Propylene oxidation to acrolein

The Reaction. Acrolein has been produced commercially since 1938. The first commercial processes were based on the vapor-phase condensation of acetaldehyde and formaldehyde (1). In the 1940s a series of catalyst developments based on cuprous oxide and cupric selenites led to a vapor-phase propylene oxidation route to acrolein (7,8). In 1959 Shell was the first to commercialize this propylene oxidation to acrolein process. These early propylene oxidation catalysts were capable of only low per pass propylene conversions (ca 15%) and therefore required significant recycle of unreacted propylene (9—11). 

The reaction is very exothermic. The heat of reaction of propylene oxidation to acrolein is 340.8 kJ /mol (81.5 kcal/mol) the overall reactions generate approximately 837 kJ/mol (200 kcal/mol). The principal side reactions produce acryUc acid, acetaldehyde, acetic acid, carbon monoxide, and carbon dioxide. A variety of other aldehydes and acids are also formed in small amounts. Proprietary processes for acrolein manufacture have been described (25,26). 

Both fixed and fluid-bed reactors are used to produce acrylonitrile, but most modern processes use fluid-bed systems. The Montedison-UOP process (Figure 8-2) uses a highly active catalyst that gives 95.6% propylene conversion and a selectivity above 80% for acrylonitrile. The catalysts used in ammoxidation are similar to those used in propylene oxidation to acrolein. Oxidation of propylene occurs readily at... 

In the temperature range of 580-600 °C, propylene oxidation to acrolein proceeds at the commensurable rate simultaneously with propylene epoxidation. At 600-640 °C and r = 1.2 s acrolein is the predominant product with 80% average yield. 

Volta, J. C, Desquesnes, W., Moraweck, B., and Coudurier, G., A new method to obtain supported oriented oxides M0O3 graphite catalysts in propylene oxidation to acrolein, React. Kinet. Catal. Lett. 12, 241 (1979). 

There is evidence for isomerization of chemisorbed propylene oxide to acrolein on silver and for surface polymer formation on metal oxide catalysts (11,12). Formation of a surface polymeric structure has also been observed during propylene oxidation on silver (13). It appears likely that the rate oscillations are related to the ability of chemisorbed propylene oxide to form relatively stable polymeric structures. Thus chemisorbed monomer could account for the steady state kinetics discussed above whereas the superimposed fluctuations on the rate could originate from periodic formation and combustion of surface polymeric residues. 

The first real characterization of active phases has been made for the high temperature polymorph of CoMoO (called (a) by us and later (b) by other authors) in the selective oxidation of butane to butadiene (20,21), as well as for (22) and bismuth molybdates (23,24) for oxidation, and ammoxidation of propylene. Additional examples include solid solutions such as (Mo V. )90t (with 0benzene conversion to maleic anhydride (25,26 and the solid solution up to 15% of Sb O in the SnO -Sb O system for propylene oxidation to acrolein (14,2/). 

The segregation phenomena in V-Sb-0 catalyst for selective propylene oxidation to acrolein were studied by means of X-ray photoelectron spectroscopy, scanning electron microscopy with EDS, as well as electron and X-ray diffraction. The vanadium antimonate crystals were found to be a main component of the catalyst. It was stated that epitaxial layers of antimony tetroxide on the base faces of vanadium antimonate crystals, exposing (010) plane, were responsible for high catalyst selectivity. 

Acrolein is produced according to the specifications in Table 3. Acetaldehyde and acetone are the principal carbonyl impurities in freshly distilled acrolein. Acrolein dimer accumulates at 0.50% in 30 days at 25°C. Analysis by two gas chromatographic methods with thermal conductivity detectors can determine all significant impurities in acrolein. The analysis with Porapak Q, 175—300 p.m (50—80 mesh), programmed from 60 to 250°C at 10°C/min, does not separate acetone, propionaldehyde, and propylene oxide from acrolein. These separations are made with 20% Tergitol E-35 on 250—350 p.m (45—60 mesh) Chromosorb W, kept at 40°C until acrolein elutes and then programmed rapidly to 190°C to elute the remaining components. 

Oxidation Catalysis. The multiple oxidation states available in molybdenum oxide species make these exceUent catalysts in oxidation reactions. The oxidation of methanol (qv) to formaldehyde (qv) is generally carried out commercially on mixed ferric molybdate—molybdenum trioxide catalysts. The oxidation of propylene (qv) to acrolein (77) and the ammoxidation of propylene to acrylonitrile (qv) (78) are each carried out over bismuth—molybdenum oxide catalyst systems. The latter (Sohio) process produces in excess of 3.6 x 10 t/yr of acrylonitrile, which finds use in the production of fibers (qv), elastomers (qv), and water-soluble polymers. 

Exception No. 2 Group C equipment shall be permitted to be used for atmospheres containing ethylene oxide, propylene oxide, and acrolein if such equipment is isolated in accordance with Section 501-5(a) by sealing all conduit /2 -in. size or larger. 

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. 

When propylene tagged with at either Ci or C3 was oxidized to acrolein and then degraded, both CH2=CH2 and CO were radioactive, and the ratio of radioactivity was 1. 

Telescope the Process by Combining Stages. This has been done successfully in the conversion of propylene to acrylonitrile by direct ammoxidation rather than oxidation to acrolein followed by reaction with ammonia in a separate stage, as was described in the earlier patent literature. The oxychlorination of ethylene and HC1 directly to vinyl chloride monomer is another good example of the telescoping of stages to yield an economic process. 

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. 

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. 

The only direct evidence for the participation of adsorbed oxygen in the selective oxidation of propylene under reaction conditions is the work of Cant and Hall (22, 23). They reported that propylene could be oxidized to acrolein over noble metals (Au, Rh, and Ru) supported on low-surface-area a-alumina or silica. These catalysts do not contain any usable lattice oxygen, therefore, only adsorbed or gas-phase oxygen is available as a... 

The direct oxidation of propane has fewer restrictions on plant location since the alkane is easier to ship over long distances as the compressed liquid. Its oxidation to acrolein, acrylic acid and acrylonitrile is the subject of numerous studies. The synthesis of acrylonitrile has already been developed to the stage of a demonstration plant. Catalysts are based on V-Sb mixed oxides, with additional metal promoters. Propylene is generally recognized as the intermediate through which acrylonitrile is obtained. Selectivities are close to 50-60% at ca. 20% propane conversion. 

Bismuth Molybdate Catalysts. The Raman spectra of the bismuth molybdates, with Bi/Mo stoichiometric ratios between 0.67 and 14, have been examined using the FLS approach (see Section 3.2). " The bismuth molybdates fall into an unusual class of compounds, the ternary bismuth oxide systems Bi-M-0 (where M = Mo, W, V, Nb, and Ta) which exhibit a variety of interesting physical and chemical properties. Of commercial importance, the bismuth molybdates are heterogeneous catalysts for selective oxidations and ammoxidations (the Sohio process), for example, propylene ( 311 ) to acrolein (C3H4O) by oxidation or to acrylonitrile (C3H3N) by arrunoxidation. ... 

Derivation (1) Condensation of ethylene oxide with hydrocyanic acid followed by reaction with sulfuric acid at 320F (2) acetylene, carbon monoxide, and water, with nickel catalyst (3) propylene is vapor oxidized to acrolein, which is oxidized to acrylic acid at 300C with molybdenum-vanadium catalyst (4) hydrolysis of acrylonitrile. 

Derivation (1) By-product of soap manufacture (2) from propylene and chlorine to form allyl chloride, which is converted to the dichlorohydrin with hypo-chlorous acid this is then saponified to glycerol with caustic solution (3) isomerization of propylene oxide to allyl alcohol, which is reacted with peracetic acid, (the resulting glycidol is hydrolyzed to glycerol) (4) hydrogenation of carbohydrates with nickel catalyst (5) from acrolein and hydrogen peroxide. 

Riser technology appears to be quite versatile. Patience and Mills [33] investigated propylene oxidation into acrolein and found that this technique has a potential for the commercial scale production of acrolein. Their kinetic model was based on a simplified single site redox mechanism involving consecutive-parallel reactions for the partial and complete oxidation of propylene. Its predictions of the performance of the reactor gave correct trends. 

This process consists of a three-step reaction propylene is oxidized to acrolein, aaolein is hydrated to 3-hydroxypropionaldehyde, which then is reduced to PDO (Amtz 1991). 

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