CN111097398B - Catalytic composite material, preparation method thereof and catalytic oxidation method of cycloolefin - Google Patents
Catalytic composite material, preparation method thereof and catalytic oxidation method of cycloolefin Download PDFInfo
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- 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
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The present disclosure relates to a catalytic composite material, a preparation method thereof, and a catalytic oxidation method of a cycloolefin, wherein the catalytic composite material contains carbon dots and titanium oxide, and the content of the carbon dots is 2 to 40 wt%, and the content of the titanium oxide is 60 to 98 wt%, based on the total weight of the catalytic composite material. The method adopts the special catalytic composite material containing carbon points and titanium oxide as the catalyst to catalyze the oxidation reaction of the cycloolefin, can realize the selective oxidation of the cycloolefin under mild conditions, and has high conversion rate of raw materials and optimized selectivity of target products.
Description
Technical Field
The present disclosure relates to a catalytic composite material, a method of preparing the same, and a method of catalytically oxidizing a cycloolefin.
Background
Carbon-based materials include carbon nanotubes, activated carbon, graphite, graphene, fullerenes, carbon nanofibers, nanodiamonds, and the like. Scientific research on nanocarbon catalysis began in the 90's of the last century. Researches show that the surface chemical properties of the nano-carbon material (mainly carbon nano-tubes and graphene) can be flexibly regulated, and saturated and unsaturated functional groups containing heteroatoms such as oxygen, nitrogen and the like can be modified on the surface of the nano-carbon material, so that the nano-carbon material has certain acid-base properties and redox capability, and can be directly used as a catalyst material. Research and development of new catalytic materials related to fullerene (carbon nano tube) and broadening of the application of the new catalytic materials in the fields of petrochemical industry, fine chemical industry and the like have profound theoretical significance and huge potential application prospects.
Epoxidation of olefins is currently an important route for numerous chemical production and industrial applications. For example, the selective oxidation of cis-cyclooctene for the synthesis of pharmaceuticals, pesticides, and polyesters. The selective oxidation of cis-cyclooctene is often difficult, particularly under catalytic conditions, because the oxidation product of cis-cyclooctene is not a single product, with possible products including cyclooctane, 2-cyclooctenone and 1, 2-cyclooctadiene. In order to develop a catalytic system, various methods for the selective epoxidation of cis-cyclooctene have been reported. However, designing a highly selective, high yield catalyst in a process for the catalytic oxidation of cis-cyclooctene remains a significant challenge.
Disclosure of Invention
The present disclosure is directed to a catalytic composite material, a method for preparing the same, and a method for catalytic oxidation of a cycloolefin, which can achieve selective oxidation of the cycloolefin under mild conditions.
To achieve the above object, a first aspect of the present disclosure: the catalytic composite material contains carbon dots and titanium oxide, wherein the content of the carbon dots is 2-40 wt% and the content of the titanium oxide is 60-98 wt% based on the total weight of the catalytic composite material.
Optionally, the content of the carbon dots is 5 to 20 wt% and the content of the titanium oxide is 80 to 95 wt% based on the total weight of the catalytic composite material.
Optionally, the carbon dots are graphene quantum dots, carbon nanodots, or polymer dots.
Optionally, the catalytic composite has a particle size of 10 to 5000nm, preferably 10 to 1000nm.
In a second aspect of the present disclosure: there is provided a method of making a catalytic composite according to the first aspect of the disclosure, the method comprising the steps of:
(1) Mixing a first solution containing a titanium source and a first solvent with a second solution containing an acid and a second solvent under stirring to obtain a mixed solution;
(2) And (2) mixing the mixed solution obtained in the step (1) with a third solution containing carbon points, carrying out hydrothermal reaction for 0.5-48 h at 100-400 ℃, collecting a solid product, and then drying and roasting.
Optionally, in step (1), the molar ratio of the titanium source, the first solvent, the second solvent, and the acid is 1: (0.1-100): (0.1-50): (0.1 to 10);
the titanium source is tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate, titanyl sulfate or titanyl chloride, or a combination of two or three of the tetrabutyl titanate, the tetraisopropyl titanate, the tetraethyl titanate, the tetramethyl titanate, the titanyl sulfate or the titanyl chloride;
the acid is acetic acid, propionic acid, hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or a combination of two or three of them;
the first solvent is ethanol, n-propanol, isopropanol, n-butanol, tert-butanol or cyclohexanol, or a combination of two or three of the above;
the second solvent is water, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol or cyclohexanol, or a combination of two or three of them.
Optionally, the method further comprises: in the step (1), the first solution is added into the second solution at the speed of 0.1-50 mL/min;
the stirring conditions include: the stirring speed is 100-2000 r/min, preferably 200-1000 r/min, and the time is 0.1-12 h, preferably 0.5-6 h.
Optionally, in the step (2), the weight ratio of the third solution to the mixed solution is (0.01-10): 1, preferably (0.1 to 0.8): 1;
the drying conditions include: the temperature is 100-200 ℃, and the time is 1-12 h;
the roasting conditions comprise: the temperature is 250-800 ℃, and the time is 0.5-6 h.
A third aspect of the disclosure: a process for the catalytic oxidation of a cyclic olefin is provided, the process comprising: the method comprises the step of carrying out contact reaction on cycloolefins and an oxidant in the presence of a catalyst, wherein the catalyst contains the catalytic composite material disclosed by the first aspect of the disclosure.
Optionally, the reaction is carried out in a slurry bed reactor, and the amount of the catalyst is 20 to 100mg, preferably 20 to 60mg, based on 100mL of the cycloolefin.
Optionally, the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the cyclic olefin is 0.1-10 h -1 Preferably 0.2 to 5 hours -1 。
Optionally, the method further comprises: the reaction is carried out in the presence of an initiator; the initiator is tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, or a combination of two or three of the above;
preferably, the amount of the initiator is 0.1 to 0.3mL based on 100mL of the cycloolefin.
Optionally, the oxidant is an oxygen-containing gas, preferably air or oxygen;
the molar ratio of the cycloolefin to the oxygen in the oxygen-containing gas is 1: (1-5).
Optionally, the cycloolefin is one of C3-C8 cyclomonoolefin and C6-C8 cyclodiolefin, and is preferably cyclooctene or cyclohexene.
Optionally, the reaction conditions are: the temperature is 50-200 ℃, preferably 60-180 ℃; the time is 1 to 72 hours, preferably 2 to 24 hours; the pressure is 0 to 20MPa, preferably 0 to 10MPa.
Through the technical scheme, the method adopts the special catalytic composite material containing carbon dots and titanium oxide as the catalyst to catalyze the oxidation reaction of the cycloolefin, can realize the selective oxidation of the cycloolefin under mild conditions, and has high raw material conversion rate and optimized target product selectivity.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure: the catalytic composite material contains carbon dots and titanium oxide, wherein the content of the carbon dots is 2-40 wt% and the content of the titanium oxide is 60-98 wt% based on the total weight of the catalytic composite material.
According to the present disclosure, the catalytic composite material can have excellent catalytic performance for selective oxidation of cyclic olefins, such as cis-cyclooctene, under milder conditions. In order to better achieve the object of the present disclosure, it is preferable that the content of the carbon dots is 5 to 20% by weight and the content of the titanium oxide is 80 to 95% by weight, based on the total weight of the catalytic composite.
According to the present disclosure, the Carbon Dots (CDs) refer to carbon particles having fluorescent properties with a size of less than 20nm. The chemical structure of the carbon dots can be sp2 and sp3 hybridized carbon structures, single-layer or multi-layer graphite structures, and polymer aggregate particles. The carbon dots mainly comprise graphene quantum dots, carbon nano-dots and polymer dots. The graphene quantum dots refer to a carbon core structure with a single layer or less than 5 layers of graphene and chemical groups bonded at edges. The size of the graphene quantum dots has a typical anisotropy, the transverse dimension is larger than the longitudinal height, and the graphene quantum dots have a typical carbon lattice structure. Graphene quantum dots were the first type of material used by physicists to study the photoelectric bandgap of graphene, and generally required electron beam etching of large sheets of graphene. The carbon nanodots are generally spherical structures, and may be classified into lattice-distinct carbon nanodots and lattice-free carbon nanodots. Due to the diversity of the carbon nano-dot structure, the carbon nano-dot luminescent centers prepared in different modes and the luminescent mechanism have great difference. Specifically, it can be classified into carbon quantum dots with distinct lattices and carbon nanodots with/without lattices. The carbon quantum dots with obvious crystal lattices have obvious quantum size dependence, and the optimal fluorescence emission peak is red-shifted along with the size change from small to large. The lattice-free carbon nano-dots have no quantum size effect, the luminescence center of the lattice-free carbon nano-dots is not completely controlled by the carbon core, and the surface groups have non-negligible influence on luminescence. The polymer dots are typically cross-linked flexible aggregates formed from non-conjugated polymers by dehydration or partial carbonization, with no carbon lattice structure present. Polymer dots are a class of materials from which carbon dots extend. The polymer dots comprise fluorescent polymer dots formed by moderately crosslinking or carbonizing non-conjugated macromolecules and fluorescent polymer dots formed by assembling carbon cores and polymers.
Methods for preparing the carbon dots are well known to those skilled in the art in light of this disclosure. The raw material source of the carbon dots may generally include both inorganic carbon sources and organic carbon sources. The specific preparation method can comprise methods such as an arc discharge method, a laser ablation/passivation method, an electrochemical method, a pyrolysis method, a field-assisted method and the like. The carbon dots can be prepared in one step by a high temperature pyrolysis method, usually using citrate as a carbon source or using citric acid and glutathione together as a carbon source.
According to the present disclosure, the carbon dots are preferably graphene quantum dots, carbon nanodots or polymer dots, and the carbon dots are commercially available or can be prepared by methods known in the art. The particle size of the carbon dots is generally 3 to 20nm.
According to the present disclosure, the titanium oxide (TiO) 2 ) The particle size of (a) may be 10 to 5000nm.
According to the present disclosure, the catalytic composite may have a particle size of 10 to 5000nm, preferably 10 to 1000nm. In the present disclosure, the particle size refers to the maximum three-dimensional length of the particle, i.e., the maximum distance between two points on the particle.
A second aspect of the disclosure: there is provided a method of making a catalytic composite according to the first aspect of the disclosure, the method comprising the steps of:
(1) Mixing a first solution containing a titanium source and a first solvent with a second solution containing an acid and a second solvent under stirring to obtain a mixed solution;
(2) And (2) mixing the mixed solution obtained in the step (1) with a third solution containing carbon points, carrying out hydrothermal reaction for 0.5-48 h at 100-400 ℃, collecting a solid product, and then drying and roasting.
According to the present disclosure, in step (1), the molar ratio of the titanium source, the first solvent, the second solvent, and the acid may be 1: (0.1 to 100): (0.1-50): (0.1 to 10), preferably 1: (1-50): (1-25): (0.2-5). Wherein the titanium source may be a titanium-containing compound, for example, tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate, titanyl sulfate or titanyl chloride, or a combination of two or three thereof. The acid may be a common organic or inorganic acid, and may be, for example, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or a combination of two or three thereof. The first solvent and the second solvent may be water or a C2 to C6 alcohol, for example, the first solvent may be ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, or cyclohexanol, or a combination of two or three of them, the second solvent may be water, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, or cyclohexanol, or a combination of two or three of them, and the kinds of the first solvent and the second solvent may be the same or different. The pH of the second solution may be 0 to 6.
According to the present disclosure, in order to make the mixing of the first solution and the second solution more sufficient, the method may further include: in the step (1), the first solution is added into the second solution at the speed of 0.1-50 mL/min. The mixing is performed under agitation conditions, which may include: the stirring speed is 100-2000 r/min, preferably 200-1000 r/min, and the time is 0.1-12 h, preferably 0.5-6 h.
According to the disclosure, in the step (2), the third solution is used in an amount such that the content of the carbon dots in the prepared catalytic composite material is 2 to 40 wt% and the content of the titanium oxide in the prepared catalytic composite material is 60 to 98 wt%, based on the total weight of the catalytic composite material. For example, the weight ratio of the third solution to the mixed solution may be (0.01 to 10): 1, preferably (0.1 to 0.8): 1. the hydrothermal reaction may be carried out in a conventional reactor, for example in a polytetrafluoroethylene reaction vessel. The pressure of the hydrothermal reaction process is not particularly limited, and may be the autogenous pressure of the system, or may be under an additional applied pressure condition, and preferably, the hydrothermal reaction process is performed under the autogenous pressure (generally, in a closed vessel). The method of collecting the solid product after the hydrothermal reaction may be carried out by a conventional method such as filtration, centrifugation and the like. The conditions for drying and calcining the solid product may be conventional in the art, for example, the drying conditions may include: the temperature is 100-200 ℃, and the time is 1-12 h; the conditions for the firing may include: the temperature is 250-800 ℃, and the time is 0.5-6 h.
In a third aspect of the present disclosure, there is provided a process for the catalytic oxidation of a cyclic olefin, the process comprising: the method comprises the step of carrying out contact reaction on cycloolefins and an oxidant in the presence of a catalyst, wherein the catalyst contains the catalytic composite material disclosed by the first aspect of the disclosure.
The catalytic composite material containing carbon dots and titanium oxide is used as a catalyst to catalyze the oxidation reaction of the cycloolefin, so that the selective oxidation of the cycloolefin can be realized under mild conditions, and the conversion rate of raw materials and the selectivity of a target product are high.
The process of the present disclosure may be carried out in a variety of conventional catalytic reactors, for example, may be carried out in a batch tank reactor or three-neck flask, or in suitable other reactors such as fixed bed, moving bed, suspended bed, and the like.
In an alternative embodiment of the present disclosure, the reaction may be carried out in a slurry bed reactor. In this case, the amount of the catalyst may be appropriately selected depending on the amounts of the cycloolefin and the oxidizing agent, and for example, the amount of the catalyst may be 20 to 100mg, preferably 40 to 60mg, based on 100mL of the cycloolefin.
In another alternative embodiment of the present disclosure, the reaction may be carried out in a fixed bed reactor. In this case, the weight hourly space velocity of the cycloolefin may be, for example, 0.1 to 10 hours -1 Preferably 0.2 to 5 hours -1 。
According to the present disclosure, the cyclic olefin may be one selected from C3 to C8 cyclic monoolefins and C6 to C8 cyclic diolefins, and is preferably cyclooctene or cyclohexene.
The oxidizing agent is an oxidizing agent conventionally used in the art according to the present disclosure, and for example, the oxidizing agent may be an oxygen-containing gas, and further may be air or oxygen. The molar ratio of the cyclic olefin to oxygen in the oxygen-containing gas may be 1: (1-5).
According to the present disclosure, in order to promote the reaction, further improve the conversion rate of the raw material and the selectivity of the target product, the method may further include: the reaction is carried out in the presence of an initiator. The initiator may be an initiator conventionally used in the art, for example, the initiator may be t-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, or a combination of two or three thereof. The initiator can be used in a small amount, for example, 0.1 to 0.3mL based on 100mL of the cycloolefin.
According to the present disclosure, the conditions of the reaction may be: the temperature is 50-200 ℃, preferably 60-180 ℃; the time is 1 to 72 hours, preferably 2 to 24 hours; the pressure is 0 to 20MPa, preferably 0 to 10MPa. In order to make the reaction more sufficient, it is preferable that the contact reaction is carried out under stirring.
The present disclosure is described in detail below with reference to examples, but the scope of the present disclosure is not limited thereby.
Preparation examples 1 to 5 are illustrative of the catalytic composite of the present disclosure and the preparation method thereof.
In the following preparation examples, solutions containing carbon dots having a particle size of 9nm and a concentration of 0.01 wt% were purchased from Suzhou university. Titanium oxide was purchased from Yingchun corporation and had a particle size of 300nm. The particle size of the composite material was determined by TEM, and 20 particles were randomly selected from the TEM photograph, and the average size thereof was calculated. The method for measuring the content of the carbon points and the titanium oxide in the catalytic composite material is a roasting method, the catalytic composite material is roasted for 2 hours at the temperature of 400 ℃, the percentage of the residual weight to the weight before roasting is the content of the titanium oxide, and the percentage of the lost weight to the weight before roasting is the content of the carbon points.
Preparation of example 1
Tetrabutyl titanate and the first solvent absolute ethyl alcohol are vigorously stirred for 10min (the stirring speed is 800 revolutions per minute) to obtain a first solution. The glacial acetic acid, the second solvent water and the absolute ethyl alcohol are stirred vigorously (the stirring speed is 800 r/min), and hydrochloric acid is added to ensure that the pH value is less than 3, so as to obtain a second solution. Adding the first solution into the second solution at a speed of 3mL/min under the condition of vigorous stirring at a stirring speed of 800 revolutions/min in a room-temperature water bath to form a light yellow mixed solution, wherein the molar ratio of tetrabutyl titanate to the first solvent to the second solvent to the acid is 1:10:5:1. and (3) mixing the third solution containing the carbon dots with the mixed solution according to the weight ratio of 0.25:1, mixing, stirring for 0.5h, transferring into a hydrothermal kettle, carrying out hydrothermal reaction for 6h at 80 ℃, collecting a solid product, drying at 105 ℃, roasting at 500 ℃ to obtain CDs/TiO 2 Catalytic composite A1, average particle size about 150nm, CDs content 8% by weight, tiO 2 The content was 92% by weight.
Preparation of example 2
A composite material was prepared according to the method of preparation example 1, except that, during the synthesis, the weight ratio of the third solution containing carbon dots to the mixed solution of the first solution and the second solution was 0.5:1, obtaining CDs/TiO 2 Composite particles A2 having an average particle size of about 65nm and a content of TiO 15% by weight 2 The content was 85% by weight.
Preparation of example 3
A composite material was prepared according to the method of preparation example 1, except that, during the synthesis, tetrabutyl titanate, the first solvent, the second solvent and the acidIn a molar ratio of 1:60:30:10, obtaining CDs/TiO 2 Composite particles A3 having an average particle size of about 1100nm and a CDs content of 9 wt%, tiO 2 The content was 91% by weight.
Preparation of example 4
A composite material was prepared according to the method of preparation example 1, except that, during the synthesis, the weight ratio of the third solution containing carbon dots to the mixed solution of the first solution and the second solution was 1:1, obtaining CDs/TiO 2 Composite particles A4 having an average particle size of about 30nm, a CDs content of 33 wt.%, tiO 2 The content was 67% by weight.
Preparation of example 5
A composite material was prepared according to the method of preparation example 1, except that, during the synthesis, the weight ratio of the third solution containing carbon dots to the mixed solution of the first solution and the second solution was 0.05:1, obtaining CDs/TiO 2 Composite particles A5 having a mean particle size of about 420nm, a CDs content of 4% by weight, tiO 2 The content was 96% by weight.
Examples 1 to 9 are provided to illustrate the method of catalytically oxidizing a cycloolefin using the catalytic composite of the present disclosure.
In the following examples and comparative examples, the oxidation products were analyzed by gas chromatography (GC: agilent, 7890A) and gas chromatography-mass spectrometer (GC-MS: thermo Fisher Trace ISQ). Conditions of gas chromatography: nitrogen carrier gas, temperature programmed at 140K: 60 ℃,1 minute, 15 ℃/minute, 180 ℃,15 minutes; split ratio, 10:1; the injection port temperature is 300 ℃; detector temperature, 300 ℃. On the basis, the conversion rate of raw materials and the selectivity of target products are calculated by respectively adopting the following formulas:
percent cyclooctene conversion = (molar amount of cyclooctene added before reaction-molar amount of cyclooctene remaining after reaction)/molar amount of cyclooctene added before reaction × 100%;
selectivity% for cyclooctane epoxide (= molar amount of cyclooctane epoxide formed after reaction)/molar amount of cyclooctene added before reaction × 100%.
Example 1
40mg of the composite particles A1 as a catalyst and 100mL of cis-cyclooctene were charged into a 250mL autoclave, then 0.1mL of t-butyl hydroperoxide (TBHP) as an initiator was added dropwise to the above system, the system was sealed, oxygen (molar ratio of oxygen to cyclooctene: 5: 1) was introduced, the mixture was stirred at 120 ℃ for 2 hours, the temperature was lowered, the pressure was relieved, sampling was performed, the catalyst was separated by centrifugation and filtration, and the results of analysis of the oxidation product are shown in Table 1.
Examples 2 to 5
Cyclooctene was catalytically oxidized by the method of example 1, except that A1 was replaced with the same amounts of the composite particles A2 to A5, respectively. The results of the oxidation product analysis are shown in Table 1.
Example 6
60mg of the composite particles A1 as a catalyst and 100mL of cis-cyclooctene were charged into a 250mL autoclave, then 0.2mL of cumyl hydroperoxide as an initiator was added dropwise to the above system, the system was sealed, oxygen (molar ratio of oxygen to cyclooctene: 5: 1) was introduced, the mixture was stirred at 130 ℃ under 2.0MPa for 4 hours, and after cooling, pressure-releasing sampling, the catalyst was separated by centrifugation and filtration, and the results of analysis of the oxidized product are shown in Table 1.
Example 7
100mg of the composite particles A1 as a catalyst and 100mL of cis-cyclooctene were charged into a 250mL autoclave, and then 0.1mL of t-butyl hydroperoxide (TBHP) as an initiator was added dropwise to the above system, sealed, and the mixture was stirred at 160 ℃ and 3.0MPa for 1 hour with introduction of oxygen (molar ratio of oxygen to cyclooctene: 5.
Example 8
40mg of the composite particles A1 as a catalyst were loaded in a fixed bed reactor, cis-cyclooctene and tert-butyl hydroperoxide were fed into the reactor, oxygen (molar ratio of oxygen to cyclohexane 5: 1) was fed, the amount of tert-butyl hydroperoxide was 0.1mL based on 100mL of cyclooctene, and the weight hourly space velocity of cyclooctene was 5h -1 The results of the analysis of the oxidation products after 8 hours of reaction at 80 ℃ and 2MPa are shown in Table 1.
Example 9
Cyclooctene was catalytically oxidized according to the procedure of example 1, except that t-butyl hydroperoxide (TBHP) was not added as an initiator. The results of the oxidation product analysis are shown in Table 1.
Comparative example 1
Cyclooctene was catalytically oxidized according to the procedure of example 1, except that the same amount of carbon dots (CDs, particle size of 9 nm) was used in place of the composite particles A1. The results of the oxidation product analysis are shown in Table 1.
Comparative example 2
Cyclooctene was catalytically oxidized according to the method of example 1, except that the same amount of titanium oxide (TiO) was used 2 Particle size 300 nm) instead of the composite particles A1. The results of the oxidation product analysis are shown in Table 1.
Comparative example 3
Cyclooctene was catalytically oxidized by the method of example 1, except that the composite particles A1 were not used, i.e., no catalyst was added. The results of the oxidation products are shown in Table 1.
TABLE 1
| Sources of catalyst | Cyclooctene conversion% | Selectivity to epoxycyclooctane% |
| Example 1 | 16 | 62 |
| Example 2 | 15 | 61 |
| Example 3 | 14 | 60 |
| Example 4 | 13 | 57 |
| Example 5 | 11 | 55 |
| Example 6 | 15 | 60 |
| Example 7 | 14 | 57 |
| Example 8 | 17 | 64 |
| Example 9 | 12 | 61 |
| Comparative example 1 | 7 | 29 |
| Comparative example 2 | 2 | 13 |
| Comparative example 3 | 4 | 8 |
As can be seen from Table 1, the catalytic composite material containing carbon dots and titanium oxide is adopted as the catalyst, so that the selective oxidation of cyclooctene can be realized under mild conditions, and the conversion rate of raw materials and the selectivity of target products are higher.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations will not be further described in the present disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure as long as it does not depart from the gist of the present disclosure.
Claims (21)
1. A process for the catalytic oxidation of a cyclic olefin, the process comprising: the method comprises the following steps of carrying out contact reaction on a cycloolefin and an oxidant in the presence of a catalyst, wherein the cycloolefin is one of C3-C8 cyclomonoolefin and C6-C8 cyclodiolefin, the catalyst contains a catalytic composite material, the catalytic composite material contains carbon dots and titanium oxide, the content of the carbon dots is 2-40 wt% and the content of the titanium oxide is 60-98 wt% based on the total weight of the catalytic composite material;
the catalytic composite material is prepared by adopting the following method:
(1) Mixing a first solution containing a titanium source and a first solvent with a second solution containing an acid and a second solvent under stirring to obtain a mixed solution;
(2) And (2) mixing the mixed solution obtained in the step (1) with a third solution containing carbon points, carrying out hydrothermal reaction at 100-400 ℃ for 0.5-48h, collecting a solid product, and then drying and roasting.
2. The method according to claim 1, wherein the carbon dots are contained in an amount of 5 to 20 wt% and the titanium oxide is contained in an amount of 80 to 95 wt%, based on the total weight of the catalytic composite.
3. The method of claim 1 or 2, wherein the carbon dots are graphene quantum dots, carbon nanodots, or polymer dots.
4. The process of claim 1 or 2, wherein the catalytic composite has a particle size of 10 to 5000nm.
5. The method of claim 4, wherein the catalytic composite has a particle size of 10 to 1000nm.
6. The method of claim 1, wherein in step (1), the molar ratio of the titanium source, first solvent, second solvent, and acid is 1: (0.1 to 100): (0.1 to 50): (0.1 to 10);
the titanium source is tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate, titanyl sulfate or titanyl chloride, or a combination of two or three of the above;
the acid is acetic acid, propionic acid, hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or a combination of two or three of the above;
the first solvent is ethanol, n-propanol, isopropanol, n-butanol, tert-butanol or cyclohexanol, or a combination of two or three of the above;
the second solvent is water, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol or cyclohexanol, or a combination of two or three of them.
7. The method of claim 1, wherein the method further comprises: in the step (1), adding the first solution into the second solution at a speed of 0.1 to 50mL/min;
the stirring conditions include: the stirring speed is 100 to 2000 rpm, and the time is 0.1 to 12h.
8. The method of claim 7, wherein the agitation conditions comprise: the stirring speed is 200 to 1000 revolutions per minute, and the stirring time is 0.5 to 6 hours.
9. The method according to claim 1, wherein in the step (2), the weight ratio of the third solution to the mixed solution is (0.01 to 10): 1;
the drying conditions include: the temperature is 100 to 200 ℃, and the time is 1 to 12h;
the roasting conditions comprise: the temperature is 250 to 800 ℃, and the time is 0.5 to 6h.
10. The method according to claim 9, wherein in the step (2), the weight ratio of the third solution to the mixed solution is (0.1 to 0.8): 1.
11. the process as claimed in claim 1, wherein the reaction is carried out in a slurry bed reactor, and the catalyst is used in an amount of 20 to 100mg, based on 100mL of the cycloolefin.
12. The method according to claim 11, wherein the catalyst is used in an amount of 20 to 60mg based on 100mL of the cycloolefin.
13. The process as claimed in claim 1, wherein the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the cycloolefin is from 0.1 to 10h -1 。
14. The method of claim 13, wherein theThe weight hourly space velocity of the cycloolefin is 0.2 to 5h -1 。
15. The method of claim 1, wherein the method further comprises: the reaction is carried out in the presence of an initiator; the initiator is tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, or a combination of two or three of the above.
16. The method according to claim 15, wherein the amount of the initiator is 0.1 to 0.3mL based on 100mL of the cycloolefin.
17. The method of claim 1, wherein the oxidant is an oxygen-containing gas;
the molar ratio of the cycloolefin to oxygen in the oxygen-containing gas is 1: (1 to 5).
18. The method of claim 17, wherein the oxidant is air or oxygen.
19. The process of claim 1, wherein the cycloalkene is cyclooctene or cyclohexene.
20. The process according to claim 1, wherein the reaction conditions are: the temperature is 50 to 200 ℃, the time is 1 to 72h, and the pressure is 2 to 20MPa.
21. The method of claim 20, wherein the reaction conditions are: the temperature is 60 to 180 ℃, the time is 2 to 24h, and the pressure is 2 to 10MPa.
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