CN112452355A - Preparation method of carbon material catalyst applied to styrene preparation - Google Patents
Preparation method of carbon material catalyst applied to styrene preparation Download PDFInfo
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- CN112452355A CN112452355A CN202011454340.3A CN202011454340A CN112452355A CN 112452355 A CN112452355 A CN 112452355A CN 202011454340 A CN202011454340 A CN 202011454340A CN 112452355 A CN112452355 A CN 112452355A
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- styrene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 61
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 41
- 229920001690 polydopamine Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 9
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 58
- 238000001035 drying Methods 0.000 claims description 57
- 238000004140 cleaning Methods 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000003763 carbonization Methods 0.000 abstract description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- VSTOHTVURMFCGL-UHFFFAOYSA-N [C].O=[Si]=O Chemical compound [C].O=[Si]=O VSTOHTVURMFCGL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/396—
-
- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the technical field of catalyst preparation, and discloses a preparation method of a carbon material catalyst applied to styrene preparation aiming at the problem that the activity of functional groups on the surface of a carbon material is influenced by high-temperature carbonization in the prior art, wherein the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, trihydroxymethyl aminomethane and dopamine hydrochloride is 0.5-0.8 g: 1.8-2.2 ml: 0.2-0.5 g: 0.4 g. The preparation method of the poly-dopamine-coated silica catalyst is simple, does not need high-temperature carbonization, is directly used for phenylacetylene catalytic hydrogenation reaction, and shows high catalytic activity and high selectivity to styrene.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a carbon material catalyst applied to styrene preparation.
Background
In recent years, carbon materials such as carbon nanotubes, graphene, fullerene, activated carbon and the like have attracted close attention by researchers at home and abroad due to excellent physicochemical properties and unique structures of the carbon materials, are often used as catalysts and catalyst carriers in catalytic reactions, effectively improve the catalytic activity of the catalysts, and on the basis of the catalyst and the catalyst carriers, a plurality of carbon materials with different structural properties are prepared, and have potential application values in catalytic oxidation, catalytic hydrogenation and photoelectrocatalysis reactions. At present, in the prior art, the preparation of the carbon catalytic material is usually completed by a multi-step method, and finally, the carbon catalytic material is converted to a graphitized structure through high-temperature carbonization, however, the structure and the property of the carbon material are easily affected by the preparation conditions (raw material ratio, hydrothermal temperature and carbonization temperature), which causes uncontrollable preparation of functional groups, electrical structures and atom doping on the surface of the carbon material, and thus the reproducibility of the performance of the carbon material is poor.
The invention discloses a preparation method of a supported palladium-carbon catalyst, which is characterized in that firstly, silicon dioxide pellets modified by amino functional groups are dispersed in water, aqueous solution containing noble metal palladium nanoparticles is added, and the palladium nanoparticles are adsorbed on the surface of the silicon dioxide under the ultrasonic condition to form palladium/silicon dioxide composite pellets; then adding dopamine, and forming a poly-dopamine shell layer on the surface of the palladium/silicon dioxide composite ball under an alkaline condition; and then, carbonizing the polydopamine at high temperature in an inert atmosphere, embedding the palladium nanoparticles in a carbon shell layer in the process, and finally removing the silica pellets by using an alkaline solution to prepare the palladium-carbon catalyst.
The method has the disadvantages that the catalyst can be prepared only under the action of high-temperature carbonization, and the surface activity of functional groups on the surface of the carbon material can be influenced.
Disclosure of Invention
The invention aims to overcome the problem that the high-temperature carbonization in the prior art can influence the activity of functional groups on the surface of a carbon material, and provides a preparation method of a carbon material catalyst for preparing styrene.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a carbon material catalyst for preparing styrene is characterized in that the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, trihydroxymethyl aminomethane and dopamine hydrochloride is 0.5-0.8 g: 1.8-2.2 ml: 0.2-0.5 g: 0.4 g.
The preparation method is characterized in that silicon dioxide is used as a catalyst carrier, trihydroxymethyl aminomethane is used as a buffer reagent, dopamine hydrochloride is used as a carbon source, the catalyst is added according to the proportion for preparation, the polydopamine prepared by high-temperature carbonization is not needed to wrap the silicon dioxide catalyst, the polydopamine is directly used for phenylacetylene catalytic hydrogenation reaction, high catalytic activity and high selectivity to styrene are shown, the preparation method is simple, and energy consumption and cost are saved.
Preferably, the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, trihydroxymethyl aminomethane and dopamine hydrochloride is 0.6-0.7 g: 1.8-2.2 ml: 0.3-0.4 g: 0.4 g.
Preferably, the carbon material catalyst is a polydopamine-coated silica carbon catalyst.
Preferably, the method comprises the following steps:
(1) weighing silicon dioxide, putting the silicon dioxide into a container filled with deionized water for first-stage stirring, then adding trihydroxymethyl aminomethane for second-stage stirring, and then adding dopamine hydrochloride for third-stage stirring;
(2) and after stirring, filtering, cleaning and drying to prepare the carbon material catalyst.
The poly-dopamine can slowly generate self-polymerization in the tris buffer solution, so that a poly-dopamine film is formed on the surface of the silicon dioxide, and finally the poly-dopamine coated silicon dioxide is formed. The material is directly used for phenylacetylene hydrogenation without high-temperature inert atmosphere roasting, and the preparation of styrene by phenylacetylene high-selectivity catalytic hydrogenation is realized. The excellent high-selectivity catalytic hydrogenation is that polydopamine can activate hydrogen to generate an intermediate active species, so that phenylacetylene catalytic hydrogenation is realized, and in addition, the polydopamine serving as a metal-free carbon catalyst has moderate activation degree on hydrogen, so that the phenylacetylene is properly hydrogenated to obtain high styrene selectivity.
Preferably, in the step (1), the first stirring time is 40-60 min.
Preferably, in the step (1), the second-stage stirring time is 30-45 min.
Preferably, in the step (1), the stirring time of the third-stage stirring is 11-12 h.
Preferably, the drying in step (2) is a stepwise drying.
Preferably, the step drying process is as follows: drying in oven at 38-42 deg.C for 1.8-2 hr, and drying at 70-75 deg.C for 10-12 hr.
The use of staged drying enables tighter bonding between the substances in the impregnation for the following reasons: drying to promote a small part of water to volatilize, under the condition of a large amount of water content, heating can endow ions and molecules with more movement energy, and promote the full migration distribution of polydopamine attached to silicon dioxide in a catalyst, so that the polydopamine is more uniformly distributed on the surface of the silicon dioxide and is more firmly combined; under the condition that the first-stage distribution is tight and uniform, rapid moisture drying is carried out at a higher temperature, so that the moisture content in the impregnation body can be fully removed, and the position between the two components can be fixed instantly, so that the structural stability of the impregnation body after drying is higher.
Preferably, in the step (2), the cleaning method is: cleaning with pure water and anhydrous ethanol for 3-5 times.
Therefore, the invention has the following beneficial effects:
(1) the preparation method of the carbon material catalyst applied to styrene preparation is simple, does not need high-temperature carbonization, is directly used for phenylacetylene catalytic hydrogenation reaction, and shows high catalytic activity and high selectivity to styrene;
(2) the poly-dopamine coated silicon dioxide carbon catalyst with stable structure and good catalytic activity is finally prepared by adopting simple and ordered preparation steps and reasonable process parameter adjustment, and the preparation process is simple and efficient.
Detailed Description
The invention is further described with reference to specific embodiments.
General examples
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.5-0.8g of silicon dioxide, putting the silicon dioxide into a container filled with 1.8-2.2ml of deionized water, carrying out first-stage stirring for 40-60min, then adding 0.2-0.5g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 30-45min, then adding 0.4g of dopamine hydrochloride, and carrying out third-stage stirring for 11-12 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 38-42 deg.C for 1.8-2 hr, and drying at 70-75 deg.C for 10-12 hr; the cleaning mode is as follows: cleaning with pure water and anhydrous ethanol for 3-5 times.
Example 1
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.65g of silicon dioxide, putting the silicon dioxide into a container filled with 2ml of deionized water, carrying out first-stage stirring for 50min, then adding 0.35g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 38min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11.5 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 40 deg.C for 1.9 hr and at 72 deg.C for 11 hr; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Example 2
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.5g of silicon dioxide, putting the silicon dioxide into a container filled with 2.2ml of deionized water, carrying out first-stage stirring for 40min, then adding 0.2g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 45min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in an oven at 38 deg.C for 2 hr, and drying at 70 deg.C for 12 hr; the cleaning mode is as follows: and cleaning with pure water and anhydrous ethanol alternately for 3 times.
Example 3
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.8g of silicon dioxide, putting the silicon dioxide into a container filled with 1.8ml of deionized water, carrying out first-stage stirring for 60min, then adding 0.5g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 45min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11-12 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 42 deg.C for 1.8 hr and at 75 deg.C for 10 hr; the cleaning mode is as follows: and cleaning with pure water and anhydrous ethanol alternately for 5 times.
Example 4
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.6g of silicon dioxide, putting the silicon dioxide into a container filled with 1.9ml of deionized water, carrying out first-stage stirring for 45min, then adding 0.3g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 35min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11.2 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in an oven at 39 deg.C for 1.9 hr, and drying at 71 deg.C for 10.5 hr; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Example 5
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.7g of silicon dioxide, putting the silicon dioxide into a container filled with 2.1ml of deionized water, carrying out first-stage stirring for 55min, then adding 0.4g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 40min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11.8 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in an oven at 41 deg.C for 1.95h, and drying at 74 deg.C for 11.5 h; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Comparative example 1 (different from example 1 in that calcination was performed at 650 ℃ under nitrogen for 2h after completion of catalyst preparation.)
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.65g of silicon dioxide, putting the silicon dioxide into a container filled with 2ml of deionized water, carrying out first-stage stirring for 50min, then adding 0.35g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 38min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11.5 h;
(2) and after stirring, filtering, cleaning and drying in sections, and then calcining for 2 hours at 650 ℃ under nitrogen to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 40 deg.C for 1.9 hr and at 72 deg.C for 11 hr; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Comparative example 2 (different from example 1 in that the previous drying step was omitted and the final catalyst was dried at 72 ℃ for 11 h.)
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.65g of silicon dioxide, putting the silicon dioxide into a container filled with 2ml of deionized water, carrying out first-stage stirring for 50min, then adding 0.35g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 38min, and then adding 0.4g of dopamine hydrochloride, carrying out third-stage stirring for 11.5 h;
(2) and after stirring, filtering, cleaning and drying to prepare the carbon material catalyst.
The drying process comprises the following steps: drying at 72 ℃ for 11 h; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Comparative example 3 (different from example 1 in that no silica support was added during the catalyst preparation process.)
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) adding 0.35g of tris (hydroxymethyl) aminomethane into the container, stirring for the second stage for 38min, adding 0.4g of dopamine hydrochloride, and stirring for the third stage for 11.5 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 40 deg.C for 1.9 hr and at 72 deg.C for 11 hr; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Comparative example 4 (different from example 1 in that tris buffer was not added during the catalyst preparation process.)
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.65g of silicon dioxide, putting the silicon dioxide into a container filled with 2ml of deionized water, stirring for the first section for 50min, and then adding 0.4g of dopamine hydrochloride, and stirring for the third section for 11.5 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 40 deg.C for 1.9 hr and at 72 deg.C for 11 hr; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
Comparative example 5 (different from example 1 in that the effect of the degree of self-polymerization of dopamine under alkaline conditions on the catalytic activity was examined by adjusting the pH of the dopamine hydrochloride solution to 8.5 with a sodium hydroxide solution.)
A preparation method of a carbon material catalyst applied to styrene preparation is provided, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst, and comprises the following steps:
(1) weighing 0.65g of silicon dioxide, putting the silicon dioxide into a container filled with 2ml of deionized water, carrying out first-stage stirring for 50min, then adding 0.35g of tris (hydroxymethyl) aminomethane, carrying out second-stage stirring for 38min, then adding 0.4g of dopamine hydrochloride, adding a sodium hydroxide solution, regulating the pH value of the solution to be 8.5, and carrying out third-stage stirring for 11.5 h;
(2) and after stirring, filtering, cleaning and drying in sections to prepare the carbon material catalyst.
The segmented drying process comprises the following steps: drying in oven at 40 deg.C for 1.9 hr and at 72 deg.C for 11 hr; the cleaning mode is as follows: and cleaning with pure water and absolute ethyl alcohol alternately for 4 times.
And (3) testing the performance of the catalyst: weighing 30mg of catalyst, 100ul of phenylacetylene and 6ml of ethanol, putting the catalyst, 100ul of phenylacetylene and 6ml of ethanol into a 30ml stainless steel reaction kettle with a polytetrafluoroethylene lining, replacing the reaction kettle with hydrogen for 5 times before reaction to remove air in the kettle, pressurizing the reaction kettle to 4Mpa by hydrogen, heating the reaction kettle to 120 ℃ for catalytic reaction, reacting for 4 hours at the temperature, quickly cooling after the reaction is finished, adding anisole serving as an internal standard, and performing qualitative and quantitative analysis on reaction liquid by using gas chromatography to calculate the conversion rate of phenylacetylene and the selectivity of styrene. The test results for each item are shown in table 1:
table 1 performance parameters of each item and polydopamine coated silica carbon catalyst
And (4) conclusion: from examples 1 to 5, it can be seen that the added components and the added content are within the range of the present invention, and the prepared poly-dopamine-coated silica carbon catalyst has high phenylacetylene conversion rate and styrene selectivity, and the catalytic activity thereof has a long-term maintenance effect.
Comparative example 1 differs from example 1 in that calcination was carried out at 650 ℃ under nitrogen for 2-3h after the catalyst preparation was complete; the content of oxygen-containing functional groups on the carbon surface of the calcined catalyst is remarkably reduced, thereby causing the change of the carbon electrical structure, which is the main reason for reducing the catalytic activity.
The difference between the comparative example 2 and the example 1 is that the drying of the finished catalyst product omits the previous stage of drying and only dries at 72 ℃ for 11 h; the drying method can cause the moisture in the impregnant to be evaporated to dryness instantly, the combination of the silicon dioxide carrier and the polydopamine is not tight enough, the structural stability of the prepared final secondary catalyst is reduced, and the corresponding catalytic performance is also reduced.
Comparative example 3 differs from example 1 in that no silica support was added during the preparation; the dopamine hydrochloride is directly self-polymerized in the tris buffer solution to generate poly-dopamine pellets, and compared with the poly-dopamine film coated on the outer surface of silicon dioxide and the poly-dopamine pellets, the catalytic activity of the poly-dopamine film and the poly-dopamine pellets in the selective hydrogenation of phenylacetylene is reduced, and the corresponding catalytic performance is also reduced.
Comparative example 4 differs from example 1 in that no tris buffer was added during the catalyst preparation; because no buffering agent is added, the polymerization degree of dopamine hydrochloride is reduced, the hydrogenation performance of the p-phenylacetylene catalyst is further influenced, and finally the catalytic activity of the catalyst is reduced.
Comparative example 5 differs from example 1 in that the use of sodium hydroxide solution to adjust the PH of dopamine hydrochloride solution to 8.5 makes dopamine autopolymerize more readily under weak alkaline conditions, and a high degree of polymerization reduces the content of edge unsaturated carbons, and thus the catalytic activity.
From the data of examples 1-5 and comparative examples 1-5, it is clear that only the solutions within the scope of the claims of the present invention can satisfy the above requirements in all respects, leading to an optimized solution and to polydopamine coated silica carbon catalysts with optimal performance. The change of the mixture ratio, the replacement/addition/subtraction of raw materials or the change of the feeding sequence can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a carbon material catalyst for preparing styrene is characterized in that the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, trihydroxymethyl aminomethane and dopamine hydrochloride is 0.5-0.8 g: 1.8-2.2 ml: 0.2-0.5 g: 0.4 g.
2. The method for preparing the carbon material catalyst for preparing styrene according to claim 1, wherein the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, trihydroxymethyl aminomethane and dopamine hydrochloride is 0.6-0.7 g: 1.8-2.2 ml: 0.3-0.4 g: 0.4 g.
3. The method for preparing the carbon material catalyst for preparing styrene according to claim 1 or 2, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst.
4. The method for preparing a carbon material catalyst for styrene production according to claim 1, comprising the steps of:
(1) weighing silicon dioxide, putting the silicon dioxide into a container filled with deionized water for first-stage stirring, then adding trihydroxymethyl aminomethane for second-stage stirring, and then adding dopamine hydrochloride for third-stage stirring;
(2) and after stirring, filtering, cleaning and drying to prepare the carbon material catalyst.
5. The method of claim 4, wherein the first stirring time in the step (1) is 40-60 min.
6. The method for preparing a carbon material catalyst for use in the preparation of styrene as set forth in claim 4, wherein the second stirring time in the step (1) is 30-45 min.
7. The method for preparing a carbon material catalyst for use in the preparation of styrene as set forth in claim 4, wherein the stirring time of the third stirring stage in the step (1) is 11 to 12 hours.
8. The method of claim 4, wherein the drying in step (2) is a step drying.
9. The method for preparing a carbon material catalyst for use in the preparation of styrene as set forth in claim 8, wherein the step-drying process comprises: drying in oven at 38-42 deg.C for 1.8-2 hr, and drying at 70-75 deg.C for 10-12 hr.
10. The method for preparing a carbon material catalyst for use in styrene production according to claim 4, wherein in the step (2), the cleaning method is: cleaning with pure water and anhydrous ethanol for 3-5 times.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418439A (en) * | 2013-07-14 | 2013-12-04 | 北京化工大学 | Preparation method of recyclable and reusable hydrogenation catalyst |
| CN103418413A (en) * | 2013-07-14 | 2013-12-04 | 北京化工大学 | Preparation method and hydrogenation application of immobilized catalyst |
| CN104148031A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | Method for preparing poly-dopamine carbon material with high specific surface area |
| CN104971759A (en) * | 2015-06-24 | 2015-10-14 | 东华大学 | Preparation method of supported palladium-carbon catalyst |
| CN106000459A (en) * | 2016-06-06 | 2016-10-12 | 南京工业大学 | Preparation method of supported palladium nanocatalyst |
| WO2017117878A1 (en) * | 2016-01-07 | 2017-07-13 | 深圳先进技术研究院 | Silica filler, surface treatment method of silica filler and epoxy resin composite material |
| CN107634190A (en) * | 2017-08-14 | 2018-01-26 | 天津大学 | A kind of method that silica and carbon composite are prepared by high-temperature heat treatment |
| US20180085738A1 (en) * | 2016-09-29 | 2018-03-29 | Korea Institute Of Science And Technology | Catalyst for dehydrogenation reaction of formate and hydrogenation reaction of bicarbonate and preparation method thereof |
| CN110280290A (en) * | 2019-07-08 | 2019-09-27 | 华南理工大学 | One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof |
| CN110665526A (en) * | 2019-09-10 | 2020-01-10 | 华中科技大学 | Nitrogen-sulfur co-doped hollow hemispherical carbon-based material, and preparation and application thereof |
| CN110787827A (en) * | 2019-10-23 | 2020-02-14 | 华中科技大学 | Monoatomic catalyst, preparation method and application thereof |
| CN111135308A (en) * | 2020-03-05 | 2020-05-12 | 杭州师范大学 | Preparation method and application of polydopamine-coated mesoporous silica/elemene composite nanoparticle preparation |
| AU2020101077A4 (en) * | 2019-06-20 | 2020-07-23 | Xiamen University | Silicon/carbon composite and preparation method and use thereof |
-
2020
- 2020-12-10 CN CN202011454340.3A patent/CN112452355B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418413A (en) * | 2013-07-14 | 2013-12-04 | 北京化工大学 | Preparation method and hydrogenation application of immobilized catalyst |
| CN103418439A (en) * | 2013-07-14 | 2013-12-04 | 北京化工大学 | Preparation method of recyclable and reusable hydrogenation catalyst |
| CN104148031A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | Method for preparing poly-dopamine carbon material with high specific surface area |
| CN104971759A (en) * | 2015-06-24 | 2015-10-14 | 东华大学 | Preparation method of supported palladium-carbon catalyst |
| WO2017117878A1 (en) * | 2016-01-07 | 2017-07-13 | 深圳先进技术研究院 | Silica filler, surface treatment method of silica filler and epoxy resin composite material |
| CN106000459A (en) * | 2016-06-06 | 2016-10-12 | 南京工业大学 | Preparation method of supported palladium nanocatalyst |
| US20180085738A1 (en) * | 2016-09-29 | 2018-03-29 | Korea Institute Of Science And Technology | Catalyst for dehydrogenation reaction of formate and hydrogenation reaction of bicarbonate and preparation method thereof |
| CN107634190A (en) * | 2017-08-14 | 2018-01-26 | 天津大学 | A kind of method that silica and carbon composite are prepared by high-temperature heat treatment |
| AU2020101077A4 (en) * | 2019-06-20 | 2020-07-23 | Xiamen University | Silicon/carbon composite and preparation method and use thereof |
| CN110280290A (en) * | 2019-07-08 | 2019-09-27 | 华南理工大学 | One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof |
| CN110665526A (en) * | 2019-09-10 | 2020-01-10 | 华中科技大学 | Nitrogen-sulfur co-doped hollow hemispherical carbon-based material, and preparation and application thereof |
| CN110787827A (en) * | 2019-10-23 | 2020-02-14 | 华中科技大学 | Monoatomic catalyst, preparation method and application thereof |
| CN111135308A (en) * | 2020-03-05 | 2020-05-12 | 杭州师范大学 | Preparation method and application of polydopamine-coated mesoporous silica/elemene composite nanoparticle preparation |
Non-Patent Citations (4)
| Title |
|---|
| JIN YANG: "Ultrafine palladium nanoparticles confined in core–shell magnetic porous organic polymer nanospheres as highly efficient hydrogenation catalyst", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 554 * |
| 何杰等: "《工业催化》", 31 August 2014, 中国矿业大学出版社, pages: 174 * |
| 刘平生: "多巴胺负载加氢催化剂及其应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 6 * |
| 廖红光: "聚多巴胺修饰的SBA-15 负载钌催化剂 催化苯部分加氢", 石油化工, vol. 48, no. 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573429A (en) * | 2022-02-28 | 2022-06-03 | 陕西科技大学 | Preparation method of 2-methoxy-4 methylphenol based on selective hydrodeoxygenation of vanillin |
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