Propylene, catalytic oxidation

Commercial production of acetic acid has been revolutionized in the decade 1978—1988. Butane—naphtha Hquid-phase catalytic oxidation has declined precipitously as methanol [67-56-1] or methyl acetate [79-20-9] carbonylation has become the technology of choice in the world market. By-product acetic acid recovery in other hydrocarbon oxidations, eg, in xylene oxidation to terephthaUc acid and propylene conversion to acryflc acid, has also grown. Production from synthesis gas is increasing and the development of alternative raw materials is under serious consideration following widespread dislocations in the cost of raw material (see Chemurgy). 

There are currentiy two principal processes used for the manufacture of monomeric acryhc esters the semicatalytic Reppe process and the propylene oxidation process. The newer propylene oxidation process is preferred because of economy and safety. In this process acroleia [107-02-8] is first formed by the catalytic oxidation of propylene vapor at high temperature ia the preseace of steam. The acroleia is thea oxidi2ed to acryhc acid [79-10-7]. 

Acrylonitrile. Catalytic oxidation of propylene in the presence of ammonia (qv) yields acrylonitrile (95). 

Benzene is alkylated with propylene to yield cumene (qv). Cumene is catalytically oxidized in the presence of air to cumene hydroperoxide, which is decomposed into phenol and acetone (qv). Phenol is used to manufacture caprolactam (nylon) and phenoHc resins such as bisphenol A. Approximately 22% of benzene produced in 1988 was used to manufacture cumene. 

Degenerate Explosion it was a free radical autocatalytic process and control was difficult, but manageable. The main disadvantage was that it produced as much or more acrolein as propylene oxide. Because no market existed for acrolein at that time, the project was abandoned. Within two years, the acrylic market developed and a new project was initiated to make acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene. 

Much work has been invested to reveal the mechanism by which propylene is catalytically oxidized to acrolein over the heterogeneous catalyst surface. Isotope labeling experiments by Sachtler and DeBoer revealed the presence of an allylic intermediate in the oxidation of propylene to acrolein over bismuth molybdate. In these experiments, propylene was tagged once at Ci, another time at C2 and the third time at C3. 

Epoxides such as ethylene oxide and higher olefin oxides may be produced by the catalytic oxidation of olefins in gas-liquid-particle operations of the slurry type (S7). The finely divided catalyst (for example, silver oxide on silica gel carrier) is suspended in a chemically inactive liquid, such as dibutyl-phthalate. The liquid functions as a heat sink and a heat-transfer medium, as in the three-phase Fischer-Tropsch processes. It is claimed that the process, because of the superior heat-transfer properties of the slurry reactor, may be operated at high olefin concentrations in the gaseous process stream without loss with respect to yield and selectivity, and that propylene oxide and higher... 

Figure 9.18. Schematic picture ofthe different oxygen sites involved in the partial catalytic oxidation of propylene to acrolein on Bi2MoOg, along with their conceived role in the reaction...

In the case of selective oxidation catalysis, the use of spectroscopy has provided critical Information about surface and solid state mechanisms. As Is well known( ), some of the most effective catalysts for selective oxidation of olefins are those based on bismuth molybdates. The Industrial significance of these catalysts stems from their unique ability to oxidize propylene and ammonia to acrylonitrile at high selectivity. Several key features of the surface mechanism of this catalytic process have recently been descrlbed(3-A). However, an understanding of the solid state transformations which occur on the catalyst surface or within the catalyst bulk under reaction conditions can only be deduced Indirectly by traditional probe molecule approaches. Direct Insights Into catalyst dynamics require the use of techniques which can probe the solid directly, preferably under reaction conditions. We have, therefore, examined several catalytlcally Important surface and solid state processes of bismuth molybdate based catalysts using multiple spectroscopic techniques Including Raman and Infrared spectroscopies, x-ray and neutron diffraction, and photoelectron spectroscopy. 

Catalytic oxidative dehydrogenation of propane by N20 (ODHP) over Fe-zeolite catalysts represents a potential process for simultaneous functionalization of propane and utilization of N20 waste as an environmentally harmful gas. The assumed structure of highly active Fe-species is presented by iron ions balanced by negative framework charge, mostly populated at low Fe loadings. These isolated Fe sites are able to stabilize the atomic oxygen and prevent its recombination to a molecular form, and facilitate its transfer to a paraffin molecule [1], A major drawback of iron zeolites in ODHP with N20 is their deactivation by accumulated coke, leading to a rapid decrease of the propylene yield. 

The more expedient, direct catalytic oxidation route to acetone was developed in Germany in the 1960s. If you had been in charge of building the acetone business from scratch, you d probably not have built any IPA-to-acetone plants if you had known about the Wacker process. It s a catalytic oxidation of propylene at 200—250°F and 125—200 psi over palladium chloride with a cupric (copper) chloride promoter. The yields are 91-94%. The hardware for the Wacker process is probably less than for the combined IPA/acetone plants. But once the latter plants were built, the economies of the Wacker process were not sufficient to shut them down and start all over. So the new technology never took hold in the United States. 

The early ammoxidation plants were a two-step design. Propylene was catalytically oxidized to acrolein (CH2=CHCHO). The acrolein was then reacted with ammonia and air at high temperature to give acrylonitrile. The one-step process has replaced most of this hardware. 

Methyl methacrylate may be prepared by the catalytic oxidative carbonylation of propylene in the presence of methanol. 

Acrolein Production. Adams et al. [/. Catalysis, 3,379 (1964)] studied the catalytic oxidation of propylene on bismuth molybdate catalyst to form acrolein. With a feed of propylene and oxygen and reaction at 460°C, the following three reactions occur. 

The single-step production of acetone by the catalytic oxidation of propylene in the gas phase is a desirable goal, which can be achieved mainly by binary oxides.552 Acetone is obtained with better than 90% selectivity at 100-160°C when propylene is oxidized with H2O-O2 on SnC -MoOj.553 Ketone formation proceeds via hydration of the carbocation intermediate to form an adsorbed alcoholic species followed by oxydehydrogenation 553,554... 

Catalytic oxidation and ammoxidation of lower olefins to produce a,/3-unsaturated aldehyde or nitrile are widely industrialized as the fundamental unit process of petrochemistry. Propylene is oxidized to acrolein, most of which is further oxidized to acrylic acid. Recently, the reaction was extended to isobutylene to form methacrylic acid via methacrolein. Ammoxidation of propylene to produce acrylonitrile has also grown into a worldwide industry. 

Catalytic oxidation of propylene to acrolein was first discovered by the Shell group in 1948 on Cu20 catalyst (/). Both oxidation and ammoxidation were industrialized by the epoch-making discovery of bismuth molybdate catalyst by SOHIO (2-4). The bismuth molybdate catalyst was first reported in the form of a heteropoly compound supported on Si02, Bi P,Mo,2052/Si02 having Keggin structure but it was not the sole active species for the reactions. Several kinds of binary oxides between molybdenum trioxide and bismuth oxide have been known, as shown in the phase... 

Alkylation. Friedel-Crafts alkylation (qv) of benzene with ethylene or propylene to produce ethylbenzene [100-41 -4], CgH10, or isopropylbenzene [98-82-8], C9H12 (cumene) is readily accomplished in the liquid or vapor phase with various catalysts such as BF3 (22), aluminum chloride, or supported polyphosphoric acid. The oldest method of alkylation employs the liquid-phase reaction of benzene with anhydrous aluminum chloride and ethylene (23). Ethylbenzene is produced commercially almost entirely for styrene manufacture. Cumene [98-82-8] is catalytically oxidized to cumene hydroperoxide, which is used to manufacture phenol and acetone. Benzene is also alkylated with C1Q—C20 linear alkenes to produce linear alkyl aromatics. Sulfonation of these compounds produces linear alkane sulfonates (LAS) which are used as biodegradable deteigents. 

A method of considerable industrial importance for the large-scale preparation of ethylene oxide is direct oxidation of ethylene at elevated temperatures over a suitably prepared metallic silver catalyst. Although the reaction may be written aa indicated in Eq. (09), in actual practice only about half the ethylene is converted into ethylene oxide, the remainder being oxidized further to carbon dioxide and water. In spite of this seeming disadvantage, catalytic oxidation appears at present to bo economically competitive with chlorohydrin formation aa a means for the commercial production of ethylene oxide.MM Unfortunately, other olefins, such as propylene and mo-butylene for example, apparently give only carbon dioxide and water under the usual oxidation conditions,1310 so that until now the patent hu balance ethylene oxide has been the only representative accessible by tins route. 

ACRYLIC ACID AND DERIVATIVES. [CAS 79-10-7]. Acrylic acid (propenoic acid) was first prepared in 1847 by air oxidation of acrolein. Interestingly, after use of several other routes over the past half century, it is tins route, using acrolein from the catalytic oxidation of propylene, that is currently the most favored industrial process. 

Catalytic oxidation is the most important technology for the conversion of hydrocarbon feedstocks (olefins, aromatics and alkanes) to a variety of bulk industrial chemicals.1 In general, two types of processes are used heterogeneous, gas phase oxidation and homogeneous liquid phase oxidation. The former tend to involve supported metal or metal oxide catalysts e.g. in tne manufacture of ethylene oxide, acrylonitrile and maleic anhydride whilst the latter generally employ dissolved metal salts, e.g. in the production of terephthalic acid, benzoic acid, acetic acid, phenol and propylene oxide. 

Early attempts to use heteropoly compounds as catalysts are summarized in reviews published in 1952 (//) and 1978 (7). The first industrial process using a heteropoly catalyst was started up in 1972 for the hydration of propylene in the liquid phase. The essential role of the Keggin structure in a solid heteropoly catalyst was explicitly shown in 1975 in a patent concerning catalytic oxidation of methacrolein. Systematic research in heterogeneous catalysis with these materials started in the mid-1970s and led to the recognition of quantitative relationships between the acid or redox properties and catalytic performance... 

Acrylonitrile is used in the production of acrylic fibers and various resins. Acrylonitrile is produced by the catalytic oxidation of propylene and ammonia. About 0.48 tonnes of ammonia are needed to produce one tonne of acrylonitrile57. 

The Standard Oil Company of Ohio or SOHIO (now BP Amoco) developed and commercialized in 1960 a fluidized bed process in which the catalytic oxidation of a mixture of propylene and ammonia produced acrylonitrile (ACRN). By-products from this reaction are HCN and acetonitrile. The yields of HCN depend on the process conditions and on the catalyst system131. The reactions are ... 

Although the main routes to propylene oxide formation are not based on direct catalytic oxidation of propylene, the direct epox-idation of propylene on silver would be financially preferable if high yield and selectivity to propylene oxide could be achieved. Similarly to ethylene oxidation on silver part of the undesirable byproduct CO2 comes from the secondary oxidation of propylene oxide (2,3). The kinetics of the secondary silver catalyzed oxidation of propylene oxide to CO2 and H2O have been studied by very few investigators (2). 

Carbailo and Wolf(2) during the catalytic oxidation of propylene over Pt/fAl203. Propylene seems to be oxidized more readily on flat surfaces (terraces), which are more likely to occur on the larger crystallites, than on the ledges and kinks, which are more numerous on the smaller crystallites. The weaker chemisorption bonds (i.e. higher desorption rate) over the terraces might be responsible for this effect. 

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