CN102491419B - Method for comprehensively recycling waste vanadium catalyst - Google Patents
Method for comprehensively recycling waste vanadium catalyst Download PDFInfo
- Publication number
- CN102491419B CN102491419B CN2011103979782A CN201110397978A CN102491419B CN 102491419 B CN102491419 B CN 102491419B CN 2011103979782 A CN2011103979782 A CN 2011103979782A CN 201110397978 A CN201110397978 A CN 201110397978A CN 102491419 B CN102491419 B CN 102491419B
- Authority
- CN
- China
- Prior art keywords
- filtrate
- filter cake
- vanadium
- potassium
- vanadium catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
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 for the treatment of 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 such as 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 energy comprehensive reutilization then can not only effectively be avoided spent vanadium catalyst arbitrarily to stack and cause the pollution of environment, but also it can be turned waste into wealth, obtain good economic benefit.
In recent years, propose certain methods for the recycling of vanadium in the spent vanadium catalyst, be broadly divided into the molten leaching method of alkali and sour molten leaching method.Wherein, though the molten leaching method of alkali can make the metal ion such as iron separate with vanadium, there are the impurity such as silicon, aluminium of a great deal of still can enter solution, easily form colloid and be difficult to separate.And sour molten leaching method can make carrier substance a large amount of in the spent vanadium catalyst can not enter solution, is conducive to the separating-purifying of back, is comparatively desirable leaching method.
In the molten leaching method of acid, the technical process that works out at present is varied, wherein representationally is: the technical process that the steps such as that (1) Shi Zhaozhong and Cui Jinhai propose is molten by spent vanadium catalyst acidleach, reduction, thick precipitation, oxidation, alkali, precipitation, roasting form.The product purity that this technique makes is 82%, and the rate of recovery of vanadium is 90%.(2) technical process that is formed by steps such as spent vanadium catalyst water logging, reduction acidleach, purification, oxidation, ion-exchange, precipitation, roastings that proposes of the people such as Hao Xicai, Hu Binjie.The product purity that this technique makes is 99%, and the rate of recovery of vanadium is 91.7%.
As can be seen from the above, vanadium has only been reclaimed in the recycling of the spent vanadium catalyst that proposes at present, and vitriolate of tartar and silicon-dioxide are not recycled utilization, and technical process is long, raw materials consumption is more.
Except the vanadium recoverable, 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 after soda ash and quartz sand are mixed in proportion, to carry out roasting under the temperature about 1400 ℃, the material of melting through shrend, dissolving, clarification and concentrated after, can make the liquid sodium silicate product of different size.This method technical maturity, energy consumption is high, the more high deficiency of equipment maintenance cost but exist.
Vitriolate of tartar is the basic raw material of sylvite processed, as being used for salt of wormwood processed, potassium aluminium sulfate etc.; Be used for the industry such as dyestuff, glass, spices; Pharmaceutically be used as laxative etc.It is main chlorideless potassic fertilizer in agricultural, is suitable for to avoid the chlorine cash crop, such as tobacco, citrus, grape etc.At present, the main method of industrial production vitriolate of tartar sulfuric acid decomposition method (Mannheim proeess) arranged, form 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, there is not yet the relevant report of potassium, silicon comprehensive utilization wherein.
Three, summary of the invention
The present invention be directed to the existing weak point of above-mentioned prior art, aim to provide a kind of method of spent vanadium catalyst comprehensive reutilization, technical problem to be solved is when simplifying sour molten leaching method process for extracting vanadium flow process, realizes the comprehensive reutilization to potassium and silicon.More specifically provide 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.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method of spent vanadium catalyst comprehensive reutilization, take spent vanadium catalyst as 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, be 1: 1.5～5.0 to add 3～40wt%(mass percentage concentration by spent vanadium catalyst and acid solution weight ratio, sulphuric acid soln down together), add again an amount of reductive agent, reacted 0.5～4 hour under ℃ temperature of room temperature～100, acidleach is filtered to get acidleach filtrate and filter cake after finishing, and described acidleach filter cake is extremely neutral with the clear water washing, filtrate, washing lotion merge to get the filtrate I, collect respectively for subsequent use with the filter cake I.Described reductive agent is selected from potassium sulfite, sulfurous acid, sulfurous gas etc., and so-called " in right amount " refers to enough to reduce the V in the spent vanadium catalyst
2O
5
It is in above-mentioned filtrate I that described vanadium potassium separates, and adds 5～40wt% potassium hydroxide solution and regulates pickling liquor system pH to 5.0～8.0, reacts 0.5～2 hour under ℃ temperature of room temperature～95, and filtration obtains the filtrate II and the filter cake II is collected respectively for subsequent use.
The molten removal of impurities of described alkali is in the filter cake II in above-mentioned vanadium potassium separates, 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 and the impurity such as iron are insoluble, filter and obtain filtrate and filter cake; Described filter cake is extremely neutral with the clear water washing, and washing lotion and filtrate merge to get the filtrate III, and main component is oxide compound and the oxyhydroxide of iron in the neutral filter cake III, and collection can be recycled; Described oxygenant is selected from oxymuriate, persulphate, permanganate etc.; So-called " in right amount " refers to enough the tetravalence vanadium is oxidized to the pentavalent vanadium.
Described precipitation is in the filtrate III in the molten removal of impurities of above-mentioned alkali, add the 40-60wt% sulphuric acid soln, regulate pH to 7.5～8.5, add excessive precipitation agent ammonium chloride, at room temperature reacted 1～2 hour, filtration obtains ammonium meta-vanadate, and to existing without chlorion, filtrate and washing lotion merge collects elsewhere reason to ammonium meta-vanadate with the clear water washing;
Described calcining is the ammonium meta-vanadate that above-mentioned precipitation is obtained, and 450 ℃～550 ℃ temperature lower calcinations 1～2 hour, obtains Vanadium Pentoxide in FLAKES;
It is filter cake I with in the above-mentioned acidleach that described alkali soaks, be 1: 1.5～3.0 to add 8～20wt% sodium hydroxide solution according to filter cake and sodium hydroxide solution weight ratio, below boiling temperature, and be not less than to react after 0.5～2 hour under 60 ℃ the temperature condition and filter, obtain filtrate and filter cake; Described filtrate through suitably being evaporated to the liquid sodium silicate that meets national standard, is washed with water to neutrality with described 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, filter after placement for some time, the gained filter cake is namely obtained vitriolate of tartar at 105～110 ℃ of lower 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
2SO
4→2VOSO
4+K
2SO
4+2H
2O
B, vanadium potassium separate
(VO)
2SO
4+KOH→V
2O
2(OH)
4↓+2K
2SO
4
Fe
3++3OH
-→Fe(OH)
3↓
Al
3++3OH
-→Al(OH)
3↓
C, the molten removal of impurities of alkali (take sodium chlorate as example)
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·nSiO
2+H
2O
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the inventive method can make the useful components such as vanadium in the spent vanadium catalyst, potassium, silicon obtain fully effectively utilizing, and produces the 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 the present industrial production when being raw material production by quartz sand can be significantly reduced.
Four, embodiment
Embodiments of the invention carry out according to the following procedure:
Step 1: the reduction acidleach of spent vanadium catalyst
In the spent vanadium catalyst of granularity less than 200 μ m, be 1: 1.5～5 to add the sulphuric acid soln of 3～40wt% by spent vanadium catalyst and acid solution weight ratio, add again an amount of reductive agent, under ℃ temperature of room temperature～100, reacted 0.5～4 hour, acidleach is filtered to get acidleach filtrate and filter residue after finishing, described acidleach filter cake is extremely neutral with the clear water washing, collect respectively the filtrate I that filter cake I, acidleach filtrate and washing lotion merge;
Step 2: vanadium potassium separates
Dropwise add 5～40wt% potassium hydroxide solution in the step 1 in the gained acidleach filtrate I and regulate pickling liquor system pH to 5.0～8.0, under ℃ temperature of room temperature～95, reacted 1～2 hour, filter and obtain the filtrate II and the filter cake II is collected respectively for subsequent use;
Step 3: the molten removal of impurities of alkali
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 filtrate and filter cake; Filter cake is extremely neutral with the clear water washing, and washing lotion and filtrate merge to get the filtrate III, and main component is oxide compound and the oxyhydroxide of iron in the neutral filter cake III, and collection can be recycled;
Step 4: precipitation
It is 7.5～8.5 that gained filtrate III in the step 3 is regulated pH with the 40-60wt% sulphuric acid soln, adds the excess chlorination ammonium, at room temperature reacts 1～2 hour, filters and obtains ammonium meta-vanadate; Metavanadic acid is by existing without chlorion to check with the clear water washing, and filtrate 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
Be 1: 1.5～3.0 to add 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 be not less than under 60 ℃ the temperature condition and react filtered while hot after 0.5～2 hour, gained filtrate is through suitably being evaporated to the liquid sodium silicate that meets national standard;
Step 7: evaporative crystallization
Be 1.15～1.35g/cm with gained filtrate II evaporation concentration to density in the step 2
3After, be cooled to room temperature, filter after placement for some time, filter cake is namely obtained vitriolate of tartar at 105 ℃～110 ℃ lower dry 1～2h, filtrate collection can recycle.
Embodiment 1, the preparation of Vanadium Pentoxide in FLAKES, liquid sodium silicate and vitriolate of tartar, and the present embodiment carries out as follows:
1, be in the spent vanadium catalyst of 150 μ m in granularity, be to add the sulphuric acid soln of 35wt% at 1: 2 by spent vanadium catalyst and acid solution weight ratio, add again an amount of reductive agent, reaction is 1 hour under 95 ℃ of temperature, acidleach is filtered to get acidleach filtrate and filter cake after finishing, described acidleach filter cake is extremely neutral with the clear water washing, collect respectively acidleach filter cake, acidleach filtrate and washing lotion;
2, gained acidleach filtrate 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 the rear filtration of separation end obtains filtrate and filter residue is collected for 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 filtrate and filter cake, filter cake is extremely neutral with the clear water washing, and main component is the oxide compound of iron in the filter cake, and collection can be recycled;
4, gained filtrate 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 without chlorion to check with the clear water washing, filtrate collection is processed 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 filtrate is through suitably being evaporated to the liquid sodium silicate product that meets 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 filtrate in the step 2, be evaporated to density 1.15g/mL after, be cooled to room temperature, filter after placing for some time, filter cake is namely obtained potassium product at 110 ℃ of lower dry 1h.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 the present embodiment carries out as follows:
1, be in the spent vanadium catalyst of 106 μ m in granularity, be to add the sulphuric acid soln of 20wt% at 1: 3.5 by spent vanadium catalyst and acid solution weight ratio, add again an amount of reductive agent, reaction is 2 hours under 60 ℃ of temperature, acidleach is filtered to get acidleach filtrate and filter residue after finishing, described acidleach filter cake is extremely neutral with the clear water washing, collect respectively acidleach filter cake, acidleach filtrate and washing lotion;
2, gained acidleach filtrate 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 filtrate and filter residue is collected for 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 filtrate and filter residue, filter cake is extremely neutral with the clear water washing, and main component is the oxide compound of iron in the filter cake, and collection can be recycled;
4, gained filtrate 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 without chlorion to check with the clear water washing, filtrate collection is processed 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 that 1:2 adds the 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 filtrate 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 filtrate in the step 2, be evaporated to density 1.20g/mL after, be cooled to room temperature, filter after placing for some time, filter cake is namely obtained potassium product at 108 ℃ of lower dry 1.5h.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 the present embodiment carries out as follows:
1, be in the spent vanadium catalyst of 75 μ m in granularity, be to add the sulphuric acid soln of 5wt% at 1: 5 by spent vanadium catalyst and acid solution weight ratio, add again an amount of reductive agent, at room temperature reacted 4 hours, acidleach is filtered to get acidleach filtrate and filter residue after finishing, described acidleach filter cake is extremely neutral with the clear water washing, collect respectively acidleach filter cake, acidleach filtrate and washing lotion;
2, gained acidleach filtrate 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 the rear filtration of separation end obtains filtrate and the filter residue collection is for 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 filtrate and filter residue, filter cake is extremely neutral with the clear water washing, and main component is the oxide compound of iron in the filter cake, and collection can be recycled;
4, gained filtrate 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 without chlorion to check with the clear water washing, filtrate collection is processed 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 filtrate is through suitably being evaporated to the liquid sodium silicate product that meets 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 filtrate in the step 2, be evaporated to density 1.30g/mL after, be cooled to room temperature, filter after placing for some time, filter cake is namely obtained potassium product at 105 ℃ of lower dry 2h; 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 take spent vanadium catalyst as raw material, 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 adds 3～40wt% in the spent vanadium catalyst of granularity less than 200 μ m, under ℃ temperature of room temperature～100, reacted 0.5～4 hour, separate obtaining filtrate I and filter cake I, spent vanadium catalyst and acid solution mass ratio are 1: 1.5～5.0;
It is to add 5～40wt% potassium hydroxide solution to regulate pH to 5.0～8.0 in above-mentioned filtrate I that described vanadium potassium separates, and reacts 0.5～2 hour under ℃ temperature of room temperature～95, separates obtaining filtrate II and filter cake II;
The molten removal of impurities of described alkali is to add 5～40wt% sodium hydroxide solution in above-mentioned filter cake II, regulates pH greater than 13, and adds oxygenant, seethes with excitement 10～30 minutes, separates obtaining filtrate III and filter cake III;
Described precipitation is to regulate pH to 7.5～8.5 with sulphuric acid soln in above-mentioned filtrate III, adds precipitation agent ammonium chloride, reacts under room temperature 1～2 hour, separates obtaining ammonium meta-vanadate;
Described calcining is the ammonium meta-vanadate that above-mentioned 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 react 0.5～2 hour under 60 ℃ the temperature condition after filtered while hot, filtrate 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 1.15～1.35g/cm with above-mentioned filtrate II evaporation concentration to density
3After, being cooled to room temperature, standing separation namely obtains vitriolate of tartar with the gained filter cake at 105～110 ℃ of lower dry 1～2h.
2. method according to claim 1, it is characterized in that: described reductive agent is selected from potassium sulfite, sulfurous acid, sulfurous gas.
3. method according to claim 1 and 2, it is characterized in that: described oxygenant is selected from oxymuriate, persulphate, permanganate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103979782A CN102491419B (en) | 2011-12-05 | 2011-12-05 | Method for comprehensively recycling waste vanadium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103979782A CN102491419B (en) | 2011-12-05 | 2011-12-05 | Method for comprehensively recycling waste vanadium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102491419A CN102491419A (en) | 2012-06-13 |
| CN102491419B true CN102491419B (en) | 2013-09-18 |
Family
ID=46183290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103979782A Active CN102491419B (en) | 2011-12-05 | 2011-12-05 | Method for comprehensively recycling waste vanadium catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102491419B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105986123B (en) * | 2015-02-11 | 2019-01-08 | 中国科学院过程工程研究所 | A method of the reproducibility of waste catalyst containing vanadium is organic acid-leaching vanadium-extracted |
| 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 |
| CN109775681B (en) * | 2018-12-27 | 2020-08-11 | 大连博融新材料有限公司 | Method for directly preparing lithium vanadium phosphate by recovering VPO catalyst |
| CN111485121B (en) * | 2019-01-25 | 2021-06-08 | 中国科学院过程工程研究所 | Method for recovering acid liquor and separating vanadium in process of reducing, acid leaching and vanadium-containing waste catalyst |
| 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 |
| CN114291879B (en) * | 2021-11-23 | 2023-09-05 | 攀钢集团研究院有限公司 | Preparation method of aluminum silicate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009151147A1 (en) * | 2008-06-12 | 2009-12-17 | Ｊｆｅミネラル株式会社 | Process for recoverying valuable metals from waste catalyst |
| CN101457296B (en) * | 2008-10-17 | 2011-04-27 | 芜湖人本合金有限责任公司 | Method for recovering metallic oxide from waste aluminum base V-Mo-Ni catalyst |
-
2011
- 2011-12-05 CN CN2011103979782A patent/CN102491419B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102491419A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102491419B (en) | Method for comprehensively recycling waste vanadium catalyst | |
| CN103086405B (en) | Clean production method of battery level lithium carbonate | |
| CN103789550B (en) | The recovery method of vanadium potassium silicon in spent vanadium catalyst | |
| CN107352524A (en) | A kind of recovery method of waste lithium iron phosphate positive electrode | |
| CN111468103B (en) | Method for recycling waste SCR denitration catalyst to prepare new SCR denitration catalyst | |
| CN108147384B (en) | Method for preparing battery-grade lithium dihydrogen phosphate by using lithium iron phosphate waste | |
| CN101941704A (en) | New method for preparing silicon dioxide by utilizing rice hull ash | |
| CN107177737A (en) | Spent vanadium catalyst comprehensive reutilization method | |
| CN102260801B (en) | Clean conversion method of stone coal | |
| CN103241754A (en) | Production method of high-purity aluminum oxide | |
| CN107344725A (en) | The preparation technology of elemental lithium in sulfuric acid straight dipping process extraction lithium ore | |
| CN104692436B (en) | It is a kind of by coal ash for manufacturing for cryolite method | |
| CN109319792A (en) | A kind of method that high added value comprehensively utilizes silicon, aluminium, potassium in potash feldspar ore | |
| CN102674473A (en) | Process for preparing ferric oxide red by adopting iron vitriol | |
| CN102815728A (en) | Method for preparing nano-sized magnesium hydroxide and nano-silica by utilization of boron mud | |
| CN101607721B (en) | Method for preparing highly pure magnesium hydroxide and magnesium hexa-silicate by using olivine tailing mine | |
| CN106586990B (en) | With the method for Wet-process Phosphoric Acid Production potassium dihydrogen phosphate | |
| CN102897771B (en) | Silicate ore acid leaching extraction method | |
| CN102849782B (en) | Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization | |
| CN111592017A (en) | Method for preparing battery-grade lithium chloride by pressing and soaking spodumene | |
| US3712942A (en) | Method of producing vanadium compounds by alkaline leaching | |
| CN102923681B (en) | Method for directly preparing industrial monopotassium phosphate through low-grade phosphate ores by hydrochloric acid process | |
| CN104480531A (en) | Process for decomposing albite | |
| CN110482576B (en) | Method for preparing lithium salt from lepidolite through hydrothermal method | |
| CN102321803B (en) | Method for removing chloride ion from waste molasses for manganese dioxide reduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |