CN111100047B - Thioether oxidation process - Google Patents
Thioether oxidation process Download PDFInfo
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- CN111100047B CN111100047B CN201811269852.5A CN201811269852A CN111100047B CN 111100047 B CN111100047 B CN 111100047B CN 201811269852 A CN201811269852 A CN 201811269852A CN 111100047 B CN111100047 B CN 111100047B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
Abstract
The present disclosure relates to a thioether oxidation process, comprising: the thioether and the peroxide are subjected to contact reaction in the presence of a catalyst, wherein the catalyst is carbon nitride. The method not only can obtain higher thioether conversion rate and sulfoxide selectivity, but also can reduce the production cost.
Description
Technical Field
The present disclosure relates to a thioether oxidation process.
Background
As a typical representative of sulfoxide substances, dimethyl sulfoxide (DMSO) is a sulfur-containing organic compound, is a colorless transparent liquid at room temperature, and has characteristics of high polarity, high hygroscopicity, flammability, high boiling point aprotic property, and the like. Dimethyl sulfoxide is soluble in water, ethanol, acetone, diethyl ether and chloroform, is an inert solvent with strong polarity, and is widely used as a solvent and a reaction reagent. Moreover, dimethyl sulfoxide has high selective extraction capacity and can be used as an extraction solvent for separating alkane from aromatic hydrocarbon, such as: dimethyl sulfoxide can be used for extracting aromatic hydrocarbon or butadiene, and can be used as a processing solvent and a spinning solvent in acrylonitrile polymerization reaction, as a synthetic solvent and a spinning solvent for polyurethane, and as a synthetic solvent for polyamide, chlorofluoroaniline, polyimide and polysulfone. Meanwhile, in the pharmaceutical industry, dimethyl sulfoxide can be directly used as a raw material and a carrier of certain medicines, and also has the effects of diminishing inflammation, relieving pain, promoting urination, tranquilizing and the like, so that dimethyl sulfoxide is often used as an active component of an analgesic medicine to be added into the medicines. In addition, dimethyl sulfoxide can also be used as a capacitance medium, an antifreeze, brake oil, a rare metal extractant and the like.
At present, dimethyl sulfoxide is generally prepared by a dimethyl sulfide oxidation method, and the following production processes are generally adopted.
1. Methanol carbon disulfide method: methanol and carbon disulfide are taken as raw materials, and gamma-Al is taken2O3As a catalyst, dimethyl sulfide is firstly synthesized and then is oxidized by nitrogen dioxide (or nitric acid) to obtain dimethyl sulfoxide.
2. Nitrogen dioxide method: methanol and hydrogen sulfide are used as raw materials, and dimethyl sulfide is generated under the action of gamma-alumina; reacting sulfuric acid with sodium nitrite to prepare nitrogen dioxide; the generated dimethyl sulfide and nitrogen dioxide are subjected to oxidation reaction at 60-80 ℃ to generate crude dimethyl sulfoxide, and the crude dimethyl sulfoxide is also generated by directly oxidizing with oxygen; and distilling the crude dimethyl sulfoxide under reduced pressure to obtain refined dimethyl sulfoxide.
3. Dimethyl sulfate method: reacting dimethyl sulfate with sodium sulfide to prepare dimethyl sulfide; reacting sulfuric acid with sodium nitrite to generate nitrogen dioxide; and (3) carrying out oxidation reaction on the dimethyl sulfide and nitrogen dioxide to obtain crude dimethyl sulfoxide, and carrying out neutralization treatment and distillation to obtain refined dimethyl sulfoxide.
In addition, dimethyl sulfoxide can also be produced from dimethyl sulfide by anodic oxidation.
In recent years, the production of dimethyl sulfoxide from dimethyl sulfide by a peroxide oxidation method has become a hot research and development point. The peroxide oxidation method has the advantages of mild reaction conditions, simple equipment and process route, no need of alkali for neutralization of the product, and no pollution to the environment. However, in the peroxide oxidation method, the product selectivity needs to be effectively regulated, the production cost of the sulfoxide has a further reduced space, and the application range of the peroxide oxidation method is limited. Therefore, when the sulfoxide is prepared by adopting a peroxide oxidation method, how to effectively regulate and control the product selectivity and reduce the production cost of the sulfoxide is an important topic.
Disclosure of Invention
The present disclosure aims to overcome the problems of the prior art methods for preparing sulfoxides using peroxides as the oxidizing agent and to provide an alternative method for oxidizing thioethers.
In order to achieve the above object, the present disclosure provides a thioether oxidation method, comprising: the thioether and the peroxide are subjected to contact reaction in the presence of a catalyst, wherein the catalyst is carbon nitride.
Optionally, the nitrogen content of the carbon nitride is not less than 50 wt%.
Optionally, the weight of the carbon nitride with the particle size of 20-100 nm accounts for 2-30%, preferably 5-20% of the total weight of the carbon nitride.
Alternatively, the reaction is carried out without back-mixing of the materials.
Alternatively, the reaction is carried out in a slurry bed reactor with screw-propelled stirring paddles.
Optionally, the weight hourly space velocity of the dimethyl sulfide is 0.1-500 h-1。
Optionally, the molar ratio of thioether to peroxide is 1: (0.1-2), preferably 1: (0.2 to 1).
Optionally, the thioether is dimethyl sulfide, diethyl sulfide, or diethyl sulfide.
Alternatively, the peroxide is hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, cyclohexyl hydroperoxide, peroxyacetic acid, or peroxypropionic acid, or a combination of two or three thereof.
Optionally, the method further comprises: the reaction is carried out in the presence of a solvent selected from water and C1～C6Alcohol of (1), C3～C8Ketone and C2～C6One or more of (a) nitrile(s).
Optionally, the weight ratio of the solvent to the thioether is (0.1-20): 1, preferably (1-10): 1.
optionally, the conditions of the reaction include: the temperature is 0-80 ℃, and preferably 20-50 ℃; the pressure is 0-3 MPa, preferably 0.1-2.5 MPa; the time is 0.1 to 12 hours, preferably 0.2 to 5 hours.
Through the technical scheme, the carbon nitride is used as the catalyst to catalyze the thioether oxidation reaction, so that higher thioether conversion rate and sulfoxide selectivity can be obtained, and the production cost can be reduced.
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 present disclosure provides a method of oxidizing a thioether, the method comprising: the thioether and the peroxide are subjected to contact reaction in the presence of a catalyst, wherein the catalyst is carbon nitride.
According to the method, carbon nitride is used as a catalyst to catalyze the thioether oxidation reaction, so that higher thioether conversion rate and sulfoxide selectivity can be obtained, and the production cost can be reduced.
In the present disclosure, the "particle size" refers to the maximum three-dimensional length of the particle, i.e., the distance between two points on the particle having the largest distance.
According to the present disclosure, the carbon nitride may have an average particle size of 10 to 1000nm, preferably 50 to 500 nm. The inventor also unexpectedly finds that the catalyst has better performance for catalyzing thioether oxidation when the weight of carbon nitride with the particle size of 20-100 nm accounts for 2-30%, preferably 5-20% of the total weight of the carbon nitride.
The present disclosure requires a nitrogen content in the carbon nitride, for example, the nitrogen content in the carbon nitride may be not less than 50% by weight. Preferably, the catalyst is of composition C3N4The carbon nitride of (a) is,its nitrogen content was about 61 wt%.
The source of the carbon nitride is not limited in the present disclosure, and the carbon nitride can be obtained commercially or prepared by methods in the prior art.
In an alternative embodiment of the present disclosure, the carbon nitride C3N4The preparation method comprises the following steps: adding urea with different amounts into a quartz reactor, sealing, reacting at 400-800 ℃ for 1-12 h, and cooling to obtain carbon nitride C3N4. By changing the addition amount of urea, the reaction time and the temperature, the carbon nitride C with different particle sizes and different proportions of the weight of the carbon nitride with the particle size of 20-100 nm to the total weight of the carbon nitride can be obtained3N4。
According to the present disclosure, the amount of the catalyst may be appropriately selected according to the amounts of the thioether and the peroxide, for example, the weight ratio of the thioether to the catalyst may be (1-1000): 1, preferably (2-100): 1.
the process of the present disclosure can be carried out in various conventional catalytic reactors, for example, can be carried out in a batch tank reactor or a three-neck flask, or in suitable other reactors such as fixed beds, moving beds, suspended beds, and the like.
In a preferred embodiment of the present disclosure, the reaction is carried out without back-mixing of the materials. Therefore, the conversion rate of thioether and the selectivity of a target product can be further improved, and the operation cost is effectively reduced. The meaning of the material without back-mixing is well known to those skilled in the art and will not be described in detail in this disclosure.
Further, in an alternative embodiment, the reaction may be carried out in a slurry bed reactor with a screw-propelled paddle. When the spiral propelling stirring paddle rotates, the reaction materials can flow in a unidirectional mode along the axial direction of the reactor without being mixed reversely, and the flow pattern of the materials in the reactor is a similar pushing flow pattern without back mixing, so that the condition that the materials are not mixed back is realized. The propelling direction of the screw propeller is not particularly limited, and may be, for example, upward propelling, downward propellingOr in a horizontal direction. The slurry bed reactor with the screw propulsion stirring paddle can be the existing equipment and can also be built by oneself as long as the purpose can be realized. In the above embodiment, the weight hourly space velocity of the dimethyl sulfide can be varied within a wide range, and can be, for example, 0.1 to 500h-1Preferably 1 to 100 hours-1. In other embodiments of the present disclosure, the reaction may also be carried out in other reactors capable of achieving material backmixing free, such as certain microchannel reactors.
The disclosed process can oxidize various thioethers to yield the corresponding sulfoxides. The thioether can be various compounds containing an-S-bond, and is preferably a thioether with 2-18 carbon atoms, such as dimethyl thioether, methyl ethyl thioether, diethyl thioether or phenyl ethyl thioether.
The method disclosed by the invention is particularly suitable for the occasion of oxidizing thioether by taking peroxide as an oxidizing agent, so that the effective utilization rate of the peroxide can be obviously improved. The peroxide is a compound containing an-O-O-bond in the molecular structure, and can be hydrogen peroxide, organic peroxide and peracid. The organic peroxide is a substance obtained by substituting one or two hydrogen atoms in a hydrogen peroxide molecule with an organic group. The peracid refers to an organic oxyacid having an-O-O-bond in the molecular structure. Specific examples of the peroxide in the present disclosure may include, but are not limited to: hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid or propionic acid. Preferably, the oxidizing agent is hydrogen peroxide, which further reduces the separation cost.
The hydrogen peroxide may be hydrogen peroxide in various forms commonly used in the art. From the viewpoint of further improving the safety of the method according to the present disclosure, the method according to the present disclosure preferably uses hydrogen peroxide in the form of an aqueous solution. In accordance with the methods of the present disclosure, when the hydrogen peroxide is provided as an aqueous solution, the concentration of the aqueous hydrogen peroxide solution may be a concentration conventional in the art, for example: 20 to 80 wt%. Aqueous solutions of hydrogen peroxide at concentrations meeting the above requirements may be prepared by conventional methods or may be obtained commercially, for example: can be 30 percent by weight of hydrogen peroxide, 50 percent by weight of hydrogen peroxide or 70 percent by weight of hydrogen peroxide which can be obtained commercially.
The peroxide may be used in a relatively small amount to achieve the desired effect according to the present disclosure, for example, the molar ratio of thioether to peroxide may be 1: (0.1-2), preferably 1: (0.2 to 1).
According to the present disclosure, by using a solvent, the speed of the reaction can be adjusted, making the reaction more stable. Accordingly, the method may further comprise: the reaction is carried out in the presence of a solvent. The solvent may be various liquid substances capable of dissolving both the thioether and the peroxide or facilitating the mixing thereof, and dissolving the target product. For example, the solvent may be selected from water, C1～C6Alcohol of (1), C3～C8Ketone and C2～C6One or more of (a) nitrile(s). Specific examples of the solvent may include, but are not limited to: water, methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile. Preferably, the solvent is selected from water and C1～C6The alcohol of (1). More preferably, the solvent is methanol and/or water. The amount of the solvent may be appropriately selected according to the amounts of the thioether and the peroxide, for example, the weight ratio of the solvent to the thioether may be (0.1-20): 1, preferably (1-10): 1.
according to the present disclosure, the conditions of the reaction depend on the target product. In general, the conditions of the reaction may include: the temperature is 0-80 ℃, and preferably 20-50 ℃; the pressure is 0-3 MPa, preferably 0.1-2.5 MPa; the time is 0.1 to 12 hours, preferably 0.2 to 5 hours.
The method of the present disclosure may further include separating the reaction mixture obtained after the reaction to obtain the target product and unreacted reactants. The method for separating the reaction mixture may be a method conventionally selected in the art, and is not particularly limited. The separated unreacted reactant can be recycled.
The present disclosure is described in detail below with reference to examples, but the scope of the present disclosure is not limited thereby.
All other reagents were commercially available analytical grade reagents, and the pressures were measured as gauge pressures.
In the following examples and comparative examples, the contents of the respective components in the obtained reaction liquid were analyzed by gas chromatography, and on the basis of which the thioether conversion rate, the peroxide effective utilization rate, and the sulfoxide selectivity were calculated by the following formulas, respectively:
thioether conversion (X)Thioethers) (molar amount of added thioether-molar amount of unreacted thioether)/molar amount of added thioether]×100％；
Effective utilization rate (U) of peroxidePeroxides and their use in the preparation of pharmaceutical preparations) (molar amount of sulfoxide produced by reaction/(molar amount of peroxide added-molar amount of unreacted peroxide))]×100％；
Sulfoxide selectivity (S)Sulfoxide) (molar amount of sulfoxide formed by reaction/(molar amount of thioether charged-molar amount of unreacted thioether))]×100％。
Preparation examples 1 to 5 are provided to illustrate the method for preparing carbon nitride particles used in the examples.
In the preparation examples, TECNAIG (carbon nitride) of FEI was used as the average particle size of carbon nitride2Transmission electron microscope type F20(200kv) under the following test conditions: accelerating voltage of 20kV, preparing a sample by adopting a suspension method, putting the sample into a 2mL glass bottle, dispersing the sample by absolute ethyl alcohol, uniformly oscillating, taking one drop by using a dropper, dropping the drop on a sample net with the diameter of 3mm, putting the sample net into a sample injector after drying, inserting the sample into an electron microscope for observation, and randomly taking 100 carbon oxide-based material particles for carrying out particle size statistics. The carbon nitride is prepared by separating particles with the particle size of 3-20 nm by a membrane separation device (type BONA-GM-08) of Jinan Borna Biotechnology Limited company, wherein the particles with the particle size of 20-100 nm are separated, and then calculating the ratio of the weight of the particles with the particle size of 20-100 nm to the total mass of the carbon oxide based material according to the weight of the particles with the particle size of 20-100 nm and the total mass of the carbon nitride.
Preparation example 1
Placing 50g of urea in a crucible, covering and sealing the crucible, placing the crucible in a muffle furnace at 450 ℃ for roasting for 8 hours to obtain carbon nitride particles A, and detecting that the carbon nitride particles A have an average particle size of 400nm, wherein the weight of the carbon nitride with the particle size of 20-100 nm accounts for 9% of the total weight of the carbon nitride, and the nitrogen content is about 61% by weight.
Preparation example 2
Placing 40g of urea in a crucible, covering and sealing the crucible, placing the crucible in a muffle furnace at 550 ℃ for roasting for 5 hours to obtain carbon nitride particles B, and detecting that the carbon nitride particles B have an average particle size of 200nm, wherein the weight of the carbon nitride with the particle size of 20-100 nm accounts for 16% of the total weight of the carbon nitride, and the nitrogen content is about 61% by weight.
Preparation example 3
Placing 60g of urea in a crucible, covering and sealing the crucible, placing the crucible in a muffle furnace at 650 ℃ for roasting for 2 hours to obtain carbon nitride particles C, and detecting that the carbon nitride particles C have an average particle size of 600nm, wherein the weight of the carbon nitride with the particle size of 20-100 nm accounts for 2.5% of the total weight of the carbon nitride, and the nitrogen content is about 61% by weight.
Preparation example 4
20g of urea is placed in a crucible, the crucible is covered and sealed, the crucible is placed in a 400 ℃ muffle furnace for roasting for 6 hours, carbon nitride particles D are obtained, the average particle size of the carbon nitride particles D is detected to be 100nm, the weight of the carbon nitride with the particle size of 20-100 nm accounts for 23% of the total weight of the carbon nitride, and the nitrogen content is about 61% by weight.
Preparation example 5
100g of urea is placed in a crucible, the crucible is covered and sealed, the crucible is placed in a muffle furnace at the temperature of 420 ℃ for roasting for 4 hours, carbon nitride particles E are obtained, the average particle size of the carbon nitride particles E is detected to be 80nm, the weight of the carbon nitride with the particle size of 20-100 nm accounts for 5% of the total weight of the carbon nitride, and the nitrogen content is about 61% by weight.
Example 1
Dimethyl sulfide, 30 wt% hydrogen peroxide and methanol as a solvent were mixed to form a liquid mixture. Then, the bulk mixture was fed into a slurry bed reactor having a rotatable screw-up auger paddle from the feed inlet thereof to contact with carbon nitride particles A. Wherein the moles of dimethyl sulfide and hydrogen peroxideThe ratio is 1: 1, the weight ratio of dimethyl sulfide to methanol is 1: 5; the reaction temperature is 30 ℃, the pressure is 0.5MPa, and the weight hourly space velocity of the dimethyl sulfide is 2.5h-1. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 2
Dimethyl sulfide, 50 wt% hydrogen peroxide and methanol as a solvent were mixed to form a liquid mixture. Then, the bulk mixture was fed into a slurry bed reactor having a rotatable screw-up auger paddle from the feed inlet thereof to contact with carbon nitride particles B. Wherein the molar ratio of dimethyl sulfide to hydrogen peroxide is 1: 0.5, the weight ratio of dimethyl sulfide to methanol is 1: 10; the reaction temperature is 30 ℃, the pressure is 1.5MPa, and the weight hourly space velocity of the dimethyl sulfide is 10h-1. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 3
A sulfoxide was prepared by following the procedure of example 1, except that the same amount of carbon nitride particles C was used instead of carbon nitride particles a. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 4
Dimethyl sulfide, 30 wt% hydrogen peroxide and methanol as a solvent were mixed to form a liquid mixture. Then, the mixture is fed into a slurry bed reactor with a rotatable screw-up propeller stirring paddle from a feed inlet of the reactor to contact with carbon nitride particles D, and the reaction materials are not back-mixed. Wherein the molar ratio of dimethyl sulfide to hydrogen peroxide is 1: 2, the weight ratio of dimethyl sulfide to methanol is 1: 20; the reaction temperature is 20 ℃, the pressure is 1.5MPa, and the weight hourly space velocity of the dimethyl sulfide is 5h-1. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 5
Dimethyl sulfide, 30 wt% hydrogen peroxide and methanol as solventMixing to form a liquid mixture. Then, the mixture is fed into a slurry bed reactor with a rotatable screw-up propeller into contact with carbon nitride particles E from the feed inlet of the reactor without back-mixing of the reaction mass. Wherein the molar ratio of dimethyl sulfide to hydrogen peroxide is 1: 0.1, the weight ratio of dimethyl sulfide to methanol is 1: 0.2; the reaction temperature is 30 ℃, the pressure is 1.5MPa, and the weight hourly space velocity of the dimethyl sulfide is 5h-1. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 6
Thioanisole, 30 wt% t-butyl hydroperoxide and t-butanol as solvent were mixed to form a liquid mixture. Then, the mixture is fed into a slurry bed reactor with a rotatable screw-up propeller into the reactor from the feed inlet of the reactor to contact with the carbon nitride particles A without back-mixing of the reaction materials. Wherein the molar ratio of the methyl phenyl sulfide to the tert-butyl hydroperoxide is 1: 1, the weight ratio of the dimethyl benzene sulfide to the tertiary butanol is 1: 5; the reaction temperature is 40 ℃, the pressure is 0.5MPa, and the weight hourly space velocity of the dimethyl sulfide is 2.5h-1. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 7
A sulfoxide was prepared according to the procedure of example 1, except that the reaction was carried out in a slurry bed reactor without a screw-up propeller. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Example 8
A sulfoxide was prepared by the method of example 1, except that no solvent was added, and the other conditions were the same. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Comparative example 1
A sulfoxide was prepared according to the procedure of example 1, except that the reactor was not packed with carbon nitride particles. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
Comparative example 2
Sulfoxides were prepared as in example 1, except that the reactor was filled with equal amounts of urea granules. The reaction mixtures obtained after the reaction was carried out for 1 hour and 12 hours were subjected to gas chromatography, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1, under the same reaction conditions, especially under the same reactant material ratio, the method of the present disclosure can obtain higher thioether conversion rate and sulfoxide selectivity, and can significantly improve the effective utilization rate of peroxide and reduce the production cost. As can be seen from the comparison of example 1 and example 7, when the reaction is carried out under the condition of no material back mixing, the thioether conversion rate, the sulfoxide selectivity and the effective utilization rate of peroxide can be further improved. As can be seen from the comparison between example 1 and example 3, when the weight of the carbon nitride with the particle size of 20-100 nm in the catalyst accounts for 2-30%, preferably 5-20% of the total weight of the carbon nitride, the catalyst has better performance of catalyzing the oxidation of thioether, and can obtain higher thioether conversion rate and sulfoxide selectivity.
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 foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
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 spirit of the present disclosure.
Claims (16)
1. A method for preparing sulfoxide from thioether through oxidation, which comprises the following steps: the thioether and the peroxide are subjected to contact reaction in the presence of a catalyst, wherein the catalyst is carbon nitride.
2. The method of claim 1, wherein the nitrogen content of the carbon nitride is not less than 50 wt%.
3. The method according to claim 1, wherein the carbon nitride having a particle size of 20 to 100nm is present in an amount of 2 to 30% by weight based on the total weight of the carbon nitride.
4. A process according to claim 3, wherein the carbon nitride having a particle size of 20 to 100nm is present in an amount of 5 to 20% by weight based on the total weight of the carbon nitride.
5. The process of claim 1, wherein the reaction is carried out without back-mixing of the materials.
6. The process of any one of claims 1 to 5, wherein the reaction is carried out in a slurry bed reactor with screw-propelled stirring paddles.
7. The method according to claim 6, wherein the thioether is dimethyl sulfide, and the weight hourly space velocity of the dimethyl sulfide is 0.1-500 h-1。
8. A process according to any one of claims 1 to 5, wherein the molar ratio of thioether to peroxide is 1: (0.1-2).
9. The process according to claim 8, wherein the molar ratio of thioether to peroxide is 1: (0.2 to 1).
10. The method according to any one of claims 1 to 5, wherein the sulfide is dimethyl sulfide, ethyl sulfide, diethyl sulfide or ethyl sulfide.
11. The process of any one of claims 1 to 5, wherein the peroxide is hydrogen peroxide, t-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peroxyacetic acid or peroxypropionic acid, or a combination of two or three thereof.
12. The method of any one of claims 1 to 5, further comprising: the reaction is carried out in the presence of a solvent selected from water and C1～C6Alcohol of (1), C3～C8Ketone and C2～C6One or more of (a) nitrile(s).
13. The process according to claim 12, wherein the weight ratio of solvent to thioether is (0.1-20): 1.
14. the method according to claim 13, wherein the weight ratio of solvent to thioether is (1-10): 1.
15. the method according to any one of claims 1 to 5, wherein the reaction conditions comprise: the temperature is 0-80 ℃, the pressure is 0-3 MPa, and the time is 0.1-12 h.
16. The method of claim 15, wherein the conditions of the reaction comprise: the temperature is 20-50 ℃, the pressure is 0.1-2.5 MPa, and the time is 0.2-5 h.
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| CN102515999A (en) * | 2011-11-30 | 2012-06-27 | 浙江大学 | Method for selectively oxidizing sulfide |
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| CN102515999A (en) * | 2011-11-30 | 2012-06-27 | 浙江大学 | Method for selectively oxidizing sulfide |
| CN108484464A (en) * | 2018-02-01 | 2018-09-04 | 浙江工业大学 | A kind of method of selective oxidation disulfide |
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