CN111057849B - Method for removing molybdenum in tungstate by ion exchange adsorption - Google Patents
Method for removing molybdenum in tungstate by ion exchange adsorption Download PDFInfo
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- CN111057849B CN111057849B CN201911324924.6A CN201911324924A CN111057849B CN 111057849 B CN111057849 B CN 111057849B CN 201911324924 A CN201911324924 A CN 201911324924A CN 111057849 B CN111057849 B CN 111057849B
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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
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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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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Abstract
The invention discloses a method for removing molybdenum in tungstate by ion exchange adsorption, which comprises the steps of bonding amine groups onto active sites of an anion exchange resin matrix by a chemical synthesis method to obtain amine modified resin, and adding the amine modified resin into a molybdenum-containing tungstate solution after vulcanization treatment to selectively adsorb and remove thiomolybdate ions. The method provided by the invention is simple to operate, the amine modified resin for separating tungsten and molybdenum has a greater affinity to the thiomolybdate than to the tungstate radical, the tungstate radical is hardly lost in the adsorption process, the tungsten loss is greatly reduced, the separation precision is improved, the adsorption capacity is large, the separation efficiency is high, the separation process is efficient and clean, and the method can be applied to actual production activities and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for removing molybdenum in tungstate by ion exchange adsorption.
Background
Tungsten is a widely used high melting point rare metal known as "industrial teeth"; the method is mainly used for producing products such as hard alloy, special steel and the like, is widely applied to the fields of national defense and military industry, aerospace, machining, mine drilling, petroleum catalysis, electronic devices and the like, and is listed as strategic reserve materials by the world large countries. Because the atomic radius, chemical valence state and chemical property in aqueous solution of tungsten and molybdenum are all very similar, the separation of tungsten and molybdenum is a worldwide problem because of the symbiosis in minerals and tungsten and molybdenum wastes.
So far, few research reports about molybdenum removal from molybdenum-containing tungstate solutions at home and abroad exist, and few related reports about novel resin synthesis for removing molybdenum from tungstate solutions are available. With the reduction of high-grade tungsten ore resources, tungsten waste slag and scrap tungsten products become more and more important tungsten smelting sources in the tungsten smelting process, and the molybdenum content in the raw materials is very high, so that molybdenum removal becomes important work for preparing high-performance pure tungsten products.
Currently, most of industrial molybdenum removal methods utilize the property difference between thiomolybdate ions and tungstate ions in a weakly alkaline medium to separate tungsten from molybdenum, and the developed method comprises the following steps: molybdenum trisulfide precipitation method, solvent extraction method and ion exchange method.
The molybdenum trisulfide precipitation method is characterized by that it utilizes the property difference of tungsten-molybdenum compound to make the molybdenum in the molybdenum-containing tungstate solution be completely sulfurized and completely converted into thiomolybdate, and adds acidRegulation to molybdic acid (H)2MoS4) Easily decomposed into MoS due to its instability3And H2S; at pH 2.5-3, tungsten is converted to metatungstate (H)2W12O40 6-) Thereby separating from the molybdenum; the tungsten loss is large in the process and is accompanied by H2S gas is discharged, and tungsten in the mother liquor after molybdenum removal exists in the form of sodium metatungstate, so that the subsequent deposition of scheelite is not facilitated.
The solvent extraction method is an effective method for deeply separating tungsten and molybdenum, and mainly utilizes the property difference of thiomolybdate radicals and tungstate radicals, the property difference of molybdenum oxyanion and tungsten oxyanion, the property difference of peroxy complex to carry out separation and the like. In the separation of tungsten, it has been found in the literature that the anion present in the raffinate is of the type W12O39 6-、ReO4-Most of the existing extracting agents are acidic extracting agents, the application range is narrow, and adverse factors such as organic phase volatilization exist in the process.
The ion exchange method is based on the difference of affinity of thiomolybdate ions and tungstate ions to the resin to realize the separation of tungsten and molybdenum, and the quaternary ammonium type strongly basic anion exchange resin is used for WO4 2-The affinity of (A) is far less than that of the thiomolybdate, so that when the feed liquid flows through the resin, the thiomolybdate ions are adsorbed on the resin, and WO4 2-Will remain in the solution after the hybridization to become pure tungsten solution; the method has the advantages of short process flow, simple operation, easy mastering, effective impurity removal and the like, but the existing ion exchange method has the defects of low resin adsorption capacity, poor resin durability and the like.
For the reasons, the method has the problems of difficult separation, high tungsten loss, low efficiency and the like for the high-tungsten low-molybdenum solution, and is difficult to meet the production requirement of high-performance tungsten products, so the development of the high-efficiency low-performance molybdenum removal technology has higher practical significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for removing molybdenum in tungstate by ion exchange adsorption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing molybdenum in tungstate by ion exchange adsorption is characterized in that an amine group is bonded to an active site of an anion exchange resin matrix by a chemical synthesis method to obtain amine modified resin, and then the amine modified resin is added into a molybdenum-containing tungstate solution after vulcanization treatment to selectively adsorb and remove thiomolybdate ions.
The anion exchange resin comprises a macroporous type and a gel type, and after the solution is subjected to the thioation treatment, molybdenum exists in a form of thiomolybdate anions, and the ionic radius is larger, so that the macroporous anion exchange resin is selected; furthermore, in the macroporous anion exchange resin, the macroporous weakly-alkaline styrene anion exchange resin has larger full capacity; in addition, because the affinity of the amine functional group to the thiomolybdate radical is larger than that of the tungstate radical, the amine group is selected as an effective functional group, and the novel amine resin is prepared through amination reaction.
In the technical scheme, the anion exchange resin matrix is macroporous weak-base styrene anion exchange resin.
Preferably, in the above technical solution, the macroporous weakly basic styrene anion exchange resin has a crosslinking degree of 2-16%, and a particle size of 60-200 mesh.
The exchange capacity of the macroporous weak-base styrene anion exchange resin is reduced along with the increase of the crosslinking degree, and when the crosslinking degree is selected to be between 2 and 16 percent, the exchange capacity is maximum; meanwhile, the specific surface of the resin is reduced along with the increase of the particle size, the size of the specific surface can directly influence the effective contact of the thiomolybdate ions in the adsorption process, and when the particle size of the resin is 60-200 meshes, the thiomolybdate ions in the solution can be well adsorbed.
Further, in the above technical solution, the method for chemically synthesizing the amine modified resin specifically includes:
swelling and filtering the anion exchange resin matrix, washing the swelling agent carried on the surface after solid-liquid separation, then carrying out amination reaction, carrying out secondary filtration after the reaction is finished, and washing the aminating agent carried on the surface after solid-liquid separation again.
Specifically, in the technical scheme, the reaction temperature and the reaction time of the amination reaction are respectively 50-80 ℃ and 25-36 h.
Preferably, in the above technical scheme, the amination agent of the amination reaction is trioctylamine or N1923.
Further preferably, in the above technical solution, the volume of the amination agent added is 3 to 5 times of the volume of the anion exchange resin matrix.
Further, in the above technical scheme, the swelling process of the anion exchange resin matrix is specifically that a swelling agent with a volume of 4-6 times is added into the anion exchange resin matrix, and the reaction is carried out for 8-12 hours at normal temperature.
Still further, in the above technical solution, the number of times of washing of the swelling agent is 3 to 5.
Preferably, in the above technical solution, the cleaning agent used for cleaning the swelling agent for the first time is ethanol, and the cleaning agent used for cleaning the swelling agent for the second time is ethanol or water.
In a preferred embodiment, the swelling agent is N, N dimethylformamide.
Still further, in the above technical scheme, the sulfurization treatment specifically comprises adjusting the pH value of the molybdenum-containing tungstate solution to 6.5-7.2, adding a sulfurizing agent, and then preserving heat at 68-75 ℃ for 1.5-3h, wherein the adding amount of the sulfurizing agent is 4-6 times of the molar amount of the molybdenum.
Specifically, in the above technical solution, the vulcanizing agent is sodium sulfide or sodium hydrosulfide.
Specifically, in the technical scheme, the pH value of the molybdenum-containing tungstate solution is adjusted to 6.8 before adding the vulcanizing agent.
The invention also provides the application of the method in the wet tungsten metallurgy processing.
The invention has the advantages that:
(1) according to the method for removing molybdenum in tungstate by adsorption through the ion exchange method, the amine group is bonded to the active site of the anion exchange resin matrix to obtain the amine modified resin for selectively adsorbing and removing molybdenum, the method is simple to operate, and the mechanical strength of the resin can be enhanced;
(2) the amine modified resin obtained by the method for removing molybdenum in tungstate by adsorption through the ion exchange method has higher affinity to thiomolybdate than tungstate, and tungstate is hardly lost in the adsorption process, so that tungsten loss is greatly reduced, and separation precision is improved;
(3) the amine modified resin obtained by the method provided by the invention has large adsorption capacity and high separation efficiency;
(4) the method for removing molybdenum through ion exchange selective adsorption provided by the invention separates tungsten and molybdenum in a molybdenum-containing tungstate solution, has no harmful gas emission in the process, is a high-efficiency and clean tungsten and molybdenum separation method, can be applied to actual production activities, and has wide application prospect.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
The following examples are intended to illustrate the present invention, but not to limit the scope of the invention, which is defined by the claims.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment of the invention provides a method for removing molybdenum in tungstate by ion exchange adsorption, which comprises the following specific steps:
raw material liquid: the molybdenum-containing tungstate solution comprises 1.65g/L of sodium tungstate, 1.21g/L of sodium molybdate and a Mo/W molar ratio of 1: 1.
