Hydrogenation of maleic anhydride

Butyrolactone. y-Butyrolactone [96-48-0] dihydro-2(3H)-furanone, was fkst synthesized in 1884 via internal esterification of 4-hydroxybutyric acid (146). In 1991 the principal commercial source of this material is dehydrogenation of butanediol. Manufacture by hydrogenation of maleic anhydride (147) was discontinued in the early 1980s and resumed in the late 1980s. Physical properties are Hsted in Table 4. 

Survey of the patent Hterature reveals companies with processes for 1,4-butanediol from maleic anhydride include BASF (94), British Petroleum (95,96), Davy McKee (93,97), Hoechst (98), Huels (99), and Tonen (100,101). Processes for the production of y-butyrolactone have been described for operation in both the gas (102—104) and Hquid (105—108) phases. In the gas phase, direct hydrogenation of maleic anhydride in hydrogen at 245°C and 1.03 MPa gives an 88% yield of y-butyrolactone (104). Du Pont has developed a process for the production of tetrahydrofuran back-integrated to a butane feedstock (109). Slurry reactor catalysts containing palladium and rhenium are used to hydrogenate aqueous maleic acid to tetrahydrofuran (110,111). 

Succinic anhydride [108-30-5] (3,4-dihydro-2,5-furandione butanedioic anhydride tetrahydro-2,5-dioxofuran 2,5-diketotetrahydrofuran succinyl oxide), C H O, was first obtained by dehydration of succinic acid. In the 1990s anhydride is produced by hydrogenation of maleic anhydride and the acid by hydration of the anhydride, by hydrogenation of aqueous solutions of maleic acid, or as a by-product in the manufacture of adipic acid (qv) (see Maleic ANHYDRIDE, MALEIC ACID, AND FUMARIC ACID). 

Succinic anhydride is manufactured by catalytic hydrogenation of maleic anhydride [108-31-6]. In the most widely used commercial process this reaction is performed in the Hquid phase, at temperatures of 120—180°C and at moderate pressures, in the range of 500—4000 kPa (72—580 psi). Catalysts mentioned in the patent Hterature include nickel (124), Raney nickel (125,126), palladium on different carriers (127,128), and palladium complexes (129). The hydrogenation of the double bond is exothermic Ai/ = —133.89 kJ/mol (—32 kcal/mol) (130). 

In the early 1990s, processes were developed for the production of 1,4-butanediol and y-butyrolactone by gas-phase catalytic hydrogenation of maleic anhydride (131—134). Succinic anhydride is obtained as a partial hydrogenation by-product in these processes. It can be recycled to complete the hydrogenation to the desired products, or be separated and purified. This process could in the future become a significant commercial route for succinic anhydride. 

Under the present reaction conditions, we observed the formation of succinic anhydride almost simultaneously together with the formation of GBL. The hydrogaiation of maleic anhydride yields succinic anhydride, and the subsequent hydrogenation of succinic anhydride produces GBL. The rate of hydrogenation of maleic anhydride to succinic anhydride was very fast compare to that of succinic anhydride to GBL. When the reaction was CEuried out wifliout solvent, tetrahydrofiiran was not producal. The above results indicate that the Pd-Mo-Ni/SiOz catalyst under our experimental conditions played an important role for the selective formation of GBL. Therefore, it is inferred that the catalyst composition may influence the route by which tetrahydrofiiran was formed, probably due to the different absorption mechanism of maleic anhydride, succinic anhydride, and GBL. 

Hydrogenation of maleic anhydride Cu/Cr (copper y-butyrol-acetonc. Solvents... 

Herrmann U, Emig G (1997) Liquid phase hydrogenation of maleic anhydride and intermediates on copper-based and noble metal catalysts. Ind Eng Chem Res 36 2885-2896... 

Succinic acid has a diverse range of applications in the synthesis of specialty chemicals used in agriculture, foods, medicine, textiles, plating, and waste-gas scrubbing (Winstrom, 1978). Currently, succinic acid is produced via the hydrogenation of maleic anhydride to succinic anhydride and hydration to succinic acid (Winstrom, 1978 Zeikus et al., 1995). The thermophylic anaerobic bacteria Clostridium thermosuccinogenes can convert inulin to succinate and acetate as major... 

Scheme 10.7 Synthesis of y-butyrolactone, tetrahydrofuran and 1,4-butanediol by hydrogenation of maleic anhydride.

Pillai, U. Sahle-Demessi, E. Selective Hydrogenation of Maleic Anhydride to y -Butyrolactone over Pd/ALO j Catalyst Using Supercritical C02 as Solvent, Chem. Commun. 2002, 5, 422-423. 

The two reaction pathways are not unique to the corresponding molybdenum or tungsten centers. For example, both metal hydrides effect hydrogenation of maleic anhydride [58]. Thus, the hydrogenation path may involve prior hydrometallation followed by reductive elimination of the hydridoalkyltungsten adduct (Eqs 61, 62). 

Hydrogenation of maleic anhydride (69) over Cu-CrO catalysts modified with Zn+2 and gave a 75% yield of y-butryolactone (70) when the reaction was run in the vapor phase at 250 C (Eqn. 18.43). 5> 66... 

Castiglioni, G.L. Fumagalli, C. Guercio, A. Lancia, R. Messori, M. Vaccari, A. Vapor-phase hydrogenation of maleic anhydride to y-butyro-lactone 2. Role of reaction parameters. Erdol Kohle-Erdgas-Petrochem. 1994, 47, 337-341. 

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. 

The maleic-anhydride route is based on the direct hydrogenation of maleic anhydride with H20 formed as a byproduct ... 

Now, THF is produced by selective hydrogenation of maleic anhydride [6, 7] or by dehydration of 1,4 butanediol (resulting from acetylene and formaldehyde, followed by the hydrogenation of the resulting 2-butyne-l,4 diol [23]). The old technology based on furfurol may be reconsidered in the future, because it uses a renewable resource as its raw material. 

Tetrahydrofuran, Diethylene oxide te tram ethyl -ene oxide. C,HsO, mol wt 72.10. C 66.63%, H 11.18%, O 22.19%, Prepn from 1,4-butanedioh Schmoyer, Case, Nature 187, 592 (I960). Manuf by catalytic hydrogenation of maleic anhydride Gilbert, Howk, U.S. pat. 2,772,293 (1956 to du Pont) of furan Banford, Manes, U.S. pat. 2,846,449 (1958 to du Pont) Manly, US. pat. 3,021,342 (1962 to Quaker Oats). Stabilization to prevent excessive peroxide formation On storage with 0.05-1,0% p-cresol, 0.05-0.1% hydroquinone, or less than 0.01-0.1% 4,4 -thiobis(6-terr-butyl -m-cresoi) Bordner, Hinegardner, and Campbell,... 

Selective hydrogenation of maleic anhydride by modified copper chromite catalysts... 

In Fig. 13, we depict the P-hydride elimination surface reaction for the CH2(CHO)-CH2- surface species to give acrolein. This microscopic reverse of this step involves the selective hydrogenation of acrolein, a valuable selective oxidation intermediate. Acrolein is a structural moiety for maleic anhydride, and therefore an ideal model for the hydrogenation of maleic anhydride to succinic a ydride. The predicted transition state is shown in the center of Fig. 13. The corresponding barrier for addition of hydrogen to adsorbed acrolein (the reverse reaction) is +82 kJ/mol. 

Unsaturated and saturated short-chain dicarboxylic acids such as maleic, succinic and adipic acid are well-known industrial chemicals manufactured on a petrochemical basis. Besides hydrogenation of maleic anhydride or oxidation of tetrahydrofuran, white biotechnology additionally opens a new route to... 

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... 

Tetrahydrofuran can be obtained by the hydrogenation of maleic anhydride or from agricultural waste (see also Section 24). The monomer can only be cationically polymerized to poly(tetrahydrofuran)... 

Mitsubishi Chemical produces also butanediol (as well as te-trahydrofuran) by the stepwise hydrogenation of maleic anhydride to succinic anhydride, Y butyrolactone and butanediol. 

Maleic anhydride is also used, in competition with acetylene, as a starting material for the production of 1,4-butanediol. Partial hydrogenation of maleic anhydride in the liquid phase (250 °C, 140 bar) on a nickel catalyst yields y-butyrolac-tone, a starting material for Vitamin Bi. 

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