text:
|Publication number
|Publication type
|Application number
|Publication date
|Aug 24, 1982
|Filing date
|Aug 1, 1980
|Priority date
|Sep 14, 1979
|Publication number
|Hosheng Tu, Juana E. Rojo
|Original Assignee
|Uop Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (9), Referenced by (8), Classifications (8), Legal Events (2)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a division of application Ser. No. 75,576, filed Sept. 14, 1979 and now abandoned.
1. Field of the Invention
The field of art to which this invention pertains is solid-bed adsorptive separation. More specifically, the invention relates to an improved adsorbent suitable for use in a process for separating a component from a mixture comprising an aqueous solution of a mixture of different components.
It is known in the separation art that certain crystalline aluminosilicates referred to as zeolites can be used in the separation of a component from an aqueous solution of a mixture of different components. For example, adsorbents comprising crystalline aluminosilicate are used in the method described in U.S. Pat. No. 4,014,711 to separate fructose from a mixture of sugars in aqueous solution including fructose and glucose.
It is also known that crystalline aluminosilicate or zeolites are used in adsorption processing in the form of agglomerates having high physical strength and attrition resistance. Methods for forming the crystalline powders into such agglomerates include the addition of an inorganic binder, generally a clay comprising silicon dioxide and aluminum dioxide, to the high purity zeolite powder in wet mixture. The blended clay zeolite mixture is extruded into cylindrical type pellets or formed into beads which are subsequently calcined in order to convert the clay to an amorphous binder of considerable mechanical strength. As binders, clays of the kaolin type are generally used.
Zeolite crystal has long been known to have the property of gradually disintegrating as a result of continuous contact with water. It may be related to the surface migration and interaction between the charges of ions on the zeolite surface and in solution. In any event, the zeolite disintegration has been observed as a silicon presence or contamination in the solution in contact with the zeolite.
We have discovered an improved zeolite adsorbent and an improvement to an aqueous separation process which minimizes the disintegration of the zeolite and silicon contamination of the product.
It is, accordingly, a broad objective of our invention to provide an adsorbent suitable for use in the separation of a component from a feed mixture comprising different components in aqueous solution, by contacting said mixture with an adsorbent comprising a crystalline aluminosilicate, having an improvement so as to minimize the dissolution of the crystalline aluminosilicate and silica contamination of the product.
In brief summary, our invention is, in one embodiment, an adsorbent comprising a crystalline aluminosilicate which is suitable for use in a process for the separation of a component from a feed mixture comprising an aqueous solution of a mixture of components. The separation is made by contacting the solution with the adsorbent. The silicon constituent of the crystalline aluminosilicate tends to dissolve in said solution resulting in the undesirable disintegration of the crystalline aluminosilicate. The improvement to the adsorbent comprises the crystalline aluminosilicate being impregnated, prior to the contacting with the aqueous solution, with aluminum cations. The impregnation effects a chemical reaction between the crystalline aluminosilicate and the aluminum cations which substantially reduces the extent of the disintegration of the crystalline aluminosilicate.
Other objectives and embodiments of our invention encompass details about feed mixtures, adsorbents, desorbent materials and operating conditions, all of which are hereinafter disclosed in the following discussion of each of the facets of the present 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 adsorbent used in the process.
An "extract component" is a component that is more selectively adsorbed by the adsorbent while a "raffinate component" is a component that is less selectively adsorbed. The term "desorbent material" shall mean generally a material capable of desorbing an extract component. The term "desorbent stream" or "desorbent input stream" indicates the stream through which desorbent material passes to the adsorbent. The term "raffinate stream" or "raffinate output stream" means a stream through which a raffinate component is removed from the adsorbent. The composition of the raffinate stream can vary from essentially 100% desorbent material 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 desorbed by a desorbent material is removed from the adsorbent. The composition of the extract stream, likewise, can vary from essentially 100% desorbent material 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 or evaporators, where at least a portion of desorbent material 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 in higher concentrations than those found in the extract stream and the raffinate stream.
The term "selective pore volume" of the adsorbent is defined as the volume of the adsorbent which selectively adsorbs an extract component from the feed mixture. The term "non-selective void volume" of the adsorbent is the volume of the adsorbent which does not selectively retain an extract component from the feed mixture. This volume includes the cavities of the adsorbent which contain no adsorptive sites and the interstitial void spaces between adsorbent particles. The selective pore volume and the non-selective void 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 adsorbent. When adsorbent "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 counter-current direction to the adsorbent to displace the fluid present in the non-selective void volume. If the fluid flow rate passing into a zone is smaller than the non-selective void volume rate of adsorbent material passing into that zone, there is a net entrainment of liquid into the zone by the adsorbent. Since this net entrainment is a fluid present in non-selective void volume of the adsorbent, it in most instances comprises less selectively retained feed components. The selective pore volume of an adsorbent can in certain instances adsorb portions of raffinate material from the fluid surrounding the adsorbent since in certain instances there is competition between extract material and raffinate material for adsorptive sites within the selective pore volume. If a large quantity of raffinate material with respect to extract material surrounds the adsorbent, raffinate material can be competitive enough to be adsorbed by the adsorbent.
The so-called "simple sugars" are classified as monosaccharides and are those sugars which upon hydrolysis do not break down into smaller simpler sugars. One may further classify monosaccharides as aldoses or ketoses, depending upon whether they are hydroxy aldehydes or hydroxy ketones, and by the number of carbon atoms in the molecule. Most common and well known are probably the hexoses. Common ketohexoses are fructose (levulose) and sorbose; common aldohexoses are glucose (dextrose), mannose and galactose. The term "oligosaccharides" as commonly understood in the art and as used herein means simple polysaccharides containing a known number of constituent monosaccharide units. An oligosaccharide that breaks up upon hydrolysis into two monosaccharide units is called a disaccharide, examples being sucrose, maltose and lactose. Those giving three such units are trisaccharides, of which raffinose and melezitose are examples. Di-, tri- and tetra-saccharides comprise practically all of the oligosaccharides. The term "polysaccharide" includes oligosaccharides but usually it refers to carbohydrate materials of much higher molecular weight, namely, those that are capable of breaking up on hydrolysis into a large number of monosaccharide units. Typical polysaccharides are starch, glycogen, cellulose and pentosans.
Feed mixtures contemplated for use with the adsorbent of our invention may, for example, be aqueous solutions of one or more aldoses and one or more ketoses or one or more monosaccharides and one or more oligosaccharides. The concentration of solids in the solutions may range from about 0.5 wt. % to about 50 wt. % or more but preferably will be from about 5 to about 35 wt. %. Starch syrups, such as corn syrup, are examples of feed mixtures which can be charged to our process. Such syrups are produced by the partial hydrolysis of starch generally in the presence of mineral acids or enzymes. Corn syrup produced in this manner will typically contain 25 to 75 wt. % solids comprising 90 to 95% glucose and 5 to 10% maltose and higher oligosaccharides. A portion of the glucose in this corn syrup may be isomerized with an isomerizing enzyme to produce a high-fructose corn syrup, typically comprising 40-45% fructose, 50-55% glucose and 5-10% oligosaccharides, which can also be charged to our process. The pH of the aqueous solution comprising the feed mixture may be from about 5.5 to about 7.5.
Desorbent materials used in various prior art adsorptive separation processes vary depending upon such factors as the type of operation employed. In the swing-bed system in which the selectively adsorbed feed component is removed from the adsorbent by a purge stream, desorbent selection is not as critical and desorbent material comprising gaseous hydrocarbons such as methane, ethane, etc., or other types of gases such as nitrogen or hydrogen may be used at elevated temperatures or reduced pressures or both to effectively purge the adsorbed feed component from the adsorbent. However, in adsorptive separation processes which are generally operated continuously at substantially constant pressures and temperatures to insure liquid phase, the desorbent material must be judiciously selected to satisfy many criteria. First, the desorbent material should displace an extract component from the adsorbent with reasonable mass flow rates without itself being so strongly adsorbed as to unduly prevent an extract component from displacing the desorbent material in a following adsorption cycle. Expressed in terms of the selectivity (hereinafter discussed in more detail), it is preferred that the adsorbent be more selective for all of the extract components with respect to a raffinate component than it is for the desorbent material with respect to a raffinate component. Secondly, desorbent materials must be compatible with the particular adsorbent and the particular feed mixture. More specifically, they must not reduce or destroy the critical selectivity of the adsorbent for an extract component with respect to a raffinate component. Additionally, desorbent materials should not chemically react with or cause a chemical reaction of either an extract component or a raffinate component. Both the extract stream and the raffinate stream are typically removed from the adsorbent in admixture with desorbent material and any chemical reaction involving a desorbent material and an extract component or a raffinate component would reduce the purity of the extract product or the raffinate product or both. Since both the raffinate stream and the extract stream typically contain desorbent materials, desorbent materials should additionally be substances which are easily separable from the feed mixture that is passed into the process. Without a method of separating at least a portion of the desorbent material present in the extract stream and the raffinate stream, the concentration of an extract component in the extract product and the concentration of a raffinate component in the raffinate product would not be very high, nor would the desorbent material be available for reuse in the process. It is contemplated that at least a portion of the desorbent material will be separated from the extract and the raffinate streams by distillation or evaporation, but other separation methods such as reverse osmosis may also be employed alone or in combination with distillation or evaporation. Since the raffinate and extract products are foodstuffs intended for human consumption, desorbent materials should also be non-toxic. Finally, desorbent materials should also be materials which are preferably readily available and therefore reasonable in cost.
