EP1966355A2 - 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

Info

Publication number
EP1966355A2
EP1966355A2 EP06829383A EP06829383A EP1966355A2 EP 1966355 A2 EP1966355 A2 EP 1966355A2 EP 06829383 A EP06829383 A EP 06829383A EP 06829383 A EP06829383 A EP 06829383A EP 1966355 A2 EP1966355 A2 EP 1966355A2
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP06829383A
Other languages
German (de)
English (en)
Inventor
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
Publication of EP1966355A2 publication Critical patent/EP1966355A2/fr
Withdrawn legal-status Critical Current

Links

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

Landscapes

  • 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 %.
EP06829383A 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 Withdrawn EP1966355A2 (fr)

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
PCT/EP2006/011763 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

Publications (1)

Publication Number Publication Date
EP1966355A2 true EP1966355A2 (fr) 2008-09-10

Family

ID=38015387

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06829383A Withdrawn 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

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
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
DE102009006919A1 (de) * 2009-02-02 2010-08-05 Lurgi Gmbh Verfahren und Anlage zur Herstellung von Fettsäurealkylestern
WO2011008847A2 (fr) * 2009-07-14 2011-01-20 Ceramatec, Inc. Systèmes et procédés permettant l’élimination d’un catalyseur et la récupération d’acides carboxyliques libres à partir d’une réaction de transestérification

Family Cites Families (6)

* 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
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
US7626047B2 (en) * 2002-02-20 2009-12-01 Revo International Inc. Method of producing fatty acid alkyl ester for diesel fuel oil
AU2004282511B2 (en) * 2003-10-09 2007-08-09 The Dallas Group Of America, Inc. Purification of biodiesel with adsorbent materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007065679A2 *

Also Published As

Publication number Publication date
DE102005059002A1 (de) 2007-06-14
WO2007065679A3 (fr) 2007-07-26
WO2007065679A2 (fr) 2007-06-14

Similar Documents

Publication Publication Date Title
DE60108184T2 (de) Verfahren zur Herstellung von Fettsäureestern
DE69701014T2 (de) Verfahren zur Herstellung von Fettsäureäthylestern
EP1542960A1 (fr) Procede et dispositif pour produire du biodiesel
EP1972679B1 (fr) Utilisation de 2,6-di-tert.-butyl-p-krésol pour augmenter la stabilité de stockage de biodiesel
DD141271A5 (de) Verfahren zur behandlung von giftigen und gefaehrlichen abfaellen
DE2658909A1 (de) Verfahren und vorrichtung zur tertiaeren behandlung von abwaessern eines anaeroben abbaubehandlungsverfahrens
DE102008063711A1 (de) Verfahren zum Erzeugen von Biodiesel mit verbesserten Filtrationseigenschaften und entsprechend erzeugter Biodiesel
AT502218B1 (de) Verfahren zur herstellung von carbonsäurealkylestern
DE69012777T2 (de) Herstellungsverfahren für unlösliches Tannin und seine Anwendung zur Abwasserreinigung und Adsorption.
EP0017741B1 (fr) Procédé pour convertir les déchets de la purification de l'acide phosphorique par extraction en un résidu solide pouvant être mis en terril
DE1642443A1 (de) Verfahren zur Entsalzung von Kesselspeisewasser
EP1966355A2 (fr) Procédé pour éliminer des impuretés contenues dans des esters méthyliques d'acides gras à base d'huiles et de graisses naturelles
EP0708683B1 (fr) Procede de preparation de sorbants a partir de matieres premieres contenant des polysaccharides, sorbants et leur utilisation
DE2050406B2 (de) Verfahren zur reinigung von technischer phosporsaeure
DE102010011606B4 (de) Verfahren zur Aufarbeitung von Biodieselschlamm
WO2004053036A1 (fr) Procede pour ameliorer la stabilite au cours du temps de biodiesel
EP2571970B1 (fr) Procédé de fabrication de biodiesel
DE10252714B4 (de) Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel sowie die Verwendung von Mono- oder Dialkylhydroxytoluol zur Erhöhung der Oxidationsstabilität von Biodiesel
DE102007061872A1 (de) Verfahren zur Herstellung von Fettsäurealkylestern
DE102006047580A1 (de) Verfahren zur Entfernung von Verunreinigungen aus Fettsäurealkylestern
WO2004083350A1 (fr) Ester alkylique d'acide gras purifie a faible teneur en soufre et son procede de production
DE102009006920B4 (de) Verfahren zur Vermeidung von Sterolglycoside enthaltenden Ausfällungen bei der Herstellung von Fettsäurealkylestern
EP2478081B1 (fr) Procédé pour la purification d'esters alkyliques d'acides gras fortement chargés en produits de saponification
AT398777B (de) Verfahren zur reinigung von rohen pflanzenölestern
DE102008058393A1 (de) Aluminiumoxidhaltige Adsorbentien zur Aufreinigung von Biodiesel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080704

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120703