CN104370873A - Method for preparing caprolactone through cyclohexanone catalyzed oxidation - Google Patents
Method for preparing caprolactone through cyclohexanone catalyzed oxidation Download PDFInfo
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- CN104370873A CN104370873A CN201410675998.5A CN201410675998A CN104370873A CN 104370873 A CN104370873 A CN 104370873A CN 201410675998 A CN201410675998 A CN 201410675998A CN 104370873 A CN104370873 A CN 104370873A
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- caprolactone
- cyclohexanone
- hydrogen peroxide
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- catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
Abstract
The invention discloses a method for preparing caprolactone through cyclohexanone catalyzed oxidation. The method comprises the following steps: mixing aqueous solution of hydrogen peroxide and aqueous solution of formic acid, and adding a catalyst and a stabilizer, thereby preparing a mixed solution; respectively pumping cyclohexanone and the mixed solution into a micro-channel modular reaction device, reacting at the temperature of 45-100 DEG C, preserving the reaction retention time for 2-10 minutes, guiding the reaction products into a separation device, adding aqueous solution of Na2CO3 for washing and regulating the pH value to be neutral, extracting the aqueous solution by using ethyl acetate, merging obtained organic extracting solution, and performing spin evaporation to remove the solvent, thereby obtaining the target product caprolactone. The method disclosed by the invention refers to a continuous process, the preparation process is easy to operate and control, the safety is high, the reaction conditions are mild, the reaction time consumption is short, the product quality is stable, and after-treatment is simple. The method has the characteristics that the generation device is simple, easy in detachment and convenient to carry and move. Convenient adjustment can be performed by simply increasing or decreasing the number of the micro channels.
Description
Technical field
The invention belongs to chemosynthesis and Technology field, be specifically related to a kind of method being prepared caprolactone in micro passage reaction by cyclohexanone by catalytic oxidation.
Background technology
6-caprolactone (ε-CL) is a kind of important organic synthesis intermediate, just synthesizes successfully in laboratory as far back as the thirties in 20th century, but to realize its industrialization be then grow up for producing ε-caprolactam after World War II.Though the technique preparing ε-caprolactam with ε-CL ammonolysis process now already replace by the Beckmann rearrangement method of cyclohexanone-oxime, ε-CL industrially still has important value.
As the new polyester monomer be widely used, 6-caprolactone is mainly used in the polycaprolactone (PCL) synthesizing different purposes, and PCL has unique biocompatibility, biological degradability and good perviousness, is widely used at Material Field.As PCL bio-medical material can be used for suture line and the bone fracture internal fixation material (having the PCL material of shape memory) of operation.As time goes on, polyester material can be degraded at leisure and be absorbed, and can not have injury to wound and human body, can replace traditional operation method, greatly improve the accessibility of operation, can alleviate the misery of patient simultaneously.And polycaprolactone dispersion agent is mainly used in filling plastic system, due to mineral filler as the different polarities between nano-calcium carbonate and polymkeric substance is very large, mineral filler can not well be disperseed in the polymer, polycaprolactone dispersion agent has good dispersion effect, can strengthen the interface binding power of two-phase.
6-caprolactone also can with various resin copolymerization or blending and modifying, to improve product glossiness, the transparency and non-stick property etc., this series products can be used as plastic sheeting for farm use, tackiness agent, the Co ntrolled release body of fertilizer and wrapping material, through the polymethyl methacrylate (PMMA) of caprolactone modification, its performance such as snappiness, photosensitivity obviously improves.
Low relative molecular mass polymkeric substance-the polycaprolactone polyol of what 6-caprolactone can also obtain under the initiation of polyvalent alcohol have multiple terminal hydroxy group.Polycaprolactone polyol can prepare high performance polycaprolactone-type urethane with di-isocyanate reaction.Polycaprolactone polyol has the function regulating in polyurethane elastomer soft section, and the stability to hydrolysis of the urethane prepared with polycaprolactone polyol and low temperature flexibility are far superior to the urethane usually produced for starting material with polyether Glycols or other polyester diol.In addition, other conventional polyurethanes are all better than with its obtained elastomeric high-temperature adaptability, mechanical property and solvent resistance.Be widely used in the industries such as shoemaking, household electrical appliances, automobile, weaving and tire.Polycaprolactone-type urethane also has other excellent properties, as low-temperature flexibility, weather resistant, light stability, high anti-tearing strength and hydrolytic resistance etc.Comparatively extensive in the application in the fields such as high-grade synthetic leather, car paint, sole material, sizing agent.
