CN103160380A - Method for preparing biodiesel by use of 1,2,3-triazole carbene carbon dioxide adduct catalyst - Google Patents
Method for preparing biodiesel by use of 1,2,3-triazole carbene carbon dioxide adduct catalyst Download PDFInfo
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- CN103160380A CN103160380A CN2013101035234A CN201310103523A CN103160380A CN 103160380 A CN103160380 A CN 103160380A CN 2013101035234 A CN2013101035234 A CN 2013101035234A CN 201310103523 A CN201310103523 A CN 201310103523A CN 103160380 A CN103160380 A CN 103160380A
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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
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- 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 discloses a method for preparing biodiesel by use of a 1,2,3-triazole carbene carbon dioxide adduct catalyst, belonging to the technical field of bio-fuel synthesis and green renerwable energy. The method adopts a transesterification reaction between vegetable oil and low alcohol and adopts a 1,2,3-triazole carbene carbon dioxide adduct as the catalyst, wherein the reaction temperature is 65-120 DEG C, the molar ratio of the vegetable oil to low alcohol is (1:6)-(1:30), the dosage of the catalyst is 0.1-5% of the mass of the vegetable oil, and the reaction lasts for 20-100 minutes. The method disclosed by the invention has the advantages of good catalyst stability, high reaction activity, mild reaction conditions, simple product separation, safe and non-toxic reaction process and no pollutant emission.
Description
Technical field
The invention belongs to bio-oil materials synthetic, technical field of green regenerative energy sources, particularly a kind of method of novel 1,2,3-triazoles Cabbeen carbon dioxide adduct catalysis for preparing biodiesel oil.
Background technology
To the rising steadily of energy demand, fossil energy constantly reduces along with the mankind, and uneven consumer goods prices and the environment given of energy supply and demand caused very large pressure, and Renewable Energy Development has become a kind of inexorable trend.A kind of renewable energy source---biofuel becomes the emphasis of people's research gradually.
Biofuel is a kind of fatty acid methyl ester, is take vegetables oil and animal oil and discarded edible oil as raw material, carry out transesterification reaction and generate, can with petroleum diesel with any than mixing.Biofuel has safety, environmental protection, and the characteristics such as renewable, diesel engine need not done change in use, environment-protecting clean, the U.S., European Union, the countries such as Brazil put into effect multiple support policy, and China is also encouraging research and development and the use of biofuel at present.
Biofuel mainly contains following 4 kinds of synthetic methods: (1) direct mixing method: natural fats and oils is directly mixed acting as a fuel according to different ratios with petroleum diesel, solvent or alcohols.This method is simple to operate, but the product cetane value is not high, and perishable.(2) microemulsion method: animal and vegetable oil and methyl alcohol, ethanol and n-butyl alcohol equal solvent are mixed and made into microemulsion directly use.This method is simple to operate, but the product cetane value is not high, and easily causes lubricant pollution.(3) high-temperature cracking method: triglyceride level is cracked into the mixture that contains alkane, alkene, diolefine, aromatic hydrocarbons and carboxylic acid etc. in inert gas.This method technique is simple, but need at high temperature carry out, and need to add catalyzer, apparatus expensive, and reaction is difficult to control.(4) ester-interchange method: utilize triglyceride level and lower alcohol to obtain biofuel under catalyst action.By transesterification reaction, the molecular weight of natural fats and oils is down to original 1/3, viscosity reduces approximately 8 times, has also improved fuel volatility simultaneously, and indices and diesel oil are the main method of present oil modification near this.
According to the difference of selected catalyzer, ester-interchange method can be divided into again enzyme ester catalysis method, acid catalyzed process and base catalysis method.
The enzyme catalysis mild condition, but have the problems such as the enzyme cost is high, the difficult separation of product, by product restraining effect.
The acid catalyzed reaction time is longer, and more serious to equipment corrosion.
Traditional base catalyzed reactions uses NaOH, and the mineral alkalis such as KOH are as catalyzer, the carrying out of catalyzed reaction effectively, but along with the carrying out of reaction, speed of reaction is that decline gradually, and easily cause the problems such as product last handling process complexity, and can cause a large amount of discharging of waste liquid in production process.
Cabbeen is an efficient organic compound of class, is scientist's study hotspot in recent years.Two research groups of Nolan and Hedrick (G. A.Grasa, R.M.Kissling and S.P. Nolan, Org.Lett., 2002,4,3583-3586; G. W. Nyce, J.A.Lamboy and J.L. Hedrick, Org.Lett., 2002,4,3587-3590) almost reported simultaneously the transesterification reaction of N-heterocyclic carbine catalysis, for being used for catalysis biological diesel oil, Cabbeen lays a good foundation.GAO (WO2008/070756) discloses a kind of take vegetable and animals oils as substrate, the method for preparing fatty acid alkyl ester, process comprising Cabbeen alcohol adducts catalysis transesterify, some the Cabbeen alcohol adducts that relates to must heat under vacuum condition could discharge active Cabbeen, increases operation easier.1,2,3-triazoles Cabbeen carbon dioxide adduct is stable to empty G﹠W, and as catalyzer, storage is very convenient with application, and is difficult for as introducing metal ion in product.Therefore, have a good application prospect in the preparation of biofuel.
Summary of the invention
The objective of the invention is to propose a kind of method of 1,2,3-triazoles Cabbeen carbon dioxide adduct catalysis for preparing biodiesel oil, have good catalyst controllability, reactive behavior is high, and speed of response is fast, and reaction conditions is relatively gentle, do not introduce metal ion, without equipment corrosion, the advantage such as product postprocessing is simple.
The present invention proposes a kind of method for preparing biofuel, it is characterized in that under protection of inert gas, and vegetables oil and low-carbon alcohol are mixed; add 1,2,3-triazoles Cabbeen carbon dioxide adduct as catalyzer; stir, react, obtain the product biofuel after example.
In the above-mentioned method for preparing biofuel, the structural formula of described 1,2,3-triazoles Cabbeen carbon dioxide adduct is formula (I), formula (II), formula (III), formula (IV).
In the above-mentioned method for preparing biofuel, rare gas element is nitrogen or argon gas.
In the above-mentioned method for preparing biofuel, described vegetables oil is: soybean oil, rapeseed oil, sweet oil, sesame oil, plam oil, Viscotrol C, tung oil, Oleum Gossypii semen, Trisun Oil R 80, peanut oil, jatropha curcas seed oil and Ka Lanjia seeds of trees oil.
In the above-mentioned method for preparing biofuel, described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol or propyl carbinol.
In the above-mentioned method for preparing biofuel, the mol ratio of described vegetables oil and low-carbon alcohol is 1: 6～1: 30, and catalyst levels is 0.1～5% of vegetables oil quality.
In the above-mentioned method for preparing biofuel, described temperature of reaction is 65～120 ℃, and the reaction times is 20～100 minutes.
In the above-mentioned method for preparing biofuel, described separation method be under room temperature with the reaction solution standing demix, isolate upper strata ester phase, after unreacted lower alcohol is removed in distillation, obtain the product biofuel.
Profitable fruit of the present invention is to select 1,2,3-triazoles Cabbeen carbonic acid gas as catalyzer.Speed of response is fast, and reaction conditions is gentle, does not introduce metal ion, and without equipment corrosion, the product aftertreatment is simple.
Embodiment
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, and under the scope of described aim, change is included in technical scope of the present invention before and after not breaking away from.
Embodiment 1
Under nitrogen protection, soybean oil, methyl alcohol are evenly mixed (mol ratio is 1: 8), add catalyst I (catalyst quality is 0.1% of the soybean oil quality), 85 ℃ of lower stirring reactions.Finish reaction after 30 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted methyl alcohol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 93%, and fatty acid ester middle methyl esters content mutually is 97%.
Embodiment 2
Under nitrogen protection, rapeseed oil, methyl alcohol are evenly mixed (mol ratio is 1: 6), add catalyst I I (catalyst quality is 0.5% of the rapeseed oil quality), 65 ℃ of lower stirring reactions.Finish reaction after 45 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted methyl alcohol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 91%, and fatty acid ester middle methyl esters content mutually is 95%.
Embodiment 3
Under nitrogen protection, sweet oil, ethanol are evenly mixed (mol ratio is 1: 10), add catalyst I II (catalyst quality is 2% of Quality of Olive Oil Produced), 85 ℃ of lower stirring reactions.Finish reaction after 60 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted ethanol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 90%, and fatty acid ester middle methyl esters content mutually is 93%.
Embodiment 4
Under nitrogen protection, sesame oil, n-propyl alcohol are evenly mixed (mol ratio is 1: 15), add catalyst I V (catalyst quality be sesame oil quality 3%), 100 ℃ of lower stirring reactions.Finish reaction after 80 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, remove unreacted n-propyl alcohol, utilize the analysis of Agilent GC-7890A gas chromatograph, recording the fatty acid triglycercide transformation efficiency is 91%, and fatty acid ester middle methyl esters content mutually is 98%.
Embodiment 5
Under nitrogen protection, tung oil, methyl alcohol are evenly mixed (mol ratio is 1: 6), add catalyst I (catalyst quality be tung oil quality 5%), 110 ℃ of lower stirring reactions.Finish reaction after 45 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted methyl alcohol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 87%, and fatty acid ester middle methyl esters content mutually is 92%.
Embodiment 6
Under argon shield, Oleum Gossypii semen, methyl alcohol are evenly mixed (mol ratio is 1: 20), add catalyst I (catalyst quality be Oleum Gossypii semen quality 1%), 120 ℃ of lower stirring reactions.Finish reaction after 25 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted methyl alcohol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 88%, and fatty acid ester middle methyl esters content mutually is 93%.
Embodiment 7
Under argon shield, plam oil, methyl alcohol are evenly mixed (mol ratio is 1: 30), add catalyst I I (catalyst quality be plam oil quality 0.8%), 100 ℃ of lower stirring reactions.Finish reaction after 50 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted methyl alcohol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 90%, and fatty acid ester middle methyl esters content mutually is 96%.
Embodiment 8
Under argon shield, jatropha curcas seed oil, ethanol are evenly mixed (mol ratio is 1: 10), add catalyst I II (catalyst quality be jatropha curcas seed oil quality 1.5%), 65 ℃ of lower stirring reactions.Finish reaction after 40 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted ethanol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 93%, and fatty acid ester middle methyl esters content mutually is 98%.
Embodiment 9
Under argon shield, Ka Lanjia seeds of trees oil, ethanol are evenly mixed (mol ratio is 1: 10), add catalyst I II (catalyst quality be Ka Lanjia seeds of trees oil quality 1.5%), 100 ℃ of lower stirring reactions.Finish reaction after 30 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted ethanol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 93%, and fatty acid ester middle methyl esters content mutually is 98%.
Embodiment 10
Under argon shield, Trisun Oil R 80, methyl alcohol are evenly mixed (mol ratio is 1: 12), add catalyst I (catalyst quality is 1.5% of the blue Trisun Oil R 80 quality of card), 80 ℃ of lower stirring reactions.Finish reaction after 50 minutes, standing demix under room temperature is isolated the upper strata and is distilled mutually, removes unreacted methyl alcohol, utilizes the analysis of Agilent GC-7890A gas chromatograph, and recording the fatty acid triglycercide transformation efficiency is 94%, and fatty acid ester middle methyl esters content mutually is 96%.
Claims (8)
1. one kind 2; the method of 3-triazole Cabbeen carbon dioxide adduct catalysis for preparing biodiesel oil; it is characterized in that under protection of inert gas; vegetables oil and low-carbon alcohol are mixed; add 1,2,3-triazoles Cabbeen carbonic acid gas binding substances as catalyzer; mixing and stirring is reacted, and is isolated to biofuel.
2. a kind of method for preparing biofuel according to claim 1, the structural formula that it is characterized in that described a kind of 1,2,3-triazoles Cabbeen carbon dioxide adduct is formula (I), formula (II), formula (III), formula (IV):
3. a kind of method for preparing biofuel according to claim 1, is characterized in that described rare gas element is nitrogen or argon gas.
4. a kind of method for preparing biofuel according to claim 1, is characterized in that described vegetables oil is: soybean oil, rapeseed oil, sweet oil, sesame oil, plam oil, Viscotrol C, tung oil, Oleum Gossypii semen, Trisun Oil R 80, peanut oil, jatropha curcas seed oil and Ka Lanjia seeds of trees oil.
5. a kind of method for preparing biofuel according to claim 1, is characterized in that described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol or propyl carbinol.
6. a kind of method for preparing biofuel according to claim 1, the mol ratio that it is characterized in that described vegetables oil and low-carbon alcohol is 1: 6～1: 30, catalyst levels is 0.1～5% of vegetables oil quality.
7. a kind of method for preparing biofuel according to claim 1, is characterized in that described temperature of reaction is 65～120 ℃, and the reaction times is 20～100 minutes.
8. a kind of method for preparing biofuel according to claim 1, it is characterized in that described separation method be under room temperature with the reaction solution standing demix, isolate upper strata ester phase, after unreacted lower alcohol is removed in distillation, obtain the product biofuel.
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Citations (4)
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| CN101418226A (en) * | 2008-12-01 | 2009-04-29 | 南京工业大学 | Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst |
| CN101665565A (en) * | 2008-09-01 | 2010-03-10 | 南京工业大学 | Method for preparing polylactic acid through catalysis of carbine derivatives |
| CN101665567A (en) * | 2008-09-01 | 2010-03-10 | 南京工业大学 | Method for controlled ring-opening polymerization for ring compound by catalysis of carbine derivatives |
| CN102675614A (en) * | 2012-05-08 | 2012-09-19 | 南京工业大学 | Method for preparing polyamino acid block poly-hydroxy acid copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665565A (en) * | 2008-09-01 | 2010-03-10 | 南京工业大学 | Method for preparing polylactic acid through catalysis of carbine derivatives |
| CN101665567A (en) * | 2008-09-01 | 2010-03-10 | 南京工业大学 | Method for controlled ring-opening polymerization for ring compound by catalysis of carbine derivatives |
| CN101418226A (en) * | 2008-12-01 | 2009-04-29 | 南京工业大学 | Method for preparing biodiesel by using N-heterocyclic carbine carbondioxide adducts as catalyst |
| CN102675614A (en) * | 2012-05-08 | 2012-09-19 | 南京工业大学 | Method for preparing polyamino acid block poly-hydroxy acid copolymer |
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Application publication date: 20130619 |