CN106281483A - A kind of method preparing biodiesel for raw material with algae - Google Patents
A kind of method preparing biodiesel for raw material with algae Download PDFInfo
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- CN106281483A CN106281483A CN201610764763.2A CN201610764763A CN106281483A CN 106281483 A CN106281483 A CN 106281483A CN 201610764763 A CN201610764763 A CN 201610764763A CN 106281483 A CN106281483 A CN 106281483A
- Authority
- CN
- China
- Prior art keywords
- biodiesel
- raw material
- pavlova viridis
- algae
- pavlova
- Prior art date
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- Granted
Links
- 239000003225 biodiesel Substances 0.000 title claims abstract description 62
- 239000002994 raw material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 22
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 15
- 241000386616 Pavlova viridis Species 0.000 claims abstract description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000032050 esterification Effects 0.000 claims abstract description 19
- 238000005886 esterification reaction Methods 0.000 claims abstract description 19
- 239000004519 grease Substances 0.000 claims abstract description 15
- 239000001963 growth medium Substances 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- 235000014593 oils and fats Nutrition 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011782 vitamin Substances 0.000 claims description 6
- 229940088594 vitamin Drugs 0.000 claims description 6
- 229930003231 vitamin Natural products 0.000 claims description 6
- 235000013343 vitamin Nutrition 0.000 claims description 6
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000007836 KH2PO4 Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000002054 inoculum Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 6
- 239000008158 vegetable oil Substances 0.000 abstract description 6
- 102000004895 Lipoproteins Human genes 0.000 abstract description 4
- 108090001030 Lipoproteins Proteins 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- 230000029553 photosynthesis Effects 0.000 abstract description 2
- 238000010672 photosynthesis Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000003044 adaptive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000000243 photosynthetic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000011691 vitamin B1 Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 235000005637 Brassica campestris Nutrition 0.000 description 1
- 241001301148 Brassica rapa subsp. oleifera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 description 1
- 244000248162 Xanthoceras sorbifolium Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
Classifications
-
- 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
- C11B1/025—Pretreatment by enzymes or microorganisms, living or dead
-
- 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
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- 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
-
- 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
Landscapes
- 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)
- Microbiology (AREA)
- General Chemical & Material Sciences (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 method preparing biodiesel for raw material with algae, comprise the following steps: pavlova viridis is seeded to culture medium, irradiate 10 16h/ days with red blue dual-colored LED light compensating lamp, cultivate 8 10 days at 25 27 DEG C, pavlova viridis cell can be collected；The pavlova viridis cell collected adds high speed ball mill and crushes, again with organic solvent extraction, obtain microalgae grease, again microalgae grease, methanol and zeolite molecular sieve catalyst are added in reactor according to the ratio that weight ratio is 1:5 7:0.03 0.05 and carry out esterification, obtain esterification products, esterification products through separating, purifying, i.e. can get biodiesel again.The inventive method, with pavlova viridis with short production cycle, widely distributed, that photosynthesis is strong, fat content is high as raw material, solves the problem that the Vegetable oil lipoprotein raw material in biodiesel exploitation exists.The most also have that preparation technology is simple, catalytic efficiency is high, grease extraction efficiency is high, product yield advantages of higher, lay a good foundation for biodiesel industrialization, scale.
Description
Technical field
The invention belongs to biomass energy technology field, a kind of with algae for the biological bavin of raw material preparation specifically
The method of oil.
Background technology
Along with the exhaustion day by day of fossil fuel, oil price persistently sharp rises, and seeking regenerative resource has become solution
Human survival and the needs of holding World Economics sustainable development, the biodiesel as novel alternative energy source is sent out in countries in the world
Exhibition is rapidly.Biodiesel refers to oil crop such as Semen sojae atricolor, Brassica campestris L, cotton, Petiolus Trachycarpi etc., the water such as Wild oil plant and engineering microalgae
Raw vegetable oil fat and animal oil, food garbage oil etc. for raw oil by replacing that ester exchange or thermochemical processes are made
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；Preferably wettability, makes injection pump, engine cylinder-body and connecting rod
Abrasion reduce, increase the service life；In biodiesel, sulfur content is low, and the discharge of sulfur dioxide and sulfide is low, reduces environment
Pollute；Biodiesel flash-point is high, is not belonging to dangerous materials, all has superiority in transport, storage, use etc..
At present, China's industrialized production biodiesel is mainly with Oleum Brassicae campestris, Oleum Gossypii semen, Chinese tallow, shinyleaf yellowhorn oil, Oleum Camelliae
It is raw material with waste oil etc..But the limits throughput of these raw materials, the biodiesel of production can only meet current vehicle demand for fuel
The 0.3% of amount.And a large amount of Vegetable oil lipoprotein produces biodiesel, anxiety and the crops price of land resource will certainly be caused
Rise, especially in the case of 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 has been attracted with the advantage of its uniqueness.Microalgae, as a kind of important biodiesel raw material, is planted with oil plant
Thing is compared, and has that distribution is wide, Biomass high, photosynthetic efficiency is high, adaptive capacity to environment is strong, growth cycle is short, fat content is high, becomes
The significant advantages such as this lowest and environmental friendliness.
In recent years, research prepared by relevant biodiesel is concentrated mainly on the aspect such as woody oleiferous plants and disposed waste oil, from
Microalgae extracts oils and fats little for the research report preparing biodiesel.Wherein, biodiesel one is prepared with microalgae for raw material
As comprise the following steps that: Strain selection, pilot scale culture, extraction oils and fats, esterification prepare biodiesel coarse product, warp
Cross refine and i.e. can get biodiesel.The microalgae kind selecting fat content high is to prepare the key of biodiesel, cultivates simultaneously
Base and envirment factor also have important impact to the fat content of microalgae.Therefore, how to improve the nutritional labeling of culture medium and change
The changing environment factor is one of approach improving algae oils and fats productivity.Although improving microalgae fat content can be that biodiesel is laid well
Basis, but the production technology of biodiesel is most important to its yield effect.The production technology of existing biodiesel is general
There is problems in that catalytic efficiency is low, yield of biodiesel is low, response time length, etching apparatus, complex process, energy consumption are relatively big,
Relatively costly deficiency such as grade.
Pavlova viridis (Pavlova viridis), belongs to Ba Fuke, and bar husband belongs to.Pavlova viridis is due to speed of production
Hurry up, fat content is up to 30%, mainly contains C in lubricant component18、C16The fatty glyceride of carbochain, carries with from vegetable oil
The biodiesel fuel component taken is close, is the class bioenergy material with potentiality to be exploited.
Summary of the invention
The present invention is directed to the problem that Vegetable oil lipoprotein limits throughput and existing biodiesel oil preparing process exist, it is provided that a kind of with
Algae is the method that biodiesel prepared by raw material.The inventive method has that raw material sources are extensive, catalytic efficiency is high, power consumption
The advantage such as low, biodiesel production rate is high, preparation technology is simple, lays a good foundation for biodiesel industrialization, scale,
Can effective alleviating energy crisis problem.
In order to realize object above, the present invention is to be achieved through the following technical solutions:
A kind of method preparing biodiesel for raw material with algae, comprises the following steps:
S1. pavlova viridis is cultivated: with pavlova viridis as raw material, then the inoculum density with ten thousand cell/mL of 250-350
It is seeded to culture medium, irradiates 10-16h/ days with red blue dual-colored LED light compensating lamp, control intensity of illumination in 4000-5000LX, cultivation
Temperature controls at 25-27 DEG C, cultivates 8-10 days, and the density of pavlova viridis reaches concentration and reaches 80,000,000 cell/mL, collects
Pavlova viridis cell；Described 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 sea water 1L；
S2. oils and fats extracts: step S1 is collected pavlova viridis cell concentration after drying, adds high speed ball mill and crushes,
Obtaining pavlova viridis powder, adding in pavlova viridis powder with its weight ratio is the petroleum ether of 1:9-11, and mixing stands 2-6h, on
Layer liquid is oils and fats extracting solution, then by extracting solution 80-85 DEG C of distillation, i.e. can get microalgae grease；
S3. ester exchange reaction: be 1:5-7 according to weight ratio by microalgae grease, methanol and zeolite molecular sieve catalyst:
The ratio of 0.03-0.05 adds in reactor, at temperature is 50-60 DEG C, carries out esterification 90-120min, is esterified
Product；
S4. standing separation；By esterification products centrifugal 30-35min, stratification under rotating speed is 200-250r/min, divide
Separating out upper strata glycerol, lower floor is biodiesel crude product；
S5. distilation: biodiesel crude product is added to distillation column, is distilled off unnecessary methanol at 70-75 DEG C,
Obtain biodiesel.
Further, the compound method of the f2 vitamin described in above step S1 is as follows: 0.5mg vitamin B12、0.5mg
Biotin, 100mL vitamin B1 and pure water 1000mL.
Further, the HONGGUANG in above-described red blue dual-colored LED light compensating lamp is 1-2:1 with blue light proportioning, preferably joins
Ratio is 2:1.
Further, the high speed ball mill described in above step S2 crushes is to control rotating speed to break under 800-1000r/min
Broken 10-15min..
Compared with prior art, the beneficial effect that the present invention obtains:
1, the present invention prepares biodiesel with pavlova viridis for raw material, can effectively alleviate current energy crisis and environment
Pollution problem, pavlova viridis has that distribution is wide, Biomass high, photosynthetic efficiency is high, adaptive capacity to environment is strong, growth cycle is short,
The significant advantages such as fat content height, low cost and environmental friendliness, it is possible to solve the Vegetable oil lipoprotein raw material in biodiesel exploitation not
The problems such as foot, high cost.
2, the present invention adds in the medium chitosan and biogas slurry, containing nutrition such as substantial amounts of trace element, Organic substances
Composition, can accelerate microalgae speed of production and improve the oils and fats productivity of microalgae.
3, the inventive method is by using red blue dual-colored LED light compensating lamp to change illumination condition, is possible not only to improve green bar
The photosynthesis of husband algae, accelerates pavlova viridis and produces and improve yield, and the oils and fats that simultaneously can also improve pavlova viridis produces
Rate, compared with conventional electric filament lamp, fluorescent lamp or monochromatic LED lamp, the oils and fats productivity of pavlova viridis improves about 5%.
4, the present invention uses high speed ball mill crushing microalgae cells, has low cost, efficiency height, environmentally safe, consumption
The advantages such as energy is low, are one processing methods cost-effectively.
5, the inventive method uses zeolite molecular sieve as catalyst, possesses that reaction interface is big, surface area big, resistance to mass tranfer
Little, reaction condition is gentle, active height, pollution-free, the not feature such as etching apparatus, improve catalytic efficiency, shorten esterification
Time, catalytic effect is notable, improves the yield of biodiesel.
6, the inventive method have that preparation technology is simple, catalytic efficiency is high, grease extraction efficiency is high, biodiesel production rate is high,
Product purity is high, raw material sources extensively, the advantage such as low cost, power consumption be low, there is good society, ecology and economic benefit, for
Microalgae biodiesel industrialization, scale are laid a good foundation.
Detailed description of the invention
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 sea water 1L；
A kind of method preparing biodiesel for raw material with algae, comprises the following steps:
S1. pavlova viridis is cultivated: with pavlova viridis as raw material, then connect with the inoculum density of 3,500,000 cell/mL
Planting to culture medium, irradiate 10h/ days with red blue dual-colored LED light compensating lamp, wherein HONGGUANG and blue light proportioning are 1:1, control intensity of illumination
At 5000LX, cultivation temperature controls at 25 DEG C, cultivates 10 days, and the density of pavlova viridis reaches concentration and reaches 80,000,000 carefully
Born of the same parents/mL, collects pavlova viridis cell；
S2. oils and fats extracts: step S1 is collected pavlova viridis cell concentration after drying, adds high speed ball mill at rotating speed
For 15min broken under 800r/min, obtaining pavlova viridis powder, adding in pavlova viridis powder with its weight ratio is the stone of 1:9
Oil ether, mixing stands 2h, and upper liquid is oils and fats extracting solution, then by extracting solution 85 DEG C of distillations, i.e. can get microalgae grease；
S3. ester exchange reaction: be 1:5:0.05's according to weight ratio by microalgae grease, methanol and zeolite molecular sieve catalyst
Ratio adds in reactor, at temperature is 50 DEG C, carries out esterification 90min, obtains esterification products；
S4. standing separation；By esterification products centrifugal 30min, stratification under rotating speed is 250r/min, isolate upper strata
Glycerol, lower floor is biodiesel crude product；
S5. distilation: biodiesel crude product is added to distillation column, is distilled off unnecessary methanol at 70 DEG C,
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 sea water 1L；
A kind of method preparing biodiesel for raw material with algae, comprises the following steps:
S1. pavlova viridis is cultivated: with pavlova viridis as raw material, then inoculates with the inoculum density of 3,000,000 cell/mL
To culture medium, irradiating 16h/ days with red blue dual-colored LED light compensating lamp, wherein HONGGUANG and blue light proportioning are 2:1, control intensity of illumination and exist
4500LX, cultivation temperature controls at 26 DEG C, cultivates 8 days, the density of pavlova viridis reach concentration reach 80,000,000 cells/
ML, collects pavlova viridis cell；
S2. oils and fats extracts: step S1 is collected pavlova viridis cell concentration after drying, adds high speed ball mill at rotating speed
For 13min broken under 900r/min, obtaining pavlova viridis powder, adding in pavlova viridis powder with its weight ratio is the stone of 1:10
Oil ether, mixing stands 4h, and upper liquid is oils and fats extracting solution, then by extracting solution 82 DEG C of distillations, i.e. can get microalgae grease；
S3. ester exchange reaction: be 1:6:0.04's according to weight ratio by microalgae grease, methanol and zeolite molecular sieve catalyst
Ratio adds in reactor, at temperature is 55 DEG C, carries out esterification 110min, obtains esterification products；
S4. standing separation；By esterification products centrifugal 30min, stratification under rotating speed is 220r/min, isolate upper strata
Glycerol, lower floor is biodiesel crude product；
S5. distilation: biodiesel crude product is added to distillation column, is distilled off unnecessary methanol at 72 DEG C,
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 sea water 1L；
A kind of method preparing biodiesel for raw material with algae, comprises the following steps:
S1. pavlova viridis is cultivated: with pavlova viridis as raw material, then inoculates with the inoculum density of 2,500,000 cell/mL
To culture medium, irradiating 12h/ days with red blue dual-colored LED light compensating lamp, wherein HONGGUANG and blue light proportioning are 1:1, control intensity of illumination and exist
4000LX, cultivation temperature controls at 27 DEG C, cultivates 10 days, the density of pavlova viridis reach concentration reach 80,000,000 cells/
ML, collects pavlova viridis cell；
S2. oils and fats extracts: step S1 is collected pavlova viridis cell concentration after drying, adds high speed ball mill at rotating speed
For 10min broken under 1000r/min, obtaining pavlova viridis powder, adding in pavlova viridis powder with its weight ratio is 1:11's
Petroleum ether, mixing stands 6h, and upper liquid is oils and fats extracting solution, then by extracting solution 80 DEG C of distillations, i.e. can get microalgae grease；
S3. ester exchange reaction: be 1:7:0.03's according to weight ratio by microalgae grease, methanol and zeolite molecular sieve catalyst
Ratio adds in reactor, at temperature is 60 DEG C, carries out esterification 120min, obtains esterification products；
S4. standing separation；By esterification products centrifugal 35min, stratification under rotating speed is 200r/min, isolate upper strata
Glycerol, lower floor is biodiesel crude product；
S5. distilation: biodiesel crude product is added to distillation column, is distilled off unnecessary methanol at 75 DEG C,
To biodiesel.
The pavlova viridis utilizing oils and fats extraction weight method to collect above example carries out fat content mensuration, result
As shown in table 1.Wherein oils and fats total content=(microalgae grease/pavlova viridis powder) × 100%.
Table 1. pavlova viridis fat content
| Oils and fats 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 is as shown in table 2.
The properties of product of the biodiesel of table 2. the present embodiment
| Density (g/cm3) | Viscosity (40 DEG C of mm2/s) | Acid number (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 of biodiesel prepared by the present invention is above diesel fuel blending life
The standard of thing diesel oil, good market prospects.
Above content is to combine concrete/the most made for the present invention further description, it is impossible to
Assert the present invention be embodied as be confined to these explanations.General technical staff of the technical field of the invention is come
Saying, without departing from the inventive concept of the premise, these embodiments having described that can also be made some replacements or modification by it,
And these substitute or variant all should be considered as belonging to protection scope of the present invention.
Claims (3)
1. the method preparing biodiesel for raw material with algae, it is characterised in that comprise the following steps:
S1. pavlova viridis is cultivated: with pavlova viridis as raw material, then inoculates with the inoculum density of ten thousand cell/mL of 250-350
To culture medium, irradiate 10-16h/ days with red blue dual-colored LED light compensating lamp, control intensity of illumination in 4000-5000LX, cultivation temperature
Controlling at 25-27 DEG C, cultivate 8-10 days, the density of pavlova viridis reaches concentration and reaches 80,000,000 cell/mL, collects green
Bar husband's frustule；Described 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 sea water 1L；
S2. oils and fats extracts: step S1 is collected pavlova viridis cell concentration after drying, adds high speed ball mill and crushes, obtains green
Se Bafu algae powder, adding in pavlova viridis powder with its weight ratio is the petroleum ether of 1:9-11, and mixing stands 2-6h, upper liquid
It is oils and fats extracting solution, then by extracting solution 80-85 DEG C of distillation, i.e. can get microalgae grease；
S3. ester exchange reaction: be 1:5-7:0.03-according to weight ratio by microalgae grease, methanol and zeolite molecular sieve catalyst
The ratio of 0.05 adds in reactor, at temperature is 50-60 DEG C, carries out esterification 90-120min, obtains esterification products；
S4. standing separation；By esterification products centrifugal 30-35min, stratification under rotating speed is 200-250r/min, isolate
Upper strata glycerol, lower floor is biodiesel crude product；
S5. distilation: biodiesel crude product is added to distillation column, is distilled off unnecessary methanol at 70-75 DEG C, the most available
Biodiesel.
A kind of method preparing biodiesel for raw material with algae the most according to claim 1, it is characterised in that: institute
HONGGUANG in the red blue dual-colored LED light compensating lamp stated is 1-2:1 with blue light proportioning.
A kind of method preparing biodiesel for raw material with algae the most according to claim 1, it is characterised in that: institute
The high speed ball mill stated is broken is to control rotating speed broken 10-15min under 800-1000r/min.
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