Production glycolysis

The principal solvolysis reactions for PET are methanolysis with dimethyl terephthalate and ethylene glycol as products, glycolysis with a mixture of polyols and BHET as products, and hydrolysis to form terephthalic acid and ethylene glycol. The preferred route is methanolysis because the DMT is easily purified by distillation for subsequent repolymerization. However, because PET bottles are copolyesters, the products of the methanolysis of postconsumer PET are often a mixture of glycols, alcohols, and phthalate derivatives. The separation and purification of the various products make methanolysis a cosdy process. In addition to the major product DMT, methanol, ethylene glycol, diethylene glycol, and 1,4-cyclohexane dimethanol have to be recovered to make the process economical.1... 

The production of two molecules of ATP in glycolysis is an energy-requiring process ... 

Under cellular conditions, this first reaction of glycolysis is even more favorable than at standard state. As pointed out in Chapter 3, the free energy change for any reaction depends on the concentrations of reactants and products. 

The transaldolase functions primarily to make a useful glycolytic substrate from the sedoheptulose-7-phosphate produced by the first transketolase reaction. This reaction (Figure 23.35) is quite similar to the aldolase reaction of glycolysis, involving formation of a Schiff base intermediate between the sedohep-tulose-7-phosphate and an active-site lysine residue (Figure 23.36). Elimination of the erythrose-4-phosphate product leaves an enamine of dihydroxyacetone, which remains stable at the active site (without imine hydrolysis) until the other substrate comes into position. Attack of the enamine carbanion at the carbonyl carbon of glyceraldehyde-3-phosphate is followed by hydrolysis of the Schiff base (imine) to yield the product fructose-6-phosphate. 

Within glycolysis, the main allosteric control is exercised by phosphofructokinase, a complicated enzyme unusual in that its activity is stimulated by one of its products (ADP) and inhibited by one of its substrates (ATP). One further point about this enzyme which will be important to us later, in Aspergillus spp., elevated levels of ammonium ions relieve phosphofructokinase of inhibition by titrate. 

Let us consider Figure 5.3 again. Both pyruvate kinase and dtrate synthase (enzymes III and V) are inhibited by elevated ATP concentrations. During citric acid production ATP concentrations are likely to arise (ATP produced in glycolysis) and either of these enzymes could, if inhibited, slow down the process. In fact all of the evidence suggests that both enzymes are modified or controlled in some way such that they are insensitive to other cellular metabolites during citric add production. 

The major PET manufacturers are depolymerizing scrap PET with glycols (glycolysis) or methanol (methanolysis) to form low-molecular-weight polyester diols (and BHET) and dimethyl terephthalate.3 The purified products are then used to make new products. Goodyear uses glycolysis to make REPETE, a new product which contains 10-20% recycled PET. Hoechst Celanese used methanolysis to produce DMT for repolymerization. Eastman Chemicals uses depolymerization of PET to recover used X-ray scrap. 

Hydrolysis, although a simple method in theory, yields terephthalic acid (TPA), which must be purified by several recrystallizations. The TPA must be specially pretreated to blend with ethylene glycol to form premixes and slurries of the right viscosities to be handled and conveyed in modern direct polyesterification plants. Hie product of the alkaline hydrolysis of PET includes TPA salts, which must be neutralized with a mineral acid in order to collect the TPA. That results in the formation of large amounts of inorganic salts for which commercial markets must be found in order to make the process economically feasible. There is also the possibility that the TPA will be contaminated with alkali metal ions. Hydrolysis of PET is also slow compared to methanolysis and glycolysis.1... 

Methanolysis products are separated and purified by distillation. BHET, the monomer obtained by PET glycolysis, is normally purified by melt filtration under pressure. One of the problems encountered in neutral hydrolysis of PET is that the terephthalic acid isolated contains most of the impurities initially present in the PET waste. Hence very elaborate purification processes are required to obtain terephthalic acid of commercial purity. 

The glycolysis of rigid polyurethane foams produces polyol products which can be reintroduced into the production cycle of PUR insulation materials to form materials with properties practically equivalent to dtose of materials produced using virgin polyols. Aromatic amines produced as by-products in die glycolysis process are toxic and therefore undesired side products. The most frequently observed side product is diphenylmedianediamine (DMDA), which is formed... 

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