CN111135844B - Application of organic soluble molybdenum salt in preparation of molybdenum carbide catalyst, preparation method and application of molybdenum carbide catalyst - Google Patents
Application of organic soluble molybdenum salt in preparation of molybdenum carbide catalyst, preparation method and application of molybdenum carbide catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of heterogeneous catalytic cracking of aryl ether bonds, and particularly relates to application of organic soluble molybdenum salt in preparation of a molybdenum carbide catalyst, a preparation method of the molybdenum carbide catalyst and application of the molybdenum carbide catalyst in catalytic reaction of benzyl phenyl ether. The organic soluble molybdenum salt is used as a raw material for preparing the molybdenum carbide catalyst, so that the molybdenum carbide catalyst has high dispersibility and activity, and the prepared molybdenum carbide catalyst can be used for breaking two types of C-O bonds in benzyl phenyl ether molecules with high conversion rate and high selectivity without adding a noble metal catalyst in the application of the benzyl phenyl ether to obtain methylbenzene, phenol, benzyl alcohol and benzene, so that the reaction cost of catalytic conversion of the benzyl phenyl ether is reduced, and the additional value of a product is improved.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalytic cracking of aryl ether bonds, and particularly relates to application of organic soluble molybdenum salt in preparation of a molybdenum carbide catalyst, a preparation method of the molybdenum carbide catalyst and application of the molybdenum carbide catalyst in catalytic reaction of benzyl phenyl ether.
Background
The biomass energy plays a significant role in the world energy forecast by virtue of the characteristics of wide sources, rich reserves, zero carbon emission and the like. The C-O ether bond is the main connecting bond type between the basic structural units of the biomass, and the selective aryl ether bond breaking reaction has very important significance in preparing monocyclic aromatic chemicals from the biomass.
The benzyl phenyl ether has two types of C-O ether bonds in the molecular structure, namely aryl C ar -O ether linkage and fatty C al And (4) selectively breaking different types of C-O ether bonds in benzyl phenyl ether molecules by using an-O ether bond to obtain high value-added products such as phenol, toluene, benzyl alcohol, benzene and the like. However, since the C-O bond energy is large, usually 218-314kJ/mol, the C-O ether bond breaking reaction usually uses Pd, ru, pt and other metals with high hydrogenation activity as catalysts, which not only easily generates the side product of benzene ring hydrogenationReaction, make the product lose aromaticity; the use of the noble metal catalyst can greatly increase the process cost; the reaction activity is usually low by using cheap metal as a catalyst. Xie et al (Fuel Processing Technology,2019, 188, 190-196) et al convert benzyl anisole to toluene and phenol with Ru/AC, pd/AC as catalyst, however the selectivity of aromatic saturated product in the product is 7.1% -32.4%. Zhu et al (Fuel Processing Technology,2019, 194, 106126) convert benzyl anisole with Ni/AC, niCu/AC, niCo/AC as catalysts with a reaction conversion rate of only 30% -34%. Therefore, the development of a catalyst for the selective-breaking benzylphenyl ether catalytic reaction with low cost, high conversion rate and high activity has very important significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low conversion rate, low activity, high price and the like of the benzyl phenyl ether catalyst in the prior art, so that the application of the organic soluble molybdenum salt in preparing the molybdenum carbide catalyst, the preparation method of the molybdenum carbide catalyst and the application of the molybdenum carbide catalyst are provided.
Therefore, the invention provides the following technical scheme.
The invention provides application of organic soluble molybdenum salt in preparation of a molybdenum carbide catalyst.
The organic soluble molybdenum salt is molybdenum isopropoxide and/or molybdenum ethoxide.
The invention also provides a preparation method of the molybdenum carbide catalyst, which comprises the following steps,
mixing alkane, surfactant and water to obtain trans-microemulsion, adding organic soluble molybdenum salt, performing a first hydrolysis reaction, adding a silicon source, and performing a second hydrolysis reaction; adding an organic solvent, and standing for layering to obtain a molybdenum carbide precursor;
and calcining the molybdenum carbide precursor to obtain the molybdenum carbide catalyst.
The calcining temperature is 550-700 ℃, and the calcining time is 2-6h;
heating to the calcination temperature at a rate of 0.2-2 ℃/min.
The molar ratio of molybdenum in the organic soluble molybdenum salt to silicon in the silicon source is 1: (20-200);
the particle size of the molybdenum carbide catalyst is 1-5nm.
The amount of the organic soluble molybdenum salt in the trans-microemulsion is 1-20mmol/L.
The volume ratio of the surfactant to the alkane is 1: (4-20);
the volume ratio of the water to the alkane is as follows: 1: (10-100);
the surfactant is a nonionic surfactant;
the alkane is at least one of heptane, octane and nonane;
the calcining atmosphere is CH 4 And H 2 Mixed gas of (2), the CH 4 And H 2 The volume fraction ratio of (1-4): 1.
in addition, the invention also provides application of the molybdenum carbide catalyst prepared by the method in catalytic reaction of benzyl phenyl ether.
The benzyl phenyl ether catalyzed reaction comprises the following steps,
the benzyl phenyl ether, the molybdenum carbide catalyst and the hydrogen-rich solvent are subjected to catalytic reaction at 160-260 ℃, and phenol, toluene, benzene and benzyl alcohol are obtained after separation.
The reaction time is 1-6h;
the mass ratio of the benzyl phenyl ether to the molybdenum carbide catalyst is (10-100): 1; the mass ratio of the benzyl phenyl ether to the solvent is 1: (10-100);
the hydrogen-rich solvent is ethanol, propanol or isopropanol.
The first hydrolysis reaction is a hydrolysis reaction of an organic soluble molybdenum salt, and the second hydrolysis reaction is a hydrolysis reaction of a silicon source.
The technical scheme of the invention has the following advantages:
1. the organic soluble molybdenum salt is used as a raw material of the molybdenum carbide catalyst, the prepared catalyst has high dispersity and activity, high conversion rate and high selectivity, C-O ether bonds at different positions in benzyl phenyl ether molecules are broken, reaction products of toluene and phenol, benzyl alcohol and benzene are obtained, a noble metal catalyst does not need to be added in the application of benzyl phenyl ether, and a benzene ring saturation side reaction occurs, so that the catalytic conversion reaction cost of benzyl phenyl ether is reduced, and the application of the molybdenum carbide catalyst is expanded.
2. The application of the organic soluble molybdenum salt in preparing the molybdenum carbide catalyst provided by the invention is beneficial to forming the molybdenum carbide catalyst with high dispersibility and high activity by taking molybdenum isopropoxide and/or molybdenum ethoxide as the organic soluble molybdenum salt.
3. The preparation method of the molybdenum carbide catalyst comprises the steps of mixing alkane, a surfactant and water to obtain trans-microemulsion, adding organic soluble molybdenum salt, carrying out a first hydrolysis reaction, adding a silicon source, and carrying out a second hydrolysis reaction; adding an organic solvent, and standing for layering to obtain a molybdenum carbide precursor; and calcining the molybdenum carbide precursor to obtain the molybdenum carbide catalyst. Under the action of surfactant, water can be dispersed in alkane in the form of very small liquid drops to form trans-microemulsion, after the organic soluble molybdenum salt and silicon source are added, the molybdenum and silicon dissolved in organic phase can be contacted with the very small liquid drops under the action of surfactant to produce hydrolysis reaction, and after the above-mentioned materials are calcined and carbonized, the above-mentioned material can be added into the mixture 2 The surface of the carrier forms a highly dispersed molybdenum carbide catalyst with controllable particle size distribution.
The invention controls the preparation conditions of the composition, mo/Si ratio and the like of the trans-microemulsion to ensure that the molybdenum carbide catalyst is in SiO 2 The particle size on the carrier can be controllably distributed between 1 nm and 5nm. The results show that compared with the traditional impregnation synthesis method, the catalyst prepared by the method has narrower active center particle size distribution, and the molybdenum carbide catalysts with different particle size distributions can selectively break C-O ether bonds on different positions on benzyl phenyl ether molecules to obtain product results with different selectivities.
4. According to the preparation method of the molybdenum carbide catalyst, the calcination temperature of the molybdenum carbide precursor in the preparation method is 550-700 ℃, and compared with the prior art, the calcination temperature of the molybdenum carbide catalyst precursor can be reduced by 50-100 ℃.
5. The molybdenum carbide catalyst is applied to the benzyl phenyl ether catalytic reaction for the first time, can selectively break C-O ether bonds in the benzyl phenyl ether, avoids aromatic ring saturation reaction and consumption of extra expensive hydrogen, and is a catalyst for preparing toluene, phenol, benzene and benzyl alcohol with high added values.
The molybdenum carbide catalyst catalyzes benzyl phenyl ether at the temperature of 160-260 ℃ to generate toluene, phenol, benzene and benzyl alcohol; when the catalytic reaction temperature is lower than 160 ℃, the conversion rate of benzyl phenyl ether is reduced, and when the catalytic reaction temperature is higher than 260 ℃, alkylation side reaction occurs between products to obtain a byproduct containing multiple aromatic rings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM image of a catalyst in example 1 of the present invention;
FIG. 2 is a TEM image of the catalyst in example 2 of the present invention;
FIG. 3 is a TEM image of the catalyst in example 3 of the present invention;
FIG. 4 is a TEM image of the catalyst in example 4 of the present invention;
FIG. 5 is a TEM image of the catalyst in example 5 of the present invention;
FIG. 6 is a TEM image of the catalyst in example 6 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a method for preparing a molybdenum carbide catalyst, comprising,
uniformly mixing 2mL of water, 200mL of octane and 10mL of lauryl alcohol polyoxyethylene ether to obtain trans-microemulsion, adding 0.02mmol of molybdenum isopropoxide, stirring for 12h to perform a first hydrolysis reaction, adjusting the pH to be neutral, adding 3.6mmol of tetraethyl silicate solution, and stirring for 12h to perform a second hydrolysis reaction; adding methanol with the same volume as the solution into the solution, standing for layering, taking a lower-layer methanol phase, performing rotary evaporation concentration, and performing centrifugal drying to obtain a molybdenum carbide catalyst precursor;
putting the molybdenum carbide catalyst precursor into CH 4 /H 2 (v/v = 15%) in the mixed gas, the temperature was raised to 630 ℃ at a rate of 0.2 ℃/min, and the catalyst (Mo) of silica-supported molybdenum carbide was obtained after calcination for 2 hours 2 C/SiO 2 )。
Example 2
This example provides a method for preparing a molybdenum carbide catalyst, which comprises,
uniformly mixing 6mL of water, 160mL of octane and 16mL of laurinol polyoxyethylene ether to obtain trans-microemulsion, adding 0.09mmol of molybdenum isopropoxide, stirring for 12h to perform a first hydrolysis reaction, then adjusting the pH to be neutral, adding 4.5mmol of tetraethyl silicate solution, and stirring for 12h to perform a second hydrolysis reaction; adding methanol with the same volume as the solution into the solution, standing for layering, taking a lower-layer methanol phase, performing rotary evaporation concentration, and performing centrifugal drying to obtain a molybdenum carbide catalyst precursor;
putting the molybdenum carbide catalyst precursor into CH 4 /H 2 (v/v = 15%) in the mixed gas, the temperature was raised to 580 ℃ at a rate of 1 ℃/min, and the catalyst (Mo) of the silica-supported molybdenum carbide was obtained after calcination for 2 hours 2 C/SiO 2 )。
Example 3
This example provides a method for preparing a molybdenum carbide catalyst, comprising,
uniformly mixing 12mL of water, 240mL of octane and 18mL of laurinol polyoxyethylene ether to obtain trans-microemulsion, adding 0.12mmol of molybdenum isopropoxide, stirring for 12h to perform a first hydrolysis reaction, then adjusting the pH to be neutral, adding 2.4mmol of tetraethyl silicate solution, and stirring for 12h to perform a second hydrolysis reaction; adding methanol with the same volume as the solution into the solution, standing for layering, taking a lower-layer methanol phase, performing rotary evaporation concentration, and performing centrifugal drying to obtain a molybdenum carbide catalyst precursor;
putting the molybdenum carbide catalyst precursor into CH 4 /H 2 (v/v = 15%) in the mixed gas, the temperature was raised to 650 ℃ at a rate of 1.5 ℃/min, and the catalyst (Mo) of silica-supported molybdenum carbide was obtained after calcination for 2 hours 2 C/SiO 2 )。
Example 4
This example provides a method for preparing a molybdenum carbide catalyst, comprising,
uniformly mixing 6mL of water, 300mL of octane and 60mL of laurinol polyoxyethylene ether to obtain trans-microemulsion, adding 0.04mmol of molybdenum isopropoxide, stirring for 12h to perform a first hydrolysis reaction, then adjusting the pH to be neutral, adding 6mmol of tetraethyl silicate solution, and stirring for 12h to perform a second hydrolysis reaction; adding methanol with the same volume as the solution into the solution, standing for layering, taking a lower-layer methanol phase, performing rotary evaporation concentration, and performing centrifugal drying to obtain a molybdenum carbide catalyst precursor;
putting the molybdenum carbide catalyst precursor into CH 4 /H 2 (v/v = 15%) in the mixed gas, the temperature was raised to 550 ℃ at a rate of 2 ℃/min, and the catalyst (Mo) of the silica-supported molybdenum carbide was obtained after calcination for 2 hours 2 C/SiO 2 )。
Example 5
This example provides a method for preparing a molybdenum carbide catalyst, comprising,
uniformly mixing 3.6mL of water, 300mL of octane and 16mL of lauryl alcohol polyoxyethylene ether to obtain trans-microemulsion, adding 0.06mmol of molybdenum isopropoxide, stirring for 12h to perform a first hydrolysis reaction, then adjusting the pH to be neutral, adding 7.2mmol of tetraethyl silicate solution, and stirring for 12h to perform a second hydrolysis reaction; adding methanol with the same volume as the solution into the solution, standing for layering, taking a lower-layer methanol phase, performing rotary evaporation concentration, and performing centrifugal drying to obtain a molybdenum carbide catalyst precursor;
putting the molybdenum carbide catalyst precursor into CH 4 /H 2 (v/v = 15%) in the mixed gas, the temperature was raised to 700 ℃ at a rate of 0.6 ℃/min, and the catalyst (Mo) of silica-supported molybdenum carbide was obtained after calcination for 2 hours 2 C/SiO 2 )。
Example 6
This example provides a method for preparing a molybdenum carbide catalyst, comprising,
uniformly mixing 4mL of water, 280mL of octane and 35mL of laurinol polyoxyethylene ether to obtain trans-microemulsion, adding 0.03mmol of isopropanol molybdenum, stirring for 12 hours to perform a first hydrolysis reaction, then adjusting the pH value to be neutral, adding 6mmol of tetraethyl silicate solution, stirring for 12 hours to perform a second hydrolysis reaction; adding methanol with the same volume as the solution into the solution, standing for layering, taking a lower-layer methanol phase, performing rotary evaporation concentration, and performing centrifugal drying to obtain a molybdenum carbide catalyst precursor;
putting the precursor of the molybdenum carbide catalyst into CH 4 /H 2 (v/v = 15%) in the mixed gas, the temperature was raised to 600 ℃ at a rate of 1.8 ℃/min, and the catalyst (Mo) of silica-supported molybdenum carbide was obtained after calcination for 2 hours 2 C/SiO 2 )。
Example 7
This example provides the use of the molybdenum carbide catalyst of example 2 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 1g of benzyl phenyl ether, 0.1g of molybdenum carbide catalyst and 100g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, then heating the reaction kettle to 240 ℃, reacting for 5 hours, cooling, filtering, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 8
This example provides the use of the molybdenum carbide catalyst of example 6 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 3g of benzyl phenyl ether, 0.15g of molybdenum carbide catalyst and 180g of propanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air in the reaction kettle be an inert atmosphere, then heating the reaction kettle to 260 ℃, reacting for 3 hours, cooling, carrying out suction filtration, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 9
This example provides the use of the molybdenum carbide catalyst of example 3 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 2g of benzyl phenyl ether, 0.06g of molybdenum carbide catalyst and 140g of isopropanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, then heating the reaction kettle to 220 ℃, reacting for 4 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 10
This example provides the use of the molybdenum carbide catalyst of example 2 to selectively cleave the C-O ether linkage in benzyl phenyl ether, comprising,
adding 4g of benzyl phenyl ether, 0.05g of molybdenum carbide catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, then heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, filtering, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 11
This example provides the use of the molybdenum carbide catalyst of example 1 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 6g of benzyl phenyl ether, 0.08g of molybdenum carbide catalyst and 150g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, heating the reaction kettle to 190 ℃, reacting for 2 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 12
This example provides the use of the molybdenum carbide catalyst of example 4 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 5g of benzyl phenyl ether, 0.1g of molybdenum carbide catalyst and 150g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, then heating the reaction kettle to 160 ℃, reacting for 6 hours, cooling, filtering, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 13
This example provides the use of the molybdenum carbide catalyst of example 3 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 10g of benzyl phenyl ether, 0.25g of molybdenum carbide catalyst and 100g of propanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the atmosphere inert, then heating the reaction kettle to 180 ℃, reacting for 4.5 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 14
This example provides the use of the molybdenum carbide catalyst of example 5 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 7g of benzyl phenyl ether, 0.1g of molybdenum carbide catalyst and 200g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, heating the reaction kettle to 230 ℃, reacting for 1.5h, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Example 15
This example provides the use of the molybdenum carbide catalyst of example 1 for the selective cleavage of a C-O ether linkage in benzyl phenyl ether comprising,
adding 2g of benzyl phenyl ether, 0.02g of molybdenum carbide catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, then heating the reaction kettle to 240 ℃, reacting for 3 hours, cooling, filtering, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Comparative example 1
The comparative example provides a Ni/SiO 2 A process for the selective cleavage of C-O ether linkages in benzyl phenyl ethers of a catalyst, differing from example 10 in the type of catalyst, which comprises,
4g of benzyl phenyl ether, 0.05g of Ni/SiO 2 Adding a catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air in the reaction kettle be in an inert atmosphere, then heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol and toluene.
Comparative example 2
This comparative example provides a Pt/SiO 2 A process for the selective cleavage of C-O ether linkages in benzyl phenyl ethers of a catalyst, differing from example 10 in the type of catalyst, which comprises,
4g of benzyl phenyl ether, 0.05g of Pt/SiO 2 Adding a catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air in the reaction kettle be in an inert atmosphere, then heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol and toluene.
Comparative example 3
This comparative example provides a Ru/SiO solid solution 2 A process for the selective cleavage of C-O ether linkages in benzyl phenyl ethers of a catalyst, differing from example 10 in the type of catalyst, which comprises,
4g of benzyl phenyl ether and 0.05g of Ru/SiO 2 Adding catalyst and 160g of ethanol into a reaction kettle, and introducing nitrogen for replacement reactionAnd (3) introducing air in the kettle to make the air inert, heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol and toluene.
Comparative example 4
This comparative example provides a Pd/SiO 2 A process for the selective cleavage of C-O ether linkages in benzyl phenyl ethers of a catalyst, differing from example 10 in the type of catalyst, which comprises,
4g of benzyl phenyl ether and 0.05g of Pd/SiO 2 Adding a catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air inert, heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol and toluene.
Comparative example 5
This comparative example provides a Rh/SiO 2 A process for the selective cleavage of C-O ether linkages in benzyl phenyl ethers of a catalyst, differing from example 10 in the type of catalyst, which comprises,
4g of benzyl phenyl ether, 0.05g of Rh/SiO 2 Adding a catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air in the reaction kettle be in an inert atmosphere, then heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol and toluene.
Comparative example 6
This comparative example provides a Mo 2 C/SiO 2 The process for the selective cleavage of the C-O ether bond in benzyl phenyl ether of a catalyst differs from example 10 in that the catalyst is prepared by a conventional impregnation method comprising,
4g of benzyl phenyl ether, 0.05g of Rh/SiO 2 Adding a catalyst and 160g of ethanol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle to make the air in the reaction kettle be in an inert atmosphere, then heating the reaction kettle to 200 ℃, reacting for 6 hours, cooling, performing suction filtration, extracting a liquid product, and separating to obtain phenol, toluene, benzene and benzyl alcohol products.
Test examples
This experimental example provides the performance tests and results of the catalysts of examples 7-15 and comparative examples 1-6 on benzyl phenyl ether to produce phenol, toluene, benzene and benzyl alcohol, according to the formula I: samples after the reactions in examples 7-15 and comparative examples 1-6 were collected and subjected to qualitative and quantitative analysis on Agilent gas chromatograph-mass spectrometer (7890B-5975) and gas chromatograph (7890B), respectively, under the following analysis conditions: the sample inlet temperature is 280 ℃, the split ratio of the sample inlet is 50. Quantitative analysis takes mesitylene as an internal standard substance and adopts an internal standard method to carry out quantitative analysis. The calculation formula of the conversion rate of benzyl phenyl ether and the yield of the product is as follows, wherein m represents the mass of the compound;
TABLE 1 conversion Performance of benzylphenyl ether catalyzed reactions in examples 7 to 15 and comparative examples 1 to 6
As can be seen from Table 1, in examples 7-15, the volume ratio of water, alkane and surfactant, the weight ratio of molybdenum to silicon, the calcination temperature and the temperature rise rate have an influence on the performance of the molybdenum carbide catalyst, and further influence the conversion rate of benzyl phenyl ether and the selectivity of the product; the amount of benzyl phenyl ether, the amount of catalyst, the reaction temperature and the reaction time also have a certain influence on the conversion rate of benzyl phenyl ether and the selectivity of the product.
Comparative examples 1-5 all had less than 40% benzylphenyl ether conversion and no more than 25% total selectivity to phenol and toluene, indicating that when Ni/SiO is used 2 、Pt/SiO 2 、Pd/SiO 2 、Ru/SiO 2 、Rh/SiO 2 When the catalyst is used, the selectivity of the target product phenol and toluene and the conversion rate of benzyl phenyl ether are far lower than those of the high-dispersity molybdenum carbide catalyst provided by the invention.
Comparison between comparative example 6 and example 10 shows that the conversion rate of benzyl phenyl ether and the selectivity of target products of phenol, toluene, benzene and benzyl alcohol of the molybdenum carbide catalyst prepared by the method of the invention are higher than those of the molybdenum carbide catalyst prepared by the traditional impregnation method.
FIGS. 1 to 6 are TEM images of the catalysts prepared in examples 1 to 6, respectively, and it can be seen that the distribution of the molybdenum carbide active centers in the molybdenum carbide catalyst is uniform and the particle size of the molybdenum carbide catalyst can be controlled between 1 nm and 5nm.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (8)
1. The application of a molybdenum carbide catalyst in benzyl phenyl ether catalytic reaction;
the preparation method of the molybdenum carbide catalyst comprises the following steps,
mixing alkane, surfactant and water to obtain trans-microemulsion, adding organic soluble molybdenum salt, performing a first hydrolysis reaction, adding a silicon source, and performing a second hydrolysis reaction; adding an organic solvent, and standing for layering to obtain a molybdenum carbide precursor;
and calcining the molybdenum carbide precursor to obtain the molybdenum carbide catalyst.
2. Use according to claim 1, wherein the organic soluble molybdenum salt is molybdenum isopropoxide and/or molybdenum ethoxide.
3. The use according to claim 1, characterized in that the calcination temperature is 550-700 ℃ and the calcination time is 2-6h;
heating to the calcination temperature at a rate of 0.2-2 ℃/min.
4. Use according to claim 1, wherein the molar ratio of molybdenum in the organic soluble molybdenum salt and silicon in the silicon source is 1: (20-200);
the particle size of the molybdenum carbide catalyst is 1-5nm.
5. Use according to claim 1, wherein the amount of the organic soluble molybdenum salt in the trans-microemulsion is 1-20mmol/L.
6. Use according to claim 1, wherein the volume ratio of surfactant to alkane is 1: (4-20);
the volume ratio of the water to the alkane is as follows: 1: (10-100);
the surfactant is a nonionic surfactant;
the alkane is at least one of heptane, octane and nonane;
the calcining atmosphere is CH 4 And H 2 Mixed gas of (2), the CH 4 And H 2 The volume fraction ratio of (1-4): 1.
7. the use according to claim 1, characterized in that the benzylphenyl ether catalyzed reaction comprises the steps of,
the benzyl phenyl ether, the molybdenum carbide catalyst and the hydrogen-rich solvent are subjected to catalytic reaction at 160-260 ℃, and phenol, toluene, benzene and benzyl alcohol are obtained after separation.
8. Use according to claim 7, wherein the reaction time is 1-6h;
the mass ratio of the benzyl phenyl ether to the molybdenum carbide catalyst is (10-100): 1; the mass ratio of the benzyl phenyl ether to the solvent is 1: (10-100);
the hydrogen-rich solvent is ethanol, propanol or isopropanol.
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