CN101177303B - Method for removing molybdenum, arsenic, antimony and stannum from tungstate solution - Google Patents
Method for removing molybdenum, arsenic, antimony and stannum from tungstate solution Download PDFInfo
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- CN101177303B CN101177303B CN2007101767580A CN200710176758A CN101177303B CN 101177303 B CN101177303 B CN 101177303B CN 2007101767580 A CN2007101767580 A CN 2007101767580A CN 200710176758 A CN200710176758 A CN 200710176758A CN 101177303 B CN101177303 B CN 101177303B
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- tungstate solution
- arsenic
- adsorbate
- molybdenum
- antimony
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Abstract
The invention discloses a method of removing molybdenum, arsenic, antimony and tin from the tungstate solution, which belongs to technical field of chemistry and metallurgy. The invention is characterized in that firstly, the tungstate solution is vulcanized; secondly, the precipitator is added and mixed with the thiosalt of the impurity to form the organic compound sediment; thirdly, the adsorbate is added to process filter and separation; fourthly, the filtrate is tungstate solution without impurity, the filter residue is the adsorbate and the organic compound, the adsorbate can be reused through extrication- regeneration. The invention has the advantages of good performance of impurity removal, simple equipment, low production cost, short process, and convenient operation.
Description
Technical field
The invention belongs to chemistry, field of metallurgy, particularly be a kind of method of from tungstate solution, removing molybdenum, arsenic, antimony, tin during tungsten is smelted.
Background technology
Along with development of modern science and technology, on the one hand people propose more and more higher requirement to the compound of tungsten, tungstenalloy and tungsten, and particularly in recent years, high-tech area is more urgent to the demand of the tungsten of high purity and premium properties and goods thereof; Owing to the continuous exploitation of tungsten ore, the high-quality tungsten ore gradually reduces, and causes people to have to handle the tungsten ore that grade is low, impurity component is complicated in the future on the other hand.A difficult problem that exists in tungsten smelting process is exactly the separation of removal, the especially molybdenum of impurity such as molybdenum, arsenic, particularly when preparation high pure metal tungsten and compound thereof impurity such as molybdenum, arsenic etc. is had certain requirement.
At microelectronics, optics and optoelectronic areas, particularly aspect sufacing and thin-film material, market constantly enlarges the demand of target, people require also further to improve to the metal purity of target simultaneously, in order to satisfy the development of microelectronic industry metallic film technology, need to adopt high-melting-point, high resistivity, highly purified tungsten and goods thereof to make barrier material.Highly purified in addition tungsten and goods thereof also have certain application in the thermometry field, people are more and more higher to the accuracy requirement of tungsten-rhenium thermocouple, market demand also constantly increases, and has presented the situation that the part tungsten-rhenium thermocouple substitutes the precious metal platinum-rhodium thermocouple.
Present domestic most tungsten smeltery adopts ion exchange method to carry out the purification of tungsten, promptly selects for use strongly basic anion exchange resin to separate the purification sodium wolframate.When adopting strongly basic anion exchange resin to handle sodium tungstate solution, reach the purpose of separating impurity and absorption purification tungsten according to difference to the adsorption of metal ions ability.This method has flow process weak point, less investment, tungsten loss is few, the rate of recovery is high, easy and simple to handle, characteristics such as work situation is good, but this method can not be removed molybdenum effectively.If molybdenum content height then needs to increase separately and removes the molybdenum operation.Some producers adopt the moly-sulfide method to remove molybdenum, promptly at first with MoO
4 2-Be sulfided into MoS
4 2-, again through being MoS transition
3Precipitation is removed molybdenum, and the main drawback of this method is seriously polluted, promptly at MoS
3Produce toxic gas H in the forming process
2S, the loss of tungsten is also very big simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of by the method for removing molybdenum, arsenic, antimony, tin in the tungstate solution, characteristics such as this method has good impurity removing effect, and equipment is simple, cost is low.
In order to achieve the above object, the technical solution used in the present invention is: at first tungstate solution is vulcanized, make the compound of molybdenum, arsenic, antimony, tin generate corresponding sulfo-acid group; Temperature stirs the sulfo-acid group and the precipitation agent that made molybdenum, arsenic, antimony, tin in 0.5～2.5 hour and is formed with the organic compounds precipitation under 20 ℃～70 ℃ conditions; Add adsorbate at last and carry out filtering separation, filtrate is that filter residue is adsorbate and organogenous sediments except that the pure tungstate solution of impurity such as molybdenum.Adsorbate can be reused through freeing-regenerating.
For technical scheme of the present invention is described, the enforcement of the inventive method may further comprise the steps:
1. sulfuration: the sulfurized method is ripe in tungsten is smelted, and promptly adds a certain amount of S in tungstate solution
2-As Na
2S or (NH
4)
2S etc. are by controlling the corresponding sulfo-acid group of compound formation that parameters such as pH, temperature, time make molybdenum, arsenic, antimony, tin.
