NZ213584A - Selectively adsorbent molecular sieves for separation of fatty acids - Google Patents

Description

213584 Priority Date(s>: Complete Specification Filed: r?,-. r? ."".*$3 Class: BO9U J, CO^l CtZ P.O. Jccfftfs?, We?: .'sTJO. ^.

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NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION "MOLECULAR SIEVES" We, UOP INC., a corporation organized under the laws of the State of Delaware of Ten UOP Plaza, Algonquin & Mt. Prospect Roads, Des Plaines, Illinois 6Q016, 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:- 21358-4 Field of the invention The field of art to which this invention pertains is a solid Bed molecular sieve suitable for the separation of fatty acids. More specifically, the invention relates to a molecular sieve comprising silicalite suitable for a process for separating an oleic acid from a linoleic acid.

Description of the Prior Art It is known in the separation art that certain crystalline aluminosilicates can be used to separate certain esters of fatty acids from mixtures thereof. For example, in U S Patent Nos 4,048,205; 4,049,688 and 4,066,677, there are claimed processes for the separation of esters of fatty acids of various degrees of unsaturation from mixtures of esters of saturated and unsaturated fatty 2 - A* ft 2 OUMjC1985' 2 135 8.4 the separation of estow of fatty adds of various degrees of unsat— uration from miKturoG'Of ootort. of caturated and unsaturated fatty acids. These processes use adsorbents comprising an X or a Y zeolite containing a selected cation at the exchangeable cationic sites.

In contrast, this Invention relates to the separation of certain fatty acids rather than fatty acid esters. We have discovered that a specific molecular sieve that exhibits selectivity for one unsaturated fatty acid with respect to another unsaturated fatty acid thereby makes separation of such fatty acids by solid bed selective retention possible. Furthermore, we have discovered the enhanced effectiveness of specific displacement fluids at certain displacement conditions. In a specific embodiment our process is a process for separating oleic acid from linoleic acid. Substantial uses of fatty acids are in the plasticizer and surface active agent fields. Derivatives of fatty acids are of value in compounding lubricating oil, as a lubricant for the textile and molding trade, 1n special lacquers, as a waterproofing agent, in the cosmetic and pharmaceutical fields, and in biodegradable detergents.

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 first exhibits acceptance for a fatty acid with respect to a rosin acid, particularly when used with a specific displacement fluid, at specific displacement conditions, and does not exhibit reactivity with the free acids, and, second, it exhibits acceptance for oleic acid with respect to linoleic acid. 213584 BRIEF DESCRIPTION OF THE FIGURES Figure 1 represents, in schematic form, the embodiment of the present invention incorporating a simulated moving bed, hereinafter described, including adsorption column 1, manifold system 3 and various interconnecting lines.

Figures 2, 3 and 4 comprise graphical representations of data obtained for the following examples.

SUMMARY OF THE INVENTION According to a broad aspect the invention comprises a selectively adsorbent molecular sieve for separating tall oil components comprising silicalite in an inert silica matrix, said matrix comprising a gelled colloidal amorphous silica, said molecular sieve having substantially no hydroxyl groups thereon.

The sieve is useful in a process for separating oleic acid from linoleic acid contained in a feed mixture comprising the acids, the process comprising contacting the feed mixture at separation conditions with the molecular sieve comprising silicalite, thereby selectively retaining the oleic acid, removing linoleic acid from the oleic acid containing molecular sieve, and thereafter recovering the oleic acid from the molecular sieve by displacement with a displacement fluid at displacement conditions. Said process is described and claimed rN-l. inlPatent Specification No. 205543.

Other embodiments of our invention encompass detail's about 2 135 feed mixtures, molecular sieves, displacement fluids and operating conditions, all of which are hereinafter disclosed in the following discussion of each of the facets of the present invention.

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

A "feed mixture" is 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 a feed mixture which passes to the molecular sieve used in the process.

An "extract component" is a compound or type of compound that is retained by the molecular sieve while a "raffinate component" is a compound or type of compound that is not retained. In this process, oleic acid 1s an extract component and linoleic acid is a raffinate component. The term "displacement fluid" shall mean generally / a fluid capable of displacing an extract component. The term "displacement 2 1358 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 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" 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 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 1t 1s possible by the process of this invention to produce a high purity, fatty acid product or rosin acid product (or both) at high recoveries, it will be appreciated that an extract component 1s nev-er 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 in the raffinate stream. The extract and raffinate streams then are further distinguised from each other and from 2 135S4 the feed mixture by the ratio of the concentrations of an extract component and a raffinate component appearing 1n the particular stream. Pore 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 1n 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 is the volume of the molecular sieve which does not selectively retain an extract component from the feed mixture. 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-tive void volume are generally expressed 1n volumetric quantities and are of importance 1n 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 determinina 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 passina into a zone 2 1:35 8 4 1s smaller than the non-selective void volume rate of molecular 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 flulcl present in the non-selective void volume of the molecular 5 sieve, 1t 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 10 which occur as glycerides (esters of glycerol) 1n natural fats and oils. Although the term "fatty adds" has been restricted by some to the saturated acids of the acetic acid series, both normal and branched chain, it 1s now generally used, and 1s so used herein, to include also related unsaturated acids, certain substituted acids, 15 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, 20 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 add having more than one double bond per molecule. Fatty acids are typically prepared from alyceride fats or oils by one of several "splitting" or hydrolytic processes. In 25 all cases, the hydrolysis reaction may be sunmarized as the reaction of a fat or oil with water to yield fatty acids plus glycerol. In modern fatty acid plants this process 1s carried out by continuous high pressure, high temperature hydrolysis of the fat. Starting materials coirmonly used 2 (3 5S for the production of fatty acids include coconut oil, palm oil. Inedible animal fats, and the conmonly used vegetable oils, soybean oil, cottonseed oil and corn oil. r The source of fatty acids with which the present invention is 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 acids include oleic, linoleic, palmitic . and stearic adds. Linoleic and oleic acids comprise over 90% of the fatty acids present 1n tall oil. Rosin acids, such as abietic acid, are monocarboxylic acids having a molecular structure comprisinn carbon, hydrogen and oxygen with three fused six-membered carbon rings, which accounts for the much larger molecular diameter of rosin acids as compared to fatty acids.

Feed mixtures which can be charged to our process may contain, 1n addition to the components of tall oil, 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. When a diluent is employed, the concentration of diluent 1n 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 it has previously been discovered that silicalite is effective for separating esters of fatty and rosin acids, separation of the free acids from each other using silicalite has not heretofore been accomplished.

Displacement fluids used in various prior art adsorptive 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 13584 temperatures to ensure liquid phase, and which employ a molecular sieve, the displacement material must be judiciously selected 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 in a following separation cycle. Displacement fluids should additionally be substances which are easily separable from the feed mixture that is passed into the process. Both the raffinate stream and the extract stream are removed from the molecular sieve in 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 fluid be available for reuse in 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 1n the extract and raffinate streams by simple fractional distillation, thereby permitting reuse of displacement fluid in 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 5°C. 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 in cost. In the preferred isothermal, isobarlc, liquid-phase operation of the process of our Invention, we have found, as will be discussed at length 2 13534 hereinbelow, displacement fluids comprising a diluent soluble In the feed mixture and having a polarity index of at least 3.5 to be the most desirable.

A most effective displacement fluid is an organic acid. However, 1t has been observed that even silicalite may be ineffective 1n separating fatty and rosin acids or fatty acids from each other upon reuse of the molecular sieve bed for separation following the displacement step. When displacement fluid is present 1n the bed, selective retention of a fatty acid may not occur. It is hypothesized that the displacement fluid, particularly an organic acid, takes part 1n or even catalyzes hydrogen-bonded dimerization reactions 1n which there 1s an alignment between the molecules of the fatty and rosin acids and, perhaps, the molecules of the displacement fluid. These dimerization reactions may be represented by the formulas: fa + fa v e (fafa) ra + ra ^ —Mrara) fa + ra v -mfara) where FA and RA stand for fatty acids and rosin acids, respectively. The organic acid displacement fluid molecules should probably also be considered reactants and product constituents in the above equations. The dimers would preclude separation of the fatty and rosin adds by blocking access 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 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/or 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 in the diluent as well as easy separation of the diluent by conventional means, as with the displacement fluid. 2135 We have also discovered that even the above pre-flush may be avoided 1f the displacement fluid has a minimum polarity Index of 3.5. A preferred displacement fluid having a minimum polarity Index of 3.5 comprises a short chain organic acid having a chain length of 2 to 5 5 carbon atoms in solution with a diluent which exhibits the property of minimizing dimerization. The measure of this property is the polarity index of the liquid.

Polarity Index 1s as described in the article, "Classification of the Solvent Properties of Common Liquids"; Snyder, L., J. Chromatography, 92, 223 (1974), incorporated herein by reference. The diluent should comprise from about 50 to about 95 liquid volime percent of the displacement fluid. Polarity indexes for certain selected diluents are as follows: 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 Acetone, methyl ethyl ketone, and di-ethyl ketone are preferred diluents.

It is to be noted that diluents having a minimum polarity index of 3.5 are most especially preferred as displacement fluids, particularly when the temperature at which displacement is carried out 1s from about 25 120°C to about 150°C. Again, acetone, methyl ethyl ketone and di-ethyl ketone are preferred. This is an improvement over the practice of using a solution of such diluent and an organic acid as a displacement fluid for use at a relatively low temperature. A primary disadvantage of using that solution is that recovery of the organic acid from the extract product stream is 30 relatively energy Intensive and requires a significantly high temperature to achieve distillation which causes a degree of thermal degradation of the fatty acids. Another advantage is that the corrosive effects of short chain organic acids are eliminated. 2 13584 The molecular sieve to be used In the process of this Invention comprises silicalite. As previously mentioned, silicalite is a hydrophobic crystalline silica molecular sieve. Silicalite 1s 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 ion-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 acids into its channels or internal structure, while rejecting the molecules of rosin acids. 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.

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 in 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.

The silicalite is bound by silica, i.e., the silicalite is incorporated In a silica matrix. The silicalite 1s incorporated into the silica by dispersing silicalite powder into a colloidal amorphous 2 115 silica, to obtain a precursor, gelling the precursor, and then treating the gel in a manner effecting substantially complete elimination of hydroxyl groups on the slllaUte and silica matrix. The colloidal amorphous silica comprises an aqueous colHdal 5 dispersion of amorphous silica particles and the gelation 1s preferably effected by removing Mater from the dispersion, although other means of gelling may be used, such as changing pH or adding a salt or water mlscible organic solvent. The silicalite should be present in the silica matrix 1n mounts ranging from about 75 wt.X 10 to about 98 wt.t silicalite based on volatile free composition.

Prior to the treatment of the gel to eliminate hydroxyl groups 1t is preferably extruded while still 1n a plastic state and then broken Into discrete particles. The plastic state will occur during at least a portion of the time water 1s being removed to achieve 15 gelling. Following treatment, the particles may be further ground to a smaller size more physically suitable for use 1n the particular separation scheme employed, typically about 16-60 mesh (Standard U.S. Mesh).

The colloidal amorphous silica prefered for use in the 20 present invention 1s that marketed by Du Pont Co. under the trademark "Ludox." Ludox colloidal silica 1s described as discrete uniform spheres of silica which have no internal surface area or detectable crystalllnity dispersed in an alkaline medlun which reacts with the silica surface to produce a negative charge. The pH 2 135 of the alkaline medium 1s maintained from about 8.5 to about 11.0. The stabilizing cations 1n the alkaline median may comprise sodium or anmonlum ions. The concentration of silica in the colloidal dispersion may comprise from about 30 wt.JC to about 50 wt.% based on S102.

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 (S1 - 0 - Si) resulting in coalescence, interbonding 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 tall oil. Such a molecular sieve exhibits reactivity for the fatty and rosin adds and the separation achieved Is very poor in 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 formation of slloxane bonds during conventional drying are substantially true, however, there 1s still a very minute amount of hydroxyl groups (or ammonium groups where the stabilizing cations are arnnonlim Ions) left on the particles which for most practical purposes are of no consequence, but which render the adsorbent completely unsuitable for use in 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, 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 1s therefore necessary to treat the gelled silica-bound silicalite as aforesaid, to eliminate the hydroxyl groups and replace them by slloxane bonds. The resulting silicalite 1n a s111ca matrix molecular sieve obtained 1s uniquely suitable for separation of tall oil components since 1t 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 sillca-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 is 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) 1n the presence of oxygen. A third way of eliminating hydroxyl groups 1s by chlorlnatlon of the molecular sieve at elevated temperature, such as like taught 1n U.S. Patent No. 4,308,172 to McDanlel whereby the molecular sieve 1s contacted at an elevated temperature with a chlorinating agent (e.g. CCl^, C0C12, Cl2, C2C14, S02C12 or S0C12), the resulting chlorinated molecular sieve 1s dechlorlnated at an elevated temperature and the dedorinated molecular sieve Is oxidized at an elevated temperature. Another way to way to effect hydroxyl groups removal by chlorlnatlon is to contact the 21358 molecular seive at an elevated temperature with a mixture containing oxygen and silicon tetrachloride.

The molecular sieve may be employed 1n the form of a dense compact f}xed bed which 1s alternatively contacted with the feed mixture and displacement fluid. In the simplest embodiment of the Invention, the molecular sieve 1s employed 1n the form of a single static bed 1n which case the process Is only seni-continuous. In another embodiment, a set of two or more static beds may be employed 1n fixed bed contacting with appropriate valvlng so that the feed mixture 1s passed through one or more molecular sieve beds, while the displacement fluid can be passed through one or more of the other beds 1n 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 In 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 movinn bed or simulated moving bed processes, the retention and displacement operations are continuously taking place which allows both continuous production of an extract and a rafffinate stream and the continual use 2 1:33 of feed end displacement fluid streams and, for this Invention if required, a liquid flush stream. One preferred embodiment of this process utilizes what fs 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 U.S. Patent No. 2,985,589 Incorporated herein by reference. In such a system. It is the progressive movement of multiple liquid access points down a molecular sieve chamber that simulates the upward movement of molecular sieve contained 1n the chamber. Only five of the access lines are active at any one time; the feed Input stream, displacement 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 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 zones which require different flow rates. A programned 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, 1t 1s generally necessary that three separate operational zones be present 1n order for the process to take place, although 1n some Instances an optional fourth zone may be used. 2 OS.® 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 mani- * v fold system 3.

The retention zone, zone I, 1s 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 1s retained, and a raffinate stream 1s 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 in this zone 1s considered to be a downstream direction when proceeding from the feed inlet to the raffinate outlet streams. The liquid flush stream (diluent) may he Introduced 1n zone I at a point slightly downstream of the feed inlet stream. The diluent, 1f used, will be added at a rate sufficient to displace the displacement fluid associated with at least the non-selective void volume of the packed bed of molecular sieve in simulated movement 1n zone I, thereby facilitating the retention of the fatty acid.

Inrnediately upstream with respect to fluid flow In zone I 1s the purification zone, zone II. The purification zone 1s defined as the molecular sieve between the extract outlet stream and the feed inlet stream 5. The basic operations taking place 1n zone II are the 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 1s achieved by passing a portion of extract stream material leaving zone Illinto zone II at zone II's upstream boundary, the extract outlet stream, to effect the displacement of raffinate material. The flow of material in zone II 1s In a downstream direction from the extract outlet stream to the feed Inlet stream. 2 135 8 Immediately upstream of zone II with respect to the fluid flowing in zone II is the displacement zone or zone III. The displacement 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 In a prior cycle of operation. The flow of fluid in zone III is essentially in 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 raffin ate outlet stream 7 and the displacement fluid inlet stream 13, 1f used, 1s located immediately upstream with respect to the fluid flow to zone III. 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 1s removed from zone I can be passed into zone 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 in 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 III. In the instances 1n 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 from zone I into zone III so that the extract outlet stream is not 2 1351 In a preferred embodiment of the present Invention, zone IV will be employed and the liquid flush diluent stream, 1f 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 otherwise move Into zone IV from zone III as part of the simulated moving bed will be kept 1n zone III, assuring that the correct amount of liquid flush is used. This will also reduce the displacement fluid requirements. Thus, when the molcular 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 malnfold are operated 1n 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 1n a 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 streams are connected to the valve and the lines through which feed Input, extract output, displacement fluid Input and raffinate output streams pass are advanced 1n the same direction through the molecular sieve bed. Both the manifold arrangement and disc valve are known 1n the art. Specifically, rotary disc valves which can be utilized 1n this operation can be found 1n U.S. Patent Nos. 3,040,777 and 3,422,848.

Both of the aforementioned patents disclose a rotary-type connection valve 1n which the suitable advancement of the various Input and output streams from fixed sources can be achieved without difficulty.

In many Instances, one operational zone will contain a much larger quantity of molecular sieve than some other operational zone. For instance. In 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 1s used which can easily displace 2 13 5 6 4 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 of purification zone or all of them. Since 1t 1s not required that the molecular sieve be located 1n a single column, the use of multiple chambers or a series of columns 1s within the scope of the invention.

It 1s 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.

It is 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, including diluent, 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, at least a portion of the raffinate output stream will also be passed to a separation means wherein at least a portion of the diluent can be separated to produce a diluent stream which can be reused 1n the process and a raffinate product containing a reduced 2 13584 concentration of diluent. The separation means 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 ' tive Processing — A New Separation Technique"I by D. B. Broughton presented at the 34th Annual Meeting of the Society of Chemical Engineers at Tokyo, Japan on April 2, 1969, both references Incorporated herein by reference, for further explanation of the simulated moving bed countercurrent process flow scheme.

Although both liquid and vapor phase operations can be used in many adsorptive separation prpcesses, 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. 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 and a pressure sufficient to maintain liquid-phase, provided, however, that when the displacement fluid is diluent above the temperature should be at least 120°C. Displacement conditions will include the same range of temperatures and pressures as used for separation conditions.

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. 2 155 When the feedstock to the process contains rosin acids, as with tall oil, an additional step would be required to first sepsrate the rosin acids from the feedstock. This could be accomplished by contacting the rosin acid containing feed mixture with a first molecular sieve comprising silicalite, thereby selectively retaining the fatty acids to the exclusion of the rosin acid. The rosin acid would then be removed from the fatty acids containing first moleculir sieve, the mixture of fatty adds would be recovered by displacement from the first molecular sieve, and the fatty acid mixture would then be contacted with a second molecular sieve comprising the molecular sieve which effects the separation of the fatty acids from each other as aforesaid and which 1s preferably associated with the simulated moving bed embodiment.

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 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, polarlmeters 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 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 r 2 I 3 5 sieve Is filled to equilibrium with a particular displacement fluid material by passing the displacement fluid through the molecular sieve chanter. At a convenient time, a pulse of feed containing known concentrations of a tracer and of a particular extract component or of 5 a raffinate component or both, all diluted in displacement fluid 1s Injected for a duration of several minutes. Displacement fluid 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 on-stream or alternatively, 10 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 15 an extract or a raffinate component, and the rate of displacement of an extract component from the molecular sieve. The retention volume 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 in 20 terms of the volume in 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, 25 the faster the displacement 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 2 1 "55 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 are not intended 5 to unduly restrict the scope of the claims attached hereto.

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 m1/m1n. The feed stream comprised 10 wt. % fatty acid mixture and 90 wt. X displacement fluid. The fatty acid mixture was 50-50 linoleic and oleic acids. 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 1n 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 80 LV % methylethyl ketone and 20 LV % propionic acid.

The results of this example are shown on the accompanying Figure 2. It is apparent from the figure that the separation of the oleic acid from linoleic acid curves is clear and distinct, however the desorption kinetics are somewhat slow as reflected 1n the high gross retention volume which comprises the volume of displacement fluid required to achieve displacement.

The curves also illustrate that there is rtot 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. 2 13S? EXAMPLE II The above described pulse test apparatus was again used to obtain data for this example. The liquid temperature was 80°C and the flow was down the column at the rate of 1.2 ml/min. The feed stream comprised 10 wt.l tall oil and 90 wt.% displacement fluid. The colurni was packed with 23 wt.t Ludox bound silicalite (77 wt.X silicalite), as 1n Example I. The displacement fluid used was 100% acetone.

The results of this example are shown on the ecconpanying Figure 3. It is apparent from the figure that the separation of the rosin acid, oleic acid and linoleic acid is clear and distinct, however the desorptlon kenetlcs are again quite slow.

EXAMPLE 111 The test of Example II was repeated except that, in accordance with the present Invention, In addition to a displacement fluid having a polarity index of over 3.5 being usedfthe liquid temperature 1n the column was 120°C.

The results of this example are shown on the acconpanying Figure 4. Figure 4 shows a marked improvement (Increase) 1n the desorption kinetics, I.e. the gross retention volume is significantly reduced. Increased desorptlon kinetics Is, of course, desirable 1n a cornnercial enfcodiment of the invention, particularly an enfcodiment Incorporating the simulated moving bed, since 1t will have a direct effect (reduction) on the volune of displacement fluid required and resultant savings In energy because of less displacement fluid that will need to be distilled from the product streams.

Claims (5)

WHAT WE CLAIM IS: 2 1 35 $4

1. A selectively adsorbent molecular sieve for separating tall oil components comprising silicalite in an inert silica matrix, said matrix comprising a gelled colloidal amorphous silica, said molecular sieve having substantially no hydroxyl groups thereon.

2. A sieve according to claim 1 which has been extruded and broken into discrete particles.

3. A sieve according to claim 2 wherein the particles are processed to a size between 16-60 mesh.

4. A sieve according to claim 1 wherein the silicalite is present in the silica matrix in an amount from 75 wt% to 98 wt% silicalite based on volatile free composition.

5. A selectively adsorbent molecular sieve according to claim 1 substantially as herein described. UOP INC. By Their Attorneys -29- /■