CN113563176B - A Cu(II)/nitric acid binary catalytic system catalyzes O2 oxidation of cyclohexene to synthesize adipic acid in one step - Google Patents

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

A Cu(II)/nitric acid binary catalytic system catalyzes O2 oxidation of cyclohexene to hexene in one step diacid method

technical field

The invention belongs to the field of industrial catalysis and fine organic synthesis, and specifically relates to a method for synthesizing adipic acid in one step by catalyzing _O2 oxidation of cyclohexene by a Cu(II)/nitric acid binary catalytic system.

Background technique

Adipic acid, also known as fatty acid (AA for short), with molecular formula HOOC(CH ₂ ) ₄ COOH, is the most valuable dibasic acid among aliphatic dibasic acids, mainly used in the synthesis of nylon 66, polyurethane and plasticizer. In addition, adipic acid can also be used to produce high-grade lubricating oil, food additives, pharmaceutical intermediates, flavors and fragrances, dyes, etc. (Chemical Engineering, 2013, 41(07): 42-44+49.). Currently, the annual production of adipic acid is about 3 million tons, illustrating the importance of adipic acid as an industrial precursor. In the future market, the demand for adipic acid will continue to grow (European Journal of Inorganic Chemistry, 2020(03): 248–252). At present, the industrial production process of adipic acid mainly includes benzene complete hydrogenation oxidation method and benzene partial hydrogenation oxidation method. Among them, the benzene partial hydrogenation oxidation method uses benzene as a raw material, undergoes partial hydrogenation to obtain cyclohexene, and further hydrates to obtain the intermediate product cyclohexanol. Cyclohexanol is catalyzed by nitric acid to synthesize adipic acid. Problems in this process: (1) The reaction path is long, the conversion rate is reduced, the energy consumption is increased, and the production cost is increased. (2) Using nitric acid to catalyze the oxidation of cyclohexanol to obtain adipic acid will cause a large amount of nitrogen oxides (0.3 t/1 t adipic acid) to be emitted, causing irreversible damage to the ozone layer and the environment. Therefore, effectively shortening the process route of industrial production, and adopting a suitable and efficient catalyst to directly catalyze the oxidation of cyclohexene, one-step synthesis of adipic acid, and reducing the use of nitric acid will help to improve the efficiency of adipic acid production by the partial hydrogenation oxidation of benzene Improvement is also conducive to reducing and reducing industrial production costs and emissions of _NOx gases. This design idea will be a very novel process improvement in the industrial adipic acid synthesis field with great application significance.

O ₂ is the oxidizing agent most in line with the concept of green chemistry. Its oxidation by-product is H ₂ O. It has no impact on the environment, is cheap and easy to obtain, and has high atom economy. It is the most promising oxidizing agent. Nitric acid is an oxidizing agent commonly used in industry, which can effectively oxidize cyclohexanol and cyclohexanone to adipic acid, but will produce nitrogen oxides NO _x . As a commonly used transition metal, Cu(II) has the ability to catalyze oxidation reactions and can promote the reaction (Catalysis Today, 2020, 346: 40–45).

Therefore, the present 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 to directly oxidize cyclohexene to synthesize adipic acid in one step. At the same time, in the environment where water exists, nitrogen oxides NO _x produced by _O2 oxidation produce nitrogen dioxide, and oxidative nitric acid is obtained again, which enters the cycle of cyclohexene oxide. The Cu(II)/nitric acid binary catalytic system of the present invention catalyzes the method for _O2 oxidation of cyclohexene to synthesize adipic acid, which has high yield, short reaction route, less emission of nitrogen oxides _NOx , low reaction temperature, and small environmental impact , low production cost and other advantages. In addition, the catalyst used in the invention is cheap and easy to obtain, which can greatly reduce the cost of industrial production. The invention provides an efficient, feasible and green method for synthesizing adipic acid in one step through the direct catalytic oxidation of cyclohexene.

Contents of the invention

For the above-mentioned technical problem that prior art exists, the object of the present invention is to provide a kind of Cu(II)/nitric acid binary catalytic system catalyzes O oxidative cyclohexene one _- step method for the synthesis of adipic acid.

Described a kind of Cu(II)/nitric acid binary catalytic system catalyzes O _The method for synthesizing adipic acid in one step from cyclohexene, it is characterized in that nitric acid and Cu(II) salt are dispersed in cyclohexene, sealed After the reaction system is heated up to the reaction temperature with stirring, the oxidant _O2 is introduced to the reaction pressure to carry out the stirring reaction to generate the target adipic acid product, and a small amount of glutaric acid and succinic acid products.

The method for one-step synthesis of adipic acid by catalyzing _O2 oxidation of cyclohexene by the Cu(II)/nitric acid binary catalytic system is characterized in that the Cu(II) salt is Cu(CH3COO _{)2 ,} At least one of Cu(NO ₃ ) ₂ , CuSO ₄ , CuCl ₂ , copper stearate, copper oxalate, copper acetylacetonate and their hydrates, or a mixture of two or more in any proportion.

Described a kind of Cu(II)/nitric acid binary catalytic system catalyzes O _The method for synthesizing adipic acid in one step from cyclohexene, it is characterized in that, described nitric acid concentration is 3.0～15.0 mol/L, is preferably 6.0～ 13.0mol/L; the ratio of the volume of nitric acid to the amount of substance of cyclohexene is 1:0.2~10, preferably 1:0.5~2.0, the unit of volume is L, and the unit of amount of substance is mol.

Described a kind of Cu(II)/nitric acid binary catalytic system catalyzes O _The method for synthesizing adipic acid in one step of oxidized cyclohexene, it is characterized in that, the amount of substance of described Cu(II) salt and cyclohexene The ratio is 1:10~10000, preferably 1:100~1000.

The method for one-step synthesis of adipic acid by catalyzing _O2 oxidation of cyclohexene by the Cu(II)/nitric acid binary catalytic system is characterized in that the reaction temperature is 40-120°C, preferably 45-70°C.

Described a kind of Cu(II)/nitric acid binary catalytic system catalyzes O _The method for synthesizing adipic acid in one step from cyclohexene, it is characterized in that, described reaction pressure is 0.10～2.0 MPa, is preferably 0.2～1.6MPa .

Described a kind of Cu(II)/nitric acid binary catalytic system catalyzes O _The method for synthesizing adipic acid in one step from oxidized cyclohexene, it is characterized in that, the speed of described stirring is 100～1000 rpm, is preferably 200～700rpm .

Described a kind of Cu(II)/nitric acid binary catalytic system catalyzes O _The method for synthesizing adipic acid in one step from cyclohexene, it is characterized in that, the reaction time is 2.0～24.0 h, preferably 6.0～16.0h .

The present invention uses the Cu(II)/nitric acid binary catalytic system to catalyze _O2 to oxidize cyclohexene to synthesize adipic acid in one step, which not only effectively shortens the process route, reduces energy consumption, and reduces costs, but also realizes the nitric acid oxidation of cyclohexene The NO produced by alkenes further reacts with oxygen to form NO ₂ , and NO ₂ is dissolved in water to form a nitric acid solution, which realizes the recycling of nitric acid, reduces the generation of by-products, and reduces the emission of environmental pollutant NO _x gas, which is in line with the current The realistic demand of the chemical industry for "energy saving and emission reduction". The invention not only provides a method for efficiently and greenly oxidizing cyclohexene to synthesize cycloadipic acid, but also has certain reference value for the efficient preparation of aliphatic diacids by catalytic oxidation of C=C bonds of other cycloalkenes.

The beneficial effects of the present invention are mainly reflected in: the Cu(II)/nitric acid binary catalytic system of the present invention catalyzes O _The method for the one-step synthesis of adipic acid by oxidizing cyclohexene has high yield, short reaction route, and nitrogen oxide NO _X emission is less, the reaction temperature is low, the environmental impact is small, and the production cost is low. In addition, the catalyst used in the present invention (namely the Cu(II)/nitric acid binary catalytic system) is cheap and easy to obtain, which can greatly reduce the cost of industrial production. The invention provides an efficient, feasible and green method for synthesizing adipic acid in one step through catalytic oxidation of cyclohexene.

detailed description

The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.

All reagents used in the examples of the present invention are commercially available analytically pure.

Embodiment 1～embodiment 40 is the catalytic oxidation case of cyclohexene;

Embodiment 41 ~ embodiment 43 are comparative experimental cases;

Embodiment 44 is a scale-up experiment.

Example 1

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH ₃ COO) ₂ (0.01 equive) were dispersed in 50 mL with a molar concentration of 11 mol/L nitric acid solution, seal the reaction vessel, stir and raise the temperature to 60°C reaction temperature, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 81%, the yield of glutaric acid was 5%, and the yield of succinic acid was 4%.

Example 2

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1876 g anhydrous Cu(NO ₃ ) ₂ (0.01 equive) were dispersed in 50 mL with a molar concentration of 11 mol/L nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 71%, the yield of glutaric acid was 10%, and the yield of succinic acid was 3%.

Example 3

In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1345 g anhydrous CuCl ₂ (0.01 equive) were dispersed in 50 mL of nitric acid with a molar concentration of 11 mol/L solution, seal the reaction kettle, stir and heat up to 60°C reaction temperature, and feed oxygen to a pressure of 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 68%, the yield of glutaric acid was 11%, and the yield of succinic acid was 3%.

Example 4

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1596 g anhydrous CuSO ₄ (0.01 equive) were dispersed in 50 mL of nitric acid with a molar concentration of 11 mol/L solution, seal the reaction kettle, stir and heat up to 60°C reaction temperature, and feed oxygen to a pressure of 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 67%, the yield of glutaric acid was 10%, and the yield of succinic acid was 2%.

Example 5

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH ₃ COO) ₂ (0.01 equive) were dispersed in 50 mL with a molar concentration of 6 mol/L nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 59%, the yield of glutaric acid was 5%, and the yield of succinic acid was 1%.

Example 6

In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 7 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 61%, the yield of glutaric acid was 6%, and the yield of succinic acid was 1%.

Example 7

In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 8 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 65%, the yield of glutaric acid was 6%, and the yield of succinic acid was 2%.

Example 8

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 9 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 70%, the yield of glutaric acid was 6%, and the yield of succinic acid was 2%.

Example 9

In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 10 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 72%, the yield of glutaric acid was 6%, and the yield of succinic acid was 3%.

Example 10

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 12 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 68%, the yield of glutaric acid was 4%, and the yield of succinic acid was 3%.

Example 11

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 13 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 65%, the yield of glutaric acid was 3%, and the yield of succinic acid was 3%.

Example 12

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 40°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 40°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 65%, the yield of glutaric acid was 2%, and the yield of succinic acid was 1%.

Example 13

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed oxygen until the pressure is 1.0 MPa. The reaction temperature was 45°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 70%, the yield of glutaric acid was 2%, and the yield of succinic acid was 1%.

Example 14

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 50°C, and feed oxygen until the pressure is 1.0 MPa. Stir the reaction at 50°C, 1.0 MPa oxygen pressure, and 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 75%, the yield of glutaric acid was 3%, and the yield of succinic acid was 1%.

Example 15

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and raise the temperature to a reaction temperature of 55°C, and feed oxygen to a pressure of 1.0 MPa. The reaction temperature was 55°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 78%, the yield of glutaric acid was 3%, and the yield of succinic acid was 2%.

Example 16

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 65°C, and feed in oxygen until the pressure is 1.0 MPa. The reaction temperature was 65°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 74%, the yield of glutaric acid was 3%, and the yield of succinic acid was 3%.

Example 17

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 70°C, and feed in oxygen until the pressure is 1.0 MPa. The reaction temperature was 70°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 71%, the yield of glutaric acid was 4%, and the yield of succinic acid was 2%.

Example 18

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 75°C, and feed in oxygen until the pressure is 1.0 MPa. The reaction temperature was 75°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 60%, the yield of glutaric acid was 4%, and the yield of succinic acid was 1%.

Example 19

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed in oxygen until the pressure is 0.2 MPa. The reaction temperature was 60°C, the oxygen pressure was 0.2 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 55%, the yield of glutaric acid was 1%, and the yield of succinic acid was 1%.

Example 20

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed in oxygen until the pressure is 0.4 MPa. Stir the reaction at 500 rpm for 12.0 h at a reaction temperature of 60 °C, an oxygen pressure of 0.4 MPa, and 500 rpm. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 68%, the yield of glutaric acid was 3%, and the yield of succinic acid was 1%.

Example 21

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and raise the temperature to 60°C reaction temperature, and feed oxygen until the pressure is 0.6 MPa. The reaction temperature was 60°C, the oxygen pressure was 0.6 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 69%, the yield of glutaric acid was 2%, and the yield of succinic acid was 1%.

Example 22

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed in oxygen until the pressure is 0.8 MPa. The reaction temperature was 60°C, the oxygen pressure was 0.8 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 72%, the yield of glutaric acid was 3%, and the yield of succinic acid was 2%.

Example 23

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed in oxygen until the pressure is 1.2 MPa. At 60°C reaction temperature, 1.2 MPa oxygen pressure, and 500 rpm stirring reaction for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 70%, the yield of glutaric acid was 4%, and the yield of succinic acid was 3%.

Example 24

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and heat up to the reaction temperature of 60°C, and feed in oxygen until the pressure is 1.4 MPa. At 60°C reaction temperature, 1.4 MPa oxygen pressure, and 500 rpm, the reaction was stirred for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 61%, the yield of glutaric acid was 3%, and the yield of succinic acid was 2%.

Example 25

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction kettle, stir and raise the temperature to 60°C reaction temperature, and feed oxygen until the pressure is (1.6 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.6 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 50%, the yield of glutaric acid was 3%, and the yield of succinic acid was 1%.

Example 26

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 4.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 41%, the yield of glutaric acid was 1%, and the yield of succinic acid was 1%.

Example 27

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 6.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 52%, the yield of glutaric acid was 1%, and the yield of succinic acid was 1%.

Example 28

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 8.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 65%, the yield of glutaric acid was 3%, and the yield of succinic acid was 1%.

Example 29

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). At 60°C reaction temperature, 1.0 MPa oxygen pressure, and 500 rpm stirring reaction for 10.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 71%, the yield of glutaric acid was 3%, and the yield of succinic acid was 2%.

Example 30

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). At 60°C reaction temperature, 1.0 MPa oxygen pressure, and 500 rpm, the reaction was stirred for 14.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 75%, the yield of glutaric acid was 4%, and the yield of succinic acid was 2%.

Example 31

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 16.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 63%, the yield of glutaric acid was 5%, and the yield of succinic acid was 1%.

Example 32

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.0018 g anhydrous Cu(CH3COO) ₂ (0.01% equive) _were dispersed in a 50 mL molar concentration 11 mol/L nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 66%, the yield of glutaric acid was 1%, and the yield of succinic acid was 1%.

Example 33

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.0188 g anhydrous Cu(CH3COO) ₂ (0.1% equive) _were dispersed in a 50 mL molar concentration 11 mol/L nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 69%, the yield of glutaric acid was 2%, and the yield of succinic acid was 1%.

Example 34

In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 1.8760 g anhydrous Cu(CH ₃ COO) ₂ (0.1 equive) were dispersed in 50 mL with a molar concentration of 11 mol/L nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 71%, the yield of glutaric acid was 4%, and the yield of succinic acid was 3%.

Example 35

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 100 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 42%, the yield of glutaric acid was 1%, and the yield of succinic acid was 2%.

Example 36

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 200 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 52%, the yield of glutaric acid was 2%, and the yield of succinic acid was 2%.

Example 37

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). At 60°C reaction temperature, 1.0 MPa oxygen pressure, and 300 rpm, the reaction was stirred for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 59%, the yield of glutaric acid was 3%, and the yield of succinic acid was 2%.

Example 38

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 400 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 70%, the yield of glutaric acid was 4%, and the yield of succinic acid was 2%.

Example 39

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 600 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 73%, the yield of glutaric acid was 4%, and the yield of succinic acid was 3%.

Example 40

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 700 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 74%, the yield of glutaric acid was 4%, and the yield of succinic acid was 4%.

Embodiment 41 (comparative experiment)

In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, disperse 8.2140 g (100 mmol) cyclohexene in 50 mL of nitric acid solution with a molar concentration of 11 mol/L, seal the autoclave, stir and heat up to 60 °C reaction temperature, feed oxygen to a pressure of (1.0 MPa). Stir the reaction at 500 rpm at a reaction temperature of 60°C, an oxygen pressure of 1.0 MPa, and 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 44%, the yield of glutaric acid was 1%, and no succinic acid was detected.

Embodiment 42 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, disperse 0.1997 g of anhydrous Cu(CH ₃ COO) ₂ in 8.2140 g (100 mmol) of cyclohexene, seal the autoclave, stir and heat up to 60 °C Reaction temperature, feed oxygen to pressure (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction result was: the yield of adipic acid was 5%, no glutaric acid was detected, and no succinic acid was detected.

Embodiment 43 (comparative experiment)

In a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, 8.2140 g (100 mmol) cyclohexene and 0.1997 g anhydrous Cu(CH3COO) _{2 were} dispersed in 50 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, stir and heat up to 60 ºC. Stir the reaction at 60 °C reaction temperature, 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 36%, the yield of glutaric acid was 1%, and no succinic acid was detected.

Embodiment 44 (scale-up experiment)

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 were dispersed in 500 mL with a molar concentration of 11 mol/L In the nitric acid solution, seal the reaction vessel, heat up to 60°C reaction temperature with stirring, and feed oxygen until the pressure is (1.0 MPa). The reaction temperature was 60°C, the oxygen pressure was 1.0 MPa, and the reaction was stirred at 500 rpm for 12.0 h. After the reaction was completed, it was cooled to room temperature, and the reaction product was analyzed and detected. The reaction results were as follows: the yield of adipic acid was 80%, the yield of glutaric acid was 5%, and the yield of succinic acid was 5%.

The content described in this specification is only an enumeration of the implementation forms of the inventive concepts, and the protection scope of the present invention should not be regarded as limited to the specific forms stated in the embodiments.

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.