Propylene commercial production

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). 

The propylene-based process developed by Sohio was able to displace all other commercial production technologies because of its substantial advantage in overall production costs, primarily due to lower raw material costs. Raw material costs less by-product credits account for about 60% of the total acrylonitrile production cost for a world-scale plant. The process has remained economically advantaged over other process technologies since the first commercial plant in 1960 because of the higher acrylonitrile yields resulting from the introduction of improved commercial catalysts. Reported per-pass conversions of propylene to acrylonitrile have increased from about 65% to over 80% (28,68—70). 

MethylceUulose is made by reaction of alkaU ceUulose with methyl chloride until the DS reaches 1.1—2.2. HydroxypropyhnethylceUulose [9004-65-3], the most common of this family of products, is made by using propylene oxide in addition to methyl chloride in the reaction MS values of the hydroxypropyl group in commercial products are 0.02—0.3. Use of 1,2-butylene oxide in the alkylation reaction mixture gives hydroxybutyhnethylceUulose [9041-56-9, 37228-15-2] (MS 0.04—0.11). HydroxyethyhnethylceUulose [903242-2] is made with ethylene oxide in the reaction mixture. 

The dkect high temperature chlorination of propylene continues to be the primary route for the commercial production of aHyl chloride. The reaction results in aHyl chloride selectivities of 75—80% from propylene and about 75% from chlorine. Additionally, a significant by-product of this reaction, 1,3-dichloropropene, finds commercial use as an effective nematocide when used in soil fumigation. Overall efficiency of propylene and chlorine use thus is significantly increased. Remaining by-products include 1,2-dichloropropane, 2-chloropropene, and 2-chloropropane. 

Polyolefins. The most common polyolefin used to prepare composites is polypropylene [9003-07-0] a commodity polymer that has been in commercial production for almost 40 years following its controlled polymerisation by Natta in 1954 (5). Natta used a Ziegler catalyst (6) consisting of titanium tetrachloride and an aluminum alkyl to produce isotactic polypropylene directly from propylene ... 

Although the mbbery properties of ethylene—propylene copolymers are exhibited over a broad range of compositions, weight percentages of commercial products generally range from 50 50 to 75 25 ethylene propylene. 

The ATPEs have a poly(propylene oxide) backbone widi amine endgroups, as shown in Scheme 4.4. There are several routes to such materials,25 but the only one in current commercial production is die direct amination of polyether polyols. A line of uretiiane-grade ATPEs is made by Huntsman under the tradename Jeffamine. Mono-, di-, and trifunctional products are available in molecular weights up to 5000 g/m. 

All of the organohalogen compounds studied were commercial products obtained from various manufacturers and used as received. Only the DBDPO was purified further by recrystallization for some of the chromatography and thermal analysis experiments. Samples of antimony trioxide and antimony pentoxide were also obtained from commercial sources. The ultrapure antimony trioxide, bismuth trioxide, bismuth metal, antimony metal, dibenzofuran and diphenyl ether were all obtained from Aldrich Chemicals. The poly(propylene) (PP) resin was 0.7 mfi, food grade from Novamont and the poly(ethylene) was unstabilized, high molecular weight, HDPE from American Hoechst. 

The synthesis of commercial nonylphenols generally proceeds through an alkylation reaction of phenols with propylene trimer [124], which itself has a spread of isomers [47]. The alkylation occurs preferentially at the para position of the phenol, but 3-6% of ortho-nonylphenol can be found in commercial products [125]. Also meta and disubstituted species have been mentioned [47]. A common feature of the isomers appears to be a dimethyl substitution of the a-carbon atom [83]. 

Prior to this time, other ventures had already been operating to produce commercial quantities of aliphatic chemicals from petroleum sources. Truly commercial production of ethylene glycol had been achieved by 1925 (10) using natural gas fractions as a starting material, and even earlier (about 1920) there had been the manufacture of isopropyl alcohol from cracking plant propylene (20), which may be termed the pioneer operation on a successful, continuing basis in the sphere of aliphatic synthesis from petroleum. 

Methyl methacrylate is only one of a family of monomers, including the various esters of acrylic, methacrylic, and ethacrylic acids, which are polymerized to produce the thermoplastic resins known as the acrylates. A wide variety of reactions and starting materials may be utilized for their production however, the principal commercial product is polymethyl methacrylate, sold by Du Pont and Rohm Haas under the trade names of Lucite and Plexiglas, respectively. These materials were introduced to the United States market in 1936 (44) and have received widespread acceptance due principally to their outstanding optical properties. Production in 1949 was reported as about 22,000,000 to 25,000,000 pounds and peak wartime capacity was above30,000,000 pounds. While this can account for only about 2% of the current production of propylene for chemical purposes, the acrylate resins are of considerable commercial importance as they are sold at a relatively high price and are the only materials available that will meet the requirements for certain military and civilian products. 

While the use of these polyethers is widespread, the goal of discussion is to create a specialty chemical. Propylene- and ethylene-based polyols are produced for physical reasons and will serve as the backbone. Researchers should note, however, that the scope of polyethers and polyesters is much broader when they are willing to sacrifice some physical strength to gain a chemical advantage. To illustrate, we cite a particularly interesting example. Castor oil was a conunon polyol for the production of polyurethanes. It was replaced by less expensive and more predictable polyols in commercial production. Readers should be aware that mixed polyols can be used to advantage. 

Polyesters from propylene glycol and dicarboxylic acids, especially adipic and sebacic acid, are commercial products suggested for PVC as well as for cellulose esters. The well known Paraplex resins of Rohm Haas, which are compatible with nitrile and GRS rubber, belong to this group. Other products are the Ultramolls of Farbenfabriken Bayer. Some polyesters of this type have a tendency to exude on storage, especially if esterification is not complete. 

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. 

Allyl Chloride (3-chioropropene-1). [CAS 107-05-1]. Ally I chloride can be synthesized by reaction of allyl alcohol with HCI or by treatment of allyl formate with HCI in the presence of a catalyst (ZnCLV Commercial production is by chlorination of propylene at high temperatures, about 500°C. using a large excess of propylene. It is used in the synthesis of... 

Methyl cihcr finds markets in such jrtras as refrigerants, spray propellants, and extraction. Propyl and butyl eihci ate not presently large commercial products, their high price makes it difficult for them to compete as i>hew and extractant with the cheaper ethers and kclunes, Butyl ether, however, has found some uses in the polymerization of propylene and isoprcnc. 

More than a decade after the publication of the MoVNb catalyst system, scientists at Mitsubishi Chemical reported that modifying this family of mixed metal oxides with Te produced a catalyst for the amoxidation of propane to acrylonitrile [4] and the oxidation of propane to acrylic acid [5], Modification of the Union Carbide catalyst system with Te was probably not a random choice as it is a known propylene activator [5 b] and the molybdate phase TeMoO oxidizes propylene into acrolein and ammoxidizes propylene to acrylonitrile [6], a key intermediate in the commercial production of acrylic acid using Mo-based oxides. Significant efforts to optimize this and related mixed metal oxides continues for the production of both acrylic acid and acrylonitrile, with the main participants being Asahi, Rohm Hass, BASF, and BP. 

Raw-gum fluorocarbon elastomers are transparent to translucent with molecular weights from approximately 5000 (e.g., VITON LM with waxy consistency) to over 200,000. The most common range of molecular weights for commercial products is 100,000 to 200,000. Polymers with molecular weights over 200,000 (e.g., Kel-F products) are very tough and difficult to process. Elastomers prepared with vinylidene fluoride as comonomer are soluble in certain ketones and esters, copolymers of IFF and propylene in halogenated solvents perfluorinated elastomers are practically insoluble.16... 

The Ziegler-Natta catalysts have acquired practical importance particularly as heterogeneous systems, mostly owing to the commercial production of linear high- and low-density polyethylenes and isotactic polypropylene. Elastomers based on ethylene-propylene copolymers (with the use of vanadium-based catalysts) as well as 1,4-cz s-and 1,4-tran.y-poly(l, 3-butadiene) and polyisoprene are also produced. These catalysts are extremely versatile and can be used in many other polymerisations of various hydrocarbon monomers, leading very often to polymers of different stereoregularity. In 1963, both Ziegler and Natta were awarded the Nobel Prize in chemistry. 

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