Sulfuric Acid Patents (Class 423/DIG2)
  • Patent number: 5985223
    Abstract: A process for the removal of a high percentage of NOx and SOx from the gaseous effluent of a metal pickling operation comprising passing the effluent through an aqueous scrubber, treating the gaseous effluent from the scrubber with ozone, passing the effluent from the ozone treatment through a second aqueous scrubber thereby removing at least 80 vol % of the NOx and SOx present in the original effluent. The scrubbing solutions in both of the scrubbers preferably have a pH of from 7 to 14, more preferably 10 to 14. The scrubbing solutions in both scrubbers are caustic solutions containing sodium hydroxide or calcium hydroxide. The NOx and SOx in the scrubbers are converted into nitrate salts and sulfate salts, which are removed from the scrubbers.
    Type: Grant
    Filed: June 2, 1998
    Date of Patent: November 16, 1999
    Assignee: The Boc Group, Inc.
    Inventors: Neeraj Saxena, Robert Francis Workosky, Mark H. Anderson, Shuen-Cheng Hwang
  • Patent number: 5800716
    Abstract: A process for the treatment of aqueous acidic liquors containing dissolved aluminum and/or iron compounds to produce an aluminum and/or iron sulfate water-treatment product is characterized by the combination of steps comprising contacting the liquor with a basic material capable of reacting with the dissolved aluminum and/or iron compound to precipitate aluminum and/or iron values, separating the precipitate in the form of a cake or slurry from the remaining liquor, treating the cake or slurry with sulfuric acid to re-dissolve aluminum and/or iron values and to produce a solution of aluminum and/or iron sulfate and separating suspended solid matter from the solution. The liquor may be a waste product from industrial processes or may be a mine effluent and the process avoids the need to dispose of these to waste.
    Type: Grant
    Filed: July 17, 1996
    Date of Patent: September 1, 1998
    Assignee: Laporte Industries Limited
    Inventors: Neil Clarke, John Harris Newton
  • Patent number: 5730950
    Abstract: The process will recover sulfuric acid on the 90-95% concentration range by roasting of ferrous sulfate hydrate crystals at high temperature under retort conditions. In the first step of the recovery process 6 (see FIG. 1) hydroxide slurry is reacted with the waste stream, and ferrous sulfate crystals obtained. In the second step 9 iron sulfate crystals are roasted and water of hydration reacts with sulfate and sulfur trioxide to produce sulfuric acid in a retort operation. The sulfuric acid and sulfur trioxide are condensed or absorbed in water or dilute sulfuric acid and are of a high purity, leaving iron oxide as a recovered carrier. In the third step, this iron oxide/hydroxide is reduced 13 and used to produce a slurry, which is pumped back to react with the entering sulfuric acid waste stream.
    Type: Grant
    Filed: June 25, 1996
    Date of Patent: March 24, 1998
    Assignees: Jennifer L. Klotz, Laurie J. Klotz
    Inventor: William L. Klotz
  • Patent number: 5702678
    Abstract: A method is disclosed for treating sulfur containing waste streams, comprising:a) injecting said sulfur containing waste streams into a sulfuric acid regeneration unit so as to produce a sulfur dioxide containing effluent;b) passing a portion of said sulfur dioxide containing effluent to a Claus thermal reactor, andc) diverting a portion of said portion of said sulfur dioxide containing effluent of step b to a Claus catalytic reactor that is downstream from said Claus thermal reactor in an amount sufficient to maintain the average temperature in the Claus thermal reactor to be less than 3,250.degree. F.
    Type: Grant
    Filed: July 1, 1996
    Date of Patent: December 30, 1997
    Assignees: L'Air Liquide, Air Liquide America Corporation
    Inventors: Denis Cieutat, Emmanuel Schmidt
  • Patent number: 5554355
    Abstract: A method and apparatus for forming a slurry of metal oxide in a mineral or the like (e.g. of magnesium or calcium oxide) and introducing the slurry to an acid neutralization process in a time period before substantial hydration of the oxide has occurred.
    Type: Grant
    Filed: May 18, 1995
    Date of Patent: September 10, 1996
    Assignee: PSC Technologies, Inc.
    Inventor: Thomas Miller
  • Patent number: 5547655
    Abstract: Using generated active intermediates or species simultaneously to remove water and organic compounds from the spent sulfuric acid catalyst of the alkylation of olefins and alkanes is disclosed in this invention. Over 90% water and 95% organic compounds of the spent catalyst can be removed by this invention under mild operating conditions, less than 20 atms and in the temperature range from -50.degree. to 250.degree. C. This invention provides a novel process instead of the traditional or commercial process by combustion and treatment of the spent catalyst at high temperature. It is significant to simplify comparing with the traditional process, and is a safe, simple, clean or pollutionless, and cheap one-stage process.
    Type: Grant
    Filed: November 28, 1994
    Date of Patent: August 20, 1996
    Inventors: Tse-Chaun Chou, Yi-Lin Chen
  • Patent number: 5489423
    Abstract: In order to efficiently and easily recover a spent sulfuric acid exhasuted, for example, in an acid washing liquid or in producing titanium dioxide by a sulfate method in a large amount, as highly concentrated sulfuric acid, bivalent iron ions in the spent sulfuric acid containing metal sulfate are first oxidized into trivalent iron ions, hydrochloric acid is added to such a liquid and then solvent extraction is carried out.
