CN116656421B - Method for preparing bio-oil by biomass pyrolysis - Google Patents
Method for preparing bio-oil by biomass pyrolysis Download PDFInfo
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- CN116656421B CN116656421B CN202310548819.0A CN202310548819A CN116656421B CN 116656421 B CN116656421 B CN 116656421B CN 202310548819 A CN202310548819 A CN 202310548819A CN 116656421 B CN116656421 B CN 116656421B
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- 239000002028 Biomass Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000012075 bio-oil Substances 0.000 title claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims abstract description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002608 ionic liquid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- -1 1-butyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 12
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 12
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 12
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical group [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 10
- 239000010902 straw Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- NWIICCMMNLMQMY-UHFFFAOYSA-K 1-butyl-3-methylimidazol-3-ium phosphate Chemical compound [O-]P([O-])([O-])=O.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1 NWIICCMMNLMQMY-UHFFFAOYSA-K 0.000 description 1
- BSKSXTBYXTZWFI-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;acetate Chemical group CC([O-])=O.CCCC[N+]=1C=CN(C)C=1 BSKSXTBYXTZWFI-UHFFFAOYSA-M 0.000 description 1
- XUHHZNLAPUWRHH-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCCCN1CN(C)C=C1 XUHHZNLAPUWRHH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- MAZJFWHKKPFVND-UHFFFAOYSA-N aluminum propan-2-ol propan-2-olate Chemical compound [Al+3].CC(C)O.CC(C)[O-].CC(C)[O-].CC(C)[O-] MAZJFWHKKPFVND-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/12—Production of fats or fatty oils from raw materials by melting out
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/02—Pretreatment
- C11B1/04—Pretreatment of vegetable raw material
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of biomass resource utilization, in particular to a method for preparing bio-oil by biomass pyrolysis, which comprises the steps of soaking biomass raw materials in potassium phosphate solution, uniformly mixing the soaked biomass raw materials with a catalyst, heating the mixture to 500-580 ℃ for catalytic pyrolysis, wherein the catalyst comprises metal oxide.
Description
Technical Field
The invention relates to the technical field of biomass resource utilization, in particular to a method for preparing bio-oil by biomass pyrolysis.
Background
The long-term use of fossil fuels such as petroleum, coal, natural gas, etc. causes environmental pollution and greenhouse effect, causes global climate change, and also causes exhaustion of fossil fuel resources. Accordingly, there is increasing interest in developing alternative energy sources for fossil fuels, which are attractive alternative energy sources for biomass energy due to their renewable and clean nature. Therefore, the development of renewable and clean biomass energy is particularly important for the developing agriculture countries with relatively poor resources and relatively serious environmental pollution.
The catalytic pyrolysis technology can directly convert biomass raw materials into chemicals such as bio-based aromatic hydrocarbon and the like, and is a technology with great development potential. However, the biological oil prepared by catalytic pyrolysis has low calorific value, high viscosity and high organic acid content, which limits the application to a certain extent.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a method for preparing bio-oil by biomass pyrolysis.
The technical scheme adopted is as follows:
a method for preparing bio-oil by biomass pyrolysis comprises the following steps:
soaking biomass raw materials in potassium phosphate solution, mixing with a catalyst uniformly, and heating to 500-580 ℃ for catalytic pyrolysis;
the catalyst comprises a metal oxide.
Further, microwave treatment is performed while heating.
Further, the potassium phosphate salt is any one or more of potassium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium phosphate.
Further, the metal oxide is any one or more of calcium oxide, aluminum oxide, nickel oxide, iron oxide, magnesium oxide and zinc oxide.
Further, the biomass raw material is straw, and the straw is crushed, screened and dried.
Further, the catalyst also includes a molecular sieve support.
Further, the molecular sieve carrier is HZSM-5 molecular sieve.
Further, the catalyst also comprises an ionic liquid.
Further, the ionic liquid is any one or more of 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole hexafluorophosphate and 1-butyl-3-methylimidazole methylsulfonate.
Further, the preparation method of the catalyst comprises the following steps:
loading metal oxide on the molecular sieve carrier by using a solution gel method, calcining at 600-800 ℃ for 2-4 hours, finally immersing in ionic liquid for a period of time, taking out and drying.
The invention has the beneficial effects that:
in the prior art, the catalytic pyrolysis experiment of corn straw finds that the yield of the biological oil obtained by using the HZSM-5 molecular sieve to catalyze pyrolysis reaches 27.55%, the inventor further uses metal oxide to load on the surface of the HZSM-5 molecular sieve, a layer of loose metal oxide shell layer is formed on the surface of the biological oil, so that the oxygen-containing macromolecular compound from lignin can be effectively promoted to enter the pore canal to carry out shape selective catalysis, the thermal conductivity is better, the surface heat transfer of biomass raw materials is favorably increased in the catalytic pyrolysis process, the cellulose is promoted to carry out ring opening reaction and light olefin formation, the addition of ionic liquid obviously inhibits the generation of coke, the further polymerization reaction of monocyclic aromatic hydrocarbon and oxygen-containing compound is reduced, the viscosity of the prepared biological oil is reduced, the heat value of acid organic matters in the biological oil can be reduced, the corrosion of the biological oil to an internal combustion engine is also caused in the combustion process, the quality of the oil is further reduced, the storage and transportation cost is improved, and the biological oil prepared by the method has lower viscosity, the potential heat value and can be used as a potential fuel with higher acid value.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Example 1:
a method for preparing bio-oil by biomass pyrolysis comprises the following steps:
firstly, crushing rice straws by using a crusher, sieving by using a standard sample separation sieve, putting powder with the particle size of 160-200 meshes into a drying oven, drying at 105 ℃ until the mass is constant, obtaining a biomass raw material, adding monopotassium phosphate into water, uniformly stirring to obtain a monopotassium phosphate solution with the mass concentration of 50%, adding 100g of biomass raw material into 1200mL of monopotassium phosphate solution, stirring and soaking for 5 hours, filtering out, drying at 80 ℃ for 10 hours, fully mixing with a catalyst, and putting into a quartz boat, wherein the weight ratio of the biomass raw material to the catalyst is 10:1, firstly heating a muffle furnace to 550 ℃, introducing nitrogen to form an inert atmosphere, then pushing a quartz boat into the muffle furnace and reacting for 15min under the assistance of 200W microwaves, collecting the obtained biological oil after the reaction is finished, removing water by using anhydrous sodium sulfate, and preserving the biological oil under the refrigeration condition of 4 ℃, wherein the oil yield is 53.6%.
The preparation method of the catalyst comprises the following steps:
taking HZSM-5 molecular sieve as a carrier, mixing 125mL of deionized water, 5g of concentrated nitric acid and 10mL of isopropanol to prepare a water phase, adding the water phase into a three-port round bottom flask, dropwise adding 100mL of 0.1mol/L aluminum isopropoxide solution into the flask under stirring for 20min, continuing stirring for 1h after dropwise adding, standing and aging for 1h, taking out the HZSM-5 molecular sieve after soaking for 5min, calcining for 2h at 800 ℃ to obtain an intermediate, finally taking out the intermediate after soaking in 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid for 60s, and drying at 100 ℃ for 10 h.
Example 2:
a method for preparing bio-oil by biomass pyrolysis comprises the following steps:
firstly, crushing rice straws by using a crusher, sieving by using a standard sample separation sieve, putting powder with the particle size of 160-200 meshes into a drying oven, drying at 105 ℃ until the mass is constant, obtaining a biomass raw material, adding monopotassium phosphate into water, uniformly stirring to obtain a monopotassium phosphate solution with the mass concentration of 50%, adding 100g of biomass raw material into 1200mL of monopotassium phosphate solution, stirring and soaking for 5 hours, filtering out, drying at 80 ℃ for 10 hours, fully mixing with a catalyst, and putting into a quartz boat, wherein the weight ratio of the biomass raw material to the catalyst is 10:1, firstly heating a muffle furnace to 550 ℃, introducing nitrogen to form an inert atmosphere, then pushing a quartz boat into the muffle furnace and reacting for 15min under the assistance of 200W microwaves, collecting the obtained biological oil after the reaction is finished, removing water by using anhydrous sodium sulfate, and preserving the biological oil under the refrigeration condition of 4 ℃, wherein the oil yield is 50.2%.
The preparation method of the catalyst comprises the following steps:
adding 100mL of 0.1mol/L calcium ethoxide glycerol solution into a three-neck round bottom flask by taking the HZSM-5 molecular sieve as a carrier, dropwise adding 250mL of 0.08mol/L sodium hydroxide methanol solution into the flask in an ice-water bath at the temperature of 0 ℃, stirring and reacting for 30min at the temperature of 0 ℃ to obtain transparent sol, adding 50mL of distilled water into the obtained sol under stirring, standing and aging for 1h at room temperature, soaking the HZSM-5 molecular sieve in the solution for 5min, taking out the solution, calcining for 3h at the temperature of 650 ℃ to obtain an intermediate, finally soaking the intermediate in 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid for 60s, taking out the intermediate, and drying for 10h at the temperature of 100 ℃.
Example 3:
a method for preparing bio-oil by biomass pyrolysis comprises the following steps:
firstly, crushing rice straws by using a crusher, sieving by using a standard sample separation sieve, putting powder with the particle size of 160-200 meshes into a drying oven, drying at 105 ℃ until the mass is constant, obtaining a biomass raw material, adding monopotassium phosphate into water, uniformly stirring to obtain a monopotassium phosphate solution with the mass concentration of 50%, adding 100g of biomass raw material into 1200mL of monopotassium phosphate solution, stirring and soaking for 5 hours, filtering out, drying at 80 ℃ for 10 hours, fully mixing with a catalyst, and putting into a quartz boat, wherein the weight ratio of the biomass raw material to the catalyst is 10:1, firstly heating a muffle furnace to 550 ℃, introducing nitrogen to form an inert atmosphere, then pushing a quartz boat into the muffle furnace and reacting for 15min under the assistance of 200W microwaves, collecting the obtained biological oil after the reaction is finished, removing water by using anhydrous sodium sulfate, and preserving the biological oil under the refrigeration condition of 4 ℃, wherein the oil yield is 49.8%.
The preparation method of the catalyst comprises the following steps:
adding 100mL of 0.1mol/L nickel acetate ethylene glycol monomethyl ether solution into a three-necked round bottom flask by taking the HZSM-5 molecular sieve as a carrier, dropwise adding 25% ammonia water into the flask under stirring, regulating the pH of the system to 9.5, keeping the temperature in a water bath at 70 ℃ after dropwise adding, continuing stirring for 1h, standing and aging for 1h at room temperature, soaking the HZSM-5 molecular sieve in the mixture for 5min, taking out the mixture, calcining the mixture for 2h at 600 ℃ to obtain an intermediate, finally soaking the intermediate in 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid for 60s, taking out the intermediate, and drying the intermediate at 100 ℃ for 10 h.
Example 4:
substantially the same as in example 1, except that 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid was replaced with 1-butyl-3-methylimidazole tetrafluoroborate ionic liquid, the oil yield was 52.2%.
Example 5:
substantially the same as in example 1, except that 1-butyl-3-methylimidazolium phosphate ionic liquid was replaced with 1-butyl-3-methylimidazolium acetate ionic liquid, the oil yield was 48.5%.
Comparative example 1:
substantially the same as in example 1, except that the catalyst was prepared without being impregnated with an ionic liquid, the oil yield was 45.8%;
the preparation method of the catalyst comprises the following steps:
taking HZSM-5 molecular sieve as a carrier, mixing 125mL of deionized water, 5g of concentrated nitric acid and 10mL of isopropanol to prepare a water phase, adding the water phase into a three-neck round bottom flask, dropwise adding 100mL of 0.1mol/L aluminum isopropoxide isopropanol solution into the flask under stirring for 20min, continuing stirring for 1h after dropwise adding, standing and aging for 1h, immersing the HZSM-5 molecular sieve in the water phase for 5min, taking out, and calcining at 800 ℃ for 2 h.
Comparative example 2:
substantially the same as in example 1, except that the biomass feedstock was not impregnated with the potassium dihydrogen phosphate solution, the oil yield was 47.7%.
Performance test:
table 1 below shows the results of elemental and performance analysis of the bio-oils prepared in examples 1-5 and comparative examples 1-2 of the present invention.
Table 1:
from the above, the bio-oil prepared by the method of the invention has lower viscosity, fewer acid products and higher heat value, and can be used as a potential liquid fuel.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (1)
1. A method for preparing bio-oil by biomass pyrolysis is characterized in that biomass raw materials are soaked by potassium phosphate solution, then are uniformly mixed with a catalyst, and are heated to 500-580 ℃ for catalytic pyrolysis;
heating and carrying out microwave treatment at the same time;
the potassium phosphate salt is monopotassium phosphate;
the biomass raw material is straw, and the straw is crushed, screened and dried;
the catalyst comprises a metal oxide;
the metal oxide is any one or more of calcium oxide, aluminum oxide and nickel oxide;
the catalyst further comprises a molecular sieve support;
the molecular sieve carrier is an HZSM-5 molecular sieve;
the catalyst also comprises an ionic liquid;
the ionic liquid is any one or more of 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole acetate and 1-butyl-3-methylimidazole hexafluorophosphate;
the preparation method of the catalyst comprises the following steps:
loading metal oxide on the molecular sieve carrier by using a solution gel method, calcining at 600-800 ℃ for 2-4 hours, finally immersing in ionic liquid for a period of time, taking out and drying.
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| CN102070408A (en) * | 2010-12-10 | 2011-05-25 | 华北电力大学 | Method for preparing light phenol organic mixture through catalytic pyrolysis of biomass |
| CN103221130A (en) * | 2010-11-25 | 2013-07-24 | 旭化成化学株式会社 | Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body |
| WO2014123610A1 (en) * | 2013-02-08 | 2014-08-14 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-85 |
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| CN103221130A (en) * | 2010-11-25 | 2013-07-24 | 旭化成化学株式会社 | Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body |
| CN102070408A (en) * | 2010-12-10 | 2011-05-25 | 华北电力大学 | Method for preparing light phenol organic mixture through catalytic pyrolysis of biomass |
| WO2014123610A1 (en) * | 2013-02-08 | 2014-08-14 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-85 |
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