CN110961142A - NSC (non-catalytic cracking) purification catalyst of tail gas emission control purifier for internal combustion engine - Google Patents
NSC (non-catalytic cracking) purification catalyst of tail gas emission control purifier for internal combustion engine Download PDFInfo
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- CN110961142A CN110961142A CN201911297585.7A CN201911297585A CN110961142A CN 110961142 A CN110961142 A CN 110961142A CN 201911297585 A CN201911297585 A CN 201911297585A CN 110961142 A CN110961142 A CN 110961142A
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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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
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- 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
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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Abstract
The invention discloses a tail gas emission control purifier NSC purifying catalyst for an internal combustion engine, which takes a honeycomb ceramic carrier or a honeycomb metal carrier as a main substrate, and takes titanium dioxide, zeolite, manganese dioxide and silica sol as a composite base coating to jointly form a purifying catalyst carrier of the product; the tail gas emission control purifier NSC purification catalyst for the internal combustion engine is characterized in that manganese dioxide is added in the traditional purification catalyst as a sulfur removal agent according to the condition of sulfur-containing fuel oil, the manganese dioxide is uniformly distributed in base layer slurry through ion exchange after being mixed with titanium dioxide and zeolite, the uniformity of the content of a coating interval of each layer of a final product is ensured, active sites of noble metals are protected from being combined with sulfur to the maximum extent, the purpose of prolonging the service life of the purification catalyst is achieved, meanwhile, some performances of thermal shock are improved, the catalyst is low in relative cost, good in activation performance and strong in sulfur resistance, raw materials are easy to purchase, and the catalyst can be popularized and used on the internal combustion engine.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a tail gas emission control purifier NSC purification catalyst for an internal combustion engine.
Background
At present, the manufacturing industry of China is in an important transition period, the country pays more and more attention to the environmental protection, the requirement of the country to an environmental protection purifier is higher and higher, particularly, the internal combustion engine industry urgently needs to comprehensively implement an engine with low emission, and the internal combustion engine with zero emission cannot be produced by the current internal combustion engine technology and the current fuel condition.
The exhaust gas discharged by the internal combustion engine contains CO, HC, NOx and SOx, wherein the Sox is mainly derived from sulfides in fuel oil, and after the internal combustion engine burns, the sulfides are partially converted into SO2 and a small amount of SO3 with lower toxicity. The higher the oxidizing activity of the purification catalyst is, the more SO3 is generated, and similarly, when S, SO2, SO4 and the like act together to cause the activity poisoning of the purification catalyst, the purification effect of the purification catalyst on the exhaust gas is reduced, and simultaneously, the SO2 contacts with water to generate sulfuric acid to corrode the exhaust pipe, SO that the exhaust pipe is corroded to be rotten.
The NSC (NOx Storage catalyst) nitrogen oxide Storage catalytic reduction NSC system mainly comprises a carrier, a catalyst and an adsorption material. The NOx storage catalyst is composed of noble metal (Pt & Pd) and the carrier is cordierite. The NSC normally works at a rate of more than 90% without the need for additional reductant and storage device. NSC reduces NOx in two major steps, adsorption and regeneration. NSCs are susceptible to sulfur combustion products SO2 in the fuel, and eventually the catalyst fails to function, severely affecting the efficiency of NOx adsorption. Therefore, in order to exert the effect of NSC, fuel oil having a sufficiently low sulfur content must be used, but the use of sulfur-containing fuel oil cannot be completely avoided at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the following technical scheme: the tail gas discharge controlling purifier NSC purifying catalyst for internal combustion engine has honeycomb ceramic carrier or honeycomb metal carrier as main base body, titanium white powder, zeolite, manganese dioxide and silica sol as composite base layer coating to constitute the purifying catalyst carrier, and Pt and Pd noble metal nitrate solution containing active component to coat the purifying catalyst carrier precisely.
Preferably, the composite base layer coating comprises 2.10g/in3 of titanium dioxide, 0.23g/in3 of β of zeolite and 0.24g/in3 of silica sol according to the proportion of molar equivalents.
A dosing process for a base coat slurry, the dosing process comprising the steps of:
s1: measuring the granularity in the slurry after titanium dioxide, deionized water, silica sol and manganese oxide powder, wherein the granularity must meet d504.0-6.0, d 9011.0-14.5 and the PH is 6.0-7.5;
s2: when the solid content of the crucible is about 35%, the crucible enters an ion exchange process, cellulose is used for adjusting the viscosity of the slurry, the specific surface area of the slurry is not less than 190m2/g, and the stirring time is not less than 5 hours.
The proportioning process of the active coating slurry comprises the following steps:
s1: deionized water, organic acid, platinum nitrate and palladium nitrate, fully mixing, adding cellulose, and analyzing the uniformity of the slurry after the viscosity of the slurry reaches 1300 cps;
s2: the proportion and the loading amount of the noble metal are adjusted according to the emission working condition of the internal combustion engine, and the range is as follows: pt and Pd are 2:1@30-40 g.
A clean-up catalyst coating process, the coating process comprising the steps of:
uniformly coating base layer coating slurry on a honeycomb cordierite or metal carrier on the end face of the carrier on a precise coating device, adjusting the coating depth by adjusting the vacuum pressure, and then drying and stabilizing the coating by a hot air drying stabilizer;
step two, carrying out a back pressure test on the coated and dried product, ensuring that the back pressure of the finished product is qualified according to back pressure test data, then putting the product into a zoned activation and calcination furnace for activation and calcination, wherein the calcination time at high temperature is not less than 10 minutes, and the activation temperature at 250 ℃ is ensured;
step three, coating an activation layer on a product coated with a base layer coating and calcined, uniformly coating activation coating slurry on the end face of a carrier, adjusting the coating depth by adjusting the vacuum pressure, and then drying and stabilizing the coating by a hot air drying stabilizer;
and step four, after the product is checked to be qualified, putting the product into a subarea activation and calcination furnace for activation and calcination, wherein the calcination time at high temperature is not less than 10 minutes, and drying and calcining, wherein the calcination of the activation layer needs to ensure that the activation temperature and the calcination temperature are in the process specified range.
In the coating process of the purification catalyst, when the hot air drying stabilizer dries the coating in the first step, the drying and dewatering rate must be more than 80%.
Compared with the prior art, the invention has the following beneficial effects: the tail gas emission control purifier NSC purification catalyst for the internal combustion engine is characterized in that manganese dioxide is added in the traditional purification catalyst as a sulfur removal agent according to the condition of sulfur-containing fuel oil, the manganese dioxide is uniformly distributed in base layer slurry through ion exchange after being mixed with titanium dioxide and zeolite, the uniformity of the content of a coating interval of each layer of a final product is ensured, active sites of noble metals are protected from being combined with sulfur to the maximum extent, the purpose of prolonging the service life of the purification catalyst is achieved, meanwhile, some performances of thermal shock are improved, the catalyst is low in relative cost, good in activation performance and strong in sulfur resistance, raw materials are easy to purchase, and the catalyst can be popularized and used on the internal combustion engine.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The tail gas discharge controlling purifier NSC purifying catalyst for internal combustion engine has honeycomb ceramic carrier or honeycomb metal carrier as main base body, titanium white powder, zeolite, manganese dioxide and silica sol as composite base layer coating to constitute the purifying catalyst carrier, and Pt and Pd noble metal nitrate solution containing active component to coat the purifying catalyst carrier precisely.
The composition of the composite base layer coating is based on the proportion of molar equivalent of 2.10g/in3 titanium dioxide, 0.23g/in3 β zeolite and 0.24g/in3 silica sol.
When the base coating slurry is prepared, firstly, the granularity in the slurry is measured after titanium dioxide, deionized water, silica sol and manganese oxide powder are mixed, wherein the granularity must meet d504.0-6.0, d 9011.0-14.5, PH:
6.0-7.5; when the solid content of the crucible is about 35%, the crucible enters an ion exchange process, cellulose is used for adjusting the viscosity of the slurry, the specific surface area of the slurry is not less than 190m2/g, and the stirring time is not less than 5 hours.
When the active coating slurry is prepared, deionized water, organic acid, platinum nitrate and palladium nitrate are fully mixed, cellulose is added, and the uniformity of the slurry is analyzed after the viscosity of the slurry reaches 1300 cps; the proportion and the loading amount of the noble metal are adjusted according to the emission working condition of the internal combustion engine, and the range is as follows: pt and Pd are 2:1@30-40 g.
When the purifying catalyst is coated, the honeycomb cordierite or the metal carrier is uniformly coated with the base layer coating slurry on the end face of the carrier on a precise coating device, the coating depth is adjusted by adjusting the vacuum pressure, and then the coating is dried and stabilized by a hot air drying stabilizer; carrying out a backpressure test on the coated and dried product, ensuring that the backpressure of the finished product is qualified according to backpressure test data, then putting the product into a zoned activation and calcination furnace for activation and calcination, wherein the calcination time at high temperature is not less than 10 minutes, and the activation temperature at 250 ℃ is ensured; coating an activation layer on a product coated with a base layer coating and calcined, uniformly coating and placing activation coating slurry on the end face of a carrier, adjusting the coating depth by adjusting the vacuum pressure, and then drying and stabilizing the coating by a hot air drying stabilizer; and after the product is checked to be qualified, putting the product into a subarea activation and calcination furnace for activation and calcination, wherein the calcination time at high temperature is not less than 10 minutes, and drying and calcining, wherein the calcination of the activation layer needs to ensure that the activation temperature and the calcination temperature are in the process specified range.
In the coating process of the purification catalyst, when the hot air drying stabilizer dries the coating in the first step, the drying and dewatering rate must be more than 80%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The NSC purifying catalyst for tail gas exhaust controlling purifier of internal combustion engine features that the purifying catalyst has honeycomb ceramic carrier or honeycomb metal carrier as main base body, titanium white, zeolite, manganese dioxide and silica sol as composite base layer coating to constitute the purifying catalyst carrier, and the Pt and Pd noble metal nitrate solution containing active component is coated precisely on the purifying catalyst carrier.
2. The NSC purifying catalyst of the exhaust emission control purifier for the internal combustion engine as claimed in claim 1, wherein the composite base layer coating comprises titanium dioxide 2.10g/in3, β zeolite 0.23g/in3 and silica sol 0.24g/in3 according to molar equivalent ratio.
3. The process of dosing a base coat slurry of claim 1, wherein: the batching process comprises the following steps:
s1: measuring the granularity in the slurry after titanium dioxide, deionized water, silica sol and manganese oxide powder, wherein the granularity must meet d504.0-6.0, d 9011.0-14.5 and the PH is 6.0-7.5;
s2: when the solid content of the crucible is about 35%, the crucible enters an ion exchange process, cellulose is used for adjusting the viscosity of the slurry, the specific surface area of the slurry is not less than 190m2/g, and the stirring time is not less than 5 hours.
4. The process of dosing a slurry for a reactive coating according to claim 1, wherein: the batching process comprises the following steps:
s1: deionized water, organic acid, platinum nitrate and palladium nitrate, fully mixing, adding cellulose, and analyzing the uniformity of the slurry after the viscosity of the slurry reaches 1300 cps;
s2: the proportion and the loading amount of the noble metal are adjusted according to the emission working condition of the internal combustion engine, and the range is as follows: pt and Pd are 2:1@30-40 g.
5. The clean-up catalyst coating process of claim 1, wherein: the coating process comprises the following steps:
uniformly coating base layer coating slurry on a honeycomb cordierite or metal carrier on the end face of the carrier on a precise coating device, adjusting the coating depth by adjusting the vacuum pressure, and then drying and stabilizing the coating by a hot air drying stabilizer;
step two, carrying out a back pressure test on the coated and dried product, ensuring that the back pressure of the finished product is qualified according to back pressure test data, then putting the product into a zoned activation and calcination furnace for activation and calcination, wherein the calcination time at high temperature is not less than 10 minutes, and the activation temperature at 250 ℃ is ensured;
step three, coating an activation layer on a product coated with a base layer coating and calcined, uniformly coating activation coating slurry on the end face of a carrier, adjusting the coating depth by adjusting the vacuum pressure, and then drying and stabilizing the coating by a hot air drying stabilizer;
and step four, after the product is checked to be qualified, putting the product into a subarea activation and calcination furnace for activation and calcination, wherein the calcination time at high temperature is not less than 10 minutes, and drying and calcining, wherein the calcination of the activation layer needs to ensure that the activation temperature and the calcination temperature are in the process specified range.
6. The clean-up catalyst coating process of claim 5, wherein: when the hot air drying stabilizer dries the coating in the first step, the drying dehydration rate must be more than 80%.
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| CN201911297585.7A CN110961142A (en) | 2019-12-17 | 2019-12-17 | NSC (non-catalytic cracking) purification catalyst of tail gas emission control purifier for internal combustion engine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112096486A (en) * | 2020-09-04 | 2020-12-18 | 珂黎艾净化技术江苏有限公司 | Processing technology of Cu-SDPF catalytic emission control purifier |
| CN112096485A (en) * | 2020-09-04 | 2020-12-18 | 珂黎艾净化技术江苏有限公司 | Processing technology of Fe-SDPF catalytic emission control purifier |
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| US20180023436A1 (en) * | 2015-02-03 | 2018-01-25 | Honda Motor Co., Ltd. | Exhaust gas purification device for internal combustion engine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112096486A (en) * | 2020-09-04 | 2020-12-18 | 珂黎艾净化技术江苏有限公司 | Processing technology of Cu-SDPF catalytic emission control purifier |
| CN112096485A (en) * | 2020-09-04 | 2020-12-18 | 珂黎艾净化技术江苏有限公司 | Processing technology of Fe-SDPF catalytic emission control purifier |
| CN112096486B (en) * | 2020-09-04 | 2022-08-12 | 珂黎艾净化技术江苏有限公司 | Processing technology of Cu-SDPF catalytic emission control purifier |
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