CN112452355B - Preparation method of carbon material catalyst applied to preparation of styrene - Google Patents
Preparation method of carbon material catalyst applied to preparation of styrene Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 66
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 63
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 40
- 229920001690 polydopamine Polymers 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 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
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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
- 238000001035 drying Methods 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 57
- 238000004140 cleaning Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- 238000009472 formulation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 10
- 238000003763 carbonization Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 229960003638 dopamine Drugs 0.000 abstract description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012528 membrane 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
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 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
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002197 limbic effect Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 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
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000000007 visual effect Effects 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 high-temperature carbonization in the prior art can influence the activity of functional groups on the surface of a carbon material, wherein the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, tris (hydroxymethyl) aminomethane and dopamine hydrochloride is 0.5-0.8g:1.8-2.2ml:0.2-0.5g:0.4g. According to the invention, dopamine is used as a carbon source, silicon dioxide is used as a carrier, and the characteristic that dopamine is easy to self-polymerize is utilized to prepare the polydopamine coated silicon dioxide catalyst.
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, active carbon and the like are closely focused by researchers at home and abroad due to their excellent physicochemical properties and unique structures, are often used as catalysts and catalyst carriers in catalytic reactions, effectively improve the catalytic activity of the catalysts, and on the basis, a plurality of carbon materials with different structural properties are prepared and have potential application values in catalytic oxidation, catalytic hydrogenation and photoelectrocatalytic reactions. At present, in the prior art, the preparation of the carbon catalytic material is generally completed by adopting a multi-step method, and finally the transition to a certain graphitized structure is realized through high-temperature carbonization, however, the structure and the property of the carbon material are easily influenced by preparation conditions (raw material proportion, hydrothermal temperature and carbonization temperature), so that the uncontrollable preparation of the surface functional groups, the electrical structure and the atomic doping of the carbon material is caused, and 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, silica pellets modified by amino functional groups are dispersed in water, an aqueous solution containing noble metal palladium nano particles is added, and the palladium nano particles are adsorbed on the surface of the silica under the ultrasonic condition to form palladium/silica composite spheres; adding dopamine, and forming a polydopamine shell layer on the surface of the palladium/silicon dioxide composite sphere under alkaline conditions; and then carbonizing polydopamine at high temperature in an inert atmosphere, embedding palladium nano particles 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 defect that the catalyst can be prepared under the high-temperature carbonization effect finally, and the surface activity of the functional group on the surface of the carbon material can be influenced.
Disclosure of Invention
The invention provides a preparation method of a carbon material catalyst applied to styrene preparation, which aims to solve the problem that high-temperature carbonization can influence the activity of functional groups on the surface of a carbon material in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the 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, tris (hydroxymethyl) aminomethane and dopamine hydrochloride is 0.5-0.8g:1.8-2.2ml:0.2-0.5g:0.4g.
The catalyst is prepared by adding the catalyst carrier of silicon dioxide, the buffer reagent of tris (hydroxymethyl) aminomethane and the carbon source of dopamine hydrochloride according to the proportion, and the polydopamine coated silicon dioxide catalyst prepared by high-temperature carbonization is not needed and is directly used for phenylacetylene catalytic hydrogenation reaction, so that the catalyst has high catalytic activity and high selectivity to styrene, and the preparation method is simple and saves energy consumption and cost.
Preferably, the carbon material catalyst is prepared according to the following raw material formula: the proportion of silicon dioxide, deionized water, tris (hydroxymethyl) aminomethane and dopamine hydrochloride is 0.6-0.7g:1.8-2.2ml:0.3-0.4g:0.4g.
Preferably, the carbon material catalyst is a polydopamine coated silica carbon catalyst.
Preferably, the method comprises the following steps:
(1) Weighing silicon dioxide, placing the silicon dioxide into a container filled with deionized water for first-stage stirring, adding tris (hydroxymethyl) aminomethane for second-stage stirring, and adding dopamine hydrochloride for third-stage stirring;
(2) And filtering, cleaning and drying after stirring is finished, and preparing the carbon material catalyst.