We have found that water having a pH of from about 5.5 to about 7.5 satisfies these criteria and is a suitable and preferred desorbent material. The pH of the desorbent material is important because adsorption of a component by the adsorbent, removal of a raffinate stream, desorption of the component from the adsorbent and removal of an extract stream all typically occur in the presence of desorbent material. If the desorbent material is too acidic or too alkaline, chemical reactions of the components are promoted and reaction products are produced that can reduce the yield purity of either the extract or raffinate product, or both.
Water pH does of course vary widely depending upon the source of the water in addition to other factors. Methods of maintaining and controlling a desired water pH are, however, well known to those skilled in the art of water treating. Such methods generally comprise adding an alkaline compound such as sodium hydroxide or an acid compound such as hydrochloric acid to the water in amounts as necessary to achieve and maintain the desired pH.
The prior art has recognized that certain characteristics of adsorbents are highly desirable, if not absolutely necessary, to the successful operation of a selective adsorption process. Such characteristics are equally important to this process. Among such characteristics are: adsorptive capacity for some volume of an extract component per volume of adsorbent, the selective adsorption of an extract component with respect to a raffinate component and the desorbent material, and sufficiently fast rates of adsorption and desorption of an extract component to and from the adsorbent. Capacity of the adsorbent for adsorbing a specific volume of an extract component is, of course, a necessity; without such capacity the adsorbent is useless for adsorptive separation. Furthermore, the higher the adsorbent's capacity for an extract component the better is the adsorbent. Increased capacity of a particular adsorbent makes it possible to reduce the amount of adsorbent needed to separate an extract component of known concentration contained in a particular charge rate of feed mixture. A reduction in the amount of adsorbent required for a specific adsorptive separation reduces the cost of the separation process. It is important that the good initial capacity of the adsorbent be maintained during actual use in the separation process over some economically desirable life. The second necessary adsorbent characteristic is the ability of the adsorbent to separate components of the feed; or, in other words, that the adsorbent possess adsorptive selectivity, (B), for one component as compared to another component. Relative selectivity can be expressed, not only for one feed component as compared to another, but can also be expressed between any feed mixture component and the desorbent material. The selectivity, (B), as used throughout this specification, is defined as the ratio of the two components of the adsorbed phase over the ratio of the same two components in the unadsorbed phase at equilibrium conditions. Relative selectivity is shown as Equation 1 below: ##EQU1## where C and D are two components of the feed represented in volume percent and the subscripts A and U represent the adsorbed and unadsorbed phases respectively. The equilibrium conditions were determined when the feed passing over a bed of adsorbent did not change composition after contacting the bed of adsorbent. In other words, there was no net transfer of material occurring between the unadsorbed and adsorbed phases. Where selectivity of two components approaches 1.0, there is no preferential adsorption of one component by the adsorbent with respect to the other; they are both adsorbed (or non-adsorbed) to about the same degree with respect to each other. As the (B) becomes less than or greater than 1.0, there is a preferential adsorption by the adsorbent for one component with respect to the other. When comparing the selectivity by the adsorbent of one component C over component D, a (B) larger than 1.0 indicates preferential adsorption of component C within the adsorbent. A (B) less than 1.0 would indicate that component D is preferentially adsorbed leaving an unadsorbed phase richer in component C and an adsorbed phase richer in component D. Ideally, desorbent materials should have a selectivity equal to about 1 or slightly less than 1 with respect to all extract components so that all of the extract components can be desorbed as a class with reasonable flow rates of desorbent material and so that extract components can displace desorbent material in a subsequent adsorption step. While separation of an extract component from a raffinate component is theoretically possible when the selectivity of the adsorbent for the extract component with respect to the raffinate component is greater than 1.0, it is preferred that such selectivity be greater than 1.0. Like relative volatility, the higher the selectivity the easier the separation is to perform. Higher selectivities permit a smaller amount of adsorbent to be used. The third important characteristic is the rate of exchange of the extract component of the feed mixture material or, in other words, the relative rate of desorption of the extract component. This characteristic relates directly to the amount of desorbent material that must be employed in the process to recover the extract component from the adsorbent; faster rates of exchange reduce the amount of desorbent material needed to remove the extract component and therefore permit a reduction in the operating cost of the process. With faster rates of exchange, less desorbent material has to be pumped through the process and separated from the extract stream for reuse in the process.
Adsorbents comprising this invention will comprise specific crystalline aluminosilicates or molecular sieves. Particular crystalline aluminosilicates encompassed by the present invention include crystalline aluminosilicate cage structures in which the alumina and silica tetrahedra are intimately connected in an open three dimensional network to form cage-like structures with window-like pores of about 8 A free diameter. The tetrahedra are cross-linked by the sharing of oxygen atoms with spaces between the tetrahedra occupied by water molecules prior to partial or total dehydration of this zeolite. The dehydration of the zeolite results in crystals interlaced with cells having molecular dimensions and thus the crystalline aluminosilicates are often referred to as "molecular sieves" particularly when the separation which they effect is dependent essentially upon differences between the sizes of the feed molecules as, for instance, when smaller normal paraffin molecules are separated from larger isoparaffin molecules by using a particular molecular sieve.
In hydrated form, the crystalline aluminosilicates used in the process of our invention generally encompass those zeolites represented by the Formula 1 below:
M.sub.2/n O:Al.sub.2 O.sub.3 :wSiO.sub.2 :yH.sub.2 O Formula 1
where "M" is a cation which balances the electrovalence of the aluminum-centered tetrahedra and which is generally referred to as an exchangeable cationic site, "n" represents the valence of the cation, "w" represents the moles of SiO2, and "y" represents the moles of water. The generalized cation "M" may be monovalent, divalent or trivalent or mixtures thereof.
The prior art has generally recognized that adsorbents comprising X and Y zeolites can be used in certain adsorptive separation processes. These zeolites are described and defined in U.S. Pat. Nos. 2,882,244 and 3,130,007 respectively incorporated herein by reference thereto. The X zeolite in the hydrated or partially hydrated form can be represented in terms of mole oxides as shown in Formula 2 below:
(0.9�0.2)M.sub.2/n O:Al.sub.2 O.sub.3 :(2.5�0.5)SiO.sub.2 :yH.sub.2 OFormula 2
where "M" represents at least one cation having a valence of not more than 3, "n" represents the valence of "M", and "y" is a value up to about 9 depending upon the identity of "M" and the degree of hydration of the crystal. As noted from Formula 2, the SiO2 /Al2 O3 mole ratio of X zeolite is 2.5�0.5. The cation "M" may be one or more of a number of cations such as a hydrogen cation, an alkali metal cation, or an alkaline earth cation, or other selected cations, and is generally referred to as an exchangeable cationic site. As the X zeolite is initially prepared, the cation "M" is usually predominately sodium, that is, the major cation at the exchangeable cationic sites is sodium and the zeolite is therefore referred to as a sodium-X zeolite. Depending upon the purity of the reactants used to make the zeolite, other cations mentioned above may be present, however, as impurities. The Y zeolite in the hydrated or partially hydrated form can be similarly represented in terms of mole oxides as in Formula 3 below:
(0.9�0.2)M.sub.2/n O:Al.sub.2 O.sub.3 :wSiO.sub.2 :yH.sub.2 OFormula 3
where "M" is at least one cation having a valence not more than 3, "n" represents the valence of "M", "w" is a value greater than about 3 up to about 6, and "y" is a value up to about 9 depending upon the identity of "M" and the degree of hydration of the crystal. The SiO2 /Al2 O3 mole ratio for Y zeolites can thus be from about 3 to about 6. Like the X zeolite, the cation "M" may be one or more of a variety of cations, but, as the Y zeolite is initially prepared, the cation "M" is also usually predominately sodium. A Y zeolite containing predominately sodium cations at the exchangeable cationic sites is therefore referred to as a sodium-Y zeolite.
Cations occupying exchangeable cationic sites in the zeolite may be replaced with other cations by ion exchange methods well known to those having ordinary skill in the field of crystalline aluminosilicates. Such methods are generally performed by contacting the zeolite or an adsorbent material containing the zeolite with an aqueous solution of the soluble salt of the cation or cations desired to be placed upon the zeolite. After the desired degree of exchange takes place, the sieves are removed from the aqueous solution, washed, and dried to a desired water content. By such methods, the sodium cations and any non-sodium cations which might be occupying exchangeable sites as impurities in a sodium-X or sodium-Y zeolite can be partially or essentially completely replaced with other cations. It is preferred that the zeolite used in the process of our invention contain cations at exchangeable cationic sites selected from the group consisting of the alkali metals and the alkaline earth metals.
Typically, adsorbents used in separative processes contain zeolite crystals and amorphous material. The zeolite will typically be present in the absorbent in amounts ranging from about 75 wt. % to about 98 wt. % based on volatile free composition. Volatile free compositions are generally determined after the adsorbent has been calcined at 900� C. in order to drive off all volatile matter. The remainder of the adsorbent will generally be amorphous material such as silica, or silica-alumina mixtures or compounds, such as clays, which material is present in intimate mixture with the small particles of the zeolite material. This amorphous material may be an adjunct of the manufacturing process for zeolite (for example, intentionally incomplete purification of either zeolite during its manufacture), or it may be added to relatively pure zeolite, but, in either case, its usual purpose is as a binder to aid in forming or agglomerating the hard crystalline particles of the zeolite. Normally, the adsorbent will be in the form of particles such as extrudates, aggregates, tablets, macrospheres or granules having a desired particle size range. The adsorbent used in our process will preferably have a particle size range of about 16-40 mesh (Standard U.S. Mesh). Examples of suitable zeolites employed in our process, either as is or after cation exchange, are "Molecular Sieves 13X" and "SK-40", both of which are available from the Linde Company, Tonawanda, N.Y. The first material of course contains X zeolite while the latter material contains Y zeolite. We have found that X or Y zeolites possess the selectivity requirement and other necessary requirements previously discussed and are therefore suitable for use in our process.
The question arises, particularly when the amorphous binding material in the adsorbent comprises silica or silica-alumina, whether the source of the dissolved silicon in the solution in contact with the adsorbent is the zeolite or the binder material. We have found that the primary source of the silicon is in fact the zeolite. The removal of the silicon from the crystalline aluminosilicate via its dissolution in the aqueous solution causes collapse of the crystalline structure which renders the adsorbent ineffective for further use as an adsorbent.
Prior to its use, our adsorbent, as a final stage in its preparation, is impregnated with aluminum cations. We have found that this impregnation will minimize the undesirable dissolution of the silicon. The aluminum cations chemically react with the crystalline aluminosilicate.
The impregnation cannot effectively be accomplished in situ by adding the aluminum cations to the feed stream because, when that is attempted, the ions tend to precipitate outside of the adsorbent particles and will ultimately cause a severe problem of a high pressure drop in the adsorbent bed. The impregnation is preferably effected by soaking the adsorbent in an aqueous solution of aluminum cations, preferably in the form of an aluminum halide, and then evaporating the water. It is preferred that the amount of aluminum ion used is sufficient to impart a concentration of aluminum cation combined with the adsorbent by the impregnation of from about 0.01 wt. % to about 0.50 wt. % and preferably about 0.05 wt. % to about 0.20 wt. %, calculated on the basis of elemental aluminum.
The adsorbent may be employed in the form of a dense compact fixed bed which is alternatively contacted with the feed mixture and desorbent materials. In the simplest embodiment of the invention, the adsorbent 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 adsorbent beds while the desorbent materials can be passed through one or more of the other beds in the set. The flow of feed mixture and desorbent materials may be either up or down through the desorbent. Any of the conventional apparatus employed in static bed fluid-solid contacting may be used.
Counter-current moving-bed or simulated moving-bed counter-current flow systems, however, have a much greater separation efficiency than fixed adsorbent bed systems and are therefore preferred for use in our separation process. In the moving-bed or simulated moving-bed process, the adsorption and desorption operations are continuously taking place which allows both continuous production of an extract and a raffinate stream and the continual use of feed and desorbent streams. One preferred embodiment of this process utilizes what is known in the art as the simulated moving-bed counter-current flow system. The operating principles and sequence of such a flow system are described in U.S. Pat. No. 2,985,589, incorporated herein by reference thereto. In such a system, it is the progressive movement of multiple liquid access points down an adsorbent chamber that simulates the upward movement of adsorbent contained in the chamber. Only four of the access lines are active at any one time; the feed input stream, desorbent inlet stream, raffinate outlet stream, and extract outlet stream access lines. Coincident with this simulated upward movement of the solid adsorbent is the movement of the liquid occupying the void volume of the packed bed of adsorbent. So that counter-current contact is maintained, a liquid flow down the adsorbent 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 programmed flow controller may be provided to set and regulate these flow rates.
The active liquid access points effectively divided the adsorbent chamber into separate zones, each of which has a different function. In this embodiment of our process, it is generally necessary that three separate operational zones be present in order for the process to take place although in some instances an optional fourth zone may be used.
The adsorption zone, zone 1, is defined as the adsorbent located between the feed inlet stream and the raffinate outlet stream. In this zone, the feed stock contacts the adsorbent, an extract component is adsorbed, and a raffinate stream is withdrawn. Since the general flow through zone 1 is from the feed stream which passes into the zone to the raffinate stream which passes out of the zone, the flow in this zone is considered to be a downstream direction when proceeding from the feed inlet to the raffinate outlet streams.
Immediately upstream with respect to fluid flow in zone 1 is the purification zone, zone 2. The purification zone is defined as the adsorbent between the extract outlet stream and the feed inlet stream. The basic operations taking place in zone 2 are the displacement from the non-selective void volume of the adsorbent of any raffinate material carried into zone 2 by shifting of adsorbent into this zone and the desorption of any raffinate material adsorbed within the selective pore volume of the adsorbent or adsorbed on the surfaces of the adsorbent particles. Purification is achieved by passing a portion of extract stream material leaving zone 3 into zone 2 at zone 2's upstream boundary, the extract outlet stream, to effect the displacement of raffinate material. The flow of material in zone 2 is in a downstream direction from the extract outlet stream to the feed inlet stream.
Immediately upstream of zone 2 with respect to the fluid flowing in zone 2 is the desorption zone or zone 3. The desorption zone is defined as the adsorbent between the desorbent inlet and the extract outlet stream. The function of the desorption zone is to allow a desorbent material which passes into this zone to displace the extract component which was adsorbed upon the adsorbent during a previous contact with feed in zone 1 in a prior cyle of operation. The flow of fluid in zone 3 is essentially in the same direction as that of zones 1 and 2.
In some instances, an optional buffer zone, zone 4, may be utilized. This zone, defined as the adsorbent between the raffinate outlet stream and the desorbent inlet stream, if used, is located immediately upstream with respect to the fluid flow to zone 3. Zone 4 would be utilized to conserve the amount of desorbent utilized in the desorption step since a portion of the raffinate stream which is removed from zone 1 can be passed into zone 4 to displace desorbent material present in that zone out of that zone into the desorption zone. Zone 4 will contain enough adsorbent so that raffinate material present in the raffinate stream passing out of zone 1 and into zone 4 can be prevented from passing into zone 3 thereby contaminating extract stream removed from zone 3. In the instances in which the fourth operational zone is not utilized, the raffinate stream passed from zone 1 to zone 4 must be carefully monitored in order that the flow directly from zone 1 to zone 3 can be stopped when there is an appreciable quantity of raffinate material present in the raffinate stream passing from zone 1 into zone 3 so that the extract outlet stream is not contaminated.
A cyclic advancement of the input and output streams through the fixed bed of adsorbent can be accomplished by utilizing a manifold system in which the valves in 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 adsorbent in a counter-current manner. Another mode of operation which can effect the counter-current flow of solid adsorbent 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, desorbent input and raffinate output streams pass are advanced in the same direction through the adsorbent 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 in U.S. Pat. Nos. 3,040,777 and 3,422,848. 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 zone will contain a much larger quantity of adsorbent than some other operational zone. For instance, in some operations the buffer zone can contain a minor amount of adsorbent as compared to the adsorbent required for the adsorption and purification zones. It can also be seen that in instances in which desorbent is used which can easily desorb extract material from the adsorbent that a relatively small amount of adsorbent will be needed in a desorption zone as compared to the adsorbent needed in the buffer zone or adsorption zone or purification zone or all of them. Since it is not required that the adsorbent 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 in fact, in 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 desorbent material can be separated to produce an extract product containing a reduced concentration of desorbent material. 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 desorbent material can be separated to produce a desorbent stream which can be reused in the process and a raffinate product containing a reduced concentration of desorbent material. The separation means will typically be a fractionation column or an evaporator, the design and operation of either being well known to the separation art.
Reference can be made to D. B. Broughton U.S. Pat. No. 2,985,589, and to a paper entitled "Continuous Adsorptive Processing--A New Separation Technique" by D. B. Broughton presented at the 34th Annual Meeting of the Society of Chemical Engineers at Tokyo, Japan, on Apr. 2, 1969, for further explanation of the simulated moving-bed counter-current process flow scheme.
A dynamic testing apparatus is employed to test various adsorbents with a particular feed mixture and desorbent material to measure the adsorbent characteristics of adsorptive capacity, selectivity exchange rate, and extent of silicon contamination of the extract and raffinate streams. The apparatus consists of an adsorbent 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, polarimeters and chromotographs can be attached to the outlet line of the chamber and used to detect quantitatively or determine qualitatively one or more compounds in the effluent stream leaving the adsorbent chamber. A pulse test, performed using this apparatus and the following general procedure, is used to determine selectivities and other data for various adsorbent systems. The adsorbent is filled to equilibrium with a particular desorbent material by passing the desorbent material through the adsorbent chamber. At a convenient time, a pulse of feed containing known concentrations of a tracer and of a particular ketose or aldose or both all diluted in desorbent is injected for a duration of several minutes. Desorbent flow is resumed and the tracer and the ketose and aldose are eluted as in a liquid-solid chromatographic operation. The effluent can be analyzed on-stream or alternatively effluent samples can be collected periodically and later analyzed separately by analytical equipment and traces of the envelopes of corresponding component peaks developed.
From information derived from the test adsorbent, performance can be rated in terms of void volume, retention volume for an extract or a raffinate component, selectivity for one component with respect to the other, the rate of desorption of an extract component by the desorbent and the extent of silica contamination of the extract and raffinate stream. The retention volume of an extract or a raffinate component may be characterized by the distance between the center of the peak envelope of an extract or a raffinate component and the peak envelope of the tracer component or some other known reference point. It is expressed in terms of the volume in cubic centimeters of desorbent pumped during this time interval represented by the distance between the peak envelope. Selectivity, (B), for an extract component with respect to a raffinate component may be characterized by the ratio of the distance between the center of the extract component peak envelope and the tracer peak envelope (or other reference point) to the corresponding distance between the center of the raffinate component peak envelope and the tracer peak envelope. The rate of exchange of an extract component with the desorbent can generally be characterized by the width of the peak envelopes at half intensity. The narrower the peak width the faster the desorption rate.
To further evaluate promising adsorbent systems and to translate this type of data into a practical separation process requires actual testing of the best system in a continuous counter-current moving bed or simulated moving bed liquid-solid contacting device. The general operating principles of such a device are as described hereinabove. A specific laboratory-size apparatus utilizing these principles is described in deRosset et al U.S. Pat. No. 3,706,812. The equipment comprises multiple adsorbent beds with a number of access lines attached to distributors within the beds and terminating at a rotary distributing valve. At a given valve position, feed and desorbent are being introduced through two of the lines and the raffinate and extract streams are being withdrawn through two more. All remaining access lines are inactive and when the position of the distributing valve is advanced by one index all active positions will be advanced by one bed. This simulates a condition in which the adsorbent physically moves in a direction countercurrent to the liquid flow. Additional details on the above-mentioned adsorbent testing apparatus and adsorbent evaluation techniques may be found in the paper "Separation of C8 Aromatics by Adsorption" by A. J. deRosset, R. W. Neuzil, D. J. Korous, and D. H. Rosback presented at the American Chemical Society, Los Angeles, Calif., Mar. 28 through Apr. 2, 1971.
A static testing apparatus is employed, in a static dissolution test, to test the extent of silicon dissolution from a zeolite or zeolite containing adsorbent. The apparatus comprises an 800 ml glass jar, a temperature controlled liquid bath and a motorized stirrer. A quantity of adsorbent to be tested is placed in the jar which is filled with deionized water. Gentle stirring is effected to eliminate any mass transfer boundary layer around the immersed adsorbent. A sample of the water-silicon solution is taken from the jar at specific time intervals for determination of dissolved silicon concentration by an accepted method known to be accurate.
The static test simulates the embodiment of the process of this invention employing the continuous counter-current simulated moving bed liquid-solid contacting device. When the elapsed time from the start of a given test is short, the silicon concentration in the solution will be low, which is analogous to the adsorbent bed in the vicinity of the inlet ports of the contacting device, i.e. the inlet to the above described zone 1. After a certain elapsed time into the test (about 80 hours), the silicon concentration in the solution will substantially reach a maximum, which is analogous to the adsorbent bed in the vicinity of the outlet ports of the contacting device, i.e. the outlet of the above described zone 1 (raffinate stream) and zone 3 (extract stream). Elapsed times between the initiation of the test and the above certain elapsed time will be analogous to the adsorbent bed at other locations corresponding to each such elapsed times, i.e. such as zones 2 and 4.
Although both liquid and vapor phase operations can be used in many adsorptive separation processes, liquid-phase operation is required 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. Adsorption 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 range of from about atmospheric to about 500 psig. with from about atmospheric to about 250 psig. being more preferred to insure liquid phase. Desorption conditions will include the same range of temperatures and pressures as used for adsorption 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 our assignee's U.S. Pat. No. 3,706,812) to those of commercial scale and can range in flow rates from as little as a few cc an hour up to many thousands of gallons per hour.
The following examples are presented to illustrate our invention and are not intended to unduly restrict the scope and spirit of the claims attached hereto.
The purpose of this example is to demonstrate that an adsorbent comprising crystalline aluminosilicate, either bound or unbound with an amorphous binder, suffers dissolution and is a source of dissolved silicon when contacted with an aqueous medium.
For this example, two adsorbents were each subjected to a static dissolution test. The first adsorbent, hereinafter referred to as "ADS-B", comprised a pure Na-Y zeolite (Tradename Linde SK-40) pelletized and screened to a particle size between U.S. Mesh No. 30 and 50. The second adsorbent, hereinafter referred to as "ADS-A", comprised 80 wt. % ADS-B and 20 wt. % of an amorphous alpha alumina binder and was calcium cation exchanged, pelletized and screened to the same shape and size as ADS-B.
The results of the two static tests are plotted in FIG. 1. It can be seen that silicon was dissolved from both adsorbents. The adsorbent comprising pure zeolite (ADS-B) contributed a higher concentration of silicon than the adsorbent comprising the bound zeolite (ADS-A), but it is clear that substantial dissolution occurred with both adsorbents. The silicon concentrations for both tests at the 80 hour duration (18.5 ppm for ADS-B and 11.4 ppm for ADS-A) would be analogous to that in the vicinity of the outlet ports of a continuous simulated moving bed apparatus used in a saccharide separation process and would be unacceptable for use of the saccharide products as food additives. Further purification, for removal of the silicon, such as ion exchange, would be required for the saccharide products.
The purpose of this example is to demonstrate the improved adsorbent of our invention. An adsorbent, hereinafter referred to as "ADS-C", was prepared by the following steps:
(1) 50 grams of ADS-A adsorbent (see Example I) was loaded in a glass rotary impregnator.
(2) An aqueous solution containing aluminum ions was prepared by dissolving 0.72 grams of AlCl3.6H2 O in 400 ml of deionized water.
(3) 200 ml of the solution from step (2) was placed in the impregnator and the impregnator was rolled for one hour without heat.
(4) The impregnator was then heated from the outside with steam while rolling continued for another 5 hours.
(5) The ADS-C adsorbent was finally unloaded from the impregnator. The volatile matter of the adsorbent, as measured by weight loss on ignition at 900� C. was 25.5 wt. %. The aluminum content was 0.08 wt. %, calculated on the basis of elemental aluminum.
A static dissolution test was run with the ADS-C adsorbent. FIG. 2 provides a comparison of the results of the tests for the ADS-C and ADS-A adsorbents. At the initial stage, prior to 5 hours from the beginning of each, the ADS-C yielded about one half of the silicon yielded by the ADS-A. This is extremely significant because of the analogy of this stage to the vicinity of the inlet port to a simulated moving bed contacting device for use in the process of this invention. The adsorbent close to the inlet port is the most vulnerable to disintegration because of the large mass transfer driving force tending to drive the silicon into solution, i.e. the concentration of silicon in the feed solution at the inlet port is substantially less than the equilibrium concentration (about 15 ppm).
As the time of the static test for the ADS-C progressed, and through to the end of the test (80 hour duration), the rate of silicon dissolution, as compared to the corresponding time for the ADS-A test, was consistently low. Thus, the ADS-C was shown to have a higher disintegration resistance throughout the periods of the static test analogous to the zones of the simulated moving bed separation apparatus.
|Cited Patent
|Filing date
|Publication date
|Dec 24, 1953
|Apr 14, 1959
|Union Carbide Corp
|Molecular sieve adsorbents
|May 22, 1957
|May 23, 1961
|Universal Oil Prod Co
|Continuous sorption process employing fixed bed of sorbent and moving inlets and outlets
|Apr 10, 1959
|Jun 26, 1962
|Universal Oil Prod Co
|Rotary valve
|May 12, 1961
|Apr 21, 1964
|Union Carbide Corp
|Crystalline zeolite y
|Jun 9, 1966
|Jan 21, 1969
|Universal Oil Prod Co
|Multiport rotary disc valve with liner protection means
|Feb 20, 1964
|Jul 15, 1969
|Air Prod & Chem
|Cracking catalyst comprising aluminum zeolite
|Dec 7, 1970
|Dec 19, 1972
|Universal Oil Prod Co
|Fluid-solid contacting apparatus
|Feb 18, 1976
|Mar 29, 1977
|Toray Industries, Inc.
|Separation of fructose from a mixture of sugars
|May 29, 1979
|Dec 9, 1980
|Uop Inc.
|Technique to reduce the zeolite molecular sieve solubility in an aqueous system
|Citing Patent
|Filing date
|Publication date
|Jul 15, 1988
|Aug 15, 1989
|Allied-Signal Inc.
|Liquid filter with a distorting portion for transmitting hydraulic forces
|Sep 4, 1987
|Nov 14, 1989
|Process for separating ketoses from alkaline-or pyridine-catalyzed isomerization products
|Sep 8, 1988
|Dec 10, 1991
|Engelhard Corporation
|Ion-exchange agent and use thereof in extracting heavy metals from aqueous solutions
|Jun 15, 1998
|Mar 14, 2000
|Union Carbide Chemicals & Plastics Technology Corporation
|Separation processes
|Jun 15, 1998
|Apr 4, 2000
|Union Carbide Chemicals & Plastics Technology Corporation
|Separation processes
|Sep 29, 2006
|May 29, 2012
|Quantumcor, Inc.
|Surgical probe and methods for targeted treatment of heart structures
|May 15, 2007
|Dec 11, 2012
|Quantumcor, Inc
|Method for treating and repairing mitral valve annulus
|Sep 29, 2006
|Apr 3, 2008
|Duane Dickens
|Surgical probe and methods for targeted treatment of heart structures
|U.S. Classification
|127/46.3, 536/127, 210/691, 127/46.2, 502/64
|International Classification
|Cooperative Classification
|European Classification
|Sep 21, 1988
Owner name: UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD;REEL/FRAME:005006/0782
Effective date: 19880916
|Apr 27, 1989
Owner name: UOP, A GENERAL PARTNERSHIP OF NY, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UOP INC.;REEL/FRAME:005077/0005
Effective date: 19880822


text:
I have been involved in Scouting for over 14 years and have held several different positions. From 3 different positions at the Pack level to positions in the Troop, District, and Council, but the most memorable was as COurse Director for Community Day Camp. It was 2000 and we were into our second day of camp wheis little 8 year old boy walked up to me and with a grin from ear to ear said, "Mr. Nault, thank you. This was the best day ever of my entire life." And then he hugged me and ran off. That memory is why I do what I do and keep on doing it.
My son is entering his 5th and final year as cub scout. I have also been committee chairmen for a couple of years now. I look at all the opportunities that scouting has given my son and I am amazed. I just can't get over all of the outdoor activities that the scouts do right in our own neighbor hood. Also it really teaches the boys to be responsible not only for them selves but for the environment also. The boys also learn allot of useful skills to help them through life. Also the day camps that the council holds in summer and winter are very well planned out. I was kind of amazed at all of the different skills that are learned at these camps. I think that every parent should allow their boys to have a taste of scouting. I wish I would have had the opportunity to be a scout when I was younger. I think there are allot of good people in scouting who really want to see it succeed.
Growing up, I was a Cub Scout, then a Boy Scout, now I'm happy to say I'm a Cubmaster for my third year, with my 2 sons both in Cub Scouts. Seeing the boys I'm responsible for growing, and seeing the pride they take in earning their awards is such a great experience! Boy Scouts of America, and all it's options for both boys & girls to get involved in really can help our youth grow into the leaders of tomorrow! And the best part? You don't have to have a son/daughter that wants to be a scout to get involved! If you have the willingness to give a little bit of your time, you can help out. You can do anything from teaching a skill you have to becoming a leader and really get involved. To me, there is nothing better than to see the smile on a scout's face as they receive the recognition for the hard work they put in.
Prevent not Correct Scoutmaster Sam Anderson and I waited at Stoughton, WI. on the bank of the Yahara River in the spring of 1947 for canoes with the "older scouts" to arrive at the campsite. When they rounded the bend a quarter of a mile upstream excitement prevailed. Beyond the thrill of adventure Scouting's program is unequaled in its successful emphasis on ciitizensip training, fitness, service, leadership, values and character development. The cultivation of positive habits and attitudes in maturing young people far exceeds the effectiveness of the very costly remedial strategies used by society in dealing with poor behavior habits and values.
I have been a leader for the BSA in Cub Scouts and now Boys Scouts for over a year now...my sons for about 2 years. I must admit...having known nothing about the organization prior and now being fully immersed...it is overwhelmingly the most positive experience in our lives! My sons have the opportunity to explore SO MANY facets of life!! Life...that's right...made up of many different components...God, Service, Country, Family Life, Sports, Social Life, Arts, Liberty, Sports...I could go on and on. My sons are different in nature and interests, yet, they both love Scouting! What a positive influence on both my sons and our family as a whole to "Do Your Best" every day. We are not perfect, but with the guidance of the BSA, we "Do Our Best" every day!
I volunteered (or was volunteered) 3 years ago with much trepidation to become a Cub Scout Den Leader. I am now proud to say that I thoroughly enjoy being a leader in this organization. It has allowed my sons and my family to experience things within our family and within the boys peer groups that they wouldn't have had the opportunity to experience. It has strengthened my relationship not only with my sons, but also within the community.
Boy Scouting is not just about campfires. Our children are offered many extra-curricular opportunities, most of which focus on competition against other individuals or teams. The Boy Scout program focuses on character development, service to others, and developing leadership skills. Boy Scout meetings are conducted by the youth members rather than adults. Activities are planned by the youth members with adult assistance. Older boys teach the younger boys skills such as tying knots, first aid, and using a map and compass. Through these activities, the boys learn to work together and to lead others.
I recently had the privelege of conducting a scoutmaster review for an Eagle scout. I asked him how scouting had influenced him. He was quick to respond that the experience had changed his moral and ethical direction. He said that had he not joined scouting he was going down a very different path. I see a lot of young scouts grow up to be young men and Scouting always makes a positive impact.
As a homeschooling family it is important to find age appropriate activities for our sons. Cub Scouts has definitely been the best thing we have ever done! Our sons are loving every minute of it. I am even a Den Leader (not something I ever thought I would do!). The activities required in the handbook are fantastic. They are challenging without being daunting and the boys really do enjoy doing them. I just cannot say enough good things about Cub Scouts (the younger group of the Boy Scouts of America).

subset: commoncrawl


text:
Rick was originally brought in to work with a core team that would replace our enterprise back office systems with Oracle and provide business intelligence reporting and dashboards. Fourteen years later, he oversees all of our corporate business applications.
Rick works closely with leadership to identify business improvement opportunities. He also manages development and support for all of our enterprise business applications, and his team plays a key role in integrating acquisitions.
A problem solver, Rick is drawn to the challenges of a growing company. With our wide variety of business practices, lines, and sectors, as well as the needs of new acquisitions, Rick is never short of collaborative projects that search for gaps to fill, integrating new systems and building up new functionality. Rick is looking forward to transforming our systems to support global operations with the acquisition of MWH Global.
When he isn't at work, Rick might be spending time with the family, golfing, or playing baseball with the Feisty Dodgers. He's a regular traveler and enjoys spending time in Phoenix and Disneyworld.


text:
W. Clement Stone, (born May 4, 1902, Chicago, Ill.—died Sept. 3, 2002, Evanston, Ill.), American businessman and philanthropist who made a fortune in insurance but became better known for promoting his philosophy of success and for his support of political and social causes. He espoused what he called P.M.A. (positive mental attitude) as the key to achievement and wealth. A major contributor to the 1968 and 1972 presidential campaigns of Richard M. Nixon, he also supported philanthropic causes such as mental health and youth welfare. Following the Watergate Scandal (1972–75), Stone's large contributions to Nixon were sometimes cited as an example of the need for campaign finance reform. Stone's father died when he was three years old, leaving the family impoverished, and at the age of six the boy began selling newspapers. By age 13 he had his own newsstand, and three years later he moved to Detroit to help his mother in an insurance agency. He dropped out of school, although he later received a diploma from a YMCA high school. In 1922 he opened his own agency in Chicago, the Combined Insurance Company of America, selling accident and life insurance, and by 1930 he had employed some 1,000 agents across the U.S. Over the years he bought additional companies, merging them with Combined, and in 1982 he merged his company with the Ryan Insurance Group, renaming the new firm Aon Corp. in 1987. With Napoleon Hill he developed a lecture series and the magazine Success Unlimited, and the two also wrote the book Success Through a Positive Mental Attitude (1960). Among Stone's other books was The Success System That Never Fails (1962). He expected his employees to join with him in beginning each day with "I feel happy! I feel healthy! I feel ter-r-r-ific!"
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text:
The room in the Library containing the priest. His dialogue can be seen in subtitles.
|Amnesia: Justine
|Cabinet of Perturbation
|Reach the next area, either by killing or saving the prisoner.
|Danger rating
|High risk
|Location guide
| Previous
| Next
- "Father used to say, there were no right answers. Have the light guide you."
- ―Justine[src]
The library contains a main room with five side chambers, one in which is the area's hostage, Father David. The fifth room, which is opposite the area's entrance, contains a projector. Four slides and numerous notes are found in this area, along with a boarded-up door which apparently conceals a Suitor (likely Basile). The room containing the hostage also features pictures of Justine and her parents.
The puzzle in this room involves using the four slides with the projector and "Puzzle Lock" to open a hidden passage. Failing to do so will result in Father David being ripped apart.
After completing the puzzle, the player will descend into a dark underground room where he or she will encounter Basile. The dungeon and tunnels are accessed from the library, though the door to the tunnels is jammed.
Each slide found in each room has a different picture of a man: the one with open arms, the one who's kneeling, the one with the sword, and the one being blessed.
Collectibles Edit
Tinderboxes Edit
- Two tinderboxes can be found in the first room to your right as you enter the library.(1 & 2)
- Another two can be found in the room on the opposite side of the one described above.(3 & 4)
- The fifth and final tinderbox can be found in the room opposite of the room where Father David is trapped.(5)
Notes Edit
- Results - This note can be found in the first room to your right.
- Herbert's Letter - This note can be found in a bookshelf on the right side of the same room as the previous note. It can be a little tricky to spot.
- Soul Journal Entries - This note can be found in a table in the second room to the right, the room with the captured preist.
- Shipment Slip - Entering the room at the end of the hallway in the library and then taking a right and heading straight you will find yourself at a bookshelf. One of the books in this bookcase can be removed to reveal this note behind it. Finding this note will unlock the "Still Alive" Gold Trophy in the PS4 version of the game, as well as slightly altering the dialogue between Justine and Clarice at the end of the game.
|Locations of Justine
|Cabinet of Perturbation
|Cells • Library • Dungeon • Crypt
|Other Locations
|Florbelle Estate


text:
A Novel Profit Maximizing Metric for Measuring Classification Performance of Customer Churn Prediction Models
Issue No. 05 - May (2013 vol. 25)
pp: 961-973
DOI Bookmark: http://doi.ieeecomputersociety.org/10.1109/TKDE.2012.50
Bart Baesens , Katholieke Universiteit Leuven, Leuven and University of Southampton, Highfield Southampton
Wouter Verbeke , University of Edinburgh, Edinburgh
Thomas Verbraken , Katholieke Universiteit Leuven, Leuven
The interest for data mining techniques has increased tremendously during the past decades, and numerous classification techniques have been applied in a wide range of business applications. Hence, the need for adequate performance measures has become more important than ever. In this paper, a cost-benefit analysis framework is formalized in order to define performance measures which are aligned with the main objectives of the end users, i.e., profit maximization. A new performance measure is defined, the expected maximum profit criterion. This general framework is then applied to the customer churn problem with its particular cost-benefit structure. The advantage of this approach is that it assists companies with selecting the classifier which maximizes the profit. Moreover, it aids with the practical implementation in the sense that it provides guidance about the fraction of the customer base to be included in the retention campaign.
Business, Knowledge engineering, Area measurement, Receivers, Data engineering, Educational institutions, performance measures, Data mining, classification
Bart Baesens, Wouter Verbeke, Thomas Verbraken, "A Novel Profit Maximizing Metric for Measuring Classification Performance of Customer Churn Prediction Models", IEEE Transactions on Knowledge & Data Engineering, vol. 25, no. , pp. 961-973, May 2013, doi:10.1109/TKDE.2012.50


text:
Ben Needham's mother to make TV plea 24 years after toddler vanished in Greece
THE mother of missing Ben Needham has travelled to Greece to make a TV appeal alongside British police officers.
Kerry Needham and her son Ben, who went missing in 1991
Ben, from Sheffield, vanished on July 24, 1991 while holidaying on the Greek island of Kos with his mother Kerry and his grandparents. He was 21 months old.
Over the years there have been a number of possible sightings and a range of theories about what happened to the youngster, who would now be 25.
Mrs Needham and Ben's grandmother Christine will take part in the TV show on Friday, along with his sister Leighanna.
Joining them will be Detective Superintendent Matthew Fenwick and Detective Inspector Jon Cousins of South Yorkshire Police.
A smiling Ben Needham in a picture from the family album
The show about missing people is watched by around 50 per cent of the Greek TV audience.
In January, South Yorkshire Police was granted up to £700,000 of Home Office funding to support the Greek authorities in continuing inquiries to find Ben.
The force asked for the financial help to follow up information the family believes has never been properly investigated.
The Home Office backed a South Yorkshire Police operation in 2012 when land was excavated near the farmhouse from where Ben went missing. No trace of him was found.
Last year, a DNA test on a young man featured in video footage shot in Cyprus proved negative.
An artist's impression of what Ben Needham might look like in his 20s
Mrs Needham posted on her fundraising site today: "As part of the launch of Operation Ben I have arrived in Athens this morning with my family and detectives from South Yorkshire Police.
"During our five days here we will be meeting the British ambassador for the first time in 23 years to discuss Ben's case.
"Myself and family, along with British detectives, will be appearing on the Greek missing programme Nikolouli, as well as holding a press conference.
"We sincerely hope this will lead to more people coming forward with new information and will help the British and Greek police investigate into the whereabouts of Ben."


text:
Israel is left very, very damaged and vulnerable after Isaiah 17 / Psalm 83, which sets the stage for the Ezekiel 38 invasion.
Israel is left very, very damaged and vulnerable after Isaiah 17 / Psalm 83, which sets the stage for the Ezekiel 38 invasion.
I am still holding to the idea that the Church could see Isaiah 17 while it is still here, as God does not indicate His direct involvement in that event. He does, however, make clear his involvement in Ezekiel 38 & 39, making them part of His re-engagement with Israel and the gentile nations.
As far as Isaiah 17 being the catalyst for Ezekiel 38 & 39, it's hard to say with certainty, although it is certainly possible. Things are happening so rapidly now, that scenarios can change literally overnight. Russia invades Georgia and within weeks completes alliances with the remaining countries involved with Gog/Magog. Something prophecy students had been looking for for years all lined up in a matter of weeks.
How much would an Israeli attack on Iran change things? Would Syria counterattack on Iran's behalf, do something stupid and incur destruction on Damascus? Could happen. But the bigger wild card to me is the rapture. If it happened soon, things would suddenly accelerate at break neck speed.
We just don't know.
Would some one please explain ? I did not know that the millennium was eternity. I did not think eternity started until AFTER the Millennium. When the devil is released from his chains and goes about deceiving the nations , then God puts a quick stop to it He destroys the world with fire and God will create NEW Heavens and a new earth. This is when Eternity begins.
That leaves the deduction that Jordan is not involved with Ezekiel 38 to be a key point in why Ps 83/Is 17 happens first? Still unclear that there is a Biblical point here or just speculation. What if Jordan is having a major crisis or something (pestilence, famine, whatever) that prevents them from participating ins Ezek 38? Just saying, if we are going to speculate we should consider many options.
I'll have to delve into this more, but my understanding is that Edom (southern Jordan) will be so desolated so that man will never live there again and it will not be part of the MK. Moab (central Jordan) will be partially destroyed and those that remain will come to salvation and will enter the MK. Ammon will be partially destroyed and will become a possession of Israel and will enter as a nation into the MK. These, of course do not immediately speak to timing either, but if this all hinges on Jordan, than a full study of prophecy concerning Jordan - Edom, Moab and Ammon is necessary. Talk to you again tonight!
Last edited by Trust&Obey; April 21st, 2009 at 04:54 PM. Reason: confused:) replaced Ps 83/Is 17 with Ezek 38
John 14:6
Jesus answered, "I am the WAY and the TRUTH and the LIFE, no one comes to the Father except through Me."
Jillian - just a quick reply. Some have said that Ezek 38 is the war that happens when Satan is loosed at the end of the 1,000 years. I think the poster that talked about 7 years burning fuel and 7 months burying bodies was saying that this could not go into eternity. So that proves this is not the same war as at the end of the MK.
The 7 years/7months is also used by many (Fruchtenbaum for one) to say that Ezek. 38 needs to happen prior to tribulation. Frucht says 3 1/2 years prior since, he says Jews will be on the run in the last 3 1/2 years of tribulation and will not be concerned with burying bodies or burning fuel. Most agree that if it happens in the tribulation it will have to happen at the very beginning (because they do not see these things going on during the MK). I tend to think it will happen prior to the tribulation but am not dogmatic that it has to be at least 3 1/2 years prior.
John 14:6
Jesus answered, "I am the WAY and the TRUTH and the LIFE, no one comes to the Father except through Me."
Isaiah 17:13
13. The nations shall rush like the rushing of many waters: but God shall rebuke them, and they shall flee far off, and shall be chased as the chaff of the mountains before the wind, and like a rolling thing before the whirlwind.
I enjoy your discussions of these prophetic passages.
I would suggest we not forget that our Lord Jesus Christ will reign forever (Luke 1:32, 33; Daniel 7:13, 14; Revelation 11:15) upon this earth from Jerusalem (Isaiah 24:23). Therefore, there is no such thing as anything "carrying over to eternity" as taking place anywhere else than on this earth (Matthew 5:5). This earth shall never be destroyed (Ecclesiastes 1:4 and parallel passages like Psalm 78:69; Psalm 89:36, 37; Psalm 72:5, 7, 17) but will last forever. It cannot be otherwise or God would violate his Covenants with Abraham and David.
The Millennium only marks, as far as time goes, the length of time that Satan is bound. It DOES NOT mark how long Jesus reigns on the Throne of David here on this earth!
Many prophetic students today have carried over this mistaken notion from mistaken students of yesteryear in the nineteenth century, as fully documented in the wonderful but exhaustive study of these issues in George N. H. Peters' work, The Theocratic Kingdom (where he very politely and gently corrects them in detail from Scripture!).
I agree that if Psalm 83 is to be taken as prophecy and if it can be associated properly with Isaiah 17, then the events of Ezekiel 38 and Ezekiel 39 must follow in the order of things. That Psalm 83 is prophecy and not merely an echo of history is quite certain because Psalm 83:8 mentions Assur, or Assyria (and thus may possibly be linked with The Assyrian mentioned in Micah 5:5 and parallel passages), and this country and region, far as I recall, does not figure by name into the historical account alluded to in Psalm 83 in 2 Chronicles 20:5-12.
As for objections and considerations in reference to the presence of imprecatory prayer in Psalm 83, this has no bearing upon the issue. If you carefully study the subject of imprecatory prayer you will find it used in the New Testament by Paul, for example. I'm sure many may be sensitive to the issue and may not feel it their position to pray in this manner, but in the Bible many clearly within God's will did pray this way.
In the light of the fact that we are seeing a contemporary "Evangelical Collapse" so-called, when we could be seeing an "Evangelical Revival" if those who claim to be Christians would engage in personal direct study of the Bible on a regular basis, let me share some verses for you to study about imprecatory prayer:
Jeremiah 10:25. Jeremiah 11:20. Jeremiah 12:3. Jeremiah 15:15. Jeremiah 17:18. Jeremiah 18:21-23. Numbers 16:15. Deuteronomy 33:11. Joshua 8:33, 34. Judges 16:28. 1 Samuel 26:19. 2 Chronicles 24:22. Nehemiah 4:4, 5. Nehemiah 5:13. Nehemiah 6:14. Job 27:7. Psalm 5:10. Psalm 9:20. Psalm 10:2, 15. Psalm 28:4. Psalm 55:9, 15. Psalm 56:7. Psalm 59:5, 11, 13, 15. Psalm 68:1, 2. Psalm 69:22-24, 27, 28. Psalm 71:13. Psalm 79:10, 12. Psalm 94:2. Psalm 119:78, 84. Psalm 140:9, 10. Psalm 143:12. Psalm 144:6. Lamentations 1:22. Lamentations 3:64-66. 1 Corinthians 16:22. Galatians 1:8, 9. 2 Timothy 4:14. Revelation 6:10.
While we are indeed to pray for our enemies, the Bible in all the verses I just referenced for you on this subject indicates that we are also to pray against evil and evil doers. Certainly this is a part of very much needed spiritual warfare in this day.
It is clear from such a passage as Exodus 22:22, 23 that "If...and they cry at all unto me, I will surely hear their cry; [24] And my wrath shall wax hot, and I will kill you with the sword; ..." stands as a warning and moral principle found throughout the Bible. God hears the cries of those who call to Him about injustice, for example, and God most certainly does something about it in answer to these prayers both in the "here and now" and in the "hereafter" you may be sure!
To learn more (I am sure there are no lessons in your current Sunday school quarterlies about this issue) go directly to the Bible and search it out by means of the extensive cross references furnished in a study tool like Nelson's Cross Reference Guide to the Bible and look up the cross references for Exodus 22:22, 23 or any other passage you want to learn more about from the Bible itself.
Also, the burning of weapons for seven years is another difference, as someone has already pointed out. The invading army of Eze 38-39 is destroyed on the mountains of Israel, whereas the one after the Millennium is upon the breadth of the Earth. No mention of the devil is made in Eze 38-39, whereas he is seized and doomed in the Millennial one. Fire and brimstone, hailstones and an overflowing rain destroy the Eze 38-39 army, whereas fire alone (no mention of brimstone or rain or hailstones) comes down out of heaven and fire alone consumes the Millennial one. The sixth part of the Eze 38-39 army is left, whereas NONE of the Millennial one is left.
Rev 20:7 When the thousand years are over, Satan will be released from his prison 8and will go out to deceive the nations in the four corners of the earthGog and Magogto gather them for battle. In number they are like the sand on the seashore. 9They marched across the breadth of the earth and surrounded the camp of God's people, the city he loves. But fire came down from heaven and devoured them. 10And the devil, who deceived them, was thrown into the lake of burning sulfur, where the beast and the false prophet had been thrown. They will be tormented day and night for ever and ever.
These are two separate battles. To confuse them, is like confusing the first coming of Jesus with the Second. After all, they both tell of His coming. The difference is in the details.
The prophecy of the Gog-Magog assault says in Chapter 39 that God would send fire upon Magog (Gog's country) and the coastlands (the farthest reaches of the Earth away from Israel). This sounds ominously like a nuclear war between Russia and the USA. Estimates made back in the '80s during the no-nuke demonstrations days suggested that a nuclear war could wipe out 1/4th of the Earth's population. This I know, because I knew a fellow who was involved with that, and when he told me that it could wipe out a fourth, I took him to Revelation 6 and showed that to him. It stunned him.
What I am saying, is that I find it unlikely that there could be two such nuclear wars, first one prior to the seven years, and then another inside the Trib. very near the beginning of the seven years. This is why I believe that the Gog-Magog conflict triggers World War III, and that it is identified with the Second Seal (along with Seals 3 and 4).
As for the burning of weapons for seven years, once the Jews are in hiding after the AOD at the middle point of the Trib, the weapons will furnish them fuel while they are in hiding, so they don't have to try to appropriate coal, propane, etc for cooking and keeping themselves warm, The weapons will be abundant, to be burned for the asking.
If the weapons are burned for seven years, and if the Gog-Magog conflict occurs after the Tribulation, then wouldn't that necessarily mean they will be burning weapons into the Millennium? Not necessarily. Notice the following:
Daniel 12:11 "From the time that the daily sacrifice is abolished and the abomination that causes desolation is set up, there will be 1,290 days. 12 Blessed is the one who waits for and reaches the end of the 1,335 days.
There will be a blessing after 1335 days after the AOD. Apparently, the Millennium will not necessarily start IMMEDIATELY after the Second Coming, but will be delayed 30 to 75 days. If this is true, and if indeed the Gog-Magog war is the same as the Second Seal, then that means that in about 30 to 75 days after the start of the Tribulation, nuclear war will break out, the long-dreaded World War III.
Think about the implications of this. Hypothetically speaking (not date-setting), but if the Rapture were to happen, say this Summer, then in about 1 to 2-1/2 months later, nuclear mushroom clouds will be sprouting over America this year.
Chew that over a while. Even if my premise and scenario about Eze 38-39 = Seal #2 is wrong, anyone left behind will almost certainly still face mushroom cloud annihilation shortly after the Rapture, for the Second Seal still follows after the Seal #1 revelation of the Antichrist. None of the well-meaning Christian filmmakers who make all these movies about people left behind to face the Antichrist, make the proposal that those left behind will be annihilated in atomic war.
I will repeat myself. If the Rapture and Trib should start this year, this year will likely also see nuclear war.
If this frightens you, it should. But, that fear should not be for yourselves, since we will be Raptured out first, but we should fear for those whom we care about who will be left behind.
Last edited by sirgak; April 23rd, 2009 at 02:07 AM.
Your post was an interesting read. Thanks!
"We have no defenses against space junk, people!" - Take me away!
*Ask me about my testimony!*
sirgak - thanks for the very informative and well-thought out reply. I have had a similar thought that Frucht's reasoning on burning fuel didn't make sense for the same reason you stated,
I also don't like the 3 1/2 year prior because it seems to interefere with immenency of the rapture (although, if one were to believe that there could be a gap of years between the rapture and the trib, that would take care of it). I do believe the timeline you presented (tying Ezek 38-39 to the 2nd Seal) makes a lot of sense to me.As for the burning of weapons for seven years, once the Jews are in hiding after the AOD at the middle point of the Trib, the weapons will furnish them fuel while they are in hiding, so they don't have to try to appropriate coal, propane, etc for cooking and keeping themselves warm, The weapons will be abundant, to be burned for the asking.
In a conference last August (remember Georgia was going on then), I asked Dr. Fruchtenbaum what he thought the "hook in the jaw" was going to be. Paraphrased, he said Gog will be heading North until he comes back to Israel (the hook). What is north of Russia? North America. He didn't elaborate any more on that subject.
John 14:6
Jesus answered, "I am the WAY and the TRUTH and the LIFE, no one comes to the Father except through Me."
Well I have read your replies and reread my Bible carefully. Psalm 83 not only makes no mention of the Israeli military, but calls for God to wipe away Israel's enemies with fire storms and other natural disasters, which God will also use in Gog and Magog. It also says that after the event, Israel's enemies will know that the Lord is God, Just like in Ezekiel. A few years ago, there was talk of Gog and Magog being imminent. Then I suddenly got introduced to Psalm 83 and Isaiah 17, which seemed to put Gog and Magog off. With respect to all of your views, I stand by my position.
- Believers will reign with Christ for 1,000 years according to Revelation 20:6.
- There will be a new earth and a new Jerusalem according to Revelation 21:1-2.
- There will be "no more sea" in this new earth - Rev 20:1
What are in MK passages of the OT that are not in Rev 20:1? Sea
- Psalms 72:8 says Christ will rule from "sea to sea"
- Isaiah 11:9 Isaiah 11:11 also mention sea during MK
- Ezekiel 47:10, Ez 47:15, Ez 47:17-18 talks of the "sea"
- Ezekiel 48:28 mentions the "great sea"
- Zechariah 9:10 says Christ's dominion will be from "sea to sea"
The OT also verifies "new heavens and earth" in these passages:
The NT also verifies the "new heavens and earth"Isaiah 65:17 (King James Version)
17For, behold, I create new heavens and a new earth: and the former shall not be remembered, nor come into mind.
Isaiah 66:22 (King James Version)
22For as the new heavens and the new earth, which I will make, shall remain before me, saith the LORD, so shall your seed and your name remain.
Christ's reign on David's throne is not contingent on the earth not being re-created or made new.2 Peter 3:13 (King James Version)
13Nevertheless we, according to his promise, look for new heavens and a new earth, wherein dwelleth righteousness.
When I reviewed your scripture references:
- Isaiah 24:23 - no mention of eternity - just says the Lord will reign on Zion.
- Luke 1:32-33 - says Christ will sit on the throne of David, Christ will reign forever and His kingdom will not end (can be true through both MK and eternity)
- Daniel 7:13-14 - says Christ's dominion will be everlasting and His kingdom shall not pass away (again the "kingdom" won't pass away - however doesn't say God won't upgrade the earth and heaven - which is what is said in other scriptures)
- Revelation 11:15 - same concept. The definition of "kingdom" has to do with authority and royal power - Christ will reign over His kingdoms for all eternity. In Revelation 20:1 and the others I mentioned above God's Word says He will create new heavens and a new earth.
- Matthew 5:5 - refers to the MK
- Due to time/space I will summarize with this statement. It is quite possible that the earth can both be eternal and be "new". In fact, it is possible the earth is "re-created".
John 14:6
Jesus answered, "I am the WAY and the TRUTH and the LIFE, no one comes to the Father except through Me."
A quick afterthought to my last post:
God will sit on His throne both before and after the new heavens are made. His dominion does not change because He creates new heavens and a new earth. Why would Christ's?
John 14:6
Jesus answered, "I am the WAY and the TRUTH and the LIFE, no one comes to the Father except through Me."
I have been looking for something to happen to bring Iran's nuke projects to a halt without a attack by Israel. I admit that I had no idea of how this might come about, but it looks like we could be beginning to see how it could come about. Israel could still attack Iran, but right now I still think that they are going to go to a state of high alert and keep a close watch on them. I have never seen anything in scripture that makes me believe that Iran would ever be able to get a nuke bomb and use it or attempt to use it on Israel. It is still my belief that as a result of what is going on now that Iran will have to make some big changes in its plans.
1. I expect them to get desperate and have gaza's hamaz to attack Israel in every way that they can. Also look for the PLO in the west bank to attack, in spite of what they are saying now. I believe that this would come about because Iran needs something to get the people rioting against the rulers to join them and help in an attack on Israel.
2. Also look for an attack on Israel from the north by Syria and hezebolla to start with rocket attacks and maybe even a land attack to take back the Golan Heights. Also look for Damascus to be part of the attack and at some point they will be destroyed completely. Weather Israel will do it or someone else or maybe GOD will destroy Damascus, I am not sure, but it will happen. I do lean more to Israel destroying Damascus, but understand that it could be GOD that will accomplist it.
3. From scripture I also look for Jordan, Egypt, and Saudi Arabia to also get in on the attack on Israel. Israel will probably need to use everything it has to be able to defeat all those around her that will be in this attack. They will win and Iran will find itself greatly weakened after this war is over. Israel will also be weakened greatly because she had to use every thing in their pocession in order to win this war. This series of events IMHO is Isaiah 17 and Psalm 83. Israel will totaly destroy hesbolla, hamaz, and the plo and the other in this attack. Although weakened greatly, they will still be there.
4. Iran from having all the above destroyed will be left more or less alone and need help from someone. I still believe that events going on there now are somehow going to cause their nuke plans to either be destroyed or put on hold because of damaged caused by the riots. It is also possible that those wosrking on the nukes will also start to rebell and destsroy key parts of the nuke plants. If this happens and I believe that it could, Iran would need help and need it quickly.
5. That brings us up to Gog Magog war and those that join in that war. Russia will be the head and the moslem nations will follow including Iran. The combined armies will be so big, Russia and all the moslem nations that scripture list that Israel could not win even if they used all their nuke weapons. Russia may try to use nukes and chemical weapons but I believe that GOD will prevent them from working. Israel will do nothing but sit back and watch because they know that unless GOD fights for them all will be lost and they will be gone. Surprise Gog Magog and all Moslems, GOD is going to fight and only one in six of you will excape. When they try to flea back to their homelands their homelands will be destroyed too. I also think that most if not all Moslem capitols and and major cities will be gone, along with Mecca and Medena. I beleve that as a result most of the Moslem religion be cease to be a major force.
6. Another thing that could happen would for all sleeper cells in the west, and expecially in the US would attack and leave us to busy to even think about helping Israel. ALSO, THE RAPTURE PROBABLY HAPPENS SOMETIME DURING THIS TIME, probably after Isaiah 17 and Psalm 83. GOD still controls this event but I do believe that is will happen before Gog Magod.
William Beason
I've thought the same thing. Iran gets desperate to keep Israel from attacking, so they use their proxies (Hezbollah & Hamas) to start a multiple front war with Israel to keep them bogged down.1. I expect them to get desperate and have gaza's hamaz to attack Israel in every way that they can. Also look for the PLO in the west bank to attack, in spite of what they are saying now. I believe that this would come about because Iran needs something to get the people rioting against the rulers to join them and help in an attack on Israel.
2. Also look for an attack on Israel from the north by Syria and hezebolla to start with rocket attacks and maybe even a land attack to take back the Golan Heights. Also look for Damascus to be part of the attack and at some point they will be destroyed completely. Weather Israel will do it or someone else or maybe GOD will destroy Damascus, I am not sure, but it will happen. I do lean more to Israel destroying Damascus, but understand that it could be GOD that will accomplist it.
So then at what point do you see the Trib starting? After the Gog war?


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