CN103806990B - The vehicle tail gas treater preparation method of ceramic fiber catalyst carrier - Google Patents
The vehicle tail gas treater preparation method of ceramic fiber catalyst carrier Download PDFInfo
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- CN103806990B CN103806990B CN201410047919.6A CN201410047919A CN103806990B CN 103806990 B CN103806990 B CN 103806990B CN 201410047919 A CN201410047919 A CN 201410047919A CN 103806990 B CN103806990 B CN 103806990B
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- ceramic fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a kind of vehicle tail gas treater preparation method of ceramic fiber catalyst carrier, in distilled water, add the inorganic salts of cerium, zirconium, lanthanum, strontium and cobalt, after stirring, obtain aqueous catalyst solution.In aqueous catalyst solution, add colloidal sol forming agent, after stirring, then add micelle suspending agent, obtain stable catalyzer colloidal sol.By ceramic fiber cotton post, immerse in catalyzer colloidal sol, obtain the ceramic fiber cotton post of surface adhesion catalyst colloid; Drying and calcining obtain catalyst-loaded ceramic fiber cotton post again, load in the metallic case with inner thermal insulating layer, namely obtain automobile exhaust purifier.The features such as the present invention has that cost is low, technique is simple, the high and long service life of catalytic efficiency.
Description
Technical field
The present invention relates to one ceramic fiber cotton as catalyst carrier, be prepared into the method for the vehicle tail gas treater of porous.
Background technique
Along with China's economic rapid growth, automotive industry is rapidly developed, automobile increasing number.National car owning amount increases with surprising rapidity in recent years, and the health of people in the automobile exhaust pollution serious harm produced therefrom.The car check of China and maintenance system imperfection, in-use automotive vehicle condition is of poor quality, causes bicycle to discharge pollutants and exceeds world level.And China's automobile exhaust pollution thing level of control is lower, big city environmental quality is caused to worsen.NOx pollutes outstanding behaviours in the big city of population more than 1,000,000 or megalopolis, as cities such as Guangzhou, Beijing, Shanghai, Anshan, Wuhan.Part city traffic arterial highway CO and NOx concentration seriously exceed NBS.Automobile exhaust pollution has become main air pollutant and one of has originated.Research shows: in big city more than 40% NOx, the CO of more than the 80% and HC of more than 70% is from vehicle exhaust.In vehicle exhaust, main component has CO, NOx, SO
2, HC, particulate matter etc.; Administer tail gas pollution and become the problem [Zhang Jian, Li Cheng, Wu Xian etc., the application of metal fiber polyporous material in tail gas cleaner for motor-driven vehicle [J], Rare Metals Materials and engineering, 2007,36(supplementary issue 3): 378-382] paid close attention to both at home and abroad.
Cellucotton has following characteristics relative to honeycomb substrate: (1) specific surface area is large, can reach (1-9) × 10
3cm
2/ cm
3, high-specific surface area is conducive to attachment and the dispersion of catalyst activity component materials, increases the contact probability of pollutant in active component and vehicle exhaust, improves catalyzer to the transformation efficiency of pollutant.(2) aperture size is even, arbitrarily can control, and can form gradient-structure vertically, not only have good gas trafficability performance within the scope of 1-100 μm, and can stop and flue dust grain husk grain in adsorption vehicle tail gas.(3) porosity ratio is high, can reach more than 90%, in porous structure, has very high dust containing capacity, also can pulse gas jet regeneration.(4) bulk density is little, there is low heat capacity and thermal conductivity high as far as possible, to shorten the time that catalyzer arrives operating temperature, improve initial service behaviour [Zhang Jian, Li Cheng, the Wu Xian etc. of catalyzer, the application of metal fiber polyporous material in tail gas cleaner for motor-driven vehicle [J], Rare Metals Materials and engineering, 2007,36(supplementary issue 3): 378-382].
Special porosity and tortuous the being connected property in space of cellucotton carrier can change the path of the propagation of vehicle exhaust, extend area of contact and the time of contact of tail gas and catalyzer, improve contact probability, to improve the transformation efficiency of catalyzer to pollutant, its advantage is that other carriers are incomparable.
The porous ceramics that the people such as the Wang Hui of South China Science & Engineering University prepare with mullite fiber is for carrier, the nitrate aqueous solution of configuration La, Sr, Co, then by carrier impregnation in catalyst solution, finally carry out roasting, be prepared into vehicle tail gas treater [Wang Hui, Zeng Lingke, Duan Bilin etc., automobile exhaust gas purifying installation of ceramic carrier supported catalyst and preparation method thereof: Chinese patent literature CN200710026283.7].Because the viscosity of nitrate aqueous solution is lower, the adhesive ability on ceramic fiber is poor, will affect its catalytic capability.In addition, ceramic fiber need mix with Bond by this patent in advance, is prepared into porous mullite fiber ceramics, and technique is more complicated, increases the cost of product.
The people such as the Song Chonglin of University Of Tianjin have prepared K
xla
1-xcoO
3ceramic fiber as catalyzer [Song Chonglin, Gong Cairong, Fan Guoliang etc., a kind of Ca-Ti ore type fibre body composite oxide catalysts for purifying vehicle exhaust and preparation method thereof: Chinese patent literature CN200710057219.5], because the price of La and Co is higher, the purification plant cost prepared by the method is higher.
The people such as the Zhang Jian of Xibei Inst. of Non-Ferrous Metals are with the carrier of steel fiber (Aludirome) as catalyzer, draft machine tail gas purifier for motor vehicle [Zhang Jian, Tang Huiping, Kang Xinting, a kind of preparation method of metal fiber carrier for automobile exhaust purifier: Chinese patent literature CN200910021837.3].The fiber that the patent of people's applications such as Beijing Shougang Gitane New Materials Co., Ltd. Li Gang is used is also steel fiber (being mainly the alloy of Fe and Cr) [Li Gang, Malaysian celebrates, Tao Ke etc., a kind of heat resistance fiber material of catalyst carrier for purifying automobile exhaust and making method: Chinese patent literature 201010237461.2].But steel fiber is in use easily oxidized and by gas attacks such as NOx, affects its working life.
Summary of the invention
The object of this invention is to provide a kind of vehicle tail gas treater preparation method of anticorrosive, ceramic fiber catalyst carrier that catalytic capability is high, have the advantages that technique is simple, cost is low.
For reaching above object, the present invention takes following technological scheme to be achieved:
A vehicle tail gas treater preparation method for ceramic fiber catalyst carrier, is characterized in that, comprise the steps:
(1) in distilled water, add the inorganic salts of cerium, zirconium, lanthanum, strontium and cobalt, after stirring, obtain aqueous catalyst solution, in aqueous catalyst solution, add colloidal sol forming agent, after stirring, add micelle suspending agent again, obtain stable catalyzer colloidal sol, wherein: the content of zirconium atom is the 10-50% of cerium atom molal weight, the content of lanthanum atom is the 10-50% of cerium atom molal weight, and the content of strontium atom is the 10-50% of cerium atom molal weight, and the content of cobalt atom is the 10-50% of cerium atom molal weight; The molecule content of colloidal sol forming agent in catalyzer colloidal sol is the 100-300% of cerium atom molal weight; The molecule content of micelle suspending agent in catalyzer colloidal sol is the 100-300% of cerium atom molal weight; In catalyzer colloidal sol, the content of water molecule is the 100-300% for cerium atom molal weight;
(2) in the catalyzer colloidal sol of step (1), add the cotton post of ceramic alumina fiber, after soaking 2h, obtain the ceramic fiber cotton post of surface adhesion catalyst colloid;
(3) by the ceramic fiber cotton post of the surface adhesion catalyst colloid of step (2) dry 2-24h under 40-100 DEG C of condition, calcine 0.5-2h at 800-1200, obtain catalyst-loaded ceramic fiber cotton post; Catalyst-loaded ceramic fiber cotton post is loaded with in the metallic case of inner thermal insulating layer, namely obtains vehicle tail gas treater.
In such scheme, the inorganic salts of described cerium, zirconium, lanthanum, strontium and cobalt are its villaumite or nitrate.
Described colloidal sol forming agent is the one in acetic acid, citric acid, oxalic acid, tartaric acid, lactic acid.
Described micelle suspending agent is any one in propylene glycol monomethyl ether, dipropylene glycol methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether.
Ceramic alumina fiber described in step (1) is cotton, and wherein alumina content is greater than 60wt%.
The present invention's aluminium oxide base ceramic fibre is carrier, at applied atop one deck catalyst material, not only have corrosion-resistant, resistant to elevated temperatures excellent mechanical property, catalytic efficiency is all more than or equal to 90%(embodiment 1 and embodiment 6 is 90%, and embodiment 2 and embodiment 7 can up to being 99%).Have that cost is low, technique is simple, the advantages such as long service life.
Because colloidal sol is in the process of displaying, along with the prolongation of time, micelle is grown up, some micelles will condense, and form three-dimensional net structure, and the stability of colloidal sol is declined [MaterialsandManufacturingProcesses, 2011,26 (10): 1374-1377].So in present invention process, in front body colloidal sol, add micelle suspending agent, will the stability of colloidal sol be improved, extend window service time of colloidal sol, colloidal sol will be conducive to and industrially apply.
Embodiment
Below by specific embodiment, the present invention is described in further detail.
A vehicle tail gas treater preparation method for ceramic fiber catalyst carrier, comprises the following steps:
(1) in distilled water, add the inorganic salts of cerium, zirconium, lanthanum, strontium and cobalt, after stirring, obtain aqueous catalyst solution, in aqueous catalyst solution, add colloidal sol forming agent, after stirring, then add micelle suspending agent, obtain stable catalyzer colloidal sol.Table 1 lists the formula composition of 10 the embodiment's catalyzer colloidal sols being numbered 1-10 and the Stability of Sols holding time of preparation.The embodiment determination distilled water different according to table 1, cerium, zirconium, lanthanum, strontium and cobalt, colloidal sol forming agent, the addition of micelle suspending agent colloidal sol.
(2) in the catalyzer colloidal sol of step (1), add ceramic alumina fiber cotton, after soaking 2h, obtain the ceramic fiber cotton post of surface adhesion catalyst colloid;
(3) the ceramic fiber cotton post of the surface adhesion catalyst colloid of step (2) is heat-treated, obtain catalyst-loaded ceramic fiber cotton post; Finally loaded in the metallic case with inner thermal insulating layer, the vehicle tail gas treater of different formulations catalyst carrier can be obtained, heat treatment process see table 2, to the catalytic efficiency of vehicle exhaust see table 2.As can be drawn from Table 2, be 90%(embodiment 1 and embodiment 6 to the minimum treatment effeciency of tail gas), be 99%(embodiment 2 and embodiment 7 to the highest point reason efficiency of tail gas).
Table 1
Table 2
Claims (3)
1. a preparation method for the vehicle tail gas treater of ceramic fiber catalyst carrier, is characterized in that, comprises the steps:
(1) in distilled water, add the inorganic salts of cerium, zirconium, lanthanum, strontium and cobalt, after stirring, obtain aqueous catalyst solution, in aqueous catalyst solution, add colloidal sol forming agent, after stirring, add micelle suspending agent again, obtain stable catalyzer colloidal sol, wherein: the molal weight of zirconium atom is the 10-50% of cerium atom molal weight, the molal weight of lanthanum atom is the 10-50% of cerium atom molal weight, and the molal weight of strontium atom is the 10-50% of cerium atom molal weight, and the molal weight of cobalt atom is the 10-50% of cerium atom molal weight; The molal weight of colloidal sol forming agent in catalyzer colloidal sol is the 100-300% of cerium atom molal weight, and colloidal sol forming agent is the one in acetic acid, citric acid, oxalic acid, tartaric acid, lactic acid; The molal weight of micelle suspending agent in catalyzer colloidal sol is the 100-300% of cerium atom molal weight, and micelle suspending agent is any one in propylene glycol monomethyl ether, dipropylene glycol methyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether; In catalyzer colloidal sol, the molal weight of water is the 100-300% of cerium atom molal weight;
(2) in the catalyzer colloidal sol of step (1), add the cotton post of ceramic alumina fiber, after soaking 2h, obtain the ceramic fiber cotton post of surface adhesion catalyst colloid;
(3) by the ceramic fiber cotton post of the surface adhesion catalyst colloid of step (2) dry 2-24h under 40-100 DEG C of condition, at 800-1200 DEG C of calcining 0.5-2h, catalyst-loaded ceramic fiber cotton post is obtained; Catalyst-loaded ceramic fiber cotton post is loaded with in the metallic case of inner thermal insulating layer, namely obtains vehicle tail gas treater.
2. the preparation method of the vehicle tail gas treater of ceramic fiber catalyst carrier as claimed in claim 1, it is characterized in that, the inorganic salts of described cerium, zirconium, lanthanum, strontium and cobalt are its villaumite or nitrate.
3. the preparation method of the vehicle tail gas treater of ceramic fiber catalyst carrier as claimed in claim 1, is characterized in that, the ceramic alumina fiber described in step (1) is cotton, and wherein alumina content is greater than 60wt%.
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| CN106014583A (en) * | 2016-07-06 | 2016-10-12 | 世嘉宝科技（天津）有限公司 | Manufacturing method for catalysis ceramic tube and automobile exhaust purification device adopting tube |
| CN107970905A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of support type carrier and its preparation method and application |
| CN107970921A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of catalyst with catalysis organic exhaust gas combustion function and its preparation method and application and the method for catalysis organic exhaust gas burning |
| CN113117759B (en) * | 2019-12-31 | 2023-09-01 | 中国石油化工股份有限公司 | Protective agent and preparation method and application thereof |
| CN112778019B (en) * | 2021-01-05 | 2022-12-13 | 山东工业陶瓷研究设计院有限公司 | Functional ceramic membrane material for high-temperature flue gas purification and preparation method thereof |
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| CN101015800A (en) * | 2007-02-07 | 2007-08-15 | 大连理工大学 | Honeycomb metal wire net carrier catalyst for catalytically reducing nitrogen oxide and preparing method thereof |
| JP2009263179A (en) * | 2008-04-25 | 2009-11-12 | Ohara Inc | Photocatalytic glass ceramic and method of manufacturing the same |
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| DE202005018611U1 (en) * | 2005-11-28 | 2006-02-16 | Schierz, Claus, Dipl.-Ing. | Storage mat for the storage of a catalytic converter |
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| CN1504260A (en) * | 2002-12-05 | 2004-06-16 | 四川大学 | Integral fuel gas buring catalyst and process for preparing the same |
| CN1995713A (en) * | 2006-12-13 | 2007-07-11 | 北京英泰世纪环境科技有限公司 | Metal carrier triple-effect catalytic unit and method for making same |
| CN101015800A (en) * | 2007-02-07 | 2007-08-15 | 大连理工大学 | Honeycomb metal wire net carrier catalyst for catalytically reducing nitrogen oxide and preparing method thereof |
| JP2009263179A (en) * | 2008-04-25 | 2009-11-12 | Ohara Inc | Photocatalytic glass ceramic and method of manufacturing the same |
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