Sulfuric Acid Patents (Class 423/320)
  • Patent number: 4623528
    Abstract: Fluorine in phosphate ores is present as the mineral fluorapatite. When the ores are digested with sulfuric acid a slurry is formed which can be filtered to make wet-process phosphoric acid. But fluorine compounds are discharged into the surrounding air during digestion and filtration. The fluorine-containing air is scrubbed with water to prevent air pollution. Scrubber water is cooled in ponds and is recycled to the scrubber. However, fluorine compounds are emitted from the cooling ponds and cause air pollution. In the present invention, processes are disclosed for treating fluorine-containing gases without use of cooling ponds thereby eliminating the air pollution problem. A facility is provided for treating fluorine-containing gases wherein fluosilicic acid or fluosilicate salts are converted to a fluoride salt by the addition of an alkaline substance. A slightly acidic scrubber water is concentrated in an absorption tower.
    Type: Grant
    Filed: June 17, 1985
    Date of Patent: November 18, 1986
    Assignee: James C. Barber and Associates, Inc.
    Inventor: James C. Barber
  • Patent number: 4608238
    Abstract: This disclosure concerns an improved phospho-gypsum recovery process in which phospho-gypsum waste product and coke are first heated to remove moisture, some SO.sub.2 and other vaporous matter, then heated to a higher temperature in a reducing atmosphere to remove and separately recover SO.sub.2, then further heated in an oxidizing atmosphere to about 1200.degree. to 1250.degree. C. to remove any unreacted carbon and calcium sulfide before entering an electric furnace. The disclosure also concerns passing the gas stream from the condenser-heat exchanger over the clinker from the electric furnace to scrub SO.sub.2 from said gas stream. The essence of the invention is the unique absorber system used to remove any and all remaining fluorine in the gases from the calciner/furnace. If not removed, the fluorine will severely harm the catalyst used in the contact sulfuric acid plant to which the gases are sent for recovery of sulfur values.
    Type: Grant
    Filed: July 27, 1984
    Date of Patent: August 26, 1986
    Inventors: Eddie K. Wilson, Sr., Silvio J. Spigolon
  • Patent number: 4606897
    Abstract: Phosphate rock, containing appreciable quantities of organic impurities, is thermally treated under controlled conditions to fully utilize the fuel values of the organic matter contained therein. This process is beneficial for treating deposits of unaltered Idaho rock containing both higher grade phosphate rock and lower grade phosphatic shales and recovering therefrom substantially all the phosphate values as a rock product rendered more acceptable for acidulation to wet-process phosphoric acid.
    Type: Grant
    Filed: April 29, 1985
    Date of Patent: August 19, 1986
    Assignee: Tennessee Valley Authority
    Inventor: Alexander D. Mair
  • Patent number: 4592901
    Abstract: A process for removing impurities from phosphoric acid, especially concentrated wet process phosphoric acid, comprises filtering phosphoric acid through a filter cake (e.g., diatomite) on a porous member at a temperature in the range of about 57.degree. C. to about 77.degree. C. The filter cake retains some phosphate values. A major portion of the phosphate values retained by the filter cake can be introduced into the phosphoric acid manufacturing process, as by slurrying the filter cake in water, separating the aqueous phase from the solid phase, and introducing the aqueous phase to a wet process phosphoric acid process (e.g., as a "gypsum" filter wash).
    Type: Grant
    Filed: September 6, 1984
    Date of Patent: June 3, 1986
    Assignee: Occidental Petroleum Corporation
    Inventors: Hudson C. Smith, Wesley W. Atwood, John S. Myrick, Samuel F. Sweat
  • Patent number: 4588570
    Abstract: The present invention provides a continuous method for preparing phosphoric acid and calcium sulphate by reacting calcium phosphate with a mixture of sulphuric acid and phosphoric acid. Our method uses at least three successive crystallization steps: a first step of reacting the phosphate with the mixture of phosphoric and sulphuric acids and forming a-hemihydrate calcium sulphate, a second step of recrystallizing the a-hemihydrate into dihydrate and a third step of transforming the dehydrated calcium sulfate into a hemihydrate or anhydrite II or a mixture of the two. Where desired recycling of the products from the above steps can be used for increasing the efficiency of the above method.
    Type: Grant
    Filed: November 20, 1984
    Date of Patent: May 13, 1986
    Assignee: Prayon Development
    Inventors: Armand L. Davister, Andre R. Dubreuco, Francis A. Thirion
  • Patent number: 4581156
    Abstract: Significant improvements in defoaming in a wet-process phosphoric acid reactor are obtained by adding to the reactor during the digestion process both a surfactant defoamer and a polyacrylamide.
    Type: Grant
    Filed: December 3, 1984
    Date of Patent: April 8, 1986
    Assignee: United States Steel Corporation
    Inventor: Douglas M. Chatham
  • Patent number: 4577804
    Abstract: Phosphate rock contained in an acidic slurry is ground by equipment wherein the acidic slurry contacts the metallic surfaces of the equipment. A method for monitoring and controlling grinding ball consumption is provided in which acid-neutralizing particulate iron contained in the acidic slurry is measured and correlated to control curves, which relate particulate iron concentration to slurry pH and slurry pH to the rate grinding ball consumption. If the measured particulate iron concentration equates to an unacceptable ball corrosion rate, the equilibrium of the slurry pH and particulate iron concentration can be varied to maintain a predictable ball consumption. When making the slurry, waste water from other steps of the wet process manufacture of phosphoric acid can be used as part of an acidic diluting medium.
    Type: Grant
    Filed: August 7, 1984
    Date of Patent: March 25, 1986
    Assignee: Freeport Minerals Company
    Inventors: Vivian C. Astley, Rudolph R. Milan, Jody J. Taravella
  • Patent number: 4559204
    Abstract: There is disclosed a method of producing water-based phosphate matrix slurries wherein the as-mined phosphate matrix is dried prior to the formation of the slurry. Drying the matrix decreases the viscosity of the slurry and improves the clay consolidation characteristics of the by-product slimes produced during the phosphate slurry beneficiation process steps.
    Type: Grant
    Filed: August 17, 1984
    Date of Patent: December 17, 1985
    Assignee: Mobil Oil Corporation
    Inventors: Anil K. Agrawal, Stephen W. Saunders, George J. Weckesser
  • Patent number: 4557915
    Abstract: Phosphoric acid is produced, with concomitant recovery of solids comprising compounds of fluorine and silica, by (i) acidulating a first amount of phosphate ore with a strong acid to produce a first phosphoric acid slurry, (ii) filtering said first slurry to separate the liquid phosphoric acid content therefrom, (iii) concentrating a fraction of the phosphoric acid thus separated, (iv) recovering same, and (v) condensing the evolved vapors of concentration with a liquid absorbent to produce a solution of fluosilicic acid, (vi) acidulating a second amount of phosphate ore with said solution of fluosilicic acid together with a fraction of said first slurry, or together with a fraction of the phosphoric acid separated in the step (ii), to produce a second phosphoric acid slurry, (vii) filtering said second slurry to separate both the liquid phosphoric acid content and a solids fraction therefrom, said solids fraction comprising fluorine and silica compounds, (viiia) recycling the phosphoric acid thus separated f
    Type: Grant
    Filed: July 5, 1984
    Date of Patent: December 10, 1985
    Assignee: Rhone-Poulenc Chimie de Base
    Inventor: Guy Nineuil
  • Patent number: 4556545
    Abstract: There is disclosed an improved process of beneficiating phosphate-containing ores. The process comprises stabilizing a hydrocarbon oil, normally used in a conditioning step to improve separation of the ore from the solid contaminants in a flotation step, upstream of the conditioning step. The oil is stabilized by conducting it to a pre-stabilization step wherein it is mixed with at least one fatty acid or saponified fatty acid and water to form a stable, homogeneous emulsion. The emulsion is then transferred to the conditioning step wherein it is mixed with the phosphate-containing ore.
    Type: Grant
    Filed: September 5, 1984
    Date of Patent: December 3, 1985
    Assignee: Mobil Oil Corporation
    Inventor: Subrahmanyam Cheruvu
  • Patent number: 4540511
    Abstract: A defoamer composition comprising a mixture of defoaming effective amounts of monocarboxylic acid having from 12 to 26 carbon atoms, a monoalkanolamide, and an alcohol selected from the group consisting of primary linear aliphatic alcohols ranging from C.sub.4 to C.sub.20, primary branch aliphatic alcohols ranging from C.sub.4 to C.sub.20, and secondary alcohols ranging from C.sub.6 to C.sub.12 ; and a method of inhibiting foaming in a phosphate rock and sulfuric acid medium employed in the synthesis of phosphoric acid by the "wet process" manufacture of phosphoric acid which comprises adding to the reaction medium an effective amount of the above described defoamer composition.
    Type: Grant
    Filed: February 15, 1984
    Date of Patent: September 10, 1985
    Assignee: National Distillers and Chemical Corporation
    Inventors: Eugene F. McCaffrey, Alfred J. Dieterman, Luba Knazko
  • Patent number: 4524057
    Abstract: Concentrated phosphoric acid and calcium sulfate hemihydrate are directly produced by sulfuric acid attack upon calcium phosphate, the improvements comprising (i) continuously conducting the acid attack reaction, with concomitant formation of crystalline calcium sulfate hemihydrate, in but a single, homogeneous liquid reaction medium comprising the products of reaction, (ii) maintaining constant the temperature of the reaction medium as to effect formation of hemihydrated calcium sulfate, (iii) controlling the amount of reactants introduced to the reaction medium such as to maintain essentially constant, in liquid phase, a determined sulfate ion content, said content being at least 5 g/l and said determined content increasing with decreasing concentrations of P.sub.2 O.sub.5 at a given temperature, and (iv) withdrawing a fraction of reaction effluent, including the concentrated phosphoric acid, and individually separating and recovering hemihydrated calcium sulfate from said reaction effluent fraction.
    Type: Grant
    Filed: April 13, 1984
    Date of Patent: June 18, 1985
    Assignee: Rhone-Poulenc Industries
    Inventor: Bernard Bigot
  • Patent number: 4521392
    Abstract: Phosphoric acids of significantly different content of soluble impurities, especially magnesium compounds, can be blended to produce a phosphoric acid with a decreased tendency for forming detrimental solids when converted to a liquid fertilizer or on storage, or during transportation as when the acid is transported by ocean vessel or rail road tank car. The blending can be effected either before or after a concentration step or steps (e.g., evaporation to "merchant grade" or to superphosphoric acid). For example, wet process phosphoric acid produced by a dihydrate or gypsum process can be blended with a phosphoric acid produced by a hemihydrate process.
    Type: Grant
    Filed: March 14, 1983
    Date of Patent: June 4, 1985
    Assignee: Occidental Chemical Agricultural Products, Inc.
    Inventors: Harold E. Mills, David L. Murdock, Richard M. Ramer, Francis M. Sale
  • Patent number: 4505884
    Abstract: Substantially calcium-free fluoroaluminum phosphate precipitate (which also contains iron) can be produced by the aging of wet process phosphoric acid containing iron, fluorine and aluminum, preferably phosphoric acid analyzing in the range of about 15%-45 weight percent P.sub.2 O.sub.5, 2-4% Al.sub.2 O.sub.3 and 1-2% fluorine. One process involves digestion of phosphate ore matrix in recycled phosphoric acid, filtration to remove the insoluble residue, precipitation and filtration to remove gypsum, and aging of the product acid to precipitate the aluminum impurity as a fluoroaluminum phosphate compound. The fluoroaluminum phosphate can be decomposed (as by heating at about 195.degree. C.) to produce HF and aluminum phosphate.
    Type: Grant
    Filed: May 17, 1982
    Date of Patent: March 19, 1985
    Assignee: Occidental Research Corporation
    Inventors: Elie M. Chemtob, Gary L. Beer
  • Patent number: 4501724
    Abstract: An improved method for the wet process manufacture of concentrated phosphoric acid is disclosed herein. A mixture of gaseous sulfur trioxide and sulfuric acid now replaces concentrated sulfuric acid as a process reactant which results in a higher heat of reaction and the ability to evaporate out of the reaction slurry increased inputs of water. With this method the increased inputs of water, either from undried phosphate rock, wet grinding of phosphate rock, use of dilute sulfuric acid, or from other sources will not interfere with associated high P.sub.2 O.sub.5 yields, lower concentrations of filtrate phosphoric acid and/or unbalance the zero steam requirements.
    Type: Grant
    Filed: February 1, 1984
    Date of Patent: February 26, 1985
    Assignee: Goers Associates Inc.
    Inventor: Walter E. Goers
  • Patent number: 4495161
    Abstract: In conventional processes for manufacturing phosphoric acid, sulphuric acid is reacted with phosphate rock to produce weak phosphoric acid which is concentrated using steam from the associated sulphuric acid manufacturing operation. Low grade heat from the absorbers and drier of the sulphuric acid manufacturing plant has been wasted. According to the invention waste heat from the drier and one or more absorbers of the sulphuric acid manufacturing plant is used in all the evaporators of the phosphoric acid plant. The evaporators all operate at low pressures and their heaters are arranged in series, to enable the heat to be used at the relatively low temperatures available. The valuable steam is thus freed for other uses.
    Type: Grant
    Filed: April 16, 1984
    Date of Patent: January 22, 1985
    Assignee: C-I-L Inc.
    Inventors: Gordon M. Cameron, John V. Orlando
  • Patent number: 4485077
    Abstract: A method and system for conducting wet grinding of mined phosphate rock before utilizing the same for the production of phosphoric acid by the wet process method, the method comprising the steps of: (1) wet grinding the phosphate rock in a medium of fresh water at a first stage so as to form a fresh water slurry comprising ground rock and fresh water, (2) sending the fresh water slurry from the first stage to a second stage, (3) dewatering the fresh water slurry at the second stage so as to recover most of the fresh water from the slurry and leave substantially only wet ground rock, (4) recycling the fresh water recovered at the second stage back to the first stage for use in further wet grinding, (5) sending the ground rock from the second stage to a third stage, (6) refluidizing the ground rock at the third stage with acidic pond water so as to form a pond water slurry comprising ground rock and pond water, and (7) thereafter passing the pond water slurry on to a reactor for standard processing so as to pro
    Type: Grant
    Filed: August 12, 1983
    Date of Patent: November 27, 1984
    Assignee: The Badger Company, Inc.
    Inventor: John L. Martinez
  • Patent number: 4485078
    Abstract: Phosphoric acid is produced by the wet process from phosphate rock containing fluochlorapatite. The rock is ground in a crusher (10) to a size such that from about 50% to about 90% by weight will be passed by a -200 mesh U.S.S. sieve before being passed into a digestor (14) where it is mixed with sulfuric acid and recycled phosphoric acid to form a slurry. A suitable reductant such as sulphur dioxide is added to the slurry to maintain the oxidation-reduction potential in the range from about +150 mv to about +750 mv. The gypsum by-products are then removed from the slurry at filter (16) and a portion of the acid is recycled to digestor (14). The remaining acid is either concentrated and further processed to make fertilizers or is further processed via path (20) to remove aluminum and/or iron impurities. Select amounts of fluoride and sodium containing compounds are added to the acid in a stirred reactor (30) to cause precipitation of aluminum, principally as Na.sub.2 AlF.sub.5.
