CN104805298A - Method for recovering waste SCR (Selective Catalytic Reduction) denitration catalyst - Google Patents

Method for recovering waste SCR (Selective Catalytic Reduction) denitration catalyst Download PDF

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Publication number
CN104805298A
CN104805298A CN201510265236.2A CN201510265236A CN104805298A CN 104805298 A CN104805298 A CN 104805298A CN 201510265236 A CN201510265236 A CN 201510265236A CN 104805298 A CN104805298 A CN 104805298A
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extraction
vanadium
leach liquor
tungsten
solution
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CN104805298B (en
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林晓
刘晨明
李志强
潘尹银
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Suzhou Bocui Recycling Technology Co.,Ltd.
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Beijing Saike Kanglun Environmental Science & Technology Co Ltd
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Priority to JP2017561394A priority patent/JP6661665B2/en
Priority to PCT/CN2015/090081 priority patent/WO2016187993A1/en
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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

Abstract

The invention relates to a method for recovering a waste SCR (Selective Catalytic Reduction) denitration catalyst. According to the method, the waste SCR denitration catalyst is subjected to pretreatment firstly so as to remove impurities and catalysis ingredients, such as activated vanadium, tungsten and molybdenum, and then, the waste SCR denitration catalyst is subjected to leaching, so as to obtain titanium-rich leached residue and a tungsten-molybdenum-vanadium-containing leachate; valuable elements in the leachate can be subjected to resource treatment through two methods: the first method comprises the steps of synchronously purifying the valuable elements in the leachate, then, proportionally adjusting the content of each substance so as to prepare a mixture of the catalysis ingredients, and further preparing a new catalyst so as to realize remanufacturing; the second method comprises the steps of separating and purifying each valuable element in the leachate, thereby preparing different products. The method can be used for recovering the valuable elements in the waste SCR denitration catalyst, and the environmental and economic benefits are remarkable.

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, particularly relate to a kind of recovery and treatment method of useless SCR denitration.
Background technology
China is that coal resources consume big country, and the burning of coal, while offering convenience for resident living, can produce again a large amount of oxynitride (NO x) and oxysulfide (SO 2).These oxynitride and oxysulfide are the chief components of topsoil, and severe contamination air ambient on the one hand, also can form acid rain on the other hand, bring huge hidden danger to natural water resources.Selective catalytic reduction (Selective Catalytic Reduction, SCR) be the comparatively reliable and simple denitration technology of technique of the one of rising in recent years, it is normally using ammonia as denitrfying agent, under the effect of SCR catalyst, is the nitrogen of pollution-free effect by oxynitride catalytic reduction.SCR catalyst mainly contains vanadium tungsten system, vanadium molybdenum system and vanadium tungsten system.Three is with V 2o 5and TiO 2as catalytic activity main body, be with WO unlike vanadium W-Sn deposits 3as auxiliary agent, vanadium molybdenum system is with MoO 3as auxiliary agent, vanadium tungsten system is then with WO 3and MoO 3as common auxiliary agent.In SCR technology, the investment of catalyzer is core, and the activity of catalyzer directly determines the efficiency of denitration.SCR denitration in use activity can decrease, and therefore, must carry out regeneration activating to using the catalyzer after certain hour.But some SCR catalyst are after repeatedly activating use, its original physical structure is seriously damaged, and be difficult to manipulation of regeneration, these catalyzer that cannot regenerate are useless SCR catalyst.
Mention in " the coal steam-electric plant smoke denitration engineering legislation-selective catalytic reduction " within 2012, carried out, to honeycomb fashion give up SCR denitration processing mode for crush landfill.But useless SCR catalyst is because of containing V 2o 5, WO 3or MoO 3deng toxic metal oxide compound, belong to hazardous solid waste, if press land-fill method to dispose SCR spent catalyst, not only can occupy a large amount of land resources, also can bring risk by environmental pollution, also will cause economical load to power plant and engineering corporation.In fact, honeycomb fashion gives up the WO that SCR catalyst itself contains 3, MoO 3, V 2o 5and TiO 2be all valuable resource, if the mode of separating-purifying can be taked to be reclaimed, not only can produce new profit growth point, also can reach various material in denitrating flue gas industrial chain and form the good result of closed cycle.
Patent CN104192911A discloses a kind of method reclaiming tungstic oxide composition in waste and old SCR denitration.It is that waste and old SCR denitration is fully crushed to dry powder, the tungstic oxide composition of particular solution under certain condition in catalyst-solvent is utilized after high-temperature roasting, tungstic oxide is effectively separated with other composition in catalyzer, collect upper strata tungstenic clear liquid by its evaporate to dryness, by fully dry for the solid obtained, after high-temperature roasting, complete the recovery to tungstic oxide composition.
Patent CN104195342A discloses a kind of method reclaiming Vanadium Pentoxide in FLAKES composition in waste and old SCR denitration.It first utilizes reductive agent that the pentavalent vanadium in catalyzer is reduced to more easily molten tetravalence vanadium in an acidic solution, then again the tetravalence vanadium in acidic solution is oxidized to pentavalent vanadium with oxygenant, by the pH value of regulator solution, pentavalent vanadium is made fully to be hydrolyzed and to precipitate under certain condition, collecting precipitation can obtain highly purified Vanadium Pentoxide in FLAKES through calcination process, and purity of vanadium pentoxide is 98%.
Patent CN103130265A discloses a kind of method of recovery Pd white powder from waste and old SCR denitration.It first carries out dedusting to useless denitrating catalyst, pulverizes abrasive dust, then adds the vitriol oil and obtains titanyl sulfate strong solution by after its acidolysis, then thin up; Then add nonionic emulsifier as flocculation agent, sulfosalt surfactant or polycarboxylate tensio-active agent, as coagulant aids, then add Water-soluble methyl silicone oil; Pump into plate-and-frame filter press again and carry out press filtration, reheat concentrated for filter vacuum to 90 DEG C-98 DEG C and keep filtrate being hydrolyzed in 5.5 hours; Then hydrolysate is cooled to 40 DEG C, carries out vacuum filtration and metatitanic acid is deposited; After using sand leaching water and rinsed with deionized water again, add salt of wormwood or phosphoric acid obtains metatitanic acid filter cake; Calcine at 500-800 DEG C after filter cake is dried, then pulverize, levigately obtain finished titanium dioxide.
Patent CN104261415A discloses a kind of method reclaiming silicon-dioxide in discarded SCR catalyst completely.By the water soaking removal of impurities of the discarded SCR catalyst after pulverizing with 3 ~ 4 times of volumes, after removal of impurities, the powder concentrated alkali solution that excessive concentration is 60 ~ 80wt% leaches, and adopts filtration to obtain solid meta-titanium perborate Na 2tiO 3, in filtrate, add sulfuric acid, at 70 ~ 90 DEG C, regulate pH to 11.5 ~ 12.5, leave standstill 0.5 ~ 1h, filter and discard filter cake; In filtrate, add sulfuric acid to be again adjusted to pH be 9 ~ 10 filter cakes obtained is silicic acid, silicic acid filter cake, in nitration mixture 40 ~ 60 DEG C of heated and stirred 1 ~ 2h of dilute sulphuric acid and oxalic acid, filters, uses deionized water wash filter cake, wash the acid ion contained by solid off, obtain high-purity silicon dioxide through thermal degradation.
Patent CN104275178A discloses a kind of reclaiming of discarded SCR denitration and the method for regeneration SCR catalyst carrier.By discarded SCR catalyst through pulverizing, sieving, wash, after pickling, then through wet pulverization, grinding, obtain catalyst slurry.Again slurry is mixed with metatitanic acid slurries, obtain mixed serum.By mixed serum after washing, filtration, dehydration, regulating pH, add Bleached.Slurries after bleaching add water, regulate pH, add ammonium paratungstate and white carbon black, through stirring, filtering, dewater, calcine, pulverize, obtain the catalyzer of reclaiming.
Patent CN104263946A discloses a kind of method reclaiming tungsten, vanadium, titanium from SCR denitration spent catalyst.By pulverizing after the cleaning of SCR spent catalyst, sieving, mix sodium carbonate and stir, mixed powder is at high temperature sintered and obtains sintered material, then the leaching that adds water, obtain the sodium salt mixing solutions containing tungsten, vanadium; Be greater than selective extraction tungsten under the condition of 12 in solution ph, carry out back extraction with ammonium salt solution and obtain ammonium tungstate solution; Raffinate after extraction tungsten is extracting vanadium under the condition of 10 ~ 11.5 in pH value, carries out with sodium hydroxide solution the sodium vanadate solution that back extraction obtains containing a small amount of tungsten; Titanium is stayed in leached mud and is obtained rich titanium material.
Patent CN104178636A discloses a kind of activation burning reclaims Ti, V, Mo, Si in SCR spent catalyst method in conjunction with acidic leaching.Its treatment step is: first by the pre-treatment of SCR spent catalyst, then high-temperature calcination activation.Then to calcinate acidic leaching, white TiO is obtained 2powder.After leach liquor evaporation concentration, obtain white precipitate H 2moO 4.Leach liquor adds ammoniacal liquor and regulates pH to 8.0 ~ 9.0, obtains NH 4vO 3precipitation.Again leach liquor is added ammoniacal liquor and regulate pH to 8.0 ~ 9.0, then add MgCl 2obtain MgSiO 3.Filtrate after filtration enters sewage recovering system.
Patent CN104326506A discloses a kind of method for reclaiming titanium dioxide in inefficacy denitrating catalyst.It comprises the following steps: out of stock for inefficacy catalyzer is ground to and is Powderedly placed in open container by (1), drips appropriate distilled water and prevent from tying the end in open container; (2) acidolysis, massfraction be 98% the vitriol oil add open container, to open container heating make powder dissolution, in heat-processed, Keep agitation makes solid-liquid mix, when the solution in open container is brown color stop heating, be cooled to≤30 DEG C obtain titanium liquid; (3) neutralize, the lime milk solution being 80% by massfraction 50% ~ 80% Calcium of intensifiens content is dropwise added drop-wise in titanium liquid, and dropping limit, limit shakes up, and controls titanium liquid temp≤70 DEG C, is fully cooled to room temperature after reaction; (4) concentrated hydrolysis, is concentrated into 195-205g/l by the titanium liquid after neutralization, adds crystal seed heating hydrolysis, obtains titanium salt after filtration, rinsing, oven dry calcining.
The circulation that above-mentioned existing SCR denitration recycling technology all cannot realize useless SCR denitration manufactures again, also cannot realize the high efficiency separation of the valuable elements such as V, W, Mo and Ti and obtain the vanadium tungsten product of purity more than 99% simultaneously.Up to now, China does not also have the recycling Engineering Projects of the useless SCR catalyst of a set of maturation, and be does not have mature and feasible, the suitable waste catalyst recovery treatment technology promoted after all.
Summary of the invention
Based on the reality that the recycling technology of current useless SCR denitration lacks, the present invention proposes one and both can realize useless SCR denitration and manufacture, again can as required by the method for the valuable component Separation and Recovery such as vanadium tungsten and purifying, wherein the rate of recovery of valuable metal surpasses 95%, and the purity of vanadium/tungsten/vanadium molybdenum product can reach more than 99%.
For reaching this object, the present invention by the following technical solutions:
A recovery and treatment method for useless SCR denitration, comprises the steps:
(1) will give up the catalyst components such as SCR denitration pre-treatment, removal impurity, activation vanadium tungsten;
(2) the useless SCR denitration obtained after step (1) pre-treatment is leached, obtain leached mud and leach liquor;
(3) in the leach liquor obtained step (2), each valuable element is separated, and obtains vanadium purification thing and tungsten/molybdenum/tungsten enriched substance;
(4) the vanadium purification thing that step (3) obtains is further purified, for the preparation of vanadium product; Tungsten/molybdenum/tungsten the enriched substance obtained is further purified, for the preparation of tungsten/molybdenum/tungsten product.
(5) in leach liquor step (2) obtained, valuable element carries out Isolation, regulates the ratio of each substances content, thus obtains catalyst component mixture, for being prepared as new SCR denitration further.
Step (1) removes the important step of the catalyst component such as impurity in useless SCR denitration, activation vanadium tungsten.SCR denitration can carry the impurity such as some dusts, sand grains and oil content in life-time service process, and these impurity can affect the purity of subsequent product.V in addition in spent catalyst 2o 5, WO 3, MoO 3for indissoluble thing.Therefore, pre-treatment need be carried out to spent catalyst, the catalyst components such as the impurity that removal is carried and activation vanadium tungsten.In step (1), pretreatment process can be washing, pulverizing, roasting and drying etc.Washing and dry dust, sand grains and the oil content can removed spent catalyst and carry; Pulverizing can improve the specific surface area of spent catalyst; Roasting can by the V in spent catalyst 2o 5, WO 3, MoO 3activation, is converted into VO soluble in water 4 3-, WO 4 2-, MoO 4 2-.Need add additive during calcination activation, additive can be alkali metal base or salt, and for cost-saving, being preferably soda or sodium salt, such as, is NaOH or Na 2cO 3deng.The mol ratio m of additive and Metals from Spent Catalysts total amount add: m metal=1 ~ 6, such as 1.2,1.4,1.6,1.8,2.3,3,3.8,4.8,5.3 and 5.8 etc.Maturing temperature is 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) is the main process from solid phase extractions vanadium tungsten.Leaching agent can in neutral acid or alkaline, if leaching agent is in acid, then other metals such as the Ti etc. in spent catalyst except V, W and Mo also can enter solution, and this can make leach liquor composition more complicated, increases the separating difficulty of follow-up each component.Therefore, in the present invention, leaching agent is preferably neutral or alkaline.The liquid-solid ratio of leaching agent and product of roasting is 0.02 ~ 1L/g, such as, be 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 is 20 ~ 200 DEG C, such as, be 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, such as, be 0.75h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h and 4.5h etc.Leaching pressure is 0.1 ~ 1MPa, such as, be 0.2MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa and 1.0 MPa etc.Leaching stirring velocity is 100 ~ 5000r/min, such as, be 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) is the core operation that in leach liquor, each valuable element is separated.When valuable element extraction process in leach liquor is recorded separately, extraction agent can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and oximes, be such as primary amine class N1923, Primene JMT, Primene 81R and LK-N21, secondary amine class DIDA, Di-Octyl amine/octane, Di-Octyl amine/tetracol phenixin, tertiary amines Alamine 336, quaternary amine Aliquat 336, neutral phosphine class TBP, organosilane ester amyl acetate-n and organic phosphates D2EHPA, oximes Lix63; Extractant concentration is 5% ~ 30%, such as, be 10%, 15%, 20% and 25% etc.; Initial pH=1 ~ 9 of aqueous phase are such as 1.5,2,2.5,3,3.5,4,5,6,7 and 8 etc.; Extraction temperature is 10 ~ 40 DEG C, such as, be 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C and 35 DEG C etc.; Extraction time is 10 ~ 40min, such as, be 15 min, 20 min, 25 min, 30 min and 35 min etc.; When carrying out back extraction to organic phase, reverse-extraction agent can be alkali lye or ammoniacal liquor, the NH in reverse-extraction agent 4 +or OH -with the mol ratio m of total metal content nH4+/ m oH -: m metal=1 ~ 10, be such as 2,3,5,7 and 9 etc.Wherein concentration of lye is 1 ~ 10g/L, such as, be 2 g/L, 4 g/L, 6 g/L, 8 g/L and 9 g/L; Ammonia concn is 5% ~ 30%, such as, be 10%, 15%, 20%, 25% and 28% etc.Back extraction temperature is 20 ~ 70 DEG C, such as, be 30,40,50 and 60 DEG C; Stripping times is 0.5 ~ 4h, such as, be 1,1.5,2,2.5,3 and 3.5 etc.
During each valuable element Strong acid ion-exchanger in leach liquor, resin types is strong basicity or weak base anion-exchange resin, such as, be D418, D301 etc.; Leach liquor volume is 10 ~ 100 times of resin volume, such as, be 20,30,40,50,60,70,80 and 90 etc.; PH value of solution is 2 ~ 11, such as, be 2,4,6,8 and 9 etc.; Temperature is 20 ~ 90 DEG C, such as, be 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, such as, be 20 min, 40 min, 60 min and 80 min etc.; Resin regeneration liquid is highly basic or weak caustic solution, such as, be NaOH, Na 2cO 3with ammoniacal liquor etc.; Recovery time is 20 ~ 120min, such as, be 30min, 50 min, 60 min, 70 min, 80 min, 90 min and 110 min etc.; Regeneration temperature is 25 ~ 90 DEG C, such as, be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C and 80 DEG C etc.;
When each valuable element precipitator method in leach liquor are separated, precipitation agent is an alkali metal salt etc., such as, be Ca (NO 3) 2, CaCl 2, Mg (NO 3) 2, MgCl 2, BaCl 2with Ba (NO 3) 2deng; The mol ratio m of total metal content in precipitation agent and leach liquor pre: m metal=1 ~ 6, be such as 1.5,2,2.5,3,3.5,4,4.5 and 5 etc.; PH value of solution=5 ~ 11 are such as 6,7,8,9 and 10 etc.; Precipitation temperature is 20 ~ 80 DEG C, such as, be 20,30,40,50,60 and 70 DEG C; Sedimentation time is 20 ~ 120min, such as, be 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min and 110 min etc.;
Step (4) is the important step that vanadium purification thing and tungsten/molybdenum/tungsten enriched substance were further purified, prepared vanadium and tungsten/molybdenum/tungsten product respectively.The method that vanadium purification thing is further purified is precipitation, extraction, ion-exchange and membrane sepn etc.Ammonium metavanadate precipitate can obtain the Vanadium Pentoxide in FLAKES product of purity more than 99.5% through dissolving, redeposition, washing, drying and roasting.Also high purity vanadic anhydride product can be obtained containing vanadium solution extracting-back extraction precipitation-drying-sinter process.The pure vanadium liquid of lower concentration utilizes electrodialytic technique to be concentrated.Also available ions exchange process vanadium extraction from the vanadium solution of lower concentration, then can obtain vanadic salts product through resin regenerated from washing, evaporative crystallization and drying.The method that tungsten/molybdenum/tungsten enriched substance is further purified is precipitation, extraction, ion-exchange and membrane sepn etc.Sodium molybdate solution first with amine extractant extraction, then can obtain ammonium molybdate solution with ammoniacal liquor back extraction, then can obtain molybdenum trioxide product through evaporation concentration, washing, drying and roasting.Calcium wolframate precipitation can obtain pure tungsten acid calcium product through dissolving, redeposition and drying.Ammonium molybdate solution containing a small amount of vanadium can remove vanadium through nanofiltration membrane and ion-exchange, obtains pure ammonium molybdate solution.Pure sodium molybdate solution can prepare the molybdic acid product of purity more than 99.1% through acidifying, evaporation and drying.
Step (5) is the committed step of vanadium tungsten Isolation in leach liquor.There is the method for valency group Isolation can be co-precipitation, extraction and ion-exchange etc. in leach liquor.When valuable element in leach liquor is with extraction process Isolation, extraction agent can be amine, organophosphorus acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and oximes, be such as primary amine class N1923, Primene JMT, Primene 81R and LK-N21, secondary amine class DIDA, Di-Octyl amine/octane, Di-Octyl amine/tetracol phenixin, tertiary amines Alamine 336, quaternary amine Aliquat 336, neutral phosphine class TBP, organosilane ester amyl acetate-n and organic phosphates D2EHPA, oximes Lix63; Extractant concentration is 5% ~ 30%, such as, be 10%, 15%, 20% and 25% etc.; Initial pH=1 ~ 10 of aqueous phase are such as 1.5,2,2.5,3,3.5,4,5,6,7,8 and 9 etc.; Extraction temperature is 10 ~ 40 DEG C, such as, be 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C and 35 DEG C etc.; Extraction time is 10 ~ 40min, such as, be 15 min, 20 min, 25 min, 30 min and 35 min etc.; When carrying out back extraction to organic phase, reverse-extraction agent can be alkali lye or ammoniacal liquor, the NH in reverse-extraction agent 4 +or OH -with the mol ratio m of total metal content nH4+/ m oH -: m metal=1 ~ 10, be such as 2,3,5,7 and 9 etc.Wherein concentration of lye is 1 ~ 10g/L, such as, be 2 g/L, 4 g/L, 6 g/L, 8 g/L and 9 g/L; Ammonia concn is 5% ~ 30%, such as, be 10%, 15%, 20%, 25% and 28% etc.Back extraction temperature is 20 ~ 70 DEG C, such as, be 30,40,50 and 60 DEG C; Stripping times is 0.5 ~ 4h, such as, be 1,1.5,2,2.5,3 and 3.5 etc.
When valuable element in leach liquor is with ion exchange method Isolation, resin types is strong basicity or weak base anion-exchange resin, such as, be D418, D301 etc.; Leach liquor volume is 10 ~ 100 times of resin volume, such as, be 20,30,40,50,60,70,80 and 90 etc.; PH value of solution is 1 ~ 12, such as, be 2,4,6,8 and 10 etc.; Temperature is 10 ~ 100 DEG C, such as, be 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, such as, be 20 min, 40 min, 60 min, 80 min and 100 min etc.; Resin regeneration liquid is highly basic or weak caustic solution, such as, be NaOH, Na 2cO 3with ammoniacal liquor etc.; Recovery time is 20 ~ 120min, such as, be 30min, 50 min, 60 min, 70 min, 80 min, 90 min and 110 min etc.; Regeneration temperature is 20 ~ 100 DEG C, such as, be 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 leach liquor is with coprecipitation method Isolation, precipitation agent is an alkali metal salt etc., such as, be Ca (NO 3) 2, CaCl 2, Mg (NO 3) 2, MgCl 2, BaCl 2with Ba (NO 3) 2deng; Precipitation agent with
Step (5) is also the core procedure that catalyst component mixture prepares new SCR denitration.SCR denitration can be divided into particulate state and integral catalyzer according to outward appearance, and wherein integral catalyzer is divided into again board-like, cellular and waved plate catalyzer.Pellet type catalyst is adopt impregnation technology by TiO mostly 2powder fully floods and obtains through evaporate to dryness, drying and calcination in the precursor solution of ammonium meta-vanadate with other promotors.Board-like catalyzer adopts metal sieve plate as carrier, and physical strength is good, the coal-fired high grey SCR denitration occasion of particularly suitable; Honeycombed catalyst is with SCR catalyst powder for matrix, with shaping assistant etc. by mixing, mediating, extrusion molding, the process such as drying and calcination obtain.And corrugated plate dst catalyzer take corrugated as carrier, be coated with the coating containing active ingredient, active substance fewer than honeycombed catalyst 70% on its surface, after surfactant wearing and tearing are run off, catalytic activity declines very fast, and work-ing life is shorter.Cellular and board-like catalyzer is all first with V 2o 5/ TiO 2base SCR catalyst powder is raw material, fully mixes kneading obtain plasticity lotion with water, tackiness agent, extrusion aid, expanding agent, lubricant, glass fibre etc., then honeycombed catalyst with plasticity lotion for matrix obtains through extrusion molding, drying and calcination.And tabular catalyzer is evenly compressed in metal sieve plate by plasticity lotion, obtain catalyzer by dry, calcination.The mol ratio m of total metal content in leach liquor pre: m metal=1 ~ 5, be such as 1.5,2,2.5,3,3.5,4 and 4.5 etc.; PH value of solution=6 ~ 12 are such as 7,8,9,10 and 11 etc.; Precipitation temperature is 10 ~ 90 DEG C, such as, be 20,30,40,50,60,70 and 80 DEG C; Sedimentation time is 10 ~ 120min, such as, be 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 precipitator method, pickling process, hybrid system, ion exchange method, roller painting and heat melting method etc.Pickling process is that the fluent meterial leaching containing active ingredient and cocatalyst component is loaded in solid-state carrier on the surface.Its carrier utilization ratio is high, and consumption is few, and cost is low, is widely used in the preparation of loaded catalyst, is particularly useful for low content of noble metal catalyzer; The precipitator method are, with precipitation agent, the catalyst component of solubility is converted into indissoluble or insoluble compound, through being separated, washing, dry, calcining, the operation such as shaping, obtained finished catalyst.For the base metal of high-content, metal oxide, metal salt catalyst or support of the catalyst; Hybrid system equipment is simple, and easy to operate, product chemical constitution is stablized, and can be used for the multicomponent catalyst preparing high-content, especially mixed oxide catalyst, but this method dispersity is lower; Active ingredient mucilage is placed in the container that can shake by roller painting, and thereon, through rolling after a while, active ingredient just sticks to carrier surface to non-porous support bead cloth gradually.Because active ingredient is easily peeled off, roller painting potassium hydroxide; Ion exchange method makes carrier with exchanger, introduces active ingredient with the form of gegenion, the load type metal on preparation high dispersive, large surface or metal ion catalyst, is particularly useful for the noble metal catalyst preparation of low levels, high utilization rate; High-temperature melting method borrows hot conditions that each component of catalyzer fusion is become equally distributed mixture, oxide solid solution or alloy solid solution, to produce the catalyzer of property.Be mainly used in the preparation of ammonia synthesis fused iron catalyst, Fischer-Tropsch catalyst, blue Buddhist nun's skeleton catayst etc.
Integrated comparative, the present invention preferably prepares SCR catalyst powder by pickling process.
When producing preformed catalyst as board-like and honeycomb-shaped SCR denitrating catalyst, conventional forming method has: (1) spray shaping: the colloidal sol configured or suspension shower nozzle are disperseed at drying tower internal spraying, microspheroidal xerogel is become, size range 30 ~ 200 microns after warm air drying; (2) forming oil column: material solution is divided into two-way, low pressure shower nozzle is squeezed into by certain flow rate, mix and form colloidal sol rapidly in shower nozzle, being dispersed in warm light oil or transformer oil column with small droplets state after leaving shower nozzle, in several seconds, condensing into hydrogel.The product of spray shaping and forming oil column gained, regular shape, smooth surface, physical strength is good; (3) rotational forming: the powder of drying is placed in rotating disk that turn round, inclination 30 ~ 60 °, and spray into vaporific binding agent, the topical powder wet first is bonded as core.Along with the continuous motion of rotating disk, core gradually grows up as ball, little compared with large ball frictional coefficient, and rolling of floating on the surface, just rolls out from rotating disk lower edge when meeting granularity requirements; (4) extruded moulding: powder adds suitable binding agent, through roll knead after just form the good pureed mucilage of plasticity.Utilize piston or spiral to force slurry by porous plate, be cut into the isometrical bar shaped right cylinder of nearly equal length or ring cylinder, drying, calcining just obtain product.(5) compression molding: many powder materials are made the sheet right cylinder that profile is consistent, size is even, physical strength is high or ring cylinder.
As optimal technical scheme, method of the present invention, comprises the steps:
(1) will give up the catalyst components such as SCR denitration pre-treatment, removal impurity, activation vanadium tungsten;
(2) spent catalyst obtained after pre-treatment in step (1) is leached, obtain leached mud and leach liquor; Leaching agent is neutral or alkaline, and the liquid-solid ratio of leaching agent and spent catalyst is 0.02 ~ 1L/g, and extraction temperature is 20 ~ 200 DEG C, and leaching pressure is 0.1 ~ 1MPa, and extraction time is 0.5 ~ 5h, and stirring velocity is 100 ~ 5000r/min;
(3) each valuable element extraction process in step (2) leach liquor or ion exchange method or the precipitator method are separated.During extraction process, extraction agent can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and oximes, and extractant concentration is 5% ~ 30%, initial pH=1 ~ 9 of aqueous phase, and extraction temperature is 10 ~ 40 DEG C, and extraction time is 10 ~ 40min; During ion exchange method, resin types is strong basicity or weak base anion-exchange resin, leach liquor volume is 10 ~ 100 times of resin volume, pH value of solution is 2 ~ 11, temperature is 20 ~ 90 DEG C, swap time is 30 ~ 100min, resin regeneration liquid is highly basic or weak caustic solution, and the recovery time is 20 ~ 120min, and regeneration temperature is 25 ~ 90 DEG C; During coprecipitation method, the mol ratio m of total metal content in precipitation agent and leach liquor pre: m metal=1 ~ 6, pH value of solution=5 ~ 11, precipitation temperature is 20 ~ 80 DEG C, and sedimentation time is 20 ~ 120min; The vanadium purification thing obtained and tungsten/molybdenum/tungsten enriched substance are further purified, prepare vanadium and tungsten/molybdenum/tungsten product.
Or (4) by carrying out the adjustment of each matter content ratio after the valuable element Isolation in step (2) leach liquor, prepare catalyst component mixture.Valuable element extraction process in leach liquor or ion exchange method or coprecipitation method Isolation.During extraction process, extraction agent can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and oximes, and extractant concentration is 5% ~ 30%, initial pH=1 ~ 10 of aqueous phase, and extraction temperature is 10 ~ 40 DEG C, and extraction time is 10 ~ 40min; During ion exchange method, resin types is strong basicity or weak base anion-exchange resin, leach liquor volume is 10 ~ 100 times of resin volume, pH value of solution is 1 ~ 12, temperature is 10 ~ 100 DEG C, swap time is 30 ~ 120min, resin regeneration liquid is highly basic or weak caustic solution, and the recovery time is 20 ~ 120min, and regeneration temperature is 20 ~ 100 DEG C; During coprecipitation method, the mol ratio m of total metal content in precipitation agent and leach liquor pre: m metal=1 ~ 5, pH value of solution=6 ~ 12, precipitation temperature is 10 ~ 90 DEG C, and sedimentation time is 10 ~ 120min;
(5) the catalyst component mixture pickling process described in step (3) is prepared as new granular SCR denitration powder.Catalyst component mixture is first dissolved in the oxalic acid solution of 0.1 ~ 0.2mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 2 ~ 4h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 12 ~ 24h of loft drier of 105 ~ 110 DEG C.Clayed into power by dried solid mixture, then insert roasting in retort furnace, maturing temperature is 400 ~ 600 DEG C, and roasting time is 5 ~ 12h.Roasting after product is new granular SCR denitration powder;
Compared with prior art, the present invention has following beneficial effect:
1, the inventive method is fabricated to highly active raw catalyst while achieving veritably and useless SCR denitration being obtained harmless treatment again, has good environmental benefit and economic benefit;
2, the valuable elements such as V, Mo and the W in useless SCR catalyst can be obtained abstraction and purification recovery by the inventive method, and the rate of recovery of V, Mo and W is all more than 95%, and obtained vanadium/tungsten/molybdenum/tungsten product purity reaches more than 99%.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the method for the invention.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, protection scope of the present invention is as the criterion with claims.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V 2o 5content is 1.1%, MoO 3be 3.3%, TiO 2be 95.3%.
(1) get the above-mentioned spent catalyst of 10g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried spent catalyst adds NaOH and makes additive, the mol ratio m of NaOH and Metals from Spent Catalysts total amount add: m metal=1.Mix and be placed on roasting in retort furnace, maturing temperature is 650 DEG C, and roasting time is 4h;
(2) make leaching agent with neutral pure water, after step (1) roasting, leach V and Mo spent catalyst, liquid-solid ratio is 0.02L/g, extraction temperature is 20 DEG C, and leaching pressure is 0.1MPa, and extraction time is 1.5h, stirring velocity is 1000r/min, V single-stage leaching yield be 78.6%, Mo is 75.7%; Leached mud returns step (1);
(3) with primary amine kind of extractants N1923 and toluene composition extraction system for organic phase, concentration is 5%, at the initial pH=1 of aqueous phase, two compare O/A=1, extraction temperature is 10 DEG C, under the condition that extraction time is 10min, from the leach liquor described in step (2), synchronous extraction V and Mo, V percentage extraction is 100%, Mo percentage extraction is 99.99%.Then with the ammoniacal liquor of 5%, vanadium molybdenum mixed-ammonium salt solution is obtained to the synchronous back extraction of V and Mo in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=1, back extraction temperature is 20 DEG C, and Stripping times is 0.5h.Regulate the ratio of V and Mo in vanadium molybdenum mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 50 DEG C must vanadium molybdenum mixed-ammonium salt;
(4) with primary amine kind of extractants N1923 and toluene composition extraction system for organic phase, concentration is 5%, at the initial pH=6 of aqueous phase, two compare O/A=1, extraction temperature is 10 DEG C, and under the condition that extraction time is 10min, from the leach liquor described in step (2), extracting and separating V and Mo, V percentage extraction are 100%, Mo percentage extraction is 0.5%, obtains rich vanadium organic phase and contains molybdenum raffinate.Rich vanadium organic phase with 10% ammoniacal liquor back extraction, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=3, back extraction temperature is 40 DEG C, and Stripping times is 1h, and back extraction obtains ammonium metavanadate precipitate;
(5) the vanadium molybdenum mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.2mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 2h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 12h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 400 DEG C, and roasting time is 5h.Roasting after product is granular 1.2%V 2o 5-3.5%MO 3/ TiO 2it is SCR denitration;
(6) ammonium metavanadate precipitate that step (4) obtains first uses nitric acid dissolve, then regulator solution pH=7, then adds ammonium sulfate precipitation, and the ammonium metavanadate precipitate obtained is through washing, dry and roasting, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.5%; What step (4) obtained regulates pH=1.5 containing molybdenum raffinate nitric acid, and 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, V 2o 5content is 1.4%, MoO 3be 3.2%, TiO 2be 95%.
(1) get the above-mentioned spent catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried spent catalyst adds NaOH and makes additive, the mol ratio m of NaOH and Metals from Spent Catalysts total amount add: m metal=2.Mix and be placed on roasting in retort furnace, maturing temperature is 680 DEG C, and roasting time is 5h;
(2) make leaching agent with neutral pure water, after step (1) roasting, leach V and Mo spent catalyst, liquid-solid ratio is 0.06L/g, extraction temperature is 60 DEG C, and leaching pressure is 0.1MPa, and extraction time is 2h, stirring velocity is 800r/min, V single-stage leaching yield be 79.6%, Mo is 77.4%; Leached mud returns step (1);
(3) with secondary amine kind of extractants Di-Octyl amine and octane composition extraction system for organic phase, concentration is 15%, at the initial pH=3 of aqueous phase, two compare O/A=1, extraction temperature is 20 DEG C, extraction time is that under the condition of 15min, from step (2) leach liquor, synchronous extraction V and Mo, V percentage extraction is 99.6%, Mo percentage extraction is 98.8%.Then with the ammoniacal liquor of 10%, vanadium molybdenum mixed-ammonium salt solution is obtained to the synchronous back extraction of V and Mo in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=4, back extraction temperature is 45 DEG C, and Stripping times is 3h.Regulate the ratio of V and Mo in vanadium molybdenum mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 55 DEG C must vanadium molybdenum mixed-ammonium salt;
(4) with secondary amine kind of extractants Di-Octyl amine and octane composition extraction system for organic phase, concentration is 15%, at the initial pH=5 of aqueous phase, two compare O/A=1, extraction temperature is 25 DEG C, and extraction time is that under the condition of 25min, from step (2) leach liquor, extracting and separating V and Mo, V percentage extraction are 99.5%, Mo percentage extraction is 0.12%, obtains rich vanadium organic phase and contains molybdenum raffinate.Ammoniacal liquor with 15% obtains ammonium metavanadate precipitate to the back extraction of rich vanadium organic phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=10, back extraction temperature is 70 DEG C, and Stripping times is 4h;
(5) the vanadium molybdenum mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.15mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 2.5h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 15h of electric drying oven with forced convection of 105 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 450 DEG C, and roasting time is 6h.Roasting after product is granular 1.1%V 2o 5-3.1%MO 3/ TiO 2it is SCR denitration.
(6) ammonium metavanadate precipitate that step (4) obtains first uses nitric acid dissolve, then regulator solution pH=7.5, then adds ammonium nitrate precipitation, and the ammonium metavanadate precipitate obtained is through washing, dry and roasting, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.6%; What step (4) obtained regulates pH=1.2 containing molybdenum raffinate nitric acid, and then through evaporative crystallization, washing and drying, obtain molybdic acid product, purity is 99.2%.
Embodiment 3
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V 2o 5content is 1.5%, WO 3be 3.3%, TiO 2be 95%.
(1) get the above-mentioned spent catalyst of 10g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried spent catalyst adds Na 2cO 3make additive, Na 2cO 3with the mol ratio m of Metals from Spent Catalysts total amount add: m metal=6.Mix and be placed on roasting in retort furnace, maturing temperature is 500 DEG C, and roasting time is 7h;
(2) make leaching agent with neutral pure water, after step (1) roasting, leach V and W spent catalyst, liquid-solid ratio is 0.05L/g, extraction temperature is 70 DEG C, and leaching pressure is 0.1MPa, and extraction time is 1.5h, stirring velocity is 1200r/min, V single-stage leaching yield be 79.6%, W is 76.4%; Leached mud returns step (1);
(3) with tertiary amines extraction agent Alamine 336 and kerosene composition extraction system for organic phase, concentration is 25%, at the initial pH=4 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, extraction time is that under the condition of 40min, from step (2) leach liquor, synchronous extraction V and W, V percentage extraction is 98.6%, W percentage extraction is 99.6%.Then with the ammoniacal liquor of 20%, vanadium tungsten mixed-ammonium salt solution is obtained to the synchronous back extraction of V and W in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=6, back extraction temperature is 50 DEG C, and Stripping times is 3h.Regulate the ratio of V and W in vanadium tungsten mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 48 DEG C must vanadium tungsten mixed-ammonium salt;
(4) with tertiary amines extraction agent Alamine 336 and kerosene composition extraction system for organic phase, concentration is 25%, at the initial pH=1.0 of aqueous phase, two compare O/A=1, extraction temperature is 25 DEG C, and extraction time is that under the condition of 20min, from step (2) leach liquor, extracting and separating V and W, V percentage extraction are 100%, W percentage extraction is 0.2%, obtains rich vanadium organic phase and tungstenic raffinate.By the NaOH solution of 1g/L to the back extraction of rich vanadium organic phase, the OH wherein added -with the mol ratio m of total metal content in organic phase oH -: m metal=10, back extraction temperature is 70 DEG C, and Stripping times is 4h, obtains sodium vanadate solution;
(5) the vanadium tungsten mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.16mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 3h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 16h of electric drying oven with forced convection of 106 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 500 DEG C, and roasting time is 5.5h.Roasting after product is granular 1.2%V 2o 5-3.0%WO 3/ TiO 2it is SCR denitration;
(6) sodium vanadate solution that step (4) obtains regulates pH=8, adds ammonium sulfate precipitation, and the ammonium metavanadate precipitate obtained is through washing, dry and roasting, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.5%; The tungstenic raffinate nitric acid that step (4) obtains regulates pH=1.0, then through evaporative crystallization, washing and drying, obtains tungstenic acid product, and purity is 99.0%.
Embodiment 4
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V 2o 5content is 1.3%, WO 3be 3.2%, TiO 2be 95.2%.
(1) get the above-mentioned spent catalyst of 10g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried spent catalyst adds NaCl and makes additive, the mol ratio m of NaCl and Metals from Spent Catalysts total amount add: m metal=4.5.Mix and be placed on roasting in retort furnace, maturing temperature is 700 DEG C, and roasting time is 4h;
(2) make leaching agent with neutral pure water, after step (1) roasting, leach V and W spent catalyst, liquid-solid ratio is 0.1L/g, extraction temperature is 80 DEG C, and leaching pressure is 0.2MPa, and extraction time is 3h, stirring velocity is 5000r/min, V single-stage leaching yield be 78.8%, W is 75.9%; Leached mud returns step (1);
(3) with quaternary amine Aliquat 336 and kerosene composition extraction system for organic phase, concentration is 25%, at the initial pH=3 of aqueous phase, two compare O/A=1, extraction temperature is 30 DEG C, extraction time is that under the condition of 30min, from step (2) leach liquor, synchronous extraction V and W, V percentage extraction is 98.7%, W percentage extraction is 98.90%.Then with the ammoniacal liquor of 20%, vanadium tungsten mixed-ammonium salt solution is obtained to the synchronous back extraction of V and W in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=5, back extraction temperature is 45 DEG C, and Stripping times is 3h.Regulate the ratio of V and W in vanadium tungsten mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 45 DEG C must vanadium tungsten mixed-ammonium salt;
(4) with quaternary amine Aliquat 336 and kerosene composition extraction system for organic phase, concentration is 25%, at the initial pH=9.0 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, and extraction time is that under the condition of 40min, from step (2) leach liquor, extracting and separating V and W, V percentage extraction are 0.2%, W percentage extraction is 99.6%, obtains rich tungsten organic phase and contains vanadium raffinate.By the NaOH solution of 10g/L to the back extraction of rich tungsten organic phase, the OH wherein added -with the mol ratio m of total metal content in organic phase oH -: m metal=5, back extraction temperature is 30 DEG C, and Stripping times is 0.5h, obtains sodium tungstate solution;
(5) the vanadium tungsten mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.2mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 4h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 18h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 550 DEG C, and roasting time is 7h.Roasting after product is granular 1.3%V 2o 5-3.4%WO 3/ TiO 2it is SCR denitration;
(6) the sodium tungstate solution nitric acid that step (4) obtains regulates pH=1.5, and then through evaporative crystallization, washing, drying and calcining, obtain tungstic oxide product, purity is 99.2%; What step (4) obtained regulates pH=7.2 containing vanadium raffinate, then adds ammonium chloride precipitation, and the ammonium metavanadate precipitate obtained is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.6%.
Embodiment 5
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V 2o 5content is 1.3%, WO 3be 2.4%, TiO 2be 96.1%.
(1) get the above-mentioned spent catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 110 DEG C.Dried spent catalyst adds Na 2sO 4make additive, Na 2sO 4with the mol ratio m of Metals from Spent Catalysts total amount add: m metal=5.5.Mix and be placed on roasting in retort furnace, maturing temperature is 800 DEG C, and roasting time is 5h;
(2) make leaching agent with 1g/LNaOH solution, after step (1) roasting, leach V and W spent catalyst, liquid-solid ratio is 0.2L/g, extraction temperature is 100 DEG C, and leaching pressure is 0.2MPa, and extraction time is 4h, stirring velocity is 2000r/min, V single-stage leaching yield be 81.7%, W is 77.2%; Leached mud returns step (1);
(3) with neutral phosphine kind of extractants TBP and kerosene composition extraction system for organic phase, concentration is 30%, at the initial pH=6 of aqueous phase, two compare O/A=1, extraction temperature is 30 DEG C, extraction time is that under the condition of 35min, from leach liquor, synchronous extraction V and W, V percentage extraction is 99.0%, W percentage extraction is 97.6%.Then with the ammoniacal liquor of 30%, vanadium tungsten mixed-ammonium salt solution is obtained to the synchronous back extraction of V and W in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=6, back extraction temperature is 50 DEG C, and Stripping times is 4h.Regulate the ratio of V and W in vanadium tungsten mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 50 DEG C must vanadium tungsten mixed-ammonium salt;
(4) with neutral phosphine kind of extractants TBP and kerosene composition extraction system for organic phase, concentration is 30%, at the initial pH=2.5 of aqueous phase, two compare O/A=1, extraction temperature is 30 DEG C, and extraction time is that under the condition of 35min, from leach liquor, extracting and separating V and W, V percentage extraction are 99.8%, W percentage extraction is 0.3%, obtains rich vanadium organic phase and tungstenic raffinate.The 5g/LNaOH solution back extraction of rich vanadium organic phase, the OH wherein added -with the mol ratio m of total metal content in organic phase oH -: m metal=4.5, back extraction temperature is 35 DEG C, and Stripping times is 1h, obtains sodium vanadate solution;
(5) the vanadium tungsten mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.2mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 3h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 24h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 600 DEG C, and roasting time is 12h.Roasting after product is granular 1.4%V 2o 5-3.0%WO 3/ TiO 2it is SCR denitration;
(6) sodium vanadate solution that step (4) obtains regulates pH=9, then adds ammonium nitrate precipitation, and the ammonium metavanadate precipitate obtained is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.5%; Tungstenic raffinate regulates pH=6.2, then again carries tungsten with extraction process.The extraction system of neutral phosphine kind of extractants TBP and kerosene composition is organic phase, and concentration is 15%, two compare O/A=1, and extraction temperature is 30 DEG C, and extraction time is 30min, W percentage extraction is 99.5%.The 30% ammoniacal liquor back extraction of rich tungsten organic phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=5, back extraction temperature is 35 DEG C, and Stripping times is 2h, and the ammonium tungstate solution obtained, through evaporative crystallization, washing and drying, obtains ammonium paratungstate product, and purity is 99.3%.
Embodiment 6
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V 2o 5content is 1.3%, WO 3be 1.4%, MoO 3be 1.4%, TiO 2be 95.7%.
(1) get the above-mentioned spent catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried spent catalyst adds NaNO 3make additive, NaNO 3with the mol ratio m of Metals from Spent Catalysts total amount add: m metal=6.Mix and be placed on roasting in retort furnace, maturing temperature is 900 DEG C, and roasting time is 7h;
(2) make leaching agent with 1g/LNaOH solution, after step (1) roasting, leach V, W and Mo spent catalyst, liquid-solid ratio is 0.3L/g, extraction temperature is 100 DEG C, and leaching pressure is 0.4MPa, and extraction time is 5h, stirring velocity is 3000r/min, V single-stage leaching yield be 81.7%, W is 77.2%; Leached mud returns step (1);
(3) with organosilane ester amyl acetate-n and kerosene composition extraction system for organic phase, concentration is 25%, at the initial pH=10 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, and extraction time is from step (2) leach liquor, synchronously extract V, W and Mo under the condition of 40min, and V percentage extraction is 99.6%, W percentage extraction is 98.6%, Mo percentage extraction is 97.8%.Then with the ammoniacal liquor of 15%, vanadium tungsten mixed-ammonium salt solution is obtained to the synchronous back extraction of V, W and the Mo in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=5, back extraction temperature is 45 DEG C, and Stripping times is 2h.Regulate the ratio of V, W and the Mo in vanadium tungsten mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 45 DEG C must vanadium tungsten mixed-ammonium salt;
(4) with organosilane ester amyl acetate-n and kerosene composition extraction system for organic phase, concentration is 25%, at the initial pH=3.2 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, and extraction time is that under the condition of 40min, from step (2) leach liquor, extracting and separating V, W and Mo, V percentage extraction are 100%, W and Mo percentage extraction, lower than 0.2%, obtains rich vanadium organic phase and contains tungsten raffinate.Ammoniacal liquor with 15% to the back extraction of rich vanadium organic phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=4, back extraction temperature is 40 DEG C, and Stripping times is 2.5h, obtains ammonium metavanadate precipitate;
(5) the vanadium tungsten mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.2mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 4h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 24h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 600 DEG C, and roasting time is 10h.Roasting after product is granular 1.4%V 2o 5-1.2%WO 3-1.2% MoO 3/ TiO 2it is SCR denitration;
(6) ammonium metavanadate precipitate that obtains of step (4) is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.3%; What step (4) obtained regulates pH=2 containing tungsten raffinate, and then through evaporative crystallization, washing, drying and calcining, obtain molybdic oxide and tungstic oxide mix product, purity is 99.0%.
Embodiment 7
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V 2o 5content is 1.2%, MoO 3be 2.5%, TiO 2be 96%.
(1) get the above-mentioned spent catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C;
(2) make leaching agent with 2g/LNaOH solution, from the dry rear spent catalyst of step (1), leach V and Mo, liquid-solid ratio is 0.5L/g, extraction temperature is 200 DEG C, and leaching pressure is 1 MPa, and extraction time is 5h, stirring velocity is 5000r/min, V single-stage leaching yield be 84.1%, Mo is 80.1%; Leached mud returns step (1);
(3) with organic phosphine class D2EHPA and kerosene composition extraction system for organic phase, concentration is 15%, at the initial pH=8.5 of aqueous phase, two compare O/A=1, extraction temperature is 30 DEG C, extraction time is that under the condition of 30min, from step (2) leach liquor, synchronous extraction V and Mo, V percentage extraction is 99.8%, Mo percentage extraction is 98.9%.Then with the ammoniacal liquor of 20%, vanadium molybdenum mixed-ammonium salt solution is obtained to the synchronous back extraction of V and Mo in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=6, back extraction temperature is 30 DEG C, and Stripping times is 2.5h.Regulate the ratio of V and Mo in vanadium molybdenum mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 40 DEG C must vanadium molybdenum mixed-ammonium salt;
(4) with organic phosphine class D2EHPA and kerosene composition extraction system for organic phase, concentration is 15%, at the initial pH=2 of aqueous phase, two compare O/A=1, extraction temperature is 30 DEG C, and extraction time is that under the condition of 30min, from step (2) leach liquor, extracting and separating V and Mo, V percentage extraction are 0.1%, Mo percentage extraction is 99.9%, obtains rich molybdenum organic phase and contains vanadium raffinate.By the NaOH solution of 1g/L to the back extraction of rich molybdenum organic phase, the OH wherein added -with the mol ratio m of total metal content in organic phase oH -: m metal=5, back extraction temperature is 30 DEG C, and Stripping times is 0.5h, obtains sodium molybdate solution;
(5) the vanadium molybdenum mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.1mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 4h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 24h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 600 DEG C, and roasting time is 9h.Roasting after product is granular 1.5%V 2o 5-2.6%MO 3/ TiO 2it is SCR denitration;
(6) sodium molybdate solution that obtains of step (4) is through evaporative crystallization, washing and drying, and obtain Sodium orthomolybdate product, purity is 99.5%; What step (4) obtained first regulates pH=8.5 containing vanadium raffinate, then adds ammonium sulfate precipitation, and the ammonium metavanadate precipitate obtained is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.6%.
Embodiment 8
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V 2o 5content is 1.5%, MoO 3be 2.3%, TiO 2be 96.1%.
(1) get the above-mentioned spent catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C;
(2) make leaching agent with 5g/LNaOH solution, from the dry rear spent catalyst of step (1), leach V and Mo, liquid-solid ratio is 0.6L/g, extraction temperature is 150 DEG C, and leaching pressure is 0.5 MPa, and extraction time is 5h, stirring velocity is 5000r/min, V single-stage leaching yield be 80.1%, Mo is 81.1%; Leached mud returns step (1);
(3) with oximes extraction agent Lix63 and kerosene composition extraction system for organic phase, concentration is 30%, at the initial pH=6 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, extraction time is that under the condition of 40min, from step (2) leach liquor, synchronous extraction V and Mo, V percentage extraction is 98.7%, Mo percentage extraction is 98.9%.Then with the ammoniacal liquor of 20%, vanadium molybdenum mixed-ammonium salt solution is obtained to the synchronous back extraction of V and Mo in extraction phase, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=5, back extraction temperature is 20 DEG C, and Stripping times is 3h.Regulate the ratio of V and Mo in vanadium molybdenum mixed-ammonium salt solution, then dry at evaporation, crystallization, washing and 40 DEG C must vanadium molybdenum mixed-ammonium salt;
(4) with oximes extraction agent Lix63 and kerosene composition extraction system for organic phase, concentration is 30%, at the initial pH=2 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, and extraction time is that under the condition of 40min, from leach liquor, extracting and separating V and Mo, V percentage extraction are 99.7%, Mo percentage extraction is 0.4%, obtains rich vanadium organic phase and contains molybdenum raffinate.By the rich vanadium organic phase of 15% ammoniacal liquor back extraction, the mol ratio m of total metal content in the ammonium ion wherein added and organic phase nH4+: m metal=5, back extraction temperature is 45 DEG C, and Stripping times is that 2.5h obtains ammonium metavanadate precipitate;
(5) the vanadium molybdenum mixed-ammonium salt that step (3) obtains first is dissolved in the oxalic acid solution of 0.1mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 4h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 24h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 600 DEG C, and roasting time is 9h.Roasting after product is granular 1.4%V 2o 5-2.2%MO 3/ TiO 2it is SCR denitration;
(6) ammonium metavanadate precipitate that obtains of step (4) is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.7%; What step (4) obtained regulates pH=1 containing molybdenum raffinate, and then through evaporative crystallization, washing, drying and calcining, obtain molybdenum trioxide product, purity is 99.4%.
Embodiment 9
The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V 2o 5content is 1.2%, WO 3be 3.3%, TiO 2be 95.3%.
(1) get the above-mentioned spent catalyst of 50g, first shatter to 100 orders, then wash with water, filter and 105 DEG C of dryings;
(2) make leaching agent with the sodium hydroxide solution of 2g/L, from step (1) dried spent catalyst, leach V and W, liquid-solid ratio is 1L/g, extraction temperature is 200 DEG C, and leaching pressure is 1MPa, and extraction time is 5h, stirring velocity is 100r/min, V single-stage leaching yield be 77.2%, W is 75.6%; Leached mud carries out secondary leaching;
(3) the leach liquor nitric acid that step (2) obtains regulates pH=6, then adds nitrocalcite co-precipitation, the mol ratio m of total metal content in nitrocalcite and leach liquor pre: m metal=1, temperature of reaction is 10 DEG C, and sedimentation time is 10min, can obtain calcium vanadate and calcium wolframate mixed precipitation.By mixed precipitation nitric acid dissolve, after regulator solution pH=6, then add nitrocalcite co-precipitation, the precipitation obtained is pure vanadium tungsten mixing calcium salt through washing, drying.Vanadium tungsten mixing calcium salt nitric acid dissolve regulator solution pH=1.5, the then ratio of V and W in regulator solution.Vanadium tungsten solution is after drying at evaporation, crystallization, washing and 105 DEG C, and roasting at 600 DEG C further, obtains vanadium tungsten mixed oxide;
(4) the leach liquor precipitator method that step (2) obtains are separated V and W.Regulate leach liquor pH=5, then add ammonium sulfate precipitation, the mol ratio m of vanadium metal in ammonium sulfate and leach liquor pre: m metal=1, precipitation temperature is 20 DEG C, and sedimentation time is 20min, filters to obtain ammonium metavanadate precipitate and tungstenic solution;
(5) the vanadium tungsten mixed oxide hybrid system that step (3) obtains prepares vanadium tungsten system SCR catalyst powder.First vanadium tungsten mixed oxide is crushed to 100 orders, then with TiO 2wet ball grinding mixing 5h is carried out according to certain ratio.After mixing terminates, be placed in the dry 12h of baking oven of 110 DEG C together.Dried product is 1.3%V 2o 5-3.2%WO 3/ TiO 2it is SCR catalyst powder.Get the catalyst powder that 50g is milled to 0.1mm, then add tackiness agent polyacrylamide 4.5g and particle diameter is be dry mixed 15min after the absorbent charcoal powder body 2.5g of 0.1mm.After mixing, add 10mL water and extrusion aid thanomin 4mL successively, then with rolling rod, kneading operation being carried out to wet stock, obtaining plasticity lotion.Plasticity lotion is loaded honeycombed catalyst mould upstream, uses pressing plate to be pressed into by force by plasticity lotion between the sizing bar of bottom.Mould containing catalyzer lotion is heated in 65 DEG C of baking ovens, until be coated in advance sizing bar and die surface on paraffin melting after, by mould take out obtain half-dried catalyzer idiosome.Catalyzer idiosome prior to dry 12h in 105 DEG C of baking ovens, then at 450 DEG C roasting 12h, obtain cellular 1.3%V 2o 5-3.3%WO 3/ TiO 2it is SCR denitration;
(6) ammonium metavanadate precipitate that obtains of step (4) is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.1%; Tungstenic solution that step (4) obtains regulates pH=8, then adds nitrocalcite precipitation, the mol ratio m of tungsten in nitrocalcite and leach liquor pre: m metal=6, temperature of reaction is 50 DEG C, and sedimentation time is 50min, can obtain calcium wolframate precipitation.Calcium wolframate precipitation obtains calcium wolframate product through washing and drying, and purity is 99.3%.
Embodiment 10
The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V 2o 5content is 1.1%, MO 3be 2.5%, TiO 2be 96.2%.
(1) get the above-mentioned spent catalyst of 50g, first shatter to 100 orders, then wash with water, to filter and dry.Dried spent catalyst adds NaNO 3make additive, NaNO 3with the mol ratio m of Metals from Spent Catalysts total amount add: m metal=4.5.Mix and be placed on roasting in retort furnace, maturing temperature is 700 DEG C, and roasting time is 6h;
(2) leaching agent is made with the sodium hydroxide solution of 2g/L, V and Mo is leached from the spent catalyst after step (1) roasting, liquid-solid ratio is 0.2L/g, extraction temperature is 120 DEG C, leaching pressure is 0.5MPa, and extraction time is 5h, and stirring velocity is 1000r/min, V single-stage leaching yield is 74.9%, Mo is 72.7%; Leached mud carries out secondary leaching;
(3) leach liquor described in step (2) regulates pH=12, then adds calcium chloride co-percipitation, the mol ratio m of total metal content in calcium chloride and leach liquor pre: m metal=5, temperature of reaction is 90 DEG C, and sedimentation time is 120min, can obtain calcium vanadate and calcium molybdate mixed precipitation.By mixed precipitation nitric acid dissolve, after regulator solution pH=12, then add calcium chloride co-percipitation, the precipitation obtained is pure vanadium molybdenum mixing calcium salt through washing, drying.Vanadium molybdenum mixing calcium salt nitric acid dissolve regulator solution pH=1.5, the then ratio of V and Mo in regulator solution.Vanadium molybdenum solution is dry at evaporation, crystallization, washing and 105 DEG C, and roasting at 650 DEG C further, obtains vanadium molybdenum mixed oxide;
(4) precipitator method of the leach liquor described in step (2) are separated V and Mo.Regulate leach liquor pH=11, then add ammonium chloride precipitation, the mol ratio m of vanadium metal in ammonium chloride and leach liquor pre: m metal=6, precipitation temperature is 80 DEG C, and sedimentation time is 120min, filters to obtain ammonium metavanadate precipitate and containing molybdenum solution;
(5) the vanadium molybdenum mixed oxide that step (3) obtains first is dissolved in the oxalic acid solution of 0.1mol/L, then adds TiO in proportion 2.System is inserted ultrasonic mixing 4h in ultrasonic cleaner.After ultrasonic end, system is stirred evaporate to dryness.The solid mixture obtained after evaporate to dryness is put into the dry 24h of electric drying oven with forced convection of 110 DEG C.Clayed into power by dried solid mixture, then put into crucible and insert retort furnace roasting, maturing temperature is 600 DEG C, and roasting time is 9h.Product of roasting is 1.2%V 2o 5-2.5%MO 3/ TiO 2it is SCR catalyst powder.Get the catalyst powder that 50g is milled to 0.1mm, then add tackiness agent polyacrylamide 5g and particle diameter is be dry mixed 20min after the absorbent charcoal powder body 2.5g of 0.1mm.After mixing, add 8mL water and extrusion aid thanomin 3.5mL successively, then with rolling rod, kneading operation being carried out to wet stock, obtaining plasticity lotion.Plasticity lotion is loaded honeycombed catalyst mould upstream, uses pressing plate to be pressed into by force by plasticity lotion between the sizing bar of bottom.Mould containing catalyzer lotion is heated in 60 DEG C of baking ovens, until be coated in advance sizing bar and die surface on paraffin melting after, by mould take out obtain half-dried catalyzer idiosome.Catalyzer idiosome prior to dry 24h in 110 DEG C of baking ovens, then at 450 DEG C roasting 12h, obtain cellular 1.3%V 2o 5-2.4%WO 3/ TiO 2it is SCR denitration.
(6) ammonium metavanadate precipitate that obtains of step (4) is through washing, dry and calcining, and obtain Vanadium Pentoxide in FLAKES product, purity is 99.5%; What step (4) obtained regulates pH=10 containing molybdenum solution, then adds calcium chloride precipitation, the mol ratio m of metal molybdenum in nitrocalcite and leach liquor pre: m metal=6, temperature of reaction is 50 DEG C, and sedimentation time is 120min, can obtain calcium molybdate precipitation.Calcium molybdate precipitation obtains calcium molybdate product through washing and drying, and purity is 99.6%.
Embodiment 11
The useless vanadium molybdenum system SCR catalyst that certain laboratory provides, V 2o 5content is 1.1%, MO 3be 2.0%, TiO 2be 96.7%.
(1) after getting the above-mentioned spent catalyst of 50g, first shatter to 100 orders, wash with water, filtering, dry at 105 DEG C.Dried spent catalyst adds NaCl and makes additive, the mol ratio m of NaCl and Metals from Spent Catalysts total amount add: m metal=6.Mix and be placed on roasting in retort furnace, maturing temperature is 900 DEG C, and roasting time is 7h;
(2) leaching agent is made with the sulphuric acid soln of 1g/L, V and Mo is leached from the spent catalyst after step (1) roasting, liquid-solid ratio is 1L/g, extraction temperature is 100 DEG C, and leaching pressure is 0.2MPa, and extraction time is 0.5h, stirring velocity is 5000r/min, V single-stage leaching yield is 96.2%, Mo be 95.2%, Ti is 86.1%; Leached mud returns step (1);
(3) V, Mo and Ti weak base anion-exchange resin D418 simultaneous extraction in the leach liquor obtained in step (2).Leach liquor volume is 10 times of resin volume, pH value of solution=1, and temperature is 10 DEG C, and the permutoid reaction time is 30min, V extraction yield be 94.3%, Mo be 95.8%, Ti is 96.2%, and mother liquor carries out second extraction.Ammoniacal liquor with 15% is to resin regenerated from washing, and the recovery time is 20min, and regeneration temperature is 20 DEG C, obtains vanadium molybdenum titanium mixed-ammonium salt solution;
(4) leach liquor described in step (2) first regulates pH=9, filters to obtain sodium titanate precipitation and vanadium molybdenum solution.Vanadium molybdenum solution weak base anion-exchange resin D418 is separated, and leach liquor volume is 10 times of resin volume, pH value of solution=2, and temperature is 20 DEG C, and the permutoid reaction time is 30min, V extraction yield be 99.3%, Mo is 0.2%, obtains negative vanadium resin and containing liquid more than molybdenum.With the Na of 2g/L 2cO 3solution is to resin regenerated from washing, and the recovery time is 20min, and regeneration temperature is 25 DEG C, obtains sodium vanadate solution;
(5) the vanadium molybdenum titanium mixed-ammonium salt solution precipitator method that step (3) obtains prepare vanadium molybdenum system SCR denitration powder.First vanadium molybdenum titanium mixed-ammonium salt solution is regulated pH=7.5, then add nitrocalcite, filter and obtain the mixed precipitation of vanadium molybdenum titanium.Mixed precipitation first uses nitric acid dissolve, and continues to be acidified to pH=1.1, then through evaporative crystallization, washing, 105 DEG C of dryings and 750 DEG C of roastings, obtains 1.2%V 2o 5-2.0%MoO 3/ TiO 2it is SCR catalyst powder.Get the catalyst powder that 50g is milled to 0.1mm, then add tackiness agent methylcellulose gum 5.5g and particle diameter is be dry mixed 18min after the absorbent charcoal powder body 3.5g of 0.1mm.After mixing, add 8mL water, extrusion aid thanomin 4mL and lubricating oil glycerine 2.5mL successively, then with rolling rod, kneading operation being carried out to wet stock, obtaining plasticity lotion.With the stainless steel flat plate with sieve aperture of 55*100mm for carrier, plate thickness is 0.5mm, and aperture lmm, pitch of holes are 1.5mm, equilateral triangle arrangement, and the thick plasticity lotion of 0.5mm is evenly suppressed in the upper and lower both sides of sieve plate.By the dry 12h at 105 DEG C of the sieve plate with plasticity lotion, and then at 500 DEG C after calcination 24h, obtaining thickness is 1.5mm catalyzer veneer, it is assembled in Stainless Steel Shell and obtains board-like catalyzer;
(6) sodium vanadate solution that step (4) obtains regulates pH=8, adds ammonium sulfate precipitation, and the ammonium metavanadate precipitate obtained is through washing, drying and calcine, the Vanadium Pentoxide in FLAKES product obtained, and purity is 99.5%; What step (4) obtained regulates pH=1.2 containing liquid more than molybdenum, and then through evaporative crystallization, washing and drying, obtain molybdic acid product, purity is 99.0%.
Embodiment 12
The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V 2o 5content is 1.3%, WO 3be 2.4%, TiO 2be 96.1%.
(1) after getting the above-mentioned spent catalyst of 50g, first shatter to 100 orders, wash with water, filtering, dry at 105 DEG C;
(2) make leaching agent with 1g/LNaOH solution, from step (1), leach V and W, liquid-solid ratio is 0.7L/g, and extraction temperature is 150 DEG C, leaching pressure is 0.5MPa, and extraction time is 2h, and stirring velocity is 4000r/min, V single-stage leaching yield is 87.2%, W be 86.3%, Ti is 84.3%; Leached mud returns step (1);
(3) V and the W strongly basic anion exchange resin D201 simultaneous extraction in the leach liquor obtained in step (2).Leach liquor volume is 100 times of resin volume, pH value of solution=12, and temperature is 100 DEG C, and the permutoid reaction time is 120min, V extraction yield be 99.1%, W is 98.9%, and mother liquor carries out second extraction.With 2g/LNaOH solution to resin regenerated from washing, the recovery time is 120min, and regeneration temperature is 100 DEG C, obtains vanadium tungsten mixed sodium salts solution;
(4) V with the W strongly basic anion exchange resin D201 in the leach liquor described in step (2) is separated.Leach liquor volume is 100 times of resin volume, pH value of solution=11, and temperature is 90 DEG C, and the permutoid reaction time is 100min, V extraction yield be 99.1%, W is 0.1%, obtains liquid more than negative vanadium resin and tungstenic.By the NaOH solution of 5g/L to resin regenerated from washing, the recovery time is 120min, and regeneration temperature is 90 DEG C, obtains sodium vanadate solution;
(5) the vanadium tungsten mixed sodium salts solution that step (3) obtains first regulates the ratio of V and W, then regulates pH=3, then dissolves in Na in proportion 2tiO 3, the vanadium tungsten titanium mixing solutions precipitator method obtained prepare vanadium tungsten system SCR denitration powder.First vanadium tungsten titanium mixing solutions is regulated pH=8, then add nitrocalcite, filter and obtain the mixed precipitation of vanadium tungsten titanium.Mixed precipitation first uses nitric acid dissolve, and continues to be acidified to pH=1.5, then through evaporative crystallization, washing, 105 DEG C of dryings and 700 DEG C of roastings, obtains 1.2%V 2o 5-2.3%WO 3/ TiO 2it is SCR catalyst powder.Get the catalyst powder that 50g is milled to 0.1mm, then add tackiness agent methylcellulose gum 5g and particle diameter is be dry mixed 20min after the absorbent charcoal powder body 3g of 0.1mm.After mixing, add 10mL water, extrusion aid thanomin 5mL and lubricating oil glycerine 2mL successively, then with rolling rod, kneading operation being carried out to wet stock, obtaining plasticity lotion.With the corrugated fibreboard of 50*100mm for carrier, fiberboard thickness is 0.5mm, and the upper and lower both sides of fiberboard evenly coat the thick plasticity lotion of 0.5mm.By the dry 24h at 105 DEG C of the sieve plate with plasticity lotion, and then at 450 DEG C after calcination 20h, obtain 1.3%V 2o 5-2.2%WO 3/ TiO 2it is corrugated plate dst catalyzer;
(6) sodium vanadate solution that step (4) obtains regulates pH=9, adds ammonium nitrate precipitation, and the ammonium metavanadate precipitate obtained is through washing, drying and calcine, the Vanadium Pentoxide in FLAKES product obtained, and purity is 99.7%; More than the tungstenic that step (4) obtains, liquid regulates pH=1.5, and then through evaporative crystallization, washing and drying, obtain tungstenic acid product, purity is 99.5%.
Finally it should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted; although with reference to preferred embodiment to invention has been detailed description; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement; and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the protection domain of claim of the present invention.

Claims (10)

1. a recovery and treatment method for useless SCR denitration, is characterized in that, comprises the steps:
(1) will give up the catalyst components such as SCR denitration pre-treatment, removal impurity, activation vanadium tungsten;
(2) the useless SCR denitration obtained after step (1) pre-treatment is leached, obtain leached mud and leach liquor;
(3) in the leach liquor obtained step (2), each valuable element is separated, and obtains vanadium purification thing and tungsten/molybdenum/tungsten enriched substance;
(4) the vanadium purification thing that step (3) obtains is further purified, for the preparation of vanadium product; Tungsten/molybdenum/tungsten the enriched substance obtained is further purified, for the preparation of tungsten/molybdenum/tungsten product.
2. the method for claim 1, it is characterized in that, in the leach liquor that step (2) obtains by (5), valuable element carries out Isolation, regulates the ratio of each substances content, thus obtain catalyst component mixture, for being prepared as new SCR denitration further.
3. method as claimed in claim 1 or 2, it is characterized in that, leaching agent during step (2) leaches can be neutrality or acid or basic solution, the liquid-solid ratio of leaching agent and spent catalyst is 0.02 ~ 1L/g, extraction temperature is 20 ~ 200 DEG C, leaching pressure is 0.1 ~ 1MPa, and extraction time is 0.5 ~ 5h, and stirring velocity is 100 ~ 5000r/min;
Preferably, leaching agent is neutral or basic solution.
4. the method for claim 1, it is characterized in that, when in leach liquor described in step (3), each valuable element extraction process is separated, extraction agent can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and oximes, extractant concentration is 5% ~ 30%, initial pH=1 ~ 9 of aqueous phase, extraction temperature is 10 ~ 40 DEG C, and extraction time is 10 ~ 40min.
5. the method for claim 1, it is characterized in that, in leach liquor described in step (3) during each valuable element Strong acid ion-exchanger, resin types is strong basicity or weak base anion-exchange resin, and leach liquor volume is 10 ~ 100 times of resin volume, and pH value of solution is 2 ~ 11, temperature is 20 ~ 90 DEG C, swap time is 30 ~ 100min, resin regeneration liquid is strong basicity or weakly alkaline solution, and the recovery time is 20 ~ 120min, and regeneration temperature is 25 ~ 90 DEG C.
6. the method for claim 1, is characterized in that, when each valuable element precipitator method in the leach liquor described in step (3) are separated, and the mol ratio m of total metal content in precipitation agent and leach liquor pre: m metal=1 ~ 6, pH value of solution=5 ~ 11, precipitation temperature is 20 ~ 80 DEG C, and sedimentation time is 20 ~ 120min.
7. method as claimed in claim 2, it is characterized in that, when in leach liquor described in step (3), valuable element is with extraction process Isolation, extraction agent can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt or oximes extraction agent, extractant concentration is 5% ~ 30%, initial pH=1 ~ 10 of aqueous phase, extraction temperature is 10 ~ 40 DEG C, and extraction time is 10 ~ 40min.
8. method as claimed in claim 2, it is characterized in that, when valuable element in leach liquor described in step (3) is with ion exchange method Isolation, resin types is strong basicity or weak base anion-exchange resin, and leach liquor volume is 10 ~ 100 times of resin volume, and pH value of solution is 1 ~ 12, temperature is 10 ~ 100 DEG C, swap time is 30 ~ 120min, resin regeneration liquid is strong basicity or weakly alkaline solution, and the recovery time is 20 ~ 120min, and regeneration temperature is 20 ~ 100 DEG C.
9. method as claimed in claim 2, is characterized in that, when the valuable element in the leach liquor described in step (3) is with coprecipitation method Isolation, and the mol ratio m of total metal content in precipitation agent and leach liquor pre: m metal=1 ~ 5, pH value of solution=6 ~ 12, precipitation temperature is 10 ~ 90 DEG C, and sedimentation time is 10 ~ 120min.
10. as the method as described in arbitrary in claim 2,7,8 or 9, it is characterized in that, the method that catalyst component mixture described in step (4) prepares new SCR catalyst is pickling process, hybrid system and the precipitator method, and new SCR catalyst is particulate state, board-like, cellular and corrugated plate dst;
Preferably, the method that catalyst component mixture prepares new SCR catalyst is pickling process, and new SCR catalyst is particulate state.
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CN109607612A (en) * 2018-12-24 2019-04-12 孙昕 Vanadium in a kind of discarded SCR denitration, tungsten, titanium resource recycling method
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CN115404360A (en) * 2021-10-28 2022-11-29 韩国地质资源研究院 Method for selectively recovering vanadium and cesium from waste vanadium sulfate catalyst, and high-quality vanadium aqueous solution and cesium alum prepared by same
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US11807544B2 (en) 2021-10-28 2023-11-07 Korea Institute Of Geoscience And Mineral Resources Selective recovery method of vanadium and cesium from waste sulfuric acid vanadium catalyst, and high-quality vanadium aqueous solution and cesium alum produced thereby
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