WO2016187993A1 - 一种废scr脱硝催化剂的回收处理方法 - Google Patents

一种废scr脱硝催化剂的回收处理方法 Download PDF

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WO2016187993A1
WO2016187993A1 PCT/CN2015/090081 CN2015090081W WO2016187993A1 WO 2016187993 A1 WO2016187993 A1 WO 2016187993A1 CN 2015090081 W CN2015090081 W CN 2015090081W WO 2016187993 A1 WO2016187993 A1 WO 2016187993A1
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vanadium
leachate
tungsten
catalyst
molybdenum
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PCT/CN2015/090081
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English (en)
French (fr)
Chinese (zh)
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林晓
刘晨明
李志强
潘尹银
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北京赛科康仑环保科技有限公司
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Priority to JP2017561394A priority Critical patent/JP6661665B2/ja
Publication of WO2016187993A1 publication Critical patent/WO2016187993A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • 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
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • 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
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention belongs to the field of solid waste treatment, and in particular relates to a method for recycling and treating a waste SCR denitration catalyst.
  • SCR Selective Catalytic Reduction
  • the SCR catalysts are mainly vanadium tungsten, vanadium molybdenum and vanadium tungsten molybdenum. All of them use V 2 O 5 and TiO 2 as catalytic main bodies. The difference is that vanadium and tungsten catalysts use WO 3 as an auxiliary agent, vanadium and molybdenum is MoO 3 as an auxiliary agent, and vanadium tungsten and molybdenum is based on WO 3 and MoO 3 act as a co-agent.
  • the investment of the catalyst is the core part, and the activity of the catalyst directly determines the efficiency of denitration.
  • the SCR denitration catalyst has a reduced activity during use, and therefore it is necessary to regenerate and activate the catalyst after a certain period of use.
  • some SCR catalysts have been severely damaged after repeated activation and use, and it has been difficult to regenerate.
  • These non-renewable catalysts are waste SCR catalysts.
  • the treatment method for the honeycomb waste SCR denitration catalyst is crushed landfill.
  • the waste SCR catalyst is a dangerous solid waste because it contains toxic metal oxides such as V 2 O 5 , WO 3 or MoO 3 . If the SCR waste catalyst is disposed of by landfill, it will not only occupy a large amount of land resources, but also environmental pollution. Bringing risks will also create an economic burden on power plants and engineering companies.
  • WO 3 , MoO 3 , V 2 O 5 and TiO 2 contained in the honeycomb waste SCR catalyst are valuable resources. If they can be recovered by means of separation and purification, not only can new profit growth points be generated. It can also achieve good results in the formation of closed loops of various substances in the flue gas denitration industrial chain.
  • Patent CN104192911A discloses a method for recovering a tungsten trioxide component in a spent SCR denitration catalyst.
  • the slag denitration catalyst is fully pulverized to dry powder.
  • the tungsten trioxide component in the catalyst is dissolved under a certain condition by using a specific solution, and the tungsten trioxide is effectively separated from other components in the catalyst, and the upper layer containing tungsten is collected.
  • the liquid was evaporated to dryness, and the obtained solid was sufficiently dried, and after high-temperature calcination, recovery of the tungsten trioxide component was completed.
  • Patent CN104195342A discloses a process for recovering the vanadium pentoxide component of a spent SCR denitration catalyst. Firstly, the reducing agent is used to reduce the pentavalent vanadium in the catalyst to a more soluble tetravalent vanadium in an acidic solution, and then the oxidizing agent further oxidizes the tetravalent vanadium in the acidic solution to pentavalent vanadium by adjusting the pH value of the solution. Under certain conditions, the pentavalent vanadium is fully hydrolyzed and precipitated, and the collected precipitate is calcined to obtain high-purity vanadium pentoxide, and the vanadium pentoxide purity is 98%.
  • Patent CN103130265A discloses a method for recovering titanium dioxide from a spent SCR denitration catalyst.
  • the dust removal catalyst is firstly dedusted and pulverized, and then concentrated sulfuric acid is added to acidify the solution to obtain a concentrated solution of titanyl sulfate, and then diluted with water; then a nonionic emulsifier is added as a flocculating agent, a sulfonate surfactant.
  • a polycarboxylate surfactant as a coagulant followed by the addition of water-soluble methyl silicone oil; pumped into a plate and frame filter press for pressure filtration, the filtrate is concentrated in vacuo and heated to 90 ° C -98 ° C for 5.5 hours The filtrate is hydrolyzed; then the hydrolyzate is cooled to 40 ° C, vacuum filtration is carried out to deposit metatitanic acid; after rinsing with sand water and deionized water, potassium carbonate or phosphoric acid is added to obtain a metatitanic acid filter cake; After calcination at 500-800 ° C, followed by pulverization and grinding to obtain a finished titanium dioxide.
  • Patent CN104261415A discloses a process for the complete recovery of silica from spent SCR catalysts.
  • the pulverized waste SCR catalyst is immersed in 3 to 4 volumes of water to remove impurities, and after the impurity removal, the powder is leached with an excess concentration of 60-80% by weight of a concentrated alkali solution, and filtered to obtain solid sodium metasilicate titanate Na 2 TiO.
  • Patent CN104275178A discloses a method for recycling and regenerating an SCR catalyst carrier for a spent SCR denitration catalyst.
  • the waste SCR catalyst is pulverized, sieved, washed with water, and acid washed, and then wet pulverized and ground to obtain a catalyst slurry.
  • the slurry is then mixed with a titanate slurry to obtain a mixed slurry.
  • the mixed slurry is washed with water, filtered, dehydrated, adjusted to pH, and then bleached with a reducing agent.
  • the bleached slurry is added with water, the pH is adjusted, ammonium paratungstate and white carbon black are added, and the catalyst is recovered by stirring, filtering, dehydrating, calcining and pulverizing.
  • Patent CN104263946A discloses a process for recovering tungsten, vanadium, titanium from an SCR denitration spent catalyst.
  • the SCR spent catalyst is washed, pulverized, sieved, mixed with sodium carbonate and stirred uniformly, and the mixed powder is sintered at a high temperature to obtain a sintered material, which is further leached with water to obtain a mixed solution of sodium salt containing tungsten and vanadium; the pH of the solution is greater than 12
  • Selective extraction of tungsten, stripping with ammonium salt solution to obtain ammonium tungstate solution
  • a sodium vanadate solution containing a small amount of tungsten; titanium is left in the leaching residue to obtain a titanium-rich material.
  • Patent CN104178636A discloses a method for activating calcination in combination with acid leaching to recover Ti, V, Mo, Si from spent SCR spent catalyst.
  • the treatment steps are as follows: pretreatment of the SCR spent catalyst, followed by high temperature calcination activation.
  • the calcined product was then acid leached to obtain a white TiO 2 powder.
  • a white precipitate of H 2 MoO 4 was obtained .
  • the leachate was added with ammonia to adjust the pH to 8.0 to 9.0 to obtain NH 4 VO 3 precipitation.
  • the leachate was further added with ammonia to adjust the pH to 8.0 to 9.0, and then MgCl 2 was added to obtain MgSiO 3 .
  • the filtered filtrate enters the wastewater recovery system.
  • Patent CN104326506A discloses a process for recovering titanium dioxide from a spent denitration catalyst. The method comprises the following steps: (1) grinding the fail-out catalyst into a powder form and placing it in an open container, adding an appropriate amount of distilled water to the open container to prevent the bottom; (2) acid hydrolysis, concentrated sulfuric acid having a mass fraction of 98% Adding to the open container, heating the open container to dissolve the powder, and continuously stirring during heating to make the solid and liquid evenly mixed.
  • the present invention proposes a method for re-manufacturing waste SCR denitration catalyst, and separating and recovering valuable components such as vanadium tungsten molybdenum as needed, wherein The recovery rate of valuable metals is over 95%, and the purity of vanadium/tungsten/vanadium molybdenum products is over 99%.
  • a method for recycling waste SCR denitration catalyst comprises the following steps:
  • the vanadium extract obtained in the step (3) is further purified for use in preparing a vanadium product; the obtained tungsten/molybdenum/tungsten-molybdenum concentrate is further purified for use in preparing a tungsten/molybdenum/tungsten-molybdenum product.
  • Step (1) is an important step of removing impurities in the spent SCR denitration catalyst and activating catalytic components such as vanadium tungsten molybdenum.
  • SCR denitration catalysts carry impurities such as dust, sand and oil during long-term use, which can affect the purity of subsequent products. Further, V 2 O 5 , WO 3 and MoO 3 in the spent catalyst are poorly soluble. Therefore, the spent catalyst needs to be pretreated to remove the carried impurities and activate the catalytic components such as vanadium tungsten molybdenum.
  • the pretreatment method in the step (1) may be washing, pulverization, calcination, drying, or the like.
  • Washing and drying can remove dust, sand and oil carried by the spent catalyst; pulverization can increase the specific surface area of the spent catalyst; roasting can activate V 2 O 5 , WO 3 , MoO 3 in the spent catalyst to be easily soluble in water. VO 4 3- , WO 4 2- , MoO 4 2- .
  • an additive may be added, and the additive may be an alkali metal base or a salt. To save cost, a sodium base or a sodium salt, such as NaOH or Na 2 CO 3 , etc., is preferred.
  • the baking temperature is 500 to 900 ° C, for example, 550 ° C, 600 ° C, 650 ° C, 700 ° C, 750 ° C, 800 ° C, and 850 ° C.
  • the calcination time is 1 to 7 h, for example, 1.5 h, 2 h, 3 h, 4 h, 5 h, and 6 h.
  • Step (2) is the main process for extracting vanadium tungsten molybdenum from the solid phase.
  • the leaching agent can be neutral or acidic or alkaline. If the leaching agent is acidic, other metals such as Ti, other than V, W and Mo, in the spent catalyst will also enter the solution, which makes the composition of the leaching liquid more complicated and increases the difficulty of separation of subsequent components. Therefore, the leaching agent in the present invention is preferably neutral or alkaline.
  • the liquid-solid ratio of the leaching agent to the calcined product is 0.02 to 1 L/g, for example, 0.025 L/g, 0.05 L/g, 0.1 L/g, 0.15 L/g, 0.2 L/g, 0.25 L/g, 0.5 L.
  • the leaching temperature is 20 to 200 ° C, for example, 25 ° C, 40 ° C, 60 ° C, 80 ° C, 100 ° C, 120 ° C, 140 ° C, 160 ° C, 180 ° C, and the like.
  • the leaching time may be 0.5 to 5 hours, for example, 0.75h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, and 4.5h.
  • the leaching pressure is 0.1 to 1 MPa, for example, 0.2 MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa, and 1.0 MPa.
  • the leaching stirring speed is 100 to 5000 r/min, for example, 400 r/min, 800 r/min, 1200 r/min, 1600 r/min, 2000 r/min, 2400 r/min, 2800 r/min, 3200 r/min, 3600 r/min, 4000 r/ Min, 4400r/min and 4800r/min, etc.
  • Step (3) is the core operation for separating the valuable elements in the leachate.
  • the extracting agent may be an amine, an organic phosphonic acid, an organic ester, a neutral phosphine, a quaternary ammonium salt and a terpenoid, such as a primary amine N1923, Primene.
  • extractant concentration is 5% to 30%, for example, 10%, 15%, 20%, and 25%;
  • the initial pH of the aqueous phase is 1 to 9, for example 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7, and 8, etc.;
  • extraction temperature is 10 to 40 ° C, for example, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, etc.; extraction time For 10 to 40 minutes, for example, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, etc.; when the organic phase
  • the concentration of the alkali solution is 1 to 10 g/L, for example, 2 g/L, 4 g/L, 6 g/L, 8 g/L, and 9 g/L; and the aqueous ammonia concentration is 5% to 30%, for example, 10%, 15%, 20%, 25% and 28%, etc.
  • the stripping temperature is 20 to 70 ° C, for example, 30, 40, 50, and 60 ° C; the stripping time is 0.5 to 4 h, for example, 1, 1.5, 2, 2.5, 3, and 3.5.
  • the resin type is a strongly basic or weakly basic anion exchange resin, for example, D418, D301, etc.
  • the volume of the leachate is 10 to 100 times the volume of the resin, for example, 20, 30, 40, 50, 60, 70, 80 and 90, etc.
  • solution pH is 2 to 11, for example, 2, 4, 6, 8, and 9, etc.
  • temperature is 20 to 90 ° C, for example, 20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C and 80 ° C, etc.
  • exchange time is 30 ⁇ 100min, such as 20min, 40min, 60min and 80min; etc.
  • resin regeneration liquid is a strong base or weak alkaline solution, such as NaOH, Na 2 CO 3 and ammonia water
  • regeneration time is 20-120 min, for example 30 min, 50 min, 60 min, 70 min, 80 min, 90 min and 110 min
  • regeneration temperature is 25-90 ° C, for example 30 ° C
  • the precipitating agent is an alkali metal salt or the like, and is, for example, Ca(NO 3 ) 2 , CaCl 2 , Mg(NO 3 ) 2 , MgCl 2 , BaCl 2 , and Ba (NO 3 ).
  • the precipitation temperature is 20-80 ° C, for example 20, 30, 40, 50, 60 and 70 ° C;
  • the precipitation time is 20-120 min, for example 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min and 110 min, etc.;
  • Step (4) is an important step for further purification of vanadium extract and tungsten/molybdenum/tungsten-molybdenum enrichment to prepare vanadium and tungsten/molybdenum/tungsten-molybdenum products, respectively.
  • Further purification of the vanadium extract is by precipitation, extraction, ion exchange and membrane separation.
  • the ammonium metavanadate precipitate is dissolved, reprecipitated, washed, dried and calcined to obtain a vanadium pentoxide product having a purity of more than 99.5%.
  • the vanadium-containing solution can also be obtained by a high-purity vanadium pentoxide product by an extraction-back extraction vanadium-drying-baking process.
  • the low concentration pure vanadium solution can be concentrated by electrodialysis.
  • the vanadium salt product can also be obtained by extracting vanadium from a low concentration vanadium solution by ion exchange, followed by resin washing regeneration, evaporation crystallization and drying. Further purification of tungsten/molybdenum/tungsten-molybdenum enrichment by precipitation, extraction, ion exchange and membrane separation Wait.
  • the sodium molybdate solution is first extracted with an amine extractant, and then extracted with ammonia water to obtain an ammonium molybdate solution, which is then concentrated by evaporation, washed, dried and calcined to obtain a molybdenum trioxide product.
  • the pure calcium tungstate product can be obtained by dissolving, reprecipitating and drying the calcium tungstate precipitate.
  • the vanadium molybdate solution containing a small amount of vanadium can be removed by a nanofiltration membrane and ion exchange to obtain a pure ammonium molybdate solution.
  • the pure molybdate solution is acidified, evaporated and dried to prepare a molybdic acid product having a purity of more than 99.1%.
  • Step (5) is a key step in the simultaneous purification of vanadium, tungsten and molybdenum in the leachate.
  • the method for simultaneous purification of the valuable group in the leachate may be coprecipitation, extraction and ion exchange.
  • the extracting agent may be amines, organic phosphoric acids, organic esters, neutral phosphines, quaternary ammonium salts and anthraquinones, such as primary amines N1923, Primene JMT.
  • the concentration of the alkali solution is 1 to 10 g/L, for example, 2 g/L, 4 g/L, 6 g/L, 8 g/L, and 9 g/L; and the aqueous ammonia concentration is 5% to 30%, for example, 10%, 15%, 20%, 25% and 28%, etc.
  • the stripping temperature is 20 to 70 ° C, for example, 30, 40, 50, and 60 ° C; the stripping time is 0.5 to 4 h, for example, 1, 1.5, 2, 2.5, 3, and 3.5.
  • the resin type is a strongly basic or weakly basic anion exchange resin, for example, D418, D301, etc.
  • the volume of the leachate is 10 to 100 times the volume of the resin, for example, 20, 30, 40, 50, 60, 70, 80, 90, etc.
  • the pH of the solution is 1 to 12, for example, 2, 4, 6, 8, and 10
  • the temperature is 10 to 100 ° C, for example, 20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C and 90 ° C
  • exchange time is 30 ⁇ 120min, such as 20min, 40min, 60min, 80min and 100min
  • resin regeneration liquid is a strong base or weak alkali solution, For example, NaOH, Na 2 CO 3 and ammonia water
  • regeneration time is 20-120 min, for example 30 min, 50 min, 60 min, 70 min, 80 min, 90 min and 110 min
  • regeneration temperature is 20-100 ° C
  • the precipitating agent is an alkali metal salt or the like, and is, for example, Ca(NO 3 ) 2 , CaCl 2 , Mg(NO 3 ) 2 , MgCl 2 , BaCl 2 , and Ba (NO). 3 ) 2 and so on.
  • Step (5) is also the core step in the preparation of the new SCR denitration catalyst from the catalytic component mixture.
  • the SCR denitration catalyst can be classified into a granular and monolithic catalyst according to its appearance, wherein the monolithic catalyst is further divided into a plate type, a honeycomb type and a corrugated plate catalyst.
  • Most of the particulate catalysts are obtained by fully impregnating the TiO 2 powder in a precursor solution of ammonium metavanadate and other promoters by an impregnation process, followed by evaporation, drying and calcination.
  • the plate catalyst adopts metal sieve plate as the support, and has good mechanical strength, and is especially suitable for the case of desulfurization of coal-fired high-ash SCR;
  • the honeycomb catalyst is based on the SCR catalyst powder, and is mixed, kneaded, extruded, and dried with a molding aid. And the process of calcination and so on.
  • the corrugated plate catalyst is a corrugated fiberboard as a support, and the surface of the coating is coated with an active component.
  • the active material is 70% less than the honeycomb catalyst. When the surface active material is worn away, the catalytic activity decreases rapidly. Short life.
  • Both honeycomb and plate catalysts are firstly mixed with water, binder, sweller, pore expander, lubricant, glass fiber, etc., using V 2 O 5 /TiO 2 -based SCR catalyst powder as raw material.
  • the plastic paste is then obtained by extrusion molding, drying and calcining the honeycomb catalyst with the plastic paste as a matrix.
  • the plate-shaped catalyst is obtained by uniformly pressing the plastic paste onto a metal sieve plate, followed by drying and calcination to obtain a catalyst.
  • the SCR catalyst powder is prepared by a precipitation method, a dipping method, a mixing method, an ion exchange method, a roll coating method, and a hot melt method.
  • the impregnation method is to impregnate a liquid material containing the active component and the cocatalyst component onto the surface of the solid support.
  • the carrier has high utilization rate, low dosage and low cost, and is widely used for the preparation of supported catalysts, especially for low-content precious metal catalysts; precipitation method is to convert soluble catalyst components into insoluble or insoluble compounds by using a precipitating agent. The process of separating, washing, drying, calcining, molding, etc., to obtain a finished catalyst.
  • the mixing method is simple, easy to operate, stable in chemical composition, and can be used to prepare high-content multi-component catalysts, especially mixed oxide catalysts.
  • the dispersion degree of the method is low; the active component paste is placed in a shakeable container by a roll coating method, and a non-porous carrier ball is placed thereon, and after a period of rolling, the active component gradually adheres to the carrier. surface.
  • the roll coating method is not commonly used; the ion exchange method uses an exchanger as a carrier to introduce the active component in the form of a counter ion to prepare a highly dispersed, large-surface supported metal or metal ion catalyst, and is particularly suitable. It is prepared by using a low-content, high-utilization precious metal catalyst; the high-temperature melting method is to melt the various components of the catalyst into a uniformly distributed mixture, an oxide solid solution or an alloy solid solution by a high temperature condition to obtain a catalyst with special properties. It is mainly used for the preparation of ammonia synthesis molten iron catalyst, Fischer-Tropsch synthesis catalyst, Lanier framework catalyst and the like.
  • the present invention preferably produces an SCR catalyst powder by an impregnation method.
  • the usual molding methods are as follows: (1) Spray molding: the prepared sol or suspension is spray-dispersed in a drying tower by a spray head, and becomes a microsphere after being dried by hot air. Dry gel, particle size range 30 ⁇ 200 microns; (2) oil column forming: the raw material solution is divided into two ways, into the low pressure nozzle at a certain flow rate ratio, rapidly mixing in the nozzle and forming a sol, After leaving the nozzle, it is dispersed in a small light droplet state in a warm light oil or transformer oil column, and condenses into a hydrogel within a few seconds.
  • the slurry is forced to pass through the perforated plate by a piston or a spiral, and cut into strips or ring cylinders of almost equal length and the like, and dried and calcined to obtain a product.
  • Tablet molding Many powder materials are made into a sheet-like cylinder or ring cylinder with uniform shape, uniform size and high mechanical strength.
  • the method of the present invention comprises the following steps:
  • the leaching agent is neutral or alkaline
  • the liquid-solid ratio of the leaching agent to the spent catalyst is 0.02 to 1 L/g
  • the leaching temperature is 20 to 200 ° C
  • the leaching pressure is 0.1 to 1 MPa
  • the leaching time is 0.5 to 5 h
  • the stirring speed is 100 to 5000 r/min;
  • Step (2) Each valuable element in the leachate is separated by an extraction method, an ion exchange method or a precipitation method.
  • the extracting agent may be an amine, an organic phosphonic acid, an organic ester, a neutral phosphine, a quaternary ammonium salt and a hydrazine, and the concentration of the extracting agent is 5% to 30%, and the initial pH of the aqueous phase is 1 ⁇ .
  • the extraction temperature is 10 ⁇ 40 ° C
  • the extraction time is 10 ⁇ 40min
  • the resin type is a strong alkaline or weakly basic anion exchange resin
  • the volume of the leachate is 10 ⁇ 100 times the volume of the resin
  • the pH of the solution is 2 ⁇ 11
  • temperature is 20 ⁇ 90°C
  • exchange time is 30 ⁇ 100min
  • resin regeneration liquid is strong alkali or weak alkali solution
  • regeneration time is 20 ⁇ 120min
  • regeneration temperature is 25 ⁇ 90°C
  • the obtained vanadium purified material and the tungsten/molybdenum/tungsten-molybdenum enriched material are further purified to prepare vanadium and tungsten/molybdenum/tungsten-mol
  • the extracting agent may be an amine, an organic phosphonic acid, an organic ester, a neutral phosphine, a quaternary ammonium salt and a hydrazine, and the concentration of the extracting agent is 5% to 30%, and the initial pH of the aqueous phase is 1 ⁇ .
  • the extraction temperature is 10 ⁇ 40 ° C, the extraction time is 10 ⁇ 40min;
  • the resin type is a strong alkaline or weakly basic anion exchange resin
  • the volume of the leachate is 10 ⁇ 100 times the volume of the resin
  • the pH of the solution is 1 ⁇ 12
  • temperature is 10 ⁇ 100°C
  • exchange time is 30 ⁇ 120min
  • resin regeneration liquid is strong alkali or weak alkali solution
  • regeneration time is 20 ⁇ 120min
  • regeneration temperature is 20 ⁇ 100°C
  • the catalytic component mixture described in the step (3) is prepared into a new granular SCR denitration catalyst powder by an impregnation method.
  • the catalytic component mixture is first dissolved in an oxalic acid solution of 0.1 to 0.2 mol/L, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 2 to 4 hours. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness is placed in a drying oven at 105 to 110 ° C for 12 to 24 hours.
  • the dried solid mixture is ground into a powder, and then placed in a muffle furnace for calcination at a calcination temperature of 400 to 600 ° C and a calcination time of 5 to 12 h.
  • the calcined product is a new granular SCR denitration catalyst powder.
  • the present invention has the following beneficial effects:
  • the method of the invention truly realizes the new catalyst which is re-manufactured to be highly active while the waste SCR denitration catalyst is harmlessly treated, and has good environmental and economic benefits;
  • the method of the present invention can separate valuable elements such as V, Mo and W in the waste SCR catalyst. And the recovery and recovery, the recovery of V, Mo and W are more than 95%, and the purity of the prepared vanadium/tungsten/molybdenum/tungsten-molybdenum product is over 99%.
  • Figure 1 is a process flow diagram of the method of the present invention.
  • the waste vanadium molybdenum-based SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.1%, a MoO 3 content of 3.3%, and a TiO 2 content of 95.3%.
  • the temperature was 20 ° C and the stripping time was 0.5 h. Adjusting the ratio of V and Mo in the mixed vanadium-molybdenum ammonium salt solution, and then evaporating, crystallizing, washing and drying at 50 ° C to obtain a vanadium-molybdenum mixed ammonium salt;
  • the vanadium molybdenum mixed ammonium salt obtained in the step (3) is first dissolved in a 0.2 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 2 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 12 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 400 ° C and a calcination time of 5 h.
  • the calcined product is a granular 1.2% V 2 O 5 -3.5% MO 3 /TiO 2 -based SCR denitration catalyst;
  • the waste vanadium molybdenum-based SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.4%, a MoO 3 content of 3.2%, and a TiO 2 content of 95%.
  • the extraction time was 15 min, and V and Mo were simultaneously extracted from the leachate of step (2).
  • the extraction rate of V was 99.6%, and the extraction rate of Mo was 98.8%.
  • the extraction time was 25 min, and V and Mo were extracted and extracted from the leachate of step (2).
  • the extraction rate of V was 99.5%, and the extraction rate of Mo was 0.12%, and a vanadium-rich organic phase and a molybdenum-containing raffinate were obtained.
  • the vanadium metavanadate was precipitated by the reverse extraction of vanadium-rich organic with 15% ammonia water.
  • the time is 4h;
  • the vanadium molybdenum mixed ammonium salt obtained in the step (3) is first dissolved in a 0.15 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 2.5 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 105 ° C for 15 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 450 ° C and a calcination time of 6 h.
  • the calcined product was a particulate 1.1% V 2 O 5 -3.1% MO 3 /TiO 2 -based SCR denitration catalyst.
  • the waste vanadium-tungsten SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.5%, WO 3 of 3.3%, and TiO 2 of 95%.
  • the temperature was 50 ° C and the stripping time was 3 h. Adjusting the ratio of V and W in the vanadium-tungsten mixed ammonium salt solution, and then evaporating, crystallizing, washing and drying at 48 ° C to obtain a vanadium-tungsten mixed ammonium salt;
  • Sodium vanadate solution
  • the vanadium-tungsten mixed ammonium salt obtained in the step (3) is first dissolved in a 0.16 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 3 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 106 ° C for 16 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 500 ° C and a calcination time of 5.5 h.
  • the calcined product is a granular 1.2% V 2 O 5 -3.0% WO 3 /TiO 2 -based SCR denitration catalyst;
  • the waste vanadium-tungsten SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.3%, WO 3 of 3.2%, and TiO 2 of 95.2%.
  • the temperature was 45 ° C and the stripping time was 3 h. Adjusting the ratio of V and W in the vanadium-tungsten mixed ammonium salt solution, and then evaporating, crystallizing, washing and drying at 45 ° C to obtain a vanadium-tungsten mixed ammonium salt;
  • the vanadium-tungsten mixed ammonium salt obtained in the step (3) is first dissolved in a 0.2 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 4 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 18 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 550 ° C and a calcination time of 7 h.
  • the calcined product is a granular 1.3% V 2 O 5 -3.4% WO 3 /TiO 2 -based SCR denitration catalyst;
  • the waste vanadium-tungsten-based SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.3%, WO 3 of 2.4%, and TiO 2 of 96.1%.
  • the liquid-solid ratio is 0.2 L/g
  • the leaching temperature is 100 ° C
  • the leaching pressure is 0.2 MPa
  • the leaching time is 4h
  • the stirring speed is 2000r/min
  • the V single-stage leaching rate is 81.7%
  • W is 77.2%
  • the leaching residue returns to the step (1);
  • V and W were simultaneously extracted from the leachate under the condition of 35 min, the V extraction rate was 99.0%, and the W extraction rate was 97.6%.
  • the temperature was 50 ° C and the stripping time was 4 h. Adjusting the ratio of V and W in the vanadium-tungsten mixed ammonium salt solution, and then evaporating, crystallizing, washing and drying at 50 ° C to obtain a vanadium-tungsten mixed ammonium salt;
  • the extraction rate of V was 99.8%, and the extraction rate of W was 0.3%, and a vanadium-rich organic phase and a tungsten-containing raffinate were obtained.
  • Sodium solution
  • the vanadium-tungsten mixed ammonium salt obtained in the step (3) is first dissolved in a 0.2 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 3 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 24 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 600 ° C and a calcination time of 12 h.
  • the calcined product is a granular 1.4% V 2 O 5 -3.0% WO 3 /TiO 2 -based SCR denitration catalyst;
  • the ammonium acid solution was crystallized by evaporation, washed and dried to give an ammonium paratungstate product having a purity of 99.3%.
  • the waste vanadium-tungsten-molybdenum SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.3%, WO 3 of 1.4%, MoO 3 of 1.4%, and TiO 2 of 95.7%.
  • the liquid-solid ratio is 0.3 L/g
  • the leaching temperature is 100 ° C
  • the leaching pressure is 0.4 MPa.
  • the leaching time is 5h
  • the stirring speed is 3000r/min
  • the V single-stage leaching rate is 81.7%
  • W is 77.2%
  • the leaching residue returns to step (1);
  • the V, W and Mo were simultaneously extracted from the leachate of step (2) under the condition of 40 min, the V extraction rate was 99.6%, the W extraction rate was 98.6%, and the Mo extraction rate was 97.8%.
  • the stripping temperature was 45 ° C and the stripping time was 2 h. Adjusting the ratio of V, W and Mo in the vanadium-tungsten-molybdenum mixed ammonium salt solution, and then evaporating, crystallizing, washing and drying at 45 ° C to obtain a vanadium-tungsten-molybdenum mixed ammonium salt;
  • the vanadium-tungsten-molybdenum mixed ammonium salt obtained in the step (3) is first dissolved in a 0.2 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 4 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 24 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 600 ° C and a calcination time of 10 h.
  • the calcined product is a granular 1.4% V 2 O 5 -1.2% WO 3 -1.2% MoO 3 /TiO 2 -based SCR denitration catalyst;
  • the waste vanadium molybdenum-based SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.2%, a MoO 3 of 2.5%, and a TiO 2 of 96%.
  • the liquid-solid ratio is 0.5L/g
  • the leaching temperature is 200°C
  • the leaching pressure is 1MPa
  • the leaching time is 5h
  • the stirring speed is 5000r/min
  • the V single-stage leaching rate is 84.1%
  • Mo is 80.1%
  • the leaching residue returns to the step (1);
  • the V and Mo were simultaneously extracted from the leachate in step (2) under the conditions of V.
  • the extraction rate of V was 99.8%, and the extraction rate of Mo was 98.9%.
  • the temperature was 30 ° C and the stripping time was 2.5 h. Adjusting the ratio of V and Mo in the mixed vanadium-molybdenum ammonium salt solution, and then evaporating, crystallizing, washing and drying at 40 ° C to obtain a vanadium-molybdenum mixed ammonium salt;
  • V and Mo were separated and extracted from the leachate of step (2), the extraction rate of V was 0.1%, and the extraction rate of Mo was 99.9%, and a molybdenum-rich organic phase and a vanadium-containing raffinate were obtained.
  • the vanadium molybdenum mixed ammonium salt obtained in the step (3) is first dissolved in a 0.1 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 4 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 24 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 600 ° C and a calcination time of 9 h.
  • the calcined product is a granular 1.5% V 2 O 5 -2.6% MO 3 /TiO 2 -based SCR denitration catalyst;
  • the waste vanadium molybdenum-based SCR denitration catalyst provided by a laboratory has a V 2 O 5 content of 1.5%, a MoO 3 of 2.3%, and a TiO 2 of 96.1%.
  • the liquid-solid ratio is 0.6L/g
  • the leaching temperature is 150°C
  • the leaching pressure is 0.5MPa
  • the leaching time is 5h
  • the stirring speed is 5000r/min
  • the V single-stage leaching rate is 80.1%
  • Mo is 81.1%
  • the leaching residue returns to the step (1);
  • the temperature was 20 ° C and the stripping time was 3 h. Adjusting the ratio of V and Mo in the mixed vanadium-molybdenum ammonium salt solution, and then evaporating, crystallizing, washing and drying at 40 ° C to obtain a vanadium-molybdenum mixed ammonium salt;
  • the extraction rate of V was 99.7%, and the extraction rate of Mo was 0.4%.
  • the vanadium-rich organic phase and the molybdenum-containing raffinate were obtained.
  • the vanadium molybdenum mixed ammonium salt obtained in the step (3) is first dissolved in a 0.1 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 4 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 24 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 600 ° C and a calcination time of 9 h.
  • the calcined product is a granular 1.4% V 2 O 5 -2.2% MO 3 /TiO 2 based SCR denitration catalyst;
  • the waste vanadium-tungsten-based SCR catalyst provided by a laboratory has a V 2 O 5 content of 1.2%, a WO 3 of 3.3%, and a TiO 2 of 95.3%.
  • the liquid-solid ratio is 1 L/g
  • the leaching temperature is 200 ° C
  • the leaching pressure is 1 MPa.
  • the leaching time is 5h
  • the stirring speed is 100r/min
  • the V single-stage leaching rate is 77.2%
  • W is 75.6%
  • the leaching slag is subjected to secondary leaching;
  • the vanadium tungsten solution is evaporated, crystallized, washed and dried at 105 ° C, and further calcined at 600 ° C to obtain a vanadium tungsten mixed oxide;
  • a vanadium-tungsten-based SCR catalyst powder is prepared by a mixed method of the vanadium-tungsten mixed oxide obtained in the step (3).
  • the vanadium-tungsten mixed oxide was first pulverized to 100 mesh, and then wet-milled and mixed with TiO 2 at a certain ratio for 5 hours. After the end of the mixing, they were placed in an oven at 110 ° C for 12 h. The dried product was 1.3% V 2 O 5 -3.2% WO 3 /TiO 2 -based SCR catalyst powder.
  • the mold containing the catalyst paste was heated in an oven at 65 ° C, and after the paraffin wax which was previously applied to the sizing rod and the surface of the mold was melted, the mold was taken out to obtain a semi-dry catalyst body.
  • the catalyst embryo body was dried in an oven at 105 ° C for 12 h and then calcined at 450 ° C for 12 h to obtain a honeycomb 1.3% V 2 O 5 -3.3% WO 3 /TiO 2 -based SCR denitration catalyst;
  • the waste vanadium-tungsten-based SCR catalyst provided by a laboratory has a V 2 O 5 content of 1.1%, a MO 3 of 2.5%, and a TiO 2 of 96.2%.
  • the mixed precipitate is dissolved in nitric acid, and after adjusting the pH of the solution to 12, the calcium chloride is coprecipitated, and the obtained precipitate is washed and dried to be a pure vanadium-molybdenum mixed calcium salt.
  • the vanadium-molybdenum solution is evaporated, crystallized, washed and dried at 105 ° C, and further calcined at 650 ° C to obtain a vanadium-molybdenum mixed oxide;
  • the vanadium molybdenum mixed oxide obtained in the step (3) is first dissolved in a 0.1 mol/L oxalic acid solution, and then TiO 2 is added in proportion.
  • the system was placed in an ultrasonic cleaner and ultrasonically mixed for 4 h. After the end of the ultrasound, the system was stirred and evaporated to dryness.
  • the solid mixture obtained after evaporation to dryness was placed in an electric blast drying oven at 110 ° C for 24 h.
  • the dried solid mixture was ground into a powder, placed in a crucible and placed in a muffle furnace for calcination at a calcination temperature of 600 ° C and a calcination time of 9 h.
  • the calcined product was a 1.2% V 2 O 5 -2.5% MO 3 /TiO 2 -based SCR catalyst powder. 50 g of the catalyst powder ground to 0.1 mm was taken, and then 5 g of a binder polyacrylamide and 2.5 g of activated carbon powder having a particle diameter of 0.1 mm were added, followed by dry mixing for 20 minutes. After the mixture was uniformly mixed, 8 mL of water and 3.5 mL of the eluating agent ethanolamine were sequentially added, and then the wet material was kneaded with a crucible bar to obtain a plastic paste.
  • the plastic paste was placed in the upper portion of the honeycomb catalyst mold, and the plastic paste was forcibly pressed between the lower shaping rods using a press plate.
  • the mold containing the catalyst paste was heated in an oven at 60 ° C, and after the paraffin wax which was previously applied to the sizing rod and the surface of the mold was melted, the mold was taken out to obtain a semi-dried catalyst body.
  • the catalyst body was dried in an oven at 110 ° C for 24 h and then calcined at 450 ° C for 12 h to obtain a honeycomb 1.3% V 2 O 5 -2.4% WO 3 /TiO 2 -based SCR denitration catalyst.
  • the calcium precipitation, the molar ratio of calcium nitrate to metal molybdenum in the leachate mpre:mmetal 6, the reaction temperature is 50 ° C, the precipitation time is 120 min, and calcium molybdate precipitation can be obtained.
  • the calcium molybdate precipitate was washed and dried to obtain a calcium molybdate product having a purity of 99.6%.
  • the waste vanadium molybdenum-based SCR catalyst provided by a laboratory has a V 2 O 5 content of 1.1%, a MO 3 of 2.0%, and a TiO 2 of 96.7%.
  • the liquid-solid ratio is 1 L/g
  • the leaching temperature is 100 ° C
  • the leaching pressure is 0.2 MPa.
  • the leaching time is 0.5h
  • the stirring speed is 5000r/min
  • the V single-stage leaching rate is 96.2%
  • the Mo is 95.2%
  • the Ti is 86.1%
  • the leaching residue is returned to the step (1);
  • V, Mo and Ti in the leachate obtained in the step (2) are simultaneously extracted by the weakly basic anion exchange resin D418.
  • the volume of the leachate was 10 times the volume of the resin, the pH of the solution was 1, the temperature was 10 ° C, the exchange reaction time was 30 min, the V extraction rate was 94.3%, the Mo was 95.8%, the Ti was 96.2%, and the mother liquor was subjected to secondary extraction.
  • the resin was washed and regenerated with 15% ammonia water, the regeneration time was 20 min, and the regeneration temperature was 20 ° C, obtained vanadium molybdenum titanium mixed ammonium salt solution;
  • the vanadium-molybdenum solution was separated by a weakly basic anion exchange resin D418.
  • the volume of the leachate was 10 times the volume of the resin, the pH of the solution was 2, the temperature was 20 ° C, the exchange reaction time was 30 min, the V extraction rate was 99.3%, and Mo was 0.2%.
  • a negative vanadium resin and a molybdenum containing residue are obtained.
  • the resin was washed and regenerated with a 2 g/L Na 2 CO 3 solution, the regeneration time was 20 min, and the regeneration temperature was 25 ° C to obtain a sodium vanadate solution;
  • the vanadium molybdenum-titanium mixed ammonium salt solution obtained in the step (3) is prepared by a precipitation method to prepare a vanadium molybdenum-based SCR denitration catalyst powder.
  • a plastic paste After mixing uniformly, 8 mL of water, 4 mL of the eluating agent ethanolamine and 2.5 mL of lubricating oil glycerin were sequentially added, and then the wet material was kneaded with a crucible bar to obtain a plastic paste.
  • the 55*100mm stainless steel plate with mesh holes is used as the support.
  • the thickness of the sieve plate is 0.5mm, the hole diameter is 1mm, the hole pitch is 1.5mm, and the triangles are arranged in a regular triangle shape.
  • the 0.5mm thick plastic paste is uniformly pressed on the lower and upper sides of the sieve plate.
  • the sieve plate with the plastic paste was dried at 105 ° C for 12 h, and then calcined at 500 ° C for 24 h to obtain a catalyst veneer having a thickness of 1.5 mm, which was assembled in a stainless steel casing to obtain a plate catalyst;
  • the waste vanadium-tungsten-based SCR catalyst provided by a laboratory has a V 2 O 5 content of 1.3%, WO 3 of 2.4%, and TiO 2 of 96.1%.
  • step (2) Using 1g/L NaOH solution as leaching agent, leaching V and W from step (1), liquid-solid ratio of 0.7L/g, leaching temperature of 150°C, leaching pressure of 0.5MPa, leaching time of 2h, stirring The speed is 4000r/min, the V single-stage leaching rate is 87.2%, W is 86.3%, Ti is 84.3%; the leaching residue returns to step (1);
  • V and W in the leachate obtained in the step (2) are simultaneously extracted by the strongly basic anion exchange resin D201.
  • the volume of the leachate was 100 times the volume of the resin, the pH of the solution was 12, the temperature was 100 ° C, the exchange reaction time was 120 min, the V extraction rate was 99.1%, and the W was 98.9%.
  • the mother liquor was subjected to secondary extraction.
  • the resin was washed and regenerated with 2 g/L NaOH solution, the regeneration time was 120 min, and the regeneration temperature was 100 ° C to obtain a vanadium-tungsten mixed sodium salt solution;
  • V and W in the leachate described in the step (2) are separated by a strong basic anion exchange resin D201.
  • the volume of the leachate was 100 times the volume of the resin, the pH of the solution was 11, the temperature was 90 ° C, the exchange reaction time was 100 min, the V extraction rate was 99.1%, and the W was 0.1%, and a negative vanadium resin and a tungsten-containing residual liquid were obtained.
  • the resin was washed and regenerated with a 5 g/L NaOH solution, the regeneration time was 120 min, and the regeneration temperature was 90 ° C to obtain a sodium vanadate solution;

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