CN105964299B - A kind of porous type imitates enzyme solid acid catalyst and its preparation method and application - Google Patents
A kind of porous type imitates enzyme solid acid catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN105964299B CN105964299B CN201610492630.4A CN201610492630A CN105964299B CN 105964299 B CN105964299 B CN 105964299B CN 201610492630 A CN201610492630 A CN 201610492630A CN 105964299 B CN105964299 B CN 105964299B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- powder
- porous type
- preparation
- mixed
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000011973 solid acid Substances 0.000 title claims abstract description 54
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 43
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002678 cellulose Polymers 0.000 claims abstract description 24
- 239000001913 cellulose Substances 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 239000004376 Sucralose Substances 0.000 claims description 17
- BAQAVOSOZGMPRM-QBMZZYIRSA-N sucralose Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 BAQAVOSOZGMPRM-QBMZZYIRSA-N 0.000 claims description 17
- 235000019408 sucralose Nutrition 0.000 claims description 17
- 238000012719 thermal polymerization Methods 0.000 claims description 17
- 238000010828 elution Methods 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 13
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical class CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910006069 SO3H Inorganic materials 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 238000005287 template synthesis Methods 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 17
- 229960002163 hydrogen peroxide Drugs 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
- Silicon Polymers (AREA)
Abstract
The preparation method of enzyme solid acid catalyst is imitated the invention provides a kind of porous type and its catalytic cellulose generates the application of levulic acid in aqueous phase.The porous type imitates enzyme solid acid catalyst by Template synthesis, has loose structure, simultaneously containing cellulose binding domain (Cl) and catalysis region (SO3H), there is the design feature of enzyme catalyst, cellulose can be directly converted in aqueous phase is levulic acid, and catalyst can be used repeatedly, and levulic acid yield may be up to 65%.And Binding Capacity functional group (Cl) derives from biomass, SO in the method for preparing catalyst of the present invention3H is obtained using oxidation in situ, the dangerous material such as no concentrated sulfuric acid participate in, more efficiently, environmental protection.
Description
Technical field
The present invention relates to a kind of technical field of bionics solid catalyst, more particularly to a kind of porous type imitates enzyme solid acid
Catalyst and its preparation method and application.
Background technology
Seriously polluted with the increasingly depleted of the non-renewable resources such as coal, oil and its to caused by environment, to environment friend
The energy exploitation and application of good type renewable resource, the sustainable development for human society are most important.Cellulose is as the earth
On most abundant natural polymerses, there is many advantages, such as wide material sources, renewable, environment-friendly, can effectively convert
For high valuable chemicals such as 5 hydroxymethyl furfural, furfural, lactic acid, levulic acids.Wherein, levulic acid is arranged by USDOE
For one of ten big most valuable carbohydrate.Levulic acid has good reactivity, can carry out redox, ester
Change, substitute, polymerizeing etc., so as to be converted into a variety of high added value energy chemistry product, such as BDO, gamma-butyrolacton, maleic
Dicarboxylic anhydride etc..Therefore, the technological development that cellulose is converted into levulic acid has great importance.
At present, mainly there are two kinds of biological fermentation process and chemical catalysis by the method that raw material produces levulic acid of biomass.
The traditional biological fermentation method reaction time grows (3~5 days), and efficiency is low.Chemical catalysis application is more extensive, is comparatively easier to
Industrialization.At present levulic acid generally use liquid acid (sulfuric acid, hydrochloric acid etc.) or solid acid are prepared by raw material of biomass resource
As catalyst.Wherein liquid acid is strong to consersion unit corrosivity due to existing, and accessory substance is more, it is difficult to recycle, and two
The deficiencies of secondary discharge causes environmental pollution, is gradually substituted by solid acid.Although solid acid is without liquid acid corrosion production equipment
Etc. many deficiencies, but because solid acid and cellulose are not soluble in water, between the two in the presence of serious mass transfer and limit so that solid
The avtive spot of acid and β-Isosorbide-5-Nitrae-glycosidic bond of cellulosic molecule are difficult to contact, thus leverage the catalytic of solid acid
Energy.
The content of the invention
In view of this, present invention aims at provide a kind of porous type to imitate enzyme solid acid catalyst and preparation method thereof and answer
With it is poor to solve solid acid catalytic performance existing for catalytic cellulose generation levulic acid process in aqueous phase, the problems such as low yield.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of porous type to imitate enzyme solid acid catalyst, including following preparation process：
(1) by F127, ethanol and mixed in hydrochloric acid；
(2) mixed solution for obtaining the step (1) and Sucralose, tetraethyl orthosilicate and the ethoxy of 3- mercaptos propyl group three
Solvent is removed after base silane mixing, forms gel；
(3) gel for obtaining the step (2) carries out thermal polymerization, obtains C-Si composites；
(4) powder is made in the C-Si composites obtained in the step (3), elutes the F127 in the powder；
(5) powder after the elution F127 is mixed with methanol, hydrogen peroxide and carries out oxidation reaction, obtained porous type and imitate
Enzyme solid acid catalyst；
Preferable catalyst has micro- meso-hole structure, and the specific surface area of preferable catalyst is 300~500m2/ g, wherein
Mesoporous area is 200~400m2/ g, micropore area are 100~150m2/g；The pore volume of preferable catalyst for 0.15~
0.6cm3/g。
The invention provides the preparation method that the porous type described in a kind of such scheme imitates enzyme solid acid catalyst, including with
Lower step：
(1) by F127, ethanol and mixed in hydrochloric acid；
(2) mixed solution for obtaining the step (1) and Sucralose, tetraethyl orthosilicate and the ethoxy of 3- mercaptos propyl group three
Solvent is removed after base silane mixing, forms gel；
(3) gel that the step (2) obtains is subjected to thermal polymerization and obtains C-Si composites；
(4) powder is made in the C-Si composites obtained in the step (3), elutes the F127 in the powder；
(5) powder after the elution F127 is mixed with methanol, hydrogen peroxide and carries out oxidation reaction, obtained porous type and imitate
Enzyme solid acid catalyst；
It is preferred that step (1) in F127 quality and ethanol and the volume ratio of hydrochloric acid be 2~4g：
15~25ml：0.15~0.20ml；
The mass concentration of preferable hydrochloric acid is 6%~8%；
It is preferred that step (2) in Sucralose, the mol ratio of tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes
For 0.5~1.5：1~3：0.5~1.5；
It is preferred that step (3) in thermal polymerization temperature be 150~200 DEG C, the time of thermal polymerization is 10~15h；
It is preferred that step (4) in elution be specially：The powder is mixed with absolute ethyl alcohol, is evaporated backflow, often
An absolute ethyl alcohol is changed every 6~8h；
The mass ratio of preferable powder and single absolute ethyl alcohol is 1:25~40；
The temperature of preferable evaporation backflow is 60~100 DEG C；The time of preferable evaporation backflow is 12~24h.
It is preferred that step (5) in methanol and hydrogen peroxide volume ratio be 1：0.9~1.2；
The mass concentration of preferable hydrogen peroxide is 20%~35%；
The time of preferable oxidation reaction is 10~14h.
A kind of catalyst obtained the invention provides such scheme catalytic cellulose in aqueous phase is prepared in levulic acid
Application, comprise the following steps：Porous type is imitated into enzyme solid acid catalyst to mix with cellulose aqueous solution, at 160 DEG C~220 DEG C
Under conditions of react 6~15h, obtain levulic acid；
The mass concentration of cellulose is 1%~5% in preferable cellulose aqueous solution.
The invention provides a kind of porous type to imitate enzyme solid acid catalyst, is prepared by the method comprised the following steps：
By F127, ethanol and mixed in hydrochloric acid；By mixed solution and Sucralose, tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes
Mixing；Solvent in mixed solution is removed, forms gel, gel progress thermal polymerization is obtained into C/Si composites；It will obtain
C/Si composites powder is made, elute the F127 in the powder；Powder is mixed into progress with methanol, hydrogen peroxide afterwards
Oxidation reaction, obtain porous type and imitate enzyme solid acid catalyst.Porous type provided by the invention is imitated in enzyme solid acid catalyst structure
Contain substrate-binding region (- Cl) and catalysis region (- SO simultaneously3H), there is the design feature of enzyme catalyst, have micro- mesoporous
Structure, during the course of the reaction intermediate product can enter catalyst aperture interior catalyst point position, catalytic reaction is efficiently carried out；This
The imitative enzyme solid acid catalyst of porous type that invention provides can be applied to the catalytic cellulose in aqueous phase and be converted into levulic acid,
Yield can reach 65%, and catalyst can be used repeatedly.
Porous type provided by the invention, which is imitated in the preparation method of enzyme solid acid catalyst, uses biomass to provide Binding Capacity
Functional group (- Cl), obtain being catalyzed functional group (- SO using oxidation in situ3H), raw material is easy to get, and cost is low, and whole process is green
Color, efficient, environmental protection.
Brief description of the drawings
Fig. 1 is the infrared structure collection of illustrative plates that porous type made from embodiment 1 imitates enzyme solid acid catalyst；
Fig. 2 is the XPS collection of illustrative plates that porous type made from embodiment 1 imitates enzyme solid acid catalyst；
Fig. 3 is that porous type imitates the graph of a relation that enzyme solid acid catalyst reuses number and levulic acid yield.
Embodiment
The invention provides the preparation method that a kind of porous type imitates enzyme solid acid catalyst, comprise the following steps：
(1) by F127, ethanol and mixed in hydrochloric acid；
(2) mixed solution for obtaining the step (1) and Sucralose, tetraethyl orthosilicate and the ethoxy of 3- mercaptos propyl group three
Solvent is removed after base silane mixing to remove, and forms gel；
(3) gel that the step (2) obtains is subjected to thermal polymerization and obtains C-Si composites；
(4) powder is made in the C-Si composites obtained in the step (3), elutes the F127 in the powder；
(5) powder after the elution F127 is mixed with methanol, hydrogen peroxide and carries out oxidation reaction, obtained porous type and imitate
Enzyme solid acid catalyst.
F127, ethanol and mixed in hydrochloric acid are obtained mixed solution first by the present invention first, in the present invention, the matter of the F127
Amount and the volume ratio of ethanol and hydrochloric acid are preferably 2~4g：15~25ml：0.15~0.20ml, more preferably 3~3.5g：16~
20ml：0.16~0.18ml；The hydrochloric acid adds preferably in the form of hydrochloric acid solution, and the mass concentration of the hydrochloric acid solution is preferred
For 6%~8%, more preferably 6.5%~7.5%.The present invention mixes F127, ethanol and hydrochloric acid preferably under conditions of ultrasound
Close, the ultrasonic power is preferably
500~800W, more preferably 600~750W.In the present invention, the time of the mixing is preferably
10~60min, more preferably 20~40min.
After the mixed solution for obtaining including F127, ethanol and hydrochloric acid, the present invention by obtained mixed solution and Sucralose,
Tetraethyl orthosilicate and the mixing of 3- mercaptopropyltriethoxysilanes, obtain mixed solution second, remove solvent afterwards, obtain gel.
In the present invention, the mol ratio of the Sucralose, tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes be preferably 0.5~
1.5：1~3：0.5~1.5, more preferably 0.8~1.2:1.5~2.5:08~1.2, most preferably 1:2:1；The trichlorine sugarcane
Sugar and F127 mass ratio are preferably 0.2~1:1, more preferably 0.3~0.8:1.The present invention will preferably under conditions of ultrasound
The mixed solution of step (1) mixes with Sucralose, tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes, described ultrasonic
Power is preferably 500~800W, more preferably 600~750W, and the ultrasonic time is preferably 10~30min, more preferably
15~20min.
After obtaining mixed solution second, the present invention removes the etoh solvent in mixed solution, obtains gel.It is of the invention preferred
Ethanol is removed by way of volatilizing naturally.In the present invention, the time volatilized naturally is preferably 12~24h, more excellent
Elect 15~20h as.
After obtaining gel, the gel is carried out thermal polymerization by the present invention, obtains C-Si composites.In the present invention, institute
The temperature for stating thermal polymerization is preferably 150~200 DEG C, more preferably 160~180 DEG C；The time of the thermal polymerization is preferably 10~
15h, more preferably 12~13h.The present invention by the use of Sucralose as carbon matrix precursor and Binding Capacity functional group (- Cl) donor,
Make tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes that dehydrating condensation generation SiO occur using heat polymerization2, trichlorine sugarcane
Sugar is inlayed wherein as C presomas, forms C/Si composites.
After obtaining C/Si composites, powder is made in C-Si composites by the present invention, elutes the F127 in powder.This hair
It is bright that C-Si composites are preferably made by powder by the method for grinding；In the present invention, the particle diameter of the powder is preferably
0.01~0.05mm, more preferably 0.02~0.03mm；In the present invention, the specific steps of the elution are preferably：By described in
Powder is mixed with absolute ethyl alcohol, is evaporated backflow, and an absolute ethyl alcohol is changed every 6~8h.In the present invention, the powder
Mass ratio with single absolute ethyl alcohol is preferably 1:25~40, more preferably 1:30~35；The temperature of the evaporation backflow is preferred
For 60~100 DEG C, more preferably 70~90 DEG C；The time of the evaporation backflow is preferably 12~24h, more preferably 15~22h,
Most preferably 16~20h；After the completion of elution, the present invention preferably filters the solid powder after elution, and deionized water is used after filtering
Rinse with ethanol 3~5 times, be dried after the completion of flushing repeatedly, described drying temperature is preferably 70~90 DEG C, more preferably
80 DEG C, described drying time is preferably 10~15h, more preferably 11~13h, most preferably 12h.
In the present invention, high-temperature calcination can also be used to remove F127, concretely comprised the following steps：The powder that such scheme is obtained
1~3h is calcined at end at 300~500 DEG C, and calcining is dried after being rinsed repeatedly with deionized water and ethanol after terminating.In the present invention
In, the temperature of the calcining is preferably 300~500 DEG C, and more preferably 350~450 DEG C are most preferably；The time of the calcining is excellent
Elect 1~3h, more preferably 1.5~2.5h as.In the present invention, the method for described flushing and drying is consistent with such scheme,
It will not be repeated here.
The present invention is template using F127, removes and forms with micro- meso-hole structure by thermal polymerization solidification, template
C/Si composites, improve the specific surface area of solid acid catalyst.
After F127 is eluted, the powder after elution is mixed and carries out oxidation reaction by the present invention with methanol, hydrogen peroxide, is obtained
Porous type imitates enzyme solid acid catalyst.In the present invention, the volume ratio of the methanol and hydrogen peroxide is preferably 1：0.9~1.2,
More preferably 1:1；The hydrogen peroxide adds preferably in the form of hydrogenperoxide steam generator, and the quality of the hydrogenperoxide steam generator is dense
Degree is preferably 20%~35%, more preferably 25%~33%, most preferably 30%.In the present invention, the oxidation reaction
Time is preferably 10~14h, more preferably 11~13h, most preferably 12h；The temperature of the oxidation reaction is preferably 20~30
DEG C, more preferably 25 DEG C, mixed solution is preferably placed in shaking table oscillator by the present invention to be aoxidized, the shaking table oscillator
It is preferably 200~500 beats/min to shake frequency, more preferably 300~400 beats/min.The present invention is with methanol and hydrogen peroxide
Mixture be oxidant, by oxidation in situ obtain be catalyzed functional group (- SO3H), so as to obtaining final product porous type
Imitative enzyme solid acid catalyst.
After the completion of oxidation reaction, obtained reaction solution is preferably filtered, washed, being dried by the present invention, obtains imitative enzyme type
Solid acid catalyst product.In the present invention, it is described filtering, washing, dry method with it is above-mentioned solid powder is filtered,
Washing, the method dried are consistent, will not be repeated here.
Present invention also offers the catalyst that preparation method described in above-mentioned technical proposal obtains.Catalyst provided by the invention
With micro- meso-hole structure, the specific surface area of catalyst is preferably 300~500m2/ g, wherein mesoporous area are 200~400m2/ g,
Micropore area is 100~150m2/g；The pore volume of catalyst is preferably 0.15~0.6cm3/g。
The catalyst obtained the invention provides preparation method described in a kind of such scheme catalytic cellulose system in aqueous phase
Application in standby levulic acid, comprises the following steps：Porous type is imitated into enzyme solid acid catalyst to mix with cellulose aqueous solution,
6~15h is reacted under conditions of 160 DEG C~220 DEG C, obtains levulic acid.
In the present invention, the mass concentration of cellulose is preferably 1%~5% in the cellulose aqueous solution, more preferably
2%~4%；The temperature of the reaction is preferably 160 DEG C~220 DEG C, more preferably 180~200 DEG C；The time of the reaction is excellent
Elect 6~15h, more preferably 8~12h as；The ratio between the quality of the catalyst and the volume of cellulose aqueous solution preferably 1~
5g：100ml, more preferably 2~3g：100ml.
In the present invention, it is preferred to carry out separating-purifying to product by following steps, pure levulic acid is obtained：To anti-
Solution carries out centrifugal treating after should terminating, and obtains supernatant；The supernatant is rotated to 1/3rd, Zhi Houjia of original volume
Enter ethyl acetate extraction, ethyl acetate phase is evaporated at 60~80 DEG C, obtains pure levulic acid.In the present invention, institute
The speed for stating centrifugation is preferably 1500~2000r/min, more preferably 1600~1800r/min；The time of the centrifugation is preferred
For 10~30min, more preferably 15~25min；The temperature of the revolving is preferably 80~95 DEG C, more preferably 85~90 DEG C；
The time of the revolving is preferably 20~40min, more preferably 15~30min；The volume ratio of the extractant and supernatant is excellent
Elect 2~3 as:1, more preferably 2.5:1；The evaporating temperature of the ethyl acetate phase is preferably 60~80 DEG C, more preferably 65~
75℃。
Catalyst provided by the invention has micro- meso-hole structure, and specific surface area is big, and stability is good, is directly catalyzed in aqueous phase
The catalytic site that the hydrolysis intermediate product of cellulose raw into cellulose during levulic acid can enter inside solid acid catalyst aperture
Position, makes catalytic reaction efficiently carry out, levulic acid yield is up to 65%.
Enzyme solid acid catalyst and its preparation method and application is imitated to porous type provided by the invention with reference to embodiment
It is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
2.5gF127 is weighed, is added in 20mL absolute ethyl alcohols, the hydrochloric acid that 0.18ml mass concentrations are 8% is added dropwise and is catalyzed
Agent, ultrasonic 30min, it is 700W to control ultrasonic power, F127 is fully dissolved；According to Sucralose after F127 dissolvings：TEOS is (former
Tetraethyl orthosilicate):MPTES (3- mercaptopropyltriethoxysilanes) mol ratio is 1：1.8：1 ratio sequentially adds presoma, control
Ultrasonic power processed is 700W, and continuing ultrasonic 20min makes it fully dissolve, and forms stable homogeneous system；Mixed solution is placed in
Volatilize 12h naturally in fume hood, after ethanol is thoroughly evaporated completely formed self-organizing gel, by gel under the conditions of 160 DEG C hot polymerization
12h is closed, obtains C-Si composites；C-Si composites are ground into powder of the particle diameter for 0.02mm or so, take 3g powder to use
150mL ethanol evaporations flow back, and it is 80 DEG C to control evaporation reflux temperature, changes an ethanol every 6h, flow back 24h altogether；After eluting
Powder filter, be placed in after being rinsed repeatedly with deionized water and ethanol in 80 DEG C of thermostatic drying chamber dry 12h, dry after the completion of
Add 100mL methanol/hydrogen peroxide (1:1) mixed liquor, it is placed in and swings frequency for 200 beats/min, temperature is to be filled in 25 DEG C of shaking table
Divide oxidation 12h, by reacting liquid filtering after the completion of oxidation, obtained solid catalyst is dried in 70 DEG C of thermostatic drying chamber
10h, obtain porous type and imitate enzyme solid acid catalyst product.
The structure of gained solid acid catalyst is analyzed using FTIS, obtained INFRARED SPECTRUM
Figure is as shown in Figure 1；According to Fig. 1 as can be seen that simultaneously containing-Cl and-SO in the structure of catalyst3H functional groups.
The carbon of gained solid acid catalyst is analyzed using x-ray photoelectron spectroscopy, obtained XPS spectrum figure
As shown in Figure 2；According to Fig. 2 as can be seen that C1s combinations can be 286ev or so, peak intensity is high, and the symmetry at peak is preferable, shows
The surface concentration of carbon is higher in solid acid catalyst, and carbon high sensitivity, and catalytic activity is good.
Specific surface area and pore volume to gained solid acid catalyst are measured and can obtained：Total specific surface area 399m2/ g, it is mesoporous
Specific surface area 298m2/ g, micropore specific area 101m2/ g, pore volume 0.25cm3/g。
Embodiment 2
3gF127 is weighed, is added in 20mL absolute ethyl alcohols, the hydrochloric acid that 0.15ml mass concentrations are 6% is added dropwise and is catalyzed
Agent, ultrasonic 20min, it is 500W to control ultrasonic power, F127 is fully dissolved；Sucralose is sequentially added after F127 dissolvings
1mol, TEOS (tetraethyl orthosilicate) 2mol, MPTES (3- mercaptopropyltriethoxysilanes) 1mol, controls the ultrasonic power to be
500W, continuing ultrasonic 30min makes it fully dissolve, and forms stable homogeneous system；Mixed solution is placed in fume hood natural
Volatilize 24h, after ethanol is thoroughly evaporated completely formed self-organizing gel, by gel under the conditions of 180 DEG C thermal polymerization 13h, obtain C-
Si composites；C-Si composites are ground into powder of the particle diameter for 0.05mm or so, take 3g powder 130mL ethanol evaporations
Backflow, it is 100 DEG C to control evaporation reflux temperature, changes an ethanol every 8h, flow back 12h altogether；By the powder filter after elution, use
Deionized water and ethanol, which are placed in after rinsing repeatedly in 70 DEG C of thermostatic drying chamber, dries 12h, and 100mL first is added after the completion of drying
Alcohol/hydrogen peroxide (1:1.1) mixed liquor, it is placed in and swings frequency for 500 beats/min, fully oxidized 10h in the shaking table that temperature is 20 DEG C,
By reacting liquid filtering after the completion of oxidation, obtained solid catalyst is dried into 15h in 80 DEG C of thermostatic drying chamber, obtained porous
Type imitates enzyme solid acid catalyst product.
Enzyme solid acid catalysis is imitated to gained porous type using FTIS and x-ray photoelectron spectroscopy
Agent product is analyzed, and obtained infared spectrum and XPs collection of illustrative plates are similar to Example 1.
Specific surface area and pore volume to gained solid acid catalyst are measured and can obtained：Total specific surface area 480m2/ g, it is mesoporous
Specific surface area 350m2/ g, micropore specific area 130m2/ g, pore volume 0.41cm3/g。
Embodiment 3
3gF127 is weighed, is added in 25mL absolute ethyl alcohols, the hydrochloric acid that 0.20ml mass concentrations are 7.5% is added dropwise and is catalyzed
Agent, ultrasonic 25min, it is 600W to control ultrasonic power, F127 is fully dissolved；Sucralose is sequentially added after F127 dissolvings
1.2mol, TEOS (tetraethyl orthosilicate) 2mol, MPTES (3- mercaptopropyltriethoxysilanes) 1.1mol, control ultrasonic power
For 600W, continuing ultrasonic 10min makes it fully dissolve, and forms stable homogeneous system；Mixed solution is placed in fume hood certainly
So volatilization 20h, after ethanol is thoroughly evaporated completely formed self-organizing gel, by gel under the conditions of 170 DEG C thermal polymerization 15h, obtain
C-Si composites；C-Si composites are ground into powder of the particle diameter for 0.03mm or so, take 3g powder 100mL ethanol to steam
Stream is beamed back, it is 90 DEG C to control evaporation reflux temperature, changes an ethanol every 7h, flow back 12h altogether；By the powder filter after elution,
It is placed in after being rinsed repeatedly with deionized water and ethanol in 70 DEG C of thermostatic drying chamber and dries 20h, adds 50mL's after the completion of drying
Methanol/hydrogen peroxide (1:1.1) mixed liquor, it is placed in and swings frequency for 300 beats/min, it is fully oxidized in the shaking table that temperature is 25 DEG C
11h, by reacting liquid filtering after the completion of oxidation, obtained solid catalyst is dried into 12h in 80 DEG C of thermostatic drying chamber, obtained
Porous type imitates enzyme solid acid catalyst product.
Enzyme solid acid catalysis is imitated to gained porous type using FTIS and x-ray photoelectron spectroscopy
Agent product is analyzed, and obtained infared spectrum and XPs collection of illustrative plates are similar to Example 1.
Specific surface area and pore volume to gained solid acid catalyst are measured and can obtained：Total specific surface area 490m2/ g, it is mesoporous
Specific surface area 365m2/ g, micropore specific area 125m2/ g, pore volume 0.35cm3/g。
Embodiment 4
3gF127 is weighed, is added in 20mL absolute ethyl alcohols, the hydrochloric acid that 0.15ml mass concentrations are 7% is added dropwise and is catalyzed
Agent, ultrasonic 40min, it is 800W to control ultrasonic power, F127 is fully dissolved；Sucralose is sequentially added after F127 dissolvings
1.0mol, TEOS (tetraethyl orthosilicate) 2.1mol, MPTES (3- mercaptopropyltriethoxysilanes) 1.1mol, controls ultrasonic work(
Rate is 800W, and continuing ultrasonic 25min makes it fully dissolve, and forms stable homogeneous system；Mixed solution is placed in fume hood
Naturally volatilize 15h, after ethanol is thoroughly evaporated completely formed self-organizing gel, by gel under the conditions of 165 DEG C thermal polymerization 14h, obtain
To C-Si composites；C-Si composites are ground into powder of the particle diameter for 0.01mm or so, take 3g powder 110mL ethanol
Evaporation backflow, it is 85 DEG C to control evaporation reflux temperature, changes an ethanol every 7h, flow back 18h altogether；By the powder mistake after elution
Filter, it is placed in after being rinsed repeatedly with deionized water and ethanol in 75 DEG C of thermostatic drying chamber and dries 16h, 60mL is added after the completion of drying
Methanol/hydrogen peroxide (1:1.1) mixed liquor, it is placed in and swings frequency for 350 beats/min, it is fully oxidized in the shaking table that temperature is 30 DEG C
14h, by reacting liquid filtering after the completion of oxidation, obtained solid catalyst is dried into 10h in 75 DEG C of thermostatic drying chamber, obtained
Porous type imitates enzyme solid acid catalyst product.
Enzyme solid acid catalysis is imitated to gained porous type using FTIS and x-ray photoelectron spectroscopy
Agent product is analyzed, and obtained infared spectrum and XPs collection of illustrative plates are similar to Example 1.
Specific surface area and pore volume to gained solid acid catalyst are measured and can obtained：Total specific surface area 501m2/ g, it is mesoporous
Specific surface area 370m2/ g, micropore specific area 131m2/ g, pore volume 0.37cm3/g。
Embodiment 5
The porous type for taking 0.05g embodiments 1~4 to prepare imitates enzyme solid acid catalyst and 0.05g microcrystalline celluloses, adds
5mL deionized water, catalytic reaction is carried out in autoclave, controlling reaction temperature is 200 DEG C, mixing speed 900r/
Min, reaction time 12h, the mixed solution after reaction terminates are filtered, using the production concentration in HPLC detection filtrates simultaneously
Calculated yield, HPLC condition are：Mobile phase 0.05M H2SO4, 30 DEG C, flow velocity 0.5mL/min of column temperature, Composition distribution；
The concentration that detection can obtain levulic acid in filtrate is 6.512g/L, yield 65.12%.
Embodiment 6
The porous type for taking 0.1g embodiments 1~4 to prepare imitates enzyme solid acid catalyst and 0.1g microcrystalline celluloses, adds 5mL
Deionized water, carry out catalytic reaction in autoclave, controlling reaction temperature is 160 DEG C, mixing speed 900r/min,
Reaction time is 6h, and the mixed solution after reaction terminates is filtered, and production concentration and calculating in filtrate are detected using HPLC
Yield, HPLC condition are：Mobile phase 0.05M H2SO4, 30 DEG C, flow velocity 0.5mL/min of column temperature, Composition distribution；
The concentration that detection can obtain levulic acid in filtrate is 12.56g/L, yield 62.80%.
As seen from the above embodiment, imitative enzyme type solid acid catalyst provided by the invention has micro- meso-hole structure, compares surface
Product is big, and stability is high, and catalytic activity is good, can directly by cellulose catalytic be levulic acid, high conversion rate, and preparation in water-based
Method is simple, and raw material is simple and easy to get, whole process green high-efficient.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of porous type imitates enzyme solid acid catalyst, it is characterised in that is prepared by the method comprised the following steps：
(1) by F127, ethanol and mixed in hydrochloric acid；
(2) mixed solution for obtaining the step (1) and Sucralose, tetraethyl orthosilicate and 3- mercapto propyl-triethoxysilicanes
Solvent is removed after alkane mixing, forms gel；The Sucralose, tetraethyl orthosilicate and 3- mercaptopropyltriethoxysilanes rub
You are than being 0.5~1.5：1~3：0.5~1.5；
(3) gel for obtaining the step (2) carries out thermal polymerization, obtains C-Si composites；
(4) powder is made in the C-Si composites obtained in the step (3), elutes the F127 in the powder；
(5) powder after the elution F127 is mixed with methanol, hydrogen peroxide and carries out oxidation reaction, obtained the imitative enzyme of porous type and consolidate
Body acid catalyst.
2. catalyst according to claim 1, it is characterised in that the catalyst has micro- meso-hole structure, the catalysis
The specific surface area of agent is 300~500m2/ g, wherein mesoporous area are 200~400m2/ g, micropore area are 100~150m2/g；
The pore volume of the catalyst is 0.15~0.6cm3/g。
3. the porous type described in claim 1 or 2 imitates the preparation method of enzyme solid acid catalyst, it is characterised in that including following
Step：
(1) by F127, ethanol and mixed in hydrochloric acid；
(2) mixed solution for obtaining the step (1) and Sucralose, tetraethyl orthosilicate and 3- mercapto propyl-triethoxysilicanes
Solvent is removed after alkane mixing, forms gel；
(3) gel for obtaining the step (2) carries out thermal polymerization, obtains C-Si composites；
(4) powder is made in the C-Si composites that the step (3) obtains, elutes the F127 in the powder；
(5) powder after the elution F127 is mixed with methanol, hydrogen peroxide and carries out oxidation reaction, obtained the imitative enzyme of porous type and consolidate
Body acid catalyst.
4. preparation method according to claim 3, it is characterised in that in the step (1) F127 quality and ethanol and
The volume ratio of hydrochloric acid is 2~4g：15~25ml：0.15~0.20ml；
The mass concentration of the hydrochloric acid is 6%~8%.
5. preparation method according to claim 3, it is characterised in that Sucralose, orthosilicic acid four in the step (2)
The mol ratio of ethyl ester and 3- mercaptopropyltriethoxysilanes is 0.5~1.5：1~3：0.5~1.5.
6. preparation method according to claim 3, it is characterised in that the temperature of the thermal polymerization in the step (3) is 150
~200 DEG C, the time of thermal polymerization is 10~15h.
7. preparation method according to claim 3, it is characterised in that the elution in the step (4) is specially：By described in
Powder is mixed with absolute ethyl alcohol, is evaporated backflow, and an absolute ethyl alcohol is changed every 6~8h；
The mass ratio of the powder and single absolute ethyl alcohol is 1:25~40；
The temperature of the evaporation backflow is 60~100 DEG C；The time of the evaporation backflow is 12~24h.
8. preparation method according to claim 3, it is characterised in that methanol and hydrogen peroxide in the step (5)
Volume ratio is 1：0.9~1.2；
The mass concentration of the hydrogen peroxide is 20%~35%；
The time of the oxidation reaction is 10~14h.
9. preparation method described in the catalyst or claim 3~8 any one described in claim 1~2 any one obtains
Catalyst in aqueous phase catalytic cellulose prepare application in levulic acid, comprise the following steps：Porous type is imitated into enzyme solid
Acid catalyst is mixed with cellulose aqueous solution, and 6~15h is reacted under conditions of 160~220 DEG C, obtains levulic acid.
10. application according to claim 9, it is characterised in that the mass concentration of cellulose in the cellulose aqueous solution
For 1%~5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610492630.4A CN105964299B (en) | 2016-06-27 | 2016-06-27 | A kind of porous type imitates enzyme solid acid catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610492630.4A CN105964299B (en) | 2016-06-27 | 2016-06-27 | A kind of porous type imitates enzyme solid acid catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105964299A CN105964299A (en) | 2016-09-28 |
| CN105964299B true CN105964299B (en) | 2018-04-10 |
Family
ID=57020913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610492630.4A Expired - Fee Related CN105964299B (en) | 2016-06-27 | 2016-06-27 | A kind of porous type imitates enzyme solid acid catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105964299B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940362A (en) * | 2018-08-13 | 2018-12-07 | 南京林业大学 | A kind of preparation method of sulfonic acid funtionalized amylose solid acid catalyst and products thereof, application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114470C (en) * | 1999-05-24 | 2003-07-16 | 中国科学院山西煤炭化学研究所 | Preparation of organic functional mesoporous molecular sieve with double pore distribution |
| US8148553B2 (en) * | 2009-06-23 | 2012-04-03 | Wisconsin Alumni Research Foundation | Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities |
| US8399688B2 (en) * | 2011-05-25 | 2013-03-19 | Wisconsin Alumni Research Foundation | Production of levulinic acid, furfural, and gamma valerolactone from C5 and C6 carbohydrates in mono- and biphasic systems using gamma-valerolactone as a solvent |
| CN103084188B (en) * | 2012-12-20 | 2015-03-11 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN103159876B (en) * | 2013-01-30 | 2015-12-09 | 中国科学技术大学 | A kind of preparation method of the macromolecule solid acid catalyst based on the modification of chlorine ball |
| CN105149007A (en) * | 2015-09-21 | 2015-12-16 | 淮阴师范学院 | Preparation method of magnetic biomimetic carbon-based solid acid catalyst |
-
2016
- 2016-06-27 CN CN201610492630.4A patent/CN105964299B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105964299A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xing et al. | Preparation and analysis of straw activated carbon synergetic catalyzed by ZnCl2-H3PO4 through hydrothermal carbonization combined with ultrasonic assisted immersion pyrolysis | |
| CN103084187B (en) | Carbon-based solid acid and preparation method thereof | |
| CN108516548A (en) | A kind of preparation method of high mesoporous rate activated carbon and its activated carbon of acquisition | |
| CN102583311A (en) | Method for preparing biomass carbon by utilizing agricultural and forestry waste | |
| CN107628597B (en) | By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method | |
| CN104118863B (en) | A kind of ionic liquid activation rice husk prepares the method for porous carbon material for supercapacitor | |
| CN103877971A (en) | Efficient visible-light-induced photocatalyst and preparation method thereof | |
| CN103833003A (en) | Method for preparing larch based ordered mesoporous carbon by virtue of soft template | |
| CN108043407A (en) | A kind of Co/ sepiolites catalyst and its preparation method and application | |
| CN106560234A (en) | Method for preparing carbon aerogel by using plant biomorphic material | |
| CN112495441A (en) | Cerium dioxide coated ZIF-67 catalyst for synthesizing cyclic carbonate and preparation thereof | |
| CN110327939B (en) | Preparation method and application of esterification-saponification reaction catalyst | |
| CN102430414A (en) | Zirconium-based magnetic solid superacid catalyst, its preparation and method for preparing levoglucose ketone by catalytic pyrolysis of cellulose or biomass | |
| CN105964299B (en) | A kind of porous type imitates enzyme solid acid catalyst and its preparation method and application | |
| CN108014782A (en) | A kind of method of catalytic degradation lignin | |
| CN110421665B (en) | Energy storage wood takes titanium dioxide loaded rhodamine red as heat conduction filler | |
| CN106423214A (en) | Method for preparing carbon-based solid acid with high specific surface area and high acid content from corncob hydrolysis residues | |
| CN105131128A (en) | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents | |
| CN102380402A (en) | Titanium-based magnetic solid super-acid catalyst and preparation thereof and method for preparing laevoglucose ketone by means of catalytic pyrolysis of cellulose or biomass | |
| CN108014779A (en) | A kind of preparation method of efficiently mesoporous photocatalyst of zinc oxide | |
| CN103084162B (en) | Composite oxides solid catalyst of lanthanum load and preparation method thereof and application | |
| CN103219160B (en) | Scattering layer is by progressive TiO 2the semiconductor film membrane preparation method that particle is formed | |
| CN112479205A (en) | Narrow-pore bamboo sheath activated carbon and preparation method thereof | |
| CN114570389B (en) | Sulfonic carbon catalyst and preparation method and application thereof | |
| CN104230708B (en) | A kind of preparation method of methyl-formiate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180410 Termination date: 20200627 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |