CN114835669A - Microfluidic synthesis method of high-purity epsilon-caprolactone - Google Patents
Microfluidic synthesis method of high-purity epsilon-caprolactone Download PDFInfo
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000001308 synthesis method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 74
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000007524 organic acids Chemical class 0.000 claims abstract description 34
- 150000002825 nitriles Chemical class 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 51
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
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- 239000002994 raw material Substances 0.000 claims description 18
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- SQFYHAFSDZOUDE-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxybenzaldehyde Chemical compound NCCN.OC1=CC=CC=C1C=O.OC1=CC=CC=C1C=O SQFYHAFSDZOUDE-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
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- 230000001939 inductive effect Effects 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a microfluidic synthesis method of high-purity epsilon-caprolactone, which comprises two-stage reaction in series, wherein the feed of the first-stage reaction comprises hydrogen peroxide and an organic acid solution mixed with a first-stage catalyst, and the reaction generates intermediate peroxy acid; the feeding of the second-stage reaction comprises the discharging of the first-stage reaction and cyclohexanone solution mixed with a second-stage catalyst, and caprolactone is generated by reaction; the first-stage catalyst and the second-stage catalyst both comprise one or a mixture of organic amine, organic nitrile and organic acid, and at least one of the first-stage catalyst and the second-stage catalyst comprises organic amine or organic nitrile. The microfluidic synthesis method provided by the invention improves the conversion rate of cyclohexanone and the selectivity of caprolactone without removing water, maintains the stability of a target product, realizes that the conversion rate of cyclohexanone and the selectivity of caprolactone are more than 99.5%, the purity of caprolactone is more than or equal to 99.5%, the yield is more than or equal to 99%, and the process flow is simple and easy to realize.
Description
Technical Field
The invention belongs to the technical field of epsilon-caprolactone synthesis, and particularly relates to a microfluidic synthesis method of high-purity epsilon-caprolactone.
Background
Poly epsilon-caprolactone (PCL) as polymeric polyester has excellent thermal stability and hydrothermal stability, and can be completely decomposed into CO in soil after 6-12 months as one of sources of degradable plastics 2 And H 2 O, therefore, the high-performance plastic is often applied to packaging materials and medical materials with high added values, is 2-8 times of the price of common plastics, and has great economic value and market application; the monomer epsilon-caprolactone has good biocompatibility, nontoxicity and degradability, and is also used as an active material for regenerating and repairing various tissues and organs in biomedical engineering, so that the purity requirement of the epsilon-caprolactone is very strict. Epsilon-caprolactone is mainly produced abroad by companies such as swedish boston (Perstorp), basf, xylonite, ucc (union carbide) and the like, and at present, domestic companies only realize mass production of the pellin and the Hunan polymeric kernel, but are limited by process technology and capacity, and the domestic market still has short supply and demand for caprolactone and polycaprolactone. Meanwhile, in order to reduce the cost of preparing the degradable plastic monomer, the development of the advanced synthesis technology of caprolactone has great significance.
At present, the synthesis process of epsilon-caprolactone mainly comprises three processes: a peroxy acid oxidation process, a 6-hydroxycaproic ester cyclization process and a catalytic oxidation process. The peroxyacid oxidation method is the most widely applied synthesis process at present, but the synthesis efficiency and the subsequent separation energy consumption are high, so that the development of the domestic epsilon-caprolactone industry is slow. Although various patent technologies (CN108218823A, CN105646433A, CN107163018A, CN102584775A) report methods for improving the purity of caprolactone by continuous refining-separation, the production intensity and equipment investment of caprolactone still cannot form competitive advantages, and especially, progress is slow in improvement of synthesis process. In addition, in the intermediate link of caprolactone synthesis, namely a peroxy acid unit, in order to ensure the conversion rate of cyclohexanone and the selectivity of caprolactone, azeotropic distillation is generally required to remove water in advance, and energy consumption is high, for example, CN1071923A proposes that hydrogen peroxide and carboxylic acid are utilized to synthesize peroxycarboxylic acid under the catalysis of a boric acid catalyst, and then the peroxycarboxylic acid reacts with cyclohexanone to generate caprolactone, but the azeotropic removal of water is always kept in the synthesis process, and meanwhile, an acid catalyst causes hydrolysis of products to a certain degree, and the subsequent separation process is complex; similarly, CN106543132A reports that synthesis of peroxy acid is catalyzed by disulfonic acid polyethylene styrene resin, then azeotropic distillation is used to remove water, and then the peroxy acid is reacted with cyclohexanone to generate caprolactone.
In order to further improve the synthesis efficiency and selectivity of caprolactone, the microfluidic synthesis technology is applied to the continuous synthesis of caprolactone by virtue of the outstanding advantages of enhancing reaction heat and mass transfer, accurately controlling temperature and the like. CN113429376A reports a method for synthesizing caprolactone by a microfluidic technology, in which hydrogen peroxide and cyclohexanone are used under the action of a catalyst bis-salicylaldehyde ethylene diamine Schiff base ferrous complex, the conversion rate of the cyclohexanone is 94% at most, the selectivity of the caprolactone is 93% at most, and meanwhile, a product needs to be quenched at a low temperature in time to prevent the product from being hydrolyzed. CN103539770B reports that in microreactors with different structures, acetic anhydride and hydrogen peroxide are firstly oxidized into peracetic acid, and the peracetic acid and cyclohexanone are used for synthesizing caprolactone after water removal, so that the raw material cost in the synthesis process is high, early-stage water removal and later-stage purification are required, and the energy consumption for separation is high; CN104370873A proposes that hydrogen peroxide and formic acid are synthesized into peroxyformic acid under concentrated sulfuric acid catalyst and stabilizer, then reacted with cyclohexanone in a microchannel reactor, and the outlet crude product is passed through Na 2 CO 3 The solution neutralizes acid and is extracted with ethyl acetate to obtain the target product caprolactone, but the process has high material cost and difficult removal of metal ion and sulfate ion. CN112239450A proposes to use homogeneous catalyst containing sodium tungstate to oxidize cyclohexanone in micro-channel with oxidant to prepare caprolactone, but the introduction of excessive water into the raw material is liable to result in excessive hydrolysis of product and lower product yield. Although the continuous synthesis process of caprolactone is improved by utilizing the microfluidic synthesis technology at present, the energy consumption for removing water from raw materials and the subsequent higher energy consumption for separation still restrict the development of the microfluidic synthesis technology of caprolactone.
Disclosure of Invention
Aiming at the defects of the existing caprolactone synthesis process, the invention provides a catalyst combination type for promoting cyclohexanone conversion and inhibiting caprolactone hydrolysis based on a caprolactone synthesis mechanism and kinetics, discloses a green circulating caprolactone microfluidic synthesis process, and solves the problem of realizing the synthesis of caprolactone with high conversion rate, high selectivity, high stability and low energy consumption under the condition that raw materials are not dehydrated.
The invention provides a microfluidic synthesis method of high-purity epsilon-caprolactone, which comprises a series-connected two-stage reaction, wherein the feed of the first-stage reaction comprises hydrogen peroxide and an organic acid solution mixed with a first-stage catalyst, and the reaction generates intermediate peroxy acid; the feeding of the second-stage reaction comprises the discharging of the first-stage reaction and cyclohexanone solution mixed with a second-stage catalyst, and caprolactone is generated by reaction; the first-stage catalyst and the second-stage catalyst both comprise one or a mixture of organic amine, organic nitrile and organic acid, and at least one of the first-stage catalyst and the second-stage catalyst comprises organic amine or organic nitrile.
The invention is further provided that the reaction temperature of the first stage reaction is 50-90 ℃, preferably 60 ℃, and the reaction residence time is 30-60 minutes, preferably 60 minutes; the reaction temperature of the second stage reaction is 70-90 ℃, preferably 85 ℃, and the reaction residence time is 15-20 minutes, preferably 18 minutes.
The organic amine, the organic nitrile and the organic acid of the first-stage catalyst and the second-stage catalyst are preferably triethylamine, acetonitrile and formic acid respectively.
The invention further provides that the first-stage catalyst comprises organic amine and organic nitrile, and the mass ratio of the organic amine to the organic nitrile is not more than 1:1, preferably (0-0.8): 1; the second stage catalyst comprises an organic acid and an organic nitrile, the mass ratio of the organic acid to the organic nitrile is not less than 4:1, and preferably (4-9): 1.
the invention is further configured that the first stage catalyst is preferably a mixture of triethylamine and acetonitrile.
The invention further provides that the second stage catalyst is preferably a mixture of formic acid and acetonitrile.
The invention is further provided that the proportion of the first-stage catalyst in the raw material organic acid is not more than 25 percent, preferably 10 to 25 percent.
The invention is further provided that the proportion of the second-stage catalyst in the raw material cyclohexanone is not more than 35 percent, preferably 10-35 percent.
The invention further provides that the feeds of the secondary reaction are mixed by a T-shaped or branched microchannel mixer, and the outlet channel size of the microchannel mixer is preferably 0.3-1.5 mm.
The invention is further set that the material at the outlet of the second-stage reactor is enriched and then is cooled, crystallized and separated to obtain high-purity caprolactone, and the temperature range of recrystallization of the target product caprolactone is-5 ℃ to-10 ℃.
The invention is further configured such that the cooling crystallization is controlled in stages, specifically as follows: the cooling rate in the temperature range of 25 ℃ to 10 ℃ is 5-10 ℃/min, and the constant temperature of 10 ℃ is kept for 10-20 minutes; the cooling rate in the temperature range of 10 ℃ to 2 ℃ is 3-5 ℃/min, and the temperature is kept for 5-15 minutes at the constant temperature of 2 ℃; the cooling rate in the temperature range of 2 ℃ to-5 ℃ is 1-2 ℃/min, and the constant temperature is kept for 5-15 minutes at-5 ℃; the temperature reduction rate in the temperature range of-5 ℃ to-10 ℃ is 3-5 ℃/min, and the constant temperature of-10 ℃ is kept for 10-20 minutes.
The invention is further set to obtain solid crystal by continuous low-temperature suction filtration or centrifugation in each segmented temperature control interval from 25 ℃ to-5 ℃, wherein the crystallized organic acid or the solid component of the catalyst is recycled as reaction raw material after being dissolved by the same organic acid as the raw material.
The invention has the following beneficial effects:
according to the microfluidic synthesis method, under the condition of no water removal, the conversion rate and caprolactone selectivity of cyclohexanone are more than 99.5% by using hydrogen peroxide, organic acid and cyclohexanone through a serial microfluidic reactor, the purity of caprolactone is more than or equal to 99.5%, the yield is more than or equal to 99%, and the process flow is simple and easy to realize; the method utilizes cooling crystallization to separate and obtain high-purity caprolactone, and utilizes the cooling crystallization to control the crystallization of organic acid or catalyst in a segmented manner to be recycled as reaction raw materials, so that the method has the characteristics of green recycling of the raw materials and low separation energy consumption, and improves the economic benefit of the caprolactone.
Drawings
FIG. 1 is a flow diagram of a microfluidic synthesis process of caprolactone in series.
Detailed Description
The reaction equations of the synthesis of caprolactone by oxidizing cyclohexanone and the side reaction of caprolactone hydrolysis are shown in formulas (1) and (2), respectively, wherein peroxy acid is peroxyacetic acid as an example:
the inventor has conducted extensive and intensive research, and according to theoretical calculation and kinetic analysis on a caprolactone synthesis mechanism, the strong protonic acid serving as a catalyst promoter has the capability of catalyzing the carbonyl addition of cyclohexanone, but can significantly promote hydrolysis of a target product caprolactone; the hydrogen bond-induced different water cluster forms have different capabilities of inducing hydrolysis of caprolactone, and the strong polar solvent is used as an inhibitor to complex water molecule clusters, so that the hydrogen bond acting force of the water molecules and the stability of the water clusters are improved, and the hydrolysis of the caprolactone is completely avoided. Therefore, the invention regulates and controls the composition proportion and the adding mode of the accelerator and the inhibitor in the catalyst, and optimizes the coupling process conditions, so that the synthesis of the caprolactone is close to full conversion rate and full selectivity, the long-period stability of the target product is ensured, and meanwhile, the organic catalyst is easy to separate and recycle, thereby realizing the green, economic and efficient synthesis of the caprolactone.
Specifically, the invention provides a microfluidic synthesis process of caprolactone, as shown in fig. 1, a microfluidic synthesis system comprises a first-stage mixer, a first-stage reactor, a second-stage mixer and a second-stage reactor which are connected in series in sequence, wherein:
the first-stage mixer and the first-stage reactor are used for first-stage reaction, namely synthesis of intermediate peroxy acid, the first-stage mixer comprises two feeds, one feed is hydrogen peroxide, the other feed is an organic acid solution mixed with a first-stage catalyst, and the feeds are mixed by the first-stage mixer and then introduced into the first-stage reactor for reaction;
the second-stage mixer and the second-stage reactor are used for second-stage reaction, namely synthesis of a target product caprolactone, the second-stage mixer comprises two feeds, one feed is the discharge of the first-stage reactor, the other feed is a cyclohexanone solution mixed with a second-stage catalyst, and the feeds are mixed by the second-stage mixer and then introduced into the second-stage reactor for reaction.
The caprolactone is synthesized by adopting a serial micro-fluidic technology, a mixer and a reactor of an adopted micro-channel are common devices or commercially available devices in the prior art, the first-stage mixer and the second-stage mixer adopt T-shaped or branched micro-channel mixers with shear flow characteristics, and the size of an outlet channel formed by mixing materials in the mixers is 0.3-1.5 mm; the reaction channel materials of the first-stage reactor and the second-stage reactor can be Hastelloy tubes, titanium tubes, stainless steel tubes or polytetrafluoroethylene tubes, and the inner diameter of the reaction channel is 1-3 mm.
Further, the mixer and the reactor in the same stage of the invention can be an integrated structure; or may be independent structures connected in series. Further, the serial microfluidic technology disclosed by the invention is a continuous synthesis process for synthesizing caprolactone; batch or semi-batch synthesis processes may also be employed.
Further, the reaction temperature of the first stage reaction is 50-90 ℃, preferably 60 ℃, and the reaction residence time is 30-60 minutes, preferably 60 minutes; hydrogen peroxide in the feed can be selected from 60-70% mass fraction high-concentration commercial hydrogen peroxide, and the organic acid raw material is one or more of formic acid, acetic acid and propionic acid, preferably acetic acid, and 15-25% mass fraction intermediate peroxy acid is generated; the first-stage catalyst comprises one or a mixture of several of organic amine, organic nitrile and organic acid, wherein the organic amine, the organic nitrile and the organic acid are preferably triethylamine, acetonitrile and formic acid respectively; the first-stage catalyst preferably comprises organic amine and organic nitrile, and the mass ratio of the organic amine to the organic nitrile is not more than 1:1, more preferably triethylamine and acetonitrile; the proportion of the first-stage catalyst in the raw material organic acid is not more than 25 percent by mass percent, and preferably 10 to 25 percent by mass percent.
Further, the reaction temperature of the second-stage reaction is 70-90 ℃, preferably 85 ℃, and the reaction residence time is 15-20 minutes, preferably 18 minutes; the second-stage catalyst in the feeding comprises one or a mixture of more of organic amine, organic nitrile and organic acid, wherein the organic amine, the organic nitrile and the organic acid are preferably triethylamine, acetonitrile and formic acid respectively; the second-stage catalyst preferably comprises an organic acid and an organic nitrile, and the mass ratio of the organic acid to the organic nitrile is not less than 4:1, more preferably formic acid and acetonitrile; the proportion of the second-stage catalyst in the raw material cyclohexanone is not more than 35 percent by mass percent, and preferably 10-35 percent.
Furthermore, in the first-stage catalyst and the second-stage catalyst, organic amine and organic nitrile are used as strong polar solvents containing N, so that the hydrolysis of a target product is inhibited, excessive water generated when organic acid is oxidized by hydrogen peroxide to generate peroxy acid can be complexed, and a certain space complexing effect can be generated by adding a small amount of organic amine, so that the stability of water molecule clusters is further promoted; the organic acid is used as strong protonic acid and has catalytic action on the carbonyl addition of the cyclohexanone; at least one of the first stage catalyst and the second stage catalyst comprises organic amine or organic nitrile for inhibiting the hydrolysis of the target product.
Further, after the material at the outlet of the second-stage reactor is enriched, high-purity caprolactone is obtained by cooling, crystallizing and separating, and the cooling rate and the temperature control of the cooling crystallization are controlled in a segmented manner; specifically, the cooling rate in the temperature range of 25 ℃ to 10 ℃ is 5-10 ℃/min, and the constant temperature of 10 ℃ is kept for 10-20 minutes; the cooling rate in the temperature range of 10 ℃ to 2 ℃ is 3-5 ℃/min, and the temperature is kept for 5-15 minutes at the constant temperature of 2 ℃; the cooling rate in the temperature range of 2 ℃ to-5 ℃ is 1-2 ℃/min, and the constant temperature is kept for 5-15 minutes at-5 ℃; the temperature reduction rate in the temperature range of-5 ℃ to-10 ℃ is 3-5 ℃/min, and the constant temperature of-10 ℃ is kept for 10-20 minutes.
Further, in each segmented temperature control interval of 25 ℃ to-5 ℃, obtaining a solid crystal through continuous low-temperature suction filtration or centrifugation, separating and separating water, organic acid and a catalyst, wherein the crystallized organic acid or the solid component of the catalyst is dissolved by the same organic acid as the raw material and then is recycled as a reaction raw material; in the temperature range of-5 ℃ to-10 ℃, the purity of the target product caprolactone is improved to be more than 99.5 percent through recrystallization, and the yield is more than 99 percent.
The technical solution of the present invention is clearly and completely described below with reference to specific embodiments. It is to be understood that the described embodiments are only a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, fall within the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. All percentages, ratios, proportions, or parts are by weight unless otherwise specified.
The product evaluation indexes related to the invention comprise: conversion, selectivity, stability, purity and yield of cyclohexanone. Wherein, the conversion rate and the selectivity of the cyclohexanone are obtained from the chromatographic analysis result of the outlet product of the microfluidic second-stage reactor; the stability of the caprolactone is the proportion of the caprolactone converted into the byproduct 6-hydroxycaproic acid after the outlet product of the microfluidic second-stage reactor is stood for 30 hours; the purity and yield of caprolactone are measured after separation by cooling crystallization.
Example 1
The two feeds of the first-stage reaction respectively comprise, by mass percent, 70% of hydrogen peroxide and 75% of acetic acid + 25% of a first-stage catalyst, wherein the first-stage catalyst is prepared from the following components in a mass ratio of 1:1, feeding triethylamine and acetonitrile, wherein the feeding flow rates are respectively 0.75 mL/min and 2.0mL/min, the first-stage mixer is a T-shaped mixer, the size of an outlet channel of the first-stage mixer is 1.0 mm, the reaction temperature is 70 ℃, and the retention time is 50 minutes;
the feed for the second-stage reaction comprises, by mass percent, 70% of cyclohexanone and 30% of a second-stage catalyst, wherein the second-stage catalyst is prepared from the following components in a mass ratio of 4:1 formic acid and acetonitrile, feed flow rate 1.5mL/min, reaction temperature 70 ℃, residence time 15 minutes.
And (3) cooling and crystallizing after the product at the outlet of the second-stage reactor is collected for about 2 hours, wherein the cooling procedure is as follows: cooling from 25 deg.C to 10 deg.C at 8 deg.C/min, maintaining at constant temperature for 15 min, and vacuum filtering at constant temperature; cooling to 2 deg.C at 4 deg.C/min, maintaining the temperature for 7 min, and vacuum filtering at constant temperature; cooling to-5 deg.C at 1 deg.C/min, maintaining the temperature for 5 min, and vacuum filtering at constant temperature; cooling to-10 deg.C at 4 deg.C/min, holding the temperature for 15 min, and performing rapid low-temperature centrifugation to obtain the final product.
Sampling and analyzing: 2mL of the product at the outlet of the second-stage reactor is cooled and quenched by glacial acetone, and then the conversion rate and the selectivity of the product are analyzed by chromatography in time; taking 2mL of the second-stage reactor outlet product, standing for 30 hours, and carrying out chromatographic analysis on the stability of the second-stage reactor outlet product; and (5) carrying out chromatographic analysis on the purity of the sample after the secondary recrystallization.
The process has the following effects: the conversion rate of cyclohexanone is 99.9%, the selectivity of caprolactone is 99.7%, the stability of caprolactone is-0.3%, the purity of caprolactone is 99.7% and the yield of caprolactone is 99.5%.
Example 2
The two feeds of the first-stage reaction respectively comprise, by mass percent, 60% of hydrogen peroxide and 90% of propionic acid + 10% of a first-stage catalyst, wherein the first-stage catalyst is acetonitrile, the feed flow rates are respectively 1.5mL/min and 3.0mL/min, the first-stage mixer is selected to be a T-shaped mixer, the size of an outlet channel of the first-stage mixer is 0.3 mm, the reaction temperature is 90 ℃, and the retention time is 30 minutes;
the feed for the second-stage reaction comprises, in mass percent, 65% of cyclohexanone and 35% of a second-stage catalyst, wherein the second-stage catalyst is prepared from the following components in a mass ratio of 9: 1, at a feed flow rate of 1.5mL/min, a reaction temperature of 80 ℃ and a residence time of 18 minutes.
And (3) cooling and crystallizing after the product at the outlet of the second-stage reactor is collected for about 2 hours, wherein the cooling procedure is as follows: cooling from 25 deg.C to 10 deg.C at 10 deg.C/min, maintaining at constant temperature for 20 min, and vacuum filtering at constant temperature; cooling to 2 deg.C at 5 deg.C/min, maintaining the temperature for 10 min, and vacuum filtering at constant temperature; cooling to-5 deg.C at a rate of 2 deg.C/min, maintaining the temperature for 5 min, and vacuum filtering at constant temperature; cooling to-10 deg.C at 5 deg.C/min, holding the temperature for 10 min, and performing rapid low-temperature centrifugation to obtain the final product.
The sampling analysis method is the same as that of the example 1, and the process has the following effects: the conversion rate of cyclohexanone is 99.6%, the selectivity of caprolactone is 99.9%, the stability of caprolactone is-0.2%, the purity of caprolactone is 99.8% and the yield of caprolactone is 99.5%.
Example 3
The two feeds of the first-stage reaction respectively comprise, by mass percent, 70% of hydrogen peroxide and 80% of glacial acetic acid + 20% of a first-stage catalyst, wherein the mass ratio of the first-stage catalyst is 1: 4: 5, feeding flow rates of formic acid, triethylamine and acetonitrile are respectively 0.5mL/min and 1.5mL/min, the first-stage mixer is a T-shaped mixer, the size of an outlet channel of the first-stage mixer is 0.5 mm, the reaction temperature is 50 ℃, and the retention time is 60 minutes;
the feed for the second stage reaction comprises, in mass percent, 90% cyclohexanone + 10% second stage catalyst, wherein the second stage catalyst is formic acid, the feed flow rate is 1.0mL/min, the reaction temperature is 90 ℃, and the residence time is 15 minutes.
And (3) cooling and crystallizing after the product at the outlet of the second-stage reactor is collected for about 2 hours, wherein the cooling procedure is as follows: cooling from 25 deg.C to 10 deg.C at 10 deg.C/min, maintaining at constant temperature for 10 min, and vacuum filtering at constant temperature; cooling to 2 deg.C at 3 deg.C/min, maintaining the temperature for 10 min, and vacuum filtering at constant temperature; cooling to-5 deg.C at a rate of 1 deg.C/min, maintaining the temperature for 10 min, and vacuum filtering at constant temperature; cooling to-10 deg.C at 5 deg.C/min, holding the temperature for 10 min, and performing rapid low-temperature centrifugation to obtain the final product.
The sampling analysis method is the same as that of the example 1, and the process has the following effects: the conversion rate of cyclohexanone is 99.5%, the selectivity of caprolactone is 99.6%, the stability of caprolactone is-0.4%, the purity of caprolactone is 99.8% and the yield of caprolactone is 99.3%.
Example 4
The two feeds of the first-stage reaction respectively comprise, by mass percent, 70% of hydrogen peroxide and 75% of glacial acetic acid + 25% of a first-stage catalyst, wherein the mass ratio of the first-stage catalyst is 2: 3, feeding the ethylenediamine and the acetonitrile at the flow rates of 2.0 and 2.0mL/min respectively, wherein the first-stage mixer is a T-shaped mixer, the size of an outlet channel of the first-stage mixer is 1.0 mm, the reaction temperature is 80 ℃, and the retention time is 50 minutes;
the feed for the second stage reaction comprises, in mass percent, 80% cyclohexanone + 20% second stage catalyst, wherein the second stage catalyst is formic acid, the feed flow rate is 2.0mL/min, the reaction temperature is 90 ℃, and the residence time is 30 minutes.
And (3) cooling and crystallizing after the product at the outlet of the second-stage reactor is collected for about 2 hours, wherein the cooling procedure is as follows: cooling from 25 deg.C to 10 deg.C at 5 deg.C/min, maintaining at constant temperature for 20 min, and vacuum filtering at constant temperature; cooling to 2 deg.C at 4 deg.C/min, maintaining the temperature for 15 min, and vacuum filtering at constant temperature; cooling to-5 deg.C at a rate of 1 deg.C/min, maintaining the temperature for 15 min, and vacuum filtering at constant temperature; cooling to-10 deg.C at 5 deg.C/min, holding the temperature for 15 min, and performing rapid low-temperature centrifugation to obtain the final product.
The sampling analysis method is the same as that of the example 1, and the process has the following effects: the conversion rate of cyclohexanone is 99.8%, the selectivity of caprolactone is 99.7%, the stability of caprolactone is-0.2%, the purity of caprolactone is 99.6% and the yield of caprolactone is 99.5%.
Example 5
The two feeds of the first-stage reaction respectively comprise, by mass percent, 70% of hydrogen peroxide and 90% of glacial acetic acid plus 10% of a first-stage catalyst, wherein the first-stage catalyst is benzonitrile, the feed flow rates are respectively 1.5mL/min and 0.5mL/min, the first-stage mixer is a T-shaped mixer, the size of an outlet channel of the first-stage mixer is 0.5 mm, the reaction temperature is 60 ℃, and the retention time is 40 minutes;
the feed for the second-stage reaction comprises, by mass percent, 70% of cyclohexanone and 30% of a second-stage catalyst, wherein the second-stage catalyst is prepared from the following components in a mass ratio of 5: 1, feed flow rate of 2.0mL/min, reaction temperature of 90 ℃, residence time of 30 minutes.
And (3) cooling and crystallizing after the product at the outlet of the second-stage reactor is collected for about 2 hours, wherein the cooling procedure is as follows: cooling from 25 deg.C to 10 deg.C at 10 deg.C/min, maintaining at constant temperature for 10 min, and vacuum filtering at constant temperature; cooling to 2 deg.C at 5 deg.C/min, maintaining the temperature for 15 min, and vacuum filtering at constant temperature; cooling to-5 deg.C at a rate of 1 deg.C/min, maintaining the temperature for 15 min, and vacuum filtering at constant temperature; cooling to-10 deg.C at 5 deg.C/min, holding the temperature for 10 min, and performing rapid low-temperature centrifugation to obtain the final product.
The sampling analysis method is the same as that of the example 1, and the process has the following effects: the conversion rate of cyclohexanone is 99.9%, the selectivity of caprolactone is 99.7%, the stability of caprolactone is-0.4%, the purity of caprolactone is 99.5% and the yield of caprolactone is 99.3%.
Comparative example 1
This example is a comparative example without the addition of the catalyst according to the invention.
The two feeds of the first-stage reaction respectively comprise 60 mass percent of hydrogen peroxide and glacial acetic acid liquid, the flow rates of the feeds are 0.8 and 2.2mL/min, the first-stage mixer is a T-shaped mixer, the size of an outlet channel of the first-stage mixer is 1.5 mm, the reaction temperature is 60 ℃, and the retention time is 60 minutes;
the feed to the second stage reaction comprised 100% mass fraction cyclohexanone liquid, the feed flow rate was 1mL/min, the reaction temperature was 90 ℃ and the residence time was 18 minutes.
And (3) cooling and crystallizing after the product at the outlet of the second-stage reactor is collected for about 2 hours, wherein the cooling procedure is as follows: cooling from 25 deg.C to 10 deg.C at 5 deg.C/min, maintaining at constant temperature for 10 min, and vacuum filtering at constant temperature; cooling to 2 deg.C at 3 deg.C/min, maintaining the temperature for 5 min, and vacuum filtering at constant temperature; cooling to-5 deg.C at a rate of 1 deg.C/min, maintaining the temperature for 10 min, and vacuum filtering at constant temperature; cooling to-10 deg.C at 3 deg.C/min, holding the temperature for 20 min, and performing rapid low-temperature centrifugation to obtain the final product.
The sampling analysis method is the same as that of the example 1, and the process has the following effects: the conversion rate of cyclohexanone is 88 percent, the selectivity of caprolactone is 90 percent, the stability of caprolactone is-18 percent, the purity of caprolactone is 90 percent and the yield of caprolactone is 75 percent.
Claims (10)
1. A microfluidic synthesis method of high-purity epsilon-caprolactone is characterized by comprising two-stage reactions connected in series, wherein the feed of the first-stage reaction comprises hydrogen peroxide and an organic acid solution mixed with a first-stage catalyst, and the reaction generates intermediate peroxy acid; the feeding of the second-stage reaction comprises the discharging of the first-stage reaction and cyclohexanone solution mixed with a second-stage catalyst, and caprolactone is generated by reaction; the first-stage catalyst and the second-stage catalyst both comprise one or a mixture of organic amine, organic nitrile and organic acid, and at least one of the first-stage catalyst and the second-stage catalyst comprises organic amine or organic nitrile.
2. The microfluidic synthesis method according to claim 1, wherein the first-stage catalyst accounts for no more than 25% of the raw organic acid by mass, and preferably 10-25% of the raw organic acid by mass.
3. The microfluidic synthesis method according to claim 1, wherein the proportion of the second stage catalyst in the raw material cyclohexanone is not more than 35% by mass, preferably 10% -35%.
4. The microfluidic synthesis method according to claim 1, wherein the first-stage catalyst comprises organic amine and organic nitrile, and the mass ratio of the organic amine to the organic nitrile is not more than 1:1, preferably (0-0.8): 1; the second-stage catalyst comprises an organic acid and an organic nitrile, wherein the mass ratio of the organic acid to the organic nitrile is not less than 4:1, preferably (4-9): 1.
5. the microfluidic synthesis method according to claim 4, wherein the first stage catalyst is triethylamine and acetonitrile; the second stage catalyst is formic acid and acetonitrile.
6. The microfluidic synthesis method according to claim 1, wherein the reaction temperature of the first stage reaction is 50-90 ℃, preferably 60 ℃, and the reaction residence time is 30-60 minutes, preferably 60 minutes; the reaction temperature of the second stage reaction is 70-90 ℃, preferably 85 ℃, and the reaction residence time is 15-20 minutes, preferably 18 minutes.
7. The microfluidic synthesis method according to claim 1, wherein the feeds for the secondary reaction are mixed by a T-shaped or branched microchannel mixer, and the outlet channel size of the microchannel mixer is 0.3-1.5 mm.
8. The microfluidic synthesis method according to claim 1, wherein the caprolactone is obtained by cooling, crystallizing and separating the material at the outlet of the second-stage reactor after enrichment, and the recrystallization temperature range of the caprolactone is from-5 ℃ to-10 ℃.
9. The microfluidic synthesis method according to claim 8, wherein the cooling crystallization is performed by a segment control, and the segment control is as follows:
the temperature reduction rate is 5-10 ℃/min between 25 ℃ and 10 ℃, and the constant temperature retention time is 10-20 minutes at 10 ℃;
the temperature reduction rate is 3-5 ℃/min between 10 ℃ and 2 ℃, and the temperature is kept for 5-15 minutes at the constant temperature of 2 ℃;
the temperature reduction rate is 1-2 ℃/min between 2 ℃ and-5 ℃, and the constant temperature is kept for 5-15 minutes at-5 ℃;
the temperature reduction rate is 3-5 ℃/min between the temperature of minus 5 ℃ and minus 10 ℃, and the constant temperature retention time is 10-20 minutes at the temperature of minus 10 ℃.
10. The microfluidic synthesis method according to claim 9, wherein the solid crystals are obtained by continuous low-temperature suction filtration or centrifugation in each temperature-controlled section of 25 ℃ to-5 ℃, and the solid components of the crystallized organic acid or catalyst are dissolved by the same organic acid as the raw material and then recycled as the reaction raw material.
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