CN116237071A - Metal oxide modified Pt/SiC catalyst and preparation method and application thereof - Google Patents
Metal oxide modified Pt/SiC catalyst and preparation method and application thereof Download PDFInfo
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- CN116237071A CN116237071A CN202211482379.5A CN202211482379A CN116237071A CN 116237071 A CN116237071 A CN 116237071A CN 202211482379 A CN202211482379 A CN 202211482379A CN 116237071 A CN116237071 A CN 116237071A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a Pt/SiC catalyst modified by metal oxide, and a preparation method and application thereof. The effect of different metal oxides and the content of metal oxides on the catalyst activity was investigated. According to the catalyst, the alkaline sites on the catalyst are increased by utilizing metal oxide modification, pt nano particles can be stably and highly dispersed on the SiC surface, meanwhile, the hydrogen overflow on the surface can be enhanced by oxide modification, the active hydrogen concentration on the surface of a carrier is improved, and the selective hydrogenation of cinnamaldehyde can be realized on the premise of low Pt loading. The SiC modified by the oxide is used as a carrier, and the high-selectivity hydrogenation of the cinnamaldehyde can be realized under mild conditions.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a metal oxide modified Pt/SiC catalyst, and a preparation method and application thereof.
Background
Cinnamyl alcohol is an important organic intermediate and is commonly used for synthesizing medicines, essence and the like. Currently, most of the industry directly reduces cinnamaldehyde by a reducing agent to obtain cinnamyl alcohol. The reducing agent is generally aluminum isopropoxide, sodium borohydride or lithium aluminum tetrahydroide, which is expensive and has harsh reaction conditions, the reducing agent is difficult to separate, more three wastes are generated, the pollution to the environment is large, and the environment is not in line with the concept of green chemistry. Catalytic hydrogenation is a green production method, but since cinnamaldehyde molecules contain both a c=c double bond and a c=o double bond, the bond energy of the c=c double bond is low, and it is very difficult to achieve high-selectivity hydrogenation of the c=o double bond from the thermodynamic and kinetic viewpoints.
Supported catalysts are often used for the selective hydrogenation of cinnamaldehyde, wherein noble metals Pt, ru, au, etc. are often used as the active components of the supported catalysts. In general, it is difficult to achieve high selectivity of these supported catalysts on the premise of high activity. According to literature reports, siC-C is used as a catalyst carrier to load 5wt% of Pt for the selective hydrogenation reaction of cinnamaldehyde, and the selectivity of cinnamyl alcohol is about 80% under the pressure of 2MPa H2. In general, pure SiC is used as a carrier to load Pt catalyst, so that the selectivity of the Pt catalyst to cinnamyl alcohol is low. In addition, it has been also known to use a Pt catalyst supported on a microporous cerium oxide, and react at 70 ℃ and a pressure of 2mpa H2 for 6 hours, with a conversion rate of 97% for cinnamaldehyde and a selectivity of about 88% for cinnamyl alcohol.
Aiming at the problems of low selectivity, relatively harsh reaction conditions and the like of the traditional system, the invention utilizes the hydrogen overflow existing on the surface of SiC, improves the hydrogen overflow concentration on the surface of SiC by modifying rare earth metal oxide and the like on the surface of SiC, and simultaneously can preferentially adsorb and activate C=O bonds at rich oxygen sites on the surface of rare earth oxide, thereby being capable of obtaining the cinnamyl alcohol with high selectivity under the mild conditions of low Pt load.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of a Pt/SiC catalyst modified by metal oxide.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a Pt/SiC catalyst modified by metal oxide.
As a preferable scheme of the preparation method of the metal oxide modified Pt/SiC catalyst, the preparation method comprises the following steps: the metal oxide includes Al 2 O 3 、CeO 2 、ZrO 2 One of them.
As a preferable scheme of the preparation method of the metal oxide modified Pt/SiC catalyst, the preparation method comprises the following steps: the modification method comprises the steps of,
dispersing SiC and a metal oxide precursor in water, and stirring for 5-12 h;
and (3) drying, and then placing into a Joule heating device, and heating at 600-1000 ℃ for 1-6 min to obtain the SiC modified by the metal oxide.
As a preferable scheme of the preparation method of the metal oxide modified Pt/SiC catalyst, the preparation method comprises the following steps: the mass fraction of the metal oxide precursor is 0.1-20 wt.% of SiC.
As a preferable scheme of the preparation method of the metal oxide modified Pt/SiC catalyst, the preparation method comprises the following steps: the loading of Pt on the surface of the carrier by the liquid phase reduction method includes,
will H 2 PtCl 4 ·6H 2 Adding the O solution and the KOH solution into a beaker filled with 25ml of glycol, carrying out ultrasonic treatment for 5min, and adding SiC modified by metal oxide, and carrying out ultrasonic treatment for 30min;
after ultrasonic treatment, the beaker is placed into a microwave oven to be heated for 1 to 3 minutes, and the beaker is filtered, washed and dried.
As a preferable scheme of the preparation method of the metal oxide modified Pt/SiC catalyst, the preparation method comprises the following steps: the content of platinum in the Pt/SiC catalyst is 0.1-3 wt.% of the mass fraction of silicon carbide.
As a preferable scheme of the preparation method of the metal oxide modified Pt/SiC catalyst, the preparation method comprises the following steps: the temperature of the drying is 40-100 ℃ and the time is 6-12 h.
It is a further object of the present invention to overcome the deficiencies of the prior art and to provide the use of a metal oxide modified Pt/SiC catalyst.
In order to solve the technical problems, the invention provides the following technical scheme: the application is to catalyze the selective hydrogenation of cinnamaldehyde to prepare cinnamyl alcohol, comprising,
uniformly mixing cinnamaldehyde, an organic solvent and a Pt/SiC catalyst to form a suspension;
transferring the suspension into a high-pressure reaction kettle for sealing, flushing with hydrogen, pressurizing, and stirring at 20-100 ℃ for 2-8 h.
As a preferred embodiment of the application of the metal oxide modified Pt/SiC catalyst of the present invention, wherein: the organic solvent is one of ethanol, methanol, isopropanol, DMF and 1, 4-dioxane, wherein the mass ratio of the cinnamaldehyde to the solvent is 0.01-0.1: 5 to 50, and the mass ratio of the catalyst to the catalyst is 1:0.1 to 0.5.
As a preferred embodiment of the application of the metal oxide modified Pt/SiC catalyst of the present invention, wherein: the pressurizing after the purging with hydrogen comprises that after the reaction kettle is purged with hydrogen for three times, the hydrogen pressure of the reaction kettle is maintained to be 0.5-2 MPa.
The invention has the beneficial effects that:
according to the invention, the SiC surface is modified by using the metal oxide, and the metal oxide surface has a certain oxygen vacancy, so that C=O double bonds can be preferentially adsorbed to activate the SiC surface. Meanwhile, the modification of the metal oxide enhances the concentration of active hydrogen on the surface of SiC, reduces the load of noble metal, has good catalytic activity and has higher selectivity on cinnamyl alcohol. The conversion rate and selectivity of the method for the cinnamyl alcohol can reach 100 percent. The method is environment-friendly, low in cost, mild in reaction, simple in operation and high in product yield.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
980mg of SiC and 74.0mg of Ce (NO) were weighed 3 ) 3 ·6H 2 O, adding 10ml deionized water, stirring for 12h, oven drying at 60deg.C for 12h, placing into Joule heating device, and introducing 10% O 2 Maintaining the mixed gas of Ar and Ar at 900 ℃ for 3min, and cooling to obtain 3 percent of CeO 2 -SiC。
Will 6.65ml H 2 PtCl 4 ·6H 2 Neutralization of O solution 0.3M KOH solution was added to a beaker containing 20ml of ethylene glycol and sonicated for 5 minutes and 990mg of 3% CeO was added continuously 2 -SiC ultrasound for 30min. The beaker was placed in a microwave oven and heated for 1.5min. Filtering, washing and drying to obtain 1wt.% Pt/3% CeO 2 -SiC catalyst.
30mg of 1wt.% Pt/3% CeO prepared by the method described above was weighed 2 Placing the SiC catalyst in a high-pressure reaction kettle, measuring 10ml of ethanol, placing 1mmol of cinnamaldehyde in the reaction kettle, sealing the reaction kettle for 3 times, maintaining the hydrogen pressure at 0.5MPa, and heating the reaction system to 30 ℃ under stirring for 3 hours. Wherein the conversion rate of cinnamaldehyde is 100%, and the selectivity of cinnamyl alcohol is 100%.
Example 2
This example differs from example 1 in that CeO was adjusted 2 The influence of the modified amount on the catalytic activity was investigated, and the other preparation processes were the same as in comparative document 1, and the results are shown in Table 1.
1wt.％Pt/0％CeO 2 -SiC catalyst preparation method:
6.65ml H 2 PtCl 4 ·6H 2 neutralizing the O solution, adding the 0.3M KOH solution into a beaker filled with 20ml of ethylene glycol, carrying out ultrasonic treatment for 5min, and continuously adding 990mg of SiC for ultrasonic treatment for 30min; heating the beaker in a microwave oven for 1.5min, filtering, washing and drying to obtain 1wt.% Pt/0% CeO 2 -SiC catalyst.
TABLE 1 CeO different 2 Influence of the modified amount of (2) on the catalytic Activity
| CeO 2 Modification amount | Conversion (%) | Selectivity (%) |
| 1wt.％Pt/0％CeO 2 -SiC | 51 | 78 |
| 1wt.％Pt/1％CeO 2 -SiC | 71 | 85 |
| 1wt.％Pt/2％CeO 2 -SiC | 78 | 90 |
| 1wt.％Pt/3％CeO 2 -SiC | 100 | 100 |
| 1wt.％Pt/5％CeO 2 -SiC | 100 | 87 |
As can be seen from Table 1, the catalytic activity was improved by modifying the SiC surface with a metal oxide, and the catalytic activity was increased with the increase of the content of cerium oxide, but when the mass fraction of cerium oxide was more than 3%, the conversion of cinnamaldehyde was not changed, but the selectivity for cinnamyl alcohol was decreased, so 3% CeO was used 2 SiC is the catalyst support.
Example 3
This example differs from example 1 in that the type of metal oxide was adjusted to investigate its effect on catalytic activity, and the rest of the preparation process was the same as that of comparative document 1, and the results are shown in table 2.
TABLE 2 influence of various metalloid oxide modifications on catalytic activity
| Metal oxide species | Conversion (%) | Selectivity (%) |
| 1wt.％Pt/3％CeO 2 -SiC | 100 | 100 |
| 1wt.％Pt/3％Al 2 O 3 -SiC | 70 | 80 |
| 1wt.％Pt/3％ZrO 2 -SiC | 78 | 82 |
As can be seen from table 2, the modification of the metal oxide can improve the catalytic activity and has good selectivity to cinnamyl alcohol. The interaction between the metal and the carrier can be changed through the modification of the metal oxide, so that the catalytic activity is improved. The surface of the metal oxide has rich oxygen vacancies, and can preferentially adsorb and activate C=O double bonds. Wherein CeO is used as 2 The modification effect is optimal. This is because of CeO 2 Ce of surface 4+ Will be converted into Ce 3+ More oxygen vacancies are formed, facilitating the adsorption activation of c=o bonds. Meanwhile, hydrogen overflow effect exists on the SiC surface, but the hydrogen overflow can only be around Pt sites, ceO 2 The presence of (2) enhances this effect, allowing reactant molecules remote from the Pt sites to activate the reaction.
Example 4
This example is different from example 1 in that the kind of the organic solvent in the selective hydrogenation reaction of cinnamaldehyde was adjusted, the influence on the catalytic activity was investigated, the rest of the preparation process was the same as that of comparative document 1, and the results are shown in table 3.
TABLE 3 influence of different types of organic solvents on catalytic Activity
| Organic solvent species | Conversion (%) | Selectivity (%) |
| Ethanol | 100 | 100 |
| Isopropyl alcohol | 83 | 86 |
| Methanol | 85 | 80 |
| DMF | 60 | 78 |
| 1, 4-Dioxahexacyclic ring | 50 | 82 |
From table 3, it can be seen that the proton type solvent is more favorable for selective hydrogenation of cinnamaldehyde molecules, and-OH in the proton type solvent can interact with c=o bond, so as to have a promoting effect on conversion of cinnamaldehyde.
Example 5
This example differs from example 1 in that the time of the selective hydrogenation of cinnamaldehyde was adjusted, the effect on the catalytic activity was investigated, the rest of the preparation process was the same as that of comparative document 1, and the results are shown in table 3.
TABLE 4 influence of different reaction times on the catalytic activity
| Time | Conversion (%) | Selectivity (%) |
| 1 | 30 | 78 |
| 2 | 55 | 89 |
| 3 | 100 | 100 |
| 4 | 100 | 93 |
| 5 | 100 | 87 |
As can be seen from table 4, the reaction time has a certain effect on the selective hydrogenation of cinnamaldehyde under the same catalyst, and the selectivity of cinnamyl alcohol tends to be increased and then decreased as the conversion rate is continuously increased with the extension of the reaction time. This is because, when the reaction is started, cinnamaldehyde molecules have two different adsorption modes, namely, c=o bond horizontal adsorption and vertical adsorption, on the surface of the catalyst, and as the reaction proceeds, the molecules adsorbed on the surface of the catalyst are more, and the horizontal adsorption of c=o bonds is prevented due to the steric hindrance effect, so that the selectivity is improved, and when the reaction time exceeds 3 hours, the selectivity to cinnamyl alcohol is reduced, so that the optimal reaction time is 3 hours.
According to the invention, the SiC surface is modified by using the metal oxide, and the C=O double bond can be preferentially adsorbed to activate the SiC surface because the metal oxide surface has a certain oxygen vacancy. Meanwhile, the concentration of active hydrogen on the surface of SiC is enhanced by modifying the metal oxide, because in general, when the load is lower, the conversion rate of reactants is lower, the conversion rate is continuously increased along with the increase of the load, but the excessive load can cause excessive hydrogenation of the reaction to generate saturated alcohol, but the concentration of active hydrogen on the surface of SiC is enhanced by modifying the metal oxide, so that the high conversion rate can be realized on the premise of low load, and meanwhile, the high selectivity to cinnamyl alcohol is also realized.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a Pt/SiC catalyst modified by metal oxide is characterized by comprising the following steps of: comprising the steps of (a) a step of,
and taking the SiC modified by the metal oxide as a catalyst carrier, and loading Pt on the surface of the carrier by a liquid phase reduction method to obtain the Pt/SiC catalyst modified by the metal oxide.
2. The method for preparing a metal oxide modified Pt/SiC catalyst according to claim 1, wherein: the metal oxide includes Al 2 O 3 、CeO 2 、ZrO 2 One of them.
3. The method for preparing a metal oxide modified Pt/SiC catalyst according to claim 1, wherein: the modification method comprises the steps of,
dispersing SiC and a metal oxide precursor in water, and stirring for 5-12 h;
and (3) drying, and then placing into a Joule heating device, and heating at 600-1000 ℃ for 1-6 min to obtain the SiC modified by the metal oxide.
4. A method of preparing a metal oxide modified Pt/SiC catalyst as claimed in claim 3, wherein: the mass fraction of the metal oxide precursor is 0.1-20 wt.% of SiC.
5. The method for preparing a metal oxide modified Pt/SiC catalyst according to claim 1, wherein: the loading of Pt on the surface of the carrier by the liquid phase reduction method includes,
will H 2 PtCl 4 ·6H 2 Adding the O solution and the KOH solution into a beaker filled with 25ml of glycol, carrying out ultrasonic treatment for 5min, and adding SiC modified by metal oxide, and carrying out ultrasonic treatment for 30min;
after ultrasonic treatment, the beaker is placed into a microwave oven to be heated for 1 to 3 minutes, and the beaker is filtered, washed and dried.
6. The method of preparing a metal oxide modified Pt/SiC catalyst according to claim 5, wherein: the content of platinum in the Pt/SiC catalyst is 0.1-3 wt.% of the mass fraction of silicon carbide.
7. The method of preparing a metal oxide modified Pt/SiC catalyst according to claim 5, wherein: the temperature of the drying is 40-100 ℃ and the time is 6-12 h.
8. Use of a metal oxide modified Pt/SiC catalyst prepared by the method of any one of claims 1 to 7, wherein: the application is to catalyze the selective hydrogenation of cinnamaldehyde to prepare cinnamyl alcohol, comprising,
uniformly mixing cinnamaldehyde, an organic solvent and a Pt/SiC catalyst to form a suspension;
transferring the suspension into a high-pressure reaction kettle for sealing, flushing with hydrogen, pressurizing, and stirring at 20-100 ℃ for 2-8 h.
9. The use of a metal oxide modified Pt/SiC catalyst according to claim 8, wherein: the organic solvent is one of ethanol, methanol, isopropanol, DMF and 1, 4-dioxane, wherein the mass ratio of the cinnamaldehyde to the solvent is 0.01-0.1: 5 to 50, and the mass ratio of the catalyst to the catalyst is 1:0.1 to 0.5.
10. The use of a metal oxide modified Pt/SiC catalyst according to claim 8, wherein: the pressurizing after the purging with hydrogen comprises that after the reaction kettle is purged with hydrogen for three times, the hydrogen pressure of the reaction kettle is maintained to be 0.5-2 MPa.
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