CN102585875B - Method for refining bio-oil - Google Patents
Method for refining bio-oil Download PDFInfo
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- CN102585875B CN102585875B CN201210055550.4A CN201210055550A CN102585875B CN 102585875 B CN102585875 B CN 102585875B CN 201210055550 A CN201210055550 A CN 201210055550A CN 102585875 B CN102585875 B CN 102585875B
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention provides a 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
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 preparing bio-oil be one to solving the current energy and ecocrisis, especially tackle liquid fuel shortage one of technology preferably.The development since coming out the eighties in last century of biomass pyrolysis liquefaction technology is rapid, now researched and developed in the world multiple pyrolysis reactor, some has entered the Demonstration Application stage, as Canada has built up the pyrolysis liquefaction Industrial demonstration device of processing 100 tons of wood chips day in 2006, bio oil productive rate is more than 60wt%, and oil product is 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, as China Science & Technology University utilizes the combustion heat of pyrolysis byproduct powdered carbon and combustible gas, it is pyrolysis thermal source, successfully develop the self-heated pyrolysis liquefaction test device of processing power from 20kg/h to 120kg/h different scales, and build up the pyrolysis liquefaction industrialization device that a processing power is 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 by the rapid heating pyrolyze of biological particles, more a kind of brownish black liquid obtaining after condensation rapidly.Biological oil composition and structure are very complicated, and fuel characteristic is poor heat stability especially, main manifestations is: moisture content and oxygen level are high, viscosity is large, calorific value and volatility low, have acidity and corrodibility, thermostability and poor chemical stability, not only cannot be directly as automotive fuel but also do not dissolve each other with fossil fuel oil.Therefore, bio oil is a kind of low-grade liquid fuel, needs just can in existing heat power equipment especially oil engine, to use by petroleum replacing fuel through refining processing.
Although at present the purification techniques of bio oil is had much and studied in great detail, every kind of technology has many good qualities, due to the peculiar property of bio oil, these methods are all only effective to part component in model compound or bio oil.In prior art, bio-oil upgrading carries out above at 200 ℃ conventionally, separate the xylogen oligopolymer in bio oil in collecting process charing coking very easily occurs, produce a large amount of coke and tar compounds, and be deposited on catalyst surface, covering catalyst avtive spot, make catalyst deactivation, reduced thus the depolymerization rate of bio oil.And above-mentioned xylogen oligopolymer makes it be difficult for occurring depolymerization owing to having the shortcoming of complex structure, poor thermal conductivity.
Therefore, by xylogen oligopolymer catalytic degradation, be the key of refining biological oil, depolymerization method is also effective to other larger molecular organics in bio oil simultaneously, finally reaches the object 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 the method has higher depolymerization rate to the xylogen oligopolymer in bio oil, and the grade of bio oil obtained by this method is higher.
A kind of method that the invention discloses refining biological oil, comprising: under the condition of illumination, and under the effect of visible light catalyst, the larger molecular organics generation depolymerization in bio oil.
Preferably, described visible light catalyst is loaded catalyst or doping type catalyzer.
Preferably, the load transition element of described loaded catalyst is Fe, Ru, Co, Rh, Ni, Pt, Pd, Ag, Au, Zn or Cu; The nonmetal of described doping type catalyzer doping is nitrogen, sulphur, halogen or carbon, and transition metal ion is Fe
3+, Mo
4+, Ru
3+, Os
3+, Re
5+, V
4+or Rh
3+.
Preferably, the carrier of described 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, described loaded catalyst is Pt-Ru/CdS-TiO
2.
Preferably, the light source of described illumination is sunlight.
Preferably, the wavelength region of described illumination is 0.32～4.0um.
Preferably, the luminous power of described illumination is 260～5000mw/cm
3.
Preferably, the mass ratio of described visible light catalyst and described bio oil is (1 * 10
-6～1 * 10
-2): 1.
Preferably, the temperature of reaction of described depolymerization reaction is 0～60 ℃, and the reaction pressure of described 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 depolymerization bio oil.In reaction process, xylogen oligopolymer in bio oil issues life-stylize in the catalyst effect that absorbs certain wavelength light, not xylogen oligopolymer absorbs heat energy from environment, this only has a small amount 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 molecule more, dissimilar in the bio oil energy that almost synchronization gain activation needs, thereby make in bio oil more xylogen oligopolymer in unsettled excited state.The xylogen oligopolymer being excited by photochemical catalysis has higher-energy, the trend of oriented low-yield conversion, therefore under the effect of photocatalyst, resolve into some as free radical, product that diradical equal-energy is higher, effectively overcome the feature of xylogen oligomer structure complexity, make oligopolymer in bio oil resolve into small molecules simple in structure.And to other larger molecular organics except xylogen oligopolymer in bio oil, under photocatalyst and illumination condition, also can activate, resolve into small molecules simple in structure.
In sum, the present invention utilizes larger molecular organics in photochemical catalysis depolymerization bio oil, successfully the larger molecular organics that comprises xylogen oligopolymer in bio oil is catalytically conveted to small molecules fuel element, overcome the generation of bio oil coking, the depolymerization rate that has improved bio oil, has 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, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
A kind of method that the embodiment of the invention discloses refining biological oil, comprising: under the condition of illumination, and under the effect of visible light catalyst, the larger molecular organics generation depolymerization in bio oil.
The present invention utilizes visible light catalyst, larger molecular organics under the condition of illumination in catalytic degradation bio oil, the principle of this method is while being equal to or greater than the spectral illumination of catalyzer energy gap with energy, electronics in catalyzer valence band is excited and transits to conduction band, in valence band, produce corresponding hole, so just in inner electronics and the hole pair of generating of semi-conductor simultaneously.After electronics is separated with hole generation, move to the different positions of particle surface, be oxidized or reduction reaction with being adsorbed on the lip-deep material generation of catalyst particle, thus depolymerization oligopolymer.
Photochemical catalysis depolymerization reaction is very complicated, relates to a plurality of processes and stepwise reaction, is mainly 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; In formula, K is visible light catalyst, K
*for the visible light catalyst of activation, A
+and B
-for 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 in catalyzer electronics separated with hole, thereby with the material that is adsorbed on catalyst pellets sub-surface, oxidation or reduction reaction occur, and then depolymerization xylogen oligopolymer.Above-mentioned visible light catalyst is preferably loaded catalyst or doping type 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; Nonmetal nitrogen, sulphur, halogen or the carbon of being preferably of above-mentioned doping type catalyzer doping, 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 xylogen oligopolymer, as preferred version, the present invention adopts sunlight as light source, in the electromagnetic spectrum of sunlight except accounting for the visible ray of total emitted energy 50% left and right, account in addition the infrared spectra of total emitted energy 43% left and right, therefore under the illumination condition of sunlight refining biological oil not only take full advantage of sunlight in visible light part also utilized the energy of infrared spectra, 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
3if luminous power is lower than 260mw/cm
3, catalytic degradation reaction is extremely slow, thereby affects production efficiency, if luminous power is too high, material is vaporized, thereby causes the product liquid rate of 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 like this with regard to making the reaction conditions of depolymerization reaction.In this case, the rate constant of the primary light catalytic process of depolymerization reaction raises and increases with temperature.So, the combination of illumination condition and heating condition be not catalyzer photocatalysis performance and thermocatalysis performance simply adding and, but a kind of brand-new reaction path, activation method and the reaction path of reactant molecule all change, thereby are more conducive to the depolymerization of the larger molecular organics in bio oil.Above-mentioned Heating temperature is preferably 0～60 ℃, and more preferably 30～50 ℃, if the too low rate of catalysis reaction of temperature is slower, because bio oil oligopolymer thermo-sensitivity is higher, when temperature is higher, its condensation polycondensation is strong, thereby increases the difficulty of refining biological oil.
In refining biological oil process, the larger molecular organics in 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 is very few, the catalytic efficiency of reactive system is low, and along with the increase of catalyst levels, catalytic efficiency progressively improves, but reaches after some amount, and catalytic efficiency increases not obvious even decline.
The present invention, in the process of refining biological oil, utilizes visible light catalyst, the larger molecular organics under the condition of illumination in depolymerization bio oil.In this process, under illumination condition, xylogen oligopolymer issues life-stylize in the katalysis that absorbs the catalyzer of certain wavelength light, not xylogen oligopolymer absorbs heat energy from environment, this only has a small amount 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 molecule more, dissimilar in the bio oil energy that almost synchronization gain activation needs, start to transform.The xylogen oligopolymer being 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 playing pendulum can resolve into some as free radical, the product that diradical equal-energy is higher, effectively overcome the feature of xylogen oligomer structure complexity, make xylogen oligopolymer resolve into small molecules simple in structure, and to other larger molecular organicses except xylogen oligopolymer in bio oil, under photocatalyst and illumination condition, also can there is activation and resolve into small organic molecule simple in structure.
In addition, in catalytic degradation reaction, light is used to reaction, and therefore, the reaction that cannot carry out under mild conditions on some thermodynamics also can have been carried out, thereby reduced to the full extent the generation of oligomer condensation polycondensation, improved bio-oil upgrading efficiency.
In sum, the present invention utilizes visible light catalyst, larger molecular organics under illumination condition in depolymerization bio oil, the larger molecular organics that comprises xylogen oligopolymer in bio oil can be catalytically conveted to small molecules fuel element, overcome the generation of bio oil coking in treating process, increase substantially the depolymerization rate of bio oil, solved a difficult problem for biomass pyrolytic preparing 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 is described in detail, protection scope of the present invention is not limited by the following examples.
The bio oil of using in embodiment is to take rice husk by fast pyrolysis, to make as raw material.The main chemical compositions of gained bio oil and content (area percentage thereof, bio-oil composition detects by area normalization method, and the content that the method obtains 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 1000g bio oil and put into quartz apparatus, measure the previously prepared particle diameter of 0.1g is 200 object Pt-Ru/CdS-TiO simultaneously
2catalyzer is put into the vessel that fill bio oil, and puts into 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, and air enters before reactor successively the vessel through filling discolour silica gel and gac.Opening, adjust light source, to make the luminous power in reactor be 2000mw/cm
2, adjustments of gas flow velocity is distributed in reaction liquid gas uniform;
3) regulate water coolant flow velocity in light source and reactor interlayer, it is 35 ℃ that the heating unit of simultaneously opening quartz apparatus bottom makes the homo(io)thermism in reaction system, and the wavelength of light source is 0.32～4um;
4) in reaction process, every 1 hour, from reactor thief hole, take out bio oil, and utilize supercentrifuge by the catalyzer in bio oil and separated the removing of unreacted super large molecular components, by the component of the bio oil after GC/MS analytical separation; Utilize gas phase chromatographic analysis instrument 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) temperature of reaction system is reduced to after room temperature, takes out the mixture of refining biological oil and catalyzer, utilizes high speed rotating whizzer to isolate catalyzer for recycling.
With the change of molecular weight of gel chromatography analytical test refining biological oil, with GC/MS, analyze component and the variation thereof of treated oil.Result shows, the molecular weight reduction by 46% of refining biological oil, and phenol and the small molecules ester content increasing degree that contains phenyl ring are respectively 80% and 78%.
Embodiment 2
1) measure 1000g bio oil and put into quartz apparatus, measure the previously prepared particle diameter of 0.1g is 200 object Pt-Ru/CdS-TiO simultaneously
2catalyzer is put into the vessel that fill bio oil, and puts into 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, and air enters before reactor successively the vessel through filling discolour silica gel and gac.Opening, adjust light source, to make the luminous power in reactor be 2000mw/cm
2, adjustments of gas flow velocity is distributed in reaction liquid gas uniform;
3) regulate water coolant flow velocity in light source and reactor interlayer, it is 45 ℃ that the heating unit of simultaneously opening quartz apparatus bottom makes the homo(io)thermism in reaction system, and the wavelength of light source is 0.32～4um;
4) in reaction process, every 1 hour, from reactor thief hole, take out bio oil, and utilize supercentrifuge by the catalyzer in bio oil and separated the removing of unreacted super large molecular components, by the component of the bio oil after GC/MS analytical separation; Utilize gas phase chromatographic analysis instrument 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) temperature of reaction system is reduced to after room temperature, carefully takes out the mixture of refining biological oil and catalyzer, utilizes high speed rotating whizzer to isolate catalyzer for recycling.
With the change of molecular weight of gel chromatography analytical test refining biological oil, with GC/MS, analyze component and the variation thereof of treated oil.Result shows, the molecular weight reduction by 69% of refining biological oil, and phenol and the small molecules ester content increasing degree that contains phenyl ring are respectively 88% and 86%.
Embodiment 3
1) measure 1000g bio oil and put into quartz apparatus, measure the previously prepared particle diameter of 0.5g is 200 object Pt-Ru/CdS-TiO simultaneously
2catalyzer is put into the vessel that fill bio oil, and puts into 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, and air enters before reactor successively the vessel through filling discolour silica gel and gac.Opening, adjust light source, to make the luminous power in reactor be 2000mw/cm
2, adjustments of gas flow velocity is distributed in reaction liquid gas uniform;
3) regulate water coolant flow velocity in light source and reactor interlayer, it is 45 ℃ that the heating unit of simultaneously opening quartz apparatus bottom makes the homo(io)thermism in reaction system, and the wavelength of light source is 0.32～4um;
4) in reaction process, every 1 hour, from reactor thief hole, take out bio oil, and utilize supercentrifuge by the catalyzer in bio oil and separated the removing of unreacted super large molecular components, by the component of the bio oil after GC/MS analytical separation; Utilize gas phase chromatographic analysis instrument 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) temperature of reaction system is reduced to after room temperature, carefully takes out the mixture of refining biological oil and catalyzer, utilizes high speed rotating whizzer to isolate catalyzer for recycling.
With the change of molecular weight of gel chromatography analytical test refining biological oil, with GC/MS, analyze component and the variation thereof of treated oil.Result shows, the molecular weight reduction by 87% of refining biological oil, and phenol and the small molecules ester content increasing degree that contains phenyl ring are respectively 93% and 95%.
Embodiment 4
1) measure 1000g bio oil and put into quartz apparatus, measure the previously prepared particle diameter of 0.1g is 200 object Pt-Ru/CdS-TiO simultaneously
2catalyzer is put into the vessel that fill bio oil, and puts into 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, and air enters before reactor successively the vessel through filling discolour silica gel and gac.Opening, adjust light source, to make the luminous power in reactor be 2000mw/cm
2, adjustments of gas flow velocity is distributed in reaction liquid gas uniform;
3) regulate water coolant flow velocity in light source and reactor interlayer, it is 40 ℃ that the heating unit of simultaneously opening quartz apparatus bottom makes the homo(io)thermism in reaction system, and the wavelength of light source is 0.32～4um;
4) in reaction process, every 1 hour, from reactor thief hole, take out bio oil, and utilize supercentrifuge by the catalyzer in bio oil and separated the removing of unreacted super large molecular components, by the component of the bio oil after GC/MS analytical separation; Utilize gas phase chromatographic analysis instrument 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) temperature of reaction system is reduced to after room temperature, carefully takes out the mixture of refining biological oil and catalyzer, utilizes high speed rotating whizzer to isolate catalyzer for recycling.
With the change of molecular weight of gel chromatography analytical test refining biological oil, with GC/MS, analyze component and the variation thereof of treated oil.Result shows, the molecular weight reduction by 53% of refining biological oil, and phenol and the small molecules ester content increasing degree that contains phenyl ring are respectively 83% and 81.5%.
Embodiment 5
1) measure 1000g bio oil and put into quartz apparatus, measure the previously prepared particle diameter of 0.1g is 200 object Pt-Ru/CdS-TiO simultaneously
2catalyzer is put into the vessel that fill bio oil, and puts into 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, and air enters before reactor successively the vessel through filling discolour silica gel and gac.Opening, adjust light source, to make the luminous power in reactor be 2000mw/cm
2, adjustments of gas flow velocity is distributed in reaction liquid gas uniform;
3) regulate water coolant flow velocity in light source and reactor interlayer, it is 50 ℃ that the heating unit of simultaneously opening quartz apparatus bottom makes the homo(io)thermism in reaction system, and the wavelength of light source is 0.32～4um;
4) in reaction process, every 1 hour, from reactor thief hole, take out bio oil, and utilize supercentrifuge by the catalyzer in bio oil and separated the removing of unreacted super large molecular components, by the component of the bio oil after GC/MS analytical separation; Utilize gas phase chromatographic analysis instrument 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) temperature of reaction system is reduced to after room temperature, carefully takes out the mixture of refining biological oil and catalyzer, utilizes high speed rotating whizzer to isolate catalyzer for recycling.
With the change of molecular weight of gel chromatography analytical test refining biological oil, with GC/MS, analyze component and the variation thereof of treated oil.Result shows, the molecular weight reduction by 66% of refining biological oil, and phenol and the small molecules ester content increasing degree that contains phenyl ring are respectively 87% and 84%.
Embodiment 6
1) measure 1000g bio oil and put into quartz apparatus, measure the previously prepared particle diameter of 1.0g is 200 object Pt-Ru/CdS-TiO simultaneously
2catalyzer is put into the vessel that fill bio oil, and puts into 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, and air enters before reactor successively the vessel through filling discolour silica gel and gac.Opening, adjust light source, to make the luminous power in reactor be 2000mw/cm
2, adjustments of gas flow velocity is distributed in reaction liquid gas uniform;
3) regulate water coolant flow velocity in light source and reactor interlayer, it is 45 ℃ that the heating unit of simultaneously opening quartz apparatus bottom makes the homo(io)thermism in reaction system, and the wavelength of light source is 0.32～4um;
4) in reaction process, every 1 hour, from reactor thief hole, take out bio oil, and utilize supercentrifuge by the catalyzer in bio oil and separated the removing of unreacted super large molecular components, by the component of the bio oil after GC/MS analytical separation; Utilize gas phase chromatographic analysis instrument 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) temperature of reaction system is reduced to after room temperature, carefully takes out the mixture of refining biological oil and catalyzer, utilizes high speed rotating whizzer to isolate catalyzer for recycling.
With the change of molecular weight of gel chromatography analytical test refining biological oil, with GC/MS, analyze component and the variation thereof of treated oil.Result shows, the molecular weight reduction by 89% of refining biological oil, and phenol and the small molecules ester content increasing degree that contains phenyl ring are respectively 94% and 96%.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (6)
1. a method for 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 bio oil; Described visible light catalyst is loaded catalyst; The load transition element of described loaded catalyst is Fe, Ru, Co, Rh, Ni, Pt, Pd, Ag, Au, Zn or Cu; The carrier of described visible light catalyst is TiO
2film, SiO
2-TiO
2film, Sb doped Ti O
2film, CdS, CdS-TiO
2composite semiconductor, ZnO or WO
3;
The wavelength region of described illumination is 0.32～4.0um.
2. method according to claim 1, is characterized in that, described loaded catalyst is Pt-Ru/CdS-TiO
2.
3. method according to claim 1, is characterized in that, the light source of described illumination is sunlight.
4. method according to claim 1, is characterized in that, the luminous power of described illumination is 260～5000mw/cm
3.
5. method according to claim 1, is characterized in that, the mass ratio of described visible light catalyst and described bio oil is (1 * 10
-6～1 * 10
-2): 1.
6. method according to claim 1, is characterized in that, the temperature of reaction of described depolymerization reaction is 0～60 ℃, and the reaction pressure of described depolymerization reaction is 0.001～2MPa.
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| 张金龙，安保正一.贵金属负载光催化剂在丙炔光催化水解反应中的研究.《高等学校化学学报》.2004,第25卷(第4期), * |
| 张金龙,赵文娟,陈海军,徐华胜,陈爱平,安保正一.负载贵金属光催化剂的光催化活性研究.《物理化学学报》.2004,第20卷(第4期), * |
| 陈达，林德娟，颜建群.纳米TiO2的制备及其油脂降解和净水效果的研究.《漳州师范学院学报（自然科学版）》.2003,第16卷(第3期), * |
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