Acrolein, manufacture

In 1957 Standard Oil of Ohio (Sohio) discovered bismuth molybdate catalysts capable of producing high yields of acrolein at high propylene conversions (>90%) and at low pressures (12). Over the next 30 years much industrial and academic research and development was devoted to improving these catalysts, which are used in the production processes for acrolein, acryUc acid, and acrylonitrile. AH commercial acrolein manufacturing processes known today are based on propylene oxidation and use bismuth molybdate based catalysts. 

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). 

Fig. 1. A typical process flowsheet for acrolein manufacture. A, Fixed-bed or fluid-bed reactor B, quench cooler C, absorber D, stripper E and F,...

Liquid-Phase Oxidation of Acrolein. As discussed before, the most attractive process for the manufacture of acrylates is based on the two-stage, vapor-phase oxidation of propylene. The second stage involves the oxidation of acrolein. Considerable art on the Hquid-phase oxidation of acrolein (17) is available, but this route caimot compete with the vapor-phase technology. 

Isopropyl alcohol can be oxidized by reaction of an a,P-unsaturated aldehyde or ketone at high temperature over metal oxide catalysts (28). In one Shell process for the manufacture of aHyl alcohol, a vapor mixture of isopropyl alcohol and acrolein, which contains two to three moles of alcohol per mole of aldehyde, is passed over a bed of uncalcined magnesium oxide [1309-48-4] and zinc oxide [1314-13-2] at 400°C. The process yields about 77% aHyl alcohol based on acrolein. 

Hydroxy-4-methylthiobutyric acid [583-91 -5] the hydroxy analogue of the amino acid methionine, is manufactured by acid hydrolysis of 3-methylthiopropionaldehyde cyanohydrin [17773-41-0] which is produced by the reaction of methyl mercaptan with acrolein (qv). 

Paint and varnish manufacturing Resin manufacturing closed reaction vessel Varnish cooldng-open or closed vessels Solvent thinning Acrolein, other aldehydes and fatty acids (odors), phthalic anhydride (sublimed) Ketones, fatty acids, formic acids, acetic acid, glycerine, acrolein, other aldehydes, phenols and terpenes from tall oils, hydrogen sulfide, alkyl sulfide, butyl mercaptan, and thiofen (odors) Olefins, branched-chain aromatics and ketones (odors), solvents Exhaust systems with scrubbers and fume burners Exhaust system with scrubbers and fume burners close-fitting hoods required for open kettles Exhaust system with fume burners... 

In the manufacture of varnish, heat is necessary for formulation and purificahon. The same may be true of operations preparing paints, shellac, inks, and other protective or decorative coahngs. The compounds emitted to the atmosphere are gases, some with extremely low odor thresholds. Acrolein, with an odor threshold of about 4000 /xg/m, and reduced sulfur compounds, with odor thresholds of 2 are bofh possible emissions... 

Acrolein contaminated by 3% water was obtained by the submitters from Aldrich Chemical Company, Inc., and was purified by distillation from anhydrous calcium sulfate, b.p. 53°. The checkers used acrolein purchased from MC and B Manufacturing Chemists. 

C09-0009. Acrolein. H2 CCHCHO, is used to manufacture polymers for plastics. Draw the Lewis stmcture of acrolein. 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

The hydroformylation of acrolein cyclic acetals has received considerable attention in the recent patent literature as a route to 1,4-butanediol (76-52). This diol is a comonomer for the production of polybutylene terephthalate, an engineering thermoplastic. The standard method for its manufacture has been from acetylene and formaldehyde, as shown in Eqs. (37) and (38) ... 

Acrolein is manufactured from low-cost propylene, and its hydroformyl-ation to 1,4-butanediol or a precursor of it could provide a more economical route. 

Used industrially for the manufacture of flavorings, perfumes, acrolein, diallyl phthalate, diallyl isophthalate, and pharmaceuticals used to denature alcohol. Used agriculturally as herbicide and fungicide. 

Acrolein enters the environment as a result of normal metabolic processes incomplete combustion of coal, wood, plastics, tobacco, and oil fuels and industrial emissions. Acrolein has been detected in smog, foods, and water. It is used extensively in chemical manufacture, for control of fouling organisms, and as an herbicide to control submerged weeds in irrigation canals. 

There are several other routes to acetone of minor importance air oxidation of IPA reaction between IPAand acrolein for the production of allyl alcohol, with acetone as the by-product vapor phase oxidation of butane coproduction when IPA is oxidized yielding acetone and H2O2, hydrogen peroxide, the principal ingredient of bleach and by-product production from the manufacture of methyl ethyl ketone. 

Well, not quite. First, they sound similar because at one time, one of them, acrylonitrile, was based solely on manufacture from acrolein, a pungent liquid whose roots in Latin are aca- meaning sharp, and oiere, meaning smell. Acrylonitrile was made from acrolein, and acrylates were derivatives of acrylonitrile. But acrylates also are made from acrylic acid, which is also a derivative of acrylonitrile. So the name, acrylo, covers an extended farnily of relations. 

Uses Manufacture of acrolein, allyl compounds, glycerol, plasticizers, resins, military poison gas contact pesticide for weed seeds and certain fungi intermediate for pharmaceuticals and other organic compounds herbicide. 

The next aldehyde is acetaldehyde, a colorless liquid with a pungent taste and a fruity odor. Its molecular formula is CH,CHO. It has a flash point of -40°F, an ignition temperature of 340°F, and is toxic by inhalation. Acetaldehyde is used in die manufacture of many other chemicals. Other important aldehydes are propionaldehyde, butyraldehyde, and acrolein. 

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. 

Acrolein and Acrylic Acid. Acrolein and acrylic acid are manufactured by the direct catalytic air oxidation of propylene. In a related process called ammoxida-tion, heterogeneous oxidation of propylene by oxygen in the presence of ammonia yields acrylonitrile (see Section 9.5.3). Similar catalysts based mainly on metal oxides of Mo and Sb are used in all three transformations. A wide array of single-phase systems such as bismuth molybdate or uranyl antimonate and multicomponent catalysts, such as iron oxide-antimony oxide or bismuth oxide-molybdenum oxide with other metal ions (Ce, Co, Ni), may be employed.939 The first commercial process to produce acrolein through the oxidation of propylene, however, was developed by Shell applying cuprous oxide on Si-C catalyst in the presence of I2 promoter. 

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