CN1226270C - Prepn of fatty alcohol acetate - Google Patents
Prepn of fatty alcohol acetate Download PDFInfo
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- CN1226270C CN1226270C CN 02110798 CN02110798A CN1226270C CN 1226270 C CN1226270 C CN 1226270C CN 02110798 CN02110798 CN 02110798 CN 02110798 A CN02110798 A CN 02110798A CN 1226270 C CN1226270 C CN 1226270C
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- fatty alcohol
- ritalin
- alcohol
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- amyl acetate
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Abstract
The present invention relates to a method for preparing corresponding fatty alcohol ester acetate, which takes methyl acetate and fatty alcohol as raw material. Ester exchange reaction is carried out to the fatty alcohol and the methyl acetate under the condition that catalysts exist, the reaction temperature is from 70 to 180 DEG C, the reaction pressure is from 0.15 to 2.0MPa, and the product fatty alcohol ester acetate is obtained by rectifying and separating after reaction material reacts for 2 to 6 hours. The fatty alcohol can be one of ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol and isooctanol. The present invention solves the technical problem that because the boiling point of the methyl acetate is lower than that of other substances in the ester exchange reaction system, the ester exchange reaction of the methyl acetate and other fatty alcohol can not occur with a conventional method to prepare the corresponding fatty alcohol ester acetate. The positive significance of the present invention lies in searching a use method with higher benefit for byproduct methyl acetate in the process of polyvinyl alcohol prepared by the alcoholysis of polyvinyl acetate and methanol.
Description
Technical field
The invention belongs to a kind of is raw material with ritalin and Fatty Alcohol(C12-C14 and C12-C18), prepares the method for corresponding amyl acetate fatty alcohol in the presence of catalyzer by transesterification reaction.
Background technology
At present, the suitability for industrialized production polyvinyl alcohol generally is to make Vinyl Acetate Copolymer earlier, and alcoholysis in alkaline aqueous solution makes polyvinyl alcohol with Vinyl Acetate Copolymer and methyl alcohol then.In this process, will produce a large amount of by-product methyl acetates.The ritalin of this by-product exists with the form of mixtures of ritalin, methyl alcohol, water and small amount of impurities, wherein the content of ritalin is about 60～85%, the content of methyl alcohol is about 15～40%, the content of water is about 0.5%～10%, the content of impurity is about 0.1～5%, because by-product ritalin purity is not high, contains more methyl alcohol, so direct using value is little.Therefore, industrial many ritalin mixtures with this by-product are hydrolyzed and reclaim acetic acid and methyl alcohol is applied mechanically.But, in the prior art by-product methyl acetate hydrolysis reclaim operational path long, relate to that appliance arrangement is many, complicated operation, energy consumption greatly, production cost is higher.Particularly produce the industrialization of acetic acid along with carbonylating process, making that the production cost of acetic acid is low greatly reduces, and the method that still adopts the hydrolysis recovery set to use to the ritalin of by-product just seems very uneconomical.
Theoretically, ester compound can make by direct esterification reaction or transesterify (comprise ester and alcohol, ester and the exchange of acid or the exchange of ester and the ester) reaction of alcohol with acid, and ritalin can make corresponding amyl acetate fatty alcohol by transesterification reaction with Fatty Alcohol(C12-C14 and C12-C18).Many amyl acetate fatty alcohols all have higher using value, can be used in the perfume industry as N-BUTYL ACETATE, and also can be used as solvent and be used for industry such as plastics, coating, nitrocotton, imitation leather, or as extraction agent, band aqua etc.; Propyl acetate can be used as the retentivity quick dry agent, is used for printing-ink or is used for nitrocellulose, chlorinated rubber and resol etc. as solvent; Amyl acetate-n can be used as solvent, is used for coating, spices, makeup, wood binder, or is used for imitation leather, weaving processing, film and gunpowder manufacture view; Isobutyl acetate except that as nitrocotton and the solvent of paint, be commonly used for fruit flavors or as the aromatics modifier of rose.But, ritalin and Fatty Alcohol(C12-C14 and C12-C18) carry out transesterification reaction and prepare corresponding amyl acetate fatty alcohol and but face such problem: the boiling point (54 ℃) of the azeotrope that ritalin or it and methyl alcohol form is usually less than the boiling point of other materials in the transesterification reaction system (reactant or reaction product), therefore, in the transesterify process, the evaporation because of ritalin in the reaction system makes that transesterification reaction is difficult to carry out.So, can't make ritalin and other Fatty Alcohol(C12-C14 and C12-C18) generation transesterification reactions prepare corresponding amyl acetate fatty alcohol with conventional method.
Summary of the invention
It is raw material with ritalin and Fatty Alcohol(C12-C14 and C12-C18) that technical problem to be solved by this invention provides a kind of, prepares the method for corresponding amyl acetate fatty alcohol by transesterification reaction.Particularly being prepared the mixture that is rich in ritalin of by-product in the polyvinyl alcohol process by Vinyl Acetate Copolymer and methyl alcohol alcoholysis, and Fatty Alcohol(C12-C14 and C12-C18) is raw material, prepares corresponding amyl acetate fatty alcohol by transesterification reaction.It will for the ritalin of this by-product seek a kind of benefit higher utilize method.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of is raw material with ritalin and Fatty Alcohol(C12-C14 and C12-C18), the method for preparing corresponding amyl acetate fatty alcohol, used ritalin raw material is for being prepared the mixture that is rich in ritalin of by-product in the polyvinyl alcohol process by Vinyl Acetate Copolymer and methyl alcohol alcoholysis, wherein the content of ritalin is 60～85%.Fatty Alcohol(C12-C14 and C12-C18) and ritalin mixture are carried out transesterification reaction in the presence of catalyzer, temperature of reaction is 70～180 ℃, and reaction pressure is 0.15～2.0MPa, reacts 2～6 hours afterreaction materials and gets product amyl acetate fatty alcohol through rectifying separation.Catalyzer is sal enixum, tosic acid or HZSM-5 molecular sieve, and catalyst consumption is 0.1%～8% of a reaction mass total mass.
Above-mentioned Fatty Alcohol(C12-C14 and C12-C18) can be in ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, hexanol, isohexyl alcohol, enanthol, iso-heptanol, octanol or the isooctyl alcohol a kind of.
Feeding intake of transesterification reaction raw material is can ritalin excessive, and at this moment, Fatty Alcohol(C12-C14 and C12-C18) and ritalin feed intake with following mol ratio and carry out transesterification reaction:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1: 1.1～1: 3.5, and the contriver more recommends:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1: 1.5～1: 1.9;
Feeding intake also of transesterification reaction raw material is can Fatty Alcohol(C12-C14 and C12-C18) excessive, and at this moment, Fatty Alcohol(C12-C14 and C12-C18) and ritalin feed intake with following mol ratio and carry out transesterification reaction:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1.1: 1～3.0: 1, and the contriver more recommends:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1.5: 1～1.9: 1.
The contriver finds that through after a large amount of tests reaction pressure is very big to above-mentioned transesterification reaction influence, suitably improves the trim point that reaction pressure can change reaction, makes reaction be easy to carry out.
Compared with prior art, positive effect of the present invention has been to provide that a kind of to be easy to industrialized ritalin and the Fatty Alcohol(C12-C14 and C12-C18) for preparing by-product in the polyvinyl alcohol process with Vinyl Acetate Copolymer and methyl alcohol alcoholysis be raw material, prepare the method for corresponding amyl acetate fatty alcohol by transesterification reaction, for the ritalin of this by-product sought a kind of benefit higher utilize method.
Embodiment
To come below that the invention will be further described by some specific embodiments, in an embodiment, the yield of the transformation efficiency of ritalin, amyl acetate fatty alcohol is defined as:
[embodiment 1～4]
With purity is the ritalin mixture (ritalin content is 60～85%) of Fatty Alcohol(C12-C14 and C12-C18), Vinyl Acetate Copolymer and methyl alcohol alcoholysis system polyvinyl alcohol by-product more than 95%, add one by required feed ratio and have in the enamel reactor of the cool condenser that refluxes, and add the catalyzer of aequum.Reactant is heated to suitable temperature while stirring under pressurized conditions.The content of each component in the material chromatographically detection reaction product is answered in negate after the suitable reaction times of process, calculates reaction result.Reaction end afterreaction product separates purification and obtains corresponding amyl acetate fatty alcohol product.
Concrete Fatty Alcohol(C12-C14 and C12-C18) raw material, catalyzer and consumption thereof, concrete reaction conditions see Table 1 and table 2, and reaction result sees Table 3.
Table 1.
| The Fatty Alcohol(C12-C14 and C12-C18) raw material | Feed ratio | Catalyzer | |
| Embodiment 1 | Butanols | 3∶2 | Sal enixum |
| Embodiment 2 | Primary isoamyl alcohol | 6∶2 | HZSM-5 |
| Embodiment 3 | Isooctyl alcohol | 3∶2 | Sal enixum |
| Embodiment 4 | Butanols | 3∶2 | Tosic acid |
Table 2.
| Catalyst levels (%) | Temperature of reaction (℃) | Reaction pressure (MPa) | Reaction times (hr) | |
| Embodiment 1 | 1.2 | 135～140 | 0.75～0.88 | 5 |
| Embodiment 2 | 2.0 | 160～170 | 1.53～1.75 | 6 |
| Embodiment 3 | 1.2 | 160～170 | 1.53～1.75 | 5 |
| Embodiment 4 | 0.9 | 135～140 | 0.75～0.88 | 5 |
Annotate: feed ratio is a Fatty Alcohol(C12-C14 and C12-C18): ritalin (mol ratio); Catalyst levels is the weight percentage in the reaction mass total mass.
Table 3.
| Ritalin transformation efficiency (%) | Amyl acetate fatty alcohol yield (%) | |
| Embodiment 1 | 56.7 | 45.9 |
| Embodiment 2 | 48.1 | 39.9 |
| Embodiment 3 | 51.4 | 40.2 |
| Embodiment 4 | 52.3 | 42.7 |
Table 2.
| Catalyst levels (%) | Temperature of reaction (℃) | Reaction pressure (MPa) | Reaction times (hr) | |
| Embodiment 1 | 1.2 | 85～90 | 0.25～0.31 | 5 |
| Embodiment 2 | 1.2 | 115～120 | 0.51～0.62 | 5 |
| Embodiment 3 | 1.2 | 135～140 | 0.75～0.88 | 5 |
| Embodiment 4 | 1.2 | 165～170 | 1.53～1.75 | 5 |
| Embodiment 5 | 0.8 | 135～140 | 0.75～0.88 | 4 |
| Embodiment 6 | 2.0 | 165～170 | 1.53～1.75 | 6 |
| Embodiment 7 | 0.9 | 135～140 | 0.75～0.88 | 5 |
| Embodiment 8 | 2.0 | 160～170 | 1.53～1.75 | 6 |
| Embodiment 9 | 1.2 | 135～140 | 0.75～0.88 | 5 |
| Embodiment 10 | 1.2 | 135～140 | 0.75～0.88 | 5 |
| Embodiment 11 | 2.0 | 160～170 | 1.53～1.75 | 6 |
| Embodiment 12 | 0.8 | 135～140 | 0.75～0.88 | 5 |
| Embodiment 13 | 1.2 | 160～170 | 1.53～1.75 | 5 |
| Embodiment 14 | 1.0 | 135～140 | 0.75～0.88 | 4 |
| Embodiment 15 | 0.9 | 135～140 | 0.75～0.88 | 5 |
Annotate: feed ratio is a Fatty Alcohol(C12-C14 and C12-C18): ritalin (mol ratio); Catalyst levels is the weight percentage in the reaction mass total mass.
Table 3.
| Ritalin transformation efficiency (%) | Amyl acetate fatty alcohol yield (%) | |
| Embodiment 1 | 53.1 | 44.8 |
| Embodiment 2 | 56.2 | 45.5 |
| Embodiment 3 | 57.8 | 46.3 |
| Embodiment 4 | 58.5 | 47.6 |
| Embodiment 5 | 85.4 | 44.9 |
| Embodiment 6 | 50.3 | 43.2 |
| Embodiment 7 | 53.6 | 44.0 |
| Embodiment 8 | 49.1 | 42.5 |
| Embodiment 9 | 37.2 | 31.5 |
| Embodiment 10 | 56.7 | 45.9 |
| Embodiment 11 | 48.1 | 39.9 |
| Embodiment 12 | 88.2 | 41.3 |
| Embodiment 13 | 51.4 | 40.2 |
| Embodiment 14 | 48.5 | 38.1 |
| Embodiment 15 | 52.3 | 42.7 |
Claims (6)
1, a kind of is raw material with ritalin and Fatty Alcohol(C12-C14 and C12-C18), the method for preparing corresponding amyl acetate fatty alcohol, used ritalin raw material is for being prepared the mixture that is rich in ritalin of by-product in the polyvinyl alcohol process by Vinyl Acetate Copolymer and methyl alcohol alcoholysis, wherein the content of ritalin is 60～85%, Fatty Alcohol(C12-C14 and C12-C18) and ritalin mixture are carried out transesterification reaction in the presence of catalyzer, temperature of reaction is 70～180 ℃, reaction pressure is 0.15～2.0MPa, react 2～6 hours afterreaction materials and get product amyl acetate fatty alcohol through rectifying separation, catalyzer is a sal enixum, tosic acid or HZSM-5 molecular sieve, catalyst consumption are 0.1%～8% of reaction mass total mass.
2, the method for preparing the amyl acetate fatty alcohol according to claim 1 is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is a kind of in ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, hexanol, isohexyl alcohol, enanthol, iso-heptanol, octanol or the isooctyl alcohol.
3, the method for preparing the amyl acetate fatty alcohol according to claim 1, it is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) and ritalin feed intake with following mol ratio carries out transesterification reaction:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1: 1.1～1: 3.5.
4, the method for preparing the amyl acetate fatty alcohol according to claim 3, it is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) and ritalin feed intake with following mol ratio carries out transesterification reaction:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1: 1.5～1: 1.9.
5, the method for preparing the amyl acetate fatty alcohol according to claim 1, it is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) and ritalin feed intake with following mol ratio carries out transesterification reaction:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1.1: 1～3.0: 1.
6, the method for preparing the amyl acetate fatty alcohol according to claim 5, it is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) and ritalin feed intake with following mol ratio carries out transesterification reaction:
Fatty Alcohol(C12-C14 and C12-C18): ritalin=1.5: 1～1.9: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02110798 CN1226270C (en) | 2002-02-07 | 2002-02-07 | Prepn of fatty alcohol acetate |
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| CN 02110798 CN1226270C (en) | 2002-02-07 | 2002-02-07 | Prepn of fatty alcohol acetate |
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| CN1226270C true CN1226270C (en) | 2005-11-09 |
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| CN107522616B (en) * | 2017-08-11 | 2020-12-22 | 山东达冠生化科技股份有限公司 | Synthesis process of sun-screening agent isooctyl p-methoxycinnamate |
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Granted publication date: 20051109 Termination date: 20110207 |