CN103877990A - Polynary metallic oxide denitration catalyst - Google Patents
Polynary metallic oxide denitration catalyst Download PDFInfo
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- CN103877990A CN103877990A CN201410145531.XA CN201410145531A CN103877990A CN 103877990 A CN103877990 A CN 103877990A CN 201410145531 A CN201410145531 A CN 201410145531A CN 103877990 A CN103877990 A CN 103877990A
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- metal oxide
- denitrating catalyst
- element metal
- presoma
- oxide denitrating
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Abstract
The invention discloses a polynary metallic oxide denitration catalyst. The catalyst comprises the active ingredients of iron sesquioxide, manganese dioxide, vanadium pentoxide and chromium sesquioxide, and a carrier comprises the following components: titanium dioxide, aluminum oxide and silicon dioxide. The catalyst comprises the following components in percentage by weight: 15-30 percent of the iron sesquioxide, 3-7 percent of the manganese dioxide, 1-3 percent of the vanadium pentoxide, 1-3 percent of the chromium sesquioxide, 5-15 percent of the titanium dioxide, 25-40 percent of the aluminum oxide and 15-30 parts of the silicon dioxide. The polynary metallic oxide denitration catalyst is prepared by adopting a relatively simple impregnation method. A large amount of cost can be saved under the condition that the high/low-temperature catalytic activity is relatively well guaranteed, and the catalyst is particularly used in environments such as thermal power plants in which the flue gas emission load is particularly large, the treatment capacity on nitric oxides is particularly high and the treatment cost serves as one of main indexes.
Description
Technical field
The present invention relates to the denitrating catalyst being formed by several metal oxides.
Background technology
In the flue gas discharging after burning under high temperature and high pressure environment in internal combustion engine and heat power plant boiler etc., contain a large amount of nitrogen oxide, these nitrogen oxide are the primary pollution source that produces photochemical fog, acid rain and damage the ozone layer etc.Therefore, just need carry out harmless treatment to these nitrogen oxide in flue gas---industrial being called " denitration ".One of method of denitration is selective catalytic reduction (Selective Catalytic Reduction, SCR).The method is with ammonia (NH
3) as reducing agent, under the effect of denitrating catalyst by nitrogen oxide (NO
x) be reduced into nitrogen (N
2) and water (H
2o).The quality of the method denitration effect and the activity under high/low temperature condition, all mainly determined by the performance of denitrating catalyst.Be current common one by denitrating catalyst that several metal oxide forms, publication number is that CN101898136A name is called " wide temperature window NH
3-SCR removes diesel engine NO
xtitanium Quito unit composite oxide catalysts " technical scheme be exactly one of them.Metal oxide in the component of this technical scheme has, as the V of major catalyst
2o
5, CeO
2, MnO
2and Fe
2o
3, as the WO of co-catalyst
3(tungsten oxide) and MoO
3(molybdenum oxide), and as the TiO of carrier
2.With respect to other denitrating catalysts, when the activity when low temperature of this technical scheme and high temperature, selectively there is an expansion by a relatively large margin, in 100～550 ℃ of wide temperature ranges, all can more effectively reduce the amount of nitrogen oxides in flue gas.But, in the catalyst component in the prior art, CeO
2(cerium oxide) is rare-earth oxide, WO
3and MoO
3be all again rare metal oxide, price is all more expensive, and therefore, the prior art exists the deficiency that cost is higher.
Summary of the invention
The object of this invention is to provide a kind of catalytic activity and prior art suitable, but the lower multi-element metal oxide denitrating catalyst of its cost.
The technical scheme that realizes described object is so a kind of multi-element metal oxide denitrating catalyst, and aspect same as the prior art is, its active component has di-iron trioxide, manganese dioxide and vanadic anhydride, and its carrier components comprises titanium dioxide.Its improvements are in described carrier components, to also have alundum (Al2O3) and silica; In this multi-element metal oxide denitrating catalyst, each component is calculated according to mass percent, be respectively: di-iron trioxide 15%～30%, manganese dioxide 3%～7%, vanadic anhydride 1～3%, titanium dioxide is 5%～15%, alundum (Al2O3) 25%～40%, silica is 15%～30%; This multi-element metal oxide denitrating catalyst is prepared from as follows:
(1) solution preparation: presoma using nine water ferric nitrates as di-iron trioxide, the four water acetic acid manganese presoma as the presoma of manganese dioxide, ammonium metavanadate as vanadic anhydride, join in the lump in deionized water, and fully mix under 70～90 ℃ of water bath condition, incorporation time is all dissolved in deionized water as degree take each presoma;
Wherein, the consumption of each presoma, all according to each corresponding component, the proportional quantity in described multi-element metal oxide denitrating catalyst is determined after converting; The quality of deionized water, determines according to 0.9～1.1 times of the gross mass of the each component of described multi-element metal oxide denitrating catalyst;
(2) solidliquid mixture preparation: the presoma using gel aluminum hydroxide as alundum (Al2O3), add together with titanium dioxide with silica in the solution preparing in step (1), and fully mix under 70～90 ℃ of water bath condition;
Wherein, the consumption of gel aluminum hydroxide, determines after the proportional quantity according to corresponding alundum (Al2O3) in described multi-element metal oxide denitrating catalyst converts; The consumption of silica and titanium dioxide, the proportional quantity according to them in described multi-element metal oxide denitrating catalyst is determined;
(3) moulding: step (2) gained mixture is placed in to 70～90 ℃ of baking ovens, ageing 15～24 hours; Pugging, rubbing, granulation;
(4) roasting: step (3) gained particle is placed in to 70～90 ℃ of baking ovens dry 3～4 hours, and then by the roasting one hour under 250～270 ℃ of temperature conditions of these particles; Roasting three hours under 490～510 ℃ of temperature conditions more afterwards; After this, stove is chilled to room temperature, obtains being granular multi-element metal oxide denitrating catalyst.
From scheme, can find out, in the active component of product of the present invention, not use cerium oxide of the prior art, tungsten oxide and molybdenum oxide.Owing to not adopting these expensive metal oxides, therefore, cost of the present invention just greatly reduces naturally again.From scheme, it can also be seen that, product of the present invention has increased alundum (Al2O3) and silica in carrier components, and has reduced the proportional quantity of titanium dioxide simultaneously.Checking shows, by adjusting the mode to catalytic activity also influential carrier components, can make the present invention in the situation that its cost reduces greatly, within the scope of 100～550 ℃, still there is good catalytic activity---be particularly suitable for smoke discharge amount large especially, large especially to the treating capacity of nitrogen oxide, therefore treatment cost is also used in the environment such as the thermal power plant of one of leading indicator.In addition, prepare because the present invention adopts relatively simple infusion process, therefore, also guaranteed the further reduction of the cost of multi-element metal oxide denitrating catalyst of the present invention from manufacture aspect.
Below in conjunction with the specific embodiment, the present invention is further illustrated.
The specific embodiment
A kind of multi-element metal oxide denitrating catalyst, its active component has di-iron trioxide, manganese dioxide and vanadic anhydride, and its carrier components comprises titanium dioxide (TiO
2).In the present invention, in described carrier components, also have alundum (Al2O3) and silica (SiO
2); In this multi-element metal oxide denitrating catalyst, each component is calculated according to mass percent, be respectively: di-iron trioxide 15%～30%, manganese dioxide 3%～7%, vanadic anhydride 1～3%, titanium dioxide is 5%～15%, alundum (Al2O3) 25%～40%, silica is 15%～30%; This multi-element metal oxide denitrating catalyst is prepared from as follows:
(1) solution preparation: with nine water ferric nitrate ［ Fe (NO
3)
39H
2o ］ as di-iron trioxide (Fe
2o
3) presoma, four water acetic acid manganese ［ Mn (CH
3cOO)
24H
2o ］ as manganese dioxide (MnO
2) presoma, ammonium metavanadate (NH
4vO
3) as vanadic anhydride (V
2o
5) presoma, join in deionized water in the lump, and fully mix under 70～90 ℃ of water bath condition, incorporation time is all dissolved in deionized water as degree (it will be apparent to those skilled in that take each presoma, want course of dissolution and complete sooner, be by modes such as stirrings.Under stirring state, conventionally just can allow each presoma all be dissolved in deionized water with 25～35 minutes and suffer);
Wherein, the consumption of each presoma, all according to each corresponding component, the proportional quantity in described multi-element metal oxide denitrating catalyst is determined and ［ for example, is supposed to calculate di-iron trioxide (Fe by proportioning after converting
2o
3) consumption is 2.3 grams, so, the nine water ferric nitrate ［ Fe (NO that determine after converting
3)
39H
2o ］ consumption just should be 11.615 grams ］; The quality of deionized water, determines according to 0.9～1.1 times of the gross mass of the each component of described multi-element metal oxide denitrating catalyst;
(2) solidliquid mixture preparation: with gel aluminum hydroxide ［ Al (OH)
3as alundum (Al2O3) (Al
2o
3) presoma, add together with titanium dioxide with silica in the solution preparing in step (1), and under 70～90 ℃ of water bath condition fully mix (it will be apparent to those skilled in that, guarantee that abundant mixing also will be by modes such as stirrings.Under stirring state, conventionally with within 25～35 minutes, just guaranteeing abundant mixing);
Wherein, the consumption of gel aluminum hydroxide, determines after the proportional quantity according to corresponding alundum (Al2O3) in described multi-element metal oxide denitrating catalyst converts; The consumption of silica and titanium dioxide, the proportional quantity according to them in described multi-element metal oxide denitrating catalyst is determined;
(3) moulding: step (2) gained mixture is placed in to 70～90 ℃ of baking ovens, ageing 15～24 hours; Pugging, rubbing, granulation;
(4) roasting: step (3) gained particle is placed in to 70～90 ℃ of baking ovens dry 3～4 hours, and then by the roasting one hour under 250～270 ℃ of temperature conditions of these particles; Roasting three hours under 490～510 ℃ of temperature conditions more afterwards; After this, stove is chilled to room temperature, obtains being granular multi-element metal oxide denitrating catalyst.
Further, owing to working as TiO
2on carrier, there is non-crystallized Cr
2o
3time, can improve catalytic efficiency and to N
2selective, so, for obtaining better effect, in described active component, also have chrome green (Cr
2o
3), that in step (1), add is the nine water chromic nitrate ［ Cr (NO as this chrome green presoma
3)
39H
2o ］; The consumption of this nine water chromic nitrate, the mass percent according to corresponding chrome green in described multi-element metal oxide denitrating catalyst be 1～3% convert after determine.
Further say, for effect of the present invention can be brought into play better, 0.5～1 centimetre of the particle diameter of the particle of step (4) gained multi-element metal oxide denitrating catalyst.Obviously, in the time of the particle diameter of the made particle of determining step (3), just should rule of thumb estimate (and even do necessary calculate), with guarantee dry, double roasting by step (4) and cooling after, the particle diameter of final products is still 0.5～1 centimetre.
The experimental verification that the present invention has passed through to do in laboratory, preparation checking is identical with step described in the specific embodiment by the step of multi-element metal oxide denitrating catalyst.The result table proof list.
When checking, adopting homemade internal diameter is the stainless steel multichannel continuous flow reactor of fixed bed of 14mm, and each road gas is respectively with entering blender after mass flowmenter metering.With NO, O
2and N
2simulate industrial smoke, with NH
3for reducing agent.The determination of activity of multi-element metal oxide denitrating catalyst of the present invention is carried out in fixed bed reaction pipe.Total gas flow rate is 262mL/min, and air speed is 10000h
-1.Being configured to of simulated flue gas: 500ppmNO, 500ppmNH
3, 2%O
2, N
2for Balance Air.By the concentration of NO in FGA-4100 type exhaust gas analyzer assaying reaction pipe tail gas.Be calculated as follows denitration rate:
In formula:
for denitration rate;
for the concentration of the NO of air inlet place;
for the concentration of the NO of gas outlet place.
Note: because the consumption of each presoma is all to determine according to the proportioning of each corresponding component, therefore, each component and the corresponding proportioning in notebook invention multi-element metal oxide denitrating catalyst only in proof list, and do not record the each presoma in preparation process.In addition, due to the deionized water amount ranges of step in preparation process (1), the bath temperature scope of step (2), the Aging Temperature scope of step (3), the temperature range of the baking temperature of step (4) and time range, double roasting, be " franchise " (the not tolerance of impact effect) in suitability for industrialized production, therefore, be not documented in proof list yet.In table, " digestion time (h) " is the digestion time in step (3).
Proof list:
From proof list, can find out, the present invention is in the situation that providing cost savings with respect to prior art, and the catalytic activity (denitration rate) under condition of different temperatures is still suitable with prior art.This has also proved, it is large, large especially to the treating capacity of nitrogen oxide especially that the present invention is particularly suitable for smoke discharge amount really, therefore treatment cost is also used in the environment such as the thermal power plant of one of leading indicator.
Claims (3)
1. a multi-element metal oxide denitrating catalyst, its active component has di-iron trioxide, manganese dioxide and vanadic anhydride, and its carrier components comprises titanium dioxide; It is characterized in that in described carrier components, also having alundum (Al2O3) and silica; In this multi-element metal oxide denitrating catalyst, each component is calculated according to mass percent, be respectively: di-iron trioxide 15%～30%, manganese dioxide 3%～7%, vanadic anhydride 1～3%, titanium dioxide is 5%～15%, alundum (Al2O3) 25%～40%, silica is 15%～30%; This multi-element metal oxide denitrating catalyst is prepared from as follows:
(1) solution preparation: presoma using nine water ferric nitrates as di-iron trioxide, the four water acetic acid manganese presoma as the presoma of manganese dioxide, ammonium metavanadate as vanadic anhydride, join in the lump in deionized water, and fully mix under 70～90 ℃ of water bath condition, incorporation time is all dissolved in deionized water as degree take each presoma;
Wherein, the consumption of each presoma, all according to each corresponding component, the proportional quantity in described multi-element metal oxide denitrating catalyst is determined after converting; Described deionized water quality, determines according to 0.9～1.1 times of the gross mass of the each component of described multi-element metal oxide denitrating catalyst;
(2) solidliquid mixture preparation: the presoma using gel aluminum hydroxide as alundum (Al2O3), add together with titanium dioxide with silica in the solution preparing in step (1), and fully mix under 70～90 ℃ of water bath condition;
Wherein, the consumption of described gel aluminum hydroxide, determines after the proportional quantity according to corresponding alundum (Al2O3) in described multi-element metal oxide denitrating catalyst converts; The consumption of silica and titanium dioxide, the proportional quantity according to them in described multi-element metal oxide denitrating catalyst is determined;
(3) moulding: step (2) gained mixture is placed in to 70～90 ℃ of baking ovens, ageing 15～24 hours; Pugging, rubbing, granulation;
(4) roasting: step (3) gained particle is placed in to 70～90 ℃ of baking ovens dry 3～4 hours, and then by the roasting one hour under 250～270 ℃ of temperature conditions of these particles; Roasting three hours under 490～510 ℃ of temperature conditions more afterwards; After this, stove is chilled to room temperature, obtains being granular multi-element metal oxide denitrating catalyst.
2. multi-element metal oxide denitrating catalyst according to claim 1, is characterized in that, also has chrome green in described active component, and what in step (1), add is the nine water chromic nitrates as this chrome green presoma; The consumption of this nine water chromic nitrate, the mass percent according to corresponding chrome green in described multi-element metal oxide denitrating catalyst be 1～3% convert after determine.
3. according to multi-element metal oxide denitrating catalyst described in claim 1 or 2, it is characterized in that, at the particle diameter 0.5～1cm of the particle of step (4) gained multi-element metal oxide denitrating catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145531.XA CN103877990A (en) | 2014-04-14 | 2014-04-14 | Polynary metallic oxide denitration catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145531.XA CN103877990A (en) | 2014-04-14 | 2014-04-14 | Polynary metallic oxide denitration catalyst |
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| Publication Number | Publication Date |
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| CN103877990A true CN103877990A (en) | 2014-06-25 |
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ID=50947310
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| CN201410145531.XA Pending CN103877990A (en) | 2014-04-14 | 2014-04-14 | Polynary metallic oxide denitration catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971605A (en) * | 2015-06-24 | 2015-10-14 | 方耀 | Coal-fired flue gas treatment method |
| CN106186480A (en) * | 2016-09-06 | 2016-12-07 | 苏州方舟环保科技有限公司 | The technique of a kind of compound advanced catalytic oxidation and device |
| CN106902891A (en) * | 2017-03-31 | 2017-06-30 | 安徽中煦环保新材料科技有限公司 | A kind of high-efficiency denitration catalyst |
| CN109433217A (en) * | 2018-11-29 | 2019-03-08 | 山东大学 | A kind of red mud denitrating catalyst and preparation method thereof |
| CN111282562A (en) * | 2018-12-10 | 2020-06-16 | 中国石油化工股份有限公司 | Manganese-based catalyst and preparation method and application thereof |
| CN113634254A (en) * | 2021-08-13 | 2021-11-12 | 交通运输部天津水运工程科学研究所 | Non-road field denitration catalyst coating material and application thereof |
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2014
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| JP4259633B2 (en) * | 1997-09-08 | 2009-04-30 | 北海道電力株式会社 | Method for producing smoke treatment agent |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971605A (en) * | 2015-06-24 | 2015-10-14 | 方耀 | Coal-fired flue gas treatment method |
| CN106186480A (en) * | 2016-09-06 | 2016-12-07 | 苏州方舟环保科技有限公司 | The technique of a kind of compound advanced catalytic oxidation and device |
| CN106902891A (en) * | 2017-03-31 | 2017-06-30 | 安徽中煦环保新材料科技有限公司 | A kind of high-efficiency denitration catalyst |
| CN109433217A (en) * | 2018-11-29 | 2019-03-08 | 山东大学 | A kind of red mud denitrating catalyst and preparation method thereof |
| CN109433217B (en) * | 2018-11-29 | 2020-07-17 | 山东大学 | Red mud denitration catalyst and preparation method thereof |
| CN111282562A (en) * | 2018-12-10 | 2020-06-16 | 中国石油化工股份有限公司 | Manganese-based catalyst and preparation method and application thereof |
| CN113634254A (en) * | 2021-08-13 | 2021-11-12 | 交通运输部天津水运工程科学研究所 | Non-road field denitration catalyst coating material and application thereof |
| CN113634254B (en) * | 2021-08-13 | 2023-02-14 | 交通运输部天津水运工程科学研究所 | Non-road field denitration catalyst coating material and application thereof |
| WO2023015890A1 (en) * | 2021-08-13 | 2023-02-16 | 交通运输部天津水运工程科学研究所 | Denitration catalyst coating material for non-road field and use thereof |
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Application publication date: 20140625 |