CN101862648A - SCR deNOx catalyst added with attapulgite and preparation method thereof - Google Patents
SCR deNOx catalyst added with attapulgite and preparation method thereof Download PDFInfo
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- CN101862648A CN101862648A CN201010191089A CN201010191089A CN101862648A CN 101862648 A CN101862648 A CN 101862648A CN 201010191089 A CN201010191089 A CN 201010191089A CN 201010191089 A CN201010191089 A CN 201010191089A CN 101862648 A CN101862648 A CN 101862648A
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Abstract
The invention relates to a method for preparing an SCR deNOx catalyst added with attapulgite, which comprises the following steps of: (1) purifying the attapulgite by adopting a dry or wet method to make the purity of the attapulgite reach over 60 percent, and dispersing attapulgite crystal fibers; (2) adding water to the purified attapulgite, titanium dioxide, active ingredients and a forming aid in a certain ratio, performing high-speed stirring, homogenizing, filtering, and fully mixing the raw materials by using a mixing mill; (3) forming the mixed slurry by using an extruder according to engineering requirement; and (4) drying at certain humidity and temperature to obtain a catalyst blank, and sintering the blank in a sintering furnace to obtain the finished product. The invention also relates to the SCR deNOx catalyst prepared by the method. The attapulgite is added to form a pore structure in the SCR deNOx catalyst, so that the catalyst has elasticity and thermal stress resistance, and can be used for removing NOx from flue gas of heat-engine plants and industrial stoves.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to a kind of SCR denitrating catalyst that is used for thermal power plant and Industrial Stoves flue gas and preparation method thereof.
Background technology
Nitrogen oxide (NOx) is one of atmosphere pollution main outside smoke abatement and the sulfur dioxide, lets alone discharging and will cause danger to natural environment and health.The external history that the technology and the research in policy of nitrogen oxide reduction of discharging were had an appointment 30 years.The Eleventh Five-Year Plan period, China begins to start nitrogen oxide reduction of discharging work, especially at the more serious Beijing-Tianjin Ji of nitrogen oxides pollution, the Yangtze River Delta and area, Pearl River Delta.The nitrogen oxide that discharges in view of the thermal power generation industry accounts for about 40% of China's total release, require after 2010 in the Beijing-Tianjin Ji in " 2009-2010 the whole nation prevention and cure of pollution key work ", the Yangtze River Delta and area, Pearl River Delta, the necessary synchronized construction denitrification apparatus of newly-built thermal power plant, and the active service unit will all be finished the denitration transformation before the end of the year in 2015.Therefore, will form great demand during China " 12 " to denitration technology.
In the out of stock technology of present main flow, (SelectiveCatalytic Reduction, SCR) technology is main denitrating technique with SCR in external denitration engineering employing more than 90%.The SCR technology has the highest denitration efficiency and better economic, and its core is a selective reduction catalyst.Under the condition that catalyst exists, the ammonia that sprays in the flue gas can optionally form N with the NOx reaction
2And H
2Thereby O denitration.The main flow of SCR catalyst is the V-W-Ti catalyst at present, and composition is with TiO
2Be carrier, with V
2O
5Or WO
3-V
2O
5Be active component, add MnO simultaneously
2And MoO
3Deng as anti-sintering and anti-poisoning component.Find in the out of stock engineering of domestic part that because ature of coal is relatively poor, factor such as burning control etc., cause flue dust in the flue gas, arsenic and alkaline-earth metal that catalyst is caused the infringement of physics and catalytic performance, active decline is comparatively serious, generally is difficult to reach 36000h service life.More catalyst changeout makes the economy of SCR technology descend in advance, therefore needs can improve so that the smoke condition of its suitable China the antitoxin performance of catalyst, mechanical strength and sintering resistance.
The SCR course of reaction is the heterogeneous reaction that a catalyst participates in, bigger surface area, the pore passage structure of more active sites and optimization provides advantage for absorption, reaction and the desorption of reactant, therefore an important process that improves the SCR catalyst performance is optimized its microstructure exactly, and keeps the stable of microstructure.The multi-stage artery structure of micropore-mesopore-Hong hole combination is favourable to absorption, reaction and the mass transfer of catalytic process.Multiple nonmetallic ore has a natural peacekeeping two-dimensional structure on the earth, is therefore paid close attention to and is applied in the catalyst.
U.S. Pat 4188365 discloses a kind of with TiO
2With average grain diameter be the SCR catalyst that the kaolin particle mixture of the montmorillonite type of 0.1-100 micron is done carrier, the material that has wherein added other fibre structures is optimized the structural behaviour of carrier.
It is the catalyst for denitration by SCR method with low cost and preparation method thereof of carrier with flyash that domestic patent CN200810195864.8 discloses a kind of, wherein adds Ludox, clay, glass fiber to increase catalyst strength.
Attapulgite (Attapulgite) claims palygorskite (Palygorskite) or Palygorskite again, be a kind of have enrich microstructure contain Shuifu County's magnesium silicate mineral.The crystal of attapulgite is needle-like, fibrous or fiber collection shape, has the duct of the about 200-2000nm of diameter 20nm length on the microcosmic, presents the feature of one-dimensional nano structure; Show on the macroscopic view have bigger specific area, ammine selective absorption and ion exchange property.These features make attapulgite become feasible as the structure optimization component of SCR denitrating catalyst.China has the resources advantage of attapulgite, accounts for the whole world and has verified 44% of attapulgite clay reserves.So far do not have as yet and add attapulgite to improve the research and the reported literature of SCR catalyst performance.
Summary of the invention
The objective of the invention is to add attapulgite to improve the performance of SCR denitrating catalyst, its mechanism is to make the SCR catalyst have micropore-mesopore-crosslinked network structure in Hong hole, optimize the elasticity and the intensity of catalyst simultaneously, thereby promote the performance of mass transfer, anti-poisoning performance and the anti-fly ash erosion of catalyst.The SCR denitrating catalyst of the present invention preparation can be used for removing of NOx in thermal power plant and the Industrial Stoves flue gas.
The technical solution adopted for the present invention to solve the technical problems is: in SCR denitration catalyst agent prescription, add the attapulgite of 3-50% mass ratio.Preparing the raw materials used proportioning of this SCR denitrating catalyst (mass percent) is:
Titanium dioxide 40-90
Attapulgite 3.0-50.0
Active component: V
2O
5, MoO
3, WO
3, MnO
21-10
Shaping assistant: sodium carboxymethylcellulose, polyvinyl alcohol, carbon fiber 1-10
Its production technology may further comprise the steps:
(1) purification of attapulgite
By dry method or wet purification attapulgite, purity reaches more than 60%, with dolomite, calcite, opal, quartz and a small amount of heavy metal of removing wherein association, and disperses the attapulgite crystal fibre.
(2) preparation of slurry
By a certain percentage the attapulgite of purifying and titanium dioxide, active component and shaping assistant are added water and carry out high-speed stirred, filter behind the homogeneous, utilize mixing roll fully mixing then raw material.
(3) shaping of catalyst
Slurry after mixing is by the extruder moulding, and extruded velocity is a prerequisite with the outward appearance of keeping catalyst.Extrude the back by the engine request cutting, make the honeycomb fashion catalyst.Also the slurry after mixing can be made board-like catalyst.
(4) dry and burn till
Dry under certain humidity and temperature conditions, obtain the catalyst blank.Blank is sent into sintering furnace and is burnt till, and heats up from 120 ℃ of start programs, and 1 ℃/min of control heating rate was 450 ℃ of insulations 0.5-4 hour.Rate of temperature fall is controlled less than 5 ℃/min, and coming out of the stove less than 50 ℃ when temperature obtains finished product.
Compared with prior art, the present invention has following advantage:
1. behind the interpolation attapulgite, form multi-stage artery structure in the SCR catalyst, the aperture mainly is distributed in from 200
3000
With 50000
Contain micropore-mesopore and grand hole yardstick.Multistage pore structure helps mass transfer, and harmful substance is difficult for the deposition on catalyst in the flue gas, thereby slows down the poisoning of catalyst.
2. the nano pore structure of attapulgite has water imbibition and water-retaining property, makes catalyst have elasticity and thermal stress resistance ability.Preferred catalyst can keep the denitration rate more than 85% in 200-500 ℃ of scope, 600-800 ℃ of denitration rate that keeps 70-75%, and the intensification of the 100 ℃/min that can bear simultaneously and cooling circulation 278 times.The elasticity of catalyst helps to resist the abrasion of flying dust.
3. attapulgite helps the absorption of reactant and the carrying out of reduction reaction to the selective adsorption capacity of ammonia.
The invention will be further described below in conjunction with embodiment.
The specific embodiment
Embodiment 1
Adopt dry purification high-adhesive attapulgite purity to 70%, be ground to 400 orders.Attapulgite, titanium dioxide, active component and shaping assistant were by mass ratio 15: 72: 9: 4 add water carries out high-speed stirred, filters behind the homogeneous, utilizes mixing roll fully mixing to raw material then.Slurry after mixing is provided with hole count 18 * 18, section 150mm * 150mm, wall thickness 1.2mm, pitch 8.2mm by the extruder moulding.Humidity 50% and 43 ℃ of dryings obtain the catalyst blank.Blank is sent into sintering furnace and is burnt till, and heats up from 120 ℃ of start programs, and 1 ℃/min of control heating rate was 450 ℃ of insulations 0.5-4 hour.Rate of temperature fall is controlled less than 5 ℃/min, and coming out of the stove less than 50 ℃ when temperature obtains finished product.Finished product percent opening 82.1%, specific area 504m
2/ m
3, mechanical strength 213N/cm.
Utilize above-mentioned catalyst that simulated flue gas is carried out the denitration experiment, NO concentration is 500ppm in the air inlet, control NH
3With the NO mol ratio be 1: 1, O
2Concentration is 5%, N
2Be balance gas, air speed is controlled at 32000h
-1Catalyst has the denitration efficiency more than 85% in 200-500 ℃ of scope.
Embodiment 2
Adopt wet purification high-adhesive attapulgite purity to 90%, be ground to 400 orders.Attapulgite, titanium dioxide, active component and shaping assistant were by mass ratio 15: 72: 9: 4 add water carries out high-speed stirred, filters behind the homogeneous, utilizes mixing roll fully mixing to raw material then.Slurry after mixing is provided with hole count 18 * 18, section 150mm * 150mm, wall thickness 1.2mm, pitch 8.2mm by the extruder moulding.Humidity 50% and 43 ℃ of dryings obtain the catalyst blank.Blank is sent into sintering furnace and is burnt till, and heats up from 120 ℃ of start programs, and 1 ℃/min of control heating rate was 450 ℃ of insulations 0.5-4 hour.Rate of temperature fall is controlled less than 5 ℃/min, and coming out of the stove less than 50 ℃ when temperature obtains finished product.Finished product percent opening 87.9%, specific area 524m
2/ m
3, mechanical strength 243N/cm.
Utilize above-mentioned catalyst that simulated flue gas is carried out the denitration experiment, NO concentration is 500ppm in the air inlet, control NH
3With the NO mol ratio be 1: 1, O
2Concentration is 5%, N
2Be balance gas, air speed is controlled at 32000h
-1Catalyst has the denitration efficiency more than 92% in 200-500 ℃ of scope.
Embodiment 3
Adopt dry purification absorbent-type attapulgite purity to 60%, be ground to 400 orders.Attapulgite, titanium dioxide, active component and shaping assistant were by mass ratio 15: 72: 9: 4 add water carries out high-speed stirred, filters behind the homogeneous, utilizes mixing roll fully mixing to raw material then.Slurry after mixing is provided with hole count 18 * 18, section 150mm * 150mm, wall thickness 1.2mm, pitch 8.2mm by the extruder moulding.Humidity 50% and 40 ℃ of dryings obtain the catalyst blank.Blank is sent into sintering furnace and is burnt till, and heats up from 120 ℃ of start programs, and 1 ℃/min of control heating rate was 450 ℃ of insulations 0.5-4 hour.Rate of temperature fall is controlled less than 5 ℃/min, and coming out of the stove less than 50 ℃ when temperature obtains finished product.Finished product percent opening 68.1%, specific area 423m
2/ m
3, mechanical strength 167N/cm.
Utilize above-mentioned catalyst that simulated flue gas is carried out the denitration experiment, NO concentration is 500ppm in the air inlet, control NH
3With the NO mol ratio be 1: 1, O
2Concentration is 5%, N
2Be balance gas, air speed is controlled at 32000h
-1Catalyst has the denitration efficiency more than 81% in 200-500 ℃ of scope.
Embodiment 4
Adopt wet purification absorbent-type attapulgite purity to 80%, be ground to 400 orders.Attapulgite, titanium dioxide, active component and shaping assistant were by mass ratio 15: 72: 9: 4 add water carries out high-speed stirred, filters behind the homogeneous, utilizes mixing roll fully mixing to raw material then.Slurry after mixing is provided with hole count 18 * 18, section 150mm * 150mm, wall thickness 1.2mm, pitch 8.2mm by the extruder moulding.Humidity 50% and 40 ℃ of dryings obtain the catalyst blank.Blank is sent into sintering furnace and is burnt till, and heats up from 120 ℃ of start programs, and 1 ℃/min of control heating rate was 450 ℃ of insulations 0.5-4 hour.Rate of temperature fall is controlled less than 5 ℃/min, and coming out of the stove less than 50 ℃ when temperature obtains finished product.Finished product percent opening 73.3%, specific area 467m
2/ m
3, mechanical strength 177N/cm.
Utilize above-mentioned catalyst that simulated flue gas is carried out the denitration experiment, NO concentration is 500ppm in the air inlet, control NH
3With the NO mol ratio be 1: 1, O
2Concentration is 5%, N
2Be balance gas, air speed is controlled at 32000h
-1Catalyst has the denitration efficiency more than 84% in 200-500 ℃ of scope.
Claims (4)
1. a preparation method who adds the SCR denitrating catalyst of attapulgite comprises the steps:
(1) purification of attapulgite comprises: by dry method or wet purification attapulgite, purity reaches more than 60%, with dolomite, calcite, opal, quartz and a small amount of heavy metal of removing wherein association, and the fiber of dispersion attapulgite.
(2) preparation of slurry comprises: by a certain percentage the attapulgite of purifying and titanium dioxide, active component and shaping assistant are added water and carry out high-speed stirred, filter behind the homogeneous, utilize mixing roll fully mixing to raw material then.
(3) shaping of catalyst comprises that " slurry after mixing is by the extruder moulding, and extruded velocity is a prerequisite with the outward appearance of keeping catalyst.Extrude the back by the engine request cutting, make the honeycomb fashion catalyst.Also the slurry after mixing can be made board-like catalyst.
(4) dry and burn till, comprising: dry under certain humidity and temperature conditions, obtain the catalyst blank.Blank is sent into sintering furnace and is burnt till, and heats up from 120 ℃ of start programs, and 1 ℃/min of control heating rate was 450 ℃ of insulations 0.5-4 hour.Rate of temperature fall is controlled less than 5 ℃/min, and coming out of the stove less than 50 ℃ when temperature obtains finished product.
2. the described preparation method of claim 1 is characterized in that adding in the step (2) mass ratio 3.0-50.0% attapulgite.
3. the described preparation method of claim 1 is characterized in that adding attapulgite purity in the step (2) is more than 60%.
4. a SCR denitrating catalyst that adds attapulgite is characterized in that containing in the finished product mass ratio 3.0-50.0% attapulgite.
Priority Applications (1)
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| CN201010191089A CN101862648A (en) | 2010-06-03 | 2010-06-03 | SCR deNOx catalyst added with attapulgite and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607180A (en) * | 2015-01-21 | 2015-05-13 | 常州大学 | Mixed-crystal MnO2/rod-like clay low-temperature denitration catalyst and preparation method thereof |
| CN106311331A (en) * | 2016-08-31 | 2017-01-11 | 南京禾宇化工有限公司 | Preparation method of denitration catalyst with attapulgite-cordierite honeycomb ceramics-TiO2 as carries |
| CN106345269A (en) * | 2016-10-24 | 2017-01-25 | 马鞍山科宇环境工程有限公司 | Coal denitration agent |
| CN106362806A (en) * | 2016-08-31 | 2017-02-01 | 南京禾宇化工有限公司 | Application of catalyst with attapulgite-cordierite honeycomb ceramic-TiO2 serving as carrier to denitration |
| CN106390995A (en) * | 2016-08-31 | 2017-02-15 | 南京禾宇化工有限公司 | Denitration catalyst taking attapulgite-cordierite honeycomb ceramic-TiO2 as carrier |
| CN106540684A (en) * | 2016-12-06 | 2017-03-29 | 北京国电龙源环保工程有限公司 | High activity honeycomb fashion SCR catalyst and preparation method thereof |
| CN107138152A (en) * | 2017-07-04 | 2017-09-08 | 合肥市大卓电力有限责任公司 | A kind of denitrating catalyst of high intensity and preparation method thereof |
| CN110204351A (en) * | 2019-06-26 | 2019-09-06 | 江苏龙净科杰环保技术有限公司 | A method of ceramic honey comb is prepared with denitrating catalyst waste material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607180A (en) * | 2015-01-21 | 2015-05-13 | 常州大学 | Mixed-crystal MnO2/rod-like clay low-temperature denitration catalyst and preparation method thereof |
| CN106311331A (en) * | 2016-08-31 | 2017-01-11 | 南京禾宇化工有限公司 | Preparation method of denitration catalyst with attapulgite-cordierite honeycomb ceramics-TiO2 as carries |
| CN106362806A (en) * | 2016-08-31 | 2017-02-01 | 南京禾宇化工有限公司 | Application of catalyst with attapulgite-cordierite honeycomb ceramic-TiO2 serving as carrier to denitration |
| CN106390995A (en) * | 2016-08-31 | 2017-02-15 | 南京禾宇化工有限公司 | Denitration catalyst taking attapulgite-cordierite honeycomb ceramic-TiO2 as carrier |
| CN106345269A (en) * | 2016-10-24 | 2017-01-25 | 马鞍山科宇环境工程有限公司 | Coal denitration agent |
| CN106540684A (en) * | 2016-12-06 | 2017-03-29 | 北京国电龙源环保工程有限公司 | High activity honeycomb fashion SCR catalyst and preparation method thereof |
| CN106540684B (en) * | 2016-12-06 | 2019-05-10 | 北京国电龙源环保工程有限公司 | The preparation method of high activity honeycomb fashion SCR catalyst |
| CN107138152A (en) * | 2017-07-04 | 2017-09-08 | 合肥市大卓电力有限责任公司 | A kind of denitrating catalyst of high intensity and preparation method thereof |
| CN110204351A (en) * | 2019-06-26 | 2019-09-06 | 江苏龙净科杰环保技术有限公司 | A method of ceramic honey comb is prepared with denitrating catalyst waste material |
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Address after: 311814, Zhejiang, Zhuji province Jiefang Road Town, No. 386, Hoi Liang group, 3 floor Applicant after: Shi Lei Address before: 310012 Pension Platan Xihu District 258 Xueyuan Road Zhejiang Hangzhou 5-502 Applicant before: Shi Lei |
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