CN109970688B - Method for preparing epoxy plasticizer from waste grease and product - Google Patents
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- C07—ORGANIC CHEMISTRY
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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Abstract
The invention discloses a method for preparing an epoxy plasticizer by using waste cooking oil and a product, which mainly comprise the following steps: firstly, freezing and separating the waste oil, removing saturated oil components which do not contribute to epoxy, then carrying out esterification reaction on a catalyst of solid acid and alcohol to reduce the acid value, and finally adding formic acid and hydrogen peroxide to carry out epoxidation reaction. The epoxy plasticizer prepared by the method has the advantages of good plasticizing effect, high flash point, small thermal weight loss, difficult oil production of PVC products and the like. The method has simple preparation process and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of a fine organic chemical product plasticizer, in particular to a preparation method of an epoxy plasticizer prepared from waste grease and a product.
Background
The oil consumption is high in large-scale countries, and a large amount of oil is consumed every year, particularly vegetable oil such as soybean oil, peanut oil, palm oil, rapeseed oil and the like is a main soybean oil import country. But at the same time, more waste catering grease is generated. According to statistics, three to four million waste cooking oil, hogwash oil and swill-cooked dirty oil are generated every year in China, if the waste cooking oil, the hogwash oil and the swill-cooked dirty oil cannot be recycled, the waste cooking oil can flow back to a dining table again, and the health of people is threatened.
The nontoxic environment-friendly plasticizer is mainly epoxy, and comprises epoxy vegetable oil, epoxy fatty acid ester and the like. The epoxy vegetable oil is prepared by using vegetable oil such as soybean oil, rapeseed oil, corn oil, cottonseed oil and the like as raw materials and obtaining the nontoxic epoxy vegetable oil plasticizer through epoxidation, and the cost is higher.
At present, the document reports that the waste oil is adopted to prepare the epoxy fatty acid methyl ester plasticizer: CN 200710022603-method for producing epoxy plasticizer by using waste oil adopts waste oil as raw material, and the method comprises pretreating to obtain glyceride, performing ester exchange with methanol under the catalysis of alkali to obtain fatty acid methyl ester, and finally performing epoxidation reaction to obtain epoxy fatty acid methyl ester plasticizer. CN 201310751024-method for preparing biological plasticizer epoxy fatty acid methyl ester from kitchen waste oil & fat, namely, removing impurities from kitchen waste oil & fat, performing molecular distillation to obtain low-acid-value treated oil & fat, performing transesterification reaction on the treated oil and methanol with sodium hydroxide as a catalyst to obtain fatty acid methyl ester, and finally performing epoxidation reaction to obtain epoxy fatty acid methyl ester plasticizer. In the methods, glyceride is converted into fatty acid methyl ester through ester exchange, a large amount of methanol is consumed, and glycerin is discarded, so that the cost is high, and the post-treatment process is complicated.
Disclosure of Invention
The invention provides a preparation method of a biomass epoxy plasticizer capable of realizing comprehensive utilization of waste grease.
The invention also provides an epoxy plasticizer prepared from the waste oil, and the epoxy plasticizer has the advantages of high flash point, small thermal weight loss, good biocompatibility and difficult oil production.
A method of preparing an epoxy plasticizer from waste grease comprising:
gradually adding alcohol into the waste oil in the presence of an esterification catalyst, optionally carrying out esterification reaction under a vacuum condition, and stopping the esterification reaction until the acid value of a system is less than a set value to obtain a mixture of fatty acid ester and glyceride with a low condensation point; and (3) carrying out epoxidation reaction on the mixture of the fatty acid ester with the low condensation point and the glyceride to obtain the final epoxy plasticizer.
In the present invention, the alcohol is selected from one or more of methanol, butanol, isobutanol, octanol, and isooctanol. Further preferably, the alcohol is butanol, isobutanol, octanol, isooctanol. The adding amount is 5 to 40 percent of the waste grease; preferably, in the invention, the esterification reaction temperature is 100-250 ℃.
When the alcohol is methanol, the esterification reaction can be carried out under normal pressure; the excess methanol evaporates rapidly at the above reaction temperature. When the alcohol is one or more of butanol, isobutanol, octanol and isooctanol, the esterification reaction is carried out under the vacuum condition of-0.09 to-0.10 MPa. The reaction time is 2-8 hours. Preferably, the reaction temperature is 125 ℃ to 220 ℃.
