CN102993007A - Alcohol acetate preparation method - Google Patents
Alcohol acetate preparation method Download PDFInfo
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- CN102993007A CN102993007A CN2011102689782A CN201110268978A CN102993007A CN 102993007 A CN102993007 A CN 102993007A CN 2011102689782 A CN2011102689782 A CN 2011102689782A CN 201110268978 A CN201110268978 A CN 201110268978A CN 102993007 A CN102993007 A CN 102993007A
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Abstract
The invention relates to a preparation method of alcohol acetate having a structural formula represented by formula (I). The method comprises the following steps: carrying out a contact reaction of sec-butyl acetate and alcohol in the presence of an ester exchange catalyst under an ester exchange reaction condition, and separating products obtained after the contact reaction to obtain the alcohol acetate of formula (I), wherein the general formula of the alcohol is R1(OH) n, and R1 and n are same to R1 and n in the formula (I). The method has the advantages of high conversion rate of the alcohol as a reaction raw material, and high alcohol acetate selectivity. The formula (I) is shown in the specification.
Description
Technical field
The present invention relates to a kind of preparation method of acetic acid alcohol ester.
Background technology
Usually, the preparation method of acetic acid alcohol ester generates corresponding acetic ester with acetic acid, diacetyl oxide or alkali salt acetate (sylvite, sodium salt etc.) and the reaction under the effect of catalyzer of corresponding alcohol.Yet this method causes equipment corrosion easily, causes environmental pollution, and the product separation complex process, and cost is higher.
Ester exchange method also is a kind of method for preparing the acetic acid alcohol ester relatively more commonly used, concrete, the method mainly is that ester and alcohol are reacted under the katalysis of transesterification catalyst (such as an acidic catalyst, basic catalyst, biological enzyme agent etc.), generate a kind of new ester and a kind of new alcohol, this reaction is the alcoholysis reaction of ester, is the reversed reaction of the esterification of acid and alcohol.Because this reaction is reversible, so the yield of general objectives product is lower, this also is that transesterification reaction is used one of principal element of not too popularizing in industrial production.
What industrial application was slightly many at present generally is to adopt the alcohol of the cheaper lower member ester of the prices such as methyl acetate, ethyl acetate and higher carbon number to carry out the senior ester of transesterify production acetic acid, yet still there are the shortcomings such as low conversion rate, product separation complexity in present Technology.
Summary of the invention
The objective of the invention is to have the complicated shortcoming of low conversion rate, product separation in order to overcome the existing method for preparing the acetic acid alcohol ester, a kind of preparation method of new acetic ester is provided.
The invention provides a kind of structural formula suc as formula the preparation method of the acetic acid alcohol ester shown in (I),
Formula (I):
Wherein, R
1Be the n valency alkyl of C5-C20, the n valency thiazolinyl of C5-C20, the n valency cycloalkyl of C5-C12 or the n valency aryl of C7-C20, n is the integer of 1-5, and x is the integer of 0-4, and x is less than n;
The method comprises: in the presence of transesterification catalyst, under the transesterification reaction condition, with sec-butyl acetate and pure contact reacts, isolate described structural formula the product that after described contact reacts, obtains suc as formula the acetic acid alcohol ester shown in (I), the general formula of described alcohol is R
1(OH)
n, wherein, R
1Identical with in n and the above-mentioned formula (I).
The preparation method of acetic acid alcohol ester according to the present invention can obtain transformation efficiency and the acetic acid alcohol ester selectivity of higher alcohol as reaction raw materials.
Method according to the present invention, technique is simple, and lower to the production unit requirement, raw material is easy to get, and energy consumption is low, thereby greatly reduces production cost; And, need not to use acetic acid, sulfuric acid etc. as raw material, reduced equipment corrosion and environmental pollution.
Embodiment
The invention provides a kind of preparation method of acetic acid alcohol ester, the structural formula of this acetic acid alcohol ester is suc as formula shown in (I),
Formula (I)
Wherein, R
1Be the n valency alkyl of C5-C20, the n valency thiazolinyl of C5-C20, the n valency cycloalkyl of C5-C12 or the n valency aryl of C7-C20, n is the integer of 1-5, and x is the integer of 0-4, and x is less than n;
Described method comprises: in the presence of transesterification catalyst, under the transesterification reaction condition, with sec-butyl acetate and pure contact reacts, isolate described structural formula the product that obtains suc as formula the acetic acid alcohol ester shown in (I) after described contact reacts.
In the present invention, n valency alkyl refers to that corresponding alkane loses n hydrogen atom structure afterwards.Similarly, n valency thiazolinyl refers to that corresponding alkene loses n hydrogen atom structure afterwards; N valency cycloalkyl refers to that corresponding naphthenic hydrocarbon loses n hydrogen atom structure afterwards; N valency aryl refers to that corresponding aromatic hydrocarbons loses n hydrogen atom structure afterwards.Wherein n hydrogen atom can also can be the hydrogen atom on the different carbon atoms for the hydrogen atom on the same carbon atom.
In the present invention, the general formula of described alcohol is R
1(OH)
n, wherein, R
1Be the n valency alkyl of C5-C20, the n valency thiazolinyl of C5-C20, the n valency cycloalkyl of C5-C12 or the n valency aryl of C7-C20, n is the integer of 1-5.
Under the preferable case, in the general formula and formula (I) of described alcohol, R
1Be the n valency alkyl of C5-C18, the n valency thiazolinyl of C5-C12, the n valency cycloalkyl of C5-C8 or the n valency aryl of C7-C10, n is 1 or 2.Concrete, what described alcohol can be in primary isoamyl alcohol, octanol, nonyl alcohol, Geraniol, undecyl alcohol, lauryl alcohol, hexadecanol, stearyl alcohol, hexalin, cyclopentanol, methyl-cyclohexanol, Terpineol 350, rosin alcohol, phenylcarbinol, phenylethyl alcohol, methylbenzyl alcohol and the styryl carbinol is at least a.
Method according to the present invention, described transesterification reaction condition can suitably be selected in the transesterification reaction condition of routine.Under the preferable case, described transesterification reaction condition comprises: temperature of reaction is 100-200 ℃, and the reaction times is 3-10 hour.
Method according to the present invention, the mol ratio of sec-butyl acetate and described alcohol can be 2-5: 1.
Method according to the present invention, described transesterification catalyst can use with the catalytic amount of routine.Under the preferable case, with respect to the consumption of the described polyol alkyl ether of 100 weight parts, the consumption of described transesterification catalyst is the 1-5 weight part.
Method according to the present invention, described transesterification catalyst can be the conventional various transesterification catalysts that use in this area, for example can be in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, cesium carbonate, tosic acid, zinc acetate, lead acetate, cadmium acetate, calcium oxide, zinc oxide, plumbous oxide, sodium methylate, tetrabutyl titanate, stannous octoate, sulfuric acid, phosphoric acid, polyphosphoric acid, acidic molecular sieve and the ion exchange resin at least a.Described acidic molecular sieve for example can be ZSM-5 molecular sieve, Y zeolite and H beta-molecular sieve.Described ion exchange resin can be acidic ion exchange resin or deacidite, and described acidic ion exchange resin for example can be styrene type cation exchange resin (such as commercially available D001 type, D201 type and D732 type Zeo-karb) or sulfonic group Zeo-karb (such as commercially available DWN type Zeo-karb); The anionite-exchange resin that described deacidite for example can obtain after the sodium hydroxide solution pre-treatment for quaternary ammonium group anionite-exchange resin, tertiary amine fundamental mode anionite-exchange resin or these anionite-exchange resin is such as 201 * 4 commercially available types, 201 * 4H type, D201 type and D301 type anionite-exchange resin.
Method according to the present invention, isolating the method for the acetic acid alcohol ester shown in the above-mentioned formula (I) the product that obtains after described contact reacts can implement according to the separation method of routine, for example can adopt the method for distillation to separate, concrete, for example can comprise that the product that will obtain after the described contact reacts injects distillation tower, control top gaseous phase reflux temperature, to remove unreacted sec-butyl acetate in the described product and newly-generated sec-butyl alcohol, then by tower bottoms being carried out atmospheric flashing or the polyol alkyl ether acetic ester is collected in vacuum flashing.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the transformation efficiency of alcohol and the selectivity of acetic acid alcohol ester calculate according to following calculating formula respectively:
The charging capacity of the transformation efficiency of alcohol=(residual volume of the alcohol that adds as reaction raw materials in the charging capacity-reaction product of alcohol)/alcohol * 100%
The mole number of the alcohol of the mole number of the acetic acid alcohol ester that the selectivity of acetic acid alcohol ester=reaction generates/be converted * 100%
Embodiment 1
Present embodiment is used for illustrating the preparation method of described acetic acid alcohol ester of the present invention.
Sec-butyl acetate and lauryl alcohol are added in the tank reactor as 3: 1 take mol ratio, and with respect to the add-on of the described lauryl alcohol of 100 weight parts, to the D301 anionite-exchange resin that wherein adds 2 weight parts (available from Langfang prosperous chemical building material of prosperous Sheng company limited) as catalyzer, under normal pressure, 140 ℃ of lower reactions 3 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out vacuum flashing, collects lauryl acetate.
Learn that by calculating the selectivity of lauryl acetate is 100%, the transformation efficiency of lauryl alcohol is 99.4%.
Comparative Examples 1
Method according to embodiment 1 prepares lauryl acetate, and difference is to replace sec-butyl acetate with methyl acetate.
Learn that by calculating the selectivity of lauryl acetate is 89.7%, the transformation efficiency of lauryl alcohol is 86.5%.
Embodiment 2
Present embodiment is used for illustrating the preparation method of described acetic acid alcohol ester of the present invention.
Sec-butyl acetate and phenylethyl alcohol are added in the tank reactor as 3: 1 take mol ratio, and with respect to the add-on of the described phenylethyl alcohol of 100 weight parts, to the cesium carbonate that wherein adds 3 weight parts as catalyzer, under normal pressure, 150 ℃ of lower reactions 3 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out vacuum flashing, collects Phenylethyl ethanoate.
Learn that by calculating the selectivity of Phenylethyl ethanoate is 100%, the transformation efficiency of phenylethyl alcohol is 99.6%.
Embodiment 3
Present embodiment is used for illustrating the preparation method of described acetic acid alcohol ester of the present invention.
Sec-butyl acetate and geraniol are added in the tank reactor as 3: 1 take mol ratio, and with respect to the add-on of the described geraniol of 100 weight parts, to the zinc oxide that wherein adds 2 weight parts as catalyzer, under normal pressure, 120 ℃ of lower reactions 3 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out vacuum flashing, collects citronellyl acetate.
Learn that by calculating the selectivity of citronellyl acetate is 100%, the transformation efficiency of geraniol is 99.3%.
Embodiment 4
Present embodiment is used for illustrating the preparation method of described acetic acid alcohol ester of the present invention.
Sec-butyl acetate and styryl carbinol are added in the tank reactor as 3: 1 take mol ratio, and with respect to the add-on of the described styryl carbinol of 100 weight parts, to the tosic acid that wherein adds 2 weight parts as catalyzer, under normal pressure, 115 ℃ of lower reactions 3 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out vacuum flashing, collects cinnamyl acetate.
Learn that by calculating the selectivity of cinnamyl acetate is 100%, the transformation efficiency of styryl carbinol is 99.7%.
Embodiment 5
Present embodiment is used for illustrating the preparation method of described acetic acid alcohol ester of the present invention.
Sec-butyl acetate and cyclopentanol are added in the tank reactor as 5: 1 take mol ratio, and with respect to the add-on of the described cyclopentanol of 100 weight parts, to the styrene type cation exchange resin that wherein adds 5 weight parts (available from Changsha Da Yu chemical industry company limited, trade mark D001) as catalyzer, under normal pressure, 125 ℃ of lower reactions 5 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out vacuum flashing, collects the acetic acid cyclopentyl ester.
Learn that by calculating the selectivity of acetic acid cyclopentyl ester is 100%, the transformation efficiency of cyclopentanol is 99.6%.
Embodiment 6
Present embodiment is used for illustrating the preparation method of described acetic acid alcohol ester of the present invention.
Sec-butyl acetate and Terpineol 350 are added in the tank reactor as 4: 1 take mol ratio, and with respect to the add-on of the described Terpineol 350 of 100 weight parts, to the ZSM-5 molecular sieve that wherein adds 4 weight parts (available from Nanjing Ji Cang nanosecond science and technology company limited) as catalyzer, under normal pressure, 135 ℃ of lower reactions 5 hours.Reaction is added to the product that obtains in the knockout tower after finishing, and control top gaseous phase reflux temperature is 100 ℃, to remove the azeotrope of sec-butyl acetate and sec-butyl alcohol, then the tower reactor cut is carried out vacuum flashing, collects terpinyl acetate.
Learn that by calculating the selectivity of terpinyl acetate is 100%, the transformation efficiency of Terpineol 350 is 99.4%.
Result by above-described embodiment can find out, method according to the present invention can obtain higher raw alcohol transformation efficiency and acetic acid alcohol ester selectivity.Particularly, embodiment 1 is compared and can find out with Comparative Examples 1, with respect to transformation efficiency and the reaction preference of using methyl acetate and raw alcohol to carry out transesterify, by selecting sec-butyl acetate and raw alcohol to carry out transesterification reaction, obtained raw alcohol transformation efficiency and the acetic acid alcohol ester selectivity of obvious raising among the present invention.
Claims (7)
1. a structural formula is suc as formula the preparation method of the acetic acid alcohol ester shown in (I),
Formula (I)
Wherein, R
1Be the n valency alkyl of C5-C20, the n valency thiazolinyl of C5-C20, the n valency cycloalkyl of C5-C12 or the n valency aryl of C7-C20, n is the integer of 1-5, and x is the integer of 0-4, and x is less than n;
The method comprises: in the presence of transesterification catalyst, under the transesterification reaction condition, with sec-butyl acetate and pure contact reacts, isolate described structural formula the product that after described contact reacts, obtains suc as formula the acetic acid alcohol ester shown in (I), the general formula of described alcohol is R
1(OH)
n, wherein, R
1Identical with in n and the above-mentioned formula (I).
2. method according to claim 1, wherein, described transesterification reaction condition comprises: temperature of reaction is 100-200 ℃, the reaction times is 3-10 hour.
3. method according to claim 1, wherein, the mol ratio of sec-butyl acetate and described alcohol is 2-5: 1.
4. according to claim 1 or 3 described methods, wherein, in the general formula and formula (I) of described alcohol, R
1Be the n valency alkyl of C5-C18, the n valency thiazolinyl of C5-C12, the n valency cycloalkyl of C5-C8 or the n valency aryl of C7-C10, n is 1 or 2.
5. method according to claim 4, wherein, described alcohol is at least a in primary isoamyl alcohol, octanol, nonyl alcohol, Geraniol, undecyl alcohol, lauryl alcohol, hexadecanol, stearyl alcohol, hexalin, cyclopentanol, methyl-cyclohexanol, Terpineol 350, rosin alcohol, phenylcarbinol, phenylethyl alcohol, methylbenzyl alcohol and the styryl carbinol.
6. method according to claim 1, wherein, with respect to the consumption of the described alcohol of 100 weight parts, the consumption of described transesterification catalyst is the 1-5 weight part.
7. according to claim 1 or 6 described methods, wherein, described transesterification catalyst is at least a in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, cesium carbonate, tosic acid, zinc acetate, lead acetate, cadmium acetate, calcium oxide, zinc oxide, plumbous oxide, sodium methylate, tetrabutyl titanate, stannous octoate, sulfuric acid, phosphoric acid, polyphosphoric acid, acidic molecular sieve and the ion exchange resin.
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|---|---|---|---|
| CN2011102689782A CN102993007A (en) | 2011-09-13 | 2011-09-13 | Alcohol acetate preparation method |
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|---|---|---|---|
| CN2011102689782A CN102993007A (en) | 2011-09-13 | 2011-09-13 | Alcohol acetate preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898157A (en) * | 2019-11-18 | 2021-06-04 | 石家庄圣泰化工有限公司 | Synthesis method of di (2,2, 2-trifluoroethyl) carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734182A1 (en) * | 1977-07-07 | 1980-05-15 | Ярославский политехнический институт | Method of producing secondary butanol |
| RU2150473C1 (en) * | 1999-08-09 | 2000-06-10 | Государственное унитарное предприятие Центральный научно-исследовательский и проектный институт лесохимической промышленности | Method of synthesis of betulinol diacetate |
-
2011
- 2011-09-13 CN CN2011102689782A patent/CN102993007A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734182A1 (en) * | 1977-07-07 | 1980-05-15 | Ярославский политехнический институт | Method of producing secondary butanol |
| RU2150473C1 (en) * | 1999-08-09 | 2000-06-10 | Государственное унитарное предприятие Центральный научно-исследовательский и проектный институт лесохимической промышленности | Method of synthesis of betulinol diacetate |
Non-Patent Citations (1)
| Title |
|---|
| 黄化民等: "不饱和酸酯的酯交换反应", 《吉林大学自然科学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898157A (en) * | 2019-11-18 | 2021-06-04 | 石家庄圣泰化工有限公司 | Synthesis method of di (2,2, 2-trifluoroethyl) carbonate |
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Application publication date: 20130327 |