CN102936049B - Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst - Google Patents
Method for extracting tungsten, titanium and vanadium from waste SCR (selective catalytic reduction) catalyst Download PDFInfo
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Abstract
The invention discloses a method for extracting tungsten, titanium and vanadium from a waste SCR (selective catalytic reduction) catalyst, which comprises the following steps: crushing the waste SCR catalyst, adding a strongly alkaline solution, and reacting; filtering, separating, then adding strong acid into the sodium tungstate and sodium vanadate mixed solution, and reacting to obtain tungstic acid and a sodium salt and vanadic acid mixed solution; regulating the pH value of the sodium salt and vanadic acid mixed solution until precipitate is separated out, thus obtaining ammonium vanadate; then adding sulfuric acid into the tungsten-and-vanadium-removed SCR catalyst, and reacting to obtain a titanyl sulfate solution and solids such as aluminum slag and the like; then adding water into the titanyl sulfate solution, and hydrolyzing to obtain titanic acid and a waste acid solution; and finally, respectively calcining the obtained ammonium vanadate, tungstic acid and titanic acid to obtain vanadium pentoxide, tungsten trioxide and titanium dioxide. According to the invention, tungsten, titanium and vanadium can be extracted from the SCR catalyst through the reaction with strong alkali and strong acid at a low temperature, the equipment requirement is low, the energy consumption is low, some products having added values can be coproduced, and no secondary pollution is generated, thereby facilitating popularization and application.
Description
Technical field
The invention belongs to discarded catalyst recovery and utilize technical field, be specifically related to a kind of method of extracting tungsten, titanium, vanadium from discarded SCR catalyzer.
Background technology
SCR(SCR) the catalyzer nitrogen oxides pollution thing that to be fuel-burning power plant produce for removing burning, wherein also contains V
2o
5etc. objectionable impurities.Data show, cut-off was to 2008, the SCR device of the existing 2,000 ten thousand kilowatts of fired power generating unit of China puts into operation, and 2009 is 10,000 ten thousand kilowatts in the SCR device installed capacity of building, cause therefrom SCR catalyst recovery process recycling problem and also bring into schedule.Estimate, by 2010, the installed capacity of domestic SCR device will reach 32,000 ten thousand kilowatts, and the initial amount of fill of its catalyzer will reach 260000m
3.Calculate work-ing life according to 3 years left and right of SCR catalyzer, by 2012,260000m will have an appointment
3discarded catalyzer produce.If a large amount of discarded catalyzer are in addition suitable processing not, the accumulation of accumulating over a long period will form " mine, city ", what bring us is not only the waste in resource, but also can cause serious environmental pollution, wherein comparatively serious is groundwater pollution, and the water of pollution can bring great impact to people's health again.And discarded SCR catalyzer belongs to special article, must reasonably dispose by certain standard and rules, therefore, the recovery and utilization technology of research and development catalyzer is all very important (Wang Hu from the angle of Economic development or the angle of environmental protection, the recycling of metal oxide [J] in SCR denitrating catalyst. Gansu power technology, 2011(02): 29-30).
Although the regeneration of discarded SCR catalyzer had the experience of successful operation abroad, domestic not yet have a relevant catalyst regeneration experience.Moreover have data to think, the regeneration cost of discarded catalyzer is very expensive.Therefore for the consideration of economy and other side, processing or the utilization of discarded catalyzer being carried out to other seem particularly important, especially along with fuel-burning power plant selective reduction denitration project is built on a large scale, the sharply increase of discarded catalytic amount, reasonable disposal to discarded catalyzer and utilization will be new research topic (Xu Furong, the Zhou Lirong that scientific worker faces; The SCR of coal-burning power plant denitrification apparatus spent catalyst processing scheme is inquired into [J]. China environmental protection industry, 2010, (11): 25-27).
At present, other approach of discarded catalyst treatment and utilization has: (1) landfill disposal; (2) return to catalyzer retailer; (3) as cement raw material or aggregate; (4) grind rear and coal multifuel combustion; (5) reclaim useful metal material wherein.The useful metal material of wherein recycling is wherein a kind of processing mode of environmental protection more, and its method is out recycle of extracting section useful in discarded catalyzer by various physics, chemical process.Because by the recycling to discarded catalyzer, the recyclable TiO of discarded catalyzer of every cubic metre
2about 800kg; WO
3+ V
2o
5+ MoO
3about 90kg.If can recycle to the above discarded catalyzer when the time comes recyclable TiO
2208000 tons; WO
3+ V
2o
5+ MoO
32340 tons.According to TiO in the market
2: 1.5 ~ 20,000 yuan/ton; WO
3: 15 ~ 160,000 yuan/ton; V
2o
5: 11 ~ 120,000 yuan/ton; MoO
3: the calculation of price of 15 ~ 160,000 yuan/ton, every cubic metre of discarded catalyzer can produce the output value of at least 2.55 ten thousand yuans, and its gross output value will reach at least 66.3 hundred million Renminbi.If calculated according to 30% profit, can produce every year nearly 2,000,000,000 Renminbi profit (Wang Hu, the recycling of metal oxide [J] in SCR denitrating catalyst. Gansu power technology, 2011(02): 29-30).Even so, but current this treatment process price is still more expensive, thereby also not application on a large scale.But along with the progress of technology, this treatment process be expected to become main flow treatment process (Xu Furong, the SCR of Zhou Lirong coal-burning power plant denitrification apparatus spent catalyst processing scheme inquire into [J]. China environmental protection industry, 2010, (11): 25-27).
Chinese invention patent number is 201010254247 to disclose " a kind of method that reclaims metal oxide from waste flue gas denitration catalyst ", and the method is first after High Temperature Pre calcination process, to add in proportion Na by carrying out after waste flue gas denitration catalyst fragmentation
2cO
3and mix, pulverize, then carry out high-temperature roasting.Agglomerate drops into agitation leach in hot water after pulverizing.Gained titanate adds sulfuric acid, after filtration, washing, roasting, can obtain TiO
2.Filtrate after leaching adds sulphur acid for adjusting pH value to 8.0 ~ 9.0, then adds excessive NH
4cl precipitation.The NH that filtration is obtained
4vO
3through pyrolytic decomposition, make V
2o
5finished product.Filtrate salt adding acid for adjusting pH value to 4.5 ~ 5.0 after precipitation, then add CaCl
2heavy molybdenum, tungsten.Filter gained CaMoO
4and CaWO
4get final product to obtain MoO through roasting again with salt acid treatment
3with WO
3.Because the method needs repeatedly at high temperature roasting, equipment requirements is high, and investment is large, and energy consumption is high, and the method need use excessive sodium carbonate, and this will produce a large amount of carbon dioxides, and environment is caused to serious pollution.
Summary of the invention
The object of the invention is the deficiency existing for above-mentioned prior art, a kind of method of extracting tungsten, titanium, vanadium from discarded SCR catalyzer is provided.
The method of extracting tungsten, titanium, vanadium from discarded SCR catalyzer provided by the invention, processing step and the condition of the method are as follows:
1) discarding SCR catalyst powder, to be broken to granularity be 100～200 orders, then adding mass percent concentration is 20～30% strong base solutions, at 150～200 ℃ of temperature, react 3～6 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, and the mass ratio of discarded SCR catalyzer and highly basic is 10:3～6;
2) be first 1:3～6 by the mass ratio of strong acid and sodium wolframate and sodium vanadate solution, be made into mass percent concentration and be 70～80% strong acid solution, then add in sodium wolframate, vanadic acid sodium mixing solutions, at 150～200 ℃, react 1～4 hour, filtering separation obtains tungstic acid solid and sodium salt, vanadic acid mixing solutions, in sodium salt, vanadic acid mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.00 ~ 8.00 again, Precipitation, filtering separation obtains ammonium vanadate and ammonium salt solution, and the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid;
3) be that to be made into mass percent concentration be 90 ~ 98% sulphuric acid soln to 10 ~ 14:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 200～250 ℃, react 2～4 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag;
4) in titanyl sulfate solution, 1:10 ~ 13 add water by volume, and in 80 ~ 100 ℃ of hydrolysis 1 ~ 2 hour, filtering separation obtained metatitanic acid solid and waste acid liquor;
5) ammonium vanadate, wolframic acid, the metatitanic acid that above step are obtained, calcine and can obtain respectively Vanadium Pentoxide in FLAKES, tungstic oxide and titanium dioxide by existing Technology.
Above method steps 2) in the tungstic acid solid that obtains can purify by such method: in tungstic acid solid, add ammoniacal liquor for 1:20～30 in mass ratio, then at 100～120 ℃, react 1～3 hour, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, in ammonium tungstate solution, adding mass percent concentration is 70～80% strong acid solution again, in 120～150 ℃ of acidifyings 1～3 hour, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, and the mass ratio of ammonium tungstate solution and strong acid is 3 ~ 5:1;
Discarded SCR catalyzer described in the step 1) of above method and the mass ratio of highly basic are preferably 10:3 ~ 5, and temperature of reaction is preferably 150 ~ 180 ℃, and the reaction times is preferably 3 ~ 5 hours.
The step 2 of above method) described in strong acid and the mass ratio of sodium wolframate, sodium vanadate solution be preferably 1:3 ~ 5, the reaction times is preferably 1 ~ 3 hour.
Reaction times described in the step 3) of above method is preferably 2 ~ 3 hours.
Highly basic described in above method is preferably sodium hydroxide or potassium hydroxide; Described strong acid is preferably any in sulfuric acid, hydrochloric acid or nitric acid.
Compared with the prior art, the invention has the advantages that:
1, because the present invention is without calcination repeatedly at high temperature, only need can from SCR catalyzer, extract the useful metal such as tungsten, titanium, vanadium by substep by just reacting with highly basic and/or strong acid at a lower temperature, thereby not only low for equipment requirements, energy consumption is low, and has effectively solved again the problem of SCR catalyst contamination environment.
2, because the present invention is extracting in the metal process such as tungsten, vanadium, silicon, only need to adopt some conventional raw materials such as alkali, acid, ammoniacal liquor, cheap, material consumption is few in addition, thereby extraction cost is low, more easily applies.
3, the sial slag producing in the metal process such as extraction tungsten, vanadium, silicon due to the present invention can be used as producing the raw material of materials for wall, ammonium salts etc. can be used as fertilizer, hydrolysis water can recycle, thereby the designed operational path of the method both can coproduction some products with added value reduce production costs, can not produce again secondary pollution, meet very much the requirement of modern cleaner production.
4, due to simply maturation of technique of the present invention, condition is easy to control, and easily grasps, and production cost is low in addition, thereby provides the path that can apply on a large scale for carrying out recycle with chemical process extraction recovery metal oxide from discarded catalyzer.
Embodiment
Provide embodiment below so that the invention will be further described.
Embodiment 1
(1) by being crushed to the discarded SCR catalyzer of 120 orders, to add mass percent concentration be 20% sodium hydroxide solution, at 200 ℃ of temperature, react 3 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and sodium hydroxide 10:6 in mass ratio;
(2) first press sulfuric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:3, be made into mass percent concentration and be 70% sulphuric acid soln, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 150 ℃, react 4 hours, filtering separation obtains tungstic acid solid and sodium sulfate, vanadic acid sodium mixing solutions, again at sodium sulfate, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.00, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:20 adds ammoniacal liquor, then at 120 ℃, react 3 hours, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 70% sulphuric acid soln, in 120 ℃ of acidification reactions 1 hour, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and sulfuric acid is 3:1,
(3) be that to be made into mass percent concentration be 90% sulphuric acid soln to 10:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 250 ℃, react 2 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag, in titanyl sulfate solution, 1:13 adds water by volume again, and in 100 ℃ of hydrolysis reaction 1 hour, filtering separation obtained metatitanic acid solid and waste acid liquor (capable of circulation be with);
(4) the ammonium vanadate solid above step being obtained makes Vanadium Pentoxide in FLAKES 800 ~ 850 ℃ of calcining and decomposing, and high purity tungstic acid solid makes tungstic oxide 700 ~ 750 ℃ of calcinings, and metatitanic acid solid is calcined to obtain titanium dioxide at 650 ~ 850 ℃.
Embodiment 2
(1) by being crushed to the discarded SCR catalyzer of 200 orders, to add mass percent concentration be 30% potassium hydroxide solution, at 180 ℃ of temperature, react 5.5 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and potassium hydroxide 10:4.5 in mass ratio;
(2) first press sulfuric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:4.5, be made into mass percent concentration and be 76% sulphuric acid soln, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 160 ℃, react 2.5 hours, filtering separation obtains tungstic acid solid and sodium sulfate, vanadic acid sodium mixing solutions, again at sodium sulfate, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.20, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:30 adds ammoniacal liquor, then at 105 ℃, react 3 hours, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 80% sulphuric acid soln, in 130 ℃ of acidification reactions 3 hours, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and sulfuric acid is 5:1,
(3) be that to be made into mass percent concentration be 98% sulphuric acid soln to 13:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 200 ℃, react 4 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag, in titanyl sulfate solution, 1:10 adds water by volume again, and in 90 ℃ of hydrolysis reaction 1.5 hours, filtering separation obtained metatitanic acid solid and waste acid liquor;
(4) with embodiment 1, slightly.
Embodiment 3
(1) by being crushed to the discarded SCR catalyzer of 170 orders, to add mass percent concentration be 26% sodium hydroxide solution, at 150 ℃ of temperature, react 4 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and sodium hydroxide 10:5 in mass ratio;
(2) first press sulfuric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:5, be made into mass percent concentration and be 80% sulphuric acid soln, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 170 ℃, react 3.5 hours, filtering separation obtains tungstic acid solid and sodium sulfate, vanadic acid sodium mixing solutions, again at sodium sulfate, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 8.00, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:24 adds ammoniacal liquor, then at 120 ℃, react 2 hours, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 74% sulphuric acid soln, in 150 ℃ of acidification reactions 2.5 hours, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and sulfuric acid is 4.5:1,
(3) be that to be made into mass percent concentration be 96% sulphuric acid soln to 12:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 240 ℃, react 3.5 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag, in titanyl sulfate solution, 1:11 adds water by volume again, and in 100 ℃ of hydrolysis reaction 1 hour, filtering separation obtained metatitanic acid solid and waste acid liquor;
(4) with embodiment 1, slightly.
Embodiment 4
(1) by being crushed to the discarded SCR catalyzer of 140 orders, to add mass percent concentration be 22% potassium hydroxide solution, at 170 ℃ of temperature, react 6 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and potassium hydroxide 10:3.5 in mass ratio;
(2) first press hydrochloric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:3.5, be made into mass percent concentration and be 72% hydrochloric acid soln, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 180 ℃, react 2 hours, filtering separation obtains tungstic acid solid and sodium-chlor, vanadic acid sodium mixing solutions, again at sodium-chlor, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.60, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:26 adds ammoniacal liquor, then at 110 ℃, react 2.5 hours, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 78% hydrochloric acid soln, in 125 ℃ of acidification reactions 2 hours, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and hydrochloric acid is 3:1,
(3) be that to be made into mass percent concentration be 92% sulphuric acid soln to 12:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 220 ℃, react 3 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag, in titanyl sulfate solution, 1:12 adds water by volume again, and in 85 ℃ of hydrolysis reaction 1.5 hours, filtering separation obtained metatitanic acid solid and waste acid liquor;
(4) with embodiment 1, slightly.
Embodiment 5
(1) by being crushed to the discarded SCR catalyzer of 170 orders, to add mass percent concentration be 24% potassium hydroxide solution, at 190 ℃ of temperature, react 3.5 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and potassium hydroxide 10:4 in mass ratio;
(2) first press hydrochloric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:4, be made into mass percent concentration and be 78% hydrochloric acid soln, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 190 ℃, react 1 hour, filtering separation obtains tungstic acid solid and sodium-chlor, vanadic acid sodium mixing solutions, again at sodium-chlor, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.80, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:28 adds ammoniacal liquor, then at 100 ℃, react 1 hour, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 72% hydrochloric acid soln, in 140 ℃ of acidification reactions 1.5 hours, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and sulfuric acid is 3.5:1,
(3) be that to be made into mass percent concentration be 94% sulphuric acid soln to 11:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 230 ℃, react 2.5 hours, filtering separation obtain the solid such as titanyl sulfate solution and aluminium slag (, in titanyl sulfate solution, 1:10 adds water by volume again, and in 95 ℃ of hydrolysis reaction 1.5 hours, filtering separation obtained metatitanic acid solid and waste acid liquor;
(4) with embodiment 1, slightly.
Embodiment 6
(1) by being crushed to the discarded SCR catalyzer of 100 orders, to add mass percent concentration be 28% sodium hydroxide solution, at 160 ℃ of temperature, react 4.5 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and sodium hydroxide 10:5.5 in mass ratio;
(2) first press nitric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:5, be made into mass percent concentration and be 74% salpeter solution, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 200 ℃, react 3 hours, filtering separation obtains tungstic acid solid and SODIUMNITRATE, vanadic acid sodium mixing solutions, again in SODIUMNITRATE, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.40, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:22 adds ammoniacal liquor, then at 115 ℃, react 1.5 hours, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 76% salpeter solution, in 145 ℃ of acidification reactions 2.5 hours, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and nitric acid is 4:1,
(3) be that to be made into mass percent concentration be 98% sulphuric acid soln to 14:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 210 ℃, react 4 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag, in titanyl sulfate solution, 1:13 adds water by volume again, and in 80 ℃ of hydrolysis reaction 2 hours, filtering separation obtained metatitanic acid solid and waste acid liquor;
(4) with embodiment 1, slightly.
Embodiment 7
(1) by being crushed to the discarded SCR catalyzer of 200 orders, to add mass percent concentration be 20% sodium hydroxide solution, at 180 ℃ of temperature, react 5 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, wherein discarded SCR catalyzer and sodium hydroxide 10:3 in mass ratio;
(2) first press nitric acid and sodium wolframate, the mass ratio of vanadic acid sodium mixing solutions is 1:4, be made into mass percent concentration and be 70% salpeter solution, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 180 ℃, react 1.5 hours, filtering separation obtains tungstic acid solid and SODIUMNITRATE, vanadic acid sodium mixing solutions, again in SODIUMNITRATE, in vanadic acid sodium mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7.40, Precipitation, filtering separation obtains ammonium vanadate solid and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid, and in tungstic acid solid in mass ratio for 1:26 adds ammoniacal liquor, then at 100 ℃, react 2 hours, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, continuing to add mass percent concentration in ammonium tungstate solution is 80% salpeter solution, in 135 ℃ of acidification reactions 3 hours, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and nitric acid is 5:1,
(3) be that to be made into mass percent concentration be 90% sulphuric acid soln to 10:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 230 ℃, react 3 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag, in titanyl sulfate solution, 1:10 adds water by volume again, and in 95 ℃ of hydrolysis reaction 2 hours, filtering separation obtained metatitanic acid solid and waste acid liquor;
(4) with embodiment 1, slightly.
In addition, it should be noted that, the specific embodiment described in this specification sheets, its formula, title that technique is named etc. can be different.In every case equivalence or the simply change made according to the described feature of patent conception of the present invention and principle, include and be in protection scope of the present invention.Those skilled in the art can make various modifications or supplement or adopt similar mode to substitute described specific embodiment; only otherwise depart from scope as defined in the claims of the present invention, all should belong to protection scope of the present invention.
Claims (8)
1. a method of extracting tungsten, titanium, vanadium from discarded SCR catalyzer, processing step and the condition of the method are as follows:
1) discarding SCR catalyst powder, to be broken to granularity be 100～200 orders, then adding mass percent concentration is 20～30% strong base solutions, at 150～200 ℃ of temperature, react 3～6 hours, filtering separation obtains the SCR catalyzer of de-tungsten, vanadium and sodium wolframate, vanadic acid sodium mixing solutions, and wherein the mass ratio of discarded SCR catalyzer and highly basic is 10:3～6;
2) be first 1:3～6 by the mass ratio of strong acid and sodium wolframate and sodium vanadate solution, be made into mass percent concentration and be 70～80% strong acid solution, then add sodium wolframate, in vanadic acid sodium mixing solutions, at 150～200 ℃, react 1～4 hour, filtering separation obtains tungstic acid solid and sodium salt, vanadic acid mixing solutions, again the tungstic acid solid of gained is added to ammoniacal liquor in 1:20～30 in mass ratio, then at 100～120 ℃, react 1～3 hour, filtering separation obtains ammonium tungstate solution and silicic acid filter cake, in ammonium tungstate solution, adding mass percent concentration is 70～80% strong acid solution again, in 120～150 ℃ of acidifyings 1～3 hour, filtering separation obtains highly purified tungstic acid solid and ammonium salt solution, the mass ratio of ammonium tungstate solution and strong acid is 3～5:1, then at the sodium salt of gained, in vanadic acid mixing solutions, adding ammoniacal liquor, to be adjusted to pH value be 7～8, Precipitation, filtering separation obtains ammonium vanadate and ammonium salt solution, the concentrated crystallisation by cooling of ammonium salt solution obtains ammonium salt solid,
3) be that to be made into mass percent concentration be 90～98% sulphuric acid soln to 10～14:1 by sulfuric acid by the mass ratio of the SCR catalyzer of the de-tungsten obtaining with step 1), vanadium, then add in the SCR catalyzer of de-tungsten, vanadium, at 200～250 ℃, react 2～4 hours, filtering separation obtains the solid such as titanyl sulfate solution and aluminium slag;
4) in titanyl sulfate solution, 1:10～13 add water by volume, and in 80～100 ℃ of hydrolysis 1～2 hour, filtering separation obtained metatitanic acid solid and waste acid liquor;
5) ammonium vanadate, wolframic acid, the metatitanic acid that above step are obtained, calcine and can obtain respectively Vanadium Pentoxide in FLAKES, tungstic oxide and titanium dioxide by existing Technology,
Wherein said strong acid is sulfuric acid or nitric acid.
2. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer claimed in claim 1, it is characterized in that the discarded SCR catalyzer described in the step 1) of the method and the mass ratio of highly basic are 10:3～5, temperature of reaction is 150～180 ℃, and the reaction times is 3～5 hours.
3. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer described in claim 1 or 2, it is characterized in that the step 2 of the method) described in strong acid and the mass ratio of sodium wolframate, sodium vanadate solution be 1:3～5, the reaction times is 1～3 hour.
4. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer described in claim 1 or 2, it is characterized in that the reaction times described in the step 3) of the method is 2～3 hours.
5. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer claimed in claim 3, it is characterized in that the reaction times described in the step 3) of the method is 2～3 hours.
6. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer described in claim 1 or 2, it is characterized in that the highly basic described in the method is sodium hydroxide or potassium hydroxide.
7. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer claimed in claim 4, it is characterized in that the highly basic described in the method is sodium hydroxide or potassium hydroxide.
8. according to the method for extracting tungsten, titanium, vanadium from discarded SCR catalyzer claimed in claim 5, it is characterized in that the highly basic described in the method is sodium hydroxide or potassium hydroxide.
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| CN105709863A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | SCR flue gas denitration catalyst regeneration fluid and preparation method thereof |
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