Acetylene

Manufacturing Processes for Acetylene

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 CaC2synthesis. 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.

Calcium Carbide Process:

Acetylene is a colorless, combustible gas with a distinctive odor. When acetylene is liquefied, compressed, heated, or mixed with air, it becomes highly explosive. As a result

special precautions are required during its production and handling. The most common use of acetylene is as a raw material for the production of various organic chemicals including 1,4-butanediol, which is widely used in the preparation of polyurethane and polyester plastics. The second most common use is as the fuel component in oxyacetylene welding and metal cutting. Some commercially useful acetylene compounds include acetylene black, which is used in certain dry-cell batteries, and acetylenic alcohols, which are used in the synthesis of vitamins. Acetylene was discovered in 1836, when Edmund Davy was experimenting with potassium carbide. One of his chemical reactions produced a flammable gas, which is now known as acetylene. In 1859, Marcel Morren successfully generated acetylene when he used carbon electrodes to strike an electric arc in an atmosphere of hydrogen. The electric arc tore carbon atoms away from the electrodes and bonded them with hydrogen atoms to form acetylene molecules. He called this gas carbonized hydrogen. By the late 1800s, a method had been developed for making acetylene by reacting calcium carbide with water. This generated a controlled flow of acetylene that could be combusted in air to produce a brilliant white light. Carbide lanterns were used by miners and carbide lamps were used for street illumination before the general availability of electric lights. In 1897, Georges Claude and A. Hess noted that acetylene gas could be safely stored by dissolving it in acetone. Nils Dalen used this new method in 1905 to develop long-burning, automated marine and railroad signal lights. In 1906, Dalen went on to develop an acetylene torch for welding and metal cutting. In the 1920s, the German firm BASF developed a process for manufacturing acetylene from natural gas and petroleum-based hydrocarbons. The first plant went into operation in Germany in 1940. The technology came to the United States in the early 1950s and quickly became the primary method of producing acetylene. Demand for acetylene grew as new processes were developed for converting it into useful plastics and chemicals. In the United States, demand peaked sometime between 1965 and 1970, then fell off sharply as new, lower-cost alternative conversion materials

were discovered. Since the early 1980s, the demand for acetylene has grown slowly at a rate of about 2-4% per year. In 1991, there were eight plants in the United States that produced acetylene. Together they produced a total of 352 million lb (160 million kg) of acetylene per year. Of this production, 66% was derived from natural gas and 15% from petroleum processing. Most acetylene from these two sources was used on or near the site where it was produced to make other organic chemicals. The remaining 19% came from calcium carbide. Some of the acetylene from this source was used to make organic chemicals, and the rest was used by regional industrial gas producers to fill pressurized cylinders for local welding and metal cutting customers. In Western Europe, natural gas and petroleum were the principal sources of acetylene in 1991, while calcium carbide was the principal source in Eastern Europe and Japan.

Raw Materials
Acetylene is a hydrocarbon consisting of two carbon atoms and two hydrogen atoms. Its chemical symbol is C 2 H 2 . For commercial purposes, acetylene can be made from several different raw materials depending on the process used. The simplest process reacts calcium carbide with water to produce acetylene gas and a calcium carbonate slurry, called hydrated lime. The chemical reaction may be written as CaC 2 + 2 H 2 O C 2 H 2 + Ca(OH) 2 . Other processes use natural gas, which is mostly methane, or a petroleum-based hydrocarbon such as crude oil, naphtha, or bunker C oil as raw materials. Coal can also be used. These processes use high temperature to convert the raw materials into a wide variety of gases, including hydrogen, carbon monoxide, carbon dioxide, acetylene, and others. The chemical reaction for converting methane into acetylene and hydrogen may be written 2 CH 4 C 2 H 2 + 3 H 2 . The other gases are the products of combustion with oxygen. In order to separate the acetylene, it is dissolved in a solvent such as water, anhydrous ammonia, chilled methanol, or acetone, or several other solvents depending on the process.

The Manufacturing Process

There are two basic conversion processes used to make acetylene. One is a chemical reaction process, which occurs at normal temperatures. The other is a thermal cracking process, which occurs at extremely high temperatures. Here are typical sequences of operations used to convert various raw materials into acetylene by each of the two basic processes.

Chemical reaction process

Acetylene may be generated by the chemical reaction between calcium carbide and water. This reaction produces a considerable amount of heat, which must be removed to prevent the acetylene gas from exploding. There are several variations of this process in which either calcium carbide is added to water or water is added to calcium carbide. Both of these variations are called wet processes because an excess amount of water is used to absorb the heat of the reaction. A third variation, called a dry process, uses only a limited amount of water, which then evaporates as it absorbs the heat. The first variation is most commonly used in the United States and is described below. 1. Most high-capacity acetylene generators use a rotating screw conveyor to feed calcium carbide granules into the reaction chamber, which has been filled to a certain level with water. The granules measure about 0.08 in x 0.25 in (2 mm x 6 mm), which provides the right amount of exposed surfaces to allow a complete reaction. The feed rate is determined by the desired rate of gas flow and is controlled by a pressure switch in the chamber. If too much gas is being produced at one time, the pressure switch opens and cuts back the feed rate. 2. To ensure a complete reaction, the solution of calcium carbide granules and water is constantly agitated by a set of rotating paddles inside the reaction chamber. This also prevents any granules from floating on the surface where they could over-heat and ignite the acetylene 3. The acetylene gas bubbles to the surface and is drawn off under low pressure. As it leaves the reaction chamber, the gas is cooled by a spray of water. This water

spray also adds water to the reaction chamber to keep the reaction going as new calcium carbide is added. After the gas is cooled, it passes through a flash arrester, which prevents any accidental ignition from equipment downstream of the chamber. 4. As the calcium carbide reacts with the water, it forms a slurry of calcium carbonate, which sinks to the bottom of the chamber. Periodically the reaction must be stopped to remove the built-up slurry. The

Acetylene may be generated by the chemical reaction between calcium carbide and water. This reaction produces a considerable amount of heat, which must be removed to prevent the acetylene gas from exploding. slurry is drained from the chamber and pumped into a holding pond, where the calcium carbonate settles out and the water is drawn off. The thickened calcium carbonate is then dried and sold for use as an industrial waste water treatment agent, acid neutralizer, or soil conditioner for road construction.

Thermal cracking process

Acetylene may also be generated by raising the temperature of various hydrocarbons to the point where their atomic bonds break, or crack, in what is known as a thermal cracking process. After the hydrocarbon atoms break apart, they can be made to rebond to form different materials than the original raw materials. This process is widely used to convert oil or natural gas to a variety of chemicals.

There are several variations of this process depending on the raw materials used and the method for raising the temperature. Some cracking processes use an electric arc to heat the raw materials, while others use a combustion chamber that burns part of the hydrocarbons to provide a flame. Some acetylene is generated as a coproduct of the steam cracking process used to make ethylene. In the United States, the most common process uses a combustion chamber to heat and burn natural gas as described below. 1. Natural gas, which is mostly methane, is heated to about 1,200 F (650 C). Preheating the gas will cause it to self-ignite once it reaches the burner and requires less oxygen for combustion. 2. The heated gas passes through a narrow pipe, called a venturi, where oxygen is injected and mixed with the hot gas. 3. The mixture of hot gas and oxygen passes through a diffuser, which slows its velocity to the desired speed. This is critical. If the velocity is too high, the incoming gas will blow out the flame in the burner. If the velocity is too low, the flame can flash back and ignite the gas before it reaches the burner. 4. The gas mixture flows into the burner block, which contains more than 100 narrow channels. As the gas flows into each channel, it self-ignites and produces a flame which raises the gas temperature to about 2,730 F (1,500 C). A small amount of oxygen is added in the burner to stabilize the combustion. 5. The burning gas flows into the reaction space just beyond the burner where the high temperature cause about one-third of the methane to be converted into acetylene, while most of the rest of the methane is burned. The entire combustion process takes only a few milliseconds. 6. The flaming gas is quickly quenched with water sprays at the point where the conversion to acetylene is the greatest. The cooled gas contains a large amount of carbon monoxide and hydrogen, with lesser

Acetylene may also be generated by raising the temperature of various hydrocarbons to the point where their atomic bonds break, or crack, in what is known as a thermal cracking process. amounts of carbon soot, plus carbon dioxide, acetylene, methane, and other gases. 7. The gas passes through a water scrubber, which removes much of the carbon soot. The gas then passes through a second scrubber where it is sprayed with a solvent known as N-methylpyrrolidinone which absorbs the acetylene, but not the other gases. 8. The solvent is pumped into a separation tower where the acetylene is boiled out of the solvent and is drawn off at the top of the tower as a gas, while the solvent is drawn out of the bottom.

Storage and Handling

Because acetylene is highly explosive, it must be stored and handled with great care. When it is transported through pipelines, the pressure is kept very low and the length of the pipeline is very short. In most chemical production operations, the acetylene is transported only as far as an adjacent plant, or "over the fence" as they say in the chemical processing business.

When acetylene must be pressurized and stored for use in oxy-acetylene welding and metal cutting operations, special storage cylinders are used. The cylinders are filled with an absorbent material, like diatomaceous earth, and a small amount of acetone. The acetylene is pumped into the cylinders at a pressure of about 300 psi (2,070 kPa), where it is dissolved in the acetone. Once dissolved, it loses its explosive capability, making it safe to transport. When the cylinder valve is opened, the pressure drop causes some of the acetylene to vaporize into gas again and flow through the connecting hose to the welding or cutting torch.

Quality Control
Grade B acetylene may have a maximum of 2% impurities and is generally used for oxyacetylene welding and metal cutting. Acetylene produced by the chemical reaction process meets this standard. Grade A acetylene may have no more than 0.5% impurities and is generally used for chemical production processes. Acetylene produced by the thermal cracking process may meet this standard or may require further purification, depending on the specific process and raw materials.

The Future
The use of acetylene is expected to continue a gradual increase in the future as new applications are developed. One new application is the conversion of acetylene to ethylene for use in making a variety of polyethylene plastics. In the past, a small amount of acetylene had been generated and wasted as part of the steam cracking process used to make ethylene. A new catalyst developed by Phillips Petroleum allows most of this acetylene to be converted into ethylene for increased yields at a reduced overall cost.

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Acetylene production process using calcium carbide

3 3

Acetylene plants are available in capacities from 25m /hr to 200m /hr and are quite automatic in nature. The reaction of calcium carbide with water leads to the production of acetylene in a Stationary Carbideto Water type Automatic Acetylene Generator. Calcium carbide is fed from the top of the generatorshell where large quantity of water is already held and which yields the following reaction:

CaC2 + 2H2O C2H2 + Ca(OH)2 The process unit should be equipped with high level non return valves, pressure and temperature sensors for safe and control operations. Operation like production acetylene can only be done when prefect automation and controlled system are added to the system, vent valves should be highly sensitive and accurate. Flash back arrestors make the whole process run smoothly.

Acetylene gas can be produced by the following process:

1. Drums containing calcium carbide should be opened only just before filling and carbide to hoppers. 2. Carbide containing more than 15% dust and sizes exceeding beyond the limits specified should not be kept for charging in hoppers. 3. Keep the hopper change over switch to manual position if the carbide is to be charged in a running generator. 4. Close the hopper equalizer valve. Ensure zero acetylene gas pressure into hopper to be charged by opening the hopper vent valve. 5. Lift the skip containing calcium carbide with the help of pneumatic hoist. 6. Locate the skip manually above the hopper to be charged, lower the skip till inserted in the hopper slightly. 7. Draw the removable cap and poke with a brass rod, when charging is interrupted. Ensure that the skip was made empty. 8. Lift the skip. 9. Clean the carbide dust accumulated on the lids and hopper. 10. Replace the lid carefully. Stop nitrogen purging. Disconnect the nitrogen purging line. 11. Be sure that nitrogen purging is done continuously as long as the charging is undergoing.

Equipments description in the process:

Generator:

The reaction occurs in the generator where calcium carbide is reacted with water and produces acetylene gas and remains the calcium hydroxide as slurry.

Accessories fitted to the generator: 1. Twin hoopers 2. For better mixing agitator is fitted with spark proof motor. 3. Feeder for continuous feeding of calcium carbide. 4. Arrestor to prevent any kind of flash generated in the system. 5. Automatic control sensors with auto safety valve Condenser:

Generated acetylene is cooled down

High pressure drier:

Calcium carbide and water are reacted to form Acetylene and calcium hydroxide. Generator is equipped with automatic by-product discharger. High pressure drier helps in drying the acetylene gas by using anhydrous calcium chloride.

Purifier:

It is used to separate hydrogen sulphide and phosgene that were produced along with acetylene. A wire mesh works as a surface for the gases to separate easily.

Scrubber:

It is counter system, all the produced gas pass thorough the counter flow of water to remove ammonia content and any water soluble gases from acetylene.

Compressor:

Acetylene is highly flammable and so to compress it in three stage compressor is highly dangerous task, but the technique of water surrounding and sealing will make the acetylene compressor work in sealed environment avoiding the contact of air.