WO2006029162A1 - Method of continuous fire refining of copper - Google Patents
Method of continuous fire refining of copper Download PDFInfo
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- WO2006029162A1 WO2006029162A1 PCT/US2005/031731 US2005031731W WO2006029162A1 WO 2006029162 A1 WO2006029162 A1 WO 2006029162A1 US 2005031731 W US2005031731 W US 2005031731W WO 2006029162 A1 WO2006029162 A1 WO 2006029162A1
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- Prior art keywords
- copper
- liquid
- reduction
- forth
- oxidized
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 117
- 239000010949 copper Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007670 refining Methods 0.000 title claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims abstract description 8
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 238000010079 rubber tapping Methods 0.000 claims abstract 8
- 239000000567 combustion gas Substances 0.000 claims abstract 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 39
- 239000003638 chemical reducing agent Substances 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- 239000003345 natural gas Substances 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 7
- 239000003517 fume Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 239000000919 ceramic Substances 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims 1
- 229940112669 cuprous oxide Drugs 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011133 lead Substances 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 235000010269 sulphur dioxide Nutrition 0.000 claims 1
- 239000004291 sulphur dioxide Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000002792 vascular Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000512668 Eunectes Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- -1 long reduction time Chemical compound 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000010747 number 6 fuel oil Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B15/005—Smelting or converting in a succession of furnaces
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates to a method of intensive, continuous fire refining of blister copper or secondary copper.
- Fire refining of blister copper is carried out in stationary reverberatory or vascular furnaces, called anode furnaces due to the most common casting of refined copper in the form of anodes, which are transferred to electrolytical refining.
- Fire refining process is a classical batch process consisting of four stages: charging, oxidation and impurities slagging, reduction and anode casting. Time of refining cycle without the stage of melting varies from 6 to 14 hours.
- Oxidized copper after oxidation stage contains from 5000 to 10000 ppm of oxygen.
- the copper is reduced by carboneous or amonia reductant.
- the most common reductant in use are the oil or natural gas.
- the oil or natural gas are injected with air into the bath of molten copper through a tuyere or tuyeres.
- Copper reduction faces significant limitations in the process rate and efficiency of reductant utilisation.
- Reduction stage of the liquid copper charge which fluctuates from 150 to 400 t, varies in the range from 1.2 to 2.0 hours. Reported reductant efficiency is below 50%. Injection of liquid or gaseous reductant into the copper produces black fumes in off-gas due to thermal decomposition of hydrocarbons.
- Partial carbon utilisation in oxygen reduction from copper causes the presence of carbon particles in the reduction gases, which are partly combusted if the burner flame is oxidising. Carbon particles are transferred to the furnace off-gas, creating black fumes emitted through a chimney to the atmosphere.
- R. Nenych, F. Kadler and V. Sedlacek replaced the conventional reduction with wood by ammonia, what allowed for production of high quality copper.
- Ammonia consumption is about 1 kg/t of copper, when oxygen is reduced from 4000 a 1000 ppm. (R. Henych et al., "Copper refining by gaseous ammonia", J. of Metals, VoI 17, N°4, April 1955).
- N. Themelis and P.Schmidt have patented the deoxidisation of a liquid copper by injection of various reformed hydrocarbons (methane, ethane, butane) with steam, leading to the formation of the gas containing carbon monoxide and hydrogen. Patented installation was based on vascular furnace. ("Apparatus and process for the gaseous deoxidisation of molten metal, Canadian Patent N 0 827.066, November 1969).
- Figure 1 is a sketch illustrating schematically the principle of intensive, continuous fire refining of blister copper supplied from continuous Mitsubishi copper matte converting furnace.
- This invention refers to a pirometallurgical method of oxygen removal from a liquid copper by the use of solid carboneous reductant, charged on the surface of copper in addition to the injection of reductant through tuyeres or lances and simultaneous agitation of copper bath with inert gas introduced via porous plugs.
- the method in which carboneous reductant and hydrocarbons of oil or natural gas mixed with air or steam react with oxygen dissolved in copper results in high rate of reduction, shorten the time and increase of reductant efficiency.
- the invention leading to a method of oxygen extraction from a liquid copper consists of following stages:
- copper reduction (4) after oxidation and slagging of impurities, is carried out by injection of a liquid or gaseous reductant (oil, natutral gas) (3) with simultaneous addition of solid reductant (5) onto copper bath surface(4) and bath agitation with inert gas (1) through porous plugs (2)
- a liquid or gaseous reductant oil, natutral gas
- inert gas (1) Injection of inert gas (1) through the porous plug (2) prevents the formation of the gradient of oxygen content in the copper slowing down the rate of reaction. Continuous stirring of the copper bath in whole volume by inert gas (1) ensures the mass transfer onto the reaction surface (copper/charcoal).
- Floating charcoal or coke bed (5) on the copper (4) surface allows for higher flexibility of burner operation. Even in the case of oxidising flame the charcoal (5) is protecting copper against the oxidation, permitting for more efficient use of fuel and better control of copper temperature. Moreover, the excess oxygen in the burner allows for post- combustion of reduction gases (7) leaving the bath producing clean gases.
- This invention has following advantages compared with traditional methods of copper reduction: a) Application of solid carbon addition combined with bath stirring by nitrogen introduced by porous plugs during injection of liquid or gaseous reductant significantly shorten reduction time from 40 to 60% in comparison to common reduction practice. b) Efficiency of reductant (carbon and hydrocarbons) increases from 30 to 50% of the average values of traditional operation. c) Emission of gases with black fumes (carbon black) is drastically decreased reducing negative process impact on the environment. d) Higher reductant efficiency and shorter reduction time results in the decrease of unitary reductant and fuel consumption as well as in the increase of furnace productivity, e) Cost of method application is low. Necessary modifications of refining furnace are minor. f) EXAMPLE 1
- Copper refining is carried out in vascular anode furnace capacity of 150 t of copper as it is schematically illustrated in Figure 1.
- Four porous plugs (2) are mounted in the bottom part of the furnace.
- nitrogen (1) is injected into the molten copper (4).
- Nitrogen flowrate varies from 40 to 120 NmVh.
- Oxidation period is ended by skimming out of the slag.
- Oxygen content in the copper is in the level of 8000 ppm.
- 1.5 to 4 kg of charcoal (5) per tonne of copper is charged through the mouth onto copper surface.
- Flow of oil through one tuyere is put on (about 4 - 8 kg/h per tonne of copper) together with air (4 - 8 Nm 3 /h per tonne of copper).
- Furnace is tilted and the tuyere immersed starting to blow into the copper. Oil flowrate is increased gradually up to the point that black fumes are not emitted. Setting of the burner is changed. Oil flowrate through the burner is shut down and air flow is kept at the level of 3 - 20 Nm 3 /h per tonne of copper. Introduced air through the burner ensures effective post-combustion of reduction gases leaving the bath. Charcoal on the surface prevents the copper against oxidation. Produced off-gases leaving the furnace to a chimney are clean and acceptable for emission. After 45 min of reductant injection through the tuyere oil flowrate is put gradually down and the furnace is tilted putting tuyere above the bath. Next, oil and air flow is shut down. Oxygen content in copper is 400 - 800 ppm and the furnace is prepared for anode casting.
- Copper refining is carried out in stationary anode furnace of capacity 300 t of copper.
- porous plugs are installed in the bottom part of side wall against the wall with charging window. Nitrogen flowrate through porous plug is 0.3 - 1.0 Nm 3 Zh per tonne of copper. After finishing oxidation period and skimming out of refining slag the portion of 1.3 - 4.0 kg of charcoal per tonne of copper is charged through a window onto the copper surface.
- the oil flow is put on through a lance (2 - 5 kg/h per tonne of copper) together with air (2 - 5 Nm 3 /h tonne of copper). Lance is immersed into the copper and reduction. Burner is supplied by natural gas.
- Burner parameters are set: 1 - 3 Nm 3 /h of natural gas and 7 - 20 Nm 3 /h of air per tonne of copper. It ensures effective post- combustion of reduction gases and emission of clean off-gas to the atmosphere. After 100 min the lance is removed and the oil and air flows shut down. Oxygen content has been decreased from 6000 - 8000 ppm to about 400 - 800 ppm. Next, anode casting is proceeded.
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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)
Abstract
A method of intensive, continuous copper fire refining, said method comprising the stages of: continuous tapping in a liquid copper (4) into a first oxidation reactor; liquid copper oxidation with combustion gases containing oxygen or with air; simultaneous formation of slag collecting impurities; continuous tapping out of oxidized copper and refining slag from the first reactor (8); continuous tapping in of oxidized copper into a second reduction reactor; reduction of copper with carbon and reducing gases formed by partial combustion of fuel and carbon; and continuous tapping out of reduced copper (14).
Description
METHOD OF CONTINUOUS FIRE REFINING OF COPPER
BACKGROUND OF INVENTION
1. Field of Invention:
This invention relates to a method of intensive, continuous fire refining of blister copper or secondary copper.
2. Description of the Prior Art:
Smelting of copper concentrates produces matte and slag. Copper matte is converted into blister copper in Peirce-Smith, Hoboken converters or continuous converting processes such as Kennecott-Outokumpu or Mitsubishi. Blister copper is directed to fire refining process prior electrorefming.
Fire refining of blister copper is carried out in stationary reverberatory or vascular furnaces, called anode furnaces due to the most common casting of refined copper in the form of anodes, which are transferred to electrolytical refining.
Fire refining process is a classical batch process consisting of four stages: charging, oxidation and impurities slagging, reduction and anode casting. Time of refining cycle without the stage of melting varies from 6 to 14 hours.
Oxidized copper after oxidation stage contains from 5000 to 10000 ppm of oxygen. The copper is reduced by carboneous or amonia reductant. The most common reductant in use are the oil or natural gas. The oil or natural gas are injected with air into the bath of molten copper through a tuyere or tuyeres. Copper reduction faces significant limitations in the process rate and efficiency of reductant utilisation. Reduction stage of the liquid copper charge, which fluctuates from 150 to 400 t, varies in the range from 1.2 to 2.0 hours. Reported reductant efficiency is below 50%. Injection of liquid or gaseous reductant into the copper produces black fumes in off-gas due to thermal decomposition of hydrocarbons. Partial carbon utilisation in oxygen reduction from copper causes the presence of carbon particles in the reduction gases, which are partly combusted if the burner flame is oxidising.
Carbon particles are transferred to the furnace off-gas, creating black fumes emitted through a chimney to the atmosphere.
Reduction of a liquid oxidised copper is practised for centuries and it was first described by Georgious Agricola (G:Agricola: "De Re Metallica", translated from latin, la edition 1556 por Hebert C. Hoover y Lou H. Hoover, Dover Publications, 1950, 535-536). After copper oxidition with air in open hearth furnace and removal of impurities, the copper was reduced with a wood.. Copper reduction with wood (poling) is still practised in some smelters. L.Klein presented a new idea of the use of gas reductant as a substitute of a wood. (
"Gaseous reduction of oxygen-containing copper", J. of Metals, VoI 13, N°8, August 1961, 545-547 ; U.S. Patent N° 2.989.397, June 1961). The study showed that the injection of natural gas with air states a better solution than the injection of only natural gas into a liquid copper. Method of deoxidization of copper with reformed natural gas and related apparatus have been patented by Phelps Dodge Corporation in USA and Canada. (C.Kuzell, M. Fowler, S. Davis y L. Klein: "Apparatus for reforming gases" U.S. Patent N° 3.071.454, January 1963; "Gaseous reduction of oxygen containing copper", Canadian Patent N0 668.593, August 1963)
R. Nenych, F. Kadler and V. Sedlacek replaced the conventional reduction with wood by ammonia, what allowed for production of high quality copper. Ammonia consumption is about 1 kg/t of copper, when oxygen is reduced from 4000 a 1000 ppm. (R. Henych et al., "Copper refining by gaseous ammonia", J. of Metals, VoI 17, N°4, April 1955).
N. Themelis and P.Schmidt have patented the deoxidisation of a liquid copper by injection of various reformed hydrocarbons (methane, ethane, butane) with steam, leading to the formation of the gas containing carbon monoxide and hydrogen. Patented installation was based on vascular furnace. ("Apparatus and process for the gaseous deoxidisation of molten metal, Canadian Patent N0 827.066, November 1969).
R.Beck, C.Andersen and M. Messner have patented the process of copper deoxidisation with the mix of natural gas/air. ("Process for deoxidising copper with natural gas-air mixture, U.S. Patent N0 3.619.177, November 1971).
Anaconda Company patented a process of copper deoxidisation in vascular furnace by injection through lances of the mix of natural gas or Diesel oil and water vapour (W. Foard and R. Lear: "Refining copper" U.S.Patent N°3,529.956, September, 1970).
J. Henderson and W. Johnson have patented for ASARCO the method of copper reduction in a vascular furnace by natural gas injection through tuyeres ("Gas poling of copper", U.S.Patent N0 3.623.863, November 1971).
G. Mckerrow and D. Panell reviewed in a paper "Gaseous deoxidization of anode copper at the Noranda smelter" Canadian Metallurgical Quarterly, VoI 11, N°4, 1972, 629- 633, the evolution of methods of copper deoxidization in Noranda smelter using natural gas injected through tuyeres in a vascular furnace. J. Oudiz made a general review of copper reduction processes ("Poling processes for copper refining", J. of Metals, VoI 25, December 1973, 35-38). Based on industrial data the consumption of reductant, benefits and problems related with the use of various reductants, reforming reactions and reductant efficiency have been analyzed. L.Lavrov ("Deoxidization of anode copper by natural gas and steam mixture", The
Soviet Journal of Non-Ferrous Metals, VoI N°19, N°5, English translation, May 1978, 25- 26) verified the use of a mix of natural gas and steam injected through a lance.
C. Toro and V. Paredes ("Sustituciόn parcial del petrόleo diesel por Enap-6 como agente reductor en Ie proceso de obtenciόn de cobre anόdico en Ia fundiciόn Potrerillos", 34 a Convenciόn Anual IJJVICh, Noviembre 1983, Rancagua) developed in industrial scale and demonstrated the possibilities of the use of heavy oil (ENAP-6), with higher sulphur content and lower price, in copper reduction.
J. Minoura ("Bunker fuel oil poling in anode furnace at Kosaka smelter", 114th AIME Annual Meeting, 1985, NY, USA) describes the copper reduction with heavy oil (Bunker C), showing the advantages and lower costs with comparison of copper reduction with ammonia practiced since 1967.
Referencies related to the use of porous plugs in copper fire refining are fragmentary since 1980 decade (P. Goyal, N. Themelis and W. Zanchuk, "Gaseous refining of anode copper", J. of Metals, VoI 34, December 1982, 22-28; P. Goyal, S. Joshi and J.
Wang "Porous plug injection in anode refining furnace", J. of Metals, VoI 35, December
1983, 52-58). The porous plugs use was transferred from iron metallurgy and developed next in the area of metal casting. Industrial applications in copper refining were oriented first to copper desulphurisation by nitrogen stirring. The idea of copper reduction with hydrogen introduced via porous plugs was investigated only in laboratory scale. Description of industrial operation of porous plugs is presented in a paper of A,
Rigby y M. Lanyi: "Porous plug in molten copper production and refining", CEVT96, August 1996, 393-403.
Operational practice and proposed methods of injection, bath agitation and type of reductant, point out the existing problems in oxygen removal from a liquid copper, such as long reduction time, low reductant efficiency and emission of the gases with non- combusted particles.
SUMMARY OF INVENTION
It is an object of invention to provide a new method of continuous copper fire refining. This method is attained by a method, which uses solid additional reductant floating on the copper surface with simultaneous bath stirring by the inert gas supplied by porous plugs.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a sketch illustrating schematically the principle of intensive, continuous fire refining of blister copper supplied from continuous Mitsubishi copper matte converting furnace.
DETAILED DESCRIPTION OF INVENTION
This invention refers to a pirometallurgical method of oxygen removal from a liquid copper by the use of solid carboneous reductant, charged on the surface of copper in addition to the injection of reductant through tuyeres or lances and simultaneous agitation
of copper bath with inert gas introduced via porous plugs. The method in which carboneous reductant and hydrocarbons of oil or natural gas mixed with air or steam react with oxygen dissolved in copper results in high rate of reduction, shorten the time and increase of reductant efficiency. Thus, the invention leading to a method of oxygen extraction from a liquid copper consists of following stages:
a) Oxidation of copper bath to the level necessary for impurities removal; b) Addition of carboneous reductant onto copper surface, injection of the mix fuel reductat through tuyere(s) and agitacion of bath by nitrogen via porous plugs; c) Continuation of oxygen extraction from a copper up to the desire oxygen content.
According to this invention, copper reduction (4), after oxidation and slagging of impurities, is carried out by injection of a liquid or gaseous reductant (oil, natutral gas) (3) with simultaneous addition of solid reductant (5) onto copper bath surface(4) and bath agitation with inert gas (1) through porous plugs (2)
Injection of a liquid or gaseous reductant with deficient amount of air (3) into the liquid copper (4) produces chemical reactions in the gaseous jet from tuyere and generated gas bubbles (9) rising up:
• Decomposition of hydrocarbons CnHm => n C + m H2
• Partial combustion with air 2 C + O2 => 2 CO
2 H2 + O2 =^> H2O
• Reduction of copper (O)00pper + C => CO (O) copper + CO => CO2
(O) copper + H2 => H2O
Addition of charcoal or another solid carboneous reductant on the surface of copper bath initiates the reactions at the copper/carbon interface:
(O copper + C => CO
(O) copper + CO => CO2
CO2 + C => 2 CO
Injection of inert gas (1) through the porous plug (2) prevents the formation of the gradient of oxygen content in the copper slowing down the rate of reaction. Continuous stirring of the copper bath in whole volume by inert gas (1) ensures the mass transfer onto the reaction surface (copper/charcoal).
Simultaneous copper (4) reduction by injected reductant (oil, natural gas) and floating bed of charcoal or coke increases significantly the total process rate, decreasing the time of reduction and increasing furnace productivity.
Floating charcoal or coke bed (5) on the copper (4) surface allows for higher flexibility of burner operation. Even in the case of oxidising flame the charcoal (5) is protecting copper against the oxidation, permitting for more efficient use of fuel and better control of copper temperature. Moreover, the excess oxygen in the burner allows for post- combustion of reduction gases (7) leaving the bath producing clean gases.
The major problem of copper (4) reduction by injection of oil or natural gas (3) is the formation and emission of black fumes. Thermal decomposition of hydrocarbons produces hydrogen and elemental carbon (9). Carbon particles are partly reacting with oxygen from copper, but partly are rising up inside the bubbles being released from the melt. This part of carbon can be partly combusted over the melt if there is enough oxygen supplied by the burner. But, primary carbon monoxide is from reaction gases is combusting. Finally, significant part of carbon goes to chimney being emitted to the atmosphere. According to invention, floating bed of charcoal or coke on the copper surface acts as a filter for the carbon particles. The particles are caught by a filter, sintered and the carbon is used as a reductant together with charcoal. This leads to higher utilisation of carbon and higher reductant efficiency.
This invention has following advantages compared with traditional methods of copper reduction: a) Application of solid carbon addition combined with bath stirring by nitrogen introduced by porous plugs during injection of liquid or gaseous reductant significantly shorten reduction time from 40 to 60% in comparison to common reduction practice. b) Efficiency of reductant (carbon and hydrocarbons) increases from 30 to 50% of the average values of traditional operation. c) Emission of gases with black fumes (carbon black) is drastically decreased reducing negative process impact on the environment. d) Higher reductant efficiency and shorter reduction time results in the decrease of unitary reductant and fuel consumption as well as in the increase of furnace productivity, e) Cost of method application is low. Necessary modifications of refining furnace are minor. f) EXAMPLE 1
Copper refining is carried out in vascular anode furnace capacity of 150 t of copper as it is schematically illustrated in Figure 1. Four porous plugs (2) are mounted in the bottom part of the furnace. Through the porous plugs nitrogen (1) is injected into the molten copper (4). Nitrogen flowrate varies from 40 to 120 NmVh. Oxidation period is ended by skimming out of the slag. Oxygen content in the copper is in the level of 8000 ppm. Next, 1.5 to 4 kg of charcoal (5) per tonne of copper is charged through the mouth onto copper surface. Flow of oil through one tuyere is put on (about 4 - 8 kg/h per tonne of copper) together with air (4 - 8 Nm3/h per tonne of copper). Furnace is tilted and the tuyere immersed starting to blow into the copper. Oil flowrate is increased gradually up to the point that black fumes are not emitted. Setting of the burner is changed. Oil flowrate through the burner is shut down and air flow is kept at the level of 3 - 20 Nm3/h per tonne of copper. Introduced air through the burner ensures effective post-combustion of reduction gases leaving the bath. Charcoal on the surface prevents the copper against oxidation.
Produced off-gases leaving the furnace to a chimney are clean and acceptable for emission. After 45 min of reductant injection through the tuyere oil flowrate is put gradually down and the furnace is tilted putting tuyere above the bath. Next, oil and air flow is shut down. Oxygen content in copper is 400 - 800 ppm and the furnace is prepared for anode casting.
EXAMPLE 2
Copper refining is carried out in stationary anode furnace of capacity 300 t of copper. Four porous plugs are installed in the bottom part of side wall against the wall with charging window. Nitrogen flowrate through porous plug is 0.3 - 1.0 Nm3Zh per tonne of copper. After finishing oxidation period and skimming out of refining slag the portion of 1.3 - 4.0 kg of charcoal per tonne of copper is charged through a window onto the copper surface. Next, the oil flow is put on through a lance (2 - 5 kg/h per tonne of copper) together with air (2 - 5 Nm3/h tonne of copper). Lance is immersed into the copper and reduction. Burner is supplied by natural gas. Burner parameters are set: 1 - 3 Nm3 /h of natural gas and 7 - 20 Nm3/h of air per tonne of copper. It ensures effective post- combustion of reduction gases and emission of clean off-gas to the atmosphere. After 100 min the lance is removed and the oil and air flows shut down. Oxygen content has been decreased from 6000 - 8000 ppm to about 400 - 800 ppm. Next, anode casting is proceeded.
Claims
1. A method of intensive, continuous copper fire refining, said method comprising the stages of:
(a) continuous tapping in a liquid copper into first oxidation reactor;
(b) liquid copper oxidation with combustion gases containing oxygen or with air;
(c) simultaneous formation of slag collecting impurities;
(d) continuous tapping out of oxidized copper and refining slag from the first reactor;
(e) continuous tapping in of oxidized copper into the second reduction reactor;
(f) reduction of copper with carbon and reducing gases formed by partial combustion of fuel and carbon;
(g) continuous tapping out of reduced copper.
2. A method as said forth in claim 1, said copper bath consists of liquid blister copper or melted recycled solid copper or scrap, oxidised in order to remove impurities.
3. A method as said forth in claim 1, said liquid copper is dispersed by gravitational flow through a packed bed of ceramic or another chemically neutral grains, and oxidized with counter-current flowing hot gases, containing oxygen such as gases from combustion of natural gas or oil with excess oxygen, corresponding to the content of oxygen in the combustion gases from 5 to 21%.
4. A method as said forth in claim 1, said impurities with higher affinity to oxygen than copper, such as iron, zinc, lead, arsenic, antimony, are oxidized and form together with cuprous oxide a refining slag, which flows down creating a liquid layer on the surface of the oxidized copper. Dissolved sulphur forms sulphur dioxide, which is liberated from a liquid copper and flows out with combustion gases.
5. A method as said forth in claim 1, wherein in step (b) said charcoal is charged onto the surface of a liquid copper from 1 to 10 kg per tonne of copper.
6. A method as said forth in claim 1, wherein in step (b) said various solid carboneous materials can be used instead of charcoal, such as mineral coal or coke with low content of sulphur (<0.8%).
7. A method as said forth in claim 1, wherein in step (c) said the intensity of injection of a liquid or gaseous reductant (oil, natural gas) with air or inert gas can be increased from 10 to 100% of common injection rate without the decrease of reductant efficiency and generation of black fumes.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX2007002764A MX2007002764A (en) | 2004-09-07 | 2005-09-06 | Method of continuous fire refining of copper. |
| EP05796063A EP2111472A1 (en) | 2004-09-07 | 2005-09-06 | Method of continuous fire refining of copper |
| AU2005282475A AU2005282475B2 (en) | 2004-09-07 | 2005-09-06 | Method of continuous fire refining of copper |
| CA2579579A CA2579579C (en) | 2004-09-07 | 2005-09-06 | Method for continuous fire refining of copper |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CL2269 | 2004-09-07 | ||
| CL2004002269 | 2004-09-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006029162A1 true WO2006029162A1 (en) | 2006-03-16 |
Family
ID=40935504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2005/031731 WO2006029162A1 (en) | 2004-09-07 | 2005-09-06 | Method of continuous fire refining of copper |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2111472A1 (en) |
| KR (1) | KR20080100402A (en) |
| AU (1) | AU2005282475B2 (en) |
| CA (1) | CA2579579C (en) |
| MX (1) | MX2007002764A (en) |
| WO (1) | WO2006029162A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009077851A1 (en) * | 2007-12-19 | 2009-06-25 | Universidad De Chile | Continuous fire reduction of liquid copper |
| WO2009090531A1 (en) * | 2008-01-15 | 2009-07-23 | Universidad De Chile | Method for continuous conversion of copper matte - specification |
| CN102586620A (en) * | 2012-03-09 | 2012-07-18 | 广西有色再生金属有限公司 | Refining grate for smelting miscellaneous copper and smelting method thereof |
| CN102676841A (en) * | 2012-05-29 | 2012-09-19 | 江苏句容联合铜材有限公司 | Anti-oxidation process of copper rod smelting |
| CN103436713A (en) * | 2013-08-23 | 2013-12-11 | 江苏句容联合铜材有限公司 | Copper plate smelting device |
| US10648060B2 (en) | 2015-05-06 | 2020-05-12 | Outotec (Finland) Oy | Fire refining of blister copper |
| CN111363938A (en) * | 2020-03-25 | 2020-07-03 | 宁波金田铜业(集团)股份有限公司 | Modifier for scrap brass and method for producing brass alloy by using modifier |
| WO2021175703A1 (en) * | 2020-03-02 | 2021-09-10 | Montanuniversität Leoben | Apparatus and process for thermal treatment of raw material containing lithium compounds and phosphorus compounds, method of recovering lithium and/or phosphorus from residue material of lithium-ion batteries |
| CN115747508A (en) * | 2022-11-21 | 2023-03-07 | 中国恩菲工程技术有限公司 | Method for refining anode copper by anode furnace |
| US11753700B2 (en) | 2017-05-10 | 2023-09-12 | Haldor Topsøe A/S | Process for reducing the content of oxygen in metallic copper |
| CN119979888A (en) * | 2025-04-15 | 2025-05-13 | 安徽天硕金属材料有限公司 | Copper removal refining agent and production process for regenerated refined lead |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102146521A (en) * | 2010-02-08 | 2011-08-10 | 江西稀有金属钨业控股集团有限公司 | Method for reducing stannum content of liquid copper in shaft furnace for regenerating and refining recycled copper |
| CN113481381A (en) * | 2021-06-17 | 2021-10-08 | 张家港联合铜业有限公司 | Copper fire refining process based on carbon dioxide |
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| US3868248A (en) * | 1971-10-06 | 1975-02-25 | Foseco Int | Deoxidising molten non-ferrous metals |
| US5449395A (en) * | 1994-07-18 | 1995-09-12 | Kennecott Corporation | Apparatus and process for the production of fire-refined blister copper |
| US5607495A (en) * | 1992-05-23 | 1997-03-04 | The University Of Birmingham | Oxygen smelting of copper or nickel sulfides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BE622116A (en) * | 1961-09-27 | |||
| GB1146082A (en) * | 1965-03-24 | 1969-03-19 | Sumitomo Metal Mining Co | Method of fire refining copper |
| US4315775A (en) * | 1979-11-28 | 1982-02-16 | Southwire Company | Continuous melting and refining of secondary and/or blister copper |
| JP2689540B2 (en) * | 1988-11-21 | 1997-12-10 | 三菱マテリアル株式会社 | Method and apparatus for producing low oxygen content copper |
| US5849061A (en) * | 1996-09-20 | 1998-12-15 | The Trustees Of Columbia University In The City Of New York | Process for refining high-impurity copper to anode copper |
| US6395059B1 (en) * | 2001-03-19 | 2002-05-28 | Noranda Inc. | Situ desulfurization scrubbing process for refining blister copper |
-
2005
- 2005-09-06 EP EP05796063A patent/EP2111472A1/en not_active Withdrawn
- 2005-09-06 KR KR1020077007827A patent/KR20080100402A/en not_active Withdrawn
- 2005-09-06 CA CA2579579A patent/CA2579579C/en not_active Expired - Fee Related
- 2005-09-06 WO PCT/US2005/031731 patent/WO2006029162A1/en active Application Filing
- 2005-09-06 MX MX2007002764A patent/MX2007002764A/en unknown
- 2005-09-06 AU AU2005282475A patent/AU2005282475B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3868248A (en) * | 1971-10-06 | 1975-02-25 | Foseco Int | Deoxidising molten non-ferrous metals |
| US5607495A (en) * | 1992-05-23 | 1997-03-04 | The University Of Birmingham | Oxygen smelting of copper or nickel sulfides |
| US5449395A (en) * | 1994-07-18 | 1995-09-12 | Kennecott Corporation | Apparatus and process for the production of fire-refined blister copper |
Non-Patent Citations (1)
| Title |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009077851A1 (en) * | 2007-12-19 | 2009-06-25 | Universidad De Chile | Continuous fire reduction of liquid copper |
| US8801830B2 (en) | 2007-12-19 | 2014-08-12 | Universidad De Chile | Continuous fire reduction of liquid copper |
| AU2009205368B2 (en) * | 2008-01-15 | 2014-05-08 | Empresa Nacional De Mineria | Method for continuous conversion of copper matte - specification |
| WO2009090531A1 (en) * | 2008-01-15 | 2009-07-23 | Universidad De Chile | Method for continuous conversion of copper matte - specification |
| CN102586620A (en) * | 2012-03-09 | 2012-07-18 | 广西有色再生金属有限公司 | Refining grate for smelting miscellaneous copper and smelting method thereof |
| CN102676841A (en) * | 2012-05-29 | 2012-09-19 | 江苏句容联合铜材有限公司 | Anti-oxidation process of copper rod smelting |
| CN103436713A (en) * | 2013-08-23 | 2013-12-11 | 江苏句容联合铜材有限公司 | Copper plate smelting device |
| US10648060B2 (en) | 2015-05-06 | 2020-05-12 | Outotec (Finland) Oy | Fire refining of blister copper |
| US11753700B2 (en) | 2017-05-10 | 2023-09-12 | Haldor Topsøe A/S | Process for reducing the content of oxygen in metallic copper |
| WO2021175703A1 (en) * | 2020-03-02 | 2021-09-10 | Montanuniversität Leoben | Apparatus and process for thermal treatment of raw material containing lithium compounds and phosphorus compounds, method of recovering lithium and/or phosphorus from residue material of lithium-ion batteries |
| CN111363938A (en) * | 2020-03-25 | 2020-07-03 | 宁波金田铜业(集团)股份有限公司 | Modifier for scrap brass and method for producing brass alloy by using modifier |
| CN111363938B (en) * | 2020-03-25 | 2021-06-25 | 宁波金田铜业(集团)股份有限公司 | A kind of modifier of waste miscellaneous brass and method for producing brass alloy using the same |
| CN115747508A (en) * | 2022-11-21 | 2023-03-07 | 中国恩菲工程技术有限公司 | Method for refining anode copper by anode furnace |
| CN119979888A (en) * | 2025-04-15 | 2025-05-13 | 安徽天硕金属材料有限公司 | Copper removal refining agent and production process for regenerated refined lead |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2111472A4 (en) | 2009-10-28 |
| AU2005282475A1 (en) | 2006-03-16 |
| MX2007002764A (en) | 2008-12-18 |
| CA2579579A1 (en) | 2006-03-16 |
| KR20080100402A (en) | 2008-11-18 |
| CA2579579C (en) | 2017-06-13 |
| EP2111472A1 (en) | 2009-10-28 |
| AU2005282475B2 (en) | 2011-03-31 |
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