CN113828292B - CQDs-TiO for preparing cyclohexanone oxime 2 Method for preparing catalyst and method for preparing cyclohexanone oxime - Google Patents

CQDs-TiO for preparing cyclohexanone oxime 2 Method for preparing catalyst and method for preparing cyclohexanone oxime Download PDF

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CN113828292B
CN113828292B CN202111211907.9A CN202111211907A CN113828292B CN 113828292 B CN113828292 B CN 113828292B CN 202111211907 A CN202111211907 A CN 202111211907A CN 113828292 B CN113828292 B CN 113828292B
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cqds
catalyst
cyclohexanone oxime
tio
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CN113828292A (en
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刘水林
刘宁
伍素云
唐新德
龚升高
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

CQDs-TiO for preparing cyclohexanone oxime 2 A preparation method of a catalyst and a method for preparing cyclohexanone oxime, relating to the technical field of high-efficiency catalysts. Wherein CQDs-TiO for preparing cyclohexanone oxime 2 The preparation method of the catalyst comprises the following steps: mixing ammonium salt or an ammonium salt solution with a hydrochloric acid solution to obtain a solution A; uniformly stirring the CQDs solution and a titanium source to obtain a solution B; dropwise adding the solution A into the solution B under the stirring condition, and reacting for 1-4 h; under the conditions of stirring and heating, adding ammonia water to adjust the pH value to 6-8, keeping the temperature for 4-10 hours after white precipitates appear in the solution, filtering, washing, drying and roasting to obtain CQDs-TiO 2 . CQDs-TiO as described above 2 The preparation process of the catalyst is simple, and the prepared CQDs-TiO 2 The catalyst has high stability and high activity, is not easy to inactivate in the reaction process, is easy to separate and can be repeatedly used, and when the catalyst is applied to the method for preparing the cyclohexanone oxime, the reaction energy consumption and the reaction pressure can be reduced, and the conversion rate of the cyclohexylamine and the selectivity of the cyclohexanone oxime are improved.

Description

CQDs-TiO for preparing cyclohexanone oxime 2 Method for preparing catalyst and method for preparing cyclohexanone oxime
Technical Field
The invention relates to the technical field of high-efficiency catalysts, in particular to CQDs-TiO for preparing cyclohexanone oxime 2 A method for preparing the catalyst and a method for preparing cyclohexanone oxime.
Background
Cyclohexanone oxime is a key intermediate for producing epsilon-caprolactam, which is widely applied to the production of nylon 6 engineering plastics and nylon 6 fibers. At present, the synthesis method of cyclohexanone oxime mainly comprises a cyclohexanone-hydroxylamine method, a cyclohexanone-ammoximation method, a cyclohexane photonitrosation method, a nitrocyclohexane partial hydrogenation method and a cyclohexylamine oxidation method. The method for industrially producing cyclohexanone oxime mainly comprises a cyclohexanone-hydroxylamine method and a cyclohexanone-ammoximation method, wherein the two methods both use intermediate cyclohexanone as raw material, and the cyclohexanone is mainly synthesized by adopting a cyclohexane oxidation method, and the method has the major defects, such as low single pass conversion rate (about 4%) of the cyclohexane, high alkali consumption, high energy consumption and large treatment load of waste alkali liquor. The cyclohexylamine oxidation method avoids the processes of inefficient oxidation of cyclohexane, preparation of hydroxylamine and the like, and comprises a hydrogen peroxide oxidation system, a molecular oxygen phase oxidation system and a molecular oxygen liquid phase oxidation system. Among them, US20150353478 proposes that montmorillonite and saponite are used as carriers, metal elements such as Ti, Zr, Ge and Pt are loaded as catalysts, acetonitrile is used as a solvent, and the oxidation of cyclohexylamine by molecular oxygen is realized under the condition of liquid-phase overpressure to prepare cyclohexanone oxime (molecular oxygen liquid-phase oxidation system), however, in the scheme, the conversion rate of cyclohexylamine is low, an accelerator and an organic solvent are needed to be used, and a target product and the organic solvent are needed to be separated in the later stage, which is not very beneficial to large-scale industrial production. In addition, chinese patent CN107115875A discloses a green liquid phase oxidation method using titanium phosphorus oxide or supported titanium phosphorus oxide as a catalyst, which can make the conversion rate of cyclohexylamine reach more than 70%, and the selectivity of cyclohexanone oxime reach more than 90%, if large-scale industrial application is required, the method needs further improvement in reaction energy consumption, reaction pressure, conversion rate of cyclohexylamine and selectivity of cyclohexanone oxime, however, in recent years, it is only rare that a molecular oxygen liquid phase oxidation method with better index performance is reported.
