CN106268826B - 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
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- CN106268826B CN106268826B CN201610563540.XA CN201610563540A CN106268826B CN 106268826 B CN106268826 B CN 106268826B CN 201610563540 A CN201610563540 A CN 201610563540A CN 106268826 B CN106268826 B CN 106268826B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000012075 bio-oil Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 238000002407 reforming Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 18
- 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
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007788 liquid Substances 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
- 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
- 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
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 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
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 2
- 239000011833 salt mixture Substances 0.000 claims 1
- 239000002028 Biomass Substances 0.000 description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 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
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 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
- 238000007670 refining Methods 0.000 description 6
- 239000002023 wood Substances 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
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000000197 pyrolysis Methods 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
- 238000007233 catalytic pyrolysis Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000002808 molecular sieve Substances 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
- 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
- 238000004458 analytical method Methods 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
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 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
- 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
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 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
-
- 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, the catalyst is using Mg (Al) O as carrier, 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 is 25% 48%, and Mg (Al) O is 40% 48%.
Description
Technical field
The invention belongs to the utilization technical fields of biomass energy, are carried online for bio oil more particularly to one kind
The Fe based composite catalysts and its methods for making and using same of matter.
Background technology
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 caused 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 shortcomings of big is spent, its popularization and application as hydrocarbon fuel is seriously hindered.Bio oil oil quality how is improved to have become
Biomass fast pyrolysis technology is influenced using a key technical problem with economy.In order to improve the quality of bio oil,
Previous people have done many research work.
Patent " a method of improving 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 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）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 catalysts put into autoclave, in N2Protection, pressure 7.5-11MPa, 100-300 DEG C
It is reacted 3-5 hours under temperature condition, heavy constituent mass percentage is 15%-28% in refining biological oil.However, the patent uses
Supercritical, high pressure reacts, severe reaction conditions, and there are certain difficulty during actually promoting and applying, and do not refer 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 heated again after condensation collection carrying by the bio oil that biomass pyrolytic generates
Matter processing, high energy consumption, 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
It carried out in the same reactor, be not necessarily to condense bio oil and heat again, is easy to operate, is refined at low cost, becoming 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 bio oil catalysis upgrading catalyst 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 relatively low；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.
Invention content
In view of the above problems, the present invention overcomes shortcoming in the prior art, a kind of of low cost, catalytic activity is provided
The Fe based composite catalysts 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 catalysts.
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 to urge
Agent, which is characterized in that the catalyst is using Mg (Al) O as carrier, using Fe as vapor reforming main active component, CaO conducts
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 catalysts through the following steps that prepare：
（a）It is prepared by hydrotalcite precursor：By Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙
9H2O, which is dissolved in deionized water, is made into a concentration of [Mg2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Separately match
The NaOH solution of a concentration of 2 mol/L is made as precipitating reagent；Under continuous strong stirring condition, slowly by it is above-mentioned prepare it is mixed
It closes salting liquid to be continuously added dropwise in aqueous slkali, and controls final solution pH value 10.5 ~ 12, suspension is formed after being added dropwise；
The centrifugation of gained precipitation solution, washing to supernatant pH are 7 for 24 hours by crystallization at ambient temperature, are ground after dry 12h at 100 DEG C
Mill obtains the single presoma of hydrotalcite that laminate contains Fe, Ca, Mg, Al element.
（b）Calcining reduction：Weigh a certain amount of step（a）The obtained single presoma of 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 bases are compound to urge
Agent.
A kind of application process 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, obtain the biology after upgrading
Oil vapour finally carries out the online components of GC/MS and content analysis to the biological oil vapour after upgrading.
The specific feature of the present 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, the mass ratio of catalyst and biomass dosage
For 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）It is prepared by hydrotalcite precursor：By Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)2∙9H2O、Fe(NO3)3∙
9H2O, which is dissolved in deionized water, is made into a concentration of [Mg2+]+[Ca2+]+[Fe3+]+[Al3+The mixing salt solution of]=1 ~ 1.6M；Separately match
The NaOH solution of a concentration of 2 mol/L is made as precipitating reagent；Under continuous strong stirring condition, slowly by it is above-mentioned prepare it is mixed
It closes salting liquid to be continuously added dropwise in aqueous slkali, and controls final solution pH value 10.5 ~ 12, suspension is formed after being added dropwise；
The centrifugation of gained precipitation solution, washing to supernatant pH are 7 for 24 hours by crystallization at ambient temperature, are ground after dry 12h at 100 DEG C
Mill obtains the single presoma of hydrotalcite that laminate contains Fe, Ca, Mg, Al element.
（b）Calcining reduction：Weigh a certain amount of step（a）The obtained single presoma of 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 bases are compound to urge
Agent.
The specific feature of the present 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 is hydrogen or reducing atmosphere is hydrogen with nitrogen or argon gas mixing
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 topologys, while adding Mg (Al) O composite oxides as carrier
The high degree of dispersion for realizing the main active component Fe of catalyst, is remarkably improved catalytic activity and biomass fast pyrogenation is effectively prevent to produce
The carbon distribution reaction of macromolecular oligo object leads to catalyst inactivation in object.
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 have high chemical added value, be prepare phenolic resin,
The important chemical intermediate of the materials such as food additives and fine chemicals.
Specific implementation mode
Embodiment 1：A kind of preparation method of iron-based composite catalyst, it includes the following steps：
The preparation of LDHs presomas：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 and is configured to 500 ml mixed solutions, weighs 50.99gNaNO3It is mixed that addition deionized water is configured to 500 ml
Solution is closed, 56gNaOH is separately weighed and the aqueous slkali that deionized water is configured to a concentration of 2M of 800mL is added.By NaNO3Solution and NaOH
Solution pours into four-hole boiling flask, and mixing salt solution is added drop-wise in above-mentioned mixed ammonium/alkali solutions under mechanical stirring so that final molten
Liquid pH is 11.2, by gained slurries crystallization 24 hours under room temperature, is washed with deionized, centrifuge 4 times, dry at 100 DEG C
Dry 12 hours, grinding obtained LDHs presomas.
Roasting reduction：5g LDHs presomas are 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, waits for that temperature is down to room temperature and obtains Fe naturally
Based composite catalyst.
Fe based composite catalysts composition and mass percentage prepared by the above method is Fe：27.78%, CaO：28.06%,
Mg(Al)O：44.16%, other impurities object phase is not found, and wherein Fe nano-particles 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 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, obtain the biology after upgrading
Oil vapour finally carries out the online components 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 devices, 0.5mg wood powders 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, the wherein 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
Constituent content is different, wherein Mg2+：Ca2+：Fe3+：Al3+Molar ratio is about 4: 4: 1: 1.The catalyst composition and quality being prepared
Percentage composition is Fe：11.41%, CaO：42.06%, Mg (Al) O：46.53%, other impurities object phase, wherein Fe nanoparticles are not found
Sub- average-size is 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 contents reduce 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 are consistent with embodiment 1 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 nano-particles average-size is 7.3 nm.It prepares
Method is same as Example 1, and details are not described herein again.
Above-mentioned iron-based composite catalyst is used for the application process 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, makes the two be uniformly mixed.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 be substantially reduced 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 are consistent with embodiment 1 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 nano-particles average-size is 7.3 nm.It prepares
Method is same as Example 1, and details are not described herein again.
Application process by above-mentioned iron-based composite catalyst for the online upgrading of bio oil a kind of is urged above-mentioned iron-based is compound
Application process 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 compared with bio oil crude product, acid content is reduced to 2.18% in refining biological oil, hydrocarbons content
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 are consistent with embodiment 1 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 nano-particles average-size is 7.3 nm.It prepares
Method is same as Example 1, 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 is sent out
Existing, compared with bio oil crude product, hydrocarbons content increases to 54.15% in refined bio oil（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 carries
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 for the conversion of 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 are consistent with embodiment 1 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 preparation process
Middle catalyst roasting condition is different, and it is 800 DEG C that calcination temperature is increased by 500 DEG C.Characterization finds to prepare in obtained catalyst
Fe nano-particle average-sizes are 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 calcination temperature liter
At up to 800 DEG C, the main active component Fe nano-particles sizes of catalyst do not significantly increase, and then so that it is still remained higher and urge
Change activity.Surface is without apparent carbon distribution to be found to post catalyst reaction structural characterization.
Claims (2)
1. a kind of iron-based composite catalyst for the online upgrading of bio oil, which is characterized in that the catalyst is with Mg (Al) O
Carrier, using Fe as vapor reforming main active component, CaO contains as cocatalyst component and carrier, the quality percentage of each component
Amount is：Fe is 10%-30%, and CaO 25%-48%, Mg (Al) O is 40%-48%；The catalyst is prepared with following steps：
（a）It is prepared by hydrotalcite precursor：By Ca (NO3)2∙6H2O、Mg(NO3)2∙6H2O、Al(NO3)3 ∙9H2O、Fe(NO3)3∙9H2O is molten
A concentration of [Mg 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, and suspension is formed 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 obtained single presoma of 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 iron-based composite catalyst according to claim 1 for the online upgrading of bio oil, which is characterized in that the work
In the carrier, size controlling is in 5-10nm for property component Fe high degree of dispersion.
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