2 NaCl + 2 H2O → Cl2 + H2 + 2 NaOH
Chlorine can be manufactured by electrolysis of a sodiumchloride solution (brine). The production of chlorine results in the co-products caustic soda (sodium hydroxide, NaOH) and hydrogen gas (H2). These two products, as well as chlorine itself, are highly reactive. Chlorine can also be produced by the electrolysis of a solution of potassium chloride, in which case the co-products are hydrogen and caustic potash (potassium hydroxide). There are three industrial methods for the extraction of chlorine by electrolysis of chloride solutions, all proceeding according to the following equations:
Cathode: 2 H+ (aq) + 2 e− → H2 (g)
Anode: 2 Cl− (aq) → Cl2 (g) + 2 e−
Overall process: 2 NaCl (or KCl) + 2 H2O → Cl2 + H2 + 2 NaOH (or KOH)
Mercury cell electrolysis, also known as the Castner-Kellner process, was the first method used at the end of the nineteenth century to produce chlorine on an industrial scale.The "rocking" cells used have been improved over the years.Today, in the "primary cell", titanium anodes (formerly graphite ones) are placed in a sodium (or potassium) chloride solution flowing over a liquid mercury cathode. When a potential difference is applied and current flows, chlorine is released at the titanium anode and sodium (or potassium) dissolves in the mercury cathode forming an amalgam. This flows continuously into a separate reactor ("denuder" or "secondary cell"), where it is usually converted back to mercury by reaction with water, producing hydrogen and sodium (or potassium) hydroxide at a commercially useful concentration (50% by weight). The mercury is then recycled to the primary cell.
The mercury process is the least energy-efficient of the three main technologies (mercury, diaphragm and membrane) and there are also concerns about mercuryemissions.
It is estimated that there are still around 100 mercury-cell plants operating worldwide. In Japan, mercury-based chloralkali production was virtually phased out by 1987 (except for the last two potassium chloride units shut down in 2003). In the United States, there will be only five mercury plants remaining in operation by the end of 2008. In Europe, mercury cells accounted for 43% of capacity in 2006 and Western European producers have committed to closing or converting all remaining chloralkali mercury plants by 2020
In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a cathodeand an anode, preventing the chlorine forming at the anode from re-mixing with the sodium hydroxide and the hydrogen formed at the cathode This technology was also developed at the end of the nineteenth century. There are several variants of this process: the Le Sueur cell (1893), the Hargreaves-Bird cell (1901), the Gibbs cell (1908), and the Townsend cell (1904) The cells vary in construction and placement of the diaphragm, with some having the diaphragm in direct contact with the cathode.
The salt solution (brine) is continuously fed to the anode compartment and flows through the diaphragm to the cathode compartment, where the caustic alkali is produced and the brine is partially depleted.
As a result, diaphragm methods produce alkali that is quite dilute (about 12%) and of lower purity than do mercury cell methods. But diaphragm cells are not burdened with the problem of preventing mercury discharge into the environment. They also operate at a lower voltage, resulting in an energy savings over the mercury cell method,but large amounts of steam are required if the caustic has to be evaporated to the commercial concentration of 50%.
Development of this technology began in the 1970s. The electrolysis cell is divided into two "rooms" by a cation permeable membrane acting as an ion exchanger. Saturated sodium (or potassium) chloride solution is passed through the anode compartment, leaving at a lower concentration.[23] Sodium (or potassium) hydroxide solution is circulated through the cathode compartment, exiting at a higher concentration. A portion of the concentrated sodium hydroxide solution leaving the cell is diverted as product, while the remainder is diluted with deionized water and passed through the electrolysis apparatus again.
This method is more efficient than the diaphragm cell and produces very pure sodium (or potassium) hydroxide at about 32% concentration, but requires very pure brine.
Other electrolytic processes
Although a much lower production scale is involved, electrolytic diaphragm and membrane technologies are also used industrially to recover chlorine from hydrochloric acid solutions, producing hydrogen (but no caustic alkali) as a co-product.
Furthermore, electrolysis of fused chloride salts (Downs process) also enables chlorine to be produced, in this case as a by-product of the manufacture of metallic sodium or magnesium.
Sodium hydroxide is produced (along with chlorine and hydrogen) via the chloralkali process. This involves the electrolysis of an aqueous solution of sodium chloride. The sodium hydroxide builds up at the cathode, where water is reduced to hydrogen gas and hydroxide ion:
2Na+ + 2H2O + 2e− → H2 + 2NaOH
To produce NaOH it is necessary to prevent reaction of the NaOH with the chlorine. This is typically done in one of three ways, of which the membrane cell process is economically the most viable.
Mercury cell process (also called the Castner-Kellner process) – Sodium ions are reduced to sodium metal, which forms an amalgam with a mercury cathode; this sodium is then reacted with water to produce NaOH. There have been concerns about mercury releases, although modern plants claim to be safe in this regard.[2]
Diaphragm cell process – uses a steel cathode, and the reaction of NaOH with Cl2 is prevented using a porous diaphragm, often made of asbestos fibers. In the diaphragm cell process the anode area is separated from the cathode area by a permeable diaphragm. The brine is introduced into the anode compartment and flows through the diaphragm into the cathode compartment. A diluted caustic brine leaves the cell. The sodium hydroxide must usually be concentrated to 50% and the salt removed. This is done using an evaporative process with about three tonnes of steam per tonne of sodium hydroxide. The salt separated from the caustic brine can be used to saturate diluted brine. The chlorine contains oxygen and is purified by liquefaction and evaporation.[3][4]
Membrane cell process – similar to the diaphragm cell process, with a Nafion membrane to separate the cathode and anode reactions. Only sodium ions and a little water pass through the membrane. It produces a higher quality of NaOH. Of the three processes, the membrane cell process requires the lowest consumption of electric energy and the amount of steam needed for concentration of the caustic is relatively small (less than one tonne per tonne of sodium hydroxide).[5][6]
An older method for sodium hydroxide production was the Leblanc process, which produced sodium carbonate, followed by roasting to create carbon dioxide and sodium oxide. This method is still occasionally used. It helped establish sodium hydroxide as an important commodity chemical.
The LeBlanc process was superseded by the Solvay process in the late 19th century.
Electrolysis of ALUMINIM
Although aluminium is the most abundant metallic element in the Earth's crust (believed to be 7.5 to 8.1 percent), it is rare in its free form, occurring in oxygen-deficient environments such as volcanic mud, and it was once considered a precious metal more valuable than gold. Napoleon III, emperor of France, is reputed to have given a banquet where the most honoured guests were given aluminium utensils, while the other guests had to make do with gold.[11][12] The Washington Monument was completed, with the 100 ounce (2.8 kg) aluminium capstone being put in place on December 6, 1884, in an elaborate dedication ceremony. It was the largest single piece of aluminium cast at the time. At that time, aluminium was more expensive than silver, gold, or platinum. Aluminium has been produced in commercial quantities for just over 100 years.
Bauxite
Aluminium is a strongly reactive metal that forms a high-energy chemical bond with oxygen. Compared to most other metals, it is difficult to extract from ore, such as bauxite, due to the energy required to reduce aluminium oxide (Al2O3). For example, direct reduction with carbon, as is used to produce iron, is not chemically possible, since aluminium is a stronger reducing agent than carbon. Aluminium oxide has a melting point of about 2,000 °C. Therefore, it must be extracted by electrolysis. In this process, the aluminium oxide is dissolved in molten cryolite and then reduced to the pure metal. The operational temperature of the reduction cells is around 950 to 980 °C. Cryolite is found as a mineral in Greenland, but in industrial use it has been replaced by a synthetic substance. Cryolite is a chemical compound of aluminium, sodium, and calcium fluorides: (Na3AlF6). The aluminium oxide (a white powder) is obtained by refining bauxite in the Bayer process of Karl Bayer. (Previously, the Deville process was the predominant refining technology.)
The electrolytic process replaced the Wöhler process, which involved the reduction of anhydrous aluminium chloride with potassium. Both of the electrodes used in the electrolysis of aluminium oxide are carbon. Once the refined alumina is dissolved in the electrolyte, its ions are free to move around. The reaction at the cathode (negative electrode) is
Al3+ + 3 e− → Al
Here the aluminium ion is being reduced (electrons are added). The aluminium metal then sinks to the bottom and is tapped off.
At the anode (positive electrode), oxygen is formed:
2 O2− → O2 + 4 e−
This carbon anode is then oxidized by the oxygen, releasing carbon dioxide.
O2 + C → CO2
The anodes in a reduction cell must therefore be replaced regularly, since they are consumed in the process.
Unlike the anodes, the cathodes are not oxidized because there is no oxygen present, as the carbon cathodes are protected by the liquid aluminium inside the cells. Nevertheless, cathodes do erode, mainly due to electrochemical processes and metal movement. After five to ten years, depending on the current used in the electrolysis, a cell has to be rebuilt because of cathode wear.
Synthesis and production
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[16] 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 hydroxides[17] such as quicklime, 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 pressure swing adsorbers (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-Bosch process):
3 H2 + N2 → 2 NH3
Hydrogen 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.
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