CN1084575A - Ion-exchange one-stage separation of phosphorus, arsenic, silicon, molybdenum are produced the technology of pure ammonium tungstate - Google Patents
Ion-exchange one-stage separation of phosphorus, arsenic, silicon, molybdenum are produced the technology of pure ammonium tungstate Download PDFInfo
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Abstract
Be used for the production of metal and P, As, Si, the Mo of purified ion-exchange separating tungsten acid sodium solution, produce the technology of pure ammonium tungstate, it is characterized in that: finish ion-exchange by three kinds of approach and separate P, As, Si, the allotment of Mo stock liquid, strict control related process parameter, anionite-exchange resin is placed a plurality of exchange columns, just can make P, As, four kinds of impurity of Si, Mo obtain thorough separation simultaneously, and a step obtains the (NH of purification by the primary ions exchange
4)
2WO
4Solution, direct crystallization go out the effect of high-purity APT product; Technical process of the present invention is shortened, and has reduced the cost of product, is easy to the realization of suitability for industrialized production.
Description
The invention belongs to the production of metal and the extraction of refining field, especially tungsten.
In existing tungsten production technique, from Na
2WO
4Separating impurity P.As.Si.Mo is a proceed step by step in the solution.Classical chemical method and solvent extration two technologies are with free alkali in the mineral acid neutralization solution, make hydrolyzed silicate, and most of silicon is removed with the silicic acid precipitation, adopt the magnesium salts or the ammonium magnesium salts precipitator method to remove P.As and remaining Si subsequently, and Mo is then with precipitation MoS
3Method separate separately.Ion exchange method is that As.P.Si separates with W from handing over the back to discharge the liquid in adsorption process, but can not separate Mo.
CN 86105274.9 proposes the separation method of a kind of As-W, removes the Na of Si
2WO
4Solution with primary amine extraction As-W heteropolyacid, makes 80% tungsten acquisition purification in weak alkaline medium, the W that comes together altogether with As needs to reclaim separately.
In the isolating method of W-Mo, the classical molybdenum method of removing system is Na
2S
2-Or NaHS
2-Add Na
2WO
4In the solution, make molybdenum change into Thiomolybdate, use the mineral acid acidifying subsequently, Thiomolybdate is decomposed, molybdenum is with MoS
4Precipitation forms is removed.
USSR 476231, proposed to suppress the method that Mo separates out, (NH
4)
2S
2-Add (NH
4)
2WO
4In the solution, make Mo be (NH
4)
2MoS
4Form, when the crystallization ammonium paratungstate, molybdenum stays in crystalline mother solution, to obtain to remove the APT product of molybdenum.
CN 87102098, and the active carbon adsorption of proposition is from Na
2WO
4The Na of method system of middle Separation of Molybdenum
2S or NaHS
2-Make vulcanizing agent, under reasonable process conditions, make molybdenum all change into Thiomolybdate, and W seldom changes into thiqtung state, through the Na of sulfidizing
2WO
4Solution fully contacts with gac or with the certain speed granular active carbon post of flowing through, and gac is to quantitatively absorption and make W obtain to purify of molybdenum.
U.S
2-Pat 4288413, and the solvent extration of proposition is the weakly alkaline Na through sulfidizing
2WO
4Solution fully contacts with the organic solution that with quaternary ammonium salt (as Aliquat 336) is extraction agent, and Mo is with MoS
2- 4Form extracted species [R
3(CH
3) N]
2MoS
4Collection is gone into organic phase, and W stays in water and separates, and reclaims molybdenum through the oxidation back extraction.
CN 88105712.6, the method of the separation W-Mo that proposes is an ion exchange method, and it is based on when the sodium tungstate solution through sulfidizing passes through anionite-exchange resin, the thiomolybdate ion preferentially adsorbed that its exchange potential ranks first and separating with W, the concrete practice is vulcanized Na
2WO
4Solution leaks to Mo and wears with certain linear velocity ion exchange resin bed of flowing through, again with the chloride solution drip washing of certain C l concentration, leacheate with hand over back liquid to merge to reclaim W, negative Mo resin is resolved with oxidizing solution and is reclaimed molybdenum.
Solvent extration and ion exchange method also are applicable to from (NH
4)
2WO
4Separate Mo in the solution, the vulcanizing agent of use is (NH
4)
2S.
The above-mentioned method of separating impurity from sodium tungstate solution that exemplifies all can not be separated four kinds of impurity elements of P.As.Si.Mo simultaneously in an operation, can only separate Mo separately; And the ion exchange method that existing industry is used can only be separated P.As.Si, but can not separate Mo, so the use range of raw material is narrow, can only make raw material with superfine tungsten concentrate, the content requirement of Mo is lower than 0.05%, thereby causes the cost height of tungsten product.
" rare metal and Wimet " 1992 No3 P6 have reported " the liquid-film method production ammonium paratungstate " of Wang Xiangde etc., and outer water removes Na behind the Si for neutralization
2WO
4Solution, extraction agent are N263, and emulsifying agent LMA-1, interior water are A solution, and its liquid film extraction can effectively separate P.As.Mo, and a step is produced ammonium paratungstate, yet enter suitability for industrialized production distance is arranged but.
The objective of the invention is to overcome above-mentioned from sodium tungstate solution the deficiency of the method for separating impurity, just can make four kinds of impurity of P.As.Si.Mo obtain thorough separation simultaneously and provide a kind of by the primary ions exchange, and a step obtains the (NH of purification
4)
2WO
4Solution, direct crystallization go out the method for high-purity APT product, and the raw material sources that this method is used are wide, have reduced the cost of product, are easy to the realization of suitability for industrialized production.
Reaching of above-mentioned purpose of the present invention, used following method:
1, the allotment of absorption feed liquid is given accent to tungsten mineral material alkali decomposed solution pH value, carries out sulfidizing again, and then preparation ion-exchange separates the stock liquid of P.As.Si.Mo.
Thick Na
2WO
4The PH of solution gives accent, has three kinds of approach to finish, through giving the thick Na that transfers PH
2WO
4Solution is metered into solid NaHS, and free sulfonium ion concentration is 1-10g/l in the control solution, under 60-90 ℃ of temperature, keeps 0.5-4hr, perhaps, and through the thick Na of film electrolysis dealkalize
2WO
4Solution under 60-90 ℃ of temperature, feeds H
2S gas, time 0.5-2hr, in this process, molybdenum fully changes into the Thiomolybdate form, through the Na of sulfidizing
2WO
4Solution is with containing 0.1-1g/l S
2-NaHS liquid dilution, and adjust back PH to 8-9 with 1-4mol/l NaOH liquid, be made into WO
3The solution of 15-20g/l, i.e. ion-exchange separates the stock liquid of P.As.Si.Mo.
2, ion-exchange: W and Mo are adsorbed on the resin, and single-column exchange substep is resolved W and Mo, and the multicolumn exchange then divides post to resolve W and Mo.
Anionite-exchange resin places single exchange column or a plurality of exchange column, and stock liquid leaks and to wear (WO with linear velocity 1-12cm/min resin bed to the tungsten of flowing through
3＜0.1g/l) being the absorption terminal point, in this process, Mo and W are adsorbed on the resin simultaneously, and impurity P.As.Si discharges from hand over back liquid and separates.
Thereafter carry out W and Mo and resolve step by step, resolve tungsten with mixing ammonium solution earlier, feed liquor speed 0.5-6cm/min obtains directly to send the APT crystalline high-purity (NH
4)
2WO
4Solution is resolved molybdenum with the sodium hypochlorite solution alkaline again, and resin obtains regeneration simultaneously.
If the multicolumn exchange then divides post to resolve W and Mo, resolve tungsten with mixing ammonium solution, feed liquor speed 0.5-6cm/min obtains directly to send the APT crystalline high-purity (NH
4)
2WO
4Solution is resolved molybdenum and is used the sodium hypochlorite solution alkaline, and resin obtains regeneration equally.
Do detailed explanation in conjunction with the accompanying drawings:
Fig. 1-ion-exchange separating impurity operational flowchart;
Fig. 2-two post exchange synoptic diagram;
Fig. 3-three post exchange synoptic diagram;
Fig. 4-four post exchange synoptic diagram;
Thick Na2WO
4Solution derives from caustic soda and decomposes the solution of wolframite and soda high pressure and decompose the solution that wolframite and black and white are mixed tungsten ore, the solution after perfectly crystallization process or electrolysis with ion-exchange film method remove excessive free alkali. These contain the W mineral alkali decomposed solution of P.As.Si.Mo, adopt crystallisation or membrane electrolysis recovery free alkali wherein, the thick Na after the former dealkalize2WO
4Solution still has higher alkalisation, and latter's dealkalize degree of depth can arbitrarily be determined, can not need transfer directly logical H of PH2The S sulfuration.
Thick Na2WO
4The PH of solution gives accent, has three kinds of approach to finish:
(1) inorganic acid neutralization, inorganic acid can be with hydrochloric acid or sulfuric acid, concentration is 1-4mol/l, solution under strong mixing, slowly add dilute acid soln to PH=7-8 be the acidifying terminal point, also can be according to the WO in the stoste3Content, metering slowly adds inorganic acid solution for giving the accent terminal point.
(2) solvent extraction and ion-exchange, extractant can be used acid phosphorus-contained extractant, also available aliphatic acid extractant. Resin H+The type cationic ion-exchange resin. According to the terminal point pH value of the free alkalinity in the material liquid and requirement, select different extractant concentrations to compare with contacting, once contact can be finished, and in this process Na takes place+With H+Exchange and free alkali in the neutralization solution, after phase-splitting or the Separation of Solid and Liquid, organic phase or resin are regenerated with inorganic acid.
(3) single anode membrane electrolysis adopts the electrolysis unit of similar chlorine industry, with Na2WO
4Solution is made anolyte, and catholyte is sig water, under the DC electric field effect, and Na+See through cation-exchange membrane and enter cathode chamber recovery alkali, by the H of anode reaction generation+The ion neutralization solution is decided pH value to giving. Electrolytic parameter is: anolyte WO3Concentration 50-200g/l, catholyte are 0.1-2mol/1NaOH liquid (or Na2CO
3Liquid), electrolysis temperature 40-60C, membrance current density 400-1200A/M2。
After the thick Na that transfers PH2WO
4Solution is metered into solid NaHS, and free sulphion concentration is 1-10g/l in the control solution, under 60-90 ℃ of temperature, keeps 0.5-4hr, perhaps, and through the thick Na of film electrolysis dealkalize2WO
4Solution under 60-90 ℃ of temperature, passes into H2S gas, time 0.5-2hr, in this process, molybdenum fully changes into the Thiomolybdate form, through the Na of vulcanizing treatment2WO
4Solution is with containing 0.1-1g/l S2-NaHS liquid dilution, and adjust back PH=8-9 with 1-4mol/l NaOH liquid, be made into WO3The solution of 15-20g/l namely is the material liquid that ion-exchange separates P.As.Si.Mo.
Ion-exchange operation and mode:
(1) single-column: anion exchange resin, comprise gel type strong base and weak base negative resin, and macropore highly basic and macropore weak base negative resin, according to the technological parameter requirement, it is 6-12 that selected wherein any anion exchange resin places draw ratio: single exchange column of 1, the control material liquid is flowed through resin bed until (WO is worn in the tungsten leakage with linear velocity 1-12cm/min3＜0.1g/l) being the absorption terminal point, in this process, Mo and W are adsorbed on the resin simultaneously, and impurity P.As.Si discharges from hand over rear liquid and separates.
The saturated resin bed carries out W after pure water is cleaned and Mo resolves step by step. Resolve tungsten with mixing ammonium salt solution earlier, resolve agent: strong base negative resin 5M NH4Cl+2M NH
4OH solution, weak base resin 1-2M(NH4）
2CO
3+0.5-1.5M NH
4OH solution, feed liquor speed 0.5-6cm/min, high-purity (NH of APT crystallization is directly sent in acquisition4）
2WO
4Solution, Mo still stays on resin when resolving W, so W fully separates with Mo. Resolve molybdenum with the sodium hypochlorite solution alkaline afterwards, resolve effective chlorine ion concentration [Cl in the agent+] be 0.2-1mol/l, [NaOH] 0.1-0.5mol/l resolves agent and enters from the capital outflow at the bottom of post, and resin is in full suspended state, and resin obtains regeneration simultaneously in resolving the Mo process, after pure water is cleaned, can drop into to adsorb next time and use.
(2) two posts: adopt two exchange columns of S.L to go here and there mutually, S post length-to-diameter ratio (3-6): 1, L post length-to-diameter ratio (6-12): 1, use gel-type and macroporous type anionite-exchange resin, concrete which kind of type of resin of using is different because of sulfuration feed liquid preparation method, and S post resinous type is identical and different with the L post in the practical application.Stock liquid by the S post, passes through the L post with descending method with ascending method thereupon, and flow velocity is by the control of L post, linear velocity 1-12cm/min.Adsorption process is to L post WO
3Leakage is worn and is terminal point.At this moment, the S post is thiomolybdate ion and part S
2-Ion institute is saturated, and the P.As.Si that is not transformed into the sulfo-acid group all discharges from hand over back liquid, with deionized water by and the absorption same stream to eluted resin, then, S post and L post are resolved respectively, the S post is resolved Mo, the L post is resolved W; Resolve molybdenum with the sodium hypochlorite solution alkaline, resolve available chlorine ionic concn [Cl in the agent
+] be 0.2-1mol/l, [NaOH] 0.1-0.5mol/l resolves agent and enters from the capital outflow at the bottom of post, and resin is in full suspended state, and resin obtains regeneration simultaneously in resolving the Mo process, does next round absorption after cleaning, during parsing W, strong base negative resin 5M NH
4Cl+2M NH
4OH solution, weak base resin 1-2M(NH
4)
2CO
3+ 0.5-1.5M NH
4OH solution, feed liquor speed 0.5-6cm/min obtains directly to send the APT crystalline high-purity (NH
4)
2WO
4Solution.
(3) three posts: adopt three exchange columns of S1.S2.L to go here and there mutually, S1.S2 post length-to-diameter ratio (3-6): 1, L post length-to-diameter ratio (6-12): 1, use gel-type and macroporous type anionite-exchange resin, concrete which kind of type of resin of using is different because of sulfuration feed liquid preparation method, and S1.S2 post resinous type is identical and different with the L post in the practical application.Stock liquid successively by the S1.S2 post, passes through the L post with descending method with ascending method thereupon, and flow velocity is by the control of L post, linear velocity 1-12
Cm/min. adsorption process is to L post WO
3Leakage is worn and is terminal point.At this moment,
The S1 post is thiomolybdate ion and part S
2-Ion institute is saturated, and the S2 post is adsorbed with the thiomolybdate ion.S
2-Ion and part WO
2 4Ion, the P.As.Si that is not transformed into the sulfo-acid group are all discharged from hand over back liquid, with deionized water by and the absorption same stream to eluted resin, afterwards, S1 post and L post are resolved respectively, and the S1 post is resolved Mo, the L post is resolved W, resolves molybdenum with the sodium hypochlorite solution alkaline, resolves available chlorine ionic concn [Cl in the agent
+] be 0.2-1mol/l, [NaOH] 0.1-0.5mol/l, resolving agent enters from capital at the bottom of the post and flows out, resin is in full suspended state, resin obtains regeneration simultaneously in resolving the Mo process, do next round absorption after cleaning, the S2 post of last round of absorption is the S1 post of next round absorption, and the S1 post after regenerating is made the S2 post of lower whorl absorption.When resolving W, strong base negative resin 5M NH
4Cl+2M NH
4OH solution, weak base resin 1-2M(NH
4)
2CO
3+ 0.5-1.5M NH
4OH solution, feed liquor speed 0.5-6cm/min obtains directly to send the APT crystalline high-purity (NH
4)
2WO
4Solution.
(4) four posts: adopt S1.S2.S3, four exchange columns of L are gone here and there mutually, the length-to-diameter ratio of S1.S2.S3 post (3-6): 1, L post length-to-diameter ratio (6-12): 1, use gel-type and macroporous type anionite-exchange resin, concrete which kind of type of resin of using is different because of sulfuration feed liquid preparation method, and S1.S2.S3 post resinous type is identical and different with the L post in the practical application.Stock liquid successively by the S1.S2.S3 post, passes through the L post with descending method with ascending method thereupon, and flow velocity is by the control of L post, and linear velocity 1-12cm/min. adsorption process is to L post WO
3Leakage is worn and is terminal point.At this moment, the S1 post is thiomolybdate ion and part S
2-Ion institute is saturated, and the S2 post is adsorbed with the thiomolybdate ion.S
2-Ion and part WO
2- 4Ion, the S3 post is adsorbed with S
2-Ion and part WO
2- 4Ion, the P.As.Si that is not transformed into the sulfo-acid group are all discharged from hand over back liquid, with deionized water by and the absorption same stream to eluted resin, afterwards, S1 post and L post are resolved respectively, and the S1 post is resolved Mo, the L post is resolved W, resolves molybdenum with the sodium hypochlorite solution alkaline, resolves available chlorine ionic concn [Cl in the agent
+] be 0.2-1mol/l, [NaOH] 0.1-0.5mol/l, resolving agent enters from capital at the bottom of the post and flows out, resin is in full suspended state, and resin obtains regeneration simultaneously in resolving the Mo process, does next round absorption after cleaning, the S2 of last round of absorption, the S3 post is the S1 of next round absorption, the S2 post, and the S1 post after regenerating is made the S3 post of lower whorl absorption.When resolving W, strong base negative resin 5M NH
4Cl+2M NH
4OH solution, weak base resin 1-2M(NH
4)
2CO
3+ 0.5-1.5M NH
4OH solution, feed liquor speed 0.5-6cm/min obtains directly to send the APT crystalline high-purity (NH
4)
2WO
4Solution.
Use two posts. three posts. and four post mode of operation if separate L post strong base negative resin behind the W, directly change lower whorl over to and adsorb after cleaning; If the weak base negative resin makes the transition with 0.5～2M HCl solution, change lower whorl absorption after cleaning over to.
The present invention compared with prior art has following advantage:
1. realized just making four kinds of impurity of P.As.Si.Mo obtain thorough separation simultaneously, and a step obtains the (NH of purification by the primary ions exchange
4)
2WO
4Solution, direct crystallization go out high-purity APT product.
2. technical process of the present invention is shortened, thereby has reduced the loss of tungsten, has reduced the consumption of manpower and reagent; Relaxed the restriction of Mo content in the tungsten mineral material, be extended to 0.1～1.5% scope from 0.05%, thereby the use range of raw material enlarges, reduced the cost of product.
3. the present invention is easy to the realization of suitability for industrialized production, and the factory with ion exchange method production APT to existing need not do big change, can use production, its less investment, instant effect.
Embodiment:
Embodiment one
1. absorption material preparation: thick Na
2WO
4Solution W O
3104g/l, Mo 1.56g/l, As 0.0041g/l, Si 0.065g/l. adjusts solution PH to 7.2 with the naphthenic acid extraction process, adds vulcanizing agent NaHS, the free S of control solution
2-Ionic concn 3.5g/l is incubated 2hr under 70C, be cooled to room temperature, with containing S
2-0.5g/l the NaHS solution dilution and with 3M NaOH solution readjustment PH to 8.5, the feed liquid WO after the dilution
315g/l.
2. absorption: adopt the absorption of strong basicity gel-type negative resin single-column, dress post length-to-diameter ratio 10: 1, the absorption linear velocity is 6cm/min.
3. substep is resolved: use earlier 5M NH
4Cl+2M NH
4OH solution is resolved tungsten, and linear velocity 2.5cm/min separates the batch sampling of W liquid.The back is with containing 0.5mol/l available chlorine, and the NaClO solution of 0.25mol/l NaOH is resolved Mo, and linear velocity 2.5cm/min. is with the thorough parsing of Mo, and resin recovers former color and luster.
4. result: separate W liquid Mo/WO
3Than being (4.3-6.8) * 10
-5, the operating capacity of resin is 302mg WO
3/ g dried resin (Cl type), the APT product is produced in peak liquid crystallization, percent crystallization in massecuite 85.2%, product Mo content＜20ppm, all the other whole element quality reach GB10116-88 APT-0 grade standard.
Embodiment two
1. absorption material preparation: thick Na
2WO
4Solution, WO
3152g/l, Mo 2.20g/l, As 0.006g/l, Si 0.096g/l gives accent solution PH to 7.5 with 2.5M HCl, and all the other cure conditions are with example one, and sulfuration liquid is with containing S
2-0.3g/l NaHS liquid dilution and adjust back PH to 8.2, the absorption feed liquid WO that is mixed with 3M NaOH liquid
318.5g/l;
2. absorption: macroreticular weakly base negative resin, single-column absorption, length-to-diameter ratio 12: 1, absorption linear velocity 5cm/min;
3. substep is resolved: resolve W earlier, the parsing agent is 1.5mol/l(NH
4)
2CO
3With 1mol/l NH
4The OH mixing solutions, resolution speed 2cm/min, Mo is resolved in the back, and analysis condition is with example one;
4. result: separate W liquid Mo/WO
3Than being (2.6-2.7) * 10
-5, resin operating capacity 316mg WO
3/ g dried resin (Cl type). the APT product is produced in peak liquid crystallization, and percent crystallization in massecuite 90.3%, product contain Mo amount＜20ppm, and all the other whole elements reach GB10116-88 APT-0 grade standard.
Embodiment three
1. absorption material preparation: thick Na
2WO
4Solution, WO
375.6g/l, Mo 1.14g/l, As 0.003g/l, Si 0.048g/l. film electrolytic process is given and is transferred PH=7.4, and electrolytic parameter is: catholyte 0.2mol/l NaOH liquid, membrane current density 600A/M
2, 55 ℃ of electrolysis temperatures, all the other curing parameters and feed liquid modulation are with the absorption feed liquid WO of example one preparation
316g/l, PH=8.3;
2. absorption: mode of operation is referring to Fig. 3, S1, and the S2 post loads the macropore negative resin, length-to-diameter ratio 5: 1, the L post loads gel type strong base negative resin, length-to-diameter ratio 10: 1, absorption linear velocity 6cm/min;
3. divide post to resolve: the L post is resolved W, and the S1 post is resolved Mo, uses earlier 5M NH
4Cl+2M NH
4OH solution is resolved tungsten, and linear velocity 2.5cm/min separates the batch sampling of W liquid.The back is with containing 0.5mol/l available chlorine, and the NaClO solution of 0.25mol/l NaOH is resolved Mo, and linear velocity 2.5cm/min. is with the thorough parsing of Mo, and resin recovers former color and luster;
4.L when post was resolved, the desorbed solution portioning was accepted, and analyzed composition wherein, the results are shown in Table 1:
Table 1. is separated the analytical results of W liquid
| No |
| 1 | 2 | 3 | |
| WO 3?g/l | 93 | 154.5 | 135 |
| As/WO 3 | 1.72×10 -7 | 7.77×10 -8 | 7.40×10 -8 |
| SiO/WO 3 | 1.40×10 -6 | 9.70×10 -7 | 1.04×10 -6 |
| Mo/WO 3 | 6.02×10 -5 | 2.70×10 -5 | 2.37×10 -5 |
Listed sampling 1.2.3 number composition from table 1, resulting ammonium tungstate solution has been received the effect of deep impurity-removing matter after the primary ions exchange, can directly produce APT-0 level product.
Claims (8)
1, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution produces the technology of pure ammonium tungstate, successively by to the absorption of the allotment of tungsten mineral material alkali decomposed solution, ion-exchange, resolve the basic step operation, it is characterized in that:
The allotment of absorption feed liquid: thick Na
2WO
4The PH of solution gives accent, has three kinds of approach to finish; Through giving the thick Na that transfers PH
2WO
4Solution is metered into solid NaHS, and free sulfonium ion concentration is 1-10g/l in the control solution, under 60-90 ℃ of temperature, keeps 0.5-4hr, perhaps, and through the thick Na of film electrolysis dealkalize
2WO
4Solution under 60-90 ℃ of temperature, feeds H
2S gas, time 0.5-2hr, in this process, molybdenum fully changes into the Thiomolybdate form; Na through sulfidizing
2WO
4Solution is with containing 0.1-1g/lS
2-NaHS liquid dilution, and adjust back PH to 8-9 with 1-4mol/lNaOH liquid, be made into WO
3The solution of 15-20g/l, i.e. ion-exchange separates the stock liquid of P.As.Si.Mo;
Ion-exchange: anionite-exchange resin places single exchange column or a plurality of exchange column, and stock liquid leaks and to wear (WO with linear velocity 1-12cm/min resin bed to the tungsten of flowing through
3＜0.1g/l) being the absorption terminal point, in this process, Mo and W are adsorbed on the resin simultaneously, and impurity P.As.Si discharges from hand over back liquid and separates;
Thereafter carrying out W and Mo resolves step by step. and resolve tungsten with mixing ammonium solution earlier, feed liquor speed 0.5-6cm/min obtains directly to send the APT crystalline high-purity (NH
4)
2WO
4Solution is resolved molybdenum with the sodium hypochlorite solution alkaline again, and resin obtains regeneration simultaneously; If multicolumn absorption, then W and Mo divide post to resolve.
2, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1 produces the technology of pure ammonium tungstate, it is characterized in that described tungsten minerals alkali decomposed solution comprises NaOH and Na
2CO
3System and NaOH+Na
2CO
3System.
3, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1 produces the technology of pure ammonium tungstate, it is characterized in that the described Na of finishing
2WO
4The PH of solution gives three kinds of approach of accent: the neutralization of (1) mineral acid, and (2) solvent extration and ion exchange method, (3) single anode membrane electrolytic process is chosen any one kind of them.
4, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1, produce the technology of pure ammonium tungstate, the polymeric adsorbent that it is characterized in that described W and Mo is an anionite-exchange resin, comprising gel type resin and macroporous ion-exchange resin, can be that the strong basicity negative resin also can be a weakly basic anion resin.
5, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1 produces the technology of pure ammonium tungstate, it is characterized in that its length-to-diameter ratio of exchange column of described absorption usefulness is (3-6): 1 or (6-12): 1.
6, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1 produces the technology of pure ammonium tungstate, and the parsing agent that it is characterized in that described tungsten is for mixing ammonium solution, and strong base negative resin is 5M NH
4Cl+2M NH
4OH, weak base negative resin are (1-2) M(NH
4)
2CO
3+ (0.5-1.5) M NH
4OH solution.
7, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1 produces the technology of pure ammonium tungstate, and the parsing agent that it is characterized in that described molybdenum is for containing effective chlorine ion concentration [Cl
+] 0.2-1mol/l, the chlorine bleach liquor of [NaOH] 0.1-0.5mol/l.
8, the P.As.Si.Mo in the ion-exchange separating tungsten acid sodium solution according to claim 1 produces the technology of pure ammonium tungstate, it is characterized in that regenerated resin behind the described Mo of separating, and recovers former color and luster, after cleaning, returns next round absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111497.7A CN1036472C (en) | 1993-07-13 | Process for preparation of pure ammonium turgstate by ion-exchange one-stage separation of phosphorus, arsenic, silicon and molybdenum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111497.7A CN1036472C (en) | 1993-07-13 | Process for preparation of pure ammonium turgstate by ion-exchange one-stage separation of phosphorus, arsenic, silicon and molybdenum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1084575A true CN1084575A (en) | 1994-03-30 |
| CN1036472C CN1036472C (en) | 1997-11-19 |
Family
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0721017A1 (en) * | 1995-01-03 | 1996-07-10 | H.C. Starck GmbH & Co. KG | Process for preparing pure solutions of tungsten and molybdenum |
| CN1042445C (en) * | 1994-04-29 | 1999-03-10 | 中南工业大学 | Prepn. of pure tungstate by extracting tungsten from alkali leaching liquor of tungten ore |
| CN1049925C (en) * | 1997-06-19 | 2000-03-01 | 中南工业大学 | Process for removing Mo, As, Sb and Sn by precipitating of tungstate solution |
| CN1083802C (en) * | 1998-12-05 | 2002-05-01 | 中南工业大学 | Elimination of molybdenum from tungstate soltuion |
| CN1085736C (en) * | 1999-05-14 | 2002-05-29 | 潘恩树 | Molybdenum removing technology in tungsten smelting process |
| CN101177303B (en) * | 2007-11-02 | 2010-06-02 | 北京有色金属研究总院 | Method for removing molybdenum, arsenic, antimony and stannum from tungstate solution |
| CN101643245B (en) * | 2008-08-05 | 2011-11-30 | 江西稀有稀土金属钨业集团有限公司 | Process for preparing high-purity ammonium paratungstate |
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| CN107419099A (en) * | 2016-05-24 | 2017-12-01 | 北京清树科技发展有限公司 | A kind of separation and the method for tungsten and molybdenum in recovery tungstates and molybdic acid salt mixture |
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| CN1042445C (en) * | 1994-04-29 | 1999-03-10 | 中南工业大学 | Prepn. of pure tungstate by extracting tungsten from alkali leaching liquor of tungten ore |
| CN1060819C (en) * | 1995-01-03 | 2001-01-17 | H·C·施塔克公司 | Process for production of pure solutions of tungsten and molybdenum |
| EP0721017A1 (en) * | 1995-01-03 | 1996-07-10 | H.C. Starck GmbH & Co. KG | Process for preparing pure solutions of tungsten and molybdenum |
| CN1049925C (en) * | 1997-06-19 | 2000-03-01 | 中南工业大学 | Process for removing Mo, As, Sb and Sn by precipitating of tungstate solution |
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| CN101643245B (en) * | 2008-08-05 | 2011-11-30 | 江西稀有稀土金属钨业集团有限公司 | Process for preparing high-purity ammonium paratungstate |
| CN107419099B (en) * | 2016-05-24 | 2018-08-14 | 北京清树科技发展有限公司 | A method of separation and tungsten and molybdenum in recycling tungstates and molybdic acid salt mixture |
| CN107419099A (en) * | 2016-05-24 | 2017-12-01 | 北京清树科技发展有限公司 | A kind of separation and the method for tungsten and molybdenum in recovery tungstates and molybdic acid salt mixture |
| CN106673064A (en) * | 2016-12-05 | 2017-05-17 | 荆门德威格林美钨资源循环利用有限公司 | Method for producing ammonium paratungstate |
| CN108706634A (en) * | 2018-06-12 | 2018-10-26 | 崇义章源钨业股份有限公司 | Purify the device and method of ammonium tungstate solution |
| CN108706634B (en) * | 2018-06-12 | 2021-07-16 | 崇义章源钨业股份有限公司 | Apparatus and method for purifying ammonium tungstate solution |
| CN109052478A (en) * | 2018-10-18 | 2018-12-21 | 谭琴 | A kind of decomposition technique of thick order of ammoniumparatungstate crystal |
| CN109929998A (en) * | 2019-03-25 | 2019-06-25 | 湖南懋天世纪新材料有限公司 | A kind of regeneration method of copper-molybdenum saturated resin |
| CN114525415A (en) * | 2022-02-09 | 2022-05-24 | 信丰华锐钨钼新材料有限公司 | High-low molybdenum coupling system for tungsten smelting |
| CN114525415B (en) * | 2022-02-09 | 2024-01-02 | 信丰华锐钨钼新材料有限公司 | Tungsten smelting high-low molybdenum coupling system |
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