CN103266017A - Method for increasing synthesis reaction efficiency of biodiesel - Google Patents
Method for increasing synthesis reaction efficiency of biodiesel Download PDFInfo
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- CN103266017A CN103266017A CN2013102380886A CN201310238088A CN103266017A CN 103266017 A CN103266017 A CN 103266017A CN 2013102380886 A CN2013102380886 A CN 2013102380886A CN 201310238088 A CN201310238088 A CN 201310238088A CN 103266017 A CN103266017 A CN 103266017A
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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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- 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
Abstract
The invention discloses a method for increasing the synthesis reaction efficiency of biodiesel. The method comprises the following steps of: (1) feeding: adding low-carbon alcohol and raw material grease which are in the mole ratio of (5: 1) to (30: 1) into a reaction kettle, and then adding an acidic catalyst which is 0.5-5% the weight of the grease into the reaction kettle while stirring; (2) heating: heating mixed liquid of the grease, the acidic catalyst and the low-carbon alcohol to the temperature of 50-62 DEG C; (3) circulating: starting up a circulating pump, pumping the mixed liquid at the bottom of the reaction kettle to the top of the reaction kettle, enabling the mixed liquid to be sprayed by a spraying device and then fall into the reaction kettle, and carrying out cyclic reaction for 2-6 hours until a sample passing a test; and (4) separating: after the cyclic reaction is completed, carrying out standing stratification, wherein an upper layer serves as a crude biodiesel product. The method has the advantages that the liquid phase reaction and the vapor-liquid mixed phase reaction are realized simultaneously, the reaction conditions are mild, the reaction time is short, and the reaction efficiency is high, so that the large-scale industrial production is facilitated.
Description
Technical field
The invention belongs to the production of biodiesel technology category of new energy field, be specifically related to a kind of method that improves the biofuel synthesis efficiency.
Background technology
Biofuel refers to that with animal-plant oil, waste cooking oil, industrial waste oil, sewer oil, acidifying wet goods grease be raw material and low-carbon alcohol such as methyl alcohol or ethanol through esterification or transesterification reaction and synthetic fatty acid methyl ester or ethyl ester, be the reproducibility diesel oil fuel that can replace petrifaction diesel to use, have renewable, pollute little, easy degraded, burning waits characteristics fully.The biofuel building-up reactions generally needs heating, particularly is the building-up reactions of raw material with the high-acid value grease, be unable to do without heating more.And under the reacting by heating condition, low-carbon alcohol such as the methyl alcohol in the reactant or ethanol gasify easily and overflow from liquid-phase system, thereby have reduced the low-carbon alcohol reactant concn in the liquid phase reaction, cause reaction efficiency to reduce.
Authorizing publication number in the patent documentation is a kind of production of biodiesel device of " a kind of biodiesel esterification device " announcement of CN 201660618 U, be characterized in outside the biodiesel esterification still, arranging a cover solvent recovery unit, make the solvent of gas phase be condensed to be converted into liquid phase solvent by temporary jar of the solvent condenser in the solvent recovery unit, solvent and recycle pump to refill reactor, the solvent in the esterification process is constantly replenished.Compare with the biofuel reaction unit that does not have the solvent condenses retrieving arrangement, though this biodiesel esterification device can improve the biofuel transforming degree, but because vapor phase solvent is condensed and is converted into that to refill the needed process of reactor behind the liquid phase solvent longer, particularly in solvent gasifies the process of condensation again, solvent release reaction system, so the reaction times does not reach best effect, not only can not obviously improve reaction efficiency, but also waste the energy.
The patent No. is " novel process of a kind of liquid phase, vapor phase catalytic, cracking processing biological diesel-oil " patent of 200610152507.4, a kind of new technology of carrying out cracking reaction on the basis of liquid-phase catalysis is again disclosed, it is characterized in that: when grease and low-carbon alcohol are carried out alcoholysis and esterification, in esterifying kettle, add, under 70 ℃ of temperature, carry out liquid-phase catalysis, obtain crude fatty acid methyl ester; Under 200-270 ℃ of temperature, distill refining then, allow oil gas through the catalytic tower of non-hydrogen beaded catalyst is housed, further to the thick methyl esters of larger molecular weight and fail the grease of esterification and carry out cracking in vapour phase, make it to obtain to greatest extent satisfactory biofuel.Though this novel process can improve biofuel building-up reactions degree, energy consumption is big.
Summary of the invention
The objective of the invention is to overcome existence is overflowed in the present production of biodiesel technology lower alcohol steam fails effectively to participate in reaction and the production efficiency that causes is low, energy consumption is big, treatment process is many etc. weak point from liquid phase, thereby a kind of method that can improve the biofuel synthesis efficiency is provided.Production efficiency height of the present invention, device structure is simple, energy consumption is low, cost is low, is suitable for utilizing the usefulness of animal-plant oil and waste cooking oil production biofuel.
Principle of work of the present invention is as follows: stock liquid (stock oil, low-carbon alcohol and catalyzer three's mixed solution) enters reactor through the feed liquid entrance, carries out liquid phase reaction; In the reaction process, the operative liquid low-carbon alcohol becomes low carbon alcohol vapor effusion liquid level because being heated; With pump mixed solution is extracted out by the outlet of reactor bottom, the Spray liquid device that is transported to reactor liquid level top through the mixed solution circulation tube sprays or the Spray mist.Mixed solution behind spray or the Spray mist carries out reverse the contact and the vapour-liquid reaction takes place with the low carbon alcohol vapor that liquid level in reactor is overflowed toward descending, and drops to then and proceeds liquid phase reaction on the reactor liquid level, so constantly circulation; After reaction finishes, standing demix, biofuel is collected from products export, and catalyzer and byproduct of reaction are collected by catalyzer and byproduct of reaction outlet.
Technical scheme
A kind of method that improves the biofuel synthesis efficiency comprises the steps:
(1) charging: low-carbon alcohol and the raw oil material with molar ratio of methanol to oil 5:1 ~ 30:1 mixes earlier, and adds in the reactor, and the ratio consumption according to grease weight 0.5% ~ 5% adds an acidic catalyst in reactor again, opens simultaneously and stirs;
(2) heat up: grease, an acidic catalyst and low-carbon alcohol three mixed solution are warming up to 50 ℃ ~ 62 ℃;
(3) circulation: the ON cycle pump, the mixed solution bottom the reactor is transported to the reactor top, after the liquid-jet device spraying, fall back in the reactor, so circulating reaction is 2 ~ 6 hours, and is qualified up to sample examination;
(4) separate: after reaction to be recycled finishes, standing demix, the upper strata is the biofuel crude product.
Technical superiority of the present invention is: the present invention has liquid phase, two kinds of reactive modes of vapour-liquid two-phase, make raw oil material, low-carbon alcohol and liquid catalyst three mixed solution that liquid phase reaction can take place, can circulate spraying again and further carry out vapour-liquid reaction with the low carbon alcohol vapor of liquid phase reaction course vaporized in part, the following backwardness can participate in liquid phase reaction again, so continuous circulation, solved all the time because of the low-carbon alcohol problems such as the reaction that causes is thorough of overflowing, shorten the reaction times greatly (shorten to original about 40%), significantly improved production efficiency; Simultaneously, the low carbon alcohol vapor that adds thermogenesis in the reactor need just can not be got back in the reaction liquid phase through the processing of still condensed exterior, has not only saved the energy, and improved the utilization ratio of low carbon alcohol vapor, improve reaction efficiency, by original 85%～88%, brought up to 90%～98%.From as can be seen last, the present invention contrasts prior art and has following advantage: (1) device structure is simple, less investment; (2) energy consumption is low, and cost is low; (3) production of biodiesel efficient significantly improves, and the reaction times shortens greatly, is easy to large-scale industrial production.
Embodiment
Embodiment 1
In reactor, add 500g soya-bean oil (acid value is 21.4mgKOH/g), 210g methyl alcohol, the 20g vitriol oil, open to stir post-heating to 62 ℃, mixed solution arrives reactor still top shower nozzle by pump delivery, after the shower nozzle spraying, fall back in the reactor, successive reaction 6h, sampling detects the oleic acid valency and reduces to 1.8 mgKOH/g, and reaction conversion ratio is 91.6%.Reaction is left standstill half an hour after finishing, and collects supernatant liquid, and supernatant liquid is reclaimed low-carbon alcohol through vacuum distilling,, gets upper oil phase and obtains refining biodiesel product 460.8g through vacuum distilling to clarification of water with hot water wash, and the reaction total yield is 92.2%.
Embodiment two:
In reactor, add 300g waste oil (acid value is 123.1mgKOH/g), 300g ethanol, the 10g vitriol oil, open to stir post-heating to 60 ℃, arrive reactor still top shower nozzle by pump delivery, after the shower nozzle spraying, fall back in the reactor, successive reaction 2h, sampling detects the oleic acid valency and reduces to 2.2mgKOH/g, and esterification yied is 98.2%.Reaction is left standstill half an hour after finishing, and collects supernatant liquid, and supernatant liquid is reclaimed low-carbon alcohol through vacuum distilling,, gets upper oil phase and obtains refining biodiesel product 288.8g through vacuum distilling to clarification of water with hot water wash, and the reaction total yield is 96.3%.
Embodiment three:
In reactor, add 300g waste oil (acid value is 123.1mgKOH/g), 350g low-carbon alcohol, the 15g vitriol oil, open to stir post-heating to 55 ℃, arrive reactor still top shower nozzle by pump delivery, after the shower nozzle spraying, fall back in the reactor, successive reaction 2.5h, sampling detects the oleic acid valency and reduces to 3.3mgKOH/g, and esterification yied is 97.3%.Reaction is left standstill half an hour after finishing, and collects supernatant liquid, and supernatant liquid is reclaimed low-carbon alcohol through vacuum distilling,, gets upper oil phase and obtains refining biodiesel product 284.3g through vacuum distilling to clarification of water with hot water wash, and the reaction total yield is 94.8%.
Claims (7)
1. a method that improves the biofuel synthesis efficiency is characterized in that comprising the steps:
(1) charging: low-carbon alcohol and the raw oil material with molar ratio of methanol to oil 5:1 ~ 30:1 adds in the reactor earlier, and the ratio consumption according to grease weight 0.5% ~ 5% adds an acidic catalyst in reactor again, opens simultaneously and stirs;
(2) heat up: grease, an acidic catalyst and low-carbon alcohol three mixed solution are warming up to 50 ℃ ~ 62 ℃;
(3) circulation: the ON cycle pump, the mixed solution bottom the reactor is transported to the reactor top, after the liquid-jet device spraying, fall back in the reactor, so circulating reaction is 2 ~ 6 hours, and is qualified up to sample examination;
(4) separate: after reaction to be recycled finishes, standing demix, the upper strata is the biofuel crude product.
2. the described a kind of method that improves the biofuel synthesis efficiency of claim 1 is characterized in that described raw oil material is the mixture of swill oil, sewer oil, waste cooking oil, industrial waste oil, Vegetable oil lipoprotein, animal grease or microbial oil and above-mentioned grease.
3. the described a kind of method that improves the biofuel synthesis efficiency of claim 1 is characterized in that described an acidic catalyst is the vitriol oil, and its mass percent concentration is 98%, and its addition is 0.5% ~ 5% of raw oil material weight.
4. the described a kind of method that improves the biofuel synthesis efficiency of claim 1, it is characterized in that described (3) circulation: the mixed solution that refers to the reactor bottom is transported to the reactor top, through still top liquid-jet device spray or the spraying back is heated with the reactor internal cause and from the low carbon alcohol vapor generation vapour-liquid hybrid reaction that liquid level is overflowed, drop to again then in the interior liquid-phase system of reactor.
5. method that improves the biofuel synthesis efficiency, it is characterized in that: the liquid phase building-up reactions takes place in raw oil material, catalyzer and liquid phase low-carbon alcohol three below the liquid level in reactor, and vapour-liquid mixed phase building-up reactions takes place above the liquid level in reactor for grease, catalyzer and gas phase low-carbon alcohol three simultaneously.
6. method that improves the biofuel synthesis efficiency is characterized in that described reaction comprises the transesterification reaction that takes place between the esterification that takes place between free fatty acids and low-carbon alcohol and glyceryl ester and low-carbon alcohol.
7. a method that improves the biofuel synthesis efficiency is characterized in that described low-carbon alcohol comprises the mixture of methyl alcohol, ethanol, propyl alcohol and butanols and two or more material thereof.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132190A (en) * | 2015-08-21 | 2015-12-09 | 中国林业科学研究院林产化学工业研究所 | Cyclic esterification method for preparing biodiesel from high-acid-value grease |
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| CN101225321A (en) * | 2007-12-24 | 2008-07-23 | 常州市绿空能源设备有限公司 | Method for preparing biodiesel by medium-temperature low-pressure process |
| CN201292349Y (en) * | 2008-11-14 | 2009-08-19 | 昆明理工大学 | Novel biodiesel production apparatus |
| US20100095581A1 (en) * | 2008-10-22 | 2010-04-22 | Biodiesel Logic, Inc. | Biodiesel production unit |
| US20110023353A1 (en) * | 2010-10-07 | 2011-02-03 | Joe Ciciulla | Process of making biodiesel |
| CN101338215B (en) * | 2008-08-25 | 2012-02-08 | 清华大学 | Method for preparing biodiesel by catalyzing oil or fatty acid with solid |
| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225321A (en) * | 2007-12-24 | 2008-07-23 | 常州市绿空能源设备有限公司 | Method for preparing biodiesel by medium-temperature low-pressure process |
| CN101338215B (en) * | 2008-08-25 | 2012-02-08 | 清华大学 | Method for preparing biodiesel by catalyzing oil or fatty acid with solid |
| US20100095581A1 (en) * | 2008-10-22 | 2010-04-22 | Biodiesel Logic, Inc. | Biodiesel production unit |
| CN201292349Y (en) * | 2008-11-14 | 2009-08-19 | 昆明理工大学 | Novel biodiesel production apparatus |
| US20110023353A1 (en) * | 2010-10-07 | 2011-02-03 | Joe Ciciulla | Process of making biodiesel |
| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105132190A (en) * | 2015-08-21 | 2015-12-09 | 中国林业科学研究院林产化学工业研究所 | Cyclic esterification method for preparing biodiesel from high-acid-value grease |
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