CN101613639B - Method for preparing epoxidized oil under ultrasound condition - Google Patents
Method for preparing epoxidized oil under ultrasound condition Download PDFInfo
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- CN101613639B CN101613639B CN200910065464XA CN200910065464A CN101613639B CN 101613639 B CN101613639 B CN 101613639B CN 200910065464X A CN200910065464X A CN 200910065464XA CN 200910065464 A CN200910065464 A CN 200910065464A CN 101613639 B CN101613639 B CN 101613639B
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Abstract
The invention relates to a method for preparing epoxidized oil under the ultrasound condition, comprising the following steps: a. taking and placing a certain amount of plant oil into a reaction container, placing the reaction container into an ultrasound device, stirring while adding the mixed liquid of formic acid (glacial acetic acid or the mixture of formic acid and glacial acetic acid) and catalyst, adjusting temperature of the system, adding hydrogen peroxide drop by drop slowly as well as starting ultrasound, controlling frequency and power of the ultrasound, adjusting the temperature of the system after the adding of hydrogen peroxide is finished, carrying out ultrasound in a certain reaction frequency, certain reaction power and reaction time, lowering the temperature to room temperature after the reaction, removing the lower layer after stewing, and obtaining crude epoxidized plant oil; b. transferring the crude epoxidized plant oil obtained in step a to water washing equipment for washing, and removing the water layer after stewing; and c. transferring the liquid obtained in step b to a vacuum distillation unit (VDU) for vacuum distillation to remove moisture and obtaining the epoxidized plant oil product.
Description
Technical field
The present invention relates to a kind of preparation method of epoxidation grease, specifically relate to a kind of preparation method at epoxidized oil under ultrasound condition.This technology relates to the sonochemistry field, also relates to the epoxy plasticiser preparation field.
Background technology
Softening agent is an important chemical material, is widely used in the processing of plastics, rubber item.Plasticizer phthalic acid ester commonly used at present is a lower-molecular substance, is prone to make goods aging, poisonous; And along with the aggravation of oil crisis, the price of phthalic ester sharply raises.Therefore, adopt renewable resources to prepare eco-friendly softening agent and become the research focus.Epoxidized vegetable oil is a kind of product that makes with refined vegetable oil employing peroxide treatment; Be applicable to various polrvinyl chloride products; Various packaging materials for food, medical product " transfusion bags ", various films, leatheroid, plastic wallpaper and other daily plastics; Also can be used for special ink, liquid composite stabilizing agent etc.Wherein the plastics of the outdoor use of SE, plastic film etc. must use epoxidized vegetable oil to guarantee that goods are nontoxic, transparent, heat-resisting, low temperature resistant, toughness reinforcing, anti-aging etc.Epoxidized vegetable oil is the non-toxic plasticizer of admitting in the world, can be used as the auxiliary agent of wrapping material, toy and the home decoration material of food medicine.But existing epoxidized vegetable oil oxirane value and epoxy transformation efficiency are low, and the epoxidation reaction time is long, can not satisfy the needs of development.
A lot of scholars study the preparation method of epoxy grease; A kind of working method of epoxy palm oil plasticizer is disclosed like one Chinese patent application number 200810026739.4 " a kind of working methods of epoxy palm oil plasticizer "; Under the condition that does not add any solvent; Use plam oil to be raw material, with epoxidizing agent under the katalysis of the vitriol oil and/phosphoric acid, the method for synthesizing epoxy palm oil plasticizer under conditions such as certain temperature, time, proportioning.One Chinese patent application number 200610085270.2 " a kind of preparing methods of epoxy rapeseed oil " disclose rapeseed oil and epoxidizing agent have been carried out epoxidation reaction, generate the method for epoxy rapeseed oil.One Chinese patent application number 90105315.5 " working methods of epoxy grease plasticizer " then disclose under the condition that does not add any solvent; Use Oleum Gossypii semen or VT 18 to be raw material; With ydrogen peroxide 50, Glacial acetic acid min. 99.5 and the vitriol oil of lower concentration, the method for synthesizing epoxy grease plasticizer under conditions such as certain temperature, time, proportioning.But all there is the overlong time of carrying out epoxidation reaction in the disclosed method of the above patent documentation, oxirane value and the low weak point of epoxy transformation efficiency.Therefore, the preparation method who seeks a kind of better epoxy grease is very important.
