Maleic anhydride 1,4-butanediol from

Reduction. Heterogeneous catalytic reduction processes provide effective routes for the production of maleic anhydride derivatives such as succinic anhydride [108-30-5] (26), succinates, y-butyrolactone [96-48-0] (27), tetrahydrofuran [109-99-9] (29), and 1,4-butanediol [110-63-4] (28). The technology for production of 1,4-butanediol from maleic anhydride has been reviewed (92,93). 

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). 

An important future use for maleic anhydride is beUeved to be the production of products in the 1,4-butanediol—y-butyrolactone—tetrahydrofuran family. Davy Process Technology has commercialized a process (93) for producing 1,4-butanediol from maleic anhydride. This technology can be used to produce the product mix of the three molecules as needed by the producer. Another significant effort in this area is the tetrahydrofuran plant under constmction in Spain by Du Pont in which butane is oxidized and recovered as maleic acid and the maleic acid is then reduced to tetrahydrofuran (109). 

Figure 9-2. A block diagram for producing 1,4-butanediol from maleic anhydride. ...

The production of 1,4-butanediol (1,4-BDO) from propylene via the carbonylation of allyl acetate is noted in Chapter 8. 1,4-Butanediol from maleic anhydride is discussed later in this chapter. An alternative route for the diol is through the acetoxylation of butadiene with acetic acid followed by hydrogenation and hydrolysis. 

FIGURE 1 Manufacture of 1,4-butanediol from maleic anhydride. 

A new process to manufacture THF and 1,4 butanediol from maleic anhydride is currently slated for start-up by DuPont in Asturias, Spain in 1996. The process involves the oxidation of n-butane in a transport bed reactor to form maleic anhydride. Recovery of maleic anhydride is accomplished by scrubbing with water which converts the anhydride immediately to maleic acid. The maleic acid is then hydrogenated to tetrahydrofuran in a bubble column reactor. By varying operating conditions in the hydrogenation reactor the alternate or coproduction of 1,4 butanediol can be accomplished. 

The former Reppe chemistry, still practiced in Germany by BASF and in the United States by GAF, also led to new developments as demand for certain intermediates such as the 1,4-butanediol increased. This diol, now also obtained from maleic anhydride, is used to produce PBT polyesters through reaction with terephthalic acid and leads to other major derivates (tetrahydrofuran, butyrolactone, N-vinylpyrrolidone). 

Gamma-Butyrolactone (GBL) is an intermediate for the manufacture of Pyrrolidones which have a wide range of uses such as speciality solvents, functional monomers and pharmaceutical intermediates. GBL can be made by the vapour phase dehydrogenation of 1,4-butanediol over a copper/pumice catalyst at 200°C. It is also available as a by-product with THF in the Davy McKee two step butane diol process starting from maleic anhydride (MAN) via diethylmaleate [27]. 

Polyester from maleic anhydride, hexolic acid and butanediol mole ratio 1 1 2.2... 

Growth in the use of acetylene for the production of 1,4-butanediol is projected to continue at the rate of about 5% per year. However, competition from a new technology based on maleic anhydride may impact the use of acetylene in this market. 

Manufacturing. Almost all the THE in the United States is currendy produced by the acid-catalyzed dehydration of 1,4-butanediol [10-63-4]. Only one plant in the United States still makes THE by the hydrogenation of furfural (29). Du Pont recendy claimed a new low cost process for producing THE from / -butane that they plan to commercialize in 1995 (30—32). The new process transport-bed oxidizes / -butane to cmde maleic anhydride, then follows with a hydrogen reduction of aqueous maleic acid to THE (30). 

Application To produce 1,4 butanediol (BDO) from butane via maleic anhydride and hydrogen using ester hydrogenation. 

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. 

The worldwide market for butanediol (EDO) in 2003 was about 800,000 MT, of which more than half of the production used the Reppe process, which uses acetylene and formaldehyde as the raw materials. However, the industry is moving toward the cheaper technology of using maleic anhydride obtained from butane as the raw material [85]. Although other commercial processes are used to synthesize EDO starting from butadiene, dichlorobutene, or propylene oxide, we limit ourselves to processes where carbon-supported catalysts are used the... 

Davy Process Technology, U K Butanediol, 1,4- Maleic anhydride and hydrogen Process produces 1,4 butanediol (BDO) from butane via maleic anhydride and hydrogen using ester hydrogenation 11 NA... 

Several processes starting from acetylene, butadiene, maleic anhydride or propylene have been recently developped for the production of butanediol. Various possibilities are shown on Figure... 

Polybutylene Succinate (PBS). Manufacturers of polybutylene succinate, produced from polymerization of succinic acid and 1,4-butanediol, include Showa Highpoly-mer, which produces Bionolle polymers SK Polymers, which makes SkyGreen BDP and Mitsubishi Chemical. Normally, the source of both monomers is maleic anhydride. However, Mitsubishi is working with Ajinomoto to produce succinic acid by fermentation of sugar and starch, providing a biodegradable polymer that is partly biobased. ... 

Maleic anhydride is currently used in the production of unsaturated polyesters and butanediol. World consumption over the last few years has exceeded 1.3 x 10 metric tons per year. Currently, ca. 70% of MA is produced from -butane partial oxidation. In this way, partial oxidation of -butane to MA is the only... 

For example, the production of butanediol from butane involves three steps (Figure 10.2 solid arrows) (1) partial oxidation of butane to maleic anhydride, (2) selective hydrogenation of maleic anhydride to tetrahydrofuran, and (3) hydration of tetrahydrofuran to butanediol. From the stoichiometry of the reactions, for every mole of butanediol produced—even if each step proceeds with 100% yield—3 moles of hydrogen are consumed. 

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 is one of the high-volume specialty chemicals. It is produced by the catalytic hydrogenation of petrochemical maleic acid or anhydride. However, due to cost reductions delivered via the production of succinic acid from the bacterial fermentation of carbohydrates, a large-volume commodity market could be realized. Presently, the bacterial strain used for succinic acid manufacturing is Escherichia coli. However, the requirement for lower costs is moving companies toward other microorganisms, such as Coryne-type bacteria and yeast. Succinic acid can be converted to 1,4-butanediol (EDO) and other products. It also serves as a raw material for diverse important chemicals, including polymers, polybutylene terephthalate, and polybutylene succinate. 

---