US3760070A - Manufacture of copper oxide - Google Patents

Manufacture of copper oxide Download PDF

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Publication number
US3760070A
US3760070A US00183274A US3760070DA US3760070A US 3760070 A US3760070 A US 3760070A US 00183274 A US00183274 A US 00183274A US 3760070D A US3760070D A US 3760070DA US 3760070 A US3760070 A US 3760070A
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Prior art keywords
copper
solution
ammonia
oxygen
aqueous solution
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US00183274A
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English (en)
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B Joice
Mallinson R Niven
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • ABSTRACT A method for the production of copper oxide or zinc hydroxide which comprises contacting metallic copper or zinc is contacted with an aqueous solution containing oxygen or an oxygen-containing gas, ammonia and an ammonium salt which is preferably ammonium nitrate.
  • the concentration of ammonia is maintained above 4 moles per mole of dissolved copper and the aqueous solution of copper ammine or zinc ammine is separated from any undissolved metal before it becomes saturated with the metal and then heated to precipitate copper oxide or zinc hydroxide from the solu tion.
  • the heating is carried out in the absence of added alkali and in the presence of a stream of purging gas and the mother liquor and the purging gas are recycled.
  • the present invention provides a method for the manufacture of copper oxide.
  • the invention thus provides a valuable step in the manufacture of copper salts, such as copper dichromate.
  • the invention is also applicable to the manufacture of zinc hydroxide.
  • cuprammonium salts may be decomposed by heating in solution so as to recover the copper as an acid soluble oxide and the other staring materials in a form suitable for reuse in the preparation of further copper ammines.
  • Copper oxide produced according to the invention is a convenient source for the manufacture of cupric salts, including copper dichromate.
  • Our invention provides a method for the manufacture of copper oxide and/or zinc hydroxide which comprises contacting metallic copper and/or zinc with oxygen and an aqueous solution of ammonia and an ammonium salt, sufficient to dissolve the metal as a metal ammine, separating the solution of metal ammine from any undissolved metal and heating the metal ammine to precipitate copper oxide and/or zinc hydroxide.
  • the metallic copper may be granular, wire, scrap, copper rings or any other convenient physical form. Since the reaction occurs at the suface of the copper, an adequate surface area must be exposed to the reaction mixture, but it is not necessary for the copper to be very finely divided. Satisfactory reaction has been achieved in a column packed with copper rings.
  • oxygen may conveniently be bubbled through the reaction mixture in such a manner that adequate contact with the copper is achieved, by ensuring the presence of air spaces in the mass of copper.
  • oxygen may be passed into a column containing the copper and reaction solution, through suitable distribution means (e.g. a sintered glass, or other finely perforated, plate) located in the base of the column, or else through a simple inlet.
  • suitable distribution means e.g. a sintered glass, or other finely perforated, plate located in the base of the column, or else through a simple inlet.
  • the oxygen may be used as the pure gas, or diluted with inert gases.
  • air, or air enriched with oxygen may be used as the source of oxygen.
  • the pressure in the reaction vessel is not critical. We have found it convenient to dissolve the copper at atmospheric pressure, but other pressures, e.g., superatmospheric pressures could be employed.
  • the temperature of the reaction mixture may be varied within wide limits.
  • the reaction is operable at any temperature at which the reaction mixture is liquid, e.g., 10 to C.
  • the initial temperature is between 15C and 45C, e.g., from 20C to 30C. It the reaction is allowed to proceed without any cooling the temperature will rise, e.g., from 25C initial temperature to 55C final temperature. If the reaction mixture is cooled the preferred steady temperature may be between 30C and 50C.
  • the concentration of ammonia must be sufficient to dissolve metallic copper, e.g., from 0.5 percent by weight up to saturation. The higher the ammonia concentration the more rapid the dissolution of copper, but the greater the loss of ammonia from the solution.
  • concentration of ammonia in the reaction solution is from 5 percent to 20 percent by weight.
  • ammonia concentration is maintained throughout at a value greater than 4 moles per mole dissolved copper.
  • the ammonium salt may preferably be ammonium chloride, ammonium sulphate, ammonium nitrate, ammonium carbonate or mixtures of ammonium salts. Most other water soluble ammonium salts are also effective, although the chromate and dichromate are not recommended. We have discovered that the use of ammonium nitrateis particularly advantageous, in that it does not tend to form basic copper nitrate when the solution is heated to precipitate copper oxide.
  • ammonium salt may generally be present in concentrations of from 0.5 percent to saturation, it is preferred, in the case of ammonium salts other than the nitrate to employ concentrations less then 5 percent and preferably less than 2.5 percent by weight or about 0.2 molar in the reaction solution, in order to avoid formation of basic copper salts.
  • Ammonium nitrate may conveniently be employed in concentrations up to, for example, 16 percent by weight, with gains in the rate of dissolution of the copper but without formation of basic copper nitrate.
  • the rate of dissolution is proportional to the concentration of ammonium salt.
  • the rate of flow of oxygen or oxygen-containing gas through the system influences the rate of reaction and the rate of loss of ammonia.
  • the total amount of oxygen passed through the system while the reaction solution is in contact with the metallic copper is at least sufficient to provide approximately the stoichiometric quantity based on the equation:
  • NH X is a copper ammine, as defined in Chemical Elements and their Compounds by Sidgwick, Vol. 1, pages 156-157 (Oxford University Press 1950); with the corresponding zinc ammines being defined at pages 279-280. These are sometimes (and less preferably) referred to as coprammonium and zinc ammonium salts.
  • the dissolution of copper in the aqueous ammoniacal solution may be performed as a batch or a continuous or semi-continuous operation. In either case operation involves contacting copper with an aqueous solution of ammonia salt preferably containing an excess of ammonia based on the above stoichiometry.
  • the initial concentration of dissolved copper is preferably zero and in any case less than saturation andthe solution is preferably separated from the metallic copper before the concentration of dissolved copper reaches saturation, so as to avoid precipitation of copper hydroxide on the surface of the metallic copper.
  • the solution of copper ammine is heated, e.g., to a temperature above 80C and preferably to boiling point.
  • a purging gas e.g., air, is preferably passed through the heated solution to assist in removing ammonia, according to the equation:
  • the ammonia and ammonium salt may each be recovered substantially quantitatively and reused. If air or other oxygen containing gas is used to purge the solution of ammonia, it may be directly recycled to the vessel in which the metallic copper is dissolved, and used to supply both oxygen and ammonia. The copper oxide settles out as a granular precipitate which is easily filtered to leave a clear aqueous solution of the ammonium salt ready to be reused directly in the dissolution of fresh metallic copper.
  • the copper oxide may be used as such or may be dissolved in a variety of acids to form cupric salts which can otherwise be prepared commercially only by a longer or more expensive sequence of steps.
  • the copper oxide may be dissolved in chromic acid to form copper dichromate, or hydrochloric, formic, acetic or napthenic acids.
  • Example 1 A glass column, packed with gm. of copper rings, was filled with 200 ml. of a solution containing 11.2 gm. of NH;, and 20 gm. of ammonium nitrate. Air was passed into the base of the column at the rate of 250 ml.per minute, for 1 hour, and the temperature of the solution rose steadily from 25C to a maxiumum of 50C, 12.5 gm of copper were found to have dissolved at the completion of the reaction. The deep blue solution was then poured into a separate vessel, and steam and air were passed through the solution for 30 minutes. Ammonia was driven off and copper oxide was quantitatively formed as a heavy black precipitate. The clear ammonium nitrate solution was decanted, and recovered for further use.
  • Example 2 The procedure of example 1 was repeated in the absence of ammonia in the initial reaction solution. Under these conditions, only 1 gm. of copper was dissolved after 1 hour.
  • Example 3 The procedure of example 1 was carried out in the absence of ammonium nitrate in the initial reaction solution. Only 2 gm. of copper dissolved after one hour.
  • Example 4 The procedure of example 1 was carried out using 100gm. of pieces of thin zinc sheet in place of the hollow copper rings. A temperature rise-from 22C to 52C was recorded and 9.6 gm. of zinc were found to have dissolved after one hour. Air and steam were then passed through the clear colourless solution and zinc hydroxide was formed as a heavy white precipitate.
  • Example 5 The procedure of example 1 was followed using 100 gmfof hollow brass rings in place of the copper rings. 14.0 gm of the brass had dissolved after one hour.
  • Example 6 8 gm. of copper oxide, obtained according to example l, were added to 100 ml. of a cold solution of chromic acid containing 20 gm. of CrO The entire sample dissolved rapidly to yield a clear solution of copper dichromate.
  • Example 7 A sample of copper oxide, obtained according to example 1, was added to an excess of naphthenic acid NA. 180 SP (supplied by Shell Chemicals Ltd.) dissolved in white spirit. The mixture was heated and stirred for two hours, after which the copper oxide was substantially dissolved to yield a deep blue/green solution of cupric naphthenate. Commercial grades of copper oxide were found to be almost completely unattacked by the acid under the above conditions.
  • a method for the manufacture of a product selected from copper oxide and zinc hydroxide which consists in (a) contacting a metal M selected from copper, zinc and mixtures thereof with an oxygen containing gas and an aqueous solution consisting essentially of water, between 0.5 and 16 percent by weight of water soluble ammonium salt NH X, wherein X is the anion of said salt, and between 0.5 percent and saturation of ammonia, said ammonia being maintained at a concentration in said solution inan amount greater than 4 moles per mole of dissolved metal M, whereby metal M is dissolved to form the corresponding metal ammine M(NH ).,X
  • ammonium salt is ammonium nitrate in a concentration of from 5 to 16 percent by weight.
  • ammonium is selected from ammonium chloride, ammonium sulphate and ammoniumcarbonate and is present in a concentration of less than 0.2 molar.
  • step (a) The method according to claim 5 wherein the solution is cooled during step (a) to maintain a steady state temperature between 30C and 50C.
  • the oxygen containing gas is selected from oxygen, air and mixtures thereof and is bubbled through a mixture of the metal and the aqueous solution.
  • a method for the manufacture of copper oxide which comprises a. contacting metallic copper with an aqueous solution consisting essentially of water, from 5 to 16 percent by weight of ammonium nitrate and from 0.5 percent to saturation of ammonia;
  • step (e) passing a gas selected from oxygen, air and mixtures thereof through theheated solution, thereby forming a gaseous mixture of ammonia and said f. recycling said gaseous mixture from step (e) to provide at least part of the oxidising gas and the ammonia required at step (b);
  • step (g) recycling said aqueous solution from step (g) to provide at'least part of the solution required in step

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00183274A 1970-09-24 1971-09-23 Manufacture of copper oxide Expired - Lifetime US3760070A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB4549770A GB1368602A (en) 1970-09-24 1970-09-24 Manufacture of copper oxide

Publications (1)

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US3760070A true US3760070A (en) 1973-09-18

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Country Status (10)

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US (1) US3760070A (OSRAM)
AU (1) AU3354471A (OSRAM)
BE (1) BE773079A (OSRAM)
CA (1) CA954275A (OSRAM)
DE (1) DE2147591A1 (OSRAM)
FR (1) FR2107940A1 (OSRAM)
GB (1) GB1368602A (OSRAM)
IT (1) IT939862B (OSRAM)
NL (1) NL7113062A (OSRAM)
ZA (1) ZA716158B (OSRAM)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065300A (en) * 1976-06-28 1977-12-27 Poarch Archie L Method for extraction of copper products from copper bearing material
WO1991001942A1 (en) * 1989-08-01 1991-02-21 Australian Copper Company Pty. Ltd. Production of copper compounds
US5188703A (en) * 1992-01-27 1993-02-23 Diversified Recycling Technology Method and apparatus for recovering copper and regenerating ammoniacal etchant from spent ammoniacal etchant
AU635943B2 (en) * 1989-08-01 1993-04-08 Christopher John Browne Production of copper compounds
AU642895B2 (en) * 1989-08-01 1993-11-04 Australian Copper Company Pty. Ltd. Production of copper compounds
US5492681A (en) * 1993-03-22 1996-02-20 Hickson Corporation Method for producing copper oxide
US20050171369A1 (en) * 2003-11-19 2005-08-04 Pasek Eugene A. Methods for producing copper ethanolamine solutions
US20070207076A1 (en) * 2006-03-06 2007-09-06 Osmose Inc. Method of preparing metal-containing wood preserving compositions
RU2463251C1 (ru) * 2011-05-10 2012-10-10 Государственное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" Способ получения оксида меди
WO2020170011A1 (en) * 2019-02-19 2020-08-27 Upl Ltd Process for preparation of copper compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3606920A1 (de) * 1986-03-04 1987-09-10 Norddeutsche Affinerie Verfahren zur herstellung von kupferhydroxid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1608844A (en) * 1922-11-20 1926-11-30 Edwards George Waldron Treament of oxidized ores or other oxidized compounds of copper and zinc
US3652229A (en) * 1969-03-12 1972-03-28 Zane L Burke Apparatus for production of metal oxides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1608844A (en) * 1922-11-20 1926-11-30 Edwards George Waldron Treament of oxidized ores or other oxidized compounds of copper and zinc
US3652229A (en) * 1969-03-12 1972-03-28 Zane L Burke Apparatus for production of metal oxides

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065300A (en) * 1976-06-28 1977-12-27 Poarch Archie L Method for extraction of copper products from copper bearing material
WO1991001942A1 (en) * 1989-08-01 1991-02-21 Australian Copper Company Pty. Ltd. Production of copper compounds
AU635943B2 (en) * 1989-08-01 1993-04-08 Christopher John Browne Production of copper compounds
AU642895B2 (en) * 1989-08-01 1993-11-04 Australian Copper Company Pty. Ltd. Production of copper compounds
US5310533A (en) * 1989-08-01 1994-05-10 Australian Copper Company Pty. Ltd. Production of copper compounds
US5188703A (en) * 1992-01-27 1993-02-23 Diversified Recycling Technology Method and apparatus for recovering copper and regenerating ammoniacal etchant from spent ammoniacal etchant
US5492681A (en) * 1993-03-22 1996-02-20 Hickson Corporation Method for producing copper oxide
US20050171369A1 (en) * 2003-11-19 2005-08-04 Pasek Eugene A. Methods for producing copper ethanolamine solutions
US7273944B2 (en) 2003-11-19 2007-09-25 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
US20070207076A1 (en) * 2006-03-06 2007-09-06 Osmose Inc. Method of preparing metal-containing wood preserving compositions
RU2463251C1 (ru) * 2011-05-10 2012-10-10 Государственное образовательное учреждение высшего профессионального образования "Ивановский государственный химико-технологический университет" Способ получения оксида меди
WO2020170011A1 (en) * 2019-02-19 2020-08-27 Upl Ltd Process for preparation of copper compounds
IL285205B1 (en) * 2019-02-19 2024-08-01 Upl Ltd A process for preparing copper compounds
US12075783B2 (en) 2019-02-19 2024-09-03 Upl Ltd Process for preparation of copper compounds

Also Published As

Publication number Publication date
GB1368602A (en) 1974-10-02
CA954275A (en) 1974-09-10
BE773079A (fr) 1972-01-17
AU3354471A (en) 1973-03-22
DE2147591A1 (de) 1972-05-04
FR2107940A1 (OSRAM) 1972-05-12
NL7113062A (OSRAM) 1972-03-28
IT939862B (it) 1973-02-10
ZA716158B (en) 1972-05-31

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