CN106492873A - A kind of catalyst for bio oil upgrading - Google Patents
A kind of catalyst for bio oil upgrading Download PDFInfo
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- CN106492873A CN106492873A CN201611023688.0A CN201611023688A CN106492873A CN 106492873 A CN106492873 A CN 106492873A CN 201611023688 A CN201611023688 A CN 201611023688A CN 106492873 A CN106492873 A CN 106492873A
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- catalyst
- upgrading
- bio oil
- oil
- high temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000012075 bio-oil Substances 0.000 title claims abstract description 70
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 13
- 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 13
- 230000008569 process Effects 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 4
- 238000009264 composting Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 239000010813 municipal solid waste Substances 0.000 abstract description 33
- 238000003763 carbonization Methods 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000004821 distillation Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 238000010000 carbonizing Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000010791 domestic waste Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 nitrogen-containing compound Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241001327284 Sorghastrum nutans Species 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000001146 hypoxic effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical group [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention provides a kind of catalyst for bio oil upgrading, the catalyst is the ferrum-based catalyst of silicate load.The catalyst is particularly conducive to for the bio oil that high temperature garbage distills carbonization generation to carry out hydrogenation upgrading.Bio oil after upgrading has relatively low oxygen content and higher calorific value.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of catalyst for bio oil upgrading.
Background technology
Bio oil crude quality is generally poor, needs to meet demanded fuel through successive modified upgrading.Bio oil is carried
Matter mainly includes that hydrogenation deoxidation, catalytic cracking, catalytic reforming and catalytic esterification, catalysis upgrading can change the composition of bio oil,
Fundamentally change the quality of bio oil.The key technologies such as yield and efficiency in production need to be broken through, and develop efficient catalytic
Agent is the emphasis of bio oil upgrading from now on and difficult point.
At present, up to 1.8 hundred million tons of the annual production of China's domestic waste, rubbish annual production about 440 is public per capita in city
Jin, and rapidly increased with the speed more than 10% every year, it is predicted that the year two thousand thirty, Municipal Solid Waste in China annual production are up to
4.09 hundred million tons.The refuse production per capita of big and medium-sized cities, especially megalopolis is of a relatively high, and it is left that its rate of rise reaches 20%
Right.
If to these rubbish can not be appropriate process and disposal, (heavy metal, cause of disease are micro- for that poisonous and harmful substance therein
Biology etc.) will be entered in ecosystem by certain surrounding medium such as soil, air, earth's surface or subsoil water and form dirt
Dye.This not only can destroy ecological environment, cause irreversible Ecological Changes, but also animals and plants safety and the mankind can be good for
Health works the mischief.
Garbage disposal at present can only reduce waste volumes by burning disposal.It is each that burning disposal method can produce two English etc.
Environmentally hazardous polluter is planted, the garbage incineration equipment price height of safety, scale of investment are big, and burning disposal can only pass through
Handling is used for maintaining to run, and in conventional rubbish, resin, Plastic account for 10% or so, and remaining is exactly kitchen, paper, wood chip etc..
CN102218324A discloses a kind of catalyst for bio oil catalysis upgrading and preparation method, including catalyst
Active component and catalyst carrier, by mass percentage, the catalyst active component and catalyst carrier are consisted of：
NiO is 10-32wt%；MoO3For 5-18wt%；CoO is 5-15wt%；Remaining it is divided into dolomite catalysts carrier.
CN104722329A discloses the catalyst that a kind of bio-oil catalytic hydrogenation prepares alkane, with content as 10%～
50% base metal nickel slaine, molybdenum salt, cobalt slaine, tungsten slaine are used as active component, modified molecular screen/oxidation
Aluminum is used as catalyst carrier；By catalyst carrier support content be 10%～50% molybdenum, nickel, cobalt, in tungsten one or two with
Upper mixing, obtains bio-oil Hydrobon catalyst presoma；The presoma is activated under 300-600 DEG C of hydrogen atmosphere 2-
6h, obtains the catalyst that bio-oil catalytic hydrogenation prepares alkane.
CN105854872A discloses a kind of catalyst for biological oil hydrodeoxygenation and preparation method thereof, preparation method
For：Learnt from else's experience the catalyst carrier for being impregnated with active component of roasting so as to adsorb oxygen-containing inorganic acid, and through high temperature drying at
Reason, carries out vulcanizing treatment afterwards, obtains final product product；Wherein, the active component mainly by one or more in VB races metal with
One or more composition in VIIB races metal.
CN105413723A discloses a kind of preparation method of the Ni-based biological oil hydrodeoxygenation catalyst of non-loading type, belongs to
Catalyst synthesis technology field.First, by surfactant, carbamide and soluble nickel salt, solubility microcosmic salt or (and) solubility
Tungsten salt uses water dissolution respectively, 2～16h of crystallization under the conditions of 100～300 DEG C, then by filtration after filtering residue respectively with water and nothing
Water-ethanol is washed, and obtains final product non-loading type nickel-base catalyst, be finally put into non-loading type nickel-base catalyst and bio oil after drying
In batch reactor, hydrogenation deoxidation is carried out under the conditions of 2～4MPa of Hydrogen Vapor Pressure, 100～250 DEG C of temperature and reacts 1～10h, obtained
Arrive biological oil hydrodeoxygenation product.
CN104841466A discloses a kind of biological oil base oxygenatedchemicalss hydrogenation deoxidation catalyst, including carrier and load
Catalyst component on carrier, carrier are silicon dioxide, and active component is the metal phosphide and noble metal being closely contacted with each other,
Metal phosphide is nickel phosphide or phosphating sludge, and noble metal is palladium, platinum or ruthenium, and the weight/mass percentage composition of above-mentioned each component is：Metal
Phosphide 5～15%, noble metal 0.1～1.0%, balance of carrier.
CN103949281A discloses the molecular sieve carried NiO catalyst systems of ultrasonic assistant pyrolysis bio-oils Modified MCM-41
Preparation Method and application belong to bio oil modification technology；Will be with analytically pure Ni (NO3)2·6H2The nitric acid that O is prepared with deionized water
Nickel solution supersound process at 45 DEG C, while the MCM-41 molecular sieve solids powder for accounting for nickel nitrate solution gross weight 8% is added
To in nickel nitrate solution, to add and continue supersound process 30 minutes after terminating, then stand 30 minutes, then dry at 100 ± 5 DEG C
Do, crush, cross 40 mesh sieves, roasting 3 hours, obtain catalyst at 550 DEG C.
CN 104888766A disclose a kind of hydrogenation deoxidation catalyst, and the catalyst is passed through by hydrogenation active metals component
Infusion process is supported on carrier and is obtained, and the carrier is ordered mesopore carbon/oxidation aluminium silicon composite material；With carbon, silicon oxide and oxygen
Change aluminum mass percent sum for 100% meter, carbon 10-80%, balance of silicon oxide and aluminium oxide, wherein silica alumina ratio is 7-
300；The specific surface area of the catalyst is 200-450m2/ g, pore volume are 0.20-0.40cm3/ g, aperture are 3.0-6.0nm.
WO2012/166402A1 is disclosed for by the embodiment party of the method for biomass derived pyrolysis oil deoxidation and catalyst
Case, the method comprising the steps of：Make biomass derived pyrolysis oil with the first dehydrogenation catalyst under the first predetermined hydroprocessing condition
Contacted to form the derivative pyrolysis oil effluent of the first hypoxic bio matter in the presence of hydrogen gas, the first dehydrogenation catalyst includes neutrality
Catalyst carrier, nickel, cobalt and molybdenum, nickel of first dehydrogenation catalyst comprising the amount for calculating 0.1-1.5 weight % as oxide.
US2009/062241A1 discloses a kind of method that solid biomass is changed into hydrocarbon, including a) being about 50 DEG C
The solid biomass is made to contact with catalyst in the first riser operated to about 200 DEG C of temperature, biological so as to produce first
Matter-catalyst mixture and the first hydrocarbonaceous product；B) first product is separated from first biomass-catalyst mixture
Thing；C) by first biomass-catalyst mixture be added to about 200 DEG C to about 400 DEG C temperature operate the second riser
In, so as to produce the second biomass-catalyst mixture and the second hydrocarbonaceous product；D) mixed from second biomass-catalyst
Compound separates second product；E) by second biomass-catalyst mixture be added to greater than about 450 DEG C temperature operate
In 3rd riser, so as to produce dead catalyst and hydrocarbonaceous third product；And from the dead catalyst, f) isolate the 3rd stream
Go out thing.
" Fast Pyrolysis of Biomass for Producing Bio-oil ", Zhu Xifeng etc., scientific and technological Leader, 2007,25 (21)：69-75, by unit
Element analysis and modified oil structural analyses can hold the effect of catalytic hydrogenation on the whole, while in for research biomass crude oil
There is the good theoretical direction of hydrogenation deoxidation reaction offer former so as to improve biomass under the catalytic condition of MoS2 in one-component
Oily yield.
However, in above-mentioned document and other prior arts, the bio oil for using is produced usually from agricultural products, forestry
Product, water plant, the bio oil that these bio oil are obtained with domestic waste distillation carbonization have in composition and in nature larger
Difference, still lacking, the bio oil for distilling carbonization acquisition from domestic waste effectively can be carried out the catalysis of effective upgrading
Agent.
Content of the invention
For solving the above problems, the present inventor passes through and gos deep into and systematic study, fully analyzes from domestic waste
The composition of the bio oil that distillation carbonization is obtained and property, there is provided technical scheme below, effectively enter to the bio oil
Hydrogenation upgrading is gone, it is achieved thereby that the recycling treatment of rubbish and utilization.
In one aspect of the invention, there is provided a kind of catalyst for bio oil upgrading, the catalyst is negative for silicate
The ferrum-based catalyst of load.
Preferably, the silicate is molecular sieve.It is highly preferred that the molecular sieve is HZSM-5 molecular sieves.
In a particularly preferred embodiment of the present invention, the present inventor develops a kind of energy through numerous studies
The enough catalysis for effectively carrying out hydrogenation upgrading to the bio oil in the gas stream from domestic waste high temperature distillation carbonization
Agent, active component of the catalyst comprising carrier and load on the carrier, the catalyst can be the catalysis shown in following formula
Agent：Ni-Cu-Pd-Co2O3-Fe2O3The mol ratio of/HZSM-5, wherein Ni, Cu, Pd, Co, Fe is (1-2):(5-10):(0.1-
0.5):(1-2):(10-20), based on overall catalyst weight gauge, Ni-Cu-Pd-Co2O3-Fe2O3The content of active component is 1-
10%, preferably 2-8%, more preferably 3-6%, further preferred 5%, HZSM-5 are carrier.
Preferably, HZSM-5 for low silica-alumina ratio HZSM-5, for example silica alumina ratio be less than 15, more preferably less than 10, this be because
For finding that acid strong HZSM-5 is more beneficial for the cracking of bio oil heavy component, bio oil bottoms are minimum.
The composition of bio oil is usually relatively complex, and mainly may include acids, aldehydes, ketone, alcohols, phenols, furans, ester
Class, ethers and a small amount of nitrogen-containing compound and other multi-functional compounds.As bio oil heat stability is poor, acid and corrosivity
By force, water content is high, calorific value is low and is difficult the characteristic such as to dissolve each other with petroleum-based products, therefore at present bio oil can only realize primary should
With for example for the heat power equipment such as Industrial Stoves and oil burning boiler, it is impossible to which petroleum replacing product directly applies to internal combustion engine or turbine
The burning of machine, it is impossible to meet modern high-grade commercial Application.In order to improve bio oil application, need to be transformed into Gao Pin
The liquid fuel of position, reaches the requirement of transport fuel, and so as to realize substituting or part petroleum replacing product, this just must be to biology
Oil is modified upgrading so as to which chemical constituent is converted into Hydrocarbon by hydrocarbon oxygen compound.How effectively to bio oil
Carry out the exploitation that one of key of upgrading is catalyst.
Research finds, in the above-mentioned catalyst of the present invention, Niδ+Than conventional Moδ+There is higher activity, Ni makes
With can obtain C6-C12 hydrocarbon (preferably alkane) with high selectivity, the use of Cu can obtain C16 hydrocarbon (preferred alkane with high selectivity
Hydrocarbon), use while Ni, Cu, it has surprisingly been found that it may also be ensured that obtaining a certain amount of C18 and C19 hydrocarbon, surface Ni, Cu make
Effectively there are hydrogenolysis with the C-O keys in bio oil can be made.
Different from general improving quality of biomass oil, in the gas stream of the present invention, the steam containing higher proportion, therefore
Very high request is proposed to the hydrothermal stability of catalyst.The conventional catalyst for improving quality of biomass oil cannot be used for this
The upgrading of the gas stream of invention.Iron catalyst is a kind of common catalyst for removing oxygen in plant base material, but ferrum catalysis
Agent is failed when meeting water, although and palladium catalyst when meeting water effectively, the effect of its deoxygenation be not fine, and costly, and
Minimal amount of palladium is added in ferrum, can obtain good synergism.Inventor's research finds that the addition of a small amount of palladium contributes to hydrogen
Be covered in the surface of ferrum in catalyst, make reaction accelerate, and prevent water blocking react, thus hydrogen consumption little, activity, stability and
Far better than single iron catalyst in terms of selectivity, its catalytic life can improve more than 2 times.
Through research, the present inventor also has found that the addition of Co advantageously reduces the crystallite dimension of catalytic active component so as to energy
Enough it is effectively embedding in the duct of HZSM-5 molecular sieves, this is for improving the activity of catalytic active component, selectivity and stable
Property has very positive meaning.However, if Co amounts are excessive, Co can cover hydrogenation sites Ni, Cu etc., so as to reduce urging
The activity of agent.
Contain more non-aromatic hydro carbons in the bio oil of gas stream, the acid centre on HZSM-5 molecular sieves can
It is aromatic compound effectively by the non-aromatic hydrocarbon conversion.Acetyl of the carboxylic acid major part in bio oil from hemicellulose
Base, its thermal decomposition product are mainly acetic acid, and HZSM-5 molecular sieves have preferable decarboxylation ability, and the carboxylic acid in bio oil is in molecular sieve
There is decarboxylic reaction and deoxygenation under catalytic action so that carboxylic acid content is greatly decreased in the bio oil after upgrading.
Previously there is not been reported in document for above-mentioned particularly a preferred catalyst, and which is that the present invention is directed to from garbage reclamation
The concrete composition feature of gas stream and bio oil is targetedly designed, and achieves good upgrading effect.
The catalyst can be prepared using the conventional dipping calcination method in this area.Specifically, weigh according to the above ratio
A certain amount of precursor salt such as Ni (NO3)2、Cu(NO3)2、Pd(NO3)2、Co(NO3)2、Fe(NO3)3(or their hydrate forms)
And citric acid, plus deionized water dissolving, stir, be made into the solution that concentration is 0.5-1.5mol/L, weigh a certain amount of
HZSM-5 molecular sieves are put in reaction vessel, and the solution for preparing is poured in reaction vessel, are placed in the constant temperature with agitator and are added
Heating in deep fat bath apparatus, at a temperature of 60-120 DEG C stirs 1h-10h, is then placed in 100 DEG C of -150 DEG C of dryings in drying baker
The catalyst precursor for obtaining subsequently is placed in 500 DEG C -800 DEG C calcining 1h-6h in Muffle furnace, then in H by 12h2In the presence of in
Reduction activation at 200-300 DEG C, is obtained Ni-Cu-Pd-Co2O3-Fe2O3/ HZSM-5 catalyst.
In another aspect of this invention, there is provided application of the above-mentioned catalyst in bio oil upgrading.
The bio oil is preferred from composting charing process.
In grading process, the bio oil can be carried in the form of the gaseous stream comprising bio oil and water vapour
Matter.That is, the logistics comprising bio oil and vapor is directly carried out upgrading, need not isolate bio oil carries out upgrading again.
The upgrading is preferably and is hydrogenated with upgrading, more preferably hydrogenation deoxidation upgrading.
For the present invention, 3.0wt.% is preferably shorter than through the content of unsaturated phenol in the bio oil of upgrading.
Preferably, bio oil and water through upgrading will be isolated from logistics after upgrading.
It is highly preferred that the separation is carried out by distillating method.
For the present invention, the composting charing process may include following steps：(1) rubbish loading rubbish is transported
Device；(2) rubbish feeding device is made to pass through high temperature distillation carbonizing apparatus；(3) gas is taken out from high temperature distillation carbonizing apparatus top
Logistics, the gas stream include bio oil and vapor；(4) gas stream is made to pass through catalyst bed in a gaseous form；(5) will
Condensed from the effluent of catalyst bed and separated, obtained bio oil and the water through upgrading；(6) from through high temperature distillation charcoal
The rubbish feeding device that makeup is put obtains charcoal class material.
The rubbish is preferably domestic waste.
Gas stream is taken out preferably in a continuous manner from high temperature distillation carbonizing apparatus top.
High temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam.
The temperature of the high temperature anaerobic steam is preferably 300-600 DEG C.The pressure of the high temperature anaerobic steam is preferably
0.1-1.0MPa.
Preferably, include nitrogen in wherein described high temperature anaerobic steam.It is highly preferred that nitrogen content is 10-80v.%, more
It is preferred that 20-60v.%.
In the present invention, it is preferred to not carry out any pretreatment to rubbish.
For the present invention, compared with simple dry distilling of the prior art, the presence of nitrogen can avoid rubbish in carbonization
During burn, make generation charcoal have higher calorific value.In addition, compared with pure steam gasification in prior art,
The presence of nitrogen can also increase heating medium calorific value, improve the efficiency of heating surface so as to improve carbonization efficiency, while can also save
Steam consumption, more importantly, by the addition of nitrogen, can be the catalysis bar needed for the offer of the catalysis upgrading of follow-up distillation
Part, for example adjust needed for vapor partial pressure because too high vapour pressure can cause catalysis upgrading to be difficult to effectively carry out, nitrogen plus
Enter the vapor partial pressure that can reduce in gas stream i.e. distillation.
The inventors discovered that, in existing waste steam treatment technology, often have ignored the composition for rubbish has choosing
Steaming conditions are selected selecting property, the difference of rubbish composition is have ignored, is caused garbage treatment efficiency relatively low.The present inventor passes through
Numerous studies, select different steaming conditions according to different rubbish compositions, obtain good steam treatment effect.Special
Not, following high temperature distillation charing process condition is selected：(1) with the gross weight meter of rubbish, organic species in rubbish is constituted
During weight % of content >=80, the temperature of high temperature anaerobic steam is 300-450 DEG C, preferably 300-400 DEG C；In high temperature anaerobic steam
Nitrogen content is 10-30v.%, preferably 10-20v.%；The time of staying in high temperature distillation carbonizing apparatus is 8-12h；(2)
When in rubbish composition with the gross weight meter of rubbish, during organic species 80 weight % of content ＜ and preferably plastic, rubber class material
During 10 weight % of content ＜, the temperature of high temperature anaerobic steam is 450 DEG C -600 DEG C, preferably 500 DEG C -550 DEG C；High temperature anaerobic steam
In nitrogen content be 40-80v.%, preferably 60-80v.%；The time of staying in high temperature distillation carbonizing apparatus is 5-8h.
Further, for above-mentioned condition (1), when plastic, rubber class content of material >=10 weight %, high temperature anaerobic steams
The temperature of vapour is 350-380 DEG C；Nitrogen content in high temperature anaerobic steam is 10-15v.%；In high temperature distillation carbonizing apparatus
The time of staying be 8-10h；When plastic, rubber class content of material 10 weight % of ＜, the temperature of high temperature anaerobic steam is 300-
320℃；Nitrogen content in high temperature anaerobic steam is 25-30v.%；The time of staying in high temperature distillation carbonizing apparatus is 11-
14h.Research finds, high temperature distillation carbonization condition as selecting, and it is high temperature distillation carbonization due to plastic, rubber class material to be
One of source of bio oil in journey, the composition such as the rubbish from cooking that compares and wood grass, which is very quick to steam distillation carbonization condition
Sense, when its content is high, the temperature and water vapour that need application higher decompose which, but distillation carbonization time again can not mistake
Long, otherwise it is easy to make the bio oil of generation resolve into micro-molecular gas, causes biological oil yield to reduce, and produce harmful by-product
Thing.
When in rubbish, organic species content is higher, above-mentioned steaming conditions are particularly conducive to produce liquid combustible thing
Generation；And organic species content relatively low when, be particularly conducive to the generation of charcoal class material.
For the present invention, the gas stream is preferably substantially free of two English.Because of the distillation that heats up under anaerobic state, institute
So that the harmful substances such as two English will not be produced, can be with environment protection.This has very big excellent compared to common burning method
Gesture.
Preferably, the high temperature anaerobic steam wherein used in high temperature distillation carbonizing apparatus is from high pressure through-flow steam oven.
10 weight %, more preferably less than preferably shorter than 5 weight %, 2 weight % are less than through oxygen content in the bio oil of upgrading.
Further, it is more than 40MJ/kg through the higher calorific value of the bio oil of upgrading.Preferably, the pH through the bio oil of upgrading is 5-8.
Preferably, 3.0wt.% is less than through the content of unsaturated phenol in the bio oil of upgrading.
Description of the drawings
Fig. 1 is the top view of the high temperature distillation carbonizing apparatus according to the present invention；
Fig. 2 is the SEM figures of catalyst obtained according to embodiments of the present invention 1；
Fig. 3 be using according to embodiments of the present invention 1 catalyst in bio oil upgrading each component content (GC-MS always from
Subflow) variation with temperature figure.
Specific embodiment
With reference to following examples and comparative example, the present invention is described in further detail, but the embodiment party of the present invention
Formula not limited to this.
Embodiment 1
Choosing and the house refuse of garbage compression transfer station being occupied from five tunnel of Haidian District, Beijing City, the composition of the rubbish is through inspection
Survey as shown in table 1 below：
Table 1：Domestic waste is into being grouped into
High temperature distillation carbonization is carried out to above-mentioned rubbish by following steps：Rubbish is loaded rubbish feeding device；Make rubbish
Feeding device passes through high temperature distillation carbonizing apparatus；Gas stream is taken out from high temperature distillation carbonizing apparatus top；Make the gas stream
Pass through catalyst bed in a gaseous form；The effluent of self-catalysis agent in future bed is condensed and is separated, obtain liquid combustible thing and
Water；Charcoal class material is obtained from the rubbish feeding device through high temperature distillation carbonizing apparatus.The high temperature distillation carbonizing apparatus passes through
High temperature anaerobic steam is heated, and the temperature of high temperature anaerobic steam is 355 DEG C, and the nitrogen content in high temperature anaerobic steam is
12v.%, processed average time for 9.0 hours.In gas stream, combustible organic carries out upgrading, institute using hydrodeoxygenation process
The catalyst for stating catalyst bed is Ni-Cu-Pd-Co2O3-Fe2O3The mol ratio of/HZSM-5, wherein Ni, Cu, Pd, Co, Fe is 2:
8:0.15:1.5:15, based on overall catalyst weight gauge, Ni-Cu-Pd-Co2O3-Fe2O3The content of catalytic active component is 5%,
Hydrogenation upgrading condition is 300 DEG C, 3.0MPa hydrogen pressures, 3h.Coke is obtained by the method and the bio oil through upgrading.The life
Oxygen content in thing oil is 4.1wt.%, is 43MJ/kg through the higher calorific value of the bio oil of upgrading, and catalyst life is for about
722h.
Comparative example 1
The comparative example and embodiment 1 differ only in bio oil upgrading using catalyst be conventional NiMo/Al2O3
Catalyst.Oxygen content in the bio oil through upgrading for obtaining is 19.6wt.%, through the higher calorific value of the bio oil of upgrading is
28MJ/kg, catalyst life are for about 120h.
The method of the present invention clearly can be seen that by above-described embodiment and comparative example and be obtained in that substantially preferably upgrading
Effect.In addition, the bio oil of the inventive method upgrading, with relatively low oxygen content, so as to have higher calorific value, is hydrogenated with addition
The catalyst life of upgrading is also greatly improved.
This written description discloses the present invention using example, including optimal mode, and also enables those skilled in the art
Manufacture and using the present invention.The present invention can patentable scope be defined by the claims, and this area skill can be included
Other examples that art personnel expect.If other examples this have structural elements not different from the literal language of claims
Element, or if other examples this include the equivalent structure element with the literal language of claims without substantial differences,
Then other examples this are intended within the scope of claims.In the case where inconsistent degree is not resulted in, by reference to
To be incorporated herein in place of all references for referring to herein.
Claims (10)
1. a kind of catalyst for bio oil upgrading, the catalyst are the ferrum-based catalyst of silicate load.
2. catalyst according to claim 1, wherein described silicate are molecular sieve.
3. catalyst according to claim 2, wherein described molecular sieve are HZSM-5 molecular sieves.
4. application of the catalyst according to any one of claim 1-3 in bio oil upgrading.
5. application according to claim 4, the bio oil is from composting charing process.
6., according to the application of claim 4-5, wherein in grading process, the bio oil is with comprising bio oil and water vapour
The form of gaseous stream carries out upgrading.
7. application according to claim 6, wherein described upgrading are hydrogenation upgrading.
8. application according to claim 6, is wherein less than 3.0wt.% through the content of unsaturated phenol in the bio oil of upgrading.
9. application according to claim 6, will isolate bio oil and water through upgrading wherein after upgrading from logistics.
10. application according to claim 6, wherein described separation are carried out by distillating method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325835A (en) * | 2017-06-15 | 2017-11-07 | 上海交通大学 | The method that hydro-thermal method converts grease or higher fatty acids is long chain alkane |
| CN113004953A (en) * | 2021-03-16 | 2021-06-22 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN113308265A (en) * | 2020-02-26 | 2021-08-27 | 中国石油化工股份有限公司 | Method for preparing biological crude oil by catalytic conversion method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787005A (en) * | 2010-01-14 | 2010-07-28 | 浙江大学 | Method for improving quality of biological oil through one-step hydroesterification of furfural and acetic acid in the presence of catalyst |
| CN102218324A (en) * | 2011-04-19 | 2011-10-19 | 安徽理工大学 | Catalyst for removing oxygen and improving quality of bio-oil and preparation method thereof |
| CN102994137A (en) * | 2012-12-13 | 2013-03-27 | 青岛大学 | Method for preparing algae material fuel by catalytic liquefying method |
| CN103343055A (en) * | 2013-06-24 | 2013-10-09 | 合肥工业大学 | Method for quality improvement of biological oil through catalytic esterification-deoxidize reforming in subcritical alcohol system |
| CN103949281A (en) * | 2014-04-26 | 2014-07-30 | 东北农业大学 | Preparation method of ultrasonic-assisted pyrolysis bio-oil modified MCM-41 molecular sieve loaded NiO catalyst as well as application thereof |
-
2016
- 2016-11-22 CN CN201611023688.0A patent/CN106492873B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787005A (en) * | 2010-01-14 | 2010-07-28 | 浙江大学 | Method for improving quality of biological oil through one-step hydroesterification of furfural and acetic acid in the presence of catalyst |
| CN102218324A (en) * | 2011-04-19 | 2011-10-19 | 安徽理工大学 | Catalyst for removing oxygen and improving quality of bio-oil and preparation method thereof |
| CN102994137A (en) * | 2012-12-13 | 2013-03-27 | 青岛大学 | Method for preparing algae material fuel by catalytic liquefying method |
| CN103343055A (en) * | 2013-06-24 | 2013-10-09 | 合肥工业大学 | Method for quality improvement of biological oil through catalytic esterification-deoxidize reforming in subcritical alcohol system |
| CN103949281A (en) * | 2014-04-26 | 2014-07-30 | 东北农业大学 | Preparation method of ultrasonic-assisted pyrolysis bio-oil modified MCM-41 molecular sieve loaded NiO catalyst as well as application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107325835A (en) * | 2017-06-15 | 2017-11-07 | 上海交通大学 | The method that hydro-thermal method converts grease or higher fatty acids is long chain alkane |
| CN107325835B (en) * | 2017-06-15 | 2020-04-28 | 上海交通大学 | Method for converting grease or higher fatty acid into long-chain alkane by hydrothermal method |
| CN113308265A (en) * | 2020-02-26 | 2021-08-27 | 中国石油化工股份有限公司 | Method for preparing biological crude oil by catalytic conversion method |
| CN113004953A (en) * | 2021-03-16 | 2021-06-22 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN113004953B (en) * | 2021-03-16 | 2022-05-20 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
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