CN104923257A - Cyclical remanufacturing method of waste SCR (selective catalytic reduction) denitrification catalyst - Google Patents
Cyclical remanufacturing method of waste SCR (selective catalytic reduction) denitrification catalyst Download PDFInfo
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Abstract
The invention relates to a method for cyclically remanufacturing a waste SCR (selective catalytic reduction) denitrification catalyst. According to the method, a waste catalyst is first subjected to pretreatment, and after impurities and catalytic components of activated vanadium, tungsten, molybdenum and the like are removed, leaching residues and leaching liquor are obtained through leaching; after valuable elements in the leaching liquor are synchronously purified, the proportion of the content of each substance is regulated, a mixture of the catalytic components is prepared, and a new catalyst is further prepared from the mixture. By using a method for cyclically remanufacturing the waste SCR denitrification catalyst, the cyclical manufacturing of the waste SCR denitrification catalyst from a waste to the new catalyst is truly realized, and the economic benefit and the environmental benefit are obvious.
Description
Technical field
The invention belongs to field for the treatment of of solid waste, particularly relate to a kind of circulation reproducing method of useless SCR denitration.
Background technology
As everyone knows, in selective catalytic reduction, the investment of catalyst occupies about 70% of gross investment nearly, and the Appropriate application of catalyst is the key ensureing that denitrating technique normally runs.It is reported, because the requirement of country to environmental protection is more and more higher, the coming years, the speed with 15% increased the demand of SCR denitration by China.But, manufacture the cost of material of SCR denitration but in continuous growth.Therefore, denitration enterprise must find effective ways and tackle this realistic problem.Wherein valuable component in waste and old denitrating catalyst is extracted and manufactures raw catelyst again and can be used as one of thinking.After useless SCR denitration refers to that activation uses repeatedly in denitrating technique, original physical arrangement is seriously damaged, is difficult to the dead catalyst of regeneration activating.Though useless SCR catalyst cannot regenerate, the WO wherein contained
3, MoO
3, V
2o
5and TiO
2be scarce resource, can be used as the raw material that circulation manufactures SCR denitration again.WO simultaneously
3, MoO
3, V
2o
5and TiO
2also be noxious material, potential risk can be brought to environment.Therefore, to the valuable element extraction in useless SCR denitration, being also fabricated to raw catelyst again has very large economy and environment protection significance.
Patent 201410471973.3 discloses a kind of method reclaiming tungstic acid composition in waste and old SCR denitration.Waste and old SCR denitration is crushed to dry powder-shaped, the tungstic acid composition of particular solution under certain condition in catalyst-solvent is utilized after high-temperature roasting, tungstic acid is effectively separated with other composition in catalyst, 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 acid composition.
Patent 201410471988.X discloses a kind of method reclaiming vanadic anhydride composition in waste and old SCR denitration.It first utilizes reducing agent that the pentavalent vanadium in catalyst is reduced to more easily molten tetravalence vanadium in an acidic solution, then again the tetravalence vanadium in acid solution is oxidized to pentavalent vanadium with oxidant, by regulating the pH value of solution, pentavalent vanadium is made fully to be hydrolyzed and to precipitate under certain condition, collecting precipitation can obtain highly purified vanadic anhydride through calcination process, and purity of vanadium pentoxide is 98%.
Patent 201310085634.7 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 concentrated sulfuric acid and obtains titanyl sulfate concentrated solution by after its acidolysis, then be diluted with water; Then add nonionic emulsifier as flocculant, sulfosalt surfactant or polycarboxylate surfactant, as flocculation aid, then add Water-soluble methyl silicone oil; Pump into plate and frame filter press again and carry out press filtration, be heated to 90 DEG C-98 DEG C again by concentrated for filter vacuum 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 potash 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 201410526388.9 discloses a kind of method reclaiming silica 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 adds thermal agitation 1 ~ 2h in the nitration mixture 40 ~ 60 DEG C of dilute sulfuric acid and oxalic acid, filters, spends deionized water filter cake, wash the acid ion contained by solid off, obtain high-purity silicon dioxide through heat resolve.
Patent 201410483299.0 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 pulverizing, 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, through stirring, filtering, dewater, calcine, pulverize, obtain the catalyst of reclaiming.
In sum, the treatment technology major part of published useless SCR catalyst is all reclaim one or more components in dead catalyst, the circulation that all could not realize dead catalyst is prepared again, and the direct discharge of final refuse still can work the mischief to environment, cannot really realize solid waste resource reclaim, economic benefit and environmental benefit poor.Although can reclaiming catalyst in method disclosed in patent 201410483299.0, and the toxic element of catalyst poisoning easily could not be caused to remove to the impurity in dead catalyst, the Impurities In Catalyst content of reclaiming be high, easy in inactivation.
Summary of the invention
In conjunction with the Current Domestic present situation such as useless SCR denitration circulation re-manufacturing technology shortage outward, the present invention proposes a kind of Processing tecchnics that directly useless SCR catalyst can be fabricated to again new product by refuse.The components such as the vanadium tungsten in useless SCR catalyst not only can be extracted by this technique, thoroughly solve the pollution problem of solid waste, also the valuable elements such as the vanadium tungsten of extraction can be fabricated to raw catelyst again again.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A circulation reproducing method for useless SCR denitration, comprises the steps:
(1) will give up the catalyst components such as SCR denitration pretreatment, removal impurity, activation vanadium tungsten;
(2) dead catalyst obtained after pretreatment in step (1) is leached, obtain leached mud and leachate;
(3) valuable element in step (2) leachate is carried out Isolation, regulate each matter content ratio, obtain catalyst component mixture;
(4) step (3) catalyst component mixture is 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.Preprocess method can be washing, pulverizing, roasting and drying etc.Washing and dry dust, sand grains and the oil content can removed dead catalyst and carry; Pulverizing can improve the specific area of dead catalyst; Roasting can by the V in dead 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, NaCl, Na
2cO
3, the mol ratio m of total metal content in additive and catalyst
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.Sintering 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 valuable element.Leaching agent is neutral acid or alkaline, if leaching agent is acid, other elements such as the Ti etc. in dead catalyst except vanadium tungsten also can enter solution, adds the difficulty that in leachate, organic element is separated.Therefore, in the present invention, leaching agent is preferably neutral or alkaline.The liquid-solid ratio of leaching agent and dead catalyst is 0.04 ~ 1L/g, such as, be 0.05 L/g, 0.1L/g, 0.2 L/g, 0.4 L/g, 0.6 L/g and 0.8 L/g etc.Extraction temperature is 20 ~ 200 DEG C, such as, be 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C and 180 DEG C etc.Extraction time can be 0.5 ~ 5h, such as, be 1h, 2h, 3h, 4h and 4.5h etc.Leaching pressure is 0.1 ~ 1MPa, such as, be 0.2MPa, 0.4 MPa, 0.6 MPa and 0.8 MPa etc.Mixing speed 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 committed step of valuable element Isolation in leachate.In leachate, the method for valuable element Isolation can be co-precipitation, extraction and ion-exchange etc.When valuable element in leachate is with extraction Isolation, extractant can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and hydroxyl oximes, be such as 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 class TBP, organosilane ester amyl acetate and organic phosphine class 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, back washing agent can be alkali lye or ammoniacal liquor, the NH in back washing 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 leachate is with ion-exchange Isolation, resin types is strong basicity or weak-base anion-exchange resin, such as, be D418, D301 etc.; Leachate 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 leachate is with coprecipitation Isolation, precipitating reagent is 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 precipitating reagent and leachate
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.
Step (4) is the core procedure that catalyst component vanadium tungsten/vanadium molybdenum/vanadium tungsten mixture prepares new SCR denitration.SCR denitration can be divided into graininess and integral catalyzer according to outward appearance, and wherein integral catalyzer is divided into again board-like, cellular and corrugated plating catalyst.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 metavanadate with other co-catalysts.Board-like catalyst adopts metal sieve plate as carrier, and mechanical strength is good; Honeycombed catalyst is with SCR catalyst powder for matrix, with shaping assistant etc. by mixing, mediating, the process such as extruded, dry and calcination obtains.And corrugated plate dst catalyst take corrugated as carrier, be coated with the coating containing active component, active material fewer than honeycombed catalyst 70% on its surface, after surface reactive material wearing and tearing are run off, catalytic activity declines very fast, and service life is shorter.Cellular and board-like catalyst is all first with V
2o
5/ TiO
2base SCR catalyst powder is raw material, fully mixes kneading obtain plasticity lotion with water, adhesive, extrusion aid, expanding agent, lubricant, glass fibre etc., then honeycombed catalyst with plasticity lotion for matrix obtains through extruded, dry and calcination.And tabular catalyst is evenly compressed in metal sieve plate by plasticity lotion, obtain catalyst by dry, calcination.
SCR catalyst raw powder's production technology mainly contains the precipitation method, infusion process, mixing method.Infusion process is that the liquid leaching containing active component and cocatalyst component is loaded in solid-state carrier on the surface.Its carrier utilization rate is high, and consumption is few, and cost is low, is applicable to low content of noble metal catalyst; The precipitation method are, with precipitating reagent, the catalytic 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-load, metal oxide, metal salt catalyst or catalyst carrier; Mixing method equipment is simple, and easy to operate, product chemical composition is stablized, and can be used for the multicomponent catalyst preparing high-load, especially mixed oxide catalyst, but this method decentralization is lower; Because the active component content of SCR catalyst is lower, so the present invention preferably prepares SCR denitration powder by infusion process.
As optimal technical scheme, method of the present invention, comprises the steps:
(1) will give up the catalyst components such as SCR denitration pretreatment, removal impurity, activation vanadium tungsten;
(2) dead catalyst obtained after pretreatment in step (1) is leached, obtain leached mud and leachate.Leaching agent is neutral or alkaline, and the liquid-solid ratio of leaching agent and dead catalyst is 0.04 ~ 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 mixing speed is 100 ~ 5000r/min;
(3) carry out the adjustment of each matter content ratio after the valuable element Isolation in step (2) leachate, prepare catalyst component mixture.Valuable element extraction in leachate or ion-exchange or coprecipitation Isolation, during extraction, extractant can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt and hydroxyl oximes, 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; During ion-exchange, resin types is strong basicity or weak-base anion-exchange resin, leachate 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, the mol ratio m of total metal content in precipitating reagent and 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;
(4) the catalyst component mixture infusion process described in step (3) is prepared as new granular SCR denitration.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 drying box of 105 ~ 110 DEG C.Clayed into power by dried solid mixture, then insert roasting in Muffle furnace, sintering temperature is 400 ~ 600 DEG C, and roasting time is 5 ~ 12h.Roasting afterproduct is new granular SCR denitration;
the present invention has following effect:
1, the invention discloses a kind of circulation reproducing method of useless SCR denitration, the valuable metal element in useless SCR denitration is extracted regeneration by the method completely, really achieves the circulation of useless SCR denitration from refuse to raw catelyst and manufactures;
2, the resource conversion rate of this method vanadium tungsten all reaches more than 95%, the raw catelyst purity of acquisition and activity high, there is good market value, economic benefit and environmental benefit good.
Accompanying drawing explanation
Fig. 1 is the process chart of the inventive method.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, below the present invention is described in more detail.But following embodiment 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 1
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V
2o
5content is 1.5%, MoO
3be 3.4%, TiO
2be 95%.
(1) get the above-mentioned dead catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried dead 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 Muffle furnace, sintering 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 dead catalyst, liquid-solid ratio is 0.04L/g, extraction temperature is 20 DEG C, and leaching pressure is 0.1MPa, and extraction time is 1.5h, mixing speed is 1000r/min, V single-stage leaching rate be 79.5%, Mo is 74.5%; 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, extraction time is that under the condition of 10min, from leachate, synchronous extraction V and Mo, V extraction yield is 100%, Mo extraction yield 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=5, back extraction temperature is 40 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 50 DEG C must vanadium molybdenum mixed-ammonium salt;
(4) 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 Muffle furnace roasting, sintering temperature is 400 DEG C, and roasting time is 5h.Roasting afterproduct is granular 1.2%V
2o
5-3.5%MO
3/ TiO
2it is SCR denitration.
Embodiment 2
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V
2o
5content is 1.5%, MoO
3be 3.4%, TiO
2be 95%.
(1) get the above-mentioned dead catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried dead 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 Muffle furnace, sintering 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 dead catalyst, liquid-solid ratio is 0.05L/g, extraction temperature is 30 DEG C, and leaching pressure is 0.1MPa, and extraction time is 2h, mixing speed is 800r/min, V single-stage leaching rate be 76.7%, Mo is 72.3%; Leached mud returns step (1);
(3) with secondary amine kind of extractants dioctylamine and normal octane 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 20 DEG C, extraction time is that under the condition of 15min, from leachate, synchronous extraction V and Mo, V extraction yield is 99.5%, Mo extraction yield is 97.8%.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=1, 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) 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 Muffle furnace roasting, sintering temperature is 450 DEG C, and roasting time is 6h.Roasting afterproduct is granular 1.1%V
2o
5-3.1%MO
3/ TiO
2it is SCR denitration.
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 dead catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried dead catalyst adds Na
2cO
3make additive, Na
2cO
3with the mol ratio m of Metals from Spent Catalysts total amount
add: m
metal=3.Mix and be placed on roasting in Muffle furnace, sintering temperature is 500 DEG C, and roasting time is 3h;
(2) make leaching agent with neutral pure water, after step (1) roasting, leach V and W dead catalyst, liquid-solid ratio is 0.06L/g, extraction temperature is 50 DEG C, and leaching pressure is 0.1MPa, and extraction time is 1.5h, mixing speed is 1200r/min, V single-stage leaching rate be 78.6%, W is 73.6%; Leached mud returns step (1);
(3) with tertiary amines extractant 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 25 DEG C, extraction time is that under the condition of 20min, from leachate, synchronous extraction V and W, V extraction yield is 98.5%, W extraction yield is 99.6%.Then with the ammoniacal liquor of 15%, 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=2, back extraction temperature is 50 DEG C, and Stripping times is 2.5h.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) 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 Muffle furnace roasting, sintering temperature is 500 DEG C, and roasting time is 5.5h.Roasting afterproduct is granular 1.2%V
2o
5-3.0%WO
3/ TiO
2it is SCR denitration.
Embodiment 4
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V
2o
5content is 1.2%, WO
3be 3.5%, TiO
2be 95.1%.
(1) get the above-mentioned dead catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried dead catalyst adds NaCl and makes additive, the mol ratio m of NaCl and Metals from Spent Catalysts total amount
add: m
metal=3.Mix and be placed on roasting in Muffle furnace, sintering 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 dead catalyst, liquid-solid ratio is 0.1L/g, extraction temperature is 70 DEG C, and leaching pressure is 0.1MPa, and extraction time is 3h, mixing speed is 5000r/min, V single-stage leaching rate be 76.7%, W is 71.4%; 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=2 of aqueous phase, two compare O/A=1, extraction temperature is 40 DEG C, extraction time is that under the condition of 40min, from leachate, synchronous extraction V and W, V extraction yield is 98.7%, W extraction yield 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=6, 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) 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 Muffle furnace roasting, sintering temperature is 550 DEG C, and roasting time is 7h.Roasting afterproduct is granular 1.3%V
2o
5-3.4%WO
3/ TiO
2it is SCR denitration.
Embodiment 5
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V
2o
5content is 1.2%, WO
3be 2.5%, TiO
2be 96.1%.
(1) get the above-mentioned dead catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried dead catalyst adds Na
2sO
4make additive, Na
2sO
4with the mol ratio m of Metals from Spent Catalysts total amount
add: m
metal=4.Mix and be placed on roasting in Muffle furnace, sintering 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 dead 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, mixing speed is 2000r/min, V single-stage leaching rate be 80.7%, W is 78.2%; 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 leachate, synchronous extraction V and W, V extraction yield is 99.0%, W extraction yield 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) 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 Muffle furnace roasting, sintering temperature is 600 DEG C, and roasting time is 12h.Roasting afterproduct is granular 1.4%V
2o
5-3.0%WO
3/ TiO
2it is SCR denitration.
Embodiment 6
The useless vanadium tungsten system SCR denitration that certain laboratory provides, V
2o
5content is 1.2%, WO
3be 1.5%, MoO
3be 1.4%, TiO
2be 95.7%.
(1) get the above-mentioned dead catalyst of 5g, first shatter to 100 orders, after water washing, filtration, dry at 105 DEG C.Dried dead 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 Muffle furnace, sintering 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 dead catalyst, liquid-solid ratio is 0.4L/g, extraction temperature is 100 DEG C, and leaching pressure is 0.4MPa, and extraction time is 5h, mixing speed is 3000r/min, V single-stage leaching rate be 80.7%, W is 78.2%; Leached mud returns step (1);
(3) with organosilane ester amyl acetate 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 leachate, synchronously extract V, W and Mo under the condition of 40min, and V extraction yield is 99.6%, W extraction yield is 98.6%, Mo extraction yield 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) 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 Muffle furnace roasting, sintering temperature is 600 DEG C, and roasting time is 10h.Roasting afterproduct is granular 1.4%V
2o
5-1.2%WO
3-1.2% MoO
3/ TiO
2it is SCR denitration.
Embodiment 7
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V
2o
5content is 1.3%, MoO
3be 2.4%, TiO
2be 96%.
(1) get the above-mentioned dead 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 dead 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, mixing speed is 5000r/min, V single-stage leaching rate 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 leachate, synchronous extraction V and Mo, V extraction yield is 98.8%, Mo extraction yield is 97.9%.Then with the ammoniacal liquor of 15%, 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) 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 Muffle furnace roasting, sintering temperature is 600 DEG C, and roasting time is 9h.Roasting afterproduct is granular 1.5%V
2o
5-2.6%MO
3/ TiO
2it is SCR denitration.
Embodiment 8
The useless vanadium molybdenum system SCR denitration that certain laboratory provides, V
2o
5content is 1.6%, MoO
3be 2.2%, TiO
2be 96.1%.
(1) get the above-mentioned dead 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 dead 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, mixing speed is 5000r/min, V single-stage leaching rate be 80.1%, Mo is 81.1%; Leached mud returns step (1);
(3) with oximes extractant 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 35 DEG C, extraction time is that under the condition of 35min, from leachate, synchronous extraction V and Mo, V extraction yield is 98.7%, Mo extraction yield 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) 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 Muffle furnace roasting, sintering temperature is 600 DEG C, and roasting time is 9h.Roasting afterproduct is granular 1.4%V
2o
5-2.2%MO
3/ TiO
2it is SCR denitration.
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 dead 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 dead 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, mixing speed is 100r/min, V single-stage leaching rate be 75.1%, W is 71.7%; Leached mud carries out secondary leaching;
(3) the leachate nitric acid described in step (2) regulates pH=6, then adds calcium nitrate co-precipitation, the mol ratio m of total metal content in calcium nitrate and leachate
pre: m
metal=1, reaction temperature is 10 DEG C, and the sedimentation time is 10min, can obtain calcium vanadate and artificial schellite mixed precipitation.By mixed precipitation nitric acid dissolve, after regulating pH value of solution=6, then add calcium nitrate co-precipitation, the precipitation obtained is pure vanadium tungsten mixing calcium salt through washing, drying.Vanadium tungsten mixing calcium salt nitric acid dissolve also regulates pH value of solution=1.5, then regulates the ratio of V and W in 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 vanadium tungsten mixed oxide mixing method 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 adhesive 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 monoethanolamine 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 catalyst 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 catalyst idiosome.Catalyst 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.
Embodiment 10
The useless vanadium tungsten system SCR catalyst that certain laboratory provides, V
2o
5content is 1.1%, MO
3be 2.6%, TiO
2be 96.2%.
(1) get the above-mentioned dead catalyst of 50g, first shatter to 100 orders, then wash with water, to filter and dry; Dried dead 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 Muffle furnace, sintering 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 dead 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 mixing speed is 1000r/min, V single-stage leaching rate is 75.1%, Mo is 71.7%; Leached mud carries out secondary leaching;
(3) leachate 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 leachate
pre: m
metal=5, reaction temperature is 90 DEG C, and the sedimentation time is 120min, can obtain calcium vanadate and calcium molybdate mixed precipitation.By mixed precipitation nitric acid dissolve, after regulating pH value of solution=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 also regulates pH value of solution=1.5, then regulates the ratio of V and Mo in 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) 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 Muffle furnace roasting, sintering 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 adhesive 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 monoethanolamine 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 catalyst 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 catalyst idiosome.Catalyst 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.
Embodiment 11
The useless vanadium molybdenum system SCR catalyst that certain laboratory provides, V
2o
5content is 1.1%, MO
3be 2.1%, TiO
2be 96.7%.
(1) after getting the above-mentioned dead catalyst of 50g, first shatter to 100 orders, wash with water, filtering, dry at 110 DEG C; Dried dead 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 Muffle furnace, sintering temperature is 900 DEG C, and roasting time is 1h;
(2) leaching agent is made with the sulfuric acid solution of 1g/L, V and Mo is leached from the dead 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, mixing speed is 5000r/min, V single-stage leaching rate is 90.2%, Mo be 94.4%, Ti is 86.1%; Leached mud returns step (1);
(3) V, Mo and Ti in the leachate described in step (2), synchronously extract with weak-base anion-exchange resin D418.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 rate be 92.3%, Mo be 97.8%, 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) the vanadium molybdenum titanium mixed-ammonium salt solution precipitation 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 calcium nitrate, 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 adhesive methylcellulose 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 monoethanolamine 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 catalyst veneer, it is assembled in Stainless Steel Shell and obtains board-like catalyst.
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 dead catalyst of 50g, first shatter to 100 orders, wash with water, filtering, dry at 105 DEG C;
(2) make leaching agent with 1g/L sulfuric acid 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 mixing speed is 4000r/min, V single-stage leaching rate is 87.2%, W be 86.3%, Ti is 84.3%; Leached mud returns step (1);
(3) V, W and Ti in the leachate described in step (2), synchronously extract with strong-base anion-exchange resin D201.Leachate volume is 100 times of resin volume, pH value of solution=12, and temperature is 100 DEG C, and the exchange reaction time is 120min, V recovery rate be 99.1%, W be 98.9%, Ti is 98.3%, 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 titanium mixed sodium salting liquid;
(4) the vanadium tungsten titanium mixed sodium salting liquid precipitation method that step (3) obtains prepare vanadium tungsten system SCR denitration powder.First vanadium tungsten titanium mixed sodium salting liquid is regulated pH=8, then add calcium nitrate, 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 adhesive methylcellulose 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 monoethanolamine 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 fiber board 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 catalyst.
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 (7)
1. a circulation reproducing method for useless SCR denitration, is characterized in that, comprise the steps:
(1) will give up the catalyst components such as SCR denitration pretreatment, removal impurity, activation vanadium tungsten;
(2) dead catalyst obtained after pretreatment in step (1) is leached, obtain leached mud and leachate;
(3) valuable element in step (2) leachate is carried out Isolation, regulate each matter content ratio, obtain catalyst component mixture;
(4) the catalyst component mixture that step (3) obtains is prepared as new SCR denitration further.
2. the method for claim 1, it is characterized in that, it is alkaline or neutral that leaching agent in leaching described in step (2) can be acidity, the liquid-solid ratio of leaching agent and dead catalyst is 0.04 ~ 1L/g, extraction temperature is 20 ~ 200 DEG C, leaching pressure is 0.1 ~ 1MPa, and extraction time is 0.5 ~ 5h, and mixing speed is 100 ~ 5000r/min;
Preferably, leaching agent is alkalescence or neutral.
3. the method for claim 1, it is characterized in that, when valuable element in leachate described in step (3) is with extraction Isolation, extractant can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt or oximes extractant, 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.
4. the method for claim 1, it is characterized in that, when valuable element in leachate described in step (3) is with ion-exchange Isolation, resin types is strong basicity or weak-base anion-exchange resin, and leachate 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.
5. the method for claim 1, is characterized in that, when the valuable element in the leachate described in step (3) is with coprecipitation Isolation, and the mol ratio m of total metal content in precipitating reagent and 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.
6. the method for claim 1, it is characterized in that, the method that catalyst component mixture described in step (4) prepares new SCR catalyst is infusion process, mixing method or the precipitation method, and the new SCR catalyst of acquisition is graininess, board-like, cellular or corrugated plate dst;
Preferably, the method that catalyst component mixture prepares new SCR catalyst is infusion process, and new SCR catalyst is graininess.
7. a method of claim 1, is characterized in that, it comprises the following steps:
(1) will give up the catalyst components such as SCR denitration pretreatment, removal impurity, activation vanadium tungsten;
(2) dead catalyst obtained after pretreatment in step (1) is leached, obtain leached mud and leachate, leaching agent is neutral or alkaline, the liquid-solid ratio of leaching agent and dead catalyst is 0.04 ~ 1L/g, extraction temperature is 20 ~ 200 DEG C, leaching pressure is 0.1 ~ 1MPa, and extraction time is 0.5 ~ 5h, and mixing speed is 100 ~ 5000r/min;
(3) carry out the adjustment of each matter content ratio after the valuable element Isolation in step (2) leachate, prepare catalyst component mixture; Valuable element extraction in leachate or ion-exchange or coprecipitation Isolation, wherein during extraction, extractant can be amine, organic phosphine acids, organosilane ester, neutral phosphine class, quaternary ammonium salt or oximes, 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; During ion-exchange, resin types is strong basicity or weak-base anion-exchange resin, leachate volume is 10 ~ 100 times of resin volume, pH value of solution is 1 ~ 12, temperature is 10 ~ 100 DEG C, and swap time is 30 ~ 120min, and resin regeneration liquid is strong basicity or weakly alkaline solution, recovery time is 20 ~ 120min, and regeneration temperature is 20 ~ 100 DEG C; During coprecipitation, the mol ratio m of total metal content in precipitating reagent and 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;
(4) the catalyst component mixture infusion process described in step (3) is prepared as new granular SCR denitration; 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 drying box of 105 ~ 110 DEG C; Clayed into power by dried solid mixture, then insert roasting in Muffle furnace, sintering temperature is 400 ~ 600 DEG C, and roasting time is 5 ~ 12h; Roasting afterproduct is new granular SCR denitration.
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| JP2018512463A JP6563588B2 (en) | 2015-05-22 | 2015-09-21 | Recycling method of used SCR denitration catalyst |
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