CN102876462A - Method for preparing high-quality epoxidized soybean oil - Google Patents

Method for preparing high-quality epoxidized soybean oil Download PDF

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CN102876462A
CN102876462A CN2012103888400A CN201210388840A CN102876462A CN 102876462 A CN102876462 A CN 102876462A CN 2012103888400 A CN2012103888400 A CN 2012103888400A CN 201210388840 A CN201210388840 A CN 201210388840A CN 102876462 A CN102876462 A CN 102876462A
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soybean oil
quality
reaction
epoxy soybean
formic acid
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CN102876462B (en
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郭凯
方正
何伟
欧阳平凯
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Nanjing University
Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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Abstract

The invention discloses a method for preparing high-quality epoxidized soybean oil, comprising the following steps: mixing a hydrogen peroxide water solution and a formic acid water solution; then adding a catalyst and a stabilizing agent; pumping soybean oil and the mixture into a micro-channel modularized reaction device; keeping the reaction stopping time for 2-12 min; reacting at 65-95 DEG C and leading a reaction product into a separator; adding an NaCO3 water solution and statically standing to be layered to remove a water solution of the lower layer; washing an upper-layer organic phase by water; and carrying out rotary evaporation to obtain the high-quality epoxidized soybean oil. The preparation method of the high-quality epoxidized soybean oil disclosed by the invention is a continuous process; and the preparation process is easy to operate and control, the safety is high, the reaction conditions are moderate, the reaction stopping time is short, the quality of a product is stable and the epoxidized recycling rate is high. The method has the characteristics of simple production equipment, easiness for detaching and convenience for carrying and moving. The quantity of micro-channels can be simply increased and decreased to carry out convenient adjustment and an amplification effect which is similar with industrial production does not exist.

Description

A kind of method for preparing high-quality epoxy soybean oil
Technical field
The present invention relates to prepare the method for epoxy soybean oil, belong to chemosynthesis technical field.
Background technology
PVC is as a kind of traditional general-purpose plastics, and it is of many uses, and consumption is very large.Wherein the flexible PVC product can be used for film article, electric wire, outer packaging.But all to add softening agent in the flexible PVC, to improve the performance of PVC.For a long time, the softening agent that uses in the PVC plastics industry mostly is phthalate.In China, the annual production of phthalic ester plasticizer and consumption all account for more than 80% of softening agent total amount, and epoxy soybean oil (ESO) is less than 10%.But owing to depositing the potential carinogenicity of phthalic ester plasticizer, strictly controlled its use abroad.China has also formulated relevant laws and rules, will progressively eliminate phthalate in the use of the aspects such as packaging material for food, medical apparatus and toy for children.And epoxy soybean oil is to use at present more nontoxic non-benzene class environment-friendly type plastic auxiliary agent-softening agent, it has the dual property of softening agent and thermostability concurrently, and nontoxic, safety and environmental protection, meet the RoHS of European Union environmental protection instruction and U.S. FDA foodstuff additive rule fully.
Epoxy soybean oil has a wide range of applications in the industry such as plastics, coating.This softening agent is except being widely used in plastic door-window, tubing, and upholstery material outside electric wire and the film, also can be used as and makes exigent filmstrip and the special softening agent that is used for gasket on the door of refrigerator.Because epoxy soybean oil has the satisfactory stability effect to light, heat, water tolerance and oil-proofness are also good, thereby can give the good physical strength of goods, weathering resistance and electrical property, and volatility is low, transport property is little.It not only has plastification to polyvinyl chloride, and the active chlorine atom on the polyvinyl chloride chain is stablized, can absorb rapidly the hydrogenchloride of degrading out because of light and heat, thereby the continuous decomposition of retardance polyvinyl chloride, play stable effect, and with polyvinyl chloride good consistency is arranged, almost can be used for all polrvinyl chloride products.Compare with other softening agent, another distinguishing feature of epoxy soybean oil is that its low temperature plasticity is very good.Add epoxy soybean oil in polyvinyl chloride (PVC) RESINS, can obviously play plastification under low temperature condition, plasticization effect is better than other common plasticizers.
Now up-to-date studies show that, epoxy soybean oil be good plasticizer for polyvinyl chloride still not, can also be used for other field.It is reported, epoxy soybean oil can be used for the intrinsic toughening modification of resol, thereby significantly improves the toughness of product.Other has report to show, epoxy soybean oil can be used for improving penetration of bitumens and ductility.In addition, about the research of epoxy soybean oil modified epoxy resin paint and adhesive for polyurethane also has report, epoxy soybean oil has played the effect that is highly profitable in the modifying process of epoxypaint and adhesive for polyurethane.Therefore, the range of application of epoxy soybean oil and development space will be day by day wide, and it also can meet protection of the environment fully as environmentfriendly products, to the requirement of human body toxicological harmless effect, are fit to the policy of China's Sustainable development, in China great development potentiality arranged.
The production method of tradition epoxy soybean oil mainly contains solvent method and solventless method.Solvent method uses benzene and substituted benzene as solvent, and sulfuric acid is as catalyzer.Environmental pollution is heavy, and Production Flow Chart is long, and equipment is many, and three wastes treatment capacity is large, and therefore poor product quality is eliminated substantially.Solventless method is substantially all adopted in now epoxy soybean oil production.The solventless method main technique is as the active oxygen carrier with formic acid or acetic acid, the 27-50% hydrogen peroxide is as the body of giving of oxygen, under the effect of catalyzer, carry out epoxidation reaction, in a certain temperature range, the epoxy agent is added drop-wise in the soybean oil, catalyzer commonly used has sulfuric acid, storng-acid cation exchange resin, the catalyzer of synthesizing epoxy soybean oil also has solid acid (such as Tai-Ace S 150, ferric sulfate), heteropolyacid, solid super-strong acid, molecular sieve etc. in addition.React complete by alkali cleaning, washing, dehydration obtains epoxy soybean oil at last.This method is compared with solvent method, and the technological process of production is shorter, and by product is few, pollutes and lacks, and three wastes processing cost is low, more meets the requirement of environmental protection, has therefore substantially replaced now solvent method, becomes the main method of now epoxy soybean oil production.Patent CN101691524A discloses a kind of method of method for preparing epoxidized soybean oil with high epoxy value by fractional step, in soybean oil, add hydrogen peroxide and formic acid in batches or step by step, react under the processing condition of strict control, obtain the epoxy soybean oil of high epoxy value, oxirane value reaches 6.9.But the anti-surface reaction that belongs to of this class epoxidation, the reaction times is longer, and the long reaction times will inevitably cause the by product of epoxy addition under acidic conditions, thereby oxirane value is difficult to reach more than 7.0.And the adding mode of peroxy acid is for add i.e. periodical operation in batches or step by step in the method that this patent adopts.Patent CN101445485A discloses the soybean oil epoxidizing method of a kind of less energy-consumption, few waste water, epoxidation systems is hydrogen peroxide-formic acid, its focus is the aftertreatment of crude product, reach the effect of falling acid and drying products with once washing again by wet distillation, reduce the generation of trade effluent; Patent CN101235021A then discloses the method that a kind of heteropolyacid catalyst prepares epoxy soybean oil, take solid-state heteropolyacid salt QYMO (HO) as catalyzer, do not add carboxylic acid, without protonic acid, solvent-free, the no acidic waste water of epoxidation process produces, but the oxirane value of product not high (oxirane value<6.0); Patent CN10159158A discloses a kind of organic rhenium oxide-urea peroxide catalysis and has prepared the method for epoxy soybean oil, the method take urea peroxide as oxygen source, organic rhenium oxide is the active oxygen carrier, avoided simultaneously the use of carboxylic acid and strong acid, and obtained high epoxy value epoxy soybean oil (oxirane value>7), but used catalyst system cost is higher, the urea peroxide large usage quantity is the 50%-100% of soybean oil quality, and produces a large amount of by product urea after the urea peroxide reaction; Patent CN86104989A discloses a kind of production method of epoxy soybean oil, the method was reacted 7-8 hour with soybean oil, 39% hydrogen peroxide, the vitriol oil, Glacial acetic acid, single stage method sintetics epoxy soybean oil, oxirane value is at 6.0-6.4, and the easy open loop of epoxy group(ing) that this method generates is especially in the epoxidation later stage, because oxidant hydrogen peroxide concentration reduces, epoxidation speed is slower, and the production cycle is long, and temperature of reaction is wayward.The process of above synthesizing epoxy soybean oil all is conventional autoclave rhythmic reaction, aspect temperature control, all adopts the mode that drips, and prevents that temperature from raising very soon, and the oxirane value in reaction later stage is reduced.The reaction of synthetic peroxy acid is again a strong exothermal reaction, if temperature of reaction is too high the danger of blasting is arranged.Therefore for the product iodine number being reduced and can obtaining higher oxirane value, temperature of reaction is control strictly, can not be too high.
At present, the production technique of domestic epoxy soybean oil manufacturer is that the oxirane value of product is between 6-6.5 take " single stage method " solvent-free sulphuric acid catalysis as main.The problem that exists is mainly manifested in: 1. synthesis technique falls behind, and the sour water discharging is large, and temperature control is inaccurate; 2. the side reaction that 4. is difficult to avoid of the low 3. poor stability of equipment and automatic control level causes product quality not high (oxirane value is low).
Summary of the invention
Technical problem to be solved by this invention be for the soybean oil epoxidation can not accurately control temperature of reaction, selectivity is low, security is not high, epoxidation speed is low, can not produce continuously and propose a kind of method for preparing high-quality epoxy soybean oil.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of method for preparing high-quality epoxy soybean oil, aqueous hydrogen peroxide solution and aqueous formic acid are mixed, add again catalyzer and stablizer, again soybean oil and said mixture are pumped in the microchannel module reaction unit, keep reaction time 2 ~ 12min, under 65 ~ 95 ℃, react, reaction product is imported separator, add NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil.
Wherein, described formic acid is replaced with acetic acid.
Wherein, described catalyzer is the vitriol oil or strong phosphoric acid, and the described vitriol oil and strong phosphoric acid concentration are 98wt%; The adding quality of described catalyzer is 1 ~ 15% of soybean oil quality, preferred 2 ~ 15%.
Wherein, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine, preferred EDTA, urea or oxine; The adding quality of described stablizer is 1 ~ 25% of soybean oil quality, preferred 2 ~ 23%.
Wherein, the mol ratio of hydrogen peroxide and formic acid (or acetic acid) is 1:1.
Wherein, double key number purpose mol ratio is 2 ~ 18:1 in formic acid (or acetic acid) and the soybean oil, preferred 6 ~ 18:1.
Wherein, described microchannel module reaction unit comprises micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that is linked in sequence successively by pipeline, reaction raw materials is realized in input micro mixer and the equipment afterwards thereof by the pump (such as HPLC pump or syringe pump) of accurate and low pulsation, thereby is made material can realize controlling simultaneously its residence time by the microchannel module reaction unit continuously.Can also as required, connect respectively end to end raw material storage tank and product-collecting bottle to realize operate continuously.Described micro mixer is slit plate mixer LH25 (Hastelloy C); The microstructure heat exchanger is coaxial heat exchanger (Hastelloy C); Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC, preferred sandwich reactor HC.
Wherein, described NaCO 3Aqueous solution mass percentage concentration is 5%.
Wherein, the preferred 2.24 ~ 11.2min of reaction time.Reaction time is the residence time in the micro-structured reactor.
The reaction equation of technique of the present invention is as follows:
Beneficial effect:
The preparation method of epoxy soybean oil provided by the present invention is successive processes, and preparation technology's easy operation control is safe, and reaction conditions is gentle, and reaction time is short, constant product quality, and the epoxidation yield is high.Have production equipment simple, easy to assemble, the characteristics that are easy to carry and move.Can regulate easily by simple increase and decrease microchannel quantity " scale effect " that does not exist similar industrial to produce.
Simultaneously the present invention introduces novel micro-structured reactor, namely raw material in micro-structured reactor, mix, epoxidation, its passage internal diameter is much smaller than the size of popular response device, but its specific surface area can reach 10000-50000m 2/ m 3, the advantage of bringing thus is great heat exchange efficiency and mixing efficiency, can realize the accurate control of temperature of reaction is reached reaction mass with the moment mixing of accurate proportioning.These all are to improve yield, selectivity, security, and the key of quality product.
In view of micro-structured reactor has above advantage, with it for the synthesis of epoxy soybean oil, can overcome the existing problem that exists of producing, improve the transformation efficiency of vegetables oil, Reaction time shorten, the content of reduction by product, the security that greatly improves the epoxy soybean oil production process, improve simultaneously the quality of product, the oxirane value of product>7.0.
Description of drawings
Fig. 1 is the schematic diagram of microchannel module reaction unit; Wherein, 1 is raw material storage tank; 2 is T-shaped mixing tank; 3 is heat exchanger; 4 is the tubulose temperature control modules; 5 is micro-structured reactor; 6 are product-collecting bottle (cooling off termination reaction with mixture of ice and water).
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
The microchannel module reaction unit that following examples were suitable for comprises the raw material storage tank 1, micro mixer 2, microstructure heat exchanger 3, tubulose temperature control modules 4, micro-structured reactor 5 and the product-collecting bottle 6 that are linked in sequence successively by pipeline as shown in Figure 1.Reaction raw materials is realized in input micro mixer and the equipment afterwards thereof by the pump (such as HPLC pump or syringe pump) of accurate and low pulsation, thereby is made material can realize controlling simultaneously its residence time by the microchannel module reaction unit continuously.Polytetrafluoro kapillary by a segment length between micro-structured reactor 5 and the product-collecting bottle 6 connects, and can make it be immersed in ice-water bath with termination reaction.
Described micro mixer is slit plate mixer LH25 (Hastelloy C); Available from Ehrfeld Mikrotechnik BTS GmbH, model is 0109-4-0004-F.
Described microstructure heat exchanger is coaxial heat exchanger (Hastelloy C); Available from Ehrfeld Mikrotechnik BTS GmbH, model is 0309-3-0314-F.
Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC; Preferred sandwich reactor HC, available from Ehrfeld Mikrotechnik BTS GmbH, model is respectively 0211-2-0314-F; 0213-1-0004-F; 0222-2-2004-F.
The tubulose temperature control modules, available from Ehrfeld Mikrotechnik BTS GmbH, model is 0501-2-1004-F.
Embodiment 1:
Be that 1:1 mixes with the hydrogen peroxide of 30wt% and 98wt% acetic acid according to the mol ratio of hydrogen peroxide and acetic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.5ml/min, 5ml/min, so that double key number purpose mol ratio is 13.5:1 in acetic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.3%.
Embodiment 2:
Be that 1:1 mixes with 30wt% hydrogen peroxide and 98wt% acetic acid according to the mol ratio of hydrogen peroxide and acetic acid, to wherein adding the dense H of catalyzer 3PO 4With stablizer EDTA, the adding quality of catalyzer is 9.0% of soybean oil quality, and it is 13.8% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mol ratio is 10.8:1 in acetic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.07%.
Embodiment 3:
Be that 1:1 mixes with 30wt% hydrogen peroxide and formic acid according to the mol ratio of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.5ml/min, 5.0ml/min, so that double key number purpose mol ratio is 13.5:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.486%.
Embodiment 4:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes according to the mol ratio of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 3PO 4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.4ml/min, 5.1ml/min, so that double key number purpose mol ratio is 15.8:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.312%.
Embodiment 5:
Be that 1:1 mixes with 30wt% hydrogen peroxide and formic acid according to the mol ratio of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.4ml/min, 5.1ml/min, so that double key number purpose mol ratio is 15.8:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.582%.
Embodiment 6:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 2% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.5ml/min, 5ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.126%.
Embodiment 7:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 3% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.2%.
Embodiment 8:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 3% of soybean oil quality, and it is 5% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.1%.
Embodiment 9:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With stablizer EDTA, the adding quality of catalyzer is 3% of soybean oil quality, and it is 6% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.08%.
Embodiment 10:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With the stablizer urea, the adding quality of catalyzer is 3% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.13%.
Embodiment 11:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer 2SO 4With the stablizer oxine, the adding quality of catalyzer is 3% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.0%.
Embodiment 12:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer 2SO 4With the stablizer citric acid, the adding quality of catalyzer is 1% of soybean oil quality, and it is 1% of soybean oil quality that stablizer adds quality.
Embodiment 13:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer 2SO 4With the stablizer Whitfield's ointment, the adding quality of catalyzer is 15% of soybean oil quality, and it is 25% of soybean oil quality that stablizer adds quality.
Embodiment 14:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer 2SO 4With stablizer phosphoric acid.
Embodiment 15:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer 2SO 4With the stablizer maleic acid.
Embodiment 16:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer 2SO 4With the stablizer trisodium phosphate.
Embodiment 17:
With the method for embodiment 11, difference is that double key number purpose mol ratio is 2:1 in formic acid and the soybean oil.
Embodiment 18:
With the method for embodiment 11, difference is that double key number purpose mol ratio is 18:1 in formic acid and the soybean oil.
Embodiment 19:
With the method for embodiment 11, difference is that reaction time is 2.24min.
Embodiment 20:
With the method for embodiment 11, difference is that reaction time is 11.2min.

Claims (10)

1. method for preparing high-quality epoxy soybean oil, it is characterized in that, aqueous hydrogen peroxide solution and aqueous formic acid are mixed, add again catalyzer and stablizer, again soybean oil and said mixture are pumped in the microchannel module reaction unit, keep reaction time 2 ~ 12min, under 65 ~ 95 ℃, react, reaction product is imported separator, add NaCO 3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil.
2. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described formic acid is replaced with acetic acid.
3. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described catalyzer is the vitriol oil or strong phosphoric acid; The adding quality of described catalyzer is 1 ~ 15% of soybean oil quality.
4. the method for the high-quality epoxy soybean oil of preparation 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 adding quality of described stablizer is 1 ~ 25% of soybean oil quality.
5. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, the mol ratio of hydrogen peroxide and formic acid is 1:1.
6. the method for the high-quality epoxy soybean oil of preparation according to claim 2 is characterized in that, the mol ratio of hydrogen peroxide and acetic acid is 1:1.
7. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, double key number purpose mol ratio is 2 ~ 18:1 in formic acid and the soybean oil.
8. the method for the high-quality epoxy soybean oil of preparation according to claim 2 is characterized in that, double key number purpose mol ratio is 2 ~ 18:1 in acetic acid and the soybean oil.
9. the method for the high-quality epoxy soybean oil of preparation according to claim 1, it is characterized in that, described microchannel module reaction unit comprises micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that is linked in sequence successively by pipeline, and reaction raw materials is realized in input micro mixer and the equipment afterwards thereof by the pump of accurate and low pulsation.
10. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described NaCO 3Aqueous solution mass percentage concentration is 5%.
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CN103266018A (en) * 2013-06-17 2013-08-28 许昌学院 Preparation method of epoxidized soybean oil
CN103266018B (en) * 2013-06-17 2015-08-19 许昌学院 A kind of preparation method of epoxidised soybean oil
CN103274930A (en) * 2013-06-20 2013-09-04 南京工业大学 Vegetable oil polyol preparation method by using continuous method
CN103981025A (en) * 2014-06-06 2014-08-13 张家港宇新羊毛工业有限公司 Wool grease mixing device
CN103981025B (en) * 2014-06-06 2016-05-25 张家港宇新羊毛工业有限公司 A kind of yolk mixing arrangement
CN104262297A (en) * 2014-09-01 2015-01-07 南京工业大学 Method for preparing high-quality epoxy vegetable oil by using microreactor
CN104262297B (en) * 2014-09-01 2016-03-16 南京工业大学 A kind of method adopting microreactor to prepare high-quality epoxidized vegetable oil
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CN104560407B (en) * 2015-01-06 2017-08-25 中山联成化学工业有限公司 A kind of preparation method of epoxy plasticiser
CN105801520A (en) * 2016-04-07 2016-07-27 南京工业大学 Method for preparing epoxy fatty acid ester by using microreactor
US9546143B2 (en) * 2016-04-07 2017-01-17 Nanjing Tech University Method for preparing high-quality epoxidized fatty acid ester with micro-reaction device
CN108914689A (en) * 2017-10-11 2018-11-30 天津中天精科科技有限公司 A kind of paper for daily use paper pulp release agent and its preparation process
CN109574842A (en) * 2018-12-21 2019-04-05 南京工业大学 A kind of novel plant oil polyalcohol and the preparation method and application thereof
CN109608333A (en) * 2018-12-21 2019-04-12 南京工业大学 A kind of high-quality vegetable oil polyol and the preparation method and application thereof
CN109608333B (en) * 2018-12-21 2020-07-24 南京工业大学 Vegetable oil polyalcohol and preparation method and application thereof

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