CN103911514B - The recovery and treatment method of scrap hard alloy grinding material - Google Patents
The recovery and treatment method of scrap hard alloy grinding material Download PDFInfo
- Publication number
- CN103911514B CN103911514B CN201310003314.2A CN201310003314A CN103911514B CN 103911514 B CN103911514 B CN 103911514B CN 201310003314 A CN201310003314 A CN 201310003314A CN 103911514 B CN103911514 B CN 103911514B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- recovery
- grinding material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of recovery and treatment method of scrap hard alloy grinding material, mainly solve prior art and there is long flow path, equipment requirements is high, and in grinding material, cobalt tungsten separating difficulty is large, the problem that the rate of recovery is low.The present invention is comprised the following steps by employing: a) mixed with sulphuric acid soln and oxygenant I by scrap hard alloy grinding material, filters, obtain the solution of wolfram varbide filter residue and cobalt-bearing ferronickel after reaction; B) roasting after being mixed with sodium carbonate and SODIUMNITRATE by wolfram varbide filter residue, obtains material I; C) material I be impregnated in hot water, obtain the solution containing sodium wolframate; Solution containing sodium wolframate obtains sodium wolframate crystal through concentration and evaporation crystallization; D) solution of cobalt-bearing ferronickel adds oxygenant II under the condition of pH=2 ~ 5, after reaction, obtains iron precipitation and the solution containing cobalt nickel; The technical scheme that solution containing cobalt nickel obtains cobalt nickel salt crystal after treatment solves this problem preferably, can be used in the industrial production of scrap hard alloy grinding material recycling.
Description
Technical field
The present invention relates to a kind of recovery and treatment method of scrap hard alloy grinding material.
Background technology
Wimet is mainly made up of tungsten, cobalt etc., along with the widespread use of Wimet and the increase of demand, cause tungsten, cobalt resource in short supply, price increase.In recent years, many countries using the Secondary resource of waste hand alloy material as preciousness, to solve the source of raw material and to reduce the important means of CEMENTED CARBIDE PRODUCTION cost.Therefore reclaim tungsten, cobalt resource is of great immediate significance to developing national economy.
At present both at home and abroad the main method of process Wimet defective material has: metal cobalt, zinc melt method, oxidation style, sodium sulfate fuse method and electro-dissolving etc.Document CN88105175.6 discloses a kind of method regenerating Footwall drift tungsten, cobalt from waste hand alloy material, the composite technology of use heat process-hydrometallurgy, namely utilize Principles of Heating Processing to carry out oxidation powder process to waste hand alloy material, obtain tungsten cobalt mixed oxide powder; Utilize hydrometallurgical principle, Reduced separating, extraction are carried out to tungsten cobalt mixed oxide powder, obtain powdery pure metal tungsten and cobalt.This technique can obtain the product of cobalt tungsten, but long flow path, and the rate of recovery of cobalt tungsten is not high, is unsuitable for processing the Wimet containing nickel, iron etc. simultaneously.Zhang Qixun proposes the technique of electro-dissolving process Wimet, and this technique is very effective for block Wimet, but it is not high to there is electroconductibility for grinding material Wimet, the shortcomings such as current efficiency is low.Document CN200910043243.2 discloses a kind of process recovery method of hard alloy scraps.It comprises the following steps: hard alloy scraps and weighting agent carbon black load in graphite boat by a., put into carbon tube furnace high-temperature calcination, calcining temperature 1600 ~ 2400 DEG C, calcination time 30 ~ 80 minutes, hydrogen flowing quantity 1.2 ~ 2.6m under hydrogen
