CN1850944A - Method for synthesizing biodiesel - Google Patents
Method for synthesizing biodiesel Download PDFInfo
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- CN1850944A CN1850944A CNA2006100355428A CN200610035542A CN1850944A CN 1850944 A CN1850944 A CN 1850944A CN A2006100355428 A CNA2006100355428 A CN A2006100355428A CN 200610035542 A CN200610035542 A CN 200610035542A CN 1850944 A CN1850944 A CN 1850944A
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention discloses a method to compound biology diesel oil that includes the following steps: adding alcohol and alkali catalyst into animal and vegetable oils that reacting temperature is 25-45 degree centigrade, whisking to react; delaminating, the upper layer is biology diesel oil and the down layer is glycerol alcohol; adding alcohol and alkali catalyst into the biology diesel oil to react under 25-45 degree centigrade; delaminating, the upper layer is alcohol glycerol layer and the down layer is biology diesel oil layer, the biology diesel oil would be separated. The invention has low reacting temperature and high reacting yield.
Description
Technical field
The present invention relates to the technical field of utilizing of new forms of energy, be meant a kind of method of utilizing the vegetable and animals oils biodiesel synthesis especially.
Background technology
Biofuel is a kind of emerging bioenergy that develops rapidly in recent years, will become the integral part of following sustainable energy.Biofuel can be used as the surrogate of high-quality petroleum diesel, belongs to environmentally friendly green fuel, has far-reaching economic benefit and social benefit.Nineteen eighty-three, U.S. scientist Graham Quick at first is used for engine with the methyl esters of linseed oil, the 1000h that burnt, and reproducible fatty acid monoester is defined as biofuel.Fatty acid monoester mainly refers to methyl esters, ethyl ester or the propyl ester etc. from animal, plant fatty acid.Biofuel is a kind of novel renewable energy, and it is the ideal substitute of petroleum resources, and developed countries such as America and Europe, Japan have risen to strategic height to the exploitation biofuel at present.2004, European Union's yield of biodiesel was 3,000,000 tons, and the U.S. is 1,000,000 tons.According to the law of European Union, biofuel share in 2005 must account for 2%, 2010 year of petroleum-based energy and reach 5.75%, and the year two thousand twenty reaches 20%.Rose in 2009, and must forcibly add 1% biofuel in all mineral diesel of European Union, added 1.75% in 2010.
Conventional diesel need not be transformed, and can directly use 100% biofuel.In Germany, the automobile that benz, BMW, masses and Adui manufacturer produce all can use biofuel and need not engine is reequiped.Also can use the mixture of biofuel and mineral diesel, the U.S. sells the diesel product that is mixed with 20% biofuel.
The Chinese president of Chinese Academy of Engineering Xu Kuangdi was gone up in " China biodiesel plants raw material development seminar " that hold and was proposed on January 18th, 2003, be based on national raw material scale operation replacement liquid fluid fuel---biofuel, have the important strategic meaning strengthening China's oil safety.China passed through and implements " People's Republic of China's renewable energy source method " on February 28th, 2005, and biofuel is clearly listed in wherein.
Present stage, industrial mainly is raw material base catalysis method biodiesel synthesis with the vegetable and animals oils, and temperature of reaction is 50～60 ℃, and the methyl alcohol addition is 6 times of oil mol, about 1 hour reaction times.The method of this one-step catalytic biodiesel synthesis, initial acid value and moisture content to vegetable and animals oils are had relatively high expectations, because temperature of reaction is higher, energy consumption is bigger, the easy saponification neutral grease of alkaline catalysts under the high temperature reduces catalytic efficiency and product yield simultaneously, because American-European standard has strict the qualification to content of triglyceride in the biofuel, traditional that one-step catalytic technology triglyceride level transformation efficiency generally is no more than 97%, yield is no more than 95%.
Summary of the invention
In order to solve the weak point that above-mentioned prior art exists, the object of the present invention is to provide a kind of method of utilizing the vegetable and animals oils biodiesel synthesis efficiently, this method transformation efficiency is higher, and yield is higher, and is more energy-conservation.
The present invention relates to (25～45 ℃) under a kind of normal temperature, utilize the method for vegetable and animals oils two-step approach biodiesel synthesis under base catalysis, utilize the unnecessary alcohol of second step reaction to add in the first step reaction, save the use of catalyzer, the triglyceride level transformation efficiency can reach more than 99%, and bio-diesel yield surpasses 97%.
Purpose of the present invention is achieved through the following technical solutions: a kind of method for synthesizing biological fuel-oil comprises the steps:
(1) add pure and mild alkaline catalysts in the vegetable and animals oils, temperature of reaction is 25～45 ℃, and stirring reaction is 0.5～2 hour under 300～400r/min rotating speed; Standing demix or centrifugal layering, upper strata are bio-diesel layer, and lower floor is the glyceryl alcohol layer; Described pure addition is 20～30% of a vegetable and animals oils weight; The alkaline catalysts addition is 0.5～1.6% of a vegetable and animals oils weight.
(2) isolate bio-diesel layer, add pure and mild alkaline catalysts, temperature of reaction is 25～45 ℃, reacts 0.5～2 hour under 300～400r/min rotating speed stirs; Standing demix or centrifugal layering, because alcohol is more, the upper strata is pure glycerin layer after the layering, lower floor is a bio-diesel layer; Upper strata alcohol glycerin layer is added in the vegetable and animals oils of next batch as reaction raw materials, can save catalyzer and alcohol, lower floor's biofuel reclaims alcohol through evaporation, then at 60～90 ℃, 5～10% hot water (80～90 ℃) washing with accounting for biofuel weight obtains biofuel; Described pure addition is 22～35% of a vegetable and animals oils weight; The alkaline catalysts consumption is 0.5～1.6% of a vegetable and animals oils weight.
In order to realize the present invention better, described vegetable and animals oils comprises soybean oil, mixed oil, plam oil, lard or rapeseed oil or the like.Described alcohol comprises methyl alcohol or ethanol or the like, and described alkaline catalysts is dissolved in the alcohol earlier, and then adds in the vegetable and animals oils.Described alkaline catalysts comprises sodium hydroxide or potassium hydroxide etc.
Particularly preferred scheme, pure addition is 22～25% of a vegetable and animals oils weight in the described step (1), the alkaline catalysts addition is 0.8～1.4% of a vegetable and animals oils weight; Pure addition is 25～30% of a vegetable and animals oils weight in the described step (2); The alkaline catalysts consumption is 0.8～1.4% of a vegetable and animals oils weight.Described temperature of reaction is 30～40 ℃.
If employing potassium hydroxide is alkaline catalysts, preferred especially potassium hydroxide addition is 1.0～1.4% of a vegetable and animals oils weight; If employing sodium hydroxide is alkaline catalysts, preferred especially sodium hydroxide addition is 0.8～1.0% of a vegetable and animals oils weight.
The transformation efficiency gas chromatographic analysis of triglyceride level among the present invention.The washing purpose is residual glycerine and the catalyzer of removing in the biofuel product.The alcohol of follow-up the first step reaction can be saved pure consumption with the second upper strata liquid that goes on foot reaction as reactant.The pure at the middle and upper levels glycerin layer of step (2) is added to as raw material in the vegetable and animals oils of next batch question response, carries out step (1) reaction, saves pure consumption.Because temperature of reaction is low, the neutral oil saponification is few, and product yield height generally surpasses 97%; Because step (2) alcohol is excessive a lot,, generally surpass 99% so reaction conversion ratio is very high.
