Process calcium recycle

In Table 2, the nuclear electricity generation is now commercially conducted, and nuclear hydrogen production is now under research and development. As for the nuclear hydrocarbon production, a nuclear synthetic methane recycling process is being developed by the Tokyo Institute of Technology for on-board steam-methane reforming with calcium oxide for CO2 sorption (Ref. 5). 

Lime Soda. Process. Lime (CaO) reacts with a dilute (10—14%), hot (100°C) soda ash solution in a series of agitated tanks producing caustic and calcium carbonate. Although dilute alkaH solutions increase the conversion, the reaction does not go to completion and, in practice, only about 90% of the stoichiometric amount of lime is added. In this manner the lime is all converted to calcium carbonate and about 10% of the feed alkaH remains. The resulting slurry is sent to a clarifier where the calcium carbonate is removed, then washed to recover the residual alkaH. The clean calcium carbonate is then calcined to lime and recycled while the dilute caustic—soda ash solution is sent to evaporators and concentrated. The concentration process forces precipitation of the residual sodium carbonate from the caustic solution the ash is then removed by centrifugation and recycled. Caustic soda made by this process is comparable to the current electrolytic diaphragm ceU product. 

Israel Mining Industries developed a process in which hydrochloric acid, instead of sulfuric acid, was used as the acidulant (37). The acidulate contained dissolved calcium chloride which then was separated from the phosphoric acid by use of solvent extraction using a recyclable organic solvent. The process was operated commercially for a limited time, but the generation of HCl fumes was destmctive to production equipment. 

Wet Process. The sodium arsenate and stannate slag are treated by a leach and precipitation process to produce calcium arsenate, calcium stannate, and a sodium hydroxide solution for recycle. The sodium antimonate filtercake containing selenium, tellurium, and indium is treated in a special metals refinery to recover indium and tellurium. 

A diagram for one implementation of this process (61,62) is shown in Eigure 11. Recovered potassium sulfate is converted to potassium formate [590-29 ] by reaction with calcium formate [544-17-2] which is made by reacting hydrated lime, Ca(OH)2, and carbon monoxide. The potassium formate (mp 167°C), in hquid form, is recycled to the combustor at about 170°C. Sulfur is removed as soHd calcium sulfate by filtration and then disposed of (see... 

Wet-process acid is manufactured by the digestion of phosphate rock (calcium phosphate) with sulfuric acid. Depending on availabiHty, other acids such as hydrochloric may be used, but the sulfuric-based processes are by far the most prevalent. Phosphoric acid is separated from the resultant calcium sulfate slurry by filtration. To generate a filterable slurry and to enhance the P2O5 content of the acid, much of the acid filtrate is recycled to the reactor. 

The historical direct reaction route, which utilised phosgenation of a solution of BPA in pyridine, proved inefficient commercially because of the need for massive pyridine recycle. Calcium hydroxide was used as an HCl scavenger for a period of time. In the historical transesterification process, BPA and diphenyl carbonate are heated in the melt in the presence of a catalyst, driving off by-product phenol, which is recycled to diphenyl carbonate. Using a series of reactors providing higher heat and vacuum, the product polymer was eventually produced as a neat melt. 

First Carbonation. The process stream OH is raised to 3.0 with carbon dioxide. Juice is recycled either internally or in a separate vessel to provide seed for calcium carbonate growth. Retention time is 15—20 min at 80—85°C. OH of the juice purification process streams is more descriptive than pH for two reasons first, all of the important solution chemistry depends on reactions of the hydroxyl ion rather than of the hydrogen ion and second, the nature of the C0 2 U20-Ca " equiUbria results in a OH which is independent of the temperature of the solution. AH of the temperature effects on the dissociation constant of water are reflected by the pH. 

Calcium thiosulfate has been prepared from calcium sulfite and sulfur at 30—40°C, or from boiling lime and sulfur in the presence of sulfur dioxide until a colorless solution is obtained. Alternatively, a concentrated solution of sodium thiosulfate is treated with calcium chloride the crystalline sodium chloride is removed at low temperature. Concentrated solutions of calcium thiosulfate are prepared from ammonium thiosulfate and lime the Hberated ammonium ion is recycled to the ammonium thiosulfate process (85). 

Modifications of the basic process are undersoftening, spHt recarbonation, and spHt treatment. In undersoftening, the pH is raised to 8.5—8.7 to remove only calcium. No recarbonation is required. SpHt recarbonation involves the use of two units in series. In the first or primary unit, the required lime and soda ash are added and the water is allowed to settie and is recarbonated just to pH 10.3, which is the minimum pH at which the carbonic species are present principally as the carbonate ion. The primary effluent then enters the second or secondary unit, where it contacts recycled sludge from the secondary unit resulting in the precipitation of almost pure calcium carbonate. The effluent setties, is recarbonated to the pH of saturation, and is filtered. The advantages over conventional treatment ate reductions in lime, soda ash, and COg requirements very low alkalinities and reduced maintenance costs because of the stabiUty of the effluent. The main disadvantages are the necessity for very careful pH control and the requirement for twice the normal plant capacity. 

In another cocrystalHzation process, lime is mixed with 50% caustic and recycled filtrate and chlorinated to yield a slurry of calcium hypochlorite dihydrate and NaCl crystals that are separated in a hydrauHc classifier. The underflow is mixed with centrate mother Hquor and sent to a wet screen classifier the overflow is recycled to the hydroclone and the salt-rich bottoms are centrifuged. The centrate is recycled to the chlorinator and the salt used as feed to chloralkaH ceUs. The Ca(OCl)2-rich overheads from the hydroclone are centrifuged, the cake going to a dryer and the filtrate sent to the wet screen classifier (207). 

The Sbddeutsche Kalkstickstoffwerke process at Trostberg uses powdered calcium carbide along with recycle product and calcium fluoride ia a rotary kiln at 1000—1100°C. The capacity of a unit is 25 t fixed nitrogen per day. The product passes to a rotary cooler and is granular (21). 

The calcium cyanamide feed is weU mixed with the recycled slurry and filtrate ia a feed vessel. The calcium cyanamide is added at a rate to maintain a pH of 6.0—6.5 ia the cooling tank. The carbonation step can be conducted ia a turbiae absorber with a residence time of 1—2 min. After the carbonation step, the slurry is held at 30—40°C to complete the formation of calcium carbonate, after which the slurry is cooled and filtered. AH equipment for the process is preferably of stainless steel. The resulting solution is used directiy for conversion to dicyandiamide. 

Of the removal processes that have attained commercial status, the current favorite employs a shiny of lime or limestone. The activity of the reagent is promoted by the addition of small amounts of carboxylic acids such as adipic acid. The gas and the shiny are contacted in a spray tower. The calcium salt is discarded. A process that employs aqueous sodium citrate, however, is suited for the recoveiy of elemental sulfur. The citrate solution is regenerated and recycled. (Kohl and Riesenfeld, Gas Purification, Gulf, 1985, p. 356.)... 

Uchino and Azuma [498] proposed a way in which to recycle the filtrate solutions. The process consists of adding calcium hydroxide, Ca(OH)2, to the filtrate, yielding a calcium fluoride, CaF2 precipitate and gaseous ammonia, NH3. The fluorine and ammonia are recovered in forms that are suitable for reutilization. 

Making paper without pollution requires that each part of the process be nonpolluting. The chemicals most commonly used in the production of pulp are NaOH and Na2 S. In modem paper mills, sulfur-containing by-products are scmbbed from the plant exhaust, and the aqueous sodium hydroxide is reclaimed and recycled. The fillers used to make paper opaque—titanium dioxide, calcium carbonate, and kaolin (a clay)—are natural, nonpolluting minerals. The polymer binders and sizers are relatively easy to recapture from the aqueous waste stream. 

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