3/ h; B., after the hard alloy scraps after high-temperature calcination being unloaded boat, clean surface, be broken into jaw crusher and roll crusher two sections the alloy granule that granularity is 2 ~ 8mm; C. the alloy granule after fragmentation is carried out ball milling, ratio of grinding media to material (4 ~ 5): 1, Ball-milling Time 8 ~ 16 hours; D. the alloy powder after ball milling is sieved, for traditional processing technology batching after the detection of sieve lower alloy powder is qualified, manufacture Wimet.Reproduce the technique of Wimet after this method proposing high temperature in reducing atmosphere, ball mill mixing, but containing other impurity in grinding material, as abrasive material, sand, iron filings etc., can not Direct Regeneration be carried out.Document CN200510012779.X discloses a kind of method extracting rare metal from scrap hard alloy.Its technique comprises the following steps: scrap hard alloy through broken, clay into power, calcine, react with sodium hydroxide solution, sodium tungstate solution acquired by utilization adds sulfuric acid and ammoniacal liquor generates ammonium tungstate solution through extraction and back-extraction, add hydrogen reducing become metal tungsten powder through heating evaporation, crystallization, oven dry, again calcining again, and solids described in utilizing is through extracting cobalt powder and nickel powder and metal tantalum, metal niobium with sulfuric acid, ammonium oxalate.Utilize above-mentioned operation tungsten, cobalt metal, metallic nickel and metal tantalum, metal niobium can be extracted from scrap hard alloy.After this method proposing ball milling, alkali roasting, washing, extraction back extraction obtains ammonium tungstate, and residuum is through materials such as acid-soluble precipitation cobalt nickel tantalum niobiums.This process synthesis has reclaimed the various metals in Wimet, but there is the indissociable shortcomings such as alkali roasting is high to equipment requirements, cobalt nickel tantalum niobium.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists long flow path, and equipment requirements is high, and in grinding material, cobalt tungsten separating difficulty is large, and the problem that the rate of recovery is low, provides a kind of recovery and treatment method of new scrap hard alloy grinding material.The method flow process is reasonable, simple to equipment requirements, can the various metallic element such as cobalt, tungsten, nickel and iron in synthetical recovery grinding material, and the rate of recovery is high and purity is high, and environmental pollution is little.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of recovery and treatment method of scrap hard alloy grinding material, comprises the following steps:
A) be oxidized acid-soluble: by containing cobalt, nickel, iron, tungsten scrap hard alloy grinding material mix with sulphuric acid soln and oxygenant I, reaction after filtration, obtain the solution of wolfram varbide filter residue and cobalt-bearing ferronickel;
B) soda roasting wolfram varbide filter residue: roasting after being mixed with sodium carbonate and SODIUMNITRATE by wolfram varbide filter residue, obtains material I;
C) reclaim tungsten: impregnated in hot water by material I, obtain the solution containing sodium wolframate; Solution containing sodium wolframate obtains sodium wolframate crystal through concentration and evaporation crystallization;
D) Call Provision nickel: the solution of the cobalt-bearing ferronickel that step a) obtains adds oxygenant II under the condition of pH=2 ~ 5, after reaction, obtains iron precipitation and the solution containing cobalt nickel; Solution containing cobalt nickel obtains cobalt salt crystal and nickel salt crystal after extraction, washing nickel, back extraction cobalt, condensing crystal.
Preferably, described oxygenant I is selected from least one in hydrogen peroxide, sodium chlorate or potassium permanganate; Described oxygenant II is selected from hydrogen peroxide.Wherein, the concentration of hydrogen peroxide can be 2 ~ 50 % by weight.
Preferably, the concentration of step a) sulphuric acid soln is 2 ~ 4 mol/L, and the consumption of sulphuric acid soln is 1:(2 ~ 8 according to solid-to-liquid ratio); The consumption of oxygenant I is 0.1 ~ 1 times of cobalt ferronickel gross weight; Reaction times is 0.5 ~ 5 hour, and temperature of reaction is 60 ~ 100 DEG C.
Preferably, in step b), the mol ratio of wolfram varbide filter residue and sodium carbonate is 1:(0.8 ~ 2.5), mol ratio 1:(0.05 ~ 0.5 of wolfram varbide filter residue and SODIUMNITRATE); Maturing temperature is 400 ~ 600 DEG C, and roasting time is 1 ~ 4 hour.
Preferably, the temperature of step c) hot water is 40 ~ 99 DEG C, and solid-to-liquid ratio is 1:(2 ~ 10), dipping time is 1 ~ 4 hour.
Preferably, the insolubles obtained after step c) Hot water immersion is back to step a), with scrap hard alloy grinding material again together be oxidized acid-soluble.
Preferably, the solution of step d) cobalt-bearing ferronickel and the temperature of reaction of oxygenant II are 40 ~ 99 DEG C, and the reaction times is 0.5 ~ 5 hour; In solution, iron is 1:(0.05 ~ 0.6 with the mol ratio of the oxygenant II added).
Preferably, step d) is containing the solution extraction agent extracting and separating cobalt nickel of cobalt nickel, and described extraction agent comprises by weight percentage: the 2-ethylhexyl phosphonic acids single 2-ethyl base ester (P507) of 15 ~ 30%, 260 solvent oils of 70 ~ 85%; Wherein, the saponification degree of 2-ethylhexyl phosphonic acids single 2-ethyl base ester is 50 ~ 75%.
Preferably, step d) contains the solution of cobalt nickel through 8 ~ 12 grades of extractions, 8 ~ 10 grades of washing nickel, 6 ~ 10 grades of back extraction cobalts.Wherein, during back extraction cobalt, extraction agent is sulfuric acid.
Preferably, after step b) wolfram varbide filter residue mixes with sodium carbonate and SODIUMNITRATE, first under temperature is 100 ~ 200 DEG C of conditions dry 10 ~ 30 minutes, and then go roasting.
The inventive method can synthetical recovery tungsten, cobalt, the various metallic element of nickel, and the rate of recovery is high, and the rate of recovery of tungsten can reach more than 92%, and the rate of recovery of cobalt can reach more than 93%, and the rate of recovery of nickel can reach more than 92%; Obtain tungsten, cobalt, nickel product purity are high, the purity of tungsten can reach more than 98%, rose vitriol quality can reach national grade ii standard and more than, single nickel salt quality can reach national grade ii standard; Technique advantages of simple, does not produce waste water and gas waste residue substantially, little to environmental injury, and cost is low, simultaneously not high to equipment requirements simultaneously less for supplementary product onsumption, can realize continuous prodution, achieve good technique effect.
Embodiment
[embodiment 1]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3, adds oxidants chlorine acid sodium according to 0.2 times of cobalt ferronickel gross weight, 2 hours reaction times simultaneously.Temperature of reaction 90 DEG C.Cobalt contents 0.2% in final filter residue, nickel content 0.15%, iron level 0.03%, the leaching yield of cobalt ferronickel is 96%, 97%, 95% respectively.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.2kg obtained, mixes according to mol ratio 1:1.3 with soda (sodium carbonate), add SODIUMNITRATE according to wolfram varbide and SODIUMNITRATE mol ratio 1:0.1 simultaneously, roasting in rotary kiln after mixing, maturing temperature 430 DEG C, time 2 h.
C) tungsten is reclaimed.Material after roasting leaches in the hot water of 90 DEG C, solid-to-liquid ratio 1:3, agitation leach 3 hours, and the solution containing sodium wolframate 230g/l obtained, obtain sodium wolframate crystal through concentration and evaporation crystallization, purity is 98.5%.The rate of recovery 92.1% of final tungsten.The insolubles that water logging obtains is acid-soluble together with grinding material again.
D) recovery of cobalt nickel.The solution of step a) the acid-soluble cobalt-bearing ferronickel obtained adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) under pH=2.5 condition, 90 DEG C of stirring reactions 1.5 hours, obtains the precipitation of iron and the solution containing cobalt nickel.The solution P507 extraction agent extracting and separating cobalt nickel obtained, P507 extraction agent consists of 260 solvent oils of the P507+80% of 20%, and P507 saponification degree is 70%, through 9 grades of extractions, 10 grades of washing nickel, 8 grades of back extraction cobalts, separation and concentration cobalt nickel, the pure cobalt nickel solution obtained obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches national standard reference, single nickel salt reaches national grade ii standard, and the rate of recovery of cobalt nickel is 93%, 92% respectively.
[embodiment 2]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:4, adds oxidants chlorine acid sodium according to 0.25 times of cobalt ferronickel total mass, 2 hours reaction times simultaneously.Temperature of reaction 90 DEG C.Cobalt contents 0.3% in final filter residue, nickel content 0.12%, iron level 0.1%, the leaching yield of cobalt ferronickel is 96.5%, 97.8%, 96% respectively.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.6kg obtained, mixes according to mol ratio 1:14 with soda (sodium carbonate), add SODIUMNITRATE according to wolfram varbide and SODIUMNITRATE mol ratio 1:0.15 simultaneously, roasting in rotary kiln after mixing, maturing temperature 450 DEG C, time 2 h.
C) tungsten is reclaimed.Material after roasting leaches in the hot water of 95 DEG C, solid-to-liquid ratio 1:3, agitation leach 4 hours, and the solution containing sodium wolframate 250g/l obtained, obtain sodium wolframate crystal through concentration and evaporation crystallization, purity is 99.0%.The rate of recovery 92.4% of final tungsten.The insolubles that water logging obtains is acid-soluble together with grinding material again.
D) recovery of cobalt nickel.The solution of step a) the acid-soluble cobalt-bearing ferronickel obtained adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) at pH2.5, 90 DEG C of stirring reactions 2 hours, obtain the precipitation of iron and the solution containing cobalt nickel, the solution P507 extraction agent extracting and separating cobalt nickel obtained, P507 extraction agent consists of 260 solvent oils of the P507+80% of 20%, P507 saponification degree is 75%, through 9 grades of extractions, 10 grades of washing nickel, 8 grades of back extraction cobalts, separation and concentration cobalt nickel, the pure cobalt nickel solution obtained obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches national standard reference, single nickel salt reaches national grade ii standard, the rate of recovery of cobalt nickel is 94% respectively, 92%.
[embodiment 3]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added 2.5mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3.5, adds oxidants chlorine acid sodium according to 0.2 times of cobalt ferronickel total mass, 2 hours reaction times simultaneously.Temperature of reaction 90 DEG C.Cobalt contents 0.15% in final filter residue, nickel content 0.12%, iron level 0.04%, the leaching yield of cobalt ferronickel is 96.5%, 97.5%, 95% respectively.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.2kg obtained, mixes according to mol ratio 1:1.3 with soda (sodium carbonate), add SODIUMNITRATE according to wolfram varbide and SODIUMNITRATE mol ratio 1:0.2 simultaneously, roasting in rotary kiln after mixing, maturing temperature 450 DEG C, time 2 h.
C) tungsten is reclaimed.Material after roasting leaches in the hot water of 85 DEG C, solid-to-liquid ratio 1:2, agitation leach 3 hours, and the solution containing sodium wolframate 340g/l obtained, obtain sodium wolframate crystal through concentration and evaporation crystallization, purity is 98.0%.The rate of recovery 92.5% of final tungsten.The insolubles that water logging obtains is acid-soluble together with grinding material again.
D) recovery of cobalt nickel.The solution of step a) the acid-soluble cobalt-bearing ferronickel obtained adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) at pH2.5, 95 DEG C of stirring reactions 1.5 hours, obtain the precipitation of iron and the solution containing cobalt nickel, the solution P507 extraction agent extracting and separating cobalt nickel obtained, P507 extraction agent consists of 260 solvent oils of the P507+80% of 20%, P507 saponification degree is 65%, through 9 grades of extractions, 10 grades of washing nickel, 8 grades of back extraction cobalts, separation and concentration cobalt nickel, the pure cobalt nickel solution obtained obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches national grade ii standard, single nickel salt reaches national grade ii standard, the rate of recovery of cobalt nickel is 94% respectively, 93%.
[embodiment 4]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3.5, adds oxidants chlorine acid sodium according to 0.25 times of cobalt ferronickel total mass, 1.5 hours reaction times simultaneously.Temperature of reaction 90 DEG C.Cobalt contents 0.15% in final filter residue, nickel content 0.15%, iron level 0.09%, the leaching yield of cobalt ferronickel is 95%, 97%, 96% respectively.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.3kg obtained, mixes according to mol ratio 1:1.3 with soda (sodium carbonate), add SODIUMNITRATE according to wolfram varbide and SODIUMNITRATE mol ratio 1:0.15 simultaneously, roasting in rotary kiln after mixing, maturing temperature 440 DEG C, time 2 h.
C) tungsten is reclaimed.Material after roasting leaches in the hot water of 90 DEG C, solid-to-liquid ratio 1:3, agitation leach 3 hours, and the solution containing sodium wolframate 210g/L obtained, obtain sodium wolframate crystal through concentration and evaporation crystallization, purity is 98%.The rate of recovery 92.5% of final tungsten.The insolubles that water logging obtains is acid-soluble together with grinding material again.
D) recovery of cobalt nickel.The solution of the acid-soluble cobalt-bearing ferronickel obtained of the first step adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) at pH2.5, 90 DEG C of stirring reactions 1.5 hours, obtain the precipitation of iron and the solution containing cobalt nickel, the solution P507 extraction agent extracting and separating cobalt nickel obtained, P507 extraction agent consists of 260 solvent oils of the P507+80% of 20%, P507 saponification degree is 70%, through 9 grades of extractions, 10 grades of washing nickel, 8 grades of back extraction cobalts, separation and concentration cobalt nickel, the pure cobalt nickel solution obtained obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches national standard reference, single nickel salt reaches national grade ii standard, the rate of recovery of cobalt nickel is 94% respectively, 92%.
[embodiment 5]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3.5, adds oxidants chlorine acid sodium according to 0.2 times of cobalt ferronickel total mass, 2 hours reaction times simultaneously.Temperature of reaction 90 DEG C.Cobalt contents 0.17% in final filter residue, nickel content 0.14%, iron level 0.04%, the leaching yield of cobalt ferronickel is 97%, 97.5%, 95% respectively.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.2kg obtained, mix according to mol ratio 1:1.3 with soda (sodium carbonate), add SODIUMNITRATE according to wolfram varbide and SODIUMNITRATE mol ratio 1:0.25 simultaneously, mix rear elder generation under temperature is 120 DEG C of conditions dry 20 minutes, remove moisture, then roasting in rotary kiln, maturing temperature 450 DEG C, time 2 h.
C) tungsten is reclaimed.Material after roasting leaches in the hot water of 85 DEG C, solid-to-liquid ratio 1:2, agitation leach 3 hours, and the solution containing sodium wolframate 330g/L obtained, obtain sodium wolframate crystal through concentration and evaporation crystallization, purity is 98.0%.The rate of recovery 93% of final tungsten.The insolubles that water logging obtains is acid-soluble together with grinding material again.
D) recovery of cobalt nickel.The solution of the acid-soluble cobalt-bearing ferronickel obtained of the first step adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) at pH2.5, 95 DEG C of stirring reactions 1.5 hours, obtain the precipitation of iron and the solution containing cobalt nickel, the solution P507 extraction agent extracting and separating cobalt nickel obtained, P507 extraction agent consists of 260 solvent oils of the P507+80% of 20%, P507 saponification degree is 65%, through 8 grades of extractions, 10 grades of washing nickel, 8 grades of back extraction cobalts, separation and concentration cobalt nickel, the pure cobalt nickel solution obtained obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches national grade ii standard, single nickel salt reaches national grade ii standard, the rate of recovery of cobalt nickel is 94% respectively, 93%.
[comparative example 1]
Other conditions are constant, and only add oxidants chlorine acid sodium by [embodiment 1] according to 0.05 times of cobalt ferronickel total mass, cobalt contents 0.7% in final filter residue, nickel content 1.01%, iron level 0.5%, the turnover rate of cobalt ferronickel is 90%, 89%, 90% respectively.
[comparative example 2]
Other conditions are constant, and only mixed according to mol ratio 1:0.7 with soda (sodium carbonate) by wolfram varbide filter residue in [embodiment 2], eventually pass through concentration and evaporation crystallization and obtain sodium wolframate crystal, purity is 99.0%.The rate of recovery 87.2% of final tungsten.
[comparative example 3]
According to method process grinding material disclosed in document CN88105175.6.Oxide treatment under 850 DEG C of conditions, then through chilling, the steps such as hydrogenating reduction, utilize Principles of Heating Processing to carry out oxidation powder process to waste hand alloy material, obtain tungsten cobalt mixed oxide powder; Utilize hydrometallurgical principle, Reduced separating, extraction are carried out to tungsten cobalt mixed oxide powder, obtain powdery pure metal tungsten and cobalt.This technical process is long, and equipment requirements is high, and operational condition is harsh.
Result is: the rate of recovery≤90% of tungsten, the rate of recovery≤90% of cobalt, is unsuitable for processing the Wimet containing nickel, iron etc. simultaneously.
[comparative example 4]
According to method process grinding material disclosed in document CN200910043243.2.Under the condition of 2400 DEG C of logical hydrogen, high-temperature calcination 80 minutes, through broken, ball milling with sieve and obtain powdered alloy after cooling, the whole operational cycle is long, and equipment requirements is high, and operational condition is harsh, and greatly, production cost is higher for energy consumption.
Result: last and product is hybrid alloys powder, and tungsten, cobalt and nickel mix, and do not separate separately, and if containing other impurity in grinding material, as abrasive material, sand, iron filings etc., this method can not carry out Direct Regeneration.
Claims (6)
1. a recovery and treatment method for scrap hard alloy grinding material, comprises the following steps:
A) be oxidized acid-soluble: by containing cobalt, nickel, iron, tungsten scrap hard alloy grinding material mix with sulphuric acid soln and oxygenant I, reaction after filtration, obtain the solution of wolfram varbide filter residue and cobalt-bearing ferronickel;
B) soda roasting wolfram varbide filter residue: roasting after being mixed with sodium carbonate and SODIUMNITRATE by wolfram varbide filter residue, obtains material I;
C) reclaim tungsten: impregnated in hot water by material I, obtain the solution containing sodium wolframate; Solution containing sodium wolframate obtains sodium wolframate crystal through concentration and evaporation crystallization;
D) Call Provision nickel: the solution of the cobalt-bearing ferronickel that step a) obtains adds oxygenant II under the condition of pH=2 ~ 5, after reaction, obtains iron precipitation and the solution containing cobalt nickel; Solution containing cobalt nickel obtains cobalt salt crystal and nickel salt crystal after extraction, washing nickel, back extraction cobalt, condensing crystal;
The concentration of step a) sulphuric acid soln is 2 ~ 4 mol/L, and the consumption of sulphuric acid soln is 1:(2 ~ 8 according to solid-to-liquid ratio); The consumption of oxygenant I is 0.1 ~ 1 times of cobalt ferronickel gross weight; Reaction times is 0.5 ~ 5 hour, and temperature of reaction is 60 ~ 100 DEG C;
Step b) in, the mol ratio of wolfram varbide filter residue and sodium carbonate is 1:(0.8 ~ 2.5), mol ratio 1:(0.05 ~ 0.5 of wolfram varbide filter residue and SODIUMNITRATE); Maturing temperature is 400 ~ 600 DEG C, and roasting time is 1 ~ 4 hour;
Described oxygenant I is selected from least one in hydrogen peroxide, sodium chlorate or potassium permanganate; Described oxygenant II is selected from hydrogen peroxide.
2. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, is characterized in that step c) temperature of hot water is 40 ~ 99 DEG C, solid-to-liquid ratio is 1:(2 ~ 10), dipping time is 1 ~ 4 hour.
3. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, is characterized in that steps d) solution of cobalt-bearing ferronickel and the temperature of reaction of oxygenant II be 40 ~ 99 DEG C, the reaction times is 0.5 ~ 5 hour; In solution, iron is 1:(0.05 ~ 0.6 with the mol ratio of the oxygenant II added).
4. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, it is characterized in that steps d) containing the solution extraction agent extracting and separating cobalt nickel of cobalt nickel, described extraction agent comprises by weight percentage: the 2-ethylhexyl phosphonic acids single 2-ethyl base ester of 15 ~ 30%, 260 solvent oils of 70 ~ 85%; Wherein, the saponification degree of 2-ethylhexyl phosphonic acids single 2-ethyl base ester is 50 ~ 75%.
5. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, is characterized in that steps d) containing the solution of cobalt nickel through 8 ~ 12 grades of extractions, 8 ~ 10 grades of washing nickel, 6 ~ 10 grades of back extraction cobalts.
6. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, it is characterized in that step b) after wolfram varbide filter residue mixes with sodium carbonate and SODIUMNITRATE, first under temperature is 100 ~ 200 DEG C of conditions dry 10 ~ 30 minutes, and then go roasting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310003314.2A CN103911514B (en) | 2013-01-06 | 2013-01-06 | The recovery and treatment method of scrap hard alloy grinding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310003314.2A CN103911514B (en) | 2013-01-06 | 2013-01-06 | The recovery and treatment method of scrap hard alloy grinding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103911514A CN103911514A (en) | 2014-07-09 |
| CN103911514B true CN103911514B (en) | 2016-03-02 |
Family
ID=51037514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310003314.2A Active CN103911514B (en) | 2013-01-06 | 2013-01-06 | The recovery and treatment method of scrap hard alloy grinding material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103911514B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282566B (en) * | 2015-05-27 | 2020-01-21 | 云南锡业集团有限责任公司研究设计院 | Method for preparing cobalt carbonate from iron-containing tungsten-cobalt waste residue |
| CN105460981B (en) * | 2015-12-24 | 2019-04-05 | 湖南力天高新材料股份有限公司 | A method of tungsten carbide and cobalt chloride are prepared with tungsten waste |
| CN109019706B (en) * | 2018-07-17 | 2020-02-07 | 金川集团股份有限公司 | Method for producing nickel sulfate and cobalt sulfate by using waste nickel alloy |
| CN111020234A (en) * | 2019-12-27 | 2020-04-17 | 厦门钨业股份有限公司 | Method for preparing APT (ammonium paratungstate) by utilizing tungsten-containing waste |
| CN113667825B (en) | 2021-07-20 | 2022-11-15 | 广东邦普循环科技有限公司 | Ferronickel wet processing method and application thereof |
| CN114182094B (en) * | 2021-09-16 | 2024-05-24 | 王仕斌 | Comprehensive recycling method for valuable metals in hard alloy grinding material |
| CN114622096B (en) * | 2022-03-15 | 2023-09-19 | 崇义章源钨业股份有限公司 | Method for separating tungsten and cobalt from grinding material |
| CN115386733B (en) * | 2022-09-16 | 2024-04-19 | 江西理工大学 | Method for decomposing and recycling tungsten-containing waste by using mixed acid of nitrate and sulfur |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054270A (en) * | 1991-03-19 | 1991-09-04 | 国营自贡硬质合金厂 | The recovery and treatment method of waste hand alloy material |
| CN1827799A (en) * | 2006-03-24 | 2006-09-06 | 张昱 | Method for recovering nickel and cobalt from nickel oxide ore and nickel silicide ore |
| CN101225481A (en) * | 2007-01-18 | 2008-07-23 | 中国地质科学院郑州矿产综合利用研究所 | Metallurgical extraction method of molybdenum-tungsten oxide bulk concentrate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5483009B2 (en) * | 2010-02-26 | 2014-05-07 | 三菱マテリアル株式会社 | A method of recovering tungsten from cemented carbide scrap. |
-
2013
- 2013-01-06 CN CN201310003314.2A patent/CN103911514B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054270A (en) * | 1991-03-19 | 1991-09-04 | 国营自贡硬质合金厂 | The recovery and treatment method of waste hand alloy material |
| CN1827799A (en) * | 2006-03-24 | 2006-09-06 | 张昱 | Method for recovering nickel and cobalt from nickel oxide ore and nickel silicide ore |
| CN101225481A (en) * | 2007-01-18 | 2008-07-23 | 中国地质科学院郑州矿产综合利用研究所 | Metallurgical extraction method of molybdenum-tungsten oxide bulk concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103911514A (en) | 2014-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103911514B (en) | The recovery and treatment method of scrap hard alloy grinding material | |
| CN104498718A (en) | Method for treating hard alloy grinding material | |
| CN108550939B (en) | A method of selective recovery lithium and lithium carbonate is prepared from waste lithium cell | |
| CN102956936B (en) | Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile | |
| CN102206755B (en) | Method for separating and recovering valuable elements from neodymium-iron-boron wastes | |
| CN106129511A (en) | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| CN103290223B (en) | Comprehensive recovery method for multiple metals of waste catalyst | |
| CN108559846A (en) | The method of synthetical recovery waste lithium ion cell anode material | |
| CN106065435A (en) | A kind of method and system processing vanadium slag | |
| CN106611841A (en) | Method for preparing nickel-cobalt-manganese ternary material precursor by using nickel-cobalt slag material | |
| CN112831660B (en) | Process for comprehensively utilizing molybdenum ore leaching slag | |
| CN102560100A (en) | Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy | |
| CN106048251A (en) | Technological method for cleaning and efficiently treating arsenic matte | |
| CN109628744B (en) | Method for recovering tungsten and cobalt from tungsten-containing hard alloy waste | |
| CN112159897A (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| CN106065436A (en) | A kind of method and system processing vanadium slag | |
| CN106229577A (en) | The method that the mixing of a kind of waste nickel hydrogen battery both positive and negative polarity material is leached | |
| CN105039724A (en) | Smelting furnace soot treatment method | |
| CN111304446A (en) | Method for comprehensively utilizing high-temperature alloy waste through segmented leaching | |
| CN105110300B (en) | The method that a kind of compound manganese ore of Containing Sulfur manganese extracts manganese and sulphur | |
| CN101693554A (en) | Method for extracting vanadium pentoxide from stone coal ores | |
| CN109750163A (en) | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery | |
| CN108330276A (en) | Method for preparing high-purity iron powder using iron vitriol slag and products thereof and application | |
| CN116995327A (en) | Method for recycling lithium from ternary positive electrode waste | |
| CN111534699A (en) | Method for recovering valuable substances from cemented carbide scrap |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |