CN103242968A - Method for preparing biodiesel by virtue of two-step catalytic conversion of microalgae with high acid value - Google Patents
Method for preparing biodiesel by virtue of two-step catalytic conversion of microalgae with high acid value Download PDFInfo
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- CN103242968A CN103242968A CN2013101912931A CN201310191293A CN103242968A CN 103242968 A CN103242968 A CN 103242968A CN 2013101912931 A CN2013101912931 A CN 2013101912931A CN 201310191293 A CN201310191293 A CN 201310191293A CN 103242968 A CN103242968 A CN 103242968A
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- 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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Abstract
The invention relates to a method for preparing biodiesel by virtue of two-step catalytic conversion of microalgae with high acid value. The method comprises the following steps of: adding a certain amount of solid acid catalyst and methyl alcohol into the high acid value microalgae raw material, heating to certain temperature, carrying out esterification reaction for 40-60 minutes, then filtering the solid acid, continuously adding a basic catalyst (KOH-potassium hydroxide) into the reaction system for catalysis esterification reaction of the second stage, after reaction, absorbing supernatant liquid through normal hexane, then removing the normal hexane, and obtaining the biodiesel. The method can be used for both improving the yield of the biodiesel and shortening the reaction time, and is beneficial to promotion and application.
Description
One, technical field
The invention belongs to biotechnology and energy field, particularly the in-situ two-step catalyzed conversion of the little algae of a kind of high acid value prepares method of bio-diesel oil.
Two, background technology
Along with rapid economy development, the continuous deterioration of whole world fossil shortage of energy sources and environment, pressing for newborn resource replaces, little algae is fast because of its growth velocity, recyclability is strong, photosynthetic efficiency is high, the doubling time is short, and the productive rate of unit surface exceeds tens of times of higher plants, does not occupy cultivated land, can utilize seabeach, saltings and organic waste water to cultivate, fat content height, absorption CO
2For carbon source, do not strive grain and do not strive ground with grain with the people, advantages such as fat content height form focus and hot issue into people's research.The recovery energy of little algae be expected to become " back petroleum times " crack energy dilemma one JINYAOSHI.
At present, little algae to prepare the complicated cost height of production process of biofuel be one of main bottleneck of its energy of restriction.Traditional biodiesel oil preparing process at first extracts grease in little algae, then the grease that extracts effect and the alcohol by catalyzer is carried out alcoholysis or esterification.Organic solvents such as methyl alcohol, chloroform, normal hexane are mainly adopted in the extraction of grease in little algae, grease after the extraction carries out transesterification, this method causes problems such as reactions steps is many, program is complicated, cost height, is the one of the main reasons that it can not large-scale industrial production.
In recent years, little algae situ catalytic conversion method prepares biofuel and has obtained good application, so-called situ catalytic conversion method, and namely without the extraction link of grease, the grease under the effect of catalyzer in little algae directly reacts with alcohol, generates biofuel.The biodiesel oil preparing process that the situ catalytic conversion method is more traditional has reduced middle-chain, has reduced production cost.Because the catalytic efficiency of basic catalyst is the hundred times of an acidic catalyst even thousands of times, therefore in suitability for industrialized production, generally adopt basic catalyst, if but free fatty acid content is higher, basic catalyst at first can be followed free fatty acids generation saponification reaction, not only reduced the productive rate of biofuel, and the saponification resultant that generates is blended in the biofuel, causes subsequent separation process complexity and the cost height of product.The little algae powder of bibliographical information is arranged after storage after a while, part grease wherein is converted into free fatty acids under the effect of enzyme, causes the content of free lipid acid in little algae up to more than 70%; At the little algae of high acid value, it is catalyzer that people such as Man Kee Lam adopt sulfuric acid, but because an acidic catalyst catalytic efficiency is low, and entire reaction course reaches 6 hours, and methanol usage is big, molar ratio of methanol to oil reaches 180:1; It is long that this reacts not only the time, and methanol usage is big.
Three, summary of the invention
At above problem, the purpose of this invention is to provide the little algae of a kind of peracidity and prepare method of bio-diesel oil, the present invention adopts the pre-esterification of solid acid-base catalysis to transform, at first under the effect of solid acid catalyst, make free fatty acids be converted into biofuel, and then under the effect of basic catalyst, neutral ester is converted into biofuel.
The technical scheme that the present invention takes is:
The method of the in-situ two-step catalysis for preparing biodiesel oil of the little algae of a kind of high acid value comprises the steps:
(1) pre-esterification reactor: the little algae powder of 0.3～3g is joined in the reactor, add solid acid catalyst and methyl alcohol, under 60 ± 1 ℃ of water bath with thermostatic control conditions, carry out pre-esterification reactor, behind reaction 40～60min, be placed under 0～-20 ℃, reaction is stopped; Solid acid catalyst is filtered out by separating funnel;
(2) transesterification: in above-mentioned reaction system, add basic catalyst and methyl alcohol, under 60 ± 1 ℃ of water bath with thermostatic control conditions, carry out esterification, behind reaction 60～80min, be placed under 0～-20 ℃, reaction is stopped, adding 2～10mL normal hexane in the reaction system again and extract.
At the little algae of high acid value, adopt the in-situ two-step catforming: the pre-esterification of acid-base catalysis conversion method.The utilization of this method, at first under the effect of an acidic catalyst, free fatty acids is converted into biofuel, and then under the effect of basic catalyst, neutral ester is converted into biofuel, described little algae is Chlorella vulgaris or Phaeodactylum tricornutum, its acid number is 2～10gKOH/g algae powder, solid acid catalyst is Amberlyst15, and its consumption is 10%～20% of little algae quality.Methanol usage is 5～8mL/g algae powder.Described basic catalyst is potassium hydroxide or sodium hydroxide, and consumption is 4%～5% (mass/volume, unit: mg/ml) of methyl alcohol.
The present invention has the following advantages:
(1) after pre-esterification reactor is finished, solid acid catalyst is leached, and through behind the simple place, solid acid can reuse;
(2) the solid acid pre-treatment can be converted into biofuel with free fatty acids, has avoided basic catalyst and free fatty acids generation saponification reaction;
(3) the pre-esterification of solid acid-base catalysis conversion method can either be converted into fatty acid methyl ester with free fatty acids, the generation of the saponification reaction when having avoided direct base catalysis; Simultaneously, base catalysis transforms and has improved speed of reaction, has shortened the reaction times, effectively improves biodiesel production rate.
The in-situ two-step catalyzed conversion of the little algae of a kind of high acid value of the present invention prepares method of bio-diesel oil, has improved the productive rate of biofuel greatly, has shortened the reaction times of entire reaction, and is workable, easy to utilize.
Four, embodiment
Embodiment 1
The in-situ two-step catalyzed conversion of the little algae of a kind of high acid value prepares method of bio-diesel oil, comprises that step is as follows:
(1) gets 300mg Chlorella vulgaris algae powder (acid number is 4.0mgKOH/g) in the centrifuge tube of the tetrafluoroethylene of 10mL, add solid acid (Amberlyst15) 30mg(10%, catalyzer/algae powder) and methyl alcohol 1.5mL, in 60 ℃ of waters bath with thermostatic control, behind the reaction 60min, reactor is placed-20 ℃ of refrigerators, reaction is stopped, solid acid is leached, with 2mL methanol wash an acidic catalyst 3 times, with pouring in the reactor after the washings merging, with Rotary Evaporators the methanol solution in the reactor is reclaimed then.
(2) (4%, 1.5mL), reaction conditions is described with (1), behind the reaction 60min, reactor is placed-20 ℃ of refrigerators, and reaction is stopped to add potassium hydroxide methanol solution in step (1) reaction system; Standing demix, upper strata are the methyl esters phase, and lower floor is the glycerine phase, by Rotary Evaporators with Methanol Recovery.
(3) in step (2), add the 2mL normal hexane, draw the upper strata yellow liquid, be the mixed solution of normal hexane and biofuel, remove normal hexane, can obtain the biofuel component.
Through the quantitative assay of the gas chromatograph-mass spectrometer property measured, main component and the percentage composition of the biofuel behind this little algae catalyzed conversion are respectively: Uniphat A60 (C16:0), content 31.42%; Methyl palmitoleinate (C16:1), content 6.9%; 17 carbon monoenoic acid methyl esters (C17:1), content is 5.08%; Methyl stearate (C18:0), content are 9.19%; Methyl linoleate (C18:2), content 20.01%; A-Linolenic acid methylester (C18:3), content are 25.35%, and all the other 2.05% are byproduct of reaction.
Embodiment 2
(1) gets 300mg Phaeodactylum tricornutum algae powder (acid number is 3.6mgKOH/g) in the centrifuge tube of the tetrafluoroethylene of 10mL, add solid acid (Amberlyst15) 30mg(10%, catalyzer/algae powder) and methyl alcohol 1.5mL, place thermostat water bath, 60 ℃ of waters bath with thermostatic control, behind the reaction 40min, reactor is placed-20 ℃ of refrigerators, reaction is stopped, solid acid is leached, with 2mL methanol wash an acidic catalyst 3 times, pour in the reactor after washings merged, with Rotary Evaporators the methanol solution in the reactor is reclaimed then.
(2) (4%, 1.5mL), reaction conditions is described with (1), behind the reaction 60min, reactor is placed-20 ℃ of refrigerators, and reaction is stopped to add potassium hydroxide methanol solution in step (1) reaction system; Standing demix, upper strata are the methyl esters phase, and lower floor is the glycerine phase, by Rotary Evaporators with Methanol Recovery.
(3) in step (2), add the 2mL normal hexane, get the upper strata yellow liquid, be the mixed solution of normal hexane and biofuel, remove normal hexane and can obtain the biofuel component.
Measure through the gas chromatograph-mass spectrometer qualitative, quantitative, main component and the percentage composition of the biofuel behind this little algae catalyzed conversion are respectively: myristic acid methyl esters (C14:0), content are 8.4%; Pentadecylic acid methyl esters (C15:0), content are 1.95%; Uniphat A60 (C16:0), content are 25.56%; Methyl palmitoleinate (C16:1), content are 39.70%; Hexadecadienoic acid methyl esters (C16:2), content are 2.27%; Methyl stearate (C18:0), content are 3.32%; Witconol 2301 and antiform oleic acid methyl esters (C18:1), content is 7.40%; Methyl linoleate (C18:2), content are 3.38%; A-Linolenic acid methylester (C18:3), content are 1.71%; Methyl behenate (C22:0), content are 2.83%; All the other are 3.48% for byproduct of reaction.
Claims (4)
1. the two-step catalysis of the little algae of high acid value transforms the preparation method of bio-diesel oil, it is characterized in that, comprises the steps:
(1) pre-esterification reactor: the little algae powder of 0.3～3g is joined in the reactor, add solid acid catalyst and methyl alcohol, under 60 ± 1 ℃ of water bath with thermostatic control conditions, carry out pre-esterification reactor, behind reaction 40～60min, be placed under 0～-20 ℃, reaction is stopped; Solid acid catalyst is filtered out by separating funnel;
(2) transesterification: in above-mentioned reaction system, add basic catalyst and methyl alcohol, under 60 ± 1 ℃ of water bath with thermostatic control conditions, carry out esterification, behind reaction 60～80min, be placed under 0～-20 ℃, reaction is stopped, adding 2～10mL normal hexane in the reaction system again and extract.
2. the two-step catalysis as the little algae of high acid value according to claim 1 transforms the preparation method of bio-diesel oil, and it is characterized in that: solid acid catalyst is Amberlyst15, and its consumption is 10%～20% of little algae quality.
3. the two-step catalysis as the little algae of high acid value according to claim 1 transforms the preparation method of bio-diesel oil, and it is characterized in that: methanol usage is 5～8mL/g algae powder.
4. the two-step catalysis as the little algae of high acid value according to claim 1 transforms the preparation method of bio-diesel oil, and it is characterized in that: described basic catalyst is potassium hydroxide or sodium hydroxide, and consumption is 4%～5% of methyl alcohol, unit: mg/mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713736A (en) * | 2016-04-23 | 2016-06-29 | 连云港恒图农牧开发有限公司 | Method for preparing biodiesel from animal wastes and seaweed |
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| CN1900223A (en) * | 2006-07-10 | 2007-01-24 | 中国科学院广州能源研究所 | Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor |
| CN101074390A (en) * | 2007-07-19 | 2007-11-21 | 杨庆利 | Production of biological diesel oil by high-acid value grease |
| CN101497803A (en) * | 2008-01-29 | 2009-08-05 | 姚明忠 | Biodiesel and preparing technology thereof |
| CN102690720A (en) * | 2012-06-06 | 2012-09-26 | 广西大学 | Method for preparing biodiesel directly from microalgae by using microwave technology |
| CN102787023A (en) * | 2012-07-28 | 2012-11-21 | 渤海大学 | Pre-processing method for microalgae oil for preparing microalgae |
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- 2013-05-21 CN CN2013101912931A patent/CN103242968A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900223A (en) * | 2006-07-10 | 2007-01-24 | 中国科学院广州能源研究所 | Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor |
| CN101074390A (en) * | 2007-07-19 | 2007-11-21 | 杨庆利 | Production of biological diesel oil by high-acid value grease |
| CN101497803A (en) * | 2008-01-29 | 2009-08-05 | 姚明忠 | Biodiesel and preparing technology thereof |
| CN102690720A (en) * | 2012-06-06 | 2012-09-26 | 广西大学 | Method for preparing biodiesel directly from microalgae by using microwave technology |
| CN102787023A (en) * | 2012-07-28 | 2012-11-21 | 渤海大学 | Pre-processing method for microalgae oil for preparing microalgae |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713736A (en) * | 2016-04-23 | 2016-06-29 | 连云港恒图农牧开发有限公司 | Method for preparing biodiesel from animal wastes and seaweed |
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Application publication date: 20130814 |