1,3-Propanediol commercial production

Such catalyst resins are now used in the production of many industrially important materials, including solvents such as MIBK, oxygenate additives such as TAME (t-amyl methyl ether), hydrogen peroxide and 1,2 propanediol. In contrast, there is much less use of catalytic ion exchange resins in the commercial production of fine chemicals. The reasons for this might include selectivity aspects, the availability of resins in a shape that is well suited for large reactors and a lack of knowledge with respect to the accessibility and stability of the active sites. The importance and the scope of uses of such catalysts are often limited by diffusional issues and problems of mechanical and thermal stability. 

Another of the pioneer polyesters was polytrimethylene terephthalate (PTT). This was recognized very early on as a fiber with outstanding resilience. PTT has been known in many ways as an ideal textile fiber for over 60 years. It remained on the shelf until, in the last decade, it became a commercial product owing to two new routes to the crucial intermediate 1,3-propanediol. One route is petrochemically derived (hydroformylation of ethylene oxide), while the other is a fermentation route using corn sugar to make 1,3-propanediol directly using genetically modified bacteria [40]. 

Chotani G, Dodge T, Hsu A, Kumar M, LaDuca R, Trimbur D, Weyler W, Sanford K (2000) The commercial production of chemicals using pathway engineering. Biochim Biophys Acta 1543 434-455 Clark SW, Bennett GN, Rudolph FB (1989) Isolation and characterization of mutants of Clostridium acetobutylicum ATCC 824 deficient in acetoacetyl-coenzyme A acetate/butyrate coenzyme A-transferase (EC 2.8.3.9) and in other solvent pathway enzymes. Appl Environ Microbiol 55 970-976 Cocks GT, Aguilar J, Lin EGG (1974) Evolution of L-1,2-propanediol catabolism in Escherichia coli by recruitment of enzymes for L-fucose and L-lactate metabolism. J Bacteriol 118 83-88... 

The nitro alcohols in Table 1 are manufactured in commercial quantities however, three of the five of them are used only for the production of the corresponding amino alcohols. 2-Methyl-2-nitro-l-propanol (NMP) is available as the crystalline soHd or as a mixture with siHcon dioxide. 2-Hydroxymethyl-2-nitro-1,3-propanediol is available as the soHd ( 9.15/kg), a 50% solution in water ( 2.33/kg), a 25% solution in water ( 1.41/kg), or as... 

Propanediol dinitrate Commercial. Barab (Ref 4) patented liq expls contg varying amts of 1,2- and 1,3-Propanediol Dinitrates. These mixts were claimed to be as powerful as, but less sensitive than NG. The product was examined by the US BuMines and found to make up a 40% straight Dynamite that compared favorably with 40% straight NG Dynamite Ref J. Barab, USP 1371215 (1921)... 

Two options are being developed at the moment. The first is to produce 1,2-propanediol (propylene glycol) from glycerol. 1,2-Propanediol has a number of industrial uses, including as a less toxic alternative to ethylene glycol in anti-freeze. Conventionally, 1,2-propanediol is made from a petrochemical feedstock, propylene oxide. The new process uses a combination of a copper-chromite catalyst and reactive distillation. The catalyst operates at a lower temperature and pressure than alternative systems 220°C compared to 260°C and 10 bar compared to 150 bar. The process also produces fewer by-products, and should be cheaper than petrochemical routes at current prices for natural glycerol. The first commercial plant is under construction and the process is being actively licensed to other companies. 

The seventh and final paper, "Development of a Fermentation-Based Process for 1,3-Propanediol Highlights of a Successful Path from Corn to Textile Fiber," by Tyler Ames of DuPont, reviewed the multiyear effort by DuPont and its development partners (Genecor International and Tate Lyle) to commercialize a new biocatalytic process for the production of 1,3-propanediol (PDO), a key ingredient in DuPont s new Sorona advanced polymer platform. PDO is currently being produced at pilot scale at Tate Lyle s Decatur, IL, site, and construction of a commercial-scale facility is expected to begin soon. 

For DuPont, the commercialization of 1,3-propanediol and PTT has opened up markets for industrial products from renewable resources. Through a partnership with Genencor International, DuPont has recently developed a lower-cost fermentation route that converts biomass sugars into 1,3-propanediol. DuPont plans to transition to the biobased process for... 

Other Uses of Ethylene Oxide. About 2 percent of ethylene oxide is consumed in miscellaneous applications, such as its use as a raw material in manufacture of choline, ethylene chlorohydrin, hydroxyethyl starch, and hydrox-yethyl cellulose and its direct use as a fumigant/ sterilant. Production of 1,3-propanediol via hydroformylation of ethylene oxide was begun on a commercial scale in 1999. 1,3-Propanediol is a raw material for polytrimethylene terephthalate, which finds uses in fibers, injection molding, and in film. Use of ethylene oxide in making 1,3-propanediol is expected to be as much as 185 million lb by 2004, up from 12 million lb in 1999. 

Methyl a-D-glucopyranoside is the only product of commercial promise to have thus far emerged from work with protic solvents it has utility in the preparation of polyurethane foams. Mehltretter and coworkers125,126 have described the application of mixtures of D-glucosides obtained by the acid-catalyzed reaction of ethylene glycol, 1,2-propanediol ( propylene glycol ), or glycerol with starch,... 

Polyipropylene terephthalate), more often referred to as poly(trimethylene terephthalate) (PTT), was identified from research into aromatic polyesters, but was not commercialised at the time due to difficulty in obtaining pure, low-cost, 1,3-propanediol. Finally introduced into large-scale production in the late 1990s, there are great hopes for commercial application of this polymer, especially as a fibre. In general, it has properties between those of PET and PBT, but has certain unique properties of its own, including superior resilience and wear properties, giving carpets tufted with such fibres physical properties akin to the nylons, and stain resistance similar to PET. 

Poly(ethylene terephthalate), the lowest cost and most commonly used polyester, is produced using ethylene glycol (EG) and either dimethyl terephthalate (DMT) or terephthahc acid (TPA) (see Table 7.1). Processes using DMT were commercialized first, but when very pure TPA became available, TPA processes became more economical for large-scale fiber production. Poly(butylene terephthalate) (PBT), produced fi-om 1,4 butanediol and DMT, is another commercially important polyester, which is used for computer housings and many other molded products. Poly(trimethylene terephthalate) (PTT), made from TPA and 1,3 propanediol, is a relatively new commercial polyester, that shows promise for... 

This monomer, also named 9,9-dihexylfluorene-2,7-diboronic acid bis(l,3-propanediol) ester, is commercially available. The propanediol or pinacol boronate esters of dialkylfluorenes with different alkyl chain lengths are also commercially available products, and these compounds can be used directly in the following Suzuki polymerization. However, the given synthetic procedures for boronate ester monomers will be useful for preparing new fluorene monomers, which are not commercially available. 

When pentaerythritol is synthesized, 2,2 -[oxybis(methylene)]-bis[2-hydroxymethyl)-l,3-propanediol [126-58-9] (dipentaerythrito]) and 2,2-bis [3-hydroxy-2,2-bis(hydroxymethy])propoxy]methyl l,3-propanediol [78-24-0] (tri-pentaerythritol) are by-products, and commercial pentaerythritol contains some of these higher polyols. Consequently, care must be exercised in changing sources of pentaerythritol, since the amount of the higher polyols may differ. Because... 

PTT is a new member in polyester family its value as a commercial polymer has improved because its monomers are not all dependent on petroleum. DuPont has successfully commercialized the production of this polymer via 1,3-propanediol obtained by fermentation and produces Polytrimethylene terephthalate (PTT) with the brand name of Sorona. The beneficial properties of Sorona are derived from a unique, semicrystalline molecular structure featuring a pronounced kink, which means that outer forces, such as tensile or compressive forces, translate at the molecular level, causing... 

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