CN115445613A - Coating for lean-burn CNG catalyst and preparation method thereof - Google Patents

Coating for lean-burn CNG catalyst and preparation method thereof Download PDF

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Publication number
CN115445613A
CN115445613A CN202210963049.1A CN202210963049A CN115445613A CN 115445613 A CN115445613 A CN 115445613A CN 202210963049 A CN202210963049 A CN 202210963049A CN 115445613 A CN115445613 A CN 115445613A
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percent
coating
catalyst
lean
barrel
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陈雪红
袁书华
朱增赞
栾浩
徐欢
潘文
赵磊
丁宇恒
王菊
季天翔
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Kailong Lanfeng New Material Technology Co ltd
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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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • 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
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating

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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention provides a coating for a lean burn CNG catalyst and a preparation method thereof, wherein the coating comprises the following components in percentage by weight: la-Zr-Al 2 O 3 90 to 95 percent; 0.5 to 1 percent of base metal; pd0.8-1.5%; ba (OH) 2 1 to 2.3 percent; 2 to 3.5 percent of binder; 0.03 to 0.1 percent of cellulose; selecting La-Zr-Al 2 O 3 As the main component of the catalyst coating, la-Zr-Al 2 O 3 The material has larger specific surface area, and the change rate of the specific surface area is less than 12 percent in the aging process from a fresh state to high temperature, becauseThis gives the final coated catalyst a higher mechanical strength and good resistance to sintering. By optimizing the proportion of each component of the catalyst, the La-Zr-Al is exerted 2 O 3 And the base metal and the Pd further improve the mechanical strength and the specific surface area of the catalyst carrier, improve the efficiency of the catalyst and be more beneficial to the purification of lean-burn CNG tail gas.

Description

Coating for lean burn CNG catalyst and preparation method thereof
Technical Field
The invention relates to a coating for a lean-burn CNG catalyst and a preparation method thereof, and more particularly relates to optimization of the coating.
Background
Natural gas vehicles are mainly classified into Compressed Natural Gas (CNG) vehicles and Liquefied Natural Gas (LNG) vehicles. The CNG automobile fuel is prepared by compressing natural gas, storing in a vehicle-mounted high-pressure bottle, decompressing by a decompressor and supplying to an internal combustion engine, and the storage process is simple.
The natural gas is mixed with air in the engine, compared with diesel oil and gasoline, the natural gas is mixed more uniformly and combusted more fully, and compared with an automobile and a fuel oil automobile, the emission of various pollutants in CNG automobile tail gas is greatly reduced, but unburned CH in the tail gas 4 The content is still large. The main pollutant in the tail gas of CNG automobile under the condition of theoretical air-fuel ratio is CH 4 、NO X And CO. The purification requirement of the theoretical air-fuel ratio CNG automobile exhaust is higher, the requirement on the catalyst is higher than that of the gasoline automobile exhaust purification catalyst, and the purification of each component in the exhaust can be effectively completed only by a high-performance three-way catalyst.
In recent years, due to the increase of the holding amount of lean-burn CNG automobiles, unburned CH in exhaust gas 4 Will cause great pressure on the environment, CH 4 Catalytic oxidation catalysts can be broadly classified into noble metal catalysts and non-noble metal catalysts. Compared with non-noble metal catalysts, noble metal catalysts have better low-temperature activity and high-temperature stability, so that the noble metal catalysts are widely applied to methane catalytic oxidation, wherein the Pd supported catalyst has the highest methane catalytic activity. However, the lean-burn CNG automobile exhaust contains a large amount of water vapor and a small amount of SO 2 The Pd catalyst is easy to cause water poisoning and sulfur poisoning, the service life of the catalyst is greatly shortened, and the catalyst has poor water-proof thermal stability and high noble metal content.
Disclosure of Invention
In order to solve the problems of poor water-resistant thermal stability, poor sulfur resistance and high content of noble metal of the existing catalyst, the preparation method of the modified alumina carrier supported noble metal catalyst for lean burn CNG is provided.
The specific scheme is as follows:
a coating for a lean-burn CNG catalyst comprises the following components in percentage by weight:
La-Zr-Al 2 O 3 90 to 95 percent; 0.5 to 1 percent of base metal; pd 0.8-1.5%; ba (OH) 2 1 to 2.3 percent; 2 to 3.5 percent of binder; 0.03 to 0.1 percent of cellulose;
the La 2 -Zr-Al 2 O 3 Comprising 6 to 9wt% of La in the material 2 O 3 、20～30wt％ZrO 2 And 60 to 80wt% of Al 2 O 3 ；
La-Zr-Al 2 O 3 The change rate of the specific surface area from the fresh attitude to the aging is less than 12 percent; the change rate of pore volume is less than 3 percent, and La-Zr-Al is added 2 O 3 As a main raw material of the catalyst coating layer, al 2 O 3 Has larger specific surface area, and the change rate of the specific surface area is less than 12 percent in the aging process from a fresh state to a high temperature, so that the catalyst finally coated with the coating obtains excellent mechanical property and good sintering resistance.
Preferably, the cellulose is one or a mixture of hydroxyethyl cellulose and sodium carboxymethyl cellulose.
Preferably, the base metal is one or a mixture of more of Y, ce or Zr.
Preferably, said Ba (OH) 2 The content of the oxide is 40-50%; the content of the oxide of the binder is 5 to 15 percent.
A coating preparation method for a lean burn CNG catalyst comprises the following steps:
s1, weighing La 2 O 3 -ZrO 2 -Al 2 O 3 Putting into a barrel for stirring, adding base metal oxide and continuing stirring;
s2, diluting the Pd salt solution, weighing and adding the diluted Pd salt solution into a barrel to be continuously stirred for 2-5 h, and testing the pH value;
s3, weighing Ba (OH) 2 Adding into a barrel and adjusting pH;
and S4, adding a binder and cellulose, and stirring until the viscosity required by coating is reached.
Preferably, the pH in S3 is adjusted to 5 to 6.
Has the advantages that:
(1) The invention provides a coating of a catalyst for lean burn CNG and a preparation method thereof, wherein La-Zr-Al is selected 2 O 3 As the main component of the catalyst coating, adjusting and optimizing La 2 O 3 、ZrO 2 、Al 2 O 3 The weight percentage of each material is 6-9 wt% 2 O 3 、20～30wt％ZrO 2 And 60 to 80wt% of Al 2 O 3 ，La 2 -Zr-Al 2 O 3 The material has larger specific surface area, and the change rate of the specific surface area is less than 12 percent in the aging process from a fresh state to a high temperature, so that the catalyst finally coated with the coating has higher mechanical strength and good anti-sintering performance.
(2) By optimizing the proportion of each component of the catalyst, the La-Zr-Al is exerted 2 O 3 The synergistic effect of the base metal and the Pd solution further improves the mechanical strength and the specific surface area of the catalyst carrier, improves the efficiency of the catalyst,is more beneficial to the purification of the lean-burn CNG tail gas.
Drawings
FIG. 1 is a graph of hydrothermal aging first pass test performance for the catalyst prepared in example 1.
Figure 2 is a graph of hydrothermal aging second pass test performance for the catalyst prepared in example 1.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
Example 1:
a preparation method of a coating for a lean-burn CNG catalyst comprises the following steps:
(1) Preparation of the coating
The materials are prepared according to the following mass percentages:
La-Zr-Al 2 O 3 93.51％；CeO 2 0.6％；Pd 1.2％；Ba(OH) 2 1.8 percent; 2.8 percent of binder; HHBR2500.09%;
water is put into a material barrel according to the La-Zr-Al 2 O 3 Weighing the materials according to the mass percentage, putting the materials into a barrel, and adding CeO 2 Stirring, diluting the Pd salt solution with deionized water, weighing Pd solution after dilution, adding dropwise into a bucket and stirring for 4h, testing the pH of the solution at this time, and weighing Ba (OH) 2 Adding the mixture into a barrel, stirring for 5 hours, and adjusting the pH value of the solution to 5-6; the binder was weighed. Adding into a barrel, and stirring for 20min; weighing HHBR250, adding the HHBR250 into a barrel, stirring to the required coating viscosity, and judging whether the viscosity is proper according to the standard that the final slurry drops on the carrier do not flow quickly to the required coating viscosity.
(2) The slurry was coated on a catalyst and tested for catalyst performance
The hydrothermal aging first test was performed at 850 ℃ for 50h, and the test results are shown in FIG. 1:
the hydrothermal aging test was performed for a second time at 850 ℃ for 50h, and the test results are shown in fig. 2.
Example 2:
a coating preparation method for a lean burn CNG catalyst comprises the following steps:
(1) Preparation of the coating
The materials are prepared according to the following mass percentage:
La-Zr-Al 2 O 3 93.51％；YO 2 0.6％；Pd 1.2％；Ba(OH) 2 1.8 percent; 2.8% of a binder; HHBR2500.09%;
water is put into a material barrel according to the La-Zr-Al 2 O 3 Weighing the materials in percentage by mass, putting the materials into a barrel, and adding YO 2 Stirring, diluting the Pd salt solution with deionized water, weighing the Pd solution after dilution, adding dropwise into a bucket, stirring for 4h, testing the pH of the solution at this time, and weighing Ba (OH) 2 Adding the mixture into a barrel, stirring for 5 hours, and adjusting the pH value of the solution to 5-6; the binder was weighed. Adding into a barrel, and stirring for 20min; weighing HHBR250, adding the HHBR250 into a barrel, stirring to the required coating viscosity, and judging whether the viscosity is proper according to the standard that the final slurry drops on the carrier do not flow quickly to the required coating viscosity.
(2) The slurry was coated on a catalyst and tested for catalyst performance
Example 3:
a preparation method of a coating for a lean-burn CNG catalyst comprises the following steps:
(1) Preparation of the coating
The materials are prepared according to the following mass percentage:
La-Zr-Al 2 O 3 93.51％；ZrO 2 0.3％、YO 2 0.3％；Pd 1.2％；Ba(OH) 2 1.8 percent; 2.8% of a binder; HHBR2500.09%;
putting water into a material barrel according to the La-Zr-Al 2 O 3 Weighing the materials according to the mass percent, putting the materials into a barrel, adding ZrO 2 0.3％、YO 2 Stirring 0.3% uniformly, diluting the Pd salt solution with deionized water, weighing the Pd solution after dilution, dropwise adding into a bucket, stirring for 4h, testing the pH of the solution at this time, and weighing Ba (OH) 2 Adding the mixture into a barrel for stirring for 5 hours, and adjusting the pH value of the solution to 5-6; the binder was weighed. Adding into a barrel, and stirring for 20min; weighing HHBR250, adding the HHBR250 into a barrel, stirring to the required coating viscosity, and judging whether the viscosity is proper according to the standard that the final slurry drops on the carrier do not flow quickly to the required coating viscosity.
It is shown in fig. 1 and fig. 2 that the hydrothermal resistance and the sulfur resistance of the catalyst are improved after the coating prepared by the preparation method is coated on the catalyst.
As a further improvement, the above-mentioned is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A coating for a lean burn CNG catalyst is characterized by comprising the following components in percentage by weight:
La-Zr-Al 2 O 3 90 to 95 percent; 0.5 to 1 percent of base metal; pd 0.8-1.5%; ba (OH) 2 1 to 2.3 percent; 2 to 3.5 percent of binder; 0.03 to 0.1 percent of cellulose;
the La-Zr-Al 2 O 3 Comprising La of 6 to 9wt% in the material 2 O 3 、20～30wt％ZrO 2 And 60 to 80wt% of Al 2 O 3 ；
La-Zr-Al 2 O 3 The change rate of the specific surface area from a fresh state to aging is less than 12 percent; the rate of change of pore volume was < 3%.
2. The coating of claim 1, wherein the cellulose is one or a mixture of hydroxyethyl cellulose and sodium carboxymethyl cellulose.
3. The coating for the lean-burn CNG catalyst according to claim 1, wherein the base metal is one or a mixture of Y, ce or Zr.
4. The coating for lean burn CNG catalyst according to claim 1, wherein said Ba (OH) 2 The content of the oxide is 40-50%; the content of the oxide of the binder is 5 to 15 percent.
5. A method of preparing a coating for a lean burn CNG catalyst according to any of claims 1 to 4, comprising the steps of:
s1, weighing La-Zr-Al 2 O 3 Putting the mixture into a barrel for stirring, adding base metal oxides and continuously stirring;
s2, diluting the Pd salt solution, weighing and adding the diluted Pd salt solution into a barrel to be continuously stirred for 2-5 hours, and testing the pH value;
s3, weighing Ba (OH) 2 Adding into a barrel and adjusting pH;
and S4, adding the binder and the cellulose, and stirring until the required viscosity for coating is reached.
6. The method of claim 5, wherein the pH of S3 is adjusted to 5-6.
CN202210963049.1A 2022-08-11 2022-08-11 Coating for lean-burn CNG catalyst and preparation method thereof Pending CN115445613A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030024085A (en) * 2001-09-17 2003-03-26 현대자동차주식회사 A catalyst for reduction of emitted gases from automobile with lean-burn engine and the manufacturing method thereof
CA2413171A1 (en) * 2001-11-30 2003-05-30 Omg Ag & Co. Kg Catalyst for lowering the amount of nitrogen oxides in the exhaust gas from lean burn engines
US20040082469A1 (en) * 2002-10-24 2004-04-29 Gandhi Haren S Perovskite catalyst system for lean burn engines
CN102974343A (en) * 2012-11-23 2013-03-20 四川中自尾气净化有限公司 Catalyst suitable for processing tail gas of lean-burn natural gas vehicle and preparation method thereof
CN103191735A (en) * 2013-03-29 2013-07-10 无锡威孚环保催化剂有限公司 Preparation method of lean-burn type natural gas vehicle catalyst
CN104056626A (en) * 2014-07-22 2014-09-24 四川中自尾气净化有限公司 Preparation method of noble metal catalyst
CN105363486A (en) * 2014-08-12 2016-03-02 凯龙蓝烽新材料科技有限公司 A preparing method of a molecular sieve based SCR catalyst
CN109603823A (en) * 2019-01-09 2019-04-12 无锡威孚环保催化剂有限公司 The lean-burn NO of diesel engine vent gas purification systemxTrap catalyst and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030024085A (en) * 2001-09-17 2003-03-26 현대자동차주식회사 A catalyst for reduction of emitted gases from automobile with lean-burn engine and the manufacturing method thereof
CA2413171A1 (en) * 2001-11-30 2003-05-30 Omg Ag & Co. Kg Catalyst for lowering the amount of nitrogen oxides in the exhaust gas from lean burn engines
US20040082469A1 (en) * 2002-10-24 2004-04-29 Gandhi Haren S Perovskite catalyst system for lean burn engines
CN102974343A (en) * 2012-11-23 2013-03-20 四川中自尾气净化有限公司 Catalyst suitable for processing tail gas of lean-burn natural gas vehicle and preparation method thereof
CN103191735A (en) * 2013-03-29 2013-07-10 无锡威孚环保催化剂有限公司 Preparation method of lean-burn type natural gas vehicle catalyst
CN104056626A (en) * 2014-07-22 2014-09-24 四川中自尾气净化有限公司 Preparation method of noble metal catalyst
CN105363486A (en) * 2014-08-12 2016-03-02 凯龙蓝烽新材料科技有限公司 A preparing method of a molecular sieve based SCR catalyst
CN109603823A (en) * 2019-01-09 2019-04-12 无锡威孚环保催化剂有限公司 The lean-burn NO of diesel engine vent gas purification systemxTrap catalyst and preparation method thereof

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Title
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屠约峰;: "天然气汽车尾气净化催化剂研究进展", 工业催化, no. 07, pages 20 - 23 *

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