CN112441958B - Method for oxidizing tertiary butanol - Google Patents
Method for oxidizing tertiary butanol Download PDFInfo
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- CN112441958B CN112441958B CN201910818663.7A CN201910818663A CN112441958B CN 112441958 B CN112441958 B CN 112441958B CN 201910818663 A CN201910818663 A CN 201910818663A CN 112441958 B CN112441958 B CN 112441958B
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Abstract
The present disclosure relates to a process for oxidizing tert-butanol, the process comprising: the method comprises the step of carrying out contact reaction on tertiary butanol and peroxide in the presence of a catalyst, wherein the catalyst is a modified nano carbon-based material. According to the method, a special modified nano carbon-based material is used as a catalyst to catalyze and oxidize the tert-butyl alcohol, so that the tert-butyl alcohol can be oxidized under a mild condition, the raw material conversion rate and the target product selectivity are high, the effective utilization rate of peroxide can be obviously improved, and the production cost is reduced.
Description
Technical Field
The present disclosure relates to a process for oxidizing tert-butanol.
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 oxygen, nitrogen and other heteroatoms 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. Researches and develops 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 huge potential application prospect.
T-butyl hydroperoxide is an organic peroxy compound, a colorless transparent liquid at room temperature, dissolved in water, ethanol, acetone, diethyl ether and chloroform. T-butyl hydroperoxide is generally produced by the oxidation of t-butyl alcohol, and generally includes the nitric acid oxidation, the peroxide oxidation, the ozone oxidation, and the like, depending on the oxidizing agent and the oxidation method used. Wherein the reaction condition of the peroxide oxidation method is mild, the equipment and the process route are simple, the product does not need alkali for neutralization, and the environment is not polluted basically. However, in the peroxide oxidation method, the oxidizing agent is expensive and used in a large amount, which increases the production cost of t-butyl hydroperoxide and limits the application range of the peroxide oxidation method.
Therefore, when tert-butyl alcohol is oxidized by the peroxide oxidation method, it is an important subject to improve the effective utilization rate of the oxidizing agent and to reduce the production cost of tert-butyl hydroperoxide.
Disclosure of Invention
The purpose of the present disclosure is to provide a method for oxidizing tert-butanol, which can not only achieve higher raw material conversion rate and target product selectivity, but also achieve higher effective utilization rate of peroxide.
In order to achieve the above object, the present disclosure provides a method of oxidizing tert-butanol, the method comprising: the method comprises the following steps of carrying out contact reaction on tertiary butanol and peroxide in the presence of a catalyst, wherein the catalyst is a modified nano carbon-based material, and the preparation step of the modified nano carbon-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, and then putting the second conductive object into electrolyte, applying a voltage of 0.1-110V, preferably 5-80V, to perform electrolysis for 1-30 days, preferably 5-15 days, so as to obtain electrolyzed electrolyte, wherein the first conductive object is a graphite rod;
b. b, mixing the electrolyzed electrolyte obtained in the step a with hydrazine hydrate, performing first modification treatment at the temperature of between 20 and 200 ℃, preferably between 60 and 100 ℃, for 2 to 24 hours, preferably between 5 and 20 hours, 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 hydrazine hydrate, performing second modification treatment for 1-12 h, preferably 2-10 h at the temperature of 0-200 ℃, preferably 50-100 ℃, and freeze-drying the material after the second modification treatment.
Optionally, in the step a, the graphite rod has a diameter of 2-20 mm and a length of 2-100 cm; and/or the presence of a gas in the atmosphere,
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 the iron rod, the graphite rod or the copper rod, and further preferably the graphite rod matched with the first conductive object in size; and/or the presence of a gas in the gas,
the electrolyte is an aqueous solution having a water content of 85 wt% or more.
Optionally, in the step b, the weight ratio of the electrolyzed electrolyte to the hydrazine hydrate is 10: (0.01 to 5), preferably 10: (0.1 to 2); or the weight ratio of the nano carbon particles to the hydrazine hydrate is 1: (1 to 1000), preferably 1: (2-500);
the conditions for 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.
Optionally, the proportion of the hydroxyl oxygen content in the modified nanocarbon-based material to the total oxygen content is greater than 70%, preferably greater than 85%.
Optionally, the particle size of the modified nanocarbon-based material is 1 to 50nm, preferably 3 to 20nm, and more preferably 5 to 10nm.
Optionally, the oxidation reaction is performed in a slurry bed reactor, and the amount of the catalyst is 1 to 500mg, preferably 2 to 100mg, based on 10mL of the tert-butanol.
Optionally, the oxidation reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the tert-butyl alcohol is 0.1-1000 h -1 Excellence inIs selected to be 1 to 200 hours -1 。
Optionally, the reaction is carried out in a microchannel reactor, the amount of the catalyst is 0.1-50 mg, preferably 0.2-10 mg, based on 10mL of the tert-butyl alcohol, and the residence time of the reaction material is 0.1-15 min, preferably 0.5-5 min.
Optionally, the method further comprises: the oxidation reaction is carried out in the presence of a solvent; the solvent is water, C1-C6 alcohol, C3-C8 ketone and C2-C6 nitrile, or the combination of two or three of them; the weight ratio of the tert-butanol to the solvent is 1: (0.1-20).
Optionally, the peroxide is hydrogen peroxide, peracetic acid, or propionic acid, or a combination of two or three thereof; the molar ratio of the tert-butyl alcohol to the peroxide is 1: (0.1 to 10), preferably 1: (0.2-5).
Optionally, the conditions of the reaction include: the temperature is 0-80 ℃, and preferably 20-50 ℃; the pressure is 0.01 to 3MPa, preferably 0.1 to 2.5MPa; the time is 0.1 to 12 hours, preferably 0.2 to 5 hours.
According to the technical scheme, the reaction of catalyzing and oxidizing the tert-butyl alcohol by using the special modified nano carbon-based material as the catalyst can realize the oxidation of the tert-butyl alcohol under mild conditions, the conversion rate of raw materials and the selectivity of a target product are high, the effective utilization rate of peroxide can be obviously improved, and the production cost is reduced.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a process for oxidizing tert-butanol, the process comprising: the method comprises the following steps of carrying out contact reaction on tertiary butanol and peroxide in the presence of a catalyst, wherein the catalyst is a modified nano carbon-based material, and the preparation step of the modified nano carbon-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, putting the second conductive object into an electrolyte, applying a voltage of 0.1-110V, preferably 5-80V, to perform electrolysis for 1-30 days, preferably 5-15 days, and obtaining an electrolyzed electrolyte, wherein the first conductive object is a graphite rod;
b. b, mixing the electrolyzed electrolyte obtained in the step a with hydrazine hydrate, performing first modification treatment at the temperature of 20-200 ℃, preferably 60-100 ℃, for 2-24 hours, preferably 5-20 hours, and then freeze-drying the material after 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 hydrazine hydrate, performing second modification treatment at 0-200 ℃, preferably 50-100 ℃, for 1-12 h, preferably 2-10 h, and freeze-drying the material after the second modification treatment.
According to the disclosure, in step a, the graphite rod is a rod made of graphite, and the size of the rod can be changed in a wide range, for example, the diameter of the graphite rod can be 2-20 mm, and the length can be 2-100 cm, wherein the length refers to the axial length of the graphite rod.
According to the present disclosure, in step a, the second conductive material may be any of various common conductive materials, and has no requirement on material and shape, and may be, for example, a common rod or plate shape, specifically, an iron rod, an iron plate, a graphite rod, a graphite plate, a copper rod, and the like, preferably a rod shape such as an iron rod, a graphite rod, a copper rod, and the like, more preferably a graphite rod, and is not limited in size, and most preferably a graphite rod matching the size of the first conductive material. When the electrolysis is performed, a distance, for example, 3 to 10cm, may be maintained between the first conductive material and the second conductive material.
According to the present disclosure, in the step a, the electrolyte may have a resistivity of 0 to 20M Ω · cm -1 The aqueous solution of (3), further, the water content of the aqueous solution may be 85% by weight or more. The aqueous solution may also containCommon inorganic acids (such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), inorganic bases (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.), inorganic salts (such as sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, etc.), or organic solvents (such as 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.
In a first specific embodiment of the disclosure, the electrolytic solution after electrolysis is directly subjected to a first modification treatment, and then the material after the first modification treatment is subjected to freeze drying to obtain a modified nanocarbon-based material; according to the embodiment, only one step of freeze drying is carried out, so that the energy consumption is reduced, and when the prepared modified nano carbon-based material is used for catalyzing and oxidizing the reaction of tert-butyl alcohol, the target product selectivity is high. In this embodiment, the weight ratio of the electrolyzed electrolyte solution to hydrazine hydrate may be 10: (0.01 to 5), preferably 10: (0.1-2).
In a second specific embodiment of the present disclosure, the electrolyzed electrolyte is subjected to primary freeze drying, the dried nanocarbon particles are subjected to secondary modification treatment, and then subjected to primary freeze drying to obtain a modified nanocarbon-based material; compared with the first specific embodiment, the second embodiment can improve the hydrazine hydrate utilization rate in the modification treatment, the modification treatment conditions are milder, and the selectivity of the target product is higher when the prepared modified nanocarbon-based material is used for catalyzing the reaction of oxidizing tertiary butanol. In this embodiment, the weight ratio of the nanocarbon particles to hydrazine hydrate may be 1: (1 to 1000), preferably 1: (2-500).
According to the present disclosure, in step b, the freeze-drying in both embodiments can 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.
According to the present disclosure, the oxygen in the modified nanocarbon-based material is mainly present in the form of hydroxyl oxygen, the proportion of the hydroxyl oxygen content of the modified nanocarbon-based material to the total oxygen content being greater than 70%; further preferably, the proportion of the hydroxyl oxygen content to the total oxygen content is greater than 85%.
According to the present disclosure, the particle size of the modified nanocarbon-based material prepared by the above steps may be 1 to 50nm, preferably 3 to 20nm, and more preferably 5 to 10nm. 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 that are the largest in distance. The modified nanocarbon-based material of the present disclosure has a uniform particle size and a suitable hydroxyl oxygen content, and exhibits excellent catalytic oxidation performance in a catalytic oxidation reaction of t-butanol or the like.
The process for the oxidation of tert-butanol of the present disclosure may be carried out in various conventional catalytic reactors, for example, may be carried out in a batch tank reactor or a three-neck flask, or in suitable other reactors such as fixed bed, moving bed, suspended bed, microchannel reactor, and the like.
In an alternative embodiment of the present disclosure, the reaction is carried out in a slurry bed reactor, and in this case, the amount of the catalyst may be appropriately selected according to the amounts of the cyclic hydrocarbon and the peroxide, for example, the amount of the catalyst is 1 to 500mg, preferably 2 to 100mg, based on 10mL of the t-butanol.
In another alternative embodiment of the present disclosure, the reaction may be carried out in a fixed bed reactor. At this time, the weight hourly space velocity of the tertiary butanol is 0.1-1000 h -1 Preferably 1 to 200h -1 。
In another alternative embodiment of the present disclosure, the reaction is performed in a microchannel reactor, the amount of the catalyst is 0.1 to 50mg, preferably 0.2 to 10mg, based on 10mL of the tert-butyl alcohol, and the residence time of the reaction material is 0.1 to 15min, preferably 0.5 to 5min, wherein the reaction material refers to a mixture of the tert-butyl alcohol, peroxide, catalyst and the like entering the microchannel reactor to participate in the reaction.
According to the present disclosure, to increase the degree of mixing between the reaction materials, the method may further comprise: the oxidation reaction is carried out in the presence of a solvent. The solvent may be various liquid substances capable of dissolving t-butanol and peroxide or promoting the mixing of both, and promoting the dissolution of the target product. Generally, the solvent may be water, C1-C6 alcohols, C3-C8 ketones, and C2-C6 nitriles, or a combination of two or three thereof. Specific examples of the solvent may include, but are not limited to: water, methanol, ethanol, n-propanol, isopropanol, cyclohexanone, isobutanol, acetone, butanone, and acetonitrile. Preferably, the solvent is selected from water and C1-C6 alcohols. More preferably, the solvent is methanol and/or water. The amount of the solvent may be appropriately selected depending on the amounts of t-butanol and peroxide, and for example, the weight ratio of the t-butanol to the solvent may be 1: (0.1 to 20), preferably 1: (1-10).
According to the present disclosure, the peroxide may be a compound having an-O-bond in a molecular structure, and may be selected from hydrogen peroxide, hydroperoxide, and peracid. The hydroperoxide is a substance obtained by substituting one hydrogen atom in a hydrogen peroxide molecule with an organic group. The peracid refers to an organic oxyacid having an-O-O-bond in the molecular structure. Specific examples of the peroxide may include, but are not limited to, hydrogen peroxide, peracetic acid, peroxopropionic acid, cumyl peroxide, cyclohexyl hydroperoxide. Preferably, the peroxide is hydrogen peroxide, which may be in various forms commonly used in the art. From the viewpoint of further improving the safety of the process according to the present disclosure, it is preferred to use hydrogen peroxide in the form of an aqueous solution, in which case the concentration of the aqueous hydrogen peroxide solution may be conventional in the art, for example, from 20 to 80% by weight. The aqueous solution of hydrogen peroxide having a concentration satisfying the above requirements may be prepared by a conventional method or may be commercially available, for example, 30 wt% hydrogen peroxide.
According to the present disclosure, the molar ratio of the tert-butanol to the peroxide may be 1: (0.1 to 2), preferably 1: (0.2-1).
According to the present disclosure, the conditions of the oxidation reaction may be: the temperature is 0-80 ℃, and preferably 20-50 ℃; the pressure is 0.01 to 3MPa, preferably 0.1 to 2.5MPa; the time is 0.1 to 12 hours, preferably 0.2 to 5 hours.
The method for oxidizing tert-butyl alcohol disclosed by the invention can further comprise the step of separating a mixture containing tert-butyl hydroperoxide obtained by the oxidation reaction to separate the tert-butyl hydroperoxide. The method for separating t-butyl hydroperoxide from the mixture obtained by the reaction is not particularly limited in the present disclosure, and may be a routine choice in the art.
According to the method, a special modified nano carbon-based material is used as a catalyst to catalyze the oxidation reaction of tert-butyl alcohol, so that the oxidation of tert-butyl alcohol can be realized under a mild condition, the conversion rate of raw materials and the selectivity of a target product are high, the effective utilization rate of peroxide can be obviously improved, and the production cost is reduced.
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 7 are for explaining the modified nanocarbon-based material and the preparation method thereof of the present disclosure.
In the preparation examples, the average particle size of the modified nanocarbon-based material was measured using a transmission electron microscope model TECNAIG2F20 (200 kv) from FEI company 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 an electron microscope for observation, and randomly taking 100 particles for carrying out particle size statistics.
In the preparation examples, the ratio of hydroxyl oxygen content of the modified nanocarbon-based material is determined by X-ray photoelectron spectroscopy analysis XPS under the following test conditions: the test was carried out on an ESCALB 250 model X-ray photoelectron spectrometer from Thermo Scientific, equipped with Thermo Avantage V5.926 software, with an excitation source of monochromated Al K.alpha.X rays, an energy of 1486.6eV, a power of 150W, a transmission energy for narrow scanning of 30eV, a base vacuum of 6.5X 10 for the analytical test - 10 mbar, C1s peak of elemental carbon for electron binding energy (28)4.6 eV), data processing was performed on Thermo Avantage software, and quantitative analysis was performed in the analysis module using the sensitivity factor method. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3h before testing.
Preparation of example 1
500mL of a glass having a resistivity of 15 M.OMEGA.cm was added to a beaker -1 The anode graphite rod (diameter 10mm and length 30 cm) and the cathode graphite rod (diameter 10mm and length 30 cm) are placed in the ultrapure water, the distance between the anode graphite rod and the cathode graphite rod is kept at 10cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode graphite rod is connected with the negative pole of the direct current power supply, and 50V voltage is applied to electrolyze for 8 days, so that the electrolyzed electrolyte is obtained. Mixing the electrolyzed electrolyte and hydrazine hydrate according to the weight ratio of 10:1, performing modification treatment at 80 ℃ for 12h, and performing freeze drying on the modified material at-20 ℃ and 50Pa for 24h to obtain the modified carbon-based nanomaterial C1. The particle size was found to be 8nm and the proportion of hydroxyl oxygen content to total oxygen content was found to be 91%.
Preparation of example 2
500mL of a glass having a resistivity of 15 M.OMEGA.cm was added to a beaker -1 The anode graphite rod (diameter 20mm and length 30 cm) and the cathode graphite rod (diameter 20mm and length 30 cm) were placed in the ultrapure water, the distance between the anode graphite rod and the cathode graphite rod was kept at 10cm, the anode graphite rod was connected to the positive electrode of a direct current power supply and the cathode graphite rod was connected to the negative electrode of the direct current power supply, and electrolysis was carried out for 18 days by applying a voltage of 120V to obtain an electrolyzed solution. Mixing the electrolyzed electrolyte and hydrazine hydrate according to the weight ratio of 10:5, carrying out modification treatment for 6h at 100 ℃ after mixing, and then carrying out freeze drying on the modified material for 24h at-20 ℃ and 50Pa to obtain the modified carbon-based nano material C2. The particle size was found to be 21nm and the proportion of hydroxyl oxygen content to total oxygen content was found to be 81%.
Preparation of example 3
500mL of a glass having a resistivity of 15 M.OMEGA.. Cm was added to a beaker -1 The anode graphite rod (diameter: 10mm, length: 30 cm) and the cathode graphite rod (diameter: 10mm, length: 30 cm) were placed therein, and the anode was heldAnd the distance between the graphite rod and the cathode graphite rod is 10cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode graphite rod is connected with the negative pole of the direct current power supply, and a voltage of 50V is applied for electrolysis for 12 days to obtain an electrolyzed electrolyte. Mixing the electrolyzed electrolyte and hydrazine hydrate according to the weight ratio of 100:0.1, performing modification treatment at 120 ℃ for 24 hours, and performing freeze drying on the modified material at-20 ℃ and 50Pa for 24 hours to obtain the modified nano carbon-based material C3. The particle size was measured to be 5nm and the proportion of hydroxyl oxygen content to total oxygen content was 74%.
Preparation of example 4
500mL of a glass having a resistivity of 15 M.OMEGA.cm was added to a beaker -1 The anode graphite rod (diameter 10mm and length 30 cm) and the cathode graphite rod (diameter 10mm and length 30 cm) are placed in the ultrapure water, the distance between the anode graphite rod and the cathode graphite rod is kept at 10cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode graphite rod is connected with the negative pole of the direct current power supply, and 50V voltage is applied to electrolyze for 8 days to obtain the electrolyzed electrolyte. Freeze-drying the electrolyzed electrolyte for 24h at-20 ℃ and 50Pa to obtain nano carbon particles, and mixing the nano carbon particles with hydrazine hydrate according to a weight ratio of 1:3, carrying out modification treatment at 80 ℃ for 6h after mixing, and then carrying out freeze drying on the modified material at-20 ℃ and 50Pa for 24h to obtain the modified carbon-based nano material C4. The particle size was measured to be 9nm and the proportion of hydroxyl oxygen content to total oxygen content was 88%.
Preparation of example 5
1500mL of a material having a resistivity of 15 M.OMEGA.cm was added to the beaker -1 The anode graphite rod (diameter 8mm and length 50 cm) and the cathode copper rod (diameter 8mm and length 50 cm) are placed in the ultrapure water, the distance between the anode graphite rod and the cathode copper rod is kept at 5cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode copper rod is connected with the negative pole of the direct current power supply, and 30V voltage is applied to electrolyze for 5 days, so that the electrolyzed electrolyte is obtained. Freeze-drying the electrolyzed electrolyte for 12h at-25 ℃ and 80Pa to obtain nano carbon particles, and then mixing the nano carbon particles with hydrazine hydrate according to the weight ratio of 1: 15 mixing and then heating at 60 DEG CAnd (3) carrying out modification treatment for 8h, and then carrying out freeze drying on the modified material at-20 ℃ and 50Pa for 12h to obtain the modified nano carbon-based material C5. The particle size was measured to be 11nm and the proportion of hydroxyl oxygen content to total oxygen content was 82%.
Preparation of example 6
500mL of a glass having a resistivity of 15 M.OMEGA.. Cm was added to a beaker -1 The anode graphite rod (diameter 10mm and length 30 cm) and the cathode graphite rod (diameter 10mm and length 30 cm) are placed in the ultrapure water, the distance between the anode graphite rod and the cathode graphite rod is kept at 10cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode graphite rod is connected with the negative pole of the direct current power supply, and a voltage of 80V is applied for electrolysis for 10 days, so that the electrolyzed electrolyte is obtained. Freeze-drying the electrolyzed electrolyte for 12h at-20 ℃ and 50Pa to obtain nano carbon particles, and mixing the nano carbon particles with hydrazine hydrate according to a weight ratio of 1:800, performing modification treatment at 120 ℃ for 24 hours, and performing freeze drying on the modified material at-20 ℃ and 50Pa for 12 hours to obtain the modified carbon-based nano-material C6. The particle size was measured to be 5nm and the proportion of hydroxyl oxygen content to total oxygen content was 79%.
Preparation of example 7
500mL of a glass having a resistivity of 15 M.OMEGA.cm was added to a beaker -1 The anode graphite rod (diameter 10mm and length 30 cm) and the cathode graphite rod (diameter 10mm and length 30 cm) are placed in the ultrapure water, the distance between the anode graphite rod and the cathode graphite rod is kept at 10cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode graphite rod is connected with the negative pole of the direct current power supply, and 90V voltage is applied to electrolyze for 8 days to obtain the electrolyzed electrolyte. Freeze-drying the electrolyzed electrolyte for 24h at-20 ℃ and 50Pa to obtain nano carbon particles, and mixing the nano carbon particles with 50% hydrazine hydrate according to the weight ratio of 1:1.5, carrying out modification treatment for 1h at 20 ℃, and then carrying out freeze drying on the modified material for 24h at-20 ℃ and 50Pa to obtain the modified nano carbon-based material C7. The particle size was found to be 10nm and the proportion of hydroxyl oxygen content to total oxygen content was found to be 67%.
Preparation of comparative example 1
500mL of a glass having a resistivity of 15 M.OMEGA.cm was added to a beaker -1 The anode graphite rod (diameter 10mm and length 30 cm) and the cathode graphite rod (diameter 10mm and length 30 cm) are placed in the ultrapure water, the distance between the anode graphite rod and the cathode graphite rod is kept at 10cm, the anode graphite rod is connected with the positive pole of a direct current power supply, the cathode graphite rod is connected with the negative pole of the direct current power supply, and 50V voltage is applied to electrolyze for 8 days, so that the electrolyzed electrolyte is obtained. The electrolyzed electrolyte was freeze-dried at-20 ℃ and 50Pa for 24 hours to obtain comparative nanocarbon-based material D1. The particle size was found to be 27nm and the proportion of hydroxyl oxygen content to total oxygen content was found to be 58%.
Examples 1 to 13 are for explaining a method of catalyzing oxidation reaction of t-butanol using the modified nanocarbon-based material of the present disclosure. Comparative example 1 is intended to illustrate the catalytic oxidation of tert-butanol using a different catalytic material than 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:
t-butanol conversion% = (molar amount of t-butanol added before reaction-molar amount of t-butanol remaining after reaction)/molar amount of t-butanol added before reaction × 100%;
the selectivity of tert-butyl hydroperoxide in the target product is% = the molar amount of the target product tert-butyl hydroperoxide generated after the reaction/the molar amount of tert-butyl hydroperoxide added before the reaction x 100%;
peroxide effective utilization ratio% = (molar amount of target product t-butyl hydroperoxide formed after reaction)/molar amount of peroxide participating in reaction x 100%.
Example 1
Adding 2mg of the modified nanocarbon-based material C1 as a catalyst and 10mL of tert-butyl alcohol into a 100mL high-pressure reaction kettle, then adding 30 wt% of hydrogen peroxide and methanol as a solvent, wherein the molar ratio of the tert-butyl alcohol to the hydrogen peroxide is 2:1, the weight ratio of the tertiary butanol to the methanol is 1:2; stirring and reacting for 2h at 30 ℃ and 0.8MPa (nitrogen pressure), cooling, releasing pressure, sampling, centrifuging, filtering and separating the catalyst. And calculating the conversion rate of the tertiary butanol, the selectivity of the target product tertiary butyl hydroperoxide and the effective utilization rate of the hydrogen peroxide. The results are listed in table 1.
Examples 2 to 7
T-butanol was catalytically oxidized according to the method of example 1, except that C1 was replaced with the same amount of modified nanocarbon-based materials C2 to C7, respectively. The results of the oxidation product analysis are shown in Table 1.
Example 8
Tert-butanol was catalyzed according to the method of example 1 except that the weight ratio of tert-butanol to methanol was 1:25; the dosage of the modified nanocarbon-based material C1 is 1.0g based on 10mL of tertiary butanol. The results of the oxidation product analysis are shown in Table 1.
Example 9
Tert-butanol was catalyzed according to the procedure of example 1 except that the molar ratio of tert-butanol to hydrogen peroxide was 10:1, the weight ratio of the tertiary butanol to the methanol is 10:1. the results of the oxidation products are shown in Table 1.
Example 10
Tert-butanol, 30% by weight of hydrogen peroxide and methanol as solvent were mixed to form a liquid mixture. Then, the liquid mixture is fed into a reaction zone from a feed inlet at the bottom of the micro fixed bed reactor to be contacted with a modified nanocarbon-based material C1 serving as a catalyst, wherein the molar ratio of the tert-butyl alcohol to the hydrogen peroxide is 1:1, the weight ratio of the tertiary butanol to the methanol is 1:3; the reaction temperature is 30 ℃, the pressure is 1.0MPa, and the weight hourly space velocity of the tertiary butanol is 2.0h -1 . The reaction mixture obtained after the reaction was carried out for 2 hours was subjected to gas chromatography, and the results are shown in Table 1.
Example 11
Tert-butanol, 30% by weight of hydrogen peroxide and methanol as solvent were mixed to form a liquid mixture. Then, theFeeding a liquid mixture into a reaction zone from a feed inlet at the bottom of a miniature fixed bed reactor to contact with a modified nano carbon-based material C1 serving as a catalyst, wherein the molar ratio of tert-butyl alcohol to hydrogen peroxide is 1:10, the weight ratio of the tertiary butanol to the methanol is 1:4; the reaction temperature is 30 ℃, the pressure is 0.8MPa, and the weight hourly space velocity of the tertiary butanol is 0.5h -1 . The reaction mixture obtained after the reaction was carried out for 2 hours was subjected to gas chromatography, and the results are shown in Table 1.
Example 12
Mixing tert-butyl alcohol, oxydol serving as an oxidant and methanol serving as a solvent, and adding the modified nanocarbon-based material C1 serving as a catalyst to form a reaction material. The reaction mass was then fed from the feed inlet of a microchannel bed reactor (corning, usa, model HR-50) into the reaction zone, where the molar ratio of tert-butanol to hydrogen peroxide was 1:1, the weight ratio of tert-butanol to methanol was 1:2; taking 10mL of tert-butyl alcohol as a reference, wherein the dosage of the modified nano carbon-based material C1 is 2mg; the reaction temperature is 30 ℃, the pressure is normal pressure, the residence time of the reaction materials is 20min, the reaction mixture is collected at a discharge port for gas chromatography analysis, and the conversion rate of the tertiary butyl alcohol, the selectivity of the target product tertiary butyl hydroperoxide and the effective utilization rate of the hydrogen peroxide are calculated. The results are listed in table 1.
Example 13
Mixing tert-butyl alcohol, peroxyacetic acid serving as an oxidant and methanol serving as a solvent, and adding the modified nanocarbon-based material C1 serving as a catalyst to form a reaction material. The reaction mass was then fed from the feed inlet of a microchannel bed reactor (Corning, USA, model HR-50) into the reaction zone, where the molar ratio of tert-butanol to peroxyacetic acid was 1:1; taking 10mL of tert-butyl alcohol as a reference, the using amount of the modified nanocarbon-based material C1 is 2mg; the reaction temperature is 30 ℃, the pressure is 0.8MPa, the residence time of the reaction materials is 5min, the reaction mixture is collected at a discharge port for gas chromatographic analysis, and the conversion rate of the tertiary butanol, the selectivity of the target product tertiary butyl hydroperoxide and the effective utilization rate of the peroxyacetic acid are calculated. The results are listed in table 1.
Comparative example 1
T-butanol was catalyzed according to the method of example 1, except that the modified nanocarbon based material C1 was not used as a catalyst. The results of the oxidation product analysis are shown in Table 1.
Comparative example 2
T-butanol was catalyzed according to the method of example 1, except that the same amount of the non-modified nanocarbon-based material D1 was used instead of the modified nanocarbon-based material C1 as the catalyst. The results of the oxidation product analysis are shown in Table 1.
TABLE 1
According to the data in table 1, it can be found that the catalytic oxidation of tert-butyl alcohol can be realized under mild conditions by using the modified nanocarbon-based material of the present disclosure as a catalyst, and the raw material conversion rate and the target product selectivity are higher. In the preparation process of the nano-carbon-based material, a proper amount of hydrazine hydrate is added, so that the generation of hydroxyl oxygen groups can be promoted, the improvement of the catalytic oxidation performance of the nano-carbon-based material is facilitated, and under the condition that the hydroxyl oxygen content of the modified nano-carbon-based material accounts for more than 70 percent of the total oxygen proportion, the activity of the catalyst can be further improved, so that the tert-butyl alcohol reaction is promoted to generate tert-butyl hydroperoxide.
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 (22)
1. A process for the oxidation of tert-butanol, comprising: the method comprises the following steps of carrying out contact reaction on tertiary butanol and peroxide in the presence of a catalyst, wherein the catalyst is a modified nano carbon-based material, and the preparation step of the modified nano carbon-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, and then putting the second conductive object into an electrolyte, applying a voltage of 0.1-110V to carry out electrolysis for 1-30 days to obtain an electrolyzed electrolyte, wherein the first conductive object is a graphite rod, 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, and the water content of the aqueous solution is more than 85 wt%;
b. b, mixing the electrolyzed electrolyte obtained in the step a with hydrazine hydrate, then carrying out first modification treatment for 2-24 h at the temperature of 20-200 ℃, and then carrying out freeze drying on the material after 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 hydrazine hydrate, performing second modification treatment at the temperature of 0-200 ℃ for 1-12 h, and freeze-drying the material after the second modification treatment.
2. The method according to claim 1, wherein in the step a, the second conductor is electrolyzed at a voltage of 5 to 80V for 5 to 15 days;
in the step b, the temperature of the first modification treatment is 60-100 ℃, and the time is 5-20 h;
or the temperature of the second modification treatment is 50-100 ℃, and the time is 2-10 h.
3. The method according to claim 1, wherein in the step a, the graphite rod has a diameter of 2-20 mm and a length of 2-100 cm; and/or the presence of a gas in the gas,
the second conductive object is an iron rod, a graphite rod or a copper rod.
4. The method of claim 3, wherein in step a, the second conductor is a graphite rod matched to the size of the first conductor.
5. The method according to claim 1, wherein in the step b, the weight ratio of the electrolyzed electrolyte to the hydrazine hydrate is 10: (0.01-5); or the weight ratio of the nano carbon particles to the hydrazine hydrate is 1: (1-1000);
the conditions for freeze-drying include: the temperature is between 50 ℃ below zero and 0 ℃, the pressure is between 1 and 200Pa, and the time is between 1 and 96 hours.
6. The method of claim 5, wherein in the step b, the weight ratio of the electrolyzed electrolyte to the hydrazine hydrate is 10: (0.1-2); or the weight ratio of the nano carbon particles to the hydrazine hydrate is 1: (2-500);
the conditions for freeze-drying include: the temperature is between 40 ℃ below zero and 10 ℃ below zero, the pressure is between 5 and 100Pa, and the time is between 6 and 48 hours.
7. The process according to claim 1, wherein the proportion of hydroxyl oxygen content in the modified nanocarbon-based material to the total oxygen content is greater than 70%.
8. The process according to claim 7, wherein the proportion of the hydroxyl oxygen content in the modified nanocarbon-based material with respect to the total oxygen content is greater than 85%.
9. The method according to claim 1, wherein the particle size of the modified nanocarbon-based material is between 1 and 50nm.
10. The method according to claim 9, wherein the particle size of the modified nanocarbon-based material is between 3 and 20nm.
11. The method according to claim 10, wherein the particle size of the modified nanocarbon-based material is between 5 and 10nm.
12. The process of claim 1, wherein the reaction is carried out in a slurry bed reactor, and the catalyst is used in an amount of 1 to 500mg, based on 10mL of the t-butanol.
13. The process according to claim 12, wherein the catalyst is used in an amount of 2 to 100mg based on 10mL of the t-butanol.
14. The process as claimed in claim 1, wherein the reaction is carried out in a fixed bed reactor, and the weight hourly space velocity of the tert-butanol is 0.1 to 1000h -1 。
15. The process of claim 14, wherein the weight hourly space velocity of the tert-butanol is from 1 to 200h -1 。
16. The process of claim 1, wherein the reaction is carried out in a microchannel reactor, the catalyst is used in an amount of 0.1 to 50mg, and the residence time of the reaction mass is 0.1 to 15min, based on 10mL of the tert-butanol.
17. The process of claim 16, wherein the catalyst is used in an amount of 0.2 to 10mg and the residence time of the reaction mass is 0.5 to 5min, based on 10mL of the tert-butanol.
18. The method of claim 1, wherein the method further comprises: the reaction is carried out in the presence of a solvent; the solvent is water, C1-C6 alcohol, C3-C8 ketone and C2-C6 nitrile, or the combination of two or three of them;
the weight ratio of the tert-butanol to the solvent is 1: (0.1-20).
19. The process of claim 1, wherein the peroxide is hydrogen peroxide, peracetic acid, or propionic acid, or a combination of two or three thereof;
the molar ratio of the tert-butyl alcohol to the peroxide is 1: (0.1-10).
20. The process of claim 19, wherein the molar ratio of the tert-butanol to the peroxide is 1: (0.2-5).
21. The method of claim 1, wherein the conditions of the reaction comprise: the temperature is 0-80 ℃, the pressure is 0.01-3 MPa, and the time is 0.1-12 h.
22. The method of claim 21, wherein the conditions of the reaction comprise: the temperature is 20-50 ℃, the pressure is 0.1-2.5 MPa, and the time is 0.2-5 h.
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