CN116813570B - Method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene - Google Patents
Method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexeneInfo
- Publication number
- CN116813570B CN116813570B CN202310784829.4A CN202310784829A CN116813570B CN 116813570 B CN116813570 B CN 116813570B CN 202310784829 A CN202310784829 A CN 202310784829A CN 116813570 B CN116813570 B CN 116813570B
- Authority
- CN
- China
- Prior art keywords
- cyclohexene
- titanium dioxide
- tio
- catalyst
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D301/06—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 liquid phase
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种改性二氧化钛光催化环己烯合成环氧环己烷的方法，包括如下步骤：以环己烯为原料，在助氧剂的存在下，加入有机溶剂，之后加入改性二氧化钛催化剂，反应时用光照射并通氧气，加热搅拌反应得到环氧环己烷。与现有技术相比，本发明以光为能量，氧气为氧化剂，氧气来源广泛、清洁能源，降低了反应成本，具有绿色、氧化性强、反应条件温和等特点；此外，本发明具有氧化剂绿色环保，催化剂廉价易制备、易于同产物分离，助氧化剂用量少，反应条件温和、操作简单等优点，是一种绿色制备环氧环己烷的方法。
This invention relates to a method for synthesizing cyclohexane oxide from cyclohexene using photocatalysis with modified titanium dioxide, comprising the following steps: using cyclohexene as a raw material, adding an organic solvent in the presence of an oxygen-promoting agent, followed by the addition of a modified titanium dioxide catalyst; irradiating the reaction with light and passing oxygen during the reaction; and heating and stirring the reaction to obtain cyclohexane oxide. Compared with existing technologies, this invention uses light as energy and oxygen as an oxidant. Oxygen is widely available and a clean energy source, reducing reaction costs. It is characterized by being green, having strong oxidizing power, and mild reaction conditions. Furthermore, this invention has the advantages of using a green and environmentally friendly oxidant, using an inexpensive and easily prepared catalyst that is easy to separate from the product, requiring a small amount of oxygen-promoting agent, and employing mild reaction conditions and simple operation. It is a green method for preparing cyclohexane oxide.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene.
Background
The epoxycyclohexane is a colorless or light yellow liquid with fragrance, is insoluble in water, can be compatible with volatile substances such as ethanol, acetone, ether and the like, and is an important organic synthesis intermediate in industry. Because of the existence of very active epoxy groups in the molecular structure, the epoxy groups are very easy to react with amine, phenol, alcohol, carboxylic acid, water and the like in an open loop under acidic or alkaline condition, a series of compounds with high added value can be generated, and the epoxy groups can be used for preparing related products such as medicines, pesticides, curing agents, diluents, flame retardants, plasticizers, adhesives, surfactants and the like. The organic solvent is also an organic solvent with strong dissolving capacity, and can be used for diluting the epoxy resin. Therefore, the method has very wide application value.
In the prior art, the epoxycyclohexane is mainly obtained by recycling light oil fractionated in the process of preparing cyclohexanone and cyclohexanol by oxidizing cyclohexane, and the yield is limited by the yield of upstream products, thereby restricting the production and development of downstream products of the epoxycyclohexane.
In the common chemical synthesis method, the cyclohexene epoxidation is used for preparing the cyclohexene oxide, and in a specific process route, different catalysts such as metalloporphyrin, metal Schiff base, metal-EDTA, metal pyridine heterocycle, metal phthalocyanine, heteropolyacid and metal salt can be selected, and different oxidants are selected, besides common oxygen and air, TBHP, naOCl, H 2O2、PhIO、NaIO4 and the like are also generally used. However, the choice of cyclohexane oxidation is relatively complex, with two possible oxidation sites, which may occur either on the double bond or on the allylic position, resulting in low yields of epoxycyclohexane and demanding catalytic conditions. Therefore, a preparation method with high yield and mild conditions is urgently needed.
With decades of development, the use of photocatalysis in organic synthesis is becoming more and more mature. Mojarrad et al report that under the drive of photocatalysis, using a complex of para-or ortho-substituted meta-tetraarylporphyrin and Lewis acid as a photocatalyst for oxidizing olefin, the conversion rate of cyclohexene is preferably 93%, the conversion rate of cyclooctene is preferably 89％.(Mojarrad AG,et al.European Journal of Inorganic Chemistry,2017,21,2854–2862.)Hosseini-Sarvari M, and the like, styrene is selectively oxidized by Pd/ZnO nanoparticles under visible light to form styrene oxide, the conversion rate of styrene is preferably 90%, and the yield of styrene oxide is preferably 80%. (Hosseini-Sarvari M, et al chemistry select,2020,5 (28): 8853-8857.) Huang et al prepared a photocatalyst (CuNPs/TiN) with copper nanoplatelets (CuNPs) supported on titanium nitride (TiN), which was not only stable in air, but also was capable of catalyzing various olefins under light, styrene under air, conversion was 100%, and selectivity of ethylene oxide was 89%. (Huang Y, et al ACS,2017,7,4975-4985.)
The photocatalytic oxidation is a catalytic effect under the action of an external light source, takes a semiconductor as a catalyst, takes air, oxygen and the like as oxidants, takes light as energy, and has the characteristics of green, strong oxidizing property, mild reaction conditions and the like. Common photocatalysts include metal oxides, metal sulfides, bi-based photocatalysts, ag-based photocatalysts, g-C 3N4, metal organic framework materials and the like, but most photocatalysts have larger energy gaps, have narrow photoresponse range and are only active under ultraviolet light, so that the photocatalysts have low photocatalytic efficiency under visible light irradiation and are not high in application in real life.
Disclosure of Invention
The invention aims to overcome at least one of the defects in the prior art and provide a method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene, which has the advantages of high catalytic efficiency, high yield, high selectivity, high stability and low cost.
The inventor finds that cyclohexene uses aldehydes as an auxiliary oxidant under the catalysis of metal phthalocyanine derivatives/doped titanium dioxide, and the cyclohexene is catalyzed to oxidize molecular oxygen under the irradiation of visible light to prepare cyclohexene oxide, after optimizing the reaction conditions, the conversion rate of cyclohexene is more than 90%, and the yield of cyclohexene oxide in the product is more than 80%, so that the reaction selectivity is high and the operation is simple and convenient.
The aim of the invention can be achieved by the following technical scheme:
a method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis of cyclohexene comprises the following steps:
Cyclohexene is taken as a raw material, an organic solvent is added in the presence of an oxygen promoter, then a modified titanium dioxide catalyst is added, and the cyclohexene oxide is obtained by irradiation of light and oxygen introduction, heating and stirring reaction during the reaction.
Further, the oxygen-assisting agent comprises isobutyraldehyde or benzaldehyde.
Further, the organic solvent comprises any one of 1, 2-dichloroethane, ethyl acetate or acetonitrile. Wherein, the 1, 2-dichloroethane is aprotic nonpolar solvent, the ethyl acetate is aprotic weak polar solvent, and the acetonitrile is aprotic strong polar solvent.
Further, the modified titanium dioxide catalyst is a metal phthalocyanine derivative/doped titanium dioxide catalyst.
Further, the metal phthalocyanine derivative is sulfonated cobalt phthalocyanine, and the doped titanium dioxide is iron-titanium dioxide. Wherein, the metal phthalocyanine derivative is a dye (photosensitizer), and the dye sensitization is widely applied in the method for preparing the photocatalyst, and can expand the catalytic area from ultraviolet light range to visible light range. The photosensitizer which has strong light absorption performance in the visible light region and is matched with the energy level structure of the photocatalyst is loaded on the surface of the photocatalyst through physical adsorption or chemical bond combination, so that the application range is increased. Besides using metal phthalocyanine derivatives as a carrier and using doped titanium dioxide as a carrier, experiments show that the doped titanium dioxide has higher selectivity to cyclohexene oxide than pure titanium dioxide, and the use of isobutyraldehyde also greatly improves the conversion rate of cyclohexene and the selectivity of cyclohexene oxide.
Further, the preparation method of the metal phthalocyanine derivative/doped titanium dioxide catalyst comprises the following steps:
dissolving n-butyl titanate and glacial acetic acid in absolute ethyl alcohol, dropwise adding water, continuously stirring to form stable titanium dioxide sol, dissolving ferric trichloride hexahydrate in absolute ethyl alcohol, slowly dropwise adding the ferric trichloride into the prepared titanium dioxide sol, continuously stirring to obtain iron ion doped composite semiconductor sol, standing, calcining to obtain iron doped titanium dioxide powder, and marking as Fe-TiO 2;
dispersing Fe-TiO 2 in methanol solution to obtain Fe-TiO 2 suspension, adding a silane coupling agent into the methanol solution, adding ammonia water to obtain a reaction solution, adding Fe-TiO 2 suspension into the reaction solution while stirring to obtain Fe-TiO 2-NH2, centrifuging and drying, adding CoPcS and Fe-TiO 2-NH2 into water, stirring, centrifuging and drying to obtain CoPcS/Fe-TiO 2.
Further, the silane coupling agent is 3-aminopropyl triethoxysilane (APTES).
Further, the wavelength of the light is 400-800 nm. The reason why the catalyst used in the present invention is introduced into the metal phthalocyanine is to introduce the wavelength of photocatalysis into the visible light range, since Fe-TiO 2 alone can be excited at about 400nm at maximum, the application range is narrow, and the metal phthalocyanine can be excited in the visible light range, the visible light range is 400-800nm, so the wavelength range of light is selected to be 400-800nm, preferably 400-760mm.
Further, the reaction time is 12-27 h, and the reaction temperature is 10-50 ℃.
Further, the mass ratio of cyclohexene to the modified titanium dioxide catalyst is 1 (0.015-0.05), the mass ratio of cyclohexene to the auxiliary oxidant is 1 (0.5-3), the mass ratio of cyclohexene to the organic solvent is 1 (4-30), and the ratio of cyclohexene content to the flow of introduced oxygen is 1mol (800-3500 mL/min).
Compared with the prior art, the invention has obvious technical progress and has the following advantages:
(1) The invention uses light as energy and oxygen as oxidant, and has the characteristics of wide oxygen source, clean energy source, reduced reaction cost, green color, strong oxidability, mild reaction condition and the like.
(2) The modified titanium dioxide catalyst selected by the invention is metal phthalocyanine derivative/doped titanium dioxide, the carrier of the catalyst is doped titanium dioxide, and CoPcS is loaded on the surface of Fe-TiO 2 by an amino silanization method.
(3) The invention takes the metal phthalocyanine derivative/doped titanium dioxide as a catalyst, takes oxygen as an oxidant and takes aldehydes as an auxiliary oxidant, and is used for preparing the cyclohexene oxide by catalyzing cyclohexene.
(4) The method for preparing the metal phthalocyanine derivative/doped titanium dioxide is novel, simple in operation and good in loading effect, the prepared catalyst has high conversion rate of cyclohexene, high selectivity of cyclohexene oxide, and easy separation and recycling of the catalyst, and the catalytic effect is still very high after multiple uses, so that the use cost of the catalyst is greatly reduced, and the catalyst has good industrial application prospect.
(5) The method has the advantages of environment-friendly oxidant, low-cost and easy preparation of the catalyst, easy separation of the catalyst from the product, less consumption of the auxiliary oxidant, mild reaction conditions, simple operation and the like, and is a green method for preparing the cyclohexene oxide.
Drawings
FIG. 1 is a FT-IR chart of CoPcS/Fe-TiO 2 and Fe-TiO 2 in example 1;
FIG. 2 is a UV-VIS diagram of CoPcS/Fe-TiO 2 and Fe-TiO 2 in example 1;
FIG. 3 is a scanning electron microscope image of Fe-TiO 2 in example 1;
FIG. 4 is a scanning electron microscope image of CoPcS/Fe-TiO 2 in example 1.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
Example 1
1. Preparation method of CoPcS/Fe-TiO 2 catalyst
17G of n-butyl titanate and 5g of glacial acetic acid are weighed and dissolved in 25g of absolute ethyl alcohol, 1g of water is added dropwise, and stirring is continued for 1h to form stable titanium dioxide sol. Then 0.2g of ferric trichloride hexahydrate is weighed and dissolved in 10g of absolute ethyl alcohol, and is slowly dripped into the prepared titanium dioxide sol, and stirring is continued for 1h to obtain the iron ion doped compound semiconductor sol. Standing for 1d, and then placing the mixture into a muffle furnace at 500 ℃ for heat preservation for 3h to obtain the iron-doped titanium dioxide powder.
A Fe-TiO 2 suspension was prepared by adding 0.2g of Fe-TiO 2 nanoparticles to 15g of methanol solution. Adding 2g of APTES into 15g of methanol solution, adding 2g of ammonia water to prepare a reaction solution, dropwise adding Fe-TiO 2 suspension into the reaction solution under intense stirring, stirring for 24 hours to form Fe-TiO 2-NH2, centrifugally drying, adding distilled water to form Fe-TiO 2-NH2 aqueous solution, adding 0.02g of CoPcS to Fe-TiO 2-NH2 aqueous solution, stirring for 2 hours in the dark, and finally centrifugally drying in vacuum at 80 ℃ to obtain the CoPcS/Fe-TiO 2 catalyst.
In this example, the structures of Fe-TiO 2 and CoPcS/Fe-TiO 2 were characterized using FT-IR. As can be seen from FIG. 1, the absorption peaks of about 459, 1626 and 3430cm -1 exist in both Fe-TiO 2 and CoPcS/Fe-TiO 2, the absorption peak of 459cm -1 corresponds to the stretching vibration of Ti-O-Fe, and the absorption peak of 1626 and 3430cm -1 corresponds to the bending vibration and stretching vibration of-OH group, which indicates that the sample contains moisture and may not be dried completely during the test. In the infrared spectrogram of CoPcS/Fe-TiO 2, absorption peaks of 730, 756, 782, 1230, 1320, 1376 and 2923cm -1 are also found, the absorption peaks of 730, 756 and 782cm -1 are the absorption peaks of the phthalocyanine ring, the absorption peaks of 1230 and 1320cm -1 correspond to C-N, C-C bonds on the phthalocyanine ring, the absorption peak of 1376cm -1 is the characteristic absorption peak of the telescopic vibration of the sulfonic acid group O=S=O, the absorption peak at 2923cm -1 corresponds to the telescopic vibration of C-H bonds, the structure of CoPcS is confirmed, and the fact that CoPcS is loaded on the Fe-TiO 2 is explained.
The structures of CoPcS and CoPcS/Fe-TiO 2 were also characterized in this example using UV-visible absorption spectroscopy. It is known from literature (Mugadza T, nyokong T.electrochromic acta.2009,54 (26): 6347-6353) that metal phthalocyanines and their complexes have absorption peaks in the ultraviolet region of 300-400nm and in the visible region of 600-800 nm. FIG. 2 is an ultraviolet-visible absorption spectrum performed after CoPcS and CoPcS/Fe-TiO 2 are dissolved in DMSO. CoPcS has a maximum absorption wavelength around 354nm and 673nm, and CoPcS/Fe-TiO 2 also has a maximum absorption wavelength around 355nm and 672nm, indicating that CoPcS has been successfully loaded on the surface of Fe-TiO 2.
This example also uses SEM to characterize the structure of Fe-TiO 2 and CoPcS/Fe-TiO 2. FIG. 3 is a scanning electron microscope image of Fe-TiO 2 at 10000 times magnification, and FIG. 4 is a scanning electron microscope image of CoPcS/Fe-TiO 2 at 10000 times magnification. From fig. 3, it can be observed that there are some particles on the surface of TiO 2 and the adhesion is firm, indicating that iron ions have successfully entered the inside of TiO 2. From fig. 4, it can be observed that the surface of Fe-TiO 2 has larger particles and is firmly attached, indicating that the sulfonated cobalt phthalocyanine has been successfully loaded onto the surface of Fe-TiO 2.
2. Synthesis of cyclohexene oxide
0.03G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.6g of isobutyraldehyde and 8g of acetonitrile are sequentially added into the two reaction tubes, the two reaction tubes are irradiated by visible light with the wavelength of 620nm, then 20mL/min of oxygen is introduced under the normal pressure condition, the two reaction tubes are stirred for 18 hours at the constant temperature of 30 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 80.11%, and the epoxycyclohexane yield is 59.92%.
The ratio of cyclohexene, isobutyraldehyde and acetonitrile is calculated according to the mass ratio, namely cyclohexene, isobutyraldehyde and acetonitrile are 1:2:10, the addition amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene, the catalyst is 1:0.0375, and the oxygen flow is calculated according to the oxygen flow introduced per 1mol of cyclohexene being 2050 mL/min.
Example 2
The preparation of CoPcS/Fe-TiO 2 catalyst in this example corresponds to example 1.
0.03G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.6g of isobutyraldehyde and 12g of 1, 2-dichloroethane are sequentially added into the two reaction tubes, irradiation is carried out by using 670nm wavelength visible light, then 20mL/min of oxygen is introduced under normal pressure, stirring is carried out for 18h at a constant temperature of 30 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 65.63%, and the cyclohexene oxide yield is 51.57%.
The ratio of cyclohexene, isobutyraldehyde and 1, 2-dichloroethane is calculated according to the mass ratio, namely cyclohexene: isobutyraldehyde: 1, 2-dichloroethane is 1:2:15, the addition amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene: catalyst is 1:0.0375, and the oxygen flow is calculated according to the flow rate of oxygen introduced per 1mol of cyclohexene being 2050 mL/min.
Example 3
The preparation of CoPcS/Fe-TiO 2 catalyst in this example corresponds to example 1.
0.03G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.6g of isobutyraldehyde and 8g of acetonitrile are sequentially added into the two reaction tubes, the two reaction tubes are irradiated by visible light with 670nm wavelength, then 20mL/min of oxygen is introduced under normal pressure, the two reaction tubes are stirred for 18 hours at a constant temperature of 30 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 82.31%, and the epoxycyclohexane yield is 61.46%.
The ratio of cyclohexene, isobutyraldehyde and acetonitrile is calculated according to the mass ratio, namely cyclohexene, isobutyraldehyde and acetonitrile are 1:2:10, the addition amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene, the catalyst is 1:0.0375, and the oxygen flow is calculated according to the oxygen flow introduced per 1mol of cyclohexene being 2050 mL/min.
Example 4
The preparation of CoPcS/Fe-TiO 2 catalyst in this example corresponds to example 1.
0.025G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.6g of isobutyraldehyde and 8g of acetonitrile are sequentially added into the two reaction tubes, the two reaction tubes are irradiated by visible light with 670nm wavelength, then 20mL/min of oxygen is introduced under normal pressure, the two reaction tubes are stirred for 21 hours at a constant temperature of 30 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 93.33%, and the yield of the cyclohexene oxide is 73.42%.
The ratio of cyclohexene, isobutyraldehyde and acetonitrile is calculated according to the mass ratio, namely cyclohexene, isobutyraldehyde and acetonitrile are 1:2:10, the addition amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene, the catalyst is 1:0.03125, and the oxygen flow is calculated according to the oxygen flow introduced per 1mol of cyclohexene being 2050 mL/min.
Example 5
The preparation of CoPcS/Fe-TiO 2 catalyst in this example corresponds to example 1.
0.025G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.6g of isobutyraldehyde and 8g of acetonitrile are sequentially added into the two reaction tubes, the two reaction tubes are irradiated by visible light with 670nm wavelength, then 20mL/min of oxygen is introduced under normal pressure, the two reaction tubes are stirred for 21 hours at the constant temperature of 25 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 88.56%, and the yield of the cyclohexene oxide is 77.01%.
The ratio of cyclohexene, isobutyraldehyde and acetonitrile is calculated according to the mass ratio, namely cyclohexene, isobutyraldehyde and acetonitrile are 1:2:10, the addition amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene, the catalyst is 1:0.03125, and the oxygen flow is calculated according to the oxygen flow introduced per 1mol of cyclohexene being 2050 mL/min.
Example 6
The preparation of CoPcS/Fe-TiO 2 catalyst in this example corresponds to example 1.
0.025G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.2g of isobutyraldehyde and 8g of acetonitrile are sequentially added into the two reaction tubes, the two reaction tubes are irradiated by visible light with 670nm wavelength, then 20mL/min of oxygen is introduced under normal pressure, the two reaction tubes are stirred for 21 hours at the constant temperature of 25 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 94.17%, and the epoxycyclohexane yield is 82.32%.
The ratio of cyclohexene, isobutyraldehyde and acetonitrile is calculated according to the mass ratio, namely cyclohexene, isobutyraldehyde and acetonitrile are 1:1.5:10, the adding amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene, the catalyst is 1:0.03125, and the oxygen flow is calculated according to the flow rate of oxygen introduced into each 1mol of cyclohexene being 2050 mL/min.
Example 7
The preparation of CoPcS/Fe-TiO 2 catalyst in this example corresponds to example 1.
0.025G of catalyst (CoPcS/Fe-TiO 2), 0.8g of cyclohexene, 1.2g of isobutyraldehyde and 8g of acetonitrile are sequentially added into the two reaction tubes, the two reaction tubes are irradiated by visible light with 670nm wavelength, then 30mL/min of oxygen is introduced under normal pressure, the two reaction tubes are stirred for 21 hours at the constant temperature of 25 ℃, and finally, through GC detection analysis, the cyclohexene conversion rate is 90.22%, and the epoxycyclohexane yield is 76.09%.
The ratio of cyclohexene, isobutyraldehyde and acetonitrile is calculated according to the mass ratio, namely cyclohexene, isobutyraldehyde and acetonitrile are 1:1.5:10, the adding amount of the catalyst is calculated according to the mass ratio of the catalyst to cyclohexene, namely cyclohexene, the catalyst is 1:0.03125, and the oxygen flow is calculated according to the oxygen flow introduced into each 1mol of cyclohexene being 3075 mL/min.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. The method for synthesizing the cyclohexene oxide by the modified titanium dioxide photocatalysis is characterized by comprising the following steps of:
cyclohexene is taken as a raw material, an organic solvent is added in the presence of an oxygen promoter, then a modified titanium dioxide catalyst is added, and the cyclohexene oxide is obtained by irradiation of light and oxygen introduction, heating and stirring reaction during the reaction;
the modified titanium dioxide catalyst is a metal phthalocyanine derivative/doped titanium dioxide catalyst;
the metal phthalocyanine derivative is sulfonated cobalt phthalocyanine, and the doped titanium dioxide is iron-titanium dioxide;
The preparation method of the metal phthalocyanine derivative/doped titanium dioxide catalyst comprises the following steps:
Dissolving n-butyl titanate and glacial acetic acid in absolute ethyl alcohol, dropwise adding water, continuously stirring to form stable titanium dioxide sol, dissolving ferric trichloride hexahydrate in absolute ethyl alcohol, dropwise adding the ferric trichloride into the prepared titanium dioxide sol, continuously stirring to obtain iron ion doped composite semiconductor sol, standing, calcining to obtain iron doped titanium dioxide powder, and marking as Fe-TiO 2;
Dispersing Fe-TiO 2 in methanol solution to obtain Fe-TiO 2 suspension, adding a silane coupling agent into the methanol solution, adding ammonia water to obtain a reaction solution, adding Fe-TiO 2 suspension into the reaction solution while stirring to obtain Fe-TiO 2-NH2, centrifuging and drying, adding CoPcS and Fe-TiO 2-NH2 into water, stirring, centrifuging and drying to obtain CoPcS/Fe-TiO 2;
the silane coupling agent is 3-aminopropyl triethoxy silane.
2. The method for synthesizing cyclohexene oxide by photocatalysis of modified titanium dioxide according to claim 1, wherein the oxygen aid comprises isobutyraldehyde or benzaldehyde.
3. The method for synthesizing cyclohexene oxide by using modified titanium dioxide photocatalysis according to claim 1, wherein the organic solvent comprises any one of 1, 2-dichloroethane, ethyl acetate and acetonitrile.
4. The method for synthesizing cyclohexene oxide by using modified titanium dioxide and photocatalysis of cyclohexene according to claim 1, wherein the wavelength of light is 400-800 nm.
5. The method for synthesizing cyclohexene oxide by using modified titanium dioxide photocatalysis according to claim 1, which is characterized in that the reaction time is 12-27 h, and the reaction temperature is 10-50 ℃.
6. The method for synthesizing cyclohexene oxide by photocatalysis of modified titanium dioxide according to claim 1, which is characterized in that,
The mass ratio of cyclohexene to the modified titanium dioxide catalyst is 1 (0.015-0.05);
the mass ratio of cyclohexene to the auxiliary oxidant is 1 (0.5-3);
the mass ratio between cyclohexene and the organic solvent is 1 (4-30);
the ratio of cyclohexene content to the flow of the introduced oxygen is 1 mol (800-3500 mL/min).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310784829.4A CN116813570B (en) | 2023-06-29 | 2023-06-29 | Method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310784829.4A CN116813570B (en) | 2023-06-29 | 2023-06-29 | Method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116813570A CN116813570A (en) | 2023-09-29 |
| CN116813570B true CN116813570B (en) | 2025-11-21 |
Family
ID=88118062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310784829.4A Active CN116813570B (en) | 2023-06-29 | 2023-06-29 | Method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116813570B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2261080B1 (en) * | 2005-04-19 | 2007-12-16 | Universidad Politecnica De Valencia | PROCEDURE AND CATALYSTS FOR THE EXPOXIDATION OF OLEFINIC COMPOUNDS IN THE PRESENCE OF OXYGEN. |
| US20210170385A1 (en) * | 2019-12-09 | 2021-06-10 | Photonclean Inc. | Fabrication process for efficient visible light photocatalysts |
-
2023
- 2023-06-29 CN CN202310784829.4A patent/CN116813570B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| CoPc/Al2O3催化分子氧环氧化环己烯的研究;杨国玉;朱海林;周文峰;蒋登高;;化学研究与应用;20070225(02);全文 * |
| CoPc/Al2O3催化剂的制备、表征及其催化氧化性能;杨国玉;朱海林;周文峰;蒋登高;;分子催化;20071015(05);全文 * |
| 光催化环己烯氧化反应研究;汤胜山;中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑;20060415(第04期);B014-325 * |
| 多核金属磺化酞菁催化下的环己烯环氧化反应;孙强 等;东北师大学报自然科学版;19951231(第1期);79-82 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116813570A (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Visible-light-driven selective oxidation of alcohols using a dye-sensitized TiO2-polyoxometalate catalyst | |
| CN101531575B (en) | Method for preparing aldehyde or ketone by using photocatalysis to selectively oxidize primary alcohol or secondary alcohol | |
| Augugliaro et al. | Green oxidation of alcohols to carbonyl compounds by heterogeneous photocatalysis | |
| Eskandari et al. | A dendritic TiO 2–Co (ii) nanocomposite based on the melamine catalyzed one-pot aerobic photocatalytic synthesis of benzimidazoles | |
| CN115715986B (en) | Preparation method of catalyst for generating benzaldehyde by catalytic oxidation of toluene at low temperature and normal pressure | |
| CN104307514A (en) | Nano gold catalyst coated by titanium dioxide/silicon dioxide composite spherical shell and preparation method thereof | |
| CN109456161B (en) | A method for visible light catalyzed oxidative cleavage of carbon-carbon bonds | |
| Jafarpour et al. | Aerobic benzylic C–H oxidation catalyzed by a titania-based organic–inorganic nanohybrid | |
| CN102295524B (en) | Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane | |
| CN107670697B (en) | Catalyst for catalyzing selective oxidation of cyclohexane by visible light and preparation method thereof | |
| CN103721753B (en) | A kind of visible light-responded and optionally solid photocatalysts and preparation method thereof and application | |
| CN116813570B (en) | Method for synthesizing cyclohexene oxide by modified titanium dioxide photocatalysis cyclohexene | |
| CN101224433A (en) | Semiconductor TiO2 photocatalyst of surface modified cocatalyst, preparing method and uses thereof | |
| CN104817520B (en) | Method for preparing cyclohexene oxide by adopting micro-flow field reaction technology | |
| CN102964230B (en) | Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation | |
| CN106732781B (en) | In situ self-assembly preparation method of tetraphenylporphyrin zinc/zinc oxide composite film nanomaterials | |
| CN108579739B (en) | Method for preparing aldehyde/ketone by selectively oxidizing alcohol under mild condition | |
| CN101139332B (en) | Method for catalytic preparation of gamma-butyrolactone by using supported nano-gold catalyst | |
| CN113198469A (en) | Copper-titanium heterojunction photocatalyst and preparation method and application thereof | |
| CN101966464B (en) | Supported nano gold catalyst for cyclohexene oxidation and preparation method thereof | |
| CN109622040B (en) | A visible light catalyst for catalyzing the conversion of trichlorotoluene into ester and its preparation method and application | |
| CN116173985B (en) | Photocatalyst for preparing bio-based 2,5-furandicarboxylic acid and its preparation | |
| CN110813364B (en) | Preparation method of bimetallic nanocatalyst and use thereof for catalyzing oxidation of 1,2-propanediol to prepare pyruvic acid and hydroxyacetone | |
| CN108993589A (en) | A kind of preparation method of the poly- wolframic acid quaternary ammonium salt of high-quality tetramethyl ten | |
| CN111747845B (en) | Method for selectively oxidizing glucose by visible light catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |