CN102585875A - Method for refining bio-oil - Google Patents

Method for refining bio-oil Download PDF

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CN102585875A
CN102585875A CN2012100555504A CN201210055550A CN102585875A CN 102585875 A CN102585875 A CN 102585875A CN 2012100555504 A CN2012100555504 A CN 2012100555504A CN 201210055550 A CN201210055550 A CN 201210055550A CN 102585875 A CN102585875 A CN 102585875A
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oil
bio
reaction
bio oil
catalyst
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CN102585875B (en
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李文志
商丽敏
张明建
霍伟
祖帅
张腾飞
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University of Science and Technology of China USTC
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The invention provides a method for refining bio-oil. The method comprises a step that macro-molecular organic matters in the bio-oil are depolymerized in illumination conditions under the action of a visible light catalyst. By adopting the method provided in the invention, lignin oligomers in the bio-oil are activated under the catalytic action of the catalyst absorbing certain wavelength lights. The lignin oligomers excited through the photocatalysis have high energy, and high internal energy micro-molecular products are obtained to effectively overcome the complex structure characteristic of the oligomers, so the lignin oligomers in the bio-oil are decomposed into simple-structure micro-molecular organic matters, and the macro-molecular organic matters except the lignin oligomers in the bio-oil are activated and decomposed into simple-structure micro-molecules. The method which successfully depolymerizes the macro-molecular organic matters in the bio-oil into micro-molecular fuel components allows the generation of bio-oil coking to be overcome, the depolymerization rate of the bio-oil to be improved, and the high-grade bio-oil to be obtained.

Description

A kind of method of refining biological oil
Technical field
The present invention relates to biomass energy transformation technology field, relate in particular to a kind of method of refining biological oil.
Background technology
Biomass pyrolytic produce bio oil be one to solving the current energy and ecocrisis, especially tackle the liquid fuel shortage preferably the technology one of.The development since coming out the eighties in last century of biomass pyrolysis liquefaction technology is rapid; Researched and developed out multiple pyrolysis reactor in the world at present; Some has got into the Demonstration Application stage; Built up the pyrolysis liquefaction industry demonstration unit of handling 100 tons of wood chips day in 2006 like Canada, the bio oil productive rate is more than 60wt%, and oil product is used for combustion power generation.
China is since the mid-90 in last century, Agricultural University Of Shenyang carried out biomass pyrolysis liquefaction research the earliest; This technology has obtained rapid progress; Utilize the combustion heat of pyrolysis sub product powdered carbon and combustible gas to be the pyrolysis thermal source like China Science & Technology University; Successfully develop the self-heated pyrolysis liquefaction test device of processing power from 20kg/h to the 120kg/h different scales; And the pyrolysis liquefaction industrialization device that to build up a processing power be 800kg/h, the bio oil of producing is used to boiler combustion and produces steam.
Bio oil is a kind of microemulsion, and it is 500～600 ℃ of middle temperature, under the condition of starvation with the rapid heating pyrolyze of biological particles, a kind of brownish black liquid that obtains after the condensation rapidly again.Biological oil composition and structure are very complicated; And fuel characteristic is poor heat stability especially, mainly shows as: moisture content and oxygen level are high, viscosity is big, calorific value and volatility are low, have acidity and corrodibility, thermostability and poor chemical stability, not only can't be directly as automotive fuel but also do not dissolve each other with the fossil fuel oil.Therefore, bio oil is a kind of low-grade liquid fuel, needs just can to substitute oil fuel through refining processing and especially uses in the oil engine at existing heat power equipment.
Study in great detail though present purification techniques to bio oil has a lot, every kind of technology has many good qualities, because the peculiar property of bio oil, these methods are all only effective to part component in model compound or the bio oil.Bio oil is refining in the prior art is carrying out more than 200 ℃ usually; Separate that the charing coking very easily takes place the xylogen oligopolymer in the bio oil in the collecting process; Produce a large amount of coke and tar compounds, and be deposited on catalyst surface, the covering catalyst avtive spot; Make catalyst deactivation, reduced the depolymerization rate of bio oil thus.And above-mentioned xylogen oligopolymer makes it be difficult for taking place depolymerization owing to have the shortcoming of complex structure, poor thermal conductivity.
Therefore, be the key of refining biological oil with xylogen oligopolymer catalytic degradation, depolymerization method is also effective to other larger molecular organics in the bio oil simultaneously, finally reaches the purpose of refining biological oil.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of method of refining biological oil, and this method has higher depolymerization rate to the xylogen oligopolymer in the bio oil, and the grade of bio oil obtained by this method is higher.
The invention discloses a kind of method of refining biological oil, comprising: under the condition of illumination, under the effect of visible light catalyst, the larger molecular organics generation depolymerization in the bio oil.
Preferably, said visible light catalyst is loaded catalyst or doped catalyzer.
Preferably, the load transition element of said loaded catalyst is Fe, Ru, Co, Rh, Ni, Pt, Pd, Ag, Au, Zn or Cu; Said doped catalyzer adulterated nonmetal be nitrogen, sulphur, halogen or carbon, transition metal ion is Fe 3+, Mo 4+, Ru 3+, Os 3+, Re 5+, V 4+Or Rh 3+
Preferably, the carrier of said visible light catalyst is TiO 2Particle, TiO 2Film, SiO 2-TiO 2Film, Sb doped Ti O 2Film, CdS, CdS-TiO 2Composite semiconductor, ZnO and WO 3
Preferably, said loaded catalyst is Pt-Ru/CdS-TiO 2
Preferably, the light source of said illumination is a sunshine.
Preferably, the wavelength region of said illumination is 0.32～4.0um.
Preferably, the luminous power of said illumination is 260～5000mw/cm 3
Preferably, the mass ratio of said visible light catalyst and said bio oil is (1 * 10 -6～1 * 10 -2): 1.
Preferably, the temperature of reaction of said depolymerization reaction is 0～60 ℃, and the reaction pressure of said depolymerization reaction is 0.001～2MPa.
Compared with prior art, the present invention adopts visible light catalyst, the larger molecular organics under the condition of illumination in the depolymerization bio oil.In reaction process; Xylogen oligopolymer in the bio oil issues life-stylize in the catalyst effect that absorbs certain wavelength light; Be not that the xylogen oligopolymer absorbs heat energy from environment; This has only a spot of xylogen oligopolymer to obtain the problem of separating cumulative with regard to not producing because xylogen oligopolymer poor thermal conductivity causes in bio oil; But making the almost energy of synchronization gain activation needs of molecules more, dissimilar in the bio oil, more xylogen oligopolymer is in unsettled excited state in the bio oil thereby make.The xylogen oligopolymer that is excited by photochemical catalysis has higher-energy; The trend of oriented low-yield conversion; Therefore under the effect of photocatalyst; Resolve into some like radical, the higher product of diradical equal-energy, overcome the complicated characteristics of xylogen oligomer structure effectively, make that oligopolymer resolves into small molecules simple in structure in the bio oil.And to other larger molecular organics except that the xylogen oligopolymer in the bio oil, under photocatalyst and illumination condition, activation can take place also, resolve into small molecules simple in structure.
In sum; The present invention utilizes larger molecular organics in the photochemical catalysis depolymerization bio oil; Be the small molecules fuel element successfully with the larger molecular organics catalyzed conversion that comprises the xylogen oligopolymer in the bio oil; Overcome the generation of bio oil coking, improved the depolymerization rate of bio oil, obtained high-grade bio oil.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of method of refining biological oil, comprising: under the condition of illumination, under the effect of visible light catalyst, the larger molecular organics generation depolymerization in the bio oil.
The present invention utilizes visible light catalyst; Larger molecular organics under the condition of illumination in the catalytic degradation bio oil; The principle of this method is when being equal to or greater than the spectral illumination of catalyzer energy gap with energy; Electronics on the catalyzer valence band is excited and transits to conduction band, on valence band, produces corresponding hole simultaneously, and is so just right at semi-conductor inner generation electronics and hole.Electronics is moved to the different positions of particle surface with after separate in the hole, and is adsorbed on catalyst particle lip-deep material generation oxidation or reduction reaction, thus the depolymerization oligopolymer.
The photochemical catalysis depolymerization reaction is very complicated, relates to a plurality of processes and stepwise reaction, mainly is divided into " primary light catalyzed reaction " and " secondary light catalyzed reaction ".
The reaction formula of primary light catalyzed reaction is: K+hv → K *The reaction formula of secondary light catalyzed reaction is: K *+ A ++ B -→ K+A+B; K is a visible light catalyst in the formula, K *Be activatory visible light catalyst, A +And B -Be unsettled larger molecular organics, A and B are small organic molecule.
The effect of visible light catalyst described in the present invention is to absorb visible light; Produce transition of electron; Make that electronics separates with the hole in the catalyzer, thus with the material generation oxidation or the reduction reaction that are adsorbed on the catalyst pellets sub-surface, and then depolymerization xylogen oligopolymer.Above-mentioned visible light catalyst is preferably loaded catalyst or doped catalyzer, and the load transition element of above-mentioned loaded catalyst is preferably Fe, Ru, Co, Rh, Ni, Pt, Pd, Ag, Au, Zn or Cu; Adulterated nonmetal nitrogen, sulphur, halogen or the carbon of being preferably of above-mentioned doped catalyzer, transition metal ion is preferably Fe 3+, Mo 4+, Ru 3+, Os 3+, Re 5+, V 4+Or Rh 3+, the carrier of above-mentioned visible light catalyst is preferably TiO 2Particle, TiO 2Film, SiO 2-TiO 2Film, Sb doped Ti O 2Film, CdS, CdS-TiO 2Composite semiconductor, ZnO or WO 3
In order to improve the depolymerization rate of the larger molecular organics that comprises the xylogen oligopolymer; As preferred version; The present invention adopts sunshine as light source; In the electromagnetic spectrum of sunshine except the visible light that accounts for total emitted energy about 50%; Therefore account for the ir spectra of total emitted energy about 43% in addition, refining biological oil has not only made full use of the energy that visible light part in the sunshine has also been utilized ir spectra under the illumination condition of sunshine, has increased substantially the depolymerization rate of xylogen oligopolymer.
The wavelength region of above-mentioned illumination is preferably 0.32～4.0um.The luminous power of above-mentioned illumination is preferably 260～5000mw/cm 3, if luminous power is lower than 260mw/cm 3, the catalytic degradation reaction is extremely slow, thereby influences production efficiency, if luminous power is too high, material is then gasified, thereby causes the product liquid recovery low.
In order to improve the speed of reaction of depolymerization reaction, depolymerization condition of the present invention also preferably includes heating, is illumination and heating with regard to the reaction conditions that makes depolymerization reaction like this.In this case, the rate constant of the primary light catalytic process of depolymerization reaction raises with temperature increases.So; The combination of illumination condition and heating condition be not catalyzer photocatalysis performance and thermocatalysis performance simply adding with; But a kind of brand-new reaction path, the activation method and the reaction path of reactant molecule all change, thereby more help the depolymerization of the larger molecular organics in the bio oil.Above-mentioned Heating temperature is preferably 0～60 ℃, and more preferably 30～50 ℃, slower if temperature is crossed low rate of catalysis reaction, because bio oil oligopolymer thermo-sensitivity is higher, when temperature was higher, its condensation polycondensation was strong, thereby increased the difficulty of refining biological oil.
In the refining biological oil process, the larger molecular organics in the more high efficiency depolymerization bio oil obtains high-grade bio oil, and the mass ratio of above-mentioned visible light catalyst and bio oil is preferably (1 * 10 -6～1 * 10 -2): 1, when catalyst levels was very few, the catalytic efficiency (of reactive system was low, and along with the increase of catalyst levels, catalytic efficiency (progressively improves, but after reaching some amount, catalytic efficiency (increases not obvious even descends.
The present invention utilizes visible light catalyst in the process of refining biological oil, the larger molecular organics under the condition of illumination in the depolymerization bio oil.In this process; Under illumination condition; The xylogen oligopolymer issues life-stylize in the katalysis of the catalyzer that absorbs certain wavelength light, is not that the xylogen oligopolymer absorbs heat energy from environment, and this has only a spot of xylogen oligopolymer to obtain the problem of separating cumulative with regard to not producing because xylogen oligopolymer poor thermal conductivity causes in bio oil; But make the almost energy of synchronization gain activation needs of molecules more, dissimilar in the bio oil, begin to transform.The xylogen oligopolymer that is excited by photochemical catalysis has higher-energy; The trend of oriented low-yield conversion; Therefore under the effect of visible light catalyst, the xylogen oligopolymer that plays pendulum can resolve into some like radical, the higher product of diradical equal-energy, overcomes the complicated characteristics of xylogen oligomer structure effectively; Make the xylogen oligopolymer resolve into small molecules simple in structure; And to other larger molecular organicses except that the xylogen oligopolymer in the bio oil, under photocatalyst and illumination condition, activation also can take place resolve into small organic molecule simple in structure.
In addition; Light is used to reaction in the catalytic degradation reaction, and therefore, the reaction that cannot under mild conditions, carry out on some thermodynamics also can have been carried out; Thereby reduced the generation of oligomer condensation polycondensation to the full extent, improved the bio oil purification efficiency.
In sum; The present invention utilizes visible light catalyst; Larger molecular organics under illumination condition in the depolymerization bio oil can be the small molecules fuel element with the larger molecular organics catalyzed conversion that comprises the xylogen oligopolymer in the bio oil, has overcome the generation of bio oil coking in the treating process; Increase substantially the depolymerization rate of bio oil, solved the difficult problem that biomass pyrolytic is produced liquid fuel.
In order further to understand the present invention, below in conjunction with embodiment the method for refining biological oil provided by the invention has been carried out detailed introduction, protection scope of the present invention is not limited by the following examples.
Employed bio oil is to be that raw material makes through fast pyrolysis with the rice husk among the embodiment.The main chemical compositions of gained bio oil and content (area percentage thereof; Bio oil is formed through area normalization method and is detected, and then the content that obtains of this method is area percentage) be: acid 17.74%, ester 3.13%, ketone 12.87%, aldehyde 7.17%, C=C 22.67%, phenol 39.12%, glycan class 3.12% and furans 5.31%.
Embodiment 1
1) measure the 1000g bio oil and put into quartz apparatus, measuring the particle diameter that 0.1g prepares in advance simultaneously is 200 purpose Pt-Ru/CdS-TiO 2Catalyzer is put into the vessel that fill bio oil, and puts into the stirring magneton;
2) confined reaction system opens induction stirring, opens constant-flux pump, connects the cold well of air source of the gas and reactive system gas outlet, before the air admission reaction kettle successively through the vessel of filling discolour silica gel and gac.Open, adjust light source and make that the luminous power in the reactor drum is 2000mw/cm 2, the adjustments of gas flow velocity makes gas be uniformly distributed in the reaction liquid;
3) regulate water coolant flow velocity in light source and the reaction kettle interlayer, the heating unit of opening the quartz apparatus bottom simultaneously makes that the homo(io)thermism in the reaction system is 35 ℃, and the wavelength of light source is 0.32～4um;
4) whenever took out bio oil from the reaction kettle thief hole in the reaction process, and utilize supercentrifuge that the catalyzer in the bio oil is separated with unreacted super large molecular components and remove, with the component of the bio oil behind the GC/MS analytical separation at a distance from 1 hour; Utilize gas phase chromatographic analysis appearance to analyze the gas composition of corresponding time response still gas outlet;
5) reaction is after 6 hours, according to the orderly close-down reaction of closing light source, heating unit, source of the gas, constant flow pump and water coolant;
6) after the temperature of reaction system is reduced to room temperature, take out refining biological oil and mixture of catalysts, utilize the high speed rotating whizzer to isolate catalyzer and be used to recycle.
Molecular weight with gel chromatography analytical test refining biological oil changes, and analyzes the component and the variation thereof of treated oil with GC/MS.The result shows that the molecular weight of refining biological oil reduces by 46%, and phenol is respectively 80% and 78% with the small molecules ester content increasing degree that contains phenyl ring.
Embodiment 2
1) measure the 1000g bio oil and put into quartz apparatus, measuring the particle diameter that 0.1g prepares in advance simultaneously is 200 purpose Pt-Ru/CdS-TiO 2Catalyzer is put into the vessel that fill bio oil, and puts into the stirring magneton;
2) confined reaction system opens induction stirring, opens constant-flux pump, connects the cold well of air source of the gas and reactive system gas outlet, before the air admission reaction kettle successively through the vessel of filling discolour silica gel and gac.Open, adjust light source and make that the luminous power in the reactor drum is 2000mw/cm 2, the adjustments of gas flow velocity makes gas be uniformly distributed in the reaction liquid;
3) regulate water coolant flow velocity in light source and the reaction kettle interlayer, the heating unit of opening the quartz apparatus bottom simultaneously makes that the homo(io)thermism in the reaction system is 45 ℃, and the wavelength of light source is 0.32～4um;
4) whenever took out bio oil from the reaction kettle thief hole in the reaction process, and utilize supercentrifuge that the catalyzer in the bio oil is separated with unreacted super large molecular components and remove, with the component of the bio oil behind the GC/MS analytical separation at a distance from 1 hour; Utilize gas phase chromatographic analysis appearance to analyze the gas composition of corresponding time response still gas outlet;
5) reaction is after 6 hours, according to the orderly close-down reaction of closing light source, heating unit, source of the gas, constant flow pump and water coolant;
6) after the temperature of reaction system is reduced to room temperature, carefully take out refining biological oil and mixture of catalysts, utilize the high speed rotating whizzer to isolate catalyzer and be used to recycle.
Molecular weight with gel chromatography analytical test refining biological oil changes, and analyzes the component and the variation thereof of treated oil with GC/MS.The result shows that the molecular weight of refining biological oil reduces by 69%, and phenol is respectively 88% and 86% with the small molecules ester content increasing degree that contains phenyl ring.
Embodiment 3
1) measure the 1000g bio oil and put into quartz apparatus, measuring the particle diameter that 0.5g prepares in advance simultaneously is 200 purpose Pt-Ru/CdS-TiO 2Catalyzer is put into the vessel that fill bio oil, and puts into the stirring magneton;
2) confined reaction system opens induction stirring, opens constant-flux pump, connects the cold well of air source of the gas and reactive system gas outlet, before the air admission reaction kettle successively through the vessel of filling discolour silica gel and gac.Open, adjust light source and make that the luminous power in the reactor drum is 2000mw/cm 2, the adjustments of gas flow velocity makes gas be uniformly distributed in the reaction liquid;
3) regulate water coolant flow velocity in light source and the reaction kettle interlayer, the heating unit of opening the quartz apparatus bottom simultaneously makes that the homo(io)thermism in the reaction system is 45 ℃, and the wavelength of light source is 0.32～4um;
4) whenever took out bio oil from the reaction kettle thief hole in the reaction process, and utilize supercentrifuge that the catalyzer in the bio oil is separated with unreacted super large molecular components and remove, with the component of the bio oil behind the GC/MS analytical separation at a distance from 1 hour; Utilize gas phase chromatographic analysis appearance to analyze the gas composition of corresponding time response still gas outlet;
5) reaction is after 6 hours, according to the orderly close-down reaction of closing light source, heating unit, source of the gas, constant flow pump and water coolant;
6) after the temperature of reaction system is reduced to room temperature, carefully take out refining biological oil and mixture of catalysts, utilize the high speed rotating whizzer to isolate catalyzer and be used to recycle.
Molecular weight with gel chromatography analytical test refining biological oil changes, and analyzes the component and the variation thereof of treated oil with GC/MS.The result shows that the molecular weight of refining biological oil reduces by 87%, and phenol is respectively 93% and 95% with the small molecules ester content increasing degree that contains phenyl ring.
Embodiment 4
1) measure the 1000g bio oil and put into quartz apparatus, measuring the particle diameter that 0.1g prepares in advance simultaneously is 200 purpose Pt-Ru/CdS-TiO 2Catalyzer is put into the vessel that fill bio oil, and puts into the stirring magneton;
2) confined reaction system opens induction stirring, opens constant-flux pump, connects the cold well of air source of the gas and reactive system gas outlet, before the air admission reaction kettle successively through the vessel of filling discolour silica gel and gac.Open, adjust light source and make that the luminous power in the reactor drum is 2000mw/cm 2, the adjustments of gas flow velocity makes gas be uniformly distributed in the reaction liquid;
3) regulate water coolant flow velocity in light source and the reaction kettle interlayer, the heating unit of opening the quartz apparatus bottom simultaneously makes that the homo(io)thermism in the reaction system is 40 ℃, and the wavelength of light source is 0.32～4um;
4) whenever took out bio oil from the reaction kettle thief hole in the reaction process, and utilize supercentrifuge that the catalyzer in the bio oil is separated with unreacted super large molecular components and remove, with the component of the bio oil behind the GC/MS analytical separation at a distance from 1 hour; Utilize gas phase chromatographic analysis appearance to analyze the gas composition of corresponding time response still gas outlet;
5) reaction is after 6 hours, according to the orderly close-down reaction of closing light source, heating unit, source of the gas, constant flow pump and water coolant;
6) after the temperature of reaction system is reduced to room temperature, carefully take out refining biological oil and mixture of catalysts, utilize the high speed rotating whizzer to isolate catalyzer and be used to recycle.
Molecular weight with gel chromatography analytical test refining biological oil changes, and analyzes the component and the variation thereof of treated oil with GC/MS.The result shows that the molecular weight of refining biological oil reduces by 53%, and phenol is respectively 83% and 81.5% with the small molecules ester content increasing degree that contains phenyl ring.
Embodiment 5
1) measure the 1000g bio oil and put into quartz apparatus, measuring the particle diameter that 0.1g prepares in advance simultaneously is 200 purpose Pt-Ru/CdS-TiO 2Catalyzer is put into the vessel that fill bio oil, and puts into the stirring magneton;
2) confined reaction system opens induction stirring, opens constant-flux pump, connects the cold well of air source of the gas and reactive system gas outlet, before the air admission reaction kettle successively through the vessel of filling discolour silica gel and gac.Open, adjust light source and make that the luminous power in the reactor drum is 2000mw/cm 2, the adjustments of gas flow velocity makes gas be uniformly distributed in the reaction liquid;
3) regulate water coolant flow velocity in light source and the reaction kettle interlayer, the heating unit of opening the quartz apparatus bottom simultaneously makes that the homo(io)thermism in the reaction system is 50 ℃, and the wavelength of light source is 0.32～4um;
4) whenever took out bio oil from the reaction kettle thief hole in the reaction process, and utilize supercentrifuge that the catalyzer in the bio oil is separated with unreacted super large molecular components and remove, with the component of the bio oil behind the GC/MS analytical separation at a distance from 1 hour; Utilize gas phase chromatographic analysis appearance to analyze the gas composition of corresponding time response still gas outlet;
5) reaction is after 6 hours, according to the orderly close-down reaction of closing light source, heating unit, source of the gas, constant flow pump and water coolant;
6) after the temperature of reaction system is reduced to room temperature, carefully take out refining biological oil and mixture of catalysts, utilize the high speed rotating whizzer to isolate catalyzer and be used to recycle.
Molecular weight with gel chromatography analytical test refining biological oil changes, and analyzes the component and the variation thereof of treated oil with GC/MS.The result shows that the molecular weight of refining biological oil reduces by 66%, and phenol is respectively 87% and 84% with the small molecules ester content increasing degree that contains phenyl ring.
Embodiment 6
1) measure the 1000g bio oil and put into quartz apparatus, measuring the particle diameter that 1.0g prepares in advance simultaneously is 200 purpose Pt-Ru/CdS-TiO 2Catalyzer is put into the vessel that fill bio oil, and puts into the stirring magneton;
2) confined reaction system opens induction stirring, opens constant-flux pump, connects the cold well of air source of the gas and reactive system gas outlet, before the air admission reaction kettle successively through the vessel of filling discolour silica gel and gac.Open, adjust light source and make that the luminous power in the reactor drum is 2000mw/cm 2, the adjustments of gas flow velocity makes gas be uniformly distributed in the reaction liquid;
3) regulate water coolant flow velocity in light source and the reaction kettle interlayer, the heating unit of opening the quartz apparatus bottom simultaneously makes that the homo(io)thermism in the reaction system is 45 ℃, and the wavelength of light source is 0.32～4um;
4) whenever took out bio oil from the reaction kettle thief hole in the reaction process, and utilize supercentrifuge that the catalyzer in the bio oil is separated with unreacted super large molecular components and remove, with the component of the bio oil behind the GC/MS analytical separation at a distance from 1 hour; Utilize gas phase chromatographic analysis appearance to analyze the gas composition of corresponding time response still gas outlet;
5) reaction is after 6 hours, according to the orderly close-down reaction of closing light source, heating unit, source of the gas, constant flow pump and water coolant;
6) after the temperature of reaction system is reduced to room temperature, carefully take out refining biological oil and mixture of catalysts, utilize the high speed rotating whizzer to isolate catalyzer and be used to recycle.
Molecular weight with gel chromatography analytical test refining biological oil changes, and analyzes the component and the variation thereof of treated oil with GC/MS.The result shows that the molecular weight of refining biological oil reduces by 89%, and phenol is respectively 94% and 96% with the small molecules ester content increasing degree that contains phenyl ring.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (10)

1. the method for a refining biological oil is characterized in that, comprising: under the condition of illumination, and under the effect of visible light catalyst, the larger molecular organics generation depolymerization in the bio oil.
2. method according to claim 1 is characterized in that, said visible light catalyst is loaded catalyst or doped catalyzer.
3. method according to claim 2 is characterized in that, the load transition element of said loaded catalyst is Fe, Ru, Co, Rh, Ni, Pt, Pd, Ag, Au, Zn or Cu; Said doped catalyzer adulterated nonmetal be nitrogen, sulphur, halogen or carbon, transition metal ion is Fe 3+, Mo 4+, Ru 3+, Os 3+, Re 5+, V 4+Or Rh 3+
4. method according to claim 1 is characterized in that, the carrier of said visible light catalyst is TiO 2Particle, TiO 2Film, SiO 2-TiO 2Film, Sb doped Ti O 2Film, CdS, CdS-TiO 2Composite semiconductor, ZnO or WO 3
5. method according to claim 2 is characterized in that, said loaded catalyst is Pt-Ru/CdS-TiO 2
6. method according to claim 1 is characterized in that, the light source of said illumination is a sunshine.
7. method according to claim 1 is characterized in that, the wavelength region of said illumination is 0.32～4.0um.
8. method according to claim 1 is characterized in that, the luminous power of said illumination is 260～5000mw/cm 3
9. method according to claim 1 is characterized in that, the mass ratio of said visible light catalyst and said bio oil is (1 * 10 -6～1 * 10 -2): 1.
10. method according to claim 1 is characterized in that, the temperature of reaction of said depolymerization reaction is 0～60 ℃, and the reaction pressure of said depolymerization reaction is 0.001～2MPa.
CN201210055550.4A 2012-03-05 2012-03-05 Method for refining bio-oil Expired - Fee Related CN102585875B (en)

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Publication number Priority date Publication date Assignee Title
CN111320231A (en) * 2020-02-26 2020-06-23 江苏大学 System and method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis
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CN114308104A (en) * 2021-12-27 2022-04-12 华南理工大学 Preparation method and application of nitrogen-doped carbon material loaded bimetallic cobalt and vanadium catalyst
CN114308104B (en) * 2021-12-27 2023-11-03 华南理工大学 Preparation method and application of nitrogen-doped carbon material supported bimetallic cobalt and vanadium catalyst

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