CN109970688A - A kind of method and product preparing epoxy plasticizer by waste grease - Google Patents
A kind of method and product preparing epoxy plasticizer by waste grease Download PDFInfo
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- CN109970688A CN109970688A CN201910243977.9A CN201910243977A CN109970688A CN 109970688 A CN109970688 A CN 109970688A CN 201910243977 A CN201910243977 A CN 201910243977A CN 109970688 A CN109970688 A CN 109970688A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- 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 kind of methods and product that epoxy plasticizer is prepared using discarded food and drink oil, specifically include that waste grease, which is carried out freezing point, first mentions, remove the saturation lubricant component to epoxy without contribution, then carrying out esterification in the catalyst of solid acid and alcohol reduces acid value, is eventually adding formic acid, hydrogen peroxide carries out epoxidation reaction.Have many advantages, such as that plasticizing effect is good, flash-point is high, thermal weight loss is small with epoxy plasticizer prepared by this method, PVC product is not easy fuel-displaced.This method preparation process is simple, is suitable for industrialized production.
Description
Technical field
The present invention relates to the preparation methods of fine Organic chemical products plasticizer, in particular to a kind of to be prepared by waste grease
The preparation method and product of epoxy plasticizer.
Background technique
We are a populous nations, and oil consumption is more, to consume a large amount of grease, especially vegetable oil such as soybean every year
Oil, peanut oil, palm oil, rapeseed oil etc. are main soybean oil importers.But the more food and drink that can be generated at the same time is useless
Abandon grease.According to statistics, the waste cooking oil, hogwash fat, gutter oil of China annual three or four million generate, if cannot recycle,
Dining table will likely be flowed back to again, bring threat to the health of people.
The plasticizer of asepsis environment-protecting class is mainly epoxies, including epoxidized vegetable oil and epoxy aliphatic ester etc..Epoxy is planted
Object oil is with vegetable oil such as soybean oil, rapeseed oil, corn oil, cottonseed oil etc. for raw material, and nontoxic ring is obtained after epoxidation
Oxygen vegetable oil plasticizer, higher cost.
Have document report to prepare epoxy aliphatic acid methyl ester plasticizer using waste oil at present: " CN200710022603- is utilized
The method of waste grease production epoxy plasticizer " it is to use waste grease for raw material, it is preprocessed to obtain glyceride, then in alkali
Catalysis under with methanol carry out transesterification, obtain fatty acid methyl ester, finally obtain epoxy aliphatic acid methyl ester by epoxidation reaction
Plasticizer." method of CN201310751024- kitchen castoff oil and fat preparation biology plasticizer epoxy aliphatic acid methyl ester " is to adopt
Through molecular distillation after being cleaned with kitchen waste grease, low acid value processing grease is obtained, then using sodium hydroxide as catalyst and first
Alcohol transesterification reaction obtains fatty acid methyl ester, finally carries out epoxidation reaction and obtains epoxy aliphatic acid methyl ester plasticizer.It is above-mentioned this
A little methods, which are all made of, converts fatty acid methyl ester by transesterification for glyceride, needs to consume a large amount of methanol, and therein sweet
Oil is abandoned in vain, leads to higher cost, and aftertreatment technology is relatively complicated.
Summary of the invention
The present invention provides a kind of preparation methods of biomass epoxy plasticizer that can be realized waste grease comprehensive utilization.
Invention also provides a kind of epoxy plasticizer being prepared by waste grease, the plasticizer flash-point is high, warm
It is weightless small, and good biocompatibility, be not easy it is fuel-displaced.
A method of epoxy plasticizer is prepared by waste grease, comprising:
In the presence of esterification catalyst, be gradually added into alcohol into waste grease, it is selectable under vacuum conditions, carry out ester
Change reaction, until the acid value of system stops esterification after being less than setting value, obtains the aliphatic ester of low condensation point and mixing for glyceride
Close object；The aliphatic ester of the low condensation point and the mixture of glyceride obtain final epoxy using epoxidation reaction and are plasticized
Agent.
In the present invention, the alcohol is selected from one of methanol, butanol, isobutanol, octanol, isooctanol or a variety of.As into
One step is preferred, and the alcohol is butanol, isobutanol, octanol, isooctanol.Additional amount is the 5%~40% of waste grease；As excellent
It selects, in the present invention, the esterification reaction temperature is 100~250 DEG C.
When alcohol selects methanol, esterification can be carried out under normal pressure；The extra methanol meeting under above-mentioned reaction temperature
Rapid evaporation.When alcohol select butanol, isobutanol, octanol, one of isooctanol or it is a variety of when, esterification is used in vacuum item
It is carried out under part, vacuum condition is -0.09~-0.10MPa.Reaction time is 2~8 hours.Preferably, reaction temperature is 125
DEG C~220 DEG C.
The present invention is in esterification process, when selecting high-boiling point alcohol as raw material, vacuum condition is introduced, so that esterification process
The water energy of middle generation is enough to be extracted by vacuum in time, ensure that smoothly being rapidly performed by for esterification.More importantly tradition
It is usually that monoglyceride and methanol are subjected to ester exchange reaction when preparing plasticizer, is converted to fatty acid methyl ester, the glycerol of generation,
It needs to remove from system, this part alcohol is wasted；And in order to meet the requirement of transesterification, need methanol significantly excessive,
And need to carry out under reflux conditions, the amount of the methanol of consumption certainly will be caused to greatly increase in this way, while also leading to energy consumption significantly
Increase.Method of the invention carries out esterification under vacuum conditions, also will be excessive unreacted while going water removal
Alcohol is taken away in time so that be added alcohol in waste grease acid directly reacted, and no longer with monoglyceride in system into
The further ester exchange reaction of row further simplifies reaction process so also from reaction mechanism, improves reaction efficiency.When
When using methanol as alcoholic solvent, since the esterification temperature of use is higher, after methanol is reacted with the acid in system, remaining methanol
It can be evaporated from reaction system, equally no longer carry out further ester exchange reaction with monoglyceride in system.The height taken away
The methanol of boiling point alcohol perhaps recycling can apply or other raw materials use as you.The waste grease of low condensation point of the invention,
It can directly be the low condensation point waste grease of outsourcing, condensation point is -5~10 DEG C, is also possible to just be expected by simple by waste grease
Processing obtain.
Preferably, the waste grease is the waste grease of low condensation point or the low condensation point to obtain by the following method
Waste grease: waste grease is removed water, and is carried out freezing point and is mentioned, and is removed the high condensation point oil of solidification, is obtained the useless of the low condensation point
Abandon grease.
Preferably, the method for preparing epoxy plasticizer by waste grease includes the following steps:
(1) after waste grease being gone water removal and other non-oily impurity, freezing point is mentioned: first heating stirring, by all greases
Melt, then cooling is freezed, and is removed the high condensation point grease of saturation for freezing out, is obtained the waste grease of low condensation point；
(2) add esterification catalyst to the waste grease of low condensation point, alcohol is continuously added dropwise, carry out being esterified under vacuum conditions anti-
It answers, the water and most of unreacted alcohol that during which vacuum abstraction generates, until acid value stops reaction after being less than setting value；
(3) alcohol of the vacuum removal remnants after being esterified removes esterification catalyst；
(4) formic acid, hydrogen peroxide progress epoxy reaction is added, post-processing obtains final products epoxy plasticizer；
In above-mentioned reaction step, when alcohol uses methanol, the vacuum condition can be removed, i.e., carry out ester under normal pressure
Change reaction.
Raw polyol of the invention is generally added using from esterifying kettle bottom feed inlet, guarantees alcohol material first and in reaction solution
Acid contact esterification.
Waste grease as selectable step, the low condensation point after mentioning to freezing point decolourizes, or after esterification
Intermediate products decolourize.If that is, raw material color is deeper the oil decolorization after mentioning can be divided freezing, or to obtained monooctyl ester
Intermediate products after change decolourize.When color meets product requirement, above-mentioned decolorization process also can be omitted.
