CN1944582A - Method for producing biological diesel oil - Google Patents

Method for producing biological diesel oil Download PDF

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Publication number
CN1944582A
CN1944582A CNA2006101138527A CN200610113852A CN1944582A CN 1944582 A CN1944582 A CN 1944582A CN A2006101138527 A CNA2006101138527 A CN A2006101138527A CN 200610113852 A CN200610113852 A CN 200610113852A CN 1944582 A CN1944582 A CN 1944582A
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oil
biofuel
reaction
acid methyl
low
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CN100567459C (en
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杨基础
王连鸳
朱慎林
贺华阳
汤志勇
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Tsinghua University
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Tsinghua University
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    • 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
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The present invention discloses method of producing biological diesel oil. In the presence of low carbon alkoxide of alkali metal as catalyst and under the conditions of 150-300 deg.c temperature and 2-30 MPa pressure, animal and vegetable fat and low carbon alcohol are made to produce catalytic ester interexchange reaction to produce biological diesel oil. The present invention has the advantages of high reaction speed, high biological diesel oil yield, low production cost and less environmental pollution.

Description

A kind of production method of bio-diesel oil
Technical field
The present invention relates to a kind of production method of bio-diesel oil.
Background technology
In recent decades because petroleum resources is exhausted day by day, oil price go up day by day and people to the concern gradually of environmental issue, the research of the fuel used substitute of diesel motor is seemed more and more important.
The scientist of states such as the U.S. in 1984 and Germany has studied the fatty acid ester of low-carbon alcohol that is obtained by animal-plant oil, comprises fatty acid methyl ester, and (being commonly called as biofuel) such as fatty-acid ethyl ester and lipid acid propyl ester replaces diesel combustion.Biofuel is compared with traditional petrifaction diesel, has the following advantages: with reproducible animal-plant oil is raw material, can reduce demand and import volume to the fossil fuel oil; Environmental friendliness, the toxic organic compound quantity discharged in the biofuel tail gas only are 10% of petrifaction diesel, and particulate matter is 20% of an ordinary diesel oil, and carbon monoxide and CO2 emissions only are 10% of petrifaction diesel, the discharging of Toxics such as no sulfide and lead.Because the cetane value and the viscosity of biofuel are all similar with the petrifaction diesel performance, can substitute 0# diesel oil, or mix with 0# diesel oil with arbitrary proportion, need not existing diesel is changed, just can be directly used in tractor, river steamer and the diesel engine for automobile of various models.
At present, the main machining method of biofuel is a chemical method, the inorganic bronsted lowry acids and bases bronsted lowry of normal employing is made transesterification catalyst, reaction conditions is gentle, but alkali as a catalyst easily causes the saponification phenomenon, requires in the raw material water-content extremely low, and the purifying flow process of product is complicated, product need be washed purifying, produces a large amount of waste water; The metal parts of acid as catalyst corrosion engine and High Temperature High Pressure supercritical reaction apparatus.Do not add any catalyzer, also can realize transesterification reaction in the overcritical low-carbon alcohol system, speed of response is exceedingly fast, and only needs several minutes, but reaction conditions is extremely harsh, it is reported, needs 350~400 ℃ high temperature and the high pressure of 45~65MPa, is difficult on the engineering realizing.
Summary of the invention
The purpose of this invention is to provide a kind of production method of bio-diesel oil.
Production method of bio-diesel oil provided by the present invention, being to be catalyzer with basic metal low-carbon (LC) alkoxide, is 150 ℃~300 ℃ in temperature of reaction, and reaction pressure is under the condition of 2MPa~30MPa, catalysis animal-plant oil and low-carbon alcohol are carried out transesterification reaction, obtain biofuel.
In the described method, the mol ratio of described low-carbon alcohol and animal-plant oil is 12: 1~42: 1, and promptly volume ratio is 0.5: 1~1.75: 1.
In order to improve the production efficiency of biofuel, the described reaction times can be 1~60min.
In the described method, the consumption of described basic metal low-carbon (LC) alkoxide is 0.2 ‰ of animal-plant oil quality~1.0 ‰.
Described basic metal low-carbon (LC) alkoxide can be lithium methoxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium propylate, sodium isopropylate, potassium propylate, potassium isopropoxide, sodium butylate, sodium tert-butoxide, butanols potassium or potassium tert.-butoxide.
Described low-carbon alcohol can be methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol or the trimethyl carbinol.
Described animal-plant oil is the refining oil or the crude oil of animal-plant oil, as Viscotrol C, rapeseed oil, plam oil, soybean oil, leprosy fruit oil, fish oil, lard, sheep oil, butter etc.
For fast reaction speed, in the described transesterification reaction, stir with the speed of 200rpm~1000rpm.
Method of the present invention, in super (Asia) critical (150 ℃~300 ℃, in the low-carbon alcohol of 2MPa~30MPa), basic metal low-carbon (LC) alkoxide catalysis animal-plant oil and low-carbon alcohol are carried out transesterification reaction and are obtained fatty acid ester of low-carbon alcohol (biofuel), and in reaction, low-carbon alcohol is excessive, can remove excessive low-carbon alcohol by distillation, in addition, glycerine in the product and biofuel are convenient to purifying through leaving standstill the back layering.Method of the present invention, speed of response is fast, the transformation efficiency height, and the product that obtains is easy to purifying.
Easy saponified phenomenon when method of the present invention has overcome traditional mineral alkali catalysis; The consumption of basic metal low-carbon (LC) alkoxide is less, and the purifying of product need not washed, and can reach the purpose of purifying by rectifying.The transesterification reaction speed of the inventive method is very fast, and the productive rate height of biofuel has been saved production cost, reduces environmental pollution.
Embodiment
Production process of the present invention is:
(1) preheating temperature that High Temperature High Pressure supercritical reaction apparatus and preheater be set is 160 ℃~310 ℃;
(2) adding, is stirred and is made its dissolving in low-carbon alcohol based on the basic metal low-carbon (LC) alkoxide of oil quality 0.2 ‰~1.0 ‰;
(3) with pump grease and the low-carbon alcohol that is dissolved with basic metal low-carbon (LC) alkoxide are squeezed into, wherein low-carbon alcohol and greasy mol ratio are 12: 1~42: 1 (volume ratio 0.5: 1~1.75: 1), raw material flows to the preheater preheating earlier, flow into again in the High Temperature High Pressure supercritical reaction apparatus, temperature of reaction is 150 ℃~300 ℃, behind reaction 1~60min, produce biofuel.
Method among the following embodiment if no special instructions, is ordinary method.
The production of embodiment 1, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 260 ℃.0.0405g catalyzer sodium methylate is dissolved in the 90ml anhydrous methanol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, with pump 90ml (81g) rapeseed oil crude oil (molecular-weight average 900) and above-mentioned 90ml methanol solution are squeezed into that (catalyst levels is 0.5 ‰ of an oil quality, the mol ratio of methyl alcohol and rapeseed oil crude oil is 24: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 250 ℃, and reaction pressure is 7.0MPa.Behind the reaction 15min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the methyl alcohol and make its layering, the upper strata is the product fatty acid methyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the above-mentioned biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 96.2%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 2, biofuel
Except catalyzer is a potassium methylate, the reaction times is outside the 18min, and other production method is produced and obtained biofuel with embodiment 1 described method.
GC-FID analyzes the above-mentioned biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 96.5%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 3, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 260 ℃.0.0162g catalyzer sodium methylate is dissolved in the 90ml anhydrous methanol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, the methanol solution that 90ml (81g) rapeseed oil crude oil (molecular-weight average is 900) and above-mentioned 90ml is contained sodium methylate with pump squeezes into that (consumption of catalyzer sodium methylate is 0.2 ‰ of an oil quality, methyl alcohol and rapeseed oil crude oil mol ratio are 24: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 250 ℃, and reaction pressure is 7.0MPa.Behind the reaction 40min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the methyl alcohol and make its layering, the upper strata is the product fatty acid methyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 96%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 4, biofuel
Except the consumption of catalyzer sodium methylate is that time of 0.081g (used oil quality 1.0 ‰), esterification is the 12min, other production method is all carried out according to embodiment 3 described methods.
GC-FID analyzes the biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 96.5%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 5, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 260 ℃.0.0405g catalyzer sodium methylate is dissolved in the 45ml anhydrous methanol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, the methanol solution that 90ml (81g) rapeseed oil crude oil (molecular-weight average is 900) and above-mentioned 45ml is contained sodium methylate with pump squeezes into that (catalyst levels is 0.5 ‰ of an oil quality, methyl alcohol and rapeseed oil crude oil mol ratio are 12: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 250 ℃, and reaction pressure is 3.1MPa.Behind the reaction 60min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the methyl alcohol and make its layering, the upper strata is the product fatty acid methyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 89%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 6, biofuel
Except the consumption of anhydrous methanol is that 158ml (methyl alcohol and rapeseed oil crude oil mol ratio are 42: 1), reaction pressure are that 30MPa, reaction times are the 10min, other production method is all carried out according to embodiment 5 described methods.
GC-FID analyzes the biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 98%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 7, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 310 ℃.0.0405g catalyzer sodium methylate is dissolved in the 90ml anhydrous methanol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, the methanol solution that 90ml (81g) rapeseed oil crude oil (molecular-weight average 900) and above-mentioned 90ml is contained sodium methylate with pump squeezes into that (catalyst levels is 0.5 ‰ of an oil quality, the mol ratio of methyl alcohol and rapeseed oil crude oil is 24: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 300 ℃, and reaction pressure is 12MPa.Behind the reaction 1min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the methyl alcohol and make its layering, the upper strata is the product fatty acid methyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the above-mentioned biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 8 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester, eicosenoic acid methyl esters, Decosahedaenoic acid methyl esters and Lignoceric acid methyl esters, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 95.1%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 8, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 160 ℃.0.0405g catalyzer sodium methylate is dissolved in the 90ml anhydrous methanol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, the methanol solution that 90ml (81g) soybean oil (molecular-weight average 865) and above-mentioned 90ml is contained sodium methylate with pump squeezes into that (catalyst levels is 0.5 ‰ of an oil quality, the mol ratio of methyl alcohol and soybean oil is 24: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 150 ℃, and reaction pressure is 2MPa.Behind the reaction 40min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the methyl alcohol and make its layering, the upper strata is the product fatty acid methyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the above-mentioned biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 5 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate and Linolenic acid methylester, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 97.6%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 9, biofuel
Except the preheating temperature that High Temperature High Pressure supercritical reaction apparatus and preheater are set is 210 ℃, makes temperature of reaction is that 205 ℃, reaction pressure are that 3.7MPa, reaction times are the 12min, and other production method is all carried out according to embodiment 8 described methods.
GC-FID analyzes the above-mentioned biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 5 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate and Linolenic acid methylester, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 97.8%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 10, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 260 ℃.0.0405g catalyzer sodium methylate is dissolved in the 90ml anhydrous methanol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, the methanol solution that 90ml (81g) leprosy fruit crude oil (molecular-weight average 850) and above-mentioned 90ml is contained sodium methylate with pump squeezes into that (catalyst levels is 0.5 ‰ of an oil quality, the mol ratio of methyl alcohol and leprosy fruit crude oil is 24: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 250 ℃, and reaction pressure is 7.0MPa.Behind the reaction 35min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the methyl alcohol and make its layering, the upper strata is the product fatty acid methyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the above-mentioned biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty acid methyl ester in the testing sample; By the peak area size of each fatty acid methyl ester and standard model in the comparison testing sample, determine the content of fatty acid methyl ester in the testing sample.The result shows, contain 4 kinds of fatty acid methyl esters in the biofuel that this method obtains, be respectively Uniphat A60, methyl stearate, Witconol 2301 and methyl linoleate, the quality percentage composition of the total fatty acids methyl esters in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids methyl esters of total fatty acids methyl esters) is 90%.
This biofuel can further improve the content of fatty acid methyl ester by rectifying.
The production of embodiment 11, biofuel
The High Temperature High Pressure supercritical reaction apparatus (top temperature is 350 ℃, and top pressure is 45Mpa, diameter 50mm, high 128mm, Haian County, Jiangsu oil scientific research instrument plant) and the preheating temperature of preheater are set are 260 ℃.The 0.0405g sodium ethylate is dissolved in the 90ml dehydrated alcohol.High Temperature High Pressure supercritical reaction apparatus and preheater reach preheating temperature and stable after, with pump the ethanolic soln that 90ml (81g) rapeseed oil crude oil (molecular-weight average is 900) and above-mentioned 90ml contain sodium ethylate is squeezed into that (catalyst levels is for based on 0.5 ‰ of oil quality, ethanol and rapeseed oil crude oil mol ratio 24: 1), raw material flows to preheater earlier and obtains preheating, flows in the High Temperature High Pressure supercritical reaction apparatus again.Pump starts stirring (400rpm, three leaf propeller, diameter 45mm, high 15mm) when finishing material, and timing begins.Temperature of reaction maintains 250 ℃, and reaction pressure is 7.0MPa.Behind the reaction 20min, emit the product in the High Temperature High Pressure supercritical reaction apparatus, in ice-water bath, receive with Erlenmeyer flask.To receive sample and evaporate on Rotary Evaporators, and remove and to leave standstill 10min behind the ethanol and make its layering, the upper strata is the product fatty-acid ethyl ester, i.e. biofuel, and lower floor is the byproduct glycerin layer.
GC-FID analyzes the biofuel that obtains, and adopts marker method, and internal standard substance is a methyl margarate.By with the contrast of standard model retention time, determine the kind of the fatty-acid ethyl ester in the testing sample; By the peak area size of each fatty-acid ethyl ester and standard model in the comparison testing sample, determine the content of fatty-acid ethyl ester in the testing sample.The result shows, contain 8 kinds of fatty-acid ethyl esters in the biofuel that this method obtains, be respectively ethyl palmitate, Stearic ethyl stearate, ethyl oleate, ethyl linoleate, ethyl linolenate, eicosylene acetoacetic ester, Decosahedaenoic acid ethyl ester and tetracosane acetoacetic ester, the quality percentage composition of the total fatty acids ethyl ester in this biofuel (quality * 100% of the quality/biofuel of the quality percentage composition=total fatty acids ethyl ester of total fatty acids ethyl ester) is 95.3%.
This biofuel can further improve the content of fatty-acid ethyl ester by rectifying.

Claims (8)

1, a kind of production method of bio-diesel oil is to be catalyzer with basic metal low-carbon (LC) alkoxide, is 150 ℃~300 ℃ in temperature of reaction, and reaction pressure is under the condition of 2MPa~30MPa, and catalysis animal-plant oil and low-carbon alcohol are carried out transesterification reaction, obtain biofuel.
2, method according to claim 1 is characterized in that: described low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol or the trimethyl carbinol.
3, method according to claim 1 and 2 is characterized in that: in the described reaction, low-carbon alcohol is excessive.
4, according to claim 1,2 or 3 described methods, it is characterized in that: the mol ratio of described low-carbon alcohol and animal-plant oil is 12: 1~42: 1, and volume ratio is 0.5: 1~1.75: 1.
5, method according to claim 4 is characterized in that: described basic metal low-carbon (LC) alkoxide is lithium methoxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium propylate, sodium isopropylate, potassium propylate, potassium isopropoxide, sodium butylate, sodium tert-butoxide, butanols potassium or potassium tert.-butoxide.
6, method according to claim 5 is characterized in that: the consumption of described basic metal low-carbon (LC) alkoxide is 0.2 ‰ of oil quality~1.0 ‰.
7, method according to claim 6 is characterized in that: the reaction times of described transesterification reaction is 1~60min.
8, according to arbitrary described method among the claim 1-7, it is characterized in that: described animal-plant oil is the refining oil or the crude oil of Viscotrol C, rapeseed oil, plam oil, soybean oil, leprosy fruit oil, fish oil, lard, sheep oil or butter.
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CN102161933A (en) * 2011-03-10 2011-08-24 四川大学 Method for preparing biodiesel by one step based on lepra fruits as raw material
CN102796622A (en) * 2012-08-24 2012-11-28 内蒙古大学 Method of preparing biodiesel through base catalysis of animal fat
CN102839055A (en) * 2012-02-28 2012-12-26 常州大学 Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil
CN103436359A (en) * 2013-08-27 2013-12-11 河南理工大学 Preparation method of fructus momordicae seed biological oil
CN103642535A (en) * 2013-12-24 2014-03-19 济南开发区星火科学技术研究院 Bio-compound diesel oil and preparation method thereof
CN105273850A (en) * 2014-05-29 2016-01-27 中国石油化工股份有限公司 Biodiesel synthesis promoting method
CN105969531A (en) * 2016-06-24 2016-09-28 青岛福瑞斯生物能源科技开发有限公司 Preparation method of biodiesel
CN108084020A (en) * 2017-12-21 2018-05-29 武汉欧米嘉生物医药有限公司 A kind of method that omega-7 aliphatic esters are prepared using grease as raw material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161933A (en) * 2011-03-10 2011-08-24 四川大学 Method for preparing biodiesel by one step based on lepra fruits as raw material
CN102839055A (en) * 2012-02-28 2012-12-26 常州大学 Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil
CN102839055B (en) * 2012-02-28 2014-08-13 常州大学 Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil
CN102796622A (en) * 2012-08-24 2012-11-28 内蒙古大学 Method of preparing biodiesel through base catalysis of animal fat
CN103436359A (en) * 2013-08-27 2013-12-11 河南理工大学 Preparation method of fructus momordicae seed biological oil
CN103642535A (en) * 2013-12-24 2014-03-19 济南开发区星火科学技术研究院 Bio-compound diesel oil and preparation method thereof
CN105273850A (en) * 2014-05-29 2016-01-27 中国石油化工股份有限公司 Biodiesel synthesis promoting method
CN105273850B (en) * 2014-05-29 2019-05-21 中国石油化工股份有限公司 A kind of promotion biodiesel synthetic method
CN105969531A (en) * 2016-06-24 2016-09-28 青岛福瑞斯生物能源科技开发有限公司 Preparation method of biodiesel
CN108084020A (en) * 2017-12-21 2018-05-29 武汉欧米嘉生物医药有限公司 A kind of method that omega-7 aliphatic esters are prepared using grease as raw material
CN108084020B (en) * 2017-12-21 2020-11-24 武汉欧米嘉生物医药有限公司 Method for preparing omega-7 fatty acid ester by using grease as raw material

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