CN111229196B - Catalyst, process for producing the same, and process for catalytic oxidation of hydrocarbons - Google Patents
Catalyst, process for producing the same, and process for catalytic oxidation of hydrocarbons Download PDFInfo
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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Abstract
The invention relates to the field of chemical industry, and discloses a catalyst, a preparation method thereof and a catalytic oxidation method of hydrocarbons. The preparation method of the catalyst comprises the following steps: the organic acid is calcined under oxygen-free conditions to obtain the catalyst. Wherein the organic acid is at least one selected from naphthenic acid, amino acid, citric acid, malic 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 and fumaric acid. In the presence of the catalyst prepared by the method, the catalytic oxidation of the hydrocarbons can obtain higher hydrocarbon conversion rate and higher ketone selectivity and dicarboxylic acid selectivity.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for preparing a catalyst, the catalyst prepared by the method and a catalytic oxidation method of hydrocarbons.
Background
Adipic acid, also known as ethanedicarboxylic acid, commonly known as adipic acid, is the most valuable diacid of the aliphatic diacids. It can be widely used in the manufacture of nylon-66, plasticizer, food additive and fiber, and the worldwide annual output reaches 2.2X 10 6 Ton and has a growing trend.
Cyclohexanone is an important chemical raw material, a main intermediate for producing nylon, caprolactam and adipic acid, and is also an important industrial solvent, such as for paint.
From the viewpoint of environmental protection and increasing economic benefits, it is very necessary and meaningful work to research and develop clean and efficient catalyst for the catalytic selective oxidation of cyclohexane to produce cyclohexanone and adipic acid. Much work has been done by many scientific researchers, and oxygen is regarded as an inexpensive, readily available, environmentally friendly oxidant.
The oxidation of cyclohexane to prepare adipic acid is often accompanied by the production of low-carbon acid by-products such as glutaric acid, succinic acid, valeric acid, and the like. A great deal of work has been carried out on the selective oxidation of cyclohexane and its intermediates, with many positive results, but still facing many difficulties.
The existing cyclohexane oxidation methods have the problems of low conversion rate and poor selectivity, and a new cyclohexane oxidation method is needed.
Disclosure of Invention
The invention aims to overcome the problems of low hydrocarbon conversion rate and low ketone and dicarboxylic acid selectivity in the method for preparing ketones and dicarboxylic acids by catalytic oxidation of hydrocarbons in the prior art, and provides a novel catalyst preparation method and a catalyst prepared by the method.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a catalyst, the method comprising: roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is at least one selected from naphthenic acid, amino acid, citric acid, malic 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 and fumaric acid.
In a second aspect, the invention provides a catalyst prepared by the above method.
In a third aspect, the present invention provides a process for the catalytic oxidation of hydrocarbons, the process comprising: in the presence of the catalyst, the hydrocarbons and an oxidant are subjected to contact reaction to obtain ketones and dicarboxylic acids; the hydrocarbon is at least one of C6-C12 monocycloalkane and C8-C16 bicycloalkane.
In a fourth aspect, the present invention provides a process for the catalytic oxidation of hydrocarbons, the process comprising:
(1) roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is citric acid and/or malic acid; and the conditions under which the firing is carried out include: the temperature is 900-;
(2) in the presence of tert-butyl hydroperoxide and the catalyst obtained in the step (1), cyclohexane and an oxidant are subjected to contact reaction to obtain cyclohexanone and adipic acid; wherein, on the basis of 10mL of cyclohexane, the dosage of the catalyst is 20-60mg, and the dosage of the tert-butyl hydroperoxide is 0.01-0.3 mL; and the conditions under which the contact reaction is carried out include: the temperature is 60-180 ℃; the pressure is 1-3 MPa; the time is 2-24 h.
In a fifth aspect, the present invention provides a process for the catalytic oxidation of hydrocarbons, the process comprising:
(1) roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is naphthenic acid and/or glutamic acid; and the conditions under which the firing is carried out include: the temperature is 1050-;
(2) in the presence of tert-butyl hydroperoxide and the catalyst obtained in the step (1), cyclohexane and an oxidant are subjected to contact reaction to obtain cyclohexanone and adipic acid; wherein, on the basis of 10mL of cyclohexane, the dosage of the catalyst is 20-60mg, and the dosage of the tert-butyl hydroperoxide is 0.01-0.3 mL; and the conditions under which the contact reaction is carried out include: the temperature is 60-180 ℃; the pressure is 1-3 MPa; the time is 2-24 h.
By adopting the technical scheme, the conversion rate of hydrocarbons and the selectivity of ketones and dicarboxylic acids in the catalytic oxidation process of hydrocarbons can be improved.
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.
In a first aspect the present invention provides a process for the preparation of a catalyst, the process comprising: roasting organic acid under the oxygen-free condition to obtain a catalyst, wherein the organic acid is selected from at least one of naphthenic acid, amino acid, citric acid, malic acid, grape 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 and fumaric acid.
According to the present invention, the oxygen-free conditions may be achieved by methods conventional in the art, such as removing oxygen-containing gas, e.g., air, with an inert gas. The product obtained by the method is nano carbon particles, can be aggregated into bulk particles to exist, and can be directly used as a catalyst for catalytic reaction without a post-treatment process.
According to a preferred embodiment of the present invention, the organic acid is added to the crucible at normal temperature and pressure, and then the crucible is placed in a high temperature electric furnace, and air is removed by using nitrogen gas, and the catalyst is calcined in nitrogen atmosphere to obtain the catalyst. In the present invention, the normal temperature and pressure means the temperature and pressure felt by a human being, which is 25 ℃ +/-20%, and one atmosphere +/-20%.
In such an embodiment:
preferably, the organic acid is selected from at least one of citric acid, malic 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 and fumaric acid.
More preferably, the organic acid is citric acid and/or malic acid.
In order to further improve the conversion of hydrocarbons, the selectivity of ketones and dicarboxylic acids, preferably, the calcination is carried out under conditions comprising: the temperature is 800-1200 ℃, and the time is 1-48 h. More preferably, the conditions under which the firing is carried out include: the temperature is 850-1100 ℃, and the time is 2-30 h.
Particularly preferably, the conditions under which the firing is carried out include: the temperature is 900-.
According to another preferred embodiment of the invention, the organic acid is added into a quartz reactor, air is removed by using nitrogen, the quartz reactor is pressurized to more than 1MPa by using nitrogen and sealed, and then the quartz reactor is heated to the roasting temperature by using a high-temperature electric furnace to obtain the catalyst.
In such an embodiment:
the organic acid is at least one selected from naphthenic acid, amino acid, citric acid, malic 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 and fumaric acid.
Preferably, the organic acid is selected from at least one of naphthenic acid and amino acid. Wherein the naphthenic acid has the general formula C n H 2n-1 COOH, which may be a commercially available commercial product, having a molecular weight in the range of 180-350, may be a saturated monocyclic carboxylic acid (C) n H 2n- 1 COOH), saturated polycyclic carboxylic acid (C) n H 2n-3 COOH) and a fatty carboxylic acid (C) n H 2n+1 COOH).
Preferably, the amino acid is selected from at least one of alanine, valine, leucine, isoleucine, proline, phenylalanine, tryptophan, methionine, glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid, and the like.
More preferably, the organic acid is naphthenic acid and/or glutamic acid.
In order to further increase the conversion of hydrocarbons, the selectivity of ketones and dicarboxylic acids, it is preferred that the calcination is carried out under conditions comprising: the temperature is 800 ℃ and 1500 ℃, the time is 1-48h, and the pressure is 1-3 MPa. More preferably, the firing is carried out under conditions comprising: the temperature is 1000 ℃ and 1300 ℃, the time is 2-30h, and the pressure is 1-3 MPa.
Particularly preferably, the conditions under which the firing is carried out include: the temperature is 1050-.
Several preferred embodiments of the invention are provided below:
embodiment mode 1:
the method for preparing the catalyst comprises the following steps: roasting organic acid under an anaerobic condition to obtain a catalyst; the conditions under which the firing is carried out include: the temperature is 800-1200 ℃, and the time is 1-48 h; the organic acid is citric acid and/or malic acid.
In the foregoing embodiment 1, it is preferable that the firing is performed under conditions including: the temperature is 850 ℃ and 1100 ℃, and the time is 2-30 h. More preferably, the firing is carried out under conditions comprising: the temperature is 900-1050 ℃, and the time is 4-12 h.
