CN113368897B - 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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- CN113368897B CN113368897B CN202110488995.0A CN202110488995A CN113368897B CN 113368897 B CN113368897 B CN 113368897B CN 202110488995 A CN202110488995 A CN 202110488995A CN 113368897 B CN113368897 B CN 113368897B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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 an 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, and the high-activity alumina loaded platinum catalyst is obtained. The method for preparing the high-activity alumina-supported platinum catalyst by using the green and environment-friendly dielectric barrier discharge low-temperature plasma method 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 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, and particularly relates to a preparation method and application of a high-activity alumina-supported platinum catalyst, in particular to a preparation method of a dielectric barrier discharge low-temperature plasma pretreatment alumina-supported platinum catalyst and application of the catalyst in a perhydrogenation dibenzyl toluene catalytic dehydrogenation reaction.
Background
The transportation and storage of hydrogen energy are key to the large-scale application of hydrogen energy, the liquid organic matter hydrogen storage is considered as a hydrogen storage mode with great development potential, and the common liquid organic matter hydrogen storage carrier mainly comprises benzene, toluene, carbazole, indole, benzyl toluene and the like. Dibenzyl toluene is industrial heat conduction oil which is mature in application and has been 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 relatively low melting point (-34 to minus 36 ℃) and the high boiling point (390 ℃) of the dibenzyl toluene enable the dibenzyl toluene to store hydrogen under extreme conditions such as extremely cold, high heat and the like, however, the relatively high dehydrogenation temperature and the relatively low dehydrogenation activity are main problems for restricting the hydrogen storage development of the dibenzyl toluene.
In the catalytic dehydrogenation of the perhydrogenated dibenzyl toluene, pd/Al is used as a catalyst in comparison with other catalysts such as Pd/C 2 O 3 And Pd/Al 2 O 3 ，Pt/Al 2 O 3 The catalyst shows more excellent catalytic activity. Since the nature of the support has a great influence on the activity of the catalyst, modification of the support is an important method for improving the catalytic activity. The plasma is an environment-friendly treatment technology, and can be used for modifying the physical and chemical properties of the surface of the material, such as changing surface groups, generating defect sites and the like, so that the material has specific excellent properties.
Currently applied Pt/Al 2 O 3 The catalyst is not yet sufficiently active for the catalytic dehydrogenation of hydrogenated dibenzyl toluene.
Disclosure of Invention
In order to overcome the defects in 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 above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a high-activity alumina-supported platinum catalyst, which comprises the following steps:
pretreating an alumina carrier by adopting organic atmosphere dielectric barrier discharge organic atmosphere plasmas to obtain an alumina carrier grafted with organic groups; and loading platinum on the organic alumina carrier by an impregnation method to obtain the high-activity alumina-loaded platinum catalyst.
Preferably, the alumina support is plasma pretreated with a dielectric barrier discharge organic atmosphere wherein the organic atmosphere is methane or acetic acid.
Further preferably, when the organic atmosphere is methane, the method for preparing the grafted organic group alumina carrier is as follows:
by Al 2 O 3 The powder is used as a carrier precursor, the mixed gas of methane gas and argon gas is used as 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 method for preparing the organic group-grafted alumina support is as follows:
by Al 2 O 3 The powder is used as a carrier precursor, argon is used as working gas, and methane alumina carrier is obtained through a bubbler filled with acetic acid at room temperature, wherein the discharge voltage is 20-60kV of peak-to-peak value, and the discharge time is 1-20 min.
Still more preferably, the discharge medium is quartz glass, the medium thickness is 0.2-5mm, and the discharge interval is 2-50mm.
Still more preferably, the discharge voltage is 20 to 60kV in peak-to-peak value.
Preferably, the platinum is supported on the organic alumina carrier by an impregnation method, and specific operations include:
the high-activity alumina-loaded platinum catalyst is prepared by impregnating a chloroplatinic acid solution on an organic alumina carrier by an isovolumetric impregnation method, drying the solution below 100 ℃, and roasting the solution for 0.5 to 6 hours at 150 to 400 ℃ in a hydrogen atmosphere.
Further preferably, the platinum loading in the high-activity alumina-supported platinum catalyst is 0.5% -5% of the mass of the grafted organic group alumina carrier.
The invention also discloses a high-activity alumina-supported platinum catalyst prepared by the preparation method.
The invention also discloses application of the high-activity alumina supported platinum catalyst in catalyzing the dehydrogenation reaction of the full-hydrogenation dibenzyl toluene, and the conditions of catalyzing the dehydrogenation reaction of the full-hydrogenation dibenzyl toluene are as follows: the reaction temperature is 240-310 ℃; the reaction pressure is 1kPa-1MPa.
Compared with the prior art, the invention has the following beneficial effects:
the method utilizes a green and environment-friendly dielectric barrier discharge low-temperature plasma method to prepare the organic matter alumina-loaded platinum catalyst, adopts a dielectric barrier discharge method to ionize organic atmosphere to generate high-energy plasma so as to carry out surface modification on the 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 adopts methane and acetic acid, the methyl in the prepared catalyst improves the dispersity of platinum and influences the morphology of the supported platinum particles so as to show better catalytic hydrogenation dibenzyl toluene dehydrogenation activity, CH 3 The COO-group acts as an electron donor for the Pt particles resulting in a significant increase in dehydrogenation activity.
The prepared alumina platinum-carrying catalyst has good catalytic activity for catalytic dehydrogenation reaction in the hydrogen storage process of dibenzyl toluene, can effectively improve the hydrogen storage efficiency, and has good economic benefit when being popularized and applied to the liquid organic hydrogen storage process.
Further, pt/Al prepared by the method 2 O 3 -P-CH 4 Catalysts or Pt/Al 2 O 3 -P-CH 3 The COOH catalyst can be used for the high-efficiency catalytic dehydrogenation reaction of the perhydrogenated dibenzyl toluene, wherein Pt/Al 2 O 3 -P-CH 4 Has high catalytic dehydrogenation activity: under the conditions that the molar ratio of Pt to 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, and the dehydrogenation rate is improved by 19.5 percent compared with 62.2 percent of the catalyst which is not subjected to plasma treatment, and the Pt/Al ratio is improved 2 O 3 -P-CH 3 COOH had a high catalytic dehydrogenation activity, and the dehydrogenation rate was 74.2% at the same dehydrogenation conditions, compared to Pt/Al 2 O 3 The improvement is 18.5 percent.
Drawings
FIG. 1 is an infrared spectrum of an organic alumina-supported platinum catalyst prepared by the invention;
FIG. 2 is a schematic diagram of a dielectric barrier discharge low temperature plasma reactor.
Wherein: 1-high voltage electrode; 2-quartz glass; 3-zero potential electrode; 4-low temperature plasma; 5-sample.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise 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 attached drawing figures:
the catalyst adopts methane or acetic acid atmosphere dielectric barrier discharge low-temperature plasma pretreatment of alumina carrier (respectively expressed as Al) 2 O 3 -P-CH 4 Or Al 2 O 3 -P-CH 3 COOH), active component Pt is supported on Al 2 O 3 -P-CH 4 Or Al 2 O 3 -P-CH 3 On COOH, pt loading is 0.5% -5%, and the Pt loading is divided into two partsIs separately marked as Pt/Al 2 O 3 -P-CH 4 And Pt/Al 2 O 3 -P-CH 3 COOH. The preparation method comprises the following specific steps:
(1) Pretreatment of alumina carrier by adopting methane atmosphere dielectric barrier discharge low-temperature plasma
Active Al after roasting at 600 DEG C 2 O 3 Uniformly spreading the powder serving as a carrier precursor in a plasma discharge reactor, adopting quartz glass serving as a blocking medium, wherein the thickness of the medium is 0.2-5mm, the discharge interval is 2-50mm, the working gas is argon and methane mixed gas, the methane volume fraction is 5-95%, the discharge voltage is 20-60kV of peak-to-peak value, the discharge time is 1-20min, and finally obtaining the methane medium blocking discharge low-temperature plasma pretreated alumina carrier, and the mark is Al 2 O 3 -P-CH 4 ；
(2) Low-temperature plasma pretreatment of alumina carrier by adopting acetic acid atmosphere dielectric barrier discharge
Except that the working gas is acetic acid saturated gas formed by argon flowing through an acetic acid bubbler, other conditions are the same as the plasma treatment condition (1), and finally the low-temperature plasma pretreatment alumina carrier of dielectric barrier discharge in acetic acid atmosphere is obtained, and is marked as Al 2 O 3 -P-CH 3 COOH；
(3) Preparation of Pt/Al by immersion method 2 O 3 -P-CH 4 Or Pt/Al 2 O 3 -P-CH 3 COOH catalysts
According to the metering ratio, adopting an isovolumetric impregnation method to prepare the required amount of H 2 PtCl 6 Impregnating Al with solution 2 O 3 -P-CH 4 Or Al 2 O 3 -P-CH 3 On COOH, pt mass percent is 0.5-5%, then drying under 100 ℃, and roasting under hydrogen atmosphere at 150-400 ℃ for 0.5-6 hours, thus obtaining Pt/Al respectively 2 O 3 -P-CH 4 Or Pt/Al 2 O 3 -P-CH 3 COOH catalyst.
The plasma reactor for realizing the preparation method of the invention is shown in figure 2, wherein the discharge medium used in the discharge process in the (1) and (2) is quartz glass, the thickness of the medium is 0.2-5mm, and the discharge interval is 2-50mm. The peak value of the discharge voltage is 20-60kV.
Example 1
Pt/Al was prepared as follows 2 O 3 -P-CH 4 Catalyst
(1) Weigh 0.5gAl 2 O 3 And tiled in a plasma reactor, wherein the quartz glass has a thickness of 1mm and a discharge gap of 8mm. Methane and argon respectively flow through the reactor at a flow rate of 50ml/min, sinusoidal wave discharge is adopted, the voltage is 45kV of peak-to-peak value, the discharge time is 3min each time, the total discharge time is 5 times, 15 min each time interval is 15 min each time, and samples are stirred during the time interval, so that Al is finally obtained 2 O 3 -P-CH 4 ；
(2) H was impregnated with isovolumetric solution 2 PtCl 6 Impregnating Al with solution 2 O 3 -P-CH 4 Drying at 80deg.C for 12 hr, and calcining at 400deg.C in hydrogen atmosphere for 2 hr to obtain 3% Pt/Al 2 O 3 -P-H 2 A catalyst.
Putting 0.8g of the catalyst into a 50mL high-pressure stirring reaction kettle, putting 10mL of perhydrogenated dibenzyl toluene, introducing pure hydrogen for purging, and carrying out dehydrogenation reaction at the temperature of 270 ℃ under normal pressure, wherein the dehydrogenation rate of 5 hours is 74.8 percent and the ratio of Pt/Al is 3 percent 2 O 3 The dehydrogenation rate of the catalyst is 62.6%, the catalyst is improved by 19.5%, and the catalytic activity is obviously improved.
Example 2
Pt/Al was prepared as follows 2 O 3 -P-CH 3 COOH catalyst:
the rest of the preparation and implementation of the catalyst were carried out as in example 1, by controlling the argon flow to a flow rate of 100ml/min through a bubbler containing acetic acid and then through the reactor.
In the catalytic reaction, the dehydrogenation rate at 5 hours was 74.2%, which was 18.5% higher than that of the catalyst without plasma treatment, 62.6%.
Referring to FIG. 1, the Pt/Al prepared by the present invention 2 O 3 -P-CH 4 The surface has methyl and methylene groups, pt/Al 2 O 3 -P-CH 3 COOH having CH on its surface 3 COO-groups and a small amount of methyl groups; the curve (a) in fig. 1 is used for comparison to demonstrate that the surface of the support that is not treated with the dielectric barrier discharge plasma in the presence of methane and acetic acid atmospheres does not contain the relevant groups: 2964, 2930, 2877, 1456 and 1386cm in curve (b) of FIG. 1 -1 The peaks of (c) in FIG. 1 represent methyl and methylene groups, 1424, 1473 and 1608cm in curve (c) -1 The peak of (C) represents CH 3 COO-groups. The methyl improves the dispersity of platinum and influences the morphology of the supported platinum particles so as to show better catalytic hydrogenation dibenzyl toluene dehydrogenation activity and CH 3 The COO-group acts as an electron donor for the Pt particles resulting in a significant increase in dehydrogenation activity.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (5)
1. The preparation method of the high-activity alumina-supported platinum catalyst is characterized by comprising the following steps of:
pretreating an alumina carrier by adopting organic atmosphere dielectric barrier discharge organic atmosphere plasmas to obtain an alumina carrier grafted with organic groups; platinum is loaded on an organic alumina carrier by an impregnation method, so that a high-activity alumina loaded platinum catalyst is obtained;
the organic atmosphere is methane or acetic acid;
when the organic atmosphere is methane, the preparation method of the alumina carrier grafted with organic groups is as follows:
by Al 2 O 3 Taking the powder as a carrier precursor, taking a mixed gas of methane gas and argon gas as a working gas, wherein 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 as to obtain a methane alumina carrier;
when the organic atmosphere is acetic acid, the preparation method of the alumina carrier grafted with organic groups is as follows:
by Al 2 O 3 The powder is used as a carrier precursor, argon is used as working gas, and acetic acid is filled in a bubbler at room temperature, the discharge voltage is 20-60kV of peak-to-peak value, and the discharge time is 1-20min, so that the acetic acid alumina carrier is obtained.
2. The method for preparing the high-activity alumina-supported platinum catalyst according to claim 1, wherein the discharge medium is quartz glass, the thickness of the medium is 0.2-5mm, and the discharge interval is 2-50mm.
3. The method for preparing a highly active alumina supported platinum catalyst according to claim 1, wherein the platinum is supported on an organic alumina carrier by impregnation, comprising the following specific operations:
and (3) dipping the chloroplatinic acid solution on an organic alumina carrier by an isovolumetric dipping method, drying at a temperature below 100 ℃, and roasting at a temperature of 150-400 ℃ for 0.5-6 h in a hydrogen atmosphere to obtain the high-activity alumina-supported platinum catalyst.
4. The method for preparing a high-activity alumina-supported platinum catalyst according to claim 3, wherein the platinum loading amount in the high-activity alumina-supported platinum catalyst is 0.5% -5% of the mass of the grafted organic group alumina carrier.
5. The use of the high-activity alumina-supported platinum catalyst prepared by the preparation method according to any one of claims 1 to 4 for catalyzing the dehydrogenation reaction of perhydrogenated dibenzyl toluene, wherein the conditions for catalyzing the dehydrogenation reaction of perhydrogenated dibenzyl toluene are as follows: the reaction temperature is 240-310 ℃; the reaction pressure is 1kPa-1MPa.
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