DE10043644A1 - Production of biomethanol and bioethanol diesel comprises continuous re-esterification, removing glycerin after dosing the catalyst-alkanol mixture with removal of methanol in the biodiesel, and washing with phosphoric acid and water - Google Patents
Production of biomethanol and bioethanol diesel comprises continuous re-esterification, removing glycerin after dosing the catalyst-alkanol mixture with removal of methanol in the biodiesel, and washing with phosphoric acid and waterInfo
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- DE10043644A1 DE10043644A1 DE10043644A DE10043644A DE10043644A1 DE 10043644 A1 DE10043644 A1 DE 10043644A1 DE 10043644 A DE10043644 A DE 10043644A DE 10043644 A DE10043644 A DE 10043644A DE 10043644 A1 DE10043644 A1 DE 10043644A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur kontinuierlichen Herstellung von Biomethanol- und -ethanoldiesel in einer mehrstufigen Mikroreaktorkaskade aus standardisierten Glasbauelementen zur bevorzugten Anwendung in der Landwirtschaft.The invention relates to a process for the continuous production of biomethanol and ethanol diesel in a multi-stage microreactor cascade of standardized Glass components for preferred use in agriculture.
Bekannt ist, dass Biodiesel durch Umesterung von nativen Glycidestern, in Europa dominant aus Rapsöl, mit Methanol unter Einsatz von Katalysatoren, meist KOH oder NaOH, gewonnen wird (B. GUTSCHE: Technologie der Methylesterherstellung. Fett/Lipid 99 (1997) 418-27). Dabei kommen sowohl Batch-Verfahren. (Umesterung von Rapsöl zu Diesel-Alternativtreibstoff, Firmenschrift VOGEL 1990), Semi- Batch-Verfahren (E. AHN et al.: A low-waste process for the production of biodiesel, Sep. Sci. Techn. 30 (1995) 2021-33 und R. STERN u. G. HILLION: EP 0 356 317 (1988) Inst. Francais du Petrole) als auch kontinuierliche Verfahren (J. CONNE- MANNN: DP 42 09 779, US P 5 354878, EU 0 562 504 jeweils 26.3.1992) zum Einsatz. Ein spezielles, kontinuierliches Verfahren zur Biodieselherstellung auch unter Verwendung von Altfetten ist von der L. U. T. entwickelt worden (J. HAUPT: Biokraftstoff und Verfahren zu seiner Herstellung. DE 196 22 601 C1).It is known that biodiesel by transesterification of native glycid esters, in Europe dominant from rapeseed oil, with methanol using catalysts, mostly KOH or NaOH, is obtained (B. GUTSCHE: Technology of methyl ester production. Fat / Lipid 99 (1997) 418-27). Both batch processes come here. (transesterification from rapeseed oil to alternative diesel fuel, company publication VOGEL 1990), semi- Batch process (E. AHN et al .: A low-waste process for the production of biodiesel, September Sci. Techn. 30 (1995) 2021-33 and R. STERN u. G. HILLION: EP 0 356 317 (1988) Inst. Francais du Petrole) as well as continuous processes (J. CONNE- MAN: DP 42 09 779, US P 5 354878, EU 0 562 504 each 26.3.1992) for Commitment. A special, continuous process for biodiesel production too using used fats has been developed by L. U. T. (J. HAUPT: Biofuel and process for its production. DE 196 22 601 C1).
Speziell über die Umesterung von Sojaöl mit Methanol und Ethanol sowie über den Einsatz der Umesterungsprodukte in Verbrennungsmotoren berichten CLARC und Mitarbeiter (S. J. CLARK et al.: Methyl- und Ethyl Soybean Esters as Renewable Fuels for Diesel Engines JAOCS 61 (1984) 1632-38).Especially about the transesterification of soybean oil with methanol and ethanol as well as about the Use of the transesterification products in combustion engines are reported by CLARC and Staff (S. J. CLARK et al .: Methyl- and Ethyl Soybean Esters as Renewable Fuels for Diesel Engines JAOCS 61 (1984) 1632-38).
Allen genannten Verfahren ist gemein, dass die Umesterung als 2-stufiger Prozess entweder drucklos oder bis max. 62 bar betrieben wird und den Umesterungsstufen eine Methanolabtrennung sowie ein Waschprozess zur Reduzierung des Kaliumgehaltes im Hauptprodukt Biodiesel bzw. der Glycerinphase unter Gewinnung von Kaliumhydrogenphosphat nachgeschaltet sind.A common feature of all the processes mentioned is that the transesterification is a 2-stage process either without pressure or up to max. 62 bar is operated and the transesterification stages a methanol separation and a washing process to reduce the Potassium content in the main product biodiesel or the glycerin phase with recovery are followed by potassium hydrogen phosphate.
Bekannt ist ferner, dass durch Wasser und freie Fettsäuren die Ausbeute der Trans
methylierungsreaktion unter Bildung des sogenannten Seifenstockes sich erheblich
vermindern kann (B. FREEDMAN et al.: Varables Affecting the Yields of Fatty Esters
from Transesterified Vegetable Oils. JAOCS 61 (1984) 1638-43 und A. ZELLNER:
Katalytische Herstellung von Rapsölmethylester Dissertation. Diusburg 1989). Das
It is also known that water and free fatty acids can significantly reduce the yield of the trans methylation reaction to form the so-called soap stick (B. FREEDMAN et al .: Varables Affecting the Yields of Fatty Esters from Transesterified Vegetable Oils. JAOCS 61 (1984) 1638 -43 and A. ZELLNER: Catalytic production of rapeseed oil methyl ester dissertation. Diusburg 1989). The
CH3OH + KOH ⇄ CH3OK + H2O (Gl. 1)
CH 3 OH + KOH ⇄ CH 3 OK + H 2 O (Eq. 1)
CH3C=OOR + KOH ⇄ CH3OH + KO C=OR (Gl. 2)
CH 3 C = OOR + KOH ⇄ CH 3 OH + KO C = OR (Eq. 2)
HOC=OR + KOH ⇄ H2O + KO C=OR (Gl. 3)HOC = OR + KOH ⇄ H 2 O + KO C = OR (Eq. 3)
Wasser wird, dabei einmal durch die Einsatzstoffe (Rohglycid oder Methanol) zum anderen durch die Katalysatorherstellung gemäß Gl. 1 in den Prozess eingeschleppt bzw. dort selbst erzeugt Dia freien Fettsäuren gelangen über die nativen Öle in den Prozess bzw entstehen im Prozess dann, wenn die Temperatur bei er Umesterung < 60°C beträgt (M. MITTELBACH et al. Kinetics of Alkaline Catalyzed Methanolysis of Sunflower Oil. Fat. Sci. Technol. 92 (1990) 145-8) oder durch Verseifung gemäß (Gl. 2 bzw 3), als eine zwar langsam verlaufenden, aber prinzipiell nicht auszu schließenden Konkurrenzreaktion der Umesterung (Prinzip der Esterverseifung). Water becomes, through the feed materials (raw glycid or methanol) other by the catalyst preparation according to Eq. 1 introduced into the process or Dia free fatty acids generated there get into the through the native oils Process or arise in the process when the temperature during the transesterification <60 ° C (M. MITTELBACH et al. Kinetics of Alkaline Catalyzed Methanolysis of Sunflower Oil. Fat. Sci. Technol. 92 (1990) 145-8) or by saponification according to (Eq. 2 or 3), as a slowly running, but in principle not out closing competitive reaction of the transesterification (principle of ester saponification).
Dadurch entsteht ein erhöhter Verbrauch an Katalysator infolge unerwünschter Seifenbildung sowie ein erhöhter Verlust an Biodiesel durch Bildung des Seifenstockes, einem Gemenge aus Seife und Biodiesel. Dieser Seifenstock wird entweder anschließend abgetrennt, sauer mit Glycerin und Schwefelsäure wieder rückverestert und in den Prozess zurückgeführt (M. MITTELBACH: Verfahren zur Herstellung von Fettsäurealkylestern. WO 95/02661 26.1.95.) oder seine Bildung in Großanlagen der chemischen Industrie durch eine saure Vorveresterung der freien Fettsäuren unterdrückt (L. JEROMIN et al.: Verfahren zur Vorveresterung freier Fettsäuren in Rohfetten und/oder Ölen. DP 3 501 761 (1986)).This results in an increased consumption of catalyst due to undesirable Soap formation and an increased loss of biodiesel through formation of the Soap stick, a mixture of soap and biodiesel. This soap stick will either subsequently separated, acidic again with glycerol and sulfuric acid reesterified and returned to the process (M. MITTELBACH: procedure for Manufacture of fatty acid alkyl esters. WO 95/02661 26.1.95.) Or its formation in Large-scale plants in the chemical industry through acidic pre-esterification of the free Fatty acids suppressed (L. JEROMIN et al .: Process for the pre-esterification of free Fatty acids in raw fats and / or oils. DP 3 501 761 (1986)).
Nachteilig an diesen beiden Verfahrensschritten ist, dass sie wirtschaftlich nur in chemischen Großanlage anwendbar sind, in denen Methylester als Synthesevorstufen hergestellt werden, nicht aber in regional betriebenen kleinen Biodieselanlagen mit < 10 kt/a Produktionsvolumen angewendet werden können. Sympath mit der Seifenbildung und der damit verbundenen dispergierenden Wirkung des Seifenstockes wird die Phasentrennung zwischen Biodiesel und Glycerinwasserphase erschwert, was sowohl die Verseifung der Methylester beschleunigt als auch die Raum-Zeit-Ausbeute erniedrigt.The disadvantage of these two process steps is that they are economical only in large chemical plant are applicable, in which methyl ester as Synthesis precursors are produced, but not in regionally operated small ones Biodiesel plants with <10 kt / a production volume can be used. Sympathy with the soap formation and the associated dispersing effect of the soap stick is the phase separation between biodiesel and Glycerol water phase complicates both the saponification of the methyl ester accelerated as well as the space-time yield decreased.
Zur Verbesserung der Phasentrennungen werden in der Literatur deshalb unter
schiedliche Verfahren dargestellt:
To improve the phase separations, different methods are therefore presented in the literature:
- - der Einsatz von Demulgatoren (C. AUSCHRA: Dispergierwirksame Cooligomere und Copolymere. DE 44 23 358 A1 4.7.94)- the use of demulsifiers (C. AUSCHRA: dispersing cooligomers and copolymers. DE 44 23 358 A1 4.7.94)
- - der Einsatz von Koalizensabscheidern, wie Draht- oder Kunststoffgewebe, Füllkörpern oder Glasfasern (J. FALKOWSKY et al.: Verfahren zur Herstellung niederer Alkylester. DE 197 21 474 C1 23.5.1997)- the use of coal separators, such as wire or plastic mesh, Packings or glass fibers (J. FALKOWSKY et al .: Process for the production lower alkyl ester. DE 197 21 474 C1 23.5.1997)
- - oder die Waschung mit Glycerin (M. GROSS et al. WO 94/170 27 19.1.1994).- or washing with glycerin (M. GROSS et al. WO 94/170 27 19.1.1994).
Bekannt ist ferner, dass in einem von ASSMANN et al. patentierten Verfahren (G. ASSMANN et al.: Kontinuierliches Verfahren zum Herstellen niederer Alkylester. DE 39 32 514 A1 29.9.89) Mikroreaktoren in Kombination mit Rohrreaktoren für die Umesterung eingesetzt werden.It is also known that in one of ASSMANN et al. patented process (G. ASSMANN et al .: Continuous process for the preparation of lower alkyl esters. DE 39 32 514 A1 29.9.89) Microreactors in combination with tubular reactors for the Transesterification can be used.
Der Erfindung liegt die Aufgabe zugrunde, ein einfach zu handhabendes, kontinuierlich arbeitendes Verfahren zur Herstellung von Biodiesel in stationären oder mobilen Kleinstanlagen zur regionalen Versorgung vorzugsweise im ländlichen Raum zu kreieren. Als Zusatzforderung besteht darüber hinaus die Aufgabe, das Verfahren mit einer wesentlich höheren Raum-Zeit-Ausbeute im Vergleich zum bekannten Stand der Technik zu betreiben und mit der gleichen Gerätekonfiguration anfallende Nebenprodukte der Glycerinphase für den Markt wertschöpfend aufzuarbeiten.The invention has for its object to provide an easy to use continuous process for the production of biodiesel in stationary or small mobile systems for regional supply, preferably in rural areas To create space. As an additional requirement, there is also the task of Process with a much higher space-time yield compared to known state of the art to operate and with the same device configuration accruing by-products of the glycerol phase create value for the market work up.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, dass das Verfahren aus einer Kaskade von mindestens 3 Mikroreaktoren besteht. Nach jeder der drei ersten Mikroreaktorstufen erfolgt eine schnelle Abtrennung der Glycerinphase in Dekantern oder Separatoren; in einer 4. Stufe die Wäsche mit verdünnter Phosphorsäure. wird Beim vorliegenden Verfahren wird quasi drucklos und bei sehr niedrigeren Tempera turen von ca. 60°C gearbeitet. Auf eine Nachreaktionsphase in sogenannten Rohrreaktoren wird ebenfalls verzichtet, weit eine solche technische Lösung eigentlich der Thermodynamik der Gleichgewichtsreaktion widerspricht. Vielmehr werden kürzere Verweilzeiten in den Abscheidern bewusst dadurch erzwungen, dass eine Reduzierung des Wassergehaltes in den Ausgangsverbindungen vor allem der eingesetzten. Alkohole und der Katalysatoren durch eine sorgfältige Vortrocknung dieser Ausgangskomponenten vorgenommen wird. Der Wassergehalt des Eduktgemisches muss deutlich unter 1% liegen. The object is achieved in that the method from a Cascade consists of at least 3 microreactors. After each of the first three Microreactor stages rapidly separate the glycerin phase in decanters or separators; in a 4th stage, wash with dilute phosphoric acid. becomes In the present process, it is virtually depressurized and at a very low temperature worked at approx. 60 ° C. On a post-reaction phase in so-called Tube reactors are also dispensed with, as far as such a technical solution is concerned actually contradicts the thermodynamics of the equilibrium reaction. Much more shorter residence times in the separators are deliberately enforced by the fact that a reduction in the water content in the starting compounds, especially the . used Alcohols and the catalysts through careful predrying of these starting components is made. The water content of the Educt mixture must be well below 1%.
Zur Vortrocknung kann allgemein festgestellt werden, dass bereits vor der Umes terung entferntes Wasser in den Ausgangsverbindungen nicht bei der Produktauf arbeitung. z. B. zur Glyceringewinnung abgetrennt werden muss; letztlich für die ganzheitliche Aufarbeitung des eingesetzten Öles also kaum ein Mehraufwand entsteht.For pre-drying it can generally be stated that before the Umes Removed water in the starting compounds is not present in the product processing. z. B. must be separated for glycerol production; ultimately for the Holistic processing of the oil used is hardly an additional effort arises.
Wesentlich für die Umesterungsreaktion aber ist dass mit der Erniedrigung des Wassers im Reaktionsgemisch eine Verringerung der Seifenstockbildung als einsetzende Folgereaktion der Methyl bzw Ethylesterbildung einhergeht. Im speziellen Fall der Umesterung mit (Bio)ethanol kommt es überhaupt erst mit sehr gut getrockneter Alkoholkomponente zur Reaktion.It is essential for the transesterification reaction that with the lowering of the Water in the reaction mixture as a reduction in soap formation subsequent reaction of methyl or ethyl ester formation goes hand in hand. in the In the special case of transesterification with (bio) ethanol, it comes with very much well-dried alcohol component for reaction.
Soll die Umesterung als kontinuierlicher Prozess und ohne Zwischenverweilzeiten in zusätzlichen Röhrreaktoren verlaufen, bewirkt ein geringerer Seifenstockanteil eine schneller Phasentrennung der entstehenden Produkte durch eine sympath verlaufenden Verringerung der Emulgatorwirkung zwischen Biodieselphase und Glycerinphase. Damit verbunden kommt es zu einer Erhöhung der Raum-Zeit- Ausbeute. Dieser Effekt wird dahingehend unterstützt, dass bei Temperaturen < 60°C die Konkurrenzreaktion der Verseifung gemäß Gl. 2 weitgehend unterdrückt wird, mithin auch durch diese Fahrweise weniger Seife bzw. Seifenstock entstehen kann.If the transesterification is to be carried out as a continuous process and without intermediate residence times in run additional tube reactors, a lower percentage of soap bars causes a faster phase separation of the resulting products by a sympath ongoing reduction of the emulsifier effect between biodiesel phase and Glycerol phase. This leads to an increase in space-time Yield. This effect is supported in that at temperatures < 60 ° C the competition reaction of the saponification according to Eq. 2 largely suppressed will therefore also result in less soap or soap stock through this driving style can.
Die Verringerung der Seifenstockbildung erlaubt andererseits eine Verringerung des Katalysatoreinsatzes (Tabelle 1 und Ausführungsbeispiel a). So werden im eigenen Verfahren auf 1 kg unbehandeltes Rohöl nur 1,35-2,7 g Katalysator benötigt (Tabelle 1, letzte Zeile). Demgegenüber verlangt das beste Konkurrenzverfahren bei Einsatz von Neutralglyciden 2,5 g/kg an Katalysator. Da die Säurezahl vom Rapsöl im Mittel nicht wesentlich < 2 liegt, müssen für den realen technischen Prozess allerdings noch weitere 2 g/kg Einsatzmenge Öl hinzuaddiert werden (Tabelle 1, 4. Zeile).On the other hand, the reduction in the formation of soaps allows a reduction in the Catalyst insert (Table 1 and embodiment a). So be in your own Process on 1 kg of untreated crude oil only requires 1.35-2.7 g of catalyst (Table 1, last row). In contrast, the best competitive process demands Use of neutral glycides 2.5 g / kg of catalyst. Because the acid number of rapeseed oil on average not significantly <2, must be for the real technical process However, a further 2 g / kg of oil is added (Table 1, 4. Row).
Der verminderte Verbrauch des eigenen Verfahrens ist plausibel. Die nach der Rückreaktion gemäß Gl. 1 gebildete KOH kann im wässrigem Medium dissoziieren (Gl. 4). Die dabei entstehenden OH-Ionen bilden bekanntermaßen mit dem Methylester ein Gleichgewicht, aus dem das Carboxylatanion und der Methanol in einer irreversiblen Folgereaktion entstehen. Dabei werden molare Mengen an KOH verbraucht, d. h., gehen durch Bildung der Seife verloren. The reduced consumption of your own process is plausible. The after the Reverse reaction according to Eq. 1 KOH formed can dissociate in an aqueous medium (Eq. 4). The resulting OH ions are known to form with the Methyl ester is an equilibrium from which the carboxylate anion and the methanol in an irreversible subsequent reaction. Molar amounts of KOH used up, d. that is, lost through soap formation.
Damit verbunden ist ein relativ geringer Kaliumgehalt im produzierten Biodiesel von ca. 3 ppm.This is associated with a relatively low potassium content in the biodiesel produced by about 3 ppm.
Im Unterschied zu allen obengenannten Verfahren erfolgt im eigenen Verfahren keine separate Einspeisung von Katalysator und Alkoholkomponente. Vielmehr werden KOH bzw. NaOH mit dem jeweiligen Alkanol, also Methanol oder Ethanol vermischt, über Molsiebe oder mittels Membranverfahren getrocknet und dieses Gemisch mit dem nativen Lein-, Soja-, Sonnenblumen- oder Drachenkopföl und insbesondere Rapsöl im Mikroreaktor zur Reaktion gebracht. Dabei reichen Reynoldszahlen von etwa 1300 ≦ Re ≦ 1500 zum Dispergieren des Öl-Alkanol- Katalysator-Gemisches völlig aus.In contrast to all of the above-mentioned procedures, this is done in-house no separate feed of catalyst and alcohol component. Much more become KOH or NaOH with the respective alkanol, i.e. methanol or ethanol mixed, dried over molecular sieves or by membrane process and this Mix with the natural linseed, soybean, sunflower or dragon head oil and in particular rapeseed oil reacted in the microreactor. It is enough Reynolds numbers of approximately 1300 ≦ Re ≦ 1500 for dispersing the oil-alkanol Catalyst mixture completely.
KOH und Methanol (Ethanol) werden im Verhältnis 10-20 g/l Alkanol mit einander gemischt (bei NaOH als Katalysator 28 g/l) und überein Molsieb der Type 3A oder 4A so lange getrocknet, bis der Wassergehalt deutlich unter 1% liegt.KOH and methanol (ethanol) are in a ratio of 10-20 g / l alkanol with each other mixed (with NaOH as catalyst 28 g / l) and over a molecular sieve of type 3A or 4A dried until the water content is significantly below 1%.
Die Zudosierung des Katalysator-Alkanol-Gemisches zum Öl erfolgt gemäß Abb. 1 durch Dosierpumpen gesteuert so, dass insgesamt pro Mol Öl < 3 Mol Alkanol- Alkanolatlösung zur Reaktion gebracht werden. Die Vermischung der Öl- mit der Alkoholphase erfolgt stufenweise in einer Mikroreaktorkaskade bestehend aus einem Mikroreaktor und einem Separator gemäß Abb. 1. In jeder Stufe werden Biodieselphase und Glycerinphase voneinander getrennt. Nach der dritten Mikroreaktorstufe erreicht man einen Umsetzungsgrad von ca. 98%. The addition of the catalyst-alkanol mixture to the oil is controlled according to Fig. 1 by metering pumps so that a total of <3 moles of alkanol / alkanolate solution are reacted per mole of oil. The oil and alcohol phases are mixed in stages in a microreactor cascade consisting of a microreactor and a separator as shown in Fig. 1. Biodiesel phase and glycerol phase are separated from each other in each stage. After the third microreactor stage, a degree of conversion of approximately 98% is achieved.
Die vereinigten Batche mehrerer Glycerinphasen werden bis zum Erreichen des pH-Wertes 2 mit 85%-ige Phosphorsäure in der 4. Reaktorstufe miteinander vermischt und die dabei entstehenden 3 Phasen nach Entmethanolisierung voneinander getrennt. Die untere Phase, das Kaliumdihydrogenphosphat mit Wasser und dem. Überschuss an Phosphorsäure, wird mit der wässrigen Phase der Waschstufe aus der Biodiesestufe vereinigt und dient als Flüssigdünger. Die obere Phase besteht aus dem Gemisch freier Fettsäuren und Biodiesel die mittlere Phase besteht dominant aus Glycerin. Die Zusammensetzung der 3 Phasen: ca. 22% Fettsäuregemisch/Biodiesel, ca. 54% Glycerin/Wasser und 23% Kaliumhydrogenphosphat/Wasser/Restglycerin.The combined batches of several glycerol phases are until the pH 2 with 85% phosphoric acid in the 4th reactor stage with each other mixed and the resulting 3 phases after demethanolization separated from each other. The lower phase, the potassium dihydrogen phosphate with Water and the. Excess phosphoric acid, is with the aqueous phase the washing stage from the biodiesel stage and serves as liquid fertilizer. The upper phase consists of the mixture of free fatty acids and biodiesel middle phase consists predominantly of glycerin. The composition of the 3rd Phases: approx. 22% fatty acid mixture / biodiesel, approx. 54% glycerin / water and 23% potassium hydrogen phosphate / water / residual glycerin.
Aus der mittleren Phase kann mittels Sprühverdampfungseinrichtung ca. 75% des Gesamtglycerinanteils als Reinstglycerin gewonnen werden.From the middle phase, approx. 75% can be of the total glycerol content can be obtained as high-purity glycerol.
Claims (1)
der Umesterungsprozess kontinuierlich in einer mehrstufigen Mikroreaktor kaskade bei Reynoldszahlen um 1300 ≦ Re ≦ 1500 und minimaler Verweilzeit durchgeführt wird, wobei jede Kaskadenstufe aus einem Mikroreaktor und einem Separator besteht, aber keine Geräteteile zum Nachreagieren benötigt;
in 3 Stufen jeweils nach Zudosierung des Katalysator-Alkanol-Gemisches eine Zwischenabscheidung des Glycerins erfolgt, in der letzten Stufe der Biodiesel entmethanolisiert und mit Phosphorsäure und Wasser so gewaschen wird, dass das Endprodukt Kaliumgehalte von ca. 3 ppm besitzt;
die zur Umesterung eingesetzten Alkanole, wie Ethanol oder Methanol vor der Umesterung z. B. mittels Molsieben oder eines Membrantrennverfahrens so vor getrocknet werden, dass ihr Wassergehalt < 0,3% beträgt;
die eingesetzten Katalysatoren in Form der K- oder Na-Metholate bzw. -etholate nach Umsetzung der Ausgangsverbindungen in gleicher Weise getrocknet werden;
der Zwangsanfall des Nebenproduktes Seifenstock minimal klein ist und damit auch seine negativ dispergierende Wirkung auf das zu trennende System Biodieselphase/Glycerinphase;
dass allein durch die Vorwahl der Reaktorlaufzeit, aber nicht durch das Reaktorvolumen das Produktionsvolumen im Bereich von 0,2 t/d bis zu < 2,5 t/d variabel einstellbar ist;Process for the continuous production of biomethanol and bioethanol diesel in small plants, characterized in that
the transesterification process is carried out continuously in a multi-stage microreactor cascade at Reynolds numbers around 1300 ≦ Re ≦ 1500 and minimum residence time, each cascade stage consisting of a microreactor and a separator, but does not require any equipment parts for subsequent reaction;
Intermediate separation of the glycerol takes place in 3 stages each after metering in the catalyst-alkanol mixture, in the last stage the biodiesel is demethanolized and washed with phosphoric acid and water so that the end product has potassium contents of approx. 3 ppm;
the alkanols used for the transesterification, such as ethanol or methanol before the transesterification, for. B. before using molecular sieves or a membrane separation process so that their water content is <0.3%;
the catalysts used in the form of the K or Na metholates or etholates are dried in the same way after the reaction of the starting compounds;
the inevitable occurrence of the by-product soap bar is minimal and thus also its negative dispersing effect on the biodiesel phase / glycerol phase to be separated;
that the production volume can be variably adjusted in the range from 0.2 t / d to <2.5 t / d solely by preselecting the reactor runtime, but not by the reactor volume;
Priority Applications (1)
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DE10043644A DE10043644A1 (en) | 2000-09-05 | 2000-09-05 | Production of biomethanol and bioethanol diesel comprises continuous re-esterification, removing glycerin after dosing the catalyst-alkanol mixture with removal of methanol in the biodiesel, and washing with phosphoric acid and water |
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Application Number | Priority Date | Filing Date | Title |
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DE10043644A DE10043644A1 (en) | 2000-09-05 | 2000-09-05 | Production of biomethanol and bioethanol diesel comprises continuous re-esterification, removing glycerin after dosing the catalyst-alkanol mixture with removal of methanol in the biodiesel, and washing with phosphoric acid and water |
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DE10043644A1 true DE10043644A1 (en) | 2002-03-28 |
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DE10043644A Ceased DE10043644A1 (en) | 2000-09-05 | 2000-09-05 | Production of biomethanol and bioethanol diesel comprises continuous re-esterification, removing glycerin after dosing the catalyst-alkanol mixture with removal of methanol in the biodiesel, and washing with phosphoric acid and water |
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