Embodiment mode 2:
the method for preparing the catalyst comprises the following steps: roasting organic acid under an anaerobic condition to obtain a catalyst; the conditions under which the firing is carried out include: the temperature is 800-; the organic acid is naphthenic acid and/or glutamic acid.
In the foregoing embodiment mode 2, the conditions for performing the calcination preferably include: the temperature is 1000 ℃ and 1300 ℃, the time is 2-30h, and the pressure is 1-3 MPa. More preferably, the firing is carried out under conditions comprising: the temperature is 1050 ℃ and 1250 ℃, the time is 4-12h, and the pressure is 1-3 MPa.
The inventors of the present invention have found in their research that the calcined product obtained in the foregoing embodiment 1 and embodiment 2 can be used as a catalyst for the catalytic oxidation of hydrocarbons to produce ketones and dicarboxylic acids with a better hydrocarbon conversion rate and a better selectivity for ketones and dicarboxylic acids.
In a second aspect, the present invention provides a catalyst prepared by the above process.
In a third aspect, the present invention provides a process for the catalytic oxidation of hydrocarbons, the process comprising: in the presence of the catalyst, the hydrocarbons and an oxidant are subjected to contact reaction to obtain ketones and dicarboxylic acids; the hydrocarbon is C 6 -C 12 Monocycloalkane of (2) and C 8 -C 16 At least one of the bicycloalkanes of (a).
Preferably, the hydrocarbon is cyclohexane.
According to the present invention, the use of the catalyst of the present invention can achieve the object of improving the conversion of hydrocarbons and the selectivity of ketones and dicarboxylic acids. Further, for better catalytic effect, the contact reaction is carried out in the presence of an initiator. Preferably, the initiator is a peroxide. More preferably, the initiator is tert-butyl hydroperoxide (TBHP).
In the present invention, the amount of the initiator is not particularly limited. In order to further improve the hydrocarbon conversion rate and the ketone and dicarboxylic acid selectivity, the amount of the initiator is preferably 0.01-0.3mL based on 10mL of the hydrocarbon.
In order to further improve the hydrocarbon conversion rate and the ketone and dicarboxylic acid selectivity, the amount of the catalyst is preferably 10-100mg based on 10mL of the hydrocarbon. More preferably, the catalyst is used in an amount of 20-60 mg.
In the present invention, the oxidizing agent may be an oxidizing agent commonly used in the production of ketones and dicarboxylic acids by catalytic oxidation of hydrocarbons, and preferably, the oxidizing agent contains molecular oxygen from the viewpoint of environmental protection and increased economic benefit. More preferably, the oxidant is oxygen. The oxygen may be supplied from air, and the purity of the oxygen is not particularly limited in the present invention as long as the production of ketones and dicarboxylic acids by the catalytic oxidation of hydrocarbons can be achieved.
To further increase the hydrocarbon conversion and ketone and dicarboxylic acid selectivity, the contacting reaction is preferably carried out under conditions comprising: the temperature is 50-200 ℃; the pressure is 0.5-5 MPa; the time is 1-72 h. More preferably, the conditions under which the contact reaction is carried out include: the temperature is 60-180 ℃; the pressure is 1-3 MPa; the time is 2-24 h.
According to a preferred embodiment of the present invention, a process for the catalytic oxidation of hydrocarbons comprises:
(1) roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is citric acid and/or malic acid; and the conditions under which the firing is carried out include: the temperature is 900-;
(2) in the presence of an initiator and the catalyst obtained in the step (1), carrying out contact reaction on cyclohexane and an oxidant to obtain cyclohexanone and adipic acid; wherein, the dosage of the catalyst is 20-60mg based on 10mL of cyclohexane; the initiator is tert-butyl hydroperoxide; taking 10mL of cyclohexane as a reference, and the using amount of the initiator is 0.01-0.3 mL; the conditions for carrying out the contact reaction include a temperature of 60 to 180 ℃; the pressure is 1-3 MPa; the time is 2-24 h. The inventor of the present invention found in research that satisfying the above preferred embodiment can more significantly improve the conversion of cyclohexane and the selectivity of cyclohexanone and adipic acid, specifically, can improve the conversion of cyclohexane to 18% or more, improve the selectivity of cyclohexanone to 34% or more, and simultaneously improve the selectivity of adipic acid to 48% or more.
According to another preferred embodiment of the present invention, a process for the catalytic oxidation of hydrocarbons comprises:
(1) roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is naphthenic acid and/or glutamic acid; and the conditions under which the firing is carried out include: 1050 and 1250 ℃ with the time of 4-12h and the pressure of 1-3 MPa;
(2) in the presence of an initiator and the catalyst obtained in the step (1), carrying out contact reaction on cyclohexane and an oxidant to obtain cyclohexanone and adipic acid; wherein, the dosage of the catalyst is 20-60mg based on 10mL of cyclohexane; the initiator is tert-butyl hydroperoxide; the dosage of the initiator is 0.01-0.3mL based on 10mL of cyclohexane; the conditions for carrying out the contact reaction include a temperature of 60 to 180 ℃; the pressure is 1-3 MPa; the time is 2-24 h. The inventors of the present invention found in their studies that satisfying the above preferred embodiments can more significantly improve the conversion of cyclohexane and the selectivity of cyclohexanone and adipic acid, specifically, can improve the conversion of cyclohexane to 17% or more, improve the selectivity of cyclohexanone to 35% or more, and simultaneously improve the selectivity of adipic acid to 47% or more.
The present invention will be described in detail and exemplarily by the following examples, but not limited thereby in its scope. In the following examples of the present invention,
citric acid, malic acid, glutamic acid, naphthenic acid (CAS:1338-24-5), t-butyl hydroperoxide, and activated carbon were purchased from Chemicals, Inc., national drug group.
Preparation example 1
Adding 50g of citric acid into a crucible, then putting the crucible into a high-temperature electric furnace, removing air by using nitrogen, raising the temperature to 1000 ℃ in a nitrogen atmosphere, and roasting at the temperature for 4 hours to obtain the catalyst A.
Preparation example 2
Adding 50g of malic acid into a crucible, then placing the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 950 ℃ in a nitrogen atmosphere, and roasting at the temperature for 10 hours to obtain the catalyst B.
Preparation example 3
Adding 50g of citric acid into a crucible, then placing the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 800 ℃ in a nitrogen atmosphere, and roasting at the temperature for 18 hours to obtain the catalyst C.
Preparation example 4
Adding 50g of citric acid into a crucible, then placing the crucible into a high-temperature electric furnace, removing air by using nitrogen, heating to 1100 ℃ in a nitrogen atmosphere, and roasting at the temperature for 3 hours to obtain the catalyst D.
Preparation example 5
Adding 50g of naphthenic acid into a quartz reactor, firstly utilizing nitrogen to remove air, pressurizing the quartz reactor to 1.5MPa by using the nitrogen, then sealing the quartz reactor, then heating the quartz reactor to the roasting temperature of 1100 ℃ by utilizing a high-temperature electric furnace, and roasting the quartz reactor for 5 hours at the temperature to obtain the catalyst E.
Preparation example 6
Adding 50g of glutamic acid into a quartz reactor, firstly utilizing nitrogen to remove air, pressurizing the quartz reactor to 2MPa by using the nitrogen, then sealing the quartz reactor, then heating the quartz reactor to the roasting temperature of 1200 ℃ by utilizing a high-temperature electric furnace, and roasting the quartz reactor for 8 hours at the temperature to obtain the catalyst F.
Preparation example 7
Adding 50G of naphthenic acid into a quartz reactor, firstly utilizing nitrogen to remove air, pressurizing the quartz reactor to 0.5MPa by using nitrogen, then sealing, then heating the quartz reactor to the roasting temperature of 1000 ℃ by utilizing a high-temperature electric furnace, and roasting for 4 hours at the temperature to obtain the catalyst G.
Preparation example 8
Adding 50g of glutamic acid into a quartz reactor, firstly utilizing nitrogen to remove air, pressurizing the quartz reactor to 1.5MPa by using the nitrogen, then sealing the quartz reactor, then heating the quartz reactor to the roasting temperature of 1300 ℃ by utilizing a high-temperature electric furnace, and roasting the quartz reactor for 15 hours at the temperature to obtain the catalyst H.
Example 1
200mg of catalyst A obtained in preparation example 1 and 100mL of cyclohexane were charged into a 250mL autoclave with continuous stirring, respectively, and 0.4mL of t-butyl hydroperoxide (TBHP) as an initiator was added dropwise to the above system without any other solvent. Then, at 135 ℃, the mixture is stirred to react for 6 hours under the condition of introducing oxidant oxygen to the pressure of 2.0MPa, and then the mixture is cooled, decompressed, sampled, centrifuged and filtered, and after the catalyst is separated, the product is analyzed.
Examples 2 to 8
The experiment was carried out in the same manner as in example 1 except that the catalyst A was replaced with catalyst B, catalyst C, catalyst D, catalyst E, catalyst F, catalyst G and catalyst H, respectively.
Example 9
300mg of catalyst A obtained in preparation example 1 and 100mL of cyclohexane were charged into a 250mL autoclave with continuous stirring, respectively, and then 0.2mL of t-butyl hydroperoxide (TBHP) as an initiator was added dropwise to the above system without any other solvent. Then, at 80 ℃, the reaction was timed by introducing oxygen as an oxidant to a pressure of 3.0MPa, the mixture was stirred for 18 hours, then depressurized and depressurized for sampling, centrifuged and filtered, and after separating the catalyst, the product was analyzed.
Example 10
300mg of catalyst A obtained in preparation example 1 and 100mL of cyclohexane were charged into a 250mL autoclave with continuous stirring, respectively, and then 0.6mL of t-butyl hydroperoxide (TBHP) as an initiator was added dropwise to the above system without any other solvent. Then, the reaction was carried out at 150 ℃ with oxygen as an oxidant introduced to a pressure of 1.0MPa for a time-lapse reaction, and after the mixture was stirred for 5 hours, it was depressurized and sampled at a reduced pressure, centrifuged and filtered, and after separating the catalyst, the product was analyzed.
Comparative example 1
An experiment was conducted in accordance with the procedure of example 1, except that the catalyst A obtained in production example 1 was replaced with activated carbon.
Comparative example 2
The experiment was carried out according to the method of example 1, except that no catalyst was added.
Test example
The products of the examples and comparative examples were analyzed by gas chromatography (GC: Agilent, 7890A) and gas chromatography-mass spectrometer (GC-MS: Thermo Fisher Trace ISQ), and the test results are shown in Table 1.
Conditions of GC: 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 ℃.
Cyclohexane conversion% (% cyclohexane mass added before reaction-cyclohexane mass remaining after reaction)/cyclohexane mass added before reaction × 100%;
cyclohexanone selectivity ═ amount of cyclohexanone substance produced after the reaction)/amount of cyclohexane substance added before the reaction × 100%.
Adipic acid selectivity (% as the amount of cyclohexanol species formed after the reaction)/the amount of cyclohexane species added before the reaction × 100%.
TABLE 1
| Example numbering | Cyclohexane reactorPercent conversion% | Cyclohexanone Selectivity% | Adipic acid selectivity% |
| Example 1 | 18.9 | 34 | 48 |
| Example 2 | 18.2 | 41 | 50 |
| Example 3 | 13.2 | 30 | 36 |
| Example 4 | 14.1 | 33 | 38 |
| Example 5 | 17.9 | 42 | 49 |
| Example 6 | 18.1 | 35 | 47 |
| Example 7 | 13.3 | 32 | 35 |
| Example 8 | 12.9 | 33 | 34 |
| Example 9 | 19.0 | 36 | 50 |
| Example 10 | 18.7 | 40 | 48 |
| Comparative example 1 | 5 | 28 | 10 |
| Comparative example 2 | 3.1 | 25 | 3 |
The results in table 1 show that examples 1 to 10 using the catalyst provided by the present invention have significantly better effects, and can increase the conversion rate of cyclohexane to more than 10%, the selectivity of cyclohexanone to more than 30%, and the selectivity of adipic acid to more than 34%.
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 (20)
1. A method of preparing a catalyst, the method comprising: roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is selected from at least one of naphthenic acid, amino acid, citric acid, malic 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 and fumaric acid;
the roasting conditions comprise: the temperature is 800-;
when the organic acid is naphthenic acid and/or glutamic acid, the roasting pressure is 1-3 MPa.
2. The method of claim 1, wherein the organic acid is citric acid and/or malic acid; the conditions under which the firing is carried out include: the temperature is 850 ℃ and 1100 ℃, and the time is 2-30 h.
3. The process according to claim 1 or 2, wherein the organic acid is citric acid and/or malic acid; the conditions under which the firing is carried out include: the temperature is 900-1050 ℃, and the time is 4-12 h.
4. The method of claim 1, wherein the organic acid is naphthenic acid and/or glutamic acid; the conditions under which the firing is carried out include: the temperature is 1000-1300 ℃, the time is 2-30h, and the pressure is 1-3 MPa.
5. The method of claim 1 or 4, wherein the organic acid is naphthenic acid and/or glutamic acid; the conditions under which the firing is carried out include: the temperature is 1050 ℃ and 1250 ℃, the time is 4-12h, and the pressure is 1-3 MPa.
6. A catalyst prepared by the process of any one of claims 1 to 5.
7. A process for the catalytic oxidation of hydrocarbons, the process comprising: in the presence of a catalyst, a hydrocarbon is in contact reaction with an oxidant to obtain ketones and dicarboxylic acids, wherein the hydrocarbon is C 6 -C 12 Of monocycloalkane and C 8 -C 16 At least one of the bicyclic alkanes of (a); the catalyst is the catalyst described in claim 6.
8. A catalytic oxidation process according to claim 7, wherein the contact reaction is carried out in the presence of an initiator.
9. A catalytic oxidation process according to claim 8, wherein the initiator is a peroxide.
10. A catalytic oxidation process according to claim 8 or 9, wherein the initiator is tert-butyl hydroperoxide.
11. The catalytic oxidation process of claim 8 or 9, wherein the initiator is used in an amount of 0.01 to 0.3mL based on 10mL of the hydrocarbon.
12. The catalytic oxidation process according to any one of claims 7 to 9, wherein the catalyst is used in an amount of 10 to 100mg, based on 10mL of the hydrocarbon.
13. The catalytic oxidation process according to any one of claims 7 to 9, wherein the catalyst is used in an amount of 20 to 60mg, based on 10mL of the hydrocarbon.
14. The catalytic oxidation method according to any one of claims 7 to 9, wherein the oxidizing agent contains molecular oxygen.
15. The catalytic oxidation process according to any one of claims 7 to 9, wherein the oxidant is oxygen.
16. The catalytic oxidation process according to any one of claims 7 to 9, wherein the hydrocarbon is cyclohexane.
17. The catalytic oxidation process according to any one of claims 7 to 9, wherein the conditions under which the contact reaction is carried out include: the temperature is 50-200 ℃; the pressure is 0.5-5 MPa; the time is 1-72 h.
18. The catalytic oxidation process according to any one of claims 7 to 9, wherein the conditions under which the contact reaction is carried out include: the temperature is 60-180 ℃; the pressure is 1-3 MPa; the time is 2-24 h.
19. A process for the catalytic oxidation of hydrocarbons, the process comprising:
(1) roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is citric acid and/or malic acid; and the conditions under which the firing is carried out include: the temperature is 900-;
(2) in the presence of tert-butyl hydroperoxide and the catalyst obtained in the step (1), cyclohexane and an oxidant are subjected to contact reaction to obtain cyclohexanone and adipic acid; wherein, on the basis of 10mL of cyclohexane, the dosage of the catalyst is 20-60mg, and the dosage of the tert-butyl hydroperoxide is 0.01-0.3 mL; and the conditions under which the contact reaction is carried out include: the temperature is 60-180 ℃; the pressure is 1-3 MPa; the time is 2-24 h.
20. A process for the catalytic oxidation of hydrocarbons, the process comprising:
(1) roasting organic acid under an anaerobic condition to obtain a catalyst; wherein the organic acid is naphthenic acid and/or glutamic acid; and the conditions under which the firing is carried out include: the temperature is 1050-;
(2) in the presence of tert-butyl hydroperoxide and the catalyst obtained in the step (1), cyclohexane and an oxidant are subjected to contact reaction to obtain cyclohexanone and adipic acid; wherein, on the basis of 10mL of cyclohexane, the dosage of the catalyst is 20-60mg, and the dosage of the tert-butyl hydroperoxide is 0.01-0.3 mL; and the conditions under which the contact reaction is carried out include: the temperature is 60-180 ℃; the pressure is 1-3 MPa; the time is 2-24 h.
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