CN115254183A - Spherical flower-shaped composite catalyst material, preparation method thereof and preparation method of cyclohexanone oxime - Google Patents

Spherical flower-shaped composite catalyst material, preparation method thereof and preparation method of cyclohexanone oxime Download PDF

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CN115254183A
CN115254183A CN202211077463.9A CN202211077463A CN115254183A CN 115254183 A CN115254183 A CN 115254183A CN 202211077463 A CN202211077463 A CN 202211077463A CN 115254183 A CN115254183 A CN 115254183A
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mcm
cyclohexanone oxime
preparation
cyclohexylamine
catalyst
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刘水林
刘宁
唐新德
伍素云
钟哲浩
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Hunan Institute of Technology
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25

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Abstract

A spherical flower-shaped composite catalyst material, a preparation method thereof and a preparation method of cyclohexanone oxime relate to the technical field of green preparation processes of cyclohexanone oxime. The composite catalyst material assembled by the spheroidal particles with the particle size of about 4um and the columnar particles with the particle size of 0.05-0.1 um is prepared through a short process flow, the catalyst is micron-sized particles with a spherical flower-shaped appearance, and the spheroidal particles consist of a large number of two-dimensional crystal plates. Tests prove that the catalyst has good structural stability, forms a large number of active sites therein, is not easy to inactivate in the catalytic reaction process, and can be repeatedly used after being separated. Under the action of the catalyst, molecular oxygen is used as a green oxidant, the cyclohexanone oxime can be synthesized by performing liquid-phase oxidation reaction on the cyclohexylamine under mild conditions, and the synthesis process has high cyclohexylamine conversion rate and high cyclohexanone oxime selectivity and has industrial application prospect.

Description

Spherical flower-shaped composite catalyst material, preparation method thereof and preparation method of cyclohexanone oxime
Technical Field
The invention relates to the technical field of a green preparation process of cyclohexanone-oxime, and particularly relates to a spherical composite catalyst material, a preparation method thereof and a method for preparing cyclohexanone-oxime by catalytically oxidizing cyclohexylamine by using the composite catalyst material.
Background
The industrial production method of cyclohexanone oxime mainly includes cyclohexanone-hydroxylamine method and cyclohexanone-ammoximation method, and both of these two methods use intermediate cyclohexanone as raw material. Chinese patent document CN101928231A discloses synthesis of cyclohexanone oxime by reacting titanium silicate (Ti-MCM 41) with a mesoporous structure with cyclohexanone in a water-soluble organic solvent through organic peroxide, ammonia, wherein the method has high cyclohexanone conversion and cyclohexanone oxime selectivity, but the amount of waste liquid generated by the reaction is large, and the raw material cyclohexanone is mainly synthesized by a cyclohexane oxidation method, and the synthesis process has low conversion per pass (about 4%), high alkali consumption, high energy consumption and large waste alkali liquid treatment load, and has gradually been difficult to meet the environmental protection requirements.
The cyclohexanone is not needed to be used as a raw material for synthesizing cyclohexanone oxime by oxidizing the cyclohexylamine, and in recent years, two systems, namely molecular oxygen gas-phase oxidation and molecular oxygen liquid-phase oxidation, are mainly used in the cyclohexylamine oxidation method. Compared with a gas phase oxidation system, the catalyst under the molecular oxygen liquid phase oxidation system can stably work for a longer time, but most of the molecular oxygen liquid phase oxidation systems need to use an organic solvent, and three wastes generated in the reaction process are more. Chinese patent document CN103641740A discloses a method for preparing cyclohexanone oxime by catalyzing cyclohexylamine and molecular oxygen-containing gas with mesoporous silicon material (e.g. MCM) loaded with metal element (e.g. Ti), which does not need organic solvent, and is environmentally friendly, but the conversion rate of cyclohexylamine is low.
Disclosure of Invention
The invention aims to provide a preparation method of a spherical flower-shaped composite catalyst material with high conversion rate of the cyclohexylamine and high selectivity of the cyclohexanone oxime under a molecular oxygen liquid phase oxidation system.
In order to achieve the above object, the process for preparing a spherical composite catalyst material according to the present invention comprises the steps of:
(a) Adding a proper amount of molecular sieve MCM-22 and MCM-41 into water, and uniformly mixing to obtain a mixture I;
(b) One or more of ethanol, n-propanol and butanol are used as an organic solvent, a proper amount of titanium source is added into the organic solvent, and the solution II is obtained after uniform stirring;
(c) Heating the mixture I to 50-120 ℃, slowly adding the solution II into the mixture I under continuous stirring, adding ammonia water to adjust the pH value to 8-11, and continuously preserving the temperature for 1-4 hours to obtain a mixture III;
(d) And transferring the mixture III to a stainless steel crystallization kettle to react for 24-60 h at 120-180 ℃, separating the precipitate obtained by the reaction, and roasting for 2-8 h at 350-650 ℃ to obtain the target product.
Wherein the molecular sieve MCM-22 is prepared by the following steps:
preparing a mixed solution I by taking a proper amount of sodium metaaluminate, sodium hydroxide, silica gel and water as raw materials and hexamethylenetetramine as a template agent, wherein the molar ratio of Si to Al in the mixed solution I is controlled to be 25:1, magnetically stirring the mixed solution I at room temperature to obtain colloid, transferring the obtained colloid into a high-pressure reaction kettle to fully react at 120-170 ℃, filtering and separating the obtained product, and roasting at 500-600 ℃ for 3-7 h to obtain white MCM-22 powder with the silica-alumina ratio of 25.
Wherein the molecular sieve MCM-41 is prepared by the following steps:
taking a proper amount of tetraethoxysilane, sodium hydroxide and water as raw materials, taking hexadecyl trimethyl ammonium bromide as a template agent to prepare a mixed solution II, fully stirring the mixed solution II at room temperature, fully crystallizing at 70-90 ℃, filtering and separating the obtained product, and roasting for 3-7 hours at 500-600 ℃ to obtain the white MCM-41 powder.
Wherein the mass ratio of MCM-22 to MCM-41 in the step (a) is (1-2): (1-2).
Wherein, the titanium source in the step (a) is one or more of titanium tetrachloride, tetrabutyl titanate and titanyl sulfate.
Preferably, the mass of the molecular sieves MCM-22 and MCM-41 is TiO generated by hydrolysis of a titanium source 2 5 to 10 times of the mass.
Preferably, naAlO is contained in the mixed solution I 2 、NaOH、SiO 2 、H 2 The molar ratio of O to HMI is: 0.04:0.15:1:44.4:0.35.
preferably, the molar ratio of ethyl orthosilicate, sodium hydroxide, water and hexadecyl trimethyl ammonium bromide in the mixed solution II is 1:0.5:35:0.3.
in addition, the invention also relates to a spherical flower-shaped composite catalyst material and a method for preparing cyclohexanone oxime by catalytically oxidizing cyclohexylamine in a molecular oxygen liquid-phase oxidation system by taking the spherical flower-shaped composite catalyst material as a catalyst, and particularly relates to a method for preparing cyclohexanone oxime by directly carrying out an oxidation reaction on cyclohexylamine and molecular oxygen under a solvent-free condition by taking a gas containing molecular oxygen as an oxidant.
Preferably, the reaction temperature of the oxidation reaction is 70-120 ℃, the reaction pressure is normal pressure-2 MPa, and the mass ratio of the cyclohexylamine to the catalyst is 100: (1-3); more preferably, the molecular oxygen-containing gas is oxygen or oxygen and N 2 Or a mixture of Ar.
The process for preparing the catalyst is simple, the prepared product is formed by assembling spheroidal particles with the particle size of about 4um and columnar particles with the particle size of 0.05-0.1 um, the spheroidal particles are micron-sized particles with a spherical flower shape, the spheroidal particles consist of a large number of two-dimensional crystal plates, the catalyst has good structural stability, a large number of active sites are formed in the spheroidal particles, the catalyst is not easy to inactivate in the catalytic reaction process, and the catalyst is convenient to be repeatedly used after being separated. The invention takes the prepared product as a catalyst, takes molecular oxygen as a green oxidant, and carries out liquid-phase oxidation reaction on the cyclohexylamine under mild conditions to synthesize the cyclohexanone oxime, and the synthesis process has high cyclohexylamine conversion rate and high cyclohexanone oxime selectivity, thereby providing a new path for synthesizing the cyclohexanone oxime by a molecular oxygen liquid-phase oxidation system.
Description of the drawings:
FIGS. 1 and 2 are SEM and detailed enlarged views of the catalyst prepared in example 1, respectively;
FIG. 3 is a TEM image of the catalyst prepared in example 1;
fig. 4 is a graph of the result of a large-angle XRD analysis of the catalyst prepared in example 1.
Detailed Description
In order to facilitate the understanding of those skilled in the art, the present invention will be further described with reference to the following examples, which are not intended to limit the present invention. It should be noted that the following examples are performed in a laboratory, and it should be understood by those skilled in the art that the amounts of the components given in the examples are merely representative of the proportioning relationship between the components, and are not specifically limited.
In general, the following examples are based on the same process: firstly, adding a proper amount of molecular sieve MCM-22 and MCM-41 into water, and uniformly mixing to obtain a mixture I; simultaneously, taking one or more of ethanol, n-propanol and butanol as an organic solvent, adding a proper amount of titanium source into the organic solvent, and uniformly stirring to obtain a solution II; heating the mixture I to 50-120 ℃, slowly adding the solution II into the mixture I under continuous stirring, adding ammonia water to adjust the pH value to 8-11, and continuously preserving the temperature for 1-4 hours to obtain a mixture III; and then transferring the mixture III to a stainless steel crystallization kettle to react for 24-60 h at 120-180 ℃, separating the precipitate obtained by the reaction, and roasting for 2-8 h at 350-650 ℃ to obtain the composite catalyst product. And finally, taking the prepared composite catalyst material as a catalyst, taking a gas containing molecular oxygen as an oxidant, and directly carrying out oxidation reaction on the cyclohexylamine and the molecular oxygen under the solvent-free condition to prepare the cyclohexanone oxime. The different embodiments mainly lie in the type of organic solvent, the type of titanium source, the dosage of the titanium source and molecular sieve MCM-22, MCM-41, the dosage of catalyst and the oxidation reaction condition for preparing cyclohexanone oxime. Also in the following examples, the mass ratio of MCM-22 to MCM-41 was controlled to be (1-2): (1-2) the titanium source used is one or more selected from titanium tetrachloride, tetrabutyl titanate and titanyl sulfate, and the molecular sieves MCM-22 and MCM-41 are combinedThe quality is also strictly controlled in the TiO produced by the hydrolysis of the titanium source 2 Within 5-10 times of the mass.
It should be noted in advance that mesoporous molecular sieves MCM-22 and MCM-41 used in the following examples are self-made, and titanium sources, organic solvents, deionized water and ammonia water are all outsourced products. Before describing the specific experimental steps of each embodiment, it is necessary to describe the synthesis process of the mesoporous molecular sieve MCM-22 and the mesoporous molecular sieve MCM-41.
1. Synthesis of mesoporous molecular sieve MCM-22
Sodium metaaluminate, sodium hydroxide, silica gel and deionized water are used as raw materials, hexamethylenetetramine (HMI) is used as a template agent to prepare a mixed solution I, and specifically, in the mixed solution I, the molar ratio of each component is NaAlO 2 ∶NaOH∶SiO 2 ∶H 2 HMI =0.04:0.15:1:44.4:0.35 (the key point is that the molar ratio of Si to Al in the mixed solution I is 25.
The specific operation steps are as follows: first 1.5g NaOH (ca. 0.0375 mol) was added to about 200mL (ca. 11.1 mol) deionized water, stirred until the solution was clear, then 0.82g (ca. 0.01 mol) NaAlO was added 2 Stirring is continued until clear, 12.25g (about 0.0875 mol) of Hexamethylenetetramine (HMI) are added, magnetic stirring is carried out at room temperature for 1h, and finally 15g (SiO) is added 2 About 0.25 mol) silica gel, continuously magnetically stirring for 1h at room temperature, transferring the obtained colloid into a high-pressure reaction kettle to react for 72 h at 150 ℃ (the reaction can be carried out at 120-170 ℃, the reaction time is properly prolonged at lower reaction temperature), then filtering, washing, drying, and roasting for 5 h at 550 ℃ to obtain white powder MCM-22 with Si/Al of 25.
2. Synthesis of mesoporous molecular sieve MCM-41
Takes Tetraethoxysilane (TEOS), sodium hydroxide and deionized water as raw materials, cetyl Trimethyl Ammonium Bromide (CTAB) as a template agent, and the raw materials are mixed according to the proportion of TEOS, naOH and H 2 O: CTAB =1:0.5:35:0.3 mol ratio to prepare a mixed solution II, and the mixed solution II is fully stirred and then is crystallizedAnd roasting the product obtained by the reaction at high temperature to obtain the mesoporous molecular sieve MCM-41.
The specific operation steps are as follows: firstly, 10.93 g (about 0.03 mol) of hexadecyl trimethyl ammonium bromide and 2g (about 0.05 mol) of sodium hydroxide are dissolved in 63 g (about 3.5 mol) of deionized water, then 20.8 g (about 0.1 mol) of ethyl orthosilicate are added, the mixture is stirred vigorously for 48 h at room temperature, then crystallized for 24h at 80 ℃ (the reaction can be carried out at 70-90 ℃, the reaction time is properly prolonged at lower reaction temperature), and then filtered, washed and dried, and then roasted for 5 h at 550 ℃, thus obtaining white powder MCM-41.
Example 1
1. Preparation of catalyst precursor
0.6 g of molecular sieve MCM-22 and 0.6 g of molecular sieve MCM-41 (the mass ratio of the MCM-22 to the MCM-41 is 1).
0.68 g (about 0.002 mol) of tetrabutyl titanate (TiO produced by hydrolysis) was added to 30 g of ethanol at room temperature 2 About 0.16 g) was added to the reaction solution, and the mixture was stirred to homogeneity to obtain solution II.
Heating the mixture I to 80 ℃, slowly adding the solution II into the mixture I under continuous stirring, adding ammonia water to adjust the pH value to 10 (8-11, wherein the change of the pH value mainly influences the reaction rate and the yield within the pH value range), and continuously preserving the temperature for 2 hours to obtain a mixture III.
And transferring the mixture III to a stainless steel crystallization kettle to react for 48 hours at the temperature of 150 ℃ to obtain a catalyst precursor.
2. Preparation of catalyst Material
And filtering out a precursor, washing the precursor with deionized water, drying, and roasting at 550 ℃ for 4 hours to obtain the target catalyst material.
Fig. 1 and 2 are an SEM and a detailed enlarged view of the catalyst product, respectively, and it can be seen from the figure that the catalyst product is formed by assembling approximately 4um of spheroidal particles and 0.05 to 0.1um of cylindrical particles. Fig. 3 is a TEM image of the catalyst product, from which it can be seen that the spheroidal particles of the catalyst are composed mainly of some nearly parallel two-dimensional crystal plates, and from which an ordered hexagonal array can be seen. Fig. 4 shows the result of high-angle XRD detection of the catalyst product, in which distinct diffraction peaks appear at about 7.1 °, 8.1 °, 10.0 °, 14.3 °, 22.7 ° and 26.1 °, indicating that the MCM-22 molecular sieve exists in the product and the crystallinity thereof is good, and a broad diffraction peak exists at about 22 °, indicating that the MCM-41 molecular sieve exists in the product, which is consistent with the result of fig. 1, and the product has a low Ti content and no distinct diffraction peak is seen. The structural analysis of the catalyst product shows that the product is spherical particles assembled by two-dimensional crystal plates, and the spherical particles and cylindrical particles are assembled to form micron-sized particles with spherical flower-shaped appearance, so that a large number of active sites are formed in the product, and the multi-stage assembled spherical flower-shaped structure has good stability, is not easy to inactivate in the catalytic reaction process, and is convenient to be reused after separation.
3. Preparation of cyclohexanone oxime by liquid phase oxidation of cyclohexylamine molecular oxygen
Weighing 10 g of cyclohexylamine and 0.3 g of composite catalyst material, placing the materials in a 150mL pressure-resistant kettle type reactor, introducing molecular oxygen until the pressure reaches 1.0 MPa when the temperature reaches 100 ℃, keeping the pressure unchanged in the reaction process, standing, cooling and filtering after the reaction is finished.
4. Determination of the conversion of Cyclohexanamine and the selectivity of Cyclohexanone oxime
The filter cake was washed with a fixed amount of ethanol and the composition of the collected filtrate was quantitatively determined by gas chromatography internal standard method. The conversion of the cyclohexylamine was found to be 82.7% and the cyclohexanone oxime selectivity was found to be 96.9%.
5. Catalyst stability test
And (3) separating and recovering the catalyst, repeatedly applying the catalyst to the molecular oxygen liquid-phase oxidation system in the step (4) for multiple times, performing cyclic test for 20 times under the same condition, wherein the last test result shows that the catalytic activity (the reduction value of the conversion rate of the cyclohexylamine and the selectivity of the cyclohexanone oxime is lower than 0.5%) is not obviously changed after the cyclic test for 20 times, which indicates that the catalyst has high stability.
Example 2
This example differs from example 1 mainly in that the titanium source is titanium tetrachloride (TiO produced by hydrolysis of the titanium source) 2 About 0.16g) The other conditions were the same as in example 1. Finally, the conversion rate of the cyclohexylamine is 78.5 percent, and the selectivity of the cyclohexanone oxime is 93.3 percent.
Example 3
This example differs from example 1 primarily in that the titanium source is titanyl sulfate (TiO produced by hydrolysis of the titanium source) 2 About 0.16 g), and the other conditions were the same as in example 1. Finally, the conversion rate of the cyclohexylamine is 75.2 percent, and the selectivity of the cyclohexanone oxime is 88.7 percent.
Example 4
This example differs from example 1 mainly in that the titanium source is a mixture of tetrabutyl titanate and titanium tetrachloride (the mixture titanium source produces TiO by hydrolysis 2 About 0.16g, and the mass ratio of tetrabutyl titanate to titanium tetrachloride is 8: 2) The other conditions were the same as in example 1. Finally, the conversion rate of the cyclohexylamine was 83.1% and the selectivity of the cyclohexanone oxime was 95.5%.
Example 5
This example differs from example 1 mainly in that the titanium source is a mixture of tetrabutyl titanate and titanyl sulfate (TiO produced by hydrolysis of the mixture titanium source) 2 About 0.16g, and the mass ratio of tetrabutyl titanate to titanyl sulfate is 8: 2) Otherwise, the conditions were the same as in example 1. Finally, the conversion rate of the cyclohexylamine was 84.7% and the selectivity of the cyclohexanone oxime was 97.3%.
Example 6
The difference between this example and example 1 is mainly that the organic solvent is n-propanol, the other conditions are the same as example 1, and finally the conversion rate of the cyclohexylamine is 78.4% and the selectivity of the cyclohexanone oxime is 92.7%.
Example 7
The difference between this example and example 1 is mainly that the organic solvent is butanol, the other conditions are the same as example 1, and finally the conversion rate of the cyclohexylamine is 77.5% and the selectivity of the cyclohexanone oxime is 91.5%.
Example 8
The present example is different from example 1 mainly in that the organic solvent is a mixture of ethanol and n-propanol (ethanol content is 70% in the organic solvent, and n-propanol is 30%), other conditions are the same as example 1, and finally the conversion rate of the cyclohexylamine is 79.3% and the selectivity of the cyclohexanone oxime is 93.2%.
Example 9
The present example is different from example 1 mainly in that the organic solvent is a mixture of ethanol and butanol (ethanol content is 70% in the organic solvent, butanol is 30%), the other conditions are the same as example 1, and finally the conversion rate of the cyclohexylamine is 79.0% and the selectivity of the cyclohexanone oxime is 91.9%.
Example 10
The present example is different from example 1 mainly in that the organic solvent is a mixture of n-propanol and butanol (n-propanol content is 70% and butanol is 30% in the organic solvent), the other conditions are the same as those of example 1, and finally the conversion rate of the cyclohexylamine is 78.1% and the selectivity of the cyclohexanone oxime is 92.0%.
Example 11
This example differs from example 1 mainly in that the mass of the MCM-22 molecular sieve was 0.4 g, that of the MCM-41 molecular sieve was 0.8g, and that the other conditions were the same as example 1. The conversion of the obtained cyclohexylamine was found to be 80.1% and the cyclohexanone oxime selectivity was found to be 95.2%.
Example 12
This example differs from example 1 mainly in that the mass of the MCM-22 molecular sieve is 0.8g, the mass of the MCM-41 molecular sieve is 0.4 g, and the other conditions are the same as example 1. The conversion of the obtained cyclohexylamine was found to be 72.2% and the cyclohexanone oxime selectivity was found to be 93.4%.
Example 13
This example differs from example 1 mainly in that tetrabutyl titanate is used in an amount of about 1.02 g (about 0.003mol, tiO produced by hydrolysis of a titanium source 2 About 0.24 g), other conditions were the same as in example 1. The conversion of cyclohexylamine was found to be 76.4% and the cyclohexanone oxime selectivity was found to be 90.3%.
Example 14
This example differs from example 1 mainly in that tetrabutyl titanate is used in an amount of about 0.51 g (about 0.0015mol, tiO produced by hydrolysis of a titanium source 2 About 012 g), the other conditions were the same as in example 1. The conversion of cyclohexylamine was found to be 79.2% and the cyclohexanone oxime selectivity was found to be 92.5%.
Example 15
The difference between this example and example 1 is mainly that the crystallization temperature of mixture III transferred to a stainless steel crystallization kettle during the preparation of the catalyst precursor is 120 ℃, the reaction time is 60h, and the other conditions are the same as those in example 1. It was found that the conversion of cyclohexylamine was 72.8% and the cyclohexanone oxime selectivity was 92.8%.
Example 16
The difference between this example and example 1 is mainly that the crystallization temperature of mixture III transferred to a stainless steel crystallization kettle is 180 ℃ and the reaction time is 24h when preparing the catalyst precursor, and the other conditions are the same as example 1. It was found that the conversion of cyclohexylamine was 62.1% and the cyclohexanone oxime selectivity was 86.4%.
Example 17
This example differs from example 1 mainly in that in the preparation of the catalyst precursor, mixture I is heated to 50 ℃, and the other conditions are the same as in example 1. It was found that the conversion of cyclohexylamine was 80.4% and the cyclohexanone oxime selectivity was 93.7%.
Example 18
This example differs from example 6 mainly in that the mixture I was heated to 100 ℃ during the preparation of the catalyst precursor, and the other conditions were the same as in example 6. It was found that the conversion of cyclohexylamine was 80.2% and the cyclohexanone oxime selectivity was 94.0%.
Example 19
This example differs from example 7 mainly in that in the preparation of the catalyst precursor, mixture I was heated to 120 ℃ and the other conditions were the same as in example 7. It was found that the conversion of cyclohexylamine was 79.9% and the cyclohexanone oxime selectivity was 93.4%.
Example 20
The difference between this example and example 1 is mainly that the calcination temperature of the catalyst precursor is 350 ℃, the holding time is 8h, and the other conditions are the same as example 1. Finally, the conversion of cyclohexylamine was found to be 73.1% and the cyclohexanone oxime selectivity was found to be 93.9%.
Example 21
The difference between this example and example 1 is mainly that the calcination temperature of the catalyst precursor is 650 ℃, the holding time is 2h, and the other conditions are the same as example 1. Finally, the conversion of cyclohexylamine was found to be 76.7% and the cyclohexanone oxime selectivity was found to be 92.2%.
Example 22
The present example is different from example 1 mainly in that the amount of the catalyst used is 0.1g, and under the same oxidation reaction temperature, reaction pressure and reaction duration conditions as those of example 1 (about 4h for reaction completion of example 1), the conversion rate of the cyclohexylamine is 57.1% and the selectivity of the cyclohexanone oxime is 93.8%. The reason why the result obtained in this example is significantly different from that obtained in example 1 may be that the conversion rate of cyclohexylamine and the selectivity of cyclohexanone oxime may be similar to those of example 1 after the reaction time is properly prolonged because the amount of the catalyst used is relatively small.
Example 23
This example is different from example 1 mainly in that the oxidation reaction pressure was maintained at 0.5 MPa all the time, and the other conditions were the same as example 1. Finally, the conversion of cyclohexylamine was measured to be 67.5% and the cyclohexanone oxime selectivity was measured to be 94.3%.
Example 24
This example is different from example 1 mainly in that the oxidation reaction pressure was maintained at 2 MPa all the time, and the other conditions were the same as example 1. Finally, the conversion of cyclohexylamine was found to be 83.3% and the cyclohexanone oxime selectivity was found to be 92.7%.
Example 25
The present example is different from example 1 mainly in that the oxidation reaction pressure is maintained at normal pressure all the time, and the other conditions are the same as example 1. Finally, the conversion of cyclohexylamine was measured to be 32.9% and the cyclohexanone oxime selectivity was measured to be 74.8%.
Example 26
The difference between this example and example 1 is mainly that the oxidation reaction time is 2h, and the other conditions are the same as example 1. Finally, the conversion of cyclohexylamine was measured to be 48.9% and the selectivity of cyclohexanone oxime was measured to be 81.4%.
Example 27
This example differs from example 1 mainly in that the oxidation reaction temperature was 70 ℃ and the other conditions were the same as in example 1. The conversion of cyclohexylamine was measured to be 64.1% and the cyclohexanone oxime selectivity was measured to be 92.3%.
Example 28
This example differs from example 1 mainly in that the oxidation reaction temperature is 120 ℃ and the other conditions are the same as in example 1. It was found that the conversion of cyclohexylamine was 84.4% and the cyclohexanone oxime selectivity was 89.7%.
In the above embodiment, the composite catalyst material assembled by the spheroidal particles with the particle size of about 4um and the columnar particles with the particle size of 0.05-0.1 um is prepared by a short process flow, and the catalyst is micron-sized particles with a spherical flower-shaped morphology, wherein the spheroidal particles are composed of a large number of two-dimensional crystal plates. Tests show that the catalyst has good structural stability, forms a large number of active sites therein, is not easy to inactivate in the catalytic reaction process, and can be repeatedly used after being separated for many times. Under the action of the catalyst, molecular oxygen is used as a green oxidant, the cyclohexanone oxime can be synthesized by performing liquid-phase oxidation reaction on the cyclohexylamine under mild conditions, and the synthesis process has high cyclohexylamine conversion rate and high cyclohexanone oxime selectivity and has industrial application prospect.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Finally, it should be emphasized that some of the descriptions of the present invention have been simplified to facilitate the understanding of the improvements of the present invention over the prior art by those of ordinary skill in the art, and that other elements have been omitted from this document for the sake of clarity, and those skilled in the art will recognize that these omitted elements may also constitute the content of the present invention.

Claims (10)

1. The preparation method of the spherical composite catalyst material is characterized by comprising the following steps:
(a) Adding a proper amount of molecular sieve MCM-22 and MCM-41 into water, and uniformly mixing to obtain a mixture I;
(b) One or more of ethanol, n-propanol and butanol are used as an organic solvent, a proper amount of titanium source is added into the organic solvent, and the solution II is obtained after uniform stirring;
(c) Heating the mixture I to 50-120 ℃, slowly adding the solution II into the mixture I under continuous stirring, adding ammonia water to adjust the pH value to 8-11, and continuously preserving the temperature for 1-4 hours to obtain a mixture III;
(d) And transferring the mixture III to a stainless steel crystallization kettle to react for 24-60 h at 120-180 ℃, separating the precipitate obtained by the reaction, and roasting for 2-8 h at 350-650 ℃ to obtain the target product.
2. The method of claim 1, wherein the molecular sieve MCM-22 is prepared by:
preparing a mixed solution I by taking a proper amount of sodium metaaluminate, sodium hydroxide, silica gel and water as raw materials and hexamethylenetetramine as a template agent, wherein the molar ratio of Si to Al in the mixed solution I is controlled to be 25:1, magnetically stirring the mixed solution I at room temperature to obtain colloid, transferring the obtained colloid into a high-pressure reaction kettle to fully react at 120-170 ℃, filtering and separating the obtained product, and roasting at 500-600 ℃ for 3-7 h to obtain white MCM-22 powder with the silica-alumina ratio of 25.
3. The method of claim 1 or 2, wherein the molecular sieve MCM-41 is prepared by:
taking a proper amount of tetraethoxysilane, sodium hydroxide and water as raw materials, taking hexadecyl trimethyl ammonium bromide as a template agent to prepare a mixed solution II, fully stirring the mixed solution II at room temperature, fully crystallizing at 70-90 ℃, filtering and separating the obtained product, and roasting at 500-600 ℃ for 3-7 hours to obtain white MCM-41 powder.
4. The method of claim 1, wherein: in the step (a), the mass ratio of MCM-22 to MCM-41 is (1-2): (1-2).
5. The method of claim 1, wherein: in the step (a), the titanium source is one or more of titanium tetrachloride, tetrabutyl titanate and titanyl sulfate.
6. The method of claim 4, wherein: the mass of the molecular sieves MCM-22 and MCM-41 is TiO generated by hydrolysis of a titanium source 2 5 to 10 times of the mass.
7. The method of claim 2, wherein: naAlO in the mixed solution I 2 、NaOH、SiO 2 、H 2 The molar ratio of O to HMI is: 0.04:0.15:1:44.4:0.35.
8. the method of claim 3, wherein: the molar ratio of ethyl orthosilicate, sodium hydroxide, water and hexadecyl trimethyl ammonium bromide in the mixed solution II is 1:0.5:35:0.3.
9. the spherical flower-shaped composite catalyst material is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. The preparation method of cyclohexanone oxime is characterized by comprising the following steps: taking the spherical composite catalyst material of claim 9 as a catalyst, taking a gas containing molecular oxygen as an oxidant, and directly performing an oxidation reaction on cyclohexylamine and molecular oxygen under a solvent-free condition to prepare cyclohexanone oxime;
preferably, the reaction temperature of the oxidation reaction is 70-120 ℃, the reaction pressure is normal pressure-2 MPa, and the mass ratio of the cyclohexylamine to the catalyst is 100: (1-3); more preferably, the molecular oxygen-containing gas is oxygen or oxygen and N 2 Or a mixture of Ar.
CN202211077463.9A 2022-09-05 2022-09-05 Spherical flower-shaped composite catalyst material, preparation method thereof and preparation method of cyclohexanone oxime Pending CN115254183A (en)

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