CN107930642B - A kind of catalyst preparing gamma-valerolactone for levulic acid catalytic hydrogenation - Google Patents
A kind of catalyst preparing gamma-valerolactone for levulic acid catalytic hydrogenation Download PDFInfo
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- CN107930642B CN107930642B CN201710993137.5A CN201710993137A CN107930642B CN 107930642 B CN107930642 B CN 107930642B CN 201710993137 A CN201710993137 A CN 201710993137A CN 107930642 B CN107930642 B CN 107930642B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- 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 catalyst that gamma-valerolactone is prepared for levulic acid catalytic hydrogenation, and the catalyst is using Co and Re as active component.The invention discloses a kind of catalyst that gamma-valerolactone is prepared for levulic acid catalytic hydrogenation, using load type Co-Re bimetallic catalyst, the catalyst has the characteristics that content of metal is low, catalytic performance is high, catalyst stability is good, has expanded bimetallic catalyst in the application of gamma-valerolactone preparation field.
Description
Technical field
The present invention relates to organic synthesis fields, and in particular to one kind prepares gamma-valerolactone for levulic acid catalytic hydrogenation
Catalyst.
Background technique
The fossil energies such as coal, natural gas and petroleum 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, need to find a kind of novel, renewable energy
Instead of non-renewable fossil energy.Biomass due to its rich reserves, it is from a wealth of sources, 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 fragrance
Close object, solvent, food additives and liquid fuel；A series of reaction can be passed through, generate the product with surcharge, such as 2-
Methyltetrahydrofuran (2-MTHF), 1,4- pentanediol, 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 is disclosed in the Chinese patent literature of 105289592 A of Publication No. CN adds hydrogen to prepare 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%, gamma-valerolactone selectively up to 99.9%.
It is for another example disclosed in the Chinese patent literature of 102658131 A of Publication No. CN a kind of for levulic acid γ-
The ruthenium-based catalyst of valerolactone, which includes active component and catalyst carrier, using ruthenium as active component, quality hundred
Divide than being 1~10%；Rest part 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 race element, under 70~120 DEG C, 1~5MPa reaction condition, 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, noble metal is used to add hydrogen to prepare as catalysis levulic acid 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.
Summary 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 catalyst, the catalyst have the characteristics that content of metal is low, catalytic performance is high, catalyst stability is good, open up
Bimetallic catalyst has been opened up in the application of gamma-valerolactone preparation field.
Specific technical solution is as follows:
A kind of catalyst preparing gamma-valerolactone for levulic acid catalytic hydrogenation, the catalyst are with Co and Re
Active component.
In recent years, seminar where inventor is dedicated 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, anchoring synergistic effect can be formed between metal Co and metal Re, and
And it can change the electronics distribution and structure of catalyst surface, the dispersion for metal component of mutually promoting.And it has furthermore been found that should
When Co-Re bimetallic catalyst adds hydrogen to prepare gamma-valerolactone for levulic acid, only needs extremely low load capacity that height can be realized and urge
Change performance, and catalyst stabilizer is good, not easy in inactivation.
The catalyst further includes carrier, can be Common oxides or active carbon.As titanium dioxide, silica,
Gama-alumina or active carbon etc..
Preferably, the load capacity of active component is mole of 0.1~15wt%, Co and Re in terms of catalyst gross mass
Than for 1:0.2~5.Further preferably, the load capacity of active component be the molar ratio of 0.1~5wt%, Co and Re be 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 catalyst is prepared by equi-volume impregnating, basic process are as follows:
The saturated water absorption of carrier is calculated first, then is calculated separately by the molar ratio of bimetallic load capacity and Co/Re
Required cobalt salt and the quality containing rhenium compound out are dissolved in water the two is full and uniform, are slowly added to the load of certain mass
Body is placed dry 5~15h in 90~130 DEG C of vacuum ovens after 12~36h of incipient impregnation, then is obtained after reduction treatment
Catalyst.
The invention also discloses a kind of method for preparing gamma-valerolactone by levulic acid catalytic hydrogenation, specifically:
Catalyst after carrying out reduction is mixed with levulic acid and solvent, then is passed through hydrogen source, is obtained in γ-penta after reacted
Ester.
Preferably, the reduction of the catalyst carries out in a hydrogen atmosphere, reduction temperature is 300~550 DEG C, into one
Preferably 450~550 DEG C of step.
Preferably, the mass ratio of the catalyst and levulic acid is 4~16:100；
The solvent is selected from least one of 1,4- dioxane, tetrahydrofuran, methanol, ethyl alcohol, isopropanol；Into one
Step is preferably 1,4- dioxane.
The mass volume ratio of the levulic acid and solvent is 1g~10g:100ml.
Preferably, the hydrogen source is selected from least one of hydrogen, methanol, isopropanol, formic acid；Further preferably
Hydrogen.
Preferably, being passed through hydrogen source to reacting kettle inner pressure is 0.8~1.8MPa；
The temperature of the reaction is 120~220 DEG C, and the time is 3~5h；Further preferred reaction temperature be 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%,
When the molar ratio of Co and Re is 1:1, the matched optimum process condition for preparing gamma-valerolactone are as follows:
The catalyst reduction temperature is 500 DEG C；
The mass ratio of catalyst and levulic acid is 12~16:100, and the mass volume ratio of levulic acid and solvent is
0.05g/mL；
Being passed through hydrogen to reacting kettle inner pressure is 0.5MPa, and the temperature of reaction is 180~220 DEG C, time 4h.
It is described that first autoclave body is put into and is allowed to rapidly cool down in cold water after reaction, it is sampled after opening kettle, uses gas-chromatography
Instrument quantitative analysis.
Compared with prior art, the present invention has the advantage that
(1) load type bimetal catalyst that the present invention is prepared using Co and Re as active component, forms using between bimetallic
Anchoring synergistic effect, thus it is possible to vary the electronics of catalyst surface is distributed and structure, and promotes the dispersion of metal component, to obtain
Obtained the loaded catalyst for the advantages that content of metal is low, catalytic performance is high, stability is good；
(2) gamma-valerolactone is prepared through catalytic hydrogenation reaction, then pass through using levulic acid as raw material using above-mentioned catalyst
After the optimization of reaction condition, high yield and selectivity can be obtained, bimetallic has been expanded under extremely low content of metal
Application of the catalyst in gamma-valerolactone preparation field.
Detailed description of the invention
Fig. 1 is the TEM picture of catalyst prepared by embodiment 2；
Fig. 2 is the TEM picture of catalyst prepared by embodiment 4；
Fig. 3 is the TEM picture of catalyst prepared by embodiment 5.
Specific embodiment
Combined with specific embodiments below, 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 bimetallic/titanium deoxide catalyst
The saturated water absorption of titania support is calculated first, and (in terms of catalyst gross mass, bimetallic is negative as required
The molar ratio that carrying capacity is 1%, Co/Re is 0.8:0.2) calculate required Co (NO3)2·6H2O and NH4ReO4Quality, by two
Person is full and uniform to be dissolved in water, and 2g carrier is slowly added to, and incipient impregnation is placed dry in 110 DEG C of vacuum ovens afterwards for 24 hours
10h.3h is restored under last 500 DEG C of atmosphere of hydrogen.
(2) catalysis levulic acid adds hydrogen to prepare gamma-valerolactone
It tests and is carried out in the batch reactor that a volume is 35ml, Co-Re bimetallic/bis- of step (1) preparation
Reaction raw materials levulic acid 0.5g is added in titanium oxide catalyst, dosage 0.06g, and solvent Isosorbide-5-Nitrae-dioxane dosage 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, be sampled after opening 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 as in embodiment 1, and difference is only that 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.
The raw material dosage that catalysis levulic acid adds hydrogen to prepare gamma-valerolactone is identical with embodiment 1 with reaction condition,
Wherein, the levulic acid conversion ratio and gamma-valerolactone yield of each embodiment are listed in the table below in 1.
Table 1
N.D.=is not detected
Embodiment 9~12
For the Co-Re bimetallic load capacity for using embodiment 2 to be prepared for 1wt%, Co/Re molar ratio is 0.5:0.5's
Catalyst.
During catalysis levulic acid adds hydrogen to prepare gamma-valerolactone, in addition to catalyst reduction temperature is different, other reaction items
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
For the Co-Re bimetallic load capacity for using embodiment 2 to be prepared for 1wt%, Co/Re molar ratio is 0.5:0.5's
Catalyst.
During catalysis levulic acid adds hydrogen to prepare gamma-valerolactone, in addition to catalyst amount is different, other raw material dosages and
Reaction condition is identical with embodiment 2, 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
For the Co-Re bimetallic load capacity for using embodiment 2 to be prepared for 1wt%, Co/Re molar ratio is 0.5:0.5's
Catalyst.
During catalysis levulic acid adds hydrogen to prepare 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
Carrying out catalysis levulic acid with Co-Re bimetallic/titanium deoxide catalyst that embodiment 2 recycles adds hydrogen to prepare γ-
Valerolactone experiment, reaction condition and raw material dosage are identical with embodiment 2, after reaction, by catalyst Isosorbide-5-Nitrae-
After dioxane washing, with the content of aas determination solution C o, to determine the loss of metal Co in catalyst, tool
Body result see the table below 5.
Table 5
In four circulation experiments, 20 μ gl of Co concentration average out in bulk solution-1, account for about Co concentration in bulk phase catalyst
0.14%.Illustrate that Co metal slightly loses in reuse, shows that the catalyst has good repeatability.
Comparative example 1
(1) equi-volume impregnating prepares Co-Re bimetallic/SiO 2 catalyst
The saturated water absorption of silica supports is calculated first, and (bimetallic load capacity is 1%, with catalysis as required
Agent gross mass meter, wherein the molar ratio of Co/Re is 0.5:0.5) calculate required Co (NO3)2·6H2O and NH4ReO4Matter
Amount is dissolved in water the two is full and uniform, is slowly added to 2g carrier, and incipient impregnation places 110 DEG C of vacuum ovens afterwards for 24 hours
Middle dry 10h.3h is restored under last 500 DEG C of atmosphere of hydrogen.
(2) catalysis levulic acid adds hydrogen to prepare gamma-valerolactone
It tests and is carried out in the batch reactor that a volume is 35ml, Co-Re bimetallic/bis- of step (1) preparation
Reaction raw materials levulic acid 0.5g is added in silicon oxide catalyst, dosage 0.06g, and solvent Isosorbide-5-Nitrae-dioxane dosage 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, be sampled after opening 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 the process flow for adding hydrogen to prepare gamma-valerolactone of catalysis levulic acid are identical as to this example 1,
Difference is only that the catalyst of this comparative example preparation is using gama-alumina as carrier.After tested, levulic acid conversion ratio is
54.0%, gamma-valerolactone yield is 52.5%.
Comparative example 3
The preparation of catalyst and the process flow for adding hydrogen to prepare gamma-valerolactone of catalysis levulic acid are identical as to this example 1,
Difference is only that the catalyst of this comparative example preparation is using active carbon as carrier.After tested, levulic acid conversion ratio is
66.6%, gamma-valerolactone yield is 64.9%.
By comparing known to each embodiment and comparative example:
In the technique that hydrogenation catalyst levulic acid prepares gamma-valerolactone, compared to traditional silica, active carbon,
Aluminium oxide etc. shows higher production as carrier loaded bimetallic catalyst, Co-Re bimetallic/titanium deoxide catalyst
Rate and superior conversion ratio, 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, having a low-load, low dosage and the high feature of catalytic activity, are the production of gamma-valerolactone
Technique provides a kind of efficient catalyst.
Claims (4)
1. a kind of method for preparing gamma-valerolactone by levulic acid catalytic hydrogenation, which is characterized in that by after reduction catalyst with
Levulic acid and solvent mixing, then it is passed through hydrogen source, gamma-valerolactone is obtained after 180~220 DEG C of reactions；
The catalyst is using titanium dioxide as carrier, using Co and Re as active component, in terms of catalyst gross mass, and active component
Load capacity be the molar ratio of 1wt%, Co and Re be 1:1；
The reduction carries out in a hydrogen atmosphere, and reduction temperature is 450~500 DEG C.
2. the method according to claim 1 for preparing gamma-valerolactone by levulic acid catalytic hydrogenation, which is characterized in that institute
The mass ratio of the catalyst and levulic acid stated is 4~16:100；
The solvent is selected from least one of 1,4- dioxane, tetrahydrofuran, methanol, ethyl alcohol, isopropanol；
The mass volume ratio of the levulic acid and solvent is 1~10g:100ml.
3. the method according to claim 1 for preparing gamma-valerolactone by levulic acid catalytic hydrogenation, which is characterized in that institute
The hydrogen source stated is selected from least one of hydrogen, methanol, isopropanol, formic acid.
4. the method according to claim 1 for preparing gamma-valerolactone by levulic acid catalytic hydrogenation, which is characterized in that logical
Entering hydrogen source to reacting kettle inner pressure is 0.8~1.8MPa；
The time of the reaction is 3~5h.
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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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| 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 |
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