CN104651620B - 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
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- CN104651620B CN104651620B CN201510125711.6A CN201510125711A CN104651620B CN 104651620 B CN104651620 B CN 104651620B CN 201510125711 A CN201510125711 A CN 201510125711A CN 104651620 B CN104651620 B CN 104651620B
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- sulphuric acid
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 238000000034 method Methods 0.000 title claims abstract description 140
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 93
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 44
- 230000001172 regenerating effect Effects 0.000 title abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 73
- 238000002386 leaching Methods 0.000 claims abstract description 71
- 238000000605 extraction Methods 0.000 claims abstract description 56
- 238000001556 precipitation Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 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
- -1 hydrogen ions Chemical class 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 91
- 238000006396 nitration reaction Methods 0.000 claims description 76
- 239000002585 base Substances 0.000 claims description 54
- 208000035126 Facies Diseases 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 239000003085 diluting agent Substances 0.000 claims description 26
- 229920002401 polyacrylamide Polymers 0.000 claims description 26
- 239000001117 sulphuric acid Substances 0.000 claims description 26
- 235000011149 sulphuric acid Nutrition 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 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
- 239000003513 alkali Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000005189 flocculation Methods 0.000 claims description 17
- 230000016615 flocculation Effects 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 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
- 239000002904 solvent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000000889 atomisation Methods 0.000 claims description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000005518 polymer electrolyte Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 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
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 1
- 235000011941 Tilia x europaea Nutrition 0.000 claims 1
- 239000004571 lime Substances 0.000 claims 1
- 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
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 20
- 239000000284 extract Substances 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 125000002091 cationic group Chemical group 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
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 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
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- 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, and in particular to one kind regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material
Method.
Background technology
Nickel is important strategic reserves metal, is widely used in the aspects such as aviation, military project, chemical industry, electronics.China is to lack nickel
Country, with the fast development of China's economy and continually developing for new and high technology, range of application of the nickel in modern industry is not
Disconnected expansion, demand are improved constantly.China has become at present nickel country of consumption maximum in the world, but mineral resources day of nickel
It is gradually poor.Therefore, the various nickeliferous secondary resources of comprehensive development and utilization, are that the one kind for making up a mineral resources wretched insufficiency has
Effect approach and inevitable choice.
Containing substantial amounts of nickel and other valuable metals, Huge value in secondary resource nickel-base alloy waste material.Nickel-base alloy gives up
Material is mainly derived from：(1) rising head, shavings, car bits for producing in nickel-base alloy preparation process etc.；(2) nickel-base alloy component, zero
Part etc. casts and produces waste material with forging processing；(3) nickel-base alloy component, the parts of useful life are reached.
The existing reparation technology for preparing nickel sulfate such as patent CN 1544664A " water quenching converter mattes sulphuric acid Selectively leaching systems
Take LITHIUM BATTERY high-purity sulphuric acid nickel technique " it is described, a kind of method is that, by water quenching electricity nickel or Nickel tetracarbonyl. sulfuric acid dissolution, rich nickel solution steams
Send out crystallization to form；Another kind of method is to adopt low copper converter mattes or nickel-containing material for raw material, and Jing sulphuric acid pressure leachings are all valuable
Metal, then purification separation, evaporative crystallization extracting sulfuric acid nickel.
The research for regenerating high-purity sulphuric acid nickel from nickel-base alloy waste material at present not yet has been reported that.
The content of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, there is provided one kind is from nickel-base alloy
The method that high-purity sulphuric acid nickel is prepared in waste material.The method can be in efficient recovery nickel-base alloy waste material nickel and be prepared into high purity sulphur
Sour nickel so as to directly apply to the relevant industries such as accumulator, plating, with adaptability to raw material it is strong, product purity is high, environmental pollution
Little the features such as.
To solve above-mentioned technical problem, the technical solution used in the present invention is：One kind regenerates high from nickel-base alloy waste material
The method of pure nickel sulfate, it is characterised in that the method is comprised the following steps：
Step one, by nickel-base alloy scrap melting into liquid, obtain aluminium alloy；
Step 2, atomization process is carried out to aluminium alloy described in step one, obtain alloy powder；
Step 3, alloy powder described in step 2 is placed in one section leaches in acid and carry out one section of leaching process, solid-liquid point
One section of leachate and one section of leached mud are obtained after；It is 2mol/L～5mol/L that described one section is leached hydrionic concentration in acid,
Described one section volume V for leaching acid1Meet：4m1≤V1≤8m1, wherein m1For the quality of alloy powder, m1Unit be g, V1's
Unit is mL, and the temperature of one section of leaching process is 70 DEG C～90 DEG C, and the time of one section of leaching process is 1h～3h；
Step 4, one section of leachate described in step 3 and one section of leached mud are respectively processed：
The processing procedure of one section of leached mud is：One section of leached mud is placed in two-stage nitration leaching acid to be carried out at two-stage nitration leaching
Reason, obtains two-stage nitration leachate and two-stage nitration leached mud after solid-liquid separation, be then adjusted to hydrionic concentration in two-stage nitration leachate
Replace one section to leach acid after 2mol/L～5mol/L to recycle；The two-stage nitration leach hydrionic concentration in acid be 6mol/L～
9mol/L, the two-stage nitration leaches volume V of acid2Meet：3m2≤V2≤6m2, wherein m2For the quality of one section of leached mud, m2List
Position is g, V2Unit be mL, the temperature of the two-stage nitration leaching process is 70 DEG C～90 DEG C, the time of the two-stage nitration leaching process
For 1h～3h；
One section of leachate is processed by step 401 to step 407：
Step 401, adopt aqueous slkali one and carry out to one section of leachate for precipitant one section of removing impurity by means of precipitation to process, until reaction
Till the pH value of system is 3.5～4.0, liquid separator a and Solid separate b is obtained after solid-liquid separation；One section of precipitation
The temperature that remove impurity is processed is 40 DEG C～80 DEG C；
Step 402, adopt aqueous slkali two and carry out to a of liquid separator described in step 401 for precipitant two-stage nitration precipitation to remove
Reason is lived together, till the pH value of reaction system is 4.5～5.5, liquid separator c and Solid separate is obtained after solid-liquid separation
d；Containing nickel and cobalt in the liquid separator c；The temperature that the two-stage nitration removing impurity by means of precipitation is processed is 40 DEG C～80 DEG C；
Step 403, the method for employing extraction separate in the nickel in the c of liquid separator described in step 402 and cobalt, obtain richness
Cobalt extract and rich nickel raffinate；The detailed process of the extraction is：With liquid separator c as water phase, with extractant one with it is dilute
Release agent one by volume 1: the mixture that (2～5) mix is organic faciess, be (1～3) in the volume ratio of organic faciess and water phase
: 4～8 stage countercurrents extraction is carried out under conditions of 1；
Step 404, be separated off described in step 403 using the method for extraction sodium ion in rich nickel raffinate or/and
Ammonium ion, obtains rich nickel organic faciess；The detailed process of the extraction is：With rich nickel raffinate as water phase, with extractant two with it is dilute
Release agent two by volume 1: the mixture that (2～5) mix is organic faciess, be (1～3) in the volume ratio of organic faciess and water phase
: 4～8 stage countercurrents extraction is carried out under conditions of 1；
Step 405, back extraction is carried out to rich nickel organic faciess described in step 404 using sulphuric acid, obtain nickel sulfate solution；It is described
The detailed process of back extraction is：It is 1 in the volume ratio of sulphuric acid and rich nickel organic faciess: 3～6 stage countercurrents are carried out under conditions of (8～20)
Extraction；
Step 406, adopt activated carbon absorption oil removal treatment carried out to nickel sulfate solution described in step 405 for adsorbent,
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, obtains high-purity sulphuric acid nickel after crystallization；The weight/mass percentage composition of nickel is not less than 22% in the high-purity sulphuric acid nickel.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step one
The weight/mass percentage composition for stating nickel in nickel-base alloy waste material is not less than 50%.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that melt in step one
The equipment that change nickel-base alloy waste material is adopted is for medium frequency induction melting furnace, high-frequency induction smelting furnace or electric arc furnace.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step 2
The concrete atomizing type for stating atomization process is the atomization of aerosolization, water atomization or mixing wastewater with air.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step 3
State one section leach that two-stage nitration described in acid and step 4 leaches that acid is in sulphuric acid, hydrochloric acid and nitric acid one or more.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step 401
State aqueous slkali two described in aqueous slkali one and step 402 and be the mixed solution that alkali compoundss are mixed with deionized water,
Wherein alkali compoundss are the one kind or two in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate
More than kind；The aqueous slkali one is 5%～30% with the weight/mass percentage composition of the neutral and alkali compound of aqueous slkali two.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that step 3 is right
One section of Leaching Systems is carried out before solid-liquid separation, adds flocculation liquid in one section of Leaching Systems in advance, the flocculation liquid for being added
Volume is one section of leach sour volume 0.01%～0.1%；The flocculation liquid is flocculant and deionized water in mass ratio (0.1
～1): 1 mixed solution for mixing, the flocculant be cationic-type polyacrylamide, anion-polyacrylamide, two
Property Polyacrylamide or polymer electrolyte polyacrylamide.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step 403
State extractant two described in extractant one and step 404 to be in extractant P507, extractant P204 and extractant Cyanex272
One or more, the diluent one and diluent two are sulfonated kerosene or/and 260# solvent naphthas.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step 405
The concentration for stating sulphuric acid is 0.5mol/L～2.5mol/L.
The method that high-purity sulphuric acid nickel is regenerated in a kind of above-mentioned waste material from nickel-base alloy, it is characterised in that institute in step 407
The time for stating crystallization is 6h～12h.
The present invention has compared with prior art advantages below：
1st, the invention provides preparing the new approaches of high-purity sulphuric acid nickel in a kind of waste material from nickel-base alloy.The present invention can have
Effect reclaims the nickel in nickel-base alloy waste material and makes high-purity sulphuric acid nickel so as to directly apply to the relevant industries such as accumulator, plating,
With adaptability to raw material it is strong, product purity is high, environmental pollution is little the features such as.
2nd, the present invention efficiently soaks metallic nickel from nickel-base alloy waste material initially with fusing, atomization and the method for leaching
Go out and proceed in solution, then by the method for precipitation, extraction, back extraction, oil removing and evaporative crystallization rich nickel leachate is carried out by
Layer depth is purified, and finally prepares high-purity sulphuric acid nickel.
3rd, using the nickel content in the solid slag thing of present invention acquisition below 0.5%, nickel leaching rate is more than 99%, and nickel is returned
Yield is more than 96%, and the product quality of the nickel sulfate of preparation is higher than GB《GB/T26524-2011》Require.
4th, using the inventive method can be in efficient recovery nickel-base alloy waste material nickel and make high-purity sulphuric acid nickel, and can be directly
It is applied to the relevant industries such as accumulator, plating.Solid separate obtained in the present invention can be used to further reclaiming tungsten, molybdenum,
The rare elements such as tantalum, chromium.
5th, the whole technical process of the present invention is almost pollution-free to environment, is a kind of efficiency high, low cost, eco-friendly side
Method.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Description of the drawings
Fig. 1 is the process chart that the present invention regenerates high-purity sulphuric acid nickel from nickel-base alloy waste material.
Specific embodiment
Embodiment 1
With reference to Fig. 1, the present embodiment regenerates the method for high-purity sulphuric acid nickel from nickel-base alloy waste material and comprises the following steps：
Step one, nickel-base alloy waste material is fused into into liquid in high-frequency induction smelting furnace, obtains aluminium alloy；After testing,
62.34wt% containing Ni, 8.67wt% containing Co in the nickel-base alloy waste material；
Step 2, atomization process is carried out to aluminium alloy described in step one using the method for water atomization, obtain alloy powder；
Step 3, alloy powder described in step 2 is placed in one section leaches in acid and carry out one section of leaching process, solid-liquid point
One section of leachate and one section of leached mud are obtained after；It is described one section leach acid in hydrionic concentration be 2mol/L, described one section
Leach volume V of acid1Meet：V1=5m1, wherein m1For the quality of alloy powder, m1Unit be g, V1Unit be mL, it is described
The temperature of one section of leaching process is 75 DEG C, and the time of one section of leaching process is 1.5h；Described one section is leached acid and is preferably sulfur
One or more in acid, hydrochloric acid and nitric acid, adopts one section of the present embodiment leaches sour for nitric acid；
Before solid-liquid separation is carried out to one section of Leaching Systems, flocculation liquid is added in one section of Leaching Systems in advance, it is described
The volume of flocculation liquid is one section of leach sour volume 0.03%；The flocculation liquid is flocculant and deionized water in mass ratio 0.2:
1 mixed solution for mixing, the flocculant be preferably cationic-type polyacrylamide, anion-polyacrylamide, two
Property Polyacrylamide or polymer electrolyte polyacrylamide, the flocculant that the present embodiment is adopted is for cationic polyacrylamide
Amine；
Step 4, one section of leachate described in step 3 and one section of leached mud are respectively processed：
The processing procedure of one section of leached mud is：One section of leached mud is placed in two-stage nitration leaching acid to be carried out at two-stage nitration leaching
Reason, obtains two-stage nitration leachate and two-stage nitration leached mud after solid-liquid separation, be then adjusted to hydrionic concentration in two-stage nitration leachate
Replace one section to leach acid after 2mol/L to recycle；It is 6mol/L that the two-stage nitration leaches hydrionic concentration in acid, the two-stage nitration
Leach volume V of acid2Meet：V2=4.5m2, wherein m2For the quality of one section of leached mud, m2Unit be g, V2Unit be mL,
The temperature of the two-stage nitration leaching process is 85 DEG C, and the time of the two-stage nitration leaching process is 2h；The two-stage nitration leaches acid and is preferably
One or more in sulphuric acid, hydrochloric acid and nitric acid, the two-stage nitration that the present embodiment is adopted leaches acid for nitric acid；
One section of leachate is processed by step 401 to step 407：
Step 401, adopt aqueous slkali one and carry out to one section of leachate for precipitant one section of removing impurity by means of precipitation to process, until reaction
Till the pH value of system is 4.0, liquid separator a and Solid separate b is obtained after solid-liquid separation；At one section of removing impurity by means of precipitation
The temperature of reason is 70 DEG C；The mixed solution that the aqueous slkali one is mixed for alkali compoundss and deionized water, its neutral and alkali
Compound be preferably in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate one or two with
On；The aqueous slkali one that the present embodiment is adopted is for trisodium phosphate aqueous solution that weight/mass percentage composition is 5%；
In specific implementation process, can by Solid separate b acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing b proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 402, adopt aqueous slkali two and carry out to a of liquid separator described in step 401 for precipitant two-stage nitration precipitation to remove
Reason is lived together, till the pH value of reaction system is 4.5, liquid separator c and Solid separate d is obtained after solid-liquid separation；Institute
State in liquid separator c containing nickel and cobalt；The temperature that the two-stage nitration removing impurity by means of precipitation is processed is 70 DEG C；The aqueous slkali two is alkalescence
The mixed solution that compound is mixed with deionized water, wherein alkali compoundss are preferably sodium hydroxide, sodium carbonate, bicarbonate
One or more in sodium, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate；The aqueous slkali two that the present embodiment is adopted is for quality percentage
Content is 20% ammonium bicarbonate aqueous solution；
In specific implementation process, can by Solid separate d acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing d proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 403, the method for employing extraction separate in the nickel in the c of liquid separator described in step 402 and cobalt, obtain richness
Cobalt extract and rich nickel raffinate；The detailed process of the extraction is：With liquid separator c as water phase, with extractant one with it is dilute
By volume 1: 3 mixture for mixing is organic faciess to release agent one, under conditions of the volume ratio of organic faciess and water phase is for 1: 1
Carry out 4 stage countercurrent extractions；The extractant one is preferably in extractant P507, extractant P204 and extractant Cyanex272
Plant or two or more, the diluent one is preferably sulfonated kerosene or/and 260# solvent naphthas, the extractant one that the present embodiment is adopted
For extractant Cyanex272, diluent one is sulfonated kerosene；
Step 404, be separated off described in step 403 using the method for extraction sodium ion and ammonium in rich nickel raffinate from
Son, obtains rich nickel organic faciess；The detailed process of the extraction is：With rich nickel raffinate as water phase, with extractant two and diluent
Two by volume 1: 3 mixture for mixing be organic faciess, organic faciess and water phase volume ratio be 2: 1 under conditions of carry out
8 stage countercurrents extract；The extractant two be preferably extractant P507, extractant P204 and extractant Cyanex272 in one kind or
Two or more, the diluent two is preferably sulfonated kerosene or/and 260# solvent naphthas, and the extractant two that the present embodiment is adopted is extraction
Agent P507 is taken, diluent two is sulfonated kerosene；
Step 405, adopt concentration back extraction is carried out to rich nickel organic faciess described in step 404 for the sulphuric acid of 1.2mol/L, obtain
To nickel sulfate solution；The detailed process of the back extraction is：Enter under conditions of the volume ratio of sulphuric acid and rich nickel organic faciess is for 1: 15
The stage countercurrent of row 6 extracts；
Step 406, adopt activated carbon absorption oil removal treatment carried out to nickel sulfate solution described in step 405 for adsorbent,
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 into nickel ion concentration for 135g/
L, then naturally cools to crystallizing at room temperature 9h, obtains high-purity sulphuric acid nickel.
