CN101514292A - Method for preparing microbe diesel oil by ionic liquid catalysis - Google Patents
Method for preparing microbe diesel oil by ionic liquid catalysis Download PDFInfo
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- CN101514292A CN101514292A CNA2008100578942A CN200810057894A CN101514292A CN 101514292 A CN101514292 A CN 101514292A CN A2008100578942 A CNA2008100578942 A CN A2008100578942A CN 200810057894 A CN200810057894 A CN 200810057894A CN 101514292 A CN101514292 A CN 101514292A
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention relates to a method for preparing microbe diesel oil by ionic liquid catalysis, which comprises the following steps: A) using acid functional ionic liquid as a reaction catalyst to catalyze free fatty acid and short-chain alcohol to react for 6 to 12 hours at a temperature of between 60 and 120 DEG C, wherein a molar ratio of the free fatty acid to the short-chain alcohol is 1:1-1:6, and the ratio of the mass of the acid functional ionic liquid to the total mass of the reactants is 1:20-20:1; and B) cooling the reaction solution obtained in step A to room temperature, depositing the reaction solution by gravity, layering a product and the acid functional ionic liquid, and decompressing the upper layer of liquid to separate out the short-chain alcohol so as to obtain the product, wherein the acid functional ionic liquid consists of sulfonic functional alkyl pyridine anions, sulfonic functional 1, 3-dialkyl imidazole anions or sulfonic functional alkyl amine salt anions and inorganic or organic anions. The method has no environment pollution, and belongs to an environment-friendly process.
Description
Technical field
The present invention relates to the method for the ionic liquid-catalyzed esterification of a kind of acid functionalization, in detail, relate to a kind of method of cleaner production micro-biodiesel.
Background technology
Reducing day by day of petroleum resources causes rising violently of energy shortage and oil price, makes people more and more pay close attention to oil-fired substitute, and biofuel is a kind of petroleum diesel energy substitution product that receive much concern in recent years.Biofuel not only combustionproperty is suitable with petroleum diesel, and has environmental friendliness, the reproducible advantage of resource, is one of ideal fuels that substitutes petroleum diesel.Biofuel is a kind of mono alkyl ester of longer chain fatty acid, generally is to be that raw material makes with the animal-plant oil.But China has a large population, and it is rare relatively to plough, and needs a large amount of import edible oils just can guarantee supply, and is too high by rapeseed oil and soybean wet goods food oils production biofuel cost, do not meet China's actual conditions.Therefore, the relevant person is actively developing the research work that reduces production costs, as seeks cheap raw material, optimization technology, the comprehensive utilization of raising product etc.Become in recent years research focus so seek the new operational path that can reduce the production of biodiesel cost.
Because of having traditional molecular solvent and fused salt dual nature, ionic liquid at room temperature has been widely used in catalysis or the uncatalyzed reaction as eco-friendly green solvent of a class or catalyzer.In recent years, the acid functionalization ionic liquid has become the focus in the research, and its advantage is: compare favourably with solid acid, and the tart modulation is easier, meticulousr, thereby helps the research and the screening of catalyst of catalytic mechanism more; Similar with conventional acid, have the advantage of fluent material, as: good fluidity, acidic site density height and strength of acid are evenly distributed; By changing and modified ion liquid yin, yang ionic structure, can realize the optimization of heterogeneous reaction system, as: increase the solvability of substrate, simplify the separation of product, promote ion liquid recycling.Therefore, the acid functionalization ionic liquid can replace the conventional acid catalyzer, has great application potential.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing microbe diesel oil by ionic liquid catalysis is to overcome the defective that exists in the known technology.
For achieving the above object, the method for preparing microbe diesel oil by ionic liquid catalysis provided by the invention the steps include:
A) with the acid functionalization ionic liquid as catalyst for reaction, catalysis free fatty acids and short chain alcohol are 60-120 ℃ of down reaction 6-12 hour;
Described reactant is free fatty acids and short chain alcohol, and wherein free-fat and short chain alcohol mol ratio are 1: 1 to 1: 6;
Described acid functionalization ionic liquid quality and reactant total mass ratio are 1: 20 to 20: 1.
B) reaction solution that steps A is made is cooled to room temperature, gravity settling, and product and the layering of acid functionalization ionic liquid, and, obtain product with the supernatant liquid short chain alcohol that reduces pressure.
Wherein, the alkyl pyridine positively charged ion that described acid functionalization ionic liquid is a sulfonic functional, sulfonic functional 1,3-dialkylimidazolium positively charged ion or sulfonic functional alkylamine salt positively charged ion and salt inorganic or that organic anion constitutes.
Described method, wherein, described positively charged ion is 1 of sulfonic functional alkyl pyridine positively charged ion, a sulfonic functional for the nitrogen-containing heterocycle compound positively charged ion, the alkylamine salt positively charged ion of 3-dialkylimidazolium positively charged ion or sulfonic functional, its general structure is as follows
Wherein, n=2～8, R is C
1～C
12
Described method, wherein, described negatively charged ion is chlorion, fluoroboric acid root, bisulfate ion, tosic acid root or trifluoromethanesulfonic acid root negative ion.
Described method, wherein, isolated acid functionalization ionic liquid is recycled and reused for reaction among the step B.
Described method, wherein, alcohols is ethanol or methyl alcohol in the steps A.
Compare with background technology, the present invention has the following advantages:
1, reaction raw materials difference is the free fatty acids that extracts in the fermented liquid.Therefore obtained a kind of new method for synthesizing biologic diesel oil.
2, the reaction conditions gentleness is easy and simple to handle.
3, reaction product and acid functionalization ionic-liquid catalyst mixing and AUTOMATIC ZONING makes sepn process more easy easily mutually not.
4, catalyst acid functionalized ion liquid stable performance, acid nothing runs off, and can be recycled; And simple synthetic method belongs to 100% Atom economy.
5, overcome the catalyst liquid that exists in the background technology and after reaction finishes, can not recycle, and problem of environment pollution caused.
6, belong to the environmentally friendly technology route.
Embodiment
The method of preparing microbe diesel oil by ionic liquid catalysis provided by the invention is the acid functionalization ionic liquid to be used for the free fatty acids that catalystic, fermentative liquid extracts carry out esterification, for the preparation of micro-biodiesel provides an eco-friendly operational path.
The acid functionalization ionic liquid that the present invention uses is to be made of nitrogen-containing heterocycle compound positively charged ion and negatively charged ion.Wherein, the positively charged ion in the acid functionalization ionic liquid is a sulfonic functional alkyl pyridine positively charged ion, 1 for the nitrogen-containing heterocycle compound positively charged ion, 3-dialkylimidazolium positively charged ion or alkylamine salt positively charged ion; Its general structure is as follows, wherein, n=2～8, R is C
1～C
6
Constituting the ion liquid negatively charged ion of acid functionalization is negative ions such as chlorion, fluoroboric acid root, bisulfate ion, tosic acid root, trifluoromethanesulfonic acid root.
The acid functionalization ionic liquid that the present invention uses can make by the following method:
With 1,3-propane sultone obtains 1-(3-sulfonic group) propyl group-3-methylimidazole salt with the reaction of N-Methylimidazole; After the water-soluble and equimolar sulphuric acid soln reaction of 1-(3-sulfonic group) propyl group-3-methylimidazole salt, decompression dehydration obtains 1-(3-sulfonic group) propyl group-3-Methylimidazole hydrosulfate.
The present invention is with after making acid functionalization ionic liquid 1-(3-sulfonic group) propyl group-3-Methylimidazole hydrosulfate catalysis free fatty acids and short chain alcohol esterification, gravity settling, product and the layering of acid functionalization ionic liquid, tell supernatant liquid, the supernatant liquid unreacting material that reduces pressure, make micro-biodiesel, reusable after lower floor's acid functionalization ionic liquid simple process.
In sum, technical scheme of the present invention the steps include:
1) the ion liquid preparation process of acid functionalization: with 1 of 24.4 parts of quality, 3-propane sultone is dissolved in the ethyl acetate of 200 parts of quality, be warming up to 50 ℃, drip the N-Methylimidazole of 16.4 parts of quality, dropwise, insulation reaction is after 3 hours, filter, filter cake washs with ethyl acetate, and in 100 ℃ times dry 2 hours, promptly obtains white solid 1-(3-sulfonic group) propyl group-3-methylimidazole salt; Get 1-(3-sulfonic group) propyl group-3-methylimidazole salt of 20.4 parts of quality, be dissolved in the deionized water of 50 parts of quality, drip the vitriol oil (98%) of 9.8 parts of quality, after dropwising, be warming up to 90 ℃ and insulation reaction 3 hours, after reaction finished, decompression dehydration obtained light yellow viscous liquid 1-(3-sulfonic group) propyl group-3-Methylimidazole hydrosulfate.
2) preparation of micro-biodiesel: in the there-necked flask of being furnished with thermometer, reflux condensing tube and magnetic stirring apparatus, the free fatty acids, second (first) alcohol, the ionic liquid that add certain proportioning, wherein free fatty acids and short chain alcohol, mol ratio between the two is 1: 1 to 1: 6, and ionic liquid quality and reactant total mass ratio are 1: 20 to 20: 1.Be warming up to temperature of reaction and begin to react timing, to the scheduled time, stopped reaction, behind the reaction solution cooling standing demix, upper strata liquid obtains product behind distillation purifying.The resulting separation ionic liquid can repeat to use after simple process.
Below in conjunction with embodiment method of the present invention being described further, is not limitation of the invention.
Embodiment one: with 7 gram acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfates, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 96.3%.
Embodiment two: with 4 gram acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfates, 28.2 gram free fatty acidies, and 9.6 gram methyl alcohol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～80 ℃.Reacted 6 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 92.8%.
Embodiment three: with 14 gram acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazole bisulfates, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 97.1%.
Embodiment four: with 7 gram acid functionalization ionic liquid N-(3-sulfonic group propyl group) pyridine hydrosulfates, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 12 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 93.4%.
Embodiment five: with 14 gram acid functionalization ionic liquid N-(3-sulfonic group propyl group) pyridine hydrosulfates, 28.2 gram free fatty acidies, and 9.6 gram methyl alcohol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～80 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 94.8%.
Embodiment six: with 7 gram acid functionalization ionic liquid 3-sulfonic group propyl group-triethyl ammonium hydrosulfates, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 6 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 91.6%.
Embodiment seven: with 14 gram acid functionalization ionic liquid 3-sulfonic group propyl group-triethyl ammonium hydrosulfates, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 92.8%.
Embodiment eight: with 7 gram acid functionalization ionic liquid 3-sulfonic group propyl group-triethyl ammonium hydrosulfates, 28.2 gram free fatty acidies, and 9.6 gram methyl alcohol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～80 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 90.7%.
Embodiment nine: with 14 gram acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazoles tosilate, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 92.5%.
Embodiment ten: with 14 gram acid functionalization ionic liquid 1-methyl-3-(3-sulfonic group propyl group) imidazoles fluoroform sulphonates, 28.2 gram free fatty acidies, and 9.6 gram methyl alcohol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～80 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 91.6%.
Embodiment 11: with 7 gram acid functionalization ionic liquid N-(3-sulfonic group propyl group) pyridine fluoroform sulphonates, 28.2 gram free fatty acidies, and 13.8 gram ethanol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～120 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 90.1%.
Embodiment 12: with 14 gram acid functionalization ionic liquid N-(3-sulfonic group propyl group) pyridine fluoroform sulphonates, 28.2 gram free fatty acidies, and 9.6 gram methyl alcohol put into reaction flask, stir, heating, esterification reaction temperature is 60 ℃～80 ℃.Reacted 9 hours, the reaction solution standing demix, inclining the upper strata reaction solution, distillation purifying, free fatty acids transformation efficiency 92.3%.
Claims (5)
1, a kind of method of preparing microbe diesel oil by ionic liquid catalysis the steps include:
A) with the acid functionalization ionic liquid as catalyst for reaction, catalysis free fatty acids and short chain alcohol are 60-120 ℃ of down reaction 6-12 hour;
Described reactant is free fatty acids and short chain alcohol, and wherein free fatty acids and short chain alcohol mol ratio are 1: 1 to 1: 6;
Described acid functionalization ionic liquid quality and reactant total mass ratio are 1: 20 to 20: 1.
B) reaction solution that steps A is made is cooled to room temperature, gravity settling, and product and the layering of acid functionalization ionic liquid, and, obtain product with the supernatant liquid short chain alcohol that reduces pressure.
Wherein, the alkyl pyridine positively charged ion that described acid functionalization ionic liquid is a sulfonic functional, sulfonic functional 1,3-dialkylimidazolium positively charged ion or sulfonic functional alkylamine salt positively charged ion and salt inorganic or that organic anion constitutes.
2, the method for claim 1, wherein, described positively charged ion is 1 of sulfonic functional alkyl pyridine positively charged ion, a sulfonic functional for the nitrogen-containing heterocycle compound positively charged ion, the alkylamine salt positively charged ion of 3-dialkylimidazolium positively charged ion or sulfonic functional, its general structure is as follows
Wherein, n=2～8, R is C
1～C
12
3, method as claimed in claim 2, wherein, described negatively charged ion is chlorion, fluoroboric acid root, bisulfate ion, tosic acid root or trifluoromethanesulfonic acid root negative ion.
4, the method for claim 1, wherein among the step B isolated acid functionalization ionic liquid be recycled and reused for reaction.
5, the method for claim 1, wherein in the steps A alcohols be ethanol or methyl alcohol.
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| CNA2008100578942A CN101514292A (en) | 2008-02-20 | 2008-02-20 | Method for preparing microbe diesel oil by ionic liquid catalysis |
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| CNA2008100578942A CN101514292A (en) | 2008-02-20 | 2008-02-20 | Method for preparing microbe diesel oil by ionic liquid catalysis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586341A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院青岛生物能源与过程研究所 | Method for biologically catalyzing 1,3-dioxane to be converted into 1,3-propylene glycol |
| CN102628008A (en) * | 2012-03-27 | 2012-08-08 | 绍兴文理学院 | Method for synthesizing biodiesel from waste grease by catalysis of polymeric ionic liquid |
| CN103131540A (en) * | 2013-02-19 | 2013-06-05 | 华侨大学 | Method for preparing biodiesel based on ionic liquid catalyzing peracid value rice bran oil |
| CN103756791A (en) * | 2013-12-25 | 2014-04-30 | 郑州奇克生物科技有限公司 | Synthetic method of biodiesel |
| WO2014063582A1 (en) * | 2012-10-23 | 2014-05-01 | Wu Feng | Ionic liquid catalyst and fatty acid preparation method |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
-
2008
- 2008-02-20 CN CNA2008100578942A patent/CN101514292A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586341A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院青岛生物能源与过程研究所 | Method for biologically catalyzing 1,3-dioxane to be converted into 1,3-propylene glycol |
| CN102586341B (en) * | 2011-01-11 | 2014-06-25 | 中国科学院青岛生物能源与过程研究所 | Method for biologically catalyzing 1,3-dioxane to be converted into 1,3-propylene glycol |
| CN102628008A (en) * | 2012-03-27 | 2012-08-08 | 绍兴文理学院 | Method for synthesizing biodiesel from waste grease by catalysis of polymeric ionic liquid |
| CN102628008B (en) * | 2012-03-27 | 2013-03-06 | 绍兴文理学院 | Method for synthesizing biodiesel from waste grease by catalysis of polymeric ionic liquid |
| WO2014063582A1 (en) * | 2012-10-23 | 2014-05-01 | Wu Feng | Ionic liquid catalyst and fatty acid preparation method |
| CN103131540A (en) * | 2013-02-19 | 2013-06-05 | 华侨大学 | Method for preparing biodiesel based on ionic liquid catalyzing peracid value rice bran oil |
| CN103756791A (en) * | 2013-12-25 | 2014-04-30 | 郑州奇克生物科技有限公司 | Synthetic method of biodiesel |
| CN103756791B (en) * | 2013-12-25 | 2015-08-19 | 郑州奇克生物科技有限公司 | The synthetic method of biofuel |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
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Application publication date: 20090826 |