Ions, recycling

R. Weyhe, I. Desmuee, F. Tedjar, Economic Requirements on Future li-ion Recycling Processes Workshop Insights into Novel Solid Materials, their Recyclability and Integration into Li Polymer Batteries for EVs—Future Research in this Field, Timisoara (Romania) 2012. 

FIGURE 8.2 The potential energy surfaces of dioxolenium ions recyclization reactions >kJ/mol). 

The activation energy of the nonsubstituted ion recyclization 24 is 76.2 kJ/mol. Methyl groups in the 1st carbon atom in the hydroxyethyl substituent favors the cyclization by reducing the activation energy to 72.3 kJ/mol. In case of the ethyl substituent a further, but not so noticeable, decrease in this value is observed (70.8 kJ/mol). 

The ion-exclusion process for sucrose purification has been practiced commercially by Firm Sugar (104). This process operates in a cycHc-batch mode and provides a sucrose product that does not contain the highly molassogenic salt impurities and thus can be recycled to the crystallizers for additional sucrose recovery. 

Various ways of overcoming the PTA oxidation problem have been incorporated into commercial processes. The predominant solution is the use of high concentrations of manganese and cobalt ions (2,248—254), optionally with various cocatalysts (204,255,256), in the presence of an organic or inorganic bromide promoter in acetic acid solvent. Operational temperatures are rather high (ca 200°C). A lesser but significant alternative involves isolation of intermediate PTA, conversion to methyl/)-toluate, and recycle to the reactor. The ester is oxidized to monomethyl terephthalate, which is subsequentiy converted to DMT and purified by distillation (248,257—264). 

A simplified schematic layout of an ion-exchange production facihty is presented in Figure 1. Layouts vary from one company to another and are significantly more complex when recycle of streams and environmental controls are incorporated in the schematics. 

Waste Treatment. Environmental concerns have increased the need to treat Hquid discharges from all types of industrial processes, as well as mnoffs where toxic substances appear as a result of leaks or following solubilization (see Wastes, industrial). One method of treatment consists of an ion-exchange system to remove the objectionable components only. Another involves complete or partial elimination of Hquid discharges by recycling streams within the plant. This method is unacceptable unless a cycHc increase in the impurities is eliminated by removing all constituents prior to recycling. 

Electrolytic Preparation of Chlorine and Caustic Soda. The preparation of chlorine [7782-50-5] and caustic soda [1310-73-2] is an important use for mercury metal. Since 1989, chlor—alkali production has been responsible for the largest use for mercury in the United States. In this process, mercury is used as a flowing cathode in an electrolytic cell into which a sodium chloride [7647-14-5] solution (brine) is introduced. This brine is then subjected to an electric current, and the aqueous solution of sodium chloride flows between the anode and the mercury, releasing chlorine gas at the anode. The sodium ions form an amalgam with the mercury cathode. Water is added to the amalgam to remove the sodium [7440-23-5] forming hydrogen [1333-74-0] and sodium hydroxide and relatively pure mercury metal, which is recycled into the cell (see Alkali and chlorine products). 

In the first step of the reaction, the acetoxylation of propylene is carried out in the gas phase, using soHd catalyst containing pahadium as the main catalyst at 160—180°C and 0.49—0.98 MPa (70—140 psi). Components from the reactor are separated into Hquid components and gas components. The Hquid components containing the product, ahyl acetate, are sent to the hydrolysis process. The gas components contain unreacted gases and CO2. After removal of CO2, the unreacted gases, are recycled to the reactor. In the second step, the hydrolysis, which is an equhibrium reaction of ahyl acetate, an acid catalyst is used. To simplify the process, a sohd acid catalyst such as ion-exchange resin is used, and the reaction is carried out at the fixed-bed Hquid phase. The reaction takes place under the mild condition of 60—80°C and ahyl alcohol is selectively produced in almost 100% yield. Acetic acid recovered from the... 

Closed-Mill Concept. The closed-mill concept, or water circuit closure, has been studied by the pulp and paper industry for many years. In some parts of the paper manufacturing process, up to 98% of the water is recycled within the process, eg, the wet end of the paper machine. However, in the pulp mill, especiaUy kraft mills, effluents are produced owing to the need to purge from the system various metals that come in with the wood, as weU as organic by-products from the pulping process, additives, and especially chloride ions that originate in the bleach plant. 

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. 

Solvent for Displacement Reactions. As the most polar of the common aprotic solvents, DMSO is a favored solvent for displacement reactions because of its high dielectric constant and because anions are less solvated in it (87). Rates for these reactions are sometimes a thousand times faster in DMSO than in alcohols. Suitable nucleophiles include acetyUde ion, alkoxide ion, hydroxide ion, azide ion, carbanions, carboxylate ions, cyanide ion, hahde ions, mercaptide ions, phenoxide ions, nitrite ions, and thiocyanate ions (31). Rates of displacement by amides or amines are also greater in DMSO than in alcohol or aqueous solutions. Dimethyl sulfoxide is used as the reaction solvent in the manufacture of high performance, polyaryl ether polymers by reaction of bis(4,4 -chlorophenyl) sulfone with the disodium salts of dihydroxyphenols, eg, bisphenol A or 4,4 -sulfonylbisphenol (88). These and related reactions are made more economical by efficient recycling of DMSO (89). Nucleophilic displacement of activated aromatic nitro groups with aryloxy anion in DMSO is a versatile and useful reaction for the synthesis of aromatic ethers and polyethers (90). 

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. 

When antifreeze becomes unsuitable for use, either because of depletion of inhibitors, presence of corrosion products or corrosive ions, or degradation of the fluid, recycling and reuse of the antifreeze, rather than disposal, may be considered. Although ethylene glycol is readily biodegraded in typical municipal waste treatment faciHties, antifreeze disposal becomes problematic because the coolant may contain hazardous quantities of heavy metals picked up from the cooling system. Recycling may be economically preferred over coolant disposal and reduces the concern for environmental impact. 

Ideally, a system for recycling spent antifreeze consists first of the removal of the deleterious contaminants such as the corrosion products, corrosive ions, degradation products, and remaining inhibitors. Then the clean fluid could be reinhibited to a known concentration of both inhibitors and glycol. 

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