Mercury manufacture

Mercury Manufacture of certain chemicals, paper, paint Pesticides Fungicides Adverse health effects... 

Mercury manufacturing from cinnabar was well established in Europe in the 16 century, with methods like that exemplified in Figure 35.1. 

Sodium hydroxide is manufactured by electrolysis of concentrated aqueous sodium chloride the other product of the electrolysis, chlorine, is equally important and hence separation of anode and cathode products is necessary. This is achieved either by a diaphragm (for example in the Hooker electrolytic cell) or by using a mercury cathode which takes up the sodium formed at the cathode as an amalgam (the Kellner-Solvay ceW). The amalgam, after removal from the electrolyte cell, is treated with water to give sodium hydroxide and mercury. The mercury cell is more costly to operate but gives a purer product. 

Mercury compounds (for example mercury(II) chloride) are used in medicine because of their antiseptic character. The artificial red mercury(Il) sulphide is the artist s vermilion . Mercury(II) sulphate is a catalyst in the manufacture of ethanal from ethyne ... 

Early demand for chlorine centered on textile bleaching, and chlorine generated through the electrolytic decomposition of salt (NaCl) sufficed. Sodium hydroxide was produced by the lime—soda reaction, using sodium carbonate readily available from the Solvay process. Increased demand for chlorine for PVC manufacture led to the production of chlorine and sodium hydroxide as coproducts. Solution mining of salt and the avadabiHty of asbestos resulted in the dominance of the diaphragm process in North America, whereas soHd salt and mercury avadabiHty led to the dominance of the mercury process in Europe. Japan imported its salt in soHd form and, until the development of the membrane process, also favored the mercury ceU for production. 

Chlorine from Potassium Hydroxide Manufacture. One of the coproducts during the electrolytic production of potassium hydroxide employing mercury and membrane ceHs is chlorine. The combined name plate capacity for caustic potash during 1988 totaled 325,000 t/yr and growth of U.S. demand was expected to be steady at 2% through 1990 (68). 

Three forms of caustic soda are produced to meet customer needs purified diaphragm caustic (50% Rayon grade), 73% caustic, and anhydrous caustic. Regular 50% caustic from the diaphragm cell process is suitable for most appHcations and accounts for about 85% of the NaOH consumed in the United States. However, it caimot be used in operations such as the manufacture of rayon, the synthesis of alkyl aryl sulfonates, or the production of anhydrous caustic because of the presence of salt, sodium chlorate, and heavy metals. Membrane and mercury cell caustic, on the other hand, is of superior quaUty and... 

In some cases, particularly with iaactive metals, electrolytic cells are the primary method of manufacture of the fluoroborate solution. The manufacture of Sn, Pb, Cu, and Ni fluoroborates by electrolytic dissolution (87,88) is patented. A typical cell for continous production consists of a polyethylene-lined tank with tin anodes at the bottom and a mercury pool (ia a porous basket) cathode near the top (88). Pluoroboric acid is added to the cell and electrolysis is begun. As tin fluoroborate is generated, differences ia specific gravity cause the product to layer at the bottom of the cell. When the desired concentration is reached ia this layer, the heavy solution is drawn from the bottom and fresh HBP is added to the top of the cell continuously. The direct reaction of tin with HBP is slow but can be accelerated by passiag air or oxygen through the solution (89). The stannic fluoroborate is reduced by reaction with mossy tin under an iaert atmosphere. In earlier procedures, HBP reacted with hydrated stannous oxide. 

Mercury(II) fluoride has been used in the process for manufacture of fluoride glass (qv) for fiber optics (qv) appHcations (11) and in photochemical selective fluorination of organic substrates (12). It is available from Advance Research Chemicals, Aldrich Chemicals, Johnson/Matthey, Aesar, Cerac, Strem, and PCR in the United States. The 1993 annual consumption was less than 50 kg the price was 800—1000/kg. 

Indium chemicals and electroplated metal deposits ate replacing mercury (qv) in the manufacture of alkaline batteries (qv). Indium, like mercury, functions to reduce outgassing within the battery and promotes the uniform corrosion of the anode and cathode while the battery is under electrical load. Indium inorganic chemicals also find use as catalysts in various chemical processes. 

AppHcations of mercury include use in batteries (qv), chlorine and caustic soda manufacture (see Alkali and chlorine products), pigments (see Pigments, inorganic), light switches, electric lighting, thermostats, dental repair (see Dental materials), and preservative formulations for paints (qv) (1—3). As of the end of the twentieth century, however, increased awareness of and concern for mercury toxicity has resulted in both voluntary and regulatory reduction of mercury usage (see also Mercury compounds). 

The State of New Jersey has passed a law restricting the sale and disposal of batteries (qv) containing mercury, requiring manufacturers to reduce the mercury content of each battery to 1 ppm by weight by 1995, and to estabhsh a collection program for spent batteries (14). Another New Jersey law bans the sale of products having cadmium, mercury, or other toxic materials in the packaging (14) (see Cadmiumand cadmium alloys Cadmium compounds Mercury compounds). 

Catalysts. Mercury is or has been used in the catalysis (qv) of various plastics, including polyurethane [26778-67-6] poly(vinyl chloride) [9002-86-2] and poly(vinyl acetate) [9003-20-7]. Most poly(vinyl chloride) and poly(vinyl acetate) is manufactured by processes that do not use mercury (3). 

Other Uses. Other uses of mercury that have been discontinued include coatings for mirrors, manufacture of certain types of glass, treatment of felt, and as a fungicide in paper. 

AH mercury compounds should be stored in amber botties or otherwise protected from light. In manufacture, glass-lined equipment is preferred, although stainless steel may be used. Stainless steel may cause some discoloration at high temperatures if concentrated acetic acid is used. 

The primary use of mercuric acetate is as a starting material for the manufacture of organic mercury compounds. 

Prior to the 1990s phenyhnercuric acetate was the primary bactericide and fungicide in latex and waterborne paints. Because of the increasing concerns of mercury toxicity and the potential for high consumer and occupational exposures to mercury when present in paints, the U.S. Environmental Protection Agency (EPA) induced U.S. manufacturers of PMA and other mercury compounds to withdraw their registrations for use of these substances as biocides in paints (see AIercury). Mercury compounds are used only for very limited, specific purposes, such as the use of phenyhnercuric mXx.2LX.e[55-68-5] as a bactericide in cosmetic eye preparations (see Cosmetics). 

Environmental Factors. The control, recovery, and disposal of mercury-bearing waste products are as important to the mercurials industry as the manufacturing process. The difficulties involved in removing mercury from waste-product streams and the problems of recovery or disposal have resulted in a substantial reduction in the number of manufacturers of mercury compounds as well as in the variety of mercury compounds being manufactured. Moreover, the manufacturing process used for a mercury compound may not necessarily be the most efficient or economical. Rather, the choice may depend on the nature of the by-products, the toxic hazard of the process, and the ease of recovery of the mercury from the waste-product stream. 

The control of mercury in the effluent derived from the manufacturing processes used in the preparation of inorganic and organic mercurials is mandated bylaw in the United States. The concentrations and the total amounts vary with the industry and the location, but generally it is requited that the... 

Problems of removal of mercury from aqueous effluents are more comphcated in plants that manufacture a variety of inorganic and organic mercury compounds it is generally best to separate the effluent streams of inorganic and organic mercurials. When phenyhnercuric acetate is precipitated from its solution in acetic acid by addition of water, the filtrate is collected and reused for the next precipitation. This type of recycling is necessary not only for economic reasons but also to minimise recovery operations. 

Manufacture and Processing. Until World War II, phthaUc acid and, later, phthaUc anhydride, were manufactured primarily by Hquid-phase oxidation of suitable feedstocks. The favored method was BASF s oxidation of naphthalene [91-20-3] by sulfuric acid ia the presence of mercury salts to form the anhydride. This process was patented ia 1896. During World War I, a process to make phthaUc anhydride by the oxidation of naphthalene ia the vapor phase over a vanadium and molybdenum oxide catalyst was developed ia the United States (5). Essentially the same process was developed iadependendy ia Germany, with U.S. patents being granted ia 1930 and 1934 (6,7). 

Manufacture is either by reaction of molten sodium with methyl alcohol or by the reaction of methyl alcohol with sodium amalgam obtained from the electrolysis of brine in a Castner mercury cell (78). Both these methods produce a solution of sodium methylate in methanol and the product is offered in two forms a 30% solution in methanol, and a soHd, which is a dry, free-flowing white powder obtained by evaporating the methanol. The direct production of dry sodium methylate has been carried out by the introduction of methanol vapors to molten sodium in a heavy duty agitating reactor. The sohd is supphed in polyethylene bags contained in airtight dmms filled in a nitrogen atmosphere. 

Mercury thermometers are subject to separation of the mercury column or to inclusion of bubbles of the fiU gas. These may result from shipping and handling and cause a scale offset which can usually be seen upon visual examination, and they are always recogni2ed by a 0°C verification check. Manufacturers will suggest means by which these temporary defects may be cured. 

Heavy Metals. Heavy metals of particular concern in the treatment of wastewaters include copper, chromium, 2inc, cadmium, mercury, lead, and nickel. They are usually present in the form of organic complexes, especially in wastewaters generated from textiles finishing and dye chemicals manufacture. 

The limit of 1 ppm mercury placed on colors intended for use in foods was estabUshed by a letter from the Acting Director of the Division of Colors and Cosmetics to the certified color manufacturers in 1970. This action was the first step taken to replace the somewhat nebulous heavy metals specifications previously used with concrete limits for specific metals. 

The phases and their proportions present ia hardened amalgam are controlled by many factors. The composition of the alloy the size, shape, and size distribution of the particles the thermal history of the cast ingot and the comminuted alloy and the surface treatment of the particles are some of the factors for which the manufacturer is responsible. The tooth cavity preparation and the mixing, compacting, and finishing techniques of the dentist can make the difference between satisfactory and unsatisfactory restorations, even with the best of alloys. A minimal amount of residual mercury and porosity are needed to obtain the most serviceable restorations (138). 

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