CN104844542A - Method for preparing gamma-valerolactone by levulinic acid ester without solvents - Google Patents
Method for preparing gamma-valerolactone by levulinic acid ester without solvents Download PDFInfo
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- CN104844542A CN104844542A CN201510218970.3A CN201510218970A CN104844542A CN 104844542 A CN104844542 A CN 104844542A CN 201510218970 A CN201510218970 A CN 201510218970A CN 104844542 A CN104844542 A CN 104844542A
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- Prior art keywords
- valerolactone
- levulinate
- copper chromite
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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
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- Organic Chemistry (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing gamma-valerolactone by levulinic acid ester without solvents, and relates to gamma-valerolactone. A copper chromite catalyst is added into the levulinic acid ester and reacts in hydrogen atmosphere to obtain solid-liquid mixture, pressure is reduced, suction filtration is performed to obtain binary liquid mixture containing gamma-valerolactone and corresponding alcohols, and the alcohols are recovered by distillation to obtain the gamma-valerolactone. Cheap and easily separated copper chromite serving as the catalyst is added into the levulinic acid ester from biomass, and the gamma-valerolactone is prepared at one step in a solvent-free system. The copper chromite catalyst is activated in situ in the system, so that a traditional catalyst pre-hydrogenation step is omitted. The method is simple and efficient, and an effective way is provided for large-scale preparation of biomass-based gamma-valerolactone.
Description
Technical field
The present invention relates to γ-valerolactone, especially relate to a kind of method by levulinate solvent-free preparation γ-valerolactone.
Background technology
Levulinate as methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate etc. be a class can by lignocellulose degrade in alcohols preparation platform chemicals.With it for raw material, novel biomass based platform compound γ-valerolactone can be obtained.Because its higher calorific value, good dissolving power are with reactive, this material receives in recent years and pays close attention to widely and research.
Chinese patent CN200810195942.4 discloses a kind of method being prepared γ-valerolactone by levulinic acid, comprises using formic acid as solvent and hydrogen source, under ruthenium catalyst and a small amount of alkali effect, synthesize γ-valerolactone.The method need introduce formic acid and ruthenium catalyst, all proposes higher requirement to reaction vessel and cost.
Chinese patent CN201310011149.5 discloses a kind of method being prepared γ-valerolactone by levulinate, comprise under inert gas atmosphere, take secondary alcohol as solvent and hydrogen source, the activated skeleton nickel of apparatus obtains γ-valerolactone as catalyzer through hydrogen transfer reactions.The method needs a large amount of secondary alcohol as hydrogen donor, and needs the skeleton nickel of costliness, preservation condition harshness as catalyzer, and cost do not have advantage.
Chinese patent CN201310110054.9 discloses a kind of method being prepared γ-valerolactone by levulinate, is included in water or alcoholic solvent, take hydrogen as hydrogen source, obtained γ-valerolactone under load cobalt catalyst catalysis.The method needs a large amount of solvent and more complicated support of the catalyst, auxiliary agent etc. equally, and total cost of production is higher.
Chinese patent CN201310170117.X discloses a kind of method being prepared γ-valerolactone by acetyl-propionic acid raw material, and comprising with water is solvent, with formic acid or formate for hydrogen source, with water-soluble complex of iridium for catalyst preparing γ-valerolactone.The method relates to the factor that formic acid, iridium catalyst etc. cause cost higher.
Visible, report in current document and patent to have charging capacity by the method for biomass-based levulinic acid and levulinic acid Lipase absobed γ-valerolactone less, need a large amount of solvent as water, alcohols, the shortcoming that reaction efficiency is lower.Meanwhile, homogeneous catalyst conventional in reaction is as being complex structures such as iridium, ruthenium basigamy compound, expensive and be difficult to separation, and heterogeneous catalyst is as higher in costs such as palladium carbon, ruthenium carbon, Raney nickel and accumulating condition harsh.These factors directly limit the scale operation of γ-valerolactone in biomass chemical field.
Copper chromite is a kind of by the catalyzer for ester class hydrogenation reaction of more patent disclosure, and its preparation method is comparatively ripe.But in existing report, this catalyzer needs to carry out hydrogenation prereduction before for catalytic hydrogenation reaction makes it activate, and this step energy consumption is higher.
Summary of the invention
Main purpose of the present invention is to provide low cost, a kind of high efficiency method by levulinate solvent-free preparation γ-valerolactone.
Concrete steps of the present invention are as follows:
In levulinate, add copper chromite catalyst, react in a hydrogen atmosphere, obtain solidliquid mixture, then decompress filter, obtain the binary liquid mixture containing γ-valerolactone and corresponding alcohols; Again through Distillation recovery alcohols, obtain γ-valerolactone.
Described levulinate can be selected from least one in methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate etc.; Described copper chromite catalyst can adopt the copper chromite catalyst without weighted BMO spaces; The add-on of described copper chromite catalyst can be 0.2% ~ 1% of levulinate by mass percentage; The initial pressure of described hydrogen atmosphere can be 2 ~ 8MPa; The temperature of described reaction can be 200 ~ 275 DEG C, and the time of reaction can be 1 ~ 8h; In the process of described reaction, copper chromite is by in-situ activation; Copper chromite can be reclaimed after described reaction; The purity of obtained γ-valerolactone can reach more than 95%; The copper chromite catalyst that recovery obtains can be directly used in and react next time.
Reaction principle of the present invention is: in levulinate, hydrogen and the ternary system without the copper chromite catalyst of weighted BMO spaces, copper chromite generation in-situ activation is made and catalysis levulinate generation hydrogenation reaction generation intermediate 4-hydroxyl valerate by heating, can there is cyclization and remove an alcohol molecule in this intermediate, obtain the alcohols of γ-valerolactone and correspondence further.In reaction process, copper chromite does not need through traditional weighted BMO spaces, but direct in-situ activation in system, while simplification reactions steps, higher reaction efficiency can be obtained.Concrete reaction is shown below:
Wherein, R is methyl, ethyl, butyl etc.
Relative to existing report, the invention has the advantages that: the first, the method, without any need for solvent, while greatly improving reaction efficiency, simplifies follow-up separating-purifying step.The second, adopt cheap copper chromite to be catalyzer, this catalyzer is found to reduce at body series situ, eliminates the hydrogenation pre-reduction procedure of power consumption.3rd, copper chromite catalyst is found the hydrogenation reaction being highly suitable for levulinate.4th, copper chromite catalyst in the method can high efficiente callback show excellent cycle performance in follow-up reaction.5th, the method is applicable to the levulinate classes such as methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate, and product obtains γ-valerolactone by similar means separating-purifying.
To sum up, the present invention proposes a kind of copper chromite catalysis based on in-situ activation, the solvent-free method being prepared γ-valerolactone by levulinate first, and the scale operation for biomass-based γ-valerolactone provides a potential route.
Accompanying drawing explanation
Fig. 1 is the GC-MS collection of illustrative plates that ethyl levulinate prepares γ-valerolactone products therefrom.
Embodiment
Below in conjunction with embodiment, the invention will be further described, it should be noted that, embodiment does not form the restriction to application claims protection domain.
Embodiment 1
In 20g ethyl levulinate stock liquid, add the copper chromite of 0.1g without weighted BMO spaces as catalyzer, at 225 DEG C, in-situ reducing decompress filter after reacting 4h under 4MPa hydrogen pressure, obtain water white transparency liquid.After underpressure distillation removing ethanol, obtain γ-valerolactone crude product, productive rate is 57.5%.
Embodiment 2
In 20g Butyl acetylpropanoate stock liquid, add the copper chromite of 0.2g without weighted BMO spaces as catalyzer, at 250 DEG C, in-situ reducing decompress filter after reacting 4h under 2MPa hydrogen pressure, obtain water white transparency liquid.After underpressure distillation removing ethanol, obtain γ-valerolactone crude product, productive rate is 46.9%.
Embodiment 3
In 20g methyl ester levulinate stock liquid, add the copper chromite of 0.2g without weighted BMO spaces as catalyzer, at 275 DEG C, in-situ reducing decompress filter after reacting 4h under 4MPa hydrogen pressure, obtain water white transparency liquid.After underpressure distillation removing ethanol, obtain γ-valerolactone crude product, productive rate is 85.6% (as Fig. 1).
Embodiment 4
In 20g ethyl levulinate stock liquid, add the copper chromite of 0.04g without weighted BMO spaces as catalyzer, at 250 DEG C, in-situ reducing decompress filter after reacting 8h under 4MPa hydrogen pressure, obtain water white transparency liquid.After underpressure distillation removing ethanol, obtain γ-valerolactone crude product, productive rate is 55.5%.
Embodiment 5
In 20g ethyl levulinate stock liquid, add the copper chromite of 0.2g without weighted BMO spaces as catalyzer, at 200 DEG C, in-situ reducing decompress filter after reacting 4h under 8MPa hydrogen pressure, obtain water white transparency liquid.After underpressure distillation removing ethanol, obtain γ-valerolactone crude product, productive rate is 15.2%.
Embodiment 6
In 20g ethyl levulinate stock liquid, add the copper chromite of 0.2g without weighted BMO spaces as catalyzer, 225 DEG C, react 1h under 2MPa hydrogen pressure after decompress filter, obtain water white transparency liquid.After underpressure distillation removing ethanol, obtain γ-valerolactone crude product, productive rate is 36.8%.
Embodiment 7
In the mixing raw material liquid of 10g ethyl levulinate and 10g methyl ester levulinate, add the copper chromite of 0.2g without weighted BMO spaces as catalyzer, 260 DEG C, react 1h under 3MPa hydrogen pressure after decompress filter, obtain water white transparency liquid.After underpressure distillation removing methyl alcohol, ethanol, obtain γ-valerolactone crude product, overall yield is 75.5%.
Embodiment 8
In 20g ethyl levulinate stock liquid, add the not pretreated copper chromite of 0.2g as catalyzer, at 250 DEG C, in-situ reducing decompress filter after reacting 5h under 3MPa hydrogen pressure, obtain water white transparency liquid and black powder.This powder is directly used in subsequent reactions, and circulate 5 times altogether, each γ-valerolactone productive rate is respectively 81.2%, 85.5%, 83.4%, 83.5%, 84.1%.
The present invention is using copper chromite as catalyzer, and catalysis biomass base levulinate reacting by heating in hydrogen atmosphere, be separated solid liquid phase after cooling, product liquid obtains γ-valerolactone through distilation.The method adopts cheapness, segregative copper chromite prepares γ-valerolactone as catalyzer from levulinate step solvent-free system of biomass source.Copper chromite catalyst in the activation of system situ, therefore does not need the pre-hydrogenation step of traditional catalyzer.This system is simply efficient, provides the effective way that is prepared biomass-based γ-valerolactone on a large scale.
Claims (7)
1., by a method for levulinate solvent-free preparation γ-valerolactone, it is characterized in that its concrete steps are as follows:
In levulinate, add copper chromite catalyst, react in a hydrogen atmosphere, obtain solidliquid mixture, then decompress filter, obtain the binary liquid mixture containing γ-valerolactone and corresponding alcohols; Again through Distillation recovery alcohols, obtain γ-valerolactone.
2. a kind of method by levulinate solvent-free preparation γ-valerolactone as claimed in claim 1, is characterized in that described levulinate is selected from least one in methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate.
3. a kind of method by levulinate solvent-free preparation γ-valerolactone as claimed in claim 1, is characterized in that described copper chromite catalyst adopts the copper chromite catalyst without weighted BMO spaces.
4. a kind of method by levulinate solvent-free preparation γ-valerolactone as claimed in claim 1, is characterized in that the add-on of described copper chromite catalyst is 0.2% ~ 1% of levulinate by mass percentage.
5. a kind of method by levulinate solvent-free preparation γ-valerolactone as claimed in claim 1, is characterized in that the initial pressure of described hydrogen atmosphere is 2 ~ 8MPa.
6. a kind of method by levulinate solvent-free preparation γ-valerolactone as claimed in claim 1, it is characterized in that the temperature of described reaction is 200 ~ 275 DEG C, the time of reaction is 1 ~ 8h.
7. a kind of method by levulinate solvent-free preparation γ-valerolactone as claimed in claim 1, reclaims copper chromite after it is characterized in that described reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566285A (en) * | 2016-03-23 | 2016-05-11 | 厦门大学 | Method for preparing 5-methylthienyl-2-thiol from levulinic acid |
| CN107253937A (en) * | 2017-08-03 | 2017-10-17 | 厦门大学 | A kind of synthetic method of γ valerolactones |
| CN112064407A (en) * | 2020-07-31 | 2020-12-11 | 安徽美盈森智谷科技有限公司 | Preparation process of recyclable hydrophobic corrugated board for processing packaging carton |
| CN114163404A (en) * | 2021-12-24 | 2022-03-11 | 兰州大学 | Method for synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid |
-
2015
- 2015-05-04 CN CN201510218970.3A patent/CN104844542A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566285A (en) * | 2016-03-23 | 2016-05-11 | 厦门大学 | Method for preparing 5-methylthienyl-2-thiol from levulinic acid |
| CN105566285B (en) * | 2016-03-23 | 2018-01-09 | 厦门大学 | A kind of method that the mercaptan of 5 methylthiophene 2 is prepared by levulic acid |
| CN107253937A (en) * | 2017-08-03 | 2017-10-17 | 厦门大学 | A kind of synthetic method of γ valerolactones |
| CN112064407A (en) * | 2020-07-31 | 2020-12-11 | 安徽美盈森智谷科技有限公司 | Preparation process of recyclable hydrophobic corrugated board for processing packaging carton |
| CN114163404A (en) * | 2021-12-24 | 2022-03-11 | 兰州大学 | Method for synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid |
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Application publication date: 20150819 |