Calcium carbide Production

The raw materials for calcium carbide are lime, coke, and electric power (Figure 7.2-3). Thus calcium carbide production is suitable for a country with hydroelectric power but lacks petroleum reserves. Calcium carbide generates acetylene when. icted upon by water. The quantity produced may be small such as using the bright flame of acetylene for... 

The ca. 80% carbide produced, the rest being mainly calcium oxide, is formed as a liquid and is removed as blocks. Crucial in the economics of calcium carbide production is, in addition to the price of the raw materials, the electricity price, because the process is very energy intensive, 2.8 to 3.1 MWh being required per t. Calcium carbide furnaces with power demands up to 70 MW generally have to be operated with three-phase current and utilize Soderberg hollow carbon electrodes dipped deeply into the reaction mixture. 

Workers in aluminum production, coal gasification, coke production, iron and steel foundries, tar distillation, shale oil extraction, wood impregnation, roofing, road paving, carbon black production, carbon electrode production, chimney sweeping, and calcium carbide production are all exposed to PAHs and are known to have increased rates of lung cancer relative to the general population. I89 90 ... 

Calcium carbide has been used in steel production to lower sulfur emissions when coke with high sulfur content is used. The principal use of carbide remains hydrolysis for acetylene (C2H2) production. Acetylene is widely used as a welding gas, and is also a versatile intermediate for the synthesis of many organic chemicals. Approximately 450,000 t of acetylene were used aimuaHy in the early 1960s for the production of such chemicals as acrylonitrile, acrylates, chlorinated solvents, chloroprene, vinyl acetate, and vinyl chloride. Since then, petroleum-derived olefins have replaced acetylene in these uses. 

Submerged-Arc Furnace. Furnaces used for smelting and for certain electrochemical operations are similar in general design to the open-arc furnace in that they are usually three-phase, have three vertical electrode columns and a shell to contain the charge, but dkect current may also be utilised They are used in the production of phosphoms, calcium carbide, ferroalloys, siUcon, other metals and compounds (17), and numerous types of high temperature refractories. 

Although acetylene production in Japan and Eastern Europe is stiU based on the calcium carbide process, the large producers in the United States and Western Europe now rely on hydrocarbons as the feedstock. Now more than 80% of the acetylene produced in the United States and Western Europe is derived from hydrocarbons, mainly natural gas or as a coproduct in the production of ethylene. In Russia about 40% of the acetylene produced is from natural gas. 

Chemical Uses. In Europe, products such as ethylene, acetaldehyde, acetic acid, acetone, butadiene, and isoprene have been manufactured from acetylene at one time. Wartime shortages or raw material restrictions were the basis for the choice of process. Coking coal was readily available in Europe and acetylene was easily accessible via calcium carbide. 

Carbide lime is a waste lime hydrate by-product from the generation of acetylene from calcium carbide and may occur as a wet sludge or dry powder of widely varying purity and particle size. It is gray and has the pungent odor associated with acetylene (see Hydrocarbons, acetylene). 

A number of high temperature processes for the production of titanium carbide from ores have been reported (28,29). The aim is to manufacture a titanium carbide that can subsequently be chlorinated to yield titanium tetrachloride. In one process, a titanium-bearing ore is mixed with an alkah-metal chloride and carbonaceous material and heated to 2000°C to yield, ultimately, a highly pure TiC (28). Production of titanium carbide from ores, eg, ilmenite [12168-52-4], EeTiO, and perovskite [12194-71 -7], CaTiO, has been described (30). A mixture of perovskite and carbon was heated in an arc furnace at ca 2100°C, ground, and then leached with water to decompose the calcium carbide to acetjdene. The TiC was then separated from the aqueous slurry by elutriation. Approximately 72% of the titanium was recovered as the purified product. In the case of ilmenite, it was necessary to reduce the ilmenite carbothermaHy in the presence of lime at ca 1260°C. Molten iron was separated and the remaining CaTiO was then processed as perovskite. 

Because of its high reactivity, production of barium by such processes as electrolysis of barium compound solution or high temperature carbon reduction is impossible. Electrolysis of an aqueous barium solution yields Ba(OH)2, whereas carbon reduction of an ore such as BaO produces barium carbide [50813-65-5] BaC2, which is analogous to calcium carbide (see Carbides). Attempts to produce barium by electrolysis of molten barium salts, usually BaCl25 met with only limited success (14), perhaps because of the solubiUty of Ba in BaCl2 (1 )-... 

Boron Triiodide. Boron ttiiodide is not manufactured on a large scale. Small-scale production of BI from boron and iodine is possible in the temperature range 700—900°C (70—72). Excess I2 can be removed as Snl by reaction with Sn, followed by distillation (71). The reaction of metal tetrahydroborates and I2 is convenient for laboratory preparation of BI (73,74). BI can also by synthesized from B2H and HI in a furnace at 250°C (75), or by the reaction of B with excess Agl or Cul between 450—700°C, under vacuum (76). High purity BI has been prepared by the reaction of I2 with mixtures of boron carbide and calcium carbide at elevated temperatures. 

Calcium Carbide and its Derivatives. Although hydrocarbon-based acetylene production has become mote important, eady manufacture of acetylene was based on manufacture of the iatermediate, calcium carbide [73-20-7J, CaC2. This ionic acetyUde is produced by reaction of lime and carbon ia electric-arc furnaces (16). 

Commercial calcium carbide is composed of calcium carbide, calcium oxide [1305-78-8] CaO, and other impurities present ia the raw materials. The commercial product s calcium carbide content varies and is sold based on acetjiene yield. Industrial-grade calcium carbide contains about 80% as CaC2,... 

Calcium carbide was first made ia the laboratory ia the mid-1800s. Commercial production by the electric furnace method was developed about 1892 by Moissan ia France and iadependendy by Willson ia the United States. Development of the carbide iadustry for generation of acetylene began ia 1895 and expanded rapidly. 

In the United States calcium carbide-based acetylene is mainly used in the oxyacetylene welding market although some continues to be used for production of such chemicals as vinyl ethers and acetylenic alcohols. Calcium carbide is used extensively as a desulfurizing reagent in steel and ductile iron production allowing steel mills to use high sulfur coke without the penalty of excessive sulfur in the resultant steel (see Sulfurremoval and recovery). Calcium cyanamide production continues in Canada and Europe (see Cyanamides). 

Commercial calcium carbide, containing about 80% CaC2, is formed in the Hquid state. Impurities are mainly CaO and impurities present in raw materials. CO is usually collected for use as a fuel in lime production or drying of the coke used in the process. The Hquid calcium carbide is tapped from the furnace into cooling molds. 

Computer Control. The use of computer systems to control the operation of submerged arc furnaces, including calcium carbide, has been successfully demonstrated in the United States (see Expert systems Process control). Operations direcdy under control are mix batching, electrode position and sHp control, carbide gas yield, power control, and cooling water systems. Improvements in energy usage, operating time, and product quaHty are obtained. 

The largest use for calcium carbide is in the production of acetylene for oxyacetylene welding and cutting. Companies producing compressed acetylene gas are located neat user plants to minimize freight costs on the gas cylinders. Some acetylene from carbide continues to compete with acetylene from petrochemical sources on a small scale. In Canada and other countries the production of calcium cyanamide from calcium carbide continues. More recentiy calcium carbide has found increased use as a desulfurizing reagent of blast-furnace metal for the production of steel and low sulfur nodular cast iron. 

With the exception of carbon use in the manufacture of aluminum, the largest use of carbon and graphite is as electrodes in electric-arc furnaces. In general, the use of graphite electrodes is restricted to open-arc furnaces of the type used in steel production whereas, carbon electrodes are employed in submerged-arc furnaces used in phosphoms, ferroalloy, and calcium carbide. 

