Butadiene process

Behr A, Heite M (2000) Telomerization of carbon dioxide and 1,3-butadiene process development in a miniplant. Chem Eng Technol 23 952-955... 

Section, which appears every month. It also has a special section on Patents which lists new patents according to their classification. The Process Issue of the Petroleum Refiner is now carrying a special section on Petrochemical Processes. In the September 1952 issue for example, Extractive Distillation for Aromatic Recovery, Modified SO2 Extraction for Aromatic Recovery, Udex Extraction, Ethylene Manufacture by Cracking, Ethylene Production, Hypersorption, Hydrocol, Dehydrogenation (for butadiene), and Butadiene Process, were described. These descriptions include the main essentials of the process, simplified flow diagrams, and the name of the company offering it. Formerly these processes were described under the Process Section. 

Organic iodine recovery is less of a problem in a propylene process than in a butadiene process. Diiodobutene polymerizes in the quenching section, and methyl iodide-butadiene separation is difficult. 

Seta reader. K, Volkamer, K, Wagner, U, Recent improvements of BASF s butadiene process , 2 Petro-ekeoseni Iorin-Ameritwi Congress, Canpun, Mexico (12/18 Nov. 1978)... 

An industrial separation problem may be defined in terms of a process feed and specifications for the desired products. An example adapted from Hendry and Hughes/ based on a separation process for a butadiene processing plant, is given in Fig. 1.16. 

In certain cri-butadiene processes, the volume of the diluting solvent is sufficiently high that cooling is achieved by feeding cold diluent solvent to the reactor. For an end-use application, the final polymer concentration was 10%. The specific heat of the solvent is 0.96 Btu/lb°F. If the final reaction temperature is 122°F, at what temperature should the solvent be fed into the reactor so as to remove all of the heat of polymerization ... 

In the first butadiene process (process 3 in Figure 2.13) developed by DuPont [171], chlorine is reacted with butadiene at about 200°C in a mole ratio of 4.T. At a 95% yield this reaction results in the formation of both 1,4-dichlorobutene and 1,2-dichlorobutene. Treating this mixture with HCN at 130-150°C in the presence of HCl acceptors such as CaCOs yields l,4-dicyanobutene-2, which upon treatment with a basic catalyst, isomerizes to 1,4-dicyano-butene-1. Hydrogenation at 250°C and at atmospheric pressure in the gas phase using a palladium catalyst yields hexamethylene diamine directly. 

Tetraisopropyl di (dioctylphosphito) titanate Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate Vinyl butadiene processing aid, ABS Ethylene distearamide processing aid, adhesives t-Butyl alcohol C5 hydrocarbon resin, aliphatic MDI Methyl hydroxystearate Simethicone Synthetic wax processing aid, aerosols Sodium toluenesulfonate Sodium xylenesulfonate processing aid, agric. t-Butyl alcohol... 

FIGURE 13.50 Analysis for butadiene process streams with peak identifications in Table 10.6. (Reprinted with permission from Reference 120, Journal of Chromatographic Science, Copyright 1972, Preston Publications, A Division of Preston Industries, Inc.)... 

From the very beginning up to the 1960s, chloroprene was produced by the older energy-intensive acetylene process using acetylene, derived from calcium carbide [3]. The acetylene process had the additional disadvantage of high investment costs because of the difficulty of controlling the conversion of acetylene into chloroprene. The modern butadiene process, which is now used by nearly all chloroprene producers, is based on the readily available butadiene [3]. 

The DuPont direct hydrocyanation of butadiene process for the production of hexamethylene diamine can also be adapted for the production of caprolactam. Partial hydrogenation of the adiponitrile intermediate in which only one cyanide group is converted to the amine, followed by hydrolysis of the remaining cyanide group and ring closure can produce s-caprolactam. The process has not been developed commercially. It is also possible that a two-stage butadiene car-bony lation process to produce caprolactam, developed by DSM and Shell, may be further developed. 

This is an exothermic, reversible, homogeneous reaction taking place in a single liquid phase. The liquid butadiene feed contains 0.5 percent normal butane as an impurity. The sulfur dioxide is essentially pure. The mole ratio of sulfur dioxide to butadiene must be kept above 1 to prevent unwanted polymerization reactions. A value of 1.2 is assumed. The temperature in the process must be kept above 65°C to prevent crystallization of the butadiene sulfone but below lOO C to prevent its decomposition. The product must contain less than 0.5 wt% butadiene and less thM 0.3 wt% sulfur dioxide. 

Figure 4.16 Final flowsheet for the production of butadiene sulfone in a batch process.

Properly speaking, steam cracking is not a refining process. A key petrochemical process, it has the purpose of producing ethylene, propylene, butadiene, butenes and aromatics (BTX) mainly from light fractions of crude oil (LPG, naphthas), but also from heavy fractions hydrotreated or not (paraffinic vacuum distillates, residue from hydrocracking HOC). 

This form of limited-conversion hydrocracking is a process that selectively prepares high quality residues for the special manufacture of base oils of high viscosity index or treating residues having low BMCl for the conversion of heavy fractions to ethylene, propylene, butadiene and aromatics. 

Once these approximations have been made, HMO theory becomes very simple. Using 1,3-butadiene, 1, as an example, we can work through an HMO calculation in order to outline the process involved. Firstly, we assign numbers to the carbon atoms, as shown in Figure 7-19. 

Difunctionalization with similar or different nucleophiles has wide synthetic applications. The oxidative diacetoxylation of butadiene with Pd(OAc)i 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 l,4-diacetoxy-2-butene (344) has been developed using the supported Pd catalyst containing Te in AcOH. 1,4-Butanedioi and THF are produced commercially from 1,4-diacetoxy-2-butene (344)[302]. 

The conjugated diene 1 3 butadiene is used m the manufacture of synthetic rubber and IS prepared on an industrial scale m vast quantities Production m the United States is currently 4 X 10 Ib/year One industrial process is similar to that used for the prepara tion of ethylene In the presence of a suitable catalyst butane undergoes thermal dehy drogenation to yield 1 3 butadiene... 

Symmetry allowed reaction (Section 10 14) Concerted reac tion in which the orbitals involved overlap in phase at all stages of the process The conrotatory ring opening of cy clobutene to 1 3 butadiene is a symmetry allowed reaction... 

Adiponitrile is made commercially by several different processes utilizing different feedstocks. The original process, utilizing adipic acid (qv) as a feedstock, was first commercialized by DuPont in the late 1930s and was the basis for a number of adiponitrile plants. However, the adipic acid process was abandoned by DuPont in favor of two processes based on butadiene (qv). During the 1960s, Monsanto and Asahi developed routes to adiponitrile by the electrodimerization of acrylonitrile (qv). 

In a related process, 1,4-dichlorobutene was produced by direct vapor-phase chlorination of butadiene at 160—250°C. The 1,4-dichlorobutenes reacted with aqueous sodium cyanide in the presence of copper catalysts to produce the isomeric 1,4-dicyanobutenes yields were as high as 95% (58). The by-product NaCl could be recovered for reconversion to Na and CI2 via electrolysis. Adiponitrile was produced by the hydrogenation of the dicyanobutenes over a palladium catalyst in either the vapor phase or the Hquid phase (59,60). The yield in either case was 95% or better. This process is no longer practiced by DuPont in favor of the more economically attractive process described below. 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

Manufacture via this process has been completely replaced by chlorination of butadiene (3) (see Chlorocarbons and chlorohydrocarbons, chloroprene ElASTOT RS, synthetic, POLYCm OROPRENE). 

Another process, involving chlorination of butadiene, hydrolysis of the dichlorobutene, and hydrogenation of the resulting butenediol, was practiced by Toyo Soda in Japan until the mid-1980s (144). 

Acrolein a.s Dienophile. The participation of acrolein as the dienophile in Diels-Alder reactions is, in general, an exothermic process. Dienes such as cyclopentadiene and l-dieth5laniino-l,3-butadiene react rapidly with acrolein at room temperature. 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

It has been known since the early 1950s that butadiene reacts with CO to form aldehydes and ketones that could be treated further to give adipic acid (131). Processes for producing adipic acid from butadiene and carbon monoxide [630-08-0] have been explored since around 1970 by a number of companies, especially ARCO, Asahi, BASF, British Petroleum, Du Pont, Monsanto, and Shell. BASF has developed a process sufficiendy advanced to consider commercialization (132). There are two main variations, one a carboalkoxylation and the other a hydrocarboxylation. These differ in whether an alcohol, such as methanol [67-56-1is used to produce intermediate pentenoates (133), or water is used for the production of intermediate pentenoic acids (134). The former is a two-step process which uses high pressure, >31 MPa (306 atm), and moderate temperatures (100—150°C) (132—135). Butadiene,... 

Butadiene Separation. Solvent extraction is used in the separation of butadiene (qv) [106-99-0] from other C-4 hydrocarbons in the manufacture of synthetic mbber. The butadiene is produced by catalytic dehydrogenation of butylene and the Hquid product is then extracted using an aqueous cuprammonium acetate solution with which the butadiene reacts to form a complex. Butadiene is then recovered by stripping from the extract. Distillation is a competing process. 

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