CN107511177B - The method of microwave ultrasonic wave assistance multi-functional resins solid acid catalysis cellulose effectively hydrolyzing - Google Patents
The method of microwave ultrasonic wave assistance multi-functional resins solid acid catalysis cellulose effectively hydrolyzing Download PDFInfo
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- CN107511177B CN107511177B CN201710795338.4A CN201710795338A CN107511177B CN 107511177 B CN107511177 B CN 107511177B CN 201710795338 A CN201710795338 A CN 201710795338A CN 107511177 B CN107511177 B CN 107511177B
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- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920005989 resin Polymers 0.000 title claims abstract description 90
- 239000001913 cellulose Substances 0.000 title claims abstract description 55
- 229920002678 cellulose Polymers 0.000 title claims abstract description 55
- 239000011973 solid acid Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 14
- 238000007171 acid catalysis Methods 0.000 title abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 230000007062 hydrolysis Effects 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 26
- 229910052801 chlorine Inorganic materials 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 235000000346 sugar Nutrition 0.000 claims description 13
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 11
- 229920001596 poly (chlorostyrenes) Polymers 0.000 claims description 11
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002608 ionic liquid Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229950000244 sulfanilic acid Drugs 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002525 ultrasonication Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 2
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 230000009471 action Effects 0.000 abstract description 9
- 108010059892 Cellulase Proteins 0.000 abstract description 6
- 229940106157 cellulase Drugs 0.000 abstract description 6
- 229910006069 SO3H Inorganic materials 0.000 abstract description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method that microwave ultrasonic wave assists multi-functional resins solid acid catalysis cellulose effectively hydrolyzing, this method uses multi-functional resins solid acid as catalyst, and cellulose hydrolysis reaction more cleans green；Multi-functional resins solid acid has cellulose adsorption site (- Cl) and cellulose hydrolytic sites (- SO3H), the mode of action of cellulase can be imitated, so that the hydrolysis of cellulose has more directionality；Ferroso-ferric oxide component in multi-functional resins solid acid makes it have stronger magnetism, and the separation and recovery with reaction system and hydrolytic residue can be realized under the action of simple outer plus magnet.In addition to this, the present invention by two kinds of energy of microwave ultrasonic wave effective superposition, facilitate the reduction of cellulose hydrogen bond network broken with reaction activity, compared with traditional heating mode, heating speed is fast, and homogeneous heating can reduce reaction temperature, the reaction time is saved, keeps the hydrolysis condition of cellulose milder.
Description
Technical field
The invention belongs to biomass energy chemical fields, and in particular to a kind of microwave ultrasonic wave assistance multi-functional resins solid
The method of acid catalysis cellulose effectively hydrolyzing.
Background technique
It is with the continuous reduction of fossil resource reserves and getting worse for environmental pollution phenomenon, content in nature is most rich
Rich biomass components cellulose is converted into the various high valuable chemicals that necessary for human is wanted and high-quality fuel is to alleviate energy
Source crisis and the effective way for mitigating environmental pollution, and realize that the premise and basis of this effective way is then by water-insoluble
Cellulose is hydrolyzed to soluble reduced sugar even glucose by green mild efficient method.
It is well known that the problem of hydrolysis of traditional fibre element is primarily present two broad aspects: on the one hand, cellulose hydrolysis
The catalyst of middle use is inorganic liquid acid and cellulase mostly.Although inorganic liquid acid is cheap and easy to get, hydrolysis efficiency is higher,
But it has biggish corrosivity and action condition is harsher, in addition, it is not easily recycled and the waste liquid given off can be to ring
Very big pollution is caused in border, does not meet the developing direction of current Green Chemistry；Cellulase category biological agent, although its effect
Condition is milder, mode of action directionality with higher, also complies with the developing direction of Green Chemistry, but its production cost
Higher, hydrolysis required time is longer, in addition, cellulose needs to pass through pretreatment in advance when it is easy inactivation and has an effect, this
A little deficiencies limit the scale hydrolysis of cellulose to a certain extent.On the other hand, it is used in cellulose hydrolysis
Heating method is the heat transfer heating method such as oil bath and sand-bath mostly.Under normal circumstances, the rate of heat addition of heat transfer heating method
Relatively slow, reaction system uneven heating is even, or even will appear the excessively high situation of local temperature, and then lead to cellulose hydrolysis effect not
It is ideal.
Summary of the invention
The invention discloses the sides that a kind of microwave ultrasonic wave assists multi-functional resins solid acid catalysis cellulose effectively hydrolyzing
Method, this method use multi-functional resins solid acid as catalyst, and cellulose hydrolysis reaction more cleans green；It is multi-functional
Resin solid acid has cellulose adsorption site (- Cl) and cellulose hydrolytic sites (- SO3H), the work of cellulase can be imitated
With mode, so that the hydrolysis of cellulose has more directionality；Ferroso-ferric oxide component in multi-functional resins solid acid makes it
With stronger magnetism, the separation and recovery with reaction system and hydrolytic residue can be realized under the action of simple outer plus magnet.
In addition to this, the present invention by two kinds of energy of microwave ultrasonic wave effective superposition, facilitate cellulose hydrogen bond network break and
The reduction of reaction activity, compared with traditional heating mode, heating speed is fast, homogeneous heating, can reduce reaction temperature, saves
Reaction time keeps the hydrolysis condition of cellulose milder.
The first aspect of the invention provides:
A kind of resin solid acid catalyst contains-Cl on main chain, and is also grafted with-SO on resin3H。
In one embodiment, the resin solid acid catalyst is part chlorine on chlorine-containing resins by aminobenzenesulfonic acid
Base replaces.
In one embodiment, chlorine-containing resins are selected from polychlorostyrene methylstyrene resin, Corvic, chlorinated polypropylene
Resin or chlorinated polyether resin；Preferably polychlorostyrene methylstyrene resin.
In one embodiment, magnetic Fe is embedded in the duct of above-mentioned resin solid acid catalyst3O4Nanoparticle.
The second aspect of the invention provides:
The preparation method of above-mentioned resin solid acid catalyst, includes the following steps:
Step 1, chlorine-containing resins are swollen in organic solvent；
P-aminobenzene sulfonic acid is added in solution after swelling and carries out substitution sulfonating reaction, tree is washed after reaction for step 2
Rouge；
Step 3, the resin that step 2 is obtained are added to containing nanometer Fe3O4Organic solvent, make embedding in the duct of resin
Enter nanometer Fe3O4；
Step 4, then resin is washed, is dried.
In one embodiment, the chlorine-containing resins are selected from polychlorostyrene methylstyrene resin, Corvic, chlorination
Acrylic resin or chlorinated polyether resin；Preferably polychlorostyrene methylstyrene resin.
In one embodiment, the mass volume ratio of chlorine-containing resins and organic solvent is (10~30g) in step 1: (200
~400mL)；The parameter of swelling process is: 60~120 DEG C of temperature, 12~36h of time.
In one embodiment, organic solvent is in dimethylformamide, tetrahydrofuran, carbon tetrachloride, chloroform or toluene
One or several kinds of mixing, preferably dimethylformamide；
In one embodiment, the weight ratio of chlorine-containing resins and p-aminobenzene sulfonic acid is 4:3~4:1 in step 2；Replace sulphur
Change 100~140 DEG C of reaction temperature, replaces 36~72h of sulfonating reaction time.
In one embodiment, chlorine-containing resins and nanometer Fe3O4Mass ratio be 10:1~20:1.
In one embodiment, the step 3,60~120 DEG C of the temperature of reaction process preferably add during the reaction
Enter ultrasonic wave added, ultrasonication time preferably 1~4h.
In one embodiment, washing resin is successively with organic solvent and ethanol washing.
The third aspect of the invention provides:
Above-mentioned resin solid acid catalyst prepares the application in reduced sugar in cellulose hydrolysis.
The fourth aspect of the invention provides:
A kind of method that cellulose hydrolysis prepares reduced sugar, includes the following steps:
In ionic liquid be added cellulose, above-mentioned resin solid acid catalyst, water, be hydrolyzed reaction to get.
In one embodiment, ionic liquid is glyoxaline ion liquid.
In one embodiment, the glyoxaline ion liquid is selected from 1- butyl -3- methylimidazole villaumite, 1- ethyl -
One or more of 3- methylimidazole villaumite, 1- butyl -3- methylimidazole acetate, 1- ethyl-3-methylimidazole acetate
Mixing.
In one embodiment, in hydrolysis reaction, it is additionally added the effect of microwave and ultrasound.
In one embodiment, microwave frequency is 2000~3000MHz, preferably 2450MZH；Microwave power set is 100
~700W, preferably 300W；Supersonic frequency is 5~40KHz, preferably 25KHZ；Ultrasonic power is set as 100~900W, preferably
600W。
In one embodiment, 80~150 DEG C of hydrolysising reacting temperature, preferably 120 DEG C；0.5~4h of hydrolysis time,
It is preferred that 1h.
In one embodiment, the additional amount of cellulose is 2~10wt% of ionic liquid dosage, and water consumption is ionic liquid
0.5~2wt% of body dosage.
In one embodiment, resin solid acid catalyst levels are 20~60wt% of cellulose dosage.
The fifth aspect of the invention provides:
Chlorine is improving the acid catalyzed cellulose hydrolysis efficiency of resin solid as the active group of resin solid acid catalyst
In application.
The sixth aspect of the invention provides:
Nanometer Fe3O4Carrier as resin solid acid catalyst is improving the acid catalyzed cellulose hydrolysis effect of resin solid
Application in rate；The hydrolytic process is under ultrasound and microwave-assisted effect.
Beneficial effect
(1) microwave ultrasonic wave that the present invention utilizes is being rapidly heated, is being evenly heated, effectively breaking hydrogen bond network and reduction instead
It answers activation energy etc. that there is good synergistic effect, not only there is apparent facilitation to the hydrolysis of cellulose, also
Reaction temperature can be reduced, shortens the reaction time, keeps the hydrolysis condition of cellulose milder.(2) tree prepared by the present invention
Rouge solid acid catalyst contains-Cl ,-SO3A variety of functional groups such as H and ferroso-ferric oxide, the absorption for not only having cellulase are fixed
The hydrolysis high efficiency of tropism and inorganic acid can catalyzing cellulose hydrolysis be effectively reduced sugar, it is living to have shown excellent catalysis
Property, and have the Magneto separate recyclability of ferroso-ferric oxide, it can be reused for several times, show good catalysis and stablize
Property.(3) raw material that the present invention uses is cheap and easy to get, and preparation process is simple, and cost of manufacture is lower, has wide industrial prospect
With market application value.
Specific embodiment
The invention proposes a kind of resin solid acid catalyst, on the main chain of this resin catalyst in addition to be connected to-Cl it
Outside, there are also sulfonic group (- SO3H substitution) has cellulose adsorption site (- Cl) and cellulose hydrolytic sites (- SO3H), can
The mode of action for imitating cellulase, so that the hydrolysis of cellulose has more directionality.With carbon-based solid acid catalyst surface
On hydroxyl compared with carboxyl ,-Cl the group on resin catalyst main chain can form stronger hydrogen with the hydroxyl on cellulose
Key makes it have stronger suction-operated to cellulose, and then helps to improve the hydrolysis efficiency of cellulose and obtaining for reduced sugar
Rate.
This resin can be by being prepared after being replaced the chlorine on chlorine-containing resins by aminobenzenesulfonic acid base portion point, this
In used chlorine-containing resins be selected from polychlorostyrene methylstyrene resin, Corvic, chlorinated polypropylene or chlorinated polyether resin；
Preferably polychlorostyrene methylstyrene resin.
In the present invention, magnetic Fe can also be embedded in the duct of above-mentioned resin3O4Nanoparticle.On the one hand, this can be made
Catalyst more easily separates catalyst after being applied to cellulose hydrolysis, avoids the tree in traditional cellulose hydrolysis
On the other hand the problem of rouge solid acid catalyst is not easily separate can use magnetic Fe3O4Work of the particle in ultrasound and microwave
With lower absorption energy, promote the progress of hydrolysis.Since the surface of nanoparticle is hydrophily, and the surface of resin is hydrophobic
Property, there is biggish exclusion power between each other, in order to further improve Fe3O4Insertion journey of the nanoparticle in duct
Degree, preferably to Fe3O4The surface of nanoparticle carries out hydrophobic modification, and the combination degree of nanoparticle can be improved, and improves hydrolysis
Reaction effect.
The preparation of above resin solid acid catalyst can be taken by the chlorine in chlorine-containing resins by p-aminobenzene sulfonic acid part
It is obtained after generation, have main steps that: chlorine-containing resins are swollen in organic solvent；P-aminophenyl sulphur is added in solution after swelling
Acid carries out substitution sulfonating reaction, washs resin after reaction；Obtained resin is added to containing nanometer Fe3O4Organic solvent,
Make to be embedded in Fe in resin3O4On；Resin is washed again, is dried.
The mass volume ratio of chlorine-containing resins and organic solvent is (10~30g): (200~400mL)；The parameter of swelling process
It is: 60~120 DEG C of temperature, 12~36h of time.Swelling uses organic solvent for dimethylformamide, tetrahydrofuran, four chlorinations
One of carbon, chloroform or toluene or several mixing, preferably dimethylformamide.
The mass ratio of chlorine-containing resins and p-aminobenzene sulfonic acid is 4:3~4:1；100~140 DEG C of the temperature of sulfonating reaction, sulphur
Change 36~72h of reaction time.
Chlorine-containing resins and nanometer Fe3O4Weight ratio be 10:1~20:1,60~120 DEG C of the temperature of reaction process, preferably
Ultrasonic wave added, ultrasonication time preferably 1~4h are added during the reaction.
Based on above resin solid acid catalyst, the process that the cellulose hydrolysis of use prepares reduced sugar includes following step
It is rapid: in ionic liquid be added cellulose, above-mentioned resin solid acid catalyst, water, be hydrolyzed reaction to get.At this
In the process, be also added into ultrasound and it is microwave-assisted, can further promote hydrolysis and and magnetic Fe3O4It acts synergistically,
Improve hydrolysis efficiency.
After the completion of hydrolysis, magnetic Fe can will be embedded with by external magnet etc.3O4Resin carry out quick separating, keep away
The problem of resin catalyst is not easily recycled after routine hydrolysis reacts is exempted from.
The preparation of 1 resin solid acid catalyst of embodiment
(1) 20g polychlorostyrene methylstyrene resin is taken to be added in 300mL dimethylformamide, 80 DEG C of stirrings are swollen 24 h；
(2) 10g p-aminobenzene sulfonic acid, 120 DEG C of stirring 48h, with dimethylformamide and nothing are added in Xiang Shangshu mixed liquor
Water-ethanol respectively washs 6 times；
(3) the polychlorostyrene methylstyrene resin after substitution sulfonation is added to 300mL and contains 3g nanometer Fe3O4Dimethyl
In formamide, 60 DEG C of stirring 2h, then ultrasound assists stirring 3h；
(4) after reaction use dimethylformamide (corresponding with selected solvent) and ethanol washing 6 times, then 60 DEG C very
The dry 12h of sky, it can obtain multi-functional resins solid acid, be abbreviated as MR-Cl-SO3H-1。
Embodiment 2
(1) 10g Corvic is taken to be added in 200mL tetrahydrofuran, 90 DEG C of stirrings are swollen 12h；
(2) 5g p-aminobenzene sulfonic acid, 100 DEG C of stirring 60h, with tetrahydrofuran and dehydrated alcohol are added in Xiang Shangshu mixed liquor
Each washing 6 times；
(3) Corvic after substitution sulfonation is added to 300mL and contains 3g nanometer Fe3O4Tetrahydrofuran in,
60 DEG C of stirring 2h, then ultrasound assists stirring 3h；
(4) tetrahydrofuran and ethanol washing 6 times are used after reaction, then 60 DEG C of vacuum drying 10h, it can obtain more
Functional resin solid acid, is abbreviated as MR-Cl-SO3H-2。
Embodiment 3
(1) 30g chlorinated polyether resin is taken to be added in 400mL chloroform, 110 DEG C of stirrings are swollen 36h；
(2) 15g p-aminobenzene sulfonic acid is added in Xiang Shangshu mixed liquor, 120 DEG C of stirring 48h are each with chloroform and dehydrated alcohol
Washing 6 times；
(3) chlorinated polyether resin after substitution sulfonation is added to 300mL and contains 3g nanometer Fe3O4Chloroform in, 60 DEG C stirring
2h, then ultrasound assists stirring 3h；
(4) chloroform and ethanol washing 6 times are used after reaction, are then dried in vacuo for 24 hours for 60 DEG C, it can obtain multi-functional
Resin solid acid, is abbreviated as MR-Cl-SO3H-3。
Embodiment 4
(1) 20g polychlorostyrene methylstyrene resin is taken to be added in 300mL dimethylformamide, 80 DEG C of stirrings are swollen 24 h；
(2) 10g p-aminobenzene sulfonic acid, 120 DEG C of stirring 48h, with dimethylformamide and nothing are added in Xiang Shangshu mixed liquor
Water-ethanol respectively washs 6 times；
(3) the polychlorostyrene methylstyrene resin after substitution sulfonation is added to 300mL and contains 3g nanometer Fe3O4Dimethyl
In formamide, 60 DEG C of stirring 2h, then ultrasound assists stirring 3h；Nanometer Fe therein3O4It has passed through oleic acid pretreatment, it will
Fe3O4It is scattered in the suspension for being configured to 5g/L in deionized water, then adjusts pH to 8.0 or so with ammonium hydroxide, after being warming up to 70 DEG C,
Oleic acid, which is added dropwise, makes oleic acid concentration 1g/L, reacts 40min after dripping, and filters out precipitating, cleaned with deionized water and ethyl alcohol,
Drying；
(4) after reaction use dimethylformamide (corresponding with selected solvent) and ethanol washing 6 times, then 60 DEG C very
The dry 12h of sky, it can obtain multi-functional resins solid acid, be abbreviated as MR-Cl-SO3H-4。
Reference examples 1
Using Amberlyst-15 cation exchange resin as solid acid catalyst as compareing, Amberlyst-15 is positive
It is in styrene divinyl copolymer with sulfonic group (- SO that ion exchange resin, which is in crosslinking,3H cation exchange tree)
Rouge does not contain chlorine in structure.
Reference examples 2
The MR-Cl-SO prepared with embodiment 13The difference of H-1 is, R-Cl-SO3Without adding in the preparation process of H resin
Enter nanometer Fe3O4 。
The hydrolysis of 5 cellulose of embodiment
Into 2g 1- butyl -3- methylimidazole villaumite be added 100mg cellulose, 50mg solid acid catalyst and
20mgH2O, in microwave ultrasonic wave reaction system, microwave frequency 2450MZH, microwave power set 300W, supersonic frequency
For 25KHZ, ultrasonic power is set as 600W, and 120 DEG C of heating stirrings are reacted 1h, are cooled to room temperature after reaction, using DNS method
Measuring total reducing sugars yield in reaction solution is.
Embodiment 6
Difference with embodiment 5 is that microwave treatment is not added.
Into 2 g 1- butyl -3- methylimidazole villaumites be added 100mg cellulose, 50mg solid acid catalyst and
20mgH2O, in ultrasonic response system, supersonic frequency 25KHZ, ultrasonic power is set as 600W, and 120 DEG C of heating stirrings are anti-
1h is answered, is cooled to room temperature after reaction, when solid acid catalyst uses MR-Cl-SO3H-1 and R-Cl-SO3When H, using DNS
It is respectively 74.2% and 63.4% that method, which measures total reducing sugars yield in reaction solution,.
From embodiment 4 and the comparison of embodiment 5 as can be seen that microwave action can significantly improve fiber in hydrolytic process
The hydrolysis efficiency of element, improves the yield of reduced sugar.In addition, microwave action is in magnetic Fe3O4When the catalyst of carrier,
The yield of reduced sugar can be made to improve, this is mainly due to magnetic nano-particles to have stronger magnetic responsiveness, can be in magnetic field
It acts on lower electromagnetic wave absorption and generates energy, promote hydrolysis.
Embodiment 7
Difference with embodiment 5 is that ultrasonic treatment is not added.
Into 2g 1- butyl -3- methylimidazole villaumite be added 100mg cellulose, 50mg solid acid catalyst and
20mgH2O, in microwave reaction system, microwave frequency 2450MHz, microwave power set 300W, 120 DEG C of heating stirrings are anti-
1h is answered, is cooled to room temperature after reaction, when solid acid catalyst uses MR-Cl-SO3H-1 and R-Cl-SO3When H, using DNS
It is respectively 76.3% and 65.9% that method, which measures total reducing sugars yield in reaction solution,.
From embodiment 4 and the comparison of embodiment 6 as can be seen that ultrasonication can significantly improve fiber in hydrolytic process
The hydrolysis efficiency of element, improves the yield of reduced sugar.In addition, ultrasonication is in magnetic Fe3O4When the catalyst of carrier, by
It will be vibrated under the action of sound field in the microbubble being originally present in liquid, when acoustic pressure reaches certain value, bubble is increased rapidly
Then rupture suddenly, i.e. generation cavitation effect, this effect can push the magnetic nano-particle in liquid to generate quickly movement,
Promote them to deposit formation microring array environment at ambient in cellulose, facilitates the hydrolysis effect for further increasing cellulose
Rate.
Claims (2)
1. nanometer Fe3O4 Carrier as resin solid acid catalyst is improving the acid catalyzed cellulose hydrolysis efficiency of resin solid
In application, it is characterised in that: the hydrolytic process is to further include in the described application under ultrasound and microwave-assisted effect
Following steps:
The preparation of resin solid acid catalyst, includes the following steps:
Step 1, chlorine-containing resins are swollen in organic solvent；
P-aminobenzene sulfonic acid is added in solution after swelling and carries out substitution sulfonating reaction, washs resin after reaction for step 2；
Step 3, the resin that step 2 is obtained are added to containing nanometer Fe3O4Organic solvent in, make to be embedded in the duct of resin
Nanometer Fe3O4；
Step 4, then resin is washed, is dried；
The chlorine-containing resins are selected from polychlorostyrene methylstyrene resin, Corvic, chlorinated polypropylene or chlorine ether tree
Rouge；
The mass volume ratio of chlorine-containing resins and organic solvent is (10~30g): (200~400mL) in step 1；Swelling process
Parameter is: 60~120 DEG C of temperature, 12~36h of time；Organic solvent is dimethylformamide, tetrahydrofuran, carbon tetrachloride, chlorine
One of imitative or toluene or several mixing；
The mass ratio of chlorine-containing resins and p-aminobenzene sulfonic acid is 4:3~4:1 in step 2；100~140 DEG C of the temperature of sulfonating reaction,
36~72h of sulfonating reaction time；Chlorine-containing resins and nanometer Fe3O4Mass ratio be 10:1~20:1；
In the step 3,60~120 DEG C of the temperature of reaction process is added ultrasonic wave added in reaction, and the ultrasonication time 1~
4h；
In the step 4, washing resin is successively with organic solvent and ethanol washing；
Cellulose hydrolysis prepares reduced sugar and includes the following steps: that cellulose, above-mentioned resin solid acid are added in ionic liquid
Catalyst, water, be hydrolyzed reaction to get；
The ionic liquid is glyoxaline ion liquid；The glyoxaline ion liquid is selected from 1- butyl -3- methylimidazole
Villaumite, 1- ethyl-3-methylimidazole villaumite, 1- butyl -3- methylimidazole acetate, in 1- ethyl-3-methylimidazole acetate
One or more of mixing；In hydrolysis reaction, be additionally added microwave and ultrasound effect, microwave frequency be 2000~
3000MHz；Microwave power set is 100~700W；Supersonic frequency is 5~40KHz；Ultrasonic power is set as 100~900W.
2. application according to claim 1, which is characterized in that 80~150 DEG C of hydrolysising reacting temperature；Hydrolysis time
0.5~4h；The additional amount of cellulose is 2~10wt% of ionic liquid dosage, water consumption be ionic liquid dosage 0.5~
2wt%；Resin solid acid catalyst levels are 20~60wt% of cellulose dosage.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638442A (en) * | 2009-08-28 | 2010-02-03 | 中国科学院西双版纳热带植物园 | Method for hydrolyzing lignocellulose |
| CN105149007A (en) * | 2015-09-21 | 2015-12-16 | 淮阴师范学院 | Preparation method of magnetic biomimetic carbon-based solid acid catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638442A (en) * | 2009-08-28 | 2010-02-03 | 中国科学院西双版纳热带植物园 | Method for hydrolyzing lignocellulose |
| CN105149007A (en) * | 2015-09-21 | 2015-12-16 | 淮阴师范学院 | Preparation method of magnetic biomimetic carbon-based solid acid catalyst |
Non-Patent Citations (1)
| Title |
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| "Hydrolysis of cellulose by cellulase-mimetic solid catalyst";Li Shuai等;《Energy Environ. Sci.》;20121231;第5卷;第6889页左栏第1段，图1，图S1，实验部分 * |
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