CN113563176B - Cu (II)/nitric acid binary catalytic system for catalyzing O 2 Method for synthesizing adipic acid by oxidizing cyclohexene in one step - Google Patents
Cu (II)/nitric acid binary catalytic system for catalyzing O 2 Method for synthesizing adipic acid by oxidizing cyclohexene in one step Download PDFInfo
- Publication number
- CN113563176B CN113563176B CN202110981109.8A CN202110981109A CN113563176B CN 113563176 B CN113563176 B CN 113563176B CN 202110981109 A CN202110981109 A CN 202110981109A CN 113563176 B CN113563176 B CN 113563176B
- Authority
- CN
- China
- Prior art keywords
- reaction
- cyclohexene
- nitric acid
- yield
- adipic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Cu (II)/nitric acid binary catalytic system for catalyzing O 2 One-step synthesis of cyclohexene oxideThe diacid preparing process includes dispersing nitric acid and Cu (II) salt in cyclohexene, sealing the reaction system, stirring while heating to reaction temperature, and introducing oxidant O 2 Stirring and reacting under the reaction pressure to generate adipic acid product. The invention provides an efficient, feasible and green method for synthesizing adipic acid by one-step catalytic oxidation of cyclohexene.
Description
Technical Field
The invention belongs to the field of industrial catalysis and fine organic synthesis, and particularly relates to a Cu (II)/nitric acid binary catalytic system for catalyzing O 2 A method for synthesizing adipic acid by oxidizing cyclohexene in one step.
Background
Adipic acid, also known as adipic acid (AA for short), of formula HOOC (CH) 2 ) 4 COOH is the most valuable diacid among aliphatic diacid, and is mainly used for synthesizing nylon 66, polyurethane and a plasticizer. In addition, the adipic acid can also be used for producing high-grade lubricating oil, food additives, medical intermediates, flavors, fragrances, dyes and the like. (chemical engineering, 2013, 41 (07): 42-44+ 49.). Currently, the annual production of adipic acid is about 300 million tons, illustrating the importance of adipic acid as an industrial precursor. In the future markets, the demand for adipic acid is still increasing (European Journal of organic Chemistry, 2020 (03): 248-252). At present, the industrial production process of adipic acid mainly comprises a benzene complete hydro-oxidation method and a benzene partial hydro-oxidation method. The benzene partial hydrogenation oxidation method uses benzene as a raw material, partial hydrogenation is carried out to obtain cyclohexene, and further hydration is carried out to obtain cyclohexanol as an intermediate product. Cyclohexanol is oxidized and synthesized into adipic acid by nitric acid catalysis. The process has the following problems: (1) Longer reaction path, reduced conversion rate, increased energy consumption and increased production cost. (2) The adipic acid is obtained by catalytic oxidation of cyclohexanol with nitric acid, which causes emission of a large amount of nitrogen oxides (0.3 t/1 t adipic acid) and causes irreversible damage to the ozone layer and the environment. Therefore, the process route of industrial production is effectively shortened, the cyclohexene is directly catalyzed and oxidized by adopting a proper and efficient catalyst, the adipic acid is synthesized in one step, the use of nitric acid is reduced, the improvement of the efficiency of producing the adipic acid by a benzene partial hydrogenation oxidation method is facilitated, and the reduction of industrial production cost and NO are facilitated x And (4) discharging gas. The design idea is a novel process improvement with great application significance in the industrial synthesis field of adipic acid in industry.
O 2 As the oxidant which best accords with the green chemistry idea, the oxidation by-product is H 2 O, which has no influence on the environment, is cheap and easily available, has high atom economy and is the oxidant with the greatest development prospect. Nitric acid is a common oxidant in the industry and is effective in oxidizing cyclohexanol, cyclohexanone to adipic acid, but produces nitrogen oxides NO x . Cu (II), a commonly used transition metal, has the ability to catalyze oxidation reactions, and can promote the reaction (Catalysis Today, 2020, 346: 40-45).
Therefore, the invention uses Cu (II)/catalytic amount of nitric acid to form a binary catalytic oxidation system, uses Cu (II) as a catalyst and nitric acid as a direct oxidant, and directly oxidizes cyclohexene to synthesize adipic acid in one step. While in an environment where water is present, O 2 Nitrogen oxides NO formed by oxidation x Preparing nitrogen dioxide, and obtaining oxidized nitric acid again to enter the cycle of cyclohexene oxide. The Cu (II)/nitric acid binary catalytic system of the invention catalyzes O 2 The method for synthesizing adipic acid by oxidizing cyclohexene has the advantages of high yield, short reaction route and nitrogen oxide NO x Less discharge, low reaction temperature, little environmental influence, low production cost and the like. In addition, the catalyst adopted by the invention is cheap and easy to obtain, and the industrial production cost can be greatly reduced. The invention provides a method for synthesizing adipic acid by directly catalyzing and oxidizing cyclohexene in one step, which is efficient, feasible and green.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a Cu (II)/nitric acid binary catalytic system for catalyzing O 2 A method for synthesizing adipic acid by oxidizing cyclohexene in one step.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 A one-step synthesis method of adipic acid by cyclohexene oxide is characterized in that nitric acid and Cu (II) salt are dispersed in cyclohexene, a reaction system is sealed, the temperature is raised to a reaction temperature by stirring, and an oxidant O is introduced 2 Stirring and reacting under the reaction pressure to generate a target adipic acid product and a small amount of glutaric acid and succinic acid products.
The above-mentionedA Cu (II)/nitric acid binary catalytic system for catalyzing O 2 The method for synthesizing the adipic acid by oxidizing cyclohexene in one step is characterized in that the Cu (II) salt is Cu (CH) 3 COO) 2 、Cu(NO 3 ) 2 、CuSO 4 、CuCl 2 At least one of copper stearate, copper oxalate, copper acetylacetonate and hydrates thereof or a mixture of more than two of the above in any proportion.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step is characterized in that the concentration of nitric acid is 3.0-15.0 mol/L, and preferably 6.0-13.0 mol/L; the ratio of the volume of the nitric acid to the amount of the cyclohexene substance is 1.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step is characterized in that the mass ratio of the Cu (II) salt to the cyclohexene is 1 to 10 to 10000, preferably 1 to 100 to 1000.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 The method for synthesizing adipic acid by cyclohexene oxide in one step is characterized in that the reaction temperature is 40-120 ℃, and preferably 45-70 ℃.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 The method for synthesizing adipic acid by cyclohexene oxide in one step is characterized in that the reaction pressure is 0.10 to 2.0 MPa, preferably 0.2 to 1.6MPa.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 The method for synthesizing the adipic acid by oxidizing cyclohexene in one step is characterized in that the stirring speed is 100 to 1000 rpm, preferably 200 to 700rpm.
The Cu (II)/nitric acid binary catalytic system catalyzes O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step is characterized in that the reaction time is 2.0-24.0 hours, preferably 6.0-16.0 hours.
The invention uses a Cu (II)/nitric acid binary catalytic system to catalyze O 2 The cyclohexene oxide is used for synthesizing the adipic acid in one step, so that the process route is effectively shortened, and the content of the adipic acid is reducedLow energy consumption, low cost, and the further reaction of NO generated by cyclohexene oxide from nitric acid and oxygen to generate NO 2 And NO 2 And the nitric acid is dissolved in water to form nitric acid solution, thereby realizing the recycling of the nitric acid, reducing the generation of by-products and reducing environmental pollutants NO x The emission of gas meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a method for synthesizing cyclohexanedicarboxylic acid by efficient and green oxidation of cyclohexene, but also has a certain reference value for efficiently preparing aliphatic diacid by catalytic oxidation of C = C bonds of other cycloolefins.
The invention has the following beneficial effects: the Cu (II)/nitric acid binary catalytic system of the invention catalyzes O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step has the advantages of high yield, short reaction route and nitrogen oxide NO x Less discharge, low reaction temperature, little environmental influence, low production cost and the like. In addition, the catalyst (namely a Cu (II)/nitric acid binary catalytic system) adopted by the invention is cheap and easy to obtain, and the industrial production cost can be greatly reduced. The invention provides a method for synthesizing adipic acid by one step of catalytic oxidation of cyclohexene, which is efficient, feasible and green.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The reagents used in the examples of the present invention were all commercially available analytical grade.
Examples 1 to 40 are cases of catalytic oxidation of cyclohexene;
examples 41 to 43 are comparative experimental cases;
example 44 is a scale-up experiment.
Example 1
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 (0.01 equivalent) is dispersed in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is 1.0 MPa. At a reaction temperature of 60℃,1.0 MPa oxygen pressure, 500 rpm stirring reaction 12.0 h. After the reaction is finished, cooling to room temperature, and analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 81 percent, the yield of glutaric acid is 5 percent, and the yield of succinic acid is 4 percent.
Example 2
In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1876 g anhydrous Cu (NO) 3 ) 2 (0.01 equivalent) is dispersed in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 71%, the yield of glutaric acid is 10% and the yield of succinic acid is 3%.
Example 3
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1345 g anhydrous CuCl were placed in a autoclave 2 (0.01 equive) is dispersed in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, and analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 68 percent, the yield of glutaric acid is 11 percent, and the yield of succinic acid is 3 percent.
Example 4
In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1596 g anhydrous CuSO were placed in a autoclave 4 (0.01 equive) is dispersed in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 67%, the yield of glutaric acid is 10% and the yield of succinic acid is 2%.
Example 5
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 (0.01 equive) is dispersed in nitric acid solution with the molar concentration of 50 mL of 6 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 59%, the yield of glutaric acid is 5% and the yield of succinic acid is 1%.
Example 6
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 7 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 61 percent, the yield of glutaric acid is 6 percent and the yield of succinic acid is 1 percent.
Example 7
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 8 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 65%, the yield of glutaric acid is 6% and the yield of succinic acid is 2%.
Example 8
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 9 mol/L, sealing the reaction kettle, stirringStirring and heating to 60 ℃ for reaction, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 70%, the yield of glutaric acid is 6% and the yield of succinic acid is 2%.
Example 9
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 10 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 72 percent, the yield of glutaric acid is 6 percent and the yield of succinic acid is 3 percent.
Example 10
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 12 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 68 percent, the yield of glutaric acid is 4 percent, and the yield of succinic acid is 3 percent.
Example 11
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 13 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, and analyzing and detecting a reaction product, wherein the reaction result is as follows: yield of adipic acid 65%, yield of glutaric acidThe yield is 3 percent and the succinic acid yield is 3 percent.
Example 12
8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) in a 100 mL stainless steel autoclave with Teflon liner 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 40 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 40 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 65%, the yield of glutaric acid is 2% and the yield of succinic acid is 1%.
Example 13
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 45 ℃ under 1.0 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, and analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 70%, the yield of glutaric acid is 2% and the yield of succinic acid is 1%.
Example 14
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 50 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 50 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 75 percent, the yield of glutaric acid is 3 percent and the yield of succinic acid is 1 percent.
Example 15
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to 55 ℃ for reaction, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 55 ℃ under 1.0 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 78%, the yield of glutaric acid is 3% and the yield of succinic acid is 2%.
Example 16
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to 65 ℃ for reaction, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 65 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 74 percent, the yield of glutaric acid is 3 percent and the yield of succinic acid is 3 percent.
Example 17
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to 70 ℃ for reaction, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 70 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 71 percent, the yield of glutaric acid is 4 percent, and the yield of succinic acid is 2 percent.
Example 18
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 75 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 75 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, and carrying out the opposite reactionThe product is analyzed and detected, and the reaction result is as follows: the yield of adipic acid is 60 percent, the yield of glutaric acid is 4 percent, and the yield of succinic acid is 1 percent.
Example 19
8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) in a 100 mL stainless steel autoclave with Teflon liner 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 0.2 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 0.2 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 55 percent, the yield of glutaric acid is 1 percent and the yield of succinic acid is 1 percent.
Example 20
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 0.4 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 0.4 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 68 percent, the yield of glutaric acid is 3 percent, and the yield of succinic acid is 1 percent.
Example 21
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 0.6 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 0.6 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 69 percent, the yield of glutaric acid is 2 percent, and the yield of succinic acid is 1 percent.
Example 22
In a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container and 100 mL8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 0.8 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 0.8 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 72 percent, the yield of glutaric acid is 3 percent, and the yield of succinic acid is 2 percent.
Example 23
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.2 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.2 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 70%, the yield of glutaric acid is 4% and the yield of succinic acid is 3%.
Example 24
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.4 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.4 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 61 percent, the yield of glutaric acid is 3 percent, and the yield of succinic acid is 2 percent.
Example 25
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.6MPa. Reaction temperature at 60 ℃ of 1.6MPa oxygen pressure, 500 rpm stir reaction 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 50%, the yield of glutaric acid is 3% and the yield of succinic acid is 1%.
Example 26
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to react 4.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 41 percent, the yield of glutaric acid is 1 percent, and the yield of succinic acid is 1 percent.
Example 27
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to give 6.0h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 52%, the yield of glutaric acid is 1% and the yield of succinic acid is 1%.
Example 28
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to 8.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 65%, the yield of glutaric acid is 3% and the yield of succinic acid is 1%.
Example 29
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 10.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 71 percent, the yield of glutaric acid is 3 percent, and the yield of succinic acid is 2 percent.
Example 30
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was carried out at 60 ℃ under 1.0 MPa of oxygen pressure and with stirring at 500 rpm for 14.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 75 percent, the yield of glutaric acid is 4 percent and the yield of succinic acid is 2 percent.
Example 31
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to 16.0h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 63 percent, the yield of glutaric acid is 5 percent, and the yield of succinic acid is 1 percent.
Example 32
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.0018 g anhydrous Cu (CH) 3 COO) 2 (0.01% equivalent) is dispersed in nitric acid solution with the concentration of 50 mL mol concentration of 11 mol/L, and the mixture is sealed and reversely mixedThe mixture is stirred and heated to 60 ℃ reaction temperature, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 66%, the yield of glutaric acid is 1% and the yield of succinic acid is 1%.
Example 33
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.0188 g anhydrous Cu (CH) 3 COO) 2 (0.1% equivalent) is dispersed in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is (1.0 MPa). The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 69 percent, the yield of glutaric acid is 2 percent, and the yield of succinic acid is 1 percent.
Example 34
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 1.8760 g anhydrous Cu (CH) 3 COO) 2 (0.1 equive) is dispersed in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, the reaction kettle is sealed, stirred and heated to the reaction temperature of 60 ℃, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 71 percent, the yield of glutaric acid is 4 percent and the yield of succinic acid is 3 percent.
Example 35
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 100 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting the reaction product, and carrying outThe result should be: the yield of adipic acid is 42 percent, the yield of glutaric acid is 1 percent, and the yield of succinic acid is 2 percent.
Example 36
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 200 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, and analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 52 percent, the yield of glutaric acid is 2 percent, and the yield of succinic acid is 2 percent.
Example 37
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 300 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 59 percent, the yield of glutaric acid is 3 percent and the yield of succinic acid is 2 percent.
Example 38
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 400 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 70 percent, the yield of glutaric acid is 4 percent and the yield of succinic acid is 2 percent.
Example 39
In a stainless steel autoclave with a polytetrafluoroethylene inner liner, 100 mL, 8.2140 g (100 mmol) ring is placedHexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 600 rpm at 60 ℃ under 1.0 MPa of oxygen pressure to react 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 73 percent, the yield of glutaric acid is 4 percent and the yield of succinic acid is 3 percent.
Example 40
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 700rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, and analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 74 percent, the yield of glutaric acid is 4 percent, and the yield of succinic acid is 4 percent.
Example 41 (comparative experiment)
In a 100 mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 8.2140 g (100 mmol) cyclohexene is dispersed in 50 mL mol concentration of 11 mol/L nitric acid solution, the reaction kettle is sealed, stirred and heated to 60 ℃ reaction temperature, and oxygen is introduced until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid was 44% and the yield of glutaric acid was 1%, and succinic acid was not detected.
Example 42 (comparative experiment)
0.1997 g anhydrous Cu (CH) was placed in a stainless steel autoclave 100 mL with a Teflon liner 3 COO) 2 Dispersing 8.2140 g (100 mmol) cyclohexene, sealing the reaction kettle, stirring, heating to 60 deg.C, and introducing oxygen to pressure of 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, and carrying out the opposite reactionThe product is analyzed and detected, and the reaction result is as follows: the yield of adipic acid was 5%, glutaric acid was not detected, and succinic acid was not detected.
Example 43 (comparative experiment)
In a 100 mL stainless steel autoclave with teflon liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu (CH) 3 COO) 2 Dispersing in a nitric acid solution with the molar concentration of 50 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to 60 ℃. The reaction was stirred at 500 rpm at 60 ℃ for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid was 36%, the yield of glutaric acid was 1%, and succinic acid was not detected.
Example 44 (Experimental amplification)
In a 1000 mL stainless steel autoclave with polytetrafluoroethylene liner, 82.1400 g (1 mol) cyclohexene and 1.9970 g anhydrous Cu (CH) 3 COO) 2 Dispersing in nitric acid solution with the molar concentration of 500 mL of 11 mol/L, sealing the reaction kettle, stirring and heating to the reaction temperature of 60 ℃, and introducing oxygen until the pressure is 1.0 MPa. The reaction was stirred at 500 rpm at 60 ℃ under 1.0 MPa of oxygen pressure for 12.0 h. After the reaction is finished, cooling to room temperature, analyzing and detecting a reaction product, wherein the reaction result is as follows: the yield of adipic acid is 80%, the yield of glutaric acid is 5% and the yield of succinic acid is 5%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. Cu (II)/nitric acid binary catalytic system for catalyzing O 2 A one-step synthesis method of adipic acid by cyclohexene oxide is characterized in that nitric acid and Cu (II) salt are dispersed in cyclohexene, a reaction system is sealed, the temperature is raised to a reaction temperature by stirring, and an oxidant O is introduced 2 Stirring and reacting under the reaction pressure to generate an adipic acid product;
the concentration of the nitric acid is 3.0 to 15.0 mol/L, the ratio of the volume of the nitric acid to the amount of substances of the cyclohexene is 1.2 to 10, the unit of the volume is L, and the unit of the amount of the substances is mol;
the mass ratio of the Cu (II) salt to cyclohexene is 1 to 1000;
the reaction pressure is 0.10 to 2.0 MPa.
2. The Cu (II)/nitric acid binary catalytic system of claim 1 for catalyzing O 2 The method for synthesizing the adipic acid by oxidizing cyclohexene in one step is characterized in that the Cu (II) salt is Cu (CH) 3 COO) 2 、Cu(NO 3 ) 2 、CuSO 4 、CuCl 2 At least one of copper stearate, copper oxalate, copper acetylacetonate and hydrates thereof or a mixture of more than two of the above in any proportion.
3. The Cu (II)/nitric acid binary catalytic system of claim 1 for catalyzing O 2 The method for synthesizing adipic acid by one step through cyclohexene oxide is characterized in that the concentration of nitric acid is 6.0-13.0 mol/L; the ratio of the volume of the nitric acid to the amount of the substance of the cyclohexene is 1 to 0.5 to 2.0, the unit of the volume is L, and the unit of the amount of the substance is mol.
4. The Cu (II)/nitric acid binary catalytic system of claim 1 for catalyzing O 2 The method for synthesizing adipic acid by cyclohexene oxide in one step is characterized in that the reaction temperature is 40-120 ℃.
5. The Cu (II)/nitric acid binary catalytic system of claim 4 for catalyzing O 2 The method for synthesizing adipic acid by cyclohexene oxide in one step is characterized in that the reaction temperature is 45-70 ℃.
6. The Cu (II)/nitric acid binary catalytic system of claim 1 for catalyzing O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step is characterized in that the reaction pressure is 0.2 to 1.6MPa.
7. The Cu (II)/nitric acid binary catalytic system of claim 1 for catalyzing O 2 One-step synthesis of adipic acid by cyclohexene oxideThe method of (1) is characterized in that the stirring rate is 100 to 1000 rpm.
8. The Cu (II)/nitric acid binary catalytic system of claim 7 for catalyzing O 2 The method for synthesizing the adipic acid by oxidizing cyclohexene in one step is characterized in that the stirring speed is 200 to 700rpm.
9. The Cu (II)/nitric acid binary catalytic system of claim 1 for catalyzing O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step is characterized in that the reaction time is 2.0-24.0 h.
10. The Cu (II)/nitric acid binary catalytic system of claim 9 for catalyzing O 2 The method for synthesizing adipic acid by oxidizing cyclohexene in one step is characterized in that the reaction time is 6.0-16.0 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110981109.8A CN113563176B (en) | 2021-08-25 | 2021-08-25 | Cu (II)/nitric acid binary catalytic system for catalyzing O 2 Method for synthesizing adipic acid by oxidizing cyclohexene in one step |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110981109.8A CN113563176B (en) | 2021-08-25 | 2021-08-25 | Cu (II)/nitric acid binary catalytic system for catalyzing O 2 Method for synthesizing adipic acid by oxidizing cyclohexene in one step |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113563176A CN113563176A (en) | 2021-10-29 |
| CN113563176B true CN113563176B (en) | 2022-12-20 |
Family
ID=78172717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110981109.8A Active CN113563176B (en) | 2021-08-25 | 2021-08-25 | Cu (II)/nitric acid binary catalytic system for catalyzing O 2 Method for synthesizing adipic acid by oxidizing cyclohexene in one step |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113563176B (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2114635C (en) * | 1993-04-09 | 2000-05-23 | Tohru Ide | Process for preparing adipic acid |
| CN1040977C (en) * | 1993-04-16 | 1998-12-02 | 旭化成工业株式会社 | Preparation of hexandioic acid |
| JP4436905B2 (en) * | 2000-12-14 | 2010-03-24 | ダイセル化学工業株式会社 | Method for producing dicarboxylic acid |
| DE60207677D1 (en) * | 2002-01-04 | 2006-01-05 | Council Scient Ind Res | An improved process for the production of adipic acid |
| CN102329222B (en) * | 2011-07-14 | 2014-04-09 | 烟台大学 | Method for oxidizing cyclohexane to prepare hexane diacid through one-step method and catalyst used by same |
| CN102442898A (en) * | 2011-11-09 | 2012-05-09 | 河南神马尼龙化工有限责任公司 | Method for synthesizing adipic acid |
| CN104513152B (en) * | 2013-09-27 | 2016-09-07 | 中国石油天然气股份有限公司 | Method and equipment for preparing adipic acid by oxidizing alcohol ketone with nitric acid |
| WO2018128959A1 (en) * | 2017-01-04 | 2018-07-12 | Shell Oil Company | A process for the preparation of adipic acid |
| WO2018128960A1 (en) * | 2017-01-04 | 2018-07-12 | Shell Oil Company | A process for the preparation of adipic acid |
| CN110615736B (en) * | 2018-06-20 | 2021-01-26 | 中国科学院大连化学物理研究所 | Preparation method of dicarboxylic acid |
| CN112299968B (en) * | 2020-11-26 | 2022-05-06 | 广州彼西络科技有限公司 | Preparation method of chemical raw material |
-
2021
- 2021-08-25 CN CN202110981109.8A patent/CN113563176B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113563176A (en) | 2021-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110563555A (en) | Method for oxidizing cycloparaffin through synergetic catalysis of cobalt (II)/zinc (II) porphyrin salt | |
| CN109456176A (en) | Novel catalytic oxidation method of cycloparaffin promoted by copper porphyrin | |
| CN112090449B (en) | Bimetal central metalloporphyrin as well as preparation method and application thereof | |
| CN109456175A (en) | New zinc porphyrin promoted cycloparaffin catalytic oxidation method | |
| Shen et al. | Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn (AcO) 2: A practical strategy to inhibit the formation of aliphatic diacids | |
| CN111018673A (en) | Method for catalytic oxidation of cycloparaffin by limited porphyrin Co (II) | |
| CN110833844B (en) | Application of cobalt carbonate in preparing acetophenone by ethylbenzene catalytic oxidation under solvent-free catalysis of molecular oxygen | |
| Bonnet et al. | Innovative direct synthesis of adipic acid by air oxidation of cyclohexane | |
| CN113649073A (en) | Method for catalytic oxidation of cycloparaffin by metalloporphyrin bimetallic center 2D MOFs | |
| CN113563176B (en) | Cu (II)/nitric acid binary catalytic system for catalyzing O 2 Method for synthesizing adipic acid by oxidizing cyclohexene in one step | |
| CN108484383B (en) | Method for preparing glycolic acid compound | |
| CN112939765B (en) | Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane | |
| CN109369327A (en) | Novel nickel porphyrin-promoted cycloparaffin catalytic oxidation method | |
| CN110590504A (en) | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/copper (II) salt | |
| CN110563550A (en) | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt | |
| CN110590503A (en) | Method for preparing cycloalkanol and cycloalkanone by using cobalt (II) salt/copper (II) salt to synergistically catalyze selective oxidation of cycloalkane by molecular oxygen | |
| US12023649B2 (en) | Plant leaves-derived carbon material doped with two metals and preparation and use thereof | |
| CN102086152B (en) | Method for producing trifluoroacetic acid methyl ester by catalytic oxidation of methane | |
| Bhattacharyya et al. | Catalytic synthesis of lactic acid from acetaldehyde, carbon monoxide, and water | |
| CN111675599A (en) | Method for catalyzing and oxidizing aromatic benzyl tertiary C-H bond into tertiary alcohol by metalloporphyrin | |
| CN113683619B (en) | Metalloporphyrin trimetallic center 2D MOFs and preparation method and application thereof | |
| CN109575036A (en) | Two ester type compound of Metal hematoporphyrins bis ether, catalyst and preparation method thereof and catalytic oxidation of cyclohexane method | |
| CN111393397A (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN102219681B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN114105741B (en) | Preparation method of macrocyclic alcohol ketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |