CN109293601B - Method for safely synthesizing epoxypropane and co-producing adipic acid - Google Patents
Method for safely synthesizing epoxypropane and co-producing adipic acid Download PDFInfo
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/245—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of keto groups or secondary alcohol groups
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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Abstract
The invention belongs to the technical field of organic chemical industry, and relates to a method for safely synthesizing epoxypropane and co-producing adipic acid. The invention provides a method for safely synthesizing propylene oxide and co-producing adipic acid, which uses a pressurized rectifying device to recover propylene, uses oxygen decomposed by hydrogen peroxide to oxidize cyclohexanone to prepare adipic acid, removes oxygen in a gas phase, realizes co-production of high-added-value adipic acid, ensures intrinsic safety of the process, and simultaneously recovers propylene and nitrogen in tail gas for reuse, thereby realizing recycling of resources. The method has the advantages of high atom utilization rate, intrinsically safe process, reasonable utilization of resources, low VOC emission and the like.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a method for safely synthesizing epoxypropane and co-producing adipic acid, in particular to a method for preparing epoxypropane by a hydrogen peroxide direct oxidation method, wherein oxygen generated by decomposition of hydrogen peroxide in epoxidation reaction is used for oxidizing cyclohexanone, so that high-added-value adipic acid is prepared, oxygen in a system can be effectively removed, intrinsic safety of the process is ensured, and simultaneously propylene and nitrogen in tail gas are recycled, so that resource recycling is realized, wherein the epoxypropane synthesis: the yield is more than 90 percent, and the recovery rate of the pressurized rectified propylene is more than 99 percent; and (3) synthesis of adipic acid: the oxygen conversion rate is more than 99.5 percent, the selectivity is more than 80 percent, and finally the tail gas is completely compressed and returns to the synthesis of the propylene oxide, thereby realizing the complete recovery of the propylene. The method has the advantages of high atom utilization rate, intrinsically safe process, reasonable utilization of resources, low VOC emission and the like.
Background
Propylene oxide (propylene oxide) and adipic acid (adipic acid) are important basic organic chemical raw materials, propylene oxide is the second largest organic chemical product with the yield inferior to that of polypropylene in propylene derivatives, and is mainly used for producing chemical products such as polyether, propylene glycol, isopropanolamine and the like, and adipic acid is an important raw material for producing nylon 66 and polyurethane, and can be used as a plasticizer, a lubricant, a food additive and the like.
At present, the methods for producing propylene oxide mainly include a chlorohydrin method, a co-oxidation method and a direct hydrogen peroxide oxidation method. The chlorohydrin method has serious corrosion to equipment and large discharge amount of three wastes, and the chlorohydrin method device is listed as a restricted project according to the provision of the industry structure adjustment instruction catalog (2011), and is not approved to be newly built in principle. The co-oxidation method has many co-products and complex process, needs to consider both the raw material source and the co-product market, and has more restriction factors. The method for preparing the propylene oxide by directly oxidizing the propylene by the hydrogen peroxide has the advantages of high atom utilization rate and environmental friendliness, meets the development requirement of green chemistry, and is the method with the greatest development prospect for producing the propylene oxide.
However, in the process of the direct hydrogen peroxide oxidation method, a side reaction exists, hydrogen peroxide is decomposed to generate oxygen, the oxygen and gases such as propylene and nitrogen form mixed gas, the intrinsic safety of a reaction system is seriously threatened along with the increase of the oxygen content in the reaction, and patent CN201610008220.8 indicates that the direct mixing of propylene, oxygen and the like in the gas phase of the direct hydrogen peroxide oxidation method is easy to cause flash explosion accidents, and the intrinsic safety of the process is insufficient. Meanwhile, the gas phase contains organic substances such as propylene and the like, if a direct discharge or combustion discharge method is adopted, serious pollution is caused, resource waste is caused, and the economic benefit of the process is reduced, so that the propylene recovery and the oxygen treatment in the gas phase of the hydrogen peroxide direct oxidation method can directly influence the safety and the economic benefit of the process.
Patent CN201610008220.8 discloses a treatment device and process for preparing propylene oxide tail gas by direct oxidation of hydrogen peroxide, in which an absorbent is used to absorb propylene in the tail gas, and noble metals such as Pt, Pd, Ru and the like are used to remove oxygen by catalytic oxidation, but the method has the disadvantages of easy deactivation of catalyst and incomplete oxygen removal.