Summary of the invention
The object of the invention provides a kind of preparation method at epoxidized oil under ultrasound condition to existing weak point in the above-mentioned prior art just.This method mainly utilizes ultransonic cavatition, mechanical effect and ultra mixing effect to quicken the epoxidation reaction of vegetables oil; A kind of quick method for preparing epoxidized vegetable oil of compared with prior art can yet be regarded as; And can obtain oxirane value and all higher epoxidized vegetable oil product of epoxy transformation efficiency through this method, have good economic feasibility.
The object of the invention can be realized through following technique measures:
Preparing method at epoxidized oil under ultrasound condition of the present invention may further comprise the steps:
A, get a certain amount of vegetables oil and place reaction vessel, again reaction vessel is placed ultrasonic device;
B, get 10%～25% formic acid, glacial acetic acid or formic acid that a step gets the vegetables oil volume and the mixture of glacial acetic acid, and 0.75%～1.05% the catalyzer that a step is got the vegetables oil volume mixes, be prepared into mixed solution;
C, the mixed solution that the b step is prepared join in the reaction vessel of a step while stirring;
Open ultrasonic device after the temperature of d, regulation system, begin simultaneously in c step gained system, slowly to drip ydrogen peroxide 50, control ultransonic frequency and power; The temperature of system is 35 ℃～60 ℃ when dripping ydrogen peroxide 50, and the ydrogen peroxide 50 volume of dropping is 30%～70% of the vegetables oil volume of getting, and ultransonic frequency is 28kHz～100kHz, and ultrasonic power is 120w～300w;
After e, ydrogen peroxide 50 dropwise, regulation system temperature to 50 ℃～75 ℃ once more, and be 28kHz～100kHz in ultrasonic frequency, ultrasonic power is 120w～300w, the time is to carry out epoxidation reaction under 15min～75min condition; Reaction is reduced to room temperature after accomplishing, and leaves standstill the back and removes lower floor, obtains the crude epoxidation vegetables oil;
F, the crude epoxidation vegetables oil that the e step is obtained are transferred in the washing equipment, wash, and leave standstill the back and remove water layer;
G, the liquid that the f step is obtained are transferred in the vacuum distillation apparatus, and underpressure distillation removes moisture, obtains the epoxidized vegetable oil product.
Catalyzer described in the present invention is one or more in sulfuric acid, phosphoric acid, Triple Pressed Stearic Acid, oleic acid, Tai-Ace S 150, chlorsulfonic acid, tartrate, the heteropolyacid; Described vegetables oil is one or more mixtures in VT 18, Thistle oil, sunflower oil, oleum lini, Viscotrol C, rapeseed oil, tung oil, plam oil, peanut oil, the synourin oil; The mass percent concentration of described ydrogen peroxide 50 is 30%～80%.
Beneficial effect of the present invention is following:
Because ultrasonic have a tangible cavitation effect, produce during the cavitation bubble collapse moment localized hyperthermia and high pressure can quicken chemical reaction; In the liquid-liquid reactions system; Ultransonic mechanical effect and ultra melange effect can make liquid-liquid phase mix; Form very tiny emulsion, quicken chemical reaction thereby increased alternate contact, these possibly be exactly the reason that ultrasonic energy quickens the epoxidation reaction of vegetables oil.Therefore the present invention has also utilized ultrasonic distinctive these effects just; Utilize ultrasound condition to prepare epoxidized vegetable oil first; Can improve the oxirane value and the epoxy transformation efficiency of epoxidized vegetable oil simultaneously, shorten the time of epoxidation reaction simultaneously, and not use ultrasound condition to compare the epoxidation reaction time to have shortened 70%～90%; Can reduce working cost, thereby make economy of the present invention better.
Embodiment
To combine embodiment to make further detailed description below the present invention:
Embodiment 1:
A, get a certain amount of VT 18 and place reaction vessel, again reaction vessel is placed ultrasonic device;
B, get 15% the formic acid that a step is got the VT 18 volume, and 0.75% the catalyzer (sulfuric acid) that a step is got the VT 18 volume mixes, be prepared into mixed solution;
C, the mixed solution that the b step is prepared join in the reaction system of a step while stirring;
Open Vltrasonic device after the temperature of d, adjusting c step gained system, to wherein slowly dripping ydrogen peroxide 50, control ultransonic frequency and power simultaneously; The temperature of system is 35 ℃ when dripping ydrogen peroxide 50, and the mass percent concentration of the ydrogen peroxide 50 of dropping is 70%, and volume is 35% of a VT 18 volume, and ultransonic frequency is 28kHz, and ultrasonic power is 150w;
After e, ydrogen peroxide 50 dropwised, the regulation system temperature was 50 ℃ once more, and was 28kHz in ultrasonic frequency, and ultrasonic power is 120w, and the time is to carry out epoxidation reaction under the 15min condition; Reaction is reduced to room temperature after accomplishing, and leaves standstill the back and removes lower floor, obtains the crude epoxidation vegetables oil;
F, the crude epoxidation vegetables oil that the e step is obtained are transferred in the washing equipment, wash, and leave standstill the back and remove water layer;
G, the liquid that the f step is obtained are transferred in the vacuum distillation apparatus, and underpressure distillation removes moisture, obtains the epoxidized soybean oil product.Oxirane value is 6.93%, and the epoxy transformation efficiency is 89.53%.
Embodiment 2:
A, get a certain amount of VT 18 and place reaction vessel, again reaction vessel is placed ultrasonic device;
B, get 10% the glacial acetic acid that a step is got the VT 18 volume, and 0.95% the catalyzer (Triple Pressed Stearic Acid) that a step is got the VT 18 volume mixes, be prepared into mixed solution;
C, the mixed solution that the b step is prepared join in the reaction system of a step while stirring;
D, regulate and to open after the temperature of c step gained system ultrasonicly, to wherein slowly dripping ydrogen peroxide 50, control ultransonic frequency and power simultaneously.The temperature of system is 45 ℃ when dripping ydrogen peroxide 50, and the mass percent concentration of the ydrogen peroxide 50 of dropping is 30%, and volume is 70% of a VT 18 volume, and ultransonic frequency is 45kHz, and ultrasonic power is 180w;
After e, ydrogen peroxide 50 dropwised, the regulation system temperature was 70 ℃ once more, and was 100kHz in ultrasonic frequency, and ultrasonic power is 210w, and the time is to carry out epoxidation reaction under the 30min condition; Reaction is reduced to room temperature after accomplishing, and leaves standstill the back and removes lower floor, obtains crude epoxidation soya-bean oil;
F, the crude epoxidation soya-bean oil that the e step is obtained are transferred in the washing equipment, wash, and leave standstill the back and remove water layer;
G, the liquid that the f step is obtained are transferred in the vacuum distillation apparatus, and underpressure distillation removes moisture, obtains the epoxidized soybean oil product.Oxirane value is 7.26, and the epoxy transformation efficiency is 93.80%.
Embodiment 3:
A, get a certain amount of oleum lini and place reaction vessel, again reaction vessel is placed ultrasonic device;
B, get 20% the formic acid that a step is got the oleum lini volume, and 1.05% the catalyzer (phosphoric acid) that a step is got the oleum lini volume mixes, be prepared into mixed solution;
C, the mixed solution that the b step is prepared join in the reaction system of a step while stirring;
D, regulate and to open after the temperature of c step gained system ultrasonicly, to wherein slowly dripping ydrogen peroxide 50, control ultransonic frequency and power simultaneously; The temperature of system is 55 ℃ when dripping ydrogen peroxide 50, and the mass percent concentration of the ydrogen peroxide 50 of dropping is 80%, and volume is 30% of an oleum lini volume, and ultransonic frequency is 45kHz, and ultrasonic power is 300w;
After e, ydrogen peroxide 50 dropwised, the regulation system temperature was 70 ℃ once more, and was 28kHz in ultrasonic frequency, and ultrasonic power is 210w, and the time is to carry out epoxidation reaction under the 65min condition; Reaction is reduced to room temperature after accomplishing, and leaves standstill the back and removes lower floor, obtains the crude epoxidation oleum lini;
F, the crude epoxidation oleum lini that the e step is obtained are transferred in the washing equipment, wash, and leave standstill the back and remove water layer;
G, the liquid that the f step is obtained are transferred in the vacuum distillation apparatus, and underpressure distillation removes moisture, obtains the epoxidized linseed product.Oxirane value is 9.18%, and the epoxy transformation efficiency is 90.13%.
Embodiment 4:
A, get a certain amount of Oleum Gossypii semen and place reaction vessel, again reaction vessel is placed ultrasonic device;
B, get 25% the formic acid that a step is got the Oleum Gossypii semen volume, and 0.80% the catalyzer (phosphoric acid) that a step is got the Oleum Gossypii semen volume mixes, be prepared into mixed solution;
C, the mixed solution that the b step is prepared join in the reaction system of a step while stirring;
D, regulate and to open after the temperature of c step gained system ultrasonicly, to wherein slowly dripping ydrogen peroxide 50, control ultransonic frequency and power simultaneously.The temperature of system is 60 ℃ when dripping ydrogen peroxide 50, and the mass percent concentration of the ydrogen peroxide 50 of dropping is 50%, and volume is 40% of an Oleum Gossypii semen volume, and ultransonic frequency is 28kHz, and ultrasonic power is 240w;
After e, ydrogen peroxide 50 dropwised, the regulation system temperature was 50 ℃ once more, and was 45kHz in ultrasonic frequency, and ultrasonic power is 180w, and the time is to carry out epoxidation reaction under the 75min condition; Reaction is reduced to room temperature after accomplishing, and leaves standstill the back and removes lower floor, obtains the crude epoxidation Oleum Gossypii semen;
F, the crude epoxidation Oleum Gossypii semen that the e step is obtained are transferred in the washing equipment, wash, and leave standstill the back and remove water layer;
G, the liquid that the f step is obtained are transferred in the vacuum distillation apparatus, and underpressure distillation removes moisture, obtains epoxidation Oleum Gossypii semen product.Oxirane value is 5.61%, and the epoxy transformation efficiency is 87.26%.
Claims (4)
1. the preparation method of an epoxidized oil under ultrasound condition is characterized in that said method comprising the steps of:
A, get a certain amount of vegetables oil and place reaction vessel, again reaction vessel is placed ultrasonic device;
B, get 10%～25% formic acid, glacial acetic acid or formic acid that a step gets the vegetables oil volume and the mixture of glacial acetic acid, and 0.75%～1.05% the catalyzer that a step is got the vegetables oil volume mixes, be prepared into mixed solution;
C, the mixed solution that the b step is prepared join in the reaction vessel of a step while stirring;
Open ultrasonic device after the temperature of d, regulation system, begin simultaneously in c step gained system, slowly to drip ydrogen peroxide 50, control ultransonic frequency and power; The temperature of system is 35 ℃～60 ℃ when dripping ydrogen peroxide 50, and the ydrogen peroxide 50 volume of dropping is 30%～70% of the vegetables oil volume of getting, and ultransonic frequency is 28kHz～100kHz, and ultrasonic power is 120w～300w;
After e, ydrogen peroxide 50 dropwise, regulation system temperature to 50 ℃～75 ℃ once more, and be 28kHz～100kHz in ultrasonic frequency, ultrasonic power is 120w～300w, the time is to carry out epoxidation reaction under 15min～75min condition; Reaction is reduced to room temperature after accomplishing, and leaves standstill the back and removes lower floor, obtains the crude epoxidation vegetables oil;
F, the crude epoxidation vegetables oil that the e step is obtained are transferred in the washing equipment, wash, and leave standstill the back and remove water layer;
G, the liquid that the f step is obtained are transferred in the vacuum distillation apparatus, and underpressure distillation removes moisture, obtains the epoxidized vegetable oil product.
2. the preparation method of epoxidized oil under ultrasound condition according to claim 1, it is characterized in that: said catalyzer is selected from more than one in sulfuric acid, phosphoric acid, Triple Pressed Stearic Acid, oleic acid, Tai-Ace S 150, chlorsulfonic acid, tartrate, the heteropolyacid.
3. the preparation method of epoxidized oil under ultrasound condition according to claim 1, it is characterized in that: described vegetables oil is selected from more than one in VT 18, Thistle oil, sunflower oil, oleum lini, Viscotrol C, rapeseed oil, tung oil, plam oil, the peanut oil.
4. the preparation method of epoxidized oil under ultrasound condition according to claim 1, it is characterized in that: the mass percent concentration of described ydrogen peroxide 50 is 30%～80%.
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| CN200910065464XA CN101613639B (en) | 2009-07-20 | 2009-07-20 | Method for preparing epoxidized oil under ultrasound condition |
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| CN101613639B true CN101613639B (en) | 2012-01-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199480B (en) * | 2010-03-24 | 2013-05-01 | 河南工业大学 | Method for preparing lubricating agent by utilizing palm liquid oil |
| CN101942043A (en) * | 2010-09-25 | 2011-01-12 | 中国热带农业科学院农产品加工研究所 | Method for preparing epoxidized natural rubber |
| CN102703224A (en) * | 2012-06-06 | 2012-10-03 | 北京林氏精化新材料有限公司 | Method for preparing substance containing epoxyfatty acid low carbon alcohol ester plasticizer by palm oil |
| CN103382415B (en) * | 2013-01-14 | 2014-09-03 | 江苏卡特新能源有限公司 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
| CN103725348A (en) * | 2013-12-18 | 2014-04-16 | 张家港市林达外加剂厂 | Method for preparing lubricating oil base oil |
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