CN103361166A - Method for preparing biofuel by directly liquefying microalgae - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002551 biofuel Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 241000195493 Cryptophyta Species 0.000 claims description 58
- 239000000295 fuel oil Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 241000195633 Dunaliella salina Species 0.000 claims description 3
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 2
- 241000192700 Cyanobacteria Species 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 9
- 239000012075 bio-oil Substances 0.000 description 9
- 150000002632 lipids Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 150000001747 carotenoids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention relates to a method for preparing biofuel by directly liquefying microalgae; mixing microalgae and the alcohol-water mixed solution, placing the mixture into a reaction kettle, and heating the mixture for reaction; the reaction conditions are as follows: the temperature is 260-360 ℃; the pressure is 7-22 MPa; the reaction time is 15-45 min; the ratio of the microalgae to the alcohol-water mixed solution is 1: 5-20, and the unit is g/mL; in the alcohol-water mixed solution, the volume percentage of alcohol is 20-80%; after the reaction is finished, adding an organic solvent to extract reaction liquid, and dividing the reaction liquid into an organic solvent phase, an alcohol-water phase and solid residues; after extraction, carrying out suction filtration to separate out solid residues, standing and layering a liquid phase, and then separating to obtain an organic solvent phase; distilling the organic solvent phase under reduced pressure to remove the organic solvent to obtain oily liquid, namely a biofuel oil product; the conditions of reduced pressure distillation were: gauge pressure is 0.085-0.095 MPa, and temperature is 20-40 ℃; the method has simple process flow and low energy consumption; the process is environment-friendly.
Description
Technical field
The invention belongs to the biomass energy technology field, particularly the little algae of direct liquefaction prepares the method for bio-fuel-oil under a kind of Asia/supercritical water-pure condition.
Background technology
Along with the fast development of modern industry with science and technology, the problem of environmental pollution in short supply and that use fossil resource to bring of fossil resource has become two hang-ups of restriction human kind sustainable development.That biomass energy has is renewable, without CO
2Clean discharging and SO
x, NO
xThe advantages such as quantity discharged is few become the new forms of energy of people's common concern.At present, how fully effectively utilizing biomass resource has become people and has fallen over each other the focus studying and pay close attention to.The research that begins to consider to prepare take biomass as raw material the bio-fuel-oil aspect both at home and abroad mainly is that material take lignin and Mierocrystalline cellulose or hemicellulose class is as main, but because the temperature that lignin and Mierocrystalline cellulose or hemicellulose class need in pyrolytic process is high, processing condition are comparatively harsh, cause production cost to improve.Simultaneously, lignin and Mierocrystalline cellulose or hemicellulose are owing to self chemical composition and structure characteristic, and the bad of cracking gained bio-fuel-oil is compared with gasoline or diesel oil and still had larger difference, have therefore limited its development.
At present, little algae prepares biofuel and has obtained showing great attention to of countries in the world government and investigator.Little algae biofuel is considered to the third generation biofuel behind grain and the biological fuel of Mierocrystalline cellulose, algae is about to become one of most important biofuel source, be widely used little algae energy and can significantly alleviate fossil energy to the negative impact that social and environment bring, will become the trend of following bioenergy exploitation.The U.S. started " the miniature manhattan project " of obtaining energy fuel from little algae in 2007, and USDOE was issued again " national little algae bioenergy Technology Roadmap " draft in 2009.China also progressively strengthens the strategic understanding of seaweed bio fuel, the marine alga energy is being classified as the important component part of following biomass fuel industry.
Little algae is that a class formation is simple, the rapidly lower plant that grows, and it is wide at the distributed pole in the whole world, and having slightly, algae is the potential high quality raw material of preparation bioenergy owing to containing abundant grease.Compare with other higher plants, little algae has many advantages as the raw material of producing bioenergy: photosynthetic efficiency is high, growth cycle is short, adaptive capacity to environment is strong, easily cultivate, lipid content is high and process of growth in the efficient advantage such as stabilizing carbon dioxide.In addition, algal grown and procreation all are in water, do not strive ground with agricultural, do not affect agriculture production and process and can realize automatization and mass-producing.Therefore, research and develop little algal biomass energy conversion utilisation technology and have extremely important strategic importance.
Little algae recovery energy the earliest is to adopt the extracting, esterifying method, first lipid out is converted into biofuel through transesterification reaction again from the microalgae cell extracting and separating.Yet little algae is made of biochemical components such as protein, polysaccharide and lipids, and the extracting, esterifying method can only be utilized lipidic component wherein, and is high to the lipid content requirement of raw material, and the lipid composition is subjected to the lipid composition to affect very large on product property.In order to take full advantage of all components of little algae, people begin to adopt thermochemical techniques algae to be changed into the liquefied product-bio oil (bio-oil) of high-quality.Bio oil has low, the easy storage of sulphur nitrogen content, easily transportation and energy density advantages of higher, can be directly use as boiler oil, after also can promoting through upgrading as power with oil, also can be used to refine the chemical of processing high added value.
The liquefaction of little algae mainly comprises Rapid Thermal solution and direct liquefaction method etc.The Rapid Thermal solution is under the secluding air condition, adopts superelevation heating rate and ultra short contact time that little algae pyrolysis is converted into bio oil.The Rapid Thermal solution need to be carried out drying to raw material, so energy consumption is large; Next severe reaction conditions, equipment requirements is high.The direct liquefaction method claims again pressurized liquefied, refers to the method that biomass liquefy under suitable ambient condition.Wherein the direct liquefying method take water as medium claims again the hydro-thermal liquefaction process, and water medium is in Asia/supercritical state usually in little algae hydro-thermal liquefaction process.Compare with the pyrolysis liquefaction method, the hydro-thermal liquefaction process has following advantage: (1) raw material need not drying, energy consumption reduces greatly.This point is even more important (little algae water content generally surpasses 80%) to the great little algae of water content; (2) gained bio oil oxygen level and moisture obviously are better than quick cracking process; (3) the wet contained moisture of algae can provide hydrogenation liquefaction required hydrogen, is conducive to the generation of liquefaction reaction and the generation of short hydrocarbon; (4) Asia/supercritical water have macroion long-pending, to organic superpower solvability, the characteristic such as viscosity is low, resistance to mass transfer is little and diffusion is good, the liquefaction oil that hydro-thermal liquefaction produces can dissolve rapidly and spread, and has reduced the generation of condensation or the side reaction such as coking.The hydro-thermal liquefaction process of algae is subject to various countries investigator's extensive concern at present, becomes gradually the mainstream research direction in this field.Yet also there are many weak points in the liquefaction of algae hydro-thermal: (1) oily productive rate is low; (2) quality of bio-oil is undesirable.These shortcomings have seriously restricted the mass-producing of little algae hydro-thermal liquefaction process and have used.Except water as the medium, adopt the stronger solvent of other hydrogen supply capacities can improve liquefaction effect.Part alcohol also can with liquefaction intermediate lipid acid generation esterification, thereby improve bio oil productive rate and calorific value.Alcohols is cheap and easy to get, and wherein part alcohol can be obtained by biomass ferment, also has recyclability.
Mention a kind of method that from little algae, prepares biofuel in the patent of invention 200910148494.7.This patent is extracted microalgae grease and one step of production of biodiesel finishes, and simplifies processing step and equipment, saves cost; Produce used sulfuric acid and low-carbon alcohol recyclable after, the again drying recycling of anhydrating reduces the cost, and the finished product are neutrality and need not washing, alleviates aftertreatment pressure.But this patent has two deficiencies: 1. in little algae except lipid, also have the compositions such as a large amount of protein, polysaccharide not take full advantage of, caused the huge waste of resource.2. this technological process adopts the liquid sulfur acid as catalyst, and catalyzer is not easy to be recycled.If do not carry out aftertreatment, directly discharging then can cause serious environmental pollution.
Mention a kind of method of from Dunaliella salina, extracting carotenoid and liquefaction bio-fuel-oil in the patent of invention 200910238784.0.This patent extracts carotenoid first under the supercritical co condition, the algae-residue that obtains is liquefaction bio-fuel-oil processed under the condition of super/near-critical water.Raw material need not drying, energy consumption is low, and whole process environment is friendly, technique is simple; Plant factor is high.But the described algae-residue liquefaction process of this patent is to carry out under the condition of super/near-critical water, because emergent pressure and the critical temperature relatively high (Tc:374.15 ℃ and Pc:22.12Mpa) of supercritical water, the liquefaction reaction of little algae is higher to equipment requirements in Asia/supercritical water medium, and reaction conditions is relatively harsh; Simultaneously, the liquefaction process of little algae in Asia/supercritical water exists oil yield rate relatively on the low side, causes the shortcomings such as its quality is undesirable in the product bio-fuel-oil because acid number is higher.
Summary of the invention
The purpose of this invention is to provide the method that a kind of little algae direct liquefaction prepares bio-fuel-oil, for the worsening shortages of current fossil resource, and the Application and Development of biomass resource has environmental protection and reproducible characteristics.
To achieve these goals, little algae provided by the invention prepares the method for bio-fuel-oil, take little algae as raw material, (supercritical water refers to that temperature and pressure is higher than the water of stagnation point (374.2 ℃ and 22.1MPa) at Asia/supercritical water, and subcritical water refers to that temperature and pressure does not reach near the water of stagnation point, general temperature should be greater than 200 ℃)-pure condition under the little algae of direct liquefaction prepare bio-fuel-oil, it is characterized in that, the method is carried out as follows:
(1) a certain amount of little algae sample is placed reactor from the aqueous solution of different percentage composition alcohol, heat to certain temperature and react;
(2) after reaction finishes, add organic solvent extracting and extract reaction solution, reaction solution is divided into organic solvent phase, pure water and solid residue;
(3) after extraction finished, suction filtration was isolated solid residue, separated obtaining organic phase behind the liquid phase standing demix;
(4) organic solvent is removed in the organic phase underpressure distillation, obtained oily liquids and be the bio-fuel-oil product.
In the method for the present invention, described little algae is selected from one or more the mixture in Dunaliella salina, chlorella and the blue-green algae.
In the method for the present invention, the solid-liquid ratio of described little algae and Asia/supercritical water-pure blending agent is 1: 5~1: 20 (g/mL).
In the method for the present invention, in described Asia/supercritical water-pure blending agent, the volumn concentration of alcohol is 20%~80%.
In the method for the present invention, described alcohol is selected from and is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, the butanols.
In the method for the present invention, the reaction conditions of the little algae of direct liquefaction is under Asia/supercritical water-pure condition: liquefaction temperature is 260 ℃~360 ℃; Pressure is 7~22MPa; Reaction times is 15~45min.
In the method for the present invention, described organic solvent is selected from and is one or more the mixture in normal hexane, chloroform, the tetrahydrofuran (THF).
In the method for the present invention, distillation condition is under the reduced pressure described in the step (4), and pressure is 0.085~0.095MPa (gauge pressure), and temperature is 20~40 ℃.
In the method for the present invention, the liquefied fraction of the little algae of direct liquefaction is higher than 90% under described Asia/supercritical water-pure condition, and oil yield rate is 40%~70%.
Beneficial effect of the present invention is:
(1) uses little algae to be raw material, can overcome and alleviate the in short supply and problem of environmental pollution of fossil energy, also do not need raw material is carried out drying treatment simultaneously, reduced the energy consumption of process, reduced production cost;
(2) Asia/supercritical water-pure mixed solvent unique properties, the cheap environmental protection of safety.Little algae raw material does not need drying, and energy consumption reduces greatly;
(3) whole technological process is simple, energy consumption is low, easy to operate, have the industrial applications prospect;
(4) rate of the liquefied fraction of little algae and bio-fuel-oil is high, and the bio-fuel-oil water content is little, ash content is low, acid number is low, calorific value is high.
(5) three effects of introducing alcohols in the water medium: Asia/supercritical water solvent is carried out the performance regulation and control, reduce stagnation point; Little algae required hydrogen that liquefies is provided; Carry out esterification with little algae liquefaction intermediate organic acid and improve bio oil productive rate and quality.
Description of drawings
Fig. 1 is the present invention prepares bio-fuel-oil in the little algae of direct liquefaction process flow sheet
Embodiment:
Describe the present invention in detail below in conjunction with Fig. 1.Be that 1: 5~1: 20 (g/mL) takes by weighing the algae sample and water-alcohol mixture joins in the reactor according to solid-liquid ratio at first, the volumn concentration of alcohol is 20%~80% in the water-alcohol mixture medium, after the sealing reactor is transferred in the process furnace, then react under suitable reaction conditions, reaction conditions is: liquefaction temperature is 260 ℃~360 ℃; Pressure is 7~22MPa; Reaction times is 15~45min.After reaction finishes, take out reactor, be cooled to room temperature.Take out reaction product, add organic solvent and extract, the product mixed solution that obtains is divided into three parts: organic phase, pure water and solid residue; Isolate solid residue behind the mixture suction filtration, after the drying, weigh in the solid residue baking oven, calculate liquefied fraction; Filtrate is used the separating funnel standing demix, isolates pure water and organic phase, after wherein pure water is removed alcohol, obtains water soluble ingredient; Organic phase is the Distillation recovery organic solvent under the condition of underpressure distillation, obtains bio oil, weighs, and calculates oil yield rate.
Embodiment 1
Be that 1: 10 (g/mL) takes by weighing the little algae sample of 4g and the 40mL water-alcohol mixture joins in the reactor according to solid-liquid ratio, the volumn concentration of alcohol is 40% in the water-alcohol mixture medium, and liquefaction temperature is 260 ℃; Pressure is 8.45MPa; Reaction times is 30min, and the liquefied fraction of the little algae of gained is 92.84%, and oil yield rate is 47.11%.
Embodiment 2
Be that 1: 10 (g/mL) takes by weighing the little algae sample of 4g and the 40mL water-alcohol mixture joins in the reactor according to solid-liquid ratio, the volumn concentration of alcohol is 40% in the water-alcohol mixture medium, and liquefaction temperature is 340 ℃; Pressure is 14.52MPa; Reaction times is 30min, and the liquefied fraction of the little algae of gained is 99.35%, and oil yield rate is 60.56%.
Embodiment 3
Be that 1: 10 (g/mL) takes by weighing the little algae sample of 4g and the 40mL water-alcohol mixture joins in the reactor according to solid-liquid ratio, the volumn concentration of alcohol is 0% in the water-alcohol mixture medium, and liquefaction temperature is 320 ℃; Pressure is 11.27MPa; Reaction times is 30min, and the liquefied fraction of the little algae of gained is 95.39%, and oil yield rate is 48.93%.
Embodiment 4
Be that 1: 10 (g/mL) takes by weighing the little algae sample of 4g and the 40mL water-alcohol mixture joins in the reactor according to solid-liquid ratio, the volumn concentration of alcohol is 40% in the water-alcohol mixture medium, and liquefaction temperature is 320 ℃; Pressure is 13.80MPa; Reaction times is 33min, and the liquefied fraction of the little algae of gained is 98.24%, and oil yield rate is 64.68%.
Embodiment 5
Be that 1: 10 (g/mL) takes by weighing the little algae sample of 4g and the 40mL water-alcohol mixture joins in the reactor according to solid-liquid ratio, the volumn concentration of alcohol is 100% in the water-alcohol mixture medium, and liquefaction temperature is 320 ℃; Pressure is 11.30MPa; Reaction times is 33min, and the liquefied fraction of the little algae of gained is 91.81%, and oil yield rate is 49.89%.
Claims (4)
1. a little algae direct liquefaction prepares the method for bio-fuel-oil, it is characterized in that:
(1) little algae is mixed with pure water mixed solution place reactor, heating is reacted; Reaction conditions is: temperature is 260~360 ℃; Pressure is 7~22MPa; Reaction times is 15~45min;
Little algae is 1: 5~20 with pure water mixed solution ratio, the g/mL of unit;
In the alcohol water mixed solution, the volumn concentration of alcohol is 20~80%;
(2) after reaction finishes, add organic solvent extracting and extract reaction solution, reaction solution is divided into organic solvent phase, pure water and solid residue;
(3) after extraction finished, suction filtration was isolated solid residue, separated obtaining the organic solvent phase behind the liquid phase standing demix;
(4) organic solvent is removed in the underpressure distillation of organic solvent phase, obtained oily liquids and be the bio-fuel-oil product; The condition of underpressure distillation is: gauge pressure 0.085~0.095Mpa, 20~40 ℃ of temperature.
2. the preparation method of described bio-fuel-oil according to claim 1 is characterized in that: described little algae is selected from one or more the mixture in Dunaliella salina, chlorella and the blue-green algae.
3. the preparation method of described bio-fuel-oil according to claim 1 is characterized in that: described alcohol is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol, the butanols.
4. the preparation method of described bio-fuel-oil according to claim 1 is characterized in that: described organic solvent can be one or more the mixture in normal hexane, chloroform, the tetrahydrofuran (THF).
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CN104730161A (en) * | 2013-11-20 | 2015-06-24 | 江苏理工学院 | Method for detecting content of triglyceride in microalgae |
CN105018211A (en) * | 2015-07-13 | 2015-11-04 | 上海婉静纺织科技有限公司 | Cyanobacteria extract oil for biological fuel and preparation method of cyanobacteria extract oil |
CN105062576A (en) * | 2015-07-20 | 2015-11-18 | 肖宏阳 | Method for extracting liquid fuel from green algae |
CN105132043A (en) * | 2015-07-15 | 2015-12-09 | 广西南宁高斯特科贸有限公司 | Bio-fuel oil and preparation method thereof |
CN105176601A (en) * | 2015-07-13 | 2015-12-23 | 上海婉静纺织科技有限公司 | High-calorific value environmental-friendly biodiesel, and preparation method thereof |
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CN108315075A (en) * | 2018-02-11 | 2018-07-24 | 北京欧美中科学技术研究院 | A kind of high-capacity environment-protecting type biomass fuel and preparation method thereof |
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