Butanediol from 1,3-Butadiene

Selectivity to the coproducts is high, hut the ratios of the coproducts may he controlled with appropriate reactor operating conditions. Figure 9-2 is a block diagram for the hutane diol process." 1,4-Butanediol from butadiene is discussed later in this chapter. 

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. 

In the United States butadiene was prepared initially from ethanol and later by cracking four-carbon hydrocarbon streams (see Butadiene). In Germany butadiene was prepared from acetylene via the following steps acetylene — acetaldehyde — 3-hydroxybutyraldehyde — 1,3-butanediol — ... 

The pattern of commercial production of 1,3-butadiene parallels the overall development of the petrochemical industry. Since its discovery via pyrolysis of various organic materials, butadiene has been manufactured from acetylene as weU as ethanol, both via butanediols (1,3- and 1,4-) as intermediates (see Acetylene-DERIVED chemicals). On a global basis, the importance of these processes has decreased substantially because of the increasing production of butadiene from petroleum sources. China and India stiU convert ethanol to butadiene using the two-step process while Poland and the former USSR use a one-step process (229,230). In the past butadiene also was produced by the dehydrogenation of / -butane and oxydehydrogenation of / -butenes. However, butadiene is now primarily produced as a by-product in the steam cracking of hydrocarbon streams to produce ethylene. Except under market dislocation situations, butadiene is almost exclusively manufactured by this process in the United States, Western Europe, and Japan. 

Chemicals. Although the amount of butylenes produced ia the United States is roughly equal to the amounts of ethylene and propylene produced, the amount consumed for chemical use is considerably less. Thus, as shown ia Table 10, the utilisation of either ethylene or propylene for each of at least five principal chemical derivatives is about the same or greater than the utilisa tion of butenes for butadiene, their main use. This production is only about one-third of the total the two-thirds is derived directiy from butane. The undedyiag reasons are poorer price—performance compared to derivatives of ethylene and propylene and the lack of appHcations of butylene derivatives. Some of the products are more easily derived from 1-, 2-, and 3-carbon atom species, eg, butanol, 1,4-butanediol, and isobutyl alcohol (see Acetylene-DERIVED chemicals Butyl alcohols). 

Butadiene is obtained mainly as a coproduct with other light olefins from steam cracking units for ethylene production. Other sources of butadiene are the catalytic dehydrogenation of butanes and butenes, and dehydration of 1,4-butanediol. Butadiene is a colorless gas with a mild aromatic odor. Its specific gravity is 0.6211 at 20°C and its boiling temperature is -4.4°C. The U.S. production of butadiene reached 4.1 billion pounds in 1997 and it was the 36th highest-volume chemical. ... 

The most important reaction is the oxidative addition of two moles of acetic acid to butadiene to form 1,4-diacetoxy-2-butene (21) with the reduction of Pd2+ to Pd°. In this reaction, 3,4-diacetoxy-l-butene (127) is also formed. In order to carry out the reaction catalytic with regard to Pd2+, a redox system is used. This reaction attracts attention from the standpoint of industrial production of 1,4-butanediol. For this purpose, the formation of 127 should be minimized. Numerous patent applications have been made (examples 113-115), but no paper treating the systematic studies on the reaction has been published. 

Difunctionalization with similar or different nucleophiles has wide synthetic applications. The oxidative diacetoxylation of butadiene with Pd(OAc)2 affords 1,4-diacetoxy-2-butene (344) and l,2-diacetoxy-3-butene (345). The latter can be isomerized to the former. An industrial process has been developed based on this reaction. The commercial process for 1,4-diacetoxy-2-butene (344) has been developed using the supported Pd catalyst containing Te in AcOH. 1,4-Butanediol and THF are produced commercially from 1,4-diacetoxy-2-butene (344)[302],... 

The superior properties of polypropylene terephthalate) (PPT) polymer and fibers over the chemically analogous poly(ethylene terephthalate) (PET, used for soda bottles) and poly(butylene terephthalate) (PBT) have been well known for several decades PPT fibers are much more elastic and less brittle than PET and offer better recovery from stretching than PBT they are also easier to dye than either PET or PBT. Compared to the intermediate for PET, ethylene glycol, which is available inexpensively from ethylene oxide, and to that for PBT, butanediol, likewise available inexpensively from butene or butadiene, the intermediate for PPT, 1,3 propanediol (1,3-PPD or PDO), was not - and on a large scale is still not - available. Three processes, two chemical ones and one biotechnological, compete to change this situation (Figure 20.10). 

