CN1091429C - Process for preparing thiomolybdate by separating tungsten from molybdenum - Google Patents
Process for preparing thiomolybdate by separating tungsten from molybdenum Download PDFInfo
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- CN1091429C CN1091429C CN98123639A CN98123639A CN1091429C CN 1091429 C CN1091429 C CN 1091429C CN 98123639 A CN98123639 A CN 98123639A CN 98123639 A CN98123639 A CN 98123639A CN 1091429 C CN1091429 C CN 1091429C
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- thioated
- solution
- agent
- value
- thiomolybdate
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Abstract
The present invention relates to a method for preparing thiomolybdate by separating tungsten from molybdenum, which belongs to the technical field of the production and the purification of metals. The method is characterized in that a sulfur-containing organic compound is used as a sulphation agent of molybdenum instead of an inorganic sulfur-containing compound, which makes the method has the advantages of dosage reduction of an industrial sulphation agent and other matching chemical reagents, low working cost, simplified sulphation steps, short operation time and easy realization for industrialization production.
Description
The present invention relates to the extraction of the production of metal and refining field, especially tungsten, molybdenum.
In existing tungsten production technique, in all kinds of separation methods of Separation of Molybdenum, maximum from tungstate solution based on a class methods research that generates Thiomolybdate, use also successful.It is under certain process conditions, utilizes the chemical property difference of thiomolybdate complex ion and tungstate ion, can adopt multiple separation method to carry out tungsten and separate, and comprises MoS
3The precipitator method suppress method, absorption method, solvent extration and the ion exchange method that molybdenum is separated out when crystallization, precipitation tungsten compound.
The method that the inhibition molybdenum that USSR476231 proposes is separated out is with (NH
4)
2S does the thioated agent, and molybdenum stays in crystalline mother solution when crystallization ammonium paratungstate (APT), obtains to remove the APT product of molybdenum.
The active carbon adsorption that CN87102098 proposes, object solution is sodium tungstate solution, the thioated agent is Na
2S or NaHS.Fully contact with powdery or granular carbon through the pretreated sodium tungstate solution of thioated, gac quantitatively adsorbs molybdenum, makes sodium tungstate solution obtain to purify.
The solvent extration that U.S Pat.4288413 proposes, the thioated agent is Na
2S or NaHS, extraction agent are Aliquat336, and it can separate tungsten thiomolybdate complex ion quantified extract.
The ion exchange method that CN88105712.6 proposes, thioated agent are that sodium tungstate solution adopts Na
2S, NaHS, ammonium tungstate solution adopts (NH
4)
2S wears by anion exchange resin bed to molybdenum leakage through the pretreated feed liquid of thioated, again with certain C l
-The chloride solution drip washing resin of concentration, the tungsten behind leacheate and the friendship back liquid merging reclaiming clean in the solution.
The ion-exchange one-stage separation of phosphorus arsenic silicon molybdenum that CN93111497.7 proposes is produced the technology of pure ammonium tungstate, and the pretreated thioated agent of solution is NaHS or H
2S gas, through pretreated sodium tungstate solution, by the continuous ionic exchange process that need not turn and be, a step separating impurity Pb, As Si molybdenum is produced the pure tungsten acid ammonium solution.
Above-mentioned cited representative from tungstate solution the method for Separation of Molybdenum, object solution all needs the thioated pre-treatment, the thioated agent of being adopted has Na
2S, NaHS, (NH
4)
2S and H
2S all belongs to inorganic sulfocompound.
For sodium tungstate solution, according to the thioated reaction principle, the abundant thioated of molybdenum is reflected under the nearly neutrallty condition just can be finished.The general pH preset method that adopts on the technology is because of thioated agent Na
2S, NaHS is alkaline, therefore the thioated reaction itself is to release alkali reaction, general pre-adjust pH needs lower, simultaneously, for make except that molybdenum technology can with the ion exchange process organic linking of tungsten, in the higher situation of stoste free alkali, in and free alkali and pH adjust and should not adopt strong inorganic acid, influence harmful inorganic acid radical ion that tungsten ion exchanges in order to avoid too much introduce.For this reason, one of ion-exchange one-stage separation of phosphorus arsenic silicon molybdenum method of producing pure ammonium tungstate process using is to use CO
2Gas is adjusted the pH value of solution value, but CO
2Consumption big, the sodium hydroxide system is especially serious, and is obviously uneconomical.Use at present comparatively that the agent of ideal thioated is a Sodium sulfhydrate, contain NaHS only 70% in the one-level industry Sodium sulfhydrate, amount to that to become to contain S be 40%, and the price height, therefore in the processing charges of APT, the expense of thioated agent is occupied quite high deal.
The objective of the invention is to: reduce the consumption of thioated agent, the chemical reagent expense is descended, no detrimental impurity is introduced, through the pretreated tungstate solution of thioated, can be suitable for the whole bag of tricks and separate tungsten, molybdenum remove the effect excellence, and the preparation technology of Thiomolybdate simplifies.
Technical scheme of the present invention is: be used for the pretreated thioated agent of thioated and adopt sulfur-containing organic compound CS
2(dithiocarbonic anhydride) or SC (NH
2)
2(thiocarbamide), with the replacement inorganic sulfocompound, thereby the thioated pre-treatment is finished by following steps:
(1) the thioated agent dissolves in
In the alkalescence tungstate solution, be metered into sulfur-containing organic compound such as CS
2Or SC (NH
2)
2Deng, free sulfonium ion concentration 1-10g/L in the control solution is under abundant stirring situation, controlled temperature 30-70 ℃, the 0.5-3hr that holds time fully dissolves in the object solution thioated agent by its decomposition and neutralization reaction, the carrying out that the existence of free alkali can promote and accelerate decomposition is reacted is with CS
2Be example, its combined reaction is as follows:
(2) adjustment of pH value of solution value
At normal temperatures, feed CO with certain flow velocity
2The low dense strong inorganic acid solution of gas or adding makes the pH value of solution value be transferred to 8-11, does not have this step when object solution is ammonium tungstate solution.
(3) adjust standing and reacting 3-12hr under the solution normal temperature of pH value, or under 50～90 ℃ of temperature, react 3-0.5hr.Promptly make methods such as can be used for mat precipitation, absorption, extraction, ion-exchange carry out the isolating thioated of tungsten tungstate solution.
Above-mentioned three steps can be carried out in same container continuously, also can segmentation carry out in different vessels.
This has following advantage mutually with prior art in the present invention:
1. reduce thioated agent expense.As CS
2The percentage composition of middle sulphur is about 84%, compares with industrial Sodium sulfhydrate, and its relative consumption can reduce half, and the price of industrial dithiocarbonic anhydride is lower than industrial Sodium sulfhydrate, thereby thioated agent expense descends significantly.
2. and Na
2S, inorganic thioated agent such as NaHS is compared, and organic thioated agent that the present invention uses can play neutralization part free alkali, and in addition, endpoint pH allows to be higher than former technology pH preset value, when adopting CO
2Can improve CO when adjusting the pH value
2Utilization ratio, its consumption can be saved
3. the thioated step is simplified, need not adjust back operation just can with the ion-exchange organic linking of tungsten, the activity duration shortens dramatically, and has reduced chemical reagent consumption, production cost significantly reduces.
Embodiment
Embodiment one
1. the preparation of thioated feed liquid
Sodium tungstate solution contains WO
3101g/L, Mo1.49g/L, NaOH16.0g/L, treatment capacity 1L, CS
2Consumption is 5.6mL.40 ± 2 ℃ of temperature are dissolved in the thioated agent, and time 1hr uses CO
2The whole pH value of solution value of controlled atmosphere is 8.40, at 70 ℃ of reaction 1hr, removes the inspection of molybdenum effect with ion-exchange more thereafter, advances one times of the preceding solution dilution of exchange column.
2. ion-exchange removes the inspection of molybdenum effect: exchange resin is the macropore strong base negative resin, and the exchanging column resin loading capacity is 21ml, single-column absorption, and absorption flow 0.5ml/min, the outlet liquid composition behind the absorption 1500ml solution is WO
350.0g/L, Mo0.0044g/L, Mo/WO
3=8.8 * 10
-5, the WO of unit wet resin
3Treatment capacity is 3.57g/ml.
Experimental example two
1. the preparation of thioated feed liquid
Industry sodium tungstate solution composition: WO
3103.5g/L, Mo1.42g/L, NaOH8.52g/L, treatment capacity 50l, CS
2Add-on 268ml dissolves in temperature, and 30～35 ℃, time 1hr, CO
2The whole pH of controlled atmosphere is 8.88, room temperature reaction 6hr, and the feed liquid for preparing directly extracts inspection.
2. the extraction material liquid component after the thioated: WO
3103.25g/L, Mo1.41g/L, pH8.88, extracted organic phase 3%N
263-20%TBP-kerosene, single-stage extraction is compared 1: 1, duration of contact 5min, raffinate composition, WO
398.6g/L, Mo0.01g/L, Mo/WO
3=1.01 * 10
-4, percentage extraction 99.29%.
Embodiment three
1. the preparation of thioated feed liquid
The ammonium tungstate solution composition, WO
3220.5g/L, Mo0.32g/L, free ammonia 32.0g/L, treatment capacity 1L, [SC (NH
2)
2] add-on 12.5g, dissolve in 70 ± 2 ℃ of temperature, time 2hr, standing and reacting time 12hr, the thioated feed liquid directly extracts inspection.
2. the thioated effect is checked
Extracted organic phase, 3%N
263-20%TBP-kerosene, single-stage extraction is compared 1: 1, duration of contact 5min, raffinate composition, WO
3218.5g/L, Mo0.08g/L, Mo/WO
3=3.66 * 10
-4
Claims (2)
1. the isolating process for preparing thiomolybdate of tungsten is characterized in that: be used for the pretreated thioated agent of thioated and adopt sulfur-containing organic compound CS
2Or SC (NH
2)
2, with the replacement inorganic sulfocompound, thereby the thioated pre-treatment is finished by following steps:
(1) dissolving in of thioated agent: in the alkaline tungstate solution, be metered into dithiocarbonic anhydride or thiocarbamide, free sulfonium ion concentration is 1-10g/L in the control solution, under 30-70 ℃ of temperature, mix 0.5～3hr, the chemical reaction in the mat solution makes the whole pass into solutions of thioated agent;
(2) adjustment of pH value of solution value: dissolve in the tungstate solution of thioated agent, adjusting the pH value of solution value with lower concentration strong inorganic acid or slightly acidic gas is 8-11;
(3) the above-mentioned solution of the good pH value of adjusted at room temperature reacts 3-12hr, or reacts 3-0.5hr under 50-90 ℃ of temperature, promptly makes Thiomolybdate;
Above-mentioned three steps are carried out in same container continuously, or carry out stage by stage in different vessels.
2. the isolating process for preparing thiomolybdate of tungsten according to claim 1 is characterized in that described tungstate solution is sodium tungstate solution or ammonium tungstate solution, and its alkaline medium is NaOH, Na
2CO
3And NH
4OH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98123639A CN1091429C (en) | 1998-10-20 | 1998-10-20 | Process for preparing thiomolybdate by separating tungsten from molybdenum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98123639A CN1091429C (en) | 1998-10-20 | 1998-10-20 | Process for preparing thiomolybdate by separating tungsten from molybdenum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1251825A CN1251825A (en) | 2000-05-03 |
| CN1091429C true CN1091429C (en) | 2002-09-25 |
Family
ID=5228270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98123639A Expired - Fee Related CN1091429C (en) | 1998-10-20 | 1998-10-20 | Process for preparing thiomolybdate by separating tungsten from molybdenum |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745269A (en) * | 2016-12-05 | 2017-05-31 | 荆门德威格林美钨资源循环利用有限公司 | Tungsten recovery method for solving molybdenum liquid during ionic energy transfer tungsten |
| CN108726573B (en) * | 2017-04-20 | 2021-05-14 | 中国石油化工股份有限公司 | Tetrathiomolybdate solution, preparation method and application thereof |
| 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 |
| CN114988476B (en) * | 2022-05-31 | 2023-09-12 | 崇义章源钨业股份有限公司 | Sodium tungstate solution treatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037692A (en) * | 1988-05-16 | 1989-12-06 | 中南工业大学 | Molybdenum in the ion exchange method separating tungsten acid salt solution |
| CN1011228B (en) * | 1986-03-14 | 1991-01-16 | 中国科学院上海光学精密机械研究所 | Protective glass |
-
1998
- 1998-10-20 CN CN98123639A patent/CN1091429C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1011228B (en) * | 1986-03-14 | 1991-01-16 | 中国科学院上海光学精密机械研究所 | Protective glass |
| CN1037692A (en) * | 1988-05-16 | 1989-12-06 | 中南工业大学 | Molybdenum in the ion exchange method separating tungsten acid salt solution |
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| Publication number | Publication date |
|---|---|
| CN1251825A (en) | 2000-05-03 |
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