CN102154064B - Preparation method of biodiesel - Google Patents
Preparation method of biodiesel Download PDFInfo
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- CN102154064B CN102154064B CN2011100584273A CN201110058427A CN102154064B CN 102154064 B CN102154064 B CN 102154064B CN 2011100584273 A CN2011100584273 A CN 2011100584273A CN 201110058427 A CN201110058427 A CN 201110058427A CN 102154064 B CN102154064 B CN 102154064B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a preparation method of biodiesel, which comprises esterification reaction, alcoholysis reaction and the subsequent steps including dealcoholization, sedimentation, centrifugal washing separation, drying, vacuum fractionation and the like, wherein sulfonic acid organic acid is taken as catalyst in the esterification reaction, and ammonium organic base is taken as catalyst in the alcoholysis reaction. The preparation method of the biodiesel has the advantages that the organic acid and the organic base are taken as catalyst, and the biodiesel can be prepared by the esterification reaction and the alcoholysis reaction, so that solubility of methyl alcohol in oil can be enhanced, the reaction time is shortened, the production efficiency is improved, and the conversion rate of waste oil is high; the coking carbon deposition produced in the reaction processes of the oil can be reduced, and corrosion and damage to production facilities caused by metallic soaps can be prevented; and the preparation method is scientific and environment-friendly, the energy consumption is reduced, and the index value of the biodiesel meets the national standard BD100.
Description
Technical field
The present invention relates to a kind of preparation method of biofuel.
Background technology
Day by day the significant damage that the deficient and burning of fossil energy produces environment requires the human clean efficient and reproducible new forms of energy of research and development of accelerating, and how the biomass energy of utilizing of high-efficiency cleaning becomes the active demand of China's sustainable economic development.Because fatty acid methyl ester is the most approaching at aspect such as combustionproperty, characteristic and mineral diesel, have the cetane value height, do not have sulphur and do not have advantageous characteristic such as arene compound, and also biodegradable, receive extensive concern in recent years.
The preparation method of biofuel mainly contains physics method, chemical method, biological enzyme both at home and abroad at present.The physics method is not because quality product passes a test no longer development; Biological enzyme is because the higher and easy inactivation of cost of enzyme still is in the experimental study stage at present; Chemical method comprises esterification and the ester-interchange method and the supercritical methanol technology of acid or base catalysis, and wherein the supercritical methanol technology technology also is in developmental stage, and the esterification of acid or base catalysis and ester-interchange method are the relative proven technique of development.
The preparation method of conventional biofuel utilizes inorganic acid, highly basic to make catalyzer, is about to waste grease and under inorganic acid, highly basic effect, carries out esterification with low-carbon alcohol such as methyl alcohol or ethanol, generates corresponding fatty acid methyl ester or ethyl ester.Have following shortcoming with inorganic acid, highly basic as biodiesel: (1) is prone to make grease coking carbon distribution in reaction process, stops up reactor drum; (2) methyl alcohol solvability in grease is bad, causes catalysis efficiency low, long reaction time; (3) the strong basicity metallic salt is saponified, is prone to cause material to form emulsion, thereby makes that the washing water consumption is big and be difficult to carry out, and the metallic soap residual quantity is high, is prone to stop up rectifying device; (4) serious to equipment corrosion; (5) acid number of biodiesel is difficult to reach GB BD100 standard.
Summary of the invention
Goal of the invention: to the problems referred to above, the purpose of this invention is to provide a kind of is the feedstock production method of bio-diesel oil with the waste grease in the adaptation of doing with inorganic acid alkali to develop on the basis of biodiesel method, improves the transformation efficiency of waste grease.
Technical scheme: a kind of preparation method of biofuel, this method may further comprise the steps:
(1) esterification: with sulfonic acid class organic acid as catalyzer; With dissolve with methanol, with waste grease mixing heating in reaction unit, under 120 ± 10 ℃ temperature condition, feed methyl alcohol and carry out esterification then; And the moisture of continuous separating reaction generation; When the material acid number of this reaction system reached 0.2～3mg/KOH/g, stopped reaction was with lowering the temperature behind the glycerine of the settlement separate removal of material bottom and other impurity; Said sulfonic acid class organic acid usage quantity is 0.3%～2.0% of a waste grease gross weight, and said methyl alcohol feeding amount is 30%～80% of a waste grease gross weight;
(2) alcoholysis reaction: in another reaction unit, add ammonium class organic bases as catalyzer; Under 70 ℃ ± 10 ℃ temperature condition, feed the methyl alcohol mixing; The material that again step (1) sedimentation is obtained adds in this reaction unit and carries out alcoholysis reaction, and the reaction times is 10～50 minutes; The usage quantity of said ammonium class organic bases is 0.2%～2.0% of a waste grease gross weight, and said methyl alcohol feeding amount is 10%～40% of a waste grease gross weight;
(3) above-mentioned reacted product is carried out getting product after dealcoholysis, sedimentation, centrifugal washing separation, drying, the vacuum fractionation.
The sulfonic acid class organic acid as catalyzer described in the step (1) is 1,2,4-trimethylammonium-5-Phenylsulfonic acid, 2,4, a kind of in 5-tri-methyl p-toluenesulfonate, the p-methyl benzenesulfonic acid.
The ammonium class organic bases as catalyzer described in the step (2) is a kind of in hydroxide trimethylammonium ethyl ammonium, tetramethylammonium hydroxide, tetraethylammonium hydroxide, the TBAH.
Best, the usage quantity of sulfonic acid class organic acid described in the step (1) is 0.5%～1.0% of a waste grease gross weight, said methyl alcohol feeding amount is 40%～60% of a waste grease gross weight.
Best, the usage quantity of ammonium class organic bases is 0.4%～1.0% of a waste grease gross weight described in the step (2), said methyl alcohol feeding amount is 15%～35% of a waste grease gross weight.
Reaction unit described in the step (1) is a tank reactor.
Another reaction unit described in the step (2) is tank reactor or pipeline reactor.
Beneficial effect: compared with prior art, advantage of the present invention be with organic acids and base as catalyzer, prepare biofuel through over-churning and alcoholysis reaction; Strengthen the solubleness of methyl alcohol in grease; Shorten the reaction times, enhance productivity, the waste grease transformation efficiency is high; Reduce the coking carbon distribution that grease produces in reaction process, prevented corrosion and destruction that the existence of metallic soap class causes production unit; The environmental protection of preparing method's science cuts down the consumption of energy, and the biofuel desired value satisfies GB BD100 standard.
Embodiment
Below in conjunction with specific embodiment; Further illustrate the present invention; Should understand these embodiment only be used to the present invention is described and be not used in the restriction scope of the present invention; After having read the present invention, those skilled in the art all fall within the application's accompanying claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
A kind of preparation method of biofuel, this method may further comprise the steps:
(1) esterification: sulfonic acid class organic acid as catalyzer, with dissolve with methanol, is heated with waste grease mixing in tank reactor then; Under 120 ± 10 ℃ temperature condition, feed methyl alcohol and carry out esterification; And the continuous moisture that produces of separating reaction, when the material acid number of this reaction system reaches 0.2～3mgKOH/g, when being preferably 1.0～2.5mgKOH/g; Stopped reaction is with lowering the temperature behind the glycerine of the settlement separate removal of material bottom and other impurity; Said sulfonic acid class organic acid usage quantity is 0.3%～2.0% of a waste grease gross weight, is preferably 0.5%～1.0%; Said methyl alcohol feeding amount is 30%～80% of a waste grease gross weight, is preferably 40%～60%;
(2) alcoholysis reaction: in another tank reactor or pipeline reactor, add ammonium class organic bases as catalyzer; Under 70 ℃ ± 10 ℃ temperature condition, feed the methyl alcohol mixing; The material that again step (1) sedimentation is obtained adds in this reaction unit and carries out alcoholysis reaction; Reaction times is 10～50 minutes, is preferably 20～40 minutes; The usage quantity of said ammonium class organic bases is 0.2%～2.0% of a waste grease gross weight, is preferably 0.4%～1.0%; Said methyl alcohol feeding amount is 10%～40% of a waste grease gross weight, is preferably 15%～35%;
(3) above-mentioned reacted product is carried out getting product after dealcoholysis, sedimentation, centrifugal washing separation, drying, the vacuum fractionation.
Sulfonic acid class organic acid catalyst is 1,2 in the esterification of the present invention, 4-trimethylammonium-5-Phenylsulfonic acid, 2,4, a kind of in 5-tri-methyl p-toluenesulfonate, the p-methyl benzenesulfonic acid; Ammonium class organic alkali catalyst is a kind of in hydroxide trimethylammonium ethyl ammonium, tetramethylammonium hydroxide, tetraethylammonium hydroxide, the TBAH in the alcoholysis reaction.
The present invention prepares method of bio-diesel oil and utilizes the katalysis of organic acids and base to carry out the synthetic of biofuel; Adaptation is the production of raw material with the waste grease, has strengthened the solubleness of methyl alcohol in grease, shortens the reaction times; Enhance productivity, the waste grease transformation efficiency is high; The coking carbon distribution that grease produces in reaction process, stop up problem such as reactor drum be improved significantly, prevented heavy corrosion and destruction that the existence of metallic soap class causes production unit; Shortened the operational path of conventional catalyst reaction, reduced the washing water consumption, be merely 20% of traditional technology washing water consumption, greatly reduced energy consumption and environment protection treating cost, process energy consumption reduces by 40% than traditional technology energy consumption; The environmental protection of preparation method science meets the developing direction of Green Chemistry, and the biofuel desired value satisfies GB BD100 standard.
According to the said preparation method of the invention described above, the testing data statistics of preparation biofuel is listed like following table under the different parameters condition:
| 100 | 58 | 0.5 | 120±10 | 50 | 1.8 | 1 | 70±10 | 30 | 35 | 87.5 |
| 5000 | 137 | 50 | 120±10 | 2750 | 2.5 | 20 | 70±10 | 1000 | 35 | 4601 |
Visible by last table data, prepare biofuel according to the inventive method, the waste grease transformation efficiency is very high.
Claims (7)
1. the preparation method of a biofuel is characterized in that this method may further comprise the steps:
(1) esterification: with sulfonic acid class organic acid as catalyzer; With dissolve with methanol, with waste grease mixing heating in reaction unit, under 120 ± 10 ℃ temperature condition, feed methyl alcohol and carry out esterification then; And the moisture of continuous separating reaction generation; When the material acid number of this reaction system reached 0.2～3mgKOH/g, stopped reaction was with lowering the temperature behind the glycerine of the settlement separate removal of material bottom and other impurity; Said sulfonic acid class organic acid usage quantity is 0.3%～2.0% of a waste grease gross weight, and said methyl alcohol feeding amount is 30%～80% of a waste grease gross weight;
(2) alcoholysis reaction: in another reaction unit, add ammonium class organic bases as catalyzer; Under 70 ℃ ± 10 ℃ temperature condition, feed the methyl alcohol mixing; The material that again step (1) sedimentation is obtained adds in this reaction unit and carries out alcoholysis reaction, and the reaction times is 10～50 minutes; The usage quantity of said ammonium class organic bases is 0.2%～2.0% of a waste grease gross weight, and said methyl alcohol feeding amount is 10%～40% of a waste grease gross weight;
(3) above-mentioned reacted product is carried out getting product after dealcoholysis, sedimentation, centrifugal washing separation, drying, the vacuum fractionation.
2. the preparation method of biofuel according to claim 1; It is characterized in that: the sulfonic acid class organic acid as catalyzer described in the step (1) is 1,2,4-trimethylammonium-5-Phenylsulfonic acid, 2; 4, a kind of in 5-tri-methyl p-toluenesulfonate, the p-methyl benzenesulfonic acid.
3. the preparation method of biofuel according to claim 1 is characterized in that: the ammonium class organic bases as catalyzer described in the step (2) is a kind of in hydroxide trimethylammonium ethyl ammonium, tetramethylammonium hydroxide, tetraethylammonium hydroxide, the TBAH.
4. the preparation method of biofuel according to claim 1, it is characterized in that: the usage quantity of sulfonic acid class organic acid described in the step (1) is 0.5%～1.0% of a waste grease gross weight, and said methyl alcohol feeding amount is 40%～60% of a waste grease gross weight.
5. the preparation method of biofuel according to claim 1, it is characterized in that: the usage quantity of ammonium class organic bases is 0.4%～1.0% of a waste grease gross weight described in the step (2), said methyl alcohol feeding amount is 15%～35% of a waste grease gross weight.
6. the preparation method of biofuel according to claim 1, it is characterized in that: the reaction unit described in the step (1) is a tank reactor.
7. the preparation method of biofuel according to claim 1, it is characterized in that: another reaction unit described in the step (2) is tank reactor or pipeline reactor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100584273A CN102154064B (en) | 2011-03-11 | 2011-03-11 | Preparation method of biodiesel |
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| CN2011100584273A CN102154064B (en) | 2011-03-11 | 2011-03-11 | Preparation method of biodiesel |
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| CN102154064B true CN102154064B (en) | 2012-11-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103074162A (en) * | 2013-01-06 | 2013-05-01 | 盐城师范学院 | Method for preparing biodiesel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103013678B (en) * | 2011-09-20 | 2014-12-31 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN104745309B (en) * | 2013-12-27 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method for improving biodiesel yield |
| CN104694255B (en) * | 2015-03-09 | 2017-07-28 | 安徽增源生物能源有限公司 | A kind of method that low-temperature negative-pressure prepares biodiesel |
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| CN1073474A (en) * | 1992-12-26 | 1993-06-23 | 天津市轻工业化学研究所 | A kind of process for production of methyl fatty acid |
| CN101058734B (en) * | 2007-05-31 | 2010-12-01 | 张付舜 | Device for industrially synthesizing biological diesel oil by microwave and method thereof |
| CN101768517A (en) * | 2010-01-28 | 2010-07-07 | 华中农业大学 | Preparation method of biodiesel |
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| CN103074162A (en) * | 2013-01-06 | 2013-05-01 | 盐城师范学院 | Method for preparing biodiesel |
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Effective date of registration: 20160226 Address after: 401520 Chongqing Hechuan joint dam street is the No. 24 building 4 4-1, 4-2, 4-3, 4-4, 4-5 Patentee after: CHONGQING HAOTAI ENERGY CO., LTD. Address before: 212132 No. 88 Dagang grain mountain road, New District, Jiangsu, Zhenjiang Patentee before: Jiangsu Hengshunda Bio-energy Co., Ltd. |
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Granted publication date: 20121128 Termination date: 20190311 |