After testing, the product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation
Technical requirements are more as shown in table 1.
The product quality of the nickel sulfate of the present embodiment of table 1 regeneration compares catalog with national standard
As it can be seen from table 1 the product quality of nickel sulfate that the present embodiment is prepared from nickel-base alloy materials recycling is higher than state
Family's standard《GB/T 26524-2011》Technical requirements, main metal nickel content is much larger than 22%, can be widely applied to plating and battery
Industry.
Embodiment 2
With reference to Fig. 1, the present embodiment regenerates the method for high-purity sulphuric acid nickel from nickel-base alloy waste material and comprises the following steps：
Step one, nickel-base alloy waste material is fused into into liquid in electric arc furnace, obtains aluminium alloy；After testing, it is described Ni-based
58.31wt% containing Ni in alloyed scrap, 10.24wt% containing Co；
Step 2, atomization process is carried out to aluminium alloy described in step one using the method for aerosolization, obtain alloy powder；
Step 3, alloy powder described in step 2 is placed in one section leaches in acid and carry out one section of leaching process, solid-liquid point
One section of leachate and one section of leached mud are obtained after；It is described one section leach acid in hydrionic concentration be 4mol/L, described one section
Leach volume V of acid1Meet：V1=6m1, wherein m1For the quality of alloy powder, m1Unit be g, V1Unit be mL, it is described
The temperature of one section of leaching process is 80 DEG C, and the time of one section of leaching process is 2h；It is described one section leach acid be preferably sulphuric acid,
One or more in hydrochloric acid and nitric acid, adopt one section of the present embodiment leaches acid for hydrochloric acid；
Before solid-liquid separation is carried out to one section of Leaching Systems, flocculation liquid is added in one section of Leaching Systems in advance, it is described
The volume of flocculation liquid is one section of leach sour volume 0.05%；The flocculation liquid is flocculant and deionized water in mass ratio 0.5:
1 mixed solution for mixing, the flocculant be preferably cationic-type polyacrylamide, anion-polyacrylamide, two
Property Polyacrylamide or polymer electrolyte polyacrylamide, the flocculant that the present embodiment is adopted is anionic polyacrylamide
Amine；
Step 4, one section of leachate described in step 3 and one section of leached mud are respectively processed：
The processing procedure of one section of leached mud is：One section of leached mud is placed in two-stage nitration leaching acid to be carried out at two-stage nitration leaching
Reason, obtains two-stage nitration leachate and two-stage nitration leached mud after solid-liquid separation, be then adjusted to hydrionic concentration in two-stage nitration leachate
Replace one section to leach acid after 4mol/L to recycle；It is 8mol/L that the two-stage nitration leaches hydrionic concentration in acid, the two-stage nitration
Leach volume V of acid2Meet：V2=5m2, wherein m2For the quality of one section of leached mud, m2Unit be g, V2Unit be mL, institute
The temperature for stating two-stage nitration leaching process is 80 DEG C, and the time of the two-stage nitration leaching process is 2h；The two-stage nitration leaches acid and is preferably sulfur
One or more in acid, hydrochloric acid and nitric acid, the two-stage nitration that the present embodiment is adopted leaches sour for hydrochloric acid；
One section of leachate is processed by step 401 to step 407：
Step 401, adopt aqueous slkali one and carry out to one section of leachate for precipitant one section of removing impurity by means of precipitation to process, until reaction
Till the pH value of system is 3.5, liquid separator a and Solid separate b is obtained after solid-liquid separation；At one section of removing impurity by means of precipitation
The temperature of reason is 80 DEG C；The mixed solution that the aqueous slkali one is mixed for alkali compoundss and deionized water, its neutral and alkali
Compound be preferably in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate one or two with
On；The aqueous slkali one that the present embodiment is adopted is for ammonia spirit that weight/mass percentage composition is 10%；
In specific implementation process, can by Solid separate b acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing b proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 402, adopt aqueous slkali two and carry out to a of liquid separator described in step 401 for precipitant two-stage nitration precipitation to remove
Reason is lived together, till the pH value of reaction system is 5.0, liquid separator c and Solid separate d is obtained after solid-liquid separation；Institute
State in liquid separator c containing nickel and cobalt；The temperature that the two-stage nitration removing impurity by means of precipitation is processed is 60 DEG C；The aqueous slkali two is alkalescence
The mixed solution that compound is mixed with deionized water, wherein alkali compoundss are preferably sodium hydroxide, sodium carbonate, bicarbonate
One or more in sodium, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate；The aqueous slkali two that the present embodiment is adopted is for quality percentage
Content is 30% ammonium bicarbonate aqueous solution；
In specific implementation process, can by Solid separate d acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing d proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 403, the method for employing extraction separate in the nickel in the c of liquid separator described in step 402 and cobalt, obtain richness
Cobalt extract and rich nickel raffinate；The detailed process of the extraction is：With liquid separator c as water phase, with extractant one with it is dilute
By volume 1: 4 mixture for mixing is organic faciess to release agent one, under conditions of the volume ratio of organic faciess and water phase is for 2: 1
Carry out 4 stage countercurrent extractions；The extractant one is preferably in extractant P507, extractant P204 and extractant Cyanex272
Plant or two or more, the diluent one is preferably sulfonated kerosene or/and 260# solvent naphthas, the extractant one that the present embodiment is adopted
For extractant P507, diluent one is 260# solvent naphthas；
Step 404, the method for employing extraction are separated off the ammonium ion described in step 403 in rich nickel raffinate, obtain
Rich nickel organic faciess；The detailed process of the extraction is：With rich nickel raffinate as water phase, volume is pressed with extractant two and diluent two
The mixture mixed than 1: 4 is organic faciess, and under conditions of the volume ratio of organic faciess and water phase is for 2: 18 stage countercurrents are carried out
Extraction；The extractant two be preferably extractant P507, extractant P204 and extractant Cyanex272 in one or two with
On, the diluent two is preferably sulfonated kerosene or/and 260# solvent naphthas, and the extractant two that the present embodiment is adopted is for extractant
P204, diluent two is 260# solvent naphthas；
Step 405, adopt concentration back extraction is carried out to rich nickel organic faciess described in step 404 for the sulphuric acid of 1.5mol/L, obtain
To nickel sulfate solution；The detailed process of the back extraction is：Enter under conditions of the volume ratio of sulphuric acid and rich nickel organic faciess is for 1: 15
The stage countercurrent of row 3 extracts；
Step 406, adopt activated carbon absorption oil removal treatment carried out to nickel sulfate solution described in step 405 for adsorbent,
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 into nickel ion concentration for 124g/
L, then naturally cools to crystallizing at room temperature 10h, obtains high-purity sulphuric acid nickel.
After testing, the product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation
Technical requirements are more as shown in table 2.
The product quality of the nickel sulfate of the present embodiment of table 2 regeneration compares catalog with national standard
From table 2 it can be seen that the product quality of nickel sulfate that the present embodiment is prepared from nickel-base alloy materials recycling is higher than state
Family's standard《GB/T 26524-2011》Technical requirements, can be widely applied to plating and battery industry.
Embodiment 3
With reference to Fig. 1, the present embodiment regenerates the method for high-purity sulphuric acid nickel from nickel-base alloy waste material and comprises the following steps：
Step one, nickel-base alloy waste material is fused into into liquid in medium frequency induction melting furnace, obtains aluminium alloy；After testing,
50.21wt% containing Ni, 9.77wt% containing Co in the nickel-base alloy waste material；
Step 2, atomization process is carried out to aluminium alloy described in step one using the method for water atomization, obtain alloy powder；
Step 3, alloy powder described in step 2 is placed in one section leaches in acid and carry out one section of leaching process, solid-liquid point
One section of leachate and one section of leached mud are obtained after；It is described one section leach acid in hydrionic concentration be 5mol/L, described one section
Leach volume V of acid1Meet：V1=4m1, wherein m1For the quality of alloy powder, m1Unit be g, V1Unit be mL, it is described
The temperature of one section of leaching process is 70 DEG C, and the time of one section of leaching process is 3h；It is described one section leach acid be preferably sulphuric acid,
One or more in hydrochloric acid and nitric acid, adopt one section of the present embodiment leaches acid for sulphuric acid；
Before solid-liquid separation is carried out to one section of Leaching Systems, flocculation liquid is added in one section of Leaching Systems in advance, it is described
The volume of flocculation liquid is one section of leach sour volume 0.01%；The flocculation liquid is flocculant and deionized water in mass ratio 0.1:
1 mixed solution for mixing, the flocculant be preferably cationic-type polyacrylamide, anion-polyacrylamide, two
Property Polyacrylamide or polymer electrolyte polyacrylamide, the flocculant that the present embodiment is adopted is amphoteric ion type polypropylene
Amide；
Step 4, one section of leachate described in step 3 and one section of leached mud are respectively processed：
The processing procedure of one section of leached mud is：One section of leached mud is placed in two-stage nitration leaching acid to be carried out at two-stage nitration leaching
Reason, obtains two-stage nitration leachate and two-stage nitration leached mud after solid-liquid separation, be then adjusted to hydrionic concentration in two-stage nitration leachate
Replace one section to leach acid after 5mol/L to recycle；It is 8mol/L that the two-stage nitration leaches hydrionic concentration in acid, the two-stage nitration
Leach volume V of acid2Meet：V2=3m2, wherein m2For the quality of one section of leached mud, m2Unit be g, V2Unit be mL, institute
The temperature for stating two-stage nitration leaching process is 90 DEG C, and the time of the two-stage nitration leaching process is 1h；The two-stage nitration leaches acid and is preferably sulfur
One or more in acid, hydrochloric acid and nitric acid, the two-stage nitration that the present embodiment is adopted leaches sour for sulphuric acid；
One section of leachate is processed by step 401 to step 407：
Step 401, adopt aqueous slkali one and carry out to one section of leachate for precipitant one section of removing impurity by means of precipitation to process, until reaction
Till the pH value of system is 3.5, liquid separator a and Solid separate b is obtained after solid-liquid separation；At one section of removing impurity by means of precipitation
The temperature of reason is 40 DEG C；The mixed solution that the aqueous slkali one is mixed for alkali compoundss and deionized water, its neutral and alkali
Compound be preferably in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate one or two with
On；The aqueous slkali one that the present embodiment is adopted is for aqueous sodium carbonate that weight/mass percentage composition is 30%；
In specific implementation process, can by Solid separate b acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing b proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 402, adopt aqueous slkali two and carry out to a of liquid separator described in step 401 for precipitant two-stage nitration precipitation to remove
Reason is lived together, till the pH value of reaction system is 4.5, liquid separator c and Solid separate d is obtained after solid-liquid separation；Institute
State in liquid separator c containing nickel and cobalt；The temperature that the two-stage nitration removing impurity by means of precipitation is processed is 40 DEG C；The aqueous slkali two is alkalescence
The mixed solution that compound is mixed with deionized water, wherein alkali compoundss are preferably sodium hydroxide, sodium carbonate, bicarbonate
One or more in sodium, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate；The aqueous slkali two that the present embodiment is adopted is for quality percentage
Content is 5% sodium hydrate aqueous solution；
In specific implementation process, can by Solid separate b acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing b proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 403, the method for employing extraction separate in the nickel in the c of liquid separator described in step 402 and cobalt, obtain richness
Cobalt extract and rich nickel raffinate；The detailed process of the extraction is：With liquid separator c as water phase, with extractant one with it is dilute
By volume 1: 2 mixture for mixing is organic faciess to release agent one, under conditions of the volume ratio of organic faciess and water phase is for 1: 1
Carry out 8 stage countercurrent extractions；The extractant one is preferably in extractant P507, extractant P204 and extractant Cyanex272
Plant or two or more, the diluent one is preferably sulfonated kerosene or/and 260# solvent naphthas, the extractant one that the present embodiment is adopted
For the mixture that extractant P507, extractant P204 and extractant Cyanex272 in mass ratio 1: 1: 2 are mixed, diluent
One is sulfonated kerosene；
Step 404, the method for employing extraction are separated off the ammonium ion described in step 403 in rich nickel raffinate, obtain
Rich nickel organic faciess；The detailed process of the extraction is：With rich nickel raffinate as water phase, volume is pressed with extractant two and diluent two
The mixture mixed than 1: 2 is organic faciess, and under conditions of the volume ratio of organic faciess and water phase is for 1: 14 stage countercurrents are carried out
Extraction；The extractant two be preferably extractant P507, extractant P204 and extractant Cyanex272 in one or two with
On, the diluent two is preferably sulfonated kerosene or/and 260# solvent naphthas, and the extractant two that the present embodiment is adopted is for extractant
The mixture that P507 and extractant P204 in mass ratio 3: 1 are mixed, diluent two is that sulfonated kerosene and 260# solvent naphthas are pressed
The mixture that mass ratio 2: 5 is mixed；
Step 405, adopt concentration back extraction is carried out to rich nickel organic faciess described in step 404 for the sulphuric acid of 0.5mol/L, obtain
To nickel sulfate solution；The detailed process of the back extraction is：Carry out under conditions of the volume ratio of sulphuric acid and rich nickel organic faciess is for 1: 8
3 stage countercurrents extract；
Step 406, adopt activated carbon absorption oil removal treatment carried out to nickel sulfate solution described in step 405 for adsorbent,
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 into nickel ion concentration for 130g/
L, then naturally cools to crystallizing at room temperature 6h, obtains high-purity sulphuric acid nickel.
After testing, the product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation
Technical requirements are more as shown in table 3.
The product quality of the nickel sulfate of the present embodiment of table 3 regeneration compares catalog with national standard
From table 3 it can be seen that the product quality of nickel sulfate that the present embodiment is prepared from nickel-base alloy materials recycling is higher than state
Family's standard《GB/T 26524-2011》Technical requirements, can be widely applied to plating and battery industry.
Embodiment 4
With reference to Fig. 1, the present embodiment regenerates the method for high-purity sulphuric acid nickel from nickel-base alloy waste material and comprises the following steps：
Step one, nickel-base alloy waste material is fused into into liquid in electric arc furnace, obtains aluminium alloy；After testing, it is described Ni-based
50.12wt% containing Ni in alloyed scrap, 9.6wt% containing Co；
Step 2, the method being atomized using mixing wastewater with air carry out atomization process to aluminium alloy described in step one, are closed
Bronze end；
Step 3, alloy powder described in step 2 is placed in one section leaches in acid and carry out one section of leaching process, solid-liquid point
One section of leachate and one section of leached mud are obtained after；It is described one section leach acid in hydrionic concentration be 5mol/L, described one section
Leach volume V of acid1Meet：V1=8m1, wherein m1For the quality of alloy powder, m1Unit be g, V1Unit be mL, it is described
The temperature of one section of leaching process is 90 DEG C, and the time of one section of leaching process is 1h；It is described one section leach acid be preferably sulphuric acid,
One or more in hydrochloric acid and nitric acid, adopt one section of the present embodiment leaches acid for hydrochloric acid and the mix acid liquor of sulphuric acid；
Before solid-liquid separation is carried out to one section of Leaching Systems, flocculation liquid is added in one section of Leaching Systems in advance, it is described
The volume of flocculation liquid is one section of leach sour volume 0.1%；The flocculation liquid is that flocculant and deionized water in mass ratio 1: 1 are mixed
Close mixed solution, the flocculant be preferably cationic-type polyacrylamide, anion-polyacrylamide, both sexes from
Subtype polyacrylamide or polymer electrolyte polyacrylamide, the flocculant that the present embodiment is adopted is polymer electrolyte polyacrylamide；
Step 4, one section of leachate described in step 3 and one section of leached mud are respectively processed：
The processing procedure of one section of leached mud is：One section of leached mud is placed in two-stage nitration leaching acid to be carried out at two-stage nitration leaching
Reason, obtains two-stage nitration leachate and two-stage nitration leached mud after solid-liquid separation, be then adjusted to hydrionic concentration in two-stage nitration leachate
Replace one section to leach acid after 5mol/L to recycle；It is 9mol/L that the two-stage nitration leaches hydrionic concentration in acid, the two-stage nitration
Leach volume V of acid2Meet：V2=6m2, wherein m2For the quality of one section of leached mud, m2Unit be g, V2Unit be mL, institute
The temperature for stating two-stage nitration leaching process is 70 DEG C, and the time of the two-stage nitration leaching process is 3h；The two-stage nitration leaches acid and is preferably sulfur
One or more in acid, hydrochloric acid and nitric acid, the two-stage nitration that the present embodiment is adopted leaches sour for sulphuric acid and the mixed acid of hydrochloric acid
Liquid；
One section of leachate is processed by step 401 to step 407：
Step 401, adopt aqueous slkali one and carry out to one section of leachate for precipitant one section of removing impurity by means of precipitation to process, until reaction
Till the pH value of system is 4.0, liquid separator a and Solid separate b is obtained after solid-liquid separation；At one section of removing impurity by means of precipitation
The temperature of reason is 80 DEG C；The mixed solution that the aqueous slkali one is mixed for alkali compoundss and deionized water, its neutral and alkali
Compound be preferably in sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate one or two with
On；The aqueous slkali one that the present embodiment is adopted is for ammonium bicarbonate aqueous solution that weight/mass percentage composition is 15%；
In specific implementation process, can by Solid separate b acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing b proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 402, adopt aqueous slkali two and carry out to a of liquid separator described in step 401 for precipitant two-stage nitration precipitation to remove
Reason is lived together, till the pH value of reaction system is 5.5, liquid separator c and Solid separate d is obtained after solid-liquid separation；Institute
State in liquid separator c containing nickel and cobalt；The temperature that the two-stage nitration removing impurity by means of precipitation is processed is 80 DEG C；The aqueous slkali two is alkalescence
The mixed solution that compound is mixed with deionized water, wherein alkali compoundss are preferably sodium hydroxide, sodium carbonate, bicarbonate
One or more in sodium, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate；The aqueous slkali two that the present embodiment is adopted is for quality percentage
Content is 5% aqueous sodium carbonate；
In specific implementation process, can by Solid separate b acid it is molten after carry out one section of removing impurity by means of precipitation again and process, make solid point
Nickel in thing b proceeds to liquid phase, so as to effectively reduce nickel loss；
Step 403, the method for employing extraction separate in the nickel in the c of liquid separator described in step 402 and cobalt, obtain richness
Cobalt extract and rich nickel raffinate；The detailed process of the extraction is：With liquid separator c as water phase, with extractant one with it is dilute
By volume 1: 5 mixture for mixing is organic faciess to release agent one, under conditions of the volume ratio of organic faciess and water phase is for 3: 1
Carry out 4 stage countercurrent extractions；The extractant one is preferably in extractant P507, extractant P204 and extractant Cyanex272
Plant or two or more, the diluent one is preferably sulfonated kerosene or/and 260# solvent naphthas, the extractant one that the present embodiment is adopted
For extractant P507, diluent one is the mixed solution that sulfonated kerosene and 260# solvent naphthas in mass ratio 1: 1 are mixed；
Step 404, be separated off described in step 403 using the method for extraction sodium ion and ammonium in rich nickel raffinate from
Son, obtains rich nickel organic faciess；The detailed process of the extraction is：With rich nickel raffinate as water phase, with extractant two and diluent
Two by volume 1: 5 mixture for mixing be organic faciess, organic faciess and water phase volume ratio be 3: 1 under conditions of carry out
4 stage countercurrents extract；The extractant two be preferably extractant P507, extractant P204 and extractant Cyanex272 in one kind or
Two or more, the diluent two is preferably sulfonated kerosene or/and 260# solvent naphthas, and the extractant two that the present embodiment is adopted is extraction
Take the mixed solution that agent P204 and extractant Cyanex272 in mass ratio 2: 1 are mixed, diluent two be sulfonated kerosene and
The mixture that 260# solvent naphthas in mass ratio 3: 1 are mixed；
Step 405, adopt concentration back extraction is carried out to rich nickel organic faciess described in step 404 for the sulphuric acid of 2.5mol/L, obtain
To nickel sulfate solution；The detailed process of the back extraction is：Enter under conditions of the volume ratio of sulphuric acid and rich nickel organic faciess is for 1: 20
The stage countercurrent of row 6 extracts；
Step 406, adopt activated carbon absorption oil removal treatment carried out to nickel sulfate solution described in step 405 for adsorbent,
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 into nickel ion concentration for 120g/
L, then naturally cools to crystallizing at room temperature 12h, obtains high-purity sulphuric acid nickel.
After testing, the product quality and national standard of the nickel sulfate of the present embodiment regeneration《GB/T26524-2011》Correlation
Technical requirements are more as shown in table 4.
The product quality of the nickel sulfate of the present embodiment of table 4 regeneration compares catalog with national standard
From table 4, it can be seen that the product quality of nickel sulfate that the present embodiment is prepared from nickel-base alloy materials recycling is higher than state
Family's standard《GB/T 26524-2011》Technical requirements, can be widely applied to plating and battery industry.
The above, is only presently preferred embodiments of the present invention, and not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence changes that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (9)
1. a kind of method that high-purity sulphuric acid nickel is regenerated in waste material from nickel-base alloy, it is characterised in that the method is comprised the following steps：
Step one, by nickel-base alloy scrap melting into liquid, obtain aluminium alloy；
Step 2, atomization process is carried out to aluminium alloy described in step one, obtain alloy powder；
Step 3, alloy powder described in step 2 is placed in one section leach acid in carry out one section of leaching process, after solid-liquid separation
Obtain one section of leachate and one section of leached mud；It is 2mol/L～5mol/L that described one section is leached hydrionic concentration in acid, described
One section of volume V for leaching acid1Meet：4m1≤V1≤8m1, wherein m1For the quality of alloy powder, m1Unit be g, V1Unit
For mL, the temperature of one section of leaching process is 70 DEG C～90 DEG C, and the time of one section of leaching process is 1h～3h；
One section of Leaching Systems is carried out before solid-liquid separation, flocculation liquid, the wadding for being added is added in one section of Leaching Systems in advance
The volume of lime set is one section of leach sour volume 0.01%～0.1%；The flocculation liquid is that flocculant and deionized water press quality
Than (0.1～1): 1 mixed solution for mixing, the flocculant is cationic-type polyacrylamide, anionic polypropylene
Amide, amphoteric ionic polyacrylamide or polymer electrolyte polyacrylamide；
Step 4, one section of leachate described in step 3 and one section of leached mud are respectively processed：
The processing procedure of one section of leached mud is：One section of leached mud is placed in two-stage nitration leaching acid carries out two-stage nitration leaching process,
Two-stage nitration leachate and two-stage nitration leached mud are obtained after solid-liquid separation, is then adjusted to hydrionic concentration in two-stage nitration leachate
Replace one section to leach acid after 2mol/L～5mol/L to recycle；The two-stage nitration leach hydrionic concentration in acid be 6mol/L～
9mol/L, the two-stage nitration leaches volume V of acid2Meet：3m2≤V2≤6m2, wherein m2For the quality of one section of leached mud, m2List
Position is g, V2Unit be mL, the temperature of the two-stage nitration leaching process is 70 DEG C～90 DEG C, the time of the two-stage nitration leaching process
For 1h～3h；
One section of leachate is processed by step 401 to step 407：
Step 401, adopt aqueous slkali one and carry out to one section of leachate for precipitant one section of removing impurity by means of precipitation to process, until reaction system
PH value be 3.5～4.0 till, liquid separator a and Solid separate b is obtained after solid-liquid separation；One section of removing impurity by means of precipitation
The temperature of process is 40 DEG C～80 DEG C；
Step 402, adopt aqueous slkali two a of liquid separator described in step 401 is carried out at two-stage nitration removing impurity by means of precipitation for precipitant
Reason, till the pH value of reaction system is 4.5～5.5, obtains liquid separator c and Solid separate d after solid-liquid separation；Institute
State in liquid separator c containing nickel and cobalt；The temperature that the two-stage nitration removing impurity by means of precipitation is processed is 40 DEG C～80 DEG C；
Step 403, the method for employing extraction separate in the nickel in the c of liquid separator described in step 402 and cobalt, obtain rich cobalt extraction
Take liquid and rich nickel raffinate；The detailed process of the extraction is：With liquid separator c as water phase, with extractant one and diluent
One by volume 1: the mixture that (2～5) mix is organic faciess, it is (1～3) in the volume ratio of organic faciess and water phase: 1
Under the conditions of carry out 4～8 stage countercurrents extraction；
Step 404, be separated off described in step 403 using the method for extraction sodium ion or/and ammonium in rich nickel raffinate from
Son, obtains rich nickel organic faciess；The detailed process of the extraction is：With rich nickel raffinate as water phase, with extractant two and diluent
Two by volume 1: the mixture that (2～5) mix is organic faciess, it is (1～3) in the volume ratio of organic faciess and water phase: 1
Under the conditions of carry out 4～8 stage countercurrents extraction；
Step 405, back extraction is carried out to rich nickel organic faciess described in step 404 using sulphuric acid, obtain nickel sulfate solution；The back extraction
Detailed process be：It is 1 in the volume ratio of sulphuric acid and rich nickel organic faciess: 3～6 stage countercurrents extraction is carried out under conditions of (8～20)；
Step 406, adopt activated carbon absorption oil removal treatment is carried out to nickel sulfate solution described in step 405 for adsorbent, obtain
Nickel sulfate solution after oil removing；
Step 407, the nickel sulfate solution heating after oil removing described in step 406 is concentrated into into nickel ion concentration not less than 120g/
L, obtains high-purity sulphuric acid nickel after crystallization；The weight/mass percentage composition of nickel is not less than 22% in the high-purity sulphuric acid nickel.
2. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
The weight/mass percentage composition of nickel is not less than 50% in nickel-base alloy waste material described in step one.
3. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
The equipment that fusing nickel-base alloy waste material is adopted in step one is for medium frequency induction melting furnace, high-frequency induction smelting furnace or electric arc furnace.
4. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
The concrete atomizing type of atomization process described in step 2 is the atomization of aerosolization, water atomization or mixing wastewater with air.
5. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
One section is leached one kind or two that the acid of two-stage nitration leaching described in acid and step 4 is in sulphuric acid, hydrochloric acid and nitric acid described in step 3
More than kind.
6. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
Aqueous slkali two is alkali compoundss and mixes with deionized water described in aqueous slkali one described in step 401 and step 402
Mixed solution, wherein alkali compoundss be sodium hydroxide, sodium carbonate, sodium bicarbonate, tertiary sodium phosphate, ammonia and ammonium hydrogen carbonate in
One or more；The weight/mass percentage composition of the aqueous slkali one and the neutral and alkali compound of aqueous slkali two is 5%～
30%.
7. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
Extractant two described in extractant one described in step 403 and step 404 is extractant P507, extractant P204 and extractant
One or more in Cyanex272, the diluent one and diluent two are sulfonated kerosene or/and 260# solvents
Oil.
8. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
The concentration of sulphuric acid described in step 405 is 0.5mol/L～2.5mol/L.
9. the method that high-purity sulphuric acid nickel is regenerated in a kind of waste material from nickel-base alloy according to claim 1, it is characterised in that
The time crystallized described in step 407 is 6h～12h.
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| 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 |
| CN109179756B (en) * | 2018-09-26 | 2022-02-11 | 衢州华友钴新材料有限公司 | Treatment process for purifying SS from hydrometallurgical 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 |
| 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 |
| CN113666437B (en) * | 2021-07-15 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for preparing nickel sulfate from nickel-iron-copper alloy |
| CN114517263B (en) * | 2022-02-21 | 2023-07-21 | 中南大学 | Method for extracting and recovering nickel from nickel-containing waste capacitor material and preparing nickel product |
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| 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 |
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