Refractories for Electric Reduction Furnaces. Carbon hearth linings are used in submerged-arc, electric-reduction furnaces producing phosphoms, calcium carbide, all grades of ferrosilicon, high carbon ferrochromium, ferrovanadium, and ferromolybdenum. Carbon is also used in the production of beryllium oxide and beryllium copper where temperatures up to 2273 K ate requited. 

Occurrence. Carbon monoxide is a product of incomplete combustion and is not likely to result where a flame bums in an abundant air supply, yet may result when a flame touches a cooler surface than the ignition temperature of the gas. Gas or coal heaters in the home and gas space heaters in industry have been frequent sources of carbon monoxide poisoning when not provided with effective vents. Gas heaters, though properly adjusted when installed, may become hazardous sources of carbon monoxide if maintained improperly. Automobile exhaust gas is perhaps the most familiar source of carbon monoxide exposure. The manufacture and use of synthesis gas, calcium carbide manufacture, distillation of coal or wood, combustion operations, heat treatment of metals, fire fighting, mining, and cigarette smoking represent additional sources of carbon monoxide exposure (105—107). 

The high capital cost, about 1500/kW, is the principal deterrent to growth of the IGCC concept. The abiUty to remove up to 99% of the sulfur species from the combustion products make the IGCC an environmentally desirable option as make calcium carbide (see Carbides), from which acetjiene is made. Synthesis gas for methanol and ammonia production is also made from gasification of coke. 

Coatiauous kilns were first used ia Germany at Knapsack (20) and later at Trostberg (21). In the Knapsack process, calcium carbide (0.75—2 mm ia size) is fed to a rotary kiln, 3 m ia diameter and 12 m long with 1% slope 1—2% calcium chloride is added to promote the reaction. The kiln produces 12—13 t fixed nitrogen per day. The product is granular and can be sold without further processiag. 

The Sbddeutsche Kalkstickstoffwerke process at Trostberg uses powdered calcium carbide along with recycle product and calcium fluoride ia a rotary kiln at 1000—1100°C. The capacity of a unit is 25 t fixed nitrogen per day. The product passes to a rotary cooler and is granular (21). 

Reaction of coke with calcium oxide gives calcium carbide, which on treatment with water produces acetylene. This was for many years an important starting point for the production of acrylonitrile, vinyl chloride, vinyl acetate and other vinyl monomers. Furthermore, during World War II, Reppe developed routes for many other monomers although these were not viable under normal economic conditions. 

For many years a major route to the production of vinyl chloride was the addition of hydrochloric acid to acetylene (Figure 12.5). The acetylene is usually prepared by addition of water to calcium carbide, which itself is prepared by heating together coke and lime. To remove impurities such as water, arsine and phosphine the acetylene may be compressed to 15 Ibf/in (approx. 100 kPa), passed through a scrubbing tower and chilled to -10°C to remove some of the water present and then scrubbed with concentrated sulphuric acid. 

Ethylene is produced in quantity using acetylene or propylene as feedstock to make a large number of products (Figure 7.2-3) such as acetaldehyde, acrylonitrile, acetic acid, and acetic anhydride. These are made generally from acetylene which is made from calcium carbide. 

Acetylene and ethylene compete as a chemical raw material. Ethylene is generally more economical, resulting in declining use of acetylene as a raw material. Calcium carbide, a raw material for acetylene has other uses. Treated with nitrogen, it gives calcium cyanamide, valuable as a fertilizer and weed killer, and a raw material for the production of melamine, used ir ng some modern plastics. 

Calcium carbide, CaC2, is die raw material for the production of acetylene (used in welding torches). Calcium carbide is produced by reacting calcium oxide with carbon, producing carbon monoxide as a byproduct. When one mole of calcium carbide is formed, 464.8 kj is absorbed. 

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