unit processes in organic synthesis P. H,. GROGGINS TATA Mct,RAW-HILL EDITIONUnit Processes in Organic Synthesis EDITOR-IN-CHIEF P. H. GROGGINS Chemical Engineer ‘Technical Advisor, Food Machinery and Chemical Corporation Author of “Aniline and Its Derivatives” and “Chemicals and Food Production” FIFTH EDITION Tata McGraw-Hill Publishing Company Limited NEW DELHI New Delhi New York St Louis San Francisco Auckland Bogota Guatemala Hamburg Lisbon London Madrid Mexico Milan Monteal Panama Paris San Juan Sao Paulo Singapore Sydney Tokyo Torontoja U-99 Tata McGraw-Hill $2 A Division of The McGraw-Hill Companies 1ya2e® (00 ) 140263 sy72 ETH Vise UNIT PROCESSES IN ORGANIC SYNTHESIS, 5/e Copyright © 1958 by the McGraw-Hill Book Company, Inc. Copyright © 1935, 1938, 1947, 1952 by the McGraw-Hill Book Compan} All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means without permission of the publisher Tata McGraw-Hill reprint 1995 Fourth reprint 1997 « RZLCRDRRRAQDB Reprinted in India by arrangement with McGraw-Hill, Inc., New York. SALES TERRITORY : ASIA When Ordering this title, use ISBN 0-07-462143-2 Published by Tata McGraw-Hill Publishing Company Limited, 4/12 Asal Ali Road, New Delhi 110 002, and printed at Sheel Print-N-Pack, Babarpur, Delhi 110 053PREFACE A quarter of « century has elapsed since the first edition of ‘Unit Prog- esses in Organic Synthesis” went to press. During that span of years the domestic synthetic organic chemical industry has grown enormously. ‘The production of petrochemicals, plastics, protective coatings, suifactants, chlorinated solvents, and elastomers—all involving organic synthesis—has multiplied many times. New technics have been developed, and chemical engineers have contributed much to make production processes more efficient. If adoption as a teaching tool and use as a plant reference work may serve as criteria, “Unit Processes in Organic Synthesis” has apparently served ‘useful purpose. Acceptance of the work has been world-wide, and it is with gratification that the authors note that the book has been or ig cur- rently being translated into five foreign languages, Apparently this re- fects the need for such a textbook in a growing technological economy. In the preface to the first edition, the editor distinguished between the now well-established terms unit processes and unit operations and showed how they are intimately related in the chemical engineering aspects of organic synthesis. The prime objective of the present volume continues to be the presentation of the industrial technic used in converting organic raw materials into usable products by various processes. Accordingly, the underlying principles and factors for each unit process are organized in a systematic manner with most of the emphasis on fundamental scientific and technological principles. Detailed discussion of manufacturing processes is included only to the extent required for the elucidation of these basic principles. Thus it is expected that the present, volume will continue to serve as a “semiworks course” to facilitate the student’s transition from the university classroom to an industrial environment. in keeping with the modern trend toward the ¢0-called chemical engi. neering sciences, the authors have stressed fundamental advances in theary as well asin industrial practice. Thus, thermodynamics and kinetics have received increased emphasis, ‘These subjects are inextricably associated with all chemical reactions and, therefore, are particularly important in the study and practice of unit processes. In this fifth edition, three new in troductory chapters are devoted to these subjects. wiiPREFACE ‘To ensure that the present text reflects the most recent advances in the technology of unit processes, many new coauthors have been invited to contribute to its pages. These new collaborators represent an accurate cross section of the American chemical industry. Their contributions to the technical literature in their specialized fields are evidence of their competence. Their cooperation in the preparation of the present edition should assure:a technologically sound text. ‘The editor is deeply obligated to managements of many chemical organi- sations for making possible employee participation in the preparation of this volume. It is accordingly hoped that their combined contributions will make possible a better training of chemical engineers and chemists for the plants of our expanding chemical industry. P. H. GrogginsCONTENTS 1, Applications of Thermodynamics in Unit Processes. 5 =. 5 2 2 | | 1 Sources of thermodynamic data, 1. 2, Chemical Kinetics : So 3. Chemical-process Kinetics ; ” 1 Factors that affect a chemical process, 40; Reactor shape and effect of back- mixing, 43. Nitration 2... Geo pe ooe ao 8 Introduction, 60; Nitrating agents, 61; Aromatic nitration, 63; Kinetics and mechanism of aromatic nitration, 68; Nitration of paraffinic hydrocarbons, 73; Nitrate esters, 80; N-nitro compounds, 81; Thermodynamics of nitrations, 83; Process equipment for technical nitration, 96; Mixed acid for nitrations 101; Typical industrial nitration processes, 107. Amination by Reduction Introduction and definitions, 129; Methods of reduction, 133; Iron and acid (Béchamp) reduction, 135; Other metal and acid reductions, 165; Catalytic hydrogenation, 168; Sulfide reductions, 186; Electrolytic reductions, 190; Metal and alkali reductions, 192; Sulfite reductions, 198; Miscellaneous reductions, 201, Halogenation Introduction, 204; Thermodynamics and kinetics of halogenation reactions, 211; Survey of halogenations, 222; Chlorination in the presence of a catalyst, 265; Photohalogenstion, 267; Design snd construction of equipment for halo- genation, 268; Technical halogenations, 270. ‘Sulfonation and Sulfation 303, Introduction, 303; Sulfonating and sulfating agents and their principal appli- cations, 305; Chemical and physical factors in sulfonation and sulfation, 337; Kinetics, mechanism, and thermodynamics, 351; The derulfonation reaction, 358; Working-up procedures, 362; Industrial equipment and techniques, 364; ‘Transition from batch to continuous processing, 368; Technical preparation of sulfonates and sulfates, 375. Amination by Ammonolysis 388 General discussion, 388; Aminating agents, 389; Survey of amination rese- tions, 397; Physical and chemical factors affecting ammonolysis, 426; Cata- lysta used in amination reactions, 432; Corrosion and the pH of the autoclave charge, 437; Kinetics of ammonolysig, 439; Thermodynamics of ammonolysis,10, ML. 2. 13. “a 18, CONTENTS 444; Design of reactors and auxiliaries, 447; Technical manufacture of amino compounds, 450; Control of the ammonia-recovery system, 482. Oxidation : ‘Types of oxidative reactions, 486; Oxidising agente, 488; Liquid-phase oxida- tion with oxidizing compounds, 503; Liquid-phase oxidation with oxygen, 507; Vapor-phase oxidation of aliphatic compounds, 517; Vapor-phase oxidation of aromatic hydrocarbons, 534; Kinetics and thermochemistry, 542; Apparatus for oxidations, 549. Hydrogenation Introduction, 555; Hydrogen: production and. propertice, 560; Catsiytic hydrogenation and hydrogenolysis: type reactions, 574; Kinetics and ther- modynamics of hydrogenation reactions, 590; General principles concerning hydrogenation catalysts, 600; Apparatus and materials of construction, 608; Industrial processes, 612. Hydrocarbon Synthesis and Hydroformylation Introduction, 651; Technology of Fischer-Tropsch operation, 654; Catalysts, 658; Thermodynamics and kinetics of the Fischer-Tropsch reaction, 661; Reactor development, 664; Commercial operation, 671; Economies of Fischer- ‘Tropsch operations, 675; Methanation, 675; Processes related to the Fischer- ‘Tropech synthesis, 678. Esterifcation Eeterification by organic acids, 695; Eaterfication of carboxylic acid deriva- tives, 710; Esters by addition to’ unsaturated eystems, 720; Esters of inor- ganic acids, 723; Esterification practice, 726. ‘Hydrolysis ee eee Definition and scope, 750; Hydrolyzing agents, 752; Materials susceptible to hydrolysis, 756; Kinetics, thermodynamics, and mechanism of hydrolysis, 761; Equipment for hydrolysis, 772; Technical operations involving hydroly- sis, 773. Alkylation. ee Introduction, 804; Types of alkylation, 806; Alkylating agents, 815; Factors controlling alkylation, 819; Equipment for alkylations, 825; Effect of alkyla~ tion, 828; Technical alkylations, 829. Part 1. Principles of Polymer Chemistry. . Introduction, 856; Chemistry of polymerization reactions, 858; Methode of polymerization, 892; Polymerization kinetics, 904; Solution propertics of polymers, 913; Polyclectrolytes, $23; Influence of molecular characteristics on polymer properties, 939; Influence of intermolecular arrangement on polymer properties, 941. Part 2, Polymerization Practice a Industrially important polymerizations and polymere, 043. 651 750