CN109971552A - A method of epoxy plasticizer and chloro plasticizer are prepared by waste grease - Google Patents
A method of epoxy plasticizer and chloro plasticizer are prepared by waste grease Download PDFInfo
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- CN109971552A CN109971552A CN201910243965.6A CN201910243965A CN109971552A CN 109971552 A CN109971552 A CN 109971552A CN 201910243965 A CN201910243965 A CN 201910243965A CN 109971552 A CN109971552 A CN 109971552A
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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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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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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- 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
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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
- C11C3/003—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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- 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
- C11C3/10—Ester interchange
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Abstract
The invention discloses a kind of methods for preparing epoxy plasticizer and chloro plasticizer by waste grease, comprising: waste grease is carried out freezing point and is mentioned, high condensation point waste grease and low condensation point waste grease are obtained；Low condensation point waste grease is reacted with alcohol A, obtains the aliphatic ester of low condensation point and the mixture of glyceride；High condensation point waste grease and methanol carry out esterification and ester exchange reaction or directly progress transesterification obtains high condensation point fatty acid methyl ester；The aliphatic ester of low condensation point and the mixture of glyceride obtain final epoxyfatty acid ester plasticiser by epoxidation reaction；High condensation point fatty acid methyl ester passes through chlorinated fatty acid methyl esters plasticizer.The present invention is using freezing fractionation technology, the high condensation point waste grease for mainly containing saturated fatty acid is finally prepared into chlorinated fatty acid methyl esters plasticizer, the low condensation point waste grease for mainly containing unsaturated fatty acid is finally prepared into epoxy plasticizer, realizes the efficient utilization of waste grease.
Description
Technical field
The invention belongs to the preparation methods of fine Organic chemical products plasticizer, in particular to one kind is by abandoned oil
The method that rouge prepares epoxy plasticizer and chloro plasticizer.
Background technique
We are a populous nations, and oil consumption is more, to consume a large amount of grease every year, and especially vegetable oil is for example big
Soya-bean oil, peanut oil, palm oil, rapeseed oil etc. are main soybean oil importers.But the more meal that can be generated at the same time
Drink waste grease.According to statistics, the waste cooking oil, hogwash fat, gutter oil of China annual three or four million generate, if cannot recycle
It utilizes, it would be possible to flow back to dining table again, bring threat to the health of people.
On the other hand, we are still based on traditional phthalate plasticizers such as DOP.Asepsis environment-protecting class
Plasticizer is mainly epoxies, including epoxidized vegetable oil and epoxy aliphatic ester etc..Epoxidized vegetable oil is with vegetable oil such as soybean
Oil, rapeseed oil, corn oil, cottonseed oil etc. are raw material, and nontoxic epoxidized vegetable oil plasticizer, cost are obtained after epoxidation
It is higher.
There is document report to prepare epoxy aliphatic acid methyl ester plasticizer using waste oil at present: " CN200710022603- benefit
With the method for waste grease production epoxy plasticizer " it is to use waste grease for raw material, it is preprocessed to obtain glyceride, then
Transesterification is carried out with methanol under the catalysis of alkali, obtains fatty acid methyl ester, finally obtains epoxyfatty acid by epoxidation reaction
Methyl esters plasticizer." the side of CN201310751024- kitchen castoff oil and fat preparation biology plasticizer epoxy aliphatic acid methyl ester
Method " it is to obtain low acid value processing grease through molecular distillation after being cleaned using kitchen waste grease, be then to urge with sodium hydroxide
Agent and methanol ester exchange reaction obtain fatty acid methyl ester, finally carry out epoxidation reaction and obtain epoxy aliphatic acid methyl ester plasticising
Agent.These above-mentioned methods are required to consume a large amount of methanol, higher cost, and aftertreatment technology is relatively complicated.
In addition, the saturated component in vegetable fat cannot when preparing epoxy aliphatic acid methyl ester plasticizer using vegetable fat
The compatibility of plasticizer and polyvinyl chloride will affect to the no effect of the plasticizing of polyvinyl chloride by epoxy on the contrary, oil yield is big
It is big to increase.
Summary of the invention
The present invention provides a kind of methods for preparing epoxy plasticizer and chloro plasticizer by waste grease, utilize this
Method can utilize most waste grease, and according to the difference of freezing point, by the waste grease and height of low condensation point
The waste grease of condensation point prepares different plasticizer respectively, respectively obtains two kinds of plasticizer products of respective function admirable, and obtain
To two kinds of products good biocompatibility, be not easy it is fuel-displaced.
The epoxy plasticizer flash-point obtained by the present invention is high, thermal weight loss is small, and good biocompatibility, be not easy it is fuel-displaced.By this
The compatibility of chlorinated fatty acid methyl esters plasticizer and polyvinyl chloride that invention obtains is good, it is fuel-displaced to be not easy, good and cheap, has very
High cost performance.
A method of epoxy plasticizer and chloro plasticizer being prepared by waste grease, comprising: carry out waste grease
Freezing point mentions, and obtains high condensation point waste grease and low condensation point waste grease；Low condensation point waste grease is reacted with alcohol A, is obtained low solidifying
The aliphatic ester of point and the mixture of glyceride；High condensation point waste grease and methanol carry out esterification and transesterification or straight
It taps into row ester exchange reaction and obtains high condensation point fatty acid methyl ester；The aliphatic ester of low condensation point and the mixture of glyceride pass through ring
Oxidation reaction obtains final epoxyfatty acid ester plasticiser；High condensation point fatty acid methyl ester obtains chloro rouge by chlorination
Fatty acid methyl esters plasticizer.
In the present invention, the waste grease is selected from one or more of waste cooking oil, swill oil, gutter oil, certainly
It is also possible to one or more of above-mentioned waste cooking oil, hogwash fat, swill oil, gutter oil by the discarded of preliminary treatment
Grease, for example can remove the waste grease after non-oily impurity.It can be corn oil, soybean oil, peanut oil, palm oil, dish
The waste oil that one of seed oil, tea oil, ready-mixed oil etc. of various compositions generate, is also possible to soybean oil, peanut oil, palm
Waste cooking oil, swill oil, the gutter oil of two or more generation in oil, rapeseed oil, naturally it is also possible to be that they are only
From the waste cooking oil of generation, swill oil, gutter oil a variety of mixtures.
Contain a large amount of monoglyceride in common waste grease, wherein sour chain part is mostly long chain fatty acids, comprising few
Partial C12, C14, C16, C18, C20, it is most with C16~C18 content.
Preferably, the waste grease of the low condensation point of the invention be mainly contain C16~C18 unsaturation it is discarded
Grease.In the aliphatic ester of low condensation point and the mixture of glyceride be prepared by the present invention, the glyceride source of low condensation point
In original waste grease, the aliphatic ester of low condensation point is mainly free fatty acid and alcohol A progress in original waste grease
Esterification obtains.
High condensation point waste grease of the present invention be mainly the saturation waste grease containing C16.Preferably, this
The condensation point fatty acid methyl ester high as made from waste grease of invention mainly contains a small amount of C12, the saturated fat of C14, C18
Sour chain, and the saturated fatty acid chain of major part C16 ingredient.Be also possible in high condensation point fatty acid methyl ester used in the present invention containing
A small amount of unsaturated fatty acid methyl ester.The high condensation point fatty acid methyl ester a part obtained by the present invention is from original waste grease
In dissociate fatty acid and methanol esterification, fatty acid glycerine of the another part in original waste grease
Ester, the fatty glyceride react to obtain the high condensation point fatty acid methyl ester with methanol.
In the present invention, after waste grease is gone water removal and other non-oily impurity, freezing point is mentioned, the process that freezing point mentions
Are as follows: all greases are melted in first heating stirring, and then cooling is freezed, and are separated by solid-liquid separation, and solid portion is main comprising full
The fatty acid of sum or the high condensation point waste grease of saturated fatty acid glyceride, liquid portion are mainly comprising unsaturated fat
The low condensation point waste grease of acid or Unsaturatcd fatty acid glycerides.
For low condensation point waste grease, the present invention is using butanol, isobutanol, octanol, isooctanol in esterification process
When Deng for raw polyol, vacuum condition is introduced, is extracted in time by vacuum so that the water energy generated in esterification process is enough, ensure that ester
Change smoothly being rapidly performed by for reaction.More importantly be usually when tradition prepares plasticizer by monoglyceride and methanol into
Row ester exchange reaction is converted to fatty acid methyl ester, and the glycerol of generation needs to remove from system, this part alcohol is by unrestrained in vain
Take；And in order to meet the requirement of transesterification, needs methanol significantly excessive, and need to carry out under reflux conditions, be bound in this way
Cause the amount of the methanol of consumption to greatly increase, while also energy consumption being caused to greatly increase.Method of the invention, under vacuum conditions
Esterification is carried out, while going water removal, is also taken excessive unreacted alcohol in time away, so that the alcohol that is added and discarded
Acid in grease is directly reacted, and no longer carries out further ester exchange reaction with monoglyceride in system, so also from anti-
It answers in mechanism, further simplifies reaction process, improve reaction efficiency.
Preferably, the low condensation point waste grease is reacted with alcohol A, the mixed of low condensation point aliphatic ester and glyceride is obtained
Object is closed, specifically includes: in the presence of esterification catalyst I, alcohol A is continuously added dropwise into low condensation point waste grease, be esterified anti-
It answers, the water and most of unreacted alcohol A that during which vacuum abstraction generates (for methanol, do not need to be vacuumized, unreacted
Methanol at a temperature of high temperature esterification, can quickly be evaporated from system liquid), guarantee most or all of free rouge
Fat acid is reacted with alcohol A, and most or all of monoglycerides are not reacted with alcohol A, until acid value is less than setting
Stop reaction after value H1, obtains the aliphatic ester of the low condensation point and the mixture of glyceride.
Preferably, the low condensation point waste grease is reacted with alcohol A, the aliphatic ester and glyceride of low condensation point are obtained
Then mixture carries out epoxidation and obtains epoxy plasticizer, specifically comprises the following steps:
(I-1) add esterification catalyst I into the waste grease of low condensation point, alcohol is continuously added dropwise, carry out esterification, until
Acid value stops reaction after being less than setting value I；
(I-2) alcohol of vacuum removal remnants after being esterified removes esterification catalyst, obtain the aliphatic ester of low condensation point with
The mixture of glyceride；
(I-3) into the obtained aliphatic ester of above-mentioned low condensation point and the mixture of glyceride, formic acid, hydrogen peroxide is added
Epoxy reaction is carried out, post-processing obtains final products epoxy plasticizer.
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 alcohol A
Intermediate products after esterification decolourize.
Preferably, the acid value of the low condensation point waste grease is 3mgKOH/g~120mgKOH/g；As further
It is preferred that the acid value of the waste grease for the low condensation point that the freezing divides after mentioning is 3mgKOH/g~70mgKOH/g；Further
Preferably 10mgKOH/g~50mgKOH/g.The setting value H1 is 0.2~1mgKOH/g.As further preferred, the present invention
In, in esterification reaction process, the setting value I is 0.5mgKOH/g.Esterification, acid value are carried out under vacuum conditions
Less than stopping esterification after 0.5mgKOH/g.
Preferably, the condensation point of the low condensation point waste grease is -5~10 DEG C, and the high condensation point is discarded in the present invention
The condensation point of grease is 10 DEG C~40 DEG C.
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 obtains epoxy plasticizer through over-churning transesterification and chloro, low solidifying
The waste grease of point tests acid value, when acid value is greater than the set value I, then carries out subsequent esterification.Preferably, of the invention
In, the freezing divides temperature raising degree to be -10 DEG C~20 DEG C.
In the present invention, the alcohol A is selected from one of methanol, butanol, isobutanol, octanol, isooctanol or a variety of.As
Further preferably, the alcohol A is isooctanol.Additional amount is the 5%~40% of waste grease.
In above-mentioned steps (I-2), the alcohol of the vacuum removal remnants after esterification is removed by removing the modes such as filtering, sedimentation
Esterification catalyst.
Preferably, the esterification reaction temperature that the waste grease of low condensation point and alcohol A carry out esterification is 100~250
℃；When using methanol for esterification feed, preferably, reaction temperature is 100~120 DEG C, reaction carries out under normal pressure；When
Using one of butanol, isobutanol, octanol, isooctanol or it is a variety of when, as further preferred reaction temperature be 125 DEG C~
220 DEG C, and vacuum condition is used in esterification process, the vacuum condition is -0.09~-0.10MPa；The low condensation point is discarded
The weight ratio of grease and alcohol A and esterification catalyst I are as follows: low condensation point waste grease: alcohol A: esterification catalyst I=1:(0.02~
0.4): (0.001~0.05).Preferably, the reaction time is 2~8 hours.Preferably, the esterification catalyst is solid
Catalyst.The solid catalyst, which is more preferably activation temperature, can promote consolidating for esterification at 100~250 DEG C
Body acid catalyst.Commercially available product can be selected when actual selection according to actual needs；The solid acid catalyst is further preferred
For metallic catalyst.The metallic catalyst include but is not limited to metal sulfate (ferrous sulfate, zirconium sulfate etc.), sulfonate,
Metal oxide (for example can be stannous oxide), metal inorganic hydrochlorate, metal organic acid ester, loaded catalyst (such as can
To be Supported alumina solid acid catalyst, cerous sulfate solid acid catalyst, p-methyl benzenesulfonic acid of support type etc.).
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: dioxygen
Water=1:0.03~0.07:0.2~0.35；Preferably, reaction temperature is 60~80 DEG C；Preferably, iodine number to 3% with
Lower stopping reaction；
In the present invention, when necessary to the intermediate pint color method after esterification are as follows: using atlapulgite, active carbon or take off
The method of toner 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), is freezed
Divide and mention, first heating stirring, all greases are melted, and then cooling is freezed, and the grease of fractional saturation such as animal oil etc. is cold
Jelly comes out；The high condensation point grease of saturation that freezing comes out is made into fatty acid methyl ester and carries out chlorination again, obtains chlorinated fatty acid first
The waste grease of ester plasticiser, low condensation point tests acid value；
2) the low condensation point waste grease oil product deeper for color is added carclazyte and decolourizes；
3) a certain amount of alcohol of low condensation point waste grease addition freezed, 100 DEG C~250 DEG C of temperature, in urging for solid acid
Change 1~8 hour progress esterification of lower reaction；
4) oil being esterified is removed catalyst 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, when addition carclazyte is decolourized, the carclazyte additional amount is
The 1%~5% of oil, temperature are 80 DEG C~120 DEG C, and decoloration preferably carries out under vacuum conditions.
In the present invention, the high condensation point waste grease and methanol progress esterification and ester exchange reaction obtain high condensation point
Fatty acid methyl ester specifically includes:
In the presence of esterification catalyst II, high condensation point waste grease and methanol carry out esterification, and acid value is dropped to setting
Value H2 is hereinafter, removal esterification catalyst I；Ester exchange catalyst and methanol is added, carries out ester exchange reaction, reaction terminates, and removes
Glycerol and methanol obtain the high condensation point fatty acid methyl ester.
The present invention makes full use of the free saturated fatty acid or saturated fatty acid glyceride in waste oil, first will
Free saturated fatty acid mainly contains the fatty acid of saturated fatty acid and methanol is esterified, and then ester is recycled to hand over
It changes, saturated fatty acid glyceride or the glyceride for mainly containing saturated fatty acid glyceride is converted into methyl esters.Then pass through
Chloro obtains chlorinated fatty acid methyl esters.
Since the condensation point of saturated fatty acid or saturated fatty acid glyceride is relatively high, so meeting the useless of condensation point requirement
Grease, can directly carry out in esterification and transesterification or waste oil acid value lower than required value (1.5mgKOH/g or
1.5mgKOH/g or less) when, it can directly carry out esterification and ester exchange reaction.
The present invention mentions the low condensation point waste grease in expecting at the beginning of waste grease and high condensation point using freezing point before esterification
Waste grease separates, and carries out esterification and transesterification using the high condensation point waste grease, removes methanol, obtains the high condensation point
Fatty acid methyl ester.
In the present invention, when the acid value of obtained waste grease or the waste grease after freezing point mentions is lower than
When 1.5mgKOH/g, ester exchange reaction can be directly carried out.Most of waste grease its acid value directly obtained are significantly larger than
1.5mgKOH/g.Preferably, the acid value for the high condensation point waste grease that waste grease or freezing obtain after point mentioning be 5~
150KOH/g, at this time by the esterification of methanol, by the acid value of waste oil be reduced to setting value H2 (1.5mgKOH/g or
1.5mgKOH/g) below.
The acid value of the high condensation point waste grease is 3mgKOH/g~150mgKOH/g；The setting value H2 be 1~
2mgKOH/g。
As further refinement, the high condensation point fatty acid methyl ester obtains by the following method: waste grease is just expected
Non-oil impurity is removed, freezing point is carried out and mentions, remove low condensation point waste grease, obtain high condensation point waste grease；It is discarded to high condensation point
Methanol and acid catalyst is added in grease, carries out esterification, and acid value is dropped to H2 hereinafter, removing acid catalyst；Alkali is added to urge
Agent and methanol, obtain crude fatty acid methyl ester after transesterification, remove methanol and glyceride, after obtain the high condensation point fat
Sour methyl esters.
It is described epoxy plasticizer to be prepared by waste grease and chlorinated fatty acid methyl esters is plasticized as further preferred
In the method for agent, is just expected after removing water and other non-oily impurity by waste grease, after freezing point mentions, obtain high condensation point
Waste grease, then:
(II-1) a certain amount of methanol and acid catalyst is added in high condensation point waste grease, carries out esterification, acid value is dropped
To H2 hereinafter, removing acid catalyst；
(II-2) a certain amount of base catalyst and methanol are added, ester exchange reaction is carried out, obtains crude fatty acid methyl ester,
High condensation point fatty acid methyl ester is obtained after vacuum distillation.
(II-3) catalyst is added in obtained high condensation point fatty acid methyl ester, is passed through chlorine, obtains final products chloro
Fatty acid methyl ester.
Preferably, after obtaining high condensation point fatty acid methyl ester, be added into the fatty acid methyl ester of high condensation point catalyst or
Ultraviolet lighting is carried out, heating is passed through chlorine and carries out chlorination, and sampling and testing intermediate product density stops logical after density is qualified
Chlorine reaction, then removing residual and chlorine and the operation of the hydrogen chloride gas of production are carried out, stabilizer is added, chloro fat is obtained
Sour methyl esters product.Determination for above-mentioned density value, can according to need determination, in the present invention, preferably, the density
Value is 1~1.5g/cm3。
High condensation point fatty acid methyl ester of the invention, can raise height by waste grease freezing point by 5 DEG C~40 DEG C of condensation point
Then condensation point waste grease reacts to obtain the high fatty acid methyl ester for coagulating low iodine number with methanol.
The present invention waste grease processing using upper, by the saturated fatty acid methyl ester part wherein to epoxy without contribution
It separates, the excellent product of performance indicator can be obtained in this part material, and low condensation point unsaturation methylester portion is not suitable for doing chloro
The raw material of plasticizer obtains epoxy plasticizer by esterification and epoxidation, preferably sufficiently fully utilizes waste grease money
Source.
Preferably, being directed to high condensation point waste grease, the temperature of esterification is 60 DEG C~120 DEG C；In esterification,
The weight ratio of the waste grease and methanol and esterification catalyst II are as follows: waste grease: methanol: esterification catalyst II=1:
(0.02~0.4): (0.001~0.05)；The temperature of ester exchange reaction is 55 DEG C~85 DEG C；In ester exchange reaction, the alkali is urged
Agent can be the hydrogen of calcium oxide, calcium hydroxide, potassium hydroxide, sodium hydroxide, sodium methoxide and other the second Main Group Metal Elements
Oxide, additional amount are the 0.2%~2.0% of waste grease weight, the additional amount of methanol be waste grease weight 15~
30%.
In the present invention, the high condensation point fatty acid methyl ester, condensation point range be 5 DEG C~40 DEG C, iodine number range be 0%~
60%；Preferably, condensation point range is 10 DEG C~30 DEG C, iodine number is 0%~40%；
Preferably, the esterification catalyst II is solid catalyst.The solid catalyst further preferably activates
The solid acid catalyst that can promote esterification of the temperature at 60 DEG C~120 DEG C.It can be selected according to actual needs when actual selection
Select commercially available product；The solid acid catalyst is more preferably metallic catalyst.The metallic catalyst includes but unlimited
It (such as can in metal sulfate, sulfonate, metal oxide, metal inorganic hydrochlorate, metal organic acid ester, loaded catalyst
To be Supported alumina solid acid catalyst, cerous sulfate solid acid catalyst, activated carbon supported p-methyl benzenesulfonic acid etc.).
After the completion of transesterification: it is -0.09Mpa~-0.1Mpa in vacuum condition, is warming up to 110 DEG C of distillation removal methanol,
Continue to heat up, collects remaining fraction and obtain the high condensation point fatty acid methyl ester；In no preparation method mentioned using freezing point
In, after the completion of transesterification: being -0.09Mpa~-0.1Mpa in vacuum condition, be warming up to 110 DEG C of distillation removal methanol；Then phase
With under vacuum condition, rectifying collects 220 DEG C~240 degree of fraction, obtains the high condensation point fatty acid methyl ester.
In the present invention, catalyst used in chlorination be azo isobutyronitrile, peroxide ether and ultraviolet light etc., preferably,
Select ultraviolet light；
The chloro plasticizer compatbility that the present invention obtains is good, plasticizing efficiency is high, and wherein this method has process flow easily-controllable
The advantages that system, waste grease utilization rate is high.
The present invention provides a kind of method that waste oil from restaurants prepares epoxy plasticizer and chlorinated fatty acid methyl esters plasticizer.
It is extensive with raw material sources, it reduces environmental pollution and the harm to human health.Final products as plasticizer function admirable,
Renewable, biological degradability is good, alternative oil product plasticizer.
The final products that the present invention obtains are epoxyfatty acid ester plasticiser and chlorinated fatty acid methyl esters plasticizer；
Epoxy plasticizer is prepared with waste grease at present and is made as epoxy aliphatic acid methyl ester, although plasticization effect is preferable,
It is that flash-point is low, thermal weight loss is big, smell is big.
The present invention is using freezing fractionation technology, before esterification, in advance by high condensation point waste grease and low condensation point waste grease
Separation, is finally prepared into chlorinated fatty acid methyl esters plasticizer for the high condensation point waste grease for mainly containing saturated fatty acid, will lead
It to be finally prepared into epoxy plasticizer containing the low condensation point waste grease of unsaturated fatty acid, realize the efficient of waste grease
It utilizes.Technical process of the invention is simple, and industrialized production is controllable, is suitable for industrialized production.
Have plasticizing efficiency high by the epoxy plasticizer that the present invention is prepared, flash-point is high, thermal weight loss is small, is provided simultaneously with
Preferable lubricity.Since the saturated component in its raw material is removed, it is not easy with the plastic products that it is made fuel-displaced.
When handling low condensation point grease, the unreacted pure and mild reaction of vacuum extraction of the present invention is obtained during the reaction
Water, the separation of water alcohol is directly carried out by existing technique, alcohol obtained after separation can apply directly, be further reduced
The usage amount of solvent reduces the preparation cost of plasticizer product.
Using chlorinated fatty acid methyl esters plasticizer produced by the present invention, plasticization effect is good, good with the compatibility of PVC, is not easy
Fuel-displaced, condensation point is low, and smell is smaller than epoxy aliphatic acid methyl ester, and one of raw material is chlorine, is mostly the by-product of chlor-alkali enterprises,
Source is wide, and price is low (also losing money instead of making money sometimes), balances the by-product of chemical industry.Technical process of the invention is simple, industrial metaplasia
It produces controllably, is suitable for industrialized production.
The environmentally friendly chlorinated fatty acid methyl esters plasticizer prepared using method of the invention good, PVC product with plasticizing effect
It is not easy the advantages that fuel-displaced, condensation point is low, good and cheap.This method preparation process is simple, is suitable for industrialized production.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Embodiment can make researcher more preferably geographical
The solution present invention, but the invention is not limited in any way.
Embodiment 1
By go to remove water it is miscellaneous after discarded hogwash fat 200g, heat to 50 DEG C, all solids oil fraction dissolved,
Slow cooling carries out freezing point and mentions, and cryogenic temperature is 20 DEG C, and filters pressing after high condensation point grease cooling comes out obtains 20g high condensation point
Grease, acid value 11mgKOH/g；Obtain the low condensation point grease of 180g, acid value 20mgKOH/g.For obtained high condensation point grease
It is handled as follows respectively with low condensation point grease:
For high condensation point grease: acid catalyst 0.05g sodium bisulfate is added, chemical reagent is warming up to 100 DEG C, slowly drips
Add methanol 1.5g, sampling and testing acid value is 1.2mgKOH/g, and standing removes acid catalyst, add sodium hydroxide 0.18g and
Methanol 3.6g, stirring, 65 DEG C are reacted 3 hours, are stood to divide and are removed glycerol, obtain thick methyl esters, vacuum (- 0.09Mpa~-0.1Mpa)
It distills to 110 DEG C of removal methanol, continues heating and steam fatty acid methyl ester, glycerol remains in cucurbit, collects fraction and obtains
High condensation point fatty acid methyl ester (condensation point range is 30 DEG C, iodine number 5%), is added 0.02g azo isobutyronitrile, is heated to 90 DEG C, lead to
Enter chlorine and carry out chlorination, sampling and testing density is 1.10g/cm after reaction 3 hours3, stop logical chlorine, is filled with nitrogen, it will be residual
Chlorine and the byproduct hydrogen chloride removal stayed, obtain final products chlorinated fatty acid methyl esters.
For low condensation point grease: by acid value being added in reaction flask for 20mgKOH/g, 0.9g solid acid catalysis is added
Agent stannous oxide (Aladdin reagent), stirring, is heated to 170 DEG C, vacuumizes, and holding system internal pressure is -0.1MPa, using drop
The mode added is gradually passed through isooctanol 16.2g, and existing fatty acid and isooctanol in waste grease is made to carry out esterification, raw
At fatty acid monooctyl ester, the monoglyceride in system is held essentially constant, and is reacted 2 hours, and acid value drops to 0.45mgKOH/g, is stopped
Reaction continues to vacuumize remaining octanol removal, filters solid acid catalyst after cooling, obtains 187.6g esterification and produce
Product are loaded into epoxy reaction bottle, are heated to 60 DEG C, and the mixture of hydrogen peroxide 45g and formic acid 6.8g is then added dropwise, and are carried out
Epoxy reaction, sampling and testing iodine number, iodine number 4.2% stop reaction, stand to divide and remove sour water, a small amount of liquid alkaline is added and neutralizes, so
It is washed until neutrality, is obtained after obtained head product dewatering and filtering sweet containing octyl ester of epoxy fatty acid and epoxy with hot water afterwards
The final epoxy plasticizer product of grease.
Embodiment 2
By go to remove water it is miscellaneous after discarded gutter oil 200g, heat to 50 DEG C, all solids oil fraction dissolved,
Slow cooling carries out freezing point and mentions, and cryogenic temperature is 20 DEG C, and filters pressing after high condensation point grease cooling comes out obtains 22g high condensation point
Grease, acid value 45mgKOH/g；Obtain the low condensation point grease of 178g, acid value 65mgKOH/g.For obtained high condensation point grease
It is handled as follows respectively with low condensation point grease:
For high condensation point grease: 22g high condensation point grease being added in reaction flask, it is sub- that acid catalyst 0.11g sulfuric acid is added
Iron, chemical reagent-grade are warming up to 100 DEG C, and methanol 4.4g is slowly added dropwise, and sampling and testing acid value is 0.98mgKOH/g, and standing will
Acid catalyst removes, and adds sodium hydroxide 0.176g and methanol 4.4g, stirs, and 70 DEG C are reacted 3.5 hours, and standing point is gone sweet
Oil, obtains thick methyl esters, and vacuum distillation (- 0.09Mpa~-0.1Mpa) to 110 DEG C of removal methanol continues heating for fatty acid methyl
Ester steams, and collects fraction and obtains high condensation point fatty acid methyl ester (condensation point range is 25 DEG C, iodine number 15%), it is even that 0.028g is added
Nitrogen isobutyronitrile is heated to 90 DEG C, is passed through chlorine and carries out chlorination, sampling and testing density is 1.12g/cm after reaction 3 hours3,
Stop logical chlorine, be filled with nitrogen, remaining chlorine and byproduct hydrogen chloride are removed, final products chlorinated fatty acid methyl esters is obtained.
For low condensation point grease: the low condensation point grease of 178g being added in reaction flask, 1.6g aqueous sulfuric acid cerium solid acid is added
Catalyst (Aladdin reagent), stirring, is heated to 130 DEG C, vacuumizes, and holding system internal pressure is -0.1MPa, using dropwise addition
Mode is gradually passed through butanol 34g, so that existing fatty acid and butanol in waste grease is carried out esterification, generates fatty acid fourth
Ester reacts 3 hours, and acid value drops to 0.35mgKOH/g, stops reaction, continues to vacuumize by remaining butanol removal, after cooling
Solid acid catalyst is filtered, 192.6g esterification products are obtained, is loaded into epoxy reaction bottle, is heated to 60 DEG C, then
The mixture of hydrogen peroxide 50g and formic acid 8g is added dropwise, carries out epoxy reaction, sampling and testing iodine number, iodine number 2.5% stops anti-
It answers, stands to divide and remove sour water, a small amount of liquid alkaline is added and neutralizes, is then washed until neutrality with hot water, obtained head product is dehydrated
The final epoxy plasticizer product containing butyl ester of epoxy fatty acid and epoxy glyceride is obtained after filter.
Embodiment 3
By go to remove water it is miscellaneous after discarded gutter oil 200g, heat to 50 DEG C, all solids oil fraction dissolved,
Slow cooling carries out freezing point and mentions, and cryogenic temperature is 20 DEG C, and filters pressing after high condensation point grease cooling comes out obtains 25g high condensation point
Grease, acid value 5mgKOH/g；Obtain the low condensation point grease of 175g, acid value 15mgKOH/g, for obtained high condensation point grease
It is handled as follows respectively with low condensation point grease:
For high condensation point grease: 25g high condensation point grease is added in reaction flask, acid catalyst 0.12g zirconium sulfate is added,
Chemical reagent-grade is warming up to 100 DEG C, and methanol 3.8g is slowly added dropwise, and sampling and testing acid value is 0.96mgKOH/g, and standing urges acid
Agent removes, and adds sodium hydroxide 0.2g and methanol 4.8g, stirs, and 70 DEG C are reacted 3.5 hours, stands to divide and removes glycerol, obtains
Thick methyl esters, vacuum distillation (- 0.09Mpa~-0.1Mpa) to 110 DEG C of removal methanol continue heating and steam fatty acid methyl ester,
It collects fraction and obtains high condensation point fatty acid methyl ester (condensation point range is 25 DEG C, iodine number 22%), 0.032g azo isobutyronitrile is added,
90 DEG C are heated to, chlorine is passed through and carries out chlorination, sampling and testing density is 1.09g/cm after reaction 3 hours3, stop logical chlorine,
It is filled with nitrogen, remaining chlorine and byproduct hydrogen chloride are removed, final products chlorinated fatty acid methyl esters is obtained.
For low condensation point grease: the low condensation point grease of 175g being added in reaction flask, 1.05g Supported alumina solid is added
Acid catalyst, Qu Bu Hui Spring Biotechnology Co., Ltd, stirring, be heated to 130 DEG C, vacuumize, keep system internal pressure be-
0.09MPa is gradually passed through isobutanol 13.1g by the way of dropwise addition, make in waste grease existing fatty acid and isobutanol into
Row esterification generates fatty acid isobutyl ester, reacts 3 hours, and acid value drops to 0.4mgKOH/g, stops reaction, continues to vacuumize
Remaining isobutanol is removed, solid acid catalyst is filtered after cooling, 177.8g esterification products is obtained, is loaded into epoxy
In reaction flask, 60 DEG C are heated to, the mixture of hydrogen peroxide 36.8g and formic acid 5.69g is then added dropwise, carries out epoxy reaction, sampling
Iodine number is tested, iodine number 2.5% stops reaction, stands to divide and removes sour water, a small amount of liquid alkaline is added and neutralizes, is then washed with hot water
Until neutrality, the most terminal ring containing epoxyfatty acid isobutyl ester and epoxy glyceride is obtained after obtained head product dewatering and filtering
Oxygen plasticizer product.
And existing waste oil technical treatment is utilized, first the free fatty acid of the above-mentioned waste grease of 200g to be removed, acid value drop
To 1.5mgKOH/g hereinafter, obtaining the low acid value glyceride of about 186g, (the quality of waste grease and methanol is subsequently placed in methanol
Than for 1:0.2), back flow reaction (60 DEG C~80 DEG C), reaction time 2.5h, redistillation obtains the fatty acid methyl ester of about 178.9g,
Then identical epoxidation reaction is carried out, contrast sample epoxy aliphatic acid methyl ester is obtained, the yield of the waste oil of the prior art is too late
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,
Pure and mild aqueous solution reuse directly can certainly be applied to other techniques into other techniques, or by isolated alcohol
In.
Performance detection:
The epoxy plasticizer that Examples 1 to 3 is prepared, according to " GBT+1671-2008+ plasticizer flashing test
+ Cleveland is open agar diffusion method ", volatility according to " measurement of GBT 1669-2001 plasticizer heating loss ", carry out performance inspection
It surveys, while the epoxy aliphatic acid methyl ester obtained with existing waste oil disposal technology compares, as a result as follows:
| Epoxy 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 obtained product of embodiment according to the invention is than the production (i.e. above-mentioned " ring that existing waste oil disposal technology obtains
Oxygen fatty acid methyl ester ") flash-point is high, and heating loss is small.
By the epoxy plasticizer in above-mentioned several embodiments according to weight ratio: PVC 100, plasticizer 40, stabilizer 3
Formula, the tabletting on twin-roll machine, twin-roll machine temperature set 175 DEG C, and the formula of embodiment 1,2,3 is plasticized quickly, with epoxidised fatty
The plasticizing rate of sour methyl esters is suitable, and the gas of volatilization is less, and the gas of epoxy methyl esters volatilization is more.Epoxyfatty acid simultaneously
The PVC material of methyl esters formula is easier to be sticked on roller, bad to fall off, and after adding a small amount of lubricant PE wax in this recipe, holds
It is easily separated with roller, effect is identical with the PVC obtained with embodiment material effect.Illustrate to be reduced with product produced by the present invention
The yield of VOC in production process, 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 requires 0.3 part of PE wax, and 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
The measurement activated carbon method of 4458-2012 plastic plasticizer loss ", test result is as follows:
| Epoxy 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 increased with product produced by the present invention than being used as the epoxy methyl esters made from existing method
When moulding agent, plastic products go out oiliness carefully.
The chlorinated fatty acid methyl esters plasticizer condensation point that Examples 1 to 3 is prepared is according to " Imported and exported animals grease rouge
Fat acid cure solid point measuring method SNT 0801.17 " freezing point is -8 DEG C, it is solidifying than 5~15 DEG C of existing epoxy aliphatic acid methyl ester
Solid point is low, and client is facilitated to use.
By the chloro plasticizer in above-mentioned several embodiments according to weight ratio: PVC 100, plasticizer 40, stabilizer 3 are matched
Side, the tabletting on twin-roll machine, twin-roll machine temperature set 175 DEG C, the chlorinated fatty acid first being prepared using embodiment 1,2,3
The formula of ester plasticiser is plasticized quickly, slightly slower than the plasticizing rate of epoxy aliphatic acid methyl ester, and the gas of volatilization is less, smaller.
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
The measurement activated carbon method of 4458-2012 plastic plasticizer loss ", test result is as follows:
| Plasticizer | It is fuel-displaced, % |
| Embodiment 1 | 10.12 |
| Embodiment 2 | 10.01 |
| Embodiment 3 | 10.03 |
| Epoxy aliphatic acid methyl ester | 13.68 |
From the above it is found that with chlorinated fatty acid methyl esters plasticizer product ratio existing method system produced by the present invention
When being used as plasticizer of the epoxy methyl esters obtained, plastic products are not easy fuel-displaced.
Claims (10)
1. a kind of method for preparing epoxy plasticizer and chloro plasticizer by waste grease characterized by comprising will discard
Grease carries out freezing point and mentions, and obtains high condensation point waste grease and low condensation point waste grease；Low condensation point waste grease is reacted with alcohol A,
Obtain the aliphatic ester of low condensation point and the mixture of glyceride；High condensation point waste grease and methanol carry out esterification and transesterification
Reaction or directly progress transesterification obtain high condensation point fatty acid methyl ester；The aliphatic ester of low condensation point and the mixture warp of glyceride
It crosses epoxidation reaction and obtains final epoxyfatty acid ester plasticiser；High condensation point fatty acid methyl ester obtains chloro by chlorination
Fatty acid methyl ester plasticiser.
2. the method according to claim 1 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the low condensation point waste grease is reacted with alcohol A, obtains the aliphatic ester of low condensation point and the mixture of glyceride, specific to wrap
It includes: in the presence of esterification catalyst I, alcohol A being continuously added dropwise into low condensation point waste grease, carries out esterification, until acid value is small
Stop reaction after setting value H1, obtains the aliphatic ester of the low condensation point and the mixture of glyceride.
3. the method according to claim 1 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the high condensation point waste grease and methanol progress esterification and ester exchange reaction obtain high condensation point fatty acid methyl ester, have
Body includes:
In the presence of esterification catalyst II, high condensation point waste grease and methanol carry out esterification, and acid value is dropped to setting value H2
Hereinafter, removal esterification catalyst II；Ester exchange catalyst and methanol is added, carries out ester exchange reaction, reaction terminates, and removes glycerol
And methanol, obtain the high condensation point fatty acid methyl ester.
4. the method according to claim 1 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: freezing divides temperature raising degree to be -10 DEG C~20 DEG C.
5. the method according to claim 2 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the acid value of the low condensation point waste grease is 3mgKOH/g~120mgKOH/g；The setting value H1 be 0.2~
1mgKOH/g。
6. the method according to claim 3 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the acid value of the high condensation point waste grease is 3mgKOH/g~150mgKOH/g；The setting value H2 is 1~2mgKOH/
g。
7. the method according to claim 2 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: esterification reaction temperature is 100~250 DEG C；The weight ratio of low the condensation point waste grease and alcohol A and esterification catalyst I are as follows:
Low condensation point waste grease: alcohol A: esterification catalyst I=1:(0.02~0.4): (0.001~0.05).
8. the method according to claim 2 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the alcohol A is selected from one of methanol, butanol, isobutanol, octanol, isooctanol or a variety of；When selection butanol, isobutanol,
One of octanol, isooctanol or it is a variety of when, esterification carry out under vacuum conditions, vacuum condition be -0.09~-0.10MPa.
9. the method according to claim 3 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the temperature of esterification is 60 DEG C~120 DEG C；In esterification, the waste grease and methanol and esterification catalyst II
Weight ratio are as follows: waste grease: methanol: esterification catalyst II=1:(0.02~0.4): (0.001~0.05)；Ester exchange reaction
Temperature be 55 DEG C~85 DEG C；In ester exchange reaction, the base catalyst can be calcium oxide, calcium hydroxide, potassium hydroxide, hydrogen-oxygen
Change the hydroxide of sodium, sodium methoxide and other the second Main Group Metal Elements, additional amount be waste grease weight 0.2%~
2.0%, the additional amount of methanol is the 15~30% of waste grease weight.
10. the method according to claim 1 for preparing epoxy plasticizer and chloro plasticizer by waste grease, feature
Be: the waste grease is selected from one of waste cooking oil, hogwash fat, swill oil, gutter oil or the first of a variety of compositions is expected,
It is either above-mentioned just to expect and remove the processing material that non-oil impurity obtains.
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