CN104805298B - A kind of recovery and treatment method of useless SCR denitration - Google Patents

Abstract

The present invention relates to a kind of recovery and treatment method of useless SCR denitration, methods described is first pre-processed useless SCR denitration, and after removing the catalyst components such as the removal of impurity, activation vanadium tungsten, the leachate of rich titanium leached mud and the vanadium containing tungsten is obtained after leaching；Valuable element can carry out recycling treatment by two methods in leachate：The first is the proportion adjustment to carrying out each content of material after valuable component Isolation in leachate, prepares the mixture of catalyst component, and is further prepared as new catalyst, and realization remanufactures；Second is that each valuable element in leachate is separated, purified, and prepares different products.The present invention can recycle to the valuable element in SCR denitration of giving up, environmental benefit, remarkable in economical benefits.

Description

A kind of recovery and treatment method of useless SCR denitration

Technical field

The invention belongs to field for the treatment of of solid waste, more particularly to a kind of recovery and treatment method of useless SCR denitration.

Background technology

China is coal resources consumption big country, and the burning of coal can produce again while being offered convenience for resident living Substantial amounts of nitrogen oxides（NO_x）And oxysulfide（SO₂）.These nitrogen oxides and oxysulfide are the main compositions of atmosphere pollution Part, air ambient is on the one hand seriously polluted, on the other hand can also form acid rain, the water resource to nature is brought huge hidden Suffer from.Selective catalytic reduction（Selective Catalytic Reduction, SCR）It is a kind of compared with can of rising in recent years Lean on and the simple denitration technology of technique, it is typically using ammonia as denitrfying agent, in the presence of SCR catalyst, by nitrogen oxides Catalysis is reduced to the nitrogen of pollution-free effect.SCR catalyst mainly has vanadium tungsten system, vanadium molybdenum system and vanadium tungsten system.Three is with V₂O₅ And TiO₂As catalytic activity main body, the difference is that vanadium W-Sn deposits are with WO₃As auxiliary agent, vanadium molybdenum system is with MoO₃As Auxiliary agent, and vanadium tungsten system is then with WO₃And MoO₃As common auxiliary agent.In SCR technology, catalyst Investment is core, and the activity of catalyst directly determines the efficiency of denitration.SCR denitration active meeting in use Decrease, therefore, it is necessary to using the catalyst after certain time to carry out regeneration activating.But some SCR catalyst warps Cross after activating use repeatedly, its original physical arrangement has been seriously damaged, it is difficult to regeneration treatment, these catalysis that can not be regenerated Agent is useless SCR catalyst.

Carry out within 2012《Coal steam-electric plant smoke denitration engineering legislation-selective catalytic reduction》In mention, The processing mode for SCR denitration of being given up to honeycomb fashion fills for crushing.But useless SCR catalyst is because containing V₂O₅、WO₃Or MoO₃ Deng toxic metals oxide, belong to hazardous solid waste, if by land-fill method disposal SCR dead catalyst, can not only occupy a large amount of Land resource, also can environmental pollution bring risk, will also cause financial burden to power plant and engineering company.In fact, honeybee The WO that the useless SCR catalyst of socket contains in itself₃、MoO₃、V₂O₅And TiO₂All it is valuable resource, if the side of separating-purifying can be taken Formula is reclaimed, and can not only produce new profit growth point, also can reach various materials in denitrating flue gas industrial chain formed it is closed circuit The good result of circulation.

Patent CN104192911A discloses a kind of method for reclaiming tungstic acid composition in waste and old SCR denitration. It is that waste and old SCR denitration is fully crushed into dry powder-shaped, molten under certain condition using particular solution after high-temperature roasting The tungstic acid composition in catalyst is solved, tungstic acid is efficiently separated with other compositions in catalyst, it is clear to collect upper strata tungstenic Liquid is simultaneously evaporated, and obtained solid is fully dried, after high-temperature roasting, completes the recovery to tungstic acid composition.

Patent CN104195342A discloses a kind of side for reclaiming vanadic anhydride composition in waste and old SCR denitration Method.Pentavalent vanadium in catalyst is first reduced to more readily soluble tetravalence vanadium by it using reducing agent in an acidic solution, then uses oxygen Tetravalence vanadium in acid solution is oxidized to pentavalent vanadium by agent again, by adjusting the pH value of solution, makes pentavalent under certain condition Vanadium is fully hydrolyzed and precipitated, and collects the vanadic anhydride that the fired processing of precipitation can obtain high-purity, purity of vanadium pentoxide For 98%.

Patent CN103130265A discloses a kind of method that titanium dioxide is reclaimed from waste and old SCR denitration.Its elder generation Dedusting is carried out to useless denitrating catalyst, crushes milling, titanyl sulfate concentrated solution will be obtained by then adding the concentrated sulfuric acid after its acidolysis, then It is diluted with water；Nonionic emulsifier is subsequently added into as flocculant, sulfosalt surfactant or polycarboxylate surface-active Agent is subsequently added into Water-soluble methyl silicone oil as flocculation aid；Plate and frame filter press is pumped into again and carries out press filtration, by filter vacuum concentration again It is heated to 90 DEG C -98 DEG C and keeps hydrolyzing filtrate in 5.5 hours；Then hydrolysate is cooled to 40 DEG C, and carrying out vacuum filter makes Metatitanic acid is deposited；Again with after sand leaching water and deionized water rinsing, add potassium carbonate or phosphoric acid obtains metatitanic acid filter cake；To filter Calcined after cake drying at 500-800 DEG C, then crush, levigate obtain finished titanium dioxide.

The method that patent CN104261415A discloses silica in a kind of discarded SCR catalyst of recovery completely.By powder Discarded SCR catalyst after broken soaks removal of impurities with the water of 3~4 times of volumes, after removal of impurities the excessive concentration of powder be 60~ 80wt% concentrated alkali solution leaches, using being filtrated to get solid meta-titanium perborate Na₂TiO₃, add sulfuric acid into filtrate, 70~90 DEG C Lower regulation pH to 11.5~12.5,0.5~1h is stood, filtering discards filter cake；Added again into filtrate sulfuric acid be adjusted to pH for 9~ 10 obtained filter cakes are silicic acid, and silicic acid filter cake is filtered, used in dilute sulfuric acid and 40~60 DEG C of 1~2h of heating stirring of nitration mixture of oxalic acid Deionized water washs filter cake, washes the acid ion contained by solid off, heated decomposition obtains high-purity silicon dioxide.

Patent CN104275178A discloses reclaiming and the regeneration SCR catalyst of a kind of discarded SCR denitration The method of carrier.By discarded SCR catalyst by crushing, sieve, wash, after pickling, then through wet pulverizing, grinding, urged Agent slurry.Slurry is mixed with metatitanic acid slurries again, obtains mixed serum.Mixed serum process is washed, filtered, is dehydrated, After adjusting pH, Bleached is added.Slurries after bleaching add water, adjust pH, addition ammonium paratungstate and white carbon, agitated, Filtering, dehydration, calcining, crushing, obtain the catalyst of reclaiming.

Patent CN104263946A, which is disclosed, reclaims tungsten, vanadium, the method for titanium in a kind of dead catalyst from SCR denitration.By SCR Being crushed after dead catalyst cleaning, screening, incorporation sodium carbonate is stirred, and mixed-powder is sintered at high temperature to obtain sintering feed, Leaching is added water, obtains the sodium salt mixed solution containing tungsten, vanadium；The selective extraction tungsten under conditions of solution ph is more than 12, It is stripped to obtain ammonium tungstate solution with ammonium salt solution；Raffinate after extraction tungsten extracts under conditions of being 10~11.5 in pH value Vanadium, it is stripped to obtain the sodium vanadate solution containing a small amount of tungsten with sodium hydroxide solution；Titanium, which stays in, obtains rich-titanium material in leached mud.

Patent CN104178636A discloses Ti in a kind of activation burning combination acidic leaching recovery SCR spent catalysts, V, Mo, Si method.Its processing step is：First the pretreatment of SCR spent catalysts, then high-temperature calcination are activated.Then it is right Calcined product acidic leaching, obtain white TiO₂Powder.After leachate is concentrated by evaporation, white precipitate H is obtained₂MoO₄.Leachate adds Ammoniacal liquor adjusts pH to 8.0 ~ 9.0, obtains NH₄VO₃Precipitation.Leachate ammonification water is adjusted into pH to 8.0 ~ 9.0 again, adds MgCl₂ Obtain MgSiO₃.Filtrate after filtering enters sewage recovering system.

Patent CN104326506A discloses a kind of method for being used to reclaim titanium dioxide in failure denitrating catalyst.It is wrapped Include following steps：(1) the out of stock catalyst that will fail be ground to it is powdered be placed in open-top receptacle, be added dropwise into open-top receptacle appropriate Distilled water prevents from tying bottom；(2) acidolysis, the concentrated sulfuric acid that mass fraction is 98% add open-top receptacle, make powder to open-top receptacle heating Dissolving, lasting stir is well mixed solid-liquid in heating process, stops heating when the solution in open-top receptacle is in brown color, It is cooled to≤30 DEG C and obtains titanium liquid；(3) neutralize, by 50%~80% active calcium content of mass fraction be 80% lime milk solution by It is added drop-wise in titanium liquid, is shaken up when being added dropwise, room temperature is cooled to behind control titanium liquid temperature degree≤70 DEG C, fully reaction；(4) condensed water Solution, the titanium liquid after neutralization is concentrated into 195-205g/l, adds crystal seed heating and hydrolyze, titanium is obtained after filtering, rinsing, drying calcining Salt.

Above-mentioned existing SCR denitration recycling technology can not realize the circulation of useless SCR denitration again Manufacture, while can not also realize efficiently separating and obtaining vanadium tungsten production of the purity more than 99% for the valuable elements such as V, W, Mo and Ti Product.So far, China does not have after all also without the recycling Engineering Projects of a set of ripe useless SCR catalyst Mature and feasible, the waste catalyst recovery treatment technology suitably promoted.

The content of the invention

The reality that recycling technology based on current useless SCR denitration lacks, the present invention propose that one kind both can be with Realize the side that useless SCR denitration remanufactures, and the valuable components such as vanadium tungsten can be separated and recovered and purified as needed again The rate of recovery of method, wherein valuable metal surpasses 95%, and the purity of vanadium/tungsten/vanadium molybdenum product is up to more than 99%.

To use following technical scheme up to this purpose, the present invention：

A kind of recovery and treatment method of useless SCR denitration, comprises the following steps：

（1）Useless SCR denitration is pre-processed, removes the catalyst components such as the removal of impurity, activation vanadium tungsten；

（2）To step（1）The useless SCR denitration obtained after pretreatment is leached, and obtains leached mud and leachate；

（3）To step（2）Each valuable element is separated in obtained leachate, obtains vanadium purification and tungsten/molybdenum/tungsten Molybdenum enriched substance；

（4）By step（3）Obtained vanadium purification is further purified, for preparing vanadium product；Obtained tungsten/molybdenum/tungsten Enriched substance is further purified, for preparing tungsten/molybdenum/tungsten product.

（5）By step（2）Valuable element synchronizes purifying in obtained leachate, adjusts the ratio of each content of material Example, so as to obtain catalyst component mixture, for being further prepared as new SCR denitration.

Step（1）It is the important step for removing the catalyst components such as impurity in useless SCR denitration, activation vanadium tungsten.SCR Denitrating catalyst can carry the impurity such as some dusts, sand grains and oil content during long-term use, and these impurity can influence subsequently The purity of product.V in other dead catalyst₂O₅、WO₃、MoO₃For indissoluble thing.Therefore, dead catalyst need to be pre-processed, Remove the catalyst component such as the impurity carried and activation vanadium tungsten.Step（1）Middle preprocess method can be washing, crush, roasting With dry etc..Washing and dust, sand grains and the oil content for drying removable dead catalyst carrying；The ratio of dead catalyst can be improved by crushing Surface area；Roasting can be by the V in dead catalyst₂O₅、WO₃、MoO₃Activation, is converted into VO soluble in water₄ ^3-、WO₄ ^2-、MoO₄ ^2-。 It need to add additive during calcination activation, additive can be alkali metal base or salt, to be cost-effective, preferably soda or sodium salt, example Such as it is NaOH or Na₂CO₃Deng.Additive and the mol ratio m of Metals from Spent Catalysts total amount_add：m_metal=1 ~ 6, such as 1.2, 1.4th, 1.6,1.8,2.3,3,3.8,4.8,5.3 and 5.8 etc..Sintering temperature be 500 ~ 900 DEG C, such as 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C and 850 DEG C etc..Roasting time is 1 ~ 7h, such as 1.5h, 2h, 3h, 4h, 5h and 6h etc..

Step（2）It is the main process from solid phase extractions vanadium tungsten.Leaching agent can be in neutral acid or alkaline, if leaching Agent is in acidity, then other metals such as Ti in dead catalyst in addition to V, W and Mo etc. can also enter solution, and this can make ammonium acetate It is more complicated, increase the separating difficulty of follow-up each component.Therefore, leaching agent is preferably neutral or alkaline in the present invention.Leaching agent Liquid-solid ratio with product of roasting is 0.02 ~ 1L/g, for example, 0.025 L/g, 0.05 L/g, 0.1L/g, 0.15 L/g, 0.2 L/ G, 0.25 L/g, 0.5 L/g, 0.75 L/g and 0.8 L/g etc..Extraction temperature be 20 ~ 200 DEG C, for example, 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C etc..Extraction time can be 0.5 ~ 5h, for example, 0.75h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h and 4.5h etc..Leaching pressure is 0.1~1MPa, for example, 0.2MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa and 1.0 MPa etc..Leaching mixing speed is 100~5000r/min, for example, 400 r/min, 800r/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, 4400 r/min and 4800 r/min etc..

Step（3）It is the core operation of each valuable element separation in leachate.Valuable element extraction in leachate When method is recorded separately, extractant can be amine, organic phosphine acids, organosilane ester, neutral phosphine, quaternary ammonium salt and oximes, for example, primary Amine N1923, Primene JMT, Primene 81R and LK-N21, secondary amine class DIDA, dioctylamine/normal octane, dioctylamine/tetra- Chlorination carbon, tertiary amines Alamine 336, quaternary amine Aliquat 336, neutral phosphine TBP, organosilane ester amyl acetate and organic Phosphorus D2EHPA, oximes Lix63；Extractant concentration is 5%~30%, for example, 10%, 15%, 20% and 25% etc.；The initial pH of aqueous phase =1~9, for example, 1.5,2,2.5,3,3.5,4,5,6,7 and 8 etc.；Extraction temperature be 10~40 DEG C, for example, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C and 35 DEG C etc.；Extraction time is 10~40min, for example, 15 min, 20 min, 25 min, 30 min and 35 Min etc.；When being stripped to organic phase, back washing agent can be alkali lye or ammoniacal liquor, the NH in back washing agent₄ ⁺Or OH^-With total metal content Mol ratio m_NH4+/m_OH ^-:m_metal=1~10, for example, 2,3,5,7 and 9 etc..Wherein concentration of lye is 1~10g/L, for example, 2 G/L, 4 g/L, 6 g/L, 8 g/L and 9 g/L；Ammonia concn is 5%~30%, for example, 10%, 15%, 20%, 25% and 28% etc.. It is 20~70 DEG C, for example, 30,40,50 and 60 DEG C to be stripped temperature；Stripping times are 0.5~4h, for example, 1,1.5,2,2.5,3 With 3.5 etc..

During each valuable element Strong acid ion-exchanger in leachate, resin types be strong basicity or alkalescent the moon from Sub-exchange resin, for example, D418, D301 etc.；Leachate volume is 10~100 times of resin volume, for example, 20,30,40, 50th, 60,70,80 and 90 etc.；PH value of solution is 2~11, for example, 2,4,6,8 and 9 etc.；Temperature be 20~90 DEG C, for example, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C and 80 DEG C etc.；Swap time is 30~100min, for example, 20 min, 40 min, 60 Min and 80 min etc.；Resin regeneration liquid is highly basic or weak caustic solution, for example, NaOH, Na₂CO₃With ammoniacal liquor etc.；Recovery time is 20~120min, for example, 30min, 50 min, 60 min, 70 min, 80 min, 90 min and 110 min etc.；Regeneration temperature For 25~90 DEG C, for example, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C and 80 DEG C etc.；

When each valuable element in leachate is separated with the precipitation method, precipitating reagent is alkali metal salt etc., for example, Ca (NO₃)₂、CaCl₂、Mg(NO₃)₂、MgCl₂、BaCl₂With Ba (NO₃)₂Deng；The mol ratio of precipitating reagent and total metal content in leachate m_pre：m_metal=1~6, for example, 1.5,2,2.5,3,3.5,4,4.5 and 5 etc.；PH value of solution=5~11, for example, 6,7,8,9 and 10 Deng；Precipitation temperature is 20~80 DEG C, for example, 20,30,40,50,60 and 70 DEG C；Sedimentation time is 20~120min, is, for example, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min and 110 min etc.；

Step（4）It is that vanadium purification and tungsten/molybdenum/tungsten enriched substance are further purified, prepare vanadium and tungsten/molybdenum/tungsten respectively The important step of product.The method that vanadium purification is further purified is precipitation, extraction, ion exchange and UF membrane etc..Metavanadic acid Ammonium precipitation can obtain vanadic anhydride product of the purity more than 99.5% through dissolving, reprecipitation, washing, drying and roasting.Containing vanadium solution High purity vanadic anhydride product can also be made with extracting-back extraction precipitation-drying-roasting technique.The pure vanadium liquid of low concentration utilizes electricity Osmotic technique can be concentrated.Also ion-exchange vanadium extraction from the vanadium solution of low concentration can be used, then through resin regenerated from washing, Vanadic salts product can be made in evaporative crystallization and drying.The method that tungsten/molybdenum/tungsten enriched substance is further purified is precipitation, extracted, ion Exchange and UF membrane etc..Sodium molybdate solution is first extracted with amine extractant, then can obtain ammonium molybdate solution, Ran Houjing with ammoniacal liquor back extraction It is concentrated by evaporation, washs, drying and roasting can obtains molybdenum trioxide product.Wolframic acid calcium precipitate can be made through dissolving, reprecipitation and drying Pure tungsten acid calcium product.Ammonium molybdate solution containing a small amount of vanadium can remove vanadium through NF membrane and ion exchange, obtain pure ammonium molybdate solution. Pure sodium molybdate solution is acidified, evaporation and drying can prepare molybdic acid product of the purity more than 99.1%.

Step（5）It is the committed step of vanadium tungsten Isolation in leachate.The side of valuable group of Isolation in leachate Method can be co-precipitation, extraction and ion exchange etc..When valuable element in leachate is with extraction Isolation, extractant can For amine, organophosphor acids, organosilane ester, neutral phosphine, quaternary ammonium salt and oximes, for example, primary amine class N1923, Primene JMT, Primene 81R and LK-N21, secondary amine class DIDA, dioctylamine/normal octane, dioctylamine/carbon tetrachloride, tertiary amines Alamine 336, quaternary amine Aliquat 336, neutral phosphine TBP, organosilane ester amyl acetate and organic phosphates D2EHPA, oxime Class Lix63；Extractant concentration is 5%~30%, for example, 10%, 15%, 20% and 25% etc.；Initial pH=1~10 of aqueous phase, it is, for example, 1.5th, 2,2.5,3,3.5,4,5,6,7,8 and 9 etc.；Extraction temperature is 10~40 DEG C, for example, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C With 35 DEG C etc.；Extraction time is 10~40min, for example, 15 min, 20 min, 25 min, 30 min and 35 min etc.；To having When machine is mutually stripped, back washing agent can be alkali lye or ammoniacal liquor, the NH in back washing agent₄ ⁺Or OH^-With the mol ratio m of total metal content_NH4+/ m_OH ^-:m_metal=1~10, for example, 2,3,5,7 and 9 etc..Wherein concentration of lye is 1~10g/L, for example, 2 g/L, 4 g/L, 6 G/L, 8 g/L and 9 g/L；Ammonia concn is 5%~30%, for example, 10%, 15%, 20%, 25% and 28% etc..It is 20 to be stripped temperature ~70 DEG C, for example, 30,40,50 and 60 DEG C；Stripping times are 0.5~4h, for example, 1,1.5,2,2.5,3 and 3.5 etc..

When valuable element in leachate is with ion-exchange Isolation, resin types be strong basicity or alkalescent the moon from Sub-exchange resin, for example, D418, D301 etc.；Leachate volume is 10~100 times of resin volume, for example, 20,30,40, 50th, 60,70,80 and 90 etc.；PH value of solution is 1~12, for example, 2,4,6,8 and 10 etc.；Temperature be 10~100 DEG C, for example, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C and 90 DEG C etc.；Swap time is 30~120min, for example, 20 min, 40 Min, 60 min, 80 min and 100 min etc.；Resin regeneration liquid is highly basic or weak caustic solution, for example, NaOH, Na₂CO₃And ammonia Water etc.；Recovery time is 20~120min, for example, 30min, 50 min, 60 min, 70 min, 80 min, 90 min and 110 Min etc.；Regeneration temperature is 20~100 DEG C, for example, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C and 90 DEG C etc..

When valuable element in leachate is with coprecipitation Isolation, precipitating reagent is alkali metal salt etc., for example, Ca (NO₃)₂、CaCl₂、Mg(NO₃)₂、MgCl₂、BaCl₂With Ba (NO₃)₂Deng；Precipitating reagent with

Step（5）And catalyst component mixture prepares the core procedure of new SCR denitration.SCR denitration Graininess and integral catalyzer can be divided into according to outward appearance, wherein integral catalyzer is divided into board-like, cellular and corrugated plating again Catalyst.Pellet type catalyst is to use impregnation technology by TiO mostly₂Forerunner of the powder in ammonium metavanadate He other co-catalysts Be sufficiently impregnated in thing solution and through being evaporated, dry and calcination and obtain.Board-like catalyst is using metal sieve plate as carrier, machinery Intensity is good, particularly suitable coal-fired high grey SCR denitration occasion；Honeycombed catalyst is using SCR catalyst powder as matrix, with shaping The processes such as auxiliary agent etc. is by mixing, mediating, extrusion forming, drying and calcination obtain.And corrugated plate dst catalyst is with corrugated Fiberboard is carrier, applies the coating containing active component on its surface, active material fewer than honeycombed catalyst 70%, works as surface After active material abrasion is lost in, catalytic activity declines comparatively fast, and service life is shorter.Cellular and board-like catalyst be all first with V₂O₅/TiO₂Base SCR catalyst powder is raw material, abundant with water, adhesive, extrusion aid, expanding agent, lubricant, glass fibre etc. Mixing kneading obtains plasticity lotion, and then honeycombed catalyst passes through extrusion forming, drying and calcination by matrix of plasticity lotion Obtain.And tabular catalyst is that plasticity lotion is uniformly compressed in metal sieve plate, catalyst is obtained by drying, calcination.Leaching Go out the mol ratio m of total metal content in liquid_pre：m_metal=1~5, for example, 1.5,2,2.5,3,3.5,4 and 4.5 etc.；PH value of solution=6~ 12, for example, 7,8,9,10 and 11 etc.；Precipitation temperature is 10~90 DEG C, for example, 20,30,40,50,60,70 and 80 DEG C；Precipitation Time is 10~120min, for example, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 Min, 100 min and 110 min etc..

Wherein, SCR catalyst raw powder's production technology has the precipitation method, infusion process, mixing method, ion-exchange, roll coating process With heat melting method etc..Infusion process is that the liquid leaching containing active component and cocatalyst component is loaded in into solid-state carrier surface On.Its carrier utilization rate is high, and dosage is few, and cost is low, is widely used in the preparation of loaded catalyst, and the low content that is particularly suitable for use in is expensive Metallic catalyst；The precipitation method are that the catalytic component of solubility is converted into indissoluble or insoluble compound with precipitating reagent, through separating, The process such as washing, dry, calcining, shaping, finished product catalyst.Base metal, metal oxide, metal for high content Salt catalyst or catalyst carrier；Mixing method equipment is simple, easy to operate, and product chemical composition is stable, contains available for height is prepared The multicomponent catalyst of amount, especially mixed oxide catalyst, but this method decentralization is relatively low；Roll coating process is by active component mucilage It is placed in the container that can be shaken, thereon, through rolling after a while, active component just gradually adheres to non-porous support bead cloth In carrier surface.Because active component is easily peeled off, roll coating process potassium hydroxide；Ion-exchange makees carrier with exchanger, with anti- The form of ion introduces active component, prepares high dispersive, the load type metal or metal ion catalyst of large surface, especially suitable Prepared in the noble metal catalyst of low content, high usage；High-temperature melting method is to borrow hot conditions by each component of catalyst Fusion turns into equally distributed mixture, oxide solid solution or alloy solid solution, to produce the catalyst of property. It is mainly used in the preparation of ammonia synthesis fused iron catalyst, Fischer-Tropsch catalyst, blue Buddhist nun's skeleton catalyst etc..

Integrated comparative, the present invention preferably prepare SCR catalyst powder with infusion process.

When producing for example board-like preformed catalyst and honeycomb-shaped SCR denitrating catalyst, conventional forming method has：（1）Spraying Shaping：The colloidal sol configured or suspension shower nozzle are disperseed in drying tower internal spraying, done after heated-air drying as microspheroidal Gel, 30~200 microns of particle size range；（2）Forming oil column：Material solution is divided into two-way, squeezed into by certain flow rate Low pressure shower nozzle, mixed rapidly in shower nozzle and form colloidal sol, leave after shower nozzle with droplet state be dispersed in warm light oil or In transformer oil column, hydrogel is condensed into several seconds.Product obtained by spray shaping and forming oil column, regular shape, surface light Sliding, mechanical strength is good；（3）Rotational forming：Dry powder is placed in rotating disk turning round, tilting 30~60 °, sprayed into Vaporific binding agent, the topical powder wet are first bonded as core.With the continuous motion of rotating disk, core gradually grows up as ball, compared with Big ball coefficient of friction is small, rolling of floating on the surface, is just rolled out when meeting granularity requirements from rotating disk lower edge；（4）Extruded moulding ：Powder adds appropriate binding agent, and the good pureed mucilage of plasticity is just formed afterwards through rolling kneading.Compeled using piston or spiral Slurry is set to be cut into nearly equal length isometrical bar shaped cylinder or ring cylinder by porous plate, product is just obtained through drying, calcining.（5） Compression molding：Consistent, uniform in size, high mechanical strength the sheet cylinder of profile or ring cylinder is made in many powder materials.

As optimal technical scheme, method of the invention, comprise the following steps：

（1）Useless SCR denitration is pre-processed, removes the catalyst components such as the removal of impurity, activation vanadium tungsten；

（2）To step（1）The dead catalyst obtained after middle pretreatment is leached, and obtains leached mud and leachate；Leaching agent For neutral or alkalescence, the liquid-solid ratio of leaching agent and dead catalyst is 0.02 ~ 1L/g, and extraction temperature is 20 ~ 200 DEG C, leaches pressure For 0.1~1MPa, extraction time is 0.5 ~ 5h, and mixing speed is 100~5000r/min；

（3）Step（2）Each valuable element extraction or ion-exchange or precipitation method separation in leachate.Extraction During method, extractant can be that amine, organic phosphine acids, organosilane ester, neutral phosphine, quaternary ammonium salt and oximes, extractant concentration are 5%~30%, initial pH=1~9 of aqueous phase, extraction temperature is 10~40 DEG C, and extraction time is 10~40min；During ion-exchange, Resin types are strong basicity or weak-base anion-exchange resin, and leachate volume is 10~100 times of resin volume, pH value of solution For 2~11, temperature is 20~90 DEG C, swap time is 30~100min, and resin regeneration liquid is highly basic or weak caustic solution, during regeneration Between be 20~120min, regeneration temperature is 25~90 DEG C；During coprecipitation, the mol ratio of precipitating reagent and total metal content in leachate m_pre：m_metal=1~6, pH value of solution=5~11, precipitation temperature is 20~80 DEG C, and the sedimentation time is 20~120min；Obtained vanadium carries Pure thing and tungsten/molybdenum/tungsten enriched substance are further purified, prepare vanadium and tungsten/molybdenum/tungsten product.

Or（4）By step（2）The tune of each matter content ratio is carried out after valuable element Isolation in leachate Section, prepares catalyst component mixture.Valuable element extraction or ion-exchange or coprecipitation in leachate is synchronously pure Change.During extraction, extractant can be amine, organic phosphine acids, organosilane ester, neutral phosphine, quaternary ammonium salt and oximes, extractant Concentration is 5%~30%, and initial pH=1~10 of aqueous phase, extraction temperature is 10~40 DEG C, and extraction time is 10~40min；Ion is handed over When changing method, resin types are strong basicity or weak-base anion-exchange resin, and leachate volume is the 10~100 of resin volume Times, pH value of solution is 1~12, and temperature is 10~100 DEG C, swap time is 30~120min, and resin regeneration liquid is highly basic or weak base Solution, recovery time are 20~120min, and regeneration temperature is 20~100 DEG C；During coprecipitation, precipitating reagent and metal in leachate The mol ratio m of total amount_pre：m_metal=1~5, pH value of solution=6~12, precipitation temperature be 10~90 DEG C, the sedimentation time be 10~ 120min；

（5）Step（3）Described catalyst component mixture is prepared as new granular SCR denitration powder with infusion process Body.Catalyst component mixture is first dissolved in 0.1~0.2mol/L oxalic acid solution, is then proportionally added into TiO₂.By system Insert ultrasound in ultrasonic cleaner and mix 2~4h.After ultrasound terminates, system stirring is evaporated.The solid obtained after being evaporated Mixture, which is put into 105~110 DEG C of drying box, dries 12~24h.Dried solid mixture is clayed into power, then put Enter Muffle kiln roasting, sintering temperature is 400~600 DEG C, and roasting time is 5~12h.Product is new granular after roasting SCR denitration powder；

Compared with prior art, the invention has the advantages that：

1st, the inventive method veritably realize remanufactured while useless SCR denitration is obtained into harmless treatment for The raw catelyst of high activity, there is good environmental benefit and economic benefit；

2nd, the valuable elements such as V, Mo and W in useless SCR catalyst can be separated and be purified recovery by the inventive method, V, for the Mo and W rate of recovery more than 95%, obtained vanadium/tungsten/molybdenum/tungsten product purity reaches more than 99%.

Brief description of the drawings

Fig. 1 is the process chart of the method for the invention.

The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation Table or limitation the scope of the present invention, protection scope of the present invention are defined by claims.

Embodiment

Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.

For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting Embodiment is as follows：

Embodiment 1

The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V₂O₅Content is 1.1%, MoO₃For 3.3%, TiO₂For 95.3%。

（1）The above-mentioned dead catalyst of 10g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C.After drying Dead catalyst add NaOH and make additive, NaOH and the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=1.Mixing is equal Muffle kiln roasting is placed in after even, sintering temperature is 650 DEG C, roasting time 4h；

（2）Make leaching agent with the pure water of neutrality, from step（1）V and Mo is leached after roasting in dead catalyst, liquid-solid ratio is 0.02L/g, extraction temperature are 20 DEG C, and leaching pressure is 0.1MPa, extraction time 1.5h, mixing speed 1000r/min, V Single-stage leaching rate is 78.6%, Mo 75.7%；Leached mud return to step（1）；

（3）Using the extraction system that primary amine kind of extractants N1923 and toluene form as organic phase, concentration 5%, at the beginning of aqueous phase Beginning pH=1, two compare O/A=1, and extraction temperature is 10 DEG C, extraction time be 10min under conditions of from step（2）Described leaching V and Mo are synchronously extracted in liquid, V extraction yields are that 100%, Mo extraction yields are 99.99%.Then with 5% ammoniacal liquor to the V in extraction phase With Mo synchronously back extraction obtain vanadium molybdenum mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal=1, back extraction temperature is 20 DEG C, Stripping times 0.5h.Adjust the ratio of the V and Mo in vanadium molybdenum mixed-ammonium salt solution Example, then through evaporate, crystallize, wash and 50 DEG C at dry vanadium molybdenum mixed-ammonium salt；

（4）Using the extraction system that primary amine kind of extractants N1923 and toluene form as organic phase, concentration 5%, at the beginning of aqueous phase Beginning pH=6, two compare O/A=1, and extraction temperature is 10 DEG C, extraction time be 10min under conditions of from step（2）Described leaching Extract and separate V and Mo, V extraction yield are that 100%, Mo extraction yields are 0.5% in liquid, obtain rich vanadium organic phase and raffinate containing molybdenum.It is rich Vanadium organic phase with 10% ammoniacal liquor be stripped, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal= 3, back extraction temperature is 40 DEG C, Stripping times 1h, and back extraction obtains ammonium metavanadate precipitate；

（5）Step（3）Obtained vanadium molybdenum mixed-ammonium salt is first dissolved in 0.2mol/L oxalic acid solution, is then added in proportion Enter TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 2h.After ultrasound terminates, system stirring is evaporated.After being evaporated The solid mixture of acquisition, which is put into 110 DEG C of electric drying oven with forced convection, dries 12h.By dried solid mixture grinds End, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 400 DEG C, roasting time 5h.Product is after roasting Granular 1.2%V₂O₅-3.5%MO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained ammonium metavanadate precipitate is first dissolved with nitric acid, then adjusts pH value of solution=7, then adds sulfuric acid Ammonium precipitates, and obtained ammonium metavanadate precipitate is scrubbed, dries and is calcined, and obtains vanadic anhydride product, purity 99.5%；Step Suddenly（4）The obtained nitre of raffinate containing molybdenum acid for adjusting pH=1.5, then through evaporative crystallization, washing and drying, obtain molybdic acid product, Purity is 99.1%.

Embodiment 2

The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V₂O₅Content is 1.4%, MoO₃For 3.2%, TiO₂For 95%。

（1）The above-mentioned dead catalyst of 5g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C.After drying Dead catalyst add NaOH and make additive, NaOH and the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=2.Mixing is equal Muffle kiln roasting is placed in after even, sintering temperature is 680 DEG C, roasting time 5h；

（2）Make leaching agent with the pure water of neutrality, from step（1）V and Mo is leached after roasting in dead catalyst, liquid-solid ratio is 0.06L/g, extraction temperature are 60 DEG C, and leaching pressure is 0.1MPa, extraction time 2h, mixing speed 800r/min, V single-stage Leaching rate is 79.6%, Mo 77.4%；Leached mud return to step（1）；

（3）Using the extraction system that secondary amine kind of extractants dioctylamine and normal octane form as organic phase, concentration 15%, in water Mutually initial pH=3, two compare O/A=1, and extraction temperature is 20 DEG C, extraction time under conditions of 15min from step（2）Leachate Middle synchronous extraction V and Mo, V extraction yield are that 99.6%, Mo extraction yields are 98.8%.Then with 10% ammoniacal liquor to the V in extraction phase and Mo synchronously back extraction obtains vanadium molybdenum mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal=4, back extraction temperature is 45 DEG C, Stripping times 3h.The ratio of the V and Mo in vanadium molybdenum mixed-ammonium salt solution are adjusted, Then through evaporate, crystallize, wash and 55 DEG C at dry vanadium molybdenum mixed-ammonium salt；

（4）Using the extraction system that secondary amine kind of extractants dioctylamine and normal octane form as organic phase, concentration 15%, in water Mutually initial pH=5, two compare O/A=1, and extraction temperature is 25 DEG C, extraction time under conditions of 25min from step（2）Leachate Middle extract and separate V and Mo, V extraction yield are that 99.5%, Mo extraction yields are 0.12%, obtain rich vanadium organic phase and raffinate containing molybdenum.With 15% ammoniacal liquor is stripped to obtain ammonium metavanadate precipitate to rich vanadium organic phase, wherein total metal content in the ammonium ion and organic phase that add Mol ratio m_NH4+:m_metal=10, back extraction temperature is 70 DEG C, Stripping times 4h；

（5）Step（3）Obtained vanadium molybdenum mixed-ammonium salt is first dissolved in 0.15mol/L oxalic acid solution, then in proportion Add TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 2.5h.After ultrasound terminates, system stirring is evaporated.It will steam The solid mixture obtained after dry, which is put into 105 DEG C of electric drying oven with forced convection, dries 15h.Dried solid mixture is ground Into powder, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 450 DEG C, roasting time 6h.Product after roasting As granular 1.1%V₂O₅-3.1%MO₃/TiO₂It is SCR denitration.

（6）Step（4）Obtained ammonium metavanadate precipitate is first dissolved with nitric acid, then adjusts pH value of solution=7.5, then adds nitre Sour ammonium precipitation, obtained ammonium metavanadate precipitate is scrubbed, dries and roasting, obtains vanadic anhydride product, purity 99.6%； Step（4）The obtained nitre of raffinate containing molybdenum acid for adjusting pH=1.2, then through evaporative crystallization, washing and drying, obtain molybdic acid production Product, purity 99.2%.

Embodiment 3

The useless vanadium tungsten system SCR denitration that certain laboratory provides, V₂O₅Content is 1.5%, WO₃For 3.3%, TiO₂For 95%。

（1）The above-mentioned dead catalyst of 10g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C.After drying Dead catalyst add Na₂CO₃Make additive, Na₂CO₃With the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=6.Mixing Muffle kiln roasting is placed in after uniformly, sintering temperature is 500 DEG C, roasting time 7h；

（2）Make leaching agent with the pure water of neutrality, from step（1）V and W is leached after roasting in dead catalyst, liquid-solid ratio is 0.05L/g, extraction temperature are 70 DEG C, and leaching pressure is 0.1MPa, extraction time 1.5h, mixing speed 1200r/min, V Single-stage leaching rate is 79.6%, W 76.4%；Leached mud return to step（1）；

（3）The extraction system formed using tertiary amine kind of extractants Alamine 336 and kerosene is organic phase, concentration 25%, Aqueous phase initial pH=4, two compare O/A=1, and extraction temperature is 40 DEG C, extraction time be 40min under conditions of from step（2）Leach V and W are synchronously extracted in liquid, V extraction yields are that 98.6%, W extraction yields are 99.6%.Then with 20% ammoniacal liquor to the V in extraction phase and W synchronously back extraction obtains vanadium tungsten mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+: m_metal=6, back extraction temperature is 50 DEG C, Stripping times 3h.Adjust the ratio of the V and W in vanadium tungsten mixed-ammonium salt solution, Ran Houjing Dry vanadium tungsten mixed-ammonium salt at evaporation, crystallization, washing and 48 DEG C；

（4）The extraction system formed using tertiary amine kind of extractants Alamine 336 and kerosene is organic phase, concentration 25%, Aqueous phase initial pH=1.0, two compare O/A=1, and extraction temperature is 25 DEG C, extraction time be 20min under conditions of from step（2）Leaching It is that 100%, W extraction yields are 0.2% to go out extract and separate V and W, V extraction yield in liquid, obtains rich vanadium organic phase and tungstenic raffinate.With 1g/L NaOH solution is stripped to rich vanadium organic phase, wherein the OH added^-With the mol ratio m of total metal content in organic phase_OH ^-: m_metal=10, back extraction temperature is 70 DEG C, Stripping times 4h, obtains sodium vanadate solution；

（5）Step（3）Obtained vanadium tungsten mixed-ammonium salt is first dissolved in 0.16mol/L oxalic acid solution, then in proportion Add TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 3h.After ultrasound terminates, system stirring is evaporated.It will be evaporated The solid mixture obtained afterwards, which is put into 106 DEG C of electric drying oven with forced convection, dries 16h.Dried solid mixture is worn into Powder, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 500 DEG C, roasting time 5.5h.Product after roasting As granular 1.2%V₂O₅-3.0%WO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained sodium vanadate solution regulation pH=8, add ammonium sulfate precipitation, obtained ammonium metavanadate precipitate Scrubbed, dry and roasting, obtains vanadic anhydride product, purity 99.5%；Step（4）Obtained tungstenic raffinate nitre Acid for adjusting pH=1.0, then through evaporative crystallization, washing and drying, obtain tungstenic acid product, purity 99.0%.

Embodiment 4

The useless vanadium tungsten system SCR denitration that certain laboratory provides, V₂O₅Content is 1.3%, WO₃For 3.2%, TiO₂For 95.2%。

（1）The above-mentioned dead catalyst of 10g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C.After drying Dead catalyst add NaCl and make additive, NaCl and the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=4.5.Mixing Muffle kiln roasting is placed in after uniformly, sintering temperature is 700 DEG C, roasting time 4h；

（2）Make leaching agent with the pure water of neutrality, from step（1）V and W is leached after roasting in dead catalyst, liquid-solid ratio is 0.1L/g, extraction temperature are 80 DEG C, and leaching pressure is 0.2MPa, extraction time 3h, mixing speed 5000r/min, V single-stage Leaching rate is 78.8%, W 75.9%；Leached mud return to step（1）；

（3）Using the extraction system that quaternary amine Aliquat 336 and kerosene form as organic phase, concentration 25%, at the beginning of aqueous phase Beginning pH=3, two compare O/A=1, and extraction temperature is 30 DEG C, extraction time be 30min under conditions of from step（2）It is same in leachate Step extraction V and W, V extraction yield are that 98.7%, W extraction yields are 98.90%.Then it is synchronous to the V in extraction phase and W with 20% ammoniacal liquor Back extraction obtain vanadium tungsten mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal= 5, back extraction temperature is 45 DEG C, Stripping times 3h.Adjust vanadium tungsten mixed-ammonium salt solution in V and W ratio, then through evaporation, Dry vanadium tungsten mixed-ammonium salt at crystallization, washing and 45 DEG C；

（4）Using the extraction system that quaternary amine Aliquat 336 and kerosene form as organic phase, concentration 25%, at the beginning of aqueous phase Beginning pH=9.0, two compare O/A=1, and extraction temperature is 40 DEG C, extraction time be 40min under conditions of from step（2）In leachate Extract and separate V and W, V extraction yield are that 0.2%, W extraction yields are 99.6%, obtain rich tungsten organic phase and raffinate containing vanadium.Use 10g/L NaOH solution rich tungsten organic phase is stripped, wherein the OH added^-With the mol ratio m of total metal content in organic phase_OH ^-:m_metal=5, It is 30 DEG C to be stripped temperature, Stripping times 0.5h, obtains sodium tungstate solution；

（5）Step（3）Obtained vanadium tungsten mixed-ammonium salt is first dissolved in 0.2mol/L oxalic acid solution, is then added in proportion Enter TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 4h.After ultrasound terminates, system stirring is evaporated.After being evaporated The solid mixture of acquisition, which is put into 110 DEG C of electric drying oven with forced convection, dries 18h.By dried solid mixture grinds End, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 550 DEG C, roasting time 7h.Product is after roasting Granular 1.3%V₂O₅-3.4%WO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained sodium tungstate solution nitre acid for adjusting pH=1.5, then through evaporative crystallization, washing, drying and Calcining, obtains tungstic acid product, purity 99.2%；Step（4）The obtained regulation of raffinate containing vanadium pH=7.2, are then added Ammonium chloride precipitation, obtained ammonium metavanadate precipitate is scrubbed, drying and calcination, obtains vanadic anhydride product, purity is 99.6%。

Embodiment 5

The useless vanadium tungsten system SCR denitration that certain laboratory provides, V₂O₅Content is 1.3%, WO₃For 2.4%, TiO₂For 96.1%。

（1）The above-mentioned dead catalyst of 5g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 110 DEG C.After drying Dead catalyst add Na₂SO₄Make additive, Na₂SO₄With the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=5.5.It is mixed Muffle kiln roasting is placed in after closing uniformly, sintering temperature is 800 DEG C, roasting time 5h；

（2）Make leaching agent with 1g/LNaOH solution, from step（1）V and W is leached after roasting in dead catalyst, liquid-solid ratio is 0.2L/g, extraction temperature are 100 DEG C, and leaching pressure is 0.2MPa, and extraction time 4h, mixing speed 2000r/min, V are mono- Level leaching rate is 81.7%, W 77.2%；Leached mud return to step（1）；

（3）The extraction system formed using neutral phosphine extractant TBP and kerosene is organic phase, concentration 30%, at the beginning of aqueous phase Beginning pH=6, two compare O/A=1, and extraction temperature is 30 DEG C, and extraction time synchronously extracts V under conditions of being 35min from leachate And W, V extraction yield are that 99.0%, W extraction yields are 97.6%.Then the V in extraction phase and W is synchronously stripped with 30% ammoniacal liquor and obtained Vanadium tungsten mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal=6, back extraction temperature Spend for 50 DEG C, Stripping times 4h.The ratio of the V and W in vanadium tungsten mixed-ammonium salt solution are adjusted, then through evaporating, crystallizing, washing With 50 DEG C at dry vanadium tungsten mixed-ammonium salt；

（4）The extraction system formed using neutral phosphine extractant TBP and kerosene is organic phase, concentration 30%, at the beginning of aqueous phase Beginning pH=2.5, two compare O/A=1, and extraction temperature is 30 DEG C, extraction time be 35min under conditions of from leachate extract and separate V and W, V extraction yield are that 99.8%, W extraction yields are 0.3%, obtain rich vanadium organic phase and tungstenic raffinate.Rich vanadium organic phase 5g/ LNaOH solution is stripped, wherein the OH added^-With the mol ratio m of total metal content in organic phase_OH ^-:m_metal=4.5, being stripped temperature is 35 DEG C, Stripping times 1h, obtain sodium vanadate solution；

（5）Step（3）Obtained vanadium tungsten mixed-ammonium salt is first dissolved in 0.2mol/L oxalic acid solution, is then added in proportion Enter TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 3h.After ultrasound terminates, system stirring is evaporated.After being evaporated The solid mixture of acquisition, which is put into 110 DEG C of electric drying oven with forced convection, dries 24h.By dried solid mixture grinds End, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 600 DEG C, roasting time 12h.Product is after roasting For granular 1.4%V₂O₅-3.0%WO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained sodium vanadate solution regulation pH=9, then add ammonium nitrate precipitation, obtained ammonium metavanadate Scrubbed, drying and calcination are precipitated, obtain vanadic anhydride product, purity 99.5%；Tungstenic raffinate adjusts pH=6.2, so Tungsten is carried again with extraction afterwards.The extraction system of neutral phosphine extractant TBP and kerosene composition is organic phase, concentration 15%, two Compared to O/A=1, extraction temperature is 30 DEG C, and extraction time 30min, W extraction yield are 99.5%.Rich tungsten organic phase is anti-with 30% ammoniacal liquor Extraction, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal=5, back extraction temperature is 35 DEG C, back extraction Time is 2h, and obtained ammonium tungstate solution obtains ammonium paratungstate product, purity 99.3% through evaporative crystallization, washing and drying.

Embodiment 6

The useless vanadium tungsten system SCR denitration that certain laboratory provides, V₂O₅Content is 1.3%, WO₃For 1.4%, MoO₃For 1.4%, TiO₂For 95.7%.

（1）The above-mentioned dead catalyst of 5g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C.After drying Dead catalyst add NaNO₃Make additive, NaNO₃With the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=6.Mixing Muffle kiln roasting is placed in after uniformly, sintering temperature is 900 DEG C, roasting time 7h；

（2）Make leaching agent with 1g/LNaOH solution, from step（1）V, W and Mo, liquid-solid ratio are leached after roasting in dead catalyst For 0.3L/g, extraction temperature is 100 DEG C, and leaching pressure is 0.4MPa, extraction time 5h, mixing speed 3000r/min, V Single-stage leaching rate is 81.7%, W 77.2%；Leached mud return to step（1）；

（3）Using the extraction system that organosilane ester amyl acetate and kerosene form as organic phase, concentration 25%, at the beginning of aqueous phase Beginning pH=10, two compare O/A=1, and extraction temperature is 40 DEG C, extraction time be 40min under conditions of from step（2）It is same in leachate Step extraction V, W and Mo, V extraction yields are that 99.6%, W extraction yields are that 98.6%, Mo extraction yields are 97.8%.Then with 15% ammoniacal liquor pair Synchronously back extraction obtains vanadium tungsten mixed-ammonium salt solution by V, W and Mo in extraction phase, wherein golden in the ammonium ion and organic phase that add Belong to the mol ratio m of total amount_NH4+:m_metal=5, back extraction temperature is 45 DEG C, Stripping times 2h.Adjust vanadium tungsten mixed-ammonium salt solution In V, W and Mo ratio, then through evaporate, crystallize, wash and 45 DEG C at dry vanadium tungsten mixed-ammonium salt；

（4）Using the extraction system that organosilane ester amyl acetate and kerosene form as organic phase, concentration 25%, at the beginning of aqueous phase Beginning pH=3.2, two compare O/A=1, and extraction temperature is 40 DEG C, extraction time be 40min under conditions of from step（2）In leachate Extract and separate V, W and Mo, V extraction yields are 100%, W and Mo extraction yields are less than 0.2%, obtain rich vanadium organic phase and raffinate containing tungsten Liquid.Rich vanadium organic phase is stripped with 15% ammoniacal liquor, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal=4, back extraction temperature is 40 DEG C, Stripping times 2.5h, obtains ammonium metavanadate precipitate；

（5）Step（3）Obtained vanadium tungsten mixed-ammonium salt is first dissolved in 0.2mol/L oxalic acid solution, then in proportion Add TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 4h.After ultrasound terminates, system stirring is evaporated.It will be evaporated The solid mixture obtained afterwards, which is put into 110 DEG C of electric drying oven with forced convection, dries 24h.Dried solid mixture is worn into Powder, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 600 DEG C, roasting time 10h.Product after roasting As granular 1.4%V₂O₅-1.2%WO₃-1.2% MoO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained ammonium metavanadate precipitate is scrubbed, drying and calcination, obtains vanadic anhydride product, purity For 99.3%；Step（4）The obtained regulation of raffinate containing tungsten pH=2, then through evaporative crystallization, washing, drying and calcination, are obtained Molybdenum trioxide and tungstic acid mix product, purity 99.0%.

Embodiment 7

The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V₂O₅Content is 1.2%, MoO₃For 2.5%, TiO₂For 96%。

（1）The above-mentioned dead catalyst of 5g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C；

（2）Make leaching agent with 2g/LNaOH solution, from step（1）V and Mo is leached after drying in dead catalyst, liquid-solid ratio is 0.5L/g, extraction temperature are 200 DEG C, and leaching pressure is 1 MPa, extraction time 5h, mixing speed 5000r/min, V single-stage Leaching rate is 84.1%, Mo 80.1%；Leached mud return to step（1）；

（3）For the extraction system formed using organic phosphine D2EHPA and kerosene as organic phase, concentration 15% is initial in aqueous phase PH=8.5, two compare O/A=1, and extraction temperature is 30 DEG C, extraction time be 30min under conditions of from step（2）It is same in leachate Step extraction V and Mo, V extraction yield are that 99.8%, Mo extraction yields are 98.9%.Then it is same to the V in extraction phase and Mo with 20% ammoniacal liquor Step back extraction obtain vanadium molybdenum mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+: m_metal=6, back extraction temperature is 30 DEG C, Stripping times 2.5h.The ratio of the V and Mo in vanadium molybdenum mixed-ammonium salt solution are adjusted, then Through evaporate, crystallize, wash and 40 DEG C at dry vanadium molybdenum mixed-ammonium salt；

（4）For the extraction system formed using organic phosphine D2EHPA and kerosene as organic phase, concentration 15% is initial in aqueous phase PH=2, two compare O/A=1, and extraction temperature is 30 DEG C, extraction time be 30min under conditions of from step（2）Extracted in leachate It is that 0.1%, Mo extraction yields are 99.9% to separate V and Mo, V extraction yield, obtains rich molybdenum organic phase and raffinate containing vanadium.With 1g/L's NaOH solution is stripped to rich molybdenum organic phase, wherein the OH added^-With the mol ratio m of total metal content in organic phase_OH ^-:m_metal=5, instead It is 30 DEG C to extract temperature, Stripping times 0.5h, obtains sodium molybdate solution；

（5）Step（3）Obtained vanadium molybdenum mixed-ammonium salt is first dissolved in 0.1mol/L oxalic acid solution, is then added in proportion Enter TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 4h.After ultrasound terminates, system stirring is evaporated.After being evaporated The solid mixture of acquisition, which is put into 110 DEG C of electric drying oven with forced convection, dries 24h.By dried solid mixture grinds End, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 600 DEG C, roasting time 9h.Product is after roasting Granular 1.5%V₂O₅-2.6%MO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained sodium molybdate solution obtains sodium molybdate product, purity is through evaporative crystallization, washing and drying 99.5%；Step（4）Obtained raffinate containing vanadium first adjusts pH=8.5, then adds ammonium sulfate precipitation, and obtained ammonium metavanadate sinks Form sediment scrubbed, drying and calcination, obtain vanadic anhydride product, purity 99.6%.

Embodiment 8

The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V₂O₅Content is 1.5%, MoO₃For 2.3%, TiO₂For 96.1%。

（1）The above-mentioned dead catalyst of 5g is taken, first smashes to 100 mesh, after water washing, filtering, is dried at 105 DEG C；

（2）Make leaching agent with 5g/LNaOH solution, from step（1）V and Mo is leached after drying in dead catalyst, liquid-solid ratio is 0.6L/g, extraction temperature are 150 DEG C, and leaching pressure is 0.5 MPa, and extraction time 5h, mixing speed 5000r/min, V are mono- Level leaching rate is 80.1%, Mo 81.1%；Leached mud return to step（1）；

（3）Using the extraction system that oximes extractant Lix63 and kerosene form as organic phase, concentration 30% is initial in aqueous phase PH=6, two compare O/A=1, and extraction temperature is 40 DEG C, extraction time be 40min under conditions of from step（2）It is synchronous in leachate It is that 98.7%, Mo extraction yields are 98.9% to extract V and Mo, V extraction yield.Then it is synchronous to the V in extraction phase and Mo with 20% ammoniacal liquor Back extraction obtain vanadium molybdenum mixed-ammonium salt solution, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal= 5, back extraction temperature is 20 DEG C, Stripping times 3h.Adjust vanadium molybdenum mixed-ammonium salt solution in V and Mo ratio, then through evaporation, Dry vanadium molybdenum mixed-ammonium salt at crystallization, washing and 40 DEG C；

（4）Using the extraction system that oximes extractant Lix63 and kerosene form as organic phase, concentration 30% is initial in aqueous phase PH=2, two compare O/A=1, and extraction temperature is 40 DEG C, extraction time be 40min under conditions of from leachate extract and separate V and Mo, V extraction yield are that 99.7%, Mo extraction yields are 0.4%, obtain rich vanadium organic phase and raffinate containing molybdenum.Rich vanadium is stripped with 15% ammoniacal liquor Organic phase, wherein in the ammonium ion and organic phase that add total metal content mol ratio m_NH4+:m_metal=5, back extraction temperature is 45 DEG C, Stripping times are that 2.5h obtains ammonium metavanadate precipitate；

（5）Step（3）Obtained vanadium molybdenum mixed-ammonium salt is first dissolved in 0.1mol/L oxalic acid solution, is then added in proportion Enter TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 4h.After ultrasound terminates, system stirring is evaporated.After being evaporated The solid mixture of acquisition, which is put into 110 DEG C of electric drying oven with forced convection, dries 24h.By dried solid mixture grinds End, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 600 DEG C, roasting time 9h.Product is after roasting Granular 1.4%V₂O₅-2.2%MO₃/TiO₂It is SCR denitration；

（6）Step（4）Obtained ammonium metavanadate precipitate is scrubbed, drying and calcination, obtains vanadic anhydride product, purity For 99.7%；Step（4）The obtained regulation of raffinate containing molybdenum pH=1, then through evaporative crystallization, washing, drying and calcination, obtains three Molybdenum oxide product, purity 99.4%.

Embodiment 9

The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V₂O₅Content is 1.2%, WO₃For 3.3%, TiO₂For 95.3%.

（1）The above-mentioned dead catalyst of 50g is taken, is first smashed to 100 mesh, is washed with water and is washed, filters and 105 DEG C of dryings；

（2）Make leaching agent with 2g/L sodium hydroxide solution, from step（1）V and W is leached in dried dead catalyst, Liquid-solid ratio is 1L/g, and extraction temperature is 200 DEG C, and leaching pressure is 1MPa, extraction time 5h, mixing speed 100r/min, V Single-stage leaching rate is 77.2%, W 75.6%；Leached mud carries out secondary leaching；

（3）Step（2）Obtained leachate nitre acid for adjusting pH=6, then add calcium nitrate co-precipitation, calcium nitrate and leaching Go out the mol ratio m of total metal content in liquid_pre：m_metal=1, reaction temperature be 10 DEG C, sedimentation time 10min, can obtain calcium vanadate and Artificial schellite mixed precipitation.Mixed precipitation is dissolved with nitric acid, after adjusting pH value of solution=6, calcium nitrate co-precipitation is added, obtains It is pure vanadium tungsten mixing calcium salt to precipitate scrubbed, dry.Vanadium tungsten mixing calcium salt nitric acid dissolves and adjusts pH value of solution=1.5, then Adjust the ratio of V and W in solution.Vanadium tungsten solution through evaporate, crystallize, wash and 105 DEG C at dry after, further at 600 DEG C Roasting, obtains vanadium tungsten mixed oxide；

（4）Step（2）Obtained leachate separates V and W with the precipitation method.Leachate pH=5 are adjusted, then add ammonium sulfate Precipitation, the mol ratio m of ammonium sulfate and vanadium metal in leachate_pre：m_metal=1, precipitation temperature is 20 DEG C, sedimentation time 20min, Filter to obtain ammonium metavanadate precipitate and tungstenic solution；

（5）Step（3）Obtained vanadium tungsten mixed oxide prepares vanadium tungsten system SCR catalyst powder with mixing method.First by vanadium Tungsten mixed oxide is crushed to 100 mesh, then with TiO₂Wet ball grinding mixing 5h is carried out according to certain ratio.Mixing terminates Afterwards, it is placed in together in 110 DEG C of baking oven and dries 12h.Dried product is 1.3%V₂O₅-3.2%WO₃/TiO₂It is SCR catalysis Agent powder.50g is taken to be milled to 0.1mm catalyst powder, it is 0.1mm then to add adhesive polyacrylamide 4.5g and particle diameter Absorbent charcoal powder body 2.5g after dry-mixed 15min.After well mixed, 10mL water and extrusion aid monoethanolamine 4mL, Ran Houyong are sequentially added Roll rod and kneading operation is carried out to wet stock, obtain plasticity lotion.Plasticity lotion is loaded into honeycombed catalyst mould upstream, used Plasticity lotion is pressed between the sizing bar of bottom by pressing plate by force.Mould containing catalyst lotion is added in 65 DEG C of baking ovens Heat, after be coated in advance sizing bar and die surface on it is paraffin melting after, mould is taken out to obtain half-dried catalyst idiosome.Urge 12h is dried in prior to 105 DEG C baking ovens of agent idiosome, 12h is calcined at 450 DEG C, produces cellular 1.3%V₂O₅-3.3%WO₃/ TiO₂It is SCR denitration；

（6）Step（4）Obtained ammonium metavanadate precipitate is scrubbed, drying and calcination, obtains vanadic anhydride product, purity For 99.1%；Step（4）Obtained tungstenic solution regulation pH=8, then add nitric acid calcium precipitate, calcium nitrate and metal in leachate The mol ratio m of tungsten_pre：m_metal=6, reaction temperature is 50 DEG C, sedimentation time 50min, can obtain wolframic acid calcium precipitate.Wolframic acid calcium precipitate It is scrubbed and be dried to obtain wolframic acid calcium product, purity 99.3%.

Embodiment 10

The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V₂O₅Content is 1.1%, MO₃For 2.5%, TiO₂For 96.2%.

（1）The above-mentioned dead catalyst of 50g is taken, is first smashed to 100 mesh, is washed with water and is washed, filters and dry.Dried give up is urged Agent adds NaNO₃Make additive, NaNO₃With the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=4.5.It is well mixed After be placed in Muffle kiln roasting, sintering temperature is 700 DEG C, roasting time 6h；

（2）Make leaching agent with 2g/L sodium hydroxide solution, from step（1）V and Mo is leached in dead catalyst after roasting, Liquid-solid ratio is 0.2L/g, and extraction temperature is 120 DEG C, and leaching pressure is 0.5MPa, extraction time 5h, mixing speed 1000r/ Min, V single-stage leaching rate are 74.9%, Mo 72.7%；Leached mud carries out secondary leaching；

（3）Step（2）Described in leachate regulation pH=12, then add calcium chloride co-percipitation, calcium chloride and leachate The mol ratio m of middle total metal content_pre：m_metal=5, reaction temperature is 90 DEG C, sedimentation time 120min, can obtain calcium vanadate and molybdic acid Calcium mixed precipitation.Mixed precipitation is dissolved with nitric acid, after adjusting pH value of solution=12, adds calcium chloride co-percipitation, obtained precipitation Scrubbed, dry is pure vanadium molybdenum mixing calcium salt.Vanadium molybdenum mixing calcium salt nitric acid dissolves and adjusts pH value of solution=1.5, then adjusts V and Mo ratio in solution.Vanadium molybdenum solution through evaporate, crystallize, wash and 105 DEG C at dry, be further calcined at 650 DEG C, Obtain vanadium molybdenum mixed oxide；

（4）Step（2）Described in leachate with the precipitation method separate V and Mo.Leachate pH=11 are adjusted, then add chlorine Change ammonium precipitation, the mol ratio m of ammonium chloride and vanadium metal in leachate_pre：m_metal=6, precipitation temperature is 80 DEG C, and the sedimentation time is 120min, filter to obtain ammonium metavanadate precipitate and containing molybdenum solution；

（5）Step（3）Obtained vanadium molybdenum mixed oxide is first dissolved in 0.1mol/L oxalic acid solution, then in proportion Add TiO₂.System is inserted into ultrasound in ultrasonic cleaner and mixes 4h.After ultrasound terminates, system stirring is evaporated.It will be evaporated The solid mixture obtained afterwards, which is put into 110 DEG C of electric drying oven with forced convection, dries 24h.Dried solid mixture is worn into Powder, it is then placed in crucible and inserts Muffle kiln roasting, sintering temperature is 600 DEG C, roasting time 9h.Product of roasting is 1.2%V₂O₅-2.5%MO₃/TiO₂It is SCR catalyst powder.Take 50g to be milled to 0.1mm catalyst powder, then add bonding Dry-mixed 20min after the agent polyacrylamide 5g and absorbent charcoal powder body 2.5g that particle diameter is 0.1mm.After well mixed, 8mL is sequentially added Water and extrusion aid monoethanolamine 3.5mL, kneading operation then is carried out to wet stock with rolling rod, obtains plasticity lotion.By plasticity lotion Load honeycombed catalyst mould upstream, plasticity lotion is pressed between the sizing bar of bottom by force using pressing plate.It will contain and urge The mould of agent lotion heats in 60 DEG C of baking ovens, after be coated in advance sizing bar and die surface on it is paraffin melting after, by mould Tool takes out and obtains half-dried catalyst idiosome.24h is dried in prior to 110 DEG C baking ovens of catalyst idiosome, is calcined at 450 DEG C 12h, produce cellular 1.3%V₂O₅-2.4%WO₃/TiO₂It is SCR denitration.

（6）Step（4）Obtained ammonium metavanadate precipitate is scrubbed, drying and calcination, obtains vanadic anhydride product, purity For 99.5%；Step（4）What is obtained adjusts pH=10 containing molybdenum solution, then adds calcium chloride precipitation, calcium nitrate and gold in leachate Belong to the mol ratio m of molybdenum_pre：m_metal=6, reaction temperature is 50 DEG C, sedimentation time 120min, can obtain molybdic acid calcium precipitate.Calcium molybdate Precipitate scrubbed and be dried to obtain molybdic acid calcium product, purity 99.6%.

Embodiment 11

The useless vanadium molybdenum system SCR catalyst that certain laboratory provides, V₂O₅Content is 1.1%, MO₃For 2.0%, TiO₂For 96.7%.

（1）The above-mentioned dead catalyst of 50g is taken, is first smashed to 100 mesh, after being washed with water, filtering, is dried at 105 DEG C.Dry Dead catalyst afterwards adds NaCl and makees additive, NaCl and the mol ratio m of Metals from Spent Catalysts total amount_add:m_metal=6.Mixing Muffle kiln roasting is placed in after uniformly, sintering temperature is 900 DEG C, roasting time 7h；

（2）Make leaching agent with 1g/L sulfuric acid solution, from step（1）V and Mo is leached in dead catalyst after roasting, liquid is solid Than for 1L/g, extraction temperature is 100 DEG C, leaching pressure is 0.2MPa, extraction time 0.5h, mixing speed 5000r/min, V single-stages leaching rate is 96.2%, Mo 95.2%, Ti 86.1%；Leached mud return to step（1）；

（3）Step（2）In V, Mo and Ti in obtained leachate synchronously carried with weak-base anion-exchange resin D418 Take.Leachate volume is 10 times of resin volume, pH value of solution=1, and temperature is 10 DEG C, and the exchange reaction time is 30min, V recovery rates For 94.3%, Mo 95.8%, Ti 96.2%, mother liquor carries out second extraction.With 15% ammoniacal liquor to resin regenerated from washing, during regeneration Between be 20min, regeneration temperature is 20 DEG C, obtains vanadium molybdenum titanium mixed-ammonium salt solution；

（4）Step（2）Described in leachate first adjust pH=9, filter to obtain sodium titanate precipitation and vanadium molybdenum solution.Vanadium molybdenum is molten Liquid is separated with weak-base anion-exchange resin D418, and leachate volume is 10 times of resin volume, pH value of solution=2, temperature 20 DEG C, the exchange reaction time is 30min, and V recovery rates are 99.3%, Mo 0.2%, obtains negative vanadium resin and extraction raffinate containing molybdenum.Use 2g/L Na₂CO₃Solution is 25 DEG C to resin regenerated from washing, recovery time 20min, regeneration temperature, obtains sodium vanadate solution；

（5）Step（3）Obtained vanadium molybdenum titanium mixed-ammonium salt solution prepares vanadium molybdenum system SCR denitration powder with the precipitation method Body.Vanadium molybdenum titanium mixed-ammonium salt solution is first adjusted into pH=7.5, calcium nitrate is then added, is filtrated to get vanadium molybdenum titanium mixed precipitation.It is mixed Close precipitation first to be dissolved with nitric acid, and continue to be acidified to pH=1.1, then through evaporative crystallization, washing, 105 DEG C of dryings and 750 DEG C of roastings Burn, obtain 1.2%V₂O₅-2.0%MoO₃/TiO₂It is SCR catalyst powder.50g is taken to be milled to 0.1mm catalyst powder, then Adhesive methylcellulose 5.5g and particle diameter are added as dry-mixed 18min after 0.1mm absorbent charcoal powder body 3.5g.After well mixed, 8mL water, extrusion aid monoethanolamine 4mL and lubricating oil glycerine 2.5mL are sequentially added, kneading behaviour then is carried out to wet stock with rolling rod Make, obtain plasticity lotion.Using the 55*100mm stainless steel flat plate with sieve aperture as carrier, plate thickness 0.5mm, aperture Lmm, pitch of holes 1.5mm, equilateral triangle arrangement, the thick plasticity lotions of 0.5mm are uniformly suppressed in both sides to sieve plate up and down.Modeling will be carried Property lotion sieve plate at 105 DEG C dry 12h, then at 500 DEG C be calcined 24h after, it is 1.5mm catalyst lists to obtain thickness Plate, it is assembled in Stainless Steel Shell and obtains board-like catalyst；

（6）Step（4）Obtained sodium vanadate solution regulation pH=8, add ammonium sulfate precipitation, obtained ammonium metavanadate precipitate Scrubbed, drying and calcination, obtained vanadic anhydride product, purity 99.5%；Step（4）The obtained regulation of extraction raffinate containing molybdenum PH=1.2, then through evaporative crystallization, washing and drying, obtain molybdic acid product, purity 99.0%.

Embodiment 12

The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V₂O₅Content is 1.3%, WO₃For 2.4%, TiO₂For 96.1%.

（1）The above-mentioned dead catalyst of 50g is taken, is first smashed to 100 mesh, after being washed with water, filtering, is dried at 105 DEG C；

（2）Make leaching agent with 1g/LNaOH solution, from step（1）Middle leaching V and W, liquid-solid ratio 0.7L/g, extraction temperature For 150 DEG C, leaching pressure is 0.5MPa, and extraction time 2h, mixing speed 4000r/min, V single-stage leaching rate is 87.2%, W is 86.3%, Ti 84.3%；Leached mud return to step（1）；

（3）Step（2）In V in obtained leachate and W synchronously extracted with strong-base anion-exchange resin D201.Leaching It is 100 times of resin volume to go out liquid product, pH value of solution=12, and temperature is 100 DEG C, and the exchange reaction time is 120min, V recovery rates For 99.1%, W 98.9%, mother liquor carries out second extraction.It is to resin regenerated from washing, recovery time with 2g/LNaOH solution 120min, regeneration temperature are 100 DEG C, obtain vanadium tungsten mixing sodium salt solution；

（4）Step（2）Described in leachate in V and W with strong-base anion-exchange resin D201 separate.Leachate Volume is 100 times of resin volume, and pH value of solution=11, temperature is 90 DEG C, and the exchange reaction time is 100min, and V recovery rates are 99.1%, W 0.1%, obtain negative vanadium resin and tungstenic extraction raffinate.With 5g/L NaOH solution to resin regenerated from washing, recovery time For 120min, regeneration temperature is 90 DEG C, obtains sodium vanadate solution；

（5）Step（3）Obtained vanadium tungsten mixing sodium salt solution first adjusts V and W ratio, then adjust pH=3, then by than Example dissolves in Na₂TiO₃, obtained vanadium tungsten titanium mixed solution prepares vanadium tungsten system SCR denitration powder with the precipitation method.First by vanadium tungsten Titanium mixed solution adjusts pH=8, then adds calcium nitrate, is filtrated to get vanadium tungsten titanium mixed precipitation.Mixed precipitation is first molten with nitric acid Solution, and continue to be acidified to pH=1.5, then through evaporative crystallization, washing, 105 DEG C of dryings and 700 DEG C of roastings, obtain 1.2%V₂O₅- 2.3%WO₃/TiO₂It is SCR catalyst powder.Take 50g to be milled to 0.1mm catalyst powder, it is fine then to add adhesive methyl Plain 5g and particle diameter are tieed up as dry-mixed 20min after 0.1mm absorbent charcoal powder body 3g.After well mixed, 10mL water, extrusion aid are sequentially added Monoethanolamine 5mL and lubricating oil glycerine 2mL, kneading operation then is carried out to wet stock with rolling rod, obtains plasticity lotion.With 50* 100mm corrugated fiber board is carrier, and fiberboard thickness 0.5mm, both sides uniformly coat the thick plasticity of 0.5mm to fiberboard up and down Lotion.Sieve plate with plasticity lotion is dried into 24h at 105 DEG C, after being then calcined 20h at 450 DEG C, obtains 1.3% V₂O₅-2.2%WO₃/TiO₂It is corrugated plate dst catalyst；

（6）Step（4）Obtained sodium vanadate solution regulation pH=9, add ammonium nitrate precipitation, obtained ammonium metavanadate precipitate Scrubbed, drying and calcination, obtained vanadic anhydride product, purity 99.7%；Step（4）Obtained tungstenic extraction raffinate regulation PH=1.5, then through evaporative crystallization, washing and drying, obtain tungstenic acid product, purity 99.5%.

Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although reference The present invention is described in detail for preferred embodiment, it will be understood by those within the art that, can be to the present invention Technical scheme modify or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, it all should cover Among the scope of the claims of the present invention.

Claims (9)

1. a kind of recovery and treatment method of useless SCR denitration, it is characterised in that comprise the following steps：

(1) useless SCR denitration is pre-processed, removes the removal of impurity, activation vanadium tungsten catalyst component；

(2) the useless SCR denitration obtained after being pre-processed to step (1) leaches, and obtains leached mud and leachate；

(3) each valuable element separates in the leachate obtained to step (2), obtains vanadium purification and tungsten/molybdenum/tungsten is rich Collect thing；

(4) the vanadium purification that step (3) obtains is further purified, for preparing vanadium product；Obtained tungsten/molybdenum/tungsten enrichment Thing is further purified, for preparing tungsten/molybdenum/tungsten product；

(5) valuable element synchronizes purifying in the leachate for obtaining step (2), adjusts the ratio of each content of material, from And catalyst component mixture is obtained, for being further prepared as new SCR denitration；

Leaching agent in step (2) leaching is neutral or acid or alkaline solution, and the liquid-solid ratio of leaching agent and dead catalyst is 0.02~1L/g, extraction temperature are 20~200 DEG C, and leaching pressure is 0.1~1MPa, and extraction time is 0.5~5h, mixing speed For 100~5000r/min；

When each valuable element is separated with extraction in leachate described in step (3), extractant be amine, organic phosphine acids, Organosilane ester, neutral phosphine, quaternary ammonium salt and oximes, extractant concentration are 5%~30%, initial pH=1~9 of aqueous phase, extraction Temperature is 10~40 DEG C, and extraction time is 10~40min.

2. the method as described in claim 1, it is characterised in that leaching agent is neutral or alkaline solution.

3. a kind of recovery and treatment method of useless SCR denitration, it is characterised in that comprise the following steps：

(1) useless SCR denitration is pre-processed, removes the removal of impurity, activation vanadium tungsten catalyst component；

(2) the useless SCR denitration obtained after being pre-processed to step (1) leaches, and obtains leached mud and leachate；

(3) each valuable element separates in the leachate obtained to step (2), obtains vanadium purification and tungsten/molybdenum/tungsten is rich Collect thing；

(4) the vanadium purification that step (3) obtains is further purified, for preparing vanadium product；Obtained tungsten/molybdenum/tungsten enrichment Thing is further purified, for preparing tungsten/molybdenum/tungsten product；

(5) valuable element synchronizes purifying in the leachate for obtaining step (2), adjusts the ratio of each content of material, from And catalyst component mixture is obtained, for being further prepared as new SCR denitration；

Leaching agent in step (2) leaching is neutral or acid or alkaline solution, and the liquid-solid ratio of leaching agent and dead catalyst is 0.02~1L/g, extraction temperature are 20~200 DEG C, and leaching pressure is 0.1~1MPa, and extraction time is 0.5~5h, mixing speed For 100~5000r/min；

In leachate described in step (3) during each valuable element Strong acid ion-exchanger, resin types are strong basicity or weak Alkalescence anion-exchange resin, leachate volume are 10~100 times of resin volume, and pH value of solution is 2~11, and temperature is 20~90 DEG C, swap time be 30~100min, resin regeneration liquid is strong basicity or weakly alkaline solution, and the recovery time is 20~120min, Regeneration temperature is 25~90 DEG C.

4. a kind of recovery and treatment method of useless SCR denitration, it is characterised in that comprise the following steps：

(1) useless SCR denitration is pre-processed, removes the removal of impurity, activation vanadium tungsten catalyst component；

(2) the useless SCR denitration obtained after being pre-processed to step (1) leaches, and obtains leached mud and leachate；

(3) each valuable element separates in the leachate obtained to step (2), obtains vanadium purification and tungsten/molybdenum/tungsten is rich Collect thing；

(4) the vanadium purification that step (3) obtains is further purified, for preparing vanadium product；Obtained tungsten/molybdenum/tungsten enrichment Thing is further purified, for preparing tungsten/molybdenum/tungsten product；

(5) valuable element synchronizes purifying in the leachate for obtaining step (2), adjusts the ratio of each content of material, from And catalyst component mixture is obtained, for being further prepared as new SCR denitration；

Leaching agent in step (2) leaching is neutral or acid or alkaline solution, and the liquid-solid ratio of leaching agent and dead catalyst is 0.02~1L/g, extraction temperature are 20~200 DEG C, and leaching pressure is 0.1~1MPa, and extraction time is 0.5~5h, mixing speed For 100~5000r/min；

When each valuable element in leachate described in step (3) is separated with the precipitation method, precipitating reagent and metal in leachate are total The mol ratio m of amount_pre：m_metal=1~6, pH value of solution=5~11, precipitation temperature be 20~80 DEG C, the sedimentation time be 20~ 120min。

5. the method as described in claim 1, it is characterised in that valuable element extraction in the leachate described in step (5) During Isolation, extractant is amine, organic phosphine acids, organosilane ester, neutral phosphine, quaternary ammonium salt or oximes extractant, is extracted It is 5%~30% to take agent concentration, and initial pH=1~10 of aqueous phase, extraction temperature is 10~40 DEG C, and extraction time is 10~40min.

6. the method as described in claim 1, it is characterised in that the valuable element ion in leachate described in step (5) During exchange process Isolation, resin types are strong basicity or weak-base anion-exchange resin, and leachate volume is resin volume 10~100 times, pH value of solution be 1~12, temperature is 10~100 DEG C, swap time is 30~120min, and resin regeneration liquid is strong Alkalescence or weakly alkaline solution, recovery time are 20~120min, and regeneration temperature is 20~100 DEG C.

7. the method as described in claim 1, it is characterised in that the valuable element in leachate described in step (5) is with coprecipitated During the method Isolation of shallow lake, the mol ratio m of precipitating reagent and total metal content in leachate_pre：m_metal=1~5, pH value of solution=6~12, Precipitation temperature is 10~90 DEG C, and the sedimentation time is 10~120min.

8. the method as described in any claim in claim 1-7, it is characterised in that the catalyst component described in step (5) The method that mixture prepares new SCR catalyst is infusion process, mixing method and the precipitation method, and new SCR catalyst is graininess, plate Formula, cellular and corrugated plate dst.

9. method as claimed in claim 8, it is characterised in that the method that catalyst component mixture prepares new SCR catalyst For infusion process, new SCR catalyst is graininess.