CN107557582A - A kind of selective extraction and the method for being enriched with valuable metal in more metals resources - Google Patents
A kind of selective extraction and the method for being enriched with valuable metal in more metals resources Download PDFInfo
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- CN107557582A CN107557582A CN201710613387.1A CN201710613387A CN107557582A CN 107557582 A CN107557582 A CN 107557582A CN 201710613387 A CN201710613387 A CN 201710613387A CN 107557582 A CN107557582 A CN 107557582A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 127
- 239000002184 metal Substances 0.000 title claims abstract description 127
- 150000002739 metals Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000000605 extraction Methods 0.000 title claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 63
- 239000010703 silicon Substances 0.000 claims abstract description 63
- 239000002210 silicon-based material Substances 0.000 claims abstract description 33
- 239000002699 waste material Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052720 vanadium Inorganic materials 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- 239000010970 precious metal Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- -1 aluminium silicon titanium Chemical compound 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001926 trapping method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical group [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of selective extraction and the method for being enriched with valuable metal in more metals resources, belong to metals resources clean utilization technical field.More metalliferous materials, additive and silicon materials are carried out to pyrometallurgical smelting extraction valuable metal together first, obtain silicon-base alloy and waste residue；Obtained silicon-base alloy is subjected to concentration of valuable metals, valuable metal enriched substance and HIGH-PURITY SILICON are obtained after separation, waste residue is carried out to the measure of valuable metal content, carries out second extraction valuable metal or discarded as pending more metals resources materials again；HIGH-PURITY SILICON can return to as silicon materials, or for electronics or photovoltaic industry silicon material.This method is used as extraction and the main body of concentration of valuable metals using silicon substrate material, obtained HIGH-PURITY SILICON can both be used as silicon materials to recirculate and use, it can also be used for preparing solar level or the raw material of electronic-grade silicon, be a kind of green, the new technology of efficient, low cost metals resources clean utilization.
Description
Technical field
The present invention relates to a kind of selective extraction and the method for being enriched with valuable metal in more metals resources, belong to metals resources
Clean utilization technical field.
Background technology
Usually contain at least one valuable metal in more metals resources, such as caused titaniferous vanadium after vanadium titano-magnetite ironmaking
Blast furnace slag, the titanium slag containing vanadium after pyrogenic process or wet method vanadium extraction titanium, failure cleaning catalyst for tail gases of automobiles and stone containing rare precious metal
The industrial carried catalyst of oily petrochemistry, waste residue containing rare precious metal etc..More metals resources are extraction and recovery valuable metal
Important source material source, how at low cost, greenly and efficiently from more metals resources extract and reclaim valuable metal tool
There is important meaning.Because mutually complexity, element are more with thing for composition in more metals resources, the mistake of valuable metal is caused to extract and reclaimed
Cheng Tongchang is with complex process, the problem such as technological process is long, cost is high, environmental pollution is serious.
Extracting and be enriched with the valuable metal in more metals generally has two methods of pyrogenic process and wet method, but is extracting and be enriched with
It can more or less be monopolized in the engineering of valency metal with complex process, cost height, environment and intellectual property by overseas enterprise
Problem.For example, when extracting the titanium in titanium-containing blast furnace slag with aluminothermic process, substantial amounts of aluminium need to be consumed, and in obtained aluminium silicon titanium alloy
Containing substantial amounts of impurity element, limit the purposes of aluminium silicon titanium alloy product, how to remove impurity in aluminium silicon titanium alloy and
Titanium in separation aluminium silicon titanium alloy is the problem for needing to solve；Exist if with the titanium in wet underwater welding and enrichment titanium-containing blast furnace slag
Technological process length and environmental problem；Such as extracted with pyrogenic process and be enriched with cleaning catalyst for tail gases of automobiles, particularly by the use of iron or copper as
Trapping agent extracts and the technology of enriching noble metals is by external noble metal company monopolizing, and iron method of trapping and copper trapping method also have work
The shortcomings that skill long flow path.
Valuable metal in more metals is extracted and is enriched with using silicon substrate material as material selectivity the invention discloses a kind of
Method.Silicon will not be consumed largely during extracting with concentration of valuable metals, and after extracted and concentration of valuable metals
The HIGH-PURITY SILICON arrived can use as raw material repetitive cycling, or as the raw material for preparing solar level or electronic-grade silicon.This hair
Bright is a kind of non-carbon-emitting, low cost, the new technology that flow is short, environment-friendly.
The content of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of selective extraction and is enriched with more metals
The method of valuable metal in resource.The present invention contains vanadium using more metals resources as raw material such as containing V-Ti blast-furnace slag, after vanadium extraction titanium
Titanium waste residue, the spent auto-catalysts containing rare precious metal and petro chemical industry carried catalyst, the waste residue containing rare precious metal
Deng the method for selective extraction and concentration of valuable metals.This method is used as extraction and the master of concentration of valuable metals using silicon substrate material
Body, obtained HIGH-PURITY SILICON can both be used as silicon materials to recirculate and use, it can also be used to prepare solar level or electronic-grade silicon
Raw material, it is a kind of green, the new technology of efficient, low cost metals resources clean utilization.The present invention passes through following technical side
Case is realized.
A kind of selective extraction and the method for being enriched with valuable metal in more metals resources, it is comprised the following steps that：
（1）More metalliferous materials, additive and silicon materials are carried out to pyrometallurgical smelting extraction valuable metal together first, obtain silicon substrate conjunction
Gold and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals, and valuable metal enriched substance and high-purity is obtained after separation
Silicon, by step（1）Obtained waste residue carries out the measure of valuable metal content, if valuable tenor height can be used as step again
（1）In pending more metals resources materials carry out second extraction valuable metals, until valuable metal content can as little as discard；
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry silicon
Raw material.
The step（1）In more metalliferous materials be containing V-Ti blast-furnace slag, titanium containing vanadium waste residue caused by after vanadium extraction titanium, containing dilute
Waste residue of the spent auto-catalysts and petro chemical industry of noble metal with carried catalyst or containing rare precious metal.
The step（1）Middle additive is CaO, SiO2、Al2O3, one or more of arbitrary proportion mixtures in MgO, always
Addition according to circumstances depending on；But work as in more metalliferous materials and contain CaO, SiO2、Al2O3, two kinds in MgO and it is two or more when,
There can be the situation for being added without additive.
The step（1）Middle silicon materials are silicon or silicon-base alloy, and the mass ratio of silicon materials and more metalliferous materials is according to reality
Border situation is added.
The step（1）Pyrometallurgical smelting temperature is >=1450 DEG C, soaking time >=1 hour.
The step（2）Concentration of valuable metals method be electromagnetism melting technique, directional solidification technique, zone refining technology,
Monocrystalline silicon growing technology or wet processing technique.
The valuable metal that above-mentioned more metalliferous materials include is zirconium（Zr）, vanadium（V）, titanium（Ti）, platinum（Pt）, palladium（Pd）, rhodium
（Rh）, rhenium（Re）Deng rare precious metal；Cerium（Ce）, lanthanum（La）, neodymium（Nd）Deng rare earth metal；Zinc（Zn）, manganese（Mn）Deng valuable metal.
The beneficial effects of the invention are as follows：
（1）The present invention selection silicon materials selective extraction and concentration of valuable metals from more metals resources, take full advantage of silicon with
Valuable metal has characteristic that can selectively with the reaction of valuable metal compound compared with strong affinity or silicon, and silicon is in selective extraction
It is high with loss only few during concentration of valuable metals, the rate of recovery of silicon.
（2）The present invention selection silicon materials selective extraction and concentration of valuable metals from more metals resources, can reach simultaneously
To extraction valuable metal, concentration of valuable metals, a variety of purposes that silicon materials recycle, silicon purifies.
（3）The present invention takes full advantage of the peculiar property that valuable metal distributes in silicon process of setting in solid liquid interface,
It is enriched with silicon-base alloy during valuable metal, valuable metal element is enriched in liquid phase or silicon wafer circle in silicon process of setting,
Hardly it is retained in solid silicon crystal, therefore, after extracted and concentration of valuable metals, damage of the valuable metal in solid silicon
Lose negligible.
（4）The silicon materials of the present invention can be used as silicon thing again after the valuable metal in extracting and being enriched with more metals resources
Material recycles, or as the raw material for preparing solar energy level silicon or electronic-grade silicon, significantly reduces into production cost.
（5）The present invention can not only handle more metalliferous materials of the valuable metal containing ratio of medium-high grade using silicon materials, can also
Handle more metalliferous materials containing low-grade valuable metals.
（6）The present invention in more metalliferous material of the processing containing noble metal, such as the spent auto-catalysts containing rare precious metal with
Petro chemical industry carried catalyst, compared with present iron method of trapping and copper trapping method, with cost is low, flow is short, nothing
The advantages of carbon emission, silicon can recycle.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in figure 1, the selective extraction and the method for being enriched with valuable metal in more metals resources, it is comprised the following steps that：
（1）First by more metalliferous materials（Containing V-Ti blast-furnace slag, the content of wherein titanium, vanadium and manganese be respectively 11.18wt%,
0.17wt% and 0.53wt%）, additive（It is additive-free）And silicon materials（Industrial silicon, purity 98.6%, containing V-Ti blast-furnace slag and silicon
The mass ratio of material is 5:3）It is that 1450 DEG C of insulations carry out pyrometallurgical smelting extraction valuable metal for 5 hours in temperature, obtains silicon substrate conjunction
Gold and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals（It is enriched with, is oriented using directional solidification technique
The condition of solidification is：Temperature is 1450 DEG C, moved down with the speed of 0.1 mm/min, the top of solid silicon after directional solidification
For the enriched substance of titanium, vanadium and manganese, the lower end of enriched substance is more than 99.98 % HIGH-PURITY SILICON for purity）, valuable metal is obtained after separation
Enriched substance and HIGH-PURITY SILICON, by step（1）Obtained waste residue carries out the measure of valuable metal content, titanium, vanadium and manganese wherein in waste residue
Content is respectively 1.21wt%, 0.03wt% and 0.03wt%, and valuable metal content height can be used as step again（1）In it is pending
More metals resources materials carry out second extraction valuable metal, until valuable metal content can as little as discard；
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry silicon
Raw material.
Embodiment 2
As shown in figure 1, the selective extraction and the method for being enriched with valuable metal in more metals resources, it is comprised the following steps that：
（1）First will the waste residue of titanium containing vanadium caused by after vanadium extraction titanium（Content difference containing V-Ti blast-furnace slag, wherein titanium, vanadium and manganese
For 23.4wt%, 0.23wt% and 0.92wt%）, additive（CaO, account for the slag quality of titanium containing vanadium 18%）And silicon materials（Silico-aluminum,
Aluminium content is 20wt%, and the mass ratio containing V-Ti blast-furnace slag and silicon materials is 1:3）It is that 1550 DEG C of insulations carry out fire in 3 hours in temperature
Valuable metal is extracted in method melting, obtains silicon-base alloy and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals（Using wet processing technique, silicon-base alloy exists
500 DEG C are cooled to 1 DEG C/min of speed after 1450 DEG C of fusings, the silicon-base alloy after heat treatment is ground into 75 microns of silicon
Powder, with the titanium in wet-leaching silica flour, vanadium and manganese, leaching condition：With hydrofluoric acid and the nitration mixture of hydrochloric acid（Volume ratio is 1:1, mixing
The concentration of preceding hydrofluoric acid and hydrochloric acid is 10mol/L）As leachate, extraction temperature is 80 DEG C, and extraction time is 5 hours, leaching
Go out the loss of rear titanium, vanadium and manganese in solid silicon and be less than 2wt%, the titanium, vanadium and manganese more than 98% are transferred in leachate, are leached
The purity 99.9wt% of HIGH-PURITY SILICON afterwards, leachate and HIGH-PURITY SILICON containing valuable metal are obtained after separation, by step（1）What is obtained is useless
Slag carries out the measure of valuable metal content, and titanium, vanadium and manganese content total content are less than 0.2wt% wherein in waste residue, and the waste residue can give up
Abandon；
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry silicon
Raw material.
Embodiment 3
As shown in figure 1, the selective extraction and the method for being enriched with valuable metal in more metals resources, it is comprised the following steps that：
（1）First by more metalliferous materials（Spent auto-catalysts containing rare precious metal, cordierite are carrier, wherein zirconium, cerium, lanthanum,
Platinum, palladium, rhodium, the content of zinc and nickel are respectively 5.5wt%, 3.7wt%, 0.6wt%, 737ppm, 715ppm, 172ppm, 0.17wt%
And 600ppm）, additive（CaO, SiO2, Al2O3And MgO, account for respectively failure cleaning catalyst for tail gases of automobiles quality 46%,
18%th, 3% and 2%）And silicon materials（Industrial silicon, purity 98.6%, the quality of spent auto-catalysts and silicon materials containing rare precious metal
Than for 1:2）It is that 1500 DEG C of insulations carry out pyrometallurgical smelting extraction valuable metal for 7 hours in temperature, obtains silicon-base alloy and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals（It is enriched with using zone refining technology, region
Melting condition：Temperature is 1450 DEG C, and the translational speed of heating region from the bottom up is 0.1 mm/min, zirconium after zone refining,
Cerium, lanthanum, platinum, palladium, rhodium, zinc and nickel are enriched in the top of solid silicon, and the lower end of enriched substance is high-purity more than 99.9 % for purity
Silicon）, valuable metal enriched substance and HIGH-PURITY SILICON are obtained after separation, by step（1）Obtained waste residue carries out the survey of valuable metal content
Fixed, the wherein total content of platinum, palladium and rhodium is 80ppm, and zirconium, cerium, lanthanum, the total content of zinc and nickel are 2.8wt%.Valuable metal content
It is higher, again using the waste residue again as step（1）In pending more metals resources materials carry out second and third time carries
After taking valuable metal, the total content of platinum, palladium and rhodium be less than 5ppm, zirconium, cerium, lanthanum, the total content of zinc and nickel be less than 0.2wt%,
Waste residue can be with waste treatment.
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry
Use silicon material.
Embodiment 4
As shown in figure 1, the selective extraction and the method for being enriched with valuable metal in more metals resources, it is comprised the following steps that：
（1）First by more metalliferous materials（Petro chemical industry carried catalyst, aluminum oxide are carrier, platiniferous 0.35wt%）, add
Add agent（CaO, SiO2And MgO, 75%, 5% and the 6% of failure cleaning catalyst for tail gases of automobiles quality is accounted for respectively）And silicon materials（Ferrosilicon
The mass ratio of alloy, iron content 3%, petro chemical industry carried catalyst and silicon materials is 1:2）It is 1650 DEG C of insulations 1 in temperature
Hour carries out pyrometallurgical smelting extraction valuable metal, obtains silicon-base alloy and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals（It is enriched with using electromagnetism melting technique, region
Melting condition：The condition of magnetic melting is：Heating in medium frequency, heating-up temperature be 1450 DEG C, sample with the speed of 0.1 mm/min to
Lower movement, the top of solid silicon is the enriched substance of platinum after electromagnetism melting, and the lower end of enriched substance is high-purity more than 99.98 % for purity
Silicon）, valuable metal enriched substance and HIGH-PURITY SILICON are obtained after separation, by step（1）The measure of platinum content is carried out in obtained waste residue, is contained
Measure as 145ppm, again using the waste residue again as step（1）In pending more metals resources materials carry out second and extract
After valuable metal, the content of platinum is can be with waste treatment less than 10ppm, waste residue；
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry silicon
Raw material.
Embodiment 5
As shown in figure 1, the selective extraction and the method for being enriched with valuable metal in more metals resources, it is comprised the following steps that：
（1）First by more metalliferous materials（Petro chemical industry carried catalyst, aluminum oxide are carrier, 0.23wt% containing palladium and rhenium
0.13wt%）, additive（CaO, SiO280%, the 5% of failure cleaning catalyst for tail gases of automobiles quality is accounted for respectively）And silicon materials（Work
The mass ratio of industry silicon, purity 98.6%, petro chemical industry carried catalyst and silicon materials is 1:2）It is 1650 DEG C of guarantors in temperature
Temperature carries out pyrometallurgical smelting extraction valuable metal for 5 hours, obtains silicon-base alloy and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals（Monocrystalline silicon growing condition is：Growing method is to carry
Daraf(reciprocal of farad), 13 DEG C/cm of thermograde, crystal growth temperature are 1450 DEG C, and seed crystal is intrinsic<111>, the speed of seed crystal lifting is
1mm/min）, valuable metal enriched substance and HIGH-PURITY SILICON are obtained after separation（More than purity 99.99wt%）, by step（1）What is obtained is useless
The measure of palladium and rhenium content, total content 60ppm, again using the waste residue again as step are carried out in slag（1）In it is pending
More metals resources materials are carried out second after extracting valuable metal, platinum, and the content of palladium and rhenium is that can be given up less than 10ppm, waste residue
Abandon processing；
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry silicon
Raw material.
Above in association with accompanying drawing to the present invention embodiment be explained in detail, but the present invention be not limited to it is above-mentioned
Embodiment, can also be before present inventive concept not be departed from those of ordinary skill in the art's possessed knowledge
Put that various changes can be made.
Claims (6)
1. a kind of selective extraction and the method for being enriched with valuable metal in more metals resources, it is characterised in that comprise the following steps that：
（1）More metalliferous materials, additive and silicon materials are carried out to pyrometallurgical smelting extraction valuable metal together first, obtain silicon substrate conjunction
Gold and waste residue；
（2）By step（1）Obtained silicon-base alloy carries out concentration of valuable metals, and valuable metal enriched substance and high-purity is obtained after separation
Silicon, by step（1）Obtained waste residue carries out the measure of valuable metal content, if valuable tenor height can be used as step again
（1）In pending more metals resources materials carry out second extraction valuable metals, until valuable metal content can as little as discard；
（3）Step（2）Obtained HIGH-PURITY SILICON can return to step（1）As silicon materials, or for electronics or photovoltaic industry silicon
Raw material.
2. selective extraction according to claim 1 and the method for being enriched with valuable metal in more metals resources, its feature exist
In：The step（1）In more metalliferous materials be containing V-Ti blast-furnace slag, titanium containing vanadium waste residue caused by after vanadium extraction titanium, containing your dilute gold
Waste residue of the spent auto-catalysts and petro chemical industry of category with carried catalyst or containing rare precious metal.
3. selective extraction according to claim 1 and the method for being enriched with valuable metal in more metals resources, its feature exist
In：The step（1）Middle additive is CaO, SiO2、Al2O3, one or more of arbitrary proportion mixtures in MgO, total addition
Depending on measuring according to circumstances；But work as in more metalliferous materials and contain CaO, SiO2、Al2O3, two kinds in MgO and it is two or more when, can be with
There is the situation for being added without additive.
4. selective extraction according to claim 1 and the method for being enriched with valuable metal in more metals resources, its feature exist
In：The step（1）Middle silicon materials are silicon or silicon-base alloy, and the mass ratio of silicon materials and more metalliferous materials is according to actual conditions
It is added.
5. selective extraction according to claim 1 and the method for being enriched with valuable metal in more metals resources, its feature exist
In：The step（1）Pyrometallurgical smelting temperature is >=1450 DEG C, soaking time >=1 hour.
6. selective extraction according to claim 1 and the method for being enriched with valuable metal in more metals resources, its feature exist
In：The step（2）Concentration of valuable metals method is electromagnetism melting technique, directional solidification technique, zone refining technology, monocrystalline silicon
Growing technology or wet processing technique.
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