CN107008291B - Catalyst for denitrating flue gas and preparation method thereof - Google Patents
Catalyst for denitrating flue gas and preparation method thereof Download PDFInfo
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- CN107008291B CN107008291B CN201710266927.3A CN201710266927A CN107008291B CN 107008291 B CN107008291 B CN 107008291B CN 201710266927 A CN201710266927 A CN 201710266927A CN 107008291 B CN107008291 B CN 107008291B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of catalyst for denitrating flue gas and preparation method thereof.Catalyst for denitrating flue gas, including carrier and active material, the carrier is by LaMnO3And TiO2It constitutes；The active material is by V2O5It is constituted with Pd.LaMnO3With TiO2Mass ratio be 1:6~6；On the basis of carrier quality, V2O5Content be 0.5~10%, Pd content be 0.01~0.15%.The device have the advantages that.Method for preparing catalyst of the present invention is simple, and the denitrating catalyst prepared is suitable for the removing of high concentration nitrogen oxide, and the removing of nitrogen oxides at especially 200 DEG C of low temperature, denitration efficiency is high by 80% or more, is suitable for various pickling iron and steel line denitrating flue gas.
Description
Technical field
The invention belongs to catalyst to be synthetically prepared technical field, more particularly to pickling iron and steel catalyst for denitrating flue gas, with
And the preparation method of the catalyst.
Background technique
HF+HNO is widely used in stainless steel surface treatment process in ironworks3Nitration mixture pickling, therefore generate high concentration
NOx exhaust gas, due to NO2Content it is higher, show as chimney " Mao Huanglong " phenomenon, it is necessary to take at practicable method
Reason.Wherein NH3-SCR technology is more mature reliable.Pickling NOx exhaust gas has low temperature, micronic dust, is free of SO2And CO etc., concentration are high
Or the features such as fluctuation of concentration is big, oxidizability is high.
It is low to be suitable for pickling iron and steel flue gas for strict demand with country to the industries DS NOx Est such as thermoelectricity, smelting, steel
Temperature, the features such as nitrous oxides concentration is high denitrating catalyst it is extremely urgent.
Summary of the invention
The first object of the present invention is to provide a kind of catalyst for denitrating flue gas, and the second object of the present invention is to provide a kind of cigarette
The preparation method of qi exhaustion denox catalyst, to solve the problems, such as that existing catalyst denitration efficiency is low.
In order to realize that above-mentioned first purpose, the present invention provide a kind of catalyst for denitrating flue gas, including carrier and active material,
The carrier is by LaMnO3And TiO2It constitutes；The active material is by V2O5It is constituted with Pd.
Present invention catalyst for denitrating flue gas as described above, it is preferred that LaMnO3With TiO2Mass ratio be 1:6~6；With
On the basis of carrier quality, V2O5Content be 0.5~10%, Pd content be 0.01~0.15%.
Present invention catalyst for denitrating flue gas as described above, it is preferred that LaMnO3With TiO2Mass ratio be 1:5~5；With
On the basis of carrier quality, V2O5Content be 1.5~5%, Pd content be 0.01~0.1%.
Present invention catalyst for denitrating flue gas as described above, it is preferred that the V2O5Presoma be ammonium metavanadate, sulfuric acid
One of vanadyl, vanadyl acetylacetonate are a variety of.
Present invention catalyst for denitrating flue gas as described above, it is preferred that the presoma of the Pd be palladium chloride, palladium acetate,
One of four ammonia palladium of dichloro is a variety of.
The preparation method of above-mentioned catalyst for denitrating flue gas, comprising the following steps:
Step 1, LaMnO is prepared using combustion method3；Preferably, step 1 the specific steps are, weigh raw material lanthanum nitrate and
Manganese nitrate dissolves in deionized water；The alanine of 1.5 times of above-mentioned nitrate of molar ratio is dissolved in water, nitric acid is added to
In salting liquid, it is thermally formed thick solution while stirring；Then dry at 300~400 DEG C of temperature, it is to be dried after
500~700 DEG C of 3~5h of calcining in calcining furnace；Obtain carrier LaMnO3.It is furthermore preferred that the temperature heated while stirring is 60 DEG C
~80 DEG C；By carrier LaMnO3Ground 600 mesh screen is spare.
Step 2, the presoma of active material is dissolved, then with LaMnO3、TiO2It is prepared by mixing into uniformly with extrusion aid
Pug；
Step 3, pug is extruded into catalyst mud embryo using extruder；Preferably, 30 holes~60 holes.
Step 4, catalyst mud embryo is placed in hothouse dry 10d~12d, be put into after the completion of dry in tunnel kiln into
Row is fired into finished product.Preferably, 550 DEG C~650 DEG C of tunnel oven in-furnace temperature when step 4 is burnt into, firing time 12h~
72h。
The beneficial effects of the present invention are:
Preparation method of the present invention is simple, and the denitrating catalyst prepared is suitable for the removing of high concentration nitrogen oxide, especially
The removing of nitrogen oxides at 200 DEG C of low temperature, denitration efficiency is high by 80% or more, is suitable for various pickling iron and steel line denitrating flue gas.
Specific embodiment
The embodiment recorded herein is specific specific embodiment of the invention, for illustrating design of the invention,
Be it is explanatory and illustrative, should not be construed as the limitation to embodiment of the present invention and the scope of the invention.Except what is recorded herein
Outside embodiment, those skilled in the art can also based on the claim of this application book and specification disclosure of that using aobvious and
The other technical solutions being clear to, these technical solutions include using any obvious to making for the embodiment recorded herein
The technical solution of substitutions and modifications.
Extrusion aid used in following embodiment of the present invention are as follows: the excellent Dao Aoba chemical industry in the Shanghai polyethylene glycol oxide (PEO) has
Limit company, model POLYOX-TM-WSR-308.Alternatively, carboxymethyl cellulose, Shandong Yu Heng cellulose Co., Ltd, model
FH6A。
Embodiment 1
LaMnO3Preparation: weigh lanthanum nitrate and manganese nitrate according to the stoichiometry of 1:1, dissolution is in deionized water.It will
The alanine of 1.5 times of nitrate of molar ratio is dissolved in water, and is added in nitrate solution, while stirring 60 DEG C of heating, shape
At thick solution.Then it puts and dries in the drying chamber, 300 DEG C of temperature, after drying, 500 DEG C of calcining 5h in calcining furnace,
It crosses 600 mesh screens and obtains carrier LaMnO3Powder.
Then by ammonium metavanadate and palladium acetate, (active material is respectively with V in final catalyst2O5It is deposited with the mode of PdO
Changed in last sintering process.) solution is according to V2O5The load capacity that content is 1.5%, Pd0.1% is with mass ratio
The LaMnO of 1:53And TiO2Support powder mixing is added extrusion aid and is mixed into uniform pug, uses extrusion after ageing one day
Pug is extruded into catalyst mud embryo by machine, and catalyst hole count specification is 30 holes.Mud embryo is placed in 45 DEG C of hothouses dry 12d,
It is put into tunnel kiln and is burnt into after the completion of dry, 550 DEG C of in-furnace temperature, firing time for 24 hours, obtains finished product.
Embodiment 2
LaMnO3Preparation: weigh lanthanum nitrate and manganese nitrate according to the stoichiometry of 2:1, dissolution is in deionized water.It will
The alanine of 1.5 times of nitrate of molar ratio is dissolved in water, and is added in nitrate solution, while stirring 60 DEG C of heating, shape
At thick solution.Then it puts and dries in the drying chamber, 300 DEG C of temperature, after drying, 500 DEG C of calcining 5h in calcining furnace,
It crosses 600 mesh screens and obtains carrier LaMnO3Powder.
Then by ammonium metavanadate and palladium acetate solution according to V2O5Content is the load capacity and quality of 3%, Pd content 0.01%
Than the LaMnO for 1:53And TiO2Support powder mixing is added extrusion aid and is mixed into uniform pug, and ageing uses after one day
Pug is extruded into catalyst mud embryo by extruder, and catalyst hole count specification is 60 holes.Mud embryo is placed in 45 DEG C of hothouses dry
10d is put into tunnel kiln after the completion of dry and is burnt into, and 600 DEG C of in-furnace temperature, firing time for 24 hours, obtains finished product.
Embodiment 3
LaMnO3Preparation: weigh lanthanum nitrate and manganese nitrate according to the stoichiometry of 1:2, dissolution is in deionized water.It will
The alanine of 1.5 times of nitrate of molar ratio is dissolved in water, and is added in nitrate solution, while stirring 80 DEG C of heating, shape
At thick solution.Then it puts and dries in the drying chamber, 300 DEG C of temperature, after drying, 500 DEG C of calcining 5h in calcining furnace,
It crosses 600 mesh screens and obtains carrier LaMnO3Powder.
Then by ammonium metavanadate and palladium acetate solution according to V2O5The load capacity that content is 2%, Pd0.05% is with mass ratio
The LaMnO of 1:53And TiO2Support powder mixing is added extrusion aid and is mixed into uniform pug, uses extrusion after ageing one day
Pug is extruded into catalyst mud embryo by machine, and catalyst hole count specification is 50 holes.Mud embryo is placed in 45 DEG C of hothouses dry 10d,
It is put into tunnel kiln and is burnt into after the completion of dry, 650 DEG C of in-furnace temperature, firing time for 24 hours, obtains finished product.
Embodiment 4
LaMnO3Preparation: weigh lanthanum nitrate and manganese nitrate according to the stoichiometry of 1:1, dissolution is in deionized water.It will
The alanine of 1.5 times of nitrate of molar ratio is dissolved in water, and is added in nitrate solution, while stirring 70 DEG C of heating, shape
At thick solution.Then it puts and dries in the drying chamber, 300 DEG C of temperature, after drying, 500 DEG C of calcining 5h in calcining furnace,
It crosses 600 mesh screens and obtains carrier LaMnO3Powder.
Then by ammonium metavanadate and palladium acetate solution according to V2O5The load capacity and mass ratio that content is 2.5%, Pd0.03%
For the LaMnO of 1:53And TiO2Support powder mixing is added extrusion aid and is mixed into uniform pug, using crowded after ageing one day
Pug is extruded into catalyst mud embryo by machine out, and catalyst hole count specification is 40 holes.Mud embryo is placed in 45 DEG C of hothouses dry
12d is put into tunnel kiln after the completion of dry and is burnt into, and 600 DEG C of in-furnace temperature, firing time for 24 hours, obtains finished product.
Each 3ml of the denitrating catalyst of Example 1~4 is placed in fixed bed reactors, test condition are as follows: NO 500ppm,
NH3500ppm, O22%, N2For Balance Air, total gas flow rate 500ml/min, air speed 20000h–1, 120,140,160,180,
Measurement inlet and outlet NO at a temperature of 200 DEG CXConcentration, using Portable smoke analysis instrument (Shanghai Yue Ke Science and Technology Ltd.,
The enhanced flue gas analyzer of VARIO PLUS) it is detected.If the following table 1 is denitration efficiency test result.
1 conversion rate of NOx of table
Each technical characteristic of above-mentioned disclosure is not limited to disclosed and other feature combination, and those skilled in the art are also
Can carry out other combinations between each technical characteristic according to the purpose of invention, be subject to realize the present invention purpose.
Claims (9)
1. a kind of catalyst for denitrating flue gas, including carrier and active material, it is characterised in that: the carrier is by LaMnO3And TiO2
It constitutes；The active material is by V2O5It is constituted with Pd.
2. catalyst for denitrating flue gas according to claim 1, which is characterized in that LaMnO3With TiO2Mass ratio be 1:6；
On the basis of carrier quality, V2O5Content be 0.5~10%, Pd content be 0.01~0.15%.
3. catalyst for denitrating flue gas according to claim 1, which is characterized in that LaMnO3With TiO2Mass ratio be 1:5；
On the basis of carrier quality, V2O5Content be 1.5~5%, Pd content be 0.01~0.1%.
4. catalyst for denitrating flue gas according to claim 1-3, which is characterized in that the V2O5Presoma be
One of ammonium metavanadate, vanadic sulfate, vanadyl acetylacetonate are a variety of.
5. catalyst for denitrating flue gas according to claim 4, which is characterized in that the presoma of the Pd is palladium chloride, vinegar
One of sour palladium, four ammonia palladium of dichloro are a variety of.
6. the preparation method of catalyst for denitrating flue gas described in claim 1, comprising the following steps:
Step 1, LaMnO is prepared using combustion method3；
Step 2, the presoma of active material is dissolved, then with LaMnO3、TiO2Uniform mud is prepared by mixing into extrusion aid
Material；
Step 3, pug is extruded into catalyst mud embryo using extruder；
Step 4, catalyst mud embryo is placed in hothouse dry 10d~12d, is put into tunnel kiln and is burnt after the completion of dry
At obtaining finished product.
7. the preparation method of catalyst for denitrating flue gas according to claim 6, which is characterized in that the specific steps of step 1
To weigh raw material lanthanum nitrate and manganese nitrate dissolution in deionized water；The alanine of 1.5 times of above-mentioned nitrate of molar ratio is molten
Solution in water, is added in nitrate solution, is thermally formed thick solution while stirring；Then at 300~400 DEG C of temperature
It is dry, it is to be dried after in calcining furnace 500~700 DEG C of 3~5h of calcining；Obtain carrier LaMnO3。
8. the preparation method of catalyst for denitrating flue gas according to claim 7, which is characterized in that the temperature heated while stirring
Degree is 60 DEG C~80 DEG C；By carrier LaMnO3Ground 600 mesh screen is spare.
9. the preparation method of catalyst for denitrating flue gas according to claim 6, which is characterized in that when step 4 is burnt into
550 DEG C~650 DEG C of tunnel oven in-furnace temperature, firing time 12h~72h.
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| CN108187658A (en) * | 2018-01-10 | 2018-06-22 | 北京国电龙源环保工程有限公司 | 50 hole SCR denitration modules and preparation method thereof |
| CN108504413A (en) * | 2018-04-03 | 2018-09-07 | 马鞍山科宇环境工程有限公司 | A kind of efficient fuel coal desulphurization denitration additive and preparation method thereof |
| CN110787793A (en) * | 2019-09-28 | 2020-02-14 | 亿利洁能科技（乐陵）有限公司 | Boiler flue gas denitration catalyst and preparation method thereof |
| CN113198495A (en) * | 2021-05-25 | 2021-08-03 | 四川大学 | Fluorine modified lanthanum-manganese composite oxide SCR denitration catalyst and preparation method thereof |
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| CN102019188A (en) * | 2010-12-20 | 2011-04-20 | 浙江天蓝环保技术有限公司 | Magnetic catalyst for denitration of NH3-SCR smoke and application thereof |
| CN105214670A (en) * | 2015-10-14 | 2016-01-06 | 东南大学 | The preparation being low temperature support type denitrating catalyst in carrier with former iron ore and method of testing |
| CN105327706A (en) * | 2015-09-23 | 2016-02-17 | 上海交通大学 | Catalyst for low temperature catalytic removal of environment pollutants, and preparation method thereof |
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| JPS6025542A (en) * | 1983-07-21 | 1985-02-08 | Matsushita Electric Ind Co Ltd | Nox reducing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019188A (en) * | 2010-12-20 | 2011-04-20 | 浙江天蓝环保技术有限公司 | Magnetic catalyst for denitration of NH3-SCR smoke and application thereof |
| CN105327706A (en) * | 2015-09-23 | 2016-02-17 | 上海交通大学 | Catalyst for low temperature catalytic removal of environment pollutants, and preparation method thereof |
| CN105214670A (en) * | 2015-10-14 | 2016-01-06 | 东南大学 | The preparation being low temperature support type denitrating catalyst in carrier with former iron ore and method of testing |
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