EP0105066B1 - Procédé pour la séparation d'acides gras utilisant un lit fixe d'adsorbant - Google Patents

Procédé pour la séparation d'acides gras utilisant un lit fixe d'adsorbant Download PDF

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Publication number
EP0105066B1
EP0105066B1 EP82305310A EP82305310A EP0105066B1 EP 0105066 B1 EP0105066 B1 EP 0105066B1 EP 82305310 A EP82305310 A EP 82305310A EP 82305310 A EP82305310 A EP 82305310A EP 0105066 B1 EP0105066 B1 EP 0105066B1
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Prior art keywords
adsorbent
desorbent
acid
zone
adsorption
Prior art date
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Expired
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EP82305310A
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German (de)
English (en)
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EP0105066A1 (fr
Inventor
Michael Terence Cleary
Santi Kulprathipanja
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Honeywell UOP LLC
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UOP LLC
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Priority to AT82305310T priority Critical patent/ATE22323T1/de
Priority to DE8282305310T priority patent/DE3273366D1/de
Priority to EP82305310A priority patent/EP0105066B1/fr
Publication of EP0105066A1 publication Critical patent/EP0105066A1/fr
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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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/005—Splitting up mixtures of fatty acids into their constituents

Definitions

  • This invention relates to the separation of fatty acids from mixtures of fatty acids.
  • the fatty acids are a large group of aliphatic monocarboxylic acids, many of which occur as glycerides (esters of glycerol) in natural fats and oils.
  • fatty acids has been restricted by some to the saturated acids of the acetic acid series, both normal and branched chain, it is now generally used, and is so used herein, to include also related unsaturated acids, certain substituted acids, and even aliphatic acids containing alicyclic substituents.
  • the naturally occurring fatty acids with a few exceptions are higher straight chain unsubstituted acids containing an even number of carbon atoms.
  • the unsaturated fatty acids can be divided, on the basis of the number of double bonds in the hydrocarbon chain, into monoethanoid, diethanoid, triethanoid, etc. (or monoethylenic, etc.).
  • unsaturated fatty acid is a generic term for a fatty acid having at least one double bond
  • polyethanoid fatty acid means a fatty acid having more than one double bond per molecule.
  • Fatty acids are typically prepared from glyceride fats or oils by one of several "splitting" or hydrolytic processes. In all cases the hydrolysis reaction may be summarized as the reaction of a fat or oil with water to yield fatty acids plus glycerol.
  • fatty acids are in the plasticizer and surface active agent fields.
  • Derivatives of fatty acids are of value in compounding lubricating oil, as lubricants for the textile and molding trade, in special lacquers, as water-proofing agents, in the cosmetic and pharmaceutical fields, and in biodegradable detergents.
  • absorbents comprising non-ionic hydrophobic insoluble crosslinked styrene polymers exhibit adsorptive selectively for certain fatty acids with respect to other fatty acids, thereby making separation of such fatty acids by solid bed selective adsorption possible.
  • These adsorbents can be used both for separating stearic acid from its admixture with palmitic acid, and for separating oleic acid from its admixture with linoleic acid.
  • a process for separating stearic acid or oleic acid from a mixture of. stearic acid and palmitic acid or a mixture of oleic acid and linoleic acid is characterised in that the mixture is contacted with an adsorbent comprising a nonionic hydrophobic insoluble crosslinked styrene polymer whereby stearic acid or oleic acid is selectively adsorbed.
  • the process is characterised in that it comprises the steps of: (a) maintaining net fluid flow in a single direction through a column of the adsorbent, which column contains at least three zones having separate operational functions occurring therein and serially interconnected with the terminal zones of the column connected to provide a cyclic connection; (b) maintaining in the column, an adsorption zone defined by the adsorbent located between a feed mixture input at its upstream boundary and a raffinate stream output at its downstream boundary; (c) maintaining in the column, immediately upstream of the adsorption zone, a purification zone defined by the adsorbent located between an extract stream output at its upstream boundary and the feed mixture input at its downstream boundary; (d) maintaining in the column, immediately upstream of the purification zone a desorption zone defined by the adsorbent located between a desorbent input at its upstream boundary and the extract stream output at its downstream boundary; (e) passing the feed mixture into the adsorption zone at adsorption conditions effecting the selective a
  • the feed mixture is a mixture of an extract component and a raffinate component.
  • extract component is the compound that is selectively more adsorbed by the adsorbent while the “raffinate component” is the compound that is selectively less adsorbed.
  • stearic acid or oleic acid is the extract component and palmitic acid or linoleic acid is the raffinate component.
  • desorbent means a material capable of desorbing the extract component from the adsorbent.
  • raffinate stream means the stream through which the raffinate component is removed from the adsorbent.
  • the composition of the raffinate stream can vary from essentially 100% desorbent to essentially 100% raffinate component.
  • extract stream means a stream through which the extract component which has been desorbed by the desorbent is removed from the adsorbent.
  • the composition of the extract stream likewise, can vary from essentially 100% desorbent to essentially 100% extract component.
  • separation means typically fractionators where at least a portion of the desorbent is separated to produce an extract product and a raffinate product.
  • extract product and "raffinate-product” means products produced by-the process containing, respectively, the extract component and the raffinate component in higher concentrations than those found in the extract stream and the raffinate stream.
  • extract component is never completely adsorbed by the adsorbent, nor is a raffinate component completely, non-adsorbed by the adsorbent.
  • varying amounts of the raffinate component can appear in the extract stream and, likewise, varying amounts of the extract component can apepar in the raffinate stream.
  • the extract and raffinate streams then are further distinguished from each other and from the feed mixture by the ratio of the concentrations of an extract component and a raffinate component appearing in the particular stream. More specifically, the ratio of the concentration of stearic or oleic acid to that of palmitic or linoleic acid will be lowest in the raffinate stream, next highest in the feed mixture, and the highest in the extract stream.
  • feed mixture for the process of the present invention is known as "tall oil fatty acids" and typically comprises about 1 vol. % of palmitic acid, 2 vol. % stearic acid, 51 vol. % oleic acid, 45 vol. % linoleic acid and 4 vol. % others.
  • Feed mixtures which can be charged to the process may contain, in addition to fatty acids, a diluent material that is not adsorbed by the adsorbent and which is preferably separable from the extract and raffinate output streams by fractional distillation.
  • concentration of diluent in the mixture of diluent and fatty acids may be from a few vol. % up to about 90 vol. %.
  • Desorbent materials used in adsorptive separation processes vary depending upon such factors as the type of operation employed. In the swing-bed system in which a selectively adsorbed feed component is removed from the adsorbent by a purge stream desorbent selection is not as critical and desorbent materials comprising gaseous hydrocarbons such as methane or ethane or other types of gases such as nitrogen or hydrogen may be used at elevated temperatures or reduced pressures or both to effectively purge the adsorbed feed component from the adsorbent. However, in adsorptive separation processes which are generally operated continuously at substantially constant pressures and temperatures to ensure liquid phase, a desorbent material must be judiciously selected to satisfy many criteria.
  • a desorbent material should displace an extract component from an adsorbent with reasonable mass flow rates without itself being so strongly adsorbed as to unduly prevent an extract component from displacing the desorbent material in a following adsorption cycle.
  • an adsorbent be more selective for all extract components with respect to a raffinate component than it is for a desorbent material with respect to a raffinate component.
  • desorbent materials must be compatible with a particular adsorbent and a particular feed mixture. More specifically, a desorbent material must not reduce or destroy the critical selectivity of an adsorbent for an extract component with respect to a raffinate component.
  • a desorbent material should additionally be a substance which is easily separable from the feed mixture that is passed into the process.
  • a raffinate stream and an extract stream removed from an absorbent both typically contain desorbent material and without a method of separating at least a portion of the desorbent material the purity of an extract product and a raffinate product would not be very high, nor would a desorbent material be available for reuse in the process. It is therefore contemplated that any desorbent material used in this process will preferably have an average boiling point substantially different from that of a feed mixture to allow separation of at least a portion of desorbent material from feed components in an extract and a raffinate stream by simple fractional distillation, thereby permitting reuse of a desorbent material in the process.
  • substantially different means that the difference in the average boiling points between a desorbent material and a feed mixture is at least 5°C.
  • the boiling range of a desorbent material may be higher or lower than that of a feed mixture.
  • a desorbent material should also be a material which is readily available and therefore resonable in cost.
  • particularly effective desorbents comprise the mixtures acetonitrile and methanol; acetonitrile, tetrahydrofuran and water; acetone and water; dimethyl acetamide and water; methanol and water; dimethyl formamide and water; . quarternary methyl ammonium hydroxide, water and methanol; and quarternary propyl ammonium hydroxide, water and methanol.
  • the adsorbents used in the process of this invention comprise nonionic hydrophobic insoluble crosslinked styrene polymers, preferably those manufactured by the Rohm and Haas Company and sold under the Registered Trade Mark "Amberlite".
  • Types of Amberlite polymers known to be effective for use in this invention are those referred to in Rohm and Haas Company literature as Amberlite XAD-2 and Amberlite XAD-4, and described in the literature as "hard, insoluble spheres of high surface, porous polymer".
  • the various types of Amberlite polymeric adsorbents differ in physical properties such as porosity volume, surface area, average pore diameter, skeletal density and nominal mesh sizes.
  • a fundamental superiority of the Amberlite polymeric adsorbents over crystalline aluminosilicates is that the former, unlike the latter, may be used for the direct, separation of fatty acids without first converting the fatty acids to their corresponding esters.
  • the processes of the aforementioned prior art patents are applicable only to esters of fatty acids because the free carboxylic group of a fatty acid chemically reacts with the crystalline aluminosilicates used by those processes.
  • the adsorbent used according to this invention exhibits no such reactivity and, therefore, the process of this invention is uniquely suitable for the separation of fatty acids.
  • a dynamic testing apparatus has been proposed to test various adsorbents with a particular feed mixture and desorbent material to measure the adsorbent characteristics of adsorptive capacity, selectivity and exchange rate.
  • the apparatus consists of an adsorbent chamber comprising a helical column of approximately 70 ml volume having inlet and outlet portions at opposite ends of the chamber.
  • the chamber is contained within a temperature control means and, in addition, pressure control equipment is used to operate the chamber at a constant predetermined pressure.
  • Quantitative and qualitative analytical equipment such as refractometers, polarimeters and chromatographs can be attached to the outlet line of the chamber and used to detect quantitatively or determine qualitatively one or more components in the effluent stream leaving the adsorbent chamber.
  • a pulse test performed using this apparatus and the following general procedure, is used to determine selectivities and other data for various adsorbent systems.
  • the adsorbent is filled to equilibrium with a particular desorbent material by passing the desorbent material through the adsorbent chamber.
  • a pulse of feed containing known concentrations of a tracer and of a particular extract component or of a raffinate component or both all diluted in desorbent is injected for a duration of several minutes.
  • Desorbent flow is resumed, and the tracer and the extract component or the raffinate component (or both) are eluted as in a liquid-solid chromatographic operation.
  • the effluent can be analyzed onstream or alternatively effluent samples can be collected periodically and later analyzed separately by analytical equipment and traces of the envelopes of corresponding component peaks developed.
  • the retention volume of an extract or a raffinate component may be characterized by the distance between the center of the peak envelope of an extract or a raffinate component and the peak envelope of the tracer component or some other known reference point. It is expressed in terms of the volume in cubic centimeters of desorbent pumped during this time interval represented by the distance between the peak envelopes.
  • (B) for an extract component with respect to a raffinate component may be characterized by the ratio of the distance between the center of the extract component peak envelope and the tracer peak envelope (or other reference point) to the corresponding distance between the center of the raffinate component peak envelope and the tracer peak envelope.
  • the rate of exchange of an extract component with the desorbent can generally be characterized by the width of the peak envelopes at half intensity. The narrower the peak width the faster the desorption rate.
  • the desorption rate can also be characterized by the distance between the center of the tracer peak envelope and the disappearance of an extract component which has just been desorbed. This distance is again the volume of desorbent pumped during this time interval.
  • the adsorbent may be employed in the form of a dense compact fixed bed which is alternately contacted with the feed mixture and the desorbent.
  • the adsorbent is employed in the form of a single static bed in which case the process is only semi-continuous.
  • a set of two or more static beds may be employed in fixed bed contacting with appropriate valving so that the feed mixture is passed through one or more adsorbent beds while the desorbent can be passed through one or more of the other beds in the set.
  • the flow of feed mixture and desorbent may be either up or down through the adsorbent. Any of the conventional apparatus employed in static bed fluid-solid contacting may be used.
  • Countercurrent moving bed or simulated moving bed countercurrent flow systems have a much greater separation efficiency than fixed adsorbent bed systems and are therefore preferred.
  • the adsorption and desorption operations are continuously taking place, which allows both continuous production of an extract and a raffinate stream and the continual use of feed and desorbent streams.
  • One preferred embodiment of this process utilizes what is known in the art as the simulated moving bed countercurrent flow system. The operating principles and sequence of such a flow system are described in the passage of page 8 line 53-page 10 line 2 of GB-A-2049667.
  • At least a portion of the extract stream will preferably pass into a separation means wherein at least a portion of the desorbent can be separated to produce an extract product containing a reduced concentration of desorbent.
  • at least a portion of the raffinate stream will also be passed to a separation means wherein at least a portion of the desorbent can be separated to produce a desorbent stream which can be reused in the process and a raffinate product containing a reduced concentration of desorbent.
  • the separation means will typically be a fractionation column, the design and operation of which is well-known to the separation art.
  • liquid-phase operation is preferred for the process of the present invention because of its lower temperature requirements and because higher yields of extract product can be obtained with liquid-phase operation than with vapor-phase operation.
  • the adsorption is typically carried out at a temperature of from 20 to 200°C, temperatures of 20 to 100°C being preferred, and at a pressure of from atmospheric to 500 psig (3450 kPa gauge), atmospheric to 250 psig (1725 kPa gauge) being preferred to ensure liquid phase.
  • Desorption is typically and preferably carried out in the same ranges of temperatures and pressures as used for adsorption conditions.
  • the size of the units which can be utilized in the process of this invention can vary anywhere from those of pilot plant scale (see for example U.S.-A-3,706,812) to those of commercial scale and can range in flow rates from as little as a few ml an hour up to many thousands of litres per hour.
  • This Example presents selectivities for two Amberlite polymeric adsorbents, comprising Amberlite XAD-2 and Amberlite XAD.-4, for oleic acid with respect to a linoleic acid.
  • the feed mixture comprised the desorbent used in the pulse test in question and tall-oil fatty acids in a ratio of desorbent to tall-oil fatty acids of 90:10.
  • the tall-oil fatty acids had the following composition by volume:
  • Retention volumes and selectivities were obtained using the pulse test apparatus and procedure previously described. Specifically, the adsorbents were tested in a 70 ml helical coiled column using the following sequence of operations for each pulse test. Desorbent material was continuously run through the column containing the adsorbent at a nominal liquid hourly space velocity (LHSV) of about 1.0. A void volume was determined by observing the volume of desorbent required to fill the packed dry column. At a convenient time the flow of desorbent material was stopped, and a 10 ml sample of feed mixture was injected into the column via a sample loop and the flow of desorbent material was resumed. Samples of the effluent were automatically collected in an automatic sample collector and later analyzed by chromatographic analysis.
  • LHSV liquid hourly space velocity
  • the retention volume for the fatty acids were calculated by measuring the distances from time zero on the reference point to the respective midpoints of the fatty acids and subtracting the distance representing the void volume of the adsorbent.
  • the selectivities of an adsorbent for oleic acid with respect to linoleic acid in the presence of a desorbent material are in the quotients obtained by dividing the retention volume for the oleic acid by the retention volume for the linoleic acid.
  • This example presents the results of using Amberlite XAD-2 for separating stearic acid from about a 50-50 mixture of stearic and palmitic acids diluted in desorbent in a ratio of desorbent to acid mixture of 90:10.
  • the desorbent used was 85 wt.% dimethyl formamide and 15 wt.% water.
  • Data were obtained using the pulse test apparatus and procedure previously described at a temperature of 90°C. Specifically, the adsorbent was placed in a 70 ml helical coiled column and the following sequence of operations was used. Desorbent material was continuously run upflow through the column containing the adsorbent at a flow rate of 1.2 ml/min. At a convenient time the flow of desorbent material was stopped, and a 10 ml sample of feed mixture was injected into the column via a sample loop and the flow of desorbent material was resumed. Samples of the effluent were automatically collected in an automatic sample collector and later analyzed by chromatographic analysis.
  • FIG. 2 of the drawings shows that stearic acid is more strongly adsorbed than palmitic acid, particularly for the desorbent mixture used. Furthermore the separation achieved for this combination was substantial and clearly of commercial feasibility.

Claims (7)

1. Un procédé pour séparer l'acide stéarique ou l'acide oléique à partir d'un mélange d'acide stéarique et d'acide palmitique ou d'un mélange d'acide oléique et d'acide linoléique, caractérisé en ce que l'on met en contact le mélange avec un adsorbant comprenant un polymère du styrène réticulé, insoluble, hydrophobe et non-ionique, ce par quoi l'acide stéarique ou l'acide oléique est adsorbé sélectivement.
2. Un procédé selon la revendication 1, caractérisé en ce que l'on récupère l'acide stéarique ou l'acide oléique à partir de l'adsorbant, par désorption avec un désorbant.
3. Un procédé selon la revendication 2, caractérisé en ce que le désorbant comprend un mélange choisi parmi l'acétonitrile et le méthanol; l'acétonitrile, le tétrahydrofuranne et l'eau; l'acétone et l'eau; le diméthylacétamide et l'eau; le méthanol et l'eau; le diméthylformamide et l'eau; l'hydroxyde de méthylammonium quaternaire, l'eau et le méthanol; et l'hydroxyde de propylammonium quaternaire, l'eau et le méthanol.
4. Un procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'adsorption et, lorsqu'elle se produit, la désorption sont effectuées à une température comprise entre 20 et 200°C et à une pression comprise entre la pression atmosphérique et environ 3450 kPa au manomètre (500 psig).
5. Un procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il est réalisé en phase liquide.
6. Un procédé selon l'une quelconque des revendications 2 à 5, caractérisé en ce qu'il comprend les étapes suivantes:
(a) maintenir un écoulement de fluide net dans une direction unique, à travers une colonne de l'adsorbant, laquelle colonne contient au moins trois zones ayant des fonctions opérationnelles séparées se déroulant à l'intérieur de celles-ci et interconnectées en série avec les zones terminales de la colonne, connectées pour fournir une connexion cyclique;
(b) maintenir dans la colonne, une zone d'adsorption définie par l'adsorbant situé entre une entrée de mélange d'alimentation à sa limite amont et une sortie de courant raffiné à sa limite aval;
(c) maintenir dans la colonne, immédiatement en amont de la zone d'adsorption, une zone de purification définié par l'adsorbant situé entre une sortie de courant extrait à sa limite amont de l'entrée de mélange d'alimentation à sa limit aval;
(d) maintenir dans la colonne, immédiatement en amont de la zone de purification, une zone de désorption définie par l'adsorbant situé entre une entrée de désorbant à sa limite amont et la sortie de courant extrait à sa limite aval;
(e) faire passer le mélange d'alimentation dans la zone d'adsorption à des conditions d'adsorption effectuant l'adsorption sélective de l'acide stéarique ou de l'acide oléique à partir du mélange par l'adsorbant dans la zone d'adsorption, et soutirer un courant raffiné comprenant l'acide palmitique ou l'acide linoléique de la zone d'adsorption;
(f) faire passer le désorbant dans la zone de désorption à des conditions de désorption effectuant le déplacement de l'acide adsorbé à partir de l'adsorbant dans la zone de désorption;
(g) soutirer un courant extrait comprenant l'acide déplacé et le désorbant de la zone de désorption;
(h) faire passer au moins une portion du courant extrait à un moyen de séparation et y séparer au moins une portion du désorbant; et
(i) avancer périodiquement à travers la colonne d'adsorbant, dans une direction vers l'aval par rapport à l'écoulement fluide dans la zone d'adsorption: l'entrée de mélange d'alimentation, la sortie de courant raffiné, l'entrée de désorbant, et la sortie de courant extrait, pour effecteur le déplacement des zones d'adsorption, de purification et de désorption à travers l'adsorbant.
7. Un procédé selon la revendication 6, caractérisé en ce que l'on maintient une zone tampon dans la colonne, immédiatement en amont de ladite zone de désorption, la zone tampon étant définie par l'adsorbant situé entre lentrée de désorbant à sa limite aval et la sortie de courant raffiné à sal limite amont.
EP82305310A 1982-10-06 1982-10-06 Procédé pour la séparation d'acides gras utilisant un lit fixe d'adsorbant Expired EP0105066B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT82305310T ATE22323T1 (de) 1982-10-06 1982-10-06 Verfahren zur trennung von fettsaeuren unter verwendung eines festen bettes aus adsorbern.
DE8282305310T DE3273366D1 (en) 1982-10-06 1982-10-06 Process for the separation of fatty acids using a solid bed of adsorbent
EP82305310A EP0105066B1 (fr) 1982-10-06 1982-10-06 Procédé pour la séparation d'acides gras utilisant un lit fixe d'adsorbant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP82305310A EP0105066B1 (fr) 1982-10-06 1982-10-06 Procédé pour la séparation d'acides gras utilisant un lit fixe d'adsorbant

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EP0105066A1 EP0105066A1 (fr) 1984-04-11
EP0105066B1 true EP0105066B1 (fr) 1986-09-17

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Publication number Priority date Publication date Assignee Title
DE3831516A1 (de) * 1988-09-16 1990-03-22 Henkel Kgaa Verfahren zum anreichern von oelsaeure und/oder elaidinsaeure
US5288619A (en) * 1989-12-18 1994-02-22 Kraft General Foods, Inc. Enzymatic method for preparing transesterified oils

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB820272A (en) * 1958-02-21 1959-09-16 Shell Res Ltd Separation of a mixture of acidic or neutral non-hydrocarbons of which at least one is acidic
AU410318B1 (en) * 1966-07-27 1971-02-10 Universal Oil Products Company Continuous solid fluid contacting process
DE2261067A1 (de) * 1972-12-14 1974-06-27 Henkel & Cie Gmbh Verfahren zur reinigung von fettsaeureoder fettsaeureestergemischen
US4049688A (en) * 1976-08-02 1977-09-20 Uop Inc. Process for separating esters of fatty acids by selective adsorption
US4113887A (en) * 1977-02-24 1978-09-12 General Foods Corporation Adsorption process
US4329280A (en) * 1981-04-10 1982-05-11 Uop Inc. Process for separating esters of fatty and rosin acids

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ATE22323T1 (de) 1986-10-15
EP0105066A1 (fr) 1984-04-11
DE3273366D1 (en) 1986-10-23

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