CN112844352B - Application of carbon material catalyst in cyclohexane oxidative dehydrogenation - Google Patents
Application of carbon material catalyst in cyclohexane oxidative dehydrogenation Download PDFInfo
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title abstract description 29
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002113 nanodiamond Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000001307 helium Substances 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 17
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 5
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 229910021404 metallic carbon Inorganic materials 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 230000000694 effects Effects 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 238000004949 mass spectrometry Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- PQMCFTMVQORYJC-UHFFFAOYSA-N 2-aminocyclohexan-1-ol Chemical compound NC1CCCCC1O PQMCFTMVQORYJC-UHFFFAOYSA-N 0.000 description 1
- DCQQZLGQRIVCNH-UHFFFAOYSA-N 2-methoxycyclohexan-1-ol Chemical compound COC1CCCCC1O DCQQZLGQRIVCNH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 150000001935 cyclohexenes Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- -1 high Chemical compound 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
-
- 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
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/18—Carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses an application of a nano carbon material in cyclohexane oxidative dehydrogenation reaction. The nano-diamond after high-temperature roasting catalyzes cyclohexene products in a high selectivity way in a cyclohexane oxidative dehydrogenation reaction (between 300 and 500 ℃), and effectively inhibits a combustion reaction. Wherein, the selectivity of the cyclohexene product is up to 60 percent, and the selectivity of the carbon six product is over 90 percent. The catalyst has stable property, is not easy to deposit carbon, has excellent cyclohexane oxidation dehydrogenation performance, is a non-metallic carbon material, has low price and is green and environment-friendly.
Description
Technical Field
The invention relates to an application of a nano carbon material in cyclohexane oxidative dehydrogenation reaction, belonging to the technical field of catalyst preparation.
Background
Cyclohexene is an important chemical raw material, can be directly subjected to ring opening to generate hexanediol and adipic acid, and can also be subjected to alcoholysis, aminolysis and hydrolysis to obtain o-methoxycyclohexanol, o-aminocyclohexanol, 1, 2-cyclohexanediol and the like; it is also an intermediate of catechol and can be subjected to ring-opening polymerization with carbon dioxide to obtain polycarbonate. Can be widely used for organic synthesis and has wide application prospect in chemical production, pharmaceutical industry and petroleum industry.
The cyclohexene produced industrially at present is prepared by dehydrating cyclohexanol by using concentrated sulfuric acid as a catalyst, and when the cyclohexene is synthesized by adopting the method, the yield is low and the environmental pollution is serious. In the present day when sustainable development is pursued, other efficient preparation means for obtaining cyclohexene is urgently needed.
Benzene is a cheap chemical raw material, can be used as a raw material for preparing cyclohexene through selective hydrogenation, and a byproduct, namely cyclohexane, can also be used as a raw material for preparing cyclohexene through oxidative dehydrogenation, and conforms to the modern concept of green chemistry. However, the common problem in oxidative dehydrogenation of cyclohexane is that cyclohexane is easily over-oxidized to COx, and at present, the catalyst used in the oxidative dehydrogenation reaction is mainly metal, but the metal catalyst is easily over-oxidized to generate excessive COx, or over-dehydrogenation makes the selectivity of benzene particularly high, so that the selectivity of cyclohexene is improved, and the reduction of the selectivity of COx is two important problems to be solved in cyclohexene preparation, namely, the reduction of over-dissociation of C-H bonds and the inhibition of dissociation of C-C bonds.
Disclosure of Invention
In order to solve two important problems encountered in the prior oxidative dehydrogenation of cyclohexane; over-oxidation and over-dehydrogenation. The invention provides a nano carbon material with high specific surface area: the nano diamond is used as a catalyst for the oxidative dehydrogenation reaction of cyclohexane after being roasted at high temperature. The invention aims to obtain a green and environment-friendly catalyst and simultaneously has higher catalytic activity.
In order to achieve the above object, the technical solution adopted by the present invention is as follows:
the invention provides an application of a nano carbon material in a reaction of preparing cyclohexene through cyclohexane oxidative dehydrogenation, wherein the carbon material is of a core-shell structure; the core is diamond (sp3) and the shell is graphite (sp 2).
Based on the above technical scheme, preferably, the preparation method of the carbon material comprises the following steps: and roasting the nano-diamond at 900-1500 ℃ for 2-4h to obtain the carbon material.
Based on the technical scheme, preferably, the nano-diamond is washed in hydrochloric acid before being roasted; the concentration of the hydrochloric acid is 6mol/L.
Based on the technical scheme, preferably, in the reaction for preparing cyclohexene by oxidizing and dehydrogenating cyclohexane, raw material gas is cyclohexane and oxygen; taking oxygen as an oxidant and cyclohexane as a reactant; the ratio of cyclohexane to oxygen is 1: 0.25-1.25.
Based on the technical scheme, preferably, in the reaction, cyclohexane with the volume concentration of 2% and oxygen with the volume concentration of 5% are introduced, the balance gas is helium, the 2% cyclohexane/helium and the 5% oxygen/helium are mixed by a mass flow meter to form the cyclohexane-oxygen ratio of 1:1, and the flow rates of the cyclohexane/helium and the oxygen are respectively 20ml/min and 8 ml/min. The space velocity of the reaction is 2680-3600mlg -1 h- 1 。
Based on the technical scheme, the reaction temperature is preferably 300-500 ℃, preferably 300-460 ℃, and the selectivity of the C6 product is more than 90%; the selectivity of the cyclohexene product can reach 60%.
Based on the technical scheme, the particle size of the nano-diamond is preferably 5-10 nanometers, and the particle size of the calcined catalyst is basically unchanged.
Advantageous effects
1. Compared with a metal catalyst, the nano-diamond catalyst used in the invention has weaker C-H bond dissociation capability, so that excessive dehydrogenation is not easy to occur, and the generated excessive oxidation product is less than that of the metal catalyst;
2. compared with other nano carbon materials, the nano diamond catalyst used in the invention has good thermal stability, and the nano diamond still maintains unchanged activity and stability after 10h of oxidative dehydrogenation reaction, while other sp2 type carbon materials have obvious weight loss, and the weight loss of the carbon nano tube and the graphene exceeds 50%;
3. the nano diamond used in the invention has the advantages of low price, environmental protection, no metal and the like.
4. According to the invention, the diamond is subjected to high-temperature roasting treatment to prepare the non-metal catalyst which is stable in property, difficult to deposit carbon and low in price, and the non-metal catalyst is used for catalyzing cyclohexane oxidative dehydrogenation in the high-temperature oxygen atmosphere to prepare cyclohexene, the selectivity of a cyclohexene product is up to 60%, the selectivity of a carbon hexa product is over 90%, and an oxidative functional group can be generated on the surface of the catalyst in a reaction temperature interval to serve as an active center for dehydrogenation.
Drawings
FIG. 1 is an electron microscope image of catalysts obtained at different calcination temperatures in the examples of the present invention; a. no calcination is carried out; b. 900 ℃; c. 1100 ℃; d. 1200 ℃; e. 1500 ℃ in the presence of a catalyst.
FIG. 2 is an XRD pattern of the catalyst obtained by different temperatures and different calcination temperatures according to the present invention.
Detailed Description
The invention is described in detail with reference to specific examples: the nano-diamond which is washed 3-5 times by hydrochloric acid (6mol/L) to remove metal ions is calcined for 2h in inert atmosphere at different temperatures (900 ℃, 1100 ℃, 1200 ℃ and 1500 ℃) to obtain a sp3@ sp2 core-shell structure (the catalysts are respectively named as NDs, NDs-900, NDs-1100, NDs-1200 and NDs-1500), and the material is used as a catalyst to study the influence in the field of cyclohexane oxidative dehydrogenation.
Example 1
A sample of NDs-900 was loaded into a U-shaped quartz tube using 50mg of powder and tested for cyclohexane Oxidative Dehydrogenation (ODH) activity on a QMD mass spectrometry fixed bed reactor. The specific process is as follows: 5% oxygen/helium and 2% cyclohexane/helium were mixed into the reaction gas through a multichannel reaction system, the two mixed gas flows being 8ml/min and 20ml/min, respectively. The activity test was carried out at every 20 ℃ interval between 300 ℃ and 460 ℃. The reaction products (cyclohexene, benzene and carbon dioxide) can be analyzed by QMD Mass Spectrometry (MS). At 460 ℃, the conversion of cyclohexane is 12.31%, the selectivity of C6 is 89.33%, the selectivity of cyclohexene is 51.03%, and the selectivity of carbon dioxide is 10.7%; the C6 product included mainly benzene and cyclohexene.
Example 2
A sample of NDs-1100 (50 mg powder) was loaded into a U-shaped quartz tube and tested for cyclohexane Oxidative Dehydrogenation (ODH) activity on a QMD mass spectrometry fixed bed reactor. The specific process is as follows: 5% oxygen/helium and 2% cyclohexane/helium were mixed into the reaction gas through a multichannel reaction system, the two mixed gas flows being 8ml/min and 20ml/min, respectively. The activity test was carried out at every 20 ℃ interval between 300 ℃ and 460 ℃. The reaction products (cyclohexene, benzene and carbon dioxide) can be analyzed by QMD Mass Spectrometry (MS). At 460 ℃, the cyclohexane conversion was 14.93%, the C6 selectivity was 92.96%, the cyclohexene selectivity was 46.69%, and the carbon dioxide selectivity was 7.04%.
Example 3
A sample of NDs-1200 was loaded into a U-shaped quartz tube using 50mg of powder and tested for cyclohexane Oxidative Dehydrogenation (ODH) activity on a QMD mass spectrometry fixed bed reactor. The specific process is as follows: 5% oxygen/helium and 2% cyclohexane/helium were mixed into the reaction gas through a multichannel reaction system, the two mixed gas flows being 8ml/min and 20ml/min, respectively. The activity test was carried out at every 20 ℃ interval between 300 ℃ and 460 ℃. The reaction products (cyclohexene, benzene and carbon dioxide) can be analyzed by QMD Mass Spectrometry (MS). At 460 ℃, the cyclohexane conversion was 20.18%, the C6 selectivity was 95.6%, the cyclohexene selectivity was 36.75%, and the carbon dioxide selectivity was 4.6%.
Example 4
A sample of NDs-1500, 50mg powder, was loaded into a U-shaped quartz tube and tested for cyclohexane Oxidative Dehydrogenation (ODH) activity on a QMD mass spectrometric fixed bed reactor. The specific process is as follows: 5% oxygen/helium and 2% cyclohexane/helium were mixed into the reaction gas through a multichannel reaction system, the two mixed gas flows being 8ml/min and 20ml/min, respectively. The activity test was carried out at every 20 ℃ interval between 300 ℃ and 460 ℃. The reaction products (cyclohexene, benzene and carbon dioxide) can be analyzed by QMD Mass Spectrometry (MS). At 460 ℃, the conversion of cyclohexane was 13.06%, the selectivity to C6 was 94.68%, the selectivity to cyclohexene was 60.5%, and the selectivity to carbon dioxide was 5.3%.
Comparative example 1
A sample of NDs, 50mg powder, was loaded into a U-shaped quartz tube and tested for cyclohexane Oxidative Dehydrogenation (ODH) activity on a QMD mass spectrometric fixed bed reactor. The specific process is as follows: 5% oxygen/helium and 2% cyclohexane/helium were mixed into the reaction gas through a multichannel reaction system, the two mixed gas flows being 8ml/min and 20ml/min, respectively. The activity test was carried out at every 20 ℃ interval between 300 ℃ and 460 ℃. The reaction products (cyclohexene, benzene and carbon dioxide) can be analyzed by QMD Mass Spectrometry (MS). At 460 ℃, the cyclohexane conversion was 8.66%, the C6 selectivity was 84.08%, the cyclohexene selectivity was 36.49%, and the carbon dioxide selectivity was 16%.
Table 1 summarizes the catalytic performance at 460 ℃ of comparative example 1 and examples 1-4:
TABLE 1
| Catalyst and process for preparing same | C 6 H 12 Conversion rate/% | C6 Selectivity/%) | C 6 H 10 Selectivity/%) | CO 2 Selectivity/%) |
| NDs | 8.66 | 84.08 | 36.49 | 16 |
| NDs-900 | 12.31 | 89.33 | 51.03 | 10.7 |
| NDs-1100 | 14.93 | 92.96 | 46.69 | 7.04 |
| NDs-1200 | 20.18 | 95.6 | 36.75 | 4.6 |
| NDs-1500 | 13.06 | 94.68 | 60.5 | 5.3 |
Comparative example 2
A sample of carbon nanotubes, 50mg powder, was loaded into a U-shaped quartz tube and tested for cyclohexane Oxidative Dehydrogenation (ODH) activity on a QMD mass spectrometry fixed bed reactor. The specific process is as follows: 5% oxygen/helium and 2% cyclohexane/helium were mixed into the reaction gas through a multichannel reaction system, the two mixed gas flows being 8ml/min and 20ml/min, respectively. The activity test was carried out at every 20 ℃ interval between 300 ℃ and 460 ℃. The reaction products (cyclohexene, benzene and carbon dioxide) can be analysed by QMD Mass Spectrometry (MS). At 460 ℃, the cyclohexane conversion was 21.44%, the C6 selectivity was 66.1%, the cyclohexene selectivity was 7.45%, and the carbon dioxide selectivity was 33.9%.
Comparative example 3
This example illustrates catalyst 5, which shows the higher selectivity to C6 and cyclohexene in the present invention. The performance data for the catalysts of comparative examples 3 to 6 in Table 2 are reported in the literature "Aerobic oxidation of cyclohexenes with gamma-aluminous supported metallocyanines in the gas phase, Applied catalysts A: General 321(2007) 135-139"
The reaction conditions are as follows: space velocity 3305h -1 The reaction temperature T is 410 ℃, and the reaction is carried out under normal pressure.
TABLE 2
As can be seen from table 2, the catalyst of example 4 of the present invention has higher C6 selectivity and cyclohexene selectivity than the comparative catalyst, and makes full use of the reactants, and under similar conversion conditions, the catalyst of the present invention has higher selectivity, and can obtain more target products.
As can be seen from fig. 1, when the diamond is not calcined (fig. 1a), the lattice spacing d is 0.208nm, which is the (111) crystal plane of the diamond, and represents that when not calcined, the diamond structure is only present; when calcined at 900 ℃, 1100 ℃, 1200 ℃, 1500 ℃, respectively, (002) crystal planes of graphene with a lattice spacing d of 0.36nm appeared, indicating that by calcination, shells of graphene appeared, and the graphite shells became thicker as the calcination temperature increased.
As can be seen from fig. 2, as the diffraction peak of the nanodiamond gradually decreases with the increase of the firing temperature, the graphite peak gradually appears and increases, and also shows that the sp3 carbon content gradually decreases and the sp2 carbon content gradually increases.
Claims (4)
1. The application of the carbon material in the reaction of preparing cyclohexene by oxidative dehydrogenation of cyclohexane is characterized in that: the carbon material is of a core-shell structure; the core is diamond, and the shell is graphite;
the preparation method of the carbon material comprises the following steps: roasting the nano-diamond at 900-1500 ℃ for 2-4h to obtain the carbon material;
the particles of the nano diamond are 5-10 nm;
washing the nano-diamond in hydrochloric acid before roasting; the concentration of the hydrochloric acid is 6 mol/L;
the temperature of the reaction is 300-500 ℃.
2. The application of claim 1, wherein in the reaction for preparing cyclohexene by oxidative dehydrogenation of cyclohexane, raw material gases are cyclohexane and oxygen; the ratio of cyclohexane to oxygen is 1: 0.25-1.25.
3. The method as claimed in claim 2, wherein cyclohexane with a volume concentration of 2% and oxygen with a volume concentration of 5% are introduced into the reaction, the equilibrium gas is helium, and the space velocity of the reaction is 2680- -1 h -1 。
4. The use according to claim 1, wherein the selectivity to C6 product is 90% or greater; the selectivity of the cyclohexene product can reach 60%.
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