CN109225227B - Ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and preparation method thereof - Google Patents
Ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 7
- 239000005011 phenolic resin Substances 0.000 claims abstract description 7
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides an ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and a preparation method thereof, wherein a carrier is ordered mesoporous carbon, an active component is nickel, and the loading capacity of the active component accounts for 0.5-10% of the catalyst by mass; the preparation method comprises the following steps: under the alkaline condition, resorcinol and formaldehyde firstly generate a phenolic resin precursor; adding surfactant, ethanol and water, adding hydrochloric acid, adjusting the solution to acidity, and stirring to gradually turn the system to milky white; aging at room temperature, pouring clear liquid, drying at room temperature, and performing high-temperature thermal polymerization; roasting the solid in nitrogen atmosphere, and cooling to room temperature after roasting to obtain the ordered mesoporous carbon carrier; the carrier is dipped in a solution containing active metal nickel, and then the carrier is dried and roasted to prepare the catalyst for preparing the hexahydrophthalic anhydride from the tetrahydrophthalic anhydride. The catalyst prepared by the invention has the characteristic of high activity stability, and is beneficial to industrial application and popularization.
Description
Technical Field
The invention belongs to the field of industrial catalyst manufacturing, and particularly relates to an ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and a preparation method thereof.
Background
Hexahydrophthalic anhydride is called hexahydrophthalic anhydride, is white to off-white crystal, is solid with low melting point, and can be dissolved in solvents such as tetrahydrofuran, benzene, acetone and the like. Hexahydrophthalic anhydride is an indispensable raw material for producing polyester coatings, amino alkyd, polyurethane paint, powder coating and the like produced by replacing aromatic polybasic acid with hexahydrophthalic anhydride can obviously improve the distinctness of image and gloss of the coatings, and meanwhile, the hexahydrophthalic anhydride can also be used as a curing agent, an adhesive, a plasticizer and the like of epoxy resin. When used as an epoxy resin curing agent, hexahydrophthalic anhydride has the general properties of tetrahydrophthalic anhydride (high purity, light color, low viscosity, small volatility, stable performance and long working life), and also has more excellent properties than tetrahydrophthalic anhydride: colorless transparent liquid, this is because hexahydrophthalic anhydride does not contain double bond in its molecular structure.
Currently, hexahydrophthalic anhydride is industrially produced by catalytically hydrogenating tetrahydrophthalic anhydride synthesized by Diels-Alder reaction of butadiene and maleic anhydride. In the hydrogenation process, the double bond of tetrahydrophthalic anhydride is activated, the double bond is easy to transfer, so that incomplete hydrogenation is caused, and meanwhile, under the action of hydrogen atoms, the anhydride is easy to undergo side reactions such as condensation, hydrogenolysis, crosslinking and the like, so that impurities with high boiling points and low boiling points which are difficult to separate are generated, the reaction conversion rate and the yield are influenced, and the byproducts with high boiling points are easy to coke at the reaction temperature and are adsorbed on the surface of a catalyst, so that the catalyst is poisoned.
Disclosure of Invention
In order to solve the problems, the invention provides an ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
an ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride comprises a carrier and active components, and is characterized in that: the carrier is ordered mesoporous carbon, the active component is nickel, and the loading capacity of the active component accounts for 0.5-10% of the catalyst by mass.
The invention also provides a preparation method of the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride, which is characterized by comprising the following steps of: the method comprises the following specific steps:
dissolving anhydrous sodium carbonate and resorcinol in a formaldehyde solution, wherein the mass ratio of the anhydrous sodium carbonate to the resorcinol to the formaldehyde is as follows: resorcinol: formaldehyde = 0.01-0.05: 3-4: 1.2-1.4, and reacting for 0.5-3 h at 0-25 ℃ to obtain a phenolic resin precursor;
secondly, adding a surfactant, ethanol and deionized water into the phenolic resin precursor, wherein the mass ratio of the surfactant to the ethanol to the deionized water to the resorcinol is as follows: ethanol: deionized water: resorcinol = 2-3: 15:12: 3-4, hydrochloric acid is dripped to adjust the pH of the solution to 1.5-2.5, the solution is stirred, the system gradually turns to milk white, and the stirring is continued for 1-2 hours;
step three, aging the white mixed liquor obtained in the step two at room temperature, removing supernatant after the aging is finished, drying the precipitated solid at room temperature, and then carrying out thermal polymerization at high temperature;
step four, roasting the solid obtained by thermal polymerization at high temperature in the step three in a nitrogen atmosphere, and cooling at room temperature after roasting to obtain the ordered mesoporous carbon carrier;
and fifthly, loading the active component nickel on the ordered mesoporous carbon obtained in the fourth step by using an impregnation method, and then reducing for 3-12 hours in a hydrogen atmosphere at the reduction temperature of 80-250 ℃ to obtain the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride.
Further, the mass fraction of the formaldehyde solution in the first step is 37%.
Further, the surfactant in the second step is F127.
Further, in the third step, the aging time at room temperature is 10-16 h.
Further, it is characterized in that: in the third step, the drying time at room temperature is 8-14 h.
Further, after drying at room temperature, putting the dried solid into an oven for heating and polymerizing for 18-14 h, wherein the heating temperature is 80 ℃.
Further, the roasting in the fourth step is to heat up to 800 ℃ at a heating rate of 2 ℃/min in a tubular heating furnace in a nitrogen atmosphere, and roast for 3 h.
Further, the impregnation method in the fifth step is to impregnate the carrier ordered mesoporous carbon with a nickel salt aqueous solution, stir for 4-8 hours at 20-40 ℃, dry for more than 12 hours at 80-120 ℃, and roast for 2-5 hours at 400-600 ℃ in an inert atmosphere.
Further, the nickel salt is one or more of nickel nitrate, nickel sulfate and nickel chloride.
The invention has the beneficial effects that:
1. according to the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and the preparation method thereof, resorcinol and formaldehyde are firstly reacted in an alkaline environment to generate a phenolic resin precursor, the reaction time is short, the reaction conditions are easy to control, and the preparation speed of the catalyst is high and controllable;
2. the ordered mesoporous carbon is used as a carrier of the reaction catalyst, the regular mesoporous channels of the ordered mesoporous carbon can effectively prevent carbon deposition from blocking the catalyst channels, and the larger specific surface area of the ordered mesoporous carbon can provide more active sites to promote the reaction, so that the physicochemical property, the catalytic activity and the long-period running stability of the catalyst are improved, and the comprehensive performance of the catalyst is outstanding.
Detailed Description
In order that those skilled in the art will be able to better understand the technical solutions provided by the present invention, the following description is provided in conjunction with the specific embodiments.
A nickel-based supported tetrahydrophthalic anhydride hydrogenation hexahydrophthalic anhydride catalyst with ordered mesoporous carbon as a carrier is prepared by the following steps:
step 1: dissolving anhydrous sodium carbonate and resorcinol in a formaldehyde solution with the mass fraction of 37% in a container such as a stirring kettle, wherein the mass ratio of the anhydrous sodium carbonate to the resorcinol to the formaldehyde is as follows: resorcinol: formaldehyde =0.02:3:1.3, and reacting for 1h at 0-25 ℃ to obtain a phenolic resin precursor;
step 2: adding a surfactant F127, ethanol and deionized water into a container, wherein the mass ratio of the F127 to the ethanol to the deionized water to the resorcinol is as follows: ethanol: deionized water: resorcinol =2:15:12:3, hydrochloric acid is dripped to adjust the pH of the solution to 2, the solution is stirred, the system gradually becomes milky white, and the stirring is continued for 1 hour;
and step 3: aging at room temperature for 12h, pouring the supernatant after aging, drying the solid at room temperature for 12h, and performing thermal polymerization at 80 ℃ for 24 h;
and 4, step 4: heating the solid obtained by high-temperature thermal polymerization in the step 3 to 800 ℃ at a heating rate of 2 ℃/min in a tubular heating furnace in a nitrogen atmosphere, roasting for 3 hours at the temperature, turning to room temperature after roasting is finished, and grinding to obtain the ordered mesoporous carbon carrier;
and 5: and (3) taking 5g of the ordered mesoporous carbon prepared in the step (4), adding 10ml of nickel nitrate aqueous solution containing 50mg of nickel, stirring at 30 ℃ for 6h, drying at 100 ℃ for 16h, roasting at 500 ℃ for 3h in a nitrogen atmosphere, and reducing at 160 ℃ for 8h in a hydrogen atmosphere to obtain the tetrahydrophthalic anhydride catalyst.
The evaluation test of the prepared ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride is carried out in a high-pressure continuous fixed bed reactor, and the reaction effluent is collected by a cold trap. The reaction conditions are 45 ℃, 2.8MPa and 1200h-1, the tetrahydrophthalic anhydride is dissolved in tetrahydrofuran (the mass fraction of the tetrahydrophthalic anhydride is 25 percent), and the feeding hydrogen-oil ratio is 2500: 1. the reaction result of 300h for preparing hexahydrophthalic anhydride by using the catalyst tetrahydrophthalic anhydride is that the conversion rate of the tetrahydrophthalic anhydride is 98 percent and the selectivity of the hexahydrophthalic anhydride is 97 percent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. An ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride comprises a carrier and active components, and is characterized in that: the carrier is ordered mesoporous carbon, the active component is nickel, and the loading capacity of the active component accounts for 0.5-10% of the catalyst by mass;
the method comprises the following specific steps:
dissolving anhydrous sodium carbonate and resorcinol in a formaldehyde solution, wherein the mass ratio of the anhydrous sodium carbonate to the resorcinol to the formaldehyde is as follows: resorcinol: formaldehyde = 0.01-0.05: 3-4: 1.2-1.4, and reacting for 0.5-3 h at 0-25 ℃ to obtain a phenolic resin precursor;
secondly, adding a surfactant, ethanol and deionized water into the phenolic resin precursor, wherein the mass ratio of the surfactant to the ethanol to the deionized water to the resorcinol is as follows: ethanol: deionized water: resorcinol = 2-3: 15:12: 3-4, hydrochloric acid is dripped to adjust the pH of the solution to 1.5-2.5, the solution is stirred, the system gradually turns to milk white, and the stirring is continued for 1-2 hours;
step three, aging the white mixed liquor obtained in the step two at room temperature, removing supernatant after the aging is finished, drying the precipitated solid at room temperature, and then carrying out thermal polymerization at high temperature;
step four, roasting the solid obtained by thermal polymerization at high temperature in the step three in a nitrogen atmosphere, and cooling at room temperature after roasting to obtain the ordered mesoporous carbon carrier;
step five, loading an active component nickel on the ordered mesoporous carbon obtained in the step four by using an impregnation method, and then reducing for 3-12 hours in a hydrogen atmosphere at the reduction temperature of 80-250 ℃ to obtain the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride;
the reaction conditions of the prepared ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride are 45 ℃, 2.8MPa and 1200h-1Dissolving 25% of tetrahydrophthalic anhydride in tetrahydrofuran, wherein the feed hydrogen-oil ratio is 2500: 1, the catalyst is used for preparing hexahydrophthalic anhydride, and the reaction result of 300h for preparing the hexahydrophthalic anhydride by the tetrahydrophthalic anhydride has the tetrahydrophthalic anhydride conversion rate of 98 percent and the hexahydrophthalic anhydride selectivity of 97 percent.
2. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: the mass fraction of the formaldehyde solution in the first step is 37%.
3. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: the surfactant in the second step is F127.
4. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: in the third step, the aging time at room temperature is 10-16 h.
5. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: in the third step, the drying time at room temperature is 8-14 h.
6. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: after drying at room temperature, putting the dried solid into an oven, heating and polymerizing for 18-14 h at the heating temperature of 80 ℃.
7. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: in the fourth step, the roasting is carried out for 3 hours in a tubular heating furnace under the nitrogen atmosphere and at the temperature rising rate of 2 ℃/min to 800 ℃.
8. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 1, wherein: and the impregnation method in the fifth step is to impregnate the ordered mesoporous carbon with the nickel salt aqueous solution, stir for 4-8 h at 20-40 ℃, dry for more than 12h at 80-120 ℃, and roast for 2-5 h at 400-600 ℃ in an inert atmosphere.
9. The method for preparing the ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride as claimed in claim 2, wherein: the precursor of the nickel is one or more of nickel nitrate, nickel sulfate and nickel chloride.
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| CN109841857A (en) * | 2019-02-25 | 2019-06-04 | 河南豫氢动力有限公司 | A kind of preparation method of the mesoporous Pt/C of fuel-cell catalyst |
| CN110052270A (en) * | 2019-04-30 | 2019-07-26 | 天津大学 | A kind of mesoporous carbon spheres nickel-loaded iron alloy nanoparticles catalyst and the preparation method and application thereof |
| CN119701961A (en) * | 2024-12-06 | 2025-03-28 | 中国石油化工股份有限公司 | DINP hydrogenation catalyst based on carbon sphere carrier and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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