Patents Represented by Attorney Robert A. Petrusek
  • Patent number: 4292067
    Abstract: Crystalline urea phosphate mixed with sufficient quantities of previously produced urea-ammonium polyphosphate liquid to provide fluidity is pyrolyzed batchwise in one stage to give molten urea ammonium polyphosphate containing up to 50 percent of the phosphate as polyphosphate. Water or aqua ammonia can be substituted for the polyphosphate liquid if certain prescribed steps in proper sequence are followed. Heat from ammoniation of the urea phosphate provides all of the heat for pyroloysis. The molten urea-ammonium polyphosphate is then processed into high-analysis liquid fertilizer.
    Type: Grant
    Filed: February 12, 1980
    Date of Patent: September 29, 1981
    Assignee: Tennessee Valley Authority
    Inventors: John M. Stinson, James R. Burnell
  • Patent number: 4287053
    Abstract: A phosphate ore flotation process subjecting a phosphate ore containing carbonate mineral impurities to froth flotation in the presence of phosphate depressants, said depressants are alkyl phosphonic acids, and a carbonate collector, said collector is fatty acids, removing the separated carbonate minerals from the overflow, and recovering the phosphate value in the underflow. The process of the present invention can be performed either prior to or after the separation of siliceous matter from phosphate minerals by methods known in the art.
    Type: Grant
    Filed: December 22, 1980
    Date of Patent: September 1, 1981
    Assignee: Tennessee Valley Authority
    Inventors: James R. Lehr, Shuang-shii Hsieh
  • Patent number: 4282089
    Abstract: A phosphate ore flotation process subjects a phosphate ore containing silica and silicates to froth flotation in the presence of a collector, said collector being a C.sub.54 high molecular weight tribasic acid comprising three carboxylic functional groups, recovering the phosphate concentrate from the overflow, and removing the separated silica and silicates in the underflow. The tribasic acids should be used in conjunction with fuel oil, not only to reduce the reagent consumption, but also to increase the grade and recovery of phosphate concentrate. The selectivity of this collector is so great that an acceptable phosphate rock concentrate can be obtained from the phosphate ore in a single anionic circuit.
    Type: Grant
    Filed: July 14, 1980
    Date of Patent: August 4, 1981
    Assignee: Tennessee Valley Authority
    Inventors: Shuang-Shii Hsieh, Dennis G. Brooks
  • Patent number: 4256479
    Abstract: A process for granulating crystalline fertilizer borate to produce a product with exceptionally satisfactory physical and chemical properties in regard to bulk blending with other fertilizer blend materials and also in regard to storage and handling properties. The process involves specialized procedures in processing the solid feedstock and granulating the solids with use of a small amount of acid solution. Product drying is not required.
    Type: Grant
    Filed: March 5, 1979
    Date of Patent: March 17, 1981
    Assignee: Tennessee Valley Authority
    Inventor: Cecil P. Harrison
  • Patent number: 4246248
    Abstract: Particulate carbonaceous matter in ammonium polyphosphate liquid made from impure wet-process phosphoric acid is removed batchwise by intimately mixing the liquid with a combination of selected organic flocculating agents and then allowing the mixture to separate. The particulate carbonaceous matter floats and the clarified liquid is withdrawn from the bottom of the separation vessel. The particulate carbonaceous matter, a minor portion of the input ammonium polyphosphate liquid, and the flocculating agents are intimately remixed with fresh black ammonium polyphosphate liquid to allow reuse of flocculant not combined with the original particulate carbonaceous material. The flocculants may be reused as many as five times. The particulate carbonaceous matter, the inactive flocculant, and a minor portion of the input ammonium polyphosphate liquid are then processed into fluid or solid fertilizers. In some instances, more flocculant is added to the mixing vessel.
    Type: Grant
    Filed: May 7, 1979
    Date of Patent: January 20, 1981
    Assignee: Tennessee Valley Authority
    Inventors: Kenneth E. McGill, Eugene B. Wright, Jr.
  • Patent number: 4239739
    Abstract: Purified diammonium phosphate is produced by neutralizing relatively pure melamine orthophosphate, prepared from wet-process phosphoric acid, with ammonia in a hot solution of diammonium phosphate to give a slurry of melamine in concentrated diammonium phosphate solution. The liberated melamine is virtually insoluble in concentrated diammonium phosphate solutions; it is filtered from the hot mixture, washed, and recycled to produce more melamine phosphate by reaction with wet-process phosphoric acid. The hot, concentrated diammonium phosphate filtrate is cooled to precipitate purified diammonium phosphate crystals. The product is separated from its mother liquor by filtration, and the resulting filtrate is recycled to the reactor. The small amount of impurities introduced with the melamine phosphate are removed partly with the liberated melamine and partly by centrifugation of the diammonium phosphate solution. The only starting materials for the process are phosphoric acid and ammonia.
    Type: Grant
    Filed: November 6, 1979
    Date of Patent: December 16, 1980
    Assignee: Tennessee Valley Authority
    Inventors: Richard C. Sheridan, John F. McCullough
  • Patent number: 4238459
    Abstract: A method of selectively extracting calcite and dolomite away from apatite in phosphate rock or phosphatic limestone wherein the phosphate rock or phosphatic limestone is treated with a mixture of sulfur dioxide, water, and a carbonyl compound. Solids are separated from the liquid phase. The solids consist principally of apatite admixed with clay, quartz, and other accessory minerals originally in the rock. The solids are heated to drive off adhering sulfur dioxide, water, and carbonyl. The liquid phase consists of carbonyl, water, sulfur dioxide, and magnesium and calcium ions. Heating this liquid preferentially precipitates CaSO.sub.3.1/2H.sub.2 O. This solid is filtered off and the filtrate further heated to precipitate MgSO.sub.3.3H.sub.2 O largely free of CaSO.sub.3.1/2H.sub.2 O. All off gas and filtrate is returned to the process.
    Type: Grant
    Filed: June 18, 1979
    Date of Patent: December 9, 1980
    Assignee: Tennessee Valley Authority
    Inventors: John F. Phillips, Jr., Guerry H. McClellan, John F. McCullough
  • Patent number: 4237106
    Abstract: Process for the production of solid ammonium polyphosphate in which ammonium phosphate melt is prepared in a pipe reactor and is solidified by controlled cooling to form crystals of a size and in quantity suitable to yield a hard, nontacky, and friable solid. Wet-process phosphoric acid is ammoniated in a pipe reactor to an NH.sub.3 :H.sub.3 PO.sub.4 mole ratio of about 1.0, and the resulting melt is agitated and simultaneously partially cooled by application of recycled pulverized product or air or a water jacket. The partially cooled melt is then solidified continuously into nontacky sheets on a water-cooled metal surface using warm water to slowly remove sensible heat and heat of crystallization. Up to about 55 percent or higher of the P.sub.2 O.sub.5 in the product may be polyphosphate. Without controlled cooling, a supersaturated solution or a microcrystalline texture results and the product is rather like a gel.
    Type: Grant
    Filed: April 9, 1976
    Date of Patent: December 2, 1980
    Assignee: Tennessee Valley Authority
    Inventors: Gordon C. Hicks, George H. Megar
  • Patent number: 4236911
    Abstract: A method of purifying filter-grade wet-process phosphoric acid, then converting the purified phosphoric acid directly to ammonium phosphate without first concentrating the phosphoric acid. The wet-process phosphoric acid is treated with a mixture of ammonia or an ammonium salt and acetone near or at the boiling point of the mixture. Solids are separated from the phosphoric acid liquid phase. The solids are a mixture of metal phosphates, gypsum, and fluosilicates. Adhering phosphoric acid is washed free of the solids with fresh acetone. Wash liquor is combined with purified phosphoric acid. Gaseous ammonia is added to the phosphoric acid-acetone extract in the ratio necessary to produce either monoammonium phosphate (MAP) or diammonium phosphate (DAP). Ammonium phosphate is filtered from the acetone-water mother liquor, then, depending on the level of ammonium phosphate left in the mother liquor and the type of ammonium phosphate produced (MAP or DAP), the mother liquor is treated in one of several ways.
    Type: Grant
    Filed: November 8, 1979
    Date of Patent: December 2, 1980
    Assignee: Tennessee Valley Authority
    Inventor: John F. McCullough
  • Patent number: 4217128
    Abstract: Crystalline urea phosphate is pyrolyzed in one stage to give molten urea ammonium polyphosphates that contains up to 95 percent of the phosphate as polyphosphate. These are then processed into high-analysis solid or liquid fertilizers. Addition of urea to the process to maintain a urea:biuret ratio of at least 16 prevents precipitation of biuret in the liquid fertilizers.
    Type: Grant
    Filed: July 13, 1979
    Date of Patent: August 12, 1980
    Assignee: Tennessee Valley Authority
    Inventors: John M. Stinson, Horace C. Mann, Jr., John F. McCullough
  • Patent number: 4213924
    Abstract: An improved process for the granulation or coating of hygroscopic or nonhygroscopic materials where melt is sprayed onto cascading granules of common or uncommon substrate in an enclosed vessel, and where the heat given off by solidification of the melt is absorbed by evaporation of water. The water is atomized into the granulator as an extremely fine mist and evaporation is effected without impingement of mist on granules or granulator internals. An equation is developed which mathematically represents the thermodynamics of the process and specific values are presented for variables when granulating sulfur or urea.
    Type: Grant
    Filed: June 19, 1978
    Date of Patent: July 22, 1980
    Assignee: Tennessee Valley Authority
    Inventor: Arthur R. Shirley, Jr.
  • Patent number: 4180545
    Abstract: A method of recovering uranium from wet-process phosphoric acid wherein the acid is treated with a mixture of an ammonium salt or ammonia, a reducing agent, and then a miscible solvent. Solids are separated from the phosphoric acid liquid phase. The solid consists of a mixture of metal phosphates and uranium. It is washed free of adhering phosphoric acid with fresh miscible solvent. The solid is dried and dissolved in acid whereupon uranium is recovered from the solution. Miscible solvent and water are distilled away from the phosphoric acid. The distillate is rectified and water discarded. All miscible solvent is recovered for recycle.
    Type: Grant
    Filed: August 25, 1977
    Date of Patent: December 25, 1979
    Assignee: Tennessee Valley Authority
    Inventors: John F. McCullough, John F. Phillips, Jr., Leslie R. Tate
  • Patent number: 4169882
    Abstract: Impure wet-process phosphoric acid is treated with urea by known processes to produce relatively pure urea phosphate which is then treated with oxalic acid to give solid urea oxalate and purified phosphoric acid product. The urea oxalate is either treated with ammonia to give urea and ammonium oxalate or it is pyrolyzed to produce urea and oxamide.
    Type: Grant
    Filed: November 13, 1978
    Date of Patent: October 2, 1979
    Assignee: Tennessee Valley Authority
    Inventor: Richard C. Sheridan
  • Patent number: 4152402
    Abstract: An improved process for the purification of wet-process phosphoric acid (WPPA) with acetone and ammonia. The main product is the purified acid and a byproduct is the impure acid fraction in a liquid form containing most of the impurities including the added ammonia. The WPPA is mixed with acetone and the specified amount of ammonia to form two liquid phases that separate rapidly. The top layer contains about 75 percent of the phosphoric acid, nearly all the acetone, and a small fraction of the impurities. The bottom liquid layer has a viscosity usually in the range of 40 to 2500 centipoises, depending on the acid concentration and the amount of ammonia used. The acetone is distilled from the two liquid phases for recycle to the process.
    Type: Grant
    Filed: February 24, 1978
    Date of Patent: May 1, 1979
    Assignee: Tennessee Valley Authority
    Inventors: Henry K. Walters, Jr., Yong K. Kim, John D. Hatfield
  • Patent number: 4139597
    Abstract: A process for the removal and recovery of sulfur oxides from gas streams by contacting the gas stream with an aqueous suspension of melamine whereupon a mixture of solid, hydrated melamine sulfites, hydrated melamine sulfate is formed. The solids are separated from the reaction product and the clarified liquid recycled. The solids are then heated to temperatures up to 200.degree. C. to decompose the hydrated melamine sulfites into free melamine, gaseous water, and sulfur dioxide, and the gaseous water and sulfur dioxide withdrawn as product. The hot solids are cooled and split into two portions. One portion is recycled and the other portion is treated with a base stronger than melamine to decompose the contained melamine sulfate into free melamine and a basic sulfate salt solution. The basic sulfate salt solution is separated from the melamine and withdrawn as product and the melamine is recycled to the process.
    Type: Grant
    Filed: November 11, 1977
    Date of Patent: February 13, 1979
    Assignee: Tennessee Valley Authority
    Inventors: John J. Kohler, Joe Gautney, Yong K. Kim, John F. McCullough
  • Patent number: 4134750
    Abstract: A process for the production of fertilizers from phosphoric and sulfuric acids, anhydrous ammonia, and urea, and more specifically, the production of high-analysis granular ammonium phosphates, ammonium phosphate sulfates, and urea-ammonium phosphate sulfates--some with polyphosphate contents of up to 68 percent of the total P.sub.2 O.sub.5. A specially designed pipe-cross reactor is used to produce a homogeneous melt or slurry of low moisture content from the reactants and thus eliminates the need for a preneutralizer as used in many prior-art granular fertilizer processes. In addition, because of the low melt or slurry moisture content, the dryer (also used in most of the previous processes) is eliminated. The elimination of these two items greatly simplifies pollution abatement, since both items are sources of fumes and dust.
    Type: Grant
    Filed: December 19, 1977
    Date of Patent: January 16, 1979
    Assignee: Tennessee Valley Authority
    Inventors: Melvin M. Norton, Byron R. Parker
  • Patent number: 4113842
    Abstract: A method of preparing dicalcium phosphate from phosphate rock wherein the rock is treated with a mixture of water, carbonyl, and sulfur dioxide. Solids are separated from the liquid phase. The solid phase consists of a mixture of gangue, and calcium .alpha.-hydroxysulfonate. Carbonyl and part of the sulfur dioxide are recovered from the solid by low temperature thermal decomposition. Dicalcium phosphate is precipitated from the liquid phase by partial distilling of SO.sub.2. All carbonyl is recovered for recycle.
    Type: Grant
    Filed: March 18, 1977
    Date of Patent: September 12, 1978
    Assignee: Tennessee Valley Authority
    Inventors: John F. McCullough, John F. Phillips, Jr., Leslie R. Tate
  • Patent number: 4066432
    Abstract: A process for preparing concentrated, high-grade, nitrogen-phosphate (N--P.sub.2 O.sub.5) base suspension fertilizer from wet-process or other impure orthophosphoric acids. The process involves a new procedure for the direct ammoniation of orthophosphoric acid in stages for production of fluid, high-analysis, N--P.sub.2 O.sub.5 suspension fertilizer with good physical properties. The new process contains a novel method for prevention of settling of crystals in the suspension during vibration, such as that which occurs during shipment. Settling is avoided by producing small, thin crystals of diammonium phosphate through control of the N:P.sub.2 O.sub.5 ratio and temperature in the second and third ammoniation stages.
    Type: Grant
    Filed: January 28, 1977
    Date of Patent: January 3, 1978
    Assignee: Tennessee Valley Authority
    Inventor: Thomas M. Jones
  • Patent number: 4028087
    Abstract: A process for the production of a granular fertilizer material from sludge materials discharged from scrubbing processes that remove pollutants from boiler flue gases. Waste sludge discharged from flue gas scrubber systems often contain large amounts of calcium and sulfur as well as lesser amounts of other compounds known to have plant nutrient value. The sludge is treated with an acid such as phosphoric, sulfuric or nitric, or a mixture of these, and ammonia. The resulting sludge-ammonia-acid salt mixture is combined with partially dried, previously processed solid material (recycle) in a horizontal rotating vessel. Additional ammonia and/or acid is added to the rotating vessel to cause the sludge-salt mixture to solidify and granulate. Other plant nutrients may be added to the rotating vessel during granulation. The granulated material discharged from the rotary vessel is further processed (dried, cooled, and screened) to obtain desirable moisture content and particle size.
    Type: Grant
    Filed: October 18, 1976
    Date of Patent: June 7, 1977
    Assignee: Tennessee Valley Authority
    Inventors: James J. Schultz, Vincent J. Van Pelt
  • Patent number: 4017589
    Abstract: Ammonium polyphosphates are prepared by a process which comprises heating melamine orthophosphate prepared from impure wet-process phosphoric acid in a stream of gaseous ammonia at a temperature between 150.degree. C and 210.degree. C to produce a mixture of melamine and relatively pure short-chain ammonium polyphosphates. The solid product is extracted with water to remove the ammonium polyphosphates and free the insoluble, crystalline melamine for recycle. Thus, the only starting materials consumed in the process are phosphoric acid and ammonia.
    Type: Grant
    Filed: March 17, 1976
    Date of Patent: April 12, 1977
    Assignee: Tennessee Valley Authority
    Inventors: John F. McCullough, Richard C. Sheridan