CN108855101A - Utilize the method for the online improving quality of bio oil of iron-based composite catalyst - Google Patents
Utilize the method for the online improving quality of bio oil of iron-based composite catalyst Download PDFInfo
- Publication number
- CN108855101A CN108855101A CN201810576994.XA CN201810576994A CN108855101A CN 108855101 A CN108855101 A CN 108855101A CN 201810576994 A CN201810576994 A CN 201810576994A CN 108855101 A CN108855101 A CN 108855101A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- based composite
- bio oil
- biomass
- online
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000012075 bio-oil Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 30
- 239000003921 oil Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000002023 wood Substances 0.000 claims abstract description 8
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 5
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- 238000012856 packing Methods 0.000 claims abstract description 4
- 238000002407 reforming Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 9
- 229960001545 hydrotalcite Drugs 0.000 claims description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 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 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000011833 salt mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000003987 high-resolution gas chromatography Methods 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 239000000292 calcium oxide Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- -1 acids in bio oil Chemical class 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 150000002240 furans Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GGJUJWSDTDBTLX-UHFFFAOYSA-N 1-(2-Furyl)butan-3-one Chemical class CC(=O)CCC1=CC=CO1 GGJUJWSDTDBTLX-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910003111 Mg(Al)O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A method of utilizing the online improving quality of bio oil of iron-based composite catalyst, it is characterized in that, using Fe/CaO/Mg (Al) O as catalyst, using wood powder as biomass material, biomass and Catalyst packing are subjected to fast pyrogenation in the reactor, the steam that biomass pyrolytic generates directly carries out catalytic pyrolysis in catalyst surface, the biological oil vapour after obtaining upgrading, finally carries out the online component of GC/MS and content analysis to the biological oil vapour after upgrading；The catalyst is using Mg (Al) O as carrier, and using Fe as vapor reforming main active component, CaO is as cocatalyst component and carrier, the mass percentage of each component：Fe is 10%-30%, and CaO 25%-48%, Mg (Al) O are 40%-48%.
Description
It is on July 18th, 2016 that the application, which is the applying date, entitled to be used for bio oil application No. is 201610563540X
The divisional application of the Chinese invention patent application of the iron-based composite catalyst and methods for making and using same of online upgrading.
Technical field
The invention belongs to the utilization technical fields of biomass energy, mention online more particularly to one kind for bio oil
The Fe based composite catalyst and its methods for making and using same of matter.
Background technique
As a kind of reproducible clean energy resource, product liquid-bio oil that biomass is obtained by rapidly pyrolysing and liquefying
It is a kind of novel liquid fuel, with energy density height, the advantages such as easily storage transport, and sulphur, nitrogen content are low, it is expected to alleviate energy
Source is short and uses problem of environmental pollution brought by fossil fuel.However, bio oil crude product ingredient is extremely complex, almost wrap
All kinds of oxygen-bearing organic matters are contained（Acid, aldehyde, ketone, alcohol, phenol, furans, sugar etc.）, lead to that its stability is poor, acidity is high, calorific value is low, viscous
The disadvantages of big is spent, its popularization and application as hydrocarbon fuel is seriously hindered.Bio oil oil quality how is improved to have become
Influence a key technical problem of biomass fast pyrolysis technical application and economy.In order to improve the quality of bio oil,
Previous people have done many research work.
Patent " a method of improve quality of bio-oil "（CN104560102A）Disclose a kind of raising quality of bio-oil
Method, the method includes will crack generate bio oil be added autoclave, be added calcium oxide as catalyst, in N2
Under protective condition, by dividing temperature section control reaction to improve quality of bio-oil.However, biomass material must be pre- through sulfuric acid in the patent
Processing, and ingredient is still more complicated in obtained refining biological oil, target product furfuryl acetone class yield is lower than 25%, Gao Han
The group compounds of aldehydes and ketones of amount is effectively improved stability of bio-oil not.
Patent " a kind of method of improving quality of biomass oil "（CN101358138A）Disclose a kind of side of improving quality of biomass oil
Method, the method is reacted by supercritical catalyst reduces heavy constituent in bio-oil, by bio-oil, supercritical reaction medium second
Alcohol or methanol, HZSM-5 molecular sieve catalyst put into autoclave, in N2Protection, pressure 7.5-11MPa, 100-300 DEG C
It is reacted 3-5 hours under the conditions of temperature, heavy constituent mass percentage is 15%-28% in refining biological oil.However, the patent uses
Supercritical, high pressure reaction, there is certain difficulty in severe reaction conditions, and do not referred in the process of practical popularization and application to biology
Acids, aldehydes etc. influence the adjustment of formula problem of bio oil corrosivity and stability in oil.
In addition, above-mentioned patent is to be heated to mention again after the bio oil of biomass pyrolytic generation to be carried out to condensation collection
Matter processing, energy consumption is high, processing routine complexity and somewhat expensive, using also difficult on commercial technologies.
High-quality biological oil is prepared using the online catalytic pyrolysis biomass fast pyrogenation product of catalyst to react because it is entire
In the same reactor carry out, without by bio oil condense and again heating, it is easy to operate, refine it is at low cost, become current
A kind of most commonly used method is studied, and its core is the selection of catalyst.The use that each research unit reports both at home and abroad at present
In the catalyst of bio oil catalysis upgrading mainly include metal oxide, zeolite molecular sieve and precious metal.Wherein, metal
Oxide raw material is easy to get, is cheap, but its catalytic activity is lower；Precious metal based catalysts activity is high, but it is expensive and
Easy-sintering inactivates under hot conditions or when long-play；Molecular sieve catalysts can meet high activity and shape selective catalysis simultaneously
Two kinds of functions, but because its stronger acid easily carbon distribution inactivates.Therefore, find efficiently, cheap and anti-carbon, anti-sintering urge
Agent is the emphasis of online this research work of upgrading of bio oil at this stage.
Summary of the invention
In view of the above problems, the present invention overcomes shortcoming in the prior art, a kind of low in cost, catalytic activity is provided
The Fe based composite catalyst for the online upgrading of bio oil of good and anti-sintering anti-carbon；
Present invention simultaneously provides the preparation method and application methods of the Fe based composite catalyst.
The present invention solves technical problem and adopts the following technical scheme that：It is a kind of compound to be urged for the iron-based of the online upgrading of bio oil
Agent, which is characterized in that the catalyst is using Mg (Al) O as carrier, using Fe as vapor reforming main active component, CaO conduct
The mass percentage of cocatalyst component and carrier, each component is：Fe is 10%-30%, and CaO 25%-48%, Mg (Al) O is
40%-48%。
The specific feature of this programme in addition, the main active component Fe high degree of dispersion in the carrier, size controlling is in 5-
10nm。
Fe based composite catalyst through the following steps that preparation：
（a）Hydrotalcite precursor preparation：By Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
It is [Mg that concentration is made into deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
For 2 mol/L NaOH solution as precipitating reagent；It is slowly that the above-mentioned salt-mixture prepared is molten under continuous strong stirring condition
Liquid is continuously added dropwise in aqueous slkali, and controls final solution pH value 10.5 ~ 12, forms suspension after being added dropwise；In room temperature
Under the conditions of crystallization for 24 hours, by the centrifugation of gained precipitation solution, to wash to supernatant pH be 7, grinds and obtains after dry 12h at 100 DEG C
Laminate contains the single presoma of hydrotalcite of Fe, Ca, Mg, Al element.
（b）Calcining reduction：Weigh a certain amount of step（a）The single presoma of obtained hydrotalcite is placed in tube-type atmosphere furnace,
In a reducing atmosphere, temperature calcines 2h~6h under the conditions of being 500 DEG C~800 DEG C, is naturally cooling to room temperature, obtains that Fe base is compound to urge
Agent.
A kind of application method that above-mentioned iron-based composite catalyst is used for the online upgrading of bio oil, it includes the following steps：
Using Fe/CaO/Mg (Al) O as catalyst, using wood powder as biomass material, by biomass and Catalyst packing in the reactor into
Row fast pyrogenation, the steam that biomass pyrolytic generates directly carry out catalytic pyrolysis in catalyst surface, the biology after obtaining upgrading
Oil vapour finally carries out the online component of GC/MS and content analysis to the biological oil vapour after upgrading.
Specific feature of the invention is in addition, the reactor is pyrolysis-high resolution gas chromatography mass spectrometry device (Py-GC/MS)；
The pyrolysis reaction temperature is 550-700 DEG C, residence time 25s, and the mass ratio of catalyst and biomass dosage is 10-
20；
The catalyst is loaded into the one or both ends of biomass material.
A kind of preparation method of iron-based composite catalyst, it includes the following steps：
（a）Hydrotalcite precursor preparation：By Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
It is [Mg that concentration is made into deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
For 2 mol/L NaOH solution as precipitating reagent；It is slowly that the above-mentioned salt-mixture prepared is molten under continuous strong stirring condition
Liquid is continuously added dropwise in aqueous slkali, and controls final solution pH value 10.5 ~ 12, forms suspension after being added dropwise；In room temperature
Under the conditions of crystallization for 24 hours, by the centrifugation of gained precipitation solution, to wash to supernatant pH be 7, grinds and obtains after dry 12h at 100 DEG C
Laminate contains the single presoma of hydrotalcite of Fe, Ca, Mg, Al element.
（b）Calcining reduction：Weigh a certain amount of step（a）The single presoma of obtained hydrotalcite is placed in tube-type atmosphere furnace,
In a reducing atmosphere, temperature calcines 2h~6h under the conditions of being 500 DEG C~800 DEG C, is naturally cooling to room temperature, obtains that Fe base is compound to urge
Agent.
Specific feature of the invention is in addition, step（a）In middle mixing salt solution（Mg2++Ca2+）/（Fe3++Al3+）Molar ratio
For（1~4）：1, Mg2+：Ca2+：Fe3+：Al3+Molar ratio is more preferably 1：1：1：1 or 2：2：1：1 or 3：3：1：1 or 4：4：
1：1.
The step（b）Described in reducing atmosphere be hydrogen or reducing atmosphere is the mixing of hydrogen and nitrogen or argon gas
Gas, wherein H in mixed gas2Percentage by volume preferably 10%.
Compared with the prior art, the present invention has the beneficial effect that：
1, the present invention is based on the transformations of LDHs precursor construction topology, while adding Mg (Al) O composite oxides and realizing as carrier
The high degree of dispersion of the main active component Fe of catalyst, is remarkably improved catalytic activity and effectively prevent in biomass fast pyrogenation product
The carbon distribution reaction of macromolecular oligo object leads to catalyst inactivation.
2, catalyst provided by the invention can remove the unexpected compound such as acids in bio oil, aldoketones completely, have
Effect reduces its acidity and significantly improves its stability.
3, catalyst provided by the invention may advantageously facilitate the formation of phenol compound in bio oil, can to its selectivity
Up to 89.32%, effectively promoted bio oil calorific value while, also there is high chemical added value, be prepare phenolic resin,
The important chemical intermediate of the materials such as food additives and fine chemicals.
Specific embodiment
Embodiment 1：A kind of preparation method of iron-based composite catalyst, it includes the following steps：
The preparation of LDHs presoma：According to Mg2+：Ca2+：Fe3+：Al3+The ratio that molar ratio is about 1: 1: 1: 1 weighs 48.10g
Mg(NO3)2∙6H2O、44.27g Ca(NO3)2∙6H2O、75.50g Fe(NO3)3∙9H2O and 70.89g Al (NO3)2∙9H2O is added
Deionized water is configured to 500 ml mixed solutions, weighs 50.99gNaNO3Deionized water is added and is configured to 500 ml mixed solutions,
It separately weighs 56gNaOH and the aqueous slkali that deionized water is configured to 800mL concentration as 2M is added.By NaNO3Solution and NaOH solution are fallen
Enter in four-hole boiling flask, mixing salt solution is added drop-wise in above-mentioned mixed ammonium/alkali solutions under mechanical stirring, so that final solution pH is
11.2, it by gained slurries crystallization 24 hours under room temperature, is washed with deionized, is centrifuged 4 times, dry 12 is small at 100 DEG C
When, grinding obtains LDHs presoma.
Roasting reduction：5g LDHs presoma is weighed, uniformly divides and is placed in tube-type atmosphere furnace in Ci Zhou, in N2/H2
（90%/10%）Under reducing atmosphere, 500 DEG C are warming up to 10 DEG C/min, 2 hours is kept the temperature, is down to room temperature naturally to temperature and obtains Fe
Based composite catalyst.
The Fe based composite catalyst composition and mass percentage of above method preparation are Fe：27.78%, CaO：28.06%,
Mg(Al)O：44.16%, other impurities object phase is not found, and wherein Fe nanoparticle average-size is 7.3 nm.
A kind of application method that above-mentioned iron-based composite catalyst is used for the online upgrading of bio oil, it includes the following steps：
Using Fe/CaO/Mg (Al) O as catalyst, using wood powder as biomass material, by biomass and Catalyst packing in the reactor into
Row fast pyrogenation, the steam that biomass pyrolytic generates directly carry out catalytic pyrolysis in catalyst surface, the biology after obtaining upgrading
Oil vapour finally carries out the online component of GC/MS and content analysis to the biological oil vapour after upgrading.The reactor is cracking-
Gas chromatography combined with mass spectrometry device (Py-GC/MS)；The pyrolysis reaction temperature is 550-700 DEG C, residence time 25s, catalysis
The mass ratio of agent and biomass dosage is 10-20；The catalyst is loaded into the one or both ends of biomass material.Using Py-
GC/MS device, 0.5mg wood powder and 10mg catalyst, setting reaction temperature are 550 DEG C respectively for filling in sample cell, when stop
Between be 20s, clack box and transmission line temperature are 290 DEG C.
The typical component of the bio oil crude product of the direct fast pyrogenation generation of biomass is under the above-described reaction conditions：Hydro carbons
（Predominantly aliphatic hydrocarbon）Content 1.38%, phenol content are 52.53%, acids content 18.05%, aldoketones content 23.29%, furan
Class of muttering content 4.75%.
Online upgrading is carried out to the bio oil crude product of component as described above, experimental studies have found that gained refining biological oil group
Significant optimization is got, wherein the unexpected compound such as acids, aldoketones is substantially completely removed, biological acidity of oil and stability
It substantially improves.Phenolic compound becomes primary product, and content substantially increases to 89.32%, additionally contains a small amount of furans
3.04% and hydrocarbon compound 7.64%（Wherein fat hydrocarbon content is 3.21%, and arene content is 4.43%）, bio oil
Quality is obviously improved.Surface, which does not find carbon deposition phenomenon, to be found to post catalyst reaction structural characterization.
Embodiment 2：
The preparation method of catalyst place same as Example 1 repeats no more in this embodiment, the difference is that active component
Content is different, wherein Mg2+：Ca2+：Fe3+：Al3+Molar ratio is about 4: 4: 1: 1.The catalyst composition and quality percentage being prepared
Content is Fe：11.41%, CaO：42.06%, Mg (Al) O：46.53%, other impurities object phase is not found, and wherein Fe nanoparticle is flat
Having a size of 5.2 nm.
The online upgrading of bio oil crude product is carried out under cracking condition same as Example 1.Experimental studies have found that with biology
Oily crude product is compared, and acid is substantially completely removed in refining biological oil, and the content of group compounds of aldehydes and ketones is reduced to 5.46%, hydrocarbon
Kind compound content increases to 33.52%（Wherein fat hydrocarbon content is 18.89%, and arene content is 14.63%）, phenols
Compounds content slightly increases to 56.88%, and furans content is 4.14%.After upgrading in bio oil unexpected compound acids and
Aldoketones content is substantially reduced, and oxygen content and acid significant decrease, stability greatly improve, and quality is promoted.With embodiment 1
It compares, main active component Fe content reduces so that catalyst activity decreases in catalyst.To post catalyst reaction structure table
It levys existing, there is a small amount of carbon distribution on surface.
Embodiment 3：
Catalyst composition and mass percentage and embodiment 1 are consistent in this embodiment, are Fe：27.78%, CaO：28.06%, Mg
(Al)O：44.16%, other impurities object phase is not found, and wherein Fe nanoparticle average-size is 7.3 nm.Preparation method and implementation
Example 1 is identical, and details are not described herein again.
Above-mentioned iron-based composite catalyst is used for the application method place same as Example 1 of the online upgrading of bio oil no longer
It repeats, difference from Example 1 is in bio oil grading process that catalyst is different from wood powder type of feed, specially will be wooden
Powder 0.5mg, catalyst 10mg, which are fitted into sample cell to rock, is uniformly mixed the two.Experimental studies have found that after upgrading in bio oil
Acid content is 16.18%, and hydrocarbons content is 20.58%（Wherein fat hydrocarbon content is 4.32%, and arene contains
Amount is 16.26%）, content of phenolic compounds 46.29%, content of group compounds of aldehydes and ketones 10.67%, furfuran compound content
It is 6.28%.Compared with Example 1, although by the way of catalyst and biomass material mixed pyrolysis hydrocarbon in bio oil
The content of matter increased, however substantially reduce to the unexpected compound conversion capability such as acids, aldoketones, biological acidity of oil and
Stability does not make moderate progress.
Embodiment 4：
Catalyst composition and mass percentage and embodiment 1 are consistent in this embodiment, are Fe：27.78%, CaO：28.06%, Mg
(Al)O：44.16%, other impurities object phase is not found, and wherein Fe nanoparticle average-size is 7.3 nm.Preparation method and implementation
Example 1 is identical, and details are not described herein again.
It iron-based compound is urged application method that above-mentioned iron-based composite catalyst is used for the online upgrading of bio oil is a kind of above-mentioned
Application method same as Example 1 place of the agent for the online upgrading of bio oil repeats no more, the difference is that bio oil
The ratio between catalyst/wood powder dosage difference, specially wood powder loadings 0.5mg, loaded catalyst 5mg in grading process.Experiment
The study found that acid content is reduced to 2.18% in refining biological oil, hydrocarbons content compared with bio oil crude product
Increase to 38.15%（Wherein fat hydrocarbon content is 20.89%, and arene content is 17.26%）, content of phenolic compounds is
45.46%, content of group compounds of aldehydes and ketones is reduced to 8.17%, and furfuran compound content is 6.04%.It is oxygen-containing in bio oil after upgrading
Amount and acidity decrease, and stability increases, and quality is obviously improved.Compared with Example 1, catalyst loading
Reduction considerably reduces active site, so that catalyst activity decreases, to the unexpected compound such as acids, aldoketones
Conversion capability decreases.Surface is without carbon distribution to be found to post catalyst reaction structural characterization.
Embodiment 5：
Catalyst composition and mass percentage and embodiment 1 are consistent in this embodiment, are Fe：27.78%, CaO：28.06%, Mg
(Al)O：44.16%, other impurities object phase is not found, and wherein Fe nanoparticle average-size is 7.3 nm.Preparation method and implementation
Example 1 is identical, and details are not described herein again.
It is 700 DEG C that difference from Example 1, which is that biomass cracking reaction temperature is increased by 550 DEG C,.Experimental study hair
Existing, compared with bio oil crude product, hydrocarbons content increases to 54.15% in the bio oil of purification（Wherein fat hydrocarbon content
It is 39.89%, arene content is 14.26%）, content of phenolic compounds is reduced to 39.06%, content of group compounds of aldehydes and ketones drop
Down to 1.17%, furfuran compound content is 5.04%, also contains a small amount of acid in product, content is about 0.58%.It mentions
Oxygen content and acid significant decrease, stability greatly improve in bio oil after matter, and quality is obviously improved.With embodiment 1
It compares, the raising of upgrading reaction temperature is conducive to the generation of hydrocarbon compound, however the conversion for acids, group compounds of aldehydes and ketones
Ability slightly reduces., which there is a small amount of carbon distribution on surface, to be found to post catalyst reaction structural characterization.
Embodiment 6：
Catalyst composition and mass percentage and embodiment 1 are consistent in this embodiment, are Fe：27.78%, CaO：28.06%, Mg
(Al)O：44.16%.Preparation method place same as Example 1 repeats no more, the difference is that catalyst roasts in preparation step
Burning condition is different, and it is 800 DEG C that maturing temperature is increased by 500 DEG C.Characterization discovery prepares Fe nanoparticle in obtained catalyst
Average-size is increased to 9.5 nm.
The online upgrading of bio oil crude product is carried out under cracking condition same as Example 1.Experimental studies have found that with biology
Oily crude product is compared, and acids, furans are substantially completely removed in refining biological oil, and the content of group compounds of aldehydes and ketones significantly reduces
To 3.02%, hydrocarbon compound content increases to 20.52%（Wherein fat hydrocarbon content is 12.89%, and arene content is
7.63%）, content of phenolic compounds increases to 76.46%.Unexpected compounds content is substantially reduced in bio oil after upgrading, oxygen-containing
Amount and acid significant decrease, stability greatly improve, and quality is obviously improved.Compared with Example 1, when maturing temperature liter
At up to 800 DEG C, the main active component Fe nano-particles size of catalyst is not significantly increased, and then so that it is still remained higher and urge
Change activity.Surface is without obvious carbon distribution to be found to post catalyst reaction structural characterization.
Claims (4)
1. a kind of method using the online improving quality of bio oil of iron-based composite catalyst, which is characterized in that with Fe/CaO/Mg (Al) O
Biomass and Catalyst packing are subjected to fast pyrogenation, biomass in the reactor using wood powder as biomass material for catalyst
It is pyrolyzed the steam generated and directly carries out catalytic pyrolysis in catalyst surface, the biological oil vapour after obtaining upgrading, finally to upgrading
Biological oil vapour afterwards carries out the online component of GC/MS and content analysis；
The catalyst is using Mg (Al) O as carrier, and using Fe as vapor reforming main active component, CaO is as cocatalyst component
And carrier, the mass percentage of each component are：Fe is 10%-30%, and CaO 25%-48%, Mg (Al) O are 40%-48%；
The catalyst is prepared with following steps：
（a）Hydrotalcite precursor preparation：By Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
It is [Mg that concentration is made into deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
For 2 mol/L NaOH solution as precipitating reagent；It is slowly that the above-mentioned salt-mixture prepared is molten under continuous strong stirring condition
Liquid is continuously added dropwise in aqueous slkali, and controls final solution pH value 10.5 ~ 12, forms suspension after being added dropwise；In room temperature
Under the conditions of crystallization for 24 hours, by the centrifugation of gained precipitation solution, to wash to supernatant pH be 7, grinds and obtains after dry 12h at 100 DEG C
Laminate contains the single presoma of hydrotalcite of Fe, Ca, Mg, Al element；
（b）Calcining reduction：Weigh a certain amount of step（a）The single presoma of obtained hydrotalcite is placed in tube-type atmosphere furnace, also
In Primordial Qi atmosphere, temperature be 500 DEG C~800 DEG C under the conditions of calcine 2h~6h, be naturally cooling to room temperature, obtain Fe based composite catalysis
Agent.
2. the method according to claim 1 using the online improving quality of bio oil of iron-based composite catalyst, which is characterized in that institute
Stating reactor is pyrolysis-high resolution gas chromatography mass spectrometry device.
3. the method according to claim 1 using the online improving quality of bio oil of iron-based composite catalyst, which is characterized in that institute
Stating pyrolysis reaction temperature is 550-700 DEG C, residence time 25s, and the mass ratio of catalyst and biomass dosage is 10-20.
4. the method according to claim 1 using the online improving quality of bio oil of iron-based composite catalyst, which is characterized in that institute
State the one or both ends that catalyst is loaded into biomass material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810576994.XA CN108855101B (en) | 2016-07-18 | 2016-07-18 | Method for online upgrading bio-oil by using iron-based composite catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810576994.XA CN108855101B (en) | 2016-07-18 | 2016-07-18 | Method for online upgrading bio-oil by using iron-based composite catalyst |
| CN201610563540.XA CN106268826B (en) | 2016-07-18 | 2016-07-18 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610563540.XA Division CN106268826B (en) | 2016-07-18 | 2016-07-18 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108855101A true CN108855101A (en) | 2018-11-23 |
| CN108855101B CN108855101B (en) | 2020-10-20 |
Family
ID=57652042
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810576994.XA Active CN108855101B (en) | 2016-07-18 | 2016-07-18 | Method for online upgrading bio-oil by using iron-based composite catalyst |
| CN201810576993.5A Active CN108772070B (en) | 2016-07-18 | 2016-07-18 | Preparation method of iron-based composite catalyst for online upgrading of bio-oil |
| CN201610563540.XA Active CN106268826B (en) | 2016-07-18 | 2016-07-18 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810576993.5A Active CN108772070B (en) | 2016-07-18 | 2016-07-18 | Preparation method of iron-based composite catalyst for online upgrading of bio-oil |
| CN201610563540.XA Active CN106268826B (en) | 2016-07-18 | 2016-07-18 | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN108855101B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129086A (en) * | 2019-03-13 | 2019-08-16 | 盐城工业职业技术学院 | A kind of method of catalytic pyrolysis plant asphalt preparation biology boat coal |
| CN114989842A (en) * | 2022-06-09 | 2022-09-02 | 武汉轻工大学 | Method for preparing bio-oil rich in monocyclic aromatic hydrocarbon by biomass graded catalytic pyrolysis |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587672B (en) * | 2018-04-09 | 2019-07-19 | 华中科技大学 | A kind of online deoxidation method for upgrading of bio oil |
| MY193483A (en) | 2018-04-28 | 2022-10-17 | Beijing Sanju Environmental Prot & New Materials Co Ltd | Conversion process for organic material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101455964A (en) * | 2008-12-18 | 2009-06-17 | 浙江工业大学 | Preparation method of nickel based metal load type catalyst |
| US20100126910A1 (en) * | 2008-10-29 | 2010-05-27 | E. I. Du Pont De Nemours And Company | Process for flocculation of a tailings stream |
| WO2011062410A2 (en) * | 2009-11-17 | 2011-05-26 | 한국에너지기술연구원 | Method for making hydrocarbons by using a lipid derived from a biological organism and hydrotalcite |
| CN102574114A (en) * | 2009-04-22 | 2012-07-11 | 科伊奥股份有限公司 | Controlled activity pyrolysis catalysts |
| CN103415591A (en) * | 2011-03-10 | 2013-11-27 | 科伊奥股份有限公司 | Refractory mixed-metal oxides and spinel compositions for thermo-catalytic conversion of biomass |
| CN103773589A (en) * | 2014-01-15 | 2014-05-07 | 东南大学 | Method for preparing biologic oil from blue algae in catalytic cracking mode in vacuum |
| CN103922553A (en) * | 2014-04-29 | 2014-07-16 | 章琳茂 | Method for preparing raw oil from sludge |
| CN104560102A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for improving quality of bio-oil |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603498A (en) * | 2012-02-08 | 2012-07-25 | 厦门大学 | Method for extracting phenolic compounds from biological oil |
| CN102585890B (en) * | 2012-02-29 | 2014-02-26 | 厦门大学 | Separation upgrading method for biological oil |
| US9222032B2 (en) * | 2012-05-01 | 2015-12-29 | Mississippi State University | Composition and methods for improved fuel production |
| IN2015DN00325A (en) * | 2012-08-08 | 2015-06-12 | Albemarle Europe Sprl | |
| CN103301840A (en) * | 2013-06-04 | 2013-09-18 | 北京化工大学 | Supported high-dispersity Fischer-Tropsch synthesis metal catalyst, preparation method and application |
| EP3023147B1 (en) * | 2013-07-18 | 2020-12-16 | China University of Petroleum-Beijing | Iron-based hydrogenation catalyst and applications thereof |
| JP6536102B2 (en) * | 2014-12-10 | 2019-07-03 | 宇部興産株式会社 | Solidification material for neutralization treatment residue of acid water, solidification treatment product of neutralization treatment residue of acid water, and solidification treatment method of neutralization treatment residue of acid water |
| CN104801305B (en) * | 2015-03-12 | 2017-11-07 | 大连理工大学 | A kind of height is than table body phase transition metal silicide hydrogenation deoxidation catalyst, preparation method and applications |
| CN105597678B (en) * | 2016-01-11 | 2018-08-07 | 湖南大学 | A kind of the charcoal composite material and preparation method and purposes of the modification of Mg/Al hydrotalcites |
| CN106000403B (en) * | 2016-05-17 | 2018-10-23 | 北京化工大学 | A kind of Fe bases catalyst and application with higher CO hydrogenation reactions activity and yield of light olefins |
-
2016
- 2016-07-18 CN CN201810576994.XA patent/CN108855101B/en active Active
- 2016-07-18 CN CN201810576993.5A patent/CN108772070B/en active Active
- 2016-07-18 CN CN201610563540.XA patent/CN106268826B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100126910A1 (en) * | 2008-10-29 | 2010-05-27 | E. I. Du Pont De Nemours And Company | Process for flocculation of a tailings stream |
| CN101455964A (en) * | 2008-12-18 | 2009-06-17 | 浙江工业大学 | Preparation method of nickel based metal load type catalyst |
| CN102574114A (en) * | 2009-04-22 | 2012-07-11 | 科伊奥股份有限公司 | Controlled activity pyrolysis catalysts |
| WO2011062410A2 (en) * | 2009-11-17 | 2011-05-26 | 한국에너지기술연구원 | Method for making hydrocarbons by using a lipid derived from a biological organism and hydrotalcite |
| CN103415591A (en) * | 2011-03-10 | 2013-11-27 | 科伊奥股份有限公司 | Refractory mixed-metal oxides and spinel compositions for thermo-catalytic conversion of biomass |
| CN104560102A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for improving quality of bio-oil |
| CN103773589A (en) * | 2014-01-15 | 2014-05-07 | 东南大学 | Method for preparing biologic oil from blue algae in catalytic cracking mode in vacuum |
| CN103922553A (en) * | 2014-04-29 | 2014-07-16 | 章琳茂 | Method for preparing raw oil from sludge |
Non-Patent Citations (3)
| Title |
|---|
| NAZARI LALEH ET AL.: ""Hydrothermal liquefaction of woody bimass in hot-compressed water:Catalyst screening and conprehesive characterization of bio-crude oils"", 《FUEL》 * |
| 周铭昊: ""水相生物油提质制备含氧燃料催化剂制备与研究"", 《中国博士学位论文全文数据库工程科技I辑》 * |
| 尹海云等: ""HZSM-5在线提质生物油及催化失活机理分析"", 《燃料化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129086A (en) * | 2019-03-13 | 2019-08-16 | 盐城工业职业技术学院 | A kind of method of catalytic pyrolysis plant asphalt preparation biology boat coal |
| CN114989842A (en) * | 2022-06-09 | 2022-09-02 | 武汉轻工大学 | Method for preparing bio-oil rich in monocyclic aromatic hydrocarbon by biomass graded catalytic pyrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108772070B (en) | 2020-10-20 |
| CN106268826A (en) | 2017-01-04 |
| CN108772070A (en) | 2018-11-09 |
| CN106268826B (en) | 2018-08-31 |
| CN108855101B (en) | 2020-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yaman et al. | Catalytic upgrading of pyrolysis vapours: effect of catalyst support and metal type on phenolic content of bio-oil | |
| Lu et al. | Catalytic fast pyrolysis of biomass with noble metal-like catalysts to produce high-grade bio-oil: analytical Py-GC/MS study | |
| Wang et al. | Renewable aromatic hydrocarbons production from catalytic pyrolysis of lignin with Al-SBA-15 and HZSM-5: Synergistic effect and coke behaviour | |
| Wu et al. | Microwave-assisted pyrolysis of waste cooking oil for hydrocarbon bio-oil over metal oxides and HZSM-5 catalysts | |
| Ren et al. | Increasing light aromatic products during upgrading of lignite pyrolysis vapor over Co-modified HZSM-5 | |
| Dejhosseini et al. | Catalytic cracking reaction of heavy oil in the presence of cerium oxide nanoparticles in supercritical water | |
| CN106268826B (en) | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil | |
| Vichaphund et al. | In situ catalytic pyrolysis of Jatropha wastes using ZSM-5 from hydrothermal alkaline fusion of fly ash | |
| Liu et al. | Promotion of monocyclic aromatics by catalytic fast pyrolysis of biomass with modified HZSM-5 | |
| Rocha et al. | Enhancement of bio-oil obtained from co-pyrolysis of lignocellulose biomass and LDPE by using a natural zeolite | |
| CN110227468B (en) | Preparation of nickel-calcium based composite catalyst and application of nickel-calcium based composite catalyst in biomass catalytic pyrolysis process | |
| Zhou et al. | Conversion of xylose into furfural over MC-SnOx and NaCl catalysts in a biphasic system | |
| Xue et al. | Regulation mechanism of three key parameters on catalytic characterization of molybdenum modified bimetallic micro-mesoporous catalysts during catalytic fast pyrolysis of enzymatic hydrolysis lignin | |
| Zhang et al. | Enhancement of aromatics production via cellulose fast pyrolysis over Ru modified hierarchical zeolites | |
| He et al. | Selective catalytic synthesis of bio-based terephthalic acid from lignocellulose biomass | |
| Kong et al. | Production of liquid fuel intermediates from furfural via aldol condensation over La2O2CO3-ZnO-Al2O3 catalyst | |
| Bu et al. | Enhancement of bio-oil quality over self-derived bio-char catalyst via microwave catalytic pyrolysis of peanut shell | |
| CN114588910A (en) | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization | |
| CN111592906A (en) | Preparation of C from biomass6~C18Method for powering fuel | |
| Beh et al. | Flame-made amorphous solid acids with tunable acidity for the aqueous conversion of glucose to levulinic acid | |
| CN110694673A (en) | Aromatization catalyst of waste edible oil and preparation method and application thereof | |
| Uddin et al. | Efficient pyrolysis process of lignin over dual catalyst bed for the production of Phenols and Aromatics | |
| Li et al. | Enhancing bio-aromatics yield in bio-oil from catalytic fast pyrolysis of bamboo residues over bi-metallic catalyst and reaction mechanism based on quantum computing | |
| Wang et al. | A 3D porous Fe-MoS2/CMF catalyst for high-efficient catalytic reforming of lignin vapor by microwave irradiation | |
| Xue et al. | Product regulation and catalyst deactivation during ex-situ catalytic fast pyrolysis of biomass over Nickel-Molybdenum bimetallic modified micro-mesoporous zeolites and clays |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |