CN105396571A - Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof - Google Patents

Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof Download PDF

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Publication number
CN105396571A
CN105396571A CN201410468538.5A CN201410468538A CN105396571A CN 105396571 A CN105396571 A CN 105396571A CN 201410468538 A CN201410468538 A CN 201410468538A CN 105396571 A CN105396571 A CN 105396571A
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composite oxide
mesoporous
catalyst
preparing catalyst
gallium
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刘俊
侯红美
邱爱玲
殷玉圣
魏士新
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention belongs to the technical field of mesoporous oxides, and provides a mesoporous Ga/Al composite oxide catalyst, a preparation method and applications thereof. According to the present invention, the Ga/Al composite oxide having a regular mesoporous structure is prepared through a solvent evaporation induction self-assembly technology, the preparation process of the method is simple, the Ga species is highly dispersed on the Al oxide to form the solid solution, and the characteristics of ordered pore channel structure, high specific surface area and the like are provided; and with the application of the class of the oxides in the propylene production reaction through oxidative dehydrogenation of propane under the CO2 atmosphere, the excellent catalysis effect is provided, and when the reaction is performed for 10 min, the propane conversion rate is 52%, the propylene selectivity is 96%, and the propane conversion rate and the propylene selectivity are higher than the Ga/Al catalyst prepared through the impregnation method so as to provide good application prospects.

Description

A kind of mesoporous Ga/Al composite oxide catalysts and its preparation method and application
Technical field
The present invention relates to mesopore metal oxide field, specifically, the invention provides a kind of preparation method and the application with the Ga/Al composite oxide catalysts of two-dimentional hexagonal structure.
Background technology
Propylene is a kind of important industrial chemicals, can be used for the production of the materials such as polypropylene, polyacrolein and acrylic acid.But because propylene that is steamed cracking and fluid catalytic cracking production far can not meet the demand in market, in recent years, the catalytic dehydrogenation propylene of propane receives the concern of more researchers.Dehydrogenating propane is strong exothermal reaction, need high reaction temperature, but high temperature easily produces thermal cracking side reaction, result result in the generation of a large amount of micromolecular alkane and coking, thus reduce the selective of catalyst and stability, therefore substitute Non-oxidative dehydrogenation with dioxygen oxidation dehydrogenation and cause more concern.But, due to the easy deep oxidation of propane, this reaction selective extremely low.Recently, research finds with CO 2be applied to dehydrogenating low-carbon alkane reaction as mild oxidizer and achieve significant effect, higher olefine selective can also be obtained obtaining high alkane conversion while.
Ga 2o 3the especially concern of researcher is received as a kind of new catalyst, it is at first for the aromatization of propane, dehydrogenation reaction application as far back as 1998 by Japanese Nakagawa group is reported [NakagawaK.etal.ChemicalCommunications, 1998, (9): 1025-1026].In a series of commercial oxidation thing ethane dehydrogenation expression activitiy, Ga 2o 3dehydrogenation activity be considered to the stronger Cr of ability of dehydrogenation higher than tradition 2o 3and V 2o 5.Usual preparation metal oxidation catalyst mainly contains infusion process, coprecipitation, sol-gel process and mechanical mixing etc., but the deficiency such as the catalyst obtained of these methods has dispersed uneven, specific area ground and particle is large, result constrains active raising.As the Ga that the people such as Michorczyk adopt infusion process to prepare 2o 3/ Al 2o 3catalyst is in the reaction of preparing propene by oxidative dehydrogenation of propane, and the conversion ratio of propane is only 5.4%.
Since the mesoporous SiO of high-sequential in 1992 2since material is synthesized first, these mesoporous materials are because have higher specific area, pore volume, homogeneous pore-size distribution and regular structure, active specy can be made to be dispersed on the mesopore metal oxide of these high-specific surface areas, to show excellent catalysis and photoelectric properties.These characteristics mainly owing to special skin effect, quantum size effect and the effect between active material and carrier.Especially at catalytic field, these features make mesoporous material can serve as the effect of carrier well, the meso-hole structure of high-sequential can stop the sintering of metal nanoparticle, avoid catalyst because of sintering inactivation, thus to the research of mesoporous material cause more and more researcher pay close attention to.
Therefore the present invention is directed at present for CO 2the Ga of preparing propene by oxidative dehydrogenation of propane reaction under atmosphere 2o 3/ Al 2o 3catalyst there is the defects such as surface area is little, poor dispersion thus conditioned response is active and the raising of target product selectivity, propose a kind of catalyst preparing the Ga/Al composite oxides with two-dimentional six side's mesoscopic structures, to obtaining high conversion of propane and Propylene Selectivity.
Summary of the invention
An object of the present invention is to provide a kind of mesoporous Ga/Al composite oxide catalysts.
Another object of the present invention is to provide a kind of preparation method of mesoporous Ga/Al composite oxide catalysts.
Another object of the present invention is to provide a kind of application of mesoporous Ga/Al composite oxide catalysts.
The invention provides a kind of simple and easy mesoporous Ga/Al composite oxide catalysts effectively preparing high-sequential, in this catalyst, gallium oxide load is on the oxide of mesoporous aluminium, and wherein the weight content of Ga is 1-10%.This catalyst has the mesoscopic structure of high dispersive, high-specific surface area and two-dimentional six sides.
The invention provides a kind of preparation method of mesoporous Ga/Al composite oxide catalysts, adopt the preparation of solvent evaporation induced self-assembly technology, concrete steps are as follows: be first dissolved in solvent by structure directing agent, abundant stirring makes structure directing agent dissolve, then aluminium isopropoxide and isopropyl alcohol gallium join in above-mentioned solution, proceed to stir, red fuming nitric acid (RFNA) is added drop-wise in above-mentioned mixed liquor, continue to be stirred to and dissolve completely, be placed in baking oven, collect the solid matter obtained, through calcination processing, finally obtain Ga/Al composite oxide catalysts.
Usually, described structure directing agent is the combination of one or more in P123, F127, CTAB.
Described solvent is ethanol, acetonitrile, oxolane, methyl alcohol or propyl alcohol.
The mol ratio of described aluminium isopropoxide and isopropyl alcohol gallium is 20:1-5:1.
The temperature of described baking oven is 40-100 DEG C.
Describedly be placed in the baking oven time at 10-72h.
Described sintering temperature is 400-800 DEG C; Roasting time is 3-6h.
The purposes of described Ga/Al composite oxide catalysts, is characterized in that being applied to CO 2under atmosphere preparing propene by oxidative dehydrogenation of propane reaction in.
Remarkable result provided by the present invention just can obtain the Ga/Al composite oxides with meso-hole structure by easy method, the oxide of gallium can high dispersive on aluminum oxide, present regular orderly meso-hole structure, there are more four-coordination Ga species on surface, Lewis acidity is stronger, and there is good heat endurance, these significant advantages are suitable for CO 2atmosphere producing propylene by propane dehydrogenation, mixing of Al can dilute surface Ga simultaneously 3+distribution, this is very favorable for reducing generation of carbon distribution, can extend this catalyst at CO 2service life under atmosphere producing propylene by propane dehydrogenation.
Accompanying drawing explanation
Fig. 1 is the low-angle XRD collection of illustrative plates of 5%Ga/Al composite oxide catalysts in embodiment 1,1.1 oplace's appearance stronger diffraction maximum, indicates this sample and has meso-hole structure.
Fig. 2 is the TEM photo of 5%Ga/Al composite oxide catalysts in embodiment 1, can observe these composite oxides have regular orderly pore passage structure from this figure.
Detailed description of the invention
Embodiment 1
Taking 3.0gP123 is dissolved in 60.0mL ethanol, fully stirs and makes it dissolve.After P123 dissolves completely, 8.0g aluminium isopropoxide and 0.35g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h under 673K, obtains Ga/Al composite oxides.The little angle XRD of this sample is shown in Fig. 1, and TEM photo as shown in Figure 2.
Embodiment 2
Taking 3.0gF127 is dissolved in 60.0mL ethanol, fully stirs and makes it dissolve.After P123 dissolves completely, 8.0g aluminium isopropoxide and 0.35g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h under 673K, obtains Ga/Al composite oxides.The specific area of sample is 230m 2/ g.
Embodiment 3
Taking 3.0gP123 is dissolved in 60.0mL ethanol, fully stirs and makes it dissolve.After P123 dissolves completely, 10.0g aluminium isopropoxide and 1.20g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h under 673K, obtains Ga/Al composite oxides.The specific area of sample is 260m 2/ g.
Embodiment 4
Taking 3.0gP123 is dissolved in 60.0mL ethanol, fully stirs and makes it dissolve.After P123 dissolves completely, 10.0g aluminium isopropoxide and 1.20g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h at 873k, obtains Ga/Al composite oxides.The specific area of sample is 210m 2/ g.
Embodiment 5
Taking 3.0gCTAB is dissolved in 60.0mL ethanol, fully stirs and makes it dissolve.After P123 dissolves completely, 10.0g aluminium isopropoxide and 1.20g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h under 673K, obtains Ga/Al composite oxides.The specific area of sample is 240m 2/ g.
Embodiment 6
Taking 1.0gP123 and 1.0gF127 is dissolved in 60.0mL ethanol, fully stirs and makes it dissolve.After P123 dissolves completely, 10.0g aluminium isopropoxide and 1.20g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h under 673K, obtains Ga/Al composite oxides.The specific area of sample is 280m 2/ g.
Embodiment 7
Taking 3.0gP123 is dissolved in 60.0mL oxolane, fully stirs and makes it dissolve.After P123 dissolves completely, 8.0g aluminium isopropoxide and 0.35g isopropyl alcohol gallium are joined in above-mentioned solution, stir until dissolve, then drip 4.40mL red fuming nitric acid (RFNA) and be added drop-wise in this solution, cover with PE film under being placed in room temperature, abundant stirring makes it mix, again this mixed solution is placed in the baking oven 2 days that temperature is 333K, obtains solid, grind, roasting 4h under 673K, obtains Ga/Al composite oxides.
Embodiment 85%Ga/Al composite oxides are used for CO 2the catalytic performance of preparing propene by oxidative dehydrogenation of propane reaction under atmosphere
The sample prepared by embodiment 1 is adopted to be used for CO 2atmosphere producing propylene by propane dehydrogenation reacts, and sample is placed in atmospheric flow reactor, amount of samples is 0.5g, and sample granularity is 60-80 orders, and reaction temperature is 823K, and gas composition is V (C 3h 8): V (CO 2): V (N 2)=2:4:29, when reaction proceeds to 10min, the conversion ratio of propane is 52%, and the selective of propylene is 96%.
control experiment
The 5%Ga/Al composite oxides that embodiment 9 adopts infusion process to prepare are for CO 2the catalytic performance of preparing propene by oxidative dehydrogenation of propane reaction under atmosphere.Prepare the oxide of mesoporous Al according to the method for embodiment 1, then adopt infusion process gallium species to be carried on the oxide of mesoporous Al, the weight of gallium is 5%, prepares sample, be labeled as A, A is used for CO through processes such as oven dry, roastings 2atmosphere producing propylene by propane dehydrogenation reacts, and its course of reaction is with embodiment 8, and when reaction proceeds to 10min, the conversion ratio of propane is 38%, and the selective of propylene is 92%.

Claims (9)

1. a mesoporous Ga/Al composite oxide catalysts, it is characterized in that in this catalyst, gallium oxide load is on the oxide of mesoporous aluminium, wherein the weight content of Ga is 1-10%, and catalyst has the mesoscopic structure of high dispersive, high-specific surface area and two-dimentional six sides.
2. prepare the method for composite oxide catalysts according to claim 1 for one kind, it is characterized in that, adopt the preparation of solvent evaporation induced self-assembly technology, concrete steps are as follows: be first dissolved in solvent by structure directing agent, abundant stirring makes structure directing agent dissolve, then aluminium isopropoxide and isopropyl alcohol gallium join in above-mentioned solution, proceed to stir, red fuming nitric acid (RFNA) is added drop-wise in above-mentioned mixed liquor, continue to be stirred to and dissolve completely, be placed in baking oven, collect the solid matter obtained, through calcination processing, finally obtain Ga/Al composite oxide catalysts.
3. method for preparing catalyst as claimed in claim 2, is characterized in that structure directing agent is the combination of one or more in P123, F127, CTAB.
4. method for preparing catalyst as claimed in claim 2, is characterized in that solvent is ethanol, acetonitrile, oxolane, methyl alcohol or propyl alcohol.
5. method for preparing catalyst as claimed in claim 2, is characterized in that the mol ratio of aluminium isopropoxide and isopropyl alcohol gallium is 20:1-5:1.
6. method for preparing catalyst as claimed in claim 2, is characterized in that the temperature of baking oven is 40-100 DEG C.
7. method for preparing catalyst as claimed in claim 2, is characterized in that being placed in the baking oven time at 10-72h.
8. method for preparing catalyst as claimed in claim 2, is characterized in that sintering temperature is 400-800 DEG C.
9. the purposes of Ga/Al composite oxide catalysts as claimed in claim 1, is characterized in that being applied to CO 2under atmosphere preparing propene by oxidative dehydrogenation of propane reaction in.
CN201410468538.5A 2014-09-16 2014-09-16 Mesoporous Ga/Al composite oxide catalyst, preparation method and applications thereof Pending CN105396571A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109608301A (en) * 2017-10-17 2019-04-12 苏州大学 A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene
CN112973661A (en) * 2019-12-16 2021-06-18 北京中能炜业科技发展有限公司 Alkane dehydrogenation catalyst, preparation method and application thereof
US11986799B2 (en) 2018-12-28 2024-05-21 Dow Global Technologies Lllc Catalysts comprising a zirconia and gallium oxide component for production of C2 to C4 olefins

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1696085A (en) * 2005-04-28 2005-11-16 复旦大学 Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide
CN101219908A (en) * 2007-09-21 2008-07-16 南京大学 Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof
CN101411978A (en) * 2008-11-28 2009-04-22 南开大学 Catalyst for preparing propylene by propane dehydrogenation as well as preparation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1696085A (en) * 2005-04-28 2005-11-16 复旦大学 Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide
CN101219908A (en) * 2007-09-21 2008-07-16 南京大学 Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof
CN101411978A (en) * 2008-11-28 2009-04-22 南开大学 Catalyst for preparing propylene by propane dehydrogenation as well as preparation and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109608301A (en) * 2017-10-17 2019-04-12 苏州大学 A kind of method that catalytic dehydrogenation of butanes prepares butylene and butadiene
CN109608301B (en) * 2017-10-17 2021-10-19 苏州大学 Method for preparing butylene and butadiene through catalytic dehydrogenation of butane
US11986799B2 (en) 2018-12-28 2024-05-21 Dow Global Technologies Lllc Catalysts comprising a zirconia and gallium oxide component for production of C2 to C4 olefins
CN112973661A (en) * 2019-12-16 2021-06-18 北京中能炜业科技发展有限公司 Alkane dehydrogenation catalyst, preparation method and application thereof
CN112973661B (en) * 2019-12-16 2024-05-24 山西腾茂科技股份有限公司 Alkane dehydrogenation catalyst and preparation method and application thereof

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Application publication date: 20160316