United States Office of Air Quality EPA-45014-91-031 Environmental Protection Planning and Standards August 1993 Agency Research Triangle Park NC 2771 1 Air Guideline Series Control of Volatile Organic Compound Emissions from Reactor Processes and Distillation Operations Processes in the Synthetic Organic Chemical Manufacturing Industry Guideline Series Control of Volatile Organic Compound Emissions from Reactor Processes and Distillation Operations Processes in the Synthetic Organic Chemical Manufacturing Industry GUIDELINE SERIES m The guideline series of reports is issued by the Office of Air Quality Planning and Standards (OAQPS) to provide information to State and I local air pollution control agencies; for example, to provide guidance on the acquisition and processing of air qua1 ity data and on the planning and analysis requisite for the maintenance of air quality. Mention of trade .I names or comnercial products is not intended to constitute endorsement or recomnendation for use. Reports pub1 ished in this series will be available - as supplies permit - from the Library Services Office (MD-35), I U. S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, or for a nominal fee, from the National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161. I TABLE OF CONTENTS LISTOFFIGURES .......................... viii LISTOFTABLES........................... ix CHAPTER 1.0 INTRODUCTION ......................... 2.0 INDUSTRY CHARACTERISTICS AND EMISSIONS ............ 2.1 GENERAL INDUSTRY INFORMATION ............... 2.2 REACTOR PROCESSES .................... 2.2.1 Scope of Reactor ~rocesses ............ 2.2.2 Chemical Reaction Descriptions .......... 2.2.2.1 A1 kylation ............... 2.2.2.2 Ammonolysi s ............... 2.2.2.3 Carboxyl ation/Hydroformylation ..... 2.2.2.4 Cleavage ................ 2.2.2.5 Condensation .............. 2.2.2.6 Dehydration ............... 2.2.2.7 Dehydrogenation ............. 2.2.2.8 Dehydrohalogenation ........... 2.2.2.9 Esterification ............. 2.2.2.10 Halogenation .............. 2.2.2.11 Hydrodealkylation ............ 2.2.2.12 Hydrohal ogenat ion ............ 2.2.2.13 Hydrolysis/Hydration .......... 2.2.2.14 Hydrogenation .............. 2.2.2.15 Isomerization .............. 2.2.2.16 Neutralization ............. 2.2.2.17 Nitration ................ 2.2.2.18 Oligomerization ............. 2.2.2.19 Oxidation ................ 2.2.2.20 Oxyacetyl ation ............. 2.2.2.21 Oxyhalogenation ............. 2.2.2.22 Phosgenation ............... 2.2.2.23 Pyrolysis ................ 2.2.2.24 Sulfonation ............... 2.3 DISTILLATION OPERATIONS .................. 2.3.1 Types of Distillation ............... 2.3.2 Fundament a1 Di st i 11 at i on Concepts ......... 2.4 REACTOR VOLATILE ORGANIC COMPOUND EMISSIONS ....... 2.5 VOLATILE ORGANIC COMPOUND EMISS IONS FROM DISTILLATION UNITS .................... 2.6 REFERENCES ........................ TABLE OF CONTENTS (CONTINUED) CHAPTER 3.0 EMISSION CONTROL TECHNIQUES. .............. 3.1 COMBUSTION CONTROL DEVICES. ............ Flares ................... 3.1.1.1 Flare Process Description ..... 3.1.1.2 Factors Affecting Flare Efficiency. 3.1.1.3 EPA Flare Specifications. ..... 3.1.1.4 Appl icabi1 ity of Flares ...... Thermal Incinerators ............ 3.1.2.1 Thermal Incinerator Process Description ............ 3.1.2.2 Thermal Incinerator Efficiency. .. 3.1.2.3 Applicability of Thermal Incinerators. ........... Industrial Boilers/Process Heaters ..... 31.31 Industrial Boiler/Process Description ............ 3.1.3.2 Process Heater Description. .... 3.1.3.3 Industrial Boilers and Process Heater Control Efficiency ..... 3.1.3.4 Applicability of Industrial Boilers and Process Heaters ...... Catalytic Oxidizers, .......... 3.1.4.1 Catalytic Oxidation.Process Description .......... 3.1.4.2 - Catalytic Oxidizer Control Efficiency. .......... 3.1.4.3 Applicability of Catalytic Oxidizers ............ 3.2 RECOVERY DEVICES. ............... 3.2.1 Adsorption ............... 3.2.1.1 Adsorption Process Description. 3.2.1.2 Adsorption Control Efficiency . 3.2.1.3 Applicability of Adsorption . 3.2.2 Absorption .... 3.2.2.1 Absorption Process Description. 3.2.2.2 ~bsorptionControl Efficiency . 3.2.2.3 Applicability of Absorption . TABLE OF CONTENTS (CONTINUED) Paqe CHAPTER 3.2.3 Condensation ................... 3.2.3.1 Condensation Process Description..... 3.2.3.2 Condenser Control Efficiency....... 3.2.3.3 Applicability of Condensers ....... 3.3 SUMMARY ......................... 3.4 REFERENCES ........................ 4.0 ENVIRONMENTAL IMPACTS ..................... 4.1 AIR POLLUTION IMPACTS .................. 4.1.1 Volatile Organic Compound Emission Impacts .... 4.1.2 Secondary Air Impacts ............... 4.2 WATER POLLUTION IMPACTS ................. 4.3 SOLIDWASTEDISPOSAL IMPACTS ............... 4.4 ENERGY IMPACTS ...................... 4.5 REFERENCES ........................ 5.0 COSTANALYSIS......................... 5.1 INTRODUCTION....................... 5.2 COST METHODOLOGY FOR INCINERATOR SYSTEMS ......... 5.2.1 Thermal Incinerator Design Considerations ..... 5.2.1.1 Combustion Air Requirements ....... 5.2.1.2 Dilution Air Requirements ........ 5.2.1.3 Recuperative Heat Recovery ........ 5.2.1.4 Incinerator Design Temperature ...... 5.2.2 Thermal Incinerator Capital Costs ......... 5.2.3 Thermal Incinerator Annualized Cost ........ 5.2.3.1 Labor Costs ............... 5.2.3.2 Capital Charges ............. 5.2.3.3 Utility Costs .............. 5.2.3.4 Maintenance Costs ............ 5.3 COST METHODOLOGY FOR FLARE SYSTEMS ............ 5.3.1 Flare Design Considerations ............ 5.3.2 Development of Flare Capital Costs ........ 5.3.3 Development of Flare Annualized Costs ....... 5.3.3.1 Labor Costs ............... 5.3.3.2 Capital Charges ............. 5.3.3.3 Utility Costs .............. 5.3.3.4 Maintenance Costs ............ TABLE OF CONTENTS (CONTINUED) 5.4 COMPARISON OF CONTROL SYSTEM COSTS. 5.5 REFERENCES. 6.0 SELECTION OF REASONABLY AVAILABLE CONTROL TECHNOLOGY . 6.1 BACKGROUND. 6.2 TECHNICAL BAS1S FOR REASONABLY AVAILABLE CONTROL TECHNOLOGY ........................ 6.3 REASONABLY AVAILABLE CONTROL TECHNOLOGY SIZE CUTOFFS . 6.4 IHPACTS OF APPLYING VARIOUS COST EFFECTIVENESS CUTOFFS. 6.5 REASONABLY AVAILABLE CONTROL TECHNOLOGY SUMHARY . 6.6 REFERENCES. 7.0 REASONABLY AVAILABLE CONTROL TECHNOLOGY IHPLEMENTATION . 7.1 INTRODUCTION. 7.2 DEFINITIONS . '. 7.3 REGULATORY SUMMARY. 7.3.1 Air Oxidation Control Techniques' Guide1ines . 7.3.2 Air Oxidation Processes New Source Performance Standard . 7.3.3 Distillation Process New Source Performance Standard . 7.3.4 Reactor Process New Source Performance Standard . 7.4 APPLICABILITY . 7.5 FORMATOFTHESTANDARDS. 7.6 PERFORMANCE TESTING . 7.6.1 Incinerators . ; . 7.6.2 Flares ...................... 7.6.3 Boiler or Process Heater . 7.6.4 Recovery Devices . 7.7 COMPLIANCE MONITORING REQUIREMENTS. 7.7.1 Thermal Incinerators . 7.7.2 Flares . 7.7.3 Boiler or Process Heater . 7.7.4 Recovery Devices . TABLE OF CONTENTS (CONTINUED) 7.8 REPORTING/RECORDKEEPING REQUIREMENTS. .......... 7-17 7.9 REFERENCES. ....................... 7-18 APPENDICES A. LIST OF SYNTHETIC ORGANIC CHEMICAL MANUFACTURING INDUSTRY CHEMICALS. ...................... A-1 B. EMISSION DATA PROFILES. .................... B-1 C. COSTCALCULATIONS. ...................... C-1 D. SYNTHETIC ORGANIC CHEMICAL MANUFACTURING INDUSTRY CONTROL TECHNIQUES GUIDELINE EXAMPLE RULE ........... D-1 E . ENVIRONMENTAL IMPACT CALCULATIONS ............... E- 1 F. RESPONSE TO PUBLIC COMMENTS RECEIVED ON THE DRAFT SYNTHETIC ORGANIC CHEMICAL MANUFACTURING INDUSTRY REACTOR PROCESSES AND DISTILLATION OPERATIONS CONTROL TECHNIQUES GUIDELINE ............ F-1 LIST OF FIGURES Number Pape 2-1 The interwoven nature of feedstocks for the organic chemicals manufacturing industry. .............. 2-4 2-2 Chemical derivatives made from the feedstock ethylene .... 2-5 2-3 Flash distillation. ..................... 2-28 2-4 A conventional fractionating column ............. 2-29 2-5 General examples of reactor-related vent streams. ...... 2-36 2-6 Process flow di-agram for the manufacture of nitrobenzene. .. 2-37 2-7 Process flow diagram for the manufacture of ethylbenzene. .. 2-38 2-8 Process flow diagram for the manufacture of acetone ..... 2-39 2-9 Potential volatile organic compound emission points for a nonvacuum distillation column ................ 2-44 . 2-10 Potential volatile organic compound emission points for a vacuum distill ation column using steam jet ejectors with barometric condenser. .................... 2-45 2-11 Potential volatile organic compound emission points for a vacuum distillation column using steam jet ejectors ..... 2-46 2-12 Potenti a1 volatile organic compound emission points for vacuum distillation column using a vacuum pump. ....... 2-47 3-1 Steam assisted elevated flare system. ............ 3-3 3-2 Discrete burner, thermal oxidizer .............. 3-9 3-3 Distributed burner, thermal oxidizer. ............ 3-10 3-4 Catalytic oxidizer. ..................... 3-19 3-5 Two stage regenerative adsorption system. .......... 3-23 3-6 Packed tower for gas absorption ....., ......... 3-27 3-7 Condensationsystem. .................... 3-29 D- 1 Synthetic organic chemical -manufacturing industry reactor/distillation control techniques guide1 ine logic diagram per vent. ................... 0-3 LIST OF TABLES Number Paqe FEEDSTOCK CHEMICALS FOR CHEMICAL PRODUCTION PROCESSES .... 2-3 ESTIMATED PRODUCTION AND CHEMICAL COVERAGE FOR VARIOUS PRODUCTION