Report No. 76Al Interim AROMATIC AMINES by YEN-CHEN YEN July 1975 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS 1 INTRODUCTION........................ 1 2 INDUSTRY STATUS AND SUMMARY... 3 Industry Status... 3 Summary of Process Descriptions... 4 Dinitrobenzene... 4 m-phenylenediamine from Dinitrobenzene... 4 m-phenylenediamine by Direct Amination... 5 Cost Comparisons... 5 3 DINITROBENZENE... 9 Chemistry... 9 Review of Processes... 13 Nitration... 13 Reactor Type... 13 Raw Materials... 14 Acid Composition and Recycling... 14 Separation, Washing and Purification... 17 Process Description... 20 Process Discussion... 29 Cost Estimates... 31 4 META-PHENYLENEDIAMINE FROM DINITROBENZENE... 39 Chemistry... 39 Review of Processes... 41 Reduction... 41 Purification of Meta-phenylenediamine... 48 Process Description... 52 Process Discussion... 58 Cost Estimates... 59 5 m-phenylenediamine BY DIRECT AMINATION........... 65 Process Description... 66 Process Discussion... 73 Cost Estimates... 73 Alternative Cases... 77 Possibilities for Future Development... 79 vii
L CONTENTS 6 OTHER PROCESSES FOR MANUFACTURING m-phenylenediamine.... 81 Reduction of Dinitrobenzene by Iron and Hydrochloric Acid (Bechamp Process)...................... i: Reduction of Chlorodinitrobenzene............. From Isophthalic Acid via Amide.............. 82 Direct Amination of Isophthalic Acid............ 82 Amination of Aniline by Hydroxylamine Hydrochloride.... 82 From Resorcinol...................... 83 APPENDIX A DESIGN AND COST BASES............... 85 APPENDIX B PHYSICAL DATA................... 87 APPENDIX C SPECIFICATIONS OF p-phenylenediamine....... 93 APPENDIX D HAZARDS... 95 CITED REFERENCES........................ 97 PATENT REFERENCES BY COMPANY.................. 105 viii
ILLUSTRATIONS 3.1 Reaction Rates for Nitration of Benzene and Nitrobenzene... 11 3.2 Compositions of Mixed Acids Used in the Manufacture of Dinitrobenzene...................... 16 3.3 Flow Sheet... 107 3.4 Acid Cycle in the Process.................. 23 3.5 Dinitrobenzene Effect of Operating Level and Plant Capacity on Production Cost....................., 37 4.1 m-phenylenedismine from Dinitrobenzene Flow Sheet.......................... 109 4.2 Integrated Production of m-phenylenediamine from Benzene via DNB Effect of Operating Level and Plant Capacity on Production Cost....................... 63 5.1 m-phenylenediamine by Direct Amination Flow Sheet... 111 5.2 m-phenylenediamine by Direct Amination Effect of Operating Level and Plant Capacity on Production Cost....................... 76 B.l System Nitrobenzene-Sulfuric Acid-Water........... 88 ix
TABLES 2.1 2.2 3.1 3.2 3.3 3.4 3.5 3.6 3.7 4.1 4.2 4.3 4.4 Comparison of Processes for Making m-phenylenediamine... 6 Production of Aniline and m-phenylenediamine.,...... 7 Washing, Separation, and Purification of Nitrobenzene and Dinitrobenzene Patent Summary....................... 18 Design Bases and Assumptions..............., 21 Major Process Equipment and Utility Summary........ 25 Compositions of Stream Flows................ Waste Streams....................... Total Capital Investment.................. Production Costs...................... Reduction of Dinitro Aromatic Compounds to Diamines by Hydrogen Patent Summary....................... Purification of Meta-Phenylenediamine Patent Summary....................... m-phenylenediamine from Dinitrobenzene Design Basis and Assumptions................ m-phenylenediamine from Dinitrobenzene Based on Du Pont Patents Major Process Equipment and Utilities Summary....... 27 28 35 36 42 49 53 55 4.5 4.6 4.7 m-phenylenediamine from Dinitrobenzene Composition of Stream Flows....,........... m-phenylenediamine from Dinitrobenzene Based on Du Pont Patents Total Capital Investment.................. m-phenylenediamine from Dinitrobenzene Based on Du Pont Patents Production Costs...................... 57 61 62 xi
TABLES 5.1 m-phenylenediamine by Direct Amination Design Bases and Assumptions......... 5.2 m-phenylenediamine by Direct Amination Major Process Equipment and Utilities Summary 5.3 m-phenylenediamine by Direct Amination Compositions of Stream Flows.....,... 5.4 m-phenylenediamine by Direct Amination Total Capital Investment..... -...... 5.5 m-phenylenediamine by Direct Amination Production Costs............... 5.6 m-phenylenediamine by Direct Amination Comparison of Costs............. 5.7 Aniline by Direct Amination with Coproduction of m-phenylenediamine Cost Features........................ 67........ 70........ 72... 74... 75........ 78........ 80 xii