Of n-butenes

R. H. Schwaar and S. Morimoto, Methyl Ethyl Ketone by Direct Oxidation of n-Butenes, Process Economics Program, Review No. 87-2-3, SRI International, Menlo Park, Calif., Oct. 1988. 

Figure 2-1 shows the two processes for the separation of n-butenes from isobutene. ... 

Oxidation of n-hutane to maleic anhydride is becoming a major source for this important chemical. Maleic anhydride could also be produced by the catalytic oxidation of n-butenes (Chapter 9) and benzene (Chapter 10). The principal use of maleic anhydride is in the synthesis of unsaturated polyester resins. These resins are used to fabricate glass-fiber reinforced materials. Other uses include fumaric acid, alkyd resins, and pesticides. Maleic acid esters are important plasticizers and lubricants. Maleic anhydride could also be a precursor for 1,4-butanediol (Chapter 9). 

Acetic acid may also be produced by reacting a mixture of n-butenes with acetic acid over an ion exchange resin. The formed sec-butyl acetate is then oxidized to yield three moles of acetic acid ... 

This is the same case with which in Eqs. (2)-(4) we demonstrated the elimination of the time variable, and it may occur in practice when all the reactions of the system are taking place on the same number of identical active centers. Wei and Prater and their co-workers applied this method with success to the treatment of experimental data on the reversible isomerization reactions of n-butenes and xylenes on alumina or on silica-alumina, proceeding according to a triangular network (28, 31). The problems of more complicated catalytic kinetics were treated by Smith and Prater (32) who demonstrated the difficulties arising in an attempt at a complete solution of the kinetics of the cyclohexane-cyclohexene-benzene interconversion on Pt/Al203 catalyst, including adsorption-desorption steps. 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

In the case of n-butene isomerization it was demonstrated (Figure 2) that the ideal micro-pore topology led to retardation of the C8 dimer intermediate and that the catalyst based on the ferrierite structure was close to optimal in this respect [1). For selective isodewaxing a one-dimensional pore structure which constrained the skeletal isomerization transition state and thereby minimized multiple branching such as the SAPO-11 structure was found to meet these criteria. Clearly, these are ideal systems in which to apply computational chemistry where the reactant and product molecules are relatively simple and the micro-porous structures are ordered and known in detail. 

The specific interaction of the admolecule with the surface is then rather well established, while the geometry of the adsorbed species is only tentative. One important conclusion to be drawn from the study of the chemical shifts, is that they cannot by themselves indicate unambiguously the exact geometry of a "contact-type complex". Nevertheless the 7r-complex nature of the adsorbed species was also suggested by the dependence of the adsorption coefficient of n-butenes on their energy of ionization (4). 

Recent studies of the kinetics and mechanism of n-butene isomerization over lanthanum oxide by Rosynek et al. (28) indicate that for this catalyst interconversion of the two 2-butene isomers (s4 in Example 8) is very slow and in that case the system could be described by mechanism m3. Studies by Goldwasser and Hall (29) indicate that as temperature is increased, there is appreciable direct conversion via s4 so that one or both of the other two direct mechanisms may be involved. These authors suggest that further studies with all three isomers, at several temperatures and with tracers, would be desirable. 

Another point illustrated by Table XXIII is the need to carefully consider the effect of lumping isomers for convenience, when mechanistic models are generated. Thus, in Example 4, isomerization of 1-butene is neglected in selecting the elementary steps for butadiene production. In effect, it is assumed that all intermediates are indistinguishable whether 1-butene or a mixture of n-butenes reacts. If that scheme were used in the present case, we could consider a model in which only s, s2, s3, s4, s6, and s j 3 were retained, which would correspond to only a single direct mechanism. However, if instead we chose to retain all the elementary steps as possibilities except Sj j and s12, we would obtain five direct mechanisms for a system producing only 1-butene (in which p — a = 0). 

Clinoptilolite Isomerization of n-butene, the dehydration of methanol to dimethyl ether, and the hydration of acetylene to acetaldehyde... 

Another large use of normal butenes in the petrochemical industry is in the production of 1,3-butadiene (CH2 = CH = CH = CH2). In the process, a mixture of n-butenes, air, and steam is passed over a catalyst at a temperature of 500°C to 600°C. Butadiene is used extensively to produce synthetic rubbers (see Isoprene) in polymerization reactions. The greatest use of butadiene is for styrene-butadiene rubber, which contains about a 3 1 ratio of butadiene to styrene. Butadiene is also used as a chemical intermediate to produce other synthetic organics such as chloroprene, for adhesives, resins, and a variety of polymers. 

Because of their very similar boiling points and azeotrope formation, the components of the C4 fraction cannot be separated by distillation. Instead, other physical and chemical methods must be used. 1,3-Butadiene is recovered by complex formation or by extractive distillation.143-146 Since the reactivity of isobutylene is higher than that of n-butenes, it is separated next by chemical transformations. It is converted with water or methyl alcohol to form, respectively, tert-butyl alcohol and tert-butyl methyl ether, or by oligomerization and polymerization. The remaining n-butenes may be isomerized to yield additional isobutylene. Alternatively, 1-butene in the butadiene-free C4 fraction is isomerized to 2-butenes. The difference between the boiling points of 2-butenes and isobutylene is sufficient to separate them by distillation. n-Butenes and butane may also be separated by extractive distillation.147... 

The relative contribution of the two mechanisms to the actual isomerization process depends on the metals and the experimental conditions. Comprehensive studies of the isomerization of n-butenes on Group VIII metals demonstrated179-181 that the Horiuti-Polanyi mechanism, the dissociative mechanism with the involvement of Jt-allyl intermediates, and direct intramolecular hydrogen shift may all contribute to double-bond migration. The Horiuti-Polanyi mechanism and a direct 1,3 sigma-tropic shift without deuterium incorporation may be operative in cis-trans isomerization. 

Besides the rearrangement of carbocations resulting in the formation of isomeric alkylated products, alkylation is accompanied by numerous other side reactions. Often the alkene itself undergoes isomerization prior to participating in alkylation and hence, yields unexpected isomeric alkanes. The similarity of product distributions in the alkylation of isobutane with n-butenes in the presence of either sulfuric acid or hydrogen fluoride is explained by a fast preequilibration of n-butenes. Alkyl esters (or fluorides) may be formed under conditions unfavorable for the hydride transfer between the protonated alkene and the isoalkane. 

Relatively few reports of the catalysed reactions of n-butenes with hydrogen were extant up to the early 1960 s. Those studies which had been performed were mainly concerned with nickel as catalyst. The major problem was the difficulty of chemical analysis of the reaction products. However, with the advent of gas chromatography as a general analytical technique, the analysis of reaction products has become a relatively simple task and, accordingly, over the last 15 years the hydrogenation of higher olefins has received considerable attention. 

One of the earliest studies of n-butene hydrogenation was that reported by Twigg [121] who observed that, for the reaction of l butene with hydrogen over a nickel wire between 76 and 126°C, both hydrogenation and double-bond migration occurred. Hydrogenation and double-bond migration followed the same kinetic rate law, namely... 

Steam may have a positive effect on the activity according to Komaro-vskii et al. [179], A doubling of the reaction rate was observed by adding up to 20% steam to the oxidation of a mixture of n-butenes in a flow reactor over a Bi/Mo catalyst of unknown composition at 420—480°C. The same authors [179] also studied the influence of the oxygen concentration, which was found to have no effect on the kinetics at 02/butene > 0.4. Furthermore, a rather complex set of kinetic equations was derived to describe side reactions (isomerization, and formation of carbonyls, acids and furan). 

Tphe isomerization of olefins over acidic catalysts has been carefully A studied in the past few years. Hightower and Hall (1, 2) have studied the isomerization of n-butenes over silica-alumina. They were able to interpret their results in terms of a simple model involving the 2-butyl carbonium ion as a common intermediate. More recently Lombardo and Hall studied the isomerization of the same olefins over Na-Y-zeolite. They showed that the reaction was first order in conversion as well as time (3), that the isomers could be directly interconverted (4), and that activity sharply increased with water addition reaching a saturation value (5). There are, however, reports in the literature which are at variance with this idea. Dimitrov et al. (7, 8) explained their results for n-butene isomerization on Na-X-zeolite in terms of a free radical type mechanism. As discussed more thoroughly elsewhere (4) others have argued about the nature of catalytic activity on zeolites (9-13). 

Kinetics. Two series of experiments were performed, isomerizing about 55 cc (STP) of n-butenes or n-pentenes over 76 mg (dry basis) of catalyst I using 2 H20/cage as co-catalyst. The rate constant ratios were determined by either the extended Wei and Prater method (3) or the zero intercepts of the extrapolated product ratios obtained starting with different isomers. These ratios determined at different temperatures were plotted in Figure 1. The rate constant are defined as ... 

The isomerizations of n-butenes and n-pentenes over a purified Na-Y-zeolite are first-order reactions in conversion as well as time. Arrhenius plots for the absolute values of the rate constants are linear (Figure 2). Similar plots for the ratio of rate constants (Figure 1), however, are linear at low temperatures but in all cases except one became curved at higher temperatures. This problem has been investigated before (4), and it was concluded that there were no diffusion limitations involved. The curvature could be the result of redistribution of the Ca2+ ions between the Si and Sn positions, or it could be caused by an increase in the number of de-cationated sites by hydrolysis (6). In any case the process appears to be reversible, and it is affected by the nature of the olefin involved. In view of this, the following discussion concerning the mechanism is limited to the low temperature region where the behavior is completely consistent with the Arrhenius law. 

Fig. S. Hydrogen promoting effects on the cis to trans isomerization (a) and the double bond migration (b) of n-butenes on MoS2 catalyst at room temperature (36).

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