CN114749203B - Mesoporous molecular sieve HMS supported platinum nickel element catalyst - Google Patents
Mesoporous molecular sieve HMS supported platinum nickel element catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of molecular sieve catalysts, and particularly relates to a mesoporous molecular sieve-Hexagonal Mesoporous Silicon (HMS) supported platinum-nickel element catalyst. The invention synthesizes platinum-mesoporous molecular sieve by one-pot method as carrier, then loads nickel by isovolumetric impregnation method, uses nickel complex as nickel precursor, and finally obtains a dehydrogenation catalyst (nickel/platinum/mesoporous silicon) by alkali metal salt modification. The loading method is simple, convenient and effective, and solves the technical problem of forming precipitation among nickel salt, platinum salt and complex. The detection and application results show that the prepared catalyst product has the advantages of high dispersion of active components, high catalytic activity, longer service life of the catalyst, high yield of catechol as a product, low preparation cost and good industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of molecular sieve catalysts, and particularly relates to a catalyst for loading platinum and nickel elements by using mesoporous molecular sieve HMS.
Background
Catechol is used as a fine chemical intermediate product and is widely used for preparing chemicals in the fields of pharmacy, perfume, rubber and the like. The traditional catechol preparation adopts the hydrolysis process of o-methoxyphenol or o-chlorophenol, but is being phased out due to the defects of complex process, more byproducts, large production pollution, large separation difficulty and the like.
Based on the green chemical industry requirement, two process routes of a phenol hydroxylation method and a 1, 2-cyclohexanediol dehydrogenation method are further developed. The phenol hydroxylation method is characterized in that phenol is used as a raw material, hydrogen peroxide is used as an oxidant under the action of a catalyst, and the obtained product is a mixture of p-hydroxyphenol (hydroquinone) and o-hydroxyphenol (catechol), so that further separation is needed. The synthetic process route has the defects of high requirements on the concentration of hydrogen peroxide, high consumption, low phenol conversion rate, difficult product separation and the like, so that the practical application is more limited.
Along with the development of cyclohexene related technology, scientific researchers develop a new process route for preparing cyclohexene oxide by oxidizing cyclohexene as a raw material, further hydrolyzing the cyclohexene oxide to generate 1, 2-cyclohexanediol, and preparing catechol by dehydrogenation. The process route has the advantages of single product, simple separation and purification process, less three wastes in the reaction process and environmental protection. The catalyst is used for catalyzing the dehydrogenation of the 1, 2-cyclohexanediol to ensure better synthesis effect. The common catalyst takes nickel as a main active component, a small amount of elements such as platinum, palladium, rhodium, tin and the like are added, and sodium sulfate is also required to be added as a cocatalyst so as to ensure the smooth progress of dehydrogenation reaction.
Although the reaction of preparing catechol by dehydrogenating 1, 2-cyclohexanediol has been studied in a large amount, the disadvantages of low conversion rate, poor selectivity, high catalyst deactivation speed and the like still exist, which limit the application of the process. In the prior art, researchers have made more researches on catalyst carriers, active components, loading methods thereof and the like aiming at the characteristics and technical requirements of catalysts in cyclohexanediol dehydrogenation reaction. It is believed that in catalyst selection and application, there are problems with the cost of the active component, and also the effectiveness of the active component loading and feasibility of the process that are considered to be a concern for the effect of the carrier on the reaction. Therefore, a new catalyst product is designed based on the technical problems of catalyst activity, selectivity, stability and the like, and the catalyst product has important significance for the development of related industries.
Disclosure of Invention
The invention aims to provide a mesoporous molecular sieve HMS supported platinum nickel element catalyst which is used for preparing catechol by taking 1, 2-cyclohexanediol as a raw material for dehydrogenation, thereby realizing the green preparation industrialization of catechol.
