CN109772589A - A kind of combined capturing and collecting agent of the high-iron sphalerite containing indium and its application - Google Patents
A kind of combined capturing and collecting agent of the high-iron sphalerite containing indium and its application Download PDFInfo
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- CN109772589A CN109772589A CN201910062250.0A CN201910062250A CN109772589A CN 109772589 A CN109772589 A CN 109772589A CN 201910062250 A CN201910062250 A CN 201910062250A CN 109772589 A CN109772589 A CN 109772589A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 85
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 55
- 229910052950 sphalerite Inorganic materials 0.000 title claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 126
- 239000011701 zinc Substances 0.000 claims abstract description 126
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000011084 recovery Methods 0.000 claims abstract description 28
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012991 xanthate Substances 0.000 claims abstract description 18
- 238000005188 flotation Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000012141 concentrate Substances 0.000 claims description 81
- 238000000227 grinding Methods 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- 239000004576 sand Substances 0.000 claims description 24
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012190 activator Substances 0.000 claims description 15
- 239000003814 drug Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000003801 milling Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000010970 precious metal Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 235000010755 mineral Nutrition 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052683 pyrite Inorganic materials 0.000 description 7
- 239000011028 pyrite Substances 0.000 description 7
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 229910020218 Pb—Zn Inorganic materials 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 3
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229910052951 chalcopyrite Inorganic materials 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 229910001919 chlorite Inorganic materials 0.000 description 3
- 229910052619 chlorite group Inorganic materials 0.000 description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000010436 fluorite Substances 0.000 description 3
- 229910052867 ilvaite Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 229910052889 tremolite Inorganic materials 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 description 1
- HKJKONMZMPUGHJ-UHFFFAOYSA-N 4-amino-5-hydroxy-3-[(4-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 HKJKONMZMPUGHJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QHSFHBRFVUUBJK-UHFFFAOYSA-N [Cu].[Zn].[In] Chemical compound [Cu].[Zn].[In] QHSFHBRFVUUBJK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical group [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical group P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of for the flotation combined capturing and collecting agent of the high-iron sphalerite containing indium and its application, belongs to Ore Dressing Engineering field；Combined capturing and collecting agent of the present invention is made of the component of following parts by weight: 206 30~50 parts of modified xanthates, 30~50 parts of ethyl xanthate, 10~30 parts of butylamine black powder, combined capturing and collecting agent is applied to the flotation of the high-iron sphalerite containing indium, greatly improve the rate of recovery of zinc indium, combined capturing and collecting agent of the present invention is strong to the collecting ability of high-iron sphalerite containing indium, it is especially strong to the collecting agent ability of rare precious metal indium, the indium resource of zinc resource association can preferably be improved, and selectivity is good, the ingredient of combined capturing and collecting agent of the invention easily obtains, price is low, dosing is few, production cost is low, and it is nontoxic and pollution-free, it is environmentally friendly, this combined capturing and collecting agent is using easy to implement, can be carried out in the case where not changing original production technology using, scene uses simple, technique good separation effect, index is stablized.
Description
Technical field
The present invention relates to a kind of combined capturing and collecting agent of high-iron sphalerite containing indium and its applications, belong to mineral manufacture field.
Background technique
Zinc has good calenderability, wearability, corrosion resistance, castability and room temperature mechanicalness, can be with various metals system
At the alloy of function admirable, therefore it is widely used in the industries such as automobile, building, household electrical appliance, ship, light industry, machinery, battery.
The zinc resource very abundant in China, occupies the second in the world, and marmatite is one of main source mineral of zinc metal.China is some to be contained
The zinc-tin mine of the elements such as lead, zinc, copper, tin, iron, sulphur and controlling proposals all contain marmatite, such as mountain of papers to some extent
All Long Xinxikuang, Dachang, Guangxi, Mengzi Bai Niuchang polymetallic ore, three Pb-Zn deposits of river, Pan Jiachong, Hunan Huangshaping Pb-Zn Mine, HERBA ONYCHII lead
Zinc ore, Deposit In The Xitieshan Pb-zn Deposit, qinghai, Jilin Fangniugou Pyrite, event ox wash in a pan Pb-Zn deposits, Heilungkiang XiLin Pb-Zn deposits, Hezhang, Guizhou lead zinc
Mine, Guangdong thickness mother-in-law's col Pb-Zn deposits and billows deep blue Pb-Zn deposits etc..The marmatite iron content in these mines is generally 8%~12%, has
Up to 26%.In these complex multi-metal sulphide ore beds, the main preservation of indium forms marmatite containing indium in marmatite,
It is enriched in ore dressing process with zinc.It more than 2,000 ten thousand tons of Yunnan zinc metal reserves, is the first in the nation, wherein the zinc of marmatite
Metal reserves are up to more than 700 ten thousand tons, the 1/3 of Zhan Yunnan zinc metal reserves, and the reserves of all regional marmatites of dragon account for Yunnan iron
The 40% of zincblende gross reserves, yield are concentrated, and iron content is up to 10%~22% or more in minal, and wherein rare precious metal indium stores up
5470 tons of amount, position is the first in the nation, and forms high-iron sphalerite containing indium.
