Sulfuric acid recovery

Wastewater is generated in the primary zinc and primary cadmium recovery subcategories by acid plant blowdown, which results from sulfuric acid recovery, air pollution control, leaching, anode/ cathode washing, and contact cooling. The streams may contain significant concentrations of lead, arsenic, cadmium, and zinc. Tables 3.26 and 3.27 present classical and toxic pollutant data for the primary zinc and primary cadmium subcategories. 

SAR [Sulfuric Acid Recovery] A process for purifying and concentrating used sulfuric acid for re-use. The acid is heated with oxygen at 1,040°C to convert the acid to sulfur dioxide. This is then oxidized over a vanadium-containing catalyst to sulfur trioxide, which is dissolved in fresh sulfuric acid to give 98 percent acid. Developed by L Air Liquide and ICI. First demonstrated in 1991 at a methyl methacrylate plant in Taiwan. 

The sulfuric acid recovery process (SARP), developed jointly by Texaco Inc. and Stratford Engineering Corp. to reduce the acid consumption in H2S04 alkylation units, was another contribution to alkylation technology (18). In this process the spent acid from an alkylation... 

Improved product treatment Sulfuric acid recovery process Catalyst promoters... 

A number of different processes involving the absorption of olefin in recycle sulfuric acid alkylation catalyst, extraction of the dialkyl sulfate, treatment of the extract in some manner, and alkylation of the treated dialkyl sulfate have been considered. One such process which has become known in the industry as SARP is the subject of this paper. SARP stands for Sulfuric Acid Recovery Process, which obviously has a rather generic connotation. The process is rather specific. The writer prefers the name originally given to the process, namely, Extractylation. However, SARP has the advantage of being known and is short, so SARP will probably prevail. 

IV. Developments in sulfuric acid recovery and regeneration methods. 

One patented process (40) was introduced in the mid- 60s to reduce the amount of sulfuric acid required by alkylation it was called the Sulfuric Acid Recovery Process (SARP) and was jointly licensed by Texaco Development Corporation and Stratford Engineering Corporation. Chemically, SARP proved all claims made for it. Utilized only with propylene/butylene alkylation the acid requirement was reduced as much as 70% actual acid dilution rates were lower than 0. 2 acid/gallon alkylate. However, the spent acid from SARP was different and could not be regenerated at the same rate as regular spent alkylation acid. This caused the chemical companies to increase the charges for regenerating the SARP spent acid to a point where there was no economic incentive to operate SARP. The two commercial SARP installations are not in use at the present time although new possibilities for SARP have arisen just in the past few months. 

Tongwen, X. and Weihua, Y. Sulfuric acid recovery from titanium white waste liquor using diffusion dialysis with a new series of anion exchange membrane-static runs. J. Membr. Sci., 183, 193-200, 2001. 

Process used for waste sulfuric acid recovery dependent upon the impurity level ... 

Metal ion impurities in spent acid impose different recovery problems. For instance, iron residues in the spent acid from titanium dioxide manufacture may be removed by crystallization of first FeS04 7FI2O followed by crops of various iron(II) salts, or by electrodialysis [67]. Incidentally electrodialysis has also been used for sulfuric acid recovery from wastewater, either directly or after preconcentration on cation exchange resin [68]. 

The manufacture of picrite posed an extremely difficult problem in sulfuric-acid recovery for the substantial amount of spent acid produced contained only about 18% sulfuric acid. Submerged combustion was applied to this duty at ROF Bishopton and while this procedure functioned well as far as actual concentration was concerned, corrosion of the equipment by the nitrate ion present was so severe that the process could only be run intermittently and eventually had to be abandoned leaving the acid to the dealt with by neutralization with limestone followed by prolonged drainage in settling lagoons. 

SARP [Sulfuric Acid Recovery Process] A method for recovering sulfuric acid that has been used for alkylation, for reuse. The acid is reacted with propylene, yielding dipropyl sulfate, which is extracted from the acid tar with isobutane. It is not necessary to hydrolyze the sulfate to sulfuric acid because the sulfate itself... 

Small amounts of propionitrile and bis(cyanoethyl) ether are formed as by-products. The hydrogen ions are formed from water at the anode and pass to the cathode through a membrane. The catholyte that is continuously recirculated in the cell consists of a mixture of acrylonitrile, water, and a tetraalkylammonium salt the anolyte is recirculated aqueous sulfuric acid. A quantity of catholyte is continuously removed for recovery of adiponitrile and unreacted acrylonitrile the latter is fed back to the catholyte with fresh acrylonitrile. Oxygen that is produced at the anodes is vented and water is added to the circulating anolyte to replace the water that is lost through electrolysis. The operating temperature of the cell is ca 50—60°C. Current densities are 0.25-1.5 A/cm (see Electrochemical processing). 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

Normally, a slight excess of sulfuric acid is used to bring the reaction to completion. There are, of course, many side reactions involving siHca and other impurity minerals in the rock. Fluorine—silica reactions are especially important as these affect the nature of the calcium sulfate by-product and of fluorine recovery methods. Thermodynamic and kinetic details of the chemistry have been described (34). 

Production Technology. Processes for extraction of P2O3 from phosphate rock by sulfuric acid vary widely, but all produce a phosphoric acid—calcium sulfate slurry that requires soHds-Hquid separation (usually by filtration (qv)), countercurrent washing of the soHds to improve P2O3 recovery, and concentration of the acid. Volatilized fluorine compounds are scmbbed and calcium sulfate is disposed of in a variety of ways. 

The precipitated cellulose acetate is filtered from the dilute (25—36%) acetic acid. The acetic acid and salts remaining from the sulfuric acid neutrali2ation are removed by washing. The wet polymer is typically dried to a moisture content of 1—5%. The dilute acetic acid obtained from the washing and precipitation steps caimot be used in other stages of the process. Its efficient recovery and recycle are an economic necessity. 

Boron trifluoride catalyst may be recovered by distillation, chemical reactions, or a combination of these methods. Ammonia or amines are frequently added to the spent catalyst to form stable coordination compounds that can be separated from the reaction products. Subsequent treatment with sulfuric acid releases boron trifluoride. An organic compound may be added that forms an adduct more stable than that formed by the desired product and boron trifluoride. In another procedure, a fluoride is added to the reaction products to precipitate the boron trifluoride which is then released by heating. Selective solvents may also be employed in recovery procedures (see Catalysts,regeneration). 

Large-scale recovery of light oil was commercialized in England, Germany, and the United States toward the end of the nineteenth century (151). Industrial coal-tar production dates from the earliest operation of coal-gas faciUties. The principal bulk commodities derived from coal tar are wood-preserving oils, road tars, industrial pitches, and coke. Naphthalene is obtained from tar oils by crystallization, tar acids are derived by extraction of tar oils with caustic, and tar bases by extraction with sulfuric acid. Coal tars generally contain less than 1% benzene and toluene, and may contain up to 1% xylene. The total U.S. production of BTX from coke-oven operations is insignificant compared to petroleum product consumptions. 

The typical SEA process uses a manganese catalyst with a potassium promoter (for solubilization) in a batch reactor. A manganese catalyst increases the relative rate of attack on carbonyl intermediates. Low conversions are followed by recovery and recycle of complex intermediate streams. Acid recovery and purification involve extraction with caustic and heat treatment to further decrease small amounts of impurities (particularly carbonyls). The fatty acids are recovered by freeing with sulfuric acid and, hence, sodium sulfate is a by-product. 

The brine clean-up consists of skimming and settling steps to free the solution from oil, clays, and other impurities. Sulfuric acid is then added until a pH of <2.5 is reached ensuring iodine Hberation by oxidation, precipitation of the soluble barium contained in the brine, and recovery of the remaining iodine. 

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S0 3, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach Hquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH NO, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and cosdy ore particle/leach hquor separation step. 

For environmental reasons, the entire process is handled by enclosed equipment. Lead recoveries of 96% can be obtained from the raw materials, and sulfur dioxide gas released in the process is used to produce sulfuric acid. Four plants are in operation as of 1994. Three are in Russia and one is in Italy. 

Owing to the cycHc nature of the TBRC operation, waste heat recovery from the off-gases is not practical and the SO2 content of the gas varies with the converter cycle. In order to supply a relatively uniform flow and strength SO2 gas to a sulfuric acid plant, a system has been installed at RonnskAr whereby the SO2 from fluctuating smelter gases is partially absorbed in water. During smelter gas intermption, SO2 is stripped with air and the concentrated gas deflvered to the acid plant. 

The products of reaction are pumped to a filter press for separation into a sodium sulfate solution and a filter cake having a low moisture content. The filter cake is then ready to be processed for the recovery of lead. The filtrate from the process contains an excess of sodium carbonate, and can be neutralized using the sulfuric acid drained from the batteries. 

Recovery from Ores and Clays. The preferred method of extraction of lithium from spodumene ore is the sulfuric acid process (18), used on ore concentrates of 5—6% Li O, representing 62—74% pure spodumene. Methods suitable for extraction from spodumene also can be used for petaUte, because the latter mineral converts to P-spodumene—Si02 soHd solution on heating to a high temperature. 

Electrowinning from Aqueous Solutions. Electrowinriing is the recovery of a metal by electrochemical reduction of one of its compounds dissolved in a suitable electrolyte. Various types of solutions can be used, but sulfuric acid and sulfate solutions are preferred because these are less corrosive than others and the reagents are fairly cheap. From an electrochemical viewpoint, the high mobiUty of the hydrogen ion leads to high conductivity and low ohmic losses, and the sulfate ion is electrochemicaHy inert under normal conditions. 

The aqueous sodium naphthenate phase is decanted from the hydrocarbon phase and treated with acid to regenerate the cmde naphthenic acids. Sulfuric acid is used almost exclusively, for economic reasons. The wet cmde naphthenic acid phase separates and is decanted from the sodium sulfate brine. The volume of sodium sulfate brine produced from dilute sodium naphthenate solutions is significant, on the order of 10 L per L of cmde naphthenic acid. The brine contains some phenolic compounds and must be treated or disposed of in an environmentally sound manner. Sodium phenolates can be selectively neutralized using carbon dioxide and recovered before the sodium naphthenate is finally acidified with mineral acid (29). Recovery of naphthenic acid from aqueous sodium naphthenate solutions using ion-exchange resins has also been reported (30). 

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