CN108355715A - A kind of synthesis and application of grafting zirconium complex heterogeneous catalysis - Google Patents
A kind of synthesis and application of grafting zirconium complex heterogeneous catalysis Download PDFInfo
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- CN108355715A CN108355715A CN201810123844.3A CN201810123844A CN108355715A CN 108355715 A CN108355715 A CN 108355715A CN 201810123844 A CN201810123844 A CN 201810123844A CN 108355715 A CN108355715 A CN 108355715A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
The invention discloses a kind of synthesis and application of grafting zirconium complex heterogeneous catalysis, belong to solid acid catalysis field.Catalyst synthesis step prepared by the present invention is simple, and raw material is cheap and easy to get, simultaneously contain Lewis acid position andSour position, L acid promote ethyl acetate to add hydrogen, and B acid promotes intermediate product to lactonize, so that ethyl levulinate is efficiently converted into γ valerolactones.Catalyst after reaction is easily recycled, can recycled for multiple times, meet the requirement of Green Sustainable.
Description
Technical field
The present invention relates to a kind of synthesis and application of grafting zirconium complex heterogeneous catalysis, belong to solid acid catalysis neck
Domain.
Background technology
Social now, fossil energy consumes excessively, and environmental problem emerges one after another.Economic restructuring upgrading is extremely urgent,
Wherein change traditional production model, the reproducible new energy of cleaning for seeking alternative fossil energy is the most key.Biomass
As a kind of renewable resource, there is green, derive from a wealth of sources, the features such as storage level is big.Biomass can be turned by biorefinery
It is melted into kinds of platform compound, is used for pharmacy, fuel, the fields such as synthesis of polymer.For example, the lignocellulosic in biomass
The esters of important platform chemicals-levulic acid or levulic acid can be transformed by hydrogenolysis or alcoholysis.Levulic acid and
Its ester can be converted into the higher platform chemicals of added value by being efficiently catalyzed.Wherein, gamma-valerolactone is to study at present
A kind of most hot platform chemicals.It can be used as green solvent, petroleum additive, the presoma of chemical combination product and answered extensively
With.Therefore, how research is efficiently catalyzed levulic acid or its ester is converted into gamma-valerolactone, has great importance.
Gamma-valerolactone chemical property is stable and nontoxic, and has good dissolubility energy, so be one good molten
Agent can replace poisonous and hazardous solvent, the synthesis for chemicals in pharmaceuticals industry.Gamma-valerolactone itself can be used as fuel
Additive also has many advantages, such as after mixing petrol and diesel oil as fuel.Gamma-valerolactone can improve combustion cleaning degree, improve vapour bavin
The utilization ratio of oil；Gamma-valerolactone has good lubricity；Gamma-valerolactone has high flash-point, and the long-distance fortune of fuel can be improved
Defeated safety；The low temperature flow of petrol and diesel oil also can be improved in gamma-valerolactone.Its excellent modifiability of gamma-valerolactone, can turn
Turn to the compound of a variety of high values.There are many application values as the platform chemicals of biomass economy in view of gamma-valerolactone,
The efficient of gamma-valerolactone prepares the concern for being also increasingly subject to researcher.Gamma-valerolactone is mainly with biomass-based levulic acid at present
As raw material, prepared by the method for adding hydrogen to be cyclized, the hydrogen supply agent of selection has hydrogen, formic acid and other hydrogen supply agents, in addition also has
Set out the route approach of synthesis gamma-valerolactone using other raw materials such as levulinate and cellulose.
The raw material for preparing gamma-valerolactone selects ethyl levulinate.It is since ethyl levulinate is relative to other raw materials
It is easy to obtain in converting from biomass.The most important is that some catalyst are sensitive to levulic acid.According at present,
Ethyl levulinate is the preferred of production gamma-valerolactone, has been demonstrated to be easier to convert than other raw materials.Although from levulic acid
There are many report that ethyl ester prepares gamma-valerolactone, but existing catalyst have the shortcomings that it is respective.Such as：Metal directly loads
Type catalyst, it is maximum the disadvantage is that unstable；The catalyst preparation process complexity and low output of MOFs types；It is synthesized using noble metal
Catalyst it is of high cost.Therefore it is still to research and develop at present to find efficient, stable, pollution-free, recyclable catalyst
One emphasis.
Invention content
In view of the foregoing defects the prior art has, the present invention provides a kind of new catalyst, production cost is low, system
Preparation Method is simple, be easily recycled and it is recyclable be used for multiple times, catalytic activity is high, and stability is better than the catalyst of direct support type.
Experiment is supported on Zn, Zr, Ti, Cr and Cu as metal active centres on MCM-41 carriers respectively.And it investigates
It is catalyzed ethyl levulinate and is converted to the catalytic effect in gamma-valerolactone.Experiment shows urging using Zr as metal active centres
Agent has highest catalytic activity.
The first purpose of the invention is to provide a kind of new supported schiff bases zirconium metal complexs, are with schiff bases
Supported schiff bases zirconium metal complex is prepared for ligand；The schiff base ligand is by o-phenylenediamine and containing vanillic aldehyde
Ethanol solution mixes, and is prepared.
In one embodiment of the invention, the schiff base ligand is to be prepared according to the following steps：By 1mmol neighbours
Phenylenediamine is added in the ethanol solution that 30ml contains 2mmol vanillic aldehydes, N2Protection time return stirring 22~for 24 hours, by ethyl alcohol
Recrystallization is prepared.
In one embodiment of the invention, the preparation method of the supported schiff bases zirconium metal complex, packet
Include following steps：
(1) synthesis of schiff base ligand：O-phenylenediamine is added in the ethanol solution containing vanillic aldehyde, N2Protection is next time
Stream stirring for 24 hours, obtains orange red powdery product, then passes through ethyl alcohol recrystallization, obtains red acicular schiff base ligand.
(2) synthesis of zirconium presence of Schiff-base complex：By 1mmolZrCl4It is added to the first that 30ml contains 1mmol Schiff base ligands
In alcoholic solution, N2For 24 hours, suction filtration obtains Orange red solid powder to the lower reflux of protection, is then dried in vacuo.
(3) synthesis of the complex of amino functional：Take complex and 3- aminopropyl trimethoxysilanes crosslinking agent to rub
That ratio 2~3：1 ratio mixing, N2Under protection, alcohol reflux stirs for 24 hours, and after the completion of reaction, solvent is rotated to dry, gained palm fibre
Yellow solid is dried in vacuo.
(4) preparation of the presence of Schiff-base complex of immobilized Zr：By the presence of Schiff-base complex of amino functional and MCM-41 etc.
Mass ratio is added in toluene solution, N2The lower return stirring of protection is for 24 hours.It is cooled to room temperature after the completion of reaction, decompression filters, gained
Solid through absolute ethyl alcohol-acetonitrile mixture Soxhlet extraction for 24 hours.Sample dries the Schiff to get immobilized Zr under 60 DEG C of vacuum
Alkali complex.It is converted into the reaction of GVL using it as catalyst for being catalyzed ethyl levulinate.
In one embodiment of the invention, the mesoporous material is prepared according to the following steps：By 1.092g cetyls
Trimethylammonium bromide (CTAB) is added in 100ml deionized waters, and stirring is until solution is clarified, with tetraethyl orthosilicate energetically
(TEOS) it is silicon source, TEOS, ammonium hydroxide tune PH to 10.5 or so is added, continues to stir 12h.Solution washs after crystallization for 24 hours, mistake
Filter.Products therefrom is calcined into 6h at 550 DEG C, obtains Mesoporous silica MCM 41.
Second object of the present invention is to provide using the supported schiff bases zirconium metal complex as catalyst
The application of ethyl levulinate.It is heterogeneous catalysis, the high selectivity of target product in the catalytic process；Reaction system is simply easy
In processing, production cost is low；Catalyst preparation is simple, and is easily recycled to be recycled and be used for multiple times, and meets Green Sustainable.
In one embodiment of the invention, the application be by the supported schiff bases zirconium metal complex by
It is added in alcoholic solvent according to the additive amount of 0.3~0.6g catalyst/g ethyl levulinates.
In one embodiment of the invention, the alcoholic solvent includes but not limited to 2-BuOH, 2-PrOH.
In one embodiment of the invention, the application is 10~12h of reaction at 160~170 DEG C.
In one embodiment of the invention, the ethyl levulinate replaces with methyl ester levulinate or levulic acid
Butyl ester.
The present invention also provides application of the method in terms of preparing the product containing gamma-valerolactone.
The present invention compared with the existing technology, has the following advantages that and effect：
(1) catalyst during use is heterogeneous solid acid catalyst, and preparing gamma-valerolactone not only for EL has
Good catalytic effect, and can recycled for multiple times.Catalyst circulation is urged using repeatedly still having good catalytic effect
When agent recycles the 5th time, the yield of GVL is still up to 85.08%.
(2) solid acid catalyst prepared by is prepared simply, and reaction is easily isolated later, meets Green Sustainable war
Slightly.
Description of the drawings
Fig. 1 is the yield figure that solid acid catalyst is catalyzed EL reactions at a temperature of differential responses in case study on implementation 3；
Fig. 2 is the yield figure that solid acid catalyst is catalyzed EL reactions under the differential responses time in case study on implementation 4；
Fig. 3 is that the solid acid catalyst of different amounts in case study on implementation 5 is catalyzed the yield figure of EL reactions；
Fig. 4 is the yield figure that solid acid catalyst is catalyzed EL reactions after recycling；
Fig. 5 is the catalyst preparation schematic diagram of the application.
Specific implementation mode
Embodiment 1
Catalyst uses following synthetic method：
(1) preparation of Mesoporous silica MCM 41：A certain amount of cetyl trimethylammonium bromide (CTAB) is added to
In ionized water, stirring is until solution is clarified energetically, and with tetraethyl orthosilicate (TEOS) for silicon source, addition TEOS, ammonium hydroxide tune PH is extremely
10.5 or so, continue to stir 12h.Solution washs after crystallization for 24 hours, filtering.Products therefrom is calcined into 6h at 550 DEG C, is obtained
To Mesoporous silica MCM 41.After measured, the specific surface area of carrier MCM-41 is 878.9m2g-1,Acidity is
0.15mmol/g；
(2) synthesis of schiff base ligand：O-phenylenediamine is added in the ethanol solution containing vanillic aldehyde, N2Protection is next time
Stream stirring for 24 hours, obtains orange red powdery product, then passes through ethyl alcohol recrystallization, obtains red acicular schiff base ligand；
(3) synthesis of zirconium presence of Schiff-base complex：Respectively by ZrCl4, Zn (Cl)2, Ti (Cl)4, Cr (ace)4, Cu (ace)2Add
Enter into the methanol solution of Schiff base ligand, N2For 24 hours, suction filtration obtains solid powder to the lower reflux of protection, is then dried in vacuo；Zr matches
The yield for closing object is that the yield of 85.2%, Zn complexs be the yield of 67.3%, Ti complexs is the production of 45.4%, Cr complexs
Rate is that the yield of 91.3%, Cu complexs is 86.1%.
(4) synthesis of the complex of amino functional：Take complex and 3- aminopropyl trimethoxysilanes crosslinking agent with etc.
Mass ratio is 2：1 is added, N2Under protection, alcohol reflux stirs for 24 hours, and after the completion of reaction, solvent is rotated to dry, obtained solid vacuum
It is dry；
(5) preparation of supported presence of Schiff-base complex：By the matter such as the presence of Schiff-base complex of amino functional and MCM-41
Amount ratio is added in toluene solution, N2The lower return stirring of protection is for 24 hours.It is cooled to room temperature after the completion of reaction, decompression filters, and gained is solid
Body through absolute ethyl alcohol-acetonitrile mixture Soxhlet extraction for 24 hours.Sample is dry under 60 DEG C of vacuum, obtains supported schiff bases cooperation
Object, as catalyst.
Embodiment 2
By 0.1g ethyl levulinates (EL), 5mL 2-PrOH, respectively by the supported zirconium presence of Schiff-base complex of 50mg,
Supported zinc presence of Schiff-base complex, supported titanium presence of Schiff-base complex, supported chromium presence of Schiff-base complex are supported
Copper presence of Schiff-base complex is added in the hydrothermal reactor of 25ml.Above-mentioned reactor is placed in 150 DEG C of oil bath pan and is stirred
10h takes reaction solution to centrifuge to obtain supernatant after reaction is cooling, and the yield of gamma-valerolactone is measured with GC.The experimental results showed that
It is 83.56% to have the generation of gamma-valerolactone and yield when only using supported zirconium presence of Schiff-base complex as catalyst.
The catalytic efficiency of 1 immobilized metal presence of Schiff-base complex of table
Embodiment 3
0.1g ethyl levulinates (EL) are weighed, the catalyst of 50mg is added to the reaction for the 25mL for filling 5mL 2-PrOH
In device；
Change the solvent in above-mentioned reaction condition into other solvents, such as MeOH, EtOH, 3-pentanol, CyOH, 2-
BuOH, 1-PrOH, 1-BuOH, other conditions are constant；
Above-mentioned reactor is placed in 150 DEG C of oil bath pan and stirs 10h, after reaction is cooling, reaction solution is taken to centrifuge to obtain
Supernatant measures the yield of gamma-valerolactone with GC, and the results are shown in Table 2.
2 solid acid catalyst of table is catalyzed the GVL yields of EL reactions in different solvents
Embodiment 4
0.1g EL are weighed, the catalyst of 50mg is added in the reactor for the 25mL for filling 5mL 2-PrOH；Respectively will
(1) temperature setting of oil bath pan is 140,150,160,170 DEG C of stirring 11h in；
Postcooling is completed in above-mentioned reaction, and reaction solution is taken to centrifuge to obtain supernatant, and the yield of gamma-valerolactone is measured with GC,
The results are shown in Figure 1.At 150 DEG C, the yield of GVL is 75.2%；At 160 DEG C, the yield of GVL is 86.5%；At 170 DEG C, GVL
Yield be 84.2%.
Embodiment 5
0.1g EL are weighed, the catalyst of 50mg is added in the reactor for the 25mL for filling 5mL 2-PrOH；By reactor
It is placed in 160 DEG C of oil bath pan and stirs；Mixing time in oil bath pan is set as 10 respectively, 11,12,13h, other conditions are not
Become；
Postcooling is completed in above-mentioned reaction, and reaction solution is taken to centrifuge to obtain supernatant, and the yield of gamma-valerolactone is measured with GC,
The results are shown in Figure 2.When reaction carries out 11h, the yield of GVL is 84.4%；When reaction carries out 12h, the yield of GVL is
90.1%；When reaction carries out 13h, the yield of GVL is 88.6%.
Embodiment 6
0.1g EL are weighed, are added to together with catalyst in the reactor for the 25mL for filling 5mL 2-PrOH；It controls respectively
Catalyst loading be 30,40,50,60mg；
Above-mentioned reactor is placed in 160 DEG C of oil bath pan and stirs 12h, after reaction is cooling, reaction solution is taken to centrifuge to obtain
Supernatant measures the yield of gamma-valerolactone with GC, and the results are shown in Figure 3.When the dosage of catalyst is 40mg, the yield of GVL
It is 79.2%；When the dosage of catalyst is 50mg, the yield of GVL is 91.64%；When the dosage of catalyst is 60mg, the production of GVL
Rate is 89.3%.
Embodiment 7
0.1g EL are weighed, the catalyst of 50mg is added in the reactor for the 25mL for filling 5mL 2-PrOH；
Reactor is placed in 160 DEG C of oil bath pan and stirs 12h；Postcooling is completed in above-mentioned reaction, and reaction solution is taken to centrifuge
Supernatant is obtained, the yield of gamma-valerolactone is measured with GC.
Reaction substrate EL is changed to the compound with carbonyl, specially methyl ester levulinate (ML), Butyl acetylpropanoate
(BL), any one of levulic acid (LA), furfural (Fur), other conditions are constant；
3 solid acid catalyst of table reacts the yield for generating GVL under different substrates
Embodiment 7
By centrifugation, by embodiment 7, used solid acid catalyst is separated after reaction, molten with ethyl alcohol
Agent is rinsed, and is put into reactor again after drying, is weighed 0.1g EL, the catalyst of 50mg, which is added to, fills 5mL 2-PrOH's
In the reactor of 25mL；The temperature setting of oil bath pan is 160 DEG C, stirs 12h；5 cycles are carried out under best reaction condition
Experiment.The yield that γ-GVL after prepared solid acid catalyst can recycle 4 times are obtained through experimental data is still up to
85.08% (Fig. 5).Reference examples 1
For specific implementation mode with embodiment 1, difference lies in not immobilized to presence of Schiff-base complex progress (to omit step
(4)).The catalyst prepared is reacted for being catalyzed, reaction condition is：0.1g EL are weighed, the catalyst of 50mg is added to
In the reactor for filling the 25mL of 5mL 2-PrOH；Reactor is placed in 160 DEG C of oil bath pan and stirs 12h；The results show that
The yield of the yield of gamma-valerolactone is 35.6%.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (10)
1. a kind of supported schiff bases zirconium metal complex, which is characterized in that be prepared by ligand of schiff bases；It is described
Schiff base ligand is prepared after mixing o-phenylenediamine with the ethanol solution containing vanillic aldehyde.
2. supported schiff bases zirconium metal complex according to claim 1, which is characterized in that the schiff base ligand
It is to be prepared according to the following steps：By o-phenylenediamine and vanillic aldehyde according to 1：2~3 molar ratio mixing, in N2The lower reflux of protection
Stirring 22~for 24 hours, it is prepared by ethyl alcohol recrystallization.
3. a kind of method preparing supported schiff bases zirconium metal complex as claimed in claim 1 or 2, which is characterized in that
Include the following steps：
(1) synthesis of schiff base ligand：O-phenylenediamine is added in the ethanol solution containing vanillic aldehyde, N2The lower reflux of protection is stirred
Mix 20~for 24 hours, by ethyl alcohol recrystallization, obtain schiff base ligand；
(2) synthesis of zirconium presence of Schiff-base complex：By ZrCl4According to 1:1~2 molar ratio is added to the first containing Schiff base ligand
In alcoholic solution, N2The lower reflux of protection 20~for 24 hours, it filters, vacuum drying；
(3) synthesis of the complex of amino functional：Take zirconium presence of Schiff-base complex and 3- aminopropyl trimethoxies prepared by step (2)
Base silane crosslinking agent is with molar ratio 2~3：1 ratio mixing, N2Under protection, alcohol reflux stirring 22~for 24 hours, solvent is rotated
To dry, obtained solid vacuum drying；
(4) preparation of the presence of Schiff-base complex of immobilized Zr：The mass ratioes such as the complex of amino functional and MCM-41 are added
Into toluene solution, N2The lower return stirring of protection 20~for 24 hours, it is cooled to room temperature, decompression filters, and obtained solid is through absolute ethyl alcohol-
Acetonitrile mixture Soxhlet extraction 20~for 24 hours, it is dry under 50~60 DEG C of vacuum.
4. according to the method described in claim 3, it is characterized in that, the mesoporous material is prepared according to the following steps：Prepare 16
The tetraethyl orthosilicate of equimolar amounts is added in alkyl trimethyl ammonium bromide solution, and ammonium hydroxide tune pH to 10~11 stirs 10~12h,
By 20~wash after crystallization for 24 hours, it filters, 4~6h is calcined at 500~550 DEG C.
5. the application of supported schiff bases zirconium metal complex as claimed in claim 1 or 2.
6. a kind of method producing gamma-valerolactone, which is characterized in that with any supported Schiff of Claims 1 to 4
Alkali zirconium metal complex is catalyst, and alcoholic solvent is added to according to the additive amount of 0.3~0.6g catalyst/g ethyl levulinates
In carry out catalysis reaction.
7. according to the method described in claim 6, it is characterized in that, the alcoholic solvent includes 2-BuOH or 2-PrOH.
8. the method described according to claim 6 or 7, which is characterized in that react 10~12h at 160~170 DEG C.
9. according to the method described in claim 6, it is characterized in that, the ethyl levulinate replace with methyl ester levulinate or
Butyl acetylpropanoate.
10. application of any method of claim 6~9 in terms of preparing the product containing gamma-valerolactone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN107245065A (en) * | 2017-01-09 | 2017-10-13 | 贵州大学 | A kind of method that catalytic hydrogenation ethyl levulinate prepares valerolactone |
| CN106905271A (en) * | 2017-03-20 | 2017-06-30 | 江南大学 | A kind of preparation and application containing the mesoporous material heterogeneous catalysis of MCM 41 |
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| Title |
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| RUIYINGWANG ET AL.: "Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium (IV) Schiff base complexes on mesoporous silica with isopropanol as hydrogen source", 《MOLECULAR CATALYSIS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
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