S1 preparation of resin
Taking 10g of macroporous weakly basic styrene anion exchange resin as a matrix, placing the matrix in a beaker, adding 45ml of N, N dimethylformamide to swell for 12 hours at normal temperature, after solid-liquid separation, washing the fully swelled resin with ethanol, placing the swelled resin in a three-neck flask, adding 40-50ml of an aminating agent, reacting for 36 hours at 80 ℃, carrying out solid-liquid separation again, washing the resin with clear water for 3-5 times to obtain the polyamine modified resin, and sealing and storing for use at any time.
S2 adsorption of resin to remove molybdenum
The polyamine modified resin prepared in S1 is used in the solution after vulcanization treatment, 3.2g of sodium sulfide is added during vulcanization, and the reaction lasts for 2.5 hours at 73 ℃; the adsorption separation experiment needs to be carried out for 4 hours at normal temperature, the tungsten and molybdenum concentrations in the solution before and after adsorption are respectively measured, the adsorption capacity of molybdenum is 48mg/g, and the tungsten and molybdenum separation coefficient beta is 104.
Example 2
The embodiment of the invention provides a method for removing molybdenum in tungstate by ion exchange adsorption, which comprises the following specific steps:
raw material liquid: the molybdenum-containing tungstate solution is characterized by containing 16.5g/L of sodium tungstate, 1.21g/L of sodium molybdate and a Mo/W molar ratio of 1: 10.
S1 preparation of resin
Taking 10g of macroporous weakly basic styrene anion exchange resin as a matrix, placing the matrix in a beaker, adding 48ml of N, N dimethylformamide to swell for 12 hours at normal temperature, after solid-liquid separation, washing the fully swelled resin with ethanol, placing the swelled resin in a three-neck flask, adding 40-50ml of an aminating agent, reacting for 36 hours at 80 ℃, carrying out solid-liquid separation again, washing the resin with clear water for 3-5 times to obtain the polyamine modified resin, and sealing and storing for use at any time.
S2 adsorption of resin to remove molybdenum
The polyamine modified resin prepared in S1 is used in the solution after vulcanization treatment, 3.2g of sodium sulfide is added during vulcanization, and the reaction lasts for 2.5 hours at 73 ℃; the adsorption separation experiment needs to be carried out for 4 hours at normal temperature, the tungsten and molybdenum concentrations in the solution before and after adsorption are respectively measured, the adsorption capacity of molybdenum is 108mg/g, and the tungsten and molybdenum separation coefficient beta is 273.
Example 3
The embodiment of the invention provides a method for removing molybdenum in tungstate by ion exchange adsorption, which comprises the following specific steps:
raw material liquid: the molybdenum-containing tungstate solution is characterized by comprising 66g/L of sodium tungstate, 1.21g/L of sodium molybdate and a Mo/W molar ratio of 1: 40.
S1 preparation of resin
Taking 10g of macroporous weakly basic styrene anion exchange resin as a matrix, placing the matrix in a beaker, adding 50ml of N, N dimethylformamide to swell for 12 hours at normal temperature, after solid-liquid separation, washing the fully swelled resin with ethanol, placing the swelled resin in a three-neck flask, adding 40-50ml of an aminating agent, reacting for 36 hours at 80 ℃, carrying out solid-liquid separation again, washing the resin with clear water for 3-5 times to obtain the polyamine modified resin, and sealing and storing for use at any time.
S2 adsorption of resin to remove molybdenum
The polyamine modified resin prepared in S1 is used in the solution after vulcanization treatment, 3.2g of sodium sulfide is added during vulcanization, and the reaction lasts for 2.5 hours at 73 ℃; the adsorption separation experiment needs to be carried out for 4 hours at normal temperature, the tungsten and molybdenum concentrations in the solution before and after adsorption are respectively measured, the adsorption capacity of molybdenum is 160mg/g, and the tungsten and molybdenum separation coefficient beta is 1625.
According to the method for removing molybdenum in tungstate by adsorption through the ion exchange method, the amine group is bonded to the active site of the anion exchange resin matrix to obtain the amine modified resin for selectively adsorbing and removing molybdenum, and the method is simple to operate; the affinity of the amine modified resin to the thiomolybdate is greater than that of tungstate, and during the adsorption process, tungstate is hardly lost, so that tungsten loss is greatly reduced, the separation precision is improved, and the adsorption capacity is large and the separation efficiency is high; the separation process in the embodiment of the invention has no harmful gas emission, is a high-efficiency clean tungsten-molybdenum separation method, can be applied to actual production activities, and has wide application prospect.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for removing molybdenum in tungstate by ion exchange adsorption is characterized in that an amine group is bonded to an active site of an anion exchange resin matrix by a chemical synthesis method to obtain amine modified resin, and then the amine modified resin is added into a molybdenum-containing tungstate solution after vulcanization treatment to selectively adsorb and remove thiomolybdate ions; the anion exchange resin matrix is macroporous weak-base styrene anion exchange resin;
the crosslinking degree of the macroporous weakly-alkaline styrene anion exchange resin is 2-5%, and the particle size of the macroporous weakly-alkaline styrene anion exchange resin is 60-200 meshes;
the chemical synthesis method of the amine modified resin specifically comprises the following steps:
swelling and filtering the anion exchange resin matrix, washing the swelling agent carried by the surface after solid-liquid separation, then carrying out amination reaction, carrying out secondary filtration after the reaction is finished, and washing the aminating agent carried by the surface after solid-liquid separation again;
the reaction temperature and the reaction time of the amination reaction are respectively 50-80 ℃ and 25-36 h;
the amination agent of the amination reaction is trioctylamine or N1923;
the adding volume of the aminating agent is 3-5 times of that of the anion exchange resin matrix.
2. The method of claim 1,
the swelling process of the anion exchange resin matrix is specifically that a swelling agent with the volume of 4-6 times is added into the anion exchange resin matrix, and the reaction is carried out for 8-12h at normal temperature;
and/or the swelling agent is washed 3-5 times.
3. The method as claimed in claim 2, wherein the first washing with the swelling agent is performed with ethanol and the second washing with the swelling agent is performed with ethanol or water.
4. A process according to claim 2 or 3, characterised in that the swelling agent is N, N dimethylformamide.
5. The method as claimed in claim 1, wherein the sulfurization treatment is carried out by adjusting the pH value of the solution of molybdenum-containing tungstate to 6.5-7.2, adding sulfurizing agent, and keeping the temperature at 68-75 ℃ for 1.5-3h, wherein the adding amount of the sulfurizing agent is 4-6 times of the molar amount of the molybdenum.
6. The method of claim 5, wherein the sulfiding agent is sodium sulfide or sodium hydrosulfide.
7. A process according to claim 5 or 6, characterized in that the pH of the molybdenum containing tungstate solution is adjusted to 6.8 before adding the sulfiding agent.
8. Use of the method of any one of claims 1 to 7 in hydrometallurgical tungsten processing.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101496A (en) * | 1985-04-01 | 1987-01-24 | 美国道化学公司 | The high density ion exchange resin that is used for Separation of Molybdenum |
| US5082637A (en) * | 1990-11-02 | 1992-01-21 | Gte Products Corporation | Removal of potassium from ammonium molybdate |
| CN104402054A (en) * | 2014-10-27 | 2015-03-11 | 中南大学 | Method for deeply removing molybdenum from tungstate solution through ion exchange process |
| CN109534403A (en) * | 2019-01-21 | 2019-03-29 | 中南大学 | A kind of method of molybdenum in Strong acid ion-exchanger tungstate solution |
| CN110451562A (en) * | 2019-08-06 | 2019-11-15 | 湖南懋天世纪新材料有限公司 | A method of tungstates containing molybdenum produces ammonium thiomolybdate |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101496A (en) * | 1985-04-01 | 1987-01-24 | 美国道化学公司 | The high density ion exchange resin that is used for Separation of Molybdenum |
| US5082637A (en) * | 1990-11-02 | 1992-01-21 | Gte Products Corporation | Removal of potassium from ammonium molybdate |
| CN104402054A (en) * | 2014-10-27 | 2015-03-11 | 中南大学 | Method for deeply removing molybdenum from tungstate solution through ion exchange process |
| CN109534403A (en) * | 2019-01-21 | 2019-03-29 | 中南大学 | A kind of method of molybdenum in Strong acid ion-exchanger tungstate solution |
| CN110451562A (en) * | 2019-08-06 | 2019-11-15 | 湖南懋天世纪新材料有限公司 | A method of tungstates containing molybdenum produces ammonium thiomolybdate |
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