US2060073A - Copper refining method - Google Patents

Copper refining method Download PDF

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Publication number
US2060073A
US2060073A US459300A US45930030A US2060073A US 2060073 A US2060073 A US 2060073A US 459300 A US459300 A US 459300A US 45930030 A US45930030 A US 45930030A US 2060073 A US2060073 A US 2060073A
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United States
Prior art keywords
copper
carbon
molten
cuprous oxide
furnace
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Expired - Lifetime
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US459300A
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English (en)
Inventor
Russell P Heue
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American Metal Co Ltd
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American Metal Co Ltd
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Filing date
Publication date
Priority to NL37164D priority Critical patent/NL37164C/xx
Priority to BE380283D priority patent/BE380283A/xx
Application filed by American Metal Co Ltd filed Critical American Metal Co Ltd
Priority to US459300A priority patent/US2060073A/en
Priority to GB12940/31A priority patent/GB378008A/en
Priority to FR718014D priority patent/FR718014A/fr
Priority to DEA62200D priority patent/DE661792C/de
Application granted granted Critical
Publication of US2060073A publication Critical patent/US2060073A/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining

Definitions

  • My invention relates to methods for refining copper.
  • the apparatus shown-herein is claimed in my application, Serial Number 605,389, filed April 15. 1932, for copper refining apparatus.
  • a purpose of my invention is to produce commercial copper substantially free from cuprous oxide and at the same time having so few gas cavities as not to interfere with the mechanical working of the copper.
  • a further purpose is to reduce by means of carbon the content of copper oxide to a point much below that reached under the present practice.
  • a further purpose it to crowd carbon into the body of a substantially sulphur-free copper melt in order to reduce the cuprous oxide content to a minimum.
  • a further purpose is to roast solid copper cathodes to substantially eliminate the sulphur
  • a further purpose is to eliminate sulphur con- 5 tamination from solid copper by reduction with hydrogen, remove any dissolved hydrogen by melting in an oxidizing atmosphere and cast the resulting copper.
  • a further purpose is to obtain commercial copper castings free from any excess of carbon dioxide, water vapor or hydrogen, and consequently without gas cavities due to the liberation of these impurities during the solidification period of the copper.
  • a further purpose is to deoxidize copper beyond the point at which it is microscopically oxygen free so that it can be solidified intocastings substantially free from gas cavities and to cast the copper preferably while protecting it from the 40 atmosphere, desirably by carbonmonoxide free,
  • Figure l is a top plan view of
  • Figure 2 is an enlarged vertical section of the carbon reducing furnace seen in Figure 1.
  • FIGS 3 to 5 are diagrammatic views useful in explaining my invention.
  • the common practice is to melt copper cathodes in largeintermittent reverberatory furnaces. In such furnaces, the conventional mode of oper purity in the molten copper. Oxygen is also present'in thebath as dissolved cuprous oxide. The blowing, while removing part of the sulphur, increases the oxygen content of the bath and saturates the bath with nitrogen and other gases from the atmosphere.
  • the primary purpose of the poling operation is to remove the excess of oxygen, present largely in the form of cuprous oxide. In doing so, however, the bath takes up hydrogen, carbon monoxide, carbon dioxide and water vapor from the organic matter.
  • the bath lsprotected by charcoal or coke floating upon the surface.
  • the amount of reduction possible from carbon used in this manner is negligible.
  • A.Cu activity of copper
  • A.CO activity of carbon monoxide
  • A;Cu:0 activity oi cuprous oxide
  • A.C activity or carbon in the above reaction equilibrium is never reached during poling. It is only attained when the cuprous oxide is practically all removed.
  • Equation (7) becomes:
  • Equation (11) has been plotted in Figure 4, using (A.Cua0) values as the abscissae and (A.Ha) values as the ordinates.
  • the concentrations oi! hydrogen and carbon monoxide are low.
  • the concentrations of cuprous oxide fall, as shown progressively at points 11, c, and d, the concentrations of hydrogen and carbon monoxide remain substantially the same.
  • Reaction (1) can hardly take place during the solidification oi the sting, because no carbon is present at that time.
  • Reactions (2) and (3) could occur, since both carbon monoxide and hydrogen are present in copper made by the prior art commercial process.
  • My low sulphur bath does not require blowing,- and therefore does not have the high oxygen, content due to blowing, and the saturation with other atmospheric gases for which it is respon-.-
  • roasting or calcining operation to remove sulphur is best performed in the continuous fiue'of a furnace as shown in my Patent, No. 1,914,716, for Copper. melting furnace, granted June 20, 1933, or in Lukens and Heuer Patent, No. 1,733,419, for Continuous copper melting furnace, granted October 29. 1929.
  • the furnace A of Figure 1 is of the general type shown in my Patent, No. 1,914,716, above referred to.
  • Cold cathodes are charged at 9 by any suitable pusher- Ill on to the continuous hearth ll operating in the flue l2.
  • Thehearth is moved by a motor I! and any suitable connections.
  • the piles of cathodes ll are carried clockwise to the discharge point l5, where they arepicked up by the fork l6 and carried into the furnace l1 and there dropped.
  • the charging fork I8 is desirably moved in and out through a door l8. 1
  • the bath l9 desirably covered by a suitable protective slag, is heated by products of combustion from burners at 20.
  • products of combustion from burners at 20.
  • the products of combustion pass through the neck 2
  • the products of cumbustion are prevented from taking a clockwise path by the wall 23.
  • the hearth II in the flue i! may be continuous or may consist of a plurality of cars separately moved about the flue.
  • the continuous mode of operation is much superior, and therefore I indicate the hearth as extending around the flue and being turned by any suitable driving means l3.
  • the preheating and roasting chamber l2 contains a non-reducing atmosphere.
  • the copper sulphate or other sulphur compound adhering to the cathode is calcined, and is decomposed by the products of combustion.
  • The-sulphur is carried off as sulphur dioxide.
  • the cathodes should be heated to about 815 C. to complete the formation of sulphur dioxide. Lower temperatures will suffice, although operation is slower inthat case. Higher temperatures will work satisfactorily provided care is taken not to melt the cathodes in the flue. Melting here is objectionable for various reasons, metallurgically because molten copper gen sulphide. Here also, the presence of molten copper is undesirable for the reason above stated.
  • I will preferably melt the copper under slightly oxidizing furnace conditions to remove dissolved or from-the fiue gases by a suitable slag.
  • slag used may be the normal slag forming from oxidation of the copper, or it may-beaspecialslagasdesired.
  • I pour the metal from the pool ll of furnace A into furnace 88 B.
  • Furnace B is free from gases of combustion, and is heated electrically or by any other suitable means.
  • I show electrodes 2
  • any conventional electric furnace, resistance or induction, may be used as my furnace B. Copper from the bath I! is preferably charged into the inlet opening II of furnace B through a closed trough II heated by a burner 3
  • the furnace B is filled, both above and below the level of the copper, with coke or other suitable carbonaceous material which will not contaminate thecopper with hydrogenor water vapor.
  • Coke is a harmless carbonaceous reducing agent which is forced in through the openings 32 and a near the top, by means of plungers '32 and 33.
  • Theheatinginthefurnace ispartly duetothe electrical resistance of the coke surrounding the electrodes, since the electrodes will not usually be immersed in the bath.
  • the copper bath'fl may be drawn off as desired through the tap opening II and the pouring spout I at the end of the finance. 7
  • the level of the pouring spout is slightly above that of the'copper bath 34, so that the furnace must be rotated slightly in order to pour from the'spout.
  • I preferably make my furnace B cir- 7 color in cross section.
  • l'br'rotating the furnace r I provide suitable supporting rollers 31 engaging bands ll, and also a gear driving band I! engaged by a rack I which is moved backfand forth by a I screw ll through a, non-rotatable nut l2, secured used to agitate thecopper in contact with the carbon, ifdesired, but I do not consider agitation s necessary to accomplish the reduction of cuprous oxide.
  • the carbon monoxide dissolved in the copper has a "buffer" action in protecting the copper from increase in cuprous oxide content.
  • This carbon monoxide, produced by Reaction (14) is formed from carbon dioxide which wasformerly dissolved in the copper, so that after- Reaction (14) is complete, the carbon dioxide will be removed from the copper, and carbon monoxide produced instead. Notwithstanding that two volumes of carbon monoxide are produced from one volume of carbon dioxide, most of the carbon monoxide resulting from Reaction (14) will remain dissolved in the copper because carbon monoxideis quite soluble in molten copper, while carbon dioxide is only sparingly soluble under the same conditions.
  • FIG. 1 I illustrate diagrammatically conventional casting apparatus consisting of a. conventional casting wheel having supporting structure 44 and molds 45, adapted to be moved in either direction to a position registering with the pouring spout 36, when copper may be poured through openings 46 into the molds.
  • I pour preferably into vertical molds.
  • the molten copper may simply be poured in a chamber containing carbon monoxide.
  • the first step might be eliminated if sulphur-free material could be obtained, and of course the sulphur might less desirably be removed after melting.
  • the elimination of sulphur is accomplished before melting, but this is not essential, especially if the conventional copper melting reverberatory furnace is to be used, since the copper can be' charged into such a furnace either continuously or intermittently, with or without preheating, can be melted, blown to remove sulphur if desired, poled to remove part of the oxygen content, deoxidized by treatment in the deoxidation furnace'B and cast, preferably with proper protection.
  • the last step while offering a desirable combination in the practice of my invention, could be dispensed with if it were desired to transfer the copper to a storage furnace, for example.
  • the processof producing copper castings free from excessive gas cavities which consists in exposing the molten copper to a large surface of carbon submerged throughout the copper free from contamination of substances rich in hydrogen preliminary to casting, in separating the molten copper from the carbon, in casting the copper in pure condition and in protecting the copper from air during casting by surrounding the copper with carbon monoxide free from contamination with substances which will cause the liberation of carbon dioxide, hydrogen or steam in the solidifying copper.
  • the process which consistsin preheating solid copper charges, in melting the charges by fuel combustion while exposed to a bath of molten copper, in transferring the molten copper to a deoxidizing vessel, in deoxidizing the molten copper by the action of carbon monoxide free from substances which will cause hydrogen or steam to be liberated in the copper during solidification, in transferring the molten copper from the deoxidizing vessel to the point of casting and in casting the copper in pure condition while blanketing it with a gas having 'a predominantly reducing component of carbon monoxide and having a sufllciently low partial pressure of oxygen so as not to contaminote the copper with oxygen or its compounds other than carbon monoxide.
  • the process which consists in preparing oxygen-bearing molten copper in the fuel-fired furnace, in transferring the molten copper to the deoxidation furnace, removing from the molten copper substantially all of the cuprous oxide and suflicient of the gas in the with air during copper to render the remainder harmless bycarbon reduction in the deoxidation furnace in an atmosphere having insuflicient carbon dioxide and hydrogen to harmfully affect the copper, in casting the copper and in protecting thecopper from excessive contact with air during casting.
  • the method of treating copper to make castings free from cuprous oxide and objectionable gas cavities which consists in melting the copper while in contact with products of fuel combustion, and in subsequently removing from the molten copper the cuprous oxide and sufficient of its content of dissolved gas to render the remainder harmless by exposing the copper in molten condition to contact with carbon in the absence of contamination with air and with gases of combustion from hydrocarbon fuel.
  • gaseous products of the fuel combustion in casting the copper and in shielding the copper during casting from air, oxidizing gaseous products of fuel combustion and hydroen.
  • the process which consists in substantially eliminating the cuprous oxide content of oxygen-bearing molten copper by reduction with carbon in an atmos-- phere having insufllcient carbon dioxide and hydrogen to harmfully affect the copper, in prolonging the reduction until the harmful content of carbon dioxide is reduced to carbon monoxide, in maintaining carbon monoxide in the molten copper, in separating the molten copper from the carbon and in casting the copper in pure condition free from excessive contact with air.
  • the method of treating copper to produce castings free from cuprous oxide and objectionable gas cavities which consists in melting the copper by fuel combustion in which the gases of combustion are in contact with the molten copper to produce a molten bath containing cuprous oxide and in removing from the copper cuprous oxide and prolonging the deoxidation for a time sufficient to render the remainder of the oxides of carbon harmless, by maintaining .the copper in molten condition in contact with carbon in an atmosphere having so little carbon dioxideand hydrogen as not to harmfully affect the copper.
  • the process of purifying copper which consists in preparing oxygen-bearing molten copper under fuel-fired conditions in which the molten copper is exposed to the products of fuel combustion, in exposing the molten copper in a confined space to contact with carbon while protecting the copper from air and products of fuel combustion, in agitating the molten copper while it is in contact with the carbon for a time sufficient to completely deoxidize the copper and effect removal of harmful gas from the copper, in transferring the molten copper from the confined space to the point of casting and in subsequently cooling the molten copper to solidify it.
  • the method of refining metals which readily oxidize upon exposure to air in their molten state which comprises subjecting the metal to an oxidizing reaction to remove sulphur, melting the metal with fuel heating flames, subjecting the metal in molten condition to a complete reaction with a harmless carbonaceous reducing agent to remove substantially all of the metallic oxides while keeping the metal protected from the air and the contaminating products of combustion of fuel heating flames, and pouring the metal while protecting it from the air and the contaminating products of combustion of fuel heating flames.
  • the method of refining copper which comprises subjecting the metal to an oxidizing reaction to remove sulphur, melting the metal in a fuel fired reverberatory furnace, subjecting the oxidized metal in molten condition to a complete reaction with a harmless carbonaceous reducing agent to remove substantially all of the metallic oxides while fully protecting the metal from the atmospheric air and the contaminating products of combustion of fuel heating flames, and pouring the metal while protecting it from the air and the contaminating products of combustion of fuel 30.
  • the method of refining copper which comprises, melting the copper in a fuel-fired furnace which tends to oxidize the metal, transferring the metal to a treating vessel and there subjecting it in molten condition to a complete reaction with a harmless carbonaceous reducing agent by bringing all of the metal into thorough contact with the reducing agent while keeping the metal protected from the air and the contaminating products of combustion of fuel heating flames to perform a complete reducing action on the metal, and pouring the oxygen-free copper while protecting it from air by a gas composed principally as to active constituent of carbon monoxide.
  • the method of refining copper which comprises, melting the copper in a fuel fired reverberatory furnace, oxidizing the copper to remove sulphur, subjecting the copper in molten condition to a complete reaction with a harmless carbonaceous reducing agent by bringing all of the metal into thorough and intimate contact with the'reducing agent while keeping the metal protected from the air and the contaminating products of combustion of fuel heating flames to remove substantially all of the metallic oxides, and casting the metal while protecting it from oxidizing influences and the contaminating products of combustion of fuel heating flames.
  • the process which consists in treating molten copper containing cuprous oxide with carbon monoxide, thereby taking out cuprous oxide and distributing carbon dioxide in the molten copper, in reducing the carbon dioxide so formed by carbon in contact with the molten copper in a confined space free from substances which cause the liberation of hydrogen or steam in the solidifying copper, in maintaining carbon monoxide in the molten copper, in transferring the molten copper from the confined space to the point of casting and in subsequently cooling the molten copper to solidify it.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Glass Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US459300A 1930-06-05 1930-06-05 Copper refining method Expired - Lifetime US2060073A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL37164D NL37164C (en(2012)) 1930-06-05
BE380283D BE380283A (en(2012)) 1930-06-05
US459300A US2060073A (en) 1930-06-05 1930-06-05 Copper refining method
GB12940/31A GB378008A (en) 1930-06-05 1931-05-01 Improvements in copper refining methods, apparatus and products
FR718014D FR718014A (fr) 1930-06-05 1931-06-01 Procédé pour le raffinage du cuivre, appareil pour la mise en oeuvre et produits obtenus
DEA62200D DE661792C (de) 1930-06-05 1931-06-05 Verfahren zum Raffinieren von Kupfer

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Application Number Priority Date Filing Date Title
US459300A US2060073A (en) 1930-06-05 1930-06-05 Copper refining method

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US2060073A true US2060073A (en) 1936-11-10

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US459300A Expired - Lifetime US2060073A (en) 1930-06-05 1930-06-05 Copper refining method

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US (1) US2060073A (en(2012))
BE (1) BE380283A (en(2012))
DE (1) DE661792C (en(2012))
FR (1) FR718014A (en(2012))
GB (1) GB378008A (en(2012))
NL (1) NL37164C (en(2012))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732294A (en) * 1950-09-28 1956-01-24 Manufacture of copper
US3484280A (en) * 1967-04-04 1969-12-16 Gen Electric Atmosphere control in dip-forming process
CN106197005A (zh) * 2016-08-31 2016-12-07 浙江大学宁波理工学院 精炼炉

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1171161B (de) * 1961-03-04 1964-05-27 Jlario Properzi Verfahren und Lichtbogenofen zum Ein-schmelzen von Metallen, insbesondere von Kupferkathoden

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732294A (en) * 1950-09-28 1956-01-24 Manufacture of copper
US3484280A (en) * 1967-04-04 1969-12-16 Gen Electric Atmosphere control in dip-forming process
CN106197005A (zh) * 2016-08-31 2016-12-07 浙江大学宁波理工学院 精炼炉
CN106197005B (zh) * 2016-08-31 2018-04-20 浙江大学宁波理工学院 精炼炉内压力控制方法

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Publication number Publication date
GB378008A (en) 1932-08-02
NL37164C (en(2012))
FR718014A (fr) 1932-01-18
DE661792C (de) 1938-06-28
BE380283A (en(2012))

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