CN102491419A - Method for comprehensively recycling waste vanadium catalyst - Google Patents
Method for comprehensively recycling waste vanadium catalyst Download PDFInfo
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Abstract
The invention discloses a method for comprehensively recycling a waste vanadium catalyst. The method comprises the following steps of: performing reduction and acid leaching on the waste vanadium catalyst serving as a raw material, transferring vanadium and potassium into a liquid phase for realizing separation from SiO2 precipitates, and preparing SiO2 into liquid sodium silicate by performing alkali dissolving to recycle SiO2; and adding vanadium and potassium in the liquid phase into an alkaline liquor to realize separation of vanadium from potassium to prepare V2O5 and K2SO4 respectively. In the method, V2O5, K2SO4 and liquid sodium silicate are prepared by using the waste vanadium catalyst, so that synchronous recycling of vanadium, potassium and silicon is realized, the purity of V2O5 is more than or equal to 98.3 percent, the yield of V2O5 is more than or equal to 92.0 percent, the purity of K2SO4 is more than or equal to 51.2 percent counted by K2O, the yield of K2SO4 is more than or equal to 95.6 percent, Na2O in the liquid sodium silicate is more than or equal to 7.7 percent, SiO2 in the liquid sodium silicate is more than or equal to 24.6 percent, and the yield of the liquid sodium silicate is more than or equal to 93.2 percent.
Description
One, technical field
The present invention relates to a kind of treatment process of spent catalyst, exactly is a kind of method of utilizing wet processing to be produced Vanadium Pentoxide in FLAKES, vitriolate of tartar and liquid sodium silicate by spent vanadium catalyst.
Two, technical background
In sulphuric acid process, can produce a large amount of spent vanadium catalysts.These spent vanadium catalysts not only cause the wasting of resources like not treated random stacking, and can take a large amount of land resourcess, cause environmental pollution.Analytical results shows, the pentoxide content in the spent vanadium catalyst is 5%～8%, vitriolate of tartar content is 20%～25%, dioxide-containing silica is 70%～75%.If its each useful component of ability comprehensive reutilization then can not only effectively be avoided spent vanadium catalyst arbitrarily to stack and cause the pollution of environment, but also can it be turned waste into wealth, obtain good economic benefit.
In recent years, proposed certain methods, be broadly divided into alkali and dissolve the leaching method and dissolve the leaching method with acid to the recycling of vanadium in the spent vanadium catalyst.Wherein, metals ion such as iron is separated with vanadium, have the impurity such as silicon, aluminium of a great deal of still can get into solution, be prone to form colloid and be difficult to separate though alkali dissolves the leaching method.And acid is dissolved the leaching method and can be made carrier substance a large amount of in the spent vanadium catalyst can not get into solution, helps the separation purification of back, is ideal leaching method comparatively.
Dissolve in the leaching method in acid; The technical process that works out at present is varied, wherein representationally is: (1) Shi Zhaozhong and Cui Jinhai propose by spent vanadium catalyst acidleach, reduction, thick precipitation, oxidation, alkali dissolve, steps such as precipitation, roasting are formed technical process.The product purity that this technology makes is 82%, and the recovery of vanadium is 90%.(2) technical process of forming by steps such as spent vanadium catalyst water logging, reduction acidleach, purification, oxidation, IX, precipitation, roastings that proposes of people such as Hao Xicai, Hu Binjie.The product purity that this technology makes is 99%, and the recovery of vanadium is 91.7%.
Can find out that from above-mentioned vanadium has only been reclaimed in the recycling of the spent vanadium catalyst that proposes at present, and vitriolate of tartar and silicon-dioxide do not obtain recycling, and technical process is long, raw materials consumption is more.
Except the recyclable utilization of vanadium, its contained vitriolate of tartar can directly be recycled in the spent vanadium catalyst, and contained silicon-dioxide can be used to produce liquid sodium silicate etc.
The purposes of liquid sodium silicate is very extensive, almost spreads all over each department of national economy.It can be used to make the alumina silicate catalyst that petroleum catalytic cracking is used in petroleum industry; Be used for making silica gel, silicates, molecular sieve, WHITE CARBON BLACK etc. in the chemical industry.At present, the method for industrial production liquid sodium silicate mainly is the dry method sodium carbonate method.This method is with behind soda ash and the silica sand proportional mixing, under the temperature about 1400 ℃, carries out roasting, and the fused material can make the liquid sodium silicate product of different size after shrend, dissolving, clarification and concentrating.This method technical maturity, but exist energy consumption height, the more high deficiency of equipment maintenance cost.
Vitriolate of tartar is the basic raw material of system sylvite, as is used to make salt of wormwood, potassium aluminium sulfate etc.; Be used for industry such as dyestuff, glass, spices; Pharmaceutically be used as laxative etc.It is main chlorideless potassic fertilizer on agricultural, is suitable for to avoid the chlorine cash crop, like tobacco, citrus, grape etc.The main method of at present, producing vitriolate of tartar in the industry has sulfuric acid decomposition method (Mannheim proeess), forms the method for putting, solvent extration, salt manufacturing bittern comprehensive use and double decomposition etc.These methods are all utilized Repone K to be converted and are made vitriolate of tartar, thereby production cost is all higher.
Up to now, seen the recycling report of vanadium in a large amount of spent vanadium catalysts, Shang Weijian is to the relevant report of potassium, silicon comprehensive utilization wherein.
Three, summary of the invention
The present invention be directed to above-mentioned existing in prior technology weak point; Aim to provide a kind of method of spent vanadium catalyst comprehensive reutilization; Technical problem to be solved is when simplifying the molten leaching method process for extracting vanadium flow process of acid, realizes the comprehensive reutilization to potassium and silicon.More concrete provide a kind of method of utilizing wet processing to produce Vanadium Pentoxide in FLAKES, vitriolate of tartar and liquid sodium silicate by spent vanadium catalyst.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method of spent vanadium catalyst comprehensive reutilization; With the spent vanadium catalyst is raw material; Comprise that reduction acidleach, the separation of vanadium potassium, the molten removal of impurities of alkali, precipitation, calcining, alkali soak, each unit process of evaporative crystallization, it is characterized in that:
Described reduction acidleach is in the spent vanadium catalyst of granularity less than 200 μ m, is the sulphuric acid soln of 1: 1.5～5.0 addings, 3～40wt% (mass percentage concentration, down together) by spent vanadium catalyst and acid solution weight ratio; Add an amount of reductive agent again; Under ℃ temperature of room temperature～100, reacted 0.5～4 hour, acidleach finishes after-filtration and gets acidleach filtrating and filter cake, and said acidleach filter cake is extremely neutral with the clear water washing; Filtrating, washing lotion merge filtrating I, collect subsequent use respectively with filter cake I.Described reductive agent is selected from potassium sulfite, sulfurous acid, sulfurous gas etc., and so-called " in right amount " is meant the V in enough reduction spent vanadium catalysts
2O
5
It is in above-mentioned filtrating I that described vanadium potassium separates, and adds 5～40wt% potassium hydroxide solution and regulates pickling liquor system pH to 5.0～8.0, under ℃ temperature of room temperature～95, reacts 0.5～2 hour, and filtration obtains filtrate II and filter cake II collects subsequent use respectively.
It is among the filter cake II in above-mentioned vanadium potassium separates that described alkali dissolves removal of impurities; Add 5～40wt% sodium hydroxide solution, regulate pH greater than 13, and add an amount of oxygenant; Boiled 10～30 minutes; Vanadium is dissolved in the alkali lye, continues to stay in the solid matter, filter and obtain filtrating and filter cake and impurity such as iron are insoluble; With said filter cake with clear water washing to neutral, washing lotion and filtrating merge filtrate II I, staple is the oxide compound and the oxyhydroxide of iron among the neutral filter cake III, collection can be recycled; Described oxygenant is selected from oxymuriate, persulphate, permanganate etc.; So-called " in right amount " is meant enough the tetravalence vanadium is oxidized to the pentavalent vanadium.
Described precipitation is to dissolve among the filtrate II I in the removal of impurities at above-mentioned alkali; Add the 40-60wt% sulphuric acid soln, regulate pH to 7.5～8.5, add excessive precipitator ammonium chloride; At room temperature reacted 1～2 hour; Filtration obtains ammonium meta-vanadate, and metavanadic acid does not exist to there being cl ions with the clear water washing, and filtrating and washing lotion merge collects reason elsewhere;
Described calcining is the ammonium meta-vanadate that going up precipitation is obtained, and 450 ℃～550 ℃ temperature lower calcinations 1～2 hour, obtains Vanadium Pentoxide in FLAKES;
It is the filter cake I with in the above-mentioned acidleach that described alkali soaks; According to filter cake and sodium hydroxide solution weight ratio is 1: 1.5～3.0 addings, 8～20wt% sodium hydroxide solution; Below boiling temperature, and be not less than following 0.5～2 hour after-filtration of reaction of temperature condition of 60 ℃, obtain filtrating and filter cake; Said filtrating through suitably being evaporated to the liquid sodium silicate of National standard, is washed with water to neutrality with said filter cake, and washing lotion is collected and is recycled;
Described evaporative crystallization is that filtrate II evaporation concentration to the density during above-mentioned vanadium potassium is separated is 1.15～1.35g/cm
3After, be cooled to room temperature, place for some time after-filtration, the gained filter cake is promptly obtained vitriolate of tartar at 105～110 ℃ of down dry 1～2h, filtrate collection can recycle.
Each step reaction equation of the inventive method is:
The acidleach of a, spent vanadium catalyst
V
2O
5+K
2SO
3+2H
28O
4→2VOSO
4+K
28O
4+2H
2O
B, vanadium potassium separate
(VO)
2SO
4+KOH→V
2O
2(OH)
4↓+2K
28O
4
Fe
3++3OH
-→Fe(OH)
3↓
Al
3++3OH
-→Al(OH)
3↓
C, alkali dissolve removal of impurities (is example with VAL-DROP)
V
2O
2(OH)
4+NaClO
3+NaOH→NaVO
3+NaCl+H
2O
D, precipitation
NaVO
3+NH
4Cl→NH
4VO
3↓+NaCl
E, calcining
2NH
4VO
3→V
2O
5+2NH
3+H
2O
F, alkali soak
SiO
2·nH
2O+NaOH→Na
2O·nSi
2O+H
2O
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the inventive method can make useful components such as vanadium in the spent vanadium catalyst, potassium, silicon obtain fully effectively utilizing, and produces products such as the well sold and in short supply Vanadium Pentoxide in FLAKES of the market requirement, vitriolate of tartar and liquid sodium silicate.Vanadium Pentoxide in FLAKES purity>=98.3%, yield>=92.0%, vitriolate of tartar purity is in potassium oxide>=51.2%, yield>=95.6%, Na in the liquid sodium silicate
2O>=7.7%, SiO
2>=24.6%, yield>=93.2%.
Technical process when 2, the inventive method is produced Vanadium Pentoxide in FLAKES and vitriolate of tartar is brief, raw material consumption is less, production cost is lower.
The energy consumption that energy consumption when 3, the inventive method is produced liquid sodium silicate extensively adopts in present industrial production when being raw material production by silica sand can be significantly reduced.
Four, embodiment
Embodiments of the invention are undertaken by following process:
Step 1: the reduction acidleach of spent vanadium catalyst
In the spent vanadium catalyst of granularity less than 200 μ m; By spent vanadium catalyst and acid solution weight ratio is the sulphuric acid soln of 1: 1.5～5 addings, 3～40wt%; Add an amount of reductive agent again, under ℃ temperature of room temperature～100, reacted 0.5～4 hour, acidleach finishes after-filtration and gets acidleach filtrating and filter residue; Said acidleach filter cake is extremely neutral with the clear water washing, collect the filtrating I that filter cake I, acidleach filtrating and washing lotion merge respectively;
Step 2: vanadium potassium separates
In step 1, dropwise add 5～40wt% potassium hydroxide solution among the gained acidleach filtrating I and regulate pickling liquor system pH to 5.0～8.0, under ℃ temperature of room temperature～95, reacted 1～2 hour, filtration obtains filtrate II and filter cake II collects subsequent use respectively;
Step 3: alkali dissolves removal of impurities
Gained filter cake II in the step 2 is dissolved in an amount of 5～40wt% sodium hydroxide solution, regulates pH greater than 13, and add an amount of oxygenant, boiled 10～30 minutes, filter and obtain filtrating and filter cake; With filter cake with clear water washing to neutral, washing lotion and filtrating merge filtrate II I, staple is the oxide compound and the oxyhydroxide of iron among the neutral filter cake III, collection can be recycled;
Step 4: precipitation
Use the 40-60wt% sulphuric acid soln to regulate pH gained filtrate II I in the step 3 and be 7.5～8.5, add the excess chlorination ammonium, at room temperature reacted 1～2 hour, filter and obtain ammonium meta-vanadate; Metavanadic acid is by existing with the no cl ions of clear water washing to check, and filtrating and washing lotion merge collection and treatment;
Step 5: calcining
Gained ammonium meta-vanadate in the step 4 450 ℃～550 ℃ temperature lower calcinations 1～2 hour, is obtained Vanadium Pentoxide in FLAKES;
Step 6: alkali soaks
Is 1: 1.5～3.0 addings, 8～20wt% sodium hydroxide solution with gained filter residue I in the step 1 according to filter residue and sodium hydroxide solution weight ratio; Below boiling temperature; And the temperature condition that is not less than 60 ℃ reacts filtered while hot after 0.5～2 hour down, and gained filtrating is through suitably being evaporated to the liquid sodium silicate of National standard;
Step 7: evaporative crystallization
With gained filtrate II evaporation concentration to density in the step 2 is 115～1.35g/cm
3After, be cooled to room temperature, place for some time after-filtration, filter cake is promptly obtained vitriolate of tartar at 105 ℃～110 ℃ down dry 1～2h, filtrate collection can recycle.
Embodiment 1, the preparation of Vanadium Pentoxide in FLAKES, liquid sodium silicate and vitriolate of tartar, and present embodiment carries out as follows:
1, be in the spent vanadium catalyst of 150 μ m in granularity; By spent vanadium catalyst and acid solution weight ratio is the sulphuric acid soln of 1: 2 adding 35wt%; Add an amount of reductive agent again, reaction is 1 hour under 95 ℃ of temperature, and acidleach finishes after-filtration and gets acidleach filtrating and filter cake; Said acidleach filter cake is extremely neutral with the clear water washing, collect acidleach filter cake, acidleach filtrating and washing lotion respectively;
2, gained acidleach filtrating and washing lotion in the step 1 are mixed, dropwise adding 15wt% potassium hydroxide solution adjusting pickling liquor system pH is 5.5, and reaction is 1 hour under 95 ℃ of temperature, and separation end after-filtration obtains filtrating and the filter residue collection is subsequent use;
3, gained filter residue in the step 2 is dissolved in an amount of 10wt% sodium hydroxide solution, and adds an amount of oxygenant, boiled 30 minutes; Filtration obtains filtrating and filter cake; Filter cake is extremely neutral with the clear water washing, and staple is the oxide compound of iron in the filter cake, and collection can be recycled;
4, gained filtrating in the step 3 is regulated pH to 7.5 with the 50wt% sulphuric acid soln, add the excess chlorination ammonium, at room temperature reacted 2 hours, filter and obtain ammonium meta-vanadate; By existing with the no cl ions of clear water washing to check, filtrate collection is handled with metavanadic acid;
5, with gained ammonium meta-vanadate in the step 4 450 ℃ of temperature lower calcinations 2 hours, obtain the Vanadium Pentoxide in FLAKES product.Pentoxide content is 98.3% in this product, has reached the requirement of quality standard;
6, be 1: 1.8 adding 25wt% sodium hydroxide solution with gained filter residue in the step 1 according to filter residue and sodium hydroxide solution weight ratio; Filtered while hot after reacting 1 hour under 90 ℃ the temperature condition, gained filtrating is through suitably being evaporated to the liquid sodium silicate product of National standard.Sodium oxide content is 8.5% in this product, and dioxide-containing silica 24.6% has reached the requirement of quality standard;
7, with gained filtrating in the step 2, be evaporated to density 1.15g/mL after, be cooled to room temperature, place for some time after-filtration, with filter cake 110 ℃ down dry 1h promptly obtain potassium product.Potassium oxide content is 51.2% in this product, has reached the requirement of quality standard.
Embodiment 2, the preparation of Vanadium Pentoxide in FLAKES, liquid sodium silicate and vitriolate of tartar, and present embodiment carries out as follows:
1, be in the spent vanadium catalyst of 106 μ m in granularity; By spent vanadium catalyst and acid solution weight ratio is the sulphuric acid soln of 1: 3.5 adding 20wt%; Add an amount of reductive agent again, reaction is 2 hours under 60 ℃ of temperature, and acidleach finishes after-filtration and gets acidleach filtrating and filter residue; Said acidleach filter cake is extremely neutral with the clear water washing, collect acidleach filter cake, acidleach filtrating and washing lotion respectively;
2, gained acidleach filtrating and washing lotion in the step 1 are mixed, dropwise adding 20wt% potassium hydroxide solution adjusting pickling liquor system pH is 6.5, and reaction is 1.5 hours under 60 ℃ of temperature, and filtration obtains filtrating and filter residue is collected subsequent use;
3, gained filter residue in the step 2 is dissolved in an amount of 20wt% sodium hydroxide solution, and adds an amount of oxygenant, boiled 20 minutes; Filtration obtains filtrating and filter residue; Filter cake is extremely neutral with the clear water washing, and staple is the oxide compound of iron in the filter cake, and collection can be recycled;
4, gained filtrating in the step 3 is regulated pH to 8.0 with the 50wt% sulphuric acid soln, add the excess chlorination ammonium, at room temperature reacted 1.5 hours, filter and obtain ammonium meta-vanadate; By existing with the no cl ions of clear water washing to check, filtrate collection is handled with metavanadic acid;
5, with gained ammonium meta-vanadate in the step 4 500 ℃ of temperature lower calcinations 1.5 hours, obtain the Vanadium Pentoxide in FLAKES product.Pentoxide content is 98.5% in this product, has reached the requirement of quality standard;
6, be 1: 2 adding 15wt% sodium hydroxide solution with gained filter residue in the step 1 according to filter residue and sodium hydroxide solution weight ratio, filtered while hot after reacting 1.5 hours under 70 ℃ the temperature condition, gained filtrating is through suitably being evaporated to qualified liquid sodium silicate product.Sodium oxide content is 8.2% in this product, and dioxide-containing silica 24.8% has reached the requirement of quality standard;
7, with gained filtrating in the step 2, be evaporated to density 1.20g/mL after, be cooled to room temperature, place for some time after-filtration, with filter cake 108 ℃ down dry 1.5h promptly obtain potassium product.Potassium oxide content is 51.3% in this product, has reached the requirement of quality standard.
Embodiment 3, the preparation of Vanadium Pentoxide in FLAKES, liquid sodium silicate and vitriolate of tartar, and present embodiment carries out as follows:
1, be in the spent vanadium catalyst of 75 μ m in granularity; By spent vanadium catalyst and acid solution weight ratio is the sulphuric acid soln of 1: 5 adding 5wt%; Add an amount of reductive agent again, at room temperature reacted 4 hours, acidleach finishes after-filtration and gets acidleach filtrating and filter residue; Said acidleach filter cake is extremely neutral with the clear water washing, collect acidleach filter cake, acidleach filtrating and washing lotion respectively;
2, gained acidleach filtrating and washing lotion in the step 1 are mixed, dropwise adding 15wt% potassium hydroxide solution adjusting pickling liquor system pH is 7.5, at room temperature reacts 2 hours, and separation end after-filtration obtains filtrating and filter residue is collected subsequent use;
3, gained filter residue in the step 2 is dissolved in an amount of 30wt% sodium hydroxide solution, and adds an amount of oxygenant, boiled 10 minutes; Filtration obtains filtrating and filter residue; Filter cake is extremely neutral with the clear water washing, and staple is the oxide compound of iron in the filter cake, and collection can be recycled;
4, gained filtrating in the step 3 is regulated pH to 8.5 with the 50wt% sulphuric acid soln, add the excess chlorination ammonium, at room temperature reacted 1 hour, filter and obtain ammonium meta-vanadate; By existing with the no cl ions of clear water washing to check, filtrate collection is handled with metavanadic acid;
5, with gained ammonium meta-vanadate in the step 4 550 ℃ of temperature lower calcinations 1 hour, obtain the Vanadium Pentoxide in FLAKES product..Pentoxide content is 98.8% in this product, has reached the requirement of quality standard;
6, be 1: 3 adding 8wt% sodium hydroxide solution with gained filter residue in the step 1 according to filter residue and sodium hydroxide solution weight ratio; Filtered while hot after reacting 1 hour under 90 ℃ the temperature condition, gained filtrating is through suitably being evaporated to the liquid sodium silicate product of National standard.Sodium oxide content is 7.7% in this product, and dioxide-containing silica 25.6% has reached the requirement of quality standard;
7, with gained filtrating in the step 2, be evaporated to density 1.30g/mL after, be cooled to room temperature, place for some time after-filtration, with filter cake 105 ℃ down dry 2h promptly obtain potassium product; Potassium oxide content is 51.5% in this product, has reached the requirement of quality standard.
Claims (3)
1. the method for a spent vanadium catalyst comprehensive reutilization is a raw material with the spent vanadium catalyst, comprises that reduction acidleach, the separation of vanadium potassium, the molten removal of impurities of alkali, precipitation, calcining, alkali soak, each unit process of evaporative crystallization, it is characterized in that:
Described reduction acidleach is sulphuric acid soln and the reductive agent that in the spent vanadium catalyst of granularity less than 200 μ m, adds 3～40wt%; Under ℃ temperature of room temperature～100, reacted 0.5～4 hour; Separate obtain filtrating I and filter cake I, spent vanadium catalyst and acid solution mass ratio are 1: 1.5～5.0;
It is in above-mentioned filtrating I, to add 5～40wt% potassium hydroxide solution to regulate pH to 5.0～8.0 that described vanadium potassium separates, and under ℃ temperature of room temperature～95, reacts 0.5～2 hour, separates obtaining filtrate II and filter cake II;
It is in above-mentioned filter cake II, to add 5～40wt% sodium hydroxide solution that described alkali dissolves removal of impurities, regulates pH greater than 13, and adds oxygenant, seethes with excitement 10～30 minutes, separates obtaining filtrate II I and filter cake III;
Described precipitation is in above-mentioned filtrate II I, to regulate pH to 7.5～8.5 with sulphuric acid soln, adds precipitation agent ammonium chloride, under room temperature, reacts 1～2 hour, separates obtaining ammonium meta-vanadate;
Described calcining is the ammonium meta-vanadate that going up precipitation is obtained, and 450 ℃～550 ℃ temperature lower calcinations 1～2 hour, obtains Vanadium Pentoxide in FLAKES;
It is that above-mentioned filter cake I is added in 8～20wt% sodium hydroxide solution that described alkali soaks; Be not less than under 60 ℃ the temperature condition reaction filtered while hot after 0.5～2 hour; Filtrating is liquid sodium silicate, and the mass ratio of filter cake and sodium hydroxide solution is 1: 1.5～3.0;
Described evaporative crystallization is to be 115～1.35g/cm with above-mentioned filtrate II evaporation concentration to density
3After, being cooled to room temperature, standing separation promptly obtains vitriolate of tartar with the gained filter cake at 105～110 ℃ of down dry 1～2h.
2. method according to claim 1 is characterized in that: described reductive agent is selected from potassium sulfite, sulfurous acid, sulfurous gas.
3. method according to claim 1 and 2 is characterized in that: described oxygenant is selected from oxymuriate, persulphate, permanganate.
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| CN102923775A (en) * | 2012-11-27 | 2013-02-13 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of high-purity vanadium pentoxide |
| CN103789550A (en) * | 2014-01-26 | 2014-05-14 | 郝喜才 | Method for recovering vanadium, potassium and silicon from waste vanadium catalyst |
| CN104630483A (en) * | 2015-01-13 | 2015-05-20 | 漯河兴茂钛业股份有限公司 | Alkaline leaching vanadium precipitation method for comprehensive waste denitration catalyst utilization |
| CN105986123A (en) * | 2015-02-11 | 2016-10-05 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing waste catalyst reductive organic acid |
| CN107416903A (en) * | 2017-04-21 | 2017-12-01 | 广东工业大学 | A kind of method for handling spent vanadium catalyst |
| CN108878943A (en) * | 2018-06-15 | 2018-11-23 | 中国大唐集团科学技术研究院有限公司西北分公司 | A method of all-vanadium redox flow battery electrolyte is prepared using waste and old SCR catalyst |
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| CN111495354A (en) * | 2020-05-25 | 2020-08-07 | 贵州威顿催化技术有限公司 | Method for preparing catalyst by leaching waste vanadium catalyst |
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| CN113337737A (en) * | 2021-06-01 | 2021-09-03 | 贵州威顿催化技术有限公司 | Method for recovering waste vanadium catalyst by using chromatographic technique |
| CN114291879A (en) * | 2021-11-23 | 2022-04-08 | 攀钢集团研究院有限公司 | Preparation method of aluminum silicate |
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| CN103789550B (en) * | 2014-01-26 | 2015-10-28 | 开封大学 | The recovery method of vanadium potassium silicon in spent vanadium catalyst |
| CN104630483A (en) * | 2015-01-13 | 2015-05-20 | 漯河兴茂钛业股份有限公司 | Alkaline leaching vanadium precipitation method for comprehensive waste denitration catalyst utilization |
| CN105986123A (en) * | 2015-02-11 | 2016-10-05 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing waste catalyst reductive organic acid |
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| CN111495354A (en) * | 2020-05-25 | 2020-08-07 | 贵州威顿催化技术有限公司 | Method for preparing catalyst by leaching waste vanadium catalyst |
| CN111876604A (en) * | 2020-08-03 | 2020-11-03 | 江苏肯创催化剂再生技术有限公司 | Process method for treating and utilizing sulfuric acid catalyst prepared from waste vanadium-silicon system |
| CN113005305A (en) * | 2021-01-28 | 2021-06-22 | 斯瑞尔环境科技股份有限公司 | Method for recovering vanadium from FCC spent catalyst |
| CN113337737A (en) * | 2021-06-01 | 2021-09-03 | 贵州威顿催化技术有限公司 | Method for recovering waste vanadium catalyst by using chromatographic technique |
| CN114291879A (en) * | 2021-11-23 | 2022-04-08 | 攀钢集团研究院有限公司 | Preparation method of aluminum silicate |
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