CN111099572A - Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon - Google Patents
Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon Download PDFInfo
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Abstract
The present disclosure relates to a carbon oxide-based material, a method of oxidizing a carbon-based material, and a method of catalytically oxidizing a cyclic hydrocarbon, the method of catalytically oxidizing a cyclic hydrocarbon comprising: subjecting a cyclic hydrocarbon and an oxidizing agent to a contact reaction in the presence of a catalyst, wherein the catalyst contains a carbon oxide-based material. The method adopts a special carbon oxide-based material to catalyze the oxidation reaction of the cyclic hydrocarbon, can realize the selective oxidation of the cyclic hydrocarbon under mild conditions, and has high selectivity of ketones and dicarboxylic acids in the product.
Description
Technical Field
The present disclosure relates to a carbon oxide-based material, a method of oxidizing a carbon-based material, and a method of catalytically oxidizing cyclic hydrocarbons.
Background
Carbon-based materials include carbon nanotubes, activated carbon, graphite, graphene, fullerenes, carbon nanofibers, nanodiamonds, and the like. Scientific research on nanocarbon catalysis began in the last 90 s of the century. Researches show that the surface chemical properties of the nano-carbon material (mainly carbon nano-tubes and graphene) can be flexibly regulated, and saturated and unsaturated functional groups containing heteroatoms such as oxygen, nitrogen and the like can be modified on the surface of the nano-carbon material, so that the nano-carbon material has certain acid-base properties and redox capability, and can be directly used as a catalyst material. Research and development of new catalytic materials related to fullerene (carbon nano tube) and broadening of the application of the new catalytic materials in the fields of petrochemical industry, fine chemical industry and the like have profound theoretical significance and huge potential application prospects.
Disclosure of Invention
An object of the present disclosure is to provide a carbon oxide-based material having excellent catalytic performance for selective oxidation of cyclic hydrocarbons, a method for oxidation of a carbon-based material, and a method for catalytic oxidation of cyclic hydrocarbons.
To achieve the above object, a first aspect of the present disclosure: provided is a carbon oxide-based material characterized in that the carbon oxide-based material has an oxygen content of 30% by weight or less and a carbon content of 65% by weight or more, based on the total weight of the carbon oxide-based material; the average particle size of the carbon oxide-based material is 3-5000 nm;
in the carbon oxide-based material, the weight of particles with the particle size of 3-20 nm accounts for 0.1-50% of the total weight of the carbon oxide-based material, and the proportion is preferably 1-20%.
In a second aspect of the present disclosure: provided is a method for oxidizing a carbon-based material, the method including the steps of:
a. mixing a carbon source, an inorganic acid and an organic acid, reacting at 20-300 ℃, preferably 50-200 ℃, for 0.1-72 hours, preferably 1-24 hours, and then drying to obtain a solid material;
b. b, roasting the solid material obtained in the step a under a protective atmosphere;
the carbon source is coke, graphite or activated carbon, or a combination of two or three of the above.
Optionally, in step a, the weight ratio of the carbon source, the inorganic acid and the organic acid is 1: (0.1-10): (0.1 to 10), preferably 1: (0.2-5): (0.2-5);
the inorganic acid is nitric acid, sulfuric acid, perchloric acid or phosphoric acid, or a combination of two or three of the nitric acid, the sulfuric acid, the perchloric acid or the phosphoric acid;
the organic acid is citric acid, malic acid, glutamic acid, naphthenic acid, gluconic acid, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, salicylic acid, tartaric acid, ascorbic acid, cinnamic acid, benzoic acid, salicylic acid, caffeic acid, pseudolaric acid, chlorogenic acid, pyruvic acid, tetronic acid, lactic acid, sorbic acid, fumaric acid and the like, or a combination of two or three of the above.
Optionally, in step b, the protective atmosphere is a nitrogen atmosphere, a helium atmosphere, an argon atmosphere, or a neon atmosphere;
the roasting conditions are as follows: the temperature is 300-1200 ℃, preferably 400-800 ℃, and the time is 1-48 h, preferably 2-24 h.
A third aspect of the disclosure: there is provided a carbon oxide based material prepared by the method according to the second aspect of the present disclosure.
A fourth aspect of the present disclosure: there is provided a process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: subjecting a cyclic hydrocarbon and an oxidizing agent to a contact reaction in the presence of a catalyst, wherein the catalyst contains the carbon oxide-based material according to the first or third aspect of the present disclosure.
Optionally, the reaction is performed in a slurry bed reactor, and the amount of the catalyst is 10 to 100mg, preferably 20 to 60mg, based on 10mL of the cyclic hydrocarbon.
Optionally, the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the cyclic hydrocarbon is 0.01-10 h-1Preferably 0.05 to 2 hours-1。
Optionally, the method further comprises: the reaction is carried out in the presence of an initiator; the initiator is tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, or the combination of two or three of the above substances;
the dosage of the initiator is 0.01-0.3 mL based on 10mL of the cyclic hydrocarbon.
Optionally, the oxidant is an oxygen-containing gas, preferably air or oxygen;
the molar ratio of the cyclic hydrocarbon to oxygen in the oxygen-containing gas is 1: (1-5).
Optionally, the cyclic hydrocarbon is one selected from substituted or unsubstituted monocycloparaffins of C6 to C12 and substituted or unsubstituted dicycloalkanes of C8 to C16, preferably cyclohexane or methylcyclopentane.
Optionally, the reaction conditions are: the temperature is 50-200 ℃, and preferably 60-180 ℃; the time is 1-72 h, preferably 2-24 h; the pressure is 0 to 20MPa, preferably 0 to 10 MPa.
Through the technical scheme, the special carbon source is oxidized to obtain the carbon oxide-based material, and the carbon oxide-based material has a proper particle size and excellent catalytic performance. The oxidized carbon-based material is used as a catalyst to catalyze the oxidation reaction of the cyclic hydrocarbon, so that the selective oxidation of the cyclic hydrocarbon can be realized under mild conditions, and the selectivity of the ketone and the dicarboxylic acid in the product is high.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure: providing a carbon oxide-based material, wherein the carbon oxide-based material has an oxygen content of 30 wt% or less and a carbon content of 65 wt% or more, based on the total weight of the carbon oxide-based material; in addition, the carbon oxide-based material may further contain a small amount of impurity elements such as N, S, P, Cl, H, etc., the total content of the impurity elements being 5% by weight or less.
According to the present disclosure, the carbon oxide-based material has a suitable particle size distribution, and the average particle size thereof may be 3 to 5000 nm; in the carbon oxide-based material, the weight of particles with the particle size of 3-20 nm accounts for 0.1-50% of the total weight of the carbon oxide-based material, and the proportion is preferably 1-20%. 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.
In a second aspect of the present disclosure: provided is a method for oxidizing a carbon-based material, the method including the steps of:
a. mixing a carbon source, an inorganic acid and an organic acid, reacting at 20-300 ℃, preferably 50-200 ℃, for 0.1-72 hours, preferably 1-24 hours, and then drying to obtain a solid material;
b. b, roasting the solid material obtained in the step a under a protective atmosphere;
the carbon source is coke, graphite or activated carbon, or a combination of two or three of the above.
The source of the carbon source is not particularly limited in the present disclosure, and the carbon content of the carbon source may be 80 to 100 wt%.
According to the present disclosure, in the step a, the weight ratio of the carbon source, the inorganic acid and the organic acid may be 1: (0.1-10): (0.1 to 10), preferably 1: (0.2-5): (0.2-5). The inorganic acid may be, for example, nitric acid, sulfuric acid, perchloric acid, or phosphoric acid, or a combination of two or three thereof; the organic acid may be, for example, citric acid, malic acid, glutamic acid, naphthenic acid, gluconic acid, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, salicylic acid, tartaric acid, ascorbic acid, cinnamic acid, benzoic acid, salicylic acid, caffeic acid, pseudolaric acid, chlorogenic acid, pyruvic acid, tetronic acid, lactic acid, sorbic acid, fumaric acid, or the like, or a combination of two or three of them. The drying conditions may be: the temperature is 120-180 ℃, and the time is 2-12 h.
According to the present disclosure, in the step b, the protective atmosphere may be a nitrogen atmosphere, a helium atmosphere, an argon atmosphere, or a neon atmosphere. The roasting conditions can be as follows: the temperature is 300-1200 ℃, preferably 400-800 ℃, and the time is 1-48 h, preferably 2-24 h.
A third aspect of the disclosure: there is provided a carbon oxide based material prepared by the method according to the second aspect of the present disclosure. The carbon oxide-based material has an oxygen content of 30 wt% or less and a carbon content of 65 wt% or more, based on the total weight of the carbon oxide-based material; in addition, the carbon oxide-based material may further contain a small amount of impurity elements such as N, S, P, Cl, H, etc., the total content of the impurity elements being 5% by weight or less. The carbon oxide-based material has a proper particle size distribution, and the average particle size of the carbon oxide-based material can be 3-5000 nm; further, in the carbon oxide-based material, the weight of particles with a particle size of 3 to 20nm in the carbon oxide-based material accounts for 0.1 to 50 percent of the total weight of the carbon oxide-based material, and preferably 1 to 20 percent of the total weight of the carbon oxide-based material.
The oxidized carbon-based material of the present disclosure has a suitable particle size distribution and excellent catalytic performance, and is particularly suitable for catalytic oxidation of cyclic hydrocarbons. Accordingly, the fourth aspect of the present disclosure: there is provided a process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: subjecting a cyclic hydrocarbon and an oxidizing agent to a contact reaction in the presence of a catalyst, wherein the catalyst contains the carbon oxide-based material according to the first or third aspect of the present disclosure.
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 an alternative embodiment of the present disclosure, the reaction may be carried out in a slurry bed reactor. In this case, the amount of the catalyst may be appropriately selected according to the amounts of the cyclic hydrocarbon and the oxidizing agent, and for example, the amount of the catalyst may be 20 to 100mg, preferably 40 to 60mg, based on 10mL of the cyclic hydrocarbon.
In another alternative embodiment of the present disclosure, the reaction may be carried out in a fixed bed reactor. In this case, the weight hourly space velocity of the cyclic hydrocarbon may be, for example, 0.01 to 10 hours-1Preferably 0.05 to 2 hours-1。
According to the present disclosure, the cyclic hydrocarbon may be one selected from substituted or unsubstituted monocycloparaffins of C5 to C12 and substituted or unsubstituted bicycloalkanes of C8 to C16. Further, when the cyclic hydrocarbon is one selected from the group consisting of a substituted monocycloparaffin of C5 to C12 and a substituted bicycloalkane of C8 to C16, the substituent thereof may be a halide or a methyl group. For example, the cyclic hydrocarbon may be cyclohexane, cyclopentane, methylcyclohexane, halogenated cyclohexane, methylcyclopentane, halogenated cyclopentane, and the like, with cyclohexane being preferred.
The oxidizing agent is an oxidizing agent conventionally used in the art according to the present disclosure, and for example, the oxidizing agent may be an oxygen-containing gas, and further may be air or oxygen. The molar ratio of the cyclic hydrocarbon to oxygen in the oxygen-containing gas may be 1: (1-5).
According to the present disclosure, in order to promote the reaction, further improve the conversion rate of the raw material and the selectivity of the target product, the method may further include: the reaction is carried out in the presence of an initiator. The initiator may be an initiator conventionally used in the art, for example, the initiator may be t-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, or a combination of two or three thereof. The initiator can achieve the purpose under the condition of small dosage, for example, the dosage of the initiator can be 0.01-0.3 mL based on 10mL of the cyclic hydrocarbon.
According to the present disclosure, the conditions of the reaction may be: the temperature is 50-200 ℃, and preferably 60-180 ℃; the time is 1-72 h, preferably 2-24 h; the pressure is 0 to 20MPa, preferably 0 to 10 MPa. In order to make the reaction more sufficient, it is preferable that the contact reaction is carried out under stirring.
The oxidized carbon-based material is used as a catalyst to catalyze the oxidation reaction of the cyclic hydrocarbon, so that the selective oxidation of the cyclic hydrocarbon can be realized under mild conditions, and the selectivity of ketones and dicarboxylic acids in the product is high.
The present disclosure is described in detail below with reference to examples, but the scope of the present disclosure is not limited thereby.
Preparation examples 1 to 5 are illustrative of the carbon oxide-based material and the method for preparing the same according to the present disclosure.
In the preparation examples, the coke was obtained from the petrochemical Yanshan division of China, and had a carbon content of 91.8 wt%, an ash content of 6.8 wt%, a sulfur content of 0.3 wt%, and a volatile matter content of 1.1 wt%. The graphite is from chemical reagent of national drug group, the carbon content is 99.9 wt%, and the ash content is 0.1 wt%. Average particle size of the carbon oxide-based Material TECNAIG available from FEI2Transmission 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 proportion of particles with the particle size of 3-20 nm in the carbon oxide material is separated by adopting a membrane of the Jinan Borna Biotechnology Limited companyAnd (3) separating small particles within the range of 3-20 nm by using a device (type BONA-GM-08), and calculating the ratio of the weight of the small particles with the particle size within the range of 3-20 nm to the total mass of the carbon oxide-based material according to the weight of the small particles with the particle size within the range of 3-20 nm and the total mass of the carbon oxide-based material.
Preparation of example 1
Adding 10g of coke into a reflux flask under normal pressure, adding 20g of nitric acid and 10g of citric acid, carrying out reflux reaction for 6h at 60 ℃, drying for 5h at 120 ℃, transferring the solid material into a crucible, putting the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 500 ℃ in a nitrogen atmosphere, and roasting for 8h to obtain an oxidized carbon-based material C1, wherein the average particle size of the oxidized carbon-based material C1 is 600nm, and the particles with the particle size of 3-20 nm account for 8 wt%.
Preparation of example 2
Under normal pressure, adding 10g of coke into a reflux flask, adding 10g of perchloric acid and 20g of oxalic acid, refluxing for 6h at 80 ℃, drying for 6h at 120 ℃, transferring the solid material into a crucible, putting the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 600 ℃ in a nitrogen atmosphere, and roasting for 8h to obtain an oxidized carbon-based material C2, wherein the average particle size of the oxidized carbon-based material C2 is 300nm, and the particles with the particle size of 3-20 nm account for 12 wt%.
Preparation of example 3
Under normal pressure, adding 10g of graphite into a reflux flask, adding 5g of phosphoric acid and 50g of naphthenic acid, refluxing for 6h at 70 ℃, drying for 3h at 150 ℃, transferring the solid material into a crucible, putting the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 800 ℃ in a nitrogen atmosphere, and roasting for 8h to obtain an oxidized carbon-based material C3, wherein the average particle size of the oxidized carbon-based material C3 is 1000nm, and the particles with the particle size of 3-20 nm account for 20 wt%.
Preparation of example 4
Under normal pressure, adding 10g of coke into a reflux flask, adding 60g of nitric acid and 80g of citric acid, refluxing for 6 hours at 90 ℃, drying for 8 hours at 120 ℃, transferring the solid material into a crucible, putting the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 500 ℃ in a nitrogen atmosphere, and roasting for 8 hours to obtain an oxidized carbon-based material C4, wherein the average particle size of the oxidized carbon-based material C4 is 500nm, and the particles with the particle size of 3-20 nm account for 25 wt%.
Preparation of example 5
Under normal pressure, adding 10g of coke into a reflux flask, adding 20g of nitric acid and 10g of citric acid, carrying out reflux reaction at 140 ℃ for 30h, drying at 160 ℃ for 2h, transferring the solid material into a crucible, putting into a high-temperature electric furnace, removing air by using nitrogen, heating to 1000 ℃ in a nitrogen atmosphere, and roasting for 8h to obtain an oxidized carbon-based material C5, wherein the average particle size of the oxidized carbon-based material C5 is 1500nm, and the particles with the particle size of 3-20 nm account for 0.8 wt%.
Examples 1-11 are presented to illustrate methods of catalytically oxidizing cyclic hydrocarbons using the oxidized carbon-based materials of the present disclosure. Comparative examples 1-2 are presented to illustrate processes for the catalytic oxidation of cyclic hydrocarbons using catalysts different from the present disclosure.
In the following examples and comparative examples, the oxidation products were analyzed by gas chromatography (GC: Agilent, 7890A) and gas chromatography-mass spectrometer (GC-MS: Thermo Fisher Trace ISQ). Conditions of gas chromatography: nitrogen carrier gas, temperature programmed at 140K: 60 ℃, 1 minute, 15 ℃/minute, 180 ℃, 15 minutes; split ratio, 10: 1; the injection port temperature is 300 ℃; detector temperature, 300 ℃. On the basis, the conversion rate of raw materials and the selectivity of target products are calculated by respectively adopting the following formulas:
the conversion of cyclic hydrocarbon = (the molar amount of cyclic hydrocarbon added before the reaction-the molar amount of cyclic hydrocarbon remaining after the reaction)/the molar amount of cyclic hydrocarbon added before the reaction × 100%;
target product selectivity ═ molar amount of target product formed after the reaction)/molar amount of cyclic hydrocarbon added before the reaction × 100%.
Example 1
50mg of the oxidized carbon-based material C1 as a catalyst and 10mL of cyclohexane were charged into a 250mL autoclave, and then 0.1mL of t-butyl hydroperoxide (TBHP) as an initiator was added dropwise to the above system, and the system was sealed, and after stirring the mixture at 130 ℃ and 2.0MPa with introduction of oxygen (molar ratio of oxygen to cyclohexane: 5: 1) for 5 hours, the mixture was cooled, sampled at reduced pressure, centrifuged and filtered to separate the catalyst, and the results of analyzing the oxidized product are shown in Table 1.
Examples 2 to 5
Cyclohexane was catalytically oxidized by the method of example 1, except that the same amount of the oxidized carbon-based materials C2 to C5 was used instead of C1, respectively. The results of the oxidation product analysis are shown in Table 1.
Example 6
60mg of the oxidized carbon-based material C1 as a catalyst and 10mL of cyclohexane were charged into a 250mL autoclave, and then 0.2mL of cumyl hydroperoxide as an initiator was added dropwise to the above system, sealed, and the mixture was stirred at 100 ℃ and 2.5MPa by introducing oxygen (molar ratio of oxygen to cyclohexane was 2: 1) for 8 hours, and after cooling, pressure-releasing sampling, the catalyst was separated by centrifugation and filtration, and the results of analyzing the oxidized product are shown in Table 1.
Example 7
10mg of the oxidized carbon-based material C1 as a catalyst and 10mL of cyclohexane were charged into a 250mL autoclave, and then 0.1mL of t-butylhydroperoxide as an initiator was added dropwise to the above system, sealed, and the mixture was stirred at 130 ℃ and 2.0MPa with introduction of oxygen (molar ratio of oxygen to cyclohexane was 4: 1) for 5 hours, and after cooling, pressure-releasing sampling, the catalyst was separated by centrifugation and filtration, and the results of analysis of the oxidized product are shown in Table 1.
Example 8
80mg of the oxidized carbon-based material C1 as a catalyst and 10mL of cyclohexane were charged into a 250mL autoclave, and then 0.1mL of t-butylhydroperoxide as an initiator was added dropwise to the above system, sealed, and the mixture was stirred at 130 ℃ and 2.0MPa with introduction of oxygen (molar ratio of oxygen to cyclohexane was 1: 1) for 5 hours, and after cooling, pressure-releasing sampling, the catalyst was separated by centrifugation and filtration, and the results of analysis of the oxidized product are shown in Table 1.
Example 9
50mg of the oxidized carbon-based material C1 was packed in a fixed bed reactor as a catalyst, cyclohexane and t-butyl hydroperoxide were fed into the reactor, oxygen (molar ratio of oxygen to cyclohexane 5: 1) was fed, the amount of t-butyl hydroperoxide was 0.1mL based on 10mL of cyclohexane, and the weight hourly space velocity of cyclohexane was 1h-1The results of the analysis of the oxidation products after 5 hours at 130 ℃ and 2.0MPa are shown in Table 1.
Example 10
Cyclohexane was catalytically oxidized according to the procedure of example 1, except that t-butyl hydroperoxide was not added as an initiator. The results of the oxidation product analysis are shown in Table 1.
Example 11
50mg of the oxidized carbon-based material C1 as a catalyst and 10mL of methylcyclopentane were charged into a 250mL autoclave, then 0.1mL of t-butylhydroperoxide as an initiator was added dropwise to the above system, the system was sealed, oxygen (molar ratio of oxygen to cyclohexane 5: 1) was introduced, the mixture was stirred at 130 ℃ and 2.0MPa for 5 hours, and after cooling, pressure-releasing sampling, the catalyst was separated by centrifugation and filtration, and the result of analysis of the oxidized product was: the methylcyclopentane conversion was 12.7%, the methylcyclopentanone selectivity was 32%, and the dicarboxylic acid selectivity was 36%.
Comparative example 1
Cyclohexane was catalytically oxidized by the method of example 1, except that the carbon oxide-based material C1 was not used as a catalyst. The results of the oxidation product analysis are shown in Table 1.
Comparative example 2
Cyclohexane was catalytically oxidized by the method of example 1, except that the same amount of coke was used as a catalyst instead of the carbon oxide-based material C1. The results of the oxidation product analysis are shown in Table 1.
TABLE 1
As can be seen from table 1, the use of the carbon oxide-based material of the present disclosure as a catalyst enables selective oxidation of cyclic hydrocarbons under mild conditions, and the conversion of raw materials and the selectivity of target products are higher.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the 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 (12)
1. A carbon oxide-based material, characterized in that the carbon oxide-based material has an oxygen content of 30% by weight or less and a carbon content of 65% by weight or more, based on the total weight of the carbon oxide-based material; the average particle size of the carbon oxide-based material is 3-5000 nm;
in the carbon oxide-based material, the weight of particles with the particle size of 3-20 nm accounts for 0.1-50% of the total weight of the carbon oxide-based material, and the proportion is preferably 1-20%.
2. A method for oxidizing a carbon-based material, comprising the steps of:
a. mixing a carbon source, an inorganic acid and an organic acid, reacting at 20-300 ℃, preferably 50-200 ℃, for 0.1-72 hours, preferably 1-24 hours, and then drying to obtain a solid material;
b. b, roasting the solid material obtained in the step a under a protective atmosphere;
the carbon source is coke, graphite or activated carbon, or a combination of two or three of the above.
3. The method according to claim 2, wherein in the step a, the weight ratio of the carbon source, the inorganic acid and the organic acid is 1: (0.1-10): (0.1 to 10), preferably 1: (0.2-5): (0.2-5);
the inorganic acid is nitric acid, sulfuric acid, perchloric acid or phosphoric acid, or a combination of two or three of the nitric acid, the sulfuric acid, the perchloric acid or the phosphoric acid;
the organic acid is citric acid, malic acid, glutamic acid, naphthenic acid, gluconic acid, oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, salicylic acid, tartaric acid, ascorbic acid, cinnamic acid, benzoic acid, salicylic acid, caffeic acid, pseudolaric acid, chlorogenic acid, pyruvic acid, tetronic acid, lactic acid, sorbic acid or fumaric acid, or a combination of two or three of the above.
4. The method according to claim 2, wherein in step b, the protective atmosphere is a nitrogen atmosphere, a helium atmosphere, an argon atmosphere, or a neon atmosphere;
the roasting conditions are as follows: the temperature is 300-1200 ℃, preferably 400-800 ℃, and the time is 1-48 h, preferably 2-24 h.
5. A carbon oxide-based material prepared by the method of any one of claims 2 to 4.
6. A process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: a cyclic hydrocarbon and an oxidizing agent are subjected to a contact reaction in the presence of a catalyst, wherein the catalyst contains the carbon oxide-based material according to claim 1 or 5.
7. The process according to claim 6, wherein the reaction is carried out in a slurry bed reactor, and the amount of the catalyst is 10 to 100mg, preferably 20 to 60mg, based on 10mL of the cyclic hydrocarbon.
8. The method of claim 6, wherein the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the cyclic hydrocarbon is 0.01-10 h-1Preferably 0.05 to 2 hours-1。
9. The method of claim 6, wherein the method further comprises: the reaction is carried out in the presence of an initiator; the initiator is tert-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide or peroxypropionic acid, or the combination of two or three of the above substances;
the dosage of the initiator is 0.01-0.3 mL based on 10mL of the cyclic hydrocarbon.
10. The process according to claim 6, wherein the oxidant is an oxygen-containing gas, preferably air or oxygen;
the molar ratio of the cyclic hydrocarbon to oxygen in the oxygen-containing gas is 1: (1-5).
11. The method according to claim 6, wherein the cyclic hydrocarbon is one selected from the group consisting of a substituted or unsubstituted monocycloparaffin of C6-C12 and a substituted or unsubstituted bicycloalkane of C8-C16, preferably cyclohexane or methylcyclopentane.
12. The process of claim 6, wherein the reaction conditions are: the temperature is 50-200 ℃, and preferably 60-180 ℃; the time is 1-72 h, preferably 2-24 h; the pressure is 0 to 20MPa, preferably 0 to 10 MPa.
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