CN110144466A - A method of recycling tungsten is efficiently separated from alkali leaching tungsten slag - Google Patents
A method of recycling tungsten is efficiently separated from alkali leaching tungsten slag Download PDFInfo
- Publication number
- CN110144466A CN110144466A CN201910397311.9A CN201910397311A CN110144466A CN 110144466 A CN110144466 A CN 110144466A CN 201910397311 A CN201910397311 A CN 201910397311A CN 110144466 A CN110144466 A CN 110144466A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- roasting
- slag
- recycling
- leaching
- Prior art date
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound 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[W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 112
- 239000010937 tungsten Substances 0.000 title claims abstract description 112
- 239000002893 slag Substances 0.000 title claims abstract description 58
- 239000003513 alkali Substances 0.000 title claims abstract description 47
- 238000002386 leaching Methods 0.000 title claims abstract description 46
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- 239000000463 materials Substances 0.000 claims abstract description 57
- 238000002844 melting Methods 0.000 claims abstract description 23
- 239000011901 water Substances 0.000 claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound 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[Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000000034 methods Methods 0.000 claims abstract description 16
- 238000009837 dry grinding Methods 0.000 claims abstract description 14
- XMVONEAAOPAGAO-UHFFFAOYSA-N Sodium tungstate Chemical compound 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[Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound 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[Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims description 19
- 241001081830 Degeneriaceae Species 0.000 claims description 15
- 230000000996 additive Effects 0.000 claims description 15
- 239000000654 additives Substances 0.000 claims description 15
- 239000007787 solids Substances 0.000 claims description 14
- 239000011649 sodium carbonate Substances 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 239000000571 coke Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound 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[O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound 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- 238000003723 Smelting Methods 0.000 claims description 6
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O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- WVBBLATZSOLERT-UHFFFAOYSA-N [Au].[W] Chemical compound 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- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound 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[Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000001123 sodium sulphates Substances 0.000 description 1
- 238000006467 substitution reactions Methods 0.000 description 1
- 230000000576 supplementary Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound 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[O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste materials Substances 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- 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
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- 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
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- 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
- C22B7/04—Working-up slag
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- 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
Abstract
Description
Technical field
The invention belongs to environmental protection and resource circulation utilization field, it is related to the technology recycled containing secondary tungsten resource, More particularly to a kind of method for efficiently separating recycling tungsten from alkali leaching tungsten slag.
Background technique
China is tungsten resource big country, but recently as economy and development in science and technology, domestic and international tungsten product demand is increased sharply, I State's tungsten concentrate yield accounts for 80% or more Gross World Product, and for tungsten resource by exhaustive exploitation, exploitation guarantees that the time limit only remains 16 years.Tungsten The serious sustainable development for restricting society is greatly developed secondary tungsten resource and recycled by resource exhaustive exploitation, with resource Recycling substitution raw ore exploitation, is the fundamental way for solving tungsten resource shortage.It is useless for tungstenics such as hard alloy scraps and its grinding materials The alkali leaching tungsten slag for recycling industry generation of material, wherein tungsten metal average content is (with WO3Meter) it is up to 60% or more, it is great The secondary tungsten raw material of recovery value.
It includes oxidizing roasting-alkaline leaching, sodium salt fusion method, alkali leaching-magnesium that the prevailing technology of tungsten is currently recycled from tungsten slag Insoluble tungsten is changed into soluble tungsten, is reached from tungsten by salt method of purification etc., above-mentioned technique by roasting, melting or wet-leaching The purpose of tungsten is separated and recovered in slag.There is the deficiency high using cost of supplementary product, technical process energy consumption is high in above-mentioned technology;In addition For above-mentioned roasting process technique, because material heating conduction difference causes material local temperature to be difficult to reach technological temperature requirement, directly It connects and limits the scale and efficiency of tungsten Slag treatment.
Summary of the invention
In view of the above problems, the purpose of the present invention is to provide a kind of sides that recycling tungsten is efficiently separated from alkali leaching tungsten slag Method, it is intended to solve the local material that at high cost in the prior art, technical process energy consumption is high and occurs by maturing temperature deficiency Incomplete problem is reacted, ensure that the high efficiente callback of tungsten resource in alkali leaching tungsten slag recycles, promote following for secondary tungsten resource Ring utilizes technological progress, has been effectively relieved China's tungsten resource there is lack of raw materials problem, met call and the market of national energy conservation and emission reduction Demand, have more considerable economic value and society, Significance for Environment.
In order to achieve the above objectives, the method applied in the present invention includes the following steps:
Step S1, alkali is soaked into the drying of tungsten slag, ball milling, screening process;
Step S2, the alkali leaching tungsten slag after screening is mixed in a certain ratio uniformly with sulfate, carbonate, combustion-supporting medium, Then obtained mixed material is subjected to roasting melting, obtains roasting material;
Step S3, the resulting roasting material is crushed, and using ball mill dry grinding sieving;
Step S4, the roasting material after sieving is subjected to water logging, controls extraction temperature, extraction time and leaches liquid-solid ratio, Sodium tungstate separation and concentration in roasting material is recycled in water phase.
Specifically, the main component of the alkali leaching tungsten slag is tungsten carbide, and when ball milling sieves, control is at least in step S1 The tungsten solid impurity particle granularity of 80wt% is less than 100 mesh.
Specifically, in step S2, the sulfate is anhydrous sodium sulfate, additive amount be wolfram element additive amount 10~ 20wt%, the carbonate are sodium carbonate, and additive amount is 60~70wt% of wolfram element additive amount.
Specifically, in step S2, roasting melting is carried out to mixed material using Muffle furnace, smelting temperature control 650~ 800 DEG C, smelting time is 5~15h.
Specifically, when dry grinding is sieved, control at least 85wt%'s crosses roasting material grain graininess less than 100 mesh in step S3.
Specifically, the combustion-supporting medium is one or more of coal, coke, carbon, stalk, additive amount is that alkali soaks tungsten The 20wt% of slag slag weight.
Specifically, in step S4, extraction temperature is 50~100 DEG C, and extraction time is 3~4h, leachings liquid-solid ratio for 4:1~ 7:1。
The beneficial effects of the present invention are:
1, the present invention can provide weak oxide environment, favorably using the mixed salt system of sulfate, carbonate in roasting process In the oxidation and recycling of low price tungsten, the technical bottleneck that alkali leaching tungsten slag one-step method efficiently separates recycling tungsten is breached, tungsten is shortened and returns The flow line of receipts, improves productivity;
2, the present invention increases combustion-supporting medium (coal, coke, carbon, stalk etc.) when roasting melting, can be effectively improved material The phenomenon that layer heating conduction, reduction bed of material different parts uneven heating, is conducive to improve tungsten recovery rate;
3, for the present invention using the tungstates in water seaoning enrichment roasting material, leaching rate is high, leaches at low cost, environmental pollution Small, the valuable elements content such as leached mud visual its cobalt, nickel carries out later separation recycling.
Detailed description of the invention
Fig. 1 is the process flow chart for efficiently separating the method for recycling tungsten in the embodiment of the present invention from alkali leaching tungsten slag.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.
The method that recycling tungsten is efficiently separated from alkali leaching tungsten slag provided by the invention, includes the following steps:
Step S1, alkali soaks the sample preparation of tungsten slag.
Alkali is soaked into the drying of tungsten slag, ball milling, screening process.The leaching tungsten slag of alkali described in this step is for hard alloy scraps and its mill The alkali leaching tungsten slag for recycling industry generation of the tungsten wastes such as material is cut, main component is tungsten carbide, and wherein tungsten metal averagely contains Amount is (with WO3Meter) it is up to 60% or more.When ball milling sieves, the tungsten solid impurity particle granularity of at least 80wt% is controlled less than 100 mesh.
Step S2, double salt meltings.
Specifically, the alkali leaching tungsten slag after screening is mixed in a certain ratio uniformly with sulfate, carbonate, combustion-supporting medium, Then obtained mixed material is subjected to roasting melting, obtains roasting material.
In this step, the sulfate is anhydrous sodium sulfate, and additive amount is 10~20wt% of wolfram element additive amount, institute Stating carbonate is sodium carbonate, and additive amount is 60~70wt% of wolfram element additive amount, and the combustion-supporting medium is coal, coke, charcoal One or more of essence, stalk, additive amount are the 20wt% that alkali soaks tungsten slag slag weight, are carried out using Muffle furnace to mixed material Melting is roasted, at 650~800 DEG C, smelting time is 5~15h for smelting temperature control.In this step, due to not being in Muffle furnace Enclosure space has oxygen and enters participation reaction, reacts with the tungsten carbide in alkali leaching tungsten slag and generates WO3, reaction equation is such as Under:
2WC+5O2=2WO3+2CO2
Anhydrous sodium sulfate adopted in this step plays oxidation, since the oxygen in Muffle furnace is not enough to a WC whole It is oxidized to WO3, need to be added a certain amount of sodium sulphate deoxidation WC, reaction equation is as follows:
WC+2Na2SO4=Na2WO4+Na2S+CO2↑+SO2↑
Sodium carbonate adopted in this step is reacted with cobaltous tungstate a small amount of in alkali leaching tungsten slag generates sodium tungstate, while sodium carbonate It is reacted with the tungstic acid that alkali leaching tungsten slag roasting generates and generates sodium tungstate, reaction equation is as follows:
Na2CO3+CoWO4=CoCO3+Na2WO4
WO3+Na2CO3=Na2WO4+CO2↑
Combustion-supporting medium adopted in this step is reacted with the oxygen in Muffle furnace releases heat, plays and provides the work of heat source With, can stable thermal equilibrium, at 650~800 DEG C of the temperature, the extent of reaction of combustion-supporting medium and anhydrous sodium sulfate is seldom, It can be ignored.
Step S3, roasting material is broken and sample preparation.
The resulting roasting material is crushed, and using ball mill dry grinding sieving.In this step, the roasting material is logical It crosses jaw crusher to be crushed, when dry grinding is sieved, control at least 85wt%'s crosses roasting material grain graininess less than 100 mesh.
Step S4, roasting material water logging.
Roasting material after sieving is subjected to water logging, control extraction temperature, extraction time and leaches liquid-solid ratio, in roasting material Sodium tungstate separation and concentration recycled in water phase.In this step, extraction temperature be 50~100 DEG C, extraction time be 3~ 4h, leaching liquid-solid ratio are 4:1~7:1, and gained liquid is wolframic acid sodium water solution, and solid is leached mud.
In order to illustrate technical solutions according to the invention, the following is a description of specific embodiments.
Embodiment one:
1. obtaining the alkali after sample preparation using the method for multipoint random sampling soaks tungsten slag, its essential element content has been carried out point Analysis detection, by percentage to the quality, testing result are as follows: WO369.17%, Co 7.14%, Ni1.58%, Fe 1.37%.
2. weighing 200g alkali leaching tungsten slag, 65.82g sodium carbonate (the 60% of tungsten amount of metal), 21.94g anhydrous sodium sulfate (tungsten gold The 20% of category amount) and 40g coke (the 20% of alkali leaching tungsten slag slag weight), it is uniformly mixed and is placed in magnetic boat, be then put into magnetic boat Carry out roasting melting in Muffle furnace, Muffle furnace continues melting 5h from room temperature to being kept the temperature after 750 DEG C.
