CN106588824A - Method for producing environmentally friendly plasticizer from biodiesel - Google Patents
Method for producing environmentally friendly plasticizer from biodiesel Download PDFInfo
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- CN106588824A CN106588824A CN201611054045.2A CN201611054045A CN106588824A CN 106588824 A CN106588824 A CN 106588824A CN 201611054045 A CN201611054045 A CN 201611054045A CN 106588824 A CN106588824 A CN 106588824A
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- Prior art keywords
- fatty acid
- biodiesel
- environment
- friendly plasticizer
- acid isooctyl
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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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- 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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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention relates to the technical field of plasticizer manufacturing and discloses a method for producing an environmentally friendly plasticizer from biodiesel. The method comprises that biodiesel as a main raw material and isooctanol as a reaction raw material undergo an interesterification reaction in the presence of KOH, NaOH or monobutyl tin oxide as a catalyst and phosphoric acid as a neutralizing reagent in the nitrogen protective atmosphere to produce aliphatic isooctyl ester with an octanol group, the aliphatic isooctyl ester as a main raw material and hydrogen peroxide as a reaction raw material undergo an aliphatic isooctyl ester epoxidation reaction in the presence of formic acid as a catalyst and diatomite and carclazyte as filtering agents to produce epoxidized aliphatic acid isooctyl ester, and the epoxidized aliphatic acid isooctyl ester is subjected to water washing, refining and filtration so that the high-quality environmentally friendly plasticizer is obtained. The method utilizes biodiesel to produce the environmentally friendly plasticizer, reasonably utilizes resources, realizes maximization of resource utilization, protects the environment and reduces a production cost. Compared with the common plasticizer, the environmentally friendly plasticizer has obvious advantages.
Description
Technical field
The present invention relates to plasticizer manufacturing technology field, particularly relates to a kind of utilization production of biodiesel environment-friendly plasticizer
Method.
Background technology
As rubber and filler, plasticizer is represent for tire (pneumatic tire, bicycle tyre, solid rubber
Tire) rubber composition in and industrial rubber articles (flexible pipe, driving belt, other belts, cloth inserted rubber printing plate, thin film, pad
Piece, air spring, air bag, automotive interior panel, synthetic leather) in another kind of important class additive.A large amount of plasticizers
Sometimes it is added in rubber composition, in order to reducing the cost of mixture, improving the flow behavior (during processing of mixture
Save energy, avoid energy peak), improve filler dispersion, improve deep processing behavior and adhesion behavior and change mixture
With the physical characteristics from its curing rubber for producing.
Nearly all plasticizer used in rubber industry is based generally on oil.For environment reason, especially consider
To current contamination discharge level and current raw material it is in short supply, for the production of following plasticizer, oil is no longer
It is a kind of acceptable parent material.
Under the situation of petroleum resources worsening shortages, developing a kind of green, the plasticizer of environmental protection becomes the heat of everybody concern
Point.
The content of the invention
The present invention is intended to provide a kind of method of utilization production of biodiesel environment-friendly plasticizer, solves existing plasticizer and deposits
Original material be restricted and have to environment the problem of pollution, biodiesel can obtain with multiple channel, make rational use of resources.
To achieve these goals, present invention employs following technical scheme：It is a kind of environmentally friendly using production of biodiesel
The method of plasticizer, comprises the steps of：
A () prepares fatty acid isooctyl by main material of biodiesel；
B () prepares environment-friendly plasticizer by main material of fatty acid isooctyl.
Above-mentioned steps a are specifically comprised the steps of：
1) choose raw material：With biodiesel as main material, reaction raw materials are isooctanol, catalyst is KOH, neutralization reagent is
Phosphoric acid, nitrogen are shielding gas；
2) air being first passed through in nitrogen displacement kettle, on pipeline, circuit in equipment；
3) isooctanol and catalyst are added in catalyst dissolution kettle, isooctanol addition accounts for biodiesel weight
40% to 50%, KOH addition accounts for the 0.1% to 0.3% of biodiesel weight, dissolves in catalyst dissolution kettle, obtains different pungent
The catalyst solution of alcohol；
4) catalyst solution of isooctanol is pumped in fatty acid isooctyl reactor, while biodiesel is added, temperature
Degree is set to 160 DEG C, quick to stir, and is passed through nitrogen as shielding gas, in fatty acid isooctyl reactor, reacts 3 hours, obtains
The different monooctyl ester of croude fatty acids containing isooctanol；
5) phosphoric acid is added in fatty acid isooctyl reactor, finely tune PH to 7 (neutrality), by what is contained in fatty acid isooctyl
Isooctanol is removed；
6) the solution Jing circulating pumps in fatty acid isooctyl reactor are pumped in flash tank, continuous to circulate, temperature sets
For 180 DEG C, vacuum is -0.1MPa, continues to be passed through nitrogen, maintains 2 hours with this understanding；
7) stop heating, stop vacuum, under atmospheric pressure state, continue to be passed through nitrogen, in fatty acid isooctyl reactor
Solution is cooled within 80 DEG C through cooler, filters out impurity through filter, obtains fatty acid isooctyl.
Above-mentioned steps b are specifically comprised the steps of：
1) choose raw material：With fatty acid isooctyl as main material, reaction raw materials are hydrogen peroxide, and catalyst is formic acid, are filtered
Agent is kieselguhr, hargil；
2) with nitrogen as shielding gas, be first passed through nitrogen displacement environment-friendly plasticizer reactor, neutralization dissolving tank in, pipeline and
Air on circuit in equipment, makes the air in equipment, pipeline thoroughly replace；
3) fatty acid isooctyl is pumped in environment-friendly plasticizer reactor, opens stirring, be warmed up to 65 DEG C, by hydrogen peroxide and
Formic acid is slowly added in environment-friendly plasticizer reactor, and hydrogen peroxide addition accounts for 40% of fatty acid isooctyl weight or so,
The addition of formic acid accounts for 4% of fatty acid isooctyl weight or so, and the addition time is 1-2 hour, with 60 DEG C of cooling water temperature control,
Quickly stir under atmospheric pressure state, be incubated 3-5 hour；
4) after hydrogen peroxide, formic acid are added and finished, with 65 DEG C of cooling water temperature control, normal pressure is quick to stir, and is incubated 3-5 hour,
After completion of the reaction, 2 hours are stood, releases the sewage of lower part；
5) solution in above-mentioned environment-friendly plasticizer reactor is pumped in neutralization dissolving tank, adds sodium carbonate liquor, carbon
The 10% of acid sodium solution addition fatty acid isooctyl weight, stirs 10 minutes, stands 2 hours, release lower part containing miscellaneous
The sewage of matter；
6) solution in neutralization dissolving tank is pumped back in environment-friendly plasticizer reactor, then is pumped in flash tank, temperature
105 DEG C are upgraded to, and vacuum is -0.1MPa, continuous to circulate, and moisture content is removed through flash tank；
7) be finally pumped in filtration mixing kettle, it is quick to stir, addition account for the 1% of fatty acid isooctyl weight hargil,
1% kieselguhr, temperature are 95 DEG C, adsorption reaction half an hour, are filtrated to get finished product environment-friendly plasticizer through vertical filter.
Wherein, the catalyst is NaOH or Mono-n-butyltin.
Wherein, the acid value of the biodiesel is within 0.2mgKOH/g, anhydrous without miscellaneous.
The beneficial effects of the present invention is：The present invention with biodiesel as waste, low cost, avirulence, to environment
Pollution-free and environmental-protecting performance is strong, and it not only has plasticization to PVC, can improve the plasticity of PVC product, enhanced stability and weather-proof
Property, effectively extend the service life of PVC product.
The environment-friendly plasticizer synthesized by this method has that density is little, flash-point is high, condensation point is low, and the spy such as physiological-toxicity-free
Point, its combination property are projected, and are located in the production of PVC high-end products, the environment-friendly plasticizer performance advantage of this method production
Substantially.
Specific embodiment
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described enforcement
Example is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the embodiment in the present invention, this area is common
The every other embodiment obtained under the premise of creative work is not made by technical staff, belongs to the model of present invention protection
Enclose.
A kind of method of utilization production of biodiesel environment-friendly plasticizer, comprises the steps of：
A () prepares fatty acid isooctyl by main material of biodiesel；
B () prepares environment-friendly plasticizer by main material of fatty acid isooctyl.
Above-mentioned steps a are specifically comprised the steps of：
1) choose raw material：With biodiesel as main material, reaction raw materials are isooctanol, catalyst is KOH, neutralization reagent is
Phosphoric acid, nitrogen are shielding gas；
2) air being first passed through in nitrogen displacement kettle, on pipeline, circuit in equipment；
3) isooctanol and catalyst are added in catalyst dissolution kettle, isooctanol addition accounts for biodiesel weight
40% to 50%, KOH addition accounts for the 0.1% to 0.3% of biodiesel weight, dissolves in catalyst dissolution kettle, obtains different pungent
The catalyst solution of alcohol；
4) catalyst solution of isooctanol is pumped in fatty acid isooctyl reactor, while biodiesel is added, temperature
Degree is set to 160 DEG C, quick to stir, and is passed through nitrogen as shielding gas, in fatty acid isooctyl reactor, reacts 3 hours, obtains
The different monooctyl ester of croude fatty acids containing isooctanol；
5) phosphoric acid is added in fatty acid isooctyl reactor, finely tune PH to 7 (neutrality), by what is contained in fatty acid isooctyl
Isooctanol is removed；
6) the solution Jing circulating pumps in fatty acid isooctyl reactor are pumped in flash tank, continuous to circulate, temperature sets
For 180 DEG C, vacuum is -0.1MPa, continues to be passed through nitrogen, maintains 2 hours with this understanding；
7) stop heating, stop vacuum, under atmospheric pressure state, continue to be passed through nitrogen, in fatty acid isooctyl reactor
Solution is cooled within 80 DEG C through cooler, filters out impurity through filter, obtains fatty acid isooctyl.
Preferably, other catalyst can also be adopted, catalyst is NaOH or Mono-n-butyltin etc., amount and KOH
It is identical.
This product index：Outward appearance is faint yellow, odorlessness, acid value 0.2mgKOH/g or so, fatty acid isooctyl content are more than
98%.
Biodiesel (Fatty acid methyl ester) can be obtained with multiple channel, such as adopts water from washing rice oil extract, so both reasonable
Resource is make use of, cost is reduced again, is protected environment.
By ester exchange being carried out to biodiesel and isooctanol, obtain the fatty acid isooctyl with capryl alcohol base, in case
After use.
Above-mentioned steps b are specifically comprised the steps of：
1) choose raw material：With fatty acid isooctyl as main material, reaction raw materials are hydrogen peroxide, and catalyst is formic acid, are filtered
Agent is kieselguhr, hargil；
2) with nitrogen as shielding gas, be first passed through nitrogen displacement environment-friendly plasticizer reactor, neutralization dissolving tank in, pipeline and
Air on circuit in equipment, makes the air in equipment, pipeline thoroughly replace；
3) fatty acid isooctyl is pumped in environment-friendly plasticizer reactor, opens stirring, be warmed up to 65 DEG C, by hydrogen peroxide and
Formic acid is slowly added in environment-friendly plasticizer reactor, and hydrogen peroxide addition accounts for 40% of fatty acid isooctyl weight or so,
The addition of formic acid accounts for 4% of fatty acid isooctyl weight or so, and the addition time is 1-2 hour, with 60 DEG C of cooling water temperature control,
Quickly stir under atmospheric pressure state, be incubated 3-5 hour；
4) after hydrogen peroxide, formic acid are added and finished, with 65 DEG C of cooling water temperature control, normal pressure is quick to stir, and is incubated 3-5 hour,
After completion of the reaction, 2 hours are stood, releases the sewage of lower part；
5) solution in above-mentioned environment-friendly plasticizer reactor is pumped in neutralization dissolving tank, adds sodium carbonate liquor, carbon
The 10% of acid sodium solution addition fatty acid isooctyl weight, stirs 10 minutes, stands 2 hours, release lower part containing miscellaneous
The sewage of matter；
6) solution in neutralization dissolving tank is pumped back in environment-friendly plasticizer reactor, then is pumped in flash tank, temperature
105 DEG C are upgraded to, and vacuum is -0.1MPa, continuous to circulate, and moisture content is removed through flash tank；
7) be finally pumped in filtration mixing kettle, it is quick to stir, addition account for the 1% of fatty acid isooctyl weight hargil,
1% kieselguhr, temperature are 95 DEG C, adsorption reaction half an hour, are filtrated to get finished product environment-friendly plasticizer through vertical filter.
Finished product is colourless, tasteless epoxy, low condensation point the features such as.
Epoxyfatty acid isooctyl is obtained by fatty acid isooctyl epoxidation reaction, through washing, refining filtering operation
Obtain the environment-friendly plasticizer of high-quality.Performance is with the obvious advantage with other plasticizers.
The environment-friendly plasticizer synthesized by this method is compared with common plasticizers DOP performance indications：
The environment-friendly plasticizer synthesized by this method has that density is little, flash-point is high, condensation point is low, and the spy such as physiological-toxicity-free
Point, its combination property are projected, and are located in the production of PVC high-end products, the environment-friendly plasticizer of visible above this method production
Performance advantage is obvious.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (5)
1. a kind of method of utilization production of biodiesel environment-friendly plasticizer, it is characterised in that comprise the steps of：
（a）Fatty acid isooctyl is prepared by main material of biodiesel；
（b）Environment-friendly plasticizer is prepared by main material of fatty acid isooctyl.
2. the method for utilization production of biodiesel environment-friendly plasticizer according to claim 1, it is characterised in that above-mentioned steps
A is specifically comprised the steps of：
1）Choose raw material：With biodiesel as main material, reaction raw materials are isooctanol, catalyst is KOH, neutralization reagent is phosphorus
Acid, nitrogen are shielding gas；
2）The air being first passed through in nitrogen displacement kettle, on pipeline, circuit in equipment；
3）Isooctanol and catalyst are added in catalyst dissolution kettle, isooctanol addition account for the 40% of biodiesel weight to
50%, KOH addition accounts for the 0.1% to 0.3% of biodiesel weight, dissolves in catalyst dissolution kettle, obtains urging for isooctanol
Agent solution；
4）The catalyst solution of isooctanol is pumped in fatty acid isooctyl reactor, while adding biodiesel, temperature to set
It is for 160 DEG C, quick to stir, nitrogen is passed through as shielding gas, in fatty acid isooctyl reactor, react 3 hours, obtain containing different
The different monooctyl ester of croude fatty acids of capryl alcohol；
5）Phosphoric acid is added in fatty acid isooctyl reactor, PH to 7 is finely tuned（It is neutral）, it is different pungent by what is contained in fatty acid isooctyl
Alcohol is removed；
6）Solution Jing circulating pumps in fatty acid isooctyl reactor are pumped in flash tank, continuous to circulate, temperature is set to 180
DEG C, vacuum is -0.1MPa, continues to be passed through nitrogen, maintains 2 hours with this understanding；
7）Stop heating, stop vacuum, under atmospheric pressure state, continue to be passed through nitrogen, the solution in fatty acid isooctyl reactor
Cool within 80 DEG C through cooler, impurity is filtered out through filter, obtain fatty acid isooctyl.
3. the method for utilization production of biodiesel environment-friendly plasticizer according to claim 1 and 2, it is characterised in that above-mentioned
Step b is specifically comprised the steps of：
1）Choose raw material：With fatty acid isooctyl as main material, reaction raw materials are hydrogen peroxide, and catalyst is formic acid, and filtering agent is
Kieselguhr, hargil；
2）With nitrogen as shielding gas, nitrogen displacement environment-friendly plasticizer reactor, interior neutralization dissolving tank, pipeline and circuit are first passed through
Air in upper equipment, makes the air in equipment, pipeline thoroughly replace；
3）Fatty acid isooctyl is pumped in environment-friendly plasticizer reactor, stirring is opened, is warmed up to 65 DEG C, by hydrogen peroxide and formic acid
It is slowly added in environment-friendly plasticizer reactor, hydrogen peroxide addition accounts for 40% of fatty acid isooctyl weight or so, formic acid
Addition account for the 4% or so of fatty acid isooctyl weight, the addition time is 1-2 hour, with 60 DEG C of cooling water temperature control, normal
Quickly stir under pressure condition, be incubated 3-5 hour；
4）Hydrogen peroxide, formic acid are added after finishing, and with 65 DEG C of cooling water temperature control, normal pressure is quick to stir, and is incubated 3-5 hour, reacts
After finishing, 2 hours are stood, release the sewage of lower part；
5）Solution in above-mentioned environment-friendly plasticizer reactor is pumped in neutralization dissolving tank, sodium carbonate liquor, sodium carbonate is added
The 10% of solution addition fatty acid isooctyl weight, stirs 10 minutes, stands 2 hours, releases the impure of lower part
Sewage；
6）Solution in neutralization dissolving tank is pumped back in environment-friendly plasticizer reactor, then is pumped in flash tank, temperature is upgraded to
105 DEG C, vacuum is -0.1MPa, continuous to circulate, and removes moisture content through flash tank；
7）Finally be pumped in filtration mixing kettle, it is quick to stir, addition account for the hargil of the 1% of fatty acid isooctyl weight, 1%
Kieselguhr, temperature are 95 DEG C, adsorption reaction half an hour, are filtrated to get finished product environment-friendly plasticizer through vertical filter.
4. the method for utilization production of biodiesel environment-friendly plasticizer according to claim 2, it is characterised in that the catalysis
Agent is NaOH or Mono-n-butyltin.
5. the method for utilization production of biodiesel environment-friendly plasticizer according to claim 1, it is characterised in that the biology
The acid value of diesel oil is within 0.2mgKOH/g, anhydrous without miscellaneous.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611054045.2A CN106588824A (en) | 2016-11-25 | 2016-11-25 | Method for producing environmentally friendly plasticizer from biodiesel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611054045.2A CN106588824A (en) | 2016-11-25 | 2016-11-25 | Method for producing environmentally friendly plasticizer from biodiesel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106588824A true CN106588824A (en) | 2017-04-26 |
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ID=58593294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611054045.2A Pending CN106588824A (en) | 2016-11-25 | 2016-11-25 | Method for producing environmentally friendly plasticizer from biodiesel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727308A (en) * | 2018-05-16 | 2018-11-02 | 浙江工业大学 | A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel |
-
2016
- 2016-11-25 CN CN201611054045.2A patent/CN106588824A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727308A (en) * | 2018-05-16 | 2018-11-02 | 浙江工业大学 | A kind of technique that the different monooctyl ester of epoxyfatty acid is prepared based on biodiesel |
| CN108727308B (en) * | 2018-05-16 | 2020-06-09 | 浙江工业大学 | Process for preparing epoxy fatty acid isooctyl ester based on biodiesel |
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