CN104148056A - Conducting flue gas denitration catalyst and preparation method thereof - Google Patents
Conducting flue gas denitration catalyst and preparation method thereof Download PDFInfo
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- CN104148056A CN104148056A CN201410446327.1A CN201410446327A CN104148056A CN 104148056 A CN104148056 A CN 104148056A CN 201410446327 A CN201410446327 A CN 201410446327A CN 104148056 A CN104148056 A CN 104148056A
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- flue gas
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Abstract
The invention relates to a conducting flue gas denitration catalyst and a preparation method thereof. The conducting flue gas denitration catalyst is prepared from the following raw materials in percentage by weight: 60 to 90 percent of titanium dioxide, 3 to 9 percent of tungsten trioxide, 0.1 to 2 percent of vanadium pentoxide, 1 to 5 percent of silicon dioxide, 1 to 5 percent of rare earth, 3 to 10 percent of C fibers and the balance of a forming agent. The conducting flue gas denitration catalyst has a wire function, implements low-temperature catalysis, has high denitration efficiency, a low SO2/SO3 conversion rate, a low ammonia escape rate, wear resistance, high intensity, a long chemical service life and a long mechanical service life and has low output of domestic sewage.
Description
Technical field
The present invention relates to a kind of SCR catalyst for denitrating flue gas, be specifically related to a kind of conduction catalyst for denitrating flue gas and preparation method thereof.
Background technology
NOx in flue gas is the major source of pollutant that causes atmosphere pollution, and it not only can damage multiple human organ, even carcinogenic.For denitrating flue gas, the technology of maturation is SCR denitration technology the most in the world at present.SCR denitration technology refers under the effect of denitrating catalyst, the NOx in flue gas and spray into the reducing agent (NH in flue gas
3) there is reduction reaction, generate N
2and H
2o.But the SCR denitrating catalyst reaction temperature of employing is normally within the scope of 350 DEG C～400 DEG C at present, namely usually said middle temperature denitrating catalyst.For ensureing the reaction temperature of denitrating catalyst and avoiding stopping up inactivation because the too low production sulphur of reaction temperature ammonium salt causes catalyst, after reactor is disposed in boiler conventionally.But, in the flue gas of this arrangement, contain a large amount of SO
2, K
2o, CaO and As
2o
3deng, can cause catalyst poisoning, and the flying dust of high concentration can cause obstruction and the corrosion of catalyst, reduce its service life.And due to the limitation of space and pipeline, the expense of in the existing steam generator system of some power plant, the SCR system being arranged on above desulfurizing dust-collector being transformed is very high.
These external other denitration applications are as denitration peculiar to vessel, sulfuric acid plant, coke-oven plant etc., and exhanst gas outlet temperature is lower, and current used middle temperature denitrating catalyst (generally taking V-Ti-W as main) can not meet the requirement of denitration.Domestic and international each scientific research institutions and colleges and universities are are also all actively researching and developing various low-temperature denitration catalysts at present, but the low-temperature denitration catalyst of development wants denitration efficiency very low at present, service life very short, can not meet commercial Application at all.
Summary of the invention
The object of this invention is to provide a kind of conduction catalyst for denitrating flue gas and preparation method thereof, realize low-temperature denitration, have reaction temperature window wide, denitration efficiency is high, SO
2/ SO
3low conversion rate, the escaping of ammonia rate is low, wear-resistant, intensity is high, and chemical lifetime is long, and mechanical life is long.
A kind of conduction catalyst for denitrating flue gas of the present invention, made by the raw material of following percentage by weight: titanium dioxide 60% ?90%, tungstic acid 3% ?9%, vanadic anhydride 0.1% ?2%, silica 1 % ?5%, rare earth 1% ?5%, C fiber 3% ?10%, surplus is forming agent.
Rare earth is one or both in cerium or lanthanum.
Forming agent is one or more in lactic acid, first class cellulose or polyethylene glycol.
The preparation method of conduction catalyst for denitrating flue gas, preparation process is as follows:
After being mixed, titanium dioxide, tungstic acid, vanadic anhydride, silica, rare earth add C fiber and forming agent mixing; Material after mixing old 12 ?after 36 hours, carry out cooling processing, through filtering, extrude in advance, extrude, wet cutting, twice dry after calcining obtain product.
The condition of primary drying be baking temperature be from room temperature to 80 DEG C of 70 ?, dry humidity is that 10 ?90%, drying time are 72 ?240 hours; Redrying condition be baking temperature be from room temperature to 100 DEG C of 90 ?, dry humidity is that 10 ?60%, drying time are 12 ?36 hours.
Mixing temperature is 30-60 DEG C, and mixing time is 1-6 hour.
C fiber use before use soaking in alcohol process 12 ?24h.
C fibre diameter be 5 ?10 μ m, length be 3 ?10mm, water content be 1 ?10%.
Calcining heat be from room temperature to 650 ?750 DEG C.
Calcination time be 24 ?72 hours.
Extruding in advance, extrude and be continuous operation, is routine operation.Extrusion temperature is below 50 DEG C.
In catalyst, add C fiber and rare earth element thereof, catalyst body not only has electric conductivity but also have certain resistance, the heating of energising rear catalyst body self-heating cooking energising rear catalyst, by the flue gas to 300 DEG C contacting with catalyst surface, so, improve the denitration efficiency of catalyst, suppressed again SO
2/ SO
3conversion.
The concrete preparation method of conduction catalyst for denitrating flue gas is:
(1) mixing: after titanium dioxide, tungstic acid, vanadic anhydride, silica, rare earth are mixed, to add C fiber and forming agent, carry out mixing;
(2) filter and extrude in advance: after the old 12-36 of material that step (1) is obtained hour, filter, the material filtering out carries out directly extruding in advance after cooling processing;
(3) extrude: the pre-extrudate that step (2) is obtained, by mold integral extrusion molding;
(4) wet cutting: step (3) is obtained conducting electricity catalyst for denitrating flue gas and be cut into pieces;
(5) dry: the catalyst that step (4) is obtained carries out primary drying and redrying processing;
(6) calcining: will calcine through twice dried catalytic agent for denitrating smoke.
The reaction temperature window of product of the present invention is 180 DEG C-420 DEG C.
Compared with prior art, the present invention has following beneficial effect:
Catalyst for denitrating flue gas of the present invention has conductive exothermal function, through catalyzed dose of own heating of flue gas of catalyst surface, reaches denitration temperature requirement, has realized low-temperature denitration, has reaction temperature window wide, and denitration efficiency is high, SO
2/ SO
3low conversion rate, the escaping of ammonia rate is low, wear-resistant, intensity is high, and chemical lifetime is long, and mechanical life is long, can apply widely and the low-temperature denitration fields such as denitration peculiar to vessel, nitric plant's denitration, coke-oven plant's denitration.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The present embodiment conduction catalyst for denitrating flue gas, is made up of the raw material of following percetage by weight: titanium dioxide 62%, tungstic acid 9%, vanadic anhydride 1%, silica 2%, cerium 2%, C fiber 10%, lactic acid 6%, first class cellulose 4% and surplus are polyethylene glycol.
The concrete preparation method of conduction catalyst for denitrating flue gas is:
(1) mixing: after titanium dioxide, tungstic acid, vanadic anhydride, silica, cerium are mixed, to add C fiber, lactic acid, first class cellulose and polyethylene glycol, carry out mixing;
(2) filter and extrude in advance: the material that step (1) is obtained, after old 12 hours, filters, and the material filtering out carries out directly extruding in advance after cooling processing;
(3) extrude: the pre-extrudate that step (2) is obtained, by mold integral extrusion molding;
(4) wet cutting: step (3) is obtained conducting electricity catalyst for denitrating flue gas and be cut into pieces;
(5) dry: the catalyst that step (4) is obtained carries out primary drying and redrying processing;
(6) calcining: will be raised to 650 DEG C from room temperature through twice dried catalyst, and calcine 30 hours.
Wherein, in step (1), mixing temperature is 60 DEG C, and mixing time is 1 hour.
The condition of primary drying be baking temperature be from room temperature to 80 DEG C, dry humidity be 15%, be 72 hours drying time.
The condition of redrying be baking temperature be from room temperature to 90 DEG C, dry humidity be 20%, be 15 hours drying time.
Denitration efficiency>=90% of product, SO
2/ SO
3conversion ratio < 1%, chemical lifetime>=24000h, mechanical life>=80000h.
Embodiment 2
The de-conduction of the present embodiment denitrating flue gas catalyst for denitrating flue gas, is made up of the raw material of following percetage by weight: titanium dioxide 90%, tungstic acid 3%, vanadic anhydride 0.1%, silica 1 %, lanthanum 1%, C fiber 3%, first class cellulose 1.5% and surplus polyethylene glycol.
The concrete preparation method of conduction catalyst for denitrating flue gas is:
(1) mixing: after titanium dioxide, tungstic acid, vanadic anhydride, silica, lanthanum are mixed, to add C fiber, first class cellulose and polyethylene glycol, carry out mixing;
(2) filter and extrude in advance: the material that step (1) is obtained, after old 30 hours, filters, and the material filtering out carries out directly extruding in advance after cooling processing;
(3) extrude: the pre-extrudate that step (2) is obtained, by mold integral extrusion molding;
(4) wet cutting: step (3) is obtained conducting electricity catalyst for denitrating flue gas and be cut into pieces;
(5) dry: the catalyst that step (4) is obtained carries out primary drying and redrying processing;
(6) calcining: will be raised to 700 DEG C from room temperature through twice dried catalyst, and calcine 65 hours.
Wherein, in step (1), mixing temperature is 50 DEG C, and mixing time is 2 hours.
The condition of primary drying be baking temperature be from room temperature to 70 DEG C, dry humidity be 50%, be 200 hours drying time.
Redrying condition be baking temperature be from room temperature to 100 DEG C, dry humidity be 30%, be 36 hours drying time.
Denitration efficiency>=90% of product, SO
2/ SO
3conversion ratio < 1%, chemical lifetime>=24000h, mechanical life>=80000h.
Embodiment 3
The present embodiment conduction catalyst for denitrating flue gas, made by the raw material of following percetage by weight: titanium dioxide 75%, tungstic acid 5%, vanadic anhydride 1%, silica 5%, lanthanum 1.5%, cerium 1%, C fiber 5%, surplus is lactic acid.
The concrete preparation method of conduction catalyst for denitrating flue gas is:
(1) mixing: after titanium dioxide, tungstic acid, vanadic anhydride, silica, lanthanum and cerium are mixed, to add C fiber and lactic acid, carry out mixing;
(2) filter and extrude in advance: the material that step (1) is obtained, after old 20 hours, filters, and the material filtering out carries out directly extruding in advance after cooling processing;
(3) extrude: the pre-extrudate that step (2) is obtained, by mold integral extrusion molding;
(4) wet cutting: step (3) is obtained conducting electricity catalyst for denitrating flue gas and be cut into pieces;
(5) dry: the catalyst that step (4) is obtained carries out primary drying and redrying processing;
(6) calcining: will be raised to 750 DEG C from room temperature through twice dried catalyst, and calcine 72 hours.
Wherein, in step (1), mixing temperature is 40 DEG C, and mixing time is 3 hours.
The condition of primary drying be baking temperature be from room temperature to 75 DEG C, dry humidity be 60%, be 240 hours drying time.
Redrying condition be baking temperature be from room temperature to 95 DEG C, dry humidity be 40%, be 36 hours drying time.
Denitration efficiency>=90% of product, SO
2/ SO
3conversion ratio < 1%, chemical lifetime>=24000h, mechanical life>=80000h.
Embodiment 4
The present embodiment conduction catalyst for denitrating flue gas, made by the raw material of following percetage by weight: titanium dioxide 80%, tungstic acid 2%, vanadic anhydride 0.5%, silica 2%, cerium 1% and lanthanum 3%, C fiber 7%, lactic acid 1% and surplus are polyethylene glycol.
The concrete preparation method of conduction catalyst for denitrating flue gas is:
(1) mixing: after titanium dioxide, tungstic acid, vanadic anhydride, silica, cerium and lanthanum are mixed, to add C fiber, lactic acid and polyethylene glycol, carry out mixing;
(2) filter and extrude in advance: the material that step (1) is obtained, after old 36 hours, filters, and the material filtering out carries out directly extruding in advance after cooling processing;
(3) extrude: the pre-extrudate that step (2) is obtained, by mold integral extrusion molding;
(4) wet cutting: step (3) is obtained conducting electricity catalyst for denitrating flue gas and be cut into pieces;
(5) dry: the catalyst that step (4) is obtained carries out primary drying and redrying processing;
(6) calcining: will be raised to 660 DEG C from room temperature through twice dried catalyst, and calcine 40 hours.
Wherein, in step (1), mixing temperature is 30 DEG C, and mixing time is 4 hours.
The condition of primary drying be baking temperature be from room temperature to 100 DEG C, dry humidity be 70%, be 150 hours drying time.
Redrying condition be baking temperature be from room temperature to 90 DEG C, dry humidity be 60%, be 13 hours drying time.
Denitration efficiency>=90% of product, SO
2/ SO
3conversion ratio < 1%, chemical lifetime>=24000h, mechanical life>=80000h.
Embodiment 5
The present embodiment conduction catalyst for denitrating flue gas, made by the raw material of following percetage by weight: titanium dioxide 70%, tungstic acid 3%, vanadic anhydride 1.5%, silica 4%, cerium 5%, C fiber 9%, surplus is polyethylene glycol.
The concrete preparation method of conduction catalyst for denitrating flue gas is:
(1) mixing: after titanium dioxide, tungstic acid, vanadic anhydride, silica, cerium are mixed, to add C fiber and polyethylene glycol, carry out mixing;
(2) filter and extrude in advance: the material that step (1) is obtained, after old 25 hours, filters, and the material filtering out carries out directly extruding in advance after cooling processing;
(3) extrude: the pre-extrudate that step (2) is obtained, by mold integral extrusion molding;
(4) wet cutting: step (3) is obtained conducting electricity catalyst for denitrating flue gas and be cut into pieces;
(5) dry: the catalyst that step (4) is obtained carries out primary drying and redrying processing;
(6) calcining: will be raised to 720 DEG C from room temperature through twice dried catalyst, and calcine 60 hours.
Wherein, in step (1), mixing temperature is 60 DEG C, and mixing time is 2 hours.
The condition of primary drying be baking temperature be from room temperature to 80 DEG C, dry humidity be 60%, be 200 hours drying time.
Redrying condition be baking temperature be from room temperature to 95 DEG C, dry humidity be 15%, be 36 hours drying time.
Denitration efficiency>=90% of product, SO
2/ SO
3conversion ratio < 1%, chemical lifetime>=24000h, mechanical life>=80000h.
Claims (9)
1. a conduction catalyst for denitrating flue gas, is characterized in that, is made up: titanium dioxide 60%-90% of the raw material of following percentage by weight, tungstic acid 3%-9%, vanadic anhydride 0.1%-2%, silica 1 %-5%, rare earth 1%-5%, C fiber 3%-10%, surplus is forming agent.
2. conduction catalyst for denitrating flue gas according to claim 1, is characterized in that, rare earth is one or both in cerium or lanthanum.
3. conduction catalyst for denitrating flue gas according to claim 1, is characterized in that, forming agent is one or more in lactic acid, first class cellulose or polyethylene glycol.
4. a preparation method for conduction catalyst for denitrating flue gas claimed in claim 1, is characterized in that, preparation process is as follows:
After being mixed, titanium dioxide, tungstic acid, vanadic anhydride, silica, rare earth add C fiber and forming agent mixing; After the old 12-36 of material after mixing hour, carry out cooling processing, through filtering, extrude in advance, extrude, wet cutting, twice dry rear calcining obtains product.
5. the preparation method of conduction catalyst for denitrating flue gas according to claim 4, is characterized in that, the condition of primary drying be baking temperature be from room temperature to 70-80 DEG C, dry humidity is that 10-90%, drying time are 72-240 hour; Redrying condition be baking temperature be from room temperature to 90-100 DEG C, dry humidity is that 10-60%, drying time are 12-36 hour.
6. the preparation method of conduction catalyst for denitrating flue gas according to claim 4, is characterized in that, calcining heat is from room temperature to 650-750 DEG C.
7. the preparation method of conduction catalyst for denitrating flue gas according to claim 4, is characterized in that, calcination time is 24-72 hour.
8. the preparation method of conduction catalyst for denitrating flue gas according to claim 4, is characterized in that, before C fiber uses, uses soaking in alcohol to process 12-24h.
9. the preparation method of conduction catalyst for denitrating flue gas according to claim 4, is characterized in that, C fibre diameter is 5-10 μ m, and length is 3-10mm, and water content is 1-10%.
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| CN104841489A (en) * | 2015-05-29 | 2015-08-19 | 山东爱亿普环保科技有限公司 | Rare-earth-based composite multi-component denitration and dioxin-removing catalyst and preparation method thereof |
| CN104857948A (en) * | 2015-04-13 | 2015-08-26 | 宜兴市宜刚环保工程材料有限公司 | Medium-low-temperature flue gas condition denitration catalyst and preparation method thereof |
| CN106861713A (en) * | 2017-01-24 | 2017-06-20 | 东南大学 | A kind of integrated low temperature SCR denitration and preparation method thereof |
| CN108940299A (en) * | 2018-01-08 | 2018-12-07 | 南京东南工业装备股份有限公司 | A kind of diesel engine vent gas NOxPurify vanadium Ti-base catalyst and preparation method |
| CN113874107A (en) * | 2019-03-07 | 2021-12-31 | 中国电力株式会社 | Denitration catalyst and method for producing same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104857948A (en) * | 2015-04-13 | 2015-08-26 | 宜兴市宜刚环保工程材料有限公司 | Medium-low-temperature flue gas condition denitration catalyst and preparation method thereof |
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| CN106861713A (en) * | 2017-01-24 | 2017-06-20 | 东南大学 | A kind of integrated low temperature SCR denitration and preparation method thereof |
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| CN113874107A (en) * | 2019-03-07 | 2021-12-31 | 中国电力株式会社 | Denitration catalyst and method for producing same |
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