CN1332045C - Hydrothermal method for recovering metal from waste hard alloy - Google Patents
Hydrothermal method for recovering metal from waste hard alloy Download PDFInfo
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- CN1332045C CN1332045C CNB2006100205399A CN200610020539A CN1332045C CN 1332045 C CN1332045 C CN 1332045C CN B2006100205399 A CNB2006100205399 A CN B2006100205399A CN 200610020539 A CN200610020539 A CN 200610020539A CN 1332045 C CN1332045 C CN 1332045C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002699 waste material Substances 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 61
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 41
- 239000010941 cobalt Substances 0.000 claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910009043 WC-Co Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 12
- 229910001080 W alloy Inorganic materials 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 238000005243 fluidization Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- -1 cobalt metals Chemical class 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 229910002441 CoNi Inorganic materials 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000012634 fragment Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910008947 W—Co Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 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
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention provides a novel method for recovering cobalt and other metallic elements from waste hard alloy, namely a hydro-thermal method which comprises: broken waste hard alloy is soaked in HNO3 and then is treated in an autoclave, and cobalt and other elements are separated out by nitrate solution; WC, etc. are oxidized to WO3 powder, and then, the WO3 powder is converted into WC-Co, etc. through the thermal chemical reaction technology of a fluidized bed. The method of the present invention has the advantages of short process, simple technical equipment, low energy consumption, high efficiency, no pollution and easy expansion of mass production and is suitable for recovering WC-Ni, WC-NiFe, WC-TiC-Co, WC-Mo2C-Co, WC-(Nb. Ta)C-Co, WC-VC-Co, WC-Cr3C2-Co, WC-TiC-CoNi and other hard alloy.
Description
Technical field
The present invention relates to reclaim in a kind of WC-Co alloy the method for Co, W, belong to field of inorganic chemical engineering.
Background technology
The WC-Co alloy is the material of WC by the Co connection, is widely used as cutting tool, mould etc. in industrial circles such as space flight, automobile, electronics.China's annual output reaches 1.5 ten thousand tons, and wherein cobalt is the 900-3750 ton, but its waste and old product recovery utilization rate is extremely low, and the U.S. is more than 60%, and Japan is 20%.Co is strategic materials, is poor source in China, so its recycling is very important.Traditional recovery method has three kinds, i.e. high temperature expansion crush method, zinc alloy method and HCl or FeCO
3The leaching method.The former at first is heated to 1800-2300 ℃ of high temperature with the WC-Co fragment in indifferent gas gas, quenches then to make alloy pulverization because of Co expands, and further behind the ball milling and reclaim and obtain WC-Co.But this method energy consumption is big, cost is high, and form in removal process not only that some do not wish to occur as W
2C, free C and η be (W mutually
3nCo
3nC
nOr W
6nCo
6nC
n).The zinc alloy method is that the WC-Co fragment at first is immersed in 950 ℃ the fusing zinc water, zinc and cobalt generation eutectic reaction form low melting point Zn-Zo alloy and make the efflorescence of WC-Co fragment, make the zinc evaporation 1000-1050 ℃ of vacuum distilling then, and reclaim the spongy WC-Co that easily pulverizes.This method energy consumption is still very high, and reclaims impure inevitably Zn in the product.The third recovery method is with HCl, FeCO
3, HCl+FeCO
3For leaching the hydro-thermal extraction process of solvent, though this method energy consumption is low, this method is difficult to recycle the WC-Co content of fine particle WC and low Co content.Cl
-Ion tool severe corrosive, and bring impurities such as Fe impurity.
Summary of the invention
The objective of the invention is to overcome above Technology shortcoming, the flow process to simplify under the less energy-consumption condition makes various trade mark WC-Co alloys all can be recovered as powder such as high-purity Nano-class WC-Co or WC, W, Co.
The method that reclaims Co, W in the WC-Co alloy provided by the invention ties up in the autoclave, and waste and old WC-Co alloy forms Co salt and WO through the hydrothermal oxidization reaction
30.33H
2O and being recovered also can further be converted to WC-Co or Co, W, WC.
Wherein said hydrothermal oxidization method is with HNO
3Be extraction and oxidation solvent.Owing to react under High Temperature High Pressure, speed of reaction is fast, and is easy to make the alloy reaction process to tend to be balanced, and through at a certain temperature, behind the reaction certain hour, Co forms Co salt Co (NO among the WC-Co
3)
2, WC is converted into WO
30.33H
2O.
Co salt and WO
30.33H
2O can make it directly to be recovered as WC-Co or WC, W, Co through " closed loop level Four fluidization process ", " closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process ".Reclaim after product tool nano-scale particle size powder, be not with any metallic impurity, chlorion, with the goods that make of weight sintering, keep even surpassed the mechanics and the physicals level of former powder-product.
Specifically, the method that reclaims Co, W in the WC-Co alloy provided by the invention may further comprise the steps:
A, waste and old cobalt, tungstenalloy are particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO
3Be solvent soaking; Wherein the grain fineness number of WC is approximately 0.5-5 μ m, and Co content is 6-25
Wt%;
B, in the autoclave of band magnetic stirring apparatus, titanium alloy lining 100-200 ℃ of constant temperature, handled 10-48 hour under the rotating speed 100-200rpm condition, W is converted into WO among the WC-Co
30.33H
2O, Co is converted into Xiao Suangu;
C, separation solid, liquid phase; Liquid phase is a cobalt salt solution, and solid phase is WO
30.33H
2O.
With WO
30.33H
2The O solid phase is diluted to the 20-30% solids solution with deionized water, and 8000-30000rpm high speed shear emulsification instrument was sheared 30 minutes.With inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, supersonic spraying drying, decomposition and inversion are WO
3Carry out thermal chemical reaction through fluidized-bed and obtain nanometer W or WC;
With inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is CoO that supersonic spraying makes solution drying, decomposition and inversion with cobalt nitrate solution; Carry out thermal chemical reaction through fluidized-bed and obtain nano Co.
Also not separated solid, liquid mixture can be sheared 30 minutes with 8000-30000rpm high speed shear emulsification instrument, make the further dispersing and disintegrating of solid phase in the solution, with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is WO that supersonic spraying makes the dry decomposition and inversion of mixed solution
3-CoO; Obtain the nano WC-Co powder through the fluid bed heat chemical reaction.
Described fluid bed heat chemical reaction is a kind of in " closed loop level Four fluidization process ", " the closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process ".
In the aforesaid method, as the described waste and old cobalt of a step, tungstenalloy WC grain degree 1-5 μ m, Co content 10-23
Wt%, then HNO
3Concentration 2-3M; 130-150 ℃ of b step process temperature, time 4-24 hour.
As the described waste and old cobalt of a step, tungstenalloy WC grain degree 0.5-1 μ m, Co content 10-13
WtBelow the %, HNO then
3Concentration 3-11M; 150-200 ℃ of b step process temperature, time 24-40 hour.
The c step is separated employing membrane separation process, membrane pore size 0.08-0.6 μ m.
Above-mentioned recovery technology in like manner is applicable to the recycling of alloys such as WC-CoNi, WC-CoNiFe, WC-TiC-CoNi.Only different is that liquid phase is the nitrate solution of cobalt, nickel or cobalt, nickel, iron or cobalt, nickel, and solid phase is WO
30.33H
2O or WO
3-TiO
2Deng.Recovery method may further comprise the steps:
The alloy of the carbide of a, waste and old cobalt and/or nickel and/or iron and IVB, VB or group vib element is particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO
3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, the carbide of IVB, VB or group vib element is converted into oxide compound in the alloy, and cobalt, nickel or iron are converted into nitrate: such as, WC is converted into WO in the alloy
30.33H
2O, or WC-TiC is converted into WO
3-TiO
2Cobalt, nickel or iron are converted into nitrate;
C, separation solid, liquid phase; Liquid phase is cobalt, nickel or iron nitrate solution, and solid phase is the oxide compound of IVB, VB or group vib element, as WO
30.33H
2O or WO
3-TiO
2
Advantage of the present invention:
1, temperature of reaction is low, energy consumption is low.
