CN106268826A - Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil - Google Patents
Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil Download PDFInfo
- Publication number
- CN106268826A CN106268826A CN201610563540.XA CN201610563540A CN106268826A CN 106268826 A CN106268826 A CN 106268826A CN 201610563540 A CN201610563540 A CN 201610563540A CN 106268826 A CN106268826 A CN 106268826A
- Authority
- CN
- China
- Prior art keywords
- bio oil
- catalyst
- based composite
- iron
- composite catalyst
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000012075 bio-oil Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 238000002407 reforming Methods 0.000 claims abstract description 3
- 239000002028 Biomass Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052599 brucite Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 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 5
- 239000007788 liquid Substances 0.000 claims description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 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 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000011833 salt mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000003987 high-resolution gas chromatography Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 21
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000292 calcium oxide Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 150000002576 ketones Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- -1 phenol compound Chemical class 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000007670 refining Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000010970 precious metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 239000000126 substance Substances 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit 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
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 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
- 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
- 230000002779 inactivation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 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
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
-
- B01J35/393—
-
- B01J35/399—
-
- 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
Abstract
A kind of iron-based composite catalyst for the online upgrading of bio oil, it is characterized in that, described catalyst with Mg (Al) O as carrier, using Fe as vapor reforming main active component, CaO is as cocatalyst component and carrier, the weight/mass percentage composition of each component is: Fe is 10% 30%, and CaO is 25% 48%, and Mg (Al) O is 40% 48%.
Description
Technical field
The invention belongs to biomass energy utilizes technical field, carries online for bio oil more particularly to one
The Fe based composite catalyst of matter and methods for making and using same thereof.
Background technology
As a kind of reproducible clean energy resource, product liquid-bio oil that biomass are obtained by rapidly pyrolysing and liquefying
It is a kind of novel liquid fuel, there is energy density high, easily store transport, and the advantage such as sulfur, nitrogen content be low, it is expected to alleviate energy
The problem of environmental pollution that source shortage and use Fossil fuel are brought.But, the thick product composition of bio oil is extremely complex, almost wraps
Contain all kinds of oxygen-bearing organic matter (acid, aldehyde, ketone, alcohol, phenol, furan, sugar etc.), cause its poor stability, acidity height, calorific value low, viscous
The shortcomings such as degree is big, seriously hinder its popularization and application as hydrocarbon fuel.How to improve bio oil oil quality to have become as
Affect the application of biomass fast pyrolysis technology and a key technical problem of economy.In order to improve the quality of bio oil,
People had done the research work of many in the past.
Patent " a kind of method improving quality of bio-oil " (CN104560102A) discloses a kind of raising quality of bio-oil
Method, described method include will cracking produce bio oil add autoclave, add calcium oxide as catalyst, at N2
Under protective condition, control reaction by a point temperature section and improve quality of bio-oil.But, in this patent, biomass material must be pre-through sulphuric acid
Processing, and in the refining biological oil obtained, composition is the most more complicated, target product furfuryl acetone class productivity is less than 25%, Gao Han
The group compounds of aldehydes and ketones of amount makes stability of bio-oil be not effectively improved.
Patent " a kind of method of improving quality of biomass oil " (CN101358138A) discloses the side of a kind of improving quality of biomass oil
Method, described method reduces heavy constituent in bio-oil, by bio-oil, supercritical reaction medium second by supercritical catalyst reaction
Alcohol or methanol, HZSM-5 molecular sieve catalyst input autoclave, at N2Protection, pressure is 7.5-11MPa, 100-300 DEG C
Reacting 3-5 hour under temperature conditions, in refining biological oil, heavy constituent weight/mass percentage composition is 15%-28%.But, this patent uses
Supercritical, high pressure reacts, and severe reaction conditions exists certain difficulty during actual popularization and application, and and not mentioned to biology
In oil, acids, aldehydes etc. affect the adjustment of formula problem of bio oil corrosivity and stability.
Additionally, above-mentioned patent is all to carry out the bio oil that biomass pyrolytic produces again heating after condensation is collected carrying
Matter processes, and energy consumption is high, processing routine complexity and somewhat expensive, applies the most difficult on commercial technologies.
Catalyst online catalytic pyrolysis biomass fast pyrogenation product is used to prepare high-quality biological oil because of its whole reaction
Same reactor is carried out, without by bio oil condensation heating again, low cost simple to operate, refined, becoming current
Study a kind of most commonly used method, and its core is the selection of catalyst.The use of current domestic and international each research unit report
Catalyst in bio oil catalysis upgrading mainly includes metal-oxide, zeolite molecular sieve and precious metal.Wherein, metal
Oxide raw material is easy to get, cheap, but its catalysis activity is relatively low；Precious metal based catalysts activity is high, but expensive and
Easy-sintering inactivation under hot conditions or during long-play；Molecular sieve catalysts can meet high activity and shape selective catalysis simultaneously
Two kinds of functions, but inactivate because of its stronger acidity easily carbon distribution.Therefore, find efficiently, the urging of cheap and anti-carbon, anti-sintering
Agent, is the emphasis of present stage bio oil this research work of online upgrading.
Summary of the invention
For problem above, the present invention overcomes weak point in prior art, it is provided that a kind of with low cost, catalysis activity
Good and the anti-anti-carbon Fe based composite catalyst for the online upgrading of bio oil of sintering；
Present invention simultaneously provides the preparation method and application method of this Fe based composite catalyst.
The present invention solves technical problem and adopts the following technical scheme that a kind of iron-based for the online upgrading of bio oil is compound and urge
Agent, it is characterised in that described catalyst with Mg (Al) O as carrier, using Fe as vapor reforming main active component, CaO conduct
Cocatalyst component and carrier, the weight/mass percentage composition of each component is: Fe be 10%-30%, CaO be that 25%-48%, Mg (Al) O is
40%-48%。
The concrete feature of this programme also has, and in the carrier, its size controlling is at 5-for described main active component Fe high degree of dispersion
10nm。
Fe based composite catalyst through the following steps that preparation:
A prepared by () hydrotalcite precursor: by Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
Concentration it is made into for [Mg in deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
It is that the NaOH solution of 2 mol/L is as precipitant；Under continuous strong stirring condition, slowly by molten for the above-mentioned salt-mixture prepared
Liquid drops in aqueous slkali continuously, and controls final solution pH value 10.5 ~ 12, forms suspension after dropping；In room temperature
Under the conditions of crystallization 24h, be 7 by centrifugal for gained precipitation solution, washing to supernatant pH, grind after being dried 12h at 100 DEG C and obtain
Laminate contains the single presoma of brucite of Fe, Ca, Mg, Al element.
(b) calcining reduction: weigh the single presoma of brucite that a certain amount of step (a) obtains and be placed in tube-type atmosphere furnace,
In reducing atmosphere, temperature calcine 2h～6h under the conditions of being 500 DEG C～800 DEG C, be naturally cooling to room temperature, obtain that Fe base is compound urges
Agent.
A kind of application process that above-mentioned iron-based composite catalyst is used for the online upgrading of bio oil, it comprises the steps:
With Fe/CaO/Mg (Al) O as catalyst, with wood powder as biomass material, biomass are entered in the reactor with Catalyst packing
Row fast pyrogenation, the steam that biomass pyrolytic produces directly carries out catalytic pyrolysis at catalyst surface, it is thus achieved that the biology after upgrading
Oil vapour, finally carries out the online component of GC/MS and content analysis to the bio oil steam after upgrading.
The concrete feature of the present invention also has, and described reactor is pyrolysis-high resolution gas chromatography mass spectrometry device (Py-GC/MS)；
Described pyrolysis reaction temperature is 550-700 DEG C, and the time of staying is 25s, and catalyst is 10-with the mass ratio of biomass consumption
20；
Described catalyst is loaded into the one or both ends of biomass material.
The preparation method of a kind of iron-based composite catalyst, it comprises the steps:
A prepared by () hydrotalcite precursor: by Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
Concentration it is made into for [Mg in deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
It is that the NaOH solution of 2 mol/L is as precipitant；Under continuous strong stirring condition, slowly by molten for the above-mentioned salt-mixture prepared
Liquid drops in aqueous slkali continuously, and controls final solution pH value 10.5 ~ 12, forms suspension after dropping；In room temperature
Under the conditions of crystallization 24h, be 7 by centrifugal for gained precipitation solution, washing to supernatant pH, grind after being dried 12h at 100 DEG C and obtain
Laminate contains the single presoma of brucite of Fe, Ca, Mg, Al element.
(b) calcining reduction: weigh the single presoma of brucite that a certain amount of step (a) obtains and be placed in tube-type atmosphere furnace,
In reducing atmosphere, temperature calcine 2h～6h under the conditions of being 500 DEG C～800 DEG C, be naturally cooling to room temperature, obtain that Fe base is compound urges
Agent.
The concrete feature of the present invention also has, (Mg in mixing salt solution in step (a)2++Ca2+)/(Fe3++Al3+) mol ratio
For (1 ~ 4): 1, Mg2+: Ca2+: Fe3+: Al3+Mol ratio more preferably 1:1:1:1 or 2:2:1:1 or 3:3:1:1 or 4:4:
1:1.
Reducing atmosphere described in described step (b) is hydrogen or reducing atmosphere is hydrogen and nitrogen or the mixing of argon
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 changes based on LDHs precursor construction topology, adds Mg (Al) O composite oxides simultaneously and realizes as carrier
The high degree of dispersion of main active component Fe of catalyst, is remarkably improved catalysis activity and effectively prevents in biomass fast pyrogenation product
The carbon distribution reaction of macromolecular oligo thing causes catalysqt deactivation.
2, the catalyst that the present invention provides can remove the unexpected compound of acids, aldoketones etc. in bio oil completely, has
Effect reduces its acidity and significantly improves its stability.
3, the catalyst that the present invention provides may advantageously facilitate the formation of phenol compound in bio oil, can to its selectivity
Up to 89.32%, while effectively promoting bio oil calorific value, it also has high chemical added value, be prepare phenolic resin,
The important chemical intermediate of the material such as food additive and fine chemicals.
Detailed description of the invention
Embodiment 1: the preparation method of a kind of iron-based composite catalyst, it comprises the steps:
The preparation of LDHs presoma: according to Mg2+: Ca2+: Fe3+: Al3+Mol ratio is about the ratio of 1: 1: 1: 1 and 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 adds
Deionized water is configured to 500 ml mixed solutions, weighs 50.99gNaNO3Add deionized water and be configured to 500 ml mixed solutions,
Separately weigh 56gNaOH addition deionized water and be configured to the aqueous slkali that 800mL concentration is 2M.By NaNO3Solution and NaOH solution are fallen
Enter in four-hole boiling flask, under mechanical stirring mixing salt solution is added drop-wise in above-mentioned mixed ammonium/alkali solutions so that final solution pH is
11.2, by crystallization 24 hours under gained serosity room temperature condition, it is washed with deionized, is centrifuged 4 times, at 100 DEG C, be dried 12 little
Time, grind and obtain LDHs presoma.
Roasting reduction: weigh 5g LDHs presoma, uniformly divide in Ci Zhou is placed in tube-type atmosphere furnace, at N2/H2
Under (90%/10%) reducing atmosphere, it is warming up to 500 DEG C with 10 DEG C/min, is incubated 2 hours, treat that temperature is naturally down to room temperature and is obtained Fe
Based composite catalyst.
Fe based composite catalyst composition and weight/mass percentage composition prepared by said method are Fe:27.78%, CaO:28.06%,
Mg (Al) O:44.16%, does not finds other impurity thing phases, and wherein Fe nanoparticle average-size is 7.3 nm.
A kind of application process that above-mentioned iron-based composite catalyst is used for the online upgrading of bio oil, it comprises the steps:
With Fe/CaO/Mg (Al) O as catalyst, with wood powder as biomass material, biomass are entered in the reactor with Catalyst packing
Row fast pyrogenation, the steam that biomass pyrolytic produces directly carries out catalytic pyrolysis at catalyst surface, it is thus achieved that the biology after upgrading
Oil vapour, finally carries out the online component of GC/MS and content analysis to the bio oil steam after upgrading.Described reactor for cracking-
Gas chromatography combined with mass spectrometry device (Py-GC/MS)；Described pyrolysis reaction temperature is 550-700 DEG C, and the time of staying is 25s, catalysis
Agent is 10-20 with the mass ratio of biomass consumption；Described catalyst is loaded into the one or both ends of biomass material.Use Py-
GC/MS device, filling 0.5mg wood powder and 10mg catalyst respectively in sample cell, arranging reaction temperature is 550 DEG C, during stop
Between be 20s, clack box and transmission line temperature are 290 DEG C.
The typical component of the thick product of bio oil that the direct fast pyrogenation of biomass produces is under the above-described reaction conditions: hydro carbons
(predominantly aliphatic hydrocarbon) content 1.38%, phenol content is 52.53%, acids content 18.05%, aldoketones content 23.29%, furan
Class of muttering content 4.75%.
The thick product of bio oil of component described above is carried out online upgrading, experimental studies have found that gained refined biological line of oils
Having got significant optimization, wherein the unexpected compound such as acids, aldoketones is substantially completely removed, bio oil acidity and stability
It is substantially improved.Phenolic compound becomes primary product, and content significantly 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%, arene content is 4.43%), bio oil
Quality is obviously improved.Finding post catalyst reaction structural characterization, its surface does not finds carbon deposition phenomenon.
Embodiment 2:
In this embodiment, the preparation method of catalyst part same as in Example 1 repeats no more, and difference is active component
Content is different, wherein Mg2+: Ca2+: Fe3+: Al3+Mol ratio is about 4: 4: 1: 1.The catalyst composition prepared and percent mass
Content is Fe:11.41%, CaO:42.06%, Mg (Al) O:46.53%, does not finds other impurity thing phases, and wherein Fe nanoparticle is put down
The most a size of 5.2 nm.
Bio oil thick On-line Product upgrading is carried out under cracking condition same as in Example 1.Experimental studies have found that, with biology
The thick product of oil is compared, and in refining biological oil, acid is substantially completely removed, and the content of group compounds of aldehydes and ketones is reduced to 5.46%, hydrocarbon
It is 18.89% that kind compound content increases to 33.52%(wherein fat hydrocarbon content, 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 substantially reduces, and oxygen content and acidity significantly reduce, and stability is greatly improved, and quality has promoted.With embodiment 1
Comparing, in catalyst, the reduction of main active component Fe content makes catalyst activity decrease.To post catalyst reaction structural table
Levying existing, there is a small amount of carbon distribution on its surface.
Embodiment 3:
In this embodiment, catalyst composition and weight/mass percentage composition are consistent with embodiment 1, for Fe:27.78%, CaO:28.06%, Mg
(Al) O:44.16%, does not finds other impurity thing phases, and wherein Fe nanoparticle average-size is 7.3 nm.Preparation method and enforcement
Example 1 is identical, and here is omitted.
Above-mentioned iron-based composite catalyst is used for the application process part same as in Example 1 of the online upgrading of bio oil no longer
Repeating, difference from Example 1 is in bio oil grading process that catalyst is different from wood powder type of feed, is specially wood
Powder 0.5mg, catalyst 10mg load to rock in sample cell makes both mix homogeneously.Experimental studies have found that, after upgrading in bio oil
Acid content is 16.18%, hydrocarbons content be 20.58%(wherein fat hydrocarbon content be 4.32%, arene contains
Amount is 16.26%), content of phenolic compounds is 46.29%, and content of group compounds of aldehydes and ketones is 10.67%, furfuran compound content
It is 6.28%.Compared with Example 1, although using catalyst and hydrocarbon in the mode bio oil of biomass material mixed pyrolysis
The content of matter increased, but compound conversion capability unexpected to acids, aldoketones etc. is substantially reduced, bio oil acid and
Stability does not make moderate progress.
Embodiment 4:
In this embodiment, catalyst composition and weight/mass percentage composition are consistent with embodiment 1, for Fe:27.78%, CaO:28.06%, Mg
(Al) O:44.16%, does not finds other impurity thing phases, and wherein Fe nanoparticle average-size is 7.3 nm.Preparation method and enforcement
Example 1 is identical, and here is omitted.
A kind of being combined by above-mentioned iron-based of application process that above-mentioned iron-based composite catalyst is used for the online upgrading of bio oil is urged
Agent repeats no more for the application process part same as in Example 1 of the online upgrading of bio oil, and difference is bio oil
In grading process, the ratio of catalyst/wood powder consumption is different, specially wood powder loadings 0.5mg, loaded catalyst 5mg.Experiment
Research finds, compared with product thick with bio oil, in refining biological oil, acid content is reduced to 2.18%, hydrocarbons content
Increasing 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%.After upgrading oxygen-containing in bio oil
Amount and acidity decrease, and stability increases, and quality is obviously improved.Compared with Example 1, catalyst loading
Reduce and considerably reduce active site so that catalyst activity decreases, compound unexpected to acids, aldoketones etc.
Conversion capability decreases.Finding post catalyst reaction structural characterization, its surface is without carbon distribution.
Embodiment 5:
In this embodiment, catalyst composition and weight/mass percentage composition are consistent with embodiment 1, for Fe:27.78%, CaO:28.06%, Mg
(Al) O:44.16%, does not finds other impurity thing phases, and wherein Fe nanoparticle average-size is 7.3 nm.Preparation method and enforcement
Example 1 is identical, and here is omitted.
Difference from Example 1 is that biomass cracking reaction temperature is risen a height of 700 DEG C by 550 DEG C.Experimentation is sent out
Existing, compared with product thick with bio oil, in refined bio oil, hydrocarbons content increases to 54.15%(wherein fat hydrocarbon content
Being 39.89%, arene content is 14.26%), content of phenolic compounds is reduced to 39.06%, and content of group compounds of aldehydes and ketones drops
As little as 1.17%, furfuran compound content is 5.04%, and possibly together with a small amount of acid in product, content is about 0.58%.Carry
After matter, in bio oil, oxygen content and acidity significantly reduce, and stability is greatly improved, and quality is obviously improved.With embodiment 1
Compare, the generation raising beneficially hydrocarbon compound of upgrading reaction temperature, but for acids, the conversion of group compounds of aldehydes and ketones
Ability slightly reduces.Finding post catalyst reaction structural characterization, there is a small amount of carbon distribution on its surface.
Embodiment 6:
In this embodiment, catalyst composition and weight/mass percentage composition are consistent with embodiment 1, for Fe:27.78%, CaO:28.06%, Mg
(Al) O:44.16%.Preparation method part same as in Example 1 repeats no more, and difference is catalyst roasting in preparation process
Burning condition is different, and sintering temperature is risen a height of 800 DEG C by 500 DEG C.Characterize Fe nanoparticle in the catalyst found obtained by preparing
Average-size is increased to 9.5 nm.
Bio oil thick On-line Product upgrading is carried out under cracking condition same as in Example 1.Experimental studies have found that, with biology
The thick product of oil is compared, and in refining biological oil, acids, furans are substantially completely removed, and the content of group compounds of aldehydes and ketones significantly reduces
To 3.02%, it is 12.89% that hydrocarbon compound content increases to 20.52%(wherein fat hydrocarbon content, and arene content is
7.63%), content of phenolic compounds increases to 76.46%.After upgrading, in bio oil, unexpected compounds content substantially reduces, oxygen-containing
Amount and acidity significantly reduce, and stability is greatly improved, and quality is obviously improved.Compared with Example 1, when sintering temperature liter
When up to 800 DEG C, catalyst main active component Fe nano-particles size does not significantly increase, and then makes it still maintain higher urging
Change activity.Finding post catalyst reaction structural characterization, its surface is without obvious carbon distribution.
Claims (10)
1. the iron-based composite catalyst for the online upgrading of bio oil, it is characterised in that described catalyst with Mg (Al) O is
Carrier, contains as cocatalyst component and carrier, the percent mass of each component using Fe as vapor reforming main active component, CaO
Amount is: Fe be 10%-30%, CaO be 25%-48%, Mg (Al) O be 40%-48%.
Iron-based composite catalyst for the online upgrading of bio oil the most according to claim 1, it is characterised in that described work
In the carrier, its size controlling is at 5-10nm for property component Fe high degree of dispersion.
Iron-based composite catalyst for the online upgrading of bio oil the most according to claim 1, it is characterised in that this catalysis
Prepared by agent following steps:
A prepared by () hydrotalcite precursor: by Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
Concentration it is made into for [Mg in deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
It is that the NaOH solution of 2 mol/L is as precipitant；Under continuous strong stirring condition, slowly by molten for the above-mentioned salt-mixture prepared
Liquid drops in aqueous slkali continuously, and controls final solution pH value 10.5 ~ 12, forms suspension after dropping；In room temperature
Under the conditions of crystallization 24h, be 7 by centrifugal for gained precipitation solution, washing to supernatant pH, grind after being dried 12h at 100 DEG C and obtain
Laminate contains the single presoma of brucite of Fe, Ca, Mg, Al element；
B () calcining reduction: weigh the single presoma of brucite that a certain amount of step (a) obtains and be 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.
4. the method utilizing iron-based composite catalyst online improving quality of bio oil, it is characterised in that with Fe/CaO/Mg (Al) O
For catalyst, with wood powder as biomass material, biomass and Catalyst packing are carried out fast pyrogenation, biomass in the reactor
The steam that pyrolysis produces directly carries out catalytic pyrolysis at catalyst surface, it is thus achieved that the bio oil steam after upgrading, finally to upgrading
After bio oil steam carry out the online component of GC/MS and content analysis.
The method utilizing iron-based composite catalyst online improving quality of bio oil the most according to claim 4, it is characterised in that institute
Stating reactor is pyrolysis-high resolution gas chromatography mass spectrometry device.
The method utilizing iron-based composite catalyst online improving quality of bio oil the most according to claim 4, it is characterised in that institute
Stating pyrolysis reaction temperature and be 550-700 DEG C, the time of staying is 25s, and catalyst is 10-20 with the mass ratio of biomass consumption.
The method utilizing iron-based composite catalyst online improving quality of bio oil the most according to claim 4, it is characterised in that institute
State catalyst and be loaded into the one or both ends of biomass material.
8. the preparation method for the iron-based composite catalyst of the online upgrading of bio oil, it is characterised in that it includes as follows
Step:
A prepared by () hydrotalcite precursor: by Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙9H2O is molten
Concentration it is made into for [Mg in deionized water2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Another compound concentration
It is that the NaOH solution of 2 mol/L is as precipitant；Under continuous strong stirring condition, slowly by molten for the above-mentioned salt-mixture prepared
Liquid drops in aqueous slkali continuously, and controls final solution pH value 10.5 ~ 12, forms suspension after dropping；In room temperature
Under the conditions of crystallization 24h, be 7 by centrifugal for gained precipitation solution, washing to supernatant pH, grind after being dried 12h at 100 DEG C and obtain
Laminate contains the single presoma of brucite of Fe, Ca, Mg, Al element；
B () calcining reduction: weigh the single presoma of brucite that a certain amount of step (a) obtains and be 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.
The preparation method of the iron-based composite catalyst for the online upgrading of bio oil the most according to claim 8, its feature
It is, (Mg in mixing salt solution in step (a)2++Ca2+)/(Fe3++Al3+) mol ratio is (1 ~ 4): 1；Mg2+: Ca2+: Fe3+:
Al3+Mol ratio is 1:1:1:1 or 2:2:1:1 or 3:3:1:1 or 4:4:1:1.
The preparation method of the iron-based composite catalyst for the online upgrading of bio oil the most according to claim 8, its feature
Being, reducing atmosphere described in step (b) is hydrogen or reducing atmosphere is hydrogen and nitrogen or the gaseous mixture of argon, Qi Zhongqing
Gas percentage by volume in mixed gas is 10%.
Priority Applications (3)
| 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 |
| CN201810576993.5A CN108772070B (en) | 2016-07-18 | 2016-07-18 | Preparation method of iron-based composite catalyst for online upgrading of bio-oil |
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810576993.5A Division CN108772070B (en) | 2016-07-18 | 2016-07-18 | Preparation method of iron-based composite catalyst for online upgrading of bio-oil |
| CN201810576994.XA Division CN108855101B (en) | 2016-07-18 | 2016-07-18 | Method for online upgrading bio-oil by using iron-based composite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106268826A true CN106268826A (en) | 2017-01-04 |
| CN106268826B CN106268826B (en) | 2018-08-31 |
Family
ID=57652042
Family Applications (3)
| 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 |
| CN201810576994.XA Active CN108855101B (en) | 2016-07-18 | 2016-07-18 | Method for online upgrading bio-oil by using iron-based composite catalyst |
| 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 Before (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 |
| CN201810576994.XA Active CN108855101B (en) | 2016-07-18 | 2016-07-18 | Method for online upgrading bio-oil by using iron-based composite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN108772070B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587672A (en) * | 2018-04-09 | 2018-09-28 | 华中科技大学 | A kind of online deoxidation method for upgrading of bio oil |
| WO2019205682A1 (en) * | 2018-04-28 | 2019-10-31 | 北京三聚环保新材料股份有限公司 | Conversion process for organic matter |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129086B (en) * | 2019-03-13 | 2021-07-13 | 盐城工业职业技术学院 | Method for preparing biological aviation kerosene by catalytic cracking of plant asphalt |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3023147A1 (en) * | 2013-07-18 | 2016-05-25 | China University of Petroleum-Beijing | Iron-based hydrogenation catalyst and applications thereof |
| CN106000403A (en) * | 2016-05-17 | 2016-10-12 | 北京化工大学 | Fe-based catalyst having high CO hydrogenation reaction activity and low carbon olefin yield and application |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2009314391B2 (en) * | 2008-10-29 | 2012-08-30 | The Chemours Company Fc, Llc. | Treatment of tailings streams |
| CN101455964B (en) * | 2008-12-18 | 2012-06-27 | 浙江工业大学 | Preparation method of nickel based metal load type catalyst |
| CN102574114B (en) * | 2009-04-22 | 2015-12-02 | 科伊奥股份有限公司 | The pyrolysis catalysts of controlled activity |
| KR101140340B1 (en) * | 2009-11-17 | 2012-05-03 | 한국에너지기술연구원 | Method of hydrocarbon production from biological origins using hydrotalcites as catalysts |
| US8921628B2 (en) * | 2011-03-10 | 2014-12-30 | Kior, Inc. | Refractory mixed-metal oxides and spinel compositions for thermo-catalytic conversion of biomass |
| 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 |
| JP2015529556A (en) * | 2012-08-08 | 2015-10-08 | アルベマール・ユーロプ・エスピーアールエル | Selective catalytic deoxygenation of biomass and catalyst therefor |
| CN104560102B (en) * | 2013-10-29 | 2016-05-18 | 中国石油化工股份有限公司 | A kind of method that improves quality of bio-oil |
| CN103773589B (en) * | 2014-01-15 | 2016-01-27 | 东南大学 | The method of blue-green algae vacuum catalytic cracking preparing bio-oil |
| CN103922553B (en) * | 2014-04-29 | 2015-11-18 | 章琳茂 | A kind of method of raw materials oil from mud |
| 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 |
-
2016
- 2016-07-18 CN CN201810576993.5A patent/CN108772070B/en active Active
- 2016-07-18 CN CN201810576994.XA patent/CN108855101B/en active Active
- 2016-07-18 CN CN201610563540.XA patent/CN106268826B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3023147A1 (en) * | 2013-07-18 | 2016-05-25 | China University of Petroleum-Beijing | Iron-based hydrogenation catalyst and applications thereof |
| CN106000403A (en) * | 2016-05-17 | 2016-10-12 | 北京化工大学 | Fe-based catalyst having high CO hydrogenation reaction activity and low carbon olefin yield and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587672A (en) * | 2018-04-09 | 2018-09-28 | 华中科技大学 | A kind of online deoxidation method for upgrading of bio oil |
| 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 |
| WO2019205682A1 (en) * | 2018-04-28 | 2019-10-31 | 北京三聚环保新材料股份有限公司 | Conversion process for organic matter |
| US11198820B2 (en) | 2018-04-28 | 2021-12-14 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an organic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108855101B (en) | 2020-10-20 |
| CN108772070A (en) | 2018-11-09 |
| CN106268826B (en) | 2018-08-31 |
| CN108772070B (en) | 2020-10-20 |
| CN108855101A (en) | 2018-11-23 |
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 | |
| Wu et al. | Microwave-assisted pyrolysis of waste cooking oil for hydrocarbon bio-oil over metal oxides and HZSM-5 catalysts | |
| Palizdar et al. | Catalytic upgrading of beech wood pyrolysis oil over iron-and zinc-promoted hierarchical MFI zeolites | |
| CN110227468B (en) | Preparation of nickel-calcium based composite catalyst and application of nickel-calcium based composite catalyst in biomass catalytic pyrolysis process | |
| CN106268826A (en) | Iron-based composite catalyst and methods for making and using same for the online upgrading of bio oil | |
| Liu et al. | Promotion of monocyclic aromatics by catalytic fast pyrolysis of biomass with modified HZSM-5 | |
| Chang et al. | Study on products characteristics from catalytic fast pyrolysis of biomass based on the effects of modified biochars | |
| CN102029157A (en) | Catalyst used for coal tar pitch hydrocracking lightening reaction | |
| Zhang et al. | Enhancement of aromatics production via cellulose fast pyrolysis over Ru modified hierarchical zeolites | |
| 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 | |
| Ji et al. | More than a support: the unique role of Nb 2 O 5 in supported metal catalysts for lignin hydrodeoxygenation | |
| Fang et al. | Influence of metal (Fe/Zn) modified ZSM‐5 catalysts on product characteristics based on the bench‐scale pyrolysis and Py‐GC/MS of biomass | |
| Beh et al. | Flame-made amorphous solid acids with tunable acidity for the aqueous conversion of glucose to levulinic acid | |
| Tang et al. | Study of Mo‐based sepiolite catalyst on depolymerization of lignin under supercritical ethanol | |
| CN111592906A (en) | Preparation of C from biomass6~C18Method for powering fuel | |
| Shen et al. | Pyrolysis of cellulose with cathode materials recovered from spent binary and ternary lithium-ion batteries | |
| Wu et al. | Aqueous‐phase ketonization of acetic acid over Zr/Mn mixed oxides | |
| CN109529853B (en) | Preparation method of hierarchical pore carbon-based catalyst for catalytic modification of coal tar | |
| 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 | |
| Zhang et al. | Defect‐Decorated NiFe Bimetallic Nanocatalysts for the Enhanced Hydrodeoxygenation of Guaiacol | |
| Wang et al. | A 3D porous Fe-MoS2/CMF catalyst for high-efficient catalytic reforming of lignin vapor by microwave irradiation | |
| Chou et al. | Full utilization of lignocellulose through one-pot in-situ hydro-liquefaction with versatile Pt/CeCrO2− x catalyst | |
| CN105647582A (en) | Method for synthesis of aviation kerosene cycloalkane and aromatic hydrocarbon components from bio-oil | |
| Hu et al. | Microwave‐Assisted Rapid Preparation of Vermiculite‐Loaded Nano‐Nickel Oxide As a Highly Efficient Catalyst for Acetylene Carbonylation to Synthesize Acrylic Acid | |
| Özbay et al. | Effect of preparation method and B-side metal type on the physicochemical properties of LaBO3 perovskite catalyst and its catalytic behaviour in the biomass pyrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |