CN112125795A - Method for preparing adipic acid by oxidizing cyclohexane - Google Patents
Method for preparing adipic acid by oxidizing cyclohexane Download PDFInfo
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- 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
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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, and the metal catalysts enter soil and water along with waste residues and waste liquid to cause serious environmental pollution and the like. A 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 promoter 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 solved well, and the method can be used for industrial production of adipic acid by air oxidation of cyclohexane.
Description
Technical Field
The invention relates to a method for preparing adipic acid by oxidizing cyclohexane.
Background
Adipic acid (adipic acid), also known as adipic acid, is an important organic diacid, and is an important raw material for preparing polyurethane and nylon 66. The international application field of adipic acid in nylon 66 is over 70 percent, and the international application field of adipic acid in polyurethane is 78 percent. At present, the world has four methods for producing adipic acid, namely a phenol method, a cyclohexane method, a cyclohexene method, a butadiene method and the like. Before the fifty years, the production of adipic acid mainly uses phenol as a raw material, and the production of adipic acid by using a phenol method is a more classical method. But the phenol resource is limited, the price is expensive, the product cost 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 of adipic acid synthesis. The first step of oxidizing cyclohexane to give cyclohexanol and cyclohexanone (KA oil), followed by separation of the reaction mixture, recycling of unreacted cyclohexane, and the second step of oxidizing the KA oil to adipic acid with nitric acid. The method has the advantages that: the process is mature, the process is dominant in the production of adipic acid, byproducts are mainly succinic acid and glutaric acid, the separation is easy, and the product is relatively pure. The disadvantages are as follows: in the process of synthesizing KA oil, the conversion per pass is low, the conversion rate is generally 5% -12%, and a large amount of strong acid and strong alkali solution is needed, so that equipment is corroded, and the environment is polluted; in the second step, in the process of preparing adipic acid by oxidizing KA oil, the used oxidant is nitric acid, 68 percent of nitric acid is consumed for producing 1t of adipic acid product, the corrosion to equipment is serious, and a large amount of nitrogen oxide compounds which seriously pollute the environment can be generated.
In order to solve the problem, researchers explore a more environment-friendly and simple process route for synthesizing adipic acid by taking cyclohexane as a raw material and air or oxygen as an oxidant.
Chinese invention patents CN 1247501C (title of the invention: cyclohexane catalytic oxidation process), CN 1218922C (title of the invention: method for preparing adipic acid by air oxidation of hexacyclic carbon ring compound) and CN 1231449C (title of the invention: method for preparing adipic acid by biomimetic catalytic oxygen oxidation of cyclohexane) disclose methods for preparing adipic acid by air oxidation of cyclohexane using metalloporphyrin as a catalyst. Chinese invention patents CN 101239899B (title of the invention: a method for preparing adipic acid by one-step catalytic oxidation of cyclohexane) and CN 101337878B (title of the invention: a method for directly producing adipic acid by catalytic oxidation of cyclohexane) disclose a method for preparing adipic acid by one-step oxidation of cyclohexane by using a carbon material as a carrier to load a nano ruthenium dioxide catalyst or directly as a catalyst.
In the literature Organic Process Research&Development 1998,2,255-260 (article title: Direct Conversion of cyclic hexane in o-adaptive Acid with Molecular oxygenated catalyst bound by N-Hydroxyphthalimide bound with Mn (acac)2and Co(OAc)2) In Ishii et al use a free radical catalyst NHPI, and addA small amount of a transition metal promoter is added to oxidize cyclohexane directly to adipic acid with oxygen. The reaction was carried out in acetic acid solvent with NHPI (10 mol%) and manganese acetylacetonate (1 mol%) as catalysts at 100 ℃ for 20 hours, with a cyclohexane conversion of 73% and an adipic acid yield of 53%.
The methods well solve the problem of synthesis of adipic acid from various angles, but have some defects and shortcomings, and all the methods need to adopt various metal catalysts, and the metal catalysts enter soil and water along with waste residues and waste liquids to cause serious environmental pollution and the like, and have a certain distance from industrial production of adipic acid.
Disclosure of Invention
The invention mainly solves the problems that in the reaction for 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 to cause serious environmental pollution and the like in the prior art.
In order to solve the technical problems, the method for preparing adipic acid by oxidizing cyclohexane provided by the invention comprises the following steps:
the technical scheme 1: the method for preparing adipic acid by oxidizing cyclohexane comprises the following steps of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of a reaction promoter and a solvent to obtain adipic acid; the reaction promoter includes an organic azo compound, or the reaction promoter includes a quinone.
The invention has the advantage that metal elements can not be used as catalyst components, thereby reducing the pressure of the metal on the environment. Furthermore, the addition of an organic azo compound can increase the conversion of cyclohexane and the selectivity of adipic acid, and/or the quinone can increase the conversion of cyclohexane and the selectivity of adipic acid.
The technical scheme 2 is as follows: in the technical scheme, the reaction promoter comprises an organic azo compound and quinone, and the preferable molar ratio of the organic azo compound to the quinone is 0.1-10. The quinone and the organic azo compound have a mutually enhancing effect in increasing the conversion of cyclohexane and the selectivity of adipic acid. More preferably, the molar ratio of the organic azo compound to the 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 mutually enhanced effects on the aspects of improving the conversion rate of cyclohexane and the selectivity of adipic acid; the molar ratio of the organic azo compound to the nitroxide radical organic compound is preferably 0.1 to 10, for example, 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, and the like. The nitroxide free radical organic compound and the quinone have an interaction promoting effect on the improvement of the conversion rate of cyclohexane and the selectivity of adipic acid, and the molar ratio of the quinone to the nitroxide free radical organic compound is preferably 0.1-10. 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.
The technical scheme 4 is as follows: in the above technical solution, the nitroxide radical organic compound is preferably a diimide nitroxide radical organic compound. The imide nitroxide radical containing organic compound is more preferably an N-hydroxy group containing imide compound. The imide nitroxide radical organic compound preferably corresponds to the following structural formula 1:
for example, but not limited to, the imide nitroxide radical organic compound can be selected from at least one of N-hydroxyphthalimide (NHPI) or N-hydroxysuccinimide (NHS).
The technical scheme 5 is as follows: in the above technical solution, the organic azo compound preferably conforms to the following structure:
wherein R is1And R2Independently preferably selected from C1-C10 hydrocarbon groups. Further preferred is a C1-C10 alkyl group such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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).
The technical scheme 6 is as follows: in the above technical scheme, the quinone is preferably ortho-diquinone and/or para-diquinone.
The technical scheme 7 is as follows: in the above technical scheme, the p-diquinone can be selected according to the following structural formula 3:
the technical scheme 8 is as follows: in the above technical scheme, the ortho-diquinone can be selected according to the following structure of 4:
by way of non-limiting example, the para-diquinone may be selected from para-phenylene benzoquinone (PBQ for short) and the ortho-diquinone may be selected from ortho-benzoquinone.
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 scheme, the oxidant containing oxygen molecules can be selected from pure oxygen, oxygen-enriched oxygen, air or oxygen-depleted oxygen.
The technical key of the invention is the selection of the promoter, and the technical conditions of the reaction, such as the dosage of the promoter, the proportion of the solvent, the cyclohexane and the oxidant, and the like, can be reasonably selected by a person skilled in the art without creative labor.
By way of non-limiting example, in the above technical solution, the molar ratio of the 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, and the like.
By way of non-limiting example, in the above-mentioned embodiments, the molar ratio of promoter 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.
By way of non-limiting example, in the above technical scheme, the reaction temperature is preferably 50 to 150 ℃. For example, but not limited to, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg..
By way of non-limiting example, in the above technical scheme, the pressure of the reaction is preferably 0 to 5 MPa. 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 hour, 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, and the like.
In order to solve the above technical problems, the present invention provides an accelerator composition comprising:
technical scheme 10: an accelerator composition comprising at least two selected from the group consisting of nitroxide radical organic compounds, organic azo compounds and quinones. The accelerator composition can improve the conversion rate of cyclohexane and the selectivity of adipic acid; further, the accelerator composition of the invention may or may not include a metal element component, and when the metal element component is not included, the stress of the metal element on the environment can be alleviated.
As one of the preferable embodiments of claim 10, the composition preferably includes an organic azo compound and a nitroxide radical organic compound. The nitroxide radical organic compound and the organic azo compound have mutually enhanced effects in improving the conversion rate of cyclohexane and the selectivity of adipic acid. In the technical scheme that the composition comprises the organic azo compound and the nitroxide radical organic compound, the molar ratio of the organic azo compound to the nitroxide radical organic compound is preferably 0.1-10, 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, and the like.
As a second preferred embodiment of claim 10, the composition preferably comprises an organic azo compound and a quinone. The quinone and the organic azo compound have a mutually enhancing effect in increasing the conversion of cyclohexane and the selectivity of adipic acid. In the technical scheme that the composition preferably comprises an organic azo compound and quinone, the molar ratio of the organic azo compound to the quinone is preferably 0.1-10. 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 radical organic compound and a quinone. The nitroxide radical organic compound and the quinone have an interaction promoting effect in improving the conversion rate of cyclohexane and the selectivity of adipic acid. In the technical scheme that the composition preferably comprises the nitroxide free radical organic compound and the quinone, the molar ratio of the nitroxide free radical organic compound to the quinone is preferably 0.1-1. 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 comprises an organic azo compound, a nitroxide radical organic compound and a quinone at the same time. In this case, the organic azo compound, the nitroxide radical organic compound and the quinone have a ternary combination effect in increasing the conversion rate of cyclohexane and the selectivity of adipic acid.
Technical scheme 12: in the above technical solution, in the technical solution simultaneously including the organic azo compound, the nitroxide radical organic compound and the quinone, the composition preferably includes, in terms of mole parts:
0.1 to 10 parts of an organic azo compound, such as, but not limited to, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1.2 part, 1.4 part, 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;
nitroxide radical organic compounds are 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;
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 imide nitroxide radical containing organic compound is preferably an N-hydroxy group containing imide compound. The imide nitroxide radical organic compound preferably corresponds to the following structural formula 1:
by way of non-limiting example, for example and without limitation, the imide nitroxide radical organic compound can 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 hydrocarbon groups. C1 to C10 alkyl groups are preferred, such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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-diquinone and/or para-diquinone. Preferably, the para-diquinone can optionally correspond to the following structural formula 3:
preferably the vicinal diquinone optionally conforms to the following structure 4:
by way of non-limiting example, the para-diquinone may be selected from para-phenylene benzoquinone (PBQ for short) and the ortho-diquinone may be selected from ortho-benzoquinone.
The accelerator composition can be prepared by mixing the components, and then adding the mixture into a process of preparing adipic acid by taking cyclohexane and an oxidant containing oxygen molecules as raw materials through an oxidation reaction; the components of the accelerator composition may be added to the process of preparing adipic acid by oxidation reaction using cyclohexane and an oxidant containing oxygen molecules as raw materials without mixing in advance, and the order of addition is not particularly limited.
In order to solve the above technical problems, the accelerator composition provided by the present invention is applied as follows:
technical scheme 16: the accelerator composition according to any one of the technical schemes 10 to 15 is applied to a process of preparing adipic acid by using cyclohexane and an oxidant containing oxygen molecules as raw materials to perform an oxidation reaction.
The technical key to the use of the accelerator composition is the choice of the accelerator components, and the method of application can be chosen reasonably and without inventive effort by the person skilled in the art, given the composition of the accelerator. The following specific methods of use and the specific process conditions involved in the methods of use are merely non-limiting examples:
the method for preparing adipic acid by oxidizing cyclohexane comprises the step of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of the promoter and the solvent to obtain the 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 scheme, the oxidant containing oxygen molecules can be selected from pure oxygen, oxygen-enriched oxygen, air or oxygen-depleted oxygen.
The technical key of the invention is the selection of the promoter, and the technical conditions of the reaction, such as the dosage of the promoter, the proportion of the solvent, the cyclohexane and the oxidant, and the like, can be reasonably selected by a person skilled in the art without creative labor.
By way of non-limiting example, in the above technical solution, the molar ratio of the 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, and the like.
By way of non-limiting example, in the above-mentioned embodiments, the molar ratio of promoter 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.
By way of non-limiting example, in the above technical scheme, the reaction temperature is preferably 50 to 150 ℃. For example, but not limited to, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C, 140 deg..
By way of non-limiting example, in the above technical scheme, the pressure of the reaction is preferably 0 to 5 MPa. 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 hour, 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, and the like.
The pressures stated in the present invention are gauge pressures.
The selectivity of the product adipic acid is detected by liquid phase HPLC. The solid-liquid mixed product obtained by the reaction of preparing adipic acid by oxidizing cyclohexane is electromagnetically stirred and dissolved by water and methanol in a ratio of 90:10(V/V), and is filtered and diluted into a high-efficiency liquid phase for detection. Chromatographic analysis conditions: the chromatography column model is ZORBAX SAX 4.6mm X250 mm 5 μm, and the mobile phase is methanol: 50mmol/L KH2PO4The column temperature was 25 ℃, the flow rate was 1.0mL/min, the amount of sample was 20 μ L, and the detection wavelength was 210 nm.
By adopting the technical scheme of the invention, the conversion rate of cyclohexane is up to 70 percent, the selectivity of adipic acid is up to 95 percent, and compared with the prior art, the conversion rate is lower than 50 percent, and the selectivity is lower than 70 percent, so that the method has better technical effect, and can be used in the industrial production of preparing adipic acid by directly oxidizing cyclohexane.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Acetic acid (5 mol), promoter (NHPI: DEAD: PBQ ═ 1:1:1) and cyclohexane (1 mol) were added to a 1-liter autoclave (equipped with a reflux condenser, which was open to the atmosphere via a back pressure valve), heated to 115 ℃ under sealed stirring, and air was continuously introduced at 3 liters/min, the autoclave pressure was controlled to be 3.0MPa, and after 5 hours of reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was taken out for analysis, showing 70% cyclohexane conversion and 95% adipic acid selectivity, for convenience of comparison, the main reaction conditions and the reaction results are shown in Table 1.
[ example 2 ]
Adding 5mol of acetic acid, 0.03mol of total amount of accelerator (DEAD) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture, analyzing, and analyzing the result: cyclohexane conversion was 18% and adipic acid selectivity was 62%, and the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 3 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are DEAD: PBQ ═ 1:1) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 60% and adipic acid selectivity 90%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 4 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are NHPI: DEAD is 1:1) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-retaining valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 58% and adipic acid selectivity 86%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 5 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are NHS: DIAD: o-phenylenediquinone is 1:1:1) and 1mol of cyclohexane into a 1-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 3.0MPa all the time, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 68% and adipic acid selectivity was 92%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 6 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are NHPI: DEAD: PBQ ═ 1:1:1) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 100 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 3.0MPa all the time, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 60% and adipic acid selectivity 90%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 7 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are NHPI: DEAD: PBQ ═ 1:1:1) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 1.5MPa all the time, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 65% and adipic acid selectivity was 92%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 8 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the ratio of the accelerant are NHPI: DEAD: PBQ is 0.1:1:1) and 1mol of cyclohexane into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-supply valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 58% and adipic acid selectivity 85%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 9 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are NHPI: DEAD: PBQ ═ 5:1:1) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 3.0MPa all the time, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 75% and adipic acid selectivity was 94%, and the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 10 ]
Adding 5mol of acetic acid, 0.03mol of total amount of an accelerant (wherein the composition and the proportion of the accelerant are NHPI: DEAD: PBQ ═ 1:1:5) and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 3.0MPa all the time, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion of 72% and adipic acid selectivity of 92%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ COMPARATIVE EXAMPLE 1 ]
5mol of acetic acid and 0.03mol of total amount of accelerator (wherein the composition and the ratio of the accelerator are NHPI: Mn (acac))2：Co(CH3COO)21:1:1) and 1mol of cyclohexane are added into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-retaining valve), sealed and stirred, heated to 115 ℃, continuously introduced with air at the rate of 3.0 liters/minute, the pressure in the kettle is controlled to be kept at 3.0MPa all the time, after 5 hours of reaction, cooled to room temperature, taken out of the reaction mixture for analysis, and the analysis result is as follows: cyclohexane conversion was 28% and adipic acid selectivity was 65%, and the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ COMPARATIVE EXAMPLE 2 ]
Adding 5mol of acetic acid, 0.03mol of Cosalen/NaY and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), hermetically stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture, analyzing, and obtaining an analysis result: cyclohexane conversion was 21% and adipic acid selectivity was 58%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ COMPARATIVE EXAMPLE 3 ]
Adding 5mol of acetic acid, 0.03mol of TPPMnCl and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-retaining valve), hermetically stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 22% and adipic acid selectivity was 62%, and the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ COMPARATIVE EXAMPLE 4 ]
Adding 5mol of acetic acid, 0.03mol of NHPI and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), hermetically stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 12% and adipic acid selectivity was 58%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ example 11 ]
Adding 5mol of acetic acid, 0.03mol of PBQ and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), hermetically stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/min, controlling the pressure in the kettle to be kept at 3.0MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 22% and adipic acid selectivity was 64%, the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
[ COMPARATIVE EXAMPLE 5 ]
Adding 5mol of acetic acid and 1mol of cyclohexane into a 1-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 115 ℃, continuously introducing air at 3.0 liters/minute, controlling the pressure in the kettle to be kept at 3.0MPa, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture, analyzing, and obtaining an analysis result: cyclohexane conversion was 2% and adipic acid selectivity was 18%, and the prevailing reaction conditions and reaction results are shown in Table 1 for ease of comparison.
TABLE 1
Note: mn (acac)2Manganese acetylacetonate, TPPMnCl is tetraphenylporphyrin manganese chloride, Cosalen is a cobalt N, N-bis (salicylaldehyde) ethylene diamine complex.
Claims (16)
1. The method for preparing adipic acid by oxidizing cyclohexane comprises the following steps of reacting cyclohexane with an oxidant containing oxygen molecules in the presence of a reaction promoter and a solvent to obtain adipic acid; the reaction promoter includes an organic azo compound, or the reaction promoter includes a quinone.
2. The method as set forth in claim 1, wherein the reaction accelerator comprises an organic azo compound and a quinone, preferably the molar ratio of the organic azo compound to the quinone is 0.1 to 10.
3. The method of claim 1, wherein the promoter comprises a nitroxide radical organic compound. Preferably, the molar ratio of the organic azo compound to the nitroxide radical organic compound is 0.1-10; or preferably the molar ratio of the quinone to the nitroxide radical organic compound is 0.1-10.
4. The method as set forth in claim 3, wherein the nitroxide radical organic compound is a diimide nitroxide radical organic compound. The imide nitroxide radical containing organic compound is preferably an N-hydroxy group containing imide compound. The imide nitroxide radical organic compound preferably corresponds to the following structural formula 1:
5. the process according to claim 1, wherein the organic azo compound corresponds to the following structure:
wherein R1 and R2 are independently selected from C1-C10 hydrocarbon groups. C1 to C10 alkyl groups are preferred, such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. Such as, but not limited to, at least one of diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).
6. The method as set forth in claim 1, wherein the quinone is a vicinal diquinone and/or a para diquinone.
7. The method according to claim 6, wherein said vicinal diquinone corresponds to the structure shown in formula 3 below:
8. the method of claim 7, wherein the p-diquinone corresponds to the structure of formula 4:
9. the method as set forth in claim 1, characterized in that the solvent preferably comprises acetic acid. The molecular oxygen-containing oxidant preferably comprises pure oxygen, oxygen-enriched, air or oxygen-depleted. The reaction temperature is preferably 50-150 ℃. The reaction pressure is preferably 0-5 MPa. The reaction time is preferably 0.1 to 7 hours.
10. An accelerator composition comprising at least two selected from the group consisting of nitroxide radical organic compounds, organic azo compounds and quinones. Preferably, the composition comprises an organic azo compound and a nitroxide radical organic compound, and more preferably, the molar ratio of the organic azo compound to the nitroxide radical organic compound is 0.1-1; or preferably the composition comprises an organic azo compound and a quinone, more preferably the molar ratio of the organic azo compound to the quinone is 0.1-1; or preferably, the composition comprises the nitroxide free radical organic compound and the quinone, and more preferably, the molar ratio of the nitroxide free radical organic compound to the quinone is 0.1-1.
11. The composition as set forth in claim 10, characterized in that the composition comprises an organic azo compound, a nitroxide radical organic compound and a quinone.
12. The composition of claim 11, wherein the composition is characterized by, in mole parts:
0.1-10 parts of organic azo compound;
0.1-10 parts of nitroxide radical organic compound;
0.1-10 parts of quinone.
13. The composition as set forth in claim 10, characterized in that the nitroxide radical organic compound is a diimide nitroxide radical organic compound. The imide nitroxide radical containing organic compound is preferably an N-hydroxy group containing imide compound. The imide nitroxide radical organic compound preferably corresponds to the following structural formula 1:
14. the composition according to claim 10, characterized in that the organic azo compound corresponds to the following structure:
wherein R1 and R2 are independently selected from C1-C10 hydrocarbon groups. C1 to C10 alkyl groups are preferred, such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. Such as, but not limited to, at least one of diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).
15. The composition as set forth in claim 10, wherein the quinone is a vicinal diquinone and/or a para diquinone. Preferably, the para-diquinone can optionally correspond to the following structural formula 3:
preferably the vicinal diquinone optionally conforms to the following structure 4:
16. use of the accelerator composition according to any one of claims 10 to 15 in the preparation of adipic acid by oxidation of cyclohexane and an oxygen-containing molecular oxidant.
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