CN108727308A - A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel - Google Patents
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel Download PDFInfo
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- CN108727308A CN108727308A CN201810469604.9A CN201810469604A CN108727308A CN 108727308 A CN108727308 A CN 108727308A CN 201810469604 A CN201810469604 A CN 201810469604A CN 108727308 A CN108727308 A CN 108727308A
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- different monooctyl
- monooctyl ester
- biodiesel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a kind of technique preparing the different monooctyl ester of epoxyfatty acid based on biodiesel, which includes the following steps：Using biodiesel as raw material, in the presence of solid base catalyst, ester exchange reaction occurs with isooctanol, after reaction the different monooctyl ester of rectifying is obtained through evaporation removing isooctanol, thick different monooctyl ester rectification working process, the different monooctyl ester of gained carries out epoxidation reaction with formic acid, hydrogen peroxide, is layered, washes after reaction, flash distillation obtains the different monooctyl ester of high-quality product epoxyfatty acid.Present invention process high-efficiency environment friendly, axunge interchange esterification conversion rate is high, and solid catalyst may be reused, heat recovery and utilization, and epoxy wastewater processing is simple, is suitble to industrialized production.Energy steady production of the invention obtains the different monooctyl ester of epoxyfatty acid of high-quality, is widely used in the fields such as plastic processing as green bio base auxiliary agent, can improve the added value of biodiesel, promotes Biodiesel fast-developing.
Description
Technical field
The invention belongs to biodiesel Downstream Products technical fields, and in particular to one kind preparing ring based on biodiesel
The technique of oxygen fatty acid isooctyl.
Background technology
It is a series of high additional by platform chemicals exploitation synthesis of biodiesel with greatly developing for Biodiesel
Value chemical product becomes hot spot instantly.This can not only improve biodiesel added value, be also beneficial to domestic Biodiesel
Healthy and sustainable development.Wherein, the different monooctyl ester of epoxyfatty acid as it is a kind of green, environmental protection biological base auxiliary agent in recent years by state
Inside and outside extensive concern.It can be used as a kind of environment-friendly plasticizer, partially or completely replace adjacent benzoic acid ester plasticizer（As DOP,
DBP etc.）, it is applied to PVC industries；It is also used as stabilizer, patch plus agent and lubricant etc..In addition, the different monooctyl ester of epoxyfatty acid
It can also be used to synthesize numerous chemicals, including polyalcohols and polymer etc..
Chinese patent CN 106588824A disclose a kind of method using production of biodiesel environment-friendly plasticizer, with life
Object diesel oil and isooctanol are raw material, obtain fatty acid isooctyl through ester exchange reaction, then anti-by epoxidation with formic acid, hydrogen peroxide
It should obtain the different monooctyl ester of epoxyfatty acid.But transesterification used catalyst in the technique（KOH, NaOH, Mono-n-butyltin）It can make
It at reactant good fortune or is dissolved in raw material, causes subsequent products separation more intractable；And the technique also needs to be added and neutralizes examination
Agent phosphoric acid, filtering agent diatomite etc., operating process are complicated.Chinese patent CN10658825A disclose it is a kind of utilize biodiesel
The device of environment-friendly plasticizer is produced, including prepares fatty acid isooctyl system and prepares environment-friendly plasticizer system two large divisions, is closed
At the different monooctyl ester of epoxyfatty acid have many advantages, such as that density is small, flash-point is high, non-toxic.However, the transesterification that the above method uses
Catalysts are mostly homogeneous catalyst, and it is difficult that this can cause product and catalyst to detach, and it is useless to use method for washing will produce
Water.106381229 A of Chinese patent CN disclose a kind of preparation method of fatty acid isooctyl, are reacted and are filled using static mixing
The ester exchange reaction for carrying out biodiesel and isooctanol is set, has many advantages, such as that high-efficiency environment friendly, operating process are simple.Biodiesel with
Isooctanol Exchange Ester Process needs to make reaction balance carry out needing to be added excessive isooctanol to the right after the completion of transesterification
Separating-purifying is carried out to monooctyl ester, raw material is provided for subsequent epoxidation reaction.Moreover, because the boiling point of fatty acid isooctyl compared with
Height can cause energy consumption higher using conventional rectification mode.Above-mentioned technique does not consider fatty acid isooctyl subtractive process and its energy
Consumption problem.
