CN112125795B - Method for preparing adipic acid by oxidizing cyclohexane - Google Patents
Method for preparing adipic acid by oxidizing cyclohexane Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
Abstract
The invention relates to a method for preparing adipic acid by cyclohexane oxidation, which mainly solves the problems that in the reaction for preparing adipic acid by cyclohexane oxidation in the prior art, a plurality of metal catalysts are needed to be adopted, and the metal catalysts enter soil and water along with waste residues and waste liquid, so that serious environmental pollution is caused, and the like. The method for preparing adipic acid by adopting cyclohexane oxidation comprises the steps of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of a reaction accelerator and a solvent to obtain adipic acid; the reaction promoter comprises an organic azo compound or the reaction promoter comprises quinone, so that the problem is well solved, and the method can be used for industrial production of adipic acid by cyclohexane air oxidation.
Description
Technical Field
The invention relates to a method for preparing adipic acid by oxidizing cyclohexane.
Background
Adipic acid (adipic acid), also known as fatty acid, is an important organic dibasic acid, and is an important raw material for preparing polyurethane and nylon 66. The international adipic acid is more than 70% in the field of nylon 66, and the national adipic acid is 78% in the field of polyurethane. The world adipic acid production methods currently include four methods, namely a phenol method, a cyclohexane method, a cyclohexene method and a butadiene method. In the fifty years ago, adipic acid was produced mainly by taking phenol as a raw material, and the method for producing adipic acid by using phenol is a classical method, and has the advantages of high product purity, mature production technology and no need of stainless steel materials. But the phenol resources are limited and expensive, the cost of the products is high, and the phenol is basically eliminated at present. The modern industrial production mainly adopts a cyclohexane method, the yield of which accounts for about 93 percent of the total yield, and the method mainly comprises two steps for synthesizing adipic acid. The first step of oxidizing cyclohexane to form cyclohexanol and cyclohexanone (KA oil) is followed by separation of the reaction mixture, recycling of unreacted cyclohexane, and the subsequent second step of oxidizing KA oil to adipic acid with nitric acid. The method has the advantages that: the process is mature, the production process is dominant in adipic acid production, byproducts are mainly succinic acid and glutaric acid, the separation is easy, and the product is purer. The defects are that: in the process of synthesizing KA oil, the single pass conversion rate is lower, the conversion rate is generally 5% -12%, and a large amount of strong acid and alkali solution is needed to corrode equipment, so that the environment is polluted; in the second step of oxidizing KA oil to prepare adipic acid, the oxidant is nitric acid, and each 1t of adipic acid product consumes 1.3t of 68% nitric acid, so that equipment corrosion is serious, and a large amount of oxynitride with serious pollution to the environment can be generated.
In order to solve the problem, scientific researchers explore a process route for synthesizing adipic acid by taking cyclohexane as a raw material and taking air or oxygen as an oxidant, wherein the process route is more environment-friendly and concise.
Chinese patent nos. CN 1247501C (title: catalytic oxidation of cyclohexane), CN 1218922C (title: method for preparing adipic acid by air oxidation of hexacarbocyclic compound), and CN 1231449C (title: method for preparing adipic acid by biomimetic catalytic oxidation of cyclohexane by oxygen) disclose methods for preparing adipic acid by air oxidation of cyclohexane using metalloporphyrin as a catalyst. Chinese patent nos. CN 101239899B (title: a method for preparing adipic acid by catalytic oxidation of cyclohexane in one step) and CN 101337878B (title: a method for directly producing adipic acid by catalytic oxidation of cyclohexane) disclose a method for preparing adipic acid by oxidizing cyclohexane in one step by using a carbon material as a carrier to support a nano ruthenium dioxide catalyst or directly using the carbon material as a catalyst.
In document Organic Process Research&Development 1998,2,255-260 (article title: direct Conversion of Cyclohexane into Adipic Acid with Molecular Oxygen Catalyzed by N-Hydroxyphthalimide Combined with Mn (acac)) 2 and Co(OAc) 2 ) In Ishii et al, a free radical catalyst NHPI was used, and a small amount of a transition metal promoter was added to oxidize cyclohexane directly to adipic acid with oxygen. In acetic acid solvent, NHPI (10 mol%) and manganese acetylacetonate (1 mol%) are used as catalysts, the reaction is carried out at 100 ℃ for 20 hours, the cyclohexane conversion reaches 73%, and the yield of adipic acid is 53%.
