CN110257641A - A method of silica-base material and low Fe eutectic Al-Si alloy are prepared using titanium-contained slag and scrap aluminium alloy - Google Patents
A method of silica-base material and low Fe eutectic Al-Si alloy are prepared using titanium-contained slag and scrap aluminium alloy Download PDFInfo
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- CN110257641A CN110257641A CN201910535953.0A CN201910535953A CN110257641A CN 110257641 A CN110257641 A CN 110257641A CN 201910535953 A CN201910535953 A CN 201910535953A CN 110257641 A CN110257641 A CN 110257641A
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- 239000002893 slag Substances 0.000 title claims abstract description 92
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 50
- 229910021364 Al-Si alloy Inorganic materials 0.000 title claims abstract description 45
- 230000005496 eutectics Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 77
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 76
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000010703 silicon Substances 0.000 claims abstract description 51
- 239000012535 impurity Substances 0.000 claims abstract description 41
- 238000007711 solidification Methods 0.000 claims abstract description 36
- 230000008023 solidification Effects 0.000 claims abstract description 36
- 239000002210 silicon-based material Substances 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910008332 Si-Ti Inorganic materials 0.000 claims abstract description 30
- 229910006749 Si—Ti Inorganic materials 0.000 claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 229910004349 Ti-Al Inorganic materials 0.000 claims abstract description 21
- 229910004692 Ti—Al Inorganic materials 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 238000005272 metallurgy Methods 0.000 claims abstract description 17
- 229910008479 TiSi2 Inorganic materials 0.000 claims abstract description 14
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- 229910009871 Ti5Si3 Inorganic materials 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- 238000003723 Smelting Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910001020 Au alloy Inorganic materials 0.000 claims description 2
- 230000005674 electromagnetic induction Effects 0.000 claims description 2
- 239000003353 gold alloy Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010931 gold Substances 0.000 abstract description 8
- 229910052737 gold Inorganic materials 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 60
- 229910052782 aluminium Inorganic materials 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 26
- 239000004411 aluminium Substances 0.000 description 20
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 229910002796 Si–Al Inorganic materials 0.000 description 6
- 229910000676 Si alloy Inorganic materials 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910000632 Alusil Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- -1 skin material Chemical compound 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- 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
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Abstract
The present invention relates to a kind of methods for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy, belong to solid wastes recycling and technical field of material.By the reduction melting together with low pure silicon material after mixing of titanium-contained slag and additive, Si-Ti alloy and waste residue are obtained after the separation of slag gold；By Si-Ti alloy and scrap aluminium alloy, melting formation Si-Ti-Al intermediate alloy is oriented solidification separation in directional solidification furnace and purification obtains alloy pig；Alloy pig will be obtained by machine cuts separation to cut, and obtain Ti5Si3、TiSi2, super metallurgy grade silicon, low Fe eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.Using the method for the invention, titanium-containing blast furnace slag is prepared into Ti simultaneously using low pure silicon material5Si3、TiSi2, super metallurgy grade silicon, a variety of high value added products such as low Fe eutectic Al-Si alloy, i.e., multiple product is obtained by 1 process route simultaneously.
Description
Technical field
The present invention relates to a kind of sides that silica-base material and low Fe eutectic Al-Si alloy are prepared using titanium-contained slag and scrap aluminium alloy
Method belongs to solid wastes recycling and technical field of material.
Background technique
China's vanadium and titanium resources reserves are about 98.3 hundred million tons, account for the 33% of world's gross reserves.Fe and V warp in vanadium titano-magnetite
Metal is converted into after blast furnace reduction to be utilized, but Ti enters slag in blast furnace reduction process, form Ti and sample low (TiO2Content
About 20%-24%), mine phase composition and complicated titanium-containing blast furnace slag.The titanium-containing blast furnace slag accumulating amount in China is more than 70,000,000
Ton, and with the increase of more than annual 360 ten thousand tons of speed.The bulk deposition of titanium-containing blast furnace slag is not only the serious waste of titanium resource,
Lead to serious environmental problem.In decades, although China to titanium-containing blast furnace slag using having carried out a large amount of research, but still
Titanium-containing blast furnace slag bulk deposition is not solved the problems, such as.Therefore, how the titanium-containing blast furnace slag of clean utilization bulk deposition is still
China's Industrial Solid Waste recycling one of significant problem to be resolved.
