CN110157898B - Method for removing phosphorus, arsenic and silicon from solution containing tungstate and/or molybdate - Google Patents

Method for removing phosphorus, arsenic and silicon from solution containing tungstate and/or molybdate Download PDF

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CN110157898B
CN110157898B CN201910470898.1A CN201910470898A CN110157898B CN 110157898 B CN110157898 B CN 110157898B CN 201910470898 A CN201910470898 A CN 201910470898A CN 110157898 B CN110157898 B CN 110157898B
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molybdate
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CN110157898A (en
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陈星宇
赵中伟
季磊
刘旭恒
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • 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
    • C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B34/34—Obtaining molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The invention relates to a method for removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate. The method comprises the following steps: 1) adding hydrogen peroxide into a solution containing tungstate and/or molybdate, and then adjusting the pH value of the solution to 7-10; 2) adding a calcium-containing compound into the solution after the pH value is adjusted in the step 1), and then filtering to obtain a solution containing peroxytungstate and/or peroxymolybdate. The method provided by the invention can effectively remove the phosphorus, arsenic and silicon impurities without causing the loss of molybdenum and/or tungsten.

Description

Method for removing phosphorus, arsenic and silicon from solution containing tungstate and/or molybdate
Technical Field
The invention relates to the technical field of metal smelting, in particular to a method for removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate.
Background
In the prior art, when tungsten ore, molybdenum-containing raw materials or tungsten-molybdenum ore is treated by an alkaline method, a crude tungstate solution, a crude molybdate solution or a mixed solution of the two is obtained. Because the molybdenum smelting raw material or the tungsten smelting raw material contains more or less certain amount of impurities such as phosphorus, arsenic, silicon and the like, and the impurities also enter the molybdate solution together. To produce an acceptable molybdenum or tungsten product, the phosphorus, arsenic, silicon, etc., must be removed from the molybdate and/or tungstate solution. The more common method is magnesium salt precipitation. The method utilizes the fact that the oxygen acid radical ions of the phosphorus, arsenic and silicon can be combined with magnesium ions under proper conditions to generate magnesium phosphate with small solubility product, magnesium arsenate and magnesium silicate precipitate. However, if conditions are not properly controlled, especially the pH and Mg of the solution2+Poor concentration control can lead to incomplete phosphorus removal, arsenic removal and silicon removal, and in addition, magnesium ions are hydrolyzed to generate a large amount of magnesium hydroxide precipitate which can adsorb molybdenum or tungsten, so that the loss of molybdenum and/or tungsten is increased.
Disclosure of Invention
In fact, besides magnesium ions which form corresponding precipitates with P, As, Si, there are other ions which form corresponding precipitates with P, As, Si, for example calcium ions. Furthermore, the solubility product of magnesium phosphate was found by analysis (1.62X 10)-25) Solubility product of calcium phosphate (2.0X 10)-29) Smaller, the efficiency of precipitated phosphorus removal should be higher. However, calcium salts have not been used as reagents for removing phosphorus, arsenic and silicon. The key reason is that calcium ions can also form insoluble calcium molybdate or calcium tungstate with molybdate or tungstate, so that a large amount of molybdenum is lost when phosphorus, arsenic and silicon are removed.
If calcium is used as the reagent for removing phosphorus, arsenic and silicon, the precipitation reaction of molybdate radicals or tungstate radicals and calcium ions must be avoided. Analysis shows that the formation of calcium tungstate or calcium molybdate is avoided by changing the existence form of tungsten in tungstate radical or molybdenum in molybdate radical. Based on the discovery, a proper amount of hydrogen peroxide is further added into the solution containing tungstate and/or molybdate, so that molybdate radicals are coordinated with the hydrogen peroxide to form peroxymolybdate radicals, and tungstate radicals are coordinated with the hydrogen peroxide to form peroxytungstate radicals. Of course, whether calcium can be used to remove phosphorus, arsenic and silicon is critical in that the peroxymolybdate radical or peroxytungstate radical cannot react with calcium to generate precipitate. After intensive research, we found that peroxymolybdate or peroxymolybdate and calcium do not generate any precipitate.
Based on this, we propose a method for removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate, which can effectively remove phosphorus, arsenic and silicon impurities without causing molybdenum and/or tungsten loss.
A method for removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate comprises the following steps:
1) adding hydrogen peroxide into a solution containing tungstate and/or molybdate, and then adding acid to adjust the pH value of the solution to 7-10;
2) adding a calcium-containing compound into the solution obtained after the pH value is adjusted in the step 1), and then filtering to obtain a peroxytungstate and/or peroxymolybdate solution after impurity removal.
Preferably, in the step 1), the molar ratio of the hydrogen peroxide to tungsten and/or molybdenum in the solution is 1-5: 1 adding hydrogen peroxide into the solution containing tungstate and/or molybdate.
Further, in step 1), hydrochloric acid and/or nitric acid is added to adjust the pH value to 7-10.
Preferably, the calcium-containing compound comprises one or more of calcium chloride, calcium sulfate, calcium carbonate, calcium nitrate, calcium oxide and calcium hydroxide.
Further, the method also comprises the following steps after the step 2):
3) and adding acid into the solution of the peroxytungstate and/or peroxymolybdate after impurity removal until the solution is an acidic solution, and then heating and decomposing the acidic solution to obtain solid tungstic acid and/or solid molybdic acid.
Preferably, in step 3), the acid is added until the solution is an acidic solution, wherein the pH of the acidic solution is less than or equal to 1.5.
Preferably, in the step 3), the acidic solution is subjected to the thermal decomposition at a temperature of 70-120 ℃.
More preferably, in the step 3), the time for the thermal decomposition is 0.5 to 3 hours.
Further, the method also comprises the following steps after the step 3):
4) dissolving the solid tungstic acid and/or the solid molybdic acid obtained in the step 3) in hydrogen peroxide again, and then performing spray pyrolysis to obtain tungsten oxide and/or molybdenum oxide powder; or dissolving the solid tungstic acid and/or solid molybdic acid obtained in the step 3) in ammonia water to obtain an ammonium tungstate and/or ammonium molybdate solution, and then carrying out evaporative crystallization to obtain ammonium paratungstate and/or ammonium tetramolybdate; or calcining the solid tungstic acid and/or the solid molybdic acid obtained in the step 3) to obtain tungsten oxide and/or molybdenum oxide.
Compared with the prior art, the invention has the advantages that: adding hydrogen peroxide into a solution containing tungstate and/or molybdate to convert tungstate into peroxytungstate, converting molybdate into peroxymolybdate, adjusting the pH value of the solution to 7-10, ensuring that a calcium-containing compound can generate corresponding precipitated calcium phosphate, calcium hydrophosphate, calcium arsenate and calcium silicate with the oxygen-containing acid radical ions of phosphorus-arsenic-silicon impurities after being added under the condition of the pH value, and simultaneously avoiding the hydrolysis of calcium ions into calcium hydroxide, and simultaneously using PO for phosphorus at the pH value4 3-Or HPO4 2-Can form a precipitate with calcium without precipitationBy H which cannot form precipitates with calcium2PO4 -When the calcium-containing compound exists, the calcium-containing compound is added under the condition of pH value of 7-10, so that phosphorus is precipitated as calcium phosphate or calcium hydrogen phosphate, arsenic is precipitated as calcium arsenate and silicon is precipitated as calcium silicate, and peroxytungstate or peroxymolybdate does not precipitate with calcium, therefore, the solution containing peroxytungstate and/or peroxymolybdate for removing the phosphorus-arsenic-silicon impurities can be obtained by filtering, and the molybdenum and/or tungsten can not be lost while the phosphorus-arsenic-silicon impurities are effectively removed.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The specific embodiment provides a method for removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate, which comprises the following steps:
1) adding hydrogen peroxide into a solution containing tungstate and/or molybdate according to the molar ratio of 1-5: 1 adding hydrogen peroxide, then adding acid to adjust the pH value of the solution to 7-10, and further adding hydrochloric acid and/or nitric acid to adjust the pH value to 7-10.
2) Adding a calcium-containing compound into the solution with the pH value adjusted in the step 1), and filtering to obtain an impurity-removed peroxytungstate and/or peroxymolybdate solution; the calcium-containing compound comprises one or more of calcium chloride, calcium sulfate, calcium carbonate, calcium nitrate, calcium oxide and calcium hydroxide.
3) Adding one or more of hydrochloric acid, nitric acid and sulfuric acid into a peroxytungstate solution and/or a peroxymolybdate solution until the solution is an acidic solution, further until the pH of the acidic solution is less than or equal to 1.5, and then heating and decomposing the acidic solution at the temperature of 70-120 ℃ for 0.5-3 hours to obtain solid tungstic acid and/or solid molybdic acid.
4) Dissolving the solid tungstic acid and/or the solid molybdic acid obtained in the step 3) in hydrogen peroxide again, and then performing spray pyrolysis to obtain tungsten oxide and/or molybdenum oxide powder; or dissolving the solid tungstic acid and/or solid molybdic acid obtained in the step 3) in ammonia water to obtain an ammonium tungstate and/or ammonium molybdate solution, and then carrying out evaporative crystallization to obtain ammonium paratungstate and/or ammonium tetramolybdate; or calcining the solid tungstic acid and/or the solid molybdic acid obtained in the step 3) to obtain tungsten oxide and/or molybdenum oxide.
To illustrate the method of removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate according to this embodiment, the following examples are given.
Example 1
The crude sodium tungstate solution in this example is obtained by pressure boiling tungsten ore with sodium hydroxide, and the crude sodium tungstate solution contains WO3140.0g/L，P0.3g/L，As0.25g/L，Si0.5g/L。
The embodiment provides a method for removing phosphorus, arsenic and silicon from a crude sodium tungstate solution, which comprises the following steps:
1) adding hydrogen peroxide into the crude sodium tungstate solution according to the molar ratio of 1: 1 adding hydrogen peroxide, and then adding hydrochloric acid to adjust the pH value of the solution to 8;
2) adding calcium chloride into the solution with the pH value adjusted in the step 1), and filtering to obtain a sodium peroxotungstate solution; the sodium peroxytungstate solution contains 0.002g/L of phosphorus, 0.003g/L of arsenic and 0.005g/L of silicon;
3) adding acid into the sodium peroxytungstate solution until the pH value of the solution is less than or equal to 1.5, and then heating and decomposing the acid solution at the temperature of 110-120 ℃ for 1 hour to obtain solid tungstic acid;
4) dissolving the solid tungstic acid obtained in the step 3) in hydrogen peroxide again, and then performing spray pyrolysis to obtain tungsten oxide powder.
Example 2
The crude sodium tungstate solution in this example is obtained by pressure boiling tungsten ore with sodium carbonate, and the crude sodium tungstate solution contains WO3280.0g/L，P4.5g/L，As3.6g/L，Si2.7g/L。
The embodiment provides a method for removing phosphorus, arsenic and silicon from a crude sodium tungstate solution, which comprises the following steps:
1) adding hydrogen peroxide into the crude sodium tungstate solution according to the molar ratio of 3: 1 adding hydrogen peroxide, and then adding nitric acid to adjust the pH value of the solution to 7;
2) adding calcium carbonate into the solution with the pH value adjusted in the step 1), and filtering to obtain a sodium peroxotungstate solution; the sodium peroxytungstate solution contains 0.003g/L of phosphorus, 0.001g/L of arsenic and 0.002g/L of silicon;
3) adding acid into the sodium peroxytungstate solution until the pH value of the solution is less than or equal to 1.5, and then heating and decomposing the acid solution at the temperature of 70-80 ℃ for 3 hours to obtain solid tungstic acid;
4) dissolving the solid tungstic acid obtained in the step 3) in ammonia water to obtain an ammonium tungstate solution, and then carrying out evaporative crystallization to obtain ammonium paratungstate.
Example 3
In the embodiment, the mixed solution of sodium tungsten molybdate is obtained by leaching oxidized roasted sodium carbonate and mixed sodium hydroxide alkali of tungsten molybdenum ore, and the mixed solution of sodium tungsten molybdate contains Mo85.3g/L and WO330.52g/L，P5.3g/L，As4.2g/L，Si1.2g/L。
The embodiment provides a method for removing phosphorus, arsenic and silicon from a sodium tungsten molybdate mixed solution, which comprises the following steps:
1) adding hydrogen peroxide into the sodium tungsten molybdate mixed solution according to the molar ratio of hydrogen peroxide to the total content of tungsten and molybdenum in the solution of 4: 1 adding hydrogen peroxide, and then adding hydrochloric acid to adjust the pH value of the solution to 10;
2) adding calcium oxide into the solution with the pH value adjusted in the step 1), and filtering to obtain a mixed solution of sodium peroxytungstate and sodium peroxymolybdate; the mixed solution of sodium peroxytungstate and sodium peroxymolybdate contains 0.001g/L of phosphorus, 0.004g/L of arsenic and 0.001g/L of silicon.
3) Adding acid into the mixed solution of sodium peroxytungstate and sodium peroxymolybdate until the pH value of the solution is less than or equal to 1.5, and then heating and decomposing the acidic solution at the temperature of 90-100 ℃ for 2 hours to obtain a mixture of solid tungstic acid and solid molybdic acid.
4) Calcining the mixture of the solid tungstic acid and the solid molybdic acid obtained in the step 3) to obtain a mixture of tungsten oxide and molybdenum oxide.
Example 4
The crude sodium molybdate solution in the example was obtained from molybdenum ore by alkaline process and contained Mo149g/L, P3.3g/L, As2.5g/L, and Si3.6 g/L.
The embodiment provides a method for removing phosphorus, arsenic and silicon from a crude sodium molybdate solution, which comprises the following steps:
1) adding hydrogen peroxide into the crude sodium molybdate solution according to the molar ratio of 5: 1 adding hydrogen peroxide, and then adding hydrochloric acid to adjust the pH value of the solution to 9;
2) adding calcium hydroxide into the solution with the pH value adjusted in the step 1), and filtering to obtain a sodium peroxomolybdate solution; the sodium peroxomolybdate solution contains 0.001g/L of phosphorus, 0.001g/L of arsenic and 0.003g/L of silicon;
3) adding acid into the sodium peroxymolybdate solution until the pH value of the solution is less than or equal to 1.5, and then heating and decomposing the acidic solution at the temperature of 80-90 ℃ for 0.5 hour to obtain solid molybdic acid.
4) Dissolving the solid molybdic acid obtained in the step 3) in ammonia water to obtain an ammonium molybdate solution, and then evaporating and crystallizing to obtain ammonium tetramolybdate.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

Claims (8)

1. A method for removing phosphorus, arsenic and silicon from a solution containing tungstate and/or molybdate, which is characterized by comprising the following steps:
1) adding hydrogen peroxide into a solution containing tungstate and/or molybdate, and then adding acid to adjust the pH value of the solution to 7-10; according to the molar ratio of the hydrogen peroxide to tungsten and/or molybdenum in the solution of 1-5: 1 adding hydrogen peroxide into the solution containing tungstate and/or molybdate;
2) adding a calcium-containing compound into the solution obtained after the pH value is adjusted in the step 1), and then filtering to obtain a peroxytungstate and/or peroxymolybdate solution after impurity removal.
2. The method according to claim 1, characterized in that in step 1) the pH is adjusted to 7-10 by adding hydrochloric acid and/or nitric acid.
3. The method of claim 1, wherein in step 2), the calcium-containing compound comprises one or more of calcium chloride, calcium sulfate, calcium carbonate, calcium nitrate, calcium oxide, and calcium hydroxide.
4. The method of claim 1, further comprising, after step 2), the steps of:
3) and adding acid into the solution of the peroxytungstate and/or peroxymolybdate after impurity removal until the solution is an acidic solution, and then heating and decomposing the acidic solution to obtain solid tungstic acid and/or solid molybdic acid.
5. The method of claim 4, wherein in step 3), the acid is added to a pH of the acidic solution of ≤ 1.5.
6. The method according to claim 4, wherein in the step 3), the thermal decomposition is performed on the acidic solution at a temperature of 70 to 120 ℃.
7. The method according to claim 6, wherein in the step 3), the time for the thermal decomposition is 0.5 to 3 hours.
8. The method of claim 4, further comprising, after step 3), the steps of:
4) dissolving the solid tungstic acid and/or the solid molybdic acid obtained in the step 3) in hydrogen peroxide again, and then performing spray pyrolysis to obtain tungsten oxide and/or molybdenum oxide powder; or dissolving the solid tungstic acid and/or solid molybdic acid obtained in the step 3) in ammonia water to obtain an ammonium tungstate and/or ammonium molybdate solution, and then carrying out evaporative crystallization to obtain ammonium paratungstate and/or ammonium tetramolybdate; or calcining the solid tungstic acid and/or the solid molybdic acid obtained in the step 3) to obtain tungsten oxide and/or molybdenum oxide.
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CN110790312B (en) * 2019-11-13 2022-05-17 厦门钨业股份有限公司 Method for preparing ammonium paratungstate by utilizing tungsten-containing waste material
CN113621834A (en) * 2021-08-28 2021-11-09 信丰华锐钨钼新材料有限公司 Method for selectively dephosphorizing molybdenum and phosphorus mixed solution
CN113860373B (en) * 2021-10-19 2023-11-24 中国有色集团（广西）平桂飞碟股份有限公司 Method for removing phosphorus in crude sodium tungstate solution by using industrial gypsum and preparation method of ammonium paratungstate
CN115125401A (en) * 2022-07-28 2022-09-30 深圳星河环境股份有限公司 Method for removing impurity phosphorus during molybdenum recovery from waste molybdenum-nickel catalyst

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