CN101200675A - Pretreatment method of high-acid-value material for preparing biodiesel - Google Patents
Pretreatment method of high-acid-value material for preparing biodiesel Download PDFInfo
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- CN101200675A CN101200675A CNA2007100317613A CN200710031761A CN101200675A CN 101200675 A CN101200675 A CN 101200675A CN A2007100317613 A CNA2007100317613 A CN A2007100317613A CN 200710031761 A CN200710031761 A CN 200710031761A CN 101200675 A CN101200675 A CN 101200675A
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- esterification
- methyl alcohol
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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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- 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
- 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
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- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention relates to a method of the pretreatment of high acid number for preparing biological diesel oil. The method comprises the steps as follows: high-acid-number raw material oil is warmed up, excessive methanol and vitriol mixture is added for the esterification to obtain esterified raw material oil, the acid number of which is less than 1mgKOH/g. Reaction liquid after each time of esterification is processed for the centrifugal separation to obtain an upper layer of methanol and vitriol mixed solution. According to the status of the experiment, vitriolic methanol solution is used to complement the weight loss of the mixed solution each time to be used repeatedly in next pretreatment esterification. The excessive methanol and vitriol mixture is used for disposing the raw material oil, which can finish the esterification of free fatty acid rapidly, reduces the acid number of the raw material and improves the production efficiency. The methanol and concentrated vitriol are used repeatedly, which ensures that consumption of the methanol and the concentrated vitriol averaged to the single time of the pretreatment is reduced greatly and reduces the cost of the pretreatment.
Description
Technical field
The present invention relates to a kind of preprocessing method of raw materials for preparing biofuel, especially relate to a kind of pretreatment process for preparing the high-acid-value material of biofuel.
Technical background
At present, it is higher with the animal-plant oil to be that raw material is made the cost of biofuel.For China, at nearly 5 years, even within 10 years, the preparation raw material of biofuel was mainly various waste cooking oils, sewer oil, acidifying oil and oil foot etc.These waste animal vegetable oils all contain a large amount of free fatty acidies, if adopt traditional base catalysis technology, need elder generation under an acidic catalyst effect, carry out the esterification pre-treatment, otherwise free fatty acids can generate with alkali reaction saponified.The transesterification reaction of base catalysis requires greasy acid number to be preferably lower than 1mgKOH/g.For the higher waste oil of acid number, often need just can make greasy acid number reach requirement through two steps even multistep esterification, so complex operation, big, the long reaction time of methanol consumption amount.Therefore, it is imperative to develop a kind of efficient and cost-effective high-acid-value material pretreatment process.
Summary of the invention
The object of the present invention is to provide a kind of high-acid-value material grease pretreatment process for preparing biofuel, it adopts the mixture of the excessive methyl alcohol and the vitriol oil to handle raw oil material, finish the esterification of free fatty acids rapidly, reduce the raw material acid number, to satisfy the ester exchange process of base catalysis.
For achieving the above object, the technical solution used in the present invention is:
A kind of high-acid-value material pretreatment process for preparing biofuel mainly comprises the steps:
With acid number is the high-acid-value material grease of 4mgKOH/g-30mgKOH/g, the elementary mixed solution that adds the methyl alcohol and the vitriol oil after the preheating carries out esterification, wherein, the weight of the vitriol oil is the 0.8%-1.6% of raw oil material weight in the described elementary mixed solution, the mol ratio of methyl alcohol and the contained free fatty acids of raw oil material is 81-270 in the elementary mixed solution, temperature of reaction is controlled at 60 ℃-75 ℃, and stirring velocity is 300rpm, and the reaction times is 10min-80min; Carry out centrifugation then, obtain acid number less than the esterification feed grease of 1mgKOH/g and centrifugal after methyl alcohol and sulfuric acid mixture liquid.The vitriol oil is that laboratory concentration commonly used is 98.3% and the above vitriol oil.
Further, adding in methyl alcohol after centrifugal and the sulfuric acid mixture liquid and containing mass percent concentration is 0.5%-2% vitriolic methanol solution, and add-on is the bodies lost weight of elementary mixed solution.Compensate to the weight of elementary mixed solution each time according to this method, the repeated use when being re-used as the pre-treatment of high-acid-value material next time.
Preferably, the weight of the vitriol oil is the 1.2%-1.5% of raw oil material weight in the described elementary mixed solution;
The methyl alcohol in the described elementary mixed solution and the mol ratio of the contained free fatty acids of raw oil material are 150-270.
Compared with prior art, the advantage and the effect that have of the present invention is as follows:
(1) the present invention adopts the mixture of the excessive methyl alcohol and the vitriol oil to handle the high-acid-value material grease, can guarantee that the esterification of free fatty acids is finished in a short period of time, reduces the raw material acid number, enhances productivity.
(2) esterification of the present invention obtains the mixed solution of the methyl alcohol and the vitriol oil, with by reusing, makes on average to significantly reduce to pretreated methyl alcohol of single and vitriol oil consumption, reduces the pre-treatment cost.In addition, the various processing parameters in the technical scheme all are to draw on a large amount of experimental basis as component concentration, temperature of reaction, reaction times etc., are the parameter value of reaction process the best.
Description of drawings
Accompanying drawing is an operational flowchart of the present invention.
Embodiment
Embodiment 1
Step (1): adding the 20g acid number in two mouthfuls of flasks of 100ml is the Cortex jatrophae oil of 10.4mgKOH/g, is preheating to 60 ℃.The elementary mixed solution that adds the vitriol oil of methyl alcohol and 98.3% then carries out esterification, wherein, the vitriol oil weight that joins this elementary mixed solution be Cortex jatrophae oil heavy 1.6%, be 0.32g, the mol ratio of methyl alcohol and the contained free fatty acids of Cortex jatrophae oil is 270, (mole number that is methyl alcohol is 1002.9mmol).Temperature of reaction is controlled at 60 ℃, and stirring velocity is 300rpm, and the reaction times is 11min, carries out centrifugation then, obtains the esterification feed grease of acid number less than 1mgKOH/g, and isolating upper strata methyl alcohol and sulfuric acid mixture liquid 18.6g.
Step (2): at isolating upper strata methyl alcohol and sulfuric acid mixture liquid, it is 1% vitriolic methanol solution that adding 1.4g contains mass percent concentration, compensates the weight loss of elementary mixed solution, as the repeated use of esterification next time.
After reusing 20 times, average reaction time is 26 minutes, and average each used sulfuric acid amount is 0.21% (w/w) of Cortex jatrophae oil, and quantity of methyl alcohol is 21% (w/w) of Cortex jatrophae oil.
Embodiment 2
Step (1): adding the 20g acid number in two mouthfuls of flasks of 100ml is the raw oil material (acidifying oil) of 15.8mgKOH/g, is preheating to 70 ℃.The elementary mixed solution of the vitriol oil that adds methyl alcohol and 98.3% then carries out esterification, wherein, join 98.3% vitriol oil weight in this elementary mixed solution and be raw oil material heavy 1.2%, be 0.24g, the mol ratio of methyl alcohol and the contained free fatty acids of raw oil material is 180,1015.7mmol.Temperature of reaction is controlled at 70 ℃, and stirring velocity is 300rpm, and the reaction times is 21min, carries out centrifugation then, obtains the esterification feed grease of acid number less than 1mgKOH/g, and isolating upper strata methyl alcohol and sulfuric acid mixture liquid 18.6g.
Step (2): at isolating upper strata methyl alcohol and sulfuric acid mixture liquid, it is 1% vitriolic methanol solution that adding 1.4g contains mass percent concentration, compensates the weight loss of elementary mixed solution, as the repeated use of esterification next time.
After reusing 20 times, average reaction time is 51 minutes, and average each used sulfuric acid amount is 0.19% (w/w) of raw oil material, and quantity of methyl alcohol is 19% (w/w) of raw oil material.
Embodiment 3
Step (1): adding the 20g acid number in two mouthfuls of flasks of 100ml is the raw oil material (acidifying oil) of 25.5mgKOH/g, is preheating to 75 ℃.The vitriol oil mixed solution that adds methyl alcohol and 98.3% then carries out esterification, wherein, join 98%.3 vitriol oil weight in this elementary mixed solution and be raw oil material heavy 1.5%, be 0.3g, the mol ratio of methyl alcohol and the contained free fatty acids of raw oil material is 250 (mole number that is methyl alcohol is 2276.8mmol).Temperature of reaction is controlled at 75 ℃, and stirring velocity is 300rpm, and the reaction times is 25min, carries out centrifugation then, obtains the esterification feed grease of acid number less than 1mgKOH/g, and isolating upper strata methyl alcohol and sulfuric acid mixture liquid 18.6g.
Step (2): at isolating upper strata methyl alcohol and sulfuric acid mixture liquid, it is 1% vitriolic methanol solution that adding 1.4g contains mass percent concentration, compensates the weight loss of elementary mixed solution, as the repeated use of esterification next time.
After reusing 20 times, average reaction time is 57 minutes, and average each used sulfuric acid amount is 0.21% (w/w) of raw oil material, and quantity of methyl alcohol is 21% (w/w) of raw oil material.
Claims (4)
1. pretreatment process for preparing the high-acid-value material of biofuel, it is characterized in that, mainly comprise the steps: with acid number to be that the elementary mixed solution that adds the methyl alcohol and the vitriol oil after the high-acid-value material grease preheating of 4mgKOH/g-30mgKOH/g carries out esterification, wherein, the weight of the vitriol oil is the 0.8%-1.6% of raw oil material weight in the described elementary mixed solution, the methyl alcohol in the described elementary mixed solution and the mol ratio of the contained free fatty acids of raw oil material are 81-270, temperature of reaction is controlled between 60 ℃-75 ℃, stirring velocity is 300rpm, and the reaction times is 10min-80min; Carry out centrifugation then, obtain acid number less than the esterification feed grease of 1mgKOH/g and centrifugal after methyl alcohol and sulfuric acid mixture liquid.
2. the pretreatment process of the high-acid-value material of preparation biofuel according to claim 1, it is characterized in that, it is 0.5%-2% vitriolic methanol solution that adding in methyl alcohol after centrifugal and the sulfuric acid mixture liquid is contained mass percent concentration, the weight that this methanol solution adds is the weight of the loss of above-mentioned elementary mixed solution, with the weight loss of elementary mixed solution after the compensation esterification.
3. the pretreatment process of the high-acid-value material of preparation biofuel according to claim 1 is characterized in that, the weight of the vitriol oil is the 1.0%-1.5% of raw oil material weight in the described elementary mixed solution.
4. the pretreatment process of the high-acid-value material of preparation biofuel according to claim 1 is characterized in that, the methyl alcohol in the described elementary mixed solution and the mol ratio of the contained free fatty acids of raw oil material are 150-270.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100317613A CN101200675A (en) | 2007-11-28 | 2007-11-28 | Pretreatment method of high-acid-value material for preparing biodiesel |
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| CNA2007100317613A CN101200675A (en) | 2007-11-28 | 2007-11-28 | Pretreatment method of high-acid-value material for preparing biodiesel |
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| CN101200675A true CN101200675A (en) | 2008-06-18 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880603A (en) * | 2010-07-01 | 2010-11-10 | 云南铭惠石化有限公司 | Method for preparing low condensation point biodiesel from high acid value oil |
| CN102191133A (en) * | 2011-04-13 | 2011-09-21 | 云南师范大学 | Process for preparing bio-diesel through fatty acid two-step esterifying method |
| CN102787023A (en) * | 2012-07-28 | 2012-11-21 | 渤海大学 | Pre-processing method for microalgae oil for preparing microalgae |
| CN103013676A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN104862018A (en) * | 2015-04-13 | 2015-08-26 | 内乡县龙翔生物科技有限公司 | Production process of antioxidant biodiesel |
| CN115895786A (en) * | 2022-12-08 | 2023-04-04 | 荆州大地生物工程股份有限公司 | Method for preparing biodiesel from hogwash oil |
-
2007
- 2007-11-28 CN CNA2007100317613A patent/CN101200675A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880603A (en) * | 2010-07-01 | 2010-11-10 | 云南铭惠石化有限公司 | Method for preparing low condensation point biodiesel from high acid value oil |
| CN102191133A (en) * | 2011-04-13 | 2011-09-21 | 云南师范大学 | Process for preparing bio-diesel through fatty acid two-step esterifying method |
| CN103013676A (en) * | 2011-09-20 | 2013-04-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN103013676B (en) * | 2011-09-20 | 2014-12-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN102787023A (en) * | 2012-07-28 | 2012-11-21 | 渤海大学 | Pre-processing method for microalgae oil for preparing microalgae |
| CN104862018A (en) * | 2015-04-13 | 2015-08-26 | 内乡县龙翔生物科技有限公司 | Production process of antioxidant biodiesel |
| CN115895786A (en) * | 2022-12-08 | 2023-04-04 | 荆州大地生物工程股份有限公司 | Method for preparing biodiesel from hogwash oil |
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Open date: 20080618 |