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WO2007065679A2 - Procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles - Google Patents

Procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles Download PDF

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Publication number
WO2007065679A2
WO2007065679A2 PCT/EP2006/011763 EP2006011763W WO2007065679A2 WO 2007065679 A2 WO2007065679 A2 WO 2007065679A2 EP 2006011763 W EP2006011763 W EP 2006011763W WO 2007065679 A2 WO2007065679 A2 WO 2007065679A2
Authority
WO
WIPO (PCT)
Prior art keywords
fame
starch
methanol
glycerol
biodiesel
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2006/011763
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German (de)
English (en)
Other versions
WO2007065679A3 (fr
Inventor
Helmut KÖRBER
Friedemann Pieschel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to EP06829383A priority Critical patent/EP1966355A2/fr
Publication of WO2007065679A2 publication Critical patent/WO2007065679A2/fr
Publication of WO2007065679A3 publication Critical patent/WO2007065679A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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

Definitions

  • the invention relates to a method for removing impurities from fatty acid methyl esters based on natural fats and oils, in particular for the separation of glycerol and traces of alkali metal compounds.
  • FAME Fatty Acid Methyl Ester
  • Glycerin must be removed by a final cleaning and the remaining of its fatty acid esters (mono-, di- and triglycerides) must be avoided by as complete a conversion as possible, because otherwise deposits of carbonization products can occur during the combustion process in the diesel engine.
  • the biodiesel must be dewatered after washing, for example by treatment under vacuum and at temperatures above 100 ° C.
  • the invention has for its object to provide a method with which it is possible to almost completely remove impurities such as glycerol and traces of alkali metal compounds from fatty acid methyl esters based on natural fats and oils with relatively little effort.
  • a first process step a the crude product obtained from the transesterification process is treated with a neutralizing agent which is insoluble in the crude product before being brought into contact with the absorbent. This is necessary because, before the methanol is distilled off, the transesterification catalyst residues NaOH and Na methylate or KOH and K methylate must be rendered ineffective. Otherwise, as is well known, there is a risk that the glycerol residues will slightly reverse the transesterification when the methanol disappears when distilling off.
  • the soda is so much weaker basic that it cannot catalyze the transesterification.
  • Acid anhydrides are also suitable, but they only bind the hydroxides.
  • Carbon dioxide is particularly well suited, since an excess of carbon dioxide remaining in the biodiesel when it comes into contact with water can only give a very weak acid and is not corrosive.
  • Methylate only reacts with carbon dioxide when the exact amount of water required to hydrolyze the methylate is added. The resulting salts can be separated very well and completely by settling alone.
  • the crude product treated with neutralizing agent is freed from methanol by distillation, preferably by means of an evaporator, such as a thin-film evaporator.
  • the resulting methanol is anhydrous and can be immediately returned to the Transesterification process can be traced back, which is economically advantageous.
  • distillation at reduced pressure and correspondingly low condenser temperatures is recommended.
  • glycerin in the raw product is really dissolved and is in the concentration range of about 500 to 1000 mg / kg.
  • the crude product containing glycerol is brought into contact with a phosphorylated and carbamidated starch phosphate, both genuinely dissolved and dispersed glycerol and traces of alkali metals being absorbed by the latter.
  • the anhydroglucose units of the starch phosphate are substituted by phosphate ester groups and carbamide groups, preferably with an average degree of substitution DS of the carbamide groups and the phosphate ester groups of 0.1 to 1.
  • the starch phosphates are preferably used as a granular product. They have a density that is significantly higher than that of glycerin. Due to the difference in density between glycerin and biodiesel, separation takes place by sedimentation even when a high level of saturation with glycerin has already been reached and the density of the swollen particles approaches that of glycerin.
  • the starch phosphates used according to the invention can be used as unpurified raw products which still contain unreacted, excess urea and ammonium phosphates / polyphosphates as impurities. This does not increase the phosphorus and nitrogen content of the biodiesel, as control studies have shown.
  • the absorption is preferably carried out in the filter bed or by means of batch sorption.
  • the required quantities of starch phosphate are 0.1 g to 1.0 g per liter of FAME raw product.
  • all of the starch phosphates specified in the aforementioned publication can be used. Starch phosphates with a high water retention capacity are particularly suitable.
  • the glycerol dispersed in the biodiesel can, of course, also be separated off by simple settling or by means of a centrifuge, as a result of which the consumption of absorbent can be reduced.
  • This phase separation poses hardly any problems in comparison with the water washing known per se, since on the one hand the difference in density is more than twice as large and on the other hand the interfacial activity of possible impurities, in particular of Soaps (alkali salts of fatty acids) do not play a role here.
  • soap solutions in water soap solutions in glycerin do not emulsify oils and fats.
  • the residual content of the substance to be separated depends on the loading of the sorbent.
  • the sorption equilibrium With increasing saturation of the starch phosphate particles with glycerin, the sorption equilibrium naturally approaches the solubility limit of the glycerol in biodiesel. This behavior depends on the synthesis conditions of the carbamidated and phosphorylated starch, in particular the starch used, but also the degree of phosphorylation and carbamidation and the absorption capacity for glycerol achieved in this way.
  • starch phosphates with different degrees of substitution both of the carbamide groups and of the phosphate ester groups, preferably in the range from 0.1 to 1, can be prepared.
  • starting strengths e.g. Pea, wheat, corn or potato starches as well as so-called starch-soluble as well as cold water-soluble starches can be used.
  • Phosphoric acid of any technical quality can be used as the phosphorylating agent, the commercially available 85% strength being particularly suitable. Instead of phosphoric acid, ammonium phosphates, potassium phosphates or sodium phosphates and mixtures of these phosphates can also be used.
  • the reaction takes place under reduced pressure of less than 13.3 kPa.
  • the carbamidation and phosphorylation reaction is preferably carried out under vacuum at temperatures from 90 to 140 ° C.
  • starch phosphates At reaction temperatures above 120 0 C starch phosphates are obtained which give particles with a high water retention. These have a high absorption capacity for glycerin.
  • the starch phosphates according to the invention can thus also be used as glycerol stores.
  • starch phosphate particles are able to absorb several times their own weight of glycerin, a very good cleaning effect is achieved.
  • starch phosphate particles loaded with glycerin are made from biodegradable material, there are several possible uses.
  • the sorbent particles can be disposed of by composting or, if necessary, also used for biogas production. In both cases, phosphorus and nitrogen are formed in non-toxic, plant-available form during the degradation process.
  • a 1 ml sample of the crude product treated with bicarbonate was shaken with 1 ml of distilled water in a test tube and then a pH of 8.0 was determined in the aqueous phase.
  • the raw crude starch phosphate product was broken up into small particles (approx. 2 to 5 mm large granules or grains).
  • Glycerol content 0.01% (according to DIN EN 14105)
  • Alkali content (Na + K): 1.0 mg / kg (according to E DIN EN 14538)
  • Glycerol content 0.01% (according to DIN EN 14105)
  • Alkali content (Na + K): 1.0 mg / kg (according to E DIN EN 14538).
  • the raw crude starch phosphate product was broken up into small particles (approx. 2 to 5 mm granules).
  • the loading of the granulate was calculated from the decrease in the glycerol content of the first 28 samples, from which the maximum glycerol content of

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

Abstract

L'invention concerne un procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles, en particulier pour extraire la glycérine et des traces de composés de métaux alcalins. L'objectif de cette invention est de pallier les inconvénients de la technique actuelle connue en élaborant un procédé permettant d'éliminer presque totalement des impuretés, telles que la glycérine et des traces de composés de métaux alcalins, contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles, d'une manière relativement simple. A cet effet, ledit procédé consiste a) à traiter le produit brut d'esters méthyliques d'acides gras à l'aide d'un agent de neutralisation insoluble dans le produit brut afin d'éliminer le catalyseur de transestérification, b) à éliminer ensuite le méthanol par distillation puis c) à mettre en contact une ou plusieurs fois le produit brut d'esters méthyliques d'acides gras sans méthanol avec des particules de phosphate d'amidon phosphorylées et carbamidées, la glycérine contenue dans le produit brut d'esters méthyliques d'acides gras étant absorbée par les particules de phosphate d'amidon. Les particules de phosphate d'amidon susmentionnées peuvent extraire du biodiesel une quantité de glycérine égale à environ 10 fois leur poids propre et permettent ainsi d'obtenir une teneur résiduelle maximale en glycérine de 0,02 %.
PCT/EP2006/011763 2005-12-08 2006-12-07 Procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles Ceased WO2007065679A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06829383A EP1966355A2 (fr) 2005-12-08 2006-12-07 Procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005059002A DE102005059002A1 (de) 2005-12-08 2005-12-08 Verfahren zur Entfernung von Verunreinigungen aus Fettsäuremethylestern auf Basis natürlicher Fette und Öle
DE102005059002.0 2005-12-08

Publications (2)

Publication Number Publication Date
WO2007065679A2 true WO2007065679A2 (fr) 2007-06-14
WO2007065679A3 WO2007065679A3 (fr) 2007-07-26

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/011763 Ceased WO2007065679A2 (fr) 2005-12-08 2006-12-07 Procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles

Country Status (3)

Country Link
EP (1) EP1966355A2 (fr)
DE (1) DE102005059002A1 (fr)
WO (1) WO2007065679A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009006919A1 (de) * 2009-02-02 2010-08-05 Lurgi Gmbh Verfahren und Anlage zur Herstellung von Fettsäurealkylestern
DE102009006922A1 (de) * 2009-02-02 2010-08-05 Lurgi Gmbh Verfahren, Anlage und Mittel zur Vermeidung von Sterolglycoside enthaltenden Ausfällen bei der Herstellung von Fettsäurealkylestern
MY153091A (en) * 2009-07-14 2014-12-31 Ceramatec Inc Systems and methods for removing catalyst and recovering free carboxylic acids from transesterification reaction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4301686C1 (de) 1993-01-22 1994-03-31 Chem & Pharm Patent Hold Ltd Verfahren zur Herstellung von Fettsäureestern niederer Alkohole
DE19739203A1 (de) 1997-09-08 1999-03-11 Bayer Ag Verfahren zur Reinigung von Esterölen
EP1477549A1 (fr) 2002-02-20 2004-11-17 Revo International Inc. Procede de production d'alkyl ester d'acide gras destine a de l'huile combustible pour diesel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5972057A (en) * 1997-11-11 1999-10-26 Lonford Development Limited Method and apparatus for producing diesel fuel oil from waste edible oil
DE19859123C1 (de) * 1998-12-21 2000-03-16 Eisu Innovative Ges Fuer Techn Stärke-phosphate, Verfahren zu deren Herstellung sowie deren Verwendung
CA2541327C (fr) * 2003-10-09 2012-07-10 The Dallas Group Of America, Inc. Purification de biodiesel a l'aide de matieres adsorbantes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4301686C1 (de) 1993-01-22 1994-03-31 Chem & Pharm Patent Hold Ltd Verfahren zur Herstellung von Fettsäureestern niederer Alkohole
DE19739203A1 (de) 1997-09-08 1999-03-11 Bayer Ag Verfahren zur Reinigung von Esterölen
EP1477549A1 (fr) 2002-02-20 2004-11-17 Revo International Inc. Procede de production d'alkyl ester d'acide gras destine a de l'huile combustible pour diesel

Also Published As

Publication number Publication date
WO2007065679A3 (fr) 2007-07-26
DE102005059002A1 (de) 2007-06-14
EP1966355A2 (fr) 2008-09-10

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