The synthesis of ε-CL is due to aspects such as raw materials quality, stability and safety, and technical requirements is high, and difficulty is large.At present, only have little several companies production of American and Britain, Deng state, and China mainly relies on import.In recent years, with the continuous expansion of ε-CL purposes, its market requirement also strengthens gradually.Therefore, the research that ε-CL synthesizes, not only technically can fill the domestic gaps, and have tremendous economic prospect.
According to the synthesis technique of ε-CL and the difference of raw material, the synthetic method of ε-CL has: 1,6-hexylene glycol dehydriding, 6 hydroxycaproic acid intramolecular condensation method, hexanodioic acid acidization, oxidizing cyclohexanone method etc.Consider the factors such as raw material, device and reaction conditions, oxidizing cyclohexanone method is the most effective method, is also the method for current suitability for industrialized production ε-CL.
Being mainly contained by the method for pimelinketone through Baeyer-Villger oxidative synthesis caprolactone of current bibliographical information: peroxy acid oxidation style, O
2/ air oxidation process, biological oxidation process and H
2o
2oxidation style, but all there is this lot of deficiency in these synthetic methods: the concentrated and subsequent purification process pre-synthesis phase of chemical peroxy acid oxidation style produces the obstacle that higher, the explosive superoxide of concentration is this technique practical application, there is the problem of the waste of carboxylic acid in the separation difficulty of later product and reaction process, and corrosive equipment, contaminate environment; O
2the activity of/air oxidation process Middle molecule oxygen is lower, makes severe reaction conditions and productive rate is lower, the less effective of the method so far; Find suitable microorganism in biological oxidation process or biological enzyme more difficult, and severe reaction conditions, restive, be unsuitable for suitability for industrialized production; H
2o
2the H of lower concentration in oxidation style
2o
2cheap and easy to get, use safety, cleanliness without any pollution, meets green chemistry instantly.H
2o
2oxidation capacity is not very strong, institute in this way in add a certain amount of catalyzer, to improve catalytic activity.Catalyzer for the method has homogeneous catalyst (mainly containing Lewis acid and organometallics) and heterogeneous catalyst (mainly containing loaded catalyst, metal oxide and solid acid etc.).These catalyzer often exist that reactive behavior is low, preparation process is complicated or the problem such as recycling difficulty.
Therefore, in order to overcome the shortcoming of above-mentioned technique, research micro passage reaction continuous synthesis caprolactone is significant.
Summary of the invention
Technical problem to be solved by this invention be prepare that caprolactone accurately can not control temperature of reaction, selectivity is low, security is not high, epoxidation speed is low, by product is many for oxidizing cyclohexanone, can not continuous prodution and propose a kind of method being prepared 6-caprolactone by cyclohexanone by catalytic oxidation.
For above-mentioned current production caprolactone Problems existing, the present invention proposes corresponding solution, adopt corresponding concrete scheme as follows:
Prepared a method for 6-caprolactone by cyclohexanone by catalytic oxidation, by aqueous hydrogen peroxide solution and aqueous formic acid mixing, then add catalyzer and stablizer, obtained mixing solutions; Again pimelinketone and above-mentioned mixing solutions are pumped in microchannel module reaction unit respectively, react in 45 ~ 100 DEG C, keep reaction time 2 ~ 10min, by reaction product lead-in separation device, add Na
2cO
3solution washing regulates pH weakly acidic pH (pH6.5 ~ 7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.
Wherein, in aqueous hydrogen peroxide solution, the mass percent concentration of solute hydrogen peroxide is 20 ~ 50%, preferably 30%.
Wherein, in aqueous formic acid, the mass percent concentration of solute formic acid is 80 ~ 98%, preferably 98%.
Wherein, described formic acid acetic acid is replaced.
Wherein, described catalyzer is the vitriol oil or strong phosphoric acid, and the concentration of the vitriol oil or strong phosphoric acid is 98wt%, and the add-on of described catalyzer is 1 ~ 8% of hydrogen peroxide quality, preferably 2 ~ 7%.
Wherein, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine; The add-on of described stablizer is 1 ~ 17% of hydrogen peroxide quality, preferably 2 ~ 13%.
Wherein, the mol ratio 1:1 of hydrogen peroxide and formic acid or acetic acid.
Wherein, the reaction mol ratio 1 ~ 3:1 of formic acid or acetic acid and pimelinketone.
Wherein, described microchannel module reaction unit comprises the micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that are linked in sequence successively by pipeline, reaction raw materials passes through accurately and the pump of low pulse (as syringe pump) realizes in input micro mixer and subsequent equipment, thus the serialization that can realize raw material enters into microchannel module reaction unit, and control its residence time simultaneously.Head tank and product collecting device can also connected end to end respectively to realize continuous operation truly according to the actual needs.Described microstucture mixer is slit plate mixerLH25 (Hastelloy C); Microstructure heat exchanger is coaxial heatexchanger (Hastelloy C); Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixedbed meander reactor HC, preferred sandwich reactor HC.
Wherein, described Na
2cO
3in the aqueous solution, solute Na
2cO
3mass percent be 7%.
The reaction equation of present invention process is as follows:
Beneficial effect: the preparation method of caprolactone provided by the present invention is continuous process, preparation technology's easy operation control, and security is high, reaction conditions is gentle, and reaction time is short, constant product quality, and product yield is high.There is production equipment simple, easy to assemble, be easy to carry and the feature of movement.Can be regulated easily by simple increase and decrease microchannel quantity, not exist " scale effect " that similar industrial is produced.
The present invention by micro-structured reactor for the synthesis of caprolactone, existing production Problems existing can be overcome, improve the transformation efficiency of raw material, Reaction time shorten, reduce the content of by product, shortened process, reduce production cost, substantially increase the security of caprolactone production process, improve the quality of product simultaneously.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Following examples the microchannel module reaction unit that is suitable for as shown in Figure 1, comprise the raw material storage tank 1, micro mixer 2, microstructure interchanger 3, tubulose temperature control modules 4, micro-structured reactor 5 and the product-collecting bottle 6 that are linked in sequence successively by pipeline.Reaction raw materials passes through accurately and the pump of low pulse (as syringe pump) realizes in input micro mixer and subsequent equipment, thus the serialization that can realize raw material enters into microchannel module reaction unit, and controls its residence time simultaneously.Connected by the polytetrafluoro kapillary of a segment length between micro-structured reactor 5 and product-collecting bottle 6, it can be made to be immersed in ice-water bath with termination reaction.
Described micro mixer is slit plate mixer LH25 (Hastelloy C); Purchased from Ehrfeld MikrotechnikBTS GmbH, model is 0109-4-0004-F.
Described microstructure heat exchanger is coaxial heatexchanger (Hastelloy C); Purchased from EhrfeldMikrotechnik BTS GmbH, model is 0309-3-0314-F.
Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixedbed meander reactorHC, preferred sandwich reactor HC, purchased from Ehrfeld Mikrotechnik BTS GmbH, model is respectively 0211-2-0314-F; 0213-1-0004-F; 0222-2-2004-F.
Tubulose temperature control modules, purchased from from in Ehrfeld Mikrotechnik BTS GmbH, model is 0501-2-1004-F.
Embodiment 1:
By the hydrogen peroxide of 30wt% and 98wt% acetic acid according to hydrogen peroxide: be that 1:1 mixes with the mol ratio of acetic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 6.31% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 12.23%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.0ml/min, 4.6ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.3:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 93.3% of pimelinketone, caprolactone selectivity 98.3%, the productive rate 91.7% of caprolactone.
Embodiment 2:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% acetic acid according to the mol ratio of hydrogen peroxide and acetic acid, add the dense H of catalyzer wherein
3pO
4with stablizer EDTA, the add-on of catalyzer is 4.32% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 9.68%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.2ml/min, 4.4ml/min, the mol ratio of acetic acid and pimelinketone is made to be 1.6:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 88.3% of pimelinketone, caprolactone selectivity 99.1%, the productive rate 87.5% of caprolactone.
Embodiment 3:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 6.32% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 12.23%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.0ml/min, 4.6ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.3:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 95.3% of pimelinketone, caprolactone selectivity 98.5%, the productive rate 93.9% of caprolactone.
Embodiment 4:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
3pO
4with stablizer EDTA, the add-on of catalyzer is 6.32% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 12.23%.The flow velocity of pimelinketone and said mixture is controlled respectively at 1.8ml/min, 4.8ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.5:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 93.7% of pimelinketone, caprolactone selectivity 98.8%, the productive rate 92.6% of caprolactone.
Embodiment 5:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 6.32% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 12.23%.The flow velocity of pimelinketone and said mixture is controlled respectively at 1.8ml/min, 4.8ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.5:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 96.4% of pimelinketone, caprolactone selectivity 98.7%, the productive rate 95.1% of caprolactone.
Embodiment 6:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 2.0% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 3.5%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.0ml/min, 4.6ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.0:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 90.3% of pimelinketone, caprolactone selectivity 98.9%, the productive rate 89.3% of caprolactone.
Embodiment 7:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 3.0% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 3.5%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.2ml/min, 4.4ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.0:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 91.3% of pimelinketone, caprolactone selectivity 98.7%, the productive rate 90.1% of caprolactone.
Embodiment 8:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 3.0% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 6.0%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.2ml/min, 4.4ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.0:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 90.0% of pimelinketone, caprolactone selectivity 98.1%, the productive rate 88.3% of caprolactone.
Embodiment 9:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer EDTA, the add-on of catalyzer is 3.0% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 7.5%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.2ml/min, 4.4ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.0:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 89.8% of pimelinketone, caprolactone selectivity 98.0%, the productive rate 88.0% of caprolactone.
Embodiment 10:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer urea, the add-on of catalyzer is 3.0% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 3.5%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.2ml/min, 4.4ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.0:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 90.2% of pimelinketone, caprolactone selectivity 98.3%, the productive rate 88.7% of caprolactone.
Embodiment 11:
Be that 1:1 mixes by the hydrogen peroxide of 30wt% and 98wt% formic acid according to the mol ratio of hydrogen peroxide and formic acid, add the dense H of catalyzer wherein
2sO
4with stablizer oxine, the add-on of catalyzer is 3.0% of hydrogen peroxide quality, stablizer add that quality is hydrogen peroxide quality 3.5%.The flow velocity of pimelinketone and said mixture is controlled respectively at 2.2ml/min, 4.4ml/min, the mol ratio of acetic acid and pimelinketone is made to be 2.0:1, through microchannel module reaction unit, react in the micro-structured reactor at 72 DEG C, reaction retention time is 5.6min.Connect the polytetrafluoro kapillary of a segment length after microchannel module reaction unit, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reactant is imported separator, adds 7wt%Na
2cO
3solution washing regulates pH weakly acidic pH (6.5-7.5), re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.The component of gas chromatograph to product is used to analyze, reaction result: the transformation efficiency 89.8% of pimelinketone, caprolactone selectivity 98.1%, the productive rate 88.1% of caprolactone.
Embodiment 12:
With the method for embodiment 11, difference is, adds the dense H of catalyzer wherein
2sO
4with stablizer citric acid, add that quality is hydrogen peroxide quality 1% of catalyzer, it is hydrogen peroxide quality 1% that stablizer adds quality.
Embodiment 13:
With the method for embodiment 11, difference is, adds the dense H of catalyzer wherein
2sO
4with stablizer citric acid, add that quality is hydrogen peroxide quality 8% of catalyzer, it is hydrogen peroxide quality 17% that stablizer adds quality.
Embodiment 14:
With the method for embodiment 11, difference is, adds the dense H of catalyzer wherein
2sO
4with stablizer phosphoric acid.
Embodiment 15:
With the method for embodiment 11, difference is, adds the dense H of catalyzer wherein
2sO
4with stablizer maleic acid.
Embodiment 16:
With the method for embodiment 11, difference is, adds the dense H of catalyzer wherein
2sO
4with stablizer trisodium phosphate.
Embodiment 17:
With the method for embodiment 11, difference is, formic acid and pimelinketone mol ratio be 1:1.
Embodiment 18:
With the method for embodiment 11, difference is, formic acid and pimelinketone mol ratio be 3:1.
Embodiment 19:
With the method for embodiment 11, difference is, reaction time is 2.24min.
Embodiment 20:
With the method for embodiment 11, difference is, reaction time is 9.49min.
Claims (10)
1. prepared a method for caprolactone by cyclohexanone by catalytic oxidation, it is characterized in that, by aqueous hydrogen peroxide solution and aqueous formic acid mixing, then add catalyzer and stablizer, obtained mixing solutions; Again pimelinketone and above-mentioned mixing solutions are pumped in microchannel module reaction unit respectively, react in 45 ~ 100 DEG C, keep reaction time 2 ~ 10min, by reaction product lead-in separation device, add Na
2cO
3solution washing regulates pH weakly acidic pH, re-uses ethyl acetate and extracts the above-mentioned aqueous solution, obtains organic extract liquid and merges, revolve steaming and desolventize, obtain target product caprolactone.
2. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, is characterized in that, described formic acid acetic acid is replaced.
3. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, is characterized in that, described catalyzer is the vitriol oil or strong phosphoric acid; The add-on of described catalyzer is 1 ~ 8% of pimelinketone quality.
4. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, is characterized in that, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine; The add-on of described stablizer is 1 ~ 17% of hydrogen peroxide quality.
5. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, is characterized in that, the mol ratio 1:1 of hydrogen peroxide and formic acid.
6. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 2, is characterized in that, the mol ratio 1:1 of hydrogen peroxide and acetic acid.
7. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, is characterized in that, the mol ratio 1 ~ 3:1 of formic acid and pimelinketone.
8. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 2, is characterized in that, the mol ratio 1 ~ 3:1 of acetic acid and pimelinketone.
9. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, it is characterized in that, described microchannel module reaction unit comprises the micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that are linked in sequence successively by pipeline, and reaction raw materials passes through accurately and the pump of low pulse realizes in input micro mixer and preparation afterwards thereof.
10. the method being prepared caprolactone by cyclohexanone by catalytic oxidation according to claim 1, is characterized in that, described Na
2cO
3in the aqueous solution, solute Na
2cO
3mass percent be 7%.
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| CN106279093A (en) * | 2016-07-22 | 2017-01-04 | 南京工业大学 | A kind of method utilizing micro-reaction device to prepare ε caprolactone |
| CN107118199A (en) * | 2017-06-09 | 2017-09-01 | 中山大学惠州研究院 | A kind of method of purification by liquid extraction ε caprolactones |
| CN107129483A (en) * | 2017-06-09 | 2017-09-05 | 中山大学惠州研究院 | A kind of method of crystallization and purification ε caprolactones |
| WO2017155441A1 (en) * | 2016-03-09 | 2017-09-14 | Perstorp Ab | Production equipment for production of caprolactone |
| WO2017155442A1 (en) * | 2016-03-09 | 2017-09-14 | Perstorp Ab | Production equipment for production of a caprolactone |
| JP2019043922A (en) * | 2017-09-06 | 2019-03-22 | 宇部興産株式会社 | Method for producing composition derived from ester compound using acid |
| CN112239450A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Method for synthesizing epsilon-caprolactone |
| CN114835669A (en) * | 2022-03-23 | 2022-08-02 | 华东理工大学 | Microfluidic synthesis method of high-purity epsilon-caprolactone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017155441A1 (en) * | 2016-03-09 | 2017-09-14 | Perstorp Ab | Production equipment for production of caprolactone |
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| CN107118199A (en) * | 2017-06-09 | 2017-09-01 | 中山大学惠州研究院 | A kind of method of purification by liquid extraction ε caprolactones |
| CN107129483A (en) * | 2017-06-09 | 2017-09-05 | 中山大学惠州研究院 | A kind of method of crystallization and purification ε caprolactones |
| JP2019043922A (en) * | 2017-09-06 | 2019-03-22 | 宇部興産株式会社 | Method for producing composition derived from ester compound using acid |
| CN112239450A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Method for synthesizing epsilon-caprolactone |
| CN112239450B (en) * | 2019-07-16 | 2021-12-28 | 中国石油化工股份有限公司 | Method for synthesizing epsilon-caprolactone |
| CN114835669A (en) * | 2022-03-23 | 2022-08-02 | 华东理工大学 | Microfluidic synthesis method of high-purity epsilon-caprolactone |
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