CN116408126B - Preparation method and application of nano zinc oxide/nitrogen doped carbon catalyst - Google Patents
Preparation method and application of nano zinc oxide/nitrogen doped carbon catalyst Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 30
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 30
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 19
- 239000001294 propane Substances 0.000 claims abstract description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 13
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 102000020897 Formins Human genes 0.000 claims description 8
- 108091022623 Formins Proteins 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000003993 interaction Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- -1 VO x Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a preparation method of a nano zinc oxide/nitrogen doped carbon catalyst, which comprises the following steps: adding polyamide-imide into N, N-dimethylformamide at room temperature, stirring and dissolving to obtain the polyamide-imide with the concentration of 0.10-0.25 g.mL ‑1 Is a mixed solution of (a) and (b); adding Zn salt and hexamethylenetetramine into the mixed solution, stirring and curing the mixed solution at 120-200 ℃ until the mixed solution is sticky, and then carrying out vacuum curing to obtain a catalyst precursor; roasting the catalyst precursor to obtain the nano zinc oxide/nitrogen doped carbon catalyst. The method is simple, the obtained nano zinc oxide/nitrogen-doped carbon catalyst has high dispersity of active components, znO and a nitrogen-doped carbon carrier have strong interaction, and the small-size zinc oxide/nitrogen-doped carbon catalyst material inhibits aggregation and loss of the active components in the process of preparing propylene by propane dehydrogenation, and has higher propylene selectivity and catalytic stability.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a preparation method and application of a nano zinc oxide/nitrogen doped carbon catalyst.
Background
In recent years, low-carbon olefin has been attracting attention as the most important base raw material and core product in petrochemical industry, wherein propylene is the most important base petrochemical raw material except ethylene in the low-carbon olefin, and is a key raw material for producing plastics, packaging materials and synthetic fibers. Propylene is mainly derived from naphtha cracking and heavy oil cracking, and future chemical processes based on non-petroleum resources such as shale gas tend to influence the source of propylene to a large extent. The production of propylene by dehydrogenation of propane has received considerable attention in recent years due to the domestic oil/gas resource reserves and the year-by-year increase in propylene market demand. The current national propane dehydrogenation project accounts for 15.8% of the total propylene productivity, has a significant position, but adopts foreign UOP and Lumms process technologies. Therefore, the development of the efficient and stable catalyst for preparing propylene by dehydrogenating propane has great theoretical research value and significance in China.
Research on low-carbon alkane dehydrogenation technology originates from the 30 th century, and has achieved high cost and CrO of industrialized Pt-based catalysts x The environmental problems of the base catalysts have stimulated the development of new generation high efficiency stable non-toxic low cost catalysts in recent years. The direct dehydrogenation of propane to propylene has strong heat absorption and needs to be carried out at a higher temperature, so the problems of stability such as catalyst sintering and carbon deposition are faced. Many catalyst systems include metal oxides such as VO x 、FeO x The research and study work of ZnO and the like, metal sulfides, carbon materials, monoatomic catalysts and the like has important reference values. Among them, metal oxide ZnO has been paid attention to in dehydrogenation reaction due to its excellent dehydrogenation activity and low cost, but there is still a controversy about the knowledge of the nature of the active site of dehydrogenation reaction and the interaction with the carrier. Since propane dehydrogenation is a strong endothermic reaction, it is usually carried out at a relatively high temperature, whereas Zn is volatile at a high temperature and is easily agglomerated, resulting in a decrease in reactivity. Thus, improving the catalytic activity and stability of Zn-based catalysts is currently the main goal.
Nanocarbon materials have also been used in recent years as a good nonmetallic material for low-carbon alkane dehydrogenation reactions. However, the carbon material carbonized at high temperature is susceptible to side reactions in dehydrogenation reaction and has poor long-term stability, so that modification of the carbon material is required.
Disclosure of Invention
The invention aims to provide a preparation method of a nano zinc oxide/nitrogen doped carbon catalyst with simple method and good performance.
Another technical problem to be solved by the present invention is to provide an application of the nano zinc oxide/nitrogen doped carbon catalyst.
In order to solve the problems, the preparation method of the nano zinc oxide/nitrogen doped carbon catalyst is characterized by comprising the following steps of: adding polyamide-imide into N, N-dimethylformamide at room temperature, stirring and dissolving to obtain the polyamide-imide with the concentration of 0.10-0.25 g.mL -1 Is a mixed solution of (a) and (b); adding Zn salt and hexamethylenetetramine into the mixed solution, stirring and curing the mixed solution at 120-200 ℃ until the mixed solution is sticky, and then carrying out vacuum curing to obtain a catalyst precursor; roasting the catalyst precursor to obtain the nano zinc oxide/nitrogen doped carbon catalyst.
The solid content of the polyamide-imide is 30-40%, and the viscosity is 2000-7000 cps.
The Zn salt refers to zinc nitrate Zn (NO) 3 ) 2 ·6H 2 O, zinc acetate C 4 H 6 O 4 Zn·2H 2 O and Zinc chloride ZnCl 2 One of them.
The mass ratio of the Zn salt to the polyamide-imide is 0.2-1.2: 1.
the mass ratio of the hexamethylenetetramine to the polyamide-imide is 1:5-1:10.
The vacuum curing condition means that the vacuum degree is 0.06-0.08 MPa, the temperature is 100-150 ℃ and the time is 4-24 hours.
The roasting condition refers to that the mixture is roasted at the temperature of 1 ℃ mm under the atmosphere of nitrogen -1 And (3) heating to 500-800 ℃ at a heating rate, and roasting for 2.0-4.0 h.
The active component of the nano zinc oxide/nitrogen-doped carbon catalyst is ZnO nano particles with an average particle size of 5.1-8.6 nm, the mass fraction of ZnO is 5-30%, and the carrier is nitrogen-doped carbon material.
The nano zinc oxide/nitrogen doped carbon catalyst is applied to the reaction of preparing propylene by dehydrogenating propane.
Compared with the prior art, the invention has the following advantages:
1. because Zn can be bonded with N in polyamide-imide in a Zn-N coordination bond mode, znO has good dispersibility after roasting, and Zn and a nitrogen-doped carbon carrier have stronger interaction, the small-size zinc oxide/nitrogen-doped carbon catalytic material can be obtained.
2. The preparation method is simple, the obtained nano zinc oxide/nitrogen-doped carbon catalyst has high dispersity of active components, znO and a nitrogen-doped carbon carrier have strong interaction, and the small-size zinc oxide/nitrogen-doped carbon catalyst material inhibits aggregation and loss of the active components in the process of preparing propylene by propane dehydrogenation, and has higher propylene selectivity and catalytic stability.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 is a TEM image of a nano zinc oxide/nitrogen doped carbon catalyst prepared in example 1 of the present invention.
Fig. 2 is a TEM image of a nano zinc oxide/nitrogen doped carbon catalyst prepared in example 1 of the present invention after propane dehydrogenation reaction of 3.5. 3.5 h.
Detailed Description
A preparation method of a nano zinc oxide/nitrogen doped carbon catalyst, which comprises the following steps:
adding polyamide-imide into N, N-dimethylformamide at room temperature, stirring and dissolving to obtain the polyamide-imide with the concentration of 0.10-0.25 g.mL -1 Is a mixed solution of (a) and (b). Adding Zn salt and hexamethylenetetramine into the mixed solution, wherein the mass ratio (g/g) of the Zn salt to the polyamide-imide is 0.2-1.2: 1, a step of; the mass ratio (g/g) of the hexamethylenetetramine to the polyamide-imide is 1:5-1:10. Stirring and curing at 120-200 ℃ until the catalyst precursor is sticky, and then vacuum curing at 0.06-0.08 MPa and 100-150 ℃ for 4-24 hours to obtain the catalyst precursor; catalyst precursor at 1 ℃ mim under nitrogen atmosphere -1 And (3) heating to 500-800 ℃ at a heating rate, and roasting for 2.0-4.0 h to obtain the nano zinc oxide/nitrogen doped carbon catalyst.
Wherein: the solid content of the polyamide-imide is 30-40%, and the viscosity is 2000-7000 cps.
Zn salt refers to zinc nitrate Zn (NO) 3 ) 2 ·6H 2 O, zinc acetate C 4 H 6 O 4 Zn·2H 2 O and Zinc chloride ZnCl 2 One of them.
The active component of the obtained nano zinc oxide/nitrogen-doped carbon catalyst is ZnO nano particles with an average particle size of 5.1-8.6 nm, the mass fraction of ZnO is 5-30%, and the carrier is nitrogen-doped carbon material.
The nano zinc oxide/nitrogen doped carbon catalyst is applied to the reaction of preparing propylene by dehydrogenating propane.
Example 1
5.0. 5.0 g Polyamide-imide (solid content: 38%) was added to 30 mL of N, N-dimethylformamide at room temperature and dissolved with stirring to give a concentration of 0.17 g. Mu.mL -1 Is a uniform mixed solution of (a) and (b). 3.23 g Zn (NO) was added 3 ) 2 ·6H 2 O and 1.0 g hexamethylenetetramine are heated to 120 ℃ and stirred and cured to be sticky, and then are placed under 0.08 MPa and 150 ℃ for vacuum curing for 4 h, thus obtaining the Zn-loaded polyamide-imide precursor. The precursor is processed under nitrogen atmosphere at 1 ℃ for min -1 And (3) heating to 600 ℃ and roasting 3.0. 3.0 h to obtain the nano zinc oxide/nitrogen doped carbon catalyst. The mass fraction of ZnO on the catalyst is 15%, and the average size of nano particles is 5.1 and nm.
When the obtained catalyst was observed by a transmission electron microscope, as shown in fig. 1, it was found that ZnO particles on the catalyst had a size of about 5.1. 5.1 nm and were uniformly distributed on the carrier.
Example 2
7.5. 7.5 g Polyamide-imide (38% solids) was added to 30 mL of N, N-dimethylformamide at room temperature and dissolved with stirring to give a concentration of 0.25 g. Mu.mL -1 Is a uniform mixed solution of (a) and (b). 1.44 g Zn (NO) was added 3 ) 2 ·6H 2 O and 0.75. 0.75 g hexamethylenetetramine are heated to 200 ℃, stirred and cured to be sticky, and then placed under 0.06MPa and 100 ℃ for vacuum curing of 12 h, thus obtaining the Zn-loaded polyamide-imide precursor. The precursor is processed under nitrogen atmosphere at 1 ℃ for min -1 Roasting 2.0. 2.0 h to 700 deg.c to obtain nanometer zinc oxide/nitrogen doped carbon catalystAnd (3) an agent. The mass fraction of ZnO on the catalyst is 5%, and the average size of nano particles is 6.6 nm.
Example 3
3.0. 3.0 g Polyamide-imide (solid content: 30%) was added to 30 mL of N, N-dimethylformamide at room temperature and dissolved with stirring to give a concentration of 0.10 g. Mu.mL -1 Is a uniform mixed solution of (a) and (b). 2.02 g of C are added 4 H 6 O 4 Zn·2H 2 O and 0.6. 0.6 g hexamethylenetetramine are heated to 150 ℃, stirred and cured to be sticky, and then placed under 0.07 MPa and 120 ℃ for vacuum curing for 24 h, thus obtaining the Zn-loaded polyamide-imide precursor. The precursor is processed under nitrogen atmosphere at 1 ℃ for min -1 And (5) heating to 500 ℃ and roasting to 4.0 and h to obtain the nano zinc oxide/nitrogen doped carbon catalyst. The mass fraction of ZnO on the catalyst is 20%, and the average size of nano particles is 6.9 and nm.
Example 4
6.0. 6.0 g Polyamide-imide (solid content 40%) was added to 30 mL of N, N-dimethylformamide at room temperature and dissolved with stirring to give a concentration of 0.20 g. Mu.mL -1 Is a uniform mixed solution of (a) and (b). 4.31 g ZnCl was added 2 And 0.8 g hexamethylenetetramine, heating to 180 ℃, stirring and curing to be sticky, and then placing the sticky and sticky mixture at 0.08 MPa and 120 ℃ for vacuum curing of 12 h to obtain the Zn-loaded polyamide-imide precursor. The precursor is processed under nitrogen atmosphere at 1 ℃ for min -1 And (5) heating to 800 ℃ and roasting 2.0 and h to obtain the nano zinc oxide/nitrogen doped carbon catalyst. The mass fraction of ZnO on the catalyst is 30%, and the average size of nano particles is 8.6 and nm.
Example 5
5.0. 5.0 g Polyamide-imide (38% solids) was added to 30 mL of N, N-dimethylformamide at room temperature and dissolved with stirring to give a concentration of 0.20 g. Mu.mL -1 Is a uniform mixed solution of (a) and (b). 6.09 g Zn (NO) 3 ) 2 ·6H 2 O and 1.0 g hexamethylenetetramine are heated to 180 ℃ and stirred and cured to be sticky, and then are placed under 0.08 MPa and 120 ℃ for vacuum curing of 12 h, thus obtaining the Zn-loaded polyamide-imide precursor. The precursor is processed under nitrogen atmosphere at 1 ℃ for min -1 Roasting 2.0. 2.0 h to 800 deg.c to obtain nanometer zinc oxide/nitrogen doped carbon catalystAnd (3) a chemical agent. The mass fraction of ZnO on the catalyst is 25%, and the average size of nano particles is 7.2 nm.
Comparative example 1
5.0. 5.0 g Polyamide-imide (solid content: 38%) was added to 30 mL of N, N-dimethylformamide at room temperature and dissolved with stirring to give a concentration of 0.17 g. Mu.mL -1 Is a uniform mixed solution of (a) and (b). Adding 1.0 g hexamethylenetetramine, heating to 120 ℃, stirring and curing to be sticky, and then placing under 0.08 MPa and 150 ℃ for vacuum curing 12 h to obtain the polyamide-imide precursor. The precursor is processed under nitrogen atmosphere at 1 ℃ for min -1 And (5) heating to 600 ℃ and roasting 2.0 and h to obtain the nitrogen-doped carbon catalyst.
Comparative example 2
3.0. 3.0 g of the nitrogen-doped carrier prepared in comparative example 1 was added to a crucible under irradiation of an infrared lamp, and 1.94 g of Zn (NO 3 ) 2 ·6H 2 O is dissolved in 5 mL water to obtain a precursor solution, the precursor solution is added into a crucible, the crucible is immersed while stirring, the crucible is dried in an oven at 120 ℃ for overnight after the solvent is evaporated, and the crucible is heated in a nitrogen atmosphere at 1 ℃ for min -1 And (3) heating to 600 ℃ and roasting 2.0. 2.0 h to obtain the post-loaded zinc oxide/nitrogen-doped carbon catalyst. The mass fraction of ZnO on the catalyst is 15%, and the average size of nano particles is 170 nm.
The specific reaction conditions for propane or dehydrogenation reactions using the catalysts prepared in examples 1-5 and comparative examples 1-2 were: the propane dehydrogenation reaction is carried out on a fixed bed microreaction device.
And (3) weighing 0.3-g catalyst (60-80 meshes), placing the catalyst in a constant temperature section of a reaction tube, and filling the catalyst under a bed layer by using 1.0-g quartz sand with 60-80 meshes as a support. Catalyst in N 2 After the atmosphere is raised to the reaction temperature, transferring propane into the reactor at normal pressure, and analyzing the product on line after the reaction system is stabilized for 0.5 h. The reaction products were analyzed by gas chromatograph (shimadzu GC 2014) double column double detector. The hydrocarbon product being formed from gamma-Al 2 O 3 (30 m X0.53 mm X10.0 μm) separation, FID detection. CO x Separated by TDX packed column, TCD detection. The catalyst performance test results are average values within 3.5 h, as shown in table 1 below:
table 1 results of dehydrogenation reactions of propane with catalysts prepared in examples 1 to 5 and comparative examples 1 to 2
It can be seen from table 1 that the nano zinc oxide/nitrogen doped carbon catalyst prepared by the method of the present invention has good propylene selectivity. Comparing examples 1-5 with comparative example 1, the nano zinc oxide/nitrogen doped carbon catalyst is due to the presence of Zn 2+ The active sites and their strong interactions with the support have higher propane conversion and propylene selectivity compared to nitrogen-doped carbon catalysts alone. Comparing examples 1-5 with comparative example 2, the nano zinc oxide/nitrogen doped carbon catalyst has higher propylene selectivity compared with the catalyst prepared in comparative example 2 because the ZnO nanoparticles are small and strongly interact with the support.
The catalysts of example 1 and comparative example 2 were subjected to stability test, and the catalyst performance test results are shown in table 2 below:
TABLE 2 reaction results of dehydrogenation of propane over time for the catalysts prepared in example 1 and comparative example 2
As can be seen from table 2, the catalyst prepared by the method of the present invention has good catalytic reaction stability compared to the post-supported zinc oxide/nitrogen doped carbon catalyst at the same reaction time.
Meanwhile, after the catalyst obtained in example 1 is subjected to a transmission electron microscope observation after the propane dehydrogenation reaction is carried out by 3.5 and h, as shown in fig. 2, the ZnO particle size on the catalyst after the reaction is about 5.7 and nm, almost no agglomeration phenomenon exists, and the ZnO particle size is uniformly distributed on a carrier, so that the active components on the catalyst form stronger interaction with the carrier, and the catalyst has higher catalytic stability.
It should be understood that the foregoing is only a few embodiments of the present invention, and it should be noted that other modifications and improvements can be made by those skilled in the art without departing from the inventive concept of the present invention, which fall within the scope of the present invention.
Claims (5)
1. A preparation method of a nano zinc oxide/nitrogen doped carbon catalyst is characterized by comprising the following steps: adding polyamide-imide into N, N-dimethylformamide at room temperature, stirring and dissolving to obtain the polyamide-imide with the concentration of 0.10-0.25 g.mL -1 Is a mixed solution of (a) and (b); adding Zn salt and hexamethylenetetramine into the mixed solution, stirring and curing the mixed solution at 120-200 ℃ until the mixed solution is sticky, and then carrying out vacuum curing to obtain a catalyst precursor; roasting the catalyst precursor to obtain the nano zinc oxide/nitrogen doped carbon catalyst; the active component of the nano zinc oxide/nitrogen-doped carbon catalyst is ZnO nano particles with an average particle size of 5.1-8.6 nm, the mass fraction of ZnO is 5-30%, and the carrier is a nitrogen-doped carbon material; the solid content of the polyamide-imide is 30-40%, and the viscosity is 2000-7000 cps; the vacuum curing condition means that the vacuum degree is 0.06-0.08 MPa, the temperature is 100-150 ℃ and the time is 4-24 hours; the roasting condition is that under the nitrogen atmosphere, the temperature is 1 ℃ for min -1 And (3) heating to 500-800 ℃ at a heating rate, and roasting for 2.0-4.0 h.
2. The method for preparing the nano zinc oxide/nitrogen doped carbon catalyst according to claim 1, which is characterized in that: the Zn salt refers to zinc nitrate Zn (NO) 3 ) 2 ·6H 2 O, zinc acetate C 4 H 6 O 4 Zn·2H 2 O and Zinc chloride ZnCl 2 One of them.
3. The method for preparing the nano zinc oxide/nitrogen doped carbon catalyst according to claim 1, which is characterized in that: the mass ratio of the Zn salt to the polyamide-imide is 0.2-1.2: 1.
4. the method for preparing the nano zinc oxide/nitrogen doped carbon catalyst according to claim 1, which is characterized in that: the mass ratio of the hexamethylenetetramine to the polyamide-imide is 1:5-1:10.
5. The nano zinc oxide/nitrogen doped carbon catalyst prepared by the preparation method of claim 1 is applied to the reaction of preparing propylene by propane dehydrogenation.
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