Manufacture Based on Calcium Carbide The worldwide production of Calcium carbide from the strongly endothermic (H = + 111 kcal

or 465 kJ/mol) electrothermal reaction between quicklime and coke at 2200-2300 C reached a maximum of about 107 tonnes per year in 1960. Current production worldwide is about 5106 tonnes per year. Production figures for several nations can be seen in the accompanying table. Despite the decline in production, new interest in modern carbide/acetylene manufacture has been awakened in several countries. This is shown, for example, by research at the US Institute of Gas Technology on the use of solar energy for CaC2 synthesis. Calcium carbide can be converted into acetylene and calcium hydroxide in an exothermic reaction with H 2O:

Industrially, acetylene is formed in one of two types of generators. In the wet generator, an excess of water is used. In a dry generator, an approximately stoichiometric amount of water is used, and the calcium hydroxide is obtained as a pourable powder. The heat of reaction is removed by evaporation of a portion of the added water. Continuously operating large-scale dry generators with an output up to 3750 m3/h C2H2 = 32000 tonnes per year have been developed by Knapsack and Shawinigan. The byproduct calcium hydroxide is either recycled (up to 50%) for carbide manufacture or employed in construction, in the chemical industry, or in agriculture. Before being used as a chemical feedstock, C2H2 is washed in three steps. After removing basic products such as NH3 by means of a H2SO4 wash, impurities containing P and S are oxidized either with chlorine water or 98% H2SO4 and scrubbed. In the third step, traces of acid are removed with caustic soda solution. Thermal Processes Numerous processes for the manufacture of C2H2 are based on the uncatalyzed pyrolysis of hydrocarbons in the C-range from methane to light petrol to crude oil. With newer process developments, higher boiling fractions, residual oils, and even coal can also be used. In principle, thermodynamics and kinetics have a deciding influence on the choice of reaction conditions. Important for all processes are a rapid energy transfer at a high temperature level (> 1400 C), very short residence times of the feed or reaction products (10-2 to 10-3 s), low partial pressure of acetylene, and rapid quenching of the pyrolyzed gases. The C2H2 present in the cracked gas is relatively dilute, about 5-20 vol%. It is extracted from the gas mixture by means of selective solvents such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), kerosene, methanol or acetone and purified in further steps. The individual acetylene processes differ mainly in the type of generation and transfer of the high4emperature heat required for the pyrolysis reaction. From basic principles, three processes can be differentiated: 1. Allothermal processes with direct heat transfer, usually with electrical heating. 2. Allothermal processes with indirect heat transfer by heat transfer agent. 3. Autothermal processes in which heat from a partial combustion of the feed serves to crack the remainder endothermally. To 1: The Hls electric arc process belongs to this group. This process has been operated on an industrial scale since 1955 in a plant in Germany with an annual capacity (1993) of 120000 tonnes C 2H2 and ca. 50000 tonnes C2H4, as well as in a smaller plant in Rumania. In this process, hydrocarbons with boiling points up to 200 C are cracked in a meter-long stabilized arc with internal temperatures of up to 20000 C. At the end of the burner, the gas mixture has a working pressure of about 1.2 bar and a temperature of ca. 1800C, which is quickly lowered to 200C with a water spray. The residence time of the gas in the arc furnace is a few milliseconds. The yields of acetylene and ethylene attained are 1.0 and 0.42 tonnes per 1.8 tonnes of hydrocarbon feed, respectively. Huls discontinued operation of this large plant in 1993 and, due to a smaller demand for this energy-intensive acetylene (e. g., for 1,4-butanediol and tetra-hydrofuran), started up a modern, environmentally friendly 40 000 tonne-per-year plant.

Another H2 electric arc process called the plasma process (Hoechst-Huls) was tested in two large-scale pilot plants. The heat-transfer agent, H2, is initially heated by an electric arc to 3000-4000 C, whereby 30-65% is dissociated into atoms. In the coupled reactor, all types of hydrocarbons - from methane to crude oil - can be introduced into the plasma and cracked. The cracked gas is quickly quenched and separated. With light gasoline as feedstock, yields of acetylene and ethylene of ca. 80 wt% can be obtained if byproducts are recycled to the cracking process. The acetylene concentration in the cracked gas reaches almost 14 vol%. Plasma processes have also been developed in the USA and the CIS, but none has been used industrially. A modified electric arc process was developed by Du Pont; a plant with a production capacity of 25 000 tonnes per year was operated in the USA from 1963 to 1968. Recently, the use of coal as a feedstock for plasma pyrolysis has been investigated on a pilot plant scale by Huls in Germany and AVCO in the USA. Here - analogous to the process with hydrocarbons - powdered coal is introduced into a hydrogen plasma arc. With a residence time of a few milliseconds, and with optimal temperature and pressure conditions, a C2H2 yield of 35 wt% can be attained, depending on the type of coal used. The cracked gas is quenched with water, and the unreacted solid is recycled. The separation of the mixture is more complicated than with a hydrocarbon feed, both because of the slag produced and because of the formation of compounds formed from the N, O, and S contained in the coal. Due to low oil prices, commercial realization of this technology is not currently possible. To 2: The Wulff process, which operates a regeneration by alternate heating in fire-resistant lined ovens and subsequent cracking, belongs to this group. This process was developed mainly by UCC. However, the relatively large formation of soot, as compared to the electrothermal or partial oxidation processes, and the excessively long residence times for the acetylene could not be prevented. All such plants in the USA, Brazil and Europe were shut down at the end of the 1960s. A novel high-temperature cracking process using superheated steam (ca. 2000 C) from the combustion of H2/CH4, mixtures was developed by Kureha in Japan. The feedstock of crude oil or residual oils gives a 46% yield of C2H2 /C2H4 in approximately equal amounts. This process, first tested in a pilot plant in 1970, is the forerunner of the ACR process developed in conjunction with UCC and Chiyoda. To 3: Two BASF processes belong to this group. The first, and that with the greatest application, is the SachsseBartholome process. Worldwide, thirteen plants with a total capacity of 400000 tonnes per year C2H2 have used this technology. In 1991 only seven plants with a total capacity of 330000 tonnes per year were still in operation. This process will be described in more detail below. The second BASF process is the submerged-flame process in which an oil/O2 flame conducts the cracking in the oil phase. Sisas plants in Italy use this technology to produce 110000 tonnes per year of C2H2 and C2H4.