    Type: Grant
    Filed: October 29, 1992
    Date of Patent: February 6, 1996
    Assignee: Nittetsu Mining Co., Ltd.
    Inventors: Yasuie Mikami, Nobuyoshi Iyatomi
  • Patent number: 5409679
    Abstract: The production of titanium dioxide by the sulphate process generates waste substances such as the wash filtrates, which are formed in the washing of titanium dioxide hydrate, and waste gases which contain sulphur dioxide. In this improved process the wash filtrate is used to remove the sulphur dioxide from the waste gas while the sulphuric acid content of the wash filtrate is raised and the sulphuric acid-containing process solution thus obtained is used within the scope of the titanium dioxide production process. The waste gas and the wash filtrate are passed countercurrently through a series of several washing steps and are contacted with each other by introducing the wash liquid into the waste gas in a finely divided form in scrub towers. The sulphuric acid content of the washing fluid is stepwise changed from washing stage to washing stage. The sulphur dioxide content of the waste gas is reduced to values that may be discharged into the ambient atmosphere.
    Type: Grant
    Filed: July 5, 1990
    Date of Patent: April 25, 1995
    Assignee: Kronos, Inc.
    Inventor: Achim Hartmann
  • Patent number: 5356602
    Abstract: Aluminum sulfate that is less colored is prepared by adjusting the concentration of hydrogen peroxide in sulfuric acid to 0.1% by weight or less, and contacting the sulfuric acid with an alumina-containing compound.
    Type: Grant
    Filed: December 22, 1992
    Date of Patent: October 18, 1994
    Assignee: Sumitomo Chemical Company, Ltd.
    Inventors: Mitsuo Tanjo, Toshio Ashitani, Tetsuo Fujita, Katsuhiro Sakata, Mikitoshi Nakada
  • Patent number: 5344572
    Abstract: A method for treating waste pickle liquor solution comprising the steps of (a) adding a flocculating agent to the pickle liquor solution; (b) allowing at least some of the silica in the pickle liquor to begin to flocculate; (c) again adding a flocculating agent to the pickle liquor solution; (d) allowing the floccules containing silica formed in step (b) to increase in size; and (e) physically separating floccules formed in step (d) from the pickle liquor solution.
    Type: Grant
    Filed: July 10, 1992
    Date of Patent: September 6, 1994
    Inventor: Satish C. Wadhawan
  • Patent number: 5308600
    Abstract: Process for conditioning waste sulfuric acid which is prone to precipitation of tars or resins, which comprises adding emulsifiers, preferably long-chain polyethers, to the waste sulfuric acid.
    Type: Grant
    Filed: October 23, 1992
    Date of Patent: May 3, 1994
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Helmold von Plessen, Wolfram Fritsche-Lang, Horst Lorke
  • Patent number: 5266297
    Abstract: A liquid oxidizing system has a closed circuit in which a liquid containing matter to be oxidized is circulated. The circuit is provided with an ejector for forming a jet stream of the liquid into which oxygen, or both oxygen and an oxidizing catalyst are supplied. The oxygen (and the catalyst) rapidly contacts the matter to be oxidized in the jet stream and oxidizes it. The system is not only applicable to the treatment of waste water, such as from factories, but also useful for making a product by oxidizing a liquid, e.g. iron polysulfate which is a good coagulant.
    Type: Grant
    Filed: October 29, 1992
    Date of Patent: November 30, 1993
    Assignee: Sugita Wire Mfg. Co., Ltd.
    Inventor: Shigemi Kodama
  • Patent number: 5228885
    Abstract: The process of concentrating a dilute sulfuric acid in a three-stage vacuum evaporation plant includes feeding an entry dilute sulfuric acid to a first evaporation stage of a vacuum evaporation plant to form an overhead vapor (6), withdrawing a finally concentrated sulfuric acid from the third evaporation stage (3), using steam or the overhead vapor (6) of the first evaporation stage as a heating fluid in the three-stage vacuum evaporation plant, maintaining the entry dilute sulfuric acid under a pressure of 0.4 to 0.7 bar and at a temperature of 80.degree. to 120.degree. C. in the first evaporation stage (1), maintaining the partially concentrated sulfuric acid under a pressure of 0.02 to 0.06 bar and at a temperature of 50.degree. to 90.degree. C. in the second evaporation stage (2), maintaining the further concentrated sulfuric acid under a pressure of 0.02 to 0.06 bar and at a temperature of 80.degree. to 120.degree. C.
    Type: Grant
    Filed: September 20, 1991
    Date of Patent: July 20, 1993
    Assignee: Metallgesellschaft Aktiengesellschaft
    Inventors: Hartmut Wagner, Volker Wichert, Roland Fach, Klaus Engels, Gunter Okon
  • Patent number: 5171547
    Abstract: The present invention is directed to a method for treating a sludge containing substantial amounts of chromium, aluminum, calcium, iron, and phosphorous. The method comprises forming a slurry of the sludge; reacting the slurry with an acid to dissolve substantially all the aluminum and chromium and provide a solids residue comprising mostly calcium sulfate; separating the chromium/aluminum-containing solution from the solids residue; raising the pH of the chromium/aluminum solution to precipitate chromium as chromium hydroxide; and separating the chromium hydroxide from the remaining aluminum-containing solution. The chromium hydroxide is then enriched with an alkali or earth alkali compound and calcined in an oxidizing atmosphere to convert the chromium to a chromate. The calcine is leached in an aqueous medium at a controlled pH to yield a high concentration, high purity chromate solution suitable for producing metallic chromium or a variety of chromium chemicals.
    Type: Grant
    Filed: September 19, 1990
    Date of Patent: December 15, 1992
    Assignee: Amax, Inc.
    Inventors: Ranko Crnojevich, Andrew B. Case, Felix D. Rando, John D. Sweeney
  • Patent number: 5089040
    Abstract: Water-soluble iron complexes are produced by forming an aqueous reaction medium (a) comprising a sulfate source (e.g., ferric sulfate) and a ferric source (e.g., the ferric sulfate and a different ferric salt) and (b) having a pH and sulfate ion to ferric ion molar ratio sufficient to form the water-soluble iron complexes. Preferably, the molar ratio of sulfate ion to ferric ion in the reaction medium is about 0.5:1 to about 1.5:1. It is also preferred that the pH of the reaction medium be about 1 to about 3.
    Type: Grant
    Filed: February 24, 1989
    Date of Patent: February 18, 1992
    Assignee: Union Oil Company of California
    Inventors: Roger A. Brown, Donald C. Young, Alex E. Miller
  • Patent number: 5075097
    Abstract: Dilute waste sulfuric acid is concentrated by heating it against product acid and then passing it through two contact zones separated by a collection zone. The dilute acid scrubs vapour produced in the collection zone and from a high temperature acid reboiler. In the collection zone acid is drawn off, heated, and recirculated to the collection zone where part of the liquid flashes to vapour. The main heat input is to the more dilute low temperature recirculating acid from the first contact zone rather than to the more concentrated high temperature acid in the reboiler. As a result, less sulfuric acid vapour is generated; the major portion of the heat can be fed to the process at low temperature; and only a single column is required, having a single cool clear water vapour exit stream to dispose of.
    Type: Grant
    Filed: October 11, 1990
    Date of Patent: December 24, 1991
    Inventor: Gordon M. Cameron
  • Patent number: 5061472
    Abstract: A process for the recovery of sulphuric acid from waste acids containing metal sulphates by evaporative concentration and separation of the metal sulphates from the suspension obtained by evaporation, the improvement wherein vapors leaving the evaporators together with droplets of sulphuric acid containing metal sulphates and solid metal sulphates are condensed by direct contact with cooled contaminated vapor condensate, cooling of this vapor condensate which is circulated as cooling medium is carried out in a flash evaporator and the vapors leaving the flash evaporator free from metal sulphates and sulphuric acid are directly or indirectly condensed by means of cooling agent.
    Type: Grant
    Filed: August 1, 1990
    Date of Patent: October 29, 1991
    Assignee: Bayer Aktiengesellschaft
    Inventors: Gunter Lailach, Rudolf Gerken
  • Patent number: 5032376
    Abstract: An improved method for producing aluminum titanate powder material for making aluminum titanate ceramics.
    Type: Grant
    Filed: September 28, 1989
    Date of Patent: July 16, 1991
    Assignee: Maschinenfabrik Andritz Actiengesellschaft
    Inventor: Wolfgang Kladnig
  • Patent number: 5015458
    Abstract: A method is disclosed for removing iron from iron-contaminated sulfuric acid to render the sulfuric acid suitable for ion membrane processing which comprises contacting the iron-contaminated sulfuric acid with an oxidizing agent to oxidize essentially all of the iron to the +3 oxidation state, contacting the resulting iron-contaminated sulfuric acid containing oxidized iron with a complexing agent which can be citric acid, oxalic acid, and tartaric acid, with the amount of the complexing agent being sufficient to complex essentially all of the oxidized iron, and contacting the resulting iron-contaminated sulfuric acid containing the complexed iron with activated carbon to remove essentially all of the iron and produce a purified sulfuric acid solution.
    Type: Grant
    Filed: April 4, 1990
    Date of Patent: May 14, 1991
    Assignee: GTE Products Corporation
    Inventors: Clarence D. Vanderpool, Timothy J. Hoffman
  • Patent number: 5009868
    Abstract: The present invention discloses a process for rejuvenation of strip acid employed in the reclamation of expended lead-acid battery acid through extraction and filtration for removing metallic impurities from the battery acid. In the process of removing impurities from battery acid through extraction, the extractant becomes loaded with impurities and loses its effectiveness. Extractant may be regenerated by contacting it with an strip acid. In the present invention, a reduction process is employed to regenerate the strip acid so that it may be used repeatedly. By recycling the extractant and the strip acid in the present invention, the present process further increases the effectiveness of battery acid regeneration--producing a reclaimed battery acid fluid which performs very well in new batteries and substantially reducing by-product waste in the regeneration of the battery acid.
    Type: Grant
    Filed: December 21, 1989
    Date of Patent: April 23, 1991
    Assignee: East Penn Manufacturing Co., Inc.
    Inventors: Robert A. Spitz, Mark Bricker
  • Patent number: 4971780
    Abstract: The present invention discloses a process of extraction and filtration for removing metallic impurities from the acid in used lead-acid batteries. Produced is a reclaimed battery acid fluid which performs very well in new batteries and which avoids the severe costs and environmental risks entailed in present methods of battery acid fluid disposal.
    Type: Grant
    Filed: February 17, 1989
    Date of Patent: November 20, 1990
    Assignee: East Penn Manufacturing Co., Inc.
    Inventor: Robert A. Spitz
  • Patent number: 4968503
    Abstract: A process for the production of sodium dichromate comprising reacting sodium chromate with acids, the acids being sulfuric acid and NaHSO.sub.4 formed as a waste product in the production of CrO.sub.3 and thus being contaminated with chromium compounds, adding PO.sub.4 ions in excess to the NaHSO.sub.4 contaminated with chromium compounds and precipitating the Cr(III) present therein as CrPO.sub.4 at a temperature of 50.degree. to 100.degree. C. and at a pH value of 3 to 6.
    Type: Grant
    Filed: April 24, 1989
    Date of Patent: November 6, 1990
    Assignee: Bayer Aktiengesellschaft
    Inventor: Albert E. B. Glissmann
  • Patent number: 4952387
    Abstract: A process for the separation of metal sulphates from dilute sulphuric acid by evaporative concentration of the sulphuric acid to a concentration of from 55 to 75% by weight H.sub.2 SO.sub.4, cooling of the resulting solution or suspension and mechanically separating the solid metal sulphates and/or hydrogen sulphates, wherein an Fe(III) content of at least 0.01% by weight is ensured before the separation.
    Type: Grant
    Filed: July 13, 1988
    Date of Patent: August 28, 1990
    Assignee: Bayer Aktiengesellschaft
    Inventors: Gunter Lailach, Rudolf Gerken, Wolfgang Rens
  • Patent number: 4952378
    Abstract: A method for neutralization of sulfuric acid containing Fe ions, comprising adding ions selected from the group consisting of Na ions, K ions, Mg ions, Ca ions and NH.sub.4 ions in the form of a compound containing chlorine to a sulfuric acid solution to be treated in an amount corresponding at least to the chemical equivalent to SO.sub.4.sup.2-, and bringing the resultant solution into contact with an organic solvent containing oxygen or comprising alkylamine for extracting Fe ions from said aqueous solution into the organic phase as chloride complex. Iron chloride can be recovered from the organic phase by distilling or evaporating the organic solvent or by extracting back it into water.
    Type: Grant
    Filed: June 28, 1988
    Date of Patent: August 28, 1990
    Assignee: Solex Research Corporation of Japan
    Inventors: Morio Watanabe, Renpei Sei
  • Patent number: 4891206
    Abstract: A process for the extensive removal of undesirable metal ions, particularly vanadium ions, in the course of the concentration of dilute iron(II) sulfate-containing sulfuric acid solutions. The sulfuric acid solutions are concentrated by the evaporation of water and the separation of iron(II) sulfate to a content of 60 to 70% by weight H.sub.2 SO.sub.4. According to the invention, the content of trivalent titanium in the solution is adjusted such that the content of trivalent iron does not exceed 0.1 g/l. The trivalent titanium may be added from the outside, if not already present in an adequate amount in the solution, or may be formed in situ from the tetravalent titanium present in the solution by the addition of a reducing agent. Prior to the final concentration, part of the iron may be precipitated and separated as iron(II) sulfate heptahydrate by means of preconcentration and cooling of the preconcentrated sulfuric acid solution.
    Type: Grant
    Filed: August 17, 1984
    Date of Patent: January 2, 1990
    Assignee: Kronos Titan, GmbH
    Inventors: Achim M. Kulling, Helmut Steinhausen
  • Patent number: 4889697
    Abstract: According to the subject method of refining a ferrous ion-containing acid solution, a metal selected from a group including Al, Cr, V, B, and Zn or an acid solution of that metal is added to a ferrous ion-containing acid solution, such as an acid solution which remains after steel is washed with an acid. The pH value of the acid solution is controlled to be within the range of 3.5 to 6 by adding an alkali liquid to the acid solution, whereby a hydroxide salt of the added metal is produced in the acid solution and the impurities in the acid solution are captured by the produced hydroxide salt. As a result, the impurities can be eliminated from the acid solution such that the Si component (e.g., SiO.sub.2) content in the acid solution is within the range of 2 to 3 ppm or less. Since the content of the other impurities such as Al, Ti, and Cr can also be reduced, a high-purity iron oxide can be obtained from the resultant acid solution.
    Type: Grant
    Filed: December 5, 1988
    Date of Patent: December 26, 1989
    Assignees: NKK Corporation, Kokan Mining Co., Ltd.
    Inventors: Tsutomu Fukushima, Tsugio Nakao, Kasane Yamashita, Takao Komuro, Katsuhiro Nishi
  • Patent number: 4822575
    Abstract: The invention concerns processes for the preparation of zirconium compositions which on calcination form zirconia. The zirconium compositions are prepared by the addition of an ammonia source to an aqueous zirconium sulfate solution to give a solution pH in the range of from 0.1 to 2.5 and preferably 1.0 to 2.0. The zirconium composition precipitated from solution appears crystalline, is readily collected by filtration and has low levels of metallic impurities. Therefore, the process of the invention may be used to advantage in the purification zirconium compounds.The invention also includes the zirconium compositions and processes for the purification of zirconium compounds including zirconia.
    Type: Grant
    Filed: January 2, 1987
    Date of Patent: April 18, 1989
    Assignee: ICI Australia Limited
    Inventors: Kian F. Ngian, Angus J. Hartshorn, David H. Jenkins
  • Patent number: 4792349
    Abstract: The present invention teaches a technique and provides for apparatus eminently useful for the econimic recovery of Fe, Zn, and S from waste galvinizer sulfuric acid and crystals of iron sulfate and zinc sulfate. The technique or method of the instant invention involves the ammoniation of the acid or a solution prepared from such crystals followed by the partial oxidation of the resulting ammoniated suspension to a point where the desired product magnetite is formed in the separated from a marketable solution of ammoniacal zinc sulfate. The effecting of the instant technique requires only a minimal amount of relatively inexpensive equipment and is simply and easily placed into practice by, for example, sparging anhydrous ammonia into a stirred tank of waste acid until the Ph is elevated to about 10. Air can be sparged through the resulting slurry to oxidize the iron in the acid. After a proper incubation period, the desired stable product, e.g.
    Type: Grant
    Filed: November 3, 1987
    Date of Patent: December 20, 1988
    Assignee: Tennessee Valley Authority
    Inventors: Joe R. Trimm, Louis A. Stumpe
  • Patent number: 4758414
    Abstract: The precipitation of iron and aluminum from their solutions in strong acids, eg. 18% HCl and 25% H.sub.2 SO.sub.4, is accomplished by adding to the acid solution certain organic aminophosphonic acids in which at least 50% of the amine hydrogens have been substituted with methylenephosphonic acid groups. Particularly preferred compounds are the methylenephosphonic acid derivatives of ammonia and polyalkylenepolyaminepoly(methylenephosphonic acids). The completely phosphonomethylated derivatives are most preferred.
    Type: Grant
    Filed: June 30, 1987
    Date of Patent: July 19, 1988
    Assignee: The Dow Chemical Company
    Inventors: Dennis R. Gifford, Marvin L. Dettloff
  • Patent number: 4755270
    Abstract: A method of processing waste solutions containing metal salts or complex involves applying ultra-sonic vibrations to a container in which the solution is placed and treating the solution or the generated misting therefrom to insure that the metallic ions remain behind and then finally exhausting the vapor through an activated charcoal filter to remove any organic contaminants and insure that the discharge is environmentally safe.
    Type: Grant
    Filed: April 17, 1987
    Date of Patent: July 5, 1988
    Inventor: Joseph Aliotta
  • Patent number: 4741776
    Abstract: A method of processing waste material comprises treating the material with flue dust and bonding it to form a solid mass with cement powder, e.g. Portland cement. Acidic liquors containing heavy metals can be processed. Suitable flue dust is obtained from cement manufacture.
    Type: Grant
    Filed: July 30, 1985
    Date of Patent: May 3, 1988
    Assignee: Blue Circle Industries Limited
    Inventors: Gerald C. Bye, Kenneth B. Matthews
  • Patent number: 4707349
    Abstract: A process is provided for preparing a preferred ferric sulfate solution. The product of the process is particularly suited for use in water treatment and purification. According to the process, iron oxides or iron, are dissolved in sulfuric acid to form ferrous sulfate. In a first step of oxidation, the ferrous sulfate is partially oxidized to ferric sulfate in the presence of dissolved oxygen. In a second stage of oxidation, remaining ferrous sulfate is oxidized to ferric sulfate by the action of a non-molecular oxygen oxidizing agent such as hydrogen peroxide. During both stages of oxidation, a catalyst such as copper sulfate or copper ammonium sulfate may be used. Careful control of added sulfuric acid is maintained, to avoid excess or free sulfuric acid in the reaction product. The final reaction product is generally characterized by having: between about 10% and 12% iron by weight; substantially all iron present in the ferric form; and, by having less than 0.5% free or excess acid, by weight.
    Type: Grant
    Filed: February 28, 1986
    Date of Patent: November 17, 1987
    Inventor: Norman B. Hjersted
  • Patent number: 4698139
    Abstract: The purpose of the method is to remove chlorides and fluorides from a valuable metal raw material by leaching the raw material into sulphuric acid solution and by crystallizing the valuable metal sulphate selectively out of the solution. The valuable metal sulphate crystals are washed in sulphuric acid solution, and the recovered dechlorinated and defluorinated crystals are leached into water and conducted into electrolysis. The sulphuric acid solution employed in the raw material leaching and in the crystal washing is preferably the same as the return acid of the electrolysis. Chlorides and fluorides are removed from the mother liquor of crystallization in the bleed.
    Type: Grant
    Filed: January 6, 1986
    Date of Patent: October 6, 1987
    Assignee: Outokumpu Oy
    Inventors: Sigmund P. Fugleberg, Jaakko I. Poijarvi
  • Patent number: 4663145
    Abstract: A device for and method of working up etching and pickling liquids consisting of a vertical furnace having one or more vertical reaction spaces through which balls move at a maximum packing density.The furnace has a temperature gradient from the bottom (high) to the top (low). The reaction space and the balls consist of a material which is inert with respect to the liquid to be worked up. The liquid is introduced into the upper side of the furnace so that a film is formed in the heated surface of the balls. The salt dissolved in the liquid decomposes pyrolytically. The metal oxide is deposited on the surface of the balls and is removed therefrom after leaving the reaction space. The acid residue vapours are drained at the top and recovered in a separate absorber to the original pickling or etching acid.
    Type: Grant
    Filed: September 10, 1985
    Date of Patent: May 5, 1987
    Assignee: U.S. Philips Corporation
    Inventors: Peter J. T. Van den Berk, Berend Knol, Franciscus J. M. Dubois
  • Patent number: 4659555
    Abstract: The invention relates to a process for the preparation of basic copper carbonate by reacting copper salts with alkali carbonate in aqueous solution at elevated temperatures and with stirring and subsequently isolating the copper carbonate. In this process, a waste solution from copper etching processes which contains hydrochloric acid and sodium chloride, is stirred into a 5 to 15 weight percent solution of alkali carbonate heated to 40.degree. to 70.degree. C., the pH of the solution not being allowed to fall below 6.5, and the precipitated basic copper carbonate is separated from the aqueous solution in a known manner. A light green, basic copper carbonate is obtained, which is free of copper chloride and copper oxide.
    Type: Grant
    Filed: April 26, 1985
    Date of Patent: April 21, 1987
    Assignee: Th. Goldschmidt AG 03
    Inventors: Werner Gottfried, Ernst Mack, Lothar Witzke
  • Patent number: 4619814
    Abstract: This invention relates to the development of a viable metallurgical process capable of treating low grade concentrates, bulk concentrates, dirty concentrates, or ore directly for the recovery of non-ferrous metals such as zinc, lead, copper, and precious metals and accordingly is significant to the development of massive fine grained sulphide ore bodies found throughout the world. The process involves the consecutive steps of sulphatizing roasting in a fluidized bed reactor, a two stage leach, metal recovery from solution by conventional processes such as electrowinning and precipitation, and recycling of residue wash waters and leach liquors containing high concentrations of iron and minor impurity elements to the roaster or a spray dryer for thermal decomposition. Simple and efficient rejection of iron from the circuit to residue as stable hematite is the net result of the recirculation and thermal decomposition.
    Type: Grant
    Filed: September 7, 1983
    Date of Patent: October 28, 1986
    Assignee: Provincial Holdings Ltd.
    Inventors: Robert S. Salter, Roy S. Boorman, Igor A. E. Wilkomirsky
  • Patent number: 4565675
    Abstract: A process for treating and recovering pickling waste liquids used for the pickling of stainless steel such as nitric-hydrofluoric acid, nitric acid, hydrochloric acid and, sulfuric acid is disclosed, which comprises recovering the nitric-hydrofluoric acid and the iron oxide or metallic ion from the waste liquids of nitric-hydrofluoric acid and nitric acid by two solvent extraction processes and recovering the Cr and Ni containing ferrite from the waste liquids of sulfuric acid or hydrochloric acid by a ferrite formation process. When the waste acid is sulfuric acid, gypsum of a high purity can be obtained.
    Type: Grant
    Filed: March 20, 1985
    Date of Patent: January 21, 1986
    Assignees: Kawasaki Steel Corporation, Research Development Corporation, Solex Research Corporation of Japan
    Inventors: Kazuhiro Uchino, Toshio Watanabe, Yoshio Nakazato, Minoru Hoshino, Noboru Ishihara
  • Patent number: 4440734
    Abstract: The disclosure describes the recovery of sulfuric acid from industrial liquors containing the same. A selective liquid-liquid extraction of said liquors is carried out under conditions producing an organic phase containing the sulfuric acid and an aqueous phase eventually containing impurities. The organic phase is treated with a base, such as gaseous NH.sub.3, in order to separate the sulfuric acid. This process is simple, non-polluting, and requires little energy.
    Type: Grant
    Filed: February 11, 1982
    Date of Patent: April 3, 1984
    Assignee: Gouvernement du Quebec
    Inventor: Demetre Kougioumoutzakis
  • Patent number: 4436545
    Abstract: A process having the two-fold result of the disposal of waste pickle liquor and the production of a highly useful fertilizer in which urea is mixed with waste pickle liquor to produce a stable liquid fertilizer.
    Type: Grant
    Filed: July 30, 1982
    Date of Patent: March 13, 1984
    Assignee: Leggett & Platt, Incorporated
    Inventors: Donald W. Lyons, Jr., Everette L. Wyatt
  • Patent number: 4415540
    Abstract: The specification discloses a method for recovering non-ferrous metals such as zinc or copper iron from their concentrates, ores or any other metal containing materials into a solution containing these non-ferrous metals as sulphates and a minimal amount of dissolved iron. The resultant solution is suited without or with minimum pre-purification treatment for conventional electrowinning processes to recover such non-ferrous metals with less difficulties than the previous methods involving complex iron-removal processing. There is disclosed a method for recovering at least one non-ferrous metal soluble in sulphuric acid from a strong sulphuric acid solution containing said metal and iron as sulphates, said method comprising the following consecutive steps:subjecting said solution in a sub-divided form to thermal decomposition in a fluidized bed reactor at a temperature of from 600.degree. to 750.degree. C.
    Type: Grant
    Filed: February 8, 1982
    Date of Patent: November 15, 1983
    Assignee: Provincial Holdings Ltd.
    Inventors: Igor A. E. Wilkomirsky, Roy S. Boorman, Robert S. Salter
  • Patent number: 4317803
    Abstract: The specification discloses a method for recovering non-ferrous metals such as zinc or copper from their concentrates, ores or any other metal containing materials into a solution containing these non-ferrous metals as sulphates and a minimal amount of dissolved iron. The resultant solution is suited without or with minimum pre-purification treatment for conventional electrowinning processes to recover such non-ferrous metals with less difficulties than the previous methods involving complex iron-removal processing. There is disclosed a method for recovering at least one non-ferrous metal soluble in sulphuric acid from a strong sulphuric acid solution containing said metal and iron as sulphates, said method comprising the following consecutive steps:subjecting said solution in a sub-divided form to thermal decomposition in a fluidized bed reactor at a temperature of from 600.degree. to 750.degree. C.
    Type: Grant
    Filed: September 22, 1980
    Date of Patent: March 2, 1982
    Assignee: Provincial Holdings Ltd.
    Inventors: Igor A. E. Wilkomirsky, Roy S. Boorman, Robert S. Salter
  • Patent number: 4304759
    Abstract: The invention provides a process for thermally decomposing salts, containing mainly ferrous sulfate wherein said feed material is contacted in a single suspension-type exchanger with exhaust gases formed by reaction of the oxygen-containing gases in the fluidized bed reactor, the fluidizing gas and at least a partial stream of the secondary gas stream are heated by an indirect heat exchange in a fuel-heated heat exchanger, and the quantity of oxygen introduced via which consists of the fluidizing gas and the secondary gas, is controlled in dependence on the quantity of fuel in order to receive an exhaust gas from the suspension-type exchanger with a free oxygen content of 1-6% by volume and a temperature of 300.degree.-450.degree. C.
    Type: Grant
    Filed: May 1, 1980
    Date of Patent: December 8, 1981
    Assignee: Metallgesellschaft AG
    Inventors: Georg Daradimos, Martin Hirsch, Lothar Reh, Jorg Thomas
  • Patent number: 4292085
    Abstract: Ferrous sulphate heptahydrate obtained as a by-product of the production of titanium dioxide by the sulphate process is converted into a non-polluting, free-flowing particulate neutralization product by contacting said sulphate with calcium hydroxide as a neutralizing agent in a molar ratio between said neutralizing agent and said ferrous sulphate of at least 1:1, and reacting the resulting mixture under agitation at a temperature not exceeding 60.degree. C. and for a contact time not exceeding five minutes.
    Type: Grant
    Filed: September 14, 1979
    Date of Patent: September 29, 1981
    Assignee: Euteco Impianti S.p.A.
    Inventors: Luigi Piccolo, Tullio Corsini, Antonio Paolinelli, Gaudenzio Ferri, Angelo La Rovere
  • Patent number: 4264570
    Abstract: A method of producing magnesium sulphate comprises the steps of interacting ferrous sulphate with compounds including magnesium carbonates, oxides and hydroxides, with magnesium sulphate being produced. The step of interacting the starting reagents is conducted in water medium in the presence of carbon dioxide and is effected in the range of temperatures of 80.degree. to 100.degree. C.
    Type: Grant
    Filed: February 27, 1979
    Date of Patent: April 28, 1981
    Inventors: Igor D. Sokolov, Oleg D. Kashkarov, Jury S. Safrygin, Alexandr V. Muraviev, Nina K. Andreeva
  • Patent number: 4224122
    Abstract: The specification discloses a method for recovering non-ferrous metals such as zinc or copper from their concentrates, ores or any other metal containing materials into a solution containing these non-ferrous metals as sulphates and a minimal amount of dissolved iron. The resultant solution is suited without or with minimum pre-purification treatment for conventional electrowinning processes to recover such non-ferrous metals with less difficulties than the previous methods involving complex iron-removal processing. There is disclosed a method for recovering at least one non-ferrous metal soluble in sulphuric acid from a strong sulphuric acid solution containing said metal and iron as sulphates, said method comprising the following consecutive steps:subjecting said solution in a sub-divided form to thermal decomposition in a fluidized bed reactor at a temperature of from 600.degree. to 750.degree. C.
    Type: Grant
    Filed: September 11, 1978
    Date of Patent: September 23, 1980
    Assignee: New Brunswick Research and Productivity Council
    Inventors: Igor A. E. Wilkomirsky, Roy S. Boorman, Robert S. Salter
  • Patent number: 4208393
    Abstract: A process for the treatment of aqueous sulphuric acid solutions containing dissolved ferrous sulphate comprising forming such a solution containing from 140 to 220 grams/liter free sulphuric acid in a first zone; adjusting the pH value of the solution in this zone to one in the range 3 to 4 by the addition of finely-divided calcium carbonate thereby precipitating calcium sulphate; passing the slurry thus produced to a second zone; adding to the second zone an aqueous solution of sulphuric acid containing from 3 to 80 grams/liter of free sulphuric acid; adjusting the pH value of the mixture in the second zone to one in the range 3.5 to 6 by the addition of finely-divided calcium carbonate thereby precipitating calcium sulphate and thereafter recovering from the second zone calcium sulphate suitable for use in the manufacture of plasterboard.
    Type: Grant
    Filed: September 14, 1978
    Date of Patent: June 17, 1980
    Assignee: Tioxide Group Limited
    Inventor: Gratian LeBel
  • Patent number: 4197139
    Abstract: A process for reclaiming pickling liquor acid from spent pickle liquor comprises injecting the spent liquor from a metal pickling process into a container having an upper section, a lower liquid holding section and a heating means. The spent pickle liquor in the container lower section is heated, and the water therein is vaporized and returned to the pickling process in a vapor state to be absorbed therein and provide heat thereto. A substantial portion of the unused acid is removed from the spent pickle liquor and is also returned to the pickling process without cooling.
    Type: Grant
    Filed: August 23, 1978
    Date of Patent: April 8, 1980
    Inventor: Norman B. Hjersted
  • Patent number: 4163047
    Abstract: A process for the recovery of sulfuric acid from waste sulfuric acid containing iron sulfate and from solid iron sulfate of high water content of crystallization which consists essentially of:A. concentrating waste sulfuric acid to an acid concentration of 25-55 weight percent, based upon the suspension, by removing water therefrom;B. mixing the concentrated acid of Step A with recycled concentrated sulfuric acid obtained from Step E to form a resultant acid mixture of acid concentration of 30-65 weight percent, based upon the suspension;C. adding said solid iron sulfate of high water content of crystallization to the acid mixture of Step B thereby obtaining iron sulfate of low water content of crystallization;D. separating the iron sulfate of low water content from the resultant sulfuric acid solution of Step C;E. concentrating the separated sulfuric acid solution of Step D to an acid concentration of 45-70 weight percent, based on salt-free acid, and recycling at least a portion thereof to Step B; andF.
    Type: Grant
    Filed: June 30, 1977
    Date of Patent: July 31, 1979
    Assignees: Metallgesellschaft Aktiengesellschaft, Bayer Aktiengesellschaft
    Inventors: Karl-Heinz Dorr, Georg Daradimos, Hugo Grimm, Georg Schmidt, Rudolf Gerken, Christoph Mucke, Hermann Wieschen
  • Patent number: 4153628
    Abstract: Spent sulphuric acid, either alongside or mixed with contaminated metal salts such as iron sulphate heptahydrate, is regenerated to fresh acid by countercurrent contact with gases from cleavage of the sulphate salts, such gases containing SO.sub.3 which effects build up of the acid concentration. The built up acid is evaporated in another stage to obtain pure acid. The metal sulphate solids are subjected to high temperature cleavage, generating SO.sub.3 which effects the previous concentration. Cleavage also produces some SO.sub.2 which is converted to SO.sub.3 by wet catalysis.
    Type: Grant
    Filed: September 26, 1977
    Date of Patent: May 8, 1979
    Assignees: Bayer Aktiengesellschaft, Metallgesellschaft Aktiengesellschaft
    Inventors: Rudolf Gerken, Hans Guth, Christoph Mucke, Willi Potes, Hermann Wieschen
  • Patent number: 4137293
    Abstract: Gypsum and magnetite which are both coarse and of good quality can simultaneously be produced by introducing calcium carbonate into an aqueous solution containing ferrous sulfate while an oxidizing gas is blown, and then carrying out a neutralizing and oxidizing operation at a pH of 5-6 and a temperature of 60-80.degree. C, and can be separately recovered by magnetic separation.
    Type: Grant
    Filed: December 16, 1977
    Date of Patent: January 30, 1979
    Assignee: Ishihara Sangyo Kaisha, Ltd.
    Inventors: Koichi Nagata, Kokichi Miyazawa, Takeshi Sato, Masashi Tsuchimoto, Junichi Kawashima