CN107253937A - A kind of synthetic method of γ valerolactones - Google Patents
A kind of synthetic method of γ valerolactones Download PDFInfo
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- CN107253937A CN107253937A CN201710659480.6A CN201710659480A CN107253937A CN 107253937 A CN107253937 A CN 107253937A CN 201710659480 A CN201710659480 A CN 201710659480A CN 107253937 A CN107253937 A CN 107253937A
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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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Abstract
The invention discloses a kind of synthetic method of γ valerolactones, comprise the following steps：(1) methyl ester levulinate is sufficiently mixed with alcohol, the concentration for obtaining methyl ester levulinate in mixed material liquid, mixed material liquid is 2~12wt%；(2) bimetallic catalyst is added in above-mentioned mixed material liquid, 170~290 DEG C of 0.5~9h of reaction is heated in autoclave, room temperature is cooled to.The present invention applies copper-based bimetallic catalyst, adjusts catalyst activity by second active metal that adulterates, and then can realize catalyzing alcohols original position production hydrogen and optionally be catalyzed methyl ester levulinate Hydrogenation for γ valerolactones.
Description
Technical field
The invention belongs to organic catalysis synthesis technical field, and in particular to a kind of synthetic method of gamma-valerolactone.
Background technology
Gamma-valerolactone has nontoxic, biodegradable characteristic, it is considered to be the most biomass-based platform of application prospect
One of compound, can produce carbon-based chemicals and the energy as reproducible carbon source.In recent years increasingly by academia and work
The attention of industry.Gamma-valerolactone can participate in Ivanov reaction synthetic drugs as raw material, can be with phenyl aromatic compound
The reaction such as Friedel-Crafts reactions and cyclisation, reduction and dehydration is synthesized in the luxuriant and rich with fragrance class compounds of various polysubstituted naphthalene anthracenes, γ-penta
Ester may also pass through cyclisation and decarboxylation/hydrogenation is respectively synthesized penetenoic acid, butylene, valeric acid and butyl ketone；In addition, gamma-valerolactone is opened
Ring position is different, and obtained product is also different, and Isosorbide-5-Nitrae-pentanediol and 2- methyltetrahydrofurans are all fine-chemical intermediates.Isosorbide-5-Nitrae-
Pentanediol can be used for preparing high performance biodegradable polyesters, and 2- methyltetrahydrofurans are then a kind of solvents of function admirable
And fuel additive.On the other hand, gamma-valerolactone may also serve as the raw material of synthetic polymeric material.Gamma-valerolactone and formaldehyde
In Ba/SiO2It is unique in the lower novel monomeric alpha-methylene-gamma-valerolactone with similar acrylate structural of catalysis, its molecule
Cyclic ester structure so that poly- alpha-methylene-gamma-valerolactone material have it is preferably more thermally-stabilised than conventional polypropylene acid esters material
Property, its glass transition temperature (Tg) more than 200 DEG C can be reached.Catalyzed conversion gamma-valerolactone can also synthesize dicarboxylic acids esters monomer
Or another very important polymeric material --- polyurethane.Also there are some researches show, gamma-valerolactone inherently than ethanol more
Good gasoline additive, because gamma-valerolactone has the energy density of lower saturated vapour pressure and Geng Gao.And different from second
Alcohol, it is more energy efficient that gamma-valerolactone will not form separating-purifying ethanol in azeotropic mixture, zymotic fluid with water.
Chinese patent 104496945A discloses a kind of method that levulic acid hydrogenation cyclisation prepares gamma-valerolactone.By two
Titanium oxide is added in levulic acid isopropanol reaction liquid, is vacuumized or is passed through under noble metal source solution, magnetic agitation while adding
After argon gas deoxygenation, noble metal source is reduced into by noble metal granule by photocatalysis in situ using ultraviolet lamp source, titanium dioxide is loaded to
Titanium surface, starts the hydrogenation cyclisation of photocatalysis levulic acid and prepares gamma-valerolactone.This method not only needs precious metal catalyst,
And the reaction time is longer, it is necessary to 10-36 hours.
Chinese patent 104693159A discloses the catalysis that a kind of liquid-phase hydrogenatin prepares the method for gamma-valerolactone and its used
Agent.Under the conditions of low-temp low-pressure, high selectivity hydrogenation is carried out to alpha-angelica lactone using loaded catalyst, reaction is prepared into
To gamma-valerolactone, and disclose described loaded catalyst and preparation method thereof and its liquid-phase hydrogenatin prepare γ-penta in
Application in ester method.The active metal of the loaded catalyst is precious metal palladium or palladium-nickel alloy, with high costs, it is necessary to certain
Outer hydrogenation pressure could realize higher hydrogenation selectivity.
Chinese patent 105566258A discloses a kind of ethyl levulinate and prepares the method for gamma-valerolactone in reproducibility
Under atmosphere, after ethyl levulinate, molecular sieve carried Pt catalyst and reaction dissolvent hybrid reaction, gamma-valerolactone is obtained.
Molecular sieve carried Pt catalyst systems can efficient catalytic biomass-based ethyl levulinate hydrogenation prepare gamma-valerolactone, be recycled
Using more than 5 times, the yield of reaction product gamma-valerolactone is reduced within 5%.But the catalyst uses noble metal
Pt, and higher outer hydrogenation pressure (4~8MPa) is needed, the temperature of reaction still needs reaction 6-24 hours at 200-240 DEG C,
Catalytic process holistic cost is high.
Chinese patent 1349853A discloses a kind of preparation method for the catalyst and lactones for preparing lactones.Catalyst is carried
The one kind of body in silica, aluminum oxide and its mixture, and load copper compound, zinc compound and at least one alkaline earth
Metallic compound.Can catalytic diol carry out dehydrogenation reaction in gas phase, prepare 11 kinds of lactones including gamma-valerolactone.Urge
Agent needs to activate 6-20h at 180-250 DEG C, activate after in fixed bed in hydrogen and the butanol of Isosorbide-5-Nitrae-two mol ratio 12: 1
It is catalyzed under atmosphere.Raw material needed for preparing the catalyst is more, and preparation flow is complicated, and time-consuming for activation, and catalysis prepares lactones
When need to consume a large amount of hydrogen, these factors directly limit this method be used for gamma-valerolactone in biomass chemical field
Large-scale production.
CN 102617519A disclose a kind of by method of the levulic acid Hydrogenation for gamma-valerolactone.Made using skeletal copper
For catalyst, as containing group VIII transition metal in the albronze of catalyst precursors, the work to improve catalyst
Property and selectivity.Albronze can obtain skeletal copper catalyst through inorganic base aqueous solution extracting activation.Levulic acid liquid-phase hydrogenatin
Need to add appropriate skeletal copper catalyst, auxiliary agent and solvent in system, catalyst can be applied mechanically continuously.But the catalyst preparation
Flow is relatively tediously long, and system composition is complex, and the also separation to subsequent products causes certain difficulty, and holistic cost is not low.
CN104844542A discloses a kind of by the solvent-free method for preparing gamma-valerolactone of levulinate.In levulinic
Copper chromite catalyst is added in acid esters, is reacted under 2-8MP hydrogen atmospheres, solidliquid mixture is obtained through depressurizing suction filtration, is contained
There is the binary liquid mixture of gamma-valerolactone and corresponding alcohols；Again through being distilled to recover alcohols, gamma-valerolactone is produced.The catalyst is cheap
Easily separated, a step prepares gamma-valerolactone in system situ is activated and realizes solvent-free system.But the catalyst is except group
Into including outside to human body and the disagreeableness chromium of environment, copper chromite catalyst is also easily reunited in itself, causes catalytic effect
It is unstable, and course of reaction needs external hydrogen source, improves the requirement to equipment, adds holistic cost.
CN 104829559A disclose a kind of method that gamma-valerolactone is prepared by methyl ester levulinate.In levulic acid first
The Copper-Chromium Oxide Catalysts without weighted BMO spaces are added in the mixed liquor of ester and methanol, solidliquid mixture is obtained after reaction；Through
Cupric and chromic oxide can be reclaimed and obtain the thick liquid of gamma-valerolactone by decompression suction filtration.Reclaim obtained Copper-Chromium Oxide Catalysts direct
For next secondary response.The quality of the methanol of addition can be low up to the 8% of methyl ester levulinate, only as hydrogen donor.The catalysis
Agent is cheap efficiently, while production hydrogen reaction in situ and the hydrogenation reaction of methyl ester levulinate of catalysis methanol.But the catalysis
The composition of agent is included to human body and the disagreeableness chromium of environment, for environmental requirement, it is necessary to consider to chromium in the catalyst and copper
Synthetical recovery.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of synthetic method of gamma-valerolactone.
Technical scheme is as follows：
A kind of synthetic method of gamma-valerolactone, comprises the following steps：
(1) methyl ester levulinate is sufficiently mixed with alcohol, obtains methyl ester levulinate in mixed material liquid, mixed material liquid
Concentration is 2~12wt%；
(2) bimetallic catalyst is added in above-mentioned mixed material liquid, 170~290 DEG C is heated in autoclave
0.5~9h is reacted, room temperature is cooled to；
Bimetallic in above-mentioned bimetallic catalyst includes the first metal and the second metal, wherein the first metal is Cu, the
Two metals are Zr, Al, Mg, Ca, Zn, Ba or Ni, and the first metal and bimetallic mol ratio are 1~10: 1~10.
In a preferred embodiment of the invention, the alcohol is methanol, ethanol, isopropanol or n-butyl alcohol.
In a preferred embodiment of the invention, in the mixed material liquid concentration of methyl ester levulinate for 2~
10wt%.
In a preferred embodiment of the invention, the step (2) is：Double gold are added in above-mentioned mixed material liquid
Metal catalyst, 180~280 DEG C of 0.5~8h of reaction are heated in autoclave, room temperature is cooled to.
In a preferred embodiment of the invention, first metal and bimetallic mol ratio be 1~8: 1~
8。
Beneficial effects of the present invention：
1st, the copper-based bimetallic catalyst of present invention application, catalyst activity is adjusted by second active metal that adulterates, and then
Catalyzing alcohols original position production hydrogen can be realized and methyl ester levulinate Hydrogenation is optionally catalyzed for gamma-valerolactone.
2nd, catalyst of the invention is cheap and easy to get, and stable in catalytic performance, reusability is good, is also not in excessive hydrogenation production
Thing, and entirely reaction need not be hydrogenated with hydrogen environment, with relatively strong industrial processing safety, with very good
Industrial applications potentiality.
3rd, the present invention uses alcohol simultaneously as hydrogen donor and reaction media, it is not necessary to external hydrogen source and other solvents, reaction
System is simple, is conducive to the separation of purpose product.
4th, the present invention will not produce excessive hydrogenation product by reducing methyl ester levulinate with being cyclized hydrogenation selectivity.
5th, catalyst of the invention composition active metal and carrier are cheap and easy to get, good economy performance.
Brief description of the drawings
Fig. 1 is the GC collection of illustrative plates of gamma-valerolactone prepared by the embodiment of the present invention 8.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1~7
0.5 methyl ester levulinate and 19.5g methanol (2.5wt%) are added into 100mL autoclave, then is separately added into
0.2g CuMgO2、CuZnO2、CuCaO2、CuZrO3、CuAlO2.5、CuNiO2.5、CuBaO2(mol ratio of two kinds of metals is 1：1)
As catalyst, reactor is sealed, (500rpm) is stirred vigorously, be heated to 220 DEG C and kept for 4 hours, terminated reaction and be cooled to
Room temperature is simultaneously sampled, and qualitative and quantitative detection is carried out using GC-MS (Shimadzu) and GC (Agilent), and testing result is listed in Table 1 below sequence
Number be 1~7.
Embodiment 8
1.0g methyl ester levulinates and 19.0 isopropanols (5wt%) are added into 100mL autoclave, 0.2g is added
Cu4MgO5(mol ratio of copper and magnesium is 4: 1) seals reactor, is stirred vigorously (500rpm), is heated to 240 DEG C as catalyst
And kept for 2 hours, terminate reaction and be cooled to room temperature and sample, carried out using GC-MS (Shimadzu) and GC (Agilent) qualitative and fixed
Amount detection (as shown in Figure 1), testing result is listed in Table 1 below serial number 8.
Embodiment 9~12
0.8g methyl ester levulinates and 19.2g n-butyl alcohols (4wt%) are added into 100mL autoclave, then is separately added into
0.2g CuMg2O3、CuZn2O3、CuCa2O3、CuBa2O3(mol ratio of Cu and another active metal be 1: 2) as catalyst,
Reactor is sealed, (500rpm) is stirred vigorously, 260 DEG C is heated to and is kept for 1 hour, terminates reaction and is cooled to room temperature and samples,
Qualitative and quantitative detection is carried out using GC-MS (Shimadzu) and GC (Agilent), the testing result of different catalysts is listed in Table 1 below sequence
Number be 9~12.
Embodiment 13~14
2g methyl ester levulinates and 18g ethanol (10wt%) are added into 100mL autoclave, then is separately added into 0.2g
Cu2NiO3.5、Cu2ZrO4As catalyst (mol ratio of Cu and another active metal is 2: 1), reactor is sealed, is acutely stirred
(500rpm) is mixed, 280 DEG C is heated to and is kept for 0.5 hour, terminates reaction and is cooled to room temperature and samples, use GC-MS (Shimadzu)
Qualitative and quantitative detection is carried out with GC (Agilent), testing result is listed in Table 1 below serial number 13~14.
Embodiment 15~18
0.4g methyl ester levulinates and 19.6g methanol (2wt%) are added into 100mL autoclave, 0.2g is added
Cu8ZnO9、Cu8MgO9、CuZn8O9、CuMg8O9(Cu/Zn and Cu/Mg mol ratios are 8: 1 and 1: 8), as catalyst, sealing is anti-
Kettle is answered, (500rpm) is stirred vigorously, 180 DEG C~240 DEG C is heated separately to and is kept for 2~8 hours, terminates reaction and is cooled to room temperature
And sample, carry out qualitative and quantitative detection, the testing result row of differential responses condition using GC-MS (Shimadzu) and GC (Agilent)
The serial number 15~18 in table 1.
Embodiment 19~22
0.6g methyl ester levulinates and 19.4g methanol (3wt%) are added into 100mL autoclave, 0.2g is added
Cu6AlO7.5、CuAl6O10、Cu6CaO7、CuCa6O (Cu/Al and Cu/Ca mol ratios are 6: 1 and 1: 6) is used as catalyst, sealing
Reactor, is stirred vigorously (500rpm), is heated to 180 DEG C and is kept for 3 hours, terminates reaction and is cooled to room temperature and samples, uses
GC-MS (Shimadzu) and GC (Agilent) carries out qualitative and quantitative detection, and the testing result of differential responses condition is listed in Table 1 below sequence number
For 19~22.
Embodiment 23~24
1.6g methyl ester levulinates and 18.4g methanol (8wt%) are added into 100mL autoclave, 0.2g is added
Cu5Ni2O8、Cu2Ni5O9.5(Cu/Ni mol ratios are 5: 2 and 2: 5) seals reactor, is stirred vigorously as catalyst
(500rpm), is heated separately to 200 DEG C and is kept for 7 hours, terminates reaction and is cooled to room temperature and samples, uses GC-MS (Shimadzu)
Qualitative and quantitative detection is carried out with GC (Agilent), the testing result of differential responses condition is listed in Table 1 below serial number 23~24.
Embodiment 25
1.2g methyl ester levulinates and 18.8g methanol (6wt%) are added into 100mL autoclave, 0.2g is added
CuZr4O9(Cu/Zr mol ratios are 1: 4) seals reactor, is stirred vigorously (500rpm), is heated separately to 230 as catalyst
DEG C and kept for 2 hours, terminate reaction and be cooled to room temperature and sample, using GC-MS (Shimadzu) and GC (Agilent) carry out it is qualitative with
Quantitative detection, the testing result of differential responses condition is listed in Table 1 below serial number 25.
Testing result in each embodiment of table 1
Those of ordinary skill in the art understand that technical scheme when changing in following ranges, is remained able to
To technique effect same as the previously described embodiments or close, protection scope of the present invention is still fallen within：
A kind of synthetic method of gamma-valerolactone, comprises the following steps：
(1) methyl ester levulinate is sufficiently mixed with alcohol, obtains methyl ester levulinate in mixed material liquid, mixed material liquid
Concentration is 2~12wt%, preferably 2~10wt%；The alcohol is methanol, ethanol, isopropanol or n-butyl alcohol；
(2) bimetallic catalyst is added in above-mentioned mixed material liquid, 170~290 DEG C is heated in autoclave
(preferably 180~280 DEG C) react 0.5~9h (preferably 0.5~8h), are cooled to room temperature；
Bimetallic in above-mentioned bimetallic catalyst includes the first metal and the second metal, wherein the first metal is Cu, the
Two metals are Zr, Al, Mg, Ca, Zn, Ba or Ni, and the first metal and bimetallic mol ratio are 1~10: 1~10 (preferably 1
~8: 1~8).
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (5)
1. a kind of synthetic method of gamma-valerolactone, it is characterised in that：Comprise the following steps：
(1) methyl ester levulinate is sufficiently mixed with alcohol, obtains the concentration of methyl ester levulinate in mixed material liquid, mixed material liquid
For 2-12wt%；
(2) bimetallic catalyst is added in above-mentioned mixed material liquid, 170-290 DEG C of reaction is heated in autoclave
0.5~9h, is cooled to room temperature；
Bimetallic in above-mentioned bimetallic catalyst includes the first metal and the second metal, wherein the first metal is Cu, the second gold medal
Belong to for Zr, Al, Mg, Ca, Zn, Ba or Ni, and the first metal and bimetallic mol ratio are 1-10: 1-10.
2. synthetic method as claimed in claim 1, it is characterised in that：The alcohol is methanol, ethanol, isopropanol or n-butyl alcohol.
3. synthetic method as claimed in claim 1, it is characterised in that：The concentration of methyl ester levulinate in the mixed material liquid
For 2~10wt%.
4. synthetic method as claimed in claim 1, it is characterised in that：The step (2) is：Add in above-mentioned mixed material liquid
Enter bimetallic catalyst, 180~280 DEG C of 0.5~8h of reaction are heated in autoclave, room temperature is cooled to.
5. synthetic method as claimed in claim 1, it is characterised in that：First metal and bimetallic mol ratio are 1
~8: 1~8.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108165330A (en) * | 2018-01-30 | 2018-06-15 | 中山大学 | A kind of method of one step recycling of plant and energy after soil remediation |
| CN108355715A (en) * | 2018-02-07 | 2018-08-03 | 江南大学 | A kind of synthesis and application of grafting zirconium complex heterogeneous catalysis |
| CN109395778A (en) * | 2018-11-13 | 2019-03-01 | 北京林业大学 | A kind of phytic acid niobium supported nano-gold category catalyst system for levulic acid and ester through hydrogenation |
| CN109694363A (en) * | 2018-07-18 | 2019-04-30 | 吉林大学 | In-situ reducing basic copper carbonate/aluminum oxyhydroxide is catalyzed levulic acid or levulinate to the method for gamma-valerolactone |
| CN109999775A (en) * | 2019-05-15 | 2019-07-12 | 贵州大学 | A kind of preparation of metal-doped mesoporous silicon oxide solid catalyst and its application in biomass conversion |
| CN111434657A (en) * | 2019-01-15 | 2020-07-21 | 吉林大学 | Preparation method of gamma-valerolactone and levulinic acid ester compounds |
| 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 |
| CN112898244A (en) * | 2019-12-03 | 2021-06-04 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
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| CN108165330A (en) * | 2018-01-30 | 2018-06-15 | 中山大学 | A kind of method of one step recycling of plant and energy after soil remediation |
| CN108355715A (en) * | 2018-02-07 | 2018-08-03 | 江南大学 | A kind of synthesis and application of grafting zirconium complex heterogeneous catalysis |
| CN109694363A (en) * | 2018-07-18 | 2019-04-30 | 吉林大学 | In-situ reducing basic copper carbonate/aluminum oxyhydroxide is catalyzed levulic acid or levulinate to the method for gamma-valerolactone |
| CN109694363B (en) * | 2018-07-18 | 2022-10-11 | 吉林大学 | Method for catalyzing levulinic acid or levulinic acid ester to gamma-valerolactone by in-situ reduction of basic copper carbonate/aluminum oxyhydroxide |
| CN109395778B (en) * | 2018-11-13 | 2021-10-22 | 北京林业大学 | Niobium phytate supported nano metal catalytic system for levulinic acid and ester hydrogenation |
| CN109395778A (en) * | 2018-11-13 | 2019-03-01 | 北京林业大学 | A kind of phytic acid niobium supported nano-gold category catalyst system for levulic acid and ester through hydrogenation |
| CN111434657B (en) * | 2019-01-15 | 2023-06-16 | 吉林大学 | Preparation method of gamma-valerolactone and levulinate ester compound |
| CN111434657A (en) * | 2019-01-15 | 2020-07-21 | 吉林大学 | Preparation method of gamma-valerolactone and levulinic acid ester compounds |
| CN109999775B (en) * | 2019-05-15 | 2022-02-18 | 贵州大学 | Preparation of metal-doped mesoporous silica solid catalyst and application of metal-doped mesoporous silica solid catalyst in biomass conversion |
| CN109999775A (en) * | 2019-05-15 | 2019-07-12 | 贵州大学 | A kind of preparation of metal-doped mesoporous silicon oxide solid catalyst and its application in biomass conversion |
| CN112898244A (en) * | 2019-12-03 | 2021-06-04 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| CN112898244B (en) * | 2019-12-03 | 2022-12-13 | 南京理工大学 | Method for synthesizing gamma-valerolactone |
| 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 |
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