CN109304199B - Heteroatom-containing nano carbon material, preparation method thereof and thioether oxidation method - Google Patents

Heteroatom-containing nano carbon material, preparation method thereof and thioether oxidation method Download PDF

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CN109304199B
CN109304199B CN201710631554.5A CN201710631554A CN109304199B CN 109304199 B CN109304199 B CN 109304199B CN 201710631554 A CN201710631554 A CN 201710631554A CN 109304199 B CN109304199 B CN 109304199B
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CN109304199A (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
    • C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton

Abstract

The invention discloses a heteroatom-containing nano-carbon material and a preparation method thereof, and the method comprises the steps of contacting a raw material nano-carbon material with an oxidant at 10-40 ℃, dispersing the oxidized nano-carbon material and an organic base in water, reacting the obtained water dispersion in a closed container at the temperature of 110-180 ℃, wherein the organic base is amine and/or quaternary ammonium base, and roasting the nano-carbon material treated by the organic base at the temperature of 550-1200 ℃ in a non-active atmosphere. The invention also discloses a thioether oxidation method using the heteroatom-containing nano carbon material as a catalyst, compared with an untreated nano carbon material, the method can obtain higher thioether conversion rate even if the oxidation reaction is carried out at lower temperature, and can obtain obviously improved product selectivity, especially selectivity to sulfoxide.

Description

Heteroatom-containing nano carbon material, preparation method thereof and thioether oxidation method
Technical Field
The invention relates to a preparation method of a heteroatom-containing nano carbon material, the heteroatom-containing nano carbon material prepared by the method, and a thioether oxidation method using the heteroatom-containing nano carbon material as a catalyst.
Background
The sulfoxide is an important sulfur-containing compound, such as dimethyl sulfoxide (DMSO), which is a sulfur-containing organic compound, is a colorless transparent liquid at normal temperature, and has the characteristics of high polarity, high hygroscopicity, flammability, high boiling point, non-proton and the like. Dimethyl sulfoxide is soluble in water, ethanol, acetone, diethyl ether and chloroform, is a highly polar inert solvent, and is widely used as a solvent and a reaction reagent, for example, as a processing solvent and a spinning solvent in acrylonitrile polymerization, as a synthesis solvent and a spinning solvent for polyurethane, and as a synthesis solvent for polyamide, chlorofluoroaniline, polyimide and polysulfone. 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. 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.
Dimethyl sulfoxide can also be produced from dimethyl sulfide by the anodic oxidation method, but the anodic oxidation method has high cost and is not suitable for large-scale production.
Disclosure of Invention
The present invention aims to provide a heteroatom-containing nanocarbon material which can be obtained by using dimethyl sulfide as a catalyst and dimethyl sulfoxide obtained by oxidizing dimethyl sulfide with an oxidizing agent, and which can achieve high dimethyl sulfide conversion rate and dimethyl sulfoxide selectivity.
According to a first aspect of the present invention, there is provided a method for preparing a heteroatom-containing nanocarbon material, the method comprising the steps of:
(1) contacting a raw material nano carbon material with at least one oxidant at the temperature of 10-40 ℃ to obtain an oxidized nano carbon material;
(2) dispersing the nano-carbon material subjected to oxidation treatment and at least one organic base in water, and reacting the obtained aqueous dispersion in a closed container to obtain the nano-carbon material subjected to organic base treatment, wherein the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion is kept within the range of 110-180 ℃ in the reaction process; and
(3) the nano carbon material treated by the organic alkali is roasted in an inactive atmosphere at the temperature of 550-1200 ℃.
According to a second aspect of the present invention there is provided a heteroatom-containing nanocarbon material produced by the method of the first aspect of the invention.
According to a third aspect of the present invention, there is provided a thioether oxidation process comprising contacting, under oxidation reaction conditions, a thioether, an oxidant and optionally a solvent, with a heteroatom-containing nanocarbon material, wherein the heteroatom-containing nanocarbon material is the heteroatom-containing nanocarbon material according to the second aspect of the present invention.
Compared with the untreated nano carbon material as the catalyst, the nano carbon material containing the hetero atoms as the catalyst for the thioether oxidation reaction can obtain higher thioether conversion rate even if thioether is oxidized at lower temperature, and can obtain obviously improved product selectivity, especially the selectivity for sulfoxide.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a heteroatom-containing nano carbon material, which comprises the following steps:
(1) contacting a raw material nano carbon material with at least one oxidant at the temperature of 10-40 ℃ to obtain an oxidized nano carbon material;
(2) dispersing the nano-carbon material subjected to oxidation treatment and at least one organic base in water, and reacting the obtained aqueous dispersion in a closed container to obtain the nano-carbon material subjected to organic base treatment, wherein the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion is kept within the range of 110-180 ℃ in the reaction process; and
(3) the nano carbon material treated by the organic alkali is roasted in an inactive atmosphere at the temperature of 550-1200 ℃.
In the step (1), the oxidizing agent is preferably one or more of an acid having oxidizing properties, hydrogen peroxide, and an organic peroxide. In a preferred embodiment of the present invention, the oxidizing agent is selected from HNO3、H2SO4One or more than two of hydrogen peroxide and organic peroxide shown in formula I,
Figure BDA0001363970400000041
in the formula I, R1And R2Each is selected from H, C4-C12Straight or branched alkyl of (2), C6-C12Aryl of (C)7-C12Aralkyl and
Figure BDA0001363970400000042
and R is1And R2Not simultaneously being H or R3Is C4-C12Or linear or branched alkyl, or C6-C12Aryl group of (1).
In the present invention, C4-C12Specific examples of the alkyl group of (a) may include, but are not limited to, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, hexyl (including various isomers of hexyl), cyclohexyl, octyl (including various isomers of octyl), nonyl (including various isomers of nonyl), decyl (including various isomers of decyl), undecyl (including various isomers of undecyl), and dodecyl (including various isomers of dodecyl).
In the present invention, C6-C12Specific examples of the aryl group of (a) may include, but are not limited to, phenyl, naphthyl, methylphenyl and ethylphenyl.
In the present invention, C7-C12Specific examples of the aralkyl group of (a) may include, but are not limited to, a phenylmethyl group, a phenylethyl group, a phenyl-n-propyl group, a phenyl-n-butyl group, a phenyl-tert-butyl group, a phenyl-isopropyl group, a phenyl-n-pentyl group and a phenyl-n-butyl group.
Specific examples of the oxidizing agent may include, but are not limited to: HNO3、H2SO4Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide and lauroyl peroxide.
The oxidizing agent is preferably an acid having oxidizing property from the viewpoint of further improving the catalytic activity of the finally produced heteroatom-containing nanocarbon material. More preferably, the oxidizing agent is HNO3And/or H2SO4. Further preferably, the oxidant is HNO3And H2SO4. Even more preferably, the oxidizing agent is HNO3And H2SO4And HNO3And H2SO4In a molar ratio of 1: 1-10, preferably 1: 1.5 to 8, more preferably 1: 2-4.
In step (1), the oxidizing agent may be provided in the form of a pure substance or may be provided in the form of a solution (preferably, an aqueous solution). Where the oxidant is provided in the form of a solution, the concentration of the solution may be conventionally selected.
In the step (1), the oxidizing agent may be used in an amount of 5 to 2000 parts by weight, preferably 10 to 1000 parts by weight, relative to 100 parts by weight of the raw nanocarbon material. In a preferred embodiment, the oxidant is used in an amount of 100-1000 parts by weight, preferably 200-1000 parts by weight, relative to 100 parts by weight of the raw nanocarbon material, and the nanocarbon material containing heteroatoms prepared thereby is particularly suitable as a catalyst for a reaction for preparing benzyl sulfoxide by oxidizing benzyl sulfide. In another preferred embodiment, the oxidant is used in an amount of 10 to 200 parts by weight, preferably 40 to 200 parts by weight, relative to 100 parts by weight of the raw nanocarbon material, and thus prepared heteroatom-containing nanocarbon material is particularly suitable as a catalyst for a reaction of preparing dimethyl sulfoxide by oxidation of dimethyl sulfide.
In the step (1), the raw material nanocarbon material contains an oxygen element, a hydrogen element and a carbon element, and the content of the oxygen element may be 0.1 to 1% by weight, preferably 0.15 to 0.8% by weight, and more preferably 0.25 to 0.6% by weight, in terms of element, based on the total amount of the raw material nanocarbon material; the content of the hydrogen element may be 0.1 to 1% by weight, preferably 0.2 to 0.9% by weight, more preferably 0.4 to 0.6% by weight; the content of the carbon element may be 98 to 99.8% by weight, preferably 98.3 to 99.65% by weight, more preferably 98.8 to 99.35% by weight.
The content of each element in the raw material nano carbon material is determined by adopting an element analysis method. In the invention, the elemental analysis is carried out on an element analyzer of Elementar Micro Cube, and the specific operation method and conditions are as follows: weighing 1-2mg of a sample in a tin cup, placing the sample into an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (atmosphere interference during sample feeding is removed, helium is adopted for blowing), carbon dioxide and water formed by combustion are separated through three desorption columns, and a Thermal Conductivity Detector (TCD) is used for detecting in sequence. The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
The total amount of surface elements of the raw nanocarbon material determined by X-ray photoelectron spectroscopy is determined by the X-ray photoelectron spectroscopy
Figure BDA0001363970400000061
The content of oxygen element determined by the peak of the radical may be 0.1 to 0.5 mol%, preferably 0.2 to 0.45 mol%, more preferably 0.3 to 0.45 mol%.
The raw material nano carbon material has X-ray photoelectron spectrum with oxygen content determined by the peak corresponding to C-O group and the peak corresponding to C-O group
Figure BDA0001363970400000062
The molar ratio of the content of oxygen elements determined by the peaks of the radicals may be between 0.1 and 1: 1, preferably 0.3 to 0.9: 1, more preferably 0.75 to 0.85: 1.
the raw material nano carbon material has X-ray photoelectron spectrum corresponding to that of
Figure BDA0001363970400000063
The content of oxygen determined by the peak of the radical corresponds to
Figure BDA0001363970400000064
The molar ratio of the content of oxygen elements determined by the peaks of the radicals may be between 0.1 and 2: 1, preferably 0.5 to 1.8: 1, more preferably 0.8 to 1.2: 1.
in the invention, the content of oxygen elements on the surface of the nano carbon material and the content of each oxygen species are measured by adopting an X-ray photoelectron spectroscopy, and the specific method comprises the following steps:
(1) performing X-ray photoelectron spectroscopy analysis on the nano carbon material to obtain an X-ray photoelectron spectroscopy spectrum, and taking the ratio of the peak area of the 1s spectral peak of one element to the sum of the peak areas of the 1s spectral peaks of the elements as the molar content of the element, wherein the molar content of the oxygen element is recorded as XO；
(2) The peak of O1s spectrum in the X-ray photoelectron spectrum(generally in the range of 531-535eV, the peak area was designated as AO) Performing peak separation, respectively corresponding to
Figure BDA0001363970400000065
Peaks of the radicals (generally in the range 532.3 + -0.2 eV), corresponding to the CO radicals (generally in the range 533.7 + -0.2 eV), and corresponding to the CO radicals
Figure BDA0001363970400000066
The peak of the spectrum for the radical (which generally appears in the range 531.1. + -. 0.2 eV), will correspond to
Figure BDA0001363970400000067
The peak area of the peak of the radical is recorded as ACOOThe peak area of the peak corresponding to the CO group was designated as AC-OWill correspond to
Figure BDA0001363970400000071
The peak area of the peak of the radical is recorded as AC＝O；
(3) The following formula is adopted to calculate the equation
Figure BDA0001363970400000072
Molar content X of oxygen determined by the peaks of the radicalsCOO：
Figure BDA0001363970400000073
(4) A is to beC-O/ACOOThe content of oxygen element determined as a function of the peak corresponding to the CO group and the ratio of oxygen element determined as a function of the peak corresponding to the CO group
Figure BDA0001363970400000074
The molar ratio of the content of the oxygen element determined by the peak of the group;
(5) a is to beC＝O/ACOOAs corresponding to
Figure BDA0001363970400000075
The content of oxygen determined by the peak of the radical corresponds to
Figure BDA0001363970400000076
The peak of the radical spectrum determines the molar ratio of the content of the oxygen element.
In the step (1), the raw material nanocarbon material may be any nanocarbon material having various existing forms. Specifically, the raw material nanocarbon material may be, but is not limited to, one or a combination of two or more of carbon nanotubes, graphene, nanodiamonds, thin-layer graphites, nanocarbon particles, nanocarbon fibers, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. Preferably, the raw material nanocarbon material is a carbon nanotube, more preferably a multiwall carbon nanotube.
In a preferred embodiment, the raw material nanocarbon material is a multi-walled carbon nanotube, and the specific surface area of the multi-walled carbon nanotube may be 50 to 500m2(ii) in terms of/g. Preferably, the specific surface area of the multi-walled carbon nanotube is 70-300m2And/g, when the specific surface area of the multi-wall carbon nano tube is within the range, the finally obtained heteroatom-containing nano carbon material has better catalytic activity, and particularly can obtain better catalytic effect when being used as a catalyst for the reaction of oxidizing thioether. More preferably, the multi-walled carbon nanotubes have a specific surface area of 80 to 200m2/g。
When the raw material nano carbon material is the multi-walled carbon nanotube, the weight loss rate of the multi-walled carbon nanotube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01-0.3. More preferably, w500/w800In the range of 0.02 to 0.2, the thus-prepared heteroatom-containing nanocarbon material shows a better catalytic effect, and particularly when used as a catalyst for a reaction of oxidizing thioether, a better catalytic effect can be obtained. Further preferably, w500/w800In the range of 0.05-0.15.
The total amount (in terms of elements) of the non-metallic hetero atoms (such as phosphorus atoms, nitrogen atoms, and sulfur atoms) other than oxygen atoms and hydrogen atoms in the raw material nanocarbon material may be a conventional amount. Generally, the total amount of the remaining non-metallic hetero atoms other than oxygen atoms and hydrogen atoms in the raw material nanocarbon material is not more than 1% by weight, preferably not more than 0.5% by weight. The raw material nanocarbon material may contain some metal elements depending on the source, and the content of the metal elements is generally 1 wt% or less, preferably 0.5 wt% or less, which is generally derived from the catalyst used in the production of the raw material nanocarbon material.
In the step (1), the raw material nano carbon material may be pretreated (e.g., washed) by a method commonly used in the art before use to remove some impurities on the surface of the raw material nano carbon material; the raw material nano carbon material can also be directly used without pretreatment, and in the embodiment disclosed by the invention, the raw material nano carbon material is not pretreated before being used.
In the step (1), the raw material nanocarbon material and the oxidizing agent may be contacted in a liquid dispersion medium. The liquid dispersion medium may be selected according to the amount of the raw nanocarbon material used. Preferably, the liquid dispersion medium is water. The amount of the liquid dispersion medium may be selected depending on the amounts of the raw nanocarbon material and the oxidizing agent. Generally, the amount of the liquid dispersion medium may be 500-. The oxidant contains HNO3When used, the liquid dispersion medium is preferably used in such an amount that HNO is present3Is 0.01 to 5mol/L, more preferably such that HNO is present3Is 0.02 to 2mol/L, and further preferably HNO is added3Is 0.03 to 1mol/L, and further preferably HNO is caused to be present in an amount of3The concentration of (A) is 0.05-0.8 mol/L. In the presence of H in the oxidizing agent2SO4When used, the liquid dispersion medium is preferably used in such an amount that H2SO4Is 0.05 to 5mol/L, more preferably such that H2SO4Is 0.1 to 3mol/L, and it is further preferable that H is added2SO4In a concentration of0.15-2mol/L。
The raw nanocarbon material is contacted with the oxidizing agent at a temperature of 10-40 deg.C, such as 10 deg.C, 11 deg.C, 12 deg.C, 13 deg.C, 14 deg.C, 15 deg.C, 16 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C, 30 deg.C, 31 deg.C, 32 deg.C, 33 deg.C, 34 deg.C, 35 deg.C, 36 deg.C, 37 deg.C, 38 deg.C, 39 deg.C, or 40 deg.C. Preferably, the raw nanocarbon material is contacted with the oxidizing agent at a temperature of 20 to 40 ℃.
In the step (1), the raw material nanocarbon material is contacted with the oxidizing agent, preferably in the presence of ultrasonic waves, from the viewpoint of further improving the catalytic activity of the finally prepared heteroatom-containing nanocarbon material in the oxidation reaction of thioether. The contacting in the presence of ultrasonic waves may be achieved by placing the raw nanocarbon material and the oxidizing agent in an ultrasonic cleaner. The frequency of the ultrasonic wave can be 25-100kHz, and is preferably 40-80 kHz.
In the step (1), the time for contacting the raw nanocarbon material with the oxidizing agent may be selected according to the temperature at which the contact is performed. In general, the duration of the contact may be from 0.5 to 8 hours, preferably from 1 to 4 hours.
In the step (1), when the raw nanocarbon material is contacted with the oxidizing agent in the liquid dispersion medium, after the contact is completed, the method according to the present invention further comprises separating a solid substance from the mixture obtained by the contact, and drying the solid substance, thereby obtaining the oxidation-treated nanocarbon material.
The solid matter can be separated from the mixture obtained by the contact by a common solid-liquid separation method such as one or a combination of two or more of centrifugation, filtration and decantation. The separated solid material is preferably dried after washing with water (e.g. deionized water) to neutrality (typically to a pH of 6-7 for the wash water). The drying conditions are such that the liquid dispersion medium contained in the separated solid matter can be removed. In general, the drying may be carried out at a temperature of from 80 to 180 ℃ and preferably at a temperature of from 100 to 160 ℃. The duration of the drying may be selected according to the temperature at which the drying is carried out. In general, the duration of the drying may be from 0.5 to 24 hours, preferably from 1 to 20 hours, more preferably from 6 to 12 hours. The drying may be performed in an oxygen-containing atmosphere or in an oxygen-free atmosphere. Such as an air atmosphere, and a non-oxygen-containing atmosphere such as a nitrogen atmosphere, a group zero gas atmosphere (e.g., an argon atmosphere).
In the step (2), the quaternary ammonium base may be a compound represented by formula II:
Figure BDA0001363970400000101
in the formula II, R4、R5、R6And R7Each may be C1-C20Alkyl (including C)1-C20Straight chain alkyl of (2) and C3-C20Branched alkyl of) or C6-C12Aryl group of (1). Said C is1-C20Specific examples of the alkyl group of (a) may include, but are not limited to: one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. Said C is6-C12Specific examples of the aryl group of (a) may include, but are not limited to, phenyl, naphthyl, methylphenyl and ethylphenyl. Preferably, R4、R5、R6And R7Each is C1-C10Alkyl (including C)1-C10Straight chain alkyl of (2) and C3-C10Branched alkyl groups of (a). Further preferably, R4、R5、R6And R7Each is C1-C6Alkyl (including C)1-C6Straight chain alkyl of (2) and C3-C6Branched alkyl groups of (a).
The amine refers to a substance in which one, two or three hydrogens in an ammonia molecule are replaced with an organic group, which may be bonded to a nitrogen atom to form a cyclic structure. The organic group may be a substituted (e.g., hydroxyl-substituted) or unsubstituted aliphatic hydrocarbon group and/or a substituted (e.g., hydroxyl-substituted) or unsubstituted aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic hydrocarbon group, and a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic hydrocarbon group. Specifically, the amine may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted heterocyclic amine, and a substituted (e.g., hydroxyl-substituted) or unsubstituted arylamine.
The unsaturated aliphatic amine refers to an aliphatic chain amine having an unsaturated group in a molecular structure, and the unsaturated group is preferably an alkenyl group (i.e., -C ═ C —). The number of the unsaturated group and the amino group may be one or two or more, respectively, and is not particularly limited.
In step (2), specific examples of the organic base may include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, sec-butylamine, diisobutylamine, triisobutylamine, tert-butylamine, n-pentylamine, di-n-pentylamine, tri-n-pentylamine, neopentylamine, isoamylamine, diisopentylamine, triisopentylamine, tert-pentylamine, n-hexylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecyldimethylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, monoethanolamine, triethanolamine, triisopropanolamine, diethanolamine, di-n-propanolamine, tri-n-propanolamine, di-n-butanolamine, tri-n-butanolamine, di-n-pentanolamine, di-n-pentanolamine, di-n-pentanolamine, tri-pentanol, iso-pentanol, sec-butanol, and sec-butanol, and the like, Dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, ethylenediamine, propylenediamine, butylenediamine, pentyldiamine, hexyldiamine, substituted or unsubstituted pyrrole, substituted or unsubstituted tetrahydropyrrole, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline, substituted or unsubstituted pyrimidine, aniline, diphenylamine, benzidine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-toluidine, m-toluidine, p-toluidine, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, p-toluidine, p-toluene, n, p-toluene, p-xylene, p-toluene, n, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, o-ethylaniline, N-butylaniline, 2, 6-diethylaniline, cyclohexylamine, cyclopentylamine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including various isomers thereof, such as tetra-N-propylammonium hydroxide and tetraisopropylammonium hydroxide), tetrabutylammonium hydroxide (including various isomers thereof, such as tetra-N-butylammonium hydroxide, tetra-sec-butylammonium hydroxide, tetra-isobutylammonium hydroxide and tetra-tert-butylammonium hydroxide), and tetrapentylammonium hydroxide (including various isomers thereof).
In step (2), the amine is preferably a compound represented by formula III, a compound represented by formula IV, or a compound represented by general formula R15(NH2)2One or more of the substances shown,
Figure BDA0001363970400000121
Figure BDA0001363970400000122
in the formula III, R8、R9And R10Are each H, C1-C6Alkyl or C6-C12And R is an aryl group of8、R9And R10Not H at the same time. In the present invention, C1-C6Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl. In the present invention, C6-C12Specific examples of aryl groups of (a) include, but are not limited to, phenyl, naphthyl, methylphenyl, and ethylphenyl.
In the formula IV, R11、R12And R13Each is-R14OH or hydrogen, and R11、R12And R13At least one of which is-R14OH，R14Is C1-C4An alkylene group of (a). In the present invention, C1-C4Alkylene of (A) includes C1-C4Linear alkylene of (A) and (C)3-C4Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, and tert-butylene.
General formula R15(NH2)2In, R15Can be C1-C6Alkylene or C6-C12An arylene group of (a). In the present invention, C1-C6Alkylene of (A) includes C1-C6Linear alkylene of (A) and (C)3-C6Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, and n-hexylene. In the present invention, C6-C12Specific examples of the arylene group of (a) include, but are not limited to, phenylene and naphthylene.
Preferably, the organic base is a quaternary ammonium base.
In the step (2), the nano carbon material subjected to oxidation treatment: the weight ratio of the organic base can be 1: in the range of 0.1-20. In a preferred embodiment, the oxidation-treated nanocarbon material: the weight ratio of the organic base is 1: in the range of 2 to 20, the nanocarbon material containing hetero atoms prepared according to the preferred embodiment is particularly suitable as a catalyst for a reaction for preparing methyl phenyl sulfoxide by oxidizing methyl phenyl sulfide. In another preferred embodiment, the oxidation-treated nanocarbon material: the weight ratio of the organic base is 1: the nanocarbon material containing hetero atoms prepared according to this preferred embodiment is particularly suitable as a catalyst for the reaction of preparing dimethyl sulfoxide by oxidation of dimethyl sulfide in the range of 0.1 to 10.
In the step (2), the amount of water in the aqueous dispersion may be selected according to the amount of the organic base and the amount of the oxidized nanocarbon material. Generally, the oxidation-treated nanocarbon material: h2The weight ratio of O can be 1: in the range of 5 to 200, preferably in the range of 1: in the range of 5 to 100, more preferably in the range of 1: in the range of 10-50.
In the step (2), the temperature of the aqueous dispersion is kept within the range of 110-180 ℃ during the reaction. When the prepared nano carbon material containing the heteroatom is used as a catalyst for the reaction of oxidizing the methyl sulfide to prepare the methyl sulfoxide, the temperature of the aqueous dispersion is kept within the range of 140-180 ℃ in the reaction process. When the prepared heteroatom-containing nano carbon material is used as a catalyst for the reaction for preparing dimethyl sulfoxide by oxidizing dimethyl sulfide, the temperature of the aqueous dispersion is kept within the range of 110-180 ℃ in the reaction process.
In step (2), the duration of the reaction may be selected according to the temperature of the reaction. In general, the duration of the reaction may be in the range of 1 to 24 hours, preferably in the range of 4 to 20 hours, more preferably in the range of 8 to 16 hours.
In the step (2), the aqueous dispersion may be formed by various methods commonly used, for example, the oxidized nanocarbon material may be dispersed in water (preferably deionized water), and then the organic base may be added to obtain the aqueous dispersion. In order to further improve the dispersion effect of the oxidized nanocarbon material and shorten the dispersion time, the raw nanocarbon material may be dispersed in water by ultrasonic oscillation. The conditions of the ultrasonic oscillation may be conventionally selected, and in general, the frequency of the ultrasonic oscillation may be 10 to 100kHz, preferably 40 to 80kHz, and the duration of the ultrasonic oscillation may be 0.1 to 6 hours, preferably 0.5 to 2 hours. The organic base is preferably provided in the form of a solution, preferably an aqueous solution.
In the step (2), the reaction is carried out in a closed container. The reaction may be carried out under autogenous pressure (i.e., without additional application of pressure) or under pressurized conditions. Preferably, the reaction is carried out under autogenous pressure. The closed container can be a common reactor capable of realizing sealing and heating, such as a high-pressure reaction kettle.
The step (2) may further comprise separating solid matter from the mixture obtained from the reaction, and drying the separated solid matter to obtain the organic base-treated nanocarbon material. The solid matter can be separated from the mixture obtained by the reaction by a conventional solid-liquid separation method such as one or a combination of two or more of centrifugation, filtration and decantation. The drying conditions may be chosen conventionally, so as to be able to remove volatile substances from the separated solid material. Generally, the drying may be carried out at a temperature of from 50 to 200 ℃, preferably at a temperature of from 80 to 180 ℃, more preferably at a temperature of from 100 ℃ to 160 ℃, even more preferably at a temperature of from 120 ℃ to 150 ℃. The duration of the drying may be selected according to the temperature and manner of drying. In general, the duration of the drying may be from 0.5 to 48 hours, preferably from 3 to 24 hours, more preferably from 5 to 12 hours. The drying may be carried out under normal pressure (1 atm), or under reduced pressure. From the viewpoint of further improving the efficiency of drying, the drying is preferably performed under reduced pressure.
In the step (3), the organic base treated nano-carbon material is calcined at the temperature of 550-1200 ℃ in an inactive atmosphere. Compared with roasting in an inert atmosphere at the temperature lower than 550 ℃ or higher than 1200 ℃, the heteroatom-containing nano carbon material obtained by roasting in the inert atmosphere at the temperature of 550-1200 ℃ shows more excellent catalytic activity in the reaction of oxidizing thioether, and can obviously improve the conversion rate of raw materials and the selectivity of products. Preferably, the calcination is carried out at a temperature of 600-. From the viewpoint of further improving the product selectivity of the finally prepared heteroatom-containing nanocarbon material in the reaction for oxidizing thioether, the calcination is further preferably carried out at a temperature of 700-1100 ℃.
In the step (3), the duration of the calcination may be selected according to the temperature at which the calcination is performed. In general, the duration of the calcination may be from 2 to 24 hours, preferably from 2 to 12 hours, more preferably from 2.5 to 5 hours.
In the step (3), the inert atmosphere refers to a chemically inert atmosphere. The inert gas atmosphere may be specifically an atmosphere formed by an inert gas, and the inert gas may be, for example, one or two or more of nitrogen and a group zero gas (e.g., helium, argon). Preferably, the nanocarbon material treated with an organic base is calcined in a nitrogen atmosphere.
According to a second aspect of the present invention there is provided a heteroatom-containing nanocarbon material produced by the method of the first aspect of the invention.
According to a third aspect of the present invention, there is provided a thioether oxidation process comprising contacting, under oxidation reaction conditions, a thioether, an oxidant and optionally a solvent, with a heteroatom-containing nanocarbon material, wherein the heteroatom-containing nanocarbon material is the heteroatom-containing nanocarbon material according to the second aspect of the present invention.
According to the thioether oxidation method of the present invention, the heteroatom-containing nanocarbon material may be used as a catalyst directly or in the form of a shaped catalyst. The shaped catalyst may contain the heteroatom-containing nanocarbon material and a binder. The binder may be selected according to the specific application of the formed catalyst, and may be, for example, an organic binder and/or an inorganic binder, so as to meet the application requirements.
According to the thioether oxidation process of the invention, the peroxide may be a substance sufficient to oxidize the thioether. The peroxide is a compound containing an-O-O-bond in the molecular structure, and can be selected from hydrogen peroxide, hydroperoxide and peracid. The hydroperoxide is a substance obtained by substituting one hydrogen atom 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 oxidizing agent may include, but are not limited to: hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid and 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 safety, the production method according to the present invention preferably uses hydrogen peroxide in the form of an aqueous solution. Where the hydrogen peroxide is provided as an aqueous solution, the concentration of the aqueous hydrogen peroxide solution may be conventional in the art, for example: 20-80 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 amount of the oxidizing agent to be used may be selected depending on the desired oxidation product, and is not particularly limited. Where the desired oxidation product is a sulfoxide, the molar ratio of thioether to oxidant may be 1: 0.1 to 2, preferably 1: 0.5-1.5, more preferably 1: 0.6-1.
According to the method for oxidizing thioether of the present invention, the contacting of thioether and peroxide with the heteroatom-containing nanocarbon material is preferably carried out in the presence of at least one solvent. The solvent may be a variety of liquid substances that are capable of dissolving the thioether and peroxide or facilitating mixing of the two, as well as dissolving the target oxidation product. In general, the solvent may be selected from water, C1-C6Alcohol of (1), C3-C8Ketone and C2-C6A nitrile of (a). Specific examples of the solvent may include, but are not limited to: water, methanol, ethanol, n-propanol, isopropanol, tert-butanol and isobutanolAlcohols, acetone, butanone and acetonitrile.
The amount of the solvent may be appropriately selected depending on the amount of the thioether and the peroxide and the heteroatom-containing nanocarbon material. Generally, the molar ratio of solvent to thioether may be from 0.1 to 200: 1, preferably 20 to 100: 1, more preferably 50 to 80: 1.
according to the thioether oxidation process of the invention, the oxidation reaction conditions may be selected according to the desired target oxidation product. Generally, the thioethers and peroxides can be carried out with the heteroatom-containing nanocarbon material at a temperature of 10 to 100 ℃. According to the thioether oxidation method, even if the oxidation reaction is carried out at a lower reaction temperature, higher thioether conversion rate and product selectivity can be obtained. Preferably, according to the method for oxidizing thioether of the present invention, the thioether and the peroxide are preferably contacted with the heteroatom-containing nanocarbon material at a temperature of 20 to 60 ℃, more preferably at a temperature of 30 to 50 ℃. The pressure in the reactor in which the thioether and the peroxide are contacted with the heteroatom-containing nanocarbon material may be in the range of 0 to 3MPa, preferably 0 to 1.5MPa, as gauge pressure.
According to the thioether oxidation method, thioether and peroxide can be contacted with the heteroatom-containing nano carbon material in a common reactor, wherein the reactor can be a batch reactor or a continuous reactor. In one embodiment, the thioether and the peroxide are contacted with the heteroatom-containing nanocarbon material in a fixed bed reactor, and in this embodiment, the weight hourly space velocity of the thioether can be in the range of 0.1 to 500h-1Preferably 5-300h-1More preferably 10-100h-1More preferably 20 to 60 hours-1. In another embodiment, the thioether and the peroxide are contacted with the heteroatom-containing nanocarbon material in a tank reactor.
The thioether oxidation process according to the invention may further comprise separating the reaction mixture to obtain the target oxidation product (e.g. sulfoxide) 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.
According to the method for oxidizing thioether of the present invention, the thioether may be any of various compounds having an-S-bond, and preferably the thioether is selected from the group consisting of thioethers having 2 to 18 carbon atoms, more preferably dimethyl sulfide and/or dimethyl sulfide.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following preparation examples and comparative preparations, X-ray photoelectron spectroscopy was carried out on an ESCALB 250 type X-ray photoelectron spectrometer equipped with Thermo Avantage V5.926 software, manufactured by Thermo Scientific, with an excitation source of monochromated Al K.alpha.X rays, an energy of 1486.6eV, a power of 150W, a transmission energy for narrow scanning of 30eV, and a base vacuum of 6.5X 10 during analytical testing-10mbar, electron binding energy was corrected for the C1s peak (284.6eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 c and 1 atm under a helium atmosphere for 3 hours before testing.
In the following preparation examples and comparative preparations, the ASAP2000 type N from micrometrics, USA, was used2The physical adsorption apparatus measures the specific surface area.
In the following preparation examples and comparative preparations, elemental analysis was performed on an Elementar Micro Cube elemental analyzer, and the specific operating methods and conditions were as follows: the sample is weighed in a tin cup to be about 1-2mg, placed in an automatic sample feeding disc, enters a combustion tube through a ball valve for combustion, the combustion temperature is 1000 ℃ (atmospheric interference is removed during sample feeding, helium is adopted for blowing), carbon dioxide and water formed by combustion are separated through three desorption columns, and a TCD detector is sequentially used for detection. The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
In the following preparation examples and comparative preparations, thermogravimetric analysis was performed on a TA5000 thermal analyzer under the test conditions of an air atmosphere, a temperature rise rate of 10 ℃/min, and a temperature range ofRoom temperature (25 ℃) to 1000 ℃. The samples were dried at a temperature of 150 c and 1 atm under a helium atmosphere for 3 hours before testing. The method adopts ASAP2000 type N of Micromertrics corporation in America2The physical adsorption apparatus measures the specific surface area.
In the following examples and comparative examples, the contents of the respective components in the obtained reaction liquids were analyzed by gas chromatography, and on the basis of the contents, the thioether conversion rate and the sulfoxide selectivity were calculated by the following formulas, respectively.
XThioethers＝[(mo Thioethers－mThioethers)/mo Thioethers]×100％
Wherein, XThioethersRepresents the conversion of thioether;
mo thioethersRepresents the mass of thioether added;
mthioethersRepresents the mass of unreacted thioether.
SSulfoxide＝[nSulfoxide/(no Thioethers－nThioethers)]×100％
Wherein S isSulfoxideRepresents the sulfoxide selectivity;
no thioethersRepresents the molar amount of thioether added;
nthioethersRepresents the molar amount of unreacted thioether;
nsulfoxideRepresents the molar amount of sulfoxide produced by the reaction.
Preparation examples 1 to 16 heteroatom-containing nanocarbon materials used in the present invention.
The property parameters of the raw material nanocarbon materials used in preparation examples 1 to 16 are shown in table 1 below.
TABLE 1
Figure BDA0001363970400000191
Preparation of example 1
(1) 10g of multiwall carbon nanotube A (available from GmbH, national academy of sciences) as a raw nanocarbon material and 350mL of acid solution: (H2SO4Has a concentration of 69g/L, HNO3Is 12g/L, and the solvent of the acid solution is water), and the obtained dispersion is put into an ultrasonic cleaner for ultrasonic treatment, wherein the temperature of the dispersion in the ultrasonic cleaner is controlled to be 40 ℃, the duration of the ultrasonic treatment is 4 hours, and the frequency of the ultrasonic wave is 45 kHz. And after the ultrasonic treatment is finished, filtering the dispersion liquid, washing the collected solid matters by using deionized water until the pH value of the washing liquid is in the range of 6-7, and drying the washed solid matters in an air atmosphere at the temperature of 100 ℃ for 12 hours to obtain the nano carbon material subjected to oxidation treatment.
(2) Dispersing 10g of the oxidation-treated nanocarbon material and tetrapropylammonium hydroxide in 150g of deionized water to obtain an aqueous dispersion, wherein the oxidation-treated nanocarbon material: the weight ratio of tetrapropylammonium hydroxide is 1: and 2, dispersing under ultrasonic oscillation conditions, wherein the ultrasonic oscillation conditions comprise: the frequency was 40kHz and the time was 2 hours. The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at 180 ℃ under autogenous pressure for 8 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. The collected solid matter was dried at 150 ℃ for 8 hours under normal pressure (1 atm, the same applies below) to obtain an organic base-treated nanocarbon material.
(3) The nanocarbon material treated with the organic base was calcined at a temperature of 720 ℃ for 5 hours in a nitrogen atmosphere, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of comparative example 1
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 1, except that the step (2) was not performed, but the oxidized nanocarbon material obtained in the step (1) was directly fed to the step (3) to be calcined.
Preparation of comparative example 2
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that the step (1) was not performed.
Preparation of example 2
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that, in step (3), the calcination was performed at a temperature of 550 ℃, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of comparative example 3
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that, in step (3), the calcination was carried out at a temperature of 450 ℃.
Preparation of example 3
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 1, except that in step (1), H was not used2SO4Thereby obtaining the heteroatom-containing nano-carbon material according to the invention.
Preparation of example 4
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that HNO was not used in step (1)3Thereby obtaining the heteroatom-containing nano-carbon material according to the invention.
Preparation of example 5
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that, in step (1), the amount of the acid solution was 250mL, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of comparative example 4
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that, in step (1), the temperature of the dispersion in the ultrasonic cleaner was controlled to 60 ℃.
Preparation of comparative example 5
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 1, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at 200 ℃ under autogenous pressure for 8 hours.
Preparation of example 6
(1) 10g of multiwall carbon nanotube B (available from GmbH, national academy of sciences) as a raw nanocarbon material and 500mL of an acid solution (H)2SO4Has a concentration of 150g/L, HNO345g/L, the solvent of the acid solution is water), and the obtained dispersion is placed in an ultrasonic cleaner for ultrasonic treatment, wherein the temperature of the dispersion in the ultrasonic cleaner is controlled to be 20 ℃, the duration of the ultrasonic treatment is 4 hours, and the frequency of the ultrasonic wave is 60 kHz. And after the ultrasonic treatment is finished, filtering the dispersion liquid, washing the collected solid matters by using deionized water until the pH value of the washing liquid is in the range of 6-7, and drying the washed solid matters for 10 hours at the temperature of 120 ℃ in an air atmosphere to obtain the nano carbon material subjected to oxidation treatment.
(2) Dispersing 10g of the oxidation-treated nanocarbon material and tetraethylammonium hydroxide in 150g of deionized water to obtain an aqueous dispersion, wherein the oxidation-treated nanocarbon material: the weight ratio of tetraethyl ammonium hydroxide is 1: 10, the dispersion is carried out under ultrasonic oscillation conditions comprising: the frequency was 40kHz and the time was 2 hours. The resulting aqueous dispersion was placed in a high-pressure autoclave with a polytetrafluoroethylene liner and reacted at 140 ℃ under autogenous pressure for 16 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. Drying the collected solid matter at 150 deg.c and normal pressure for 7 hr to obtain the organic alkali treated nanometer carbon material.
(3) The nanocarbon material treated with the organic base was calcined at 1050 ℃ for 2.5 hours in a nitrogen atmosphere, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of example 7
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (3), the calcination temperature was 1200 ℃.
Preparation of comparative example 6
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (3), the calcination temperature was 1300 ℃.
Preparation of comparative example 7
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 6, except that the step (2) was not performed, but the oxidized nanocarbon material obtained in the step (1) was directly fed to the step (3) to be calcined.
Preparation of comparative example 8
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that the step (1) was not performed.
Preparation of example 8
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at 110 ℃ under autogenous pressure for 16 hours, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of example 9
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 6, except that, in step (1), H2SO4Has a concentration of 15g/L, HNO3Is 4.5g/L, thereby obtaining a heteroatom-containing nanocarbon material according to the invention.
Preparation of comparative example 9
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 6, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at 100 ℃ under autogenous pressure for 16 hours, thereby obtaining a nanocarbon material containing hetero atoms.
Preparation of example 10
(1) 10g of multiwall carbon nanotube C (available from GmbH, national academy of sciences) as a raw nanocarbon material and 500mL of an acid solution (H)2SO4Has a concentration of 69g/L, HNO3The concentration of (2) is 12g/L, and the solvent of the acid liquorWater) was added, and the obtained dispersion was subjected to ultrasonic treatment in an ultrasonic cleaner, wherein the temperature of the dispersion in the ultrasonic cleaner was controlled to 30 ℃, the duration of the ultrasonic treatment was 1 hour, and the frequency of the ultrasonic wave was 80 kHz. And after the ultrasonic treatment is finished, filtering the dispersion liquid, washing the collected solid matters by using deionized water until the pH value of the washing liquid is in the range of 6-7, and drying the washed solid matters for 6 hours at the temperature of 160 ℃ in an air atmosphere to obtain the nano carbon material subjected to oxidation treatment.
(2) Dispersing 10g of the oxidation-treated nanocarbon material and tetramethylammonium hydroxide in 320g of deionized water to obtain an aqueous dispersion, wherein the oxidation-treated nanocarbon material: the weight ratio of the tetramethylammonium hydroxide is 1: 20, the dispersion is carried out under ultrasonic oscillation conditions comprising: the frequency was 40kHz and the time was 2 hours. The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at 160 ℃ under autogenous pressure for 12 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. Drying the collected solid matter at 120 deg.c for 12 hr under normal pressure to obtain the organic alkali treated nanometer carbon material.
(3) The nanocarbon material treated with the organic base was calcined at a temperature of 850 ℃ for 4 hours in a nitrogen atmosphere, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of example 11
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 10, except that in step (2), tetramethylammonium hydroxide was replaced with n-propylamine of an equal weight, thereby obtaining a heteroatom-containing nanocarbon material according to the invention.
Preparation of example 12
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 10, except that, in step (2), tetramethylammonium hydroxide was replaced with diethanolamine in an equal weight, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of example 13
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 10, except that, in step (2), tetramethylammonium hydroxide was replaced with diethylamine in an equal weight, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of comparative example 10
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 10, except that the step (2) was not performed, but the oxidized nanocarbon material obtained in the step (1) was directly fed to the step (3) to be calcined.
Preparation of comparative example 11
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 10, except that the step (1) was not performed.
Preparation of example 14
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 10, except that the amount of the acid solution used in step (1) was 100mL, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Preparation of example 15
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 14, except that, in step (2), the oxidation-treated nanocarbon material: the weight ratio of the tetramethylammonium hydroxide is 1: 10, thereby obtaining the heteroatom-containing nanocarbon material according to the invention.
Preparation of example 16
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 15, except that, in step (1), the acid solution was replaced with hydrogen peroxide of the same volume, and the content of hydrogen peroxide in the hydrogen peroxide was 80g/L, thereby obtaining a heteroatom-containing nanocarbon material according to the present invention.
Examples 1-16 are intended to illustrate the thioether oxidation process according to the invention.
Examples 1 to 16
0.2g (packing volume of 0.5mL) of each of the nanocarbon materials containing hetero atoms prepared in preparation examples 1 to 16 was packed as a catalyst in a universal type fixed bed micro quartz tube reactor sealed at both ends with quartz sand. The thioether (dimethyl sulfide or thioanisole), the peroxide and the solvent are continuously fed into the reactor and continuously carried out for 6 hours. The composition of the reaction mixture output from the reactor was determined by gas chromatography and the thioether conversion and sulfoxide selectivity were calculated, the specific reaction conditions and experimental results are listed in table 2.
Comparative examples 1 to 11
Thioethers were oxidized in the same manner as in examples 1 to 16, except that the heteroatom-containing nanocarbon materials used in the preparation of the heteroatom-containing nanocarbon materials prepared in comparative examples 1 to 11, respectively, were used, and the experimental results are shown in Table 2.
Comparative examples 12 to 14
Thioether was oxidized in the same manner as in examples 1-16, except that comparative examples 12 and 13 used a titanium silicalite TS-1 (having a titanium oxide content of 2.5 wt% prepared according to the method described in Zeolite, 1992, Vol. 12, pp. 943-950) and comparative example 14 used a hollow titanium silicalite (having a titanium oxide content of 2.5 wt% prepared according to the method disclosed in CN 1132699C).
Comparative examples 1 to 3
Thioethers were oxidized in the same manner as in examples 1-16, except that multi-walled carbon nanotubes A, B and C were used as catalysts, respectively, and the results of the experiments are shown in Table 2.
TABLE 2
Figure BDA0001363970400000271
The results in table 2 demonstrate that the heteroatom-containing nanocarbon material prepared by the method of the present invention shows significantly improved catalytic activity when used as a catalyst for thioether oxidation reaction, and can achieve higher thioether conversion rate and product selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (66)

1. A method for oxidizing a thioether, comprising contacting, under oxidation reaction conditions, a thioether, an oxidizing agent, and optionally a solvent, with a heteroatom-containing nanocarbon material, wherein the heteroatom-containing nanocarbon material is prepared by a process comprising the steps of:
(1) contacting a raw material nano-carbon material with at least one oxidant at the temperature of 10-40 ℃ to obtain an oxidized nano-carbon material, wherein the oxidant is HNO3And H2SO4The oxidant is HNO3And H2SO4And HNO3And H2SO4In a molar ratio of 1: 1-10;
(2) dispersing the nano-carbon material subjected to oxidation treatment and at least one organic base in water, and reacting the obtained aqueous dispersion in a closed container to obtain the nano-carbon material subjected to organic base treatment, wherein the organic base is amine and/or quaternary ammonium base, and the temperature of the aqueous dispersion is kept within the range of 110-180 ℃ in the reaction process; and
(3) the nano carbon material treated by the organic alkali is roasted in an inactive atmosphere at the temperature of 550-1200 ℃.
2. The method according to claim 1, wherein in step (1), HNO3And H2SO4In a molar ratio of 1: 1.5-8.
3. The process according to claim 2, wherein in step (1), HNO3And H2SO4In a molar ratio of 1: 2-4.
4. The method according to any one of claims 1 to 3, wherein the oxidizing agent is used in an amount of 5 to 2000 parts by weight, relative to 100 parts by weight of the raw nanocarbon material, in step (1).
5. The method according to claim 4, wherein the oxidizing agent is used in an amount of 10 to 1000 parts by weight, relative to 100 parts by weight of the raw nanocarbon material in step (1).
6. The method according to any one of claims 1 to 3, wherein, in step (1), the raw nanocarbon material is contacted with the oxidizing agent in the presence of ultrasonic waves.
7. The method of claim 6, wherein the frequency of the ultrasonic waves is 25-100 kHz.
8. The method of claim 7, wherein the frequency of the ultrasonic waves is 40-80 kHz.
9. The method according to any one of claims 1 to 3, wherein in step (1), the contacting is carried out in water.
10. The method as claimed in claim 9, wherein the amount of water is 500-10000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
11. The method as claimed in claim 10, wherein the amount of water is 1000-8000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
12. The method as claimed in claim 11, wherein the amount of water used is 4000-6000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
13. The process according to any one of claims 1 to 3, wherein in step (1), the contacting is carried out at a temperature of 20 to 40 ℃.
14. The method of claim 13, wherein in step (1), the duration of the contacting is 0.5-8 hours.
15. The method of claim 14, wherein in step (1), the duration of the contacting is 1-4 hours.
16. The method according to any one of claims 1 to 3, wherein the step (1) further comprises separating a solid substance from the mixture obtained by the contacting, and drying the solid substance to obtain the oxidation-treated nanocarbon material.
17. The method according to claim 16, wherein, in step (1), the drying is performed at a temperature of 80-180 ℃.
18. The method as claimed in claim 17, wherein the drying is performed at a temperature of 100-160 ℃ in step (1).
19. The method according to claim 16, wherein, in step (1), the duration of the drying is 0.5 to 24 hours.
20. The method according to claim 19, wherein in step (1), the duration of the drying is 1-20 hours.
21. The method according to claim 20, wherein in step (1), the duration of the drying is 6-12 hours.
22. The method according to claim 1, wherein, in the step (2), the oxidation-treated nanocarbon material: the weight ratio of the organic base is 1: in the range of 0.1-20.
23. The method according to claim 22, wherein, in the step (2), the oxidation-treated nanocarbon material: the weight ratio of water is 1: in the range of 5-200.
24. The method according to claim 23, wherein, in the step (2), the nano-carbon material subjected to the oxidation treatment: the weight ratio of water is 1: in the range of 5-100.
25. The method according to claim 24, wherein, in the step (2), the oxidation-treated nanocarbon material: the weight ratio of water is 1: in the range of 10-50.
26. The process of any one of claims 1 and 22-25, wherein in step (2), the organic base is selected from the group consisting of a compound of formula II, a compound of formula III, a compound of formula IV, and a general formula R15(NH2)2A substance represented by R15Is C1-C6Alkylene or C6-C12An arylene group of (a) to (b),
Figure FDA0003451362510000041
in the formula II, R4、R5、R6And R7Each is C1-C20Alkyl or C6-C12Aryl of (a);
Figure FDA0003451362510000042
in the formula III, R8、R9And R10Are each H, C1-C6Alkyl or C6-C12And R is an aryl group of8、R9And R10Not H at the same time;
Figure FDA0003451362510000043
in the formula III, R11、R12And R13Each is-R14OH, hydrogen or C1-C6And R is alkyl of11、R12And R13At least one of which is-R14OH，R14Is C1-C4An alkylene group of (a).
27. The method according to claim 1, wherein in step (2), the duration of the reaction is in the range of 1-24 hours.
28. The process of claim 27, wherein in step (2), the duration of the reaction is in the range of 4-20 hours.
29. The process of claim 28, wherein in step (2), the duration of the reaction is in the range of 8-16 hours.
30. The method according to any one of claims 1 and 27 to 29, wherein step (2) further comprises separating solid matter from the mixture obtained from the reaction and drying the separated solid matter.
31. The method according to claim 30, wherein, in the step (2), the drying is performed at a temperature of 50-200 ℃.
32. The method according to claim 31, wherein, in the step (2), the drying is performed at a temperature of 80-180 ℃.
33. The method as claimed in claim 32, wherein, in the step (2), the drying is carried out at a temperature of 100 ℃ and 160 ℃.
34. The method according to claim 30, wherein in step (2), the duration of the drying is 0.5 to 48 hours.
35. The method according to claim 34, wherein in step (2), the duration of the drying is 3-24 hours.
36. The method according to claim 35, wherein in step (2), the duration of the drying is 5-12 hours.
37. The method as claimed in claim 1, wherein, in the step (3), the calcination is carried out at a temperature of 600-1200 ℃.
38. The method as claimed in claim 37, wherein, in the step (3), the calcination is carried out at a temperature of 700 ℃ and 1100 ℃.
39. The method of any one of claims 1, 37 and 38, wherein in step (3), the duration of the roasting is 2-24 hours.
40. The method as claimed in claim 39, wherein, in the step (3), the duration of the roasting is 2-12 hours.
41. The method as claimed in claim 40, wherein, in the step (3), the duration of the roasting is 2.5-5 hours.
42. The method according to claim 1, wherein, in the step (3), the inert atmosphere is an atmosphere formed of nitrogen and/or a group zero gas.
43. The method according to claim 1, wherein the raw nanocarbon material contains an oxygen element, a hydrogen element and a carbon element, and the content of the oxygen element is 0.1 to 1% by weight, the content of the hydrogen element is 0.1 to 1% by weight and the content of the carbon element is 98 to 99.8% by weight, in terms of element, based on the total amount of the raw nanocarbon material.
44. The method according to claim 43, wherein the content of the oxygen element is 0.15 to 0.8% by weight, the content of the hydrogen element is 0.2 to 0.9% by weight, and the content of the carbon element is 98.3 to 99.65% by weight, in terms of element, based on the total amount of the raw nanocarbon material.
45. The method according to claim 44, wherein the content of the oxygen element is 0.25 to 0.6% by weight, the content of the hydrogen element is 0.4 to 0.6% by weight, and the content of the carbon element is 98.8 to 99.35% by weight, in terms of element, based on the total amount of the raw nanocarbon material.
46. The method according to any one of claims 1 and 43 to 45, wherein the raw nanocarbon material has an X-ray photoelectron spectrum obtained by measuring the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum
Figure FDA0003451362510000071
The content of oxygen element determined by the peak of the group is 0.1-0.5 mol%, and the content of oxygen element determined by the peak corresponding to C-O group
Figure FDA0003451362510000072
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-1: 1.
47. the method according to claim 46, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to a total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum
Figure FDA0003451362510000073
The content of oxygen element determined by the peak of the radical is 0.2-0.45 mol%.
48. Root of herbaceous plantA method as claimed in claim 47, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum
Figure FDA0003451362510000074
The content of oxygen element determined by the peak of the radical is 0.3-0.45 mol%.
49. The method according to claim 46, wherein in the X-ray photoelectron spectrum of the raw material nanocarbon material, the content of oxygen element determined from a peak corresponding to a C-O group and the content of oxygen element determined from a peak corresponding to a C-O group are determined based on the total amount of surface elements of the raw material nanocarbon material determined from the X-ray photoelectron spectrum
Figure FDA0003451362510000081
The molar ratio of the content of oxygen element determined by the peak of the group is 0.3-0.9: 1.
50. the method according to claim 49, wherein in the X-ray photoelectron spectrum of the raw material nanocarbon material, the content of oxygen element determined from a peak corresponding to a C-O group and the content of oxygen element determined from a peak corresponding to a C-O group are determined based on the total amount of surface elements of the raw material nanocarbon material determined from the X-ray photoelectron spectrum
Figure FDA0003451362510000082
The molar ratio of the oxygen content determined by the peak of the radical is 0.75-0.85: 1.
51. the method of any one of claims 1 and 43-45, wherein the starting nanocarbon material has an X-ray photoelectron spectrum corresponding to that of X-ray photoelectron spectroscopy
Figure FDA0003451362510000083
The content of oxygen determined by the peak of the radical corresponds to
Figure FDA0003451362510000084
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-2: 1.
52. the method according to claim 51, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to that of the sample material nanocarbon
Figure FDA0003451362510000085
The content of oxygen determined by the peak of the radical corresponds to
Figure FDA0003451362510000086
The molar ratio of the content of oxygen element determined by the peak of the group is 0.5-1.8: 1.
53. the method of claim 52, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to that of the sample nanocarbon
Figure FDA0003451362510000087
The content of oxygen determined by the peak of the radical corresponds to
Figure FDA0003451362510000088
The molar ratio of the oxygen content determined by the peak of the radical is 0.8-1.2: 1.
54. the method of any one of claims 1-3, 22-25, 27-29, 37, 38, and 42-45, wherein the feedstock nanocarbon material is carbon nanotubes.
55. The method of claim 54, wherein the feedstock nanocarbon material is multi-walled carbon nanotubes.
56. The method of claim 55, wherein the multi-walled carbon nanotubes have a specific surface area of 50-500m2/g。
57. The method of claim 56, wherein said multi-walled carbon nanotubes have a specific surface area of 70-300m2/g。
58. The method of claim 57, wherein said multi-walled carbon nanotubes have a specific surface area of 80-200m2/g。
59. The process according to claim 1, wherein the molar ratio of thioether to peroxide is 1: 0.1-2.
60. The method of claim 59, wherein the molar ratio of thioether to peroxide is from 1: 0.5-1.5.
61. The method of claim 60, wherein the molar ratio of thioether to peroxide is from 1: 0.6-1.
62. The method of any one of claims 1 and 59-61, wherein the sulfide is dimethyl sulfide and/or benzyl sulfide.
63. The process of any one of claims 1 and 59 to 61, wherein the oxidizing agent is one or more of hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, cyclohexyl hydroperoxide, peroxyacetic acid and peroxypropionic acid.
64. The method of any one of claims 1 and 59-61, wherein the oxidation reaction conditions comprise: the temperature is 10-100 ℃, and the pressure is 0-3MPa in gauge pressure.
65. The method of claim 64, wherein the oxidation reaction conditions comprise: the temperature is 20-60 ℃, and the pressure is 0-1.5MPa in gauge pressure.
66. The method of claim 65, wherein the oxidation reaction conditions comprise: the temperature is 30-50 ℃.
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