CN108212203A - A kind of copper-based molecular sieve denitrating catalyst of automobile-used extruded type and preparation method thereof - Google Patents
A kind of copper-based molecular sieve denitrating catalyst of automobile-used extruded type and preparation method thereof Download PDFInfo
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
- B01D2255/504—ZSM 5 zeolites
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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
- B01D2258/01—Engine exhaust gases
Abstract
The invention discloses a kind of automobile-used copper-based molecular sieve denitrating catalysts of extruded type, are synthesized by following ingredient：Molecular sieve, talcum, water-washed kaoline, calcined kaolin, hydroxypropyl methyl cellulose, polyethylene glycol, lactic acid, stearic acid, glass fibre, Tong Yuan；It is calculated based on the amount of copper oxide：The talcum, water-washed kaoline, calcined kaolin, hydroxypropyl methyl cellulose, polyethylene glycol, lactic acid, stearic acid, glass fibre, copper source addition be respectively 7% the 15% of molecular sieve, 2% 6%, 6% 13%, 1% 5%, 4% 6%, 2% 5%, 2% 5%, 1% 5%, 3% 6%.Catalyst prod made from technical scheme of the present invention has apparent advantage.The problems such as relative to the coated copper based molecular sieve catalyst pulp technique on cordierite carrier, extruded type molecular sieve catalyst preparation process is simple, and catalytic activity is good, avoids easy plug-hole, and expulsion rate is big is conducive to save raw material, reduces production cost.
Description
Technical field
The present invention relates to a kind of catalyst, particularly for the copper-based molecular sieve denitration catalyst of the extruded type of vehicle maintenance service
Agent and preparation method thereof.
Background technology
Coal, oil are the main energy sources in China, and when burning can generate a large amount of sulfur dioxide (SO2), nitrogen oxides (NOx)
With the harmful components such as dust.Wherein nitrogen oxides (NOx) as one of main pollutant, discharge is not only good for the body of people
Health is harmful to, and the serious environmental problems such as Chou oxygen layer Kong Dong ﹑ Suan Yu ﹑ greenhouse effects and photochemical fog is also resulted in, so effectively
Control NOxDischarge be China's important atmosphere polluting problem urgently to be resolved hurrily in the recent period.
In recent years, selective catalytic reduction (Selective Catalytic Reduction, SCR) is removing NOxIt is harmful
The most effectual way of gas.Removing NO is tied up to the caltalyst of molecular sieve carried metalxIt has been embodied very in terms of pernicious gas
Good application prospect.The preparation method of current automobile-used molecular sieve catalyst is generally：Metal/molecular sieve is prepared into catalyst slurry
Material be coated in drying on ceramic honey comb (generally cordierite) carrier, firing and etc. be made.But prepared by this method
Coating type molecular sieve catalyst there are activity component load quantity is low, easy plug-hole, preparation process condition are harsh, on cordierite surface
The problems such as covering of molecular sieve is uneven, molecular sieve and carrier-bound firmness are not easy to fall off enough.
The copper-based molecular sieve catalyst of extruded type is that molecular sieve, Tong Yuan, auxiliary agent are passed through kneading, pugging, aging, molding, dry
The series of processes such as dry, firing prepare the active Faveolate denitration catalyst of certain mesh number, this extruded type catalyst
Catalytic active component can be made to be evenly distributed on carrier, improve the combined with firmness of carrier and catalyst, save production
Process eliminates coating step, so as to improve the production efficiency of catalyst.Simultaneously because the introducing of copper, extruded type cupper-based catalyst
Agent has good low-temperature catalytic activity.
Invention content
The present invention for removal of nitrogen oxide problem, provide a kind of copper-based molecular sieve denitrating catalyst of automobile-used extruded type and
Preparation method, technology preparation catalyst process is simple, and catalytic activity is high.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of copper-based molecular sieve denitrating catalyst of automobile-used extruded type, is synthesized by following ingredient：Molecular sieve, talcum, washing are high
Ridge soil, calcined kaolin, hydroxypropyl methyl cellulose, polyethylene glycol, lactic acid, stearic acid, glass fibre, Tong Yuan；
It is calculated based on the amount of copper oxide：The talcum, water-washed kaoline, calcined kaolin, hydroxypropyl methyl are fine
Tie up element, polyethylene glycol, lactic acid, stearic acid, glass fibre, copper source addition be respectively the 7%-15% of molecular sieve,
2%-6%, 6%-13%, 1%-5%, 4%-6%, 2%-5%, 2%-5%, 1%-5%, 3%-6%.
The polyethylene glycol is PEG-400 polyethylene glycol；
A kind of copper-based molecular sieve denitrating catalyst of automobile-used extruded type, preparation method include the following steps：
(1) molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine and be uniformly mixed；
(2) hydroxypropyl methyl cellulose, stearic acid, glass fibre is added in into step (1) to be uniformly mixed；
(3) polyethylene glycol, lactic acid, Tong Yuan, deionized water is added in into step (2) to be mediated；
(4) by the kneaded aging 24-48h of pug of step (3)；
(5) it by good pug pugging 2-3 times in vacuum deairing machine aging in step (4), is put into molding machine and is extruded into
Type；
(6) by the catalyst microwave drying of forming in step (5), microwave frequency 2400-2500MHZ；
(7) by catalyst dried in step (6), Muffle kiln roasting is put into, sintering curve is：Initial temperature
100 DEG C, hereinafter, with the heating rate of 0.5-2 DEG C of heating per minute, are warming up to 200-300 DEG C of calcining dumping, are continuously heating to
550-700 DEG C of 120-240min of burning, both obtains finished catalyst.
The molecular sieve is the mixture of the silica that molar ratio range is 5-150 and aluminium oxide, MFI structure type
Any one of molecular sieve, ZSM-5, ZBH, LZ-105, ZMQ-TB；
The 8 ring small pore molecular sieves with CHA crystal types for example aluminosilicate zeolites, SSZ-13, SSZ-62, SAPO-34,
Any one of SAPO-47, ZSM-5；
And any one of Y type molecular sieve, beta-molecular sieve, H beta-molecular sieves.
The draw ratio of glass fibre is 3-6 in the step (2).
Copper source is Cu (NO in the step (3)3)2·3H2The mixture of O and copper acetate；Cu (the NO3)2·3H2O
With the mixture of copper acetate, addition accounts for the percentage calculating of powder gross mass by copper oxide is converted to.
It is respectively 3%-6% that copper oxide, which accounts for powder weight, after described step (7) the Muffle kiln roasting.
The present invention has advantageous effect, has through the copper-based molecular sieve catalyst product of extruded type made from above step apparent
Advantage.Relative to the coated copper based molecular sieve catalyst pulp technique on cordierite carrier, extruded type catalyst preparation process
Simply, easy plug-hole is avoided, the problems such as expulsion rate is big is conducive to save raw material, reduces production cost.Simultaneously because copper draws
Enter, the copper-based molecular sieve catalyst of the extruded type prepared has good low-temperature catalytic activity.
Specific embodiment
In order to better understand the present invention, present disclosure is further illustrated with reference to example, but the present invention's is interior
Appearance is not limited solely to the following examples.
Embodiment 1
(1) each component of following parts by weight is weighed according to following ratio：100 parts of SSZ-13,7 parts of talcum, washing kaolinite
2 parts of soil, 6 parts of calcined kaolin, 1 part of hydroxypropyl methyl cellulose, 2 parts of stearic acid, 1 part of glass fibre, 4 parts of polyethylene glycol, breast
2 parts of acid, 3 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine and mixed
It closes uniformly, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 2
(1) each component of following parts by weight is weighed according to following ratio：100 parts of SSZ-13,15 parts of talcum, washing are high
Ridge soil 6 parts, 13 parts of calcined kaolin, 5 parts of hydroxypropyl methyl cellulose, 5 parts of stearic acid, 5 parts of glass fibre, 5 parts of polyethylene glycol,
3 parts of lactic acid, 4 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine
It is uniformly mixed, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 3
(1) each component of following parts by weight is weighed according to following ratio：100 parts of SSZ-13,10 parts of talcum, washing are high
Ridge soil 5 parts, 10 parts of calcined kaolin, 3 parts of hydroxypropyl methyl cellulose, 4 parts of stearic acid, 3 parts of glass fibre, 6 parts of polyethylene glycol,
5 parts of lactic acid, 6 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine
It is uniformly mixed, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 4
(1) each component of following parts by weight is weighed according to following ratio：50 parts of SSZ-62,50 parts of ZSM-5, talcum 7
Part, 2 parts of water-washed kaoline, 6 parts of calcined kaolin, 1 part of hydroxypropyl methyl cellulose, 2 parts of stearic acid, 1 part of glass fibre, poly- second
4 parts of glycol, 2 parts of lactic acid, 3 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in
It is uniformly mixed in kneading machine, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding poly-
Ethylene glycol, lactic acid, Tong Yuan, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum
Pugging 2-3 times in pug mill, is put into extrusion molding in molding machine, the catalyst microwave drying of forming, it is dried after by its
Muffle kiln roasting (550-700 DEG C of firing temperature) is put into, is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 5
(1) each component of following parts by weight is weighed according to following ratio：50 parts of SAPO-34,50 parts of ZSM-5, talcum
15 parts, 6 parts of water-washed kaoline, 13 parts of calcined kaolin, 5 parts of hydroxypropyl methyl cellulose, 5 parts of stearic acid, 5 parts of glass fibre,
5 parts of polyethylene glycol, 3 parts of lactic acid, 4 parts of copper source, appropriate amount of deionized water.By molecular sieve, talcum, water-washed kaoline, calcined kaolin
It adds in kneading machine and is uniformly mixed, then add in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, finally add
Enter polyethylene glycol, lactic acid, Tong Yuan, deionized water to be mediated, the aging 24-48h of kneaded pug exists aging good pug
Pugging 2-3 times in vacuum deairing machine is put into extrusion molding in molding machine, the catalyst microwave drying of forming, after dried
Muffle kiln roasting (550-700 DEG C of firing temperature) is put it into, is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 6
(1) each component of following parts by weight is weighed according to following ratio：100 parts of ZSM-5,10 parts of talcum, washing kaolinite
5 parts of soil, 10 parts of calcined kaolin, 3 parts of hydroxypropyl methyl cellulose, 4 parts of stearic acid, 3 parts of glass fibre, 6 parts of polyethylene glycol, breast
5 parts of acid, 6 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine and mixed
It closes uniformly, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 7
(1) each component of following parts by weight is weighed according to following ratio：100 parts of SAPO-34,7 parts of talcum, washing are high
Ridge soil 2 parts, 6 parts of calcined kaolin, 1 part of hydroxypropyl methyl cellulose, 2 parts of stearic acid, 1 part of glass fibre, 4 parts of polyethylene glycol,
2 parts of lactic acid, 3 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine
It is uniformly mixed, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 8
(1) each component of following parts by weight is weighed according to following ratio：100 parts of SAPO-34,15 parts of talcum, washing are high
Ridge soil 6 parts, 13 parts of calcined kaolin, 5 parts of hydroxypropyl methyl cellulose, 5 parts of stearic acid, 5 parts of glass fibre, 5 parts of polyethylene glycol,
3 parts of lactic acid, 4 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine
It is uniformly mixed, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Embodiment 9
(1) each component of following parts by weight is weighed according to following ratio：100 parts of SAPO-34,10 parts of talcum, washing are high
Ridge soil 5 parts, 10 parts of calcined kaolin, 3 parts of hydroxypropyl methyl cellulose, 4 parts of stearic acid, 3 parts of glass fibre, 6 parts of polyethylene glycol,
5 parts of lactic acid, 6 parts of copper source, appropriate amount of deionized water.Molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine
It is uniformly mixed, then adds in hydroxypropyl methyl cellulose, stearic acid, glass fibre and be uniformly mixed, be eventually adding polyethylene glycol, breast
Acid, copper source, deionized water are mediated, the aging 24-48h of kneaded pug, by aging good pug in vacuum deairing machine
Pugging 2-3 times, is put into extrusion molding in molding machine, and the catalyst microwave drying of forming puts it into Muffle after dried
Kiln roasting (550-700 DEG C of firing temperature), is prepared into copper-based molecular sieve catalyst.
(2) the copper-based molecular sieve catalyst prepared is cut into height 20mm, the cylinder shape catalyst of diameter 20mm is put into
In sample evaluating apparatus, in simulated experiment gas component N2、CO2、NH3、NO、O2Lower progress sample evaluation, air speed is kept in experiment
For 50000h-1, ammonia nitrogen ratio is 1:1, the NO concentration of inlet and outlet is detected respectively, calculates the denitration efficiency of catalyst.
Each example sample evaluation effect see the table below：
| Detection project | Mesh number | Cu based molecular sieves (NOXConversion ratio >=80%) |
| Embodiment 1 | 300 | 205.1-457.3℃ |
| Embodiment 2 | 300 | 218.5-456.5℃ |
| Embodiment 3 | 300 | 197.5-471.9℃ |
| Embodiment 4 | 300 | 221.2-430.9℃ |
| Embodiment 5 | 300 | 230.4-450.9℃ |
| Embodiment 6 | 300 | 207.3-450.7℃ |
| Embodiment 7 | 300 | 210.1-458.3℃ |
| Embodiment 8 | 300 | 223.5-455.6℃ |
| Embodiment 9 | 300 | 192.5-462.6℃ |
By testing and verification, have through the copper-based molecular sieve catalyst product of extruded type made from above step apparent excellent
Gesture.Relative to the coated copper based molecular sieve catalyst pulp technique on cordierite carrier, extruded type catalyst preparation process is simple,
Easy plug-hole is avoided, the problems such as expulsion rate is big is conducive to save raw material, reduces production cost.Simultaneously because the introducing of copper, prepares
The copper-based molecular sieve catalyst of extruded type gone out has good low-temperature catalytic activity.