The polydopamine can slowly self-polymerize in the tris buffer solution, so that polydopamine membranes are formed on the surface of the silicon dioxide, and finally the polydopamine-coated silicon dioxide is formed. The material is directly used for hydrogenation of phenylacetylene without roasting in a high-temperature inert atmosphere, and high-selectivity catalytic hydrogenation of phenylacetylene is realized to prepare styrene. The excellent high-selectivity catalytic hydrogenation is characterized in that polydopamine can activate hydrogen to generate intermediate active species, so that the catalytic hydrogenation of phenylacetylene is realized, and in addition, the activation degree of polydopamine serving as a metal-free carbon catalyst to hydrogen is moderate, so that the phenylacetylene is moderately hydrogenated to obtain high styrene selectivity.
Preferably, in the step (1), the first stirring time is 40-60min.
Preferably, in the step (1), the second stirring time is 30-45min.
Preferably, in the step (1), the stirring time of the third stirring stage is 11-12h.
Preferably, the drying in step (2) is a sectional drying.
Preferably, the step-drying process is as follows: drying in oven at 38-42deg.C for 1.8-2 hr, and drying at 70-75deg.C for 10-12 hr.
The adoption of the sectional drying can enable the bonding among substances in the impregnation body to be more compact for the following reasons: the first step of drying, namely promoting the volatilization of a small part of water, and under the condition of a large amount of water content, heating can endow ions and molecules with more movement energy, so that the polydopamine attached to the silicon dioxide in the catalyst is fully migrated and distributed, and the polydopamine is distributed more uniformly on the surface of the silicon dioxide and is combined more firmly; under the condition of compact and uniform distribution in the first stage, the rapid moisture drying is performed at a higher temperature, so that the moisture content in the impregnated body can be sufficiently removed on one hand, and the position between the two components can be instantly fixed on the other hand, so that the structure stability of the impregnated body after drying is higher.
Preferably, in the step (2), the cleaning mode is as follows: alternately cleaning with pure water and absolute ethanol for 3-5 times.
Therefore, the invention has the following beneficial effects:
(1) The preparation method of the carbon material catalyst for preparing styrene 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 preparation method has the advantages that the preparation steps are simple and orderly, the polydopamine coated silica carbon catalyst with stable structure and good catalytic activity is finally prepared through reasonable process parameter adjustment, and the preparation process is simple and efficient.
Detailed Description
The invention is further described below in connection with the following detailed description.
General examples
The preparation method of the carbon material catalyst applied to preparing styrene, 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, placing the silicon dioxide into a container containing 1.8-2.2ml of deionized water, stirring for 40-60min in the first stage, adding 0.2-0.5g of tris (hydroxymethyl) aminomethane, stirring for 30-45min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11-12h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 38-42deg.C for 1.8-2 hr, and drying at 70-75deg.C for 10-12 hr; the cleaning mode is as follows: alternately cleaning with pure water and absolute ethanol for 3-5 times.
Example 1
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2ml of deionized water, stirring for 50min in the first stage, adding 0.35g of tris (hydroxymethyl) aminomethane, stirring for 38min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11.5h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 40deg.C for 1.9 hr, and drying at 72deg.C for 11 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Example 2
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2.2ml of deionized water, stirring for 40min in the first stage, adding 0.2g of tris (hydroxymethyl) aminomethane, stirring for 45min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 38deg.C for 2 hr, and drying at 70deg.C for 12 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 3 times.
Example 3
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 1.8ml of deionized water, stirring for 60min in the first stage, adding 0.5g of tris (hydroxymethyl) aminomethane, stirring for 45min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11-12h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 42deg.C for 1.8 hr, and drying at 75deg.C for 10 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 5 times.
Example 4
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 1.9ml of deionized water, stirring for 45min in the first stage, adding 0.3g of tris (hydroxymethyl) aminomethane, stirring for 35min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11.2h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in an oven at 39deg.C for 1.9h and at 71 deg.C for 10.5h; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Example 5
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2.1ml of deionized water, stirring for 55min in the first stage, adding 0.4g of tris (hydroxymethyl) aminomethane, stirring for 40min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11.8h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 41deg.C for 1.95h and at 74 deg.C for 11.5h; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Comparative example 1 (differing from example 1 in that calcination was carried out under nitrogen at 650 ℃ C. For 2 hours after completion of the catalyst preparation.)
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2ml of deionized water, stirring for 50min in the first stage, adding 0.35g of tris (hydroxymethyl) aminomethane, stirring for 38min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11.5h in the third stage;
(2) Filtering, cleaning and drying in sections after stirring, and calcining at 650 ℃ under nitrogen for 2 hours to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 40deg.C for 1.9 hr, and drying at 72deg.C for 11 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Comparative example 2 (differing from example 1 in that the drying of the finished catalyst product was carried out by omitting the previous drying, drying at 72℃for 11h only.)
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2ml of deionized water, stirring for 50min in the first stage, adding 0.35g of tris (hydroxymethyl) aminomethane, stirring for 38min in the second stage, and adding 0.4g of dopamine hydrochloride, stirring for 11.5h in the third stage;
(2) And filtering, cleaning and drying after stirring is finished, and preparing the carbon material catalyst.
The drying process is as follows: drying at 72 ℃ for 11 hours; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Comparative example 3 (differing from example 1 in that no silica carrier was added during the catalyst preparation process.)
The preparation method of the carbon material catalyst applied to preparing styrene, 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 a container for second-stage stirring for 38min, and adding 0.4g of dopamine hydrochloride for third-stage stirring for 11.5h;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 40deg.C for 1.9 hr, and drying at 72deg.C for 11 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Comparative example 4 (differing from example 1 in that no tris buffer was added during the catalyst preparation)
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2ml of deionized water, stirring for 50min in the first stage, and adding 0.4g of dopamine hydrochloride for stirring for 11.5h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 40deg.C for 1.9 hr, and drying at 72deg.C for 11 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Comparative example 5 (the difference from example 1 is that the pH of dopamine hydrochloride solution was controlled to 8.5 by sodium hydroxide solution, and the influence of the degree of self-polymerization of dopamine under alkaline conditions on the catalytic activity was examined.)
The preparation method of the carbon material catalyst applied to preparing styrene, 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 containing 2ml of deionized water, stirring for 50min in the first stage, adding 0.35g of tris (hydroxymethyl) aminomethane, stirring for 38min in the second stage, adding 0.4g of dopamine hydrochloride, adding sodium hydroxide solution, regulating the pH value of the solution to 8.5, and stirring for 11.5h in the third stage;
(2) And filtering, cleaning and drying in sections after stirring is finished, so as to prepare the carbon material catalyst.
The sectional drying process comprises the following steps: drying in oven at 40deg.C for 1.9 hr, and drying at 72deg.C for 11 hr; the cleaning mode is as follows: and adopting pure water and absolute ethyl alcohol to alternately clean for 4 times.
Catalyst performance test: 30mg of catalyst, 100ul of phenylacetylene and 6ml of ethanol are weighed and put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is replaced by hydrogen for 5 times before reaction, so as to remove air in the kettle, then the hydrogen is pressurized to 4Mpa, the reaction kettle is heated to 120 ℃ for catalytic reaction, the reaction is carried out for 4 hours at the temperature, the reaction kettle is cooled quickly after the reaction is finished, anisole is added as an internal standard, and the reaction liquid is subjected to qualitative and quantitative analysis by utilizing gas chromatography, so that the phenylacetylene conversion rate and the styrene selectivity are calculated. The visual test results are shown in table 1:
table 1 shows performance parameters of the various items and polydopamine-coated silica carbon catalyst
Conclusion: from examples 1 to 5, it can be seen that each additive component and each additive content are within the scope of the invention, and the prepared polydopamine coated silica carbon catalyst has higher phenylacetylene conversion rate and styrene selectivity, and the catalytic activity of the polydopamine coated silica carbon catalyst has a long-time maintaining effect.
Comparative example 1 differs from example 1 in that the catalyst preparation was completed and then calcined at 650 ℃ under nitrogen for 2-3 hours; the content of oxygen-containing functional groups on the carbon surface of the catalyst after calcination is significantly reduced, thus leading to a change in the carbon electrical structure, which is a major cause of the reduction in catalytic activity.
Comparative example 2 differs from example 1 in that the drying of the finished catalyst product omits the previous drying stage, which is only 72 ℃ for 11 hours; the drying mode can lead the moisture in the impregnated body to volatilize and evaporate instantly, the combination of the silicon dioxide carrier and polydopamine is not tight enough, the structural stability of the final secondary catalyst is reduced, and the corresponding catalytic performance is also reduced.
Comparative example 3 differs from example 1 in that no silica carrier was added during the preparation; dopamine hydrochloride directly self-polymerizes in a tris buffer solution to form polydopamine pellets, and compared with polydopamine membranes wrapped on the outer surface of silicon dioxide and polydopamine pellets, the catalytic activity of the polydopamine membranes and polydopamine pellets in phenylacetylene selective hydrogenation 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; as no buffer is added, the polymerization degree of dopamine hydrochloride is reduced, the hydrogenation performance of the poly-dopamine polymerization degree p-phenylacetylene catalyst is further affected, and finally the catalytic activity of the catalyst is reduced.
Comparative example 5 differs from example 1 in that the ph=8.5 of dopamine hydrochloride solution was controlled using sodium hydroxide solution, dopamine was made easier to self-polymerize under weakly alkaline conditions, and the high degree of polymerization reduced the content of limbic carbon, thus reducing the catalytic activity.
From the data of examples 1-5 and comparative examples 1-5, it is evident that the above requirements can be met in all respects only with the solutions within the scope of the claims of the present invention, leading to an optimized solution and an optimally performing polydopamine-coated silica carbon catalyst. And the corresponding negative effects are brought to the change of the proportion, the replacement/addition of the raw materials or the change of the feeding sequence.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. The application of the carbon material catalyst in 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, tris (hydroxymethyl) aminomethane and dopamine hydrochloride is 0.5-0.8g:1.8-2.2ml:0.2-0.5g:0.4g;
the preparation method of the carbon material catalyst comprises the following steps:
(1) Weighing silicon dioxide, placing the silicon dioxide into a container filled with deionized water for first-stage stirring, adding tris (hydroxymethyl) aminomethane for second-stage stirring, and adding dopamine hydrochloride for third-stage stirring;
(2) Filtering, cleaning and drying after stirring is finished to prepare the carbon material catalyst; the drying is sectional drying.
2. The use of a carbon material catalyst according to claim 1 in the preparation of styrene, wherein the carbon material catalyst is prepared according to the following raw material formulation: the proportion of silicon dioxide, deionized water, tris (hydroxymethyl) aminomethane and dopamine hydrochloride is 0.6-0.7g:1.8-2.2ml:0.3-0.4g:0.4g.
3. Use of a carbon material catalyst according to claim 1 or 2 for the preparation of styrene, wherein the carbon material catalyst is a polydopamine-coated silica carbon catalyst.
4. The use of a carbon material catalyst according to claim 1 for the preparation of styrene, wherein in step (1), the first stirring period is 40-60min.
5. The use of a carbon material catalyst according to claim 1 for the preparation of styrene, wherein in step (1), the second stirring period is 30-45min.
6. The use of a carbon material catalyst according to claim 1 in the preparation of styrene, wherein in step (1), the third stirring period is 11-12 hours.
7. Use of a carbon material catalyst according to claim 1 in the preparation of styrene, wherein the staged drying process is: drying in oven at 38-42deg.C for 1.8-2 hr, and drying at 70-75deg.C for 10-12h.
8. The use of a carbon material catalyst according to claim 1 in the preparation of styrene, wherein in step (2), the cleaning mode is: alternately cleaning with pure water and absolute ethanol for 3-5 times.
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