CN109382084B - Mesoporous carbon material and preparation method and application thereof - Google Patents
Mesoporous carbon material and preparation method and application thereof Download PDFInfo
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- CN109382084B CN109382084B CN201810427761.3A CN201810427761A CN109382084B CN 109382084 B CN109382084 B CN 109382084B CN 201810427761 A CN201810427761 A CN 201810427761A CN 109382084 B CN109382084 B CN 109382084B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 35
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 24
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 229920003987 resole Polymers 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000013335 mesoporous material Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B01J35/617—
-
- B01J35/647—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Abstract
The invention relates to a mesoporous carbon material and a preparation method and application thereof. The mesoporous material has an ordered mesoporous pore structure and contains zinc element zinc with the mass content of 0-30.0%. The preparation method comprises the steps of mixing a template agent, an organic solvent, a carbon source and a zinc-containing precursor to obtain a colloidal solution, removing the organic solvent in the colloidal solution, then curing to obtain a compound, calcining the compound in an inert atmosphere to remove the template agent, and then carbonizing to obtain the zinc-containing mesoporous carbon material. The preparation method is simple and easy to implement, has good repeatability, controllable zinc content and good dispersibility. The material has better catalytic activity for producing vinyl acetate by an acetylene method.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a mesoporous carbon material and a preparation method and application thereof.
Technical Field
The mesoporous carbon material is a porous carbon material with the pore diameter within the range of 2-50 nm, and has a mesoporous pore channel structure which is orderly arranged, a relatively stable framework structure, better thermal stability, good dispersibility on noble metal atoms, excellent adsorption performance and the like, so that the mesoporous carbon material has a unique application value and a wide application prospect in the field of catalysis.
Through surface functionalization, the mesoporous carbon material can have wide application prospects in the aspects of electrochemistry and the like. The post-treatment method is one of methods for functionalizing a mesoporous carbon material, and is to perform surface treatment on an obtained ordered mesoporous carbon material, that is, to perform surface modification on the mesoporous carbon material by methods such as grafting and modification, for example, patents such as CN201410173888 and CN201410190170 perform metal modification on the mesoporous carbon.
In the industrial production of vinyl acetate by acetylene method, a zinc acetate/activated carbon catalyst (CN201310023091) is adopted, but the catalyst has the defects of quick activity reduction, low stability, insufficient production capacity, short service life and the like. The main reason for the deactivation and the reduction of the service life of the catalyst is that the by-products are coked on the surface of the catalyst to block the effective pore structure of the catalyst. CN201310023093 uses carbon to deposit silicon carbide loaded zinc acetate.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides a mesoporous carbon material and a preparation method and application thereof.
The mesoporous carbon material provided by the invention has an ordered mesoporous pore structure and contains zinc element.
According to some embodiments of the mesoporous carbon material of the present invention, the mesoporous carbon material has an average pore diameter of 2-5nm, such as 3-5nm, and a specific surface area of 500-700m2/g。
According to some embodiments of the mesoporous carbon material of the invention, the content of zinc element is below 30wt%, such as 1-30wt%, preferably 2-20 wt%, such as 2-15 wt%; more preferably 5-20 wt%, such as 5-10 wt%.
The preparation method of the mesoporous carbon material provided by the invention comprises the following steps: mixing a template agent, an organic solvent, a carbon source and a zinc-containing precursor to obtain a colloidal solution, removing the organic solvent in the colloidal solution, then curing to obtain a compound, calcining the compound under an inert atmosphere to remove the template agent, and then carbonizing to obtain the zinc-containing mesoporous carbon material.
According to a preferred embodiment of the method of the present invention, the mass ratio of the templating agent, the carbon source and the organic solvent is (1-3): (5-10): (10-30), such as 1:5: 20.
According to a preferred embodiment of the method of the present invention, the zinc-containing precursor is at least one selected from the group consisting of zinc acetate, zinc nitrate, zinc carbonate, zinc chloride and zinc hydroxide, and preferably the mass ratio of the zinc-containing precursor to the carbon source is 0.3:1 or less, preferably (0.02-0.3): 1, more preferably (0.05-0.3):1, such as (0.05-0.2): 1.
according to a preferred embodiment of the method of the present invention, the templating agent is a triblock copolymer, preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide, more preferably F127, F108, P123 or mixtures thereof.
According to a preferred embodiment of the method of the present invention, the carbon source comprises one or more of a resole prepolymer, an epoxy prepolymer, sucrose and a resorcinol/formaldehyde resin. The carbon source can be made by self or purchased commercially. According to a preferred embodiment of the present invention, the method for synthesizing the resol prepolymer comprises the following steps: mixing phenol and formaldehyde solution under alkaline catalyst condition, magnetically stirring (at 70 deg.C) for reaction for a certain time (1 hr), adjusting pH to neutral, rotary evaporating at 45 deg.C to remove water, dissolving the obtained viscous liquid in a certain amount of ethanol, neutralizing to obtain salt, crystallizing, filtering, and collecting filtrate. The alkaline catalyst was a 20 wt.% NaOH solution with a phenolic molar ratio of 1: 2. In a preferred embodiment, the resol prepolymer solution contains 10 to 30wt%, such as 20 wt% of resol prepolymer.
According to a preferred embodiment of the method according to the invention, the curing temperature is between 80 and 150 ℃ and the curing time is between 12 and 36 hours.
According to a preferred embodiment of the method of the present invention, the temperature of the calcination is 300-400 ℃, such as 350 ℃, and the time of the calcination is 3-8h, such as 5 h.
According to a preferred embodiment of the method of the present invention, the carbonization temperature is 500-800 ℃ and the carbonization time is 3-8h, such as 5 h.
According to an embodiment mode of the invention, the method for synthesizing the mesoporous carbon material containing zinc by in-situ synthesis comprises the following steps: dissolving a template agent in absolute ethyl alcohol, slowly adding a carbon source and a zinc-containing precursor, and magnetically stirring for 10min to form a semitransparent colloidal solution; transferring the solution into a culture dish, and volatilizing at room temperature for 6-8 h until a transparent film is formed; then placing the culture dish into an oven, and thermally polymerizing and curing for 24 hours at the temperature of 100 ℃ to obtain a yellow transparent film-shaped compound; placing the composite in a quartz boat, and placing the quartz boat in a tube furnace, in N2And heating to 350 ℃ at the speed of 1 ℃/min under the atmosphere, keeping for 5 hours, removing the template agent, heating to 500-800 ℃ at the speed of 2 ℃/min, and carbonizing for 5 hours to obtain the zinc-containing mesoporous carbon sample.
According to a particularly preferred embodiment of the invention, the operating conditions of the reaction may be those conventional in the art, such as: the temperature is 180 ℃ and 300 ℃, the pressure is 0.1-0.5MPa, and the reaction space velocity is 250 ℃ and 350h-1The molar ratio of acetylene to acetic acid is (5-12): 1.
The invention further provides application of the mesoporous carbon material in production of vinyl acetate by an acetylene method, and the mesoporous carbon material is preferably used as a catalyst.
The preparation method provided by the invention is simple and easy to implement, good in repeatability, controllable in zinc content and good in dispersibility. According to the invention, the zinc-containing mesoporous carbon synthesized in situ has the advantages of large specific surface area, large pore volume, uniform pore size distribution, regular and ordered mesoporous channel structure with proper strength; the content of the prepared mesoporous carbon containing zinc is controllable within the range of below 30wt%, and the thermal stability is good; the prepared zinc-containing mesoporous carbon is applied to the catalytic reaction of vinyl acetate produced by an acetylene method, and has good activity, high stability and small diffusion resistance. The catalyst has good carbon deposition resistance, can react at higher temperature, and still has good reaction effect after the catalyst runs for a long time under the reaction condition of 240 ℃. Compared with the catalyst in the prior art, the catalyst has better acetic acid conversion rate, the selectivity of vinyl acetate in the product is improved, and the space-time yield of the product is improved.
Drawings
Fig. 1 shows a nitrogen adsorption-desorption isotherm diagram of a mesoporous carbon material containing zinc prepared according to an embodiment of the present invention;
FIG. 2 shows a pore size distribution diagram of a mesoporous carbon material containing zinc prepared according to one embodiment of the present invention;
fig. 3 shows an XRD pattern of a mesoporous carbon material containing zinc prepared according to an embodiment of the present invention;
fig. 4 shows a transmission electron micrograph of a mesoporous carbon material containing zinc prepared according to an embodiment of the present invention.
Detailed Description
The invention is further described in the following with reference to examples and the accompanying drawings of the specification, which are not to be construed as limiting the invention in any way.
The test method comprises the following steps:
1. testing the specific surface area, pore distribution and other pore structure properties of the catalyst by adopting a nitrogen isothermal adsorption-desorption method;
2. the crystal form of the catalyst is tested by adopting Japanese D/MAX-2500 type XRD;
3. the ordered mesoporous structure of the catalyst was tested using FEI Tecnai G2F 20 field emission transmission electron microscopy in the Netherlands.
Example 1.
Weighing 36.6g of phenol, melting at 40-42 ℃, slowly adding 7.8g of 20 wt.% NaOH solution at the temperature, magnetically stirring for 10min, then adding 63g of 37 wt.% formaldehyde solution (the molar ratio of phenolic aldehyde is 1:2), heating to 70 ℃, magnetically stirring for reacting for 1h, and stopping the reaction. After the temperature of the reaction solution was lowered to room temperature, the pH was adjusted to neutral with 0.6mol/L HCl solution. The mixture was then transferred to a rotary evaporator and the water contained therein was removed by rotary evaporation at below 45 ℃. Dissolving the obtained viscous liquid in a certain amount of ethanol, crystallizing and separating out NaCl salt generated by neutralization reaction, filtering to remove the NaCl salt, and collecting filtrate for later use. The composition of the obtained resol prepolymer solution is as follows: the mixed solution (1.0 g) contained 0.2g of a phenol resin (0.122g of phenol and 0.078g of formaldehyde).
Weighing 2g of F127 and 0.3g of zinc acetate, dissolving in absolute ethanol to form a colorless transparent solution, slowly adding 10g of the prepared phenolic resol prepolymer solution, and magnetically stirring for about 10min to form a semitransparent colloidal solution (wherein the mass ratio of the F127 to the phenolic resin prepolymer solution to the ethanol is 1:5: 20). The solution was then transferred to a petri dish and allowed to evaporate at room temperature for 8h until a clear film formed. The culture dish is put into an oven and thermally polymerized and cured for 24 hours at 100 ℃ to obtain a yellow transparent film-shaped phenolic resin/F127 compound. Weighing a certain amount of the compound in a quartz boat, placing the quartz boat in a tube furnace, and reacting in N2Heating to 350 ℃ at the temperature of 1 ℃/min under the atmosphere, keeping for 5h to fully remove the template agent F127, then heating to 700 ℃ at the temperature of 2 ℃/min, and carbonizing for 5h to obtain the zinc-containing ordered mesoporous carbon sample.
The zinc-containing ordered mesoporous carbon described above was tested and characterized as shown in fig. 1-4.
As can be seen from fig. 1, the N2 adsorption-desorption isotherm of the catalytic material is a typical type IV adsorption isotherm, which indicates that the material contains a large amount of mesoporous structures.
As can be seen from FIG. 2, the material exhibits typical mesoporous characteristics, the pore size distribution is narrow, the pore sizes are basically concentrated in the range of 2-5nm, and the average pore size is 3.9 nm.
From fig. 3 it can be seen that the catalytic material has a distinct characteristic peak of ZnO, indicating that zinc is present in the material predominantly in the form of zinc oxide.
It can be seen from fig. 4 that the catalytic material has a distinct ordered mesoporous structure.
Example 2.
The same procedure as in example 1 was repeated, except that 0.4g of zinc acetate was added.
Example 3.
The same procedure as in example 1 was repeated, except that 0.1g of zinc acetate was added.
Example 4.
The same procedure as in example 1 was repeated, except that 0.6g of zinc acetate was added.
Example 5.
The same procedure as in example 1 was followed, except that the final calcination temperature was 600 ℃.
Example 6 (comparative).
This example is a comparative example. Weighing 1g of activated carbon powder, and measuring the saturated water absorption capacity of the activated carbon powder after vacuum drying for 4 hours at 150 ℃; dissolving 2.0g of zinc acetate in distilled water at 80 ℃, wherein the volume of the distilled water is five times of the saturated water absorption capacity, dropwise adding a certain amount of glacial acetic acid into the distilled water to prevent the zinc acetate from hydrolyzing, weighing 10g of activated carbon dried in vacuum at 150 ℃, pouring the activated carbon into the solution, heating and stirring the activated carbon in a water bath at 80 ℃ for 1 hour, and performing ultrasonic treatment for 2 hours; standing at room temperature for more than 24h, and drying in an oven at 80 ℃ for 12 h; tabletting and screening to obtain 20-40 mesh catalyst particles, which are marked as 20% Zn (OAc)2/AC。
Example 7.
The catalysts prepared in examples 1-6 were evaluated for activity in a fixed bed microreactor. Molar ratio of acetylene to acetic acid R (C)2H2HAc 5.5:1, volume space velocity GHSV 340h-1The reaction temperature: 210 ℃, reaction pressure: 0.02MPa, and sampling and analyzing after the reaction is stable (about 1-2 hours). The data are shown in Table 1.
Examples 8 to 9.
Acceleration of the catalysts prepared in examples 1-2 in a fixed bed microreactorAnd (5) evaluating carbon deposition experiments. Molar ratio of acetylene to acetic acid R (C)2H2HAc 5.5:1, volume space velocity GHSV 340h-1The reaction temperature: 240 ℃, reaction pressure: 0.02 MPa. After 10 hours of reaction, the reaction was sampled and analyzed. The data are shown in Table 1.
TABLE 1 evaluation results of catalyst Activity
X denotes the conversion of acetic acid, S denotes the selectivity of vinyl acetate, STY denotes the activity of the catalyst, i.e.the space-time yield of the product.
From the above data, it can be seen that the catalyst activity is high, the conversion of the feedstock is high, and the product selectivity is high according to the process of the present invention. The carbon deposition resistance of the catalyst is remarkably improved, the catalyst still keeps better performance after being analyzed after reacting for 10 hours at high temperature, and still has very high acetic acid conversion rate, vinyl acetate selectivity and space-time yield.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (15)
1. The application of the mesoporous carbon material is characterized in that the mesoporous carbon material is used as a catalyst in the production of vinyl acetate by an acetylene method, has an ordered mesoporous pore structure and contains zinc element; the average pore diameter of the mesoporous carbon material is 2-5nm, and the specific surface area is 500-700m2The content of zinc element in the mesoporous carbon material is 1-30 wt%;
the preparation method of the mesoporous carbon material comprises the following steps:
mixing a template agent, an organic solvent, a carbon source and a zinc-containing precursor to obtain a colloidal solution, removing the organic solvent in the colloidal solution, then curing to obtain a compound, calcining the compound under an inert atmosphere to remove the template agent, and then carbonizing to obtain the mesoporous carbon material.
2. The use according to claim 1, wherein the mesoporous carbon material contains 2 to 30wt% of zinc.
3. The use according to claim 1, wherein the mesoporous carbon material contains 5 to 20 wt% of zinc.
4. The use of claim 1, wherein the mass ratio of the template, the carbon source and the organic solvent is (1-3): (5-10): (10-30).
5. Use according to claim 1, wherein the zinc-containing precursor is selected from at least one of zinc acetate, zinc nitrate, zinc carbonate, zinc chloride and zinc hydroxide.
6. The use according to any one of claims 1 to 5, wherein the mass ratio of the zinc-containing precursor to the carbon source is 0.3:1 or less.
7. The use according to any one of claims 1 to 5, wherein the mass ratio of the zinc-containing precursor to the carbon source is (0.02-0.3): 1.
8. the use according to any one of claims 1 to 5, wherein the mass ratio of the zinc-containing precursor to the carbon source is (0.05-0.3): 1.
9. Use according to any one of claims 1 to 5, wherein the templating agent is a triblock copolymer.
10. Use according to any one of claims 1 to 5, wherein the templating agent is polyethylene oxide-polypropylene oxide-polyethylene oxide.
11. Use according to any one of claims 1 to 5, wherein the templating agent is at least one of triblock copolymer F127, triblock copolymer F108, triblock copolymer P123.
12. Use according to any one of claims 1 to 5, wherein the carbon source comprises one or more of a resole prepolymer, an epoxy prepolymer, sucrose and a resorcinol-formaldehyde resin.
13. Use according to any one of claims 1 to 5, wherein the curing temperature is between 80 and 150 ℃ and the curing time is between 12 and 36 hours.
14. The method as claimed in any one of claims 1 to 5, wherein the calcination temperature is 300 ℃ to 400 ℃, and the calcination time is 3 to 8 hours.
15. The use according to any one of claims 1 to 5, wherein the temperature of the carbonization is 500 ℃ and 800 ℃, and the time of the carbonization is 3 to 8 hours.
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| CN113526503A (en) * | 2021-06-22 | 2021-10-22 | 河南师范大学 | Method for synthesizing oxygen reduction catalyst from carbon-based material derived from doped chrysanthemum leaves in one step |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107833A (en) * | 1986-11-17 | 1988-07-20 | 吉林省化学纤维技术研究所 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
| WO2002040551A1 (en) * | 2000-11-14 | 2002-05-23 | Atofina Research | Polymerisation catalyst systems and their preparation |
| CN101234341A (en) * | 2008-02-28 | 2008-08-06 | 上海交通大学 | Method for preparing functional polymer-active carbon composite material for water treatment |
| WO2009107678A1 (en) * | 2008-02-26 | 2009-09-03 | 日産自動車株式会社 | Microporous carbonaceous material, manufacturing method thereof, and hydrogen storage method using a microporous carbonaceous material |
| CN102755888A (en) * | 2012-07-04 | 2012-10-31 | 中昊(大连)化工研究设计院有限公司 | Preparation and application of synthesizing chloroethylene mercury free catalyst through acetylene method |
| CN103073296A (en) * | 2013-02-05 | 2013-05-01 | 东华大学 | Preparation method for mesoporous carbon-ZAO compound material |
| CN104888779A (en) * | 2015-05-05 | 2015-09-09 | 中国矿业大学 | Preparation method of Cu nanoparticle-loaded ordered mesoporous carbon catalyst |
-
2018
- 2018-05-07 CN CN201810427761.3A patent/CN109382084B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107833A (en) * | 1986-11-17 | 1988-07-20 | 吉林省化学纤维技术研究所 | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene |
| WO2002040551A1 (en) * | 2000-11-14 | 2002-05-23 | Atofina Research | Polymerisation catalyst systems and their preparation |
| WO2009107678A1 (en) * | 2008-02-26 | 2009-09-03 | 日産自動車株式会社 | Microporous carbonaceous material, manufacturing method thereof, and hydrogen storage method using a microporous carbonaceous material |
| CN101234341A (en) * | 2008-02-28 | 2008-08-06 | 上海交通大学 | Method for preparing functional polymer-active carbon composite material for water treatment |
| CN102755888A (en) * | 2012-07-04 | 2012-10-31 | 中昊(大连)化工研究设计院有限公司 | Preparation and application of synthesizing chloroethylene mercury free catalyst through acetylene method |
| CN103073296A (en) * | 2013-02-05 | 2013-05-01 | 东华大学 | Preparation method for mesoporous carbon-ZAO compound material |
| CN104888779A (en) * | 2015-05-05 | 2015-09-09 | 中国矿业大学 | Preparation method of Cu nanoparticle-loaded ordered mesoporous carbon catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and Infrared Stealth Property of Ordered Mesoporous Carbon-Aluminum-Doped Zinc Oxide Composites;Wang, Wei，et al;《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》;20131030;第52卷(第43期);第15066-15074页 * |
| 有序介孔炭的合成及其磺化制备固体酸;高振华等;《化学工业与工程》;20160131;第33卷(第1期);第21-24页 * |
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