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Aromatics Amines, Supp. B t.. - 2, SRI INTERNATIONAL Manlo Park, California 94025 Abstract Process Economics Program Report No. 76B AROMATIC AMINES (April 1981) The processes for making aniline by hydrogenation and by amination of phenol are updated. The former process is more economical than the latter under most conditions. Another process, using iron reduction, is evaluated. This process is economic if the coproduced iron oxide is sold as pigment. Other processes for making aniline are discussed. Two processes for making nitrobenzene, a precursor of aniline, are evaluated. The newly developed adiabatic nitration process has some cost advantage over the conventional nitration process. Several important aniline derivatives are evaluated: N,N-dimethylaniline made from methanol by a liquid phase process, N-ethylaniline and N,N-diethylaniline jointly made from ethanol by a gas phase process, o-ethylaniline and 2,6-diethylaniline,jointly made from ethylene by a batch process, and diphenylamine from aniline condensation. Other derivatives of aniline are described. PEP'80 YCY Report No. 76B AROMATIC AMINES SUPPLEMENT B by YEN-CHEN YEN FENG -HSIN HUANG I 1 April 1981 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SKI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe. ii CONTENTS 0 1 INTRODUCTION. 1 2 SUMMARY ............................ 3 General Aspects--Aniline. ................... 3 General Aspects--Aniline Derivatives. ............. 6 Technical Aspects ....................... 6 Nitrobenzene by the Conventional Nitration Process. ..... 6 Nitrobenzene by the Adiabatic Nitration Process ....... 6 Aniline by Hydrogen Reduction of Nitrobenzene ........ 9 Aniline by Phenol Ammonolysis ................ 9 Aniline from Nitrobenzene by Iron Reduction ......... 10 N,N-Dimethylaniline from Aniline and Methanol ........ 10 N-Ethylaniline and N,N-Diethylaniline from Aniline and Ethanol ..................... 11 ortho-Ethylaniline and 2,6-Diethylaniline from Aniline and Ethylene. .................... 11 3 INDUSTRY STATUS. ....................... 13 Producers and Production Capacity of Aniline. ......... 13 l Markets for Aniline ...................... 13 Aniline Derivatives ...................... 13 U.S. Production Statistics for Aniline. ............ 18 4 NITROBENZENE MANUFACTURE. ................... 23 Review of Processes ...................... 23 Tubular Reactor or Pump Reactor ............... 23 Adiabatic Nitration Process Using Mixed Acid. ........ 24 Nitration Without Sulfuric Acid ............... 25 A Conventional Nitration Process for Making Nitrobenzene. ... 26 Process Description ..................... 26 Process Discussion ..................... 37 Cost Estimates ....................... 38 An Adiabatic Nitration Process for Making Nitrobenzene. .... 42 Process Description ..................... 42 Process Discussion ..................... 49 Cost Estimates ....................... 49 5 ANILINE FROM NITROBENZENE BY HYDROGEN REDUCTION ........ 55 Review of Processes ...................... 55 Process Description ...................... 55 Process Discussion ...................... 67 Cost Estimates ........................ 68 iii CONTENTS .............. 79 6 ANILINE FROM PHENOL BY AMMONOLYSIS. 0 Review of Processes ...................... 79 Process Description ...................... 79 ProcessDiscussion ...................... 91 Cost Estimates ........................ 91 7 ANILINE FROM NITROBENZENE BY IRON REDUCTION .......... 99 0 Chemistry ........................... 99 Review of Processes ...................... 99 A Process for Producing Aniline from Nitrobenzene by Iron Reduction, with Coproduction of Pigment. ......... 100 Process Description ..................... 100 Process Discussion ..................... 110 Cost Estimates ....................... 110 8 OTHER PROCESSES FOR PRODUCING ANILINE ............. 117 Processes Starting from Nitrobenzene. ............. 117 Reduction by Carbon Monoxide. ................ 117 Reduction by Methane. .................... 117 0 Reduction by Cyclohexene. .................. 118 Reduction by Hydrazine. ................... 118 Reduction by Hydrogen Sulfide ................ 118 Reduction by Cyclohexanol in Conjunction with Water and Cyclohexylamine .................. 118 Electrolytic Reduction ................... 118 Coproduction of Styrene from Ethylbenzene .......... 119 Reduction by Metal Chelate Polymers ............. 119 Direct Amination Processes ................. 120 Thallium Intermediate .................... 120 By Hydroxylamine ...................... 