CN107855127B - Preparation of high-temperature stable supported cobaltosic oxide catalyst based on strong interaction of metal and carrier, product and application - Google Patents
Preparation of high-temperature stable supported cobaltosic oxide catalyst based on strong interaction of metal and carrier, product and application Download PDFInfo
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- CN107855127B CN107855127B CN201711098478.2A CN201711098478A CN107855127B CN 107855127 B CN107855127 B CN 107855127B CN 201711098478 A CN201711098478 A CN 201711098478A CN 107855127 B CN107855127 B CN 107855127B
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a preparation method, a product and an application of a high-temperature stable supported cobaltosic oxide catalyst based on strong interaction between metal and a carrier3O4A catalyst; putting cobalt nitrate and cerium-zirconium-aluminum solid solution into a beaker, adding deionized water solution, stirring to completely dissolve the cobalt nitrate, slowly adding sodium carbonate solution into the suspension, adjusting the pH to 9, stirring and ultrasonically oscillating, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3 hours to obtain powdery Co3O4A CeZrAlO material. The catalyst is applied to propane catalytic combustion reaction after being treated at the high temperature of 800 ℃, and still has good activity. The catalyst has the advantages of easily available raw materials, simple process, good high-temperature stability and good application prospect.
Description
Technical Field
The invention relates to the field of preparation of nano materials, in particular to a preparation method of a high-temperature stable supported cobaltosic oxide catalyst based on strong interaction between metal and a carrier, a product and application.
Background
Hydrocarbons (HC) are one of the main pollution sources of urban air, most of which are toxic, and some of which are even potential carcinogens, seriously harming the environment and human health. In addition, HC reacts photochemically with NOx, possibly causing photochemical smog pollution, with more serious impact on human health and the ecological environment. The products of catalytic combustion are carbon dioxide and water, so that the method has no secondary pollution and is an ideal method for treating HC pollution.
Low-chain HC has the characteristics of non-polarity, chemical stability and the like, and can be subjected to catalytic combustion reaction at high temperature. Therefore, the development of high activity and high temperature stability catalysts is an urgent and challenging issue. Cobalt oxide has the weakest M-O bond, shows activity comparable to that of a noble metal catalyst in alkane catalytic combustion reaction, and attracts more and more attention.
Nano, sub-nano cobaltosic oxide (Co)3O4) The material has higher specific surface area, more active sites, selectively exposed high-index crystal faces, more high-density step sites, kinking site atoms and the like, and can effectively improve Co3O4Activity of the catalyst. However, under high temperature conditions, the above-mentioned Co3O4The catalyst is easy to agglomerate, have a recombinant structure and the like, and the stability is reduced. Therefore, there is an urgent need to develop high-temperature stable Co3O4A catalyst.
Activated alumina (gamma-Al)2O3) Has the characteristics of rich pore structure, high specific surface area, low price and the like, and is one of the most widely applied catalyst carriers. The catalyst can effectively improve the dispersity of the active components and improve the activity and stability of the catalyst. However, gamma-Al2O3And Co3O4Under the condition of high temperature, inert cobalt aluminate compounds are generated, and the activity of the catalyst is reduced. Under the condition of high temperature for a long time, inert cobalt aluminate or inert cobalt aluminate is completely generated to convert Co3O4Complete coating and complete deactivation of the catalyst.
The cerium-zirconium-aluminum solid solution (CeZrAlO) has good oxygen storage and release capacity and high specific surface area at high temperature. By adjusting the proportion of cerium, zirconium and aluminum, Co is prepared by a reasonable preparation method3O4The carrier is directionally supported at the junction of aluminum and cerium zirconium in the carrier. Hopefully, a small amount of cobalt aluminate is formed at the interface to convert Co into Co under the high-temperature condition3O4Firmly fixed to the carrier surface and having an interfaceThe cerium and the zirconium provide active oxygen to further improve Co3O4Activity of (2).
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to: provides a preparation method of a high-temperature stable supported cobaltosic oxide catalyst based on strong interaction between metal and a carrier.
Yet another object of the present invention is to: provides a product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme:
in order to achieve the purpose, the invention adopts the following technical scheme: a process for preparing the high-temp stable carried cobaltosic oxide catalyst based on the strong interaction between metal and carrier features that the Co nitrate as Co source, sodium carbonate as precipitant and the Ce-Zr-Al sosoloid as carrier are deposited to prepare the carried Co based on the strong interaction between metal and carrier3O4A catalyst comprising the steps of:
the deposition and precipitation method comprises the following specific steps: weighing a proper amount of cobalt nitrate and 1.5g of cerium-zirconium-aluminum solid solution in a beaker, adding 100ml of deionized water solution, stirring to completely dissolve the cobalt nitrate, slowly adding 1mol/L of sodium carbonate solution into the suspension, adjusting the pH to 9, continuously stirring for at least 15min in the process, ultrasonically oscillating for 15-30min to uniformly disperse the cobalt nitrate, filtering, washing and freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain powdery Co, wherein the powdery Co is prepared by3O4A CeZrAlO material; wherein the supported Co3O4Co in catalyst3O4The supporting amount of (B) is 5-25%.
The invention uses cobalt nitrate as a cobalt source, sodium carbonate as a precipitator and CeZrAlO as a carrier to prepare supported Co by a deposition precipitation method3O4. Under high temperature conditions, on the one hand, aluminum and Co3O4Cobalt aluminate formed Co3O4Firmly fixed on the surface of the carrier and maintains Co3O4Higher degree of dispersion; on the other hand, cerium and zirconium provide active oxygen to maintain Co3O4High activity ofAnd (4) sex. The catalyst of the invention has easily obtained raw materials and simple process.
The molar ratio of cerium, zirconium and aluminum in the cerium-zirconium-aluminum solid solution is 1:1: 0.5-1: 1: 2.
The invention provides a high-temperature stable supported cobaltosic oxide catalyst based on strong interaction between metal and a carrier, which is prepared by the method. As a catalyst, the catalyst has good high-temperature stability and excellent application prospect.
The invention provides an application of a high-temperature stable supported cobaltosic oxide catalyst based on strong interaction between metal and a carrier, and the catalyst is applied to a propane catalytic combustion reaction after being subjected to high-temperature treatment at 800 ℃, and still has good activity.
Preparation of a carrier cerium zirconium aluminum solid solution: proper amounts of cerium nitrate, zirconium nitrate and aluminum nitrate were weighed into a beaker, 100ml of deionized water solution was added, and stirred to dissolve completely. Slowly adding 1mol/L sodium carbonate solution into the above solution, adjusting pH to 9, and continuously stirring for at least 15 min. The solution is mixed and then is vibrated for 15-30min by ultrasonic wave to be dispersed evenly. And filtering, washing, freeze-drying and roasting the obtained product at 800 ℃ for 3 hours to obtain a light yellow powdery cerium-zirconium-aluminum solid solution.
Compared with the prior art, the invention has the following advantages:
(1) prepared Co3O4CeZrAlO catalyst, with a small amount of cobalt aluminate to form Co at the interface3O4Firmly fixed on the surface of the carrier and improves Co3O4A degree of dispersion; at the same time, the aluminum at the interface cannot completely consume Co3O4The cobalt aluminate produced is also insufficient to convert Co to3O4And (4) completely coating. Thus, Co produced3O4the/CeZrAlO catalyst has good high-temperature stability.
(2) Prepared Co3O4The CeZrAlO catalyst has good oxygen storage and release capacity at high temperature, and the interface cerium and zirconium can provide active oxygen for reaction to further improve Co3O4Activity of (2).
(3) The method has the characteristics of easily obtained raw materials, simple process, high catalyst activity and the like, and has good application prospect.
Detailed Description
Example 1
S1, weighing 4.341g of cerium nitrate, 4.293g of zirconium nitrate and 1.875g of aluminum nitrate, placing the materials in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the materials.
S2, slowly adding 1mol/L sodium carbonate solution into the solution, adjusting the pH to 9, and continuously stirring for at least 15min in the process. The solution is mixed and then is vibrated for 15-30min by ultrasonic wave to be dispersed evenly.
And S3, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3 hours to obtain a light yellow powdery cerium-zirconium-aluminum solid solution.
S4, weighing 0.5455g of cobalt nitrate and 1.5g of cerium-zirconium-aluminum solid solution in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the cobalt nitrate.
S5, slowly adding 1mol/L sodium carbonate solution into the suspension, adjusting the pH to 9, and continuously stirring for at least 15min in the process. And ultrasonically oscillating for 15-30min to uniformly disperse.
S6, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain black-gray solid powdery Co3O4The material is CeZrAlO-1.
Example 2
S1, weighing 4.341g of cerium nitrate, 4.293g of zirconium nitrate and 3.75g of aluminum nitrate, placing the materials in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the materials.
S2, slowly adding 1mol/L sodium carbonate solution into the solution, adjusting the pH to 9, and continuously stirring for at least 15min in the process. The solution is mixed and then is vibrated for 15-30min by ultrasonic wave to be dispersed evenly.
And S3, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3 hours to obtain a light yellow powdery cerium-zirconium-aluminum solid solution.
S4, weighing 0.5455g of cobalt nitrate and 1.5g of cerium-zirconium-aluminum solid solution in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the cobalt nitrate.
S5, slowly adding 1mol/L sodium carbonate solution into the suspension, adjusting the pH to 9, and continuously stirring for at least 15min in the process. And ultrasonically oscillating for 15-30min to uniformly disperse.
S6, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain black-gray solid powdery Co3O4The material is CeZrAlO-2.
Example 3
S1, weighing 4.341g of cerium nitrate, 4.293g of zirconium nitrate and 5.625g of aluminum nitrate, placing the materials in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the materials.
S2, slowly adding 1mol/L sodium carbonate solution into the solution, adjusting the pH to 9, and continuously stirring for at least 15min in the process. The solution is mixed and then is vibrated for 15-30min by ultrasonic wave to be dispersed evenly.
And S3, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3 hours to obtain a light yellow powdery cerium-zirconium-aluminum solid solution.
S4, weighing 0.5455g of cobalt nitrate and 1.5g of cerium-zirconium-aluminum solid solution in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the cobalt nitrate.
S5, slowly adding 1mol/L sodium carbonate solution into the suspension, adjusting the pH to 9, and continuously stirring for at least 15min in the process. And ultrasonically oscillating for 15-30min to uniformly disperse.
S6, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain black-gray solid powdery Co3O4The material is CeZrAlO-3.
Example 4
S1, weighing 4.341g of cerium nitrate, 4.293g of zirconium nitrate and 7.5g of aluminum nitrate, placing the materials in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the materials.
S2, slowly adding 1mol/L sodium carbonate solution into the solution, adjusting the pH to 9, and continuously stirring for at least 15min in the process. The solution is mixed and then is vibrated for 15-30min by ultrasonic wave to be dispersed evenly.
And S3, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3 hours to obtain a light yellow powdery cerium-zirconium-aluminum solid solution.
S4, weighing 0.5455g of cobalt nitrate and 1.5g of cerium-zirconium-aluminum solid solution in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the cobalt nitrate.
S5, slowly adding 1mol/L sodium carbonate solution into the suspension, adjusting the pH to 9, and continuously stirring for at least 15min in the process. And ultrasonically oscillating for 15-30min to uniformly disperse.
S6, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain black-gray solid powdery Co3O4The material is CeZrAlO-4.
Comparative example 1
S1, weighing 0.5455g of cobalt nitrate and 1.5g of Al2O3100ml of deionized water solution is added into a beaker, and the mixture is stirred to completely dissolve the cobalt nitrate.
S2, slowly adding 1mol/L sodium carbonate solution into the suspension, adjusting the pH to 9, and continuously stirring for at least 15min in the process. And ultrasonically oscillating for 15-30min to uniformly disperse.
S3, filtering, washing, freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain blue solid powdery Co3O4/Al2O3A material.
Application example 1
The evaluation of the catalytic performance of the catalyst was carried out in a quartz tube reactor having an inner diameter of 8mm and a length of 250 mm. The space velocity of the raw material gas is 30000mLg-1 cath-1The concentration of propane is 1000ppm, and the balance gas is air. The results of the catalytic performance tests are shown in table 1.
The foregoing description of specific embodiments of the present invention has been presented. It should be noted that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various changes or modifications within the scope of the claims without affecting the essence of the present invention.
Claims (3)
1. A preparation method of a high-temperature stable supported cobaltosic oxide catalyst based on strong interaction between metal and a carrier is characterized by comprising the following steps: cobalt nitrate is used as a cobalt source, sodium carbonate is used as a precipitator, a cerium-zirconium-aluminum solid solution is used as a carrier, and a deposition precipitation method is utilized to prepare supported Co3O4A catalyst comprising the steps of:
weighing a proper amount of cobalt nitrate and 1.5g of cerium-zirconium-aluminum solid solution in a beaker, adding 100ml of deionized water solution, stirring to completely dissolve the cobalt nitrate, slowly adding 1mol/L of sodium carbonate solution into the suspension, adjusting the pH to 9, continuously stirring for at least 15min in the process, ultrasonically oscillating for 15-30min to uniformly disperse the cobalt nitrate, filtering, washing and freeze-drying the obtained product, and roasting at 800 ℃ for 3h to obtain powdery Co, wherein the powdery Co is prepared by3O4A CeZrAlO material; wherein the supported Co3O4Co in catalyst3O4The loading amount of the catalyst is 5-25%; wherein the content of the first and second substances,
the molar ratio of cerium, zirconium and aluminum in the cerium-zirconium-aluminum solid solution is 1:1: 0.5-2;
preparation of a carrier cerium zirconium aluminum solid solution: weighing a proper amount of cerium nitrate, zirconium nitrate and aluminum nitrate, placing the weighed materials in a beaker, adding 100ml of deionized water solution, and stirring to completely dissolve the materials; slowly adding 1mol/L sodium carbonate solution into the solution, adjusting the pH to 9, and continuously stirring for at least 15min in the process; mixing the solutions, and ultrasonically oscillating for 15-30min to disperse them uniformly; and filtering, washing, freeze-drying and roasting the obtained product at 800 ℃ for 3 hours to obtain a light yellow powdery cerium-zirconium-aluminum solid solution.
2. A high temperature stable supported cobaltosic oxide catalyst based on strong interaction of metal and support, characterized in that it is prepared according to the method of claim 1.
3. The use of the high temperature stable supported cobaltosic oxide catalyst based on strong interaction of metals with the support according to claim 2, characterized in that: the catalyst is applied to propane catalytic combustion reaction after being treated at the high temperature of 800 ℃, and still has good activity.
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| JP2013505996A (en) * | 2010-07-10 | 2013-02-21 | 住友化学株式会社 | Process for producing olefin oxide |
| CN103846089A (en) * | 2014-01-14 | 2014-06-11 | 台州欧信环保净化器有限公司 | Homogeneous solid-solution cerium-zirconium-cobalt-aluminum composite material and preparation method thereof |
| CN104014340A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported cobaltosic oxide catalyst, and preparation method and application thereof |
| CN104971729A (en) * | 2015-07-10 | 2015-10-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Monolithic catalyst for catalytic combustion of propane, and preparation method thereof |
| CN105817229A (en) * | 2016-04-25 | 2016-08-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Rare earth element modified load type cobaltosic oxide catalyst and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013505996A (en) * | 2010-07-10 | 2013-02-21 | 住友化学株式会社 | Process for producing olefin oxide |
| CN103846089A (en) * | 2014-01-14 | 2014-06-11 | 台州欧信环保净化器有限公司 | Homogeneous solid-solution cerium-zirconium-cobalt-aluminum composite material and preparation method thereof |
| CN104014340A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported cobaltosic oxide catalyst, and preparation method and application thereof |
| CN104971729A (en) * | 2015-07-10 | 2015-10-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Monolithic catalyst for catalytic combustion of propane, and preparation method thereof |
| CN105817229A (en) * | 2016-04-25 | 2016-08-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Rare earth element modified load type cobaltosic oxide catalyst and preparation method thereof |
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