CN105130812A - Synthetic method for isopropyl palmitate - Google Patents
Synthetic method for isopropyl palmitate Download PDFInfo
- Publication number
- CN105130812A CN105130812A CN201510560031.7A CN201510560031A CN105130812A CN 105130812 A CN105130812 A CN 105130812A CN 201510560031 A CN201510560031 A CN 201510560031A CN 105130812 A CN105130812 A CN 105130812A
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- CN
- China
- Prior art keywords
- wickenol
- synthetic method
- reaction
- virahol
- temperature
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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
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthetic method for isopropyl palmitate, and belongs to the technical field of synthesizing ester compounds in organic chemistry. The synthetic method includes the steps that methyl palmitate and isopropanol are mixed in a pipeline mixer according to a certain ratio, enter a flow reactor which a catalyst adheres to after being mixed evenly and heated to certain temperature, and are controlled to perform transesterification at certain pressure, and reaction product methanol is continuously separated at the same time. The reaction mixture enters an isopropyl ester dealcoholizing tower, the redundant isopropanol and methanol which is generated in the reaction process and not removed are removed at certain pressure and temperature, and the kettle material is cooled through a heat exchanger and then output as an isopropyl palmitate finished product. The high-purity methyl palmitate obtained through a fractionation technology in the process of producing biodiesel is used as a raw material, the reaction product methanol is continuously removed through a continuous catalytic reaction, the technological flow path is shortened, process energy consumption and raw material consumption are reduced, the yield of the isopropyl palmitate is increased, and the product quality of the isopropyl palmitate is improved.
Description
Technical field
The present invention relates to a kind of derived product of biofuel, belong to the synthesis technical field of ester compound in organic chemistry; More particularly, a kind of synthetic method of Wickenol 111 is related to.
Background technology
Biofuel was born in Germany in 1988, and China is production biofuel from calendar year 2001.Biofuel is the lipid acid monoalkyl fat obtained through transesterification reaction by animal and plant grease and alcohol, and most typical biofuel is Fatty acid methyl ester.Biofuel worldwide becomes the focus of new energy development with its superior environmental-protecting performance.Overwhelming majority biofuel uses as fuel, but biofuel is also good chemical intermediate.The exploitation of its derivative, also will become the only way of each enterprise high speed development from now on.After the sustainable development of the energy becomes the basis of national strategy safety control, the sustainable recycling economy of chemical industry also comes into one's own and widespread use day by day.Therefore, the fatty acid methyl ester (biofuel) utilizing waste grease to produce and derived product thereof, have wide market outlook.
Wickenol 111 (Isopropyl Palmitate, IPP) is a kind of low viscosity lipophilicity nonionic surface active agent, is extremely valuable auxiliary material in makeup, is important additive and promoting agent in the superior cosmetics such as cream frost, hair conditioner.IPP is water insoluble, can with the immiscible organic solvents such as alcohol, ether, METHYLENE CHLORIDE, grease, general consumption be 2% ~ 10% (massfraction) just can make lotion and emulsion pure white, bright, fine and smooth, improve the quality of products.The solvent etc. of humextant, permeate agent and spices and colorant is also commonly used in industry.When product molding, also play the effect of tackifier, softening agent and opalizer, the product in order to preparation is considered to one of best product of seepage force, has splendid water conservation wettability, along with the raising day by day of living standards of the people, the demand of this series products will constantly increase.In view of these physics and chemistry characteristics of IPP, can expect that IPP will become one of important source material of following cosmetic industry application.
From natural fats and oils, extract IPP the earliest, output is very limited.In order to adapt to ever-increasing industry and civilian demand, various chemical synthesising technology arises at the historic moment, and has developed multiple production method and synthesis route so far.
At present both at home and abroad the preparation method of Wickenol 111 mainly with palmitinic acid and Virahol for raw material, adopt and have the traditional method such as chloride method, direct esterification to synthesize.Owing to there is SO
2, HCl, H
2sO
4etc. chemical substance, there is strong toxicity and chemical corrosivity in aforesaid method, and the anti-leak of whole system and requirement for anticorrosion are all extremely strict, and there is complex manufacturing, and one-time investment is large, and operation controls loaded down with trivial details; Production cost is high, poor selectivity, side reaction are many, poor product quality, be unfavorable for the shortcomings such as cleaner production.
Summary of the invention
1. invent the technical problem that will solve
For the problems referred to above, the invention provides a kind of with solid acid as catalyst, with Uniphat A60 and Virahol for raw material, prepare the method for high-quality Wickenol 111; It is raw material that the present invention utilizes producing the high purity palmitic acid methyl esters obtained through fractionation process in biodiesel process, pass through continuous catalytic reaction, remove reaction product methyl alcohol continuously, shortened process, reduction process energy consumption and raw material consumption, improve yield and the quality product of Wickenol 111.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The synthetic method of a kind of Wickenol 111 of the present invention, adopts transesterification reaction single stage method to obtain Wickenol 111.One is shorten technical process, avoid strong toxicity and chemical corrosivity, reduces investment and operation easier; Two is solve that poor selectivity, side reaction are many, poor product quality, be unfavorable for the difficult problem of cleaner production; Three is adopt automatically-controlled continuous system to decrease energy loss, reduces production cost.Compared with conventional traditional technology, be replaced the change of group owing to there is lipid acid and fatty acid methyl ester, the selection of catalyzer and reaction conditions is core of the present invention.
Key step of the present invention is as follows:
Step one, transesterification reaction: by mass percent concentration be more than 99.5% high purity palmitic acid methyl esters and Virahol mix in line mixer by a certain percentage, mix and enter the flow reactor being attached with catalyzer after being heated to certain temperature, control to carry out transesterification reaction under a certain pressure, be continuously separated reaction product methyl alcohol simultaneously.
The mol ratio of Uniphat A60 described in step one and Virahol is 1:3 ~ 8, and preferred molar ratio is 1:4, and under said ratio, the alcohol of excess can fast reaction speed, simultaneously the concentration of diluting reaction Methanol product, improves the transformation efficiency of reaction product.Described temperature of reaction is 60 ~ 120 DEG C, preferably 80 ~ 90 DEG C, and this temperature of reaction removes reaction product methyl alcohol continuously, the key of fast reaction speed.The selection of described catalyzer is the key realizing successive reaction, improve selectivity of product, avoid traditional technology drawback, and selecting catalyst of the present invention is supported solid catalyst Zr (SO
4)
2/ SiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2+ ZrO
2or the one in sulfonic acid ion exchange resin.Described reactor pressure is 0.5 ~ 0.8MPa, preferably 0.15 ~ 0.35MPa, and this pressure is fast reaction speed, realizes the key removing reaction product methyl alcohol continuously.Described reactor is the one in pipeline reactor, tower reactor, tank reactor.
Step 2, dealcoholysis: after step one reaction terminates, reaction mixture enters isopropyl ester dealcoholize column, remove under certain pressure and temperature in excessive Virahol and reaction process and generate and the methyl alcohol that do not remove, kettle material is Wickenol 111 product, exports after interchanger cooling as Wickenol 111 finished product.Pressure described in step 2 is 20 ~ 80KPaA, preferably 30 ~ 50KPaA; Described dealcoholysis temperature is 80 ~ 160 DEG C, preferably 110 ~ 140 DEG C.
Step 3, alcohol are refining: after step 2 terminates, isopropyl ester dealcoholize column tower top is separated the alcohol mixture obtained and enters alcohol mixture knockout tower together with the condensed methyl alcohol of methanol condenser, alcohol mixture is separated under certain temperature, normal pressure, recovered overhead methyl alcohol is as the raw material of production biofuel, and tower reactor reclaims Virahol for recycling.The separation temperature of alcohol mixture described in step 3 is 90 ~ 140 DEG C, preferably 100 ~ 130 DEG C.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following unusual effect:
(1) synthetic method of a kind of Wickenol 111 of the present invention, in the transesterification reaction stage, application Uniphat A60 and Virahol are raw material, make use of the good mutual solubility of Uniphat A60 and alcohol, breaching traditional technology uses lipid acid and alcohol can not form the shortcoming of even phase system, and break the normal procedure employ higher alcohols displacement low-carbon alcohol synthetic route, improve the transformation efficiency of Wickenol 111 product;
(2) synthetic method of a kind of Wickenol 111 of the present invention, in view of relative traditional technology, there is the change that palmitinic acid and Uniphat A60 are substituted group, the selection of catalyzer and reaction conditions affects the selectivity of Wickenol 111 and the transforming degree of Uniphat A60 to a great extent, this invention exploits applicable catalyzer and processing condition, utilize the solid catalyst of attachment, the means removing reaction product methyl alcohol under certain processing condition have continuously broken molecular balance, achieve continuous seepage, improve quality product and yield, reduce production cost, solve the strong toxicity and chemical corrosivity that exist in traditional technology, and complex manufacturing, one-time investment is large, operation controls loaded down with trivial details, production cost is high, poor selectivity, side reaction is many, poor product quality, be unfavorable for the shortcomings such as cleaner production, synthetic method science of the present invention environmental protection, the Wickenol 111 quality index obtained meets enterprise's mark requirement completely.
Embodiment
For understanding content of the present invention further, below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The synthetic method of a kind of Wickenol 111 of the present embodiment, utilizes and is producing the high purity palmitic acid methyl esters that obtains through fractionation process in biodiesel process as the raw material producing high quality Wickenol 111.The mass percent concentration of described high purity palmitic acid methyl esters is 99.5%.From the production technique of biofuel, obtain the fractionation process of high purity palmitic acid methyl esters see patent No. CN200610112322.0.The synthesis mechanism of Wickenol 111 is:
Uniphat A60 and Virahol react under catalyzer existence condition, and generate Wickenol 111, reaction equation is as follows:
RCOOCH
3+(CH
3)
2CHOH→RCOOCH(CH
3)
2+CH
3OH
The detailed process of the present embodiment synthesis Wickenol 111 is as follows:
Reaction well heater is entered after the proportioning being 1:4 in molar ratio by high purity palmitic acid methyl esters and Virahol mixes in line mixer, enter pipeline reactor after being heated to 90 DEG C and carry out transesterification reaction, the catalyzer adhered in pipeline reactor is load-type solid acid---Zr (SO4)
2/ SiO
2, controlling reaction pressure in pipeline reactor is 0.2MPa, the CH generated in reaction process
3finally enter alcohol mixture knockout tower after entering methanol condenser condensation after OH vaporization to be separated.Reaction terminates rear reaction mixture and enters isopropyl ester dealcoholize column and remove in excessive Virahol and reaction process and generate and the methyl alcohol of not vaporizing, and kettle material is Wickenol 111 product, exports after interchanger cooling as Wickenol 111 finished product.In isopropyl ester dealcoholize column, temperature is 135 DEG C, and pressure is 45KPaA.Isopropyl ester dealcoholize column tower top is separated the alcohol mixture obtained and enters alcohol mixture knockout tower together with the condensed methyl alcohol of methanol condenser and be separated, and recovered overhead methyl alcohol is as biodiesel raw material, and tower reactor reclaims Virahol and can be recycled.In alcohol mixture knockout tower, temperature is 110 DEG C, atmospheric operation.Products obtained therefrom Wickenol 111 yield is 99.93%, and quality meets company standard requirement.
Embodiment 2
By mass percent concentration be 99.6% high purity palmitic acid methyl esters and Virahol in molar ratio for the proportioning of 1:3 mix in line mixer after enter reaction well heater, enter tower reactor after being heated to 80 DEG C and carry out transesterification reaction, the catalyzer adhered in tower reactor is load-type solid acid---SO
4 2-/ ZrO
2, controlling reaction pressure in tower reactor is 0.35MPa, the CH generated in reaction process
3finally enter alcohol mixture knockout tower after entering methanol condenser condensation after OH vaporization to be separated.Reaction terminates rear reaction mixture and enters isopropyl ester dealcoholize column and remove in excessive Virahol and reaction process and generate and the methyl alcohol of not vaporizing, and kettle material is Wickenol 111 product, exports after interchanger cooling as Wickenol 111 finished product.In isopropyl ester dealcoholize column, temperature is 140 DEG C, and pressure is 50KPaA.Isopropyl ester dealcoholize column tower top is separated the alcohol mixture obtained and enters alcohol mixture knockout tower together with the condensed methyl alcohol of methanol condenser and be separated, and recovered overhead methyl alcohol is as biodiesel raw material, and tower reactor reclaims Virahol and can be recycled.In alcohol mixture knockout tower, temperature is 130 DEG C, atmospheric operation.Products obtained therefrom Wickenol 111 yield is 99.91%, and quality meets company standard requirement.
Embodiment 3
By mass percent concentration be 99.55% high purity palmitic acid methyl esters and Virahol in molar ratio for the proportioning of 1:5 mix in line mixer after enter reaction well heater, enter tank reactor after being heated to 85 DEG C and carry out transesterification reaction, the catalyzer adhered in tank reactor is load-type solid acid---SO
4 2-/ TiO
2+ ZrO
2, controlling reaction pressure in tank reactor is 0.15MPa, the CH generated in reaction process
3finally enter alcohol mixture knockout tower after entering methanol condenser condensation after OH vaporization to be separated.Reaction terminates rear reaction mixture and enters isopropyl ester dealcoholize column and remove in excessive Virahol and reaction process and generate and the methyl alcohol of not vaporizing, and kettle material is Wickenol 111 product, exports after interchanger cooling as Wickenol 111 finished product.In isopropyl ester dealcoholize column, temperature is 110 DEG C, and pressure is 30KPaA.Isopropyl ester dealcoholize column tower top is separated the alcohol mixture obtained and enters alcohol mixture knockout tower together with the condensed methyl alcohol of methanol condenser and be separated, and recovered overhead methyl alcohol is as biodiesel raw material, and tower reactor reclaims Virahol and can be recycled.In alcohol mixture knockout tower, temperature is 100 DEG C, atmospheric operation.Products obtained therefrom Wickenol 111 yield is 99.89%, and quality meets company standard requirement.
Embodiment 4
By mass percent concentration be 99.8% high purity palmitic acid methyl esters and Virahol in molar ratio for the proportioning of 1:6 mix in line mixer after enter reaction well heater, enter pipeline reactor after being heated to 60 DEG C and carry out transesterification reaction, the catalyzer adhered in pipeline reactor is sulfonic acid ion exchange resin, controlling reaction pressure in pipeline reactor is 0.4MPa, the CH generated in reaction process
3finally enter alcohol mixture knockout tower after entering methanol condenser condensation after OH vaporization to be separated.Reaction terminates rear reaction mixture and enters isopropyl ester dealcoholize column and remove in excessive Virahol and reaction process and generate and the methyl alcohol of not vaporizing, and kettle material is Wickenol 111 product, exports after interchanger cooling as Wickenol 111 finished product.In isopropyl ester dealcoholize column, temperature is 145 DEG C, and pressure is 20KPaA.Isopropyl ester dealcoholize column tower top is separated the alcohol mixture obtained and enters alcohol mixture knockout tower together with the condensed methyl alcohol of methanol condenser and be separated, and recovered overhead methyl alcohol is as biodiesel raw material, and tower reactor reclaims Virahol and can be recycled.In alcohol mixture knockout tower, temperature is 135 DEG C, atmospheric operation.
Claims (10)
1. a synthetic method for Wickenol 111, the steps include:
Step one, Uniphat A60 and Virahol are mixed post-heating to 60 ~ 120 DEG C, under pressure is 0.5 ~ 0.8MPa and catalysts conditions, carries out transesterification reaction, is continuously separated reaction product methyl alcohol simultaneously;
Step 2, be 20 ~ 80KPaA at pressure, the methyl alcohol that temperature is Virahol under 80 ~ 160 DEG C of conditions in removing step one gained reaction mixture and does not remove, after cooling Wickenol 111 finished product.
2. the synthetic method of a kind of Wickenol 111 according to claim 1, is characterized in that: step 2 is separated the alcohol mixture that obtains and is 90 ~ 140 DEG C in temperature, is separated under condition of normal pressure, the Virahol recycle of recovery.
3. the synthetic method of a kind of Wickenol 111 according to claim 1 and 2, is characterized in that: step one used catalyst is supported solid catalyst Zr (SO
4)
2/ SiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2+ ZrO
2or the one in sulfonic acid ion exchange resin.
4. the synthetic method of a kind of Wickenol 111 according to claim 3, is characterized in that: in step one, the mass percent concentration of Uniphat A60 is more than 99.5%.
5. the synthetic method of a kind of Wickenol 111 according to claim 4, is characterized in that: in step one, the mol ratio of Uniphat A60 and Virahol is 1:3 ~ 8.
6. the synthetic method of a kind of Wickenol 111 according to claim 5, is characterized in that: the preferred 1:4 of the mol ratio of Uniphat A60 and Virahol in step one.
7. the synthetic method of a kind of Wickenol 111 according to claim 6, is characterized in that: temperature of reaction described in step one preferably 80 ~ 90 DEG C.
8. the synthetic method of a kind of Wickenol 111 according to claim 7, is characterized in that: the preferably 0.15 ~ 0.35MPa of pressure described in step one.
9. the synthetic method of a kind of Wickenol 111 according to claim 8, is characterized in that: the preferably 30 ~ 50KPaA of pressure described in step 2.
10. the synthetic method of a kind of Wickenol 111 according to claim 9, is characterized in that: temperature described in step 2 preferably 110 ~ 140 DEG C.
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|---|---|---|---|
| CN201510560031.7A CN105130812B (en) | 2015-09-06 | 2015-09-06 | Synthetic method for isopropyl palmitate |
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|---|---|---|---|
| CN201510560031.7A CN105130812B (en) | 2015-09-06 | 2015-09-06 | Synthetic method for isopropyl palmitate |
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| CN105130812B CN105130812B (en) | 2017-01-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047045A (en) * | 2017-12-13 | 2018-05-18 | 中国科学院青岛生物能源与过程研究所 | A kind of two step transesterification of palm oil is combined to the method and device of isopropyl palmitate |
Citations (3)
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| CN1858160A (en) * | 2006-06-02 | 2006-11-08 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
| CN101230309A (en) * | 2008-01-11 | 2008-07-30 | 四川大学 | Method for preparing biodiesel by lowering value of high acid palm oil |
| CN101914021A (en) * | 2010-08-23 | 2010-12-15 | 孝感市易生新材料有限公司 | Method for producing high-content and high-optical purity butyl lactate with two-step method |
-
2015
- 2015-09-06 CN CN201510560031.7A patent/CN105130812B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858160A (en) * | 2006-06-02 | 2006-11-08 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
| CN101230309A (en) * | 2008-01-11 | 2008-07-30 | 四川大学 | Method for preparing biodiesel by lowering value of high acid palm oil |
| CN101914021A (en) * | 2010-08-23 | 2010-12-15 | 孝感市易生新材料有限公司 | Method for producing high-content and high-optical purity butyl lactate with two-step method |
Non-Patent Citations (2)
| Title |
|---|
| 刘学民: "棕榈酸异丙酯的合成", 《香料香精化妆品》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047045A (en) * | 2017-12-13 | 2018-05-18 | 中国科学院青岛生物能源与过程研究所 | A kind of two step transesterification of palm oil is combined to the method and device of isopropyl palmitate |
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| CN105130812B (en) | 2017-01-18 |
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Effective date of registration: 20180523 Address after: 243000 No. 259 South Hu Road, Ma'anshan economic and Technological Development Zone, Ma'anshan, Anhui Patentee after: Anhui racing Energy Technology Co., Ltd. Address before: 243000 No. 207 Yutian Road, Ma'anshan economic and Technological Development Zone, Anhui Patentee before: Anhui Zeng Yuan bioenergy company limited |
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Effective date of registration: 20201202 Address after: 246500 Susong Economic Development Zone, Anhui, Anqing Patentee after: ANHUI DASONG RESIN Co.,Ltd. Address before: 243000 Anhui city of Ma'anshan province Ma'anshan economic and Technological Development Zone West Road No. 259 Patentee before: Anhui racing Energy Technology Co.,Ltd. |