CN113368897A - High-activity alumina-supported platinum catalyst and preparation method and application thereof - Google Patents
High-activity alumina-supported platinum catalyst and preparation method and application thereof Download PDFInfo
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- CN113368897A CN113368897A CN202110488995.0A CN202110488995A CN113368897A CN 113368897 A CN113368897 A CN 113368897A CN 202110488995 A CN202110488995 A CN 202110488995A CN 113368897 A CN113368897 A CN 113368897A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
Abstract
The invention discloses a high-activity alumina-supported platinum catalyst, and a preparation method and application thereof, and belongs to the field of catalytic reaction engineering. The technical scheme of the invention is as follows: pretreating the alumina carrier by adopting dielectric barrier discharge organic plasma to obtain the alumina carrier grafted with organic groups; platinum is loaded on the pretreated alumina carrier by an impregnation method, so that the high-activity alumina-loaded platinum catalyst is obtained. The high-activity alumina supported platinum catalyst is prepared by utilizing a green and environment-friendly dielectric barrier discharge low-temperature plasma method, the prepared catalyst has good catalytic activity on catalytic dehydrogenation reaction in the dibenzyl toluene hydrogen storage process, can effectively improve the hydrogen storage efficiency, is popularized and applied to the preparation of liquid organic hydrogen storage carriers, and has good economic benefit.
Description
Technical Field
The invention belongs to the field of catalytic reaction engineering, particularly relates to a preparation method and application of a high-activity alumina-supported platinum catalyst, and particularly relates to a preparation method of a dielectric barrier discharge low-temperature plasma pretreated alumina platinum catalyst and application of the catalyst in catalytic dehydrogenation reaction of perhydrogenated dibenzyltoluene.
Background
The transportation and storage of hydrogen energy are the key points of large-scale application of hydrogen energy, liquid organic hydrogen storage is considered as a hydrogen storage mode with great development potential, and common liquid organic hydrogen storage carriers mainly comprise benzene, toluene, carbazoles, indoles, benzyl toluene and the like. Dibenzyl toluene is a mature industrial heat conducting oil and is applied to the field of hydrogen storage. It has a high theoretical hydrogen storage density (6.2 wt%) and good thermal stability. In addition, the dibenzyl toluene has a lower melting point (-34 to-36 ℃) and a high boiling point (390 ℃) so that the dibenzyl toluene can store hydrogen under extreme conditions of extreme cold, extreme heat and the like, however, the higher dehydrogenation temperature and the lower dehydrogenation activity are main problems restricting the development of the dibenzyl toluene hydrogen storage.
In the catalytic dehydrogenation reaction of perhydrodibenzyltoluene, compared with other catalysts such as Pd/C, Pd/Al2O3And Pd/Al2O3，Pt/Al2O3The catalyst shows more excellent catalytic activity. Since the carrier has a great influence on the catalyst activity, modification of the carrier is an important method for improving the catalytic activity. The plasma is a green and environment-friendly treatment technology, and can be used for modifying the surface physical and chemical properties of the material, such as changing surface groups, generating defect sites and the like, so that the material has specific excellent properties.
Pt/Al currently used2O3The catalyst is not sufficiently active for the catalytic dehydrogenation of hydrogenated dibenzyltoluene.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-activity alumina-supported platinum catalyst, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a high-activity alumina supported platinum catalyst, which comprises the following steps:
pretreating the alumina carrier by adopting organic atmosphere dielectric barrier discharge organic atmosphere plasma to obtain the alumina carrier grafted with organic groups; platinum is loaded on an organic alumina carrier by an impregnation method to obtain the high-activity alumina-loaded platinum catalyst.
Preferably, the alumina support is pre-treated with a dielectric barrier discharge organic atmosphere plasma wherein the organic atmosphere is methane or acetic acid.
Further preferably, when the organic atmosphere is methane, the preparation method of the grafted organic group alumina carrier is as follows:
by using Al2O3The powder is used as a carrier precursor, a mixed gas of methane gas and argon gas is used as a working gas, the volume fraction of methane is 5% -95%, the discharge voltage is 20-60kV of peak-to-peak value, and the discharge time is 1-20min, so that the methane alumina carrier is obtained.
Further preferably, when the organic atmosphere is acetic acid, the preparation method of the organic group grafted alumina carrier is as follows:
by using Al2O3The powder is used as a carrier precursor, argon is used as working gas, the powder passes through a bubbler filled with acetic acid at room temperature, the discharge voltage is 20-60kV at the peak-peak value, and the discharge time is 1-20min, so that the methane alumina carrier is obtained.
Further preferably, the discharge medium is made of quartz glass, the thickness of the medium is 0.2-5mm, and the discharge distance is 2-50 mm.
Still more preferably, the discharge voltage is 20 to 60kV peak-to-peak.
Preferably, the platinum is loaded on the organic alumina carrier by an impregnation method, and the specific operations comprise:
dipping a chloroplatinic acid solution on an organic alumina carrier by an isometric dipping method, drying at the temperature of below 100 ℃, and roasting at the temperature of 150-400 ℃ for 0.5-6 h in a hydrogen atmosphere to obtain the high-activity alumina supported platinum catalyst.
Further preferably, the loading amount of platinum in the high-activity alumina-supported platinum catalyst is 0.5-5% of the support amount of the organic group grafted alumina carrier.
The invention also discloses the high-activity alumina supported platinum catalyst prepared by the preparation method.
The invention also discloses an application of the high-activity alumina-supported platinum catalyst in catalyzing dehydrogenation reaction of fully hydrogenated dibenzyl toluene, wherein the conditions for catalyzing dehydrogenation reaction of fully hydrogenated dibenzyl toluene are as follows: the reaction temperature is 240-310 ℃; the reaction pressure is 1kPa-1 MPa.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes a green and environment-friendly dielectric barrier discharge low-temperature plasma method to prepare an organic alumina supported platinum catalyst, ionizes organic atmosphere by adopting a dielectric barrier discharge method to generate high-energy plasma so as to modify the surface of an alumina carrier, grafts organic groups on the surface of the carrier, and then carries out Pt loading on the carrier to prepare the target catalyst.
Furthermore, the organic atmosphere used in the invention selects methane and acetic acid, and the methyl in the prepared catalyst improves the dispersity of platinum and influences the appearance of platinum-loaded particles, thereby showing better catalytic hydrogenation dibenzyl toluene dehydrogenation activity, CH3The COO-group acts as an electron donor for the Pt particles resulting in a large increase in dehydrogenation activity.
The prepared platinum catalyst with alumina oxide has good catalytic activity on catalytic dehydrogenation reaction in the hydrogen storage process of dibenzyl toluene, can effectively improve the hydrogen storage efficiency, is popularized and applied to the liquid organic hydrogen storage process, and has good economic benefit.
Further, the Pt/Al prepared by the invention2O3-P-CH4Catalyst or Pt/Al2O3-P-CH3The COOH catalyst can be used for the high-efficiency catalytic dehydrogenation reaction of perhydro dibenzyl toluene, wherein Pt/Al2O3-P-CH4Has high catalytic dehydrogenation activity: under the conditions that the molar ratio of the Pt to the H18-DBT is 0.003, the reaction temperature is 270 ℃, and the reaction pressure is atmospheric pressure, the dehydrogenation amount reaches 74.8 percent in 5 hours, the dehydrogenation rate is improved by 19.5 percent compared with 62.2 percent of the dehydrogenation rate of a catalyst without plasma treatment, and the Pt/Al catalyst is prepared by adding Pt and H18-DBT into the catalyst2O3-P-CH3COOH has high catalytic dehydrogenation activity, and the dehydrogenation rate of the COOH under the same dehydrogenation conditions is 74.2 percent, compared with Pt/Al2O3The improvement is 18.5%.
Drawings
FIG. 1 is an infrared spectrum of an organic alumina supported platinum catalyst prepared according to the present invention;
FIG. 2 is a schematic diagram of a dielectric barrier discharge low temperature plasma reactor.
Wherein: 1-a high voltage electrode; 2-quartz glass; 3-a zero potential electrode; 4-low temperature plasma; 5-sample.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the catalyst adopts methane or acetic acid atmosphere medium to block discharge low-temperature plasma to pre-treat an alumina carrier (respectively expressed as Al)2O3-P-CH4Or Al2O3-P-CH3COOH), the active component Pt is supported on Al2O3-P-CH4Or Al2O3-P-CH3COOHThe Pt loading is 0.5-5%, which is respectively marked as Pt/Al2O3-P-CH4And Pt/Al2O3-P-CH3COOH. The preparation method comprises the following specific steps:
(1) pretreatment of alumina carrier by adopting methane atmosphere dielectric barrier discharge low-temperature plasma
Adopting active Al after being roasted at 600 DEG C2O3Powder is used as a carrier precursor, the powder is evenly paved in a plasma discharge reactor, quartz glass is used as a barrier medium, the thickness of the medium is 0.2-5mm, the discharge distance is 2-50mm, the volume fraction of methane in a working gas of argon and methane mixed gas is 5% -95%, the discharge voltage is 20-60kV at the peak value, the discharge time is 1-20min, and finally the methane medium barrier discharge low-temperature plasma pretreated alumina carrier marked as Al is obtained2O3-P-CH4；
(2) Pretreatment of alumina carrier by adopting acetic acid atmosphere dielectric barrier discharge low-temperature plasma
Except that the working gas is acetic acid saturated gas formed by flowing argon through a bubbler filled with acetic acid, the other conditions are the same as the plasma treatment condition (1), and finally the low-temperature plasma pretreated alumina carrier with the acetic acid atmosphere dielectric barrier discharge is obtained, and the mark is Al2O3-P-CH3COOH；
(3) Preparation of Pt/Al by dipping method2O3-P-CH4Or Pt/Al2O3-P-CH3COOH catalyst
According to the metering ratio, the required amount of H is added by adopting an equal volume immersion method2PtCl6Impregnating Al with the solution2O3-P-CH4Or Al2O3-P-CH3On COOH, the Pt mass percentage content is 0.5-5%, then dried under 100 ℃, and roasted for 0.5-6 hours under the atmosphere of hydrogen at the temperature of 150-400 ℃ to respectively obtain Pt/Al2O3-P-CH4Or Pt/Al2O3-P-CH3A COOH catalyst.
The plasma reactor for implementing the preparation method of the invention is shown in fig. 2, wherein the discharge medium used in the discharge process described in (1) and (2) above is quartz glass, the thickness of the medium is 0.2-5mm, and the discharge distance is 2-50 mm. The peak value of the discharge voltage is 20-60 kV.
Example 1
Pt/Al is prepared as follows2O3-P-CH4Catalyst and process for preparing same
(1) Weighing 0.5gAl2O3And laid in a plasma reactor with a quartz glass thickness of 1mm and a discharge gap of 8 mm. Methane and argon respectively flow through the reactor at flow rates of 50ml/min, sinusoidal waveform discharge is adopted, the voltage is 45kV at the peak-peak value, the discharge time is 3min each time, 5 times of discharge are carried out totally, 15 minutes are carried out between every two times, and the sample is stirred during the period, so that Al is finally obtained2O3-P-CH4；
(2) Impregnating H with equal volume2PtCl6Impregnating Al with the solution2O3-P-CH4Drying at 80 deg.C for 12 hr, and calcining at 400 deg.C for 2 hr in hydrogen atmosphere to obtain 3% Pt/Al2O3-P-H2A catalyst.
Putting 0.8g of the catalyst into a 50mL high-pressure stirring reaction kettle, putting 10mL of perhydro dibenzyltoluene, introducing pure hydrogen for purging, keeping the pressure at normal pressure, raising the temperature to 270 ℃ for dehydrogenation reaction, wherein the dehydrogenation rate is 74.8 percent in 5 hours, and the dehydrogenation rate is 3 percent of Pt/Al2O3The dehydrogenation rate is improved by 19.5 percent and is 62.6 percent, and the catalytic activity is obviously improved.
Example 2
Pt/Al is prepared as follows2O3-P-CH3COOH catalyst:
the flow rate of argon gas was controlled to be 100ml/min, and the flow was passed through a bubbler containing acetic acid and then through a reactor, and the rest of the preparation and implementation of the catalyst were the same as in example 1.
In the catalytic reaction, the dehydrogenation rate in 5 hours is 74.2 percent, which is 18.5 percent higher than that of the catalyst without plasma treatment, wherein the dehydrogenation rate is 62.6 percent.
Referring to FIG. 1, Pt/Al prepared by the invention2O3-P-CH4Surface ofHaving methyl and methylene groups, Pt/Al2O3-P-CH3The surface of COOH has CH3A COO-group and a small amount of methyl; the curve (a) in fig. 1 is used for comparison to show that the support surface not treated with methane and acetic acid atmosphere dbd-discharge plasma does not contain relevant groups: 2964, 2930, 2877, 1456 and 1386cm in curve (b) in FIG. 1-1Represents methyl and methylene, 1424, 1473 and 1608cm in curve (c) in FIG. 1-1The peak of (A) represents CH3A COO-group. The methyl improves the dispersity of platinum and influences the appearance of platinum-loaded particles, thereby showing better catalytic hydrogenation dibenzyl toluene dehydrogenation activity, CH3The COO-group acts as an electron donor for the Pt particles resulting in a large increase in dehydrogenation activity.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a high-activity alumina-supported platinum catalyst is characterized by comprising the following steps:
pretreating the alumina carrier by adopting organic atmosphere dielectric barrier discharge organic atmosphere plasma to obtain the alumina carrier grafted with organic groups; platinum is loaded on an organic alumina carrier by an impregnation method to obtain the high-activity alumina-loaded platinum catalyst.
2. The method for preparing a high-activity alumina-supported platinum catalyst according to claim 1, wherein the alumina support is pre-treated with a dielectric barrier discharge plasma in an organic atmosphere, wherein the organic atmosphere is methane or acetic acid.
3. The method for preparing a high-activity alumina-supported platinum catalyst according to claim 2, wherein when the organic atmosphere is methane, the method for preparing the organic group-grafted alumina carrier comprises the following steps:
with Al2O3The powder is used as a carrier precursor, a mixed gas of methane gas and argon gas is used as a working gas, the volume fraction of methane is 5% -95%, the discharge voltage is 20-60kV of peak-to-peak value, and the discharge time is 1-20min, so that the methane alumina carrier is obtained.
4. The method for preparing a high-activity alumina-supported platinum catalyst according to claim 2, wherein when the organic atmosphere is acetic acid, the method for preparing the organic group-grafted alumina carrier is as follows:
by using Al2O3The powder is used as a carrier precursor, argon is used as working gas, the powder passes through a bubbler filled with acetic acid at room temperature, the discharge voltage is 20-60kV at the peak-peak value, and the discharge time is 1-20min, so that the methane alumina carrier is obtained.
5. The method for preparing a highly active alumina-supported platinum catalyst according to claim 3 or 4, wherein the discharge medium is quartz glass, the thickness of the medium is 0.2 to 5mm, and the discharge distance is 2 to 50 mm.
6. The method for preparing a highly active alumina-supported platinum catalyst according to claim 3 or 4, wherein a discharge voltage is 20 to 60kV at a peak-to-peak value.
7. The method for preparing the high-activity alumina-supported platinum catalyst according to claim 1, wherein platinum is supported on an organic alumina carrier by an impregnation method, and the specific operations comprise:
dipping a chloroplatinic acid solution on an organic alumina carrier by an isometric dipping method, drying at the temperature of below 100 ℃, and roasting at the temperature of 150-400 ℃ for 0.5-6 h in a hydrogen atmosphere to obtain the high-activity alumina supported platinum catalyst.
8. The method of claim 7, wherein the amount of platinum carried on the highly active alumina-supported platinum catalyst is 0.5% to 5% of the weight of the organic group-grafted alumina carrier.
9. The high-activity alumina-supported platinum catalyst prepared by the preparation method of any one of claims 1 to 7.
10. The use of the highly active alumina-supported platinum catalyst of claim 9 to catalyze the dehydrogenation of perhydrogenated dibenzyltoluene under the conditions: the reaction temperature is 240-310 ℃; the reaction pressure is 1kPa-1 MPa.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080056928A1 (en) * | 2003-10-15 | 2008-03-06 | Timothy Rex Bunce | Functionalisation of Particles |
| US20080145553A1 (en) * | 2006-07-31 | 2008-06-19 | Tekna Plasma Systems Inc. | Plasma surface treatment using dielectric barrier discharges |
| CN101602017A (en) * | 2009-07-22 | 2009-12-16 | 大连理工大学 | Utilize low temperature plasma to prepare the method for load type metal catalyst |
| CN105536777A (en) * | 2015-12-17 | 2016-05-04 | 杭州电子科技大学 | Catalytic combustion active ingredient highly-dispersed catalyst and preparation method thereof |
| CN107008511A (en) * | 2017-04-13 | 2017-08-04 | 大连大学 | A kind of method that atmosphere cold plasma reduction prepares load type metal catalyst |
| CN107649121A (en) * | 2017-10-24 | 2018-02-02 | 石河子大学 | The method of modifying and modified manganese based denitration catalyst and preparation method of a kind of manganese based denitration catalyst |
| US20190321799A1 (en) * | 2018-04-18 | 2019-10-24 | California Institute Of Technology | Dielectric barrier discharge reactor for catalytic nonthermal plasma production of hydrogen from methane |
-
2021
- 2021-04-29 CN CN202110488995.0A patent/CN113368897B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080056928A1 (en) * | 2003-10-15 | 2008-03-06 | Timothy Rex Bunce | Functionalisation of Particles |
| US20080145553A1 (en) * | 2006-07-31 | 2008-06-19 | Tekna Plasma Systems Inc. | Plasma surface treatment using dielectric barrier discharges |
| CN101573467A (en) * | 2006-07-31 | 2009-11-04 | 泰克纳等离子系统公司 | Plasma surface treatment using dielectric barrier discharges |
| CN101602017A (en) * | 2009-07-22 | 2009-12-16 | 大连理工大学 | Utilize low temperature plasma to prepare the method for load type metal catalyst |
| CN105536777A (en) * | 2015-12-17 | 2016-05-04 | 杭州电子科技大学 | Catalytic combustion active ingredient highly-dispersed catalyst and preparation method thereof |
| CN107008511A (en) * | 2017-04-13 | 2017-08-04 | 大连大学 | A kind of method that atmosphere cold plasma reduction prepares load type metal catalyst |
| CN107649121A (en) * | 2017-10-24 | 2018-02-02 | 石河子大学 | The method of modifying and modified manganese based denitration catalyst and preparation method of a kind of manganese based denitration catalyst |
| US20190321799A1 (en) * | 2018-04-18 | 2019-10-24 | California Institute Of Technology | Dielectric barrier discharge reactor for catalytic nonthermal plasma production of hydrogen from methane |
Non-Patent Citations (4)
| Title |
|---|
| LANBO DI ET AL.,: "An alternative atmospheric-pressure cold plasma method for synthesizing Pd/P25 catalysts with the assistance of ethanol", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 42, no. 16, pages 1, XP085008265, DOI: 10.1016/j.ijhydene.2017.02.212 * |
| LIBIN SHI ET.,: "Pt Catalysts Supported on H2 and O2 Plasma-Treated Al2O3 for Hydrogenation and Dehydrogenation of the Liquid Organic Hydrogen Carrier Pair Dibenzyltoluene and Perhydrodibenzyltoluene", ACS CATALYSIS, vol. 10, no. 18, pages 2 * |
| 代斌,宫为民,张秀玲,何仁: "等离子体技术在催化剂制备中的应用", 现代化工, vol. 21, no. 12, pages 13 * |
| 田树勋,李振花,王海涛,何菲: "空气低温等离子体对Ni基催化剂的改性作用", 化学反应工程与工艺, vol. 20, no. 02, pages 97 - 103 * |
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