CN104651620A - Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material - Google Patents
Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material Download PDFInfo
- Publication number
- CN104651620A CN104651620A CN201510125711.6A CN201510125711A CN104651620A CN 104651620 A CN104651620 A CN 104651620A CN 201510125711 A CN201510125711 A CN 201510125711A CN 104651620 A CN104651620 A CN 104651620A
- Authority
- CN
- China
- Prior art keywords
- nickel
- section
- acid
- waste material
- leach
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000000034 method Methods 0.000 title claims abstract description 167
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 90
- 239000000956 alloy Substances 0.000 title claims abstract description 79
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 29
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 135
- 238000000926 separation method Methods 0.000 claims abstract description 72
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 51
- 238000002386 leaching Methods 0.000 claims abstract description 49
- 238000001556 precipitation Methods 0.000 claims abstract description 47
- 239000012535 impurity Substances 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 102
- 239000007788 liquid Substances 0.000 claims description 96
- 239000002585 base Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 46
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims description 44
- 239000012074 organic phase Substances 0.000 claims description 42
- 239000012670 alkaline solution Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 36
- 238000005189 flocculation Methods 0.000 claims description 34
- 230000016615 flocculation Effects 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 229920002401 polyacrylamide Polymers 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000008346 aqueous phase Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000003350 kerosene Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000000889 atomisation Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 239000002594 sorbent Substances 0.000 claims description 6
- 238000010891 electric arc Methods 0.000 claims description 4
- 238000009692 water atomization Methods 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 3
- 238000012387 aerosolization Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- -1 hydrogen ions Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- DYPAOELAZODIQL-UHFFFAOYSA-N S(O)(O)(=O)=O.[C]=O Chemical compound S(O)(O)(=O)=O.[C]=O DYPAOELAZODIQL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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)
Abstract
The invention provides a method for regenerating high-purity nickel sulfate from a nickel-based alloy waste material. The method comprises the following steps of: 1, fusing the nickel-based alloy waste material; 2, atomizing; 3, carrying out first-stage leaching treatment to obtain a first-stage leaching solution and a first-stage leaching residue; 4, respectively treating the first-stage leaching solution and the first-stage leaching residue, carrying out second-stage leaching on the first-stage leaching residue, then regulating the concentration of hydrogen ions contained in a second-stage leaching solution, and then substituting for first-stage leaching acid for recycling; sequentially carrying out first-stage precipitation impurity removal, second-stage precipitation impurity removal, nickel and cobalt extraction separation, sodium ion or/and ammonium ion extraction removal, sulfuric acid reverse extraction, oil adsorption removal and evaporative crystallization treatment on the first-stage leaching solution to obtain the high-purity nickel sulfate. The method provided by the invention can be used for effectively recovering nickel contained in the nickel-based alloy waste material so as to be prepared into the high-purity nickel sulfate and directly applying the high-purity nickel sulfate to related industries, such as accumulators and electroplating, and has the characteristics of high raw material adaptability, high product purity, less environmental pollution and the like.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, be specifically related to a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material.
Background technology
Nickel is important strategic reserves metal, is widely used in the aspects such as aviation, military project, chemical industry, electronics.China is the country of scarce nickel, and along with the fast development of China's economy and continually developing of new and high technology, the range of application of nickel in modern industry constantly expands, demand improves constantly.China has become nickel country of consumption maximum in the world at present, but nickel Mineral resources are day by day poor.Therefore, the various nickeliferous secondary resource of comprehensive development and utilization is a kind of effective way and the inevitable choice that make up a Mineral resources wretched insufficiency.
Containing a large amount of nickel and other valuable metal in secondary resource nickel-base alloy waste material, Huge value.Nickel-base alloy waste material is mainly derived from: the rising head produced in (1) nickel-base alloy preparation process, shavings, car bits etc.; (2) casting such as nickel-base alloy component, component is processed with forging and is produced waste material; (3) nickel-base alloy component, the component of time limit of service are arrived.
The existing reparation technology preparing single nickel salt is as described in patent CN 1544664A " shrend converter mattes sulfuric acid Selectively leaching produces cell-grade high-purity sulphuric acid nickel technique ", and a kind of method is that rich nickel solution evaporative crystallization forms by shrend electricity nickel or nickle carbonoxide sulfuric acid dissolution; Another kind method adopts low copper converter mattes or nickel-containing material to be raw material, through the whole valuable metal of sulfuric acid pressure leaching, then purification separation, evaporative crystallization extracting sulfuric acid nickel.
The research regenerating high-purity sulphuric acid nickel at present from nickel-base alloy waste material not yet has report.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of method preparing high-purity sulphuric acid nickel from nickel-base alloy waste material.The method can nickel in efficient recovery nickel-base alloy waste material be prepared into high-purity sulphuric acid nickel, makes it directly apply to the relevant industries such as store battery, plating, have the features such as adaptability to raw material is strong, product purity is high, environmental pollution is little.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, and it is characterized in that, the method comprises the following steps:
Step one, nickel-base alloy scrap melting is become liquid, obtain aluminium alloy;
Step 2, aluminium alloy described in step one carried out to atomization process, obtain powdered alloy;
Step 3, powdered alloy described in step 2 is placed in one section and leaches acid and carry out one section and leach process, after solid-liquid separation, obtain one section of leach liquor and one section of leached mud; In described one section of leaching acid, hydrionic concentration is 2mol/L ~ 5mol/L, and described one section is leached sour volume V
1meet: 4m
1≤ V
1≤ 8m
1, wherein m
1for the quality of powdered alloy, m
1unit be g, V
1unit be mL, described one section leach process temperature be 70 DEG C ~ 90 DEG C, described one section leach process time be 1h ~ 3h;
Step 4, one section of leach liquor described in step 3 and one section of leached mud to be processed respectively:
The treating processes of described one section of leached mud is: one section of leached mud is placed in two sections of leaching acid and carries out two sections of leaching process, obtaining two sections of leach liquors and two sections of leached muds after solid-liquid separation, is then replace one section to leach acid after 2mol/L ~ 5mol/L to recycle by hydrionic concentration adjustment in two sections of leach liquors; In described two sections of leaching acid, hydrionic concentration is 6mol/L ~ 9mol/L, and described two sections are leached sour volume V
2meet: 3m
2≤ V
2≤ 6m
2, wherein m
2be the quality of one section of leached mud, m
2unit be g, V
2unit be mL, described two sections leach process temperature be 70 DEG C ~ 90 DEG C, described two sections leach process times be 1h ~ 3h;
Described one section of leach liquor is processed to step 407 by step 401:
Step 401, adopt alkaline solution one to carry out one section of removing impurity by means of precipitation process for precipitation agent to one section of leach liquor, be till 3.5 ~ 4.0 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing a and Solid separate b; The temperature of described one section of removing impurity by means of precipitation process is 40 DEG C ~ 80 DEG C;
Step 402, adopt alkaline solution two to carry out two sections of removing impurity by means of precipitation process to the thing of liquid separation described in step 401 a for precipitation agent, be till 4.5 ~ 5.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing c and Solid separate d; Containing nickel and cobalt in described liquid separation thing c; The temperature of described two sections of removing impurity by means of precipitation process is 40 DEG C ~ 80 DEG C;
Nickel in the thing of liquid separation described in step 402 c is separated with cobalt by the method for step 403, employing extraction, obtains rich cobalt extraction liquid and rich nickel raffinate; The detailed process of described extraction is: with liquid separation thing c for aqueous phase, with extraction agent one and thinner one by volume 1: the mixture that (2 ~ 5) mix, for organic phase, is (1 ~ 3) in the volume ratio of organic phase and aqueous phase: carry out 4 ~ 8 stage countercurrents under the condition of 1 and extract;
Sodium ion in rich nickel raffinate described in the method separation removing step 403 of step 404, employing extraction, or/and ammonium ion, obtains rich nickel organic phase; The detailed process of described extraction is: with rich nickel raffinate for aqueous phase, with extraction agent two and thinner two by volume 1: the mixture that (2 ~ 5) mix, for organic phase, is (1 ~ 3) in the volume ratio of organic phase and aqueous phase: carry out 4 ~ 8 stage countercurrents under the condition of 1 and extract;
Step 405, employing sulfuric acid carry out back extraction to nickel organic phase rich described in step 404, obtain nickel sulfate solution; The detailed process of described back extraction is: be 1 in the volume ratio of sulfuric acid and rich nickel organic phase: carry out 3 ~ 6 stage countercurrents extractions under the condition of (8 ~ 20);
Step 406, employing gac carry out absorption oil removal treatment for sorbent material to nickel sulfate solution described in step 405, obtain the nickel sulfate solution after oil removing;
Step 407, the nickel sulfate solution heating after oil removing described in step 406 is concentrated into nickel ion concentration and is not less than 120g/L, after crystallization, obtain high-purity sulphuric acid nickel; In described high-purity sulphuric acid nickel, the mass percentage of nickel is not less than 22%.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, is characterized in that, in the waste material of nickel-base alloy described in step one, the mass percentage of nickel is not less than 50%.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, is characterized in that, melting the equipment that nickel-base alloy waste material adopts in step one is medium frequency induction melting furnace, high-frequency induction smelting furnace or electric arc furnace.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, is characterized in that, the concrete atomizing type being atomized process described in step 2 is aerosolization, water atomization or mixing wastewater with air atomization.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, is characterized in that, described in step 3 one section to leach described in acid and step 4 two sections leach sour be in sulfuric acid, hydrochloric acid and nitric acid one or more.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, it is characterized in that, alkaline solution two described in alkaline solution one described in step 401 and step 402 is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; Described alkaline solution one is 5% ~ 30% with the mass percentage of alkaline solution two neutral and alkali compound.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, it is characterized in that, step 3 is before carrying out solid-liquid separation to one section of Leaching Systems, in one section of Leaching Systems, add flocculation liquid in advance, the volume of the flocculation liquid added is one section and leaches 0.01% ~ 0.1% of sour volume; Described flocculation liquid be flocculation agent and deionized water in mass ratio (0.1 ~ 1): 1 mixing solutions mixed, described flocculation agent is cationic-type polyacrylamide, anion-polyacrylamide, amphoteric ionic polyacrylamide or polymer polyacrylamide.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, it is characterized in that, described in extraction agent one described in step 403 and step 404, extraction agent two is one or more in extraction agent P507, extraction agent P204 and extraction agent Cyanex272, and described thinner one and thinner two are sulfonated kerosene or/and 260# solvent oil.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, is characterized in that, the concentration of sulfuric acid described in step 405 is 0.5mol/L ~ 2.5mol/L.
A kind of above-mentioned method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material, is characterized in that, the time of crystallization described in step 407 is 6h ~ 12h.
The present invention compared with prior art has the following advantages:
1, the invention provides a kind of new approaches preparing high-purity sulphuric acid nickel from nickel-base alloy waste material.The present invention can nickel in efficient recovery nickel-base alloy waste material make high-purity sulphuric acid nickel, makes it directly apply to the relevant industries such as store battery, plating, have the features such as adaptability to raw material is strong, product purity is high, environmental pollution is little.
2, first the present invention adopts fusing, atomization and the method that leaches to be leached efficiently by metallic nickel from nickel-base alloy waste material and proceed in solution, then by the method for precipitation, extraction, back extraction, oil removing and evaporative crystallization, successively deep purifying is carried out to rich nickel leach liquor, finally prepare high-purity sulphuric acid nickel.
3, the nickel content in the solid slag thing adopting the present invention to obtain is below 0.5%, and nickel leaching yield is greater than 99%, and nickel recovery is greater than 96%, and the quality product of the single nickel salt of preparation is higher than GB " GB/T26524-2011 " requirement.
4, adopt the inventive method can nickel in efficient recovery nickel-base alloy waste material make high-purity sulphuric acid nickel, and the relevant industries such as store battery, plating can be directly applied to.The Solid separate obtained in the present invention can be used for reclaiming the rare elements such as tungsten, molybdenum, tantalum, chromium further.
5, the whole technological process of the present invention is almost pollution-free to environment, is that a kind of efficiency is high, cost is low, eco-friendly method.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material.
Embodiment
Embodiment 1
Composition graphs 1, the method that the present embodiment regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material comprises the following steps:
Step one, nickel-base alloy waste material is fused into liquid state in high-frequency induction smelting furnace, obtains aluminium alloy; After testing, containing Ni 62.34wt% in described nickel-base alloy waste material, containing Co 8.67wt%;
The method of step 2, employing water atomization carries out atomization process to aluminium alloy described in step one, obtains powdered alloy;
Step 3, powdered alloy described in step 2 is placed in one section and leaches acid and carry out one section and leach process, after solid-liquid separation, obtain one section of leach liquor and one section of leached mud; In described one section of leaching acid, hydrionic concentration is 2mol/L, and described one section is leached sour volume V
1meet: V
1=5m
1, wherein m
1for the quality of powdered alloy, m
1unit be g, V
1unit be mL, described one section leach process temperature be 75 DEG C, described one section leach process time be 1.5h; Described one section leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, it is nitric acid that the present embodiment one section of adopting leaches acid;
Before carrying out solid-liquid separation to one section of Leaching Systems, add flocculation liquid in advance in one section of Leaching Systems, the volume of described flocculation liquid is one section and leaches 0.03% of sour volume; Described flocculation liquid is flocculation agent and deionized water 0.2: 1 mixing solutions mixed in mass ratio, described flocculation agent is preferably cationic-type polyacrylamide, anion-polyacrylamide, amphoteric ionic polyacrylamide or polymer polyacrylamide, and the flocculation agent that the present embodiment adopts is cationic-type polyacrylamide;
Step 4, one section of leach liquor described in step 3 and one section of leached mud to be processed respectively:
The treating processes of described one section of leached mud is: one section of leached mud is placed in two sections of leaching acid and carries out two sections of leaching process, obtaining two sections of leach liquors and two sections of leached muds after solid-liquid separation, is then replace one section to leach acid after 2mol/L to recycle by hydrionic concentration adjustment in two sections of leach liquors; In described two sections of leaching acid, hydrionic concentration is 6mol/L, and described two sections are leached sour volume V
2meet: V
2=4.5m
2, wherein m
2be the quality of one section of leached mud, m
2unit be g, V
2unit be mL, described two sections leach process temperature be 85 DEG C, described two sections leach process times be 2h; Described two sections leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, it is nitric acid that the present embodiment two sections of adopting leach acid;
Described one section of leach liquor is processed to step 407 by step 401:
Step 401, adopt alkaline solution one to carry out one section of removing impurity by means of precipitation process for precipitation agent to one section of leach liquor, be till 4.0 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing a and Solid separate b; The temperature of described one section of removing impurity by means of precipitation process is 70 DEG C; Described alkaline solution one is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution one for mass percentage be the trisodium phosphate aqueous solution of 5%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate b, make the nickel in Solid separate b proceed to liquid phase, thus effectively reduce nickel loss;
Step 402, adopt alkaline solution two to carry out two sections of removing impurity by means of precipitation process to the thing of liquid separation described in step 401 a for precipitation agent, be till 4.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing c and Solid separate d; Containing nickel and cobalt in described liquid separation thing c; The temperature of described two sections of removing impurity by means of precipitation process is 70 DEG C; Described alkaline solution two is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution two for mass percentage be the ammonium bicarbonate aqueous solution of 20%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate d, make the nickel in Solid separate d proceed to liquid phase, thus effectively reduce nickel loss;
Nickel in the thing of liquid separation described in step 402 c is separated with cobalt by the method for step 403, employing extraction, obtains rich cobalt extraction liquid and rich nickel raffinate; The detailed process of described extraction is: with liquid separation thing c for aqueous phase, with extraction agent one and thinner one by volume 1: 3 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 1: 1, carry out 4 stage countercurrent extractions; Described extraction agent one be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner one is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent one that the present embodiment adopts is extraction agent Cyanex272, and thinner one is sulfonated kerosene;
Sodium ion in rich nickel raffinate described in the method separation removing step 403 of step 404, employing extraction and ammonium ion, obtain rich nickel organic phase; The detailed process of described extraction is: with rich nickel raffinate for aqueous phase, with extraction agent two and thinner two by volume 1: 3 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 2: 1, carry out 8 stage countercurrent extractions; Described extraction agent two be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner two is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent two that the present embodiment adopts is extraction agent P507, and thinner two is sulfonated kerosene;
The sulfuric acid that step 405, employing concentration are 1.2mol/L carries out back extraction to nickel organic phase rich described in step 404, obtains nickel sulfate solution; The detailed process of described back extraction is: under the volume ratio of sulfuric acid and rich nickel organic phase is the condition of 1: 15, carry out 6 stage countercurrent extractions;
Step 406, employing gac carry out absorption oil removal treatment for sorbent material to nickel sulfate solution described in step 405, obtain the nickel sulfate solution after oil removing;
Step 407, by the nickel sulfate solution heating after oil removing described in step 406, to be concentrated into nickel ion concentration be 135g/L, then naturally cools to crystallizing at room temperature 9h, obtain high-purity sulphuric acid nickel.
After testing, the quality product of the single nickel salt of the present embodiment regeneration is more as shown in table 1 with the associated specifications of national standard " GB/T26524-2011 ".
The quality product of the single nickel salt of table 1 the present embodiment regeneration compares table look-up with national standard
As can be seen from Table 1, the quality product of the single nickel salt that the present embodiment is prepared from nickel-base alloy materials recycling is higher than national standard " GB/T 26524-2011 " technical requirements, and main metallic nickel content, much larger than 22%, can be widely used in plating and battery industry.
Embodiment 2
Composition graphs 1, the method that the present embodiment regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material comprises the following steps:
Step one, nickel-base alloy waste material is fused into liquid state in electric arc furnace, obtains aluminium alloy; After testing, containing Ni 58.31wt% in described nickel-base alloy waste material, containing Co 10.24wt%;
The method of step 2, employing aerosolization carries out atomization process to aluminium alloy described in step one, obtains powdered alloy;
Step 3, powdered alloy described in step 2 is placed in one section and leaches acid and carry out one section and leach process, after solid-liquid separation, obtain one section of leach liquor and one section of leached mud; In described one section of leaching acid, hydrionic concentration is 4mol/L, and described one section is leached sour volume V
1meet: V
1=6m
1, wherein m
1for the quality of powdered alloy, m
1unit be g, V
1unit be mL, described one section leach process temperature be 80 DEG C, described one section leach process time be 2h; Described one section leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, it is hydrochloric acid that the present embodiment one section of adopting leaches acid;
Before carrying out solid-liquid separation to one section of Leaching Systems, add flocculation liquid in advance in one section of Leaching Systems, the volume of described flocculation liquid is one section and leaches 0.05% of sour volume; Described flocculation liquid is flocculation agent and deionized water 0.5: 1 mixing solutions mixed in mass ratio, described flocculation agent is preferably cationic-type polyacrylamide, anion-polyacrylamide, amphoteric ionic polyacrylamide or polymer polyacrylamide, and the flocculation agent that the present embodiment adopts is anion-polyacrylamide;
Step 4, one section of leach liquor described in step 3 and one section of leached mud to be processed respectively:
The treating processes of described one section of leached mud is: one section of leached mud is placed in two sections of leaching acid and carries out two sections of leaching process, obtaining two sections of leach liquors and two sections of leached muds after solid-liquid separation, is then replace one section to leach acid after 4mol/L to recycle by hydrionic concentration adjustment in two sections of leach liquors; In described two sections of leaching acid, hydrionic concentration is 8mol/L, and described two sections are leached sour volume V
2meet: V
2=5m
2, wherein m
2be the quality of one section of leached mud, m
2unit be g, V
2unit be mL, described two sections leach process temperature be 80 DEG C, described two sections leach process times be 2h; Described two sections leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, it is hydrochloric acid that the present embodiment two sections of adopting leach acid;
Described one section of leach liquor is processed to step 407 by step 401:
Step 401, adopt alkaline solution one to carry out one section of removing impurity by means of precipitation process for precipitation agent to one section of leach liquor, be till 3.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing a and Solid separate b; The temperature of described one section of removing impurity by means of precipitation process is 80 DEG C; Described alkaline solution one is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution one for mass percentage be the ammonia soln of 10%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate b, make the nickel in Solid separate b proceed to liquid phase, thus effectively reduce nickel loss;
Step 402, adopt alkaline solution two to carry out two sections of removing impurity by means of precipitation process to the thing of liquid separation described in step 401 a for precipitation agent, be till 5.0 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing c and Solid separate d; Containing nickel and cobalt in described liquid separation thing c; The temperature of described two sections of removing impurity by means of precipitation process is 60 DEG C; Described alkaline solution two is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution two for mass percentage be the ammonium bicarbonate aqueous solution of 30%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate d, make the nickel in Solid separate d proceed to liquid phase, thus effectively reduce nickel loss;
Nickel in the thing of liquid separation described in step 402 c is separated with cobalt by the method for step 403, employing extraction, obtains rich cobalt extraction liquid and rich nickel raffinate; The detailed process of described extraction is: with liquid separation thing c for aqueous phase, with extraction agent one and thinner one by volume 1: 4 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 2: 1, carry out 4 stage countercurrent extractions; Described extraction agent one be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner one is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent one that the present embodiment adopts is extraction agent P507, and thinner one is 260# solvent oil;
The method of step 404, employing extraction is separated the ammonium ion in rich nickel raffinate described in removing step 403, obtains rich nickel organic phase; The detailed process of described extraction is: with rich nickel raffinate for aqueous phase, with extraction agent two and thinner two by volume 1: 4 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 2: 1, carry out 8 stage countercurrent extractions; Described extraction agent two be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner two is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent two that the present embodiment adopts is extraction agent P204, and thinner two is 260# solvent oil;
The sulfuric acid that step 405, employing concentration are 1.5mol/L carries out back extraction to nickel organic phase rich described in step 404, obtains nickel sulfate solution; The detailed process of described back extraction is: under the volume ratio of sulfuric acid and rich nickel organic phase is the condition of 1: 15, carry out 3 stage countercurrent extractions;
Step 406, employing gac carry out absorption oil removal treatment for sorbent material to nickel sulfate solution described in step 405, obtain the nickel sulfate solution after oil removing;
Step 407, by the nickel sulfate solution heating after oil removing described in step 406, to be concentrated into nickel ion concentration be 124g/L, then naturally cools to crystallizing at room temperature 10h, obtain high-purity sulphuric acid nickel.
After testing, the quality product of the single nickel salt of the present embodiment regeneration is more as shown in table 2 with the associated specifications of national standard " GB/T26524-2011 ".
The quality product of the single nickel salt of table 2 the present embodiment regeneration compares table look-up with national standard
As can be seen from Table 2, the quality product of the single nickel salt that the present embodiment is prepared from nickel-base alloy materials recycling, higher than national standard " GB/T 26524-2011 " technical requirements, can be widely used in plating and battery industry.
Embodiment 3
Composition graphs 1, the method that the present embodiment regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material comprises the following steps:
Step one, nickel-base alloy waste material is fused into liquid state in medium frequency induction melting furnace, obtains aluminium alloy; After testing, containing Ni 50.21wt% in described nickel-base alloy waste material, containing Co 9.77wt%;
The method of step 2, employing water atomization carries out atomization process to aluminium alloy described in step one, obtains powdered alloy;
Step 3, powdered alloy described in step 2 is placed in one section and leaches acid and carry out one section and leach process, after solid-liquid separation, obtain one section of leach liquor and one section of leached mud; In described one section of leaching acid, hydrionic concentration is 5mol/L, and described one section is leached sour volume V
1meet: V
1=4m
1, wherein m
1for the quality of powdered alloy, m
1unit be g, V
1unit be mL, described one section leach process temperature be 70 DEG C, described one section leach process time be 3h; Described one section leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, it is sulfuric acid that the present embodiment one section of adopting leaches acid;
Before carrying out solid-liquid separation to one section of Leaching Systems, add flocculation liquid in advance in one section of Leaching Systems, the volume of described flocculation liquid is one section and leaches 0.01% of sour volume; Described flocculation liquid is flocculation agent and deionized water 0.1: 1 mixing solutions mixed in mass ratio, described flocculation agent is preferably cationic-type polyacrylamide, anion-polyacrylamide, amphoteric ionic polyacrylamide or polymer polyacrylamide, and the flocculation agent that the present embodiment adopts is amphoteric ionic polyacrylamide;
Step 4, one section of leach liquor described in step 3 and one section of leached mud to be processed respectively:
The treating processes of described one section of leached mud is: one section of leached mud is placed in two sections of leaching acid and carries out two sections of leaching process, obtaining two sections of leach liquors and two sections of leached muds after solid-liquid separation, is then replace one section to leach acid after 5mol/L to recycle by hydrionic concentration adjustment in two sections of leach liquors; In described two sections of leaching acid, hydrionic concentration is 8mol/L, and described two sections are leached sour volume V
2meet: V
2=3m
2, wherein m
2be the quality of one section of leached mud, m
2unit be g, V
2unit be mL, described two sections leach process temperature be 90 DEG C, described two sections leach process times be 1h; Described two sections leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, it is sulfuric acid that the present embodiment two sections of adopting leach acid;
Described one section of leach liquor is processed to step 407 by step 401:
Step 401, adopt alkaline solution one to carry out one section of removing impurity by means of precipitation process for precipitation agent to one section of leach liquor, be till 3.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing a and Solid separate b; The temperature of described one section of removing impurity by means of precipitation process is 40 DEG C; Described alkaline solution one is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution one for mass percentage be the aqueous sodium carbonate of 30%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate b, make the nickel in Solid separate b proceed to liquid phase, thus effectively reduce nickel loss;
Step 402, adopt alkaline solution two to carry out two sections of removing impurity by means of precipitation process to the thing of liquid separation described in step 401 a for precipitation agent, be till 4.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing c and Solid separate d; Containing nickel and cobalt in described liquid separation thing c; The temperature of described two sections of removing impurity by means of precipitation process is 40 DEG C; Described alkaline solution two is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution two for mass percentage be the aqueous sodium hydroxide solution of 5%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate b, make the nickel in Solid separate b proceed to liquid phase, thus effectively reduce nickel loss;
Nickel in the thing of liquid separation described in step 402 c is separated with cobalt by the method for step 403, employing extraction, obtains rich cobalt extraction liquid and rich nickel raffinate; The detailed process of described extraction is: with liquid separation thing c for aqueous phase, with extraction agent one and thinner one by volume 1: 2 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 1: 1, carry out 8 stage countercurrent extractions; Described extraction agent one be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner one is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent one that the present embodiment adopts is extraction agent P507, extraction agent P204 and extraction agent Cyanex272 1: 1: 2 mixture mixed in mass ratio, and thinner one is sulfonated kerosene;
The method of step 404, employing extraction is separated the ammonium ion in rich nickel raffinate described in removing step 403, obtains rich nickel organic phase; The detailed process of described extraction is: with rich nickel raffinate for aqueous phase, with extraction agent two and thinner two by volume 1: 2 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 1: 1, carry out 4 stage countercurrent extractions; Described extraction agent two be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner two is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent two that the present embodiment adopts is extraction agent P507 and extraction agent P204 3: 1 mixtures mixed in mass ratio, and thinner two is sulfonated kerosene and 260# solvent oil 2: 5 mixtures mixed in mass ratio;
The sulfuric acid that step 405, employing concentration are 0.5mol/L carries out back extraction to nickel organic phase rich described in step 404, obtains nickel sulfate solution; The detailed process of described back extraction is: under the volume ratio of sulfuric acid and rich nickel organic phase is the condition of 1: 8, carry out 3 stage countercurrent extractions;
Step 406, employing gac carry out absorption oil removal treatment for sorbent material to nickel sulfate solution described in step 405, obtain the nickel sulfate solution after oil removing;
Step 407, by the nickel sulfate solution heating after oil removing described in step 406, to be concentrated into nickel ion concentration be 130g/L, then naturally cools to crystallizing at room temperature 6h, obtain high-purity sulphuric acid nickel.
After testing, the quality product of the single nickel salt of the present embodiment regeneration is more as shown in table 3 with the associated specifications of national standard " GB/T26524-2011 ".
The quality product of the single nickel salt of table 3 the present embodiment regeneration compares table look-up with national standard
As can be seen from Table 3, the quality product of the single nickel salt that the present embodiment is prepared from nickel-base alloy materials recycling, higher than national standard " GB/T 26524-2011 " technical requirements, can be widely used in plating and battery industry.
Embodiment 4
Composition graphs 1, the method that the present embodiment regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material comprises the following steps:
Step one, nickel-base alloy waste material is fused into liquid state in electric arc furnace, obtains aluminium alloy; After testing, containing Ni 50.12wt% in described nickel-base alloy waste material, containing Co 9.6wt%;
Step 2, the method adopting mixing wastewater with air to be atomized carry out atomization process to aluminium alloy described in step one, obtain powdered alloy;
Step 3, powdered alloy described in step 2 is placed in one section and leaches acid and carry out one section and leach process, after solid-liquid separation, obtain one section of leach liquor and one section of leached mud; In described one section of leaching acid, hydrionic concentration is 5mol/L, and described one section is leached sour volume V
1meet: V
1=8m
1, wherein m
1for the quality of powdered alloy, m
1unit be g, V
1unit be mL, described one section leach process temperature be 90 DEG C, described one section leach process time be 1h; Described one section leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, the present embodiment one section of adopting leaches the mix acid liquor that acid is hydrochloric acid and sulfuric acid;
Before carrying out solid-liquid separation to one section of Leaching Systems, add flocculation liquid in advance in one section of Leaching Systems, the volume of described flocculation liquid is one section and leaches 0.1% of sour volume; Described flocculation liquid is flocculation agent and deionized water 1: 1 mixing solutions mixed in mass ratio, described flocculation agent is preferably cationic-type polyacrylamide, anion-polyacrylamide, amphoteric ionic polyacrylamide or polymer polyacrylamide, and the flocculation agent that the present embodiment adopts is polymer polyacrylamide;
Step 4, one section of leach liquor described in step 3 and one section of leached mud to be processed respectively:
The treating processes of described one section of leached mud is: one section of leached mud is placed in two sections of leaching acid and carries out two sections of leaching process, obtaining two sections of leach liquors and two sections of leached muds after solid-liquid separation, is then replace one section to leach acid after 5mol/L to recycle by hydrionic concentration adjustment in two sections of leach liquors; In described two sections of leaching acid, hydrionic concentration is 9mol/L, and described two sections are leached sour volume V
2meet: V
2=6m
2, wherein m
2be the quality of one section of leached mud, m
2unit be g, V
2unit be mL, described two sections leach process temperature be 70 DEG C, described two sections leach process times be 3h; Described two sections leach that acid is preferably in sulfuric acid, hydrochloric acid and nitric acid one or more, the present embodiment two sections of adopting leach the mix acid liquor that acid are sulfuric acid and hydrochloric acid;
Described one section of leach liquor is processed to step 407 by step 401:
Step 401, adopt alkaline solution one to carry out one section of removing impurity by means of precipitation process for precipitation agent to one section of leach liquor, be till 4.0 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing a and Solid separate b; The temperature of described one section of removing impurity by means of precipitation process is 80 DEG C; Described alkaline solution one is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution one for mass percentage be the ammonium bicarbonate aqueous solution of 15%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate b, make the nickel in Solid separate b proceed to liquid phase, thus effectively reduce nickel loss;
Step 402, adopt alkaline solution two to carry out two sections of removing impurity by means of precipitation process to the thing of liquid separation described in step 401 a for precipitation agent, be till 5.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing c and Solid separate d; Containing nickel and cobalt in described liquid separation thing c; The temperature of described two sections of removing impurity by means of precipitation process is 80 DEG C; Described alkaline solution two is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is preferably one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; The present embodiment adopt alkaline solution two for mass percentage be the aqueous sodium carbonate of 5%;
In specific implementation process, can again carry out one section of removing impurity by means of precipitation process after acid-soluble for Solid separate b, make the nickel in Solid separate b proceed to liquid phase, thus effectively reduce nickel loss;
Nickel in the thing of liquid separation described in step 402 c is separated with cobalt by the method for step 403, employing extraction, obtains rich cobalt extraction liquid and rich nickel raffinate; The detailed process of described extraction is: with liquid separation thing c for aqueous phase, with extraction agent one and thinner one by volume 1: 5 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 3: 1, carry out 4 stage countercurrent extractions; Described extraction agent one be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner one is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent one that the present embodiment adopts is extraction agent P507, and thinner one is sulfonated kerosene and 260# solvent oil 1: 1 mixing solutions mixed in mass ratio;
Sodium ion in rich nickel raffinate described in the method separation removing step 403 of step 404, employing extraction and ammonium ion, obtain rich nickel organic phase; The detailed process of described extraction is: with rich nickel raffinate for aqueous phase, with extraction agent two and thinner two by volume 1: 5 mixture mixed for organic phase, under the volume ratio of organic phase and aqueous phase is the condition of 3: 1, carry out 4 stage countercurrent extractions; Described extraction agent two be preferably in extraction agent P507, extraction agent P204 and extraction agent Cyanex272 one or more, described thinner two is preferably sulfonated kerosene or/and 260# solvent oil, the extraction agent two that the present embodiment adopts is extraction agent P204 and extraction agent Cyanex272 2: 1 mixing solutionss mixed in mass ratio, and thinner two is sulfonated kerosene and 260# solvent oil 3: 1 mixtures mixed in mass ratio;
The sulfuric acid that step 405, employing concentration are 2.5mol/L carries out back extraction to nickel organic phase rich described in step 404, obtains nickel sulfate solution; The detailed process of described back extraction is: under the volume ratio of sulfuric acid and rich nickel organic phase is the condition of 1: 20, carry out 6 stage countercurrent extractions;
Step 406, employing gac carry out absorption oil removal treatment for sorbent material to nickel sulfate solution described in step 405, obtain the nickel sulfate solution after oil removing;
Step 407, by the nickel sulfate solution heating after oil removing described in step 406, to be concentrated into nickel ion concentration be 120g/L, then naturally cools to crystallizing at room temperature 12h, obtain high-purity sulphuric acid nickel.
After testing, the quality product of the single nickel salt of the present embodiment regeneration is more as shown in table 4 with the associated specifications of national standard " GB/T26524-2011 ".
The quality product of the single nickel salt of table 4 the present embodiment regeneration compares table look-up with national standard
As can be seen from Table 4, the quality product of the single nickel salt that the present embodiment is prepared from nickel-base alloy materials recycling, higher than national standard " GB/T 26524-2011 " technical requirements, can be widely used in plating and battery industry.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. from nickel-base alloy waste material, regenerate a method for high-purity sulphuric acid nickel, it is characterized in that, the method comprises the following steps:
Step one, nickel-base alloy scrap melting is become liquid, obtain aluminium alloy;
Step 2, aluminium alloy described in step one carried out to atomization process, obtain powdered alloy;
Step 3, powdered alloy described in step 2 is placed in one section and leaches acid and carry out one section and leach process, after solid-liquid separation, obtain one section of leach liquor and one section of leached mud; In described one section of leaching acid, hydrionic concentration is 2mol/L ~ 5mol/L, and described one section is leached sour volume V
1meet: 4m
1≤ V
1≤ 8m
1, wherein m
1for the quality of powdered alloy, m
1unit be g, V
1unit be mL, described one section leach process temperature be 70 DEG C ~ 90 DEG C, described one section leach process time be 1h ~ 3h;
Step 4, one section of leach liquor described in step 3 and one section of leached mud to be processed respectively:
The treating processes of described one section of leached mud is: one section of leached mud is placed in two sections of leaching acid and carries out two sections of leaching process, obtaining two sections of leach liquors and two sections of leached muds after solid-liquid separation, is then replace one section to leach acid after 2mol/L ~ 5mol/L to recycle by hydrionic concentration adjustment in two sections of leach liquors; In described two sections of leaching acid, hydrionic concentration is 6mol/L ~ 9mol/L, and described two sections are leached sour volume V
2meet: 3m
2≤ V
2≤ 6m
2, wherein m
2be the quality of one section of leached mud, m
2unit be g, V
2unit be mL, described two sections leach process temperature be 70 DEG C ~ 90 DEG C, described two sections leach process times be 1h ~ 3h;
Described one section of leach liquor is processed to step 407 by step 401:
Step 401, adopt alkaline solution one to carry out one section of removing impurity by means of precipitation process for precipitation agent to one section of leach liquor, be till 3.5 ~ 4.0 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing a and Solid separate b; The temperature of described one section of removing impurity by means of precipitation process is 40 DEG C ~ 80 DEG C;
Step 402, adopt alkaline solution two to carry out two sections of removing impurity by means of precipitation process to the thing of liquid separation described in step 401 a for precipitation agent, be till 4.5 ~ 5.5 until the pH value of reaction system, after solid-liquid separation, obtain liquid separation thing c and Solid separate d; Containing nickel and cobalt in described liquid separation thing c; The temperature of described two sections of removing impurity by means of precipitation process is 40 DEG C ~ 80 DEG C;
Nickel in the thing of liquid separation described in step 402 c is separated with cobalt by the method for step 403, employing extraction, obtains rich cobalt extraction liquid and rich nickel raffinate; The detailed process of described extraction is: with liquid separation thing c for aqueous phase, with extraction agent one and thinner one by volume 1: the mixture that (2 ~ 5) mix, for organic phase, is (1 ~ 3) in the volume ratio of organic phase and aqueous phase: carry out 4 ~ 8 stage countercurrents under the condition of 1 and extract;
Sodium ion in rich nickel raffinate described in the method separation removing step 403 of step 404, employing extraction, or/and ammonium ion, obtains rich nickel organic phase; The detailed process of described extraction is: with rich nickel raffinate for aqueous phase, with extraction agent two and thinner two by volume 1: the mixture that (2 ~ 5) mix, for organic phase, is (1 ~ 3) in the volume ratio of organic phase and aqueous phase: carry out 4 ~ 8 stage countercurrents under the condition of 1 and extract;
Step 405, employing sulfuric acid carry out back extraction to nickel organic phase rich described in step 404, obtain nickel sulfate solution; The detailed process of described back extraction is: be 1 in the volume ratio of sulfuric acid and rich nickel organic phase: carry out 3 ~ 6 stage countercurrents extractions under the condition of (8 ~ 20);
Step 406, employing gac carry out absorption oil removal treatment for sorbent material to nickel sulfate solution described in step 405, obtain the nickel sulfate solution after oil removing;
Step 407, the nickel sulfate solution heating after oil removing described in step 406 is concentrated into nickel ion concentration and is not less than 120g/L, after crystallization, obtain high-purity sulphuric acid nickel; In described high-purity sulphuric acid nickel, the mass percentage of nickel is not less than 22%.
2. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, is characterized in that, in the waste material of nickel-base alloy described in step one, the mass percentage of nickel is not less than 50%.
3. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, is characterized in that, melting the equipment that nickel-base alloy waste material adopts in step one is medium frequency induction melting furnace, high-frequency induction smelting furnace or electric arc furnace.
4. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, is characterized in that, the concrete atomizing type being atomized process described in step 2 is aerosolization, water atomization or mixing wastewater with air atomization.
5. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, is characterized in that, described in step 3 one section to leach described in acid and step 4 two sections leach sour be in sulfuric acid, hydrochloric acid and nitric acid one or more.
6. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, it is characterized in that, alkaline solution two described in alkaline solution one described in step 401 and step 402 is the mixing solutions that basic cpd and deionized water mix, and wherein basic cpd is one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammoniacal liquor and bicarbonate of ammonia; Described alkaline solution one is 5% ~ 30% with the mass percentage of alkaline solution two neutral and alkali compound.
7. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, it is characterized in that, before solid-liquid separation being carried out to one section of Leaching Systems in step 3, in one section of Leaching Systems, add flocculation liquid in advance, the volume of the flocculation liquid added is one section and leaches 0.01% ~ 0.1% of sour volume; Described flocculation liquid be flocculation agent and deionized water in mass ratio (0.1 ~ 1): 1 mixing solutions mixed, described flocculation agent is cationic-type polyacrylamide, anion-polyacrylamide, amphoteric ionic polyacrylamide or polymer polyacrylamide.
8. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, it is characterized in that, described in extraction agent one described in step 403 and step 404, extraction agent two is one or more in extraction agent P507, extraction agent P204 and extraction agent Cyanex272, and described thinner one and thinner two are sulfonated kerosene or/and 260# solvent oil.
9. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, is characterized in that, the concentration of sulfuric acid described in step 405 is 0.5mol/L ~ 2.5mol/L.
10. a kind of method regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material according to claim 1, is characterized in that, the time of crystallization described in step 407 is 6h ~ 12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510125711.6A CN104651620B (en) | 2015-03-20 | 2015-03-20 | Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510125711.6A CN104651620B (en) | 2015-03-20 | 2015-03-20 | Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104651620A true CN104651620A (en) | 2015-05-27 |
| CN104651620B CN104651620B (en) | 2017-04-12 |
Family
ID=53243256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510125711.6A Active CN104651620B (en) | 2015-03-20 | 2015-03-20 | Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104651620B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151739A (en) * | 2017-07-07 | 2017-09-12 | 金川集团股份有限公司 | A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel |
| CN109179756A (en) * | 2018-09-26 | 2019-01-11 | 衢州华友钴新材料有限公司 | A kind for the treatment of process purifying SS from hydrometallurgy cobalt copper solution |
| CN109750167A (en) * | 2019-03-20 | 2019-05-14 | 东北大学 | A method of recycling nickel from nickel base superalloy waste cut materials |
| CN109852794A (en) * | 2019-03-11 | 2019-06-07 | 西安蓝晓科技新材料股份有限公司 | A method of being used to prepare LITHIUM BATTERY nickel sulfate |
| CN110607439A (en) * | 2019-09-12 | 2019-12-24 | 金川集团股份有限公司 | Spherical nickel protoxide sectional oxidation acid leaching treatment method |
| CN111304446A (en) * | 2020-03-31 | 2020-06-19 | 中国科学院金属研究所 | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching |
| CN112897598A (en) * | 2021-02-07 | 2021-06-04 | 阳江市联邦金属化工有限公司 | Preparation method of superfine nickel protoxide |
| CN114517263A (en) * | 2022-02-21 | 2022-05-20 | 中南大学 | Method for extracting and recovering nickel from nickel-containing waste capacitor material and preparing nickel product |
| WO2023284441A1 (en) * | 2021-07-15 | 2023-01-19 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate from nickel-iron-copper alloy |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195870A (en) * | 2007-12-25 | 2008-06-11 | 金川集团有限公司 | Method for processing waste alloy of nickel cobalt |
| CN101824540A (en) * | 2009-12-10 | 2010-09-08 | 佛山市邦普镍钴技术有限公司 | Method for separating and reclaiming metal nickel and tin from waste materials containing nickel and tin |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
| CN102925695A (en) * | 2012-10-20 | 2013-02-13 | 贵研铂业股份有限公司 | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material |
| CN103131859A (en) * | 2013-03-06 | 2013-06-05 | 昆明理工大学 | Comprehensive recycling method for metals in superalloy scrap |
| CN103334017A (en) * | 2013-07-01 | 2013-10-02 | 贵研铂业股份有限公司 | Method for preparing high-purity nickel powder from waste high-temperature alloy |
-
2015
- 2015-03-20 CN CN201510125711.6A patent/CN104651620B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195870A (en) * | 2007-12-25 | 2008-06-11 | 金川集团有限公司 | Method for processing waste alloy of nickel cobalt |
| CN101824540A (en) * | 2009-12-10 | 2010-09-08 | 佛山市邦普镍钴技术有限公司 | Method for separating and reclaiming metal nickel and tin from waste materials containing nickel and tin |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
| CN102925695A (en) * | 2012-10-20 | 2013-02-13 | 贵研铂业股份有限公司 | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material |
| CN103131859A (en) * | 2013-03-06 | 2013-06-05 | 昆明理工大学 | Comprehensive recycling method for metals in superalloy scrap |
| CN103334017A (en) * | 2013-07-01 | 2013-10-02 | 贵研铂业股份有限公司 | Method for preparing high-purity nickel powder from waste high-temperature alloy |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151739B (en) * | 2017-07-07 | 2019-06-25 | 金川集团股份有限公司 | A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel |
| CN107151739A (en) * | 2017-07-07 | 2017-09-12 | 金川集团股份有限公司 | A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel |
| CN109179756A (en) * | 2018-09-26 | 2019-01-11 | 衢州华友钴新材料有限公司 | A kind for the treatment of process purifying SS from hydrometallurgy cobalt copper solution |
| CN109852794B (en) * | 2019-03-11 | 2022-02-15 | 西安蓝晓科技新材料股份有限公司 | Method for preparing battery-grade nickel sulfate |
| CN109852794A (en) * | 2019-03-11 | 2019-06-07 | 西安蓝晓科技新材料股份有限公司 | A method of being used to prepare LITHIUM BATTERY nickel sulfate |
| CN109750167A (en) * | 2019-03-20 | 2019-05-14 | 东北大学 | A method of recycling nickel from nickel base superalloy waste cut materials |
| CN110607439A (en) * | 2019-09-12 | 2019-12-24 | 金川集团股份有限公司 | Spherical nickel protoxide sectional oxidation acid leaching treatment method |
| CN111304446A (en) * | 2020-03-31 | 2020-06-19 | 中国科学院金属研究所 | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching |
| CN112897598A (en) * | 2021-02-07 | 2021-06-04 | 阳江市联邦金属化工有限公司 | Preparation method of superfine nickel protoxide |
| WO2023284441A1 (en) * | 2021-07-15 | 2023-01-19 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate from nickel-iron-copper alloy |
| GB2620310A (en) * | 2021-07-15 | 2024-01-03 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing nickel sulfate from nickel-iron-copper alloy |
| US11952289B2 (en) | 2021-07-15 | 2024-04-09 | Guangdong Brunp Recycling Technology Co., Ltd. | Method for preparing nickel sulfate from nickel-iron-copper alloy |
| CN114517263A (en) * | 2022-02-21 | 2022-05-20 | 中南大学 | Method for extracting and recovering nickel from nickel-containing waste capacitor material and preparing nickel product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104651620B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104651620B (en) | Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material | |
| CN107267759B (en) | A kind of comprehensive recovering process of anode material for lithium-ion batteries | |
| CN103168107B (en) | Method for recovering valuable metals from lithium secondary battery wastes | |
| CN111270073A (en) | Method for recovering valuable metals from leachate of waste lithium ion battery electrode material | |
| CN106611841B (en) | A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge | |
| CN106829907A (en) | A kind of method that nickel-contained pig iron prepares nickel sulfate solution and battery-grade iron phosphate | |
| CN104087755B (en) | A kind of recovery method of neodymium iron boron waste material rare earth elements | |
| CN104911359A (en) | Process method for extracting cobalt and nickel from manganese waste slag | |
| CN103849775B (en) | A kind of method reclaiming nickel and cobalt from high-temperature alloy waste material | |
| CN101824540A (en) | Method for separating and reclaiming metal nickel and tin from waste materials containing nickel and tin | |
| CN113060712B (en) | Method for preparing iron phosphate and nickel cobalt manganese hydroxide battery precursor material from metal nickel cobalt iron powder | |
| CN109811127A (en) | A method of recycling valuable metal from battery electrode material leachate | |
| CN108023134A (en) | The recovery method of valuable element in a kind of waste lithium ion battery electrode material | |
| CN102912137B (en) | Method for recovering cobalt and nickel from waste iron nickel cobalt alloy | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| CN109536728A (en) | A method of recycling nickel cobalt from battery electrode material leachate | |
| CN104388711A (en) | Method for recovering rare earth by leaching rare earth oxide molten slag | |
| CN105039724A (en) | Smelting furnace soot treatment method | |
| CN104674298B (en) | A kind of method that recovery prepares high purity nickel in return material from nickel base superalloy | |
| CN103334017A (en) | Method for preparing high-purity nickel powder from waste high-temperature alloy | |
| CN106981699A (en) | A kind of method that lithium is reclaimed from waste lithium iron phosphate battery | |
| CN102337412A (en) | Process for recovering zinc and iron from steel-making dust of waste galvanized plates | |
| CN103320624A (en) | Method for selectively extracting gold and silver from copper anode slime | |
| CN112481492A (en) | Method for recovering valuable metals from waste lithium battery lithium cobaltate positive electrode material | |
| CN116646633A (en) | Method for recycling active substances in lithium ion positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material Effective date of registration: 20190417 Granted publication date: 20170412 Pledgee: Xi'an Science and Technology Financial Service Center Co., Ltd. Pledgor: Xi'an Ruixinke Metal Material Co., Ltd. Registration number: 2019610000069 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20200401 Granted publication date: 20170412 Pledgee: Xi'an Science and Technology Financial Service Center Co., Ltd. Pledgor: XI'AN RAREALLOYS Co.,Ltd. Registration number: 2019610000069 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for regenerating high-purity nickel sulfate from nickel-based alloy waste material Effective date of registration: 20200408 Granted publication date: 20170412 Pledgee: Xi'an Science and Technology Financial Service Center Co., Ltd. Pledgor: XI'AN RAREALLOYS Co.,Ltd. Registration number: Y2020610000036 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20211214 Granted publication date: 20170412 Pledgee: Xi'an Science and Technology Financial Service Center Co.,Ltd. Pledgor: XI'AN RAREALLOYS CO.,LTD. Registration number: Y2020610000036 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for regenerating high purity nickel sulfate from nickel base alloy waste Effective date of registration: 20211215 Granted publication date: 20170412 Pledgee: Xi'an Science and Technology Financial Service Center Co.,Ltd. Pledgor: XI'AN RAREALLOYS CO.,LTD. Registration number: Y2021610000425 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |