AP42 Section 6.10 Background Ref: 4 Title: Source Assessment: Maleic Anhydride Manufacture US EPA Dec 1978 * :: 11 .T, ... ....... .. , . .~....... ........... SOURCE ASSESSMENT: MALEIC ANHYDRIDE MANUFACTURE bY W; A. Lewis, Jr., G. M. Rinaldi, and T. W. Hughes Monsanto Research Corporation Dayton, Ohio 45407 Contract No. 68-02-1874 Task Officer Ronald J. Turner Industrial Pollution Control Division I ndu str i a1 Env i ronmentd 1 Research La bora tory Cincinnati, Ohio 45268 .. ... ... .. .,. .. .. .. ............... INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 ... ......,. .. ... ........ ...... .. __- '[I\ *, .... ,....... .. .. ., ., . .. .. .. ..... .. DISCLAIMER ....... .. .. .. This report has been reviewed by the Industrial Environmental .,.. .... ......... i Research Laboratory-Cincinnati, U.S. Environmental Protection 1; Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. .... ... .. .,. ., .......... .. ... ......... ... .. ... .. .. .. .. ........ .. ii , - .... ....... .. .. ., .. .. .. ..., .. FOREWORD ..... .... .... ...... .. .. When energy and material resources are extracted, processed, converted, and used, the related pollutional impacts on our environment and even on our health often require that new and increasingly more efficient pollution control methods be used. The Industrial Environmental Research Laboratory - Cincinnati (IEFU-Ci) assists in developing and demonstrating new and improved methodologies that will meet these needs both efficient- ly apd economically. This report contains an assessment of air emissions from the production of maleic anhydride. Further information on this subject may be obtained from the Organic Chemicals and Products Branch, Industrial Pollution Control Division, Industrial Environmental Research Laboratory, Cincinnati, Ohio 45268. David G. Stephan Director Industrial Environmental Research Laboratory Cincinnati ........ ..... .. ........ .... ...... , , . .. ......... .. .. .. .. .. ,.... iii ...... , . .. .. .. ........ .. .. .. ... ... PREFACE ......... The Industrial Environmental Research Laboratory (IERL) of the ,... ,. ... .... .. U.S. Environmental Protection Agency (EPA) has the responsibility ..... for insuring that pollution control technology is available for stationary sources to meet the requirements of the Clean Air Act; the Federal Water Pollution Control Act, and solid waste legis- lation. If.control technology is unavailable, inadequate, or uneconomical, then financial support is provided for the develop- ment of the needed control techniques for chemical and extractive process industries. Approaches considered include: process modifications, feedstock modifications, add-on control devices, and complete process substitution. The scale of the control technology programs ranges. from bench- to full-scale demonstra- tion plants. Monsanto Research Corporation (MRC) has contracted with EPA to investigate the environmental impact of various industries that represent sources of emissions in accordance with EPA's responsi- bility, as outlined above. Dr. Robert C. Binning serves as Program Manager in this overall program, entitled, "Source Assessment," which includes the investigation of sources in each of four categories: combustion, organic materials, inorganic materials, and open sources. Dr. Dale A. Denny'of the Indus- trial Processes Division at Research Triangle Park serves as EPA Project Officer for this series. This study of maleic anhydride plants was initiated by IERL-Research Triangle Park, in Septem- ber 1975; Mr. Edward J. Wooldridge served as EPA Task Officer. The project was transferred to the Industrial Pollution Control Division, IERL-Cincinnati in October 1976; Mr. Ronald J. Turner served as EPA Task Officer from that time through completion of the study. Source Assessment Documents prepared in this program contain data on emissions from specific industries. Such data are gathered from the literature, government agencies and cooperating com- ................. .. panies. Sampling and analysis are also performed by the contrac- .....~~.. ....... tor when the available information does not adequately charac- terize the source emissions. ..... ,. ... .... .. ...... ...... iv t ........ .... .. ....... .. ABSTRACT ... ........... .. .... .. This report describes a study of air emissions from maleic .......... anhydride production. Maleic anhydride is manufactured primarily by the catalytic oxidation of benzene; some butane feedstock is also used domestically. Emission points in a maleic anhydride plant include the product recovery scrubber; the refining vacuum system; flaking, pelletizing, and packaging: aqueous waste storage; raw material and product storage tanks; and fugitive sources. To assess the environmental impact of this industry, source severity was defined as the ratio of the time-averaged maximum ground level concentration of an emission to a potentially hazardous concentration from a given point. Source severities for a representative plant producing 23,900 metric tons/yr of product are 0.73 for carbon monoxide and up to 25.1 for hydro- carbons from various points. Severities for noncriteria pol- lutants were also calculated. ...... Maleic anhydride production contributes 0.15% of the total carbon monoxide emitted in the U.S. and 0.14% of the hydrocarbons. This report was submitted in partial fulfillment of Contract NO. 68-02-1874 by Monsanto Research Corporation under the sponsorship of the U.S. Environmental Protection Agency. This report covers the period September 1975 to December 1978. ... ........ ... .. .. ........ .. .. .. ...... .... .. .. ... ...... .. V c ................... ............... ........... CONTENTS 1 ............ ........ Foreword.. iii .......... ........................ Preface ........................... iv Abstract.. ......................... v Figures .......................... viii Tables.. .......................... ix Abbreviations and Symbols ...................xi Conversion Factors and Metric Prefixes ........... xiV 1. Introduction ............. .... .... 1 2. Summary ................. .... .... 3 3. Source Description .............. .... 6 Process description ........ ........ 6 Material flow ............... .... 20 Geographical distribution ..... .... .... 20 4. Emissions ................... .... 27 Selected pollutants ........ ........ 27 Location and description ..... .... ....30 Environmental effects ........... ....3 4 5. Control Technology .......... .... ....43 Installed controls ........ .... ....43 Assessment of air pollution control methods ....45 6. Growth and Nature of the Industry ... .... ....65 Present technology ........ .... ... .65 Emerging technology ........ .... ....65 Marketing strengths and weaknesses ........66 References .......................... 70 Appendices A. Storage tank calculations ................77 B. Derivations of source severity equations ....... 81 C. Maleic anhydride plant emission factors obtained from industry 95 .... ...................... ..................... D. Pre-survey sampling and analysis results for a maleic ................. anhydride plant product recovery scrubber. ..... 97 Glossary.. ........................ 105 ..... ................ ........... vii ........... ................ ........... FIGURES ..... ....................... Number Page ................... 1 Maleic anhydride flow diagram ........... 8 2 Maleic anhydride plant locations .........26 3 Steps required for successful incineration of 46 dilute fumes .................. 46 4 Coupled effects of temperature and time on rate of pollutant oxidation ............... 48 5 Hydrocarbon oxidation rates in absence of flame . 49 6 Thermal incinerator with waste heat boiler ....51 7 Thermal incinerator with feed gas preheater ....51 8 Thermal incinerator-scrubber control system ....52 9 Adsorption efficiency of a carbon bed for a single organic compound ................57 10 Adsorption efficiency of a carbon bed for a three- component mixture ................58 11 Carbon adsorption system for emissions from maleic anhydride production ..............59 12 Control of benzene emissions from maleic anhydride production by three-bed carbon adsorption ....60 13 Wet scrubber/waste disposal system ........61 14 Schematic diagram of scrubber for emissions from maleic anhydride production ............62 15 Schematic diagram of thermal incinerator for scrubber purge liquor .............. 64 16 Uses of maleic anhydride .............67 ................. ....... ......... ..... ........... ................ viii .......... ................ .................... TABLES , ..... ................ ................. ........... Number 1 Source Severities and Industry Contribution to Total Emissions for Maleic Anhydride Production . 5 2 Steam Code for Maleic Anhydride Process Illus- trated in Figure 1 ................9 3 Performance of Five Azeotropic Agents in Dehydra- tion.of Maleic Acid ...............13 4 Summary of Tankage Requirements for a 23,900-Metric Ton/Yr Benzene-Based Maleic Anhydride Plant ... 15 Maleic Anhydride Wastewater Discharges .......17 Heats of Reaction for the Oxidation of Benzene . 19 Reactor System Heat Balance for Production of ........... Maleic Anhydride from Benzene .........