Pyrolysis acetylene

In 1869 Berthelot- reported the production of styrene by dehydrogenation of ethylbenzene. This method is the basis of present day commercial methods. Over the year many other methods were developed, such as the decarboxylation of acids, dehydration of alcohols, pyrolysis of acetylene, pyrolysis of hydrocarbons and the chlorination and dehydrogenation of ethylbenzene." ... 

This evidence that benzyne is at least one of the intermediates in acetylene pyrolysis has many implications. However, as the ratios of products from acetylene and hexafluorobenzene differ appreciably from those obtained from phthalic anhydride, it might be best at this point to call acetylene a benzynoid precursor. Additional data will be needed and are being accumulated to determine to what extent acetylene reactions proceed at high temperatures through a benzyne intermediate (Fields and Meyerson, 1967a). 

Keywords MCM-41 silica, surface silicon hydride groups, gold and silver in situ reduction, nickel, cobalt, and iron aeetylacetonates, acetylene pyrolysis, carbon nanotubes... 

Vlayl fluoride [75-02-5] (VF) (fluoroethene) is a colorless gas at ambient conditions. It was first prepared by reaction of l,l-difluoro-2-bromoethane [359-07-9] with ziac (1). Most approaches to vinyl fluoride synthesis have employed reactions of acetylene [74-86-2] with hydrogen fluoride (HF) either directly (2—5) or utilizing catalysts (3,6—10). Other routes have iavolved ethylene [74-85-1] and HF (11), pyrolysis of 1,1-difluoroethane [624-72-6] (12,13) and fluorochloroethanes (14—18), reaction of 1,1-difluoroethane with acetylene (19,20), and halogen exchange of vinyl chloride [75-01-4] with HF (21—23). Physical properties of vinyl fluoride are given ia Table 1. 

Concentrations depend on severity of pyrolysis. At a high severity (- 2000° C) acetylene/ethylene ratio is 1, but at lower severity acetylene concentration is reduced and ethylene is increased. 

Flame or Partial Combustion Processes. In the combustion or flame processes, the necessary energy is imparted to the feedstock by the partial combustion of the hydrocarbon feed (one-stage process), or by the combustion of residual gas, or any other suitable fuel, and subsequent injection of the cracking stock into the hot combustion gases (two-stage process). A detailed discussion of the kinetics for the pyrolysis of methane for the production of acetylene by partial oxidation, and some conclusions as to reaction mechanism have been given (12). 

Hoechst HTP Process. The two-stage HTP (high temperature pyrolysis) process was operated by Farbwerke Hoechst ia Germany. The cracking stock for the HTP process can be any suitable hydrocarbon. With hydrocarbons higher than methane, the ratio of acetylene to ethylene can be varied over a range of 70 30 to 30 70. Total acetylene and ethylene yields, as wt % of the feed, are noted ia Table 11. 

Regenerative pyrolysis processing is very versatile it can handle varied feedstocks and produce a range of ethylene to acetylene. The acetylene content of the cracked gases is high and this assists purification. On the other hand, the plant is relatively expensive and requires considerable maintenance because of the wear and tear on the refractory of cycHc operation. 

Acetylene traditionally has been made from coal (coke) via the calcium carbide process. However, laboratory and bench-scale experiments have demonstrated the technical feasibiUty of producing the acetylene by the direct pyrolysis of coal. Researchers in Great Britain (24,28), India (25), and Japan (27) reported appreciable yields of acetylene from the pyrolysis of coal in a hydrogen-enhanced argon plasma. In subsequent work (29), it was shown that the yields could be dramatically increased through the use of a pure hydrogen plasma. 

Pyrolysis. Vinyl chloride is more stable than saturated chloroalkanes to thermal pyrolysis, which is why nearly all vinyl chloride made commercially comes from thermal dehydrochlorination of EDC. When vinyl chloride is heated to 450°C, only small amounts of acetylene form. Litde conversion of vinyl chloride occurs, even at 525—575°C, and the main products are chloroprene [126-99-8] and acetylene. The presence of HCl lowers the amount of chloroprene formed. 

By-products from EDC pyrolysis typically include acetjiene, ethylene, methyl chloride, ethyl chloride, 1,3-butadiene, vinylacetylene, benzene, chloroprene, vinyUdene chloride, 1,1-dichloroethane, chloroform, carbon tetrachloride, 1,1,1-trichloroethane [71-55-6] and other chlorinated hydrocarbons (78). Most of these impurities remain with the unconverted EDC, and are subsequendy removed in EDC purification as light and heavy ends. The lightest compounds, ethylene and acetylene, are taken off with the HCl and end up in the oxychlorination reactor feed. The acetylene can be selectively hydrogenated to ethylene. The compounds that have boiling points near that of vinyl chloride, ie, methyl chloride and 1,3-butadiene, will codistiU with the vinyl chloride product. Chlorine or carbon tetrachloride addition to the pyrolysis reactor feed has been used to suppress methyl chloride formation, whereas 1,3-butadiene, which interferes with PVC polymerization, can be removed by treatment with chlorine or HCl, or by selective hydrogenation. 

Alternatives to oxychlorination have also been proposed as part of a balanced VCM plant. In the past, many vinyl chloride manufacturers used a balanced ethylene—acetylene process for a brief period prior to the commercialization of oxychlorination technology. Addition of HCl to acetylene was used instead of ethylene oxychlorination to consume the HCl made in EDC pyrolysis. Since the 1950s, the relative costs of ethylene and acetylene have made this route economically unattractive. Another alternative is HCl oxidation to chlorine, which can subsequently be used in dkect chlorination (131). The SheU-Deacon (132), Kel-Chlor (133), and MT-Chlor (134) processes, as well as a process recently developed at the University of Southern California (135) are among the available commercial HCl oxidation technologies. Each has had very limited industrial appHcation, perhaps because the equiHbrium reaction is incomplete and the mixture of HCl, O2, CI2, and water presents very challenging separation, purification, and handling requkements. HCl oxidation does not compare favorably with oxychlorination because it also requkes twice the dkect chlorination capacity for a balanced vinyl chloride plant. Consequently, it is doubtful that it will ever displace oxychlorination in the production of vinyl chloride by the balanced ethylene process. 

Outside the realm of typical hydrocarbon pyrolysis is the high temperature pyrolysis of methane. In one variant of this process, which has only been commercialized to produce acetylene (with some BTX), methane reacts in an electric arc at about 1500°C (17) with very short contact times. At higher temperatures or with a catalyst and added hydrogen, BTX is produced with fairly high selectivity (18). 

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. 

Pyrolysis. Pyrolysis of 1,2-dichloroethane in the temperature range of 340—515°C gives vinyl chloride, hydrogen chloride, and traces of acetylene (1,18) and 2-chlorobutadiene. Reaction rate is accelerated by chlorine (19), bromine, bromotrichloromethane, carbon tetrachloride (20), and other free-radical generators. Catalytic dehydrochlorination of 1,2-dichloroethane on activated alumina (3), metal carbonate, and sulfate salts (5) has been reported, and lasers have been used to initiate the cracking reaction, although not at a low enough temperature to show economic benefits. 

Perhaps the most firmly based report for the formation of an azete involves flash pyrolysis of tris(dimethylamino)triazine (303). This gave a red pyrolysate believed to contain the highly stabilized azete (304) on the basis of spectroscopic data. The putative azete decomposed only slowly at room temperature, but all attempts to trap it failed (73AG(E)847). Flash pyrolysis of other 1,2,3-triazines gives only acetylenes and nitriles and it is not possible to tell whether these are formed by direct <,2-l-<,2-l-<,2 fragmentation of the triazine or by prior extrusion of nitrogen and collapse to an azete (81JCR(S)162). 

Heat is transferred by direct contact with solids that have been preheated by combustion gases. The process is a cycle of alternate heating and reactingperiods. The Wulf process for acetylene by pyrolysis of natural gas utilizes a heated brick checker work on a 4-min cycle of heating and reacting. The temperature play is 15°C (59°F), peak temperature is 1,200°C (2,192°F), residence time is 0.1 s of wmich 0.03 s is near the peak (Faith, Keyes, and Clark, Industrial Chemicals, vol. 27, Wiley, 1975). 

Burning a portion of a combustible reactant with a small additive of air or oxygen. Such oxidative pyrolysis of light hydrocarbons to acetylene is done in a special burner, at 0.001 to 0.01 s reaction time, peak at 1,400°C (2,552°F), followed by rapid quenching with oil or water. 

The monomer is produced from trichloroethane by dehydrochlorination Figure 17.2). This may be effected by pyrolysis at 400°C, by heating with lime or treatment with caustic soda. The trichlorethane itself may be obtained from ethylene, vinyl chloride or acetylene. 

The as-produced filaments were very strongly covered by amorphous carbon produced by thermal pyrolysis of acetylene. The amount of amorphous carbon varied with the reaction conditions. It increased with increasing reaction temperature and with the percentage of acetylene in the reaction mixture. Even in optimal conditions not less than 50% of the carbon was deposited in the form of amorphous carbon in accordance with [13]. 

The six-membered nng in polyfluoropyndazmes is much more stable, and pyrolysis at 680-725 °C is needed to eliminate mirogen, resulting m various fluonnated acetylene compounds in 80-90% yield [77](equation 46)... 

Similarly, low-temperature photolysis of 4,5,6-fluorosubstituted 1,2,3-tna zines results in the elimination of nitrogen, but the product composition depends on the substituents When the substituents are fluonne atoms, the intermediate product IS a four-membered, mtrogen-contaming ring that quickly dimenzes When all the substituents are perfluoroalkyl groups, the pyrolysis results in a mixture perfluoroalkyl acetylenes and perfluoroalkyl cyanides [79] (equations 48 and 49). 

A typical ethane cracker has several identical pyrolysis furnaces in which fresh ethane feed and recycled ethane are cracked with steam as a diluent. Figure 3-12 is a block diagram for ethylene from ethane. The outlet temperature is usually in the 800°C range. The furnace effluent is quenched in a heat exchanger and further cooled by direct contact in a water quench tower where steam is condensed and recycled to the pyrolysis furnace. After the cracked gas is treated to remove acid gases, hydrogen and methane are separated from the pyrolysis products in the demethanizer. The effluent is then treated to remove acetylene, and ethylene is separated from ethane and heavier in the ethylene fractionator. The bottom fraction is separated in the deethanizer into ethane and fraction. Ethane is then recycled to the pyrolysis furnace. 

Dihydro-2f/-pyran-2-one has been prepared by reductive cycliza-tion of 5-hydroxy-2-pentynoic acid [2-Pentynoic acid, 5-hydroxy-], which is obtained in two steps from acetylene [Ethyne] and ethylene oxide [Oxirane] 3 and by the reaction of dihydropyran [277-Pyran, 3,4-dihydro-] with singlet oxygen [Oxygen, singlet].4,5 2ff-Pyran-2-one has been prepared by pyrolysis of heavy metal salts of coumalic acid [2//-Pyran-5-carboxylic acid, 2-oxo-],8 by pyrolysis of a-pyrone-6-carboxylic acid [211 - Pyran-6-carboxyl ic acid, 2-oxo-] over copper,7 and by pyrolysis of coumalic acid over copper (66-70% yield).8... 

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