The method well solves the problem of adipic acid synthesis from various angles, but has some defects and disadvantages, and the method needs to adopt various metal catalysts, and the metal catalysts cause serious environmental pollution and other problems along with the waste residue and liquid entering soil and water, and has a certain distance from the industrial production of adipic acid.
Disclosure of Invention
The invention mainly solves the problems that in the prior art, in the reaction of preparing adipic acid by oxidizing cyclohexane, a plurality of metal catalysts are needed, and the metal catalysts enter soil and water along with waste residues and waste liquid, so that serious environmental pollution is caused, and the like.
In order to solve the technical problems, the method for preparing adipic acid by oxidizing cyclohexane provided by the invention comprises the following steps:
technical scheme 1: the method for preparing adipic acid by oxidizing cyclohexane comprises the steps of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of a reaction accelerator and a solvent to obtain adipic acid; the reaction promoter comprises an organic azo compound, or the reaction promoter comprises a quinone.
The invention has the advantage that metal elements can be not used as catalyst components, thereby reducing the pressure of metal on the environment. Furthermore, the addition of the organic azo compound can increase the conversion of cyclohexane and the selectivity to adipic acid, and/or the quinone can increase the conversion of cyclohexane and the selectivity to adipic acid.
Technical scheme 2: in the above technical scheme, the reaction promoter comprises an organic azo compound and quinone, and the molar ratio of the organic azo compound to the quinone is preferably 0.1-10. The quinone and the organic azo compound have mutually reinforcing effects in improving the conversion rate of cyclohexane and the selectivity of adipic acid. More preferably, the molar ratio of the organic azo compound to quinone is 0.1 to 10. Such as but not limited to 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.
Technical scheme 3: in the above technical solution, the accelerator preferably includes a nitroxide radical organic compound. The nitroxide radical organic compound and the organic azo compound have mutual enhancement effect in terms of improving the conversion rate of cyclohexane and the selectivity of adipic acid; the molar ratio of the organic azo compound to the nitroxide free radical organic compound is preferably from 0.1 to 10, such as, but not limited to, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc. The nitroxide organic compound and quinone have a mutual promoting effect in terms of improving the conversion of cyclohexane and the selectivity of adipic acid, and the molar ratio of quinone to nitroxide organic compound is preferably 0.1 to 10. Such as but not limited to 0.2, 0.4, 0.6, 0.8, 1.2, 1.4, 2.2, 2.6, 3.2, 3.6, 4.2, 4.6, 5.2, 5.6, 6.2, 6.6, 7.2, 7.6, 8.2, 8.6, 9.2, 9.6, etc.
Technical scheme 4: in the above technical solution, the nitroxide radical organic compound is preferably a diimide nitroxide radical organic compound. The diimide nitroxide radical organic compound is more preferably an N-hydroxydiimide-containing compound. The diimide nitroxide radical organic compound preferably corresponds to the following formula 1:
for example, but not limited to, the diimide nitroxide radical organic compound may be selected from at least one of N-hydroxyphthalimide (NHPI) or N-hydroxysuccinimide (NHS).
Technical scheme 5: in the above technical solution, the organic azo compound preferably conforms to the following structure:
wherein R is 1 And R is 2 Independently, a hydrocarbon group of C1 to C10 is preferred. Further preferred are C1-C10 alkyl groups such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and the like. Such as but not limited to at least one of the organic azo compounds diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).
Technical scheme 6: in the above technical scheme, the quinone is preferably ortho-position biquinone and/or para-position biquinone.
Technical scheme 7: in the above technical scheme, the para-diquinone may optionally conform to the following structural formula 3:
technical scheme 8: in the above technical scheme, the ortho-diquinone optionally conforms to the following structure 4:
by way of non-limiting example, the para-diphenoquinone may be selected from terephthalquinone (abbreviated as PBQ) and the ortho-diphenoquinone may be selected from ortho-diphenoquinone.
Technical scheme 9: in the above technical solution, the solvent preferably includes acetic acid, more preferably the solvent is substantially acetic acid, and most preferably the solvent is acetic acid.
In the above technical solution, the oxidizing agent containing oxygen molecules may include pure oxygen, oxygen-enriched air or oxygen-depleted air.
The technical key of the invention is the choice of the promoter, and the process conditions of the reaction, such as the amount of the promoter, the proportion of the solvent, the cyclohexane and the oxidant, etc., can be reasonably selected by the person skilled in the art without creative effort.
By way of non-limiting example, in the above embodiments, the molar ratio of solvent to cyclohexane may be 1 to 10, such as 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.
By way of non-limiting example, in the above embodiments, the molar ratio of accelerator to cyclohexane may be greater than 0 and less than 0.05, such as 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, and the like.
As a non-limiting example, in the above technical scheme, the reaction temperature is preferably 50 to 150 ℃. Such as, but not limited to, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃,115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, and the like.
As a non-limiting example, in the above technical scheme, the pressure of the reaction is preferably 0 to 5MPa. Such as but not limited to 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, etc
As a non-limiting example, in the above technical scheme, the reaction time is preferably 0.1 to 7 hours. Such as, but not limited to, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, etc.
In order to solve the technical problems, the accelerator composition provided by the invention comprises the following components:
the technical scheme 10 is as follows: an accelerator composition comprising at least two selected from the group consisting of nitroxide-free organic compounds, organic azo compounds and quinones. The promoter composition is capable of increasing the conversion of cyclohexane and the selectivity to adipic acid; furthermore, the accelerator composition of the present invention may or may not include a metal element component, and when the metal element component is not included, the pressure of the metal element on the environment can be reduced.
As one of the preferable embodiments of claim 10, the composition preferably includes an organic azo compound and a nitroxide-free radical organic compound. The nitroxide-free radical organic compound and the organic azo compound have mutual reinforcing effects in terms of improving the conversion rate of cyclohexane and the selectivity of adipic acid. In embodiments where the composition includes an organic azo compound and a nitroxide free radical organic compound, it is preferred that the molar ratio of the organic azo compound to the nitroxide free radical organic compound is from 0.1 to 10, such as, but not limited to, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.
As a second preferred embodiment of claim 10, the composition preferably comprises an organic azo compound and quinone. The quinone and the organic azo compound have mutually reinforcing effects in improving the conversion rate of cyclohexane and the selectivity of adipic acid. In the embodiment wherein the composition preferably comprises an organic azo compound and a quinone, the molar ratio of the organic azo compound to the quinone is preferably from 0.1 to 10. Such as but not limited to 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.
As a third preferred embodiment of claim 10, the composition preferably comprises a nitroxide organic compound and a quinone. The nitroxide organic compound interacts with the quinone in improving the conversion of cyclohexane and the selectivity of adipic acid. In the embodiment wherein the composition preferably comprises a nitroxide organic compound and a quinone, the molar ratio of nitroxide organic compound to quinone is preferably from 0.1 to 1. Such as but not limited to 0.2, 0.4, 0.6, 0.8, 1.2, 1.4, 2.2, 2.6, 3.2, 3.6, 4.2, 4.6, 5.2, 5.6, 6.2, 6.6, 7.2, 7.6, 8.2, 8.6, 9.2, 9.6, etc.
Technical scheme 11: in the above technical solution, the composition more preferably includes an organic azo compound, a nitroxide radical organic compound and quinone at the same time. In this case, the three components of the organic azo compound, the nitroxide-based organic compound and the quinone have a ternary combination effect in terms of improving the conversion of cyclohexane and the selectivity of adipic acid.
Technical scheme 12: in the above technical solution, in the technical solution including the organic azo compound, the nitroxide radical organic compound and the quinone at the same time, the composition preferably includes, in parts by mole:
the organic azo compound is 0.1 to 10 parts such as, but not limited to, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.2 parts, 1.4 parts, 2.2 parts, 2.6 parts, 3.2 parts, 3.6 parts, 4.2 parts, 4.6 parts, 5.2 parts, 5.6 parts, 6.2 parts, 6.6 parts, 7.2 parts, 7.6 parts, 8.2 parts, 8.6 parts, 9.2 parts, 9.6 parts, etc.;
the nitroxide radical organic compound is 0.1-10 parts such as, but not limited to, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.2 parts, 1.4 parts, 2.2 parts, 2.6 parts, 3.2 parts, 3.6 parts, 4.2 parts, 4.6 parts, 5.2 parts, 5.6 parts, 6.2 parts, 6.6 parts, 7.2 parts, 7.6 parts, 8.2 parts, 8.6 parts, 9.2 parts, 9.6 parts, etc.;
the quinone is 0.1 to 10 parts such as, but not limited to, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.2 parts, 1.4 parts, 2.2 parts, 2.6 parts, 3.2 parts, 3.6 parts, 4.2 parts, 4.6 parts, 5.2 parts, 5.6 parts, 6.2 parts, 6.6 parts, 7.2 parts, 7.6 parts, 8.2 parts, 8.6 parts, 9.2 parts, 9.6 parts, and the like.
Technical scheme 13: in the above technical solution, the nitroxide radical organic compound is preferably a diimide nitroxide radical organic compound. The diimide nitroxide radical organic compound is preferably an N-hydroxydiimide-containing compound. The diimide nitroxide radical organic compound preferably corresponds to the following formula 1:
by way of non-limiting example, such as but not limited to the diimide nitroxide radical organic compound may be selected from at least one of N-hydroxyphthalimide (NHPI) or N-hydroxysuccinimide (NHS).
Technical scheme 14: in the above technical solution, the organic azo compound preferably conforms to the following structure:
wherein R1 and R2 are independently selected from C1-C10 hydrocarbyl. C1-C10 alkyl groups are preferred, such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and the like. Such as, but not limited to, at least one of diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).
Technical scheme 15: in the technical scheme, the quinone is ortho-position biquinone and/or para-position biquinone. Preferably, the para-diquinone optionally corresponds to the following structural formula 3:
preferably the vicinal biquinone optionally corresponds to the structure 4:
by way of non-limiting example, the para-diphenoquinone may be selected from terephthalquinone (abbreviated as PBQ) and the ortho-diphenoquinone may be selected from ortho-diphenoquinone.
The accelerator composition can be used for preparing adipic acid by mixing the components and adding an oxidant which takes cyclohexane and oxygen-containing molecules as raw materials for oxidation reaction; the components in the accelerator composition may be added, without mixing, to the process of preparing adipic acid by oxidation reaction using cyclohexane and an oxidant containing oxygen molecules as raw materials, and the order of addition is not particularly limited.
In order to solve the technical problems, the accelerator composition provided by the invention is applied as follows:
technical scheme 16: the use of the accelerator composition according to any one of the above technical schemes 10 to 15 in the process of preparing adipic acid by oxidation reaction with cyclohexane and an oxidant containing oxygen molecules as raw materials.
The technical key to the use of accelerator compositions is the choice of accelerator components, and the method for a particular application can be reasonably selected by those skilled in the art without the need for inventive effort given the accelerator composition. The following specific application methods and specific process conditions involved in the application methods are merely non-limiting examples:
a method for preparing adipic acid by oxidizing cyclohexane, comprising the step of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of a promoter and a solvent to obtain adipic acid.
In the above technical solution, the solvent preferably includes acetic acid, more preferably the solvent is substantially acetic acid, and most preferably the solvent is acetic acid.
In the above technical solution, the oxidizing agent containing oxygen molecules may include pure oxygen, oxygen-enriched air or oxygen-depleted air.
The technical key of the invention is the choice of the promoter, and the process conditions of the reaction, such as the amount of the promoter, the proportion of the solvent, the cyclohexane and the oxidant, etc., can be reasonably selected by the person skilled in the art without creative effort.
By way of non-limiting example, in the above embodiments, the molar ratio of solvent to cyclohexane may be 1 to 10, such as 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc.
By way of non-limiting example, in the above embodiments, the molar ratio of accelerator to cyclohexane may be greater than 0 and less than 0.05, such as 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, and the like.
As a non-limiting example, in the above technical scheme, the reaction temperature is preferably 50 to 150 ℃. Such as, but not limited to, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃,115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, and the like.
As a non-limiting example, in the above technical scheme, the pressure of the reaction is preferably 0 to 5MPa. Such as but not limited to 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, etc
As a non-limiting example, in the above technical scheme, the reaction time is preferably 0.1 to 7 hours. Such as, but not limited to, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, etc.
The pressures described in this invention are gauge pressures.
The adipic acid selectivity of the product is obtained through liquid-phase HPLC detection. And (3) dissolving a solid-liquid mixture product obtained by the reaction of preparing adipic acid by oxidizing cyclohexane by using water and methanol=90:10 (V/V) electromagnetic stirring, filtering and diluting the mixture into a high-efficiency liquid phase for detection. Chromatographic conditions: the column model was ZORBAX SAX 4.6mm.times.250mm 5 μm, and the mobile phase was methanol: 50mmol/L KH 2 PO 4 Aqueous solution=5:95 (V/V), column temperature 25 ℃, flow rate 1.0mL/min, sample injection 20 μl, detection wavelength 210nm.
By adopting the technical scheme of the invention, the conversion rate of cyclohexane is up to 70%, the selectivity of adipic acid is up to 95%, compared with the prior art, the conversion rate is lower than 50%, the selectivity is lower than 70%, and the method has good technical effect and can be used in industrial production for preparing adipic acid by directly oxidizing cyclohexane.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the composition and the proportion of the accelerator are NHPI: DEAD: PBQ=1:1:1) and 1mol of cyclohexane (added into a 1 liter autoclave (with a reflux condensing device which is communicated with the atmosphere through a back-up pressure valve) are stirred in a sealing manner, heated to 115 ℃, continuously introduced with air at 3 liter/min, the pressure in the autoclave is controlled to be kept at 3.0MPa all the time, reacted for 5 hours, cooled to room temperature, and the reaction mixture is taken out for analysis, and the analysis results are that the cyclohexane conversion rate is 70%, the adipic acid selectivity is 95%, and the main reaction conditions and the reaction results are listed in Table 1 for convenience.
[ example 2 ]
5mol of acetic acid, 0.03mol of total accelerator (DEAD) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (provided with a reflux condensing device, the reflux condensing device is communicated with the atmosphere through a pressure preparation valve), the mixture is stirred in a sealing way, heated to 115 ℃, air is continuously introduced at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is obtained: cyclohexane conversion was 18%, adipic acid selectivity was 62%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 3 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are DEAD: pbq=1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (provided with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is taken out: cyclohexane conversion was 60%, adipic acid selectivity was 90%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 4 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are NHPI: DEAD=1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (provided with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is taken out: cyclohexane conversion 58%, adipic acid selectivity 86% and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 5 ]
5mol of acetic acid, 0.03mol of total accelerator (the composition and the proportion of the accelerator are NHS: DIAD: o-phthalquinone=1:1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device, the reflux condensing device is communicated with the atmosphere through a back-up pressure valve), the mixture is stirred in a sealing way, heated to 115 ℃, air is continuously introduced at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is taken out: cyclohexane conversion was 68%, adipic acid selectivity was 92%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 6 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are NHPI: DEAD: PBQ=1:1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 100 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, the mixture is cooled to room temperature after being reacted for 5 hours, and the analysis result is obtained: cyclohexane conversion was 60%, adipic acid selectivity was 90%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 7 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are NHPI: DEAD: PBQ=1:1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 1.5MPa all the time, the mixture is cooled to room temperature after being reacted for 5 hours, and the analysis result is obtained: cyclohexane conversion was 65%, adipic acid selectivity was 92%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 8 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are NHPI: DEAD: PBQ=0.1:1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device which is communicated with the atmosphere through a back-up pressure valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is taken out: cyclohexane conversion was 58%, adipic acid selectivity was 85%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 9 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are NHPI: DEAD: PBQ=5:1:1) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, the mixture is cooled to room temperature after being reacted for 5 hours, and the analysis result is obtained: cyclohexane conversion was 75%, adipic acid selectivity was 94%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 10 ]
5mol of acetic acid, 0.03mol of total accelerator (wherein the accelerator composition and the proportion are NHPI: DEAD: PBQ=1:1:5) and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, the mixture is cooled to room temperature after being reacted for 5 hours, and the analysis result is obtained: cyclohexane conversion was 72%, adipic acid selectivity was 92%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ comparative example 1 ]
5mol of acetic acid and 0.03mol of total accelerator (wherein the composition and the proportion of the accelerator are NHPI: mn (acac) 2 ：Co(CH 3 COO) 2 =1:1:1) and 1mol of cyclohexane were added to a 1-liter autoclave (with reflux condenser in communication with the atmosphere via a back-up pressure valve), stirred hermetically, heated to 115 ℃, continuously vented with air at 3.0 liters/min, the pressure in the autoclave was kept at 3.0MPa, after 5 hours of reaction, cooled to room temperature, and the reaction mixture was taken out for analysis, and the analysis results were: cyclohexane conversion was 28%, adipic acid selectivity was 65%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ comparative example 2 ]
5mol of acetic acid, 0.03mol of Cosalen/NaY and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device which is communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, air is continuously introduced at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is obtained by taking out the reaction mixture: cyclohexane conversion 21%, adipic acid selectivity 58% and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ comparative example 3 ]
5mol of acetic acid, 0.03mol of TPPMnCl and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device communicated with the atmosphere through a pressure preparation valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, the reaction is carried out for 5 hours, the reaction mixture is cooled to room temperature, and the analysis result is taken out: cyclohexane conversion was 22%, adipic acid selectivity was 62%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ comparative example 4 ]
5mol of acetic acid, 0.03mol of NHPI and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is obtained, wherein the analysis result is that the reaction mixture is taken out: cyclohexane conversion 12%, adipic acid selectivity 58%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ example 11 ]
5mol of acetic acid, 0.03mol of PBQ and 1mol of cyclohexane are added into a 1-liter pressure reaction kettle (with a reflux condensing device communicated with the atmosphere through a pressure-preparing valve), the mixture is stirred in a sealing way, heated to 115 ℃, continuously introduced with air at 3.0 liter/min, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after the reaction is carried out for 5 hours, the mixture is cooled to room temperature, and the analysis result is obtained: cyclohexane conversion 22%, adipic acid selectivity 64% and the main reaction conditions and reaction results are shown in Table 1 for comparison.
[ comparative example 5 ]
5mol of acetic acid and 1mol of cyclohexane were added to a 1-liter autoclave (having a reflux condensing device which was vented to the atmosphere through a back-up pressure valve), and the autoclave was stirred in a sealed condition, heated to 115℃and continuously vented with air at 3.0 liters/min, the pressure in the autoclave was kept at 3.0MPa, and after 5 hours of reaction, cooled to room temperature, and the reaction mixture was taken out for analysis, and the analysis result was: cyclohexane conversion was 2%, adipic acid selectivity was 18%, and the main reaction conditions and reaction results are shown in Table 1 for comparison.
TABLE 1
Note that: mn (acac) 2 Manganese acetylacetonate, TPPMnCl, cosalen and N, N-bis salicylaldehyde ethylenediamine cobalt complex.
Claims (5)
1. The method for preparing adipic acid by oxidizing cyclohexane comprises the steps of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of a reaction accelerator and a solvent to obtain adipic acid; the reaction accelerator comprises an organic azo compound, quinone and a diimide nitroxide organic compound, wherein the quinone is ortho-position diquinone and/or para-position diquinone, the mol ratio of the organic azo compound to the quinone is 0.1-10, the mol ratio of the organic azo compound to the nitroxide organic compound is 0.1-10, the solvent is acetic acid,
the diimide nitroxide radical organic compound is at least one selected from N-hydroxyphthalimide or N-hydroxysuccinimide,
the organic azo compound accords with the structure shown in the following structural formula 2:
the structural formula 2 is shown in the specification,
wherein R1 and R2 are independently selected from C1-C10 alkyl,
the ortho-diquinone is selected from the group consisting of ortho-diquinones and the para-diquinone is selected from the group consisting of para-diquinones.
2. The method according to claim 1, wherein the molar ratio of quinone to nitroxide organic compound is 0.1-10.
3. The method of claim 1, wherein the organic azo compound comprises at least one of diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).
4. The method according to claim 1, wherein the oxidizing agent containing oxygen molecules is selected from pure oxygen, oxygen-enriched air or oxygen-depleted air, the reaction temperature is 50-150 ℃, the reaction pressure is 0-5 mpa, and the reaction time is 0.1-7 hours.
5. The use of the promoter according to any one of claims 1 to 4 in the preparation of adipic acid by oxidation reaction of cyclohexane and an oxidant containing oxygen molecules.
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