CN101613639A - Preparation method of epoxidized oil under ultrasonic condition - Google Patents

Abstract

The present invention relates to a kind of preparation method of epoxidized grease under ultrasonic condition, described preparation method comprises: a. take a certain amount of vegetable oil in reaction container, place reaction container in ultrasonic equipment, add formic acid (ice) while stirring A mixture of acetic acid or formic acid and glacial acetic acid) and catalyst. Adjust the temperature of the system, slowly add hydrogen peroxide dropwise, and turn on the ultrasound at the same time to control the frequency and power of the ultrasound; At room temperature, remove the lower layer after standing still to obtain crude epoxidized vegetable oil; b. transfer the crude epoxidized vegetable oil obtained in step a to a water washing device, wash with water, and remove the water layer after standing; c. The liquid is transferred to a vacuum distillation device, and the moisture is removed by vacuum distillation to obtain an epoxidized vegetable oil product.

Description

Preparation method of epoxidized oil under ultrasonic condition

technical field

The invention relates to a preparation method of epoxidized oil, in particular to a preparation method of epoxidized oil under ultrasonic conditions. The technology relates to the field of sonochemistry, and also relates to the field of epoxy plasticizer preparation.

Background technique

Plasticizer is an important chemical raw material, which is widely used in the processing of plastic and rubber products. Currently commonly used plasticizers, phthalates, are low-molecular substances, which tend to age products and are toxic; and with the intensification of the oil crisis, the price of phthalates has risen sharply. Therefore, the use of renewable resources to prepare environmentally friendly plasticizers has become a research hotspot. Epoxy vegetable oil is a product obtained by treating refined vegetable oil with peroxide. It is suitable for various polyvinyl chloride products, various food packaging materials, medical products "blood transfusion bags", various films, artificial leather, plastic wallpapers And other daily-use plastic products, can also be used in special inks, liquid composite stabilizers, etc. Among them, the plastic products and plastic films used for PVC outdoors must use epoxy vegetable oil to ensure that the products are non-toxic, transparent, heat-resistant, low-temperature resistant, toughened, and anti-aging. Epoxy vegetable oil is a non-toxic plasticizer recognized in the world, and can be used as an auxiliary agent for food and drug packaging materials, toys and home decoration materials. However, the existing epoxy vegetable oil has low epoxy value and epoxy conversion rate, and the epoxidation reaction time is long, which cannot meet the needs of development.

Many scholars have carried out research on the preparation method of epoxy grease, as Chinese patent application number 200810026739.4 " a kind of production method of epoxy palm oil plasticizer " discloses a kind of production method of epoxy palm oil plasticizer, in Under the condition of not adding any solvent, use palm oil as raw material, and under the catalysis of concentrated sulfuric acid and/phosphoric acid with epoxy oxidizing agent, the method for synthesizing epoxy palm oil plasticizer under certain conditions such as temperature, time, proportioning etc. . Chinese Patent Application No. 200610085270.2 "A Preparation Method of Epoxy Rapeseed Oil" discloses a method of epoxidizing rapeseed oil with an epoxidizing agent to generate epoxidized rapeseed oil. Chinese Patent Application No. 90105315.5 "Production Method of Epoxy Grease Plasticizer" discloses that under the condition of not adding any solvent, cottonseed oil or soybean oil is used as raw material, and hydrogen peroxide, glacial acetic acid and concentrated sulfuric acid of low concentration are used in A method for synthesizing epoxy grease plasticizer under certain temperature, time, proportioning and other conditions. However, the methods disclosed in the above-mentioned patent documents all have the disadvantages that the time for the epoxidation reaction is too long, and the epoxy value and the epoxy conversion rate are low. Therefore, it is very necessary to seek a better preparation method of epoxy grease.

Contents of the invention

The purpose of the present invention is just to provide a kind of preparation method of epoxidized grease under the ultrasonic condition in view of the deficiencies existing in the above-mentioned prior art. This method mainly utilizes ultrasonic cavitation, mechanical action and super-mixing action to accelerate the epoxidation reaction of vegetable oil. The epoxy vegetable oil product with high oxygen value and epoxy conversion rate has good economic feasibility.

The purpose of the present invention can be achieved through the following technical measures:

The preparation method of epoxidized grease under ultrasonic condition of the present invention comprises the following steps:

a. Take a certain amount of vegetable oil and place it in a reaction vessel, and then place the reaction vessel in an ultrasonic device;

B, take 10%～25% formic acid, glacial acetic acid or the mixture of formic acid and glacial acetic acid of the volume of vegetable oil taken in step a, and the catalyst of 0.75%～1.05% of the volume of vegetable oil taken in step a, stir and mix, and prepare the mixture liquid;

c, adding the mixed solution prepared in step b into the reaction vessel of step a while stirring;

d. After adjusting the temperature of the system, turn on the ultrasonic equipment, and at the same time start to slowly add hydrogen peroxide to the system obtained in step c, and control the frequency and power of the ultrasonic; 30% to 70% of the volume of the vegetable oil taken, the frequency of ultrasound is 28kHz to 100kHz, and the power of ultrasound is 120w to 300w;

e. After the addition of hydrogen peroxide is completed, adjust the temperature of the system again to 50°C-75°C, and carry out the epoxidation reaction under the conditions of ultrasonic frequency of 28kHz-100kHz, ultrasonic power of 120w-300w, and time of 15min-75min; the reaction is completed Afterwards, be down to room temperature, remove lower layer after leaving standstill, obtain crude epoxidized vegetable oil;

f, transfer the crude epoxidized vegetable oil obtained in step e to water washing equipment, wash with water, and remove the water layer after standing;

g. Transfer the liquid obtained in step f to a vacuum distillation device, and remove moisture by vacuum distillation to obtain an epoxidized vegetable oil product.

The catalyst described in the present invention is one or more of sulfuric acid, phosphoric acid, stearic acid, oleic acid, aluminum sulfate, chlorosulfonic acid, tartaric acid, heteropoly acid; the vegetable oil is soybean oil, safflower oil, sunflower oil, linseed oil, castor oil, rapeseed oil, tung oil, palm oil, peanut oil, dehydrated castor oil, or a mixture of more than one; the mass percent concentration of the hydrogen peroxide is 30% to 80%.

The beneficial effects of the present invention are as follows:

Due to the obvious cavitation effect of ultrasound, the instantaneous local high temperature and high pressure generated when the cavitation bubble collapses can accelerate the chemical reaction; in the liquid-liquid reaction system, the mechanical action and super-mixing effect of ultrasound can make the liquid-liquid phase mix, The formation of very fine emulsions increases the contact between phases and accelerates chemical reactions. These may be the reasons why ultrasound can accelerate the epoxidation of vegetable oils. Therefore the present invention just utilizes these unique effects of ultrasound, and utilizes ultrasonic conditions to prepare epoxy vegetable oil for the first time, which can simultaneously improve the epoxy value and epoxy conversion rate of epoxidized vegetable oil, and shorten the time of epoxidation reaction simultaneously Compared with the condition of not using ultrasonic, the epoxidation reaction time is shortened by 70% to 90%, which can reduce the operating cost, so that the present invention has better economy.

Detailed ways

The present invention will be described in further detail below in conjunction with embodiment:

Example 1:

a. Take a certain amount of soybean oil and place it in a reaction vessel, and place the reaction vessel in an ultrasonic device;

B, get the formic acid of 15% of the volume of soybean oil taken in step a, and the catalyst (sulfuric acid) of 0.75% of the volume of soybean oil taken in step a, stir and mix, and prepare a mixed solution;

c, adding the mixed solution prepared in step b to the reaction system in step a while stirring;

d. After adjusting the temperature of the system obtained in step c, turn on the ultrasonic device, and slowly add hydrogen peroxide dropwise to it, and control the frequency and power of the ultrasonic wave; when adding hydrogen peroxide, the temperature of the system is 35°C, and the concentration of the dropped hydrogen peroxide is 70% by mass. %, the volume is 35% of the soybean oil volume, the ultrasonic frequency is 28kHz, and the ultrasonic power is 150w;

e. After the addition of hydrogen peroxide is completed, adjust the temperature of the system to 50°C again, and carry out the epoxidation reaction under the conditions of ultrasonic frequency of 28kHz, ultrasonic power of 120w, and time of 15min; Remove the lower layer to obtain crude epoxidized vegetable oil;

f, transfer the crude epoxidized vegetable oil obtained in step e to water washing equipment, wash with water, and remove the water layer after standing;

g. Transfer the liquid obtained in step f to a vacuum distillation device, and remove moisture by vacuum distillation to obtain an epoxidized soybean oil product. The epoxy value is 6.93%, and the epoxy conversion rate is 89.53%.

Example 2:

a. Take a certain amount of soybean oil and place it in a reaction vessel, and place the reaction vessel in an ultrasonic device;

B, get the glacial acetic acid of 10% of the volume of soybean oil taken in step a, and the catalyst (stearic acid) of 0.95% of the volume of soybean oil taken in step a, stir and mix, and prepare a mixed solution;

c, adding the mixed solution prepared in step b to the reaction system in step a while stirring;

d. After adjusting the temperature of the system obtained in step c, turn on the ultrasonic wave, and slowly add hydrogen peroxide thereinto, and control the frequency and power of the ultrasonic wave. When hydrogen peroxide is added dropwise, the temperature of the system is 45°C, the mass percent concentration of the hydrogen peroxide added is 30%, the volume is 70% of the volume of soybean oil, the ultrasonic frequency is 45kHz, and the ultrasonic power is 180w;

e. After the addition of hydrogen peroxide is completed, adjust the temperature of the system to 70°C again, and carry out the epoxidation reaction under the conditions of ultrasonic frequency of 100kHz, ultrasonic power of 210w, and time of 30min; Remove the lower layer to obtain crude epoxidized soybean oil;

f, the crude epoxidized soybean oil obtained in step e is transferred to water washing equipment, washed with water, and the water layer is removed after standing;

g. Transfer the liquid obtained in step f to a vacuum distillation device, and remove moisture by vacuum distillation to obtain an epoxidized soybean oil product. The epoxy value is 7.26, and the epoxy conversion rate is 93.80%.

Example 3:

a. Take a certain amount of linseed oil and place it in a reaction vessel, and then place the reaction vessel in an ultrasonic device;

B, get the formic acid of 20% of the volume of linseed oil taken in step a, and the catalyst (phosphoric acid) of 1.05% of the volume of linseed oil taken in step a, stir and mix, and prepare mixed solution;

c, adding the mixed solution prepared in step b to the reaction system in step a while stirring;

d. Turn on the ultrasound after adjusting the temperature of the system obtained in step c, and slowly add hydrogen peroxide dropwise therein to control the frequency and power of the ultrasound; when adding hydrogen peroxide, the temperature of the system is 55°C, and the concentration of the hydrogen peroxide dropped is 80% by mass , the volume is 30% of the volume of linseed oil, the ultrasonic frequency is 45kHz, and the ultrasonic power is 300w;

e. After the addition of hydrogen peroxide is completed, adjust the temperature of the system to 70°C again, and carry out the epoxidation reaction under the conditions of ultrasonic frequency of 28kHz, ultrasonic power of 210w, and time of 65min; The lower layer is removed to obtain crude epoxidized linseed oil;

f, the thick epoxidized linseed oil obtained in e step is transferred to the water washing equipment, washed with water, and the water layer is removed after standing;

g. The liquid obtained in step f is transferred to a vacuum distillation device, and moisture is removed by vacuum distillation to obtain an epoxidized linseed oil product. The epoxy value is 9.18%, and the epoxy conversion rate is 90.13%.

Example 4:

a. Take a certain amount of cottonseed oil and place it in a reaction vessel, and place the reaction vessel in an ultrasonic device;

B, get the formic acid of 25% of the volume of cottonseed oil taken in step a, and the catalyst (phosphoric acid) of 0.80% of the volume of cottonseed oil taken in step a, stir and mix, and prepare a mixed solution;

c, adding the mixed solution prepared in step b to the reaction system in step a while stirring;

d. After adjusting the temperature of the system obtained in step c, turn on the ultrasonic wave, and slowly add hydrogen peroxide thereinto, and control the frequency and power of the ultrasonic wave. When the hydrogen peroxide is added dropwise, the temperature of the system is 60°C, the concentration of the hydrogen peroxide dropped is 50% by mass, the volume is 40% of the volume of cottonseed oil, the ultrasonic frequency is 28kHz, and the ultrasonic power is 240w;

e. After the addition of hydrogen peroxide is completed, adjust the temperature of the system to 50°C again, and carry out the epoxidation reaction under the conditions of ultrasonic frequency of 45kHz, ultrasonic power of 180w, and time of 75min; The lower layer is removed to obtain crude epoxidized cottonseed oil;

f, transfer the thick epoxidized cottonseed oil that step e obtains to washing equipment, wash with water, and remove the water layer after standing;

g. Transfer the liquid obtained in step f to a vacuum distillation device, and remove moisture by vacuum distillation to obtain an epoxidized cottonseed oil product. The epoxy value is 5.61%, and the epoxy conversion rate is 87.26%.

Claims (4)

1, a preparation method of epoxidized grease under ultrasonic conditions, it is characterized in that described method comprises the following steps: a. Take a certain amount of vegetable oil and place it in a reaction vessel, and then place the reaction vessel in an ultrasonic device; B, take 10%～25% formic acid, glacial acetic acid or the mixture of formic acid and glacial acetic acid of the volume of vegetable oil taken in step a, and the catalyst of 0.75%～1.05% of the volume of vegetable oil taken in step a, stir and mix, and prepare the mixture liquid; c, adding the mixed solution prepared in step b into the reaction vessel of step a while stirring; d. After adjusting the temperature of the system, turn on the ultrasonic equipment, and at the same time start to slowly add hydrogen peroxide to the system obtained in step c, and control the frequency and power of the ultrasonic; 30% to 70% of the volume of the vegetable oil taken, the frequency of ultrasound is 28kHz to 100kHz, and the power of ultrasound is 120w to 300w; e. After the addition of hydrogen peroxide is completed, adjust the temperature of the system again to 50°C-75°C, and carry out the epoxidation reaction under the conditions of ultrasonic frequency of 28kHz-100kHz, ultrasonic power of 120w-300w, and time of 15min-75min; the reaction is completed Afterwards, be down to room temperature, remove lower layer after leaving standstill, obtain crude epoxidized vegetable oil; f, transfer the crude epoxidized vegetable oil obtained in step e to water washing equipment, wash with water, and remove the water layer after standing; g. Transfer the liquid obtained in step f to a vacuum distillation device, and remove moisture by vacuum distillation to obtain an epoxidized vegetable oil product. 2. The method for preparing epoxidized grease under ultrasonic conditions according to claim 1, characterized in that: the catalyst is sulfuric acid, phosphoric acid, stearic acid, oleic acid, aluminum sulfate, chlorosulfonic acid, tartaric acid, miscellaneous One or more of the polyacids. 3. The method for preparing epoxidized oil under ultrasonic conditions according to claim 1, wherein said vegetable oil is soybean oil, safflower oil, sunflower oil, linseed oil, castor oil, rapeseed oil, One or more mixtures of tung oil, palm oil, peanut oil, dehydrated castor oil. 4. The method for preparing epoxidized grease under ultrasonic conditions according to claim 1, characterized in that: the mass percent concentration of the hydrogen peroxide is 30%-80%.