In order to achieve the aim of the invention, the catalyst is prepared by taking a mesoporous molecular sieve as a carrier and platinum and nickel as catalytic active components, and is prepared by the following steps:
preparation of mesoporous molecular sieve carrier
1. Weighing cationic surfactant, ethanol I and water, and fully stirring until the mixture is clear to obtain solution A;
the cationic surfactant is as follows: any one of n-octylamine, n-nonylamine, n-decylamine and undecylamine-octadecylamine (such as dodecylamine and hexadecylamine);
2. weighing tetraethoxysilane, ethanol II and chloroplatinic acid, and fully stirring and uniformly mixing to obtain solution B;
3. slowly adding the solution B into the solution A which is vigorously stirred at room temperature, stirring, standing and aging;
4. filtering, washing, drying (the reference setting temperature is 120 ℃), roasting (480-600 ℃) (preferably roasting at the heating rate of 1-3 ℃/min for 1-4 hours at the temperature of 500-600 ℃) to obtain the mesoporous molecular sieve carrier;
ethyl orthosilicate: cationic surfactant: ethanol I: ethanol II: chloroplatinic acid=1: 0.1-0.5:5-10:0.5-2:0.002-0.004; the preferable proportion is as follows: 1:0.2-0.3:6-8:0-1.8:0.0025-0.0035.
(II) Nickel-carrying
Weighing soluble salt and complex of nickel by using an isovolumetric impregnation method, and uniformly mixing in a solvent; adding the solution into the mesoporous molecular sieve carrier obtained in the step (one), stirring under ultrasound, drying and roasting (480-530 ℃).
The soluble salts of nickel are: soluble nickel salts such as nickel nitrate or nickel sulfate;
the complex is as follows: any one of amine, ethylenediamine tetraacetic acid and salts thereof, hydrazine, glycine and lysine;
the complex comprises the following components in percentage by mass: nickel salt = 6-1:1, a step of;
the solvent is water, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide or a mixture of two or more of the above;
the nickel salt comprises the following components in percentage by mass: mesoporous molecular sieve support = 0.15-0.3: 1.
sodium sulfate modification
And (3) loading 2-4wt% sodium sulfate on the powder obtained in the step (II) by using an isovolumetric impregnation method, and drying to obtain the 1, 2-cyclohexanediol dehydrogenation catalyst. Based on the mass of the silicon dioxide, the nickel loading is about 5-7wt% and the platinum loading is about 0.5-1.2wt%.
The invention has the advantages that: 1. hexagonal Mesoporous Silica (HMS) in a mesoporous molecular sieve is selected as the catalyst support. Aiming at the fact that the mechanism of the 1, 2-cyclohexanediol reaction and the traditional dehydrogenation catalyst that strong acid sites are needed to adsorb C-H bonds is different, weak acid mesoporous silica is selected, and side reaction products in the product can be reduced. Meanwhile, the existing dehydrogenation reaction temperature is high, and the product is phenols, so that carbon deposition in the reaction process can be reduced by virtue of excellent diffusion conditions, and the service life of the catalyst is prolonged. According to the invention, when the nickel complex is used for loading, the mesoporous molecular sieve is used as a carrier, and the metal platinum can be loaded in situ by using a one-pot method by using a simple synthesis method of HMS, so that the formation of precipitation with platinum salt is avoided.
2. The invention adopts an isovolumetric impregnation method to load nickel, and a nickel complex is used as a precursor during the loading. The method has the advantages that the solvent is used in a small amount in the isovolumetric impregnation method, and the structure of the mesoporous molecular sieve HMS can be protected. Meanwhile, the invention also aims at the problem that aggregation is easy to occur at certain parts of the carrier in the nickel loading process, and the active component nickel complex is used for impregnation. The acting force of the active component and the carrier is weakened in the impregnation process, aggregation of the active component in the impregnation process is avoided, and the dispersity of the active component is obviously improved, so that higher selectivity and longer service life are brought to the catalytic reaction.
Based on the characteristics of the catalytic reaction and the design method of the catalyst, the mesoporous molecular sieve HMS is invented as a carrier of a supported catalyst, and platinum is supported by a one-pot method in the synthesis process of the molecular sieve HMS. After HMS in which platinum element has been dispersed is obtained using a one-pot method, an isovolumetric impregnation method is employed, using a nickel complex as a nickel source to support nickel. Preliminary detection and application results show that the usage amount of active components in the prepared catalyst product is obviously reduced compared with the prior study, the platinum-nickel content is reduced by a plurality of times compared with the prior study, the nickel content is generally 20-35 wt%, the noble metal content is 0-4 wt%, the noble metal content is 6wt%, and the noble metal content is 1wt%. The catalyst has good activity, the optimal conversion rate reaches 100%, the selectivity reaches 99.7%, and the service life reaches 150h (the yield is more than 79%). The catalyst shows outstanding performance in long-time experiments, and the characterization finds that the active components of the catalyst are highly dispersed, and the catalyst has the advantages of simple and convenient preparation method, low preparation cost and good industrialized application prospect.
Drawings
FIG. 1 is a network diagram of a dehydrogenation reaction relationship of 1, 2-cyclohexanediol;
FIG. 2 is an X-ray diffraction chart of the catalyst prepared in example 1 and comparative example 3 of the present invention;
FIG. 3 is a graph showing the diffuse reflection spectrum of ultraviolet-visible light of the catalyst prepared in example 1 and comparative example 3 of the present invention;
FIG. 4 is a photograph showing the distribution of the results of scanning electron micrographs and energy scattering type X-ray fluorescence spectrometer scanning (EDX mapping) analyses of the catalysts prepared in example 1 and comparative example 3 of the present invention;
FIG. 5 is a long-period evaluation result of the catalyst prepared in example 1 of the present invention in catalyzing the dehydrogenation of 1, 2-cyclohexanediol.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention may be made without departing from the spirit and nature of the invention and are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
Example 1
In the preparation process of the catalyst, a mesoporous silicon HMS carrier containing platinum is synthesized firstly, then nickel is loaded, finally cocatalyst sodium sulfate is continuously loaded, and finally the catalyst product is obtained. Specific examples of the related preparation process are as follows.
One-pot method for preparing platinum-containing mesoporous molecular sieve HMS carrier
1. 1.667g of a dodecyl amine cationic surfactant, 11.402g of ethanol and 16.203g of water are weighed and fully stirred until the mixture is clear, so as to obtain a solution A;
2. 6.944g of ethyl orthosilicate, 2.420g of ethanol and 0.042g of chloroplatinic acid are weighed and fully stirred and uniformly mixed to obtain solution B;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, and standing and aging for 24h at 25 ℃;
filtering, washing and drying (drying at 120 ℃ for 4 h); finally, roasting the product at 550 ℃ for 4 hours (heating rate: 2 ℃/min) to remove the template agent, and obtaining the mesoporous molecular sieve carrier containing platinum.
(II) Nickel-carrying
Using an isovolumetric impregnation method, weighing 0.297g of nickel nitrate, dissolving 0.184g of complex ethylenediamine in deionized water, and uniformly mixing;
taking 1g of the mesoporous molecular sieve carrier obtained in the step (I), loading nickel element by using an isovolumetric impregnation method, drying at 60 ℃ for 4 hours, and roasting at 480 ℃ for 4 hours (heating rate: 2 ℃/min).
(III) alkali Metal modification
Weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 60 ℃ for 4 hours; tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt%, and the platinum loading is about 0.5-1.2wt% (based on the mass of silicon dioxide), and the catalyst is recorded as ML-1.
Example 2
In the step (one), the step (c),
in the solution A: the cationic surfactant is hexadecylamine; the specific dosage is 2.42g of hexadecylamine, 21.002g of ethanol and 5.367g of water;
and in the solution B: the specific dosage is 10.734g of ethyl orthosilicate, 6.944g of ethanol and 0.042g of chloroplatinic acid;
and slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 20min after the dripping is finished, and standing and aging for 20h. Filtering, washing and drying (drying at 130 ℃ for 4 hours); finally, roasting the product for 4 hours at 550 ℃ (heating rate: 2 ℃/min) to remove the template agent, thereby obtaining the mesoporous molecular sieve carrier containing platinum;
in the step (two), the step (C),
the specific dosage is 0.297g of nickel nitrate, 0.184g of ethylenediamine, dissolved in deionized water,
taking 1g of the mesoporous molecular sieve carrier obtained in the step (one), loading nickel element by using an isovolumetric impregnation method, and drying at 60 ℃ for 4 hours; finally, the product was calcined at 480℃at a rate of 2℃per minute (rate of temperature increase: 2℃per minute) for 4 hours.
In the step (three), the step (c),
weighing 0.03g of alkali metal salt (sodium sulfate) and adding into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying at 70 ℃ for 4 hours; tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt%, and the platinum loading is about 0.5-1.2wt% (based on the mass of silicon dioxide), and the catalyst is recorded as ML-2.
Example 3
In the step (one), the step (c),
in the solution A: the cationic surfactant is dodecyl amine; the specific dosage is 1.667g of laurylamine, 11.402g of ethanol and 16.203g of water;
and in the solution B: the specific dosage is 6.944g of tetraethoxysilane, 2.420g of ethanol and 0.034g of chloroplatinic acid;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, standing and aging for 24h;
filtering, washing and drying (drying at 120 ℃ for 5 h); finally, roasting the product for 4 hours at 550 ℃ (heating rate: 2 ℃/min) to obtain a mesoporous molecular sieve carrier containing platinum;
in the step (two), the step (C),
the specific dosage is 0.297g of nickel nitrate, 0.184g of ethylenediamine, dissolved in deionized water,
taking 1g of the mesoporous molecular sieve carrier obtained in the step (one), loading nickel element by using an isovolumetric impregnation method, and drying at 60 ℃ for 4 hours; finally, the product was calcined at 500℃for 3h (rate of temperature increase: 2 ℃ C./min).
In the step (three), the step (c),
weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 60 ℃ for 4 hours; tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt%, and the platinum loading is about 0.5-1.2wt% (based on the mass of silicon dioxide), and the catalyst is recorded as ML-3.
Example 4
In the step (one), the step (c),
in the solution A: the cationic surfactant is dodecyl amine; the specific dosage is 1.667g of laurylamine, 11.402g of ethanol and 16.203g of water;
and in the solution B: the specific dosage is 6.944g of tetraethoxysilane, 2.420g of ethanol and 0.042g of chloroplatinic acid;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, standing and aging for 24h;
filtering, washing and drying (drying at 120 ℃ for 4 h); finally, roasting the product for 4 hours at 550 ℃ (heating rate: 2 ℃/min) to obtain a mesoporous molecular sieve carrier containing platinum;
in the step (two), the step (C),
the specific dosage is 0.297g of nickel nitrate, 0.123g of hydrazine hydrate, and the solution is dissolved in deionized water;
taking 1g of the mesoporous molecular sieve carrier obtained in the step (one), loading nickel element by using an isovolumetric impregnation method, and drying at 60 ℃ for 4 hours; finally, the product was calcined at 480℃for 4h (rate of temperature increase: 2 ℃ C./min).
In the step (three), the step (c),
weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 60 ℃ for 4 hours; tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt%, and the platinum loading is about 0.5-1.2wt% (based on the mass of silicon dioxide), and the catalyst is recorded as ML-4.
Example 5
In the step (one), the step (c),
in the solution A: the cationic surfactant is dodecyl amine; the specific dosage is 1.667g of laurylamine, 11.402g of ethanol and 16.203g of water;
and in the solution B: the specific dosage is 6.944g of tetraethoxysilane, 2.420g of ethanol and 0.034g of chloroplatinic acid;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, standing and aging for 24h;
filtering, washing and drying (drying at 120 ℃ for 4 h); finally, roasting the product for 3 hours at 560 ℃ at a heating rate of 2 ℃/min to obtain a mesoporous molecular sieve carrier containing platinum;
in the step (two), the step (C),
the specific amount of nickel nitrate hexahydrate 0.297g, ethylenediamine 0.184g, dissolved in N, N-diethylformamide:
taking 1g of the mesoporous molecular sieve carrier obtained in the step (one), loading nickel element by using an isovolumetric impregnation method, and drying at 60 ℃ for 4 hours; finally, the product was calcined at 480℃for 4h (rate of temperature increase: 2 ℃ C./min).
In the step (three), the step (c),
weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 70 ℃ for 4 hours; tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt%, and the platinum loading is about 0.5-1.2wt% (based on the mass of silicon dioxide), and the catalyst is recorded as ML-5.
Comparative example 1:
preparation of mesoporous molecular sieve carrier
1.667g of dodecyl amine, 11.402g of ethanol and 16.203g of water are weighed and fully stirred until the mixture is clear, so as to obtain solution A;
6.944g of ethyl orthosilicate and 2.420g of ethanol are weighed, fully stirred and uniformly mixed to obtain solution B;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, and standing and aging for 25h at 25 ℃;
filtering, washing and drying (drying at 120 ℃ for 4 h); finally, roasting the product for 4 hours at 550 ℃ (heating rate: 2 ℃/min) to remove the template agent, thus obtaining the mesoporous molecular sieve carrier;
(II) Nickel-carrying
Weighing 0.297g of nickel nitrate by using an isovolumetric impregnation method, and uniformly mixing the nickel nitrate with deionized water;
taking 1g of the mesoporous molecular sieve carrier obtained in the step (I), loading nickel element by using an isovolumetric impregnation method, drying at 60 ℃ for 4 hours, and roasting at 480 ℃ for 4 hours (heating rate: 2 ℃/min).
(III) alkali Metal modification
Weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 60 ℃ for 4 hours; tabletting and crushing to 40-60 meshes, wherein the nickel loading is about 5-7wt% (based on the mass of the silicon dioxide), and is recorded as CP-1.
Comparative example 2:
preparation of mesoporous molecular sieve carrier
1.667g of dodecyl amine, 11.402g of ethanol and 16.203g of water are weighed and fully stirred until the mixture is clear, so as to obtain solution A;
6.944g of ethyl orthosilicate and 2.420g of ethanol are weighed and fully stirred and mixed uniformly to be called as solution B;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, and standing and aging for 25h at 25 ℃;
filtering, washing and drying (drying at 120 ℃ for 4 h); finally, roasting the product for 4 hours at 550 ℃ (heating rate: 2 ℃/min) to remove the template agent, thus obtaining the mesoporous molecular sieve carrier;
(II) Nickel-carrying
Weighing 0.297g of nickel nitrate and ethylenediamine complex by using an isovolumetric impregnation method, and uniformly mixing in deionized water;
taking 1g of the mesoporous molecular sieve carrier obtained in the step (I), loading nickel element by using an isovolumetric impregnation method, drying at 60 ℃ for 4 hours, and roasting at 480 ℃ for 4 hours (heating rate: 2 ℃/min).
(III) alkali Metal modification
Weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 60 ℃ for 4 hours; tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt% (based on the mass of silicon dioxide), and the catalyst is recorded as CP-2.
Comparative example 3:
preparation of mesoporous molecular sieve carrier
1.667g of dodecyl amine, 11.402g of ethanol and 16.203g of water are weighed and fully stirred until the mixture is clear, so as to obtain solution A;
6.944g of ethyl orthosilicate and 2.420g of ethanol are weighed, fully stirred and uniformly mixed to obtain solution B;
slowly adding the solution B into the vigorously stirred solution A at room temperature, continuously stirring for 15min after the dripping is finished, and standing and aging for 25h at 25 ℃;
filtering, washing and drying (drying at 120 ℃ for 4 h); finally, roasting the product for 4 hours at 550 ℃ (heating rate: 2 ℃/min) to remove the template agent, thus obtaining the mesoporous molecular sieve carrier;
(II) Nickel and platinum Supported
Using an isovolumetric impregnation method, weighing 0.297g of nickel nitrate and 0.021g of chloroplatinic acid, and uniformly mixing in deionized water;
taking 1g of the mesoporous molecular sieve carrier obtained in the step (I), loading nickel element by using an isovolumetric impregnation method, drying at 60 ℃ for 4 hours, and roasting at 480 ℃ for 4 hours (heating rate: 2 ℃/min).
(III) alkali Metal modification
Weighing 0.03g of sodium sulfate, adding the sodium sulfate into water, loading the powder obtained in the step (II) by adopting an isovolumetric impregnation method, and drying the powder at 60 ℃ for 4 hours;
tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel loading is about 5-7wt% and the platinum loading is about 0.5-1.2wt% (based on the mass of silicon dioxide), and the catalyst is recorded as CP-3.
Comparative example 4 (25 wt% nickel/4 wt% platinum silica mass catalyst):
130.4g of urea solution (7.5 wt%) was weighed and 9.783g of silica sol (30 wt%) was added with vigorous stirring, called solution A;
weighing 0.528g of chloroplatinic acid, 6.279g of nickel nitrate hexahydrate, dissolving in 10ml of water, adding into the solution A, refluxing at 95 ℃ for 5 hours, standing, cooling to room temperature, filtering, drying at 95 ℃ for 6 hours, and roasting in a muffle furnace at 450 ℃ for 4 hours;
and then adopting an isovolumetric impregnation method to load 2wt% of sodium sulfate, drying at 90 ℃, tabletting, crushing to 40-60 meshes, and obtaining the catalyst, wherein the nickel load is about 24-26wt% and the platinum load is about 3.5-5.5wt% (based on the mass of silicon dioxide). And is designated CP-4.
And (3) experimental verification:
catalyst performance was tested on a catalyst evaluation device (WFSM-3060):
the catalyst was first reduced before the reaction, at 480.+ -. 10 ℃ with H 2 (hydrogen flow rate is 40 ml/min) for 4h;
after the reduction is finished, the temperature is reduced to the reaction temperature, and reactants are introduced;
the raw material used was 10% by weight of 1, 2-cyclohexanediol (9.+ -. 1 ml/(h.g) cal ) Liquid time speed feeding), the feeding firstly passes through a vaporizer and then enters a reactor for reaction; in the reaction process, carrier gas adopts H 2 The flow rate was 20ml/min and the whole reaction was carried out at normal pressure. After the reaction is finished, the outlet material flow of the reactor is condensed, gas-liquid separation is carried out, and the liquid phase product is taken for composition analysis.
Qualitative and quantitative detection of the products was carried out by gas chromatography (tomorrow GC7900P chromatography workstation) equipped with FID detector. The conversion of 1, 2-cyclohexanediol is defined as X, the selectivity to catechol product is defined as S, and the selectivity to product is defined as follows:
wherein X0 and X1 represent the quantitative composition of the reactants and the material of 1, 2-cyclohexanediol in the product; yi is the composition of the amounts of the substances of component i.
The catalyst performance is shown in table 1 below:
| catalyst numbering | 1, 2-cyclohexanediol conversion/% | Catechol selectivity/% |
| ML-1 | 100 | 99.73 |
| ML-2 | 100 | 99.72 |
| ML-3 | 100 | 99.10 |
| ML-4 | 100 | 98.34 |
| ML-5 | 100 | 99.88 |
| CP-1 | 75.84 | 62.91 |
| CP-2 | 86.24 | 72.18 |
| CP-3 | 100 | 91.11 |
| CP-4 | 95.32 | 93.86 |
TABLE 2 analysis of elemental content of the catalyst prepared in example 1 of the present invention
Claims (3)
1. The mesoporous molecular sieve-HMS supported platinum and nickel catalyst is characterized by being prepared by the following steps:
i, preparing a platinum-containing mesoporous molecular sieve HMS carrier by a one-pot method:
(1) Weighing cationic surfactant, ethanol I and water, and fully stirring until the mixture is clear to obtain solution A;
the cationic surfactant is as follows: any one of n-octylamine, n-nonylamine, n-decylamine and n-undecyl-octadecylamine;
(2) Weighing tetraethoxysilane, ethanol II and chloroplatinic acid, and fully stirring and uniformly mixing to obtain solution B;
(3) Slowly adding the solution B into the solution A which is vigorously stirred at room temperature, stirring, standing and aging;
(4) Filtering, washing, drying and roasting to obtain a mesoporous molecular sieve carrier containing platinum;
II, nickel loading:
(1) Weighing soluble salt and complex of nickel by using an isovolumetric impregnation method, and uniformly mixing in a solvent; adding the mesoporous molecular sieve into the mesoporous molecular sieve carrier prepared in the step I, stirring, drying and roasting under ultrasound;
the soluble salts of nickel are: nickel nitrate or nickel sulfate;
the complex is as follows: any one of ethylenediamine, ethylenediamine tetraacetic acid and salts thereof, hydrazine, glycine and lysine;
the solvent is water, N-dimethylformamide, N-diethylformamide, dimethyl sulfoxide or a mixture thereof;
III, modifying sodium sulfate:
loading sodium sulfate on the powder obtained in the step II by using an isovolumetric impregnation method, and drying to obtain a target product;
the target is based on the mass of silicon dioxide, the loading of nickel is 5-7wt% and the loading of platinum is 0.5-1.2wt%.
2. The mesoporous molecular sieve HMS supported platinum and nickel catalyst according to claim 1, wherein,
in the step I, according to the mass ratio of substances, tetraethoxysilane: cationic surfactant: ethanol I: ethanol II: chloroplatinic acid=1: 0.1 to 0.5:5-10:0.5 to 2: 0.002-0.004.
3. The mesoporous molecular sieve HMS supported platinum and nickel catalyst according to claim 1, wherein,
in the step II, the nickel salt is calculated according to the mass ratio: complex = 1:1 to 6;
in the step II, the mass ratio of the nickel salt is as follows: mesoporous molecular sieve support = 0.15-0.3: 1.
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