CN101074191A - Esterification of non-solvent aliphatic ester - Google Patents
Esterification of non-solvent aliphatic ester Download PDFInfo
- Publication number
- CN101074191A CN101074191A CN 200610080720 CN200610080720A CN101074191A CN 101074191 A CN101074191 A CN 101074191A CN 200610080720 CN200610080720 CN 200610080720 CN 200610080720 A CN200610080720 A CN 200610080720A CN 101074191 A CN101074191 A CN 101074191A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- acid
- reaction
- fatty acid
- catalyst
- 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.)
- Pending
Links
Abstract
Production of aliphatic ester utilizes homogeneous and heterogeneous reactive acid catalyst. The process is carried out by taking fatty aid, monobasic alcohol, dibasic alcohol, tribasic alcohol, tetrabasic alcohol, polybasic alcohol and polyethylene glycol as raw materials, and preparing obtaining fatty acid monoester, fatty acid multi-ester, and fatty acid polyethylene glycol. It's simple and cheap, has more yield, friendly reactive environment and no environmental pollution and need for azeotropic solvent.
Description
(1) technical field
The present invention relates to the fatty acid esterification reaction.More particularly, esterification takes place with alcohol in lipid acid under the situation of not using azeotropic solvent exactly, and homogeneous phase and heterogeneous reaction acid catalyst are used in reaction.
(2) background technology
Well-known lipid acid and pure reaction can prepare fatty acid ester, and prepared fatty acid ester is widely used, and is often used in makeup and lubricant.In order to make reaction carry out generally a kind of reactant to the positive reaction direction is excessive.Esterification is generally carried out under mineral acid or organic acid catalysis, such as sulfuric acid and tosic acid.Commercial normally used be the homogeneous reaction acid catalyst.
Industrial also have the method for many production fatty acid esters to carry out in flow reactor or cylindrical reactor.U.S.Pat.No.5008046 discloses lipid acid and the esterification of alcohol in the convection type reactor, and the time of alcohol adverse current in liquid phase is 20min at least, and the pressure of reaction column is 200-900kPa.The mixture of water and oil is by rectifying tower, and fatty acid ester flows out from pillar.No.CN 1504452 discloses the esterification in the post, and what be rich in alcohol enters cylindrical reactor to gas by distiller, and water is discharged pillar as strippant.
Patent DE-A 2 913 218 discloses esterification and has utilized the azeotropic method, and such as the toluene equal solvent is added in the reactant, this solvent can form azeotropic mixture with the water that esterification generates, and takes water out of reaction system, and reaction is carried out fully.
However, the esterification of lipid acid is carried out in the tank reactor at intermittence usually, and uses the azeotropic solvent such as toluene.U.S.Pat.No.119137 discloses a kind of method of the production cetylate that consumes energy little, and the cetylate of being produced is as lubricant.Cetylate is that the esterification by palmitinic acid obtains, and needs toluene as azeotropic solvent.Yet this method comes with some shortcomings, as azeotropic solvent cost costliness, poisonous and not enough environmental friendliness.Product needed is through extra separation and purification in addition.
(3) summary of the invention:
Adding excessive reactant in the esterification reaction process is for reaction is carried out fully, add excessive monohydroxy-alcohol in the solvent-free fatty acid esterification reaction process provided by the present invention, water as butanols and esterification generation forms azeotropic mixture, make that water is easier to be told from reaction system, water constantly divides the esterification yield of sening as an envoy to reach the highest from reactant.Azeotropic mixture presents two-layer in water trap, and the upper strata is an organic phase, and lower floor is a water, and in the reaction process, organic phase can be back to and continue to participate in reaction in the reactor.
Do not use under the situation of azeotropic solvent (as toluene), the esterification of lipid acid is under comparatively gentle temperature and in the short time, the water that uses excessive reactant and esterification to generate forms azeotrope, and water is removed from reaction system, and reaction is carried out to positive dirction.
The present invention is applicable to the alcohol of 4-12 C atom, and the pure boiling point that is less than 4 C is low and water-soluble, is not suitable for solvent-free esterification.4 above alcohol of C can form azeotropic mixture and layering in water trap with water, and organic phase can be back to and continue reaction in the reaction system.Along with the increase of C atomicity, temperature of reaction raises, and the water that reaction generates is easy to tell reaction system, and reaction is carried out fully.
In order to prepare fatty acid poleysters and fatty acid polyglycol second diester, with excess fats acid as reactant, for the water that makes generation steams temperature of reaction system must be greater than 100 ℃, but temperature can not surpass the boiling point of reactant, water is constantly steamed in reaction process, reactant and product are still stayed in the reactor, make esterification yield reach the highest.
Esterification is carried out under homogeneous phase and heterogeneous reaction catalyst, temperature of reaction is at 80-250 ℃, the esterification reaction temperature of lipid acid and monohydroxy-alcohol and isomers is 80-180 ℃, the esterification reaction temperature of lipid acid and dibasic alcohol, trivalent alcohol, tetravalent alcohol, polyvalent alcohol or its isomers or polyoxyethylene glycol is 100-250 ℃, and the reaction times is less than 6h.
Reaction finishes the back excessive reactant removes from the fatty acid ester that generates by underpressure distillation, and the homogeneous reaction acid catalyst is removed by continuous alkali cleaning washing, and then further removes unreacted lipid acid of residue and impurity.
When using the heterogeneous reaction acid catalyst, the separation of catalyzer is very simple, just catalyzer can be separated with product by simple filtering.
The present invention prepares the following description of concrete grammar of fatty acid ester:
1. the preparation of fatty acid monoester:
The mixture of lipid acid and monohydroxy-alcohol and catalyzer are packed in the reactor, alcohol is excessive, reflux condensing tube is housed, water trap, thermometer on the reactor, heat temperature raising under the agitation condition, temperature of reaction has the layering in water trap of monobasic alcohol and water azeotrope during near 80-180 ℃, and organic phase flows back in the reactor heavily again reacts, water is told reaction system, and the reaction times is less than 6h.
Reaction finishes the thick product in back and is cooled to room temperature, if use the homogeneous reaction acid catalyst, the homogeneous reaction acid catalyst will be by continuous alkali cleaning washing till product be neutrality, and the water in the product is removed by distillation.Excessive reactant is separated by underpressure distillation with unreacted lipid acid.Unreacted lipid acid is as resistates, and fatty acid monoester is as fraction collection.If use heterogeneous acid catalyst only to need just catalyzer to be removed by simple filtering.
2. the preparation of fatty acid poleysters and fatty acid polyglycol second diester:
The mixture of lipid acid and dibasic alcohol, trivalent alcohol, tetravalent alcohol, polyvalent alcohol or polyoxyethylene glycol is packed in the reactor, wherein lipid acid is excessive, reflux condensing tube is housed, water trap, thermometer on the reactor, agitation condition adds catalyzer and heat temperature raising down, temperature of reaction between 100-250 ℃, the layering in water trap of organic phase and water, organic phase flows back in the reactor heavily again reacts, water is told reaction system, and the reaction times is less than 6h.
Reaction finishes the thick product in back and is cooled to room temperature, if use homogeneous catalyst, homogeneous catalyst will be by continuous alkali cleaning washing till product be neutrality, and the water in the product is removed by distillation.Fatty acid poleysters and fatty acid polyglycol second diester are as fraction collection, and excess fats acid, how pure and mild polyoxyethylene glycol are as resistates.If use heterogeneous acid catalyst only to need just can remove catalyzer, do not need washing by simple filtering.
For the ease of understanding some used in this claim words, do with explanation at this.
1. described lipid acid refers to saturated fatty acid that contains 8-22 C atom and the unsaturated fatty acids that extracts from plant or mineral, and isomers or mixture.
2. described monohydroxy-alcohol refers to the alcohol that contains 4-12 C atom, and isomers and their mixture.
3. described dibasic alcohol, trivalent alcohol, tetravalent alcohol, polyvalent alcohol refer to the alcohol that contains 4-12 C atom, and isomers and their mixture.
4. described polyoxyethylene glycol refers to the polyoxyethylene glycol of molar mass at 200-20000g/mol.
5. the catalyzer that described homogeneous reaction acid catalyst refers to liquid, solid or powder is dissolved in reaction system in reaction process, comprise sulfuric acid, tosic acid, and the sulfoacid compound of hydro carbons, zirconium sulfate, heteropolyacid.
6. described heterogeneous reaction acid catalyst refers to solid or powder and does not dissolve in reaction process and become the biphase catalyzer with reactant, comprise ion exchange resin, molecular sieve, metal oxide, metallic salt, heteropolyacid, super acids and carried heteropoly acid, loading metal-salt, metal oxide-loaded, Nafion-H.
7. described acid catalyst refers to homogeneous acid catalyst and heterogeneous acid catalyst.
8. described reactant refers to lipid acid, monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol, polyvalent alcohol, polyoxyethylene glycol and isomers or their mixture.
10. described product fatty acid ester refers to the fatty acid monoester that obtains in the fatty acid esterification reaction, fatty acid poleysters, fatty acid polyglycol second diester.
11. described solvent refers to volatile azeotropic solvent, comprises toluene, dimethylbenzene, benzene, hexanaphthene, contains the saturated alkane and the isomers thereof of 5-12 C atom.
12. described fatty acid ester refers to lipid acid and the monohydroxy-alcohol esterification makes, wherein the mol ratio of monohydroxy-alcohol and lipid acid is greater than 1:
Lipid acid+monohydroxy-alcohol → fatty acid ester+water
13. described fatty acid poleysters is made by lipid acid and polyvalent alcohol esterification reaction, wherein lipid acid is excessive:
Lipid acid+polyvalent alcohol → fatty acid poleysters+water
14. described fatty acid polyglycol second diester refers to lipid acid and polyoxyethylene glycol esterification reaction makes, wherein lipid acid is excessive:
Lipid acid+polyoxyethylene glycol → fatty acid polyglycol second diester+water
(4) the concrete mode of implementing
Embodiment 1:
Synthesizing of the butyl laurate of use homogeneous acid catalyst
In there-necked flask, add 1: 1.2 lauric acid of mol ratio and butanols, load onto in addition magnetic agitation and add and account for the vitriol oil of reaction-ure mixture 5% of thermometer, reflux condensing tube and water trap as catalyzer.When the temperature of reaction soln reaches 110 ℃, continue reacting by heating and be no more than 4h, water constantly steams reactor by water trap so that reaction is carried out to the positive reaction direction as the by product of esterification.Lauric transformation efficiency reaches 93%.
Reaction finishes the thick product in back and is cooled to room temperature, and by alkali cleaning is until neutrality repeatedly, the water in the product is removed by distillation.Responseless butanols and lauric acid are discharged by underpressure distillation.Unreacted lauric acid is as resistates, and butyl laurate is collected as overhead product.
Embodiment 2:
Use other homogeneous catalyst to prepare butyl laurate:
The preparation method of butyl ester uses tosic acid with example 1, and silicotungstic acid, phospho-wolframic acid replace sulfuric acid as catalyzer, and lauric transformation efficiency is respectively 87.8%, 87.2% and 81.1%.
Embodiment 3:
Use the preparation of the butyl laurate of heterogeneous acid catalyst:
The preparation method of butyl ester is with example 1, spent ion exchange resin, and the phospho-wolframic acid of MCM-41 load, Nafion-H replace sulfuric acid as heterogeneous acid catalyst, and lauric transformation efficiency is respectively 84.4%, 84.6% and 36.2%.
After reaction finished, crude product was cooled to room temperature, filtered and told catalyzer, and unreacted butanols and lauric acid are removed by underpressure distillation,
Embodiment 4:
The homogeneous catalysis of butyl oleate
The preparation method of butyl oleate is with example 1, and butyl oleate replaces butyl laurate as fraction collection.Oleic transformation efficiency is 85%, and the oleic acid transformation efficiency is 90% when zirconium sulfate replaces sulfuric acid as homogeneous catalyst.
Embodiment 5:
The heterogeneous catalyst of butyl oleate
The preparation method of butyl oleate is with example 1, and butyl oleate replaces butyl laurate as fraction collection.Ion exchange resin, the zirconium sulfate of HZSM-5 load, activated carbon supported zirconium sulfate, silicon dioxide carried zirconium sulfate and HZSM-5 replace the catalyzer of sulfuric acid as heterogeneous catalyst, and oleic transformation efficiency is respectively 85.2%, 92.0%, 91.8%, 91.0% and 30.8%.
Embodiment 6:
The homogeneous catalysis of palmitinic acid second diester
With mol ratio is that 2.2: 1 palmitinic acid and ethylene glycol are packed in the reactor, loads onto thermometer, reflux condensing tube and water trap and magnetic agitation in addition.When the temperature of reaction soln reaches 150 ℃, add and account for the tosic acid of reaction-ure mixture 5% as catalyzer.Continue reacting by heating and be no more than 6h, water constantly steams reactor by water trap so that reaction is carried out to the positive reaction direction as the by product of esterification.The water that generates is constantly discharged reactor, and the transformation efficiency of palmitinic acid is 70.6%.
Reaction finishes the thick product in back and is cooled to room temperature, and acid catalyst will be by continuous alkali cleaning washing till product be neutrality, and the water in the product is removed by distillation.Unreacted butanols and unreacted palmitinic acid are removed by underpressure distillation.Unreacted gets palmitinic acid as resistates, and palmitinic acid second diester is collected as overhead product.If use heterogeneous acid catalyst only to need just can remove by simple filtering.
Embodiment 7:
The homogeneous catalysis of the poly-second diester of lauric acid
With mol ratio is that polyoxyethylene glycol that 2.2: 1 lauric acid and molar mass are 600g/mol is packed in the reactor, loads onto thermometer, reflux condensing tube and water trap and magnetic agitation in addition, heats with heating jacket.When the temperature of reaction soln reaches 160 ℃, add and account for the tosic acid of reaction-ure mixture 5% as catalyzer.Continue reacting by heating 6h, water constantly steams reactor by water trap so that reaction is carried out to the positive reaction direction as the by product of esterification.The water that generates is constantly discharged reactor, and lauric transformation efficiency is 68.7%.
Reaction finishes the thick product in back and is cooled to room temperature, and excessive reactant is removed by rotary evaporation, will be till product be neutrality for removing acid catalyst by continuous alkali cleaning washing, and the water in the product is removed by distillation.Unreacted lipid acid is removed by underpressure distillation.If use heterogeneous acid catalyst only to need just can remove catalyzer by simple filtering.
Claims (10)
1. the invention provides the new method and new technology of preparation fatty acid ester under no azeotropic solvent condition, it is characterized in that under the situation of not using azeotropic solvent, esterification taking place with the lipid acid of 8-22 C atom or their mixture and monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol, polyvalent alcohol or polyoxyethylene glycol, the water that generates in the reaction process is constantly told by the water trap distillation, and reaction is isolated acid catalyst and purified reaction product after finishing.
2. be the alcohol that contains 4-12 C atom according to claim 1 described monohydroxy-alcohol, and isomers and their mixture.
3. dibasic alcohol according to claim 1, trivalent alcohol, tetravalent alcohol, polyvalent alcohol are the alcohol that contains 4-12 C atom, and isomers and their mixture.
4. be the alcohol of molar mass according to claim 1 described polyoxyethylene glycol, comprise that molar mass is polyoxyethylene glycol and isomer and their mixture of 600g/mol at 200-20000g/mol.
5. the azeotropic solvent that method according to claim 1 need not be used comprises toluene, dimethylbenzene, benzene, hexanaphthene, contains the unsaturated alkane and the isomers thereof of 5-12 C atom.
6. homogeneous acid catalyst according to claim 1 comprises the vitriol oil, phosphoric acid, and hydrofluoric acid, tosic acid and the stable hydrocarbon sulfonic acid and the isomers thereof that contain 6-18 C are dissolvable in water the acid of reactant, and catalyst levels accounts for the 1%-10% of reaction-ure mixture.
7. heterogeneous reaction acid catalyst according to claim 1 comprises ion exchange resin, molecular sieve, metal oxide, metal-salt, heteropolyacid, super acids and loading type inorganic salts, load metal oxide, load type metal salt, carried heteropoly acid, catalyst levels account for the 1%-10% of reaction-ure mixture.
8. the method feature according to the described preparation fatty acid monoester of claim 1 is, lipid acid and monohydroxy-alcohol are under the situation that catalyzer exists, temperature of reaction is 80-180 ℃, reaction times is less than 6h, the mol ratio of monohydroxy-alcohol and lipid acid is greater than 1 in the reaction system, do not use azeotropic solvent in the reaction process, reacted product need separate acid catalyst and purification.
9. the method feature according to the described preparation fatty acid poleysters of claim 1 is, lipid acid and dibasic alcohol, trivalent alcohol, tetravalent alcohol, polyvalent alcohol are under the situation that catalyzer exists, temperature of reaction is 100-250 ℃, reaction times is less than 6h, lipid acid is excessive in the reaction system, do not use azeotropic solvent in the reaction process, reacted product need separate acid catalyst and purification.
10. the method feature according to the described preparation fatty acid polyglycol of claim 1 second diester is, lipid acid and polyoxyethylene glycol are under the situation that catalyzer exists, temperature of reaction is 100-250 ℃, reaction times is less than 6h, lipid acid is excessive in the reaction system, do not use azeotropic solvent in the reaction process, reacted product need separate acid catalyst and purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610080720 CN101074191A (en) | 2006-05-15 | 2006-05-15 | Esterification of non-solvent aliphatic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610080720 CN101074191A (en) | 2006-05-15 | 2006-05-15 | Esterification of non-solvent aliphatic ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101074191A true CN101074191A (en) | 2007-11-21 |
Family
ID=38975487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610080720 Pending CN101074191A (en) | 2006-05-15 | 2006-05-15 | Esterification of non-solvent aliphatic ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101074191A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789030A (en) * | 2015-04-29 | 2015-07-22 | 福建省创益建材科技有限公司 | Film-forming assistant for environment-friendly latex paints and preparation method thereof |
| CN110511795A (en) * | 2019-08-31 | 2019-11-29 | 中海油天津化工研究设计院有限公司 | A kind of process of preparing of novel ester type diesel antiwear additive |
| CN111423324A (en) * | 2020-02-26 | 2020-07-17 | 沈阳张明化工有限公司 | Process for synthesizing fatty acid ester by catalyzing tin oxide |
-
2006
- 2006-05-15 CN CN 200610080720 patent/CN101074191A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789030A (en) * | 2015-04-29 | 2015-07-22 | 福建省创益建材科技有限公司 | Film-forming assistant for environment-friendly latex paints and preparation method thereof |
| CN110511795A (en) * | 2019-08-31 | 2019-11-29 | 中海油天津化工研究设计院有限公司 | A kind of process of preparing of novel ester type diesel antiwear additive |
| CN111423324A (en) * | 2020-02-26 | 2020-07-17 | 沈阳张明化工有限公司 | Process for synthesizing fatty acid ester by catalyzing tin oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1084324C (en) | Continuous preparation of alkyl esters of (meth) acrylic acid and apparatus for this purpose | |
| WO2006019495A1 (en) | Improved process for production of organic acid esters | |
| CN103193594A (en) | Method for separating ethylene glycol and 1, 2-butanediol | |
| CN1204640A (en) | Preparation of esters | |
| CN1184095A (en) | Production process for (poly) alkylene glycol monoalkyl ether | |
| FI106796B (en) | Process for the preparation of carboxylic acids or esters thereof by oxidative digestion of unsaturated fatty acids or esters thereof | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN103772146A (en) | Method for separating glycol and 1,2-butanediol | |
| CN101074191A (en) | Esterification of non-solvent aliphatic ester | |
| WO2015038885A1 (en) | Hydrolysis at high ester to water ratios | |
| CN101065347A (en) | Method for the production of phthalic dichloride | |
| CN106892798B (en) | Process for preparing dichloropropanol | |
| CN114656358A (en) | Method for preparing ester compound containing olefin under catalysis of deep eutectic solvent | |
| CN1332924C (en) | Method for esterifying organic acid | |
| CN1166608C (en) | Three-phase phase-transfer catalytic synthesis process of 9,9-dimethoxyl methyl) fluorene | |
| CN114181040B (en) | Preparation method of dichloropropanol | |
| CN1537848A (en) | Process for simultaneous production of maleic anlydride and its hydrogenated derivatives | |
| CN1087013C (en) | Esterification of (meth) acrylic acid with alkanol | |
| CN1158840A (en) | Esterification of (meth) acrylic acid with alkanol | |
| CN1325840A (en) | Process for preparing ethyl acetate | |
| CN1753859A (en) | Process for conducting equilibrium-limited reactions | |
| CN108864010B (en) | Method for preparing phthalic anhydride from 5-hydroxymethylfurfural | |
| CN1566064A (en) | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation | |
| CN1079955A (en) | Dehydrolysation of dicarboxylate of alkyl | |
| CN1098712A (en) | 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |