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Method for oxidizing cyclohexane to prepare hexane diacid through one-step method and catalyst used by same

A technology for oxidizing cyclohexane and adipic acid, which is applied in the direction of oxidative preparation of carboxylic acid, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of long reaction time, pollution of the environment, high operating cost, etc., and achieve strong catalysis The effect of activity and selectivity

Inactive Publication Date: 2014-04-09
YANTAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Its disadvantages: the single-pass conversion rate of the synthesis of KA oil is low, especially with cyclohexane, the conversion rate is generally 5% to 12%, and the oxidant used when oxidizing KA to adipic acid is nitric acid. It will release a large amount of nitrogen oxides, seriously pollute the environment, coupled with high temperature and high pressure, high energy consumption
[0004] Chinese patents ZL03118249.6 and CN101337879B disclose a method for synthesizing adipic acid from metalloporphyrin catalyzed oxygen, cyclohexane oxide or cyclohexane, cyclohexanone, and cyclohexanol mixture, which is a homogeneous reaction with high catalytic efficiency , but the metal porphyrin type catalyst is expensive, the preparation method is complicated, the reaction time is long, and there are many reaction by-products
In addition, Chinese patents CN101337878B and CN1020405A disclose a method for preparing adipic acid by oxidizing cyclohexane with carbon nanotubes as a catalyst. This method is a heterogeneous reaction, and the catalyst can be reused many times, but a large amount of solvent and initiator are required in the reaction process , increasing the cost
Chinese patent CN101239899B discloses a method in which ruthenium oxide supported by a solid carrier is used as a catalyst to oxidize cyclohexane to generate adipic acid, but it also requires a large amount of solvent and initiator, and the operating cost is relatively high

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Catalyst Preparation: As an illustrative example, the

[0046] Na 11 [WZnRu 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ]·42H 2 O6.23g (1mmol) was dissolved in 40mL of deionized water, another 3.82g (11mmol) of octadecyltrimethylammonium chloride was dissolved in 40mL of absolute ethanol, heated slightly to dissolve it completely, and slowly dripped into Na 11 [WZnRu 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ] in aqueous solution, while vigorously stirring, the obtained yellow precipitate was filtered, washed, and dried at 60°C for 24 hours under vacuum to obtain the catalyst

[0047] [(C 18 h 37 ) 2 N(CH 3 ) 2 ] 11 [WZnRu 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ].

[0048] Oxidation of cyclohexane to prepare adipic acid: add 50mL of cyclohexane into a 160mL autoclave, and the above molecular formula is [(C 18 h 37 ) 2 N(CH 3 ) 2 ]11[WZnRu 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ] Dissolve the heteropolyacid catalyst in cyclohexane, stir magnetically, the concentration of the catalyst ...

Embodiment 2

[0053] The preparation method of catalyzer is the same as embodiment 1, but the sandwich type heteropolyacid containing noble metal is obtained

[0054] Na 12 [WZnPt 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ]·42H 2 O, quaternary ammonium salt (C 16 h 37 )N(CH 3 ) 3 Cl (6mmol), obtains catalyst [(C 16 h 37 )N(CH 3 ) 3 ] 6 Na 6 [WZnPt 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ].

[0055] Oxidation of cyclohexane to prepare adipic acid: 50mL of cyclohexane is added in a 160mL autoclave, and the above molecular formula is [(C 16 h 37 )N(CH 3 ) 3 ] 12 [WZnPt 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ] was dissolved in cyclohexane, magnetically stirred, the concentration of the catalyst was 10ppm, and then oxygen was introduced until the pressure in the autoclave was 0.2MPa, the temperature was raised to 140°C, and oxygen was continued to be introduced into the autoclave Oxygen pressure was stabilized to 0.5MPa, reacted for 9 hours, stopped the reaction to obtain a reaction product mixture...

Embodiment 3

[0057] The preparation method of catalyst is the same as embodiment 1, but sandwich type heteropolyacid gets Na 12 [WZnPd 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ]·42H 2 O, quaternary ammonium salt [(π~C 5 h 5 N + C 16 h 33 ]Cl (12mmol), the catalyst [(π~C 5 h 5 N + C 16 h 33 ] 12 [WZnPt 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ].

[0058] Oxidation of cyclohexane to prepare adipic acid: add 50mL of cyclohexane into a 160mL autoclave, and the above molecular formula is [(π~C 5 h 5 N + C 16 h 33 ] 12 [WZnPt 2 (OH)(H 2 O)(ZnW 9 o 34 ) 2 ] Dissolve the heteropolyacid catalyst in cyclohexane, stir it magnetically, the concentration of the catalyst is 10ppm, then feed oxygen until the pressure in the autoclave is 0.5MPa, raise the temperature to 147°C, and continue to feed oxygen into the autoclave Oxygen pressure was stabilized to 2.5MPa, reacted for 12 hours, stopped the reaction to obtain a reaction product mixture, cooled the obtained reaction product mixture to room t...

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Abstract

The invention discloses a method for oxidizing cyclohexane to prepare hexane diacid through a one-step method, which comprises the following steps: a, mixing the cyclohexane with a phase transfer catalyst, adequately agitating the mixture, adding an oxidant to the mixture, and reacting the mixture for 4-12 h under the conditions that a temperature is 140-180 DEG C and a pressure is 0.5-2.5 MPa to obtain a reaction product mixture, wherein the phase transfer catalyst is [(C18H37)2n(CH3)2]11[WZnRu2(OH)(H2o)(ZnW9O34)2], [(C16H37)N(CH3)3]6Na6[WZnPt2(OH)(H2O)(ZnW9O34)2], or [(C16H33)N(CH3)3]12[WZn2Ru(OH)(H2O)(ZnW9O34)21]; and b, after the reaction product mixture is cooled to a room temperature, filtering and washing the reaction product mixture to obtain a solid, and drying the solid to obtain the hexane diacid. The invention further provides a catalyst for oxidizing the cyclohexane to prepare the hexane diacid; the catalyst has extremely strong catalytic activity and selectivity; in the method provided by the invention, not only is the cyclohexane a reactant, but also the cyclohexane is a solvent; air or oxygen is used as the oxidant; other side products are not generated; and the pollution to the environment is avoided.

Description

technical field [0001] The invention relates to a method for preparing adipic acid by one-step oxidation of cyclohexane and a catalyst used in the method. Background technique [0002] Adipic acid, also known as fatty acid, is an important organic dibasic acid, which can react with polyols to produce polyester polyols, and then produce polyurethane products; adipic acid is a component of nylon 66 fiber and nylon resin An important raw material; adipic acid can also be used in lubricants, plasticizers and pharmaceutical industries. Internationally, adipic acid is used in more than 70% of nylon 66 fields, and in my country, adipic acid is used in polyurethane fields to reach 78%. In 2009, the global adipic acid production capacity reached 3.3 million tons. At present, the industrial synthesis of adipic acid is mainly carried out by nitric acid oxidation. Due to the use of strong oxidizing concentrated nitric acid in this method, the equipment is severely corroded, and the pr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C55/14C07C51/31B01J31/16
Inventor 吕宏缨任万忠郝冬梅孙逢新
Owner YANTAI UNIV