Zinc oxide production

For the most part, the zinc materials recovered from secondary materials such as slab zinc, alloys, dusts, and compounds are comparable in quality to primary products. Zinc in brass is the principal form of secondary recovery, although secondary slab zinc has risen substantially over the last few years because it has been the principal zinc product of electric arc furnace (EAF) dust recycling. Impure zinc oxide products and zinc-bearing slags are sometimes used as trace element additives in fertilizers and animal feeds. About 10% of the domestic requirement for zinc is satisfied by old scrap. 

J. P. Kuz mina, V.A. Nikitenko, Zinc Oxide. Production and Optical Properties [in Russian], Moscow (1984). 

In another example, Beveridge studied the oxidation of zinc sulfide spheres and reported that the global rate was, in turn, controlled by the surface chemical reaction at low temperatures, diffusion through the zinc oxide product layer at intermediate temperatures, and external mass transfer resistance at higher temperatures. 

The zinc oxidation products form a hard cementlike layer in the silicic acid film. Resistance to diffusion is increased and attack of atmospheric oxygen on the substrate is thus slowed down (barrier protection). 

Kuz mina, I.P. and Nikitenko, V.A. (1984) Zinc Oxides Production and Optical Properties, Nauka, Moscow. 

Zinc is also used extensively to galvanize other metals such as iron to prevent corrosion. Zinc oxide is a unique and very useful material for modern civilization. It is widely used in the manufacture of paints, rubber products, cosmetics, pharmaceuticals, floor coverings, plastics, printing inks, soap, storage batteries, textiles, electrical equipment, and other products. Lithopone, a mixture of zinc sulfide and barium sulfate, is an important pigment. 

Isobutyl alcohol [78-83-1] forms a substantial fraction of the butanols produced by higher alcohol synthesis over modified copper—zinc oxide-based catalysts. Conceivably, separation of this alcohol and dehydration affords an alternative route to isobutjiene [115-11 -7] for methyl /-butyl ether [1624-04-4] (MTBE) production. MTBE is a rapidly growing constituent of reformulated gasoline, but its growth is likely to be limited by available suppHes of isobutylene. Thus higher alcohol synthesis provides a process capable of supplying all of the raw materials required for manufacture of this key fuel oxygenate (24) (see Ethers). 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

Many methods for the conversion of acid copolymers to ionomers have been described by Du Pont (27,28). The chemistry involved is simple when cations such as sodium or potassium are involved, but conditions must be controlled to obtain uniform products. Solutions of sodium hydroxide or methoxide can be fed to the acid copolymer melt, using a high shear device such as a two-roU mill to achieve uniformity. AH volatile by-products are easily removed during the conversion, which is mn at about 150°C. A continuous process has been described, using two extmders, the first designed to plasticate the feed polymer and mix it rapidly with the metal compound, eg, zinc oxide, at 160°C (28). Acetic acid is pumped into the melt to function as an activator. Volatiles are removed in an extraction-extmder which follows the reactor-extmder, and the anhydrous melt emerges through a die-plate as strands which are cut into pellets. 

Sulfamic acid at concentrations of 2—6%, in conjunction with the proper proprietary inhibitor, can be effective in removing zinc oxides and corrosion by-products without attacking the zinc metal. 

The zinc oxide component of the catalyst serves to maintain the activity and surface area of the copper sites, and additionally helps to reduce light ends by-product formation. Selectivity is better than 99%, with typical impurities being ethers, esters, aldehydes, ketones, higher alcohols, and waxes. The alumina portion of the catalyst primarily serves as a support. 

Henkel Rearrangement of Benzoic Acid and Phthalic Anhydride. Henkel technology is based on the conversion of benzenecarboxyhc acids to their potassium salts. The salts are rearranged in the presence of carbon dioxide and a catalyst such as cadmium or zinc oxide to form dipotassium terephthalate, which is converted to terephthahc acid (59—61). Henkel technology is obsolete and is no longer practiced, but it was once commercialized by Teijin Hercules Chemical Co. and Kawasaki Kasei Chemicals Ltd. Both processes foUowed a route starting with oxidation of napthalene to phthahc anhydride. In the Teijin process, the phthaHc anhydride was converted sequentially to monopotassium and then dipotassium o-phthalate by aqueous recycle of monopotassium and dipotassium terephthalate (62). The dipotassium o-phthalate was recovered and isomerized in carbon dioxide at a pressure of 1000—5000 kPa ( 10 50 atm) and at 350—450°C. The product dipotassium terephthalate was dissolved in water and recycled as noted above. Production of monopotassium o-phthalate released terephthahc acid, which was filtered, dried, and stored (63,64). 

Historically, ZnO is an older pigment than Ti02. In France, the industrial production of zinc oxide started in 1840. In the French process, zinc... 

Two classes of grinding equipment are used to prepare dispersions. The first, the coUoid mill, does not effect a particle size reduction but does break down aggregates of fine particles. CoUoid mills are used for such powders as clays, precipitated whiting, etc. Sometimes these mills are used to process zinc oxide but for dipped mbber products that is not satisfactory. 

Cure Characteristics. Methods of natural rubber production and raw material properties vary from factory to factory and area to area. Consequentiy, the cure characteristics of natural mbber can vary, even within a particular grade. Factors such as maturation, method and pH of coagulation, preservatives, dry mbber content and viscosity-stabilizing agents, eg, hydroxylamine-neutral sulfate, influence the cure characteristics of natural mbber. Therefore the consistency of cure for different grades of mbber is determined from compounds mixed to the ACSl formulation (27). The ACSl formulation is as follows natural mbber, 100 stearic acid, 0.5 zinc oxide, 6.0 sulfur, 3.5 and 2-mercaptobenzothiazole (MBT), 0.5. 

Hydrogenation. Gas-phase catalytic hydrogenation of succinic anhydride yields y-butyrolactone [96-48-0] (GBL), tetrahydrofiiran [109-99-9] (THF), 1,4-butanediol (BDO), or a mixture of these products, depending on the experimental conditions. Catalysts mentioned in the Hterature include copper chromites with various additives (72), copper—zinc oxides with promoters (73—75), and mthenium (76). The same products are obtained by hquid-phase hydrogenation catalysts used include Pd with various modifiers on various carriers (77—80), Ru on C (81) or Ru complexes (82,83), Rh on C (79), Cu—Co—Mn oxides (84), Co—Ni—Re oxides (85), Cu—Ti oxides (86), Ca—Mo—Ni on diatomaceous earth (87), and Mo—Ba—Re oxides (88). Chemical reduction of succinic anhydride to GBL or THF can be performed with 2-propanol in the presence of Zr02 catalyst (89,90). 

Zinc compounds are generally colorless unless the other component, eg, chromate, is colored. The lack of color of most zinc compounds in visible light is a great advantage in that they do not color paint films, plastics, mbber, cosmetics, etc. However, when excited by various types of radiation and at various temperatures, zinc oxide, sulfide, selenide [1315-09-9], and related compounds exhibit luminescence, ie, they emit colored light (see Luminescent materials). Zinc-based phosphors can be produced in many colors, depending upon the added dopants. They are used in television tubes, luminescent glasses, and various specialty products. 

Leaded Zinc Oxide. Oxides containing more than 5 wt % basic lead sulfate are classified as leaded and are made ia the American process from high lead materials, usually lead sulfide mineral, or by blending ziac oxide and basic lead sulfate. There is only one manufacturer ia the United States and the product contains 20—28 wt % basic lead sulfate. Leaded oxides are used only ia mbber ia the United States. 

Economic Aspects. Table 3 shows that mbber production is the largest market for zinc oxide the downturn in 1980 resulted from a drop in tire production because of the production trend to smaller tires, more importation of tires, and a recession. The drop in paint usage reflects the trend to water-base paints, which originally contained no zinc oxide. However, its growing use in such paints is based upon improved formulations based on zinc oxide. The increased use in agriculture is a result of the realization of the importance of zinc as a trace element. The rise in use of zinc-oxide-coated paper for photocopying is followed by a slackening in use because of a shift to plain-paper copiers. 

Table 5. U.S. Production and Importation of Zinc Oxide, Sulfate, and Chloride, Metric Tons ...

It is also possible to deflect uv radiation by physically blocking the radiation using an opaque makeup product. A low particle size titanium dioxide can reflect uv light without the undesirable whitening effect on the skin that often results from products containing, for example, zinc oxide or regular grades of titanium dioxide. 

The compositions of zinc oxide—eugenol impression pastes are similar to those of the zinc oxide—eugenol cements (86). Variations in specific characteristics are achieved by the proportions of the ingredients (87). Properties vary in commercial products (88). The modifications of the zinc oxide—eugenol system intended for bite-registration pastes may include agents to increase the body or thixotropic character of the unset mix to improve... 

Calcium Chelates (Salicylates). Several successhil dental cements which use the formation of a calcium chelate system (96) were developed based on the reaction of calcium hydroxide [1305-62-0] and various phenohc esters of sahcyhc acid [69-72-7]. The calcium sahcylate [824-35-1] system offers certain advantages over the more widely used zinc oxide—eugenol system. These products are completely bland, antibacterial (97), facihtate the formation of reparative dentin, and do not retard the free-radical polymerization reaction of acryhc monomer systems. The principal deficiencies of this type of cement are its relatively high solubihty, relatively low strength, and low modulus. Less soluble and higher strength calcium-based cements based on dimer and trimer acid have been reported (82). 

The formulation of calcium chelate materials is based upon the formation of a low-solubiUty chelate between calcium hydroxide and a sahcylate. Dycal utilizes the reaction product of a polyhydric compound and sahcyhc acid. Other sahcyhc acid esters can be similarly used. Vehicles used to carry the calcium hydroxide, extenders, and fillers may include mineral oil, A/-ethyl- -toluenesulfonamide [80-39-7] and polymeric fluids. The filler additions may include titanium dioxide [13463-67-7] zinc oxide, sihca [7631-86-9], calcium sulfate, and barium sulfate [7727-43-7]. Zinc oxide and barium sulfate are useflil as x-ray opacifying agents to ensure a density greater than that of normal tooth stmcture. Resins, rosin, limed rosins, and modified rosins may serve as modifiers of the physical characteristics in both the unset and set states. 

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