CN109971552B - Method for preparing epoxy plasticizer and chlorinated plasticizer from waste grease - Google Patents
Method for preparing epoxy plasticizer and chlorinated plasticizer from waste grease Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
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- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
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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 and a chlorinated plasticizer from waste grease, which comprises the following steps: freezing and separating the waste grease to obtain high-condensation-point waste grease and low-condensation-point waste grease; reacting the low-condensation-point waste oil with alcohol A to obtain a mixture of fatty acid ester and glyceride with low condensation point; carrying out esterification reaction and ester exchange reaction on the high-condensation-point waste oil and methanol or directly carrying out ester exchange to obtain high-condensation-point fatty acid methyl ester; the mixture of the fatty acid ester with low condensation point and the glyceride is subjected to epoxidation reaction to obtain a final epoxy fatty acid ester plasticizer; the high freezing point fatty acid methyl ester passes through a chlorinated fatty acid methyl ester plasticizer. According to the invention, a freezing fractionation process is adopted, the high-condensation-point waste oil mainly containing saturated fatty acid is finally prepared into the chlorinated fatty acid methyl ester plasticizer, the low-condensation-point waste oil mainly containing unsaturated fatty acid is finally prepared into the epoxy plasticizer, and the efficient utilization of the waste oil is realized.
Description
Technical Field
The invention belongs to a preparation method of a fine organic chemical product plasticizer, and particularly relates to a method for preparing an epoxy plasticizer and a chlorinated plasticizer from waste grease.
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, and 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.
On the other hand, we are still based on traditional phthalate plasticizers such as DOP. 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 performing epoxidation to obtain a nontoxic epoxy vegetable oil plasticizer, and the cost is high.
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 and fat adopts waste oil and fat 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. All of the above methods require the consumption of a large amount of methanol, and are costly and complicated in post-treatment process.
In addition, when the vegetable oil is adopted to prepare the epoxy fatty acid methyl ester plasticizer, saturated components in the vegetable oil cannot be epoxidized, so that the plasticizer has no effect on the plasticization of polyvinyl chloride, the compatibility of the plasticizer and polyvinyl chloride is influenced, and the oil yield is greatly increased.
Disclosure of Invention
The invention provides a method for preparing an epoxy plasticizer and a chlorinated plasticizer from waste oil, which can utilize almost all the waste oil, and respectively prepare different plasticizers from the waste oil with low condensation point and the waste oil with high condensation point according to different freezing points to respectively obtain two plasticizer products with excellent respective performances, and the two obtained plasticizer products have good biocompatibility and are difficult to produce oil.
The epoxy plasticizer prepared by the method has the advantages of high flash point, small thermal weight loss, good biocompatibility and difficult oil production. The chlorinated fatty acid methyl ester plasticizer obtained by the method has good compatibility with polyvinyl chloride, is difficult to produce oil, is cheap and good, and has high cost performance.
A method for preparing epoxy plasticizer and chlorinated plasticizer from waste grease comprises the following steps: freezing and separating the waste grease to obtain high-condensation-point waste grease and low-condensation-point waste grease; reacting the low-condensation-point waste grease with alcohol A to obtain a mixture of fatty acid ester and glyceride with low condensation point; carrying out esterification reaction and ester exchange on the high condensation point waste grease and methanol or directly carrying out ester exchange reaction to obtain high condensation point fatty acid methyl ester; the mixture of the fatty acid ester with low condensation point and the glyceride is subjected to epoxidation reaction to obtain a final epoxy fatty acid ester plasticizer; and carrying out chlorination reaction on the high condensation point fatty acid methyl ester to obtain the chlorinated fatty acid methyl ester plasticizer.
In the invention, the waste grease is selected from one or more of waste cooking oil, swill oil and waste ditch oil, and certainly can also be one or more of the waste cooking oil, swill oil and waste ditch oil which is subjected to primary treatment, such as waste grease from which non-oily impurities can be removed. The waste oil can be waste oil generated by one of corn oil, soybean oil, peanut oil, palm oil, rapeseed oil, tea oil, blend oil with various compositions and the like, waste cooking oil, swill oil and swill oil generated by two or more of soybean oil, peanut oil, palm oil and rapeseed oil, and a plurality of mixtures of the waste cooking oil, the swill oil and the swill oil which are generated by the two or more of the soybean oil, the peanut oil, the palm oil and the rapeseed oil.
The common waste oil contains a large amount of glycerate, wherein the acid chain part is mostly long-chain fatty acid, and the glycerate comprises a small amount of C12, C14, C16, C18 and C20, and the content of C16-C18 is the maximum.
Preferably, the low-freezing-point waste oil or fat of the present invention is an unsaturated waste oil or fat mainly containing C16 to C18. In the mixture of the low-freezing-point fatty acid ester and the glyceride prepared by the invention, the glyceride with the low freezing point is derived from the original waste oil, and the low-freezing-point fatty acid ester is mainly obtained by carrying out esterification reaction on free fatty acid in the original waste oil and alcohol A.
The high-condensation-point waste grease is saturated waste grease mainly containing C16. Preferably, the high freezing point fatty acid methyl ester produced from the waste oil and fat of the present invention mainly contains a small amount of saturated fatty acid chains of C12, C14 and C18, and a large amount of saturated fatty acid chains of C16 components. The high condensation point fatty acid methyl ester used in the present invention may contain a small amount of unsaturated fatty acid methyl ester. Part of the high condensation point fatty acid methyl ester obtained by the method comes from esterification reaction of free fatty acid in the original waste oil and methanol, and the other part comes from fatty glyceride in the original waste oil and the fatty glyceride reacts with the methanol to obtain the high condensation point fatty acid methyl ester.
In the invention, after removing water and other non-oily impurities from the waste grease, freezing and separating, wherein the freezing and separating process comprises the following steps: firstly heating and stirring, melting all the grease, then cooling and freezing, and carrying out solid-liquid separation, wherein the solid part is the high-condensation-point waste grease mainly containing saturated fatty acid or saturated fatty glyceride, and the liquid part is the low-condensation-point waste grease mainly containing unsaturated fatty acid or unsaturated fatty glyceride.
Aiming at the waste oil with low condensation point, the invention introduces vacuum condition when adopting butanol, isobutanol, octanol, isooctanol and the like as alcohol raw materials in the esterification process, so that water generated in the esterification process can be timely pumped out in vacuum, and the smooth and rapid proceeding of the esterification reaction is ensured. More importantly, during the traditional preparation of the plasticizer, glycerate and 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 alcohol is wasted; in order to meet the requirements of ester exchange, a large excess of methanol is required, and the reaction is carried out under reflux conditions, which inevitably increases the amount of methanol consumed and also increases the energy consumption. 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.
Preferably, the low-freezing-point waste oil and fat is reacted with alcohol A to obtain a mixture of low-freezing-point fatty acid ester and glyceride, and the method specifically comprises the following steps: continuously dropwise adding alcohol A into the waste oil with low freezing point in the presence of an esterification catalyst I to perform esterification reaction, and during the period, vacuumizing to remove the generated water and most of unreacted alcohol A (for methanol, vacuumizing is not needed, and unreacted methanol can quickly volatilize from system liquid at a high-temperature esterification temperature), so as to ensure that most or all free fatty acid reacts with the alcohol A, most or all glycerate does not react with the alcohol A, and the reaction is stopped until the acid value is less than a set value H1, thus obtaining the mixture of the fatty acid ester with low freezing point and the glyceride.
Preferably, the low-condensation-point waste oil and fat is reacted with alcohol A to obtain a mixture of low-condensation-point fatty acid ester and glyceride, and then epoxidation is carried out to obtain the epoxy plasticizer, and the method specifically comprises the following steps:
(I-1) adding an esterification catalyst I into the waste oil with low condensation point, continuously dropwise adding alcohol, carrying out esterification reaction, and stopping the reaction until the acid value is less than a set value I;
(I-2) removing residual alcohol in vacuum after esterification, and removing an esterification catalyst to obtain a mixture of fatty acid ester and glyceride with a low condensation point;
and (I-3) adding formic acid and hydrogen peroxide into the obtained mixture of the fatty acid ester with the low condensation point and the glyceride to perform an epoxy reaction, and performing post-treatment to obtain a final product, namely the 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. That is, if the color of the raw material is darker, the oil after freeze fractionation may be decolorized, or the resulting alcohol A may be treated
And (4) decoloring the esterified intermediate product.
Preferably, the acid value of the waste oil and fat with low condensation point is 3mgKOH/g to 120mgKOH/g; more preferably, the acid value of the waste oil and fat with low freezing point after freeze fractionation is 3mgKOH/g to 70mgKOH/g; more preferably 10mgKOH/g to 50mgKOH/g. The set value H1 is 0.2-1 mgKOH/g. In the present invention, it is further preferable that the value I is 0.5 mgKOH/g during the esterification reaction. 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.
Preferably, in the invention, the low-condensation-point waste oil and fat has a condensation point of-5 to 10 ℃ and the high-condensation-point waste oil and fat has a condensation point of 10 to 40 ℃.
In the invention, during freezing fractionation, firstly heating and stirring (for example, the temperature can be raised to 40-60 ℃, and the temperature is determined according to the performance of actual waste oil and fat), melting all the oil and fat, then cooling and freezing, and freezing out partially saturated oil and fat such as animal oil and the like; and (3) carrying out esterification ester exchange and chlorination on the frozen saturated high-condensation-point grease to obtain an epoxy plasticizer, testing the acid value of the waste grease with a low condensation point, and carrying out subsequent esterification reaction when the acid value is greater than a set value I. Preferably, the present invention
Wherein the freezing and fractionation temperature is-10 ℃ to 20 ℃.
In the present invention, the alcohol a is selected from one or more of methanol, butanol, isobutanol, octanol and isooctanol. As a further preference, the alcohol a is isooctanol. The adding amount is 5-40% of the waste grease.
In the step (I-2), residual alcohol is removed in vacuum after esterification, and the esterification catalyst is removed by removing, filtering, settling and the like.
Preferably, the esterification reaction temperature of the esterification reaction of the waste oil and fat with low condensation point and the alcohol A is 100-250 ℃; when methanol is used as the raw material for esterification, the reaction temperature is preferably 100-120 ℃, and the reaction is carried out under normal pressure; when the temperature is higher than the set temperature
When one or more of butanol, isobutanol, octanol and isooctanol are adopted, the reaction temperature is further optimized to be 125-220 ℃, and vacuum conditions are adopted in the esterification process, wherein the vacuum conditions are-0.09 to-0.10 MPa; the weight ratio of the low-condensation-point waste grease to the alcohol A to the esterification catalyst I is as follows: low freezing point waste grease: alcohol A: esterification catalyst I =1: (0.02-0.4): (0.001-0.05). Preferably, the reaction time is 2 to 8 hours. Preferably, the esterification catalyst is a solid catalyst. The solid catalyst is more preferably a solid acid catalyst having an activation temperature of 100 to 250 ℃ and capable of promoting the 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 (ferrous sulfate, zirconium sulfate, etc.), 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, supported p-toluenesulfonic acid, etc.).
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 finished at a reaction 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; preferably, the reaction temperature is 60 to 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 waste oil, freezing, separating, heating and stirring to melt all oil, cooling, and freezing to obtain partially saturated oil such as animal oil; preparing the frozen saturated high-condensation-point grease into fatty acid methyl ester, and performing chlorination reaction to obtain chlorinated fatty acid methyl ester plasticizer, and testing the acid value of the waste grease with low condensation point;
2) Adding clay into the waste oil with deep color and low condensation point for decoloring;
3) Adding a certain amount of alcohol into the frozen low-condensation-point waste oil, reacting for 1-8 hours at the temperature of 100-250 ℃ under the catalysis of solid acid to perform esterification reaction;
4) The esterified oil is filtered or centrifuged to remove the catalyst;
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 water, washing with alkali, washing with water, dehydrating in vacuum and drying to obtain the final product.
In the step 2), when the oil product with a dark color is decolorized by adding clay, the clay is added in an amount of 1-5% of the oil, the temperature is 80-120 ℃, and the decolorization is preferably performed under a vacuum condition.
In the invention, the esterification reaction and the ester exchange reaction are carried out on the high condensation point waste grease and methanol to obtain the high condensation point fatty acid methyl ester, which specifically comprises the following steps:
in the presence of an esterification catalyst II, carrying out esterification reaction on the high-condensation-point waste oil and methanol, reducing the acid value to be below a set value H2, and removing the esterification catalyst I; and adding a transesterification catalyst and methanol to perform transesterification reaction, removing glycerol and methanol after the reaction is finished, and obtaining the high-condensation-point fatty acid methyl ester.
The method fully utilizes free saturated fatty acid or saturated fatty acid glyceride in the waste oil, firstly esterifies the free saturated fatty acid or fatty acid mainly containing the saturated fatty acid with methanol, and then converts the saturated fatty acid glyceride or glyceride mainly containing the saturated fatty acid glyceride into methyl ester by ester exchange. And then chlorinated to obtain chlorinated fatty acid methyl ester.
Because the condensation point of the saturated fatty acid or the saturated fatty acid glyceride is relatively high, the waste oil meeting the condensation point requirement can be directly subjected to esterification and ester exchange, or the esterification and ester exchange reaction can be directly performed when the acid value in the waste oil is lower than a required value (1.5 mg KO H/g or less than 1.5 mg KOH/g).
Before esterification, low freezing point waste oil and high freezing point waste oil in the waste oil initial material are separated by utilizing freezing fractionation, and the high freezing point waste oil is utilized for esterification and ester exchange to remove methanol, so that the high freezing point fatty acid methyl ester is obtained.
In the present invention, when the acid value of the obtained waste oil or fat after freeze fractionation is less than 1.5 mgKOH/g, the transesterification reaction can be directly carried out. Most of the directly obtained waste oil and fat have an acid value far higher than 1.5 mgKOH/g. Preferably, the acid value of the waste oil or fat having a high freezing point obtained by freeze fractionation is 5 to 150KOH/g, and in this case, the acid value of the waste oil or fat is lowered to a value of H2 (1.5 mgKOH/g or 1.5 mgKOH/g) or less by esterification with methanol.
The acid value of the waste oil with high condensation point is 3 mgKOH/g-150 mgKOH/g; the set value H2 is 1 to 2mgKOH/g.
As a further refinement, the high condensation point fatty acid methyl ester is obtained by the following method: removing non-oil impurities from the waste oil initial material, and performing freezing fractionation to remove the low-condensation-point waste oil to obtain high-condensation-point waste oil; abandon to high condensation point
Adding methanol and an acid catalyst into the grease, carrying out esterification reaction, reducing the acid value to be below H2, and removing the acid catalyst; and adding an alkali catalyst and methanol, performing ester exchange to obtain crude fatty acid methyl ester, and removing the methanol and glyceride to obtain the high condensation point fatty acid methyl ester.
More preferably, in the method for preparing the epoxy plasticizer and the methyl chloride fatty acid ester plasticizer from the waste oil, water and other non-oily impurities are removed from the waste oil initial material, and then the waste oil with high condensation point is obtained after freezing and separating, and then:
(II-1) adding a certain amount of methanol and an acid catalyst into the waste oil with high condensation point, carrying out esterification reaction, reducing the acid value to be lower than H2, and removing the acid catalyst;
(II-2) adding a certain amount of alkali catalyst and methanol, carrying out ester exchange reaction to obtain crude fatty acid methyl ester, and carrying out vacuum distillation to obtain the high condensation point fatty acid methyl ester.
(II-3) adding a catalyst into the obtained high condensation point fatty acid methyl ester, and introducing chlorine gas to obtain a final product of chlorinated fatty acid methyl ester.
Preferably, after obtaining fatty acid methyl ester with high condensation point, adding a catalyst into the fatty acid methyl ester with high condensation point or carrying out ultraviolet irradiation, heating and introducing chlorine gas to carry out chlorination reaction, sampling and testing the density of an intermediate product, stopping the chlorination reaction after the density is qualified, then carrying out operations of removing residual chlorine gas and produced hydrogen chloride gas, and adding a stabilizer to obtain a chlorinated fatty acid methyl ester product. The density value can be determined as needed, and in the present invention, the density value is preferably 1 to 1.5 g/cm3.
The high freezing point fatty acid methyl ester has a freezing point of 5-40 ℃, can be prepared by freezing and extracting waste oil to obtain high freezing point waste oil, and then reacts with methanol to obtain high freezing point fatty acid methyl ester with a low iodine value.
In the invention, in the aspect of treatment and utilization of waste grease, the saturated fatty acid methyl ester which does not contribute to epoxy is separated, the part of raw materials can obtain products with excellent performance indexes, the unsaturated methyl ester with low condensation point is not suitable for being used as the raw material of chlorinated plasticizer, and the epoxy plasticizer is obtained through esterification and epoxidation, so that the waste grease resource is fully and comprehensively utilized.
Preferably, the temperature of the esterification reaction is 60-120 ℃ for the waste oil with high condensation point; in the esterification reaction, the weight ratio of the waste grease to the methanol to the esterification catalyst II is as follows: waste grease: methanol: esterification catalyst II =1: (0.02-0.4): (0.001-0.05); the temperature of the ester exchange reaction is 55-85 ℃; in the ester exchange reaction, the alkali catalyst can be calcium oxide, calcium hydroxide, potassium hydroxide, sodium methoxide and other hydroxides of metal elements in a second main group, the adding amount of the alkali catalyst is 0.2-2.0% of the weight of the waste oil, and the adding amount of the methanol is 15-30% of the weight of the waste oil.
In the invention, the condensation point range of the high condensation point fatty acid methyl ester is 5-40 ℃, and the iodine value range is 0-60%; preferably, the condensation point range is 10-30 ℃, and the iodine value is 0-40%;
preferably, the esterification catalyst II is a solid catalyst. The solid catalyst is more preferably a solid acid catalyst having an activation temperature of 60 to 120 ℃ and capable of promoting the 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, sulfonate, metal 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.).
After the ester exchange is completed: heating to 110 ℃ under the vacuum condition of-0.09 Mpa to-0.1 Mpa, distilling to remove methanol, continuously heating, and collecting the rest fractions to obtain the high condensation point fatty acid methyl ester; in the preparation method without using freeze fractionation, after the completion of the transesterification: heating to 110 ℃ under the vacuum condition of-0.09 Mpa to-0.1 Mpa, and distilling to remove methanol; then rectifying under the same vacuum condition, and collecting 220-240 ℃ fractions to obtain the high condensation point fatty acid methyl ester.
In the invention, the catalyst used in the chlorination reaction is azoisobutyronitrile, peroxide ether, ultraviolet light and the like, preferably, ultraviolet light is selected;
the chlorinated plasticizer obtained by the invention 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 provides a method for preparing an epoxy plasticizer and a chlorinated fatty acid methyl ester 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 an epoxy fatty acid ester plasticizer and a chlorinated fatty acid methyl ester plasticizer;
the prior method for preparing the epoxy plasticizer by using the waste oil is to prepare epoxy fatty acid methyl ester, and although the plasticizing effect is good, the flash point is low, the heat loss is large, and the odor is large.
According to the invention, a freezing fractionation process is adopted, high-condensation-point waste oil and low-condensation-point waste oil are separated in advance before esterification, the high-condensation-point waste oil mainly containing saturated fatty acid is finally prepared into chlorinated fatty acid methyl ester plasticizer, and the low-condensation-point waste oil mainly containing unsaturated fatty acid is finally prepared into epoxy plasticizer, so that the efficient utilization of the waste oil is realized. The method has the advantages of simple process and controllable industrial production, and is suitable for industrial production.
The epoxy plasticizer prepared by the invention has the advantages of high plasticizing efficiency, high flash point, small thermal weight loss and better lubricity. Because the saturated components in the raw materials are removed, the plastic products made of the raw materials are not easy to produce oil.
When the low-condensation-point grease is treated, the unreacted alcohol extracted in vacuum in the reaction process and the water obtained by the reaction are directly subjected to water-alcohol separation by the existing process, and the alcohol obtained after separation can be directly reused, so that the use amount of a solvent is further reduced, and the preparation cost of a plasticizer product is reduced.
The chlorinated fatty acid methyl ester plasticizer prepared by the method has the advantages of good plasticizing effect, good compatibility with PVC, difficult oil production, low condensation point, less smell than epoxy fatty acid methyl ester, chlorine as one of the raw materials, mostly a byproduct of chlor-alkali enterprises, wide source, low price (sometimes reverse sticking), and balance of byproducts in the chemical industry. The method has the advantages of simple process and controllable industrial production, and is suitable for industrial production.
The environment-friendly chlorinated fatty acid methyl ester plasticizer prepared by the method has the advantages of good plasticizing effect, difficult oil production of PVC products, low condensation point, low price, high quality and the like. The method has simple preparation process and is suitable for industrial production.
Detailed Description
The present invention is further illustrated by the following specific examples. Embodiments may enable researchers to better understand
The present invention is to be considered as illustrative and not restrictive in any way.
Example 1
Heating 200g of waste hogwash oil with water impurities removed to 50 ℃, dissolving all solid grease parts, slowly cooling, performing freeze fractionation, cooling the grease with a freezing temperature of 20 ℃, and performing filter pressing after the grease with a high condensation point is cooled out to obtain 20g of grease with a high condensation point
The acid value of the grease is 11mgKOH/g; 180g of a low-freezing-point oil having an acid value of 20mgKOH/g was obtained. The obtained high-freezing-point grease and low-freezing-point grease are respectively treated as follows: aiming at the grease with high condensation point: adding 0.05 g of acid catalyst sodium bisulfate and a chemical reagent, heating to 100 ℃, slowly adding 1.5 g of methanol dropwise, sampling to test that the acid value is 1.2 mgKOH/g, standing to remove the acid catalyst, adding 0.18 g of sodium hydroxide and 3.6 g of methanol, stirring, reacting at 65 ℃ for 3 hours, standing to remove glycerol to obtain crude methyl ester, distilling to 110 ℃ under vacuum (-0.09 Mpa to-0.1 Mpa) to remove the methanol, continuously heating to evaporate the fatty acid methyl ester, leaving glycerol in a distillation flask, collecting fractions to obtain high condensation point fatty acid methyl ester (the condensation point range is 30 ℃ and the iodine value is 5%), adding 0.02 g of azoisobutyronitrile, heating to 90 ℃, introducing chlorine gas to carry out chlorination reaction, sampling to test that the density is 1.10 g/cm & lt 3 & gt after reacting for 3 hours, stopping introducing the chlorine gas, introducing the nitrogen gas, removing the residual chlorine gas and the byproduct hydrogen chloride, and obtaining the final product of the chlorinated fatty acid methyl ester.
Aiming at the low freezing point grease: adding a product with an acid value of 20mgKOH/g into a reaction bottle, adding 0.9 g of stannous oxide (an avadin reagent) as a solid acid catalyst, stirring, heating to 170 ℃, vacuumizing, keeping the internal pressure of a system at-0.1 MPa, gradually introducing 16.2 g of isooctanol by adopting a dropwise adding mode, carrying out esterification reaction on fatty acid and isooctanol existing in waste grease to generate octyl fatty acid ester, keeping the glyceryl oleate in the system basically unchanged, reacting for 2 hours, reducing the acid value to 0.45 mgKOH/g, stopping the reaction, continuously vacuumizing to remove residual octanol, filtering the solid acid catalyst after cooling to obtain 187.6 g of an esterified product, filling the esterified product into an epoxy reaction bottle, heating to 60 ℃, dropwise adding a mixture of 45g and 6.8 g of formic acid to carry out an epoxy reaction, sampling to test an iodine value, keeping the iodine value to be 4.2%, stopping the reaction, standing to remove acid water, adding a small amount of liquid alkali to neutralize, washing to be neutral, and obtaining a final epoxy glyceride product containing epoxy fatty acid octyl ester and epoxy glyceride plasticizer after dehydration and filtration of the primary product.
Example 2
Heating 200g of waste gutter oil with water impurities removed to 50 ℃, dissolving all solid grease parts, slowly cooling, performing freezing fractionation, cooling to 20 ℃, and performing filter pressing after high-condensation-point grease is cooled out to obtain 22g of high-condensation-point grease, wherein the acid value is 45mgKOH/g; 178g of low-freezing-point oil and fat having an acid value of 65mgKOH/g were obtained. The obtained high-freezing-point grease and low-freezing-point grease are respectively treated as follows:
aiming at the grease with high condensation point: adding 22g of high condensation point grease into a reaction bottle, adding 0.11 g of ferrous sulfate serving as an acid catalyst, adding a chemical reagent grade, heating to 100 ℃, slowly dropwise adding 4.4 g of methanol, sampling to test the acid value to be 0.98 mgKOH/g, standing to remove the acid catalyst, adding 0.176 g of sodium hydroxide and 4.4 g of methanol, stirring, reacting at 70 ℃ for 3.5 hours, standing to remove glycerol to obtain crude methyl ester, vacuum distilling (-0.09 to-0.1 Mpa) to 110 ℃ to remove methanol, continuously heating to evaporate the fatty acid methyl ester, collecting fractions to obtain the high condensation point fatty acid methyl ester (the condensation point range is 25 ℃ and the iodine value is 15%), adding 0.028 g of azoisobutyronitrile, heating to 90 ℃, introducing chlorine to perform chlorination reaction, sampling to test the density to be 1.12 g/cm < 3 > after reacting for 3 hours, stopping introducing chlorine, introducing nitrogen, removing residual chlorine and hydrogen chloride serving as a byproduct, and obtaining the final product of chlorinated fatty acid methyl ester.
Aiming at the grease with low condensation point: 178g of low freezing point grease is added into a reaction bottle, 1.6 g of aqueous cerium sulfate solid acid catalyst (an avadin reagent) is added, the mixture is stirred, the temperature is raised to 130 ℃, the vacuum pumping is carried out, the internal pressure of the system is kept to be-0.1 MPa, 34g of butanol is gradually introduced in a dropwise adding mode, the fatty acid and the butanol existing in the waste grease are subjected to esterification reaction to generate fatty acid butyl ester, the acid value is reduced to 0.35 mgKOH/g, the reaction is stopped, the vacuum pumping is continued to remove the residual butanol, the solid acid catalyst is filtered after the temperature is reduced to obtain 192.6 g of esterified product, the esterified product is put into an epoxy reaction bottle, the esterified product is heated to 60 ℃, then a mixture of 50g of hydrogen peroxide and 8g of formic acid is dropwise added to perform epoxy reaction, the sampling test iodine value is carried out, the iodine value is 2.5%, the reaction is stopped, the acid water is separated by standing, a small amount of liquid alkali is added to neutralize, then the esterified product is washed by hot water until the neutral, and the obtained primary product is dehydrated and filtered to obtain the final epoxy plasticizer product containing epoxy fatty acid butyl ester and epoxy glyceride.
Example 3
Heating 200g of waste illegal cooking oil with water impurities removed to 50 ℃, dissolving all solid grease parts, slowly cooling, performing freezing fractionation, cooling the high freezing point grease to 20 ℃, and performing filter pressing to obtain 25g of high freezing point grease with an acid value of 5mgKOH/g; 175g of low-freezing-point oil and fat with an acid value of 15mgKOH/g were obtained, and the high-freezing-point oil and the low-freezing-point oil and fat were treated as follows:
aiming at the grease with high condensation point: adding 25g of high condensation point grease into a reaction bottle, adding 0.12 g of zirconium sulfate as an acid catalyst and a chemical reagent, heating to 100 ℃, slowly dropwise adding 3.8 g of methanol, sampling and testing the acid value to be 0.96 mgKOH/g, standing to remove the acid catalyst, adding 0.2 g of sodium hydroxide and 4.8 g of methanol, stirring, reacting at 70 ℃ for 3.5 hours, standing to remove glycerol to obtain crude methyl ester, vacuum distilling (-0.09 Mpa to-0.1 Mpa) to 110 ℃ to remove methanol, continuously heating to evaporate the fatty acid methyl ester, collecting fractions to obtain the high condensation point fatty acid methyl ester (the condensation point range is 25 ℃ and the iodine value is 22%), adding 0.032 g of azoisobutyronitrile, heating to 90 ℃, introducing chlorine to perform chlorination, reacting for 3 hours, sampling and testing the density to be 1.09 g/cm < 3 >, stopping introducing chlorine, introducing nitrogen, removing residual chlorine and byproduct hydrogen chloride, and obtaining the final product of chlorinated fatty acid methyl ester.
Aiming at the low freezing point grease: adding 175g of low-condensation-point oil into a reaction bottle, adding 1.05 g of a loaded alumina solid acid catalyst, stirring, heating to 130 ℃, vacuumizing, keeping the internal pressure of a system at-0.09 MPa, gradually introducing 13.1 g of isobutanol by adopting a dropwise manner, performing esterification reaction on fatty acid and isobutanol existing in waste oil to generate fatty acid isobutyl ester, reacting for 3 hours, reducing the acid value to 0.4 mgKOH/g, stopping the reaction, continuously vacuumizing to remove residual isobutanol, filtering the solid acid catalyst after cooling to obtain 177.8 g of an esterified product, filling the esterified product into an epoxy reaction bottle, heating to 60 ℃, then dropwise adding a mixture of 36.8 g of hydrogen peroxide and 5.69 g of formic acid to perform an epoxy reaction, sampling to test the iodine value, stopping the reaction, standing to separate acid water, adding a small amount of liquid alkali to neutralize, washing to neutrality by using hot water, dehydrating and filtering the obtained primary product to obtain a final epoxy product plasticizer containing epoxy fatty acid and epoxy glyceride.
The prior waste oil treatment technology is adopted, 200g of free fatty acid of the waste oil is removed, and the acid value is reduced
Obtaining about 186g of low acid value glyceride when the oil content is below 1.5 mgKOH/g, then placing the glyceride in methanol (the mass ratio of the waste oil to the methanol is 1.
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 epoxy plasticizers obtained in examples 1 to 3 were tested for their properties according to GBT +1671-2008+ determination of flash point of plasticizer + Cleveland open cup method and for their volatility according to GBT 1669-2001 determination of plasticizer heating loss, and compared with epoxy fatty acid methyl esters obtained by the prior art of waste oil treatment, the results were as follows:
it can be seen that the product obtained according to the example of the present invention has a higher flash point and a smaller heating loss than those obtained by the conventional waste oil treatment techniques (i.e., the above-mentioned "epoxidized fatty acid methyl esters").
The epoxy plasticizer in the above several examples is prepared according to the following weight ratio: the formulations of PVC 100, plasticizer 40, stabilizer 3 were sheeted on a twin-roll machine set at 175 ℃ and the formulations of examples 1,2,3 plasticized very quickly, at a rate comparable to the rate of plasticizing epoxy fatty acid methyl ester, with less gas evolved and more gas evolved from epoxy 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, and after a small amount of PE wax serving as a lubricant is added into the formula, the PVC material 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 of the invention has better lubricating performance, the usage 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-out test according to the activated carbon method for determining loss of the HG _ T4458-2012 plastic plasticizer, and the test result is as follows:
from the above results, it is understood that the oil-yielding property of the plastic product is better in the product obtained by the present invention than in the case where the methyl epoxy ester obtained by the conventional method is used as a plasticizer.
The freezing point of the chlorinated fatty acid methyl ester plasticizer prepared in the embodiment 1-3 is-8 ℃ according to the determination method of the freezing point of fatty acid of import and export animal fat and oil, SNT 0801.17, and is lower than the freezing point of the prior epoxidized fatty acid methyl ester at 5-15 ℃, so that the chlorinated fatty acid methyl ester plasticizer is convenient for customers to use.
The chlorinated plasticizer in the above several embodiments is prepared according to the following weight ratio: PVC 100, plasticizer 40, stabilizer 3, on a twin-roll machine, the temperature of the twin-roll machine was set at 175 ℃, the chlorinated fatty acid methyl ester plasticizer prepared in examples 1,2,3 plasticizes rapidly, slightly slower than the epoxidized fatty acid methyl ester, and less volatile gas.
The plastic product obtained by the double-roller tabletting is subjected to an oil-yielding test according to the activated carbon method for determining the loss of the plastic plasticizer HG _ T4458-2012, and the test result is as follows:
from the above results, it is understood that the chlorinated fatty acid methyl ester plasticizer product obtained by the present invention is more excellent than the chlorinated fatty acid methyl ester plasticizer product obtained by the conventional method
When the obtained epoxy methyl ester is used as a plasticizer, the plastic product is not easy to produce oil.
Claims (2)
1. A method for preparing epoxy plasticizer and chlorinated plasticizer from waste grease is characterized by comprising the following steps:
freezing and separating the waste grease to obtain high-condensation-point waste grease and low-condensation-point waste grease;
reacting the low-condensation-point waste oil with alcohol A to obtain a mixture of fatty acid ester and glyceride with low condensation point; carrying out esterification reaction and ester exchange reaction on the high-condensation-point waste oil and methanol or directly carrying out ester exchange to obtain high-condensation-point fatty acid methyl ester; the mixture of the fatty acid ester with low condensation point and the glyceride is subjected to epoxidation reaction to obtain a final epoxy fatty acid ester plasticizer; carrying out chlorination reaction on the high condensation point fatty acid methyl ester to obtain a chlorinated fatty acid methyl ester plasticizer;
the freezing fractionation temperature is-10 ℃ to 20 ℃; the condensation point of the waste oil with the low condensation point is-5 to 10 ℃, and the condensation point of the waste oil with the high condensation point is 10 to 40 ℃;
the low-condensation-point waste grease is reacted with alcohol A to obtain a mixture of low-condensation-point fatty acid ester and glyceride, and the method specifically comprises the following steps: continuously dropwise adding alcohol A into the waste oil with low freezing point in the presence of an esterification catalyst I, carrying out esterification reaction, stopping the reaction until the acid value is less than a set value H1, and obtaining a mixture of the fatty acid ester with low freezing point and glyceride; the alcohol A is selected from one or more of methanol, butanol, isobutanol, octanol and isooctanol; when one or more of butanol, isobutanol, octanol and isooctanol is selected, the esterification is carried out under the vacuum condition of-0.09 to-0.10 Mpa; the catalyst I is selected from stannous oxide, cerium sulfate or a loaded alumina solid acid catalyst;
the acid value of the waste oil with low condensation point is 3 mgKOH/g-120 mgKOH/g; the set value H1 is 0.2 to 1mgKOH/g;
the method comprises the following steps of carrying out esterification reaction and ester exchange reaction on the high-condensation-point waste grease and methanol to obtain high-condensation-point fatty acid methyl ester, and specifically comprises the following steps:
in the presence of an esterification catalyst II, carrying out esterification reaction on the high-condensation-point waste oil and methanol, reducing the acid value to be below a set value H2, and removing the esterification catalyst II; adding an ester exchange catalyst and methanol to perform ester exchange reaction, removing glycerol and methanol after the reaction is finished, and obtaining the high condensation point fatty acid methyl ester; the catalyst II is selected from sodium bisulfate, ferrous sulfate and zirconium sulfate;
the acid value of the waste oil with high condensation point is 3 mgKOH/g-150 mgKOH/g; the set value H2 is 1 to 2mgKOH/g;
the esterification reaction temperature in the reaction of the low-condensation-point waste oil and the alcohol A is 100-250 ℃; the weight ratio of the low-condensation-point waste grease to the alcohol A to the esterification catalyst I is as follows: low freezing point waste grease: alcohol A: esterification catalyst I =1: (0.02-0.4) and (0.001-0.05);
in the esterification reaction and the ester exchange reaction of the high condensation point waste oil and methanol, the temperature of the esterification reaction is 60-120 ℃; in the esterification reaction, the weight ratio of the waste oil to the methanol to the esterification catalyst II is as follows: methanol: esterification catalyst II =1: (0.02-0.4) and (0.001-0.05); the temperature of the ester exchange reaction is 55-85 ℃; in the ester exchange reaction, the alkali catalyst can be calcium oxide, calcium hydroxide, potassium hydroxide, sodium methoxide and hydroxides of other metal elements in a second main group, the addition amount of the alkali catalyst is 0.2-2.0% of the weight of the waste oil, and the addition amount of the methanol is 15-30% of the weight of the waste oil.
2. The method for preparing epoxy plasticizer and chlorinated plasticizer from waste grease according to claim 1, wherein: the waste grease is an initial material consisting of one or more of waste cooking oil, hogwash oil, swill oil and swill-cooked dirty oil, or a treatment material obtained by removing non-oil impurities from the initial material.
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| CN111517951A (en) * | 2020-05-15 | 2020-08-11 | 福建致尚生物质材料发展有限公司 | Method for preparing methyl chloropalmitate plasticizer by using palmitic acid |
| CN112126121B (en) * | 2020-09-03 | 2021-11-30 | 合肥飞木生物科技有限公司 | Method for preparing cold-resistant and extraction-resistant rubber plasticizer by using unsaturated fatty acid methyl ester |
| CN112961404B (en) * | 2020-12-24 | 2022-11-25 | 中国林业科学研究院林产化学工业研究所 | Epoxy oligoetherglyceride plasticizer and preparation method thereof |
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| CN115074183B (en) * | 2022-07-12 | 2023-02-17 | 陕西海斯夫生物工程有限公司 | Environment-friendly plasticizer prepared from waste oil and fat, preparation method and application thereof |
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