Reference Document on Best Available Techniques for the

7,41
MB Manufacture of Organic Fine Chemicals

456
stron

6062
ID JRC-IPTS Instituto de Prospectiva Tecnológica (IPTS)

2006
rok

EXECUTIVE SUMMARYI

PREFACEXI

SCOPE . XXVII

1 GENERAL INFORMATION. 1

1.1 The sector 1

1.2 Environmental issues 4

1.3 Some products 5

1.3.1 Organic dyes and pigments 5

1.3.1.1 Overview .5

1.3.1.2 Pigments 6

1.3.1.3 Economics .7

1.3.2 Active pharmaceutical ingredients (APIs) 8

1.3.2.1 Overview .8

1.3.2.2 Legal requirements and process modifications .8

1.3.2.3 Economics .9

1.3.3 Vitamins 9

1.3.4 Biocides and plant health products. 10

1.3.4.1 Overview .10

1.3.4.2 Process modifications in manufacturing crop protection agents .11

1.3.4.3 Economics of crop protection .12

1.3.5 Fragrances and flavours 13

1.3.6 Optical brighteners . 14

1.3.7 Flame-retardants. 15

1.3.8 Plasticisers. 16

1.3.9 Explosives 17

2 APPLIED PROCESSES AND TECHNIQUES 19

2.1 Conception: unit processes and operations . 19

2.1.1 Intermediates 20

2.1.2 Isomers and by-products 21

2.2 Multipurpose plants 22

2.3 Equipment and unit operations . 24

2.3.1 Reactors. 24

2.3.1.1 Liquid addition to reactors 25

2.3.2 Equipment and operations for product work-up. 25

2.3.2.1 Drying25

2.3.2.2 Liquid-solid separation .26

2.3.2.3 Distillation .26

2.3.2.4 Liquid-liquid extraction 26

2.3.3 Cooling 27

2.3.4 Cleaning . 27

2.3.5 Energy supply. 28

2.3.6 Vacuum systems. 29

2.3.7 Recovery/abatement of exhaust gases 30

2.3.8 Recovery/abatement applied to waste water streams . 31

2.3.9 Groundwater protection and fire fighting water . 32

2.3.10 Solvent recovery 33

2.4 Site management and monitoring . 34

2.4.1 Emission inventories and monitoring. 34

2.4.2 Overview to sources and parameters/pollutants . 35

2.4.2.1 Waste gas emissions .35

2.4.2.2 Solvents and volatile organic compounds.36

2.4.2.3 Waste water emissions37

2.4.2.4 Biodegradability and elimination of organic compounds38

2.5 Unit processes and connected operations 40

2.5.1 N-acylation.40

2.5.2 Alkylation with alkyl halides 41

2.5.3 Condensation 42

2.5.4 Diazotisation and azo coupling.43

2.5.5 Esterification45

2.5.6 Halogenation48

2.5.7 Nitration.51

2.5.8 Manufacture of nitrated alcohols 53

2.5.9 Oxidation with inorganic agents .54

2.5.10 Phosgenation 55

2.5.11 Reduction of aromatic nitro compounds.56

2.5.11.1 Catalytic reduction with hydrogen56

2.5.11.2 Reduction with iron 57

2.5.11.3 Alkali sulphide reduction58

2.5.11.4 Product work-up .58

2.5.12 Sulphonation59

2.5.13 Sulphonation with SO3 .61

2.5.14 Sulphochlorination with chlorosulphonic acid .63

2.5.15 Wittig reaction65

2.5.16 Processes involving heavy metals 66

2.6 Fermentation .68

2.6.1 Operations68

2.6.2 Environmental issues 70

2.7 Associated activities72

2.7.1 Formulation72

2.7.2 Extraction from natural materials .73

3 CURRENT EMISSION AND CONSUMPTION LEVELS .75

3.1 Emissions to air .75

3.1.1 VOC emissions: overview 75

3.1.2 Concentration values and DeNOX efficiencies .76

3.1.3 Mass flows 79

3.2 Waste water82

3.2.1 Reported COD and BOD5 emissions and elimination efficiencies .82

3.2.2 Reported emissions for inorganic parameters and related elimination efficiencies 85

3.2.3 Reported emission values for AOX and toxicities 87

3.3 Waste88

4 TECHNIQUES TO CONSIDER IN THE DETERMINATION OF BAT89

4.1 Prevention of environmental impact .90

4.1.1 Green chemistry90

4.1.2 Integration of EHS considerations into process development.92

4.1.3 Example for a solvent selection guide 94

4.1.4 Examples for alternative synthesis and reaction conditions98

4.1.4.1 Sulphonation with SO3 in gas-liquid reaction.98

4.1.4.2 Dry acetylation of a naphthylamine sulphonic acid 99

4.1.4.3 Recycling instead of treatment/disposal of TPPO.100

4.1.4.4 Enzymatic processes versus chemical processes.103

4.1.4.5 Catalytic reduction105

4.1.4.6 Microstructured reactor systems .106

4.1.4.7 Reactions in ionic liquids108

4.1.4.8 Cryogenic reactions 110

4.1.4.9 Reactions in supercritical CO2 111

4.1.4.10 Substitution of butyllithium113

4.1.5 Extraction from natural products 114

4.1.5.1 Extraction from natural products with liquid CO2 114

4.1.5.2 Countercurrent band extraction.115

4.1.5.3 Enabling the re-use of residual plant material from extraction .116

4.1.6 Safety assessment .117

4.1.6.1 Physico-chemical safety assessment of chemical reactions 117

4.1.6.2 About the prevention of runaway reactions 122

4.1.6.3 Useful links and further information.123

4.2 Minimisation of environmental impacts124

4.2.1 A “state of the art” multipurpose plant .124

4.2.2 Site assessment before process launch . 126

4.2.3 Precautions in the production of herbicides . 128

4.2.4 Improvement of “letter acid” production 130

4.2.5 Water-free vacuum generation . 132

4.2.6 Liquid ring vacuum pumps using solvents as the ring medium 134

4.2.7 Closed cycle liquid ring vacuum pumps. 136

4.2.8 Pigging systems 137

4.2.9 Indirect cooling 140

4.2.10 Pinch methodology 141

4.2.11 Energetically coupled distillation. 144

4.2.12 Optimised equipment cleaning (1) . 146

4.2.13 Optimised equipment cleaning (2) . 147

4.2.14 Minimisation of VOC emissions (1) 148

4.2.15 Minimisation of VOC emissions (2) 149

4.2.16 Airtightness of vessels . 151

4.2.17 Shock inertisation of vessels 152

4.2.18 Liquid addition into vessels . 154

4.2.19 Solid-liquid separation in closed systems 155

4.2.20 Minimisation of exhaust gas volume flows from distillation. 156

4.2.21 Segregation of waste water streams . 158

4.2.22 Countercurrent product washing 160

4.2.23 Example for reaction control: azo coupling . 162

4.2.24 Avoidance of mother liquors with high salt contents. 163

4.2.25 Reactive extraction. 165

4.2.26 Use of pressure permeation in dye manufacture 166

4.2.27 Ground protection 168

4.2.28 Retention of fire fighting and contaminated surface water 170

4.2.29 Example: training of phosgenation operators. 171

4.2.30 Example: Handling of phosgene 173

4.3 Management and treatment of waste streams . 175