CN114369722B - Method for combined treatment of hard alloy grinding waste and scheelite - Google Patents
Method for combined treatment of hard alloy grinding waste and scheelite Download PDFInfo
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- CN114369722B CN114369722B CN202011116835.5A CN202011116835A CN114369722B CN 114369722 B CN114369722 B CN 114369722B CN 202011116835 A CN202011116835 A CN 202011116835A CN 114369722 B CN114369722 B CN 114369722B
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- sodium phosphate
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- 238000000227 grinding Methods 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000956 alloy Substances 0.000 title claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 33
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 88
- 238000002386 leaching Methods 0.000 claims abstract description 86
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 69
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 64
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 64
- 238000000926 separation method Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000002893 slag Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 24
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 24
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 24
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims abstract description 24
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims abstract description 24
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 14
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 abstract description 26
- 239000010937 tungsten Substances 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 description 20
- 229910017052 cobalt Inorganic materials 0.000 description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000004575 stone Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002351 wastewater Substances 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910052742 iron 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
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for jointly treating hard alloy grinding waste and scheelite, which comprises the following steps: stirring, mixing and leaching the hard alloy grinding waste and phosphoric acid, and then carrying out solid-liquid separation to obtain solid slag containing tungsten carbide and leaching liquid containing cobalt phosphate; stirring and mixing the leaching solution with alkali liquor for reaction, and then carrying out solid-liquid separation to obtain solid slag containing cobalt salt and alkaline sodium phosphate solution; cooling the alkaline sodium phosphate solution, and then carrying out solid-liquid separation to obtain a saturated sodium phosphate solution and sodium phosphate crystals; mixing scheelite with saturated sodium phosphate solution, ball milling, leaching the obtained ore pulp with sodium phosphate crystal and water, and then carrying out solid-liquid separation to obtain scheelite decomposition slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate. Therefore, the method realizes the efficient decomposition of the hard alloy grinding waste and scheelite by the circulation of phosphoric acid-sodium phosphate, realizes the combined treatment of primary and secondary tungsten resources, reduces the production cost and improves the utilization rate of tungsten resources.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal wet smelting, and particularly relates to a method for jointly treating hard alloy grinding waste and scheelite.
Background
The tungsten-based hard alloy can generate a large amount of grinding scraps in the grinding process, and the scraps contain a large amount of tungsten, a considerable amount of cobalt and a small amount of impurity elements such as silicon, copper, iron, chromium, vanadium, titanium, tantalum, niobium, nickel and the like, so that valuable metals in the scraps are recovered, and the comprehensive utilization of tungsten secondary resources can be realized. Based on the characteristic of coexistence of multiple elements in the hard alloy grinding material, in a wet recovery process adopted by the waste, an acid leaching process is generally adopted to separate tungsten from cobalt-nickel-iron and other impurity elements, so that tungsten exists in a solid phase in a tungsten carbide form, the cobalt-nickel-iron and other impurity elements enter a liquid phase in an ion form, and the tungsten is respectively transferred into a subsequent smelting process for treatment.
Research has found that PO 4 3- Easy to combine with Ca 2+ The formation of very poorly soluble compounds results in a great thermodynamic driving force for the decomposition of scheelite with phosphate, a good reagent for the decomposition of scheelite.
Thus, a method for combined treatment of cemented carbide grinding wastes and scheelite has yet to be studied.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, one purpose of the invention is to provide a method for jointly treating the grinding waste of hard alloy and scheelite, and the method is used for jointly treating the grinding waste and scheelite, so that the joint treatment of primary and secondary tungsten resources is realized, the production cost is greatly reduced, the utilization rate of tungsten resources is improved, and the method is environment-friendly.
The invention provides a method for jointly treating hard alloy grinding waste and scheelite. According to an embodiment of the present invention, the method for combined treatment of cemented carbide grinding waste and scheelite comprises:
(1) Mixing and leaching the hard alloy grinding waste with phosphoric acid with stirring, and then carrying out solid-liquid separation to obtain solid slag containing tungsten carbide and leaching liquid containing cobalt phosphate;
(2) Mixing the leaching solution containing cobalt phosphate with alkali liquor for reaction with stirring, and then carrying out solid-liquid separation to obtain solid slag containing cobalt salt and alkaline sodium phosphate solution;
(3) Cooling the alkaline sodium phosphate solution, and then performing solid-liquid separation to obtain a saturated sodium phosphate solution and sodium phosphate crystals;
(4) Mixing scheelite with the saturated sodium phosphate solution for ball milling, leaching the obtained ore pulp with the sodium phosphate crystal and water for solid-liquid separation, so as to obtain scheelite decomposition slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate.
According to the method for jointly treating the hard alloy grinding waste and the scheelite, disclosed by the embodiment of the invention, the hard alloy grinding waste and phosphoric acid are mixed and leached under the condition of stirring, metal elements such as nickel and cobalt in the hard alloy grinding waste react with the phosphoric acid to generate soluble phosphate, tungsten carbide in the hard alloy grinding waste still exists in a solid state, then solid-liquid separation is carried out, so that solid slag containing tungsten carbide and leaching liquid containing cobalt phosphate can be obtained through separation, the leaching liquid containing cobalt phosphate and alkaline liquor are mixed and reacted under the condition of stirring, cobalt in the leaching liquid reacts with the alkaline liquor to generate cobalt salt precipitate, and then solid-liquid separation is carried out, so that solid slag containing cobalt salt and alkaline sodium phosphate solution can be obtained, and the recovery of the metal elements such as cobalt in tungsten secondary resources is completed; then cooling the alkaline sodium phosphate solution, separating out a large number of sodium phosphate crystals from the solution, and performing solid-liquid separation after cooling to obtain a saturated sodium phosphate solution and sodium phosphate crystals; finally mixing scheelite with saturated sodium phosphate solution for ball milling, and leaching the obtained ore pulp, sodium phosphate crystal and water for reaction, wherein Ca in scheelite 2+ With PO (PO) 4 3- Binding to produce Ca 3 (PO 4 ) 2 And part of the basic calcium phosphate enters the slag phase, WO 4 2- And (3) the solution enters a liquid phase, and solid-liquid separation is carried out to obtain white tungsten decomposed slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate. Therefore, the method flexibly realizes the efficient decomposition of the hard alloy grinding waste and the scheelite by the circulation of the phosphoric acid-sodium phosphate, realizes the combined treatment of the primary resource and the secondary resource of tungsten, greatly reduces the production cost, improves the utilization rate of tungsten resources, and ensures the whole productionThe wastewater in the production process is discharged zero and is environment-friendly.
In addition, the method for combined treatment of cemented carbide grinding waste and scheelite according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, in step (1), the stirring rate is 100 to 500rpm and the mixed leaching time is 3 to 12 hours. Therefore, the uniformity and the sufficiency of the mixed leaching process of the hard alloy grinding waste and the phosphoric acid can be ensured, and a certain mixed leaching rate can be ensured, so that the production efficiency is improved.
In some embodiments of the invention, in step (1), the solid to liquid ratio of the cemented carbide grinding waste to the phosphoric acid is 1kg: (0.8-3) L. Therefore, on one hand, the leaching rate can be improved; on the other hand, the increase of the load of leaching and solid-liquid separation equipment or the loss of phosphoric acid can be avoided.
In some embodiments of the invention, in step (1), the phosphoric acid is used in an amount of 1.1 to 4 times the total theoretical amount required to leach the metal ions in the cemented carbide grinding waste. Therefore, on one hand, the sufficiency of the mixed leaching process of the hard alloy grinding waste and the phosphoric acid can be ensured; on the other hand, the loss of raw materials can be reduced.
In some embodiments of the invention, in step (2), the stirring rate is 100 to 500rpm. Therefore, the uniformity of the mixing reaction of the leaching solution containing the cobalt phosphate and the alkali liquor can be ensured, and a certain reaction rate can be ensured, so that the production efficiency is improved.
In some embodiments of the invention, in step (2), the temperature of the mixing reaction is 80-100 ℃ for 1-5 hours. Therefore, on one hand, the mixed reaction of the leaching solution containing the cobalt phosphate and the alkali liquor can be ensured to be carried out thoroughly; on the other hand, precipitation of sodium phosphate crystals can be avoided.
In some embodiments of the invention, in step (2), the amount of base in the lye is 3 to 6 times the amount of phosphoric acid in step (1). Thus, co in the leaching solution containing cobalt phosphate can be ensured 2+ The plasma precipitation is more thorough.
