NZ205542A - Separating fatty acids from rosin acids using molecular sieves - Google Patents

Description

205542 Priority Date(s): Complete Specification Filed: Class: CJ J Q.|.QS.i .CQ9.f.'J.

CfiTCffl Publication P.O. Journal, No: .13-23 r, V* -9 itr $83 N.Z.No.

NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "PROCESS FOR SEPARATING FATTY ACIDS FROM ROSIN ACIDS." We, UOP INC., a corporation organized under the laws of the State of Delaware, of Ten UOP Plaza, Algonquin & Mt.Prospect Roads, De& Plaines, Illinois 60016, United States of America do hereby declare the invention, for which we pray that a Patent may be granted to us< and the method by which it is to be performed, to be particularly described in and by the following statement : - ~ ■*" (Followed by 1A.) £0554-2. have been employed in processes to separate individual hydrocarbon isomers. As a few examples, adsorbents comprising X and Y zeolites are used in the process described in U.S. Patent No. 3,114,782 to separate alkyl-trisubstituted benzene"Isomers; in the process described 1n U.S. Patent No. 3,864,416 to separate alkyl-tetrasubstltuted monocyclic aromatic Isomers; and in the process described in U.S. Patent No. 3,668,267 to separate specific alkyl-substituted naphthalenes. Because of t+ie commercial Importance of para-xylene, perhaps the more well-known and extensively used hydrocarbon isomer separation processes are those for separating para-xylene from a mixture of Cfi aromatics. In processes described in U.S. Patent Nos.

Otd N- Z.. sp6aiica>5o / 549/5 3,558,730; 3,558,732; 3,626,020; 3,663,638; and 3,734,974,[for example, adsorbents comprising particular zeolites are used to separate para-xylene from feed mixtures comprising para-xylene and at least one other xylene isomer by selectively adsorbing para-xylene over the other xylene isomers.

In contrast, this invention relates to the separation of non-hydrocarbons and more specifically to the separation of fatty acids.

Substantial uses of fatty acids are in the plasticizer and surface active agent fields. Derivatives of fatty acids are of value 1n compounding lubricating oil, as a lubricant for the textile and molding trade, in special lacquers, as a water-proofing agent, in the cosmetic and pharmaceutical fields, and in biodegradable detergents.

It is known from U.S. Patent No. 4,048,205 to use type X and type Y zeolites for the separation of unsaturated from saturated esters of fatty acids. The type X and type Y zeolites, however, will not separate the esters of rosin acids found 1n tall oil from the esters of fatty acids nor the free acids, apparently because the pore sizes of those zeolites (over 7 angstroms) are large enough to 20554# accommodate and retain the relatively large diameter molecules of esters of rosin acids as well as the smaller diameter molecules of esters of fatty acids (.as well as the respective free acids) . Type A Zeolite, on the other hand, has a pore size (about 5 angstroms) which is unable to accommodate either of the above type esters (or free acids) and is, therefore, unable to separate them. An additional problem when a zeolite is used to separate free acids is the reactivity between the zeolite and free acids.

We have discovered that silicalite, a non-zeolitic hydrophobic crystalline silica molecular sieve, is uniquely suitable for the separation process of this invention in that it exhibits acceptance for a fatty acid with respect to a rosin acid, particularly when used with a specific displacement fluid, and does not exhibit reactivity with the free acids.

SUMMARY OF THE INVENTION According to a broad aspect of the invention there is provided a process for separating a fatty acid from a feed mixture comprising a fatty acid and a rosin acid, said process comprising contacting said feed mixture at separation conditions with a molecular sieve comprising silicalite, thereby selectively retaining said fatty acid, removing rosin acid from the fatty acid containing molecular sieve and thereafter recovering said fatty acid from said molecular sieve by displacement with a displacement fluid at displacement conditions.

In another embodiment, our invention is a process for separating a fatty acid from a mixture comprising a fatty acid and a rosin acid, which process comprises the steps: (a) maintaining net flow through a column of the molecular sieve in a single direction, which column contains at least three zones having separate operational functions occurring - 205542 therein and being serially interconnected with the terminal zones of the column connected to provide a continuous connection of the zones; (b) maintaining a retention zone 1n the column, the zone defined by the molecular sieve located between a feed Inlet stream at an upstream boundary 5 of the zone and a raffinate outlet stream at a downstream boundary of the zone; (c) maintaining a purification zone Immediately upstream from the retention zone, the purification zone defined by the molecular sieve located between an extract outlet stream at an upstream boundary of the purification zone and the feed Inlet stream at a downstream boundary of 10 the purification zone; (d) maintaining a displacement zone Inmediately upstream from the purification zone, the displacement zone defined by the molecular sieve located between a displacement fluid Inlet stream at an upstream boundary of the zone and the extract outlet stream at a downstream boundary of the zone; (e) passing the feed stream Into the 15 retention zone at separation conditions to effect the selective retention of fatty acid by the molecular sieve 1n the retention zone and withdrawing a raffinate outlet stream from the retention zone; (f) passing a displacement fluid Into the displacement zone at displacement conditions to effect the displacement of the fatty acid from the^wSwrt^TnSthe^displacement i/ zone; (g) withdrawing an extract stream comprising the fatty acid and displacement fluid from the displacement zone; and, (h) periodically advancing through the column of molecular sieve 1n a downstream direction with respect to fluid flow in the retention zone, the feed inlet stream, ■raffinate outlet stream, displacement fluid inlet stream, and extract 25 outlet and raffinate outlet streams.

Other embodiments of our Invention encompass details about feed mixtures, molecular sieves, displacement fluids and operating conditions, all of which are hereinafter.disclosed*1n the following discussion of each of the facets of the present Invention.

IU ' 6 DEC ms' 205542 y BRIEF DESCRIPTION OF THE FIGURES Figure 1 represents, 1n schematic form, the embodiment of the present Invention incorporating a simulated moving bed, hereinafter described, including adsorption column 1, manifold system 3 and various interconnect-5 ing lines.

Figures 2 and 3 comprise graphical representations of data obtained-"for the following examples.

DESCRIPTION OF THE INVENTION At the outset the definitions of various terms used throughout 10 the specification will be useful 1n maktng clear the operation, objects and advantages of our process.

A "feed mixture" 1s a mixture containing one or more extract components and one or more raffinate components to be separated by our process. The term "feed stream" Indicates a stream of 15 a feed mixture which passes to the molecular sieve used 1n the process.

An "extract component" Is a compound or type of compound that is retained by the molecular sieve while a "raffinate component" 1s a compound or type of compound that Is not retained. In this process, a fatty acid 1s an extract component and a rosin acid 1s a 20 raffinate component. The term "displacement fluid" shall mean generally a fluid capable of displacing an extract component. The term "displacement fluid stream" or'displacement fluid input stream" Indicates the stream through which displacement fluid passes to the molecular sieve. The term "diluent" or "diluent stream" Indicates the stream through which diluent 25 passes to the molecular sieve. The term "raffinate stream" or "raffinate output stream" means a stream through which a raffinate component 1s removed from the molecular sieve. The composition of the raffinate stream can vary from essentially a 100% displacement fluid to essentially 100% raffinate components. The term "extract stream" or "extract output stream" 30 shall mean a stream through which an extract material which has been displaced by a displacement fluid Is removed from the molecular sieve. The composition of the extract stream, likewise, can vary from essentially 100% displacement fluid to essentially 100% extract components. At least 205542 a portion of the extract stream and preferably at least a portion of the raffinate stream from the separation process are passed to separation means, typically fractionators, where at least a portion of displacement fluid and diluent is separated to produce an extract product and a raffinate product. The terms "extract product" and "raffinate product" mean products produced by the process containing, respectively, an extract component and a raffinate component 1n higher concentrations than those found in the extract stream and the raffinate stream. Although it is possible by the process of this invention to produce a high purity, fatty acid product or rosin acid product (or both) athigh recoveries, it will be appreciated that an extract component is never completely retained by the molecular sieve, nor is a raffinate component completely not retained by the molecular sieve. Therefore, varying amounts of a raffinate component can appear in the extract stream and, likewise, varying amounts of an extract component can appear 1n 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 a fatty acid to that of non-retained rosin acid will be lowest in the raffinate stream, next highest in the feed mixture, and the highest in the extract stream. Likewise, the ratio of the concentration of rosin acid to that of the retained fatty acid will be highest in the raffinate stream, next highest in the feed mixture, and the lowest in the extract stream.

The term "selective pore volume" of the molecular sieve is defined as the volume of the molecular sieve which selectively retains an extract component from the feed mixture. The term "non-selective void volume" of the molecular sieve 1s the volume of the molecular sieve which does not selectively retain an extract component from the feed mix 205542 ture. This volume includes the cavities of the molecular sieve which admit raffinate components and the interstitial void spaces between molecular sieve particles. The selective pore volume and the non-selec-tlve volcl volume are generally expressed in volumetric quantities and are of importance in determining the proper flow rates of fluid required to be passed into an operational zone for efficient operations to take place for a given quantity of molecular.sieve. When molecular sieve "passes" into an operational zone (hereinafter defined and described) employed in one embodiment of this process its non-selective void volume together with its selective pore volume carries fluid into that zone. The non-selective void volume is utilized in determining the amount of fluid which should pass into the same zone In a countercurrent direction to the molecular sieve to displace the fluid present in the non-selective void volume. If the fluid flow rate passing into a zone 1s smaller than the non-selective void volume rate of moleculisr sieve material passing Into that zone, there is a net entrainment of liquid into the zone by the molecular sieve. Since this net entrainment is a fluid present 1n the non-selective void volume of the molecular sieve, it in most instances comprises non-retained feed components.

Before considering feed mixtures which can be charged to the process of this invention, brief reference is first made to the terminology and to the general production of fatty acids. The fatty acids are a large group of aliphatic monocarboxylic acids, many of which occur as glycerides (esters of glycerol) 1n natural fats and oils. Although the term "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 205542 include also related unsaturated adds, certain substituted acids, and even aliphatic acids containing alicyclic substituents. The naturally occurring fatty acids with a few exceptions are higher straight chain unsubstftuted adds containing an even number of carbon atoms. The un-5 saturated fatty acids can be divided, on the basis of the number of double bonds in the hydrocarbon chain, into monoethanoid, diethanoid, triethanoid, etc. (or monethylenic, etc.). Thus the term "unsaturated fatty acid" is a generic term for a fatty acid having at least one double bond, and the term "polyethanoid fatty acid" means a fatty acid having more than one 10 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. In modern fatty acid plants this process Is carried out by continuous high pressure, 15 high temperature hydrolysis of the fat. Starting materials commonly used for the production of fatty acids include coconut oil, palm oil, inedible animal fats, and the commonly used vegetable oils, soybean oil, cottonseed oil and corn oil.

The source of fatty acids with which the present invention is 20 primarily concerned is tall oil, a by-product of the wood pulp Industry, usually recovered from pine wood "black liquor" of the sulfate or kraft paper process. Tall oil contains about 50-60% fatty acids and about 34-40% rosin acids. The fatty adds include oleic, linoleic, palmitic and stearic adds. Rosin acids, such as abietic acid, are monocarboxylic acids having 25 a molecular structure comprising carbon, hydrogen and oxygen with three fused s1x-membered carbon rings, which accounts for the much larger molecular diameter of rosin acids as compared to fatty acids.

-B- 205542 Feed mixtures which can be charged to our process may contain, in addition to the components of tall oil, a diluent material that is not adsorbed by the adsorbent and which 1s preferably separable from the extract and raffinate output streams by fractional distillation. Hhen a diluent 1s employed, the concentration of diluent in the mixture of diluent and acids will preferably be from a few vol.* up to about 75 vol.% with the remainder being fatty acids and rosin acids. Although we have previously discovered that silicalite Is effective for separating esters of fatty and rosin adds, separation of the free acids using silicalite has not heretofore been accomplished.

Displacement fluids used 1n various prior art adsorptlve and molecular sieve separation processes vary depending upon such factors as the type of operation employed. In separation processes which are generally operated continuously at substantially constant pressures and temperatures to ensure liquid phase, and which employ a molecular sieve, SeJeeJ-cJ the displacement material must be judiciously frlcected to satisfy many criteria. First, the displacement material should displace an extract component from the molecular sieve with reasonable mass flow rates but yet allow access of an extract component into the molecular sieve so as not to unduly prevent an extract component from displacing the displacement material 1n a following separation cycle. Displacement fluids should additionally be substances which are easily separable from the feed mixture that 1s passed into the process. Both the raffinate stream and the .extract stream are removed from the molecular sieve 1n admixture with displacement fluid and without a method of separating at least a portion of the displacement fluid, the purity of the extract product and the raffinate product would not be very high nor would the displacement 205542 fluid be available for reuse 1n the process. It is therefore contemplated that any displacement fluid material used 1n this process will preferably have a substantially different average boiling point than that of the feed mixture to allow separation of at least a portion of displacement fluid from feed components in the extract and raffinate streams by simple fractional distillation, thereby permitting reuse of displacement fluid 1n the process. The term "substantially different" as used herein shall mean that the difference between the average boiling points between the displacement fluid and the feed mixture shall be at least about 5eC. The boiling range of the displacement fluid may be higher or lower than that of the feed mixture. Finally, displacement fluids should also be materials which are readily available and therefore reasonable 1n cost. In the Isothermal, isobaric, liquid-phase operation of the process of our Invention,^we have found displacement fluids comprising organic acids to be effective with short chain organic adds having from '* 2 to 5 carbon atoms preferred, particularly when, as discussed hereinafter, a diluent is used. However, we have found the optimum displacement fluid as discussed hereinafter, to be a solution of light ketone (di-ethylketone or lighter) and water.

It has been observed that even silicalite may be ineffective in separating fatty and rosin adds upon reuse of the molecular sieve bed for separation following the displacement step. When displacement fluid 1s present 1n the bed, selective retention of the fatty add may not occur. It 1s hypothesized that the displacement fluid, particularly an organic acid, takes part 1n or even catalyzes hydrogen-bonded dimerization reactions 1n which there is an alignment between the molecules of the fatty and rosin adds and, perhaps, the molecules of the displacement fluid. These dimerization reactions may be represented by the formulas: - 205542 FA + FA ^— -^(FAFA) RA + RA^= —*(RARA) FA + RA^: where FA and RA stand for fatty acids arid rosin;ac1ds, respectively. The organic acid displacement fluid molecules, 1f used, would probably also be considered reactants and product constituients 1n the above equations. The dimers would preclude separation of the fatty and rosin acids by blocking aceess of the former Into the pores of the molecular sieve.

This hindrance to separation caused by the presence of dimers does not appear to be a significant problem in the aforementioned process for separation of esters of fatty and rosin acids.

We have discovered that the above dimerization reactions may be minimized, at least to the extent required to enable separation of the rosin and fatty acids, by first flushing the molecular sieve with a suitable diluent. The diluent serves to remove displacement fluid at least from the non-selective void volume of the molecular sieves.

Proper selection first requires solubility of the feed stream components 1n the diluent as well as easy separation of the diluent by conventional means, as with the displacement fluid. < We have also discovered that even the above pre-flush is unnecessary if the displacement fluid comprises the organic add in solution with a properly selected diluent. There are diluents which exhibit the property of minimizing dimerization. The measure of this property was found to be the polarity Index of the liquid. Polarity Index is as described 1n the article, "classification of the Solvent Properties of Conmon Liquids Synder, L.» J. Chromatography, 92, 205542 223 (1974), incorporated herein by reference. The minimum polarity index of the displacement fluid-diluent required for the process of the present Invention,1f pre-flush Is to be avoided 1s 3.5, particularly when the displacement fluid 1s a short chain organic acid as discussed above. The 5 diluent should comprise from about 50 to about 95 liquid volume percent of the displacement fluid. Polarity Indexes for certain selected diluents are as follows.

I SOLVENT POLARITY INDEX Isooctane -0.4 n-Hexane 0.0 Toluene 2.3 p-Xylene 2.4 Benzene 3.0 Methyl ethyl ketone 4.5 Acetone 5.4 c ' We have most recently found that the optimum displacement fluid which makes preflush unnecessary is a solution of water soluble high polarity index material, i.e., light ketones selected from the group comprising acetone, methyl-ethylketone, or di-ethylketone, and water. It should be realized that the polarity index of water is 9.0 and, therefore, a blend of water and, for example, 20 acetone has a very high polarity index since the polarity indexes of the components of such a blend are additive, i.e., the polarity index of a 50-50 blend of acetone and water would be equal to: .5 x 5.4 + .5 x 9.0 + 7.2. The ketone is essential, of course, not only because of its contribution to polarity Index, but also to obtain displacement 25 fluid which is soluble in the tall oil feedstock. The water-ketone blend even further improves the tall oil separation with silicalite both by virtue of Its very high polarity Index and by, It is hypothesized, providing water which bonds to the double bonded oxygen (donor atom) in the carboxylic groups of the fatty and rosin acids thus precluding bonding of those oxygens 30 with the active hydrogen in other carboxylic groups and formation of dimers. 2055 There are additional advantages to an acid-free aqueous displacement fluid. One advantage 1s that the corrosive effects of the short chain organic acids are eliminated. Another advantage is that the water in the displacement fluid will keep the molecular sieve from deactivating due to highly polar compounds such as mineral salts, particularly sodium sulfate found in crude tall oil, by dissolving and carrying away such compounds. The presence of water will also reduce the formation of esters from the alcohols present in crude tall oil by forcing to the left the reaction in which acid plus alcohol yields esters plus water.

The molecular sieve to be used ip the process of'this Invention comprises silicalite. As previously mentioned, silicalite 1s a hydrophobic crystalline silica molecular sieve. Silicalite is disclosed and claimed 1n U.S. Patent Nos. 4,061,724 and 4,104,294 to Grose et al, Incorporated herein by reference. Due to its aluminum-free structure, silicalite does not show 1on-exchange behavior, and is hydrophobic and organophilic. Silicalite thus comprises a molecular sieve, but not a zeolite. Silicalite 1s uniquely suitable for the separation process of this invention for the presumed reason that Its pores are of a size and shape that enable the silicalite to function as a molecular sieve, i.e. accept the molecules of fatty adds Into its channels or internal structure, while rejecting the molecules of rosin adds. A more detailed discussion of silicalite may be found 1n the article, "Silicalite, A New Hydrophobic Crystalline Silica Molecular Sieve"; Nature, Vol. 271, 9 February 1978, Incorporated herein by reference. 205542 Silicalite, like prior art adsorbents, or molecular sieves, is most advantageously used when associated with an appropriate binder material. The binder aids in forming or agglomerating the crystalline particles of the silicalite which otherwise would comprise a fine powder.

All binders heretofore attempted are not suitable for use 1n separating the components of tall oil because of the binder's reactivity or interference with the separation. We have discovered a binder which when incorporated with the silicalite provides a new molecular sieve uniquely suitable for the separation of the components of tall oil. 10 The silicalite is bound by silica, i.e., the silicalite is incorporated in a silica matrix. The silicalite is incorporated into the silica by dispersing silicalite powder into a colloidal amorphous silica, to obtain a precursor, gelling the precursor, and then treating the gel in a manner effecting substantially complete elimination of hydroxyl groups on 15 the silicalite and silica matrix. The colloidal amorphous silica comprises an aqueous colloidal dispersion of amorphous silica particles and the gelation is preferably effected by removing water from the dispersion, although other means of gelling may be used, such as changing pH or adding a salt or water miscible organic solvent. The silicalite should be present in the silica 20 matrix in amounts ranging from about 75 wt. % to about 98 wt. % silicalite based on volatile free composition. Prior to the treatment of the gel to eliminate hydroxyl groups it is preferably extruded while still in a plastic state and then broken into discrete particles. The plastic state will occur during at least a portion of the time water is being removed to achieve 25 gelling. Following treatment, the particles may be further ground to a smaller size more physically suitable for use in the particular separation scheme employed, typically about 16-60 mesh (Standard U.S. Mesh).

The colloidal amorphous silica preferred for use in the present invention is that marketed by DuPont Co. under the Trademark "Ludox." Ludox 30 colloidal silica is described as discrete uniform spheres of silica which have no internal surface area or detectable crystal Unity dispersed 1n an alkaline medium which reacts with the silica surface to produce a negative charge. The pH 205542 of the alkaline medium 1s maintained from about 8.5 to about 11.0. The stabilizing cations 1n the alkaline medium may comprise sodium or ammonium ions. The concentration of silica 1n the colloidal dispersion may comprise from about 30 wt.X to about 50 wt.X based on 5 Si02.

The Du Pont Co. literature describing Ludox colloidal silica states that during drying the hydroxyl groups on the surface of the silica particles condense by splitting out water to form siloxane bonds (Si - 0 - Si) resulting 1n coalescence, 1nterbond1ng 10 and particles which are chemically Inert and heat-resistant. It was found, however, that mere drying of the silica-bound silicalite at conditions accepted 1n the art to be drying conditions. I.e. heating 1n air 1n an oven at a temperature slightly above 100°C, produces a molecular sieve unacceptable for use 1n separating the components of 15 tall oil. Such a molecular sieve exhibits reactivity for the fatty and rosin acids and the separation achieved 1s very poor 1n that there are severe tailings of the rosin acid components Into the fatty add components. The reason hypothesized for such behavior 1s that the statements in the Du Pont Co. literature concerning the 20 formation of siloxane bonds during conventional drying are substantially true, however, there is still a very minute amount of hydroxyl groups (or ammonium groups where the stabilizing cations are ammonium 1ons) left on the particles which for most practical purposes are of no consequence, but which render the adsorbent 25 completely unsuitable for use 1n the process of the present invention. It should also be mentioned at this point that other binders for silicalite have been tried, but with equally poor results. Organic binders such as polyvinyl alcohol are unsuitable, 205542 probably because of the presence of hydroxyl groups. Natural clay binders exhibit selectivity for various constituents of tall oil and therefore interfere with the effect of the silicalite.

It is therefore necessary to treat the gelled silica-bound silicalite as aforesaid, to eliminate the hydroxyl groups and replace them by siloxane bonds. Thfe resulting silicalite in a silica matrix molecular sieve obtained is uniquely suitable for separation of tall oil components since it achieves the excellent separation of pure silicalite and, at the same time, provides a physically strong and stable molecular sieve suitable for commercial separaration applications.

There are numerous ways of treating the gelled silica-bound silicate to achieve substantially complete elimination of hydroxyl groups. One way 1s thermal treatment at a temperature of from about 450°C to about 1000°C for a minimum time of from about 3 hours to about 48 hours which may occur in the presence of oxygen, nitrogen and/or hydrogen. Another way 1s by first contacting the molecular sieve with an alcohol, such as ethanol, and then thermally treating the molecular sieve at elevated temperature (1n excess of about 350°C) in the presence of oxygen. A third way of eliminating hydroxyl groups 1s by chlorlnation of the molecular sieve at elevated temperature, such as like taught 1n U.S. Patent No. 4,308,172 to McDaniel whereby the molecular sieve 1s contacted at an elevated temperature with a chlorinating agent (e.g. CCl^, COClg, Cl2, ^Cl^, S°2C12 or SOClg), the resulting chlorinated molecular sieve is dechlorinated at an elevated temperature and the declorlnated molecular sieve 1s oxidized at an elevated temperature. Another way to way to effect hydroxyl groups removal by chlorlnation is to contact the 205542 molecular sieve at an elevated temperature with a mixture containing oxygen and silicon tetrachloride.

- The molecular sieve may be employed in the form of a dense compact fixed bed which is alternatively contacted with the feed mixture and displacement fluid. In the simplest embodiment of the invention, the molecular sieve is employed in the form of a single static bed in which case the process is only semi-continuous. In another embodiment, 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 molecular sieve beds, while the displacement fluid can be passed 205542 through one or more of the other beds in the set. The flow of feed mixture and displacement fluid may be either up or down through the molecular sieve. Any of the conventional apparatus employed 1n static bed fluid-solid contacting may be used.

Countercurrent moving bed or simulated moving bed counter- current flow systems, however, have a much greater separation efficiency than fixed bed systems and are therefore preferred. In the moving bed or simulated moving bed processes, the retention and displacement operations are continuously taking place which allows both continuous 10 production of an extract and a raffinate stream and the continual use of feed and displacement fluid streams and, for this Invention 1f required, a liquid flush stream. 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 15 described in U.S. Patent No. 2,985,589 Incorporated herein by reference.

In such a system, it 1s the progressive movement of multiple liquid access points down a molecular sieve chamber that simulates the upward movement of molecular sieve contained in the chamber. Only five of the access lines are active at any one time; the feed Input stream, displacement 20 fluid inlet stream, liquid flush inlet stream, raffinate outlet stream, and extract outlet stream access lines. Coincident with this simulated upward movement of the solid molecular sieve is the movement of the liquid occupying the void volume of the packed bed of molecular sieve. So that countercurrent contact 1s maintained, a liquid flow down the 25 molecular sieve chamber may be provided by a pump. As an active liquid access point moves through a cycle, that Is, from the top of the chamber to the bottom, the chamber circulation pump moves through different 205542 zones which require different flow rates. A programmed flow controller may be provided to set and regulate these flow rates.

The active liquid access points effectively divide the molecular sieve chamber Into separate zones, each of which has a different function. In this embodiment of the process, It 1s generally necessary that three separate operational zones be present in order for the process to take place, although 1n some Instances an optional fourth zone may be used.

There is a net positive fluid flow through all portions of the column in the same direction, although the composition and rate of the fluid will, of course, vary from point to point. With reference to Figure 1, zones I, II, III and IV are shown as well as manifold system 3, pump 2, which maintains the net positive fluid flow, and line 4 associated with pump 2. Also shown and identified are the inlet and outlet lines to the process which enter or leave via manifold system 3.

The retention zone, zone I, is defined as the molecular sieve located between the feed Inlet stream 5 and the raffinate outlet stream 7. In this zone, the feedstock contacts the molecular sieve, an extract component is retained, and a raffinate stream is withdrawn. Since the general flow through zone I 1s from the feed stream which passes Into the zone to the raffinate stream which passes out of the zone, the flow 1n this zone is considered to be a downstream direction when proceeding from the feed inlet to the raffinate outlet streams.

The liquid flush stream (diluent) may be introduced in Zone I at a point slightly downstream of the feed inlet stream. The diluent, If used: will be added at a rate sufficient to displace the displacement fluid associated with at least the non-selective void yoluroe of the packed bed of molecular sieve in simulated moyement in Zone I, thereby facilitating the retention of the fatty acid. 205542 Immediately upstream with respect to fluid flow in zone I 1s the purification zone, zone II. The purification zone is defined as the molecular sieve between the extract outlet stream and the feed inlet stream 5. The basic operations taking place in zone II are the 5 displacement from the non-selective void volume of the molecular sieve by a circulating stream of any raffinate material carried into zone II by the shifting of molecular sieve into this zone. Purification is achieved by passing a portion of extract stream material leaving zone III into zone II at zone II's upstream boundary, the extract outlet 10 stream,.to teffect the displacement of raffinate material. The flow of material in zone II is 1n a downstream direction from the extract outlet stream to the feed inlet stream.

Iumediately upstream of zone II with respect to the fluid flowing in zone II is the displacement zone or zone III. The displacement 15 zone is defined as the molecular sieve between the displacement fluid inlet 13 and the extract outlet stream 11. The function of the displacement zone is to allow a displacement fluid which passes Into this zone to displace the extract component which was retained in the molecular sieve during a previous contact with feed in zone I 1n a prior cycle of 20 operation. The flow of fluid in zone III is essentially 1n the same direction as that of zones I and II.

In some instances an optional buffer zone, zone IV, may be utilized. This zone, defined as the molecular sieve between the raffinate outlet stream 7 and the displacement fluid inlet stream 13, if used, 2055 1s located immediately upstream with respect to the fluid flow to zone 111. Zone IV would be utilized to conserve the amount of displacement fluid utilized in the displacement step since a portion of the raffinate stream which is removed from zone I can be passed Into zone 5 IV to displace molecular sieve present 1n that zone out of that zone into the displacement zone. Zone IV will contain enough molecular sieve so that raffinate material present 1n the raffinate stream passing out of zone I and into zone IV can be prevented from passing into zone III, thereby contaminating extract stream removed from zone 10 III. In the instances in which the fourth operational zone is not utilized, the raffinate stream which would have passed from zone I to zone IV must be carefully monitored in order that the flow directly from zone I to zone III can be stopped when there Is an appreciable quantity of raffinate material present in the raffinate stream passing 15 from zone I into zone III so that the extract outlet stream is not contaminated. 205542 In the most preferred embodiment of the present Invention, zone IV will be employed and the liquid flush diluent stream, If used, may be introduced not into zone I but into zone IV at the upstream boundary of zone IV. In this way, the displacement fluid that would 5 otherwise move into zone IV from zone III as part of the simulated moving bed will be kept 1n zone II, assuming that the correct amount * of liquid flush is used. This will also reduce the displacement fluid requirements. Thus, when the molecular sieve enters zone I it will have the proper minimum displacement fluid environment.

A cyclic advancement of the input and output streams through the fixed bed of molecular sieve can be accomplished by utilizing a manifold system 1n which the valves 1n the manifold are operated in a sequential manner to effect the shifting of the input and output streams, thereby allowing a flow of fluid with respect to solid molecular sieve in a 15 countercurrent manner. Another mode of operation which can effect the countercurrent flow of solid molecular sieve with respect to fluid Involves the use of a rotating disc valve In which the Input and output •5 streams are connected to the valve and the lines through which feed input, extract output, displacement fluid" Input and raffinate output 20 streams pass are advanced in the same direction through the molecular sieve bed. Both the manifold arrangement and disc valve are known in the art. Specifically, rotary disc valves which can be utilized in this operation can be found 1n U.S. Patent Nosr 3|04CU777 and 3,422,848avtJ M-2..

'Both of the aforementioned patents disclose a rotary-type connection valve In which the suitable advancement of the various Input and output streams from fixed sources can be achieved without difficulty.

In many instances, one operational sone will contain a much larger quantity of molecular sieve than some other operational zone. For instance, 1n some operations the buffer zone can contain a minor amount of molecular sieve as compared to the molecular sieve required for the retention and purification zones. It can also be seen that in instances 1n which displacement fluid is used which can easily displace extract material from the molecular sieve, that a relatively small amount of molecular sieve will be needed 1n a displacement zone as compared to the molecular sieve needed in the buffer zone or retention zone or purification zone or all of them. Since 1t 1s not required that the molecular sieve be located in a single column, the use of multiple chambers or a series of columns is within the scope of the Invention.

It is not necessary that all of the input or output streams be simultaneously used and, 1n fact, 1n many instances some of the streams can be shut off while others effect an Input or output of material. The apparatus which can be utilized to effect the process of this invention can also contain a series of individual beds connected by connecting conduits upon which are placed Input or output taps to which the various Input or output streams can be attached and alternately and periodically shifted to effect continuous operation. In some Instances, the connecting conduits can be connected to transfer taps which during the normal operations do not function as a conduit through which material passes into or out of the process. £ &Q5542 It 1s contemplated that at least a portion of the extract output stream will pass Into a separation means wherein at least a portion of the displacement fluid can be separated to produce an extract product containing a reduced concentration of displacement fluid. Preferably, but not necessary to the operation of the process, 5 at least a portion of the raffinate output stream will also be passed to a separation means wherein at least a portion of the displacement fluid can be separated to produce a displacement fluid stream which can be reused in the process and a raffinate product containing a reduced concentration of displacement fluid. The separation means 10 will typically be a fractionation column, the design and operation of which 1s well known to the separation art.

Reference can be made to D. B. Broughton U.S. Patent No. 2,985,589 and to a paper entitled "Continuous Adsorptive Processing — A New Separation Technique" by D. B. Broughton presented at 15 the 34th Annual Meeting of the Society of Chemical Engineers at Tokyo, Japan on April 2, 1969, both references Incorporated herein r-ite (atttf IHJVW floaMajA on fewest, by reference,!for further explanation of the simulated moving bed countercurrent process flow scheme.

Regarding separation conditions, although both liquid and vapor phase operations can be used in many adsorptive separation processes, liquid-phase operation is preferred for this process because of the lower temperature requirements and because of the higher yields of extract product that can be obtained with liquid-phase operation over those obtained with vapor-phase operation. When the displacement fluid comprises an organic 25 acid, separation conditions will Include a temperature range of from about 20°C to about 200°C with about 20°C to about 100°C being more preferred.

When the displacement fluid comprises a solution of light ketones and water, separation conditions will include a temperature range of from about 90°C to about 140°C with 120°C being more preferred. In any case, separa-30 tion conditions will include a pressure sufficient to maintain liquid phase. Displacement conditions will Include the same range of temperatures^ pressures as used for separation conditions. 205542 The size of the units which can utilize the process of this invention can vary anywhere from those of pilot-plant scale (see for example U.S. Patent No. 3,706,812) to those of commercial scale and can range 1n flow rates from as little as a few cc an hour up to many thousands of gallons per hour.

A dynamic testing apparatus Is employed to test various molecular sieves with a particular feed mixture and displacement fluid to measure the molecular sieve characteristics of retention capacity and exchange rate. The apparatus consists of a helical molecular sieve chamber of approximately 70 cc volume having inlet and outlet portions at opposite ends of the chamber. The chamber 1s contained within a temperature control means and, 1n 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 1n the effluent stream leaving the molecular sieve chamber. A pulse test, performed using this apparatus and the following general procedure, 1s used to determine data for various molecular sieve systems. The molecular sieve Is filled to equilibrium with a particular displacement fluid material by passing the displacement fluid through the molecular sieve chamber. At a convenient time, 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 displacement fluid 1s 205542 Injected for a duration of several minutes. Displacement fluid flow 1s resumed, and the tracer and the extract component or the raffinate component (or both) are eluted as 1n a liquid-solid chromatographic operation. The effluent can be analyzed on-stream or alternatively, 5 effluent samples can be collected periodically and later analyzed separately by analytical equipment and traces of the envelopes or corresponding component peaks developed.

From information derived from the test, molecular sieve performance can be rated in terms of void volume, retention volume for 10 an extract or a raffinate component, and the rate of displacement of an extract component from thfc molecular sieve. The retention volune of an extract or a raffinate component may be characterized by the distance between the center of the peak envelope of the tracer component or some other known reference point. It is expressed 1n terms of the volume 1n 15 cubic centimeters of displacement fluid pumped during this time Interval represented by the distance between the peak envelopes. The rate of exchange of an extract component with the displacement fluid can generally be characterized by the width of the peak envelopes at half Intensity. The narrower the peak width, the faster the displacement 20 rate. The displacement 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 displaced. This distance Is again the volume of displacement fluid pumped during this time Interval.

'.The following non-limiting working examples are presented to Illustrate the process of the present Invention and 1s not Intended to unduly restrict the scope of the claims attached hereto. 2 0 55 42 EXAMPLE I The above described pulse test apparatus was used to obtain data for this example. The liquid temperature was 60°C and the flow was up the column at the rate of 1.2 ml/min. The feed stream comprised 20 wt. % distilled tall oil, and 80wt. % displacement fluid. The column was packed with 23 wt. % Ludox bound silicalite (77 wt. % silicalite) which had been prepared as preferred in, the practice of the present invention, including gelation by removal of water (drying) followed by treatment for removal of hydroxyl groups, which in this case was by heating in air at 1000°C for 48 hours. The resulting molecular sieve was then ground and screened to 20-50 mesh. The displacement fluid used was 89 LV % methyl ethyl ketone and 20 LV % acetic acid.

The results of this example are shown on the accompanying Figure 2. It is apparent from Figure 2 that the separation achieved is quite good. The separation of the rosin acid from fatty acid curves is clear and distinct, although there is a moderate amount of overlap (tailings) between the rosin acid and linoleic acid curves and tailing from the linoleic acid into the oleic acid curve.

The curves also illustrate that there is not a trace of the aforementioned reactivity between adsorbent and feed components previously observed to occur with the silicalite with an organic binder and silicalite with a silica binder not thermally treated in accordance with the present invention.

Additional runs on the pulse test apparatus were carried out, also in accordance with the present invention, but with different displacement fluids such as a propionic acid and heptane mixture and pentanoic acid. The results varied somewhat, as to the quality of separation, but in all cases clear separations were achieved. Effective and practical separation of tall oil components has thus become a reality.

It is possible, however, as shown in the next example, to obtain an even better separation. 205542 EXAMPLE II The pulse test of Example I was repeated except that the displacement fluid used was a solution of 90 LV % acetone and 10 LV % water and the column temperature was 120°c. The temperature was raised to preclude formation of two liquid phases in the column, but is not believed to otherwise have affected the quality of the separation one way or the other.

The results of this example are shown on accompanying Figure 3. The separation achieved via the improvement of the present invention is vividly illustrated. Tailings from the rosin acids into the fatty acids are practically nil. Furthermore, the overlap between the linoleic and oleic acid curves is greatly diminished which is indicative of an ability to separate those two acids from each other in a second pass following removal of the rosin acids in a first pass.

Claims (1)

1. WHAT WE CLAIM IS: 1. A process for separating a fatty acid from a feed mixture comprising a fatty acid and a rosin acid, said process comprising contacting said feed mixture at separation conditions with a molecular sieve comprising silicalite, thereby selectively retaining said fatty acid, removing rosin acid from the fatty acid containing molecular sieve and thereafter recovering said fatty acid from said molecular sieve by displacement with a displacement fluid at displacement conditions, 2. The process of Claim 1 wherein said displacement fluid comprises an organic acid and said process is cyclical and said molecular sieve is flushed with a diluent at flushing conditions prior to each contacting of said feed mixture with said molecular sieve and wherein said separation, flushing and displacement conditions include a tempera- Swbsfevttiady s*bs+«*s>atly ture within the range of from 20 C to about 200°C and a pressure sufficient to maintain liquid phase. 3. The process of Claim 1 wherein said displacement fluid comprises a solution of organic acid and diluent, said diluent being soluble 1n said feed mixture and having a polarity index of at least 3.5. 4. The process of Claim 3 wherein said organic acid comprises a compound having from 2 to 5 carbon atoms per molecule and said diluent is chosen from the group comprising acetone, methytethylketone wcuti di-ethylketone and wherein said separation and displacement conditions stibifad'Oilty jubsfaididl/ include a temperature within the range of from about 20bC to about 20o°C and a pressure sufficient to maintain liquid phase. 5. The process of Claim 1 wherein said displacement fluid comprises an aqueous solution of a ketone from the group comprising acetone, cm) methyl-ethyl ketone di-ethylketone. ^05542, 6. The process of Claim 5 wherein said displacement fluid substantially suhsfaufraHy comprises from 5 to Mewt 307liquid volume percent water and wherein said separation and displacement conditions include a tempera- subs~knifiafly JubshrfhicJty ture within the range of from about 90°C to about 1406C and a pressure sufficient to maintain liquid phase. 7. The process of Claim 1 wherein said molecular sieve comprises silicalite dispersed in a silica matrix, the precursor of said molecular sieve comprising silicalite powder dispersed in colloidal amorphous silica, said precursor having been gelled and then treated in a manner effecting substantially complete elimination of hydroxyl groups on said molecular sieve. 8. The molecular sieve of Claim 7 wherein said precursor comprises an aqueous colloidal dispersion of amorphous silica particles and silicalite powder and said gelation is effected by removing water from said dispersion. 205542 9. A process for separating a fatty acid from a mixture comprising a fatty acid and a rosin acid, which process employs a molecular sieve comprising silicalite, which process comprises the steps of: (a) maintaining net liquid flow through a column of said molecular sieve in a single direction, which column contains at least three zones having separate operational functions occurring therein and being serially Interconnected with the terminal zones of said column connected to provide a continuous connection of said zones; (b) maintaining a retention zone 1n said column, said zone defined by the molecular sieve located between a feed inlet stream at an upstream boundary of said zone and a raffinate outlet stream at a downstream boundary of said zone; (c) maintaining a purification zone immediately upstream from said retention zone, said purification zone defined by the molecular sieve located between an extract outlet stream at an upstream boundary of said purification zone and said feed Inlet stream at a downstream boundary of said purification zone; (d) maintaining a displacement zone Immediately upstream from said purification zone, said displacement zone defined by the molecular sieve located between a displacement fluid inlet stream at an upstream boundary of said zone and said extract outlet stream at a downstream boundary of said zone; (e) passing said feed stream into said retention zone at separation conditions to effect the selective retention of fatty acid by said molecular sieve 1n said retention zone and withdrawing a raffinate outlet stream from said retention zone; -31- f 205542 (f) passing a displacement fluid into said displacement zone at displacement conditions to effect the Said MoltouJcw displacement of said fatty acid from the adoorbent in said displacement zone; (g) withdrawing an extract stream comprising said fatty acid and displacement fluid from said displacement zone; (h) periodically advancing through said column of molecular sieve in a downstream direction with respect to fluid flow in said retention zone, the feed inlet stream, raffinate outlet Btroam, displacement fluid inlet stream, and extract outlet and raffinate outlet streams. 10. The process of claim 9 further characterized in that it includes the steps of maintaining a buffer zone immediately upstream from said displacement zone, said buffer zone defined as the molecular sieve located between the displacement fluid input stream at a downstream boundary of said buffer zone and a raffinate output stream at an upstream boundary of said buffer zone. streanj is passed into said retention zone downstream of said feed inlet stream to effect the flushing of said molecular sieve in said retention zone, said diluent inlet stream being advanced with the other process streams as in step (h). 11. The process of Claim 9 wherein a diluent inlet cAai«n 12. A process according to f( A* substantially as herein described or exemplified. 33. A fatty acid separated by a process according ft of the preceding claims. UOP INC., By Their Attorneys f-6DECI985S V /- 32