CN115382564A - Preparation method of hierarchical porous carbon-doped boron nitride catalyst, catalyst and application thereof - Google Patents
Preparation method of hierarchical porous carbon-doped boron nitride catalyst, catalyst and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052796 boron Inorganic materials 0.000 claims abstract description 32
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 32
- 235000013312 flour Nutrition 0.000 claims abstract description 31
- 239000001294 propane Substances 0.000 claims abstract description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
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- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
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- 238000003756 stirring Methods 0.000 claims description 3
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- 238000003837 high-temperature calcination Methods 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011148 porous material Substances 0.000 abstract description 15
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J35/61—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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention discloses a preparation method of a hierarchical pore carbon-doped boron nitride catalyst, a catalyst and application thereof, wherein flour is used as a carbon source during the preparation of the catalyst, the flour and the boron source are mixed and fermented in situ to generate rich pore channels, so that boron is uniformly dispersed in a fermented dough, and then high-temperature roasting is carried out in a nitrogen-element-containing gas atmosphere, so that carbon decomposed by the flour at high temperature can be successfully doped to the defect position of boron nitride, and rich pore channels can be generated after the flour is combusted, so that the activity, selectivity and stability of the catalyst are improved; the preparation method has the advantages that the prepared raw materials are cheap and easy to obtain, the preparation method is simple and easy to operate, the prepared catalyst has a hierarchical pore structure, the transmission and the diffusion of the raw material gas and the product are facilitated, the activation capability of propane and the selectivity of olefin can be improved, and the preparation method has wide application value.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a hierarchical pore carbon-doped boron nitride catalyst, the catalyst and application thereof.
Background
With the reduction of the global oil resource reserves and the increasing of the market demand of the low-carbon olefins, the existing production process of the low-carbon olefins is difficult to meet the market demand, so that the search for a new production process of the low-carbon olefins is urgent. China is a typical oil-poor and gas-rich country, and because resources such as natural gas, shale gas and the like are rich in low-carbon alkane, the China is prompted to convert from the preparation of low-carbon olefin from traditional petroleum resources to the production of low-carbon olefin by taking the natural gas and the shale gas as raw materials. The existing low-carbon olefin production methods mainly comprise petroleum steam cracking, fluid Catalytic Cracking (FCC), methanol To Olefin (MTO) and Fischer-Tropsch to olefin (FTO), but the above technologies all have the defects of high energy consumption and large carbon emission, and are inconsistent with the policy of low carbon and energy conservation. In recent years, the rising wave of shale gas revolution has attracted extensive attention for the catalytic conversion of low-carbon alkanes into high-value-added chemicals (olefins). Over the last several decades, researchers have found that metal oxide catalysts are an excellent class of oxidative dehydrogenation of propane (ODHP) catalysts, but still face the problem of low product selectivity due to deep oxidation reactions.
Recently, non-metal Boron Nitride (BN) can catalyze the conversion of low-carbon alkane into low-carbon olefin, and has better activity and stability. Boron nitride has excellent mechanical strength, heat conductivity and chemical stability, and is a material with wide application. Wherein hexagonal boron nitride (h-BN) has the same structure as graphite, and B atoms and N atoms are alternately arranged to form hexagonalA honeycomb structure. Nearly simultaneously, as early as 2016, hermans and Lu et al reported that h-BN exhibited unique and heretofore unexpected oxidative dehydrogenation properties of propane with excellent selectivity (Science, 2016,354, 1570-1573. For example, when the h-BN catalyst is applied to the OHDP reaction, the propane conversion rate is 19.1% at a reaction temperature of 500 ℃, and the ethylene selectivity of 11.5% and the propylene selectivity of 76.0% are maintained at the moment, while the CO is maintained x (CO+CO 2 ) The selectivity of (a) is only 9.4%. The performance evaluation results are superior to the optimal results of the currently reported supported vanadium-based catalyst, and the catalyst has good stability, so that a new research direction for producing olefin from low-carbon alkane can be provided. However, a number of studies have shown that: only B-O and B-OH at h-BN edge and/or defect position are active sites for activating and converting alkane, and in order to further improve the catalytic performance of the h-BN catalyst, the design and preparation of the BN catalyst with high content and uniformly dispersed B-O and B-OH sites are important.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a hierarchical pore carbon-doped boron nitride catalyst, a catalyst and an application thereof, so as to improve B-O and B-OH sites in the catalyst and improve the performance of the catalyst.
In one aspect, the invention provides a preparation method of a hierarchical pore carbon-doped boron nitride catalyst, which comprises the following steps:
s1: fully mixing flour, yeast and a boron source, adding water, uniformly stirring, standing and fermenting to obtain a flour-boron source precursor with a honeycomb structure;
s2: freeze-drying the flour-boron source precursor to obtain a dehydrated flour-boron source precursor;
s3: and (3) putting the dehydrated flour-boron source precursor into a tubular furnace, introducing gas containing nitrogen elements, heating and roasting at high temperature to obtain the product.
Preferably, the boron source is any one of boric acid, metaboric acid or sodium borohydride.
Further preferably, in step S1, the mass ratio of the flour to the boron source is 0.3 to 3.0.
More preferably, in step S2, the flour-boron source precursor is subjected to vacuum degree of 10 -6 -10 -3 Freeze drying under MPa.
Further preferably, the freeze-drying time is 30-60h.
More preferably, in step S3, the gas containing nitrogen is one of ammonia and nitrogen.
More preferably, in step S3, the temperature of the high-temperature calcination is 1000 to 1500 ℃.
More preferably, in step S3, the rate of temperature rise is 2 ℃/min.
On the other hand, the invention also provides a hierarchical pore carbon-doped boron nitride catalyst, which is prepared by any one of the methods, wherein the catalyst has both mesoporous and macroporous structures, and the surface area of the catalyst is 110-140m 2 /g。
In addition, the invention also provides an application of the hierarchical pore carbon-doped boron nitride catalyst, and particularly, the catalyst is used for propane oxidative dehydrogenation.
According to the preparation method of the hierarchical pore carbon doped boron nitride catalyst, flour is used as a carbon source, the flour and the boron source are mixed and fermented in situ to generate rich pore channels, so that boron is uniformly dispersed in a fermented dough, and then high-temperature roasting is carried out in a nitrogen element-containing gas atmosphere, so that carbon decomposed by the flour at high temperature can be successfully doped to the defect position of boron nitride, and rich pore channels can be generated after the flour is combusted, so that the activity, selectivity and stability of the catalyst are improved.
The preparation method of the hierarchical pore carbon-doped boron nitride catalyst provided by the invention has the advantages that the prepared raw materials are cheap and easy to obtain, the preparation method is simple and easy to operate, the prepared catalyst has a hierarchical pore structure, the transmission and the diffusion of raw material gas and products are facilitated, the activation capacity of propane and the selectivity of olefin are improved, the conversion rate, the selectivity and the stability are excellent, the technical and economic effects are obvious, and the application value is wide.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an optical and SEM photograph of a multi-stage porous carbon-doped boron nitride catalyst prepared in example 1 of the present disclosure, wherein, a and b are optical photographs before firing, c is an optical photograph after firing, and d is an SEM photograph after firing;
FIG. 2 is a graph of N for a hierarchical pore carbon doped boron nitride catalyst and commercial boron nitride prepared in example 1 of the present disclosure 2 Comparing adsorption-desorption isotherms;
FIG. 3 is a graph comparing the performance of a multi-stage pore carbon-doped boron nitride catalyst prepared in accordance with the disclosed example with commercial boron nitride in a propane oxidative dehydrogenation reaction;
fig. 4 is a graph showing the stability of the multi-pore carbon-doped boron nitride catalyst prepared in example 1 of the present disclosure in the oxidative dehydrogenation of propane.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, and the following embodiments are only used for more clearly illustrating the technical solutions of the present invention, and therefore are only used as examples, and the protection scope of the present invention is not limited thereby.
The test methods in the following examples are all conventional methods unless otherwise specified.
The experimental materials used in the following examples are not specifically described, and are all purchased from a conventional reagent store.
In the quantitative experiments in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In order to improve the catalytic performance of the h-BN catalyst, BO in the catalyst is improved x And the content of B-OH sites and the uniformity of dispersion, the embodiment provides a novel and efficient preparation method of a hierarchical pore carbon-doped boron nitride catalyst, biomass is adopted as a template in the preparation method, a pore structure is generated through fermentation, and then high-temperature roasting is matched, so that carbon is uniformly doped into a BN structure, and the catalyst for propane oxidative dehydrogenation reaction with high activity, high selectivity and high stability is obtained.
S1: fully mixing flour, yeast and a boron source, adding water, uniformly stirring, standing and fermenting to obtain a flour-boron source precursor with a honeycomb structure;
s2: freeze-drying the flour-boron source precursor in the step S1 to obtain a dehydrated flour-boron source precursor;
s3: and (3) putting the flour-boron source precursor dehydrated in the step (S2) into a tube furnace, introducing gas containing nitrogen elements, and heating for high-temperature roasting to obtain a product.
In the preparation method, flour is used as a carbon source, rich pore channels are generated in a fermentation mode, and in the preparation process, the flour and the boron source are subjected to in-situ mixing fermentation, so that boron in the formed fermented dough is uniformly dispersed, carbon decomposed by the flour can be successfully doped to the defect position of boron nitride in subsequent high-temperature roasting, and the rich pore channels can be generated after the flour is combusted, so that a multi-level pore structure is formed in a catalyst.
In the step S1 of the above embodiment, the flour may be any one of low gluten flour, medium gluten flour or high gluten flour or a mixture of a plurality of the flour, preferably high gluten flour; the boron source used can be any one of boric acid, metaboric acid or sodium borohydride, preferably boric acid, and the boric acid is a cheap and easily-obtained precursor and does not introduce other impurity elements after being decomposed as the boron source; the yeast can be selected from any one of common dry yeast powder or high-activity fresh yeast; the mass ratio of the flour to the boron source in the step S1 is 0.3-3.0, preferably 0.38-0.50, and the following tests prove that: if the ratio of the flour to the boric acid is too high to exceed 3.0, the content of carbon in the synthesized carbon-doped boron nitride material is high, and the reaction stability of the material is reduced, while if the ratio of the flour to the boric acid is too low to be 0.3, the flour is difficult to ferment.
In step S2 of the above embodiment, the flour-boron source precursor is subjected to vacuum degree of 10 -6 -10 -3 Freeze-drying under MPa for 30-60 hr, preferably 40-48 hr.
In step S3 of the above embodiment, the gas containing nitrogen element may be any one of ammonia gas or nitrogen gas, preferably ammonia gas, because ammonia gas has certain corrosivity, ammonia gas can etch away excess carbon during the baking process; wherein, the high-temperature roasting temperature is 1000-1500 ℃, the high-temperature roasting temperature is maintained for 2-10h, preferably 1200 ℃, the heating rate during the high-temperature roasting is preferably 2 ℃/min, if the heating rate is too fast, the decomposition rate of boric acid and flour is accelerated, so that the substances are possible to be incompletely decomposed and influence on the porous structure of the catalyst, otherwise, the too slow heating rate can prolong the reaction time, and the production cost is increased invisibly.
The catalyst prepared by the method has both mesoporous and macroporous structures, and the surface area of the catalyst is 110-140m 2 /g。
The hierarchical pore carbon-doped boron nitride catalyst prepared by the method can obviously reduce the formation energy of active oxygen species by doping carbon into boron nitride, is favorable for the formation of the active oxygen species, can be used for oxidation dehydrogenation reaction of propane, is favorable for the activation and conversion of propane molecules, and can reduce the occurrence of several deep oxidation reactionsThe conversion rate of propane of the catalyst is as high as 62.1% at 520 ℃, and the selectivity of total olefin is 68.8%. Wherein, the catalyst is applied to the propane oxidative dehydrogenation reaction, and the preferable reaction conditions are as follows: the reaction temperature is 450-530 ℃, and the space velocity is 0.17-0.67g cat /mL·min。
The present invention will be further explained with reference to specific examples, but the present invention is not limited to the scope of the present invention.
Example 1
The preparation method of the carbon-doped boron nitride catalyst with the hierarchical pore structure comprises the following specific preparation steps:
(1) Grinding and uniformly mixing commercially available high gluten flour and boric acid (the mass ratio of the high gluten flour to the boric acid is 0.38), then adding 2g of high-activity yeast powder, continuously grinding and mixing, then adding a small amount of distilled water, uniformly mixing, and standing at room temperature for 24 hours to obtain the flour-boric acid precursor with the honeycomb structure.
(2) Carrying out freeze drying treatment on the flour-boric acid precursor obtained in the step (1), wherein the drying conditions are as follows: vacuum degree of 10 -6 -10 -3 And (5) drying for 48 hours under the MPa condition to obtain the dehydrated flour-boric acid precursor.
(3) Transferring the dehydrated flour-boric acid precursor to a tubular furnace, roasting for 2 hours at 1000 ℃ in an ammonia atmosphere, and cooling to room temperature to obtain the multi-level porous carbon-doped boron nitride catalyst.
The morphology of the prepared hierarchical pore carbon-doped boron nitride catalyst is shown in fig. 1, wherein a and b in fig. 1 are optical photographs of the hierarchical pore carbon-doped boron nitride before roasting, c is an optical photograph of the hierarchical pore carbon-doped boron nitride after roasting, and d is an SEM photograph of the hierarchical pore carbon-doped boron nitride, and it can be seen that the honeycomb structure is well maintained before and after the catalyst is roasted.
FIG. 2 is a graph of N for bulk phase boron nitride and the multi-level pore carbon doped boron nitride prepared in this example 2 Adsorption-desorption isotherms are compared. As can be seen from FIG. 2, the hierarchical porous carbon-doped boron nitride material has obvious nitrogen adsorption at a low-pressure section, which indicates that the prepared material has a microporous structure; at the same time, the surface appears in the middle-pressure section and the high-pressure sectionThe hysteresis loop is shown, which indicates that the catalyst prepared in the example has a mesoporous structure. Because the carbon-doped boron nitride has a multi-stage pore channel structure, the reaction feed gas can be better contacted with the active site of the catalyst, so that reactant molecules can be better activated; the developed pore structure is also beneficial to the diffusion of reactants and products, so that the occurrence of deep oxidation reaction can be avoided.
Example 2
A hierarchical pore carbon-doped boron nitride catalyst was prepared according to the method of example 1, except that: in the step (1), boric acid is replaced by metaboric acid, and the mass ratio of the flour to the boron source is 1.0; in the step (2), the freeze drying time is prolonged to 60h; in the step (3), the calcination temperature is 1500 ℃.
Example 3
In this embodiment, the hierarchical porous carbon-doped boron nitride porous carbon catalyst (P-CBN) prepared in example 1 is applied to the preparation of propylene and ethylene by oxidative dehydrogenation of propane, and the performance of the hierarchical porous carbon-doped boron nitride porous carbon catalyst for the oxidative dehydrogenation reaction of propane is evaluated, specifically, the following process is performed:
(1) Reaction and detection device
The performance evaluation of the catalyst for the propane oxidative dehydrogenation reaction is carried out on a fixed bed microreactor, the catalyst is placed in the center of a quartz reaction tube (the inner diameter is 6mm, the outer diameter is 8 mm), and reaction gas and products directly enter an Agilent 7890B gas chromatography for detection.
(2) Test conditions
The particle size of the catalyst is 60-80 meshes, the volume ratio of the raw material gas is 1.
(3) Analytical method
The conversion of propane, the selectivity of the olefin and its yield were calculated by means of a carbon balance. The specific method is as follows:
Y i (%)=Conv(C 3 H 8 )×S i /100;
wherein i represents the product, carb i Is the number of carbon atoms of component i.
FIG. 3 is a graph showing the comparison of the activity of the P-CBN catalyst prepared in example 1 and a commercial boron nitride catalyst in the oxidative dehydrogenation of propane to produce propylene and ethylene under the reaction conditions of T =510 ℃ C 3 H 8 :O 2 :N 2 1 and m =0.1g. As can be seen from fig. 3: at 510 ℃, the oxidative dehydrogenation performance of propane on the P-CBN catalyst is far higher than that of an activated bulk BN catalyst. At a propane conversion of 40.5% on P-CBN catalyst, the propane conversion on activated bulk BN catalyst was only 16%. In addition, it can be seen that the P-CBN catalyst can still achieve a higher olefin yield while maintaining a higher propane conversion, where the total olefin (propylene + ethylene) yield over the P-CBN catalyst is 31.5%, which is about 2.2 times that of the commercial bulk BN catalyst.
Example 4
In this embodiment, the physical properties of the hierarchical pore carbon-doped boron nitride catalyst prepared in example 1 are detected as follows: the specific surface area of the catalyst was 137m 2 (ii)/g, pore volume and pore diameter are 0.08cm 3 G and 4.3nm.
The hierarchical pore carbon-doped boron nitride catalyst (P-CBN catalyst) prepared in example 1 is applied to the reaction of preparing low-carbon olefin by propane oxidative dehydrogenation, and the reaction condition (C) is maintained 3 H 8 :O 2 :N 2 1 =1 and 4, the reaction temperature was 490 ℃), and a graph of the propane conversion and the propylene selectivity as a function of the reaction time was obtained, as shown in fig. 4. As can be seen from the figure, the propane conversion and propylene selectivity remained essentially stable for 60 hours, indicating that the P-CBN catalyst prepared in example 1 was stable under the given reaction conditions.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. A preparation method of a hierarchical pore carbon-doped boron nitride catalyst is characterized by comprising the following steps:
s1: fully mixing flour, yeast and a boron source, adding water, uniformly stirring, standing and fermenting to obtain a flour-boron source precursor with a honeycomb structure;
s2: freeze-drying the flour-boron source precursor to obtain a dehydrated flour-boron source precursor;
s3: and (3) putting the dehydrated flour-boron source precursor into a tube furnace, introducing nitrogen-containing gas, heating and roasting at high temperature to obtain the product.
2. The method for preparing a hierarchical pore carbon-doped boron nitride catalyst according to claim 1, wherein the boron source is any one of boric acid, metaboric acid or sodium borohydride.
3. The method for preparing the hierarchical pore carbon-doped boron nitride catalyst according to claim 1, wherein in the step S1, the mass ratio of the flour to the boron source is 0.3-3.0.
4. The method for preparing the hierarchical pore carbon-doped boron nitride catalyst according to claim 1, wherein in the step S2, the flour-boron source precursor is subjected to a vacuum degree of 10 -6 -10 -3 Freeze drying under MPa.
5. The method for preparing the hierarchical pore carbon-doped boron nitride catalyst according to claim 4, wherein the freeze-drying time is 30-60h.
6. The method for preparing the hierarchical pore carbon-doped boron nitride catalyst according to claim 1, wherein in the step S3, the gas containing the nitrogen element is any one of ammonia gas and nitrogen gas.
7. The method for preparing the hierarchical pore carbon-doped boron nitride catalyst according to claim 1, wherein in the step S3, the high-temperature calcination temperature is 1000-1500 ℃.
8. The method for preparing a hierarchical pore carbon-doped boron nitride catalyst according to claim 1, wherein in step S3, the temperature rise rate is 2 ℃/min.
9. A hierarchical pore carbon-doped boron nitride catalyst, characterized in that the catalyst is prepared by any one of the methods of claims 1-8, both mesoporous and macroporous structures are present in the catalyst, and the surface area of the catalyst is 110-140m 2 /g。
10. The application of the hierarchical pore carbon-doped boron nitride catalyst is characterized in that the hierarchical pore carbon-doped boron nitride catalyst is used for propane oxidative dehydrogenation.
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CN106140240A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院金属研究所 | A kind of low-carbon alkanes or alkylbenzene oxidative dehydrogenation boron nitride catalyst and its preparation method and application |
CN106694017A (en) * | 2016-11-30 | 2017-05-24 | 大连理工大学 | Catalyst for oxidative dehydrogenation of light alkane to prepare olefin, optimization method and application thereof |
CN108371953A (en) * | 2018-02-07 | 2018-08-07 | 青岛大学 | It is a kind of for the BCN catalyst of Knoevenagel condensation reactions and its preparation and application |
CN113058632A (en) * | 2021-03-26 | 2021-07-02 | 福州大学 | Platinum-series catalyst with hexagonal boron carbon nitride as carrier and preparation method thereof |
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CN106140240A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院金属研究所 | A kind of low-carbon alkanes or alkylbenzene oxidative dehydrogenation boron nitride catalyst and its preparation method and application |
CN106694017A (en) * | 2016-11-30 | 2017-05-24 | 大连理工大学 | Catalyst for oxidative dehydrogenation of light alkane to prepare olefin, optimization method and application thereof |
CN108371953A (en) * | 2018-02-07 | 2018-08-07 | 青岛大学 | It is a kind of for the BCN catalyst of Knoevenagel condensation reactions and its preparation and application |
CN113058632A (en) * | 2021-03-26 | 2021-07-02 | 福州大学 | Platinum-series catalyst with hexagonal boron carbon nitride as carrier and preparation method thereof |
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