CN111809062A - Method for recycling tungsten-containing tailings in fluorine dressing and metallurgy - Google Patents
Method for recycling tungsten-containing tailings in fluorine dressing and metallurgy Download PDFInfo
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- CN111809062A CN111809062A CN202010713529.3A CN202010713529A CN111809062A CN 111809062 A CN111809062 A CN 111809062A CN 202010713529 A CN202010713529 A CN 202010713529A CN 111809062 A CN111809062 A CN 111809062A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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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
The invention relates to the field of comprehensive utilization of chemical waste residues, and particularly provides a method for recycling fluorine-containing tungsten tailings. The method for recycling the fluorine-smelting tungsten-containing tailings comprises the following steps: firstly, adding sylvite into ore pulp prepared from fluorine dressing and smelting tailings; then adding ammonia water and resin into the ore pulp, and leaching tungsten and generating calcium salt and potassium sulfate in the form of ammonium tungstate; and finally, eluting the ammonium tungstate adsorbed in the resin, recovering the ammonium tungstate, and recovering calcium salt and potassium sulfate from the ore pulp after reaction. According to the method, the ammonium tungstate can be obtained by leaching tungsten with ammonia water and preparing the potassium sulfate, low-value calcium sulfate can be converted into the potassium sulfate with high added value, and the economic benefit is high; the whole process does not need to be carried out under the conditions of high temperature and high pressure, the cost is low, a large amount of sodium carbonate or caustic soda is not needed, subsequent pollutants are not generated, the environment is more friendly, and the economic benefit is good.
Description
Technical Field
The invention relates to the field of comprehensive utilization of chemical waste residues, in particular to a method for recycling tungsten-containing tailings in fluorine separation and metallurgy.
Background
The main minerals of the ore zone are: WO3、Bi、Mo、CaF2And Fe3O4The current general beneficiation production flow for the above mineral strip is as follows: 1. carrying out magnetic separation on the raw ore to obtain iron ore concentrate; 2. selecting sulfide ore from the tailings subjected to magnetic separation by adopting a full flotation process, and performing flotation to obtain Mo concentrate, Bi middling and sulfur concentrate; 3. WO is mainly contained in tailings of full flotation3、CaF2And SiO2And the oxidized ore is taken as the main part, and after 2-3 times of scavenging and fine selection, fluorite concentrate and rough tungsten concentrate are obtained; 4. the scheelite concentrate is obtained after 2-3 times of fine concentration of the rough wolframite concentrate, and the tailings are subjected to table concentrator beneficiation to obtain the wolframite concentrate and the CaF-containing wolframite concentrate2、SiO2The tailings of (2). And respectively carrying out corresponding treatment on the concentrates obtained by the beneficiation process, wherein the fluorite concentrate is used as a raw material for producing hydrogen fluoride, and the beneficiation-metallurgy recovery rate of fluorine is 30-40%.
In order to improve the fluorine concentration recovery rate, the tailings after the sulfide ore flotation is used as a cut-in point, silicon dioxide and garnet in the tailings are removed by a mineral separation means, so that fluorite and tungsten mixed concentrate (hereinafter referred to as mixed concentrate) is obtained, the mixed concentrate is used as a raw material for producing hydrogen fluoride, and the fluorine concentration recovery rate is 70-80%.
In addition, tungsten in tailings (mainly fluorgypsum) can be recovered and extracted, if only tungsten is recovered, the alkali consumption is large, the tungsten is required to be decomposed under the enhanced conditions of high temperature and high pressure, and subsequent pollutants (such as waste water, NaCl or Na after the tungsten is adsorbed by ion exchange) are generated2SO4Etc.) are serious, which is not favorable for the economic development of China. In addition, a large amount of low-value calcium sulfate is also stored in the tailings, and the tungsten is recycled and simultaneously the low value is realizedThe calcium sulfate is converted into chemical products with high added value, and the method has high practical significance and economic significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for recycling tungsten-containing tailings in fluorine dressing and metallurgy, which can be used for obtaining ammonium tungstate, converting low-value calcium sulfate into potassium sulfate with high added value and has high economic benefit; the whole process does not need to be carried out under the conditions of high temperature and high pressure, the cost is low, a large amount of sodium carbonate or caustic soda is not needed, subsequent pollutants are not generated, the environment is more friendly, and the economic benefit is good.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for recycling fluorine-containing tungsten tailings, which comprises the following steps:
firstly, adding resin and sylvite into ore pulp prepared from fluorine-containing tungsten tailings;
then adding ammonia water into the ore pulp to leach tungsten and generate calcium salt and potassium sulfate in the form of ammonium tungstate;
and finally, eluting the ammonium tungstate adsorbed in the resin, recovering the ammonium tungstate, and recovering calcium salt and potassium sulfate from the ore pulp after reaction.
As a further preferred embodiment, the potassium salt includes potassium chloride, potassium fluoride, or potassium carbonate.
As a further preferred technical scheme, the resin is a strong-base anion exchange resin.
In a further preferred embodiment, the resin is a strongly basic styrene anion exchange resin.
In a more preferred embodiment, the resin is a 201-W strongly basic styrene anion exchange resin.
As a further preferable technical scheme, the concentration of the ammonia water is 20% -25%.
As a further preferable technical scheme, the reaction temperature after adding ammonia water is 30-35 ℃.
As a further preferable technical scheme, the reaction time after adding the ammonia water is 1 to 3 hours.
As a further preferable technical scheme, the eluent adopted during elution is ammonia water with the concentration of 10% -14%, the dosage of the ammonia water is 1.5-3 times of the volume of the resin, the elution temperature is 35-55 ℃, and the elution pressure is 0.1-0.3 MPa.
Compared with the prior art, the invention has the beneficial effects that:
the method for recycling the tungsten-containing tailings in the fluorine dressing smelting process utilizes ammonia water to leach tungsten and simultaneously prepare potassium sulfate, so that ammonium tungstate can be obtained, low-value calcium sulfate can be converted into potassium sulfate with high added value, and the economic benefit is high.
The method has simple process steps, short flow and easy operation, only needs to leach tungsten in the tungsten-containing tailings in the fluorine separation metallurgy in the form of ammonium tungstate, adds resin into ore pulp before adding ammonia water for leaching to adsorb the leached ammonium tungstate into the resin, avoids further proceeding of leaching reaction due to overlarge concentration of tungstate radicals in the ore pulp, thereby enabling the leaching reaction of tungsten to be more thorough, improving the leaching rate of tungsten, and finally eluting and recycling the ammonium tungstate adsorbed in the resin to extract the tungsten in the tailings; meanwhile, calcium sulfate reacts with potassium salt to generate potassium sulfate and calcium salt under the condition that ammonia water is used as a catalyst, part of calcium salt is easy to react with tungstate radical to generate calcium tungstate originally, and the tungstate radical is adsorbed into resin in the form of ammonium tungstate, so that the formation of calcium tungstate can be effectively avoided.
The whole process of the method does not need to be carried out under the conditions of high temperature and high pressure, has low cost, does not need to use a large amount of sodium carbonate or caustic soda, does not produce subsequent pollutants, is more environment-friendly and has good economic benefit.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
In at least one embodiment, a method for resource utilization of fluorine-containing tungsten tailings is provided, which comprises the following steps:
firstly, adding resin and sylvite into ore pulp prepared from fluorine-containing tungsten tailings;
then adding ammonia water into the ore pulp to leach tungsten and generate calcium salt and potassium sulfate in the form of ammonium tungstate;
and finally, eluting the ammonium tungstate adsorbed in the resin, recovering the ammonium tungstate, and recovering calcium salt and potassium sulfate from the ore pulp after reaction.
According to the method for recycling the tungsten-containing tailings in the fluorine concentration smelting process, the ammonium tungstate can be obtained by leaching tungsten with ammonia water and preparing potassium sulfate at the same time, low-value calcium sulfate can be converted into potassium sulfate with high added value, and the economic benefit is high.
The method has simple process steps, short flow and easy operation, only needs to leach tungsten in the tungsten-containing tailings in the fluorine separation metallurgy in the form of ammonium tungstate, adds resin into ore pulp before adding ammonia water for leaching to adsorb the leached ammonium tungstate into the resin, avoids further proceeding of leaching reaction due to overlarge concentration of tungstate radicals in the ore pulp, thereby enabling the leaching reaction of tungsten to be more thorough, improving the leaching rate of tungsten, and finally eluting and recycling the ammonium tungstate adsorbed in the resin to extract the tungsten in the tailings; meanwhile, calcium sulfate reacts with potassium salt to generate potassium sulfate and calcium salt under the condition that ammonia water is used as a catalyst, part of calcium salt is easy to react with tungstate radical to generate calcium tungstate originally, and the tungstate radical is adsorbed into resin in the form of ammonium tungstate, so that the formation of calcium tungstate can be effectively avoided.
The whole process of the method does not need to be carried out under the conditions of high temperature and high pressure, has low cost, does not need to use a large amount of sodium carbonate or caustic soda, does not produce subsequent pollutants, is more environment-friendly and has good economic benefit.
In a preferred embodiment, the potassium salt comprises potassium chloride, potassium fluoride or potassium carbonate. No matter potassium chloride, potassium fluoride or potassium carbonate, ammonia water can be added into ore pulp to leach tungsten in the form of ammonium tungstate, and potassium sulfate with high added value and corresponding calcium salt can be obtained. The potassium salt has low cost and easily obtained raw materials, and is beneficial to popularization and application.
In a preferred embodiment, the resin is a strongly basic anion exchange resin. Strongly basic anion exchange resins contain strongly basic groups, e.g. quaternary ammonium groups (also known as quaternary amino groups) -NR3OH (R is a hydrocarbon group) capable of dissociating OH in water-The resin is strong in basicity, and the positive electricity group of the resin can be adsorbed and combined with anions in a solution, so that an anion exchange effect is generated, the strong basicity anion exchange resin is strong in dissociation property and can normally work under different pH values, and the strong base can be used for regeneration.
In a preferred embodiment, the resin is a strongly basic styrenic anion exchange resin.
In a preferred embodiment, the resin is a 201-W strongly basic styrenic anion exchange resin. The dispute 201-W strong base styrene anion exchange resin is 'dispute' 201-W strong base styrene anion exchange resin produced by Zhejiang dispute industries, Inc., and has quaternary ammonium group [ -N (CH) on crosslinked styrene-divinylbenzene copolymer3)3OH]The anion exchange resin has the characteristics of high exchange capacity, good adsorption effect and the like.
In a preferred embodiment, the concentration of ammonia is 20% to 25%. The concentration of ammonia is typically, but not limited to, 20%, 21%, 22%, 23%, 24%, or 25%. The ammonia water has moderate concentration, can effectively form ammonium tungstate with tungsten in ore pulp, and promotes the reaction between calcium sulfate and sylvite.
In a preferred embodiment, the reaction temperature after addition of the aqueous ammonia is from 30 to 35 ℃. The above reaction temperature is typically, but not limited to, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ or 35 ℃. If the reaction temperature is too low, the leaching rate of tungsten is not high enough, the generation of potassium sulfate and calcium salt is influenced, if the reaction temperature is too high, energy sources are wasted, and continuous experiments show that the leaching rate, the generation of potassium sulfate and calcium salt and the energy consumption can be considered when the reaction temperature is between 30 and 35 ℃.
In a preferred embodiment, the reaction time after addition of the aqueous ammonia is from 1 to 3 hours. The above reaction time is typically, but not limited to, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours.
In a preferred embodiment, the eluent used in elution is ammonia water with the concentration of 10% -14%, the dosage of the ammonia water is 1.5-3 times of the volume of the resin, the elution temperature is 35-55 ℃, and the elution pressure is 0.1-0.3 MPa. The concentration of the above-mentioned aqueous ammonia is typically, but not limited to, 10%, 11%, 12%, 13% or 14%; the amount of ammonia is typically, but not limited to, 1.5 times, 2 times, 2.5 times, or 3 times the volume of the resin; the above elution temperature is typically, but not limited to, 35 deg.C, 36 deg.C, 37 deg.C, 38 deg.C, 39 deg.C, 40 deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C, 49 deg.C, 50 deg.C, 51 deg.C, 52 deg.C, 53 deg; the above elution pressure is typically, but not limited to, 0.1MPa, 0.12MPa, 0.14MPa, 0.16MPa, 0.18MPa, 0.2MPa, 0.22MPa, 0.24MPa, 0.26MPa, 0.28MPa or 0.3 MPa. The preferred embodiment provides optimized elution conditions, including the concentration, the dosage, the elution temperature and the elution pressure of ammonia water, and through the elution of the preferred elution conditions, the ammonium tungstate adsorbed in the resin can be completely and thoroughly eluted, so that the elution effect is good, and the efficiency is high.
It should be noted that the method also comprises the steps of removing impurities and then evaporating for crystallization after the ammonium tungstate is eluted, and finally ammonium tungstate crystals are obtained; and filtering, washing and drying the ore pulp after reaction to obtain potassium sulfate powder.
It is understood that the amount or concentration of the potassium salt added may be adapted to the amount or concentration of calcium sulfate in the pulp, as will be appreciated by those skilled in the art.
The leaching rate of tungsten obtained by the method is more than 75%, the adsorption rate of tungsten is more than 95%, the elution rate of tungsten is more than 95%, and the conversion rate of sulfate radicals is more than 90%; when the grade of tungsten in the mineral is improved to 1% -2%, the leaching rate of tungsten can reach more than 95%.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A method for recycling fluorine-containing tungsten tailings comprises the following steps:
firstly, adding D310 macroporous weak-base styrene anion exchange resin and potassium chloride into ore pulp prepared from tungsten-containing tailings in fluorine dressing and metallurgy;
then adding ammonia water with the concentration of 14% into the ore pulp to leach tungsten and generate calcium chloride and potassium sulfate in the form of ammonium tungstate, wherein the reaction temperature is 25 ℃, and the reaction time is 4 hours;
and finally, eluting the ammonium tungstate adsorbed in the resin and recovering the ammonium tungstate, and recovering calcium chloride and potassium sulfate from the ore pulp after reaction, wherein the eluent adopted in elution is ammonia water with the concentration of 15%, the using amount of the ammonia water is 1.3 times of the volume of the resin, the elution temperature is 30 ℃, and the elution pressure is 0.4 MPa.
In this example, the leaching rate of tungsten was 75.0%, the adsorption rate of tungsten was 95.3%, the elution rate of tungsten was 95.4%, and the conversion rate of sulfate was 90.5%.
Example 2
A method for utilizing tungsten-containing tailings in fluorine separation metallurgy in a resource mode is different from that in example 1, D201 macroporous strong-base ion exchange resin is adopted in the embodiment, and the rest steps and parameters are the same as those in example 1.
In this example, the leaching rate of tungsten was 75.3%, the adsorption rate of tungsten was 96.0%, the elution rate of tungsten was 95.3%, and the conversion rate of sulfate was 91.3%.
Example 3
A method for utilizing tungsten-containing tailings in fluorine separation metallurgy in a resource mode is different from that in the embodiment 1, D202 macroporous strong-base ion exchange resin is adopted in the embodiment, and the rest steps and parameters are the same as those in the embodiment 1.
In this example, the leaching rate of tungsten was 76.4%, the adsorption rate of tungsten was 96.2%, the elution rate of tungsten was 96.3%, and the conversion rate of sulfate was 92.3%.
Example 4
A method for utilizing tungsten tailings in fluorine concentration is different from the embodiment 1 in that the 201-W strong base styrene anion exchange resin is adopted in the embodiment, and the rest steps and parameters are the same as the embodiment 1.
In this example, the leaching rate of tungsten was 81.8%, the adsorption rate of tungsten was 97.1%, the elution rate of tungsten was 97.2%, and the conversion rate of sulfate was 93.5%.
Example 5
The difference between the method for recycling the tungsten-containing tailings in the fluorine separation and metallurgy process and the embodiment 4 is that the concentration of ammonia water is 20 percent, the reaction temperature is 35 ℃, the reaction time is 1 hour, and the rest steps and parameters are the same as those in the embodiment 4.
In this example, the leaching rate of tungsten was 86.3%, the adsorption rate of tungsten was 97.7%, the elution rate of tungsten was 97.4%, and the conversion rate of sulfate was 94.3%.
Example 6
A method for utilizing tungsten tailings in fluorine dressing metallurgy in a resource mode is different from embodiment 4 in that the concentration of ammonia water in the embodiment is 23%, the reaction temperature is 32 ℃, the reaction time is 2 hours, and the rest steps and parameters are the same as those in embodiment 4.
In this example, the leaching rate of tungsten was 87.5%, the adsorption rate of tungsten was 98.2%, the elution rate of tungsten was 98.2%, and the conversion rate of sulfate was 94.6%.
Example 7
A method for utilizing tungsten tailings in fluorine dressing metallurgy in a resource mode is different from embodiment 4 in that the concentration of ammonia water in the embodiment is 25%, the reaction temperature is 30 ℃, the reaction time is 3 hours, and the rest steps and parameters are the same as those in embodiment 4.
In this example, the leaching rate of tungsten was 88.8%, the adsorption rate of tungsten was 98.7%, the elution rate of tungsten was 98.8%, and the conversion rate of sulfate was 95.1%.
Example 8
The difference between the method and the embodiment 7 is that the elution solution adopted in the elution in the embodiment is 10% ammonia water, the dosage of the ammonia water is 3 times of the volume of the resin, the elution temperature is 35 ℃, the elution pressure is 0.3MPa, and the rest steps and parameters thereof are the same as those in the embodiment 7.
In this example, the leaching rate of tungsten was 89.3%, the adsorption rate of tungsten was 99.0%, the elution rate of tungsten was 99.2%, and the conversion rate of sulfate was 95.5%.
Example 9
The difference between the method and the embodiment 7 is that the elution solution adopted in the elution in the embodiment is 12% ammonia water, the dosage of the ammonia water is 2 times of the volume of the resin, the elution temperature is 45 ℃, the elution pressure is 0.2MPa, and the rest steps and parameters thereof are the same as those in the embodiment 7.
In this example, the leaching rate of tungsten was 89.2%, the adsorption rate of tungsten was 98.5%, the elution rate of tungsten was 99.4%, and the conversion rate of sulfate was 95.8%.
Example 10
The difference between the method and the embodiment 7 is that the eluent adopted in the elution in the embodiment is ammonia water with the concentration of 14 percent, the dosage of the ammonia water is 1.5 times of the volume of the resin, the elution temperature is 55 ℃, the elution pressure is 0.1MPa, and the other steps and parameters are the same as those in the embodiment 7.
In this example, the leaching rate of tungsten was 89.4%, the adsorption rate of tungsten was 99.2%, the elution rate of tungsten was 99.5%, and the conversion rate of sulfate was 96.3%.
Example 11
A method for utilizing tungsten-containing tailings in fluorine dressing metallurgy in a resource mode is different from that in example 1, in the embodiment, potassium carbonate is replaced by potassium chloride, calcium carbonate and potassium sulfate are correspondingly generated and recovered, and the rest steps and parameters are the same as those in example 1.
In this example, the leaching rate of tungsten was 88%, the adsorption rate of tungsten was 97.5%, the elution rate of tungsten was 96.3%, and the conversion rate of sulfate was 99.3%.
Comparative example 1
A method for recycling fluorine-containing tungsten tailings comprises the following steps: firstly, adding potassium chloride and 14% ammonia water into ore pulp prepared from tungsten-containing tailings in the fluorine dressing metallurgy in the form of ammonium tungstate to leach tungsten and generate calcium chloride and potassium sulfate, wherein the reaction temperature is 25 ℃ and the reaction time is 4 hours;
then, adsorbing ammonium tungstate in the leaching solution by using D310 macroporous weakly-basic styrene anion exchange resin;
and finally, eluting the ammonium tungstate adsorbed in the resin and recovering the ammonium tungstate, and recovering calcium chloride and potassium sulfate from the ore pulp after reaction, wherein the eluent adopted in elution is ammonia water with the concentration of 15%, the using amount of the ammonia water is 1.3 times of the volume of the resin, the elution temperature is 30 ℃, and the elution pressure is 0.4 MPa.
Unlike example 1, in this comparative example, ammonium tungstate was adsorbed by using a D310 macroporous weakly basic styrenic anion exchange resin after ammonium tungstate was leached with aqueous ammonia.
The leaching rate of tungsten in the comparative example is 71.5%, the adsorption rate of tungsten is 90.3%, the elution rate of tungsten is 94.2%, and the conversion rate of sulfate radical is 72.1%.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (9)
1. A method for recycling fluorine-smelting tungsten-containing tailings is characterized by comprising the following steps:
firstly, adding resin and sylvite into ore pulp prepared from fluorine-containing tungsten tailings;
then adding ammonia water into the ore pulp to leach tungsten and generate calcium salt and potassium sulfate in the form of ammonium tungstate;
and finally, eluting the ammonium tungstate adsorbed in the resin, recovering the ammonium tungstate, and recovering calcium salt and potassium sulfate from the ore pulp after reaction.
2. The method for recycling the tungsten-containing tailings in the fluorine concentration process according to claim 1, wherein the potassium salt comprises potassium chloride, potassium fluoride or potassium carbonate.
3. The method for recycling the tungsten-containing tailings in the fluorine concentration process according to claim 1, wherein the resin is a strongly basic anion exchange resin.
4. The method for recycling the tungsten-containing tailings in the fluorine concentration process according to claim 1, wherein the resin is strongly basic styrene anion exchange resin.
5. The method for recycling the tungsten-containing tailings in the fluorine concentration process according to claim 1, wherein the resin is a 201-W strong basic styrene anion exchange resin.
6. The method for resource utilization of the tungsten-containing tailings in fluorine concentration according to claim 1, wherein the concentration of the ammonia water is 20% -25%.
7. The method for resource utilization of the fluorine-dressing metallurgy tungsten-containing tailings according to claim 1, wherein the reaction temperature after adding the ammonia water is 30-35 ℃.
8. The method for resource utilization of the tungsten-containing tailings in fluorine concentration according to claim 1, wherein the reaction time after adding the ammonia water is 1-3 hours.
9. The method for resource utilization of the tungsten tailings in the fluorine dressing and metallurgy according to any one of claims 1 to 8, wherein the eluent used in the elution is ammonia water with the concentration of 10 to 14 percent, the dosage of the ammonia water is 1.5 to 3 times of the volume of the resin, the elution temperature is 35 to 55 ℃, and the elution pressure is 0.1 to 0.3 MPa.
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