In some embodiments of the invention, in step (4), the solid-to-liquid ratio of the scheelite to the saturated sodium phosphate solution is 1kg: (0.2-1) L. Therefore, a certain ball milling efficiency can be ensured.
In some embodiments of the invention, in step (4), the particle size of scheelite in the slurry after ball milling is not less than 325 mesh. Thus, the leaching rate of scheelite can be increased.
In some embodiments of the invention, in step (4), the sodium phosphate crystals are added in an amount of 1.2 to 2 times the theoretical amount required for the decomposition of the scheelite. Thereby, the sufficiency of the scheelite decomposition can be ensured.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic flow diagram of a method for combined treatment of cemented carbide grinding waste and scheelite according to one embodiment of the invention;
fig. 2 is a schematic process flow diagram of the combined treatment of cemented carbide grinding waste and scheelite according to one embodiment of the invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The invention provides a method for jointly treating hard alloy grinding waste and scheelite. Referring to fig. 1-2, the method according to an embodiment of the present invention includes:
s100: mixing and leaching the hard alloy grinding waste and phosphoric acid with stirring, and then carrying out solid-liquid separation
In the step, the hard alloy grinding waste and phosphoric acid are mixed and leached under the conditions of room temperature and normal pressure with stirring, metal elements such as cobalt and the like react with the phosphoric acid to be converted into soluble ions, the soluble ions enter a liquid phase, tungsten element continuously exists in a solid phase in a form of tungsten carbide, and the pulp is subjected to solid-liquid separation after mixed leaching so as to obtain solid slag containing the tungsten carbide and leaching liquid containing the cobalt phosphate. Further, the stirring rate is 100 to 500rpm, preferably 300 to 400rpm. The mixed leaching time is 3-12 h, preferably 5-8 h. The inventors found that if the stirring rate is too low, the rate and uniformity of the mixed leaching will be affected; if the stirring rate is too high, the mixed leaching rate reaches a limit, and at the moment, the stirring rate is increased again, so that the mixed leaching rate is not increased continuously, but the energy consumption of equipment is increased. Meanwhile, if the mixed leaching time is too short, the leaching rate can be reduced; if the time of mixed leaching is too long, the production efficiency is reduced.
Further, the solid-to-liquid ratio of the cemented carbide grinding waste to the phosphoric acid is 1kg: (0.8 to 3) L, preferably 1kg: (1.2-1.8) L. The inventor finds that if the solid-liquid ratio of the hard alloy grinding waste to the phosphoric acid is too high, the viscosity of the ore pulp is increased, so that the mass transfer speed between solid and liquid phases is reduced, the leaching rate is reduced, and the stirring, conveying and solid-liquid separation of the ore pulp are not facilitated; if the solid-liquid ratio is too low, the load on the leaching and solid-liquid separation equipment or the loss of the leaching agent increases.
In addition, the phosphoric acid is used in an amount of 1.1 to 4 times, preferably 1.3 to 2.8 times, the total theoretical amount required for leaching the metal ions in the cemented carbide grinding waste. The inventor finds that if the ratio of the consumption of phosphoric acid to the total theoretical amount required for leaching the metal ions in the hard alloy grinding waste is too small, a part of metal elements such as cobalt in the hard alloy grinding waste can not be dissolved into a liquid phase, so that the recovery rate of the metal elements such as cobalt is reduced; if the ratio of the amount of phosphoric acid to the total theoretical amount required for leaching the metal ions in the cemented carbide grinding waste is too large, the loss of phosphoric acid is increased, and the production cost is increased.
It should be noted that, a person skilled in the art may select specific types of the stirring apparatus and the solid-liquid separation apparatus according to actual needs, so long as the above functions can be achieved.
S200: mixing the leaching solution containing cobalt phosphate with alkali liquor with stirring, and performing solid-liquid separation
In this step, co in the leaching solution containing cobalt phosphate is mixed with alkali liquor by stirring to react 2+ The plasma cations are combined with anions in the alkali liquor to form a precipitate, and solid-liquid separation is carried out after the mixed reaction so as to obtain solid slag containing cobalt salt and alkaline sodium phosphate solution, thereby completing recovery of metal elements such as cobalt and the like in tungsten secondary resources and conversion of phosphoric acid into sodium phosphate. The inventors found that increasing the alkali solution concentration can increase the concentration of ions in the solution after the reaction, which is advantageous for the subsequent precipitation of sodium phosphate crystals, whereas if a solid alkali is used, it may cause precipitation on the surface of the solid alkali to inhibit the further progress of the reaction, and therefore, a saturated alkali solution is preferably used. Notably, to prevent Na during the mixing reaction 3 PO 4 The crystal is precipitated at the reaction temperature, and the water addition amount is determined according to the solubility of sodium phosphate at the reaction temperature. Further, the stirring rate is 100 to 500rpm, preferably 300 to 400rpm. The inventor finds that if the stirring speed is too low, the mixing reaction speed is reduced, and the mixing reaction time is prolonged; and if the stirring rate is too high, the energy consumption increases.
Further, the temperature of the mixing reaction is 80-100 ℃, preferably 85-95 ℃, and the time is 1-5 hours, preferably 2-3 hours. The inventor finds that if the temperature of the mixing reaction is too low, the mixing reaction rate is reduced, the mixing reaction time is prolonged, and sodium phosphate in a liquid phase is easy to precipitate at too low temperature; if the temperature of the mixing reaction is too high, the load of the subsequent cooling step increases.
In addition, the amount of alkali in the alkali solution is 3 to 6 times, preferably 3.5 to 5 times, the amount of phosphoric acid in step S100. The inventors found that if the ratio of the amount of alkali in the alkali solution to the amount of phosphoric acid in step S100 is too small, it is impossible to obtain a solutionCo in leaching solution containing cobalt phosphate 2+ The plasma is thoroughly precipitated, so that the recovery rate of metal elements such as cobalt and the like can be reduced; if the ratio of the amount of alkali in the alkali solution to the amount of phosphoric acid in step S100 is too large, the alkali loss increases.
It should be noted that, a person skilled in the art may choose a specific type of lye according to actual needs, for example, the lye is at least one of a sodium hydroxide solution and a sodium carbonate solution. In addition, the specific types of the stirring device and the solid-liquid separation device are the same as those described above, and are not repeated here.
S300: cooling the alkaline sodium phosphate solution and then carrying out solid-liquid separation
In this step, the alkaline sodium phosphate solution obtained in step S200 is cooled, and as the solution temperature decreases, the solubility of sodium phosphate also decreases, and a supersaturated solution is formed, and at this time, sodium phosphate is crystallized from the solution, and is cooled to room temperature and then subjected to solid-liquid separation, so that a saturated sodium phosphate solution and sodium phosphate crystals are obtained. It should be noted that, the solid-liquid separation apparatus is the same as the above description, and will not be repeated here.
S400: mixing scheelite with saturated sodium phosphate solution, ball milling, leaching the obtained ore pulp with sodium phosphate crystal and water, and solid-liquid separation
In this step, the scheelite and saturated sodium phosphate solution are fed into a ball mill to be mixed and ball-milled, and the obtained pulp is leached with sodium phosphate crystals and water at high temperature, and in this process CaWO in the scheelite 4 With PO (PO) 4 3- Reacting to generate calcium phosphate and partial basic calcium phosphate, entering a slag phase to generate sodium tungstate, entering a liquid phase, and carrying out solid-liquid separation after the reaction is finished so as to obtain white tungsten decomposed slag containing the calcium phosphate and the basic calcium phosphate and a solution containing crude sodium tungstate. The inventor discovers that if the alkaline sodium phosphate solution obtained in the step S200 is directly mixed with scheelite without cooling for ball milling and leaching, the solution concentration is high, and the solution is likely to be precipitated due to temperature reduction in the process of transferring the solution, so that a pipeline is blocked, or the obtained alkaline sodium phosphate solution cannot be timely obtainedWhen the process is transferred to the next process and must be stored, crystallization will occur in the storage tank. Therefore, the alkaline sodium phosphate solution needs to be stabilized at room temperature and then transferred to the next process. Preferably, the leaching process described above is carried out in an autoclave. Further, the solid-to-liquid ratio of the scheelite to the saturated sodium phosphate solution is 1kg: (0.2 to 1) L, preferably 1kg: (0.5-0.8) L. The inventor finds that if the solid-to-liquid ratio is too small, the viscosity of ore pulp is small, the buoyancy of the ore pulp to the ball stones in the ball mill is small, scheelite is not easy to adhere to the surfaces of the ball stones, direct contact between the ball stones is easy to be caused, the grinding and crushing effects on the scheelite are difficult to be achieved, the ball milling efficiency is reduced, and the abrasion of the ball stones is increased; if the solid-liquid ratio is too large, the ore pulp is adhered to the surface of the ball stone and is not easy to separate, the ore pulp and the ball stone cannot perform relative grinding movement, the grinding effect on scheelite cannot be achieved, and the direct collision between the ball stone wrapped with scheelite and the ball stone or between the ball stone and the lining of the ball mill is caused seriously, so that the ball stone is broken and the lining is damaged.
Further, the particle size of scheelite in the ore pulp after ball milling is not less than 325 meshes. The inventors found that if the particle size of the scheelite after ball milling is too large, the leaching rate is reduced.
The amount of the sodium phosphate crystal to be used is 1.2 to 2 times, preferably 1.4 to 1.8 times, the theoretical amount required for decomposing the scheelite. The inventor finds that if the ratio of the dosage of the sodium phosphate crystal to the theoretical amount required by the decomposition of scheelite is too small, the leaching rate of tungsten element is low; if the ratio of the amount of sodium phosphate crystals to the theoretical amount required for decomposing scheelite is too large, the loss of sodium phosphate crystals increases.
It should be noted that, a person skilled in the art may select a specific type of the ball mill according to actual needs, so long as the above functions can be achieved. Meanwhile, the type of the solid-liquid separation device is the same as that described above, and the description thereof is omitted here.
The inventor found that by mixing and leaching the hard alloy grinding waste material and phosphoric acid under the condition of stirring, metal elements such as nickel, cobalt and the like in the hard alloy grinding waste material react with the phosphoric acid to generate soluble phosphate, and the hard alloy grinding waste materialThe tungsten carbide still exists in a solid state, then solid-liquid separation is carried out, namely solid slag containing tungsten carbide and leaching solution containing cobalt phosphate can be obtained by separation, the leaching solution containing cobalt phosphate and alkali liquor are mixed and reacted under the condition of stirring, cobalt in the leaching solution and the alkali liquor react to generate cobalt salt precipitate, and then solid-liquid separation is carried out, namely solid slag containing cobalt salt and alkaline sodium phosphate solution can be obtained by separation, so that recovery of cobalt and other metal elements in tungsten secondary resources is completed; then cooling the alkaline sodium phosphate solution, separating out a large number of sodium phosphate crystals from the solution, and performing solid-liquid separation after cooling to obtain a saturated sodium phosphate solution and sodium phosphate crystals; finally mixing scheelite with saturated sodium phosphate solution for ball milling, and leaching the obtained ore pulp, sodium phosphate crystal and water for reaction, wherein Ca in scheelite 2+ With PO (PO) 4 3- Binding to produce Ca 3 (PO 4 ) 2 And part of the basic calcium phosphate enters the slag phase, WO 4 2- And (3) the solution enters a liquid phase, and solid-liquid separation is carried out to obtain white tungsten decomposed slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate. Therefore, the method flexibly realizes the efficient decomposition of the hard alloy grinding waste and scheelite by the circulation of the phosphoric acid-sodium phosphate, realizes the combined treatment of primary and secondary tungsten resources, greatly reduces the production cost, improves the utilization rate of tungsten resources, and has zero wastewater discharge in the whole production process and is environment-friendly.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
And 1, weighing 1kg of hard alloy grinding waste, adding phosphoric acid which is 1.3 times of the total theoretical amount required by leaching out impurity elements such as cobalt and the like, simultaneously adding a proper amount of water to enable the liquid-solid ratio to be 1L to 1kg, stirring, mixing and leaching at room temperature for 10h, stirring at a speed of 200rpm, and carrying out solid-liquid separation after the reaction is finished to obtain solid slag containing tungsten carbide and leaching solution containing cobalt phosphate, wherein the leaching rate of cobalt element is 96.5%.
And 2, adding sodium hydroxide and 1.8L of pure water which are 3.5 times the phosphoric acid consumption in the step 1 into the obtained leaching solution containing the cobalt phosphate, stirring at 80 ℃ for reaction for 2 hours, stirring at 300rpm, and filtering while the reaction is hot after the reaction is finished to perform solid-liquid separation to obtain solid slag containing the cobalt hydroxide and an alkaline sodium phosphate solution.
And step 3, cooling the alkaline sodium phosphate solution to room temperature, precipitating a large amount of sodium phosphate crystals, and carrying out solid-liquid separation to obtain sodium phosphate crystals and saturated sodium phosphate solution.
And step 4, weighing 1kg of scheelite, adding saturated sodium phosphate solution according to the liquid-solid ratio of 0.3L to 1kg, mixing, supplying to a ball mill for ball milling, transferring ore pulp to a high-pressure reaction kettle after the scheelite granularity is below 325 meshes, adding 0.5L of pure water and sodium phosphate crystals which are 1.4 times of the theoretical amount required for decomposing the scheelite for high-temperature leaching, and carrying out solid-liquid separation after the reaction is finished to obtain scheelite decomposition slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate, wherein the tungsten leaching rate reaches 94.2%.
Example 2
1kg of hard alloy grinding waste is weighed, phosphoric acid which is 2 times of the total theoretical amount required by leaching out impurity elements such as cobalt and the like is added, meanwhile, a proper amount of water is added to enable the liquid-solid ratio to be 2L:1kg, stirring, mixing and leaching are carried out for 6 hours at room temperature, stirring speed is 400rpm, solid-liquid separation is carried out after the reaction is finished, solid slag containing tungsten carbide and leaching liquid containing cobalt phosphate are obtained, and the leaching rate of cobalt element is 98.8%.
And 2, adding sodium hydroxide and 2.8L of pure water which are 4.4 times the amount of phosphoric acid added in the step 1 into the obtained leaching solution containing the cobalt phosphate, stirring at 90 ℃ for reaction for 1h, stirring at 200rpm, and filtering while the reaction is hot after the reaction is finished to perform solid-liquid separation to obtain solid slag containing the cobalt hydroxide and an alkaline sodium phosphate solution.
And step 3, cooling the alkaline sodium phosphate solution to room temperature, precipitating a large amount of sodium phosphate crystals, and carrying out solid-liquid separation to obtain sodium phosphate crystals and saturated sodium phosphate solution.
And step 4, weighing 1kg of scheelite, adding saturated sodium phosphate solution according to the liquid-solid ratio of 0.5L to 1kg, mixing, then supplying to a ball mill for ball milling, transferring ore pulp into a high-pressure reaction kettle after the scheelite granularity is below 325 meshes, adding 0.3L of pure water and sodium phosphate crystals with the theoretical amount of 1.8 times that required by decomposing the scheelite for high-temperature leaching, and carrying out solid-liquid separation after the reaction is finished to obtain scheelite decomposed slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate, wherein the tungsten leaching rate reaches 96.8 percent.
Example 3
1kg of hard alloy grinding waste is weighed, phosphoric acid with the total theoretical amount of 2.5 times of the total theoretical amount required by leaching out impurity elements such as cobalt and the like is added, meanwhile, proper amount of water is added to enable the liquid-solid ratio to be 2.5L to 1kg, stirring, mixing and leaching are carried out at room temperature for 8 hours, stirring speed is 300rpm, solid-liquid separation is carried out after the reaction is completed, and solid slag containing tungsten carbide and leaching liquid containing cobalt phosphate are obtained, wherein the leaching rate of cobalt element is 99.2%.
And 2, adding sodium carbonate and 2L of pure water which are 4.9 times the amount of phosphoric acid added in the step 1 into the obtained leaching solution containing the cobalt phosphate, stirring at 85 ℃ for reaction for 3 hours, stirring at 300rpm, and filtering while the reaction is hot after the reaction is finished to perform solid-liquid separation to obtain solid slag containing the cobalt carbonate and alkaline sodium phosphate solution.
And step 3, cooling the alkaline sodium phosphate solution to room temperature, precipitating a large amount of sodium phosphate crystals, and carrying out solid-liquid separation to obtain sodium phosphate crystals and saturated sodium phosphate solution.
And step 4, weighing 1kg of scheelite, adding saturated sodium phosphate solution according to the liquid-solid ratio of 0.4L to 1kg, mixing, then supplying to a ball mill for ball milling, transferring ore pulp into a high-pressure reaction kettle after the scheelite granularity is below 325 meshes, adding 0.4L of pure water and sodium phosphate crystals with the theoretical amount of 1.6 times that required by decomposing the scheelite for high-temperature leaching, and carrying out solid-liquid separation after the reaction is finished to obtain scheelite decomposed slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate, wherein the tungsten leaching rate reaches 97.1 percent.
Example 4
And 1, weighing 1kg of hard alloy grinding waste, adding phosphoric acid with the total theoretical amount of 2.9 times of the total theoretical amount required by leaching out impurity elements such as cobalt and the like, simultaneously adding a proper amount of water to ensure that the liquid-solid ratio is 3L to 1kg, stirring, mixing and leaching for 9 hours at room temperature, stirring at the speed of 200rpm, and carrying out solid-liquid separation after the reaction is finished to obtain solid slag containing tungsten carbide and leaching solution containing cobalt phosphate, wherein the leaching rate of cobalt element is 99.5%.
And 2, adding sodium carbonate and 2.4L of pure water which are 5.7 times the amount of phosphoric acid added in the step 1 into the obtained leaching solution containing the cobalt phosphate, stirring and reacting for 1h at 95 ℃, stirring at 200rpm, and filtering while the reaction is hot after the reaction is finished, so as to obtain solid slag containing the cobalt carbonate and an alkaline sodium phosphate solution.
And step 3, cooling the alkaline sodium phosphate solution to room temperature, precipitating a large amount of sodium phosphate crystals, and carrying out solid-liquid separation to obtain sodium phosphate crystals and saturated sodium phosphate solution.
And step 4, weighing 1kg of scheelite, adding saturated sodium phosphate solution according to a liquid-solid ratio of 0.6L to 1kg, mixing, then supplying to a ball mill for ball milling, transferring ore pulp into a high-pressure reaction kettle after the scheelite granularity is below 325 meshes, adding 0.3L of pure water and sodium phosphate crystals which are 2 times of the theoretical amount required for decomposing the scheelite for high-temperature leaching, and carrying out solid-liquid separation after the reaction is finished to obtain scheelite decomposition slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate, wherein the tungsten leaching rate reaches 97.9 percent.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A method for combined treatment of cemented carbide grinding waste and scheelite comprising:
(1) Mixing and leaching the hard alloy grinding waste with phosphoric acid with stirring, and then carrying out solid-liquid separation to obtain solid slag containing tungsten carbide and leaching liquid containing cobalt phosphate;
(2) Mixing the leaching solution containing cobalt phosphate with alkali liquor for reaction with stirring, and then carrying out solid-liquid separation to obtain solid slag containing cobalt salt and alkaline sodium phosphate solution;
(3) Cooling the alkaline sodium phosphate solution, and then performing solid-liquid separation to obtain a saturated sodium phosphate solution and sodium phosphate crystals;
(4) Mixing scheelite with the saturated sodium phosphate solution for ball milling, leaching the obtained ore pulp with the sodium phosphate crystal and water for solid-liquid separation, so as to obtain scheelite decomposition slag containing calcium phosphate and basic calcium phosphate and solution containing crude sodium tungstate.
2. The method according to claim 1, wherein in the step (1), the stirring speed is 100 to 500rpm, and the mixed leaching time is 3 to 12 hours.
3. The method according to claim 1 or 2, characterized in that in step (1), the solid-to-liquid ratio of the cemented carbide grinding waste to the phosphoric acid is 1kg: (0.8-3) L.
4. A method according to claim 3, characterized in that in step (1) the phosphoric acid is used in an amount of 1.1-4 times the total theoretical amount required for leaching the metal ions in the cemented carbide grinding waste.
5. The method according to claim 1, wherein in step (2), the stirring speed is 100 to 500rpm.
6. The method according to claim 1 or 5, wherein in step (2), the temperature of the mixing reaction is 80 to 100 ℃ for 1 to 5 hours.
7. The process according to claim 6, wherein in step (2) the amount of alkali in the lye is 3 to 6 times the amount of phosphoric acid in step (1).
8. The method according to claim 1, wherein in step (4), the solid-to-liquid ratio of the scheelite to the saturated sodium phosphate solution is 1kg: (0.2-1) L.
9. The method according to claim 1 or 8, wherein in the step (4), the particle size of scheelite in the slurry after ball milling is not less than 325 mesh.
10. The method according to claim 9, wherein in the step (4), the sodium phosphate crystals are added in an amount of 1.2 to 2 times the theoretical amount required for the decomposition of the scheelite.
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