CN104437634A - Hydrophobic organic solid acid catalyst and preparation method thereof - Google Patents
Hydrophobic organic solid acid catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104437634A CN104437634A CN201410610714.4A CN201410610714A CN104437634A CN 104437634 A CN104437634 A CN 104437634A CN 201410610714 A CN201410610714 A CN 201410610714A CN 104437634 A CN104437634 A CN 104437634A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- acid
- organic solid
- water
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a hydrophobic organic solid acid catalyst and a preparation method thereof, belonging to the field of solid catalysts. The hydrophobic organic solid acid catalyst solves the technical problems that many catalysts are used in the reaction of preparing 5-hydroxymethylfurfural (HMF) by cellulose, the yield of the HMF is not improved and the HMF can be further transformed into a by-product in the reaction. A high-internal-phase emulsion method is adopted for preparing macro-porous organic solid catalyst, and the macro-porous organic solid catalyst is subjected to acid and hydrophobic modification, and then is used as the catalyst for transforming the cellulose into HMF.
Description
Technical field
The invention belongs to solid catalyst field, especially organic solid hydrophobic acid Catalysts and its preparation method.
Background technology
A kind of macromolecular polysaccharide that cellulose is the widest as occurring in nature distribution, content is maximum is one of biomass energy of the most Research Significance of producing important fine chemical material-5 hydroxymethyl furfural (HMF); The acidic site that acidic catalyst provides plays vital effect for cellulose conversion processes, as inorganic bronsted acid, lewis acid, organic acid etc., but owing to easily reclaiming, to advantages such as equipment corrosion degree are low, low in the pollution of the environment, heterogeneous catalysis shows more potential trend; The acidic resins of perfluorosulfonic acid type are that the solid acid synthesizing the hydrophobic network structure of heat-flash stability provides correct direction, but hole is lacked and the little application that have impact on as effective acid catalyst of specific area.At present, the factor main manifestations of restriction product HMF yield is: (1) catalyst amount is more, and HMF yield but can not get improving.(2) in reaction system, the stability of HMF is not high, easily continues to be converted into accessory substance.
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of organic solid hydrophobic acid Catalysts and its preparation method, by High Internal Phase Emulsion legal system for organic solid catalyst, and carry out acidity and hydrophobically modified, obtain the hydrophobic organic solid acid catalyst of macropore, be used as the catalyst that HMF prepared by cellulose; The preparation of HMF can be realized with small amount catalyst, and the HMF of higher yields can be obtained, and stop it that side reaction generation accessory substance occurs further.
The present invention realizes above-mentioned technical purpose by following technological means.
A preparation method for organic solid hydrophobic acid catalyst, carries out in accordance with the following steps:
(1) phenylacetyl sodium sulfonate, water-soluble thermal initiator, water-soluble cross-linker, nonionic surface active agent are dissolved in as aqueous phase in deionized water, dropwise add oil phase and make High Internal Phase Emulsion, carry out thermal-initiated polymerization reaction at 60 ~ 80 DEG C; Product is through liquid-solid separation device wash-out nonionic surface active agent and oil phase, and abrasive dust after dry, adds to polymer powder in inorganic acid solution, stirs, vacuum drying;
(2) step (1) product is scattered in organic solvent, adds molecular weight regulator, stir, vacuum drying.
Aqueous phase and oil phase form High Internal Phase Emulsion system under surfactant emulsifies effect, utilize heat to cause and are polymerized, prepare macroporous polymer; Carry out ion-exchange with hydrogen ion after macroporous polymer abrasive dust, obtain macroreticular acidic catalyst; With molecular weight regulator, subsequent treatment is carried out to macroreticular acidic catalyst and obtain the super-hydrophobic acidic catalyst of macropore.
Further, described water-soluble thermal initiator is potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide or azo diisobutyl amidine hydrochloride; Described water-soluble cross-linker is N, N-methylene-bisacrylamide; Described nonionic surface active agent is Tween-85, Si Ban-20, fatty acid methyl ester APEO; Described molecular weight regulator is lauryl mercaptan.
In such scheme, described oil phase is non-polar hydrocarbon or paraffin.
In such scheme, described liquid-solid separation device is Soxhlet extraction device.
In such scheme, step (1) the described thermal-initiated polymerization reaction time is 18 ~ 24h, and described mixing time is 20 ~ 24h;
Step (2) described mixing time is 18 ~ 24h.
In such scheme, the mass ratio of described phenylacetyl sodium sulfonate, water-soluble thermal initiator, water-soluble cross-linker, nonionic surface active agent, deionized water is (1.08 ~ 1.32): (0.03 ~ 0.05): (0.0258 ~ 0.0360): (0.028 ~ 0.052): (3.256 ~ 4.744); The volume ratio of described oil phase and deionized water is (18.45 ~ 26.88): (3.256 ~ 4.744).
In such scheme, described inorganic acid is sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, chloric acid, and described inorganic acid solution provides hydrogen ion, and described hydrionic concentration is 1.5 ~ 2.5mol/L; The consumption of described polymer powder adds 7.5 ~ 12.5g powder in often liter of inorganic acid.
In such scheme, described organic solvent is methyl alcohol, acetonitrile, acetone, chloroform, and the ratio of described step (1) product quality, molecular weight regulator volume, organic solvent volume is (0.108 ~ 0.292) g:(4.32 ~ 5.68) mL:(7.256 ~ 12.744) mL.
Present invention also offers one and obtain organic solid hydrophobic acid catalyst by above-mentioned preparation method.
Further, described catalyst diameter macropores is 8.5 ~ 24.5 μm, and connecting hole diameter is 1.4 ~ 6.7 μm, and acidity is 4.749mmol/g, and the contact angle of catalyst and deionized water is 150 °.
The invention has the advantages that:
(1) preparation method of organic solid hydrophobic acid catalyst provided by the invention, obtains mainly through emulsion polymerization, and preparation process is simple, is easy to reclaim;
(2) the organic solid hydrophobic acid catalyst obtained has hollow macroporous structure, the transmission speed of reactant can be improved, Reaction time shorten, for reaction substrate and active site provide larger reaction contact area, and connected by inner connecting hole between macropore, make this material possess higher permeability and low-density, be conducive to making catalytic condition gentleer and reduce catalyst amount;
(3) by the modification to macropore organic solid acid catalyst, make it possess ultra-hydrophobicity, can effectively stablize the HMF obtained in reaction system, stop it further side reaction to occur, thus the effective yield improving HMF.
Accompanying drawing explanation
Fig. 1 is the optical microscope picture of High Internal Phase Emulsion in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of organic solid hydrophobic acid catalyst in embodiment 1.
Fig. 3 is the infrared spectrogram of organic solid hydrophobic acid catalyst in embodiment 1.
Fig. 4 is the x-ray photoelectron spectrogram of organic solid hydrophobic acid catalyst in embodiment 1.
Fig. 5 is the NH of organic solid hydrophobic acid catalyst in embodiment 1
3temperature programming collection of illustrative plates.
Fig. 6 is the contact angle of organic solid hydrophobic acid catalyst and deionized water in embodiment 1.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1
(1) preparation of organic solid hydrophobic acid catalyst
By 1.08g to phenylacetyl sodium sulfonate (SS), 0.03g ammonium persulfate, 0.0258g N, N-methylene-bisacrylamide, 0.028g Si Ban-20 joins in 3.256mL deionized water and forms mixed solution as aqueous phase, stirs 20 ~ 30min and makes it mix; Getting 18.45mL paraffin as oil phase, not stopping dropwise to be joined in aqueous phase by oil phase under stirring to mix, being prepared into stable High Internal Phase Emulsion system (HIPEs); After stirring 10 ~ 20min, emulsion keeps 18h to carry out thermal-initiated polymerization reaction at 60 DEG C; The polymer acetone obtained is through surname extraction eluting surface activating agent and paraffin, and product is dry 20 ~ 24h under 50 ~ 55 DEG C of vacuum, obtains macropore organic solid polymer;
The hydrochloric acid solution of configuration 1.5mol/mL, adds configured 50mL 0.78mol/mL H by the material obtaining 0.38g in previous step after being ground into powder
2sO
4in solution, stir 20h, at 70 ~ 80 DEG C, vacuum drying obtains macropore organic solid acidic polymer;
Homogeneous system is formed by the ultrasonic 7.256mL of the being dispersed in acetonitrile of macropore organic solid acidic polymer of above-mentioned for 0.108g acquisition, then in this system, 4.32mL lauryl mercaptan is added, this mixed system at room temperature stirs and carries out hydrophobically modified reaction in 18 hours, and vacuum drying finally obtains the hydrophobic organic solid acid catalyst of macropore.
From several microns to 100 microns not etc., because dispersed phase volume fraction is too high, the tightly packed one-tenth of the drop in decentralized photo is interconnective spherical for the diameter of HIPEs drop as seen from Figure 1;
The organic solid hydrophobic acid catalyst obtained as seen from Figure 2 has perforate hollow structure, is connected between macropore by internal crosslinking hole, makes catalyst have performance such as height permeability, low-density etc.;
In the infrared spectrum of Fig. 3 2930,1664,1013cm
-1the peak of corresponding is C – H, C=O and C – S, 1038,1131 and 1182cm
-1be the absworption peak of O=S=O, as can be seen from the figure successfully prepared organic solid hydrophobic acid catalyst;
Can be found out further by Fig. 4 and successfully prepare organic solid hydrophobic acid catalyst;
The organic solid hydrophobic acid catalyst prepared as seen from Figure 5, both containing weak acid district (120 ~ 400 DEG C), also contains strong acid district (400 ~ 800 DEG C);
The organic solid hydrophobic acid catalyst prepared as seen from Figure 6 and the contact angle of deionized water are 150 °, illustrate that this catalyst has ultra-hydrophobicity.
(2) catalytic performance analytical test
The cellulose crystals of 2g ionic liquid 1-butyl-3-methyl imidazolium chlorine ([EMIM]-Cl) and 0.1g is joined in the single port flask of 25mL, system in the oil bath pan of 120 DEG C, pre-reaction 0.5h under the rotating speed of 800r/min; Then the catalyst of 0.04g is joined in reaction system, continue reaction 0.5h; After having reacted, in the middle of products therefrom constant volume to volumetric flask, after be diluted to 5000 times; Catalysate high performance liquid chromatography (HPLC) detects, testing conditions is: column temperature is 30 DEG C, mobile phase is methyl alcohol: water=7:3, flow velocity is 1mL/min, determined wavelength is 283nm, sample size is 22.5 μ L, and sample standard curve is y=0.0019x+3.4903 (y is the concentration that HMF is corresponding, and x is peak area); According to acquired results, calculate cellulosic conversion ratio Y (yield):
Y＝5000y(％)
After wherein y represents dilution according to calibration curve the concentration (mg/L) calculated, Y represents cellulosic conversion ratio (%).
Result shows: product can reach higher productive rate, is 49.5%, and the reaction time is 0.5h, and the catalytic performance of this catalyst is higher, and catalysis time is shorter, can reduce catalysis expense to a great extent.
(3) regeneration test
Product after catalysis is through centrifugal, separation obtains can be used for regenerating primary catalyst, the catalyst that centrifugal, drying obtains is for regeneration test, and Using such method carries out four regeneration tests, and measured catalysate detection method and experiment condition are with above-mentioned catalytic test.
Result shows: in regenerative process, loss of catalyst activity is lower, and regenerate in one to four process of the test, cellulose conversion is that the productive rate of HMF is followed successively by 48.9%, 48.6%, 47.4% and 47%.
Embodiment 2
(1) preparation of organic solid hydrophobic acid catalyst
By 1.2g SS, 0.04g potassium peroxydisulfate, 0.0309g N, N-methylene-bisacrylamide, 0.04g Tween-85 joins in 4mL deionized water and forms mixed solution as aqueous phase, stirs 20 ~ 30min and makes it mix; Getting 22.67mL paraffin as oil phase, not stopping dropwise to be joined in aqueous phase by oil phase under stirring to mix, being prepared into stable HIPEs; After stirring 10 ~ 20min, emulsion keeps 21h to carry out thermal-initiated polymerization reaction at 65 DEG C; The polymer acetone obtained is through surname extraction eluting surface activating agent and paraffin, and product is dry 20 ~ 24h under 50 ~ 55 DEG C of vacuum, obtains macropore organic solid polymer;
The sulfuric acid solution of configuration 1mol/mL, subsequently, adds configured 50mL 1mol/mL H by the material obtaining 0.5g in previous step after being ground into powder
2sO
4in solution, stir 22h, at 70 ~ 80 DEG C, vacuum drying obtains macropore organic solid acidic polymer;
Homogeneous system is formed by the ultrasonic 10mL of the being dispersed in methyl alcohol of macropore organic solid acidic polymer of above-mentioned for 0.2g acquisition, then in this system, 5mL lauryl mercaptan is added according to a certain percentage, this mixed system at room temperature stirs 21h and carries out hydrophobic modified reaction, finally obtains the hydrophobic organic solid acid catalyst of macropore.
(2) catalytic performance analytical test
Catalytic performance analysis test method is with embodiment 1.
Result shows: it is 48.8% that product can reach higher productive rate, and the reaction time is 0.5h, and the catalytic performance of this catalyst is higher, and catalysis time is shorter, can reduce catalysis expense to a great extent.
(3) regenerability analytical test
Regenerability analysis test method is with embodiment 1.
Result shows: in regenerative process, loss of catalyst activity is lower, and regenerate in one to four process of the test, cellulose conversion is that the productive rate of HMF is followed successively by 48.5%, 47.9%, 47.5% and 47%.
Embodiment 3
(1) preparation of organic solid hydrophobic acid catalyst
By 1.32g SS, 0.05g azo diisobutyl amidine hydrochloride, 0.036g N, N-methylene-bisacrylamide, 0.052g fatty acid methyl ester APEO joins in 4.744mL deionized water and forms mixed solution as aqueous phase, stirs 20 ~ 30min and makes it mix; Getting 26.88mL paraffin as oil phase, not stopping dropwise to be joined in aqueous phase by oil phase under stirring to mix, being prepared into stable HIPEs; After stirring 10 ~ 20min, emulsion keeps 24h to carry out thermal-initiated polymerization reaction at 80 DEG C; The polymer acetone obtained is through surname extraction eluting surface activating agent and dodecane, and product is dry 20 ~ 24h under 55 DEG C of vacuum, obtains macropore organic solid polymer;
The salpeter solution of configuration 2.5mol/mL, subsequently, adds configured 50mL 1.22mol/mL H by the material obtaining 0.62g in previous step after being ground into powder
2sO
4in solution, stir 24h, at 70 ~ 80 DEG C, vacuum drying obtains macropore organic solid acidic polymer;
Homogeneous system is formed by the ultrasonic 12.744mL of the being dispersed in acetone of macropore organic solid acidic polymer of above-mentioned for 0.292g acquisition, then in this system, 5.68mL lauryl mercaptan is added according to a certain percentage, this mixed system at room temperature stirs 24h and carries out hydrophobic modified reaction, finally obtains the hydrophobic organic solid acid catalyst of macropore.
(2) catalytic performance analytical test
Catalytic performance analysis test method is with embodiment 1.
Result shows: it is 49% that product can reach higher productive rate, and the reaction time is 0.5h, and the catalytic performance of this catalyst is higher, and catalysis time is shorter, can reduce catalysis expense to a great extent.
(3) regenerability analytical test
Regenerability analysis test method is with embodiment 1.
Result shows: in regenerative process, loss of catalyst activity is lower, and regenerate in one to four process of the test, cellulose conversion is that the productive rate of HMF is followed successively by 48.5%, 48.2%, 47.8% and 47.1%.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (10)
1. a preparation method for organic solid hydrophobic acid catalyst, is characterized in that, carries out as follows:
(1) phenylacetyl sodium sulfonate, water-soluble thermal initiator, water-soluble cross-linker, nonionic surface active agent are dissolved in as aqueous phase in deionized water, dropwise add oil phase and make High Internal Phase Emulsion, carry out thermal-initiated polymerization reaction at 60 ~ 80 DEG C; Product is through liquid-solid separation device wash-out nonionic surface active agent and oil phase, and abrasive dust after dry, adds to polymer powder in inorganic acid solution, stirs, vacuum drying;
(2) step (1) product is scattered in organic solvent, adds molecular weight regulator, stir, vacuum drying.
2. the preparation method of catalyst as claimed in claim 1, it is characterized in that, described water-soluble thermal initiator is potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide or azo diisobutyl amidine hydrochloride;
Described water-soluble cross-linker is N, N-methylene-bisacrylamide;
Described nonionic surface active agent is Tween-85, Si Ban-20, fatty acid methyl ester APEO;
Described molecular weight regulator is lauryl mercaptan.
3. the preparation method of catalyst as claimed in claim 1, it is characterized in that, described oil phase is non-polar hydrocarbon or paraffin.
4. the preparation method of catalyst as claimed in claim 1, it is characterized in that, described liquid-solid separation device is Soxhlet extraction device.
5. the preparation method of catalyst as claimed in claim 1, it is characterized in that, step (1) the described thermal-initiated polymerization reaction time is 18 ~ 24h, and described mixing time is 20 ~ 24h;
Step (2) described mixing time is 18 ~ 24h.
6. the preparation method of catalyst as claimed in claim 1, it is characterized in that, the mass ratio of described phenylacetyl sodium sulfonate, water-soluble thermal initiator, water-soluble cross-linker, nonionic surface active agent, deionized water is (1.08 ~ 1.32): (0.03 ~ 0.05): (0.0258 ~ 0.0360): (0.028 ~ 0.052): (3.256 ~ 4.744); The volume ratio of described oil phase and deionized water is (18.45 ~ 26.88): (3.256 ~ 4.744).
7. the preparation method of catalyst as claimed in claim 1, it is characterized in that, described inorganic acid is sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, chloric acid, and described inorganic acid solution provides hydrogen ion, and described hydrionic concentration is 1.5 ~ 2.5mol/L; The consumption of described polymer powder adds 7.5 ~ 12.5g powder in often liter of inorganic acid.
8. the preparation method of catalyst as claimed in claim 1, it is characterized in that, described organic solvent is methyl alcohol, acetonitrile, acetone, chloroform, and the ratio of described step (1) product quality, molecular weight regulator volume, organic solvent volume is (0.108 ~ 0.292) g:(4.32 ~ 5.68) mL:(7.256 ~ 12.744) mL.
9. as in claim 1 ~ 8 arbitrarily as described in the organic solid hydrophobic acid catalyst that obtains of the preparation method of catalyst.
10. organic solid hydrophobic acid catalyst as claimed in claim 9, it is characterized in that, described catalyst diameter macropores is 8.5 ~ 24.5 μm, and connecting hole diameter is 1.4 ~ 6.7 μm, acidity is 4.749mmol/g, and the contact angle of catalyst and deionized water is 150 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410610714.4A CN104437634B (en) | 2014-11-03 | 2014-11-03 | hydrophobic organic solid acid catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410610714.4A CN104437634B (en) | 2014-11-03 | 2014-11-03 | hydrophobic organic solid acid catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437634A true CN104437634A (en) | 2015-03-25 |
| CN104437634B CN104437634B (en) | 2017-01-18 |
Family
ID=52884843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410610714.4A Expired - Fee Related CN104437634B (en) | 2014-11-03 | 2014-11-03 | hydrophobic organic solid acid catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437634B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166499A (en) * | 2016-07-25 | 2016-11-30 | 江苏大学 | A kind of method that in green solvent system, catalysis fibre element converts preparation 5 Hydroxymethylfurfural |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993140A (en) * | 2012-12-13 | 2013-03-27 | 浙江大学 | Method for preparing 5-hydroxymethyl furfural by catalyzing biomass conversion |
| WO2014058859A2 (en) * | 2012-10-11 | 2014-04-17 | Wisconsin Alumni Research Foundation | Method to convert monosaccharides to 5-(hydroxymethyl) furfural (hmf) using biomass-derived solvents |
| CN103992425A (en) * | 2014-05-16 | 2014-08-20 | 江苏大学 | Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization |
-
2014
- 2014-11-03 CN CN201410610714.4A patent/CN104437634B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014058859A2 (en) * | 2012-10-11 | 2014-04-17 | Wisconsin Alumni Research Foundation | Method to convert monosaccharides to 5-(hydroxymethyl) furfural (hmf) using biomass-derived solvents |
| CN102993140A (en) * | 2012-12-13 | 2013-03-27 | 浙江大学 | Method for preparing 5-hydroxymethyl furfural by catalyzing biomass conversion |
| CN103992425A (en) * | 2014-05-16 | 2014-08-20 | 江苏大学 | Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization |
Non-Patent Citations (1)
| Title |
|---|
| HEPING GAO ET AL.: "Synthesis and evaluation of macroporous polymerized solid acid derived from Pickering HIPEs for catalyzing cellulose into 5-hydroxymethylfurfural in an ionic liquid", 《RSC ADVANCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166499A (en) * | 2016-07-25 | 2016-11-30 | 江苏大学 | A kind of method that in green solvent system, catalysis fibre element converts preparation 5 Hydroxymethylfurfural |
| CN106166499B (en) * | 2016-07-25 | 2018-08-10 | 江苏大学 | A kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437634B (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437632B (en) | A kind of macropore soda acid difunctional organic solid catalyst and preparation method and application | |
| CN104741146B (en) | Multi-grade-pore acid and alkali double-functional solid catalyst and preparation method thereof | |
| CN105272950B (en) | A method of 5 hydroxymethyl furfural is produced by carbohydrate | |
| CN103657684B (en) | The preparation method of the acid composite catalyst of a kind of halloysite nanotubes-sulfonic group-Cr (III) ion | |
| CN103183832B (en) | A kind of preparation method of magnetic cellulose-chitosan composite microsphere | |
| CN105642233B (en) | A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons | |
| CN106311345A (en) | Acid-base bifunctional solid catalyst and preparation method thereof | |
| CN103788034A (en) | Preparation method for 5-hydroxymethylfurfural | |
| CN106905271B (en) | A kind of preparation and application of the heterogeneous catalysis of mesoporous material containing MCM-41 | |
| CN107952486A (en) | A kind of compound acidic solid catalyst PVP-HNTs@UiO-66-SO3H and preparation method thereof | |
| CN103301469B (en) | Preparation method of sephadex microsphere with smooth surfaces | |
| WO2017158117A1 (en) | Ionic polymers and use thereof in processing of biomass | |
| CN105251514A (en) | Carbon-containing hierarchical pore Brnsted acid/Lewis acid dual-functional catalyst, preparation method and applications | |
| CN103156784B (en) | Chitosan-fullerol compound, preparation method thereof compound and moisture-preserving antioxidant | |
| CN104437634B (en) | hydrophobic organic solid acid catalyst and preparation method thereof | |
| CN105618133B (en) | Magnetic glucosyl group solid acid catalyst and its preparation method and application | |
| CN103756992A (en) | Chocolate microbacterium magnetic cell as well as preparation method and application thereof | |
| CN106166499B (en) | A kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system | |
| CN105642345A (en) | Preparation method of hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst | |
| CN106187957A (en) | A kind of preparation method of 5 Hydroxymethylfurfural | |
| CN106111194A (en) | A kind of preparation method of the solid multi-stage porous catalyst containing Br*nsted and Lewis acid | |
| CN103354144A (en) | Magnetic composite microsphere as well as preparation method and application thereof | |
| CN106513038B (en) | Nanotube-shaped hollow difunctional solid catalyst of soda acid of one kind and preparation method thereof | |
| CN103980426B (en) | A kind of chemical bond is connected to the preparation method of the graphene hybrid material of carbene derivant | |
| CN102627701A (en) | Preparation method of galloyl konjac glucomannan |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170118 Termination date: 20171103 |