CN1312300C - Method for recovering valuable metal from waste containing V, Mo and Ni - Google Patents
Method for recovering valuable metal from waste containing V, Mo and Ni Download PDFInfo
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- CN1312300C CN1312300C CNB2003801052925A CN200380105292A CN1312300C CN 1312300 C CN1312300 C CN 1312300C CN B2003801052925 A CNB2003801052925 A CN B2003801052925A CN 200380105292 A CN200380105292 A CN 200380105292A CN 1312300 C CN1312300 C CN 1312300C
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- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 63
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title abstract description 27
- 239000002184 metal Substances 0.000 title abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 64
- 239000000956 alloy Substances 0.000 claims abstract description 64
- 239000002893 slag Substances 0.000 claims abstract description 60
- 229910017318 Mo—Ni Inorganic materials 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- 230000002829 reductive effect Effects 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000006722 reduction reaction Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000010970 precious metal Substances 0.000 claims description 17
- 230000004927 fusion Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000003287 bathing Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 48
- 239000000203 mixture Substances 0.000 description 44
- 239000002994 raw material Substances 0.000 description 33
- 238000006477 desulfuration reaction Methods 0.000 description 19
- 230000023556 desulfurization Effects 0.000 description 19
- 238000011084 recovery Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000009847 ladle furnace Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 229910000952 Be alloy Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000272165 Charadriidae Species 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- VAWNDNOTGRTLLU-UHFFFAOYSA-N iron molybdenum nickel Chemical compound [Fe].[Ni].[Mo] VAWNDNOTGRTLLU-UHFFFAOYSA-N 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for recovering a valuable metal from a waste containing V, Mo and Ni, which comprises a step of drying the waste containing V, Mo and Ni, a step of charging the dried waste containing V, Mo and Ni, Fe as a reducing agent, and a flux into a heating furnace and heating and reducing them, to thereby form a V-containing slag and an Fe-Mo-Ni based alloy, and a step of adding Al as an reducing agent to the V-containing slag and reacting them, to thereby form an Fe-V based alloy and a CaO-Al2O3 slag. The method ca be used for recovering an Fe-Mo-Ni based alloy and an Fe-V based alloy from a waste containing V, Mo and Ni, with stability in good yield.
Description
Technical field
The present invention relates to from used desulfurization catalyst, Boiler Ash, boiler mud, nickel class mud, ammonium meta-vanadate the like waste, reclaim the method for precious metals.
Background technology
Be in the boiler of fuel with the oil fuel as the power house, heavy metal Ni, V are condensing in the Boiler Ash that the boiler mud, the dust removal installation that are deposited on boiler bottom are captured with the form of oxide compound.Heavy metal V is also condensing in the ammonium meta-vanadate that Boiler Ash is carried out obtaining after the wet type alkaline purification with the form of oxide compound.
In fields such as petroleum refinement, gas processing industry, be provided with desulfurization catalyst in the treating process.Heavy metal Ni, Mo, V also can be condensing in these used desulfurization catalysts with the form of oxide compound.As waste effectively utilize mode, expectation can be reclaimed the oxide compound of these Ni, Mo, V with metal form.
One of this recovery technology, its method (refers to Patent Document 1, claim 1) be: the waste that will contain V is 450～950 ℃ of heating down, remove the S composition in the waste, after N composition and the C composition, this waste and source of iron and reductive agent mixed together, the pulverizing postforming is a particulate state, then, 1150～1350 ℃ of heating down, Fe composition in the raw material, the Ni composition, the Mo composition by solid phase reduction after, be encased in and heat in the electric furnace to generate Fe, Ni, Mo is the metal of main component and the fused solution of rich V, to this with Fe, Ni, Mo is that the metal of main component takes off the P processing, obtain low P alloy, on the other hand, in container, reducing material is joined in the fused solution of rich V, stir simultaneously with strong mixing function, thereby the V in the reducing and smelting liquid, obtaining Fe-V is alloy.
As other recovery technology, its method is disclosed (refer to Patent Document 2, claim 1).This method has: roasting contains the 1st procedure of the waste of V, Mo, Co and Ni; Being equivalent to Mo, Ni and Co oxide compound are reduced to the metal Si and/or the metal A l of metal necessary stoichiometric 50～120% by interpolation, melting after adding thermal reduction, is that alloy or Mo-Co are that alloy or Mo-Ni-Co are alloy and CaO-Al with Mo-Ni
2O
3The class slag separates, respectively the 2nd procedure of Hui Shouing; For above-mentioned CaO-Al
2O
3The class slag, the V oxide compound that is equivalent to contain in this slag by interpolation is reduced to the necessary chemical equivalent of metal or this metal Si and/or metal A l more than chemical equivalent, melts after adding thermal reduction, be that alloy or V-Al are alloy and CaO-Al with V-Si
2O
3The class slag separates, respectively the 3rd procedure of Hui Shouing.
[patent documentation 1] spy opens the 2000-204420 communique
[patent documentation 2] spy opens the 2001-214423 communique
But, in the recovery method of in patent documentation 1, being put down in writing, use dust coal or coke reductive agent (referring to Patent Document 1, the 0022nd section) as Fe, Ni in the solid phase reduction raw material and Mo composition.Therefore, generation is residual in the metal of main component carbon to be arranged with Fe, Ni, Mo.Because carbon is easy to combine with Fe-Mo, Fe-Ni etc. in the metal, therefore remove the carbon difficulty that becomes in the operation afterwards.In addition, when also having solid phase reduction, Mo becomes branch to distil in stove, causes the problem of Mo composition rate of recovery variation.More there is the numerous length of operation, the problem that cost of equipment increases.
In patent documentation 2, in the recovery method of record, in the 1st procedure, waste is not made particle, but powdery direct roasting (referring to Patent Document 2, the 0010th sections).Therefore, have waste sintering in stove, immobilising problem becomes.
In addition, in the 2nd procedure,, for example, in smelting furnace, produce phenomenon built on stilts or that up blow floating owing to, cause the working of a furnace to worsen with powdered state fusing waste.Working of a furnace deterioration can cause that the unit power consumption amount increases and the instability of operation.Have again, in the 2nd procedure,, can produce the problem of V composition and Mo, Ni component separating difficulty owing to use metal Si and/or metal A l as reductive agent.That is to say, reduce the amount of metal Si and/or metal A l, when carrying out weak reduction, the yield rate variation of Mo and Ni composition contains in the slag of V and can sneak into Mo and Ni composition.On the other hand, when reducing by force, it is in the alloy that the V that not only is reduced becomes branch to be blended into Mo-Ni, and it is in the alloy that Si and/or Al reductive agent also can be blended into Mo-Ni.If particularly use Al as reductive agent, Al can react with the oxygen in the atmosphere, and oxidation loss is increased.
Summary of the invention
The present invention in view of the above fact, its purpose be to provide a kind of can be from the waste that contains V, Mo and Ni, it is that alloy and Fe-V are the method for alloy that stable, high rate of finished products ground reclaims Fe-Mo-Ni.
The present inventor is conceived to Ni, the Mo under 1400 ℃～1800 ℃ of melting and reducing temperature, the oxygen affinity of V.And, notice that the oxygen affinity of Fe is stronger than Ni and Mo shown in Fig. 1 (the standard free energy of formation figure of oxide compound), a little less than V, therefore learn, be alloy if use Fe can separate the slag and the Fe-Mo-Ni that contain V to high rate of finished products as reductive agent.
Promptly, the present invention has solved above-mentioned problem by a kind of method that reclaims precious metals, this method has following operation: contain the operation of the waste of V, Mo and Ni in roasting below 950 ℃ more than 800 ℃, contain the waste of V, Mo and Ni with Fe reduction, generate and contain the slag of V and the operation that Fe-Mo-Ni is alloy; Add reductive agent in the slag of the above-mentioned V of containing, generating Fe-V is the operation of alloy.
In addition, the present invention is a kind of method that reclaims precious metals from the waste that contains V, Mo and Ni, and this method has following operation: contain the operation of the waste of V, Mo and Ni in roasting below 950 ℃ more than 800 ℃; By with the waste of the above-mentioned V of containing, Mo and Ni, pack in the process furnace as the iron of reductive agent and fusing assistant, they are added thermal reduction, generate and contain the slag of V and the operation that Fe-Mo-Ni is alloy; Add reductive agent Al in the above-mentioned slag that contains V, generating Fe-V is alloy and CaO-Al
2O
3The operation of class slag.
In slag that generates the above-mentioned V of containing and operation that Fe-Mo-Ni is alloy, behind the above-mentioned waste that contains V, Mo and Ni of above-mentioned iron reduction, also can use at least a reduction among Al, Si and the C to reduce the Fe oxide compound of generation with above-mentioned Fe.
According to the present invention, the Fe oxide compound that can use reduction reaction to generate is the source of iron of alloy as Fe-MO-Ni.In addition, the Fe content in the slag that contains V can be adjusted, and then the Fe content specification that to make its Fe-V that meets final acquisition be alloy can be adjusted.
In the operation of the above-mentioned waste that contains V, Mo and Ni of drying, wish behind the above-mentioned waste that contains V, Mo and Ni of drying, to pulverize, be configured as nodulizing, and it is carried out roasting.
According to the present invention, directly do not pack in the process furnace with powdery owing to be not the waste that will contain V, Mo and Ni, therefore can not produce phenomenon built on stilts or that blow floating from bottom to up, therefore, can carry out stable operation.
In addition, carry out in the operation of roasting at waste to the above-mentioned V of containing, Mo and Ni, also can be after the above-mentioned waste that contains V, Mo and Ni of roasting, reshape and be nodulizing.
Contain in the slag of V and the operation that Fe-Mo-Ni is alloy in above-mentioned generation, can be pre-formed iron and bathe, the waste of the above-mentioned V of containing, Mo and Ni is encased in this iron carries out fusion reduction reaction in bathing.
According to the present invention, can improve the reaction efficiency of reduction reaction, and can improve thermo-efficiency.Working continuously of process furnace also becomes possibility in addition.
Containing in the slag of V and the operation that Fe-Mo-Ni is alloy in above-mentioned generation, can be the slag after separating of alloy and the above-mentioned V of containing with above-mentioned Fe-Mo-Ni, carries out above-mentioned Fe-Mo-Ni and be taking off S, take off P, taking off C of alloy.
According to the present invention, can remove impurity S composition, P composition and C composition, making Fe-Mo-Ni is that alloy is up to specification.In addition, roasting be configured as nodulizing contain the waste of V, Mo and Ni the time, the S composition that contains in the waste is with SO
xForm is discharged, and the C composition is with CO
2Form is discharged, and Fe-Mo-Ni to be alloy take off S, take off C, the burden when alleviating roasting thus with the slag after separating that contains V.
Can be shared be that alloy takes off S, takes off P, takes off the heating of using among the C and drop into reductive agent with container with in the slag of the above-mentioned V of containing to above-mentioned Fe-Mo-Ni, generating Fe-V is the heating container that uses in the operation of alloy.
According to the present invention, can realize implementing recovery method with least equipment.
In slag that generates the above-mentioned V of containing and operation that Fe-Mo-Ni is alloy, above-mentioned Fe-Mo-Ni is that alloy is once come out of the stove during the fused solution, the slag of the above-mentioned V of the containing fused solution of can repeatedly coming out of the stove.
The Fe-Mo-Ni that generates is that the alloy amount is compared considerably less with the slag that contains V.According to the present invention, by making the slag that the contains V fused solution of frequently coming out of the stove, thereby improve thermo-efficiency.In addition, Fe-Mo-Ni is that the alloy fused solution of also coming out of the stove is compared when coming out of the stove fused solution with every batch of slag that contains V, has improved productivity.
The simple declaration of accompanying drawing
The standard free energy of formation figure of Fig. 1 oxide compound.
Fig. 2 illustrates the schema of the precious metals recovery method in one embodiment of the invention.
Fig. 3 is with the schema of the flowchart graphization of Fig. 2.
Fig. 4 illustrate Fe, Ni in the metal in the electric furnace, Mo composition over time with electric furnace in the synoptic diagram of fused solution quantitative changeization.
Fig. 5 illustrates the figure of other examples of the recovery method flow process of precious metals.
