Green Biofuels Ireland Ltd. Application for an IPPC Licence · Thirteen of the tanks will be placed...

Green Biofuels Ireland Ltd. July 2007 Application for an IPPC Licence Attachment H.1 –Raw Materials, Intermediaries and P roduct Handling

Malone O’Regan

Green Biofuels Ireland Ltd. Application for an IPPC Licence

Attachment H.1

Raw Materials, Intermediaries, Products Handling

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Table of Contents Section Page No 1.0 Introduction ……………………………………………………………………. 2 2.0 Material Storage ………………………………………………………………. 2 2.1 List of Primary Input Raw Materials………………………………………….. 2 2.2 List of Ancillary Input Raw Materials….……………………………………… 2 2.3 List of Finished and Side Products…………………………………………… 2 2.4 Raw Materials, Finished Products and Ancillary Production Materials…… 2 3.0 Movement of Materials on Site ……………………………………………… 4 3.1 Tank Farm – Loading and Unloading………………………………………… 4 3.2 Tank Farm to Wharf Connection……………………………………………… 6 3.3 Piping and Reaction Vessels ………………………………………………… 6 3.3.1 Piping ………………………………………………………………….. 6 3.3.2 Reaction Vessels and Pressure Testing …………………………… 7 4.0 Bunded Structure Management …………………………………………… 8 Appendices

H.1.1 Raw Material and Chemical Storage Areas H.1.2 Details of the Pipeline System (confidential file – presented

separately) H.1.3 Material Safety Data Sheets

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1.0 INTRODUCTION This section of the IPPC Licence application details information to allow an assessment of the handling arrangements for raw materials, ancillary production materials and finished product at the Green Biofuels Ireland Limited (GBI) site. The process at the GBI facility is designed to minimise any waste generated during the process of converting indigenous resources (such as rapeseed oil, tallow and used vegetable oils) to a high quality, biodegradable fuel (BioDiesel) meeting the EU quality standard EN14214 for use as a safe fuel alternative. 2.0 MATERIAL STORAGE 2.1 List of Primary Input Raw Materials The list of primary input raw materials for the production process are summarised below:

o Tallow o Recycled Vegetable Oils (RVO) o Rapeseed Oil and other virgin oils

2.2 List of Ancillary Input Raw Materials The remaining ancillary raw materials required for the production process are summarised below.

o Methanol o Potassium Hydroxide (KOH) o Sulphuric Acid o Phosphoric Acid o Nitrogen o Gas Oil o CFPP – Additive o Water Additives o Antioxidant

2.3 List of Finished and Side Products The list of finished and side-products from the production process is summarised below:

o BioDiesel o Crude Glycerine o Fertiliser o Bio-heating oil by-product (lower grade bio-heating fuel)

2.4 Raw Materials, Finished Products and Ancillary Production Materials Materials at the GBI site will be stored in discrete locations depending on the nature/status of the material. The locations of material storage areas within the facility are indicated on a drawing of the site as shown in Appendix H.1.1. Material Safety Data Sheets for the raw materials used at the GBI facility and finished products are presented in Appendix H.1.3. Nineteen bulk tanks will be used on site to store raw materials, finished product and ancillary production materials. The bulk storage pipes and direct pipelines will keep

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handling and container changes to a minimum to reduce waste generation and potential handling spills. The quantity of finished product stored on site will be in the region of 2,000 tonnes. In addition, a number of additional tallow tanks will be used to store tallow. Thirteen of the tanks will be placed in a general bunded area or tank farm covering an area of 1,622 m2 as shown on Appendix H.1.1 depicting the proposed site layout. The methanol and gas oil tanks will be stored in their own bunded areas within the tank farm as shown on Appendix H.1.1. Both the sulphuric acid and phosphoric acid tanks will be placed together in a separate bunded area within the tank farm. The nitrogen storage tank and the fertiliser silo will be stored in separate areas as shown as shown on Appendix H.1.1. Potassium hydroxide (KOH) (catalyst) together with used KOH big bags will be stored in the main process building. Chemicals will be transferred to and from the process building via an enclosed piped system, the schematic of which is shown on Appendix H.1.2 (with enclosed stream list and equipment list codes). (Note: The information on the pipeline system is considered confidential and as such is presented separately in an envelope). The storage tanks are designed in accordance with latest guidance on energy efficiency, environmental protection and as such represent BAT for materials storage. Table 1 below outlines the storage and list of raw materials, finished products and ancillary materials on site. An internal dedicated chemical store will be used to store all dry materials. This is primarily potassium hydroxide. Drums where used will be properly secured and provided with adequate drip trays.

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Table 1 Storage of Raw Materials, Finished Products & Ancillary Materials on Site

Tank Capacity

Total Storage Capacity

Tank Height

Material No. of Tanks

m3 m3 m Rapeseed Oil 1 200 200 7.5 RVO 1 200 200 7.5 Tallow (feedstock) 2 200 400 7.5 Additional feedstock tank to act as temporary wastewater storage tank in short term

1 200 200 7.0

Tallow / virgin oil storage 2 1000 2000 12 BioDiesel 2 1000 2000 12 Crude Glycerine 1 160 160 7 Methanol 1 100 100 6.5 Gas oil (boiler fuel) 1 50 50 5.5 Sulphuric Acid 1 25 25 3.6 Bio-heating oil by product 1 40 40 4.2 Phosphoric Acid 1 25 25 3.6 Nitrogen 1 10 10 3.5 Fertiliser Silo 25 25 3.6 Quality Tank 1 200 200 7.5 Additive tank 1 25 25 3.6

3.0 MOVEMENT OF MATERIALS ON SITE Materials will move on site via enclosed pipelines within the process building as well as to and from the tank farm. BioDiesel will also be piped to the wharf at Marshmeadows. 3.1 Tank Farm – Loading and Unloading

BioDiesel storage FME (fatty acid methylester) the main product of the BioDiesel process is alternately collected with additives in a BioDiesel quality tank containing a capacity of 200 m³. The BioDiesel complying with the European BioDiesel standard (ascertained by analysis) is pumped from this quality tank to two dedicated long term storage tanks with a capacity of 1000 m³. Finally, BioDiesel from any BioDiesel tank can be loaded to road tankers by the top loading device at the loading station. All BioDiesel storage tanks are equipped with heating coil and with thermal insulation.

Feedstock storage The feedstock is firstly pumped from the unloading station (incoming road tankers) or through the pipeline to any of the raw material storage tanks (capacity of each 200 m³). Tanks are equipped with heating coils to prevent plugging of the feedstock at lower (ambient) temperatures. All feedstock tanks are also equipped with thermal insulation.

Feedstock from ships is pumped into one of the two 1000 m³ storage tanks. Road tankers unload at the designated unloading station on the site while the ship

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unloading station takes place at the jetty. Tank farm and port are connected with a pipeline system. Tallow/RVO storage tanks are featured with thermal insulation and a heating coil for an appropriate use.

Crude Glycerine Crude Glycerine, one of the side products of the BioDiesel process, is stored in a dedicated tank with a capacity of maximum 160 m³. The tank is equipped with a heating coil and thermal insulation. Loading is executed by a separated top loading device at the loading station. Fertiliser Fertiliser, another side product, is conveyed to a 25-tonne silo from where it is bagged off, in powder format, into 1-tonne bags and stored undercover for shipment. Potassium hydroxide (KOH) Potassium hydroxide (KOH) is used for the preparation of MEK. The potassium hydroxide (KOH) is delivered in Big-Bags with a weight of about 1000 kg. The transfer to the MEK preparation takes place by fork lift truck and by hoist. Sulphuric acid Sulphuric acid is stored in a dedicated storage tank with a capacity of 25 m³, which is located in a separate bund. The unloading process from the road tankers takes place at the unloading station. Bio-Heating Oil Bio-heating oil side product is stored in a storage tank with a capacity of 40 m³. The tank is equipped with a heating coil and thermal insulation. Gas Oil Gas Oil is stored in a dedicated storage tank with a capacity of approx. 50 m³ and is located in a separate bund. Methanol Methanol is stored in a dedicated storage tank with a capacity of 100 m³, which is erected in a separate bund. The unloading from the road tankers takes place at the unloading station. By filling the storage tank the displaced gas volume is vented back to the emptied road tanker by a separate pipe. There are no emissions of evaporated liquid. The flame arrestor at tank ventilation guarantees that the displacement of gases will take place by having a certain pressure loss.

Nitrogen The nitrogen system consists of a liquid nitrogen storage tank with a capacity of 10 m³. The system is equipped with a vaporizer to supply the plant with gaseous nitrogen. Filling of the tank takes place by the road tankers. Loading system The BioDiesel is pumped from one of the 2 no. 1000 m³ storage tanks to either a road tanker or boat. The road tankers are filled by movable top loading arms. A flow meter counts the amount of the loaded product. A maximum level switch stops the loading procedure for safety reasons.

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3.2 Tank Farm to Wharf Connection

BioDiesel will be piped to the wharf at Marshmeadows through a system of pipelines from the tank farm at the GBI facility. It is estimated that they will be used for approximately one import / export per month. The pipelines will be full of product for a period of approximately 6 hours during pumping and will be entirely emptied upon completion of this activity. These pipelines will be constructed of schedule 40 welded heavy-duty steel with pressure testing on completion. They will also be trace heated and insulated as required. The integrity of the pipes will also be tested annually.

3.3 Piping and Reaction Vessels 3.3.1 Piping

All pipelines installed will be in accordance with BS 8000:1989 Part 14, BS 8010: Code of Practice for Pipelines and BS 8301:1985 Code of practice for Building Drainage.

Pipeline connections and monitoring

Outside the process building the piping system to the tank farm, loading/unloading station, methanol tank and to the fire extinguishing basin is mounted on pipe bridges. The pipe bridges are installed at a sufficient height above ground to avoid damage and enable leaks to be visible. The pipe bridges are steel constructions with reinforced concrete pedestals. The extension compensating of the pipes is realized with clamps on movable bearings and with compensators. For equi-potential bonding the pipe bridge is connected with the grounding system. All pipe joints (e.g. flanges) are only situated either inside the tank wall or the process building, both equipped with spill containment to prevent run-off into drains. Continuous pressure monitoring and alarm systems are established to detect accidental spillage during transfer of materials. Pipeline material Material of pipes depends on the medium. The listed pipe classes are referring to a certain standard of material. All available pipe material is mentioned in the list of ‘Pipe classes’ shown below. The required material is a result of the medium inside.

Pipe class / PN / Material of pipes 111 / PN 10 / (EN10088/1-3) 114 / Vakuum / 1.4301 (EN 10088/1-3) 122 / PN 10 / 1.4571 (EN10088/1-3) 132 / PN 10 / 1.4539 (EN10088/1-3) 152 / PN 10 / Hastelloy 161 / PN 10 / S235JRG2 (St.37.0) 172 / PN 10 / PVDF 243 / PN 16 / P235G1TH (St.35.8) 343 / PN 25 / P235G1TH (St.35.8) 443 / PN 40 / P235G1TH (St.35.8) 920 / PN 200 / 1.4571 Ermeto

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Corrosion protection Basically in the BioDiesel plant the pipelines are made of stainless steel with exemption of pipelines for steam and hot water, which are made of carbon steel. These pipes are sand blasted and coated with primer and are to be insulated. Heat insulation Due to technical, economical and safety reasons all pipes with extraordinary hot or cold surfaces are thermally insulated. Thereby the thickness and type of insulation depends on the diameter of the pipe and the difference in temperature as well (see below mentioned list is referring separately to hot and to cold pipelines). The standard design of insulation is with Rockwool and cladding with aluminium sheets. Heating Some raw materials and some co-products of the BioDiesel process tend to solidification at lower temperatures (e.g. ambient temperatures). To prevent certain media from solidification the related pipelines are equipped with heat tracing.

In hazardous areas there are used self-limiting heating tapes with a temperature controller. In non hazardous areas, flexible single core heating cable with a temperature controller and an overheating protection are used. Self-limiting heat tracing The power consumption of the self-limiting cable is adjusted in relation to the surface temperature and ambient temperature. The temperature increases the resistance increase in the cable. As consequence the power consumption decreases with increasing temperatures. Additionally the self-limiting cable can be equipped with a temperature controller. Because of the parallel power supply the heating tape can be cut to any required length. Flexible single core heat tracing The flexible single core heat tracing is used for heating of large surfaces to provide appropriate process temperatures, viscosities of media and other conditions. The design is based on a silicon rubber lamination technology. The single core heat tracing is available in a variety of configurations including: drum heaters, tapes, blankets of many sizes with and without adhesives. Drum heaters and some tapes are equipped with integrated thermostatic controllers. Blankets and other tapes require a temperature controller. Approximate diameter of pipelines All pipes of the BioDiesel plant have to comply with ISO class I. The pipe material is specified in accordance with DIN in the following table e.g. 1.4301 = AISI 304; 1.4571 = AISI 316L; 1.4539 = 904L; St 37.0 = carbon steel low quality for hot water; PVDF = Teflon for acids; St 35.8 I = for steam pipes. 3.3.2 Reaction Vessels and Pressure Testing All implemented simple pressure vessels and pressure vessels comply with legal requirements regarding design and manufacture according to the European Pressure Equipment Directives. For this purpose the vessels are verified by pressure tests as well as weld strength. The vessels are featured with a name plate containing details about maximum operating pressure and temperature,

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volume, medium, manufacturer as well as factory-number. The vessels are resistant against their contents and are equipped with level control and an overfill protection. Simple pressure vessels ‘Simple pressure vessels’ are any welded vessel subjected to an internal gauge pressure greater than 0.5 bar which is intended to contain air or nitrogen and which is not intended to be fired. The parts and assemblies contributing to the strength of the vessel are made either of non-alloy quality steel or of non-alloy aluminium or non-age hardening aluminium alloys. The materials used for manufacturing the pressurized components are capable of being welded, ductile and tough, so that a rupture at minimum working temperature does not give rise to either fragmentation or brittle-type fracture and it is not adversely affected by ageing. All un-pressurized components of welded vessels are of materials which are compatible with that of the parts to which they are welded. According to the harmonisation of the laws of the Member States relating to simple pressure vessels (87/404/EEC) all vessels used in the BioDiesel plant meet the standards in terms of certification procedures, EC conformity and marking. Pressure vessels Pressure vessels are made for loadings appropriate to its intended use and other reasonably foreseeable operating conditions. The method of operation specified for pressure equipment is such as to preclude any reasonably foreseeable risk in operation of the equipment. Based on calculations according to AD2000 the vessels used in the plant are up to the Directive of pressure equipment (97/23/EG) and therefore conform to international standards. All pressure vessels delivered by BioDiesel International suppliers are already certified and ready for installation. If necessary, adequate protection against corrosion or other chemical effect is provided, taking due account of the designated use. Adequate measures (e.g. appropriate design, additional material thickness as well as cladding materials) are taken to avoid conditions of erosion or abrasion. Final acceptance of pressure vessels includes a technical inspection for the pressure containment aspect, usually in form of a hydrostatic pressure test.

4.0 BUNDED STRUCTURE MANAGEMENT All liquid wastes and potentially hazardous wastes will be stored either inside the main building, in dedicated containers, or in the bunded tank farm. Furthermore, all areas of the proposed site at Marshmeadows, New Ross will be concrete surfaced, with surface water discharging via a high specification interceptor system. The process building is also designed within a bund. All spillages are collected in the catchpit of the process building and pumped to the wastewater tank. The tank farm bund and methanol bund walls are designed as water retaining concrete structures to BS 8007:1987 to accommodate 25% of the total tank volume in accordance with CIRIA report 163. The contents of the IPPC Guidance Note prepared by the EPA on Storage and Transfer of Materials for Scheduled Activities will be noted. There is no direct connection from the bunds to the drainage system under normal conditions.

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GBI intends to assess the integrity of all site bunded areas, pipes and tanks as part of the construction process, commissioning phase and thereafter on a routine basis as well as incorporating adequate leak detection systems. Records of bund inspections and integrity tests will be kept on site.

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Appendix H.1.1

Raw Material and Chemical Storage Areas

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Appendix H.1.3

Material Safety Data Sheets

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Safety Data Sheet 976206/01Date of issue: November 29, 2004 Page 01 of 05Revised: August 27, 2002

1. Identification of the substance/preparation and the company

Baynox bio diesel stabilizer

LANXESS Deutschland GmbH, TS−HSEQDM&I51369 Leverkusen, Germany, Telephone: +49 214 30 65109In case of emergency:Germany: +49 214 30 99300 (Sicherheitszentrale Bayer)United Kingdom: +44 1635 563000 (Bayer UK Ltd., Newbury)

2. Composition/information on ingredientspreparation contains

fatty acid methylesterweight %: 77,6CAS No.: 67762−40−7 Index No.: −−hazard symbol: −− EINECS No.: 267−018−0R−phrases: −−

2,6−di−tert.−butyl−p−cresolweight %: 22,4CAS No.: 128−37−0 Index No.: −−hazard symbol: −− EINECS No.: 204−881−4R−phrases: −−

3. Hazards identificationHazard warning not required.

4. First−aid measuresGENERALINFORMATION: Also heed the risks to your own person. Bring accidentvictim out of danger zone. Remove all contaminated clothing.FOLLOWINGSKIN CONTACT: Wash the skin immediately with plenty of soap andwater; cleaning immediately with polyethyleneglycol 400 and washing subse−quently with plenty of soap and water would be more effective. Consult adoctor.FOLLOWINGEYE CONTACT: Open the eyelids and rinse for an adequate length oftime with water. Consult an eye specialist immediately.UPONINHALATION: Supply fresh air. If patient has difficulty in breathing,administer oxygen, keep him calm and protect him from loss of warmth. Inany case consult a physician.UPONSWALLOWING:The mouth should be rinsed out several times. Ensure thatthe patient drinks water. Consult a doctor.

INFORMATION FOR THE PHYSICIAN:Therapeutic measures: Basic aid, decontamination, symptomatic treatment.

5. Fire−fighting measuresExtinguishing media: All extinguishing materials are suitable.

Firemen have to wear self−contained breathing apparatus. Fight fire inearly stages if safe to do so. Containers at risk from fire should becooled with water and, if possible, removed from the danger area.Do not let enter contaminated extinguishing water into the soil,groundwater or surface waters.

in accordance with the EU Directives (gb)

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Safety Data Sheet 976206/01Date of issue: November 29, 2004 Page 02 of 05Revised: August 27, 2002Baynox bio diesel stabilizer

6. Accidental release measuresTake up mechanically, possibly after first having surrounded the substancewith absorbent material, e.g. sawdust or sand, and waiting until it hassolidified or been absorbed. Fill into labelled, sealable containers.

Use the necessary personal protective equipment when handling.

7. Handling and storageStore tightly sealed in original container.

VCI storage class: 10

Ensure effective ventilation. Vent waste air only via suitable separatorsor scrubbers.

Precautions should generally be taken against electrostatic charges accord−ing to the equipment used and the way the product is handled and packaged.

8. Exposure controls/Personal protectionRespiratory protection: combination filter, e.g. DIN 3181 ABEK, if productforms vapours.Eye protection: gogglesHand protection: e.g. gloves of rubber or PVCAfter contamination with product change the gloves immediately and removethem according to relevant national and local regulationsOther protective equipment: Wear protective clothing.

Avoid contact with skin and eyes and the inhalation of vapour. Wash handsbefore breaks and at end of work. Keep working clothes separate.

9. Physical and chemical properties tested in accordance withForm: liquidDensity: 0,892 kg/l at 20 °C DIN 51757Vapour pressure: 19 hPa at 20 °C

42 hPa at 50 °C47 hPa at 55 °C

Miscibility with water: Product is not miscible.Flash point: 138 °C DIN EN 22719Ignition temperature: 255 °C DIN 51794

10. Stability and reactivityThermal decomposition: No thermal decomposition when stored and handledcorrectly.Hazardous decomposition products: No hazardous decomposition products whenstored and handled correctly. Formation of carbon monoxide, carbon dioxideand other toxic gases in the event of fire or during thermal decomposition.Hazardous reactions: No hazardous reaction when used as directed.


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11. Toxicological informationFor risk assessment data on fatty acid methylester and 2,6−di−tert.−butyl−p−cresol:

Acute toxicity:

fatty acid methylester:LD50 oral, rat: > 2000 mg/kg [1]

2,6−di−tert.−butyl−p−cresol:LD50 oral, rat: > 2000 mg/kg [2]

Skin and mucous membrane compatibility:

fatty acid methylester:Irritation of the eyes/rabbit: non irritant (OECD) [1]

2,6−di−tert.−butyl−p−cresol:Effect on the eyes: Slight irritation (rabbit) [2]Effect on the skin: Slight irritation (rabbit) [2]

Sensitisation:

2,6−di−tert.−butyl−p−cresol:No sensitization (guinea pig) [2]

[1] Details from safety data sheet OELMÜHLELEER CONNEMANNGmbH§ Co[2] unpublished results

12. Ecological informationFor risk assessment data on fatty acid methylester and 2,6−di−tert.−butyl−p−cresol:

fatty acid methylester:

Degradability:> 60 % BSB/CSB (28 days)> 70 % DOC−degradationEasily biodegradable.

2,6−di−tert.−butyl−p−cresol:

Biodegradability: 30 % after 14 days; MITI−test II


Acute bacterial toxicity: No inhibition within the range of water solubili−ty.


Acute bacterial toxicity::No inhibition within the range of water solubility.


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12. Ecological information (Continuation)2,6−di−tert.−butyl−p−cresol:

Toxicity for Daphnia:Acute toxicity:EC0 = above 0,3 mg/lTested on Daphnia magna; duration of test = 48 h(No harmful effect at saturation conc..)

Reproduction toxicity:NOEC= 0,14 mg/l; LOEC = 0,39 mg/lTested on Daphnia magna; duration of test = 21 d


Acute fish toxicity:LC50 : > 100 mg/l, chronical


Acute fish toxicity: LC0 = above 0,5 mg/lTested on Brachydanio rerio; duration of test: 96 h.(No harmful effect at saturation conc..)


Acute toxicity for algae: EC50 = above 0,4 mg/lTested on scenedesmus subs.; duration of test = 72 h

Water pollution class (WGK): 1 − slightly hazardous to waterWGK= Classification in accordance with the German Water Resources Act(in accordance with Annex 4 to the Directive on Water−Hazardous Substances)

The product does not contain any organically bonded halogens which can leadto AOX values in the waste water.

13. Disposal considerationsExamine possibilities for re−utilization. Product residues and uncleanedempty containers should be packaged, sealed, labelled, and disposed of orrecycled according to relevant national and local regulations. Where largequantities are concerned, consult the supplier. When uncleaned emptycontainers are passed on, the recipient must be warned of any possiblehazard that may be caused by residues.

For disposal within the EC, the appropriate code according to the EuropeanWaste Catalogue (EWC) should be used.

14. Transport informationGGVSee/IMDG Code: −− UN No.: −− EmS: −−PG: −− MPO: NOGGVSE: Class −− PG: −− RID/ADR: Class −− PG: −−ADNR: Class −− PG: −− Cat −− ICAO/IATA−DGR: not restr.

(to be continued)


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14. Transport information (Continuation)Declaration for land shipment: −−Declaration for sea shipment: −−Declaration for shipment by air: −−Other information:Not dangerous cargo. Keep separated from foodstuffs.

15. Regulatory informationNo labelling is required in accordance with the EEC directives.

Not subject to the German Regulation on Flammable Liquids (VbF).

16. Other information

The data given here is based on current knowledge and experience. The purposeof this Safety Data Sheet is to describe the products in terms of their safetyrequirements. The above details do not imply any guarantee concerning composition,properties or performance.

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SIGMA-ALDRICH________________________________________________________________________ Material Safety Data Sheet

Date Printed: 08/FEB/2006 Date Updated: 03/MAY/2004 Version 1.0 According to 91/155/EEC________________________________________________________________________1 - Product and Company Information________________________________________________________________________Product Name ARQUAD 2HT-75Product Number 64402

Company Sigma-Aldrich Company Ltd. The Old Brickyard New Road, Gillingham SP8 4XT United KingdomTechnical Phone # 44-(0)-1747-833000Fax 44-(0)-1747-833313Emergency Phone # 44-(0)-1747-833100________________________________________________________________________2 - Composition/Information on Ingredients________________________________________________________________________Product Name CAS # EC no Annex I Index NumberARQUAD 2HT-75 61789-80-8 263-090-2 None

Ingredient Name Percent CAS # EC no Annex I Index NumberThe hazards identified None None Nonewith this product arethose associated withthe residual solventsthat are used in themanufacturing process.

WATER >= 8 7732-18-5 231-791-2 None <= 12

2-PROPANOL >= 12 67-63-0 200-661-7 603-117-00-0 <= 17Symbols: F-XiR-Phrases: 11-36-67 Highly flammable. Irritating to eyes. Vapors may cause drowsiness and dizziness.

Synonyms Adogen 442 * Adogen 448 * Adogen 442-100 P * Aliquat 264 * Ammonyx 2200 * Arquad 2HT * Arquad 2HT75 * Ditallow dimethyl ammonium chloride * Kemamine Q 9702C * Kemamine qsml2 * Noramium M 2SH * Noramium M 2SH15 * Prapagen WK * Prapagen WKT * Quaternium-18________________________________________________________________________3 - Hazards Identification________________________________________________________________________SPECIAL INDICATION OF HAZARDS TO HUMANS AND THE ENVIRONMENT Flammable.

________________________________________________________________________

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4 - First Aid Measures________________________________________________________________________AFTER INHALATION If inhaled, remove to fresh air. If not breathing give artificial respiration. If breathing is difficult, give oxygen.

AFTER SKIN CONTACT In case of contact, immediately wash skin with soap and copious amounts of water.

AFTER EYE CONTACT In case of contact, immediately flush eyes with copious amounts of water for at least 15 minutes. Assure adequate flushing of the eyes by separating the eyelids with fingers.

AFTER INGESTION If swallowed, wash out mouth with water provided person is conscious. Call a physician.________________________________________________________________________5 - Fire Fighting Measures________________________________________________________________________EXTINGUISHING MEDIA Suitable: Carbon dioxide, dry chemical powder, or appropriate foam.

SPECIAL RISKS Specific Hazard(s): Flammable solid. Explosion Hazards: Container explosion may occur under fire conditions.

SPECIAL PROTECTIVE EQUIPMENT FOR FIREFIGHTERS Wear self-contained breathing apparatus and protective clothing to prevent contact with skin and eyes.

SPECIFIC METHOD(S) OF FIRE FIGHTING Use water spray to cool fire-exposed containers.________________________________________________________________________6 - Accidental Release Measures________________________________________________________________________PERSONAL PRECAUTION PROCEDURES TO BE FOLLOWED IN CASE OF LEAK OR SPILL Evacuate area. Shut off all sources of ignition. Use nonsparking tools.

PROCEDURE(S) OF PERSONAL PRECAUTION(S) Wear self-contained breathing apparatus, rubber boots, and heavy rubber gloves.

METHODS FOR CLEANING UP Avoid raising dust. Sweep up, place in a bag and hold for waste disposal. Ventilate area and wash spill site after material pickup is complete.________________________________________________________________________7 - Handling and Storage________________________________________________________________________HANDLING Directions for Safe Handling: Avoid prolonged or repeated exposure. Avoid contact with eyes, skin, and clothing. Avoid breathing dust.

STORAGE

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Conditions of Storage: Keep tightly closed. Keep away from heat, sparks, and open flame.________________________________________________________________________8 - Exposure Controls / Personal Protection________________________________________________________________________ENGINEERING CONTROLS Safety shower and eye bath. Use nonsparking tools. Mechanical exhaust required.

GENERAL HYGIENE MEASURES Remove and wash contaminated clothing promptly. Wash thoroughly after handling.

PERSONAL PROTECTIVE EQUIPMENT Respiratory Protection: Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU). Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Hand Protection: Compatible chemical-resistant gloves. Eye Protection: Chemical safety goggles.________________________________________________________________________9 - Physical and Chemical Properties________________________________________________________________________Appearance Physical State: Solid Form: Paste

Property Value At Temperature or Pressure

pH 6.0 - 9.0BP/BP Range N/AMP/MP Range 30.0 - 40.0 °CFlash Point 25 °C Method: closed cupFlammability N/AAutoignition Temp N/AOxidizing Properties N/AExplosive Properties N/AExplosion Limits N/AVapor Pressure N/ASG/Density N/APartition Coefficient N/AViscosity N/AVapor Density N/ASaturated Vapor Conc. N/AEvaporation Rate N/ABulk Density N/ADecomposition Temp. N/ASolvent Content N/AWater Content N/ASurface Tension N/AConductivity N/AMiscellaneous Data N/ASolubility N/A________________________________________________________________________10 - Stability and Reactivity________________________________________________________________________STABILITY Stable: Stable.

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Materials to Avoid: Oxidizing agents, Acids, Acid anhydrides, Halogens, Aluminum.

HAZARDOUS DECOMPOSITION PRODUCTS Hazardous Decomposition Products: Carbon monoxide, Carbon dioxide.

HAZARDOUS POLYMERIZATION Hazardous Polymerization: Will not occur________________________________________________________________________11 - Toxicological Information________________________________________________________________________RTECS NUMBER: UZ2997000

ACUTE TOXICITY

LD50 LD50 Oral Oral Rat Rat > 9850 mg/kg > 9850 mg/kg

LD50 Intraperitoneal Mouse 1230 MG/KG Remarks: Behavioral:Somnolence (general depressed activity). Behavioral:Change in motor activity (specific assay).

IRRITATION DATA

Skin Skin Rabbit Rabbit 50 mg 50 mg 21D 21D Remarks: Mild irritation effect Mild irritation effect

Eyes Eyes Rabbit Rabbit 100 mg 100 mg

SIGNS AND SYMPTOMS OF EXPOSURE To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated. Drowsiness. Can cause CNS depression. Prolonged exposure can cause: Nausea, headache, and vomiting. Narcotic effect.

ROUTE OF EXPOSURE Skin Contact: Causes skin irritation. Skin Absorption: May be harmful if absorbed through the skin. Eye Contact: Causes eye irritation. Inhalation: Material may be irritating to mucous membranes and upper respiratory tract. May be harmful if inhaled. Ingestion: May be harmful if swallowed.

TARGET ORGAN INFORMATION Kidneys. Nerves. G.I. System. Cardiovascular system.

CHRONIC EXPOSURE - CARCINOGEN Result: This product is or contains a component that is not classifiable as to its carcinogenicity based on its IARC, ACGIH, NTP, or EPA classification.

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________________________________________________________________________12 - Ecological Information________________________________________________________________________No data available.________________________________________________________________________13 - Disposal Considerations________________________________________________________________________SUBSTANCE DISPOSAL Contact a licensed professional waste disposal service to dispose of this material. Burn in a chemical incinerator equipped with an afterburner and scrubber but exert extra care in igniting as this material is highly flammable. Observe all federal, state, and local environmental regulations.________________________________________________________________________14 - Transport Information________________________________________________________________________RID/ADR UN#: 1274 Class: 3 PG: III Proper Shipping Name: n-Propanol

IMDG UN#: 1274 Class: 3 PG: III Proper Shipping Name: PROPANOL Marine Pollutant: No Severe Marine Pollutant: No

IATA UN#: 1274 Class: 3 PG: III Proper Shipping Name: n-Propanol Inhalation Packing Group I: No________________________________________________________________________15 - Regulatory Information________________________________________________________________________CLASSIFICATION AND LABELING ACCORDING TO EU DIRECTIVES R-PHRASES: 10 Flammable.

COUNTRY SPECIFIC INFORMATION

Germany WGK: 1 Self-Classification________________________________________________________________________16 - Other Information________________________________________________________________________WARRANTY The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Inc., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice

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or packing slip for additional terms and conditions of sale. Copyright 2006 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only.

DISCLAIMER For R&D use only. Not for drug, household or other uses.

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SIGMA-ALDRICH Material Safety Data Sheet Date Printed: 08/FEB/2006 Date Updated: 07/FEB/2006 Version 1.11 According to 91/155/EEC 1 - Product and Company Information Product Name METHANOL SPECTROPHOTOMETRIC GRADE Product Number M3641 Company Sigma-Aldrich Ireland Ltd. Airton Road, Tallaght Dublin 24 Ireland Technical Phone # 353-1404-1900 Fax 353-1404-1910 2 - Composition/Information on Ingredients Product Name CAS # EC no Annex I Index Number METHANOL 67-56-1 200-659-6 603-001-00-X Formula CH4O Molecular Weight 32.04 AMU Synonyms Alcool methylique (French) * Alcool metilico (Italian) * Bieleski's solution * Carbinol * Colonial Spirit * Columbian Spirit * Metanolo (Italian) * Methanol (ACGIH) * Methyl alcohol (DOT:OSHA) * Methylol * Methylalkohol (German) * Methyl hydrate * Methyl hydroxide * Metylowy alkohol (Polish) * Monohydroxymethane * Pyroxylic Spirit * RCRA waste number U154 * Wood alcohol * Wood naphtha * Wood Spirit * METHYL ALCOHOL * WOOD ALCOHOL 3 - Hazards Identification SPECIAL INDICATION OF HAZARDS TO HUMANS AND THE ENVIRONMENT Highly flammable. Toxic by inhalation, in contact with skin and if swallowed. Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. 4 - First Aid Measures AFTER INHALATION If inhaled, remove to fresh air. If not breathing give artificial respiration. If breathing is difficult, give oxygen. AFTER SKIN CONTACT In case of skin contact, flush with copious amounts of water for at least 15 minutes. Remove contaminated clothing and shoes. Call a physician. AFTER EYE CONTACT In case of contact with eyes, flush with copious amounts of

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water for at least 15 minutes. Assure adequate flushing by separating the eyelids with fingers. Call a physician. AFTER INGESTION If swallowed, wash out mouth with water provided person is conscious. Call a physician immediately. 5 - Fire Fighting Measures EXTINGUISHING MEDIA Suitable: Water spray. Carbon dioxide, dry chemical powder, or appropriate foam. SPECIAL RISKS Specific Hazard(s): Flammable liquid. Emits toxic fumes under fire conditions. Explosion Hazards: Vapor may travel considerable distance to source of ignition and flash back. Container explosion may occur under fire conditions. SPECIAL PROTECTIVE EQUIPMENT FOR FIREFIGHTERS Wear self-contained breathing apparatus and protective clothing to prevent contact with skin and eyes. 6 - Accidental Release Measures PERSONAL PRECAUTION PROCEDURES TO BE FOLLOWED IN CASE OF LEAK OR SPILL Evacuate area. Shut off all sources of ignition. PROCEDURE(S) OF PERSONAL PRECAUTION(S) Wear self-contained breathing apparatus, rubber boots, and heavy rubber gloves. ENVIRONMENTAL PRECAUTION(S) Do not allow material to enter drains or water courses. METHODS FOR CLEANING UP Cover with dry-lime, sand, or soda ash. Place in covered containers using non-sparking tools and transport outdoors. Ventilate area and wash spill site after material pickup is complete. 7 - Handling and Storage HANDLING Directions for Safe Handling: Do not breathe vapor. Avoid contact with eyes, skin, and clothing. Avoid prolonged or repeated exposure. STORAGE Conditions of Storage: Keep container closed. Keep away from heat, sparks, and open flame. 8 - Exposure Controls / Personal Protection ENGINEERING CONTROLS Safety shower and eye bath. Use nonsparking tools. Use only in a chemical fume hood. GENERAL HYGIENE MEASURES Wash contaminated clothing before reuse. Wash thoroughly after handling. SIGMA - M3641 www.sigma-aldrich.com Page 2

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EXPOSURE LIMITS Country Source Type Value Poland NDS 100 MG/M3 Poland NDSCh 300 MG/M3 Poland NDSP - EXPOSURE LIMITS - DENMARK Source Type Value OEL TWA 260 mg/m3 200 ppm Remarks: H EXPOSURE LIMITS - GERMANY Source Type Value TRGS 900 OEL 260 mg/m3 200 ppm Remarks: 4 Remarks: H EXPOSURE LIMITS - NORWAY Source Type Value OEL TWA 130 mg/m3 100 ppm Remarks: H EXPOSURE LIMITS - SWEDEN Source Type Value LLV (Level250 mg/m3 200 ppm Remarks: H EXPOSURE LIMITS - SWITZERLAND Source Type Value OEL OEL 260 mg/m3 200 ppm Remarks: H M C EXPOSURE LIMITS - UNITED KINGDOM Source Type Value OEL OEL 266 mg/m3 200 ppm OEL STEL 333 mg/m3 250 ppm Remarks: Skin Indicative limit value PERSONAL PROTECTIVE EQUIPMENT Respiratory Protection: Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU). Use supplied-air or SCBA respirators. Europe permits the use of type AXBEK full-face cartridge respirators (EN 14387). Hand Protection: Compatible chemical-resistant gloves. Eye Protection: Chemical safety goggles. 9 - Physical and Chemical Properties Appearance Physical State: Liquid Color: Colorless Property Value At Temperature or Pressure pH N/A SIGMA - M3641 www.sigma-aldrich.com Page 3

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BP/BP Range 64.0 - 65.0 °C 760 mmHg MP/MP Range - 98.0 °C Flash Point 11 °C Method: closed cup Flammability N/A Autoignition Temp 385 °C Oxidizing Properties N/A Explosive Properties N/A Explosion Limits Lower: 6 % Upper: 36 % Vapor Pressure 97.68 mmHg 20 °C SG/Density 0.791 g/cm3 Partition Coefficient Log Kow: - 0.770 Viscosity N/A Vapor Density 0.79 g/l Saturated Vapor Conc. N/A Evaporation Rate N/A Bulk Density N/A Decomposition Temp. N/A Solvent Content N/A Water Content N/A Surface Tension N/A Conductivity N/A Miscellaneous Data N/A Solubility Solubility in Water:Miscible. 10 - Stability and Reactivity STABILITY Stable: Stable. Materials to Avoid: Acids, Acid chlorides, Acid anhydrides, Oxidizing agents, Alkali metals, Reducing agents. HAZARDOUS DECOMPOSITION PRODUCTS Hazardous Decomposition Products: Carbon monoxide, Carbon dioxide. HAZARDOUS POLYMERIZATION Hazardous Polymerization: Will not occur 11 - Toxicological Information RTECS NUMBER: PC1400000 ACUTE TOXICITY LDLO Oral Man 6422 mg/kg Remarks: Gastrointestinal:Nausea or vomiting. Lungs, Thorax, or Respiration:Dyspnea. Brain and Coverings:Changes in circulation (hemorrhage,thrombosis, etc.). LDLO Oral Human 428 mg/kg Remarks: Behavioral:Headache. Lungs, Thorax, or Respiration:Other changes. LDLO Oral Human SIGMA - M3641 www.sigma-aldrich.com Page 4

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143 mg/kg Remarks: Sense Organs and Special Senses (Nose, Eye, Ear, and Taste):Eye:Optic nerve neuropathy. Lungs, Thorax, or Respiration:Dyspnea. Gastrointestinal:Nausea or vomiting. LD50 Oral Rat 5628 mg/kg LC50 Inhalation Rat 64,000 ppm 4H LD50 Intraperitoneal Rat 7529 MG/KG LD50 Intravenous Rat 2131 MG/KG LD50 Oral Mouse 7300 mg/kg LD50 Intraperitoneal Mouse 10765 MG/KG LD50 Subcutaneous Mouse 9800 MG/KG LD50 Intravenous Mouse 4710 MG/KG LD50 Oral Monkey 7000 mg/kg Remarks: Behavioral:Coma. Behavioral:Ataxia. Behavioral:Muscle weakness. LD50 Oral Rabbit 14200 mg/kg LD50 Skin Rabbit 15800 mg/kg SIGMA - M3641 www.sigma-aldrich.com Page 5

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LD50 Intraperitoneal Rabbit 1826 MG/KG LD50 Intravenous Rabbit 8907 MG/KG LD50 Intraperitoneal Guinea pig 3556 MG/KG LD50 Intraperitoneal Hamster 8555 MG/KG IRRITATION DATA Skin Rabbit 20 mg 24H Remarks: Moderate irritation effect Eyes Rabbit 40 mg Remarks: Moderate irritation effect Eyes Rabbit 100 mg 24H Remarks: Moderate irritation effect SIGNS AND SYMPTOMS OF EXPOSURE Nausea, headache, and vomiting. Gastrointestinal disturbances. Dizziness. Weakness. Confusion. Drowsiness. Unconsciousness. May cause convulsions. Ingestion can cause: Methyl alcohol may be fatal or cause blindness if swallowed. Cannot be made non-poisonous. ROUTE OF EXPOSURE Skin Contact: Causes skin irritation. Skin Absorption: Toxic if absorbed through skin. Eye Contact: Causes eye irritation. Inhalation: Material may be irritating to mucous membranes and upper respiratory tract. Toxic if inhaled. Ingestion: Toxic if swallowed. TARGET ORGAN INFORMATION Eyes. Kidneys. Liver. Heart. Central nervous system. CHRONIC EXPOSURE - MUTAGEN Human 300 MMOL/L SIGMA - M3641 www.sigma-aldrich.com Page 6

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Cell Type: lymphocyte DNA inhibition Rat 10 UMOL/KG Oral DNA damage Mouse 7900 MG/L (+S9) Cell Type: lymphocyte Mutation in microorganisms Mouse 1 GM/KG Oral Cytogenetic analysis Mouse 75 MG/KG Intraperitoneal Cytogenetic analysis CHRONIC EXPOSURE - TERATOGEN Species: Rat Dose: 35295 MG/KG Route of Application: Oral Exposure Time: (1-15D PREG) Result: Effects on Newborn: Biochemical and metabolic. Effects on Embryo or Fetus: Fetotoxicity (except death, e.g., stunted fetus). Species: Rat Dose: 20000 PPM/7H Route of Application: Inhalation Exposure Time: (1-22D PREG) Result: Specific Developmental Abnormalities: Urogenital system. Specific Developmental Abnormalities: Cardiovascular (circulatory) system. Specific Developmental Abnormalities: Musculoskeletal system. Species: Rat Dose: 20000 PPM/7H Route of Application: Inhalation Exposure Time: (7-15D PREG) Result: Specific Developmental Abnormalities: Endocrine system. Specific Developmental Abnormalities: Musculoskeletal system. Species: Rat Dose: 10000 PPM/7H Route of Application: Inhalation Exposure Time: (7-15D PREG) Result: Effects on Embryo or Fetus: Fetotoxicity (except death, e.g., stunted fetus). Species: Rat Dose: 5200 UL/KG Route of Application: Oral Exposure Time: (10D PREG) Result: Specific Developmental Abnormalities: Urogenital system. Specific Developmental Abnormalities: Eye, ear. Effects on SIGMA - M3641 www.sigma-aldrich.com Page 7

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Embryo or Fetus: Fetotoxicity (except death, e.g., stunted fetus). Species: Mouse Dose: 40 GM/KG Route of Application: Oral Exposure Time: (6-15D PREG) Result: Specific Developmental Abnormalities: Craniofacial (including nose and tongue). Effects on Embryo or Fetus: Fetotoxicity (except death, e.g., stunted fetus). Species: Mouse Dose: 4 GM/KG Route of Application: Oral Exposure Time: (7D PREG) Result: Specific Developmental Abnormalities: Musculoskeletal system. Specific Developmental Abnormalities: Craniofacial (including nose and tongue). Species: Mouse Dose: 1500 PPM/6H Route of Application: Inhalation Exposure Time: (7-9D PREG) Result: Specific Developmental Abnormalities: Central nervous system. Species: Mouse Dose: 5000 PPM/7H Route of Application: Inhalation Exposure Time: (6-15D PREG) Result: Specific Developmental Abnormalities: Craniofacial (including nose and tongue). Specific Developmental Abnormalities: Central nervous system. Species: Mouse Dose: 2000 PPM/7H Route of Application: Inhalation Exposure Time: (6-15D PREG) Result: Specific Developmental Abnormalities: Musculoskeletal system. CHRONIC EXPOSURE - REPRODUCTIVE HAZARD Species: Rat Dose: 7500 MG/KG Route of Application: Oral Exposure Time: (17-19D PREG) Result: Effects on Newborn: Behavioral. Species: Rat Dose: 35295 MG/KG Route of Application: Oral Exposure Time: (1-15D PREG) Result: Effects on Fertility: Post-implantation mortality (e.g., dead and/or resorbed implants per total number of implants). Effects on Fertility: Pre-implantation mortality (e.g., reduction in number of implants per female; total number of implants per corpora lutea). Effects on Fertility: Female fertility index (e.g., # females pregnant per # sperm positive females; # females pregnant per # females mated ). Species: Rat SIGMA - M3641 www.sigma-aldrich.com Page 8

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Dose: 20 GM/KG Route of Application: Oral Exposure Time: (6-15D PREG) Result: Effects on Fertility: Litter size (e.g.; # fetuses per litter; measured before birth). Effects on Fertility: Post-implantation mortality (e.g., dead and/or resorbed implants per total number of implants). Species: Rat Dose: 200 PPM/20H Route of Application: Oral Exposure Time: (78W MALE) Result: Paternal Effects: Testes, epididymis, sperm duct. Species: Mouse Dose: 7500 PPM/7H Route of Application: Inhalation Exposure Time: (6-15D PREG) Result: Effects on Embryo or Fetus: Fetal death. Effects on Fertility: Post-implantation mortality (e.g., dead and/or resorbed implants per total number of implants). Species: Mouse Dose: 15000 PPM Route of Application: Inhalation Exposure Time: (7-9D PREG) Result: Effects on Embryo or Fetus: Fetotoxicity (except death, e.g., stunted fetus). Effects on Fertility: Post-implantation mortality (e.g., dead and/or resorbed implants per total number of implants). Species: Mouse Dose: 5 GM/KG Route of Application: Intraperitoneal Exposure Time: (5D MALE) Result: Paternal Effects: Spermatogenesis (including genetic material, sperm morphology,motility, and count). 12 - Ecological Information ECOTOXICOLOGICAL EFFECTS Test Type: LC50 Fish Species: Onchorhynchus mykiss (Rainbow trout) Time: 96 h Value: 19,000 mg/l Test Type: LC50 Fish Species: Cyprinus carpio Time: 48 h Value: 36,000 mg/l Test Type: EC50 Daphnia Species: Daphnia magna Time: 48 h Value: 24,500 mg/l Test Type: EC100 Daphnia Species: Daphnia magna Time: 24 h Value: 10,000 mg/l SIGMA - M3641 www.sigma-aldrich.com Page 9

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13 - Disposal Considerations SUBSTANCE DISPOSAL Contact a licensed professional waste disposal service to dispose of this material. Burn in a chemical incinerator equipped with an afterburner and scrubber but exert extra care in igniting as this material is highly flammable. Observe all federal, state, and local environmental regulations. 14 - Transport Information RID/ADR UN#: 1230 Class: 3 PG: II Subrisk: 6.1 Proper Shipping Name: Methanol IMDG UN#: 1230 Class: 3 PG: II Subrisk: 6.1 Proper Shipping Name: Methanol Marine Pollutant: No Severe Marine Pollutant: No IATA UN#: 1230 Class: 3 PG: II Subrisk: 6.1 Proper Shipping Name: Methanol Inhalation Packing Group I: No 15 - Regulatory Information CLASSIFICATION AND LABELING ACCORDING TO EU DIRECTIVES ANNEX I INDEX NUMBER: 603-001-00-X INDICATION OF DANGER: F-T Highly Flammable. Toxic. R-PHRASES: 11-23/24/25-39/23/24/25 Highly flammable. Toxic by inhalation, in contact with skin and if swallowed. Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. S-PHRASES: 7-16-36/37-45 Keep container tightly closed. Keep away from sources of ignition - no smoking. Wear suitable protective clothing and gloves. In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). COUNTRY SPECIFIC INFORMATION Germany WGK: 1 ID-Number: 145 KBwS-Decision SWITZERLAND SWISS POISON CLASS: 3 SIGMA - M3641 www.sigma-aldrich.com Page 10

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NORWAY Declaration Number: 1931 16 - Other Information WARRANTY The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Inc., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale. Copyright 2006 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only. DISCLAIMER For R&D use only. Not for drug, household or other uses. SIGMA - M3641 www.sigma-aldrich.com Page 11

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Safety Data

Nitrogen refrigerated

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Safety Data Sheet

6. ACCIDENTAL RELEASE MEASURES

7. HANDLING AND STORAGE

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

Personal precautionsEvacuate area. Use protective clothing.Wear self-contained breathing apparatus when entering areaunless atmosphere is proved to be safe.Ensure adequate air ventilation.

Environmental precautionsTry to stop release.Prevent from entering sewers, basements and workpits, or anyplace where its accumulation can be dangerous.

Clean up methodsVentilate area.

Suck back of water into the container must be prevented.Do not allow backfeed into the container.Use only properly specified equipment which is suitable for thisproduct, its supply pressure and temperature. Contact your gassupplier if in doubt.Refer to supplier's container handling instructions.Keep container below 50°C in a well ventilated place.

Ensure adequate ventilation. Protect eyes, face and skin from liquid splashes.

9. PHYSICAL AND CHEMICAL PROPERTIES

Molecular weight28

Melting point-210°C

Boiling point-196˚C

Critical temperature-147˚C

Relative density, gas0.97 (air=1)

Relative density, liquid0.8 (water=1)

Vapour Pressure 20˚CNot applicable.

Solubility mg/l water20 mg/l

Appearance/ColourColourless liquid.

OdourNo odour warning properties.

Other dataGas/vapour heavier than air. May accumulate in confinedspaces, particularly at or below ground level.

1. IDENTIFICATION OF THE SUBSTANCE/PREPARATION AND OF THE COMPANY

2. COMPOSITION/INFORMATION ON INGREDIENTS

3. HAZARDS IDENTIFICATION

4. FIRST AID MEASURES

MSDS Nr089B

Product nameNitrogen (refrigerated)

Chemical formulaN2

Company identificationsee footer

Emergency phone numbersee footer

InhalationIn high concentrations may cause asphyxiation. Symptoms mayinclude loss of mobility/consciousness. Victim may not be awareof asphyxiation. Remove victim to uncontaminated area wearing self-containedbreathing apparatus. Keep victim warm and rested. Call a doctor. Apply artificial respiration if breathing stopped.

Skin/eye contactImmediately flush eyes thoroughly with water for at least 15 minutes.In case of frostbite, spray with water for at least 15 minutes.Apply a sterile dressing.Obtain medical assistance

IngestionIngestion is not considered a potential route of exposure.

Substance/PreparationSubstance

Components/ImpuritiesContains no other components or impurities which will influencethe classification of the product.

CAS Nr07727-37-9

EEC Nr (from EINECS)231-783-9

Refrigerated liquefied gas. Contact with product may cause coldburns or frostbite.

In high concentrations may cause asphyxiation.

5. FIRE FIGHTING MEASURES

Specific hazardsExposure to fire may cause containers to rupture/explode.Non flammable.

Hazardous combustion productsNone.

Suitable extinguishing mediaAll known extinguishants can be used.

Specific methodsIf possible, stop flow of product. Move container away or coolwith water from a protected position.

If leaking, do not spray water onto container. Water surroundingarea (from protected position) to contain fire.

Special protective equipment for fire fightersIn confined space use self-contained breathing apparatus.

Safety Data Sheet Nitrogen refrigerated089B

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10. STABILITY AND REACTIVITY

Stable under normal conditions. Liquid spillages can causeembrittlement of structural materials.

11. TOXICOLOGICAL INFORMATION

GeneralNo known toxicological effects from this product.

12. ECOLOGICAL INFORMATION

15. REGULATORY INFORMATION

13. DISPOSAL CONSIDERATIONS

14. TRANSPORT INFORMATION

16. OTHER INFORMATIONGeneralDo not discharge into any place where its accumulation could bedangerous.Contact supplier if guidance is required.

GeneralCan cause frost damage to vegetation.

Number in Annex I of Dir 67/548Not included in Annex I.

EC ClassificationNot classified as dangerous substance.

EC Labelling (Symbols, R&S phrases)No EC labelling required.

May cause frostbite. Asphyxiant in high concentrations.

Keep container in well ventilated place.

Do not breathe the gas.

Ensure all national/local regulations are observed.

The hazard of asphyxiation is often overlooked and must bestressed during operator training.

Contact with liquid may cause cold burns/frost bite.

Before using this product in any new process or experiment, athorough material compatibility and safety study should becarried out.

Details given in this document are believed to be correct at thetime of going to press. Whilst proper care has been taken in thepreparation of this document, no liability for injury or damageresulting from its use can be accepted.

Proper shipping nameNitrogen, refrigerated liquid.

UN Nr1977

Class/Div2.2

ADR/RID Item Nr2.3°A

ADR/RID Hazard Nr22

Tremcard Nr112

Groupcard Nr20g22

Labelling ADRLabel 2: non-flammable non-toxic gas.

Other transport informationAvoid transport on vehicles where the load space is not separated from the driver’s compartment.Ensure vehicle driver is aware of the potential hazards of theload and knows what to do in the event of an accident or anemergency.Before transporting product containers ensure that they arefirmly secured and:- there is adequate ventilation.- comply with applicable regulations.

Air Products Plc, Hersham Place, Molesey Road, Walton-on-Thames, Surrey, KT12 4RZ.www.airproducts.com


Emergency Telephone: 0500 020202Version1.18 29.06.99Material safety data sheets are updated as required - the most up-to-date version of this safety sheet can be found on

the Air Products’ website - www.airproducts.com/msds

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SPECIFICATION

PHYSICAL PROPERTIESMolecular weight 28.016Boiling point at 1 atm -195.8ºCMelting point at 1 atm -209.9ºCDensity of gas at 20°C, 1 atm 1.16g/litreDensity of liquid at Boiling point 0.808 g/mlSpecific gravity of gas (Air=1) 0.967Critical temperature -147.0ºCCritical pressure 32.85 bar (g)Solubility in water at 10°C,1 atm 0.0025wt%Latent heat of vaporisation at Boiling point 1336 caI/g - mole

GENERAL PROPERTIES1. Gaseous nitrogen is colourless, odourless and tasteless and

is slightly lighter than air at equal temperatures; coldnitrogen vapour is, however, denser than atmospheric air.

2. Liquid nitrogen is odourless, colourless and boils at -195.8°C. One volume of liquid nitrogen givesapproximately 700 volumes of gas at ambient conditions.

3. Nitrogen is not flammable. It is chemically inert, except athigh temperatures and pressures. Its volume concentrationin air is 78%.

4. Liquid nitrogen and cold gaseous nitrogen can cause severeburns or frostbite when in contact with the skin orrespiratory tract.

5. Nitrogen is non-corrosive, non-toxic, does not support lifeand acts as an asphyxiant.

SAFETYThe following information is for guidance of customers usingnitrogen. It is strongly recommended that users know andunderstand the properties of the gas before handling it.

FIRE AND EXPLOSION HAZARDSNeither gaseous nor liquid nitrogen is flammable and does not initself constitute a fire or explosion risk. However, both gaseousand liquid nitrogen are normally stored under pressure and thestorage vessels, whether gas containers or liquid tanks, shouldnot be located in areas where there is a high risk of fire or wherethey may normally be exposed to excessive heat. Containerscontaining compressed gaseous nitrogen may rupture violently ifoverheated as a result of exposure to fire.At equal pressures the boiling point of liquid nitrogen is lowerthan that of liquid air. Air will condense on the external surfacesof vessels or pipework containing liquid nitrogen at anequilibrium pressure less than 1.5 bars absolute if the vessels

are either unlagged, or lagged with a porous cellular typeinsulant.

The liquid air produced can result in oxygen enrichment of theatmosphere local to the equipment. Special precautions musttherefore be taken with regard to the insulation of the vesselbefore any maintenance or repair work is started, particularlywhere the use of open flames or other potential sources ofignition is intended.

MATERIAL HAZARDSCertain steels such as carbon steel and some other materials areunsuitable for service at sub-zero temperatures because theylose impact strength and become extremely brittle. Carbon steelcannot be used safely at temperatures below -30°C (-20°F) andis obviously unsuitable for service with liquid nitrogen. Materialsnormally suitable for service at low temperatures are theaustenitic stainless steels, aluminium and copper and its alloys.In an area where liquid nitrogen spillage can occur, care shouldbe taken to ensure that the liquid does not come into contactwith vulnerable steel structures and vehicle tyres. Care should betaken to ensure that liquid nitrogen and cold nitrogen vapour arenot trapped in a closed system without any form of automaticpressure relief. Otherwise pressures well in excess of theequipment working pressure will be generated as the systemwarms up, thus creating a possible rupture hazard.

HEALTH HAZARDSAsphyxiaNitrogen, although non-toxic, can constitute an asphyxiationhazard through the displacement of the oxygen in theatmosphere. The potential for this type of hazard is significantbecause of the widespread use of nitrogen as a purging orblanketing gas in chemical, metallurgical. and other industrialoperations and because neither nitrogen gas nor oxygendepletion are detectable by the normal human senses. Unlessadequate precautions are taken, persons can be exposed tooxygen deficient atmospheres if they enter equipment or areaswhich have contained or have been purged with nitrogen.

BREATHING A PURE NITROGEN ATMOSPHERE WILL PRODUCEIMMEDIATE LOSS OF CONSCIOUSNESS AND ALMOSTIMMEDIATE DEATH.

Cold burnsLiquid nitrogen and cold nitrogen vapours or gases can produceeffects on the skin similar to a burn. Naked parts of the bodycoming into contact with uninsulated parts of equipment mayalso stick fast (because all available moisture is frozen) and theflesh may be torn on separation.

FrostbiteSevere or prolonged exposure to cold nitrogen vapour and gascan cause frostbite. Local pain usually gives warning of freezingbut sometimes no pain is experienced. Frozen tissues arepainless and appear waxy with a pallid yellowish colour. Thawingof the frozen tissues can cause intense pain. Shock may alsooccur if the burns are at all extensive.

Effects of cold on lungsProlonged breathing of extremely cold atmospheres may damagethe lungs.

HypothermiaLow environmental temperatures can cause hypothermia and allpersons at risk should wear warm clothing. Hypothermia ispossible in any environmental temperature below 10°C (50°F).

PRECAUTIONSOperation and maintenanceIt is essential that operations involving the use of gaseous orliquid nitrogen, particularly where large quantities are used, are

N2 %nitrogen plus inert rare gases (guaranteed by % volume) >99.999oxygen (guaranteed ppm by volume) <5water (guaranteed ppm by volume) <2Typical Analysis (by volume)nitrogen 99.999%oxygen <2ppmwater <1ppmCarbon dioxide/carbon monoxide/nitrous oxide/hydrocarbons/methane/acetylene

These impurities maybe present in trace

quantities

The information within this guidance note is believed to be accurateand is given in good faith. It is for the user of the gas to determinethe correct approach to safe use of the gas and the actions to takein any site emergency involving a release of the gas.

Information on all gases supplied by Air Products can also be foundin the material safety data sheets issued to all customers.


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conducted in well ventilated areas to prevent the formation ofoxygen deficient atmospheres.

Ideally, nitrogen should be vented into the open air well awayfrom areas frequented by personnel. Nitrogen should NEVER bereleased or vented in enclosed areas or buildings where theventilation is inadequate.

Before entering areas, vessels or other equipment formaintenance (or other purposes in which the atmosphere is, ormay become, deficient in oxygen) action should be taken tomake the equipment safe. Preparatory work will includeequipment isolation from hazardous processes, purging andcontinued ventilation with air as appropriate. Equipment inservice with flammable gases should be purged with nitrogenprior to purging with air to avoid the formation of flammablemixtures.

Prior to entry, the atmospheres should be tested with a portableoxygen analyser (calibrated before use) to ensure that theoxygen content lies between 20% and 22% by volume. The useof a safety work permit system is strongly recommended. Itshould be recognised that although nitrogen is slightly lighterthan air at equal temperatures, liquid nitrogen and cold nitrogenvapour are denser than air and can accumulate in low lying areassuch as pits and trenches. Where large spills of liquid nitrogenoccur, a fog is formed in the vicinity of the spill caused by thecondensation of water vapour in the surrounding air. The fog, inaddition to severely reducing visibility, may contain oxygenconcentrations appreciably lower than that of air, thus presentinga local asphyxiation hazard.

Personnel protectionIt is recommended that persons handling gas cylinders shouldwear safety glasses, safety footwear and clean, stout gloves.

Persons handling equipment in service with liquid nitrogenshould wear protective face shields, loose fitting leather orinsulated gauntlets.

EMERGENCIESIn the event of accident or emergency, the instructionsbelow should be implemented without delay. Afteremergency action has been taken, contact Air Products forfurther advice.

AsphyxiationPersons showing symptoms of oxygen deprivation should bemoved immediately to a normal atmosphere. Persons who areunconscious or not breathing must receive immediate first aid.Medical assistance should be summoned without delay. First aidmeasures include inspection of the victim’s airway forobstruction, artificial respiration and simultaneous administrationof oxygen. The victim should be kept warm and resting.

It is important to note that personnel carrying out rescueoperations must minimise the risk to themselves.

A RESCUER SHOULD NOT ENTER AN OXYGEN DEFICIENTATMOSPHERE WITHOUT USING SUITABLE SELF-CONTAINEDBREATHING APPARATUS, OTHERWISE HE MAY HIMSELF BEOVERCOME.

Many double fatalities have occurred in industry as a result ofpersonnel who, with the best intentions but without properbreathing apparatus and equipment, have entered an oxygendeficient atmosphere in an attempt to rescue a colleague.

Treatment of cold burns and frostbiteCold burns should receive medical attention as quickly aspossible. However, such injuries are not an everyday occurrenceand doctors, hospital staff or works first aid personnel may notbe aware of the basic methods of treatment. The following notes

describe the first aid treatment and recommended advice forfurther treatment to be given by a medical practitioner or ahospital.

1. First aidIn severe cases summon medical attention at once. Flushaffected areas of skin with copious quantities of tepid water toreduce freezing of tissue. Loosen any clothing that may restrictblood circulation. Move the victim to a warm place but not to ahot environment and do not apply direct heat to the affectedparts. Every effort should be made to protect the frozen partsfrom infection and further injury. Dry, sterile, bulky dressingsmay be used but should not be applied so tightly that bloodcirculation is restricted.

2. Treatment by medical practitioner or hospitala) Remove any clothing that may constrict the circulation to

the frozen area. Remove patient to sick bay or hospital.

b) Immediately place the part of the body exposed to thecryogenic material in a water bath which has a temperatureof not less than 40ºC (1O4ºF) but not more than 45ºC(113ºF). (See below for exceptions to this recommendation).NEVER USE DRY HEAT OR HOT WATER. Temperatures in excess of 45ºC will superimpose a burnupon the frozen tissue.

c) If there has been massive exposure to the super-cooledmaterial so that the general body temperature is depressed,the patient must be re-warmed gradually. Shock may occurduring re-warming, especially if this is rapid.

d) Frozen tissues are painless and appear waxy with a pallidyellowish colour. They become painful, swollen and veryprone to infection when thawed. Therefore do not re-warmrapidly if the accident occurs in the field and the patientcannot be transported to hospital immediately. Thawingmay take from 15 to 60 minutes and should be continueduntil the blue, pale colour of the skin turns to pink or red.Morphine or some other potent analgesic is required tocontrol the pain during thawing and should be administeredunder professional medical supervision.

e) If the frozen part of the body has thawed by the timemedical attention has been obtained, do not re-warm.Under these circumstances cover the area with dry, steriledressings with a large, bulky, protective covering.

f) Administer a tetanus booster after hospitalisation.

HypothermiaPersons suspected to be suffering from hypothermia should bewrapped in blankets and moved to a warm place. Slowrestoration of temperature is necessary and forms of locallyapplied heat should not be used. Summon medical attention.

Fire fightingNitrogen is not flammable and no special fire fighting precautionsor equipment are needed. If an outbreak of fire occurs in thevicinity of nitrogen storage equipment the local fire brigadeshould be summoned at once. Unless containers containingcompressed gaseous nitrogen can be removed safely to anunaffected area every effort should be made to keep them coolby spraying them with large quantities of water.

Liquid nitrogen spillageIf large spills of liquid nitrogen occur, large quantities of watershould be used to increase the rate of liquid vaporisation.Vehicles involved in a heavy liquid spillage should not be movedas the tyres may be frozen to the ground and the rubber will bebrittle.


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LPG

P

SafetyDistances

Nitrogen

Flammable liquid or gas pipelineswithout mechanicaljoints

Vehicle parkingareas

Property boundaries

Fuel gas vents Ventilator air intakes

LPG or bulkflammable storage

Flammable gascylinder storage*

Small woodenstructures, (huts,sheds), stocks ofcombustiblematerial

Pits, ducts,untrapped drains

Flanges, unions inpipelines containingflammable gases orliquids

Doors/windows ofoffices, canteens,etc.

Public roads,railway lines

Notes:Separation distancesbased on Code ofPractice CP21published by BritishCompressed Gas Association(BCGA). Tel: 023 8064 1488Fax: 023 8064 1477

* See BCGA CP8 forhydrogen cylinderseparationdistances

See BCGA CP6 foracetylene cylinderseparationdistances

1m

1.5m

3m

5m

L5663/5

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C:\DOCUME~1\ADMINI~1\LOCALS~1\Temp\1\2552297810924919490.doc Page 1 of 5

Material Safety Data Sheet

WHMIS Protective Clothing TDG Road / Rail

Section 1: Product Identification and Uses

Common/Trade name Prayphos P5-75 CI# Not applicable Synonyms Phosphoric acid 75%; orthophosphoric acid75% DSL CEPA DSL: Prayphos P5-75 Chemical Name Phosphoric acid 75% solution CAS# 7664-38-2 Chemical Formula H3PO4 Code PHO Chemical Family Acid. Molecular Weight Not applicable. Minor Update February 10, 2003 Manufacturer Prayon-Rupel Supplier Benson Chemicals Limited 1012 Gore Rd. Freelton, Ontario L0R 1K0 Tel: 800-265-0014 or 905-659-3351 Fax: 905-659-1689

Material Uses Other non specified industry: Fertilizer. Detergent. Water treatment

Section 1A: First Aid Measures Eye Contact Check for and remove any contact lenses. Immediately flush eyes with running water for at least

15 minutes, keeping eyelids open. COLD water may be used. DO NOT use an eye ointment. Seek medical attention.

Skin Contact If the chemical got into the clothed portion of the body, remove the contaminated clothes as quickly as possible, protecting your own hands and body. Place the victim under a deluge shower. If the chemical touches the victim’s exposed skin, such as the hands: Gently and thoroughly wash the contaminated skin with running water and non-abrasive soap. Be particularly careful to clean folds, crevices, creases and groin. COLD water may be used. If irritation persists, seek medical attention. Wash contaminated clothing before reusing.

Hazardous Skin Contact Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek immediate medical attention.

Slight Inhalation Allow the victim to rest in a well ventilated area. Seek immediate medical attention. Hazardous Inhalation Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a collar,

tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is not breathing, perform mouth-to-mouth resuscitation. WARNING: It may be hazardous to the person providing aid to give mouth-to-mouth resuscitation when the inhaled material is toxic, infections or corrosive. Seek immediate medical attention.

Slight Ingestion DO NOT induce vomiting. Examine the lips and mouth to ascertain whether the tissues are damaged, a possible indication that the toxic material was ingested; the absence of such signs, however, is not conclusive. Loosen tight clothing such as a collar, tie, belt or waistband. If the victim is not breathing, perform mouth-to-mouth resuscitation. Give water or milk. Seek immediate medical attention.

Hazardous Ingestion No additional information.

Section 2: Hazardous Ingredients

Name CAS # % by Weight Exposure Limits LC50/LD50

1) Prayphos P5-75 7664-38-2 75 TWA: 1 STEL: 3 ORAL (LD50): Acute 1530 mg/kg [Rat]. DERMAL (LD50): Acute: 2740 mg/kg [Rabbit].

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PHOSPHORIC ACID Update Feb 10, 2003


Section 3: Physical Data Physical State and Liquid. (Syrupy liquid.) Appearance

Odor Odourless

pH (1% Soln/Water) 0 to 1 [Acidic.] Taste Not available. Odor Threshold Not available. Color Colourless Volatility Not available Melting/Freezing Point -20°C (-4° F) Boiling/Condensation Point 135° C (275° F) Specific Gravity 1.574 @ 20° C (Water = 1) Vapor Density Not available. Vapor Pressure 5.76 mm of Hg (@ 20° C) LogKOW Not available. Ionicity (Surface Active Agent) Not available. Critical Temperature Not available. Instability Temperature Not available. Conditions of Instability No additional remark. Dispersion Properties See solubility in water. Solubility Soluble in cold water.

Section 4: Fire and Explosion Data The Product is: Non-flammable Auto-ignition Temperature Not applicable. Fire Degradation Products Phosphorous oxides may be released. This may form an explosive mixture with air

when in contact with certain metals. Flash Points Not applicable.

Flammable Limits Not applicable.

Fire Extinguishing Procedures Wear NIOSH approved self-contained breathing apparatus (SCBA) when either in confined areas or exposed to combustion products. Use water spray to cool fire exposed containers. Water spray may also be used to control vapours.

Flammability Not applicable.

Risks of Explosion Risks of explosion of the product in presence of mechanical impact: Not available. Risks of explosion of the product in presence of static discharge: Not available. No specific information is available in our database regarding the product’s risks of

explosion in the presence of various materials.

Section 5: Reactivity Data Stability The product is stable. Avoid contact with bases, fluorides, silicides, carbides, strong

oxidizing and reducing agents. Product also attacks metals. Hazardous Decomposition Not available. Products Degradability Not available. Products of Degradation Possible hazardous short term degradation products are not likely. However, long

term degradation products may arise.

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Corrosivity No specific information is available in our database regarding the corrosivity of this product in presence of various materials.

Reactivity Bases. Sulphides, phosphides, cyanides, acetylides, fluorides, silicides and carbides.

Section 6: Toxicological Properties

Routes of Entry Absorbed through skin. Eye contact. Inhalation. Ingestion.

TLV TWA: 1 STEL: 3 Consult local authorities for acceptable exposure limits. Toxicity to Animals Acute oral toxicity (LD50): 1530 mg/kg [Rat]. Acute dermal toxicity (LD50): 2740 mg/kg [Rabbit] Acute Effects on Humans Corrosive to skin and eyes on contact. Liquid or spray mist may produce tissue

damage particularly on mucous membranes of eyes, mouth and respiratory tract. Skin contact may produce burns. Inhalation of the spray mist may produce severe irritation of respiratory tract, characterized by coughing, choking, or shortness of breath. Severe over-exposure can result in death.

Chronic Effects on Humans CARCINOGENIC EFFECTS: Not available. MUTAGENIC EFFECTS: Not available. TERATOGENIC EFFECTS: Not available. DEVELOPMENTAL TOXICITY: Not available. Repeated or prolonged contact with spray mist may produce chronic eye irritation and

severe skin irritation. Repeated or prolonged exposure to spray mist may produce respiratory tract irritation leading to frequent attacks of bronchial infection. Repeated exposure to a highly toxic material may produce general deterioration of health by an accumulation in one or many human organs. Dermatitis may occur from prolonged or repeated skin contact.

Section 7: Preventive Measures Waste Information Neutralized product may be deposited in a chemical dump. Waste Stream Not available. Storage Corrosive materials should be stored in a separate safety storage cabinet or room.

Keep container tightly closed in a cool, well-ventilated place. Protect from freezing. Keep away from incompatibles. To prevent crystallization of concentrated phosphoric acid solutions minimum storage temperatures are 21° C for 85% solution, 4° C for 80% solution and -18° for 75% solution.

Precautions Keep locked up. Keep container dry. DO NOT ingest. Do not breathe gas, fumes, vapor or spray. Never add water to this product. Wear suitable protective clothing. If ingested, seek medical advice immediately and show the container or the label.

Small Spill and Leak Absorb with an inert material and place in an appropriate waste disposal container. Small spills may be neutralized with sodium bicarbonate or a mixture of soda ash/slaked lime.

Large Spill and Leak Corrosive liquid. Stop leak if without risk. Absorb with DRY earth, sand or other non-combustible material. DO NOT get water inside container. DO NOT touch spilled material. Use water spray curtain to divert vapor drift. Prevent entry into sewers, basements or confined areas; dike if needed. Call for assistance on disposal. Larger spills shall be recovered and placed in a suitable container. Once recovered, the solution may then be cautiously neutralized with lime (CaO) or soda ash (Na2CO3).

Protective Clothing Splash goggles. Full suit. Boots. Gloves. Suggested protective clothing might not be sufficient; consult a specialist BEFORE handling this product. Vapor respirator or a

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self contained breathing apparatus.

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Section 8: Classification

TDG Road / Rail Phosphoric acid, liquid 75%, CLASS 8, UN 1805, PG III WHMIS WHMIS CLASS E: Corrosive liquid. Federal and Provincial CEPA DSL: Prayphos P5-75 Regulations

Section 9: Protective Measures

Protective Clothing Face shield. Full suit. Gloves (impervious). Boots. Vapor respirator or a self contained breathing apparatus.

Engineering Controls Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapors below their respective threshold limit value. Ensure that eyewash stations and safety showers are proximal to the work-station location.

Section 10: Other Information

References Manufacturer’s Material Safety Data Sheet

Acidity – Strong acid, K1: 7.1 x 10(-3), K2: 8.0 x 10(-8), K3: 4.8 x 10(-13).

EMERGENCY – 24 HRS/DAY – 7 DAYS/WEEK EVERYWHERE IN CANADA / BENSON CHEMICALS LTD. - CALL 1-519-821-0215 To the best of our knowledge, the information contained herein is accurate. However, neither the above named supplier nor any of its subsidiaries assumes any liability whatsoever for the accuracy or completeness of the information contained herein. Final determination of suitability of any material is the sole responsibility of the user. All materials may present unknown hazards and should be used with caution. Although certain hazards are described herein, we cannot guarantee that these are the only hazards that exist.

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LEAST SLIGHT MODERATE HIGH EXTREMEHAZARD RATING

0 1 2 3 4

WHMIS

416-984-3000

NFPA

%

Specific Gravity (H2O = 1)

Percent Volatileby Volume (%)

The information contained herein is furnished without warranty of any kind. Employers should use this information only as a supplement to other informationgathered by them and must make independent determinations of suitability and completeness of information from all sources to assure proper use of these materialsand the safety and health of employees. For laboratory use only. Not for drug, food or household use. Keep out of reach of children. Printed on recycled paper.

TLV Units

Evaporation Rate ( Ether =1)

Discharge, treatment, or disposal may be subject to local laws.Consult your local or regional authorities.

Date Approved

SECTION V REACTIVITY DATA

SECTION VI TOXICOLOGICAL PROPERTIES

SECTION VII PREVENTIVE MEASURES

SECTION VIII FIRST AID MEASURES

Rev. No.

SECTION IX PREPARATION OF THE MSDS

Specific first aidmeasures

Precautions

Waste Disposal

Storage

Spill or leak

Protective Clothing

Acute effects onhumans

Chronic effects onhumans

Toxicity for animals

TLV

Route of Entry

Incompatible withOther products

HazardousDecompositionProducts

Reactive underwhat conditions

ChemicalStability

If no, under what conditions?

Flammable Limits in Air % by Volume

Lower Upper

SECTION II DANGEROUS INGREDIENTS

SECTION I NAME 24 HOUR EMERGENCY ASSISTANCE

Product

ChemicalSynonyms

Formula

CAS No.

Name

SECTION III PHYSICAL DATAMelting Point (°C)

Boiling Point (°C)

Vapor Pressure (mm Hg)

Vapor Density (Air=1)

Solubility in Water

Appearance & Odor

FirefightingProcedures

Flash point

TDG

Flammability andExplosion Hazards

Michael Raszeja

Health

Flammability

Reactivity

Yes

No

Yes

No

SECTION IV FIRE AND EXPLOSION HAZARD DATA

MATERIAL SAFETY DATA SHEETX

X9473306 9473307December 2, 2002

0

1

0

0 01

Use dry chemical, CO2, alcohol foam, or water spray. Use water withcaution. Material can float on water and spread. In fire conditions, fire-fighters should wear an appropriate mask or a self-containing breathingapparatus.

Ingestion: Call physician or Poison Control Center immediately. Induce vomiting only ifadvised by the appropriate medical personnel. Eye contact: Check for and remove anycontact lenses. Immediately flush eyes with running water for at least 15 minutes, keepingeyelids open. Seek medical attention. Skin contact: Gently and thoroughly wash thecontaminated skin with running water and non-abrasive soap. Inhalation: Move victim tofresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.Allow victim to rest in a well ventilated area. Seek immediate medical attention.

2 December 2, 2002

VV0020

MSDS No.Effective Date:

5100 W. Henrietta Rd.West Henrietta, NY 14586TEL: (866) 260-0501

Combustible at elevated temperatures. Can react vigorously with oxidizingmaterials. Fire or excessive heat may produce hazardous decompositionproducts to be produced as dust or fume.

Ignition temperature: 445°C

Vegetable Oil

Soybean Oil

Natural Product

8001-22-7

Vegetable oil 100% N/A

CAUTION!

22 - 31°C 0.924 - 0.929 @ 60°C

N/A Negligible @ 25°C

N/A > 1

N/A

Insoluble.

Clear, light yellow, oily liquid; faint odor.

255°C (CC) Unknown

Not controlled under TDG.

Carbon oxides.

Oxidizing materials.

Slightly reactive with oxidizing agents. Avoid excessive temperature, heat, spark and flames.

No specific information is available.

There is no known effects from chronic exposure to this product. Target organs: Noneknown.

N/A

N/A

Inhalation.

Splash goggles, lab coat, vapor respirator, gloves.

Absorb with an inert DRY material and place in an appropriate waste disposal container.Wash spill area well with soap and water.

Avoid contact with skin and eyes. Do not inhale vapor or spray. DO NOT ingest. Ifingested, seek medical advice immediately.

Keep container dry. Keep in a cool place. Keep container tightly closed. Keep away fromoxidizing agents and flammable materials. Solidifying point -15 to -8°C.

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Minime Légere Modéré Serieux Extréme

Niveau de risque

0 1 2 3 4

WHMIS

416-984-3000

NFPA

%

Gravité spécifique (Eau = 1)

Volatilité % par volume

oui

TWA

Taux d'évaporation ( Éther =1)

non

Consulter vos autorités locales ou régionales.

Date Vérifié par

SECTION V Données sur la Réactivité

SECTION VI Propriétés Toxicologiques

SECTION VII Mesures Préventives

SECTION VIII Premiers Soins

# Rev.

SECTION IX Renseignements sur la Préparation de la FS

Premier SoinsParticuliers àAdministrer

Précautions

Éliminationdes résidus

Entreposage

Déversementou fuite

Vêtements deprotection

Effets aiguésur les humains

Effets chroniquessur les humains

Toxicité pour lesanimaux

LMP

Voies d'absorption

Incompatibilité avecd'autres produits

Produits dedecompositiondangereux

Conditions deRéactivité

ChimiqueStabilité

Si non, dans quelles condition?

Limites d'inflmmabilité% par volume

Seuil minimal Seuil maximal

SECTION II Ingrédients Dangereux

SECTION I Identification Telephone D'urgence

Produit

Synonymes

Formule

# CAS

Nom

Point de fusion (°C)

Point d'ebullition (°C)

Tension de vapeur (mm Hg)

Densité de la vapeur (Air=1)

Solubilité

Odeur et apparence

Moyensd'extinction

Point d'éclair

TMD

Inflammabilité etrisques d'explosion

Michael Raszeja

Santé

Flammabilité

Reactivité

Au meilleur de nos connaissances, l'information contenue dans ce document est exacte. Toutefois, ni le fournisseur ci-haut mentionné ni aucune de sessuccursales ne peut assumer quelque responsabilité que ce soit en ce qui à trait à l'exactitude ou à l'état complet de l'information contenue dans ce document.La détermination finale de la convenance de tout matérial ou produit est la responsabilité exclusive de l'utilisateur. Tous les matériaux ou produits peuventprésenter certains risques et devraient être utilisés avec prudence. Bien que certains risques soient décrits dans ce document, nous ne pouvons garantir quece sont les seuls risques qui existent.

non

oui

SECTION III Caractéristiques Physiques

SECTION IV Risques D'incendie ou D'explosion

Fiche Signalétique

Ingestion: Consulter une médecin ou le centre de poison commande immédiatement.Induisez le vomissement seulement s’informé par le personnel médical approprié. Contactoculaire: Vérifer si la victime porte des verres de contact et dans ce cas lui les enlever.Rincer les yeux immèdiatement à l'eau courante pendant au moins 15 minutes en gardantles paupiéres ouvertes. Obtenir de l'aide médicale. Contact cutane: Laver doucement etentièrement la peau contaminée à l'eau courante avec un savon doux et non-abrasif.Inhalation: Sortir la victime à l'air frais. Si elle ne respire plus il faut lui donner de larespiration artificielle. Si la respiration est difficile, donnez l'oxygène. Assurez-vous que lavictime se repose dans un endroit bien aéré. Obtenir immédiatement de l'aide médicale.

Utiliser des poudres chimiques sèches, du CO2, une mousse d'alcoolou de l'eau pulvérisée. Employez l’eau avec prudence. La matérielpeut flotter sur l’eau et écarter. En cas de feu, sapeur-pompeir devraporter en masque adéquate ou un respirateur autonome.

X

X

0

1

0

0 01

2 2 decembre, 2002

VV0020

# MSDSValidé par:

5100 W. Henrietta Rd.West Henrietta, NY 14586TEL: (866) 260-0501

9473306 94733072 decembre, 2002

Combustibe à la températures elevees. Peut vigoureusement réagiravec le matières d'oxydants. Le feu ou la chaleur excessive peutproduire les produits dangereux de décomposition à produire commepoussière ou vapeur.

Témperature d'ignition: 445°C

Substance non réglementée par le TMD (Canada).

255°C (CC) Inconnu.

Huile végétale

Huile de soja

Produit au naturel

8001-22-7

Huile végétale 100% Sans objet.

ATTENTION!

22 - 31°C 0,924 - 0,929 @ 60°C

Sans objet. Négligeable @ 25°C

Sans objet. > 1

Sans objet.

Insoluble.

Liquide huilex, jaune pâle, incolore; léger odeur.

Oxydes de carbones.

Matières oxydantes.

Légèrement réactif à réactif avec les agents comburants. Évitez la température excessive,la chaleur, étincelle et flamme.

Évitez la température excessive, la chaleur, étincelle et flamme.

Il n'y a aucun effet connu dû à une exposition chronique à ce produit. On ne connaît aucunorgane de cible.

Sans objet.

Sans objet.

Inhalation.

Lunettes de sécurité, blouse de laboratoire, respirateur anti-poussières, gants.

Utiliser les instruments nécessaires pour mettre le solide répandu dans un contenant derécupération approprié. Bien laver la surface où le solide était répandu avec du savon et del'eau.

Éviter tout contact avec la peau et les yeux. NE PAS inhaler les poussières. NE PASingérer. Si ingéré, consulter immédiatement un médecin. Conserver à l'écart de oxydantes.

Conserver le récipient à l'abri de l'humidité. Conserver dans un endroit frais. Conserver lerécipient bien fermé. Conserver a l’ecart les agents comburants et matières inflammable.Point de solidification -15/-8°C.

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Bio-Heating Oil The BioDiesel distillation by-product is designated as Bio-Heating Oil. It consists of:

40 - 80 % wt Methyl ester 1- 30 % wt Dimere Methyl ester (depending on polymers

from UCO) 1- 25 % wt Mono,-Di- und Triglycerides

1 - 5 % wt Fatty acids 1 - 5 % wt Organic components from feedstock (colour,

non-saponifiable) 0.1– 0.4 % wt ash

Max. 2000 ppm sulphur (depending on feedstock) -Traces of other impurities from feedstock like polyethylene, bone meal and water. Physical properties: • General information

Physical condition: liquid at temperatures above 60 to 80 cent. Colour: dark brown or black Odour: characteristic, depends on feedstock

• Flashpoint: about 170 cent. • Inflammation temperature: about 400 cent. • Explosion hazard: at ambient temperature the product does not

represent an explosion hazard • Density at 40 cent: approx. 914 kg/m³ to 935 kg/m³ • Density at 80 cent: approx. 885 kg/m³ to 907 kg/m³ • Viscosity at 40 cent: 50mm²/s to 500 mm²/s • Viscosity at 80 cent: 13mm²/s to 50 mm²/s • Flammability: At ambient temperature auto-ignition of the

product is not possible • Electrical conductivity: 0.2 µS/cm • Dielectricity constant: 3.9

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SIGMA-ALDRICH Material Safety Data Sheet Date Printed: 08/FEB/2006 Date Updated: 15/MAR/2004 Version 1.1 According to 91/155/EEC 1 - Product and Company Information Product Name GLYCERINE CARBONATE - 250mg Product Number S362158 Company Sigma-Aldrich Ireland Ltd. Airton Road, Tallaght Dublin 24 Ireland Technical Phone # 353-1404-1900 Fax 353-1404-1910 2 - Composition/Information on Ingredients Product Name CAS # EC no Annex I Index Number 4-(HYDROXYMETHYL)-1,3-DIOXOLAN-2-O 931-40-8 213-235-0 None NE Formula C4H6O4 Molecular Weight 118.09 AMU 3 - Hazards Identification SPECIAL INDICATION OF HAZARDS TO HUMANS AND THE ENVIRONMENT Not hazardous according to Directive 67/548/EEC. 4 - First Aid Measures AFTER INHALATION If inhaled, remove to fresh air. If breathing becomes difficult, call a physician. AFTER SKIN CONTACT In case of contact, immediately wash skin with soap and copious amounts of water. AFTER EYE CONTACT In case of contact with eyes, flush with copious amounts of water for at least 15 minutes. Assure adequate flushing by separating the eyelids with fingers. Call a physician. AFTER INGESTION If swallowed, wash out mouth with water provided person is conscious. Call a physician. 5 - Fire Fighting Measures EXTINGUISHING MEDIA Suitable: Water spray. Carbon dioxide, dry chemical powder, or appropriate foam.

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SPECIAL RISKS Specific Hazard(s): Emits toxic fumes under fire conditions. SPECIAL PROTECTIVE EQUIPMENT FOR FIREFIGHTERS Wear self-contained breathing apparatus and protective clothing to prevent contact with skin and eyes. 6 - Accidental Release Measures METHODS FOR CLEANING UP Absorb on sand or vermiculite and place in closed containers for disposal. Ventilate area and wash spill site after material pickup is complete. 7 - Handling and Storage HANDLING Directions for Safe Handling: Avoid inhalation. Avoid contact with eyes, skin, and clothing. Avoid prolonged or repeated exposure. STORAGE Conditions of Storage: Keep tightly closed. 8 - Exposure Controls / Personal Protection ENGINEERING CONTROLS Safety shower and eye bath. Mechanical exhaust required. GENERAL HYGIENE MEASURES Wash thoroughly after handling. PERSONAL PROTECTIVE EQUIPMENT Respiratory Protection: Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU). Respiratory protection is not required. Where protection is desired, use multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges. Hand Protection: Protective gloves. Eye Protection: Chemical safety goggles. 9 - Physical and Chemical Properties Appearance Physical State: Liquid Property Value At Temperature or Pressure pH N/A BP/BP Range 137.0 - 140.0 °C 0.5 mmHg MP/MP Range N/A Flash Point 110 °C Method: closed cup Flammability N/A Autoignition Temp N/A Oxidizing Properties N/A Explosive Properties N/A Explosion Limits N/A Vapor Pressure N/A SG/Density 1.4 g/cm3 Partition Coefficient N/A Viscosity N/A Vapor Density N/A ALDRICH - S362158 www.sigma-aldrich.com Page 2

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Saturated Vapor Conc. N/A Evaporation Rate N/A Bulk Density N/A Decomposition Temp. N/A Solvent Content N/A Water Content N/A Surface Tension N/A Conductivity N/A Miscellaneous Data N/A Solubility N/A 10 - Stability and Reactivity STABILITY Stable: Stable. Materials to Avoid: Strong oxidizing agents. HAZARDOUS DECOMPOSITION PRODUCTS Hazardous Decomposition Products: Carbon monoxide, Carbon dioxide. HAZARDOUS POLYMERIZATION Hazardous Polymerization: Will not occur 11 - Toxicological Information SIGNS AND SYMPTOMS OF EXPOSURE To the best of our knowledge, the chemical, physical, and toxicological properties have not been thoroughly investigated. ROUTE OF EXPOSURE Skin Contact: May cause skin irritation. Skin Absorption: May be harmful if absorbed through the skin. Eye Contact: May cause eye irritation. Inhalation: Material may be irritating to mucous membranes and upper respiratory tract. May be harmful if inhaled. Ingestion: May be harmful if swallowed. 12 - Ecological Information No data available. 13 - Disposal Considerations SUBSTANCE DISPOSAL Contact a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. Observe all federal, state, and local environmental regulations. 14 - Transport Information RID/ADR Non-hazardous for road transport. IMDG Non-hazardous for sea transport. IATA Non-hazardous for air transport. 15 - Regulatory Information ALDRICH - S362158 www.sigma-aldrich.com Page 3

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Not hazardous according to Directive 67/548/EEC. COUNTRY SPECIFIC INFORMATION Germany WGK: 1 ID-Number: 2998 Classification according to appendix 3. 16 - Other Information WARRANTY The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. Sigma-Aldrich Inc., shall not be held liable for any damage resulting from handling or from contact with the above product. See reverse side of invoice or packing slip for additional terms and conditions of sale. Copyright 2006 Sigma-Aldrich Co. License granted to make unlimited paper copies for internal use only. DISCLAIMER For R&D use only. Not for drug, household or other uses. ALDRICH - S362158 www.sigma-aldrich.com Page 4

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SAFETY DATA SHEETBased on Directive 2001/58/EC et seq. of the Commission of the European Communities

Printing date : 07-2002 1/7Compiled by : Brandweerinformatiecentrum voor Gevaarlijke Stoffen vzw (BIG)

Technische Schoolstraat 43 A, B-2440 Geel( +32 14 58 45 47 http://www.big.be E-mail: [email protected]

MSDS established : Revision date : 07-03-2002Reference number : BIG\37754GB Revision number : 001Reason for revision : Directive 2001/58/EC

POTASSIUM SULPHATE FERTILISER

1.1 Identification of the substance or preparation:

Synonyms: noneCAS No. : 7778-80-5 BCR number : BCR-114EC index No. : N.A. NFPA code : 1-0-0(*)EINECS No. : 231-915-5 Molecular weight : 174.26RTECS No. : TT5900000 Formula : K2SO4

1.2 Use of the substance or the preparation:Certified reference material for laboratory use only

1.3 Company/undertaking identification:Institute for Reference Materials and MeasurementsRetiesewegB-2440 GeelTel. : +32 14 57 12 11Fax : +32 14 58 42 73

1.4 Telephone number for emergency:+32 70 245 245Antigifcentrump/a Militair Hospitaal Koningin Astrid, Bruynstraat, B-1120 Brussel

Hazardous ingredients CAS No.EINECS No.

Conc.in %

Hazardsymbol

Risks(R-phrases)

potassium sulphate 7778-80-5

231-915-5

100 - -

- No hazard classification

4.1 Eye contact:- Consult a doctor/medical service if irritation persists- Rinse immediately with water

4.2 Skin contact:- Consult a doctor/medical service if irritation persists- Wash with water and soap

4.3 After inhalation:- Consult a doctor/medical service if breathing problems develop- Remove the victim into fresh air- Unconscious: maintain adequate airway and respiration

4.4 After ingestion:- Consult a doctor/medical service if you feel unwell- Immediately give lots of water to drink-- Never give water to an unconscious person- Victim is fully conscious: immediately induce vomiting

2. Composition/information on ingredients

1. Identification of the substance/preparation and of the company/undertaking

3. Hazards identification

4. First aid measures

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Printing date : 07-2002 2/7


5.1 Suitable extinguishing media:- For surrounding fires:- all extinguishing media allowed

5.2 Unsuitable extinguishing media:- No data available

5.3 Special exposure hazards:- No data available

5.4 Instructions:- Dilute toxic gases with water spray

5.5 Special protective equipment for firefighters:- Heat/fire exposure: compressed air/oxygen apparatus- Heat/fire exposure: gas-tight suit

6.1 Personal protection/precautions: see heading 8.1/8.3/10.3

6.2 Environmental precautions:- Not applicable

6.3 Methods for cleaning up:- Stop dust cloud by covering with sand/earth- Scoop solid spill into closing containers- Wash down leftovers with plenty of water

7.1 Handling:- Observe normal hygiene standards- Avoid raising dust

7.2 Storage:- Keep container tightly closed- Store at room temperature- Store in a dry area- Meet the legal requirements- Keep away from: heat sources

Storage temperature : N.D. °CQuantity limits : N.D. kgStorage life : N.D.Materials for packaging :

- suitable :wood, glass

- to avoid :aluminium

7.3 Specific uses: N.D.

5. Fire-fighting measures

6. Accidental release measures

7. Handling and storage

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8.1 Exposure limit values:

TLV-TWA : mg/m3 ppmTLV-STEL : mg/m3 ppmTLV-Ceiling : mg/m3 ppm

OES-LTEL : 4 R/10 I mg/m3 - ppmOES-STEL : - mg/m3 - ppm

MAK : 1.5 A/4 E mg/m3 ppmTRK : mg/m3 ppm

MAC-TGG 8h : 5 R/10 I mg/m3

MAC-TGG 15 min. : mg/m3

MAC-Ceiling : mg/m3

VME-8h : 5 A/10 T mg/m3 - ppmVLE-15 min. : - mg/m3 - ppm

GWBB-8h : 3 R/10 I mg/m3 - ppmGWK-15 min. : - mg/m3 - ppmMomentary value : mg/m3 ppm

EC : mg/m3 ppmEC-STEL : mg/m3 ppm

Sampling methods:

- Potassium and compounds OSHA ID 121- Sulfites, & Sulfates NIOSH 6004

8.2 Exposure controls:

8.2.1 Occupational exposure controls:- Measure the concentration in the air regularly- Work under local exhaust/ventilation

8.2.2 Environmental exposure controls: see heading 13

8.3 Personal protection:

8.3.1 respiratory protection:- Dust production: dust mask with filter type P2

8.3.2 hand protection:- Gloves

Suitable materials: Rubber

- Breakthrough time: N.D.

8.3.3 eye protection:- Safety glasses- In case of dust production: protective goggles

8.3.4 skin protection:- Protective clothing

Suitable materials: Rubber

8. Exposure controls/Personal protection

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9.1 General information:

Appearance (at 20°C) : Crystalline solid / PowderOdour : OdourlessColour : Colourless to white

9.2 Important health, safety and environmental information:

pH value : 5.5/8 (5 %)Boiling point/boiling range : 1689 °CFlashpoint : N.A. °CExplosion limits : N.A. vol% ( °C)Vapour pressure (at 20°C) : N.D. hPaVapour pressure (at 50°C) : N.D. hPaRelative density (at 20°C) : 2.7Water solubility : 11 g/100 mlSoluble in : N.D.Relative vapour density : N.D.Viscosity : N.D. Pa.sPartition coëfficient n-octanol/water : N.D.Evaporation rate

ratio butyl acetate : N.D.ratio ether : N.D.

9.3 Other information:

Melting point/melting range : 1067 °CAuto-ignition point : N.A. °CSaturation concentration : N.D. g/m3

10.1 Conditions to avoid/reactivity:- Stable under normal conditions

10.2 Materials to avoid:- Keep away from: heat sources, aluminium

10.3 Hazardous decomposition products:- Decomposes on exposure to temperature rise: release of toxic and corrosive

gases/vapours (sulphur oxides)- In molten state: reacts violently with (some) metals

11.1 Acute toxicity:

LD50 oral rat : 6600 mg/kgLD50 dermal rat : N.D. mg/kgLD50 dermal rabbit : N.D. mg/kgLC50 inhalation rat : N.D. mg/l/4 hLC50 inhalation rat : N.D. ppm/4 h

9. Physical and chemical properties

10. Stability and reactivity

11. Toxicological information

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11.2 Chronic toxicity:

EC carc. cat. : not listedEC muta. cat. : not listedEC repr. cat. : not listed

Carcinogenicity (TLV) : not listedCarcinogenicity (MAC) : not listedCarcinogenicity (VME) : not listedCarcinogenicity (GWBB) : not listed

Carcinogenicity (MAK) : not listedMutagenicity (MAK) : not listedTeratogenicity (MAK) : not listed

IARC classification : not listed

11.3 Routes of exposure: ingestion, inhalation, eyes and skin

11.4 Acute effects/symptoms:

- AFTER INHALATION OF DUST:- Coughing

- AFTER ABSORPTION OF HIGH QUANTITIES:- Gastrointestinal complaints- Nausea- Diarrhoea- Irritation of the gastric/intestinal mucosa- Decreased renal function- Disturbances of heart rate

- AFTER SKIN CONTACT- Slight irritation

- AFTER EYE CONTACT- ON CONTINUOUS EXPOSURE/CONTACT:- Redness of the eye tissue- Irritation of the eye tissue

11.5 Chronic effects:

- Not listed in carcinogenicity class (IARC,EC,TLV,MAK)- Not listed in mutagenicity class (EC,MAK)- Not classified as toxic to reproduction (EC)

12.1 Ecotoxicity:

- LC50 (96 h) : 653/796 mg/l (LEPOMIS MACROCHIRUS)- EC50 (48 h) : 890 mg/l (DAPHNIA MAGNA)- EC50 (72 h) : 2900 mg/l (SCENEDESMUS SUBSPICATUS)

12.2 Mobility:

- Volatile organic compounds (VOC): N.A.%

- Soluble in waterFor other physicochemical properties see heading 9.

12.3 Persistence and degradability:

- biodegradation BOD5 : N.D.

- water : N.D.

- soil : N.D.

12.4 Bioaccumulative potential:- log Pow : N.D.- BCF : N.D.- Not bioaccumulative

12. Ecological information

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12.5 Other adverse effects:

- WGK : 1 (Classification in compliance with Verwaltungsvorschriftwassergefährdender Stoffe (VwVwS) of 17 May 1999)

- Effect on the ozone layer : Not dangerous for the ozone layer(Council Regulation (EC) No3093/94, O.J. L333 of 22/12/94)

- Greenhouse effect : no data available- Effect on waste water purification : no data available

13.1 Provisions relating to waste:- Waste material code (75/442/EEC, Council Decision 2001/118/EC, O.J. L47 of

16/2/2001): 06 03 14 (solid salts and solutions other than those mentionedin 06 03 11 and 06 03 13)

- Waste material code (Flanders): 213- Waste code (Germany): 51540

13.2 Disposal methods:- Precipitate/make insoluble- Remove to an authorized dump (Class I)

13.3 Packaging/Container:- Waste material code packaging (75/442/EEC, Council Decision 2001/118/EC,

O.J. L47 of 16/2/2001): 15 01 03 (wooden packaging)- Waste material code packaging (75/442/EEC, Council Decision- 2001/118/EC, O.J. L47 of 16/2/2001): 15 01 07 (glass packaging)

14.1 Classification of the substance in compliance with UN RecommendationsUN number :CLASS : -SUB RISKS :PACKING :PROPER SHIPPING NAME :

14.2 ADR (transport by road)CLASS : NOT SUBJECTPACKING :DANGER LABEL TANKS :DANGER LABEL PACKAGES :

14.3 RID (transport by rail)CLASS : NOT SUBJECTPACKING :DANGER LABEL TANKS :DANGER LABEL PACKAGES :

14.4 ADNR (transport by inland waterways)CLASS : NOT SUBJECTPACKING :DANGER LABEL TANKS :DANGER LABEL PACKAGES :

14.5 IMDG (maritime transport)CLASS : NOT SUBJECTSUB RISKS :PACKING :MFAG :EMS :MARINE POLLUTANT :

14.6 ICAO (air transport)CLASS : NOT SUBJECTSUB RISKS :PACKING :PACKING INSTRUCTIONS PASSENGER AIRCRAFT :PACKING INSTRUCTIONS CARGO AIRCRAFT :

14.7 Special precautions in connection with : not restricted for any mode of

13. Disposal considerations

14. Transport information

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POTASSIUM SULPHATE FERTILISERtransport international transport

Classification according to directives 67/548/EEC et sequens

NOT APPLICABLE

The information provided on this MSDS is correct to the best of our knowledge, informationand belief at the date of its publication. The information given is designed only as aguidance for safe handling, use, processing, storage, transportation, disposal and releaseand is not to be considered as a warranty or quality specification. The information relatesonly to the specific material designated and may not be valid for such material used incombination with any other material or in any process, unless specified in the text.

N.A. = NOT APPLICABLEN.D. = NOT DETERMINED* = INTERNAL CLASSIFICATION

Exposure limits:TLV : Threshold Limit Value - ACGIH USA 2000OES : Occupational Exposure Standards - United Kingdom 1999MEL : Maximum Exposure Limits - United Kingdom 1999MAK : Maximale Arbeitsplatzkonzentrationen - Germany 2001TRK : Technische Richtkonzentrationen - Germany 2001MAC : Maximale aanvaarde concentratie - The Netherlands 2002VME : Valeurs limites de Moyenne d’Exposition - France 1999VLE : Valeurs limites d’Exposition à court terme - France 1999GWBB : Grenswaarde beroepsmatige blootstelling - Belgium 1998GWK : Grenswaarde kortstondige blootstelling - Belgium 1998EC : Indicative occupational exposure limit values - directive 2000/39/EC

I : Inhalable fraction = T: Total dust = E: Einatembarer AerosolanteilR : Respirable fraction = A: Alveolengängiger Aerosolanteil/Alveolar dustC : Ceiling limit

15. Regulatory information

16. Other information

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Green Biofuels Ireland Ltd. July 2007 Application for an IPPC Licence Attachment H.2 –Wastes Handling

Malone O’Regan


Attachment H.2

Wastes Handling

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Table of Contents

Section Page No 1.0 Introduction ……………………………………………………………………. 2 2.0 Waste Arisings & Storage …………………………………………………... 2 2.1 Waste Arisings………………………………………………………………….. 2 2.2 Waste Storage….………………………………………………………………. 4 2.3 Wastewater Storage – Temporary Arrangements………………………….. 4 3.0 Management of Waste Materials …………………………………………… 5 3.1 Overview ………………………………………………………………………… 5 3.2 General Provisions……………………………………………………………… 5 3.3 Duty of Care…………………………………………………………………….. 6 3.4 Hazardous Waste Management………………………………………………. 6 3.5 Packaging Waste………………………………………………………………. 7 3.6 Empty Drums…………………………………………………………………… 7 3.7 Waste Disposal Arrangements ………………………………………………. 7 4.0 Waste Handling Summary …………………………………………………… 8 Appendix

H.2.1 Plan of Waste Storage Areas

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1.0 INTRODUCTION This section of the IPPC Licence application details information on waste materials generated at the Green Biofuels Ireland Limited (GBI) site, including name, description and nature as well as the source(s) of waste and handling arrangements. The process at the (GBI) facility is designed to minimise any waste generated. A small amount of waste will be produced from offices and general day to day activities at the site. This will mainly consist of packaging and canteen waste. However raw materials will generally be delivered by tanker, thus minimising packaging waste. There will be no reject finished product as material will be returned to the distillation process for further distillation if necessary. 2.0 WASTE ARISINGS & STORAGE 2.1 Waste Arisings The plant and process design to be implemented by GBI has been developed to ensure waste generation is minimised at source, as far as possible. The focus of the waste management aspects of the Environmental Management System (EMS) to be implemented will be to ensure that those wastes arising which cannot be reduced or eliminated through changes to plant design and operation will be dealt with in an appropriate manner. GBI activities associated with the installation will generate both solid and liquid wastes. The wastes likely to be generated, the activities generating them and the fate of each waste stream are summarised in Table 1 below, as well as the waste code according to European Waste Catalogue 94/3/EC. Each waste is further categorised into either Hazardous or Non-Hazardous, as far as practicable, as defined in the Waste Management Act, 1996 to 2003. As the facility is not yet operational, there is no empirical data on waste quantities. However, some indication can be gained from the experience of the plant suppliers, BioDiesel International (BDI), at other BioDiesel plants they have constructed. These are also indicated below where possible.

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Table 1 GBI Waste Streams Waste

Description Est.

Annual Amount

(T/Yr)

Hazardous (H) / Non-

Hazardous (N-H)

EWC Waste Code

Source Fate

Laboratory waste 0.1 H / N-H 06 01 99 Laboratory Off-site treatment and disposal

Waste mineral oils (machinery, lubricating, and gear oil)

<0.2

H

13 02 08

Maintenance & repair

Recovery*

Interceptor cleaning wastes

N/A H 13 05 03 Interceptor Off-site treatment or disposal

Iron & steel 0.1 N-H 16 01 17 16 01 18


Recovery / recycle*

Empty Drums (may contain residues) organic / inorganic fluid

<0.5

H **

13 02 06 13 02 07 15 01 02 16 01 18 16 01 99

Maintenance chemical storage

Off-site treatment or disposal

KOH Empty Big Bags

1.0 – 2.0 H 16 08 07 Delivery of KOH*** Return to KOH provider

Impured operating material(Gloves, oil rags

N/A

H / N-H

15 02 02 15 02 03


Landfill*

Paper <0.50 N-H 15 01 01 Delivery of parts, office

Recovery / recycle*

Cardboard <0.50 N-H 15 01 01 Delivery of parts, office

Recovery / recycle*

Plastic <1.0 N-H 15 01 02 Delivery of parts, office

Recovery / recycle*

General office waste

1.0

N-H

15 01 /

20 01

Office, administration and laboratory areas

Recovery / recycle*

Fluorescent tubes

N/A H 20 01 21 Buildings Recovery*

Domestic waste 1.0 N-H 20 01 08 01

Canteen, social areas

Recovery / recycle*/landfill

Ion-exchange resin

N/A N-H 06 13 99 Ion-exchanger Recovery*

De-ionisation concentrate

N/A N-H 06 13 99 Water supply Recovery*

K2SO4 filters <0.50 N-H 16 11 K2SO4 filtering Landfill* ****Organic or inorganic liquid waste

1-40 H/ N-H 07 01 99 Maintenance, repair of process vessels, spillage

Sewer after testing or /off site treatment

*details will be provided once waste management contracts are in place; waste segregation will take place where possible; **Drums should be checked for hazardous residues prior to waste disposal ***KOH (Potassium Hydroxide) big bags are inside contaminated with remaining KOH dust. After discharging the big bags they will be closed again, collected and returned to the KOH provider. Samples, which are taken for quality control and are not used anymore, are recycled in the process. **** This is a potential waste and may not arise.

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2.2 Waste Storage The GBI production process is designed ecologically. By-products are purified and surplus material streams are led in a closed circuit, e.g. the free fatty acids from the glycerine phase are esterified into methyl ester, the excess methanol is purified and reused in the process. Therefore the amount of waste is limited. All liquid wastes and potentially hazardous wastes will be stored either inside the main building, in dedicated containers, or in the tank farm. All waste stored will be clearly labelled and disposed of / recovered according to waste management procedures. A list of the potential waste arisings and proposed waste storage areas for the GBI facility is presented below:

o Waste KOH bags (within KOH room); o Waste metals and lubrication oil from maintenance (in workshop); o Laboratory waste (within lab); o Interceptor cleaning waste (suctioned directly out of interceptor); o Dirty rags and gloves (workshop); o Batteries and fluorescent tubes; (workshop); o Canteen waste (designated area); o Spent Deionisation concentrate (utilities building); o Spent K2SO4 filters (workshop); o General office waste (designated area); o Paper, cardboard, plastic which may arise (designated area); o Organic and inorganic fluid waste which can arise from maintenance and

repair of process (stored in 200 lt drums in the process area) Appendix H.2.1 contains a plan of waste storage areas for the above waste arisings. Waste streams will be stored in segregated bins or suitable containers such as individual chemistores. Bins / containers will be in good condition and free from corrosion or wear, and located on good quality surfaced and level ground if not within the process building. Access to waste storage bins will be controlled and they will be sign-posted to specify permitted and prohibited wastes. They will also be checked regularly to ensure that only permitted wastes are being deposited in them as agreed with the approved waste contractor. 2.3 Wastewater Storage –Temporary Arrangements

In the short term, wastewater will be stored in Tank No. 19 and regularly pumped to a tanker and disposed of at Wexford County Council’s Wastewater Treatment Plant for Wexford Town, together with sanitary waste which will be pumped from a holding tank into Tank No. 19. This is because the wastewater treatment works for New Ross town and Environs on an adjoining site at Marshmeadows will not be built before the BioDiesel plant is expected to come on-line. The waste from the proposed GBI facility will be tested regularly during the commissioning phase.

All connections between storage and transportation will be secured and procedures will be implemented to ensure that the operation is attended by trained personnel at all times.

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3.0 MANAGEMENT OF WASTE MATERIALS Most materials brought onto the GBI site are in bulk, thereby minimising the amount of packaging wastes. The closed nature of the production process and small numbers of personnel on site will help to keep waste emissions to a minimum. GBI will retain accurate records of the type and volume of general and special waste generated by the BioDiesel plant. All waste streams will be managed to ensure compliance with relevant environmental legislation and in such a way that no significant environmental impacts are associated with the wastes whilst on site. 3.1 Overview The main environmental aspects associated with on site waste management are the potential for wastes to spill or to be entrained in rainwater and hence contaminate the drainage system or to become a nuisance such as windblown litter impacting on neighbouring land. Emissions to air may also occur with dusty wastes or if a chemical reaction occurs by mixing acidic and other wastes. These potential releases will be avoided through effective management and storage of waste materials, and appropriate process design. In terms of off-site impact, there is the potential, if the wastes are mismanaged, for them to be disposed of to unlicensed facilities or fly-tipped. However, the waste management and tracking systems to be put in place by GBI will eliminate this possibility. There are not expected to be any significant differences in the types of wastes generated during the commissioning phase. Any sub-standard BioDiesel produced during trials will be recycled back into the process. The plant will utilise waste materials therefore the overall impact on the waste infrastructure in Ireland can only be viewed as positive. 3.2 General Provisions GBI will ensure that all wastes are stored in appropriate containers, clearly sign posted, and are placed in designated, properly contained areas and that all staff are aware of the correct storage arrangements. All staff will have a clear understanding of which wastes can and cannot be placed in certain areas or receptacles. Appendix H.2.1 shows a plan of the proposed waste storage area on the GBI site. GBI will:

o Implement a system for recording production and disposal of different waste types;

o Designate a responsible person(s) for the storage, handling, on-site treatment and disposal of all wastes generated on the site and provide training and instruction on the objectives and tasks of the role;

o Draw up a written procedure and programme of regular, documented inspection of waste storage areas to ensure that only appropriate wastes are being stored in the respective areas and that quantities of wastes stored are kept to a practical minimum; and

o Ensure that waste disposal cannot occur without it being co-ordinated by the facility’s designated waste manager.

All waste arisings at the site will be identified by provenance, quantity and type, and the amounts produced should be minimised to the extent that this is practicable in the context of the business.

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3.3 Duty of Care All waste materials produced at the site will be properly handled, stored and managed, so as to prevent their release to the environment, until such time as they are collected by registered or exempted waste carriers for treatment or disposal at properly licensed waste facilities. Responsibility for adequate waste management disposal, including documentation and disposal arrangements, rests with GBI and will not be deferred or delegated to waste contractors. GBI will, under its compliance with the duty of care requirements of the EPA Act 1992, and Protection of the Environment Act 2003, ensure the following is adhered to:

• All wastes, whether regular arisings or one-offs, will be identified and characterised for adequate disposal in line with waste transfer purposes;

• All wastes will be stored and handled so that they cannot ‘escape from the control’ of the company or other parties involved in the disposal chain (i.e. drums will be sealed, bins kept covered etc);

• The contractor used to dispose of the waste is a registered waste carrier, or is legally exempt. The contractor must produce evidence to this effect and GBI will contact the EPA to confirm that the details the contractor has provided are accurate and correct;

• Properly completed waste consignment notes will be produced and maintained;

• The disposal, treatment or transfer facility(s) used for its wastes will be checked to ensure that it is properly licensed or legally exempt to accept those wastes. Further confirmation of this will be checked with the EPA.

When selecting a new waste contractor, GBI will not rely on the price of the contractor’s bid alone, but will also examine and test the contractor’s understanding of and compliance with duty of care and other legislation. Duty of care training and instruction will be given to all new employees and existing employees that either generate or handle wastes. As part of the company’s EMS and environmental audit, GBI will:

• Assess the commitment of the company to good waste management practice; • Check that the information gained by the facility operators is sufficient to be

able to treat / dispose of the waste properly and without risk to health, safety and the environment;

• Ensure that any spills, leaks, air emissions, drainage of wastes or by-products are controlled, so that they are not having any adverse environmental impact; and

• Ensure that the site is managed in a way that complies with legislation governing its operation.

3.4 Hazardous Waste Management GBI recognise that problems and uncertainties may arise when attempting to define whether certain wastes are sufficiently hazardous to be classified as such. In these instances, the identification of these substances as hazardous wastes or otherwise will be agreed with the EPA. If in doubt the waste will be consigned as hazardous

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waste. All liquid wastes and potentially hazardous wastes will be stored either inside the main building, in dedicated containers, or in the tank farm. All hazardous waste will be stored to minimise the risk of escape and release into the environment or risk to the health of people on-site.

• All waste containers will be in good condition and not subject to corrosion or wear.

• Liquid waste containers will be secondarily contained in a bunded area, with the capability of holding 110% of a single container capacity.

• Waste containers will be labelled immediately to minimise the incidence of “unknowns”.

• Incompatible waste materials will be segregated. 3.5 Packaging Waste It is not anticipated that a significant quantity of packaging materials will be used and handled by the BioDiesel plant. Notwithstanding this, in the development and maintenance of waste contracts, GBI will preferentially contract with firms that offer recycling and recovery options for the waste streams in question. 3.6 Empty Drums Empty drums may arise from maintenance chemical storage. It will be assumed that empty drums will usually contain residues of material, unless the contents have evaporated. If drums contain residues, they will be referred to as “nominally empty” and the waste classification given will relate to the nature of the residues. For this waste, the following options for disposal will be considered:

• Return to the supplier, where the supplier will be requested to take back any empty drums.

• Drum reclamation company, where drums in good condition can be cleaned and ‘reclaimed’ by specialist companies.

• Scrap metal – drums in poor condition may only have value, in terms of recycling, as scrap metal. However, unless the scrap merchant has the facilities to properly handle residues (this will be checked) or the drums are uncontaminated, this route will be avoided.

• Waste disposal – if drums have significant residues of hazardous materials or residues of a particularly hazardous nature, a waste disposal contractor will be employed to safely dispose of them.

Nominally, empty drums will be either stored horizontally or vertically in a contained area, within the maintenance area in order to protect site drainage from any leaks. Drums will be lidded, capped or in a covered area to prevent water ingress. Drums will also be labelled to show that they are empty, however, information on possible residues will be included for proper handling by recycling and waste contractors. All wastes will be removed from site by local authority licensed waste collection agents, for disposal at permitted waste disposal facilities as discussed above. 3.7 Waste Disposal Arrangements In the case of waste generated at the GBI facility to be disposed of off-site, GBI will,

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with final approval from the EPA, agree a contract with suitable and licensed waste disposal contractors for both hazardous and non-hazardous waste types. A provisional guidance list of suitable waste undertakers for the GBI facility is outlined below:

o ENVA - comprehensive chemical and biological treatment and disposal options for hazardous / non-hazardous wastes generated by all industries. The recovery and disposal of a diverse range of waste.

o Indaver Ireland– Recovery and disposal of wastes; waste management facility.

o Cork Metals – Recovery and recycling of metals. o Domestic type waste – Greenstar –recycling and materials recovery; Wexford

County Council local authority.

The contracted waste disposal company(s) will be approved by the EPA in terms of its suitability and compliance with current legislative standards when dealing with the recovery of wastes arising from the GBI facility and potential disposal at suitably licensed landfills. 4.0 WASTE HANDLING SUMMARY The whole process at GBI is designed to minimise waste generation. However, the GBI installation at Marshmeadows, New Ross will generate small quantities of both liquid and solid wastes from the process and auxiliary activities. It is only possible to make estimates at the moment in terms of the level of generation of these wastes. It should be noted that waste handling will form an intrinsic part of the EMS and will be applied across the entire BioDiesel facility, in the form of a suitable waste management plan. Good industry practice (i.e. through the application of Best Available Technology (BAT)) will be adopted for waste handling. This will include clear sign posting and labelling of all waste receptacles, auditing of waste areas and waste contractors, segregation of incompatible wastes (either through statutory designation or chemical incompatibility) and prevention of the escape of wastes from receptacles and storage areas. As part of its drive for continual improvements in environmental performance GBI will keep accurate records of all waste arisings and agreed and approved waste disposal arrangements. This information will be provided annually to the Environmental Protection Agency in the facility’s annual environmental (AER) report.

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Appendix H.2.1

Plan of Waste Storage Areas

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Green Biofuels Ireland Ltd. Application for an IPPC Licence · Thirteen of the tanks will be placed...

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