AU2023201416A1 - Method for preparing levoglucosan by catalytic pyrolysis of celluloses - Google Patents
Method for preparing levoglucosan by catalytic pyrolysis of celluloses Download PDFInfo
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- celluloses
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- levoglucosan
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 28
- 235000010980 cellulose Nutrition 0.000 title claims abstract description 27
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 31
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 17
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 17
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 17
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 17
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 230000009920 chelation Effects 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000011973 solid acid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 5
- 239000000047 product Substances 0.000 abstract description 6
- 239000001913 cellulose Substances 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 239000012265 solid product Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910017112 Fe—C Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- HITOXZPZGPXYHY-UJURSFKZSA-N levoglucosenone Chemical compound O=C1C=C[C@H]2CO[C@@H]1O2 HITOXZPZGPXYHY-UJURSFKZSA-N 0.000 description 1
- HITOXZPZGPXYHY-UHFFFAOYSA-N levoglucosenone Natural products O=C1C=CC2COC1O2 HITOXZPZGPXYHY-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sustainable Development (AREA)
- Catalysts (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention discloses a method for preparing levoglucosan by catalytic pyrolysis
of celluloses. Zinc oxide is added into a sodium carboxymethylcellulose solution to form a
mixture; the mixture is added into a ferric sulfate solution for chelation to produce precipitates;
the precipitates are filtered and collected, washed with deionized water, dried, and then calcined
in an inert atmosphere to obtain a magnetic solid acid-base amphoteric catalyst. The magnetic
solid acid-base amphoteric catalyst Znnl@Fe-CT and cellulose are mechanically mixed, and then
rapidly pyrolyzed at 200-600°C; and a resulting pyrolysis gas is condensed to obtain a
levoglucosan-enriched liquid product. The magnetic solid acid-base amphoteric catalyst
Znn@Fe-CT can effectively promote the directional pyrolysis of the celluloses at a lower
temperature; the yield of the levoglucosan in the product is high; and the catalyst can be very
conveniently recovered from a solid product by using a permanent magnet, and can be used
cyclically multiple times.
Description
[0001] The present invention belongs to the field of technologies for production of environment friendly new energy, and in particular relates to a method for preparing levoglucosan by catalytic pyrolysis of celluloses.
[0002] Celluloses react at around 500°C for a very short time (about 2 seconds) and are rapidly pyrolyzed to produce levoglucosan (1,6-anhydro-p-D-glucopyranose). The levoglucosan is an important monomer for synthesis of stereo-compounds, and can be used as chiral synthons to synthesize oligosaccharides, high polymers, resins, drugs, and related products. Microorganisms can directly or indirectly use the levoglucosan as a substrate to produce itaconic acid, citric acid, lipids, ethanol, etc. It is a very advantageous and promising method to prepare the levoglucosan by rapid pyrolysis of biomasses.
[0003] Generally, the biomasses are impregnated to load a liquid acid for catalytic pyrolysis. At present, liquid acids for the catalytic pyrolysis of biomasses mainly include phosphoric acid and sulfuric acid. Although these liquid acids can significantly change the distribution of pyrolysis products of the biomasses to obtain dehydrated saccharide products, impregnation with the liquid acids easily results in a large amount of waste liquid that is difficult to handle. Moreover, the liquid acids are prone to corroding equipment during experiments, and cannot be recycled after the experiments, leading to high experimental cost and cumbersome experimental operation, which is not conducive to large-scale application. Compared with the liquid acids, solid acid catalysts have the advantages of recyclability and low pollution. Although many solid acids have achieved good results in catalyzing the pyrolysis of biomasses, the yield of a target product among pyrolysis products resulting from the catalysis by these solid acids is still low. Furthermore, the acidity of liquid and solid acids used in relevant researches is difficult to control. Once the catalyst is slightly stronger in acidity, the further dehydration of levoglucosan will be caused to boost the formation of levoglucosenone and other by-products.
[0004] In view of the defects of the prior art, an object of the present invention is to provide a magnetic solid acid-base amphoteric catalyst, by which the pyrolysis of the celluloses can be catalyzed at a lower temperature to prepare levoglucosan at high efficiency.
[0005] The magnetic solid acid-base amphoteric catalyst of the present invention is prepared by a method including the steps of:
[0006] adding zinc oxide into a sodium carboxymethylcellulose solution to form a mixture; adding the mixture into a ferric sulfate solution for chelation to produce precipitates; filtering and collecting the precipitates; washing the precipitates with deionized water; drying the precipitates; and then calcining the dried precipitates in an inert atmosphere to obtain the magnetic solid acid-base amphoteric catalyst.
[0007] Preferably, a mass ratio of the sodium carboxymethylcellulose used to the zinc oxide used is 1:1-2.
[0008] Preferably, adding the mixture into the ferric sulfate solution for chelation to produce the precipitates includes performing chelation under a constant temperature condition at 70°C.
[0009] Preferably, the drying includes drying in a vacuum drying oven at 105°C.
[0010] Preferably, the calcining is performed at 300-600°C for 2 hours.
[0011] Preferably, the inert atmosphere is a nitrogen atmosphere.
[0012] A second object of the present invention is to provide a method for preparing levoglucosan by catalytic pyrolysis of celluloses. The method includes the steps of: mixing the aforementioned magnetic solid acid-base amphoteric catalyst with the celluloses; and performing pyrolysis in a pyrolysis reactor to obtain the levoglucosan. After the reaction ends, the magnetic solid acid-base amphoteric catalyst is recovered by a permanent magnet, and can be recycled for the catalyzed pyrolysis reaction of the celluloses.
[0013] Preferably, the celluloses are microcrystalline celluloses, and are crushed and sieved through a 200-mesh screen prior to use.
[0014] Preferably, a pyrolysis temperature is 200-600°C.
[0015] Preferably, the celluloses and the magnetic solid acid-base amphoteric catalyst are mixed at a mass ratio of 1:1-3.
[00161 Preferably, the pyrolysis is performed in an atmosphere of nitrogen or argon.
[0017] Preferably, the pyrolysis is performed for 1-360 s.
[0018] Further preferably, the pyrolysis is performed at a temperature of 290°C for 20 s.
[0019] Compared with the prior art, the present invention has the following advantages:
[0020] 1. the use of the magnetic solid acid-base amphoteric catalyst Zn@Fe-CTin the present application can promote the directional pyrolysis of the celluloses at a milder condition to convert the celluloses to the levoglucosan; and
[0021] 2. with respect to a conventional solid or liquid acid catalyst, the magnetic solid acid base amphoteric catalyst can be recycled, showing better economy and environment friendliness.
[0022] The present invention is further explained below in combination with embodiments.
[0023] For better understanding of the present invention, the content of the present invention is further explained by the following exemplary embodiments, but is not limited thereto.
[0024] Contrast experiment 1
[00251 A certain amount of celluloses was weighed out and then rapidly pyrolyzed in a rapid pyrolyzer for 360 s at a pyrolysis temperature of 300°C in a pyrolysis atmosphere of nitrogen, with a heating rate of10°C/ms; and the conversion rate from the celluloses to levoglucosan was 15.0%.
[0026] Contrast experiment 2
[0027] A certain amount of celluloses was weighed out and then rapidly pyrolyzed in a rapid pyrolyzer at a pyrolysis temperature of 500°C in a pyrolysis atmosphere of nitrogen for 20 s, with a heating rate of 10°C/ms; and the conversion rate from the celluloses to levoglucosan was 60.0%.
[0028] Embodiment 1
[0029] Under heating conditions, 4 g of sodium carboxymethylcellulose was weighed out, dissolved in 200 mL of deionized water, and stirred with a glass rod until a clear viscous liquid was obtained, whereby a sodium carboxymethylcellulose solution was prepared. Subsequently, 4 g of solid granules of zinc oxide was weighed out, added into the sodium carboxymethycellulose solution, and stirred with the glass rod to mix them well. 79.98 g of ferric sulfate and 200 mL of deionized water were weighed out, and added into a heat-collection type constant-temperature heating magnetic stirrer to prepare a ferric sulfate solution in an oil bath pan at a constant temperature of 70°C over magnetic stirring. While constant temperature and magnetic stirring were kept, the mixed sodium carboxymethylcellulose solution was added dropwise to the ferric sulfate solution with a 5 mL syringe for 3-hour chelation to produce precipitates. The precipitates were filtered and washed with deionized water till PH was approximately equal to 7. After the precipitates were dried in a vacuum drying oven at 105°C, the resulting dry solids were calcined in a high-temperature box-type furnace at 600°C in a nitrogen atmosphere for 2 hours, and the calcined solids were ground and sieved through a 200 mesh screen to obtain a magnetic solid acid-base amphthermic catalyst Zn4@Fe-C 600. At a mass ratio of 1:1, celluloses and the Zn4@Fe-C 600 were weighed at a proper amount, and pyrolyzed for 360 s at a pyrolysis temperature of 500°C in a pyrolysis atmosphere of nitrogen, and the yield of levoglucosan was 35%.
[0030] Embodiment 2
[0031] Under heating conditions, 4 g of sodium carboxymethylcellulose was weighed out, dissolved in 200 mL of deionized water, and stirred with a glass rod until a clear viscous liquid was obtained, whereby a sodium carboxymethylcellulose solution was prepared. Subsequently, 8 g of solid granules of zinc oxide was weighed out, added into the sodium carboxymethylcellulose solution, and stirred with the glass rod to mix them well. 79.98 g of ferric sulfate and 200 mL of deionized water were weighed out, and added into a heat-collection type constant-temperature heating magnetic stirrer to prepare a ferric sulfate solution in an oil bath pan at a constant temperature of 70°C over magnetic stirring. While constant temperature and magnetic stirring were kept, the mixed sodium carboxymethycellulose solution was added dropwise to the ferric sulfate solution with a 5 mL syringe for 3-hour chelation to produce precipitates. The precipitates were filtered and washed with deionized water till PH was approximately equal to 7. After the precipitates were dried in a vacuum drying oven at 105°C, the resulting dry solids were calcined in a high-temperature box-type furnace at 500°C in a nitrogen atmosphere for 2 hours, and the calcined solids were ground and sieved through a 200 mesh screen to obtain a magnetic solid acid-base amphthermic catalyst Zn4@Fe-C5 oo. At a mass ratio of 1:1, celluloses and the Zn4@Fe-C 5 00were weighed at a proper amount, and pyrolyzed for 360 s at a pyrolysis temperature of 600°C in a pyrolysis atmosphere of argon, and the yield of levoglucosan was 28%.
[0032] Embodiment 3
[0033] Under heating conditions, 4 g of sodium carboxymethylcellulose was weighed out, dissolved in 200 mL of deionized water, and stirred with a glass rod until a clear viscous liquid was obtained, whereby a sodium carboxymethylcellulose solution was prepared. Subsequently, 4 g of solid granules of zinc oxide was weighed out, added into the sodium carboxymethylcellulose solution, and stirred with the glass rod to mix them well. 79.98 g of ferric sulfate and 200 mL of deionized water were weighed out, and added into a heat-collection type constant-temperature heating magnetic stirrer to prepare a ferric sulfate solution in an oil bath pan at a constant temperature of 70°C over magnetic stirring. While constant temperature and magnetic stirring were kept, the mixed sodium carboxymethycellulose solution was added dropwise to the ferric sulfate solution with a 5 mL syringe for 3-hour chelation to produce precipitates. The precipitates were filtered and washed with deionized water till PH was approximately equal to 7. After the precipitates were dried in a vacuum drying oven at 105°C, the resulting dry solids were calcined in a high-temperature box-type furnace at 500°C in a nitrogen atmosphere for 2 hours, and the calcined solids were ground and sieved through a 200 mesh screen to obtain a magnetic solid acid-base amphthermic catalyst Zn4@Fe-C5 oo. At a mass ratio of 1:3, celluloses and the Zn 4 @Fe-C 5 oowere weighed at a proper amount, and pyrolyzed for 1 s at a pyrolysis temperature of 200°C in a pyrolysis atmosphere of nitrogen, and the yield of levoglucosan was 3%.
[0034] Embodiment 4
[0035] Under heating conditions, 4 g of sodium carboxymethylcellulose was weighed out, dissolved in 200 mL of deionized water, and stirred with a glass rod until a clear viscous liquid was obtained, whereby a sodium carboxymethylcellulose solution was prepared. Subsequently, 4 g of solid granules of zinc oxide was weighed out, added into the sodium carboxymethylcellulose solution, and stirred with the glass rod to mix them well. 79.98 g of ferric sulfate and 200 mL of deionized water were weighed out, and added into a heat-collection type constant-temperature heating magnetic stirrer to prepare a ferric sulfate solution in an oil bath pan at a constant temperature of 70°C over magnetic stirring. While constant temperature and magnetic stirring were kept, the mixed sodium carboxymethycellulose solution was added dropwise to the ferric sulfate solution with a 5 mL syringe for 3-hour chelation to produce precipitates. The precipitates were filtered and washed with deionized water till PH was approximately equal to 7. After the precipitates were dried in a vacuum drying oven at 105°C, the resulting dry solids were calcined in a high-temperature box-type furnace at 500°C in a nitrogen atmosphere for 2 hours, and the calcined solids were ground and sieved through a 200 mesh screen to obtain a magnetic solid acid-base amphthermic catalyst Zn4@Fe-C5 oo. At a mass ratio of 1:3, celluloses and the Zn4@Fe-C5 00 were weighed at a proper amount, and pyrolyzed at a pyrolysis temperature of 290°C in a pyrolysis atmosphere of nitrogen for 20 s, and the yield of levoglucosan was 84%. After the reaction ended, the magnetic solid acid-base catalyst was recovered by a permanent magnet. The recovered magnetic solid acid-base catalyst was mixed with celluloses again for experiments in cycles. After five cycles, the yield of levoglucosan was still up to 64.2 wt%.
[0036] Although the above embodiments of the present invention are described, the present invention is not limited to the above specific embodiments and application fields, the above specific embodiments are merely for schematic and instructive purposes, rather than a restrictive purpose. Under the teaching of the Description, those of ordinary skills in the art may also create a variety of forms without departing from the scope claimed by the claims of the present invention, and these forms should be included within the protection of the present invention.
Claims (10)
- CLAIMS What is claimed is: 1. A preparation method for a magnetic solid acid-base amphoteric catalyst, comprising the steps of: adding zinc oxide into a sodium carboxymethylcellulose solution to form a mixture; adding the mixture into a ferric sulfate solution for chelation to produce precipitates; filtering and collecting the precipitates; washing the precipitates with deionized water; drying the precipitates; and then calcining the dried precipitates in an inert atmosphere to obtain the magnetic solid acid base amphoteric catalyst.
- 2. The preparation method according to claim 1, wherein a mass ratio of the sodium carboxymethylcellulose used to the zinc oxide used is 1:1-2.
- 3. The preparation method according to claim 1, wherein adding the mixture into the ferric sulfate solution for chelation to produce the precipitates comprises performing chelation under a constant temperature condition at 70°C, and the drying comprises drying in a vacuum drying oven at 105°C.
- 4. The preparation method according to claim 1, wherein the calcining comprises calcining at 300-600°C for 2 hours; and the inert atmosphere is a nitrogen atmosphere.
- 5. A magnetic solid acid-base amphoteric catalyst prepared with the preparation method according to claim 1, 2, 3 or 4.
- 6. A method for preparing levoglucosan by catalytic pyrolysis of celluloses, comprising the steps of: mixing the magnetic solid acid-base amphoteric catalyst according to claim 5 with the celluloses; and performing pyrolysis in a pyrolysis reactor to obtain the levoglucosan.
- 7. The method according to claim 6, wherein the celluloses are microcrystalline celluloses, and are crushed and sieved through a 200-mesh screen prior to use.
- 8. The method according to claim 6, wherein the pyrolysis is performed at a temperature of 200-600°C in an atmosphere of nitrogen or argon for 1-360 s.
- 9. The method according to claim 6, wherein the celluloses and the magnetic solid acid-base amphoteric catalyst are mixed at a mass ratio of 1:1-3.
- 10. The method according to claim 8, wherein the pyrolysis is performed at a temperature of 290°C for 20 s.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210231712.9 | 2022-03-10 | ||
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