3. closing Muffle furnace after melting and keeping the temperature program, make its cooled to room temperature, take out magnetic boat, use jaw Roasting material is crushed by formula crusher, and with ball mill dry grinding sample preparation, the roasting material grain graininess of crossing for controlling at least 90wt% is less than 100 mesh.
4. the good roasting material of sample preparation of dry grinding is carried out water logging, extraction temperature is 70 DEG C, liquid-solid ratio 7:1, and extraction time is 3.5h, to water logging after, obtain sodium tungstate solution through solid-liquor separation, wherein W content is (with WO3Meter) it is 74.01g/L, it leaches Slag is washed, after drying, and W content is (with WO3Meter) it is 1.23%, the rate of recovery of tungsten is 99.38%.
Embodiment two:
1. obtaining the alkali after sample preparation using the method for multipoint random sampling soaks tungsten slag, its essential element content has been carried out point Analysis detection, by percentage to the quality, testing result are as follows: WO362.87%, Co 6.89%, Ni 1.22%, Fe 1.79%.
2. weighing 200g alkali leaching tungsten slag, 69.80g sodium carbonate (the 70% of tungsten amount of metal), 14.96g anhydrous sodium sulfate (tungsten gold The 15% of category amount) and 40g coke (the 20% of alkali leaching tungsten slag slag weight), it is uniformly mixed and is placed in magnetic boat, be then put into magnetic boat Carry out roasting melting in Muffle furnace, Muffle furnace continues melting 6h from room temperature to being kept the temperature after 780 DEG C.
3. closing Muffle furnace after melting and keeping the temperature program, make its cooled to room temperature, take out magnetic boat, use jaw Roasting material is crushed by formula crusher, and with ball mill dry grinding sample preparation, the roasting material grain graininess of crossing for controlling at least 90wt% is less than 100 mesh.
4. the good roasting material of sample preparation of dry grinding is carried out water logging, extraction temperature is 60 DEG C, liquid-solid ratio 6:1, and extraction time is 4h, to water logging after, obtain sodium tungstate solution through solid-liquor separation, wherein W content is (with WO3Meter) it is 46.89g/L, leached mud After washed, drying, W content is (with WO3Meter) it is 0.58%, the rate of recovery of tungsten is 98.68%.
Comparative example one:
Technique used by this comparative example is similar with embodiment one, and difference is, using sodium carbonate mono-salt molten system Tungsten is recycled, key step is as follows:
1. the sample being the same as example 1 and the method for sampling are selected, after obtaining sample preparation using the method for multipoint random sampling Alkali soak tungsten slag, analysis detection, by percentage to the quality, testing result have been carried out to its essential element content are as follows: WO3 69.17%, Co 7.14%, Ni 1.58%, Fe 1.37%.
2. 200g alkali leaching tungsten slag, 65.82g sodium carbonate (the 60% of tungsten amount of metal) and 40g coke (the 20% of slag weight) are weighed, It is uniformly mixed and is placed in magnetic boat, then magnetic boat is put into Muffle furnace and carries out roasting melting, Muffle furnace is from room temperature to 750 It is kept the temperature after DEG C, continues melting 5h.
3. closing Muffle furnace after melting and keeping the temperature program, make its cooled to room temperature, take out magnetic boat, use jaw Roasting material is crushed by formula crusher, and with ball mill dry grinding sample preparation, the roasting material grain graininess of crossing for controlling at least 90wt% is less than 100 mesh.
4. the good roasting material of sample preparation of dry grinding is carried out water logging, extraction temperature is 70 DEG C, liquid-solid ratio 7:1, and extraction time is 3.5h, to water logging after, obtain sodium tungstate solution through solid-liquor separation, wherein W content is (with WO3Meter) it is 63.94g/L, it leaches Slag is washed, after drying, and W content is (with WO3Meter) it is 8.33%, the rate of recovery of tungsten is 94.64%.
Comparative example two:
Technique used by this comparative example is similar with embodiment one, and difference is, does not add coke and recycles to tungsten, Key step is as follows:
1. the sample being the same as example 1 and the method for sampling are selected, after obtaining sample preparation using the method for multipoint random sampling Alkali soak tungsten slag, analysis detection, by percentage to the quality, testing result have been carried out to its essential element content are as follows: WO3 69.17%, Co 7.14%, Ni 1.58%, Fe 1.37%.
2. weighing 200g alkali leaching tungsten slag, 65.82g sodium carbonate (the 60% of tungsten amount of metal) and 21.94g anhydrous sodium sulfate (tungsten The 20% of amount of metal), it is uniformly mixed and is placed in magnetic boat, then magnetic boat is put into Muffle furnace and carries out roasting melting, Muffle furnace From room temperature to being kept the temperature after 750 DEG C, continue melting 5h.
3. closing Muffle furnace after melting and keeping the temperature program, make its cooled to room temperature, take out magnetic boat, use jaw Roasting material is crushed by formula crusher, and with ball mill dry grinding sample preparation, the roasting material grain graininess of crossing for controlling at least 90wt% is less than 100 mesh.
4. the good roasting material of sample preparation of dry grinding is carried out water logging, extraction temperature is 70 DEG C, liquid-solid ratio 7:1, and extraction time is 3.5h, to water logging after, obtain sodium tungstate solution through solid-liquor separation, wherein W content is (with WO3Meter) it is 67.01g/L, it leaches Slag is washed, after drying, and W content is (with WO3Meter) it is 12.52%, the rate of recovery of tungsten is 92.37%.
It is by embodiment one and comparative example one as it can be seen that mixed using anhydrous sodium sulfate and sodium carbonate in the embodiment of the present invention one Salt system provides weak oxide environment in roasting process, is conducive to the oxidation and recycling of low price tungsten, the rate of recovery of tungsten reaches 99.38%, in comparative example one, using sodium carbonate mono-salt molten system, compared to the mixed salt body of anhydrous sodium sulfate and sodium carbonate System, furnace charge degree of oxidation is weaker, and tungsten recovery rate is declined, and is 94.64%.By embodiment one and comparative example two as it can be seen that In the present embodiment one, coke joined when roasting melting, can effectively improve bed of material heating conduction, reduce bed of material different parts The phenomenon that uneven heating, is conducive to improve tungsten recovery rate, and without addition coke in comparative example two, furnace charge heating conduction is by shadow It rings, tungsten recovery rate decreases, and is 92.37%.
In embodiments of the present invention, it using anhydrous sodium sulfate and sodium carbonate mixed salt system, can be provided in roasting process weak Oxidation environment is conducive to the oxidation and recycling of low price tungsten, breaches the technology bottle that alkali leaching tungsten slag one-step method efficiently separates recycling tungsten Neck, shorten tungsten recycling flow line, improve productivity, at the same in fused materials be added combustion-supporting medium (coal, coke, Carbon, stalk etc.), the phenomenon that bed of material heating conduction can be effectively improved, reduce bed of material different parts uneven heating, be conducive to improve Tungsten recovery rate, and using the tungstates in water seaoning enrichment roasting material, leaching rate is high, leaching is at low cost, environmental pollution is small, leaching The valuable elements contents such as visual its cobalt, nickel of slagging tap carry out later separation recycling.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
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CN103614545A (en) * | 2013-11-22 | 2014-03-05 | 中南大学 | Method for treating low-grade tungsten concentrate and tungsten slag |
CN109554534A (en) * | 2018-12-18 | 2019-04-02 | 信丰华锐钨钼新材料有限公司 | A kind of method that tungstenic mixture efficiently leaches tungsten |
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JP2011047013A (en) * | 2009-08-28 | 2011-03-10 | Mitsubishi Materials Corp | Recovery treatment method for tungsten |
CN102978381A (en) * | 2012-12-25 | 2013-03-20 | 陈检辉 | Technology for producing tungsten trioxide by prilling and roasting of tungsten slag |
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