CN102993133B - The method of epoxy aliphatic acid methyl ester is prepared by microreactor single stage method - Google Patents
The method of epoxy aliphatic acid methyl ester is prepared by microreactor single stage method Download PDFInfo
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Abstract
The invention discloses a kind of method that microreactor single stage method prepares epoxy aliphatic acid methyl ester, grease, low-carbon alcohol and basic catalyst are injected in the first micro-structured reactor of microchannel module reaction unit, the mol ratio of grease and low-carbon alcohol is 1:11 ~ 17, at 65 ~ 85 DEG C, stop 3 ~ 10min; First micro-structured reactor discharging mixes the second micro-structured reactor injecting microchannel module reaction unit with hydrogen peroxide, organic acid, an acidic catalyst and stablizer, the double key number object mol ratio controlled in organic acid and grease is 11 ~ 17:1,1 ~ 5min is stopped at 65 ~ 95 DEG C, first micro-structured reactor discharging imports in separator, stratification, removes the aqueous solution of lower floor, upper organic phase is washed to pH6.5 ~ 7.5, drying, obtains epoxy aliphatic acid methyl ester.
Description
Technical field
The present invention relates to the preparation method of epoxy aliphatic acid methyl ester, particularly relating to a kind of is the method that raw material single stage method in micro-structured reactor prepares softening agent epoxy aliphatic acid methyl ester with grease, formic acid (or acetic acid), sulfuric acid (or phosphoric acid) and hydrogen peroxide.
Background technology
Engineering plastics are as high in polyvinyl chloride (PVC) exists second-order transition temperature, are difficult to thermoplastic machine-shaping, must add softening agent to increase material plasticity, make it easy processing, give product softness.Adjacent benzene class softening agent is the maximum important additives of a class consumption of plastic working, accounts for 90% of plasticizer consumption, but finds in application process that O-phthalic acids softening agent has persistent genotoxicity.EU chemicals management board expressly forbade using in industries such as electronics, food, daily necessities and toys in October, 2008, how to develop the focus that alternative O-phthalic acids environmental protection non-toxic plasticizer is present global concern.
Epoxy aliphatic acid methyl ester is that one uses nontoxic polyvinyl chloride softening agent widely, its volatility is low, DOP is replaced for replacing epoxy soybean oil and part in polrvinyl chloride product processing completely, its consistency is better than DOP, can significantly improve the physicals of goods and extend the duration of service of goods in the processing of goods.Itself and metal(lic)stabilizer used time, there is good synergisticing stable effect.In addition the production cost of epoxy aliphatic acid methyl ester is low is its outstanding feature, and price is usually less than conventional epoxy soybean oil one class softening agent.Except there is the features such as epoxidized vegetable oil is nontoxic as product when softening agent and stablizer, photo and thermal stability good, consistency good, volatility is low, transport property is little, epoxy aliphatic acid methyl ester also has more excellent oilness, dispersiveness, has very large development prospect in softening agent market, epoxy coating, epoxy resin, polyurethane material, lubricant and adhesive field.China is one of country that vegetable oil resource is the abundantest in the world, and utilize reproducible plant oil based raw material to carry out epoxidation and prepare fine chemical product, petroleum replacing Chemicals have good economic and social benefit.
