CN114832816A - Low-carbon alkane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Low-carbon alkane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 51
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/024—Multiple impregnation or coating
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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Abstract
The invention relates to the field of low-carbon alkane dehydrogenation, and discloses a low-carbon alkane dehydrogenation catalyst, and a preparation method and application thereof. The catalyst comprises a carbon nano tube and a platinum component and a gallium component which are loaded on the carbon nano tube; wherein, based on the total weight of the light alkane dehydrogenation catalyst, the content of the carbon nano tube is 85-98 wt%, the content of the platinum component calculated by platinum element is 1-10 wt%, the content of the gallium component calculated by gallium element is 1-5 wt%, and at least part of the platinum component is positioned in the tube of the carbon nano tube. The catalyst of the invention has better conversion rate, selectivity and stability when being used for dehydrogenation reaction of low-carbon alkane.
Description
Technical Field
The invention relates to the field of low-carbon alkane dehydrogenation, in particular to a low-carbon alkane dehydrogenation catalyst and a preparation method and application thereof, and more particularly relates to a low-carbon alkane dehydrogenation catalyst taking carbon nanotubes as carriers and a preparation method and application thereof.
Background
The Pt-based catalyst is one of the commonly used catalysts for propane dehydrogenation. Propane dehydrogenation is a reversible reaction with strong heat absorption and increased molecular number, the dehydrogenation reaction is favorably carried out at high temperature and low pressure, the common reaction temperature is about 600 ℃, the higher reaction temperature causes the aggravation of propane cracking and propane deep dehydrogenation degree, the selectivity of propylene is reduced, and the aggravation of carbon deposit on the surface of a catalyst can also cause the inactivation of the catalyst.
In recent years, carbon nanotubes have been widely studied as a novel nanocarbon material. The carbon nanotubes can encapsulate the active components of the catalyst in the nano-scale cavity of the catalyst, thereby changing the catalytic activity of the catalyst nanoparticles. The catalytic properties of carbon nanotubes are mainly manifested in their specific architecture and nanoscale dimensions. On one hand, the coiled structure causes the change of the carbon layer structure, and the electron density is transferred from the inside of the tube to the outside of the tube to form an internal and external potential difference, so that the characteristics of substances which react in the internal and external potential difference are changed; on the other hand, as the nano-particles, the carbon nano-tubes have a typical confinement effect, that is, when the system is scaled down to a nano-scale, the movement of electrons in the system is limited by space, the electronic state changes, and the catalytic performance of the system also changes accordingly.
Disclosure of Invention
The invention aims to solve the problem of poor stability of a Pt-based low-carbon alkane dehydrogenation catalyst in the prior art, and provides the low-carbon alkane dehydrogenation catalyst, and a preparation method and application thereof.
In order to achieve the above objects, an aspect of the present invention provides a light alkane dehydrogenation catalyst comprising a carbon nanotube and a platinum component and a gallium component supported on the carbon nanotube; wherein, based on the total weight of the light alkane dehydrogenation catalyst, the content of the carbon nano tube is 85-98 wt%, the content of the platinum component calculated by platinum element is 1-10 wt%, the content of the gallium component calculated by gallium element is 1-5 wt%, and at least part of the platinum component is positioned in the tube of the carbon nano tube.
Preferably, the content of the carbon nanotubes is 87 to 96 weight percent, the content of the platinum component is 2 to 8 weight percent calculated by platinum element, and the content of the gallium component is 2 to 5 weight percent calculated by gallium element, based on the total weight of the light alkane dehydrogenation catalyst.
Preferably, the gallium component comprises an oxide of gallium.
Preferably, the platinum component comprises elemental platinum.
Preferably, the pore diameter of the light alkane dehydrogenation catalyst is 3-17nm, the specific surface area is 104-300m 2 (ii)/g, total pore volume of 0.1-1cm 3 /g。
Preferably, the carbon nanotubes are multi-walled carbon nanotubes.
The second aspect of the present invention provides a preparation method of a low-carbon alkane dehydrogenation catalyst, which comprises the following steps:
(1) carrying out oxidation treatment on the carbon nano tube by using an acid solution, and sequentially carrying out washing and first drying to obtain a carbon nano tube carrier;
(2) and (2) carrying out first impregnation on the carbon nano tube carrier in the step (1) by using a platinum-containing compound solution, then carrying out second impregnation by using a gallium-containing compound solution, and then sequentially carrying out second drying and reduction treatment.
Preferably, in step (1), the acid solution is concentrated nitric acid or a mixture of concentrated sulfuric acid and concentrated nitric acid, preferably, the concentration of the concentrated nitric acid is 20-80 wt%, preferably 60-70 wt%, and the concentration of the concentrated sulfuric acid is 90-98 wt%.
Preferably, the time of the oxidation treatment is 2-18h, and the temperature is 40-180 ℃.
Preferably, the conditions of the first drying include: the temperature is 60-160 ℃, and the time is 8-36 h.
Preferably, in the step (2), the platinum-containing compound in the platinum-containing compound solution is one or more of platinum nitrate, chloroplatinic acid, potassium chloroplatinate, tetraammineplatinum dichloride and platinum acetylacetonate.
Preferably, the solvent of the platinum compound-containing solution is one or more of water, methanol, ethanol and acetone.
Preferably, the method of first impregnation comprises ultrasonic impregnation, preferably comprises ultrasonic impregnation and first agitated impregnation.
Preferably, the ultrasonic dipping time is 0.3-5h, and the first stirring dipping time is 0.5-6 h.
Preferably, the first impregnation temperature is 15-45 ℃.
Preferably, the volume of the platinum-containing compound solution is 5-30mL relative to 1g of the carbon nanotube carrier, and the platinum content in the platinum-containing compound solution is 1-8 mg/mL.
Preferably, in step (2), the gallium-containing compound in the gallium-containing compound solution is one or more of gallium nitrate, gallium chloride, gallium oxide or gallium acetylacetonate.
Preferably, the solvent of the gallium-containing compound solution is one or more of water, methanol, ethanol, and acetone.
Preferably, the second impregnation method is a second agitation impregnation; more preferably, the second impregnation is carried out for a time of 5-60min and at a temperature of 70-120 ℃.
Preferably, the volume of the gallium-containing compound solution is 5-30mL relative to 1g of the carbon nanotube carrier, and the content of gallium in the gallium-containing compound solution is 2-6 mg/mL.
Preferably, in the step (2), the conditions of the second drying include: the drying temperature is 80-130 ℃, and the drying time is 8-30 h.
Preferably, in the step (2), the reduction treatment comprises reduction with a reducing agent or hydrogen gas, and preferably the reducing agent is one or more of ethylene glycol, a carboxylic acid of C1-C3, and a sodium carboxylate of C1-C3.
Preferably, when reducing by using the reducing agent, the molar ratio of the reducing agent to platinum element is 10-20: 1, the reduction temperature is 50-300 ℃.
Preferably, the reduction temperature is 550-650 ℃ when hydrogen is used for reduction.
Preferably, the carbon nanotubes are multi-walled carbon nanotubes.
In a third aspect, the present invention provides a method for dehydrogenating a lower alkane, including a step of subjecting the lower alkane to a contact reaction with a catalyst under a dehydrogenation reaction condition, where the catalyst is the catalyst according to the first aspect of the present invention or the catalyst prepared by the preparation method according to the second aspect of the present invention.
Preferably, the dehydrogenation reaction conditions include: the temperature is 500 ℃ and 650 ℃, and the pressure is 0.1-0.5 MPa.
According to the technical scheme, the processed carbon nano tube is used as a carrier, and the catalyst is prepared by loading the metal platinum component and the metal gallium component, and the prepared catalyst is used for dehydrogenation reaction of low-carbon alkane, and has high selectivity and performance stability of dehydrogenation products.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of a catalyst obtained in example 1 of the present invention.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of a catalyst prepared in comparative example 4 of the present invention.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of a catalyst prepared in comparative example 3 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a light alkane dehydrogenation catalyst comprising a carbon nanotube and a platinum component and a gallium component supported on the carbon nanotube; wherein, based on the total weight of the light alkane dehydrogenation catalyst, the content of the carbon nano tube is 85-98 wt%, the content of the platinum component calculated by platinum element is 1-10 wt%, the content of the gallium component calculated by gallium element is 1-5 wt%, and at least part of the platinum component is positioned in the tube of the carbon nano tube.
According to the present invention, preferably, the content of the carbon nanotubes is 87 to 96 wt%, the content of the platinum component calculated as platinum element is 2 to 8 wt%, and the content of the gallium component calculated as gallium element is 2 to 5 wt%, based on the total weight of the light alkane dehydrogenation catalyst.
The content of the specific platinum component in terms of platinum element may be 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%; as a content of the specific gallium component in terms of gallium element, it may be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%; the content of the carbon nanotube may be 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, or 98 wt%.
In the present invention, the carbon nanotube is not particularly limited, and may be one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. From the viewpoint of easy availability of materials and performance of preparing the low-carbon alkane dehydrogenation catalyst, the multi-wall carbon nanotube is preferred. The multi-walled carbon nanotube can be prepared by Chemical Vapor Deposition (CVD), for example, the catalyst used in the preparation is a supported nickel catalyst, the raw material is hydrocarbon, and the preparation temperature can be 500-700 ℃.
According to the present invention, the existence form of the platinum component and the gallium component is not particularly limited as long as the lower alkane dehydrogenation catalytic activity can be provided. Preferably under the circumstancesThe platinum component comprises elemental platinum and/or an oxide of platinum (e.g., PtO 2 ) Preferably, the platinum element accounts for more than 70%, more preferably more than 80%, for example 80-98% of the total platinum element; the gallium component comprises elemental gallium, an oxide of gallium (for example, Ga) 2 O、GaO、Ga 2 O 3 Etc., among them, Ga is preferred 2 O 3 ) Gallium nitride (for example, GaN), and the like, and Ga is preferably calculated as gallium 2 O 3 More than 20%, more preferably more than 25%, such as 25-60%, of the total gallium element, preferably less than 50%, such as 30-50%, of the total gallium element.
According to the invention, the pore diameter of the low-carbon alkane dehydrogenation catalyst is preferably 3-17nm, and the specific surface area is 104-300m 2 (ii)/g, total pore volume of 0.1-1.0cm 3 (ii)/g; preferably, the pore diameter of the low-carbon alkane dehydrogenation catalyst is 8-15nm, and the specific surface area is 200-300m 2 (ii)/g, total pore volume of 0.4-1.0cm 3 (ii) in terms of/g. According to a preferred embodiment of the present invention, the pore diameter of the light alkane dehydrogenation catalyst is 14-17nm, and the specific surface area is 250-270m 2 (ii)/g, total pore volume of 0.9-1.0cm 3 /g。
In the present invention, "at least a part of the platinum component is located in the tube of the carbon nanotube" means that at least a part of the platinum component enters and is supported in the tube of the carbon nanotube, and it is preferable that a large amount of the platinum component is located in the tube of the carbon nanotube (for example, 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, or 90 wt% or more) from the viewpoint of improving the dehydrogenation catalytic activity of the lower alkane.
In addition, it is preferable that at least a part of the gallium component is located outside the tube of the carbon nanotube, and it is more preferable that the entire gallium component is located outside the tube of the carbon nanotube. The gallium component located outside the tube of the carbon nanotube may be 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, or 90 wt% or more, for example.
Specifically, the existence positions of the platinum component and the gallium component can be judged by, for example, transmission electron microscopy and etching XPS result observation.
The low-carbon alkane dehydrogenation catalyst can further improve the catalytic activity and selectivity by properly controlling the existence positions of the gallium component and the platinum component.
The second aspect of the present invention provides a preparation method of a low-carbon alkane dehydrogenation catalyst, which comprises the following steps:
(1) carrying out oxidation treatment on the carbon nano tube by using an acid solution, and sequentially carrying out washing and first drying to obtain a carbon nano tube carrier;
(2) and (2) performing first impregnation on the carbon nano tube carrier in the step (1) by using a platinum-containing compound solution, performing second impregnation by using a gallium-containing compound solution, and performing second drying and reduction treatment.
The preparation method of the second aspect of the present invention can be used for preparing the light alkane dehydrogenation catalyst of the first aspect, and the raw material carbon nanotubes and the like are defined the same, and are not described herein again.
In the present invention, the step (1) is used to treat the carbon nanotubes, facilitating the loading of the platinum component and the gallium component.
According to the present invention, in step (1), the acid solution used in the oxidation treatment may be concentrated nitric acid or a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein the concentration of the concentrated nitric acid may be 20 to 80 wt%, preferably 60 to 70 wt%, and more preferably 65 to 68 wt%; the concentrated sulfuric acid has a concentration of 90 to 98 wt.%, preferably 95 to 98 wt.%. When a mixture of concentrated sulfuric acid and concentrated nitric acid is used, the volume ratio of concentrated nitric acid to concentrated sulfuric acid is preferably 1: 2.5-3.5, e.g. 1: 3. the time of the oxidation treatment can be 2-18h, preferably 4-16h, and the temperature can be 40-180 ℃, preferably 120-150 ℃. The amount of the nitric acid solution may be 40-60mL with respect to 1g of the carbon nanotubes.
According to the invention, in the step (1), the carbon nano tube after oxidation treatment is washed and dried for loading active components. The washing may be performed using water, for example, and preferably, the conditions of the first drying may include: the temperature is 60-160 ℃, and the time is 8-36 h; preferably, the temperature is 80-120 ℃ and the time is 10-30 h.
In the present invention, the step (2) is for forming a platinum component and a gallium component supported on the carbon nanotube.
According to the present invention, the platinum-containing compound in the platinum-containing compound solution is not particularly limited, and may be, for example, one or more of platinum nitrate, chloroplatinic acid, potassium chloroplatinate, tetraammineplatinum dichloride, and platinum acetylacetonate. Preferably, the solvent of the platinum compound-containing solution is one or more of water, methanol, ethanol and acetone, preferably methanol and/or ethanol. By using the above solvent, the desired platinum component can be more preferably produced.
In order to allow at least part of the formed platinum component to be located inside the tube of the carbon nanotube, it is preferable that the method of the first impregnation includes ultrasonic impregnation, more preferably includes ultrasonic impregnation and first agitation impregnation, and more preferably, the first agitation impregnation is performed both before and after the ultrasonic impregnation.
From the viewpoint of improving the activity of the catalyst to be obtained, it is preferable that the ultrasonic impregnation time is 0.3 to 5 hours, preferably 2 to 3 hours, and the first agitation impregnation time is 0.5 to 6 hours, preferably 0.5 to 2 hours. In addition, the first impregnation temperature is 15 to 45 ℃, preferably 20 to 30 ℃. In order to further improve the activity of the prepared catalyst, preferably, the volume of the platinum-containing compound solution is 10-30mL, preferably 10-20mL, relative to 1g of the carbon nanotube carrier, and the platinum content in the platinum-containing compound solution is 1-8mg/mL, preferably 2-6 mg/mL.
According to the present invention, the gallium-containing compound in the gallium-containing compound solution is not particularly limited, and may be, for example, one or more of gallium nitrate, gallium chloride, gallium oxide, and gallium acetylacetonate. Preferably, the solvent of the gallium-containing compound solution is one or more of water, methanol, ethanol and acetone, preferably methanol and/or ethanol. By using the above solvent, the desired gallium component can be more preferably produced.
In order to cause the formed gallium component to be supported on the carbon nanotube, it is preferable that the method of the second impregnation is a second agitation impregnation. More preferably, the time of the second impregnation is 5-60min, preferably 10-20min, and the temperature is 70-120 ℃, preferably 100-120 ℃. In order to further improve the activity of the prepared catalyst, preferably, the volume of the gallium-containing compound solution is 10-30mL, preferably 10-20mL, relative to 1g of the carbon nanotube carrier, and the gallium content in the gallium-containing compound solution is 2-6mg/mL, preferably 3-5 mg/mL.
According to the present invention, in the step (2), the conditions of the second drying may include: the drying temperature is 80-130 ℃, and the drying time is 8-30 h; preferably, the drying temperature is 90-110 ℃ and the drying time is 15-25 h.
According to the invention, in the step (2), the reduction treatment may comprise reduction with a reducing agent or hydrogen gas, preferably the reducing agent is one or more of ethylene glycol, a carboxylic acid of C1 to C3, and a sodium carboxylate of C1 to C3, such as formic acid and/or sodium formate. When reducing with a reducing agent, the molar ratio of the reducing agent to platinum element may be 10 to 20: 1, preferably 13 to 16: 1, the reduction temperature can be 50-300 ℃, and preferably 90-150 ℃; when hydrogen is adopted for reduction, the reduction temperature can be 550-650 ℃, and preferably 570-610 ℃; the reduction time is, for example, 0.1 hour or more, preferably 0.5 to 3 hours.
In a third aspect of the present invention, a method for dehydrogenating a light alkane is provided, which includes subjecting the light alkane to a contact reaction with a catalyst under a dehydrogenation reaction condition, where the catalyst is the catalyst of the first aspect of the present invention or the catalyst prepared by the preparation method of the second aspect of the present invention.
According to the present invention, preferably, the dehydrogenation reaction conditions include: the temperature is 500 ℃ and 650 ℃, and the pressure is 0.1-0.5 MPa; more preferably, the temperature is 550 ℃ and 620 ℃ and the pressure is 0.1-0.3 MPa.
Examples of the lower alkane include C3-C5 alkanes such as propane, butane and/or pentane.
The present invention will be described in detail below by way of examples. In the following examples, the TEM used is a transmission electron microscope with Tecnai G2F 20S-TWIN TMP field emission and XPS VG Scientific ESCALab220 i-XL. In the performance measurement of the catalyst, according to a nitrogen absorption-desorption curve, a BET equation is adopted to obtain a specific surface area, and a BJH equation is adopted to obtain an aperture and a total pore volume.
Example 1
(1) Preparation of multiwalled carbon nanotube carrier
Taking 2.5g of multi-wall carbonThe nano tube (purity is more than 98 wt.%, ash content is less than 1.5 wt.%, provided by national institute of science and technology organic chemistry, Inc., TNSM3, is prepared by Chemical Vapor Deposition (CVD), and is prepared by using a supported nickel catalyst at 500-700 ℃) and using 125mL of 66.0 wt.% concentrated HNO 3 And (3) carrying out immersion oxidation treatment at 140 ℃ for 14h, washing the immersed solid with deionized water, and drying in the air at 110 ℃ for 12h to obtain the multi-wall carbon nano tube carrier CNTs.
(2) Preparation of the catalyst
Putting 0.3g of the multi-walled carbon nanotube carrier CNTs prepared in the step (1), 3mL of ethanol solution of chloroplatinic acid with the concentration of 5mg/mL calculated by Pt and 3mL of absolute ethanol into a 50mL beaker, stirring for 0.5h at 25 ℃, then treating for 3h by ultrasonic at 25 ℃, and then stirring for 0.5 h; then, 3mL of an ethanol solution of gallium nitrate having a concentration of 3mg/mL in terms of Ga was added thereto, and the mixture was stirred at 100 ℃ for 20 min. Then dried at 110 ℃ for 24H, H at 580 DEG C 2 And reducing for 1h to obtain the catalyst C1.
Example 2
A catalyst was prepared as described in example 1, except that the ethanol solution of chloroplatinic acid used in the impregnation of the carrier with the ethanol solution of chloroplatinic acid in step (2) was 0.6mL and ethanol was 5.4mL, to obtain catalyst C2.
Example 3
A catalyst was prepared as described in example 1, except that the ethanol solution of chloroplatinic acid used in the impregnation of the carrier with the ethanol solution of chloroplatinic acid in step (2) was 1.8mL and ethanol was 4.2mL, to obtain catalyst C3.
Example 4
Catalyst C4 was prepared by the method of example 1, except that a 1mg/mL ethanol solution of gallium nitrate in terms of Ga was used in step (2).
Example 5
Catalyst C5 was prepared by the method of example 1, except that a solution of gallium nitrate in ethanol at a concentration of 6mg/mL in terms of Ga was used in step (2).
Example 6
A catalyst C6 was prepared by following the procedure in example 1, except that the reduction temperature in step (2) was 300 ℃.
Example 7
A catalyst was prepared by following the procedure of example 1, except that the ultrasonic treatment was not conducted in the step (2), to obtain catalyst C7.
Example 8
A catalyst was prepared by following the procedure of example 1, except that the nitric acid solution used in step (1) had a concentration of 80% by weight, to obtain catalyst C8.
Example 9
A catalyst was prepared by following the procedure of example 1, except that the nitric acid solution used in step (1) had a concentration of 20% by weight, to obtain catalyst C9.
Example 10
A catalyst was prepared by following the procedure of example 1, except that the ethanol solution was replaced with an acetone solution in the step (2), to obtain catalyst C10.
Comparative example 1
A catalyst was prepared as described in example 1, except that 0.3g of the multi-walled carbon nanotube support CNTs prepared in step (1), 3mL of an ethanol solution of gallium nitrate having a concentration of 3mg/mL in terms of Ga, and 3mL of anhydrous ethanol were placed in a 50mL beaker in step (2), stirred at 25 ℃ for 0.5h, then sonicated at 25 ℃ for 3h, then stirred for 0.5h, then 3mL of an ethanol solution of chloroplatinic acid having a concentration of 5mg/mL in terms of Pt was added, and stirred at 100 ℃ for 20 min. Then dried at 110 ℃ for 24H, H at 580 DEG C 2 And reducing for 1h to obtain the catalyst DC 1.
Comparative example 2
A catalyst was prepared as described in example 1, except that step (2) was not performed, i.e., the multi-walled carbon nanotube support was not loaded with any metal component, to prepare a catalyst DC 2.
Comparative example 3
A catalyst was prepared by following the procedure of example 1 except that the ethanol solution of gallium nitrate was replaced with absolute ethanol in the step (2), to obtain a catalyst DC 3.
Comparative example 4
A catalyst was prepared by the method of example 1, except that the ethanol solution of chloroplatinic acid was replaced with absolute ethanol in the step (2), to obtain a catalyst DC 4.
Comparative example 5
A catalyst was prepared as described in example 1, except for step (2). And (2) putting 0.3g of the multi-wall carbon nano tube carrier CNTs prepared in the step (1), 3mL of ethanol solution of gallium nitrate with the Ga concentration of 3mg/mL and 3mL of absolute ethanol into a 50mL beaker, stirring for 0.5h at 25 ℃, then carrying out ultrasonic treatment for 3h at 25 ℃, then stirring for 0.5h, then adding 3mL of absolute ethanol, and stirring for 20min at 100 ℃. Then dried at 110 ℃ for 24H and at 580 ℃ in H 2 And reducing for 1h to obtain the catalyst DC 5.
Comparative example 6
A catalyst was prepared by following the procedure of example 1, except that the treatment in step (1) was not conducted, to obtain catalyst DC 6.
Test example 1
The catalyst of example 1 was measured for its performance, and found to have a pore diameter of 14.7nm and a specific surface area of 265.4m 2 (g) total pore volume of 0.98cm 3 The transmission electron micrograph is shown in FIG. 1.
Transmission electron micrographs of the catalysts prepared in comparative examples 4 and 3 are shown in fig. 2 and 3, respectively.
The results of X-ray photoelectron spectroscopy (XPS) measurement of the catalysts C1, DC4 and DC3 are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
As can be seen from a comparison of fig. 1 and 2, the catalyst DC4 of comparative example 4, to which chloroplatinic acid was not added, did not show black particles, and it can be seen from the XPS characterization results of table 1 that the catalyst DC4 contains a Ga component, but the distribution of the Ga component cannot be determined.
As can be seen from a comparison of fig. 1 and 3, the inner surfaces of the carbon nanotubes in catalyst DC3 of comparative example 3, to which gallium nitrate was not added, had black particles as in fig. 1. Meanwhile, as can be seen from the XPS results in table 2, the black particles are Pt particles, which indicates that the Pt component is supported on the inner surface of the carbon nanotube of the catalyst C1 at this time.
From fig. 1 in conjunction with the above analysis, it can be presumed that the surface particles of the catalyst C1 of example 1 are Pt components, but the distribution position of the Ga component cannot be confirmed.
In order to further clarify the distribution of the platinum component and the gallium component in the catalyst, catalyst C1 of example 1 was measured by etching X-ray photoelectron spectroscopy (XPS), and the results are shown in table 3. In table 3, 0(nm) represents the element distribution on the surface of the carbon nanotube measured by the probe in the XPS measurement; 5(nm) represents the element distribution inside the carbon nanotube measured by a probe after etching the carbon nanotube to a depth of 5nm at a rate of 0.02nm/s using an argon ion gun.
TABLE 3
As can be seen from the measurement results in table 3, the Ga content of the catalyst C1 having an etching depth of 5nm was less than 0nm, and the Pt content was more than 0nm, whereby it was confirmed that the Pt component was mainly located inside the multi-walled carbon nanotube and the Ga component was mainly supported outside the carbon nanotube.
In addition, as can be seen from table 1, in catalyst C1, 39 mol% of Ga species have a valence of 0, and 29 mol% of Ga species have a valence of + 3. As can be seen from Table 2, in the catalyst C1, 85 mol% of Pt species has a valence of 0, 7 mol% of Pt species has a valence of +2, and 8 mol% of Pt species has a valence of + 4.
Test example 2
This test example was used to evaluate the propane dehydrogenation performance of the catalyst.
0.2g of each of the catalysts of example and comparative example was packed in a microreaction device, and propane and N were added in a volume fraction of 5% based on propane 2 The mixture of (A) is a reactionRaw material, at 600 ℃, 0.10MPa and propane feeding weight space velocity of 1.8h -1 The average values of the conversion of propane and the selectivity of propylene during the reaction were calculated for 5 hours, and the catalysts used and the reaction results for each example are shown in Table 4.
TABLE 4
Numbering | Conversion of propane,% by weight | Propylene selectivity, wt.% |
Example 1 | 15.45 | 94.20 |
Example 2 | 8.82 | 89.19 |
Example 3 | 7.93 | 86.36 |
Example 4 | 10.32 | 85.23 |
Example 5 | 11.53 | 91.34 |
Example 6 | 11.36 | 90.46 |
Example 7 | 10.45 | 90.27 |
Example 8 | 8.32 | 88.70 |
Example 9 | 7.34 | 89.45 |
Example 10 | 13.56 | 93.42 |
Comparative example 1 | 7.12 | 87.98 |
Comparative example 2 | 4.06 | 73.66 |
Comparative example 3 | 4.62 | 82.89 |
Comparative example 4 | 3.86 | 74.76 |
Comparative example 5 | 4.10 | 75.17 |
Comparative example 6 | 6.89 | 84.65 |
It can be seen from the results of table 4 that the catalysts of examples 1-10, which employ the process of the present invention, have significantly better propane conversion and propylene selectivity relative to comparative examples 1-6.
As can be seen from a comparison of example 1 with comparative example 1, by supporting the Pt component first and then supporting the Ga component so that at least part of the Pt component is located in the tube of the carbon nanotube, it is possible to achieve the effect of simultaneously improving the propane conversion rate and propylene selectivity of the produced catalyst.
As can be seen from a comparison of examples 1 to 5, the content of the platinum component calculated as platinum element is preferably from 2 to 8% by weight and the content of the gallium component calculated as gallium element is preferably from 2 to 5% by weight, based on the total weight of the catalyst.
As can be seen from a comparison of example 1 with example 6, the preferred reduction temperature is 570-610 ℃.
As can be seen from the comparison of example 1 with example 7, the propane conversion and propylene selectivity of the catalyst produced can be further improved by performing the ultrasonic treatment so that more Pt component enters the tube of the carbon nanotube.
It can be seen from a comparison of example 1 with examples 8 to 9 that the propane conversion and propylene selectivity of the catalyst obtained can be further improved by using a nitric acid solution having a concentration of from 65 to 68% by weight.
As can be seen by comparing example 1 with example 10, the use of an ethanol solution as the impregnation solvent further improves the propane conversion and propylene selectivity of the catalyst produced.
Test example 3
0.2g of catalyst C1 prepared in example 1 was charged in a microreaction device and propane and N were added in a volume fraction of 5% based on propane 2 The mixture of (A) is a reactionRaw material, at 600 ℃, 0.11MPa and propane feeding mass space velocity of 1.8h -1 The dehydrogenation reaction was carried out under the conditions of (1), and the results of the reaction for 10 hours are shown in Table 5.
TABLE 5
Reaction time, h | Conversion of propane,% by weight | Propylene selectivity, wt.% |
0 | 26.08 | 95.67 |
0.5 | 17.91 | 94.75 |
1 | 16.15 | 94.47 |
1.5 | 15.08 | 94.26 |
2 | 14.21 | 94.08 |
2.5 | 13.64 | 93.94 |
3 | 13.27 | 93.76 |
3.5 | 12.90 | 93.80 |
4 | 12.64 | 93.61 |
4.5 | 12.32 | 93.39 |
5 | 12.12 | 93.33 |
5.5 | 11.89 | 93.33 |
6 | 11.56 | 93.26 |
6.5 | 11.54 | 93.28 |
7 | 11.45 | 93.26 |
7.5 | 11.40 | 93.12 |
8 | 11.35 | 93.11 |
8.5 | 11.25 | 93.09 |
9 | 11.20 | 93.18 |
9.5 | 11.20 | 93.16 |
10 | 11.15 | 93.15 |
As can be seen from the results in Table 5, the catalyst of the present invention has superior propane dehydrogenation activity and stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A low-carbon alkane dehydrogenation catalyst is characterized by comprising a carbon nano tube, and a platinum component and a gallium component which are loaded on the carbon nano tube;
wherein, based on the total weight of the light alkane dehydrogenation catalyst, the content of the carbon nano tube is 85-98 wt%, the content of the platinum component calculated by platinum element is 1-10 wt%, the content of the gallium component calculated by gallium element is 1-5 wt%, and at least part of the platinum component is positioned in the tube of the carbon nano tube.
2. The light alkane dehydrogenation catalyst of claim 1, wherein the carbon nanotubes comprise 87-96 wt%, the platinum component comprises 2-8 wt% as elemental platinum, and the gallium component comprises 2-5 wt% as elemental gallium, based on the total weight of the light alkane dehydrogenation catalyst;
preferably, the gallium component comprises an oxide of gallium;
preferably, the platinum component comprises elemental platinum.
3. The light alkane dehydrogenation catalyst according to claim 1 or 2, wherein the pore diameter of the light alkane dehydrogenation catalyst is 3-17nm, and the specific surface area is 104-300m 2 (ii)/g, total pore volume of 0.1-1cm 3 /g。
4. The light alkane dehydrogenation catalyst of claim 1 or 2, wherein the carbon nanotubes are multi-walled carbon nanotubes.
5. The preparation method of the low-carbon alkane dehydrogenation catalyst is characterized by comprising the following steps of:
(1) carrying out oxidation treatment on the carbon nano tube by using an acid solution, and sequentially carrying out washing and first drying to obtain a carbon nano tube carrier;
(2) and (2) carrying out first impregnation on the carbon nano tube carrier in the step (1) by using a platinum-containing compound solution, then carrying out second impregnation by using a gallium-containing compound solution, and then sequentially carrying out second drying and reduction treatment.
6. The method according to claim 5, wherein in step (1), the acid solution is concentrated nitric acid or a mixture of concentrated sulfuric acid and concentrated nitric acid, preferably, the concentration of the concentrated nitric acid is 20-80 wt%, and the concentration of the concentrated sulfuric acid is 90-98 wt%;
preferably, the time of the oxidation treatment is 2-18h, and the temperature is 40-180 ℃;
preferably, the conditions of the first drying include: the temperature is 60-160 ℃, and the time is 8-36 h.
7. The method according to claim 5 or 6, wherein in the step (2), the platinum-containing compound in the platinum-containing compound solution is one or more of platinum nitrate, chloroplatinic acid, potassium chloroplatinate, tetraammineplatinum dichloride and platinum acetylacetonate;
preferably, the solvent of the platinum compound-containing solution is one or more of water, methanol, ethanol and acetone;
preferably, the method of first impregnation comprises ultrasonic impregnation, preferably comprises ultrasonic impregnation and first agitated impregnation,
preferably, the ultrasonic dipping time is 0.3-5h, and the first stirring dipping time is 0.5-6 h;
preferably, the first impregnation temperature is 15-45 ℃;
preferably, the volume of the platinum-containing compound solution is 10-30mL relative to 1g of the carbon nanotube carrier, and the platinum content in the platinum-containing compound solution is 1-8 mg/mL.
8. The method according to any one of claims 5 to 7, wherein in step (2), the gallium-containing compound in the gallium-containing compound solution is one or more of gallium nitrate, gallium chloride, gallium oxide or gallium acetylacetonate;
preferably, the solvent of the gallium-containing compound solution is one or more of water, methanol, ethanol and acetone;
preferably, the second impregnation method is a second agitation impregnation; more preferably, the time of the second impregnation is 5-60min, and the temperature is 70-120 ℃;
preferably, the volume of the gallium-containing compound solution is 10-30mL relative to 1g of the carbon nanotube carrier, and the content of gallium in the gallium-containing compound solution is 2-6 mg/mL.
9. The method according to any one of claims 5 to 8, wherein in step (2), the conditions of the second drying comprise: the drying temperature is 80-130 deg.C, and the drying time is 8-30 h.
10. The method according to any one of claims 5 to 9, wherein in step (2), the reduction treatment comprises reduction with a reducing agent or hydrogen gas, preferably the reducing agent is one or more of ethylene glycol, a carboxylic acid of C1 to C3, and a sodium carboxylate of C1 to C3;
preferably, when reducing by using the reducing agent, the molar ratio of the reducing agent to platinum element is 10-20: 1, the reduction temperature is 50-300 ℃;
preferably, the reduction temperature is 550-650 ℃ when hydrogen is used for reduction.
11. The method of any one of claims 5-10, wherein the carbon nanotubes are multi-walled carbon nanotubes.
12. A method for dehydrogenating light alkane, which is characterized in that the method comprises the step of carrying out contact reaction on the light alkane and a catalyst under dehydrogenation reaction conditions, wherein the catalyst is the catalyst in any one of claims 1 to 4 or the catalyst prepared by the preparation method in any one of claims 5 to 11.
13. The method of claim 12, wherein the dehydrogenation reaction conditions comprise: the temperature is 500 ℃ and 650 ℃, and the pressure is 0.1-0.5 MPa.
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