Feedstock succinic acid

Butane from natural gas is cheap and abundant in the United States, where it is used as an important feedstock for the synthesis of acetic acid. Since acetic acid is the most stable oxidation product from butane, the transformation is carried out at high butane conversions. In the industrial processes (Celanese, Hills), butane is oxidized by air in an acetic acid solution containing a cobalt catalyst (stearate, naphthenate) at 180-190 °C and 50-70 atm.361,557 The AcOH yield is about 40-45% for ca. 30% butane conversion. By-products include C02 and formic, propionic and succinic acids, which are vaporized. The other by-products are recycled for acetic acid synthesis. Light naphthas can be used instead of butane as acetic adic feedstock, and are oxidized under similar conditions in Europe where natural gas is less abundant (Distillers and BP processes). Acetic acid can also be obtained with much higher selectivity (95-97%) from the oxidation of acetaldehyde by air at 60 °C and atmospheric pressure in an acetic acid solution and in the presence of cobalt acetate.361,558... 

Platform chemicals are compounds that serve as building blocks for numerous chemical intermediates and end products. An example is ethylene, which serves as the feedstock for derivatives such as acetaldehyde, ethylene dichloride, ethylene oxide, polyethylene, vinyl acetate, and ethyl acetate. Biobased chemicals such as succinic acid, 3-hydroxypropionic acid (3-HP), and butanol also have the potential to be converted into multiple derivatives, some of which are commodity chemicals and others that are higher-value chemicals. 

Interest in bioconversion of polysaccharides into refined chemicals has vacillated with the market price of traditional sources. Due to its relatively low production cost, Jerusalem artichoke-derived inulin is an attractive feedstock for commercial production of several common reagents (e.g., ethanol, acetone, butanol, 2,3-butanediol, lactic acid, succinic acid) (Barthomeuf et al., 1991 Drent and Gottschal, 1991 Drent et al., 1991,1993 Fages et al., 1986 Fuchs, 1987 Marchal et al., 1985 Middlehoven et al., 1993). Selection of the appropriate microorganism (Table 5.8) and fermentation conditions is essential for maximizing the yield of a desired component. 

Succinic acid is currently manufactured by the hydrogenation of maleic anhydride to succinic anhydride, followed by hydration to succinic acid. A fermentation process for succinic acid production is desirable because in such processes, renewable resources such as starchy crops and other agricultural products can be used as feedstock for the biological production of succinic acid. It addition, a high purity product, which is required as raw material for polymer manufacture, can be obtained. 

Succinic acid, known as amber acid or butanedioic acid, is a four-carbon dicarboxylic acid produced as an intermediate of the tricarboxylic acid cycle (TCA) [1,2]. Succinic acid and its derivative have wide industrial applications such as the feedstock of food and pharmaceutical products, as the intermediate of chemical synthesis of surfactants, detergents, green solvents, and biodegradable plastics, and also as ingredients of animal feeds to stimulate animal and... 

Initially, cyclohexane is oxidized to the intermediate cyclohexyl hydroperoxide, CHHP. Then, the obtained CHHP is decomposed into the desired components cyclohexanone and cyclohexanol however, it is also partly decomposed into undesired by-products. A part of the formed cyclohexanol is further oxidized to cyclohexanone and a part of the formed cyclohexanone is converted to by-products. Part of the cyclohexane oxidation by-products are further destroyed (not shown in this figure). The by-products finally obtained include, in various amounts, acids such as adipic acid, e-hydroxycaproic acid, glutaric acid, succinic acid, valeric acid, caproic acid, propionic acid, acetic acid, formic acid, and noncondensable gases such as CO and CO2. In addition, several esters are formed between mainly cyclohexanol and the various carboxylic acids. The destinations of these by-products are quite diverse and depend on the producer for example, some of these byproducts are fed to combustion units for heat recovery purposes, while others are used as feedstock for chemicals such as 1,5-pentanediol, 1,6-hexanediol (HDO), and caprolactone. In general cyclohexanol is recovered from esters in a biphasic saponification step. 

Succinic acid plays an important role in the Krebs cycle and can deliver electrons to the electron transport chain. Succinic acid has been found in a very wide range of plant and animal tissues, though its purification challenged chemists for a long time before it was fincdly successfully purified from tissues. Today succinic acid can be produced readily in the laboratory, and one method even can use corn as a feedstock. In addition to its role in the Krebs cycle, succinic acid has been used as an intermediate in dyes, perfumes, paints, inks, and fibers. 

At present succinic acid is a specialty chemical with an annual production volume of about 30 000 tons worldwide. Fossil-based succinic acid is most commonly prepared via hydrogenation of maleic anhydride (by oxidation of n-butane or benzene) [73]. In the field of bio-based chemicals and building blocks succinic acid is considered to be one of the most important platform chemicals [1, 74, 75], and as a result of the introduction of biosuccinic acid the production volume is expected to double or triple within years. Several fermentation processes have been described to produce bio-based succinic acid. Common feedstocks for these processes include glucose, starch and xylose [76]. The commercial potential for bio-succinic acid is illustrated by the numerous initiatives by companies that are working towards, or already... 

Myriant (United States) received a grant Irom the US Department of Energy for their activities on the production of bio-succinic acid. These activities include building of a 20 000 litre reactor in Louisiana, modification of a leased facility of 15 000 ton/year and the construction of a greenfield plant also with a capacity of 15 000 ton/year. The Myriant process uses E. coli and unrefined sugar as feedstock. 

Routes towards based 1,4-BDO are currently under development. The production of succinic acid from biomass is currently being commercialized by companies like for example, BioAmber and the DSM-Roquette joint venture Reverdia [126]. Succinic acid is a potential feedstock for the production of 1,4-BDO via reduction of the diacid to the diol [127]. The US based company Genomatica claims it has been successful in developing technology for the direct biotechnological production of 1,4-BDO (see www.genomatica.com, accessed 22 June 2013 see also section 9.4.2). 

Succinic acid currently is manufactured by chemical processes (1). Many attempts have been made to develop a fermentation process for the production of succinic acid from renewable feedstocks such as corn-derived glucose. A number of patents have been issued on the microbial production of succinic acid (4-7). However, none of these has been applied toward the commercial production of succinic acid. 

As shown in Table III, the BDSA process offers significant advantages in two primary areas. First, the process has a significantly lower estimated production cost for BDO, succinic acid, and several other commodity chemicals, as well as lower energy consumption during production. Current com production could easily supply the 100 to 200 hundred million pounds of com sugar required for each major chemical plant, and use of this feedstock would decrease petroleum consumption and imports. Further analysis by ACC and New Horizon of the production cost for succinic acid in our fermentation process has included several process modifications to further decrease costs. The estimated costs in 1998 were 0.20/lb sodium succinate. However, the petrochemical routes to BDO have also had further improvements, increased capacity and presumably lowered the target price. 

Abstract Succimc add is an important platform chemical derived from petrochemical or bio-based feedstocks and can be transformed into a wide range of chemicals and polymers. Increasing demand for biodegradable poly(butylene succinate) (PBS) will open up a new market for succinic acid. In this chapter, the synthesis of succinic acid is briefly reviewed. We focus on the polymerization, crystalline structure, thermal and mechanical properties, and biodegradability of PBS and its copolymers. PBS shows balanced mechanical properties similar to those of polyethylene and excellent performance during thermal processing. In addition, PBS and its copolymers can biodegrade in various enviromnents, such as soil burial, river, sea, activated... 

At the present stage, petroleum- or coal-based succinic acid is still cheaper than bio-based feedstock. With future development of fermentation technology and the finding of new microbial strains, bio-based succinic acid will become competitive. 

PCL -OCH CH CH CH CH CO-ln) is a partially-crystalline polyester that is biodegraded by microbial lipases and esterases. The plastic is made from petrochemical feedstocks. It has too low a melting point (60°C) to be useful in any packaging applications. Higher aliphatic polyesters such as poly(butylene succinate) (PBS) (-0(CH2) OC(CH2)2CO-)n and poly(ethylene succinate) (PES) (-OCCH l OOCCCH l CO-) are also biodegradable at a rate that depends on environmental factors (Kasuya et al., 1997). They have higher melting points of 112-114°C and 103-106°C, respectively, and the properties compare well to those of polyolefins. As succinic acid can be derived from plant sources, the polysuccinates can be potentially a bio-based polymer. 

Introduction of bio-based succinic acid as a significant step toward a sustainable chemical industry depends on two important economic parameters. The first is summarized under the term of the production costs. Major constituents along the production process are the costs and the availability of the feedstock with 10-15%, the fermentation process itself contributing to 20-25% of the costs, and the purification of the final producf, which may utilize between 60% and 70% of the total costs. All these parameters can be improved to reduce the succinic acid price. For example, processes and/or producer strains capable of utilizing different kinds of feedstocks... 

Conventional processes for the production of 1,4-butanediol use fossil fuel feedstocks such as acetylene and formaldehyde. The biobased process involves the use of glucose from renewable resources to produce succinic acid followed by a chemical reduction to produce butanediol. PBS is produced by transesterification, direct polymerization, and condensation polymerization reactions. PBS copolymers can be produced by adding a third monomer such as sebacic acid, adipic acid and succinic acid, which is also produced by renewable resources [34]. 

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