CN106281483B - A method of preparing biodiesel by raw material of algae - Google Patents

A method of preparing biodiesel by raw material of algae Download PDF

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CN106281483B
CN106281483B CN201610764763.2A CN201610764763A CN106281483B CN 106281483 B CN106281483 B CN 106281483B CN 201610764763 A CN201610764763 A CN 201610764763A CN 106281483 B CN106281483 B CN 106281483B
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biodiesel
pavlova viridis
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grease
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CN106281483A (en
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黄健峻
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Duan Tanlong
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Nanning Overseas Chinese Investment Zone Sun Trading Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, 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
    • C11B1/00Production of fats or fatty oils from raw materials
    • C11B1/02Pretreatment
    • C11B1/025Pretreatment by enzymes or microorganisms, living or dead
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, 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
    • C11B3/00Refining fats or fatty oils
    • C11B3/12Refining fats or fatty oils by distillation
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10Ester interchange
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention discloses a kind of methods preparing biodiesel as raw material using algae, include the following steps:Pavlova viridis is seeded to culture medium, with red blue dual-colored LED light filling light irradiation 10 16h/ days, is cultivated 8 10 days at 25 27 DEG C, you can collection pavlova viridis cell;It is broken that the pavlova viridis 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 weight ratio is 1:5‑7:0.03 0.05 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 pavlova viridis 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 preparing biodiesel by raw material of algae
Technical field
The invention belongs to biomass energy technology fields, specifically a kind of to prepare biological bavin by raw material of algae The method of oil.
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.
Pavlova viridis (Pavlova viridis), belongs to Ba Fuke, and bar husband belongs to.Pavlova viridis is due to speed of production Soon, fat content is up to 30%, and C is mainly contained in lubricant component18、C16The fatty glyceride of carbochain, carries with from vegetable oil The biodiesel fuel component taken is close, is a kind of bioenergy material with potentiality to be exploited.
Invention content
The present invention for vegetable fat limits throughput and existing biodiesel oil preparing process there are the problem of, provide it is a kind of with Algae is the method that raw material prepares biodiesel.The method of the present invention has extensive raw material sources, high catalytic efficiency, energy consumption Low, the advantages that biodiesel production rate is high, preparation process is simple, lays a good foundation for biodiesel industrialization, scale, Problem of energy crisis can be effectively relieved.
In order to achieve the goal above, the present invention is achieved through the following technical solutions:
A method of biodiesel being prepared by raw material of algae, is included the following steps:
S1. pavlova viridis culture:Using pavlova viridis as raw material, then with the inoculum density of ten thousand cell/mL of 250-350 It is seeded to culture medium, with red blue dual-colored LED light filling light irradiation 10-16h/ days, control intensity of illumination was cultivated in 4000-5000LX Temperature is controlled at 25-27 DEG C, is cultivated 8-10 days, and the density of pavlova viridis reaches concentration and reaches 80,000,000 cell/mL, is collected Pavlova viridis cell;The culture medium is composed of the following components:Glucose 25-30mg/L, NaNO31.6-2.0mg/L、 KH2PO41.2-1.5mg/L、Na2SiO30.8-1.0mg/L, chitosan 1.0-1.4mg/L, biogas slurry 7-10mg/L, f2 vitamin 3- 4mL and seawater 1L;
S2. grease extracts:After step S1 is collected the drying of pavlova viridis cell concentration, high speed ball mill is added and is crushed, Pavlova viridis powder is obtained, it is 1 to be added in pavlova viridis powder with its weight ratio:The petroleum ether of 9-11, mixing stand 2-6h, on Layer liquid is grease extracting solution, then extracting solution is distilled at 80-85 DEG C, you can obtains microalgae grease;
S3. ester exchange reaction:By microalgae grease, methanol and zeolite molecular sieve catalyst according to weight ratio be 1:5-7: The ratio of 0.03-0.05 is added in reactor, in the case where temperature is 50-60 DEG C, carries out esterification 90-120min, is esterified Product;
S4. standing separation;Esterification products are centrifuged into 30-35min in the case where rotating speed is 200-250r/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 70-75 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 pavlova viridis, and current energy crisis and environment can be effectively relieved Pollution problem, pavlova viridis 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 green bar The photosynthesis of husband algae accelerates pavlova viridis production and improves yield, while can also improve the grease production of pavlova viridis Rate, compared with common incandescent lamp, fluorescent lamp or monochromatic LED lamp, the lipid-producing of pavlova viridis 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 pavlova viridis culture medium:Glucose 25mg/L, NaNO32.0mg/L、KH2PO41.2mg/L、 Na2SiO30.8mg/L, chitosan 1.0mg/L, biogas slurry 7mg/L, f2 vitamin 3mL and seawater 1L;
A method of biodiesel being prepared by raw material of algae, is included the following steps:
S1. pavlova viridis culture:Using pavlova viridis as raw material, then connect with the inoculum density of 3,500,000 cell/mL Kind to culture medium, with red blue dual-colored LED light filling light irradiation 10h/ days, wherein feux rouges and blue light proportioning were 1:1, control intensity of illumination In 5000LX, cultivation temperature is controlled at 25 DEG C, is cultivated 10 days, and the density of pavlova viridis reaches concentration and reaches 80,000,000 thin Born of the same parents/mL collect pavlova viridis cell;
S2. grease extracts:After step S1 is collected the drying of pavlova viridis cell concentration, high speed ball mill is added in rotating speed To be crushed 15min under 800r/min, pavlova viridis powder is obtained, it is 1 to be added in pavlova viridis powder with its weight ratio:9 stone Oily ether, mixing stand 2h, and upper liquid is grease extracting solution, then extracting solution is distilled at 85 DEG C, you can obtains microalgae grease;
S3. ester exchange reaction:By microalgae grease, methanol and zeolite molecular sieve catalyst according to weight ratio be 1:5:0.05 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 30min in the case where rotating speed is 250r/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 70 DEG C, you can To biodiesel.
Embodiment 2
The preparation of pavlova viridis culture medium:Glucose 28mg/L, NaNO31.8mg/L、KH2PO41.4mg/L、 Na2SiO30.9mg/L, chitosan 1.2mg/L, biogas slurry 10mg/L, f2 vitamin 4mL and seawater 1L;
A method of biodiesel being prepared by raw material of algae, is included the following steps:
S1. pavlova viridis culture:Using pavlova viridis as raw material, then with the inoculum density inoculation of 3,000,000 cell/mL To culture medium, with red blue dual-colored LED light filling light irradiation 16h/ days, wherein feux rouges and blue light proportioning were 2:1, control intensity of illumination exists 4500LX, cultivation temperature are controlled at 26 DEG C, are cultivated 8 days, the density of pavlova viridis reach concentration reach 80,000,000 cells/ ML collects pavlova viridis cell;
S2. grease extracts:After step S1 is collected the drying of pavlova viridis cell concentration, high speed ball mill is added in rotating speed To be crushed 13min under 900r/min, pavlova viridis powder is obtained, it is 1 to be added in pavlova viridis powder with its weight ratio:10 stone Oily ether, mixing stand 4h, and upper liquid is grease extracting solution, then extracting solution is distilled at 82 DEG C, you can obtains microalgae grease;
S3. ester exchange reaction:By microalgae grease, methanol and zeolite molecular sieve catalyst according to weight ratio be 1:6:0.04 Ratio is added in reactor, in the case where temperature is 55 DEG C, carries out esterification 110min, obtains esterification products;
S4. standing separation;Esterification products are centrifuged into 30min in the case where rotating speed is 220r/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 72 DEG C, you can To biodiesel.
Embodiment 3
The preparation of pavlova viridis culture medium:Glucose 30mg/L, NaNO31.6mg/L、KH2PO41.5mg/L、 Na2SiO31.0mg/L, chitosan 1.4mg/L, biogas slurry 9mg/L, f2 vitamin 3mL and seawater 1L;
A method of biodiesel being prepared by raw material of algae, is included the following steps:
S1. pavlova viridis culture:Using pavlova viridis as raw material, then with the inoculum density inoculation of 2,500,000 cell/mL To culture medium, with red blue dual-colored LED light filling light irradiation 12h/ days, wherein feux rouges and blue light proportioning were 1:1, control intensity of illumination exists 4000LX, cultivation temperature are controlled at 27 DEG C, are cultivated 10 days, the density of pavlova viridis reach concentration reach 80,000,000 cells/ ML collects pavlova viridis cell;
S2. grease extracts:After step S1 is collected the drying of pavlova viridis cell concentration, high speed ball mill is added in rotating speed To be crushed 10min under 1000r/min, pavlova viridis powder is obtained, it is 1 to be added in pavlova viridis powder with its weight ratio:11 Petroleum ether, mixing stand 6h, 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 weight ratio be 1:7:0.03 Ratio is added in reactor, in the case where temperature is 60 DEG C, carries out esterification 120min, obtains esterification products;
S4. standing separation;Esterification products are centrifuged into 35min 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 75 DEG C, you can To biodiesel.
Weight method is extracted using grease, fat content measurement is carried out to the collected pavlova viridis of above example, as a result As shown in table 1.Wherein grease total content=(microalgae grease/pavlova viridis powder) × 100%.
1. pavlova viridis fat content of table
Grease total content (%)
Embodiment 1 34
Embodiment 2 36
Embodiment 3 33
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 5.46 0.52 151 63
Embodiment 2 0.87 4.98 0.66 179 77
Embodiment 3 0.83 5.13 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 (1)

1. a kind of method preparing biodiesel as raw material using algae, which is characterized in that include the following steps:
S1. pavlova viridis culture:Using pavlova viridis as raw material, then with the inoculum density inoculation of ten thousand cell/mL of 250-350 To culture medium, with red blue dual-colored LED light filling light irradiation 10-16h/ days, intensity of illumination is controlled in 4000-5000LX, cultivation temperature Control is cultivated 8-10 days at 25-27 DEG C, and the density of pavlova viridis reaches concentration and reaches 80,000,000 cell/mL, collects green Se Bafu frustules;The culture medium is composed of the following components:Glucose 25-30mg/L, NaNO3 1.6-2.0mg/L、 KH2PO41.2-1.5mg/L、Na2SiO30.8-1.0mg/L, chitosan 1.0-1.4mg/L, biogas slurry 7-10mg/L, f2 vitamin 3- 4mL and seawater 1L;
S2. grease extracts:After step S1 is collected the drying of pavlova viridis cell concentration, high speed ball mill is added and is crushed, obtains green Se Bafu algae powder, it is 1 to be added in pavlova viridis powder with its weight ratio:The petroleum ether of 9-11, mixing stand 2-6h, upper liquid As grease extracting solution, then extracting solution is distilled at 80-85 DEG C, you can obtain microalgae grease;
S3. ester exchange reaction:By microalgae grease, methanol and zeolite molecular sieve catalyst according to weight ratio be 1:5-7:0.03- 0.05 ratio is added in reactor, in the case where temperature is 50-60 DEG C, carries out esterification 90-120min, obtains esterification products;
S4. standing separation;Esterification products are centrifuged into 30-35min in the case where rotating speed is 200-250r/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 70-75 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;
The broken high speed ball mill is that control rotating speed is crushed 10-15min at 800-1000r/min.
CN201610764763.2A 2016-08-30 2016-08-30 A method of preparing biodiesel by raw material of algae Active CN106281483B (en)

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