CN101440434A - Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method - Google Patents
Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method Download PDFInfo
- Publication number
- CN101440434A CN101440434A CNA2008102337175A CN200810233717A CN101440434A CN 101440434 A CN101440434 A CN 101440434A CN A2008102337175 A CNA2008102337175 A CN A2008102337175A CN 200810233717 A CN200810233717 A CN 200810233717A CN 101440434 A CN101440434 A CN 101440434A
- Authority
- CN
- China
- Prior art keywords
- copper
- electrodeposition
- leaching
- extraction
- raffinate
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 239000011575 calcium Substances 0.000 title claims description 9
- 229910052791 calcium Inorganic materials 0.000 title claims description 9
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 title claims description 8
- 239000011777 magnesium Substances 0.000 title claims description 6
- 229910052749 magnesium Inorganic materials 0.000 title claims description 6
- 238000000034 method Methods 0.000 title abstract description 28
- 238000000605 extraction Methods 0.000 claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000012141 concentrate Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000007654 immersion Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000003500 flue dust Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 16
- 239000011707 mineral Substances 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000292 calcium oxide Substances 0.000 abstract description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000395 magnesium oxide Substances 0.000 abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- YYPPWPYJZPASPV-UHFFFAOYSA-H calcium copper magnesium trisulfite Chemical compound S(=O)([O-])[O-].[Cu+2].[Mg+2].[Ca+2].S(=O)([O-])[O-].S(=O)([O-])[O-] YYPPWPYJZPASPV-UHFFFAOYSA-H 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 235000011194 food seasoning agent Nutrition 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- QNRJHHHLRLQLER-UHFFFAOYSA-N [Cu]=S.[Mg] Chemical compound [Cu]=S.[Mg] QNRJHHHLRLQLER-UHFFFAOYSA-N 0.000 description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910001608 iron mineral Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000721047 Danaus plexippus Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a process for extracting copper from high calcium-magnesium copper sulphite by a wet method. The process uses large amount of calcium oxide and magnesium oxide in mineral to absorb sulfur dioxide gas generated during roasting to reach the effect of self-cleaning roasting, and uses the primary mineral to neutralize redundant immersion liquid and electrolytic residual liquid for extraction to reach water balance and acid balance. At the same time, the process makes full use of copper concentrate containing sulfur, does not need to increase additional fuel, coverts the sulfur to sulfate radical at the same time, reduces acid loss during roasting and leaching, and improves leaching rate. The process overcomes multiple defects in the prior process, and combines main advantages of wet processing. Shown by test results, the leaching rate of cupric acid is more than 99 percent, integrative reclaiming rate of copper is more than 96 percent, rate of dregs is smaller than 40 percent, the weight of electrolytic copper is more than 99. 95 percent, all technical indexes reach domestic advanced level, and tailings are comprehensively utilized, so the process is environment-friendly.
Description
Technical field
The present invention relates to the chemical industry metallurgical technical field, specifically a kind of technology of extracting copper from high-calcium high-magnesium cupric sulfide by wet.
Background technology
It is the flotation concentrate pyrometallurgical smelting that traditional copper-sulphide ores reclaims technology.Thermal process maturation, stable operation, but investment is big, has SO
2Smoke problem.Since the sixties in 20th century, in order to eliminate SO
2Pollute, the hydrometallurgy copper-sulphide ores has been carried out many researchs, but because of economic target still is not so good as pyrogenic process, wet processing rests on test and small-scale production stage mostly.Wet type copper smelting is mainly used in the processing copper oxide ore at present, has direct acidleach of copper oxide ore and ammonia to soak methods such as (or ammonia soak after the reducing roasting); Acidleach is used wider, and ammonia soaks to be limited to handles the higher associativity oxidized ore of calcic magnesium.Handle that copper-sulphide ores is used sulfurization roasting-leaching more or directly with methods such as ammonia or chloride solution leachings.Directly handling copper sulfide concentrate with solvent has pressurization to leach and two kinds of methods of biological agitation leach.The existing literature disclosed method is as follows:
1) Jiang Yi (company limited of Lanzhou Non-ferrous Metallurgy Design ﹠ Research Inst., 2005) has done introduction to the design of Yulong copper mine hydrometallurgical processes in its article.Strip mining transformation is adopted in the mine, for copper sulfide ore, ore dressing recommend to adopt bulk flotation-copper sulphur content from-technical process that mine tailing reproduces, dressing product is copper ore concentrates and sulphur concentrate, adopt the concentrate boiling roaster respectively, the mixed sulfuric acid of flue gas, the total of sulphuric acid output and copper hydrometallurgy realizes balance with the acid amount; Oxidized ore adopts the metallurgical technology of " strengthening leaching-extraction-electrodeposition ", the copper ore concentrates calcining is incorporated oxidized ore leaching system into and is handled, for the impurity concentration of control in the extraction liquid certain below horizontal, part (about 25%) raffinate is opened a way, add in the limestone powder and the back discharging, and associated element cobalt, the zinc in the open circuit discharging raffinate reclaimed, sulphur concentrate calcining is because copper grade is low, no longer leaches and abandons.[document 1] this art breading is primarily aimed at the oxidized ore treatment process, and sulphur concentrate calcining because copper grade is low, is no longer leached and abandons, and copper recovery is low, and this technology can't be handled the high contents of calcium and magnesium copper sulfide concentrate mainly on ore dressing is handled.
2) Song Ning (Kunming University of Science and Technology, 2005) etc. has proposed chalcopyrite sulfidation roasting under low temperature, protection of inert gas-villaumite and leaches new process for extracting copper and produce smart copper.The chalcopyrite sulfidation roasting is converted into covellite (CuS) and pyrite (FeS
2), there is not S0 in the process
2Produce.Very easily oxidized molten the soaking of the CuS that produces, FeS
2Then opposite, thus realize that copper iron separates.This technology has that leaching agent can be recycled, facility investment is little, flow process is short, leaching rate is high, do not produce SO
2, do not produce colloid, leaching solution during molten soaking and easily filter, moltenly soak advantages such as number of times is few.[document 2] this technology needs produce smart copper under protection of inert gas, be not suitable for than large-scale industrial production, and production cost is higher, and this technology mainly proposes villaumite and leaches, with this technology mainly be that multistage leaches, have than big difference.
3) Zhang Yu (Yunnan Copper Industry Science and Technology Development Co., Ltd., 2002) etc. discloses a kind of hydrometallurgical processes of copper ore concentrates, and its technical process is: the mixed copper concentrate-oxidation leaching-iron purification-two-way electrodeposition-electrolytic copper of copper manganese.It is to add sulfuric acid and MnO that oxidation is leached
2Carry out high temperature and leach, iron purification forms jarosite, two-way electrodeposition output electro deposited copper and active MnO
2Yunnan Mouding copper mine selected to build up a kind of wet method copper-extracting process of copper ore concentrates in 1997, i.e. copper ore concentrates-rotary kiln sulfurization roasting-agitation leach-extraction-electrodeposition, and leached mud is floatation recovery Cu, Ag, Au again.[document 3] Yunnan Mouding copper mine once adopted this wet method copper-extracting process in 1997, and its technical process is: copper ore concentrates-rotary kiln sulfurization roasting-agitation leach-extraction-electrodeposition, leached mud is floatation recovery Cu, Ag, Au again.There is design defect in this technology, leached mud cupric height (3～4%), and copper exists with the coppeferrite form, can't floatation recovery; Adopt the extracting and purifying deironing, the cost height, thereby in stopping production in 1998.
4) Yang Jiuyi (Hebei University of Science and Technology, 2003) etc. discloses a kind of method for preparing copper sulfate with copper ore concentrates.This method is to add complex additive in copper concentrate powder, make the iron in the copper ore concentrates in roasting process, form the ferric subsulfate double salt precipitation that is insoluble in dilution heat of sulfuric acid with it, when the copper sulfate of leaching copper calcining, this precipitation leaches with residue, filtrate can purify without deironing, directly decrease temperature crystalline filters, and just can obtain the copper sulfate qualified product.Described complex additive is by Na
2CO
3And Na
2B
4O
710H
2The O cooperation forms.[document 4] this technology is mainly produced preparation copper sulfate, mainly is to produce copper sulfate by roasting, leaching and interpolation additive, and extract technology is different with this technology.
5) He Zhusheng (Baoji Teacher's College, 1992) discloses a kind of technology and fluidizing reactor thereof of the copper concentrate powder direct production copper sulfate by cupric sulfide or Containing Sulfur copper.Described technology mainly comprises: add the inorganic salt mixing, roasting at a lower temperature, leaching, purification and impurity removal, crystallisation by cooling, centrifugation.The inorganic salt that add in the raw material can be vitriolate of tartar or sodium sulfate or saltcake or SODIUMNITRATE or saltpetre or sodium bicarbonate or yellow soda ash or salt of wormwood or saleratus.The adding of these inorganic salt helps decomposition and the further oxidation that cupric sulfide is oxidized to the reaction of copper sulfate and promotes ferrous sulfate.[document 5] this technology is mainly produced preparation copper sulfate, mainly is directly to produce copper sulfate by roasting and leaching, and extract technology is different with this technology.