2, flow process is brief, the rate of recovery is high, product purity is high.
3, equipment is simple, cost is low, be easy to enlarge batch process.
Below by embodiment, the present invention being further described, is limitation of the present invention but should not be construed as.Below be specific embodiment, those of ordinary skills can also make modification, replacement, the change of various ways according to technique scheme.All modification, replacement, changes of doing based on above-mentioned technological thought all belong to scope of the present invention.
Embodiment 1:
Getting wc grain size is 1-5 μ m, and Co content is the WC-Co fragment 0.23-0.24Mol of 20% massfraction, adds 3M HNO
330ml moves in the autoclave of titanium alloy lining, handles to make in 24 hours reacting completely 150 ℃ of rotating speed 120rpm magnetic agitation.The WO30.33H2O that obtains after the membrane sepn washing wherein contains the W75.2% massfraction with the EDS analysis, contain oxygen 24.5% massfraction, and Co is a trace, only less than 0.3% massfraction.The filtrate that obtains is analyzed with ICP-AES, and Co content is 98.5% massfraction of Co content in the former state (WC-Co fragment), and only several ppm of W content.
Embodiment 2:
Getting wc grain size is 0.5-1 μ m, and Co content is the WC-Co alloy fragment 0.23-0.24Mol of 13% massfraction, adds 30ml 7M HNO
3Move into autoclave and handled 24 hours at 160 ℃, the solid WO30.33H2O that obtains confirms that with XRD analysis solids is entirely WO
3Spectral line, when when 200 ℃ are handled, CoWO is arranged in the solid
4Phase.Analyzing Co with EDS, ICP-AES is trace.W is a trace in the analysis gained solution, and the Co rate of recovery is 98.5%.
Embodiment 3:
Getting wc grain size is 0.5 μ m, and Co content is the WC-Co fragment 0.23-0.24Mol of 6% massfraction, adds 30ml 9M HNO
3After, move into autoclave and handled 28 hours at 170 ℃.Through XRD, ICP-AES instrumental analysis, prove that respectively the WC complete oxidation is WO
3Wherein only there is trace Co; And only containing several ppmW in the Co salts solution that obtains, 96.5% above Co is extracted in the raw material.
Embodiment 4:
Getting wc grain size is 0.5-1 μ m, and Co content is the WC-Co alloy fragment 30Mol of 13% massfraction, adds liter 7M HNO
3, moving into titanium lined alloy volume is the autoclave of 5 liters, and 150 ℃ through temperature reaction 24 hours, and the gained reaction product is through sampling analysis, WO
3Middle Co is a trace, and W is a trace in the cobalt nitrate solution.Confirmatory reaction fully after, in mixture solution, add 1: 1 ethanolic soln, be diluted to that solid content is 40 in the solution
Wt% sheared 30 minutes with 8000-3000rpm high speed shear emulsification instrument, and ullrasonic spraying drying then is at last by carrying out thermal chemical reaction one of in patent " closed loop level Four rotary fluid method ", " the closed loop level Four fluidized bed process " or " closed loop level Four displacement fluidization process ".Promptly in first reactor 350-450 ℃, N
2/ 10%H
2In carried out the first step low-temperature reduction one hour, generate WO
2.9-CoO; In the reactor of the second stage 500-600 ℃, N
2/ 10%H
2In carry out the second step reduction reaction 1.5 hours, generate W-Co; The CO/CO of carbon activity in third stage reactor＞1
2In the atmosphere, 800-850 ℃ was carried out carburizing reagent 2 hours; Activity is 0.4 CO in fourth stage reactor
2In/CO the atmosphere, 700-750 ℃ is gone uncombined carbon reaction 1 hour.Product WC-Co powder granularity＜0.2 μ m, no η phase, nothing trip carbon.
Embodiment 5
Get the WC-6%Co-20%Ni that the WC grain degree is 1-5 μ m (Wt%) alloy particle (φ 1-3mm) 0.23-0.24Mol and be dissolved in 3M HNO
3Behind the 30ml, move in the autoclave of band magnetic agitation, titanium alloy lining 150 ℃ of reactions 24 hours, WO
30.33H
2O analyzes tungstenic 73.2% massfraction through EDS, and Co is a trace, and Ni content is less than 0.15%; Cobalt, nickel total amount are 97.8% of former content in the nitrate solution, and tungsten is trace.
Embodiment 6
Get the WC-6%Co-16%Ni-4%Fe that the WC grain degree is 1-5 μ m (Wt%) alloy particle (φ 1-3mm) 0.23-0.24Mol and be dissolved in 3M HNO
3Among the 30ml, move in the titanium lining autoclave of band magnetic stirring apparatus, 150 ℃ were reacted 26 hours, got WO
30.33H
2O, analyzing tungsten recovery rate through EDS is 97.8%, cobalt, nickel, iron total content＜0.3% massfraction; Cobalt, nickel, iron total amount are 96.7% of former content in the nitrate solution, and tungsten is trace.
Embodiment 7
Get the WC-15%TiC-6%Co-20% that the WC grain degree is 1-5 μ m (Wt%) Ni alloy particle (φ 1-3mm) 0.23-0.24Mol and be dissolved in 3M HNO
3Among the 30ml, move in the titanium lining autoclave of band magnetic stirring apparatus,, get WO 150 ℃ of magnetic agitation reactions 24 hours
3-TiO
2, analyze WO through X ray fluorescent spectrometer
379.6% massfraction, TiO
220.20% massfraction, cobalt, nickel trace; Cobalt, nickel total content are 98% massfraction of its former total content in the nitrate solution, and tungsten is trace.
In a word, the novel method flow process that reclaims metallic elements such as cobalt from hard alloy scraps provided by the invention is short, processing unit is simple, energy consumption is low, efficient is high, pollution-free, easy expansion is produced in batches, and is suitable for WC-Ni, WC-NiFe, WC-TiC-Co, WC-Mo
2C-Co, WC-(Nb.Ta) C-Co, WC-VC-Co, WC-Cr
3C
2Wimet such as-Co, WC-TiC-CoNi reclaims, and the alloy purity height of recovery is not with any metallic impurity, chlorion etc.
Claims (13)
1, a kind of method that reclaims metal from scrap hard alloy may further comprise the steps:
The surplus or excess alloy of the carbide of a, IVB, VB or group vib element and cobalt and/or nickel and/or ferrous metal is particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO
3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, the carbide of IVB, VB or group vib element is converted into oxide compound in the alloy, and cobalt, nickel or iron are converted into nitrate;
C, separation solid, liquid phase; Liquid phase is cobalt, nickel or iron nitrate solution, and solid phase is the oxide compound of IVB, VB or group vib element;
Wherein said IVB, VB or group vib element are tungsten, molybdenum, chromium, vanadium, niobium, tantalum, titanium, zirconium or hafnium.
2, the method that from scrap hard alloy, reclaims metal according to claim 1, it is characterized in that: described surplus or excess alloy is that waste and old cobalt, tungstenalloy may further comprise the steps:
A, waste and old cobalt, tungstenalloy are particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO
3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, W is converted into WO among the WC-Co
30.33H
2O, Co is converted into Xiao Suangu;
C, separation solid, liquid phase; Liquid phase is a cobalt salt solution, and solid phase is WO
30.33H
2O.
3, the method for recovery cobalt metal according to claim 2, tungsten is characterized in that:
The WO that the c step is obtained
30.33H
2The O solid phase is diluted to the 20-30% solids solution with deionized water, and 8000-30000rpm high speed shear emulsification instrument was sheared 30 minutes, and with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, supersonic spraying drying, decomposition and inversion are WO
3Carry out thermal chemical reaction through fluidized-bed and obtain nanometer W or WC;
With inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is CoO that supersonic spraying makes solution drying, decomposition and inversion with cobalt nitrate solution; Carry out thermal chemical reaction through fluidized-bed and obtain nano Co.
4, the method for recovery cobalt metal according to claim 3, tungsten is characterized in that: described fluid bed heat chemical reaction is a kind of in " closed loop level Four fluidization process ", " the closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process ".
5, according to the method for each described recovery cobalt metal of claim 2-4, tungsten, it is characterized in that: the described waste and old cobalt of a step, tungstenalloy WC grain degree 1-5 μ m, Co content 10-23
Wt%, then HNO
3Concentration 2-3M; 130-150 ℃ of b step process temperature, time 4-24 hour.
6, the method for recovery cobalt metal according to claim 5, tungsten is characterized in that: the c step is separated employing membrane separation process, membrane pore size 0.08-0.6 μ m.
7, according to the method for each described recovery cobalt metal of claim 2-4, tungsten, it is characterized in that: the described waste and old cobalt of a step, tungstenalloy WC grain degree 0.5-1 μ m, Co content 10-13
WtBelow the %, HNO then
3Concentration 3-11M; 150-200 ℃ of b step process temperature, time 24-40 hour.
8, the method for recovery cobalt metal according to claim 7, tungsten is characterized in that: the c step is separated employing membrane separation process, membrane pore size 0.08-0.6 μ m.
9, according to the method for each described recovery cobalt metal of claim 2-4, tungsten, it is characterized in that: the c step is separated employing membrane separation process, membrane pore size 0.08-0.6 μ m.
10, a kind of method that reclaims the method for cobalt metal, tungsten from scrap hard alloy is characterized in that:
A, waste and old cobalt, tungstenalloy are particle diameter 1-3mm through mechanical fragmentation, with concentration 2-11M HNO
3Be solvent soaking;
B, handled 10-48 hour under 100-200 ℃ of constant temperature in the autoclave of band magnetic stirring apparatus, titanium alloy lining, W is converted into WO among the WC-Co
30.33H
2O, Co is converted into Xiao Suangu;
C, not separated solid, liquid mixture was sheared 30 minutes with 8000-30000rpm high speed shear emulsification instrument, make the further dispersing and disintegrating of solid phase in the solution, with inlet temperature 230-250 ℃, temperature out 110-120 ℃ condition, it is WO that supersonic spraying makes the dry decomposition and inversion of mixed solution
3-CoO; Obtain the nano WC-Co powder through the fluid bed heat chemical reaction.
11, the method for recovery cobalt metal according to claim 10, tungsten is characterized in that: described fluid bed heat chemical reaction is a kind of in " closed loop level Four fluidization process ", " the closed loop level Four rotary fluid method " or " closed loop level Four displacement fluidization process ".
12, according to the method for claim 10 or 11 described recovery cobalt metals, tungsten, it is characterized in that: the described waste and old cobalt of a step, tungstenalloy WC grain degree 1-5 μ m, Co content 10-23
Wt%, then HNO
3Concentration 2-3M; 130-150 ℃ of b step process temperature, time 4-24 hour.
13, according to the method for claim 10 or 11 described recovery cobalt metals, tungsten, it is characterized in that: the described waste and old cobalt of a step, tungstenalloy WC grain degree 0.5-1 μ m, Co content 10-13
WtBelow the %, HNO then
3Concentration 3-11M; 150-200 ℃ of b step process temperature, time 24-40 hour.
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| 从钴废料回收钴产品 潘泽强，中南大学硕士学位论文 2004 * |
| 从钴废料回收钴产品 潘泽强，中南大学硕士学位论文 2004;废弃物料中钴、镍的回收 唐娜娜，马少键，有色矿冶，第21卷增刊 2005 * |
| 废弃物料中钴、镍的回收 唐娜娜，马少键，有色矿冶，第21卷增刊 2005 * |
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