LUFTSCHADSTOFFE ... 397 A. Dutch classification for air emissions
... 397 A. Niederländische Einstufung für luftseitige
Emissionen ... 397 B. UK categorisation of Volatile Organic
Compounds... 416
.B. Britische Einteilung für Flüchtige Organische Verbindungen ... 416
Herstellung organischer Grundchemikalien xxxix 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 chemical industry ...3 Figure 1.4: Cycle of cash cost margin in the basic petrochemicals industry ...5 Figure 2.1: Schematic production of Large Volume Organic Chemicals ...7 Figure 5.1: Abfallminimierungstechniken ...87 Figure 5.2: Anwendbarkeit von Minderungsstechniken in Abhängigkeit von Massenstrom und
Konzentration der VOCs [Environment Agency (E&W), 1999 #6]...103 Figure 7.1: Uses of ethylene ...143 Figure 7.2: Price fluctuations of Lower Olefin feedstock and products ...147 Figure 7.3: Production costs curve for ethylene ...148 Figure 7.4: Ethylene and butadiene production costs trend ...149 Figure 7.5: Typical block flow diagram for a front-end de-methaniser sequence ...151 Figure 7.6: Typical cracking furnace configuration...152 Figure 7.7: Major profiles for a typical naphtha pyrolysis coil...157 Figure 7.8: Extractive distillation of butadiene with NMP...159 Figure 7.9: Age distribution of European crackers ...163 Figure 7.10: Cracker energy consumption (per tonne of ethylene and high value (HV) products) ...171 Figure 7.11: Carbon dioxide emissions (per tonne of ethylene and high value (HV) products)...172 Figure 7.12: Energy consumption and plant age...172 Figure 7.13: Energy consumption and plant size...172 Figure 8.1: Uses of benzene...195 Figure 8.2: Uses of toluene...196 Figure 8.3: Uses of xylenes ...196 Figure 8.4: Price trend for European spot prices of benzene (1993 - 1998) ...198 Figure 8.5: Price trend for European spot prices of paraxylene (1993 - 1998)...199 Figure 8.6: Benzene production from pygas using extractive distillation...204 Figure 8.7: Production of benzene and para-xylene from reformate ...205 Figure 8.8: Cyclohexane production...206 Figure 9.1: Ethylene oxide derivatives ...221 Figure 9.2: Ethylene oxide and ethylene glycol cash cost margin curve ...224 Figure 9.3: Schematic ethylene oxide / ethylene glycol process with pure oxygen feed...226 Figure 9.4: Schematic ethylene oxide / ethylene glycol process with air feed ...227 Figure 9.5: Impact of catalyst selectivity on raw material consumption ...231 Figure 9.6: Impact of catalyst selectivity on carbon dioxide production ...231 Figure 9.7: Impact of catalyst selectivity on ‘heat of reaction’ produced...232 Figure 10.1: Schematic of silver process ...249 Figure 10.2: Schematic of partial methanol conversion in the silver process...251 Figure 10.3: Schematic of oxide process ...251 Figure 11.1: Uses of acrylonitrile in Europe...267 Figure 11.2: Acrylonitrile demand and production capacity in the world and Europe ...268 Figure 11.3: Typical production costs of acrylonitrile in 1998...269 Figure 11.4: Acrylonitrile cash cost margin history ...269 Figure 11.5: The BP/SOHIO acrylonitrile process ...270 Figure 12.1: Cash cost margins for EDC and VCM in Western Europe ...292 Figure 12.2: Balanced production of EDC and VCM...294 Figure 13.1: The chemistry of TDI production...326 Figure 13.2: A schematic TDI production sequence...326 Figure 13.3: Waste gas and waste water from the manufacture of DNT ...327 Figure 13.4: Waste gas and waste water from the manufacture of TDA...328 Figure 13.5: Waste gas and waster water from the manufacture of TDI ...329 Abbildung 14.1: Gantt-Diagramm für das Arbeitsprogramm zur Erstellung des BVT-Merkblatts zu den organischen Grundchemikalien ...341
xl Herstellung organischer Grundchemikalien List of tables
Table 2.1: Unit processes used in the manufacture of 140 organic compounds... 8 Table 2.2: Unit processes used in organic chemical production... 9 Table 2.3: Unit operations used in the manufacture of 140 organic compounds... 16 Table 2.4: Applications of some selected separation techniques... 17 Table 3.1: Lower Olefin products with European production capacities in excess of 100 kt/yr ... 29 Table 3.2: Quantification of waste water arisings from olefin processes ... 30 Table 3.3: Treatment techniques for olefin process waste waters (excluding biological treatment) ... 30 Table 3.4: Aromatic products with European production capacities in excess of 100 kt/yr... 31 Table 3.5: Quantification of waste water arisings from aromatic processes ... 33 Table 3.6: Non-biological treatment techniques for aromatic process waste waters... 33 Table 3.7: Oxygenated organics with European production capacities in excess of 100 kt/yr... 34 Table 3.8: Implementation of N2O abatement options at European adipic acid plants ... 44 Table 3.9: Summary of the cost of N2O abatement from adipic acid plants... 44 Table 3.10: Quantification of waste water arisings from oxygenated processes ... 50 Table 3.11: Non-biological treatment techniques for oxygenated process waste waters ... 50 Table 3.12: Nitrogenated organics with European production capacities in excess of 100 kt/yr ... 51 Table 3.13: Quantification of waste water arisings from nitrogenated processes ... 58 Table 3.14: Non-biological treatment techniques for nitrogenated process waste waters... 58 Table 3.15: Halogenated organics with European production capacities in excess of 100 kt/yr... 59 Table 3.16: Comparison of halogenating agents ... 60 Table 3.17: Quantification of waste water arisings from halogenated processes ... 61 Table 3.18: Non-biological treatment techniques for halogenated process waste waters... 61 Table 3.19: Key process units and releases in lead compound production ... 67 Table 3.20: Main process steps in the production of n-butyllithium ... 68 Table 3.21: Production of organo-magnesium compounds... 68 Tabelle 5.1: Nutzen durch die Vermeidung von Umweltverschmutzung... 86 Tabelle 5.2: Grundsätze der Grünen Chemie ... 88 Tabelle 5.3: Praktische Beispiele für prozessintegrierte Maßnahmen für neue und bestehende LVOC-Anlagen99
Tabelle 5.4: Beispiele von Techniken zur Verminderung von Emissionen in die Luft in der LVOC-Industrie [InfoMil, 2000
#83] ... 100
Tabelle 5.5: Zusammenfassung der Stärken und Schwächen von Techniken zur Minderung von VOC [Environment Agency (E&W), 1999 #6] ... 102
Tabelle 5.6: Kosten der Verbrennung oder Adsorption von VOC ... 103 Tabelle 5.7: Kosten der Verbrennung oder Adsorption in Abhängigkeit von der Prozessaufgabe ... 104 Tabelle 5.8: Mit den besten verfügbaren Techniken verbundene Benchmark-Werte von GB... 104 Tabelle 5.9: Kosten der Sicherheitsmaßnahmen für Lagerung und Transport von VOCs ... 106 Tabelle 5.10: Hierarchie von Primärmaßnahmen zur Minimierung von Verlusten aus der Lagerung... 106 Tabelle 5.11: Durchschnittliche US-EPA-Emissionsfaktoren... 110 Tabelle 5.12: Kosten der Stickoxidvermeidung ... 114 Tabelle 5.13: Mit BAT verbundene Emissionswerte ... 115 Tabelle 5.14: Medienübergreifende Emissionen aus Abwasserbehandlungsanlagen [InfoMil, 2000 #83]119 Tabelle 5.15: Kosten der Behandlung eines organisch hoch belasteten Abwassers... 120 Tabelle 5.16: Kosten der Behandlung eines halogenhaltigen Abwassers... 120 Tabelle 5.17: Zielwerte für externen industriellen Lärm aus neuen und bestehenden Anlagen ... 124 Tabelle 5.18: Vergleich von Aufstellungs- und Anschlusskosten... 128
Tabelle 5.19: Zusätzlich zu den Grundkosten einer Umweltschutz-Investition erforderliche Kapitalkosten [InfoMil, 2000
#83] ... 128 Tabelle 6.1: BVT-assozierte Werte für die Rückgewinnung / Verminderung von VOC ... 137 Tabelle 6.2: BVT-assoziierte Werte für die Verminderung anderer LVOC-Luftschadstoffe... 138
Tabelle 6.3: Luftemissionswerte, die mit den BVT für Prozessabgase in der LVOC-Industrie verbunden werden 139 Tabelle 6.4: BVT-Werte für Abwasser ... 141
Table 7.1: Location of ethylene plants in the European Union and wider Europe ... 145 Table 7.2: Ethylene plant investment costs for different feedstocks ... 146 Table 7.3: Cash costs of production for Lower Olefins - West European leader plants... 147 Table 7.4: Product yields (as %) for different feedstocks... 154 Table 7.5: Principle emissions from Lower Olefin processes ... 163 Table 7.6: CEFIC survey response on CO and NOx emissions ... 164 Table 7.7: Effluent pollutants and their sources ... 167 Table 7.8: CEFIC survey results for total aqueous effluent before and after treatment ... 169 Table 7.9: Survey response on arisings of catalyst / desiccants, organic sludges and coke ... 170 Table 7.10: Energy consumption with different feedstocks ... 171
Herstellung organischer Grundchemikalien xla Table 7.11: Air emissions from three Dutch steam crackers in 1998 ...173
Table 7.12: Waste water emissions from three Dutch steam crackers in 1998...173 Table 7.13: Efficiency of central WWTP treating effluent from two Dutch crackers ...173 Table 7.14: Emission / consumption data for German steam crackers ...174 Table 7.15: 1998 emissions from a Swedish ethylene cracker ...175 Tabelle 7.16: Hauptquellen und Zusammensetzung der luftseitigen Emissionen [CEFIC, 2000 #111]..176
Tabelle 7.17: Kosten von NOx-Minderungstechniken für neue und für nachgerüstete bestehende Öfen [CEFIC, 2000 #111]
...179
Tabelle 7.18: Emissionsfaktoren, Investitionen, Betriebskosten und Emissionsminderung bei Steamcrackern [Rentz, 1999
#114]...184 Tabelle 7.19: BVT-assoziierte Werte für gasbefeuerte Öfen...190 Tabelle 7.20: BVT-assoziierte Werte für den Ablauf einer zentralen Abwasserbehandlungsanlage...192 Table 8.1: European aromatic production sites...197 Table 8.2: Location of EU aromatics plants ...197 Table 8.3: Aromatics cost indices 1993 - 99...199 Table 8.4: Typical unit operations for aromatic recovery...200 Table 8.5: Summary of typical processes for the production of aromatics...203 Table 8.6: Typical consumption and production performances from aromatics processes ...208 Table 8.7: Emission sources and substances from various aromatics plants ...209 Table 8.8: Combustion emissions to air from aromatics processes (in kg/t feedstock) ...209 Table 8.9: Emissions to air ...210 Table 8.10: Emissions to water from two Dutch aromatics processes...211 Table 8.11: Waste arisings from two Dutch aromatics processes...212 Table 9.1: European ethylene oxide production sites ...222 Table 9.2: Cash costs of production for ethylene oxide and ethylene glycols ...223 Table 9.3: Difference between leader and laggard cash costs...223 Table 9.4: Raw materials consumption of ethylene oxide / ethylene glycols processes...232 Table 9.5: VOC arisings from ethylene oxide plants...233 Table 9.6: Carbon dioxide removal vent before and after treatment ...233 Table 9.7: Inerts vent before and after treatment ...234 Table 9.8: Emissions from ethylene oxide plants in Germany ...236 Table 9.9: Emissions to air in 1998 from two ethylene oxide plants in The Netherlands...236 Table 9.10: Emissions to water in 1998 from two ethylene oxide plants in The Netherlands ...237 Table 9.11: Efficiency of central waste water treatment plant in Dutch plant...237 Table 9.12: By-product / waste generation by Producer B in The Netherlands...237 Table 10.1: European formaldehyde production capacity ...247 Table 10.2: Methanol contract prices in north-west Europe (DM/t)...248 Table 10.3: Trade-off between yield, steam export and electricity consumption ...253 Table 10.4: Waste air streams before and after treatment...254 Table 10.5: VOC emissions from formaldehyde storage and handling ...255 Table 10.6: Air emissions from Dutch formaldehyde plants ...255 Table 10.7: Emissions from a Swedish formaldehyde plant in 1998...255 Table 10.8: Air emissions from gas engines and steam boilers on an Austrian formaldehyde plant...256 Table 10.9: Review of air emission factors for formaldehyde plants ...256 Table 10.10: Waste arisings from Dutch and German formaldehyde plants ...257 Tabelle 10.11: Vergleich des Silber- und Oxidprozesses ...258 Tabelle 10.12: Maximale Arbeitsplatzkonzentration für Formaldehyd in Europa (März 1999)...261 Tabelle 10.13: Kosten der Emissionsminderung bei der Formaldehydproduktion [Environment Agency (E&W), 1998 #1]...262 Table 11.1: European acrylonitrile production ...267 Table 11.2: Reaction yields from acrylonitrile catalysts...274 Table 11.3: Typical raw material consumptions...275 Table 11.4: European absorber vent concentration ranges before and after treatment ...276 Table 11.5: Emissions from acrylonitrile storage and handling...276 Table 11.6: 1999 air emissions from an acrylonitrile plant in the Netherlands ...277 Table 11.7: European ranges for quench effluent before and after treatment...277 Table 11.8: European ranges for stripper bottoms effluent before and after treatment ...278 Table 11.9: 1999 water arisings and emissions from an acrylonitrile plant in The Netherlands ...278 Table 11.10: 1999 waste arisings from an acrylonitrile plant in The Netherlands...279 Table 11.11: Emission / consumption data for a German acrylonitrile plant) ...279 Table 12.1: Location of EDC/VCM plants in Western Europe ...291 Table 12.2: Leader and laggard Cash Costs for EDC/VCM (Western Europe in 1997)...293 Table 12.3: Typical Cost Breakdown for a 400 kt/yr VCM plant...293
xlb Herstellung organischer Grundchemikalien Table 12.4: Raw material and energy consumption in European example plants ... 300
Table 12.5: Emissions to air from German EDC/VCM plants ... 301 Table 12.6: 1998 emissions to air from Italian EDC/VCM plants ... 301 Table 12.7: Emissions to air from Swedish EDC/VCM plants ... 301 Table 12.8: Emissions to air from a Dutch EDC/VCM plant (1998) ... 302 Table 12.9: Review of air emission factors for EDC/VCM plants... 303 Table 12.10: Waste water from a Dutch EDC/VCM plant before and after treatment (1998) ... 304 Table 12.11: Effluent from German EDC/VCM plants... 304 Table 12.12: Waste water from three Italian EDC/VCM plants (prior to treatment) ... 304 Table 12.13: Waste generation by a Dutch EDC/VCM plant... 306 Tabelle 12.14: Maximale Emissionswerte in behandelter Abluft [CEFIC, 2000 #105]... 310 Tabelle 12.15: Leistung von Abwasserbehandlungsanlagen... 313 Tabelle 12.16: Kostenvergleich für Emissionsminderungsmaßnahmen bei der EDC/VC-Herstellung ... 315 Tabelle 12.17: ECVM-Emissionsgrenzwerte für Luft und Wasser [ECVM, #10]... 316 Tabelle 12.18: OSPAR-Emissionsgrenzwerte für Luft und Wasser... 316 Tabelle 12.19: Angegebene erreichbare Konzentrationen im Abwasser einiger Anlagen ... 316 Table 13.1: European producers of TDI in 1998... 325 Table 13.2: Specific emission from the TDI process prior to biological treatment... 331 Tabelle 13.3: Erreichbare Emissionswerte bei neuen TDI-Verfahren... 336