CN104591282A - High-temperature activation method for comprehensively utilizing waste denitration catalyst - Google Patents
High-temperature activation method for comprehensively utilizing waste denitration catalyst Download PDFInfo
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- CN104591282A CN104591282A CN201510014333.4A CN201510014333A CN104591282A CN 104591282 A CN104591282 A CN 104591282A CN 201510014333 A CN201510014333 A CN 201510014333A CN 104591282 A CN104591282 A CN 104591282A
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- denitration catalyst
- waste denitration
- activation method
- temperature activation
- vanadium pentoxide
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Abstract
The invention discloses a high-temperature activation method for comprehensively utilizing a waste denitration catalyst. The high-temperature activation method comprises the following steps: pulverizing the waste denitration catalyst; introducing air to burn fine-particle denitration catalyst at a certain temperature; soaking the burnt denitration catalyst into an NH4HCO3 solution with a certain concentration, and filtering to obtain filtrate and filter residue; precipitating and roasting the filtrate to recycle vanadium pentoxide. According to the high-temperature activation method, consumption of acid and alkaline is less in a soaking process, and vanadium pentoxide can be recycled by performing molybdenum precipitation once, wherein a recovery rate of vanadium pentoxide is up to 84%, the content of TiO2 in the filtered filter residue is not lower than 80%, and vanadium pentoxide can be used as a raw material for producing titanium dioxide through a sulfuric acid method by replacing ilmenite, so that the comprehensive utilization of the waste denitration catalyst is realized.
Description
Technical field
The present invention relates to the method for a kind of waste denitration catalyst comprehensive utilization, especially a kind of high-temperature activation method of waste denitration catalyst comprehensive utilization.
Background technology
In China's energy structure, mainly based on Coal Energy Source, burning coal will produce oxynitride, oxynitride (NO
x) mainly comprise NO, NO
2, N
2o etc., not only can form acid rain, can also cause chemical smoke, and harm humans is healthy, NO
xcause atmospheric pollution more and more to cause the attention of people, the regulation of relevant controlling discharge is also being gradually improved.At present, SCR (SCR) method is considered to best gas denitrifying technology, have higher denitration efficiency (can reach 90%), and technology is comparatively ripe, non-secondary pollution, is more and more applied at home and abroad.
What current SCR method was conventional is high temperature catalyst, and it is with TiO
2for carrier, main component is V
2o
5-WO
3(MoO
3) etc. metal oxide, these compositions account for more than 90% of catalyzer total amount, and the concrete coal that remaining minor component uses according to boiler is added.
The mounting means that SCR denitration adopts usually " 2+1 ", namely first installs 2 layers of catalyzer, installs the 3rd layer after about 3 years again additional, within 3 years, changes the 1st layer of catalyzer afterwards, within after this every 2 years, changes one deck catalyzer.Calculate there will be at least 27 ten thousand m by 2015 the work-ing life of about 3 years according to SCR catalyst
3waste catalyst produce.
How the waste catalyst of a large amount of inefficacy processes, disposes the great attention causing countries in the world.If do not add disposal to these waste catalyst and arbitrarily bank up, a large amount of land resources can be taken on the one hand, increase the cost of enterprise; Some poisonous and harmful substances that another aspect catalyzer adsorbs in the middle of use procedure and some metallic elements contained by self can enter into physical environment due to various effect, and particularly water body, brings serious harm to environment; The third aspect, spent catalyst abandons, and wherein contained various valuable metal resources fail to be recycled utilization, can cause the huge waste of efficient resource.So the recycling carrying out waste catalyst both can be turned waste into wealth, changed evil for benefit, and corresponding a series of potential problem of environmental pollution can also be solved, thus bring considerable economic benefit and social benefit.
Summary of the invention
The object of this invention is to provide a kind of denitrating catalyst from discarding and reclaim vanadium component, high-temperature activation method is adopted first to be separated with other metal oxides by the Vanadium Pentoxide in FLAKES in waste denitration catalyst, and then purify, and the raw material that will the material after Vanadium Pentoxide in FLAKES be isolated be used for replacing ilmenite as Titanium White Production By Sulfuric Acid Process, realize the comprehensive utilization of waste denitration catalyst.
Technical scheme provided by the invention is as follows:
The high-temperature activation method of this waste denitration catalyst comprehensive utilization is pulverized by discarded denitrating catalyst, then reached the object of separating-purifying Vanadium Pentoxide in FLAKES by operations such as high temperature sintering, leaching, precipitation and deaminations, specifically comprise the following steps:
(1) pulverize: waste denitration catalyst being crushed to median size is 0.10-0.30mm;
(2) high temperature sintering: the waste denitration catalyst after being pulverized by step (1) gained passes into air under the high temperature conditions and carries out calcination 2-3 hour;
(3) leach: step (2) is obtained the waste denitration catalyst particle after calcination and immerses certain density NH
4hCO
3solution, the immersion time is 2-3 hour, filters and obtains filtrate a and filter residue b;
(4) precipitation: add excess chlorination ammonium under 50-70 DEG C of condition in filtrate a, stirs 1-2 hour, then leaves standstill 2-4 hour, filters and obtains ammonium meta-vanadate;
(5) deamination: the ammonium meta-vanadate that step (4) obtains is calcined 1-2 hour under 450-550 DEG C of condition, obtains Vanadium Pentoxide in FLAKES.
Hot conditions in described step (2) is 600-800 DEG C.
NH in described step (3)
4hCO
3the concentration of solution is 1.0 × 10
-3~ 1.2 × 10
-3mol/g.
Filter residue b in described step (3) is for replacing ilmenite as the raw material of Titanium White Production By Sulfuric Acid Process.
Vanadium Pentoxide in FLAKES in waste denitration catalyst is first separated with other metal oxides by the present invention, and then purifies, and reclaims the Vanadium Pentoxide in FLAKES of the market requirement.The Vanadium Pentoxide in FLAKES rate of recovery>=84%; Reclaim TiO in the filter residue after Vanadium Pentoxide in FLAKES
2content>=80%, may be used for replacing ilmenite as the raw material of Titanium White Production By Sulfuric Acid Process, thus realize the comprehensive utilization of waste denitration catalyst.
Embodiment
The invention provides the high-temperature activation method of a kind of waste denitration catalyst comprehensive utilization, below by specific embodiment, the present invention is further elaborated.
Embodiment 1
Be under 600 DEG C of conditions, pass into air calcination 3 hours in the waste denitration catalyst of 0.10mm by being crushed to median size, then immersing concentration is 1.0 × 10
-3rare NH of mol/g
4hCO
3in solution, the immersion time is 3 hours, filters and obtains filtrate and filter residue, filter residue is delivered to sulfuric acid method titanium pigment raw materials for production warehouse, in filtrate, excess chlorination ammonium is added under 50 DEG C of conditions, stir 2 hours, then leave standstill 2 hours, filter and obtain ammonium meta-vanadate, by ammonium metavanadate precipitate, calcine 1 hour under 550 DEG C of conditions, obtain Vanadium Pentoxide in FLAKES finished product, the Vanadium Pentoxide in FLAKES rate of recovery>=84%.
Embodiment 2
Be under 700 DEG C of conditions, pass into air calcination 2.5 hours in the waste denitration catalyst of 0.20mm by being crushed to median size, then immersing concentration is 1.1 × 10
-3rare NH of mol/g
4hCO
3in solution, the immersion time is 2.5 hours, filters and obtains filtrate and filter residue, filter residue is delivered to sulfuric acid method titanium pigment raw materials for production warehouse, in filtrate, excess chlorination ammonium is added under 60 DEG C of conditions, stir 1.5 hours, then leave standstill 3 hours, filter and obtain ammonium meta-vanadate, by ammonium metavanadate precipitate, calcine 1.5 hours under 500 DEG C of conditions, obtain Vanadium Pentoxide in FLAKES finished product, the Vanadium Pentoxide in FLAKES rate of recovery>=84%.
Embodiment 3
Be under 800 DEG C of conditions, pass into air calcination 2 hours in the waste denitration catalyst of 0.30mm by being crushed to median size, then immersing concentration is 1.2 × 10
-3rare NH of mol/g
4hCO
3in solution, the immersion time is 2 hours, filtration obtains filtrate and filter residue, filter residue is delivered to sulfuric acid method titanium pigment raw materials for production warehouse, under 70 DEG C of conditions, adds excess chlorination ammonium in filtrate, stir 1 hour, then leave standstill 4 hours, filter and obtain ammonium meta-vanadate, by ammonium metavanadate precipitate, calcine 2 hours under 450 DEG C of conditions, obtain Vanadium Pentoxide in FLAKES finished product.The Vanadium Pentoxide in FLAKES rate of recovery >=84%.
In above-described embodiment, leaching process is few to bronsted lowry acids and bases bronsted lowry consumption, and through a precipitation and recyclable Vanadium Pentoxide in FLAKES, the Vanadium Pentoxide in FLAKES rate of recovery is high.
Claims (4)
1. a high-temperature activation method for waste denitration catalyst comprehensive utilization, is characterized in that, comprise following processing step:
(1) pulverize: waste denitration catalyst being crushed to median size is 0.10-0.30mm;
(2) high temperature sintering: the waste denitration catalyst after being pulverized by step (1) gained passes into air under the high temperature conditions and carries out calcination 2-3 hour;
(3) leach: step (2) is obtained the waste denitration catalyst particle after calcination and immerses certain density NH
4hCO
3solution, the immersion time is 2-3 hour, filters and obtains filtrate a and filter residue b;
(4) precipitation: add excess chlorination ammonium under 50-70 DEG C of condition in filtrate a, stirs 1-2 hour, then leaves standstill 2-4 hour, filters and obtains ammonium meta-vanadate;
(5) deamination: the ammonium meta-vanadate that step (4) obtains is calcined 1-2 hour under 450-550 DEG C of condition, obtains Vanadium Pentoxide in FLAKES.
2. the high-temperature activation method of waste denitration catalyst comprehensive utilization as claimed in claim 1, is characterized in that: the hot conditions in described step (2) is 600-800 DEG C.
3. the high-temperature activation method of waste denitration catalyst comprehensive utilization as claimed in claim 1, is characterized in that: NH in described step (3)
4hCO
3the concentration of solution is 1.0 × 10
-3~ 1.2 × 10
-3mol/g.
4. the high-temperature activation method of the waste denitration catalyst comprehensive utilization as described in claim 1 or 3, is characterized in that: the filter residue b in described step (3) is for replacing ilmenite as the raw material of Titanium White Production By Sulfuric Acid Process.
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|---|---|---|---|
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|---|---|---|---|
| CN201510014333.4A CN104591282A (en) | 2015-01-13 | 2015-01-13 | High-temperature activation method for comprehensively utilizing waste denitration catalyst |
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ID=53117399
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923458A (en) * | 2019-12-29 | 2020-03-27 | 江苏龙清环境技术有限公司 | Method for preparing titanium-tungsten powder by recycling waste SCR catalyst |
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| US20070025899A1 (en) * | 2005-07-29 | 2007-02-01 | Chevron U.S.A. Inc. | Process for metals recovery from spent catalyst |
| CN103952565A (en) * | 2014-04-11 | 2014-07-30 | 中国科学院过程工程研究所 | Method used for preparing ammonium metavanadate from vanadium slag via ammonium salt leaching |
| CN103966447A (en) * | 2014-05-20 | 2014-08-06 | 漯河兴茂钛业股份有限公司 | Comprehensive utilization method of waste denitration catalyst |
| CN104003442A (en) * | 2014-05-23 | 2014-08-27 | 中国科学院过程工程研究所 | Method for extracting vanadium by leaching vanadium-containing raw material roasted clinker with ammonium bicarbonate solution |
-
2015
- 2015-01-13 CN CN201510014333.4A patent/CN104591282A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070025899A1 (en) * | 2005-07-29 | 2007-02-01 | Chevron U.S.A. Inc. | Process for metals recovery from spent catalyst |
| CN103952565A (en) * | 2014-04-11 | 2014-07-30 | 中国科学院过程工程研究所 | Method used for preparing ammonium metavanadate from vanadium slag via ammonium salt leaching |
| CN103966447A (en) * | 2014-05-20 | 2014-08-06 | 漯河兴茂钛业股份有限公司 | Comprehensive utilization method of waste denitration catalyst |
| CN104003442A (en) * | 2014-05-23 | 2014-08-27 | 中国科学院过程工程研究所 | Method for extracting vanadium by leaching vanadium-containing raw material roasted clinker with ammonium bicarbonate solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923458A (en) * | 2019-12-29 | 2020-03-27 | 江苏龙清环境技术有限公司 | Method for preparing titanium-tungsten powder by recycling waste SCR catalyst |
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Application publication date: 20150506 |