6) Gu Wancheng (Beijing Inst. of Chemical Metallurgy, Ministry of Nuclear Industry, 2004) adopts low temperature (250 ℃) roasting-sulfuric acid leaching-S-WAT reduction-NaCl depositing technology, prepares cuprous chloride with copper sulfide concentrate.In the research copper sulfide concentrate has been carried out the leaching test of high temperature (650 ℃) and low temperature (250 ℃) roasting test and roasting ash, the result shows: the transformation efficiency of cupric sulfide is higher during low-temperature bake; The copper leaching rate of low-temperature bake ash and high-temperature roasting ash are basic identical, but the leaching yield of impurity iron is much lower, and particularly evident is that the sour consumption range of decrease of leaching is very big, more than 17%.In other words, adopt the low-temperature bake technology to adopt the high-temperature roasting technology to cut down the consumption of energy significantly and sour consumption, and the yield of copper is higher, can obtain tangible economic benefit and environmental benefit.[document 6] this project is mainly studied low temperature (250 ℃) roasting effect, and it is main mainly preparing cuprous chloride technology, different with this technology.
7) Cai Chaojun (Kunming University of Science and Technology, 2004) etc. has carried out comparative study with the reaction mechanism that copper sulfide concentrate adds lime carbonate roasting and copper sulfide concentrate roasting.The result shows: the sulfide that adds copper sulfide concentrate roasting copper when 673～857K of lime carbonate is oxidized to vitriol; The vitriol that generates when 857～1073K can decompose.[document 7] this project is mainly studied the backing mechanism research of copper sulfide concentrate, and unreacted goes out copper sulfide concentrate to the whole technological process that provides.
In sum, the hydrometallurgy of copper sulfide concentrate normally utilizes sulfurization roasting that copper sulfide concentrate is carried out pre-treatment, copper is converted into soluble sulphate, and then produces electro deposited copper with Wet-process metallurgy method.
Reference:
1. Jiang Yi. Yulong copper mine sulphide ores dressing product scheme optimization is selected. non-ferrous metal design .2005,32 (4) .-8-15,29
2. Song Ning etc. chalcopyrite adds sulphur roasting new process for extracting copper. non-ferrous metal .2005,57 (2)
3. Zhang Yu etc. wet method copper-extracting process. Chinese patent CN1465724
4. poplar justice of a specified duration etc. a kind of method for preparing copper sulfate with copper ore concentrates. Chinese patent CN1544663
5. what post is given birth to. the production technique of copper sulfate and fluidizing reactor thereof. and Chinese patent CN1079207
6. paddy is ten thousand one-tenth. and with the copper sulfide concentrate raw material production cuprous chloride technical study. hydrometallurgy .2004,23 (1)
7. monarch Cai Chao etc. copper sulfide concentrate adds the research of lime carbonate roasting apparent kinetics. non-ferrous metal (smelting part) 2004, (3)
Summary of the invention
The technology that the purpose of this invention is to provide a kind of extracting copper from high-calcium high-magnesium cupric sulfide by wet is utilized the sulfur dioxide gas that a large amount of calcium oxide, magnesium oxide mineral absorption roasting process produce in the mineral, reaches the effect of " self-cleaning " roasting; Utilize in the raw ore to extract with unnecessary immersion liquid and electrodeposition raffinate, weighing apparatus, acid balance are up to the standard.
The present invention is directed to the high copper sulfide concentrate of calcium-magnesium content, adopt " sulfurization roasting-acidleach (multistage)-extraction-electrodeposition (cathode copper) " explained hereafter electro deposited copper, characteristics are: the high contents of calcium and magnesium copper sulfide concentrate adopts the low temperature sulfurization roasting; Utilize the sulfur dioxide gas that a large amount of calcium oxide, magnesium oxide mineral absorption roasting process produce in the mineral, reach the effect of " self-cleaning " roasting; Utilize in the raw ore to extract with unnecessary immersion liquid and electrodeposition raffinate, weighing apparatus, acid balance are up to the standard.The high contents of calcium and magnesium copper sulfide concentrate hydrometallurgy copper-extracting process that is adopted is different from existing similar technology.
Concrete technical process is as follows:
(1) concentrate is prepared; (2) roasting; (3) leach; (4) washing; (5) neutralization; (6) extraction; (7) electrodeposition.Be described below respectively:
(1) concentrate is prepared: at first seasoning uses the wheel roller crushing and screening to 2mm to water ratio 5%～10% then, and seasoning is 3～7 days on the smooth place that cement is built, and the raw material ore storage bin is gone in the back storage;
(2) roasting: the dried concentrate that is stored in the raw material ore storage bin adds fluidizing furnace continuously equably by screw feeder, maturing temperature is controlled at 600～650 ℃, blast the Boiling Combustion in stove of air and concentrate, residing time in furnace 10-15h, utilize the sulfur dioxide gas that a large amount of calcium oxide, magnesium oxide mineral absorption roasting process produce in the mineral, generate calcium sulfate and sal epsom, reduce the discharging of sulfur dioxide gas, reach the effect of " self-cleaning " roasting.Iron mineral is transformed into ferric oxide in the material, stays in the solid phase, and sulphur is converted into sulfurous gas, combines with a large amount of calcium oxide, magnesium oxide mineral in the mineral, generates vitriol, and the roasted ore some is overflowed by the fluidizing furnace discharge gate, is called calcining; A part of taken out of outside the stove by air-flow, enter dust collecting system in addition collecting obtain flue dust;
(3) leach: calcining and flue dust carry out oarizations in the pulp groove, by solid-to-liquid ratio 1:2-3, add entry and carry out pulp, carry out one section leaching after the pulp, (for the first time) adds sulfuric acid to make acid concentration is 60～85g/l as leach liquor and (add two sections leach liquors later on and replenish, and to keep acid concentration be 60～85g/l), steam heating at this moment, temperature control〉90 ℃, extraction time 2-3h, after leaching finished, ore pulp pumped into filter press, obtain leach liquor and filter residue, leach liquor pumps into one section immersion liquid storage tank, for direct electrodeposition, obtains electro deposited copper and electrodeposition raffinate, one section is soaked slag and returns in the leaching vat two sections leachings of confession; One section is soaked slag and carries out two sections when leaching, add the electrodeposition raffinate by solid-to-liquid ratio 1:2-3 and carry out two sections leachings, acid concentration is 240～260g/l behind the additional sulfuric acid, steam heating, temperature control〉90 ℃, extraction time 2-3h, after leaching finishes, ore pulp pumps into filter press, and filtrate pumps into two sections immersion liquid storage tanks and uses for one section leach liquor, and two sections are soaked slag and use for washing.
(4) washing: two sections are soaked slag and return in the leaching vat, add entry (for the first time) by solid-to-liquid ratio 1:10-15 at normal temperatures and wash, and wash with raffinate later on, after stirring 0.5-1h, pump into filter press, obtain washings and filter residue, washings enters neutralizing zone, and filter residue is sent to the stockyard and stacks;
(5) neutralization: washings pumps into leaching vat, adds electrodeposition raffinate, raw ore stirring, carries out neutralizing treatment, and with slag and neutralizer, final neutralizer reaches pH=4-5, enters extraction process in the acquisition;
(6) extraction: neutralizer enters extraction process, and adding concentration is 30% (V/V) LIX5640 (ethylidenehydroxylamine) extraction agent (thinner is common kerosene), and the ratio of neutralizer and extraction agent is 1:0.5-1; Temperature is in room temperature; The load organic phases that obtains is carried out back extraction, and reverse-extraction agent is that water adds sulfuric acid, and acid concentration is 250g/l, and mixing time is 3min; Clarifying speed, 3m
3/ m
2.h, (30～80g/l) power supplies of Cu+ concentration are long-pending, and raffinate is washed usefulness for soaking wash heat to extract rich copper liquid.
(7) electrodeposition: get electro deposited copper and electrodeposition raffinate behind the rich copper liquid electrodeposition, the electrodeposition raffinate returns back extraction and recycles.
The present invention produces used raw material one copper sulfide concentrate, the calcium-magnesium content height, and sulphur content is lower.The copper ore concentrates of this low-sulfur high alkalinity gangue, pyrogenic process or common wet processing are all more difficult.Utilize sulfurization roasting technology, sulphur in the copper ore concentrates and calcium magnesium generation chemical reaction suppress the discharge of sulfur dioxide gas, reach the purpose of " self-cleaning roasting ".Make full use of the copper ore concentrates sulfur-bearing simultaneously, can increase additional fuel, sulphur is converted into sulfate radical simultaneously, reduces calcining and leaches the acid consumption, improves leaching yield.Overcome many shortcomings of traditional technology, combined the major advantage of wet processing again.Test-results gets the copper acidleach and goes out rate〉99%, the copper comprehensive recovery 96%, slag rate＜40%, electro deposited copper quality 99.95%, technical indicator has all reached advanced international level, be the major technological breakthrough of high contents of calcium and magnesium copper-sulphide ores hydrometallurgy, for new thinking is introduced in the wet processing of high contents of calcium and magnesium copper mine.Exhaust gas emission is far below national standard; Utilize in the raw ore to extract with unnecessary immersion liquid and electrodeposition raffinate, leach liquor, electric effusion, raffinate recycle, be up to the standard weighing apparatus, acid balance are realized zero release; The tailings comprehensive reutilization is realized environmental friendliness.Overall flow be up to the standard weighing apparatus, acid balance, and realize soaking surplus liquid and the recycle of electrodeposition raffinate.
Description of drawings
Fig. 1 is traditional common copper sulfide concentrate wet processing schema.
Fig. 2 is sulfurization roasting-acidleach of the present invention-extraction-electro deposited copper process flow sheet.
Embodiment
Embodiment 1:
(1) concentrate is prepared: Dongchuan, Yunnan is because of people's copper ore concentrates drying seasoning on the smooth place that cement is built (3～7 days), water ratio 5～10%, drying finish after broken (＜2mm) storage is gone into the roasting ore storage bin and is prepared into stove.
(2) roasting: the dried concentrate that is stored in the raw material ore storage bin adds fluidizing furnace continuously equably by screw feeder, maturing temperature is controlled at 600 ℃, blast the Boiling Combustion in stove of air and concentrate, residing time in furnace 10h, utilize the sulfur dioxide gas that a large amount of calcium oxide, magnesium oxide mineral absorption roasting process produce in the mineral, generate calcium sulfate and sal epsom, reduce the discharging of sulfur dioxide gas, reach the effect of " self-cleaning " roasting.The roasted ore some is overflowed by the fluidizing furnace discharge gate, is called calcining; A part of taken out of outside the stove by air-flow, enter dust collecting system in addition collecting obtain flue dust;
(3) leach: calcining and flue dust carry out oarizations in the pulp groove, by solid-to-liquid ratio 1:2, add entry and carry out pulp, carry out one section leaching after the pulp, (for the first time) adds sulfuric acid to make acid concentration is 60g/l as leach liquor (add two sections leach liquors later on and replenish, and keep acid concentration be 60g/l), steam heating at this moment, temperature control〉90 ℃, extraction time 2h, after leaching finished, ore pulp pumped into filter press, obtain leach liquor and filter residue, leach liquor pumps into one section immersion liquid storage tank, for direct electrodeposition, obtains electro deposited copper and electrodeposition raffinate, one section is soaked slag and returns in the leaching vat two sections leachings of confession; One section is soaked slag and carries out two sections when leaching, add the electrodeposition raffinate by solid-to-liquid ratio 1:2 and carry out two sections leachings, acid concentration is 240g/l behind the additional sulfuric acid, steam heating, temperature control〉90 ℃, extraction time 2h, after leaching finishes, ore pulp pumps into filter press, and filtrate pumps into two sections immersion liquid storage tanks and uses for one section leach liquor, and two sections are soaked slag and use for washing.
(4) washing: two sections are soaked slag and return in the leaching vat, add entry (for the first time) by solid-to-liquid ratio 1:10 at normal temperatures and wash, and wash with raffinate later on, after stirring 0.5-1h, pump into filter press, obtain washings and filter residue, washings enters neutralizing zone, and filter residue is sent to the stockyard and stacks;
(5) neutralization: washings pumps into leaching vat, adds electrodeposition raffinate, raw ore stirring, carries out neutralizing treatment, and with slag and neutralizer, final neutralizer reaches pH=4, enters extraction process in the acquisition;
(6) extraction: neutralizer enters extraction process, and adding concentration is 30% (V/V) LIX5640 (ethylidenehydroxylamine) extraction agent (thinner is common kerosene), and the ratio of neutralizer and extraction agent is 1:1; Temperature is in room temperature; The load organic phases that obtains is carried out back extraction, and reverse-extraction agent is that water adds sulfuric acid, and acid concentration is 250g/l, and mixing time is 3min; Clarifying speed, 3m
3/ m
2.h, (30～80g/l) power supplies of Cu+ concentration are long-pending, and raffinate is washed usefulness for soaking wash heat to extract rich copper liquid.
(7) electrodeposition: get electro deposited copper and electrodeposition raffinate behind the rich copper liquid electrodeposition, the electrodeposition raffinate returns back extraction and recycles.Electrodeposition system power density: 120～150A/m
2, bath voltage: 1.8～2.0V, direct current consumption: 2200～2500kWh/tCu.
Embodiment 2:
(1) concentrate is prepared: the Tang Dan copper sulfide concentrate seasoning of Dongchuan, Yunnan uses the wheel roller crushing and screening to 2mm to moisture 5%～10% then, and seasoning is 3～7 days on the smooth place that cement is built, and the raw material ore storage bin is gone in the back storage;
(2) roasting: the dried concentrate that is stored in the raw material ore storage bin adds fluidizing furnace continuously equably by screw feeder, maturing temperature is controlled at 650 ℃, blast the Boiling Combustion in stove of air and concentrate, residing time in furnace 15h, utilize the sulfur dioxide gas that a large amount of calcium oxide, magnesium oxide mineral absorption roasting process produce in the mineral, generate calcium sulfate and sal epsom, reduce the discharging of sulfur dioxide gas.Iron mineral is transformed into ferric oxide in the material, stays in the solid phase, and sulphur is converted into sulfurous gas, combines with a large amount of calcium oxide, magnesium oxide mineral in the mineral, generates vitriol, and the roasted ore some is overflowed by the fluidizing furnace discharge gate, is called calcining; A part of taken out of outside the stove by air-flow, enter dust collecting system in addition collecting obtain flue dust;
(3) leach: calcining and flue dust carry out oarizations in the pulp groove, by solid-to-liquid ratio 1:3, add entry and carry out pulp, carry out one section leaching after the pulp, (for the first time) adds sulfuric acid to make acid concentration is 85g/l as leach liquor (add two sections leach liquors later on and replenish, and keep acid concentration be 85g/l), steam heating at this moment, temperature control〉90 ℃, extraction time 3h, after leaching finished, ore pulp pumped into filter press, obtain leach liquor and filter residue, leach liquor pumps into one section immersion liquid storage tank, for direct electrodeposition, obtains electro deposited copper and electrodeposition raffinate, one section is soaked slag and returns in the leaching vat two sections leachings of confession; One section is soaked slag and carries out two sections when leaching, add the electrodeposition raffinate by solid-to-liquid ratio 1:3 and carry out two sections leachings, acid concentration is 260g/l behind the additional sulfuric acid, steam heating, temperature control〉90 ℃, extraction time 3h, after leaching finishes, ore pulp pumps into filter press, and filtrate pumps into two sections immersion liquid storage tanks and uses for one section leach liquor, and two sections are soaked slag and use for washing.
(4) washing: two sections are soaked slag and return in the leaching vat, add entry (for the first time) by solid-to-liquid ratio 1:15 at normal temperatures and wash, and wash with raffinate later on, after stirring 0.5-1h, pump into filter press, obtain washings and filter residue, washings enters neutralizing zone, and filter residue is sent to the stockyard and stacks;
(5) neutralization: washings pumps into leaching vat, adds electrodeposition raffinate, raw ore stirring, carries out neutralizing treatment, and with slag and neutralizer, final neutralizer reaches pH=5, enters extraction process in the acquisition;
(6) extraction: neutralizer enters extraction process, and adding concentration is 30% (V/V) LIX5640 (ethylidenehydroxylamine) extraction agent (thinner is common kerosene), and the ratio of neutralizer and extraction agent is 1:1; Temperature is in room temperature; The load organic phases that obtains is carried out back extraction, and reverse-extraction agent is that water adds sulfuric acid, and acid concentration is 250g/l, and mixing time is 3min; Clarifying speed, 3m
3/ m
2.h, (30～80g/l) power supplies of Cu+ concentration are long-pending, and raffinate is washed usefulness for soaking wash heat to extract rich copper liquid.
(7) electrodeposition: get electro deposited copper and electrodeposition raffinate behind the rich copper liquid electrodeposition, the electrodeposition raffinate returns back extraction and recycles.Electrodeposition system power density: 120～150A/m
2, bath voltage: 1.8～2.0V, direct current consumption: 2200～2500kWh/tCu.
Claims (1)
1, a kind of technology of extracting copper from high-calcium high-magnesium cupric sulfide by wet is characterized in that carrying out according to the following steps:
(1) concentrate is prepared: be dried to water ratio 5%～10%, then, crushing and screening to 2mm, the raw material ore storage bin is gone in storage;
(2) roasting: dried concentrate adds fluidizing furnace, maturing temperature is controlled at 600～650 ℃, blast the Boiling Combustion in stove of air and concentrate, residing time in furnace 10-15h, roasted ore is a part of to be overflowed by the fluidizing furnace discharge gate for calcining, a part of taken out of outside the stove by air-flow, enter dust collecting system in addition collecting obtain flue dust;
(3) leach: calcining and flue dust carry out oarizations in the pulp groove, by solid-to-liquid ratio 1:2-3, add entry and carry out pulp, carry out one section leaching after the pulp, this moment add sulfuric acid make acid concentration be 60～85g/l as leach liquor, steam heating, temperature control〉90 ℃, extraction time 2-3h, leach finish after, ore pulp pumps into filter press, obtains leach liquor and filter residue, and leach liquor pumps into one section immersion liquid storage tank, for direct electrodeposition, obtain electro deposited copper and electrodeposition raffinate, one section is soaked slag and returns in the leaching vat two sections leachings of confession; One section is soaked slag and carries out two sections when leaching, add the electrodeposition raffinate by solid-to-liquid ratio 1:2-3 and carry out two sections leachings, acid concentration is 240～260g/l behind the additional sulfuric acid, steam heating, temperature control〉90 ℃, extraction time 2-3h, after leaching finishes, ore pulp pumps into filter press, and filtrate pumps into two sections immersion liquid storage tanks and uses for one section leach liquor, and two sections are soaked slag and use for washing;
(4) washing: two sections are soaked slag and return in the leaching vat, add entry by solid-to-liquid ratio 1:10-15 at normal temperatures and wash, and wash with raffinate later on, after stirring 0.5-1h, pump into filter press, obtain washings and filter residue, washings enters neutralizing zone, and filter residue is sent to the stockyard and stacks;
(5) neutralization: washings pumps into leaching vat, adds electrodeposition raffinate, raw ore stirring, carries out neutralizing treatment, and with slag and neutralizer, final neutralizer reaches pH=4-5, enters extraction process in the acquisition;
(6) extraction: neutralizer enters extraction process, and adding concentration is 30% (V/V) LIX5640 extraction agent, and the ratio of neutralizer and extraction agent is 1:0.5-1; Temperature is in room temperature; The load organic phases that obtains is carried out back extraction, and reverse-extraction agent is that water adds sulfuric acid, and acid concentration is 250g/l, and mixing time is 3min; Clarifying speed, 3m
3/ m
2.h, (30～80g/l) power supplies of Cu+ concentration are long-pending, and raffinate is washed usefulness for soaking wash heat to extract rich copper liquid.
(7) electrodeposition: get electro deposited copper and electrodeposition raffinate behind the rich copper liquid electrodeposition, the electrodeposition raffinate returns back extraction and recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102337175A CN101440434A (en) | 2008-12-17 | 2008-12-17 | Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102337175A CN101440434A (en) | 2008-12-17 | 2008-12-17 | Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101440434A true CN101440434A (en) | 2009-05-27 |
Family
ID=40725042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102337175A Pending CN101440434A (en) | 2008-12-17 | 2008-12-17 | Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101440434A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961673A (en) * | 2010-09-03 | 2011-02-02 | 罗光臣 | Combined dressing and smelting method for mixed copper ore |
| CN107523694A (en) * | 2017-09-11 | 2017-12-29 | 中南大学 | A kind of method of Bellamya aeruginosa roasting Strengthen education |
| CN108070712A (en) * | 2017-12-15 | 2018-05-25 | 郴州市金贵银业股份有限公司 | The recovery method of valuable metal in a kind of silver electrolysis mother liquor purification slag |
| CN110564950A (en) * | 2019-08-26 | 2019-12-13 | 金川集团股份有限公司 | refining method of copper-cobalt mixed ore |
| CN111225988A (en) * | 2018-09-29 | 2020-06-02 | 长沙有色冶金设计研究院有限公司 | Oxygen pressure leaching method of copper sulfide concentrate and copper smelting method |
| CN118006919A (en) * | 2024-04-10 | 2024-05-10 | 矿冶科技集团有限公司 | A method for improving the leaching effect of copper sulfide ore by collaborative treatment |
-
2008
- 2008-12-17 CN CNA2008102337175A patent/CN101440434A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961673A (en) * | 2010-09-03 | 2011-02-02 | 罗光臣 | Combined dressing and smelting method for mixed copper ore |
| CN101961673B (en) * | 2010-09-03 | 2014-03-26 | 罗光臣 | Combined dressing and smelting method for mixed copper ore |
| CN107523694A (en) * | 2017-09-11 | 2017-12-29 | 中南大学 | A kind of method of Bellamya aeruginosa roasting Strengthen education |
| CN108070712A (en) * | 2017-12-15 | 2018-05-25 | 郴州市金贵银业股份有限公司 | The recovery method of valuable metal in a kind of silver electrolysis mother liquor purification slag |
| CN108070712B (en) * | 2017-12-15 | 2019-12-03 | 郴州市金贵银业股份有限公司 | A kind of silver is electrolysed the recovery method of valuable metal in mother liquor purification slag |
| CN111225988A (en) * | 2018-09-29 | 2020-06-02 | 长沙有色冶金设计研究院有限公司 | Oxygen pressure leaching method of copper sulfide concentrate and copper smelting method |
| CN110564950A (en) * | 2019-08-26 | 2019-12-13 | 金川集团股份有限公司 | refining method of copper-cobalt mixed ore |
| CN110564950B (en) * | 2019-08-26 | 2021-09-24 | 金川集团股份有限公司 | Refining method of copper-cobalt mixed ore |
| CN118006919A (en) * | 2024-04-10 | 2024-05-10 | 矿冶科技集团有限公司 | A method for improving the leaching effect of copper sulfide ore by collaborative treatment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101509072B (en) | Method for extracting valuable metals from laterite nickel ore by hydrochloric acid fully closed loop method | |
| US4619814A (en) | Process for the recovery of non-ferrous metals from sulphide ores and concentrates | |
| MX2008000888A (en) | Integrated hydrometallurgical and pyrometallurgical processing of base-metal sulphides. | |
| CN102251122B (en) | Silver-extracting process of lead-silver slag acidification roasting leaching | |
| CN102181627B (en) | A kind of acid-mixed ripening method for treating primary low-grade high-phosphorus manganese ore | |
| CN106636667B (en) | A method of recycling manganese and silver from manganese-silver ore | |
| CN103526017A (en) | Extraction method of valuable elements from acid mud produced in sulfuric acid production by copper smelting flue gas | |
| CN108754148B (en) | Treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel | |
| CN106868306A (en) | A kind of method of zinc leaching residue valuable metal high efficiente callback | |
| CN101113490B (en) | A method for leaching indium from indium sulfide concentrate | |
| CN101440434A (en) | Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method | |
| CN102212683A (en) | Wet metallurgical method with comprehensive reclamation, basically no three wastes and zero discharge | |
| CN102345018B (en) | A method for processing nickel oxide ore | |
| CN104195345A (en) | Process for recovering sulfur, lead, zinc and silver from oxygen-enriched directly leached residues of zinc concentrates or lead-zinc mixed ores | |
| CN101787439B (en) | Method for recovering valuable metals from metallurgical waste | |
| CN102994746B (en) | Method for producing nickel sulfide ore concentrate by use of industrial waste acid | |
| CN102534195B (en) | Gold extraction process method for refractory gold ore | |
| Wang et al. | A new method of full resource utilization of copper slag | |
| CN112593074B (en) | Low-temperature roasting, leaching and recycling iron removal process of yellow sodium ferroaluminate | |
| CN102703694A (en) | Method for treating low-grade zinc oxide ores by wet method | |
| CN103498052A (en) | Method for efficiently enriching rare precious metals from complex low-grade heat filter residues | |
| Mu et al. | Eco-friendly and selective separation of nickel and copper from low-grade nickel sulfide ore via sulfur fixation roasting with MgCO3 followed by sulfuric acid leaching | |
| CN106893862A (en) | A kind of processing method of zinc leaching residue | |
| CN104789771A (en) | Valuable metal separation method for complex copper, lead, zinc and silver mixed concentrates | |
| CN115216633A (en) | A method for separating copper, arsenic and directly solidifying arsenic from black copper mud |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20090527 |