CN109651304A - A kind of method that catalytic hydrogenation levulic acid prepares gamma-valerolactone - Google Patents
A kind of method that catalytic hydrogenation levulic acid prepares gamma-valerolactone Download PDFInfo
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- CN109651304A CN109651304A CN201910075175.1A CN201910075175A CN109651304A CN 109651304 A CN109651304 A CN 109651304A CN 201910075175 A CN201910075175 A CN 201910075175A CN 109651304 A CN109651304 A CN 109651304A
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- 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
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Abstract
The present invention relates to a kind of methods that catalytic hydrogenation levulic acid prepares gamma-valerolactone, i.e., levulic acid is in Ag/ZrO2Selective hydrogenation generates gamma-valerolactone under the action of catalyst.Using Ag/ZrO2Catalyst is under the reaction condition in 220 DEG C and 4MPa Hydrogen Vapor Pressure, and the conversion ratio of levulic acid is up to 99.5%, and the yield and selectivity of gamma-valerolactone are respectively up to 99.3% and 99.8%.Ag/ZrO2The precious metal based catalysts such as catalyst ratio Pt, Pd are cheap, in catalyst Ag can in-situ reducing, therefore, the catalyst is using preceding needing not move through high temperature pre-reduction treatment；Ag and Zr component is not precipitated in hydrogenation process simultaneously, and can be used for aqueous phase reactions, to reaction catalytic activity with higher and selectivity, has industrial application value.
Description
Technical field
The present invention relates to a kind of methods that catalytic hydrogenation levulic acid prepares gamma-valerolactone, and in particular to a kind of Ag/ZrO2
Catalyst, the preparation method of the catalyst and the catalyst are preparing the application in gamma-valerolactone.
Background technique
The increasingly depleted and global warming of fossil resource has caused concern of the people to novel renewable energy.And it gives birth to
Substance is widely present on earth, is a kind of renewable energy, and biomass energy also complies with the original of Green Chemistry in use
Then.Levulic acid (Levulinate, LA) is a kind of platform chemicals that can be obtained by cellulose series biomass, and 2000 beautiful
National energy portion, state renewable energy laboratory is chosen as one of 12 big biomass materials.Under the action of catalyst, LA carbonyl adds
Then hydrogen is esterified available gamma-valerolactone (γ-Valerolactone, GVL).GVL is widely used, except can be used as solvent, food
The additive of product additive and ethanol petrol fuel, research also found recently, can be converted GVL using means such as " catalytic decarbonations "
For C8-C18Liquid hydrocarbon fuel.In addition, the excellent macromolecule polymeric material of a variety of thermal stabilities can also be synthesized by GVL,
Composite material including nylon-type, polyacrylate has important application value.This is pushed to react the key of industrialization
It is to develop effective catalyst, GVL is made to become large platform chemicals.
Homogeneous catalyst in a mild condition selective hydrogenation prepare shown in the reaction of GVL it is good activity and selection
Property.However, these homogeneous catalysts in general exist it is expensive, be easy to run off and the disadvantages of more difficult recycling.Currently, the field
Used heterogeneous catalysis mainly includes platinum-group noble metals catalyst (Ru/C, Pd/C, Pt/C) and nickel-base catalyst (Ni/
Al2O3, Ni-MoOx/C), copper-based catalysts (Cu/Cr2O3、Cu/SiO2) etc. non-precious metal catalysts.Although more so far
Noble metal catalyst can obtain preferable catalytic effect, but due to the disadvantages of it is expensive and limitation large-scale use, and one
A little researchers focus on non-precious metal catalyst.Hengne AM, Rode C V, Cu-ZrO2nanocomposite
catalyst for selective hydrogenation oflevulinic acid and its ester toγ-
Valerolactone [J] .Green Chemistry, 2012,14 (4): 1064-1072 is used under 350 DEG C of atmosphere of hydrogen also
Former Cu/Al2O3And Cu/ZrO2Catalyst takes water as a solvent, in 3.45MPaH2LA selective hydrogenation preparation is catalyzed under pressure
GVL, the yield for obtaining GVL is 100%.But there is also some disadvantages for this kind of copper-based catalysts, for example, Cu/ in water
Al2O3Active ingredient copper can be precipitated.Although methanol replace water as solvent when can it is a degree of inhibition copper component precipitation,
But the selectivity of GVL has but been down to 90%.Putrakumar B,Nagaraju N,Kumar V P,et
al.Hydrogenation oflevulinic acid toγ-valerolactone over copper catalysts
supported onγ-Al2O3[J] .Catalysis Today, 2015,250:209-217 use Cu/Al2O3At 265 DEG C
Reaction, Yan K, Chen A.Selective hydrogenation offurfural and levulinic acid to
Biofuels on the ecofriendly Cu-Fe catalyst [J] .Fuel, 2014,115:101-108 use Cu-Fe
Catalyst is in 7MPa H2The analysis of active ingredient copper in catalyst can be effectively suppressed using high temperature and high pressure for reaction under pressure
Out.However, the condition of these reactions is all harsher, the reaction under high-temperature and high-pressure conditions will also result in high energy consumption, reaction temperature
Carbon distribution is often formed when higher, leads to catalyst serious inactivation.In addition, copper-based catalysts mentioned above often need before the reaction
It will be in 300-400 DEG C of H2Prereduction under atmosphere.Li Zhang,Jingbo Mao,Shenmin Li,Jingmei Yin,
Xudong.Sun,Xinwen.Guo,Chunshan Song,Jinxia Zhou,Hydrogenation of levulinic
acid into gamma-valerolactone over in situ reduced CuAg bimetallic catalyst:
Strategy and mechanism ofpreventing Cu leaching,Appl.Catal.B:Environ.,2018,
232 (15), 1-10 use CuAg/Al2O3Catalyst with tetrahydrofuran (THF) be solvent, in 180 DEG C and 1.4MPa H2It is mild
Reaction condition under, CuAg/Al2O3Catalyst can convert completely LA without reduction pretreatment, GVL yield close to
100mol%, and Cu component is not precipitated.But because Al2O3Catalyst structure can be caused to collapse, caused with LA reactant aqueous solution
The catalyst cannot be used for aqueous phase reactions.
Summary of the invention
In order to overcome the disadvantages of the above prior art and insufficient, the present invention provides a kind of Ag/ZrO2Catalyst and its catalysis
The method for adding hydrogen levulic acid to prepare gamma-valerolactone.
Inventive concept of the invention is: the catalyst is using cheap precious metals ag as hydrogenation active component and with ZrO2For acid
Catalyst component needs not move through high temperature pre-reduction treatment, can be used for aqueous phase reactions, and silver metal component is not analysed in reaction process
Out, ZrO2It will not be corroded by acid LA.The catalyst is anti-under conditions of 4MPa Hydrogen Vapor Pressure and 220 DEG C in aqueous solution
6h is answered, LA can be converted completely, GVL yield is close to 100%.GVL is prepared for LA selective hydrogenation, and a kind of new and effective urge is provided
Agent.
The purpose of the present invention is being achieved by the following technical programs, a kind of catalytic hydrogenation levulic acid preparation γ-penta
The method of lactone, is realized by following steps: being taken water as a solvent, levulic acid is in Ag/ZrO2Under the action of catalyst with H2It carries out anti-
It answers, obtains GVL.
The Ag/ZrO2Catalyst has following composition and preparation process:
That the catalyst provides hydrogenation catalyst function is metal Ag；
That the catalysis provides acid catalysis function is ZrO2；
The catalyst is prepared using coprecipitation, specific steps are as follows:
(1) preparation of salting liquid: a certain amount of AgNO is taken respectively3With Zr (NO3)4·5H2O is made of deionized water dissolving
Salting liquid；
(2) preparation of precipitating reagent: NaOH is dissolved in deionized water, is made into the NaOH solution of 0.2M；
(3) it being co-precipitated: salting liquid is placed on magnetic stirring apparatus, aqueous slkali is added dropwise into salting liquid for 1000rpm stirring,
And the pH value of solution is surveyed, when pH=12 or so, stop that lye is added dropwise, continues to stir 4h, close stirring, be aged 12h；
(4) it filters: solution being filtered with Buchner funnel, until filter cake ethanol washing to neutrality；
(5) dry: filter cake in step (4) being placed in a vacuum drying oven 110 DEG C of dry 12h, is ground, is made with agate mortar
It becomes powder；
(6) it roasts: powdered samples prepared by step (5) being put into crucible, are placed in Muffle furnace through 3h temperature programming
By room temperature to 500 DEG C, the constant temperature calcining 3h at 500 DEG C takes out sample sealed storage when temperature is down to 100 DEG C.
AgNO is configured in the step (1)3With Zr (NO3)4·5H2When O salting liquid, the molar ratio of Ag and Zr be 1:10~
2:1 preferentially uses the molar ratio of 1:5~1:1.
Prepared Ag/ZrO2Catalyst needs not move through hydrogen reduction pretreatment, that is, can produce catalytic activity.
The reaction takes water as a solvent, and levulic acid hydrogenation reaction temperature is 200~240 DEG C, and Hydrogen Vapor Pressure is 3~5MPa.
Preferably, levulic acid hydrogenation reaction temperature is 220 DEG C, Hydrogen Vapor Pressure 4MPa, reacts 6h.
The present invention has the following advantages compared with the prior art and effect:
(1)Ag/ZrO2Active metal component Ag is not precipitated catalyst in the reaction.Since the reduction temperature of Ag is very low
(70 degree or so), even if in freshly synthesized fresh Ag/ZrO2Contain some Ag in catalyst2O, but be converted in situ into quickly
Simple substance Ag, and LA will not be reacted with simple substance Ag, so Ag/ZrO2The problem of catalyst is precipitated there is no metal component.
(2)ZrO2It will not be reacted with LA.With Al in compared with the prior art2O3The catalyst of carrier is made, because LA can be with
Al2O3Reaction, causes catalyst structure to be destroyed, and post catalyst reaction generates Swelling.And ZrO2In LA aqueous solution very
Stablize, post catalyst reaction is not swollen.So Ag/ZrO of the present invention2Catalyst can adapt to aqueous solvent reaction system.
(3) although Ag belongs to noble metal, but compared with Au, Pt, Pd, Ru etc., belongs to cheap noble metal, furthermore
Ag/ZrO2Catalyst needs not move through high temperature pre-reduction treatment, will not inactivate because of oxidation.Ag/ZrO2Catalyst is using coprecipitated
The preparation of shallow lake method, preparation method is simple, is suitble to heavy industrialization preparation.Reaction temperature is controlled at 220 DEG C or less, Ag/ZrO2
Catalyst will not dissociate C-C key, so not will lead to GVL decomposition, at 220 DEG C, 4MPa H2, under conditions of 6h, gamma-valerolactone
Yield up to 99.3%, embody to the very high selectivity of GVL.
In conclusion Ag/ZrO2Catalyst has reactivity high, selective when being catalyzed levulic acid hydrogenation reaction
The features such as high, the conversion ratio of the reaction levulic acid is up to 100.0%, and close to 100%, metal component silver is not precipitated selectivity,
Acidic components ZrO2It is not acted on LA, which needs not move through high temperature prereduction during the reaction, and be that can be used for water
The catalyst of phase system, it is environmentally protective, there is apparent advantage and industrial application value.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Unless otherwise specified, experimental method of the present invention is conventional method, experiment equipment used, material, reagent etc.
Chemically company buys.
The intermittent reaction of embodiment 1-4 differential responses temperature
1. catalyst preparation: preparing Ag/ZrO using coprecipitation2Catalyst, specific steps are as follows:
(1) preparation of salting liquid: AgNO is taken respectively30.5mmol and Zr (NO3)4·5H2O 0.5mmol deionized water is molten
200ml salting liquid is made in solution；
(2) preparation of precipitating reagent: the deionized water wiring solution-forming of 250ml is added in the sodium hydroxide of 2000mg；
(3) it being co-precipitated: salting liquid is placed on magnetic stirring apparatus, aqueous slkali is added dropwise into salting liquid for 1000rpm stirring,
And the pH value of solution is surveyed with pH meter, when pH meter measures pH=12 or so, stop that lye is added dropwise, continues to stir 4h, closing is stirred
It mixes, is aged 12h；
(4) it filters: solution being filtered with Buchner funnel, until filter cake ethanol washing to neutrality；
(5) dry: filter cake in step (4) being placed in a vacuum drying oven 110 DEG C of dry 12h, is ground, is made with agate mortar
It becomes powder；
(6) it roasts: powdered samples prepared by step (5) being put into crucible, are placed in Muffle furnace through 3h temperature programming
By room temperature to 500 DEG C, the constant temperature calcining 3h at 500 DEG C takes out sample sealed storage when temperature is down to 100 DEG C.
2. reaction test: testing Ag/ZrO using intermittent reaction2The performance of catalyst levulic acid hydrogenation reaction, tool
Body step are as follows:
(1) magnetic agitation autoclave is taken, 200.0mg levulic acid, 8ml water, 100mg Ag/ZrO are added thereto2
Reaction kettle is tightened simultaneously check device air-tightness, it is ensured that 4MPaH is passed through after device is air tight by catalyst2, 400rpm stirring speed
Rate, setting assigned temperature react 6h.
(2) after reaction, collect liquid product, be added internal standard compound triethylene glycol dimethyl ether 150mg, with gas-chromatography into
Row analysis.Catalyst is recycled by centrifugation.
Wherein: the conversion ratio of levulic acid=(reaction starting when levulic acid substance amount-reaction at the end of levulic acid
The amount of substance)/reaction starting when levulic acid substance amount × 100%
Levulic acid substance when the amount of gamma-valerolactone substance/reactant starting at the end of yield=product of gamma-valerolactone
Amount × 100%
Selectivity=gamma-valerolactone yield/levulic acid conversion ratio × 100% of gamma-valerolactone
Chromatographiccondition are as follows: use hydrogen flame detector (FID), hydrogen is as carrier gas, internal standard method, triethylene glycol diformazan
Ether is internal standard compound.
3. reaction result is shown in Table 1
The result of 1 differential responses temperature of table
Embodiment 1-4 is as it can be seen that 200 DEG C -220 DEG C and 4MPa H2Under conditions of react 6h when, LA is almost converted,
And it is only selective close to 100% in 220 DEG C of LA.When temperature is lower than 220 DEG C, with the presence of intermediate product；When temperature is higher than 220
DEG C when, have part GVL decomposition, cause its yield reduction.So the reaction is suitble to carry out at 220 DEG C or less.
Embodiment 3 after reaction, filter while hot, the solution after being reacted.It is sent out with inductance coupled plasma
Penetrate the content that spectrometer (ICP-OES, Optima7000DV, Perkin Elmer Ltd.) has detected Ag and Zr in solution, equal table
It is bright in the solution without Ag or Zr ion.Illustrate that LA will not during the reaction will not with Ag or Zr component reaction, the catalyst
Precipitating metal component.
The intermittent reaction of 5,6 different catalysts dosage of embodiment
1. catalyst preparation: with the catalyst preparation process in embodiment 1.
2. reaction test: specific reaction condition: with reaction test process in embodiment 1 200.0mg second is added in operating process
Reaction kettle is tightened simultaneously check device air-tightness, it is ensured that device is air tight by acyl propionic acid, 8ml water and dosage catalyst as shown in table 2
It is passed through 4MPa H later2, reaction temperature is fixed as 220 DEG C by 400rpm stirring rate, and the reaction time is fixed as 6h.
3. reaction result is shown in Table 2.
The result of 2 different catalysts dosage of table
When catalyst amount increases, GVL does not decline selectively, illustrates that product is very stable in the catalyst system.
The intermittent reaction of silver-colored zirconium different proportion in embodiment 7-11 catalyst
1. catalyst preparation: with the catalyst preparation process in embodiment 1, guaranteeing that total amount of metal is certain, but need to be by each
The variation of amount of metal salts adjusts silver-colored zirconium ratio.
2. reaction test: operating process is fixed as 220 DEG C with reaction test process in embodiment 1, by reaction temperature, reaction
Time is fixed as 6h, and see Table 3 for details for silver-colored zirconium different proportion.Reaction condition: 200.0mg levulic acid, 8ml water, 100mgAg/ is added
ZrO2Reaction kettle is tightened simultaneously check device air-tightness, it is ensured that 4MPa H is passed through after device is air tight by catalyst2, 400rpm stirs
Rate is mixed, 6h is reacted.
3. reaction result is shown in Table 3.
The result of silver-colored zirconium different proportion in 3 catalyst of table
Work as n it is obvious from the above resultsAg: nZrReaction effect is best when=1:1, this illustrates the active group of the catalyst
The progress for dividing silver-colored zirconium to need a suitable efficient catalytic hydrogenation reaction of proportion ability.
Above embodiments show Ag/ZrO2Catalyst when being catalyzed levulic acid hydrogenation reaction, have reactivity it is high,
The features such as selectivity is high, the conversion ratio of the reaction levulic acid is up to 100.0%, and selectivity is close to 100%, and metal component silver is not
It is precipitated, acidic components ZrO2It is not acted on LA, which needs not move through high temperature prereduction during the reaction, and be available
It is environmentally protective in the catalyst of aqueous phase system, there is apparent advantage.
1 Cu/ZrO of comparative example2The intermittent reaction of catalyst
1. catalyst preparation: preparing Cu/ZrO using coprecipitation2Catalyst, specific steps are as follows:
(1) preparation of salting liquid: Cu (NO is taken respectively3)2·3H2O 0.5mmol and Zr (NO3)4·5H2O0.5mmol is spent
200ml salting liquid is made in ionized water dissolution；
Remaining preparation step is the same as embodiment 1-4.
2. reaction test: testing function Cu/ZrO using intermittent reaction2The performance of catalyst levulic acid hydrogenation reaction,
The specific steps are same embodiment 1-4.
Reaction result shows that the catalyst does not have catalytic activity, and Cu is precipitated serious.
2 Ag/Al of comparative example2O3The intermittent reaction of catalyst
1. catalyst preparation: preparing AgAl using equi-volume impregnating2O3Catalyst, specific steps are as follows:
(1) pretreatment of carrier: Al2O3550 DEG C of roastings in Muffle furnace；
(2) the water suction measurement of carrier: toward the Al of 1g2O3Middle dropwise addition water is surveyed until water is absorbed completely without residue
Obtain water absorption 0.8ml/g.
(3) preparation of salting liquid: AgNO is taken respectively31.6mmol spends the dissolution of 0.8ml ionized water and Ag salting liquid is made；
(4) it impregnates: by the roasting Al of 1g2O3It pours into the Ag salting liquid of step (3) preparation, and quickly stirs, until complete
It is absorbed entirely；
(5) dry: by product in step (4) in 110 DEG C of dry 12h；
(6) it roasts: product in step (5) is roasted into 3h in 450 DEG C of air atmospheres.
Remaining preparation step is the same as embodiment 1-4.
2. reaction test: testing Ag/Al using intermittent reaction2O3The performance of catalyst levulic acid hydrogenation reaction, tool
Body step is with embodiment 1-4.
Reaction result shows the LA conversion ratio 42.5% under the catalyst action, GVL selectivity 76.9%.It is catalyzed after reaction
Agent expansion is loose, illustrates LA and Al2O3Carrier function makes its structure collapses.And on year-on-year basis under the conditions of, Ag/ZrO of the invention2It urges
Agent can be such that LA converts completely, and GVL yield is close to 100%.
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (5)
1. a kind of method that catalytic hydrogenation levulic acid prepares gamma-valerolactone, which is characterized in that realized by following steps: with water
For solvent, levulic acid is in Ag/ZrO2Under the action of catalyst with H2It is reacted, obtains GVL；
The Ag/ZrO2Catalyst has following composition and preparation process:
That the catalyst provides hydrogenation catalyst function is metal Ag；
That the catalysis provides acid catalysis function is ZrO2；
The catalyst is prepared using coprecipitation, specific steps are as follows:
(1) preparation of salting liquid: a certain amount of AgNO is taken respectively3With Zr (NO3)4·5H2It is molten that salt is made with deionized water dissolving in O
Liquid；
(2) preparation of precipitating reagent: NaOH is dissolved in deionized water, is made into the NaOH solution of 0.2M；
(3) it is co-precipitated: salting liquid is placed on magnetic stirring apparatus, 1000rpm stirring aqueous slkali is added dropwise into salting liquid, and survey
The pH value of solution when pH=12 or so stops that lye is added dropwise, and continues to stir 4h, closes stirring, is aged 12h；
(4) it filters: solution being filtered with Buchner funnel, until filter cake ethanol washing to neutrality；
(5) dry: filter cake in step (4) being placed in a vacuum drying oven 110 DEG C of dry 12h, is ground with agate mortar, makes its change
At powder；
(6) it roasts: powdered samples prepared by step (5) being put into crucible, are placed in Muffle furnace through 3h temperature programming by room
Temperature is to 500 DEG C, the constant temperature calcining 3h at 500 DEG C, and sample sealed storage is taken out when temperature is down to 100 DEG C.
2. the method that a kind of catalytic hydrogenation levulic acid according to claim 1 prepares gamma-valerolactone, which is characterized in that
AgNO is configured in the step (1)3With Zr (NO3)4·5H2When O salting liquid, the molar ratio of Ag and Zr are 1:10~2:1.
3. the method that a kind of catalytic hydrogenation levulic acid according to claim 1 prepares gamma-valerolactone, which is characterized in that
AgNO is configured in the step (1)3With Zr (NO3)4·5H2When O salting liquid, the molar ratio of Ag and Zr are 1:5~1:1.
4. the method that a kind of catalytic hydrogenation levulic acid according to claim 1 prepares gamma-valerolactone, which is characterized in that
The reaction takes water as a solvent, and levulic acid hydrogenation reaction temperature is 200~240 DEG C, and Hydrogen Vapor Pressure is 3~5MPa, reacts 4-
7h。
5. the method that a kind of catalytic hydrogenation levulic acid according to claim 4 prepares gamma-valerolactone, which is characterized in that
Levulic acid hydrogenation reaction temperature is 220 DEG C, Hydrogen Vapor Pressure 4MPa, reacts 6h.
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| CN109999799A (en) * | 2019-05-28 | 2019-07-12 | 云南大学 | Preparation, performance test methods and the application of the ruthenium catalyst of loaded nano containing zirconium |
| CN109999799B (en) * | 2019-05-28 | 2020-09-18 | 云南大学 | Preparation method, performance test method and application of zirconium-containing supported nano ruthenium catalyst |
| CN111253347A (en) * | 2020-02-14 | 2020-06-09 | 大连大学 | Method for preparing gamma-valerolactone by catalytic hydrogenation of levulinic acid |
| CN116003247A (en) * | 2022-12-30 | 2023-04-25 | 上海太和水科技发展股份有限公司 | ZrO (ZrO-like grain) 2 Method for preparing organic acid by catalytic oxidation of chitin |
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Application publication date: 20190419 |