EP1314775A1 - Process for the deacidification of natural fats and oils - Google Patents
Process for the deacidification of natural fats and oils Download PDFInfo
- Publication number
- EP1314775A1 EP1314775A1 EP02025227A EP02025227A EP1314775A1 EP 1314775 A1 EP1314775 A1 EP 1314775A1 EP 02025227 A EP02025227 A EP 02025227A EP 02025227 A EP02025227 A EP 02025227A EP 1314775 A1 EP1314775 A1 EP 1314775A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- enzymes
- oils
- oil
- alcohols
- deacidification
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003921 oil Substances 0.000 title claims abstract description 16
- 239000003925 fat Substances 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 23
- 108090000790 Enzymes Proteins 0.000 claims abstract description 16
- 102000004190 Enzymes Human genes 0.000 claims abstract description 16
- 150000001298 alcohols Chemical class 0.000 claims abstract description 9
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000019198 oils Nutrition 0.000 claims description 14
- 235000019197 fats Nutrition 0.000 claims description 13
- 239000000969 carrier Substances 0.000 claims description 6
- 235000021588 free fatty acids Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003240 coconut oil Substances 0.000 claims description 4
- 235000019864 coconut oil Nutrition 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004367 Lipase Substances 0.000 claims description 3
- 102000004882 Lipase Human genes 0.000 claims description 3
- 108090001060 Lipase Proteins 0.000 claims description 3
- 235000019421 lipase Nutrition 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003346 palm kernel oil Substances 0.000 claims description 2
- 235000019865 palm kernel oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 230000002255 enzymatic effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 238000011138 biotechnological process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
-
- 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
- C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead
Abstract
Description
Die Erfindung befindet sich auf dem Gebiet der oleochemischen Grundstoffe und betrifft ein biotechnologisches Verfahren zur Entsäuerung von Fetten und Ölen.The invention is in the field of oleochemical raw materials and relates to a biotechnological process for deacidifying fats and oils.
Natürliche Fette und Öle enthalten infolge enzymatischer Zersetzungsprozesse, die unmittelbar nach dem Ernten der Ölfrüchte einsetzen, stets einen Anteil an freien Fettsäuren, der in der Literatur als FFA-Wert ("Free Fatty Acids") oder Säurezahl bezeichnet wird. Der FFA-Wert gilt als eines der Qualitätskriterien für Fette und Öle, da kleine Säurezahlen für vergleichsweise reine und nicht etwa alte, ranzige Ware steht. Für die weitere Verarbeitung der Fette und Öle sind darin enthaltene Fettsäuren unerwünscht, da diese mit basischen Katalysatoren, wie sie beispielsweise in der Umesterung eingesetzt werden, Seifen bilden, welche nicht weiter reagieren und später als Abfallstoffe entsorgt werden müssen. Man umgeht dieses Problem in der Praxis durch eine sogenannte "Entsäuerung", bei der es sich um eine vorgelagerte Veresterung vorzugsweise mit Methanol handelt. Auf diese Weise wird die Säurezahl praktisch auf Null gebracht, während die resultierenden Methylester in der weiteren Verarbeitung der Fette und Öle analog den Glycerinester abreagieren und somit nicht stören.Natural fats and oils contain, due to enzymatic decomposition processes, the immediate use after harvesting the oil fruits, always a proportion of free fatty acids, which is referred to in the literature as the FFA value ("Free Fatty Acids") or acid number becomes. The FFA value is one of the quality criteria for fats and oils because of its low acid numbers stands for comparatively pure and not old, rancid goods. For the further Processing of the fats and oils are undesirable because they contain fatty acids these with basic catalysts, such as those used in transesterification will form soaps that do not react any further and are later disposed of as waste Need to become. This problem is avoided in practice by so-called "deacidification", which is an upstream esterification, preferably with methanol is. In this way, the acid number is practically brought to zero, while the resulting methyl ester in the further processing of fats and oils analogous to React glycerol esters and do not interfere.
Üblicherweise wird diese Vorveresterung mit heterogenen Katalysatoren, beispielsweise Zink oder Zinnverbindungen durchgeführt, wie sie etwa in den Druckschriften DE 19956599 A1, DE 19600025 C2 und EP 0192035 B1 beschrieben werden. Wie schon oben erläutert, ist das Verfahren im Hinblick auf die angestrebte Säurezahlerniedrigung durchaus effektiv, von Nachteil ist aber, dass die Katalysatoren mit hohem technischen Aufwand abgetrennt werden müssen, in der Regel nicht zu regenerieren sind und damit den Prozess von der ökonomischen Seite her betrachtet erheblich belasten. Des weiteren ist ein kontinuierlicher Betrieb nicht möglich und vielfach beobachtet man, dass die Methylester zurückgespalten werden, d.h. die Erniedrigung der Säurezahl nicht von Dauer ist. This pre-esterification is usually carried out using heterogeneous catalysts, for example zinc or tin compounds, as are described, for example, in documents DE 19956599 A1, DE 19600025 C2 and EP 0192035 B1 . As already explained above, the process is quite effective with regard to the target acid number reduction, but the disadvantage is that the catalysts have to be separated with a high level of technical complexity, generally cannot be regenerated, and the process is therefore considered from an economic point of view significantly burden. Furthermore, continuous operation is not possible and it is frequently observed that the methyl esters are split back, ie the reduction in the acid number is not permanent.
Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, ein verbessertes kontinuierliches Verfahren zur dauerhaften Entsäuerung von Fetten und Ölen zur Verfügung zu stellen, welches sich gleichzeitig dadurch auszeichnet, dass eine dauerhafte Säurezahlsenkung bis unter einen Wert von 1 erreicht wird, hohe Durchsätze erzielt werden und die Katalysatorkosten durch Wiederverwertung gegenüber dem Stand der Technik nachhaltig gesenkt werdenThe object of the present invention was therefore an improved one continuous process for permanent deacidification of fats and oils available to provide, which is also characterized by the fact that a permanent Lowering the acid number to below a value of 1 achieves high throughputs and the catalyst costs by recycling compared to the state of the Technology can be reduced sustainably
Gegenstand der Erfindung sind Verfahren zur Entsäuerung von natürlichen Fetten und Ölen, bei dem man Glyceride mit Säurezahlen im Bereich von 5 bis 20 mit niederen Alkoholen behandelt und so freie Fettsäuren in Ester überführt, das sich dadurch auszeichnet, dass man die Reaktion in Gegenwart von Enzymen durchführt, die auf Trägern immobilisiert sind, die einen Durchmesser im Bereich von 1 bis 5 mm aufweisen.The invention relates to processes for deacidifying natural fats and Oils, in which one uses glycerides with acid numbers in the range from 5 to 20 with lower alcohols treated and thus free fatty acids converted into esters, which is characterized by that the reaction is carried out in the presence of enzymes that are on supports are immobilized, which have a diameter in the range of 1 to 5 mm.
Überraschenderweise wurde gefunden, dass Enzyme, die auf Trägern mit definierten Durchmessern immobilisiert vorliegen, nicht nur vorzüglich für die Vorveresterung von sauren Fetten und Ölen geeignet sind, sondern dabei vor allem auch hohe Strömungsgeschwindigkeiten und damit hohe Durchsätze im kontinuierlichen Betrieb ermöglichen. Die dabei erhaltenen Umsetzungsprodukte weisen vorzugsweise Säurezahlen unter 1 auf.Surprisingly, it was found that enzymes defined on carriers with Diameter immobilized, not only excellent for the pre-esterification of acidic fats and oils are suitable, but above all high flow velocities and thus enable high throughputs in continuous operation. The the reaction products obtained preferably have acid numbers below 1.
Das erfindungsgemäße Verfahren kann grundsätzlich auf alle natürlichen Fette und Öle angewendet werden, die infolge partieller enzymatischer Spaltung über einen Gehalt an freien Fettsäuren verfügen, d.h. eine Säurezahl aufweisen. Insofern ist die Auswahl der Triglyceride wenig kritisch. Dabei ist das Verfahren jedoch vorzugsweise für solche Fette und Öle ge-eignet, die eine vergleichsweise hohe Qualität also niedrige Säurezahl, beispielsweise von maximal 20 und vorzugsweise 10 bis 15 aufweisen. Grundsätzlich lassen sich auch Einsatzstoffe mit höherer Säurezahl auf diese Weise entsäuern, allerdings kann es sein, dass letztlich nur Säurezahlen von 5 bis 10 erreicht werden oder zur weiteren Absenkung hohe Enzymkonzentrationen und/oder lange Reaktionszeiten erforderlich sind. Vorzugsweise kommen als Rohstoffe jedoch Kokosöl, Palmöl, Palmkernöl, Sonnenblumenöl und Rapsöl sowie deren Gemische in Frage, welche Säurezahlen im Bereich von 5 bis 20 und vorzugsweise 10 bis 15 aufweisen. The method according to the invention can in principle be applied to all natural fats and oils are applied, which as a result of partial enzymatic cleavage over a content free fatty acids, i.e. have an acid number. In this respect, the selection of Triglycerides not critical. However, the method is preferred for such fats and oils are suitable which have a comparatively high quality, for example a low acid number have a maximum of 20 and preferably 10 to 15. Basically leave In this way, feedstocks with a higher acid number can also be deacidified it may be that in the end only acid numbers of 5 to 10 are reached or for the further Lowering of high enzyme concentrations and / or long reaction times required are. However, coconut oil, palm oil, palm kernel oil and sunflower oil are preferably used as raw materials and rapeseed oil and their mixtures in question, what acid numbers in the range have from 5 to 20 and preferably 10 to 15.
Das Prinzip der Säurezahlreduktion besteht in einer Veresterung der freien Fettsäuren
mit Hilfe von Alkoholen, vorzugsweise niederen Alkoholen, die der Formel (I) folgen,
in der R für einen linearen oder verzweigten Alkylrest mit 1 bis 4 Kohlenstoffatomen steht. Typische Beispiele sind Ethanol sowie die isomeren Propanole und Butanole, vorzugsweise wird natürlich Methanol eingesetzt. Üblicherweise werden die Alkohole dabei in Mengen von 1 bis 10 und vorzugsweise 2 bis 5 Gew.-% - bezogen auf die Triglyceridmenge - eingesetzt.in the R for a linear or branched alkyl radical having 1 to 4 carbon atoms stands. Typical examples are ethanol and the isomeric propanols and butanols, preferably methanol is of course used. The alcohols are usually used in amounts of 1 to 10 and preferably 2 to 5% by weight, based on the amount of triglyceride - used.
Im Sinne des erfindungsgemäßen Verfahrens kommen als Enzyme vorzugsweise Lipasen in Betracht. Typische Beispiele für geeignete Lipasen sind die Handelsprodukte Novozym 388 L, Novozym SP 525 L, Lipozym TL 100 und Amano G. Die Enzyme werden in der Regel als verdünnte Suspensionen oder wässrige Konzentrate eingesetzt, wobei die Einsatzkonzentration in der Regel 0,5 bis 10, vorzugsweise 1 bis 2 Gew.-% - bezogen auf die Triglyceridmenge - beträgt. Um eine kontinuierliche Fahrweise und hohe Durchsätze zu erzielen, ist es erforderlich, die Enzyme auf geeigneten Trägern zu immobilisieren. Entscheidend für die Auswahl der Träger ist dabei weniger ihre chemische Natur, sondern ihr Durchmesser. Dieser muss klein genug sein, um eine hohe Oberfläche zu gewährleisten, auf der anderen Seite aber auch grob genug, um eine Reaktion bei hohen Strömungsgeschwindigkeiten der Einsatzstoffe zu gewährleisten. Vorzugsweise handelt es sich dabei um Polyolefingranulate und insbesondere Polypropylengranulate mit einem mittleren Durchmesser von 1 bis 5 und vorzugsweise ungefähr 3 mm. Enzyme und die Träger werden dabei vorzugsweise im Gewichtsverhältnis 1 : 1 bis 100 : 1 und insbesondere 1 : 5 bis 1 : 10 eingesetzt. For the purposes of the method according to the invention, lipases are preferably used as enzymes into consideration. The commercial products Novozym are typical examples of suitable lipases 388 L, Novozym SP 525 L, Lipozym TL 100 and Amano G. The enzymes are in the Usually used as dilute suspensions or aqueous concentrates, the Use concentration generally 0.5 to 10, preferably 1 to 2 wt .-% - based on the amount of triglyceride - is. For a continuous driving style and high throughput To achieve this, it is necessary to immobilize the enzymes on suitable carriers. What is decisive for the selection of the carriers is less their chemical nature, but their diameter. This must be small enough to have a high surface area ensure, on the other hand, but rough enough to react at high To ensure flow rates of the feed materials. Preferably acts it is polyolefin granules and in particular polypropylene granules with a average diameter of 1 to 5 and preferably about 3 mm. Enzymes and the Carriers are preferably in a weight ratio of 1: 1 to 100: 1 and in particular 1: 5 to 1:10 used.
Die Entsäuerung der Fette und Öle kann in der für die kontinuierliche enzymatische Veresterung von Fettsäuren an sich bekannten Art und Weise durchgeführt werden. Die Reaktionstemperatur richtet sich dabei natürlich nach dem Aktivitätsoptimum der eingesetzten Enzyme und liegt daher im Bereich von 20 bis 50 und vorzugsweise 25 bis 35 °C. Die immobilisierten Enzyme werden als Schüttung in einen Rohrreaktor gegeben und das zu entsäuernde Einsatzprodukt aufgeströmt, wobei die Verweilzeit im kontinuierlichen Betrieb in der Regel 1 bis 20 und vorzugsweise 5 bis 8 h beträgt. Das Verfahren kann einstufig betrieben werden, im Hinblick auf eine Verminderung der Menge an einzusetzendem Methanol hat es sich jedoch als vorteilhaft erwiesen, zwei bis fünf Reaktoren in Reihe zu schalten und die Reaktion mehrstufig durchzuführen. The deacidification of fats and oils can be used for the continuous enzymatic esterification of fatty acids in a manner known per se. The The reaction temperature is of course based on the optimum activity of the used Enzymes and is therefore in the range of 20 to 50 and preferably 25 to 35 ° C. The immobilized enzymes are poured into a tube reactor and that The product to be deacidified is poured on, the residence time being continuous Operation is usually 1 to 20 and preferably 5 to 8 hours. The procedure can be operated in one stage with a view to reducing the amount of used However, methanol has proven to be advantageous in two to five reactors Switch series and carry out the reaction in several stages.
Beispiel 1. 6 g des Enzymkatalysators, bestehen aus einer 1:1-Mischung SP 525 I und
Poly-propylengranulat, wurden in ein Glasrohr gegeben. Aus einem mechanisch gerührten
Vorratsgefäß wurde eine Mischung aus 250 g entschleimten Kokosöl und 5 Gew.-%
Methanol bei 30 °C mittels einer peristaltischen Pumpe kontinuierlich über die Schüttung
gepumpt (Aufstrom) und die Abnahme der Säurezahl durch Probennahme verfolgt. Die
Ergebnisse sind in Tabelle 1 zusammengefasst:
Male wiederverwendet. Bei jedem der drei Läufe wurde 1 kg Kokosöl vorverestert. In
Tabelle 2 ist der zeitliche Verlauf der Abnahme der Säurezahl im dritten Durchlauf wiedergegeben.
Es zeigt sich, dass die Aktivität des Katalysators im Prinzip konstant hoch
bleibt.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10157067A DE10157067A1 (en) | 2001-11-21 | 2001-11-21 | Process for deacidifying natural fats and oils |
| DE10157067 | 2001-11-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1314775A1 true EP1314775A1 (en) | 2003-05-28 |
| EP1314775B1 EP1314775B1 (en) | 2005-01-19 |
Family
ID=7706415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02025227A Expired - Lifetime EP1314775B1 (en) | 2001-11-21 | 2002-11-12 | Process for the deacidification of natural fats and oils |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6897328B2 (en) |
| EP (1) | EP1314775B1 (en) |
| AT (1) | ATE287437T1 (en) |
| DE (2) | DE10157067A1 (en) |
| ES (1) | ES2234974T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833844A (en) * | 2016-03-24 | 2016-08-10 | 董晓 | Preparation method of deacidifying agent with lotus leaves |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009100437A1 (en) * | 2008-02-10 | 2009-08-13 | Hemisphere Gps Llc | Antenna alignment and monitoring system and method using gnss |
| WO2010106439A2 (en) * | 2009-03-16 | 2010-09-23 | Le Sage Hendrikus A | Aisg inline tilt sensor system and method |
| US9046601B2 (en) | 2009-06-15 | 2015-06-02 | Hendrikus A. Le Sage | Handheld antenna attitude measuring system |
| US8307535B2 (en) | 2010-07-20 | 2012-11-13 | Hemisphere Gps Llc | Multi-frequency antenna manufacturing method |
| US8686899B2 (en) | 2010-08-26 | 2014-04-01 | Hemisphere GNSS, Inc. | GNSS smart antenna and receiver system with weatherproof enclosure |
| US9328054B1 (en) | 2013-09-27 | 2016-05-03 | Travis Danner | Method of alcoholisis of fatty acids and fatty acid gyicerides |
| EP3750405A1 (en) * | 2018-03-02 | 2020-12-16 | Fuji Oil Holdings Inc. | Production method for oil/fat composition rich in palmitic acid at position 2 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678580A (en) * | 1986-01-27 | 1987-07-07 | Akzo America Inc. | Hydrolysis of fats |
| WO1991014784A1 (en) * | 1990-03-23 | 1991-10-03 | Novo Nordisk A/S | A process for increasing the amount of triglyceride of a fat or oil |
| US5713965A (en) * | 1996-04-12 | 1998-02-03 | The United States Of America As Represented By The Secretary Of Agriculture | Production of biodiesel, lubricants and fuel and lubricant additives |
| DE19956599A1 (en) * | 1999-11-25 | 2001-06-13 | Cognis Deutschland Gmbh | Process for the production of deacidified triglycerides |
| US6398707B1 (en) * | 2001-05-31 | 2002-06-04 | Wen-Teng Wu | Method of preparing lower alkyl fatty acids esters and in particular biodiesel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3501761A1 (en) | 1985-01-21 | 1986-07-24 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRE-Esterification OF FREE FATTY ACIDS IN RAW FATS AND / OR OILS |
| DE19600025C2 (en) | 1996-01-03 | 1998-12-03 | Henkel Kgaa | Process for the production of fatty substances |
-
2001
- 2001-11-21 DE DE10157067A patent/DE10157067A1/en not_active Withdrawn
-
2002
- 2002-11-12 ES ES02025227T patent/ES2234974T3/en not_active Expired - Lifetime
- 2002-11-12 EP EP02025227A patent/EP1314775B1/en not_active Expired - Lifetime
- 2002-11-12 AT AT02025227T patent/ATE287437T1/en not_active IP Right Cessation
- 2002-11-12 DE DE50202037T patent/DE50202037D1/en not_active Expired - Lifetime
- 2002-11-21 US US10/301,333 patent/US6897328B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4678580A (en) * | 1986-01-27 | 1987-07-07 | Akzo America Inc. | Hydrolysis of fats |
| WO1991014784A1 (en) * | 1990-03-23 | 1991-10-03 | Novo Nordisk A/S | A process for increasing the amount of triglyceride of a fat or oil |
| US5713965A (en) * | 1996-04-12 | 1998-02-03 | The United States Of America As Represented By The Secretary Of Agriculture | Production of biodiesel, lubricants and fuel and lubricant additives |
| DE19956599A1 (en) * | 1999-11-25 | 2001-06-13 | Cognis Deutschland Gmbh | Process for the production of deacidified triglycerides |
| US6398707B1 (en) * | 2001-05-31 | 2002-06-04 | Wen-Teng Wu | Method of preparing lower alkyl fatty acids esters and in particular biodiesel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833844A (en) * | 2016-03-24 | 2016-08-10 | 董晓 | Preparation method of deacidifying agent with lotus leaves |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1314775B1 (en) | 2005-01-19 |
| ES2234974T3 (en) | 2005-07-01 |
| US20030124694A1 (en) | 2003-07-03 |
| ATE287437T1 (en) | 2005-02-15 |
| US6897328B2 (en) | 2005-05-24 |
| DE50202037D1 (en) | 2005-02-24 |
| DE10157067A1 (en) | 2003-05-28 |
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