In contrast to the results reported by Behr under biphasic conditions, the activity of the system increased considerably with the longer-chain alcohols, going from an initial turnover frequency of 7,200 h-1 for ethylene glycol to 321,000 h 1 for 1,2-butanediol. This remarkable increase in activity was attributed to the increased hydrophobicity and the resulting better solubility of the diol in 1,3-butadiene, where the ligand is preferentially found. In addition, the yield of di-telomers was remarkably lower than for ethylene glycol. The highest TOF recorded for diols under these conditions was 400,000 h-1 for 1,5-pentanediol [84],... 

The thermal stability of this polymer has been studied, and by heating from ambient to 500° C the polymer generates butadiene, tetrahydrofuran, dihydrofuran, water, the cyclic ester of phenylphosphonic acid and 1,4-butanediol, phenylphosphonic acid, and butanediol [1]. The same report evaluates thermal decomposition of this polymer end capped with phenylisocyanate. In addition to the same compounds as for the main polymer, CO2 and aniline were detected from the polymer decomposition. 

The solvent properties of alcohols with short carbon chains are similar to those of water and such alcohols could be used as the nonaqueous catalyst phase when the products are apolar in nature. The first commercial biphasic process, the Shell Higher Olefin Process (SHOP) developed by Keim et al. [4], is nonaqueous and uses butanediol as the catalyst phase and a nickel catalyst modified with a diol-soluble phosphine, R2PCH2COOH. While ethylene is highly soluble in butanediol, the higher olefins phase-separate from the catalyst phase (cf. Section 2.3.1.3). The dimerization of butadiene to 1,3,7-octatriene was studied using triphenylphosphine-modified palladium catalyst in acetonitrile/hexafluoro-2-phe-nyl-2-propanol solvent mixtures [5]. The reaction of butadiene with phthalic acid to give octyl phthalate can be catalyzed by a nonaqueous catalyst formed in-situ from Pd(acac)2 (acac, acetylacetonate) and P(0CeH40CH3)3 in dimethyl sulfoxide (DMSO). In both systems the products are extracted from the catalyst phase by isooctane, which is separated from the final products by distillation [5]. 

Small amounts of butadiene can be prepared conveniently as follows from 1,3-butanediol, a starting material supplied by Aldrich and by Eastman a mixture of 45 g. of the diol, 200 g. of phthalic anhydride, and 5 g. of benzenesulfonic acid on distillation for 2 hrs. affords butadiene in 47% yield. 

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... 

First there was the chemistry of olefins which owing to Germany s oil deficiency could not be obtained by cracking, but had to be produced by hydrogenation of acetylene originating from coal via calcium carbide. At the beginning of the 1920 s, acetylene was used first for addition reactions at normal pressure the most important product was acetaldehyde which via aldol, 1,3-butanediol, and butadiene led to synthetic rubber. Other important products were ethylene oxide, acrylic esters, styrene, etc. 

The Reppe process is based on acetylene as a raw material. These reactions were developed by Reppe et al. [2]. In accordance with the rise of the petrochemical industry, most processes switched from acetylene to olefins as raw material. However, only the 1,4-butanediol production process continued to rely on the Reppe process. Mitsubishi Chemical Corporation developed a totally different production method that uses 1,3-butadiene to produce 1,4-butanediol and THF. Commercial production was launched in 1982 and has been continued ever since. This process ended the over-half-century monopoly of the Reppe method. The Mitsubishi Chemical method has an advantage over the Reppe method with respect to the handling of raw materials and production costs, but in recent years, Chinese companies that can take advantage of inexpensive natural gas and coal have built a new production plant by using the Reppe method and international competition is getting more intense. 

The 1,3-butadiene-based 1,4-butanediol process was reviewed in this chapter. This method ended the half-century monopoly of the acetylene-based Reppe method. This development was in line with the switch from coal to petroleum feedstock. Because the acetoxylation of 1,3-butadiene was the first successful commercial... 

---