CN106632161A - Method used for preparing gamma-valerolactone via high-selectivity catalysis - Google Patents
Method used for preparing gamma-valerolactone via high-selectivity catalysis Download PDFInfo
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- CN106632161A CN106632161A CN201610979878.3A CN201610979878A CN106632161A CN 106632161 A CN106632161 A CN 106632161A CN 201610979878 A CN201610979878 A CN 201610979878A CN 106632161 A CN106632161 A CN 106632161A
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- gamma
- valerolactone
- high selectivity
- catalytic preparation
- mixture
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Abstract
The invention discloses a method used for preparing gamma-valerolactone via high-selectivity catalysis. According to the method, an acetyl propionate, an organic solvent, and a binary catalyst are taken as raw materials, ultrasonic oscillation is adopted, and heating reaction is carried out under microwave conditions so as to prepare gamma-valerolactone. The method is mild in reaction conditions, and high in conversion rate; less by-product is generated; and the method is especially suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to the field of chemical synthesis, more particularly to a kind of method of high selectivity catalytic preparation of gamma-valerolactone.
Background technology
Environmental pollution and shortage of resources have become two big outstanding problems of current social development.With non-renewable resources
Increasingly reduction, exploitation and the use of renewable resource is the important directions now concerning energy research.Biomass energy is that one kind can
The renewable resource of liquid fuel and carbon-based chemicals is converted into, it is converted in eco-friendly medium, with important
Practical value.Biomass can be converted into levulic acid or levulinate, further be converted into afterwards in γ-penta
Ester, gamma-valerolactone can be converted into 2- methyl-tetrahydro furans.2- methyl-tetrahydro furans is generally acknowledged regeneratable liquors fuel
Substitute.
Gamma-valerolactone have as the good physical and chemical performance of energy substance, have higher boiling point, relatively low fusing point,
Lightning temperature is high, nontoxic and with readily identified smell is revealed, and belongs to environmentally friendly resource.With traditional liquid fuel phase
Than gamma-valerolactone has relatively low vapour pressure, with very low volatility.In addition, gamma-valerolactone is also used as car
Used with liquid fuel.
Prepare gamma-valerolactone and there are multiple pathways using levulic acid and levulic acid esters compound, urge for example with acid
Change method, microbiological process, transition metal-catalyzed method or homogeneous catalysis reducing process etc..Wherein, using acid catalyzed process preparation process
Middle needs can just be prepared into gamma-valerolactone after being first acidified after Degradation and Transformation, and process is complex, and yield is relatively low；
Microbiological process prepares gamma-valerolactone, poor process control, and yield is equally than relatively low.Using transition metal-catalyzed method and
Homogeneous catalysis reducing process is at the hot focus of nearest research.
Chinese patent ZL201310011149.5 discloses the side that high selectivity under a kind of temperate condition prepares gamma-valerolactone
Method, the method be by levulic acid esters compound in room temperature preferably under inert gas conditions, with secondary alcohol as hydrogen source, apparatus
Activated skeleton nickel obtains gamma-valerolactone as catalyst through hydrogen transfer reaction.The yield of the method gamma-valerolactone is high,
But operation is complex, and required environmental condition is harsher.
The content of the invention
It is an object of the invention to provide a kind of method of high selectivity catalytic preparation of gamma-valerolactone, the method reaction condition
Gently, high conversion rate, accessory substance is few, is very suitable for large-scale industrial production.
For achieving the above object, the present invention is employed the following technical solutions：
The method of catalytic preparation of gamma-valerolactone, comprises the following steps under a kind of temperate condition：
(1) levulic acid esters, organic solvent and binary catalyst are well mixed, ultrasonic vibration 2-4h；
(2) feed the mixture in microwave equipment, setting power is 300W, under the conditions of 100-120 DEG C, react 90-
120min, afterwards rapidly lowers the temperature reactant, separated prepared gamma-valerolactone.
Wherein, binary catalyst is the mixture of aluminium isopropoxide and pyrovinic acid.
Preferably, the levulic acid esters are methyl ester levulinate, acetate propionate ethyl ester, levulic acid propyl ester or acetyl
One or more mixture in butyl propionate.
Preferably, the organic solvent is 1 for the volume ratio of isopropanol and methyl alcohol:2 mixture.
Preferably, the binary catalyst and the mass ratio that feeds intake of levulic acid esters are 1:2-6.
Preferably, the mass ratio of aluminium isopropoxide and pyrovinic acid is 5 in the binary catalyst:1.
Preferably, the levulic acid esters quality and the volume ratio of organic solvent are 30-50g/L.
The invention has the advantages that, it is catalyzed using binary catalyst so that levulic acid esters can be relatively low
Temperature conditionss under, be efficiently converted into gamma-valerolactone.The method simple production process, reaction condition is gentle, without the need for too high
Temperature and pressure, low production cost.Prepare the purity height of gamma-valerolactone product using the method simultaneously, yield is high, with higher
Economic worth.
Specific embodiment
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
The method of catalytic preparation of gamma-valerolactone, comprises the following steps under a kind of temperate condition：
(1) methyl ester levulinate 100g, organic solvent 2L and binary catalyst 20g are well mixed, ultrasonic vibration 2h, its
Middle binary catalyst is 5 for the mass ratio of aluminium isopropoxide and pyrovinic acid:1 mixture, organic solvent is isopropanol and methyl alcohol
Volume ratio is 1:2 mixture；(2) feed the mixture in microwave equipment, setting power is 300W, under the conditions of 110 DEG C, instead
120min is answered, reactant is lowered the temperature rapidly afterwards, separated prepared gamma-valerolactone.The yield of wherein gamma-valerolactone is
89.20%.
Embodiment 2
The method of catalytic preparation of gamma-valerolactone, comprises the following steps under a kind of temperate condition：
(1) acetate propionate ethyl ester 100g, organic solvent 3L and binary catalyst 45g are well mixed, ultrasonic vibration 3h, its
Middle binary catalyst is 5 for the mass ratio of aluminium isopropoxide and pyrovinic acid:1 mixture, organic solvent is isopropanol and methyl alcohol
Volume ratio is 1:2 mixture；(2) feed the mixture in microwave equipment, setting power is 300W, under the conditions of 100 DEG C, instead
90min is answered, reactant is lowered the temperature rapidly afterwards, separated prepared gamma-valerolactone.The yield of wherein gamma-valerolactone is
94.35%.
Embodiment 3
The method of catalytic preparation of gamma-valerolactone, comprises the following steps under a kind of temperate condition：
(1) levulic acid propyl ester 100g, organic solvent 2.8L and binary catalyst 20g are well mixed, ultrasonic vibration 4h,
Wherein binary catalyst is 5 for the mass ratio of aluminium isopropoxide and pyrovinic acid:1 mixture, organic solvent is isopropanol and methyl alcohol
Volume ratio be 1:2 mixture；(2) feed the mixture in microwave equipment, setting power is 300W, under the conditions of 120 DEG C,
Reaction 90min, afterwards rapidly lowers the temperature reactant, separated prepared gamma-valerolactone.The yield of wherein gamma-valerolactone is
97.67%.
Embodiment 4
The method of catalytic preparation of gamma-valerolactone, comprises the following steps under a kind of temperate condition：
(1) Butyl acetylpropanoate 100g, organic solvent 3L and binary catalyst 30g are well mixed, ultrasonic vibration 2h, its
Middle binary catalyst is 5 for the mass ratio of aluminium isopropoxide and pyrovinic acid:1 mixture, organic solvent is isopropanol and methyl alcohol
Volume ratio is 1:2 mixture；(2) feed the mixture in microwave equipment, setting power is 300W, under the conditions of 100 DEG C, instead
120min is answered, reactant is lowered the temperature rapidly afterwards, separated prepared gamma-valerolactone.The yield of wherein gamma-valerolactone is
92.87%.
Embodiment 5
The method of catalytic preparation of gamma-valerolactone, comprises the following steps under a kind of temperate condition：
(1) by the mixture 100g of methyl ester levulinate and acetate propionate ethyl ester, organic solvent 3.3L and binary catalyst
25g is well mixed, and ultrasonic vibration 3h, wherein binary catalyst are 5 for the mass ratio of aluminium isopropoxide and pyrovinic acid:1 mixture,
Organic solvent is 1 for the volume ratio of isopropanol and methyl alcohol:2 mixture；(2) feed the mixture in microwave equipment, work(is set
Rate is 300W, under the conditions of 110 DEG C, reacts 120min, and reactant is lowered the temperature rapidly afterwards, separated prepared gamma-valerolactone.Its
The yield of middle gamma-valerolactone is 89.37%.
Claims (6)
1. a kind of method of high selectivity catalytic preparation of gamma-valerolactone, it is characterised in that comprise the following steps：
(1) levulic acid esters, organic solvent and binary catalyst are well mixed, ultrasonic vibration 2-4h；
(2) feed the mixture in microwave equipment, setting power is 300W, under the conditions of 100-120 DEG C, react 90-120min,
Reactant is lowered the temperature rapidly afterwards, separated prepared gamma-valerolactone, wherein binary catalyst are aluminium isopropoxide and pyrovinic acid
Mixture.
2. the method for a kind of high selectivity catalytic preparation of gamma-valerolactone according to claim 1, it is characterised in that：It is described
Levulic acid esters be methyl ester levulinate, acetate propionate ethyl ester, levulic acid propyl ester or Butyl acetylpropanoate in one kind or
Various mixtures.
3. the method for a kind of high selectivity catalytic preparation of gamma-valerolactone according to claim 1, it is characterised in that：It is described
Organic solvent is 1 for the volume ratio of isopropanol and methyl alcohol:2 mixture.
4. the method for a kind of high selectivity catalytic preparation of gamma-valerolactone according to claim 1, it is characterised in that：It is described
Binary catalyst feeds intake mass ratio for 1 with levulic acid esters:2-6.
5. the method for a kind of high selectivity catalytic preparation of gamma-valerolactone according to claim 1, it is characterised in that：It is described
The mass ratio of aluminium isopropoxide and pyrovinic acid is 5 in binary catalyst:1.
6. the method for a kind of high selectivity catalytic preparation of gamma-valerolactone according to claim 1, it is characterised in that：It is described
Levulic acid esters quality is 30-50g/L with the volume ratio of organic solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111434657A (en) * | 2019-01-15 | 2020-07-21 | 吉林大学 | Preparation method of gamma-valerolactone and levulinic acid ester compounds |
| CN115069309A (en) * | 2022-07-25 | 2022-09-20 | 国家纳米科学中心 | Enzyme-like catalyst based on metal organic framework material and preparation method and application thereof |
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| US2713074A (en) * | 1949-08-25 | 1955-07-12 | Exxon Research Engineering Co | Aluminum alcoholate reduction of oxo aldehyde mixtures |
| CN1190386A (en) * | 1996-03-05 | 1998-08-12 | 花王株式会社 | Process for producing unsaturated alcohols |
| CN101376650A (en) * | 2008-09-08 | 2009-03-04 | 中国科学技术大学 | Method for directly preparing gamma-valerolactone from acetylpropionic acid and aminic acid |
| CN103012334A (en) * | 2013-01-11 | 2013-04-03 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
-
2016
- 2016-11-08 CN CN201610979878.3A patent/CN106632161A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2713074A (en) * | 1949-08-25 | 1955-07-12 | Exxon Research Engineering Co | Aluminum alcoholate reduction of oxo aldehyde mixtures |
| CN1190386A (en) * | 1996-03-05 | 1998-08-12 | 花王株式会社 | Process for producing unsaturated alcohols |
| CN101376650A (en) * | 2008-09-08 | 2009-03-04 | 中国科学技术大学 | Method for directly preparing gamma-valerolactone from acetylpropionic acid and aminic acid |
| CN103012334A (en) * | 2013-01-11 | 2013-04-03 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
Non-Patent Citations (2)
| Title |
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| BOWMAN,R.E.等: "Synthesis of carbonyl compounds. IV", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
| 蒋龙飞等: "多项催化乙酰丙酸甲酯合成γ-戊内酯的研究", 《食品工业科技》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111434657A (en) * | 2019-01-15 | 2020-07-21 | 吉林大学 | Preparation method of gamma-valerolactone and levulinic acid ester compounds |
| CN111434657B (en) * | 2019-01-15 | 2023-06-16 | 吉林大学 | Preparation method of gamma-valerolactone and levulinate ester compound |
| CN115069309A (en) * | 2022-07-25 | 2022-09-20 | 国家纳米科学中心 | Enzyme-like catalyst based on metal organic framework material and preparation method and application thereof |
| CN115069309B (en) * | 2022-07-25 | 2024-03-05 | 国家纳米科学中心 | Enzyme-like catalyst based on metal organic framework material and preparation method and application thereof |
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