CN111760565B - Modified nano carbon-based material, preparation method thereof and catalytic oxidation method of cyclic hydrocarbon - Google Patents
Modified nano carbon-based material, preparation method thereof and catalytic oxidation method of cyclic hydrocarbon Download PDFInfo
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Abstract
The present disclosure relates to a modified nanocarbon-based material, a method for preparing the same, and a method for catalytic oxidation of cyclic hydrocarbons. The catalytic oxidation method of the cyclic hydrocarbon comprises the following steps: the cyclic hydrocarbon and the oxygen-containing gas are contacted in the presence of a catalyst to react, wherein the catalyst comprises a modified nanocarbon-based material. The method adopts special modified nano carbon-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 higher raw material conversion rate and target product selectivity.
Description
Technical Field
The present disclosure relates to a modified nanocarbon-based material, a method for preparing the same, and a method for catalytic oxidation of cyclic hydrocarbons.
Background
Carbon-based materials include carbon nanotubes, activated carbon, graphite, graphene, fullerenes, carbon nanofibers, nanodiamonds, and the like. The scientific research of nanocarbon catalysis began in the 90 s of the last century. Researches show that the surface chemical properties of the nano carbon material (mainly comprising nano carbon tubes and graphene) can be flexibly regulated and controlled, and saturated and unsaturated functional groups containing hetero atoms 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 oxidation-reduction capability, and is directly used as a catalyst material. The research and development of new catalytic materials related to fullerene (carbon nano tube) widens the application of the new catalytic materials in the fields of petrochemical industry, fine chemical industry and the like, and has profound theoretical significance and great potential application prospect.
Disclosure of Invention
An object of the present disclosure is to provide a modified nanocarbon-based material having excellent catalytic performance for selective oxidation of cyclic hydrocarbons, a method for preparing the same, and a method for catalytic oxidation of cyclic hydrocarbons.
To achieve the above object, a first aspect of the present disclosure: the preparation method of the modified nano carbon-based material comprises the following steps:
a. connecting a first conductive object with a positive electrode of a direct current power supply, connecting a second conductive object with a negative electrode of the direct current power supply, placing the second conductive object in an electrolyte, and applying a voltage of 0.1-110V, preferably 5-80V, to carry out electrolysis for 1-30 days, preferably 5-15 days, so as to obtain an electrolyzed electrolyte, wherein the first conductive object is a graphite rod;
b. mixing the electrolyzed electrolyte obtained in the step a with an oxidant, performing first modification treatment for 2-24 hours, preferably 5-20 hours at 20-200 ℃, preferably 60-100 ℃, and then performing freeze drying on the material subjected to the first modification treatment;
or, freeze-drying the electrolyzed electrolyte obtained in the step a to obtain nano carbon particles, mixing the nano carbon particles with an oxidant, performing second modification treatment at 0-200 ℃ and preferably 50-100 ℃ for 1-12 hours and preferably 2-10 hours, and freeze-drying the material after the second modification treatment.
Optionally, in the step a, the diameter of the graphite rod is 2-20 mm, and the length is 2-100 cm; and/or the number of the groups of groups,
the second conductive object is an iron rod, an iron plate, a graphite rod, a graphite plate, a copper plate or a copper rod, preferably an iron rod, a graphite rod or a copper rod, and more preferably a graphite rod matched with the size of the first conductive object; and/or the number of the groups of groups,
the electrolyte is an aqueous solution having a water content of 85 wt% or more.
Optionally, in step b, the oxidizing agent is hydrogen peroxide, peracetic acid, peroxypropionic acid, or t-butyl hydroperoxide, or a combination of two or three thereof;
the weight ratio of the electrolyzed electrolyte to the oxidant is 1: (1 to 500), preferably 1: (2-100); alternatively, the weight ratio of the nano carbon particles to the oxidant is 1: (0.2 to 100), preferably 1: (1-50);
the conditions of the freeze-drying include: the temperature is-50 ℃ to 0 ℃, preferably-40 ℃ to-10 ℃; the pressure is 1 to 200Pa, preferably 5 to 100Pa; the time is 1 to 96 hours, preferably 6 to 48 hours.
A second aspect of the present disclosure: there is provided a modified nanocarbon-based material prepared by the method of the first aspect of the present disclosure.
Alternatively, the particle size of the modified nanocarbon-based material is 1 to 50nm, preferably 3 to 20nm.
A third aspect of the present disclosure: there is provided a process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: the cyclic hydrocarbon and the oxygen-containing gas are contacted in the presence of a catalyst to react, wherein the catalyst comprises the modified nanocarbon-based material of the second aspect of the disclosure.
Alternatively, the reaction is carried out in a slurry bed reactor, the catalyst being used in an amount of from 2 to 100mg, preferably from 5 to 50mg, based on 10mL of the cyclic hydrocarbon.
Alternatively, the reaction is carried out in a fixed bed reactor, the cyclic hydrocarbon having a weight hourly space velocity of 0.01 to 10 hours -1 Preferably 0.05 to 2 hours -1 。
Optionally, the oxygen-containing gas is air or oxygen;
the molar ratio of the cyclic hydrocarbon to oxygen in the oxygen-containing gas is 1: (1-5).
Alternatively, the cyclic hydrocarbon is one selected from the group consisting of a C6 to C12 substituted or unsubstituted monocycloalkane and a C8 to C16 substituted or unsubstituted bicycloalkane, preferably cyclohexane or methylcyclopentane.
Alternatively, the conditions of the reaction are: the temperature is 50-200 ℃, preferably 60-180 ℃; the time is 1 to 72 hours, preferably 2 to 24 hours; the pressure is 0 to 20MPa, preferably 0 to 10MPa.
Through the technical scheme, the special modified nano carbon-based material is adopted as the catalyst for catalyzing the oxidation reaction of the cyclic hydrocarbon, so that the selective oxidation of the cyclic hydrocarbon can be realized under mild conditions, and the raw material conversion rate and the selectivity of the target product are higher.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The first aspect of the present disclosure: the preparation method of the modified nano carbon-based material comprises the following steps:
a. connecting a first conductive object with a positive electrode of a direct current power supply, connecting a second conductive object with a negative electrode of the direct current power supply, placing the second conductive object in an electrolyte, and applying a voltage of 0.1-110V, preferably 5-80V, to carry out electrolysis for 1-30 days, preferably 5-15 days, so as to obtain an electrolyzed electrolyte, wherein the first conductive object is a graphite rod;
b. mixing the electrolyzed electrolyte obtained in the step a with an oxidant, performing first modification treatment for 2-24 hours, preferably 5-20 hours at 20-200 ℃, preferably 60-100 ℃, and then performing freeze drying on the material subjected to the first modification treatment;
or, freeze-drying the electrolyzed electrolyte obtained in the step a to obtain nano carbon particles, mixing the nano carbon particles with an oxidant, performing second modification treatment at 0-200 ℃ and preferably 50-100 ℃ for 1-12 hours and preferably 2-10 hours, and freeze-drying the material after the second modification treatment.
According to the present disclosure, in the step a, the graphite rod is a rod made of graphite, and the size thereof may vary within a wide range, for example, the diameter of the graphite rod may be 2 to 20mm, and the length thereof may be 2 to 100cm, wherein the length refers to the axial length of the graphite rod.
According to the present disclosure, in the step a, the second conductive material may be various common conductive materials, and there is no requirement on materials and shapes, such as shapes may be common rod-shaped or plate-shaped, specifically, such as an iron rod, an iron plate, a graphite rod, a graphite plate, a copper rod, etc., preferably, a rod-shaped, such as an iron rod, a graphite rod, a copper rod, etc., further preferably, a graphite rod, and further preferably, there is no limitation on the size, and most preferably, a graphite rod matching the size of the first conductive material. The electrolysis may be performed with a distance between the first and second conductors, for example 3-10 cm.
According to the present disclosure, in the step a, the electrolyte may have a resistivity of 0 to 20mΩ·cm -1 Further, the aqueous solution may have a water content of 85% by weight or more. The aqueous solution may also contain common inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), inorganic bases (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.), inorganic salts (e.g., sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, etc.), or organic solvents (e.g., alcohols, ketones, aldehydes, esters, etc.). The amount of the electrolyte is not particularly limited and may be adjusted according to the material and size of the conductive material and the electrolysis conditions.
According to the disclosure, the electrolytic solution obtained in the step a contains a nano carbon-based material, and the step b is a step of modifying the nano carbon-based material by using an oxidant. Wherein the oxidizing agent may be hydrogen peroxide, peracetic acid, peroxypropionic acid, or t-butyl hydroperoxide, or a combination of two or three thereof. The oxidizing agent may be in the form of an aqueous solution having a concentration, for example, an aqueous solution having a concentration of 5 to 70% by weight.
In a first specific embodiment of the disclosure, the electrolyzed electrolyte is directly subjected to a first modification treatment, and then the material subjected to the first modification treatment is subjected to freeze drying to obtain a modified nano carbon-based material; according to the embodiment, only one freeze-drying step is carried out, so that the energy consumption is reduced, and the selectivity of ketones in the target product is higher when the prepared modified nano carbon-based material is used for catalyzing the oxidation reaction of cyclic hydrocarbon. In this embodiment, the weight ratio of the electrolyzed electrolyte to the oxidizing agent may be 1: (1 to 500), preferably 1: (2-100).
In a second specific embodiment of the disclosure, the electrolyzed electrolyte is subjected to primary freeze drying, the dried nano carbon particles are subjected to a second modification treatment, and then the modified nano carbon-based material is obtained through secondary freeze drying; compared with the first specific embodiment, the second embodiment can reduce the amount of the oxidant used in the modification treatment, and the modification treatment condition is milder, so that the selectivity of the acid in the target product is higher when the prepared modified nano carbon-based material is used for catalyzing the oxidation reaction of the cyclic hydrocarbon. In this embodiment, the weight ratio of the nano-carbon particles to the oxidizing agent may be 1: (0.2 to 100), preferably 1: (1-50).
According to the present disclosure, in step b, the freeze-drying in both embodiments described above may be performed using conventional conditions. For example, the freeze-drying conditions may include: the temperature is-50 ℃ to 0 ℃, preferably-40 ℃ to-10 ℃; the pressure is 1 to 200Pa, preferably 5 to 100Pa; the time is 1 to 96 hours, preferably 6 to 48 hours.
A second aspect of the present disclosure: there is provided a modified nanocarbon-based material prepared by the method of the first aspect of the present disclosure. Wherein, the particle size of the modified nano carbon-based material can be 1-50 nm, and is preferably 3-20 nm. In the present disclosure, the "particle size" refers to the maximum three-dimensional length of a particle, i.e., the distance between two points on the particle where the distance is the greatest. The modified nano carbon-based material has proper particle size and excellent catalytic performance, and is especially suitable for the catalytic oxidation of cyclic hydrocarbon and the like.
A third aspect of the present disclosure: there is provided a catalytic oxidation process for cyclic hydrocarbons, characterized in that the process comprises: the cyclic hydrocarbon and the oxygen-containing gas are contacted in the presence of a catalyst to react, wherein the catalyst comprises the modified nanocarbon-based material of the second aspect of the disclosure.
The process of the present disclosure may be carried out in various conventional catalytic reactors, for example, in batch tank reactors or three-neck flasks, 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 depending on the amounts of the cyclic hydrocarbon and the oxidizing agent, and for example, the catalyst may be used in an amount of 2 to 100mg, preferably 5 to 50mg, 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 -1 Preferably 0.05 to 2 hours -1 。
According to the present disclosure, the cyclic hydrocarbon may be one selected from the group consisting of a C5 to C12 substituted or unsubstituted monocycloalkane and a C8 to C16 substituted or unsubstituted bicycloalkane. Further, when the cyclic hydrocarbon is one selected from the group consisting of a C5 to C12 substituted monocyclic hydrocarbon and a C8 to C16 substituted bicyclic hydrocarbon, the substituent thereof may be a halide or a methyl group. For example, the cyclic hydrocarbon may be cyclohexane, cyclopentane, methylcyclohexane, halocyclohexane, methylcyclopentane, halocyclopentane, or the like, with cyclohexane being preferred.
According to the present disclosure, the oxygen-containing gas may be air or oxygen. The molar ratio of the cyclic hydrocarbon to oxygen in the oxygen-containing gas may be 1: (1-5).
In general, in the selective oxidation of alkanes with oxygen or air as an oxidizing agent, the reaction is often carried out in the presence of an initiator in order to promote the progress of the reaction and further improve the conversion of the raw material and the selectivity of the target product. The initiator may be, for example, t-butyl hydroperoxide, cumyl hydroperoxide, ethylbenzene hydroperoxide, peroxypropionic acid, or the like. The initiator may be used in an amount of 0.01 to 0.3mL based on 10mL of the cyclic hydrocarbon. According to the method, the alkane selective oxidation reaction using oxygen or air as an oxidant can be performed under the condition that an initiator is not needed, the technical effect that the reaction is performed in the presence of the initiator can be completely achieved, the addition of the initiator is avoided, and convenience is provided for the subsequent separation and purification of the product.
According to the present disclosure, the conditions of the reaction may be: the temperature is 50-200 ℃, preferably 60-180 ℃; the time is 1 to 72 hours, preferably 2 to 24 hours; the pressure is 0 to 20MPa, preferably 0 to 10MPa. In order to make the reaction more sufficient, it is preferable that the contact reaction is carried out under stirring.
The modified nano carbon-based material is used as a catalyst for catalyzing the oxidation reaction of the cyclic hydrocarbon, the selective oxidation of the cyclic hydrocarbon can be realized under mild conditions, and the selectivity of ketones and acids in the product is high.
The present disclosure is described in detail below in connection with examples, but is not thereby limiting the scope of the present disclosure.
Preparation examples 1 to 7 are provided to illustrate the modified nanocarbon-based material of the present disclosure and a preparation method thereof.
In the preparation example, the modified nanocarbon-based material has an average particle size of TECNAIG from FEI Co 2 F20 The (200 kv) type transmission electron microscope was used for measurement under the following conditions: accelerating voltage 20kV, adopting a suspension method to sample, placing the sample into a 2mL glass bottle, using no-loadDispersing with water and ethanol, shaking uniformly, taking one drop with a dropper, dripping on a sample net with the diameter of 3mm, drying, placing in a sample injector, inserting an electron microscope for observation, and randomly taking 100 particles for particle size statistics.
Preparation example 1
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 An anode graphite rod (diameter: 10mm length: 30 cm) and a cathode graphite rod (diameter: 10mm length: 30 cm) were placed therein, the distance between the anode graphite rod and the cathode graphite rod was maintained at 10cm, the anode graphite rod was connected to the positive electrode of a direct current power supply, the cathode graphite rod was connected to the negative electrode of the direct current power supply, and electrolysis was carried out by applying a voltage of 50V for 8 days, to obtain an electrolytic solution after electrolysis. The electrolyte after electrolysis and 30 weight percent hydrogen peroxide are mixed according to the weight ratio of 1:5, carrying out modification treatment for 12 hours at 80 ℃, and freeze-drying the modified material at-20 ℃ and 50Pa for 24 hours to obtain the modified nano carbon-based material C1 with the particle size of 8nm.
Preparation example 2
Into a beaker was charged 1500mL of a glass having a resistivity of 15MΩ cm -1 An anode graphite rod (diameter: 20mm, length: 30 cm) and a cathode graphite rod (diameter: 20mm, length: 30 cm) were placed therein, the distance between the anode graphite rod and the cathode graphite rod was kept at 5cm, the anode graphite rod was connected to the positive electrode of a direct current power supply, the cathode graphite rod was connected to the negative electrode of the direct current power supply, and electrolysis was carried out by applying a voltage of 100V for 18 days, to obtain an electrolytic solution after electrolysis. The electrolyte after electrolysis and 30 weight percent hydrogen peroxide are mixed according to the weight ratio of 1:80, and then carrying out modification treatment for 18h at 100 ℃, and freeze-drying the modified material for 24h at-20 ℃ and 50Pa to obtain the modified nano carbon-based material C2 with the particle size of 23nm.
Preparation example 3
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 An anode graphite rod (diameter: 10mm length: 30 cm) and a cathode graphite rod (diameter: 10mm length: 30 cm) were placed therein, the distance between the anode graphite rod and the cathode graphite rod was maintained at 10cm, and the anode graphite rod was connected to the positive electrode of a DC power supply andand connecting the cathode graphite rod with the negative electrode of a direct current power supply, and applying a voltage of 50V to carry out electrolysis for 12 days to obtain the electrolyzed electrolyte. The electrolyte after electrolysis and 30 weight percent hydrogen peroxide are mixed according to the weight ratio of 1:120, and then carrying out modification treatment for 24 hours at 120 ℃, and freeze-drying the modified material for 24 hours at-20 ℃ and 50Pa to obtain the modified nano carbon-based material C3 with the particle size of 5nm.
Preparation example 4
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 An anode graphite rod (diameter: 10mm length: 30 cm) and a cathode graphite rod (diameter: 10mm length: 30 cm) were placed therein, the distance between the anode graphite rod and the cathode graphite rod was maintained at 10cm, the anode graphite rod was connected to the positive electrode of a direct current power supply, the cathode graphite rod was connected to the negative electrode of the direct current power supply, and electrolysis was carried out by applying a voltage of 50V for 8 days, to obtain an electrolytic solution after electrolysis. Freeze-drying the electrolyzed electrolyte for 24 hours at the temperature of minus 20 ℃ and the pressure of 50Pa to obtain nano carbon particles, and then mixing the nano carbon particles with 30 weight percent hydrogen peroxide according to the weight ratio of 1:2, carrying out modification treatment for 6 hours at 70 ℃, and then carrying out freeze drying on the modified material at-20 ℃ and 50Pa for 24 hours to obtain the modified nano carbon-based material C4 with the particle size of 9nm.
Preparation example 5
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 Then adding 36% of strong ammonia water to form 2% ammonia water electrolyte by weight, placing an anode graphite rod (diameter 8mm length 50 cm) and a cathode copper rod (diameter 8mm length 50 cm) therein, keeping the distance between the anode graphite rod and the cathode copper rod at 10cm, connecting the anode graphite rod with the positive electrode of a direct current power supply and connecting the cathode copper rod with the negative electrode of the direct current power supply, and applying a voltage of 25V to electrolyze for 5 days to obtain the electrolyzed electrolyte. Freeze-drying the electrolyzed electrolyte at-25 ℃ and 80Pa for 24 hours to obtain nano carbon particles, and then mixing the nano carbon particles with 30 weight percent of peracetic acid according to the weight ratio of 1:15, then carrying out modification treatment for 10 hours at 60 ℃, and then carrying out freeze drying for 24 hours at-20 ℃ and 50Pa on the material after modification treatment to obtain the modified nanometerCarbon-based material C5, the particle size of which is 6nm.
Preparation example 6
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 An anode graphite rod (diameter: 10mm length: 30 cm) and a cathode graphite rod (diameter: 10mm length: 30 cm) were placed therein, the distance between the anode graphite rod and the cathode graphite rod was maintained at 10cm, the anode graphite rod was connected to the positive electrode of a direct current power supply, the cathode graphite rod was connected to the negative electrode of the direct current power supply, and electrolysis was carried out by applying a voltage of 80V for 10 days, to obtain an electrolytic solution after electrolysis. Freeze-drying the electrolyzed electrolyte for 24 hours at the temperature of minus 20 ℃ and the pressure of 50Pa to obtain nano carbon particles, and then mixing the nano carbon particles with 30 weight percent hydrogen peroxide according to the weight ratio of 1:80, then carrying out modification treatment for 12h at 120 ℃, and freeze-drying the modified material for 24h at-20 ℃ and 50Pa to obtain modified nano carbon-based material C6 with the particle size of 5nm.
Preparation example 7
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 An anode graphite rod (diameter: 10mm length: 30 cm) and a cathode graphite rod (diameter: 10mm length: 30 cm) were placed therein, the distance between the anode graphite rod and the cathode graphite rod was maintained at 10cm, the anode graphite rod was connected to the positive electrode of a direct current power supply, the cathode graphite rod was connected to the negative electrode of the direct current power supply, and electrolysis was carried out by applying a voltage of 90V for 8 days, to obtain an electrolytic solution after electrolysis. Freeze-drying the electrolyzed electrolyte for 24 hours at the temperature of minus 20 ℃ and the pressure of 50Pa to obtain nano carbon particles, and then mixing the nano carbon particles with 30 weight percent hydrogen peroxide according to the weight ratio of 1: and (3) mixing 0.5, performing modification treatment at 20 ℃ for 1h, and performing freeze drying on the modified material at-20 ℃ and 50Pa for 24h to obtain modified nano carbon-based material C7 with the particle size of 10nm.
Preparation of comparative example 1
500mL of a 15MΩ cm resistivity solution was added to the beaker -1 An anode graphite rod (diameter: 10mm length: 30 cm) and a cathode graphite rod (diameter: 10mm length: 30 cm) were placed therein with a distance between the anode graphite rod and the cathode graphite rod maintained at 10cm, and the anode graphite rod and the cathode graphite rod were then separated from each otherThe positive electrode of the direct current power supply is connected, the cathode graphite rod is connected with the negative electrode of the direct current power supply, and 50V voltage is applied to carry out electrolysis for 8 days, so that the electrolyzed electrolyte is obtained. And freeze-drying the electrolyzed electrolyte for 24 hours at the temperature of minus 20 ℃ and the pressure of 50Pa to obtain the nano carbon-based material D1, wherein the particle size of the nano carbon-based material D1 is 9nm.
Examples 1-14 are presented to illustrate a method for catalytic oxidation of cyclic hydrocarbons using the modified nanocarbon-based materials of the present disclosure. Comparative examples 1-2 are presented to illustrate a process for the catalytic oxidation of cyclic hydrocarbons using a different catalyst 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 spectrometry (GC-MS: thermo Fisher Trace ISQ). Conditions of gas chromatography: nitrogen carrier gas, temperature rise at 140K procedure: 60 ℃,1 minute, 15 ℃/minute, 180 ℃ and 15 minutes; split ratio, 10:1, a step of; the temperature of the sample inlet is 300 ℃; detector temperature, 300 ℃. The following formulas are used on this basis to calculate the feedstock conversion and target product selectivity, respectively:
% conversion of cyclic hydrocarbon = (molar amount of cyclic hydrocarbon added before reaction-molar amount of cyclic hydrocarbon remaining after reaction)/molar amount of cyclic hydrocarbon added before reaction x 100%;
target product selectivity% = (molar amount of target product formed after reaction)/molar amount of cyclic hydrocarbon added before reaction x 100%.
Example 1
50mg of modified nano carbon-based material C1 as a catalyst and 100mL of cyclohexane were added into a 250mL autoclave, the autoclave was sealed, oxygen was introduced (the molar ratio of oxygen to cyclohexane was 5:1), the mixture was stirred at 130 ℃ and 2.0MPa for 2 hours, the catalyst was separated by centrifugation and filtration after cooling and pressure relief sampling, and the results of analysis of the oxidation products were shown in Table 1.
Examples 2 to 7
Cyclohexane was catalytically oxidized in the same manner as in example 1, except that the same amounts of modified nanocarbon-based materials C2 to C7 were used in place of C1, respectively. The results of analysis of the oxidation products are shown in Table 1.
Example 8
300mg of modified nano carbon-based material C1 as a catalyst and 100mL of cyclohexane are added into a 250mL high-pressure reaction kettle for sealing, oxygen is introduced (the molar ratio of the oxygen to the cyclohexane is 2:1), the mixture is stirred at 100 ℃ and 2.5MPa for reaction for 8 hours, and then the catalyst is separated by cooling, pressure relief, sampling, centrifugation and filtration, and the oxidation product analysis results are shown in Table 1.
Example 9
20mg of modified nano carbon-based material C1 as a catalyst and 100mL of cyclohexane were added into a 250mL autoclave, the autoclave was sealed, oxygen was introduced (the molar ratio of oxygen to cyclohexane was 4:1), the mixture was stirred at 130 ℃ and 2.0MPa for reaction for 5 hours, the catalyst was separated by centrifugation and filtration after cooling and pressure relief sampling, and the results of analysis of the oxidation products were shown in Table 1.
Example 10
800mg of modified nano carbon-based material C1 as a catalyst and 100mL of cyclohexane are added into a 250mL high-pressure reaction kettle for sealing, oxygen is introduced (the molar ratio of the oxygen to the cyclohexane is 1:1), the mixture is stirred at 130 ℃ and 2.0MPa for reaction for 4 hours, and after cooling, pressure relief sampling, centrifugation and filtration are carried out to separate the catalyst, and the result of analysis of oxidation products is shown in Table 1.
Example 11
Filling the modified nano carbon-based material C1 serving as a catalyst into a fixed bed reactor, feeding cyclohexane into the reactor, and simultaneously introducing oxygen (the molar ratio of the oxygen to the cyclohexane is 5:1), wherein the weight hourly space velocity of the cyclohexane is 1h -1 After 5 hours of reaction at 130℃and 2.0MPa, the results of analysis of the oxidation products are shown in Table 1.
Example 12
Cyclohexane was catalytically oxidized according to the method of example 11, except that the same amount of modified nanocarbon-based material C4 was used instead of C1. The results of analysis of the oxidation products are shown in Table 1.
Example 13
Cyclohexane was catalytically oxidized as in example 1, except that 1ml of t-butyl hydroperoxide was added as an initiator. The results of analysis of the oxidation products are shown in Table 1.
Example 14
50mg of modified nano carbon-based material C1 serving as a catalyst and 100mL of methylcyclopentane are added into a 250mL high-pressure reaction kettle for sealing, oxygen is introduced (the molar ratio of the oxygen to the cyclohexane is 5:1), the mixture is stirred at 130 ℃ and 2.0MPa for reaction for 5 hours, and then the catalyst is separated by cooling, pressure relief, sampling, centrifugation and filtration, and the analysis result of the oxidation product is as follows: the methylcyclopentane conversion was 25.1% and the methylcyclopentanone selectivity was 68%.
Comparative example 1
Cyclohexane was catalytically oxidized according to the method of example 1, except that the modified nanocarbon-based material C1 was not used as a catalyst. The results of analysis of the oxidation products are shown in Table 1.
Comparative example 2
Cyclohexane was catalytically oxidized according to the method of example 1, except that the same amount of unmodified nanocarbon-based material D1 was used instead of the modified nanocarbon-based material C1 as the catalyst. The results of analysis of the oxidation products are shown in Table 1.
TABLE 1
| Catalyst source | Cyclohexane conversion% | Cyclohexanone selectivity,% | Adipic acid selectivity,% |
| Example 1 | 21.7 | 76 | 5 |
| Example 2 | 19.8 | 74 | 6 |
| Example 3 | 19.4 | 71 | 8 |
| Example 4 | 19.5 | 53 | 28 |
| Example 5 | 17.9 | 55 | 27 |
| Example 6 | 18.3 | 56 | 25 |
| Example 7 | 15.7 | 58 | 23 |
| Example 8 | 18.6 | 72 | 7 |
| Example 9 | 9.9 | 64 | 13 |
| Example 10 | 19.1 | 69 | 9 |
| Example 11 | 15.4 | 79 | 2 |
| Example 12 | 13.5 | 56 | 24 |
| Example 13 | 21.1 | 76 | 3 |
| Comparative example 1 | 3.6 | 34 | 9 |
| Comparative example 2 | 8.8 | 37 | 3 |
As can be seen from table 1, the use of the modified nanocarbon-based material of the present disclosure as a catalyst can achieve selective oxidation of cyclic hydrocarbons under mild conditions, and the feedstock conversion and target product selectivity are higher.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (28)
1. A process for the catalytic oxidation of a cyclic hydrocarbon, the process comprising: the cyclic hydrocarbon and the oxygen-containing gas are contacted and reacted in the presence of a catalyst, the catalyst containing a modified nanocarbon-based material, and the method for preparing the nanocarbon-based material comprises the following steps:
a. connecting a first conductive object with the positive electrode of a direct current power supply, connecting a second conductive object with the negative electrode of the direct current power supply, placing the second conductive object in electrolyte, and applying a voltage of 0.1-110V for electrolysis for 1-30 days to obtain electrolyzed electrolyte, wherein the first conductive object is a graphite rod;
b. c, mixing the electrolyzed electrolyte obtained in the step a with an oxidant, performing first modification treatment for 2-24 hours at 20-200 ℃, and then performing freeze drying on the material subjected to the first modification treatment;
or, freeze-drying the electrolyzed electrolyte obtained in the step a to obtain nano carbon particles, mixing the nano carbon particles with an oxidant, performing second modification treatment at 0-200 ℃ for 1-12 h, and freeze-drying the material after the second modification treatment;
in the step b, the oxidant is hydrogen peroxide, peracetic acid, peroxypropionic acid or tert-butyl hydroperoxide, or a combination of two or three of the above;
the weight ratio of the electrolyzed electrolyte to the oxidant is 1: (1-500); alternatively, the weight ratio of the nano carbon particles to the oxidant is 1: (0.2-100);
the molar ratio of the cyclic hydrocarbon to oxygen in the oxygen-containing gas is 1: (1-5);
the reaction conditions are as follows: the temperature is 50-200 ℃, the time is 1-72 h, and the pressure is 0-20 MPa.
2. The method of claim 1, wherein in step a, the voltage of the electrolysis is 5-80 v.
3. The method according to claim 1, wherein in step a, the electrolysis is performed for a period of 5 to 15 days.
4. The method according to claim 1, wherein in the step b, the temperature of the first modification treatment is 60-100 ℃.
5. The method according to claim 1, wherein in the step b, the time of the first modification treatment is 5-20 hours.
6. The method according to claim 1, wherein in the step b, the temperature of the second modification treatment is 50-100 ℃.
7. The method according to claim 1, wherein in the step b, the time of the second modification treatment is 2-10 hours.
8. The method according to claim 1, wherein in the step a, the diameter of the graphite rod is 2-20 mm, and the length is 2-100 cm;
the second conductive object is an iron rod, an iron plate, a graphite rod, a graphite plate, a copper plate or a copper rod;
the electrolyte is an aqueous solution having a water content of 85 wt% or more.
9. The method of claim 8, wherein the second conductive object is an iron rod, a graphite rod, or a copper rod.
10. The method of claim 9, wherein the second conductive object is a graphite rod that matches the size of the first conductive object.
11. The method of claim 1, wherein the freeze-drying conditions comprise: the temperature is between-50 ℃ and 0 ℃, the pressure is between 1 and 200Pa, and the time is between 1 and 96 hours.
12. The method of claim 1, wherein the weight ratio of the electrolyzed electrolyte to the oxidant is 1: (2-100).
13. The method of claim 1, wherein the weight ratio of the nanocarbon particles to the oxidizing agent is 1: (1-50).
14. The method of claim 11, wherein the freeze-drying temperature is from-40 ℃ to-10 ℃.
15. The method of claim 11, wherein the pressure of the freeze drying is 5-100 pa.
16. The method of claim 11, wherein the freeze-drying time is 6-48 hours.
17. The method of claim 1, wherein the particle size of the modified nanocarbon-based material is 1-50 nm.
18. The method of claim 17, wherein the modified nanocarbon-based material has a particle size of 3-20 nm.
19. The method according to claim 1, wherein the reaction is carried out in a slurry bed reactor, and the catalyst is used in an amount of 2 to 100mg based on 10mL of the cyclic hydrocarbon.
20. The method of claim 19, wherein the catalyst is used in an amount of 5 to 50mg based on 10mL of the cyclic hydrocarbon.
21. The method according to claim 1, 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 -1 。
22. The method of claim 21, wherein the cyclic hydrocarbon has a weight hourly space velocity of 0.05 to 2 hours -1 。
23. The method of claim 1, wherein the oxygen-containing gas is air or oxygen.
24. The method according to claim 1, wherein the cyclic hydrocarbon is one selected from the group consisting of a C6-C12 substituted or unsubstituted monocyclic hydrocarbon and a C8-C16 substituted or unsubstituted bicyclic hydrocarbon.
25. The method of claim 24, wherein the cyclic hydrocarbon is cyclohexane or methylcyclopentane.
26. The method of claim 1, wherein the temperature of the reaction is 60-180 ℃.
27. The method of claim 1, wherein the reaction time is 2-24 hours.
28. The method of claim 1, wherein the reaction pressure is 0-10 mpa.
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