Production of Ehtane in Industries 1 Ethane is an important petrochemical feedstock, and it is separated from the other components of natural gas

in most well-developed gas fields. Ethane can also be separated from petroleum gas, a mixture of gaseous hydrocarbons that arises as a byproduct of petroleum refining. Economics of building and running processing plants can change, however. If the relative value of sending the unprocessed natural gas to a consumer exceeds the value of extracting ethane, then the plant may not be run. This can cause operational issues managing the changing quality of the gas in downstream systems. Ethane is most efficiently separated from methane by liquefying it at cryogenic temperatures. Various refrigeration strategies exist: the most economical process presently in wide use employs turboexpansion, and can recover over 90% of the ethane in natural gas. In this process, chilled gas expands through a turbine; as it expands, its temperature drops to about -100 C. At this low temperature, gaseous methane can be separated from the liquefied ethane and heavier hydrocarbons by distillation. Further distillation then separates ethane from the propane and heavier hydrocarbons.

Production of Ethlyene in Industries

1 Ethylene is produced in the petrochemical industry by steam cracking. In this process, gaseous or light liquid hydrocarbons are heated to 750950 C, inducing numerous free radical reactions followed by immediate quench to freeze the reactions. This process converts large hydrocarbons into smaller ones and introduces unsaturation. Ethylene is separated from the resulting complex mixture by repeated compression and distillation. In a related process used in oil refineries, high molecular weight hydrocarbons are cracked over zeolite catalysts. Heavier feedstocks, such as naphtha and gas oils require at least two "quench towers" downstream of the cracking furnaces to recirculate pyrolysisderived gasoline and process water. When cracking a mixture of ethane and propane, only one water quench tower is required. The areas of an ethylene plant are: 1. steam cracking furnaces; 2. primary and secondary heat recovery with quench; 3. a dilution steam recycle system between the furnaces and the quench system; 4. primary compression of the cracked gas (3 stages of compression); 5. hydrogen sulfide and carbon dioxide removal (acid gas removal); 6. secondary compression (1 or 2 stages); 7. drying of the cracked gas; 8. cryogenic treatment; 9. all of the cold cracked gas stream goes to the demethanizer tower. The overhead stream from the demethanizer tower consists of all the hydrogen and methane that was in the cracked gas stream. Different methods of cryogenically treating this overhead stream results in the separation of the hydrogen and the methane. This usually involves liquid methane at a temperature around -250 degrees F. Complete recovery of all the methane is critical to the economical operation of an ethylene plant. Often one or two Turboexpanders are used for Methane recovery from the demethanizer overhead stream. 10. the bottom stream from the demethanizer tower goes to the deethanizer tower. The overhead stream from the deethanizer tower consists of all the C2,'s that were in the cracked gas stream. The C2's then go to a C2 splitter. The product ethylene is taken from the overhead of the tower and the ethane coming from the bottom of the splitter is recycled to the furnaces to be cracked again; 11. the bottom stream from the deethanizer tower goes to the depropanizer tower. The overhead stream from the depropanizer tower consists of all

the C3's that were in the cracked gas stream. Prior to sending the C3's to the C3 splitter this stream is hydrogenated in order to react out the methylacetylene and propadiene. Then this stream is sent to the C3 splitter. The overhead stream from the C3 splitter is product propylene and the bottom stream from the C3 splitter is propane which can be sent back to the furnaces for cracking or used as fuel. 12. The bottom stream from the depropanizer tower is fed to the debutanizer tower. The overhead stream from the debutanizer is all of the C4's that was in the cracked gas stream. The bottom stream from the debutanizer consists of everything in the cracked gas stream that is C5 or heavier. This could be called a light pyrolysis gasoline. Since the production of ethylene is energy intensive, much effort has been dedicated recovering heat from the gas leaving the furnaces. Most of the energy recovered from the cracked gas is used to make high pressure (1200 psig) steam. This steam is in turn used to drive the turbines for compressing cracked gas, the propylene refrigeration compressor, and the ethylene refrigeration compressor. An ethylene plant, once running, does not need to import any steam to drive its steam turbines. A typical world scale ethylene plant (about 1.5 billion pounds of ethylene per year) uses a 45,000 horsepower cracked gas compressor, a 30,000 horsepower propylene compressor, and a 15,000 horsepower ethylene compressor. When starting an ethylene plant it is important to start the cooling systems in the proper order. The cooling systems consist of Cooling Tower Water (CTW); propylene refrigeration with four or five different levels or stages. Each level corresponds to a particular pressure and temperature; and three or four stages of ethylene regfrigeration. The CTW must be started first because the propylene system needs it to condense propylene and the ethylene refrigeration systems needs it to desuperheat high pressure ethylene. The propylene system must start next because the ethylene system needs high pressure propylene for desuperheating the high pressure ethylene stage and the low pressure propylene stage for condensing the high pressure ethylene. While the ethylene plant is running, the plant can continue to run for a time if the ethylene refrigeration compressor shuts down. However, if the propylene compressor shuts down the whole plant must be shut down immediately.

2 Ethylene is produced in all higher plants and is produced from methionine in essentially all tissues. Production of ethylene varies with the type of tissue, the plant species, and also the stage of development. The mechanism by which ethylene is produced from methionine is a 3 step process (McKeon et al., 1995; Salisbury and Ross, 1992). ATP is an essential component in the synthesis of ethylene from methionine. ATP and water are added to methionine resulting in loss of the three phosphates and S-adenosyl methionine. 1-amino-cyclopropane-1-carboxylic acid synthase (ACC-synthase) facilitates the production of ACC from SAM. Oxygen is then needed in order ro oxidize ACC and produce ethylene. This reaction is catalyzed by an oxidative enzyme called ethylene forming enzyme. The control of ethylene production has received considerable study. Study of ethylene has focused around the synthesis promoting effects of auxin, wounding, and drought as well as aspects of fruit-ripening. ACC synthase is the rate limiting step for ethylene production and it is this enzyme that is manipulated in biotechnology to delay fruit ripening in the "flavor saver" tomatoes (Klee and Lanahan, 1995).

Production of Ethanol in Industries

Ethylene hydration
Ethanol for use as industrial feedstock is most often made from petrochemical feed stocks, typically by the acid-catalyzed hydration of ethylene, represented by the chemical equation C2H4(g) + H2O(g) CH3CH2OH(l) The catalyst is most commonly phosphoric acid,[17] adsorbed onto a porous support such as diatomaceous earth or charcoal. This catalyst was first used for large-scale ethanol production by the Shell Oil Company in 1947.[18] The reaction is carried out with an excess of high pressure steam at 300C. In an older process, first practiced on the industrial scale in 1930 by Union Carbide,[19] but now almost entirely obsolete, ethylene was hydrated indirectly by reacting it with concentrated sulfuric acid to produce ethyl sulfate, which was then hydrolyzed to yield ethanol and regenerate the sulfuric acid:[14] C2H4 + H2SO4 CH3CH2SO4H CH3CH2SO4H + H2O CH3CH2OH + H2SO4

2 Fermentation
Ethanol for use in alcoholic beverages, and the vast majority of ethanol for use as fuel, is produced by fermentation. When certain species of yeast, most importantly, Saccharomyces cerevisiae, metabolize sugar in the absence of oxygen, they produce ethanol and carbon dioxide. The chemical equation below summarizes the conversion: C6H12O6 2 CH3CH2OH + 2 CO2 The process of culturing yeast under conditions to produce alcohol is called fermentation. Ethanol's toxicity to yeast limits the ethanol concentration obtainable by brewing. The most ethanol-tolerant strains of yeast can survive up to approximately 15% ethanol by volume.[20] The fermentation process must exclude oxygen. If oxygen is present, yeast undergo aerobic respiration which produces carbon dioxide and water rather than ethanol. In order to produce ethanol from starchy materials such as cereal grains, the starch must first be converted into sugars. In brewing beer, this has traditionally been accomplished by allowing the grain to germinate, or malt, which produces the enzyme, amylase. When the malted grain is mashed, the amylase converts the remaining starches into sugars. For fuel ethanol, the hydrolysis of starch into glucose can be accomplished more rapidly by treatment with dilute sulfuric acid, fungally produced amylase, or some combination of the two.[21]

3 Prospective technologies
The anaerobic bacterium Clostridium ljungdahlii, recently discovered in commercial chicken wastes, can produce ethanol from single-carbon sources including synthesis gas, a mixture of carbon monoxide and hydrogen that can be generated from the partial combustion of either fossil fuels or biomass. Use of these bacteria to produce ethanol from synthesis gas has progressed to the pilot plant stage at the BRI Energy facility in Fayetteville, Arkansas.[28] Another prospective technology is the closed-loop ethanol plant.[29] Ethanol produced from corn has a number of critics who suggest that it is primarily just recycled fossil fuels because of the energy required to grow the grain and convert it into ethanol. There is also the issue of competition with use of corn for food production. However, the closed-loop ethanol plant attempts to address this criticism. In a closed-loop plant, the energy for the distillation comes from fermented manure, produced from cattle that have been fed the by-products from the distillation. The leftover manure is then used to fertilize the soil used to grow the grain. Such a process is expected to have a much lower fossil fuel requirement.[30] Though in an early stage of research, there is some development of alternative production methods that use feed stocks such as municipal waste or recycled products, rice hulls, sugarcane bagasse, small diameter trees, wood chips, and switchgrass.[31]

Production of Acetic Acid in Industries

1 Methanol carbonylation Most virgin acetic acid is produced by methanol carbonylation. In this process, methanol and carbon monoxide react to produce acetic acid according to the chemical equation: CH3OH + CO CH3COOH The process involves iodomethane as an intermediate, and occurs in three steps. A catalyst, usually a metal complex, is needed for the carbonylation (step 2). (1) CH3OH + HI CH3I + H2O (2) CH3I + CO CH3COI (3) CH3COI + H2O CH3COOH + HI By altering the process conditions, acetic anhydride may also be produced on the same plant. Because both methanol and carbon monoxide are commodity raw materials, methanol carbonylation long appeared to be an attractive method for acetic acid production. Henry Drefyus at British Celanese developed a methanol carbonylation pilot plant as early as 1925.[12] However, a lack of practical materials that could contain the corrosive reaction mixture at the high pressures needed (200 atm or more) discouraged commercialization of these routes. The first commercial methanol carbonylation process, which used a cobalt catalyst, was developed by German chemical company BASF in 1963. In 1968, a rhodiumbased catalyst (cis[Rh(CO)2I2]) was discovered that could operate efficiently at lower pressure with almost no by-products. The first plant using this catalyst was built by US chemical company Monsanto in 1970, and rhodium-catalysed methanol carbonylation became the dominant method of acetic acid production (see Monsanto process). In the late 1990s, the chemicals company BP Chemicals commercialized the Cativa catalyst ([Ir(CO)2I2]), which is promoted by ruthenium. This iridium-catalysed process is greener and more efficient[13] and has largely supplanted the Monsanto process, often in the same production plants.

2 Acetaldehyde oxidation
Prior to the commercialization of the Monsanto process, most acetic acid was produced by oxidation of acetaldehyde. This remains the second most important manufacturing method, although it is uncompetitive with methanol carbonylation. The acetaldehyde may be produced via oxidation of butane or light naphtha, or by hydration of ethylene. When butane or light naphtha is heated with air in the presence of various metal ions, including those of manganese, cobalt and chromium; peroxides form and then decompose to produce acetic acid according to the chemical equation 2 C4H10 + 5 O2 4 CH3COOH + 2 H2O Typically, the reaction is run at a combination of temperature and pressure designed to be as hot as possible while still keeping the butane a liquid. Typical reaction conditions are 150 C and 55 atm. Side products may also form, including butanone, ethyl acetate, formic acid, and propionic acid. These side products are also commercially valuable, and the reaction conditions may be altered to produce more of them if this is economically useful. However, the separation of acetic acid from these by-products adds to the cost of the process. Under similar conditions and using similar catalysts as are used for butane oxidation, acetaldehyde can be oxidized by the oxygen in air to produce acetic acid 2 CH3CHO + O2 2 CH3COOH Using modern catalysts, this reaction can have an acetic acid yield greater than 95%. The major side products are ethyl acetate, formic acid, and formaldehyde, all of which have lower boiling points than acetic acid and are readily separated by distillation.[14]

3 Anaerobic fermentation
Species of anaerobic bacteria, including members of the genus Clostridium, can convert sugars to acetic acid directly, without using ethanol as an intermediate. The overall chemical reaction conducted by these bacteria may be represented as: C6H12O6 3 CH3COOH More interestingly from the point of view of an industrial chemist, these acetogenic bacteria can produce acetic acid from one-carbon compounds, including methanol, carbon monoxide, or a mixture of carbon dioxide and hydrogen: 2 CO2 + 4 H2 CH3COOH + 2 H2O This ability of Clostridium to utilize sugars directly, or to produce acetic acid from less costly inputs, means that these bacteria could potentially produce acetic acid more efficiently than ethanol-oxidizers like Acetobacter. However, Clostridium bacteria are less acid-tolerant than Acetobacter. Even the most acid-tolerant Clostridium strains can produce vinegar of only a few per cent acetic acid, compared to Acetobacter strains that can produce vinegar of up to 20% acetic acid. At present, it remains more cost-effective to produce vinegar using Acetobacter than to produce it using Clostridium and then concentrating it. As a result, although acetogenic bacteria have been known since 1940, their industrial use remains confined to a few niche applications.