Compared with common zincblende, there are larger differences for the flotation behavior of the high-iron sphalerite containing indium.High-speed rail containing indium dodges zinc
Zinc atom is replaced by iron atom and phosphide atom in lattice in mine, and hydroxide ion and hydrone are easier in iron atom and indium original
Adsorbed on son, enhance the hydrophily of the high-iron sphalerite containing indium, and lead to the reduction of its native floatability, cause in ore dressing process zinc and
The rate of recovery of indium is too low.Therefore, the zinc indium recycling of the high-iron sphalerite containing indium how is promoted by new process, new medicament and new equipment
Rate is the emphasis and difficult point of dresser's author investigation, is also of great significance to the cleanly production of mineral resources.
Tong Xiong et al. has been invented and has been total to the method for recycling rich indium marmatite in association polymetallic ore from copper zinc indium under low alkali
(ZL201611018948.5), by reducing inhibitor dosage in copper zinc assorting room, the pH of flotation pulp is reduced, flotation is simplified
Process improves the recovery rate in ore-dressing of flotation efficiency and zinc indium.This method recycles rich indium marmatite by improving ore pulp environment
Rate effect is preferable, but still uses traditional butyl xanthate as collecting agent, does not solve from medicament collecting intensity and selectivity
High-iron sphalerite containing indium is difficult to the problem of collecting.
Currently, marmatite floating agent mainly has xanthate collectors, cation-collecting agent, combined capturing and collecting agent, chelating
Collecting agent and new collector etc..With the growth of hydrocarbon chain, adsorbance of the xanthate on not activated zincblende increases.Without
The zincblende or marmatite of activation need to generally use long-chain class xanthate just can flotation.There are commonly ethyl Huangs for xanthate collectors
Medicine, butyl xanthate and isoamyl xanthate etc..In order to sort marmatite effectively with pyrite, in addition to selecting to be suitable for
Outside flowage structure and pH value, select excellent collecting agent selectively good to marmatite, weak to pyrite collecting ability very heavy
It wants.It is learnt from the data of report, the mixing based on the diesel oil to marmatite with preferable selectivity, supplemented by butyl xanthate
Collecting agent can preferably solve the problems, such as that marmatite and pyrite sort, but lack the collecting for having ignored rare precious metal indium
Effect.Therefore, current combined capturing and collecting agent and new collector do not consider the height containing indium just for marmatite
Marmatite.
Summary of the invention
Low, the lower problem of the rate of recovery of rare and scatter element indium, the purpose of the present invention for the solution high-iron sphalerite rate of recovery
One of be to provide it is a kind of it is efficient, economic and environment-friendly, stablize mature combined capturing and collecting agent, combined capturing and collecting agent of the present invention is to the sudden strain of a muscle of high-speed rail containing indium
Zinc ore collecting ability is strong, especially strong to the collecting agent ability of rare precious metal indium, can preferably improve the indium money of zinc resource association
Source, and selectivity is good.This method can rich Indium-Zinc concentrate in high efficiente callback complex multi-metal mine in zinc indium ore resources.
The combined capturing and collecting agent of present invention high-iron sphalerite containing indium, the combined capturing and collecting agent by following parts by weight component group
At: 206 30~50 parts of modified xanthates, 30~50 parts of ethyl xanthate, 10~30 parts of butylamine black powder.
The method that the combined capturing and collecting agent of this high-iron sphalerite containing indium is used to promote zinc indium recovery, the specific steps are as follows:
(1) ore of granularity≤250mm carries out ore grinding after will be broken, and ore milling product is sieved with drum sieve, oversize
Material returns to ore grinding, undersize material carries out cyclone classification, and obtaining sand setting and grinding fineness is that -0.074mm accounts for 60~72% and overflows
Stream, sand setting are carried out regrinding rear re-grading, be formed closed circuit；
(2) the overflow pulp concentration of set-up procedure (1) is 33~40wt%, then sequentially add 200 into ore pulp~
The activator of 350g/t, the combined capturing and collecting agent of 30~80g/t, 10~30g/t foaming agent, it is thick to carry out zinc within stirring 3 minutes or more
Choosing, obtains zinc rougher concentration and zinc rougher tailings；
(3) the zinc rougher tailings of step (2) is scanned three times, wherein scanning successively 30~80g/t of addition for the first time
Activator, 5~20g/t combined capturing and collecting agent, stirring 3 minutes or more scans the activation for successively adding 20~50g/t for the second time
Agent, 5~10g/t combined capturing and collecting agent, stirring 3 minutes or more scans do not add any medicament for the third time, in addition, for the first time, the
Secondary tailing of scanning carries out scanning in next step respectively, and scanning tailing for the third time is finally to scan tailing, is scanned for the second time, for the third time
Concentrate return respectively upper level scan it is middle selected again, formed it is closed circuit；
(4) the zinc rougher concentration of step (2) is subjected to the mixed choosing of a zinc sulphur, the in the tailing of the mixed choosing of zinc sulphur and step (3)
After the concentrate mixing of once purging selection in return roughing, formation is closed circuit, and the concentrate of the mixed choosing of zinc sulphur is classified, overflow is obtained and sinks
Sand, sand setting are classified again after regrinding, by granularity after classification be -0.037mm account for 70~80% overflow carry out three times zinc it is selected,
In, each zinc is selected to add inhibitor respectively, in addition, for the first time, that the selected concentrate of second of zinc carries out next stage respectively is selected,
The selected concentrate of third time zinc is the concentrate of the final zinc containing indium, the selected tailing of third time zinc return upper level zinc it is selected in, shape
At closed circuit；
(5) zinc concentrate is scanned three times for the tailing selected to first time zinc in step (4) progress, wherein first time zinc concentrate
Scan 20~80g/t of middle addition activator, 5~10g/t of collecting agent, second, third time zinc concentrate scan not adding medicine, this
Outside, the concentrate that first time zinc concentrate the is scanned tailing selected with second of zinc mix after return first time zinc it is selected in, for the first time,
The tailing that second of zinc concentrate is scanned sequentially enters during next stage zinc concentrate scans, and the tailing that third time zinc concentrate is scanned is final
Zinc concentrate scans tailing, second, the concentrate scanned of third time zinc concentrate successively return during upper level zinc concentrate scans, formation is closed
Road.
The grinding operation that ore in the step (1) carries out is the two of SAB grinding flowsheet, SABC grinding flowsheet or classics
The fully closed road grinding flowsheet of section, ore milling concentration are 70~84%.
The activator is lived for one of copper sulphate, ammonium carbonate, X-43 activator or arbitrarily than several mixtures
Agent is 1~10% using mass percent concentration is preceding diluted with water to.
The foaming agent is one of terpenic oil, MIBC or any mixture for comparing two kinds.
The inhibitor is milk of lime.
The selected flotation column that is all made of of zinc three times in the step (4) carries out.
The combined capturing and collecting agent is in use, after mixing by 206 modified xanthates, ethyl xanthate and butylamine black powder, add water
It is configured to the solution that mass concentration is 1~10%.
Each selected inhibitor added respectively of zinc in the step (4), in terms of the concentrate dry weight selected by each zinc, addition
The inhibitor of 400-900g/t.
Also contain copper in the high-iron sphalerite containing indium, increases between step (1) and step (2) and select copper operation, obtain
Copper tailing is carried out zinc roughing by copper concentrate and copper tailing again.
206 modified xanthates are sold by the preferential company's production of Kunming iron peak beneficiation reagent.
MIBC is efficient foaming agent, is produced and is sold by Qingdao Xin Yuan auxiliary chemicals Co., Ltd.
X-43 is produced by Yunnan Yuan Kuang Science and Technology Development Co., Ltd. and is sold.
Combined capturing and collecting agent of the invention is strong to the collecting ability of the high-iron sphalerite containing indium, especially catches to rare precious metal indium
Receipts ability is strong, and selectivity is good.
The beneficial effects of the present invention are:
(1) 206 modified xanthate of ingredient, ethyl xanthate and the butylamine black powder of combined capturing and collecting agent of the invention easily obtain, price
Low, dosing is few, and production cost is low, and nontoxic and pollution-free, environmentally friendly.
(2) combined capturing and collecting agent of the invention is with strong points, has filled up the combined capturing and collecting agent of high-iron sphalerite containing indium both at home and abroad
Blank, combined capturing and collecting agent are strong to the collecting ability of high-iron sphalerite containing indium, especially strong to the collecting agent ability of rare precious metal indium, lead to
Beneficiation flowsheet of the invention is crossed, ore dressing can be obtained from low-grade high-iron sphalerite containing indium (containing zinc 2~3%, 30~50g/t containing indium)
To 91% or more the rate of recovery, the zinc concentrate of 48% or more grade, the rate of recovery of indium is up to 60% or more.
(3) selectivity of combined capturing and collecting agent of the invention is strong, can be very good that indium high-iron sphalerite point will be contained from ore pulp
It separates out and, substantially reduce the inhibitor dosage of selected middle addition.
(4) field application of the present invention is easy to implement, can carry out using scene in the case where not changing original production technology
Using simple, technique good separation effect, index is stablized.
Combined capturing and collecting agent of the invention has been applied successfully in all imperial mining area of Yunnan mountain of papers at present, improves zinc indium recovery.
Detailed description of the invention
Fig. 1 is the process flow diagram that combined capturing and collecting agent of the invention is applied in flotation.
Specific embodiment
The present invention is described further with attached drawing with reference to embodiments, but the present invention is not limited to ranges as described below.
Embodiment 1: high-iron sphalerite containing indium is derived from Yunnan mountain of papers, valuable element cupric 0.151%, zinc in sample
4.19%, tin 0.37%, iron 21.70%, sulphur 7.9%, rare precious metal indium, silver content be respectively 76.41g/t, 9.52g/t,
Silica 24.06%, aluminum oxide 5.35%, magnesia 4.47%, calcium oxide 3.19%.Through finding out, major metal
Mineral are marmatite, chalcopyrite, magnetic iron ore, pyrite, cassiterite, magnetic iron ore and a small amount of mispickel；Gangue mineral is mainly
Quartz, mica, the tremolite, ilvaite, chlorite, talcum, dolomite and fluorite etc., the main preservation of indium is in marmatite, shape
At high-iron sphalerite containing indium.Collecting indium zinc is carried out using combined capturing and collecting agent to this ore, combined capturing and collecting agent is by following parts by weight
Component composition: 206 40 parts of modified xanthates, 40 parts of ethyl xanthate, 20 parts of butylamine black powder, combined capturing and collecting agent is in use, modified by 206
Xanthate, ethyl xanthate and butylamine black powder after mixing, add water to be configured to the solution that mass concentration is 5%.
Using process flow as shown in Figure 1, specific process parameter and mineral processing index are as follows:
(1) will it is broken after the ore of granularity≤250mm ore grinding is carried out using SAB grinding flowsheet, SAB ore grinding stream include half from
Mill and ball milling, wherein Semi-Autogenous ore milling concentration is 84%, Semi-Autogenous ore milling product is sieved by drum sieve, wherein on sieve
Material returns in Semi-Autogenous, and undersize material carries out cyclone classification, obtains sand setting and grinding fineness is that -0.074mm accounts for 72%
Overflow, Grading Overflow enter sorting operation, and sand setting is classified again after being regrinded, so as to form closed cycle；
(2) it first carries out the overflow of step (1) to select copper operation, obtains copper concentrate and copper tailing；
(3) pulp density of the copper tailing of set-up procedure (2) is 38wt%, then sequentially adds 300g/t's into ore pulp
X-43 activator, the combined capturing and collecting agent of 60g/t, 20g/t terpenic oil, stir progress roughing in 10 minutes, X-43 activator makes
The solution that mass percent concentration is 5% is configured to preceding plus water to use, and obtains rougher concentration and rougher tailings；
(4) rougher tailings of step (3) is scanned three times, wherein scanning the X-43 for successively adding 50g/t for the first time
The combined capturing and collecting agent of activator, 15g/t stirs 3 minutes, scans the X-43 activator, 5g/t for successively adding 30g/t for the second time
Combined capturing and collecting agent stirs 3 minutes, scans do not add any medicament for the third time, in addition, scanning tailing difference for the first time, for the second time
Carry out in next step scan, scan for the third time tailing be finally scan tailing, for the second time, third time scavenger concentrate return to upper one respectively
Grade scan it is middle selected again, formation it is closed circuit；
(5) rougher concentration of step (3) is subjected to the mixed choosing of a zinc sulphur, zinc sulphur mixes first in the tailing and step (3) of choosing
After the secondary concentrate mixing scanned in return roughing, formation is closed circuit, and the concentrate of the mixed choosing of zinc sulphur is classified, overflow is obtained and sinks
Sand, sand setting are classified again after regrinding, by granularity after classification be -0.037mm account for 75% overflow carry out three times zinc it is selected, wherein
Zinc is selected every time adds inhibitor respectively, and the amount of the inhibitor of addition adds 600g/t in terms of the selected concentrate dry weight of each zinc
Milk of lime, in addition, for the first time, the selected concentrate of second of zinc carries out next stage respectively selected, the selected concentrate of third time zinc
For the concentrate of the finally zinc containing indium, the selected tailing of third time zinc return upper level zinc it is selected in, formed closed circuit, and zinc is selected three times
It is all made of flotation column progress；
(contain zinc 4.19%, contain indium 76.41g/t) under the premise of raw ore is higher containing indium containing zinc, obtaining grade is
48.87%, the zinc concentrate that the rate of recovery 93.41%, concentration ratio are 13.23, zinc concentrate 830.24g/t containing indium, the rate of recovery of indium
It is 73.17%.This index is to be directed to index best in the ore dressing open source literature and data of the high-iron sphalerite containing indium at present, with
The single collecting agent of tradition is compared, and has collecting ability strong, and selectivity is good, and production target stability is good, the low advantage of production cost.
Embodiment 2: high-iron sphalerite containing indium takes to all imperial ore body of mining area 13 in Yunnan, valuable element cupric in sample
0.123%, zinc 2.89%, tin 0.20%, iron 18.70%, sulphur 5.4%, rare precious metal indium, silver-colored content are respectively 51.27g/
T, 11.52g/t, silica 28.47%, aluminum oxide 6.42%, magnesia 4.89%, calcium oxide 3.76%.Mainly
Metalliferous mineral is marmatite, chalcopyrite, magnetic iron ore, pyrite, cassiterite, magnetic iron ore and a small amount of mispickel；Gangue mineral master
It to be quartz, mica, the tremolite, ilvaite, chlorite, talcum, dolomite and fluorite etc..Combined capturing and collecting agent is used to this ore
Collecting indium zinc is carried out, combined capturing and collecting agent is made of the component of following parts by weight: 206 30 parts of modified xanthates, 40 parts of ethyl xanthate, fourth
30 parts of amido black medicine, combined capturing and collecting agent is in use, after mixing by 206 modified xanthates, ethyl xanthate and butylamine black powder, add water to match
It is set to the solution that mass concentration is 10%.
The method that combined capturing and collecting agent is used to promote zinc indium recovery, the specific steps are as follows:
(1) ore of granularity≤250mm carries out ore grinding using SABC grinding flowsheet after will be broken, wherein Semi-Autogenous ore grinding
Concentration is 80%, and Semi-Autogenous ore milling product is sieved by drum sieve, and wherein on-the-sieve material returns in Semi-Autogenous, undersize material
Cyclone classification is carried out, sand setting is obtained and grinding fineness is the overflow that -0.074mm accounts for 69%, Grading Overflow enters sorting operation,
Sand setting is classified again after being regrinded, so as to form closed cycle；
(2) it first carries out the overflow of step (1) to select copper operation, obtains copper concentrate and copper tailing；
(3) pulp density of the copper tailing of set-up procedure (2) is 40wt%, then sequentially adds 200g/t's into ore pulp
Ammonium carbonate, the combined capturing and collecting agent of 30g/t, 10g/t MIBC, stir progress roughing in 15 minutes, ammonium carbonate is matched using preceding plus water
It is set to the solution that mass percent concentration is 10% to use, obtains rougher concentration and rougher tailings；
(4) rougher tailings of step (3) is scanned three times, wherein scanning the carbonic acid for successively adding 30g/t for the first time
The combined capturing and collecting agent of ammonium, 5g/t stirs 3 minutes, scans the combination collecting for successively adding the ammonium carbonate, 7g/t of 20g/t for the second time
Agent, stir 3 minutes, scan do not add any medicament for the third time, in addition, for the first time, for the second time scan tailing carry out respectively it is next
Step is scanned, and scanning tailing for the third time is finally to scan tailing, and for the second time, third time scavenger concentrate returns respectively during upper level scans
It is selected, is formed closed circuit again；
(5) rougher concentration of step (3) is subjected to the mixed choosing of a zinc sulphur, zinc sulphur mixes first in the tailing and step (3) of choosing
After the secondary concentrate mixing scanned in return roughing, formation is closed circuit, and the concentrate of the mixed choosing of zinc sulphur is classified, overflow is obtained and sinks
Sand, sand setting are classified again after regrinding, by granularity after classification be -0.037mm account for 70% overflow carry out three times zinc it is selected, wherein
Zinc is selected every time adds inhibitor respectively, and the amount of the inhibitor of addition adds 400g/t in terms of the selected concentrate dry weight of each zinc
Milk of lime, in addition, for the first time, the selected concentrate of second of zinc carries out next stage respectively selected, the selected concentrate of third time zinc
For the concentrate of the finally zinc containing indium, the selected tailing of third time zinc return upper level zinc it is selected in, formed closed circuit, and zinc is selected three times
It is all made of flotation column progress；
More medium (containing zinc 3.21%, contain indium 51.27g/t) containing indium containing zinc in raw ore, obtaining grade is
48.48%, the zinc concentrate that the rate of recovery is 92.51%, zinc concentrate 695.47g/t containing indium, the rate of recovery of indium are 70.46%.This
Index is at present for index best in the ore dressing open source literature of the high-iron sphalerite containing indium and data, with the single collecting agent of tradition
It compares, has collecting ability strong, selectivity is good, and production target stability is good, the low advantage of production cost.
Embodiment 3: the high-iron sphalerite containing indium of the present embodiment takes to all imperial ore body of mining area 24 in Yunnan, valuable member in sample
Plain cupric 0.144%, zinc 2.23%, tin 0.18%, iron 16.48%, sulphur 3.57%, rare precious metal indium, silver-colored content are respectively
34.5g/t, 10.49g/t, silica 30.24%, aluminum oxide 5.75%, magnesia 5.07%, calcium oxide are
3.84%.Major metal mineral are marmatite, chalcopyrite, magnetic iron ore, pyrite, cassiterite, magnetic iron ore and a small amount of mispickel；
Gangue mineral is mainly quartz, mica, the tremolite, ilvaite, chlorite, talcum, dolomite and fluorite etc..This ore is used
Combined capturing and collecting agent carries out collecting indium zinc, and combined capturing and collecting agent is made of the component of following parts by weight: 206 50 parts of modified xanthates, ethyl
30 parts of xanthate, 20 parts of butylamine black powder, combined capturing and collecting agent is in use, 206 modified xanthates, ethyl xanthate and butylamine black powder are mixed equal
After even, water is added to be configured to the solution that mass concentration is 10%.
The method that combined capturing and collecting agent is used to promote zinc indium recovery, the specific steps are as follows:
(1) after broken, the granularity for entering ore grinding stone is less than 15mm, carries out ore grinding using two sections of fully closed road grinding flowsheets,
One section of mill ore milling concentration is 70%, and one section of mill ore milling product passes through cyclone classification, and wherein sand setting returns in one section of mill, cyclone
Overflow carries out cyclone classification again, and classification sand setting returns to two sections of ball millings and carries out ore grinding, and Grading Overflow enters sorting operation, final to grind
Mine fineness is that -0.074mm accounts for 60%；
(2) it first carries out the overflow of step (1) to select copper operation, obtains copper concentrate and copper tailing；
(3) pulp density of the copper tailing of set-up procedure (2) is 33wt%, then sequentially adds 350g/t's into ore pulp
Copper sulphate, the combined capturing and collecting agent of 80g/t, the MIBC of 30g/t and terpenic oil mixture, stir progress roughing in 15 minutes, sulfuric acid
Copper is being configured to the solution use that mass percent concentration is 1% using preceding plus water, obtains rougher concentration and rougher tailings；
(4) rougher tailings of step (3) is scanned three times, wherein scanning the sulfuric acid for successively adding 80g/t for the first time
The combined capturing and collecting agent of copper, 20g/t stirs 3 minutes, and the combination for scanning the successively copper sulphate, 10g/t of addition 50g/t for the second time is caught
Receive agent, stir 3 minutes, scan do not add any medicament for the third time, in addition, for the first time, scan tailing for the second time and carry out down respectively
One step is scanned, and scanning tailing for the third time is finally to scan tailing, and for the second time, third time scavenger concentrate returns to upper level respectively and scan
It is middle to be selected again, it is formed closed circuit；
(5) rougher concentration of step (3) is subjected to the mixed choosing of a zinc sulphur, zinc sulphur mixes first in the tailing and step (3) of choosing
After the secondary concentrate mixing scanned in return roughing, formation is closed circuit, and the concentrate of the mixed choosing of zinc sulphur is classified, overflow is obtained and sinks
Sand, sand setting are classified again after regrinding, by granularity after classification be -0.037mm account for 80% overflow carry out three times zinc it is selected, wherein
Zinc is selected every time adds inhibitor respectively, and the amount of the inhibitor of addition adds 900g/t in terms of the selected concentrate dry weight of each zinc
Milk of lime, in addition, for the first time, the selected concentrate of second of zinc carries out next stage respectively selected, the selected concentrate of third time zinc
For the concentrate of the finally zinc containing indium, the selected tailing of third time zinc return upper level zinc it is selected in, formed closed circuit, and zinc is selected three times
It is all made of flotation column progress；
(contain zinc 2.23%, contain indium 34.50g/t) in the case where raw ore is more relatively low containing indium containing zinc, obtains grade
The zinc concentrate for being 91.43% for the 48.17%, rate of recovery, zinc concentrate 587.6g/t containing indium, the rate of recovery of indium are 67.43%.This
Index is at present for index best in the ore dressing open source literature of the high-iron sphalerite containing indium and data, with the single collecting agent of tradition
It compares, has collecting ability strong, selectivity is good, and production target stability is good, the low advantage of production cost.
Embodiment 4: the high-iron sphalerite containing indium of the present embodiment is derived from Guangxi somewhere, contains zinc 3.62%, iron content in ore
38.79%, the content of rare precious metal indium is 46.28g/t, carries out collecting, this combined capturing and collecting agent using combined capturing and collecting agent of the present invention
It is made of the component of following parts by weight: 206 40 parts of modified xanthates, 50 parts of ethyl xanthate, 10 parts of butylamine black powder.Combined capturing and collecting agent makes
Used time, after mixing by 206 modified xanthates, ethyl xanthate and butylamine black powder, add water be configured to mass concentration be 10% it is molten
Liquid.The method that combined capturing and collecting agent is used to promote zinc indium recovery, the specific steps are as follows:
(1) ore of granularity≤250mm carries out ore grinding using SAB grinding flowsheet after will be broken, wherein Semi-Autogenous ore grinding
Concentration is 80%, and Semi-Autogenous ore milling product is sieved by drum sieve, and wherein on-the-sieve material returns in Semi-Autogenous, undersize material
Cyclone classification is carried out, sand setting is obtained and grinding fineness is the overflow that -0.074mm accounts for 70%, Grading Overflow enters sorting operation,
Sand setting is classified again after being regrinded, so as to form closed cycle；
(2) the overflow pulp concentration of set-up procedure (1) is 36wt%, and the carbonic acid of 200g/t is then sequentially added into ore pulp
The mixture of ammonium and X-43, the combined capturing and collecting agent of 30g/t, 10g/t MIBC, stir progress roughing in 15 minutes, ammonium carbonate and X-
43 are being configured to the solution use that mass percent concentration is 8% using preceding plus water, obtain rougher concentration and rougher tailings；
(3) rougher tailings of step (2) is scanned three times, wherein scanning the carbonic acid for successively adding 40g/t for the first time
The combined capturing and collecting agent of the mixture of ammonium and X-43,10g/t stirs 3 minutes, scans the ammonium carbonate for successively adding 25g/t for the second time
With the combined capturing and collecting agent of the mixture of X-43,8g/t, stirs 3 minutes, scan do not add any medicament for the third time, in addition, first
It is secondary, scan for the second time tailing carry out respectively in next step scan, scan for the third time tailing be finally scan tailing, for the second time, third
Secondary scavenger concentrate return respectively upper level scan it is middle selected again, formed it is closed circuit；
(4) rougher concentration of step (2) is subjected to the mixed choosing of a zinc sulphur, zinc sulphur mixes first in the tailing and step (3) of choosing
After the secondary concentrate mixing scanned in return roughing, formation is closed circuit, and the concentrate of the mixed choosing of zinc sulphur is classified, overflow is obtained and sinks
Sand, sand setting are classified again after regrinding, by granularity after classification be -0.037mm account for 78% overflow carry out three times zinc it is selected, wherein
Zinc is selected every time adds inhibitor respectively, and the amount of the inhibitor of addition adds 500g/t in terms of the selected concentrate dry weight of each zinc
Milk of lime, in addition, for the first time, the selected concentrate of second of zinc carries out next stage respectively selected, the selected concentrate of third time zinc
For the concentrate of the finally zinc containing indium, the selected tailing of third time zinc return upper level zinc it is selected in, formed closed circuit, and zinc is selected three times
It is all made of flotation column progress.
Contain zinc 3.62% in raw ore, under 46.28g/t containing indium, obtains that grade is 70.19%, the rate of recovery is 94.87%
Zinc concentrate, zinc concentrate 792.36g/t containing indium, the rate of recovery of indium are 80.94%, and effect is preferable.
Above in conjunction with attached drawing, the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (9)
1. a kind of combined capturing and collecting agent of high-iron sphalerite containing indium, which is characterized in that the combined capturing and collecting agent is by following parts by weight
Component composition: 206 30~50 parts of modified xanthates, 30~50 parts of ethyl xanthate, 10~30 parts of butylamine black powder.
2. the method that the combined capturing and collecting agent of the high-iron sphalerite described in claim 1 containing indium is used to promote zinc indium recovery, special
Sign is that specific step is as follows:
(1) ore of granularity≤250mm carries out ore grinding after will be broken, and ore milling product is sieved with drum sieve, and on-the-sieve material is returned
Ore grinding is returned, undersize material carries out cyclone classification, obtains sand setting and grinding fineness is the overflow that -0.074mm accounts for 60~72%, sink
Sand carries out regrinding rear re-grading, is formed closed circuit；
(2) the overflow pulp concentration of set-up procedure (1) is 33~40wt%, and 200~350g/t is then sequentially added into ore pulp
Activator, the combined capturing and collecting agent of 30~80g/t, 10~30g/t foaming agent, carry out zinc roughing within stirring 3 minutes or more, obtain
Zinc rougher concentration and zinc rougher tailings；
(3) the zinc rougher tailings of step (2) is scanned three times, wherein scanning the work for successively adding 30~80g/t for the first time
The combined capturing and collecting agent of agent, 5~20g/t stirring 3 minutes or more, scans the activator for successively adding 20~50g/t, 5 for the second time
The combined capturing and collecting agent of~10g/t stirring 3 minutes or more, is scanned do not add any medicament for the third time, in addition, for the first time, for the second time
It scans tailing to carry out scanning in next step respectively, scanning tailing for the third time is finally to scan tailing, second, third time scavenger concentrate
Respectively return upper level scan it is middle selected again, formation it is closed circuit；
(4) the zinc rougher concentration of step (2) is subjected to the mixed choosing of a zinc sulphur, zinc sulphur mixes in the tailing and step (3) of choosing for the first time
It being returned in roughing after the concentrate mixing scanned, formation is closed circuit, and the concentrate of the mixed choosing of zinc sulphur is classified, overflow and sand setting are obtained,
Sand setting is classified again after regrinding, by granularity after classification be -0.037mm account for 70~80% overflow carry out three times zinc it is selected, wherein
Zinc is selected adds inhibitor respectively every time, in addition, for the first time, that the selected concentrate of second of zinc carries out next stage respectively is selected, the
The selected concentrate of zinc is the concentrate of the final zinc containing indium three times, the selected tailing of third time zinc return upper level zinc it is selected in, formed
It is closed circuit；
(5) zinc concentrate is scanned three times for the tailing selected to first time zinc in step (4) progress, wherein first time zinc concentrate is scanned
20~80g/t of middle addition activator, 5~10g/t of collecting agent, second, third time zinc concentrate scan not adding medicine, in addition,
The concentrate that first time zinc concentrate the is scanned tailing selected with second of the zinc of step (4) returned after mixing first time zinc it is selected in, the
Once, the tailing that second of zinc concentrate is scanned sequentially enters during next stage zinc concentrate scans, the tailing that third time zinc concentrate is scanned
Scan tailing for final zinc concentrate, second, the concentrate scanned of third time zinc concentrate successively return during upper level zinc concentrate scans,
It is formed closed circuit.
3. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: the grinding operation that the ore in the step (1) carries out is SAB grinding flowsheet, SABC grinding flowsheet or classics
Two sections of fully closed road grinding flowsheets, ore milling concentration be 70~84%.
4. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: the activator is one of copper sulphate, ammonium carbonate, X-43 activator or arbitrarily than several mixtures,
And activator is 1~10% using mass percent concentration is preceding diluted with water to.
5. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: the foaming agent is one of terpenic oil, MIBC or any mixture for comparing two kinds.
6. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: the inhibitor is milk of lime.
7. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: the selected flotation column that is all made of of zinc three times in the step (4) carries out.
8. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: each selected inhibitor added respectively of zinc in the step (4), in terms of the concentrate dry weight selected by each zinc,
Add the inhibitor of 400-900g/t.
9. the method that the combined capturing and collecting agent of the high-iron sphalerite according to claim 2 containing indium is used to promote zinc indium recovery,
It is characterized by: also containing copper in the high-iron sphalerite containing indium, increases between step (1) and step (2) and select copper operation, obtain
To copper concentrate and copper tailing, copper tailing is subjected to zinc roughing again.
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