CN104118911B - A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely - Google Patents

A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely Download PDF

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CN104118911B
CN104118911B CN201410334663.7A CN201410334663A CN104118911B CN 104118911 B CN104118911 B CN 104118911B CN 201410334663 A CN201410334663 A CN 201410334663A CN 104118911 B CN104118911 B CN 104118911B
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scr catalyst
tungstic oxide
discarded scr
filtrate
alkali
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CN104118911A (en
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李锋
吕腾飞
杨俊杰
王一罕
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Shenyang Yuanda solid waste treatment Co. Ltd.
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SHENYANG YUANDA TECHNOLOGY PARK Co Ltd
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    • 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
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    • 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 present invention relates to denitrating flue gas field, be specially a kind of method reclaiming tungstic oxide in discarded SCR catalyst completely.By the water soaking removal of impurities of the waste catalyst after pulverizing with 3 ~ 4 times of volumes; Powder after removal of impurities adds the alkaline solution that excessive concentration is 60 ~ 80wt%, keeps 140 ~ 150 DEG C to soak 3 ~ 5 hours, and filters; Filtrate concentration and recovery alkali; Separate out concentrated liquid acid adding modulation pH value to 7 ~ 8 after alkali, silica removal, the silicic acid that filtering generates; Filtrate pH value is transferred to more than 10, boils and carry out wolframate radical unification; Filtrate is cooled to 60 ~ 80 DEG C, is added drop-wise in the nitric acid of isopyknic 8 ~ 12mol/L, cold filtration, obtains highly purified yellow wolframic acid.The present invention does not need roasting just can make the complete sodium of tungstic oxide, and the tungstic oxide of low levels can be converted into wolframic acid completely, and can silica removal completely, greatly reduces the energy consumption of a cost and the operation of founding the factory.

Description

A kind of method reclaiming tungstic oxide in discarded SCR catalyst completely
Technical field
The present invention relates to denitrating flue gas field, be specially a kind of method reclaiming tungstic oxide in discarded SCR catalyst completely.
Background technology
It is high that selective catalytic reduction (SCR) gas denitrifying technology has denitration efficiency, selectivity is good, and the advantages such as mature and reliable are widely used in thermal power station, be the main flow of coal unit denitration, SCR method denitration catalyst activity material main chemical compositions has TiO 2, V 2o 5, WO 3and MoO 3, these compositions account for more than 90% of catalyzer composition.But the metals such as one side tungsten, vanadium, titanium are all from external import, and cost is very expensive.Another aspect catalyzer belongs to a kind of and consumes thing, can slowly lose original effect after using for some time, needs to activate, at present the domestic activating technology that yet there are no maturation.Further, the work-ing life of catalyzer also only has 3 ~ 4 years, and the needs that exceed the time limit are changed in time, and how a large amount of spent catalyst lost efficacy processes, disposes the great attention causing countries in the world.If do not add disposal to these spent catalyst and arbitrarily bank up, a large amount of land resources can be taken on the one hand, increase the cost of enterprise; Some poisonous and harmful substances that another aspect catalyzer adsorbs in the middle of use procedure and some metallic elements contained by self can enter into physical environment due to various effect, and particularly water body, brings serious harm to environment; The third aspect, spent catalyst abandons, and wherein contained various valuable metal resources could not be recycled utilization, cause the huge waste of efficient resource.So carrying out spent catalyst recovery and utilizing both can turn waste into wealth, changed evil for benefit, and corresponding a series of potential problem of environmental pollution can also be solved, thus bring considerable economic benefit and social benefit.
Chinese invention patent application (publication number CN102557142A) provide a kind of method reclaiming tungstic oxide and ammonium meta-vanadate from SCR denitration, by SCR denitration pulverize, sieve after make catalyst fines, stir after mixing sodium carbonate, then mixed powder is put into sintering oven calcining and become sintered material, be incubated after 1 hour and pulverize, sieve and make sintered material powder, then pour the Na that warm water makes in sintered material powder into 2wO 4and NaVO 3abundant dissolving, after filtration, discard precipitation after obtain Na 2wO 4and NaVO 3mixing solutions; Behind adjust ph to 6.5 ~ 7.5, add bicarbonate of ammonia or ammonium chloride solution, separate out ammonium metavanadate precipitate, first with rare ammonium bicarbonate soln washing 2 ~ 3 times after filtration, then use the washing with alcohol 1 ~ 2 time of 30%, after oven dry ammonium meta-vanadate finished product; Na in surplus solution 2wO 4convert ammonium paratungstate to, by obtained for surplus solution evaporation order of ammoniumparatungstate crystal, then carry out calcining obtained tungstic oxide.Its weak point is, calcination process considerably increases the energy consumption of a cost and the operation of founding the factory.
Summary of the invention
The object of the present invention is to provide a kind of method reclaiming tungstic oxide in discarded SCR catalyst completely, do not need roasting process, the tungstic oxide of low levels can be enable to be converted into yellow wolframic acid completely, reclaim tungstic oxide more than 99%.
Technical scheme of the present invention is:
Reclaim a method for tungstic oxide in discarded SCR catalyst completely, by the water soaking removal of impurities of the waste catalyst after pulverizing with 3 ~ 4 times of volumes; Powder after removal of impurities adds the alkaline solution that excessive concentration is 60 ~ 80wt%, keeps 140 ~ 150 DEG C to soak 3 ~ 5 hours, and filters; Filtrate concentration and recovery alkali; Separate out concentrated liquid acid adding modulation pH value to 7 ~ 8 after alkali, silica removal, the silicic acid that filtering generates; Filtrate pH value is transferred to more than 10, boils and carry out wolframate radical unification; Filtrate is cooled to 60 ~ 80 DEG C, is added drop-wise in the nitric acid of isopyknic 8 ~ 12mol/L, cold filtration, obtains highly purified yellow wolframic acid.
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, the concrete steps reclaiming tungstic oxide in discarded SCR catalyst are completely as follows:
1) pulverize: discarded SCR catalyst is crushed to more than 150 orders, for subsequent use;
2) water soaking powder impurity elimination: by the water soaking of the discarded SCR catalyst after pulverizing with 3 ~ 4 times of volumes, remove the arsenic of absorption, mercury, an alkali metal salt and organic substance, the waste water filtered out, after charcoal absorption arsenic, mercury and organic substance, recycles;
3) leach: the wet powder after impurity elimination add 4 ~ 6 times of volumes, concentration is the alkaline solution of 60 ~ 80wt%, be heated to 140 ~ 150 DEG C, soak 3 ~ 5 hours, make V 2o 5, WO 3, MoO 3, TiO 2sodium, generates NaVO 3, Na 2wO 4, Na 2moO 4solution and Na 2tiO 3filter cake precipitates, and adopts and filter Na 2tiO 3filter cake precipitates;
4) reclaim alkali: by step 3) filter after liquid heat be concentrated into 1/5 ~ 1/15 of original volume, separate out solid alkali, solid alkali reuse after filtering, filtrate enters next operation;
5) silica removal: by step 4) filter after filtrate adjusted to ph under the condition of boiling be 7 ~ 8, seethe with excitement 10 ~ 30 minutes, filtration, filter cake is silicic acid;
6) wolframate radical is unified: by step 5) filter after filtrate adjusted to ph under the condition of boiling be more than 10, boil 0.5 ~ 5 hour, reach unified wolframate radical WO 4 2-;
7) precipitate yellow wolframic acid: by step 6) filtrate at 60 ~ 80 DEG C, be added drop-wise in isopyknic 8 ~ 12mol/L nitric acid, cold filtration, obtain yellow wolframic acid WO 32H 2o.
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, step 1) in, it is 150 order ~ 400 orders that discarded SCR catalyst is crushed to granularity.
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, step 3) in, there is following chemical reaction in leaching process:
V 2O 5+2NaOH→2NaVO 3+H 2O；
WO 3+2NaOH→Na 2WO 4+H 2O；
MoO 3+2NaOH→Na 2MoO 4+H 2O；
TiO 2+2NaOH→Na 2TiO 3+H 2O。
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, step 3) in, when containing tetravalence vanadium V in discarded SCR catalyst 2o 4or VOSO 4time, adding concentration is that the Potcrate aqueous solution of 1 ~ 2wt% is oxidized to pentavalent vanadium, and its reaction formula is as follows:
3V 2O 4+6NaOH+KClO 3→6NaVO 3+KCl+3H 2O；
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, by step 3) in filter after the washing of filter cake 3 ~ 5 times of volumes, then filter cake is after filtering sodium titanate product; After washing filter cake, the filtrate that produces is by step 4) in the solid alkali of separating out add supplementary solid alkali, be mixed with the alkaline solution that concentration is 60 ~ 80wt%, the step 3 as removal process next time) in alkali leaching liquor.
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, step 5) in, the purity >=98wt% of silicic acid.
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, step 6) in, the reaction formula precipitating yellow wolframic acid is as follows:
Na 2WO 4·2H 2O+2HNO 3→WO 3·2H 2O+2NaNO 3+H 2O。
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, in discarded SCR catalyst, the content of tungstic oxide is 2 ~ 10wt%, the complete sodium of tungstic oxide, the tungstic oxide of low levels can be converted into yellow wolframic acid completely, and obtaining yellow wolframic acid purity is more than 99wt%.
The described method reclaiming tungstic oxide in discarded SCR catalyst completely, alkaline solution is the NaOH aqueous solution, and solid alkali is solid NaOH.
Advantage of the present invention and beneficial effect are:
1, the present invention does not need roasting process in an alkali leaching, and only the concentrated alkali solution of need about 145 DEG C, about 70wt% soaks 4 hours, just can make the complete sodium of tungstic oxide, and the tungsten in waste catalyst and vanadium can be made to generate Na 2wO 4and Na 2vO 3, greatly reduce the energy consumption of a cost and the operation of founding the factory.
2, the present invention can enable the tungstic oxide of low levels be converted into wolframic acid completely, and can silica removal completely.
3, the present invention can reclaim more than tungstic oxide 99wt%, does not need roasting, and waste water can directly discharge.
Embodiment
In a specific embodiment, the present invention reclaims the method for tungstic oxide in discarded SCR catalyst completely, by the water soaking removal of impurities of the waste catalyst (its granularity is 150 order ~ 400 orders) after pulverizing with 3 ~ 4 times of volumes, after removal of impurities, powder adds the alkaline solution that excessive concentration is 60 ~ 80wt%, 140 ~ 150 DEG C are kept to soak 3 ~ 5 hours, and filter (after adding excess base solution, generation NaVO 3, Na 2wO 4, Na 2moO 4solution and Na 2tiO 3precipitation, and adopted and filter Na 2tiO 3precipitation); Filtrate concentration and recovery alkali, remaining liq acid adding modulation pH value to 7 ~ 8, silica removal, the silicic acid that filtering generates; Filtrate pH value is transferred to more than 10, boils and carry out wolframate radical unification; Filtrate is cooled to 60 ~ 80 DEG C, is added drop-wise in the nitric acid of isopyknic 8 ~ 12mol/L, cold filtration, obtains highly purified yellow wolframic acid (its purity is more than 99wt%).
Below by embodiment, the present invention is described in more detail.
Embodiment 1
In the discarded SCR catalyst of the present embodiment, V 2o 5account for 1.34wt%, WO 3account for 3.02wt%, MoO 3account for 0.002wt%, TiO 2account for 85wt%, SiO 2account for 7.5wt%.The concrete steps reclaiming tungstic oxide in discarded SCR catalyst are completely as follows:
1) pulverize: discarded SCR catalyst is crushed to 150 orders, for subsequent use.
2) water soaking powder impurity elimination: by the water soaking of the discarded SCR catalyst after pulverizing with 3.5 times of volumes, remove the arsenic of absorption, mercury, an alkali metal salt and organic substance, the waste water filtered out, after charcoal absorption arsenic, mercury and organic substance, can recycle.
3) leach: the wet powder after impurity elimination add 5 times of volumes, concentration is the NaOH aqueous solution of 70wt%, be heated to 145 DEG C, soak 4 hours, most of vanadium, tungsten, molybdenum and titanium can leach, and make V 2o 5, WO 3, MoO 3, TiO 2sodium.Mainly there is following chemical reaction in leaching process:
V 2O 5+2NaOH→2NaVO 3+H 2O
WO 3+2NaOH→Na 2WO 4+H 2O
MoO 3+2NaOH→Na 2MoO 4+H 2O
TiO 2+2NaOH→Na 2TiO 3+H 2O
If containing tetravalence vanadium (V in raw material (discarded SCR catalyst) 2o 4, VOSO 4), need add concentration is that the Potcrate aqueous solution of 1 ~ 2wt% is oxidized to pentavalent vanadium, and its reaction formula is as follows:
3V 2O 4+6NaOH+KClO 3→6NaVO 3+KCl+3H 2O
4) reclaim alkali: by step 3) filter after liquid heat be concentrated into 1/10 of original volume, separate out solid alkali (NaOH), solid alkali reuse after filtering, filtrate enters next operation.
By step 3) in filter after the filter cake washing of 4 times of volumes, by the NaVO that sodium titanate and described filter cake are adhered to 3, Na 2wO 4, Na 2moO 4separate completely, then filter cake is after filtering sodium titanate product.After washing filter cake, the filtrate that produces is by step 4) in the solid alkali (NaOH) of separating out add supplementary solid alkali (NaOH), be mixed with the NaOH aqueous solution that concentration is 70wt%, the step 3 as removal process next time) in alkali leaching liquor.
5) silica removal: by step 4) filter after filtrate adjusted to ph under the condition of boiling be 7.5, seethe with excitement 20 minutes, filtration, filter cake is high purity (>=98wt%) silicic acid.
6) wolframate radical is unified: by step 5) filter after filtrate adjusted to ph under the condition of boiling be more than 10, boil 1 hour, reach wolframate radical unified.
In the present invention, the reason of carrying out wolframate radical unified is as follows: under weakly alkaline and silicon-dioxide are the condition of catalyzer, wolframate radical (WO 4 2-) easily generate poly wolframate radical (W 7o 24 6-), such wolframate radical can not be settled out yellow wolframic acid at sour environment.Therefore, pH value is adjusted to more than 10, and boils 1 hour, making wolframate radical unified is the activated wolframate radical (WO of tool 4 2-) ion.
7) precipitate yellow wolframic acid: by step 6) filtrate at 70 DEG C, be added drop-wise in the nitric acid of isopyknic 10mol/L, cold filtration, obtain yellow wolframic acid (WO 32H 2o), its reaction formula is as follows:
Na 2WO 4·2H 2O+2HNO 3→WO 3·2H 2O+2NaNO 3+H 2O
In the present embodiment, in an alkali leaching, do not need roasting process, just can make the complete sodium of tungstic oxide, the tungstic oxide of low levels can be converted into yellow wolframic acid completely, and reclaim more than tungstic oxide 99wt%, waste water can directly discharge.
Embodiment 2
In the discarded SCR catalyst of the present embodiment, V 2o 5account for 1.34wt%, WO 3account for 3.02wt%, MoO 3account for 0.002wt%, TiO 2account for 85wt%, SiO 2account for 7.5wt%.Difference from Example 1 is, the concrete steps reclaiming tungstic oxide in discarded SCR catalyst are completely as follows:
1) pulverize: discarded SCR catalyst is crushed to 200 orders, for subsequent use;
2) water soaking powder impurity elimination: by the water soaking of the discarded SCR catalyst after pulverizing with 3 times of volumes, remove the arsenic of absorption, mercury, an alkali metal salt and organic substance, the waste water filtered out, after charcoal absorption arsenic, mercury and organic substance, recycles;
3) leach: the wet powder after impurity elimination add 4 times of volumes, concentration is the NaOH aqueous solution of 80wt%, be heated to 150 DEG C, soak 5 hours, vanadium, tungsten, molybdenum and titanium can leach, and make V 2o 5, WO 3, MoO 3, TiO 2sodium;
4) reclaim alkali: by step 3) filter after liquid heat be concentrated into 1/15 of original volume, separate out solid NaOH, solid NaOH reuse after filtering, filtrate enters next operation;
By step 3) in filter after the filter cake washing of 3 times of volumes, by the NaVO that sodium titanate and described filter cake are adhered to 3, Na 2wO 4, Na 2moO 4separate completely, then filter cake is after filtering sodium titanate product.After washing filter cake, the filtrate that produces is by step 4) in the solid alkali (NaOH) of separating out add supplementary solid alkali (NaOH), be mixed with the NaOH aqueous solution that concentration is 80wt%, the step 3 as removal process next time) in alkali leaching liquor.
5) silica removal: by step 4) filter after filtrate adjusted to ph under the condition of boiling be 7, seethe with excitement 30 minutes, filtration, filter cake is silicic acid, the purity >=98wt% of silicic acid;
6) wolframate radical is unified: by step 5) filter after filtrate adjusted to ph under the condition of boiling be more than 10, boil 4 hours, reach unified wolframate radical WO 4 2-;
7) precipitate yellow wolframic acid: by step 6) filtrate at 60 DEG C, be added drop-wise in isopyknic 8mol/L nitric acid, cold filtration, obtain yellow wolframic acid WO 32H 2o, yellow wolframic acid purity is more than 99wt%.
Embodiment 3
In the discarded SCR catalyst of the present embodiment, V 2o 5account for 1.34wt%, WO 3account for 3.02wt%, MoO 3account for 0.002wt%, TiO 2account for 85wt%, SiO 2account for 7.5wt%.Difference from Example 1 is, the concrete steps reclaiming tungstic oxide in discarded SCR catalyst are completely as follows:
1) pulverize: discarded SCR catalyst is crushed to 300 orders, for subsequent use;
2) water soaking powder impurity elimination: by the water soaking of the discarded SCR catalyst after pulverizing with 4 times of volumes, remove the arsenic of absorption, mercury, an alkali metal salt and organic substance, the waste water filtered out, after charcoal absorption arsenic, mercury and organic substance, recycles;
3) leach: the wet powder after impurity elimination add 6 times of volumes, concentration is the NaOH aqueous solution of 60wt%, be heated to 140 DEG C, soak 3 hours, vanadium, tungsten, molybdenum and titanium can leach, and make V 2o 5, WO 3, MoO 3, TiO 2sodium;
4) reclaim alkali: by step 3) filter after liquid heat be concentrated into 1/5 of original volume, separate out solid NaOH, solid NaOH reuse after filtering, filtrate enters next operation;
By step 3) in filter after the filter cake washing of 4 times of volumes, by the NaVO that sodium titanate and described filter cake are adhered to 3, Na 2wO 4, Na 2moO 4separate completely, then filter cake is after filtering sodium titanate product.After washing filter cake, the filtrate that produces is by step 4) in the solid alkali (NaOH) of separating out add supplementary solid alkali (NaOH), be mixed with the NaOH aqueous solution that concentration is 60wt%, the step 3 as removal process next time) in alkali leaching liquor.
5) silica removal: by step 4) filter after filtrate adjusted to ph under the condition of boiling be 8, seethe with excitement 10 minutes, filtration, filter cake is silicic acid, the purity >=98wt% of silicic acid;
6) wolframate radical is unified: by step 5) filter after filtrate adjusted to ph under the condition of boiling be more than 10, boil 3 hours, reach unified wolframate radical WO 4 2-;
7) precipitate yellow wolframic acid: by step 6) filtrate at 80 DEG C, be added drop-wise in isopyknic 12mol/L nitric acid, cold filtration, obtain yellow wolframic acid WO 32H 2o, yellow wolframic acid purity is more than 99wt%.
Embodiment 4
In the discarded SCR catalyst of the present embodiment, V 2o 5account for 1.34wt%, WO 3account for 3.02wt%, MoO 3account for 0.002wt%, TiO 2account for 85wt%, SiO 2account for 7.5wt%.Difference from Example 1 is, the concrete steps reclaiming tungstic oxide in discarded SCR catalyst are completely as follows:
1) pulverize: discarded SCR catalyst is crushed to 400 orders, for subsequent use;
2) water soaking powder impurity elimination: by the water soaking of the discarded SCR catalyst after pulverizing with 3.5 times of volumes, remove the arsenic of absorption, mercury, an alkali metal salt and organic substance, the waste water filtered out, after charcoal absorption arsenic, mercury and organic substance, recycles;
3) leach: the wet powder after impurity elimination add 5 times of volumes, concentration is the NaOH aqueous solution of 70wt%, be heated to 145 DEG C, soak 4 hours, vanadium, tungsten, molybdenum and titanium can leach, and make V 2o 5, WO 3, MoO 3, TiO 2sodium;
4) reclaim alkali: by step 3) filter after liquid heat be concentrated into 1/8 of original volume, separate out solid NaOH, solid NaOH reuse after filtering, filtrate enters next operation;
By step 3) in filter after the filter cake washing of 3.5 times of volumes, by the NaVO that sodium titanate and described filter cake are adhered to 3, Na 2wO 4, Na 2moO 4separate completely, then filter cake is after filtering sodium titanate product.After washing filter cake, the filtrate that produces is by step 4) in the solid alkali (NaOH) of separating out add supplementary solid alkali (NaOH), be mixed with the NaOH aqueous solution that concentration is 70wt%, the step 3 as removal process next time) in alkali leaching liquor.
5) silica removal: by step 4) filter after filtrate adjusted to ph under the condition of boiling be 7.2, seethe with excitement 15 minutes, filtration, filter cake is silicic acid, the purity >=98wt% of silicic acid;
6) wolframate radical is unified: by step 5) filter after filtrate adjusted to ph under the condition of boiling be more than 10, boil 2 hours, reach unified wolframate radical WO 4 2-;
7) precipitate yellow wolframic acid: by step 6) filtrate at 75 DEG C, be added drop-wise in isopyknic 9mol/L nitric acid, cold filtration, obtain yellow wolframic acid WO 32H 2o, yellow wolframic acid purity is more than 99wt%.
Embodiment result shows, the present invention does not need roasting just can make the complete sodium of tungstic oxide, and the tungstic oxide of low levels can be converted into wolframic acid completely, and can silica removal completely, greatly reduces the energy consumption of a cost and the operation of founding the factory.

Claims (9)

1. reclaim a method for tungstic oxide in discarded SCR catalyst completely, it is characterized in that, concrete steps are as follows:
1) pulverize: discarded SCR catalyst is crushed to more than 150 orders, for subsequent use;
2) water soaking powder impurity elimination: by the water soaking of the discarded SCR catalyst after pulverizing with 3 ~ 4 times of volumes, remove the arsenic of absorption, mercury, an alkali metal salt and organic substance, the waste water filtered out, after charcoal absorption arsenic, mercury and organic substance, recycles;
3) leach: the wet powder after impurity elimination add 4 ~ 6 times of volumes, concentration is the alkaline solution of 60 ~ 80wt%, be heated to 140 ~ 150 DEG C, soak 3 ~ 5 hours, make V 2o 5, WO 3, MoO 3, TiO 2sodium, generates NaVO 3, Na 2wO 4, Na 2moO 4solution and Na 2tiO 3filter cake precipitates, and adopts and filter Na 2tiO 3filter cake precipitates;
4) reclaim alkali: by step 3) filter after liquid heat be concentrated into 1/5 ~ 1/15 of original volume, separate out solid alkali, solid alkali reuse after filtering, filtrate enters next operation;
5) silica removal: by step 4) filter after filtrate adjusted to ph under the condition of boiling be 7 ~ 8, seethe with excitement 10 ~ 30 minutes, filtration, filter cake is silicic acid;
6) wolframate radical is unified: by step 5) filter after filtrate adjusted to ph under the condition of boiling be more than 10, boil 0.5 ~ 5 hour, reach unified wolframate radical WO 4 2-;
7) precipitate yellow wolframic acid: by step 6) filtrate at 60 ~ 80 DEG C, be added drop-wise in isopyknic 8 ~ 12mol/L nitric acid, cold filtration, obtain yellow wolframic acid WO 32H 2o.
2., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, step 1) in, it is 150 order ~ 400 orders that discarded SCR catalyst is crushed to granularity.
3., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, step 3) in, there is following chemical reaction in leaching process:
V 2O 5+2NaOH→2NaVO 3+H 2O；
WO 3+2NaOH→Na 2WO 4+H 2O；
MoO 3+2NaOH→Na 2MoO 4+H 2O；
TiO 2+2NaOH→Na 2TiO 3+H 2O。
4., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, step 3) in, when containing tetravalence vanadium V in discarded SCR catalyst 2o 4or VOSO 4time, adding concentration is that the Potcrate aqueous solution of 1 ~ 2wt% is oxidized to pentavalent vanadium, and its reaction formula is as follows:
3V 2O 4+6NaOH+KClO 3→6NaVO 3+KCl+3H 2O；
5., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, by step 3) in filter after the washing of filter cake 3 ~ 5 times of volumes, then filter cake is after filtering sodium titanate product; After washing filter cake, the filtrate that produces is by step 4) in the solid alkali of separating out add supplementary solid alkali, be mixed with the alkaline solution that concentration is 60 ~ 80wt%, the step 3 as removal process next time) in alkali leaching liquor.
6., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, step 5) in, the purity >=98wt% of silicic acid.
7., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, step 6) in, the reaction formula precipitating yellow wolframic acid is as follows:
Na 2WO 4·2H 2O+2HNO 3→WO 3·2H 2O+2NaNO 3+H 2O。
8. according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, in discarded SCR catalyst, the content of tungstic oxide is 2 ~ 10wt%, the complete sodium of tungstic oxide, the tungstic oxide of low levels can be converted into yellow wolframic acid completely, and obtaining yellow wolframic acid purity is more than 99wt%.
9., according to the method reclaiming tungstic oxide in discarded SCR catalyst completely according to claim 1, it is characterized in that, alkaline solution is the NaOH aqueous solution, and solid alkali is solid NaOH.
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