On the other hand, aluminium and aluminium alloy are the 2nd big metal materials that yield and dosage are only second to steel in the world.Aluminium is one
Kind resource can be recycled, secondary aluminium refer to the aluminium alloy or metal obtained after refuse refines after recycling aluminium product
Aluminium.Compared with the primary aluminum of production equivalent, produces 1 ton of secondary aluminium and be equivalent to 3.4 tons of standard coals of saving, save 14 cubic meter of water, subtract
20 tons of solid waste are discharged less.China is the maximum aluminium producing country in the whole world.2017, China's primary aluminum yield was 3227.3 ten thousand tons,
Account for the half of global primary aluminum total output.But the explored bauxite exploitation in China can not meet 30 years, there is 30%-50% every year
Aluminium oxide rely on import.On the other hand, China is also the consumption big country of global aluminum product.The year two thousand twenty is expected, China is waste and old
The occurrence quantity of aluminium alloy will surmount the U.S. and occupy the whole world the 1st, will account for the 40% of global total amount to the year two thousand thirty waste aluminium alloy quantity
More than.The problem of bauxite resource scarcity and a large amount of waste aluminium alloys are accumulated seriously limits the high speed hair of China's aluminum alloy materials
Exhibition.Develop secondary aluminium industry, can not only alleviate the increasingly deficient situation of China's alumina resource, also help economy, environment and
The sustainable development of resource.
Currently, metallothermic processes is to handle one of the method for titanium-containing blast furnace slag.Metallothermic processes includes being made using aluminium
Titanium and silicon in titanium-containing blast furnace slag, which are extracted, for reducing agent forms Ti-Si-Al alloy；And it is high as reducing agent extraction titaniferous using silicon
Titanium in clinker forms Si-Ti alloy.But the Ti-Si-Al alloy and Si-Ti alloy how to efficiently use are to be solved
Main problem.The application field of the Ti-Si-Al alloy and Si-Ti alloy that obtain at present is narrow, only can be used as smelting iron and steel
Oxygen scavenger and alloying agents in the process seriously limit the hair of thermit reduction and silicothermic reduction processing titanium-containing blast furnace slag technology
Exhibition.On the other hand, the various problem of dopant species will be faced during scrap aluminium alloy regeneration.Impurity in aluminium alloy is to material
Material performance has different degrees of influence, wherein especially the most obvious with the influence of Fe.Fe can be in aluminium alloy especially Al-Si alloy
It is middle to form acicular, hard but also crisp β-Al not only5FeSi phase, isolates aluminum substrate, the serious plasticity for damaging material, corrosion resistance and resists tired
The performances such as labor.Therefore, the focus that the harm of Fe is current secondary aluminium research how is reduced.Contain Fe although modifying agent is added and changes
The pattern of impurity phase can reduce the harm of Fe impurity, but Fe impurity remains in aluminium alloy, ultimately causes Fe in aluminium alloy
It is constantly accumulated in recycling, following process is created great difficulties.Therefore, the Fe removed to the maximum extent in aluminium alloy is to keep away
Exempt from the most basic method of Fe impurity harm.
The present invention with that application No. is 201811269950.9 patents is " a kind of to prepare titanium silicon and aluminium silicon using titanium-containing blast furnace slag
The method of alloy " the main distinction have: 1. patent 201811269950.9 be using aluminium material as reducing agent reduction titaniferous height
TiO in clinker2And SiO2Ti-Si-Al alloy is formed, but since aluminium not only restores the TiO of titanium-containing blast furnace slag2, also restore titaniferous
The SiO of blast furnace slag2, cause aluminium supplies consumption big；And the present invention first uses silicon materials as the TiO in reducing agent reduction titanium-contained slag2
Ti-Si alloy is formed, then melting forms Ti-Si-Al alloy together with scrap aluminium alloy；Since the silicon materials in the present invention only restore
TiO in titanium-contained slag2, silicon materials consumption is small, and the not waste of aluminium；2. present invention employs scrap aluminium alloy and Si-Ti to close
Gold synthesis Ti-Si-Al alloy, highlights the regeneration of scrap aluminium alloy, and using aluminium in patent 201811269950.9
And aluminium alloy, without reference to scrap aluminium alloy regeneration problem；3. can be again in the mechanical flow diagram of patent 201811269950.9
What is utilized is Al-Si alloy, but recycling in process flow chart of the invention is silicon；4. the present invention is highlighted to scrap aluminium alloy
The removal of Fe impurity acts on, and product obtains the eutectic Al-Si alloy of low Fe, but retouches in patent 201811269950.9 without correlation
It states.Therefore, the present invention is essentially different with patent 201811269950.9.In addition, the present invention with application No. is
201811323583.6 patent " a method of prepare titanium, silicon and titanium silicon using titanium-contained slag " main distinction has: 1. specially
Benefit 201811323583.6 is the Si-Ti alloy obtained using directional solidification technique separation silicothermic reduction titanium-containing blast furnace slag, mainly
It is the clean utilization for titanium-contained slag；And the present invention is the Si-Ti alloy and aluminium scrap for first obtaining silicothermic reduction titanium-containing blast furnace slag
Melting obtains Si-Ti-Al alloy to alloy together, then separates and purify Si-Ti-Al alloy by directional solidification, not only realizes
The utilization of titanium-contained slag also achieves the regeneration of scrap aluminium alloy；2. the present invention separates Si-Ti-Al using directional solidification technique
Alloy, and 201811323583.6 directional solidification technique of patent separates Si-Ti alloy, the alloy species of the two separation are different；③
The regeneration of scrap aluminium alloy can be achieved in the present invention, and does not have the step of scrap aluminium alloy regeneration in patent 201811323583.6
Suddenly；4. the present invention can be achieved to prepare the eutectic Al-Si alloy of low Fe, and patent 201811323583.6 is without associated description.Therefore,
The present invention is essentially different with patent 201811323583.6.
The clean utilization of titanium-containing blast furnace slag and the regeneration of the scrap aluminium alloy research field that be two different, have respective
Different process routes.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of utilization titanium-contained slag and scrap aluminium alloy system
The method of standby silica-base material and low Fe eutectic Al-Si alloy.The present invention can reach through a process route while handle titaniferous
The purpose of blast furnace slag and scrap aluminium alloy.Firstly, extracting the Ti in titanium-contained slag for low pure silicon material as reducing agent, and through slag gold point
The Si-Ti alloy of block is obtained from after；Then, obtained Si-Ti alloy is placed on directional solidification furnace together with scrap aluminium alloy
Middle progress melting obtains Si-Ti-Al alloy, then is separated and purified above-mentioned Si-Ti-Al alloy using directional solidification technique；Orientation
After solidification, Si-Ti-Al alloy is separated into high-temperature structural material Ti5Si3And TiSi2, high-purity super metallurgy grade silicon and low Fe
A variety of high value added products such as eutectic Al-Si alloy.The present invention not only realizes the clean utilization of titanium-containing blast furnace slag, also achieves
Scrap aluminum resources regeneration.
A method of silica-base material and low Fe eutectic Al-Si alloy being prepared using titanium-contained slag and scrap aluminium alloy, it is specific
Step includes:
Step 1, by titanium-contained slag and additive after mixing together with low pure silicon material in the case where reduction temperature is 1723K ~ 1973K
0.5 ~ 10h of reduction melting, low pure silicon material restore the titanium oxide in titanium-contained slag, obtain Si-Ti after the separation of slag gold
Alloy and waste residue；
Step 2, the Si-Ti alloy that step 1 is obtained and the scrap aluminium alloy smelting temperature in directional solidification furnace are 1673K ~ 1973K
Lower melting forms Si-Ti-Al intermediate alloy, and Si-Ti-Al intermediate alloy is oriented solidification separation and purification, is analysed according to crystal
Sequence out, obtains Ti5Si3、TiSi2, super metallurgy grade silicon, low Fe eutectic Al-Si alloy high value added product alloy pig,
In will form the impurity layer of the major impurity containing Fe and Mn before forming low Fe eutectic Al-Si alloy；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains Ti5Si3、TiSi2, super metallurgy grade
Silicon, low Fe eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
Titanium-contained slag is the slag containing titanium oxide, including titanium-containing blast furnace slag or titanium oxide and oxidation in the step 1
The slag that object is formed.
Additive is CaO, MgO, SiO in the step 12、Al2O3One or more of mixture, additive capacity and mixed
Complex ratios can also be added without additive depending on the composition of titanium-contained slag.
Low pure silicon material is low pure industrial silicon, scrap silicon and silicon-base alloy in the step 1, and wherein scrap silicon includes losing
Imitate the useless silicon material of silicon chip of solar cell, edge skin material or Buddha's warrior attendant wire cutting.
Directional solidification furnace includes the directional solidification of the directional solidification furnace of resistance heating, electromagnetic induction heating in the step 2
Furnace or zone refining furnace.
Displacement speed is more than or equal to 10 μm/min in directional solidification in the step 2.
The beneficial effects of the present invention are:
(1) the method for the invention is used, titanium-containing blast furnace slag is prepared into Ti simultaneously using low pure silicon material5Si3、TiSi2、
A variety of high value added products such as high-purity super metallurgy grade silicon, low Fe eutectic Al-Si alloy are obtained more simultaneously by 1 process route
Kind product.
(2) method of the invention can handle a variety of solid waste resources such as scrap aluminium alloy, titanium-containing blast furnace slag and scrap silicon simultaneously.
(3) present invention is a kind of no exhaust gas and spent acid generation, non-carbon-emitting, low cost, environmental-friendly and efficient skill
Art.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Figure 1, the method for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy,
Specific steps include:
Step 1, by titanium-contained slag (slag containing titanium oxide, TiO2Content is 21wt%) and additive (CaO, Al2O3And MgO,
Additive additive amount is respectively 10%, the 6% of titanium-contained slag and 5%) (low pure silicon material is low pure with low pure silicon material after mixing
Industrial silicon, purity 98wt%, low pure silicon quality of material is the 80% of titanium-contained slag) reduction melting in the case where reduction temperature is 1723K together
10h, low pure silicon material restore the titanium oxide in titanium-contained slag, obtain Si-Ti alloy and waste residue after the separation of slag gold；
(Al is 90.1 wt%, and the content of impurity F e, Mn and Si are for step 2, the Si-Ti alloy that step 1 is obtained and scrap aluminium alloy
Respectively 1.5 wt%, 0.3 wt%, 5.4 wt%；Si-Ti alloy and aluminium scrap silicon alloy mass ratio are 3:1) in directional solidification furnace
Smelting temperature is that for 0.5 H-shaped of melting at Si-Ti-Al intermediate alloy, Si-Ti-Al intermediate alloy is oriented solidification point under 1673K
From (displacement speed is 10 μm/min) in directional solidification, according to the sequence that crystal is precipitated, obtains TiSi with purification2, super smelting
The conjunction of golden grade silicon (silicon purity is 99.96 wt%), low Fe eutectic Al-Si alloy (amount containing Fe is 0.65wt%) high value added product
Ingot, wherein will form the impurity layer of the major impurity containing Fe and Mn before forming low Fe eutectic Al-Si alloy；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains TiSi2, super metallurgy grade silicon, low Fe
Eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
Above-mentioned super metallurgy grade silicon can be used as silicon materials and recirculate use, or solar-electricity is prepared after further purifying
Pond silicon wafer.
Embodiment 2
As shown in Figure 1, the method for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy,
Specific steps include:
Step 1, by titanium-contained slag (slag containing titanium oxide, TiO2Content is 35wt%) and additive (CaO and SiO2, addition
Agent additive amount is respectively the 8% of titanium-contained slag and 5%) (low pure silicon material is failure solar-electricity with low pure silicon material after mixing
Pond silicon wafer, low pure silicon quality of material are the 70% of titanium-contained slag) reduction melting 0.5h, low pure silicon in the case where reduction temperature is 1973K together
Material restores the titanium oxide in titanium-contained slag, obtains Si-Ti alloy and waste residue after the separation of slag gold；
(Al is 97.1 wt%, and the content of impurity F e, Mn and Si are for step 2, the Si-Ti alloy that step 1 is obtained and scrap aluminium alloy
Respectively 1.2wt%, 0.2 wt%, 0.6 wt%；Si-Ti alloy and aluminium scrap silicon alloy mass ratio are 4:1) in directional solidification furnace
Smelting temperature is that for 1.5 H-shaped of melting at Si-Ti-Al intermediate alloy, Si-Ti-Al intermediate alloy is oriented solidification point under 1973K
From (displacement speed is 15 μm/min) in directional solidification, according to the sequence that crystal is precipitated, obtains TiSi with purification2, super smelting
The conjunction of golden grade silicon (silicon purity is 99.95 wt%), low Fe eutectic Al-Si alloy (amount containing Fe is 0.68wt%) high value added product
Ingot, wherein will form the impurity layer of the major impurity containing Fe and Mn before forming low Fe eutectic Al-Si alloy；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains TiSi2, super metallurgy grade silicon, low Fe
Eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
Above-mentioned super metallurgy grade silicon can be used as silicon materials and recirculate use, or solar-electricity is prepared after further purifying
Pond silicon wafer.
Embodiment 3
As shown in Figure 1, the method for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy,
Specific steps include:
Step 1, by titanium-contained slag, (slag that titanium oxide and oxide are formed, contains TiO2For the TiO of 90wt%2The out of stock catalyst of base
With CaO, SiO2And Al2O3It is mixed to form titanium-containing oxide slag, wherein TiO2Content is 30wt%, CaO content 30wt%, SiO2Contain
Amount is 25wt% and Al2O3Content is 15wt%), additive (CaO, additive additive amount are respectively the 5% of titanium-contained slag) and low pure silicon
Material (low pure silicon material is the useless silicon material of Buddha's warrior attendant wire cutting, and low pure silicon quality of material is the 30% of titanium-contained slag) after mixing, is being gone back
Former temperature is reduction melting 5h under 1823K, and low pure silicon material restores the titanium oxide in titanium-contained slag, after the separation of slag gold
Obtain Si-Ti alloy and waste residue；
(Al is 86.2 wt%, and the content of impurity F e, Mn and Si are for step 2, the Si-Ti alloy that step 1 is obtained and scrap aluminium alloy
Respectively 1.4 wt%, 0.4 wt%, 8.2 wt%；Si-Ti alloy and aluminium scrap silicon alloy mass ratio are 2:1) in directional solidification furnace
Smelting temperature is that for 2 H-shaped of melting at Si-Ti-Al intermediate alloy, Si-Ti-Al intermediate alloy is oriented solidification separation under 1673K
With purification (displacement speed is 15 μm/min in directional solidification), according to the sequence that crystal is precipitated, Ti is obtained5Si3, low Fe it is total
The alloy pig of brilliant Al-Si alloy (amount containing Fe is 0.66wt%) high value added product, wherein forming low Fe eutectic Al-Si alloy
It will form the impurity layer of the major impurity containing Fe and Mn before；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains Ti5Si3, low Fe eutectic Al-Si
Alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
Embodiment 4
As shown in Figure 1, the method for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy,
Specific steps include:
Step 1, by titanium-contained slag (by titanium-containing blast furnace slag, TiO2Content is 21wt%), additive (additive 0) and low pure silicon object
Expect (low pure silicon material is silicon edge skin material, and purity 99.9wt%, low pure silicon quality of material is the 60% of titanium-contained slag) after mixing,
Reduction temperature is reduction melting 10h under 1823K, and low pure silicon material restores the titanium oxide in titanium-contained slag, through slag gold point
Si-Ti alloy and waste residue are obtained from after；
Step 2, by Si-Ti alloy and scrap aluminium alloy that step 1 obtains, (content of Al 93.1wt%, impurity F e, Mn and Si is
Respectively 1.2wt%, 0.2 wt%, 3.5 wt%；Si-Ti alloy and aluminium scrap silicon alloy mass ratio are 3.5:1) in directional solidification furnace
Middle smelting temperature is oriented solidification at Si-Ti-Al intermediate alloy, Si-Ti-Al intermediate alloy for 0.5 H-shaped of melting under 1723K
Separation and purification (displacement speed is 15 μm/min in directional solidification), according to the sequence that crystal is precipitated, obtain TiSi2, it is super
Metallurgical grade silicon (silicon purity is 99.94 wt%), low Fe eutectic Al-Si alloy (amount containing Fe is 0.62wt%) high value added product
Alloy pig, wherein will form the impurity layer of the major impurity containing Fe and Mn before forming low Fe eutectic Al-Si alloy；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains TiSi2, super metallurgy grade silicon, low Fe
Eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
Above-mentioned super metallurgy grade silicon can be used as silicon materials and recirculate use, or solar-electricity is prepared after further purifying
Pond silicon wafer.
Embodiment 5
As shown in Figure 1, the method for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy,
Specific steps include:
Step 1, by titanium-contained slag (by titanium-containing blast furnace slag, TiO2Content is 21wt%), additive (additive 0) and low pure silicon object
Expect (low pure silicon material is alusil alloy, is 5wt% containing Al, and low pure silicon quality of material is the 70% of titanium-contained slag) after mixing,
Reduction temperature is reduction melting 6h under 1823K, and the titanium oxide in titanium-contained slag is restored, separated through slag gold by low pure silicon material
After obtain Si-Ti alloy and waste residue；
(content of Al 85wt%, impurity F e, Mn and Si are point for step 2, the Si-Ti alloy that step 1 is obtained and scrap aluminium alloy
It Wei not 1.8wt%, 0.3 wt%, 10 wt%；Si-Ti alloy and aluminium scrap silicon alloy mass ratio are 3.5:1) it is melted in directional solidification furnace
Refine temperature be 1723K under 1 H-shaped of melting at Si-Ti-Al intermediate alloy, Si-Ti-Al intermediate alloy be oriented solidification separation and
Purification (displacement speed is 10 μm/min in directional solidification), according to the sequence that crystal is precipitated, obtains TiSi2, super metallurgy grade
The alloy pig of silicon (silicon purity is 99.95wt%), low Fe eutectic Al-Si alloy (amount containing Fe is 0.68wt%) high value added product,
It wherein will form the impurity layer of the major impurity containing Fe and Mn before forming low Fe eutectic Al-Si alloy；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains TiSi2, super metallurgy grade silicon, low Fe
Eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
Above-mentioned super metallurgy grade silicon can be used as silicon materials and recirculate use, or solar-electricity is prepared after further purifying
Pond silicon wafer.
In conjunction with attached drawing, the embodiment of the present invention is explained in detail above, 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 (6)
1. a kind of method for preparing silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy, feature exist
Include: in specific steps
Step 1, by titanium-contained slag and additive after mixing together with low pure silicon material in the case where reduction temperature is 1723K ~ 1973K
0.5 ~ 10h of reduction melting, low pure silicon material restore the titanium oxide in titanium-contained slag, obtain Si-Ti after the separation of slag gold
Alloy and waste residue；
Step 2, the Si-Ti alloy that step 1 is obtained and the scrap aluminium alloy smelting temperature in directional solidification furnace are 1673K ~ 1973K
Lower melting forms Si-Ti-Al intermediate alloy, and Si-Ti-Al intermediate alloy is oriented solidification separation and purification, is analysed according to crystal
Sequence out, obtains Ti5Si3、TiSi2, super metallurgy grade silicon, low Fe eutectic Al-Si alloy high value added product alloy pig,
In will form the impurity layer of the major impurity containing Fe and Mn before forming low Fe eutectic Al-Si alloy；
Step 2 is obtained alloy pig and is cut by step 3 by machine cuts separation, obtains Ti5Si3、TiSi2, super metallurgy grade
Silicon, low Fe eutectic Al-Si alloy, and machine cuts remove impurity layer, achieve the purpose that remove the major impurities such as Fe and Mn.
2. according to claim 1 prepare silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy
Method, it is characterised in that: titanium-contained slag is the slag containing titanium oxide, including titanium-containing blast furnace slag or titanyl in the step 1
The slag that compound and oxide are formed.
3. according to claim 1 prepare silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy
Method, it is characterised in that: in the step 1 additive be CaO, MgO, SiO2、Al2O3One or more of mixture, add
Add dosage and mixture ratio depending on the composition of titanium-contained slag.
4. according to claim 1 prepare silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy
Method, it is characterised in that: low pure silicon material is low pure industrial silicon, scrap silicon and silicon-base alloy, wherein silicon in the step 1
Waste material includes failure silicon chip of solar cell, edge skin material or the useless silicon material of Buddha's warrior attendant wire cutting.
5. according to claim 1 prepare silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy
Method, it is characterised in that: directional solidification furnace includes the directional solidification furnace of resistance heating, electromagnetic induction heating in the step 2
Directional solidification furnace or zone refining furnace.
6. according to claim 1 prepare silica-base material and low Fe eutectic Al-Si alloy using titanium-contained slag and scrap aluminium alloy
Method, it is characterised in that: in the step 2 in directional solidification displacement speed be more than or equal to 10 μm/min.
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| CN111348653A (en) * | 2020-03-16 | 2020-06-30 | 昆明理工大学 | Method for preparing high-purity silicon, titanium white and high-purity fluoride by using titanium-containing slag and low-purity silicon material |
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Application publication date: 20190920 |