CN117380258B - Catalyst for treating automobile exhaust and its process - Google Patents
Catalyst for treating automobile exhaust and its process Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 239000011248 coating agent Substances 0.000 claims abstract description 54
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 41
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000011149 active material Substances 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 10
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 7
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 abstract description 15
- 230000035939 shock Effects 0.000 abstract description 15
- 239000004094 surface-active agent Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- 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
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- B01J37/0228—Coating in several steps
-
- 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
- B01J37/08—Heat treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (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)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and provides an automobile tail gas treatment catalyst and a process thereof, wherein the catalyst consists of a carrier and a coating coated on the carrier, and the coating comprises the following components in parts by weight: 1.5-2 parts of ammonium metavanadate solution, 10-15 parts of tungsten-titanium powder, 0.1-0.5 part of cerium-zirconium powder, 1-2 parts of active material, 2-4 parts of nonionic surfactant, 14-16 parts of modified silica sol, 160-180 parts of deionized water and 1-3 parts of Cu-SSZ molecular sieve slurry; the modified silica sol is obtained by treating silica sol with a silane coupling agent KH-550 and triphenyl silanol; the carrier is cordierite honeycomb ceramic. By the technical scheme, the problem that the catalyst coating in the prior art is poor in erosion resistance and thermal shock resistance is solved.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an automobile exhaust treatment catalyst and a process thereof.
Background
At present, the reduction of automobile exhaust emission mainly comprises: the pre-machine measures, the in-machine measures and the post-machine measures, wherein the post-machine measures for installing the automobile exhaust catalytic cleaner are considered to be a more effective method for controlling the automobile exhaust emission, and the automobile exhaust catalytic cleaner consists of a shell, a gasket and a catalyst 3.
The cordierite honeycomb ceramics which are commonly used at present as catalyst carriers have the advantages of low thermal expansion coefficient, excellent thermal stability and good impact resistance, but the specific surface area is smaller (less than 1 m) 2 And/g), a coating layer is required to be coated on the surface of the cordierite honeycomb ceramic to increase the specific surface area. The bonding strength of the coating can directly influence the catalytic effect, and when the bonding strength of the coating and the carrier is low, the coating is easy to crack and peel due to temperature change and erosion of air flow, and the catalytic conversion effect on tail gas can be greatly reduced, so that the erosion resistance and the thermal shock resistance of the catalyst coating are required to be improved.
Disclosure of Invention
The invention provides an automobile exhaust treatment catalyst and a process thereof, which solve the problems of poor erosion resistance and thermal shock resistance of a catalyst coating in the related art.
The technical scheme of the invention is as follows:
the automobile exhaust treatment catalyst consists of a carrier and a coating coated on the carrier, wherein the catalytic coating comprises the following components in parts by weight: 1.5-2 parts of ammonium metavanadate solution, 10-15 parts of tungsten-titanium powder, 0.1-0.5 part of cerium-zirconium powder, 1-2 parts of active material, 2-4 parts of nonionic surfactant, 14-16 parts of modified silica sol, 16-20 parts of deionized water and 1-3 parts of Cu-SSZ molecular sieve slurry; the modified silica sol is obtained by treating silica sol with a silane coupling agent KH-550 and triphenyl silanol; the carrier is cordierite honeycomb ceramic.
As a further technical scheme, the preparation method of the Cu-SSZ molecular sieve slurry comprises the following steps: mixing the Cu-SSZ molecular sieve, the alumina sol micropowder and water in a mass ratio of 1:0.5:3.5 to obtain the Cu-SSZ molecular sieve slurry.
As a further technical scheme, the preparation method of the modified silica sol comprises the following steps:
a1, adding silica sol into an ethanol water solution, and uniformly mixing to obtain a mixture;
and A2, adding a silane coupling agent KH-550 and triphenyl silanol into the mixture to react, and obtaining the modified silica sol.
As a further technical scheme, the mass sum of the silane coupling agent KH-550 and the triphenylsilanol is 15-20% of the mass of the silica sol.
As a further technical scheme, the reaction temperature in the A2 is 45-65 ℃ and the reaction time is 24-36h.
As a further technical scheme, the mass ratio of the silane coupling agent KH-550 to the triphenyl silanol is 1-2:1.
As a further technical scheme, the mass ratio of the silane coupling agent KH-550 to the triphenyl silanol is 1.5:1.
According to the invention, when the mass ratio of the silane coupling agent KH-550 to the triphenylsilanol is 1.5:1, not only can the hydroxyl groups on the surface of the silica sol be further reduced and the dispersibility of the silica sol be improved, but also the coating material has good thermal shock resistance when coated on a carrier.
As a further technical scheme, the active material consists of chromium nitrate, copper nitrate, nickel oxide, manganese nitrate and cobalt nitrate.
As a further technical scheme, the mass ratio of the chromium nitrate to the copper nitrate to the nickel oxide to the manganese nitrate to the cobalt nitrate is 3.5:24.2:94:4.2:5.2.
As a further technical scheme, the mass concentration of ammonium metavanadate in the ammonium metavanadate solution is 30% -35%.
As a further technical scheme, the solvent of the ammonium metavanadate solution is oxalic acid.
As a further technical scheme, the nonionic surfactant is a TX-series nonionic surfactant and/or an NP-series nonionic surfactant.
As a further technical scheme, the nonionic surfactant is composed of a TX-series nonionic surfactant and an NP-series nonionic surfactant, and the mass ratio of the TX-series nonionic surfactant to the NP-series nonionic surfactant is 1:1.
As a further technical scheme, the NP series nonionic surfactant is NP-40 surfactant, and the TX series nonionic surfactant is TX-10 surfactant.
The present invention defines the nonionic surfactant as a TX-series nonionic surfactant and/or an NP-series nonionic surfactant, and finds that when the nonionic surfactant is composed of an NP-40 surfactant and a TX-10 surfactant, the prepared coating can further improve the erosion resistance and thermal shock resistance of the catalyst coating after being coated on the carrier.
The invention also comprises a preparation method of the automobile exhaust treatment catalyst, which comprises the following steps:
s1, mixing all components in the coating to obtain a coating material;
s2, coating the coating material on a carrier, drying and calcining to obtain the catalyst.
As a further technical scheme, the calcining temperature is 500-550 ℃ and the calcining time is 1.5-2.5h.
As a further technical scheme, the drying temperature is 80-120 ℃ and the drying time is 2h.
The working principle and the beneficial effects of the invention are as follows:
the modified silica sol is added into the catalyst coating, after the silica sol is modified together by the silane coupling agent KH-550 and the triphenyl silanol, the hydroxyl groups on the surface of the silica sol are reduced, the compatibility and interface cohesiveness of the silica sol and other components of the coating are improved, the modified silica sol is added into the coating, the erosion resistance of the coating is improved, and the introduction of the triphenyl silanol further improves the thermal shock resistance of the coating. In addition, the addition of the nonionic surfactant improves the dispersibility of each component in the coating, and each component can be uniformly dispersed in the coating, so that the bonding strength of the coating and the carrier is improved, and the coating of the catalyst has good erosion resistance and thermal shock resistance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples:
cordierite honeycomb ceramic carrier, cat No.: GL-389, available from: COLIN (CORPORATION of Duckweed, inc.) of environmental protection technology;
silica sol, cat No.: JR1007b, purchased from: henan jin Fu Xin He Ling New Material Co., ltd;
the preparation method of the Cu-SSZ molecular sieve slurry comprises the following steps: mixing a Cu-SSZ molecular sieve, alumina sol micropowder and deionized water in a mass ratio of 1:0.5:3.5 to obtain a Cu-SSZ molecular sieve slurry; wherein the Cu-SSZ molecular sieve is purchased from Sichuan Hao New Material technology Co., ltd; aluminum sol micropowder, model JHALH-15, available from crystal fire technology glass inc. In texas;
the active materials are composed of chromium nitrate, copper nitrate, nickel oxide, manganese nitrate and cobalt nitrate, and the mass ratio of the chromium nitrate to the copper nitrate to the nickel oxide to the manganese nitrate to the cobalt nitrate is 3.5:24.2:94:4.2:5.2.
Example 1
A method for preparing a catalyst comprising the steps of:
s1, mixing 7.5g of ammonium metavanadate solution (the mass concentration is 30%), 50g of tungsten-titanium powder, 0.5g of cerium-zirconium powder, 5g of active material, 5g of NP-40 surfactant, 5gTX-10 surfactant, 70g of modified silica sol, 80g of deionized water and 5g of Cu-SSZ molecular sieve slurry to obtain a coating material;
s2, coating the coating material on 5mL of cordierite honeycomb ceramic carrier, drying at 80 ℃ for 2h, and calcining at 500 ℃ for 2.5h to obtain the catalyst.
The preparation method of the modified silica sol comprises the following steps:
a1, adding 40 parts of silica sol into 240 parts of ethanol water solution, and uniformly mixing to obtain a mixture;
a2, adding 3.6 parts of a silane coupling agent KH-550 and 2.4 parts of triphenyl silanol into the mixture, and reacting at 45 ℃ for 36 hours to obtain the modified silica sol.
Example 2
A method for preparing a catalyst comprising the steps of:
s1, 8.5g of ammonium metavanadate solution (the mass concentration is 33%), 68g of tungsten titanium powder, 1.5g of cerium zirconium powder, 7.5g of active material, 7.5g of NP-40 surfactant, 7.5g of gTX-10 surfactant, 75g of modified silica sol, 85g of deionized water and 10g of Cu-SSZ molecular sieve slurry are mixed to obtain a coating material;
s2, coating the coating material on 5mL of cordierite honeycomb ceramic carrier, drying at 100 ℃ for 2h, and calcining at 530 ℃ for 2h to obtain the catalyst.
The preparation method of the modified silica sol comprises the following steps:
a1, adding 40 parts of silica sol into 240 parts of ethanol water solution, and uniformly mixing to obtain a mixture;
a2, adding 4.3 parts of silane coupling agent KH-550 and 2.9 parts of triphenyl silanol into the mixture, and reacting for 30 hours at 50 ℃ to obtain the modified silica sol.
Example 3
A method for preparing a catalyst comprising the steps of:
s1, mixing 10g of ammonium metavanadate solution (the mass concentration is 35%), 75g of tungsten-titanium powder, 2.5g of cerium-zirconium powder, 10g of active material, 10g of NP-40 surfactant, 10gTX-10 surfactant, 80g of modified silica sol, 100g of deionized water and 15g of Cu-SSZ molecular sieve slurry to obtain a coating material;
s2, coating the coating material on 10mL of cordierite honeycomb ceramic carrier, drying at 120 ℃ for 2h, and calcining at 550 ℃ for 1.5h to obtain the catalyst.
The preparation method of the modified silica sol comprises the following steps:
a1, adding 40 parts of silica sol into 240 parts of ethanol water solution, and uniformly mixing to obtain a mixture;
a2, adding 4.8 parts of silane coupling agent KH-550 and 3.2 parts of triphenyl silanol into the mixture, and reacting for 24 hours at 65 ℃ to obtain the modified silica sol.
Example 4
Example 4 is different from example 1 in that 3 parts of the silane coupling agent KH-550 and 3 parts of the triphenyl silanol are used.
Example 5
Example 5 is different from example 1 in that 4 parts of the silane coupling agent KH-550 and 2 parts of triphenyl silanol.
Example 6
Example 6 differs from example 1 in that the NP-40 surfactant was replaced by an equivalent amount of TX-10 surfactant.
Example 7
Example 7 differs from example 1 in that the TX-10 surfactant was replaced with an equivalent amount of NP-40 surfactant.
Example 8
Example 8 differs from example 1 in that the TX-10 surfactant is replaced with an equivalent amount of TX-100 surfactant.
Comparative example 1
A method for preparing a catalyst comprising the steps of:
s1, mixing 7.5g of ammonium metavanadate solution (the mass concentration is 30%), 50g of tungsten-titanium powder, 0.5g of cerium-zirconium powder, 5g of active material, 5g of NP-40 surfactant, 5gTX-10 surfactant, 70g of silica sol, 80g of deionized water and 5g of Cu-SSZ molecular sieve slurry to obtain a coating material;
s2, coating the coating material on 5mL of cordierite honeycomb ceramic carrier, drying at 80 ℃ for 2h, and calcining at 500 ℃ for 2.5h to obtain the catalyst.
Comparative example 2
In comparison with example 1, comparative example 2 was not added with the silane coupling agent KH-550, and the other is the same as example 1.
Comparative example 3
In contrast to example 1, comparative example 3 was not added with triphenyl silanol, and the other is the same as example 1.
Comparative example 4
Comparative example 4 replaces TX-10 surfactant with an equal amount of OP-10 surfactant as compared to example 1, with the other being the same as in example 1.
Comparative example 5
Comparative example 5 was conducted in the same manner as in example 1 except that the NP-40 surfactant and the TX-10 surfactant were not added as in example 1.
Test examples
(1) The thermal shock resistance and the erosion resistance of the catalyst coatings prepared in examples 1 to 8 and comparative examples 1 to 5 were measured as follows:
thermal shock resistance: putting the catalyst into a muffle furnace at 1000 ℃, adding the catalyst for 2min, rapidly taking out the catalyst, cooling the catalyst in air, repeating the cooling process for 8 times, and calculating the coating falling rate;
erosion resistance: washing the catalyst with water flow of 14.4L/min for 10min, then blowing the catalyst with air of 0.4MPa and 7.7m/s flow rate for 10min, repeating for 2 times, and calculating the coating falling rate;
coating shedding rate (%) = (pre-treatment catalyst weight-post-treatment catalyst weight)/pre-treatment catalyst weight×100%;
the measurement results are shown in Table 1.
TABLE 1 measurement results of examples 1-8 and comparative examples 1-5
Compared with the example 1, the comparative example 1 does not modify the silica sol, the comparative example 2 does not add the silane coupling agent KH-550, the comparative example 3 does not add the triphenylsilanol, and as a result, the catalyst coating of the comparative examples 1-3 has higher falling rate than the catalyst coating of the example 1 in the thermal shock and erosion resistance test, which indicates that the silane coupling agent KH-550 and the triphenylsilanol together modify the silica sol, so that the thermal shock resistance and erosion resistance of the catalyst coating can be improved.
Compared with example 1, examples 4-5 change the mass ratio of the silane coupling agent KH-550 to the triphenyl silanol, and as a result, the falling rate of the coating of the catalyst coating of examples 4-5 is higher than that of example 1 in the thermal shock resistance and the erosion resistance test, which shows that the modified silica sol prepared when the mass ratio of the silane coupling agent KH-550 to the triphenyl silanol is 1.5:1 is added into the coating, so that the thermal shock resistance and the erosion resistance of the coating can be improved.
In example 6, the NP-40 surfactant was replaced with an equivalent amount of TX-10 surfactant, example 7, the TX-10 surfactant was replaced with an equivalent amount of NP-40 surfactant, example 8, the TX-10 surfactant was replaced with an equivalent amount of TX-100 surfactant, comparative example 4, the TX-10 surfactant was replaced with an equivalent amount of OP-10 surfactant, comparative example 5, and no NP-40 surfactant or TX-10 surfactant was added, as a result, the shedding rate of the coatings in both the thermal shock and erosion resistance tests was higher for the catalyst coatings of examples 6-7 and comparative examples 4-5 than for example 1, indicating that the thermal shock and erosion resistance of the catalyst coatings could be further improved when the nonionic surfactant consisted of NP-40 surfactant or TX-10 surfactant in the present invention.
(2) Examples 1-3 evaluation of the conversion Effect of the catalyst on NOx
The activity evaluation test was performed on a catalyst activity evaluation device under the following conditions: the temperature is 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ respectively, and the reaction simulates automobile exhaust and reaction gas: NO and NH 3 500ppm,10% O 2 ，10%H 2 O，N 2 To balance the gas, the reaction space velocity is 50000h -1 The NOx conversion was measured, and the measurement results are shown in table 2.
TABLE 2 NOx conversion (%)
As can be seen from Table 2, the catalysts prepared in examples 1-3 of the present invention have good conversion rates for NOx in the range of 200-550 ℃.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. The automobile exhaust treatment catalyst is characterized by comprising a carrier and a coating coated on the carrier, wherein the coating comprises the following components in parts by weight: 1.5-2 parts of ammonium metavanadate solution, 10-15 parts of tungsten-titanium powder, 0.1-0.5 part of cerium-zirconium powder, 1-2 parts of active material, 2-4 parts of nonionic surfactant, 14-16 parts of modified silica sol, 16-20 parts of deionized water and 1-3 parts of Cu-SSZ molecular sieve slurry; the modified silica sol is obtained by treating silica sol with a silane coupling agent KH-550 and triphenyl silanol; the carrier is cordierite honeycomb ceramics;
the preparation method of the modified silica sol comprises the following steps:
a1, adding silica sol into an ethanol water solution, and uniformly mixing to obtain a mixture;
a2, adding a silane coupling agent KH-550 and triphenyl silanol into the mixture to react, so as to obtain modified silica sol;
the mass sum of the silane coupling agent KH-550 and the triphenyl silanol is 15% -20% of the mass of the silica sol;
the mass ratio of the silane coupling agent KH-550 to the triphenyl silanol is 1-2:1;
the active material consists of chromium nitrate, copper nitrate, nickel oxide, manganese nitrate and cobalt nitrate;
the nonionic surfactant is a TX-series nonionic surfactant and/or an NP-series nonionic surfactant.
2. An automobile exhaust treatment catalyst according to claim 1, wherein the reaction temperature in A2 is 45-65 ℃ and the reaction time is 24-36 hours.
3. An automobile exhaust treatment catalyst according to claim 1, wherein the mass concentration of ammonium metavanadate in the ammonium metavanadate solution is 30% -33%.
4. The method for preparing an automobile exhaust gas treatment catalyst according to claim 1, comprising the steps of:
s1, mixing all components in the coating to obtain a coating material;
s2, coating the coating material on a carrier, drying and calcining to obtain the catalyst.
5. The method for preparing an automobile exhaust gas treatment catalyst according to claim 4, wherein the calcination temperature is 500-550 ℃ and the calcination time is 1.5-2.5h.
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| WO2023085269A1 (en) * | 2021-11-09 | 2023-05-19 | 株式会社カネカ | Adhesive composition for polyester |
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| CN1530406A (en) * | 2003-03-12 | 2004-09-22 | 中 徐 | Ceramic thermal insulative pigment |
| CN103168080A (en) * | 2010-10-27 | 2013-06-19 | 施敏打硬株式会社 | Curable composition |
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