Chinese patent CN102936074A discloses a kind of preprocess method of epoxy plasticiser production waste water, method packet
Include Production Wastewater By Combined Acidification And Demulsification, aeration oil removing, pH adjustings, air-flotation process, filtering.Chinese patent CN disclosing of 101224937A
The process for reclaiming of work plasticizer waste water, to belonging to the waste water of high COD（Such as epoxy-ester alkali-wash waste water）It is needed after being pre-processed
Enter back into biochemical system processing.Chinese patent CN101891279A disclose epoxy plasticizer production wastewater processing system and its
Method preheats epoxy soybean oil waste water, then by reaching emission request after membrane module vacuum membrane distillation.Chinese patent
CN 104291526A disclose a kind of epoxy plasticizer waste water that can improve biochemical sludge performance, this method first to wastewater pH into
Row is adjusted, and ferrous sulfate heating is then added, while needing that biochemical sludge is added.Chinese patent CN 106698783A are disclosed
A kind for the treatment of process of epoxy grease plasticizer production waste water includes mainly that neutralization, heat pump distillation, evaporative crystallization and activated carbon are inhaled
Annex IV part.The above method realizes the processing to epoxy wastewater, but processing step is more, complicated for operation, equipment investment
It is larger.And the specific processing method that waste water is produced in relation to the different monooctyl ester of epoxyfatty acid does not have been reported that in the prior art.
Invention content
It is an object of the invention to overcome the shortcomings of the prior art, and one kind is provided, epoxy is prepared based on biodiesel
The technique of fatty acid isooctyl.
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel, it is characterised in that with biodiesel
Ester exchange reaction occurs with isooctanol in the presence of solid base catalyst for raw material, it is different pungent through evaporation removing after reaction
Alcohol, thick different monooctyl ester rectification working process obtain the different monooctyl ester of rectifying, and the different monooctyl ester of gained carries out epoxidation reaction, reaction with formic acid, hydrogen peroxide
After layering, washing, flash distillation obtain the different monooctyl ester of high-quality product epoxyfatty acid.
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel, it is characterised in that ester exchange reaction
In solid base catalyst use potassium carbonate, post catalyst reaction sedimentation to stay in retort and is reused, catalyst is heavy
Time dropped less than 30 minutes.
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel, it is characterised in that evaporation removing is different
It is negative pressure 1000-2500Pa that octanol process, which uses vacuum distillation mode, vacuum distillation condition, and bottom temperature is controlled in 100-120
DEG C, the isooctanol for evaporating removing returns to transesterification process progress ester exchange reaction.
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel, it is characterised in that different monooctyl ester rectifying
It is negative pressure 200-500Pa that process, which uses high temperature high vacuum rectification, rectifying condition, and bottom temperature is controlled at 230-260 DEG C.
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel, it is characterised in that the different monooctyl ester of rectifying
The different monooctyl ester vapour phase of high temperature that process obtains, by steam generator recovery section heat, generates steam pressure gauge pressure as heat carrier
In 101-202kPa, it is used as the heat source of removing isooctanol process.
A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel, it is characterised in that different monooctyl ester epoxy
Change layered after reaction and washing, the wastewater mother liquor and washing waste water being layered merge, and heat by waste water system
Hydrogen peroxide carries out oxidation reaction processing and reaches discharge standard, and reaction temperature is 70-90 DEG C, and processing time is 2-5 hours.
By using above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows：
1）The transesterification process of the present invention carries out catalysis reaction using solid base catalyst, keeps its process efficient environmentally friendly, stearic
High conversion rate is exchanged, post catalyst reaction is easy to recycle and reuse, and product is without washing, so as to avoid the generation of sewage,
Meet environment protection requirement；
2）The different monooctyl ester steam that the different monooctyl ester rectification working process of the present invention generates recycles heat through steam generator, and by the heat of recycling
Heat source for evaporating de- isooctanol process is heated, and energy consumption is considerably reduced, and reduces cost；
3）The waste water that the different monooctyl ester epoxidation process of the present invention generates, without adding oxidant, by waste water system after heating
Hydrogen peroxide carry out oxidation processes reach discharge standard, processing mode is simple and efficient, and waste water COD is made quickly to drop to 500 mg/L
Hereinafter, reaching state three grade emissioning standard；
4）This technique is suitble to industrialized production, energy steady production to obtain the different monooctyl ester of epoxyfatty acid of high-quality.
Description of the drawings
Fig. 1 is a kind of process flow diagram for the technique preparing the different monooctyl ester of epoxyfatty acid based on biodiesel.
Specific implementation mode
The following is specific embodiments of the present invention, and in conjunction with attached drawing, technical scheme of the present invention will be further described, but
Protection scope of the present invention is not limited to that.
Embodiment 1：
As shown in Figure 1, under conditions of solid base potassium carbonate is as catalyst ester exchange reaction occurs for biodiesel and isooctanol,
Reaction condition is：Molar ratio of methanol to oil is 3:1, catalyst amount is the 3wt.% of oil weight, and reaction temperature is 180 DEG C, the reaction time
For 1 h, fatty acid isooctyl is obtained.Under this condition, biodiesel conversion rate can reach 100%.And catalyst can be direct
It is reused, reuses 5 conversion ratios and be above 99%.
Embodiment 2：
The boiling point of fatty acid isooctyl is very high, needs to carry out high temperature high vacuum rectification to purify to obtain product.As shown in Figure 1, different
When monooctyl ester rectifying, control bottom temperature is 230 DEG C, and tower top temperature is 200 DEG C, pressure 200Pa.The condition that steams of isooctanol is
Bottom temperature is controlled at 100 DEG C, tower top temperature is at 70 DEG C, pressure 1000Pa.Change operating condition, such as table 1：
It can be seen that recycling heat through steam generator using the fatty acid isooctyl vapour phase that tower top steams, steam pressure is generated（Gauge pressure）
For 101-202kPa, the heat of step recycling is used as distilling the heat source of removing recycling isooctanol after ester exchange reaction.Production
The enough heating recovery excess isooctanol of raw steam, so as to avoid process heat-energy losses.
Embodiment 3：
As shown in Figure 1, fatty acid isooctyl and hydrogen peroxide, formic acid carry out epoxidation reaction, reaction condition：Fatty acid isooctyl is double
Linkage content/hydrogen peroxide/formic acid is 1/1.5/0.25（Molar ratio）, reaction temperature is 65 DEG C, and the reaction time is 10 hours, epoxidation
Reactant is layered after reaction, upper oil phase is the different monooctyl ester of thick epoxyfatty acid, and lower layer's water phase is mother liquor containing formic acid wastewater,
The thick different monooctyl ester of epoxyfatty acid is washed through hot water to neutrality, then obtains the different monooctyl ester of refined epoxyfatty acid by flash distillation；Containing first
Sour wastewater mother liquor, washing waste water and flash off waste water merge after using in waste water system hydrogen peroxide progress advanced oxidation at
It manages, hydrogen peroxide concentration is about the 5% of wastewater flow rate in system, and concrete operations condition is：Controlled at 90 DEG C, processing time 2
Hour, processing procedure order is efficient, and waste water COD drops below 500 mg/g, can be with qualified discharge.
Above-described embodiment is served only for explaining the present invention, but does not limit protection scope of the present invention, in addition to the implementation, all
The technical solution formed using equivalent substitution or equivalent transformation, is fallen within the scope of protection required by the present invention.
Claims (6)
1. a kind of technique preparing the different monooctyl ester of epoxyfatty acid based on biodiesel, it is characterised in that using biodiesel as raw material,
In the presence of solid base catalyst, ester exchange reaction occurs with isooctanol, after reaction through evaporation removing isooctanol, thick different pungent
Ester rectification working process obtains the different monooctyl ester of rectifying, and the different monooctyl ester of gained carries out epoxidation reaction with formic acid, hydrogen peroxide, divides after reaction
Layer, washing, flash distillation obtain the different monooctyl ester of high-quality product epoxyfatty acid.
2. a kind of technique being prepared the different monooctyl ester of epoxyfatty acid based on biodiesel according to claim 1, feature are existed
Solid base catalyst in ester exchange reaction uses potassium carbonate, and post catalyst reaction sedimentation, which stays in retort, repeat making
With catalyst settling time is less than 30 minutes.
3. a kind of technique being prepared the different monooctyl ester of epoxyfatty acid based on biodiesel according to claim 1, feature are existed
It is negative pressure 1000-2500Pa, bottom temperature control to use vacuum distillation mode, vacuum distillation condition in evaporation removing isooctanol process
For system at 100-120 DEG C, the isooctanol for evaporating removing returns to transesterification process progress ester exchange reaction.
4. a kind of technique being prepared the different monooctyl ester of epoxyfatty acid based on biodiesel according to claim 1, feature are existed
It is negative pressure 200-500Pa to use high temperature high vacuum rectification, rectifying condition in different monooctyl ester rectification working process, and bottom temperature is controlled in 230-
260℃。
5. a kind of technique being prepared the different monooctyl ester of epoxyfatty acid based on biodiesel according to claim 1, feature are existed
It is generated by steam generator recovery section heat as heat carrier in the different monooctyl ester vapour phase of high temperature that the different monooctyl ester process of rectifying obtains
Steam pressure gauge is pressed in 101-202kPa, is used as the heat source of removing isooctanol process.
6. a kind of technique being prepared the different monooctyl ester of epoxyfatty acid based on biodiesel according to claim 1, feature are existed
Layered and washing, the wastewater mother liquor and washing waste water that are layered merge after different monooctyl ester epoxidation reaction, heating by
Hydrogen peroxide in waste water system carries out oxidation reaction processing and reaches discharge standard, and reaction temperature is 70-90 DEG C, processing time 2-
5 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810469604.9A CN108727308B (en) | 2018-05-16 | 2018-05-16 | Process for preparing epoxy fatty acid isooctyl ester based on biodiesel |
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| CN201810469604.9A CN108727308B (en) | 2018-05-16 | 2018-05-16 | Process for preparing epoxy fatty acid isooctyl ester based on biodiesel |
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| CN108727308A true CN108727308A (en) | 2018-11-02 |
| CN108727308B CN108727308B (en) | 2020-06-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790668A (en) * | 2019-10-22 | 2020-02-14 | 浙江工业大学 | Continuous production method for preparing fatty acid butyl ester based on biodiesel |
| CN110804029A (en) * | 2019-11-08 | 2020-02-18 | 浙江工业大学 | Epoxy plasticizer and preparation method thereof |
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| US6414168B1 (en) * | 1998-12-28 | 2002-07-02 | Caschem, Inc. | Epoxidation of ricinic compounds using a phase-transfer catalyst |
| CN106381229A (en) * | 2016-09-14 | 2017-02-08 | 浙江工业大学 | Preparation method of fatty acid iso-octyl ester |
| CN106588824A (en) * | 2016-11-25 | 2017-04-26 | 四川金谷能源科技有限公司 | Method for producing environmentally friendly plasticizer from biodiesel |
| CN107760442A (en) * | 2017-11-09 | 2018-03-06 | 山东鼎裕生物能源有限公司 | Biodiesel rectifying waste heat recycling system and technique |
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2018
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Patent Citations (4)
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|---|---|---|---|---|
| US6414168B1 (en) * | 1998-12-28 | 2002-07-02 | Caschem, Inc. | Epoxidation of ricinic compounds using a phase-transfer catalyst |
| CN106381229A (en) * | 2016-09-14 | 2017-02-08 | 浙江工业大学 | Preparation method of fatty acid iso-octyl ester |
| CN106588824A (en) * | 2016-11-25 | 2017-04-26 | 四川金谷能源科技有限公司 | Method for producing environmentally friendly plasticizer from biodiesel |
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Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790668A (en) * | 2019-10-22 | 2020-02-14 | 浙江工业大学 | Continuous production method for preparing fatty acid butyl ester based on biodiesel |
| CN110804029A (en) * | 2019-11-08 | 2020-02-18 | 浙江工业大学 | Epoxy plasticizer and preparation method thereof |
| CN110804029B (en) * | 2019-11-08 | 2022-04-29 | 浙江工业大学 | Epoxy plasticizer and preparation method thereof |
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| CN108727308B (en) | 2020-06-09 |
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