CN103060075A - Method for preparing biological oil through catalytic liquefaction of microalgae - Google Patents
Method for preparing biological oil through catalytic liquefaction of microalgae Download PDFInfo
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Abstract
The invention discloses a method for preparing biological oil through catalytic pyrolysis of a microalgae biomass. The method is as follows: pyrolysis liquefaction is carried out on microalgae in the presence of a catalyst in an intermittent high-pressure reaction kettle so as to prepare the biological oil. Reduced high-pressure gas is filled into the reaction kettle. A catalyst is added to the pyrolysis reaction, and the catalyst is a loaded noble metal catalyst, molybdenum-based catalyst, active carbon and the like. The microalgae comprise chlorella, spirulina, micro-green-algae, dunaliella salina and the like. The microalgae have the advantages of various types, high photosynthetic efficiency, high oil content, short production period, high oil production rate per unit area, easiness for culturing, no farmland occupation and the like and is a good raw material for preparing biological oil fuel. In addition, diesel type hydrocarbon can be prepared through modifying and upgrading the microalgae biological oil, and dependence of people on fossil fuel can be expected to be relieved.
Description
Technical field
The invention belongs to biotechnology and new energy field, be specifically related to a kind of method that catalytic liquefaction prepares bio oil of carrying out take little algae as raw material.
Background technology
Along with the petering out and use the caused increasing environmental pollution of fossil oil of fossil oil, seeking renewable, pollution-free alternative new forms of energy becomes the task of top priority.In the middle of all renewable new forms of energy, biomass become the focus of falling over each other to study with the plurality of advantages such as its high yield, low pollution, carbon dioxide zero discharge.Little algae, and receives much attention because of its wide, outstanding feature such as photosynthetic efficiency is high, adaptive capacity to environment is strong, growth cycle is short that distributes day by day as a kind of important renewable biomass.Therefore, the utilization of little algae and transformation technology become one of problem of lot of domestic and foreign scholar primary study gradually, and research mainly concentrates on the preparation field of little algae bio-oil fuel.But utilize the little algae of the extensive conversion of traditional method to prepare bio-oil fuel and have two large barriers: the one, the high algae kind of palpus screening and culturing oleaginousness; The 2nd, must carry out dry and extraction oil content wherein to the high-moisture algae kind of results.So, have the problems such as early investment is large, energy consumption is high, raw material availability is low, and many gordian techniquies remain to be broken through.Therefore, researching and developing little algae bio-oil fuel, to prepare new way extremely urgent.
Pyrolysis is a kind of thermochemistry method for transformation, can directly biomass at high temperature be liquefied to be coarse biometric oil.According to the difference of temperature rise rate, pyrolysis can be divided into fast pyrogenation and slow pyrolysis.The primary product of slow pyrolysis is coke and the main products of fast pyrogenation is bio oil, and fast pyrogenation has higher Wood Adhesives from Biomass efficient.The pyrolysis for little algae both at home and abroad also has correlative study, such as publication number be CN1446883A patent disclosure a kind of little algae fast pyrogenation prepare the method for bio oil, the mean calorie that obtains bio oil is about 29MJ/kg.Yet the bio oil productive rate that obtains by direct rapidly pyrolysing and liquefying is generally lower, and pyrolysis oil is a kind of thick liquid of brownish black, and moisture and oxygen, nitrogen content are all higher, and the quality of oil is relatively relatively poor.Therefore, how effectively under the condition of less energy-consumption, to obtain another focus that high-quality biological oil becomes the actual utilization of biomass liquefied oil.
In the pyrolytic process of biomass, the use of catalyzer can effectively improve the productive rate of bio oil and improve the quality of bio oil.Therefore, the selection of catalyzer is one of key of catalyse pyrolysis technology.At present, the employed catalyzer of biomass pyrolytic mainly comprises zeolite molecular sieve, carbonate, metal oxide and diatomite etc.Such as publication number be CN101624530A patent disclosure a kind of biomass liquefied oil and preparation method thereof, by pyrolytic technique little algae is carried out thermochemistry and transforms, added carbonate catalyst in the reaction, and obtained high-quality bio oil.And for example publication number be CN101514295A patent disclosure a kind of molecular sieve catalytic pyrolysis height contain the method that the little algae of fat amount prepares bio oil, utilize HZSM-5, MCM-48 or HY molecular sieve catalyst to obtain high-quality high yield bio oil.Publication number be CN102531816A patent disclosure a kind of method of preparing low-carbon alkene by catalytic cracking of micro algae, wherein used to comprise that solid acid and solid base catalyst carry out scission reaction.Yet, up to the present, rarely have report for application in little algae catalyse pyrolysis such as loaded noble metal catalyst, catalyst with base of molybdenum and gacs both at home and abroad, the further research to little algae pyrolysis to the catalytic effect of little algae pyrolysis of probing into these catalyzer is significant.
Summary of the invention
The object of the invention is to: at first, investigate dissimilar catalyzer to the impact of little algae catalyse pyrolysis liquefaction behavior, therefrom filter out preferably catalyzer of effect; Secondly, utilize this catalyzer to inquire into temperature of reaction, time, catalyst loading and reducing gas pressure to the rule that affects of bio oil productive rate and oil product, thereby optimize best little algae pyrolytic reaction condition.
The embodiment of the invention is achieved in that a kind ofly utilizes little algae catalyse pyrolysis to prepare the method for bio oil, and described method comprises the steps:
Little algae of drying is pulverized in pulverizer, obtain little algae particle;
Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor, add catalyzer, pour the high pressure reducing gas, sealing;
Autoclave is put into melting salt, the control temperature at 200~410 ℃, reaction times at 0~240min catalyst loading 0.02-1.2g, reducing gas gas pressure intensity 2-10MPa;
Cooling reactor after reaction finishes, inclining mixture in the reactor;
With organic solvent reaction mixture is extracted, remove by filter filter residue and obtain organic phase;
Revolve with Rotary Evaporators and to steam the solvent remove in the organic phase, resultant product is the bio oil product.
Further, described algae comprises chlorella, spirulina, little green alga and salt algae etc.
Further, the median size of described little algae particle is about 100 orders.
Further, described catalyzer is gac, Pd/C, Ru/C, Rh/C, Pt/C, Pt/C-S, MoS
2, Mo
2C, CoMo/ γ-Al
2O
3
Further, its kind is preferably noble metal catalyst, more preferably contains the Mo catalyzer, more preferably Mo
2C; The preferred amounts of described catalyzer is 0.02~1.2g.
Further, described high pressure reducing gas is preferably hydrogen, and its pressure is preferably 2~10MPa.
Further, described temperature of reaction is preferably 200~410 ℃, and more preferably 290~350 ℃, more preferably 310~330 ℃.
Further, the described reaction times is preferably 0~240min, more preferably 20~40min.
Further, described organic solvent for extraction is methylene dichloride, chloroform, benzene, ethylene dichloride, Virahol, ethyl acetate and ether, is preferably methylene dichloride.
Further, described bio oil productive rate is 13.7~52.6%, and its method of calculation are: bio oil productive rate (%)=(m
Oil÷ m
Raw material) * 100%
12, further, described bio oil chief component is ketone, ester class, alcohols, alkyl-substituted compound and hydrocarbon compound.
The present invention has following multiple advantage:
Little algae is a kind of growing plants that all has in land, ocean and lake, can directly cultivate in water, does not occupy cultivated land ground.China is populous, and cultivated land resource is nervous, and little algae does not strive the place of production with grain in process of growth, can effectively alleviate the threat that farm crop production is caused because of Biomass Energy Utilization.
Little algae contains a large amount of protein, carbohydrate and lipid, and xylogen and content of cellulose are relatively low, and this reaches maximum liquefaction productive rate and more reduce energy consumption so that little algae pyrolysis liquefaction treatment temp is lower.
Catalyse pyrolysis is than the pyrolytic reaction that does not add catalyzer, and the bio oil viscosity that obtains is low, good fluidity, and quality and productive rate are higher, can be directly as boiler oil or through upgrading upgrading preparation diesel hydrocarbons fuel.
The extraction solvent that the present invention uses can reclaim, and carries out recycle.
Pyrolytic reaction does not need other reaction mediums, has saved the expense on medium separates.
Description of drawings
Fig. 1 is that little algae catalyse pyrolysis that utilizes that the embodiment of the invention provides prepares the schema of the method for bio oil.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage more cheer and bright, below in conjunction with accompanying drawing 1 and embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 45.2wt.%.
Embodiment 2
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Pt/C catalyzer of 0.2g, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 46.17wt.%.
Embodiment 3
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Pd/C catalyzer of 0.2g, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 45.55wt.%.
Embodiment 4
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add CoMo/ γ-Al of 0.2g
2O
3Catalyzer pours the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 48.53wt.%.
Embodiment 6
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Ru/C catalyzer of 0.2g, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 46.25wt.%.
Embodiment 7
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Pt/C-S catalyzer of 0.2g, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 45.93wt.%.
Embodiment 8
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the MoS of 0.2g
2Catalyzer pours the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 51.68wt.%.
Embodiment 9
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Mo of 0.2g
2The C catalyzer pours the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 50.92wt.%.
Embodiment 10
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the activated-carbon catalyst of 0.2g, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 47.63wt.%.
Embodiment 11
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Rh/C catalyzer of 0.2g, pour the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is 48.43wt.%.
Embodiment 12
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add CoMo/ γ-Al of 0.2g
2O
3Or MoS
2Or Mo
2The C catalyzer is done three groups of experiments, pours the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is respectively 33.5%, 36.2%, 41.05%.
Temperature is on the impact of oily productive rate
Embodiment 13
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Mo of 0.2g
2The C catalyzer pours the hydrogen of 6MPa, sealing.Autoclave is put into high-temperature fusion salt, 11 groups of experimental temperatures are respectively 200 ℃, 230 ℃, 250 ℃, 290 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 370 ℃, 410 ℃, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is respectively 13.7wt.%, 30.7wt.%, 41.05wt.%, 47.8wt.%, 50.85wt.%, 51.7wt.%, 51.15wt.%, 50.25wt.%, 48.85wt.%, 46.95wt.%, 42.4wt.%.
Time is on the impact of oily productive rate
Embodiment 14
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Mo of 0.2g
2The C catalyzer pours the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, and 9 groups of experiment residence time are respectively 0min, 5min, 10min, 20min, 30min, 40min, 50min, 90min, 240min, and reaction finishes, and take out reactor and place room temperature water to cool off rapidly.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is respectively 48.2wt.%, 49.45wt.%, 49.9wt.%, 50.85wt.%, 52.6wt.%, 51.75wt.%, 51.2wt.%, 51.05wt.%, 49.7wt.%.
Catalyst loading is on the impact of oily productive rate
Embodiment 15
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, Mo is added in seven groups of experiments
2The amount of C catalyzer is respectively 0.02g, 0.1g, 0.2g, 0.4g, 0.6g, 0.8g, 1.2g, pours the hydrogen of 6MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is respectively 48.15wt.%, 49.8wt.%, 50.8wt.%, 52.4wt.%, 51.1wt.%, 50.15wt.%, 50.1wt.%.
Reducing gas pressure is on the impact of oily productive rate
Embodiment 16
Little algae of drying is pulverized in pulverizer, obtain little algae particle.Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor of 17.2mL, add the Mo of 0.2g
2The C catalyzer, 5 groups of experiments are poured hydrogen and are respectively 2MPa, 4MPa, 6MPa, 8MPa, 10MPa, sealing.Autoclave is put into 310 ℃ melting salt, take out reactor and place room temperature water to cool off rapidly behind the reaction 20min.The question response still is cooled to room temperature, with hair dryer reactor is dried up, and then opens valve reactor is reduced pressure.Open reactor, inclining mixture in the still, with methylene dichloride reaction mixture is extracted, and removes by filter filter residue and obtains organic phase.Revolve steaming with Rotary Evaporators and remove organic phase, surplus materials is bio oil, and its productive rate is respectively 49.0wt.%, 50.05wt.%, 50.7wt.%, 51.6wt.%, 50.9wt.%.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. one kind is utilized little algae catalyse pyrolysis to prepare the method for bio oil, it is characterized in that described method comprises the steps:
Little algae of drying is pulverized in pulverizer, obtain little algae particle;
Take by weighing the little algae 2.0g that handles well, place the intermittent high-pressure reactor, add catalyzer, pour the high pressure reducing gas, sealing;
Autoclave is put into high-temperature fusion salt, 200-410 ℃ of control temperature, reaction times 0-240min, catalyst loading 0.02-1.2g, reducing gas pressure 2-10MPa;
Cooling reactor after reaction finishes, inclining mixture in the reactor;
With organic solvent reaction-ure mixture is extracted, remove by filter filter residue and obtain organic phase;
Revolve with Rotary Evaporators and to steam the solvent remove in the organic phase, resultant product is the bio oil product.
2. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that described algae comprises chlorella, spirulina, little green alga and salt algae.
3. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that the median size of described little algae particle is about 100 orders.
4. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that described catalyzer is gac, Pd/C, Ru/C, Rh/C, Pt/C, Pt/C-S, MoS
2, Mo
2C, CoMo/ γ-Al
2O
3
5. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that its kind is preferably noble metal catalyst, more preferably contain the Mo catalyzer, more preferably Mo
2C; The preferred amounts of described catalyzer is 0.02~1.2g.
6. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that described reducing gas is hydrogen, its pressure is preferably 2~10MPa.
7. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that described temperature of reaction is preferably 200~410 ℃, more preferably 290~350 ℃, more preferably 310~330 ℃.
8. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that the described reaction times is preferably 0~240min, more preferably 20~40min.
9. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that, described organic solvent for extraction is methylene dichloride, chloroform, benzene, ethylene dichloride, Virahol, ethyl acetate and ether.
10. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that the productive rate of described bio oil is 13.7~52.6wt.%.
11. utilize little algae catalyse pyrolysis to prepare the method for bio oil according to claims 1 are described, it is characterized in that described biological main body of oil has ketone, ester class, alcohols, alkyl-substituted compound and hydrocarbon compound.
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CN103484234A (en) * | 2013-09-18 | 2014-01-01 | 河南理工大学 | Method for preparing biological oil through catalyzing and liquefying microalgae |
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