CN114618538A - Rh/AlPO4Preparation method of (A) and application of (A) in TWC - Google Patents
Rh/AlPO4Preparation method of (A) and application of (A) in TWC Download PDFInfo
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- CN114618538A CN114618538A CN202210118094.7A CN202210118094A CN114618538A CN 114618538 A CN114618538 A CN 114618538A CN 202210118094 A CN202210118094 A CN 202210118094A CN 114618538 A CN114618538 A CN 114618538A
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- alpo
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- 238000000034 method Methods 0.000 title description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000010405 reoxidation reaction Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000010948 rhodium Substances 0.000 description 32
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- 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
- B01D2258/018—Natural gas engines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides Rh/AlPO4The preparation method and the application thereof in the TWC comprise the following steps of (1) mixing H3PO4Dropwise addition of the solution to Al (NO)3)3In the solution, quickly stirring to obtain a solution A; (2) standing the solution A, taking a supernatant of the solution A, and adjusting the pH of the supernatant to 4-5 by using an alkaline substance to obtain a white colloid; (3) washing and drying the white colloid, and heating in the air; (4) for Rh (NH) in aqueous solution3+Carrying out equilibrium adsorption to obtain Rh/AlPO4。AlPO4As an effective and strong support material, leading to optimal metal-support interaction, Rh loading can be significantly reduced, saving on Rh element usage. By the pair Rh/AlPO4Detection of catalyst Performance, Rh/AlPO4Exhibits higher stability against heat aging under oxidizing conditions, and is compatible with Al2O3In contrast, the load is in AlPO4Rh of (a) exhibits a higher resistance to reoxidation.
Description
Technical Field
The invention relates to the field of preparation methods and applications of metal phosphate catalysts, and particularly relates to Rh/AlPO4Use in a natural gas engine aftertreatment TWC.
Background
The metal-support interaction is the core of the field of catalytic chemistry, in the three-way catalysts (TWC) most widely used for gasoline-fueled engines, Rh, PD, Pt are used to efficiently convert exhaust gases containing carbon monoxide, nitrogen oxides, hydrocarbons into harmless non-pollutants, rhodium being responsible for the removal of NOxThis is particularly important because it is not substitutable and its use in TWCs accounts for over 80% of the demand, and since Rh is one of the most scarce platinum group metals, it is of practical interest to reduce the use of Rh in TWCs. However, when exposed to high-temperature exhaust gas, the metal nanoparticles are aggregated into large particles having a low specific surface area and thus have low catalytic activity. Therefore, the conventional TWC requires an excessive amount of metal carrier against deactivation by sintering, and the kind, properties, and the like of the carrier largely affect the performance of the catalyst, and thus the carrier is an indispensable part in the preparation process of the catalyst. The choice of a suitable carrier is generally made according to the reaction requirements and the physicochemical properties of the active ingredient and the carrier. To overcome this problem, several recent catalysts have been developed that use the anchoring effect, and although the effect is well known for supported Pt and PD catalysts, the detailed anchoring mechanism of Rh catalysts has not been systematically established so far.
In the prior art, Rh is Al2O3Machine workAs a carrier, a carrier having characteristics of a wide source of alumina, surface acid centers and surface alkali centers, and a wide selectivity due to the presence of different transition phases in a wide temperature range is generally used as a catalyst carrier, but a carrier used in TWC is required to have strong stability against thermal aging and oxidation reduction at high temperature.
Disclosure of Invention
In order to solve the defects of the prior art, the Rh/AlPO is provided4A process for their preparation and their use in TWC.
Rh/AlPO4The preparation method comprises the following steps:
s1, mixing H3PO4Dropwise addition of the solution to Al (NO)3)3In the solution, quickly stirring to obtain a solution A;
s2, standing the solution A, taking the supernatant of the solution A, and adjusting the pH of the supernatant to 4-5 by using an alkaline substance to obtain a white colloid;
s3, washing and drying the white colloid, and heating in the air;
s4 preparation of Rh (NH) in aqueous solution3+Carrying out equilibrium adsorption to obtain Rh/AlPO4。
Preferably, H in S13PO4The concentration of the solution was 1 mol/L.
Preferably, Al (NO) in S13)3The concentration of the solution was 1 mol/L.
Preferably, the alkaline substance of S2 is ammonia water, and the concentration of the ammonia water is 20-30%.
Preferably, the heating time in S3 is 4-6 h.
Preferably, the heating temperature in the S3 is 1000-1500 ℃.
Rh/AlPO4Rh/AlPO prepared by the preparation method4Application in TWC.
Has the advantages that:
(1) in contrast to the conventional support using alumina as the metal catalyst, the use of phosphate as the support anchors Rh nanoparticles even in a high-temperature environment. AlPo4As aAn effective and robust support material, resulting in optimal metal-support interaction, can significantly reduce Rh loading, saving Rh element usage.
(2) By the pair Rh/AlPO4Detection of catalyst Performance, Rh/AlPO4Exhibits higher heat aging resistance stability under oxidation conditions, and Al2O3In contrast, the load is in AlPO4Rh of (a) exhibits a higher resistance to reoxidation.
Drawings
FIG. 1 is Rh/AlPO4With Rh/Al2O3The catalytic activity of (a) is related to the aging temperature.
FIG. 2 is Rh/AlPO4With Rh/Al2O3The catalytic activity of (a) is related to the reduction temperature.
Detailed Description
For the purpose of enhancing 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 provided for illustration only and are not intended to limit the scope of the present invention.
Preparation of catalyst
Rh/AlPO4The preparation method comprises the following steps:
(1) h is to be3PO4Dropwise addition to Al (NO)3)3In solution and rapidly stirred to obtain solution A, wherein H3PO4Has a concentration of 1mol/L, Al (NO)3)3The concentration of (A) is 1 mol/L;
(2) standing the solution A, taking a supernatant of the solution A, and adjusting the pH of the supernatant to 4-5 by using ammonia water to obtain a white colloid, wherein the concentration of the ammonia water is 20-30%;
(3) washing and drying the white colloid, and heating the white colloid in the air at 1000 ℃ for 5 hours;
(4) to Rh (NH) in aqueous solution3+Carrying out equilibrium adsorption to obtain Rh/AlPO4。
II, preparing a reference catalyst
(1) Rh (NO)3)3Is impregnated into gamma-Al2O3Performing the following steps;
(2) air drying at 100 deg.C;
(3) after the air drying is finished, forging for 3h at 600 ℃ to prepare Rh/Al2O3。
Thirdly, detecting the performance of the catalyst
The prepared Rh/AlPO4And Rh/Al2O3At 10% H2Heating in O/air at 900-1050 ℃ for 25h, and detecting the thermal stability of the two catalysts in an oxidation environment;
catalyst aged at 900 deg.C followed by 20% H2Heating in the/He atmosphere at 200-800 ℃ for 5h, and detecting the thermal stability of the two catalysts in a reduction environment.
Rh/AlPO4Exhibits higher stability against heat aging under oxidizing conditions, and is compatible with Al2O3In contrast, the load is in AlPO4Rh of (a) exhibits a higher resistance to reoxidation.
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 (7)
1. Rh/AlPO4The preparation method is characterized by comprising the following steps:
s1, mixing H3PO4Dropwise addition of the solution to Al (NO)3)3In the solution, quickly stirring to obtain a solution A;
s2, standing the solution A, taking the supernatant of the solution A, and adjusting the pH of the supernatant to 4-5 by using an alkaline substance to obtain a white colloid;
s3, washing and drying the white colloid, and heating in the air;
s4 reaction of Rh (NH) with aqueous solution3+Carrying out equilibrium adsorption to obtain Rh/AlPO4。
2. According to claim 1The Rh/AlPO4Characterized in that H in S1 is3PO4The concentration of the solution was 1 mol/L.
3. An Rh/AlPO according to claim 14Characterized in that Al (NO) in S13)3The concentration of the solution was 1 mol/L.
4. An Rh/AlPO according to claim 14The preparation method is characterized in that the alkaline substance of S2 is ammonia water, and the concentration of the ammonia water is 20-30%.
5. An Rh/AlPO according to claim 14The preparation method is characterized in that the heating time in the S3 is 4-6 h.
6. An Rh/AlPO according to claim 14The preparation method is characterized in that the heating temperature of S3 is 1000-1500 ℃.
7. An Rh/AlPO according to any one of claims 1 to 64Rh/AlPO prepared by the preparation method4Application in TWC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210118094.7A CN114618538A (en) | 2022-02-08 | 2022-02-08 | Rh/AlPO4Preparation method of (A) and application of (A) in TWC |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210118094.7A CN114618538A (en) | 2022-02-08 | 2022-02-08 | Rh/AlPO4Preparation method of (A) and application of (A) in TWC |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114618538A true CN114618538A (en) | 2022-06-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210118094.7A Pending CN114618538A (en) | 2022-02-08 | 2022-02-08 | Rh/AlPO4Preparation method of (A) and application of (A) in TWC |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114618538A (en) |
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2022
- 2022-02-08 CN CN202210118094.7A patent/CN114618538A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| MASATO MACHIDA ET AL.: ""Unusual Redox Behavior of AlPO4 and Its Impact on Three-Way Catalysis"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》, vol. 119, no. 1, pages 374 * |
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Application publication date: 20220614 |