CN102617519B - Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation - Google Patents
Method for using levulinic acid to prepare gamma-valerolactone by hydrogenation Download PDFInfo
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- CN102617519B CN102617519B CN201210053605.8A CN201210053605A CN102617519B CN 102617519 B CN102617519 B CN 102617519B CN 201210053605 A CN201210053605 A CN 201210053605A CN 102617519 B CN102617519 B CN 102617519B
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- levulinic acid
- hydrogenation
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- valerolactone
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for using levulinic acid to prepare gamma-valerolactone by hydrogenation. Skeleton copper is used as a catalyst, copper-aluminum alloy as a catalyst precursor contains Group VIII transition metals to improve the activity and selectivity of the skeletal copper catalyst, the copper-aluminum alloy is extracted and activated by inorganic base solution to prepare the skeletal copper catalyst with the functions of hydrogenation and the functions of a molecule lactonization loop-locked, appropriate quantities of skeletal copper catalyst, additives and solvent added into the liquid-phase hydrogenation system of levulinic acid, and the catalyst can be continuously recycled. The method has the advantages of low catalyst cost, simple process, easiness in operation and high yield of gamma-valerolactone.
Description
Technical field:
The present invention relates to a kind of method of being prepared γ-valerolactone by levulinic acid.
Background technology:
Levulinic acid (LA) is a kind of product after hexose acidolysis, and can obtain from cellulose substances hydrolysis.Under suitable catalyst action, LA and ester shortening thereof can be prepared high added value product γ-valerolactone (GVL, also referred to as 5-valerolactone or 5-methyl butyrolactone).
GVL can be used for food flavour or flavouring essence for tobacco, also can be used as solvent, fine chemistry industry synthetic intermediate etc. simultaneously.Prepare GVL by LA and can adopt chemical reduction method and shortening method, chemical reduction method cost is higher, is only applicable to small-scale production, uses KBH as Chinese patent CN101633649B discloses LA in NaOH solution
4the method of GVL is prepared in chemical reduction.
LA and ester shortening legal system thereof generally adopt the method for heterogeneous catalysis for GVL.LA heterogeneous catalysis hydrogenation can carry out in gas phase or liquid phase, and liquid phase reaction can adopt organic solvent or the aqueous solution, and catalyzer can use the precious metals such as ruthenium, also can adopt the base metal such as nickel, copper, and active metal loads on carbonaceous carrier or SiO
2or Al
2o
3on.
USP 2,368,366 has reported that nickel formate decomposes the result of the nickel catalyzator obtaining catalysis LA liquid-phase hydrogenatin under 900Psi hydrogen pressure; USP 2,786,852 discloses the copper silicon of reduction or the Cu-Cr catalyst catalysis LA vapor phase Hydrogenation method for GVL that uses; USP 4,420, when the 622 direct catalysis LA of the non-precious metal catalyst gas phase hydrogenation for the group VIIIs such as nickel, cobalt, copper and IB family, the catalytic activity problem faster that declines, proposes to adopt the cobalt of loading type, the method that copper catalysis levulinate gas phase hydrogenation is prepared GVL; There are document (Allen B.B., Wyatt B.W., Henze H.R.J.Am.Chem.Soc.1939,61,843-846; Christian R.V., Jr Brown H.D., Hixon R.M.J.Am.Chem.Soc.1947,69,1961-1963) report Raney's nickel can be used for the hydrogenation of levulinic acid sodium-salt aqueous solution, in solution, contain excessive NaOH, the sodium salt that hydrogenation products is γ-hydroxypentanoic acid, can obtain GVL after acidifying.WO 02/074,760 disclose LA under the effect of noble metal catalyst with the hydrogen reaction of 700-800Psi, the yield of GVL can reach 97%; WO 2007/099,111 A1 discloses employing cellulose hydrolysis by product formic acid as hydrogen supply agent, and with the loaded catalyst containing Pt, levulinate gas phase hydrogenation reaction is prepared the method for GVL; USP 5,883,266 discloses precious metal or the non-precious metal catalyst such as Ru, Pd, Ni, Re that utilize loading type, adopts one kettle way to be prepared the method for the multiple product including GVL by LA, and this patent declares that catalyzer has hydrogenation and open loop is difunctional; USP 6,617,464 adopts oxidation-stabilized carbon support carried noble metal, and group VIII and I B-group metal are auxiliary agent, and GVL is prepared in catalysis LA liquid-phase hydrogenatin, catalyzer have hydrogenation and closed loop difunctional; USP 6,946,563 adopts and USP 6,617,464 identical methods are prepared loaded noble metal catalyst, discloses in supercutical fluid catalysis LA Hydrogenation for the method for GVL.
Because chemical reduction method cost is higher, be difficult to adapt to large-scale commercial production, the publication of shortening method adopts the noble metal catalyst such as Ru, Pt mostly, exists equally catalyzer cost higher, is difficult to the problem of industrial application.Adopt the patented method of the non-precious metal catalysts such as nickel, copper, due to the acidity of raw material LA itself, cause catalyst activity reduction problem faster, as adopt Raney's nickel, for keeping catalyst activity, need first LA to be converted into corresponding sodium salt, after hydrogenation, also want the acidified GVL that just can obtain, operating process is comparatively loaded down with trivial details, and the yield of product GVL is not high.
Summary of the invention:
The object of the invention is for prior art exist problem provide a kind of by levulinic acid Hydrogenation the preparation method for γ-valerolactone.
Object of the present invention realizes by following technical scheme.Adopt skeletal copper as levulinic acid liquid-phase hydrogenatin prepare the catalyzer of γ-valerolactone, in catalyst precursors X alloy, contain appropriate group VIII transition metal, in order to improve the activity and selectivity of skeletal copper catalyst.X alloy can obtain skeletal copper catalyst through inorganic base aqueous solution extracting activation, has not only had the function of hydrogenation but also has had the lactonize function of closed loop of molecule, also needs to add appropriate amount of addition agent and solvent in levulinic acid liquid-phase hydrogenatin system, specifically realizes in the steps below:
(1) X alloy activation, washing: the quality percentage composition of X alloy is metallic aluminium 40-55%, metallic copper 40-55% and group VIII transition metal 0.1-10%, and group VIII transition metal is one or more in iron, cobalt, nickel.With the metallic aluminium in inorganic alkali solution extracting alloy, alkali consumption is 0.5-3 times of copper-aluminium alloy powder weight, and preferably doubly, be mixed with mass concentration is 1%-40% to 1-2, preferably the inorganic base aqueous solution of 10-25%; Copper-aluminum alloy powder is at room temperature slowly added in inorganic base aqueous solution, then heat up and carry out extracting, extraction temperature is 40-100 DEG C, preferably 60-80 DEG C, and the extracting time is 0.5-3 hour, preferably 1-2 hour.Mineral alkali is selected from NaOH, KOH and Na
2cO
3, preferably NaOH.Catalyzer after extracting is 7-10 with the deoxygenation deionized water wash of 40-80 DEG C to pH, and preferably pH=8-9, is kept at the skeletal copper of gained in the NaOH solution of deionized water, dehydrated alcohol or 0.1mol/L.
(2) levulinic acid liquid-phase hydrogenatin reaction: will press the good skeletal copper catalyst of above-mentioned steps extracting, prepare γ-valerolactone for levulinic acid liquid-phase hydrogenatin, skeletal copper catalyst consumption accounts for the 5-20% of levulinic acid, preferably 6-15%, and auxiliary agent is selected from NaOH, KOH or Na
2cO
3, preferably NaOH, the consumption of auxiliary agent accounts for the 0.05-0.8% of levulinic acid, and preferably 0.1-0.4%, is more than mass percent; Solvent is selected from the small molecule alcohol such as dioxane or methyl alcohol, ethanol, particular methanol, and the volume ratio of solvent and levulinic acid is 9: 1-1: 1, preferably 5: 1-3: 1.First solvent and skeletal copper catalyst are joined in reactor, then add through the levulinic acid that heating is in a liquid state in advance, and appropriate amount of addition agent, control certain reaction conditions and carry out hydrogenation reaction.Hydrogenation reaction temperature is 100-200 DEG C, preferably 120-160 DEG C; Hydrogen pressure 1.0-8.0MPa, preferably 3.0-5.0MPa.
(3) separation of reaction product: the liquid product that above-mentioned reaction is obtained is through normal pressure fractionation by distillation solvent, then can obtain the more than 99% γ-valerolactone product of purity through underpressure distillation.
The invention has the beneficial effects as follows and adopt skeletal copper to make catalyzer, because metallic copper is compared comparatively inertia of metallic nickel, under reaction conditions, can tolerate the acidity of raw material LA and levulinic acid itself, be unlikely to make in use active decline of catalyzer, select suitable solvent and auxiliary agent, under the temperature of reaction and pressure lower than carried copper-base catalyst, can obtain excellent hydrogenation activity and selectivity of product, and catalyzer can continuous several times be applied mechanically.Skeletal copper catalyst is compared copper catalyst prepared by coprecipitation method or pickling process and is had higher low temperature hydrogenation catalytic activity in addition, can obviously reduce hydrogenation reaction temperature, reduce energy consumption, thereby the present invention has that cost is low, technique simple, easy handling, high, the good in economic efficiency feature of product yield.
Embodiment:
Further illustrate the present invention below by embodiment, but invention is not limited.
Embodiment 1: 10 grams of nickeliferous 5.48% copper-aluminium alloy powders, under room temperature, slowly add 65 milliliters of inorganic alkali solutions that contain 15 grams of NaOH, under stirring, be warmed up to 70 DEG C of activation 1 hour, with the deionized water wash of 500 milliliters, 60 DEG C to pH be 8, then replace deionized water with dehydrated alcohol.Levulinic acid heats and is in a liquid state a little, and the skeletal copper catalyst of getting 50 milliliters and 200 ml methanol, above-mentioned preparation adds in autoclave simultaneously, adds 0.6 gram of NaOH.Controlling hydrogenation reaction temperature is 130-140 DEG C, hydrogen pressure 3.0MPa, and successive reaction 2 hours, recording levulinic acid transformation efficiency is 99.8%, γ-valerolactone selectivity 97.2%.
Embodiment 2: 12 grams of nickeliferous 5.48% copper-aluminium alloy powders, under room temperature, slowly add 70 milliliters of inorganic alkali solutions that contain 16 grams of NaOH, under stirring, be warmed up to 60 DEG C of activation 1.5 hours, with the deionized water wash of 500 milliliters, 50 DEG C to pH be 8, then replace deionized water with dehydrated alcohol.Levulinic acid heats and is in a liquid state a little, and the skeletal copper catalyst of getting 60 milliliters and 190 milliliters of dioxane, above-mentioned preparation adds in autoclave simultaneously, adds 0.4 gram of KOH.Controlling hydrogenation reaction temperature is 130-140 DEG C, hydrogen pressure 4.0MPa, and successive reaction 2.5 hours, levulinic acid transformation efficiency is 99.7%, γ-valerolactone selectivity 95.6%.
Embodiment 3: change the copper-aluminium alloy powder activation condition in embodiment 1 into 70 DEG C of activation 1.5 hours, levulinic acid hydrogenation reaction solvent is dehydrated alcohol, other catalyst activation process and hydrogenation conditions are constant with embodiment 1, levulinic acid hydrogenation conversion is 99.5%, γ-valerolactone selectivity 96.8%.
Embodiment 4: the X alloy in embodiment 1 is changed to the copper-aluminium alloy powder of iron content 3.52%, other catalyst activation process and hydrogenation conditions are constant with embodiment 1, levulinic acid hydrogenation conversion is 99.2%, γ-valerolactone selectivity 96.3%.
Embodiment 5: the X alloy in embodiment 2 is changed to the copper-aluminium alloy powder containing cobalt 4.03%, levulinic acid hydrogenation reaction solvent is methyl alcohol, other catalyst activation process and hydrogenation conditions are constant with embodiment 2, and levulinic acid transformation efficiency is 99.3%, γ-valerolactone selectivity 96.9%.
Embodiment 6: reacted catalyzer in embodiment 1 is reclaimed by centrifugation, through absolute ethanol washing, and supplement according to the fresh skeletal copper catalyst 1.5g of embodiment 1 method activation, repeat the levulinic acid Hydrogenation Experiment in embodiment 1, levulinic acid hydrogenation conversion is 99.6%, γ-valerolactone selectivity 96.7%.
Contrast experiment: adopt coprecipitation method to prepare the CuO/SiO of copper charge capacity 30%
2catalyzer 15g, before using first 300 DEG C of hydrogen reducings 8 hours.Levulinic acid hydrogenation reaction temperature is 150-160 DEG C, hydrogen pressure 5.OMPa, and other condition is with embodiment 1, and levulinic acid transformation efficiency is 98.9%, γ-valerolactone selectivity 92.5%.
From above embodiment, in the present invention, with the liquid-phase hydrogenatin of skeletal copper catalysis levulinic acid, under relatively low hydrogen pressure and temperature of reaction, levulinic acid can transform substantially completely, and obtains higher γ-valerolactone productive rate.Skeletal copper catalyst can repeat to apply mechanically, and only needs to supplement a small amount of live catalyst and can realize similar levulinic acid hydrogenation effect.
Elementary composition variation before and after table 1 X alloy, skeletal copper catalyst catalysis levulinic acid hydrogenation
Can be found out by data in table 1, crystal phase structure before and after skeletal copper catalyst catalysis levulinic acid hydrogenation reaction and elementary compositionly substantially remain unchanged, catalyzer is applied mechanically experiment and is also shown that catalyst activity reduction amplitude is less, can keep higher hydrogenation activity as supplemented a small amount of fresh skeletal copper catalyst.
Claims (2)
- One kind by levulinic acid Hydrogenation the method for γ-valerolactone, adopt skeletal copper as catalyzer, in catalyst precursors X alloy, contain VIII group 4 transition metal, in order to improve the activity and selectivity of skeletal copper catalyst, X alloy can obtain skeletal copper catalyst through NaOH aqueous solution extracting activation, has not only had the function of hydrogenation but also has had the lactonize function of closed loop of molecule, also needs to add auxiliary agent and solvent in levulinic acid liquid-phase hydrogenatin system, it is characterized in that, specifically realize in the steps below:(1) X alloy activation, washing: the quality percentage composition of X alloy is metallic aluminium 40-55%, metallic copper 40-49% and VIII group 4 transition metal 0.1-10%, and described VIII group 4 transition metal is one or more in iron, cobalt, nickel; The NaOH consumption of described extracting X alloy is 1-2 times of copper-aluminium alloy powder quality; Being mixed with mass concentration is the NaOH aqueous solution of 10%-25%, and extraction temperature is 60-80 DEG C, and the extracting time is 1-2 hour; Skeletal copper after extracting with the deoxygenation deionized water wash of 50-60 DEG C to pH be 7-10, the skeletal copper of gained is kept in the NaOH solution of 0.1mol/L;(2) levulinic acid liquid-phase hydrogenatin reaction: by the skeletal copper catalyst activating by above-mentioned steps extracting, prepare γ-valerolactone for levulinic acid liquid-phase hydrogenatin, skeletal copper catalyst consumption accounts for the 6-15% of levulinic acid; Auxiliary agent is selected from NaOH, KOH or Na 2cO 3, the consumption of auxiliary agent accounts for the 0.1-0.4% of levulinic acid, is more than mass percent; Solvent is selected from dioxane or methyl alcohol or ethanol, and the volume ratio of solvent and levulinic acid is 5: 1-3: 1; Hydrogenation reaction temperature is 120-160 DEG C, hydrogen pressure 3.0-5.0MPa;(3) separation of reaction product: the liquid product that above-mentioned reaction is obtained is through normal pressure fractionation by distillation solvent, then can obtain the more than 99% γ-valerolactone product of purity through underpressure distillation.
- According to claimed in claim 1 by levulinic acid Hydrogenation the method for γ-valerolactone, it is characterized in that solvent particular methanol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9884834B2 (en) | 2015-12-23 | 2018-02-06 | Neste Oyj | Combined levulinic acid and furfural production from biomass |
| US9914714B2 (en) | 2015-12-23 | 2018-03-13 | Neste Oy J | Selective process for conversion of levulinic acid to gammavalerolactone |
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| CN103012334B (en) * | 2013-01-11 | 2015-05-27 | 中国科学技术大学 | Method for preparing gamma-valerolactone with high selectivity under mild condition |
| CN103497168B (en) * | 2013-10-18 | 2016-05-18 | 厦门大学 | A kind of levulic acid and ester class transfer hydrogenation thereof are prepared the method for gamma-valerolactone |
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| CN109485621A (en) * | 2018-11-30 | 2019-03-19 | 中国科学技术大学 | A method of producing gamma valerolactone |
| CN110479279A (en) * | 2019-07-03 | 2019-11-22 | 天津大学 | For synthesizing the preparation method and application of the catalyst of gamma-valerolactone |
| CN111153875A (en) * | 2020-01-06 | 2020-05-15 | 上海海洋大学 | Gamma valerolactone and method for preparing gamma valerolactone by utilizing levulinate |
| CN111116524A (en) * | 2020-01-06 | 2020-05-08 | 上海海洋大学 | Gamma valerolactone and method for preparing gamma valerolactone by utilizing levulinate |
| US20220355276A1 (en) * | 2020-11-11 | 2022-11-10 | Ningbo Institute Of Materials Technology & Engineering, Chinese Academy Of Sciences | Raney copper catalyst as well as preparation method and use thereof |
| CN116764672A (en) * | 2022-03-08 | 2023-09-19 | 中国科学院大连化学物理研究所 | Efficient and stable bifunctional catalyst, preparation method thereof and application thereof in valerate fuel molecule preparation reaction |
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| US9884834B2 (en) | 2015-12-23 | 2018-02-06 | Neste Oyj | Combined levulinic acid and furfural production from biomass |
| US9914714B2 (en) | 2015-12-23 | 2018-03-13 | Neste Oy J | Selective process for conversion of levulinic acid to gammavalerolactone |
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