The method of current production epoxy aliphatic acid methyl ester is generally carried out epoxidation in the presence of a catalyst and is obtained, such as Guidotti (Green Chem., 2003,5, (4), 421-424.) etc. people take tertbutyl peroxide as oxygenant, carries out epoxidation with the fatty acid methyl ester synthesized by sunflower oil (pros-and-cons type Witconol 2301 mixture), and catalyzer is neutral molecule sieve Ti-MCM-41.Reaction result show transformation efficiency and selectivity higher.Patent 1966497A with fatty acid methyl ester, hydrogen peroxide, formic acid is raw material, the vitriol oil is catalyzer, loading in enamel still, being warmed up to 48 DEG C when stirring according to certain proportioning raw materials, stop heating, start to drip the hydrogen peroxide that concentration is 35%, due to exothermic heat of reaction, adopt water coolant temperature adjustment,, to ensure that temperature in the kettle is for 50-70 DEG C, hydrogen peroxide time for adding is 3.5-4.5h, drip off rear insulation 3-4 hour, obtain epoxy aliphatic acid methyl ester product through separation, washing, dehydration, press filtration.After fatty acid methyl ester, organic acid and magnetic catalyst mix by patent CN101139328 in the reactor, stirring is warmed up to 50-70 DEG C, drips a certain amount of 25-50% hydrogen peroxide, drips in two hours, continue insulation 3-6 hour, when the oxirane value of product reaches more than 3.0, stopped reaction, additional certain magnetic field makes catalyzer suction to the both sides of reactor, reaction product is imported separator, stratification, upper oil phase alkali cleaning, drying obtains epoxy aliphatic acid methyl ester product.Ionic liquid is used for, in the epoxidation reaction of fatty acid methyl ester, removing catalyzer after completion of the reaction by patent CN101284812A, directly centrifugally obtains epoxy aliphatic acid methyl ester.Compared with traditional method, speed of response is fast, and technical process is short, and aftertreatment is simple, and corrode low, catalyzer is reusable.Patent 101885710A magnetic nano solid acid is catalyzer, with fatty acid methyl ester, formic acid for raw material, by dripping the mode of hydrogen peroxide, obtain reaction product, this method avoids traditional technology and uses sulfuric acid or organic acid for catalyzer is to the corrosion of equipment, product oxirane value is high, lighter color, has extremely strong industrial application value.Patent CN102060812A adopts solid catalyst (mixed catalyst of sodium pyrosulfate, ferric sulfate, calcium sulfate or sodium pyrosulfate) catalytic epoxidation, under the condition that catalytic activity and sulfuric acid phase are worked as, reaction conditions is gentle, production security is good, and products therefrom oxirane value is high, can reach more than 3.5, and reduce epoxidation temperatures to a certain extent, product color is easy and clean bright, greatly reduces the corrodibility to equipment, and catalyzer can reclaim.Patent CN102161938A take sewer oil as raw material, and first carry out esterification with methyl alcohol, then carry out epoxidation reaction after carrying out molecule rectification and purification, this method is by sewer oil utilization of waste material, saved cost, environmental protection, energy consumption is low, technique is simple, and operational safety, quality product is high.Patent CN102517517 A is with the rubber seed oil after coming unstuck and methyl alcohol carries out pre-esterification and transesterification reaction obtains rubber seed oil fatty acid methyl ester crude product, the rubber seed oil fatty acid methyl ester obtaining the UFAMEs being rich in polyenoid is separated through low temperature crystallization, again through epoxidation reaction, obtain rubber seed oil-based epoxy fatty acid methyl ester, this method abundant raw material is easy to get, with low cost.Patent CN201010245634.5, to mix sewer oil or to walk drink swill wet goods waste vegetable oil for raw material, first carries out alcoholysis, leaves standstill and discharge raw glycerine, then carry out epoxidation reaction, obtain epoxy aliphatic acid methyl ester.The mixture (with the addition of a small amount of catalyzer, stablizer) of fatty acid methyl ester and hydrogen peroxide, first (second) acid is pumped into micro-structured reactor by patent CN201010222889X, goes out epoxy aliphatic acid methyl ester from reacted feed separation.The process of above synthesizing epoxy fatty acid methyl ester is all conventional autoclave rhythmic reaction, in temperature control, all adopts the mode of dropping, prevents temperature from raising very soon, and the oxirane value in later stage is reduced.In the preparation of product, be all first prepare fatty acid methyl ester, then preparing epoxy aliphatic acid methyl ester, can not continuous seepage.The reaction of synthesis peroxy acid is again the reaction of a strong heat release, if temperature is higher the danger of blasting.Therefore, for making product iodine number reduce and can obtain higher oxirane value, temperature of reaction especially keeps temperature strictly to control, can not be too high.At present, domestic had tens manufacturer production epoxy plasticizer, and production technique is based on " single stage method " solvent-free sulphuric acid catalysis.Problems existing is mainly manifested in: 1. the little 2. synthesis technique of output falls behind, and sour water discharge is large, and the inaccurate 3. equipment of temperature control and the low 4. batch operation of automatic control level, can not realize continuous prodution.
Summary of the invention
Technical problem to be solved by this invention is that the fatty acid methyl ester epoxidation that exists for existing technologies can not accurate control temperature, selectivity is low, security is not high, epoxidation speed is low, can not continuous seepage, especially need first to prepare and purification of fatty acid methyl esters, directly can not prepare epoxy aliphatic acid methyl ester by grease single stage method and propose a kind of method that microreactor single stage method prepares epoxy aliphatic acid methyl ester.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of microreactor single stage method prepares the method for epoxy aliphatic acid methyl ester, grease, low-carbon alcohol and basic catalyst are injected in the first micro-structured reactor of microchannel module reaction unit, the mol ratio of grease and low-carbon alcohol is 1:11 ~ 17, at 65 ~ 85 DEG C, stop 3 ~ 10min; First micro-structured reactor discharging mixes the second micro-structured reactor injecting microchannel module reaction unit with hydrogen peroxide, organic acid, an acidic catalyst and stablizer, the double key number object mol ratio controlled in organic acid and grease is 11 ~ 17:1,1 ~ 5min is stopped at 65 ~ 95 DEG C, second micro-structured reactor discharging imports in separator, stratification, removes the aqueous solution of lower floor, upper organic phase is washed to pH6.5 ~ 7.5, drying, obtains epoxy aliphatic acid methyl ester.
Wherein, described microchannel module reaction unit comprises the first raw material storage tank, the second raw material storage tank, the first microstucture mixer, the first heat exchanger, the first tubulose temperature control modules, the first micro-structured reactor, the 3rd raw material storage tank, the second microstucture mixer, the second heat exchanger, the second tubulose temperature control modules, the second micro-structured reactor and product-collecting bottle; Wherein, first raw material storage tank is connected with the first microstucture mixer respectively by pipeline with the second raw material storage tank, first microstucture mixer is connected with the first heat exchanger, the first tubulose temperature control modules, the first micro-structured reactor by pipeline successively, first micro-structured reactor discharge port is connected with the second microstucture mixer respectively by pipeline with the 3rd raw material storage tank, and the second microstucture mixer is connected with the second heat exchanger, the second tubulose temperature control modules, the second micro-structured reactor and product-collecting bottle successively by pipeline; Receiving flask can carry out termination reaction with mixture of ice and water cooling.Reaction raw materials and product pass through accurately and the pump of low pulse (as HPLC pump or syringe pump) realizes input and output.Described microstucture mixer is slit plate mixer LH25 (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 grease is rapeseed oil, soybean oil, peanut oil, Oleum Gossypii semen, Semen Maydis oil, plam oil, Thistle oil, Oleum Cocois, Viscotrol C or sesame oil.
Wherein, described low-carbon alcohol is methyl alcohol or ethanol.
Wherein, the mol ratio of grease and low-carbon alcohol is preferably 1:13 ~ 15.
Wherein, described basic catalyst is potassium hydroxide, sodium hydroxide or sodium methylate, add that quality is oil quality 1 ~ 4% of basic catalyst.
Wherein, described organic acid is formic acid or acetic acid.
Wherein, the double key number object mol ratio in organic acid and grease is preferably 13 ~ 15:1.
Wherein, the mol ratio of organic acid and hydrogen peroxide is 1:1.
Wherein, described an acidic catalyst is the vitriol oil or strong phosphoric acid; The described vitriol oil and strong phosphoric acid concentration are 98wt%; Add that quality is oil quality 2 ~ 5% of an acidic catalyst.
Wherein, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine, preferred EDTA, urea or oxine.
Wherein, stablizer add that quality is oil quality 2 ~ 5%.
Wherein, reaction time of the present invention is the residence time in micro-structured reactor.
The reaction equation of present invention process is as follows:
Beneficial effect:
The preparation method of epoxy aliphatic acid methyl ester provided by the present invention is successive processes, preparation technology's easy operation control, and security is high, and reaction conditions is gentle, and reaction time is short, constant product quality, and epoxidation 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.Especially, this invention, in the process preparing epoxy aliphatic acid methyl ester, does not need refined fat acid methyl esters, directly the reaction product of the first step is carried out epoxidation reaction, thus prepare epoxy aliphatic acid methyl ester.
Simultaneously the present invention introduces novel micro-structured reactor, namely raw material mix in micro-structured reactor, epoxidation, its channel internal diameter is much smaller than the size of conventional reactor, but its specific surface area can reach 10000-50000m
2/ m
3, the advantage brought thus is great heat exchange efficiency and mixing efficiency, can realize the accurate control of temperature of reaction and mix instantaneously with accurate proportioning reaction mass.These are all improve yield, selectivity, security, and the key of quality product.
In view of micro-structured reactor has above advantage, by it for the synthesis of epoxy aliphatic acid methyl ester, existing production Problems existing can be overcome, do not need first to prepare fatty acid methyl ester, Reaction time shorten, shortened process, reduce production cost, reduce the content of by product, greatly improve the security of epoxy aliphatic acid methyl ester production process, improve the quality of product, the oxirane value of product is higher simultaneously.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of microchannel module reaction unit; Wherein, 1 first raw material storage tank, 2 second raw material storage tanks, 3 first microstucture mixer, 4 first heat exchangers, 5 first tubulose temperature control modules, 6 first micro-structured reactors, 7 the 3rd raw material storage tanks, 8 second microstucture mixer, 9 second heat exchangers, 10 second tubulose temperature control modules, 11 second micro-structured reactors, 12 product-collecting bottles.
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.Microchannel module reaction unit comprises the first raw material storage tank 1, second raw material storage tank 2, first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5, first micro-structured reactor 6, the 3rd raw material storage tank 7, second microstucture mixer 8, second heat exchanger 9, second tubulose temperature control modules 10, second micro-structured reactor 11 and product-collecting bottle 12; Wherein, first raw material storage tank 1 is connected with the first microstucture mixer 3 respectively by pipeline with the second raw material storage tank 2, first microstucture mixer 3 is connected with the first heat exchanger 4, first tubulose temperature control modules 5, first micro-structured reactor 6 by pipeline successively, first micro-structured reactor 6 discharge port is connected with the second microstucture mixer 8 respectively by pipeline with the 3rd raw material storage tank 7, and the second microstucture mixer 8 is connected with the second heat exchanger 9, second tubulose temperature control modules 10, second micro-structured reactor 11 and product-collecting bottle 12 successively by pipeline.
Reaction raw materials by accurately and the pump of low pulse (as HPLC pump or syringe pump) realize in input micro mixer and equipment afterwards thereof, thus enable material realize continuing through microchannel module reaction unit to control its residence time simultaneously.Connected by the polytetrafluoro kapillary of a segment length between second micro-structured reactor 11 and product-collecting bottle 12, it can be made to be immersed in ice-water bath with termination reaction.
Described microstucture mixer is slit plate mixer LH25 (Hastelloy C), valve-assistedmixer (Hastelloy C); Purchased from Ehrfeld Mikrotechnik BTS GmbH, model is respectively 0109-4-0004-F; 0111-2-0014-F.
Described microstructure heat exchanger is coaxial heat exchanger (Hastelloy C); Purchased from EhrfeldMikrotechnik BTS GmbH, model is 0309-3-0314-F.
Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactorHC, Hastelloy kapillary; Preferred sandwich reactor HC, purchased from Ehrfeld Mikrotechnik BTSGmbH, model is respectively 0211-2-0314-F; 0213-1-0004-F; 0222-2-2004-F.
Tubulose temperature control modules, purchased from Ehrfeld Mikrotechnik BTS GmbH, model is 0501-2-1004-F.
The hydrogen peroxide concentration that following examples use is mass percent concentration, and catalyzer and stabilizing agent dosage are the per-cent of the quality accounting for grease.
Embodiment 1:
By the methanol solution (wherein sodium methylate accounts for 1wt%(second raw material storage tank 2 of soybean oil) of soybean oil (the first raw material storage tank 1) and sodium methylate according to the mol ratio of soybean oil and methyl alcohol be 1:13 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 75 DEG C, stop 7min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% formic acid, the mixture (the 3rd raw material storage tank 7) of the 98wt% vitriol oil and EDTA, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and formic acid is 1:1, the vitriol oil add that quality is soybean oil quality 3%, add that quality is soybean oil quality 3% of EDTA, and ensure that the double key number object mol ratio in formic acid and soybean oil is 12:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 75 DEG C, stop 3min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 4.85%.
Embodiment 2:
By the methanol solution (wherein sodium methylate accounts for soybean oil 1wt%(second raw material storage tank 2) of soybean oil (the first raw material storage tank 1) and sodium methylate according to the mol ratio of soybean oil and methyl alcohol be 1:15 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 75 DEG C, stop 7min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% formic acid, the mixture (the 3rd raw material storage tank 7) of the 98wt% vitriol oil and urea, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and formic acid is 1:1, the vitriol oil add that quality is soybean oil quality 4%, add that quality is soybean oil quality 3% of urea, and ensure that the double key number object mol ratio in formic acid and soybean oil is 14:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 85 DEG C, stop 4min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 5.0%.
Embodiment 3-8:
Adopt with the identical reaction conditions of embodiment 1, difference is, embodiment 3-4 replaces soybean oil with Oleum Gossypii semen; Embodiment 5-6 replaces soybean oil with peanut oil, replaces formic acid with acetic acid simultaneously; Embodiment 7-8 replaces soybean oil with rapeseed oil; Obtain epoxy aliphatic acid methyl ester product, its oxirane value is in table 1.
Table 1
| Embodiment is numbered | Product oxirane value (%) |
| 3 | 1.58 |
| 4 | 1.32 |
| 5 | 2.53 |
| 6 | 1.98 |
| 7 | 1.5 |
| 8 | 1.2 |
Embodiment 9:
By the methanol solution (wherein sodium methylate accounts for soybean oil 1wt%(second raw material storage tank 2) of soybean oil (the first raw material storage tank 1) and sodium methylate according to the mol ratio of soybean oil and methyl alcohol be 1:13 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 75 DEG C, stop 7min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% acetic acid, the mixture (the 3rd raw material storage tank 7) of 98wt% strong phosphoric acid and EDTA, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and acetic acid is 1:1, strong phosphoric acid add that quality is soybean oil quality 3%, add that quality is soybean oil quality 3% of EDTA, and ensure that the double key number object mol ratio in acetic acid and soybean oil is 14:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 85 DEG C, stop 4min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 4.3%.
Embodiment 10:
By the methanol solution (wherein sodium methylate accounts for 1wt%(second raw material storage tank 2 of soybean oil) of soybean oil (the first raw material storage tank 1) and sodium methylate according to the mol ratio of soybean oil and methyl alcohol be 1:15 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 75 DEG C, stop 7min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% acetic acid, the mixture (the 3rd raw material storage tank 7) of 98wt% strong phosphoric acid and oxine, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and acetic acid is 1:1, strong phosphoric acid add that quality is soybean oil quality 3%, add that quality is soybean oil quality 3% of oxine, and ensure that the double key number object mol ratio in acetic acid and soybean oil is 15:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 85 DEG C, stop 4min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 4.5%.
Embodiment 11-16:
Adopt with the identical reaction conditions of embodiment 10, difference is, soybean oil replaced by embodiment 11-12 Oleum Gossypii semen, replaces acetic acid with formic acid; Soybean oil replaced by embodiment 13-14 peanut oil; Soybean oil replaced by embodiment 15-16 rapeseed oil; The oxirane value of the epoxy aliphatic acid methyl ester obtained is in table 2.
Table 2
| Embodiment is numbered | Product oxirane value |
| 11 | 1.59 |
| 12 | 1.45 |
| 13 | 2.34 |
| 14 | 1.89 |
| 15 | 3.0 |
| 16 | 1.45 |
Embodiment 17:
By the methanol solution (wherein sodium methylate accounts for 1wt%(second raw material storage tank 2 of Oleum Gossypii semen) of Oleum Gossypii semen (the first raw material storage tank 1) and sodium methylate according to the mol ratio of Oleum Gossypii semen and methyl alcohol be 1:13 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 75 DEG C, stop 7min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% formic acid, the mixture (the 3rd raw material storage tank 7) of the 98wt% vitriol oil and urea, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and formic acid is 1:1, the vitriol oil add that quality is Oleum Gossypii semen quality 5%, add that quality is Oleum Gossypii semen quality 4% of urea, and ensure that the double key number object mol ratio in formic acid and Oleum Gossypii semen is 15:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 85 DEG C, stop 4min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 4.85%.
Embodiment 18:
By the methanol solution (wherein sodium hydroxide accounts for 4wt%(second raw material storage tank 2 of Oleum Gossypii semen) of Oleum Gossypii semen (the first raw material storage tank 1) and sodium methylate according to the mol ratio of Oleum Gossypii semen and methyl alcohol be 1:11 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 85 DEG C, stop 10min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% formic acid, the mixture (the 3rd raw material storage tank 7) of the 98wt% vitriol oil and urea, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and formic acid is 1:1, the vitriol oil add that quality is Oleum Gossypii semen quality 5%, add that quality is Oleum Gossypii semen quality 5% of urea, and ensure that the double key number object mol ratio in formic acid and Oleum Gossypii semen is 11:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 95 DEG C, stop 1min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 4.37%.
Embodiment 19:
By the methanol solution (wherein potassium hydroxide accounts for 1wt%(second raw material storage tank 2 of Oleum Gossypii semen) of Oleum Gossypii semen (the first raw material storage tank 1) and sodium methylate according to the mol ratio of Oleum Gossypii semen and methyl alcohol be 1:17 successively by the first microstucture mixer 3, first heat exchanger 4, first tubulose temperature control modules 5 and the first micro-structured reactor 6, in the first micro-structured reactor 6, at normal pressure and 65 DEG C, stop 3min react.Meanwhile, by 30wt% hydrogen peroxide, 98wt% formic acid, the mixture (the 3rd raw material storage tank 7) of the 98wt% vitriol oil and urea, the second microstucture mixer 8 is injected respectively by another constant flow pump and the first micro-structured reactor 6 discharging, wherein, the mol ratio of hydrogen peroxide and formic acid is 1:1, the vitriol oil add that quality is Oleum Gossypii semen quality 2%, add that quality is Oleum Gossypii semen quality 2% of urea, and ensure that the double key number object mol ratio in formic acid and Oleum Gossypii semen is 17:1, material is more successively by the second heat exchanger 9, second tubulose temperature control modules 10 and the second micro-structured reactor 11, in the second micro-structured reactor 11, at normal pressure and 65 DEG C, stop 5min react, second micro-structured reactor 11 discharging enters product-collecting bottle 12 by the polytetrafluoro kapillary of a segment length, polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Product after reaction terminates imports separator, stratification, and except the aqueous solution of sub-cloud, upper organic phase being washed to pH value is 6.5-7.5, and dry, obtain epoxy aliphatic acid methyl ester, oxirane value is 4.46%.
Claims (3)
1. prepare the method for epoxy aliphatic acid methyl ester by microreactor single stage method for one kind, it is characterized in that, grease, low-carbon alcohol and basic catalyst are injected in the first micro-structured reactor of microchannel module reaction unit, the mol ratio of grease and low-carbon alcohol is 1:11 ~ 17, at 65 ~ 85 DEG C, stop 3 ~ 10min; First micro-structured reactor discharging mixes the second micro-structured reactor injecting microchannel module reaction unit with hydrogen peroxide, organic acid, an acidic catalyst and stablizer, the double key number object mol ratio controlled in organic acid and grease is 11 ~ 17:1,1 ~ 5min is stopped at 65 ~ 95 DEG C, second micro-structured reactor discharging imports in separator, stratification, removes the aqueous solution of lower floor, upper organic phase is washed to pH6.5 ~ 7.5, drying, obtains epoxy aliphatic acid methyl ester;
Wherein, described low-carbon alcohol is methyl alcohol;
Wherein, described basic catalyst is potassium hydroxide, sodium hydroxide or sodium methylate, add that quality is oil quality 1 ~ 4% of basic catalyst;
Wherein, described organic acid is formic acid or acetic acid;
Wherein, the mol ratio of organic acid and hydrogen peroxide is 1:1;
Wherein, described an acidic catalyst is the vitriol oil or strong phosphoric acid; Add that quality is oil quality 2 ~ 5% of an acidic catalyst;
Wherein, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine;
Wherein, stablizer add that quality is oil quality 2 ~ 5%.
2. microreactor single stage method according to claim 1 prepares the method for epoxy aliphatic acid methyl ester, it is characterized in that, described microchannel module reaction unit comprises the first raw material storage tank, the second raw material storage tank, the first microstucture mixer, the first heat exchanger, the first tubulose temperature control modules, the first micro-structured reactor, the 3rd raw material storage tank, the second microstucture mixer, the second heat exchanger, the second tubulose temperature control modules, the second micro-structured reactor and product-collecting bottle; Wherein, first raw material storage tank is connected with the first microstucture mixer respectively by pipeline with the second raw material storage tank, first microstucture mixer is connected with the first heat exchanger, the first tubulose temperature control modules, the first micro-structured reactor by pipeline successively, first micro-structured reactor discharge port is connected with the second microstucture mixer respectively by pipeline with the 3rd raw material storage tank, and the second microstucture mixer is connected with the second heat exchanger, the second tubulose temperature control modules, the second micro-structured reactor and product-collecting bottle successively by pipeline; Reaction raw materials and product are by accurately and the pump of low pulse realizes input and output.
3. microreactor single stage method according to claim 1 prepares the method for epoxy aliphatic acid methyl ester, it is characterized in that, described grease is rapeseed oil, soybean oil, peanut oil, Oleum Gossypii semen, Semen Maydis oil, plam oil, Thistle oil, Oleum Cocois, Viscotrol C or sesame oil.
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