Conversion of succinic acid

The fungal production of fumaric acid using rice bran and subsequent bacterial conversion of succinic acid using fungal culture broth were investigated. Since the rice bran contains abundant proteins, amino acids, vitamins, and minerals, it is suitable material that fungi use as a nitrogen source. The effective concentration of rice bran to produce fumaric acid was 5 g/L. 

Derivation Conversion of succinic acid to succi-namide, followed by heating ammonia splits off to give a diacyl-substituted derivative (succinimide). 

To eliminate the possible catalytic activity of the reactor walls and internal parts, we verified that under the standard reaction conditions, uncatalysed experiments gave negligible conversion of succinic acid (only 11 % conversion after 4 h at 190°C, compared to complete eonversion within 1 h in the catalyzed experiment). Also, negligible adsorption of the produets on the support was verified by measuring the same concentration of succinic acid in solution at 190°C, in the presence and absence of support. 

A rapid and linear conversion of succinic acid was observed with initial reaetion rates of 15 mol yf, h mol j and 61 mol,- h molR , resulting in complete eonversion within one hour. The intermediate produets detected were acrylic and acetic acids (maximum yields 10.5 and 2 mmol 1, respectively), which were then converted into carbon dioxide and water. Acrylic acid disappeared rapidly and completely during the first hour, but aeetic acid, known as a refractory molecule towards oxidation, was decomposed at a lower rate. There was a continuous TOC reduction throughout the course of oxidation with the rate of TOC removal progressively decreasing at the end of the reaction. Nevertheless, more than 99% of TOC removal was measured after 6 h of reaction - only traces of acetic acid were then detected (TOC < 9 mg 1, i.e. 0.4 pmol 1 ). Malonic acid, oxalic acid or formic acid were not detected by HPLC, probably due to their rapid oxidation. Indeed, separate experiments on the malonic acid vide infra) and previous results [9] have shown that these acids were oxidized to CO, and H,0 at a very high rate at the present reaction conditions. As expected, the acidity of the solution... 

In neutral medium ( run 4) a slight decrease in the initial rate was observed. After 6 h of reaction, total conversion of succinic acid was not achieved, compared to less than 2 hours for the reference experiment. The TOC abatement was 81.6 % at 6 h, because acetic acid was formed in larger amounts and was also barely oxidized. 

Succinic acid is a chemical which has found applications in many areas the most important ones being food additives, soldering fluxes, and pharmaceutical products (1). The conversion of succinic acid to industrially important chemicals such as 1,4-butanediol (EDO), tetrahydrofuran (THF), y butyrolactone (GEL), N-methyl pyrrolidinone (NMP), and 2-pyrrolidinone (2P) recently has been made possible by the development of a number of catalytic processes (2,3). This new development is expected to considerably expand the market for succinic acid. 

The MAH contents of the xylene-soluble and xylene-insoluble fractions were determined by heating a 1-2 g sample in refluxing xylene to dissolve or swell the polymer and then, on conversion of succinic acid to anhydride units, to remove a xylene-water azeotrope in a Dean-Stark tube. The xylene solution or suspension was cooled to about 60 C and 0.5N methanolic KOH was added through the condenser. The mixture was refluxed for 1.5 hrs, cooled and titrated with a 0.25N isopropanolic HCl solution to a phenolphthalein end point. 

The other important aspect of the development of the succinic acid market is the chemical conversion of succinic acid to other products. Selective and low-cost catalyst development is needed to enable lower-cost economics. The chemistry of succinic acid catalysis has been reviewed by Varadarajan and Miller (1999), and the summary of the various derived products that follow is from that work. Succinic acid can be readily converted into alkyl esters that have uses as industrial solvents and paint removers. Succinic acid, its anhydride or its esters, can be hydrogenated to the product family of 1,4-butanediol however, this conversion has not been as well studied as the hydrogenation of maleic acid or anhydride. A third important product family that can be derived from ammonium succinate, succinimide, or succinic acid is based on 2-pyrroHdinones. They are used for polyvinylpyrrolidone (PVP) production, which has an estimated minimum market value of 150 million per year. Other uses for 2-pyrrolidinones include solvents and plasticizers. The commercial production depends upon petrochemical-based... 

Succinic acid, 2,2-difluoeo-, 42, 44 SuCCINIMIDE, N-IODO-, 42, 73 Sulfonation of pyridine, 43, 97 Sulfur tetrafluoride, in conversion of carboxylic acids to 1,1,1-trifluoro compounds, 41, 104/ toxicity of, 41,105 / ... 

In addition to the isomerization of glutamic acid, several other coenzyme B12-catalyzed reactions have now been discovered (I, 9, 15, 31, 51). The conversion of methylmalonic acid to succinic acid is very similar, and has been shown to occur through the migration of a carboxyl group, and postulated to involve free radical itermediates, as follows (15) ... 

FIGURE 16-22 Relationship between the glyoxylate and citric acid cycles. The reactions of the glyoxylate cycle (in glyoxysomes) proceed simultaneously with, and mesh with, those of the citric acid cycle (in mitochondria), as intermediates pass between these compartments. The conversion of succinate to oxaloacetate is catalyzed by citric acid cycle enzymes. The oxidation of fatty acids to acetyl-CoA is described in Chapter 17 the synthesis of hexoses from oxaloacetate is described in Chapter 20. 

The synthesis of succinic acid derivatives, /3-alkoxy esters, and a,j3-unsaturated esters from olefins by palladium catalyzed carbonylation reactions in alcohol have been reported (24, 25, 26, 27), but full experimental details of the syntheses are incomplete and in most cases the yields of yS-alkoxy ester and diester products are low. A similar reaction employing stoichiometric amounts of palladium (II) has also been reported (28). In order to explore the scope of this reaction for the syntheses of yS-alkoxy esters and succinic acid derivatives, representative cyclic and acyclic olefins were carbonylated under these same conditions (Table I). The reactions were carried out in methanol at room temperature using catalytic amounts of palladium (II) chloride and stoichiometric amounts of copper (II) chloride under 2 atm of carbon monoxide. The methoxypalladation reaction of 1-pentene affords a good conversion (55% ) of olefin to methyl 3-methoxyhexanoate, the product of Markov-nikov addition. In the carbonylation of other 1-olefins, f3-methoxy methyl esters were obtained in high yields however, substitution of a methyl group on the double bond reduced the yield of ester markedly. For example, the carbonylation of 2-methyl-l-butene afforded < 10% yield of methyl 3-methyl-3-methoxypentanoate. This suggests that unsubstituted 1-olefins may be preferentially carbonylated in the presence of substituted 1-olefins or internal olefins. The reactivities of the olefins fall in the order RCH =CHo ]> ci -RCH=CHR > trans-RCH =CHR >... 

Since in the citric acid cycle there is no net production of its intermediates, mechanisms must be available for their continual production. In the absence of a supply of oxalacetic acid, acctaic" cannot enter the cycle. Intermediates for the cycle can arise from the carinxylation of pyruvic acid with CO, (e.g., to form malic acid), the addition of CO > to phosphcnnlpyruvic acid to yield oxalacetic acid, the formation of succinic acid from propionic acid plus CO, and the conversion of glutamic acid and aspartic acid to alpha-ketoglutaric acid and oxalacetic acid, respectively. See Fig. 3. 

The simplest unsaturated dicarboxylic acids are maleic acid and fumaric acid, both of which are cheap, commercially available, materials. They are geometric isomers maleic acid is the (Z) isomer (19), and fumaric acid is the (E) isomer (20). Maleic acid forms an internal anhydride, maleic anhydride (21), which is widely used to form adducts with conjugated dienes (the Diels-Alder reaction, Section 7.6). The formation of the anhydride from maleic acid and the conversion of maleic acid into fumaric acid are described in Expt 5.218. The hydrogenation of maleic acid to succinic acid is of value as a means of evaluating the activity of a catalyst for use in hydrogenations at atmospheric pressure the experimental procedure is given in Section 2.17.1, p. 87. 

Production of Fumaric Acid Using Rice Bran and Subsequent Conversion to Succinic Acid Through a Two-Step Process... 

In this section, we seek to identify materials that are the reasonable first structures to arise from biomass deconstruction, and to describe how chemically catalyzed processes are being developed for their production. For that reason, commercially practiced processes that use catalysis, such as the reduction of glucose to sorbitol, are mentioned only briefly or not at all. Chemical catalysis will certainly play an additional role in the further conversion of these initial building blocks into secondary intermediates or final marketplace products (e.g., oxidative conversion of levulinic acid into succinic acid), but such multistep possibilities are outside the scope of this discussion. 

In the conversion of malic acid to chlorosuccinic acid, an inversion of configuration at C-2 was presumed. This point is immaterial, however, since chirality is finally lost at this position. The (2/ )-[2-2H]succinic acid, 89, had a plain negative ORD curve. The configurational assignment rests on the correctness of that for malic acid. 

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