EP2142286A1 - Procédé servant à purifier un mélange de produits généré par des réactions de transestérification - Google Patents

Procédé servant à purifier un mélange de produits généré par des réactions de transestérification

Info

Publication number
EP2142286A1
EP2142286A1 EP08735138A EP08735138A EP2142286A1 EP 2142286 A1 EP2142286 A1 EP 2142286A1 EP 08735138 A EP08735138 A EP 08735138A EP 08735138 A EP08735138 A EP 08735138A EP 2142286 A1 EP2142286 A1 EP 2142286A1
Authority
EP
European Patent Office
Prior art keywords
bar
organic phase
electrolyte
glycerol
membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08735138A
Other languages
German (de)
English (en)
Inventor
Michael Traving
Johannes-Peter Schaefer
Rafael Warsitz
Waldemar Widuch
Werner BÄCKER
Uwe SPÖRER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer Technology Services GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Technology Services GmbH filed Critical Bayer Technology Services GmbH
Publication of EP2142286A1 publication Critical patent/EP2142286A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/025—Bobbin units
    • 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 present invention relates to a process for the purification of product mixtures from transesterification reactions comprising a polar, electrolyte-containing organic phase by nanofiltration.
  • a disadvantage of this method for working up of electrolyte-containing organic product mixtures is the high use of additional water, which is loaded after purification by dialysis with electrolyte. Especially in view of the increasingly stringent environmental regulations, the disposal of large saline water volumes in industrial processes is an important and costly aspect. A thermal work-up of the additional water causes further energy costs, as in the alternative method of distillation.
  • Another work-up method involves the desalination of the organic phase via special
  • Ion exchangers which show a good separation of the electrolytes at high throughput.
  • the modern ion exchangers are tailor-made for this task
  • Another method described for the purification of electrolyte-containing product mixtures from transesterification reactions is the precipitation of the salts after separation of methanol and water by the addition of short-chain alcohols in a defined phase ratio of 1: 0.3 to 1: 4 (for example, glycerol to alcohol).
  • the salt can be suitably keptf ⁇ ltert.
  • the object of the present invention is therefore to provide a simplified process for the purification of an electrolyte-containing product from the mixture of a transesterification reaction in the highest possible quality, taking into account the requirement to integrate the process on an industrial scale in particular in a continuous overall process.
  • this object is achieved by a process for purifying the product mixture of a transesterification reaction with a polar, electrolyte-containing organic phase, in which the electrolytes are separated from the permeating polar organic phase by means of a nanofluidation step.
  • Transesterification reactions are an industrially important class of organic reactions in which an ester is converted by exchange of the acid groups or by exchange of the alcoholic groups for another ester. If the transesterification takes place by exchanging the alcoholic groups, this is also called alcoholysis. In alcoholysis, the alcohol to be replaced is generally added in excess to obtain a high yield of the desired ester. Because the transesterification reaction is an equilibrium reaction, which is usually already triggered by mixing the reactants. However, the reaction proceeds so slowly that a catalyst for acceleration is required for commercial purposes.
  • An example of an economically important transesterification reaction is the preparation of fatty acid esters of short-chain alcohols, in which a product mixture of different fatty acid esters which can be used as fuel is obtained by transesterification of natural fats or oils, such as rapeseed oil or soybean oil.
  • Fats and oils of biological origin consist predominantly of glycerides (mono-, di- and triglyceride).
  • the Bradshaw process for the transesterification of fats and oils with methanol is frequently used. But also various modifications of the process are common. Especially in the field of catalysts used, there is a wide variation.
  • acid-catalyzed processes and enzymatic methods are also conceivable. - A -
  • electrolyte-containing product is understood according to the invention as the proportion of the product mixture from the transesterification reaction, which in addition to the electrolyte also contains those compounds which have one or more free hydroxyl or acid groups. For example, it is glycerol and short-chain alcohols and, to a lesser extent, free fatty acids (FFA) and water.
  • electrolytes all salt-like organic or inorganic compounds are referred to here and below. These include, for example, the catalysts preferably used in the transesterification reaction, such as sodium or potassium hydroxide, ammonium compounds or sulfuric acid compounds. However, even those salts which enter the reaction mixture as part of the educts used are to be grouped together under the term electrolytes according to the present invention.
  • the electrolyte-containing product contains methanol, ethanol, isopropanol, water and / or glycerol.
  • nanofiltration is understood according to the invention to mean a pressure-driven membrane separation process which retains particles in the nanometer range. Such particles are, for example, bivalent ions.
  • nanofiltration is based on its separation performance between reverse osmosis, in which all dissolved substances are retained, and ultrafiltration, in which larger particles can be separated, for example, between 2 nm and 0.1 ⁇ m.
  • ultrafiltration in which larger particles can be separated, for example, between 2 nm and 0.1 ⁇ m.
  • Both non-porous and porous membranes can be used.
  • nanofiltration is not used in the known sense to separate electrolytes and dissolved substances from an aqueous phase. Rather, in the present case, an electrolyte-containing organic phase is subjected to nanofiltration.
  • the filtration temperature is not critical and can be varied in other areas.
  • the nanofiltration at a temperature between 15 ° C and 90 0 C, preferably between 20 0 C and 60 0 C, more preferably between 30 0 C and 40 0 C, performed.
  • the method according to the invention it is possible for the first time to provide an industrially usable process for the purification of electrolyte-containing organic product mixtures from transesterification reactions, which, in addition to considerably simplified process control, permits a simplified integration into the overall process on account of the now continuously mobile process.
  • the separation according to the invention of the electrolytes from the permeating organic phase by means of a nanofiltration step it is advantageously achieved that the mixture passing through the membrane, which preferably consists of glycerol, methanol and water, is almost completely freed of the electrolytes.
  • phase change separation processes work without phase change
  • significantly less energy is required for the separation process than comparable phase change separation processes such as, for example, distillative processes.
  • Another advantage is that the purification by nanofiltration allows a considerably simplified apparatus design.
  • the purification can be carried out at room temperature or slightly elevated temperature, which, in addition to the mentioned energy saving, proceeds much more gently for the organic products, so that they can be obtained with a higher quality yield.
  • the erfmdungshacke method is carried out so that first a reaction mixture for the transesterification of educt ester, catalyst and alcohol is stirred for a certain time in a reaction vessel.
  • the reaction temperature, pressure and reaction time are not critical and are chosen so that as complete a conversion as possible is achieved with the lowest possible residence time.
  • the resulting product mixture is fed to a separation stage which separates the non-polar product ester phase from the polar organic phase with the alcohol, glycerin and catalyst components.
  • the separated polar organic phase with the alcohol, glycerol and catalyst components can be worked up in further steps, for example, initially provide for neutralization of the basic or acidic catalysts used.
  • the neutralization step converts the bases or acids used as catalyst into salts.
  • the salt cargo thus produced can then be separated according to the invention.
  • the salt load can be reduced by simply separating off the already precipitated salt before the nanofluidization step.
  • the organic phase obtained from the neutralization is subjected to nanofiltration.
  • a suitable non-porous or porous membrane under a filtration pressure between 5 bar and 70 bar, preferably between 10 bar and 60 bar, more preferably between 15 bar and 50 bar, an almost completely electrolyte-free mixture is obtained according to the invention.
  • the mixture may preferably consist of glycerol, short-chain alcohols such as methanol, ethanol and / or isopropanol and small amounts of water.
  • electrolyte-free is understood here and below that an electrolyte content of less than 0.01 wt .-% based on divalent ions in the mixture can be present. Preferably, only an electrolyte content of less than 0.005 wt .-% based on divalent ions in the permeated mixture detectable.
  • the retained salt which is concentrated in a residual portion of the mixture, can be added, for example, in the biodiesel process to the glycerol acidification, that is to the separation stage of free fatty acids, salt and glycerol phase. As a result, an additional use of excipients or the generation of additional waste streams is avoided.
  • the membrane used for nano-filtration can consist of a porous or non-porous membrane known to the person skilled in the art.
  • the membrane used is preferably a polyamide-based membrane such as a DOW Filmtech NF membrane and may in particular have a pore size of 0.005 microns to 0.1 microns, more preferably from 0.01 microns to 0.05 microns.
  • the membrane should be chosen so that preferably given against the background of a large-scale design, a high permeation flux and a good resistance of the membrane.
  • the membrane is a polymer membrane.
  • the polymer membranes used are in particular membranes based on polyamide, polysulfone, polyethersulfone, cellulose triacetate, cellulose acetate, thin film composite, silicones and combinations of these compounds.
  • polar organic solvents and / or water may be added prior to filtration.
  • the viscosity of the mixture to be filtered can be adjusted by simple addition of short-chain alcohols such as methanol or ethanol to the optimal specifications of the process.
  • the process according to the invention can be conducted either as a batch process or as a continuous process. It is particularly preferably conducted as a continuous process.
  • a method according to the present invention can be used particularly preferably for the recovery of glycerol from the transesterification reaction of biological, that is to say vegetable and / or animal, fats or oils.
  • a glycerine mixture was passed through a crossflow unit with water, methanol, K 2 SO 4 .
  • the membrane used was the membrane DK2540F1073 from GE Osmonics.
  • the membrane was used with a membrane area of 44 cm 2 and a volume flow of 450 l / h.
  • a transmembrane pressure of 59 bar By applying a transmembrane pressure of 59 bar, a permeate could be achieved, which has a mean conductivity of 0.31 mS.
  • Example 2 As can be clearly seen from Table 1, the electrolyte ions of the organic feed are effectively retained by the nanoflutration, so that the permeate can be recovered almost free from electrolyte after a single filtration step.
  • Example 2 As can be clearly seen from Table 1, the electrolyte ions of the organic feed are effectively retained by the nanoflutration, so that the permeate can be recovered almost free from electrolyte after a single filtration step.
  • a glycerine mixture was passed through a crossflow unit with water, methanol and K 2 SO 4 .
  • the membrane used was a NF membrane from DOW Filmtech.
  • the membrane was tested with a membrane area of 44 cm 2 and a flow rate of 410 l / h.
  • a transmembrane pressure of 20 bar By applying a transmembrane pressure of 20 bar, a permeate could be achieved which has a mean conductivity of 0.49 mS.
  • the analytical examination of the samples of both solutions gave the following measurement data:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne un procédé industriel servant à purifier un mélange de produits de réaction de transestérification présentant une phase polaire organique contenant un électrolyte, ce qui consiste à séparer l'électrolyte de la phase polaire organique de perméation au moyen d'une étape de nanofiltration.
EP08735138A 2007-04-23 2008-04-10 Procédé servant à purifier un mélange de produits généré par des réactions de transestérification Withdrawn EP2142286A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007019379A DE102007019379A1 (de) 2007-04-23 2007-04-23 Verfahren zur Aufreinigung von Produktgemischen aus Umesterungsreaktionen
PCT/EP2008/002828 WO2008128652A1 (fr) 2007-04-23 2008-04-10 Procédé servant à purifier un mélange de produits généré par des réactions de transestérification

Publications (1)

Publication Number Publication Date
EP2142286A1 true EP2142286A1 (fr) 2010-01-13

Family

ID=39578638

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08735138A Withdrawn EP2142286A1 (fr) 2007-04-23 2008-04-10 Procédé servant à purifier un mélange de produits généré par des réactions de transestérification

Country Status (6)

Country Link
US (1) US20100145108A1 (fr)
EP (1) EP2142286A1 (fr)
CA (1) CA2684646A1 (fr)
DE (1) DE102007019379A1 (fr)
RU (1) RU2009142822A (fr)
WO (1) WO2008128652A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008060888A1 (de) 2008-12-09 2010-06-10 Evonik Stockhausen Gmbh Verfahren zur Herstellung von Acrolein umfassend die Aufarbeitung einer Rohglycerin-Phase
US9018424B2 (en) * 2011-03-30 2015-04-28 Toray Industries, Inc. Method of producing diol or triol
RU2665041C2 (ru) * 2016-12-30 2018-08-27 Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" Способ получения биодизельного топлива

Family Cites Families (9)

* Cited by examiner, † Cited by third party
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US2271619A (en) 1939-04-19 1942-02-03 Du Pont Process of making pure soaps
US2360844A (en) 1941-11-26 1944-10-24 Du Pont Preparation of detergents
US3422008A (en) * 1963-10-24 1969-01-14 Dow Chemical Co Wound hollow fiber permeability apparatus and process of making the same
DE19925871A1 (de) 1999-06-07 2000-12-21 At Agrar Technik Gmbh Verfahren zur Herstellung von Fettsäureestern einwertiger Alkylalkohole und deren Verwendung
HU0104786D0 (en) 2001-11-08 2002-01-28 Kovacs Andras Dr Method for producing of vegetable oil-methyl-esther
KR20030026269A (ko) 2003-02-14 2003-03-31 강봉규 이온교환막전기탈염장치(Electrodeionzation, EDI)를이용한 글리세린용액의 탈염 정제방법
DE102004044660A1 (de) 2004-09-15 2006-03-30 Siegfried Prof. Dr. Peter Verfahren zur Umesterung von Fetten und Ölen biologischen Ursprungs mittels Alkoholyse unter Verwendung spezieller Kohlensäuresalze
US20070232818A1 (en) * 2005-11-15 2007-10-04 Domestic Energy Leasing, Llc Transesterification of oil to form biodiesels
US20070175092A1 (en) * 2005-11-28 2007-08-02 Ames Randall S Continuous flow biodiesel processor

Non-Patent Citations (1)

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Title
See references of WO2008128652A1 *

Also Published As

Publication number Publication date
DE102007019379A1 (de) 2008-10-30
RU2009142822A (ru) 2011-05-27
CA2684646A1 (fr) 2008-10-30
WO2008128652A1 (fr) 2008-10-30
US20100145108A1 (en) 2010-06-10

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