CN101108801A - Method for manufacturing fatty acid ester continuously in ultrasonic field - Google Patents
Method for manufacturing fatty acid ester continuously in ultrasonic field Download PDFInfo
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- CN101108801A CN101108801A CNA2006100366297A CN200610036629A CN101108801A CN 101108801 A CN101108801 A CN 101108801A CN A2006100366297 A CNA2006100366297 A CN A2006100366297A CN 200610036629 A CN200610036629 A CN 200610036629A CN 101108801 A CN101108801 A CN 101108801A
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- acid ester
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The objective of the invention is to provide a method continuously preparing the fatty acid ester in the ultrasonic field, which relates to the technology fields of the renewable energy, the chemical intermediates and the inert ingredient. The invention comprises the following steps: (1) the alkali is dissolved in the low carbon alcohol to alcoholic solution; (2) the alcoholic solution and the animal fats are first measured, preheated and then are premixed via a pipeline mixer, and continuously enter a high shear emulsified equipment and a sonochemical reactor; the gained product gains the raw ester through centrifugation; (3) the coarse ester removes the low carbon alcohol and is washed by diluted acid or running water, and then carries out the vacuum dehydration to gain the fatty acid ester. The effects of the invention are that adopting the method of the invention can realize rapid and continuous preparation of the fatty acid ester with simple technology and little usage of the catalyst, which solves the problems that the ultrasonic equipments in the intermittent preparation are difficult to enlarge, the reaction time in the traditional method is long, post treatment is complex and the environment pollution is serious.
Description
Technical field
The present invention relates to technical fields such as renewable energy source, chemical intermediate, inert ingredient, specifically being meant a kind of is raw material with the animal-plant oil, and alkali is catalyzer, carries out the reaction of animal-plant oil and low-carbon alcohol in ultrasonic field, prepares the method for fatty acid ester continuously.
Background technology
In recent years, reducing day by day and human concern along with prospective oil to the global environment influence that oil combustion brought.Develop new environment amenable renewable fuel oil one biological diesel oil, become many scientific workers' the objective of the struggle.Biofuel mainly is a fatty acid methyl ester, belongs to a kind of of renewable energy source, and its appearance can solve energy dilemma, environmental regulation and agricultural restructuring Three Difficult Issues.Because material such as sulfur-bearing, aromatic hydrocarbon not in the biofuel does not discharge sulfurous gas during burning, the obnoxious flavour of discharge reduces about 70% than petroleum diesel, helps ecological environmental protection, is a new research field of rising both at home and abroad at present.
Simultaneously, fatty acid ester, especially fatty acid methyl ester or fatty-acid ethyl ester also are the important chemical intermediates, and they can be used for preparing chemical such as Fatty Alcohol(C12-C14 and C12-C18), alkylolamide.They also are widely used in the leather chemical industry industry, to strengthen leather hand feeling, improve strength of leather, surface layer luminance brightness, ventilation property and water tolerance.In addition, fatty acid ester still is the lime soap dispersing agent of excellent property, eco-friendly inert ingredient.
The production technology of existing fatty acid ester mainly is liquid caustic soda catalytic transesterification, perhaps acid catalyzed esterification.The catalyzer of transesterify often is KOH, NaOH, CH
3ONa, CH
3OK, K
2CO
3, Na
2CO
3, necessary strict anhydrous, the no free acid of this processing requirement raw oil material and low-carbon alcohol, otherwise easily form milk, and activity of such catalysts is subjected to very big infringement.Simultaneously, this reaction times is also longer.Acid catalyzed esterification technology is not strict to ingredient requirement, but acid is corrosive to equipment, and by product be difficult to separate the postprocessing working procedures complexity.Problems such as all there is complex process in these two kinds of methods, and three waste discharge is many, and environmental pollution is serious.Therefore, find a kind of appropriate preparation method, simplify technology, reduce environmental pollution, reduce production costs, become the focus of people's Recent study.
Ultrasonic wave can produce a series of extreme conditions when propagating in liquid, as deep discharge, generation part, high temperature, high pressure and the association intensive shockwave of moment, this energy not only can excite or promote many chemical reactions, fast reaction speed, even can also change the direction of some chemical reaction, produce some unexpected effects.Ultransonic this effect has caused people's attention.Have the report of ultrasound-enhanced grease and methyl alcohol transesterification reaction both at home and abroad, the ultrasonic device that they adopt is cleaning groove type or horn immerseable, and the process of preparation fatty acid methyl ester all is an intermittent type, since ultrasonic when in liquid, propagating decay very fast, so in scale-up, remain in problems such as ultrasonic device amplification difficulties.
Summary of the invention
The objective of the invention is to, proposing a kind of physical field one ultrasonic field of leaning on promotes grease and low-carbon alcohol to prepare the method for fatty acid ester continuously under base catalysis, solved ultrasonic device amplification difficulty in the batch preparation, and alkali is big as catalyst levels, reaction times is longer, the aftertreatment complexity, problem such as environmental pollution is serious.
The present invention realizes above-mentioned purpose by following steps:
1. alkali is dissolved in low-carbon alcohol, obtains alcoholic solution.
2. alcoholic solution and animal-plant oil metering earlier, be preheated to 35-140 ℃ then, carry out pre-mixing through line mixer again, enter high-shear emulsifying equipment continuously, make between alcoholic solution and the animal-plant oil and fully disperse, enter the phonochemical reaction device more continuously and carry out transesterification reaction, products therefrom obtains thick ester through centrifugation.
3. low-carbon alcohol is removed in thick ester distillation, again with diluted acid or tap water washing 1-3 time, dewaters under 100-105 ℃, vacuum tightness are the condition of 0.01-0.098MPa then, promptly gets fatty acid ester.
1. above-mentioned steps of the present invention can be operate continuously, also can be periodical operation; Step 2., 3. step be operate continuously.
Fig. 1 is seen in technical process of the present invention.
Vegetable and animals oils of the present invention is soybean oil, rapeseed oil, Oleum Gossypii semen, peanut oil, plam oil, lard, butter, Viscotrol C, sunflower seed oil, tung oil.
Alkali of the present invention is sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, yellow soda ash, salt of wormwood.
Low-carbon alcohol of the present invention is methyl alcohol, ethanol, propyl alcohol.
The quality of catalyzer of the present invention is the 0.05-1.1% of oil quality; Alcohol oil mole proportioning 3: 1-25: 1.
Alcoholic solution of the present invention and animal-plant oil are respectively after the liquid meter metering, more respectively by the interchanger continuously pre-heating.
Phonochemical reaction device of the present invention is made up of circular or square stainless steel pipes (1) and the individual ultrasonic transducer (2) that is fixed on pipeline outer wall of 2-500.Phonochemical reaction device structural representation is seen Fig. 2.Ultrasonic transducer (2) can be even, also can be non-uniformly distributed in stainless steel pipes (1) outer wall; Ultrasonic transducer (2) to launch frequency of ultrasonic be 16-300kHz, each ultrasonic transducer (2) launch frequency of ultrasonic can be identical, also can be different.The power of phonochemical reaction device is 100-25000W.During work, material flows into from stainless steel pipes (1) one end continuously, and the other end flows out.
Diluted acid that the present invention adopts is dilute sulphuric acid, dilute hydrochloric acid, dilute phosphoric acid, dilute acetic acid; Diluted acid amount of substance concentration is 0.02-0.5mol/L; The quality of the diluted acid that adopts or tap water be the 0.5-30% of oil quality.
Advantage of the present invention is: 1, raw material sources are extensive, and are renewable; 2, flow process is simple, and the process serialization is easy to amplify, and is easy to control, the reaction conditions gentleness; 3, adopt continuous production, when having solved batch production, ultrasonic device amplifies the problem of difficulty; 4, carry out chemical reaction in the ultrasonic field, be the physical field enhancement method, can significantly reduce catalyst levels, accelerate speed of reaction, reduced waste water, be the environmentally friendly technology process.5, reaction conversion ratio can reach more than 98.5%.
Description of drawings
Fig. 1 is the process flow sheet for preparing fatty acid ester in the ultrasonic field continuously.
Fig. 2 is a phonochemical reaction device structural representation;
Embodiment
In order to make the present invention clear more complete, be described further below in conjunction with embodiment.
Raw material: plam oil, methyl alcohol, sodium hydroxide
1.2 gram sodium hydroxide are dissolved in the 600mL methyl alcohol, obtain alcoholic solution, be stored in the jar, the 2000mL plam oil is stored in another jar, behind under meter, by pump these two kinds of liquid is sent into the interchanger preheating, methanol temperature is 43-45 ℃ after the preheating, and grease is 80-83 ℃.By the line mixer pre-mixing, enter the high-shear emulsifying dispersion machine more then, enter 28kHz more continuously, the phonochemical reaction device of 300W is from the effusive liquid of the reactor the other end, through centrifugal thick ester, after the thick ester distillation for removing methanol, again with the dilute sulphuric acid 40mL of 0.3mol/L wash 1 time, wash 2 times 120mL at every turn from the beginning, then at 105 ℃, vacuum tightness is to dewater under the condition of 0.03MPa, obtains fatty acid methyl ester, i.e. biofuel, after measured, reaction conversion ratio can reach 99.1%.
Raw material: soybean oil, methyl alcohol, sodium hydroxide
1.8 gram sodium hydroxide are dissolved in the 600ml methyl alcohol, obtain alcoholic solution, be stored in the jar, the 2000mL soybean oil is stored in another jar, behind under meter, by pump these two kinds of liquid is sent into the interchanger preheating, methanol temperature is 50-53 ℃ after the preheating, and grease is 92-95 ℃.Then by the line mixer pre-mixing, enter the high-shear emulsifying dispersion machine again, ingoing power is the phonochemical reaction device of 200W continuously again, and this phonochemical reaction utensil has two frequency-25kHz and 50kHz, during work, the ultrasonic wave of these two frequencies acts on liquid simultaneously.From the effusive liquid of the reactor the other end, through centrifugal thick ester, after the thick ester distillation for removing methanol, again with the dilute phosphoric acid 60mL of 0.4mol/L wash 1 time, wash 2 times 120mL at every turn from the beginning, then at 100 ℃, vacuum tightness is to dewater under the condition of 0.02MPa, obtains fatty acid methyl ester, i.e. biofuel, after measured, reaction conversion ratio can reach 98.8%.
Embodiment 3
Raw material: plam oil, ethanol, potassium hydroxide
1.8 gram potassium hydroxide are dissolved in the 1500ml ethanol, obtain alcoholic solution, be stored in the jar, the 2000mL plam oil is stored in another jar, behind under meter, by pump these two kinds of liquid are sent into the interchanger preheating, ethanol, greasy temperature are 75-78 ℃ after the preheating.By the line mixer pre-mixing, enter the high-shear emulsifying dispersion machine more then, enter 40kHz more continuously, the phonochemical reaction device of 200W.From the effusive liquid of the reactor the other end, through centrifugal thick ester, after the thick ester distillation for removing methanol, again with the dilute hydrochloric acid 100mL of 0.3mol/L wash 1 time, wash 2 times from the beginning, each 150mL is then at 100 ℃, vacuum tightness is to dewater under the condition of 0.08MPa, obtain fatty-acid ethyl ester, after measured, reaction conversion ratio can reach 99.0%.
Embodiment 4
Raw material: lard, methyl alcohol, sodium methylate
1.0 gram sodium methylates are dissolved in the 1200mL methyl alcohol, obtain alcoholic solution, be stored in the jar, the preheating of 2000mL lard is in a liquid state it and is stored in afterwards in another jar, behind under meter, by pump these two kinds of liquid are sent into the interchanger preheating, methyl alcohol, greasy temperature are 60-62 ℃ after the preheating.By the line mixer pre-mixing, enter the high-shear emulsifying dispersion machine more then, enter 40kHz more continuously, the phonochemical reaction device of 500W.From the effusive liquid of the reactor the other end, through centrifugal thick ester, after the thick ester distillation for removing methanol, again with washing from the beginning 3 times, each 150mL, then at 100 ℃, vacuum tightness is to dewater under the condition of 0.04MPa, obtain fatty acid methyl ester, after measured, reaction conversion ratio can reach 98.9%.
Claims (6)
1. prepare the method for fatty acid ester in the ultrasonic field continuously, it is characterized in that with the animal-plant oil being raw material, alkali is catalyzer, carries out the reaction of animal-plant oil and low-carbon alcohol in ultrasonic field, prepares fatty acid ester continuously, comprises the steps:
(1) alkali is dissolved in low-carbon alcohol, obtains alcoholic solution;
(2) alcoholic solution and animal-plant oil are earlier by metering, preheating, carry out pre-mixing through line mixer again, enter high-shear emulsifying equipment then continuously, make between alcoholic solution and the animal-plant oil and fully disperse, enter the phonochemical reaction device more continuously and carry out transesterification reaction, products therefrom obtains thick ester through centrifugation;
(3) low-carbon alcohol is removed in thick ester distillation, and with diluted acid or tap water washing, vacuum hydro-extraction then promptly gets fatty acid ester again.
2. prepare the method for fatty acid ester in the ultrasonic field according to claim 1 continuously, it is characterized in that: the animal-plant oil that is adopted is soybean oil, rapeseed oil, Oleum Gossypii semen, peanut oil, plam oil, lard, butter, Viscotrol C, sunflower seed oil, tung oil; The alkali that is adopted is sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, yellow soda ash, salt of wormwood; The low-carbon alcohol that is adopted is methyl alcohol, ethanol, propyl alcohol.
3. prepare the method for fatty acid ester in the ultrasonic field according to claim 1 continuously, it is characterized in that: the quality of catalyzer is the 0.05-1.1% of oil quality; Alcohol oil mole proportioning 3: 1-25: 1; Alcoholic solution and the animal-plant oil temperature after preheating is 35-140 ℃.
4. prepare the method for fatty acid ester in the ultrasonic field according to claim 1 continuously, it is characterized in that: alcoholic solution and animal-plant oil are respectively after the liquid meter metering, respectively by the interchanger continuously pre-heating.
5. prepare continuously the method for fatty acid ester in the ultrasonic field according to claim 1, it is characterized in that: the phonochemical reaction device that is adopted is made up of circular or square stainless steel pipes (1) and the individual ultrasonic transducer (2) that is fixed on pipeline outer wall of 2-500.Ultrasonic transducer (2) can be even, also can be non-uniformly distributed in stainless steel pipes (1) outer wall; Ultrasonic transducer (2) to launch frequency of ultrasonic be 16-300kHz, each ultrasonic transducer (2) launch frequency of ultrasonic can be identical, also can be different.The power of phonochemical reaction device is 100-25000W.During work, material flows into from stainless steel pipes (1) one end continuously, and the other end flows out.
6. prepare the method for fatty acid ester in the ultrasonic field according to claim 1 continuously, it is characterized in that: used diluted acid is dilute sulphuric acid, dilute hydrochloric acid, dilute phosphoric acid, dilute acetic acid; Diluted acid amount of substance concentration is 0.02-0.5mol/L; Diluted acid or tap water washing times are 1-3 time; The quality of used diluted acid or tap water is the 0.5-30% of oil quality; Temperature during dehydration is 100-105 ℃, and vacuum tightness is 0.01-0.098MPa.
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|---|---|---|---|
| CNA2006100366297A CN101108801A (en) | 2006-07-21 | 2006-07-21 | Method for manufacturing fatty acid ester continuously in ultrasonic field |
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|---|---|---|---|
| CNA2006100366297A CN101108801A (en) | 2006-07-21 | 2006-07-21 | Method for manufacturing fatty acid ester continuously in ultrasonic field |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816644A (en) * | 2012-06-26 | 2012-12-12 | 林成原 | Supersonic reaction procedure of biodiesel extraction technology |
| MD4173C1 (en) * | 2011-02-08 | 2013-01-31 | Государственный Университет Молд0 | Process for the production of biodiesel fuel |
| CN102942969A (en) * | 2012-11-29 | 2013-02-27 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by castor oil |
| CN103074162A (en) * | 2013-01-06 | 2013-05-01 | 盐城师范学院 | Method for preparing biodiesel |
| CN105950299A (en) * | 2016-06-28 | 2016-09-21 | 梁红 | Biodiesel |
| CN107255692A (en) * | 2017-08-04 | 2017-10-17 | 中南林业科技大学 | A kind of method that aliphatic acid is directly quickly analyzed using micro tung oil tree benevolence |
| CN108048180A (en) * | 2017-12-06 | 2018-05-18 | 田秋珍 | A kind of preparation method of biodegradation type wire drawing oil |
-
2006
- 2006-07-21 CN CNA2006100366297A patent/CN101108801A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MD4173C1 (en) * | 2011-02-08 | 2013-01-31 | Государственный Университет Молд0 | Process for the production of biodiesel fuel |
| CN102816644A (en) * | 2012-06-26 | 2012-12-12 | 林成原 | Supersonic reaction procedure of biodiesel extraction technology |
| CN102942969A (en) * | 2012-11-29 | 2013-02-27 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel by castor oil |
| CN102942969B (en) * | 2012-11-29 | 2015-07-29 | 青岛福瑞斯生物能源科技开发有限公司 | A kind of method of production of biodiesel from castor oil |
| CN103074162A (en) * | 2013-01-06 | 2013-05-01 | 盐城师范学院 | Method for preparing biodiesel |
| CN105950299A (en) * | 2016-06-28 | 2016-09-21 | 梁红 | Biodiesel |
| CN107255692A (en) * | 2017-08-04 | 2017-10-17 | 中南林业科技大学 | A kind of method that aliphatic acid is directly quickly analyzed using micro tung oil tree benevolence |
| CN108048180A (en) * | 2017-12-06 | 2018-05-18 | 田秋珍 | A kind of preparation method of biodegradation type wire drawing oil |
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