CN109456167A - A method of using micro passage reaction by cyclohexanone synthesizing adipic acid - Google Patents
A method of using micro passage reaction by cyclohexanone synthesizing adipic acid Download PDFInfo
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- CN109456167A CN109456167A CN201811560273.6A CN201811560273A CN109456167A CN 109456167 A CN109456167 A CN 109456167A CN 201811560273 A CN201811560273 A CN 201811560273A CN 109456167 A CN109456167 A CN 109456167A
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- reaction
- adipic acid
- micro passage
- cyclohexanone
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- 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
Abstract
The invention belongs to organic synthesis applied technical fields, and in particular to a method of using micro passage reaction by cyclohexanone synthesizing adipic acid.It is one kind in micro passage reaction, and using cyclohexanone and oxygen as raw material, cobalt complex is catalyst, prepares the new process of adipic acid in of short duration reaction time internal oxidition.Material is after metering pump is passed through micro passage reaction, and by preheating, mixing, oxidation reaction post-processes to obtain adipic acid product.The method of the present invention is easy to operate and safe, high yield continuous production adipic acid product, and the technique uses oxygen molecule as oxidant, and environmental pollution substantially reduces.
Description
Technical field
The invention belongs to organic synthesis applied technical fields, and in particular to using cyclohexanone, hexamethylene and oxygen as raw material, cobalt
Complex compound is catalyst, and oxidation reaction is carried out in continuous flow micro passage reaction and prepares adipic acid product.More specifically, it is
In high-throughput microchannel continuous flow micro passage reaction, the technique for preparing adipic acid using dioxygen oxidation cyclohexanone.
Background technique
Adipic acid (adipic acid, 1,6-hexanedioic acid, C6H10O4), alias adipic acid, white crystalline,
Fusing point is 152 DEG C, and boiling point is 337 DEG C, and density is 1.36 g/cm3, it is soluble in ethyl alcohol；It is slightly soluble in water under room temperature, but it is with temperature
It is larger to increase changes in solubility in water.Adipic acid is most large one of industrial chemicals, and annual requirement is more than 2,500,000 tons, main
To be applied to nylon 6,6 to produce, be also commonly used for the industries such as resin, polyurethane, plasticizer, lubricant and food additives.
The catalyst system of synthesizing adipic acid is more, metallic salt catalyst system be it is studied earliest, also applied earliest
In industrialized production adipic acid.Early in nineteen thirty-seven, DuPont Corporation just realizes oneself by " two-step method " using hexamethylene as raw material
Diacid industrial production.Currently, the industrial process of adipic acid still be mainly hexamethylene method, the process route account for about the whole world oneself
The 93% of diacid total productive capacity.
1998, Sato etc. report for the first time one kind using cyclohexene as the method for raw material, " green " synthesizing adipic acid, with
Na2WO4For catalyst, with [CH3(n-C8Hl7)3N]HSO4It is oxidant for consisting of phase-transferring agent, 30wt.% aqueous hydrogen peroxide solution, no
Solubilizer and halogen additive, cyclohexene direct oxidation synthesizing adipic acid, by-product is water.Cyclohexene: tungsten: consisting of phase-transferring agent mole
Than reacting 8h at 75 DEG C~90 DEG C, 161g sterling adipic acid (after purification) at most can be generated in 100g cyclohexene for 100:1:1
(highest yield 90%).Because of the good spatter property and high efficiency of reaction process, cyclohexene direct oxidation synthesizing adipic acid starts
It enjoys great popularity, and mostly using wolframic acid or its esters as catalyst.The disadvantage is that the reaction time is long, the high (production of hydrogen peroxide consumption
1mol adipic acid consumes 4mol hydrogen peroxide).
1990s, DuPont develop biocatalysis technique, converted D2 glucose to using Escherichia coli it is suitable, it is cis-
Then hexadienoic acid is hydrogenated to adipic acid.Later the said firm developed new bioprocess technology method again, with from aerobic denitration bacterial strain
In a kind of gene cluster for separating enzyme is encoded, to obtain the synzyme that cyclohexanol converts adipic acid processed.The synthesis
Cyclohexanol can be selectively converted to adipic acid under suitable growth conditions by the mutation chief cell of enzyme.
The material HN0 as used in " hexamethylene two-step method " system3With a large amount of solvent (being largely glacial acetic acid) meeting
Heavy corrosion is generated to equipment, in addition, some systems need a large amount of catalyst, some even need to add a large amount of promotor with
Co-catalyst, such as acetaldehyde, nitrogen hydroxyl phthalimide (NHPI).The KA oil generated by hexamethylene is oxidized in nitric acid effect
Adipic acid, although higher conversion ratio and selectivity can be obtained, there are serious environmental pollutions for the process.With environmental protection pressure
It is increasing, for the nitrogen oxygen for using corrosivity nitric acid material and the serious pollution environment of generation present in adipic acid production process
The problems such as compound, nitric acid vapor and acid pickle, the process for cleanly preparing of adipic acid becomes the emphasis of research and development at present.Therefore,
The friendly process of research synthesizing adipic acid has great significance, and how to reduce cost of material, reduces energy consumption, improves adipic acid production
Rate, reduce environmental pollution be synthesizing adipic acid oxidation technology development direction.
Summary of the invention
A kind of efficient the present invention is directed to overcome the deficiencies of the prior art and provide, highly-safe, more clean adipic acid closes
At process flow.The present invention is used using cyclohexanone and oxygen as raw material, and hexamethylene is solvent, and cobalt complex is catalyst, NHPI
Oxidation reaction, which is carried out, for co-catalyst prepares adipic acid.The reaction mechanism of oxidizing cyclohexanone synthesizing adipic acid such as Fig. 3, hexamethylene
Ketone is oxidized to caprolactone first, is further oxidized to adipic acid.
In order to achieve the above object, the technical solution adopted by the present invention are as follows: synthesized using micro passage reaction by cyclohexanone
Adipic acid.Its operating process carries out as steps described below:
(1) preparation of reaction solution: cobalt-containing catalyst, co-catalyst, cyclohexanone, hexamethylene are mixed, and obtain catalysis oxidation mixing
Material；
(2) step (1) mixed material is pumped into microreactor, material respectively enters warm-up block, and preheating reaches estimated anti-
Temperature is answered, set temperature is controlled by external heat exchanger, and heat transferring medium is conduction oil；Oxygen passes through oxygen pressure reducing valve, mistake
Flow is controlled by gas mass flow controller after filter, preheating section is flowed through and is preheated；Material and oxygen after preheated is in T
It is contacted in type mixer, into reaction zone mixing, reaction, mixing temperature is equally controlled by external heat exchanger；Reaction process
After the completion, the efflux of reaction zone is adipic acid crude product；
(3) reaction region effluent, which flows through counterbalance valve and enters gas-liquid separator, is separated, and liquid product is collected into product bottle, gas
Mutually empty；The additional condenser jacket of gas-liquid separator；
(4) adipic acid isolates and purifies and catalyst recycling: obtained solution of adipic acid is placed 0 DEG C of cooling 2h, suction filtration, ice
For several times, vacuum filtration, drying can obtain adipic acid crystals to water washing；It is anti-that mother liquor can be used for catalysis next time after revolving water removal concentration
It answers.
The total conversion of cyclohexanone is 100%, adipic acid selectivity about 95.8%, product purity 99%, wherein Main By product
For oxidizing cyclohexanone reaction intermediate.Reaction system pressure is 0~0 .7MPa；Reaction temperature is 90 ~ 130 DEG C.
The mass ratio of the reaction solution cyclohexanone and hexamethylene is 4:1, and flow velocity is 0.002 ~ 0.01m/s, wherein containing cobalt
The concentration of catalyst is 200ppm, cocatalyst concentration 200ppm；Oxidant oxygen, flow velocity are 1 ~ 2m/s；Material is reacting
The residence time in area is 1~60min.
The catalyst of class containing cobalt is cobalt complex, cobalt complex (II), one of cobalt complex (III)；Described
Co-catalyst is nitrogen hydroxyl phthalimide (NPHI).
Microchannel structure in the micro passage reaction reaction zone module is enhancing mixed type channel design；Wherein increase
Strong mixed type channel design is spherical structure, spherical band one of baffle arrangement, drops structure, and channel hydraulic diameter is
0.8mm, length 20m；Module material is special glass, the stainless steel or metal alloy for being coated with corrosion resistant coating；Reaction system can
Anti-corrosion pressure resistance, voltage endurance capability view material is different and different, and it is 15~30bar that Maximum safe pressure is reacted in system.
Microreactor obtains great specific surface because of the geometrical property of its own " small " in the reaction compartment of very little
Product.Relative to traditional batch reaction process, microreactor application process has mixed at high speed, efficient mass transfer and heat transfer, narrow
Residence time destribution, the residence time is adjustable, convenient for automation control, reaction volume it is small, almost without enlarge-effect and high peace
The advantages that full performance.Therefore, microreaction technology is in the moment reaction controlled by microcosmic mixed effect, in mass transport process
Many reaction classes such as middle fast reaction, the relatively unstable consecutive reaction of intermediate product and the strongly exothermic explosive reaction of control
Huge application prospect is shown in type.Organic matter liquid phase oxidation reaction process is mostly complicated free chain reaction, is deposited
The problems such as intermediate product is more, reaction selectivity is poor or transmittance process is complex.These problems are to liquid phase oxidation reaction
The design of device and the operation control of reaction process are a challenges.Bubble tower, stirring bubbling reactor, Airlift circulating reaction
It is anti-that the traditional reactors such as device, trickle bed reactor, filler tower reactor and board-like tower reactor are usually used in organic matter liquid phase oxidation
Answer process, however these reactors microcosmic mixing, heat and mass transport and it is potential in terms of can not be suitble to many
The response characteristic of organic matter liquid phase oxidation cannot obtain ideal reaction result.Reactor technology has efficient microcosmic mixing
The advantages that characteristic, good mass transfer and heat transfer property and higher safety operation performance, the above problem can be overcome；It is as a kind of
Process intensification technology, be used widely in many organic matter liquid phase oxidation reactions and achieve good conversion ratio or
Selectivity.
The present invention has following main feature compared with prior art:
1, the present invention has apparent Green Chemistry advantage: abundance according to molecular oxygen is used as oxygen source, cheap and easy to get, right
Equipment is corrosion-free, not generation environment pollutant.
2, the present invention uses the continuous synthesizing adipic acid of micro passage reaction, and the reaction time shortens to several from traditional a few hours
To a few minutes, reaction rate is significantly improved within ten seconds.
3, the micro passage reaction used enhances the mass transfer of reaction, heat transfer property, keeps reaction temperature constant, avoids
Occurs phenomena such as temperature runaway, slug, runaway reaction when reaction, operability and safety greatly improve.
Detailed description of the invention
Fig. 1 is continuous flow micro passage reaction device figure used in the present invention: 1,5 head tank, 2,6- feed pump, 3,7-
Pressure gauge, the microchannel 4-, 5- heat exchanger, 9- product are collected；
Fig. 2 is form figure in microchannel used in the present invention and specific size: 1- spherical shape microchannel, 2- spherical shape microchannel add
The baffle of 0.6mm wide, 3- droplet-shaped microchannel.
Fig. 3 reaction mechanism figure of the present invention.
Specific embodiment
Embodiment 1
(1) equipment therefor: continuous flow micro passage reaction (" ball-type " structure function module), hybrid reaction number of modules is according to flow velocity
Determine that heat transferring medium is conduction oil with reaction time.
(2) head tank 1 has configured reaction solution, (cyclohexanone and hexamethylene mass ratio 4:1, the concentration of cobalt ions are 200ppm,
NPHI concentration is 200ppm).Control reaction flow velocity: 0.5mL/min, control oxygen gas flow rate: 10mL/min beats material respectively
Enter in each straight channel warm-up block, controlling reaction temperature is 110 DEG C, pressure 0.7MPa；Reaction solution is driven into micro- with oxygen
It is reacted in mixer.Reaction time is 30min, after reaction product passes through cooling coil ice-water bath, with high score dephasing
Continuous stream mode outflow reactor.
(3) crystallized dry the adipic acid product of reaction solution.Cyclohexanone total conversion is 20%, and adipic acid selectivity is about
95%。
Embodiment 2
(1) equipment therefor: continuous flow micro passage reaction (droplet-shaped channel), hybrid reaction number of modules are stopped according to flow velocity with reacting
The time is stayed to determine that heat transferring medium is conduction oil.
(2) head tank 1 has configured reaction solution, (cyclohexanone and hexamethylene mass ratio 4:1, the concentration of cobalt ions are 200ppm,
NPHI concentration is 200ppm).Control reaction flow velocity: 0.25mL/min, control oxygen gas flow rate: 8mL/min beats material respectively
Enter in each straight channel warm-up block, controlling reaction temperature is 110 DEG C, pressure 0.7MPa；Reaction solution is driven into micro- with oxygen
It is reacted in mixer.Reaction time is 40min, after reaction product passes through cooling coil ice-water bath, with high score dephasing
Continuous stream mode outflow reactor.
(3) crystallized dry the adipic acid product of reaction solution.Cyclohexanone total conversion is 20%, and adipic acid selectivity is about
94%。
Embodiment 3
(1) equipment therefor: continuous flow micro passage reaction (ball-type shift-up template channel), hybrid reaction number of modules according to flow velocity with
Reaction time determines that heat transferring medium is conduction oil.
(2) head tank 1 has configured reaction solution, (cyclohexanone and hexamethylene mass ratio 4:1, the concentration of cobalt ions are 200ppm,
NPHI concentration is 200ppm).Control reaction flow velocity: 0.7mL/min, control oxygen gas flow rate: 14mL/min beats material respectively
Enter in each straight channel warm-up block, controlling reaction temperature is 110 DEG C, pressure 0.7MPa；Reaction solution is driven into micro- with oxygen
It is reacted in mixer.Reaction time is 35min, after reaction product passes through cooling coil ice-water bath, with high score dephasing
Continuous stream mode outflow reactor.
(3) crystallized dry the adipic acid product of reaction solution.Cyclohexanone total conversion is 20%, and adipic acid selectivity is about
95%。
Claims (10)
1. it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, it is characterised in that: as steps described below into
Row:
(1) preparation of reaction solution: by cobalt-containing catalyst, co-catalyst nitrogen hydroxyl phthalimide NPHI, cyclohexanone, hexamethylene
Mixing, obtains catalysis oxidation mixed material, and wherein the concentration of cobalt-containing catalyst is 200ppm, cocatalyst concentration 200ppm；
(2) step (1) mixed material is pumped into the microreactor of designed, designed processing, material respectively enters warm-up block, in advance
Heat reaches estimated reaction temperature, and set temperature is controlled by external heat exchanger, and heat transferring medium is conduction oil；Oxygen passes through
Flow is controlled by gas mass flow controller after oxygen pressure reducing valve, filter, preheating section is flowed through and is preheated；After preheated
Material contacts in T-type straight channel with oxygen, and into reaction zone mixing, reaction, mixing temperature is equally carried out by external heat exchanger
Control；After the completion of reaction process, the efflux of reaction zone is adipic acid crude product；
(3) reaction region effluent, which flows through counterbalance valve and enters gas-liquid separator, is separated, and liquid product is collected into product bottle, gas
It mutually empties, the additional condenser jacket of gas-liquid separator；
(4) adipic acid isolates and purifies and catalyst recycling: obtained solution of adipic acid is placed 0 DEG C of cooling 2h, suction filtration, ice
For several times, vacuum filtration is dried to obtain adipic acid crystals to water washing；It is anti-that mother liquor can be used for catalysis next time after revolving water removal concentration
Answer.
2. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: in reaction solution, the mass ratio of cyclohexanone and hexamethylene is 4:1.
3. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: reaction flow velocity is 0.002 ~ 0.01m/s in step (2).
4. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: oxygen gas flow rate is 1 ~ 2m/s in step (2).
5. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: the catalyst of class containing cobalt is cobalt complex, cobalt complex (II), one of cobalt complex (III).
6. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: the microchannel structure in the micro passage reaction reaction zone module is enhancing mixed type channel design；Wherein enhance
Mixed type channel design is spherical structure, spherical band one of baffle arrangement, drops structure, and channel hydraulic diameter is
0.8mm, length 20m.
7. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: step (2) reaction system pressure is 0~0 .7MPa.
8. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: reaction temperature described in step (2) is 90 ~ 130 DEG C.
9. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: the material is 1~60min in the residence time of reaction zone.
10. it is according to claim 1 it is a kind of using micro passage reaction by the method for cyclohexanone synthesizing adipic acid, feature
Be: the module material of micro passage reaction used is special glass, the stainless steel or metal alloy for being coated with corrosion resistant coating；Instead
Answer system can anti-corrosion pressure resistance, voltage endurance capability regards material is different and different, and it is 15~30bar that Maximum safe pressure is reacted in system.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110319731A (en) * | 2019-04-10 | 2019-10-11 | 厦门大学 | A kind of efficient drag reduction reinforcing micro-channel heat exchanger device |
| CN112191217A (en) * | 2020-11-10 | 2021-01-08 | 中国平煤神马能源化工集团有限责任公司 | Novel continuous flow tube type reaction system and process for synthesizing adipic acid |
| CN112209816A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of adipic acid |
| CN112206727A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method |
| CN113150021A (en) * | 2021-04-08 | 2021-07-23 | 上海化工研究院有限公司 | Method for synthesizing boron trifluoride complex by using microchannel reactor |
| CN113402377A (en) * | 2021-07-27 | 2021-09-17 | 中国石油化工股份有限公司 | Production method and production system of terephthalic acid |
| CN113563146A (en) * | 2021-08-13 | 2021-10-29 | 苏州大学 | Catalytic oxidation device and method |
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| CN110319731A (en) * | 2019-04-10 | 2019-10-11 | 厦门大学 | A kind of efficient drag reduction reinforcing micro-channel heat exchanger device |
| CN112209816A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Preparation method of adipic acid |
| CN112206727A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method |
| CN112209816B (en) * | 2019-07-10 | 2022-09-06 | 中国石油化工股份有限公司 | Preparation method of adipic acid |
| CN112206727B (en) * | 2019-07-10 | 2024-01-05 | 中国石油化工股份有限公司 | Microchannel gas-liquid reaction device and method for strengthening gas-liquid reaction and method for preparing adipic acid |
| CN112191217A (en) * | 2020-11-10 | 2021-01-08 | 中国平煤神马能源化工集团有限责任公司 | Novel continuous flow tube type reaction system and process for synthesizing adipic acid |
| CN113150021A (en) * | 2021-04-08 | 2021-07-23 | 上海化工研究院有限公司 | Method for synthesizing boron trifluoride complex by using microchannel reactor |
| CN113402377A (en) * | 2021-07-27 | 2021-09-17 | 中国石油化工股份有限公司 | Production method and production system of terephthalic acid |
| CN113563146A (en) * | 2021-08-13 | 2021-10-29 | 苏州大学 | Catalytic oxidation device and method |
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Application publication date: 20190312 |