PROGRESS - Europaeippcb.jrc.ec.europa.eu/reference/BREF/LVOC042014.pdf · WORKING DRAFT IN PROGRESS This document is one from the series of foreseen documents listed below (at the

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Best Available Techniques (BAT) Reference Document in the

Large Volume Organic Chemical Industry

Industrial Emissions Directive 2010/75/EU

(Integrated Pollution Prevention and Control)

JOINT RESEARCH CENTRE

Institute for Prospective Technological Studies

Sustainable Production and Consumption Unit

European IPPC Bureau

Draft 1 (April 2014)

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This document is one from the series of foreseen documents listed below (at the time of writing

not all of the documents have been drafted)

Best Available Techniques Reference Document Code

Ceramic Manufacturing Industry CER

Common Waste Water and Waste Gas Treatment/Management Systems in the Chemical

Sector CWW

Emissions from Storage EFS

Energy Efficiency ENE

Ferrous Metals Processing Industry FMP

Food, Drink and Milk Industries FDM

Industrial Cooling Systems ICS

Intensive Rearing of Poultry and Pigs IRPP

Iron and Steel Production IS

Large Combustion Plants LCP

Large Volume Inorganic Chemicals Ammonia, Acids and Fertilisers Industries LVIC-AAF

Large Volume Inorganic Chemicals Solids and Others Industry LVIC-S

Large Volume Organic Chemical Industry LVOC

Management of Tailings and Waste-rock in Mining Activities MTWR

Manufacture of Glass GLS

Manufacture of Organic Fine Chemicals OFC

Non-ferrous Metals Industries NFM

Production of Cement, Lime and Magnesium Oxide CLM

Production of Chlor-alkali CAK

Production of Polymers POL

Production of Pulp, Paper and Board PP

Production of Speciality Inorganic Chemicals SIC

Refining of Mineral Oil and Gas REF

Slaughterhouses and Animals By-products Industries SA

Smitheries and Foundries Industry SF

Surface Treatment of Metals and Plastics STM

Surface Treatment Using Organic Solvents STS

Tanning of Hides and Skins TAN

Textiles Industry TXT

Waste Incineration WI

Waste Treatments Industries WT

Wood and Wood Products Preservation with Chemicals WPC

Wood-based Panels Production WBP

Reference Document

Economics and Cross-media Effects ECM

General Principles of Monitoring MON

Electronic versions of draft and finalised documents are publicly available and can be

downloaded from http://eippcb.jrc.ec.europa.eu

http://eippcb.jrc.ec.europa.eu/

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Colour code:

Yellow: TWG decisions reminders + other tasks to do + various additional comments to TWG

Green: Text to be updated or deleted, according to information still awaited

Text: new text proposed D1

Text: old text removed D1

Red: remaining work for the EIPPCB

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Preface

SH/TS/EIPPCB/LVOC Draft 1 April 2014 i

PREFACE

1. Status of this document

Unless otherwise stated, references to the Directive in this document refer to Directive

2010/75/EU of the European Parliament and the Council on industrial emissions (integrated

pollution prevention and control) (Recast).

This document is a working draft of the European IPPC Bureau (of the Commission's Joint

Research Centre). It is not an official publication of the European Union and does not

necessarily reflect the position of the European Commission.

2. Participants in the information exchange

As required in Article 13(3) of the Directive, the Commission has established a forum to

promote the exchange of information, which is composed of representatives from Member

States, the industries concerned and non-governmental organisations promoting environmental

protection (Commission Decision of 16 May 2011 establishing a forum for the exchange of

information pursuant to Article 13 of the Directive 2010/75/EU on industrial emissions (2011/C

146/03), OJ C 146, 17.05.2011, p. 3).

Forum members have nominated technical experts constituting the technical working group

(TWG) that was the main source of information for drafting this document. The work of the

TWG was led by the European IPPC Bureau (of the Commission's Joint Research Centre).

3. Structure and contents of this document

Chapters 1 and 3 provide general information on the Large Volume Organic Chemicals sector as

a whole and on the industrial processes and techniques used within this sector.

[Note to TWG: TWG members are asked to consider whether it would be better to reverse the

order of Chapters 2 and 3.]

Chapter 2 describes in more detail those processes and techniques which are generally applied

across the sector.

Sections 1 and 2 of Chapter 2 provide general information on the industrial process or processes and on the techniques used in the sector.

Section 3 of Chapter 2 provides data and information concerning the environmental performance of installations in the sector, and in operation at the time of writing, in

terms of current emissions, consumption and nature of raw materials, water

consumption, use of energy and the generation of waste.

Section 4 of Chapter 2 describes in more detail the techniques to prevent or, where this is not practicable, to reduce the environmental impact of installations in the sector that

were considered in determining the BAT. This information includes, where relevant, the

environmental performance levels (e.g. emission and consumption levels) which can be

achieved by using the techniques, the associated monitoring and the costs and the cross-

media issues associated with the techniques.

Section 5 of Chapter 3 presents information on 'emerging techniques' as defined in Article 3(14) of the Directive.

Chapters 4 to 16 describe 13 processes which are illustrative of the Large Volume Organic

Chemicals Sector. Each chapter follows the structure below:

Sections 1 and 2 of Chapters 4 to 16 provide general information on the industrial process or processes and on the techniques used within this part of the sector.

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Preface

ii April 2014 SH/TS/EIPPCB/LVOC Draft 1

Section 3 of Chapters 4 to 16 provides data and information concerning the environmental performance of installations within this part of the sector, and in

operation at the time of writing, in terms of current emissions, consumption and nature

of raw materials, water consumption, use of energy and the generation of waste.

Section 4 of Chapters 4 to 16 describes in more detail the techniques to prevent or, where this is not practicable, to reduce the environmental impact of installations in this

part of the sector that were considered in determining the BAT. This information

includes, where relevant, the environmental performance levels (e.g. emission and

consumption levels) which can be achieved by using the techniques, the associated

monitoring and the costs and the cross-media issues associated with the techniques.

Section 5 of Chapters 4 to 16 presents information on 'emerging techniques' as defined in Article 3(14) of the Directive for this part of the sector.

Chapter 17 presents the BAT conclusions as defined in Article 3(12) of the Directive.

[Note to TWG: In the final version of the BREF, the emerging techniques will probably be

pulled together into a single chapter.]

Concluding remarks and recommendations for future work are presented in Chapter 18.

4. Information sources and the derivation of BAT

This document is based on information collected from a number of sources, in particular

through the TWG that was established specifically for the exchange of information under

Article 13 of the Directive. The information has been collated and assessed by the European

IPPC Bureau (of the Commission's Joint Research Centre) who led the work on determining

BAT, guided by the principles of technical expertise, transparency and neutrality. The work of

the TWG and all other contributors is gratefully acknowledged.

The BAT conclusions have been established through an iterative process involving the

following steps:

identification of the key environmental issues for the sector; examination of the techniques most relevant to address these key issues; identification of the best environmental performance levels, on the basis of the available

data in the European Union and worldwide;

examination of the conditions under which these environmental performance levels were achieved, such as costs, cross-media effects, and the main driving forces involved

in the implementation of the techniques;

selection of the best available techniques (BAT), their associated emission levels (and other environmental performance levels) and the associated monitoring for this sector

according to Article 3(10) of, and Annex III to, the Directive.

Expert judgement by the European IPPC Bureau and the TWG has played a key role in each of

these steps and the way in which the information is presented here.

Where available, economic data have been given together with the descriptions of the

techniques presented in Chapter 2 and Chapters 4 to 16. These data give a rough indication of

the magnitude of the costs and benefits. However, the actual costs and benefits of applying a

technique may depend strongly on the specific situation of the installation concerned, which

cannot be evaluated fully in this document. In the absence of data concerning costs, conclusions

on the economic viability of techniques are drawn from observations on existing installations.

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Preface

SH/TS/EIPPCB/LVOC Draft 1 April 2014 iii

5. Review of BAT reference documents (BREFs)

BAT is a dynamic concept and so the review of BREFs is a continuing process. For example,

new measures and techniques may emerge, science and technologies are continuously

developing and new or emerging processes are being successfully introduced into the industries.

In order to reflect such changes and their consequences for BAT, this document will be

periodically reviewed and, if necessary, updated accordingly.

6. Contact information

All comments and suggestions should be made to the European IPPC Bureau at the Institute for

Prospective Technological Studies at the following address:

European Commission

Joint Research Centre

Institute for Prospective Technological Studies

European IPPC Bureau

Edificio Expo

c/ Inca Garcilaso, 3

E-41092 Seville, Spain

Telephone: +34 95 4488 284

Fax: +34 95 4488 426

E-mail: [email protected]

Internet: http://eippcb.jrc.ec.europa.eu

mailto:[email protected]://eippcb.jrc.ec.europa.eu/

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iv April 2014 SH/TS/EIPPCB/LVOC Draft 1

Best Available Techniques Reference Document in the Large Volume Organic Chemical Industry

PREFACE ........................................................................................................................ I

SCOPE ........................................................................................................................ XXI

1 BACKGROUND INFORMATION ....................................................................... 1

1.1 ECONOMIC TRENDS IN LVOC ........................................................................................ 5

2 GENERIC LVOC PRODUCTION PROCESSES ................................................ 7

2.1 CHEMICAL REACTIONS IN LVOC PRODUCTION ........................................................... 7

2.2 APPLIED PROCESSES AND TECHNIQUES ......................................................................... 9

2.2.1 Oxidation ..................................................................................................................... 9

2.2.2 Halogenation ............................................................................................................... 9

2.2.3 Hydrogenation ........................................................................................................... 10

2.2.4 Esterification ............................................................................................................. 11

2.2.5 Alkylation .................................................................................................................. 12

2.2.6 Sulphonation ............................................................................................................. 12

2.2.7 Dehydrogenation ....................................................................................................... 13

2.2.8 Cracking .................................................................................................................... 13

2.2.9 Hydrolysis ................................................................................................................. 14

2.2.10 Reforming ................................................................................................................. 14

2.2.11 Carbonylation ............................................................................................................ 14

2.2.12 Oxyacetylation .......................................................................................................... 15

2.2.13 Nitration .................................................................................................................... 15

2.2.14 Dehydration ............................................................................................................... 16

2.2.15 Ammonolysis ............................................................................................................ 16

2.2.16 Condensation ............................................................................................................. 16

2.2.17 Dealkylation .............................................................................................................. 17

2.2.18 Ammoxidation .......................................................................................................... 17

2.2.19 Fermentation ............................................................................................................. 17

2.3 CURRENT EMISSION AND CONSUMPTION LEVELS ....................................................... 19

2.3.1 Factors influencing consumption and emissions ....................................................... 19

2.3.2 Emissions to air ......................................................................................................... 21

2.3.3 Emissions to water .................................................................................................... 24

2.3.4 Raw material consumption ........................................................................................ 31

2.3.5 Energy consumption.................................................................................................. 31

2.3.6 Water consumption ................................................................................................... 32

2.3.7 Co-products, by-products and waste generation ....................................................... 32

2.3.8 Emission sources ....................................................................................................... 32

2.3.9 Pollutant types ........................................................................................................... 33

2.4 TECHNIQUES TO CONSIDER IN THE DETERMINATION OF BAT .................................. 34

2.4.1 Management techniques ............................................................................................ 38

2.4.2 Monitoring of emissions ........................................................................................... 38

2.4.3 Waste gas collection systems .................................................................................... 41

2.4.4 Techniques for the treatment of emissions to air ...................................................... 43

2.4.5 Techniques to reduce emissions to water .................................................................. 58

2.4.6 Techniques to reduce raw material consumption ...................................................... 63

2.4.7 Techniques to reduce energy consumption ............................................................... 67

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2.4.8 Techniques to reduce water consumption................................................................. 70

2.4.9 Techniques to reduce waste generation .................................................................... 71

2.4.10 Techniques to reduce odour ...................................................................................... 74

2.4.11 Techniques to reduce noise and vibration ................................................................ 75

2.4.12 Techniques to reduce other than normal operating conditions ................................. 76

2.5 EMERGING TECHNIQUES .............................................................................................. 83

2.5.1 Waste gas treatments ................................................................................................ 83

2.5.2 Waste water treatments ............................................................................................. 84

2.5.3 Waste recovery ......................................................................................................... 84

3 CHEMICALS PRODUCED IN LVOC INSTALLATIONS ............................. 87

3.1 GENERAL INFORMATION .............................................................................................. 87

3.2 APPLIED PROCESSES AND TECHNIQUES ...................................................................... 88

3.2.1 Simple hydrocarbons ................................................................................................ 88

3.2.2 Oxygen-containing hydrocarbons ............................................................................. 90

3.2.3 Sulphurous hydrocarbons ....................................................................................... 113

3.2.4 Nitrogenous hydrocarbons ...................................................................................... 118

3.2.5 Phosphorous-containing hydrocarbons ................................................................... 126

3.2.6 Halogenic hydrocarbons ......................................................................................... 127

3.2.7 Organometallic compounds .................................................................................... 130

3.3 EMERGING TECHNIQUES ............................................................................................ 133

3.3.1 Bio-based LVOCs process routes ........................................................................... 133

3.3.2 Sugar fermentation route ........................................................................................ 134

3.3.3 Sugar thermochemical route ................................................................................... 135

4 LOWER OLEFINS .............................................................................................. 137

4.1 GENERAL INFORMATION ............................................................................................ 137

4.2 APPLIED PROCESSES AND TECHNIQUES .................................................................... 140

4.2.1 Process options ....................................................................................................... 140

4.2.2 Steam cracking process .......................................................................................... 141

4.2.3 Other than normal operating conditions ................................................................. 146

4.2.4 Equipment important for environmental protection ............................................... 148

4.3 CURRENT EMISSION AND CONSUMPTION LEVELS ..................................................... 149

4.3.1 Emissions to air ...................................................................................................... 149

4.3.2 Emissions to water .................................................................................................. 156

4.3.3 Raw material consumption ..................................................................................... 158

4.3.4 Energy consumption ............................................................................................... 160

4.3.5 Water consumption ................................................................................................. 161

4.3.6 Co-products, by-products and waste generation ..................................................... 163

4.4 TECHNIQUES TO CONSIDER IN THE DETERMINATION OF BAT ................................ 166

4.4.1 Techniques to reduce emissions to air .................................................................... 166

4.4.2 Techniques to reduce emissions to water ............................................................... 183

4.4.3 Techniques to reduce raw material consumption ................................................... 189

4.4.4 Techniques to reduce energy consumption ............................................................. 191

4.4.5 Techniques to reduce water consumption............................................................... 193

4.4.6 Techniques to reduce waste generation .................................................................. 194

4.4.7 Techniques to reduce emissions at other than normal operating conditions .......... 197


4.5.1 Olefin metathesis .................................................................................................... 198

4.5.2 SHOP Shell Higher Olefins Process ....................................................................... 198

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4.5.3 Fischer-Tropsch process.......................................................................................... 199

4.5.4 Oxidative coupling of methane ............................................................................... 200

4.5.5 Dehydrogenation of ethane or propane ................................................................... 201

5 ETHANOLAMINES ............................................................................................ 203


5.2 APPLIED PROCESSES AND TECHNIQUES ..................................................................... 205

5.2.1 Process options ........................................................................................................ 205

5.2.2 Reaction of ethylene oxide with ammonia .............................................................. 205

5.2.3 Aqueous process ..................................................................................................... 205

5.2.4 Anhydrous Process .................................................................................................. 206

5.2.5 Other than normal operating conditions .................................................................. 207

5.2.6 Equipment important for environmental protection ................................................ 208


5.3.1 Emissions to air ....................................................................................................... 210


5.3.3 Raw material consumption ...................................................................................... 215

5.3.4 Energy consumption................................................................................................ 215





5.4.2 Reduction of ammonia emissions from the process ................................................ 218

5.4.3 Techniques to reduce emissions to water ................................................................ 222

5.4.4 Techniques to reduce raw material consumption .................................................... 224


5.4.6 Techniques to reduce water consumption ............................................................... 229

5.4.7 Techniques to reduce waste generation ................................................................... 230

5.4.8 Techniques to reduce other than normal operating conditions................................ 231

5.5 EMERGING TECHNIQUES ............................................................................................. 232

5.5.1 Aminonitrile process ............................................................................................... 232

6 TOLUENE DIISOCYNATE (TDI) AND METHYLENEDIPHENYL ISOCYANATE (MDI) ......................................................................................... 233



6.2.1 Process options ........................................................................................................ 236

6.2.2 Basic process steps .................................................................................................. 238




6.3.1 Emissions to air ....................................................................................................... 242









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6.4.4 To use gas phase phosgenation ............................................................................... 273



6.4.7 Techniques to reduce other than normal operating conditions ............................... 280


6.5.1 Phosgene-free process for TDI ............................................................................... 283

6.5.2 Gas phase phosgenation.......................................................................................... 283

6.5.3 Phosgene-free route to MDI ................................................................................... 284

7 ETHYLENE OXIDE AND ETHYLENE GLYCOLS ...................................... 285



7.2.1 Process options ....................................................................................................... 287

7.2.2 Direct oxidation route ............................................................................................. 290




7.3.1 Emissions to air ...................................................................................................... 295













7.5.1 Co-production of DPC and PPG ............................................................................. 325

7.5.2 Catalytic conversion of ethylene oxide................................................................... 325

7.5.3 Biomass gasification ............................................................................................... 326

7.5.4 MEG via dimethyl oxalate ...................................................................................... 326

8 AROMATICS ....................................................................................................... 327



8.2.1 Process options in aromatic complexes .................................................................. 330

8.2.2 Building blocks of the aromatics process ............................................................... 331




8.3.1 Emissions to air ...................................................................................................... 338







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8.4.6 Techniques to consider reducing other than normal operations .............................. 371


8.5.1 Ion Liquid for Aromatic extraction ......................................................................... 374

8.5.2 Membranes for recovery of solvents ....................................................................... 374

8.5.3 Light alkane dehydrogenation technologies ............................................................ 374

8.5.4 Benzene from methane ............................................................................................ 374

8.5.5 Bio-routes to p-Xylene ............................................................................................ 375

9 ACRYLONITRILE ............................................................................................. 377



9.2.1 Process options ........................................................................................................ 378

9.2.2 BP/SOHIO process ................................................................................................. 378




9.3.1 Emissions to air ....................................................................................................... 383






9.3.7 Example plants ........................................................................................................ 388







9.5 BEST AVAILABLE TECHNIQUES CONCLUSIONS .......................................................... 395

9.5.1 Process selection ..................................................................................................... 395

9.5.2 Plant design ............................................................................................................. 395

9.5.3 Air emissions ........................................................................................................... 396

9.5.4 Water emissions ...................................................................................................... 397

9.5.5 By-products and wastes........................................................................................... 397


10 FORMALDEHYDE ............................................................................................. 399



10.2.1 Process options ........................................................................................................ 402

10.2.2 Catalytic oxidation of methanol .............................................................................. 402




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SH/TS/EIPPCB/LVOC Draft 1 April 2014 ix

10.3.1 Emissions to air ...................................................................................................... 409











10.4.6 Techniques to reduce other than normal operations ............................................... 427


10.5.1 High pressure route ................................................................................................. 428

10.5.2 Bio-based formaldehyde ......................................................................................... 428

11 PHENOL ............................................................................................................... 429



11.2.1 Process options ....................................................................................................... 430

11.2.2 Cumene oxidation process ...................................................................................... 430




11.3.1 Emissions to air ...................................................................................................... 433












11.4.6 Techniques to reduce other than normal operating conditions ............................... 460


11.5.1 Direct catalysed oxidation of benzene .................................................................... 462

11.5.2 Oxidation of toluene ............................................................................................... 462

12 ETHYLBENZENE............................................................................................... 465



12.2.1 Process options ....................................................................................................... 467

12.2.2 Alkylation route ...................................................................................................... 468




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12.3.1 Emissions to air ....................................................................................................... 470








12.4.5 Techniques to reduce water consumption ............................................................... 487


12.4.7 Techniques to reduce other than normal operating conditions................................ 492


13 STYRENE FROM ETHYLBENZENE DEHYDROGENATION .................. 495



13.2.1 Process options ........................................................................................................ 497

13.2.2 The dehydrogenation process .................................................................................. 497




13.3.1 Emissions to air ....................................................................................................... 501












13.5.1 Dimerisation of 1,3-butadiene to 4-vinylcyclohexene ............................................ 527

14 CO-PRODUCTION OF STYRENE AND PROPYLENE OXIDE ................. 529



14.2.1 Process options ........................................................................................................ 531

14.2.2 Indirect oxidation process ....................................................................................... 532




14.3.1 Emissions to air ....................................................................................................... 534






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14.4.6 Techniques to consider reducing other operating conditions ................................. 560


14.5.1 Cumene hydroperoxide route to PO ....................................................................... 563

14.5.2 Hydrogen peroxide-based propylene oxidation ...................................................... 563

15 HYDROGEN PEROXIDE .................................................................................. 565



15.2.1 Process options ....................................................................................................... 567

15.2.2 The autoxidation process ........................................................................................ 568




15.3.1 Emissions to air ...................................................................................................... 572












15.4.6 Techniques to consider reducing other operations ................................................. 607


15.5.1 Direct synthesis process to H2O2 ............................................................................ 609

16 ETHYLENE DICHLORIDE AND VINYL CHLORIDE MONOMER ......... 611



16.2.1 Process options ....................................................................................................... 613

16.2.2 Key process step ..................................................................................................... 613




16.3.1 Emissions to air ...................................................................................................... 616






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16.5.1 Ethane-based VCM ................................................................................................. 661

16.5.2 Alternatives to avoid Oxychlorination .................................................................... 661

17 BEST AVAILABLE TECHNIQUES CONCLUSIONS ................................... 663

17.1 SCOPE ........................................................................................................................... 663

17.2 GENERAL CONSIDERATIONS ....................................................................................... 665

17.2.1 Averaging periods and reference conditions for emissions to air ........................... 665

17.2.2 Averaging periods and reference conditions for emissions to water ....................... 666

17.2.3 Definitions and acronyms ....................................................................................... 666

17.3 GENERAL BAT CONCLUSIONS .................................................................................... 668

17.3.1 Environmental management systems ...................................................................... 668

17.3.2 BAT conclusions on monitoring ............................................................................. 668

17.3.3 BAT conclusions on emissions to air ...................................................................... 670

17.3.4 BAT conclusion on emissions to water ................................................................... 677

17.3.5 BAT conclusions on raw material consumption ..................................................... 678

17.3.6 BAT conclusions on energy efficiency ................................................................... 679

17.3.7 BAT conclusions on water consumption ................................................................ 679

17.3.8 BAT conclusion on residues and waste .................................................................. 680

17.3.9 BAT conclusions on odour...................................................................................... 681

17.3.10 BAT conclusions on noise emissions ...................................................................... 681

17.3.11 BAT conclusions on other than normal operating conditions ................................. 681

17.4 BAT CONCLUSIONS FOR LOWER OLEFIN PRODUCTION ............................................ 682


17.4.2 BAT conclusions on emissions to water ................................................................. 685

17.4.3 BAT conclusion on waste generation and product recovery ................................... 688

17.5 BAT CONCLUSIONS FOR ETHANOLAMINE PRODUCTION .......................................... 689



17.5.3 BAT conclusions on raw material consumption ..................................................... 690

17.6 BAT CONCLUSIONS FOR TDI AND MDI PRODUCTION .............................................. 692



17.6.3 BAT conclusions on energy efficiency ................................................................... 698

17.6.4 BAT conclusions on waste generation and product recovery ................................. 698

17.7 BAT CONCLUSIONS FOR ETHYLENE OXIDE AND ETHYLENE GLYCOL PRODUCTION700



17.7.3 BAT conclusion on raw material consumption ....................................................... 703

17.7.4 BAT conclusions on waste generation and product recovery ................................. 704

17.8 BAT CONCLUSIONS FOR AROMATICS PRODUCTION ................................................. 705


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17.8.3 BAT conclusion on energy efficiency .................................................................... 707

17.8.4 BAT conclusions on waste generation and product recovery................................. 708

17.8.5 BAT conclusions on other than normal operating conditions ................................ 709

17.9 BAT CONCLUSIONS FOR FORMALDEHYDE PRODUCTION ......................................... 710

17.9.1 BAT conclusions on emissions to air ..................................................................... 710

17.9.2 BAT conclusion on emissions to water .................................................................. 711

17.9.3 BAT conclusions on waste generation ................................................................... 711

17.10 BAT CONCLUSIONS FOR PHENOL PRODUCTION ....................................................... 713



17.10.3 BAT conclusion on waste generation and product recovery .................................. 715

17.10.4 BAT conclusion on other than normal operating conditions .................................. 715

17.11 BAT CONCLUSIONS FOR ETHYLBENZENE PRODUCTION .......................................... 716




17.12 BAT CONCLUSIONS FOR STYRENE PRODUCTION FROM ETHYLBENZENE DEHYDROGENATION ................................................................................................... 718



17.12.3 BAT conclusions on energy efficiency................................................................... 719


17.13 BAT CONCLUSIONS FOR CO-PRODUCTION OF STYRENE AND PROPYLENE OXIDE .. 721




17.13.4 BAT conclusion on other than normal operating conditions .................................. 725

17.14 BAT CONCLUSIONS FOR HYDROGEN PEROXIDE PRODUCTION ................................ 726




17.14.4 BAT conclusions on other than normal operating conditions ................................ 730

17.15 BAT CONCLUSIONS FOR ETHYLENE DICHLORIDE AND VINYL CHLORIDE PRODUCTION ............................................................................................................... 731




18 CONCLUDING REMARKS AND RECOMMENDATIONS FOR FUTURE WORK................................................................................................................... 741

18.1 REVIEW OF THE INFORMATION EXCHANGE .............................................................. 741

18.1.1 Timing of the review process ................................................................................. 741

18.1.2 Degree of consensus reached during the information exchange............................. 741

18.1.3 Consultation of the Forum and subsequent formal adoption procedure of the BAT Conclusions ............................................................................................................ 741

18.2 RECOMMENDATIONS FOR FUTURE WORK ................................................................. 741

18.2.1 Suggested topics for future R&D work .................................................................. 741

REFERENCES ............................................................................................................ 743

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GLOSSARY ................................................................................................................. 753

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List of Figures Figure 1.1: Structure of industrial organic chemistry ............................................................................... 1 Figure 1.2: Interface between petrochemical and hydrocarbon industries ............................................... 2 Figure 1.3: Pathways in the organic chemistry industry ......................................................................... 3 Figure 2.1: Block flow diagram of a chemical oxidation system ........................................................... 61 Figure 3.1: Alkylation of benzene with propene and distillation to purify cumene ............................... 89 Figure 3.2: Tran esterification of fatty acids from vegetable oils or animal fats .................................. 107 Figure 4.1: Typical ethylene steam cracker furnace ............................................................................. 142 Figure 4.2: Process flow diagram for lower olefin production by steam cracking with front-end

demethaniser ...................................................................................................................... 143 Figure 4.3: Waterfall curve of NOx emissions from steam cracker furnaces. ...................................... 150 Figure 4.4: Histogram chart showing the distribution of NOX emissions ............................................ 171 Figure 4.5: Boxplot type chart of NOX emissions form the cracker furnaces ...................................... 171 Figure 4.6: NOx emissions with application of a combination of the relevant techniques .................. 172 Figure 4.7: Effect of SCR to reduction of NOx emissions from the cracker furnaces ......................... 173 Figure 4.8: Boxplot chart of NOX emissions from cracker furnaces with and without SCR systems .. 174 Figure 4.9: CO emissions from steam cracker furnaces ....................................................................... 175 Figure 5.1: Flow chart showing process steps in production of ethanolamines by the aqueous route . 205 Figure 5.2: Flow chart showing process steps in production of ethanolamines by the anhydrous route

........................................................................................................................................... 206 Figure 6.1: MDI and TDI routes with respect to other Large Volume chemical processes ................. 236 Figure 6.2: Block flow diagram of a TDI manufacturing process ........................................................ 242 Figure 6.3: Block flow diagram of a MDI manufacturing process....................................................... 242 Figure 6.4: US EPA block flow diagram section of a TDI plant .......................................................... 255 Figure 6.5: US EPA block flow diagram on vent treatment system ..................................................... 256 Figure 6.6: Block flow diagram of chemical oxidation system ............................................................ 269 Figure 7.1: Process flow diagram for ethylene glycol production........................................................ 289 Figure 7.2: Process flow diagram for ethylene oxide production ......................................................... 290 Figure 7.3: Inert purge in a block flow diagram of an EO plant .......................................................... 296 Figure 7.4: CO2 purge in a block flow diagram of an EO plant ........................................................... 297 Figure 7.5: Fractionation vent in a block flow diagram of an EG plant ............................................... 298 Figure 7.6: Recycle water purge in a block flow diagram of an EG plant ........................................... 300 Figure 7.7: Water purge in a block flow diagram of an EG plant ........................................................ 301 Figure 8.1: Block flow diagram of basic pygas complex ..................................................................... 330 Figure 8.2: Block flow diagram of standard reformate complex.......................................................... 330 Figure 8.3: Block flow diagrams with similar emission types ............................................................. 335 Figure 9.1: Process flow diagram for acrylonitrile production ............................................................ 378 Figure 10.1: Process flow diagram for formaldehyde production using the silver oxide process (total

methanol conversion) ......................................................................................................... 404 Figure 10.2: Process flow diagram for formaldehyde production using the silver oxide process (partial

methanol conversion) ......................................................................................................... 404 Figure 10.3: Process flow diagram for formaldehyde production using the metal oxide process .......... 406 Figure 11.1: Phenol production process block flow diagram ................................................................. 433 Figure 11.2: Low pressure oxidation process block flow diagram ......................................................... 444 Figure 11.3: VOC emissions downstream of adsorber systems in hydrogen peroxide production ........ 445 Figure 11.4: Ion exchange chamber ...................................................................................................... 451 Figure 11.5: Sodium Phenate + Decanter ............................................................................................... 451 Figure 11.6: Diamine salt ....................................................................................................................... 451 Figure 11.7: Block flow diagram of phenol recovery set-up .................................................................. 454 Figure 12.1 EB manufacturing process block flow diagram ................................................................. 470 Figure 12.2: Process flow diagram for AlCl3 process ........................................................................... 483 Figure 13.1: Block flow diagram of EB dehydrogenation process ........................................................ 501 Figure 14.1: SMPO process block flow diagram ................................................................................... 534 Figure 14.2 Example of SMPO manufacturing process covering all air emissions .............................. 544 Figure 15.1: Block flow diagram of a hydrogen peroxide manufacturing process ................................ 572 Figure 16.1: Block flow diagram of a VCM manufacturing process ..................................................... 616

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List of Tables Table 2.1: Unit processes used in the manufacture of 140 organic compounds ...................................... 7 Table 2.2: Unit processes used in organic chemical production .............................................................. 8 Table 2.3: Emissions and abatement techniques of LVOC production installations 2011 revision ...... 27 Table 2.4: Information for each technique ............................................................................................ 35 Table 2.5: Techniques to reduce emissions from thermal oxidisers ...................................................... 50 Table 2.6: Holistic approach to waste water management at chemical sites ......................................... 59 Table 3.1: Oxygenated organics with European production capacities in excess of 100 kt/yr .............. 91 Table 3.2: Implementation of N2O abatement options at European adipic acid plants ....................... 104 Table 3.3: Summary of the cost of N2O abatement from adipic acid plants ........................................ 104 Table 3.4: Quantification of waste water arisings from oxygenated processes ................................... 112 Table 3.5: Non-biological treatment techniques for oxygenated process waste waters ...................... 113 Table 3.6: Nitrogenated organics with European production capacities in excess of 100 kt/yr .......... 119 Table 3.7: Quantification of waste water arisings from nitrogenated processes ................................. 126 Table 3.8: Non-biological treatment techniques for nitrogenated process waste waters ..................... 126 Table 3.9: Halogenated organics with European production capacities in excess of 100 kt/yr ........... 127 Table 3.10: Comparison of halogenating agents ................................................................................... 128 Table 3.11: Quantification of waste water arisings from halogenated processes .................................. 130 Table 3.12: Non-biological treatment techniques for halogenated process waste waters ...................... 130 Table 3.13: Key process units and releases in lead compound production ........................................... 131 Table 3.14: Main process steps in the production of n-butyllithium ..................................................... 132 Table 3.15: Production of organo-magnesium compounds ................................................................... 132 Table 3.16 Global market projection for platforms and fine chemicals (1) by bio based process routes

............................................................................................................................................ 133 Table 3.17 Predicted North American markets for some high growth chemical intermediates in 2020

............................................................................................................................................ 133 Table 4.1: Producers of lower olefins in the EU ................................................................................. 138 Table 4.2: Product yields (as %) for different feedstocks.................................................................... 146 Table 4.3: Emissions to air from steam cracker furnaces* .................................................................. 149 Table 4.4: Use of different feedstock types in lower olefins production ............................................. 151 Table 4.5: Ammonia slip from SCR (with half hourly averaging periods) ......................................... 153 Table 4.6: Feedstock characterisation (breakdown of the data reported by the plants, representing

averages over a year) .......................................................................................................... 153 Table 4.7: Emissions from hydrogenation catalyst regeneration furnaces .......................................... 156 Table 4.8: Use of hydrogen coming from the cracker ......................................................................... 160 Table 4.9: Methane from cracker ........................................................................................................ 163 Table 4.10: How pyrolysis oils and pyrolysis gasoline are handled ...................................................... 164 Table 4.11: Monitoring of NOX emissions carried out in lower olefin steam crackers in the EU ......... 167 Table 4.12: Coke Prevention and abatement techniques and number of sites that reported using these

techniques ........................................................................................................................... 176 Table 4.13: Dust emission data measured during decoking .................................................................. 177 Table 4.14: Techniques used by LO operators to manage fugitive VOC emissions ............................. 183 Table 4.15: How pyrolysis oils and pyrolysis gasoline are handled ...................................................... 194 Table 4.16: How the decoking sludge handled ...................................................................................... 196 Table 5.1: European producers of ethanolamines................................................................................ 203 Table 5.2: Data on emissions to water ................................................................................................ 213 Table 6.1: European producers of TDI and MDI ................................................................................ 234 Table 6.2: Example values of emissions from nitration to air ............................................................. 243 Table 6.3: Example values of emissions from hydrogenation to air.................................................... 243 Table 6.4: Example values of emissions to air from phosgenation ..................................................... 244 Table 6.5: Example of a Polish TDI plant's ELVs for overall installation (75 kt/y) ........................... 245 Table 6.6: Example of a German TDI plant's ELVs for shared incinerator ........................................ 245 Table 6.7: Example of a Spanish MDI/TDI plant's ELVs for shared incinerator ................................ 245 Table 6.8: Example values of emissions to air from shared vent treatment systems ........................... 245 Table 6.9: Emission limit values in a MDI plant in Portugal .............................................................. 246 Table 6.10: Limit values from a Polish TDI installation upstream of WWT unit ................................. 248 Table 6.11 Example values of emissions to water ............................................................................... 250 Table 6.12: Usages of a MDI plant ....................................................................................................... 250 Table 6.13: Energy usage in 1 kg of MDI plant .................................................................................... 251 Table 6.14: MDI Plant No.1 .................................................................................................................. 260 Table 6.15: MDI Plant No.2 .................................................................................................................. 261

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Table 6.16: Example of Dutch MDI plant emission values from end-of-pipe device........................... 262 Table 6.17: Chemical oxidation performance ....................................................................................... 269 Table 6.18: MDI streams that are treated in incinerator of Portuguese installation .............................. 280 Table 7.1: European producers of ethylene oxide and ethylene glycol ............................................... 286 Table 7.2: Specific air emissions from EO ......................................................................................... 295 Table 7.3: Specific air emissions from EO ......................................................................................... 295 Table 7.4: Specific air emissions from EO processes ......................................................................... 297 Table 7.5: Monitoring methods - emissions to air .............................................................................. 298 Table 7.6: Raw materials consumption of ethylene oxide / ethylene glycols processes ..................... 302 Table 7.7: Emissions from the 2013 EIPPCB questionnaire .............................................................. 311 Table 8.1: European producers of aromatics ...................................................................................... 328 Table 8.2: Energy supply-related emissions from BB1 type of units (1) ............................................ 339 Table 8.3: Energy supply-related emissions from BB2 units.............................................................. 339 Table 8.4: Fugitive emissions data in BB2 units (1) ............................................................................ 340 Table 8.5: Combustion-related emission data in BB3 units. ............................................................... 340 Table 8.6: Fugitive emissions data in BB3 units (1). ........................................................................... 340 Table 8.7: Combustion related emission data in BB4 units. ............................................................... 341 Table 8.8: Energy usage ...................................................................................................................... 347 Table 8.9: Other values from literature on energy usage .................................................................... 347 Table 8.10: Example values from EIPPCB questionnaires ................................................................... 349 Table 8.11: Other products from aromatic units ................................................................................... 350 Table 8.12: Emission to air from BB1 units application of techniques ............................................. 355 Table 8.13: Emission to air from BB2 units application of techniques ............................................. 356 Table 8.14: Emission to air from BB3 units application of techniques ............................................. 357 Table 8.15: Emission to air from BB4 units application of techniques ............................................. 357 Table 8.16: Emission to water from BB1 units application of techniques ......................................... 359 Table 8.17: Emission to water from BB2 units application of techniques ......................................... 359 Table 8.18: Emission to water from BB3 units application of techniques ......................................... 360 Table 8.19: Gaseous effluents during catalyst regeneration in selective hydrogenation ....................... 372 Table 9.1: European producers of acrylonitrile................................................................................... 377 Table 9.2: Reaction yields from acrylonitrile catalysts ...................................................................... 382 Table 9.3: European absorber vent concentration ranges before and after treatment ........................ 383 Table 9.4: Emissions from acrylonitrile storage and han

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