2. precipitate: join after a certain amount of precipitation agent is dissolved in pure water through in the sulfurized tungstate solution, temperature stirred 0.5～2.5 hour under 20 ℃～70 ℃ conditions, and purpose is to make the sulfo-acid group of molybdenum, arsenic, antimony, tin and precipitation agent be formed with the organic compounds precipitation.
3. filter: purpose is that the organogenous sediments that contains impurity element that will form separates from tungstate solution, and filtrate is the tungstate solution after the removal of impurities, and filter residue is an organogenous sediments.
When filtering, can also add adsorbate absorption organogenous sediments and again it be carried out filtering separation.The adsorbate that is adopted is gac and goods thereof, and can adopt wherein a kind of, or two or more mixtures uses simultaneously as adsorbate.
The available clear water of freeing-regenerate of adsorbate cleans, and can also adopt method such as heating to regenerate.
Filter operation can also adopt array mode to carry out, that is: at first adopt fibre product or weaving, chemically woven fabrics and goods thereof that organogenous sediments is carried out filtering separation to the tungstate solution of post precipitation or leave standstill the regular hour and carry out filtering separation again; Secondly add adsorbate and make further absorption and filtering separation in this filtrate, filtrate is pure tungstate solution.
Tungstate solution among the present invention can be a sodium tungstate solution, can also be ammonium tungstate solution or ammonium paratungstate (APT) crystalline mother solution.
The precipitation agent that adds during precipitation is a quaternary ammonium salt cationic surfactant, a kind of in preferred Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, the octadecyl trimethyl ammonium chloride, or two or more mixtures, its add-on is 0.7～10 times of theoretical amount.
Advantage of the present invention is a good impurity removing effect, and equipment is simple, and production cost is low, and flow process is short, easy handling.
Description of drawings
The technical process that Fig. 1 purifies for the tungstate solution removal of impurities;
Embodiment
The following stated embodiment describes the present invention in detail.
Embodiment 1
Get ammonium tungstate solution 100ml, wherein WO
3220g/l, Mo 1.70g/l.At first at when sulfuration S
2-Add-on add Na by calculating excessive 3.5g/l
2S, 20 ℃ were vulcanized 24 hours down; Next adds precipitation agent octadecyl trimethylammonium bromide, and add-on is 0.9 times of theoretical amount, is about in the pure water dissolved organism precipitation agent and joins ammonium tungstate solution and stirred 1.5 hours under 20 ℃; The activated carbon fiber that adds the 15g shred at last stirred 0.5 hour, left standstill after 0.5 hour and filtered.Ammonium tungstate solution after the filtration contains Mo 0.05g/l, removes molybdenum rate 95.1%, and activated carbon fiber contains W＜20ppm after the pure water secondary washing.
Embodiment 2
Get ammonium tungstate solution 100ml, wherein WO
3120g/l, Mo 0.25g/l.When sulfuration, S
2-Add-on add Na according to calculating by excessive 3.0g/l
2S; Add Dodecyl trimethyl ammonium chloride in sulfuration under 20 ℃ after 24 hours, the precipitation agent add-on is 5 times of theoretical amount, and soon dissolved organism precipitation agent joins ammonium tungstate solution stirring 2.0 hours in the pure water under 20 ℃; Add the 15g gac afterwards again and stirred 0.5 hour, after filtration, filtrate contains Mo 0.002g/l, and removing the molybdenum rate is 99.0%.
Embodiment 3
Get sodium tungstate solution 100ml, wherein WO
380g/l, Mo 2.0g/l.Under the situation of sodium tungstate solution pH=7.0, vulcanize S during sulfuration
2-Add-on add Na according to calculating excessive 2.6g/l
2S; Add palmityl trimethyl ammonium chloride after 2.0 hours and stirred 0.5 hour 70 ℃ of sulfurations, the precipitation agent add-on is 3 times of theoretical amount; Leave standstill and adopt non-woven fabrics to carry out filtering separation after 0.5 hour, filtrate contains Mo 0.1g/l, and removing the molybdenum rate is 93.5%.
Embodiment 4
In the filtrate of embodiment 3, add gac 20g and stirred 2 hours, after leaving standstill 1 hour, filter, filtrate after testing: Mo＜0.002g/l.
Embodiment 5
Get ammonium tungstate solution 100ml, wherein WO
3220g/l, Mo 0.030g/l, As 0.012g/l, Sb 0.010g/l, Sn 0.009g/l.S during sulfuration
2-Add-on add (NH according to calculating by excessive 2.25g/l
4)
2S; Add octadecyl trimethyl ammonium chloride in sulfuration under 20 ℃ after 24 hours, add-on is 5 times of theoretical amount, and the organism precipitation agent adds back stirring 2.5 hours down in 20 ℃; Adding gac 5g stirring at last left standstill 1.0 hours after 0.5 hour again.The content of filtrate filtered Mo, As, Sb, Sn in the ammonium paratungstate (APT) that evaporative crystallization obtains is all less than 1ppm.
Claims (3)
1. method of from tungstate solution, removing molybdenum, arsenic, antimony, tin, comprise that the tungstate solution to containing in molybdenum, arsenic, antimony, the tin any one or two or more impurity elements vulcanizes, make impurity element change into corresponding sulfo-acid group, it is characterized in that, join in the tungstate solution after the sulfuration as precipitation agent with quaternary ammonium salt cationic surfactant, under 20 to 70 ℃ of conditions, stirred 0.5～2.5 hour, make the thiosalt of itself and above-mentioned impurity element be formed with the organic compounds precipitation; Add gac at last and goods adsorb as adsorbate, the filtrate after the filtering separation is the tungstate solution after the removal of impurities, and filter residue is adsorbate and organogenous sediments.
2. method according to claim 1, it is characterized in that, described precipitation agent quaternary ammonium salt cationic surfactant is one or more the mixture in Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide and the octadecyl trimethyl ammonium chloride, and its add-on is 0.7～10 times of theoretical amount.
3. method according to claim 1 is characterized in that, described tungstate solution is sodium tungstate solution or ammonium tungstate solution or ammonium para-tungstate crystal mother solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101767580A CN101177303B (en) | 2007-11-02 | 2007-11-02 | Method for removing molybdenum, arsenic, antimony and stannum from tungstate solution |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN2007101767580A CN101177303B (en) | 2007-11-02 | 2007-11-02 | Method for removing molybdenum, arsenic, antimony and stannum from tungstate solution |
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| CN101177303B true CN101177303B (en) | 2010-06-02 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863569B (en) * | 2010-05-28 | 2012-01-11 | 厦门嘉鹭金属工业有限公司 | Tungsten-containing wastewater treatment method in tungsten smelting |
| CN104789791B (en) * | 2015-04-14 | 2017-06-23 | 吉林省有色金属地质勘查局研究所 | The automatic releasing device of steel foams gold |
| CN105986160A (en) * | 2016-06-24 | 2016-10-05 | 贵研铂业股份有限公司 | Method for preparing large-size high-purity tungsten titanium alloy target materials |
| CN112301218A (en) * | 2020-09-02 | 2021-02-02 | 崇义章源钨业股份有限公司 | Method for separating molybdenum-containing precipitate in tungstate solution by adopting filtration-adsorption column |
| CN114921649B (en) * | 2022-03-22 | 2023-11-10 | 湖北绿钨资源循环有限公司 | Method for recycling soluble tungstate in tungsten-containing waste |
| CN114855000B (en) * | 2022-04-28 | 2023-08-22 | 湖北绿钨资源循环有限公司 | Method for separating and removing impurities from tungsten and molybdenum in tungsten smelting process |
Citations (5)
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|---|---|---|---|---|
| US4278642A (en) * | 1979-05-14 | 1981-07-14 | Gte Products Corporation | Method for removing molybdenum from tungstate solutions by solvent extraction |
| CN1084575A (en) * | 1993-07-13 | 1994-03-30 | 中南工业大学 | Ion-exchange one-stage separation of phosphorus, arsenic, silicon, molybdenum are produced the technology of pure ammonium tungstate |
| RU2102326C1 (en) * | 1996-12-04 | 1998-01-20 | Институт общей и неорганической химии им. Н.С.Курнакова РАН | Method for processing sodium tungstate liquors |
| CN1203279A (en) * | 1997-06-19 | 1998-12-30 | 中南工业大学 | Process for removing Mo, As, Sb and Sn by precipitating of tungstate solution |
| CN1225075A (en) * | 1996-07-05 | 1999-08-04 | H·C·施塔克公司 | Process for preparing pure alkali and/or ammonium tungstate solutions |
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|---|---|---|---|---|
| US4278642A (en) * | 1979-05-14 | 1981-07-14 | Gte Products Corporation | Method for removing molybdenum from tungstate solutions by solvent extraction |
| CN1084575A (en) * | 1993-07-13 | 1994-03-30 | 中南工业大学 | Ion-exchange one-stage separation of phosphorus, arsenic, silicon, molybdenum are produced the technology of pure ammonium tungstate |
| CN1225075A (en) * | 1996-07-05 | 1999-08-04 | H·C·施塔克公司 | Process for preparing pure alkali and/or ammonium tungstate solutions |
| RU2102326C1 (en) * | 1996-12-04 | 1998-01-20 | Институт общей и неорганической химии им. Н.С.Курнакова РАН | Method for processing sodium tungstate liquors |
| CN1203279A (en) * | 1997-06-19 | 1998-12-30 | 中南工业大学 | Process for removing Mo, As, Sb and Sn by precipitating of tungstate solution |
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Effective date of registration: 20200225 Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone Branch Hing Street No. 11 Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Patentee before: GENERAL RESEARCH INSTITUTE FOR NONFERROUS METALS |