CN107970910A - A kind of method that spent vanadium catalyst recycles - Google Patents
A kind of method that spent vanadium catalyst recycles Download PDFInfo
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- CN107970910A CN107970910A CN201610932088.XA CN201610932088A CN107970910A CN 107970910 A CN107970910 A CN 107970910A CN 201610932088 A CN201610932088 A CN 201610932088A CN 107970910 A CN107970910 A CN 107970910A
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- vanadium catalyst
- recycles
- spent
- spent vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
A kind of method that spent vanadium catalyst recycles, is related to environmental technology field and field of catalyst preparation.After the present invention is by the way that spent vanadium catalyst is milled, vanadium, potassium is set to be transferred to liquid phase by acidleach, silicon in phase analysis recycles after alkali neutralization, and the liquid phase containing vanadium, potassium is mixed after being tuned into certain pH value with aqueous slkali with diatomite, then obtains vanadium catalyst by extruded moulding, drying, calcining.The present invention by spent vanadium catalyst silicon separate, while realize vanadium, vanadium catalyst is made in the recycling of potassium, have technique it is simple, it is environmentally protective, economic value is high the advantages of.
Description
Technical field
A kind of method that spent vanadium catalyst recycles, is related to environmental technology field and field of catalyst preparation.
Background technology
Sulfuric acid industry process units can produce substantial amounts of spent vanadium catalyst, be very difficult to the dangerous waste with processing.Useless vanadium catalysis
Agent is mainly formed as vanadic anhydride（5%-8%）, potassium sulfate（20%~25%）, silica（70%-75%）If
These components can be recycled or recycled, can not only alleviate pollution caused by dead catalyst, moreover it is possible to obtain good warp
Ji benefit.
Sodium metasilicate is commonly called as sodium silicate, waterglass, and liquid sodium silicate is colourless, slightly colored transparent or semitransparent thick liquid
Body.Sodium silicate solid is colourless, slightly colored transparent or semitransparent glass blocks.It is that a kind of ore deposit binder is widely used in
The various fields such as conventional cast, hot investment casting, papermaking, ceramics, clay, ore dressing, kaolin, washing.
At present, the recoverying and utilizing method of spent vanadium catalyst mainly leaches method by alkali soluble and the molten leaching method of acid separates respectively
Going out vanadium potassium silicon, its operating process needs that the processes such as soda acid dissolving, filtering, extraction are repeated, and not only produces a large amount of spent acid salkali waste,
Also need to largely use organic extractant.Patent CN102491419A " a kind of spent vanadium catalyst synthesis as disclosed in bright grade less
The method of recycling ", by spent vanadium catalyst by reducing acidleach, vanadium, potassium is transferred in liquid phase, containing SiO2Precipitation passes through alkali
Molten preparation withdrawal liquid sodium metasilicate, vanadium, potassium in liquid phase add the separation that lye realizes vanadium and potassium, then by precipitating, evaporating, tying
Crystalline substance prepares V respectively2O5And K2SO4.Hao likes ability etc. and discloses the patent CN 103789550A " recycling of vanadium potassium silicon in spent vanadium catalyst
Method ", first carries out spent vanadium catalyst water logging, reduction acidleach, and silicon is present in phase analysis, is separated with the vanadium in leachate and potassium.
The raffinate phase of leachate recycles potassium through evaporative crystallization preparing potassium sulfate, and extraction phase is prepared through processes such as back extraction, precipitation and roastings
Vanadic anhydride recycles vanadium.The processing step of the recoverying and utilizing method of these spent vanadium catalysts is all very complicated, and useless vanadium catalysis
Vanadium potassium silicon in agent cannot recycle completely, and processing procedure can produce secondary pollution.
The content of the invention
The problem of being difficult to processing recycling the purpose of the present invention is to solve spent vanadium catalyst, propose a kind of spent vanadium catalyst
The method of recycling, is separated vanadium, potassium with silicon using acid solution, then will be used to prepare vanadium catalysis after vanadium, potassium adjustment pH value
Agent, the silicon by-product sodium silicate solution isolated, has the characteristics of technical process is simple, environmentally protective, economic value is high.
Technical scheme：A kind of method that spent vanadium catalyst recycles, includes below scheme：（1）By useless vanadium
Catalyst is milled to particle diameter less than 400 μm, and adding salpeter solution makes spent vanadium catalyst fully dissolve, and filtrate is respectively obtained after filtering
And filter residue；（2）Filtrate adjusts pH value with KOH solution, is uniformly mixed after adding diatomite, then is molded with banded extruder, passes through
Vanadium catalyst is obtained after dry, calcining；（3）Filter residue is added in NaOH solution, is filtered after reacting after a while, is obtained
Filtrate is sodium silicate solution.
As further improved technical scheme of the present invention, the flow（1）, the concentration for further including salpeter solution is 5-
50wt%, is further optimized for 10-40 wt%, and spent vanadium catalyst is 1 with salpeter solution mass ratio:1-1:5, further optimization
For 1:2-1:4.
As further improved technical scheme of the present invention, the flow（2）, it is 10- to further include KOH solution concentration
30wt%, pH value 1-4, is further optimized for 2-3.
As further improved technical scheme of the present invention, the flow（2）, further include diatomite addition and filtrate matter
Amount is than being 10:3-10:6, incorporation time 20-60min, is further optimized for 30-50min.
As further improved technical scheme of the present invention, the flow（2）, it is 120-180oC to further include drying temperature,
Drying time is 6-10h.
As further improved technical scheme of the present invention, the flow（3）, the concentration for further including NaOH solution is 5-
30wt%, filter residue are 1 with NaOH solution mass ratio:1-1:5, further it is optimized for 1:1-1:3.
As further improved technical scheme of the present invention, the flow（3）, it is 50-100 oC to further include reaction temperature,
Reaction time is 1-5h, is further optimized for 1-3h.
Beneficial effect
1. the present invention utilizes the vanadium potassium in spent vanadium catalyst to prepare vanadium catalyst, isolate silicon and prepare sodium silicate solution, by useless vanadium
Catalyst is fully utilized；
2. the present invention does not produce spent acid salkali waste, there is the advantages of technique is simple, environmentally protective, economic value is high.
Brief description of the drawings
Fig. 1 recycles flow diagram for spent vanadium catalyst of the embodiment of the present invention.
Embodiment
Vanadium catalyst determination of activity condition in following embodiments：The stainless steel reaction pipe of a diameter of 40mm, catalyst filling
Measure as 30ml, SO2Concentration is 10%, air speed 3600h-1, reaction temperature 485 oC, measures initial activity；It is warming up to 700 oC is resistance to
After hot 5h, 485 are cooled to oActivity after C measure is heat-resisting.Fig. 1 is shown in technological process.
Embodiment one
5Kg spent vanadium catalysts are milled to particle diameter less than 400 μm, 25wt% salpeter solution 15Kg is added, fills spent vanadium catalyst
Divide dissolving, filtrate and filter residue are respectively obtained after filtering.Filtrate adjusts pH value to 3 with 20wt%KOH solution, adds 32.5 Kg silicon
It is uniformly mixed after diatomaceous earth, then is molded with banded extruder, vanadium catalyst, active testing result table is obtained after drying, calcining
Bright initial activity is 89%, and active after heat-resisting is 84%.Filter residue is added in 10Kg 20wt%NaOH solution, and 80o2h is reacted under C
After filter, obtained filtrate is sodium silicate solution, the rate of recovery 94.6%, sodium oxide content 7.9%, and dioxide-containing silica is
26%。
Embodiment two
8Kg spent vanadium catalysts are milled to particle diameter less than 400 μm, 30wt% salpeter solution 30Kg is added, fills spent vanadium catalyst
Divide dissolving, filtrate and filter residue are respectively obtained after filtering.Filtrate adjusts pH value to 2 with 30wt%KOH solution, adds 51 Kg diatoms
Be uniformly mixed after soil, then be molded with banded extruder, by drying, calcining after obtain vanadium catalyst, active testing the result shows that
Initial activity is 90%, and active after heat-resisting is 83%.Filter residue is added in 20Kg 25wt%NaOH solution, and 90o2.5h is reacted under C
After filter, obtained filtrate is sodium silicate solution, the rate of recovery 95.3%, sodium oxide content 8.1%, and dioxide-containing silica is
26.4%。
Claims (8)
1. a kind of method that spent vanadium catalyst recycles, it is characterised in that include below scheme：
（1）Spent vanadium catalyst is milled to particle diameter less than 400 μm, adding salpeter solution dissolves spent vanadium catalyst, divides after filtering
Filtrate and filter residue are not obtained；
（2）Filtrate adjusts pH value with KOH solution, is stirred after adding diatomite, then is molded with banded extruder, by drying, forges
Vanadium catalyst is obtained after burning；
（3）Filter residue is added in NaOH solution and reacts, and is filtered after reaction, and obtained filtrate is sodium silicate solution.
2. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（1）Middle nitric acid is molten
The concentration of liquid is 5-50wt%, and spent vanadium catalyst is 1 with salpeter solution mass ratio:1-1:5.
3. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（2）Middle KOH solution
Concentration is 10-30wt%, pH value 1-4.
4. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（2）Middle diatomite
Addition is 10 with filtrate quality ratio:3-10:6, incorporation time 20-60min.
5. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（2）Middle dry temperature
Spend for 100-200oC, drying time 5-12h.
6. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（2）Middle calcining temperature
Spend for 350-450 oC, calcination time 6-12h.
7. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（3）Middle NaOH is molten
The concentration of liquid is 5-30wt%, and filter residue is 1 with NaOH solution mass ratio:1-1:5.
8. the method that spent vanadium catalyst as claimed in claim 1 recycles, it is characterised in that the flow（3）Middle reaction temperature
Spend for 50-100 oC, reaction time 1-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610932088.XA CN107970910A (en) | 2016-10-25 | 2016-10-25 | A kind of method that spent vanadium catalyst recycles |
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| CN201610932088.XA CN107970910A (en) | 2016-10-25 | 2016-10-25 | A kind of method that spent vanadium catalyst recycles |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114082416A (en) * | 2021-11-25 | 2022-02-25 | 贵州威顿催化技术有限公司 | Method for recycling waste vanadium catalyst by using D280 resin |
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| US6878668B1 (en) * | 1999-07-14 | 2005-04-12 | E. I. Du Pont De Nemours And Company | Process for manufacture of an attrition resistant catalyst |
| CN101054635A (en) * | 2007-05-28 | 2007-10-17 | 德物华经济信息研究院有限公司 | Method for extracting vanadium pentoxide from Stone-like coal vanadium ore and special device for the same |
| CN102259000A (en) * | 2011-06-02 | 2011-11-30 | 中国石油化工集团公司 | Recycling method for dead catalyst containing nickel |
| CN102732730A (en) * | 2012-06-28 | 2012-10-17 | 江苏龙源催化剂有限公司 | Recovery method for vanadium component in selective catalytic reduction denitration catalyst |
| CN103420520A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Processing method of vanadium-containing aluminum-containing wastewater |
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2016
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Patent Citations (5)
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|---|---|---|---|---|
| US6878668B1 (en) * | 1999-07-14 | 2005-04-12 | E. I. Du Pont De Nemours And Company | Process for manufacture of an attrition resistant catalyst |
| CN101054635A (en) * | 2007-05-28 | 2007-10-17 | 德物华经济信息研究院有限公司 | Method for extracting vanadium pentoxide from Stone-like coal vanadium ore and special device for the same |
| CN102259000A (en) * | 2011-06-02 | 2011-11-30 | 中国石油化工集团公司 | Recycling method for dead catalyst containing nickel |
| CN103420520A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Processing method of vanadium-containing aluminum-containing wastewater |
| CN102732730A (en) * | 2012-06-28 | 2012-10-17 | 江苏龙源催化剂有限公司 | Recovery method for vanadium component in selective catalytic reduction denitration catalyst |
Non-Patent Citations (2)
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| 刘彬，: ""废钒催化剂综合回收利用技术研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114082416A (en) * | 2021-11-25 | 2022-02-25 | 贵州威顿催化技术有限公司 | Method for recycling waste vanadium catalyst by using D280 resin |
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