CN103911514A - Waste hard alloy grinding material recovery treatment method - Google Patents
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Abstract
The invention relates to a waste hard alloy grinding material recovery treatment method, wherein problems of low process, high equipment requirements, high cobalt-tungsten separation difficulty in a grinding material, and low recovery rate in the existing technology are mainly solved. The technical scheme of the waste hard alloy grinding material recovery treatment method comprises: a) mixing a waste hard alloy grinding material, a sulfuric acid solution and an oxidant I, carrying out a reaction, and filtering to obtain tungsten carbide filter residue and a cobalt-nickel-iron-containing solution; b) mixing the tungsten carbide filter residue, sodium carbonate and sodium nitrate, and calcining to obtain a material I; c) immersing the material I in hot water to obtain a solution containing sodium tungstate, and carrying out concentration evaporation crystallization on the solution containing sodium tungstate to obtain a sodium tungstate crystal; and d) adding an oxidant II to the cobalt-nickel-iron-containing solution under a condition of the pH value of 2-5, carrying out a reaction to obtain iron precipitate and a nickel-cobalt-containing solution, and treating the nickel-cobalt-containing solution to obtain a cobalt-nickel salt crystal. According to the present invention, with the technical scheme, the problems in the prior art are well solved, and the method can be used for the waste hard alloy grinding material recovery treatment in the industrial production.
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, has caused the in short supply of tungsten, cobalt resource, price increase.In recent years, many countries are using waste hand alloy material as valuable Secondary resource, to solve the source of raw material and the important means of reduction CEMENTED CARBIDE PRODUCTION cost.Therefore reclaim tungsten, cobalt resource is of great immediate significance to developing national economy.
The main method of processing at present Wimet defective material both at home and abroad has: metal cobalt, the molten method of zinc, oxidation style, the fused method of sodium sulfate and electro-dissolving etc.Document CN88105175.6 discloses a kind of regeneration from waste hand alloy material and has reclaimed the method for tungsten, cobalt, the composite technology of use heat processing-hydrometallurgy, utilize Principles of Heating Processing to be oxidized powder process to waste hand alloy material, obtain tungsten cobalt mixed oxide powder; Utilize hydrometallurgical principle, tungsten cobalt mixed oxide powder is carried out to Reduced separating, extraction, 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 that contains nickel, iron etc. simultaneously.Zhang Qixun proposes the technique of electro-dissolving processing Wimet, and this technique is very effective for block Wimet, but has the shortcomings such as electroconductibility is not high, and current efficiency is low for grinding material Wimet.Document CN200910043243.2 discloses a kind of processing recovery method of hard alloy scraps.It comprises the following steps: a. packs hard alloy scraps and weighting agent carbon black in graphite boat into, puts into carbon tube furnace high-temperature calcination under hydrogen, 1600～2400 DEG C of calcining temperatures, calcination time 30～80 minutes, hydrogen flowing quantity 1.2～2.6m
3/ h; B. the hard alloy scraps after high-temperature calcination is unloaded after boat, clean surface, be broken into the alloy granule that granularity is 2～8mm with two sections of jaw crusher and roll crushers; C. the alloy granule after fragmentation is carried out to 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, after the lower alloy powder detection of sieve is qualified, for traditional processing technology batching, manufacture Wimet.The method has proposed in reducing atmosphere, after high temperature, ball mill mixing, to reproduce the technique of Wimet, but in grinding material, contains other impurity, as abrasive material, sand, iron filings etc., can not carry out Direct Regeneration.Document CN200510012779.X discloses a kind of method of extracting rare metal from scrap hard alloy.Its technique comprises the following steps: scrap hard alloy through broken, clay into power, calcine, with in sodium hydroxide solution, react, utilize obtained sodium tungstate solution to add sulfuric acid and ammoniacal liquor to generate ammonium tungstate solution through extraction and back-extraction, again through heating evaporation, crystallization, oven dry, calcining adds hydrogen reducing to become metal tungsten powder again, and utilize described solids through and sulfuric acid, ammonium oxalate extract cobalt powder and nickel powder and metal tantalum, metal niobium.Utilize above-mentioned operation tungsten, cobalt metal, metallic nickel and metal tantalum, metal niobium to be extracted from scrap hard alloy.After the method has proposed 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 has 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 comprehensively reclaim the various metallic elements such as cobalt in grinding material, tungsten, nickel and iron, 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: will mix with sulphuric acid soln and oxygenant I containing the scrap hard alloy grinding material of cobalt, nickel, iron, tungsten, reaction is filtration afterwards, obtains the solution of wolfram varbide filter residue and cobalt-bearing ferronickel;
B) soda roasting wolfram varbide filter residue: roasting after wolfram varbide filter residue is mixed with sodium carbonate and SODIUMNITRATE, obtains material I;
C) reclaim tungsten: material I be impregnated in hot water, obtain the solution containing sodium wolframate; Solution process concentration and evaporation crystallization containing sodium wolframate obtains sodium wolframate crystal;
D) reclaim cobalt nickel: the solution of the cobalt-bearing ferronickel that step a) obtains adds oxygenant II under the condition of pH=2 ~ 5, after reaction, obtain 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 obtaining after step c) Hot water immersion is back to step a), is oxidized together with more acid-soluble with scrap hard alloy grinding material.
Preferably, the temperature of reaction of the solution of step d) cobalt-bearing ferronickel and oxygenant II is 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 adding).
Preferably, step d) is containing the extraction agent extracting and separating cobalt nickel for solution of cobalt nickel, and described extraction agent comprises by weight percentage: 15 ~ 30% 2-ethylhexyl phosphonic acids single 2-ethyl base ester (P507), 70 ~ 85% 260 solvent oils; Wherein, 2-ethylhexyl phosphonic acids single 2-ethyl the saponification degree of base ester be 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, extraction agent is sulfuric acid when back extraction cobalt.
Preferably, after step b) wolfram varbide filter residue mixes with sodium carbonate and SODIUMNITRATE, be to be first dried 10 ~ 30 minutes under 100 ~ 200 DEG C of conditions in temperature, and then go roasting.
The inventive method can comprehensively reclaim tungsten, cobalt, the various metallic elements of nickel, and the rate of recovery is high, and the rate of recovery of tungsten can reach more than 92%, more than the rate of recovery of cobalt can reach 93 %, more than the rate of recovery of nickel can reach 92 %; Obtain tungsten, cobalt, nickel product purity high, the purity of tungsten is 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 serialization and produce, and has obtained good technique effect.
Embodiment
[embodiment 1]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added to 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3, add oxidants chlorine acid sodium, 2 hours reaction times according to 0.2 times of cobalt ferronickel gross weight simultaneously.90 DEG C of temperature of reaction.Cobalt contents 0.2% in final filter residue, nickel content 0.15%, iron level 0.03%, the leaching yield of cobalt ferronickel is respectively 96%, 97%, 95%.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.2kg obtaining, 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, 430 DEG C of maturing temperatures, time 2 h.
C) reclaim tungsten.Material after roasting leaches in the hot water of 90 DEG C, solid-to-liquid ratio 1:3, and agitation leach 3 hours, the solution containing sodium wolframate 230g/l obtaining, through concentration and evaporation, crystallization obtains sodium wolframate crystal, and 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.Step a) the solution of the acid-soluble cobalt-bearing ferronickel obtaining adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) under pH=2.5 condition, 90 DEG C of stirring reactions 1.5 hours, and the solution that obtains the precipitation of iron and contain cobalt nickel.P507 extraction agent extracting and separating cobalt nickel for the solution obtaining, P507 extraction agent consists of 260 solvent oils of 20% P507+80%, 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 obtaining obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches country-level standard, single nickel salt reaches national grade ii standard, and the rate of recovery of cobalt nickel is respectively 93%, 92%.
[embodiment 2]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added to 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:4, add oxidants chlorine acid sodium, 2 hours reaction times according to 0.25 times of cobalt ferronickel total mass simultaneously.90 DEG C of temperature of reaction.Cobalt contents 0.3% in final filter residue, nickel content 0.12%, iron level 0.1%, the leaching yield of cobalt ferronickel is respectively 96.5%, 97.8%, 96%.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.6kg obtaining, 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, 450 DEG C of maturing temperatures, time 2 h.
C) reclaim tungsten.Material after roasting leaches in the hot water of 95 DEG C, solid-to-liquid ratio 1:3, and agitation leach 4 hours, the solution containing sodium wolframate 250g/l obtaining, through concentration and evaporation, crystallization obtains sodium wolframate crystal, and 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.Step a) the solution of the acid-soluble cobalt-bearing ferronickel obtaining adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) at pH2.5, 90 DEG C of stirring reactions 2 hours, the solution that obtains the precipitation of iron and contain cobalt nickel, P507 extraction agent extracting and separating cobalt nickel for the solution obtaining, P507 extraction agent consists of 260 solvent oils of 20% P507+80%, 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 obtaining obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches country-level standard, single nickel salt reaches national grade ii standard, the rate of recovery of cobalt nickel is respectively 94%, 92%.
[embodiment 3]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added to 2.5mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3.5, add oxidants chlorine acid sodium, 2 hours reaction times according to 0.2 times of cobalt ferronickel total mass simultaneously.90 DEG C of temperature of reaction.Cobalt contents 0.15% in final filter residue, nickel content 0.12%, iron level 0.04%, the leaching yield of cobalt ferronickel is respectively 96.5%, 97.5%, 95%.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.2kg obtaining, 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, 450 DEG C of maturing temperatures, time 2 h.
C) reclaim tungsten.Material after roasting leaches in the hot water of 85 DEG C, solid-to-liquid ratio 1:2, and agitation leach 3 hours, the solution containing sodium wolframate 340g/l obtaining, through concentration and evaporation, crystallization obtains sodium wolframate crystal, and 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.Step a) the solution of the acid-soluble cobalt-bearing ferronickel obtaining adds hydrogen peroxide (hydrogen peroxide of 20 % by weight) at pH2.5, 95 DEG C of stirring reactions 1.5 hours, the solution that obtains the precipitation of iron and contain cobalt nickel, P507 extraction agent extracting and separating cobalt nickel for the solution obtaining, P507 extraction agent consists of 260 solvent oils of 20% P507+80%, 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 obtaining 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 respectively 94%, 93%.
[embodiment 4]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added to 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3.5, add oxidants chlorine acid sodium, 1.5 hours reaction times according to 0.25 times of cobalt ferronickel total mass simultaneously.90 DEG C of temperature of reaction.Cobalt contents 0.15% in final filter residue, nickel content 0.15%, iron level 0.09%, the leaching yield of cobalt ferronickel is respectively 95%, 97%, 96%.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.3kg obtaining, 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, 440 DEG C of maturing temperatures, time 2 h.
C) reclaim tungsten.Material after roasting leaches in the hot water of 90 DEG C, solid-to-liquid ratio 1:3, and agitation leach 3 hours, the solution containing sodium wolframate 210g/L obtaining, through concentration and evaporation, crystallization obtains sodium wolframate crystal, and 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 obtaining 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, the solution that obtains the precipitation of iron and contain cobalt nickel, P507 extraction agent extracting and separating cobalt nickel for the solution obtaining, P507 extraction agent consists of 260 solvent oils of 20% P507+80%, 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 obtaining obtains rose vitriol nickel salt crystal through condensing crystal, final rose vitriol reaches country-level standard, single nickel salt reaches national grade ii standard, the rate of recovery of cobalt nickel is respectively 94%, 92%.
[embodiment 5]
Step is as follows:
A) be oxidized acid-soluble.Grinding material 10Kg is added to 2mol/l sulphuric acid soln according to solid-to-liquid ratio 1:3.5, add oxidants chlorine acid sodium, 2 hours reaction times according to 0.2 times of cobalt ferronickel total mass simultaneously.90 DEG C of temperature of reaction.Cobalt contents 0.17% in final filter residue, nickel content 0.14%, iron level 0.04%, the leaching yield of cobalt ferronickel is respectively 97%, 97.5%, 95%.
B) soda roasting wolfram varbide slag.Acid-soluble rear filtration, the wolfram varbide filter residue 8.2kg obtaining, 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, mixing rear elder generation is to be dried 20 minutes under 120 DEG C of conditions in temperature, removes moisture, then roasting in rotary kiln, 450 DEG C of maturing temperatures, time 2 h.
C) reclaim tungsten.Material after roasting leaches in the hot water of 85 DEG C, solid-to-liquid ratio 1:2, and agitation leach 3 hours, the solution containing sodium wolframate 330g/L obtaining, through concentration and evaporation, crystallization obtains sodium wolframate crystal, and 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 obtaining 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, the solution that obtains the precipitation of iron and contain cobalt nickel, P507 extraction agent extracting and separating cobalt nickel for the solution obtaining, P507 extraction agent consists of 260 solvent oils of 20% P507+80%, 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 obtaining 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 respectively 94%, 93%.
[comparative example 1]
Other conditions are constant, only will in [embodiment 1], add oxidants chlorine acid sodium according to 0.05 times of cobalt ferronickel total mass, cobalt contents 0.7% in final filter residue, and nickel content 1.01%, iron level 0.5%, the turnover rate of cobalt ferronickel is respectively 90%, 89%, 90%.
[comparative example 2]
Other conditions are constant, only wolfram varbide filter residue in [embodiment 2] mixed according to mol ratio 1:0.7 with soda (sodium carbonate), and finally through concentration and evaporation, crystallization obtains sodium wolframate crystal, and purity is 99.0%.The rate of recovery 87.2% of final tungsten.
[comparative example 3]
Process grinding material according to the disclosed method of 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 be oxidized powder process to waste hand alloy material, obtain tungsten cobalt mixed oxide powder; Utilize hydrometallurgical principle, tungsten cobalt mixed oxide powder is carried out to Reduced separating, extraction, obtain powdery pure metal tungsten and cobalt.This technical process is long, and equipment requirements is high, operational condition harshness.
Result is: the rate of recovery≤90% of tungsten, the rate of recovery≤90% of cobalt is unsuitable for processing the Wimet that contains nickel, iron etc. simultaneously.
[comparative example 4]
Process grinding material according to the disclosed method of document CN 200910043243.2.Under the condition of 2400 DEG C of logical hydrogen, high-temperature calcination 80 minutes, cooling after through broken, ball milling with sieve and obtain powdered alloy, the whole operational cycle is long, equipment requirements is high, operational condition harshness, energy consumption is large, production cost is higher.
Result: last and product is hybrid alloys powder, and tungsten, cobalt and nickel mix, does not separate separately, and if in grinding material, contain other impurity, as abrasive material, sand, iron filings etc., this method can not be carried out Direct Regeneration.
Claims (9)
1. a recovery and treatment method for scrap hard alloy grinding material, comprises the following steps:
A) be oxidized acid-soluble: will mix with sulphuric acid soln and oxygenant I containing the scrap hard alloy grinding material of cobalt, nickel, iron, tungsten, reaction is filtration afterwards, obtains the solution of wolfram varbide filter residue and cobalt-bearing ferronickel;
B) soda roasting wolfram varbide filter residue: roasting after wolfram varbide filter residue is mixed with sodium carbonate and SODIUMNITRATE, obtains material I;
C) reclaim tungsten: material I be impregnated in hot water, obtain the solution containing sodium wolframate; Solution process concentration and evaporation crystallization containing sodium wolframate obtains sodium wolframate crystal;
D) reclaim cobalt nickel: the solution of the cobalt-bearing ferronickel that step a) obtains adds oxygenant II under the condition of pH=2 ~ 5, after reaction, obtain 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.
2. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, is characterized in that described oxygenant I is selected from least one in hydrogen peroxide, sodium chlorate or potassium permanganate; Described oxygenant II is selected from hydrogen peroxide.
3. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, the concentration that it is characterized in that step a) sulphuric acid soln is 2 ~ 4 mol/L, 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.
4. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, it is characterized in that 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.
5. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, the temperature that it is characterized in that step c) hot water is 40 ~ 99 DEG C, solid-to-liquid ratio is 1:(2 ~ 10), dipping time is 1 ~ 4 hour.
6. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, is characterized in that 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 adding).
7. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, it is characterized in that step d) contains the solution extraction agent extracting and separating cobalt nickel of cobalt nickel, described extraction agent comprises by weight percentage: 15 ~ 30% 2-ethylhexyl phosphonic acids single 2-ethyl base ester, 70 ~ 85% 260 solvent oils; Wherein, 2-ethylhexyl phosphonic acids single 2-ethyl the saponification degree of base ester be 50 ~ 75%.
8. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, is characterized in that solution that step d) contains cobalt nickel is through 8 ~ 12 grades of extractions, 8 ~ 10 grades of washing nickel, 6 ~ 10 grades of back extraction cobalts.
9. the recovery and treatment method of scrap hard alloy grinding material according to claim 1, after it is characterized in that step b) wolfram varbide filter residue mixes with sodium carbonate and SODIUMNITRATE, is first under 100 ~ 200 DEG C of conditions dry 10 ~ 30 minutes in temperature, and then goes roasting.
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Cited By (8)
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| CN105460981A (en) * | 2015-12-24 | 2016-04-06 | 湖南力天钨业股份有限公司 | Method for preparing tungsten carbide and cobalt chloride by tungsten-containing waste |
| CN106282566A (en) * | 2015-05-27 | 2017-01-04 | 云南锡业集团有限责任公司研究设计院 | A kind of method of the tungsten cobalt waste residue cobalt carbonate of iron content |
| CN109019706A (en) * | 2018-07-17 | 2018-12-18 | 金川集团股份有限公司 | A method of utilizing useless nickel alloy production nickel sulfate and cobaltous sulfate |
| 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 |
| CN113667825A (en) * | 2021-07-20 | 2021-11-19 | 广东邦普循环科技有限公司 | Ferronickel wet processing method and application thereof |
| CN114182094A (en) * | 2021-09-16 | 2022-03-15 | 王仕斌 | Comprehensive recycling method for valuable metals in hard alloy grinding material |
| CN114622096A (en) * | 2022-03-15 | 2022-06-14 | 崇义章源钨业股份有限公司 | Method for separating tungsten and cobalt in grinding material |
| CN115386733A (en) * | 2022-09-16 | 2022-11-25 | 江西理工大学 | Method for decomposing and recycling tungsten-containing waste by using nitric-sulfuric mixed acid |
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| CN105460981A (en) * | 2015-12-24 | 2016-04-06 | 湖南力天钨业股份有限公司 | Method for preparing tungsten carbide and cobalt chloride by tungsten-containing waste |
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| CN114182094A (en) * | 2021-09-16 | 2022-03-15 | 王仕斌 | Comprehensive recycling method for valuable metals in hard alloy grinding material |
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| CN114622096A (en) * | 2022-03-15 | 2022-06-14 | 崇义章源钨业股份有限公司 | Method for separating tungsten and cobalt in grinding material |
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| CN115386733A (en) * | 2022-09-16 | 2022-11-25 | 江西理工大学 | Method for decomposing and recycling tungsten-containing waste by using nitric-sulfuric mixed acid |
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