CN108359799A - A kind of method of green reclaim titanium containing tungsten vanadium catalyst - Google Patents
A kind of method of green reclaim titanium containing tungsten vanadium catalyst Download PDFInfo
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- CN108359799A CN108359799A CN201810194421.0A CN201810194421A CN108359799A CN 108359799 A CN108359799 A CN 108359799A CN 201810194421 A CN201810194421 A CN 201810194421A CN 108359799 A CN108359799 A CN 108359799A
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- solid
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- tungsten vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods of green reclaim titanium containing tungsten vanadium catalyst, include the following steps：The flue dust and salt enriched substance of cleaning catalyst cellular cavity entrainment；Carry out depth crushing；Sodium hydroxide solution is added in said mixture, it is 100~500g/L to make its naoh concentration；Step 4：The material that the reaction was complete is separated by solid-liquid separation, solid is cleaned to pH=7~10；With the solid-to-liquid ratio of the solid obtained in dilute sulfuric acid regulating step four, heat, then be separated by solid-liquid separation；The solid obtained after liquid is detached adjusts solid-to-liquid ratio using dilute sulfuric acid, heats, heat preservation, it is separated by solid-liquid separation again, solid is washed till pH ＞ 5 with clear water, by Solid Conveying and Melting to rotary kiln center, it is calcined at a temperature of 1000 DEG C, calcined product is titanium dioxide, crushes, packs.The method of green reclaim titanium containing the tungsten vanadium catalyst, can high efficiency recycle catalyst, economize on resources.
Description
Technical field
The present invention relates to a kind of methods of green reclaim titanium containing tungsten vanadium catalyst, belong to chemical field.
Background technology
Currently, with nitrogen oxides pollution object emission reduction work propulsion and《Fossil-fuel power plant atmospheric pollutant emission standard》Reality
It applies, more and more power plant and enterprise's boiler are required for installation catalyst, and such catalyst is substantially the members such as tungsten titanium vanadium molybdenum
Based on element.With the propulsion of time, such catalyst comes into the peak period scrapped, and domestic many enterprises at present can only
Regeneration treatment is carried out, there is no the abilities of each elements such as recycling tungsten vanadium titanium completely, lead to the wasting of resources.
It is therefore desirable to design a kind of method of green reclaim titanium containing tungsten vanadium catalyst, to overcome the above problem.
Invention content
It is an object of the invention to overcome the defect of the prior art, a kind of green reclaim titanium containing tungsten vanadium catalyst is provided
Method, can high efficiency recycle catalyst, economize on resources.
The invention is realized in this way：
The present invention provides a kind of method of green reclaim titanium containing tungsten vanadium catalyst, includes the following steps：
Step 1：The flue dust and salt enriched substance of cleaning catalyst cellular cavity entrainment；
Step 2：Depth crushing is carried out, 200 mesh mixture below is obtained；
Step 3：Sodium hydroxide solution is added in said mixture, it is 100~500g/L to make its naoh concentration,
It is heated 1-5 hours in autoclave or atmospheric kettle；
Step 4：The material that the reaction was complete in step 3 is separated by solid-liquid separation, solid is cleaned to pH=7~10, liquid
Repeat step 3；
Step 5：It with the solid-to-liquid ratio of the solid obtained in dilute sulfuric acid regulating step four, can stir dynamic, be heated to 80
DEG C or more, 0.5-3 hours are kept the temperature, then be separated by solid-liquid separation, liquid repeats the operation of step 5；
Step 6：The solid obtained after step 5 is separated by solid-liquid separation adjusts solid-to-liquid ratio using dilute sulfuric acid, can stir
It is dynamic, 80 DEG C or more are heated to, keeps the temperature 0.5-3 hours, then be separated by solid-liquid separation, liquid repeats step 6 operation, solid clear water
PH ＞ 5 are washed till, Solid Conveying and Melting to rotary kiln center is calcined at a temperature of 1000 DEG C, calcined product is titanium dioxide, carries out powder
Broken, packaging.
Further, it in step 2, is crushed using vibrations ball mill, 200 mesh sieve below is arranged in discharge port.
Further, when tungstic acid solubility is more than 60g/L in the liquid of step 4, condensing crystallizing is carried out, crystal is
The mixture of tungsten vanadium sodium salt, mother liquor reuse step 3.
Further, tungsten vanadium sodium salt pH, extraction and separation tungsten vanadium are adjusted, or tungsten is precipitated as the form of wolframic acid, solid-liquid point
From rear, liquid extraction goes out vanadium, and tungsten continues to be processed into ammonium paratungstate product.
The invention has the advantages that：
Currently available technology carries out flue dust cleaning primarily directed to the intact dead catalyst of appearance, is used back after regeneration
The desulfuring and denitrifying apparatus such as power plant, the catalyst activation that at most can only achieve new product 80% after regeneration.The technical scheme is that
Chemically angle is set out, turn waste into wealth, extract valuable metal, saves social resources；Technical scheme of the present invention uses wet method smelting
Refining, low energy consumption；Tungsten titanium recovery rate is up to 90% or more.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the flow chart of the method for green reclaim titanium containing tungsten vanadium catalyst provided in an embodiment of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained without making creative work it is all its
Its embodiment, shall fall within the protection scope of the present invention.
Such as Fig. 1, the embodiment of the present invention provides a kind of method of green reclaim titanium containing tungsten vanadium catalyst, including following step
Suddenly：
Step 1：The flue dust and salt enriched substance of cleaning catalyst cellular cavity entrainment.The catalyst is dead catalyst,
Contain the elements such as tungsten, titanium, vanadium.
Step 2：After cleaning, depth crushing is carried out using vibrations ball mill, 200 mesh sieve below is arranged in discharge port,
It is 200 mesh mixture below to obtain granularity.
Step 3：It carries out matching alkali technique.Sodium hydroxide solution is added in said mixture, makes its naoh concentration be
100~500g/L is heated 1-5 hours in autoclave or atmospheric kettle.Wherein, the ratio of adjusting intermixture and liquid is needed,
So that whole system has good mobility.
Step 4：The material that the reaction was complete in step 3 is separated by solid-liquid separation, solid is cleaned to pH=7~10, liquid
Step 3 is repeated, solid is the enriched substance of titanium.
Step 5：Complex acid 1 is carried out, with the solid-to-liquid ratio of the solid (enriched substance of titanium) obtained in dilute sulfuric acid regulating step four,
It can stir dynamic, be heated to 80 DEG C or more, keep the temperature 0.5-3 hour, then be separated by solid-liquid separation, the behaviour of liquid repetition step 5
Make, solid is continued to employ.
Step 6：Complex acid 2 is carried out, the solid obtained after step 5 is separated by solid-liquid separation adjusts solid-to-liquid ratio using dilute sulfuric acid, makes
It can stir dynamic, be heated to 80 DEG C or more, keep the temperature 0.5-3 hour, then be separated by solid-liquid separation, and liquid repeats step 6 and operates,
Solid is washed till pH ＞ 5 with clear water, and Solid Conveying and Melting to rotary kiln center is calcined, calcined product is titanium at a temperature of 1000 DEG C
White powder crushes after cooling, is packaged to be titanium dioxide product.
Wherein, when tungstic acid solubility is more than 60g/L in the liquid of step 4, condensing crystallizing is carried out, crystal is tungsten vanadium
The mixture of sodium salt, mother liquor reuse step 3.Tungsten vanadium sodium salt pH, extraction and separation tungsten vanadium are adjusted, or tungsten is precipitated as wolframic acid
Form, after separation of solid and liquid, liquid extraction goes out vanadium, i.e. vanadium product；Tungsten continues to be processed into ammonium paratungstate product, i.e. tungsten product.
In conclusion currently available technology carries out flue dust cleaning primarily directed to the intact dead catalyst of appearance,
With desulfuring and denitrifying apparatus such as telegram in reply factories after regeneration, the catalyst activation that at most can only achieve new product 80% after regeneration.The present invention's
Technical solution is that chemically angle is set out, turn waste into wealth, extract valuable metal, saves social resources；Technical scheme of the present invention
Using hydrometallurgy, low energy consumption；Tungsten titanium recovery rate is up to 90% or more.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (4)
1. a kind of method of green reclaim titanium containing tungsten vanadium catalyst, which is characterized in that include the following steps：
Step 1：The flue dust and salt enriched substance of cleaning catalyst cellular cavity entrainment；
Step 2：Depth crushing is carried out, 200 mesh mixture below is obtained；
Step 3：Sodium hydroxide solution is added in said mixture, it is 100~500g/L to make its naoh concentration, in height
It is heated 1-5 hours in pressure kettle or atmospheric kettle；
Step 4：The material that the reaction was complete in step 3 is separated by solid-liquid separation, solid is cleaned to pH=7~10, and liquid repeats
Step 3；
Step 5：With the solid-to-liquid ratio of the solid obtained in dilute sulfuric acid regulating step four, can stir it is dynamic, be heated to 80 DEG C with
On, 0.5-3 hours are kept the temperature, then be separated by solid-liquid separation, liquid repeats the operation of step 5；
Step 6：The solid obtained after step 5 is separated by solid-liquid separation adjusts solid-to-liquid ratio using dilute sulfuric acid, can stir dynamic, adds
Heat keeps the temperature 0.5-3 hours, then be separated by solid-liquid separation to 80 DEG C or more, and liquid repeats step 6 operation, and solid is washed till pH with clear water
＞ 5 is calcined Solid Conveying and Melting to rotary kiln center at a temperature of 1000 DEG C, and calcined product is titanium dioxide, crushes, wraps
Dress.
2. the method for green reclaim titanium containing tungsten vanadium catalyst as described in claim 1, it is characterised in that：In step 2, adopt
It is crushed with vibrations ball mill, 200 mesh sieve below is arranged in discharge port.
3. the method for green reclaim titanium containing tungsten vanadium catalyst as claimed in claim 1 or 2, it is characterised in that：Work as step 4
Liquid in tungstic acid solubility be more than 60g/L when, carry out condensing crystallizing, crystal be tungsten vanadium sodium salt mixture, mother liquor reuse
Step 3.
4. the method for green reclaim titanium containing tungsten vanadium catalyst as claimed in claim 3, it is characterised in that：Adjust tungsten vanadium sodium salt
PH, extraction and separation tungsten vanadium, or tungsten is precipitated as the form of wolframic acid, after separation of solid and liquid, liquid extraction goes out vanadium, and tungsten continues to be processed into
Ammonium paratungstate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810194421.0A CN108359799A (en) | 2018-03-09 | 2018-03-09 | A kind of method of green reclaim titanium containing tungsten vanadium catalyst |
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| CN201810194421.0A CN108359799A (en) | 2018-03-09 | 2018-03-09 | A kind of method of green reclaim titanium containing tungsten vanadium catalyst |
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| CN201810194421.0A Pending CN108359799A (en) | 2018-03-09 | 2018-03-09 | A kind of method of green reclaim titanium containing tungsten vanadium catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113528819A (en) * | 2021-07-12 | 2021-10-22 | 安徽思凯瑞环保科技有限公司 | Method for tungsten-vanadium alkaline extraction and realizing alkali liquor recycling |
| SE2050961A1 (en) * | 2020-08-19 | 2022-02-20 | Hong Jing Metal Corp | Method for recycling metals from carbon-containing waste molybdenum catalysts |
| CN114984947A (en) * | 2022-06-13 | 2022-09-02 | 安徽元琛环保科技股份有限公司 | Method for preparing denitration and dioxin removal catalyst by using waste SCR denitration catalyst |
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| KR20020035085A (en) * | 2002-04-23 | 2002-05-09 | 유정근 | Method for seperating V,W,Ti components from waste de-Nox catalyst |
| CN103484678A (en) * | 2013-09-09 | 2014-01-01 | 北京化工大学 | Method for recovering vanadium, tungsten and titanium from waste vanadium-tungsten-titanium-based denitration catalyst |
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Patent Citations (6)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE2050961A1 (en) * | 2020-08-19 | 2022-02-20 | Hong Jing Metal Corp | Method for recycling metals from carbon-containing waste molybdenum catalysts |
| SE544907C2 (en) * | 2020-08-19 | 2022-12-27 | Hong Jing Metal Corp | Method for recycling metals from carbon-containing waste molybdenum catalysts |
| CN113528819A (en) * | 2021-07-12 | 2021-10-22 | 安徽思凯瑞环保科技有限公司 | Method for tungsten-vanadium alkaline extraction and realizing alkali liquor recycling |
| CN114984947A (en) * | 2022-06-13 | 2022-09-02 | 安徽元琛环保科技股份有限公司 | Method for preparing denitration and dioxin removal catalyst by using waste SCR denitration catalyst |
| CN114984947B (en) * | 2022-06-13 | 2023-11-14 | 安徽元琛环保科技股份有限公司 | Method for preparing denitration and dioxin removal catalyst by using waste SCR denitration catalyst |
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Application publication date: 20180803 |