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ECO-PROFILES

of the European plastics industry

PVC CONVERSION PROCESSES

Ian Boustead

A Report for the Technical and Environmental Centre

of the Association of Plastics Manufacturers in Europe (APME)

Brussels

October 2002

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Contents

INTRODUCTION ______________________________________________3

THE SYSTEMS EXAMINED_____________________________________3

OMISSIONS FROM THE SYSTEMS ______________________________4

CARBON DIOXIDE ____________________________________________6

PRODUCTION OF SUSPENSION PVC ____________________________6

DELIVERY OF POLYMER RESINS______________________________13

UPVC FILM PRODUCTION ____________________________________19

CALENDERED RIGID PVC SHEET _____________________________26

PVC INJECTION MOULDING __________________________________34

PVC PIPE EXTRUSION________________________________________42

POSTSCRIPT ________________________________________________49

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INTRODUCTION In 1996, the Technical and Environmental Centre of the Association of Plastics Manufacturers in Europe (APME) produced a report covering some of the procedures employed in the conversion of polymer resins into usable products.1 In 2002 the data on PVC resin production have been updated and so the present report gives revised data for the production of some PVC products.

THE SYSTEMS EXAMINED The operations comprising the conversion systems are as shown in Figure 1. The three main groups of operations covered in this report are the transport of the resin to the converter, the conversion process itself and the packaging of the finished component for onward despatch. Transport of the finished product to the user is not included. Data on the production of PVC resin is taken from the revised APME/ECVM report2 and is discussed further below. Data for the fuel producing industries have been derived principally from IEA/OECD statistics3 supplemented where necessary from national statistics. Data on the conversion processes relate to practices in 1993-1995 although it is thought that these will not have changed significantly in the intervening years.

1 I Boustead. Eco-profiles of the European plastics industry. Report 10: Polymer Conversion. APME, Brussels, May 1997. 2 I Boustead. Eco-profiles of the European plastics industry. Polyvinyl Chloride (PVC). APME/ECVM, Brussels, March 2002. 3 IEA/OECD Coal information 1996. ISBN 92-64-15588-0, Oil information 1996, ISBN 92-64-05533-9, Electricity information 1996, ISBN 92-64-15585-6, Natural Gas Information 1996, ISBN 92-64-15592-9. All published by OECD, Paris 1997. (Note that these are annual publications and the ISBN will change from year to year).

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Raw materialsfrom the earth

Production ofpolymer resin

Transport ofresin to converter

Conversion process

Packaging foronward despatch

Production ofpackaging materials

Fuel producing industries



Figure 1. Principal groups of operations included within the system boundary for the conversion processes. Note that the fuel producing industries will feed all of the operations but these links have been omitted from the diagram.

OMISSIONS FROM THE SYSTEMS In the calculations, no account has been taken of capital energy and emissions; that is, the burdens associated with the production of the plant and machinery used in the conversion process. In general, this omission is not thought to introduce any significant errors and is usually less than 1% of the total system energy.4 The reason for this is not difficult to visualise. Although the energy and associated burdens needed to construct machinery and buildings are high, the total throughput of components in their lifetimes is such that the proportion of these burdens attributable to each component is trivial. There is however one exception to this approach: road transport. The calculations make an allowance for the construction of the vehicle and for the replacement of components such as tyres and batteries that must be replaced during the lifetime of the vehicle as well as for the garage maintenance of the vehicle. 4 Boustead, I & Hancock, G F. Handbook of Industrial Energy Analysis. ISBN 0-85312-064-1. Ellis Horwood, Chichester/John Wiley, New York. 1979.

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The calculations also omit any burdens associated with the humans who operate the machines. Again this is not thought to introduce any significant error. For example, if a human is regarded as an industrial operation fuelled by the energy consumed as food, then the daily intake of energy as food is of the order of 40 kcal per day per kg of live bodyweight.5 For a human of mass 70 kg this corresponds to a daily energy intake of the order of 11.7 MJ. Of this about 80% is needed to keep the human functioning as a living organism. Hence the energy available for useful external work is of the order of 2.3 MJ per day. Contrast this with the energy associated with a simple conversion process. Suppose that the human supervises a machine capable of converting 100 tonne of polymer resin per day. The energy associated with the conversion of this resin might typically be of the order of 10 MJ/kg so that the energy of the conversion process is of the order of 106 MJ. In comparison the food energy of the human is negligible. It is frequently argued that humans travel to work by car and therefore the energy associated with this transport should be attributed to the products produced at work. Again it is possible to estimate the contribution that this operations makes to the production system. Suppose that the round trip distance to and from work is 40 km and that the car has a performance of 10 km per litre of fuel. The gross energy required to produce a litre of gasoline is of the order of 36 MJ and therefore the energy associated with the journey to and from work will be 144 MJ. Comparing this with the 106 MJ of energy that is 'handled' while at work shows that the transport would add only an additional 0.01%. Again this is thought to be an insignificant addition. The calculations take no account of any air emissions arising directly from the conversion process. While it is impossible to carry out any such process without generating some emissions, the quantities involved are thought to be very small and not significant compared with the burdens imported with the inputs to the system.6 The emissions that arise during the production of the fuels and ancillary materials imported into the system have however been taken into account.

5 Odum, E P. Fundamentals of ecology. ISBN 0-7216-6941-7. W B Saunders Company, Philadelphia. 1971. 6 Patel, S H & Xanthos, M. Volatile emissions during thermoplastic processing - A review. Advances in Polymer Technology. Vol 14, No 1, 67-77, (1995).

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CARBON DIOXIDE Carbon dioxide is always emitted when carbonaceous fuels are burned since the combustion process follows the reaction: C + O2 → CO2 and the stoichiometry of the reaction predicts that- 1 kg of carbon in a fuel will give rise to 3.67 kg of carbon dioxide. When however, wood products, such as wood, paper or board are used as packaging materials, in many of the systems described in this report, it is necessary to account for the carbon dioxide that was taken up by the tree while it was growing and fixed using solar energy. If wood products are considered as cellulose with an empirical formula C6H10O5 then carbon makes up 44% by mass and this will have been derived by the absorption of 0.44 x 3.67 kg = 1.61 kg of carbon dioxide per kg of cellulose. In the tables describing the air emissions, such packaging materials give rise to negative carbon dioxide values corresponding to that taken up during growth of the wood from which the packaging materials were made.

PRODUCTION OF SUSPENSION PVC All of the conversion processes reported here use suspension PVC as the starting resin. 26 plants producing a total of 3.15 million tonnes of PVC supplied data on the production of suspension PVC. Average process requirements are given in Table 1. The gross energy required to produce 1 kg of suspension PVC is 59.0 MJ with a range of values extending from 48.4 MJ to 72.3 MJ. The detailed gross energy required to produce 1 kg of suspension PVC is given in Table 2 and the corresponding gross primary fuel requirements are shown in Table 3. The gross primary fuels expressed in mass terms are given in Table 4. Table 5 shows the consumption of water resources by all of the processes leading to the production of suspension PVC and Table 6 shows the consumption of raw materials. The cumulative air emissions are shown in Table 7 and the corresponding water emissions are given in Table 8. The total cumulative solid waste generated during the production of 1 kg of suspension PVC is given in Table 9.

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Table 1 Average process requirements for the production of 1 kg of suspension PVC. Input Quantity Vinyl chloride monomer 1.008 kg Other chemicals 0.001 kg Nitrogen 0.001 kg Compressed air 0.127 cu m Process water 3.289 kg Cooling water 13.992 kg Electricity 0.853 MJ Thermal fuels 0.732 MJ Steam 0.969 kg Table 2 Gross energy in MJ required to produce 1 kg of suspension PVC. Totals may not agree because of rounding. Fuel type Fuel prod'n Energy content Energy use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Electricity 9.50 4.55 0.04 0.00 14.10 Oil fuels 0.34 5.19 0.15 11.27 16.95 Other fuels 1.76 15.30 0.05 10.92 28.03 Totals 11.60 25.04 0.24 22.20 59.07

Table 3 Gross primary fuels and feedstocks, expressed as energy in MJ, required to produce 1 kg of suspension PVC. Totals may not agree because of rounding. Fuel type Fuel prod'n Energy content Fuel use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Coal 2.25 2.65 <0.01 <0.01 4.90 Oil 0.97 5.55 0.21 11.29 18.02 Gas 3.33 14.15 0.03 10.89 28.39 Hydro 0.52 0.43 <0.01 - 0.94 Nuclear 3.84 1.84 <0.01 - 5.69 Lignite 0.53 0.24 <0.01 - 0.77 Wood - - - 0.01 0.01 Sulphur <0.01 <0.01 <0.01 0.01 0.02 Biomass 0.05 0.03 <0.01 <0.01 0.08 Hydrogen <0.01 0.92 <0.01 - 0.92 Recovered energy <0.01 -0.90 <0.01 - -0.90 Unspecified 0.10 0.14 <0.01 - 0.23 Peat 0.01 <0.01 <0.01 - 0.01 Geothermal <0.01 <0.01 <0.01 - 0.01 Solar <0.01 <0.01 <0.01 - <0.01 Wave/tidal <0.01 <0.01 <0.01 - <0.01 Totals 11.60 25.04 0.24 22.20 59.08

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Table 4 Gross primary fuels and feedstock resources, expressed as mass in mg, required to produce 1 kg of suspension PVC. Fuel type Input in mg Crude oil 400,000 Gas/condensate 540,000 Coal 170,000 Metallurgical coal 120 Lignite 51,000 Peat 860 Wood 1,000 Biomass 8,600

Table 5 Gross water resources in mg required to produce 1 kg of suspension PVC. Totals may not agree because of rounding. Source Use for Use for Totals processing cooling (mg) (mg) (mg) Public supply 4,900,000 - 4,900,000 River canal 580,000 36,000,000 37,000,000 Sea 230,000 28,000,000 28,000,000 Unspecified 2,600,000 11,000,000 14,000,000 Well 530,000 250,000 780,000 Totals 8,800,000 75,000,000 84,000,000

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Table 6 Gross raw materials consumption in mg to produce 1 kg of suspension PVC. Raw material Input in mg air 340,000 animal matter <1 barytes 96 bauxite 260 bentonite 39 calcium sulphate (CaSO4) 4 chalk (CaCO3) <1 clay 8 Cr <1 Cu 77 dolomite 4 Fe 330 feldspar <1 ferromanganese <1 fluorspar 2 granite <1 gravel 1 limestone (CaCO3) 23,000 Mg <1 N2 49,000 Ni <1 O2 74,000 olivine 3 Pb 1 phosphate as P2O5 3 potassium chloride (KCl) 31,000 quartz (SiO2) <1 rutile <1 S (bonded) 330 S (elemental) 1,800 sand (SiO2) 530 shale 11 sodium chloride (NaCl) 660,000 sodium nitrate (NaNO3) <1 unspecified <1 Zn <1

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Table 7 Gross air emissions in mg associated with the production of 1 kg of suspension PVC. Totals may not agree because of rounding. Emission From From From From From Totals fuel fuel transport process biomass production use operations operations use (mg) (mg) (mg) (mg) (mg) (mg) Dust 2,300 590 8 300 - 3,200 CO 410 850 89 21 - 1,400 CO2 670,000 1,200,000 14,000 31,000 -9,600 1,900,000 SOX 5,800 3,600 130 61 - 9,600 NOX 4,500 4,900 130 150 - 9,700 N2O <1 <1 - - - <1 Hydrocarbons 1,400 290 37 520 - 2,300 Methane 7,100 1,700 - 110 - 8,900 H2S <1 - - 2 - 2 HCl 62 10 - 71 - 140 Cl2 - - - 2 - 2 HF 3 <1 - <1 - 4 Lead(Pb) - <1 - <1 - <1 Metals 1 2 - <1 - 4 F2 - - - <1 - <1 Mercaptans - <1 - <1 - <1 Organo-Cl <1 - - 12 - 12 Aromatic-HC - - - 6 - 6 Polycyclic-HC - - - <1 - <1 Other organics - - - 19 - 19 CFC/HCFC - - - 28 - 28 Aldehydes (CHO) - - - <1 - <1 HCN - - - <1 - <1 H2SO4 - - - <1 - <1 Hydrogen (H2) 13 - - 1,600 - 1,600 Mercury (Hg)* - - - 1 - 1 Ammonia (NH3) - - - 82 - 82 CS2 - - - <1 - <1 DCE - - - 78 - 78 VCM - - - 88 - 88 VOC - - - 6 - 6 methylene chloride - - - <1 - <1 Cu (process) - - - <1 - <1 As (process) - - - <1 - <1 Cd (process) - - - <1 - <1 Ag (process) - - - <1 - <1 Zn (process) - - - <1 - <1 Cr (process) - - - <1 - <1 Se (process) - - - <1 - <1 Ni (process) - - - <1 - <1 Sb (process) - - - <1 - <1 Ethylene - - - 2 - 2 * According to recent information from EuroChlor, the mercury emission to air is 0.29 mg/kg PVC

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Table 8 Gross water emissions in mg associated with the production of 1 kg of suspension PVC. Totals may not agree because of rounding. Emission From From From From Totals fuel fuel transport process production use operations operations (mg) (mg) (mg) (mg) (mg) COD 6 - - 1,500 1,500 BOD 3 - - 340 340 Acid (H+) 3 - - 31 34 Dissolved solids 29 - - 14,000 14,000 Hydrocarbons 8 <1 - 19 26 NH4 3 - - 48 50 Suspended solids 57 - - 5,000 5,100 Phenol 3 - - <1 3 Al+++ - - - <1 <1 Ca++ - - - 250 250 Cu+/Cu++ - - - <1 <1 Fe++/Fe+++ - - - 1 1 Hg* - - - <1 <1 Pb - - - <1 <1 Mg++ - - - 1 1 Na+ - - - 26,000 26,000 K+ - - - 960 960 Ni++ - - - <1 <1 Zn++ - - - <1 <1 Other metals 1 - - 87 88 NO3- - - - 6 6 Other nitrogen <1 - - 12 12 BrO3- - - - 1 1 CrO3 - - - <1 <1 Cl- - - - 44,000 44,000 ClO3- - - - 200 200 CN- - - - <1 <1 F- - - - <1 <1 SO4-- - - - 2,100 2,100 CO3-- - - - 690 690 Phosphate as P2O5 - - - 100 100 AOX - - - 6 6 TOC - - - 10 10 Arsenic - - - <1 <1 DCE - - - 2 2 VCM - - - 4 4 Detergent/oil - - - 79 79 Dissolved Cl2 - - - 6 6 Organo-chlorine - - - 60 60 Dissolved organics - - - 30 30 Other organics - - - 160 160 Sulphur/sulphide - - - <1 <1 * According to recent information from EuroChlor, the mercury emission to water is 0.02 mg/kg PVC

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Table 9 Gross solid waste in mg associated with the production of 1 kg of suspension PVC. Totals may not agree because of rounding. Type From From From From Totals

fuel fuel transport process

production use operations operations

(mg) (mg) (mg) (mg) (mg)

