CN109971551A - A kind of method and product preparing environmentally friendly chloro plasticizer by waste grease - Google Patents
A kind of method and product preparing environmentally friendly chloro plasticizer by waste grease Download PDFInfo
- Publication number
- CN109971551A CN109971551A CN201910243298.1A CN201910243298A CN109971551A CN 109971551 A CN109971551 A CN 109971551A CN 201910243298 A CN201910243298 A CN 201910243298A CN 109971551 A CN109971551 A CN 109971551A
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- waste grease
- acid methyl
- methyl ester
- condensation point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a kind of methods for preparing environmentally friendly chloro plasticizer by waste grease, comprising: using waste grease as raw material, carries out esterification and transesterification with methanol, obtains the mainly high condensation point fatty acid methyl ester containing saturated fatty acid methyl ester；High condensation point saturated fatty acid methyl ester is passed through chlorine under the action of catalyst, and post-processing obtains chlorinated fatty acid methyl esters.Have many advantages, such as that plasticizing effect is good, PVC product is not easy that fuel-displaced, condensation point is low, good and cheap using environmentally friendly chlorinated fatty acid methyl esters plasticizer prepared by method of the invention.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 environmentally friendly chloro 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., but is planted
Saturated component in object grease cannot will affect on the contrary plasticizer and polychlorostyrene to the no effect of the plasticizing of polyvinyl chloride by epoxy
The compatibility of ethylene, oil yield greatly increase.
Summary of the invention
The present invention provides a kind of preparations of biomass environment-friendly chloro plasticizer that can be realized waste grease comprehensive utilization
Method.
Invention also provides a kind of chlorinated fatty acid methyl esters plasticizer being prepared by waste grease, the plasticizer
With the compatibility of polyvinyl chloride it is good, be not easy it is fuel-displaced, it is good and cheap, have very high cost performance.
A method of environmentally friendly chloro plasticizer is prepared by waste grease, comprising: using waste grease as raw material, with methanol into
Row esterification and transesterification directly carry out transesterification with methanol, obtain the mainly high condensation point fatty acid containing saturated fatty acid methyl ester
Methyl esters；High condensation point saturated fatty acid methyl ester is passed through chlorine under the action of catalyst, and post-processing obtains chlorinated fatty acid methyl esters.
The present invention makes full use of the saturated fatty acid glyceride of free saturated fatty acid or high condensation point in waste oil,
By the saturated fatty acid of free high condensation point or mainly contain the fatty acid of saturated fatty acid and methanol is esterified first, so
After recycle transesterification, saturated fatty acid glyceride or the glyceride for mainly containing saturated fatty acid glyceride are converted into first
Ester.Then pass through chloro, obtain chlorinated fatty acid methyl esters.
Since the condensation point of saturated fatty acid or saturated fatty acid glyceride is relatively high, so meeting the waste oil of condensation point requirement
Rouge, can directly carry out esterification and transesterification, either when collect waste oil in acid value lower than required value (1.5mgKOH/g or
1.5mgKOH/g or less) when, ester exchange reaction can be directly carried out without esterification.When waste grease condensation point is unsatisfactory for requiring
When, high condensation point fatty acid methyl ester can be obtained first, then carries out subsequent chlorination reaction again by the following two kinds method:
First method, expect at the beginning of point mentioning removal waste grease using freezing before esterification in low condensation point waste grease,
High condensation point waste grease raw material is obtained, carries out esterification and transesterification or directly and first using the high condensation point waste grease and methanol
Alcohol carries out transesterification, removes methanol, obtains the high condensation point fatty acid methyl ester；Alternatively, directly being utilized using second method
Waste grease, which is just expected, carries out esterification and transesterification with methanol, obtains crude fatty acid methyl ester, and rectifying obtains the high condensation point rouge
Fatty acid methyl esters.
The setting value or required value are 1~2mgKOH/g.
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 waste grease that waste grease or freezing divide after mentioning is 5~150KOH/g, at this time
By the esterification of methanol, the acid value of waste oil is reduced to 1.5mgKOH/g or 1.5mgKOH/g or less.
As further refinement, two methods are respectively as follows:
First method, the high condensation point fatty acid methyl ester, obtains by the following method: waste grease is just expected, and it is non-to remove
Oily impurity carries out freezing point and mentions, removes low condensation point waste grease, obtain high condensation point waste grease；Add to high condensation point waste grease
Enter methanol and acid catalyst, carry out esterification, acid value is dropped into 1.5mgKOH/g or 1.5mgKOH/g and is urged hereinafter, removing acid
Agent；Base catalyst and methanol are added, crude fatty acid methyl ester is obtained after transesterification, and (waste grease after freezing point mentions is initial
Material can directly carry out ester exchange reaction when meeting acid value requirement), remove methanol and glyceride, after obtain the high condensation point
Fatty acid methyl ester.
Second method, the high condensation point fatty acid methyl ester, obtains by the following method: waste grease is just expected, and it is non-to remove
Methanol and acid catalyst is added in oily impurity, carries out esterification, acid value is dropped into 1.5mgKOH/g or 1.5mgKOH/g hereinafter,
Remove acid catalyst；Base catalyst and methanol are added, crude fatty acid methyl ester is obtained after transesterification (when giving up for the non-oil impurity of removing
Abandon grease just to expect when meeting acid value requirement, can directly carry out ester exchange reaction), methanol is removed, rectifying obtains target fraction:
High condensation point fatty acid methyl ester.
Preferably, the method for preparing chlorinated fatty acid methyl esters plasticizer by waste grease includes the following steps:
(1) waste grease is just expected after removing water and other non-oily impurity, freezing point mentions: first heating stirring, by institute
There is grease thawing, then cooling is freezed, and the waste grease of high condensation point is obtained after filters pressing, the waste grease of low condensation point separately does him
With；
(2) a certain amount of methanol and acid catalyst is added in high condensation point waste grease, carries out esterification, acid value is dropped to and is set
(for example setting value is 1.5mgKOH/g) below definite value, removes acid catalyst；
(3) a certain amount of base catalyst and methanol are added, ester exchange reaction is carried out, obtains crude fatty acid methyl ester, vacuum
High condensation point fatty acid methyl ester is obtained after distillation.
(4) catalyst is added in obtained high condensation point fatty acid methyl ester, is passed through chlorine, obtains final products chloro fat
Sour methyl esters.
Or it comprises the steps of:
(1) waste grease is just expected and removes non-oil impurity, a certain amount of methanol and acid catalyst is added, be esterified anti-
It answers, acid value is dropped into setting value (for example setting value is 1.5mgKOH/g), removes acid catalyst；
(2) a certain amount of base catalyst and methanol are added, obtains crude fatty acid methyl ester after transesterification；
(3) saturation methacrylate compound is cut into, obtains the high condensation point fatty acid methyl ester by rectification under vacuum；
(4) catalyst is added in obtained high condensation point fatty acid methyl ester, is passed through chlorine, obtains final products chloro fat
Sour methyl esters.
In above-mentioned steps (3), the low condensation point saturated fatty acid methyl ester that rectifying obtains can directly carry out epoxidation reaction, obtain
To epoxy plasticizer.
From the point of view of operation ease and energy consumption size, preferably, we prepare institute using first method
The high condensation point fatty acid methyl ester stated.Using first method, does not need to carry out subsequent distillation operation, operate simpler, energy
It is lower to consume cost.
A method of chlorinated fatty acid methyl esters plasticizer being prepared by waste grease, comprising: to what is prepared by waste grease
Catalyst is added in the fatty acid methyl ester of high condensation point or carries out ultraviolet lighting, heating is passed through chlorine and carries out chlorination, sampling
Intermediate product density is tested, stops logical chlorine reaction after density is qualified, then carry out the hydrogen chloride gas of removing residual and chlorine and production
Gymnastics is made, and adds stabilizer, obtains chlorinated fatty acid methyl esters product.Determination for above-mentioned density value, can according to need
It determines, 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 Gao Ning by waste grease freezing point by 5 DEG C~40 DEG C of condensation point
Then point waste grease is reacted to obtain the high fatty acid methyl ester for coagulating low iodine number with methanol, can also be reacted by waste grease and methanol
It after obtaining crude fatty acid methyl ester, is evaporated in vacuo, cutting obtains saturated fatty acid methyl ester part.
The present invention waste grease processing using upper, will the wherein saturated fatty acid methyl ester part to epoxy without contribution point
It separates out and, 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 increasing
The raw material for moulding agent separately does him and uses, preferably sufficiently fully utilizes waste grease resource.
In the present invention, the waste grease is just expected or waste grease is in waste cooking oil, swill oil, gutter oil
It is one or more kinds of, naturally it is also possible to be one or more of above-mentioned waste cooking oil, hogwash fat, swill oil, gutter oil warp
The waste grease of preliminary treatment is crossed, for example can remove the waste grease after non-oily impurity.Can be corn oil, soybean oil,
The waste oil that one of peanut oil, palm oil, rapeseed oil, tea oil, ready-mixed oil etc. of various compositions generate, is also possible to soybean
Oil, peanut oil, palm oil, in rapeseed oil two or more generation waste cooking oil, swill oil, gutter oil, certainly
It can be a variety of mixtures of waste cooking oil, swill oil, gutter oil that they generate alone.
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, of the invention is described by waste grease
High condensation point fatty acid methyl ester obtained mainly contains a small amount of C12, the saturated fatty acid chain of C14, C18, and major part C16 ingredient
Saturated fatty acid chain.It is 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 fatty acid to be dissociated in original waste grease by the obtained high condensation point fatty acid methyl ester a part of the present invention with
The esterification of methanol, fatty glyceride of the another part in original waste grease, the fatty glyceride with
Methanol reacts to obtain the high condensation point fatty acid methyl ester.
In the present invention, when freezing point mentions, first heating stirring (for example can be and be warming up to 40~60 DEG C), all greases are melted
Change, then cooling is freezed, and the freezings such as the grease of fractional saturation such as animal oil are come out；The high condensation point oil of the saturation that freezing comes out
Rouge is step by step rapid under continuing.
Preferably, the freezing divides temperature raising degree to be -10 DEG C~20 DEG C.
In the present invention, in the technique of not chilled point of the step of mentioning, fatty acid methyl ester is made by waste grease and carries out vacuum
When rectifying, since the smaller boiling point of molecular weight is lower, C12, C14, C16 saturated fatty acid methyl ester component are first distilled off, doping
Small part C18 methyl esters collects this fractional saturation fatty acid methyl ester to obtain high condensation point fatty acid methyl ester of the present invention,
Remaining is unsaturated methyl esters.
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%；
In the present invention, in esterification, the weight ratio of the waste grease and methanol and acid catalyst are as follows: waste grease:
Methanol: acid catalyst=1:(0.02~0.4): (0.001~0.05).
In the present invention, in ester exchange reaction, the base catalyst can be calcium oxide, calcium hydroxide, potassium hydroxide, hydroxide
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.
In the present invention, the temperature of esterification is 60 DEG C~120 DEG C；Further preferably 100~120 DEG C；Transesterification is anti-
The temperature answered is 55 DEG C~85 DEG C.
Preferably, the esterification catalyst is solid catalyst.The solid catalyst further preferably activates temperature
Spend the solid acid catalyst that can promote esterification at 60 DEG C~120 DEG C.It can be selected according to actual needs when actual selection
Commercially available product；The solid acid catalyst is more preferably metallic catalyst.The metallic catalyst includes but is not limited to
Metal sulfate (such as ferrous sulfate), metal hydrogen sulfate (such as sodium bisulfate), sulfonate, metal oxide, metal without
Machine hydrochlorate, metal organic acid ester, loaded catalyst (for example can be Supported alumina solid acid catalyst, cerous sulfate solid
Acid catalyst, p-methyl benzenesulfonic acid of property charcoal load etc.).Preferably, transesterification is complete in the preparation method mentioned using freezing point
Cheng Hou: being -0.09Mpa~-0.1Mpa in vacuum condition, is warming up to 110 DEG C of distillation removal methanol, continues to heat up, collect remaining
Fraction obtains the high condensation point fatty acid methyl ester；In no preparation method mentioned using freezing point, after the completion of transesterification: true
Empty condition is -0.09Mpa~-0.1Mpa, is warming up to 110 DEG C of distillation removal methanol；Then under identical vacuum condition, rectifying is received
The fraction of 220 DEG C~240 degree of collection, 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,
Ultraviolet light is selected, or directly carries out chlorination with thermal energy；
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 chlorinated fatty acid methyl esters plasticizer；
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, and smell is big, is increased using chlorinated fatty acid methyl esters produced by the present invention
Agent is moulded, plasticization effect is good, good with the compatibility of PVC, is not easy fuel-displaced, and condensation point is low, and smell is smaller than epoxy aliphatic acid methyl ester, and raw material
One of be chlorine, be mostly the by-product of chlor-alkali enterprises, source is wide, and price is low (also losing money instead of making money sometimes), balances chemical industry
By-product.Technical process of the invention is simple, and industrialized production is controllable, 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 be such that researcher more fully understands
The 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, delay
Slow cool down carries out freezing point and mentions, and cryogenic temperature is 20 DEG C, filters pressing after high condensation point grease cooling comes out, obtained high condensation point grease
Test acid value be 11mgKOH/g, acid catalyst 0.5g sodium bisulfate is added, chemical reagent is warming up to 100 DEG C, is slowly added dropwise
Methanol 15g, sampling and testing acid value are 1.2mgKOH/g, and standing removes acid catalyst, add sodium hydroxide 1.8g and methanol
36g, stirring, 65 DEG C are reacted 3 hours, are stood to divide and are removed glycerol, and thick methyl esters is obtained, and vacuum (- 0.09Mpa~-0.1Mpa) distillation is arrived
110 DEG C of removal methanol continue heating and steam fatty acid methyl ester, collect fraction and obtain high condensation point fatty acid methyl ester (condensation point range
It is 30 DEG C, iodine number 5%), 0.2g azo isobutyronitrile is added, is heated to 90 DEG C, is passed through chlorine and carries out chlorination, reaction 3 is small
When after sampling and testing density be 1.10g/cm3, stop logical chlorine, be filled with nitrogen, remaining chlorine and byproduct hydrogen chloride are removed,
Obtain final products chlorinated fatty acid methyl esters.
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, delay
Slow cool down carries out freezing point and mentions, and cryogenic temperature is 20 DEG C, filters pressing after high condensation point grease cooling comes out, obtained high condensation point grease
Test acid value be 45mgKOH/g, acid catalyst 1.0g ferrous sulfate is added, chemical reagent-grade is warming up to 100 DEG C, slowly drips
Add methanol 40g, sampling and testing acid value is 0.98mgKOH/g, and standing removes acid catalyst, add sodium hydroxide 1.6g and
Methanol 45g, stirring, 70 DEG C are reacted 3.5 hours, are stood to divide and are removed glycerol, obtain thick methyl esters, be evaporated in vacuo (- 0.09Mpa~-
0.1Mpa) to 110 DEG C of removal methanol, continue heating and steam fatty acid methyl ester, collects fraction and obtain high condensation point fatty acid methyl ester
(condensation point range is 25 DEG C, iodine number 15%), is added 0.25g azo isobutyronitrile, is heated to 90 DEG C, and it is anti-to be passed through chlorine progress chloro
It answers, sampling and testing density is 1.12g/cm after reaction 3 hours3, stop logical chlorine, nitrogen be filled with, by remaining chlorine and by-product
Hydrogen chloride removal, obtains final products chlorinated fatty acid methyl esters.
Embodiment 3
By go to remove water it is miscellaneous after discarded gutter oil 200g, test acid value is 102mgKOH/g, be added acid catalyst 1.5g from
The activated carbon supported p-methyl benzenesulfonic acid of system, is warming up to 100 DEG C, methanol 55g is slowly added dropwise, sampling and testing acid value is
1.31mgKOH/g, standing remove acid catalyst, add sodium hydroxide 2.0g and methanol 50g, stir, and 70 DEG C of reactions 3.5 are small
When, it stands to divide and removes glycerol, obtain thick methyl esters, vacuum (- 0.09Mpa~-0.1Mpa) is distilled to 110 DEG C of removal methanol, after of continuing rising
Temperature, by fatty acid methyl ester rectifying, is collected front-end volatiles (220 DEG C~240 degree of temperature) and obtains high condensation point fatty acid methyl with kirschner Rectification head
Ester (condensation point range be 20 DEG C, 20%) is added 0.15g azo isobutyronitrile, is heated to 100 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, nitrogen be filled with, by remaining chlorine and by-product chlorine
Change hydrogen removal, obtains final products chlorinated fatty acid methyl esters.
The plasticizer condensation point that Examples 1 to 3 is prepared is according to " Imported and exported animals oil fatty acid kryoscopy side
Method SNT 0801.17 " freezing point be -8 DEG C, freezing point of 5~15 DEG C than epoxy aliphatic acid methyl ester is low, and client is facilitated to use.
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, than the plasticizing rate of epoxy aliphatic acid methyl ester
Slightly slow, 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 4458-
The measurement activated carbon method of 2012 plastic plasticizers loss ", test result is as follows:
| Plasticizer | It is fuel-displaced, % |
| Embodiment 1 | 10.12 |
| Embodiment 2 | 10.01 |
| Embodiment 3 | 9.93 |
| 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, plastic products are not easy fuel-displaced.
Claims (10)
1. a kind of method for preparing environmentally friendly chloro plasticizer by waste grease characterized by comprising with waste grease be original
Material carries out esterification and transesterification with methanol or directly carries out transesterification with methanol, obtains mainly containing saturated fatty acid methyl ester
High condensation point fatty acid methyl ester；High condensation point saturated fatty acid methyl ester is passed through chlorine under the action of catalyst, and post-processing obtains chloro rouge
Fatty acid methyl esters.
2. the method according to claim 1 for preparing environmentally friendly chloro plasticizer by waste grease, it is characterised in that: be esterified
The preceding low condensation point waste grease mentioned in removal waste grease using freezing point, is obtained high condensation point waste grease raw material, utilizes the height
Condensation point waste grease and methanol carry out esterification and transesterification or directly carry out transesterification with methanol, remove methanol and glycerol, obtain
To the high condensation point fatty acid methyl ester；Alternatively, directly carrying out esterification and transesterification or direct using waste grease and methanol
Transesterification is carried out with methanol, obtains crude fatty acid methyl ester, rectifying obtains the high condensation point fatty acid methyl ester.
3. the method according to claim 1 for preparing environmentally friendly chloro plasticizer by waste grease, which is characterized in that the height
Condensation point fatty acid methyl ester, obtains by the following method: waste grease being carried out freezing point and is mentioned, low condensation point waste grease is removed, obtains
High condensation point waste grease；Methanol and acid catalyst is added to high condensation point waste grease, carries out esterification, acid value is dropped into setting
Value I is hereinafter, remove acid catalyst；Add base catalyst and methanol, obtain crude fatty acid methyl ester after transesterification, removal methanol and
Glycerol obtains the high condensation point fatty acid methyl ester；Alternatively, the high condensation point fatty acid methyl ester, obtains by the following method: to useless
It abandons and methanol and acid catalyst is added in grease, carry out esterification, acid value is dropped into setting value II hereinafter, removing acid catalyst；
Base catalyst and methanol are added, crude fatty acid methyl ester is obtained after transesterification, rectifying obtains high condensation point fatty acid methyl ester.
4. the method according to claim 2 for preparing environmentally friendly chloro 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 according to claim 2 for preparing environmentally friendly chloro plasticizer by waste grease, which is characterized in that esterification is anti-
Ying Zhong, the weight ratio of the waste grease and methanol and acid catalyst are as follows: waste grease: methanol: acid catalyst=1:(0.02~
0.4): (0.001~0.05)；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.
6. the method according to claim 2 for preparing environmentally friendly chloro plasticizer by waste grease, which is characterized in that esterification is anti-
The temperature answered is 60 DEG C~120 DEG C；The temperature of ester exchange reaction is 55 DEG C~85 DEG C.
7. the method according to claim 3 for preparing environmentally friendly chloro plasticizer by waste grease, which is characterized in that using
In the preparation method that freezing point mentions, after the completion of transesterification: being -0.09Mpa~-0.1Mpa in vacuum condition, be warming up to 110 DEG C of steamings
It evaporates except methanol, continues to heat up, collect remaining fraction and obtain the high condensation point fatty acid methyl ester；Freezing point is used to mention no
In preparation method, after the completion of transesterification: being -0.09Mpa~-0.1Mpa in vacuum condition, be warming up to 110 DEG C of distillation removal first
Alcohol；Then under identical vacuum condition, rectifying collects 220 DEG C~240 degree of fraction, obtains the high condensation point fatty acid methyl ester.
8. the method according to claim 1 for preparing environmentally friendly chloro plasticizer by waste grease, which is characterized in that the height
Condensation point fatty acid methyl ester, iodine number range are 0~60%.
9. the method according to claim 1 for preparing environmentally friendly chloro plasticizer by waste grease, which is characterized in that described useless
First expecting of the abandoning grease selected from one or more of waste cooking oil, hogwash fat, swill oil, gutter oil composition, or on
It states just to expect and removes the processing material that non-oil impurity obtains.
10. a kind of prepare environmentally friendly chloro plasticizer by waste grease, which is characterized in that it is as described in any one of claim 1~9
Method be prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910243298.1A CN109971551B (en) | 2019-03-28 | 2019-03-28 | Method for preparing environment-friendly chlorinated plasticizer from waste oil and fat and product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910243298.1A CN109971551B (en) | 2019-03-28 | 2019-03-28 | Method for preparing environment-friendly chlorinated plasticizer from waste oil and fat and product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109971551A true CN109971551A (en) | 2019-07-05 |
| CN109971551B CN109971551B (en) | 2022-09-20 |
Family
ID=67081308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910243298.1A Active CN109971551B (en) | 2019-03-28 | 2019-03-28 | Method for preparing environment-friendly chlorinated plasticizer from waste oil and fat and product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109971551B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2021212703A1 (en) * | 2020-04-20 | 2021-10-28 | 山东岩海建设资源有限公司 | Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor |
| CN115181328A (en) * | 2022-07-21 | 2022-10-14 | 浙江嘉澳环保科技股份有限公司 | Preparation method of chlorinated epoxy fatty acid methyl ester compound or main plasticizer and product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818125A (en) * | 2015-05-04 | 2015-08-05 | 浙江大学 | Method for using waste oil and grease as raw material to prepare fatty acid methyl ester |
| CN105154225A (en) * | 2015-10-09 | 2015-12-16 | 湖北天基生物能源科技发展有限公司 | Dry fractionation method for swill-cooked dirty oil fatty acid methyl ester |
-
2019
- 2019-03-28 CN CN201910243298.1A patent/CN109971551B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818125A (en) * | 2015-05-04 | 2015-08-05 | 浙江大学 | Method for using waste oil and grease as raw material to prepare fatty acid methyl ester |
| CN105154225A (en) * | 2015-10-09 | 2015-12-16 | 湖北天基生物能源科技发展有限公司 | Dry fractionation method for swill-cooked dirty oil fatty acid methyl ester |
Non-Patent Citations (1)
| Title |
|---|
| 莫贯田，等: "氯化脂肪酸甲酯合成及应用", 《广州化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021212703A1 (en) * | 2020-04-20 | 2021-10-28 | 山东岩海建设资源有限公司 | Chlorinated fatty acid ester environment-friendly plasticizer and preparation method therefor |
| 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 |
| CN115181328A (en) * | 2022-07-21 | 2022-10-14 | 浙江嘉澳环保科技股份有限公司 | Preparation method of chlorinated epoxy fatty acid methyl ester compound or main plasticizer and product |
| CN115181328B (en) * | 2022-07-21 | 2024-04-02 | 浙江嘉澳环保科技股份有限公司 | Preparation method of chloroepoxy fatty acid methyl ester compound or primary plasticizer and product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109971551B (en) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109971551A (en) | A kind of method and product preparing environmentally friendly chloro plasticizer by waste grease | |
| CN109971552A (en) | A method of epoxy plasticizer and chloro plasticizer are prepared by waste grease | |
| Vicente et al. | Integrated biodiesel production: a comparison of different homogeneous catalysts systems | |
| JP4990455B2 (en) | Single-phase process to produce fatty acid methyl esters from mixtures of triglycerides and fatty acids | |
| Stavarache et al. | Ultrasonic versus silent methylation of vegetable oils | |
| CN103988266B (en) | As insulation and heat transfer unit (HTU) fluid composition, comprise the electric device of described compositionss and the preparation method of such composition | |
| Alabi et al. | Analysis of Fatty Acid Composition of Thevetia peruviana and Hura crepitans Seed oils using GC-FID | |
| CN104186705B (en) | Method based on enzymatic acidolysis palmitic acid three Lipase absobed structured lipid | |
| Ziyada et al. | Physical and ChemicalCharacteristics of Citrullus lanatus Var. Colocynthoide Seed Oil | |
| CN102311883A (en) | Method for preparing high-purity biodiesel | |
| CN104212848B (en) | Microbial grease preparation method by carbon source of biological diesel oil byproduct crude glycerine | |
| CN102228092A (en) | Method for preparing low/zero-trans fatty acid shortening by enzymatic interesterification | |
| CN100999698A (en) | Greasy of containing glycerin ester type conjugate linolic acid and protuction process thereof | |
| CN105001922B (en) | The preparation method of biodiesel | |
| CN108084020A (en) | A kind of method that omega-7 aliphatic esters are prepared using grease as raw material | |
| CN101108338A (en) | Resin carrier solid alkali catalyst and method for synthesizing biological diesel oil with animal vegetable oil | |
| CN102807470A (en) | Method for preparing high-grade aliphatic alcohol | |
| Rachmaniah et al. | A study on acid-catalyzed transesterification of crude rice bran oil for biodiesel production | |
| CN103087788A (en) | Method for preparing biodiesel by using high-acid value oil | |
| CN109970688A (en) | A kind of method and product preparing epoxy plasticizer by waste grease | |
| CN105475517B (en) | A kind of human body easily absorbs baking basic oil and preparation method thereof | |
| CN1974724B (en) | High efficiency preparation process of biological diesel oil | |
| CN104152501A (en) | Gradual cooling auxiliary enzymatic method for glycerolysis preparation of lard diglyceride | |
| CN108927217A (en) | A kind of solid base catalyst based on polyaniline-coated carbon material and its application in preparation biodiesel | |
| CN108927218A (en) | A kind of polyaniline-coated biology carbon material and its preparing the application in solid base |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |