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WO1991001942A1 - Production de composes de cuivre - Google Patents

Production de composes de cuivre Download PDF

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Publication number
WO1991001942A1
WO1991001942A1 PCT/AU1990/000323 AU9000323W WO9101942A1 WO 1991001942 A1 WO1991001942 A1 WO 1991001942A1 AU 9000323 W AU9000323 W AU 9000323W WO 9101942 A1 WO9101942 A1 WO 9101942A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
solution
ammine
oxygen
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU1990/000323
Other languages
English (en)
Inventor
Christopher John Browne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Australian Copper Co Pty Ltd
Original Assignee
Australian Copper Co Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU58043/90A external-priority patent/AU635943B2/en
Application filed by Australian Copper Co Pty Ltd filed Critical Australian Copper Co Pty Ltd
Priority to DE69018645T priority Critical patent/DE69018645T2/de
Priority to PCT/AU1990/000323 priority patent/WO1991001942A1/fr
Priority to EP90911864A priority patent/EP0500533B1/fr
Publication of WO1991001942A1 publication Critical patent/WO1991001942A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/04—Halides
    • C01G3/06—Oxychlorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/08—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/14—Complexes with ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B01J2219/00063—Temperature measurement of the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00177—Controlling or regulating processes controlling the pH
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical

Definitions

  • the present invention relates to the treatment of metallic copper to produce intermediates which may themselves be readily processed into a wide range of copper compounds.
  • Copper sulphate (CuSO 4 .5H 2 0) is a compound used extensively in such areas as agriculture (as a soil additive in pesticides and as a feed additive), medicine, electric batteries, steel manufacture and the petroleum industry.
  • the difficulty in providing a starting point for manufacture of copper chemicals has always been the relative inactivity of the metal.
  • the metal can be oxidised by heating in air, but this is expensive and slow, and the resultant oxide is not satisfactory as a source of cupric salts.
  • the reaction is endothermic and will not proceed at a satisfactory rate unless the temperature of the solution is maintained at a minimum of 70°C, and usually at more than 80°, for example to a temperature in the range 80°C to 90°C.
  • the reaction is usually carried out by pumping the acid through towers packed with scrap copper, through which air is blown, or in submerged reactors, where the acid is agitated in a tank packed with scrap, and air is introduced by submerged aerators.
  • Air addition rates are usually required to be 7 to 10 times the stoichiometric amount, based on its oxygen content, giving an oxygen level of 7 times the stoichiometric amount.
  • the reaction is usually conducted batchwise, and is complete when the residual acid level falls to an acceptable level .
  • the resultant copper sulphate solution is cooled and the copper sulphate crystallises out and subsequently removed, usually by centrifuge.
  • the crystals are dried and packed and the mother liquid is usually returned after acid enrichment, to the next batch.
  • reaction rate is not fast, and production rates of 0.05t/hour/m 3 of reactor volume are common.
  • the air effluent can contain sulphur dioxide, acid droplets and copper sulphate mist, and must be treated in some way.
  • energy costs may amount to in excess of $50/t of product.
  • US-A-3,760,070 discloses a process in which a reaction according to equation 3 is carried out.
  • the copper ammine solution is then heated to produce copper oxide, and the ammonia and ammonium salt are recycled.
  • An alternative ammonia/ammonium salt process uses organic strippers.
  • the organic layer is then separated for re-use, while the aqueous phase is evaporated, cooled, and the copper sulphate recovered in the usual way.
  • Losses of organic stripper can usually be reckoned to be in the order of $10 to 50 per tonne of copper sulphate product.
  • the invention provides, a method of producing copper compounds, including the step of contacting metallic copper with oxygen or an oxygen-containing gas, and an aqueous solution consisting essentially of water in solution in which, to a concentration up to the limit of solubility thereof, is a soluble ammonium salt NH 4 X, where X is the anion of said salt, together with ammonia in an amount such that initially said solution is alkaline, whereby as a result of said contact said metallic copper is initially dissolved to form a copper ammine Cu(NH 3 ) 4 X said ammine formation proceeding until the saturation concentration of said ammine is reached, whereafter said ammine continuously breaks down to form the water insoluble tribasic salt 3Cu(OH) 2 .CuX 2 , and the water-soluble products of the decomposition of said ammine continuously reform the said ammine by further reaction with said metallic copper and said oxygen or oxygen-containing gas until said solution becomes exhausted of the said anion.
  • the invention also provides apparatus for carrying out a method of producing copper compounds, including a cylindrical reaction tank fitted with a circular screen such that copper metal is confined to the area between the screen and the tank walls, and having a bladed agitator located inside the screen driven at a minimum tip speed of 500 metres/minute, and also providing for the introduction of an oxygen containing gas at or near the agitator blades; said tank being provided with means of adding acid at a controlled rate; and said tank being fitted with a solids removal system such that the said water insoluble tribasic copper salt is removed from the reacting solution at a controlled rate.
  • an aqueous solution of an ammonium salt of any of the common acids for example sulphuric, hydrochloric or nitric
  • this solution is made alkaline with aqueous ammonia, preferably to a pH of 7.0 to 8.0, and this solution is then allowed to react with copper metal in the presence of oxygen, then an aqueous medium is produced, which is capable of rapid conversion of copper metal, in the presence of oxygen, into the insoluble tribasic salt, under certain minimum conditions of agitation and aeration, until all the acid ions contained in the original aqueous solution are exhausted.
  • the nett effect is a continuous process for conversion of copper metal into solid 3Cu(0H) 2 .CuS0 4 (Brochantite) in the case of ammonium sulphate, 3Cu(OH) 2 .CuCl 2 (Atacamite or copper oxychloride) in the case of ammonium chloride, or 3Cu(OH) 2 .Cu(N0 3 ) 2 in the case of ammonium nitrate.
  • This process can be controlled, if necessary, to produce direct crystalline salts, by use of the acid in concentrated form.
  • the tribasic salt can easily be converted to copper hydroxide by addition of a stoichiometric quantity of an alkali such as sodium hydroxide, according to the equation
  • the insoluble hydroxide can be recovered by filtration and washing.
  • tribasic salts themselves, particularly the sulphate and chloride, find direct application as fungicides.
  • the invention thus also provides a direct method for the manufacture of such tribasic salts.
  • the reaction mechanism appears to involve initial formation of copper ammine, according to the equation
  • reaction continues to produce tribasic copper salt, while maintaining the copper ammine level in the reaction liquor at the saturation concentration.
  • Fig. 1 is a section through one reactor capable of carrying out the process in accordance with the invention
  • Fig. 2 is a graph showing results of Example 1;
  • Fig. 3 is a graph showing results of Examples 2,3 and 4;
  • Fig. 4 is a graph showing results of Examples 5 and 6;
  • Fig. 5 is a graph showing the results of Example 8; and Fig. 6 is a section through another reactor capable of carrying out the process in accordance with the invention.
  • the process of the present invention involves the exposure of copper metal to the reacting solution in the presence of oxygen or an oxygen containing gas, and depends on a reaction between these components at the copper surface.
  • Such reactions are usually conducted by either pumping the reacting solution through a vessel containing the copper metal, into which oxygen or air is blown, or by agitating the reaction solution in a vessel in which the copper metal is placed, whilst blowing oxygen or air into the solution.
  • reaction of this invention involves the formation of solids in suspension in the reacting solution, resulting in changes in solution viscosity and density, the latter method is preferred, to avoid such problems as tower blockage, channelling and the like.
  • a preferred reactor to carry out the process of the present invention has been designed.
  • a laboratory model constructed to the design is shown in Fig. 1.
  • the reactor 10 has a circular body 12 (preferably formed from a 13cm length of 10cm diameter PVC pipe) with a solid base 14 (preferably also of PVC) and a screw top lip 16 preferably also of PVC.
  • the internal volume was one litre, and is fitted with a circular screen 36.
  • Agitation of the contents is effected by an agitator 20 (preferably bladed, preferably of 2cm diameter and being preferably a polythene turbo agitator located axially) driven by a motor (not shown), preferably a 12v DC motor capable of being located beneath the reactor 10.
  • a preferred speed for the agitator 20 is up to 9,000 rpm.
  • Air entry ports 22,24 are located close to agitator 20 and preferably diametrically opposite one another, towards the base 14 of the reactor 10.
  • the points 22,24 are serviced by, preferably, a constant speed positive displacement air pump (not shown) located outside reactor 10.
  • Other air supply means may be used. For example, air could be introduced through the agitator shaft 38.
  • thermometer 26 and pH probe 28 external through lid 16 so that they are immersed in the liquid 30.
  • An air vent 32 is also located in lid 16.
  • copper scrap (for example copper wire) 34 is placed between screen 36 and walls 12, to a depth of 2cm, and the reactor Gharged with 400ml of reaction solution. Air was supplied at the rate of 1 litre/minute from a positive displacement air ump (not shown) and introduced into the solution at a point adjacent to the agitator blades.
  • Example 1 Several trials were conducted with the reactor of Fig. 1, and are described in the form of Examples 1 to 6 inclusive.
  • Example 1
  • the minimum pH period corresponded to the period of initial solid formation in the liquor, at a copper content of 28 g/1. Thereafter solid formation continued at a rapid rate, such that the total copper content of the reaction liquor rose at a constant rate of 100 gram/litre/hour, whilst the soluble copper content of the liquor remained at around 28 g/1.
  • Example No. 4 This was identical to Example No. 1, except that an initial pH of 8.0 was used. The results are shown in Fig. 3, line A.
  • Example No. 3 This was identical to Example No. 1, except that an initial pH of 8.0 was used. The results are shown in Fig. 3, line B.
  • Example No. 4 This was identical to Example No. 1, except that an initial pH of 8.0 was used. The results are shown in Fig. 3, line B.
  • Example No. 5 This was identical to Example No. 1, except that an agitator speed of 6000 rpm was used. The results are shown in Fig. 3, line C.
  • Example No. 5 This was identical to Example No. 1, except that an agitator speed of 6000 rpm was used. The results are shown in Fig. 3, line C.
  • Example No. 5 This was identical to Example No. 1, except that an agitator speed of 6000 rpm was used. The results are shown in Fig. 3, line C.
  • Example No. 5 Example No. 5
  • Example No. 6 This was identical to Example No. 1, except that ammonium chloride was used in place of ammonium sulphate. The results appear in Fig. 4, line A. The solid precipitate formed was identified as 3.Cu(0H) 2 .CuCl 2 . Example No. 6
  • Example No. 4 This was identical to Example No. 1, except that ammonium nitrate was used. The results appear in Fig. 4, line B. The solid precipitate formed was identified as 3Cu(0H) 2 .Cu(N0 3 ) 2 .
  • the reactor 100 is formed from a generally circular tank 102, preferably formed from stainless steel. Preferred dimensions are 1.5m diameter and 1.5m in depth.
  • Tank 102 has a top portion 104, with an exhaust vent 106 therein.
  • An agitator 114 has a shaft 112 driven by a drive 108, preferably an electric motor.
  • the shaft 112 is located within a tube 116 into which air from a blower or the like is introduced via an inlet 110. Air exits from the base of tube 116 as indicated by the arrows near the base of tank 102.
  • the preferred-dimension tank has a capacity of 15001, and the agitator design may be scaled up from the Fig. 1 arrangement to suit that capacity.
  • the agitator speed is adjusted so that the tip speed is identical with the reactor of Fig. 1, used in Examples 1 to 5.
  • a generally cylindrical screen 118 is located in tank 102, and copper scrap 122 (in the form of copper wire or the like) is located in reaction liquor 120 between screen 118 and tank walls 102.
  • the reactor was charged with 3/4 tonne of copper scrap in the form of wire, bales and cut piping, which was confined between the tank walls and a circular screen, 1500 litres of 150 g/1 ammonium sulphate was introduced into the reactor, and the liquor pH was adjusted to 7.3 using aqueous ammonia.
  • the reactor was operated for 3 hours and the pH, temperature and copper content of the liquor were monitored. The results were identical to those shown in Fig. 2.
  • Example No. 7 was repeated, but after the pH had risen to 7.3 (80 minutes elapsed time) the pH was monitored to 7.3 ⁇ 0.1 by addition of concentrated sulphuric acid, run in from a head tank through a control valve. The example was operated for a total of 4 hours and the results appear in Fig. 5.
  • the final copper liquor was a very thick slurry which became difficult to agitate.
  • the final copper content was 480 g/1, of which only 28g/l was present as soluble copper.
  • a reaction rate of 153 g/1 copper/hour was achieved, after pH adjustment was introduced.
  • the solid precipitate formed was identified as
  • the present invention could be considered as a fuel cell, that is, a process or device which produces energy from the interaction of certain substances.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Selon un procédé de production de composés de cuivre, on met du cuivre métallique en contact avec de l'oxygène ou avec un gaz contenant de l'oxygène, avec une solution aqueuse composée essentiellement d'eau dans laquelle est dissout un sel soluble d'ammonium, NH4X, X étant un anion du sel, et avec une quantité telle de gaz ammoniac que la solution soit initialement alcaline. Suite à ce contact, le cuivre métallique commence par se dissoudre, formant une ammine de cuivre (Cu(NH3)4X, la formation d'ammine se poursuivant jusqu'à ce que la concentration de saturation de l'ammine soit atteinte. Par la suite, l'ammine se décompose en continu, formant 3Cu(OH)2.CuX2, et les produits solubles dans l'eau de la décomposition de l'ammine reforment en continu l'ammine en continuant à réagir avec le cuivre métallique et avec l'oxygène dans le gaz contenant de l'oxygène.
PCT/AU1990/000323 1989-08-01 1990-08-01 Production de composes de cuivre Ceased WO1991001942A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69018645T DE69018645T2 (de) 1989-08-01 1990-08-01 Herstellung von kupferverbindungen.
PCT/AU1990/000323 WO1991001942A1 (fr) 1989-08-01 1990-08-01 Production de composes de cuivre
EP90911864A EP0500533B1 (fr) 1989-08-01 1990-08-01 Production de composes de cuivre

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
AUPJ555289 1989-08-01
AUPJ5552 1989-08-01
AU58043/90 1990-06-29
AU58043/90A AU635943B2 (en) 1989-08-01 1990-06-29 Production of copper compounds
PCT/AU1990/000323 WO1991001942A1 (fr) 1989-08-01 1990-08-01 Production de composes de cuivre

Publications (1)

Publication Number Publication Date
WO1991001942A1 true WO1991001942A1 (fr) 1991-02-21

Family

ID=27155169

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1990/000323 Ceased WO1991001942A1 (fr) 1989-08-01 1990-08-01 Production de composes de cuivre

Country Status (1)

Country Link
WO (1) WO1991001942A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2161128C1 (ru) * 1999-09-27 2000-12-27 Акимов Анатолий Евгеньевич Способ получения хлорокиси меди (ii)
US7273944B2 (en) 2003-11-19 2007-09-25 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
CN102659553A (zh) * 2012-03-30 2012-09-12 常州工学院 用铜包铝导线废料制备有机铜杀菌剂的方法
FR3092727A1 (fr) 2019-02-19 2020-08-21 Upl Limited Procédé de préparation de composés de cuivre

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR793932A (fr) * 1934-11-10 1936-02-04 Carbonates Francais Sa Des Procédé de fabrication de carbonate basique de cuivre et d'hydrate d'oxyde cuivrique
US3760070A (en) * 1970-09-24 1973-09-18 B Joice Manufacture of copper oxide
US3961908A (en) * 1974-02-27 1976-06-08 Freeport Minerals Company Autoclave system for leaching sulfide concentrates
EP0253841A1 (fr) * 1986-01-06 1988-01-27 Pechiney Procede d'elaboration de poudres de metaux de transition par electrolyse en bains de sels fondus.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR793932A (fr) * 1934-11-10 1936-02-04 Carbonates Francais Sa Des Procédé de fabrication de carbonate basique de cuivre et d'hydrate d'oxyde cuivrique
US3760070A (en) * 1970-09-24 1973-09-18 B Joice Manufacture of copper oxide
US3961908A (en) * 1974-02-27 1976-06-08 Freeport Minerals Company Autoclave system for leaching sulfide concentrates
EP0253841A1 (fr) * 1986-01-06 1988-01-27 Pechiney Procede d'elaboration de poudres de metaux de transition par electrolyse en bains de sels fondus.

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Journal of Applied Chemistry of the USSR No 8 1983, TRAVKIN V.F. et al, "Cu extraction from Ammonical Solutions", see pages 1616 to 1620. *
See also references of EP0500533A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2161128C1 (ru) * 1999-09-27 2000-12-27 Акимов Анатолий Евгеньевич Способ получения хлорокиси меди (ii)
US7273944B2 (en) 2003-11-19 2007-09-25 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
CN102659553A (zh) * 2012-03-30 2012-09-12 常州工学院 用铜包铝导线废料制备有机铜杀菌剂的方法
FR3092727A1 (fr) 2019-02-19 2020-08-21 Upl Limited Procédé de préparation de composés de cuivre
US12075783B2 (en) 2019-02-19 2024-09-03 Upl Ltd Process for preparation of copper compounds

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