C4-Hydrocarbons and Derivatives: Resources, Production, Marketing

249 Pages·1989·5.345 MB·English

by  Prof. Dr.-Ing. Joachim Schulze, Dr.-Ing. Malte Homann (auth.)

J. Schulze M. Homann
C -Hydrocarbons
4
and Derivatives
Resources, Production, Marketing
Translation from the German by M. R. F. Ashworth
With 63 Figures and 89 Tables
Springer-Verlag Berlin Heidelberg New York
London Paris Tokyo Hong Kong
Prof. Dr.-Ing. Joachim Schulze
Technische Universitat Berlin
Institut fur Technische Chemie
FB Physikalische und Angewandte Chemie
StraBe des 17. Juni 135, D-lOOO Berlin 12
Dr.-Ing. Malte Homann
Deutsche Shell Chemie GmbH
KaIner Str. 6, D-6236 Eschborn
Translator:
Prof. Dr. M. R. F. Ashworth
Universitat des Saarlandes
Fachrichtung 13.5, Organische und
Instrumentelle Analytik
D-6600 Saarbrucken
ISBN-13: 978-3-642-73860-9 e-ISBN-I3 :978-3-642-73858-6
DOl: 10.1007/978-3-642-73858-6
Library of Congress Cataloging-in-Publication Data.
Schulze, Joachim.
C4-hydrocarbons and derivatives: resources, production, marketing 1 J. Schulze, M. Homann; translation from the
German by M. R. F. Ashworth.
Bibliography: p. Includes index.
ISBN-I3:978-3-642-73860-9 (U. S.)
1. Hydrocarbons. I. Homann, M. (Malte), 1956 ~. II. Title.
TP692.4.H9S33 1989661' .81--dc20 89-6398 CIP
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permitted under the provisions of the German Copyright Law of September 9,1965, in its version of June 24,1985,
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© Springer-Verlag Berlin Heidelberg 1989
Softcover reprint of the hardcover 1st edition 1989
The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific
statement, that such names are exempt from the relevant protective laws and regulations and therefore free for
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Typesetting: Pustet, Regensburg
2151/3030-543210 ~ Printed on acid-free paper
Foreword
The book treats the C -hydrocarbons and their secondary products as a contribution
4
to chemical engineering economics, applying this field of teaching and research to the
technical processes for making and processing this group of products, so important to
the chemical industry.
As early as tpe 1950s the then director of the Institute for Technical Chemistry of
the Berlin Technical University, Professor Herbert Kolbel, took the' initiative in the
domain of Chemical Engineering Economics and began systematic studies of Project
Engineering and Cost Estimation in connection with chemical plants. He also started
a course on technical chemical processes in 1966. Properties, production procedures,
plant equipment, and also the uses of technically interesting products are the central
features of Chemical Technology. The information is to be found in the large
encyclopedias of Technical Chemistry.
On the other hand, Chemical Engineering Economics deals with all the economic
conditions of usage of the raw materials, possibilities of utilizing co-products, and the
integration of these products into definite production programmes, from the stand
point of the chemical and technical fundamentals of the processes. Further important
viewpoints are the costs of the products, taking into consideration important and
variable influences on these costs, the situation and development of the market for the
products and, of increasing significance, also the ecological global conditions for
procuring raw materials and the production and marketing of the particular products.
Industrial chemistry is also touched on. This has been neglected in Western
Europe and the German Federal Republic for a long time but some interesting books
have been published in recent years. The present book provides, for the first time, a
self-contained summary of industrial C -chemistry together with the peculiarities of
4
Chemical Engineering Economics. The analysis of competitiveness of the processes
and products in the C -field has been especially stressed.
4
We would like to express our thanks for the kind cooperation of Hi.i1s AG, Marl,
the leading company for industrial C -chemistry in Western Europe.
4
We would also like to thank Dipl. Ing. Werner Dabelstein of the Deutsche
Shell AG, Hamburg, for his expert assistance in the chapter on fuel components;
Dr. Wolfgang Jakel of the Deutsche Shell Chemie GmbH, Eschborn, for his compe
tent supplementary information concerning markets; and also Dipl. Chem. Peter
Enders for the good cooperation with Springer-Verlag and for arranging for the
translation into English.
We are further indebted to Hi.i1s AG, Marl; ROW, Wesseling; and Deutsche
Shell AG, Hamburg, for contributing several photographs.
Berlin and Eschborn, March 1989 J. Schulze· M. Homann
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1
1 Fundamentals of C -Hydrocarbons . . . . . . . . . . . . . . . 5
4
1.1 Nomenclature and Chemical Structure of the C4-Hydrocarbons 5
1.2 Definition of the C -Cut from Steam Crackers
4
and Its Raffinates . . . . . . . . . . . . . . . . . . . . . . . 6
1.3 Terms for the C -Hydrocarbon Streams Within the Refinery 6
4
1.4 Product Specifications ................... . 7
2 Production Scheme for C -Hydrocarbons 9
4
2.1 Methods for Establishing the Production Scheme 9
2.2 Production of C -Hydrocarbons 9
4
2.2.1 C -Hydrocarbons from Natural Sources .. . 11
4
2.2.2 C -Hydrocarbons from Refinery Gases ... . 16
4
2.2.3 C -Cut as Co-product of Ethylene Production 19
4
2.2.4 C -Hydrocarbons Through Synthesis 23
4
2.2.4.1 Petrochemical Syntheses . 23
2.2.4.2 Syntheses Based on Coal . . . . . . 26
2.2.4.3 Biotechnological Syntheses . . . . . 28
2.3 Production of C -Aldehydes and Alcohols 29
4
2.3.1 Butanals .. 30
2.3.2 Butanols 31
2.3.3 Butanediols 33
3 Processes of Separation and Transformation
in C -Chemistry . . . . . . . . . . . . . . . 35
4
3.1 Separation of the C -Cut and C -Gases from Refineries 35
4 4
3.1.1 Separation Processes for Obtaining Butadiene 36
3.1.2 Separation Processes for Obtaining Butenes 38
3.1.2.1 Survey .......... . 38
3.1.2.2 Sulfuric Acid Processes .. 40
3.1.2.3 Molecular Sieve Processes 41
3.1.2.4 Other Processes ..... . 42
VIII Contents
3.2 Processes of Butane Conversion 46
3.2.1 Isomerisation . . 46
3.2.2 Dehydrogenation 47
3.2.3 Oxidation 51
3.2.4 Alkylation. 54
3.2.5 Chlorination 56
3.2.6 Cyc1isation 58
3.2.7 Other Applications 59
3.3 Processes of Butene Conversion 60
3.3.1 Components of Gasoline Fuels 61
3.3.1.1 Polymer Gasoline . . . . . . . . 61
3.3.1.2 Methyl tert-Butyl Ether (MTBE) 62
3.3.2 Chemical Secondary Products from Raffinate I . 67
3.3.2.1 Polybutene . . . . . 67
3.3.2.2 Di- and Tri-i-butenes 68
3.3.2.3 Propene ...... . 68
3.3.2.4 Specialities .... . 69
3.3.3 Chemical Secondary Products from Raffinate II 69
3.3.3.1 Oligomers of n-Butenes . 69
3.3.3.2 Butadiene ..... . 71
3.3.3.3 Methyl Ethyl Ketone 72
3.3.3.4 Maleic Anhydride . 72
3.3.3.5 Acetic Acid . . . 73
3.3.3.6 Specialities ..... 74
3.3.4 Chemical Secondary Products from Pure i-Butene 74
3.3.4.1 Poly-i-butene . . . . 75
3.3.4.2 Butyl Rubber . . 75
3.3.4.3 Methacryl Compounds 76
3.3.4.4 Isoprene ....... . 82
3.3.4.5 Specialities ..... . 85
3.3.5 Chemical Secondary Products from Pure n-Butenes 85
3.3.5.1 Poly-I-butene . . . .. .. 85
3.3.5.2 HDPE-Comonomer and LLDPE .. 86
3.3.5.3 1,2-Butene Oxide ......... . 87
3.4 Processes of Butadiene Conversion . 89
3.4.1 Butadiene Polymers and Copolymers . 89
3.4.1.1 Polybutadiene . .. .., 89
3.4.1.2 Polychloroprene .... 92
3.4.1.3 Styrene-butadiene Rubber 95
3.4.1.4 Nitrile Rubber .... 96
3.4.1.5 Acrylonitrile-butadiene-styrene Polymers 96
3.4.1.6 Ethylene-propene-diene Polymers . . . . 97
3.4.1.7 Rubber and Latex Specialities Containing Butadiene 97
3.4.2 Styrene ........ .. 99
3.4.3 Polyamides . . . . .. ... 99
3.4.4 1,4-Butanediol and Derivatives 102
3.4.5 Anthraquinone . . . . . . . . 103
Contents IX
3.4.6 Sulfolane ......... . 104
3.4.7 Other Butadiene Specialities 104
4 Processing Scheme for C4-Hydrocarbons 107
4.1 Method of Ascertaining the Processing Scheme 107
4.2 Analysis of the Processing Scheme for Butane Secondary Products 112
4.2.1 Butane Derivatives Processing Scheme ...... . 112
4.2.2 Production Amounts of Butane Secondary Products 112
4.2.3 Specific Butane Consumption Coefficients
for the Secondary Products . . . . . . . . . . . . . . . . . . . . . 113
4.2.4 Processing Scheme for Butanes . . . . . . . . . . . . . . . . . . . 113
4.3 Analysis of the Processing Scheme for Butene Secondary Products 113
4.3.1 Butene Derivatives Processing Scheme . . . . . . . 113
4.3.2 Production Amounts of Butene Secondary Products 116
4.3.3 Specific Butene Consumption Coefficients
for the Secondary Products . . . . . . . . . . . . 119
4.3.4 Processing Scheme for Butenes ......... . 119
4.4 Analysis of the Processing Scheme for Butadiene
Secondary Products . . . . . . . . . . . . . . . . 119
4.4.1 Butadiene Derivatives Processing Scheme
4.4.2 Production Amounts of Butadiene Secondary Products . . . . . . . 119
4.4.3 Specific Butadiene Consumption Coefficients
for the Secondary Products . . . . 124
4.4.4 Processing Scheme for Butadiene ...... . 125
5 Competition Factors of the C -Hydrocarbons 126
4
5.1 Macroeconomic Competition Factors . . . . . 126
5.1.1 Competition Criteria of Products in the Application Hierarchy 126
5.1.2 Limiting Factors of Trading . . . . . . . 128
5.1.3 Threshold Effects of Market Changes ........ . 130
5.2 Microeconomic Factors of Competition ....... . 132
5.2.1 Competition Factors Related to Products and Suppliers 132
5.2.2 Criteria of Quality as Factors in Competition. . . . . . 133
5.2.2.1 Classification of Product Properties According to the Application
Hierarchy .................... . 133
5.2.2.2 Economic and Metaeconomic Criteria for Quality 136
5.2.2.3 Property Standards of Products . . . . . . . . . . 136
5.2.3 Prices as Factors of Competition . . . . . . . . . 137
5.2.3.1 Prices After Fulfilment of Standards of Minimum Properties 137
5.2.3.2 Economically Calculable Application Properties of a Product
as Price Parameter . . . . . . . . . . . . . . . . . . . 137
5.2.3.3 Price Evaluation of the Metaeconomic Benefits of Use 139
5.2.4 Quantity as a Factor in Competition . . . . . . . . . . 140
5.3 Costs as a Basis of Price Competitiveness of a Product . 141
5.3.1 Cost Reduction via Increased Sales . 141
5.3.1.1 Lowering the Procurement Costs ........... . 141
x Contents
5.3.1.2 Lowering the Production Costs 142
5.3.1.3 Lowering Marketing Costs . . 144
5.3.1.4 Recovery of Rand D Costs . . 144
5.3.2 Lowering Costs by Utilization of Technological Progress. 145
5.3.2.1 Cost Reduction by Routine Work and Automatization. 145
5.3.2.2 Cost Reduction by Process Changes . . . . . . . 145
5.3.2.3 Cost Advantages Through Production Integration 148
5.3.2.4 Cost Increases or Decreases Through Co-products 148
5.3.3 Full Costs as Price Parameters . . . . . . . . . . 149
5.3.3.1 Problems of Evaluating Full Costs of Co-products 149
5.3.3.2 Company-Related Interpretations of Full Costs for Co-products. 150
5.3.3.3 Intercompany Transfer Prices. . 151
5.3.4 Methods of Cost Estimation .. 151
5.3.4.1 Estimation of Production Costs. 151
5.3.4.2 Forecasting Costs ....... . 155
5.3.4.3 Forecasting the Resource Costs of the Products 155
5.3.4.4 Forecasts of Costs on the Basis of Energy and Crude Oil
Equivalents . . . . . . . . . . . . . . . . . . . . . 155
6 Analyses of Competition of C "Chemical Products . . . 156
4
6.1 Prospects for C -Technologies in the Field of Gasoline
4
Components for Increasing Octane Numbers .... 156
6.1.1 The Need for High-Octane Components . . . . . . 156
6.1.2 Material Balance in Optimising the Octane Number 159
6.1.3 Technical Alternatives in Production of Gasoline
of High Octane Number .. . . 162
6.1.3.1 Survey ...................... . 162
6.1.3.2 Direct Blending of Refinery B-B ........ . 163
6.1.3.3 Conversion of Refinery B-B into Liquid Components 165
6.1.4 Comparison of Quantities. . . . . . . . 166
6.1.5 Comparison of Costs . . . . . . . . . . 169
6.1.5.1 Production Costs for Alkylate Gasoline 169
6.1.5.2 Production Costs for Polymer Gasoline. 171
6.1.5.3 Production Costs for MTBE . . . . . . 172
6.1.5.4 Production Costs for TBA . . . . . . . 173
6.1.5.5 Production Costs for MTBE and TBA from Butanes. 175
6.1.5.6 Production Costs for SBA ............ . 178
6.1.6 Evaluation of Profit for High-Octane Components . 178
6.1.6.1 Comparison of Properties . . . . . . . 179
6.1.6.2 Comparison of Profitability . . . . . . . . . . . . 181
6.1.7 Market Development for Oxygenates ..... . 185
6.2 Prospects for C -Technologies in the Plastics Field 188
4
6.2.1 C -Products in the Plastics Field . . . . . . 188
4
6.2.2 Costs of Obtaining Pure C -Base Chemicals 190
4
6.2.2.1 Production of Pure i-Butene 190
6.2.2.2 Production of Pure I-Butene ....... . 191
Contents XI
6.2.2.3 Production of Pure Butadiene ........ . 191
6.2.3 Butane Secondary Products in the Plastics Field 197
6.2.3.1 Maleic Anhydride and Fumaric Acid . . . . . . 197
6.2.3.2 Other Secondary Products . . . . . . . . . . . 202
6.2.4 Butene Secondary Products in the Plastics Field 203
6.2.4.1 Methyl Methacrylate 203
6.2.4.2 Poly-i-butene . . . . . . . . . . . . . . . . . . 206
6.2.4.3 Poly-I-butene . . . . . . . . . . . . . . . . . . 207
6.2.4.4 Processing of Other Polyolefines by Use of I-Butene
as Comonomer 214
7 Summary 221
References . . . 226
Company Index. 235
SUbject Index . . 237
Introduction
In contrast to manufacturers who apply mechanical processing and finishing methods,
the producers of chemical compounds can always markedly improve their competitive
position when they succeed in making high-grade secondary products from the
compounds for which there has been hitherto no, or only low-value, uses. Their
special attention is thus directed towards finding a more profitable use - as
economically and ecologically reasonable as possible - of the co-products which are
unavoidably yielded.
The usual bottleneck on the way to solving this problem is in the development of
suitable processes for utilizing these chemicals. It is not enough for the processes to be
technologically suitable for profiting from these alternative starting materials; proof
of their superior competitive ability is finally decisive for their usefulness.
Studies of the competitive power, especially intermediate-and long-term, of new
chemical technologies or products are complicated and have thus been treated up to
now in an inadequately scientific way. They consist of analyses and forecasts of the
economic values of competing processes and products, and also take into considera
tion criteria of competition which cannot be evaluated by economic parameters.
Evidence of economic success requires special consideration of marginal cost prob
lems which are complicated when co-products arise; this is because co-products are
yielded in different proportions and also usually of different type in differing
processes and/or with other starting materials. Further, changes in processes and/or
the choice of a different base chemical generally alter the property range of the
products and hence their market value; the estimation of the benefits from the
products to be prepared must be considered in relation to the evidence for economic
success. The analyses of application, profitability and substitution necessary for this
extend from the feedstocks right up to the end uses in the consumer goods sphere.
Competitive factors which cannot be evaluated economically also have an influ
ence above all as ecological interests and political dependence on the procurement,
production and/or sales chances of chemical products and the profitability of chemical
engineering innovations.
Such analyses and forecasts therefore demand comprehensive, systematic know
ledge along the lines of technology and ecology, production, strategies of procure
ment and utilization, cost calculation and political economy. It is true that in manage
ment science it is now stressed so that planning for success presupposes thinking of
decisions in several dimensions, as required in scenario analyses design. So far there
has been a lack of scientific work which has dealt with these problems of multi-layered
tasks of decision making in practice.
The aim of the present investigation is, taking the example of the chemistry of the