Dehydrogenation butan

Two or more soHd catalyst components can be mixed to produce a composite that functions as a supported catalyst. The ingredients may be mixed as wet or dry powders and pressed into tablets, roUed into spheres, or pelletized, and then activated. The promoted potassium ferrite catalysts used to dehydrogenate ethylbenzene in the manufacture of styrene or to dehydrogenate butanes in the manufacture of butenes are examples of catalysts manufactured by pelletization and calcination of physically mixed soHd components. In this case a potassium salt, iron oxide, and other ingredients are mixed, extmded, and calcined to produce the iron oxide-supported potassium ferrite catalyst. 

Phillips (3) A two-stage process for dehydrogenating butane to butadiene. 

Butadiene is made commercially by dehydrogenating butanes or butenes in the presence of a catalyst, by reacting ethanol and acetalde... 

New processes such as isomerization and the dehydrogenation of n-butane will make their appearance. 

Dehydrogenation (Section 5 1) Elimination in which H2 is lost from adjacent atoms The term is most commonly en countered in the mdustnal preparation of ethylene from ethane propene from propane 1 3 butadiene from butane and styrene from ethylbenzene... 

Natural gas Hquids represent a significant source of feedstocks for the production of important chemical building blocks that form the basis for many commercial and iadustrial products. Ethyleae (qv) is produced by steam-crackiag the ethane and propane fractions obtained from natural gas, and the butane fraction can be catalyticaHy dehydrogenated to yield 1,3-butadiene, a compound used ia the preparatioa of many polymers (see Butadiene). The / -butane fractioa can also be used as a feedstock ia the manufacture of MTBE. 

Dehydrogenation. Dehydrogenation of / -butane was once used to make 1,3-butadiene, a precursor for synthetic mbber. There are currently no on-purpose butadiene plants operating in the United States butadiene is usually obtained as a by-product from catalytic cracking units. 

Production of maleic anhydride by oxidation of / -butane represents one of butane s largest markets. Butane and LPG are also used as feedstocks for ethylene production by thermal cracking. A relatively new use for butane of growing importance is isomerization to isobutane, followed by dehydrogenation to isobutylene for use in MTBE synthesis. Smaller chemical uses include production of acetic acid and by-products. Methyl ethyl ketone (MEK) is the principal by-product, though small amounts of formic, propionic, and butyric acid are also produced. / -Butane is also used as a solvent in Hquid—Hquid extraction of heavy oils in a deasphalting process. 

About 35% of total U.S. LPG consumption is as chemical feedstock for petrochemicals and polymer iatermediates. The manufacture of polyethylene, polypropylene, and poly(vinyl chloride) requires huge volumes of ethylene (qv) and propylene which, ia the United States, are produced by thermal cracking/dehydrogenation of propane, butane, and ethane (see Olefin polymers Vinyl polymers). 

Butadiene. Although butadiene was produced in the United States in the eady 1920s, it was not until the start of Wodd War 11 that significant quantities were produced to meet the war effort. A number of processes were investigated as part of the American Synthetic Rubber Program. Catalytic dehydrogenation of / -butenes and / -butanes (Houdry process) and thermal cracking of petroleum hydrocarbons were chosen (12). 

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. 

Dehydrogenation of /i-Butane. Dehydrogenation of / -butane [106-97-8] via the Houdry process is carried out under partial vacuum, 35—75 kPa (5—11 psi), at about 535—650°C with a fixed-bed catalyst. The catalyst consists of aluminum oxide and chromium oxide as the principal components. The reaction is endothermic and the cycle life of the catalyst is about 10 minutes because of coke buildup. Several parallel reactors are needed in the plant to allow for continuous operation with catalyst regeneration. Thermodynamics limits the conversion to about 30—40% and the ultimate yield is 60—65 wt % (233). 

During World War II, production of butadiene (qv) from ethanol was of great importance. About 60% of the butadiene produced in the United States during that time was obtained by a two-step process utilizing a 3 1 mixture of ethanol and acetaldehyde at atmospheric pressure and a catalyst of tantalum oxide and siHca gel at 325—350°C (393—397). Extensive catalytic studies were reported (398—401) including a fluidized process (402). However, because of later developments in the manufacture of butadiene by the dehydrogenation of butane and butenes, and by naphtha cracking, the use of ethanol as a raw material for this purpose has all but disappeared. 

Timoshenko et al (1967) recommended running a set of experiments in a CSTR on feed composition (now called feed-forward study), and then statistically correlating the discharge concentrations and rates with feed conditions by second order polynomials. In the second stage, mathematical experiments are executed on the previous empirical correlation to find the form and constants for the rate expressions. An example is presented for the dehydrogenation of butane. 

The term, metal dusting, was first used about this time to describe the phenomenon associated with hydrocarbon processing. Butane dehydrogenation plant personnel noted how iron oxide and coke radiated outward through catalyst particles from a metal contaminant which acted as a nucleating point. The metal had deteriorated and appeared to have turned to dust. The phenomenon has been called catastrophic carburization and metal deterioration in a high temperature carbonaceous environment, but the term most commonly used today is metal dusting. 

The conjugated diene 1,3-butadiene is used in the manufacture of synthetic rubber and is prepared on an industrial scale in vast quantities. Production in the United States is currently 4X10 Ib/yearc One industrial process is similar- to that used for the preparation of ethylene In the presence of a suitable catalyst, butane undergoes thermal dehydrogenation to yield 1,3-butadiene. 

Butadiene is an industrial chemical and is prepared by dehydrogenation of butane. Elimination reactions such as dehydration and dehydro-halogenation are common routes to alkadienes. 

Butane is primarily used as a fuel gas within the LPG mixture. Like ethane and propane, the main chemical use of butane is as feedstock for steam cracking units for olefin production. Dehydrogenation of n-butane to butenes and to butadiene is an important route for the production of synthetic rubber. n-Butane is also a starting material for acetic acid and maleic anhydride production (Chapter 6). 

Dehydrogenation of butanes is a second source of butenes. However, this source is becoming more important because isobutylene (a butene isomer) is currently highly demanded for the production of oxygenates as gasoline additives. 

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. ... 

Butadiene could also be produced by the catalytic dehydrogenation of butanes or a butane/butene mixture. 

The first step involves dehydrogenation of the butanes to a mixture of butenes which are then separated, recycled, and converted to butadiene. Figure 3-16 is the Lummus fixed-bed dehydrogenation of C4 mixture to butadiene. The process may also be used for the dehydrogenation of mixed amylenes to isoprene. In the process, the hot reactor effluent is quenched, compressed, and cooled. The product mixture is extracted unreacted butanes are separated and recycled, and butadiene is recovered. 

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