Catalysis : an Integrated Approach to Homogeneous ...

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2 -CATALYTIC PROCESSES IN INDUSTRY Scale - U 0 0 c K 0 20 c gasoline 5 butylenes s - - 60 50 E] 40 I I 0 Fig. 2.23. Product yields in catalytic cracking vs. ZSM content in FCC catalyst. Snamprogretti isomerisat ion (modified alumina) Fig. 2.24. Two routes for isobutene from butane. MTBE is the fastest growing chemical of the last decade. Presently, over 11 million t/y capacity has been installed. Further growth is foreseen. Essentially the success of MTBE is founded (i) on its outstanding antiknock properties as a gasoline component, and (ii) its function as a key product in the C4 hydrocarbon processing within a refinery. Process Description The synthesis of MTBE is carried out in the liquid phase over a fixed bed of ion - 59
60 7. -CATALYTIC PROCESSES IN INDUSTRY exchange resin in the H+ form. The rate of reaction of isobutene with methanol is much higher than that of the n-butenes (isobutene forms a relatively stable tertiary carbenium ion in the first step), which enables the selective conversion of isobutene in the presence of the n-butenes. In fact, streams with an isobutene content as low as 5% can be converted. A C4 fraction and methyl alcohol (molar ratio methyl alcohol:i-C4 = 1:l) is preheated to about 70°C before being sent to the reactor containing a fixed bed of sulphonated polystyrene resin. The reaction is exothermic (AH298 = -37.7 kJ/mol) and the heat produced is removed by means of cooling jackets so as to keep the temperature below 120°C. The reaction mixture from the top of the reactor is distilled and any unreacted butene is collected overhead with the azeotropic amount of methyl alcohol. The bottom contains pure MTBE. The distillate, together with additional methyl alcohol, is passed to a second reactor. The products from the second stage are extracted with water to remove residual methyl alcohol. The water-methyl alcohol solution is distilled to recover methyl alcohol, which is recycled. The second stage in the process is required because the MTBE formation is an equilibrium reaction. The temperature needed (-100°C) to achieve a sufficiently high rate of conversion means a decrease in isobutene equilibrium conversion (X~B = 0.9 at 65°C) X ~B = -0.75 at l0OOC). The main side reaction in the MTBE process is the dimerization of isobutene towards di-isobutene (two isomers). Side reactions with essentially no significance are the formation of t-butyl alcohol (due to the presence of water as feed impurity), the formation of dimethyl ether from methyl alcohol, and the oligomerization of isobutene towards tri- and tetramers. A (three stage) process is also in operation which tolerates butadiene. The butadiene/methyl alcohol reaction is faster than that of the n-butenes but considerably slower than that of isobutene, so high isobutene selectivity can still be obtained. Similar liquid phase processes, as described above for MTBE, are recommended for the reaction of isopentenes and methanol to yield TAME and for the conversion of isobutene and ethanol to give ETBE. The use of higher iso-olefins - as for TAME - leads to somewhat lower yields of methyl t-alkyl ethers than are obtained for MTBE. As an alternative to fixed bed catalytic conversion the formation of MTBE by ‘reactive distillation’ is applied. Here in situ separation of feed and product components is aimed at, leading to a higher isobutene conversion. A flow scheme is given in Fig. 2.25. The Catalyst The catalysts used industrially in the MTBE process are sulphonated polystyrene resins of the macroreticular type, These strongly acidic materials are prepared by copolymerizing styrene and p-divinylbenzene in the presence of an organic compound that is a good solvent for the monomers but a poor swelling
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Studies in Surface Science and Cata
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Studies in Surface Science and Cata
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Preface Catalysis is a fascinating
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industrial context of the features
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Contents Preface ..................
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4.3.4 P-Elimination and Deinsertion
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7.4.1 Scope .......................
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12.3 Adsorption Isotherms .........
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List of contributors E.B.M. Doesbur
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Introductory section
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Chapter 1 History of catalysis 1.1
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1 -HISTORY OF CATALYSIS 5 One of th
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1 - HISTORY OF CATALYSIS 7 was disc
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Chapter 5 Heterogeneous catalysis 5
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5 -HETEROGENEOUS CATALYSIS 161 a. _
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5 -HETEROGENEOUS CATALYSIS 163 appr
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5 -HETEROGENEOUS CATALYSIS 165 In r
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5 - HETEROGENEOUS CATALYSIS 167 lit
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5 - HETEROGENEOUS CATALYSIS 169 An
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5 -HETEROGENEOUS CATALYSIS 171 A ma
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5 - HETEROGENEOUS CATALYSIS 173 2 L
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5 - HETEROGENEOUS CATALYSIS 175 (3)
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5 -HETEROGENEOUS CATALYSIS 177 20 '
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5 -HETEROGENEOUS CATALYSIS 179 with
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5 -HETEROGENEOUS CATALYSIS 183 Info
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5 -HETEROGENEOUS CATALYSIS 185 0 20
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5 - HETEROGENEOUS CATALYSIS 187 TAB
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5 -HETEROGENEOUS CATALYSIS 189 i)U
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5 -HETEROGENEOUS CATALYSIS 600 560
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5 -HETEROGENEOUS CATALYSIS 193 b H
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Chapter 6 Homogeneous catalysis wit
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6 -HOMOGENEOUS CATALYSIS WlTH TRANS
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6 - HOMOGENEOUS CATALYSIS WlTH TRAN
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6 -HOMOGENEOUS CATALYSIS WITH TRANS
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6 - HOMOGENEOUS CATALYSIS WlTH TRAN
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6 - HOMOGENEOUS CATALYSIS WITH TRAN
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6 -HOMOGENEOUS CATALYSIS WTH TRANSI
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Applied catalysis
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Chapter 7 Catalytic reaction engine
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7 -CATALYTIC REACTION ENGINEERING 2
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Ca ta I ys t preparation
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Chapter 8 Preparation of catalyst s
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8 - PREPARATION OF CATALYST SUPPORT
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8 -PREPARATION OF CATALYST SUPPORTS
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Chapter 9 Preparation of supported
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PREPARATION OF SUPPORTED CATALYSTS
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Catalyst characterization
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Chapter 10 Ca ta I yst characteriza
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10 -CATALYST CHARACTERIZATION WITH
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Chapter 11 Temperature programmed r
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11 -TEMPERATURE PROGRAMMED REDUCTIO
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Chapter 12 The use of adsorption me
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12 -ADSORPTION METHODS 421 pairs of
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12 -ADSORPTION METHODS 423 of multi
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12 -ADSORPTION METHODS 425 son of t
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12 - ADSORPnON METHODS 427 equation
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12 - ADSOWON METHODS / Fig. 12.4. T
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12 - ADSOFSTION METHODS 431 - a i-
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12 -ADSORPTION METHODS 433 uptake o
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12 - ADSOlU'TION METHODS 435 gives
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12 - ADSOFSTION METHODS 437 condens
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Future trends
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Chapter 13 Future trends The large
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13 - FUTURE TRENDS 443 control of t
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13 -FUTURE TRENDS 445 the conversio
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Subject Index x-Acceptor Iigands, 2
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SUBJECT INDEX 449 - see also Extend
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SUBJECr INDEX 451 Ethane, 143 Ethen
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SUBJECT INDEX 453 Hydrogen peroxide
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SDJJTT INDEX 455 Octane number, 24,
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SUBJECT INDEX 457 RBS, 383 Reaction
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SUBJECT INDEX 459 - see also Ruther
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STUDIES IN SURFACE SCIENCE AND CATA
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Volume 35 Volume 36 Volume 37 Volum
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Volume 70 Volume 71 Volume 72 Volum
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