WO2007068137A1 - Procede pour la preparation de biodiesel - Google Patents

Procede pour la preparation de biodiesel Download PDF

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Publication number
WO2007068137A1
WO2007068137A1 PCT/CN2005/001940 CN2005001940W WO2007068137A1 WO 2007068137 A1 WO2007068137 A1 WO 2007068137A1 CN 2005001940 W CN2005001940 W CN 2005001940W WO 2007068137 A1 WO2007068137 A1 WO 2007068137A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
methanol
acid
acid catalyst
refining
Prior art date
Application number
PCT/CN2005/001940
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English (en)
Chinese (zh)
Inventor
Siu Wai Chiu
Yiu Kwong Wong
Original Assignee
The Chinese University Of Hong Kong
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Chinese University Of Hong Kong filed Critical The Chinese University Of Hong Kong
Priority to PCT/CN2005/001940 priority Critical patent/WO2007068137A1/fr
Publication of WO2007068137A1 publication Critical patent/WO2007068137A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • 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
    • 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

Definitions

  • the invention relates to a method for producing biodiesel by using vegetable oil refining by-product as a raw material, and the special method relates to a method for producing biodiesel by esterification using a physical refining and deodorizing distillate as a raw material.
  • Biodiesel is one of the newly developed alternative energy sources. Compared with petrochemical diesel, it has many advantages, such as biodegradability, low toxicity, pollution-free, low pollutant emissions, etc., which is beneficial to the environment.
  • biodiesel production mainly uses vegetable oil as a raw material, and a few include animal fats, such as Chinese Patent Shenqi No. 98811443.7 and US Patent Application No. 20040074760.
  • biodiesel from vegetable oil is mainly carried out by chemical catalysis or enzymatic transesterification (Hsu et al., 2002; Xu et al., 2003).
  • the free fatty acids (C 14 -C 22 ) and glycerides in vegetable oil are reacted to produce fatty acids.
  • Oxime ester is reacted to produce fatty acids.
  • the product can be extracted and refined by various physical and chemical methods, such as saponification, esterification and distillation, see Chinese Patent Application No. 98811443.7.
  • Another potential biodiesel feedstock is a by-product of vegetable oil refining.
  • Vegetable oil refining methods include chemical refining and physical refining. Compared with chemical refining, physical refining has many advantages such as oil production, short refining time, low equipment and operating costs (Kellens & Greyt, 2000; Zlich, 2000), so it is more and more widely used.
  • steaming method is used for deodorization.
  • the above deodorized distillate usually contains: free fatty acid, glyceride, unsaponifiable
  • DODp deodorized distillate
  • the present invention provides a method of preparing biodiesel from a vegetable oil refining by-product. After conducting research on the preparation of biodiesel with various raw materials, the inventors unexpectedly found that: under acidic and heated conditions, direct reaction with methanol and physical refining deodorized distillate by-product in vegetable oil refining can produce high purity and high purity. Yield of biodiesel. Compared with the prior art, the method is simple and low in cost.
  • the method comprises:
  • the acid catalyst used in the present invention may be any acid catalyst conventionally used for fatty acid esterification, including but not limited to protic acids such as sulfuric acid, nitric acid, phosphoric acid, boric acid and organic sulfonic acids, solid acids such as strongly acidic cation exchange resins and zeolite-type catalysts.
  • protic acids such as sulfuric acid, nitric acid, phosphoric acid, boric acid and organic sulfonic acids
  • solid acids such as strongly acidic cation exchange resins and zeolite-type catalysts.
  • Heteropolyacids such as tungstic acid, phosphotungstic acid, silicic acid, phosphomolybdic acid, and certain salts such as sodium hydrogen sulfate, preferably turmeric acid, more preferably concentrated sulfuric acid having both dehydration effects.
  • the molar ratio of the physical refining deodorized distillate, decyl alcohol and acid catalyst is 1:9-11:0.20, preferably 1:11:0.20, but more excess methanol does not adversely affect the reaction. .
  • the reaction temperature of the step a) is preferably from 65 to 85 ° C, more preferably about 75. C.
  • the reaction time is preferably from 15 to 60 minutes, more preferably about 30 minutes.
  • Step a) The composition of the reaction mixture after esterification is complex and has similar physicochemical properties, so the yield and purity of the conventional separation method are not satisfactory.
  • step b) employs molecular distillation at about 140-145. Perform at the temperature of C.
  • the separation may employ a thin film evaporator at 160-170. C and 1 mm Hg were carried out under reduced pressure.
  • the present invention provides physical refining deodorization distillation for treating by-products in vegetable oil refining Method of matter, including the following steps
  • step a) and step b) are as defined in the first aspect above.
  • step c) is carried out by adding the residue to a polar organic solvent and crystallizing the plant alcohol at low temperatures.
  • the polar organic solvent usable in the present invention includes, but not limited to, an alcohol, a ketone, an ether, an ester, a halogenated hydrocarbon, etc., preferably an alcohol, a ketone, and a mixed solvent thereof, and more preferably a mixed solvent of methanol and acetone.
  • the volume ratio of sterol to acetone in the mixed solvent is preferably about 8:2.
  • the temperature of the crystallization process is preferably not higher than -20 ° C, more preferably about -20. C, the crystallization time is preferably about 16 to 24 hours.
  • the method further comprises the step of extracting vitamin E from the mother liquor after crystallization of the plant sterol of step c).
  • the present invention provides a method of treating a physically refined deodorized distillate by-product in vegetable oil refining, comprising the steps of:
  • step b) is carried out by adding the residue to a polar organic solvent and crystallizing the plant alcohol at a low temperature.
  • polar organic solvent and crystallization conditions are as defined in the second aspect above.
  • the acid catalyst used in step c) may be any acid catalyst conventionally used for fatty acid esterification, including but not limited to protic acids such as sulfuric acid, nitric acid, phosphoric acid, boric acid and organic sulfonic acids, solid acids such as strongly acidic cation exchange resins and The zeolite type catalyst, heteropoly acid such as tungstic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and certain salts such as sodium hydrogen hydride, preferably a protic acid, more preferably concentrated sulfuric acid having a dehydrating action.
  • protic acids such as sulfuric acid, nitric acid, phosphoric acid, boric acid and organic sulfonic acids
  • solid acids such as strongly acidic cation exchange resins
  • the zeolite type catalyst heteropoly acid such as tungstic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and certain salts such as sodium hydrogen hydride, preferably
  • the molar ratio of the fatty acid, methanol and acid catalyst is from 1:9 to 1:0.20, more preferably from about 1:11:0.20.
  • step c) is at 65-85. It is carried out under C, more preferably at about 75. C is carried out.
  • the reaction time is preferably from 15 to 60 minutes, more preferably from about 30 minutes.
  • the method further comprises the step of extracting vitamin E from the mother liquor after crystallization of the plant alcohol of step b).
  • step a) further comprises: 1) reacting the physical refining deodorized distillate with a base to saponify the free fatty acid;
  • the saponified product is reacted with an acid to release a fatty acid. It is limited to argon oxygen, - carbonic acid i: potassium argon oxide and potassium carbonate, and more preferably potassium hydroxide.
  • the acid used in the step 3) is preferably a protic acid, including but not limited to hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc., more preferably 25% sulfuric acid.
  • step a) further comprises:
  • the urea in methanol solution used in step 1) has a urea content of about 0.33 g/mL of methanol.
  • the volume ratio of 75% methanol to hexane in the mixed solvent of the step 3) is preferably 2:1.
  • the method of the present invention is applicable to refinery by-products of vegetable oils from various sources, such as sunflower seeds, rapeseed, cottonseed, palm, rice bran, soybean, canola and peanuts, and has a wide range of raw materials, regardless of geographical and seasonal influences.
  • the method of the present invention uses a physical refining and deodorizing distillate which is by-produced in vegetable oil refining as a raw material, and can obtain products of high yield and high purity such as biodiesel and phytol, which are significantly reduced in cost compared with the prior art. - detailed description
  • the free fatty acid of the physical refining deodorized distillate is converted to fatty acid methyl ester using an excess of methanol under the action of an acid catalyst.
  • the remaining methanol can be distilled and reused, and the acidified wastewater can be neutralized with a base, for example, by neutralizing with potassium carbonate when concentrated sulfuric acid is used to produce K 2 SO 4 fertilizer.
  • the plant alcohol is insoluble in the polar solvent at a low temperature, so the residue obtained by preparing the fatty acid methyl ester in the physical refining deodorized distillate is mixed with the polar solvent, and is allowed to stand at a low temperature, and the plant alcohol crystallizes and can be separated by filtration ( Kircher & Rosenstein, 1973; Lin & Koseoglu, 2003; Pan et al., 2005).
  • the alcoholic part contains different concentrations of natural vitamin E and shark Alkene can be recycled as needed. Saponification reaction
  • the saponification reaction refers to a reaction in which a fat or oil forms a fatty acid metal salt under the action of a base, including hydrolysis of an ester and neutralization of a fatty acid.
  • Bases commonly used in the saponification reaction include alkali metal hydroxides and alkali metal carbonates, particularly hydroxides and carbonates of Na and K.
  • Urea-fatty acid complex
  • Urea combines with carbohydrates, fatty acids, and fatty acid methyl esters to form a water-insoluble crystalline complex (Hayes et al., 2000; U.S. Patent No. 5,078,920).
  • cyclic compounds, aromatic compounds such as plant alcohols and the like do not crystallize with urea.
  • the raw material physical refining deodorized distillate contains 70-90% of free fatty acid and is acidic, while the product fatty acid methyl ester is insoluble in water, so the pH of the reaction mixture rises during the esterification process.
  • the efficiency of the esterification reaction can be monitored and estimated in real time using pH reagents.
  • the physical refining deodorized distillate is a brown solid at room temperature
  • the fatty acid methyl ester of the present invention is a yellow clarified liquid, so that the transmittance can be used as a coarse indicator of the progress of the reaction.
  • the acid value (acid no.) can also be determined by conventional titration (e.g., ASTM D664) to calculate the efficiency of the esterification reaction and determine the end point of the reaction.
  • Randomly sampled samples can be analyzed by gas chromatography mass spectrometry (GC-MS) to verify concentration and purity.
  • the content of fatty acid methyl esters in biodiesel is typically greater than 98% to meet biodiesel standards in the area of use (eg, US).
  • the product phytosterol is a white powdery crystal which can also be analyzed by gas chromatography mass spectrometry (GC-MS) to determine the yield and purity.
  • GC-MS gas chromatography mass spectrometry
  • the physical refined deodorized distillate used in the following examples is supplied by Hexing Edible Oil Refinery (Address: Hexing Building, No. 9 Pingtang East Street, Tangren New Village, Yuen Long, New Territories, Hong Kong).
  • the alcohol 130g Yue, 7g concentrated ⁇ ) acid (98%) with 100g Physical refining deodorization distillate (peanuts, free fatty acids 85%, 10% glycerol, 1.3% phytosterols) were mixed, reacted at 75 ° C for 30 minutes
  • the solution is layered.
  • the lower liquid layer was separated at a feed rate of 1 ml/min, a rotating piece speed of 10-20 rpm, and a distillation temperature of 140.
  • the obtained reaction mixture was subjected to molecular distillation under the conditions of C to obtain a fatty acid decyl ester having a purity of 98.6% in a yield of 86.1%.
  • the physical and chemical properties of the obtained fatty acid oxime ester were tested according to the biodiesel test method of ASTM D6751. The results are shown in Table 2.
  • hexane extract was at 45 °C. C distillation, recovery of hexane, the residue was added to 350 mL of a mixed solvent of methanol and acetone (8:2), and allowed to stand at minus 20 degrees Celsius for 24 hours to separate the precipitated phytosterol crystals with a purity of 96% and a yield of 77%. .
  • Example 3
  • urea 150 g was dissolved in 450 mL of methanol, and then 100 g of physical refining deodorized distillate (soybean, free fatty acid 80%, glyceride 9.5%, phytosterol 1.8%) was poured and stirred at 65 ° C for 30 minutes. The reaction mixture was then brought to -20. C was allowed to stand for three hours to precipitate a crystal of the urea-fatty acid complex. The crystals were filtered and washed with 200 mL of hexane. 50 mL of water was poured into the filtrate, and the filtrate was layered. The upper organic layer was separated and was at 45 °C.
  • the hexane was recovered by distillation, and the residue was added to 350 mL of a mixed solvent of methanol and acetone (8:2) at -20. C is allowed to stand for 24 hours. The precipitated phytosterol crystals were separated to a purity of 95.5% and a yield of 73%.
  • the urea-fatty acid crystals were dissolved in a mixture of 600 mL of hexane and 75% methanol (1:2), and the layers were allowed to stand at room temperature.
  • the lower layer is a diluted sterol layer, which can be distilled to recover sterol, while the urea crystals precipitate.
  • the upper organic layer is at 40. After distilling hexane from C, the residue was charged with 120 mL of methanol and 5.6 g of concentrated sulfuric acid (98%) at 75. C reacts for half an hour.
  • the fatty acid methyl ester was isolated to give 74.8 g, purity 98%, yield 77.2%. Comparison of various indexes of fatty acid methyl ester products of the invention with American standards