It certainly, can when the waste grease, which is just expected, directly meets low condensation point requirement (i.e. without containing high condensation point grease)
After being directly over water removal or remove other non-oily impurity, in esterification.In the waste grease is just expected
Not comprising water or when other non-oily impurity, and when meeting low condensation point simultaneously and requiring, can be carried out directly as raw material above-mentioned
Esterification, it can omit above-mentioned steps (1).
In the present invention, it is a variety of or can also that the waste grease is selected from one of waste cooking oil, swill oil, gutter oil person
To be that a variety of materials by preliminary treatment of one of waste cooking oil, swill oil, gutter oil person are (such as conventional except living together
Reason, drying process or other conventional preprocessing process).It can be corn oil, soybean oil, peanut oil, palm oil, vegetable seed
The waste oil that one of oil, tea oil, ready-mixed oil etc. of various compositions generate, be also possible to soybean oil, peanut oil, palm oil,
The waste oil of two or more generation in rapeseed oil, naturally it is also possible to be a variety of mixed of the waste oil that they generate alone
Close object.
Contain a large amount of monoglyceride in common waste grease, wherein sour chain part is mostly long chain fatty acids, with C16~
C18 content is most.Preferably, the waste grease of the invention is just expected or the waste grease of low condensation point is to mainly contain
The unsaturated waste grease of C16~C18 chain.The acid value of the waste grease is 3mgKOH/g~120mgKOH/g.As into one
Preferably, the acid value for the waste grease that the freezing divides after mentioning is 3mgKOH/g~70mgKOH/g to step；Still more preferably it is
10mgKOH/g~50mgKOH/g.
In the aliphatic ester of low condensation point and the mixture of glyceride be prepared by the present invention, the glyceride master of low condensation point
Original waste grease is derived from, the aliphatic ester of low condensation point is mainly the free fatty acid and alcohol in original waste grease
A reacts to obtain.
In the present invention, when freezing point mentions, first heating stirring (for example can be and be warming up to 40~60 DEG C, temperature needs basis
The performance of practical waste oil determines), all greases are melted, then cooling is freezed, by the grease of fractional saturation such as animal
The freezings such as oil come out；The high condensation point grease of saturation that freezing comes out is used as other purposes, and the waste grease of low condensation point tests acid value, into
Row next step step.Preferably, the freezing divides temperature raising degree to be -10 DEG C~20 DEG C in the present invention.
In the present invention, in esterification reaction process, the setting value is 0.2~1mgKOH/g, further preferably
0.5mgKOH/g.Esterification is carried out under vacuum conditions, and acid value stops esterification after being less than 0.5mgKOH/g.
In above-mentioned steps (3), the alcohol of the vacuum removal remnants after esterification is esterified by modes such as removing filtering, sedimentations and is urged
Agent.
Preferably, the esterification catalyst is solid catalyst.The solid catalyst further preferably activates temperature
Spend the solid acid catalyst that can promote esterification at 100~250 DEG C.City can be selected when actual selection according to actual needs
The product sold；The solid acid catalyst is more preferably metallic catalyst.The metallic catalyst includes but is not limited to gold
Belong to that sulfate (such as ferrous sulfate), disulfate (sodium bisulfate), sulfonate, (for example to can be oxidation sub- for metal oxide
Tin), metal inorganic hydrochlorate, metal organic acid ester, loaded catalyst (such as can be Supported alumina solid acid catalyst,
Cerous sulfate solid acid catalyst, activated carbon supported p-methyl benzenesulfonic acid etc.).
For methanol, the esterification temperature is generally 100~120；Catalyst is preferably sodium bisulfate, ferrous sulfate, work
Property charcoal load p-methyl benzenesulfonic acid.
For butanol, isobutanol, octanol, isooctanol, preferably, esterification reaction temperature is 125 DEG C~220 DEG C, and
It is carried out under vacuum condition.Under the reaction temperature, preferred catalyst is stannous oxide, Supported alumina solid acid catalyst, sulphur
Sour cerium solid acid catalyst etc..
In the present invention, the weight ratio of the waste grease and pure and mild esterification catalyst are as follows: waste grease: alcohol: catalyst=
1:(0.02~0.4): (0.001~0.05).
In the present invention, the mass ratio of waste grease and formic acid, hydrogen peroxide after the esterification are as follows: waste grease after esterification:
Formic acid: hydrogen peroxide=1:(0.01~0.10): (0.2~0.5)；Reaction temperature is 50~90 DEG C, and iodine number terminates anti-less than 6%
Answer, iodine number less than 3% it is further preferred that.Preferably, the additional amount of formic acid and hydrogen peroxide are as follows: waste grease after esterification: formic acid: hydrogen peroxide
=1:0.03~0.07:0.2~0.35；Preferably, reaction temperature is 60~80 DEG C；Preferably, iodine number is to 3% or less
Stop reaction；
In the present invention, when necessary to the intermediate pint color method after esterification are as follows: use atlapulgite, active carbon or decoloration
The method of agent is decolourized；
Post-processing is carried out in the present invention, after epoxy reaction to refer to using alkali cleaning, washing, vacuum dehydration, stripping, filters pressing
And etc.；
As further preferred, a method of environment-friendly plasticizer is prepared by waste grease, is included the following steps:
1) waste grease is removed into non-oily impurity (including water and other visible non-oily impurity), carries out freezing point
Mention: all greases are melted in first heating stirring, and then cooling is freezed, and the grease of fractional saturation such as animal oil etc. is freezed
Out；The high condensation point grease of saturation that freezing comes out is used as other purposes, and the waste grease of low condensation point tests acid value；
2) oil product deeper for color is added carclazyte and decolourizes；
3) a certain amount of alcohol is added in the waste grease freezed, 100 DEG C~250 DEG C of temperature, anti-under the catalysis of solid acid
Answer 1~8 hour progress esterification；
4) for the oil of esterification, catalyst is removed by filtering or being centrifuged；
5) turn to expect epoxy reaction kettle, a certain amount of formic acid and hydrogen peroxide is added, be heated to 55-65 degree, it is anti-to carry out epoxy
It answers, iodine number stops reaction when dropping to 6% or less；
6) head product after epoxy is stood, and divides sour water, and alkali cleaning, after washing, vacuum dehydration is dry, obtains final products.
Above-mentioned steps 2) in, the oil product deeper for color is described white when carclazyte is added being decolourized under vacuum condition
Native additional amount is the 1%~5% of oil, and temperature is 80 DEG C~120 DEG C.
A kind of epoxy plasticizer prepares epoxy plasticizer by waste grease as described in any of the above-described technical solution
Method is prepared.
The plasticizer compatbility that the present invention obtains is good, plasticizing efficiency is high, and wherein this method has process flow easy to control, gives up
Abandon the advantages that Lipid use rate is high.
That present invention simultaneously provides a kind of compatibilities is good, is not easy fuel-displaced environmentally friendly biomass plasticizer.
The present invention provides a kind of method that waste oil from restaurants prepares epoxy plasticizer.It is extensive with raw material sources, reduce ring
Border pollution and the harm to human health.Final products are as plasticizer function admirable, and renewable, biological degradability is good, can replace
For oil product plasticizer.
The final products that the present invention obtains are the mixture of epoxidised fatty acid glyceride and epoxy aliphatic ester.
Effective effect of the invention are as follows: epoxy plasticizer is prepared with waste grease at present and is made as epoxy aliphatic acid methyl ester,
Although plasticization effect is preferable, flash-point is low, thermal weight loss is big, will increase in product use process higher for processing temperature
The discharge of VOC.Have plasticizing efficiency high with epoxy plasticizer prepared by the present invention at present, flash-point is high, thermal weight loss is small, is provided simultaneously with
Preferable lubricity.In addition, mentioning due to having carried out freezing point to waste grease, saturated component is removed, the plastics made with it
Product is not easy fuel-displaced.Technical process of the invention is simple, and industrialized production is controllable, is suitable for industrialized production.
The epoxy plasticizer prepared using method of the invention is with plasticizing effect is good, flash-point is high, thermal weight loss is small, PVC system
Product are not easy the advantages that fuel-displaced.This method preparation process is simple, is suitable for industrialized production.
The water that the unreacted pure and mild reaction of vacuum extraction of the present invention obtains, directly passes through existing technique and carries out water alcohol point
From alcohol obtained after separation can be applied directly, and the usage amount of solvent is further reduced, and reduce the preparation of plasticizer product
Cost.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Embodiment can be such that researcher more fully understands
The present invention, but the invention is not limited in any way.
Embodiment 1
The high acid value used edible oil that the acid value that freezing divides after mentioning (freezing divides temperature raising degree to be 20 DEG C) is 20mgKOH/g
200g is added in reaction flask, is added 1.0g solid acid catalyst stannous oxide (Aladdin reagent), and stirring is heated to 170 DEG C,
It vacuumizes, holding system internal pressure is -0.1MPa, and isooctanol 18g is gradually passed through by the way of dropwise addition, makes to exist in waste grease
Fatty acid and isooctanol carry out esterification, generate fatty acid monooctyl ester, the monoglyceride in system is held essentially constant, and is reacted
2 hours, acid value dropped to 0.45mgKOH/g, stopped reaction, continued to vacuumize by remaining octanol removal, by solid acid after cooling
Catalyst filtration obtains 208.5g esterification products, is loaded into epoxy reaction bottle, is heated to 60 DEG C, hydrogen peroxide is then added dropwise
The mixture of 50g and formic acid 7.5g carry out epoxy reaction, sampling and testing iodine number, and iodine number 4.2% stops reaction, stand to divide and go
Sour water is added a small amount of liquid alkaline and neutralizes, then washed until neutrality with hot water, contained after obtained head product dewatering and filtering
The final epoxy plasticizer product of octyl ester of epoxy fatty acid and epoxy glyceride.
Embodiment 2
The high acid value used edible oil that the acid value that freezing divides after mentioning (freezing divides temperature raising degree to be 20 DEG C) is 65mgKOH/g
200g is added in reaction flask, is added 1.8g aqueous sulfuric acid cerium solid acid catalyst (Aladdin reagent), and stirring is heated to 130
DEG C, it vacuumizes, holding system internal pressure is -0.1MPa, and butanol 38g is gradually passed through by the way of dropwise addition, makes waste grease memory
Fatty acid and butanol carry out esterification, generate fatty acid butyl ester, react 3 hours, acid value drops to 0.35mgKOH/g, stops
It only reacts, continues to vacuumize remaining butanol removal, filter solid acid catalyst after cooling, obtain 216.4g esterification and produce
Product are loaded into epoxy reaction bottle, are heated to 60 DEG C, and the mixture of hydrogen peroxide 56g and formic acid 9g is then added dropwise, and carry out epoxy
Reaction, sampling and testing iodine number, iodine number 2.5% stop reaction, stand to divide and remove sour water, a small amount of liquid alkaline is added and neutralizes, then with heat
Water washing is obtained after obtained head product dewatering and filtering containing butyl ester of epoxy fatty acid and epoxy glyceride most until neutral
Whole epoxy plasticizer product.
Embodiment 3
Acid value is that the low condensation of the high acid value of 15mgKOH/g (setting temperature is 5~10 DEG C) point used edible oil 200g adds
Enter into reaction flask, 1.2g Supported alumina solid acid catalyst, Qu Bu Hui Spring Biotechnology Co., Ltd is added, stirring adds
Heat is vacuumized to 130 DEG C, and holding system internal pressure is -0.09MPa, and isobutanol 15g is gradually passed through by the way of dropwise addition, makes rouge
Fat acid and isobutanol reaction, generate fatty acid isobutyl ester, react 1 hour, and acid value drops to 0.4mgKOH/g, stops reaction, continue
It vacuumizes and removes remaining isobutanol, solid acid catalyst is filtered after cooling, 203.19g esterification products is obtained, is filled
Enter in epoxy reaction bottle, be heated to 60 DEG C, the mixture of hydrogen peroxide 42g and formic acid 6.5g is then added dropwise, carries out epoxy reaction,
Sampling and testing iodine number, iodine number 2.5% stop reaction, stand to divide and remove sour water, a small amount of liquid alkaline is added and neutralizes, then uses hot water wash
It washs until neutrality, is obtained after obtained head product dewatering and filtering final containing epoxyfatty acid isobutyl ester and epoxy glyceride
Epoxy plasticizer product.
And existing waste oil technical treatment is utilized, first the free fatty acid of 1 waste grease of 200g above-described embodiment to be removed,
Acid value drops to 1.5mgKOH/g hereinafter, obtaining the low acid value glyceride of about 186g, is subsequently placed in methanol (waste grease and methanol
Mass ratio is 1:0.2), back flow reaction (60 DEG C~80 DEG C), reaction time 2.5h, redistillation obtains the fatty acid methyl of about 178.9g
Then ester carries out identical epoxidation reaction, obtain contrast sample epoxy aliphatic acid methyl ester, the yield of the waste oil of the prior art is not
And technology of the invention, while distilled fatty acid methyl esters needs to consume a large amount of energy consumption.
Using method of the invention, the pure and mild aqueous solution of vacuum extraction can be directly used existing technique, such as can be with
Using rectification process, realize the separation of alcohol and water, the alcohol of recycling can in the preparation of direct reuse to plasticizer of the invention, when
So directly pure and mild aqueous solution reuse can also be applied in other techniques into other techniques, or by isolated alcohol.
Performance detection:
The plasticizer flash-point that Examples 1 to 3 is prepared according to " flashing test of GBT+1671-2008+ plasticizer+
Cleveland is open agar diffusion method ", volatility according to " measurement of GBT 1669-2001 plasticizer heating loss ", carry out performance detection,
The epoxy aliphatic acid methyl ester obtained simultaneously with existing waste oil disposal technology compares, as a result as follows:
| Plasticizer | Flash-point, DEG C | Heating loss, % |
| Embodiment 1 | 216 | 0.06% |
| Embodiment 2 | 206 | 0.12% |
| Embodiment 3 | 208 | 0.10% |
| Epoxy aliphatic acid methyl ester | 175 | 0.21% |
It can be seen that the product that embodiment according to the invention obtains is higher than the product flash-point that existing waste oil disposal technology obtains, add
Heat decrement is small.
By above-mentioned several plasticizer according to weight ratio: PVC 100, plasticizer 40, the formula of stabilizer 3, on twin-roll machine
Tabletting, twin-roll machine temperature set 175 DEG C, and the formula of embodiment 1,2,3 is plasticized quickly, the plasticizing rate with epoxy aliphatic acid methyl ester
Quite, the gas of volatilization is less, and the gas of epoxy methyl esters volatilization is more.The PVC of epoxy aliphatic acid methyl ester formula expects ratio simultaneously
It is easier to be sticked on roller, it is bad to fall off, after adding a small amount of lubricant PE wax in this recipe, it is easy to separate with roller, effect and use
The PVC material effect that embodiment obtains is identical.Illustrate the generation that VOC in production process can be reduced with product produced by the present invention
Amount, while the greasy property of product of the invention is more preferable, it is possible to reduce the usage amount of lubricant, the prior art generally require 0.3
The PE wax of part, the present invention can save 0.1-0.15 parts of PE waxes.
The plastic products that above-mentioned twin-roll machine tabletting is obtained carry out out oiliness test, and test method is according to " HG_T 4458-
The measurement activated carbon method of 2012 plastic plasticizers loss ", test result is as follows:
| Plasticizer | It is fuel-displaced, % |
| Embodiment 1 | 11.07 |
| Embodiment 2 | 11.40 |
| Embodiment 3 | 11.35 |
| Epoxy aliphatic acid methyl ester | 13.68 |
From the above it is found that being used as plasticising than the epoxy methyl esters made from existing method with product produced by the present invention
When agent, the fuel-displaced of plastic products is substantially reduced, and performance is more preferable.
Claims (10)
1. a kind of method for preparing epoxy plasticizer by waste grease characterized by comprising in the presence of esterification catalyst,
It is gradually added into alcohol into waste grease, carries out esterification, until the acid value of system stops esterification after being less than setting value, obtains
The aliphatic ester of low condensation point and the mixture of glyceride；The aliphatic ester of the low condensation point and the mixture of glyceride are using ring
Oxidation reaction obtains final epoxy plasticizer.
2. the method according to claim 1 for preparing epoxy plasticizer by waste grease, which is characterized in that the abandoned oil
Rouge is the waste grease of low condensation point or the waste grease for the low condensation point obtained by the following method: waste grease is freezed
Divide and mention, remove the high condensation point grease of solidification, obtains the waste grease of the low condensation point.
3. the method according to claim 1 for preparing epoxy plasticizer by waste grease, which is characterized in that including walking as follows
It is rapid:
(1) waste grease is carried out freezing point to mention, removes the high condensation point grease of saturation for freezing out, obtains the abandoned oil of low condensation point
Rouge；
(2) add esterification catalyst into the waste grease of low condensation point, alcohol is continuously added dropwise, carry out esterification, during which vacuum extracts
The water of generation and most of unreacted alcohol, until acid value stops reaction after being less than setting value；
(3) after being esterified, the alcohol of vacuum removal remnants removes esterification catalyst；
(4) formic acid, hydrogen peroxide progress epoxy reaction is added, post-processing obtains final products epoxy plasticizer；
As selectable step, the waste grease of the low condensation point after mentioning to freezing point decolourizes, or in after esterification
Between product decolourize.
4. the method according to claim 2 or 3 for preparing epoxy plasticizer by waste grease, which is characterized in that described cold
Jelly divides temperature raising degree to be -10 DEG C~20 DEG C.
5. the method described in any one of claim 1 to 3 for preparing epoxy plasticizer by waste grease, feature exist
In the acid value of the waste grease is 3mgKOH/g~120mgKOH/g；The setting value is 0.2~1mgKOH/g.
6. the method described in any one of claim 1 to 3 for preparing epoxy plasticizer by waste grease, feature exist
In the alcohol is methanol, and reaction temperature is 100~250 DEG C.
7. the method described in any one of claim 1 to 3 for preparing epoxy plasticizer by waste grease, feature exist
In the alcohol is one of butanol, isobutanol, octanol, isooctanol or a variety of；Esterification reaction temperature is 100~250 DEG C, ester
Change in reaction process, keep vacuum condition, the vacuum condition is -0.09~-0.10MPa.
8. the method described in any one of claim 1 to 3 for preparing epoxy plasticizer by waste grease, feature exist
It is selected from that one of waste cooking oil, hogwash fat, swill oil, gutter oil person is a variety of or the abandoned oil in, the waste grease
Rouge is selected from one of waste cooking oil, hogwash fat, swill oil, gutter oil or a variety of materials after tentatively cleaning.
9. the method described in any one of claim 1 to 3 for preparing epoxy plasticizer by waste grease, feature exist
In the weight ratio of the waste grease and pure and mild esterification catalyst are as follows: waste grease: alcohol: catalyst=1:(0.02~0.4):
(0.001~0.05).
10. a kind of epoxy plasticizer, which is characterized in that it prepares ring by waste grease by according to any one of claims 1 to 9
The method of oxygen plasticizer is prepared.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372539A (en) * | 2008-07-31 | 2009-02-25 | 浙江嘉澳化工有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
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| CN101372539A (en) * | 2008-07-31 | 2009-02-25 | 浙江嘉澳化工有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
Non-Patent Citations (1)
| Title |
|---|
| 刘朋 等: "高酸值废弃油脂制备生物柴油的预酯化", 《化工进展》 * |
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| CN110804029A (en) * | 2019-11-08 | 2020-02-18 | 浙江工业大学 | Epoxy plasticizer and preparation method thereof |
| CN110804029B (en) * | 2019-11-08 | 2022-04-29 | 浙江工业大学 | Epoxy plasticizer and preparation method thereof |
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