CN114907366A - Method for preparing LGO through catalytic pyrolysis - Google Patents
Method for preparing LGO through catalytic pyrolysis Download PDFInfo
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- CN114907366A CN114907366A CN202210670823.XA CN202210670823A CN114907366A CN 114907366 A CN114907366 A CN 114907366A CN 202210670823 A CN202210670823 A CN 202210670823A CN 114907366 A CN114907366 A CN 114907366A
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- lgo
- phosphorus
- metal oxide
- cellulose
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 46
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 229920002678 cellulose Polymers 0.000 claims abstract description 34
- 239000001913 cellulose Substances 0.000 claims abstract description 34
- 239000012263 liquid product Substances 0.000 claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000002950 deficient Effects 0.000 claims abstract 3
- 239000001301 oxygen Substances 0.000 claims abstract 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 3
- 235000010980 cellulose Nutrition 0.000 claims description 33
- 239000011964 heteropoly acid Substances 0.000 claims description 18
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 16
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 16
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 16
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 16
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical group O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 18
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- HITOXZPZGPXYHY-UJURSFKZSA-N levoglucosenone Chemical compound O=C1C=C[C@H]2CO[C@@H]1O2 HITOXZPZGPXYHY-UJURSFKZSA-N 0.000 abstract 1
- HITOXZPZGPXYHY-UHFFFAOYSA-N levoglucosenone Natural products O=C1C=CC2COC1O2 HITOXZPZGPXYHY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 15
- 239000011363 dried mixture Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 241000219000 Populus Species 0.000 description 7
- -1 phosphorus-molybdenum-aluminum Chemical compound 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UNYDVZRQKCZWEV-UHFFFAOYSA-N [Mo].[P].[Sn] Chemical compound [Mo].[P].[Sn] UNYDVZRQKCZWEV-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 241000609240 Ambelania acida Species 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 239000010905 bagasse Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YYBIUOYMDJXHEP-UHFFFAOYSA-N [Mo].[P].[Ti] Chemical compound [Mo].[P].[Ti] YYBIUOYMDJXHEP-UHFFFAOYSA-N 0.000 description 2
- MWWIFNPJDDXQLZ-UHFFFAOYSA-N [P].[W].[Zr] Chemical compound [P].[W].[Zr] MWWIFNPJDDXQLZ-UHFFFAOYSA-N 0.000 description 2
- KRNGOPGOPDDXRD-UHFFFAOYSA-N [W].[Sn].[P] Chemical compound [W].[Sn].[P] KRNGOPGOPDDXRD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DCNMIDLYWOTSGK-ZLUOBGJFSA-N (3R,4S,5S)-3,4,5,6-tetrahydroxy-2-oxohexanal Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)C(=O)C=O DCNMIDLYWOTSGK-ZLUOBGJFSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RVKVAHZFSBLGPL-UHFFFAOYSA-N [W].[Ti].[P] Chemical compound [W].[Ti].[P] RVKVAHZFSBLGPL-UHFFFAOYSA-N 0.000 description 1
- JQHFYGBZRPZIQW-UHFFFAOYSA-N [Zn].[P].[Mo] Chemical compound [Zn].[P].[Mo] JQHFYGBZRPZIQW-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 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 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of biomass energy utilization, and particularly relates to a method for preparing levoglucosenone (LGO, 1, 6-dehydration-3, 4-dideoxy-beta-D-pyranose alkene-2-ketone) by catalytic pyrolysis. The method takes phosphorus-containing composite metal oxide as a catalyst, cellulose/biomass as a raw material, adopts mechanical mixing, carries out fast pyrolysis in an inert oxygen-free or oxygen-deficient environment at 300-500 ℃, and obtains a liquid product rich in LGO through fast condensation of pyrolysis gas. In addition, the catalyst has stable performance and is easy to regenerate, and can be recycled for many times by roasting in the air.
Description
Technical Field
The invention belongs to the field of utilization of biomass energy, and particularly relates to a method for preparing LGO through catalytic pyrolysis.
Background
L-glucosone (LGO, 1, 6-anhydro-3, 4-dideoxy-beta-D-pyranose-2-one) is an important dehydrated sugar derivative formed by dehydration reaction of cellulose and partial hemicellulose in the biomass pyrolysis process. LGO has a highly active keto and acetal center, is an important raw material in the fields of chemical engineering, medical treatment and the like, and has high application and commercial values. In general, LGO can be produced from the depolymerization, dehydration, etc. of cellulose during pyrolysis. However, conventional pyrolysis products of cellulose are very complex, and yield and selectivity of LGO are extremely low, resulting in difficulty in further extraction and separation. Therefore, the cellulose/biomass pyrolysis process must be regulated by appropriate means to promote the production of LGO while suppressing the production of other products, thereby achieving high yield and high selectivity production of LGO.
Research shows that adding a proper acid catalyst in the pyrolysis process of cellulose or biomass has a remarkable promoting effect on the generation of LGO. Chinese patent application 201110134871.9 discloses a method for preparing LGO by using sulfuric acid as a core to prepare a series of liquid acids or solid acids to catalyze the pyrolysis of cellulose/biomass, but considering that the catalyst prepared by sulfuric acid has strong acidity, the loss of acid sites is easy to occur due to the existence of water vapor during the pyrolysis process, and at the same time, secondary reaction of LGO is caused, so that the LGO is difficult to exist stably. In addition, chinese patent application 201110430778.2 discloses a method for preparing LGO by catalyzing cellulose/biomass pyrolysis with magnetic solid phosphoric acid, which uses silica or alumina combined with magnetic matrix as carrier, and adopts solid phosphoric acid catalyst prepared by isovolumetric impregnation method, not only solving the problems that strong acid type catalyst pollutes environment and causes secondary reaction of LGO, but also realizing recovery of catalyst by external magnetic field, but also requiring further improvement of yield and selectivity of LGO. On the basis, the Chinese patent application 201710092409.4 discloses a method for preparing LGO by catalyzing biomass pyrolysis with biomass-based phosphoric acid activated carbon, wherein biochar is used as a carrier, phosphoric acid is impregnated to prepare a phosphoric acid activated carbon catalyst, and in a pyrolysis experiment in which poplar is used as a raw material, the yield of the obtained LGO is 10.4 wt%, but the catalyst cannot be recycled and regenerated due to the biochar carrier, so that the economic performance is restricted. In addition to the traditional catalyst, the Chinese invention patent 202011332857.9 discloses a method for preparing LGO by pyrolyzing cellulose by using waste strong acid macroporous resin Amberlyst-15, which avoids a complex catalyst preparation process and simultaneously provides a recycling mode of waste resin resources, however, considering that the yield and acidity of waste resin are unstable, the industrial requirements cannot be met. Therefore, it has been urgently required to provide a production process which is green and free from contamination, has a strong regeneration ability, and has a high LGO yield.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing LGO by catalytic pyrolysis.
The invention provides a method for preparing LGO by catalytic pyrolysis, which comprises the steps of firstly dipping a heteropoly acid or heteropoly acid salt containing phosphorus in an acidic metal oxide by an isometric dipping method, and then roasting at high temperature to obtain a composite metal oxide catalyst containing phosphorus, wherein the composite metal oxide catalyst containing phosphorus is used for catalytically pyrolyzing cellulose/biomass to realize high yield and selective preparation of LGO. In addition, the phosphorus-containing composite metal oxide has stable catalytic performance and simple regeneration mode, can be directly roasted in the air atmosphere for regeneration after being separated and recovered by a solid product, and still has catalytic capability after being recycled for multiple times.
Specifically, the method comprises the steps of taking a phosphorus-containing composite metal oxide as a catalyst, taking cellulose/biomass as a raw material, mechanically mixing the phosphorus-containing composite metal oxide and the cellulose/biomass, enabling the mass ratio of the raw material to the catalyst to meet (5: 1) - (1: 5), carrying out fast pyrolysis in an inert oxygen-free environment at 300-500 ℃, enabling the heating rate to be not lower than 100 ℃/min, enabling the pyrolysis reaction time to be not more than 60s, and carrying out fast condensation on pyrolysis gas to obtain a liquid product rich in LGO.
The preparation method of the catalyst comprises the following steps: firstly, taking a certain amount of acidic metal oxide as a carrier, then loading the phosphorus-containing heteropoly acid or heteropoly acid salt on the acidic oxide by an isometric immersion method, carrying out ultrasonic treatment for 0.5h, standing overnight, drying in an oven at 100 ℃ for 10h, and roasting at 400-550 ℃ for 5h to obtain the phosphorus-containing composite metal oxide catalyst.
Preferably, the acidic metal oxide is SnO 2 、ZnO、TiO 2 、ZrO 2 Or gamma-Al 2 O 3 。
More preferably, the acidic metal oxide is SnO 2 。
Preferably, the phosphorus-containing heteropolyacid or heteropolyacid salt is phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, ammonium phosphomolybdate or ammonium phosphotungstate.
More preferably, the phosphorus-containing heteropolyacid or heteropolyacid salt is phosphomolybdic acid or phosphotungstic acid.
Preferably, the phosphorus-containing heteropoly acid or heteropoly acid salt impregnated in the phosphorus-containing composite metal oxide catalyst accounts for 20-80% by mass.
More preferably, the impregnated phosphorus-containing heteropoly acid or heteropoly acid salt accounts for 45-55% by mass.
The cellulose comprises microcrystalline cellulose or alpha-cellulose; the biomass comprises wood, crop straw or herbaceous biomass. The raw materials should be crushed to a particle size of less than 1mm before use.
The inert oxygen-free condition means that the carrier gas in the reaction is nitrogen, argon or helium.
The invention has the beneficial effects that:
the invention takes the phosphorus-containing composite metal oxide as a catalyst, and the phosphorus-containing composite metal oxide is pyrolyzed at a medium and low temperature after being mechanically mixed with cellulose/biomass, so that a liquid product rich in LGO can be obtained. Studies have shown that acidic catalysts with phosphorus-containing active sites can promote the formation of LGO. The phosphorus-containing acidic group of the catalyst can promote the formation of an unsaturated structure and a bicyclic structure, and the acidity of the acidic oxide has certain functions of promoting the depolymerization and dehydration of cellulose. In addition, Mo of the catalyst 6+ Or W 6+ The species has good deoxidizing and hydrogenating capacity, the general deoxidizing reaction activity of the oxygen functional group is C-OH > C ═ O > C-O-C, the species plays a key role in reducing the bond energy of C-O and promoting the depolymerization of cellulose, and is favorable for promoting the secondary conversion of the main pyrolysis product of the cellulose, namely, levoglucosan, to generate LGO. The above numerous advantages together enable the high yield and selective production of LGO.
The invention also has the beneficial effect of avoiding using a catalyst with stronger acidity. The strong acid catalyst not only causes the problems of environmental pollution and the like, but also more importantly, the loss of acid sites is easy to occur due to the existence of water vapor in the pyrolysis process, and the secondary reaction of LGO is caused, so that the LGO is difficult to exist stably, the loss of LGO is caused, and great difficulty is brought to the preservation of the pyrolysis liquid product. The phosphorus-containing composite metal oxide catalyst mainly depends on proper amount of phosphorus-containing acidic sites (PO) 4 3- Species and P intercalated in acidic oxide support 5+ Species), various metal oxides inside the catalyst are combined to play a multi-aspect synergistic effect, and LGO high-yield and high-selectivity preparation is realized.
In addition, the phosphorus-containing composite metal oxide catalyst is simple to regenerate, after catalytic pyrolysis reaction, regeneration can be realized in a roasting mode in the air atmosphere, and the catalytic effect is not obviously reduced after the catalyst is recycled for multiple times. Realizes the environment-friendly, low-cost and high-efficiency preparation of LGO.
Detailed Description
The present invention provides a method for preparing LGO by catalytic pyrolysis, and the invention is further described below with reference to specific embodiments. It should be understood that the following detailed description is illustrative of the invention only and is not intended to limit the scope of the invention.
