CN102527373A - Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier - Google Patents
Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier Download PDFInfo
- Publication number
- CN102527373A CN102527373A CN2010106129323A CN201010612932A CN102527373A CN 102527373 A CN102527373 A CN 102527373A CN 2010106129323 A CN2010106129323 A CN 2010106129323A CN 201010612932 A CN201010612932 A CN 201010612932A CN 102527373 A CN102527373 A CN 102527373A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- tio
- active ingredient
- barium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention aims to provide a selective catalytic reduction (SCR) denitration catalyst in which a reinforcing material is not required to be added and TiO2 is taken as a carrier and which has high catalytic activity, and a manufacturing method for the SCR denitration catalyst. In the catalyst, barium-added TiO2 is taken as the carrier, wherein barium oxide accounts for 5 to 20 percent of the mass of the catalyst; and V2O5 is an active ingredient of the catalyst. The barium-added TiO2 accounts for 95 to 99 percent of the mass of active ingredients of the catalyst; and ammonium metavanadate is taken as a precursor of V2O5, and V2O5 accounts for 1 to 5 percent of the mass of the active ingredients of the catalyst. Compared with the prior art, the catalyst has the advantages that: the reinforcing material is not required to be added when the catalyst is prepared, so the active ingredients are more centralized and the activity is stronger, which are one of key breakthroughs of the invention. In addition, the catalyst has a high forming property and high strength. The SCR denitration catalyst has high catalytic activity; the catalytic activity of the SCR denitration catalyst is tested in flue gas ingredients simulated in a laboratory, NH3 is taken as a reducer, and the concentration of the SCR denitration catalyst is 1,000ppm; when the space velocity is 6,000h<-1>, the concentration of NOx is 1,000ppm, the volume percentage of O2 is 5 percent, and the balance is nitrogen; and the conversion rate of nitric oxide is 80 to 99 percent when the temperature is 300 to 450 DEG C.
Description
Technical field
The invention belongs to chemical field, particularly a kind of is the SCR denitrating catalyst and the manufacturing approach thereof of carrier with TiO2.
Background technology
Nitrogen oxide (NOx) is main atmosphere pollution, the destruction that can cause acid rain, photochemical fog, greenhouse effects and ozone layer.The nitrogen oxide of the annual discharging of power plants at present accounts for the over half of all nitrogen oxide emissions more than 1,000 ten thousand tons.Strengthen each item rules and the policy of restriction discharged nitrous oxides and stepping up to formulate or be about to appearance, the technology of therefore controlling discharged nitrous oxides also receives all circles and extensively payes attention to.
Reduce the NOx discharging two approach of Combustion Process Control and burning back denitrating flue gas are arranged.After adopting the low nitrogen burning technology, the discharged nitrous oxides concentration of unit does not still reach the discharge standard limit value, should set up equipment for denitrifying flue gas.Gas denitrifying technology mainly comprises SNCR technology (SNCR) and SCR technology (SCR).The SNCR technical matters is simple, but the denitration efficiency of this technology is low, is merely about 50%, is difficult to satisfy the high large coal-fired boiler of environmental requirement.With respect to other technology, the SCR technology has low cost and high-efficiency characteristics, is the main flow of denitrification process on the our times.
The core of SCR technology is a high performance catalyst; That catalyst mainly contains in form is board-like, three kinds of honeycomb fashion and corrugated plate dsts, compares board-like catalyst, and the honeycomb fashion catalyst can be regulated the aperture of honeycomb easily through changing the extruder mould; Thereby raising surface area; Therefore range of application is wideer, obtains higher denitration efficiency down in very high air speed (GHSV), and its market rate accounts for 70%.
Domestic applications at present have tens of kinds about the denitrating catalyst patent, can find out from disclosed patent, and carrier commonly used has TiO
2, Al
2O
3, molecular sieve, active carbon etc., wherein TiO
2Use the most extensive because having advantages of high catalytic activity.Nano-TiO
2Powder forming property is poor, so some materials are used as enhancement component or as matrix.Publication number is that the patent of invention report of CN101474565A adopts glass fibre to make honeycombed catalyst as enhancement component.Publication number is that the patent of invention of CN101396656A strengthens body the most with clay and glass fibre.Publication number is that the CN101185886A patent of invention is with Al
2O
3-SiO
2-TiO
2For complex carrier is coated on the cordierite honeycomb ceramic matrix again with the infusion process load active component.Publication number is that the patent of invention of CN1792431A is framework material with the cordierite honeycomb ceramic, double oxide Al
2O
3And TiO
2Be complex carrier, Al
2O
3Be internal layer carrier, TiO
2Be outer carrier, the dipping active component.Although reinforcing material improves the catalyst mechanical strength, its active constituent content is few, and catalytic activity reduces.
Summary of the invention
The object of the present invention is to provide a kind of need not to add reinforcing material, formability is good, intensity is high, and catalytic activity high be the SCR denitrating catalyst and the manufacturing approach thereof of carrier with TiO2.
Catalyst active ingredient of the present invention is:
To add barium type TiO
2Be carrier, wherein barium monoxide quality percentage composition is 5%～20%; V
2O
5For the catalyst activity composition, with V
2O
5The mass percent that calculating accounts for catalyst active ingredient is 1%～5%.
Add barium type TiO
2Accounting for catalyst active ingredient mass percent is 95%～99%; With the ammonium metavanadate is V
2O
5Presoma, V
2O
5Accounting for catalyst active ingredient mass percent is 1%～5%.
Method for preparing catalyst of the present invention may further comprise the steps:
1) mixing process:
With V
2O
5The mass percent that calculating accounts for catalyst active ingredient is 1%～5% to take by weighing ammonium metavanadate, with ammonium metavanadate and the abundant mixed dissolution of oxalic acid, adds barium type TiO
2And shaping additive, mechanical agitation is to mixing, and the content liquid of mixture is about 20%～50% mass percent.
The said barium type TiO that adds
2Be barium monoxide quality percentage composition be 5%～20% add barium type TiO
2, add barium type TiO
2Accounting for catalyst active ingredient mass percent is 95%～99%.
Said shaping additive comprises adhesive, plasticizer, lubricant and solvent, and wherein preferred version is following:
Adhesive is a polyvinyl alcohol, and extent of polymerization n is 1500～1700, and consumption is 5g～50g/1kg catalyst active ingredient;
As plasticizer and lubricant, consumption is 5g～50g/1kg catalyst active ingredient with glycerine;
With water is solvent, and consumption is 200ml～1000ml/1kg catalyst active ingredient.
2) extrusion molding process:
Larger particles in the mixture is extruded and removed by filter to the mixture that step 1) obtains through filtering extruder; Again through bipolar pug mill vacuum refining; Remove the gas that adsorbs in the pug, the pug after the refining carries out old, is squeezed into the ceramic honeycomb catalyst blank through the vacuum extruding form machine again.Preferred parameter is following:
Filtering the extruder extrusion pressure is 8MPa; Old 2～8 hours; Be squeezed into the ceramic honeycomb catalyst blank through the vacuum extruding form machine again, extrusion pressure is 8～12MPa, and extruded velocity is 0.5～2m/min.
3) dry run:
Remove moisture after the above-mentioned catalyst blank drying, preferred parameter is following:
Above-mentioned catalyst blank adopts hothouse dry, and temperature is controlled at 80 ℃～120 ℃, and heating rate is 10～50 ℃/hour, humidity control 20%～70%, dry 8～12 hours of blank.
4) sintering procedure:
Dry rear catalyst is fired into finished product, and its preferred parameter is following:
Above-mentioned catalyst adopts shuttle kiln to fire, and heating rate is 1～10 ℃/minute, rises to firing temperature from 100 ℃, and firing temperature is 450 ℃～550 ℃, stablizes 2～6 hours at firing temperature, and stove is chilled to 100 ℃.
Catalyst of the present invention is because preparation the time need not to add reinforcing material, so active ingredient is more concentrated, and activity is stronger, and this is the present invention than one of important breakthrough of prior art.In addition, shaped catalyst property of the present invention is good, intensity is high.SCR denitrating catalyst catalytic activity of the present invention is high, and its catalytic activity of test is a reducing agent with NH3 in the laboratory simulation smoke components, and its concentration is 1000ppm, is 6000h in air speed
-1, NO
xConcentration is 1000ppm, O
2Percentage by volume is 5%, and all the other are nitrogen, and when temperature range was 300 ℃～450 ℃, the conversion ratio of nitrogen oxide was 80%～99%.
The specific embodiment
Through specific embodiment the present invention is further specified below.
Embodiment 1:
With V
2O
5Account for catalyst active ingredient mass percent and be 1% and calculate and take by weighing the 400g ammonium metavanadate, 600g oxalic acid, 30L water, the 500g polyvinyl alcohol, 500g glycerine, abundant mixed dissolution, what add 30kg barium monoxide percentage composition 20% adds barium type TiO
2Powder, mechanical agitation was mixed 1 hour.Mixture filters through filtering extruder, passes through the pug mill vacuum refining again, old 2 hours of gained pug.Be squeezed into the ceramic honey comb blank through vacuum-extruder again, extrusion pressure is 10MPa.Blank gets into 100 ℃ of dryings of hothouse 12 hours.Dry good blank gets into shuttle kiln and fires, and heating rate is 1 ℃/minute, rises to firing temperature from 100 ℃, and firing temperature is 450 ℃, stablizes 4 hours at firing temperature, and stove is chilled to below 100 ℃.
Embodiment 2:
With V
2O
5Account for catalyst active ingredient mass percent and be 5% and calculate and take by weighing the 2000g ammonium metavanadate, 3000g oxalic acid, 30L water, the 500g polyvinyl alcohol, 500g glycerine, abundant mixed dissolution, what add 30kg barium monoxide percentage composition 20% adds barium type TiO
2Powder, mechanical agitation was mixed 1 hour.Mixture filters through filtering extruder, passes through the pug mill vacuum refining again, old 4 hours of gained pug.Be squeezed into the ceramic honey comb blank through vacuum-extruder again, extrusion pressure is 12MPa.Blank gets into 100 ℃ of dryings of hothouse 12 hours.Dry good blank gets into shuttle kiln and fires, and heating rate is 1 ℃/minute, rises to firing temperature from 100 ℃, and firing temperature is 500 ℃, stablizes 4 hours at firing temperature, and stove is chilled to below 100 ℃.
Embodiment 3:
With V
2O
5Account for catalyst active ingredient mass percent and be 1% and calculate and take by weighing the 400g ammonium metavanadate, 600g oxalic acid, 20L water, the 1500g polyvinyl alcohol, 1500g glycerine, abundant mixed dissolution, what add 30kg barium monoxide percentage composition 5% adds barium type TiO
2Powder, mechanical agitation was mixed 1 hour.Mixture filters through filtering extruder, passes through the pug mill vacuum refining again, old 4 hours of gained pug.Be squeezed into the ceramic honey comb blank through vacuum-extruder again, extrusion pressure is 10MPa.Blank gets into 100 ℃ of dryings of hothouse 8 hours.Dry good blank gets into shuttle kiln and fires, and heating rate is 2 ℃/minute, rises to firing temperature from 100 ℃, and firing temperature is 450 ℃, stablizes 6 hours at firing temperature, and stove is chilled to below 100 ℃.
Embodiment 4:
With V
2O
5Account for catalyst active ingredient mass percent and be 5% and calculate and take by weighing the 2000g ammonium metavanadate, 3000g oxalic acid, 30L water, the 1500g polyvinyl alcohol, 1500g glycerine, abundant mixed dissolution, what add 30kg barium monoxide percentage composition 5% adds barium type TiO
2Powder, mechanical agitation was mixed 1 hour.Mixture filters through filtering extruder, passes through the pug mill vacuum refining again, old 4 hours of gained pug.Be squeezed into the ceramic honey comb blank through vacuum-extruder again, extrusion pressure is 12MPa.Blank gets into 100 ℃ of dryings of hothouse 12 hours.Dry good blank gets into shuttle kiln and fires, and heating rate is 1 ℃/minute, rises to firing temperature from 100 ℃, and firing temperature is 500 ℃, stablizes 4 hours at firing temperature, and stove is chilled to below 100 ℃.
Embodiment 1～4 described catalyst is tested its catalytic activity in the laboratory simulation smoke components, with NH
3Be reducing agent, its concentration is 1000ppm, is 6000h in air speed
-1, NO
xConcentration is 1000ppm, O
2Percentage by volume is 5%, and all the other are under the condition of nitrogen gas, and the transformation efficiency of the oxides of nitrogen of catalyst under different temperatures is as shown in table 1.
Transformation efficiency of the oxides of nitrogen/the % of table 1 catalyst under different temperatures
Claims (5)
1. one kind with TiO
2Be the SCR denitrating catalyst of carrier, it is characterized in that to add barium type TiO
2Be carrier, wherein barium monoxide quality percentage composition is 5%～20%; V
2O
5Be the catalyst activity composition.
2. according to claim 1 with TiO
2Be the SCR denitrating catalyst of carrier, it is characterized in that adding barium type TiO
2Accounting for catalyst active ingredient mass percent is 95%～99%; With the ammonium metavanadate is V
2O
5Presoma, V
2O
5Accounting for catalyst active ingredient mass percent is 1%～5%.
3. claim 1 is described with TiO
2Preparation method for the SCR denitrating catalyst of carrier is characterized in that may further comprise the steps:
(1) with V
2O
5The mass percent that calculating accounts for catalyst active ingredient is 1%～5% to take by weighing ammonium metavanadate, with ammonium metavanadate and the abundant mixed dissolution of oxalic acid, adds barium type TiO
2And shaping additive, mechanical agitation is to mixing, and the content liquid of mixture is about 20%～50% mass percent.
(2) larger particles in the mixture is extruded and removed by filter to the mixture that obtains of step 1) through filtering extruder; Again through bipolar pug mill vacuum refining; Remove the gas that adsorbs in the pug, the pug after the refining carries out old, is squeezed into the ceramic honeycomb catalyst blank through the vacuum extruding form machine again;
(3) remove moisture after the above-mentioned catalyst blank drying;
(4) dry rear catalyst is fired into finished product.
4. as claimed in claim 3 with TiO
2Be the preparation method of the SCR denitrating catalyst of carrier, it is characterized in that described in the step 1) that in the shaping assistant, adhesive is a polyvinyl alcohol, extent of polymerization n is 1500～1700, and consumption is 5g～50g/1kg catalyst active ingredient; Glycerine is plasticizer and lubricant, and consumption is 5g～50g/1kg catalyst active ingredient; Water is solvent, and consumption is 200ml～1000ml/1kg catalyst active ingredient.
5. as claimed in claim 3 with TiO
2Preparation method for the SCR denitrating catalyst of carrier is characterized in that adding described in the step 1) barium type TiO
2Be barium monoxide quality percentage composition be 5%～20% add barium type TiO
2, add barium type TiO
2Accounting for catalyst active ingredient mass percent is 95%～99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106129323A CN102527373A (en) | 2010-12-29 | 2010-12-29 | Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106129323A CN102527373A (en) | 2010-12-29 | 2010-12-29 | Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102527373A true CN102527373A (en) | 2012-07-04 |
Family
ID=46336124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106129323A Pending CN102527373A (en) | 2010-12-29 | 2010-12-29 | Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102527373A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537297A (en) * | 2012-07-13 | 2014-01-29 | 中国钢铁股份有限公司 | Plate-shaped catalyst composition for selective catalytic reduction reaction and method for producing same |
| CN111135820A (en) * | 2019-12-30 | 2020-05-12 | 安徽元琛环保科技股份有限公司 | Preparation method of barium-containing flue gas denitration catalyst and prepared denitration catalyst |
| CN114308008A (en) * | 2021-11-24 | 2022-04-12 | 安徽元琛环保科技股份有限公司 | Porous reduced TiO based on Ba doping2Preparation method of ultralow-temperature denitration catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214343A (en) * | 1982-06-04 | 1983-12-13 | Ube Ind Ltd | Formation of honeycomb denitration catalyst |
| CN1768953A (en) * | 2004-10-29 | 2006-05-10 | 韩国电力公社 | Method of regenerating honeycomb type SCR catalyst by air lift loop reactor |
| CN101658793A (en) * | 2009-09-29 | 2010-03-03 | 浙江三龙催化剂有限公司 | Titania-based catalytic agent in coal steam-electric plant smoke SCR denitration and preparation method thereof |
-
2010
- 2010-12-29 CN CN2010106129323A patent/CN102527373A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214343A (en) * | 1982-06-04 | 1983-12-13 | Ube Ind Ltd | Formation of honeycomb denitration catalyst |
| CN1768953A (en) * | 2004-10-29 | 2006-05-10 | 韩国电力公社 | Method of regenerating honeycomb type SCR catalyst by air lift loop reactor |
| CN101658793A (en) * | 2009-09-29 | 2010-03-03 | 浙江三龙催化剂有限公司 | Titania-based catalytic agent in coal steam-electric plant smoke SCR denitration and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537297A (en) * | 2012-07-13 | 2014-01-29 | 中国钢铁股份有限公司 | Plate-shaped catalyst composition for selective catalytic reduction reaction and method for producing same |
| CN103537297B (en) * | 2012-07-13 | 2015-08-19 | 中国钢铁股份有限公司 | Plate-shaped catalyst composition for selective catalytic reduction reaction and method for producing same |
| CN111135820A (en) * | 2019-12-30 | 2020-05-12 | 安徽元琛环保科技股份有限公司 | Preparation method of barium-containing flue gas denitration catalyst and prepared denitration catalyst |
| CN114308008A (en) * | 2021-11-24 | 2022-04-12 | 安徽元琛环保科技股份有限公司 | Porous reduced TiO based on Ba doping2Preparation method of ultralow-temperature denitration catalyst |
| CN114308008B (en) * | 2021-11-24 | 2024-01-23 | 安徽元琛环保科技股份有限公司 | Porous reduction TiO based on Ba doping 2 Preparation method of ultra-low temperature denitration catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101706881B1 (en) | Apparatus and process for continuous production of scr plate-type denitrated catalyst | |
| CN101444727B (en) | Preparation method of integral honeycombed catalyst for SCR flue-gas denitration | |
| CN101428212B (en) | Selective catalysis reduction denitrate catalyst for composite carrier flue gas and preparation method thereof | |
| CN106140150A (en) | A kind of honeycomb fashion cerium zirconium manganese titanio denitrating catalyst and preparation method thereof | |
| CN103861628A (en) | Flue-gas denitration catalyst incapable of being deactivated by basic metallic oxides, preparation method thereof and applications thereof | |
| CN106732751B (en) | Desulfurization and denitrification catalyst, and preparation method and use method thereof | |
| CN101676024A (en) | Faviform ammonia-method selective-catalytic-reduction denitrified catalyst and preparation method thereof | |
| CN102698810B (en) | Honeycomb type denitration catalyst and preparation method thereof | |
| CN105435776A (en) | Honeycomb-like cerium-zirconium-tungsten-titanium-based denitration catalyst and preparation method thereof | |
| CN104162421A (en) | Preparation method of high temperature resistant vanadium tungsten titanium oxide catalyst | |
| CN103769239A (en) | Honeycomb-type denitration catalyst with hierarchical pore structure and preparation method for honeycomb-type denitration catalyst | |
| CN106140143A (en) | A kind of non-homogeneous honeycomb type denitrating catalyst and preparation method thereof | |
| CN105597730A (en) | Honeycomb vanadium series denitration preformed catalyst, and preparation method and use thereof | |
| CN103301831A (en) | Catalyst for removing nitrogen oxide in emission exhaust and preparation method thereof | |
| CN105772075A (en) | MnOx/SAPO-34 low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst, and preparation method and application thereof | |
| CN105833901A (en) | PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof | |
| CN106268786A (en) | A kind of low-temperature denitration catalyst and preparation method thereof | |
| CN107456994A (en) | High temperature honeycomb catalyst and preparation method thereof | |
| CN107442164A (en) | Extruded type molecular sieve honeycomb catalyst and preparation method thereof | |
| CN105435769A (en) | Honeycomb-like cerium-zirconium-titanium-based denitration catalyst and preparation method thereof | |
| CN103263914A (en) | Honeycomb-shaped SCR denitration catalysis material for cement kiln and preparation method thereof | |
| CN101862648A (en) | SCR deNOx catalyst added with attapulgite and preparation method thereof | |
| CN102527373A (en) | Selective catalytic reduction (SCR) denitration catalyst with TiO2 as carrier | |
| CN107754810A (en) | A kind of wide temperature smoke denitrating catalyst of non-vanadium base monolithic, preparation method and application | |
| CN104607198A (en) | Vanadium-free plate-like denitration catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |