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Sunday, March 22, 2009

Petrochemicals

Petrochemicals are chemical products made from raw materials of petroleum or other hydrocarbon origin. Although some of the chemical compounds that originate from petroleum may also be derived from coal and natural gas, petroleum is the major source. The largest petrochemical industries are to be found in the USA and Western Europe, though the major growth in new production capacity is in the Middle East and Asia. There is a substantial inter-regional trade in petrochemicals of all kinds. World production of ethylene is around 110 million tons per year, of propylene 65 million tons, and of aromatic raw materials 70 million tons.

C1- Groups.
Methanol: Production.
Today, synthesis gas is most commonly produced from the methane component in natural gas rather than from coal. Three processes are commercially practiced. At moderate pressures of 4 MPa (10–20 atm) and high temperatures (around 850 °C), methane reacts with steam on a nickel catalyst to produce syngas according to the
chemical equation:
CH4 + H2O → CO + 3 H2
This reaction, commonly called steam-methane reforming or SMR, is endothermic and the heat transfer limitations place limits on the size of and pressure in the catalytic reactors used. Methane can also undergo partial oxidation with molecular oxygen to produce syngas, as the following equation shows:
2 CH4 + O2 → 2 CO + 4 H2
this reaction is exothermic and the heat given off can be used in-situ to drive the steam-methane reforming reaction. When the two processes are combined, it is referred to as autothermal reforming. The ratio of CO and H2 can be adjusted to some extent by the water-gas shift reaction,
CO + H2O → CO2 + H2,
to provide the appropriate stoichiometry for methanol synthesis.
The carbon monoxide and hydrogen then react on a second catalyst to produce methanol. Today, the most widely used catalyst is a mixture of copper, zinc oxide, and alumina first used by ICI in 1966. At 5–10 MPa (50–100 atm) and 250 °C, it can catalyze the production of methanol from carbon monoxide and hydrogen with high selectivity
CO + 2 H2 → CH3OH
It is worth noting that the production of synthesis gas from methane produces 3 moles of hydrogen for every mole of carbon monoxide, while the methanol synthesis consumes only 2 moles of hydrogen for every mole of carbon monoxide. One way of dealing with the excess hydrogen is to inject carbon dioxide into the methanol synthesis reactor, where it, too, reacts to form methanol according to the chemical equation:
CO2 + 3 H2 → CH3OH + H2O
Although natural gas is the most economical and widely used feedstock for methanol production, other feedstocks can be used. Coal is increasingly being used as a feedstock for methanol production, particularly in China. In addition, mature technologies available for biomass gasification are being utilized for methanol production.

Tuesday, February 3, 2009

Because of its many uses, ammonia is one of the most highly produced inorganic chemicals. Dozens of chemical plants worldwide produce ammonia. The worldwide ammonia production in 2004 was 109 million metric tonnes.[15] The People's Republic of China produced 28.4% of the worldwide production followed by India with 8.6%, Russia with 8.4%, and the United States with 8.2%.[15] About 80% or more of the ammonia produced is used for fertilizing agricultural crops.[15]
Before the start of World War I, most ammonia was obtained by the dry distillation of nitrogenous vegetable and animal waste products, including camel dung, where it was distilled by the reduction of nitrous acid and nitrites with hydrogen; in addition, it was produced by the distillation of coal, and also by the decomposition of ammonium salts by alkaline hydroxide such as quicklme, the salt most generally used being the chloride (sal-ammoniac) thus:
2 NH4Cl + 2 CaO → CaCl2 + Ca(OH)2 + 2 NH3
(Two molecules of ammonium chloride plus two calcium oxide yields calcium chloride and calcium hydroxide and two molecules of ammonia)
Today, the typical modern ammonia-producing plant first converts natural gas (i.e., methane) or liquified petroleum gas (such gases are propane and butane) or petroleum naphtha into gaseous hydrogen. The processes used in producing the hydrogen begins with removal of sulfur compounds from the natural gas (because sulfur deactivates the catalysts used in subsequent steps). Catalytic hydrogenation converts organosulfur compounds into gaseous hydrogen sulfide:
H2 + RSH → RH + H2S(g)
The hydrogen sulfide is then removed by passing the gas through beds of zinc oxide where it is absorbed and converted to solid zinc sulfide:
H2S + ZnO → ZnS + H2O
Catalytic steam reforming of the sulfur-free feedstock is then used to form hydrogen plus carbon monoxide:
CH4 + H2O → CO + 3 H2
In the next step, the water gas shift reaction is used to convert the carbon monoxide into carbon dioxide and more hydrogen:
CO + H2O → CO2 + H2
The carbon dioxide is then removed either by absorption in aqueous ethanolamine solutions or by adsorption in pres. swingadsorbers (PSA) using proprietary solid adsorption media.
The final step in producing the hydrogen is to use catalytic methanation to remove any small residual amounts of carbon monoxide or carbon dioxide from the hydrogen:
CO + 3 H2 → CH4 + H2O
CO2 + 4 H2 → CH4 + 2 H2O
To produce the desired end-product ammonia, the hydrogen is then catalytically reacted with nitrogen (derived from process air) to form anhydrous liquid ammonia. This step is known as the ammonia synthesis loop (also referred to as the haber-boch process):
3 H2 + N2 → 2 NH3
H2 required for ammonia synthesis could in principle be obtained from other sources, but these alternatives - apart from the electrolysis of water into oxygen + hydrogen - are presently impractical. At one time, most of Europe's ammonia was produced from the Hydro plant at Vemork, via the electrolysis route. Various renewable energy electricity sources are also potentially applicable.