EP1752522A1 - Process for treatment of fats - Google Patents
Process for treatment of fats Download PDFInfo
- Publication number
- EP1752522A1 EP1752522A1 EP06015943A EP06015943A EP1752522A1 EP 1752522 A1 EP1752522 A1 EP 1752522A1 EP 06015943 A EP06015943 A EP 06015943A EP 06015943 A EP06015943 A EP 06015943A EP 1752522 A1 EP1752522 A1 EP 1752522A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- carbon atoms
- mono
- saturated
- fatty substances
- 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- Withdrawn
Links
Images
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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/06—Refining fats or fatty oils by chemical reaction with bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
-
- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
Definitions
- the invention is in the field of oleochemistry and relates to a novel process for working up fatty substances from esterification and transesterification reactions, especially for refining and deacidification.
- Dry refining uses solid or bound sodium hydroxide. If necessary, soaps are produced as neutralization products in these processes. In contrast, in the wet refining, aqueous caustic soda solution or crystal soda solution and a large amount of water are added, so that subsequent separation of the water is required. In addition, formed soap must be separated by washing several times from the reaction mixture. Subsequently, the reaction product optionally undergoes deodorization, drying and filtration steps.
- the complex object of the present invention was therefore to develop an improved process for the workup of products from esterification and transesterification reactions for refining and deacidification, which is characterized in comparison to the prior art in that the number of purification steps and the amount of Wastewater is significantly reduced. At the same time, the loss due to product saponification should also be reduced. Finally, the process should be designed so that catalyst contaminants, e.g. Sulfate anions and mono- or polyvalent metal cations can be removed.
- catalyst contaminants e.g. Sulfate anions and mono- or polyvalent metal cations
- the invention relates to a process for working up fatty substances from esterification and transesterification reactions, which is characterized in that they are treated with ion exchangers.
- the advantage of the method according to the invention is in particular that the free acid is bound directly to the ion exchanger by the use of anion exchangers.
- water is formed only in stoichiometric amounts, which is then removed in the drying process.
- the complex washing out of the soap and the filtration omitted at the same time the amount of wastewater is significantly reduced. Due to the lower basicity of the anion exchangers and the milder reaction temperatures, there is less loss due to product saponification in comparison to conventional wet refining. At the same time, other interfering anions, especially the undesirable sulfates, are removed.
- monovalent or polyvalent metal cations can be separated by series connection of cation and anion exchange steps. The regeneration of the ion exchanger is possible as in aqueous ion exchanger systems with dilute aqueous sodium or potassium hydroxide solution and dilute hydrochloric or sulfuric acid.
- esterification or transesterification products is not very critical to the process according to the invention.
- glycerides of the formula (I) can be worked up as fatty substances, in the R 1 CO for a saturated and mono- or polyunsaturated acyl radical having 2 to 22 carbon atoms, and R 2 and R 3 are independently hydrogen or saturated and mono- or polyunsaturated acyl radicals having 2 to 22, preferably 6 to 18 carbon atoms stand.
- Typical examples are vegetable oils such as coconut oil, palm oil, palm kernel oil, olive oil, sunflower oil, thistle oil, rapeseed oil, almond oil and the like.
- esters of monocarboxylic acids of the formula (II) can also be used as fatty substances, R 4 COO-R 5 (II) wherein R 4 CO is a saturated and mono- or polyunsaturated acyl radical having 2 to 22, preferably 6 to 18 and in particular 12 to 14 carbon atoms and R 5 is a saturated or mono- or polyunsaturated, optionally substituted alk (en) ylrest with 2 to 22, preferably 6 to 18 and especially 12 to 14 carbon atoms or the rest of a (poly) alkylene glycol, especially of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol.
- Typical examples are wax esters based on fatty acids having 6 to 22 and preferably 12 to 18 carbon atoms and corresponding fatty alcohols also having 6 to 22 and preferably 12 to 18 carbon atoms, such as myristyl myristate, myristyl palmitate, stearyl palmitate, stearyl stearate, cetearyl stearate, oleyl oleate and the like.
- suitable starting materials are esters of dicarboxylic acids of the formula (III) , R 6 OOC- (A) n -COOR 7 (III) in the A for a linear or branched alkylene or alkenylene group having 1 to 10 carbon atoms or a phenyl radical, n is 0 or 1, R 6 and R 7 are independently saturated or mono- or polyunsaturated, optionally substituted alk (en) yl radicals with 2 to 22, preferably 6 to 22 and especially 12 to 18 carbon atoms or the radicals of a (poly) alkylene glycol, especially of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol. Typical examples are the stearyl, palmityl or oleyl esters of malonic acid or adipic acid.
- the starting materials may preferably have acid numbers in the range of 0.5 to 10.
- ion exchangers for workup and catalysis in aqueous systems are well known in the art, e.g. Softening or desalination of water, recovery of metal. Otherwise, ion exchangers are used in chromatography. In oleochemistry, ion exchangers are used to purify glycerin (desalting). Another application is the use of cation exchangers for acid catalysis in esterification reactions (eg in the preparation of isopropyl myristate / palmitate). However, they have not yet been considered for the deacidification of esterification and transesterification products.
- anion exchangers or combinations of series-connected anion and cation exchangers, depending on whether only free fatty acids and optionally further interfering anions or, in addition, metal cations are to be separated off.
- ion exchangers based on polymeric resins and other solid matrices having functional groups are suitable (for example zeolites or oxidic ion exchangers).
- anion exchangers are polymeric matrices based on polystyrene-divinylbenzene-dimethylamine, polystyrene-divinylbenzene-trimethylammonium chloride or polyacrylodimethylamine, as are commercially available, for example, from Purolite.
- Typical examples of cation exchangers are polystyrene-divinylbenzene resins having sulfonic acid or carboxyl groups.
- both weakly basic and strongly basic anion exchangers or strongly acidic or weakly acidic cation exchangers are suitable, with particle sizes in the range from 50 to 1000 .mu.m, preferably between 300 and 800 .mu.m, having proved to be particularly advantageous.
- the ion exchangers have a range of application between 0 and 200 ° C, depending on the type; Synthetic resin-based cation exchangers can usually be used up to a maximum of 150 ° C. Synthetic resin based anion exchangers are common can be used up to a maximum of 70 ° C.
- the workup is therefore carried out at temperatures in the range of 0 to 150 ° C, more preferably in the range of 25 to 95 ° C.
- the anion exchangers can be used directly after conditioning. A drying of the anion exchanger and a pretreatment with organic substances are not necessary for use.
- the loading capacity of the anion exchangers in the organic system differs only slightly from that in the aqueous system. The regeneration with dilute sodium hydroxide solution can be repeated several times.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Die Erfindung befindet sich auf dem Gebiet der Oleochemie und betrifft ein neues Verfahren zur Aufarbeitung von Fettstoffen aus Ver- und Umesterungsreaktionen, speziell zur Raffination und Entsäuerung.The invention is in the field of oleochemistry and relates to a novel process for working up fatty substances from esterification and transesterification reactions, especially for refining and deacidification.
Bei der Raffination von Fettstoffen aus Ver- und Umesterungsreaktionen werden freie Säuren durch chemische oder physikalische Methoden entfernt, um die Lagerstabilität und die Produktqualität zu erhöhen. Die einfachste Methode besteht dabei darin, die freien Säuren durch Zugabe von Alkali zu verseifen. In diesem Zusammenhang wird zwischen der Trocken- und Nassraffination unterschieden.In the refining of fatty substances from esterification and transesterification reactions, free acids are removed by chemical or physical methods in order to increase storage stability and product quality. The simplest method is to saponify the free acids by adding alkali. In this context, a distinction is made between dry and wet refining.
Bei der Trockenraffination wird festes oder gebundenes Natriumhydroxid verwendet. Bei diesen Verfahren entstehen gegebenenfalls Seifen als Neutralisationsprodukte. Im Gegensatz dazu wird bei der Nassraffination wässrige Natronlauge oder Kristallsodalösung und eine große Wassermenge zugegeben, so dass anschließend eine Abtrennung des Wassers erforderlich ist. Außerdem muss gebildete Seife durch mehrmaliges Waschen aus dem Reaktionsgemisch abgetrennt werden. Anschließend durchläuft das Reaktionsprodukt gegebenenfalls Desodorierungs-, Trocknungs- und Filtrationsschritte.Dry refining uses solid or bound sodium hydroxide. If necessary, soaps are produced as neutralization products in these processes. In contrast, in the wet refining, aqueous caustic soda solution or crystal soda solution and a large amount of water are added, so that subsequent separation of the water is required. In addition, formed soap must be separated by washing several times from the reaction mixture. Subsequently, the reaction product optionally undergoes deodorization, drying and filtration steps.
Den Verfahren des Stands der Technik haftet der Nachteil an, dass infolge der quantitativen Überführung der Säuren in Seifen aufwendige Reinigungsschritte, insbesondere Wäschen und Filtrationen erforderlich sind, die Zeit und Energie erfordern. Gleichzeitig fallen große Mengen an Abwasser an, die ebenfalls wieder aufwendig gereinigt oder teuer entsorgt werden müssen. Nach Abschluss der Raffination liegen die in den Produkten aus der Ver- oder Umesterung enthaltenen freien Säuren schließlich als Seifen vor.The prior art processes have the disadvantage that, as a result of the quantitative conversion of the acids into soaps, complicated purification steps, in particular washes and filtrations, are required which require time and energy. At the same time, large amounts of wastewater accumulate, which likewise have to be laboriously cleaned or disposed of expensively. After refining, the free acids contained in the products of the transesterification or transesterification are finally present as soaps.
Die komplexe Aufgabe der vorliegenden Erfindung hat demnach darin bestanden, ein verbessertes Verfahren zur Aufarbeitung von Produkten aus Ver- und Umesterungsreaktionen zur Raffination und Entsäuerung zu entwickeln, dass sich im Vergleich zum Stand der Technik dadurch auszeichnet, dass die Zahl der Reinigungsschritte sowie die Menge an Abwasser signifikant vermindert wird. Gleichzeitig soll auch der Verlust durch Produktverseifung reduziert werden. Schließlich sollte das Verfahren so ausgestaltbar sein, dass auch Katalysatorverunreinigungen wie z.B. Sulfatanionen sowie ein- oder mehrwertige Metallkationen entfernt werden können.The complex object of the present invention was therefore to develop an improved process for the workup of products from esterification and transesterification reactions for refining and deacidification, which is characterized in comparison to the prior art in that the number of purification steps and the amount of Wastewater is significantly reduced. At the same time, the loss due to product saponification should also be reduced. Finally, the process should be designed so that catalyst contaminants, e.g. Sulfate anions and mono- or polyvalent metal cations can be removed.
Gegenstand der Erfindung ist ein Verfahren zur Aufarbeitung von Fettstoffen aus Ver- und Umesterungsreaktionen, welches sich dadurch auszeichnet, dass man diese mit Ionenaustauschern behandelt.The invention relates to a process for working up fatty substances from esterification and transesterification reactions, which is characterized in that they are treated with ion exchangers.
Der Vorteil des erfindungsgemäßen Verfahrens besteht insbesondere darin, dass durch die Verwendung von Anionenaustauschern die freie Säure direkt an den Ionenaustauscher gebunden wird. Dabei wird Wasser nur in stöchiometrischen Mengen gebildet, das anschließend im Trocknungsprozess entfernt wird. Insbesondere das aufwendige Auswaschen der Seife und die Filtration entfallen, gleichzeitig wird die Menge an Abwasser signifikant vermindert. Bedingt durch die geringere Basizität der Anionenaustauscher und die milderen Reaktionstemperaturen entsteht im Vergleich zur klassischen Nassraffination auch weniger Verlust durch Produktverseifung. Gleichzeitig werden auch andere störende Anionen, speziell die unerwünschten Sulfate entfernt. Durch Reihenschaltung von Kationen- und Anionenaustauschschritten können zudem auch ein- oder mehrwertige Metallkationen abgetrennt werden. Die Regeneration der Ionenaustauscher ist wie in wässrigen lonenaustauschersystemen mit verdünnter wässriger Natron- oder Kalilauge sowie verdünnter Salz- oder Schwefelsäure möglich.The advantage of the method according to the invention is in particular that the free acid is bound directly to the ion exchanger by the use of anion exchangers. In this case, water is formed only in stoichiometric amounts, which is then removed in the drying process. In particular, the complex washing out of the soap and the filtration omitted, at the same time the amount of wastewater is significantly reduced. Due to the lower basicity of the anion exchangers and the milder reaction temperatures, there is less loss due to product saponification in comparison to conventional wet refining. At the same time, other interfering anions, especially the undesirable sulfates, are removed. In addition, monovalent or polyvalent metal cations can be separated by series connection of cation and anion exchange steps. The regeneration of the ion exchanger is possible as in aqueous ion exchanger systems with dilute aqueous sodium or potassium hydroxide solution and dilute hydrochloric or sulfuric acid.
Die Auswahl der Ver- bzw. Umesterungsprodukte ist für das erfindungsgemäße Verfahren wenig kritisch.The selection of the esterification or transesterification products is not very critical to the process according to the invention.
In einer ersten und bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens können als Fettstoffe Glyceride der Formel (I) aufgearbeitet werden,
In einer alternativen Ausführungsform können als Fettstoffe auch Ester von Monocarbonsäuren der Formel (II) eingesetzt werden,
R4COO-R5 (II)
wobei R4CO für einen gesättigten sowie ein- oder mehrfach ungesättigten Acylrest mit 2 bis 22, vorzugsweise 6 bis 18 und insbesondere 12 bis 14 Kohlenstoffatomen und R5 für einen gesättigten oder ein- oder mehrfach ungesättigten, gegebenenfalls substituierten Alk(en)ylrest mit 2 bis 22, vorzugsweise 6 bis 18 und insbesondere 12 bis 14 Kohlenstoffatomen oder den Rest eines (Poly-)Alkylenglycols, speziell von Ethylenglycol, Diethylenglycol, Propylenglycol oder Dipropylenglycol steht. Typische Beispiele sind Wachsester auf Basis von Fettsäuren mit 6 bis 22 und vorzugsweise 12 bis 18 Kohlenstoffatomen und entsprechenden Fettalkoholen mit ebenfalls 6 bis 22 und vorzugsweise 12 bis 18 Kohlenstoffatomen, wie beispielsweise Myristylmyristat, Myristylpalmitat, Stearylpalmitat, Stearylstearat, Cetearylstearat, Oleyloleat und dergleichen.In an alternative embodiment, esters of monocarboxylic acids of the formula (II) can also be used as fatty substances,
R 4 COO-R 5 (II)
wherein R 4 CO is a saturated and mono- or polyunsaturated acyl radical having 2 to 22, preferably 6 to 18 and in particular 12 to 14 carbon atoms and R 5 is a saturated or mono- or polyunsaturated, optionally substituted alk (en) ylrest with 2 to 22, preferably 6 to 18 and especially 12 to 14 carbon atoms or the rest of a (poly) alkylene glycol, especially of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol. Typical examples are wax esters based on fatty acids having 6 to 22 and preferably 12 to 18 carbon atoms and corresponding fatty alcohols also having 6 to 22 and preferably 12 to 18 carbon atoms, such as myristyl myristate, myristyl palmitate, stearyl palmitate, stearyl stearate, cetearyl stearate, oleyl oleate and the like.
Schließlich kommen als Ausgangsstoffe auch Ester von Dicarbonsäuren der Formel (III) in betracht,
R6OOC-(A)n-COOR7 (III)
in der A für eine lineare oder verzweigte Alkylen- oder Alkenylengruppe mit 1 bis 10 Kohlenstoffatomen oder einen Phenylrest, n für 0 oder 1, R6 und R7 unabhängig voneinander für gesättigte oder ein- oder mehrfach ungesättigte, gegebenenfalls substituierte Alk(en)ylreste mit 2 bis 22, vorzugsweise 6 bis 22 und insbesondere 12 bis 18 Kohlenstoffatomen oder den Reste eines (Poly-)alkylenglycols, speziell von Ethylenglycol, Diethylenglycol, Propylenglycol oder Dipropylenglycol stehen. Typische Beispiele sind die Stearyl-, Palmityl- oder Oleylester der Malonsäure oder Adipinsäure.Finally, suitable starting materials are esters of dicarboxylic acids of the formula (III) ,
R 6 OOC- (A) n -COOR 7 (III)
in the A for a linear or branched alkylene or alkenylene group having 1 to 10 carbon atoms or a phenyl radical, n is 0 or 1, R 6 and R 7 are independently saturated or mono- or polyunsaturated, optionally substituted alk (en) yl radicals with 2 to 22, preferably 6 to 22 and especially 12 to 18 carbon atoms or the radicals of a (poly) alkylene glycol, especially of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol. Typical examples are the stearyl, palmityl or oleyl esters of malonic acid or adipic acid.
In Summe besonders bevorzugt sind synthetische oder natürliche Tri- und Partialglyceride und Alkylester, die nach der Raffination Verwendung in kosmetischen Zubereitungen oder im Nahrungsmittelbereich finden. Bezüglich der Menge an freien Säuren können die Ausgangsstoffe vorzugsweise Säurezahlen im Bereich von 0,5 bis 10 aufweisen.In total, synthetic and natural tri- and partial glycerides and alkyl esters which find use in cosmetic preparations or in the food sector after refining are particularly preferred. With respect to the amount of free acids, the starting materials may preferably have acid numbers in the range of 0.5 to 10.
Die Anwendung von Ionenaustauschern zur Aufarbeitung und Katalyse in wässrigen Systemen ist Stand der Technik, wie z.B. Enthärtung oder Entsalzung von Wasser, Rückgewinnung vom Metall. Ansonsten finden Ionenaustauscher bei der Chromatographie Anwendung. In der Oleochemie werden Ionenaustauscher zur Reinigung von Glycerin (Entsalzung) eingesetzt. Eine weitere Anwendung ist der Einsatz von Kationenaustauschern zur sauren Katalyse bei Veresterungsreaktionen (z. B. bei der Herstellung von Isopropylmyristat/-palmitat). Für die Entsäuerung von Ver- und Umesterungsprodukten, wurden sie indes noch nicht in Betracht gezogen.The use of ion exchangers for workup and catalysis in aqueous systems is well known in the art, e.g. Softening or desalination of water, recovery of metal. Otherwise, ion exchangers are used in chromatography. In oleochemistry, ion exchangers are used to purify glycerin (desalting). Another application is the use of cation exchangers for acid catalysis in esterification reactions (eg in the preparation of isopropyl myristate / palmitate). However, they have not yet been considered for the deacidification of esterification and transesterification products.
Im Sinne des erfindungsgemäßen Verfahrens können Anionenaustauscher oder Kombinationen aus hintereinander geschalteten Anionen- und Kationenaustauschern eingesetzt werden, abhängig davon, ob lediglich freie Fettsäuren sowie gegebenenfalls weitere störende Anionen oder zudem auch Metallkationen abgetrennt werden sollen. Dabei kommen sowohl Ionenaustauscher auf Basis von polymeren Harzen als auch anderen festen Matrizen mit funktionellen Gruppen in Betracht (z.B. Zeolithe oder oxidische Ionenaustauscher). Typische Beispiele für Anionenaustauscher sind polymere Matrizes auf Basis von Polystyroldivinylbenzoldimethylamin, Polystyroldivinylbenzoltrimethylammoniumchlorid oder Polyacrylodimethylamin, wie sie beispielsweise von der Firma Purolite im Handel erhältlich sind. Typische Beispiele für Kationenaustauscher sind Polystyrol-Divinylbenzolharze mit Sulfonsäure- oder Carboxylgruppen.For the purposes of the process according to the invention, it is possible to use anion exchangers or combinations of series-connected anion and cation exchangers, depending on whether only free fatty acids and optionally further interfering anions or, in addition, metal cations are to be separated off. Both ion exchangers based on polymeric resins and other solid matrices having functional groups are suitable (for example zeolites or oxidic ion exchangers). Typical examples of anion exchangers are polymeric matrices based on polystyrene-divinylbenzene-dimethylamine, polystyrene-divinylbenzene-trimethylammonium chloride or polyacrylodimethylamine, as are commercially available, for example, from Purolite. Typical examples of cation exchangers are polystyrene-divinylbenzene resins having sulfonic acid or carboxyl groups.
Im Sinne des erfindungsgemäßen Verfahrens sind sowohl schwach basische wie stark basische Anionenaustauscher bzw. stark saure wie schwach saure Kationenaustauscher geeignet, wobei sich Partikelgrößen im Bereich von 50 bis 1000 µm, bevorzugt zwischen 300 und 800 µm, als besonders vorteilhaft bewährt haben. Die Ionenaustauscher besitzen je nach Typ einen Anwendungsbereich zwischen 0 und 200 °C; Kationenaustauscher auf Kunstharzbasis sind gewöhnlich bis maximal 150 °C einsetzbar. Anionenaustauscher auf Kunstharzbasis sind gewöhnlich bis maximal 70 °C einsetzbar. Üblicherweise wird die Aufarbeitung daher bei Temperaturen im Bereich von 0 bis 150 °C durchgeführt, besonders bevorzugt im Bereich von 25 bis 95 °C.For the purposes of the process according to the invention, both weakly basic and strongly basic anion exchangers or strongly acidic or weakly acidic cation exchangers are suitable, with particle sizes in the range from 50 to 1000 .mu.m, preferably between 300 and 800 .mu.m, having proved to be particularly advantageous. The ion exchangers have a range of application between 0 and 200 ° C, depending on the type; Synthetic resin-based cation exchangers can usually be used up to a maximum of 150 ° C. Synthetic resin based anion exchangers are common can be used up to a maximum of 70 ° C. Usually, the workup is therefore carried out at temperatures in the range of 0 to 150 ° C, more preferably in the range of 25 to 95 ° C.
Bezogen auf die Entfernung von freien Säuren aus den Ver- und Umesterungsprodukten erfolgt die Reaktion nach dem Prinzip von Säure-Base-Reaktionen. Die Säureanionen werden an Anionenaustauscher gebunden, wobei stöchiometrisch Wasser gebildet wird:
RCOOH + RS-OH → RS-OOCR + H2O
Based on the removal of free acids from the esterification and transesterification products, the reaction takes place according to the principle of acid-base reactions. The acid anions are bound to anion exchangers, wherein stoichiometrically water is formed:
RCOOH + RS-OH → RS-OOCR + H 2 O
Zur Entfernung der freien Säure können die Anionenaustauscher direkt nach der Konditionierung eingesetzt werden. Eine Trocknung der Anionenaustauscher und eine Vorbehandlung mit organischen Substanzen sind für den Einsatz nicht notwendig. Die Beladungskapazität der Anionenaustauscher im organischen System unterscheidet sich nur unwesentlich von derjenigen im wässrigen System. Die Regeneration mit verdünnter Natronlauge ist mehrmals wiederholbar.To remove the free acid, the anion exchangers can be used directly after conditioning. A drying of the anion exchanger and a pretreatment with organic substances are not necessary for use. The loading capacity of the anion exchangers in the organic system differs only slightly from that in the aqueous system. The regeneration with dilute sodium hydroxide solution can be repeated several times.
50 g des Rohproduktes Capryl-/Caprinsäuretriglycerid (Myritol® 318, Cognis Deutschland GmbH & Co. KG) wurden mit 2 g Polystyroldivinylbenzoldimethylamin (PFA 100, Purolite) in einem Schüttelkolben gemischt und bei Raumtemperatur ständig gerührt. Die Säurezahl des Gemischs wurde nach Probenahme in bestimmten Zeitabständen gemessen (DGF-Einheitsmethode C-V 2(81)). Die Änderung der Säurezahl mit der Zeit wird in Abbildung 1 gezeigt. Eine Abnahme der Säurezahl ist eindeutig zu erkennen.50 g of the crude product caprylic / capric triglyceride (Myritol ® 318, Cognis Germany GmbH & Co. KG) was mixed with 2 g Polystyroldivinylbenzoldimethylamin (PFA 100, Purolite) in a shake flask and stirred continuously at room temperature. The acid number of the mixture was measured after sampling at specific intervals (DGF unit method CV 2 (81)). The change in acid number over time is shown in Figure 1. A decrease in the acid number is clearly visible.
1290 g des Rohproduktes Capryl-/Caprinsäuretriglycerid (Myritol® 318, Cognis Deutschland GmbH & Co. KG) wurden mit 60 g Polystyroldivinylbenzoltrimethylammoniumchlorid (PPA-400, Purolite) in einem Rührkessel bei 25 °C gerührt. Die Säurezahl des Gemischs wurde nach Probenahme in bestimmten Zeitabständen gemessen (DGF-Einheitsmethode C-V 2(81)). Die Änderung der Säurezahl mit der Zeit ist in Abbildung 4 dargestellt. Eine Abnahme der Säurezahl ist eindeutig zu erkennen.1,290 g of the crude product caprylic / capric triglyceride (Myritol ® 318, Cognis Germany GmbH & Co. KG) were mixed with 60 g Polystyroldivinylbenzoltrimethylammoniumchlorid (PPA-400, Purolite) stirred in a stirred vessel at 25 ° C. The acid number of the mixture was measured after sampling at specific intervals (DGF unit method CV 2 (81)). The change in acid number over time is shown in Figure 4. A decrease in the acid number is clearly visible.
Ein Festbett mit einem Durchmesser von 3 cm, gepackt mit 42 g Polystyroldivinylbenzoltrimethylammoniumchlorid (PPA 400, Purolite) wurde bei Raumtemperatur mit dem Rohprodukt Capryl-/Caprinsäuretriglycerid (Myritol® 318, Cognis Deutschland GmbH & Co. KG), durchströmt. Die Durchbruchskurve des Produktes wurde mit Hilfe der Messung der Säurezahl bestimmt (DGF-Einheitsmethode C-V 2(81)) und ist in Abbildung 3 aufgetragen. Die lineare Beladungsgeschwindigkeit beträgt 1 cm/min.A fixed bed with a diameter of 3 cm, packed with 42 g Polystyroldivinylbenzoltrimethylammoniumchlorid (PPA 400, Purolite) was at room temperature with the crude product caprylic / Caprinsäuretriglycerid (Myritol ® 318, Cognis Germany GmbH & Co. KG), flows through. The breakthrough curve of the product was determined by means of the acid number measurement (DGF unit method CV 2 (81)) and is plotted in FIG. The linear loading speed is 1 cm / min.
50 g des Rohproduktes Isopropylmyristat (Cognis Deutschland GmbH & Co. KG) wurden mit 4 g Polystyroldivinylbenzoltrimethylammoniumchlorid (PFA 400, Purolite) in einem Schüttelkolben gemischt und bei Raumtemperatur gerührt. Das Rohprodukt enthält Schwefelsäure als Katalysator und nicht umgesetzte Fettsäure aus der Veresterungsreaktion. Die Säurezahl des Gemischs wurde nach Probenahme in bestimmten Zeitabständen gemessen (DGF-Einheitsmethode C-V 2(81)). Die Änderung der Säurezahl mit der Zeit wird in Abbildung 4 wiedergegeben. Eine Abnahme der Säurezahl ist eindeutig zu erkennen.50 g of the crude product isopropyl myristate (Cognis Deutschland GmbH & Co. KG) were mixed with 4 g of polystyrene-divinylbenzenetrimethylammonium chloride (PFA 400, Purolite) in a shaking flask and stirred at room temperature. The crude product contains sulfuric acid as catalyst and unreacted fatty acid from the esterification reaction. The acid number of the mixture was measured after sampling at specific time intervals (DGF unit method C-V 2 (81)). The change in acid number over time is shown in Figure 4. A decrease in the acid number is clearly visible.
Claims (10)
R4COO-R5 (II)
wobei R4CO für einen gesättigten sowie ein- oder mehrfach ungesättigten Acylrest mit 2 bis 22 Kohlenstoffatomen und R5 für einen gesättigten oder ein- oder mehrfach ungesättigten, gegebenenfalls substituierten Alk(en)ylrest mit 2 bis 22 Kohlenstoffatomen oder den Rest eines (Poly-)Alkylenglycols steht.Process according to claims 1 or 2, characterized in that esters of monocarboxylic acids of the formula (II) are worked up as fatty substances,
R 4 COO-R 5 (II)
where R 4 CO is a saturated and mono- or polyunsaturated acyl radical having 2 to 22 carbon atoms and R 5 is a saturated or mono- or polyunsaturated, optionally substituted alk (en) yl radical having 2 to 22 carbon atoms or the radical of a (poly -) Alkylenglycols stands.
R6OOC-(A)n-COOR7 (III)
in der A für eine lineare oder verzweigte Alkylen- oder Alkenylengruppe mit 1 bis 10 Kohlenstoffatomen oder einen Phenylrest, n für 0 oder 1, R6 und R7 unabhängig voneinander für gesättigte oder ein- oder mehrfach ungesättigte, gegebenenfalls substituierte Alk(en)ylreste mit 2 bis 22 Kohlenstoffatomen oder den Reste eines (Poly-) alkylenglycols stehen.Process according to claims 1 or 2, characterized in that esters of dicarboxylic acids of the formula (III) are worked up as fatty substances,
R 6 OOC- (A) n -COOR 7 (III)
in the A is a linear or branched alkylene or alkenylene group having 1 to 10 carbon atoms or a phenyl radical, n is 0 or 1, R 6 and R 7 are independently are saturated or mono- or polyunsaturated, optionally substituted alk (en) yl radicals having 2 to 22 carbon atoms or the radicals of a (poly) alkylene glycol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005037707A DE102005037707A1 (en) | 2005-08-10 | 2005-08-10 | Process for the processing of fatty substances |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1752522A1 true EP1752522A1 (en) | 2007-02-14 |
Family
ID=37430106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06015943A Withdrawn EP1752522A1 (en) | 2005-08-10 | 2006-08-01 | Process for treatment of fats |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20070060763A1 (en) |
| EP (1) | EP1752522A1 (en) |
| DE (1) | DE102005037707A1 (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB762362A (en) * | 1953-06-10 | 1956-11-28 | Unilever Ltd | Improvements in the treatment of solutions containing carboxylic acids and derivatives thereof |
| GB934681A (en) * | 1960-10-27 | 1963-08-21 | Armour & Co | Improvements in or relating to the preparation of mixed glycerol esters of fatty and lactic acids |
| DE2743443A1 (en) * | 1976-09-30 | 1978-04-06 | Rohm & Haas | PROCEDURE FOR THE REMOVAL OF ORGANIC LEWIS ACIDS FROM A FLUID NOT MIXABLE WITH WATER |
| JPS54152672A (en) * | 1978-05-24 | 1979-12-01 | Asahi Chem Ind Co Ltd | Preparation of sebacic acid |
| EP0333472A2 (en) * | 1988-03-16 | 1989-09-20 | PALM OIL RESEARCH & DEVELOPMENT BOARD | Production of high concentration tocopherols and tocotrienols from palm oil by-products |
| DE19739203A1 (en) * | 1997-09-08 | 1999-03-11 | Bayer Ag | Separating polyols and ester oil |
| DE20202083U1 (en) * | 2002-02-12 | 2002-07-18 | Kuntschar + Schlüter GmbH Energietechnik, 34466 Wolfhagen | Plant for the esterification of vegetable fats containing glycerin, in particular fatty oils and here in particular used cooking oils with several plant components |
| WO2003040081A1 (en) * | 2001-11-08 | 2003-05-15 | Kovacs Andras | Improvements in or relating to a method for transesterifying vegetable oils |
| WO2004065532A1 (en) * | 2003-01-22 | 2004-08-05 | Cognis Ip Management Gmbh | Reducing the odor of oil components by means of adsorption with polymeric adsorbing agents |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382124B1 (en) * | 1958-07-18 | 1994-10-04 | Rohm & Haas | Process for preparing macroreticular resins, copolymers and products of said process |
| US6316647B1 (en) * | 1993-02-26 | 2001-11-13 | Shiseido Company, Ltd. | Cation-exchanged clay mineral, packing material for chromatography using the same and method of producing the same |
| JP4278910B2 (en) * | 2002-03-13 | 2009-06-17 | 花王株式会社 | Esters manufacturing method |
-
2005
- 2005-08-10 DE DE102005037707A patent/DE102005037707A1/en not_active Withdrawn
-
2006
- 2006-08-01 EP EP06015943A patent/EP1752522A1/en not_active Withdrawn
- 2006-08-09 US US11/463,396 patent/US20070060763A1/en not_active Abandoned
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB762362A (en) * | 1953-06-10 | 1956-11-28 | Unilever Ltd | Improvements in the treatment of solutions containing carboxylic acids and derivatives thereof |
| GB934681A (en) * | 1960-10-27 | 1963-08-21 | Armour & Co | Improvements in or relating to the preparation of mixed glycerol esters of fatty and lactic acids |
| DE2743443A1 (en) * | 1976-09-30 | 1978-04-06 | Rohm & Haas | PROCEDURE FOR THE REMOVAL OF ORGANIC LEWIS ACIDS FROM A FLUID NOT MIXABLE WITH WATER |
| JPS54152672A (en) * | 1978-05-24 | 1979-12-01 | Asahi Chem Ind Co Ltd | Preparation of sebacic acid |
| EP0333472A2 (en) * | 1988-03-16 | 1989-09-20 | PALM OIL RESEARCH & DEVELOPMENT BOARD | Production of high concentration tocopherols and tocotrienols from palm oil by-products |
| DE19739203A1 (en) * | 1997-09-08 | 1999-03-11 | Bayer Ag | Separating polyols and ester oil |
| WO2003040081A1 (en) * | 2001-11-08 | 2003-05-15 | Kovacs Andras | Improvements in or relating to a method for transesterifying vegetable oils |
| DE20202083U1 (en) * | 2002-02-12 | 2002-07-18 | Kuntschar + Schlüter GmbH Energietechnik, 34466 Wolfhagen | Plant for the esterification of vegetable fats containing glycerin, in particular fatty oils and here in particular used cooking oils with several plant components |
| WO2004065532A1 (en) * | 2003-01-22 | 2004-08-05 | Cognis Ip Management Gmbh | Reducing the odor of oil components by means of adsorption with polymeric adsorbing agents |
Non-Patent Citations (2)
| Title |
|---|
| DATABASE FSTA [online] INTERNATIONAL FOOD INFORMATION SERVICE (IFIS), FRANkFURT-MAIN, DE; 1993, DEWETTINCK K ET AL: "Lipase-catalysed interesterification of milkfat: influence on the free fatty acid profile.", XP002409057, Database accession no. 93-1-09-p0001 * |
| MEDEDELINGEN VAN DE FACULTEIT LANDBOUWWETENSCHAPPEN RIJKSUNIVERSITEIT GENT, vol. 57, no. 4B, 1992, LAB. OF FOOD TECH., CHEM. & MICROBIOL., FAC. OF AGRIC. SCI., UNIV. OF GHENT, B-9000 GHENT, BELGIUM, pages 1905 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102005037707A1 (en) | 2007-02-15 |
| US20070060763A1 (en) | 2007-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69312841T2 (en) | Improved process for the production of esters from natural fats | |
| DE60108184T2 (en) | Process for the preparation of fatty acid esters | |
| DE60023710T2 (en) | A one-phase process for the preparation of fatty acid methyl esters from mixtures of triglycerides and fatty acids | |
| BRPI0905878B1 (en) | PROCESS AND SYSTEM FOR PURIFICATION OF FATTY ACID ALKYL ESTERS | |
| EP2175012B1 (en) | Method and device for manufacturing biodiesel | |
| DE102006062417A1 (en) | Producing biodiesel from waste oil by basic transesterification, comprises activating free fatty acids in oil by adding carboxylic acid chloride to give mixed anhydrides and reacting anhydrides with alcohol to fatty acid methyl ester | |
| DE19908978B4 (en) | Process for the preparation of fatty acid methyl esters from triglycerides and fatty acids | |
| EP2358851B1 (en) | Use of methanesulfonic acid for producing fatty acid esters | |
| DE19600025A1 (en) | Preparation of fatty acids with low acid values, useful as precursors for esterification reactions | |
| AT502218A1 (en) | PROCESS FOR PREPARING CARBONIC ACID ALKYL ESTERS | |
| DE602004010596T2 (en) | Process for the preparation of a fatty acid ester | |
| CH698774B1 (en) | A process for the manufacture of a talc product having a high degree of purity. | |
| DE10257525A1 (en) | Process for the production of linear or branched fatty acid esters by heterogeneously catalyzed reactive rectification with a pre-reactor | |
| EP1752522A1 (en) | Process for treatment of fats | |
| DE102010011606B4 (en) | Process for processing biodiesel sludge | |
| AT394571B (en) | Process for the preparation of fatty acid esters of short- chain alcohols | |
| DE102007052065A1 (en) | Continuous process for heterogeneously catalyzed esterification of fatty acids | |
| EP2311929A1 (en) | Method for processing slightly saponifiable crude oil from animal or vegetable sources for further processing into biodiesel | |
| EP2571970B1 (en) | Process for production of biodiesel | |
| DE19626458C2 (en) | Process for the preparation of esters of the low volatility alcohols trismethylolpropane, trismethylolethane and pentaerythritol with native fatty acids | |
| EP2478081B1 (en) | Method for purifying fatty acid alkyl esters highly charged with saponification products | |
| DE102007052064A1 (en) | Reducing content of free fatty acids, useful for biodiesel production, comprises reacting fatty acids with an alcohol under use of ion-exchange-resin catalyst, separating water and alcohol and further reacting fatty acids with alcohol | |
| DE102009006920B4 (en) | A method for preventing sterol glycoside-containing precipitates in the production of fatty acid alkyl esters | |
| DE102006047580A1 (en) | Purifying natural fat and oil-based fatty acid alkyl esters, especially biodiesel, by contacting with sodium-, potassium- and/or ammonium formate as absorbent | |
| AT519685B1 (en) | Process for the preparation of a fatty acid alkyl ester |
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: 20060801 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 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 |
|
| AX | Request for extension of the european patent |
Extension state: AL BA HR MK YU |
|
| 17Q | First examination report despatched |
Effective date: 20070614 |
|
| AKX | Designation fees paid |
Designated state(s): DE ES FR GB IT |
|
| 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: 20071025 |