CN106268964A - A kind of base supported multifunction catalyst of polyacid and preparation method thereof - Google Patents
A kind of base supported multifunction catalyst of polyacid and preparation method thereof Download PDFInfo
- Publication number
- CN106268964A CN106268964A CN201510237871.XA CN201510237871A CN106268964A CN 106268964 A CN106268964 A CN 106268964A CN 201510237871 A CN201510237871 A CN 201510237871A CN 106268964 A CN106268964 A CN 106268964A
- Authority
- CN
- China
- Prior art keywords
- polyacid
- base supported
- multifunctional composite
- catalyst
- hkust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
A kind of base supported multifunction catalyst of polyacid and preparation method thereof, belongs to technical field of function materials.This material is by γ-Al2O3, boehmite and SiO2Doping type γ-Al2O3Or one of which is carrier, prepared by a step hydrothermal synthesis method, its preparation method: second alcohol and water is configured to mixed solution, add Gerhardite and trimesic acid and polyacid, after stirring and dissolving, add carrier；Being moved into by gained mixed solution in liner still and carry out hydro-thermal reaction, hydrothermal condition keeps 20 hours, naturally cools to room temperature；Products therefrom is separated with mother solution, is dried after washing and had both obtained complex POMs@MOFs@γ-Al2O3.This catalyst belongs to multifunction catalyst, has good acid catalysis, redox catalysis performance, and reusable, satisfactory mechanical property, separate, reclaim, reuse very convenient.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of base supported multifunction catalyst of polyacid
And preparation method thereof.
Background technology
Polyacid be a class by early transition metal ion (Fe, Co, Ni, W, Mo, V, Mn, Nb, Ta,
Cu, Ti, Zn etc.) the simple oxysalt anion that forms dehydrating condensation under certain pH conditions produces
The general name of multi-metal oxygen cluster compound (POMs).Polyacid have excellence chemical stability, superpower acidity and
Unique oxidation-reduction quality, has the advantage that corrosivity is little, non-volatile, nontoxic, as a class green catalyst
It is widely studied and applies.But the major defect itself being had also can not be ignored, concrete table
It is now: (1) is highly soluble in polar solvent (such as water, acetonitrile etc.) due to polyacid, often in polar solvent
Reaction all there is catalyst and reclaim the problem of difficulty, cause the waste of catalyst to run off and dirt to environment
Dye is destroyed；(2) specific surface area of the many acid catalysts of solid is smaller (less than 10m2.g-1), so naked
The avtive spot of dew is few, is unfavorable for giving full play to its catalysis activity.The way solving this problem typically will
Polyacid is carried on the porous carrier with bigger serface effectively, carries out heterogeneous catalytic reaction.
Metal-organic framework compound (MOFs) is that a class is passed through coordinate bond from group by metal center and organic ligand
Fill has the periodically cancellated porous crystalline material of multidimensional, has high specific surface area and uniqueness
Pore structure, therefore show the load characteristic that the general carrier such as specific activity carbon and zeolite molecular sieve is the most excellent.
Have researcher multiple Keggin-type polyacid is included silico-tungstic acid, silicomolybdic acid, germanotungstic acid, arsenic molybdic acid, phosphotungstic acid,
In the duct of phosphomolybdic acid embedding MOFs (HKUST-1) (J.Am.Chem.Soc., 2009,131,1883)
Obtain POMs@HKUST-1 hybrid material.Due to many acid molecules size and HKUST-1 (Science,
1999,283,1148-1150) the A duct in molecule is suitable, and what polyacid not only can be complete is present in duct
Inside avoid loss, and expand the specific surface area of polyacid, add avtive spot.But should in reality
Still there are several very distinct issues during with: (1) MOFs due to its be organic ligand and metal from
Son is formed by coordinate bond, and what coordinate bond bond energy was generally little than other Chemical bond energy nature of MOFs
Hydrothermal stability is often not high enough to, the harsh conditions lower part coordinate bonds such as high temperature hydro-thermal can occur fracture and
Isomery is recombinated；(2) generally synthesizing the POMs@HKUST-1 material obtained is powder body, bad mechanical strength,
In actual industrial operating process, it is difficult in adapt to the impact load that environment produces, causes recovery inconvenience and be difficult to weight
Multiple utilization, thus cause the unnecessary wasting of resources；(3) gained POMs@HKUST-1 powder body is in conduct
When catalyst uses, reactant molecule is due to sterically hindered and kinetic factor, the most only POMs@
The region close to outer surface of HKUST-1 granule can fully participate in catalytic reaction, and reaction molecular be difficult to into
Enter to granule inside thus cause catalysis capabilities of catalysts to be difficult to give full play to.
For solving the problems referred to above, we select has good physicochemical properties and by actual wide range of industrial applications
Aluminium oxide (ZL 200610114072, ZL201110116418.5, CN 1958456 A, CN103172097A,
ZL 200910084540.1, ZL 200610114073.9, CN 103962171A, ZL 200810226494.X,
CN 101543778A, CN 100431965C) do carrier, prepare with a simple step hydrothermal synthesis method
Polyacid support type multifunction catalyst POMs@HKUST-1@Al2O3.This composite has following spy
Point: the molecular dimension of (1) polyacid is suitable with the A hole pore size of HKUST-1, the existence that polyacid is complete
In the duct of HKUST-1 thus solve loaded catalyst the most easily hold the separation of flow lose ask
Topic；(2) alumina catalyst support loads polyacid further by load HKUST-1, it is to avoid with POMs's
Directly contact, can keep the alkalescence destruction on the structure not oxidized aluminum surface of POMs；(3) due to oxidation
The confinement effect in the other duct of micro-nano in alumina supporter, causes the growth of POMs@HKUST-1 to be restricted,
Thus the micro/nano level being consistent with the other duct of micro/nano level in carrying alumina body that obtains is other
POMs@HKUST-1 granule, this increases undoubtedly and is carried on the specific surface area of polyacid on carrier, adds many
Acid effective active site in catalytic process, substantially increases its catalytic capability；(4)POMs@HKUST-1
It is carried on the POMs HKUST-1 Al obtained inside aluminium oxide duct2O3There is the highest mechanical strength
With the advantage such as outstanding chemical stability, it is possible to because rolling, falling and cause in opposing barrelling, handling process
Abrasion；The impact load that produces when being amenable to be filled to reactor and will not fragmentation or efflorescence；Can bear anti-
Answer device to go into operation, when stopping work, the thermal expansion of beds, settle, relative motion that contraction etc. causes,
The abrasion to carrier granular when fluid flows or impacts can be resisted；Produced by during being prevented from using
Physics, chemical change and crush.(5) aluminium oxide used by the present invention be spherical, bar shaped, column,
Cellular, lamellar, leafy grass shape or one therein, spherical particle diameter is 0.05～5mm, the length of bar shaped
Degree is 1～20cm so that it is be easier to separation and recovery, and catalyst just can be reclaimed after terminating by reaction with decantation.
Summary of the invention
The purpose of the present invention is on the basis of having been proven that polyacid has superior catalytic performance, for solving to urge
The actual application of agent material provides a kind of means: i.e. provide that a kind of preparation method is simple, low cost, stable
Property height, good mechanical property, reuse the high POMs Supported alumina type multifunction catalyst of efficiency and
Preparation method.
A kind of base supported multifunction catalyst of polyacid, it is characterised in that the carrier of this catalyst is γ-Al2O3、
Boehmite, SiO2Doping type γ-Al2O3Or one therein.Described Al2O3Carrier surface rich in
Hydroxyl has active chemical reactivity, can react with the MOFs with carboxylic group and realize MOFs and exist
Alumina surface immobilized.The polyacid with suitable molecular dimension is embedded in MOFs duct, it is achieved many
The steady load of acid.Polyacid the most used can be following in one: Keggin-type polyacid
HnXM12-mM’mO40；Anderson type polyacid HnXO6M6O18Or HnX(OH)6M6O18；Waugh type
Polyacid HnXM9O32；Silverton type polyacid HnXM12O42；Vindqvist type polyacid HnM6O19(wherein
X=P, Si, Ge, As, S or H, M=Mo or W, M '=V or Nb).
POMs support type multifunctional composite mechanical strength provided by the present invention is high, completes a performance
Can again recycle through simple process after application, can be used as acid catalyst synthesis and/or hydrolysis esters
Compound, as the sulfur-containing compound in oxidation catalyst catalytic eliminating fuel oil, there is good industry
Change prospect.
Accompanying drawing explanation
HPW@HKUST-1@γ-Al in Fig. 1 embodiment 12O3, HKUST-1 and blank Al2O3Infrared
Spectrogram comparison diagram；
Fig. 2 embodiment 1 is the condition of 2 in response time 2.5h, reaction temperature 75 DEG C, acid/alcohol mol ratio
Under when catalyzing and synthesizing ethyl acetate, ethanol conversion is with the change curve of different catalysts consumption；
Fig. 3 embodiment 1 is the condition of 2 in response time 8h, reaction temperature 110 DEG C, acid/alcohol mol ratio
During lower Catalytic Synthesis, n-butyl alcohol conversion ratio is with the change curve of different catalysts consumption；
In Fig. 4 embodiment 1 during catalyst synthesizing ethyl acetate, in response time 2.5h, reaction temperature
75 DEG C, acid/alcohol mol ratio be to reuse the catalytic efficiency bar diagram of 6 times under the conditions of 2.
Detailed description of the invention
Chemical drugs used in following embodiment is commercial goods than alumina.Alumina catalyst support
At 150～300 DEG C of Muffle kiln roastings 1～5h before using.
Embodiment 1
(1) second alcohol and water is configured to 12mL mixed solution according to volume ratio 1: 1, adds 1.8mM tri-
Nitric hydrate copper and 1.8mM trimesic acid；
(2) in step (1) gained solvent, add the phosphotungstic acid (H of 0.04mM3PW12O40, it is abbreviated as
HPW), stirring added 0.4g γ-Al after 5 minutes2O3Bead；
(3) step (2) gained mixed solution is moved into the 23mL hydro-thermal reaction with politef as liner
Still carries out hydro-thermal reaction, with 1.5 DEG C of .min-1Keep 20 hours after being raised to 180 DEG C, naturally cool to room temperature；
(4) with decantation by products therefrom γ-Al in step (3)2O3Bead separates with mother solution, then uses 10mL
Distillation 3 γ-Al of washing2O3Bead, is finally dried 12h in 100 DEG C of drying baker and removes moisture removal, both obtained
Complex HPW@HKUST-1@Al2O3。
Embodiment 2
(1) second alcohol and water is configured to 12mL mixed solution according to volume ratio 1: 1, adds 1.8mM tri-
Nitric hydrate copper and 1.8mM trimesic acid；
(2) in step (i) gained solvent, add the silico-tungstic acid (H of 0.04mM4SiW12O40, it is abbreviated as
HSiW), stirring added 0.4g γ-Al after 5 minutes2O3Bead；
(3) step (2) gained mixed solution is moved into the 23mL hydro-thermal reaction with politef as liner
Still carries out hydro-thermal reaction, with 1.5 DEG C of min-1Keep 20 hours after being raised to 180 DEG C, naturally cool to room temperature；
(4) with decantation by products therefrom γ-Al in step (3)2O3Bead separates with mother solution, then uses 10mL
Distillation 3 γ-Al of washing2O3Bead, is finally dried 12h in 100 DEG C of drying baker and removes moisture removal, both obtained
Complex HSiW@HKUST-1@γ-Al2O3。
Embodiment 3
(1) second alcohol and water is configured to 12mL mixed solution according to volume ratio 1: 1, adds 1.8mM tri-water
Close copper nitrate and 1.8mM trimesic acid；
(2) in step (1) gained solvent, add the phosphotungstic acid of 0.04mM, after stirring 5 minutes, add 0.4g
Siliceous Al2O3(it is designated as SiO2-Al2O3)；
(3) step (2) gained mixed solution is moved into the 23mL hydro-thermal reaction with politef as liner
Still carries out hydro-thermal reaction, with 1.5 DEG C of min-1Keep 20 hours after being raised to 180 DEG C, naturally cool to room temperature；
(4) with decantation by products therefrom SiO in step (3)2-Al2O3Separate with mother solution, then steam with 10mL
Distilled water washes 3 SiO2-Al2O3, in 100 DEG C of drying baker, finally it is dried 12h removes moisture removal, be combined
Thing HPW@HKUST-1@SiO2-Al2O3。
Test HPW@HKUST-1@Al in embodiment 12O3Complex and blank Al2O3With
The infrared spectrum (Fig. 1) of HKUST-1, complex is just catalyzing and synthesizing ethyl acetate and acetic acid as acid catalyst
The catalytic performance (Fig. 2, Fig. 3, Fig. 4) of butyl ester.
HPW@HKUST-1@Al2O3The complex acid catalysis efficiency test to Lipase absobed, for different
Ester synthesis reaction, specifically comprises the following steps that (1) synthesizing ethyl acetate, adds in 100mL three neck round bottom flask
Enter 0.6mol acetic acid and 0.3mol ethanol mix homogeneously, stirring rotator, thermometer and shunting post are installed, point
Fluidization tower condensing tube installed above collects product with connecing skirt.Heated and stirred, adds after thermometer indicates 75 DEG C
Enter a certain amount of catalyst initiation reaction；(2) synthesizing n-butyl acetate: in 150mL three neck round bottom flask
Add 0.6mol acetic acid and the corresponding alcohol of 0.3mol, add 15mL toluene and do water entrainer, stirring is installed
Rotor, thermometer and water knockout drum, the water back upper place loading 4/5 volume in water knockout drum connects condensing tube.Heating is stirred
Mix, after treating that thermometer indicates 110 DEG C, add a certain amount of catalyst initiation reaction.At interval of certain time
Catalytic conversion is tested by gas chromatogram.Under conditions of reaction temperature and reactant molar ratio are constant, along with
The increase of catalyst amount, catalytic efficiency constant after first increasing (Fig. 2, Fig. 3).
Complex HPW@HKUST-1@Al2O3With HSiW@HKUST-1@Al2O3To ethyl acetate and
Optimum reaction condition and the highest catalytic efficiency of n-butyl acetate are shown in Table 1.
The 1 two kinds of catalyst of the table optimum reaction condition to Lipase absobed
aRepresent HPW@HKUST-1@γ-Al2O3；bRepresent HSiW@HKUST-1@γ-Al2O3
By HPW@HKUST-1@Al2O3Catalyst, for being catalyzed the synthetic reaction of ethyl acetate, is most preferably tested
Under the conditions of investigate this complex repeat performance to Synthesis Diethyl ether, after often completing a catalytic reaction,
Catalyst reuses after simple washing and dried, is repeated 6 times, the catalytic efficiency of catalyst
Keep constant (Fig. 4), illustrate that this complex has preferable repeat performance when using as catalyst.
Complex HPW@HKUST-1@Al2O3As containing in oxidation catalyst catalytic eliminating simulated oil
Sulphur compound, specifically comprises the following steps that and burns to the 100mL tri-neck round bottom equipped with thermometer, condensing tube and rotor
In Ping, (sulfur content is 350ppmw for addition 20mL normal octane and 0.0406g DBTs), add 20mL second
Nitrile, as extractant, heats in the water-bath of 60 DEG C.Weigh 50mg catalyst and put into 1mL 30%H2O2
In solution, after the solution in three-necked bottle reaches 60 DEG C, by preparation containing HPW@HKUST-1@Al2O3
The H of catalyst2O2Solution is poured into and is carried out catalytic desulfurization reaction in three-necked bottle.
Testing oxidation sweetening efficiency after catalytic oxidation 1h, result shows, complex
HPW@HKUST-1@Al2O3As oxidation catalyst in oxidation sweetening, desulfuration efficiency reaches 97%,
Catalyst is reused 5 catalytic effects and is the most substantially reduced.
Claims (7)
1. the base supported multifunctional composite of polyacid, it is characterised in that this complex is made up of polyacid, metal-organic framework compound and alumina support.
Polyacid base supported multifunctional composite preparation method the most according to claim 1, it is characterised in that with aluminium oxide as carrier, comprise the following steps:
(1) it is 1: 10～10: 1 to be configured to 10～100mL mixed solutions by second alcohol and water according to volume ratio, adds 0.5～50mM Gerhardite and 0.3～20mM trimesic acid；
(2) in step (1) gained solvent, add the polyacid of 0.05～1mM, after stirring 5 minutes, add 0.5～10g carrier；
(3) step (2) gained mixed solution immigration hydrothermal reaction kettle will carry out hydro-thermal reaction, with 1～5 DEG C of min-1Heating rate be raised to 100～300 DEG C after keep 10～20 hours, naturally cool to room temperature；
(4) with decantation, products therefrom product in step (3) is separated with mother solution, then with distillation washing 3～5 times, in 100 DEG C of drying baker, be finally dried 5～20h remove moisture removal, both obtained complex POMs MOFs aluminium oxide.
Polyacid base supported multifunctional composite preparation method the most according to claim 2, it is characterised in that alumina support used is γ-Al2O3, boehmite and SiO2Doping type γ-Al2O3Or one therein.
Polyacid base supported multifunctional composite preparation method the most according to claim 2, it is characterized in that alumina support used is spherical, bar shaped, column, cellular, lamellar or leafy grass shape, spherical particle diameter is 0.05～5mm, a length of the 0.1 of bar shaped～20cm.
Polyacid base supported multifunctional composite preparation method the most according to claim 2, it is characterised in that the MOFs generated is HKUST-1.
Polyacid base supported multifunctional composite preparation method the most according to claim 2, it is characterised in that the polyacid in the base supported multifunctional composite of polyacid is by being carried on carrier in being embedded into the duct of HKUST-1.
Polyacid base supported multifunctional composite preparation method the most according to claim 2, it is characterised in that polyacid used is for including: Keggin-type polyacid HnXM12-mM’mO40；Anderson type polyacid HnXO6M6O18Or HnX(OH)6M6O18；Waugh type polyacid HnXM9O32；Silverton type polyacid HnXM12O42；Vindqvist type polyacid HnM6O19(wherein X=P, Si, Ge or As, M=Mo or W, M '=V or Nb) or one therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510237871.XA CN106268964A (en) | 2015-05-12 | 2015-05-12 | A kind of base supported multifunction catalyst of polyacid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510237871.XA CN106268964A (en) | 2015-05-12 | 2015-05-12 | A kind of base supported multifunction catalyst of polyacid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106268964A true CN106268964A (en) | 2017-01-04 |
Family
ID=57631267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510237871.XA Pending CN106268964A (en) | 2015-05-12 | 2015-05-12 | A kind of base supported multifunction catalyst of polyacid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106268964A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940217A (en) * | 2018-08-17 | 2018-12-07 | 华南协同创新研究院 | A kind of aluminium based metal organic backbone@gama-alumina composite material and its preparation and application |
| CN109513462A (en) * | 2018-11-15 | 2019-03-26 | 农业部环境保护科研监测所 | A kind of catalyst and its preparation method and application adding hydrogen for 5 hydroxymethyl furfural |
| CN109721737A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of hybrid material and preparation method thereof containing metal-organic framework materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040029724A1 (en) * | 2000-09-21 | 2004-02-12 | Yoshimasa Seo | Catalyst for methacrylic acid production,coated catalyst, and process for producing the same |
| CN104338556A (en) * | 2013-07-25 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material |
-
2015
- 2015-05-12 CN CN201510237871.XA patent/CN106268964A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040029724A1 (en) * | 2000-09-21 | 2004-02-12 | Yoshimasa Seo | Catalyst for methacrylic acid production,coated catalyst, and process for producing the same |
| CN104338556A (en) * | 2013-07-25 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for directly synthesizing mesoporous material coated heteropolyacid functionalized MOF material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721737A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of hybrid material and preparation method thereof containing metal-organic framework materials |
| CN108940217A (en) * | 2018-08-17 | 2018-12-07 | 华南协同创新研究院 | A kind of aluminium based metal organic backbone@gama-alumina composite material and its preparation and application |
| CN108940217B (en) * | 2018-08-17 | 2022-03-22 | 华南协同创新研究院 | Aluminum-based metal organic framework @ gamma-alumina composite material and preparation and application thereof |
| CN109513462A (en) * | 2018-11-15 | 2019-03-26 | 农业部环境保护科研监测所 | A kind of catalyst and its preparation method and application adding hydrogen for 5 hydroxymethyl furfural |
| CN109513462B (en) * | 2018-11-15 | 2021-07-20 | 农业部环境保护科研监测所 | Catalyst for hydrogenation of 5-hydroxymethylfurfural and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Basic ionic liquid functionalized magnetically responsive Fe3O4@ HKUST-1 composites used for biodiesel production | |
| Chen et al. | Biodiesel production in a rotating packed bed using K/γ-Al2O3 solid catalyst | |
| Xie et al. | Sustainable biodiesel production from low-quantity oils utilizing H6PV3MoW8O40 supported on magnetic Fe3O4/ZIF-8 composites | |
| Malhotra et al. | 5-Na/ZnO doped mesoporous silica as reusable solid catalyst for biodiesel production via transesterification of virgin cottonseed oil | |
| Zhang et al. | Efficient biodiesel production from oleic acid using metal–organic framework encapsulated Zr-doped polyoxometalate nano-hybrids | |
| Qiu et al. | Heterogeneous solid base nanocatalyst: preparation, characterization and application in biodiesel production | |
| Srilatha et al. | Efficient solid acid catalysts for esterification of free fatty acids with methanol for the production of biodiesel | |
| Xie et al. | Biodiesel production from acidic oils using polyoxometalate-based sulfonated ionic liquids functionalized metal–organic frameworks | |
| Wang et al. | Molybdenum and zirconium oxides supported on KIT-6 silica: A recyclable composite catalyst for one–pot biodiesel production from simulated low-quality oils | |
| Ding et al. | Mesoporous Li/ZrO2 as a solid base catalyst for biodiesel production from transesterification of soybean oil with methanol | |
| Zhang et al. | Production of diacylglycerols by esterification of oleic acid with glycerol catalyzed by diatomite loaded SO42−/TiO2 | |
| CN106861649A (en) | A kind of desulfurizing oil adsorbent based on metal-organic framework compound and preparation method thereof | |
| CN101979136B (en) | Mesoporous composite oxide type solid super acidic catalyst and preparation method thereof | |
| CN110841718B (en) | Method for packaging heteropoly acid ionic liquid through Zr-based MOFs in-situ bridging | |
| Zięba et al. | Activity and stability of polyaniline-sulfate-based solid acid catalysts for the transesterification of triglycerides and esterification of fatty acids with methanol | |
| Das et al. | Development of mesoscopically assembled sulfated zirconia nanoparticles as promising heterogeneous and recyclable biodiesel catalysts | |
| CN106268964A (en) | A kind of base supported multifunction catalyst of polyacid and preparation method thereof | |
| CN106215979A (en) | The preparation of load-type iron-based metallic organic framework oxidation-desulfurizing catalyst and application thereof | |
| CN113083368B (en) | Metal organic framework supported solid heteropolyacid oxidation desulfurization catalyst and preparation method and application thereof | |
| Rattanaphra et al. | Synthesis, characterization and catalytic activity studies of lanthanum oxide from Thai monazite ore for biodiesel production | |
| Bamoharram et al. | Catalytic performance of nano-SiO2-supported Preyssler heteropolyacid in esterification of salicylic acid with aliphatic and benzylic alcohols | |
| CN107159300A (en) | A kind of support type mesoporous molecular sieve catalyst and its preparation method and application | |
| Zhang et al. | ZrMo oxides supported catalyst with hierarchical porous structure for cleaner and sustainable production of biodiesel using acidic oils as feedstocks | |
| Ma et al. | 12-Tungstophosphoric acid-encapsulated metal-organic framework UiO-66: A promising catalyst for the esterification of acetic acid with n-butanol | |
| Mao et al. | Sulfamic acid–modified zeolitic imidazolate framework (ZIF-90) with synergetic Lewis and Brønsted acid sites for microalgal biodiesel production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170104 |
|
| WD01 | Invention patent application deemed withdrawn after publication |