The document (Jiangjie, propylene separation process safety [ J ] safety and environmental bulletin, 2014,14 (6): 28-31.) reports the explosion limit of a ternary system of propylene-oxygen-nitrogen, and indicates that the flash evaporation scheme cannot meet the requirements of gas phase explosion safety control and the intrinsic safety of the process is insufficient.
Patent CN201210389707.7 discloses a process for preparing propylene oxide by directly oxidizing propylene with hydrogen peroxide, which adopts a pressurized rectifying tower to separate propylene and non-condensable gas, wherein the propylene flows out from the bottom of the pressurized rectifying tower, the non-condensable gas containing a small amount of organic matters is directly discharged into the atmosphere after passing through a gas phase absorption device, and a large amount of VOC is discharged, thus easily causing environmental pollution.
Patent CN201410578425.0 discloses a method for synthesizing adipic acid from cyclohexanone, which uses a titanium silicalite molecular sieve modified by transition metal as a catalyst to catalyze oxygen to oxidize cyclohexanone at 40-180 ℃ under 0.1-2.0 MPa to prepare adipic acid, but the method needs azo and peroxide substances as an initiator and has insufficient process safety.
Patent CN2003118249.6 discloses a method for preparing adipic acid by air oxidation of cyclohexanone under the catalysis of iron porphyrin or manganese porphyrin, the method prepares adipic acid by air oxidation of cyclohexanone, and the process catalyst is relatively complex in preparation, easy to be oxidized and deactivated, high in catalyst cost, and low in yield of adipic acid.
Literature (Ishii. direct conversion of cyclic alkane inter-adaptive acid with molecular oxygenated by N-hydroxyphenylalimide combined with Mn (acac)2and Co(OAc)2[J].Organic Process Research&Developmen,1998, 2(4):255) proposes that manganese acetylacetonate is used as a catalyst, N-hydroxyphthalimide is used as an initiator, acetic acid is used as a solvent, cyclohexane is oxidized by oxygen to synthesize adipic acid, and after the reaction is carried out at the reaction temperature of 100 ℃ for 6 hours, the conversion rate of the cyclohexane is 36 percent, and the selectivity of the adipic acid is 40 percent.
Disclosure of Invention
The method has the advantages of high atom utilization rate, intrinsically safe process, reasonable utilization of resources, low VOC emission and the like. With the increasing requirements on safety, environmental protection and green chemistry, the intrinsic safety of the process for preparing propylene oxide by directly oxidizing propylene with hydrogen peroxide and the recycling of propylene are concerned more and more, but the practicability of the propylene recycling scheme in the prior art is not strong, and the method of burning oxygen, nitrogen and a small amount of organic gas in tail gas causes resource waste, potential safety hazard and environmental pollution.
The invention provides a method for safely synthesizing propylene oxide and co-producing adipic acid, which uses a pressurized rectifying device to recover propylene, uses oxygen decomposed by hydrogen peroxide to oxidize cyclohexanone to prepare adipic acid, removes oxygen in a gas phase, realizes co-production of high-added-value adipic acid, ensures intrinsic safety of the process, and simultaneously recovers propylene and nitrogen in tail gas for reuse, thereby realizing recycling of resources.
The invention aims to provide a novel method for safely synthesizing propylene oxide and co-producing adipic acid, which has the advantages of high atom utilization rate, intrinsically safe process, reasonable resource utilization and low VOC (volatile organic compound) emission.
The invention provides a method for safely synthesizing propylene oxide and co-producing adipic acid, which adopts hydrogen peroxide to directly oxidize propylene to prepare propylene oxide, and simultaneously utilizes oxygen generated by hydrogen peroxide decomposition to oxidize cyclohexanone and co-produce adipic acid with high added value, thereby ensuring the intrinsic safety of the process, being clean and environment-friendly, completely recycling propylene and nitrogen in a system and realizing the reasonable utilization of resources.