The foregoing is merely the preferred embodiments of the present invention, are not intended to limit the invention, all spirit in the present invention
With all any modification, equivalent and improvement made within principle etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of copper-based molecular sieve denitrating catalyst of automobile-used extruded type, which is characterized in that synthesized by following ingredient：Molecular sieve, cunning
Stone, water-washed kaoline, calcined kaolin, hydroxypropyl methyl cellulose, polyethylene glycol, lactic acid, stearic acid, glass fibre, Tong Yuan；
It is calculated based on the amount of copper oxide：The talcum, water-washed kaoline, calcined kaolin, hydroxypropyl methyl cellulose,
Polyethylene glycol, lactic acid, stearic acid, glass fibre, copper source addition be respectively 7%-15%, the 2%-6% of molecular sieve,
6%-13%, 1%-5%, 4%-6%, 2%-5%, 2%-5%, 1%-5%, 3%-6%；
The polyethylene glycol is PEG-400 polyethylene glycol.
2. a kind of automobile-used copper-based molecular sieve denitrating catalyst of extruded type as described in claim 1, it is characterised in that：Its preparation side
Method includes the following steps：
(1) molecular sieve, talcum, water-washed kaoline, calcined kaolin are added in kneading machine and be uniformly mixed；
(2) hydroxypropyl methyl cellulose, stearic acid, glass fibre is added in into step (1) to be uniformly mixed；
(3) polyethylene glycol, lactic acid, Tong Yuan, deionized water is added in into step (2) to be mediated；
(4) by the kneaded aging 24-48h of pug of step (3)；
(5) by good pug pugging 2-3 times in vacuum deairing machine aging in step (4), it is put into extrusion molding in molding machine；
(6) by the catalyst microwave drying of forming in step (5), microwave frequency 2400-2500MHZ；
(7) by catalyst dried in step (6), Muffle kiln roasting is put into, sintering curve is：100 DEG C of initial temperature
Hereinafter, with the heating rate of 0.5-2 DEG C of heating per minute, 200-300 DEG C of calcining dumping is warming up to, is continuously heating to 550-700
DEG C burn 120-240min, both finished catalyst.
3. a kind of automobile-used copper-based molecular sieve denitrating catalyst of extruded type as described in claim 1, it is characterised in that：The molecule
Sieve for molar ratio range be 5-150 silica and the mixture of aluminium oxide, the molecular sieve of MFI structure type；
The molecular sieve of MFI structure type；The molecular sieve of the MFI structure type is in ZSM-5, ZBH, LZ-105, ZMQ-TB
It is any；
8 ring small pore molecular sieves such as aluminosilicate zeolites, SSZ-13, SSZ-62, SAPO-34, SAPO- with CHA crystal types
47th, any one of ZSM-5；
And any one of Y type molecular sieve, beta-molecular sieve, H beta-molecular sieves.
4. a kind of automobile-used copper-based molecular sieve denitrating catalyst of extruded type as claimed in claim 2, it is characterised in that：Step (2)
The draw ratio of middle glass fibre is 3-6.
5. a kind of automobile-used copper-based molecular sieve denitrating catalyst of extruded type as claimed in claim 2, it is characterised in that：Step (3)
Middle copper source is Cu (NO3)2·3H2The mixture of O and copper acetate.
6. a kind of automobile-used copper-based molecular sieve denitrating catalyst of extruded type as claimed in claim 5, it is characterised in that：The Cu
(NO3)2·3H2The mixture of O and copper acetate, addition account for the percentage calculating of powder gross mass by copper oxide is converted to.
7. a kind of automobile-used copper-based molecular sieve denitrating catalyst of extruded type as claimed in claim 2, it is characterised in that：Step (7)
It is respectively 3%-6% that copper oxide, which accounts for powder weight, after Muffle kiln roasting.
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| CN112919493A (en) * | 2021-02-05 | 2021-06-08 | 正大能源材料(大连)有限公司 | Method for preparing SSZ-13 molecular sieve at low cost and application thereof |
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