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ANALYSIS OF ALTERNATIVES

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Legal name of applicants: H&R Ölwerke Schindler GmbH

H&R Chemisch-Pharmazeutische Spezialitäten GmbH (co-applicant)

Submitted by: H&R Ölwerke Schindler GmbH, on behalf of both applicants

Substance: 1,2-Dichloroethane (EC No. 203-458-1, CAS No. 107-06-2)

Use title: Industrial use as a solvent and anti-solvent of the feedstockand intermediate product streams in the combined de-waxing and de-oiling of refining of petroleum vacuumdistillates for the production of base oils and hard paraffinwaxes

Use number: 1

Copyright

©2016 H&R Ölwerke Schindler GmbH. This document is the copyright of H&R Ölwerke Schindler GmbH and is not to bereproduced or copied without its prior authority or permission.

Disclaimer

This report has been prepared by Risk & Policy Analysts Ltd, with reasonable skill, care and diligenceunder a contract to the client and in accordance with the terms and provisions of the contract. Risk& Policy Analysts Ltd will accept no responsibility towards the client and third parties in respect ofany matters outside the scope of the contract. This report has been prepared for the client and weaccept no liability for any loss or damage arising out of the provision of the report to third parties.Any such party relies on the report at their own risk.

Note

This public version of the Analysis of Alternatives includes some redacted text. The letters indicatedwithin each piece of redacted text correspond to the type of justification for confidentiality claimswhich is included as Annex 4 (Section 11) in the complete version of the document.

Table of contents

1 Summary.............................................................................................................................. 1

1.1 The Applied for Use.........................................................................................................................2

1.2 Efforts made to identify possible alternatives................................................................................3

1.3 Assessment of the feasibility and suitability of the shortlisted possible alternative .....................3

1.4 Actions needed to improve the feasibility and availability of potential alternatives.....................5

2 Analysis of substance function .............................................................................................. 7

2.1 Company overview .........................................................................................................................7

2.2 Processes and role of the substance...............................................................................................9

2.3 Technical feasibility criteria and parameters of use .....................................................................13

3 Annual tonnage .................................................................................................................. 23

3.1 Tonnage band ...............................................................................................................................23

3.2 Tonnage trends .............................................................................................................................23

4 Identification of possible alternatives.................................................................................. 25

4.1 List of possible alternatives...........................................................................................................25

4.2 Description of efforts made to identify potential alternatives.....................................................28

4.3 Screening of potential alternatives...............................................................................................36

5 Suitability and availability of possible alternatives............................................................... 43

5.1 Methyl ethyl ketone and toluene .................................................................................................43

6 Overall conclusions on suitability and availability of possible alternatives............................ 61

6.1 Summary of findings ....................................................................................................................61

6.2 Future R&D work planned by the applicants................................................................................61

7 References ......................................................................................................................... 65

8 Annex 1 – Detailed description of process unit operations ................................................... 67

8.1 Crystallisation in the presence of solvent.....................................................................................67

8.2 Filtration and filter cake washing in the presence of solvent.......................................................67

8.3 Solvent recovery section...............................................................................................................68

9 Annex 2 – Assessment of economic feasibility of MEK-Toluene ............................................ 71

9.1 Background ...................................................................................................................................71

9.2 Investment costs for the implementation of the alternative .......................................................71

9.3 Loss of past investment ................................................................................................................79

9.4 Changes in operating costs ...........................................................................................................80

9.5 Economic feasibility of MEK-Toluene in the context of competition ...........................................85

10 Annex 3 – Risk evaluation of alternative substances ............................................................ 87

10.1 Methodological approach.............................................................................................................87

10.2 Reference values (DNELs, PNECs) for EDC and the alternative ....................................................88

10.3 Exposure Assessment..................................................................................................................100

10.4 Results of the comparative exposure assessment and risk characterisation.............................103

10.5 References for Annex 3...............................................................................................................104

11 Annex 4 – Justifications for confidentiality claims.............................................................. 109

LIST OF ABBREVIATIONS

AfA Application for Authorisation

AGS Ausschuss für Gefahrstoffe

ANSES Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement etdu travail

AoA Analysis of Alternatives

ATEX ATmosphères Explosibles

ATSDR Agency for Toxic Substances and Disease Registry

BAT Best Available Techniques

BREF BAT reference documents

CMR Carcinogen-Mutagen-Reprotoxic

CoRAP Community rolling action plan

CSA Chemical Safety Assessment

CSR Chemical Safety Report

DCM Dichloromethane

DI-ME 1,2-dichloroethane-Dichloromethane

DIPE Diisopropyl ether

DMEL Derived Minimal Effect Level

DNEL Derived No Effect Level

ECB European Chemicals Bureau

ECETOC TRA ECETOC Targeted Risk Assessment tool

EDC 1,2-Dichloroethane

ERC Environmental Release Category

ESVOC SpERC European Solvents Downstream Users Group Specific Environmental ReleaseCategory

EtOH Ethanol

GC Gas chromatography

H&R AG H&R Aktiengesellschaft

H&R CPS H&R Chemisch-Pharmazeutische Spezialitäten GmbH

H&R OWS H&R Ölwerke Schindler GmbH

HPVIS High Production Volume Information System

IARC International Agency for Research on Cancer

IED Industrial Emissions Directive

IPCS International Programme on Chemical Safety

KF Karl Fischer titration

LEV Local Exhaust Ventilation

Log Kow Octanol-water partition coefficient

MEK Methyl ethyl ketone

MIBK Methyl isobutyl ketone

MPK Methyl propyl ketone

NLM U.S. National Library of Medicine

NOAEC No Observed Adverse Effect Concentration

NOEC No Observed Effect Concentration

NZ Neutralisation number

OECD Organisation for Economic Co-Operation and Development

OEL Occupational Exposure Limit

PACT-RMOA Public Activities Coordination Tool - Risk Management Option Analysis

PNEC Predicted No Effect Concentration

PPE Personal Protection Equipment

PROC Process Category

R&D Research and development

RAR Risk Assessment Report

RCR Risk Characterisation Ratio

RWE Rheinisch-Westfälisches Elektrizitätswerk AG

SCOEL Scientific Committee for Occupational Exposure Limits

SEA Socio-economic Analysis

SIDS Screening Information Dataset

STOT Specific Target Organ Toxicity

SVHC Substance of Very High Concern

TAME tert-Amyl methyl ether

TKUES ThyssenKrupp Uhde Engineering Services GmbH

TRIPS World Trade Organisation agreement on Trade-Related Aspects of IntellectualProperty Rights

WHO World Health Organization

LIST OF TABLES

Table 1-1: Summary of findings on the suitability and availability of MEK-Toluene ............................4

Table 2-1: Summary of technical feasibility criteria............................................................................13

Table 2-2: Solvent boiling point parameters for EDC and DCM affecting their distillation ................15

Table 2-3: The applicants’ key parameters for EDC use......................................................................19

Table 3-1: Quantity of EDC purchased and used by each unit (2009-2014) .......................................23

Table 4-1: Overview of European refineries using EDC for de-waxing/de-oiling ................................26

Table 4-2: Master list of potential alternatives...................................................................................27

Table 4-3: Shortlist of possible alternatives........................................................................................28

Table 4-4: Potential alternatives to EDC identified through the applicants’ R&D literature review...29

Table 4-5: Potential alternatives to EDC identified by the TKUES feasibility study commissioned bythe applicants........................................................................................................................................31

Table 4-6: Potential alternatives to EDC identified by relevant BREF Document................................32

Table 4-7: Overview of potential alternatives identified by Sequeira (1994)......................................33

Table 4-8: De-waxing processes described by Wauquier (2000).........................................................34

Table 4-9: De-waxing processes described by Lynch (2007)................................................................34

Table 4-10: De-oiling processes described by Wolfmeier et al (2012) – Ullmann’s ............................35

Table 4-11: Preferred de-waxing solvent solutions in patent literature .............................................35

Table 4-12: Screening of potential alternatives for the generation of a shortlist of possiblealternatives ...........................................................................................................................................38

Table 5-1: Identity of alternative solvents ...........................................................................................43

Table 5-2: Physicochemical properties of MEK and toluene (and comparison with EDC and DCM)...44

Table 5-3: Comparison of MEK-Toluene against the technical feasibility criteria...............................45

Table 5-4: Breakdown of costs associated with switching to alternative solvent mixture.................49

Table 5-5: Comparison of harmonised classification of EDC, DCM, MEK and toluene........................51

Table 5-6: Screening step 2: Screening of potential alternatives for hazard profile .........................52

Table 5-7: REACH registration status of MEK and toluene (and comparison to EDC and DCM) .........54

Table 5-8: Steps and time required for the theoretical conversion of the applicants’ plants to MEK-Toluene .................................................................................................................................................57

Table 1-1: Summary of suitability and availability of the MEK-Toluene alternative ..........................62

Table 6-2: Plan for continuous improvement of processes during an Authorisation review period ..64

Table 9-1: Filtering performance/operating conditions with DI-ME and MEK-Toluene.....................73

Table 9-2: Required technical changes for the theoretical implementation of MEK-Toluene and theirpractical implications ............................................................................................................................74

Table 9-3: Capacity data of specialist equipment required for the Salzbergen and Hamburg units..76

Table 9-4: Cost of plant conversion for the Salzbergen unit................................................................77

Table 9-5: Cost of plant conversion for the applicants’ units ..............................................................78

Table 9-6: Past investments by the applicants in the affected production units ................................80

Table 9-7: Overview of changes to operating costs when replacing DI-ME with MEK-Toluene .........80

Table 9-8: Energy consumption with DI-ME and MEK-Toluene..........................................................82

Table 9-9: Increase in energy consumption and associated carbon dioxide emissions in Hamburgwhen using MEK-Toluene .....................................................................................................................83

Table 10-1: PNECs for EDC – values from ECHA-CHEM compared to other assessments...................90

Table 10-2: DNELs (or DMELs) for dichloromethane from ECHA-CHEM .............................................91

Table 10-3: PNECs for toluene – values from ECHA-CHEM compared to other assessments.............94

Table 10-4: DNELs (or DMELs) for MEK from ECHA-CHEM..................................................................96

Table 10-5: PNECs for MEK – values from ECHA-CHEM (no other values available)...........................99

Table 10-6: DNELs/DMELs and PNECs used for EDC and alternative substances for the comparativerisk characterisation............................................................................................................................101

Table 10-7: Physicochemical and environmental fate properties data of alternative substances takenfrom ECHA-CHEM if not stated otherwise; ECHA, 2015a; data for EDC are from OECD (2002) ........102

Table 10-8: Result of the comparative exposure and risk characterisation, workers .......................103

Table 10-9: Result of the comparative exposure and risk characterisation, environment ...............103

LIST OF FIGURES

Figure 2-1: H&R AG corporate structure...............................................................................................8

Figure 2-2: Broad overview of operations of the applicants – Base oil production .............................9

Figure 2-3: Generic overview of operations in Salzbergen and Hamburg ..........................................10

Figure 2-4: Photographs of feedstock and products...........................................................................11

Figure 5-1: Theoretical timeline of converting one applicant unit to MEK-Toluene ..........................56

Figure 8-1: Cross-sectional view of the vacuum rotary filter..............................................................68

Figure 8-2: Overview of solvent recovery section...............................................................................69

Figure 10-1: Classification of EDC........................................................................................................89

Figure 10-2: Classification of toluene..................................................................................................91

Figure 10-3: Classification of MEK.......................................................................................................96

Important points on the identities of key stakeholders

H&R AG: H&R Aktiengesellschaft (H&R AG) is a holding company which owns (partially or wholly)several subsidiaries based around the globe which would be affected by a refused Authorisation.Among those, those more important to this analysis are the two companies who own the tworefineries that use EDC (see below).

The two refineries: at the core of H&R AG are two refineries, both located in Germany, one inHamburg and another in Salzbergen. The Hamburg refinery is owned and operated by H&R ÖlwerkeSchindler GmbH (H&R OWS), while the Salzbergen refinery is owned and operated by H&RChemisch-Pharmazeutische Spezialitäten GmbH (H&R CPS). These two companies are the applicantsfor this joint Application for Authorisation and are collectively referred to as such throughout thisdocument.

Hansen & Rosenthal Group: the Hansen & Rosenthal Group '#C#'''''''''' ''''''''' '''' '''''' '''''' '''''''' acts asselling partner directly linked to the two refineries. Four such companies are offering marketing andsales services, all based in Germany:

Hansen & Rosenthal KG Klaus Dahleke KG Tudapetrol KG H&R Wax Co.

Use number: 1 Legal name of applicants: H&R Ölwerke Schindler GmbH and H&R Chemisch-Pharmazeutische Spezialitäten GmbH

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1 Summary

The Analysis of Alternatives at a glance

1. The applicants use 1,2-dichloroethane (EDC) in a mixture with dichloromethane (DCM) as asolvent, an anti-solvent for the removal of waxes from oil raffinates and the subsequentremoval of oil from the slack waxes to obtain base oils, paraffinic waxes and a very wide rangeof specialties which are used in a variety of applications.

2. The applicants’ two refineries in Hamburg and Salzbergen have been purpose-built foroperating on the EDC-DCM (DI-ME) technology and have been using EDC since the 1960s.'#A#''''' '''''' '''''''''''''''' ''' ''''''''''''' '''''''''' '''''''''''''''''''''''''''''' ''''''''''''''''''''''''''' ''''''' '''' '''''' '''''''' ''''''''''''''''''''''''''''''''' ''' '''' '''''' '''''

3. The applicants can demonstrate a low annual EDC consumption and very high recycling rate forEDC in the current process. In addition, between 1987 and 2014, the applicants investedheavily in the minimisation of EDC losses, the improvement and modernisation of processesand the improved control of worker exposure and this will continue into the future.

4. No suitable alternative substance or technology is available to substitute EDC in the applied foruse. Only one possible alternative, the alternative solvent mixture, MEK-Toluene, has beenidentified. All other alternatives mentioned in the literature or known to industry experts areincompatible with a combined de-waxing/de-oiling operation or are not feasible for theapplicants’ feedstock and process setup or have not been proven commercially on a scalerelevant to the applicants’ operations. The applicants commissioned a detailed feasibilitystudy for the MEK-Toluene alternative to demonstrate the challenges of converting to it.

5. Substituting DI-ME with MEK-Toluene would require significant plant modifications due to thealternative’s different physicochemical properties. Its use would have significant implicationsfor energy consumption, steam use, solvent recyclability, solvent-water separation, productquality (worse oil content in slack wax and greater difficulty in achieving the desired oilcontent in hard wax) and yield. The range of products that could be manufactured would befar narrower than what can be currently achieved with the DI-ME technology. Significant plantdowntime would also be required.

6. Conversion to the alternative would be accompanied by a capital investment and downtimecost of over '#E#'''''' ''''''''''' (€100-1,000 million) and significantly increased operating costs;such worsening production economics would be prohibitive particularly against a backdrop ofincreasing global competition which has already forced several EU refineries to shut down inrecent years.

7. Although both solvent components of the alternative, MEK and toluene, are readily availableand obtaining a licence to use the technology would be straightforward, conversion of theapplicants’ three production units would require a minimum period of 12 years. Overall,although MEK-Toluene could reduce overall risks to worker’s health, it has been demonstratedto be neither suitable, nor available for the applicants’ processes and units.

The applicants will continue the monitoring of new technologies, patents and solvents, and mayundertake additional R&D work, if new technologies and solvents are identified; in addition, theapplicants are also aiming to continuously improve processes and controls, so that EDC losses andworker exposure are reduced to the extent possible and practicable.


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1.1 The Applied for Use

This is the Analysis of Alternatives (AoA) for the use of 1,2-dichloromethane (EDC) as a solvent in amixture with dichloromethane (known as “DI-ME”) for the de-waxing of base oils and the de-oiling ofslack waxes by two legal entities, H&R Ölwerke Schindler GmbH (hereafter referred to as H&R OWS)and H&R Chemisch-Pharmazeutische Spezialitäten GmbH (hereafter referred to as H&R CPS), whoare acting as joint applicants. EDC has been placed on Annex XIV on grounds of its carcinogeniceffects and as such its continued use requires a REACH Authorisation. This AoA is an essential partof an Application for Authorisation.

The feedstock for de-waxing is raffinate that contains oil fractions and wax fractions that must beseparated to yield marketable products. Initially, in de-waxing, the wax components are removedfrom the raffinate to give de-waxed base oils. The removed wax components are captured as slackwaxes, which contain significant amounts of impurity oil components. In de-oiling, the residual oilcomponents are removed from the slack waxes to give de-oiled hard paraffin waxes. The removedoil fractions are captured and are known as foots oils. EDC has two key roles, as it acts as a solvent(for oils and warm waxes) and anti-solvent (for cooled waxes), but also a third one, as a viscosity(pour point/cloud point) regulator that allows the material to flow without clogging the equipment.Without EDC, the applicants could not produce the range of base oils, waxes and other specialties(softeners, white oils) that they place on the market. The substance cannot simply be removed fromthe process without the entire DI-ME solvent mixture being replaced and the production technologybeing drastically altered.

EDC demonstrates significant advantages which any alternative would need to match:

Solubility and selectivity: EDC is a good solvent for the oil fraction, which is a liquid in theraffinate feedstock. It also has a finely tuned solubility profile with respect to the waxfraction, acting as a good solvent when warmed and a poor one—an anti-solvent—whencooled

Boiling point: EDC has a relatively low boiling point. A low boiling point is importantbecause the solvent is removed from the product streams by distillation. A high boilingpoint would mean that more energy would be required for distillation

Cloud point: EDC (with DCM) has a sufficiently low cloud point that it is fully liquid withinthe filtration temperature range

Filterability: EDC allows for minimisation of the filter area which is required for effectivefiltration

Corrosion potential: EDC is not corrosive; hydrochloric acid, a degradation product of EDC,is potentially corrosive, but in the applicants’ process, it is neutralised with sodiumhydroxide to form sodium chloride and water before any corrosion takes place

Explosion risk: the risk of explosion is extremely low with the applicants’ process Energy consumption: the process has relatively low levels of energy consumption Recycling of solvent: EDC can be continuously recycled; this ensures the quality of products

and keeps production costs low by minimising solvent waste/losses. The EDC recycling ratein the period 2009-2013 was '#A#'''''''''''''% and increased to '#A#''''''''''''''% in 2014.


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1.2 Efforts made to identify possible alternatives

The applicants have made sustained efforts to identify and develop an alternative to EDC and theirR&D work, with the explicit aim of finding an alternative to the use of EDC, started in 1999. Overthese 15+ years, a three-pronged approach has been followed by the applicants:

An extensive literature review has been undertaken Valuable business and competitor insight has been gained by participating in the

authoritative Solomon Lube Study A feasibility study on alternatives was commissioned and was undertaken by leading

industry experts, ThyssenKrupp Uhde Engineering Services GmbH (TKUES). The tasks forwhich TKUES was appointed included:

Developing a concept for finding alternative solvents for the applicants’ de-waxing/de-oiling units

Identifying, where possible and suitable, an alternative substance for EDC which canreplace this substance tonne for tonne

Investigating the advantages and disadvantages associated with alternative solvents

Establishing the changes required for the transition to an alternative solvent

Estimating the costs that would be associated with the transition to an alternativesolvent.

The feasibility study confirmed that tonne for tonne replacement of EDC cannot be carried out andthe entire DI-ME technology would need to be replaced by an alternative technology.

Through this R&D work for which the applicants have thus far invested a total of '#C#'''''''''''''''', morethan 20 potential alternative substances, mixtures and technologies have been identified. For these,a screening exercise was undertaken to establish a list of possible alternatives which can fulfil thefunction of EDC in the applied for use in the applicants’ production units. On this basis, only onealternative appears possible, the methyl ethyl ketone – toluene (MEK-Toluene) mixture (at a mixingratio of 50:50 w/w). Notably, no DI-ME unit has ever been converted to MEK-Toluene according tothe applicants’ and TKUES’ knowledge (TKUES has also been the licensor of the DI-ME technology).

1.3 Assessment of the feasibility and suitability of the shortlistedpossible alternative

The assessment of the feasibility, suitability and availability of MEK-Toluene is summarised in Table1-1. The table confirms that, in comparison to the DI-ME technology:

MEK-Toluene is not a technically feasible alternative, as it is incompatible with theapplicants’ processes, feedstock and setup, thus it fails to meet several of the identifiedtechnical feasibility criteria and its implementation would require significant modificationsto the existing units. The MEK-Toluene mixture exhibits worse selectivity towards oil/wax,higher boiling point, poorer filtration performance, higher explosion risk, significantly higherelectricity and gas consumption for both heating and cooling (i.e. a larger carbon footprint),worse oil content in slack wax and greater difficulty in achieving the desired oil content inhard wax. MEK-Toluene would also be capable of only delivering a much narrower range ofrefinery products; high-value specialties would not be possible to obtain

Use number: 1 Legal name of applicants: H&R Ölwerke Schindler GmbH and H&R Chemisch-Pharmazeutische Spezialitäten GmbH4

Table 1-1: Summary of findings on the suitability and availability of MEK-Toluene

Suitability andavailability aspects

Key findings Conclusion

Technical feasibility - Compatibility with applicants’ processes and setup: although for historical reasons, MEK-Toluene is a widely used technology, theapplicants’ de-waxing/de-oiling units have been specifically designed for the DI-ME technology and their requirements and parametersof use differ substantially from those of MEK-Toluene plants

- Performance against technical feasibility criteria: MEK-Toluene’s is technically poor and would require significant equipment andprocess modifications in order to achieve the desired product quality (hard waxes with <0.5% oil content) with regard to (a) filtration andpumping, (b) heating and cooling (including solvent recycling and associated energy costs), (c) hazard controls (increased explosion risks),and (d) maintenance Ability to generate desired products: DI-ME allows the applicants to generate a wide range of specialty productsthat are in demand across the globe as well as high quality hard waxes and microcrystalline waxes. MEK-Toluene would not allow theapplicants to maintain the existing breadth of their product portfolio

- Possibilities for improving feasibility: its physicochemical properties preclude any substantial improvement, unless the applicants’business model were to radically change, this meaning the abandonment of all those product quality and portfolio range parameterswhich are the applicants’ unique selling points vis-à-vis European and international competition

Technicallyinfeasible

Economic feasibility - Capital investment costs would be high: they have been estimated at '#E#'''''''' '''''''' ''''''''''''' '''''''' ''''''' ''''''' '''''''''''''''''''''''' '''' ''''''' ''''''''' ''''''''''''''' ''''''''''''''''''''' ''''''' '''' '''''''' ''''''''''''''' '''''' '''''''''''''''' '''''''' '''''''''' '''''' '''''''''''' ''''''''''''''''' '''''''''''''''' (range: €100-1,000 million).

- Operating costs would increase: operating costs would increase, particularly due to an increased energy cost and the cost of servicingloans. The quantified part of this cost increase is estimated at '#E#''''' '''''''' '''''''''''''' per year (range: €10-100 million per year)

- Other costs: profit margins would suffer as MEK-Toluene would generate a more narrow range of specialty products. As several MEK-Toluene units have recently closed due to fierce competition, the applicants would not be able to make a convincing case to the banks inorder to secure a loan to fund the conversion.

The above are only conservative estimates and several cost elements have not been possible to quantify, this suggesting that the real cost ofconversion could be higher

Economicallyinfeasible

Risk reductionpotential

- Hazard comparison: the substances MEK and toluene have lower toxicity and water pollution potential compared to EDC and DCM.MEK-Toluene is not accompanied by corrosion problems. On the other hand, toluene is currently under regulatory scrutiny (RMOA) andthe flash points of MEK and toluene are somewhat lower than that of EDC and DCM, although generally this should not lead toadditional explosion-proofing requirements

- Risk comparison: the alternative solvent mixture is considered to fulfil the requirement of leading to overall reduced risks, when used asan alternative to EDC

- Environmental externalities: the use of MEK-Toluene under the conditions described above would be expected to increase the energyconsumption of the process leading to an equivalent increase in CO2e releases of '#D#'''' '''''''''''''' t/y

Capable ofreducing

overall risks,if operatinghazards arecontrolled

Availability - Market availability of solvents: both MEK and toluene have been fully registered under REACH at sufficiently high tonnages- Licencing status of required technology: widely available- Implementation horizon: a theoretical minimum 12 years would be required for conversion

Not availablewithout

undue delay


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MEK-Toluene is not an economically feasible option, as it would be accompanied by veryhigh investment costs, loss through downtime, considerably increased operating costs(mainly due to increased energy consumption and loan repayments) and loss of pastinvestment. A much narrower range of refinery products would seriously undermine thefuture profitability and the applicants’ competitive position vis-à-vis competitors from boththe EU and (primarily) outside the EU. Notably, several cost elements have not beenpossible to quantify in this analysis, thus the real cost of conversion would be even higherthan shown here

MEK-Toluene is a mixture of readily available, known solvents and requires technologywhich has been licensed for years around the world. However, this alternative cannotbecome available to the applicants without undue delay. A feasibility study commissionedby the applicants has confirmed that implementation of the MEK-Toluene technology in away that (a) makes best use of the existing equipment and (b) aims to preserve the quality ofend products would require a minimum of 12 years. This time period disregards theprohibitive economics of conversion, the disadvantageous operating costs of the convertedunits and the risks that would accompany such a major construction project

MEK-Toluene could reduce worker risks in comparison to EDC; however, environmentalimpacts from the increased release of greenhouse gases (due to higher energy consumption)would increase.

Overall, MEK-Toluene cannot be considered a suitable or available alternative for the productionunits of the applicants.

1.4 Actions needed to improve the feasibility and availability ofpotential alternatives

The key shortcomings of MEK-Toluene are of a technical nature and are directly linked to thephysicochemical properties of its two solvent components. These are clearly impossible to alter. Inaddition, the inability of MEK-Toluene to deliver the full breadth of the applicants’ existing productportfolio cannot be ameliorated; MEK-Toluene is known to the sector for decades and its limitationsin the context of the applicants’ process, feedstock and setup are well-established. Therefore, evenif the implementation of this alternative could be financed, it would still remain a technicallyinfeasible alternative, unless the applicants’ business model were to radically change, with theabandonment of all those product quality and portfolio range parameters which are the applicants’unique selling points vis-à-vis European and international competition.

As regards economic feasibility and how this could be improved, the last few years have beenfinancially very challenging for the applicants and the general state of the crude oil market poses avery negative backdrop to the significant investment costs associated with the conversion of theapplicants’ production units. This AoA and particularly the accompanying Socio-economic Analysis(SEA) explain the current and foreseeable state of the market in which several less efficientEuropean refineries have recently shut down or are planning to do so soon. As MEK-Toluene isaccompanied by a prohibitive conversion cost as well as significantly worse production economics, itwould be impossible to make a convincing business case for securing the necessary bank loans whichwould be needed for funding the conversion. As a result, MEK-Toluene cannot be expected tobecome a feasible alternative in the future.


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In light of the above conclusions, during an Authorisation review period, the applicants will aim toundertake R&D work along two different directions: (a) monitoring of new technologies, patents andsolvents, including new R&D work, if new technologies and solvents are identified in order toidentify a yet unknown alternative, and (b) continuous improvement of the closed systems used inthe de-waxing/de-oiling plants, with a particular focus on minimising EDC losses and associatedworker exposure. Details of specific actions being considered are shown in Section 6.2 of this AoA.


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2 Analysis of substance function

2.1 Company overview

The applicants are affiliated companies of H&R Aktiengesellschaft (hereafter referred to as H&R AG).H&R AG is an international company that is focused on the development and manufacturing ofcrude-oil based chemical/pharmaceutical specialty products and precision plastic components. Adetailed description of the company and its subsidiaries is provided in Section 2.1.3 of the SEA andFigure 2-1 overleaf shows part of the structure of the company.

At the core of H&R AG are two refineries, both in Germany: one in Hamburg and another inSalzbergen. The Hamburg refinery is owned and operated by H&R Ölwerke Schindler GmbH (H&ROWS), while the Salzbergen refinery is owned and operated by H&R Chemisch-PharmazeutischeSpezialitäten GmbH (H&R CPS). Although their activities are highly co-ordinated to ensure maximumefficiency, with materials routinely moved from one location to the other, the refineries are, for legalreasons, owned by different companies. These two entities are the joint applicants in this jointApplication for Authorisation (AfA). In this document, the term “applicants” is used to jointly referto H&R OWS and H&R CPS.

The two applicants use EDC as a solvent, anti-solvent and a pour point/cloud point regulator in acombined de-waxing and de-oiling process. Three elements of the H&R AG business are critical tothe scope of this Analysis of Alternatives (AoA):

First, the use of EDC by H&R AG is confined to the two aforementioned refineries '#A#''''''''''''''''''''''''''''''''' '''' '''''' ''''''''''''''''' '''''''''''''' ''''''' '''''''' '''' ''''''' '''''''''''''''''''' '''''''''''''''' '''''''''''''''''''''' '''''''''''''''''''''''' ''''''' '''''''''''''''''''. None of the other units at any of the H&R AG sites around theworld are involved in any use of EDC

Second, all the products manufactured by H&R AG – as opposed to those bought and sold aspart of its trading activities — are derived from these refineries. This has significantimplications for the economic feasibility of alternatives

Third, the use of EDC is, essentially, identical across these production units. Wherenecessary, the relevant differences are explained in full with reference to the specific units.However, where no such reference is given, it can be assumed that the discussion applies, infull, to both of them.


Figure 2-1: H&R AG corporate structure


9

2.2 Processes and role of the substance

2.2.1 Overview of the process

Both refineries are processing similar raw material (Vacuum Gas Oil, Atmospheric Residue) with verysimilar main production steps (distillation, extraction, de-waxing/de-oiling and hydrofinishing). Outof the raw material-mixture more than 800 different specialty products are produced and aneffective de-waxing/de-oiling step is necessary for achieving product specifications.

The purpose of solvent de-waxing is to remove waxy components from oil products out of theextraction plants to obtain a base oil with a low pour point, see Figure 2-2.

The applicants have three de-waxing/de-oiling units. One of these units is located in Salzbergen andis called “EP”. The unit is a 2-filtration-stage process with a de-waxing stage and integrated de-oilingstage (see Figure 2-3).

Two more units are located in Hamburg. The “EP1” at the Hamburg site is a 2-filtration-stageprocess with a de-waxing and integrated de-oiling stage, and the process is similar to the Salzbergenoperation (see Figure 2-3).

At the Hamburg site there is an additional de-waxing plant called “EP2”, which is a 1-filtration-stageprocess for de-waxing only (see Figure 2-3).

The Hamburg EP1 and Salzbergen EP sites have similar processes, technical equipment and riskmanagement measures for de-waxing and de-oiling activities. Therefore, all technical descriptionsbelow and in the CSR are common for the Hamburg and Salzbergen sites (NB. the Chemical SafetyReport (CSR) also includes photographs of the plants).

The units run continuously, except for scheduled stops as required by legislation, and as described inthe applicants’ CSR.

Figure 2-2: Broad overview of operations of the applicants – Base oil production

Base oil

Waxes

De-waxing/De-oiling

Asphalt

PDA

Hydrofinishing

Extracts

FeedDistillates Extraction Raffinates

(ATM/AGO)Distillation

DAO


10

2.2.2 De-waxing and de-oiling

Step 1: De-waxing

This first filtration stage is the so called de-waxing stage. In this step, the wax is separated from thebase oil. Therefore, the raffinate has to be diluted with a selective solvent and chilled to a lowtemperature (e.g. -20 °C). By lowering the temperature the waxy components begin to crystallise.The solid waxy crystals can then be removed by filtration. Important for quality aspects and productyield is the effective washing of these crystals to remove oily components out of the filter cake.

The quality properties set by the de-waxing process include pour point of the dewaxed oil, filtrationrate and oil content of the paraffinic filter cake.

Following the separation of solvent, the oil is a base oil ready for sale or further processing (e.g.hydrofinishing). On the other hand, the produced wax is called slack wax. It contains some oilfraction (typically, 3% to 16%).

Step 2: De-oiling

The separated paraffinic fraction is not a fully de-oiled paraffinic product, because some oilycomponents still remain in the wax. To further remove these oily fractions, a second filtration stageis needed. The intermediate slack wax mix from the de-waxing stage, which is stored in a mix-vessel,is mixed with additional solvent and heated up for de-oiling. The temperature rise from the de-waxing temperature to de-oiling temperature is dependent on the feed-fraction (typically between 0and +5 °C). The lower wax fractions are melted and soft waxes and oily occlusions in the wax crystalstructure are solved. The warm slack wax/solvent mixture is then directed to a second filter stage.The process of filtering is the same as in the first filtration stage. The difference is the higherfiltration temperature. The liquid phase is the occluded oil, which is called foots oil (a soft wax). Theremaining wax is a so called hard wax. Both products contain solvent after the filtration, which isremoved in the recovery section. Each stream has its own recovery section.

Solvent Recovery (Foots Oil) Tanks Footsoil

Solvent Recovery (Hardwax)Warm up 2. Filtration

Solvent Recovery (Base Oil)

Tanks Paraffin

Tanks Baseoil

Feed Crystallisation 1. Filtration

EP Salzbergen, EP1 Hamburg (de-waxing with integrated de-oiling)

Solvent Recovery (Hardwax) Tanks SlackwaxFeed Crystallisation 1. Filtration

Solvent Recovery (Base Oil) Tanks Baseoil

EP2 Hamburg (de-waxing without integrated de-oiling)

Figure 2-3: Generic overview of operations in Salzbergen and Hamburg


11

The quality criteria in the second filtration stage include the permeability of the filter cake, and,furthermore, effective washing to remove oily components out of the filter cake, which iselementary for this process.

The produced hard waxes have very low oil content and can then be hydrofinished or sold directly tothe different industries.

A more detailed description of the steps taken during de-waxing and de-oiling is provided in Annex 1(Section 8) of this AoA.

Range of products

The basic products of the above processes are shown in Figure 2-4.

De-waxing: feedstock (raffinate, left), base oil product (middle), and slack wax (right)

Combined De-waxing and De-oiling: feedstock (raffinate, far left), base oil product (second left),hard paraffin wax (second right), foots oil (far right)

Figure 2-4: Photographs of feedstock and products


12

Within limits, key parameters of the applicants’ process can be changed during normal operation toaccommodate the different feedstock grades and generate the full range of products. The filtrationtemperature in the de-waxing unit, for example, is varied between -25 and -10 °C. Changing aparameter generates a different “run” with different tolerances and outcomes.

In total, the applicants use '#A#'''' runs (different feedstock for the de-waxing/de-oiling process, allderived from the refinery feedstock) and at least nine feedstock grades ('#A#' different cuts, plus de-asphalted oil, derived from vacuum residue) leading to more than 800 different products andspecialities.

The blend components are treated and combined—in many different permutations—to generatethe full range of the applicants’ products.

Tasks performed by EDC

EDC is not a reactant; it largely remains chemically unchanged through the process (except somedegradation during the process). Additionally, the solvent—and therefore EDC—is recovered and re-used as part of a closed system.

EDC performs essentially two roles: pour point/cloud point regulator and a solvent and anti-solventof the feedstock and intermediate product streams.

Pour point/cloud point (viscosity) regulator

The solvent is used to lower the viscosity of the product streams at various points in the process sothat the material flows through the system correctly. Without it, the solid material would clog theequipment.

Viscosity and solvation are both dependent on temperature. Typically, at lower temperatures,viscosity increases and solvation becomes harder. Therefore, the critical temperature is the lowestin the process, which occurs during the de-waxing stage of filtration. The oil rich filtrate, a mixtureof oil components and solvent, is able to move through the wax cake and the filter cloth at between-25 and -10 °C due to the solvent’s effect on viscosity.

Solvent and anti-solvent

During crystallisation, the solid wax fraction in the warm raffinate slurry is dissolved in solvent andthen cooled so that it precipitates as a more crystalline solid. The temperature range for thisprocess is -25 to 90 °C. With respect to the wax components, the solvent goes from very lowsolvating potential at the bottom of this range to very high solubilising potential at the top.

DCM is a good solvent for the wax components, while EDC is a relatively poor one, and so it istogether that they generate the required behaviour within this temperature range. Without EDC,the solution would have to be cooled to a much lower temperature before the wax componentscould crystallise. This would be problematic because of the increased energy consumption involved.In addition, DCM on its own is not technically feasible as an alternative to DI-ME (see Section 4 forfull details).


13

2.3 Technical feasibility criteria and parameters of use

2.3.1 Technical feasibility criteria

Technical feasibility criteria were derived from the parameters of use based on the applicants’ ownknowledge and through analysis of data gathered from literature searches. Given that EDC is onlyused as a solvent in a production process and does not play a role in the final products, consultationwith other actors along the supply chain was not deemed necessary. Table 2-1 summarises thecriteria with their respective thresholds (which will help establish the feasibility of any alternative),where available. The criteria are discussed in detail below the table. Notably, EDC is used in amixture with DCM. Consequently, the technical feasibility criteria referred to below are those of thesolvent mixture, not the individual substance.

Table 2-1: Summary of technical feasibility criteria

#Technicalfeasibility criterion

RelevanceTechnical requirements for theapplicants’ processesSolvent

propertyProcess safetyand efficiency

Productspecification

1Solubility andselectivity

Relevant to the product qualitycriterion of <0.5% oil in hard wax

2

Boiling point

As low aspossible (i.e.similar orlower thanDI-ME)

By comparison:EDC: 84.1 °CDCM: 39.7 °C

Specific heatcapacity

By comparison:EDC: 1.298 kJ/kgKDCM: 1.156 kJ/kgK

Latent heat ofvaporisation

By comparison:EDC: 324 kJ/kgDCM: 329 kJ/kg

3 Cloud point -25 °C or lower

4 Filterability

Need to produce products ofacceptable oil/wax content using afiltration area similar or smallerthan the currently (≤''#A#'''''' m

2in

Salzbergen and ≤'#A#''''''' m2

inHamburg)

5 Corrosion potential

Zero tolerance for solvents causingcorrosion of pipework; minimaltolerance for corrosiveness ofdegradation products

6 Explosion risk

As low aspossible.Explosionlimits needto be similarto or higherthan DI-ME

By comparison: gaslower explosionlimit: 6.2%-13%(EDC-DCM); gasupper exposurelimit: 16%-22%(EDC-DCM)

7Energyconsumption

Similar to or lower than DI-ME tominimise impact on productioneconomics


14

Table 2-1: Summary of technical feasibility criteria

#Technicalfeasibility criterion

RelevanceTechnical requirements for theapplicants’ processesSolvent

propertyProcess safetyand efficiency

Productspecification

8

Slack wax oilcontent

6-8% or less

Hard paraffin waxoil content

<0.5%

9Production of asufficiently widerange of specialties

An alternative should ideallygenerate a wide range of highlymarketable specialties '#A#'''''''''''''''''''''''' '''''' ''''''''' ''''' ''''''' '''''''''''''''''''''''''''''''''''''''''' '''''''''''''' ''' '''''''''''''''''''''''

Technical feasibility criterion 1: Solubility and selectivity

Importance of the criterion

The solvent must be able to solvate the oil fraction well within the process temperature of -25 °C to90°C. If the solvent is not a good solvent, it forms a two-phase emulsion with the oil fraction, whichlowers the performance of the system.

In addition, the solvent must have a precise solubility profile with respect to the wax fraction, actingas a good solvent when warmed and a poor one—an anti-solvent—at or near ambient temperature.The EDC component should facilitate the anti-solvent behaviour by being a poorer solvent than DCMwith respect to the wax fraction.

Technical requirements of the applicants’ processes

An alternative solvent must behave as described above to the extent that the waxes can berecovered from the solution effectively so that the oil levels in hard wax are less than 0.5%.

Technical feasibility criterion 2: Boiling point, specific heat capacity and latent heat ofvaporisation


The boiling point is the temperature above which a liquid spontaneously changes to a gas. Thespecific heat capacity of a material is, in simple terms, the energy required to raise the temperatureof that system. For example, the specific heat capacity of water at ambient temperature is about 4kJ kg-1 K-1. This means that 4 kJ of energy is required to raise the temperature of 1 kg of water by 1 K(or 1 °C). The latent heat of vaporisation is the energy required for the liquid-to-gas phase change.For example, the latent heat of vaporisation of water is about 40 kJ/mol at ambient pressure. Thismeans that 40 kJ of energy is required to turn 1 mol of water from a liquid into a gas.

The solvent is removed from the product streams by distillation and as such all three—boiling point,specific heat capacity and latent heat of vaporisation—should be low. The higher they are the moreenergy is required to perform the distillation.


15


Table 2-2 gives the relevant data for EDC and DCM. An alternative should ideally have values as lowas possible, i.e. similar ow lower than the values of the DI-ME mixture.

Technical feasibility criterion 3: Cloud point


The cloud point (also known as the congealing or crystallisation point) is the temperature belowwhich a material in liquid form will spontaneously form solid particles. In most systems, hysteresis inthe phase change profile means that the cloud point is slightly lower than the melting point, which isto say that a liquid can usually be cooled below its melting point before any precipitation occurs.The solvent should have a sufficiently low cloud point to be able to fully transform into a liquid at thefiltration temperature.


The filtration temperature in the de-waxing unit varies between -26 and -10 °C. Therefore, the cloudpoint for the solvent should be below -26 °C.

Technical feasibility criterion 4: Filterability


A solvent of good filterability requires a smaller filter area and therefore fewer/smaller rotary drumfilters thus limiting investment and operating costs and ensuring speedier processing.


'#A#'''''' ''''''''''''''''''' ''''''''' ''''''' '''''''' ''''''''''''''''' ''''''''''''' '''''''''''''''''''' ''''''''''''''''''' ''''' '''''''''''''''''' ''''''' ''''''''' '''''''''''''' ''''' '''''''' ''''''' ''''''' ''''''' ''''''''' ''''' ''''''''' ''''' '''''''' '''''''' '''''''''' ''' ''''''''' '''''''''' '''''''''' ''' ''''''' '''''

'#A#''' '''''''''''''''''''' ''''''' ''''''' '''''''' ''''''' ''' ''''''''' ''''''''' '''''''' '''' ''''''' ''''''' ''''''' ''''' ''''''' ''''''' ''''''' '''''''' '''''''''' '''''''''''''' ''''''' '''''' ''''''''' '''''''' '''''''''''''''''''''' ''''''''' '''''''' ''' ''''''' ''''''' '''''''''' ''''''''' The grant total filter area acrossall relevant operations of the applicants is '#A#'''''' m2.

A technically feasible alternative would require a similar or smaller filtration area.

Table 2-2: Solvent boiling point parameters for EDC and DCM affecting their distillation

SubstanceBoiling point

(°C)Specific heat capacity

(kJ kg-1

K-1

at 20°C)Latent heat of vaporisation

(kJ/kg)

EDC 84.1 1.30 324

DCM 39.7 1.16 329


16

Technical feasibility criterion 5: Corrosion potential


The solvent should not corrode the equipment, either directly or via its degradation products.Corrosion would lead to increased risk to human health resulting from two impacts. First, therewould be a greater risk of leaks at the plant. Second, the equipment would need to be repaired orreplaced more frequently. Both of these effects would make worker exposure to the solvent morelikely.

Neither EDC nor DCM are corrosive. Hydrochloric acid, a degradation product of EDC, is corrosive,but in the applicants’ process it is neutralised with sodium hydroxide at H&R OWS’s plant and amixture of ammonium derivatives at H&R CPS’ plant to form sodium chloride and water before anycorrosion takes place.


There is a clear relationship between corrosion potential and risk to worker health. Any corrosion ofthe pipework or equipment dramatically increases the likelihood of solvent leakage and workerexposure. As such, there must be essentially no corrosion of pipework or equipment by the solventor its degradation products. Given the high volumes and that the process is run continuously, 365days per year, 24 hours per day; this implies no corrosive properties being tolerated. Some potentialfor corrosion associated with the degradation products might be tolerated if those products formvery slowly and can be monitored and removed easily—as is the case for the current solvent.

Technical feasibility criterion 6: Explosion risk


The applicants’ process currently presents very low explosion risk. DCM is a non-flammable solvent(with no flashpoint and ignition energy 10,000 times higher than most solvents)1. This helps mitigatethe flammability of EDC, thereby helping to lower the explosion risk associated with the process.This needs to be maintained if the solvent is to be replaced. An increase in explosion risk wouldrequire changes to existing equipment and processes to ensure that the risk is adequately mitigated.


The gas lower explosion limit for EDC is 6.2% (by volume in air) and 13% for DCM. The gas upperexposure limit is 16% for EDC and 22% for DCM. Alternative solvents should ideally have explosionlimits similar to or higher than those of EDC and DCM.

1http://www.echa.europa.eu/web/guest/information-on-chemicals/registered-substances, accessed on 19February 2015.


17

Technical feasibility criterion 7: Energy consumption


The process should have low levels of energy consumption; higher energy consumption would implyhigher costs, which the business might not be able to absorb.


Ideally, an alternative solvent mixture should lead to similar or lower energy consumption levels orelse manufacturing costs would increase.

Technical feasibility criterion 8: Product impurity profile


Base oil wax content: the wax contents of the de-waxed base oils should be low to ensure that theend use base oils have low pour points. The pour point is the temperature below which the oil is tooviscous to flow. A base oil used, for example, for lubricating an automotive engine will continue tofunction correctly in low temperature climates if it has a sufficiently low pour point.

Slack wax oil content: the applicants use the majority of the slack waxes generated during de-waxing as the feedstock for the de-oiling unit. The oil contents must therefore be sufficiently low tobe compatible with the process. '#A#''' '''''''''''''''' '''''' ''''''''''''''''' '''''''''' '''''''''' '''''''''' '''''''''''' ''''''''' ''''''''''''''''''''' '''''''''''''''' '''''''''''''''' ''''''' ''''''''''''''''''''' ''''''' ''''''''''''''' ''''''''''''''''''' This means the oil contents mustalso be sufficiently low to satisfy market expectations for speciality slack waxes.

Hard paraffin wax oil content: the oil contents of the de-oiled hard paraffin waxes should be low toensure that the end use paraffin waxes are fit for purpose.


For base oils, there is a limit for the wax in oil. If there are certain paraffin molecules in a base oiland the oil is cooled down (e.g. -12 °C), the oil gets cloudy. However, the wax content is notmeasured directly.

On the other hand, the oil content in slack wax should be as low as possible, practically, <12% inorder to proceed to the de-oiling stage, where the de-oiling of the slack wax can result in an oilcontent in hard wax of <0.5%. This oil content in hard wax is a quality criterion. Only when an oilcontent of <0.5% is achieved, can the product be called a hard wax.

If the oil content of the slack wax is higher than 12%, it is impossible for the applicants’ feedstockand refinery setup to reach oil contents in the hard wax lower than 0.5%.

The applicants currently achieve an oil content of 6-8% in slack wax; therefore it is feasible to obtainan oil content of <0.5% in hard wax. Any alternative should be able to achieve oil content below thislevel, as this is a fundamental product quality criterion.


18

Technical feasibility criterion 9: Production of a sufficiently wide range of specialties


The DI-ME technology allows the applicants to manufacture a very wide range of highly marketable,high-value specialties in addition to base oils and waxes, such as softeners and white oils. Thismakes the applicants considerably different to their direct competitors and H&R AG has a leadingposition globally as a supplier of such specialties.

Section 2.2.2 of the SEA explains that the applicants are expected to benefit from the gradualwithdrawal of the big oil companies from the crude-oil-based specialty products business. InWestern Europe alone, the Group I refineries' generating capacity could drop by around one-fifthover the next two years or so2. By contrast, the applicants’ refineries can continue to provide theseproducts and the fact that a higher share of their capacity is devoted to specialty products than tolubricants would mean that they would have another advantage over the remaining Group Irefineries. Ability to generate a range of specialties is fundamental to the applicants’ futurecompetitive position.


'#I#'''''''''''''''' '''' ''''''''''''''''''''' '''''''''''''''''''' ''''''''''''''' '''' ''''''' ''''''''''''''''''''' ''''''''''' ''''''''''''''''' ''''''''''''''''' '''''''''''''''''''''''''''''''' '''''''''''''''''''' '''''''' '''''''' ''''''' ''''''''''''''''''''''' '''''''''''''''''''' ''''''''''''''' '''''''''''''' on average, theapplicants’ refineries production consists of '#A#'''''% by volume of specialties. A feasible alternativeshould be able to achieve a similar breakdown of refinery products.

2The applicants’ refineries belong to the Group I base oil refineries. Groups I to III are refined base oils,meaning that they are produced from the refining of crude oil. Group IV oils are synthetic base oils in thatthey are produced by chemical modification (also see discussion in Section 2.2.2 of the SEA). The last fewyears have been particularly challenging for refined Group I base oil producers. Several refineries in the EUand globally have ceased or are planning to cease operations, as shown in Table 2-9 of the SEA.


19

2.3.2 Summary of parameters of EDC use

The key parameters of for EDC use are summarised in Table 2-3. These include the role of EDC, itscritical properties and the conditions under which it is used.

Table 2-3: The applicants’ key parameters for EDC use

Parameter Description

Tasks performed bythe substance

EDC acts as:- Pour point/cloud point (viscosity) regulator- Solvent and anti-solvent:EDC is not a reactant; it largely remains chemically unchanged through the process(except for some degradation) within a closed system

Physical form of theproduct

Liquid; used as 100% wt. EDC. Specifications:- Density of EDC at 20 °C: 1,250 - 1,260 g/mL- Water content (KF): <300ppm- Boiling point (DIN 51751): 81-85 °C (84.1 °C for pure EDC)- Purity (GC): >99.5%- Content on higher hydro carbons: <0.1%- Free HC: < 0.005%- Acid number (NZ): <0.1%- Cloud point: < -26 °C

Concentration of thesubstance in theproduct

Used in a mixture with DCM, '#B#''''''''' by weight. EDC content in the end oil/wax-product is below 5ppm (detection limit)

Critical properties andquality criteria thesubstance must fulfil

Criterion Importance Technicalrequirements

Solubility andselectivity

EDC (with DCM) is a good solvent for the oilfraction, which is a liquid in the raffinatefeedstock. It also has a finely tuned solubilityprofile with respect to the wax fraction, actingas a good solvent when warmed and a poorone—an anti-solvent—when cooled

An alternative hasto show similar orbetter behaviourregarding therecovery of waxes

Boiling point,specific heatcapacity andlatent heat ofvaporisation

These are all relatively low for EDC (withDCM), which is important because it isremoved from the product streams bydistillation. If the values were higher, moreenergy would be required for distillation

As low as possible,i.e. similar orlower to DI-ME

Cloud point EDC (with DCM) has a sufficiently low cloudpoint that it is fully liquid within the filtrationtemperature range

-26 °C or lower

Filterability Filtration needs to use the smallest possiblefilter area. The current area is '#A#'''''' m

2

(total)

Alternative shouldrequire similar orsmaller thancurrent filtrationarea ('#A#''''''' m

2)


20



Corrosionpotential

The solvent does not corrode the equipment,neither directly or via its degradationproducts. Neither EDC nor DCM is corrosive.Hydrochloric acid, a degradation product, ispotentially corrosive, but in the applicantsprocess it is neutralised with sodiumhydroxide to form sodium chloride and waterbefore any corrosion takes place

Zero tolerance forsolvents causingcorrosion ofpipework

Frequency ofsubstance use andusage quantities

Continuous use by recycling of solvent; only solvent losses are periodicallyreplenished

Process andperformanceconstraintsconcerning the use ofthe substance

Constraint Importance

Liquid at lowtemperature

See cloud point above (-26 °C)

Explosion risk The risk of explosion is extremely low with the applicants’ process.A higher risk of explosion would imply a higher risk to human healthor higher costs associated with risk management. The gas lowerexplosion limit for EDC is 6.2% (by volume in air) and 13% for DCM.The gas upper exposure limit is 16% for EDC and 22% for DCM.Alternative solvents should ideally have explosion limits similar to orhigher than those of EDC and DCM

Continuousprocess

The de-waxing and de-oiling plants work continuously, 365 days peryear, 24 hours per day. Occasionally, maintenance stops do takeplace and there are different maintenance strategies. With a viewto equipment reliability, there are options for general maintenancewithin 2 to 5 years according to German regulations. On average,the maintenance duration is about 4 days a year

Energyconsumption

The process has relatively low levels of energy consumption. Higherlevels of energy consumption would imply higher costs, which couldnot be absorbed by the business

Recycling ofsolvent

Continuous solvent recycling needs to be maintained to ensure thequality of products and economics that are favourable to theproduction process (by minimising solvent waste/losses)

Conditions underwhich the use of thesubstance could beeliminated

The substance is not associated with any processes that could be altered in order toeliminate or limit the use of EDC. If EDC is removed from the process, it should bereplaced by an alternative solvent system for the process to continue. Replacementby a single solvent (that would theoretically be used alongside DCM or on its own) isnot possible

Customerrequirementsassociated with theuse of the substance

Through the use of EDC as a solvent (in combination with DCM), the applicants areable to produce base oils, slack waxes and hard paraffin waxes with low levels ofimpurities (waxes and oils, respectively) which meet customer requirements, asshown below

Product Impurity content

Oil content in slack waxes 6-8% or less

Oil content in hard paraffin waxes <0.5%


21



Industry sector andlegal requirementsfor technicalacceptability thatmust be met

End products that depend on the applicants’ products are regulated under a range ofdifferent legislative instruments in various sectors. The substitution of DI-ME with anew solvent must interfere with the ability of the end products of customers to meetexisting legal requirements. Examples of legislation of relevance are given below.Food contact: end use paraffin waxes marketed by the applicants are used inmaterials that come into contact with food, for example, food packaging, and as suchconform to requirements imposed by legislation covering such materials (Regulation(EC) No 1935/2004 on materials and articles intended to come into contact with food;Commission Directive 2007/42/EC relating to materials and articles made ofregenerated cellulose film intended to come into contact with foodstuffs).Hydrotreating is needed for the food grade productsPharmaceuticals: European Pharmacopoeia includes monographs on hard paraffin,white soft paraffin, yellow soft paraffin, light liquid paraffin and liquid paraffin. Also,Regulation (EC) No 726/2004 and Directive 2001/83/EC, relating to medicinalproducts for human use, prescribe that medicines placed on the market need to havea Marketing Authorisation; a change in their formulation would require a variation tothe Marketing AuthorisationCosmetics: mineral hydrocarbons may be used as raw material for cosmeticproducts, which are likely to be ingested in a significant manner (oral and lip care).Class I white mineral oils (like the applicants’ products) are allowed for use but Class IIand Class III are not permitted to be used in lip care products.Plant protection products: paraffin oils may be used as an active substance in suchproducts. Their manufacturers have to register them at the national level inaccordance with Regulation (EC) 1107/2009


22


23

3 Annual tonnage

3.1 Tonnage band

3.1.1 Tonnage of EDC consumed

Confidential annual tonnage: '#B#'''' ''''''''''''''' '''''' ''''''''' '''''''''''''''''''' '''''' '''''' '''' '''''''' ''''''''''' '''''''''''''''''''''''''''' '''' '''''' ''''''''''''' ''''''''''''''''''''''' ''''''' ''''''''' '''' ''''''''''''' '''''''''' ''''''''''''''''''' '''' ''''''''''' '''' '''''''''' '''''''''''''''' '''''''''''''''''''''''' '''''''' '''' ''''''''''''''''' '''' ''''''''''''''' '''' ''''' ''''' '''''' ''''' '''''' ''''''''''''''''' '''''''''''''''''''''' ''''''' '''''''''''' '''''' ''''''' '''''''

Annual tonnage band: 10-100 tonnes per year.

The quantity of EDC in circulation at each unit during normal operation is shown in Table 3-1. Thetable confirms that the applicants run an extremely efficient recycling operation with a minutepercentage of EDC lost and replenished each year. It can be confirmed that EDC losses havegradually been reducing over the last 5 years. For Salzbergen in particular, EDC losses in 2014 (as a%) are 30 times lower than in 2009.

3.2 Tonnage trends

During the period 2009-2013, the applicants experienced a significant decrease in the consumptionof ‘fresh’ EDC, of more than 25%. The reason for this decrease is continuous process improvementsaimed at minimising the losses of EDC from the production process. More specifically, the applicantshave successfully established an excess gas recycling and cleaning technology.

In the foreseeable future, the applicants do not expect to see any significant change in the amountof EDC consumed, as losses cannot be eliminated for two key reasons: firstly, there are regularturnarounds of the process units, and this cannot be avoided, as they are required by legislation.The applicants are required to maintain their units at regular intervals; turnaround stops every 5years (maximum) by law. Secondly, EDC decomposes in the production units, as described earlier.

Table 3-1: Quantity of EDC purchased and used by each unit (2009-2014)

Date

H&R OWS H&R CPS

EDC recyclingEDC

purchaseEDC

recyclingratio

EDClosses

EDC recyclingEDC

purchaseEDC

recyclingratio

EDClosses

t/y t/h t/y t/y t/h t/y

Averagefor2009-2013

'#B# allTable 3-

1''''''''''''''''''

''''''' ''''''' ''''''''''''''''' '''''''''''''' '''''''''''''' ''''''' ''''''''' '''''''''''''''' ''''''''''''''

2014 '''''''''''''''' ''''''' ''''' ''''''''''''''' ''''''''''''''' '''''''''''''''' '''''''' ''' '''''''''''''''''''' '''''''''''''''''


24


25

4 Identification of possible alternatives

4.1 List of possible alternatives

4.1.1 Applicants’ history of EDC use

Applicants’ knowledge of alternatives and alternative technologies

The use of EDC in the production of base oils and slack waxes/hard waxes goes back several decades,both for H&R and other companies. Importantly, the applicants are not engineering or licensingcompanies and only use technology that is licensed from third parties.

By way of a historical background to the applicants’ use of EDC (in a mixture with DCM), theapplicants have been using the ‘Edeleanu’ (most recently known as the Thyssen Krupp Uhde) EDCprocess since the 1960s/1970s and are very satisfied with its performance. As a result, theapplicants have had no need or incentive to find a newer or better performing solvent mixture,although consistent efforts have been made towards the improvement of the controls on EDCreleases and exposure, by optimisation of work routines and training of the operators andchanges/improvements to the units.

'#A#'''''''''''''''''''''''''' ''''''' ''''''''''''''''''' ''''' ''''''''' '''''''''' '''''''''''''''''''' ''''''''' '''''''''''''''''' ''''''''''''''''''''''''' ''''''''''''''''''''''' '''''''''''' '''''''''''''' ''''''' ''''''' '''' ''' '''''''''''''' '''''''''''''' ''''''''''''''''''' ''''''''''''' ''''''''' '''''''''''' ''''''' ''''''''''''''''''''''' ''''''''''''' '''' '''''''''''''''''''''''''''' '''' '''''' '''''''''''' '''''' ''''''' '''''''''''''''''' '''''''' ''''''''''''''''''''''''' ''''''''''''''''''''''''''''''''''''''''''''''''' '''''''' '''''''' ''''''' ''''''' ''''''''''''''' ''''''''''''''''''''' '''''''' ''''''' ''''''''''''''''''''' '''''' '''''''' ''''''''''''''''''''''''''''''' ''''''' '''''''' ''''''''' ''''''''''''''''''''' ''''''' ''''''''''''' '''''''''''''''''''''''''''''''''' '''''''''' ''' ''' ''''''''''''''''''' '''' ''''''''' ''''''''''''''' '''''''''''''''' '''''''' '''''''''' '''''''''''''''' '''''' '''''''''''''' ''''''''''''''''''' ''''''' '''''' '''''''''''''''' '''''''''''' '''' ''''''' ''''''''''''''''''''''''''''' ''''''''' ''''' '''''''''''' '''' '''''''''''' ''''''''''''''''''''''' ''''' ''''''' ''''''''''''''''''''''''' ''''''''''''' '''''''''''''''' ''

H&R is also working with some partner refineries worldwide; the vast majority of these refineries areusing the MEK-Toluene process, which generates products of a poorer quality. '#I#''''''' '''''''' '''''''''''''''''''''''''''''''' ''' ''''''''' ''' ''''''''''''''''''' ''''''''''''''''''' ''''''''''''''' '''''''''''''' '''''''''' '''''''''' ''''''''' '''' ''''''''' '''''' '''''''' ''''''''''''''''''' ''''''''''''' ''''''' ''''''''''' ''''' ''''''' ''''''''''''''''''' '''''''''''''''

History of licensing of the EDC solvent de-waxing/de-oiling process

Edeleanu GmbH was founded in 1930 and was later acquired by the Deutsche Erdöl AG (DEA).Edeleanu GmbH invented the EDC de-waxing/de-oiling process and licensed the process in manyEuropean refineries; Edeleanu GmbH was not large enough to compete against other licensesworldwide, their main market was Europe (especially Germany, the UK and Eastern Europe).Nevertheless, as the process was (and still is) technically more attractive to many base oil/waxproducers in comparison to the MEK-Toluene process, Edeleanu GmbH was able to convinceEuropean refiners to opt for the EDC license instead of the Shell or Texaco MEK-Toluene licenses.Accordingly, most of the Edeleanu GmbH EDC units were built during the period 1950-1970.

However, things gradually changed. In 1966, Deutsche Texaco acquired DEA and, in 1988, RWE AGtook over Deutsche Texaco. Eventually, in 2000 RWE made the decision to stop licensing the EDC


26

license. Instead, RWE (later Uhde, ThyssenKrupp Uhde, and then ThyssenKrupp Uhde EngineeringServices GmbH (TKUES)) used the Texaco license for the MEK-Toluene process.

Thus, while the licensing of what was known as the Edeleanu process (DI-ME solvent de-waxing andde-oiling) stopped, the main competitors, Shell and Texaco, have been licensing the MEK-Tolueneprocess for decades across the world. This has meant that the majority of units for de-waxing andde-oiling are, on a global scale, MEK-Toluene units.

Table 4-1 summarises information available to the applicants regarding the use of EDC in Europe inoperations similar to those covered by the present AoA. The table shows that the use of EDC by theapplicants dates back to the 1960s and confirms that, after the early 1980s, no DI-ME unit wasinstalled in Europe. To the applicants’ knowledge none of these units were converted to MEK-Toluene after their shutdown.

Table 4-1: Overview of European refineries using EDC for de-waxing/de-oiling

Company Plant location Operation Year built Shut down

Shell, formerly Texaco Hamburg, Germany DI-ME de-waxing 1950 Yes

Shell, formerly Texaco Hamburg, Germany DI-ME de-oiling 1966 Yes

H&R AG, OWS Hamburg, Germany DI-ME de-waxing 1960

H&R AG, OWS Hamburg, Germany DI-ME de-oiling 1960

H&R AG, CPS Salzbergen, Germany DI-ME de-waxing 1964

H&R AG, CPS Salzbergen, Germany DI-ME de-oiling 1964

Grupa LOTOS S.A. Gdansk, Poland DI-ME de-waxing 1972

Sasol, formerly ARCO Hamburg, Germany DI spray de-oiling 1960

Sasol, formerly Schümann Hamburg, Germany DI spray de-oiling 1980

Rafinerija Ulja Modrica, Bosnia-Herzegovina DI-ME de-waxing 1981 Uncertain*

Rafinerija Ulja Modrica, Bosnia-Herzegovina DI-ME de-oiling 1981 Uncertain*

BP / (Burmah Oil) Ellesmere Port, UK DI-ME de-waxing 1969 Yes

BP / (Burmah Oil) Ellesmere Port, UK DI-ME de-oiling 1969 Yes

BP Llandarcy, UK DI-ME de-waxing 1970 Yes

Source: ThyssenKrupp Industrial Solutions (TKUES) feasibility study commissioned by the applicants* the plant was severely damaged during the Civil War in Yugoslavia and restarted production in 1996, whilethe restoration of the facilities for base oils and paraffin wax production started in 2008. It is unclear whichtechnology is currently used by this company

4.1.2 Master list of potential alternatives and shortlist of possiblealternatives

Table 4-2 shows the complete list of potential alternatives considered as part of this AoA. Thenumbering of the alternatives is maintained throughout Section 4 of this AoA, for consistency andeasy reference. It is worth noting the widely known fact that better solvent-chilling de-waxingresults can be achieved if mixtures of solvents instead of single solvents are used; therefore, two-solvent systems are currently the most widely used as de-waxing solvent systems.


27

Table 4-2: Master list of potential alternatives

# Name EC # CAS # Source

Solvents and solvent-based systems

1 Acetone-Benzene 200-662-2200-753-7

67-64-171-43-2

Literature (Lynch, 2007) (Sequeira, 1994)(Wauquier, 2000)

2 Acetone-Dichloromethane 200-662-2200-838-9

67-64-175-09-2

Patents (West, 1978)

3 Acetone-Propene 200-662-2204-062-1

67-64-1115-07-1

Applicants’ R&D; Literature (Sequeira, 1994);Patents (Walker, 1970) (Biribauer, et al.,1971) (Gould, 1973) (Eagen, et al., 1973)

4 Acetone-tert-Amyl methylether

200-662-2213-611-4

67-64-1994-05-8

Applicants’ R&D

5 Acetone-Toluene 200-662-2203-625-9

67-64-1108-88-3

Applicants’ R&D

6 Benzene 200-753-7 71-43-2 Literature (Wolfmeier, et al., 2012)

7 Benzene-Toluene 200-753-7203-625-9

71-43-2108-88-3

Literature (Wolfmeier, et al., 2012)

8 Dichloromethane 200-838-9 75-09-2 Literature (Wauquier, 2000)

9 Diisopropyl ether-Methylethyl ketone

203-560-6201-159-0

108-20-378-93-3

Applicants’ R&D

10 Ethanol-Methyl tert-butylether

200-578-6216-653-1

64-17-51634-04-4

Applicants’ R&D

11 Methyl ethyl ketone 201-159-0 78-93-3 Literature (Sequeira, 1994)

12 Methyl ethyl ketone-Dichloromethane

201-159-0200-838-9

78-93-375-09-2

Patents (West, 1978)

13 Methyl ethyl ketone-Toluene

201-159-0203-625-9

78-93-3203-625-9

Applicants’ R&D; Literature ((Wolfmeier, et al.,2012) (Sequeira, 1994)

14 Methyl ethyl ketone-Methyl isobutyl ketone

201-159-0203-550-1

78-93-3108-10-1

Applicants’ R&D; Literature (EIPPCB, 2015)(Sequeira, 1994)

15 Methyl isobutyl ketone 203-550-1 108-10-1 Applicants’ R&D; Literature (Sequeira, 1994)

16 Propane 200-827-9 74-98-6 Literature (EIPPCB, 2015) (Wolfmeier, et al.,2012) (Sequeira, 1994); Patents (DeKraker,1993)

17 Sulphur dioxide-Benzene 231-195-2200-753-7

7446-09-571-43-2

Literature (Lynch, 2007)

18 Trichloroethylene 201-61-04 79-01-6 Literature (Wauquier, 2000)

19 Urea 200-315-5 57-13-6 Applicants’ R&D; Literature (Sequeira, 1994)

Solventless systems/processes

20 Cold settling N/A N/A Literature (Lynch, 2007)

21 Catalytic de-waxing N/A N/A Literature (Wolfmeier, et al., 2012) (Sequeira,1994)

22 Static (fractional)crystallisation

N/A N/A Literature (Jans & Stepanski, 1999)

23 Wax sweating N/A N/A Literature (Wolfmeier, et al., 2012) (Sequeira,1994)

The potential alternatives on the complete list were screened against a range of criteria, essentiallyavailability, hazard profile and technical feasibility, to develop a shortlist of possible alternatives.Table 4-3 shows this shortlist which comprises one alternative, the widely-used solvent combinationof MEK-Toluene.


28

Table 4-3: Shortlist of possible alternatives

List # Name EC # CAS #

13 Methyl ethyl ketone-Toluene201-159-0203-625-9

78-93-3203-625-9

4.2 Description of efforts made to identify potential alternatives

4.2.1 Research and development by the applicants aimed at identifyingalternatives for EDC

The applicants have made sustained efforts to identify or develop an alternative to EDC and theirR&D work, with the explicit aim of finding an alternative to the use of EDC, started in 1999. Overthese 15+ years, a three-pronged approach has been followed:

The applicants undertook an extensive literature review with the aim of identifyingtechnically feasible alternatives

Authoritative sources of information have been consulted. The applicants have participatedin the Solomon Lube Study

The applicants hired leading industry experts to provide an in-depth analysis of commerciallyviable alternatives for the “DI-ME” method. This was in the form of a feasibility study.

These elements of R&D are further elaborated below. Thus far, the applicants have invested a totalof '#C#''''''''''''''' in its external R&D and substantial internal efforts to identify and develop analternative to EDC.

Literature review

The literature review started in 1999 and has been maintained throughout this period with a reviewof patent literature and other scientific publications but also participation in relevant fora such asthe development of the IPPC BREF Document for the mineral oil refining industry and natural gasplants.

The outcome of this review has been a comprehensive list of potential solvent systems accompaniedby a review of their commercial status and feasibility of implementation. This is presented here asTable 4-4.

The applicants note that MEK-Toluene represents >95% of all global known solvent de-waxing/de-oiling units (expressed as a percentage of the total number of units).


29

Table 4-4: Potential alternatives to EDC identified through the applicants’ R&D literature review

#

Commonname ofsolventsystem

Solvents used

Applicability

Commercial status NotesDe-waxing De-oiling


- DI-ME EDC, DCM Proven industrially Current

13 MEK-TolueneMethyl ethyl ketoneToluene

Proven industrially

14 MEK-MIBKMethyl ethyl ketoneMethyl isobutylketone

No industrial

application knownOnly at lab

scale

4DMK(acetone)-TAME

Acetonetert- Amyl methylether

No industrial


scale

15 MIBKMethyl isobutylketone

No industrial


scale

9 DIPE-MEKDiisopropyl etherMethyl ethyl ketone

No industrial


scale

10 EtOH-MTBEMethyl tert-butyletherEthanol

No industrial


scale

5 ARTAcetoneToluene

?? ??No industrial


scale

16 Propane Propane Proven industrially

3Acetone-Propene

AcetonePropene

?? ??No industrial


scale

19 Urea

Often in combinationwith alcohols,ketones andchlorinatedhydrocarbons

?? ?? Proven industriallyVery old

technology

Solventless systems

21 Catalytic de-waxing Proven industriallyCannotproduceparaffins

23 Wax sweating Proven industrially

Cannotproduce base

oilsOnly forfraction

below N200*

Source: Applicants’ data* N200 is It is a viscosity grade. It means the base oil has a viscosity of 200 SUS at 100°F (US), ca. 45mm²/sec at40°C (Rest of World)


30

Solomon Lube Study

According to the website of Solomon Associates, the Solomon Lube Study has been designed to“assist (your) company in comprehending the activities and trends in today’s refining industry, makeyou aware of the status of your refinery in all key performance areas, and provide valuableinformation on which you can base your performance improvement efforts. Our most recentlycompleted analysis represented more than half the base oil refining capacity worldwide”3.

The participation of a refinery in the study allows access to the key findings, namely (SolomonAssociates, 2012):

A report that includes an assessment of industry trends and insights, supported by studydata

Data tables include calculation worksheets for each metric, performance rankings,aggregated peer group results, detailed gap analyses, and historical trend results

One presentation to be given at a site of the participant's choosing.

By contributing to the study, the applicants have been able to benchmark their practices againstthose of competitors and confirm their prior knowledge of the favourable performance of the DI-MEtechnology when compared with the MEK-Toluene technology that is widely used around the globe.

2014 EDC Substitution Feasibility Study

The applicants contracted ThyssenKrupp Uhde Engineering Services GmbH (TKUES) (nowamalgamated into ThyssenKrupp Industrial Solutions) in 2014 to undertake an exhaustive analysis ofthe possibilities for substitution of EDC and the feasibility of replacing EDC with one or more from alist of shortlisted alternatives. TKUES is the former licensor for the applicants’ de-waxing and de-oiling units; the company licensed DI-ME in the past and it now licenses MEK-Toluene units.

By way of background, with more than 2,000 plants to its name, TKUES is one of the world’s leadingengineering companies in the design and construction of chemical, refining and other industrialplants (ThyssenKrupp Uhde, 2015). As a subsidiary of ThyssenKrupp Uhde GmbH, TKUES focuses onmetallurgy, power plant engineering, petroleum processing and services for the chemical andpetrochemical industry. In these main business areas TKUES offers tailored solutions and premiumservices in terms of revamps, modernisations, expansions, optimisations and both full and partreplacements for plants in fields such as output optimisation, compliance with environmentalstandards and enhancing the cost-effectiveness and productivity of industrial facilities(ThyssenKrupp, 2013).

As described earlier, the applicants’ de-waxing and de-oiling units were built in the early 1960s byEdeleanu GmbH (later Uhde GmbH); therefore, TKUES is familiar with the capabilities and needs ofthe plants in question. Since then, the applicants’ plants have been modified and debottleneckedseveral times over the years. The most recent upgrade was in '#C#''''''''. Based on their ownlaboratory studies and numerous design contracts, TKUES has broad technological knowledge of andexperience in the field of de-waxing and de-oiling.

3Information on the study is available at http://solomononline.com/benchmarking-performance/refining-bm/ (accessed on 14 November 2014).


31

The tasks for which TKUES was appointed by the applicants included:

Developing a concept for finding alternative solvents for the applicants’ installations Identifying, where possible and suitable, an alternative substance for EDC which can replace

this substance tonne for tonne Investigating the advantages and disadvantages associated with alternative solvents Establishing the changes required for the conversion to an alternative solvent Estimating the costs that would be associated with the conversion to an alternative solvent.

This authoritative analysis provides the backdrop to the assessment of the technical and economicfeasibility of the only shortlisted possible alternative in Section 5 of this AoA. The feasibility studyconfirmed that tonne for tonne replacement of EDC cannot be carried out and the entire DI-MEtechnology would need to be replaced by an alternative technology.

TKUES considered a range of different alternatives. These include both industrially proven options,such as the MEK-Toluene technology, but also, alternatives that TKUES has tested in the laboratory,which could be implemented but have not yet been proven. The alternatives considered by TKUESare shown in Table 4-5.

Table 4-5: Potential alternatives to EDC identified by the TKUES feasibility study commissioned by theapplicants

#Common name of solventsystem

Solvents usedApplicability

De-waxing De-oiling

- DI-ME EDC, DCM

13 MEK-TolueneMethyl ethyl ketoneToluene

9 DIPE-MEKDiisopropyl etherMethyl ethyl ketone

4 Acetone-TAMEAcetone (Dimethyl ketone)tert-Amyl methyl ether

10 EtOH-MTBEMethyl tert-butyl etherEthanol

15 MIBK Methyl isobutyl ketone

Source: Applicants’ data (TKUES feasibility study)

4.2.2 Literature research

During the preparation of this AoA, a review of relevant literature was undertaken by the third partyauthoring this AoA document. Some relevant sources of information are presented below and anoverview of the potential alternatives identified in each source is provided.

Best Available Techniques (BAT) Reference (BREF) Document for Mineral Oil Refineries and the GasIndustry

The relevant BREF document includes specific sections on solvent de-waxing and names thefollowing solvent systems as those considered to be BAT.


32

Table 4-6: Potential alternatives to EDC identified by relevant BREF Document

# Common name of solvent system Solvents usedApplicability

De-waxing

- DI-ME EDC, DCM

16 Propane Propane

14 MEK-MIBK Methyl ethyl ketone - Methyl isobutyl ketone

13 MEK-Toluene Methyl ethyl ketone - Toluene

Source: EIPPCB (2015)

The BREF Document indicates that the solvents are chosen according to the focus of the de-waxingprocess (EIPPCB, 2015):

When aiming to remove paraffinic compounds from the feed stock in order to achieve highyields of base oil, a mixture of MEK-Toluene or MEK-MIBK might be chosen

When aiming to produce specific oil and wax qualities with special product requirements,the preferred solvent is a DI-ME mixture. The mixture composition varies from 80/20 to20/80, depending on the feedstock being treated

When the units are designed to de-oil slack wax of varying quality, a single solvent, EDC, isgenerally used.

Other publications

There is a great variety of publicly available sources that discuss de-waxing and de-oilingtechnologies. Some are briefly discussed below.

Sequeira, 1994

In 1994, Sequeira published a reference book on the processes being used for lubricant base oil andwax manufacture. This book provides an extensive analysis of different de-waxing and de-oilingprocesses and the solvent systems used. A short overview of the processes presented in this book isgiven in Table 4-7, overleaf.

Jans & Stepanski, 1999

A 1999 article published in Sulzer Technical Review describes a de-oiling technique called staticcrystallisation, which is employed at the Sasol Wax facility in Hamburg.

The technology was developed by Sulzer Chemtech with the aim to be (Jans & Stepanski, 1999):

Solvent-free Capable of increased yields compared with existing processes Highly flexible with regard to the changing characteristics of the feedstock and the end

product Accompanied by low production costs and thus high profitability.


Table 4-7: Overview of potential alternatives identified by Sequeira (1994)

Process type Solvents used # Notes

Focus on de-waxing

Ketone de-waxingprocesses

Acetone-Benzene 1 Commercialised in 1927 and has been most extensively developed by Texaco

MEK-Toluene 13 Most extensively used

MEK-MIBK 14 Most extensively used

MIBK 15 Used in some cases

Propane de-waxingprocess

Propane 16 Developed and first used in 1932 by Standard Oil Company of Indiana

Acetone-Propene 3Proposed in the 1970s; although testing was reported to have been successful, it is not known if the modified process hasbeen used commercially

Urea de-waxingprocess

Urea, used alongsideDCM

19

Normally not thought of as a solvent de-waxing process. However, considerable quantities of solvent are used in theprocess. The use of urea de-waxing on a commercial scale for the manufacture of base oils and waxes was developed byEdeleanu and was first used commercially in 1954 by Deutsche Erdöl A.G. in Heide, Germany. H&R OWS used thistechnology in the past. The unit was shut down in the 1970s

Catalytic de-waxing Solventless 21

In general, catalytic de-waxing is cheaper than solvent de-waxing, both in terms of investment and operation.Additionally, it allows for the production of oils with lower pour points: it is not typically possible to produce oils with pourpoints below -32°C with solvent de-waxing. No wax is produced as a by-product.BP process: this uses proprietary, synthetic, mordenite-containing platinum as the de-waxing catalyst. The feedstock ismixed with hydrogen, heated to reaction temperature and passed over the catalyst so that it reacts. The wax componentsare selectively cracked by reaction with the hydrogen (hydro-cracked) to give fuel gas and gasoline as by-products.Chevron process: this was commercialised in 1984 at the Chevron refinery in Richmond, California. The catalyst is “mostprobably” (according to Sequeira) a ZSM-5 or a similar zeolite containing a small quantity of a hydrogenation metal. Theoperating conditions and frequency of catalyst reactivation or regeneration for this process are not available. This unitwas converted to the Chevron “isodewaxing” process in 1993.Mobil process (Mobil lube de-waxing; MLDW): this is the most widely used of the catalytic de-waxing processes. It wasfirst demonstrated in 1978 using a converted hydro-treatment unit in Gravenchon, France. By 1993, there were tencommercial units in operation. The process is similar to the BP process; the key difference is that a second reactor,containing a different catalyst, is used for hydrogen finishing the de-waxed oil

Focus on de-oiling

Wax sweating Solventless 23 The oldest wax de-oiling process which has for the most part been replaced with the more modern processes

Fractionatecrystallisation

Ketone-based - Developed as a replacement for the wax sweating process and can be used to fractionate or de-oil all types of waxes

Spray de-oiling EDC - Not relevant as an alternative to DI-ME-based de-oiling

Source: Sequeira (1994)


34

The process is based on sweat de-oiling but employs a specially designed perforated structure forcrystallisation. This structure stops the crystal mass prematurely sliding off the heat exchangerplates and into the crystalliser during sweating.

Schümann Sasol (now known as Sasol Wax) commissioned the first de-oiling plant successfully inHamburg in 1998. The plant de-oils 100,000 tons of slack wax per year via static crystallisation. Itreplaced two older plants, in which chlorinated solvents had been used.

Wauquier, 2000

Wauquier highlights some solvents used for de-waxing. These are summarised in Table 4-8.

Table 4-8: De-waxing processes described by Wauquier (2000)

Solvent or name of process # Notes

MEK-Toluene 13 80% of industry

MIBK 15 Solvent power greater than MEK-toluene

DCM 8

Trichloroethylene 18

Propane 16 Process dating back to 1932. Now phased out

EDC/Benzene - Dating back to 1930. Now phased out

Acetone/Benzene 1 Dating back to 1927. Now phased out

Source: Wauquier (2000)

Lynch, 2007

Lynch discusses several approaches to solvent de-waxing. These are summarised in Table 4-9.

Table 4-9: De-waxing processes described by Lynch (2007)

Solvent or name ofprocess

# Notes

Cold settling 20Wax allowed to settle in cold tanks or barrels. Only suitable in winter (whencold temperature allows)

Sulphur dioxide-Benzene 17 Edeleanu process

Propane 16Developed by Standard Oil of Indiana. Still in use. Considered best for heavyfeeds such as bright stocks (high-viscosity refined and dewaxed lubricatingoils used in the compounding of motor oils)

Benzene-Acetone 1

By the Texas Company, later Texaco. Developed into MEK-toluene. Toluenereplaced benzene due to benzene’s toxicity, higher melting point and lowerfiltration rates. Acetone gave way to MEK due to the latter’s higher boilingpoint and therefore reduced solvent losses

MEK-Toluene 13 Most common solvent de-waxing process

Source: Lynch (2007)

Ullmann’s Encyclopedia of Industrial Chemistry, 2012

‘Ullmann’s’ presents an overview of de-oiling processes, and this is summarised in the followingtable. The table explains that EDC may be used in two types of de-oiling, either with or withoutDCM, depending on whether the slack wax feedstock is received from a linked de-waxing process oris bought in (also see Table 4-1 on the refineries using EDC in one of these two routes).


35

Table 4-10: De-oiling processes described by Wolfmeier et al (2012) – Ullmann’s

Company Process Solvents used # Starting material

Edeleanu Pulping (DI-ME) EDC-DCM - Slack wax-solvent mixture (from de-waxing)

Edeleanu Spray de-oiling EDC - Slack wax

Exxon Crystallisation(Dilchill)

MEK-MIBKMEK-Toluene

1413

Slack wax-solvent mixture (from de-waxing)

Texaco Crystallisation (waxfractionisation)

MEK 11 Slack wax and Slack wax-solventmixture (from de-waxing)

Texaco Pulping process (one-and two-step)

BenzeneBenzene-Toluene

67

Slack wax-solvent mixture (from de-waxing)

Union Oil Crystallisation Water-saturated MIBK 15 Slack wax

Sweat de-oiling Solventless 23 Slack wax

Source: Wolfmeier et al (2012)

Relevant patents

A large number of published patents discuss the use of a variety of solvents in de-waxing and de-oiling. Emphasis is here given to potential alternative solvents that may have not been identified inmore ‘mainstream’ sources and which may not have been identified in the applicants’ R&D. Thefocus is on what has been described in the patents as ‘preferred embodiment’. This should beconsidered, in general terms, to be more suitable than equivalents that are not discussed in terms ofpreferred embodiment. The patents presented here are generally considerably dated.

Table 4-11: Preferred de-waxing solvent solutions in patent literature

Source – Patent # Solvents Notes

(Walker, 1970) 3 Acetone-PropenePreferred solvent mixture (ethene and butenes alsoconsidered); propene content is 63-75% by volume

(Biribauer, et al., 1971) 3 Acetone-PropenePreferred solvent mixture (paraffins and olefins alsoconsidered alongside MEK, MPK, MIPK, MBK, MIBK);propene content is 87.5% by volume

(Gould, 1973) 3 Acetone-Propene

Preferred solvent mixture; the acetone is the solvent –the propene is added later and provides auto-refrigeration while further mixing the stream. MEK,acetone, MIBK, MPK and mixtures of these, as well asmixtures of these ketones with aromatic compounds,such as benzene and toluene, might be used as thesolvent instead of acetone. The author highlightsMEK–MIBK and MEK–Toluene in particular.Meanwhile, ethane, ethene or propane might be usedas the auto-refrigerant instead of propene

(Eagen, et al., 1973)3 Acetone-Propene Preferred solvent mixtures; other mixtures considered

include acetone-benzene, acetone-toluene, MEK-MIBK,benzene-toluene

13 MEK-Toluene

(Hislop & Eagen, 1973)11 MEK Preferred solvents; the composition of the mixture is

45:5514 MEK-MIBK


36

Table 4-11: Preferred de-waxing solvent solutions in patent literature

Source – Patent # Solvents Notes

(Bushnell, 1976) 3Acetone-Propene(and acetone-methanol)

A dewaxing process is provided in which a mixture of asolvent comprising propene-acetone and a waxypetroleum oil is contacted with a cold aqueous solutionof acetone and methanol. The aqueous acetone-methanol solution, which is immiscible in the waxy oil-solvent mixture, cools the mixture thereby crystallisinga substantial portion of the wax in the mixture

(West, 1978)2 Acetone-DCM

DCM content ranges from 20 to 85% by volume12 MEK-DCM

(Broadhurst, 1982) 13 MEK-ToluenePreferred solvent mixture (70/30); also consideredMEK-MIBK, acetone-toluene, acetone-propylene

(DeKraker, 1993) 16 PropanePreferred auto-refrigerative de-waxing solvent; alsoconsidered propene, butane, butene

4.2.3 Consultation with the supply chain

Given that EDC is only used as a solvent in a production process and does not play a role in the endproducts, consultation with other actors along the supply chain was not deemed necessary for thepurposes of the AoA and was not undertaken.

4.3 Screening of potential alternatives

4.3.1 Approach to screening

A screening process has been followed in order to transform the master list of potential alternativesinto a more manageable shortlist of possible alternatives which can fulfil the technical function ofEDC as a minimum. More specifically, the master list of potential alternatives was screened fortechnical feasibility to exclude those potential alternatives which would under no reasonablecircumstances be able to be successfully implemented in the applicants’ production units. In thiscontent, the screening looked at:

Applicability of an alternative for both de-waxing and de-oiling: an alternative can be arealistic proposition only if it is capable of delivering both the de-waxing and de-oilingprocesses on an industrial scale, as the applicants cannot replace the existing DI-MEtechnology with two separate technologies for the two main steps of production. If thiswere not possible, severe issues of co-ordination and compatibility between the two newseparate production lines would arise

Proven track record of an alternative on an industrial scale: possible alternatives need tohave already been proven at industrial installations of a size similar to those of theapplicants within this lube refining industry. The applicants would not wish to convert to anobsolete, inefficient technology which would certainly disadvantage them vis-à-vis theircompetitors

Compatibility with the applicants’ feedstock and production set up: alternative solventswould need to be able to deliver final products of sufficient quality (i.e. slack waxes with an


37

oil content of less than 12% and hard waxes with an oil content of less than 0.5%) startingfrom the feedstock used in Hamburg and Salzbergen (the parameters of which are variable)and under the setup and operating conditions of the applicants’ production units.

4.3.2 Results of screening

An overview of the screening process is presented in Table 4-12. Brown colour indicates an areawhere a potential alternative cannot fulfil the technical function of EDC. In general, the applicantshave no knowledge of refineries using many of the identified solvents/solvent combinations, such aspropane, ethanol, benzene, urea and methyl isobutyl ketone. The conclusion of this screening isthat there is only one possible alternative, the MEK-Toluene mixture. This is the only alternativeassessed in Section 5 of this AoA.


Table 4-12: Screening of potential alternatives for the generation of a shortlist of possible alternatives

# NameCapability for both de-

waxing and de-oiling onan industrial scale

Proven on an industrial scale and relevant to the applicant’s process, feedstock and setuprequirements

Conclusion


1 Acetone-Benzene Yes

No evidence that it is used commercially today, although it was used commercially in thepast. To the best of the applicants’ knowledge, commercial use ceased several decades ago.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology

Not a possiblealternative

2Acetone-Dichloromethane

Yes

Appears to be referred to in patents only; no evidence of current use. No commercial unitknown to the applicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


3 Acetone-Propene Unknown

Appears to be referred to in several (dated) patents only. No commercial unit known to theapplicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


4Acetone-tert-Amylmethyl ether

Yes

No evidence it has ever been used commercially '#I#'''''''''''''''' '''''''''''''' '''''''' ''''''''' ''''''''''''''''''''''''' ''''''''' '''''''''. No commercial unit known to the applicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; unproven and not astate of the art technology


5 Acetone-Toluene Unknown

No evidence it has ever been used commercially. No commercial unit known to theapplicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


6 Benzene Yes

Wolfmeier et al (2012) refer to the commercial use of benzene for de-oiling slack wax andsolvent mixtures coming directly from a de-waxing step (“pulp process (one- and two- step)”by Texaco). Use of benzene is considered obsolete, particularly in light of the veryunfavourable hazard profile of the substance. No commercial unit known to the applicantsuses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology







Conclusion

7 Benzene-Toluene Yes

Wolfmeier et al (2012) refer to the commercial use of benzene for de-oiling slack wax andsolvent mixtures coming directly from a de-waxing step (“pulp process (one-and two-step)”by Texaco). Use of benzene is considered obsolete, particularly in light of the veryunfavourable hazard profile of the substance. No commercial unit known to the applicantsuses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


8 Dichloromethane

Without EDC, the solventwould be powerfully

solvating with respect toboth the oil fraction andthe wax fraction, and asa result there would be

no opportunity forseparation of the two

No evidence it has ever been used commercially. It is unlikely to be a realistic solution forthe applicants’ feedstock and products. No commercial unit known to the applicants usesthe solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


9Diisopropyl ether-Methyl ethylketone

Yes

It has only been tested within laboratories.'#I#''' '''''''''''' '''''''''' ''' '''''' ''''''''' ''''''''''''''''''' ''''' ''''''''''' ''''' ''' '''''''''''''''' '''''''''''''''''''' ''''''''''''''''''' '''''''there has been no uptake by any plant, globally. No commercial unit known to theapplicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; unproven and not astate of the art technology


10Ethanol-Methyltert-butyl ether

Yes

It has only been tested within laboratories. No commercial unit known to the applicantsuses the solvent.Not appropriate for the applicants’ feedstock and production setup; unproven and not astate of the art technology







Conclusion

11Methyl ethylketone

Unknown

Mentioned by Sequeira (1994) but conclusive evidence of commercial use is unavailable. Noevidence it has ever been used commercially on its own. No commercial unit known to theapplicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


12Methyl ethylketone-Dichloromethane

Yes

Referred to in a patent only. No evidence of current use. No commercial unit known to theapplicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


13Methyl ethylketone-Toluene

YesState of the art technology, but requires changes to production setup95% of commercial de-waxing/de-oiling is currently based on this technology. Identified inthe BREF Document and applicants’ R&D

Possiblealternative

14Methyl ethylketone-Methylisobutyl ketone

Yes

Identified in the BREF Document but no commercial unit known to the applicants uses thesolvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


15Methyl isobutylketone

MIBK may be promisingfor EDC spray de-oiling

but not for theapplicants’ operations

The applicants believe that it has only been tested within laboratories but Sequeira (1994)suggests it has been used in some cases.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


16 Propane Yes

Identified in the BREF Document and by the applicants’ R&D as a ‘known’ process but nocommercial unit similar to the applicants’ units is known to use it.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


17Sulphur dioxide-Benzene

Yes

Identified in literature but very old technology and largely irrelevant. No commercial unitknown to the applicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology







Conclusion

18 Trichloroethylene Unknown

No evidence it has ever been used commercially. No commercial unit known to theapplicants uses the solvent.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


19 Urea Yes

Mentioned in the literature from mid-1960 that a German company used this process, butthis is no longer known to be the case.H&R used urea for de-waxing naphthenic oils. The unit was in operation for some years. Itwas demolished (in the 1970s) because the process proved to be insufficient.Not appropriate for the applicants’ feedstock and production setup; not a state of the arttechnology


Solventless systems/processes

20 Cold settling NoObsoleteNot relevant to the applicants’ operations


21 Catalytic de-waxing No

Several petroleum refiners have patented various catalytic dewaxing (selective hydro-cracking) processes for the manufacture of lubricant base oil stocks (Sequeira, 1994).Catalytic de-waxing of the raffinate would not generate the slack waxes to use as feedstockfor the de-oiling process.Not relevant to the applicants’ operations


22 Static crystallisation NoCurrently being used. Exclusively de-oiling process, cannot produce base oilsNot relevant to the applicants’ operations


23 Wax sweating No

The oldest wax de-oiling process which has for the most part been replaced with moremodern processes. No new plants are being built for this classical de-oiling process becauseof low selectivity (poor yields of hard wax), time-consuming warmup, need to use a batchprocess, and inapplicability of the method to strongly oil-binding slack waxes from mediumand heavy machine oil distillates (Wolfmeier, et al., 2012)Exclusively de-oiling processes cannot produce base oils. Only for fractions below N200Not relevant to the applicants’ operations



42


43

5 Suitability and availability of possible alternatives

5.1 Methyl ethyl ketone and toluene

5.1.1 Substance ID and properties

Name and other identifiers of the substances

Identifiers for the two substances, MEK and toluene, are presented in Table 5-1.

Physicochemical properties

Key physicochemical properties of MEK and toluene are given in Table 5-2. The information wascollected from the ECHA dissemination portal (search undertaken on 29 August 2014) and iscompared to that of EDC and DCM.

The solvent component ratio that is considered appropriate for the applicants’ operations is 50:50(w/w). '#A#'''''' '''''''''' ''''''' '''''''' '''''''''' '''''''''''''''' '''' ''''''''''''''' ''''''''''''''''''''''''' ''' ''''''''''' '''''''' '''''''''''' ''' ''''''''''''' ''''''' '''''''''''''''' '''' ''''''''''

Table 5-1: Identity of alternative solvents

ParameterMethyl ethyl ketone Toluene

Value Source Value Source

EC number 201-159-0 1 203-625-9 1

EC name Butanone 1 Toluene 1

CAS number 78-93-3 1 108-88-3 1

IUPAC name Butan-2-one 1 Toluene 1

Other namesMEK;

2-Butanone1

Methylbenzene; Toluol;Benzene, methyl-; Methacide;Methylbenzol; Phenylmethane

2

Molecular formula C4H8O 1 C7H8 1

SMILES notation CCC(=O)C 3 CC1=CC=CC=C1 3

Molecular weight 72.10572 2 92.13842 2

Molecularstructure

3 3

Sources (searches undertaken on 29 August 2014):1. European Chemicals Agency: http://echa.europa.eu/2. Pubchem: http://pubchem.ncbi.nlm.nih.gov/3. Chemspider: http://www.chemspider.com/


44

Table 5-2: Physicochemical properties of MEK and toluene (and comparison with EDC and DCM)

Property EDC DCM MEK Toluene

Physical state at 20°Cand 101.3 kPa

Liquid Liquid Liquid Liquid

Melting/freezing point -36 °C-95 °C at101.3 kPa

-86.65 °C -95 °C

Boiling point 83.6 °C 40 °C at 101.3 kPa 79.59 °C 110.6 °C

Density1.2455 g/cm

3

at 20 °C1.33 g/cm³ at

20 °C0.81 g/cm³

at 20 °C0.87 g/cm³

at 20 °C

Vapour pressure102.47 hPa

at 25 °C

584 hPa

at 25 °C

104 hPa

at 20 °C

30.8 hPa

at 21.1°C

Surface tension32.45 dynes/cm

at 20 °CNot relevant -

27.73 mN/mat 25 °C

Water solubility 7.9 g/L at 25 °C 13.2 g/L at 25 °C 2.75 g/L0.57-0.59 g/L

at 25°C

Partition coefficientLog Pow 1.45

at 20 °CLog Kow 1.34

Log Pow 0.3

at 40 °C and pH 7

Log Pow 2.73

at 20 °C and pH 7

Flash point 13 °C No flash point -9 °C 4.4 °C

Flammability

Lower explosionlimit (%): 6.2

Upper explosionlimit (%): 16

Lower explosionlimit (%): 16


Lower explosionlimit (%): 1


Lower explosionlimit (%): 1.1

Upper explosionlimit (%): 7.1

Explosive properties - - - -

Self-ignitiontemperature

440 °C 605 °C 404 °C 480 °C

Oxidising properties - - - -

Granulometry - - - -

Viscosity0.83 mPa.s

dynamic at 20 °C0.443 mPa.s

at 20 °C0.42 mPa.s

dynamic at 20 °C0.58 mPa.s

dynamic at 20 °C

Source: European Chemicals Agency: http://echa.europa.eu/

5.1.2 Technical feasibility

Over 95% of commercial de-waxing and de-oiling units worldwide (by number) use MEK-Toluene. Inthis regard, MEK-Toluene is a possible alternative which could be considered for the replacement ofDI-ME.

Table 5-3 provides a comparison of EDC and MEK-Toluene against the nine identified technicalfeasibility criteria. Where shortcomings are identified (marked by brown cell colour), the tableexplains what the technical/practical implications would be in terms of actions that would need tobe taken to address the shortcomings up to the point of achieving a minimum technical feasibilityand practicability of the alternatives. The table shows that MEK-Toluene would fail to meet seven ofthe criteria, thus indicating that in comparison to the DI-ME system, its technical feasibility for theapplicants’ plants is unacceptably poor.


Table 5-3: Comparison of MEK-Toluene against the technical feasibility criteria

#Technical feasibilitycriterion

Technicalrequirements for theapplicant’s processes

MEK-Toluene Notes and actions that would be taken to address any shortcomings

1Solubility andselectivity

Need to be sufficientto achieve 0.5% oil

content in hard waxLower

Lower solubility and selectivity would prevent the applicants from using their typicalfeedstock and obtaining the full range of products in their portfolio.Actions to be considered:1. Increase the amount of solvent circulating in the unit2. Lower the filtration temperature for de-waxing. This will maintain the low pourpoint of the base oils

2

Boiling point84.1 °C for EDC39.7°C for DCM

Higher79.6 °C for MEK

110.8 °C for TolueneActions to be considered:1. Change the heat transfer substance in the solvent recovery section2. Increase temperature and pressure of steam used for steam stripping duringsolvent recovery. DI-ME requires steam at 150 °C. The alternative is estimated torequire steam at more than 260 °C (the high boiling point of toluene requiresparticularly high temperatures for evaporation/recovery)3. Increase surface area for heat exchange

Specific heat capacity1.298 kJ/kgK for EDC1.156 kJ/kgK for DCM

Higher2.19 kJ/kgK for MEK

1.717 kJ/kgK for Toluene


324 kJ/kg for EDC329 kJ/kg for DCM

Higher444 kJ/kg for MEK

362 kJ/kg for Toluene

3 Cloud point -26 °C or lower SimilarA greater temperature difference is needed by MEK-Toluene to meet the congealingpoint.Actions to be considered: a wider temperature range for process will be needed






4 Filterability

Produce products ofacceptable oil/wax

content using afiltration area similar

or smaller thancurrent ('#D#'''''''' m

2

in Salzbergen and'#D#'''''''''' m

2in

Hamburg)

Cannot deliver level ofquality required withcurrent filtration area

Worse filterability, therefore more filter area is needed to achieve equivalent resultsActions to be considered:1. Increase the surface area for filtration by '#D#''''% to '#D#''''%, depending on theunit configuration (increase to '#D#'''''' m

2in Salzbergen and '#D#''''''' m

2in

Hamburg). This would allow the applicants to maintain the current rate of filtrationand quality of products (NB. suitable filters are very costly equipment and theapplicants’ units plants are located within existing unit complexes. There is no sparearea for the installation of additional filters)2. Make other changes relating to the lower density of MEK-Toluene compared withDI-ME, i.e. the existing vacuum drum filter and the wastewater treatment must berevamped, because DI-ME is heavier than water, but MEK-Toluene is lighter, thusthe water settler would need a different design3. Introduce de-waxing aids for some runs

5 Corrosion potentialZero tolerance forsolvents causing

corrosion of pipeworkLower -

6 Explosion risk

Explosion limitsshould be similar orhigher than EDC and

DCM.Gas lower explosion

limit: 6.2%-13% (EDC-DCM)

Gas upper exposurelimit: 16%-22% (EDC-

DCM)

HigherGas lower explosionlimit: 1%-1.1% (MEK-

Toluene)Gas upper exposure

limit: 11%-7.1% (MEK-Toluene)

EDC DCM MEK Toluene

Boiling point [°C] 84 40 80 111

Flash point [°C] 13 - -1 6

Self-ignition temperature [°C] 440 605 505 535

ATEX Classification IIA T2 IIA T1 IIA T1 IIA T1

Lower explosion limit [Vol.%] 6.2 13 1.8 1.2

Upper explosion limit [Vol.%] 16 22 11 7.1

Oxygen threshold limit[Vol.%]

5.9 9.5 9.6

Actions to be considered: the oxygen concentration in the gas filter system shouldbe monitored and when MEK-Toluene is used, be kept well below 9.5% (vol.). Thiswould mean an increase in the use of nitrogen gas for blanketing






7 Energy consumptionEnergy consumption

levels similar or lowerthan DI-ME

'#F#''''''' '''''''''''''''''''''''''''''''' ''''''' '''''' '''''''''''''''

''''''' '''''''''' '''''' '''''' '''''''''''''

This has an impact on the energy balance of the refineries. Surplus steam can nolonger be used.Actions to be considered: The refineries need additional new heating facilities, suchas hot oil systems, to generate the increased amount of energy required with naturalgas

Slack wax oil content 6-8% ''#F#'''''''''''' Under the unit’s typical operating conditions, MEK-Toluene would result in a higheroil content in slack wax which would mean that the required quality criterion of 0.5%oil in hard wax could not be metActions to be considered: changes to the filtration systems and the processconditions would be required for MEK-Toluene to deliver the required oil content(see above). Product qualities, especially for the large variety of the applicants’different products have to be screened prior to the replacement of EDC. Customerapprovals are needed for the vast majority of the applicants’ products

Hard paraffin wax oilcontent

<0.5%''#F#''''''''''' ''''' '''''''''''

'''''''''''''

9Production of asufficiently wide rangeof specialties

Need to generate arange of specialties of

similar volume/variety to DI-ME

'#I#'''''''''''''''''''''''''''''''''''''''''' '''''''''

''''''''''''''''''' ''''''''''''''''''''''''''''''' ''''''''''''''''''

''''''''''''''''''''' ''''''''''''''''''''''''''' '''''''' ''''''''''''''''''

'''''''''''''''''''''' ''''''''''''''''' ''''''''''''''''''' '''''''' ''''''''' '''''' ''''''''''''' ''''''''''''''''''''' ''''''''''''''

''''' '''''''''''''''''' '''''''''''''''''''''''''''' '''' ''''''''''' '''''''

'''''''''''''''

Very strict quality specifications such as very low oil contents are not achievable withMEK-Toluene because the solvent mixture is not as selective and the wax cake’sfilterability is worse. A too large filter area makes the handling of differentfeedstocks almost impossible because the “window of operability” for the processconditions would be too wide with MEK-Toluene.Ability to generate a wide range of specialties is fundamental to H&R AG’s strategyfor future profitability and to the applicant’s competitive position in a rapidlychanging landscape of global lubricant refining.Actions to be considered: MEK-Toluene cannot be improved; no alternative to DI-ME has demonstrated equivalent capability of specialty generation


48

MEK-Toluene is a completely different substance mixture. Due to the different physicochemicalproperties of the alternative solvent mixture, each plant would have to undergo very significantequipment and process modifications with regard to (a) filtration and pumping, (b) heating andcooling (including solvent recycling and associated energy costs), (c) hazard controls (elimination ofCMR substances but simultaneously increased explosion risks), and (d) maintenance. This wouldresult in lengthy downtime and only some of the existing equipment could still be used with MEK-Toluene.

Importantly, the MEK-Toluene alternative mixture would not allow the production of the full rangeof applicants’ existing products, particularly of the wide range of specialties which really makes theapplicants stand out among their peers. In addition, the MEK-Toluene technology would not allowthe applicants to generate the full range of its wax products; de-waxing aids would need to be usedfor some products4.

Due to these severe impacts on product range and quality, MEK-Toluene is not a technically feasibletechnology for the applicants’ production setup, feedstock and product portfolio, even if a complex(and costly) conversion of the applicants’ existing units were to be implemented. This alternativecannot become feasible, unless the applicants’ business model were to radically change, thismeaning the abandonment of all those product quality and portfolio range parameters which arethe applicants’ unique selling points vis-à-vis European and international competition. '#A#'' '''''''''''''''' ''''' '''''''''''''''''''''''' '''''''' '''''' '''''''''''''''''' '''''' ''''''''''''''' ''' ''''''''''''''''''''''''' '''''''' '''' '''''' '''''''' '''''''''''''''''''''''''''''''''' ''' '''' ''''''' ''''''''''''' ''''''''''''''''''''''' '''''''''''''''''' ''''''''''''''''''' ''''' ''''''' '''''''''''''''''''' ''''''' '''''''''''''''''''''''''''''''''''''' '''' '''''''''''''''''''''''''' ''''''''''''' ''''''''''''''''''' ''' ''''''''''''''''' ''''''''' ''''

5.1.3 Economic feasibility

Given the demonstrated lack of technical feasibility of MEK-Toluene for the applicants’ productionunits, an assessment of the economic feasibility of this solvent mixture would not be warranted.However, a very detailed assessment is available in the feasibility study that the applicants havecommissioned. These findings are presented in Annex 2 (Section 9) to this AoA.

4The relevant BREF Document recognises the superiority of the DI-ME technology for users who wish toobtain a range of end products (base oils, hard waxes, specialties) as opposed to maximising base oilproduction. The Document distinguishes between the different purposes of DI-ME and MEK-Tolueneplants (EIPPCB, 2015),

“The solvents are chosen according to the focus of the dewaxing process:

- When aiming at removing paraffinic compounds from the feed stock in order to achieve high yields ofbase oil, a mixture of MEK-Toluene or MEK-MIBK might be chosen

- When aiming at producing specific oil and wax qualities with special product requirements, thepreferred solvent is a DiMe-mixture

- When the units are designed to de-oil slack wax of various qualities, a single solvent, 1.2-Dichlorethane,is generally used.

(…) Existing units would require a feasibility study due to the specificity of the processes used which aregenerally designed for a specific type of solvent”.


49

The estimates of conversion costs and of changes to operating costs in the feasibility analysis havebeen undertaken under two fundamental conditions:

The existing equipment and plants should be re-used to the extent possible The quality of final products and the production throughput should be maintained.

Table 5-4 summarises the calculations of the quantified cost elements associated with a conversionof the applicants’ refineries to the MEK-Toluene technology, as shown in Annex 2.

Table 5-4: Breakdown of costs associated with switching to alternative solvent mixture

Type DescriptionCost

Estimated value Range

Initial costs

R&D'#E# all Table 6-4''''''''

'''''''''''' '''' '''''''''''€1-10 million

Plant conversion '''' '''''''' ''''''''''' €10-100 million

Other conversion costs (steam and gas supply,wastewater treatment)

Not quantified

Downtime''''''' '''''''''''''' '''''

'''''''''''''€10-100 million

Personnel training Not quantified

Sub-total ''''''''' ''''''''''''' €100-1,000 million

Lossinvestment

Past investment written off '''''''' ''''''''''' €1-10 million

On-goingcosts

Energy consumption ''''''''''' ''''''''''''''''' +€1-10 million/y

Materials and service costs Not quantified

Maintenance and laboratory costs Not quantified

Regulatory compliance '''''''''' '''''''''''''''' + <€1 million/y

Cost of servicing loans '''''''''''' '''''''''''' '''''''''''''' '''''''' ''''''''''' '''''''''''''''''' + €1-10 million/y

Sub-total'''''''' ''''''''''' ''

''''''''''''''+ €10-100million/y

Source: TKUES feasibility study

The summary above and the detailed analysis in Annex 2 confirm that the investment costs would betoo high at '#E#''''''''' ''''''' '''''''''''''; securing a loan to fund the conversion would be difficult as theeconomics of the converted plant would be particularly poor. The quantified cost elements amountto an additional '#E#''''' '''''''' ''''''''''''/y in costs; it is clear that MEK-Toluene systems can beaccompanied by significantly higher energy consumption and higher utility costs. The prospects ofthe converted units generating a profit would be poor.

As to whether the applicants could adjust the prices of their products to recoup the investments andabsorb the increased operating costs, it must be noted that product prices are linked to the crude oilprice and competitors operate energy-optimised units; therefore, the applicants’ revamped unitswould suffer from poor competitiveness and opportunities for market price increases for theirproducts would be very slim. This would be a major disadvantage that would be impossible tooverturn from today’s perspective.

Overall, the significant investment costs and the poor production economics, post-conversion renderMEK-Toluene an economically unviable and therefore infeasible alternative; moreover, several costelements have not been possible to quantify. The economics of conversion are prohibitive;


50

therefore, the applicants would not be able to convert even if Authorisation for the continued use ofEDC were not granted.

The economic feasibility of any other alternative that may be identified in the future will clearly needto be assessed on a case-by-case basis, however, the discussion here demonstrates the order ofmagnitude of costs that would be involved in converting to a new technology.

Actions that would be required for making the alternative economically feasible

The methodology applied in Annex 2 to estimate the costs of implementing the alternative solventmixture aimed to minimise the upfront costs by assuming that much of the existing equipmentwould still be used after the conversion of the plant. This somewhat reduces upfront costs butincreases on-going costs as energy consumption is not optimised—the applicants’ units have beenspecifically designed for operation with the DI-ME technology. An alternative approach would be tore-build the units specifically for operating on the alternative technology. This would make theoperating costs more favourable than what has been described above, but the upfront investmentcosts would increase further, and thus be entirely prohibitive. Essentially, the costs of conversionare dictated by the physicochemical properties of the MEK-Toluene mixture; these cannot bealtered5, therefore the economic feasibility of this alternative is impossible to improve to the extentthat it becomes a suitable alternative to DI-ME.

'#A#''''''''''''' ''' ''''''''' '''''''' ''''' ''''''''''' '''''''' ''''''' ''''''''''''''''' ''''''' '''''''''''''''' '' ''''''''''''''''''''''''''' ''''''' '''' ''''''' ''''''''''''''''''' ''''''' '''''''' '''''''''''''''''''' '''' ''''''' ''''''''''' '''''''''''''''''''''' '''' '''' '''''''' '''''''''''''''''''''' '''''''''''''''''''''''''' ''''''''''''''''''''''''''''''''' '''''''' '''' '''''''''' ''''''''''' '''''''''''''' '''''''''''''''''' '''' ''''''' ''''''''''' '''''''''''''''''''''''''''' '''''''''''''''' '''''''''''''''''''''''''' '''''''''''''''''''''''' '''' '''''''''''''''''''' '''' ''''''''''''''''''''''''''''' '''''''''''''''''''''' '''''' '''''''''''' '''''''' '''

5.1.4 Reduction of overall risk due to transition to the alternative

Review of the hazard profile of MEK and Toluene

The intrinsic hazard properties of these two substances were screened to identify critical properties(e.g. CMR properties), which would make them unsuitable as substitutes for EDC.

The following information was retrieved:

Registration status (which is also a first indication of market availability) EU Classification Any other relevant information on SVHC properties (e.g. existing restrictions, evaluations of

carcinogenicity by other organisations (e.g. IARC), clear evidence for endocrine disruptingactivity).

To this end, ECHA’s website6 was consulted and the respective substance searched by CAS Number.The Registration status as well as the classification of substances was retrieved from this site. Inaddition, any information on other REACH-related activities (e.g. listing as SVHC, information on

5The properties can be altered to a limited degree by changing the ratio of MEK-Toluene but the variation inthe mixtures is limited by the properties of each component.

6http://echa.europa.eu/search-chemicals


51

restrictions, or authorisation) was considered and evaluated with regard to the potentialconsequences of using this substance as an alternative to EDC. Furthermore, eChemPortal7 wasconsulted to check if there has been any involvement in other regulatory programmes or existingevaluations (e.g. OECD SIDS reports, US HPVIS, EU Risk Assessment Reports). Relevant findings aredocumented in Table 5-6.

Toluene is classified for reproductive toxicity, Cat. 2. It is also under scrutiny in a Risk ManagementOption Analysis by EU Member States Competent Authorities, but no information is available on theendpoints, which are discussed with regard to regulatory action (as of November 2014).

Comparison of hazard profile of EDC (and DCM) and MEK-Toluene

The harmonised classification of MEK and toluene is compared to that of EDC and DCM in Table 5-5and

The substances MEK and toluene have lower toxicity and water pollution potential compared to thechlorinated substances EDC and DCM.

The flash points of MEK and toluene are somewhat lower than that of EDC and DCM, althoughgenerally this should not lead to additional explosion-proofing requirements. Of more relevance isthe oxygen concentration in the gas filter system which should be monitored when MEK-Toluene isused and kept well below 9.5% (vol).

As shown earlier, EDC hydrolyses to give hydrochloric acid, as one of its hydrolysis products, whichmay result in corrosion in the system; to prevent this, sodium hydroxide is added to neutralise theacid. On the other hand, MEK-Toluene is not accompanied by corrosion problems.

Table 5-5: Comparison of harmonised classification of EDC, DCM, MEK and toluene

EDC DCM MEK Toluene

HazardClass andCategoryCode(s)

HazardStatement

Code(s)


HazardStatement

Code(s)


HazardStatement

Code(s)


HazardStatement

Code(s)

Flam. Liq. 2 H225 - - Flam. Liq. 2 H225 Flam. Liq. 2 H225

Skin Irrit. 2 H315 - - - - Skin Irrit. 2 H315

Eye Irrit. 2 H319 - - Eye Irrit. 2 H319 - -

Acute Tox. 4 H302 - - - - Asp. Tox. 1 H304

STOT SE 3 H336 - - STOT SE 3 H336STOT SE 3STOT RE 2

H336H373

Carc. 1B H350 Carc. 2 H351 - - - -

- - - - - - Repr. 2 H361d

Source: European Chemicals Agency (C&L Inventory): http://echa.europa.eu/regulations/clp/cl-inventory

7http://www.echemportal.org/echemportal/


Table 5-6: Screening step 2: Screening of potential alternatives for hazard profile

#Name EC # CAS #

Registrationstatus

Classification CommentsConclusion

13 Methylethyl ketone

201-159-0 78-93-3 Full registration>1,000 t/y

Flam. Liq. 2 H225Eye Irrit. 2 H319STOT SE 3 H336

- No obvious CMRproperties,eligible to

replace EDC

Toluene 203-625-9 108-88-3 Full registration>1,000 t/y

Flam. Liq. 2 H225Asp. Tox. 1 H304Skin Irrit. 2 H315STOT SE 3 H336Repr. 2 H361dSTOT RE 2 H373

Annex XVII RestrictionsRestriction No. 48 - Shall not be placed on the market, or used, as asubstance or in mixtures in a concentration equal to or greater than 0.1% by weight where the substance or mixture is used in adhesives orspray paints intended for supply to the general publicPACT-RMOA substancesDenmark, under development, no information on the subject availableCoRAP list of substances2012, Finland, Human health/CMR and systemic toxicity; Exposure/widedispersive use, consumer use, high aggregated tonnage, Concluded:Recommendation for review of IOEL valuesExisting Substances RegulationRAR identified risks for humans and all environmental compartmentsIARC Classification3 (Not classifiable as to its carcinogenicity to humans), Vol 47, 71 1999

Suspected ofdamaging theunborn child,

currently underinvestigation,

eligible toreplace EDC ifother reasons

apply (i.e.technical

feasibility)

Sources:ECHA Registered Substances database (http://echa.europa.eu/information-on-chemicals/registered-substances, accessed on 18 November 2014)REACH Restrictions (http://echa.europa.eu/web/guest/addressing-chemicals-of-concern/restrictions/list-of-restrictions/list-of-restrictions-table?search_criteria=108-88-3,accessed on 18 November 2014)PACT-RMOA Substances (http://echa.europa.eu/web/guest/addressing-chemicals-of-concern/substances-of-potential-concern/svhc-roadmap-implementation-plan/pact?search_criteria=108-88-3, accessed on 18 November 2014)CoRAP List of Substances (http://echa.europa.eu/documents/10162/880a5b89-c248-49b8-a24b-d32007f0875f, accessed on 14 November 2014)OECD eChemPortal (http://www.echemportal.org/echemportal/index?pageID=0&request_locale=en, accessed on 18 November 2014)ECHA Classification and Labelling Inventory (http://echa.europa.eu/information-on-chemicals/cl-inventory-database, accessed on 18 November 2014)IACR Cancer Classifications (http://monographs.iarc.fr/ENG/Classification/, accessed on 18 November 2014)


53

Comparative risk assessment of MEK-Toluene to EDC

A comparison of the risk of EDC and MEK-Toluene is provided in Annex 3 (Section 10 – see rationalein Section 10.3.1 for not including DCM in this comparison).

For this comparative risk assessment a DMELlong-term inhalation workers for EDC associated with a 1 x 10-5 risklevel was derived from the exposure-risk relationship published by the Risk Assessment Committee(ECHA, 2015).

For the environmental assessment a PNECfreshwater was used, which is the same as that derived in theregistration dossier and by other evaluating bodies.

The solvent mixture consisting of MEK and toluene was evaluated as a potential alternative in detail.

Tentative DNELlong-term inhalation workers and PNECfreshwater were derived for both substances. As exposureoccurs to both substances, when used in the mixture, RCRs obtained for the individual substanceswere added to obtain final RCRs for use of the mixture.

EDC and the solvent mixture were evaluated using a scenario of handling the substance in a closedsystem with unloading of the substance from large, dedicated facilities.

ERC: Industrial use of processing aids in processes and products, not becoming part of articles(ERC 4)

PROC: Use in closed, continuous process with occasional controlled exposure (PROC 2)

Transfer of substance or preparation (charging/discharging) from/to vessels/large containersat dedicated facilities (PROC 8b)

Use as laboratory reagent (PROC 15)

Based on these quantitative considerations, the MEK-Toluene solvent mixture seems to beadvantageous with regard to human health effects. Environmental risks are considered to be in thesame range (with RCRs in the comparative assessment being only slightly higher) for the alternativemixture compared to EDC. RCRs for the freshwater compartment in the comparative assessment arewell below 1 for both EDC and the alternative solvent mixture. Thus, the alternative solvent mixtureis considered to fulfil the requirement of leading to overall reduced risks, when used as analternative to EDC.

Environmental externalities from increased energy consumption

The use of MEK-Toluene under the conditions described above would be expected to increase theenergy consumption of the process. As described in Table 9-9 of Annex 2, an additional '#D#'''''''''''MWh/y of energy would be required in Hamburg. It can be calculated that the generation of theequivalent amount of energy would result in the release of ca. '#H#''''''''' t/y tonnes of CO2e per year.For Salzbergen, it is tentatively assumed that the respective values would be ca. '#H#''''% of theHamburg ones.


54

Monetisation of greenhouse gas emissions is based on the methodology developed by the UKgovernment for carbon valuation in public policy appraisal8. The shadow price of carbon is closer towhat would be the full social cost of carbon emissions in terms of the damages caused by carbonemissions, but also takes estimates of marginal abatement costs, etc., into account. Thus, it alsotakes policy commitments and technological issues into account. The value used in this assessmentis £31/tonne CO2 for the year 2017 (year of the Sunset Date), as shown in the relevant UKGovernment document9. The December 2014 exchange rate (£1 = €1.25) was used to convert thevalue from £ to € (€38.8/t).

Therefore, the externalities of the increased energy consumption and concomitant CO2 emissionswould be '#E#''''''''' ''' '''''''' '' ''''''''' ''' ''''''''' million per year across all production units of theapplicants. This calculation disregards any environmental externalities that would arise fromconsumption of energy and natural resources due to construction during the conversion to thealternative.

5.1.5 Availability

Market availability of MEK and toluene

Table 5-7 summarises the REACH registration information for MEK and toluene. Both MEK andtoluene have been fully registered under REACH, the former in the 100,000 - 1,000,000 t/y band andthe latter in the 1,000,000 - 10,000,000 t/y tonnage band. Both solvents are common chemicals andwidely available on the market.

Table 5-7: REACH registration status of MEK and toluene (and comparison to EDC and DCM)

Property EDC DCM MEK Toluene

Registration Full Full Full Full

Tonnage band (t/y)1,000,000 -10,000,000

100,000 -1,000,000

100,000 -1,000,000

1,000,000 -10,000,000

Source: European Chemicals Agency: http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances (accessed on 29 August 2014)

Market availability of the alternative technology

The MEK-Toluene licensed technology is also widely used around the globe with the vast majority ofde-waxing/de-oiling installations using this technology.

Overall, this alternative is considered available to the applicants and indeed it is the only knownalternative technology that has been commercially proven on the industrial scale.

8Available at https://www.gov.uk/government/publications/updated-short-term-traded-carbon-values-used-for-uk-policy-appraisal-2014 (accessed on 13 December 2014).

9Shadow value of carbon, available athttps://www.gov.uk/government/uploads/system/uploads/attachment_data/file/243825/background.pdf


55

Access to the alternative without undue delay

Although the alternative solvent mixture components and the licence to use the alternativetechnology are readily available, the technology itself would require a considerable time period forits implementation in the applicant’s production units.

As part of the feasibility study that was prepared on behalf of the applicants, a timeline forimplementation of the MEK-Toluene alternative was developed. Three distinct but also overlappingsteps would be required for the theoretical implementation of the MEK-Toluene technology at theapplicants’ plants:

1. Laboratory based R&D to research the new technology and to prepare for implementation –this would include research by customers who would need to re-qualify the products10.

2. Engineering work to remove obsolete equipment and install new equipment and make theplants operational through a series of modifications.

3. Fine-tuning of operations to ensure that each plant operates under optimal conditions andemployees become familiar with the new technology.

The applicants operate three units, one in Salzbergen and two in Hamburg. Therefore, two of theabove steps, namely, the engineering work and the fine-tuning of operations, would need to beundertaken more than once. More specifically, starting with the Salzbergen unit (which thefeasibility study assumed as the ‘model plant’ on which the conversion to MEK-Toluene was studied)the sequence of actions would be:

Step 1: Lab tests Step 2: Engineering – Salzbergen Step 3: Modification - Salzbergen Step 4: Fine-tuning – Salzbergen Step 5: Engineering – Hamburg (1st unit) Step 6: Modification – Hamburg (1st unit) Step 7: Fine-tuning – Hamburg (1st unit) Step 8: Engineering – Hamburg (2nd unit) Step 9: Modification – Hamburg (2nd unit) Step 10: Fine-tuning – Hamburg (2nd unit).

Figure 5-1 visualises the theoretical steps for converting one production unit. Table 5-8, gives moredetail on the main and the intermediate milestones of the overall conversion process and theduration of each activity. The table includes an analysis of some of the areas of potential problemsthat may arise and could potentially cause delays. The total theoretical duration of converting toMEK-Toluene would be ca. 12 years.

10It is assumed that customers would most likely accept such changes as the MEK-Toluene de-waxing/de-oiling is an established technology.


Figure 5-1: Theoretical timeline of converting one applicant unit to MEK-Toluene (#D#)


Table 5-8: Steps and time required for the theoretical conversion of the applicants’ plants to MEK-Toluene

Conversion activity Duration Examples of potential risks and other remarks

Lab research 1,370 days '#D# all Table 5-8''''''''''' ''''''''''''' ''''''' ''''''''''''''''''''' '''''''''''''''''' ''''''''''''' '''''''''''' ''''' ''''''''''''' ''''' '''''''''''''''''''' ''''''' '''''''''''''''''''''''' ''''''''''''''''''''''' '''''' '''''' ''''''''''''''''' ''''''''''' ''''''' '''' '''''''''' ''''''' ''''''''''''''''''''' ''''''''' ''''''' '''''''''''''''''' ''''''''''' ''''''''''' '''''''''''''''''' ''''''''''''''''''' '''''''''' ''''''''' '''' '''''''''''''' '''''''' '''''''''''''''''' ''''''' '''''''''''' '''' '''''' ''''''''''''' ''''' ''''''''''''''' '''''''''''' ''''''''''''''''''''''''''' '''''' '''''''''''''

Lab-scale production with MEK-Toluene for all qualities

''''''''' '''''''' ''''''''''' ''''' '''''''''''''''''''''' ''''''' ''''''''''''''''' '''''' ''''''' '''''''''' ''''''''''''''''''''' ''''''''''''''''''''''' '''' ''''''' ''''''''''''''''' ''''''' '''' ''''' ''''''''''''''''''''''''''''''' '''' '''''''''' '''''''' '''''''' ''''' '''''''''''''''''''''''' '''''''''''''''''''''' ''''' ''''''' '''''''''''''' '''''''''''''''''' '''''''' ''''' ''''' ''''''''''''''''' '''' ''''' ''''''''''''''' ''''''''''''''''''' ''''''' ''''' '''''''''''''''''''''''' '''''''''''''''' '''' ''''''''''''''' ''''''' '''''''''' ''''''' '''' ''''''' ''''''''''''''''''' '''' ''''''' ''''''''''''''''''''''' ''' '''''''''' ''''''''''' ''''''''''' ''''''''' ''''' '''''''''''''''''''

Lab hydrogenation with somequalities

''''''' ''''''''' ''''' '''''''''''

Customer approvals, durationdepends on industry

'''''''' '''''''' '''''''''''''''''' ''''''''''''''''' '''''''' ''''''''' ''''''''''''' '''''''' '''''''' ''''''''' '''''' ''''''''''''''''''' ''''''''' ''''' '''''''''''''''' '''''''' '''''''''''''''''''' ''''''''''''''''' '''''''''''''''''' '''' ''''' ''''''''''''''''' ''''''''' ''''''' ''''''' '''''''''''''' '''''' '''''''''''''' '''''''''''

Unit 1 conversion 500 days '''''' '''' ''''''''''''''''''''' '''''''' '''' '''''''''''''''''''''''''''' '' ''''''''' ''''''''''''' ''''' '''''' '''''''''''''' '''''''''''''''''' ''''''' '''''''''''''''' ''''''''' '''''''''''' '''''''''''''''''''''' ''''''''''''' ''''''' ''''''''''' ''''' ''''''''''''''''''''' ''''''''''' '''' '''''''''''''' '''' '''''''' '''''''''' ''''''' '''''''''''''''''''' ''''''''''''' ''''''''' '''' '''''''''''''''''''' '''' '''' '''''''''''''''''' '''''''''''' ''''''''' '''''''''''''' ''''''''''''' ''''''''''''''' '''''''''''''' '''''''''''''''' '''''''''''''''''' ''''''''''''''' '''''''' '''''''''''''''''''''''' '''''''''''' ''''''''''''''''' '''''''''''''''' '''''''''''''''' '''''''''''''''''''''''''' ''''''' ''''' '''''''' '''''' ''''''''''

Basic engineering '''''''' ''''''''' '''''''''''''''''''' ''''''''''''''''''''''' '''''''' '''''''''''''''''''''' '''''''''''' '''''''''''' '''''''''''''''''''' '''''''''''''' '''''' ''''' ''''''''' ''''''''''''''' '''''''''''''' '''''''''''' ''''''''''''''''''''''' '''''''''' ''''' ''''''''''''''''''''''''''''''' '''''''' '''''''''''''''' ''' ''''''' ''''''' ''''''''''''''''''''''' '''''''''''''''''''''''''''''''''''''''''' '''' '''''''''''' '''''''''' ''''''''''' ''''''''''' '''''''''''''''' ''''''''''''''' ''''''''''''' '''''''''' ''''''''''''''''''''' '''' ''''''''''''' ''''''' ''''''' ''''''''''

Public authority engineering '''''' '''''''''' ''''''''' '''''''''''''''''''''''''''' '''''''''''''''' ''''''''''''''''''''' '''''''''' '''''''''''' ''' ''''''' '''''''''''''''''''''''' ''''''''' ''''''''''''''''''''' '''' '''''''''''''''' ''''''''''''''''''''' '''''''' ''''''''''''' '''''''''''' '''''''' ''''''' ''''' '''''''' '''' '''''' '''''''''''''''''''' '''''''' ''''''''''''' ''' ''''''''''''''''' ''''''''' ''''''''''' '''''' '''' '''''' '''''''''

Acquiring planning permission '''''' '''''''' ''''' '''''''''''''


Table 5-8: Steps and time required for the theoretical conversion of the applicants’ plants to MEK-Toluene

Conversion activity Duration Examples of potential risks and other remarks

Delivery of specialist equipment ''''''' ''''''''' ''''' ''''''''''''''''''' ''''''''''''''''' '''''''''''''''''''''''''' '''''''' '''''''''''''''''''' ''''''''''' '''' ''''''' ''''''''''' '''''' ''''''' ''''' '''''''''''''' ''''''''''''''' '''''''''''''''' ''''''''''''' ''''''''''''''''''' '''''''''''''''''''''''' '''''''''''''''' '''''''''''''''''

Detailed engineering ''''''' ''''''''' ''''''''''''''''''' '''''''''''''''''' ''''''''''''''''''On-site foundation work '''''' '''''''' ''''''''''''''''''' ''''''' ''''''''''''''''' '''' ''''''''''''''' ''''''''''''''' ''''''''''''''' ''''''''' '''''''''''''' ''''''''''' ''''''''' ''''''''''' ''''''''' ''''' ''''''''''''' '''''''''' '''''''''''''''

''''''''''''''''''' '''''' '''''''''''''''''Delivery of standard equipment ''''''' '''''''' '''''''''''''''''''' '''' '''''' '''''''''''''' ''''''' ''''''''''''''''''' ''''' ''''' ''''''''''''''''''' '''''''''' '''''''''''''' ''''' '''''''' ''''''''' '''''''''' ''''' ''''''''''''' ''''''''' ''''''''''''''''

'''''' '''' '''''''''''' '''''''''''''''' ''''''''''''''' '''''''''''''' ''''''''''''''''''''''''' '''''''' ''''''''''''''''' ''''''''' '''' ''''' ''''''''''''''''' '''''''''''' '''''''''''' ''''''''''' '''''''''''''''''''' '''' '''''''''''''' ''''''''''''''''''''' ''''''''''''' ''''' '''' ''''''''''''' ''''''' ''''''''''''''' ''''''''''''

Delivery of pipes and steel ''''''' ''''''''' ''''' ''''''''''''Execution of construction work -

Downtime''''' '''''''''

Unit re-commissioning/Start-up ''''' ''''''''''

Training and modification of newprocess parameters – Unit 1

120 days ''''''''''''''''''''''' '''' '''''' ''''''''''''''' '''' '''''''''''''''' '''' '''''''''''''''' ''''''' '''''''''''' ''''''''''''''''''''''''''' '''''''''''' ''''''' ''''''''''''''''''' '''''''''''''' ''' '''''''''''''''''''' ''''''' ''''''''''''''''''''' ''''''''''''''''''' ''''' '''''''''' ''''''''' '''''' '''''''''''''''''''''' '''''''''''' '''''' '''''''''''''''' ''''''' '''''''' '''''''''''''''''''' ''''''''''''

Fine-tuning of the process ''''''' ''''''''''

All products achieving requiredspecifications

''''''' ''''''''' ''''''' '''''''' ''''''' ''''''''''''''''''''''''' ''''''' '''''' ''''' '''''''' '''''''''''''' '''' ''''''''''' ''''''''''''''''' '''''''''''''''''''''''' ''''''''''''''''''' ''''''''''''''''

Optimisation of process parameters ''''''' '''''''' ''''''''' '''' '''''''''' ''''''''' '''''''''''''''''' ''''' ''''''''''''''''''''Operator training ''''''' '''''''''

Unit 2 conversion 500 days '''' '''''''''''''''''' '''''''''' ''''''''''''''''''''''''''''''''''' '''' '''''''''''''' ''''''''''''''' '''''''''''' ''''''''' '''''''' ''''' ''''''''''''''' ''''''''''''''''''' ''''''' ''''''''''''''''''''''

Training and modification of newprocess parameters – Unit 2

120 days

Unit 3 conversion 500 days ''''' '''''''''''' ''''' '''''''''''''' '''''' ''''''' ''''''''' ''''''''' '' '''''''''''''''''''''' ''''''''''''''' ''''''''''''''''''''''''' ''''''' '''''''''' '''''''''''''''''' '''''' ''''''''''''''''

Total Ca. 4,350 days or 11 years & 11 months (assumes 22 working days per month)



59

This plan can be used as a ‘template’ for actions and time required for conversion to any alternative.However, the timeline presented here has been generated for and applies to a commercially provenalternative. For a yet unknown and unproven alternative, the time that would be required for itsidentification should also be taken into consideration; this would further prolong the time requiredfor conversion.

5.1.6 Conclusion on suitability and availability of MEK-Toluene

The MEK-Toluene solvent mixture, which has been selected as the only possible alternative,comprises solvents which, in hazard and risk terms, are more benign than EDC (in a mixture withDCM). However, the availability of the individual solvents and the wide uptake of the technology byglobal de-waxing/de-oiling units would not translate into suitability or availability for the applicants’units and processes.

Conversion to MEK-Toluene would require significant equipment and process modification withregard to (a) filtration and pumping, (b) heating and cooling (and associated energy costs), (c) hazardcontrols (elimination of CMR substances but simultaneously increased explosion risks), and (d)maintenance. Before any of these changes could be implemented, extensive R&D would need to beundertaken as the applicants would need to ensure that (a) as many products in their portfolio aspossible could be successfully produced with the MEK-Toluene technology, and (b) customers aresatisfied that the ‘new’ products meet their specifications and needs. However, insurmountableobstacles have been demonstrated: (a) technical feasibility cannot improve as it depends on thephysicochemical properties of the MEK-Toluene mixture which are simply not compatible with theexisting production units, them having been designed for use with DI-ME, and (b) the MEK-Toluenemixture is not capable of generating the wider range of high-value specialties that DI-ME canproduce.

Even if technical infeasibility could be disregarded, MEK-Toluene would not make an economicallyfeasible alternative. The applicants’ research has also shown that converting the existing productionunits to this alternative would be accompanied by high costs:

Investments amounting to over '#E#'''''' '''''''''''' (range: €100-1,000 million), dominated bythe significant cost of engineering the plant conversion

Operating costs would experience a dramatic increase, mostly due to a significant energyconsumption increase and expensive loan repayments.

These costs would make the applicants’ operations unviable and the alternative is proven to beunsuitable as a substitute for DI-ME. The argument of MEK-Toluene units being less efficient thanDI-ME units in the applicants’ refineries is supported by the recent and foreseen closures of severalMEK-Toluene units in Europe.

Finally, the de-waxing/de-oiling technology that depends on MEK-Toluene, although readily availablefor licensing and widely used, could not become available to the applicants without undue delay.The theoretical conversion of the two refineries would take an estimated theoretical minimum 12years and would deliver production units that would be far less energy efficient than the existingones and unable to generate the wide range of specialty products currently obtainable through theDI-ME technology. This theoretical conversion plan could be considered a template for thehypothetical conversion of the applicants’ units into a yet unknown, unproven alternative. In such a


60

case, however, additional time should be allowed for the identification or development and thedemonstration of the yet unknown alternatives on an industrial scale.


61

6 Overall conclusions on suitability and availability ofpossible alternatives

6.1 Summary of findings

The identification of potential alternatives and their subsequent screening has concluded that thereis only one possible alternative that has been commercially proven on an industrial scale, MEK-Toluene. As a result the focus of this analysis has been on MEK-Toluene. The overall findings aresummarised in Table 6-1.

The table confirms that MEK-Toluene can be considered neither suitable nor readily available to theapplicants as an alternative for EDC in the context of the applicants’ processes, setup and feedstockcharacteristics.

6.2 Future R&D work planned by the applicants

During an Authorisation review period, the applicants will aim to undertake R&D work along twodifferent directions:

Alternatives for EDC: monitoring of new technologies, patents and solvents, including newR&D work, if new technologies and solvents are identified. If the applicants’ R&D workreveals a new alternative which is less hazardous than EDC and able to generate new, highmargin specialties, the technical parameters and economics of the conversion will beinvestigated in detail. In this case the conversion plan discussed in this AoA for MEK-Toluenewill be adapted to the needs of the new alternative. An internal team will work incollaboration with external experts on the above mentioned tasks with an annual R&Dbudget of approximately '#G#'''''''''''''''

Process improvements: continuous improvement of the closed systems used in the de-waxing/de-oiling plants, with a particular focus on minimising EDC losses and associatedworker exposure. Details of specific actions being considered are shown in Table 6-2 (andare also discussed in the CSR).

The investment budget to be allocated is linked to the applicants’ economic situation, which in turnis dependent upon, among other things, the market conditions. Therefore, continuous monitoringof the market will be undertaken at all times to be able to adjust the investment budget accordingly.


Table 6-1: Summary of suitability and availability of the MEK-Toluene alternative

Parameter Current evaluation Actions required to make the alternative feasible Timescale of actions

Technicalfeasibility

Not feasibleDisadvantages- Worse selectivity towards oil/wax- Higher boiling point components- Cannot deliver level of quality required with current filtration area- Higher explosion risk- Significantly higher electricity consumption and gas consumption

for both heating and cooling different parts of the process- Worse slack wax oil content- Harder to achieve <0.5% oil content in hard wax- Unable to produce the range of specialties currently manufactured

in Hamburg and SalzbergenAcceptable parameters- Similar cloud point- Corrosion potential- Similar base oil wax content

1. Increase the amount of solvent circulating in theunit

2. Lower the filtration temperature for de-waxing3. Increase the surface area for filtration by

'#D#'''''''''%; purchase and install new filters andmodify the process to incorporate a new filtrationstage

4. Change the heat transfer system and substance inthe solvent recovery section

5. Increase temperature and pressure of steam usedfor steam stripping during solvent recovery

6. Increase surface area of heat exchange7. Revamp the wastewater treatment8. Introduce de-waxing aids for some runs9. Increase the use of nitrogen gas for blanketing10. Install new heating facilities, such as hot oil systems11. Renegotiate contracts with steam suppliers12. Screen product qualities and obtain customer

approvals for the ‘new’ products

1: Lab tests2: Engineering – Salzbergen3: Modification - Salzbergen4: Fine-tuning – Salzbergen5: Engineering – Hamburg (EP1)6: Modification – Hamburg (EP1)7: Fine-tuning – Hamburg (EP1)8: Engineering – Hamburg (EP2)9: Modification – Hamburg (EP2)

Total minimum duration: 12years, theoretical '#D#''''''' ''''''''''''''''''''''''''''' ''''' '''''' ''' ''''''''''''' '''''''''''''''''''''''' ''''''''''

Economicfeasibility

Not feasibleInvestment costsQuantified elements- R&D programme: ‘#E#’’’’’’’’’’’’’’ (€1-10 million)- Plant conversion: ‘#E#’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’’ (€10-100

million)- Downtime: ‘#E#’’’’’’’’’’’’’’’’’ (€10-100 million)Unquantified elements- Concrete and steel construction, bulk materials- Possible extensions of utility systems- Materials, equipment and disposal for testing and commissioning- Disposal of construction debris and contaminated excavated soil- HAZOP-related expenses- Conversion costs for ancillary operations (steam and gas supply,

The costs of conversion are dictated by thephysicochemical properties of the MEK-Toluenemixture; these cannot be altered to any significantdegree.

Cost estimates based on approach aimed at minimisingupfront investment costs; this makes the modified plantless energy efficient than it could have been (theapplicants’ units have been specifically designed foroperation with the DI-ME technology).

The applicants would be unable to secure financialbacking for such a conversion plan. The upfront costsare significant, the operating economics are poor and

The applicants would not be ableto secure the necessary financefor any conversion now or in theforeseeable future.Passing on the costs to customersis completely unrealistic, as theprices of products are linked tothe crude oil price and any priceincreases would further damagethe applicants’ competitiveness


Table 6-1: Summary of suitability and availability of the MEK-Toluene alternative

Parameter Current evaluation Actions required to make the alternative feasible Timescale of actions

wastewater treatment)- Personnel trainingOperating costsQuantified elements- Increased energy consumption: '#E#''''''''' '''''''''''''''' (€1-10

million/y)- Regulatory compliance: '#E#''''''''' ''''''''''''''''''- Loan repayments: '#E#'''''''''' '''''''''''''''''' (€1-10 million/y)Unquantified elements- Materials and service costs- Maintenance and laboratory costsPast investments- Past investment written off: '#E#'''''''' '''''''''''' (€1-10 million)

the applicants’ revamped units would be veryuncompetitive vis-à-vis competitors’ energy-optimisedunits of and thus unprofitable.

Alternatively, a grassroots plant rebuild (to build MEK-Toluene purpose-made units) would make operatingeconomics more favourable but would drasticallyincrease investment costs and would severely impactupon the applicants’ ability to manufacture a widerange of high-value specialties

Reduction ofrisks

Human healthHigher explosion risk but comparative risk assessment shows MEK-Toluene is safer than EDCEnvironmentComparative risk assessment shows MEK-Toluene, like EDC, does notraise any concerns over releases (freshwater). However, increasedenergy consumption leads to increased CO2 emissions andenvironmental externalities' #D# '''''' '''''' ''''''' ''''''''''''''''''' '''''''''' '''''''''''''''''' ''''''''' '''''''''''''''''' '''' '''''' ''''''''' '''''' '''''''''''''' ''''' '''''''''' ''''''' '''''''''''''''''''''''''''''' '''' ''''''''''''''''''''' ''''''''''''''''''''''' ''''' '''''' '''''''''''

No action required in terms of worker health impacts.With regard to environmental impacts, a grassroots unitrebuild (to build MEK-Toluene purpose-made units)would reduce energy consumption during operationbut would increase waste generation during plantdecommissioning

Not relevant

Availability MEK and toluene are widely available on the EU market. Theapplicants would require only modest quantities. The MEK-Toluenetechnology is available for licensing. Implementation, however,would require at least 12 years

It would not be possible to substantially reduce thetime required for unit conversion, particularly in light ofthe prohibitive cost of conversion

Not relevant


64

Table 6-2: Plan for continuous improvement of processes during an Authorisation review period

# Continuous ImprovementActions for 2015 onwards

Potential reduction ofsolvent loss / Increase

of safety

Affected plantcomponents

Remarks

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65

7 References

Biribauer, F. A., Bushnell, J. D. & Winsor, R. E., 1971. Low-pour Dewaxing Process Utilizing DualSolvents. USA, Patent No. US 3622496 A.

Broadhurst, T. E., 1982. Dewaxing And Wax Filterability By Reducing Scraper Speed In ScrapedSurface Chilling Units. USA, Patent No. US 4,334,978 A.

Bushnell, J. D., 1976. Immiscible Coolant In Propylene-acetone Dewaxing. USA, Patent No. US3972802 A.

DeKraker, A. R., 1993. Continuous autorefrigerative dewaxing crystallization using a centrifuge. USA,Patent No. US 5221460 A.

Eagen, J., Gudelis, D. & Perry, S., 1973. Combination Of Dilution Chilling With Scraped Surface ChillingIn Dewaxing Lubricating Oils. USA, Patent No. US 3775288 A.

ECHA, 2015. Application for authorisation: establishing a reference dose response relationship forcarcinogenicity of 1,2-Dichloroethane, RAC/33/2015/09 rev 1 Final. [Online]Available at:http://echa.europa.eu/documents/10162/13641/rac_33_dose_response+_1_2dichloroethane_en.pdf[Accessed 10 July 2015].

EIPPCB, 2015. Best Available Techniques (BAT) Reference Document for the Refining of Mineral Oiland Gas, s.l.: European Commission.

Gould, L., 1973. Continuous Dewaxing Of Oils By In Situ Refrigeration. USA, Patent No. US 3720599 A.

Hislop, D. & Eagen, J., 1973. Dewaxing Process. USA, Patent No. US 3773650 A.

Jans, B. & Stepanski, M., 1999. Solvent-free Deoiling of Paraffin. [Online]Available at: http://www.sulzer.com/tr/-/media/Documents/Cross_Division/STR/1999/1999_02_8_jans_e.pdf[Accessed 13 February 2015].

Lynch, T. R., 2007. Process Chemistry of Lubricant Base Stocks. s.l.:CRC Press.

Sequeira, A., 1994. Lubricant Base Oil and Wax Processing. s.l.:CRC Press.

Solomon Associates, 2012. Worldwide Paraffinic Lube Refinery Performance Analysis. [Online]Available at: http://solomononline.com/wp-content/uploads/2012/12/Lube-Study-2012-Invitation.pdf[Accessed 14 November 2014].

'#I#'''''''''''''''' '''''''''''''''''''''' '''''''''' ''''''''''''''''' '''''''''''''''''''' '''''''''' '''''''''''''''' '''''''''''''''''''''''''' ''''''''''''''' ''''''''''''''''''''' '''''''' '''''''''' '' ''''''''''''''''''''' '''''''''''''''''''''''' '''' '''''' ''''''' ''''''''''''''''' ''''''''''''''''''''''


66

ThyssenKrupp Uhde, 2015. Welcome. [Online]Available at: http://achema.thyssenkrupp-uhde.de/[Accessed 13 May 2015].

ThyssenKrupp, 2013. ThyssenKrupp Uhde Engineering Services GmbH. [Online]Available at: http://www.thyssenkrupp.com/en/standorte/detail.html&orga_id=205110[Accessed 17 November 2014].

Walker, J., 1970. Dewaxing Solvent. USA, Patent No. US 3503870 A.

Wauquier, J.-P., 2000. Petroleum refining, volume 2: separation processes (ISBN-10: 2710807610).s.l.:Editions Technip.

West, T. H., 1978. Dilution Chilling Dewaxing Solvent. US, Patent No. US 4,111,790 A.

Wolfmeier, U. et al., 2012. Waxes. In: Ullmann's Encyclopedia of Industrial Chemistry. s.l.:s.n., pp.112-155.


67

8 Annex 1 – Detailed description of process unit operations

The de-waxing/de-oiling process can be described in three main process unit operations (NB. theCSR includes photographs of the relevant parts of the plants):

Crystallisation in the presence of solvent Filtration and filter-cake washing in the presence of solvent Solvent recovery section

8.1 Crystallisation in the presence of solvent

The objective of the crystallisation is to solidify the waxy components out of the oily components, sothat they can be easily removed by filtration. The de-waxing units are charged with warm waxy oil(raffinate) (at 80 to 90 °C) from the tankage. Before the waxy oil begins to crystallise, it has to bediluted with a solvent.

In the applicants’ processes, the specific solvent used is EDC; it acts as one component of a two-component solvent, the other being dichloromethane (hereafter referred to as DCM, EC Number200-838-9, CAS Number: 75-09-2). The ratio of the two components is typically about '#A#''''''''''' (byweight). The two-component solvent EDC-DCM is part of a very small group of solvents universallyacknowledged as suitable for commercial de-waxing and de-oiling for the production of base oils andhard paraffin waxes. The EDC-DCM solvent system is commonly referred to as “DI-ME”.

DCM is a solvent for solving all the oily components, EDC is a solvent which is needed to precipitatewaxy components out of the solution. A specified dilution is needed to lower the viscosity of thefeed and to solve all components of the feedstock components. When it is chilled, crystals of waxycompounds build up and slowly grow. The solvent lowers the viscosity so that the material can flowthrough the system properly. Therefore, more solvent is required for more viscous grades. Thesolvent to raffinate ratio, by mass, varies from '#A#'''''' '''' ''''''.

The mixture is pre-cooled with cold filtrate from the filter section. After pre-cooling, the mixture ischilled to the filtration temperature. The filtration temperature depends on the raffinate fractionand the required pour point of the de-waxed oil. The chilling train consists of a special heatexchanger. Before the solvent raffinate mixture enters the vacuum rotary filter, it is again dilutedwith cold lean filtrate. This dilution is needed to make the slurry more liquid. The mixture of DI-MEensures a crystallisation performance which results in a good (fast) filtration rate with a permeablefilter cake in which the oily components can be washed through the filter cloth easily.

8.2 Filtration and filter cake washing in the presence of solvent

The objective of the vacuum rotary filter is to separate the slurry in wax/solvent and oil/solvent.

The slurry, at filtration temperature, enters the enclosed filter from the bottom. The filter consistsof a rotating horizontal filter drum that is partially submerged (usually to about 35%) in a vat whichcontains the slurry. The hood encloses the vat from the atmosphere and is blanketed with an inertgas. The inert gas is a mixture of vaporous solvent and nitrogen. Solvent is sprayed onto the drum.


68

The shell of the drum is divided up into small compartments. Each compartment is linked to thehead of the filter by two pipes. A grid mounted on the drum supports the filter cloth. A vacuum isused to create a pressure differential across the filter cloth. This pressure differential is the drivingforce that causes the oil and solvent system to flow through the wax cake, filter cloth and pipingsystem to the filtrate receiver. The wax crystals are retained by the cloth and form a bulky filter cakeon the cloth. Figure 8-1 is a cross-sectional view of the filter.

8.3 Solvent recovery section

The recovery (or distillation) sections in all units and for all the different streams are very similar.The recovery sections are a multiple-effect evaporation process. The number of stages used for theevaporation of the solvent has a significant effect on the energy demand of the recovery.

The principle of a solvent recovery is explained on a three-stage process, as seen in in a simplifiedscheme in Figure 8-2. Each product stream of the filtration stages that contain solvent needs its ownrecovery section.

The cold wax/solvent mix respectively the rich filtrate / solvent mix is heated up by the warm streamfrom the last stage (Column C-3) and by condensation of the solvent from the second stage (C-2).When the mixture enters the first column (C-1), the liquid temperature is above the boiling point ofDCM (>75 °C). The superheated solvent flashed in the first column. Around '#A#''''% of the solventevaporates in this stage. The remaining mix is directed to the second stage C-2. Before the mixenters the second stage, it is heated up to ca. 135 °C. The heating source is superheated steam. The

Figure 8-1: Cross-sectional view of the vacuum rotary filter


69

temperature from around 135 °C is above the evaporation temperature from EDC, so '#A#''''% of theoriginal amount of solvent evaporates in this stage. The evaporated solvent is used to heat up thecold mix stream in HX-1 by condensing. The condensed solvent is collected into a solvent receiver.After the second column, the mix (which contains ca. 5% of the original amount of solvent) entersthe last column, after the lost temperature (from evaporation of solvent) is compensated. Theheating source of the heat exchanger (HX-4) is also superheated steam.

The last columns in the recovery section are operated under vacuum conditions. The pressure in thiscolumn is in a range of 20 to 250 mbar abs, depending on the product stream. To match therequired product specifications of a solvent content <10 ppm, the column contains trays. Strippingsteam is injected into the bottom of the column. The product flows through the trays to the bottomof the column and solvent is flushed out of the products by stripping steam. The finished product iscooled down by warming up the incoming product stream and is then directed to the tank farm.

The steam/solvent mixture from the top of column C-3 is mixed with the vaporized solvent from C-1.These streams contain some water, which has to be removed from the solvent. The streams from C-1 and C-3 are therefore condensate in HX-5. The condensate is directed to the top of column C-1.The column contains some trays. The moist solvent is dried by the evaporated solvent. The moistsolvent which enters at the top of the column is dried on its way down and leaves the column waterfree. This water free solvent and the condensate solvent from C-2 are directed to a solventcollecting receiver. This solvent is used as dilution for the waxy raffinate feed and wash solvent. Inorder to be used as wash solvent, the solvent has to be chilled to the filtration temperature with anammonium chiller.

The separated water phase, which contains some remaining solvent, is sent to the wastewaterstripper. The stripped solvent is sent for drying to C-1. The solvent-free water is sent to the refinerywastewater treatment.

Figure 8-2: Overview of solvent recovery section

HX: Heat exchangerC: Column


70


71

9 Annex 2 – Assessment of economic feasibility of MEK-Toluene

9.1 Background

As mentioned in the main part of the report, the applicants contracted TKUES to undertake afeasibility study that sought answers to the following questions:

Is there an alternative substance to replace EDC on a like-for-like basis? What are the disadvantages that may be associated with alternative solvents? What is needed to convert the existing units to an alternative solvent? What costs (with an accuracy of ± 50%) are associated with a solvent change?

In establishing the answers to these questions, the following requirements were taken into account:

The plant throughput and product quality should remain constant The existing machinery and equipment would be reused, where possible, to minimise

investment costs. However, the old rotary drum vacuum filters which were installed in 1980should be replaced as their modification would be complex and economicallydisadvantageous

Energy efficiency was not optimised in this study For the estimation of the solvent switch modification, the Salzbergen unit was investigated

in detail as a case study, while cost-intensive equipment was checked individually for theHamburg units

Changes to the utility requirements caused by the solvent change are highlighted in thestudy. However, impacts on utility systems were not investigated.

The following discussion essentially summarises the authoritative analysis provided in the feasibilitystudy.

9.2 Investment costs for the implementation of the alternative

9.2.1 Overview

Investment costs that would be required for the conversion of the applicants’ units to MEK-Toluenewould include:

Cost of R&D for establishing the compatibility of MEK-Toluene with all products on the H&Rportfolio and obtaining customer approvals

Cost of plant conversion (materials and engineering) Losses from downtime of the production units Cost of fine-tuning the production units and training of personnel.


72

9.2.2 R&D costs

It was explained above that the first of the three key steps to implementing the MEK-Toluenetechnology would be the undertaking of extensive R&D work to ensure that all of the applicants’products can be successfully produced with the new technology and that the requirements andspecifications of customers are met. The applicants would need to requalify >90% of its productportfolio (the remainder are not processed in the applicants’ de-waxing/de-oiling units); they wouldhave to inform their customers that they need to change their production line and, apart fromundertaking lab tests, the applicants would need to send samples to their customers and thecustomers would in turn qualify the samples.

It was explained in Section 5.1.3 that the R&D phase would last a theoretically estimated '#G#'''''''''''''''''''''' '''''' '' '' ''''''''''' Depending on the resources and pilot units used, a cost of'#G#''''''''''''''''''''''''/day for external R&D work could be assumed, while special campaigns can easilycost up to '#G#''''''' ''''''''''''/week '#G#'''''''''''' ''''' '''''''''''''''' '''''''''' ''''' '''''' ''''''''''''''' '''''''' '''' '''''''''' ''''''''''''''' '''''''''''''''' '''''''''''. It is therefore, conservatively assumed that the cost of R&D could be '#G#''''''''''''' '''''''''''''' ''' ''''''''''' '''''''''''''' (range: €1-10 million) or higher. In any case, R&D work will normallyaccount for up to '#G#'''''''''''% of the investment budget of the project.

9.2.3 Plant conversion costs

Approach taken

The feasibility study looked at the plant conversion work with the aim of developing a cost estimate.This cost estimate also includes the costs for debottlenecking/purchasing refrigeration systems andhot oil systems (further detail is shown below).

''#D#''' '''''''''''' '''''''''''''' ''''''' ''''''''''''''''''''''''''''''''''''''''' '''' ''''''''''''''''''''' ''''''' '''''''''''''''''''''' ''''''''''''''''''''''''''''' ''''''''' '''''''''' ''''''''' '''' '''''''''''' '''' ''''''' ''''''''''''''''' ''''''''''''''''''''''' ''''''''''' ''''''' '''''''''' '''''''''''''''''''''''' '''''''' '''''''''''''''''''''''''''''''''''''' '''''' ''''''' '''''''''''''''''''''''' ''''''' '''''''''''''''' ''''''''' '''' ''''' '''''''''''''' ''''''''' ''''''''''' '''''' ''' '''''''''' ''''''''' ''''''''''''''''' '''''' ''''''''' ''''''''''''' ''''' ''''''' ''''''''''''''''' '''''''''' ''''''' ''''''''''''''''

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73

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Plant changes required to address technical shortcomings

The comparison of the technical parameters of the MEK-Toluene technology against the technicalfeasibility criteria in Section 5.1.3 provides the starting point for identifying the areas where changesto the plant would be required. These are summarised in Table 9-2 overleaf.

In light of the changes and requirements shown in the table, the following sections/systems thatrequire costly interventions were considered in detail in the feasibility study:

Filter section (Modification/new filters and additional filter stage) Vent gas system (compressor) Solvent recovery (design temperature, dimensions) Cooling system including scraped surface exchangers Hot oil system Warm water system.

Focus on filterability

Filtering plays a vital role in the separation of waxes from oils and this is why special attention mustbe given to it. MEK-Toluene generally has worse filterability than DI-ME, as explained above;therefore, a larger filter area would be needed to achieve equivalent results. The feasibility studyincluded a comparison of filtering performance between the two technologies. The comparison ispresented in Table 9-1. The table confirms that in order for the yield and product quality to remainthe same (as represented by oil yield and oil content in slack wax, see numbers in bold), the MEK-Toluene technology would require '#D#'''' ''' ''''''''''''''''''' '''''''''''''''' '''''' ''''''''''''''' '''' ''' ''''''''''''''''' '''''''''''''''' ''''' '''''''''''''''''''' ''''''''' ''''''''' '''''''''''''''' ''''''' ''''' '' '''''''''''' '''''''''''''''''' ''''''''''''''''''''''''''' ''''''' '''''''''''''''''''''''''''''''''''' ''''''''' ''''' ''''''''''''''' '''' ''''''''' '''''''''''''' '''' ''''''''''' '''' ''''''''''' '''''''''''''''''' ''''' '''''' ''''''' ''''''''''''''''''''''''''''''''''''' ''''' '''''''''''''''''' ''''' '''''' '''''''''''''''''''''

Table 9-1: Filtering performance/operating conditions with DI-ME and MEK-Toluene

Parameter DI-MEMEK-Toluene

(Base oil-optimised)MEK-Toluene

(Wax-optimised)

Number of filtering stages '#D# all Table 9-1'' '' '''

Filter surface ''''''''''' '''''''''' ''''''''''

Solvent circulation, vol% ''''''' ''''''' '''''''

Filtration temperature, ° C '''''' ''''''' '''''''

Oil yield, wt% ''''' ''''' '''''

Oil content in the slack wax, wt% '' ''''' '''



Table 9-2: Required technical changes for the theoretical implementation of MEK-Toluene and their practical implications

Technical feasibilitycriteria (selected)

Plant change required to address technical shortcomings Practical implications of the proposed changes

Solubility andselectivity

Increase the amount of solvent circulating in the unit A greater amount of the circulating solvent would increase theenergy required relative to the yield

Lower the filtration temperature for de-waxing. This would maintain thelow poor point of the base oils

The energy consumption of the plant would increase

Boiling point

Specific heat capacity


The operating temperature influences the solvent recovery and the meansof production which are used for this process. The higher boilingtemperatures of MEK and toluene would make condensation of solventvapours easier; however, MEK-Toluene would require higher evaporationtemperatures in the solvent recovery sections. Therefore, a differentheating medium would optionally be required. In addition, a higherequipment design temperature would be required.

Increase temperature and pressure of steam used for steam strippingduring solvent recovery. DI-ME requires steam at 150 °C. The alternativewould require steam at more than 260 °C.

The higher heat of vaporisation and heat capacities of MEK-Toluene resultin a higher degree of heat transfer. Therefore, additional heat exchangesurface would be needed, especially in the solvent evaporator

The energy balance of the plants would be affected. Currently,surplus steam is used for heating. Upon conversion to MEK-Toluene, the steam consumption will decrease, because it wouldno longer be used as a heating medium. The applicants woulduse heating oil instead of steam as a heating medium, and heatingoil has a higher temperature than steam. To use heating oil, theapplicants would need to install new heating facilities

The applicants would need to renegotiate their contracts withtheir steam suppliers

The higher energy steam would be more expensive to generate

Cloud pointA wider temperature range would be required for the process The increased temperature would lead to greater energy

consumption


Table 9-2: Required technical changes for the theoretical implementation of MEK-Toluene and their practical implications

Technical feasibilitycriteria (selected)

Plant change required to address technical shortcomings Practical implications of the proposed changes

Filterability

The density of the existing DI-ME solvent is significantly higher than thedensity range of oil and wax so that the wax phase (lighter paraffin) floatsin the filter instead of settling at the bottom. For MEK-Toluene (and allother tested solvents), this is not the case. With MEK-Toluene, there wouldbe a risk that wax settles in the trough and accumulates there. In addition,the permeability of the cake paraffin in DI-ME is larger; thus, the oil-solventmixture penetrates the cake faster. This allows there to be fewer filteringsteps with DI-ME than with MEK-Toluene.

Conversion to MEK-Toluene would require a different design for the drumfilter cells. In addition, the solvent pumps require larger discharge heightsat the lower density of MEK-Toluene. Generally, density has an influenceon equipment (filter) design with regard to immersion depth, wiper/scrapersystem, washer jet arrangement, position of the inspection window, etc.

With MEK-Toluene, the oil phase would dissolve noticeably less than thefilter cake. This would require larger filter areas for the alternative solventMEK-Toluene. In addition, depending on the required remaining oil contentin the filter cake, this would lead to more filter stages. By encouragingcrystal formation the performance of DI-ME could not be achieved. Thismeans that in MEK-Toluene filtration colder temperatures would beadjusted to achieve the required pour point of the oil

Increase the surface area for filtration by ''#D#'''''''''% dependingon unit configuration. For the same oil content in paraffin anadditional filter stage is needed. The applicants would have topurchase and install new filters and modify the process toincorporate a new filtration stage.

'#F#'''''' ''''''''''''''''' '''''''''' ''''''' '''''''''''' ''''''''' ''' ''''''''''''''''''''' ''''''''''''''''''''' ''''''''' '''''''' '''''' '''''''''' ''' '''''''''''''''''''''' ''' ''''''' ''''''''''''''''''''''''''''''''''''''''' ''' '''''''' ''''''''''''''''' '''''''' ''''''''' '''''''' '''''''''' ''''''''''''' ''''''''''''''''''''''''''''' '''''''''' ''''''''''' ''''''' '''' ''''' '''''''''''''''''' ''' '''''''''' '''' '''''''' '''''''''''''''''''' ''''''' '''''''''' '''' ''''' '''''' ''''''' '''''''''''''''' '''''''' '''''''' '''''''''' '''''''''''''''''' ''''''' ''''' '''''''''''''''' ''''''''' '''''' ''''''' '''''''''' ''''''''''''''' ''''''''''' '''' '''''''''''' '''''' '''''''''' ''''''''''' ''''' '''''''''' '''''' '''''' ''''''''''''''''' ''''''' '''''''''''''''''''' '''''''''''''''''' ''''''' '''''''''''''' ''''''''''''''''''' '''''' ''''''''''' '''''''''''''''''''''' ''''' ''''''''''''''''''''' '''''''''''''''' ''''''''' ''''''''''' ''''''''''''''''' '''''''''' '''''''''''''''''' ''''''' '''''''''''''''''''''''''''''''' ''''''' ''''''' '''''''''''''''''''' ''''''''''''''' ''''''''' ''''''''''''' ''''''''''''''''' ''''' ''''''''''''''

'#D#''''' '''''''''''''''''' ''''''' '''''''' '''''''' ''''''''''''' ''''''''''''''' '''''''''' ''''''''''''''''''''''''''' ''''' ''''''''''''''''''''''''''''''''''''''''' '''''' ''''''''' ''''''''''' '''''''

The applicants may need to introduce de-waxing aids for someruns to ensure an efficient filtration rate with the requiredproduct quality

Explosion riskIncrease use of nitrogen gas for blanketing The applicants would have to purchase more nitrogen gas and

treat more flue gases

Energy consumptionThe refineries would need additional new heating facilities, like hot oilsystems, to generate the needed high level energy with natural gas

Cost of installation and operation of new systems would arise



76

Estimates of plant conversion costs

With the new requirements for MEK-Toluene described above, the de-waxing/de-oiling unit inSalzbergen was examined with the help of process simulation models in accordance with applicable'#F#'''''''' runs to define the necessary conversion needs. That includes modifications, additions orreplacement of rotary drum filters, scraped surface heat exchangers, columns, pumps, heatexchangers, tanks, and auxiliary systems, such as refrigeration system, hot oil system and hot watersystem. A total of ca. 100 main pieces of equipment are assumed to be affected. Table 9-3 providesthe specifications for the capacity of specialist equipment assumed for the Salzbergen and Hamburgunits.

Table 9-3: Capacity data of specialist equipment required for the Salzbergen and Hamburg units

Capacity data of specialistequipment

UnitDI-ME MEK-Toluene

EP EP1 EP2 EP EP1 EP2

''#D#, #F#''''''''''''''''''''''''''''''''''''''''''''

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'''

''''''''''''' ''''''''''''' '''' '''''' ''''''''''''''''''''''''' '''''' '''''''''''''''

''''''''''

''''''''''''' '''''''''' ''''''''''' '''''''''''''' ''''''''''' '''''''''''

''''''''''''' ''''''''''''' '''' '''''''''''''''''''''''''' '''''''''' '''''' ''''''''

''''''''' '''''''''' ''''''''''' ''''''''''''''''''''''

'''' '''' ''''''''''''''''

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'''' '''' ''''''

''''''''''''''' ''''' ''''''' '''''''''''' '''''''''''''''''''''''''''''''''''''

'''''' '''''''''' ''''''''''' ''''''''''' '''''''''' '''''''''''' '''''''''''

Source: TKUES feasibility study''' ''''''' ''''''''''''''''''' ''''''''''' ''''''''''' ''''''''''' '''''''''' '''''' '''''''''''''''''''''''''' ''''''''' '''''' ''''' ''''''''''''''''

For the Salzbergen unit, investment costs were calculated for the main parts of equipment. The costof materials / installation costs for bulk materials (piping, instrumentation and electrical equipment)were estimated by using factors. This was done in detail when required for individual sections, asappropriate. In order to determine budgets for the elements “filter” and “refrigeration unit”,information was requested from manufacturers. Finally, the engineering costs were estimatedbased on figures provided by TKUES.


77

Still, there are cost elements that have not been considered but which cannot be ignored:

Costs for concrete and steel construction (including scaffolding, building, constructionmanagement, etc.)

For bulk materials, including piping, instruments, valves, and electrical equipment, nodetailed investigations have been made

Possible extensions of utility systems Consumption/test materials and equipment during the construction and installation phase

on site and commissioning, including electricity, water, steam, compressed air Disposal of used test/resources (including EDC/DCM) and wastewater Loading, transportation and disposal of construction debris and contaminated excavated soil Any additional expenses from HAZOP; this would be required to ensure the process safety of

the modified units Expansion or new equipment installations and auxiliary systems, unless they are part of the

machine and equipment list.

Table 9-4 shows the breakdown of site development costs for the plant at Salzbergen. This table is areduced version of a much more detailed table available in the feasibility study.

Table 9-4: Cost of plant conversion for the Salzbergen unit

Sub-total

DescriptionMaterials(€million)

Assembly/disassembly

(€million)Total (€million)

1 Direct costs – Equipment(17 items listed in the feasibility study)

'#E# all Table 9-4'''''''''''

'''''''''' ''''''''''''

2 Direct costs – Bulk materials(4 items listed in the feasibility study)

'''''''''' ''''''''''' ''''''''''

3 Direct costs – Construction(2 items listed in the feasibility study)

''' ''' '''

4 Indirect costs(3 items listed in the feasibility study)

''' ''' '''

Sub-total (1,2,3,4) '''''''''''' ''''''''' '''''''''''''

5 Other costs(3 items listed in the feasibility study)

''''''''''' ''' ''''''''''''

6 Service(6 items listed in the feasibility study)

''''''''''

7 Finance, taxation, capital costs(5 items listed in the feasibility study)

''' ''' '''

Sub-total (5,6,7) ''''''''''

8 Contingencies ''''''''''

Total cost (price base: 2nd

Quarter 2014)'''''''''''

Range: €10-100

Source: TKUES feasibility studyImportant note: for the realisation of the conversion work, a timeframe of about two years per unit isestimated, as shown in Section 5.1.3

The overall cost is given with ±'#E#''''% accuracy (without inflation being taken into account).±'#E#''''% accuracy is typical for cost estimation in a study phase.


78

In order to determine the required reconstruction measures and the estimation of the costs for theHamburg plant, the costs were calculated on scaling factors based on the system throughput bymeans of a digression exponent. The individual sections have been considered separately (scrapedsurface heat exchanger, drum cell filter, filter gas compressor and cooling installation) and some ofthe existing equipment is assumed to be suitable for re-use:

D

For all the remaining installation parts, the costs have been scaled from the EP installation inSalzbergen to correspond to the respective installation capacities for the Hamburg installation.Specialist equipment prices for the Hamburg plant were requested from manufacturers/vendors.The cost of standard equipment was determined based on TKUES’ cost database.

Table 9-5: Cost of plant conversion for the applicants’ units

SalzbergenEP

HamburgEP1

HamburgEP2

Total

''#E# all Table 9-5''''''''''''''' '''' '''''''''' '''''''' ''''' ''''' ''''' '''''

'''''''''''''''''''' ''''''''''''''''''

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Total cost '''''''''''''''''''''''''''''''''''''''

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Range: 10-100 million



79

Other costs associated with plant conversion

The installation of new equipment, including the new filters and heating systems, would represent asignificant cost to the applicants, as shown above. Some associated costs not included above butalso not quantified include the following:

Long-term contracts with the steam supplier have to be adjusted; the applicants would needless heating steam and this would have an impact on their steam supplier’s business

New heating facilities have to be built and the natural gas supply needs to be built Wastewater and gas treatment facilities require modifications for the two new substances

(MEK and toluene).

9.2.4 Downtime costs

As noted earlier, the theoretical conversion of the plants would require '#D#''' months of downtime,'#D#''''''' '''''''''''''' '''''''''' '''''''''. This downtime would lead to a loss in gross profits equivalent to a one-off estimated cost of more than '#E#'''''' ''''''''''''. This may well be a significant underestimate of thereal impact. '#E#''''''' '''''''''''''''''' '''''''''''''''''' '''''''' ''''''' '''''''''' ''''''''''''''' '''''' '''''''''' '''''''' ''''''''''' ''''''''''' '''''''''''''' ''''''''''''''''''''''''' ''''''''''''''''''''' ''''' ''''''''''''''' ''''''''''''''''''' ''''''''' '''''' ''''''' '''''''''''' '''' ''''''''' '''''''''''''''''''''''''''''''''''''''' '''' '''''' '''''' ''''''' ''''''''''' '''''''''''''''''''''''' ''''''' '''''''''''''''''''''''''' ''' ''''''''''''''''''' ''''''''''''' ''''''' ''''''''''''''''''''' ''''''''' ''''''' ''''''''''''' '''''''' '''''''''' ''''''''''''' '''''''' ''' '''''''''''''' ''''''' '''''''' '''''''' '''''''''' ''''' '''' '''''''' '''' '''''''''''''''''''' ''' ''' ''' ''''' '''''''' ''' ''''''' ''''''''''''' ''''''''''''' ''''''' ''''''' '''''''''' '''''''''''''''' ''''' '''''' ''''''''''''''''''''''''''''''''''' '''''''''''''''''''' ''''''' '''''' '''''' ''''''' ''''''''''''''''''' ''''''' '''''''''''''''' ''''''''''' '''''''''''' '''''' ''''''''''''' '''''''''''''''' '''''''''''''' ''''' ''''''''''''''''''''''' '''''' ''''''''''''' '''' '

It should also be noted that, after the production units re-start operations, there would be a periodof gradual increase in production before maximum throughput could be reached.

9.2.5 Personnel training costs

The applicants would need to retrain employees in order to switch to MEK-Toluene (or indeed anyalternative), at significant cost to the applicants. In addition, some time and experience would beneeded to reach the maximum throughput of the revamped units. The relevant cost cannot bequantified.

9.3 Loss of past investment

The applicants have invested significantly in improving the manufacturing process in Salzbergen andHamburg. Many important investments have not yet run their full lifecycle and therefore, significantchanges to the equipment and process parameters could render such improvements obsolete and aproportion of the associated funds invested would be lost. Table 9-6 summarises the importantinvestments made by the applicants in the 2000s. The table shows what the expected lifetime ofeach investment has been and the amounts invested each time. The table also calculates theresidual value of these investments in 2017 and shows that '#C#'''''''' '''''''''''' (range: €1-10 million) (in2014 prices) would stand to be forfeited if the applicants could no longer use EDC and thus theequipment referred to in the table would need to be replaced in 2017 (new filters would be neededand significant changes to the gas treatment equipment would be required owing to the need toremove different substances from the flue gases).


80

Table 9-6: Past investments by the applicants in the affected production units

Description of pastexpenditure

'#C# all Table 9-6'''''''''''''''' '''''''' '''''''''''''''''''' ''''''''''''''' '' '''''''''' '''''''' ''''''' '''''''''''''''

'''''''''''' '''''''''' ''''''''''''''''''''''' ''''''' '''''''''''''''''''

Original cost in € '''''''' ''''''''''''' '''''''' '''''''''''''

Inflation rate to 2014* '''''''''' '''''''''' ''''''''''' '''''''''''' '''''''''' ''''''''''''

Cost in 2014 prices '''''''' ''''''''''''' '''''''' '''''''''''''

Year of investment '''''''''''''''''' '''''''''' ' '''''''''

Originally expected lifetime ''''' '''''''''' ''''' ''''''''''

‘End of life’ of investment '''''''''' ''''''''''

% years remaining in 2017 ''''''''' '''''''''

Value not written off in 2017 ''''''''' '''''''''''' '''''''' ''''''''''''''

Total ''''''' '''''''''''' (€1-10 million)

* Inflation to year 2014 was calculated using http://fxtop.com/en/inflation-calculator.php (accessed on 10December 2014)

9.4 Changes in operating costs

Table 9-7 shows how operating costs at the applicants’ units may change when converting to MEK-Toluene.

Table 9-7: Overview of changes to operating costs when replacing DI-ME with MEK-Toluene

Cost component Change Description

Energy costs

Electricity Increase Electricity consumption would be expected toincrease by +'#E# all Table 9-7'''''

Gas Increase More heating and cooling energy would beneeded, gas consumption would be expected toincrease by +'''''% for heating and +'''''% forcooling

Materials and service costs

Cost of process solvent (currently EDC-DCM) Uncertain Even if the volume of solvent in the systemmight change, the new solvent would still berecycled; cost changes cannot be estimated

Raw materials (excluding water and EDC butincluding their delivery costs)

Increase More N2 would be needed to minimise thedanger of explosion.The applicants would need to use de-waxingaids with some products

Water Stable No change envisaged

Environmental service costs (e.g. wastetreatment and disposal services)

Stable No change envisaged

Transportation of end products Stable No change envisaged

Labour costs

Salaries, for workers on the production line(incl. supervisory roles)


Costs of meeting worker health and safetyrequirements (e.g. disposable gloves, masks,etc.)

Stable No change envisaged. PPE would be at thesame high level. Gloves, filters etc. might besubstituted, not eliminated and workers wouldstill undergo medical examination every year


81

Table 9-7: Overview of changes to operating costs when replacing DI-ME with MEK-Toluene

Cost component Change Description

Maintenance and laboratory costs

Costs associated with testing, equipmentdowntime for cleaning or maintenance (incl.maintenance crew costs and lab worker costs)

Increase Due to a larger amount of equipment, moremaintenance and longer downtime forinspections would be required

Other costs

Marketing, license fees and other regulatorycompliance activities

Uncertain Not possible to predict at present

Other general overhead costs (e.g. insurancepremiums, administration, etc.)



9.4.1 Energy

General

Conversion would allow the units to operate with MEK-Toluene. Afterwards, however, they wouldcompare quite unfavourably, in terms of energy consumption and efficiency, with equivalent plantselsewhere. This is because they were originally designed and built as DI-ME units: they incorporateelements that are fundamentally less suited to MEK-Toluene but could not be changed withoutrebuilding the plants from scratch. Although each of these elements may seem quite minor on theirown, the cumulative impact would be significant.

Electricity

Notably, the new heating systems installed in order to compensate for the loss of excess steam,currently used for heating, would increase energy consumption. Furthermore, energy consumptionwould increase as a consequence of the wider range of temperatures required to heat the solvent-feedstock mixture so that all fractions dissolve and then to cool it in preparation for filtration.

Calculations made by TKUES and based on experience with various studies/projects suggest that theoverall result would be an increase in electricity costs of '#E#''%; this estimate is relevant for all de-waxing/de-oiling units.

Natural gas

There are a variety of reasons why increased natural gas consumption for heating and cooling wouldarise:

Filtration performance: because of poorer MEK-Toluene crystallisation performance, thefiltration temperature would have to be lowered in order to maintain the required pourpoint of the base oil. In addition, with MEK-Toluene, the oil phase would dissolve noticeablyless from the filter cake. This would require larger filter areas for the alternative solvent.Depending on the required remaining oil content in the filter cake this can lead to anincrease in the number of filtration stages

Solvent recovery: the higher boiling temperatures of MEK and toluene would make thecondensation of solvent vapours easier; however MEK-Toluene would require higherevaporation temperatures in the solvent recovery sections. Therefore, a different heating


82

medium would optionally be required. In addition, higher design temperatures ofequipment would be required. MEK and toluene’s heat of vaporisation as well as theirspecific heat capacity are higher than those of EDC and DCM. This would lead to greaterenergy consumption and heat transfer, and would require additional heat transfer surfaces.Overall, to successfully switch to MEK-Toluene, the applicants would need to increase thetemperature of the steam used, from around 150 °C to more than 260 °C.

Table 9-8 explains the changes in consumption that would arise for a throughput of '#E#''''' t/h withDI-ME and MEK-Toluene. The figures in the table are based on the findings of the TKUES feasibilitystudy. The table confirms that, for MEK-Toluene, '#E#''''% more heating output and '#E#'''''% coldcapacity would be required.

Table 9-8: Energy consumption with DI-ME and MEK-Toluene

'#E# all Table 9-8'''''''''''' '''''''''''DI-ME

''''''''''''''''' ''''''''''' MEK-Toluene

Mass flow[t/h]

Cooling/heatingoutput[MW]

Mass flow[t/h]

Cooling/heatingoutput[MW]

Ammonia recycle '''''' '''''' '''''' '''''''

Cooling water recycle ''''''''''' '''''''' '''''''''' ''''''''

Tempered water recycle '' '' '''''''' ''''''

Hot oil recycle '' '' ''''''''''' '''''''''

Low pressure stripping steam '''''''' '' ''''''''' ''

Low pressure heating steam '''''''' '''''''' '''''' ''''''

Medium pressure stripping steam '''''''''' '' ''''''''''' ''

Medium pressure heating steam ''''''''' ''''''''' '''''' ''''''

Total capacity DI-ME Cooling/ heating output[MW]

MEK-Toluene Cooling/ heatingoutput [MW]

Chilling capacity (ammonia chilling unit) '''''' '''''' ''''''''''''''

Cooling capacity (cooling water system) ''''''''' '''''''''

Heating capacity (or steam demand) ''''''''' ''''''''' '''''''''''''


These estimates can be used to calculate the energy demand increases in the Hamburg plant, inTable 9-9.

The table suggests that an additional '#E#''''''''''''' MWh/y would be required in the form of naturalgas in Hamburg. For the purposes of this calculation we assume that the size of the Salzbergenoperations is roughly '#A#''''% of the Hamburg operations. Therefore, the energy increase across allunits can be tentatively estimated to be '#E#''''''''''' '' ''''''''' ''' '''''' ''''''''''''' MWh/y. The price paid bythe applicants for natural gas in Hamburg is €''''''''''/kWh and in Salzbergen ca. €'#E#'''''''''/kWh. Thisprice would mean an additional cost to H&R of ca. '#E#''''''''''''' ''' '''''''''' ''' '''''''''' ''' ''''''''''''' ''' ''''''''''''''''''' ''' '''''' ''''''''' million/y (range: €1-10 million/y).


83

Table 9-9: Increase in energy consumption and associated carbon dioxide emissions in Hamburg whenusing MEK-Toluene

DI-ME in Hamburg MEK-Toluene in Hamburg

'#E# allTable 9-

9''''''' '''''''''''''''''''''''''''

''''''' ''''''''''''''''''''''''''''

'''''''''''''''''''''''''''''

''''''''''''''''''''''''''''''

'''''''''''''''''''''''''''''

''''''''''''''''''''''

'''''''''''''''''''''''''''

''''''''''''''''''''

''''''''' ''''''''''''''''' '''''''

''' '''''' ''''''''''''''''' '''''' '''''''''''''' '''''''''''''' '''''''' '''''''''''''' '''''''''''''' ''''''''''' '''''

''''''''' ''''''''''''''''''''''''''

'''''''''''''''' '''''' ''' '''''' '''''''''''' ''''''''''''''' ''''''''' ''''''''''''' ''''''''''''''' '''''''''' ''''''

'''''''''''''''''''''''''''''''' '''''''

''' '''''' ''''''''''''' ''''' ''''''''''''' ''''''''''''' '''''''' '''''''''''''' '''''''''''''' ''''''''''' '''''

'''''''''''''''''''''''''''''''''''''

''''''''''''''''''''''''''''

'''''''''' ''''''

Source: TKUES feasibility study* A net calorific value of 0.2055 kg CO2 per kWh natural gas has been used

9.4.2 Materials and service costs

Solvent consumption

The applicants do not hold sufficient information to allow an estimation of the changes to operatingcosts in respect of the replacement of one solvent mixture with another to be calculated. It is alsolargely considered to be of limited significance to calculate the additional costs for the solvent inlight of the conversion costs discussed above.

Nitrogen consumption

MEK and toluene have lower toxicity and water hazard than the chlorinated substances EDC andDCM, the flash points of MEK and toluene are a little lower than those for EDC and DCM and the gasexplosion limits for MEK and toluene are also lower than for EDC and DCM (see Table 5-2). Theoxygen concentration in the filter gas system should be supervised and would have to be keptsignificantly below 9.5% v/v when using MEK-Toluene leading to an increased consumption ofnitrogen for blanketing of the filters. The applicants cannot quantify the increase in nitrogenconsumption and the associated cost.

Other additives

The applicants would need to use de-waxing aids with some products. These aids are needed forbetter crystallisation and filtration rates, which are needed for the production of specialities. Theircost cannot be quantified.

9.4.3 Labour costs

No significant changes are envisaged.


84

9.4.4 Maintenance and laboratory costs

Transferring to the alternative would leave the applicants with more equipment at both Salzbergenand Hamburg. The additional equipment would increase the costs associated with testingequipment and downtime for cleaning and maintenance, as the applicants would have to pay formaintenance crews and laboratory employees. The increased maintenance costs cannot beestimated.

9.4.5 Other costs

Regulatory compliance

Whilst elimination of EDC from the production process would reduce REACH-related compliancecosts, the increased energy consumption and concomitant increase in the release of CO2 wouldmean that additional CO2-certificates would have to be purchased by the applicants. At present, thecost of the certifications is €'#E#''''''''/tonne CO2. Therefore, the increased cost of certificates wouldbe '#E#'''''''''' ''' ''''''''''' ''' ''''''''''''''' per year for the Hamburg plant alone. If it is assumed that theemissions expected at Salzbergen would be ca. '#B#'''''% of those in Hamburg, the overall cost can beestimated at ca. €'#E#'''''' million/y (€<1 million year).

Costs of measures taken for the protection of workers’ health, including cost of Personal ProtectionEquipment (PPE), would not substantially change.

9.4.6 Cost of financing

The applicants could not finance the conversion of the Salzbergen and Hamburg units using ownfunds but instead would need to secure long-term loans to the tune of 100% of the conversion cost.'#C#'''''''''''' '''''''''' '''''''''' ''''''''' '''''''''''''''''' ''''''''''''''''''' '''''' '''''' ''''' ''''''''' '''''''''''''''''' ''''''''''' '''''' ''''''' ''''''''''''''''''' ''''''' ''''''''''' ''''''''''''' ''''''''' '''''''''' ''''''''''''''''' ''''''' '''''''''''''''''' ''' '''''''''''''''''' '''' ''''''''''''''''''' ''''''''''''''''' ''''''''''''''''''' '''''''''''''''' ''''' '''''' '''''''''' ''''''' ''''''''''''''''' '''''''''' '''''' ''''''''''' '''' '''''''''''' '''' ''''''''''''''''''' ''''''' '''''''''''''''''''''''''' there can be no guarantee that in the future profits will be sufficiently high to allow majorengineering works to be funded. In light of the applicants’ inability to self-finance the conversion ofthe production units, third-party funding would be required.

External funding would be unrealistic to obtain and, if obtained, could be expensive. Firstly, the sumrequired would be very substantial. Secondly, the benefits of conversion would be very small,essentially limited to the reduction of an already low risk to workers’ health. There would, forexample, be no benefits to product quality or yield, the specialties portfolio of the applicants wouldbe lost and energy consumption, process efficiency and operating costs would all be negativelyaffected. It would therefore be very difficult to present an attractive, long-term business case tofinancial institutions that could help the applicants raise the finance required for the conversion.

However, for the purposes of the present example calculation for the MEK-Toluene, it isoptimistically assumed that bank loans could be secured and the interest rates would not beprohibitive. Based on information from existing loans that the applicants currently holds, if financecould be obtained, a typical interest rate would be '#E#''%. A simple calculation can be made onloan repayments; assuming that the applicants would require ca. '#E#'''''''' '''''''''''''' for the plantconversion, if the term of the loan was 15 years and the interest rate was '#E#''%, the total


85

repayment would be ca. €'#E#'''''' million (effective annual rate '#E#''''''''%) which is equivalent to amonthly payment of ''#E#'''' '''''''''''' '''''''''''''' or ''#E#''''''' ''''''''''''' per year11 (range: €1-10 million/y).

9.5 Economic feasibility of MEK-Toluene in the context ofcompetition

The applicants’ refineries belong to the Group I base oil refineries. Groups I to III are refined baseoils, meaning that they are produced from the refining of crude oil. Group IV oils are synthetic baseoils in that they are produced by chemical modification (also see discussion in Section 2.2.2 of theSEA). The last few years have been particularly challenging for refined Group I base oil producers.Several refineries in the EU and globally have ceased or are planning to cease operations, as shownin Table 2-9 of the SEA. This brings to the fore two important parameters:

Profitability of MEK-Toluene Group I paraffinic oil refineries: the plants which have shutdown are all MEK-Toluene refineries. These refineries are considered to be less efficientthan DI-ME plants and which could not manufacture a wide range of highly marketablespecialties. As noted earlier, the applicants’ refineries manufacture ca. 800 differentproducts, including base oils, brightstock, lubricating oil blends, medical and technicalparaffin waxes, process oils (softeners for the tyre and rubber industry). It is this wide rangeof end products that makes the applicants’ refineries commercially successful and which canguarantee the future profitability of the refineries in the face of competition (see Section2.2.2 of the SEA for much more detail on the advantages of the applicants’ business modeland portfolio)

Level of competition: at present, Group I oils represent ca. 60% of the global demand,however, there have been suggestions that this will decline to 30-40% of the global base oilpool in the next 20-25 years (Serra-Holm, 2013). Competition from non-EU (particularlyAsian and Russian) manufacturers is increasing. Therefore, the production economics of theapplicants’ refineries following a conversion to an alternative would be critical to theprofitability of the business vis-à-vis EU and non-EU.

Here, it is useful to consider the particularities of paraffin oil refineries using the DI-ME technology.Solvent extraction is the only way of obtaining Group I base oils. Beyond base oils, no other lubebase stock production method has been able to supply aromatic process oils (needed for productssuch as tyres or technical rubber goods) or paraffin or microcrystalline waxes. However, whilst arefinery of this type is on the one hand able to produce a wide variety of end products, on the otherhand, it is not able to reduce the production of one product without lowering the production of allthe others as well; this can be described as ‘coupled production’. If a ‘coupled production’ plantloses margin on one of its products this has to be compensated by all other products.

In contrast, alternatives to the applicants’ products are typically products sourced from outside theEU or based on alternative production methods (units using the MEK-Toluene solvent mixture ornaphthenic crude feedstocks). These imported streams and different production methods

11Calculation performed using an online loan calculator,

http://www.thecalculatorsite.com/finance/calculators/loancalculator.php (accessed on 12 December2014).


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concentrate on the production of just one or few products boosting their economies of scale. Thisalready puts a lot of pressure on ‘coupled production’ refineries and any additional pressure such ashaving to invest heavily in changing the production technology would immediately disturb thisdelicately balanced production. In the long run, the applicants’ and other refineries of the sametype are aiming for an even wider variety of products all coming out of the same stream.

Therefore, any alternative to the DI-ME technology which cannot preserve the breadth of theapplicants’ portfolio and affects the applicants’ profitability could not be considered as realistic as itwould jeopardise the applicants’ business future.


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10 Annex 3 – Risk evaluation of alternative substances

10.1 Methodological approach

Article 60 (5) of REACH requires the applicant to investigate whether the use of the alternativesubstance “would result in reduced overall risks to human health and the environment” (ascompared to the Annex XIV substance, EDC).

Following the screening process presented in Section 4.3, the alternative solvent mixture methylethyl ketone/toluene (50/50) was selected for in-depth analysis.

In order to comply with the REACH requirements, the hazard profiles of the two substances in themixture are presented and suitable reference values for a quantitative comparison (DNELs forhuman health assessment, PNECs for an assessment of environmental toxicity) are either identifiedor (if no such reliable basis could be found in the public domain) derived (Section 10.2).

Literature searches (up to October 2014) for the alternative substances selected for in-depthevaluation were performed in bibliographic and other databases as appropriate (after consultationof existing assessments) as well as assessments available from eChemPortal and other sources werescreened.

More specifically, the following sources and search steps were used to retrieve relevant information:

ECHA CHEM database (http://echa.europa.eu/search-chemicals) eChemPortal (http://www.echemportal.org/echemportal/), with all related sources Bibliographic database Pubmed (http://www.ncbi.nlm.nih.gov/pubmed/) The US NLM portal TOXNET (http://toxnet.nlm.nih.gov/ including the bibliographic database

Toxline and other databases) ECOTOX database (http://cfpub.epa.gov/ecotox) The aquatic toxicity database CHRIP of the Japanese Ministry of Environment

(http://www.safe.nite.go.jp/english/db.html).

As not only is a comparison of hazard profiles required to develop a human health andenvironmental exposure scenario (Section 10.3) but also a comparison of substance properties onthe basis of risk. Exposure within this scenario is estimated using the Tier I tool ECETOC TRA v.3.1.This approach is different to that used in the CSR, as it should be applicable in a similar way for allalternative substances assessed, and, is therefore, of a more generic nature, which does not rely onspecific data (e.g. measured data). The outcome of the exposure assessment should not beconsidered a realistic estimate of exposures, but is expected to describe relative exposureintensities.

Section 10.4 finally presents the comparative risk characterisation and the overall conclusions onrisks from using the alternative substances.


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10.2 Reference values (DNELs, PNECs) for EDC and the alternative

10.2.1Introduction

In the following Sections DNELs and PNECs are discussed, which can be used for a comparativeassessment. Available monographs, data from registration dossiers as available at ECHA-CHEM(ECHA, 2015a) as well as published data (in case of inconsistencies or data gaps) are used for thispurpose.

In case no DNELs/PNECs or similar reference values are available that are compliant with therequirements of the ECHA Guidance (ECHA, 2008; 2012) (or if there is not enough informationavailable on the rationale for deriving the values, which is often the case with the values reported inECHA CHEM), then tentative DNELs/PNECs will be derived from the available data and used in thiscomparative assessment, thus retaining a harmonised approach for all of the substances. Thetentative values should not be considered to be the final evaluation of the effects of thesesubstances; these values are used for this comparative assessment only and are not intended torepresent a full assessment of the substances concerned.

For human health considerations, DNELlong-term inhalation workers and DNELlong-term dermal workers are used for allalternative substances. For EDC, the inhalation concentration associated with a risk level of 10-5

(DMEL) is used for comparison with the alternative substances.

For the environmental assessment, PNECfreshwater will be used as reference values for the comparativeassessment. In the case of organic substances and in absence of compartment-specific toxicity datareference values for other compartments (sediment, soil) are often calculated with the equilibriumpartitioning method (EPM). As the EPM method is also used for calculating exposure levels(“predicted environmental concentrations”, PEC), risk characterisation ratios calculated this way arethe same as for the freshwater compartment. Therefore, RCRs calculated for freshwater are takenas indicative for the risks to all environmental compartments.

Impacts on human health and the environment associated with DCM are not taken into account, asexplained below.


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10.2.2EDC (CAS No. 107-06-2)

Classification

Human Health

A reference value for long-term, inhalation exposure of workers of 16.7 µg/m3 associated with a risklevel of 1 x 10-5 is used for the comparative assessment with the alternative substances here. Thisvalue is based on the exposure-risk relationship presented by RAC (ECHA, 2015b) .

This reference value is used for the RCR calculations in the tables in Section 10.4.1.

RAC (ECHA, 2015b) also proposed an exposure-risk relationship for dermal exposure. As thisexposure route is considered to be negligible compared to inhalation exposure, due to thesubstance’s high volatility, no DMEL for dermal exposure is set here and this exposure route is notconsidered for this comparative assessment.

Figure 10-1: Classification of EDCSource: http://echa.europa.eu/web/guest/home, assessed on 6 August 2014


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Ecotoxicity

Existing reference values

Table 10-1: PNECs for EDC – values from ECHA-CHEM compared to other assessments

Reference value ECHA-CHEM* OECD SIDS (2002)CEPA (CanadianEnvironmental

Protection Act, 1994)

PNECfreshwater (assessment factor) 1100 µg/L (10) 1100 µg/L (10) 130 µg/L (20)

PNECmarine-water (assessment factor) 110 µg/L (100)

PNECintermittent-releases (assessmentfactor)

1360 µg/L (100)

PNECSTP (assessment factor) 27800 mg/L (100)

PNECsediment freshwater 11.1 mg/kg sed. dw. (EPM)

PNECsoil 1.8 mg/kg soil dw. (EPM)

* http://echa.europa.eu/web/guest/home, assessed on 6 August 2014

Discussion of suitability of reference values for comparative assessment

Basis for PNECfreshwater derived in ECHA CHEM and OECD SIDS (2002):

Acute and long-term aquatic toxicity data for species from three trophic levels. Lowest NOAEC of 11mg/L from daphnia magna life cycle toxicity study. Assessment factor 10.

Basis for PNECfreshwater derived by CEPA (Canadian Environmental Protection Act, 1994):

Study of effects on larval survival of north-western salamander (Ambystoma gracile), with LC50 2.54mg/L (Black et al., 1982, unpublished). Assessment factor 20.

The study by Black et al. also investigated the toxicity of EDC in several species of fish. LC50 valuesobtained were consistently and substantially lower than those from other fish toxicity studies withthe substance. The Black et al. study was criticised in OECD SIDS and was considered not reliableenough to be used for PNEC derivation, due to the non-reproducibility in other studies.

Conclusions: PNECs for comparative assessment

The PNECfreshwater as derived in the registration dossier (ECHA CHEM) and by OECD SIDS (1100 µg/L) isused for the comparative assessment.


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10.2.3Toluene (CAS No. 108-88-3)

Classification

Human Health


Table 10-2: DNELs (or DMELs) for dichloromethane from ECHA-CHEM*

Reference valueECHA-CHEM

(joint submission)

TUKES (2013)** SCOEL (2001)

DNEL long-term workers inhalation 192 mg/m³ (50 ppm) (neurotoxicity;respiratory irritation)

77 mg/m³(approx. 20 ppm)

192 mg/m³(50 ppm)

DNEL long-term workers dermal 384 mg/kg bw/d

DNEL long-term general population

inhalation

56.5 mg/m³ (15 ppm) (neurotoxicity;respiratory irritation)

DNEL long-term general population dermal 226 mg/kg bw/day

DNEL long-term general population oral 8.13 mg/kg bw/day

* http://echa.europa.eu/web/guest/home, accessed on 22 September 2014** Substance evaluation conclusion document, issued by the Finnish Safety and Chemicals Agency,http://echa.europa.eu/documents/10162/880a5b89-c248-49b8-a24b-d32007f0875f, accessed on 1 December2014

Figure 10-2: Classification of tolueneSource: http://echa.europa.eu/web/guest/home, assessed on 22 September 2014


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Toluene is a high production volume (HPV) chemical and consequently various assessments bydifferent regulatory bodies have been carried out (Anses, 2011; ATSDR, 2000; ECB, 2003; EPA, 2005;Hassauer et al., 2001; OECD, 2001).

In 2010, toluene was registered according to Regulation (EC) No 1907/2006 in a joint submission of afull registration dossier. Long-term DNELs are retrieved from ECHA-CHEM (see table above). TheDNELlong-term inhalation workers was chosen in line with the SCOEL assessment of 2001.

In the EU RAR (ECB, 2003), the critical endpoints assessed included acute neurotoxic andneurobehavioural effects identified in epidemiological studies from occupationally exposedpersonnel. For assessing chronic systemic effects, a NOAEC of 300 ppm was used, which was foundin a 2-year inhalation study with rats. This concentration was the highest dose tested and no generalsystemic adverse effects were observed. In another study with a similar exposure pattern, a LOAECof 600 ppm was identified (critical effect: erosion/degeneration of nasal cavity epithelia). In the EURAR, no definite value for risk assessment is provided, but instead relevant exposure scenarios areestablished. For each critical effect a minimal margin of safety (MOSmin) is then determined andcompared with the expected exposure for each specific situation; a conclusion is reached based oncompliance with or exceedance of MOSmin.

In the EU RAR, a further LOAEC of 88 ppm is reported for increased risk of spontaneous abortions.The LOAEC was identified in an epidemiological study via a questionnaire to female workers fromSingapore (Ng et al., 1992). This study, without confirmation of the effects and the associatedexposure levels by another study, is not considered qualified enough to serve as a basis for finalDNEL derivation. This opinion is shared with other evaluating bodies like the German PermanentSenate Commission for the Investigation of Health Hazards of Chemical Compounds in the WorkArea (MAK Commission, DFG; Greim, 1993) or as stated in the review of Bukowski (2001).

Other available assessments (e.g. OECD, 2001) did not derive reference values for worker exposureand are not reported here in detail. US EPA (EPA, 2005) in their “Toxicological review of toluene”provided a further overview of the available epidemiological data. Ten occupational studies showingneurological or neurobehavioural effects were considered relevant and were evaluated in a weight-of-evidence approach. Identified NOAECs ranged from 20 to 44 ppm. The POD identified by US EPAwas 128 mg/m³ (34 ppm).

The Scientific Committee on Occupational Exposure Limits recommends a SCOEL value of 50 ppm(SCOEL, 2001). Within the background documentation SCOEL states that ‘first effects (LOAEL) arefound at concentrations of about 75 ppm (237 mg/m3); this applies for short-term effects(Echeverria et al., 1989) and long-term effects (Foo et al., 1990).’ Many European countries adoptedOccupational Exposure Limits (OELs) of 50 ppm as well (existing National OEL are in the range of 14to 200 ppm, see GESTIS (IFA, 2014; Access date 22-09-2014)).

In a recent assessment performed by European competent authorities in the frame of substanceevaluation under REACH, the Finnish competent authority referred to the data presented in the EURisk Assessment Report and advised that a DNELlong-term workers inhalation of approx. 20 ppm12 should be

12TUKES, 2013: http://echa.europa.eu/documents/10162/880a5b89-c248-49b8-a24b-d32007f0875f,accessed on 1 December 2014.


93

used. TUKES also recommended that SCOEL should review their assessment and take the results ofthe EU Risk Assessment Report into account.

No further information relevant for deriving DNELs was found in a literature search in PubMed(NLM, 2014b) which was performed for the period 2005-2014 (older data are expected to becovered by the available review reports). Only one relevant experimental study was identified: aninhalation developmental toxicity study with a maternal and developmental NOAEL of 750 ppm(Roberts et al., 2007).


Inhalation exposure

The inhalation DNEL presented in ECHA-CHEM is based on the SCOEL recommendation of 2001. Itwas criticised by the Finnish competent authority in the frame of substance evaluation under REACH.

In the EU RAR, no definite value for risk assessment is provided. Instead, a minimal margin of safety(MOSmin) based on the effect assessed (e.g. general systemic toxicity after repeated exposure) andthe quality of the available dose descriptor (e.g. adequacy of study duration) was determined foreach specific case.

Existing OELs reported above are close to critical NOAECs identified in various studies and do notcomply with the use of assessment factors for DNEL derivation according to ECHA Guidance on IRand CSA, Chapter R.8 (ECHA, 2012). Thus these OELs are not used for the comparative assessmenthere.

The DNEL for workers inhalation exposure of approx. 20 ppm as proposed by the Finnish competentauthority is based on an experimental NOAEC of 600 ppm for developmental and fertility effects andis in agreement with other values which can be derived from the assessments of various endpointsin the EU Risk Assessment Report.

In the EU RAR (ECB, 2003) a NOAEC of 1125 mg/m³ (300 ppm) for general systemic toxicity wasidentified in a 2-year study with rats. Rats were exposed to 0, 30, 100 or 300 ppm of toluene for 6.5hours per day, 5 days a week. In the high concentration group, no effects were observed and thus aNOAEC of 300 ppm was reported.

According to ECHA REACH Guidance R.8, the following assessment factors are used:

AF for difference in duration of exposure: 1 (chronic exposure duration) AF for other interspecies differences: 2.5 remaining differences (default); 0 allometry (not

required); AF for intraspecies differences: 5.

With the correction of starting concentration based on differences between experimental andhuman conditions:

Corrected NOAEC = 1125 × 6.5 h/d / 8 h/d × 6.7 mg/m³ / 10 mg/m³= 612.42 mg/m³


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and with an overall assessment factor of 10 (see above), a tentative DNELlong-term workers inhalation of 61.2mg/m³ (= 16 ppm) is obtained.

This value is also in agreement with a DNEL, which could be derived from a substantial body ofinformation from epidemiological studies. An assessment factor of 2 would be considered sufficientto derive a DNEL from the POD identified by U.S. EPA of 128 mg/m³ (34 ppm), leading to a similarinhalation DNEL for workers.

Dermal exposure

The dermal DNEL presented in ECHA-CHEM cannot be used for comparative assessment without afull understanding of its origin. No other relevant dermal reference values could be identified.

As with EDC, this exposure route is considered to be negligible compared to inhalation exposure,due to the substance’s high volatility. Therefore the dermal exposure route is not considered for thiscomparative assessment.

Conclusion: Tentative DNELs for comparative assessment

A DNELlong-term workers inhalation of 61.2 mg/m³ (16 ppm), which is based on the NOAEL for long-terminhalation exposure as derived in the EU Risk Assessment Report, and which is in line with a DNEL ofapprox. 20 ppm, as proposed in the substance evaluation carried out by the Finnish competentauthority, is used for the comparative assessment.

Ecotoxicity


Table 10-3: PNECs for toluene – values from ECHA-CHEM compared to other assessments


(joint submission)EU RAR (ECB, 2003)

PNECfreshwater 680 µg/L 74 µg/L

PNECmarine-water 680 µg/L -

PNECintermittent-releases 680 µg/L -

PNECSTP 13.61 mg/L 8.4 mg/L

PNECsediment freshwater 13.39 mg/kg sed. dw. -

PNECsoil 2.889 mg/kg soil dw. 0.339 mg/kg soil dw.

The predicted no effect concentrations as derived according to ECHA-CHEM and EU-RAR (ECB, 2003),are given in Table 10-3. Values according to ECHA-CHEM deviate considerably from those derived inEU RAR despite the fact that key studies are identical:

Within the context of a freshwater scenario, chronic NOEC values for fish, invertebrates and algaeare available, with invertebrates being the most sensitive trophic level (Ceriodaphnia dubia, 7dNOEC 0.74 mg/L). Applying an AF of 10 in line with REACH guidance on information requirementsand chemical safety assessment, Part R.10 results in a PNECfreshwater of 74 µg/L (i.e. the value from EURAR). Methodology for PNEC derivation leading to the value according to ECHA-CHEM is notreported (only information given: statistical extrapolation, AF 1). Following REACH guidance R.10,even for PNEC derivation using species sensitivity distributions, an AF of between 5 and 1 should be


95

applied, and an AF below 5 needs to be fully justified. No such justification is available from ECHA-CHEM, but might be included in the (unpublished) chemical safety report.

In EU RAR (ECB, 2003), no values for PNECmarine water and PNECintermittent releases were derived. Valuesgiven by ECHA-CHEM are identical to PNECfreshwater (statistical extrapolation, AF1). This is surprising,because for intermittent releases acute toxicity is decisive while for marine waters either marinetoxicity data would have to be assessed (where available) or the higher level of uncertainty due toconclusions on marine water toxicity being drawn from conclusions based on freshwater toxicitymust be taken into account (usually additional AF of 10 according to the R.10 guidance document).

PNECSTP according to ECHA-CHEM is again derived by statistical extrapolation (AF 1) without furtherdetails given. Key study for microorganism toxicity is an EC50 from Nitrosomonas nitrification rateinhibition (24 h) of 84 mg/L. Using an AF of 10 according to the standard (REACH guidance), aPNECSTP of 8.4 mg/L would result. This is the value derived within the EU risk assessment (ECB,2003).

No data on sediment toxicity is available. The PNECsediment given by ECHA-CHEM was derived fromPNECfreshwater via equilibrium partitioning (EPM). No PNECsediment was derived within EU RAR.However using the same adsorption data, an EPM based on the PNECfresh water given by EU-RAR wouldresult in a much lower PNECsediment of 1.78 mg/kg sediment dw.

PNECsoil according to ECHA-CHEM was derived by EPM. According to EU-RAR, based on terrestrialdata of limited reliability a much lower PNECsoil of 300 µg/kg soil was derived, being supported by anearly identical value resulting from EPM (based on PNECfreshwater of 74 µg/L) of 314 µg/kg sedimentdw.


Reference values according to ECHA-CHEM cannot be used without a full understanding of theirorigin: while key studies are mostly identical to those taken within the EU-risk assessment (ECB,2003), the aquatic PNEC is higher by a factor of 9.2 without an explanation being available.Therefore, for comparison with EDC hazard values, PNEC values from EU-RAR are preferred, as ameaningful comparison of environmental hazards can be performed only if the methodology toderive the hazard values is the same (assessment factor method).

Furthermore, values as given by EU RAR for fresh water, STP and soil are supported by identicalvalues derived by SIDS initial assessment profile for toluene (OECD, 2001).

Conclusions: Tentative PNECs for comparative assessment

The PNECfreshwater as derived within the EU risk assessment (ECB, 2003) of 74 µg/L is used forcomparative assessment of toluene.


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10.2.4Methyl ethyl ketone (MEK) (CAS No. 78-93-3)

Classification

Human Health


Table 10-4: DNELs (or DMELs) for MEK from ECHA-CHEM


(joint submission)ECHA-CHEM

(individual submission)

DNELlong-term workers inhalation 600 mg/m3

no DNEL derived

DNELlong-term workers dermal 1161 mg/kg x d no DNEL derived

DNELlong-term general population inhalation 106 mg/m3

no DNEL derived

DNELlong-term general population dermal 412 mg/kg x d no DNEL derived

Source: http://echa.europa.eu/web/guest/home, assessed on 10 December 2014

The occupational exposure limit in Germany and the EU is 600 mg/m3 (AGS, 2012; DFG, 2014; SCOEL,1999), in Austria and Denmark it is 100 and 50 mg/m3, respectively (IFA, 2014).

The reference concentration (RfC) of the U.S.EPA for inhalation exposure of the general population is5 mg/m3 (EPA, 2003; 2014). No guidance values were derived by WHO (1993) or ATSDR (1992), thelatter with an addendum of 201013.

Acute toxicity: the acute toxicity for inhalation, oral and dermal exposure is low (LC50 rat: >5000 ppm, >14750 mg/m3; oral LD50 rat and mice: 2000-6000 mg/kg; dermal LD50 rabbit: 6400->8000 mg/kg). The substance is rapidly absorbed through human skin. MEK is only slightly irritatingto skin, but highly irritating to eyes, and is not sensitising. At air concentrations above 200-300 ppm,590-885 mg/m3 MEK irritates eyes, nose and throat and may result in headaches (ECB, 2000; ECHA,2015a; Greim, 1996; NLM, 2014a; OECD, 1997; SCOEL, 1999).

13http://www.atsdr.cdc.gov/, assessed on 10 December 2014.

Figure 10-3: Classification of MEKSource: http://echa.europa.eu/web/guest/home, assessed on 13 October 2014


97

Repeated dose toxicity: several animal studies have been performed with inhalation exposure, andthe following study is the most suitable for risk assessment (e.g. key study in registration dossier):Repeated exposure of rats (90 days, 6 h/d, 5 d/w) resulted in depression of mean body weight,reduced brain weight and a slight but significant increase in relative and absolute liver weight at anexposure concentration of 5000 ppm (8850 mg/m3). No signs of upper respiratory irritation orneuropathological/pathological lesions could be detected. No effects were observed at the lowerconcentrations (2500 and 1250 ppm, 4425 and 2213 mg/m3, respectively) (Cavender et al., 1983).

In the registration dossier (ECHA, 2015a) a NOAEC of 5000 ppm was derived from this study, indeviation from ECB (2000), SCOEL (1999) or Greim (1996), which considered the NOAEC of this studyto be 2500 ppm or at least 2500 ppm, respectively. Concentrations above 6000 ppm (17700 mg/m3)produced marked irritation of the respiratory tract of animals.

No dermal toxicity studies are available.

Reproductive and developmental toxicity: this endpoint was assessed in several studies withinhalation exposure. One of them (Schwetz et al., 1974) exposed pregnant rats to 1000 and 3000ppm (2950 and 8850 mg/m3, respectively) on gestation days 6-15 (7 h/d). At a high concentration,retarded fetal development (delayed ossification) and teratogenic effects (tail aplasia andimperforate anus) were observed in the absence of maternal toxicity. Repetitions of this experimentwith 400, 1000 and 3000 ppm for 7 h/d on gestation days 6-15 produced mild maternal toxicity(reduced weight gain) and minor fetotoxic effects (delayed ossification, skeletal variations).Teratogenicity was not observed in the study of Deacon et al. (1981).

The results of this publication are evidently identical to those of the key study in the registrationdossier.

A similar study with mice with the same exposure regimen showed indication of slight maternaltoxicity in the high dose group (increased relative liver and kidney weights). The offspring revealedslight fetotoxicity in the form of reduced pup weights and skeletal variations (misalignedsternebrae), and both effects were significant at the highest dose (NTP, 1989; Schwetz et al., 1991).These older data have been confirmed by Saillenfait et al. (2006):

A further developmental toxicity study on pregnant rats was performed by these authors (as part ofthe examination on the effects of combined exposure to ethylbenzene and MEK), using the sameexposure concentrations of 1000, or 3000 ppm MEK (2950 and 8850 mg/m3, respectively) for6 hours a day on gestation days 6–20. Maternal weight gain and food consumption was significantlydecreased at the higher exposure concentration. No significant increase in embryo/fetal lethality orincidence of malformations and variations was observed in any of the treatment groups, but fetalbody weights were significantly reduced after exposure to 3000 ppm MEK.

No dermal toxicity studies are available.

Genotoxicity and carcinogenicity: most of the available studies on genotoxicity yielded negativeresults, including tests on gene mutations in bacteria and mammalian cells in vitro, chromosomemutations and Unscheduled DNA Synthesis (UDS) in mammalian cells in vitro, and transformation ofcell culture. An in vivo micronucleus test in mice and hamsters did not observe mutagenic effects.The only positive result was observed for mitotic chromosome loss in yeast at high concentrations.Carcinogenicity was assessed by a study on male mice, where dermal application of 50 mg of a 17%


98

MEK solution applied twice per week for one year resulted in no skin tumors. No other data oncarcinogenic effects is available (ECB, 2000; ECHA, 2015a; EPA, 2003; Greim, 1996; OECD, 1997).


Inhalation exposure

The basis for derivation of the DNEL for inhalation exposure of workers in the registration dossier isnot apparent from the given information. The study by Cavender et al. is the key study for inhalationexposure, but the overall assessment factor of 1 indicates the use of human data, which is only listedas supporting data. However the DNEL of 600 mg/m3 is in agreement with the German and EUworkplace exposure limits (AGS, 2012; DFG, 2014; SCOEL, 1999), which indicates the direct adoptionof this value. The basis of the other listed DNELs is unclear. Developmental toxicity was notconsidered in any of these evaluations, despite lower effect concentrations than in the principalsubchronic animal toxicity study (Cavender et al., 1983).

If the study by Cavender et al (1983) is used for risk assessment, according to ECHA REACH GuidanceR.8 the following assessment factors have to be used:

AF for difference in duration of exposure: 2 (subchronic exposure duration) AF for other interspecies differences: 2.5 remaining differences (default); 0 allometry (not

required); AF for intraspecies differences: 5.

With the correction of starting concentration based on differences between experimental andhuman conditions:

Corrected NOAEC = 4425 × 6 h/d / 8 h/d × 6.7 mg/m³ / 10 mg/m³= 2223.6 mg/m³

and with an overall assessment factor of 25 (see above) a tentative DNELlong-term workers inhalation of 89mg/m³ (30 ppm) is obtained.

Data from developmental toxicity studies were used by EPA to derive a reference concentration(RfC) for inhalation exposure of the general public (EPA, 2003; 2014). The effect concentration inthese older studies was recently confirmed by the findings in the Saillenfait et al. (2006) study withidentical LOAEC and NOAEC values of 3000 and 1000 ppm. Benchmark dose-modelling wasperformed based on the data of Deacon et al. (1981) and Schwetz et al. (1991). A human equivalentLEC10 value of 1,517 mg/m3 was calculated, taking into account pharmacokinetic differencesbetween animals and humans. Using a total uncertainty factor of 300 (3 for remaining interspeciesdifferences on pharmacodynamics, 10 for intraspecies variance and 10 to account for database

deficiencies), a RfC of 5 mg/m3 results. As the assessment factor for database deficiencies is notincluded in the ECHA guidance R.8 methodology (ECHA, 2012), an analogue reference value wouldbe 50 mg/m3 for the general population. For workers, this value can be converted to 280 mg/m3,under consideration of 5 working days per week, a reduced intraspecies variance factor of 5 inworkers (instead of 10 for general population) and an additional factor of 2 (10 m3 respiratoryvolume/shift vs. 20 m3/day) according to ECHA (2012). It can be concluded that a DNEL based oneffects from subchronic inhalation exposure is sufficiently protective also for endpoints ofdevelopmental toxicity.


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Dermal exposure

The dermal DNEL presented in ECHA-CHEM cannot be used for comparative assessment without afull understanding of its origin. No other relevant dermal reference values could be identified.

As with EDC, this exposure route is considered to be negligible compared to inhalation exposure,due to the substance’s high volatility. Therefore the dermal exposure route is not considered for thiscomparative assessment.

Conclusion: Tentative DNELs for comparative assessment

A tentative DNELlong-term workers inhalation of 89 mg/m³, based on the NOAEC from a subchronic

experimental study, is used for comparative risk assessment.

Ecotoxicity


Table 10-5: PNECs for MEK – values from ECHA-CHEM (no other values available)

Reference value ECHA-CHEM

PNECfreshwater (assessment factor) 55.8 mg/L (1, statistical extrapolation)

PNECmarine-water (assessment factor) 55.8 mg/L (1, statistical extrapolation)

PNECintermittent-releases (assessment factor) 55.8 mg/L (1, statistical extrapolation)

PNECSTP (assessment factor) 709 mg/L (1, statistical extrapolation)

PNECsediment freshwater 284.74 mg/kg sed. dw. (EPM)

PNECsoil 22.5 mg/kg soil dw. (EPM)

Besides the values published in ECHA CHEM, no other reference values could be found. In the OECDSIDS report (OECD, 1997), no PNEC was derived. Based on a review of both experimental and QSARbased data, in the OECD SIDS report low aquatic toxicity of MEK was concluded without specifyingstudies of especial relevance.

Aquatic toxicity data are reported in ECHA CHEM (only acute data), OECD SIDS (no reliable chronicdata; OECD, 1997) and data from National Institute of Technology and Evaluation (NITE), Japan14.


The basis for PNECfreshwater derived in ECHA CHEM is not clear. An assessment factor of 1 is given inECHA-CHEM along with the statement “statistical extrapolation”. According to the ECHA guidancedocument R.10 (ECHA, 2008) requirements to allow for a statistical approach (species sensitivitydistribution) are the following: test results for at least 8 different organism groups must be availableand generally, NOECs from chronic/long-term studies are required. The study summaries included inthe registration dossier available from ECHA CHEM are restricted to acute aquatic toxicity data (withthe exception of algae/aquatic plants, which may be rated also as chronic information) and coveronly fish, crustaceans (Daphnia magna) and algae, i.e. three instead of 8 groups.

14http://www.safe.nite.go.jp/jcheck/top.action


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In addition to the acute data given by ECHA CHEM, a 21-day reproduction test with Daphnia magnais available from the National Institute of Technology and Evaluation (NITE), Japan11. Whiledocumentation of available tests within J-CHECK is poor, these tests are generally reliable andperformed according to international guidelines. According to the data given by J-CHECK, the NOEC(21d; semi-static; reproduction) was larger or equal to 100 mg/L (nominal concentration).Furthermore, from this source a prolonged toxicity test on fish (Oryzias latipes) is available. A NOEC(14d; flow through; analytical verification) of ≥ 100 mg/L was determined.

According to the acute tests available from ECHA CHEM (key studies), fish was the trophic level withthe lowest sensitivity (LC50 (Pimephales promelas; 96h; mean measured) 2993 mg/L), followed byalgae (EC50 (Pseudokirchnerella subcapitata; 72 h; growth rate 1972 mg/L) and aquatic invertebrates(EC50 (Daphnia magna; 48 h; measured initial) 308 mg/L).

Given all these data and taking the prolonged 14-day toxicity test on fish as a support, it is highlyprobable that fish are not the most sensitive trophic level, and that chronic data on aquaticinvertebrates and algae are sufficient to judge on long-term toxicity of MEK. In such circumstancesR.10 guidance (ECHA, 2008) foresees an assessment factor of 10 on the lowest long-term resultdetermined for the species being also acutely most sensitive. Thus, the 21-day NOEC for Daphniamagna reproduction of 100 mg/L is used to derive the PNECfreshwater with an assessment factor of 10:

PNECfreshwater = 10 mg/L

Conclusions: Tentative PNECs for comparative assessment

The tentative PNECfreshwater of 10 mg/L as derived above taking into consideration the chronic data onDaphnia magna and a prolonged toxicity test on freshwater fish reported by NITE, Japan, will beused for the comparative assessment.

10.3 Exposure Assessment

10.3.1Exposure scenario

EDC is used in a closed system as process chemical (solvent) for mineral oil/paraffin wax refinery inde-waxing and de-oiling processes. In this process, a solvent mixture together with DCM('#A#''''''''''', w/w) is used, which means that substituting EDC will result in a simultaneousreplacement of DCM. In the following text, only the reduced risk from substituting EDC isconsidered, as this is the Annex XIV substance under scrutiny. Furthermore, although DCM showssome carcinogenic properties15, the inhalation cancer risk assessment presented by the US EPA in201116 (inhalation unit risk of 1 × 10-8 per µg/m3, for life-long continuous exposure) indicate acarcinogenic potency substantially lower than that expressed by RAC’s exposure-risk relationship forEDC. Therefore, impacts on human health from replacing the mixture are expected to be influencedby EDC alone.

15IARC recently upgraded its classification of dichloromethane to Group 2A “probably carcinogenic tohumans” (Benbrahim et al., 2014).

16http://cfpub.epa.gov/ncea/iris/index.cfm?fuseaction=iris.showQuickView&substance_nmbr=0070,accessed on 8 January 2015.


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The following use descriptors are assigned to this use:

Exposure scenario: Use for mineral oil/paraffin wax refinery—de-waxing and de-oiling process.

ERC: Industrial use of processing aids in processes and products, not becoming part of articles(ERC 4)

PROC: Use in closed, continuous process with occasional controlled exposure (PROC 2)

Transfer of substance or preparation (charging/discharging) from/to vessels/large containersat dedicated facilities (PROC 8b) (i.e. unloading of road tankers - sampling, maintenance andcleaning activities, which are additional activities, and to which PROC8b was assigned are notconsidered here)

Use as laboratory reagent (PROC 15)

This scenario was used for performing a comparative exposure assessment and risk characterisation.Exposure modelling was done using ECETOC TRA, version 3.1.17

The following DNELs/DMELs and PNECs are used for the comparative risk characterisation (fordetails see Section 9.2).

Table 10-6: DNELs/DMELs and PNECs used for EDC and alternative substances for the comparative riskcharacterisation

Substance D(M)NELlong-term inhalation workers D(M)NELlong-term dermal workers PNECfreshwater w

EDC 16.7 µg/m3

Not applicable 1100 µg/L

Toluene 61,200 µg/m3

Not applicable 74 µg/L

MEK 89,000 µg/m3

Not applicable 10,000 µg/L

Dermal exposure

ECHA Guidance on Information Requirements and Chemical Safety Assessment, R.14, Appendix R.14-1, discusses evaporation rates and time required for complete loss of volatile substances from gloves(ECHA, 2012b). For intermittent exposure (due to splashes, as can be assumed here) and substanceswith vapour pressures of 10,000 Pa (at ambient temperatures) such as cyclohexane the evaporationtime is calculated to be 12 seconds only. For toluene with a vapour pressure of ca. 3,000 Pa it is stillonly 39 seconds.

In conclusion, dermal exposure from both EDC and the components of the alternative solventmixture are considered negligible for the following reasons:

Minimal dermal exposure is expected as the substances are handled mostly in a closedsystem

Under PROC8b and 15 as well as during sampling (PROC 2) workers wear protective clothingand gloves; occasional small splashes may occur at most and these are expected to

17http://www.ecetoc.org/tra


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evaporate rapidly from gloves; direct contact but also contact via contaminated gloves whentaking them off is not possible; therefore, for the purpose of this comparative assessment,inhalation exposure is considered the only relevant pathway for these two substances.

10.3.2Input data for exposure modelling

The following data is used for exposure modelled in the standardised exposure scenario:

Table 10-7: Physicochemical and environmental fate properties data of alternative substances taken fromECHA-CHEM if not stated otherwise; ECHA, 2015a; data for EDC are from OECD (2002)

SubstanceMolecular

weight(g/Mol)

Vapourpressure (Pa)

Log PO/W Biodegradability Water solubility [mg/L]

EDC 98.96 81300 (20°C) 1.45Not ready

biodegradable8490-9000 (20 °C)

Toluene 92.14 3089 (21°C) 2.73Readily

biodegradable580 (25°C)

MEK 72.11 10400 (20°C) * 0.3Readily

biodegradable

27.5 vol% (with density,0.81 g/L corresponds to

223000 mg/L)

* in addition, a higher value of 12600 is reported in ECHA CHEM, related to a temperature of 25°C

For the environmental assessment, it is assumed that per production unit (on a weight basis) theyearly amount consumed is:

#B#

'#A#''''''''' '''''' '''' ''''''' ''''''''''''' '''''''''''''''' '''''''' ''''' ''''' ''''''''' '''' ''''''' ''''''''''''''''' ''''''''''''''''''''''''''' ''''''''''' '''''''''''''''' ''''''' ''''''''''''''''''' '''''''' ''''' '''''''''''''''''''' ''''''''''''''''''' ''''''''''''' '''' ''''''''''''' '''''''''' '''''' '''''''''''''' '''' '''''''''''''''''''''''''' '''' '''''''''''''''''''''' '''''''''''''''''''' '''''''' ''' ''''''''''''''''''' '''''''''''''

The following assumptions were used for modelling:

Workers assessment:

PROC 2: exposure duration 8 h, indoors, LEV (efficiency 90%), no PPE

PROC 8b: exposure duration 1-4 h, outdoors, no LEV, respiratory protection (efficiency95%)

PROC 15: exposure duration 8 h, indoors LEV (fume cupboard, efficiency 90%)

Although the concentration of the solvents in the mixtures is '#A#''''''' ''''''''', this is not takeninto account, due to the banding approach used in ECETOC TRA, where all concentrations>25% are treated as neat substances


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Environmental assessment:

ERC 4: Release factors and the number of emission days according to ESVOC SpERC1.1v1, t/a used at site (see above), STP available, all other conditions (e.g. STP dischargerate, river flow rate) with identical default values.

10.4 Results of the comparative exposure assessment and riskcharacterisation

The following tables show the results of the comparative exposure assessment and riskcharacterisation.

10.4.1Occupational exposure

Similar exposure concentrations are obtained for EDC and the components of the solvent mixturewith respect to inhalation exposure of workers. However, due to the low DMEL, RCRs are muchhigher for EDC.

Table 10-8: Result of the comparative exposure and risk characterisation, workers

EDC MEK Toluene

PROC 2:Exposure concentration, chronic, inhalation

10.3 mg/m3

7.5 mg/m3

1.9 mg/m3

PROC 2: RCR 617 0.084 0.031

PROC 2: RCR (combined for mixture) 0.12

PROC 8b:Exposure concentration, chronic, inhalation

13.0 mg/m3

9.5 mg/m3

2.0 mg/m3

PROC 8b: RCR 778 0.11 0.033

PROC 8b: RCR (combined for mixture) 0.13

PROC 15:Exposure concentration, chronic, inhalation

20.6 mg/m3

15 mg/m3

3.8 mg/m3

PROC 15: RCR 1,235 0.17 0.063

PROC 15: RCR (combined for mixture) 0.23

10.4.2Environmental exposure

With regard to the environmental assessment, RCRs for the freshwater compartment are well below1 for all substances, if calculated with release factors from ESVOC SpERC 1.1.v1. Combination of theRCRs for both components of the solvent mixture (i.e. assuming additivity of effects) lead to acombined RCR similar to that of EDC (despite a substantially lower PNECfreshwater of toluene). Inconclusion, environmental risks of the solvent mixture are considered comparable to those of EDC.

Table 10-9: Result of the comparative exposure and risk characterisation, environment

EDC MEK Toluene

ERC 4 (ESVOC SpERC 1.1v1) – local PEC, freshwater: 0.0044 mg/L 0.0042 mg/L 0.00072 mg/L

RCR 0.004 0.00042 0.0098

RCR (combined for mixture) 0.010


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10.4.3Conclusions

Based on these quantitative considerations, the alternative solvent mixture seems to beadvantageous with regard to human health effects. Environmental risks are considered to be similar(or slightly higher) for the alternative mixture, based on the results of the comparative riskassessment. RCRs for the freshwater compartment in the comparative assessment are well below 1for both EDC and the alternative solvent mixture.

10.5 References for Annex 3

AGS, Ausschuss für Gefahrstoffe (2012)Technische Regeln für Gefahrstoffe – Arbeitsplatzgrenzwerte (TRGS 900). Ausgabe: zuletzt geändertund ergänzt: GMBl 2012 S. 715-716 [Nr. 40]Bundesanstalt für Arbeitsschutz und Arbeitsmedizinonline: http://www.baua.de/de/Themen-von-A-Z/Gefahrstoffe/TRGS/TRGS-900.html

Anses, Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement et du travail(2011)Valeur toxicologique de référence par inhalation du toluènehttp://www.anses.fr/Documents/CHIM2009sa0342Ra.pdf

ATSDR, Agency for Toxic Substances and Disease Registry (1992)Toxicological Profile for 2-ButanoneU.S. Department of Health and Human Services Public Health Service

ATSDR, Agency for Toxic Substances and Disease Registry (2000)Toxicological Profile for Toluene. UpdateU.S. Department of Health and Human Services; Public Health Service

Benbrahim-Tallaa, L.; Lauby-Secretan, B.; Loomis, D.; Guyton, K.Z.; Grosse, Y.; El Ghissassi, F.;Bouvard, V.; Guha, N.; Mattock, H.; Straif, K. (2014)Carcinogenicity of perfluorooctanoic acid, tetrafluoroethylene, dichloromethane, 1,2-dichloropropane, and 1,3-propane sultoneThe Lancet Oncology, 15, 924-925

Bukowski, J.A. (2001)Review of the epidemiological evidence relating toluene to reproductive outcomesRegulatory Toxicology and Pharmacology, 33, 147-156

Canadian Environmental Protection Act (1994)Priority Substances List Assessment Report. 1,2-DichloroethaneMinister of Supply and Services Canada

Cavender, F.L.; Casey, H.W.; Salem, H.; Swenberg, J.A.; Gralla, E.J. (1983)A 90-day vapor inhalation toxicity study of methyl ethyl ketoneFundamental and Applied Toxicology, 3, 264-270


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Deacon, M.M.; Pilny, M.D.; John, J.A.; Schwetz, B.A.; Murray, F.J.; Yakel, H.O.; Kuna, R.A. (1981)Embryo- and fetotoxicity of inhaled methyl ethyl ketone in ratsToxicology and Applied Pharmacology, 59, 620-622

DFG, Deutsche Forschungsgemeinschaft (2014)MAK- und BAT-Werte-Liste 2014. Senatskommission zur Prüfung gesundheitsschädlicherArbeitsstoffe. Mitteilung 50WILEY-VCH Verlag GmbH, Weinheim

ECB, European Chemicals Bureau (2000)IUCLID, International Uniform Chemical Information Database. Edition IIEUR 19559 EN European Commission

ECB, European Chemicals Bureau (2003)European Union Risk Assessment Report: Toluene. 2nd Priority List, Vol. 30EUR 20539 EN. European Commission. Joint Research Centre

ECHA, European Chemicals Agency (2008)Guidance on information requirements and chemical safety assessment. Chapter R.10:Characterisation of dose [concentration]-response for environmenthttp://guidance.echa.europa.eu/

ECHA, European Chemicals Agency (2012)Guidance on information requirements and chemical safety assessment. Chapter R.8:Characterisation of dose [concentration]-response for human health. Version: 2.1online: http://echa.europa.eu/documents/10162/17224/information_requirements_r8_en.pdf

ECHA, European Chemicals Agency (2015a)Information on Chemicals - Registered SubstancesOnline: http://echa.europa.eu/web/guest/information-on-chemicals/registered-substances

ECHA, European Chemicals Agency (2015b)Application for Authorisation: Establishing a Reference Dose Response Relationship forCarcinogenicity of 1,2-Dichloroethane. RAC/33/2015/09 Rev1 FinalHelsinki, Finland

EPA, Environmental Protection Agency (2003)Toxicological Review of Methyl Ethyl Ketone (CAS No. 78-93-3). In Support of Summary Informationon the Integrated Risk Information System (IRIS)September 2003U.S. Environmental Protection Agency, Washington DC. http://www.epa.gov/iris/subst/0071.htm

EPA, Environmental Protection Agency (2005)Toxicological Review of Toluene. In Support of Summary Information on the Integrated RiskInformation System (IRIS). EPA/635/R-05/004U.S. Environmental Protection Agency, Washington D.C.


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EPA, Environmental Protection Agency (2014)Integrated Risk Information System (IRIS)online: http://www.epa.gov/IRIS/

Greim, H. (1993)Gesundheitsschädliche Arbeitsstoffe, Toxikologisch-arbeitsmedizinische Begründungen von MAK-Werten, Loseblattsammlung, 19. LfgDFG Deutsche Forschungsgemeinschaft, VCH Verlag Weinheim

Greim, H. (1996)Gesundheitsschädliche Arbeitsstoffe, Toxikologisch-arbeitsmedizinische Begründungen von MAK-Werten, Loseblattsammlung, 22. LfgDFG Deutsche Forschungsgemeinschaft, VCH Verlag Weinheim

Hassauer, M.; Kalberlah, F.; Griem, P. (2001)Toluol. Mit Addendum 2004 (Hassauer, M., Schuhmacher-Wolz, U.)In: Eikmann, T.; Heinrich, U.; Heinzow, B.; Konietzka, R., Gefährdungsabschätzung vonUmweltschadstoffen. Ergänzbares Handbuch toxikologischer Basisdaten und ihre Bewertung,Kennziffer D 916, 4. Erg.-Lfg. 3/01 u. 9. Erg.-Lfg. 8/04, Erich Schmidt Verlag Berlin,

IFA, Institut für Arbeitsschutz der Deutschen Gesetzlichen Unfallversicherung (2014)GESTIS-Stoffdatenbank. Gefahrstoffinformationssystem der Deutschen GesetzlichenUnfallversicherunghttp://www.dguv.de/ifa/de/gestis/stoffdb/index.jsp

Ng, T.P.; Foo, S.C.; Yoong, T. (1992)Risk of spontaneous abortion in workers exposed to tolueneBritish Journal of Industrial Medicine, 49, 804-808

NLM, U.S. National Library of Medicine (2014a)Hazardous Substances Data Bank (HSDB). METHYL ETHYL KETONEhttp://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@na+METHYL%20ETHYL%20KETONE

NLM, U.S. National Library of Medicine (2014b)PubMedonline: http://www.ncbi.nlm.nih.gov/sites/entrez?db=pubmed

NTP, National Toxicology Program (1989)Inhalation developmental toxicology studies: teratology study of methyl ethyl ketone (CAS No. 78-93-3) in mice. NTP study: TER88046.Research Triangle Park, NC

OECD, Organisation for Economic Co-Operation and Development (1997)SIDS Initial Assessment Profile for SIAM 6 (Paris, France, 9-11 June 1997). Methyl Ethyl Ketone (MEK)http://webnet.oecd.org/Hpv/UI/SIDS_Details.aspx?id=31C513F8-2B0D-4DE8-9A14-8463CD709ADD


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OECD, Organisation for Economic Co-Operation and Development (2002)SIDS Initial Assessment Report for SIAM 14 (Paris, France, 26-28 March 2002). 1,2-Dichloroethanehttp://www.chem.unep.ch/irptc/sids/OECDSIDS/indexcasnumb.htm

OECD, Organisation for Economic Co-Operation and Development (2001)SIDS Initial Assessment Report for SIAM 11 (USA, 23-26 January 2001). Toluenehttp://www.chem.unep.ch/irptc/sids/OECDSIDS/indexcasnumb.htm

Roberts, L.G.; Nicolich, M.J.; Schreiner, C.A. (2007)Developmental and reproductive toxicity evaluation of toluene vapor in the rat II. DevelopmentaltoxicityReproductive Toxicology, 23, 521-531

Saillenfait, A.M.; Gallissot, F.; Sabate, J.P.; Bourges-Abella, N.; Cadot, R.; Morel, G.; Lambert, A.M.(2006)Developmental toxicity of combined ethylbenzene and methylethylketone administered byinhalation to ratsFood and Chemical Toxicology, 44, 1287-1298

Schwetz, B.A.; Leong, B.K.J.; Gehring, P.J. (1974)Embryo- and fetotoxicity of inhaled carbon tetrachloride, 1,1-dichlorethane and methyl ethyl ketonein ratsToxicology and Applied Pharmacology, 28, 442-464

Schwetz, B.A.; Mast, T.J.; Weigel, R.J.; Dill, J.A.; Morrissey, R.E. (1991)Developmental toxicity of inhaled methyl ethyl ketone in Swiss miceFundamental and Applied Toxicology, 16, 742-748

SCOEL, Scientific Committee for Occupational Exposure Limits (1999)Recommendation from the Scientific Committee on Occupational Exposure Limits for 2-Butanone.SCOEL/SUM/5. June 1999European Commission; Employment, Social Affairs and Inclusion

SCOEL, Scientific Committee for Occupational Exposure Limits (2001)Recommendation from the Scientific Committee on Occupational Exposure Limits for Toluene.SCOEL/SUM/18, March 2001EC, European Commission

WHO, World Health Organization (1993)Environmental Health Criteria 143, Methyl Ethyl KetoneIPCS International Programme on Chemical Safety; World Health Organization Geneva;http://www.inchem.org/documents/ehc/ehc/ehc143.htm


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11 Annex 4 – Justifications for confidentiality claims

This Annex is presented in the complete version of the document.


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