The present invention compared with prior art has following advantage and beneficial effect: the present invention adopts the two-step approach biodiesel synthesis, and temperature of reaction is low, than traditional technology energy-conservation 20～50%.The upper strata alcohol glycerin layer in second step can be added to the first step reaction and save catalyzer as raw material, and reaction yield height surpasses 97%; The transformation efficiency height surpasses 99%.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
The two-step approach biodiesel synthesis:
The first step reaction: get edible blend oil 100g, add methyl alcohol 25g, sodium hydroxide 1g (being dissolved in the methyl alcohol) at 25 ℃, reacted 1 hour in reactor under the 300r/min mixing speed.Standing demix, upper strata are bio-diesel layer, and lower floor is the glycerine methanol layer.The reaction of second step: get the upper strata bio-diesel layer, add 27g methyl alcohol, sodium hydroxide 1g (being dissolved in the methyl alcohol) at 25 ℃, reacted 1 hour in reactor under the 300r/min mixing speed.Use the separating funnel standing demix, because methyl alcohol is more, the upper strata is the methyl alcohol glycerin layer after the layering, and lower floor is a bio-diesel layer.Lower floor's biofuel is at absolute pressure 60kPa, reclaim methyl alcohol with the rotatory evaporator evaporation under 60 ℃ after, at 80 ℃, 10% hot water (80 ℃) washing twice with accounting for biofuel weight obtains biofuel.The calculating yield of weighing after the drying.The transformation efficiency gas chromatographic analysis of triglyceride level.Upper strata methyl alcohol glycerin layer is added in the 100g edible blend oil of next batch question response as raw material, carries out the first step reaction, saves alkaline catalysts.Two-step approach product yield is 97.8%, and the transformation efficiency of triglyceride level is 99.2%.
Embodiment 2
The first step reaction: get plam oil 500g, add methyl alcohol 100g, sodium hydroxide 3g (being dissolved in the methyl alcohol) at 40 ℃, reacted 1.5 hours in reactor under the 400r/min mixing speed.Centrifugal layering, upper strata are bio-diesel layer, and lower floor is the glycerine methanol layer.The reaction of second step: get the upper strata bio-diesel layer, add 115g methyl alcohol, sodium hydroxide 3g (being dissolved in the methyl alcohol) at 40 ℃, reacted 1 hour in reactor under the 400r/min mixing speed.Use the separating funnel standing demix, because methyl alcohol is more, the upper strata is the methyl alcohol glycerin layer after the layering, and lower floor is a bio-diesel layer.Lower floor's biofuel is at absolute pressure 60kPa, reclaim methyl alcohol with the rotatory evaporator evaporation under 60 ℃ after, at 90 ℃, 6% hot water (90 ℃) washing twice with accounting for biofuel weight obtains biofuel.The calculating yield of weighing after the drying.The transformation efficiency gas chromatographic analysis of triglyceride level.Upper strata methyl alcohol glycerin layer is added in the 500g plam oil of next batch question response as raw material, carries out the first step reaction, saves alkaline catalysts.Two-step approach product yield is 98.6%, and the transformation efficiency of triglyceride level is 99.5%.
Embodiment 3
The first step reaction: get lard 1000g, add methyl alcohol 300g, potassium hydroxide 14g (being dissolved in the methyl alcohol) at 45 ℃, reacted 2 hours in reactor under the 350r/min mixing speed.With the centrifugal layering of whizzer, the upper strata is a bio-diesel layer, and lower floor is the glycerine methanol layer.The reaction of second step: get the upper strata bio-diesel layer, add 350g methyl alcohol, potassium hydroxide 10g (being dissolved in the methyl alcohol) at 45 ℃, reacted 2 hours in reactor under the 350r/min mixing speed.With the centrifugal layering of whizzer (centrifugal condition is: under rotating speed 3000r/min, centrifugation time 10min), because methyl alcohol is more, the upper strata is the methyl alcohol glycerin layer after the layering, and lower floor is a bio-diesel layer.Lower floor's biofuel is at absolute pressure 60kPa, reclaim methyl alcohol with the rotatory evaporator evaporation under 60 ℃ after, at 80 ℃, 8% hot water (80 ℃) washing twice with accounting for biofuel weight obtains biofuel.The calculating yield of weighing after the drying.The transformation efficiency gas chromatographic analysis of triglyceride level.Upper strata methyl alcohol glycerin layer is added in the 1000g lard of next batch question response as raw material, carries out the first step reaction, saves alkaline catalysts.Two-step approach product yield is 97.8%, and the transformation efficiency of triglyceride level is 99.4%.
Embodiment 4
The first step reaction: get soybean oil 5000g, add ethanol 1000g, sodium hydroxide 40g (being dissolved in the ethanol) at 35 ℃, reacted 0.5 hour in reactor under the 300r/min mixing speed.With the centrifugal layering of whizzer, the upper strata is a bio-diesel layer, and lower floor is the glycerine alcohol layer.The reaction of second step: get the upper strata bio-diesel layer, add 1500g ethanol, sodium hydroxide 40g (being dissolved in the ethanol) at 35 ℃, reacted 0.5 hour in reactor under the 300r/min mixing speed.With the centrifugal layering of whizzer (centrifugal condition is: under rotating speed 3000r/min, centrifugation time 10min), because ethanol is more, the upper strata is the ethanol glycerin layer after the layering, and lower floor is a bio-diesel layer.Lower floor's biofuel is at absolute pressure 60kPa, reclaim ethanol with the rotatory evaporator evaporation under 65 ℃ after, at 70 ℃, 5% hot water (85 ℃) washing twice with accounting for biofuel weight obtains biofuel.The calculating yield of weighing after the drying.The transformation efficiency gas chromatographic analysis of triglyceride level.Upper strata ethanol glycerin layer is added in the 5000g soybean oil of next batch question response as raw material, carries out the first step reaction, saves alkaline catalysts.Two-step approach product yield is 97.8%, and the transformation efficiency of triglyceride level is 98.5%.
Embodiment 5
The first step reaction: get rapeseed oil 5000g, add methyl alcohol 1200g, potassium hydroxide 50g (being dissolved in the methyl alcohol) at 30 ℃, reacted 1 hour in reactor under the 300r/min mixing speed.With the centrifugal layering of whizzer, the upper strata is a bio-diesel layer, and lower floor is the glycerine methanol layer.The reaction of second step: get the upper strata bio-diesel layer, add 1400g ethanol, sodium hydroxide 50g (being dissolved in the methyl alcohol) at 30 ℃, reacted 1 hour in reactor under the 300r/min mixing speed.With the centrifugal layering of whizzer (centrifugal condition is: under rotating speed 3000r/min, centrifugation time 10min), because methyl alcohol is more, the upper strata is the methyl alcohol glycerin layer after the layering, and lower floor is a bio-diesel layer.Lower floor's biofuel is at absolute pressure 60kPa, reclaim methyl alcohol with the rotatory evaporator evaporation under 60 ℃ after, at 60 ℃, 10% hot water (80 ℃) washing twice with accounting for biofuel weight obtains biofuel.The calculating yield of weighing after the drying.The transformation efficiency gas chromatographic analysis of triglyceride level.Upper strata methyl alcohol glycerin layer is added in the 5000g rapeseed oil of next batch question response as raw material, carries out the first step reaction, saves alkaline catalysts.Two-step approach product yield is 99.2%, and the transformation efficiency of triglyceride level is 99.5%.
As mentioned above, can realize the present invention preferably.
Claims (10)
1, a kind of method for synthesizing biological fuel-oil is characterized in that comprising the steps:
(1) add pure and mild alkaline catalysts in the vegetable and animals oils, temperature of reaction is 25～45 ℃, and stirring reaction is 0.5～2 hour under 300～400r/min rotating speed; Standing demix or centrifugal layering, upper strata are bio-diesel layer, and lower floor is the glyceryl alcohol layer; Described pure addition is 20～30% of a vegetable and animals oils weight; The alkaline catalysts addition is 0.5～1.6% of a vegetable and animals oils weight;
(2) isolate bio-diesel layer, add pure and mild alkaline catalysts, temperature of reaction is 25～45 ℃, reacts 0.5～2 hour under 300～400r/min rotating speed stirs; Standing demix or centrifugal layering, the upper strata is pure glycerin layer after the layering, lower floor is a bio-diesel layer; Alcohol glycerin layer in upper strata is added to as reaction raw materials in the vegetable and animals oils of next batch, and lower floor's biofuel reclaims alcohol through evaporation, and then at 60～90 ℃, 5～10% hot water washing with accounting for biofuel weight obtains biofuel; Described pure addition is 22～35% of a vegetable and animals oils weight; The alkaline catalysts consumption is 0.5～1.6% of a vegetable and animals oils weight.
2, a kind of biofuel synthetic method according to claim 1, it is characterized in that: described vegetable and animals oils comprises soybean oil, mixed oil, plam oil, lard or rapeseed oil.
3, a kind of method for synthesizing biological fuel-oil according to claim 1 is characterized in that: described alcohol is methyl alcohol or ethanol.
4, a kind of method for synthesizing biological fuel-oil according to claim 1, it is characterized in that: described alkaline catalysts is dissolved in the alcohol earlier, and then adds in the vegetable and animals oils.
5, a kind of method for synthesizing biological fuel-oil according to claim 1, it is characterized in that: described alkaline catalysts comprises sodium hydroxide or potassium hydroxide.
6, a kind of method for synthesizing biological fuel-oil according to claim 1 is characterized in that: pure addition is 22～25% of a vegetable and animals oils weight in the described step (1), and the alkaline catalysts addition is 0.8～1.4% of a vegetable and animals oils weight.
7, a kind of method for synthesizing biological fuel-oil according to claim 1 is characterized in that: pure addition is 25～30% of a vegetable and animals oils weight in the described step (2); The alkaline catalysts consumption is 0.8～1.4% of a vegetable and animals oils weight.
8, a kind of method for synthesizing biological fuel-oil according to claim 1 is characterized in that: described temperature of reaction is 30～40 ℃.
9, a kind of method for synthesizing biological fuel-oil according to claim 5 is characterized in that: described potassium hydroxide addition is 1.0～1.4% of a vegetable and animals oils weight.
10, a kind of method for synthesizing biological fuel-oil according to claim 5 is characterized in that: described sodium hydroxide addition is 0.8～1.0% of a vegetable and animals oils weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100355428A CN100402631C (en) | 2006-05-22 | 2006-05-22 | Method for synthesizing biodiesel |
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| CNB2006100355428A CN100402631C (en) | 2006-05-22 | 2006-05-22 | Method for synthesizing biodiesel |
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| CN1850944A true CN1850944A (en) | 2006-10-25 |
| CN100402631C CN100402631C (en) | 2008-07-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654625A (en) * | 2008-08-22 | 2010-02-24 | 张伟民 | Method for refining biodiesel |
| CN102071108B (en) * | 2009-11-24 | 2012-09-12 | 中国石油化工股份有限公司 | Preparation method of biodiesel |
| CN104312735A (en) * | 2014-11-13 | 2015-01-28 | 山东华亚环保科技有限公司 | Method for producing biodiesel by utilizing waste vegetable oil |
| CN112481041A (en) * | 2020-12-15 | 2021-03-12 | 浙江工业大学 | Device and method for continuously preparing biodiesel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005052103A1 (en) * | 2003-11-24 | 2005-06-09 | Council Of Scientific And Industrial Research | An improved process for the preparation of bio-diesel |
| CN1687314A (en) * | 2005-04-27 | 2005-10-26 | 莫春礼 | Technique for producing biologic diesel oil through obsolete animal and vegetable oils in high acid value |
-
2006
- 2006-05-22 CN CNB2006100355428A patent/CN100402631C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654625A (en) * | 2008-08-22 | 2010-02-24 | 张伟民 | Method for refining biodiesel |
| CN101654625B (en) * | 2008-08-22 | 2013-08-07 | 张伟民 | Method for refining biodiesel |
| CN102071108B (en) * | 2009-11-24 | 2012-09-12 | 中国石油化工股份有限公司 | Preparation method of biodiesel |
| CN104312735A (en) * | 2014-11-13 | 2015-01-28 | 山东华亚环保科技有限公司 | Method for producing biodiesel by utilizing waste vegetable oil |
| CN112481041A (en) * | 2020-12-15 | 2021-03-12 | 浙江工业大学 | Device and method for continuously preparing biodiesel |
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| CN100402631C (en) | 2008-07-16 |
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Assignee: Foshan Gentle Biological Engineering Co., Ltd. Assignor: Jinan University Contract record no.: 2012440000336 Denomination of invention: Method for synthesizing biodiesel Granted publication date: 20080716 License type: Exclusive License Open date: 20061025 Record date: 20120621 |
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Granted publication date: 20080716 Termination date: 20190522 |