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Propylene oxide catalysts used

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. [Pg.123]

Figure 9.19. Secondary-ion mass spectrum of a promoted Fe-Sb oxide catalyst used for the selective oxidation of propylene and ammonia to acrylonitrile, showing the presence of Si, Cu, and Mo along with traces of alkali in the catalyst. [Reproduced from J.W. Niemantsverdriet, Spectres-200 gpy jfj Catalysis, 2" Edn. Figure 9.19. Secondary-ion mass spectrum of a promoted Fe-Sb oxide catalyst used for the selective oxidation of propylene and ammonia to acrylonitrile, showing the presence of Si, Cu, and Mo along with traces of alkali in the catalyst. [Reproduced from J.W. Niemantsverdriet, Spectres-200 gpy jfj Catalysis, 2" Edn.
As catalysis proceeds at the surface, a catalyst should preferably consist of small particles with a high fraction of surface atoms. This is often achieved by dispersing particles on porous supports such as silica, alumina, titania or carbon (see Fig. 1.2). Unsupported catalysts are also in use examples of these include the iron catalysts for ammonia synthesis and CO hydrogenation (the Fischer-Tropsch synthesis), or the mixed metal oxide catalysts used in the production of acrylonitrile from propylene and ammonia. [Pg.2]

All selective oxidation and ammoxidation catalysts possess redox properties. They must be capable not only of reduction during the formation of acrolein or acrylonitrile, but also subsequent catalyst reoxidation in which gaseous oxygen becomes incorporated into the lattice as to replenish catalyst vacancies (Scheme 2). As mentioned earlier, the incorporation of such redox properties into solid state metal oxides was one of the salient working hypotheses on which the development of the Sohio ammoxidation process was based (2). Later, Keulks (70) confirmed the involvement of lattice oxygen in propylene oxidation by using as a vapor phase oxidant. The results showed that the incorporation of O into the acrolein (and CO2) increases with time (Fig. 11), which is consistent with the above redox mechanism. [Pg.143]

One of the key features of the stereoselective coordination catalysts for propylene oxide polymerization is that, while they can give Isotactic polymer with a very high ratio of Isotactic to syndiotactic sequences (e.g. > 370) (34). in the same reaction mixture a large part of the polymer is amorphous. Even vdien R-propylene oxide is used as starting material, much of the product is amorphous polymer of low optical rotation containing many S-propylene oxide units (30). [Pg.10]

Today the most efficient catalysts are complex mixed metal oxides that consist of Bi, Mo, Fe, Ni, and/or Co, K, and either P, B, W, or Sb. Many additional combinations of metals have been patented, along with specific catalyst preparation methods. Most catalysts used commercially today are extmded neat metal oxides as opposed to supported impregnated metal oxides. Propylene conversions are generally better than 93%. Acrolein selectivities of 80 to 90% are typical. [Pg.123]

Processes rendered obsolete by the propylene ammoxidation process (51) include the ethylene cyanohydrin process (52—54) practiced commercially by American Cyanamid and Union Carbide in the United States and by I. G. Farben in Germany. The process involved the production of ethylene cyanohydrin by the base-cataly2ed addition of HCN to ethylene oxide in the liquid phase at about 60°C. A typical base catalyst used in this step was diethylamine. This was followed by liquid-phase or vapor-phase dehydration of the cyanohydrin. The Hquid-phase dehydration was performed at about 200°C using alkah metal or alkaline earth metal salts of organic acids, primarily formates and magnesium carbonate. Vapor-phase dehydration was accomphshed over alumina at about 250°C. [Pg.183]

Chemical Manufacturing. Chemical manufacturing accounts for over 50% of all U.S. caustic soda demand. It is used primarily for pH control, neutralization, off-gas scmbbing, and as a catalyst. About 50% of the total demand in this category, or approximately 25% of overall U.S. consumption, is used in the manufacture of organic intermediates, polymers, and end products. The majority of caustic soda required here is for the production of propylene oxide, polycarbonate resin, epoxies, synthetic fibers, and surface-active agents (6). [Pg.518]

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. [Pg.477]

Synthesis. The total aimual production of PO in the United States in 1993 was 1.77 biUion kg (57) and is expected to climb to 1.95 biUion kg with the addition of the Texaco plant (Table 1). There are two principal processes for producing PO, the chlorohydrin process favored by The Dow Chemical Company and indirect oxidation used by Arco and soon Texaco. Molybdenum catalysts are used commercially in indirect oxidation (58—61). Capacity data for PO production are shown in Table 1 (see Propylene oxide). [Pg.348]

In this process, the fine powder of lithium phosphate used as catalyst is dispersed, and propylene oxide is fed at 300°C to the reactor, and the product, ahyl alcohol, together with unreacted propylene oxide is removed by distihation (25). By-products such as acetone and propionaldehyde, which are isomers of propylene oxide, are formed, but the conversion of propylene oxide is 40% and the selectivity to ahyl alcohol reaches more than 90% (25). However, ahyl alcohol obtained by this process contains approximately 0.6% of propanol. Until 1984, ah ahyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced ahyl alcohol industriahy by a new process which they developed (6,7). This process, which was developed partiy for the purpose of producing epichlorohydrin via ahyl alcohol as the intermediate, has the potential to be the main process for production of ahyl alcohol. The reaction scheme is as fohows ... [Pg.74]

Allyl Glycidyl Ether. This ether is used mainly as a raw material for silane coupling agents and epichlorohydrin mbber. Epichlorohydrin mbber is synthesized by polymerizing the epoxy group of epichlorohydrin, ethylene oxide, propylene oxide, and aHyl glycidyl ether, AGE, with an aluminum alkyl catalyst (36). This mbber has high cold-resistance. [Pg.77]

Ethoxylation and Propoxylation. Ethylene oxide [75-21-8] or propylene oxide [75-56-9] add readily to primary fatty amines to form bis(2-hydroxyethyl) or bis(2-hydroxypropyl) tertiary amines secondary amines also react with ethylene or propylene oxide to form 2-hydroxyalkyl tertiary amines (1,3,7,33—36). The initial addition is completed at approximately 170°C. Additional ethylene or propylene oxide can be added by using a basic catalyst, usually sodium or potassium hydroxide. [Pg.219]

Molecular weights of poly(propylene oxide) polymers of greater than 100,000 are prepared from catalysts containing FeCl (40,41). The molecular weight of these polymers is gready increased by the addition of small amounts of organic isocyanates (42). Homopolymers of propylene oxide are also prepared by catalysis using diethylzinc—water (43), diphenylzinc—water (44), and trialkyl aluminum (45,46) systems. [Pg.134]

Carbon Dioxide and Carbon DisulUde. Propylene oxide and carbon dioxide react ia the presence of tertiary amine, quaternary ammonium haUdes, or calcium or magnesium haUde catalysts to produce propylene carbonate (52). Use of catalysts derived from diethyUiac results ia polycarbonates (53). [Pg.135]

Similarly, carbon disulfide and propylene oxide reactions are cataly2ed by magnesium oxide to yield episulftdes (54), and by derivatives of diethyUiac to yield low molecular weight copolymers (55). Use of tertiary amines as catalysts under pressure produces propylene trithiocarbonate (56). [Pg.135]

Hydrogen Sulfide andMercaptans. Hydrogen sulfide and propylene oxide react to produce l-mercapto-2-propanol and bis(2-hydroxypropyl) sulfide (69,70). Reaction of the epoxide with mercaptans yields 1-aLkylthio- or l-arylthio-2-propanol when basic catalysis is used (71). Acid catalysts produce a mixture of primary and secondary hydroxy products, but ia low yield (72). Suitable catalysts iaclude sodium hydroxide, sodium salts of the mercaptan, tetraaLkylammonium hydroxide, acidic 2eohtes, and sodium salts of an alkoxylated alcohol or mercaptan (26,69,70,73,74). [Pg.135]

Isomerization and Hydrogenolysis. lsomeri2ation of propylene oxide to propionaldehyde and acetone occurs over a variety of catalysts, eg, pumice, siUca gel, sodium or potassium alum, and 2eohtes (80,81). Stronger acid catalysts favor acetone over propionaldehyde (81). AHyl alcohol yields of 90% are obtained from use of a supported lithium phosphate catalyst (82). [Pg.135]

EBHP is mixed with a catalyst solution and fed to a horizontal compartmentalized reactor where propylene is introduced into each compartment. The reactor operates at 95—130°C and 2500—4000 kPa (360—580 psi) for 1—2 h, and 5—7 mol propylene/1 mol EBHP are used for a 95—99% conversion of EBHP and a 92—96% selectivity to propylene oxide. The homogeneous catalyst is made from molybdenum, tungsten, or titanium and an organic acid, such as acetate, naphthenate, stearate, etc (170,173). Heterogeneous catalysts consist of titanium oxides on a siUca support (174—176). [Pg.140]

Gas-phase oxidation of propylene using oxygen in the presence of a molten nitrate salt such as sodium nitrate, potassium nitrate, or lithium nitrate and a co-catalyst such as sodium hydroxide results in propylene oxide selectivities greater than 50%. The principal by-products are acetaldehyde, carbon monoxide, carbon dioxide, and acrolein (206—207). This same catalyst system oxidizes propane to propylene oxide and a host of other by-products (208). [Pg.141]

Propylene oxide is also produced in Hquid-phase homogeneous oxidation reactions using various molybdenum-containing catalysts (209,210), cuprous oxide (211), rhenium compounds (212), or an organomonovalent gold(I) complex (213). Whereas gas-phase oxidation of propylene on silver catalysts results primarily in propylene oxide, water, and carbon dioxide as products, the Hquid-phase oxidation of propylene results in an array of oxidation products, such as propylene oxide, acrolein, propylene glycol, acetone, acetaldehyde, and others. [Pg.141]

Propylene oxide has found use in the preparation of polyether polyols from recycled poly(ethylene terephthalate) (264), haUde removal from amine salts via halohydrin formation (265), preparation of flame retardants (266), alkoxylation of amines (267,268), modification of catalysts (269), and preparation of cellulose ethers (270,271). [Pg.143]

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). [Pg.92]

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). [Pg.51]

Other important uses of stannic oxide are as a putty powder for polishing marble, granite, glass, and plastic lenses and as a catalyst. The most widely used heterogeneous tin catalysts are those based on binary oxide systems with stannic oxide for use in organic oxidation reactions. The tin—antimony oxide system is particularly selective in the oxidation and ammoxidation of propylene to acrolein, acryHc acid, and acrylonitrile. Research has been conducted for many years on the catalytic properties of stannic oxide and its effectiveness in catalyzing the oxidation of carbon monoxide at below 150°C has been described (25). [Pg.65]


See other pages where Propylene oxide catalysts used is mentioned: [Pg.246]    [Pg.189]    [Pg.85]    [Pg.3024]    [Pg.126]    [Pg.60]    [Pg.474]    [Pg.329]    [Pg.316]    [Pg.72]    [Pg.227]    [Pg.294]    [Pg.134]    [Pg.134]    [Pg.135]    [Pg.137]    [Pg.140]    [Pg.141]    [Pg.141]    [Pg.516]   
See also in sourсe #XX -- [ Pg.124 , Pg.125 ]




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