In the esterification process, when high-boiling-point alcohol is selected as a raw material, vacuum conditions are introduced, so that water generated in the esterification process can be timely vacuumized, and the esterification reaction is ensured to be smoothly and quickly carried out. More importantly, during the traditional preparation of the plasticizer, the glycerate and the methanol are generally subjected to transesterification reaction and converted into fatty acid methyl ester, the generated glycerol needs to be removed from the system, and the part of the alcohol is wasted; in order to meet the requirements of ester exchange, the methanol is required to be greatly excessive and is required to be carried out under reflux conditions, so that the consumption of the methanol is greatly increased, and the energy consumption is also greatly increased. The method of the invention carries out esterification reaction in a vacuum state, and simultaneously removes water and timely extracts excessive unreacted alcohol, so that the added alcohol directly reacts with acid in the waste grease, and does not further carry out ester exchange reaction with glycerate in the system, thereby further simplifying the reaction process and improving the reaction efficiency from the reaction mechanism. When methanol is used as the alcohol solvent, because the esterification temperature is higher, the residual methanol can be evaporated from the reaction system after the methanol is reacted with acid in the system, and the methanol does not carry out further transesterification reaction with glycerate in the system. The pumped high boiling point alcohol or the recovered methanol can be used for reuse or used as other raw materials. The waste oil with low condensation point can be directly purchased and has the condensation point of-5-10 ℃, and can also be obtained by simply treating the initial material of the waste oil.
Preferably, the waste oil or fat is low freezing point waste oil or fat obtained by the following method: and (3) removing water from the waste oil, freezing and separating to remove solidified high-condensation-point oil, thereby obtaining the low-condensation-point waste oil.
Preferably, the method for preparing the epoxy plasticizer from the waste grease comprises the following steps:
(1) removing water and other non-oily impurities from the waste oil, freezing and separating: heating and stirring, melting all the grease, then cooling and freezing, and removing the frozen saturated high-condensation-point grease to obtain waste grease with a low condensation point;
(2) adding an esterification catalyst into the waste oil with low condensation point, continuously dropwise adding alcohol, carrying out esterification reaction under a vacuum condition, and vacuumizing generated water and most unreacted alcohol until the acid value is less than a set value, and stopping the reaction;
(3) removing residual alcohol in vacuum after esterification, and removing an esterification catalyst;
(4) adding formic acid and hydrogen peroxide to perform an epoxy reaction, and performing post-treatment to obtain a final product epoxy plasticizer;
in the above reaction step, when methanol is used as the alcohol, the vacuum condition can be removed, that is, the esterification reaction is carried out under normal pressure.
The alcohol raw material is generally added from a feed inlet at the bottom of an esterification kettle, so that the alcohol raw material is firstly contacted and esterified with acid in a reaction solution.
As an optional step, the waste oil with low freezing point after freezing fractionation is decolorized, or an intermediate product after esterification is decolorized. That is, if the color of the raw material is darker, the oil after freezing fractionation can be decolorized, or the obtained intermediate product after octylation can be decolorized. When the color meets the product requirements, the decolorization step can be omitted.
Of course, when the waste oil initial material directly meets the low freezing point requirement (i.e. does not contain high freezing point oil), the waste oil initial material can be directly used in the esterification reaction after water removal or other non-oily impurities removal. When the initial waste oil and fat material does not contain water or other non-oily impurities and simultaneously meets the requirement of low condensation point, the initial waste oil and fat material can be directly used as a raw material to carry out the esterification reaction, namely the step (1) can be omitted.
In the invention, the waste grease is selected from one or more of waste cooking oil, swill oil and swill oil, or may be one or more of waste cooking oil, swill oil and swill oil which are subjected to primary treatment (such as conventional impurity removal treatment, drying treatment or other conventional pretreatment processes). The waste oil and fat can be one of waste oil and fat generated by corn oil, soybean oil, peanut oil, palm oil, rapeseed oil, tea oil, blend oil with various compositions, two or more of waste oil and fat generated by soybean oil, peanut oil, palm oil and rapeseed oil, and a plurality of mixtures of the waste oil and fat generated by the two or more of the two or more.
The common waste oil contains a large amount of glycerate, wherein the acid chain part is mostly long-chain fatty acid, and the content of C16-C18 is the maximum. Preferably, the waste oil-and-fat initial material or the low-freezing-point waste oil-and-fat of the present invention is an unsaturated waste oil-and-fat mainly containing a C16-C18 chain. The acid value of the waste oil is 3 mgKOH/g-120 mgKOH/g. More preferably, the acid value of the waste oil and fat after freeze fractionation is 3mgKOH/g to 70 mgKOH/g; more preferably, it is from 10mgKOH/g to 50 mgKOH/g.
In the mixture of the low-freezing-point fatty acid ester and the glyceride prepared by the method, the glyceride with the low freezing point is mainly derived from the original waste oil, and the low-freezing-point fatty acid ester is mainly obtained by reacting free fatty acid in the original waste oil with the alcohol A.
In the invention, during freezing fractionation, heating and stirring (for example, heating to 40-60 ℃ and the temperature is determined according to the performance of actual waste oil), melting all oil, then cooling and freezing, and freezing out partially saturated oil such as animal oil; and (3) the frozen saturated high-condensation-point grease is used for other purposes, and the waste grease with low condensation point is used for testing the acid value and then is subjected to the next step. Preferably, in the present invention, the freezing and fractionation temperature is-10 ℃ to 20 ℃.
In the present invention, the set value is 0.2 to 1mgKOH/g, and more preferably 0.5mgKOH/g, in the esterification reaction process. Namely, the esterification reaction is carried out under the vacuum condition, and the esterification reaction is stopped after the acid value is less than 0.5 mgKOH/g.
In the step (3), residual alcohol is removed in vacuum after esterification, and the catalyst is esterified by removing filtration, sedimentation and the like.
Preferably, the esterification catalyst is a solid catalyst. The solid catalyst is further preferably a solid acid catalyst with an activation temperature of 100-250 ℃ and capable of promoting esterification reaction. The products sold in the market can be selected according to actual requirements during actual selection; the solid acid catalyst is further preferably a metal catalyst. The metal catalyst includes, but is not limited to, metal sulfate (such as ferrous sulfate), bisulfate (sodium bisulfate), sulfonate, metal oxide (such as stannous oxide), metal inorganic acid salt, metal organic acid ester, supported catalyst (such as supported alumina solid acid catalyst, cerium sulfate solid acid catalyst, activated carbon supported p-toluenesulfonic acid, etc.).
For methanol, the esterification temperature is generally 100-120 ℃; the catalyst is preferably sodium bisulfate, ferrous sulfate, and p-toluenesulfonic acid supported by activated carbon.
For butanol, isobutanol, octanol, and isooctanol, it is preferable that the esterification reaction is carried out at 125 ℃ to 220 ℃ under vacuum. At the reaction temperature, stannous oxide, a supported alumina solid acid catalyst, a cerium sulfate solid acid catalyst, and the like are preferred catalysts.
In the invention, the weight ratio of the waste oil and fat to the alcohol and esterification catalyst is as follows: waste grease: alcohol: catalyst 1: (0.02-0.4) and (0.001-0.05).
In the invention, the mass ratio of the esterified waste grease to formic acid and hydrogen peroxide is as follows: and (3) esterification of waste oil: formic acid: hydrogen peroxide 1: (0.01-0.10): (0.2 to 0.5); the reaction is terminated at a temperature of 50-90 ℃ and an iodine value of less than 6%, preferably less than 3%. Preferably, the addition amount of the formic acid and the hydrogen peroxide is as follows: and (3) esterification of waste oil: formic acid: hydrogen peroxide 1: 0.03-0.07: 0.2-0.35; preferably, the reaction temperature is 60-80 ℃; preferably, the reaction is stopped when the iodine value is less than 3%;
in the invention, the method for decoloring the intermediate product after esterification comprises the following steps: decoloring by adopting activated clay, activated carbon or a decoloring agent;
in the invention, the post-treatment after the epoxy reaction refers to the steps of alkali washing, water washing, vacuum dehydration, steam stripping, filter pressing and the like;
preferably, the method for preparing the environment-friendly plasticizer from the waste oil comprises the following steps:
1) removing non-oily impurities (including water and other visible non-oily impurities) from the waste oil and fat, and performing freeze fractionation: heating and stirring to melt all the grease, then cooling and freezing, and freezing out the partially saturated grease such as animal oil; the frozen saturated high-condensation-point grease is used for other purposes, and the acid value of the waste grease with low condensation point is tested;
2) adding clay into the oil product with dark color for decolorization;
3) adding a certain amount of alcohol into the frozen waste oil, reacting for 1-8 hours at the temperature of 100-250 ℃ under the catalysis of solid acid, and carrying out esterification reaction;
4) for esterified oils, the catalyst is removed by filtration or centrifugation;
5) transferring to an epoxy reaction kettle, adding a certain amount of formic acid and hydrogen peroxide, heating to 55-65 ℃, carrying out an epoxy reaction, and stopping the reaction when the iodine value is reduced to below 6%;
6) and standing the epoxy initial product, separating acid and water, washing with alkali, washing with water, and performing vacuum dehydration and drying to obtain the final product.
In the step 2), for the oil product with a dark color, adding clay for decoloring under a vacuum condition, wherein the adding amount of the clay is 1-5% of the oil, and the temperature is 80-120 ℃.
The epoxy plasticizer is prepared by the method for preparing the epoxy plasticizer from the waste oil and fat in any technical scheme.
The plasticizer obtained by the method has good compatibility and high plasticizing efficiency, and the method has the advantages of easily controlled process flow, high utilization rate of waste grease and the like.
The invention also provides an environment-friendly biomass plasticizer which is good in compatibility and difficult to produce oil.
The invention provides a method for preparing an epoxy plasticizer from waste cooking oil. Has wide raw material source, reduces environmental pollution and harm to human health. The final product as plasticizer has excellent performance, regeneration property and good biodegradability, and can replace petroleum product plasticizer.
The final product obtained by the invention is a mixture of epoxy fatty acid glyceride and epoxy fatty acid ester.
The invention has the following effective effects: the epoxy plasticizer prepared from the waste oil is prepared into epoxy fatty acid methyl ester at present, although the plasticizing effect is good, the flash point is low, the thermal weight loss is large, and the VOC emission can be increased in the use process of a product with higher processing temperature. The epoxy plasticizer prepared by the invention has the advantages of high plasticizing efficiency, high flash point, small thermal weight loss and better lubricity. In addition, because the waste oil is subjected to freezing and fractionation, saturated components are removed, and plastic products made of the waste oil are difficult to produce oil. The method has the advantages of simple process and controllable industrial production, and is suitable for industrial production.
The epoxy plasticizer prepared by the method has the advantages of good plasticizing effect, high flash point, small thermal weight loss, difficult oil production of PVC products and the like. The method has simple preparation process and is suitable for industrial production.
The unreacted alcohol extracted in vacuum and the water obtained by the reaction are directly subjected to water-alcohol separation by the existing process, and the alcohol obtained after the separation can be directly used, so that the using amount of the solvent is further reduced, and the preparation cost of the plasticizer product is reduced.
Detailed Description
The present invention is further illustrated by the following specific examples. The examples allow the researchers to better understand the present invention, but do not limit the present invention in any form.
Example 1
Adding 200g of high-acid-value catering waste oil with an acid value of 20mgKOH/g after freezing fractionation (the freezing fractionation temperature is 20 ℃) into a reaction bottle, adding 1.0g of stannous oxide (an avastin reagent) serving as a solid acid catalyst, stirring, heating to 170 ℃, vacuumizing, keeping the internal pressure of the system at-0.1 MPa, gradually introducing 18g of isooctanol by adopting a dropwise adding mode, so that fatty acid and isooctanol existing in the waste oil are subjected to esterification reaction to generate octyl fatty acid, the glycerate in the system basically keeps unchanged, reacting for 2 hours, reducing the acid value to 0.45mgKOH/g, stopping the reaction, continuously vacuumizing to remove residual octanol, filtering the solid acid catalyst after cooling to obtain 208.5g of an esterification product, putting the esterification product into an epoxy reaction bottle, heating to 60 ℃, then dropwise adding a mixture of 50g and 7.5g of formic acid into hydrogen peroxide to perform epoxy reaction, sampling to test the iodine value, stopping the reaction when the iodine value is 4.2%, standing to separate acid water, adding a small amount of liquid alkali to neutralize, then washing with hot water until the solution is neutral, and dehydrating and filtering the obtained initial product to obtain the final epoxy plasticizer product containing epoxy fatty acid octyl ester and epoxy glyceride.
Example 2
Adding 200g of high-acid-value catering waste oil with an acid value of 65mgKOH/g after freezing fractionation (the freezing fractionation temperature is 20 ℃) into a reaction bottle, adding 1.8g of aqueous cerium sulfate solid acid catalyst (an avadin reagent), stirring, heating to 130 ℃, vacuumizing, keeping the internal pressure of the system at-0.1 MPa, gradually introducing 38g of butanol in a dropwise adding mode, leading fatty acid and butanol in the waste oil to carry out esterification reaction to generate fatty acid butyl ester, reacting for 3 hours, reducing the acid value to 0.35mgKOH/g, stopping the reaction, continuously vacuumizing to remove residual butanol, filtering the solid acid catalyst after cooling to obtain 216.4g of esterified product, putting the esterified product into an epoxy reaction bottle, heating to 60 ℃, then dropwise adding a mixture of 56g of hydrogen peroxide and 9g of formic acid, carrying out epoxy reaction, sampling to test the iodine value, wherein the iodine value is 2.5%, stopping the reaction, standing to remove acid water, adding a small amount of liquid caustic soda for neutralization, then washing with hot water until the obtained initial product is neutral, and dehydrating and filtering the obtained initial product to obtain the final epoxy plasticizer product containing epoxy fatty acid butyl ester and epoxy glyceride.
Example 3
Adding 200g of high-acid-value low-condensation (solidification temperature is 5-10 ℃) ordering drink waste oil with an acid value of 15mgKOH/g into a reaction bottle, adding 1.2g of a supported alumina solid acid catalyst, kojikuquan biotechnology limited, stirring, heating to 130 ℃, vacuumizing, keeping the internal pressure of the system at-0.09 MPa, gradually introducing 15g of isobutanol by adopting a dropwise manner to react fatty acid and isobutanol to generate fatty acid isobutyl ester, reacting for 1 hour, reducing the acid value to 0.4mgKOH/g, stopping the reaction, continuously vacuumizing to remove residual isobutanol, filtering the solid acid catalyst after cooling to obtain 203.19g of an esterified product, filling the esterified product into an epoxy reaction bottle, heating to 60 ℃, dropwise adding a mixture of 42g and 6.5g of formic acid to perform an epoxy reaction, sampling and testing an iodine value, keeping the iodine value at 2.5%, stopping the reaction, standing and removing acid water, adding a small amount of liquid caustic soda for neutralization, then washing with hot water until the mixture is neutral, dehydrating and filtering the obtained initial product to obtain a final epoxy plasticizer product containing epoxy fatty acid isobutyl ester and epoxy glyceride.
However, the treatment by using the prior waste oil technology is to remove 200g of free fatty acid of the waste oil in the above example 1, reduce the acid value to below 1.5mgKOH/g to obtain about 186g of glyceride with low acid value, then place the glyceride in methanol (the mass ratio of the waste oil to the methanol is 1:0.2), perform reflux reaction (60 ℃ -80 ℃) for 2.5h, distill the glyceride to obtain about 178.9g of fatty acid methyl ester, and then perform the same epoxidation reaction to obtain a comparative sample of epoxy fatty acid methyl ester.
By adopting the method, the alcohol and the water solution which are pumped out in vacuum can directly adopt the existing process, for example, a rectification process can be adopted to realize the separation of the alcohol and the water, the recovered alcohol can be directly recycled to the preparation of the plasticizer, of course, the alcohol and the water solution can also be directly recycled to other processes, or the alcohol obtained by separation is applied to other processes.
And (3) performance detection:
the performance of the plasticizer flash point obtained in example 1-3 was tested according to GBT + 1671-:
| plasticizer | Flash point, DEG C | Is heated to reduce weight% |
| Example 1 | 216 | 0.06％ |
| Example 2 | 206 | 0.12％ |
| Example 3 | 208 | 0.10％ |
| Epoxidized fatty acid methyl ester | 175 | 0.21％ |
It can be seen that the product obtained according to the embodiment of the invention has higher flash point and smaller heating decrement than the product obtained by the existing waste oil treatment technology.
The plasticizer comprises the following components in percentage by weight: the formulations of PVC 100, plasticizer 40 and stabilizer 3 were pressed into sheets on a twin-roll machine set at 175 ℃ and the formulations of examples 1, 2 and 3 plasticized quickly at a rate comparable to the plasticizing rate of epoxidized fatty acid methyl ester with less volatile gas and more volatile gas of epoxidized methyl ester. Meanwhile, the PVC material in the epoxy fatty acid methyl ester formula is easy to stick on a roller and is not easy to fall off, a small amount of PE wax serving as a lubricant is added into the formula and is easy to separate from the roller, and the effect of the PVC material is the same as that of the PVC material obtained by the embodiment. The product prepared by the invention can reduce the VOC production in the production process, meanwhile, the product has better lubricating property, the using amount of the lubricant can be reduced, the prior art generally needs 0.3 part of PE wax, and the invention can save 0.1-0.15 part of PE wax.
The plastic product obtained by the double-roller tabletting is subjected to an oil-yielding test according to the activated carbon method for determining loss of HG _ T4458-2012 plastic plasticizer, and the test result is as follows:
| plasticizer | Oil out of |
| Example 1 | 11.07 |
| Example 2 | 11.40 |
| Example 3 | 11.35 |
| Epoxidized fatty acid methyl ester | 13.68 |
From the above results, it is clear that the product obtained by the present invention has significantly reduced oil yield and better performance than the product obtained by the prior art method, when methyl epoxy ester is used as a plasticizer.
Claims (4)
1. A method for preparing an epoxy plasticizer from waste grease is characterized by comprising the following steps: gradually adding alcohol into the waste oil in the presence of an esterification catalyst to perform esterification reaction, and stopping the esterification reaction when the acid value of the system is less than a set value to obtain a mixture of fatty acid ester and glyceride with low condensation point; the mixture of the fatty acid ester with the low condensation point and the glyceride is subjected to epoxidation reaction to obtain a final epoxy plasticizer;
the waste oil is low-freezing-point waste oil with a freezing point of-5-10 ℃; or the waste grease with low freezing point obtained by the following method: freezing and separating the waste oil and fat, and removing solidified high-condensation-point oil and fat to obtain the low-condensation-point waste oil and fat; the freezing fractionation temperature is-10 ℃ to 20 ℃;
the acid value of the waste oil is 3 mgKOH/g-120 mgKOH/g; the set value is 0.2-1 mgKOH/g;
the alcohol is one or more of butanol, isobutanol, octanol and isooctanol; the esterification reaction temperature is 100-250 ℃, and the vacuum condition is kept in the esterification reaction process, wherein the vacuum condition is-0.09 to-0.10 MPa.
2. The method for preparing an epoxy plasticizer from waste grease according to claim 1, comprising the steps of:
(1) freezing and separating the waste oil, and removing the frozen saturated high-condensation-point oil to obtain low-condensation-point waste oil;
(2) adding an esterification catalyst into the waste oil with low condensation point, continuously dropwise adding alcohol, carrying out esterification reaction, and vacuumizing generated water and most unreacted alcohol during the esterification reaction until the acid value is less than a set value, and stopping the reaction;
(3) after esterification, removing residual alcohol in vacuum, and removing an esterification catalyst;
(4) adding formic acid and hydrogen peroxide to perform an epoxy reaction, and performing post-treatment to obtain a final product epoxy plasticizer;
as an optional step, the waste oil with low condensation point after freezing fractionation is decolorized, or an intermediate product after esterification is decolorized.
3. The method for preparing the epoxy plasticizer from the waste grease as claimed in any one of claims 1 to 2, wherein the waste grease is selected from one or more of waste cooking oil, hogwash oil, swill oil and swill oil; or the waste grease is selected from one or more of waste cooking oil, hogwash oil, swill oil and swill-cooked dirty oil after preliminary impurity removal.
4. The method for preparing the epoxy plasticizer from the waste oil and fat according to any one of claims 1 to 2, wherein the weight ratio of the waste oil and fat to the alcohol and the esterification catalyst is as follows: waste grease: alcohol: catalyst = 1: (0.02-0.4) and (0.001-0.05).
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