Disclosure of Invention
One of the purposes of the invention is to provide CQDs-TiO for preparing cyclohexanone oxime by oxidizing cyclohexylamine with molecular oxygen 2 The preparation method of the catalyst reduces the reaction energy consumption and the reaction pressure of preparing the cyclohexanone oxime by the molecular oxygen liquid phase oxidation method by using the catalyst prepared by the method, and improves the conversion rate of the cyclohexylamine and the selectivity of the cyclohexanone oxime.
In order to achieve the purpose, the invention adopts the following scheme:
CQDs-TiO for preparing cyclohexanone oxime 2 The preparation method of the catalyst comprises the following steps:
(1) mixing ammonium salt or an ammonium salt solution with a hydrochloric acid solution to obtain a solution A;
(2) uniformly stirring a proper amount of CQDs solution and a titanium source to obtain solution B;
(3) dropwise adding the solution A into the solution B under the stirring condition, and carrying out liquid-phase hydrolysis reaction for 1-4 h;
(4) under the conditions of stirring and heating, adding ammonia water to adjust the pH value to 6-8, keeping the temperature for 4-10 hours after the solution is changed from clear transparent liquid to turbid liquid containing white precipitates, filtering, washing, drying and roasting to obtain the carbon quantum dot loaded titanium dioxide nanocomposite CQDs-TiO 2 。
Wherein the CQDs solution in the step (2) is prepared by the following steps: dissolving a proper amount of citric acid in deionized water, transferring the solution to an autoclave, keeping the temperature of the autoclave at 140-180 ℃ for 2-6 hours, and cooling to obtain a CQDs solution.
Further, citric acid for preparing CQDs solution and CQDs-TiO preparation 2 The molar ratio of the titanium source used by the catalyst is 0.05-1.0: 1.
preferably, citric acid used to prepare CQDs solution and CQDs-TiO are prepared 2 The molar ratio of the titanium source used by the catalyst is 0.1-0.3: 1.
further, the ratio of the citric acid to the deionized water is 0.024-0.192 g of citric acid to 1mL of deionized water.
Preferably, the ratio of the citric acid to the deionized water is 0.024-0.096 g of citric acid to 1mL of deionized water.
Further, when preparing CQDs solution, the proportion of citric acid and deionized water is 0.96g of citric acid corresponding to 20mL of deionized water, the heat preservation temperature is 160 ℃, and the heat preservation time is 5 hours; in the step (1), the ratio of the ammonium salt or ammonium salt solution to the hydrochloric acid solution is 45mL of ammonium salt or ammonium salt solution corresponding to 5mL of hydrochloric acid solution, wherein the concentration of the ammonium salt or ammonium salt solution is 2 mol/L; in the step (4), the heat preservation temperature is 50 ℃, the roasting temperature is 350 ℃, and the roasting time is 3.5 hours; the prepared CQDs-TiO 2 The molar ratio of carbon to titanium in the catalyst was 0.2: 1.
Further, the titanium source in the step (2) is one or more than two of titanium tetrachloride, tetrabutyl titanate and titanyl sulfate.
Further, the heating condition in the step (4) is 50-120 ℃.
It is another object of the present invention to provide a process for producing cyclohexanone oxime,using CQDs-TiO 2 The catalyst is used for preparing cyclohexanone oxime, so that the reaction energy consumption and the reaction pressure are reduced, and the conversion rate of the cyclohexylamine and the selectivity of the cyclohexanone oxime are improved.
In order to achieve the purpose, the invention adopts the following scheme:
a process for preparing cyclohexanone oxime comprising the steps of: CQDs-TiO prepared by the above preparation method 2 The catalyst is used as a catalyst, gas containing molecular oxygen is used as an oxidant, and the oxidation reaction is carried out on the cyclohexylamine and the molecular oxygen under the solvent-free condition to obtain the cyclohexanone oxime.
Wherein the reaction temperature is 30-160 ℃, the reaction pressure is normal pressure-0.8 Mpa, and the mass percent of the catalyst is 0.5-5%.
Further, the reaction temperature is 70-90 ℃.
Further, the reaction pressure was 0.5 MPa.
Further, the mass percentage of the catalyst is 1% -3%.
Further, the molecular oxygen-containing gas is oxygen or a mixture of oxygen and an inert gas.
The above CQDs-TiO for preparing cyclohexanone oxime 2 The preparation method of the catalyst has simple preparation process, and the prepared CQDs-TiO 2 The catalyst has high stability and high activity, is not easy to inactivate in the reaction process, is easy to separate and can be repeatedly used, and when the catalyst is applied to the method for preparing the cyclohexanone oxime, the reaction energy consumption and the reaction pressure can be reduced, and the conversion rate of the cyclohexylamine and the selectivity of the cyclohexanone oxime are improved. Compared with the prior art, the invention adopts the CQDs-TiO 2 In the preparation process of the cyclohexanone oxime of the catalyst, no organic solvent is used, the cyclohexylamine can be efficiently converted into the cyclohexanone oxime, the preparation process is simple, the technological process is greatly simplified, the procedure of separating a target product from the organic solvent in the later period is reduced, the reaction condition is mild, and the catalyst is stable, easy to separate, reusable, short in preparation period and beneficial to large-scale industrial production. The green catalyst of the document CN107115875A and the titanium phosphorus oxygen or the supported titanium phosphorus oxygenCompared with the color liquid phase oxidation method, the invention adopts the CQDs-TiO for preparing the cyclohexanone oxime 2 CQDs-TiO prepared by catalyst preparation method 2 The catalyst is used as a catalyst for preparing cyclohexanone oxime, the using amount of the catalyst is less, the reaction energy consumption and the reaction pressure are lower, and the conversion rate of the cyclohexylamine and the selectivity of the cyclohexanone oxime are higher.
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 carried out in the 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.
First, synthesis of carbon quantum dots CQDs.
0.96g of citric acid is fully dissolved in 20mL of deionized water, then the solution is transferred to a stainless steel autoclave lined with polytetrafluoroethylene, the stainless steel autoclave is placed in a muffle furnace and kept at 160 ℃ for 5 hours, and after cooling, a CQDs solution with slight faint yellow color can be obtained.
Di, CQDs/TiO 2 And (3) preparing a catalyst.
Mixing 45mL of 2mol/L ammonium sulfate solution with 5mL of hydrochloric acid to obtain a solution A; uniformly stirring the synthesized CQDs solution and 8.5 g of tetrabutyl titanate to obtain a solution B; under the condition of stirring, dropwise adding the solution A into the solution B to perform liquid phase hydrolysis reaction for 2 hours; placing the mixture in a constant-temperature oil bath kettle at 50 ℃, dropwise adding ammonia water to adjust the pH value to be neutral (about 6-8), changing the original clear transparent liquid into a suspension containing white precipitates, continuously preserving the heat for 4 hours, cooling to room temperature, filtering, washing with distilled water and ethanol, continuously filtering, drying white solids, and roasting in a muffle furnace at 350 ℃ for 3.5 hours to obtain the carbon quantum dot-loaded titanium dioxide nanocomposite CQDs/TiO 2 Labeled as catalyst 1.
Catalyst 2 was prepared according to the same method as above, differing from catalyst 1 in that: the CQDs solution was synthesized using 0.48g citric acid mass.
Catalyst 3 was prepared according to the same method as above, differing from catalyst 1 in that: the CQDs solution was synthesized using 1.44g of citric acid.
Catalyst 4 was prepared according to the same method as above, differing from catalyst 1 in that: the amount of deionized water used to synthesize CQDs solution was 40 mL.
Catalyst 5 was prepared according to the same method as above, differing from catalyst 1 in that: the amount of deionized water used to synthesize CQDs solution was 10 mL.
Catalyst 6 was prepared according to the same method as above, differing from catalyst 1 in that: in step II CQDs/TiO 2 The calcination temperature used in the preparation of the catalyst was 200 ℃.
Catalyst 7 was prepared according to the same method as above, differing from catalyst 1 in that: in step II CQDs/TiO 2 The calcination temperature used in the preparation of the catalyst was 500 ℃.
And thirdly, preparing cyclohexanone oxime.
Example 1: weighing 10 g of cyclohexylamine and 0.2 g of catalyst 1, placing the cyclohexylamine and the catalyst in a 150mL pressure-resistant kettle-type reactor, introducing molecular oxygen until the pressure reaches 0.5MPa when the temperature reaches 80 ℃, keeping the pressure unchanged in the reaction process, reacting for 3.5h at 80 ℃, standing, cooling and filtering, washing a filter cake with quantitative ethanol, and quantitatively measuring the composition of the collected filtrate by adopting a gas chromatography internal standard method to obtain the cyclohexylamine with the conversion rate of 83.1% and the cyclohexanone oxime selectivity of 96.5%.
Examples 2 to 9 were prepared in the same manner as in example 1, and all used catalyst 1, the points of distinction of examples 1 to 9 and the conversion of the resulting cyclohexylamine and the selectivity of cyclohexanone oxime are shown in Table 1 below.
TABLE 1
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 1 10 0.2 80 0.5 3.5 83.1 96.5
Example 2 10 0.2 80 0.5 2 74.2 92.4
Example 3 10 0.2 80 0.5 5 85.4 91.1
Example 4 10 0.2 70 0.5 3.5 75.1 91.8
Example 5 10 0.2 90 0.5 3.5 85.2 92.6
Example 6 10 0.2 80 0.3 3.5 75.8 89.3
Example 7 10 0.2 80 0.8 3.5 84.7 90.5
Example 8 10 0.1 80 0.5 3.5 76.1 91.8
Example 9 10 0.3 80 0.5 3.5 84.9 93.7
Example 10 is prepared identically to example 1, except that: example 10 employed catalyst 2.
Examples 11 to 18 were prepared in the same manner as in example 10 and all used catalyst 2, and the points of distinction of examples 10 to 18 and the conversion of the resulting cyclohexylamine and the selectivity for cyclohexanone oxime are shown in Table 2 below.
TABLE 2
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 10 10 0.2 80 0.5 3.5 75.4 90.6
Example 11 10 0.2 80 0.5 2 66.2 85.4
Example 12 10 0.2 80 0.5 5 78.3 84.1
Example 13 10 0.2 70 0.5 3.5 60.1 84.8
Example 14 10 0.2 90 0.5 3.5 82.2 85.6
Example 15 10 0.2 80 0.3 3.5 69.8 82.3
Example 16 10 0.2 80 0.8 3.5 78.2 83.5
Example 17 10 0.1 80 0.5 3.5 60.3 85.8
Example 18 10 0.3 80 0.5 3.5 79.4 88.6
Example 19 was prepared identically to example 1, except that: example 19 employed catalyst 3.
Examples 20 to 27 were prepared in the same manner as in example 19 and all used catalyst 3, and the points of distinction of examples 19 to 27 and the conversion of the resulting cyclohexylamine and the selectivity for cyclohexanone oxime are shown in Table 3 below.
TABLE 3
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 19 10 0.2 80 0.5 3.5 76.7 88.6
Example 20 10 0.2 80 0.5 2 64.4 82.5
Example 21 10 0.2 80 0.5 5 82.6 80.7
Example 22 10 0.2 70 0.5 3.5 61.2 81.8
Example 23 10 0.2 90 0.5 3.5 83.1 85.7
Example 24 10 0.2 80 0.3 3.5 70.9 81.6
Example 25 10 0.2 80 0.8 3.5 81.5 82.5
Example 26 10 0.1 80 0.5 3.5 71.7 82.4
Example 27 10 0.3 80 0.5 3.5 81.7 84.3
Example 28 was prepared identically to example 1, except that: example 28 employed catalyst 4.
Examples 29 to 36 were prepared in the same manner as in example 28 and all used catalyst 4, and the differences between examples 28 to 36 and the conversion of cyclohexylamine and the selectivity for cyclohexanone oxime were found in Table 4 below.
TABLE 4
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 28 10 0.2 80 0.5 3.5 73.5 86.8
Example 29 10 0.2 80 0.5 2 61.8 80.2
Example 30 10 0.2 80 0.5 5 80.6 81.7
Example 31 10 0.2 70 0.5 3.5 61.3 82.4
Example 32 10 0.2 90 0.5 3.5 80.2 79.7
Example 33 10 0.2 80 0.3 3.5 67.9 79.6
Example 34 10 0.2 80 0.8 3.5 79.1 81.5
Example 35 10 0.1 80 0.5 3.5 68.2 80.1
Example 36 10 0.3 80 0.5 3.5 79.5 83.9
Example 37 was prepared identically to example 1, except that: example 37 employed catalyst 5.
Examples 38 to 45 were prepared in the same manner as in example 37 and all used catalyst 5, and the points of distinction of examples 37 to 45 and the resulting conversion of cyclohexylamine and cyclohexanone oxime selectivity are shown in Table 5 below.
TABLE 5
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 37 10 0.2 80 0.5 3.5 75.7 87.4
Example 38 10 0.2 80 0.5 2 62.3 81.2
Example 39 10 0.2 80 0.5 5 81.1 82.4
Example 40 10 0.2 70 0.5 3.5 62.4 83.6
EXAMPLE 41 10 0.2 90 0.5 3.5 81.4 84.8
Example 42 10 0.2 80 0.3 3.5 68.7 81.5
Example 43 10 0.2 80 0.8 3.5 80.5 83.7
Example 44 10 0.1 80 0.5 3.5 63.4 82.5
Example 45 10 0.3 80 0.5 3.5 81.7 83.4
Example 46 is prepared identically to example 1, except that: example 46 employed catalyst 6.
Examples 47 to 54 were prepared in the same manner as in example 46 and all used catalyst 6, and the points of distinction of examples 46 to 54 and the resulting conversion of cyclohexylamine and cyclohexanone oxime selectivity are shown in Table 6 below.
TABLE 6
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 46 10 0.2 80 0.5 3.5 78.2 89.7
Example 47 10 0.2 80 0.5 2 67.6 83.5
Example 48 10 0.2 80 0.5 5 84.7 85.1
Example 49 10 0.2 70 0.5 3.5 67.6 82.2
Example 50 10 0.2 90 0.5 3.5 85.2 84.8
Example 51 10 0.2 80 0.3 3.5 71.9 82.4
Example 52 10 0.2 80 0.8 3.5 81.7 86.2
Example 53 10 0.1 80 0.5 3.5 73.4 85.8
Example 54 10 0.3 80 0.5 3.5 84.2 84.5
Example 55 was prepared identically to example 1, except that: example 55 employed catalyst 7.
Examples 56 to 63 were prepared in the same manner as in example 55 and all used catalyst 7, and the differences between examples 55 to 63 and the conversion of cyclohexylamine and the selectivity for cyclohexanone oxime were found in Table 7 below.
TABLE 7
Cyclohexylamine g Catalyst g Reaction temperature C Reaction pressure Mpa Reaction time h Conversion of cyclohexylamine% Cyclohexanone oxime selectivity%
Example 55 10 0.2 80 0.5 3.5 80.3 91.5
Example 56 10 0.2 80 0.5 2 71.1 86.4
Example 57 10 0.2 80 0.5 5 86.5 87.7
Example 58 10 0.2 70 0.5 3.5 70.4 85.9
Example 59 10 0.2 90 0.5 3.5 85.8 87.8
Example 60 10 0.2 80 0.3 3.5 74.2 81.4
Example 61 10 0.2 80 0.8 3.5 85.5 85.7
Example 62 10 0.1 80 0.5 3.5 75.4 87.6
Example 63 10 0.3 80 0.5 3.5 83.3 89.5
Comparing the preparation effects of cyclohexanone oxime in the embodiments, it can be seen that example 1 is significantly better than other examples, wherein the conversion rate of cyclohexanone amine is more than 83%, the selectivity of cyclohexanone oxime is more than 96%, and under the same other conditions and different catalysts, the preparation effects of cyclohexanone oxime are different, so that the preparation effect of example 1 is significantly better than that of other examples, which may be affected by the catalysts, and it is determined that the molar ratio of carbon to titanium of the catalyst in example 1 is about 0.2:1, and it is presumed that the difference in the molar ratio of carbon to titanium in the catalyst causes the change in the catalytic performance of the catalyst.
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 (9)

1. A process for the preparation of cyclohexanone oxime comprising the steps of: CQDs-TiO 2 The catalyst is a catalyst, gas containing molecular oxygen is used as an oxidant, and the oxidation reaction is carried out on the cyclohexylamine and the molecular oxygen under the solvent-free condition to obtain cyclohexanone oxime;
the CQDs-TiO 2 The catalyst is prepared by the following preparation method:
(1) mixing ammonium salt or an ammonium salt solution with a hydrochloric acid solution to obtain a solution A;
(2) uniformly stirring a proper amount of CQDs solution and a titanium source to obtain solution B;
(3) dropwise adding the solution A into the solution B under the stirring condition, and carrying out liquid-phase hydrolysis reaction for 1-4 h;
(4) under the conditions of stirring and heating, adding ammonia water to adjust the pH value to 6-8, keeping the temperature for 4-10 hours after the solution is changed from clear transparent liquid to turbid liquid containing white precipitates, filtering, washing, drying and roasting to obtain the carbon quantum dot loaded titanium dioxide nanocomposite CQDs-TiO 2 。
2. The process for producing cyclohexanone oxime according to claim 1, characterized in that: the oxidation reaction temperature is 30-160 ℃, the oxidation reaction pressure is normal pressure-0.8 Mpa, and the mass percentage of the catalyst is 0.5-5%.
3. The process for producing cyclohexanone oxime according to claim 2, characterized in that: the oxidation reaction temperature is 70-90 ℃.
4. The process for producing cyclohexanone oxime according to claim 2, characterized in that: the oxidation reaction pressure is 0.5 Mpa.
5. The process for producing cyclohexanone oxime according to claim 2, characterized in that: the mass percentage of the catalyst is 1-3%.
6. The method of producing cyclohexanone oxime as claimed in claim 1, wherein the CQDs solution in the step (2) is produced by the steps of: dissolving a proper amount of citric acid in deionized water, transferring the solution to an autoclave, keeping the temperature of the autoclave at 140-180 ℃ for 2-6 hours, and cooling to obtain a CQDs solution.
7. The process for producing cyclohexanone oxime according to claim 6, characterized in that: citric acid for preparing CQDs solution and CQDs-TiO 2 The molar ratio of the titanium source used by the catalyst is 0.05-1.0: 1.
8. the process for producing cyclohexanone oxime according to claim 6, characterized in that: the ratio of the citric acid to the deionized water is 0.024-0.192 g of citric acid to 1mL of deionized water.
9. The process for producing cyclohexanone oxime according to claim 6, characterized in that: when preparing CQDs solution, the ratio of citric acid to deionized water is 0.96g, and the citric acid corresponds to 20mL of deionized water, the heat preservation temperature is 160 ℃, and the heat preservation time is 5 hours;
in the step (1), the ratio of the ammonium salt or ammonium salt solution to the hydrochloric acid solution is 45mL of ammonium salt or ammonium salt solution corresponding to 5mL of hydrochloric acid solution, wherein the concentration of the ammonium salt or ammonium salt solution is 2 mol/L;
in the step (4), the heat preservation temperature is 50 ℃, the roasting temperature is 350 ℃, and the roasting time is 3.5 hours;
the prepared CQDs-TiO 2 The molar ratio of carbon to titanium in the catalyst was 0.2: 1.
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