Mineral 41,000 - - 8,100 49,000

Mixed industrial 310 - - 6,900 7,200

Slags/ash 8,100 1,600 - 3,700 13,000

Inert chemical 72 - - 3,900 4,000

Regulated chemical 10 - - 2,800 2,800

Unspecified 9 - - 8 17

Construction - - - 110 110

Metals - - - 18 18

To incinerator - - - 5,300 5,300

To recycling - - - 280 280

Paper & board - - - <1 <1

Plastics - - - 1,300 1,300

Putrescibles - - - <1 <1

Wood waste - - - 17 17

Wooden pallets - - - <1 <1

Waste returned to mine - - - 6,200 6,200

Tailings - - - 3,100 3,100

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DELIVERY OF POLYMER RESINS Polymer resins are delivered to converters either in bulk tankers or in plastic sacks. In the present report it is assumed that all resin is delivered in 20 tonne payload bulk tankers. The typical performance characteristics of a 20 tonne payload bulk tanker are shown in Tables 10 to 17 and these data have been used in the calculations. Note that the data are expressed per vehicle-km; for a fully laden tanker, this corresponds to transporting 20 tonne over a distance of 1 km. Table 10 Gross energy per vehicle-km for a 20 tonne payload bulk tanker Fuel type Fuel prod'n Energy content Energy use Feedstock Total

& delivery of delivered in energy energy

energy fuel transport

(MJ) (MJ) (MJ) (MJ) (MJ)

Electricity 0.32 - 0.14 <0.01 0.46

Oil fuels 1.67 - 16.82 0.05 18.54

Other fuels 0.03 - 0.49 0.03 0.55

Totals 2.02 - 17.45 0.08 19.55

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Table 11 Gross fuel requirements per vehicle-km for a 20 tonne payload bulk tanker Fuel type Fuel prod'n Energy content Fuel use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Coal 0.14 - 0.47 <0.01 0.61 Oil 1.22 - 16.83 0.05 18.1 Gas 0.55 - 0.11 0.03 0.69 Hydro <0.01 - <0.01 - 0.01 Nuclear 0.11 - 0.04 - 0.15 Lignite <0.01 - <0.01 - <0.01 Wood - - - <0.01 <0.01 Sulphur - - <0.01 <0.01 <0.01 Biomass <0.01 - <0.01 <0.01 <0.01 Hydrogen <0.01 - <0.01 - <0.01 Recovered energy - - <0.01 - <0.01 Unspecified <0.01 - <0.01 - <0.01 Peat <0.01 - <0.01 - <0.01 Geothermal <0.01 - <0.01 - <0.01 Solar <0.01 - <0.01 - <0.01 Wave/tidal <0.01 - <0.01 - <0.01 Totals 2.02 - 17.45 0.08 19.55

Table 12 Gross fuel requirements in mg per vehicle-km for a 20 tonne payload bulk tanker Fuel type Input in mg Crude oil 400,000 Gas/condensate 14,000 Coal 22,000 Metallurgical coal 11,000 Lignite 350 Peat 4 Wood <1 Biomass 36

Table 13 Gross water requirements in mg per vehicle-km for a 20 tonne payload bulk tanker Source Use for Use for Totals processing cooling (mg) (mg) (mg) Public supply 1,200,000 - 1,200,000 River canal 610 1,200 1,800 Sea 2,100 260,000 260,000 Unspecified 51,000 13,000 64,000 Well 130 19 140 Totals 1,200,000 270,000 1,500,000

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Table 14 Gross raw materials requirements in mg per vehicle-km for a 20 tonne payload bulk tanker Raw material Input in mg

unspecified <1

air 1,900

barytes 16

bauxite 110

bentonite 20

calcium sulphate (CaSO4) <1

chalk (CaCO3) <1

clay <1

Cr <1

dolomite 330

Fe 27,000

feldspar <1

ferromanganese 24

fluorspar 2

granite <1

gravel 100

limestone (CaCO3) 5,600

N2 2,100

Ni <1

O2 470

olivine 250

Pb 210

phosphate as P2O5 <1

potassium chloride (KCl) 7

rutile <1

S (bonded) 54

S (elemental) 110

sand (SiO2) 1

shale <1

sodium chloride (NaCl) 1,000

Zn 8

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Table 15 Gross air emissions in mg per vehicle-km for a 20 tonne payload bulk tanker Emission From From From From From Totals

fuel fuel transport process biomass

production use operations operations use

(mg) (mg) (mg) (mg) (mg) (mg)

Dust 150 70 1,000 23 - 1,300

CO 39 52 12,000 580 - 13,000

CO2 150,000 80,000 1,200,000 16,000 -32 1,500,000

SOX 1,600 160 3,100 <1 - 4,900

NOX 480 480 15,000 3 - 16,000

N2O <1 <1 - - - <1

Hydrocarbons 530 41 4,000 4 - 4,600

Methane 440 200 - 1 - 640

H2S <1 - - 1 - 1

HCl 4 2 - 1 - 6

Cl2 - - - <1 - <1

HF <1 <1 - <1 - <1

Lead(Pb) - <1 - <1 - <1

Metals <1 <1 - <1 - <1

F2 - - - <1 - <1

Mercaptans - <1 - <1 - <1

Organo-Cl - - - <1 - <1

Aromatic-HC - - - 54 - 54

Polycyclic-HC - - - <1 - <1

Other organics - - - <1 - <1

CFC/HCFC - - - <1 - <1

Aldehydes (CHO) - - - <1 - <1

HCN - - - <1 - <1

H2SO4 - - - <1 - <1

Hydrogen (H2) <1 - - 1 - 1

Mercury (Hg) - - - <1 - <1

Ammonia (NH3) - - - <1 - <1

CS2 - - - <1 - <1

DCE - - - <1 - <1

VCM - - - <1 - <1

VOC - - - <1 - <1

Cu (process) - - - <1 - <1

Cd (process) - - - <1 - <1

Zn (process) - - - <1 - <1

Sb (process) - - - <1 - <1

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Table 16 Gross water emissions in mg per vehicle-km for a 20 tonne payload bulk tanker Emission From From From From Totals fuel fuel transport process production use operations operations (mg) (mg) (mg) (mg) (mg) COD 20 - - 19 39 BOD 18 - - <1 18 Acid (H+) <1 - - 1 1 Dissolved solids <1 - - 4 4 Hydrocarbons 18 <1 - 1 19 NH4 <1 - - 1 1 Suspended solids 6 - - 2,200 2,200 Phenol 18 - - <1 18 Al+++ - - - <1 <1 Ca++ - - - <1 <1 Cu+/Cu++ - - - <1 <1 Fe++/Fe+++ - - - 1 1 Hg - - - <1 <1 Pb - - - <1 <1 Mg++ - - - <1 <1 Na+ - - - 1,100 1,100 K+ - - - <1 <1 Ni++ - - - <1 <1 Zn++ - - - <1 <1 Other metals <1 - - 1 1 NO3- - - - <1 <1 Other nitrogen <1 - - <1 <1 BrO3- - - - <1 <1 CrO3 - - - <1 <1 Cl- - - - 17 17 ClO3- - - - <1 <1 CN- - - - <1 <1 F- - - - <1 <1 SO4-- - - - 7 7 CO3-- - - - <1 <1 Phosphate as P2O5 - - - <1 <1 AOX - - - <1 <1 TOC - - - <1 <1 Arsenic - - - <1 <1 DCE - - - <1 <1 VCM - - - <1 <1 Detergent/oil - - - 1 1 Dissolved Cl2 - - - <1 <1 Organo-chlorine - - - <1 <1 Dissolved organics - - - <1 <1 Other organics - - - <1 <1 Sulphur/sulphide - - - <1 <1

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Table 17 Gross solid waste in mg per vehicle-km for a 20 tonne payload bulk tanker Type From From From From Totals




Mineral 4,200 - - 22,000 26,000

Mixed industrial 1,800 - - 830 2,600

Slags/ash 430 170 - 8,200 8,800

Inert chemical <1 - - 56 56

Regulated chemical <1 - - 2 2

Unspecified <1 - - <1 <1

Construction - - - <1 <1

Metals - - - <1 <1

To incinerator - - - 10 10

To recycling - - - <1 <1

Plastic containers - - - <1 <1

Paper & board - - - <1 <1

Plastics - - - 2 2

Putrescibles - - - 6 6

Wood waste - - - <1 <1


Waste returned to mine - - - 680 680

Tailings - - - 720 720

The delivery distance will obviously vary from one converter to another and, in all of the calculations reported here, a notional one way delivery distance of 100 km has been assumed. It is also assumed that an empty vehicle uses only 70% of the fuel of a fully laden vehicle. Since bulk tankers usually make an empty return journey, the energy associated with the round trip will be 1.7 times the one-way delivery distance rather 2 times the delivery distance, because of the lower fuel consumption on the return journey. Making these assumptions, the transport requirements per kg of polymer delivered will be 100 x 1.7/20000 = 0.0085 vehicle-km. The transport data associated with the delivery of 1 kg of polymer resin is therefore calculated by multiplying the entries in Tables 10 to 17 by the factor 0.0085.

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UPVC FILM PRODUCTION The production of unplasticised polyvinyl chloride (UPVC) film is shown schematically in Figure 2. Molten polymer is extruded as a continuous tube. As it leaves the extrusion die, the tube is inflated with air to form a bubble and when the bubble reaches the appropriate size it is cooled by air which changes it into a solid film. The region where the solidification occurs, known as the 'frost line', is the region where the required film gauge (or thickness) is reached. The tube is then guided by collapsing boards to be gradually flattened as it approaches the pinch rolls. When the lay-flat film passes between them, the top of the bubble is effectively sealed. The seal is entirely dependent upon the nip pressures since the two plastic surfaces do not stick together.

Figure 2 Schematic diagram showing the production of UPVC film. A constant bubble pressure must be maintained during a production run and, once the bubble is established, the air supply through the die merely compensates for unavoidable minor losses. The cooling system must be able to produce a uniform cooling rate around the circumference of the bubble, otherwise the blowing effect will be unbalanced and the bubble deformed.

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Inadequate cooling will, in extreme cases, lead to the film sticking in the pinch rolls. The lay-flat tubing is fed to the winding equipment via a pre-treatment and slitting unit. Slitting and trimming is a continuous cutting operation. Finally, the finished film is packaged for despatch. Data have been obtained for the production of some 10,000 tonne of UPVC film. The inputs for the production of this film are as shown in Table 18. Table 18 Inputs of materials and energy for the production of I kg of UPVC film. Input Quantity Processing PVC resin 1.03661 kg Electricity 1.69678 MJ Gas oil 0.19619 MJ Lubricating oil 0.00631 MJ Grease 0.00033 MJ Packaging Pallets 0.00707 kg LDPE film 0.00864 kg PP strapping 0.00031 kg The gross or cumulative energy to produce 1 kg of UPVC film, including packaging, is 68.58 MJ. The detailed breakdown of this energy is shown in Table 19. The corresponding gross primary fuels are given in Table 20 and Table 21 shows these fuels expressed as mass. Table 22 shows the cumulative water requirements and Table 23 shows the gross raw materials requirements. Table 24 gives the gross air emissions and Table 25 shows the emissions to water. The total solid waste generated is given in Table 26. Note that in all of these tables, the system refers to all processing operations starting with crude oil, gas and sodium chloride in the earth. Table 27 shows the relative contributions to total energy.

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Table 19 Gross energy required to produce 1 kg of UPVC film. Fuel type Fuel prod'n Energy content Energy use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Electricity 12.18 5.48 0.05 <0.01 17.71 Oil fuels 0.40 5.70 0.25 12.43 18.78 Other fuels 1.85 15.97 0.06 11.99 29.88 Totals 14.43 27.15 0.37 24.43 66.37

Table 20 Gross primary fuels required to produce 1 kg of UPVC film. Fuel type Fuel prod'n Energy content Fuel use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Coal 3.30 3.22 0.01 <0.01 6.53 Oil 0.85 5.96 0.33 12.45 19.59 Gas 3.73 14.94 0.03 11.72 30.42 Hydro 0.45 0.43 <0.01 - 0.89 Nuclear 5.49 2.40 <0.01 - 7.89 Lignite 0.49 0.21 <0.01 - 0.69 Wood - - - 0.15 0.15 Sulphur <0.01 <0.01 <0.01 0.10 0.10 Biomass 0.04 0.02 <0.01 <0.01 0.06 Hydrogen <0.01 1.00 <0.01 - 1.00 Recovered energy <0.01 -1.08 <0.01 - -1.08 Unspecified 0.07 0.05 <0.01 - 0.12 Peat <0.01 <0.01 <0.01 - <0.01 Geothermal <0.01 <0.01 <0.01 - <0.01 Solar <0.01 <0.01 <0.01 - <0.01 Wave/tidal <0.01 <0.01 <0.01 - <0.01 Totals 14.43 27.15 0.37 24.43 66.37

Table 21 Gross primary fuels in mg required to produce 1 kg of UPVC film. Fuel type Input in mg Crude oil 430,000 Gas/condensate 570,000 Coal 230,000 Metallurgical coal 310 Lignite 46,000 Peat 350 Wood 17,000 Biomass 7,200

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Table 22 Gross water requirements to produce 1 kg of UPVC film. Source Use for Use for Totals processing cooling (mg) (mg) (mg) Public supply 3,700,000 - 3,700,000 River canal 1,000,000 670,000 1,700,000 Sea 130,000 36,000,000 36,000,000 Unspecified 6,400,000 36,000,000 42,000,000 Well 180,000 10,000 190,000 Totals 11,000,000 73,000,000 84,000,000

Table 23 Gross raw materials requirements to produce 1 kg of UPVC film. Raw material Input in mg air 270,000 barytes 85 bauxite 470 bentonite 34 calcium sulphate (CaSO4) 3 chalk (CaCO3) <1 clay 9 Cr 1 dolomite 10 Fe 830 feldspar <1 ferromanganese 1 fluorspar 2 granite <1 gravel 3 limestone (CaCO3) 9,700 N2 18,000 Ni <1 O2 5,800 olivine 7 Pb 3 phosphate as P2O5 1 potassium chloride (KCl) 6,100 rutile <1 S (bonded) <1 S (elemental) 11,000 sand (SiO2) 490 shale 10 sodium chloride (NaCl) 670,000 unspecified <1 Zn <1

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Table 24 Gross air emissions associated with the production of 1 kg of UPVC film . Emission From From From From From Totals




Dust 3,100 840 16 190 - 4,100

CO 480 1,900 190 22 - 2,600

CO2 830,000 1,400,000 22,000 31,000 -22,000 2,300,000

SOX 6,800 4,600 120 15 - 12,000

NOX 5,200 6,400 240 76 - 12,000

N2O <1 <1 - <1 - <1

Hydrocarbons 1,200 300 67 1,200 - 2,700

Methane 7,500 2,500 - 180 - 10,000

H2S <1 - - 2 - 2

HCl 91 17 - 68 - 180

Cl2 - - - 2 - 2

HF 5 1 - <1 - 6

Lead(Pb) - <1 - <1 - <1

Metals 1 3 - <1 - 4

F2 - - - <1 - <1


Organo-Cl - - - 38 - 38



Other organics - - - 75 - 75

CFC/HCFC - - - 1 - 1


HCN - - - <1 - <1

H2SO4 - - - <1 - <1

Hydrogen (H2) 6 - - 310 - 310

Mercury (Hg) - - - <1 - <1

Ammonia (NH3) - - - <1 - <1

CS2 - - - <1 - <1

DCE - - - 360 - 360

VCM - - - 250 - 250

VOC - - - 13 - 13

Cu (process) - - - <1 - <1

Cd (process) - - - <1 - <1

Zn (process) - - - <1 - <1

Sb (process) - - - <1 - <1

24

Table 25 Gross water emissions associated with the production of 1 kg of UPVC film. Emission From From From From Totals fuel fuel transport process production use operations operations (mg) (mg) (mg) (mg) (mg) COD 5 - - 790 800 BOD 3 - - 88 91 Acid (H+) 2 - - 48 50 Dissolved solids 28 - - 2,700 2,700 Hydrocarbons 7 <1 - 20 28 NH4 2 - - 2 4 Suspended solids 72 - - 1,800 1,900 Phenol 3 - - <1 4 Al+++ - - - <1 <1 Ca++ - - - 49 49 Cu+/Cu++ - - - 1 1 Fe++/Fe+++ - - - 5 5 Hg - - - <1 <1 Pb - - - <1 <1 Mg++ - - - 2 2 Na+ - - - 8,500 8,500 K+ - - - 190 190 Ni++ - - - 1 1 Zn++ - - - <1 <1 Other metals 1 - - 67 67 NO3- - - - 1 1 Other nitrogen <1 - - 2 2 BrO3- - - - <1 <1 CrO3 - - - <1 <1 Cl- - - - 41,000 41,000 ClO3- - - - 10 10 CN- - - - <1 <1 F- - - - <1 <1 SO4-- - - - 4,200 4,200 CO3-- - - - 66 66 Phosphate as P2O5 - - - 17 17 AOX - - - <1 <1 TOC - - - 94 94 Arsenic - - - <1 <1 DCE - - - 2 2 VCM - - - 1 1 Detergent/oil - - - 52 52 Dissolved Cl2 - - - 2 2 Organo-chlorine - - - <1 <1 Dissolved organics - - - 1,600 1,600 Other organics - - - 3 3 Sulphur/sulphide - - - 1 1

25

Table 26 Gross solid waste associated with the production of 1 kg of UPVC film. Type From From From From Totals




Mineral 51,000 - - 8,300 59,000


Slags/ash 11,000 1,900 - 820 14,000

Inert chemical 1 - - 12,000 12,000


Unspecified 1 - - 7,500 7,500


Metals - - - 380 380




Paper & board - - - 370 370

Plastics - - - 870 870


Wood waste - - - 320 320



Tailings - - - 9 9

Table 27 Relative contributions to the energy required for the production of UPVC film. Resin production 89.13% Resin delivery 0.31% Processing 8.84% Packaging 1.72% Total 100.00%

26

CALENDERED RIGID PVC SHEET Calendering is a process used to manufacture continuous plastic sheet. Essentially a calender is a set of three or more heated rolls that convert high viscosity polymer into sheet. The polymer passes between a sequence of heated rolls that control the feed rate, the thickness of the sheet and the surface finish. The production of good quality product depends critically on the control of the temperature, the gap between the rolls and the drive system. A variety of different roll configurations are used in practice but figure 3 shows the schematic arrangement of the operations on a typical calender line. The polymer compound, usually pre-heated (1) is fed through a pair of mixing rolls to ensure a uniform consistency. The polymer compound passes through a metal separation device to remove any accidental contamination before passing to the calender itself (4). Once formed, the sheet is fed to cooling rolls (5) and after passing through a thickness measurement operation (6) is trimmed (7) before being wound onto the final rolls.

1

2 23

4

44

45 5 5

5 5

6

77

8

Figure 3 Schematic diagram of the sequence used to produce smooth or profiled calendered sheet. See text for an explanation of the symbols Data gave been obtained from four different factories operating in Germany, which produce 300mm calendered PVC sheet. The data supplied covers all operations within the factories starting with PVC resin, and following all operations through mixing, preplastifying, calendering, pulling, cooling rolls, wind-up and packaging. All internal factory transport is also included. In practice the polymer used in calendered sheet production contains 2.5% to 5.0% of additives (stabilisers, polymeric modifiers, slip agents and pigments). However, in the calculations these have all been treated as if they were PVC homopolymer.

27

The major inputs to the process are shown in Table 28 and the uses of these inputs in the various stages of the processing are shown in Table 29. Table 29 also indicates where the solid waste arises. The process generates 0.3% contaminated waste that is sent to landfill. Associated with this process are small quantities of air emissions. Per kg of saleable product the main emissions are 1 mg of dust, 0.6 mg of organo-chlorine compounds and 0.9 mg of HCl all of which are controlled. Table 30 shows the cumulative gross energy associated with the production of 1 kg of calendered PVC sheet and table 31 shows the total primary fuels. When fuels are expressed as mass the gross fuel consumption is as shown in Table 32. Table 33 gives the gross water consumption and Table 34 gives the total cumulative consumption of raw materials. The cumulative emissions to air and water are shown in Table 35 and 36 respectively and the total solid waste production is given in Table 37. The relative contributions to overall energy of the different operations are shown in Table 38. Table 28 Inputs required for the production of 1 kg of calendered PVC sheet. Input Quantity Production PVC resin 1.00340 kg Electricity 1.82250 MJ Steam 0.23475 kg Natural gas 0.17000 MJ Diesel 0.20051 MJ Lube 0.02640 MJ Grease 0.00004 MJ Propane 0.00438 MJ Water 19.0925 kg Packaging LDPE film 0.0018 kg Cardboard 0.0030 kg Pallets 0.0100 kg Cores (cardboard) 0.0080 kg

28

Table 29 Proportion (%) of the different inputs and outputs used or generated in the various stages of the calendering operation. Processing step Electricity Steam Oil Waste generation Raw materials storage 1.0 3.0 1.0 3.0 Mixing 10.0 6.0 60.0 5.0 Calendering 86.5 50.0 32.0 30.0 Slitting 1.0 11.0 5.0 50.0 Scrap treatment 1.0 2.0 1.0 7.0 Packaging 0.5 28.0 1.0 5.0 Totals 100.0 100.0 100.0 100.0 Table 30 Gross energy required to produce 1 kg of calendered PVC sheet. Fuel type Fuel prod'n Energy content Energy use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Electricity 12.02 5.50 0.07 <0.01 17.59 Oil fuels 0.41 5.71 0.25 11.88 18.24 Other fuels 1.84 16.20 0.06 11.70 29.81 Totals 14.26 27.41 0.39 23.58 65.64

Table 31 Gross primary fuels required to produce 1 kg of calendered PVC sheet. Fuel type Fuel prod'n Energy content Fuel use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Coal 2.85 3.11 0.01 <0.01 5.97 Oil 0.71 5.91 0.35 11.90 18.87 Gas 3.05 14.74 0.03 11.14 28.95 Hydro 0.50 0.45 <0.01 - 0.95 Nuclear 5.38 2.38 <0.01 - 7.77 Lignite 1.58 0.69 <0.01 - 2.27 Wood - - - 0.44 0.44 Sulphur <0.01 <0.01 <0.01 0.10 0.10 Biomass 0.05 0.02 <0.01 <0.01 0.07 Hydrogen <0.01 1.05 <0.01 - 1.05 Recovered energy <0.01 -1.01 <0.01 - -1.01 Unspecified 0.13 0.07 <0.01 - 0.20 Peat <0.01 <0.01 <0.01 - <0.01 Geothermal <0.01 <0.01 <0.01 - <0.01 Solar <0.01 <0.01 <0.01 - <0.01 Wave/tidal 0.01 <0.01 <0.01 - 0.01 Totals 14.26 27.41 0.39 23.58 65.64

29

Table 32 Gross primary fuels in mg required to produce 1 kg of calendered PVC sheet. Fuel type Input in mg

Crude oil 420,000

Gas/condensate 550,000

Coal 210,000

Metallurgical coal 360

Lignite 150,000

Peat 250

Wood 50,000

Biomass 8,300

Table 33 Gross water requirements to produce 1 kg of calendered PVC sheet. Source Use for Use for Totals

processing cooling

(mg) (mg) (mg)

Public supply 4,600,000 - 4,600,000

River canal 980,000 740,000 1,700,000

Sea 130,000 35,000,000 35,000,000

Unspecified 6,200,000 54,000,000 60,000,000

Well 180,000 11,000 190,000

Totals 12,000,000 90,000,000 102,000,000

30

Table 34 Gross raw materials requirements to produce 1 kg of calendered PVC sheet. Raw material Input in mg

air 260,000

barytes 82

bauxite 450

bentonite 33

calcium sulphate (CaSO4) 3

chalk (CaCO3) <1

clay 9

Cr 1

dolomite 11

Fe 950

feldspar <1

ferromanganese 1

fluorspar 2

granite <1

gravel 3


N2 17,000

Ni <1

O2 5,600

olivine 8

Pb 3

phosphate as P2O5 1

potassium chloride (KCl) 5,900

rutile <1

S (bonded) <1

S (elemental) 10,000

sand (SiO2) 480

shale 9


unspecified <1

Zn <1

31

Table 35 Gross air emissions associated with the production of 1 kg of calendered PVC sheet. Emission From From From From From Totals




Dust 3,800 870 17 210 - 4,900

CO 530 2,000 200 31 - 2,800

CO2 870,000 1,400,000 23,000 31,000 -53,000 2,300,000

SOX 6,000 4,700 120 82 - 11,000

NOX 4,100 6,700 250 74 - 11,000

N2O <1 <1 - <1 - <1

Hydrocarbons 1,200 340 70 1,100 - 2,700

Methane 6,800 2,600 - 200 - 9,600

H2S <1 - - 3 - 3

HCl 79 17 - 67 - 160

Cl2 - - - 2 - 2

HF 4 1 - <1 - 4

Lead(Pb) - <1 - <1 - <1

Metals 1 3 - <1 - 4

F2 - - - <1 - <1


Organo-Cl - - - 37 - 37




CFC/HCFC - - - 1 - 1


HCN - - - <1 - <1

H2SO4 - - - <1 - <1

Hydrogen (H2) 9 - - 350 - 360

Mercury (Hg) - - - <1 - <1

Ammonia (NH3) - - - <1 - <1

CS2 - - - <1 - <1

DCE - - - 340 - 340

VCM - - - 240 - 240

VOC - - - 5 - 5

Cu (process) - - - <1 - <1

Cd (process) - - - <1 - <1

Zn (process) - - - <1 - <1

Sb (process) - - - <1 - <1

32

Table 36 Gross water emissions associated with the production of 1 kg of calendered PVC sheet. Emission From From From From Totals fuel fuel transport process production use operations operations (mg) (mg) (mg) (mg) (mg) COD 5 - - 920 920 BOD 3 - - 99 100 Acid (H+) 3 - - 46 49 Dissolved solids 27 - - 2,600 2,600 Hydrocarbons 7 1 - 19 27 NH4 2 - - 2 4 Suspended solids 83 - - 1,800 1,900 Phenol 3 - - <1 3 Al+++ - - - <1 <1 Ca++ - - - 47 47 Cu+/Cu++ - - - 1 1 Fe++/Fe+++ - - - 5 5 Hg - - - <1 <1 Pb - - - <1 <1 Mg++ - - - 2 2 Na+ - - - 8,300 8,300 K+ - - - 180 180 Ni++ - - - 1 1 Zn++ - - - <1 <1 Other metals 1 - - 65 66 NO3- - - - 1 1 Other nitrogen <1 - - 4 4 BrO3- - - - <1 <1 CrO3 - - - <1 <1 Cl- - - - 39,000 39,000 ClO3- - - - 10 10 CN- - - - <1 <1 F- - - - <1 <1 SO4-- - - - 4,100 4,100 CO3-- - - - 63 63 Phosphate as P2O5 - - - 17 17 AOX - - - <1 <1 TOC - - - 91 91 Arsenic - - - <1 <1 DCE - - - 2 2 VCM - - - 1 1 Detergent/oil - - - 49 49 Dissolved Cl2 - - - 2 2 Organo-chlorine - - - <1 <1 Dissolved organics - - - 1,600 1,600 Other organics - - - 3 3 Sulphur/sulphide - - - 1 1

33

Table 37 Gross solid waste associated with the production of 1 kg of calendered PVC sheet. Type From From From From Totals




Mineral 65,000 - - 8,200 73,000


Slags/ash 15,000 1,900 - 880 17,000

Inert chemical 1 - - 12,000 12,000


Unspecified 1 - - 9,700 9,700


Metals - - - 490 490




Paper & board - - - 11,000 11,000

Plastics - - - 460 460


Wood waste - - - 370 370



Tailings - - - 10 10

Table 38 Relative contributions to the energy required for the production of calendered PVC sheet. Resin production 87.29% Resin delivery 0.31% Processing 11.03% Packaging 1.37% Total 100.00%

34

PVC INJECTION MOULDING Injection moulding is one of the most widely used polymer conversion processes and is capable of producing almost any component. In injection moulding, the polymer resin together with any additives is heated until molten and injected into a water-cooled mould. Once solid, the mould is opened and the component ejected. The cycle is then repeated. Irrespective of the type of machinery used, the sequence of events in the injection moulding process can be represented as a time cycle as shown in Figure 4.

Freezetime

Deadtime

Injectiontime

Dwelltime

Figure 4 The time cycle in injection moulding. The four elements of the cycle are (i) Injection time - the time taken to fill the mould with molten polymer. (ii) Dwell time - the time period during which the mould is full but remains under pressure. (iii) Freeze time - the time required for the moulding to set sufficiently to allow the moulding to be removed without damage. (iv) Dead time - the time required for the mould to open, for the moulding to be removed and for the mould to close again.

35

In practice, the setting process starts during the dwell time and continues during the freezing time so the boundary between these two phases of the operation is blurred. Achieving the correct proportions for these four elements of the moulding cycle is the key to ensuring that good quality mouldings are produced in the shortest possible time thereby making the most efficient use of the moulding machine. It is important to recognise that the performance of injection moulding factories can be very variable because of factors such as rate of injection (kg/hour), the design and age of the moulding machines, the general level of activity in the factory and the duration of a production sequence. As a consequence it is almost impossible to produce typical, representative figures for performance. To provide indicative values, two data sets have been obtained; one moulding PVC components and the other moulding polypropylene. Data have been obtained from two factories operating in France, which between them produce over 9000 tonne of PVC fittings for drainage pipe systems. Table 39 gives the average input data used in the calculations. These data include all operations associated with compounding, injection moulding, storage, warehousing, heating and internal transport. In the calculations fillers, stabilisers, lubricants and pigments have all been treated as if they were homopolymer. The data also include in-house scrap, which is ground and re-used. On average the process produces 0.7% unusable polymer waste but all other scrap is recycled internally. There is, in addition, a small production of landfilled other waste (2.8 g per kg product) and some regulated waste (0.1 g per kg product). Water emissions are monitored and show a COD of 28 mg per kg of product and suspended solids of 20 mg per kg product. These have been included in the calculations.

36

Table 39 Inputs required to produce I kg of saleable PVC mouldings. Inputs Quantity Process PVC resin 0.9381 kg Stabiliser 0.0388 kg Lubricant 0.0068 kg Pigment 0.0007 kg Filler 0.0227 kg Electricity 4.9486 MJ Medium fuel oil 0.3474 MJ Diesel 0.0432 MJ Lubricating oils 0.0948 MJ Butane 0.2931 MJ Propane 0.5449 MJ Grease 1.3722 MJ Solvents 0.1349 kg Water 22.2136 kg Packaging Pallets 0.0461 kg PP strapping 0.0097 kg Wood 0.0005 kg Cardboard 0.0002 kg Paper labels 0.1471 kg The cumulative energy associated with the production of 1 kg of PVC injection moulded product is given in Table 40 and the corresponding primary fuels in Table 41. When these fuels are expressed as mass the data are as shown in Table 42. The gross water requirements are given in Table 43 and the consumption of raw materials is shown in table 44. The gross emissions to air and water are given in Tables 45 and 46 respectively and the cumulative solid waste is shown in Table 47. The relative contributions of the different operations to the overall total energy are shown in Table 48. Table 40 Gross energy required to produce 1 kg of PVC injection moulding. Fuel type Fuel prod'n Energy content Energy use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Electricity 20.82 9.28 0.05 <0.01 30.16 Oil fuels 1.46 9.78 0.36 18.31 29.90 Other fuels 1.80 15.57 0.06 16.00 33.44 Totals 24.09 34.62 0.47 34.31 93.50

37

Table 41 Gross primary fuels required to produce 1 kg of PVC injection moulding. Fuel type Fuel prod'n Energy content Fuel use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Coal 2.99 3.08 0.01 <0.01 6.07 Oil 1.65 10.06 0.43 18.33 30.47 Gas 3.44 14.34 0.03 11.43 29.24 Hydro 1.11 0.71 <0.01 - 1.82 Nuclear 14.07 6.14 <0.01 - 20.22 Lignite 0.54 0.23 <0.01 - 0.77 Wood - - - 4.45 4.45 Sulphur <0.01 <0.01 <0.01 0.10 0.10 Biomass 0.15 0.07 <0.01 <0.01 0.22 Hydrogen <0.01 0.97 <0.01 - 0.97 Recovered energy <0.01 -1.06 <0.01 - -1.06 Unspecified 0.13 0.07 <0.01 - 0.20 Peat <0.01 <0.01 <0.01 - <0.01 Geothermal <0.01 <0.01 <0.01 - <0.01 Solar <0.01 <0.01 <0.01 - <0.01 Wave/tidal 0.01 <0.01 <0.01 - 0.01 Totals 24.09 34.63 0.47 34.31 93.50

Table 42 Gross primary fuels in mg required to produce 1 kg of PVC injection moulding. Fuel type Input in mg Crude oil 680,000 Gas/condensate 550,000 Coal 220,000 Metallurgical coal 1,000 Lignite 51,000 Peat 320 Wood 500,000 Biomass 25,000

Table 43 Gross water requirements to produce 1 kg of PVC injection moulding. Source Use for Use for Totals processing cooling (mg) (mg) (mg) Public supply 16,000,000 - 16,000,000 River canal 980,000 650,000 1,600,000 Sea 130,000 35,000,000 35,000,000 Unspecified 6,200,000 57,000,000 63,000,000 Well 180,000 9,800 190,000 Totals 24,000,000 93,000,000 117,000,000

38

Table 44 Gross raw materials requirements to produce 1 kg of PVC injection moulding. Raw material Input in mg

air 270,000

barytes 83

bauxite 470

bentonite 35


chalk (CaCO3) <1

clay 69

Cr 5

dolomite 32

Fe 2,700

feldspar <1

ferromanganese 2

fluorspar 2

granite <1

gravel 10


N2 17,000

Ni <1

O2 5,600

olivine 25

Pb 3

phosphate as P2O5 1


rutile <1

S (bonded) <1


sand (SiO2) 470

shale 9


unspecified 31

Zn <1

39

Table 45 Gross air emissions associated with the production of 1 kg of PVC injection moulding. Emission From From From From From Totals




Dust 2,900 860 21 510 - 4,300

CO 480 2,500 240 150 - 3,400

CO2 860,000 1,600,000 29,000 32,000 -480,000 2,000,000

SOX 7,500 7,000 160 990 - 16,000

NOX 4,900 7,800 310 190 - 13,000

N2O <1 <1 - <1 - <1

Hydrocarbons 1,500 840 87 1,200 - 3,600

Methane 7,000 2,500 - 650 - 10,000

H2S <1 - - 13 - 13

HCl 82 17 - 67 - 170

Cl2 - - - 2 - 2

HF 4 1 - <1 - 5

Lead(Pb) - <1 - <1 - <1

Metals 2 5 - <1 - 6

F2 - - - <1 - <1

Mercaptans - <1 - 3 - 3

Organo-Cl - - - 37 - 37




CFC/HCFC - - - 1 - 1


HCN - - - <1 - <1

H2SO4 - - - <1 - <1

Hydrogen (H2) 6 - - 300 - 310

Mercury (Hg) - - - <1 - <1

Ammonia (NH3) - - - <1 - <1

CS2 - - - <1 - <1

DCE - - - 340 - 340

VCM - - - 240 - 240

VOC - - - 14 - 14

Cu (process) - - - <1 - <1

Cd (process) - - - <1 - <1

Zn (process) - - - <1 - <1

Sb (process) - - - <1 - <1

40

Table 46 Gross water emissions associated with the production of 1 kg of PVC injection moulding. Emission From From From From Totals fuel fuel transport process production use operations operations (mg) (mg) (mg) (mg) (mg) COD 18 - - 2,900 2,900 BOD 14 - - 290 300 Acid (H+) 3 - - 46 49 Dissolved solids 27 - - 2,600 2,700 Hydrocarbons 18 29 - 20 68 NH4 2 - - 2 4 Suspended solids 69 - - 2,400 2,500 Phenol 14 - - <1 15 Al+++ - - - <1 <1 Ca++ - - - 47 47 Cu+/Cu++ - - - 1 1 Fe++/Fe+++ - - - 5 5 Hg - - - <1 <1 Pb - - - <1 <1 Mg++ - - - 2 2 Na+ - - - 8,300 8,300 K+ - - - 180 180 Ni++ - - - 1 1 Zn++ - - - <1 <1 Other metals 1 - - 77 78 NO3- - - - 1 1 Other nitrogen <1 - - 32 33 BrO3- - - - <1 <1 CrO3 - - - <1 <1 Cl- - - - 40,000 40,000 ClO3- - - - 10 10 CN- - - - <1 <1 F- - - - <1 <1 SO4-- - - - 4,100 4,100 CO3-- - - - 64 64 Phosphate as P2O5 - - - 20 20 AOX - - - <1 <1 TOC - - - 92 92 Arsenic - - - <1 <1 DCE - - - 2 2 VCM - - - 1 1 Detergent/oil - - - 51 51 Dissolved Cl2 - - - 2 2 Organo-chlorine - - - <1 <1 Dissolved organics - - - 1,600 1,600 Other organics - - - 3 3 Sulphur/sulphide - - - 2 2

41

Table 47 Gross solid waste associated with the production of 1 kg of PVC injection moulding. Type From From From From Totals




Mineral 49,000 - - 9,700 59,000

Mixed industrial 1,500 - - 4,000 5,500

Slags/ash 12,000 1,800 - 1,400 15,000

Inert chemical 1 - - 14,000 14,000


Unspecified 1 - - 45,000 45,000


Metals - - - 2,200 2,200




Paper & board - - - 150,000 150,000

Plastics - - - 8,200 8,200


Wood waste - - - 1,700 1,700



Tailings - - - 12 12

Table 48 Relative contributions to the energy required for the production of PVC injection moulding. Resin production 62.00% Resin delivery 0.30% Processing 28.62% Packaging 9.08% Total 100.00%

42

PVC PIPE EXTRUSION In pipe extrusion the molten polymer is extruded through an annular die and cooled by passing through a water trough. The processing sequence is shown schematically in Figure 5.

water

cooling trough

Tube die

tube

Figure 5. Schematic diagram of pipe extrusion. Data have been obtained from three factories operating in the Netherlands and producing both PVC and PE pipe and the information from these is detailed below. Note that for PVC pipe, the effects of stabilisers have been ignored. In the calculations all of the weight of the pipe is assumed to be PVC homopolymer. The inputs required to produce and pack 1 kg of PVC pipe are given in Table 49. The gross energy associated with the production of 1 kg of PVC pipe is shown in Table 50 and the corresponding primary fuels are given in Table 51. Table 52 shows these fuels expressed as mass. The water requirements are given in Table 53 and the gross raw materials consumptions are given in Table 54. The gross emissions to air and water are shown in Tables 55 and 56 respectively. The total solid waste generated is shown in Table 57. The relative contributions to gross energy of the different operations are shown in Table 58.

43

Table 49 Inputs to the production and packaging of 1 kg of PVC pipe Input Quantity Process PVC 1.0037 kg Fuel oil 0.6847 MJ Gas oil 0.008 MJ Diesel 0.0445 MJ Propane 0.0030 MJ Lubricating oil 0.0061 MJ Natural gas 0.1975 MJ Electricity 1.7276 MJ Water 14.3500 kg Packaging Wood 0.0250 kg Board 0.0009 kg Steel strapping 0.0012 kg PE film 0.0014 kg PP strapping 0.0005 kg PET film 0.0002 kg Table 50 Gross energy required to produce 1 kg of PVC pipe. Fuel type Fuel prod'n Energy content Energy use Feedstock Total

& delivery of delivered in energy energy

energy fuel transport

(MJ) (MJ) (MJ) (MJ) (MJ)

Electricity 11.27 5.34 0.05 <0.01 16.66

Oil fuels 0.43 6.09 0.25 11.90 18.67

Other fuels 1.79 15.60 0.06 11.68 29.14

Totals 13.50 27.03 0.36 23.58 64.47

44

Table 51 Gross primary fuels required to produce 1 kg of PVC pipe. Fuel type Fuel prod'n Energy content Fuel use Feedstock Total & delivery of delivered in energy energy energy fuel transport (MJ) (MJ) (MJ) (MJ) (MJ) Coal 2.73 3.01 0.01 <0.01 5.74 Oil 0.79 6.33 0.33 11.92 19.37 Gas 4.31 14.99 0.03 11.15 30.47 Hydro 0.43 0.41 <0.01 - 0.85 Nuclear 4.47 2.00 <0.01 - 6.48 Lignite 0.56 0.25 <0.01 - 0.81 Wood - - - 0.42 0.42 Sulphur <0.01 <0.01 <0.01 0.10 0.10 Biomass 0.05 0.02 <0.01 <0.01 0.08 Hydrogen <0.01 0.97 <0.01 - 0.97 Recovered energy <0.01 -1.04 <0.01 - -1.04 Unspecified 0.14 0.08 <0.01 - 0.22 Peat <0.01 <0.01 <0.01 - <0.01 Geothermal <0.01 <0.01 <0.01 - <0.01 Solar <0.01 <0.01 <0.01 - <0.01 Wave/tidal <0.01 <0.01 <0.01 - <0.01 Totals 13.50 27.03 0.36 23.58 64.47

Table 52 Gross primary fuels in mg required to produce 1 kg of PVC pipe. Fuel type Input in mg Crude oil 430,000 Gas/condensate 570,000 Coal 210,000 Metallurgical coal 630 Lignite 54,000 Peat 240 Wood 48,000 Biomass 8,700

Table 53 Gross water requirements to produce 1 kg of PVC pipe. Source Use for Use for Totals

processing cooling

(mg) (mg) (mg)

Public supply 3,700,000 - 3,700,000

River canal 980,000 640,000 1,600,000

Sea 130,000 35,000,000 35,000,000

Unspecified 6,100,000 49,000,000 55,000,000

Well 180,000 9,800 190,000

Totals 11,000,000 85,000,000 96,000,000

45

Table 54 Gross raw materials requirements to produce 1 kg of PVC pipe. Raw material Input in mg

air 260,000

barytes 82

bauxite 450

bentonite 34


chalk (CaCO3) <1

clay 9

Cr 3

dolomite 20

Fe 1,700

feldspar <1

ferromanganese 1

fluorspar 2

granite <1

gravel 6


N2 17,000

Ni <1

O2 5,600

olivine 15

Pb 3

phosphate as P2O5 1


rutile <1

S (bonded) <1


sand (SiO2) 470

shale 9


unspecified <1

Zn <1

46

Table 55 Gross air emissions associated with the production of 1 kg of PVC pipe. Emission From From From From From Totals




Dust 2,900 830 16 190 - 3,900

CO 450 1,900 180 44 - 2,600

CO2 770,000 1,400,000 22,000 31,000 -52,000 2,200,000

SOX 5,900 5,400 120 19 - 11,000

NOX 5,500 6,600 230 74 - 12,000

N2O <1 <1 - <1 - <1

Hydrocarbons 1,200 360 65 1,100 - 2,700

Methane 8,200 2,500 - 370 - 11,000

H2S <1 - - 2 - 2

HCl 71 17 - 66 - 150

Cl2 - - - 2 - 2

HF 4 1 - <1 - 4

Lead(Pb) - <1 - <1 - <1

Metals 1 3 - <1 - 5

F2 - - - <1 - <1


Organo-Cl - - - 37 - 37




CFC/HCFC - - - 1 - 1


HCN - - - <1 - <1

H2SO4 - - - <1 - <1

Hydrogen (H2) 11 - - 300 - 310

Mercury (Hg) - - - <1 - <1

Ammonia (NH3) - - - <1 - <1

CS2 - - - <1 - <1

DCE - - - 340 - 340

VCM - - - 240 - 240

VOC - - - 5 - 5

Cu (process) - - - <1 - <1

Cd (process) - - - <1 - <1

Zn (process) - - - <1 - <1

Sb (process) - - - <1 - <1

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Table 56 Gross water emissions associated with the production of 1 kg of PVC pipe. Emission From From From From Totals fuel fuel transport process production use operations operations (mg) (mg) (mg) (mg) (mg) COD 6 - - 770 780 BOD 4 - - 85 89 Acid (H+) 3 - - 46 49 Dissolved solids 27 - - 2,600 2,600 Hydrocarbons 8 <1 - 19 27 NH4 3 - - 2 4 Suspended solids 66 - - 1,800 1,900 Phenol 4 - - <1 4 Al+++ - - - <1 <1 Ca++ - - - 47 47 Cu+/Cu++ - - - 1 1 Fe++/Fe+++ - - - 5 5 Hg - - - <1 <1 Pb - - - <1 <1 Mg++ - - - 2 2 Na+ - - - 8,300 8,300 K+ - - - 180 180 Ni++ - - - 1 1 Zn++ - - - <1 <1 Other metals 1 - - 64 65 NO3- - - - 1 1 Other nitrogen <1 - - 2 2 BrO3- - - - <1 <1 CrO3 - - - <1 <1 Cl- - - - 39,000 39,000 ClO3- - - - 10 10 CN- - - - <1 <1 F- - - - <1 <1 SO4-- - - - 4,100 4,100 CO3-- - - - 63 63 Phosphate as P2O5 - - - 17 17 AOX - - - <1 <1 TOC - - - 91 91 Arsenic - - - <1 <1 DCE - - - 2 2 VCM - - - 1 1 Detergent/oil - - - 50 50 Dissolved Cl2 - - - 2 2 Organo-chlorine - - - <1 <1 Dissolved organics - - - 1,600 1,600 Other organics - - - 3 3 Sulphur/sulphide - - - 1 1

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Table 57 Gross solid waste associated with the production of 1 kg of PVC pipe. Type From From From From Totals




Mineral 47,000 - - 8,700 56,000


Slags/ash 10,000 1,800 - 1,100 13,000

Inert chemical 1 - - 12,000 12,000


Unspecified 1 - - 140 140


Metals - - - 1,200 1,200




Paper & board - - - 960 960

Plastics - - - 960 960


Wood waste - - - 900 900



Tailings - - - 9 9

Table 58 Relative contributions to the energy required for the production of PVC pipe. Resin production 88.52% Resin delivery 0.65% Processing 9.53% Packaging 1.30% Total 100.00%

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POSTSCRIPT The aim of this report has been to examine some of the techniques that are used to convert polymer resins to usable products. It was not intended to provide a comprehensive coverage of all processes for all polymers but as a means of illustrating some of the more commonly used techniques. The numerical data are thought to be reasonable typical of the expected performance characteristics of 'average' practice but it cannot be emphasised too strongly that these values should not be taken as definitive. Within the conversion industry there are wide variations in practices and these will inevitably influence performance. Well maintained, new machines matched precisely to the continuous production of a single product will always tend to exhibit better performance characteristics than poorly maintained, old machines which have to cope with short runs of a wide range of different products of different sizes.

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