Olefin hydration processes

Carbon-carbon bond formation and cleavage. In olefin hydration processes, minor amounts of dimers and polymers are produced by the mechanism... 

The hydration of acetylene produces acetaldehyde which then can be converted to acetic acid and other derivatives. The process is similar to olefin hydration employing a sulfuric acid solution containing also a mercurous sulfate catalyst. 

Direct Oxidation. Direct oxidation of petroleum hydrocarbons has been practiced on a small scale since 1926 methanol, formaldehyde, and acetaldehyde are produced. A much larger project (29) began operating in 1945. The main product of the latter operation is acetic acid, used for the manufacture of cellulose acetate rayon. The oxidation process consists of mixing air with a butane-propane mixture and passing the compressed mixture over a catalyst in a tubular reaction furnace. The product mixture includes acetaldehyde, formaldehyde, acetone, propyl and butyl alcohols, methyl ethyl ketone, and propylene oxide and glycols. The acetaldehyde is oxidized to acetic acid in a separate plant. Thus the products of this operation are the same as those (or their derivatives) produced by olefin hydration and other aliphatic syntheses. 

The catalytic hydration of olefins can also be performed in a three-phase system solid catalyst, liquid water (with the alcohol formed dissolved in it) and gaseous olefin [258,279,280]. The olefin conversion is raised, in comparison with the vapour phase processes, by the increase in solubility of the product alcohol in the excess of water [258]. For these systems with liquid and vapour phases simultaneously present, the equilibrium composition of both phases can be estimated together with vapour-liquid equilibrium data [281]. For the three-phase systems, ion exchangers, especially, have proved to be very efficient catalysts [260,280]. With higher olefins (2-methylpropene), the reaction was also performed in a two-phase liquid system with an ion exchanger as catalyst [282]. It is evident that the kinetic characteristics differ according to the arrangement (phase conditions), i.e. whether the vapour system, liquid vapour system or two-phase liquid system is used. However, most kinetic and mechanistic studies of olefin hydration were carried out in vapour phase systems. 

Lower alcohols (amyl and below) are prepared by (a) hydrogeneration of carbon monoxide (yields methanol), (b) olefin hydration (yields ethanol, isopropanol, secondary and tertiary butanol), (c) hydrolysis of alkyl chlorides, (d) direct oxidation, and (e) the 0X0 process,... 

HPAs, however, is their solubility in polar solvents or reactants, such as water or ethanol, which severely limits their application as recyclable solid acid catalysts in the liquid phase. Nonetheless, they exhibit high thermal stability and have been applied in a variety of vapor phase processes for the production of petrochemicals, e.g. olefin hydration and reaction of acetic acid with ethylene [100, 101]. In order to overcome the problem of solubility in polar media, HPAs have been immobilized by occlusion in a silica matrix using the sol-gel technique [101]. For example, silica-occluded H3PW1204o was used as an insoluble solid acid catalyst in several liquid phase reactions such as ester hydrolysis, esterification, hydration and Friedel-Crafts alkylations [101]. HPAs have also been widely applied as catalysts in organic synthesis [102]. 

Hydration of olefins to alcohols is equilibrium limited and hence CD is potentially suitable for such applications. The catalysts used for the process are acidic catalysts such as cation-exchange resins or zeolites. The hydration of isobutylene to produce tert-h ity alcohol via CD results in a higher conversion and there is no need to recycle the water. The hydration process is catalyzed by acidic ion-exchanged resins at 85°C and about 1200 kPa. The CD process configuration involves feeding the isobutylene below the catalyst zone and the water is fed above the catalyst zone. Flooding of the reaction zone is introduced in the process to improve the contact between the catalyst and the liquid and to ensure that the water is in constant contact with the catalyst sites. Flooding of the catalyst zone apparently improves the catalyst lifetime and performance because catalyst deactivation is caused by mass transfer and liquid distribution problems. Some recent publications on the hydration of isobutylene include a patent and a study of the kinetics of the hydration process and discussions on the merits of the application of CD for hydration. 

In these liquid phase hydration processes the acid plays the role of a catalyst by forming esters with the olefins, which subsequently undergo hydrolysis to yield alcohols and release the acid. In the case of the higher olefins this intermediate esterification and hydrolization occurs as the olefins are passed into the solution, and free alcohols appear in the product. With the higher olefins practically complete hydration occurs even in dilute acids.07b However, in the case of the lower olefins, which dissolve... 

The difficulties attending the catalytic vapor phase hydration of olefins, while not apparent from the claims made in the patents which have been obtained for such processes, are serious and numerous. Aside from those already mentioned, the difficulties of separating the alcohol from the dilute liquid condensate by distillation and of purifying the alcohols from hydrocarbon polymers by a process of chlorination or selective absorption must be overcome. In view of the success that has attended the hydration of olefins, particularly those higher than ethylene, by means of absorption in sulfuric acid followed by dilution and distillation, it is probable that direct hydration processes at the present stage of the art will be unable to compete as long as cheap sulfuric acid is available. 

Oxidic catalysts with acidic properties catalyze many industrial reactions, including the dehydration of alcohols, the hydration of olefins, cracking processes, and olefin polymerization. How does the acidity of such solids arise ... 

Other processes include the alkylation of phenol using alkenes, and the manufacture of acrylate and methacrylate esters from alcohols and the corresponding acids. Olefin hydration reactions require more extreme conditions but Deutsche Texaco have developed a resin-catalysed propene hydration process to form isopropyl alcohol [125]. The reaction is run at 130 C near the upper limit for sulphonic acid resins, but a species with sufficient lifetime is available. There is even some evidence that butene hydration is now carried out similarly. Finally, B.P. Chemicals have recently disclosed [126] a new olefin isomerisation process yielding 2,3-dimethylbut-l-ene. Here the conditions required to favour the isomerisation versus rapid oligomerisation had to be identified to establish a viable process. 

Pfeuffer, B., Petre, D., Kunz, U., Hoffmann, U., Turek, T. and HoU, D. (2007). Production of sec-butyl alcohol by olefin hydration — a candidate for process intensification Proceedings of the European Congress of Chemical Engineering (ECCE-6), Copenhagen, 16-20 September. 

For saturated fatty acids, the process of /3-oxidation involves a recurring cycle of four steps, as shown in Figure 24.10. The overall strategy in the first three steps is to create a carbonyl group on the /3-carbon by oxidizing the C, —C bond to form an olefin, with subsequent hydration and oxidation. In essence, this cycle is directly analogous to the sequence of reactions converting succi-... 

Efficient anti-Markonikov addition of water to terminal olefins producing primary alcohols would be one of the most desirable catalytic processes (Eq. 6.45). As one example of such a reaction, Jensen and Trogler reported the anti-Markonikov hydration of terminal olefins catalyzed by a platinum(II) trimethylphosphine complex producing primary alcohols [83]. The report, however, was claimed to be of doubtful reproducibility [84]. 

Conversion of benzene to cyclohexene by partial catalytic hydrogenation is a very important industrial process, since it provides a new route to cyclohexanol, a precursor of nylon, when combined with hydration of cyclohexene. For example, Asahi Chemical Company of Japan developed a selective bilayer catalytic system including a Ru catalyst, Zr02 and ZnS04 under 50 atm of H2 pressure, a process affording the olefin with up to 60% selectivity after 90% conversion of benzene.72... 

You may wonder why boch these processes produce isopropyl alcohol instead of (normal) propyl alcohoL With the exception of ethylene, direct or indirect hydration of an aliphatic olefin always produces an alcohol with the hydroxyl group preferentially attached to the double-bonded carbon with the least number of hydrogen atoms. 

Unfortunately, secondary and tertiary butyl alcohols (SBA and TBA) cannot be made by the Oxo process. Instead they are produced either by indirect or direct hydration of the corresponding olefin. Normal butylene gives SBA and isobutylene gives TBA. The processes are similar to the corresponding routes to IPA. 

The oxo reaction (31) is carried out in the liquid phase at high pressure using a cobalt catalyst. A mixture of aldehyde isomers is always produced, each isomer being one carbon number higher than the starting olefin. As a group the oxygenated products of the hydrocarbon synthesis (Fischer-Tropsch) process and the oxo process are primary compounds and thus (except, of course, the methyl and ethyl derivatives) differ fundamentally from the products based on alcohols made by the hydration of olefins, which are always secondary or tertiary in structure. 

There is also an apparent trend in manufacturing operations toward simplification by direct processing. Examples of this include the oxidation of ethylene for direct manufacture of ethylene oxide the direct hydration of ethylene to produce ethyl alcohol production of chlorinated derivatives by direct halogenation in place of round-about syntheses and the manufacture of acrolein by olefin oxidation. The evolution of alternate sources, varying process routes, and competing end products has given the United States aliphatic chemical industry much of its vitality and ability to adjust to varying market conditions. 

Hydration means, in general, addition of the elements of water to a substance. Most of these reactions are non-catalytic or homogeneously catalysed processes. In this section, only hydration of olefins to alcohols, of acetylene to acetaldehyde, and of alkene oxides to glycols will be treated, since they are typical reactions where the application of solid catalysts has become important. 

The several attempts, published in the literature, to describe the kinetics of vapour phase olefin (mostly ethylene) hydration can be classified into two groups according to the basic model used. One model, for reactions catalysed by phosphoric acid supported on solids, treats the kinetics as if the process were homogeneous acid catalysis and takes into account the acid strength of the supported acid. Thus, a semiempirical equation for the initial reaction rate [288]... 

Data indicative of the relative basicities of C=C and C=C bonds and relative solvation energies for protonation processes have been obtained from measurements of hydration rates of RCH=CH2 and RC=CH (R = H, Me, Bu ) in aqueous H2SO441. Enthalpies of hydration of a series of acyclic olefins producing tertiary alcohols have been determined42,43. 

The important process variables in the polymerization of olefins from cracked gases are time, catalyst activity, pressure, hydration, and temperature. All these variables are related to some extent and can be interchanged within certain narrow limits. 

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