EP1934320A1 - Procede de cristallisation de melanges de substances en solution - Google Patents

Procede de cristallisation de melanges de substances en solution

Info

Publication number
EP1934320A1
EP1934320A1 EP06792082A EP06792082A EP1934320A1 EP 1934320 A1 EP1934320 A1 EP 1934320A1 EP 06792082 A EP06792082 A EP 06792082A EP 06792082 A EP06792082 A EP 06792082A EP 1934320 A1 EP1934320 A1 EP 1934320A1
Authority
EP
European Patent Office
Prior art keywords
mixture
heat exchanger
crystals
substances
temperature
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Withdrawn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
EP06792082A
Other languages
German (de)
English (en)
Inventor
Herbert Holpe
Sigrid Kerschbaum
Klaus Schubert
Günter RINKE
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.)
Karlsruher Institut fuer Technologie KIT
Original Assignee
Forschungszentrum Karlsruhe 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 Forschungszentrum Karlsruhe GmbH filed Critical Forschungszentrum Karlsruhe GmbH
Publication of EP1934320A1 publication Critical patent/EP1934320A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
    • C11B7/0075—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of melting or solidifying points
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to a process for the solution crystallization of. liquid mixtures according to the first claim.
  • a typical example from the everyday practice to do this is diesel fuels in which certain sub-substances crystallize at low winter temperatures, the mixture thereby macroscopically occupies a gel-like substance with an increased viscosity and thus significantly hindering handling in injection components such as nozzles in diesel engines.
  • This restriction can be observed especially with so-called biodiesel, in which the substance mixture is made up of oils of different origin or production as partial substances. Crystallization is usually hampered by the addition of appropriate additives, such as in the so-called. Winter diesel usual, mixed with the mixture.
  • biodiesel is obtained from the transesterification of rapeseed oil as rapeseed methyl ester (RME).
  • RME rapeseed methyl ester
  • the cold resistance of biodiesel based on used oil base is attempted to be improved by so-called winterization.
  • the cold strength describes the temperature at which a substance from the liquid in passes the solid state and corresponds / if crystals are formed, the melting temperature of the substance. Practically, this means that the fluidity of the fuel is limited by increasing gel formation and the formation of crystals in the product and prevents motor use.
  • accompanying substances such as waxes, residues of undesirable reaction products such as glycerides and glycerol contribute to this behavior.
  • the mode of action of such products is based on the formation of a large number of crystallization seeds with a size of less than 50 ⁇ m, which prevent agglomeration in the biodiesel. Although this effectively counteracts gel or crystal formation, so that the requirements of winterization (CFPP measurement according to DIN EN 116) can be formally fulfilled, the problem is not fundamentally solved, since a crystallization of the product extremely delayed, but not prevented becomes.
  • the fractional winterization and physical filtering off open ⁇ discloses crystallized components in US 4,265,826, in which the high boiling components to crystallize out according to their boiling points.
  • the mixture is cooled until crystals form in a filterable size.
  • Be ⁇ ferred cooling rates are between 0.5 and 5 ° C / h, optio ⁇ nal at certain temperature levels residence times between 2 - h are provided 16th
  • the total yield can vary depending on the requirement of the Cold strength of the product below 30%, based on the starting material, fall and is therefore not economical.
  • DE 34 44 475 C2 also describes a device for separating crystals by means of a vacuum belt filter for the dry fractionation of fats and oils, which moves in the area of classic winterization. The process works batchwise and requires no additional chemicals.
  • the object of the invention is to propose a process for the solution crystallization of mixtures of substances, in particular of fuels such as biodiesel, which makes do without additives and is also suitable for increasing the winter strength of biodiesel fuels for larger quantities.
  • the solution is based on a process for the solution crystallization of mixtures, in particular fuels such as biodiesel.
  • a partial stream is taken from a liquid substance mixture which contains at least one sub-substance with an increased melting point.
  • This sub-stream contains all sub-substances occurring in the substance mixture and is preferably representative of the substance mixture, ie it holds the sub-substances in the same ratio to each other as the mixture.
  • the partial flow is then a heat exchanger - A - zugeschreibt and introduced into the Fluidbowungen of the heat exchanger, the partial flow flows through the heat exchanger.
  • the partial flow is cooled to a temperature below a crystallization temperature of only the partial substances of the substance mixture, while the other partial substances remain unchanged in the partial flow in the liquid phase.
  • the temperature and the flow rate are adjusted so that crystals of the crystallized partial substances form in the partial flow directly at the outlet from the heat exchanger in the partial flow.
  • the location of the crystal formation by means of a relaxation in the fluid, such as through a nozzle or a pressure reducer set additionally targeted. This is followed by a re-mixing of the partial flow with the crystals formed of one or more sub-substances in the mixture, wherein the crystals in the mixture further substances selectively bind by crystal growth itself.
  • the mixture of substances is either not rolled over (sedimentation) or mixed and cooled and held on the so-called cloud point, as the temperature at which turbidity and incipient crystallization can be detected.
  • the crystals are separated by a separation process from the mixture, for example by filtration or ultracentrifuge
  • FIG.l the schematic structure of an exemplary embodiment for carrying out the method on a laboratory scale
  • the exemplary embodiment acc. Fig.l comprises a storage vessel 1 for about 5 liters of biodiesel 2 with temperature sensor 32, and a circuit with suction 9, a pump 10 (gear pump), heat exchanger 16 (heat exchanger, in the exemplary embodiment, a cross-flow micro waremubertrager) and return 20 for the branch partial crystallization and recycling of the partial flow from and into the Vorratsgefrub.
  • the storage vessel 1, e.g. a 5-liter beaker includes a tempering, in the exemplary embodiment, a wrapping with a PVC hose as Kuhlmantel 3, which is connected as part of a closed Kuhlstoffniklaufs Kuhlstoffzutechnisch 7 and a Kuhl- medium pressure line 8 to a thermostat 5.
  • the coolant 6 is a volumetric 1: 1 mixture of ethylene glycol and water.
  • the storage vessel 1 and the Kuhlstoffzutechnisch 7 are surrounded with insulation material.
  • the biodiesel 2 in the storage vessel is optionally kept in motion by means of a magnetic stirrer 4.
  • the partial flow is sucked by the pump 10 via the suction line 9, in the exemplary embodiment, a metal hose or poleugrüssel, preferably from the lower third of the Vorratsgefackedes 1 and discharged via the return 20 into the upper third again. In this way, a large part of the biodiesel 2 in the storage vessel 1 is rolled over.
  • the pump 10 forwards the partial flow via a heat exchanger feed 12 (eg metal hose) to the heat exchanger 16 with a microfilter 11.
  • the Warmeubertragerzussel is equipped to maintain a kon ⁇ constant heat input entering temperature and to avoid premature crystal formation in the partial flow before and in the heat exchanger 16 with a tempering device for the partial flow.
  • Heat exchanger, Kuhlmediumthermostat, Kuhlmediumpumpe and a Kuhlstofffilter 25 are connected via a Kuhlstoffzutechnisch 23, a Kuhlstofftechnisch 26 Kuhlstoffabtechnisch 27 and other lines (each polyethylene hoses) to a closed Kuhlstoffnikank.
  • the heat exchanger used in the exemplary embodiment is a micro-Kreuzstromwaremubertrager with a variety of Fluidschreibungen with diameters or maximum cross-sectional dimensions less than 1 mm. Due to its fineness, the heat exchanger is characterized by a high specific heat transfer, i. large specific heat transfer planes and small heat transfer paths.
  • the fluid guides are subdivided into two fluid guide fractions, which are layered in alternating order and cross each other, preferably at right angles to one another.
  • a micro-heat exchanger is used, which comprises a layered structure with a metal foil stack, wherein the Fluidschreibungen are incorporated as kanalformige depressions in the stacked and interconnected by diffusion bonding fluid-tight individual foils. Each of these individual films has a plurality of similar, preferably parallel to each other Fluidbowungen only one Fluidbowungsfr neglect.
  • the temperature at the inlet and outlet of Biodiesel and Kuhlmediumpassagen the heat exchanger 16 with the help of Temperaturmessfuhêt (temperature sensors on the heat transfer inlet 28, the Warmeubertrageraustritt 29, the Kuhlmediumzulauf of the heat exchanger 30 and Kuhlmediumablauf the heat exchanger 31) measured and therefrom the temperature gradient determined in the heat exchanger.
  • a further temperature sensor 32 is located in the interior of the storage vessel 1.
  • 16 pressure sensors pressure sensor on the heat transfer inlet 33 and the heat exchanger outlet 34
  • This device allows the above-mentioned winterization of biodiesel fuels in two different ways as follows:
  • the temperature of the biodiesel is in the heat exchanger 16 Ich lowered by adjusting the temperature in Kuhlffenthermostaten 21 ⁇ until 18 crystals 19 show in the sight glass. Thereafter, the temperature of the Kuhlmantels 3 of the Vorratsgefackedes 1 is slowly lowered by adjusting the temperature in the thermostat 5. The temperature of the cold medium circuit in the heat exchanger 16 is kept constant. The crystals formed are passed through the partial flow circuit in the storage vessel 1 and sediment there to the ground, be but whirled up again by the magnetic stirrer 4, so that the crystals are distributed as crystallization nuclei in the entire storage vessel. By regular sampling, the decrease of the saturated fatty acid methyl ester in the liquid biodiesel can be determined by means of gas chromatography. The temperature in the storage vessel is then lowered until the desired composition of the biodiesel 2 is reached.
  • the temperature of the biodiesel is lowered in the heat exchanger 16 by adjusting the temperature in the Kuhlffenthermostaten 21 until 18 show crystals 19 in the sight glass. Thereafter, the temperature of the Kuhlmantels 3 of the Vorratsgefackedes 1 is slowly lowered by adjusting the temperature in the thermostat 5. After a certain time for crystal formation and crystal growth (about 5 hours), the two pumps IO and 24 and the magnetic stirrer 4 are switched off. In the storage vessel 1 crystals formed sink down, during which the biodiesel is sampled in the storage vessel at regular intervals and analyzed. If the concentration of the saturated fatty acid methyl ester does not change any more or only slightly, the temperature of the storage vessel 1 is further lowered via the thermostat 5. This process is repeated until the desired composition of the biodiesel is achieved.
  • biodiesel from used cooking oil was used whose composition was previously determined.
  • the proportion of saturated fatty acid methyl ester at the beginning of the experiment was 22%.
  • Figures 2 and 3 show the time course of the cumulative Kon ⁇ concentration (concentration curve 38) of the saturated Fettsauremethylester of AME and the temperature in Vorratsgefrub 1 (tempera ⁇ turverlauf 39) as functions of time for the Experimental Example 1 (Fig.2 ) or Experimental Example 2 (Fig.3).
  • FIG. 4 shows the temperature profiles for both experimental examples (via the concentration 41, in each case as a point quantity and as a geometrically-averaged straight line, straight line of test example 1 lies below that of test example 2) in the storage vessel of AME (biodiesel temperature 35) and the empirical course of FIG CFPP values 42 (CFPP value 40) as functions of the sum concentration of saturated fatty acid methyl esters (concentration 36).
  • the CFPP is a measure of the winter strength of biodiesel. It increases with increasing concentration of saturated fatty acids. During the measurements, care was taken in both of the above experimental examples that bath temperatures were above the CFPP values for the same concentration of the saturated fatty acids.
  • a further advantageous embodiment comprises a use of countercurrent micro-heat exchanger (countercurrent Mikrowarmeübertragern) instead of the cross-flow described in the exemplary embodiment Mikrowarmeubertragers. This allows a gleichschreibigere temperature distribution can be achieved at the output of the heat exchanger.

Landscapes

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

Abstract

L'invention concerne un procédé de cristallisation de mélanges de substances en solution. L'objectif de cette invention est de créer un procédé permettant d'améliorer, sans additif, la stabilité, en période hivernale, de biocarburants diesel, également en grandes quantités. A cet effet, le procédé selon l'invention consiste : à préparer un mélange de substances liquides (2) comprenant au moins une substance partielle qui présente un point de fusion élevé ; à prélever un courant partiel (9) du mélange de substances (2) ; à introduire ce courant partiel dans un échangeur thermique (16), ce courant partiel traversant l'échangeur thermique ; à refroidir le courant partiel dans l'échangeur thermique pour le porter à une température inférieure à la température de formation de cristaux, ceci uniquement pour les substances partielles du mélange de substances, la température étant réglée de manière que des cristaux (19) des substances partielles soient formés dans le courant partiel, directement à la sortie de l'échangeur thermique (16) ; à mélanger le courant partiel avec les cristaux dans le mélange de substances (2), les cristaux dans le mélange de substances se liant sélectivement avec d'autres substances par croissance cristalline, et ; à induire la sédimentation et de dépôt des cristaux dans le mélange de substances.
EP06792082A 2005-10-12 2006-09-15 Procede de cristallisation de melanges de substances en solution Withdrawn EP1934320A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005048881A DE102005048881A1 (de) 2005-10-12 2005-10-12 Verfahren zur Lösungskristallisation von Stoffgemischen
PCT/EP2006/009000 WO2007042121A1 (fr) 2005-10-12 2006-09-15 Procede de cristallisation de melanges de substances en solution

Publications (1)

Publication Number Publication Date
EP1934320A1 true EP1934320A1 (fr) 2008-06-25

Family

ID=37309003

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06792082A Withdrawn EP1934320A1 (fr) 2005-10-12 2006-09-15 Procede de cristallisation de melanges de substances en solution

Country Status (5)

Country Link
US (1) US20080276525A1 (fr)
EP (1) EP1934320A1 (fr)
CA (1) CA2620011A1 (fr)
DE (1) DE102005048881A1 (fr)
WO (1) WO2007042121A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009010329A1 (de) * 2009-02-25 2010-08-26 Karlsruher Institut für Technologie Temperaturregelung für einen Mikrostrukturverdampfer zur Kühlung von Flüssigkeiten
US11530878B2 (en) 2016-04-07 2022-12-20 Hamilton Sundstrand Corporation Spiral tube heat exchanger

Family Cites Families (18)

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Publication number Priority date Publication date Assignee Title
DE746670C (de) * 1942-02-07 1944-08-18 Der Kohlenwertstoff Verbaende Verfahren zur Verbesserung von Dieselkraftstoffen
US2672487A (en) * 1949-05-28 1954-03-16 Standard Oil Dev Co Para xylene separation process
US3450727A (en) * 1965-06-29 1969-06-17 Procter & Gamble Continuous solvent winterization of partially hydrogenated soybean oil
US3448588A (en) * 1966-07-29 1969-06-10 Phillips Petroleum Co Crystallization of a liquid mixture with subcooled crystals of one component of the mixture
IL35793A (en) * 1969-12-12 1973-10-25 Stamicarbon Continuous process for crystallization
DE2158755A1 (de) * 1971-11-26 1973-06-07 Klaus Zondek Verfahren und vorrichtung zum entfernen der kristallisierbaren bestandteile und verunreinigungen aus oelen durch auskristallisieren
AR204539A1 (es) * 1973-09-17 1976-02-12 Hercules Inc Procedimiento y aparato para la cristalizacion continua por enfriamiento de un soluto cristalizable
NL183275C (nl) * 1977-05-31 1988-09-16 Sulzer Ag Werkwijze voor het door gefractioneerde kristallisatie scheiden van stofmengsels, alsmede inrichting voor het uitvoeren van deze werkwijze.
JPS6033878B2 (ja) * 1977-12-01 1985-08-05 味の素株式会社 油脂類の自然分別法
US4354921A (en) * 1981-07-27 1982-10-19 Texaco Inc. Solvent dewaxing process
CH658163A5 (fr) * 1983-10-07 1986-10-31 Nestle Sa Procede de production de fractions comestibles de matieres grasses et leur utilisation.
US20090188157A1 (en) * 1999-10-26 2009-07-30 Holloway Jr William D Device and method for combining oils with other fluids and mixtures generated therefrom
DE10026619A1 (de) * 2000-05-29 2001-12-06 Basf Ag Vorrichtung zur Herstellung von Kristallen
PT1563041E (pt) * 2002-11-13 2008-09-25 Lanxess Deutschland Gmbh Utilização de 2,6-di-terc-butil-p-cresol para aumentar a estabilidade à armazenagem de biodiesel
WO2004064990A2 (fr) * 2003-01-22 2004-08-05 Vast Power Systems Inc. Reacteur
US20040231234A1 (en) * 2003-05-19 2004-11-25 May Choo Yuen Palm diesel with low pour point for climate countries
US6904963B2 (en) * 2003-06-25 2005-06-14 Valeo, Inc. Heat exchanger
EP1557441A3 (fr) * 2003-12-08 2006-06-28 Peter Dr. Wilharm Agent de nucléation à base de polymères hyperbranchés

Non-Patent Citations (1)

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Title
See references of WO2007042121A1 *

Also Published As

Publication number Publication date
CA2620011A1 (fr) 2007-04-19
DE102005048881A1 (de) 2007-04-19
US20080276525A1 (en) 2008-11-13
WO2007042121A1 (fr) 2007-04-19

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