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)
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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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Abstract

一种废SCR脱硝催化剂的回收处理方法，首先将废SCR脱硝催化剂进行预处理，去除杂质、活化钒钨钼等催化组分后，经过浸出后得到富钛浸出渣和含钨钼钒的浸出液；浸出液中有价元素可以通过两种方法进行资源化处理：第一种是对浸出液中有价组分同步纯化后进行各个物质含量的比例调节，制备催化组分的混合物，并进一步制备为新的催化剂，实现再制造；第二种是对浸出液中各个有价元素进行分离、纯化，制备不同的产品。

Description

一种废SCR脱硝催化剂的回收处理方法 技术领域
本发明属于固体废物处理领域，尤其涉及一种废SCR脱硝催化剂的回收处理方法。
背景技术
我国是煤炭资源消耗大国，煤炭的燃烧在为居民生活带来便利的同时，又会产生大量的氮氧化物(NOx)和硫氧化物(SO2)。这些氮氧化物和硫氧化物是大气污染的主要组成部分，一方面严重污染着空气环境，另一方面还会形成酸雨，给自然界的水资源带来巨大隐患。选择性催化还原法(Selective Catalytic Reduction，SCR)是近年来兴起的一种较可靠且工艺简单的脱硝技术，它通常是以氨作为脱硝剂，在SCR催化剂的作用下，将氮氧化物催化还原为无污染作用的氮气。SCR催化剂主要有钒钨系、钒钼系和钒钨钼系。三者都以V2O5和TiO2作为催化活性主体，不同的是钒钨系催化剂是以WO3作为助剂，钒钼系是以MoO3作为助剂，而钒钨钼系则是以WO3和MoO3作为共同的助剂。在选择性催化还原技术中，催化剂的投资是核心部分，催化剂的活性直接决定脱硝的效率。SCR脱硝催化剂在使用过程中活性会有所降低，因此，必须对使用过一定时间后的催化剂进行再生活化。但是有的SCR催化剂经过反复活化使用后，其原有物理结构已被严重破坏，已很难再生处理，这些无法再生的催化剂即为废SCR催化剂。
2012年公布执行的《火电厂烟气脱硝工程技术规范一选择性催化还原法》中提到，对蜂窝式废SCR脱硝催化剂的处理方式为压碎填埋。但废SCR催化剂因含有V2O5、WO3或MoO3等有毒金属氧化物，属于危险固体废物，若按填埋 方式处置SCR废催化剂，不仅会占据大量的土地资源，也会对环境污染带来风险，还将对电厂和工程公司造成经济负担。事实上，蜂窝式废SCR催化剂本身含有的WO3、MoO3、V2O5和TiO2都是宝贵的资源，若能采取分离提纯的方式将其回收，不仅可产生新的利润增长点，还可达到烟气脱硝产业链中各种物质形成闭路循环的良好效果。
专利CN104192911A公开了一种回收废旧SCR脱硝催化剂中三氧化钨成分的方法。其是将废旧SCR脱硝催化剂充分粉碎至干粉状，高温焙烧后利用特定溶液在一定条件下溶解催化剂中的三氧化钨成分，使三氧化钨与催化剂中其它成分有效分离，收集上层含钨清液并将其蒸干，将得到的固体充分干燥，经高温焙烧后，完成对三氧化钨成分的回收。
专利CN104195342A公开了一种回收废旧SCR脱硝催化剂中五氧化二钒成分的方法。其先在酸性溶液中利用还原剂将催化剂中的五价钒还原为更易溶的四价钒，然后用氧化剂再将酸性溶液中的四价钒氧化为五价钒，通过调节溶液的pH值，在一定条件下使五价钒充分水解而沉淀，收集沉淀经焙烧处理即可得到高纯度的五氧化二钒，五氧化二钒纯度为98％。
专利CN103130265A公开了一种从废旧SCR脱硝催化剂中回收钛白粉的方法。其先对废脱硝催化剂进行除尘、粉碎磨粉，然后加入浓硫酸将其酸解后得到硫酸氧钛浓溶液，再加水稀释；接着加入非离子型乳化剂作为絮凝剂，磺酸盐表面活性剂或聚羧酸盐表面活性剂作为助凝剂，接着加入水溶性甲基硅油；再泵入板框压滤机进行压滤，将滤液真空浓缩再加热至90℃-98℃并保持5.5小时使滤液水解；然后水解产物冷却至40℃，进行真空过滤使偏钛酸沉积出来；再用砂滤水和去离子水漂洗后，加入碳酸钾或磷酸得到偏钛酸滤饼；对滤饼烘干后在500-800℃下煅烧，接着粉碎、磨细得到二氧化钛成品。
专利CN104261415A公开了一种完全回收废弃SCR催化剂中二氧化硅的方法。将粉碎后的废弃SCR催化剂用3～4倍体积的水浸泡除杂，除杂后粉体用过量的浓度为60～80wt％的浓碱溶液浸出，采用过滤得到固体偏钛酸钠Na2TiO3，向滤液中加入硫酸，70～90℃下调节pH至11.5～12.5，静置0.5～1h，，过滤弃去滤饼；再向滤液中加入硫酸调至pH为9～10得到的滤饼为硅酸，硅酸滤饼于稀硫酸与草酸的混酸40～60℃加热搅拌1～2h，过滤，用去离子水洗涤滤饼，洗掉固体所含的酸根离子，经加热分解得到高纯度二氧化硅。
专利CN104275178A公开了一种废弃SCR脱硝催化剂的回收再生及再生SCR催化剂载体的方法。将废弃SCR催化剂经过粉碎、过筛、水洗、酸洗后，再经湿法粉碎、研磨，得到催化剂浆体。再将浆体与偏钛酸浆液混合，得到混合浆液。将混合浆液经过水洗、过滤、脱水、调节pH后，加入还原剂漂白。漂白后的浆液加水、调节pH，加入仲钨酸铵及白炭黑，经搅拌、过滤、脱水、煅烧、粉碎，得回收再生的催化剂。
专利CN104263946A公开了一种从SCR脱硝废催化剂中回收钨、钒、钛的方法。将SCR废催化剂清洗后粉碎、筛分，掺入碳酸钠搅拌均匀，将混合粉末在高温下烧结得到烧结料，再加水浸出，得到含有钨、钒的钠盐混合溶液；在溶液pH值大于12的条件下选择性萃取钨，用铵盐溶液进行反萃得到钨酸铵溶液；萃取钨后的萃余液在pH值为10～11.5的条件下萃取钒，用氢氧化钠溶液进行反萃得到含少量钨的钒酸钠溶液；钛留在浸出渣中得到富钛料。
专利CN104178636A公开了一种活化煅烧结合酸性浸出回收SCR废旧催化剂中Ti，V，Mo，Si的方法。其处理步骤为：先将SCR废旧催化剂的预处理，然后高温煅烧活化。接着对煅烧产物酸性浸出，得到白色TiO2粉末。浸出液蒸发浓缩后，得到白色沉淀H2MoO4。浸出液加氨水调节pH至8.0～9.0，得到NH4VO3 沉淀。再将浸出液加氨水调节pH至8.0～9.0，再加入MgCl2得到MgSiO3。过滤后的滤液进入废水回收***。
专利CN104326506A公开了一种用于回收失效脱硝催化剂中二氧化钛的方法。它包括以下步骤：(1)将失效脱销催化剂研磨至粉末状置于敞口容器内，向敞口容器中滴加适量蒸馏水防止结底；(2)酸解，质量分数为98％的浓硫酸加入敞口容器，对敞口容器加热使粉末溶解，在加热过程中持续搅拌使固液混合均匀，当敞口容器内的溶液呈棕黄色时停止加热，冷却至≤30℃得到钛液；(3)中和，将质量分数50％～80％活性钙含量为80％的石灰乳溶液逐滴滴加到钛液中，边滴加边摇匀，控制钛液温度≤70℃，充分反应后冷却至室温；(4)浓缩水解，将中和后的钛液浓缩至195-205g/l，加入晶种加热水解，过滤、漂洗、烘干煅烧后得钛盐。
上述现有的SCR脱硝催化剂回收处理技术均无法实现废SCR脱硝催化剂的循环再制造，同时也无法实现V、W、Mo和Ti等有价元素的高效分离并获得纯度超过99％的钒钨钼产品。迄今为止，我国还没有一套成熟的废SCR催化剂的回收处理工程案例，归根到底是没有成熟可行、适宜推广的废催化剂回收处理技术。
发明内容
基于当前废SCR脱硝催化剂的回收处理技术缺乏的现实，本发明提出一种既可以实现废SCR脱硝催化剂再制造，又可以根据需要将钒钨钼等有价组分分离回收和纯化的方法，其中有价金属的回收率超95％，钒/钨/钒钼产品的纯度可达99％以上。
为达此目的，本发明采用以下技术方案：
一种废SCR脱硝催化剂的回收处理方法，包括如下步骤：
(1)将废SCR脱硝催化剂预处理，去除杂质、活化钒钨钼等催化组分；
(2)对步骤(1)预处理后得到的废SCR脱硝催化剂进行浸出，得到浸出渣和浸出液；
(3)对步骤(2)得到的浸出液中各个有价元素进行分离，得到钒提纯物和钨/钼/钨钼富集物；
(4)将步骤(3)得到的钒提纯物进一步纯化，用于制备钒产品；得到的钨/钼/钨钼富集物进一步纯化，用于制备钨/钼/钨钼产品。
(5)将步骤(2)得到的浸出液中有价元素进行同步纯化，调节各个物质含量的比例，从而得到催化组分混合物，用于进一步制备为新的SCR脱硝催化剂。
步骤(1)是去除废SCR脱硝催化剂中杂质、活化钒钨钼等催化组分的重要步骤。SCR脱硝催化剂在长期使用过程中会携带一些灰尘、砂粒和油份等杂质，这些杂质会影响后续产品的纯度。另外废催化剂中的V2O5、WO3、MoO3为难溶物。因此，需对废催化剂进行预处理，去除携带的杂质和活化钒钨钼等催化组分。步骤(1)中预处理方法可以为洗涤、粉碎、焙烧和干燥等。洗涤和干燥可去除废催化剂携带的灰尘、砂粒和油份；粉碎可提高废催化剂的比表面积；焙烧可将废催化剂中的V2O5、WO3、MoO3活化，转化为易溶于水的VO4 3-、WO4 2-、MoO4 2-。焙烧活化时需加入添加剂，添加剂可为碱金属碱或盐，为节约成本，优选为钠碱或钠盐，例如为NaOH或Na2CO3等。添加剂与废催化剂中金属总量的摩尔比madd∶mmetal＝1～6，例如1.2、1.4、1.6、1.8、2.3、3、3.8、4.8、5.3和5.8等。焙烧温度为500～900℃，例如550℃、600℃、650℃、700℃、750℃、800℃和850℃等。焙烧时间为1～7h，例如1.5h、2h、3h、4h、5h和6h等。
步骤(2)是从固相提取钒钨钼的主要过程。浸出剂可呈中性或酸性或碱性， 若浸出剂呈酸性，则废催化剂中除V、W和Mo外的其他金属如Ti等也会进入溶液，这会使浸出液成分更复杂，加大了后续各组分的分离难度。因此，本发明中浸出剂优选为中性或碱性。浸出剂与焙烧产物的液固比为0.02～1L/g，例如为0.025L/g、0.05L/g、0.1L/g、0.15L/g、0.2L/g、0.25L/g、0.5L/g、0.75L/g和0.8L/g等。浸出温度为20～200℃，例如为25℃、40℃、60℃、80℃、100℃、120℃、140℃、160℃、180℃等。浸出时间可为0.5～5h，例如为0.75h、1h、1.5h、2h、2.5h、3h、3.5h、4h和4.5h等。浸出压力为0.1～1MPa，例如为0.2MPa、0.4MPa、0.6MPa、0.8MPa和1.0MPa等。浸出搅拌速度为100～5000r/min，例如为400r/min、800r/min、1200r/min、1600r/min、2000r/min、2400r/min、2800r/min、3200r/min、3600r/min、4000r/min、4400r/min和4800r/min等。
步骤(3)是浸出液中各个有价元素分离的核心操作。浸出液中的有价元素用萃取法分录时，萃取剂可为胺类、有机膦酸类、有机酯类、中性膦类、季铵盐类和肟类，例如为伯胺类N1923、Primene JMT、Primene 81R和LK-N21，仲胺类DIDA、二辛胺/正辛烷、二辛胺/四氯化碳，叔胺类Alamine 336，季胺盐Aliquat 336，中性膦类TBP，有机酯类醋酸戊酯和有机磷类D2EHPA，肟类Lix63；萃取剂浓度为5％～30％，例如为10％、15％、20％和25％等；水相初始pH＝1～9，例如为1.5、2、2.5、3、3.5、4、5、6、7和8等；萃取温度为10～40℃，例如为15℃、20℃、25℃、30℃和35℃等；萃取时间为10～40min，例如为15min、20min、25min、30min和35min等；对有机相进行反萃时，反萃剂可为碱液或氨水，反萃剂中的NH4 +或OH-与金属总量的摩尔比mNH4 +/mOH-∶mmetal＝1～10，例如为2、3、5、7和9等。其中碱液浓度为1～10g/L，例如为2g/L、4g/L、6g/L、8g/L和9g/L；氨水浓度为5％～30％，例如为10％、15％、20％、25％和28％等。反萃温度为20～70℃，例如为30、40、 50和60℃；反萃时间为0.5～4h，例如为1、1.5、2、2.5、3和3.5等。
浸出液中的各个有价元素用离子交换法分离时，树脂种类为强碱性或弱碱性阴离子交换树脂，例如为D418、D301等；浸出液体积为树脂体积的10～100倍，例如为20、30、40、50、60、70、80和90等；溶液pH为2～11，例如为2、4、6、8和9等；温度为20～90℃，例如为20℃、30℃、40℃、50℃、60℃、70℃和80℃等；交换时间为30～100min，例如为20min、40min、60min和80min等；树脂再生液为强碱或弱碱溶液，例如为NaOH、Na2CO3和氨水等；再生时间为20～120min，例如为30min、50min、60min、70min、80min、90min和110min等；再生温度为25～90℃，例如为30℃、40℃、50℃、60℃、70℃和80℃等；
浸出液中的各个有价元素用沉淀法分离时，沉淀剂为碱金属盐等，例如为Ca(NO3)2、CaCl2、Mg(NO3)2、MgCl2、BaCl2和Ba(NO3)2等；沉淀剂与浸出液中金属总量的摩尔比mpre∶mmetal＝1～6，例如为1.5、2、2.5、3、3.5、4、4.5和5等；溶液pH＝5～11，例如为6、7、8、9和10等；沉淀温度为20～80℃，例如为20、30、40、50、60和70℃；沉淀时间为20～120min，例如为30min、40min、50min、60min、70min、80min、90min、100min和110min等；
步骤(4)是钒提纯物和钨/钼/钨钼富集物分别进一步纯化、制备钒和钨/钼/钨钼产品的重要步骤。钒提纯物进一步纯化的方法为沉淀、萃取、离子交换和膜分离等。偏钒酸铵沉淀经溶解、再沉淀、洗涤、干燥和焙烧可得纯度超过99.5％的五氧化二钒产品。含钒溶液用萃取-反萃沉钒-干燥-焙烧工艺也可以制得高纯五氧化二钒产品。低浓度纯钒液利用电渗析技术可得到浓缩。也可用离子交换法从低浓度的钒溶液中提钒，然后经树脂洗涤再生、蒸发结晶和干燥可制得钒盐产品。钨/钼/钨钼富集物进一步纯化的方法为沉淀、萃取、离子交换和膜分离 等。钼酸钠溶液先用胺类萃取剂萃取，再用氨水反萃可得钼酸铵溶液，然后经蒸发浓缩、洗涤、干燥和焙烧可得三氧化钼产品。钨酸钙沉淀经溶解、再沉淀和干燥可制得纯钨酸钙产品。含少量钒的钼酸铵溶液经纳滤膜和离子交换可去除钒，得到纯钼酸铵溶液。纯钼酸钠溶液经酸化、蒸发和干燥可制备纯度超过99.1％的钼酸产品。
步骤(5)是浸出液中钒钨钼同步纯化的关键步骤。浸出液中有价组同步纯化的方法可以为共沉淀、萃取和离子交换等。浸出液中的有价元素用萃取法同步纯化时，萃取剂可为胺类、有机磷酸类、有机酯类、中性膦类、季铵盐类和肟类，例如为伯胺类N1923、Primene JMT、Primene 81R和LK-N21，仲胺类DIDA、二辛胺/正辛烷、二辛胺/四氯化碳，叔胺类Alamine 336，季胺盐Aliquat336，中性膦类TBP，有机酯类醋酸戊酯和有机磷类D2EHPA，肟类Lix63；萃取剂浓度为5％～30％，例如为10％、15％、20％和25％等；水相初始pH＝1～10，例如为1.5、2、2.5、3、3.5、4、5、6、7、8和9等；萃取温度为10～40℃，例如为15℃、20℃、25℃、30℃和35℃等；萃取时间为10～40min，例如为15min、20min、25min、30min和35min等；对有机相进行反萃时，反萃剂可为碱液或氨水，反萃剂中的NH4 +或OH-与金属总量的摩尔比mNH4 /mOH-∶mmetal＝1～10，例如为2、3、5、7和9等。其中碱液浓度为1～10g/L，例如为2g/L、4g/L、6g/L、8g/L和9g/L；氨水浓度为5％～30％，例如为10％、15％、20％、25％和28％等。反萃温度为20～70℃，例如为30、40、50和60℃；反萃时间为0.5～4h，例如为1、1.5、2、2.5、3和3.5等。
浸出液中的有价元素用离子交换法同步纯化时，树脂种类为强碱性或弱碱性阴离子交换树脂，例如为D418、D301等；浸出液体积为树脂体积的10～100倍，例如为20、30、40、50、60、70、80和90等；溶液pH为1～12，例如为 2、4、6、8和10等；温度为10～100℃，例如为20℃、30℃、40℃、50℃、60℃、70℃、80℃和90℃等；交换时间为30～120min，例如为20min、40min、60min、80min和100min等；树脂再生液为强碱或弱碱溶液，例如为NaOH、Na2CO3和氨水等；再生时间为20～120min，例如为30min、50min、60min、70min、80min、90min和110min等；再生温度为20～100℃，例如为30℃、40℃、50℃、60℃、70℃、80℃和90℃等。
浸出液中的有价元素用共沉淀法同步纯化时，沉淀剂为碱金属盐等，例如为Ca(NO3)2、CaCl2、Mg(NO3)2、MgCl2、BaCl2和Ba(NO3)2等。
步骤(5)也是催化组分混合物制备新SCR脱硝催化剂的核心步骤。SCR脱硝催化剂按照外观可分为颗粒状和整体式催化剂，其中整体式催化剂又分为板式、蜂窝状和波纹板催化剂。颗粒状催化剂大多是采用浸渍工艺将TiO2粉体在偏钒酸铵和其他助催化剂的前驱物溶液中充分浸渍并经蒸干、干燥和锻烧而得到。板式催化剂采用金属筛板作为担体，机械强度好，特别适用燃煤高灰SCR脱硝场合；蜂窝状催化剂是以SCR催化剂粉体为基体，与成型助剂等通过混合、捏合、挤压成型、干燥和锻烧等过程得到。而波纹板式催化剂是以波纹状纤维板为担体，在其表面涂含活性组分的涂层，活性物质要比蜂窝状催化剂少70％，当表面活性物质磨损流失后，催化活性下降较快，使用寿命较短。蜂窝状和板式催化剂都是先以V2O5/TiO2基SCR催化剂粉体为原料，与水、粘合剂、助挤剂、扩孔剂、润滑剂、玻璃纤维等充分混合揉捏得到塑性膏体，然后蜂窝状催化剂以塑性膏体为基体经过挤压成型、干燥和锻烧得到。而板状催化剂是将塑性膏体均匀压制在金属筛板上，后经干燥、锻烧得到催化剂。浸出液中金属总量的摩尔比mpre∶mmetal＝1～5，例如为1.5、2、2.5、3、3.5、4和4.5等；溶液pH＝6～12，例如为7、8、9、10和11等；沉淀温度为10～90℃，例如为20、 30、40、50、60、70和80℃；沉淀时间为10～120min，例如为20min、30min、40min、50min、60min、70min、80min、90min、100min和110min等。
其中，SCR催化剂粉体的制备方法有沉淀法、浸渍法、混合法、离子交换法、滚涂法和热熔融法等。浸渍法是将含有活性组分和助催化剂组分的液态物质浸载在固态载体表面上。其载体利用率高，用量少，成本低，广泛用于负载型催化剂的制备，尤其适用于低含量贵金属催化剂；沉淀法是用沉淀剂将可溶性的催化剂组分转化为难溶或不溶化合物，经分离、洗涤、干燥、煅烧、成型等工序，制得成品催化剂。用于高含量的非贵金属、金属氧化物、金属盐催化剂或催化剂载体；混合法设备简单，操作方便，产品化学组成稳定，可用于制备高含量的多组分催化剂，尤其是混合氧化物催化剂，但此法分散度较低；滚涂法将活性组分粘浆置于可摇动的容器中，无孔载体小球布于其上，经过一段时间的滚动，活性组分便逐渐粘附在载体表面。由于活性组分容易剥离，滚涂法已不常用；离子交换法以交换剂作载体，以反离子的形式引入活性组分，制备高分散、大表面的负载型金属或金属离子催化剂，尤其适用于低含量、高利用率的贵金属催化剂制备；高温熔融法是借高温条件将催化剂的各个组分熔合成为均匀分布的混合体、氧化物固体溶液或合金固体溶液，以制取特殊性能的催化剂。主要用于氨合成熔铁催化剂、费-托合成催化剂、兰尼骨架催化剂等的制备。
综合比较，本发明优选用浸渍法制备SCR催化剂粉体。
制取成型催化剂如板式和蜂窝状SCR脱硝催化剂时，常用的成型方法有：(1)喷雾成型：将配置好的溶胶或悬浮液用喷头在干燥塔内喷雾分散，经热风干燥后成为微球状干凝胶，粒度范围30～200微米；(2)油柱成型：将原料溶液分为两路，按一定的流速比例打入低压喷头，在喷头内迅速混合并形成溶胶， 离开喷头后以小液滴状态分散在温热的轻油或变压器油柱中，几秒内凝结成水凝胶。喷雾成型和油柱成型所得的产品，形状规则，表面光滑，机械强度良好；(3)转动成型：把干燥的粉末放在回转着的、倾斜30～60°的转盘里，喷入雾状粘结剂，润湿了的局部粉末先粘结为核。随着转盘的连续运动，核逐渐成长为圆球，较大的圆球摩擦系数小，浮在表面滚动，符合粒度要求时便从转盘下边沿滚出；(4)挤条成型：粉末加入适当的粘结剂，经碾压捏和之后便形成塑性良好的泥状粘浆。利用活塞或螺旋迫使浆料通过多孔板，切成几乎等长等径的条形圆柱体或环柱体，经干燥、煅烧便得产品。(5)压片成型：将许多粉末物料制成外形一致、大小均匀、机械强度高的片状圆柱体或环柱体。
作为优选技术方案，本发明的方法，包括如下步骤：
(1)将废SCR脱硝催化剂预处理，去除杂质、活化钒钨钼等催化组分；
(2)对步骤(1)中预处理后得到的废催化剂进行浸出，得浸出渣和浸出液；浸出剂为中性或碱性，浸出剂与废催化剂的液固比为0.02～1L/g，浸出温度为20～200℃，浸出压力为0.1～1MPa，浸出时间为0.5～5h，搅拌速度为100～5000r/min；
(3)步骤(2)浸出液中的各个有价元素用萃取法或离子交换法或沉淀法分离。萃取法时，萃取剂可为胺类、有机膦酸类、有机酯类、中性膦类、季铵盐类和肟类，萃取剂浓度为5％～30％，水相初始pH＝1～9，萃取温度为10～40℃，萃取时间为10～40min；离子交换法时，树脂种类为强碱性或弱碱性阴离子交换树脂，浸出液体积为树脂体积的10～100倍，溶液pH为2～11，温度为20～90℃、交换时间为30～100min，树脂再生液为强碱或弱碱溶液，再生时间为20～120min，再生温度为25～90℃；共沉淀法时，沉淀剂与浸出液中金属总量的摩尔比mpre∶mmetal＝1～6，溶液pH＝5～11，沉淀温度为20～80℃，沉淀时间为 20～120min；得到的钒提纯物和钨/钼/钨钼富集物进一步纯化、制备钒和钨/钼/钨钼产品。
或者(4)将步骤(2)浸出液中的有价元素同步纯化后进行各个物质含量比例的调节，制备催化组分混合物。浸出液中的有价元素用萃取法或离子交换法或共沉淀法同步纯化。萃取法时，萃取剂可为胺类、有机膦酸类、有机酯类、中性膦类、季铵盐类和肟类，萃取剂浓度为5％～30％，水相初始pH＝1～10，萃取温度为10～40℃，萃取时间为10～40min；离子交换法时，树脂种类为强碱性或弱碱性阴离子交换树脂，浸出液体积为树脂体积的10～100倍，溶液pH为1～12，温度为10～100℃、交换时间为30～120min，树脂再生液为强碱或弱碱溶液，再生时间为20～120min，再生温度为20～100℃；共沉淀法时，沉淀剂与浸出液中金属总量的摩尔比mpre∶mmetal＝1～5，溶液pH＝6～12，沉淀温度为10～90℃，沉淀时间为10～120min；
(5)步骤(3)所述的催化组分混合物用浸渍法制备为新颗粒状的SCR脱硝催化剂粉体。催化组分混合物先溶解于0.1～0.2mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀2～4h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入105～110℃的干燥箱中干燥12～24h。将干燥后的固体混合物磨成粉末，然后置入马弗炉中焙烧，焙烧温度为400～600℃，焙烧时间为5～12h。焙烧后产物为新颗粒状的SCR脱硝催化剂粉体。
与现有技术方案相比，本发明具有以下有益效果：
1、本发明方法真正地实现了将废SCR脱硝催化剂得到无害化处理的同时再制造为高活性的新催化剂，具有良好的环境效益和经济效益；
2、本发明方法将废SCR催化剂中的V、Mo和W等有价元素可得到分离 和纯化回收，V、Mo和W的回收率均超过95％，制得的钒/钨/钼/钨钼产品纯度达到99％以上。
附图说明
图1是本发明所述方法的工艺流程图。
下面对本发明进一步详细说明。但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
实施例1
某实验室提供的废钒钼系SCR脱硝催化剂，V2O5含量为1.1％，MoO3为3.3％，TiO2为95.3％。
(1)取10g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃下干燥。干燥后的废催化剂加入NaOH作添加剂，NaOH与废催化剂中金属总量的摩尔比madd∶mmetal＝1。混合均匀后置于马弗炉中焙烧，焙烧温度为650℃，焙烧时间为4h；
(2)用中性的纯水作浸出剂，从步骤(1)焙烧后废催化剂中浸出V和Mo，液固比为0.02L/g，浸出温度为20℃，浸出压力为0.1MPa，浸出时间为1.5h，搅拌速度为1000r/min，V单级浸出率为78.6％，Mo为75.7％；浸出渣返回步骤(1)；
(3)以伯胺类萃取剂N1923和甲苯组成的萃取体系为有机相，浓度为5％，在水相初始pH＝1，两相比O/A＝1，萃取温度为10℃，萃取时间为10min的条件 下从步骤(2)所述的浸出液中同步萃取V和Mo，V萃取率为100％，Mo萃取率为99.99％。然后用5％的氨水对萃取相中的V和Mo同步反萃得到钒钼混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝1，反萃温度为20℃，反萃时间为0.5h。调节钒钼混合铵盐溶液中的V和Mo的比例，然后经蒸发、结晶、洗涤和50℃下干燥得钒钼混合铵盐；
(4)以伯胺类萃取剂N1923和甲苯组成的萃取体系为有机相，浓度为5％，在水相初始pH＝6，两相比O/A＝1，萃取温度为10℃，萃取时间为10min的条件下从步骤(2)所述的浸出液中萃取分离V和Mo，V萃取率为100％，Mo萃取率为0.5％，得到富钒有机相和含钼萃余液。富钒有机相用10％的氨水反萃，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝3，反萃温度为40℃，反萃时间为1h，反萃得到偏钒酸铵沉淀；
(5)步骤(3)得到的钒钼混合铵盐先溶解于0.2mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀2h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥12h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为400℃，焙烧时间为5h。焙烧后产物即为颗粒状的1.2％V2O5-3.5％MO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的偏钒酸铵沉淀先用硝酸溶解，再调节溶液pH＝7，然后加入硫酸铵沉淀，得到的偏钒酸铵沉淀经洗涤、干燥和焙烧，得到五氧化二钒产品，纯度为99.5％；步骤(4)得到的含钼萃余液用硝酸调节pH＝1.5，然后经蒸发结晶、洗涤和干燥，得到钼酸产品，纯度为99.1％。
实施例2
某实验室提供的废钒钼系SCR脱硝催化剂，V2O5含量为1.4％，MoO3为 3.2％，TiO2为95％。
(1)取5g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃下干燥。干燥后的废催化剂加入NaOH作添加剂，NaOH与废催化剂中金属总量的摩尔比madd∶mmetal＝2。混合均匀后置于马弗炉中焙烧，焙烧温度为680℃，焙烧时间为5h；
(2)用中性的纯水作浸出剂，从步骤(1)焙烧后废催化剂中浸出V和Mo，液固比为0.06L/g，浸出温度为60℃，浸出压力为0.1MPa，浸出时间为2h，搅拌速度为800r/min，V单级浸出率为79.6％，Mo为77.4％；浸出渣返回步骤(1)；
(3)以仲胺类萃取剂二辛胺和正辛烷组成的萃取体系为有机相，浓度为15％，在水相初始pH＝3，两相比O/A＝1，萃取温度为20℃，萃取时间为15min的条件下从步骤(2)浸出液中同步萃取V和Mo，V萃取率为99.6％，Mo萃取率为98.8％。然后用10％的氨水对萃取相中的V和Mo同步反萃得到钒钼混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝4，反萃温度为45℃，反萃时间为3h。调节钒钼混合铵盐溶液中的V和Mo的比例，然后经蒸发、结晶、洗涤和55℃下干燥得钒钼混合铵盐；
(4)以仲胺类萃取剂二辛胺和正辛烷组成的萃取体系为有机相，浓度为15％，在水相初始pH＝5，两相比O/A＝1，萃取温度为25℃，萃取时间为25min的条件下从步骤(2)浸出液中萃取分离V和Mo，V萃取率为99.5％，Mo萃取率为0.12％，得到富钒有机相和含钼萃余液。用15％的氨水对富钒有机相反萃得到偏钒酸铵沉淀，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝10，反萃温度为70℃，反萃时间为4h；
(5)步骤(3)得到的钒钼混合铵盐先溶解于0.15mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀2.5h。超声结束后， 将体系搅拌蒸干。将蒸干后获得的固体混合物放入105℃的电热鼓风干燥箱中干燥15h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为450℃，焙烧时间为6h。焙烧后产物即为颗粒状的1.1％V2O5-3.1％MO3/TiO2系SCR脱硝催化剂。
(6)步骤(4)得到的偏钒酸铵沉淀先用硝酸溶解，再调节溶液pH＝7.5，然后加入硝酸铵沉钒，得到的偏钒酸铵沉淀经洗涤、干燥和焙烧，得到五氧化二钒产品，纯度为99.6％；步骤(4)得到的含钼萃余液用硝酸调节pH＝1.2，然后经蒸发结晶、洗涤和干燥，得到钼酸产品，纯度为99.2％。
实施例3
某实验室提供的废钒钨系SCR脱硝催化剂，V2O5含量为1.5％，WO3为3.3％，TiO2为95％。
(1)取10g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃下干燥。干燥后的废催化剂加入Na2CO3作添加剂，Na2CO3与废催化剂中金属总量的摩尔比madd∶mmetal＝6。混合均匀后置于马弗炉中焙烧，焙烧温度为500℃，焙烧时间为7h；
(2)用中性的纯水作浸出剂，从步骤(1)焙烧后废催化剂中浸出V和W，液固比为0.05L/g，浸出温度为70℃，浸出压力为0.1MPa，浸出时间为1.5h，搅拌速度为1200r/min，V单级浸出率为79.6％，W为76.4％；浸出渣返回步骤(1)；
(3)以叔胺类萃取剂Alamine 336和煤油组成的萃取体系为有机相，浓度为25％，在水相初始pH＝4，两相比O/A＝1，萃取温度为40℃，萃取时间为40min的条件下从步骤(2)浸出液中同步萃取V和W，V萃取率为98.6％，W萃取率为99.6％。然后用20％的氨水对萃取相中的V和W同步反萃得到钒钨混合铵盐 溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝6，反萃温度为50℃，反萃时间为3h。调节钒钨混合铵盐溶液中的V和W的比例，然后经蒸发、结晶、洗涤和48℃下干燥得钒钨混合铵盐；
(4)以叔胺类萃取剂Alamine 336和煤油组成的萃取体系为有机相，浓度为25％，在水相初始pH＝1.0，两相比O/A＝1，萃取温度为25℃，萃取时间为20min的条件下从步骤(2)浸出液中萃取分离V和W，V萃取率为100％，W萃取率为0.2％，得到富钒有机相和含钨萃余液。用1g/L的NaOH溶液对富钒有机相反萃，其中加入的OH-与有机相中金属总量的摩尔比mOH-∶mmetal＝10，反萃温度为70℃，反萃时间为4h，得到钒酸钠溶液；
(5)步骤(3)得到的钒钨混合铵盐先溶解于0.16mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀3h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入106℃的电热鼓风干燥箱中干燥16h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为500℃，焙烧时间为5.5h。焙烧后产物即为颗粒状的1.2％V2O5-3.0％WO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的钒酸钠溶液调节pH＝8，加入硫酸铵沉淀，得到的偏钒酸铵沉淀经洗涤、干燥和焙烧，得到五氧化二钒产品，纯度为99.5％；步骤(4)得到的含钨萃余液用硝酸调节pH＝1.0，然后经蒸发结晶、洗涤和干燥，得到钨酸产品，纯度为99.0％。
实施例4
某实验室提供的废钒钨系SCR脱硝催化剂，V2O5含量为1.3％，WO3为3.2％，TiO2为95.2％。
(1)取10g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃ 下干燥。干燥后的废催化剂加入NaCl作添加剂，NaCl与废催化剂中金属总量的摩尔比madd∶mmetal＝4.5。混合均匀后置于马弗炉中焙烧，焙烧温度为700℃，焙烧时间为4h；
(2)用中性的纯水作浸出剂，从步骤(1)焙烧后废催化剂中浸出V和W，液固比为0.1L/g，浸出温度为80℃，浸出压力为0.2MPa，浸出时间为3h，搅拌速度为5000r/min，V单级浸出率为78.8％，W为75.9％；浸出渣返回步骤(1)；
(3)以季胺盐Aliquat 336和煤油组成的萃取体系为有机相，浓度为25％，在水相初始pH＝3，两相比O/A＝1，萃取温度为30℃，萃取时间为30min的条件下从步骤(2)浸出液中同步萃取V和W，V萃取率为98.7％，W萃取率为98.90％。然后用20％的氨水对萃取相中的V和W同步反萃得到钒钨混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝5，反萃温度为45℃，反萃时间为3h。调节钒钨混合铵盐溶液中的V和W的比例，然后经蒸发、结晶、洗涤和45℃下干燥得钒钨混合铵盐；
(4)以季胺盐Aliquat 336和煤油组成的萃取体系为有机相，浓度为25％，在水相初始pH＝9.0，两相比O/A＝1，萃取温度为40℃，萃取时间为40min的条件下从步骤(2)浸出液中萃取分离V和W，V萃取率为0.2％，W萃取率为99.6％，得到富钨有机相和含钒萃余液。用10g/L的NaOH溶液对富钨有机相反萃，其中加入的OH-与有机相中金属总量的摩尔比mOH-∶mmetal＝5，反萃温度为30℃，反萃时间为0.5h，得到钨酸钠溶液；
(5)步骤(3)得到的钒钨混合铵盐先溶解于0.2mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀4h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥18h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙 烧温度为550℃，焙烧时间为7h。焙烧后产物即为颗粒状的1.3％V2O5-3.4％WO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的钨酸钠溶液用硝酸调节pH＝1.5，然后经蒸发结晶、洗涤、干燥和煅烧，得到三氧化钨产品，纯度为99.2％；步骤(4)得到的含钒萃余液调节pH＝7.2，然后加入氯化铵沉钒，得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.6％。
实施例5
某实验室提供的废钒钨系SCR脱硝催化剂，V2O5含量为1.3％，WO3为2.4％，TiO2为96.1％。
(1)取5g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在110℃下干燥。干燥后的废催化剂加入Na2SO4作添加剂，Na2SO4与废催化剂中金属总量的摩尔比madd∶mmetal＝5.5。混合均匀后置于马弗炉中焙烧，焙烧温度为800℃，焙烧时间为5h；
(2)用1g/LNaOH溶液作浸出剂，从步骤(1)焙烧后废催化剂中浸出V和W，液固比为0.2L/g，浸出温度为100℃，浸出压力为0.2MPa，浸出时间为4h，搅拌速度为2000r/min，V单级浸出率为81.7％，W为77.2％；浸出渣返回步骤(1)；
(3)以中性膦类萃取剂TBP和煤油组成的萃取体系为有机相，浓度为30％，在水相初始pH＝6，两相比O/A＝1，萃取温度为30℃，萃取时间为35min的条件下从浸出液中同步萃取V和W，V萃取率为99.0％，W萃取率为97.6％。然后用30％的氨水对萃取相中的V和W同步反萃得到钒钨混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝6，反萃温度为50℃，反萃时间为4h。调节钒钨混合铵盐溶液中的V和W的比例，然后经蒸发、结晶、 洗涤和50℃下干燥得钒钨混合铵盐；
(4)以中性膦类萃取剂TBP和煤油组成的萃取体系为有机相，浓度为30％，在水相初始pH＝2.5，两相比O/A＝1，萃取温度为30℃，萃取时间为35min的条件下从浸出液中萃取分离V和W，V萃取率为99.8％，W萃取率为0.3％，得到富钒有机相和含钨萃余液。富钒有机相用5g/LNaOH溶液反萃，其中加入的OH-与有机相中金属总量的摩尔比mOH-∶mmetal＝4.5，反萃温度为35℃，反萃时间为1h，得到钒酸钠溶液；
(5)步骤(3)得到的钒钨混合铵盐先溶解于0.2mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀3h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥24h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为600℃，焙烧时间为12h。焙烧后产物即为颗粒状的1.4％V2O5-3.0％WO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的钒酸钠溶液调节pH＝9，然后加入硝酸铵沉钒，得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.5％；含钨萃余液调节pH＝6.2，然后用萃取法再次提钨。中性膦类萃取剂TBP和煤油组成的萃取体系为有机相，浓度为15％，两相比O/A＝1，萃取温度为30℃，萃取时间为30min，W萃取率为99.5％。富钨有机相用30％氨水反萃，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝5，反萃温度为35℃，反萃时间为2h，得到的钨酸铵溶液经蒸发结晶、洗涤和干燥，得到仲钨酸铵产品，纯度为99.3％。
实施例6
某实验室提供的废钒钨钼系SCR脱硝催化剂，V2O5含量为1.3％，WO3为 1.4％，MoO3为1.4％，TiO2为95.7％。
(1)取5g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃下干燥。干燥后的废催化剂加入NaNO3作添加剂，NaNO3与废催化剂中金属总量的摩尔比madd∶mmetal＝6。混合均匀后置于马弗炉中焙烧，焙烧温度为900℃，焙烧时间为7h；
(2)用1g/LNaOH溶液作浸出剂，从步骤(1)焙烧后废催化剂中浸出V、W和Mo，液固比为0.3L/g，浸出温度为100℃，浸出压力为0.4MPa，浸出时间为5h，搅拌速度为3000r/min，V单级浸出率为81.7％，W为77.2％；浸出渣返回步骤(1)；
(3)以有机酯类醋酸戊酯和煤油组成的萃取体系为有机相，浓度为25％，在水相初始pH＝10，两相比O/A＝1，萃取温度为40℃，萃取时间为40min的条件下从步骤(2)浸出液中同步萃取V、W和Mo，V萃取率为99.6％，W萃取率为98.6％，Mo萃取率为97.8％。然后用15％的氨水对萃取相中的V、W和Mo同步反萃得到钒钨钼混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝5，反萃温度为45℃，反萃时间为2h。调节钒钨钼混合铵盐溶液中的V、W和Mo的比例，然后经蒸发、结晶、洗涤和45℃下干燥得钒钨钼混合铵盐；
(4)以有机酯类醋酸戊酯和煤油组成的萃取体系为有机相，浓度为25％，在水相初始pH＝3.2，两相比O/A＝1，萃取温度为40℃，萃取时间为40min的条件下从步骤(2)浸出液中萃取分离V、W和Mo，V萃取率为100％，W和Mo萃取率低于0.2％，得到富钒有机相和含钨钼萃余液。用15％的氨水对富钒有机相反萃，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝4，反萃温度为40℃，反萃时间为2.5h，得到偏钒酸铵沉淀；
(5)步骤(3)得到的钒钨钼混合铵盐先溶解于0.2mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀4h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥24h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为600℃，焙烧时间为10h。焙烧后产物即为颗粒状的1.4％V2O5-1.2％WO3-1.2％MoO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.3％；步骤(4)得到的含钨钼萃余液调节pH＝2，然后经蒸发结晶、洗涤、干燥和煅烧，得到三氧化钼和三氧化钨混合物产品，纯度为99.0％。
实施例7
某实验室提供的废钒钼系SCR脱硝催化剂，V2O5含量为1.2％，MoO3为2.5％，TiO2为96％。
(1)取5g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃下干燥；
(2)用2g/LNaOH溶液作浸出剂，从步骤(1)干燥后废催化剂中浸出V和Mo，液固比为0.5L/g，浸出温度为200℃，浸出压力为1MPa，浸出时间为5h，搅拌速度为5000r/min，V单级浸出率为84.1％，Mo为80.1％；浸出渣返回步骤(1)；
(3)以有机膦类D2EHPA和煤油组成的萃取体系为有机相，浓度为15％，在水相初始pH＝8.5，两相比O/A＝1，萃取温度为30℃，萃取时间为30min的条件下从步骤(2)浸出液中同步萃取V和Mo，V萃取率为99.8％，Mo萃取率为98.9％。然后用20％的氨水对萃取相中的V和Mo同步反萃得到钒钼混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝6，反萃温 度为30℃，反萃时间为2.5h。调节钒钼混合铵盐溶液中的V和Mo的比例，然后经蒸发、结晶、洗涤和40℃下干燥得钒钼混合铵盐；
(4)以有机膦类D2EHPA和煤油组成的萃取体系为有机相，浓度为15％，在水相初始pH＝2，两相比O/A＝1，萃取温度为30℃，萃取时间为30min的条件下从步骤(2)浸出液中萃取分离V和Mo，V萃取率为0.1％，Mo萃取率为99.9％，得到富钼有机相和含钒萃余液。用1g/L的NaOH溶液对富钼有机相反萃，其中加入的OH-与有机相中金属总量的摩尔比mOH-∶mmetal＝5，反萃温度为30℃，反萃时间为0.5h，得到钼酸钠溶液；
(5)步骤(3)得到的钒钼混合铵盐先溶解于0.1mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀4h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥24h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为600℃，焙烧时间为9h。焙烧后产物即为颗粒状的1.5％V2O5-2.6％MO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的钼酸钠溶液经蒸发结晶、洗涤和干燥，得到钼酸钠产品，纯度为99.5％；步骤(4)得到的含钒萃余液先调节pH＝8.5，然后加入硫酸铵沉钒，得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.6％。
实施例8
某实验室提供的废钒钼系SCR脱硝催化剂，V2O5含量为1.5％，MoO3为2.3％，TiO2为96.1％。
(1)取5g上述废催化剂，先粉粹至100目，水洗涤、过滤后，在105℃下干燥；
(2)用5g/LNaOH溶液作浸出剂，从步骤(1)干燥后废催化剂中浸出V和Mo，液固比为0.6L/g，浸出温度为150℃，浸出压力为0.5MPa，浸出时间为5h，搅拌速度为5000r/min，V单级浸出率为80.1％，Mo为81.1％；浸出渣返回步骤(1)；
(3)以肟类萃取剂Lix63和煤油组成的萃取体系为有机相，浓度为30％，在水相初始pH＝6，两相比O/A＝1，萃取温度为40℃，萃取时间为40min的条件下从步骤(2)浸出液中同步萃取V和Mo，V萃取率为98.7％，Mo萃取率为98.9％。然后用20％的氨水对萃取相中的V和Mo同步反萃得到钒钼混合铵盐溶液，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝5，反萃温度为20℃，反萃时间为3h。调节钒钼混合铵盐溶液中的V和Mo的比例，然后经蒸发、结晶、洗涤和40℃下干燥得钒钼混合铵盐；
(4)以肟类萃取剂Lix63和煤油组成的萃取体系为有机相，浓度为30％，在水相初始pH＝2，两相比O/A＝1，萃取温度为40℃，萃取时间为40min的条件下从浸出液中萃取分离V和Mo，V萃取率为99.7％，Mo萃取率为0.4％，得到富钒有机相和含钼萃余液。用15％氨水反萃富钒有机相，其中加入的铵离子与有机相中金属总量的摩尔比mNH4 +∶mmetal＝5，反萃温度为45℃，反萃时间为2.5h得到偏钒酸铵沉淀；
(5)步骤(3)得到的钒钼混合铵盐先溶解于0.1mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀4h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥24h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为600℃，焙烧时间为9h。焙烧后产物即为颗粒状的1.4％V2O5-2.2％MO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.7％；步骤(4)得到的含钼萃余液调节pH＝1，然后经蒸发结晶、洗涤、干燥和煅烧，得到三氧化钼产品，纯度为99.4％。
实施例9
某实验室提供的废钒钨系SCR催化剂，V2O5含量为1.2％，WO3为3.3％，TiO2为95.3％。
(1)取50g上述废催化剂，先粉粹至100目，再用水洗涤、过滤和105℃干燥；
(2)用2g/L的氢氧化钠溶液作浸出剂，从步骤(1)干燥后的废催化剂中浸出V和W，液固比为1L/g，浸出温度为200℃，浸出压力为1MPa，浸出时间为5h，搅拌速度为100r/min，V单级浸出率为77.2％，W为75.6％；浸出渣进行二次浸出；
(3)步骤(2)得到的浸出液用硝酸调节pH＝6，然后加入硝酸钙共沉淀，硝酸钙与浸出液中金属总量的摩尔比mpre∶mmetal＝1，反应温度为10℃，沉淀时间为10min，可得钒酸钙和钨酸钙混合沉淀。将混合沉淀用硝酸溶解，调节溶液pH＝6后，再加入硝酸钙共沉淀，得到的沉淀经洗涤、干燥即为纯钒钨混合钙盐。钒钨混合钙盐用硝酸溶解并调节溶液pH＝1.5，然后调节溶液中V和W的比例。钒钨溶液经蒸发、结晶、洗涤和105℃下干燥后，进一步在600℃下焙烧，得钒钨混合氧化物；
(4)步骤(2)得到的浸出液用沉淀法分离V和W。调节浸出液pH＝5，然后加入硫酸铵沉钒，硫酸铵与浸出液中金属钒的摩尔比mpre∶mmetal＝1，沉淀温度为20℃，沉淀时间为20min，过滤得偏钒酸铵沉淀和含钨溶液；
(5)步骤(3)得到的钒钨混合氧化物用混合法制备钒钨系SCR催化剂粉 体。先将钒钨混合氧化物粉碎至100目，然后与TiO2按照一定的比例进行湿法球磨混合5h。混合结束后，一起置于110℃的烘箱中干燥12h。干燥后的产物即为1.3％V2O5-3.2％WO3/TiO2系SCR催化剂粉体。取50g磨碎至0.1mm的催化剂粉体，然后加入粘合剂聚丙烯酰胺4.5g和粒径为0.1mm的活性炭粉体2.5g后干混15min。混合均匀后，依次加入10mL水和助挤剂乙醇胺4mL，然后用擀棒对湿物料进行捏合操作，得到塑性膏体。将塑性膏体装入蜂窝状催化剂模具上部，使用压板将塑性膏体强行压入下部的定型杆之间。将含有催化剂膏体的模具在65℃烘箱中加热，待预先涂在定型杆和模具表面上的石蜡融化后，将模具取出得到半干的催化剂胚体。催化剂胚体先于105℃烘箱中干燥12h，再于450℃下焙烧12h，即得蜂窝状1.3％V2O5-3.3％WO3/TiO2系SCR脱硝催化剂；
(6)步骤(4)得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.1％；步骤(4)得到的含钨溶液调节pH＝8，然后加入硝酸钙沉淀，硝酸钙与浸出液中金属钨的摩尔比mpre∶mmetal＝6，反应温度为50℃，沉淀时间为50min，可得钨酸钙沉淀。钨酸钙沉淀经洗涤和干燥得到钨酸钙产品，纯度为99.3％。
实施例10
某实验室提供的废钒钨系SCR催化剂，V2O5含量为1.1％，MO3为2.5％，TiO2为96.2％。
(1)取50g上述废催化剂，先粉粹至100目，再用水洗涤、过滤和干燥。干燥后的废催化剂加入NaNO3作添加剂，NaNO3与废催化剂中金属总量的摩尔比madd∶mmetal＝4.5。混合均匀后置于马弗炉中焙烧，焙烧温度为700℃，焙烧时间为6h；
(2)用2g/L的氢氧化钠溶液作浸出剂，从步骤(1)焙烧后的废催化剂中 浸出V和Mo，液固比为0.2L/g，浸出温度为120℃，浸出压力为0.5MPa，浸出时间为5h，搅拌速度为1000r/min，V单级浸出率为74.9％，Mo为72.7％；浸出渣进行二次浸出；
(3)步骤(2)中所述的浸出液调节pH＝12，然后加入氯化钙共沉淀，氯化钙与浸出液中金属总量的摩尔比mpre∶mmetal＝5，反应温度为90℃，沉淀时间为120min，可得钒酸钙和钼酸钙混合沉淀。将混合沉淀用硝酸溶解，调节溶液pH＝12后，再加入氯化钙共沉淀，得到的沉淀经洗涤、干燥即为纯钒钼混合钙盐。钒钼混合钙盐用硝酸溶解并调节溶液pH＝1.5，然后调节溶液中V和Mo的比例。钒钼溶液经蒸发、结晶、洗涤和105℃下干燥，进一步在650℃下焙烧，得钒钼混合氧化物；
(4)步骤(2)中所述的浸出液用沉淀法分离V和Mo。调节浸出液pH＝11，然后加入氯化铵沉钒，氯化铵与浸出液中金属钒的摩尔比mpre∶mmetal＝6，沉淀温度为80℃，沉淀时间为120min，过滤得偏钒酸铵沉淀和含钼溶液；
(5)步骤(3)得到的钒钼混合氧化物先溶解于0.1mol/L的草酸溶液中，然后按比例加入TiO2。将体系置入超声波清洁器中超声混匀4h。超声结束后，将体系搅拌蒸干。将蒸干后获得的固体混合物放入110℃的电热鼓风干燥箱中干燥24h。将干燥后的固体混合物磨成粉末，然后放入坩埚中置入马弗炉中焙烧，焙烧温度为600℃，焙烧时间为9h。焙烧产物即为1.2％V2O5-2.5％MO3/TiO2系SCR催化剂粉体。取50g磨碎至0.1mm的催化剂粉体，然后加入粘合剂聚丙烯酰胺5g和粒径为0.1mm的活性炭粉体2.5g后干混20min。混合均匀后，依次加入8mL水和助挤剂乙醇胺3.5mL，然后用擀棒对湿物料进行捏合操作，得到塑性膏体。将塑性膏体装入蜂窝状催化剂模具上部，使用压板将塑性膏体强行压入下部的定型杆之间。将含有催化剂膏体的模具在60℃烘箱中加热，待预先涂 在定型杆和模具表面上的石蜡融化后，将模具取出得到半干的催化剂胚体。催化剂胚体先于110℃烘箱中干燥24h，再于450℃下焙烧12h，即得蜂窝状1.3％V2O5-2.4％WO3/TiO2系SCR脱硝催化剂。
(6)步骤(4)得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到五氧化二钒产品，纯度为99.5％；步骤(4)得到的含钼溶液调节pH＝10，然后加入氯化钙沉淀，硝酸钙与浸出液中金属钼的摩尔比mpre∶mmetal＝6，反应温度为50℃，沉淀时间为120min，可得钼酸钙沉淀。钼酸钙沉淀经洗涤和干燥得到钼酸钙产品，纯度为99.6％。
实施例11
某实验室提供的废钒钼系SCR催化剂，V2O5含量为1.1％，MO3为2.0％，TiO2为96.7％。
(1)取50g上述废催化剂，先粉粹至100目，用水洗涤、过滤后，于105℃下干燥。干燥后的废催化剂加入NaCl作添加剂，NaCl与废催化剂中金属总量的摩尔比madd∶mmetal＝6。混合均匀后置于马弗炉中焙烧，焙烧温度为900℃，焙烧时间为7h；
(2)用1g/L的硫酸溶液作浸出剂，从步骤(1)焙烧后的废催化剂中浸出V和Mo，液固比为1L/g，浸出温度为100℃，浸出压力为0.2MPa，浸出时间为0.5h，搅拌速度为5000r/min，V单级浸出率为96.2％，Mo为95.2％，Ti为86.1％；浸出渣返回步骤(1)；
(3)步骤(2)中得到的浸出液中的V、Mo和Ti用弱碱性阴离子交换树脂D418同步提取。浸出液体积为树脂体积的10倍，溶液pH＝1，温度为10℃，交换反应时间为30min，V提取率为94.3％，Mo为95.8％，Ti为96.2％，母液进行二次提取。用15％的氨水对树脂洗涤再生，再生时间为20min，再生温度为 20℃，得钒钼钛混合铵盐溶液；
(4)步骤(2)中所述的浸出液先调节pH＝9，过滤得钛酸钠沉淀和钒钼溶液。钒钼溶液用弱碱性阴离子交换树脂D418分离，浸出液体积为树脂体积的10倍，溶液pH＝2，温度为20℃，交换反应时间为30min，V提取率为99.3％，Mo为0.2％，得到负钒树脂和含钼余液。用2g/L的Na2CO3溶液对树脂洗涤再生，再生时间为20min，再生温度为25℃，得钒酸钠溶液；
(5)步骤(3)得到的钒钼钛混合铵盐溶液用沉淀法制备钒钼系SCR脱硝催化剂粉体。先将钒钼钛混合铵盐溶液调节pH＝7.5，然后加入硝酸钙，过滤得到钒钼钛混合沉淀。混合沉淀先用硝酸溶解，并继续酸化至pH＝1.1，然后经蒸发结晶、洗涤、105℃干燥和750℃焙烧，得到1.2％V2O5-2.0％MoO3/TiO2系SCR催化剂粉体。取50g磨碎至0.1mm的催化剂粉体，然后加入粘合剂甲基纤维素5.5g和粒径为0.1mm的活性炭粉体3.5g后干混18min。混合均匀后，依次加入8mL水、助挤剂乙醇胺4mL和润滑油甘油2.5mL，然后用擀棒对湿物料进行捏合操作，得到塑性膏体。以55*100mm的带有筛孔的不锈钢平板为担体，筛板厚度为0.5mm，孔径1mm、孔间距为1.5mm，正三角形排列，筛板上下两侧均匀压制0.5mm厚的塑性膏体。将带有塑性膏体的筛板于105℃下干燥12h，然后再于500℃下锻烧24h后，得到厚度为1.5mm催化剂单板，将其在不锈钢壳体中组装得到板式催化剂；
(6)步骤(4)得到的钒酸钠溶液调节pH＝8，加入硫酸铵沉钒，得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到的五氧化二钒产品，纯度为99.5％；步骤(4)得到的含钼余液调节pH＝1.2，然后经蒸发结晶、洗涤和干燥，得到钼酸产品，纯度为99.0％。
实施例12
某实验室提供的废钒钨系SCR催化剂，V2O5含量为1.3％，WO3为2.4％，TiO2为96.1％。
(1)取50g上述废催化剂，先粉粹至100目，用水洗涤、过滤后，于105℃下干燥；
(2)用1g/LNaOH溶液作浸出剂，从步骤(1)中浸出V和W，液固比为0.7L/g，浸出温度为150℃，浸出压力为0.5MPa，浸出时间为2h，搅拌速度为4000r/min，V单级浸出率为87.2％，W为86.3％，Ti为84.3％；浸出渣返回步骤(1)；
(3)步骤(2)中得到的浸出液中的V和W用强碱性阴离子交换树脂D201同步提取。浸出液体积为树脂体积的100倍，溶液pH＝12，温度为100℃，交换反应时间为120min，V提取率为99.1％，W为98.9％，母液进行二次提取。用2g/LNaOH溶液对树脂洗涤再生，再生时间为120min，再生温度为100℃，得钒钨混合钠盐溶液；
(4)步骤(2)中所述的浸出液中的V和W用强碱性阴离子交换树脂D201分离。浸出液体积为树脂体积的100倍，溶液pH＝11，温度为90℃，交换反应时间为100min，V提取率为99.1％，W为0.1％，得到负钒树脂和含钨余液。用5g/L的NaOH溶液对树脂洗涤再生，再生时间为120min，再生温度为90℃，得钒酸钠溶液；
(5)步骤(3)得到的钒钨混合钠盐溶液先调节V和W的比例，然后调节pH＝3，再按比例溶入Na2TiO3，得到的钒钨钛混合溶液用沉淀法制备钒钨系SCR脱硝催化剂粉体。先将钒钨钛混合溶液调节pH＝8，然后加入硝酸钙，过滤得到钒钨钛混合沉淀。混合沉淀先用硝酸溶解，并继续酸化至pH＝1.5，然后经蒸发结晶、洗涤、105℃干燥和700℃焙烧，得到1.2％V2O5-2.3％WO3/TiO2系SCR催 化剂粉体。取50g磨碎至0.1mm的催化剂粉体，然后加入粘合剂甲基纤维素5g和粒径为0.1mm的活性炭粉体3g后干混20min。混合均匀后，依次加入10mL水、助挤剂乙醇胺5mL和润滑油甘油2mL，然后用擀棒对湿物料进行捏合操作，得到塑性膏体。以50*100mm的波纹纤维板为担体，纤维板厚度为0.5mm，纤维板上下两侧均匀涂制0.5mm厚的塑性膏体。将带有塑性膏体的筛板于105℃下干燥24h，然后再于450℃下锻烧20h后，得到1.3％V2O5-2.2％WO3/TiO2系波纹板式催化剂；
(6)步骤(4)得到的钒酸钠溶液调节pH＝9，加入硝酸铵沉钒，得到的偏钒酸铵沉淀经洗涤、干燥和煅烧，得到的五氧化二钒产品，纯度为99.7％；步骤(4)得到的含钨余液调节pH＝1.5，然后经蒸发结晶、洗涤和干燥，得到钨酸产品，纯度为99.5％。
最后应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求的保护范围当中。

Claims (10)

  1. 一种废SCR脱硝催化剂的回收处理方法，其特征在于，包括如下步骤：
    (1)将废SCR脱硝催化剂预处理，去除杂质、活化钒钨钼等催化组分；
    (2)对步骤(1)预处理后得到的废SCR脱硝催化剂进行浸出，得到浸出渣和浸出液；
    (3)对步骤(2)得到的浸出液中各个有价元素进行分离，得到钒提纯物和钨/钼/钨钼富集物；
    (4)将步骤(3)得到的钒提纯物进一步纯化，用于制备钒产品；得到的钨/钼/钨钼富集物进一步纯化，用于制备钨/钼/钨钼产品。
  2. 如权利要求1所述的方法，其特征在于，(5)将步骤(2)得到的浸出液中有价元素进行同步纯化，调节各个物质含量的比例，从而得到催化组分混合物，用于进一步制备为新的SCR脱硝催化剂。
  3. 如权利要求1或2所述的方法，其特征在于，步骤(2)浸出中的浸出剂为中性或酸性或碱性溶液，浸出剂与废催化剂的液固比为0.02～1L/g，浸出温度为20～200℃，浸出压力为0.1～1MPa，浸出时间为0.5～5h，搅拌速度为100～5000r/min；
    优选地，浸出剂为中性或碱性溶液。
  4. 如权利要求1所述的方法，其特征在于，步骤(3)所述的浸出液中各个有价元素用萃取法分离时，萃取剂为胺类、有机膦酸类、有机酯类、中性膦类、季铵盐类和肟类，萃取剂浓度为5％～30％，水相初始pH＝1～9，萃取温度为10～40℃，萃取时间为10～40min。
  5. 如权利要求1所述的方法，其特征在于，步骤(3)所述的浸出液中各个有价元素用离子交换法分离时，树脂种类为强碱性或弱碱性阴离子交换树脂，浸出液体积为树脂体积的10～100倍，溶液pH为2～11，温度为20～90℃、交 换时间为30～100min，树脂再生液为强碱性或弱碱性溶液，再生时间为20～120min，再生温度为25～90℃。
  6. 如权利要求1所述的方法，其特征在于，步骤(3)所述的浸出液中的各个有价元素用沉淀法分离时，沉淀剂与浸出液中金属总量的摩尔比mpre∶mmetal＝1～6，溶液pH＝5～11，沉淀温度为20～80℃，沉淀时间为20～120min。
  7. 如权利要求2所述的方法，其特征在于，步骤(3)所述的浸出液中有价元素用萃取法同步纯化时，萃取剂为胺类、有机膦酸类、有机酯类、中性膦类、季铵盐类或肟类萃取剂，萃取剂浓度为5％～30％，水相初始pH＝1～10，萃取温度为10～40℃，萃取时间为10～40min。
  8. 如权利要求2所述的方法，其特征在于，步骤(3)所述的浸出液中的有价元素用离子交换法同步纯化时，树脂种类为强碱性或弱碱性阴离子交换树脂，浸出液体积为树脂体积的10～100倍，溶液pH为1～12，温度为10～100℃、交换时间为30～120min，树脂再生液为强碱性或弱碱性溶液，再生时间为20～120min，再生温度为20～100℃。
  9. 如权利要求2所述的方法，其特征在于，步骤(3)所述的浸出液中的有价元素用共沉淀法同步纯化时，沉淀剂与浸出液中金属总量的摩尔比mpre∶mmetal＝1～5，溶液pH＝6～12，沉淀温度为10～90℃，沉淀时间为10～120min。
  10. 如权利要求2、7、8或9中任一所述的方法，其特征在于，步骤(4)所述的催化组分混合物制备新的SCR催化剂的方法为浸渍法、混合法和沉淀法，新的SCR催化剂为颗粒状、板式、蜂窝状和波纹板式；
    优选地，催化组分混合物制备新的SCR催化剂的方法为浸渍法，新的SCR催化剂为颗粒状。
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