    Type: Grant
    Filed: March 8, 1983
    Date of Patent: November 27, 1984
    Assignee: Agrico Chemical Company
    Inventors: Charles W. Weston, John W. Wen, Frederick S. Mandel
  • Patent number: 4479923
    Abstract: Phosphate rock, including low grade phosphate ore, is treated to recover phosphoric acid and other valuable products by a series of steps including contacting phosphate ore with a weak phosphoric acid to form a suspension of at least a portion of the slimes contained in the ore so that the slimes can be separated from the ore, and separating the slimes to provide a deslimed phosphate ore. Deslimed phosphate rock is solubilized with phosphoric acid to convert at least a portion of the calcium contained in the rock and form a solution of monocalcium phosphate and phosphoric acid. After removal of solids, this solution can be treated with sulfuric acid in a gypsum crystallizer to form gypsum and the phosphoric acid product wherein filterable gypsum crystals are obtained by maintaining a total SO.sub.3 content of 1.5-4 wt. % in a first crystallizer and neutralizing the SO.sub.3 in a second crystallizer.
    Type: Grant
    Filed: July 6, 1983
    Date of Patent: October 30, 1984
    Assignee: Pennzoil Company
    Inventors: John B. Sardisco, Dysart E. Holcomb, Erhart K. Drechsel, deceased
  • Patent number: 4472368
    Abstract: An economical process for treating the acidic pond water to be used in the internal grinding circuit of a wet process phosphoric acid plant. Water is added to a quantity of a hydratable calcium compound, such as quicklime, to form a slaked lime slurry. A sufficient quantity of the slaked lime slurry is reacted with the acidic pond water to obtain a low fluoride solution having a fluoride content less than about 300 ppm and a pH in the range from about 2.0 to about 3.0, preferentially in the range 2.6-2.8, whereby calcium fluoride is precipitated. The precipitate bearing low fluoride solution is then clarified and the precipitate removed as underflow from the clarifier and transferred to the gypsum pond. In the preferred embodiment, the clarified low fluoride water is fed to the ball mill and is mixed with the phosphate rock being crushed.
    Type: Grant
    Filed: December 27, 1982
    Date of Patent: September 18, 1984
    Assignee: Agrico Chemical Company
    Inventors: Padraic S. O'Neill, Charles W. Weston, Kyle D. Clevenger, Jesse S. Chang
  • Patent number: 4469504
    Abstract: A rapid, low temperature process for solubilizing phosphate rocks having high content of foreign matter or a low phosphorus content to obtain: (a) a slow release fertilizer of the NP type; (b) phosphoric acid of high concentration plus MAP; and (c) DAP.
    Type: Grant
    Filed: August 24, 1982
    Date of Patent: September 4, 1984
    Assignee: Petroleo Brasileiro S.A. - Petrobras
    Inventors: Hossam Abdel-Hehim, Wagner C. Coelho, Gloria M. G. Soares
  • Patent number: 4462972
    Abstract: A process for producing fertilizer-grade phosphoric acid is disclosed. In the process, a rock slurry is produced from a predetermined quantity of phosphate rock and a predetermined quantity of pond water neutralized with ammonia. A predetermined rate of sulfuric acid is added to the rock slurry to produce a reaction mixture. The improvement comprises maintaining an excess of sulfate ion in the reaction mixture.
    Type: Grant
    Filed: July 19, 1982
    Date of Patent: July 31, 1984
    Assignee: CF Industries, Inc.
    Inventor: William A. Satterwhite
  • Patent number: 4452770
    Abstract: A wet process for producing phosphoric acid and phosphoanhydrite by acidulation of phosphate rock with a phosphoric acid/sulfuric acid mixture containing a very high recycle content of small sized anhydrite seed crystals. A strong phosphoric acid is obtained having a concentration of at least about 35% P.sub.2 O.sub.5. Further, the phosphoanhydrite may be readily converted to an industrially usable gypsum product.
    Type: Grant
    Filed: December 14, 1981
    Date of Patent: June 5, 1984
    Assignee: United States Gypsum Company
    Inventors: Jay W. Palmer, John C. Gaynor
  • Patent number: 4447403
    Abstract: An improved method and apparatus for effecting a substantial reduction in retention time of oxidation processes by the autoclave oxidation of ion species dissolved in aqueous solutions. In one embodiment, the invention provides for oxidation of dissolved reduced ion species including ferrous iron (Fe.sup.+2), uranium (U.sup.+4) and vanadium (V.sup.+3) from wet process phosphoric acids, or for conditioning of aqueous solutions for other uses, such as corrosion control, by raising the valence state of dissolved ion species. In accordance with the present invention, pure oxygen, present in quantity of at least 94% by volume, is utilized as an oxidizing agent with specified process parameters: temperature, pressure and mixing conditions in an autoclave reaction vessel.
    Type: Grant
    Filed: September 4, 1979
    Date of Patent: May 8, 1984
    Assignee: J. R. Simplot Company
    Inventors: Laurence W. Bierman, Gary L. Long, David Bortner
  • Patent number: 4443421
    Abstract: An emobodiment of a process for filtration of a slurry containing fine particles is a process comprising:(a) filtering phosphoric acid containing sludge-forming particulate impurities through a fabric filter whereby particulate impurities are separated from the phosphoric acid and retained on the surface of the fabric filter to form a filter cake comprising particulate impurities and entrained phosphoric acid;(b) contacting the filter cake with a wash fluid (e.g., water) to remove a major portion of the entrained phosphoric acid from the filter cake, thereby forming a washed filter cake; and,(c) removing the washed filter cake to expose a fresh surface of the fabric filter, for contacting with additional phosphoric acid containing particulate impurities.Preferably, the washed filter cake is removed by the introduction of pressurized air to the side of the fabric filter opposite the washed filter cake.
    Type: Grant
    Filed: March 16, 1982
    Date of Patent: April 17, 1984
    Assignee: Occidental Chemical Corporation
    Inventors: Charles M. Hollifield, Teddy D. Smith
  • Patent number: 4439407
    Abstract: A process for the improved filterability of wet process phosphoric acid which comprises maintaining the ratio of ferric ion to ferrous ion in the wet process phosphoric acid above about 1.0 when the total iron concentration of the product wet process phosphoric acid is in the range of from about 0.5% Fe to about 0.9% Fe. The ratio of ferric ion to ferrous ion may be controlled by controlling the temperature in the final stage of a multi-stage calcining process, addition of iron in the form of a compound which yields ferric ion upon dissolution, the oxidation of the iron in the wet process phosphoric acid, or a combination of the above.
    Type: Grant
    Filed: January 19, 1983
    Date of Patent: March 27, 1984
    Assignee: Agrico Chemical Company
    Inventor: Kenneth L. Parks
  • Patent number: 4435372
    Abstract: The concentration of impurities in wet-process phosphoric acid limits the usefulness of the acid for the production of fertilizers, feedgrade phosphate and detergents. The aluminum, magnesium, and fluoride impurities are removed with the calcium sulfate hemihydrate filter cake by hydrolyzing and recycling the off-gas scrubber solutions in the presence of a ferric iron catalyst. The aluminum and magnesium are reduced to less than 0.1 percent in the acid product by the precipitation of (Ca,Mg)Al.sub.2 F.sub.8 .multidot.2H.sub.2 O, which is acid insoluble and suitable for storage with the byproduct calcium sulfate. Ferric iron also serves as a catalyst for the simultaneous precipitation of (Na,K).sub.2 SiF.sub.6. Subsequent additions of potassium as, for example, in the teachings of Gilbert (U.S. Pat. No. 3,338,675), can then be applied to obtain a purified phosphoric acid product suitable for most commercial applications.
    Type: Grant
    Filed: January 17, 1983
    Date of Patent: March 6, 1984
    Assignee: Tennessee Valley Authority
    Inventors: Alva W. Frazier, Ewell F. Dillard
  • Patent number: 4431610
    Abstract: An economically advantageous method of recovering uranium from a wet process phosphoric acid solution through the steps of making hemihydrate gypsum contact with the acid solution thereby transferring uranium from the acid solution into the gypsum, dispersing the U-containing gypsum separated from the acid solution in water to convert the gypsum to dihydrate accompanied by the transfer of uranium into water, separating the obtained U-containing aqueous solution from the dihydrate gypsum, and adding precipitant such as an inorganic base to the aqueous solution to form a precipitate comprising an insoluble uranium compound. The contact of hemihydrate gypsum with the phosphoric acid solution is preferably preceded by reduction of hexavalent uranium in the acid solution to tetravalent uranium, and can be achieved either by adding hemihydrate gypsum to the acid solution or by converting dihydrate gypsum to hemihydrate within the acid solution preferably preceded by the addition of sulfuric acid.
    Type: Grant
    Filed: February 22, 1982
    Date of Patent: February 14, 1984
    Assignee: Central Glass Company Limited
    Inventors: Soichi Asagao, Shinsuke Nakagawa, Naoki Okada, Seizi Yoshikawa
  • Patent number: 4430313
    Abstract: Black wet process phosphoric acid contains suspended and precipitated organic material and inorganic material. Upon standing, the precipitated material (mostly gypsum) forms a cake that is very difficult to be resuspended. By adding small amounts of nitric acid to the black acid, the nature of the precipitated material is changed and it does not cake and can be easily resuspended with slight agitation. Thus, the treated black acid can be shipped and stored and it can be clarified at the destination by adding water.
    Type: Grant
    Filed: April 11, 1983
    Date of Patent: February 7, 1984
    Assignee: Mobil Oil Corporation
    Inventors: Mark D. LaVanture, George L. Walker
  • Patent number: 4427641
    Abstract: In preparing wet process phosphoric acid by decomposing a phosphate rock containing uranium with sulfuric acid and phosphoric acid on condition that hemihydrate gypsum is formed in an acid solution either at the stage of decomposing the phosphate rock or subsequently, uranium contained in the phosphate rock can almost entirely be retained in the obtained phosphoric acid solution by forming the hemihydrate gypsum in the presence of an oxidizing agent, such as a soluble chlorate, hydrogen peroxide or oxygen gas, in the acid solution in a quantity sufficient to render the entire uranium dissolved in the acid solution hexavalent because hemihydrate gypsum adsorbs almost exclusively tetravalent ions of uranium. The uranium is then recovered.
    Type: Grant
    Filed: July 27, 1981
    Date of Patent: January 24, 1984
    Assignee: Central Glass Company Limited
    Inventors: Seizi Yoshikawa, Ryuichi Nakamura
  • Patent number: 4415543
    Abstract: This disclosure concerns a process for treating phospho-gypsum waste product from the wet process method of making phosphoric acid including the steps of water washing the phospho-gypsum to remove all but an acceptable level of fluorine before the phospho-gypsum is calcined. The process allows the use of high sulfur coal for the production of steam if desired for use in the overall process. The process also allows for production of SO.sub.3 from part of the phospho-gypsum in an electric furnace to enrich the SO.sub.2 stream for making sulfuric acid.
    Type: Grant
    Filed: January 25, 1982
    Date of Patent: November 15, 1983
    Inventors: Eddie K. Wilson, Sr., Silvio J. Spigolon
  • Patent number: 4405575
    Abstract: This invention comprises a method for removing fluorine from natural phosphates, superphosphate materials and wet process phosphoric acids starting materials comprising(a) admixing rock phosphate having a fluorine content above that desired with an acid mixture within the range of rock:acid mixture of about 0.8 to 1 and 1:1.4 by weight;(b) said acid mixture being substantially concentrated phosphoric acid and concentrated sulfuric acid in a range of phosphoric:sulfuric of about 1:1 to 5:1 by weight;(c) said admixing being at a temperature in the range of 215.degree. to 265.degree. F. while adding water in an amount of up to about 12% by weight of the total mixture and then subjecting the above charge;(d) in a first heating stage adding (1) recycle in an amount substantially of recycle to charge of 1:1 to 10:1 by weight (2) and water while heating to a temperature in the range of 300.degree. F. to 400.degree. F.
    Type: Grant
    Filed: April 23, 1982
    Date of Patent: September 20, 1983
    Inventor: Albert E. Henderson
  • Patent number: 4402923
    Abstract: A phosphate rock slurry, which may be used in the production of wet process phosphoric acid, is provided by wet grinding the rock with partially neutralized, acid water.In one aspect, wet process phosphoric acid is made by advantageously recycling mineral acid waste water effluent of the process. All or a portion of the effluent can be at least partially neutralized with neutralizing agent, e.g., by contact with the base-forming constituents of phosphate rock or extraneous neutralizing agent, e.g., preferably ammonia, to provide a mixture which is wet ground to produce a processable slurry. In one particularly preferred aspect, all of the acid water is at least partially neutralized with phosphate rock and a portion of this acid water is advantageously further neutralized with an extraneous neutralizing agent. The slurry is provided by such neutralization at a pH compatible with the milling, e.g., grinding, media utilized.
    Type: Grant
    Filed: September 2, 1981
    Date of Patent: September 6, 1983
    Assignee: Davy McKee Corporation
    Inventor: Warren H. Lang
  • Patent number: 4402919
    Abstract: A process for solubilizing uranium and other values in an ore containing the same together with aluminum and phosphorus and effecting regeneration of a mineral acid employed to solubilize the ore. The regeneration is effected by heating the spent acid solution resulting from solubilization of the ore in a reaction zone to a temperature above 100.degree. C. while maintaining at least the autogenic pressure of the heated solution within the reaction zone. The treatment causes aluminum phosphate to precipitate from the solution while simultaneously causing regeneration of at least a portion of the mineral acid in the solution that was consumed to originally solubilize the ore. The dissolved uranium and other elements of value can be recovered from the solution, either before or after acid regeneration, by any known technique. The regenerated mineral acid then can be used to solubilize fresh ore.
    Type: Grant
    Filed: March 19, 1981
    Date of Patent: September 6, 1983
    Assignee: Kerr-McGee Corporation
    Inventors: Dale Denham, Roland Schmidt
  • Patent number: 4393030
    Abstract: Phosphate is upgraded to remove slimes therefrom by a process which comprises the steps of:(a) contacting the phosphate ore with a phosphoric acid solution having a concentration of about 1 to 20 weight percent in a desliming unit for a sufficient time to form a suspension containing the slimes and the calcium and phosphate components;(b) passing said suspension through a solids separator to separate deslimed phosphate ore from the slime suspension and recovering the deslimed phosphate ore;(c) removing the slime suspension to a separator to separate the slime solids from the filtrate liquids; and(d) recycling the filtrate liquids to the desliming unit to provide at least a portion of the phosphoric acid solution.
    Type: Grant
    Filed: January 12, 1982
    Date of Patent: July 12, 1983
    Assignee: Pennzoil Company
    Inventors: John B. Sardisco, Dysart E. Holcomb
  • Patent number: 4393032
    Abstract: Phosphate rock, including low grade phosphate ore, is treated to recover phosphoric acid and other valuable products by a series of steps including contacting phosphate ore with a weak phosphoric acid to form a suspension of at least a portion of the slimes contained in the ore so that the slimes can be separated from the ore, and separating the slimes to provide a deslimed phosphate ore. Deslimed phosphate rock is solubilized with phosphoric acid to convert at least a portion of the calcium contained in the rock and form a solution of monocalcium phosphate and phosphoric acid. After removal of solids, this solution can be treated with sulfuric acid in a gypsum crystallizer to form gypsum and the phosphoric acid product wherein filterable gypsum crystals are obtained by maintaining a total SO.sub.3 content of 1.5-4 wt. % in a first crystallizer and neutralizing the SO.sub.3 in a second crystallizer.
    Type: Grant
    Filed: January 12, 1982
    Date of Patent: July 12, 1983
    Assignee: Pennzoil Company
    Inventors: Erhart K. Drechsel, Dysart E. Holcomb, John B. Sardisco
  • Patent number: 4391784
    Abstract: Foam generated during the digestion of phosphate rock is removed from the slurry either by overflow, mechanical sweeps, or by vacuum from strategically located nozzles connected to vacuum lines. The foam, after liquefaction, is returned to the filter where it results in improved filtration and return of soluble P.sub.2 O.sub.5.
    Type: Grant
    Filed: August 18, 1981
    Date of Patent: July 5, 1983
    Inventors: Richard N. Hill, Sr., Charles D. B. Hill
  • Patent number: 4387083
    Abstract: A process for preparing calcium sulphate anhydrite from calcium sulphate dihydrate so that the calcium sulphate anhydrite crystals will have a predetermined average particle size. The process is conducted by recrystallizing the calcium sulphate dihydrate at moderate temperatures in the presence of sulphuric acid having a concentration of 40-65% wt. calculated relative to the quantity of liquid phase in the recrystallization mixture. The particle size of the final product is controlled by varying the temperature and residence time of the recrystallization mixture in recrystallization zone and by varying the temperature in an inverse relationship to the acid concentration.Calcium sulphate anhydrite crystals having an average particle size between about 0.5 and about 3 micron are produced by maintaining the temperature between about 40.degree. C. and 90.degree. C. and the residence time from about 5 minutes to less than about 30 minutes.
    Type: Grant
    Filed: April 24, 1981
    Date of Patent: June 7, 1983
    Assignee: Stamicarbon, B.V.
    Inventors: Cornelis A. M. Weterings, Johannes A. Janssen
  • Patent number: 4387077
    Abstract: Recovery of yttrium, lanthanides and radium free calcium sulphate in a phosphoric acid process by digesting phosphate rock with an excess of phosphoric acid in the presence of more than about 5 wt.% of SO.sub.4 -ions calculated to the amount of phosphate rock, separating out the insoluble residue and recovering yttrium and lanthanides therefrom, precipitating calcium sulphate from the remaining solution with sulphuric acid and separating this calcium sulphate from the resulting phosphoric acid solution.
    Type: Grant
    Filed: December 14, 1981
    Date of Patent: June 7, 1983
    Assignee: Stamicarbon, B.V.
    Inventors: Cornelis A. M. Weterings, Louis H. M. Ramakers, Johannes A. Janssen
  • Patent number: 4379776
    Abstract: Aluminum fluorophosphate can be produced by the aging of phosphoric acid containing fluorine and aluminum, preferably phosphoric acid analyzing in the range of about 15-45 weight percent P.sub.2 O.sub.5, 2-4% Al.sub.2 O.sub.3 and 1-2% fluorine. One process involves digestion of phosphate ore matrix in recycled phosphoric acid, filtration of the insoluble residue, precipitation and filtration of gypsum, and aging of the product acid to precipitate the aluminum impurity as an aluminum fluorophosphate compound. The aluminum fluorophosphate can be decomposed (as by heating at about 195.degree. C.) to produce HF and aluminum phosphate.
    Type: Grant
    Filed: July 13, 1981
    Date of Patent: April 12, 1983
    Assignee: Occidental Research Corporation
    Inventors: Gary L. Beer, Elie Chemtob
  • Patent number: 4377560
    Abstract: A process for producing low aluminum content phosphoric acid from high aluminum matrix comprises digesting the matrix in phosphoric acid; adding a flocculant to consolidate gelatinous or fine undigested solids; separating the flocculated solids from the mother liquid comprising monocalcium phosphate; acidifying the monocalcium phosphate with sulfuric acid to precipitate solid calcium sulfate and simultaneously adding at least one sodium or potassium compound or both to co-precipitate some of the soluble fluoride with the gypsum; separating the product phosphoric acid from the precipitated solids; recycling part of the lower fluoride content phosphoric acid back to the digestion step; and, aging the remainder of the product phosphoric acid until a precipitate of aluminum fluorophosphate forms and separating the precipitate to produce a low aluminum content phosphoric acid. Additional fluorine (e.g., a fluoride compound) can be added to accellerate formation of the aluminum fluorophosphate.
    Type: Grant
    Filed: July 13, 1981
    Date of Patent: March 22, 1983
    Assignee: Occidental Research Corporation
    Inventor: Fernando Ore'
  • Patent number: 4376756
    Abstract: Phosphoric acids of significantly different content of soluble impurities, especially magnesium compounds, can be blended to produce a phosphoric acid with a decreased tendency for forming detrimental solids when converted to a liquid fertilizer or on storage, or during transportation as when the acid is transported by ocean vessel or railroad tank car. The blending can be effected either before or after a concentration step or steps (e.g., evaporation to "merchant grade" or to superphosphoric acid). For example, wet process phosphoric acid produced by a dihydrate or gypsum process can be blended with a phosphoric acid produced by a hemihydrate process.
    Type: Grant
    Filed: December 5, 1980
    Date of Patent: March 15, 1983
    Assignee: Occidental Chemical Company
    Inventors: Harold E. Mills, David L. Murdock, Richard M. Ramer, Francis M. Sale
  • Patent number: 4367197
    Abstract: Methods for control of excessive corrosion in wet process phosphoric circuits are effected by oxidation of reduced ion species in the acid with maintenance of EMF value of the acid above about 190 millivolts (S.C.E. reference) through the digestion circuit. Supplementary monitoring is by a ceric red-ox titration procedure. In one embodied form, the present invention is utilized to control corrosion in a phosphoric acid plant digestion system (and subsequent processing equipment) operating by a dihydrate (gypsum) process even when such a process employs a calcined western U.S. phosphate ore feed from a relatively highly carbonaceous ore. The invention is also applicable for treating wet process phosphoric acid in phosphoric acid plants having a digester system operating by a hemihydrate process.
    Type: Grant
    Filed: March 2, 1981
    Date of Patent: January 4, 1983
    Assignee: J. R. Simplot Company
    Inventors: Gary L. Long, Roger B. Humberger
  • Patent number: 4363786
    Abstract: An apparatus useful for the preparation of phosphoric acid from phosphate rock and a strong acid, comprises a closed vessel, a draft tube, means connected to the inner walls of said vessel amd mounting said draft tube in a vertical position within said vessel, an agitator positioned within said draft tube, a shaft for said agitator mounted axially of said vessel and extending into said draft tube, an inlet conduit to said vessel for introducing a feed slurry (e.g.
    Type: Grant
    Filed: September 22, 1980
    Date of Patent: December 14, 1982
    Assignee: Occidental Chemical Corp.
    Inventors: Allen S. Adams, Michael B. Caesar
  • Patent number: 4362705
    Abstract: Phosphate rock is digested with H.sub.2 SO.sub.4 into phosphoric acid and gypsum, the latter is separated off, washed and converted into anhydrite. After this first wash the gypsum is divided into a minor portion of fine crystals, which is discharged, and into a major portion of coarse crystals, which is subjected to a second wash, thereafter recrystallized into anhydrite by means of concentrated H.sub.2 SO.sub.4, the anhydrite being separated and washed and the recrystallization liquor returned to the digestion zone. The washing liquor obtained from the anhydrite wash is used for the second gypsum wash, the washing liquor obtained from this second wash is, together with water, used for the first gypsum wash, whereas the washing liquor obtained in this first wash is returned to the digestion zone. In this way practically all gypsum formed can be converted into anhydrite, while substantially all water can be functionally used without dilution of the H.sub.3 PO.sub.4 -product.
    Type: Grant
    Filed: July 15, 1981
    Date of Patent: December 7, 1982
    Assignee: Stamicarbon, B.V.
    Inventor: Cornelis A. M. Weterings
  • Patent number: 4350671
    Abstract: Phosphoric acid is produced by a wet process in a homogeneous medium from calcium phosphate ore, sulphuric acid and a continuously added aqueous solution of recycled acid.Part of the phosphate is treated in a primary reaction medium, prepared separately and differing in composition from the final medium sought. By regulating the compositions of the various reaction media, the present process advantageously increases the concentration of the phosphoric acid produced and/or enhances the quality of filtration, along with other advantages.The process can advantageously be applied for the economic treatment of low-grade, poorly reactive or unground phosphates.
    Type: Grant
    Filed: October 22, 1980
    Date of Patent: September 21, 1982
    Assignee: Rhone-Poulenc Industries
    Inventors: Bernard Bigot, Jean-Francois Gielly
  • Patent number: 4332779
    Abstract: An improved process for the filtration of phosphoric acid wherein the prefilt phosphoric acid produced from the "wet process" is conditioned with a flocculant and a dispersant and thereafter filtered to concentrate the acid.
    Type: Grant
    Filed: November 24, 1980
    Date of Patent: June 1, 1982
    Assignee: American Cyanamid Company
    Inventors: Michael J. Thibodeau, James S. Balcerski
  • Patent number: 4325928
    Abstract: Phosphate rock can be heat treated at 380.degree.-600.degree. C. to convert the organics to filterable carbon and the rock converted to wet process phosphoric acid of reduced color and with reduced foaming. Rocks having high acid soluble organics but low total organics, and rocks containing a high content of acid insoluble heat labile iron sulphide are especially suitable.
    Type: Grant
    Filed: February 22, 1980
    Date of Patent: April 20, 1982
    Assignee: Albright & Wilson Limited
    Inventor: Edward J. Lowe
  • Patent number: 4321238
    Abstract: High temperature phosphate are burning process in which the ore is preheated by gases produced by the combustion of a fuel in the burning zone, and then enters the burning zone and is cooled by a current of cool air which is used, at least partly, as combustion in the burning zone, characterized by the fact that burning is carried out in a static combustion chamber in which the preheated ore is placed in suspension in the current of air which has cooled the burned ore and in which fuel is injected, whereby the combustion of air and fuel supplies the required heat for burning, and that the retention time of the ore in the combustion chamber is less than thirty seconds, the burned ore being blow out of the chamber by the gases resulting from the combustion of the fuel injected into the chamber.
    Type: Grant
    Filed: April 16, 1979
    Date of Patent: March 23, 1982
    Assignee: Fives-Cail Babcock
    Inventor: Jean-Pierre Henin
  • Patent number: 4321244
    Abstract: A process for treating a rock essentially constituted by calcium aluminophosphate, comprising the treatment of the ground rock with a concentrated sulfuric acid in stoichiometric excess with respect to calcium and aluminum, at a temperature of above about 120.degree. C., for a time between a few minutes and about 5 hours, followed by controlled water take-up. Subsequently, a residue containing substantially all the calcium and the aluminum of the rock and a solution of the acids serving to digest a tricalciumphosphate charge are separated. The process is particularly suitable for the treatment of Thies phosphate ore.
    Type: Grant
    Filed: August 5, 1980
    Date of Patent: March 23, 1982
    Assignee: Groupement Franco-Senagalais d'Etudes et de Recherches Industrielles
    Inventors: Claude Magnier, Jean Grosbois