The purpose of the invention is realized by the following method:
a method for safely synthesizing propylene oxide and co-producing adipic acid specifically comprises the following steps:
(1) adding a catalyst and a solvent into a propylene oxide synthesis reaction kettle, filling propylene, adding hydrogen peroxide, and oxidizing the propylene with the hydrogen peroxide under the action of the catalyst to obtain a crude propylene oxide product;
(2) in the reaction process, the gas-phase component passes through a pressurized rectifying tower, propylene is recovered, and the propylene is applied to the synthesis reaction of the propylene oxide;
(3) introducing the noncondensable gas at the top of the pressurized rectifying tower into a cyclohexanone oxidation reactor, and oxidizing cyclohexanone by oxygen under the action of a catalyst to prepare adipic acid;
(4) and (3) compressing the gas extracted from the cyclohexanone reactor, returning the gas to the epoxypropane synthesis reaction kettle in the step (1) for recycling, and realizing the complete recycling of unconverted propylene.
The catalyst in the step (1) is one or a mixture of more of heteropoly acid or titanium silicalite molecular sieve, the heteropoly acid includes but is not limited to phosphotungstic acid, phosphomolybdic acid, phosphosilicic acid, phosphovanadic acid and phosphomolybdic vanadic acid, and the using amount of the catalyst is 0.5-20% of the mass of the propylene;
the solvent in the step (1) is one or a mixture of more of benzene, toluene, p-xylene, mesitylene, chlorobenzene, methanol, ethanol, isopropanol, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetonitrile and N, N-dimethylformamide, and the amount of the solvent is 1-10 times of the mass of propylene;
in the step (1), the mass fraction of the hydrogen peroxide is 30-75%, and the dosage of the hydrogen peroxide is 0.1-1 time of the mole number of the propylene;
the reaction pressure in the step (1) is 2-6 MPa; the reaction temperature is 30-80 ℃, and the reaction time is 2-24 hours;
the gas phase component in the step (2) is a mixture of propylene, oxygen and nitrogen;
the non-condensable gas in the step (3) is oxygen, nitrogen and a small amount of propylene, wherein the volume fraction of the propylene is less than 1%;
oxidizing cyclohexanone by using oxygen in the step (3) to prepare adipic acid, wherein a solvent is one or a mixture of more of water, chlorobenzene, acetonitrile, propionitrile, tert-butyl alcohol, ethyl acetate and acetic acid, and the using amount of the solvent is 1-10 times of the mass of the cyclohexanone;
the catalyst in the step (3) is one or a mixture of more of acetates, nitrates or porphyrin complexes of transition metals such as cobalt, copper, iron, manganese, vanadium, cadmium, tungsten and the like, and the dosage of the catalyst is 0.5-20% of the mass of cyclohexanone;
the oxidation reaction temperature of the cyclohexanone in the step (3) is 30-120 ℃, and the reaction time is 1-12 hours;
the volume fraction of oxygen in the gas returned to step (1) by compression described in step (4) above is less than 1%.
The invention adopts a direct oxidation method of hydrogen peroxide to prepare propylene oxide, and utilizes oxygen in a gas phase after the epoxidation reaction to oxidize cyclohexanone, thereby not only preparing adipic acid with high added value, but also removing oxygen in a system and recovering propylene and nitrogen in the gas phase, and the invention has the following advantages:
(1) the atom utilization rate is high: the method has the advantages that the hydrogen peroxide directly oxidizes propylene to prepare propylene oxide, and oxygen generated by decomposing the hydrogen peroxide is used for oxidizing cyclohexanone to prepare adipic acid, so that the method has the characteristics of high atom utilization rate and few byproducts.
(2) And (3) reasonable utilization of resources: according to the invention, the pressurized rectifying tower is used for recovering propylene, oxygen generated by the decomposition of the hydrogen peroxide side reaction is used for oxidizing cyclohexanone to prepare adipic acid, and meanwhile, nitrogen in the system is recycled and used completely, and unconverted propylene is completely recovered and used, so that reasonable and efficient utilization of resources is realized.
(3) The process is intrinsically safe: by oxidizing cyclohexanone by oxygen, adipic acid with high added value is prepared, oxygen in an epoxidation system is removed, oxygen accumulation in the system is avoided, and the intrinsic safety of the process is ensured.
(4) Green chemistry, environmental protection: according to the invention, the direct oxidation method of hydrogen peroxide is used for replacing a chlorohydrin method to prepare propylene oxide, so that the discharge of three wastes is reduced, and meanwhile, oxygen generated by decomposition of hydrogen peroxide is used for oxidizing cyclohexanone to prepare adipic acid, so that a NOx compound generated by preparing adipic acid by a traditional nitric acid oxidation method is avoided.
Detailed Description
Example 1
1000g of toluene and 20g of phosphotungstic acid catalyst are added into a propylene oxide synthesis reaction kettle, 500g of propylene and 300g of hydrogen peroxide with the mass fraction of 35 percent are filled, nitrogen is filled to control the reaction pressure to be 4MPa, the reaction is carried out for 2 hours at the temperature of 80 ℃, and the yield of the propylene oxide is 90.75 percent. And continuously separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components in a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas extracted from the tower top is 9.94%, the volume fraction of nitrogen is 89.93%, the volume fraction of propylene is 0.13%, and the recovery rate of propylene in the pressurized rectifying stage is 99.20%.
1000g of cyclohexanone, 20g of cobalt acetate and 1000g of acetic acid solvent are added into a cyclohexanone oxidation reactor, noncondensable gas extracted from the top of a pressurized rectifying tower is introduced to oxidize the cyclohexanone to prepare adipic acid, the reaction is carried out for 8 hours at 60 ℃, the oxygen conversion rate is 99.51%, the adipic acid selectivity is 84.51%, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.15%, the volume fraction of oxygen is 0.06%, and the volume fraction of nitrogen is 99.79%, and the mixture is compressed and returned to an epoxypropane synthesis reaction kettle for recycling, so that the complete recovery of unconverted propylene is realized.
Example 2
1000g of acetonitrile and 50g of phosphomolybdic acid catalyst are added into a propylene oxide synthesis reaction kettle, 420g of propylene and 70g of hydrogen peroxide with the mass fraction of 50 percent are filled, nitrogen is filled to control the reaction pressure to be 4MPa, the reaction is carried out for 6 hours at the temperature of 60 ℃, and the yield of the propylene oxide is 93.01 percent. And (3) separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components through a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas extracted from the tower top is 7.44%, the volume fraction of nitrogen is 92.22%, the volume fraction of propylene is 0.34%, and the recovery rate of propylene in the pressurized rectifying stage is 99.32%.
1000g of cyclohexanone, 5g of manganese acetate and 1000g of butanone solvent are added into a cyclohexanone oxidation reactor, noncondensable gas extracted from the top of a pressurized rectifying tower is introduced to oxidize the cyclohexanone to prepare adipic acid, the reaction is carried out for 4 hours at 50 ℃, the oxygen conversion rate is 99.45 percent, the adipic acid selectivity is 86.32 percent, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.37 percent, the volume fraction of oxygen is 0.04 percent, the volume fraction of nitrogen is 99.59 percent, and the gas is compressed and returned to an epoxypropane synthesis reaction kettle for recycling, so that the complete recovery of unconverted propylene is realized.
Example 3
1000g of dichloroethane and 50g of phosphorus vanadic acid catalyst are added into a propylene oxide synthesis reaction kettle, 210g of propylene and 500g of hydrogen peroxide with the mass fraction of 34 percent are filled, nitrogen is filled to control the reaction pressure to be 3MPa, the reaction is carried out for 18 hours at the temperature of 40 ℃, and the yield of the propylene oxide is 90.50 percent. And (3) separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components through a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas extracted from the tower top is 11.28%, the volume fraction of nitrogen is 88.50%, the volume fraction of propylene is 0.22%, and the recovery rate of propylene in the pressurized rectifying stage is 99.45%.
1000g of cyclohexanone, 10g of ferroporphyrin and 5000g of isobutanol solvent are added into a cyclohexanone oxidation reactor, noncondensable gas extracted from the top of a pressurized rectifying tower is introduced to oxidize the cyclohexanone to prepare adipic acid, the reaction is carried out for 2 hours at 100 ℃, the oxygen conversion rate is 99.80%, the adipic acid selectivity is 83.75%, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.03%, the volume fraction of oxygen is 0.25%, and the volume fraction of nitrogen is 99.73%, and the gas is compressed and returned to an epoxypropane synthesis reaction kettle for recycling, so that the complete recovery of unconverted propylene is realized.
Example 4
1000g of methanol and 82g of titanium silicalite molecular sieve catalyst are added into a propylene oxide synthesis reaction kettle, 420g of propylene and 200g of hydrogen peroxide with the mass fraction of 75 percent are filled, nitrogen is filled to control the reaction pressure to be 5MPa, the reaction is carried out for 24 hours at the temperature of 30 ℃, and the yield of the propylene oxide is 92.12 percent. And (3) separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components through a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas extracted from the tower top is 3.46%, the volume fraction of nitrogen is 96.29%, the volume fraction of propylene is 0.25%, and the recovery rate of propylene in the pressurized rectifying stage is 99.62%.
Adding a mixture of 1000g of cyclohexanone, 100g of copper nitrate, 8000g of acetic acid and water in equal proportion into a cyclohexanone oxidation reactor, introducing noncondensable gas extracted from the top of a pressurized rectifying tower to oxidize the cyclohexanone to prepare adipic acid, reacting at 120 ℃ for 1 hour, wherein the oxygen conversion rate is 99.85%, the adipic acid selectivity is 81.79%, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.26%, the volume fraction of oxygen is 0.01%, and the volume fraction of nitrogen is 99.73%, compressing the mixture and returning the compressed mixture to an epoxypropane synthesis reaction kettle for recycling, thereby realizing the complete recovery of unconverted propylene.
Example 5
1000g of chloroform and 50g of phosphotungstic acid catalyst are added into a propylene oxide synthesis reaction kettle, 100g of propylene and 200g of hydrogen peroxide with the mass fraction of 35 percent are filled, nitrogen is filled to control the reaction pressure to be 6MPa, the reaction is carried out for 15 hours at the temperature of 90 ℃, and the yield of the propylene oxide is 91.95 percent. And (3) separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components through a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas flowing out of the tower top is 3.67%, the volume fraction of nitrogen is 96.20%, the volume fraction of propylene is 0.13%, and the recovery rate of propylene in the pressurized rectifying stage is 99.42%.
1000g of cyclohexanone, 150g of cobalt porphyrin and 10000g of acetone solvent are added into a cyclohexanone oxidation reactor, noncondensable gas extracted from the top of a pressurized rectifying tower is introduced to oxidize the cyclohexanone to prepare adipic acid, the reaction is carried out for 5 hours at 80 ℃, the oxygen conversion rate is 99.90 percent, the adipic acid selectivity is 83.69 percent, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.26 percent, the volume fraction of oxygen is 0.01 percent, the volume fraction of nitrogen is 99.73 percent, and the gas phase is compressed and returned to an epoxypropane synthesis reaction kettle for recycling, so that the complete recovery of unconverted propylene is realized.
Example 6
1000g of p-xylene and 40g of phosphomolybdic acid catalyst are added into a propylene oxide synthesis reaction kettle, 300g of propylene and 500g of hydrogen peroxide with the mass fraction of 35 percent are filled, nitrogen is filled to control the reaction pressure to be 2MPa, the reaction lasts for 10 hours at 50 ℃, and the yield of propylene oxide is 91.12 percent. And (3) separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components through a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas flowing out of the tower top is 7.46%, the volume fraction of nitrogen is 92.20%, the volume fraction of propylene is 0.34%, and the recovery rate of propylene in the pressurized rectifying stage is 99.15%.
1000g of cyclohexanone, 200g of manganese nitrate and 3000g of acetone solvent are added into a cyclohexanone oxidation reactor, noncondensable gas extracted from the top of a pressurized rectifying tower is introduced to oxidize the cyclohexanone to prepare adipic acid, the reaction is carried out for 8 hours at 50 ℃, the oxygen conversion rate is 99.68 percent, the selectivity of the adipic acid is 84.36 percent, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.26 percent, the volume fraction of oxygen is 0.01 percent, the volume fraction of nitrogen is 99.73 percent, and the gas phase is compressed and returned to an epoxypropane synthesis reaction kettle for recycling, so that the complete recovery of unconverted propylene is realized.
Example 7
1000g of ethanol and 10g of titanium silicalite molecular sieve catalyst are added into a propylene oxide synthesis reaction kettle, 600g of propylene and 300g of hydrogen peroxide with the mass fraction of 50 percent are filled, nitrogen is filled to control the reaction pressure to be 5MPa, the reaction is carried out for 12 hours at the temperature of 60 ℃, and the yield of the propylene oxide is 89.70 percent. And (3) separating gas-phase components in the reaction process, separating and recovering propylene from the gas-phase components through a pressurized rectifying tower, wherein the volume fraction of oxygen in the non-condensable gas extracted from the tower top is 5.28%, the volume fraction of nitrogen is 94.33%, the volume fraction of propylene is 0.38%, and the recovery rate of propylene in the pressurized rectifying stage is 99.52%.
1000g of cyclohexanone, 50g of a mixture of cobalt acetate and manganese acetate in equal proportion and 2000g of methanol solvent are added into a cyclohexanone oxidation reactor, noncondensable gas extracted from the top of a pressurized rectifying tower is introduced to oxidize the cyclohexanone to prepare adipic acid, the reaction is carried out at 70 ℃ for 6 hours, the oxygen conversion rate is 99.62%, the adipic acid selectivity is 84.24%, the volume fraction of propylene in a gas phase after the oxidation reaction of the cyclohexanone is finished is 0.26%, the volume fraction of oxygen is 0.01%, the volume fraction of nitrogen is 99.73%, and the gas phase is compressed and returned to an epoxypropane synthesis reaction kettle for recycling, so that the complete recovery of unconverted propylene is realized.
Examples 8 to 12
The reaction process and conditions were the same as in example 1, and recovered propylene and nitrogen were used together to examine the use stability, and the results are as follows.
Remarking: the recovery rate of propylene is 99.20% in the pressurized rectification stage, and the gas after oxidation of cyclohexanone returns to the epoxypropane synthesis reaction kettle to realize complete recovery and reuse of propylene.
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. A method for safely synthesizing propylene oxide and co-producing adipic acid is characterized by comprising the following steps:
(1) adding a catalyst and a solvent into a propylene oxide synthesis reaction kettle, filling propylene, adding hydrogen peroxide, and oxidizing the propylene with the hydrogen peroxide under the action of the catalyst to obtain a crude propylene oxide product;
(2) in the reaction process, the gas-phase component passes through a pressurized rectifying tower, propylene is recovered, and the propylene is applied to the synthesis reaction of the propylene oxide;
(3) introducing the noncondensable gas at the top of the pressurized rectifying tower into a cyclohexanone oxidation reactor, and oxidizing cyclohexanone by oxygen under the action of a catalyst to prepare adipic acid;
(4) compressing the gas extracted from the cyclohexanone reactor and returning the gas to the epoxypropane synthesis reaction kettle in the step (1) for recycling, so as to realize complete recovery and recycling of unconverted propylene;
the catalyst in the step (1) is one or a mixture of more of heteropoly acid or titanium silicalite molecular sieve, the heteropoly acid comprises phosphotungstic acid, phosphomolybdic acid, phosphosilicic acid, phosphovanadic acid and phosphomolybdic vanadic acid, and the dosage of the catalyst is 0.5-20% of the mass of the propylene.
2. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the solvent in the step (1) is one or more of benzene, toluene, p-xylene, mesitylene, chlorobenzene, methanol, ethanol, isopropanol, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetonitrile and N, N-dimethylformamide, and the amount of the solvent is 1-10 times of the mass of propylene.
3. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the mass fraction of the hydrogen peroxide in the step (1) is 30-75%, and the amount of the hydrogen peroxide is 0.1-1 time of the mole number of the propylene.
4. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the reaction pressure in the step (1) is 2-6 MPa; the reaction temperature is 30-80 ℃, and the reaction time is 2-24 hours.
5. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the gas phase component in the step (2) is a mixture of propylene, oxygen and nitrogen.
6. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the non-condensable gas in the step (3) is oxygen, nitrogen and a small amount of propylene, and the volume fraction of the propylene is less than 1%.
7. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the step (3) further comprises a solvent, wherein the solvent is one or a mixture of more of water, chlorobenzene, acetonitrile, propionitrile, tert-butyl alcohol, ethyl acetate and acetic acid, and the amount of the solvent is 1-10 times of the mass of cyclohexanone.
8. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the catalyst in the step (3) is one or a mixture of more of acetates, nitrates or porphyrin complexes of transition metals cobalt, copper, iron, manganese, vanadium, cadmium and tungsten, and the amount of the catalyst is 0.5-20% of the mass of cyclohexanone; the reaction temperature is 30-120 ℃, and the reaction time is 1-12 hours.
9. The method for safely synthesizing propylene oxide and co-producing adipic acid according to claim 1, wherein the volume fraction of oxygen in the gas returned to the step (1) by compression in the step (4) is less than 1%.
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| CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN101885712A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN105622386A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Green process for synthesizing adipic acid from cyclohexanone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN101885712A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN105622386A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Green process for synthesizing adipic acid from cyclohexanone |
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