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Steroid Compounds (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé pour la préparation de biodiesel contenant un ester méthylique d'acide gras de pureté élevée grâce à l'utilisation d'une distillation désodorisante de raffinage physique qui est un produit secondaire d'une huile végétale comme matière première. Le procédé comprend: a) la réaction de la fraction désodorisante de raffinage physique avec du méthanol de 65 à 85 en présence de catalyseurs acides; b) la séparation d'ester méthylique d'acide gras du mélange obtenu. La présente invention concerne également un procédé pour le traitement de fraction désodorisante de raffinage physique, comprenant l'estérification d'acide gras libre dans la fraction désodorisante de raffinage physique afin d'obtenir un ester méthylique d'acide gras, et l'extraction de phytostérols depuis le résidu exempt d'acide gras. La présente invention réduit le coût grâce à l'utilisation de produit secondaire comme matière première pour la préparation de biodiesel et de phytostérols.
PCT/CN2005/001940 2005-11-17 2005-11-17 Procede pour la preparation de biodiesel WO2007068137A1 (fr)

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PCT/CN2005/001940 WO2007068137A1 (fr) 2005-11-17 2005-11-17 Procede pour la preparation de biodiesel

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747185A (zh) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 从生物柴油中分离饱和脂肪酸甲酯的方法
EP3208257A4 (fr) * 2014-10-17 2018-07-25 Zhejiang Medicine Co., Ltd. Xinchang Pharmaceutical Factory Procédé de recyclage d'urée dans un procédé à produit d'addition d'urée
CN111534382A (zh) * 2020-04-07 2020-08-14 宜春大海龟生命科学有限公司 一种用于植物油脱臭馏出物酯化反应的优化方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074217A (zh) * 1993-01-14 1993-07-14 清华大学 从植物油精炼副产物中提取维生素e和甾醇的新工艺
US6768015B1 (en) * 2003-05-16 2004-07-27 Stepan Company Method of making alkyl esters using pressure
CN1556174A (zh) * 2003-12-31 2004-12-22 中国农业科学院油料作物研究所 利用高酸值动植物油脂生产生物柴油的方法
CN1693472A (zh) * 2005-03-24 2005-11-09 合肥工业大学 植物油脱臭馏出物中维生素e、甾醇及甾醇酯分离新工艺

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074217A (zh) * 1993-01-14 1993-07-14 清华大学 从植物油精炼副产物中提取维生素e和甾醇的新工艺
US6768015B1 (en) * 2003-05-16 2004-07-27 Stepan Company Method of making alkyl esters using pressure
CN1556174A (zh) * 2003-12-31 2004-12-22 中国农业科学院油料作物研究所 利用高酸值动植物油脂生产生物柴油的方法
CN1693472A (zh) * 2005-03-24 2005-11-09 合肥工业大学 植物油脱臭馏出物中维生素e、甾醇及甾醇酯分离新工艺

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747185A (zh) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 从生物柴油中分离饱和脂肪酸甲酯的方法
EP3208257A4 (fr) * 2014-10-17 2018-07-25 Zhejiang Medicine Co., Ltd. Xinchang Pharmaceutical Factory Procédé de recyclage d'urée dans un procédé à produit d'addition d'urée
CN111534382A (zh) * 2020-04-07 2020-08-14 宜春大海龟生命科学有限公司 一种用于植物油脱臭馏出物酯化反应的优化方法

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