The preferred plan that carries out an invention
Below, describe with regard to one embodiment of the invention.In the present embodiment, be raw material with the waste that contains V, Mo and Ni.Specifically, be to use back desulfurization catalyst (direct desulfurization catalyzer, indirect desulfurization catalyzer), Boiler Ash, boiler mud, nickel class mud, ammonium meta-vanadate etc. at least a or mix the waste that they obtain and be raw material.Table 1 has been listed an example of every kind of composition in the raw material.
[table 1]
| The raw material name | Evaporate into the wt% that grades | [the average proterties of estimation of input raw material: Dry, wt%] | |||||||||||
| Ni | Mo | V | P | S | C | Fe | Al | SiO 2 | Co | Ti | W | ||
| Used direct desulfurization catalyzer | 26.0％ | 3.81％ | 5.39％ | 7.30％ | 0.80％ | 10.00％ | 23.00％ | 3.00％ | 25.00％ | 0.80％ | 0.00％ | 0.00％ | 0.00％ |
| Used indirect desulfurization catalyzer | 11.0％ | 1.20％ | 12.09％ | 0.64％ | 0.50％ | 1.00％ | 23.00％ | 3.00％ | 25.00％ | 0.00％ | 1.52％ | 0.00％ | 0.00％ |
| The petroleum coke Boiler Ash | 11.0％ | 0.50％ | 0.00％ | 1.50％ | 0.00％ | 6.50％ | 80.00％ | 0.50％ | 0 20％ | 2.00％ | 0.00％ | 0.00％ | 0.00％ |
| Carbon class mud | 50.0％ | 1.50％ | 0.00％ | 2.00％ | 0.00％ | 0.13％ | 68.00％ | 2.00％ | 0.04％ | 0.10％ | 0.00％ | 0.00％ | 0.00％ |
| Nickel class mud | 55.0％ | 8.50％ | 0.00％ | 3.50％ | 0.02％ | 0.00％ | 0.00％ | 0.10％ | 0.01％ | 0.03％ | 0.00％ | 0.00％ | 0.00％ |
| Ammonium meta-vanadate | 0.0％ | 0.00％ | 0.00％ | 43.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Heavy oil gasifying greasy filth | 75.0％ | 0.90％ | 0.00％ | 3.30％ | 0.00％ | 0.00％ | 0.00％ | 7.64％ | 1.50％ | 0.60％ | 0.00％ | 0.00％ | 0.00％ |
| The VR Boiler Ash | 50.0％ | 0.75％ | 0.00％ | 0.75％ | 0.00％ | 3.50％ | 88.00％ | 1.00％ | 1.00％ | 5.00％ | 0.00％ | 0.00％ | 0.00％ |
For example, Ni, Mo and V composition are many in the desulfurization catalyst, and C, S composition are also many.The C composition for example can contain about 80% in the Boiler Ash, and does not contain the Mo composition.Carbon class sludge water content for example can contain 50%.With the waste that contains diversified composition like this is raw material.Raw material presents the state of heavy oil or attachment of moisture.
Table 2 lists an example of the specification of the product that finally obtains.
[table 2]
| ProductName: ferrovanadium | ||||||||
| V (vanadium) | C (carbon) | Si (silicon) | P (phosphorus) | S (sulphur) | Al (aluminium) | Ni (nickel) | Mo (molybdenum) | |
| Product specification | 45 0～55.0％ | 0.2％max | 2.0％max. | 0.2％max. | 0.1％max. | 4.0％max | 1.0％max. | 1.0％max. |
| ProductName: iron nickel molybdenum; Fe-Ni-Mo | |||||||
| Ni (nickel) | Mo (molybdenum) | C (carbon) | Si (silicon) | P (phosphorus) | S (sulphur) | Cu (copper) | Co (cobalt) |
| 24.0～34.0％ | 16.0～26.0％ | 2.0％max. | 2.0％max. | 0.1％max. | 0.1％max. | 0.5％max. | 3.0％max. |
| ProductName: calcium aluminate; CaoAl 2O 3 | |||||||
| Al 2O 3(aluminum oxide) | CaO (unslaked lime) | MgO | SiO 2 | FeO | P (phosphorus) | S (sulphur) | |
| Product specification | 50.0～55.0％ | 28.0～33.0％ | 10.0％max. | 5.0％max. | 1.0％max. | 0.05％max. | 0.1％max. |
For Fe-V is that the alloy requirement reaches and is equivalent to for example specification of JIS2 standard substance.According to this specification, needing to adjust the V composition is 45～55 quality %, and inhibition C, Si, P, S become to grade for low-level, and it is low-level also will suppressing Ni, Mo and Al composition.In addition, be that alloy for example has the standard when using in iron structure for Fe-Ni-Mo, be low-level according to this standard-required control P, S composition.
Fig. 2 illustrates the flow process of precious metals recovery method, and Fig. 3 is the graphical of this flow process.At first, raw materials (S1) such as dry desulfurization catalyst (direct desulfurization catalyzer, indirect desulfurization catalyzer), Boiler Ash, carbon class mud, nickel class mud, heavy oil gasifying greasy filth.This drying process is in rotary drier raw material for example to be carried out heat drying under the temperature about 120 ℃.Moisture in the raw material for example has about 30～40% to exist as volatile component.When under the state of moisture is arranged, directly entering subsequent processing, can not form nodulizing because of excess moisture so sometimes.In addition, desulfurization catalyst and coke Boiler Ash are because moisture own seldom, therefore drops into after drying process sometimes again.
Then, pulverize the dry waste of crossing that contains V, Mo and Ni (S2).Pulverize the waste that contains V, Mo and Ni by for example moisture type runner milling.By pulverizing plurality of raw materials is mixed, and become even.
Then, the waste after pulverizing is carried out granulation, be configured as nodulizing (S3).For example crushed material is configured as granular or blocky nodulizing by tablets press or briquetting press.If raw material is not configured as nodulizing and directly enters subsequent processing with powdery, then raw material just might be in stoving oven sintering, in the process furnace of melting and reducing, can produce phenomenon built on stilts or that upwards blow floating, the working of a furnace is worsened.
Then, the raw material (S4) behind the roasting nodulizing.In this operation, the raw material behind the nodulizing is for example being heated for 800～900 ℃ times in stove.By this roasting, make S composition, C composition thermal degradation in the waste, be generated as SO
x, CO
2Deng removing.Be to be fit to that C composition attached to heavy oil on the raw material and so on becomes oxide compound and the temperature of removing is that the rate of recovery is reduced below 950 ℃ or 950 ℃ more than 800 ℃ or 800 ℃.
Then, with the raw material after the roasting, be encased in the electric furnace as process furnace as the Fe of reductive agent with as the lime of fusing assistant.Then, under about 1700 ℃ it is added thermal reduction, generating the slag and the Fe-Mo-Ni that contain V is alloy (S5).
In this operation (S5), the electric furnace of the raw material after the roasting, Fe and fusing assistant can being packed into simultaneously.Also can be pre-formed iron in addition and bathe, raw material and lime this iron of packing into is carried out fusion reduction reaction in bathing.Bathe if be pre-formed iron, can improve the reaction efficiency of reduction reaction, and can improve thermo-efficiency.
Mo oxide compound and Ni oxide compound can reduce with Fe in the raw material.Be set at the Mo oxide compound and the Ni oxide compound that roughly are equivalent in the waste that contains V, Mo and Ni as the amount of the iron of reductive agent and be reduced to the necessary chemical equivalent of metal.
Raw material adds reductive agent Al with after the Fe reduction in fused solution, with Al reductive agent also the Fe oxide compound that generates of reason Fe reduction and the Fe oxide compound in the raw material.Reducing with the Al reductive agent is for the Fe oxide compound that will generate by reduction reaction is that the source of iron of alloy is got back in the metal and gone as Fe-Mo-Ni, also is in order to adjust the Fe content in the slag that contains V in addition.The Al reductive agent is the content that is used to adjust Fe after all complementaryly.As the reductive agent of Fe oxide compound, can use any one or their composition in metal A l, metal Si, ferro-silicon, the carbon etc.
If do not add the Al reductive agent, all reduce with the Fe reductive agent, adding possibly as Fe-Mo-Ni in the amount as the Fe of reductive agent so is the component of the source of iron of alloy.But so, the Fe composition that contains in the subsequent processing in the slag of V will be too much, causes V composition reduction difficulty.Contain the more situation of Fe content in the slag of V, need in containing the slag of V, add and adjust the V that the V composition is used
2O
5Perhaps ammonium meta-vanadate.
Then, be alloy and contain the slag after separating of V at Fe-Mo-Ni, carry out Fe-Mo-Ni and be the taking off S, take off P, take off C of alloy (S6, S7).It is in the alloy that P composition in the raw material remains in Fe-Mo-Ni.Therefore the S composition must carry out desulfurization because standard is strict, and therefore the C composition must take off C because the carbon that adds from electrode is arranged.
This operation at first is that alloy molten liquid is come out of the stove and is injected in the ladle furnace as heating container (S6) with Fe-Mo-Ni.Then, pack into lime, CaO-Al
2O
3Class fusing assistant and CaO-Al
2O
3-FeO class fusing assistants etc. take off S, P, C (S7).For CaO-Al
2O
3The class fusing assistant also can utilize and described laterly contain the slag of V and the slag that generates with Al reduction.Blow Ar gas or O
2Gas (forming process) is effective.At last, will take off S, take off P, and take off Fe-Mo-Ni behind the C and be alloy and water and cast from the mold.
On the other hand, the slag that contains V also carries out the ladle furnace (S8) that fused solution is come out of the stove and injected conduct heating usefulness container.Also drop into Al reductive agent, lime in this ladle furnace and adjusted the V that the V composition is used
2O
5, thus, generating Fe-V by the slag that contains V is alloy and CaO-Al
2O
3Slag.Here, in order to use least equipment, can shared Fe-Mo-Ni be that alloy takes off S, take off P, take off ladle furnace that uses among the C and the employed ladle furnace of slag that contains V with the Al reduction.
Fig. 4 is illustrated in fusion liquid measure in the electric furnace and metal Fe, Ni, the time dependent synoptic diagram of Mo composition.By the Fe reduction, prolong in time, the Fe composition in the metal tails off, and it is many that Ni and Mo composition become, and can reach stable afterwards.In addition, if when containing the slag of V and reaching specified amount, metal will intactly be stayed in the stove so, and the slag fused solution that only will contain V is come out of the stove and injected ladle furnace, then contains the reduction of the slag of V in ladle furnace.On the other hand, the slag fused solution that contains V is come out of the stove and is injected ladle furnace number batch, and Fe-Mo-Ni is just a come out of the stove fused solution and being injected in the ladle furnace once of alloy.The refining of then, in same ladle furnace, take off S, taking off P, taking off C.
The Fe-Mo-Ni that generates is that the amount of alloy is compared very few with the slag that contains V.Come out of the stove by the frequent fused solution of the slag that will contain V, improve the thermo-efficiency of electric furnace.And Fe-Mo-Ni is that alloy molten liquid is also come out of the stove and compared when coming out of the stove with the slag fused solution that contains V at every turn, has improved productivity.
Fig. 5 illustrates other examples of the recovery method flow process of precious metals.In this flow process, the drying process of pretreatment process and calcining process carry out together, and process flow is oversimplified.At first, raw materials such as desulfurization with roasting technique catalyzer (direct desulfurization catalyzer, indirect desulfurization catalyzer), Boiler Ash, carbon class mud, nickel class mud, heavy oil gasifying greasy filth (S1 ').In this operation, for example with rotary oven with for example under 800～900 ℃ of conditions, heat.By this roasting, evaporate the moisture in the waste, and can remove S composition, C composition.
Then dusty raw materials is carried out nodulizing (S3 ').By for example tablets press or briquetting press raw material is configured as particulate state or blocky nodulizing.In order to make raw material, adopt block and when being easier to carry out nodulizing, also can before nodulizing, add pulverizing process (S2 ').Not pulverous, can not carry out nodulizing yet and directly pack into.With raw material, join (S5) later process flow in the electric furnace as process furnace because identical, and use same symbol, therefore omit its explanation with above-mentioned recovery method flow process shown in Figure 2 as the Fe of reductive agent and lime as fusing assistant.
Embodiment 1
Mixing raw material roasting in drying machine of desulfurization catalyst, Boiler Ash, nickel class mud, obtain the moiety of table 3.
Table 3
| DRY(％) | Ni | Mo | V | Co | Al 2O 3 | SiO 2 |
| The roasting raw material | 3.0 | 2.3 | 3.4 | 0.08 | 16.2 | 1.0 |
Then, in the 500KVA electric furnace, add dried feed 100kg, unslaked lime 14kg, Fe7kg,, carry out fusion reduction reaction in about 1700 ℃ of heating down.The Fe-Mo-Ni that one-tenth shown in the generation table 4 is grouped into is alloy 10kg and rich V slag.
Table 4
| Mo | Ni | Co | V | (％) | |
| Fe-Mo-Ni | 20.0 | 29.0 | 0.8 | 0.2 |
Rich V stove 57kg after the Separation and Recovery is kept 1600 ℃ in high frequency furnace, add metal A l5kg as reductive agent and lime 5kg, V
2O
57kg, being recovered to Fe-V as shown in table 5 is alloy 10kg.
Table 5
| V | Al | Mo | Ni | (％) | |
| Fe-V | 46.0 | 1.0 | 0.9 | 0.5 |
Embodiment 2
Behind raw material dryings such as desulfurization catalyst, boiler mud, nickel class mud, Boiler Ash, after the wilkinite 2% of interpolation as tackiness agent, 200 orders or carry out damping below 200 orders and pulverize in the moisture type ball mill then, are configured as spherical about diameter 10mm with pellet machine.Afterwards in vertical heater, 800 ℃ of roastings 3 hours obtain calcining matter as shown in table 6.
Table 6
| (％) | C | S | Mo | Ni | Co | V | SiO 2 | Al 2O 3 |
| Calcining matter | 0.1 | 0.4 | 5.5 | 7.5 | 0.2 | 8.4 | 2.4 | 40.0 |
In being provided with the 500KVA electric furnace of magnesia furnace lining, fusion 17kgFe is added into above-mentioned calcining matter 100kg and unslaked lime 32, Al4kg wherein in advance, and again by being blowed the stirring of Ar gas, obtaining Fe-Mo-Ni as shown in table 7 is alloy 24kg.
Table 7
| Mo | Ni | Co | V | Si | P | S | C | (％) | |
| Fe-Mo-Ni | 20.0 | 29.0 | 0.8 | 0.2 | 0.1 | 0.5 | 0.3 | 0.1 |
In high frequency furnace, be that alloy keeps heating again, take off S, P, C Fe-Mo-Ni.The results are shown in table 8.
Table 8
| P | S | C | |
| Fe-Mo-Ni | 0.04 | 0.03 | 0.05 |
Rich V slag 138kg after the Separation and Recovery is maintained at about 1600 ℃, under Ar gas, stirs.Adding is 25kg, V as the metal A l of reductive agent
2O
5Be 21kg, lime is 25kg, and being recovered to Fe-V as shown in table 9 is alloy 39kg.
Table 9
| V | Al | Mo | Ni | Si | P | (％) | |
| Fe-V | 46.8 | 0.1 | 0.9 | 0.5 | 0.4 | 0.05 |
In addition, the composition of slag is: CaO31%, Al
2O
352%, SiO
22%, MgO8%, FeO0.8%.
As described above, by the present invention, because use as the iron of reductive agent, therefore can be stablized from the waste that contains V, Mo and Ni, recovery Fe-Mo-Ni in high rate of finished products ground is that alloy and Fe-V are alloy.
Claims (9)
1. method that from the waste that contains V, Mo and Ni, reclaims precious metals, this method comprises: contain the waste of V, Mo and Ni with the iron reduction, generate contain the slag of V and operation that Fe-Mo-Ni is alloy and
Reductive agent is dropped in the slag of the above-mentioned V of containing, generating Fe-V is the operation of alloy.
2. method that from the waste that contains V, Mo and Ni, reclaims precious metals, this method comprises following operation:
Roasting contains the operation of the waste of V, Mo and Ni;
With the waste of the above-mentioned V of containing, Mo and Ni, as the Fe of reductive agent and the fusing assistant process furnace of packing into, they are added thermal reduction, contain the slag of V and the operation that Fe-Mo-Ni is alloy thereby generate;
The Al reductive agent is put in the slag of the above-mentioned V of containing, generating Fe-V is alloy and CaO-Al
2O
3The operation of slag.
3. according to claim 1 or the 2 described methods that from the waste that contains V, Mo and Ni, reclaim precious metals, it is characterized in that, in slag that generates the above-mentioned V of containing and operation that Fe-Mo-Ni is alloy, after the above-mentioned waste that contains V, Mo and Ni of above-mentioned Fe reduction, with at least a reduction among Al, Si and the C owing to reduce the Fe oxide compound that generates with above-mentioned Fe.
4. according to claim 1 or the 2 described methods that from the waste that contains V, Mo and Ni, reclaim precious metals, it is characterized in that, in the operation of the above-mentioned waste that contains V, Mo and Ni of roasting, behind the dry above-mentioned waste that contains V, Mo and Ni, pulverize, be configured as nodulizing, and it is carried out roasting.
5. according to claim 1 or the 2 described methods that from the waste that contains V, Mo and Ni, reclaim precious metals, it is characterized in that, in the operation of the above-mentioned waste that contains V, Mo and Ni of roasting, roasting is above-mentioned contain the waste of V, Mo and Ni after, be configured as nodulizing.
6. according to claim 1 or the 2 described methods that from the waste that contains V, Mo and Ni, reclaim precious metals, it is characterized in that, in slag that generates the above-mentioned V of containing and operation that Fe-Mo-Ni is alloy, generate iron in advance and bathe, the waste of the above-mentioned V of containing, Mo and Ni this iron of packing into is carried out fusion reduction reaction in bathing.
7. according to claim 1 or the 2 described methods that from the waste that contains V, Mo and Ni, reclaim precious metals, it is characterized in that, in slag that generates the above-mentioned V of containing and operation that Fe-Mo-Ni is alloy, with above-mentioned Fe-Mo-Ni is the slag after separating of alloy and the above-mentioned V of containing, to above-mentioned Fe-Mo-Ni is that alloy takes off S, take off P, take off C.
8. according to the described method that from the waste that contains V, Mo and Ni, reclaims precious metals of claim 7, it is characterized in that, can shared above-mentioned Fe-Mo-Ni be that alloy takes off S, take off P, taking off the employed heating of C uses container and reductive agent is dropped into to generate Fe-V in the slag of the above-mentioned V of containing be employed heating container in the alloy operation.
9. according to claim 1 or the 2 described methods that from the waste that contains V, Mo and Ni, reclaim precious metals, it is characterized in that, in slag that generates the above-mentioned V of containing and operation that Fe-Mo-Ni is alloy, above-mentioned Fe-Mo-Ni is that alloy is once come out of the stove during the liquation, the above-mentioned V of the containing slag liquation of can repeatedly coming out of the stove.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1150162A (en) * | 1997-08-05 | 1999-02-23 | Chubu Electric Power Co Inc | Recovery of valuable metal from heavy oil ash |
| JP2000204420A (en) * | 1999-01-14 | 2000-07-25 | Nippon Roburesu Kogyo Kk | Recovery of valuable metal from vanadium-containing waste |
| JP2001316732A (en) * | 2000-05-11 | 2001-11-16 | Nippon Cms Kk | Method for recovering valuable metal from material containing nickel and vanadium |
-
2003
- 2003-12-02 CN CNB2003801052925A patent/CN1312300C/en not_active Expired - Lifetime
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1150162A (en) * | 1997-08-05 | 1999-02-23 | Chubu Electric Power Co Inc | Recovery of valuable metal from heavy oil ash |
| JP2000204420A (en) * | 1999-01-14 | 2000-07-25 | Nippon Roburesu Kogyo Kk | Recovery of valuable metal from vanadium-containing waste |
| JP2001316732A (en) * | 2000-05-11 | 2001-11-16 | Nippon Cms Kk | Method for recovering valuable metal from material containing nickel and vanadium |
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