CN106367128B - A method of producing biodiesel using microalgae - Google Patents

A method of producing biodiesel using microalgae Download PDF

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Publication number
CN106367128B
CN106367128B CN201610766810.7A CN201610766810A CN106367128B CN 106367128 B CN106367128 B CN 106367128B CN 201610766810 A CN201610766810 A CN 201610766810A CN 106367128 B CN106367128 B CN 106367128B
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biodiesel
isochrysis galbana
microalgae
grease
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CN106367128A (en
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黄健峻
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Nanning Gongjianyuan Health Technology Co ltd
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Nanning City Enyuan Health Science And Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/02—Pretreatment
    • C11B1/04—Pretreatment of vegetable raw material
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Zoology (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention discloses a kind of methods producing biodiesel using microalgae, include the following steps：Isochrysis galbana is seeded to culture medium, with red blue dual-colored LED light filling light irradiation 18 22h/ days, is cultivated 10 12 days at 25 28 DEG C, you can collection Isochrysis galbana cell；It is broken that the Isochrysis galbana cell of collection is added high speed ball mill, then is extracted with organic solvent, obtains microalgae grease, then by microalgae grease, methanol and zeolite molecular sieve catalyst according to mass ratio is 1:3‑6:0.01 0.03 ratio is added in reactor and carries out esterification, obtains esterification products, esterification products are using separation, purification, you can obtain biodiesel.The method of the present invention solves the problems, such as that the vegetable fat raw material in biodiesel exploitation exists using the Isochrysis galbana that with short production cycle, widely distributed, photosynthesis is strong, fat content is high as raw material.Also have many advantages, such as that preparation process is simple, high catalytic efficiency, grease extraction efficiency are high, product yield is high simultaneously, lays a good foundation for biodiesel industrialization, scale.

Description

A method of producing biodiesel using microalgae
Technical field
The invention belongs to biomass energy technology field, a kind of specifically side producing biodiesel using microalgae Method.
Background technology
With the increasingly depleted of fossil fuel, oil price persistently sharp rises, and seeks regenerative resource and has become solution Human survival and the needs for keeping world economy sustainable development, the biodiesel as novel alternative energy source are sent out in countries in the world Exhibition is rapid.Biodiesel refers to oil crops such as soybean, rape, cotton, palm etc., the water such as Wild oil plant and engineering microalgae Plant grease and animal fat, food garbage oil etc. can be replaced by feedstock oil made of transesterification or thermochemical processes The reproducibility diesel fuel of petrifaction diesel.The advantage of biodiesel is not limited only to recyclability, compared with existing diesel oil, also has Following advantage：Cetane number is high so that combustibility is more preferable；Preferable wettability makes injection pump, engine cylinder body and connecting rod Abrasion reduce, prolong the service life；Sulfur content is low in biodiesel, and the discharge of sulfur dioxide and sulfide is low, reduces environment Pollution；Biodiesel flash-point is high, is not belonging to dangerous material, advantageous in transport, storage, use aspect etc..
Currently, China's industrialized production biodiesel is mainly with rapeseed oil, cottonseed oil, Chinese tallow, shinyleaf yellowhorn oil, tea oil It is raw material with gutter oil etc..But the biodiesel of the limits throughput of these raw materials, production can only meet current automobile-used demand for fuel The 0.3% of amount.And biodiesel largely is produced with vegetable fat, the anxiety and crops price of land resource will certainly be caused Rise, especially in the case where China has a large population and a few land, these are particularly problematic.In this case, microalgae biodiesel The concern of more and more people is attracted with its unique advantage.Microalgae is planted as a kind of important biodiesel raw material with oil plant Object is compared, have distribution is wide, biomass height, photosynthetic efficiency height, strong environmental adaptability, growth cycle is short, fat content is high, at Originally low and environmental-friendly equal significant advantages.
In recent years, the research that prepared by related biodiesel is concentrated mainly on woody oleiferous plants and disposed waste oil etc., from Grease is extracted in microalgae is used to prepare the research report of biodiesel seldom.Wherein, biodiesel one is prepared by raw material of microalgae As comprise the following steps that：Strain selection, pilot scale culture, extraction grease, esterification prepare biodiesel coarse product, warp It crosses refining and can be obtained biodiesel.The microalgae type for selecting fat content high is the key that prepare biodiesel, is cultivated simultaneously Base and environmental factor also have important influence to the fat content of microalgae.Therefore, how to improve the nutritional ingredient of culture medium and change The changing environment factor is to improve one of the approach of algae lipid-producing.Although it can be that biodiesel is laid well to improve microalgae fat content Basis, but the production technology of biodiesel is most important to its yield effect.The production technology of existing biodiesel is general It has the following problems：Catalytic efficiency is low, yield of biodiesel is low, the reaction time is long, etching apparatus, complex process, energy consumption are larger, The deficiencies of cost is higher.
Isochrysis galbana (Isochrysis galbana), belongs to and determines whip Chrysophyceae, equilateral chrysophyceae section.Unicellular movement Body, form is changeable, oval, acellular wall, has two isometric flagellums, and fat content 25% or so is main in lubricant component Contain C18、C16The fatty glyceride of carbochain, it is close with the biodiesel fuel component extracted from vegetable oil, be it is a kind of have open Send out the bioenergy material of potentiality.
Invention content
The present invention for vegetable fat limits throughput and existing biodiesel oil preparing process there are the problem of, a kind of profit is provided The method for producing biodiesel with microalgae.The method of the present invention has extensive raw material sources, high catalytic efficiency, low, the biological bavin of energy consumption The advantages that oily yield is high, preparation process is simple is laid a good foundation for biodiesel industrialization, scale, can effectively be delayed Solve problem of energy crisis.
In order to achieve the goal above, the present invention is achieved through the following technical solutions：
A method of biodiesel being produced using microalgae, is included the following steps:
S1. Isochrysis galbana culture：Using Isochrysis galbana as raw material, then with the inoculum density of ten thousand cell/mL of 100-200 It is seeded to culture medium, with red blue dual-colored LED light filling light irradiation 18-22h/ days, control intensity of illumination was cultivated in 3500-4500LX Temperature is controlled at 25-28 DEG C, is cultivated 10-12 days, and the density of Isochrysis galbana reaches concentration and reaches 90,000,000 cell/mL, is received Collect Isochrysis galbana cell；The culture medium is composed of the following components：Glucose 25-30mg/L, NaNO31.6-2.0mg/L、 KH2PO41.0-1.3mg/L、Na2SiO30.3-0.5mg/L, chitosan 0.8-1.0mg/L, biogas slurry 5-7mg/L, f2 vitamin 2- 3mL and seawater 1L；
S2. grease extracts：After step S1 is collected the drying of Isochrysis galbana cell concentration, high speed ball mill is added and is crushed, Isochrysis galbana powder is obtained, it is 1 to be added in Isochrysis galbana powder with its mass ratio:The petroleum ether of 7-9, mixing stand 2-6h, on Layer liquid is grease extracting solution, then extracting solution is distilled at 75-80 DEG C, you can obtains microalgae grease；
S3. ester exchange reaction：By microalgae grease, methanol and zeolite molecular sieve catalyst according to mass ratio be 1:3-6: The ratio of 0.01-0.03 is added in reactor, in the case where temperature is 50-60 DEG C, carries out esterification 90-100min, is esterified Product；
S4. standing separation；Esterification products are centrifuged into 15-18min in the case where rotating speed is 150-200r/min, stratification divides Upper layer glycerine is separated out, lower layer is biodiesel crude product；
S5. distilation：Biodiesel crude product is added into destilling tower, extra methanol is distilled off at 85-90 DEG C, you can Obtain biodiesel.
Further, the preparation method of the f2 vitamins described in above step S1 is as follows：0.5mg vitamin Bs12、0.5mg Biotin, 100mL vitamin B1s and pure water 1000mL.
Further, the feux rouges in above-described red blue dual-colored LED light compensating lamp and blue light proportioning are 1-2:1, preferably match Than being 2：1.
Further, it is that control rotating speed is broken at 800-1000r/min that the high speed ball mill described in above step S2 is broken Broken 10-15min..
Compared with prior art, the advantageous effect that the present invention obtains：
1, the present invention prepares biodiesel by raw material of Isochrysis galbana, and current energy crisis and environment can be effectively relieved Pollution problem, Isochrysis galbana have distribution wide, biomass height, photosynthetic efficiency height, strong environmental adaptability, growth cycle it is short, Fat content is high, significant advantages at low cost and environmental-friendly etc., can solve vegetable fat raw material in biodiesel exploitation not Enough, the problems such as cost is excessively high.
2, the chitosan and biogas slurry that the present invention is added in the medium, contain the nutrition such as a large amount of trace element, organic matter Ingredient can accelerate microalgae speed of production and improve the lipid-producing of microalgae.
3, the method for the present invention changes illumination condition by using red blue dual-colored LED light compensating lamp, can not only improve the whips such as ball The photosynthesis of chrysophyceae accelerates Isochrysis galbana production and improves yield, while can also improve the grease production of Isochrysis galbana Rate, compared with common incandescent lamp, fluorescent lamp or monochromatic LED lamp, the lipid-producing of Isochrysis galbana improves 5% or so.
4, the present invention uses high speed ball mill crushing microalgae cells, has at low cost, efficient, environmentally safe, consumption The low advantage of energy is a kind of cost-effectively processing method.
5, the method for the present invention using zeolite molecular sieve as catalyst, have reaction interface is big, surface area greatly, resistance to mass tranfer Small, reaction condition is mild, activity is high, pollution-free, not etching apparatus the features such as, improve catalytic efficiency, shorten esterification Time, catalytic effect is notable, improves the yield of biodiesel.
6, the method for the present invention is simple with preparation process, high catalytic efficiency, grease extraction efficiency are high, biodiesel production rate is high, Product purity is high, raw material sources are extensive, at low cost, the low advantage of energy consumption, has society, ecology and economic benefit well, is Microalgae biodiesel industrialization, scale are laid a good foundation.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is further described, but is not limited to protection scope of the present invention.
Embodiment 1
The preparation of Isochrysis galbana culture medium：Glucose 25mg/L, NaNO32.0mg/L、KH2PO41.0mg/L、 Na2SiO30.3mg/L, chitosan 0.8mg/L, biogas slurry 5mg/L, f2 vitamin 2mL and seawater 1L；
A method of biodiesel being produced using microalgae, is included the following steps：
S1. Isochrysis galbana culture：Using Isochrysis galbana as raw material, then with the inoculum density inoculation of 1,500,000 cell/mL To culture medium, with red blue dual-colored LED light filling light irradiation 18h/ days, wherein feux rouges and blue light proportioning were 1:1, control intensity of illumination exists 3500LX, cultivation temperature are controlled at 25 DEG C, are cultivated 12 days, the density of Isochrysis galbana reach concentration reach 90,000,000 cells/ ML collects Isochrysis galbana cell；
S2. grease extracts：After step S1 is collected the drying of Isochrysis galbana cell concentration, high speed ball mill is added in rotating speed To be crushed 15min under 800r/min, Isochrysis galbana powder is obtained, it is 1 to be added in Isochrysis galbana powder with its mass ratio:7 stone Oily ether, mixing stand 2h, and upper liquid is grease extracting solution, then extracting solution is distilled at 75 DEG C, you can obtains microalgae grease；
S3. ester exchange reaction：By microalgae grease, methanol and zeolite molecular sieve catalyst according to mass ratio be 1:3:0.03 Ratio is added in reactor, in the case where temperature is 50 DEG C, carries out esterification 90min, obtains esterification products；
S4. standing separation；Esterification products are centrifuged into 15min in the case where rotating speed is 200r/min, stratification isolates upper layer Glycerine, lower layer are biodiesel crude product；
S5. distilation：Biodiesel crude product is added into destilling tower, extra methanol is distilled off at 85 DEG C, you can To biodiesel.
Embodiment 2
The preparation of Isochrysis galbana culture medium：Glucose 27mg/L, NaNO31.8mg/L、KH2PO41.1mg/L、 Na2SiO30.4mg/L, chitosan 0.9mg/L, biogas slurry 6mg/L, f2 vitamin 3mL and seawater 1L；
A method of biodiesel being produced using microalgae, is included the following steps：
S1. Isochrysis galbana culture：Using Isochrysis galbana as raw material, then with the inoculum density inoculation of 2,000,000 cell/mL To culture medium, with red blue dual-colored LED light filling light irradiation 20h/ days, wherein feux rouges and blue light proportioning were 2:1, control intensity of illumination exists 4000LX, cultivation temperature are controlled at 26 DEG C, are cultivated 10 days, the density of Isochrysis galbana reach concentration reach 90,000,000 cells/ ML collects Isochrysis galbana cell；
S2. grease extracts：After step S1 is collected the drying of Isochrysis galbana cell concentration, high speed ball mill is added in rotating speed To be crushed 13min under 900r/min, Isochrysis galbana powder is obtained, it is 1 to be added in Isochrysis galbana powder with its mass ratio:8 stone Oily ether, mixing stand 4h, and upper liquid is grease extracting solution, then extracting solution is distilled at 80 DEG C, you can obtains microalgae grease；
S3. ester exchange reaction：By microalgae grease, methanol and zeolite molecular sieve catalyst according to mass ratio be 1:4:0.02 Ratio is added in reactor, in the case where temperature is 55 DEG C, carries out esterification 100min, obtains esterification products；
S4. standing separation；Esterification products are centrifuged into 16min in the case where rotating speed is 170r/min, stratification isolates upper layer Glycerine, lower layer are biodiesel crude product；
S5. distilation：Biodiesel crude product is added into destilling tower, extra methanol is distilled off at 88 DEG C, you can To biodiesel.
Embodiment 3
The preparation of Isochrysis galbana culture medium：Glucose 30mg/L, NaNO31.6mg/L、KH2PO41.3mg/L、 Na2SiO30.5mg/L, chitosan 1.0mg/L, biogas slurry 7mg/L, f2 vitamin 2mL and seawater 1L；
A method of biodiesel being produced using microalgae, is included the following steps：
S1. Isochrysis galbana culture：Using Isochrysis galbana as raw material, then with the inoculum density inoculation of 1,000,000 cell/mL To culture medium, with red blue dual-colored LED light filling light irradiation 22h/ days, wherein feux rouges and blue light proportioning were 2:1, control intensity of illumination exists 4500LX, cultivation temperature are controlled at 28 DEG C, are cultivated 11 days, the density of Isochrysis galbana reach concentration reach 90,000,000 cells/ ML collects Isochrysis galbana cell；
S2. grease extracts：After step S1 is collected the drying of Isochrysis galbana cell concentration, high speed ball mill is added in rotating speed To be crushed 10min under 1000r/min, Isochrysis galbana powder is obtained, it is 1 to be added in Isochrysis galbana powder with its mass ratio:9 stone Oily ether, mixing stand 6h, and upper liquid is grease extracting solution, then extracting solution is distilled at 78 DEG C, you can obtains microalgae grease；
S3. ester exchange reaction：By microalgae grease, methanol and zeolite molecular sieve catalyst according to mass ratio be 1:6:0.01 Ratio is added in reactor, in the case where temperature is 60 DEG C, carries out esterification 95min, obtains esterification products；
S4. standing separation；Esterification products are centrifuged into 18min in the case where rotating speed is 150r/min, stratification isolates upper layer Glycerine, lower layer are biodiesel crude product；
S5. distilation：Biodiesel crude product is added into destilling tower, extra methanol is distilled off at 90 DEG C, you can To biodiesel.
Weight method is extracted using grease, fat content measurement is carried out to the collected Isochrysis galbana of above example, as a result As shown in table 1.Wherein grease total content=(microalgae grease/Isochrysis galbana powder) × 100%.
1. Isochrysis galbana fat content of table
Grease total content (%)
Embodiment 1 28
Embodiment 2 32
Embodiment 3 31
Biodiesel prepared by above example is according to GB/T20828-2007 (diesel fuel blending biodiesel) The performance of standard detection product, testing result are as shown in table 2.
The properties of product of the biodiesel of 2. the present embodiment of table
Density (g/cm3) Viscosity (40 DEG C of mm2/s) Acid value (mgKOH/g) Flash-point (DEG C) Cetane number
Embodiment 1 0.86 6.12 0.76 151 63
Embodiment 2 0.82 5.12 0.66 144 51
Embodiment 3 0.83 5.02 0.53 163 55
Standard value 0.82-0.9 1.9-6.0 ≤0.8 ≥130℃ ＞ 49
As can be seen from the above table, the indices for the biodiesel that prepared by the present invention are above diesel fuel blending life The standard of object diesel oil, good market prospect.
It, cannot the above content is specific/preferred embodiment further description made for the present invention is combined Assert that the specific implementation of the present invention is confined to these explanations.General technical staff of the technical field of the invention is come It says, without departing from the inventive concept of the premise, some replacements or modification can also be made to the embodiment that these have been described, And these are substituted or variant all shall be regarded as belonging to protection scope of the present invention.

Claims (2)

1. a kind of method producing biodiesel using microalgae, which is characterized in that include the following steps：
S1. Isochrysis galbana culture：Using Isochrysis galbana as raw material, then with the inoculum density inoculation of ten thousand cell/mL of 100-200 To culture medium, with red blue dual-colored LED light filling light irradiation 18-22h/ days, intensity of illumination is controlled in 3500-4500LX, cultivation temperature Control is cultivated 10-12 days at 25-28 DEG C, and the density of Isochrysis galbana reaches concentration and reaches 90,000,000 cell/mL, collects ball Isochrysis galbana cell；The culture medium is composed of the following components：Glucose 25-30mg/L, NaNO3 1.6-2.0mg/L、 KH2PO41.0-1.3mg/L、Na2SiO30.3-0.5mg/L, chitosan 0.8-1.0mg/L, biogas slurry 5-7mg/L, f2 vitamin 2- 3mL and seawater 1L；
S2. grease extracts：After step S1 is collected the drying of Isochrysis galbana cell concentration, high speed ball mill is added and is crushed, obtains ball Isochrysis galbana powder, it is 1 to be added in Isochrysis galbana powder with its mass ratio:The petroleum ether of 7-9, mixing stand 2-6h, upper liquid As grease extracting solution, then extracting solution is distilled at 75-80 DEG C, you can obtain microalgae grease；
S3. ester exchange reaction：By microalgae grease, methanol and zeolite molecular sieve catalyst according to mass ratio be 1:3-6:0.01- 0.03 ratio is added in reactor, in the case where temperature is 50-60 DEG C, carries out esterification 90-100min, obtains esterification products；
S4. standing separation；Esterification products are centrifuged into 15-18min in the case where rotating speed is 150-200r/min, stratification is isolated Upper layer glycerine, lower layer are biodiesel crude product；
S5. distilation：Biodiesel crude product is added into destilling tower, extra methanol is distilled off at 85-90 DEG C, you can obtain Biodiesel；
Feux rouges and blue light proportioning in the red blue dual-colored LED light compensating lamp are 1-2:1.
2. a kind of method producing biodiesel using microalgae according to claim 1, it is characterised in that：The high speed Ball milling crusher machine is that control rotating speed is crushed 10-15min at 800-1000r/min.
CN201610766810.7A 2016-08-30 2016-08-30 A method of producing biodiesel using microalgae Expired - Fee Related CN106367128B (en)

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