The liquid product yield calculation method in the following examples is as follows:
liquid product yield ═ mass of liquid product collected ÷ mass of starting material × 100%.
In the following examples, the content of LGO in the sample was analyzed by a gas chromatograph/mass spectrometer and quantified by an external standard method, and the LGO yield was calculated as follows:
the yield of LGO is ═ mass of LGO ÷ mass of starting material × 100%.
The percentages in the following examples are by mass unless otherwise specified.
The experimental procedures in the following examples are conventional unless otherwise specified.
Example 1
50g SnO were weighed out separately 2 Mixing with 20g of phosphomolybdic acid, dissolving phosphomolybdic acid in a certain amount of deionized water to prepare a solution, and loading the phosphomolybdic acid on SnO by adopting an isometric immersion method 2 And carrying out ultrasonic treatment for 0.5h, standing overnight, then placing the mixture in a 100 ℃ oven for drying for 10h, taking out the dried mixture, and roasting the dried mixture at the temperature of 550 ℃ for 5h to obtain the phosphorus-molybdenum-tin composite metal oxide.
Taking 10g of the prepared phosphorus-molybdenum-tin composite metal oxide, taking commercial microcrystalline cellulose as a raw material (with the average particle size of 0.09mm), mechanically mixing the commercial microcrystalline cellulose and the commercial microcrystalline cellulose, controlling the mass ratio of the cellulose to the catalyst to be 1: 1, then pyrolyzing the mixture for 30s in nitrogen atmosphere at 350 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 52.8%, and the LGO content in the LGO is analyzed by a gas chromatography-mass spectrometer, and the LGO yield is calculated to be 18.7%.
Example 2
Respectively weighing 50g of ZnO and 30g of phosphomolybdic acid, dissolving phosphomolybdic acid in a certain amount of deionized water to prepare a solution, loading phosphomolybdic acid on ZnO by adopting an isometric immersion method, carrying out ultrasonic treatment for 0.5h, standing overnight, then placing in a 100 ℃ oven for drying for 10h, taking out, and roasting at the temperature of 450 ℃ for 5h to obtain the phosphomolybdic-zinc composite metal oxide.
Taking 10g of the prepared phosphorus-molybdenum-zinc composite metal oxide, taking alpha-cellulose as a raw material (with the average particle size of 0.25mm), mechanically mixing the alpha-cellulose and the catalyst, controlling the mass ratio of the cellulose to the catalyst to be 5: 1, then pyrolyzing the mixture for 30s in argon atmosphere at 320 ℃ (the heating rate is not lower than 100 ℃/min), obtaining the liquid product with the yield of 49.5%, analyzing the LGO content in the liquid product by a gas chromatography-mass spectrometer, and calculating to obtain the LGO yield of 15.6%.
Example 3
Respectively weighing 50g of gamma-Al 2 O 3 Mixing with 25g of phosphomolybdic acid, dissolving phosphomolybdic acid in a certain amount of deionized water to prepare a solution, and loading the phosphomolybdic acid on gamma-Al by adopting an isometric immersion method 2 O 3 Ultrasonic treating for 0.5 hr, standing overnight, drying in 100 deg.C oven for 10 hr, collectingAnd roasting at 400 ℃ for 5 hours to obtain the phosphorus-molybdenum-aluminum composite metal oxide.
Taking 10g of each prepared phosphorus-molybdenum-aluminum composite metal oxide, taking commercial microcrystalline cellulose as a raw material (with the average particle size of 0.05mm), mechanically mixing the commercial microcrystalline cellulose and the commercial microcrystalline cellulose, controlling the mass ratio of the cellulose to the catalyst to be 1: 3, then pyrolyzing the mixture for 40s in a nitrogen atmosphere at 400 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 57.1%, and the content of LGO in the liquid product is analyzed by a gas chromatography/mass spectrometer, and the yield of the LGO is calculated to be 17.9%.
Example 4
50g SnO were weighed out separately 2 Mixing with 25g of phosphotungstic acid, dissolving the phosphotungstic acid in a certain amount of deionized water to prepare a solution, and loading the phosphotungstic acid on SnO by adopting an isometric impregnation method 2 And carrying out ultrasonic treatment for 0.5h, standing overnight, then placing the mixture in a 100 ℃ oven for drying for 10h, taking out the dried mixture, and roasting the dried mixture at the temperature of 550 ℃ for 5h to obtain the phosphorus-tungsten-tin composite metal oxide.
Taking 10g of the phosphorus-tungsten-tin composite metal oxide prepared above, taking alpha-cellulose as a raw material (average particle size is 0.25mm), mechanically mixing the alpha-cellulose and the cellulose, and controlling the mass ratio of the cellulose to the catalyst to be 1: 2, then pyrolyzing the mixture for 60s under the helium atmosphere at 350 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 53.2%, and the LGO content in the liquid product is analyzed by a gas chromatography-mass spectrometer, and the yield of the LGO is calculated to be 17.5%.
Example 5
Respectively weighing 50g of gamma-Al 2 O 3 Mixing with 20g of phosphotungstic acid, dissolving phosphomolybdic acid in a certain amount of deionized water to prepare a solution, and loading the phosphomolybdic acid on gamma-Al by adopting an isometric immersion method 2 O 3 And carrying out ultrasonic treatment for 0.5h, standing overnight, then placing the mixture in a 100 ℃ oven for drying for 10h, taking out the dried mixture, and roasting the dried mixture at the temperature of 550 ℃ for 5h to obtain the phosphorus-tungsten-aluminum composite metal oxide.
Taking 10g of the phosphorus-tungsten-aluminum composite metal oxide prepared above, taking commercial microcrystalline cellulose as a raw material (with an average particle size of 0.05mm), mechanically mixing the two, controlling the mass ratio of the cellulose to the catalyst to be 1: 1, then pyrolyzing the mixture for 20s in a nitrogen atmosphere at 500 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 70.3%, and the content of LGO in the liquid product is analyzed by a gas chromatography/mass spectrometer, and the yield of the LGO is calculated to be 14.1%.
Example 6
50g of TiO were weighed separately 2 Mixing with 40g of ammonium phosphomolybdate, dissolving the ammonium phosphomolybdate in a certain amount of deionized water to prepare a solution, and loading phosphotungstic acid on TiO by adopting an isometric immersion method 2 And carrying out ultrasonic treatment for 0.5h, standing overnight, then placing the mixture in a 100 ℃ oven for drying for 10h, taking out the dried mixture, and roasting the dried mixture at the temperature of 500 ℃ for 5h to obtain the phosphorus-tungsten-titanium composite metal oxide.
Taking 10g of the prepared phosphorus-molybdenum-titanium composite metal oxide, taking alpha-cellulose as a raw material (with the average particle size of 0.25mm), mechanically mixing the alpha-cellulose and the cellulose, controlling the mass ratio of the cellulose to the catalyst to be 1: 5, then pyrolyzing the mixture for 60s in a nitrogen atmosphere at 300 ℃ (the heating rate is not lower than 100 ℃/min), obtaining a liquid product with the yield of 47.9%, analyzing the LGO content in the liquid product by a gas chromatography-mass spectrometer, and calculating to obtain the LGO yield of 16.8%.
Example 7
50g of ZrO were weighed out separately 2 Mixing with 10g of ammonium phosphotungstate, dissolving the ammonium phosphotungstate in a certain amount of deionized water to prepare a solution, and loading the ZrO with the phosphotungstic acid by adopting an isometric immersion method 2 And carrying out ultrasonic treatment for 0.5h, standing overnight, then placing the mixture in a 100 ℃ oven for drying for 10h, taking out the dried mixture, and roasting the dried mixture at the temperature of 550 ℃ for 5h to obtain the phosphorus-tungsten-zirconium composite metal oxide.
Taking 10g of each phosphorus-tungsten-zirconium composite metal oxide prepared in the above way, taking commercial microcrystalline cellulose as a raw material (with the average particle size of 0.05mm), mechanically mixing the two, controlling the mass ratio of the cellulose to the catalyst to be 2: 1, then pyrolyzing the mixture for 20s in a nitrogen atmosphere at 370 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 52.3%, and the content of LGO in the liquid product is analyzed by a gas chromatography/mass spectrometer, and the yield of the LGO is calculated to be 17.3%.
Example 8
50g SnO were weighed out separately 2 With 30g of phosphomolybdotungstic acid,dissolving the phosphomolybdotungstic acid in a certain amount of deionized water to prepare a solution, and loading the phosphomolybdotungstic acid on SnO by adopting an isometric impregnation method 2 And carrying out ultrasonic treatment for 0.5h, standing overnight, then placing the mixture in a 100 ℃ oven for drying for 10h, taking out the dried mixture, and roasting the dried mixture at the temperature of 550 ℃ for 5h to obtain the phosphorus-molybdenum-tungsten-tin composite metal oxide.
Taking 10g of the prepared phosphorus-molybdenum-tungsten-tin composite metal oxide, taking commercial microcrystalline cellulose as a raw material (with the average particle size of 0.05mm), mechanically mixing the commercial microcrystalline cellulose and the commercial microcrystalline cellulose, controlling the mass ratio of the cellulose to the catalyst to be 1: 2, then pyrolyzing the mixture for 30s in nitrogen atmosphere at 350 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 48.2%, and the content of LGO in the liquid product is analyzed by a gas chromatography/mass spectrometer, and the yield of the LGO is calculated to be 15.1%.
Example 9
And (3) directly roasting the solid product obtained in the pyrolysis in the embodiment 1 at the temperature of 550 ℃ for 1h in the air atmosphere to obtain the regenerated phosphorus-molybdenum-tin composite metal oxide catalyst. The method comprises the steps of taking commercial microcrystalline cellulose as a raw material (with the average particle size of 0.09mm), mechanically mixing the commercial microcrystalline cellulose and the catalyst in a mass ratio of 1: 1, pyrolyzing the mixture for 30s in a nitrogen atmosphere at 350 ℃ (the temperature rise rate is not lower than 100 ℃/min), obtaining a liquid product with the yield of 50.9%, and analyzing the content of LGO in the liquid product through a gas chromatography/mass spectrometer, wherein the LGO yield is 17.1% by calculation.
Example 10
10g of the phosphorus-molybdenum-tin composite metal oxide prepared in example 1 was taken, poplar was used as a raw material (average particle size 0.1mm), the poplar and the catalyst were mechanically mixed, the mass ratio of the poplar to the catalyst was controlled at 1: 5, the mixture was pyrolyzed for 30s in an argon atmosphere at 320 ℃ (with a temperature rise rate of not less than 100 ℃/min), the yield of the obtained liquid product was 47.6%, the LGO content therein was analyzed by a gas chromatography-mass spectrometer, and the yield of LGO was calculated to be 10.2%.
Example 11
10g of the phosphomolybdic zinc composite metal oxide prepared in example 2 was taken, bagasse was used as a raw material (average particle size 0.1mm), the bagasse and the catalyst were mechanically mixed, the mass ratio of the bagasse to the catalyst was controlled at 2: 1, and then the mixture was pyrolyzed at 300 ℃ (temperature rise rate not lower than 100 ℃/min) for 40 seconds in a nitrogen atmosphere, and the yield of the obtained liquid product was 41.5%, and the LGO content therein was analyzed by a gas chromatography-mass spectrometer, and the calculated yield of the LGO was 8.9%.
Example 12
10g of the phosphomolybdic aluminum composite metal oxide prepared in example 3 was taken, pine wood was used as a raw material (average particle size 0.1mm), the two were mechanically mixed, the mass ratio of the pine wood to the catalyst was controlled at 1: 5, then the mixture was pyrolyzed at 350 ℃ (temperature rise rate not lower than 100 ℃/min) for 60 seconds in a nitrogen atmosphere, the yield of the obtained liquid product was 52.2%, the LGO content therein was analyzed by a gas chromatography-mass spectrometer, and the calculated LGO yield was 9.5%.
Example 13
10g of the phosphorus-tungsten-aluminum composite metal oxide prepared in example 5 was taken, poplar was used as a raw material (average particle size 0.1mm), the poplar and the catalyst were mechanically mixed, the mass ratio of the poplar to the catalyst was controlled to 5: 1, the mixture was pyrolyzed for 40s in a nitrogen atmosphere at 320 ℃ (temperature rise rate not lower than 100 ℃/min), the yield of the obtained liquid product was 42.3%, the LGO content therein was analyzed by a gas chromatography-mass spectrometer, and the yield of LGO was calculated to be 9.6%.
Example 14
Taking 10g of the phosphorus-molybdenum-titanium composite metal oxide prepared in the example 6, taking wheat straws as a raw material (with an average particle size of 0.1mm), mechanically mixing the wheat straws and the catalyst, controlling the mass ratio of the wheat straws to the catalyst to be 1: 4, then pyrolyzing the mixture for 30s in a nitrogen atmosphere at 350 ℃ (the heating rate is not lower than 100 ℃/min), wherein the yield of the obtained liquid product is 53.8%, and the LGO content in the liquid product is analyzed by a gas chromatography-mass spectrometer, and the LGO yield is 8.6% by calculation.
In the above embodiments, the pyrolysis raw material includes cellulose raw materials such as microcrystalline cellulose and α -cellulose, and biomass raw materials such as wood, crop straw or herbs, and the cellulose content in the biomass raw material is about 30-50%, so that the LGO yield is reduced in comparison with the embodiment using cellulose as a raw material, but the description of the embodiment of the present invention is not affected.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A method for preparing LGO by catalytic pyrolysis is characterized in that a phosphorus-containing composite metal oxide is used as a catalyst, cellulose/biomass is used as a raw material, and the phosphorus-containing composite metal oxide and the cellulose/biomass are mechanically mixed; the mass ratio of the cellulose/biomass to the catalyst is (5: 1) - (1: 5), the fast pyrolysis is carried out in an inert oxygen-free or oxygen-deficient environment at the temperature of 300-500 ℃, the heating rate of the pyrolysis reaction is not lower than 100 ℃/min, the pyrolysis reaction time is not more than 60s, and the pyrolysis gas is fast condensed to obtain a liquid product rich in LGO.
2. A method of catalytic pyrolysis for producing LGO according to claim 1, wherein the phosphorus-containing composite metal oxide catalyst is produced by: firstly, taking a certain amount of acidic metal oxide as a carrier, then loading a heteropoly acid or heteropoly acid salt containing phosphorus on the acidic oxide by an isometric immersion method, carrying out ultrasonic treatment and drying, and then roasting at the temperature of 400-550 ℃ for 5 hours to obtain the composite metal oxide catalyst containing phosphorus.
3. A process for producing LGO by catalytic pyrolysis according to claim 2, wherein the acidic metal oxide is SnO 2 、ZnO、TiO 2 、ZrO 2 Or gamma-Al 2 O 3 。
4. A process according to claim 2, wherein said phosphorus-containing heteropolyacid or heteropolyacid salt is phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, ammonium phosphomolybdate or ammonium phosphotungstate.
5. The method for preparing LGO through catalytic pyrolysis according to claim 2, wherein the phosphorus-containing heteropoly acid or heteropoly acid salt is impregnated in the phosphorus-containing composite metal oxide catalyst and accounts for 20-80% by mass.
6. A process for catalytic pyrolysis of each LGO according to claim 1, wherein the cellulose comprises microcrystalline cellulose or α -cellulose.
7. A process for producing LGO by catalytic pyrolysis according to claim 1, wherein the biomass comprises wood, crop straw, or herbaceous biomass.
8. The process for producing LGO according to claim 1, wherein said inert oxygen-free or oxygen-deficient conditions are conditions in which the carrier gas in the reaction is nitrogen, argon or helium.
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