CN102234567B - Method for lowering acid value of biodiesel - Google Patents
Method for lowering acid value of biodiesel Download PDFInfo
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- CN102234567B CN102234567B CN2011101399157A CN201110139915A CN102234567B CN 102234567 B CN102234567 B CN 102234567B CN 2011101399157 A CN2011101399157 A CN 2011101399157A CN 201110139915 A CN201110139915 A CN 201110139915A CN 102234567 B CN102234567 B CN 102234567B
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- inorganic
- biodiesel
- calcium salt
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- strong alkali
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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
Abstract
The invention discloses a method for lowering the acid value of biodiesel. The method comprises the following steps of: mixing biodiesel containing surplus fatty acid with an inorganic strongly alkaline solution in a reactor for reacting and adding an inorganic calcium salt solution for mixing and reacting; and performing subsequent treatment such as centrifugal water-washing separation, drying, vacuum distillation and the like on mixed liquor. The method has the advantages that: fatty acid is neutralized with alkaline liquor to lower the acid value of biodiesel, and a neutralized alkali metal saponified substance reacts with the inorganic calcium salt solution to be transformed into water-dissoluble calcium soap for separating and removing, so that the alkali metal saponified substance is prevented from being emulsified severely in the water washing process, the acid value of biodiesel is lowered effectively, the quality of finished biodiesel is enhanced, the process difficulty is lowered, the amount of water for water washing is decreased, and meanwhile, the problem of corrosion of high-acid-value biodiesel on using equipment is solved.
Description
Technical field
The present invention relates to a kind of method that reduces acid number of biodiesel.
Background technology
Along with the day that world energy sources uses is becoming tight, the various new forms of energy that searching can substitute fossil energy become one of research task of various countries, the world today.And biofuel has great advantage because of it at aspects such as dynamic performance, environmental-protecting performance and safety performances, receives much concern in recent years, has obtained development faster.The effective constituent of biofuel is mainly fatty ester; The material of selecting during according to production with the grease reaction is different, be divided into fatty acid methyl ester, fatty-acid ethyl ester, and the unnecessary grease in reaction back is doped in the effective constituent of biofuel; Mostly these greases are waste grease; Its difficult quality control causes the product acid number higher, does not meet the BD100 standard.
On the problem that reduces acid number of biodiesel; Normally adopt to add in the alkali lye such as NaOH, KOH and lipid acid reduces acid number; And alkali lye and lipid acid, fatty ester all can react to generate and contain the saponified of sodium, potassium etc., this saponified in the washing refining step in later stage emulsification serious, so the add-on of alkali lye is restricted; Cause acid number of biodiesel still to be difficult to reach requirement, and technology is long, facility investment is big, seriously polluted, production cost is high.
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 method of effective reduction acid number of biodiesel, saponified easy emulsive problem in the time of can overcoming in the alkali with after washing simultaneously improves the biofuel final product quality.
Technical scheme: a kind of method that reduces acid number of biodiesel; This method is: biofuel and the inorganic strong alkali solution that will contain blubber acid add inorganic calcium salt solution hybrid reaction again after the reactor drum hybrid reaction, then with mixed solution through centrifugal washing separates, drying, the processing of vacuum fractionation subsequent step; Wherein said inorganic strong alkali is a kind of in sodium hydroxide, Pottasium Hydroxide, the hydrated barta, and said inorganic calcium salt is a kind of in calcium chloride, nitrocalcite, the Calcium hydrogen carbonate; The mass concentration of said inorganic strong alkali solution, said inorganic calcium salt solution is 3%～12%, and add-on is and contains 0.5%～5% of the sour biofuel quality of blubber; With inorganic strong alkali solution, be 60 ℃～80 ℃ with the temperature of reaction of inorganic calcium salt solution, the reaction times is 5min～50min.
Best, the mass concentration of said inorganic strong alkali solution, said inorganic calcium salt solution is 5%～10%.
Best, the add-on of said inorganic strong alkali solution, said inorganic calcium salt solution is and contains 0.8%～3.5% of the sour biofuel quality of blubber.
Best, with inorganic strong alkali solution, be 10min～30min with reaction times of inorganic calcium salt solution.
Reaction principle of the present invention: lipid acid and inorganic strong alkali solution reaction generate soap and water; The soap that generates generates fatty acid calcium and corresponding inorganic salt with inorganic calcium salt solution generation replacement(metathesis)reaction again, makes full use of the good dispersion of calcium soap and insoluble characteristic in water.
Beneficial effect: compared with prior art; Advantage of the present invention is with reducing acid number of biodiesel with lipid acid in the alkali lye, and the basic metal saponification thing after will neutralize and inorganic calcium salt solution reaction, changes into water-fast calcium soap separation removal; Prevent the serious emulsification of basic metal saponification thing in water washing process; Thereby effectively reduce acid number of biodiesel, improve the biofuel final product quality, reduce technology difficulty; Reduce the washing water consumption, solve the high acid value biofuel simultaneously using the corrosion on Equipment problem.
Embodiment
Below in conjunction with accompanying drawing and 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.
Embodiment 1: in the stirring-type reaction vessel of volume 5L, add the biofuel 2kg that contains blubber acid, its acid number is 2.80mgKOH/g, is warming up to 70 ℃; The adding mass concentration is 10% potassium hydroxide solution 50ml, constant temperature stirring reaction 10min; Add mass concentration again and be 10% ca nitrate soln 70ml, constant temperature stirring reaction 10min; Add after 0.4kg, 75 ℃ water stir 2min, 70 ℃ of insulation sedimentation 30min get upper materials and analyze to such an extent that the product acid number is 0.12mgKOH/g, and acid removal rate is 95.7%.
Embodiment 2: in the stirring-type reaction vessel of volume 5L, add the biofuel 2kg that contains blubber acid, its acid number is 4.68mgKOH/g, is warming up to 70 ℃; The adding mass concentration is 8% potassium hydroxide solution 100ml, constant temperature stirring reaction 10min; Add mass concentration again and be 8% ca nitrate soln 140ml, constant temperature stirring reaction 10min; Add after 0.4kg, 75 ℃ water stir 2min, 70 ℃ of insulation sedimentation 30min get upper materials and analyze to such an extent that the product acid number is 0.18mgKOH/g, and acid removal rate is 96.2%.
Embodiment 3: in the stirring-type reaction vessel of volume 5L, add the biofuel 2kg that contains blubber acid, its acid number is 3.32mgKOH/g, is warming up to 70 ℃; The adding mass concentration is 10% sodium hydroxide solution 55ml, constant temperature stirring reaction 10min; Add mass concentration again and be 10% calcium chloride solution 80ml, constant temperature stirring reaction 10min; Add after 0.4kg, 75 ℃ water stir 2min, 70 ℃ of insulation sedimentation 30min get upper materials and analyze to such an extent that the product acid number is 0.22mgKOH/g, and acid removal rate is 93.4%.
Embodiment 4: in the stirring-type reaction vessel of volume 5L, add the biofuel 2kg that contains blubber acid, its acid number is 1.65mgKOH/g, is warming up to 70 ℃; The adding mass concentration is 7% sodium hydroxide solution 72ml, constant temperature stirring reaction 10min; Add mass concentration again and be 7% calcium chloride solution 104ml, constant temperature stirring reaction 10min; Add after 0.4kg, 75 ℃ water stir 2min, 70 ℃ of insulation sedimentation 30min get upper materials and analyze to such an extent that the product acid number is 0.1mgKOH/g, and acid removal rate is 93.9%.
Embodiment 5: in the stirring-type reaction vessel of volume 5L, add the biofuel 2kg that contains blubber acid, its acid number is 2.85mgKOH/g, is warming up to 70 ℃; The adding mass concentration is 7% barium hydroxide solution 124ml, constant temperature stirring reaction 10min; Add mass concentration again and be 7% calcium bicarbonate solution 180ml, constant temperature stirring reaction 10min; Add after 0.4kg, 75 ℃ water stir 2min, 70 ℃ of insulation sedimentation 30min get upper materials and analyze to such an extent that the product acid number is 0.22mgKOH/g, and acid removal rate is 92.3%.
Embodiment 6: in the stirring-type reaction vessel of volume 5L, add the biofuel 2kg that contains blubber acid, its acid number is 1.85mgKOH/g, is warming up to 70 ℃; The adding mass concentration is 10% barium hydroxide solution 35ml, constant temperature stirring reaction 10min; Add mass concentration again and be 10% calcium bicarbonate solution 46ml, constant temperature stirring reaction 10min; Add after 0.4kg, 75 ℃ water stir 2min, 70 ℃ of insulation sedimentation 30min get upper materials and analyze to such an extent that the product acid number is 0.16mgKOH/g, and acid removal rate is 91.4%.
Claims (4)
1. method that reduces acid number of biodiesel; It is characterized in that this method is: biofuel and the inorganic strong alkali solution that will contain blubber acid add inorganic calcium salt solution hybrid reaction again after the reactor drum hybrid reaction, then with mixed solution through centrifugal washing separates, drying, the processing of vacuum fractionation subsequent step; Wherein said inorganic strong alkali is a kind of in sodium hydroxide, Pottasium Hydroxide, the hydrated barta, and said inorganic calcium salt is a kind of in calcium chloride, nitrocalcite, the Calcium hydrogen carbonate; The mass concentration of said inorganic strong alkali solution, said inorganic calcium salt solution is 3%～12%, and add-on is and contains 0.5%～5% of the sour biofuel quality of blubber; With inorganic strong alkali solution, be 60 ℃～80 ℃ with the temperature of reaction of inorganic calcium salt solution, the reaction times is 5min～50min.
2. the method for reduction acid number of biodiesel according to claim 1 is characterized in that: the mass concentration of said inorganic strong alkali solution, said inorganic calcium salt solution is 5%～10%.
3. the method for reduction acid number of biodiesel according to claim 1 is characterized in that: the add-on of said inorganic strong alkali solution, said inorganic calcium salt solution is and contains 0.8%～3.5% of the sour biofuel quality of blubber.
4. the method for reduction acid number of biodiesel according to claim 1 is characterized in that: with inorganic strong alkali solution, be 10min～30min with reaction times of inorganic calcium salt solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011101399157A CN102234567B (en) | 2011-05-27 | 2011-05-27 | Method for lowering acid value of biodiesel |
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| CN2011101399157A CN102234567B (en) | 2011-05-27 | 2011-05-27 | Method for lowering acid value of biodiesel |
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| CN102234567A CN102234567A (en) | 2011-11-09 |
| CN102234567B true CN102234567B (en) | 2012-11-21 |
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| CN102579543B (en) * | 2012-03-16 | 2013-12-18 | 郭建喜 | Method for extracting Traditional Chinese medicine active ingredients of marigold inflorescences |
| CN103421548A (en) * | 2012-05-14 | 2013-12-04 | 陕西德融新能源股份有限公司 | Preparation technology of biodiesel produced from non refined grease |
| CN103981026A (en) * | 2014-06-12 | 2014-08-13 | 深圳市新宝环保能源科技有限公司 | Method for lowering acid value of biodiesel |
| JP2021014476A (en) * | 2017-10-19 | 2021-02-12 | 公立大学法人大阪府立大学 | Free fatty acid and effective use method for fat including oil content |
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| CN100548963C (en) * | 2005-07-26 | 2009-10-14 | 中国石油化工股份有限公司 | A kind of method for preparing fatty acid ester |
| CN101200674B (en) * | 2006-12-13 | 2010-05-19 | 中国石油化工股份有限公司 | Method for reducing fatty acid value |
| CN101067090B (en) * | 2007-06-08 | 2010-05-19 | 西北大学 | Solid catalysis for preparing biodiesel oil |
| CN101067091B (en) * | 2007-06-08 | 2010-05-26 | 清华大学 | Solid catalysis process of preparing biodiesel oil continuously with high acid value material |
| WO2010126839A2 (en) * | 2009-05-01 | 2010-11-04 | Parma Laboratories Inc. | Processed feeds, foods and biofuels and methods of making and using them |
| CN101993776B (en) * | 2009-08-27 | 2014-07-02 | 中国石油化工股份有限公司 | Method for deacidifying biodiesel |
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Effective date of registration: 20160206 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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