120 Processes Starting from Cyclohexane .............. 121 Amination of Cyclohexane. .................. 121 Amination of Cyclohexanol-Cyclohexanone........... 121 Process Starting from Chlorobenzene .............. 121 9 N-ALKYLANILINES ........................ 123 Chemistry ........................... 123 Review of Processes ...................... 124 0 N,N-Dimethylaniline by Liquid Phase Methylation ofAniline .; ........................ 131 Process Description . : . 131 iv CONTENTS 9 N-ALKYLANILINES (continued) Process Discussion. .................... 137 Cost Estimates ...................... 137 Manufacture of N,N-Diethylaniline .............. 142 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Ethylation of Aniline .................... 144 Process Description .................... 144 Process Discussion .................... 149 Cost Estimates ...................... 149 10 RING ALKYLATED ANILINES ................... 159 Chemistry .......................... 159 Review of Processes ..................... 160 A Process for Manufacturing o-Ethylaniline and 2.6-Diethylaniline. ..................... 160 Process Description .................... 160 Process Discussion .................... 173 Cost Estimates ...................... 174 11 OTHER ANILINE AND NITROBENZENE DERIVATIVES ......... 183 Diphenylamine ........................ 183 Acetanilide ......................... 187 Sulfanilic Acid ....................... 187 Acetoacetanilide ...................... 188 Aniline Hydrochloride .................... 188 2-Anilinoethanol. ...................... 188 AnilinomethanesulfonicAcid ................. 188 Chloranil.......... ................ 189 Cyclohexylamine. ...................... 189 m-Chloroaniline ....................... 189 Hydrazobenzene ....................... 189 Metanilic Acid ....................... 189 APPENDIX A DESIGN AND COST BASIS . 191 APPENDIX B PHYSICAL DATA................... 195 APPENDIX C SIZING OF BATCH DISTILLATION COLUMN . 199 CITED REFERENCES ....................... 201 PATENT REFERENCES By COMPANY ................... 211 V ILLUSTRATIONS 4.1 Nitrobenzene by Conventional Nitration Process. 215 4.2 Nitrobenzene by Adiabatic Nitration Process . 217 5.1 Aniline by Vapor-Phase Catalytic Reduction of Nitrobenzene . 219 5.2 Aniline Production from Benzene Via Nitrobenzene Effect of Operating Level and Plant Capacity on Production Cost. 78 6.1 Aniline by Ammonolysis of Phenol. 221 6.2 Aniline by Ammonolysis of Phenol Effect of Operating Level and Plant Capacity on Production Cost, . 96 7.1 Aniline by Bechamp Reduction of Nitrobenzene. , . 223 7.2 Aniline by Bechamp Reduction of Nitrobenzene Effect of Operating Level and Plant Capacity on Production Cost. 115 7.3 Comparison of Various Processes for Aniline Production Effect of Operating Level on Product Value. 116 9.1 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline. 225 9.2 N,N-Dimethylaniline by Liquid Phase Methylation of Aniline Effect of Operating Level and Plant Capacity on Production Cost and Product Value. 141 9.3 N-Ethylaniline and N,N-Diethylaniline by Vapor Phase Methylation of Aniline. , . 227 9.4 Production Costs and Product Values of N,-Ethylaniline and N,N-Diethylaniline at Different Production Levels . 158 10.1 o-Ethylaniline and/or 2,6-DiethylanilineManufacture. 229 10.2 o-Ethylaniline and 2,6-Diethvlaniline Effect of Operating Level and Plant Capacity on Production Cost. 180 10.3 o-Ethylaniline and 2,6-Diethylaniline Effect of Operating Level and Plant Capacity on Product Value . , . 181 B.l Equilibrium Conversion of Phenol to Aniline . 198 vii TABLES 0 2.1 Aniline Production Summary of Economics. , . 4 2.2 Nitrobenzene Production Summary of Economics. 5 2.3 Alkylated Anilines Production @ Summary of Economics. , . 7 3.1 U.S. Producers of Aniline . 14 3.2 Aniline Producers Outside of the United States. 15 3.3 Market Distribution of Aniline in the United States . 17 3.4 Chemicals Made from Aniline . , . 19 3.5 Chemicals Made from Nitrobenzene. 21 3.6 U.S. Production of Aniline and Some Alkylanilines . 22 4.1 Nitrobenzene Patent Summary . 27 4.2 Nitrobenzene by Conventional Nitration Process 0 Design Bases and Assumptions. 29 4.3 Nitrobenzene Production by Conventional Nitration Process Stream Flows .,..................... 32 4.4 Nitrobenzene Production by Conventional Nitration Process Major Equipment . 34 4.5 Nitrobenzene Production by Conventional Nitration Process Utilities Summary . 36 4.6 Nitrobenzene Production by Conventional 0 Nitration Process Total Capital Investment.
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