CN107930642A - A kind of catalyst that γ valerolactones are prepared for levulic acid catalytic hydrogenation - Google Patents
A kind of catalyst that γ valerolactones are prepared for levulic acid catalytic hydrogenation Download PDFInfo
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- CN107930642A CN107930642A CN201710993137.5A CN201710993137A CN107930642A CN 107930642 A CN107930642 A CN 107930642A CN 201710993137 A CN201710993137 A CN 201710993137A CN 107930642 A CN107930642 A CN 107930642A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
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Abstract
The invention discloses a kind of catalyst that γ valerolactones are prepared for levulic acid catalytic hydrogenation, the catalyst is using Co and Re as active component.The invention discloses a kind of catalyst that γ valerolactones are prepared for levulic acid catalytic hydrogenation, using load type Co Re bimetallic catalysts, the catalyst has the characteristics that content of metal is low, catalytic performance is high, catalyst stability is good, has expanded application of the bimetallic catalyst in γ valerolactone preparation fields.
Description
Technical field
The present invention relates to organic synthesis field, and in particular to one kind prepares gamma-valerolactone for levulic acid catalytic hydrogenation
Catalyst.
Background technology
The fossil energies such as coal, natural gas and oil are the basic of human survival and development, increasingly withered with fossil resource
Exhaust, the deterioration of ecological environment, global climate warm and rapid development of economy, there is an urgent need for find a kind of new, regenerative resource
Instead of non-renewable fossil energy.Biomass due to its rich reserves, derive from a wealth of sources, it is cheap the advantages that, becoming can be again
The main source of raw fuels and chemicals.In numerous Biomass-based chemicals, gamma-valerolactone (GVL) can be used as spices
Compound, solvent, food additives and liquid fuel；A series of reaction, product of the generation with surcharge, such as 2- can be passed through
Methyltetrahydrofuran (2-MTHF), 1,4- pentanediols, butyl ketone, polyacrylate and nylon intermediates etc..Gamma-valerolactone is
A kind of important platform chemicals, can be made by levulic acid (LA) and its derivative through catalytic hydrogenation.
A kind of catalysis levulic acid Hydrogenation disclosed in the Chinese patent literature of 105289592 A of Publication No. CN for γ-
The method of valerolactone, uses load type metal ruthenium catalyst, under 50~130 DEG C of reaction temperature, 1~6MPa of reaction pressure, second
Acyl propionic acid rate is 100%, and gamma-valerolactone high selectivity is up to 99.9%.
And for example disclosed in the Chinese patent literature of 102658131 A of Publication No. CN it is a kind of be used for levulic acid γ-
The ruthenium-based catalyst of valerolactone, the ruthenium-based catalyst include active component and catalyst carrier, using ruthenium as active component, quality hundred
Divide than being 1~10%；Remainder is catalyst carrier.Alternatively, the ruthenium-based catalyst includes active component, co-catalyst and urges
Agent carrier, co-catalyst is the VIIIth race's element or the Ith B races element, under 70~120 DEG C, 1~5MPa reaction conditions, acetyl
Propionic acid can convert completely, and the yield of gamma-valerolactone is up to 99%.
For another example patent WO 02074760 and US 20030055270 disclose levulic acid in loaded noble metal catalyst
Under, 215 DEG C of reaction temperature, under the conditions of Hydrogen Vapor Pressure is 4.83~5.52MPa, the yield of gamma-valerolactone is up to 97%.
To sum up, at present in published catalytic hydrogenation method, use noble metal standby as catalysis levulic acid Hydrogenation mostly
The catalyst of gamma-valerolactone, these usual method severe reaction conditions, catalyst easy in inactivation or noble-metal-supported amount are big, it is difficult to
Adapt to the production of industrial-scale.
The content of the invention
The invention discloses a kind of catalyst that gamma-valerolactone is prepared for levulic acid catalytic hydrogenation, using support type
Co-Re bimetallic catalysts, the catalyst have the characteristics that content of metal is low, catalytic performance is high, catalyst stability is good, open up
Application of the bimetallic catalyst in gamma-valerolactone preparation field is opened up.
Concrete technical scheme is as follows：
It is a kind of to prepare the catalyst of gamma-valerolactone for levulic acid catalytic hydrogenation, the catalyst using Co and Re as
Active component.
In recent years, seminar where inventor is directed to studying the preparation and application of bimetallic catalyst, it has been investigated that,
In the bimetallic system that metal Co and metal Re is formed, grappling synergistic effect can be formed between metal Co and metal Re, and
And electronics distribution and the structure of catalyst surface can be changed, metal component of mutually promoting disperses.And it has furthermore been found that should
When Co-Re bimetallic catalysts are used for levulic acid Hydrogenation for gamma-valerolactone, only need extremely low load capacity that height can be achieved and urge
Change performance, and catalyst stabilizer is good, not easy in inactivation.
The catalyst further includes carrier, can be Common oxides or activated carbon.As titanium dioxide, silica,
Gama-alumina or activated carbon etc..
Preferably, in terms of catalyst gross mass, the load capacity of active component is mole of 0.1~15wt%, Co and Re
Than for 1:0.2~5.Further preferably, the load capacity of active component is that the molar ratio of 0.1~5wt%, Co and Re are 1:0.5~
2。
Still further preferably, the carrier is selected from titanium dioxide, in terms of catalyst gross mass, the load capacity of active component
Molar ratio for 1wt%, Co and Re is 1:1.
Load type Co-Re the bimetallic catalysts are prepared by equi-volume impregnating, and basic process is：
The saturated water absorption of carrier is calculated first, then is calculated respectively by bimetallic load capacity and the molar ratio of Co/Re
Go out required cobalt salt and the quality containing rhenium compound, be dissolved in water both are full and uniform, be slowly added to the load of certain mass
Body, dry 5~15h in 90~130 DEG C of vacuum drying chambers is placed after 12~36h of incipient impregnation, then is obtained after reduction treatment
Catalyst.
The invention also discloses a kind of method that gamma-valerolactone is prepared by levulic acid catalytic hydrogenation, is specially：
Catalyst after carrying out reduction is mixed with levulic acid and solvent, then is passed through hydrogen source, is obtained after reacted in γ-penta
Ester.
Preferably, the reduction of the catalyst carries out in a hydrogen atmosphere, reduction temperature is 300~550 DEG C, into one
Step is preferably 450~550 DEG C.
Preferably, the catalyst and the mass ratio of levulic acid are 4~16:100；
The solvent is selected from least one of 1,4- dioxane, tetrahydrofuran, methanol, ethanol, isopropanol；Into one
Step is preferably 1,4- dioxane.
The levulic acid and the mass volume ratio of solvent are 1g~10g:100ml.
Preferably, the hydrogen source is selected from least one of hydrogen, methanol, isopropanol, formic acid；More preferably
Hydrogen.
Preferably, it is 0.8~1.8MPa to be passed through hydrogen source to reacting kettle inner pressure；
The temperature of the reaction is 120~220 DEG C, and the time is 3~5h；Further preferred reaction temperature for 180~
220℃。
When the catalyst of use, carrier is selected from titanium dioxide, and in terms of carrier quality, the load capacity of active component is 1wt%,
The molar ratio of Co and Re is 1:When 1, the matched optimum process condition for preparing gamma-valerolactone is：
The catalyst reduction temperature is 500 DEG C；
The mass ratio of catalyst and levulic acid is 12~16:100, the mass volume ratio of levulic acid and solvent is
0.05g/mL；
It is 0.5MPa to be passed through hydrogen to reacting kettle inner pressure, and the temperature of reaction is 180~220 DEG C, time 4h.
It is described after reaction, first autoclave body is put into cold water and is allowed to cool down rapidly, is sampled after driving kettle, uses gas-chromatography
Instrument quantitative analysis.
Compared with prior art, the invention has the advantages that：
(1) load type bimetal catalyst that the present invention is prepared using Co and Re as active component, forms using between bimetallic
Grappling synergistic effect, thus it is possible to vary the electronics distribution of catalyst surface and structure, and promote the scattered of metal component, so as to obtain
Obtained the loaded catalyst for the advantages that content of metal is low, catalytic performance is high, stability is good；
(2) above-mentioned catalyst is used, using levulic acid as raw material, prepares gamma-valerolactone through catalytic hydrogenation reaction, then pass through
After the optimization of reaction condition, it can obtain high yield and selectivity under extremely low content of metal, expanded bimetallic
Application of the catalyst in gamma-valerolactone preparation field.
Brief description of the drawings
Fig. 1 is the TEM pictures of catalyst prepared by embodiment 2；
Fig. 2 is the TEM pictures of catalyst prepared by embodiment 4；
Fig. 3 is the TEM pictures of catalyst prepared by embodiment 5.
Embodiment
With reference to specific embodiment, the invention will be further described, but protection scope of the present invention is not limited in
This.
Embodiment 1
(1) equi-volume impregnating prepares Co-Re bimetallics/titanium deoxide catalyst
The saturated water absorption of titania support is calculated first, and (in terms of catalyst gross mass, bimetallic is born on request
The molar ratio that carrying capacity is 1%, Co/Re is 0.8:0.2) required Co (NO are calculated3)2·6H2O and NH4ReO4Quality, by two
Person is full and uniform to be dissolved in water, and is slowly added to 2g carriers, is placed after incipient impregnation 24h dry in 110 DEG C of vacuum drying chambers
10h.3h is reduced under last 500 DEG C of atmosphere of hydrogen.
(2) levulic acid Hydrogenation is catalyzed for gamma-valerolactone
Test and carried out in the batch reactor that a volume is 35ml, Co-Re bimetallic/bis- prepared by step (1)
Titanium oxide catalyst, dosage 0.06g add reaction raw materials levulic acid 0.5g, and the dosage of solvent Isosorbide-5-Nitrae-dioxane is
10ml, Hydrogen Vapor Pressure 1.5MPa, reaction temperature are 180 DEG C, reaction time 4h, after reaction, are first put into autoclave body cold
It is allowed to rapidly cool down in water, is sampled after driving kettle, with gas chromatograph quantitative analysis.
After tested, levulic acid conversion ratio is 54.0%, and gamma-valerolactone yield is 50.8%.
Embodiment 2~8
The preparation process of catalyst is identical with embodiment 1, differs only in Co-Re bimetallic/bis- being prepared
Bimetallic load capacity is different from the molar ratio of Co/Re in titanium oxide catalyst, is specifically listed in the table below in 1.
It is identical with embodiment 1 with reaction condition for the raw material dosage of gamma-valerolactone to be catalyzed levulic acid Hydrogenation,
Wherein, the levulic acid conversion ratio of each embodiment and gamma-valerolactone yield are listed in the table below in 1.
Table 1
N.D.=is not detected by
Embodiment 9~12
The Co-Re bimetallics load capacity that embodiment 2 is prepared is used as 1wt%, Co/Re molar ratios are 0.5:0.5
Catalyst.
During levulic acid Hydrogenation is catalyzed for gamma-valerolactone, in addition to catalyst reduction temperature is different, other reaction bars
Part and raw material dosage are identical with embodiment 2, and the levulic acid of specific catalyst reduction temperature and each embodiment turns
Rate and gamma-valerolactone yield are listed in the table below in 2.
Table 2
| Embodiment | Catalyst reduction temperature (DEG C) | Levulic acid conversion ratio (%) | Gamma-valerolactone yield (%) |
| 9 | 300 | 35.6 | 31.8 |
| 10 | 400 | 76.7 | 70.4 |
| 11 | 450 | 85.6 | 84.5 |
| 2 | 500 | 100.0 | 99.3 |
| 12 | 550 | 84.2 | 78.2 |
Embodiment 13~15
The Co-Re bimetallics load capacity that embodiment 2 is prepared is used as 1wt%, Co/Re molar ratios are 0.5:0.5
Catalyst.
During levulic acid Hydrogenation is catalyzed for gamma-valerolactone, in addition to catalyst amount is different, other raw material dosages and
Reaction condition is identical with embodiment 2, and the levulic acid conversion ratio and γ of specific catalyst amount and each embodiment-
Valerolactone yield is listed in the table below in 3.
Table 3
| Embodiment | Catalyst amount (g) | Levulic acid conversion ratio (%) | Gamma-valerolactone yield (%) |
| 13 | 0.02 | 37.0 | 33.0 |
| 14 | 0.04 | 69.2 | 68.1 |
| 2 | 0.06 | 100 | 99.3 |
| 15 | 0.08 | 100 | 99.5 |
Embodiment 16~20
The Co-Re bimetallics load capacity that embodiment 2 is prepared is used as 1wt%, Co/Re molar ratios are 0.5:0.5
Catalyst.
During levulic acid Hydrogenation is catalyzed for gamma-valerolactone, in addition to reaction temperature is different, other reaction conditions and original
Expect that dosage is identical with embodiment 2, in the levulic acid conversion ratio and γ-penta of specific reaction temperature and each embodiment
Ester yield is listed in the table below in 4.
Table 4
| Embodiment | Reaction temperature (DEG C) | Levulic acid conversion ratio (%) | Gamma-valerolactone yield (%) |
| 16 | 120 | 7.5 | 5.9 |
| 17 | 150 | 59.5 | 56.0 |
| 18 | 180 | 95.6 | 94.7 |
| 19 | 200 | 98.6 | 98.1 |
| 20 | 220 | 99.6 | 99.1 |
Embodiment 21~23
With embodiment 2 recycle Co-Re bimetallics/titanium deoxide catalyst carry out catalysis levulic acid Hydrogenation for γ-
Valerolactone test, reaction condition and raw material dosage are identical with embodiment 2, after reaction, by catalyst with Isosorbide-5-Nitrae-
After dioxane washing, with the content of aas determination solution C o, to determine the loss of metal Co in catalyst, have
The result is shown in table 5 below for body.
Table 5
In four circulation experiments, 20 μ gl of Co concentration average out in bulk solution-1, account for Co concentration in bulk phase catalyst
0.14%.Illustrate that Co metals slightly lose in reuse, show that the catalyst has good repeatability.
Comparative example 1
(1) equi-volume impregnating prepares Co-Re bimetallics/SiO 2 catalyst
The saturated water absorption of silica supports is calculated first, and (bimetallic load capacity is 1%, with catalysis on request
Agent gross mass meter, the wherein molar ratio of Co/Re are 0.5:0.5) required Co (NO are calculated3)2·6H2O and NH4ReO4Matter
Amount, is dissolved in water both are full and uniform, is slowly added to 2g carriers, 110 DEG C of vacuum drying chambers are placed after incipient impregnation 24h
Middle dry 10h.3h is reduced under last 500 DEG C of atmosphere of hydrogen.
(2) levulic acid Hydrogenation is catalyzed for gamma-valerolactone
Test and carried out in the batch reactor that a volume is 35ml, Co-Re bimetallic/bis- prepared by step (1)
Silicon oxide catalyst, dosage 0.06g add reaction raw materials levulic acid 0.5g, and the dosage of solvent Isosorbide-5-Nitrae-dioxane is
10ml, Hydrogen Vapor Pressure 1.5MPa, reaction temperature are 180 DEG C, reaction time 4h, after reaction, are first put into autoclave body cold
It is allowed to rapidly cool down in water, is sampled after driving kettle, with gas chromatograph quantitative analysis.
After tested, levulic acid conversion ratio is 29.0%, and gamma-valerolactone yield is 28.3%.
Comparative example 2
The preparation of catalyst and catalysis levulic acid Hydrogenation are identical with to this example 1 for the technological process of gamma-valerolactone,
Differ only in, catalyst prepared by this comparative example is used as carrier using gama-alumina.After tested, levulic acid conversion ratio is
54.0%, gamma-valerolactone yield is 52.5%.
Comparative example 3
The preparation of catalyst and catalysis levulic acid Hydrogenation are identical with to this example 1 for the technological process of gamma-valerolactone,
Differ only in, catalyst prepared by this comparative example is used as carrier using activated carbon.After tested, levulic acid conversion ratio is
66.6%, gamma-valerolactone yield is 64.9%.
Pass through more each embodiment and comparative example：
In hydrogenation catalyst levulic acid prepares the technique of gamma-valerolactone, compared to traditional silica, activated carbon,
For aluminium oxide etc. as carrier loaded bimetallic catalyst, Co-Re bimetallics/titanium deoxide catalyst, show the production of higher
Rate and superior conversion ratio, its conversion ratio may be up to 100%, and yield reaches as high as 99.5%.In addition, bimetallic catalyst phase
Than in traditional single-metal reforming catalyst, there is the characteristics of low-load, low dosage and high catalytic activity, be the production of gamma-valerolactone
Technique provides a kind of efficient catalyst.
Claims (10)
1. a kind of prepare the catalyst of gamma-valerolactone for levulic acid catalytic hydrogenation, it is characterised in that the catalyst with
Co and Re is active component.
2. the catalyst according to claim 1 that gamma-valerolactone is prepared for levulic acid catalytic hydrogenation, its feature exist
In, the catalyst further includes carrier, and in terms of catalyst gross mass, the load capacity of active component is 0.1~15wt%, Co and
The molar ratio of Re is 1:0.2~5.
3. the catalyst according to claim 1 that gamma-valerolactone is prepared for levulic acid catalytic hydrogenation, its feature exist
In the carrier is selected from titanium dioxide, silica, gama-alumina or activated carbon.
4. the catalyst for being used for levulic acid catalytic hydrogenation and preparing gamma-valerolactone according to claim 1 or 2 or 3, it is special
Sign is that the carrier is selected from titanium dioxide, and in terms of catalyst gross mass, the load capacity of active component is 0.1~5wt%,
The molar ratio of Co and Re is 1:0.5~2.
5. the catalyst according to claim 4 that gamma-valerolactone is prepared for levulic acid catalytic hydrogenation, its feature exist
In the carrier is selected from titanium dioxide, and in terms of catalyst gross mass, the load capacity of active component is rubbing for 1wt%, Co and Re
You are than being 1:1.
A kind of 6. method that gamma-valerolactone is prepared by levulic acid catalytic hydrogenation, it is characterised in that as described in Claims 1 to 5
Catalyst after carrying out reduction, mixed with levulic acid and solvent, then be passed through hydrogen source, gamma-valerolactone obtained after reacted.
7. the method according to claim 6 that gamma-valerolactone is prepared by levulic acid catalytic hydrogenation, it is characterised in that institute
The reduction for the catalyst stated carries out in a hydrogen atmosphere, and reduction temperature is 300~550 DEG C.
8. the method according to claim 6 that gamma-valerolactone is prepared by levulic acid catalytic hydrogenation, it is characterised in that institute
The catalyst and the mass ratio of levulic acid stated are 4~16:100；
The solvent is selected from least one of 1,4- dioxane, tetrahydrofuran, methanol, ethanol, isopropanol；
The levulic acid and the mass volume ratio of solvent are 1~10g:100ml.
9. the method according to claim 6 that gamma-valerolactone is prepared by levulic acid catalytic hydrogenation, it is characterised in that institute
The hydrogen source stated is selected from least one of hydrogen, methanol, isopropanol, formic acid.
10. the method according to claim 6 that gamma-valerolactone is prepared by levulic acid catalytic hydrogenation, it is characterised in that logical
It is 0.8~1.8MPa to enter hydrogen source to reacting kettle inner pressure；
The temperature of the reaction is 120~220 DEG C, and the time is 3~5h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485621A (en) * | 2018-11-30 | 2019-03-19 | 中国科学技术大学 | A method of producing gamma valerolactone |
| CN113198466A (en) * | 2021-05-14 | 2021-08-03 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of levulinic acid compounds and application of heterogeneous catalyst |
| CN113786864A (en) * | 2021-09-07 | 2021-12-14 | 安徽建筑大学 | Catalyst and method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation by using same |
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| CN1711133A (en) * | 2002-11-11 | 2005-12-21 | 巴斯福股份公司 | Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst |
| CN104557801A (en) * | 2014-10-31 | 2015-04-29 | 华东理工大学 | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst |
| CN107108538A (en) * | 2015-01-09 | 2017-08-29 | 巴斯夫欧洲公司 | The method for preparing tetrahydrofuran, 1,4 butanediols or gamma butyrolactone |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711133A (en) * | 2002-11-11 | 2005-12-21 | 巴斯福股份公司 | Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst |
| CN104557801A (en) * | 2014-10-31 | 2015-04-29 | 华东理工大学 | Method for preparing gamma-valerolactone from furfural on metal/solid acid catalyst |
| CN107108538A (en) * | 2015-01-09 | 2017-08-29 | 巴斯夫欧洲公司 | The method for preparing tetrahydrofuran, 1,4 butanediols or gamma butyrolactone |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485621A (en) * | 2018-11-30 | 2019-03-19 | 中国科学技术大学 | A method of producing gamma valerolactone |
| CN113198466A (en) * | 2021-05-14 | 2021-08-03 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of levulinic acid compounds and application of heterogeneous catalyst |
| CN113198466B (en) * | 2021-05-14 | 2022-04-29 | 浙江工业大学 | Heterogeneous catalyst for selective hydrogenation reaction of levulinic acid compounds and application of heterogeneous catalyst |
| CN113786864A (en) * | 2021-09-07 | 2021-12-14 | 安徽建筑大学 | Catalyst and method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation by using same |
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