text:
|31. März 1992
|14. Dez. 1990
|14. Dez. 1990
|Gary W. Skeels, Diane M. Chapman-Snyder, Edith M. Flanigen
|Ursprünglich Bevollmächtigter
|Zitat exportieren
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|Patentzitate (6), Referenziert von (8), Klassifizierungen (21), Juristische Ereignisse (5)
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The present invention relates in general to a method for substituting silicon atoms for framework aluminum atoms in zeolites, and, more particularly, to the method for silicon insertion wherein a crystalline zeolite is contacted in an aqueous medium with low concentrations of a bifluoride salt under reaction conditions which cause the extraction of aluminum atoms from the crystal lattice and the partial filling of the vacated lattice site by silicon atoms derived from the starting zeolite.
Heretofore, three different techniques have been proposed for increasing the framework Si/Al ratio of crystalline zeolites by the extraction of aluminum atoms and the at least partial substitution of silicon atoms into the sites previously occupied by these extracted aluminum atoms. Numerous chemical extraction procedures using mineral acids, chelating agents such as ethylene diaminetetracetic acid (EDTA), solutions of CrCl3, gaseous fluorine, phosgene and the like are also known, but the vacancies left behind by the extracted aluminum atoms are not reoccupied by silicon atoms. In the case of the CrCl3 treatment, however, the substitution of chromium atoms into the vacated sites is reported. In this regard see U.S. Pat. No. 3,937,791, Garwood et al.
Of the prior reported silicon insertion procedures, the earliest and the most thoroughly investigated involves the steaming of a hydrogen or ammonium exchanged form of the starting zeolite at temperatures usually in excess of 550° C. using a steam environment containing at least 2 psia water vapor pressure.
For example, U.S. Pat. No. 3,591,488 discloses that the hydrogen or ammonium form of a zeolite may be treated with steam at a temperature ranging from about 800° F. to about 1500° F. (about 427° C. to about 816° C.), and thereafter cation-exchanged with cations including rare earth cations.
It appears to be generally accepted among those skilled in the art that aluminum atoms extracted from the crystal lattice and moved to the interstitial space are immediately replaced by a "nest" of four hydroxyl groups and that some portion of these hydroxyl nests are in turn replaced by silicon atoms. There is not general agreement as to the source of the replacing atoms, i.e., pre-existing framework silicon atoms or occluded silicon-containing impurities, or the degree to which "healing" of the lattice occurs. It has been shown, however, that steamed faujasite type zeolites develop a secondary mesopore system with pore radii in the range of 15 to 19 A, indicating that the silicon substitution mechanism does involve the migration of framework silicon atoms and possibly the elimination of entire sodalite cages. See in this regard, U. Lohse et al, Z. Anorg. Allg. Chem., 1980, 460, 179.
U.S. Pat. No. 3,493,519 discloses a process for calcining an ammonium-Y zeolite in the presence of rapidly-flowing steam followed by base exchange and treatment of the product with a chelating agent capable of combining with aluminum whereby aluminum is extracted from zeolite Y.
U.S. Pat. No. 4,036,739 discloses a hydrothermally stable and ammonia stable Y-type zeolite intended for use as a cracking catalyst. The zeolite is prepared by partial exchange of ammonium ions for sodium ions, steam calcination under controlled conditions of time, temperature and steam partial pressure, and a second ion-exchange of ammonium ions for sodium ions to reduce the final Na2 O content to below about 1 weight percent. Following the second ion-exchange, the zeolite is calcined for a time sufficient to effect substantial deammoniation but insufficient to reduce the unit cell dimension to below about 24.40 A. According to U.S. Pat. No. 3,781,199, the second calcination may be conducted after the zeolite is admixed with a refractory oxide.
A much later developed technique for silicon insertion is reported by Beyer et al in Catalysis by Zeolites, ed. B. Imelik et al (Elsevier, Amsterdam, 1980) p. 203. In this procedure, apparently operable only in the case of zeolites of the faujasite type of structure, the starting zeolite is contacted with silicon tetrachloride vapor at elevated temperatures, typically about 400° C. to 500° C. The reaction which occurs is ideally
Na.sub.x (AlO.sub.2).sub.2 (SiO.sub.2).sub.y +SiCl.sub.4 →Na.sub.x-1 (AlO.sub.2).sub.x-1 (SiO.sub.2).sub.y+1 +AlCl.sub.3 +NaCl
It is found that the high temperatures employed and the absence of appreciable water vapor during the course of the reaction results in a product zeolite having some silicon inserted into the crystal lattice but having a relatively low cation equivalence value, indicative of conventional decationization as reported in U.S. Pat. No. 3,130,006, Rabo et al.
The third type of silicon insertion technique heretofore proposed is reported in U.S. Pat. No. 4,503,023. In that patent specification Breck and Skeels describe a process for dealuminizing a zeolite by treatment of the zeolite with a fluorosilicate salt in an amount of at least 0.0075 moles per 100 grams of the zeolite (on an anhydrous basis), the fluorosilicate salt being provided in the form of an aqueous solution having a pH in the range of 3 to about 7. The aqueous solution of the fluorosilicate salt is brought into contact with the zeolite at a rate sufficiently slow to preserve at least 80 percent, preferably at least 90 percent, of the crystallinity of the starting zeolite and silicon atoms, as SiO4 tetrahedra, are inserted into the crystal lattice in substitution for aluminum atoms. The fluorosilicate extracts aluminum from the zeolite lattice framework and substitutes silicon therein, thus increasing the SiO2 /Al2 O3 molar ratio of the zeolite without introducing large numbers of defect sites in the framework. The products of this process are referred to as LZ-210.
As already discussed, most of the prior art processes for the dealumination of zeolites introduce so many defects into the lattice framework that the thermal stability of the zeolite is adversely affected. It is known that dealumination alone, which creates unhealed defect sites, does not increase the stability of the zeolite. It is the lattice framework rearrangement caused by the thermal or hydrothermal treatment that causes the stability of the zeolite to increase, as framework aluminum is removed and silicon fills some of the defect sites produced during dealumination. In the other two prior known silicon insertion techniques, it is the insertion of extraneous silicon atoms, i.e., atoms not derived from the zeolite itself, which prevents the formation of permanent defect sites in the crystal lattice and stabilizes the crystal structure. The method used to produce the LZ-210 zeolites appears to be the most effective means for the production of a silicon-enriched framework and one that maintains the ion-exchange capacity of the zeolite. Accordingly, other methods which produce a silicon-enriched framework and also maintain the ion-exchange capacity of the zeolite are desirable. The present invention provides such a method, in which a zeolite is treated with an aqueous solution of a bifluoride salt of which the reactive moiety is presumably the bifluoride ion.
The prior art contains numerous processes involving the treatment of zeolites with various types of halogen-containing compounds, including simple fluorides. These processes are generally intended to provide residual fluoride in the zeolite.
Such processes are described in:
U.S. Pat. No. 3,594,331, in which 2 to 22 grams of available fluoride are provided per 10,000 grams of zeolite to stabilize the zeolite;
U.S. Pat. No. 3,620,960 (treatment of the zeolite with molybdenum fluoride);
U.S. Pat. No. 3,630,965 (treatment of the zeolite with hydrofluoric acid);
U.S. Pat. No. 3,644,220 (treatment of the zeolite with volatile halides selected from the group consisting of aluminum, zirconium, titanium, tin, molybdenum, tungsten, chromium, vanadium, antimony, bismuth, iron, platinum group metals and rare earths);
U.S. Pat. No. 3,575,887 and U.S. Pat. No. 3,702,312 (treatment of the zeolite with fluorides and chlorides);
U.S. Pat. No. 3,699,056 (treatment of the zeolite with halogenated hydrocarbons);
U.S. Pat. No. 4,427,788 (ammoniacal aluminum fluoride solution for treatment of zeolite having silica/alumina ratio greater than 100); and
U.S. Pat. No. 4,427,790 (complex fluoroanion treatment of zeolite having a silica/alumina ratio greater than 100).
A variation of such fluoride treatment for zeolites is disclosed in U.S. Pat. No. 3,619,412, which describes treatment of a mixture of mordenite and amorphous silica-alumina with a solution of a fluorine compound such as ammonium fluoride or hydrofluoric acid. The hydrofluoric acid treatment is said to provide stability to mordenite-containing catalysts.
Other processes involving treatments of zeolites having silica/alumina ratios greater than 100 are disclosed in U.S. Pat. No. Nos. 4,427,786; 4,427,787; 4,427,789 and 4,427,791. U.S. Pat. No. 4,427,786 discloses the treatment of supported zeolites with boron trifluoride, hydrolysis of the boron trifluoride, an ammonium salt exchange and calcination. A comparison of Examples 2 and 9 of U.S. P. 4,427,786 shows that the catalytic cracking activity of zeolites having a silica/alumina ratio of less than 70 showed a decrease as a result of this process. U.S. Pat. No. 4,427,787 discloses the treatment of an alumina-supported zeolite with a dilute aqueous solution of hydrogen fluoride; this treatment is claimed to preferentially increase the catalytic cracking activity of zeolites having silica/alumina ratios over 100. U.S. Pat. No. 4,427,789 discloses the treatment of an alumina-supported zeolite with an aqueous solution of an alkali metal fluoride, impregnation with a warm solution of an ammonium salt and calcination. U.S. Pat. No. 4,427,791 discloses a process for the treatment of an inorganic oxide material with ammonium fluoride or boron fluoride, ammonium ion exchange, and calcination. This treatment is claimed to enhance the activity of the inorganic oxide material as a result of the ammonium ion-exchange step.
U.S. Pat. No. 4,324,698 discloses a process for preparing a fluorided zeolite type cracking catalyst consisting essentially of at least 90 percent by weight of a composite of a Y-zeolite in a silica-alumina matrix and containing about 0.1 to about 5 percent by weight of fluorine. The catalyst is prepared by contacting the composite with an amount of aqueous fluorine compound just sufficient for incipient wetting of the composite. The composite is then dried and calcined. The catalyst necessarily contains high concentrations of fluoride.
This invention provides a process for increasing the framework Si/Al2 molar ratio and the thermal stability of a crystalline zeolite which comprises contacting said zeolite starting material with a solution or slurry comprising a bifluoride salt under conditions effective to cause removal of aluminum and silicon from the zeolite starting material and reinsertion of some of the removed silicon thereinto, thereby producing a zeolite having a crystal collapse temperature higher than that of the starting material. In general the process comprises contacting and reacting a zeolite starting material with an aqueous solution of a bifluoride salt in proportions such that there is from about 0.5 to 10 moles of bifluoride ion per mole of zeolitic framework aluminum, said contact between zeolite and bifluoride salt solution being carried out at a temperature of from about 60° C. to 100° C. and the starting pH of the bifluoride salt solution being not greater than 7, whereby framework silicon and aluminum atoms are removed from the zeolite and at least some of the removed silicon atoms are inserted into sites vacated by removed aluminum atoms and the product zeolite has a crystal collapse temperature higher than that of the starting zeolite.
The process of the present invention, unlike other and prior known silicon insertion processes using halogen-containing reagents, does not introduce extraneous silicon atoms into the zeolite framework, but rather, as in the case of hydrothermal (steaming) processes, utilizes silicon derived from the zeolite itself. In this aspect the process is highly surprising in that there is absent the means for silicon transport known to be provided by the steam environment in the conventional hydrothermal processes.
Although we do not want to be bound by any particular theory, it is believed that the bifluoride treatment causes extraction of both aluminum and silicon from the lattice framework of the zeolite starting material (the aluminum reacting with the H+ produced by the bifluoride ion, then being hydrolyzed and reacting with fluoride to form AlF3, which is thermodynamically favored, while the silicon in the zeolite framework is susceptible to attack by the hydrogen fluoride produced by the bifluoride ion, especially where the framework has been fragmented by aluminum removal), with subsequent redeposition of at least some of the silicon into some of the defects left where aluminum atoms were extracted. Thus, in contrast to the processes involving SiCl4 or fluorosilicate salts discussed above, in which the silicon is supplied by an external source, it appears that the process of the present invention achieves silicon resubstitution using the silicon dissolved from the zeolite itself, an "internal" silicon source. While the zeolite product of the present process has a somewhat higher defect structure factor than the starting zeolite, the change in the unit cell constant(s) of the zeolite product is measurably greater than would be the case if simple dealumination had occurred. Obviously and unexpectedly the removal and reinsertion of framework silicon is favorable to the thermal stability of the zeolite product.
It should be noted that the effects achieved by the process of the present invention are not achieved by similar processes using solutions or slurries of simple fluorides, such as sodium, potassium or ammonium fluoride. Although treatment of a zeolite with an aqueous solution or slurry of a simple fluoride can indeed result in extraction of aluminum from the zeolite, the treatment also results in much degradation of the zeolite, with production of amorphous material. In fact, it can be shown that, under certain conditions, ammonium Y zeolite will dissolve in ammonium fluoride solution. In addition, as discussed in more detail below with reference to the Examples, even under milder conditions, treatment of ammonium Y zeolite with ammonium fluoride causes much greater crystal degradation, and much greater increases in defects, than similar treatment with ammonium bifluoride. It appears that these differences between fluoride and bifluoride treatment may be due to the inability of simple fluorides to extract silicon from the zeolite lattice framework, or subtle differences in pH, so that there is no dissolved silicon available to repair some of the defects remaining after aluminum extraction.
The following Table is illustrative of the differences in pH between ammonium fluoride and ammonium bifluoride solutions:
______________________________________pH of a Typical Salt SolutionSalt: NH.sub.4 F NH.sub.4 HF.sub.2______________________________________10 wt. % Salt Solution 7.06 5.2720 wt. % Salt Solution 7.63 5.26______________________________________
It is well known that silicon species in solution will begin to polymerize at pH greater than about 7.0. While the exact mechanism of silicon substitution into the zeolite framework is not known, we believe that a monomeric silicon species in solution is required to fill a defect site. Thus, the data from the above Table indicate that a bifluoride salt would be more efficacious than the simple fluoride salt in maintaining a monomeric silicon species in solution to react with the vacant sites in the zeolite.
Furthermore, the effects of the treatment with bifluoride in the process of the present invention are not the same as treatment of the same zeolite starting materials with silicofluoride in the process of the aforementioned U.S. Pat. No. 4,503,023. Under similar reaction conditions and at the same fluoride concentration, the bifluoride treatment causes a smaller increase in the silica/alumina ratio of the starting material and a greater increase in the defect structure factor than does the silicofluoride treatment. The ion-exchange capacities of the stabilized zeolites of the present invention are comparable to those of LZ-210. The present stabilized zeolites preferably have a M+ /Al ratio of at least about 0.85, preferably in the range of 0.85 to 1.05. In the term M+ /Al, the M+ represents monovalent cation species and the Al represents the total aluminum content of the zeolite prior to any ion-exchange procedure using an aluminum salt. The products of the present invention can exhibit greater acidity than prior ar stabilized zeolites produced by thermal or hydrothermal treatment, and this greater acidity is useful in reactions which involve acid catalysis.
The zeolite starting material used in the process of the present invention may be any zeolite having a pore size sufficient to permit entry of the bifluoride ion into the zeolite; in practice, this means any zeolite having a pore size in excess of about 3 A. Thus, the zeolites conventionally used in cracking catalysts can all be subjected to the process of the present invention, since such zeolites need to have a pore size in excess of about 3 A to admit the hydrocarbon components to be cracked. In addition, since the process of the present invention depends upon acid attack upon the zeolite starting material, the starting material should not be one which undergoes excessive degradation of its crystal structure on contact with acid. The suitability of any specific zeolite for use in the present process may easily be determined empirically. The zeolite starting material may be, for example, zeolite Y, zeolite X, mordenite, erionite, chabazite, zeolite N-A (U.S. Pat. No. 3,306,922) zeolite beta (U.S. Pat. No. 3,308,069), zeolite ZK-20, zeolite ZSM-3 (U.S. Pat. No. 3,415,736), ZSM-5, ZSM-11, ZSM-12, ZSM-20 and ZSM-21, FU-1-type zeolites, and mixtures thereof. Because of its high and well-understood activity as a cracking catalyst, the preferred zeolite starting material is zeolite Y.
As is the case with zeolites in general, the thermal stability of the product of the present invention tends to increase with its silica/alumina ratio, and thus a fairly high silica/alumina ratio is desirable in the product. On the other hand, since the present process does produce some increase in the defect structure factor in the product, problems may be encountered if the present process removes a very high proportion of the aluminum in the zeolite starting material. Thus, to avoid any risk of such problems, it is normally desirable to use a starting material with a relatively high silica/alumina ratio. Thus, for example, in the case of the preferred Y zeolites, it is desirable to use a starting material having a silica/alumina ratio in the range of about 3.5 to about 5.5.
Y zeolites having silica/alumina ratios of greater than about 3.5 are disclosed in U.S.p 3,130,007. Examples of Y zeolites believed employable in the present process are those disclosed in U.S. Pat. No. Nos.: 3,835,032; 3,830,725; 3,293,192; 3,449,070; 3,839,539; 3,867,310; 3,929,620; 3,929,621; 3,933,983; 4,058,484; 4,085,069; 4,175,059; 4,192,778; 3,676,368; 3,595,611; 3,594,331; 3,536,521; 3,293,192; 3,966,643, 3,966,882; and 3,957,623. The aforementioned patents are merely representative of Y zeolites having silica/alumina ratios greater than about 3.5 and are not intended to be a complete listing of the Y zeolites employable herein.
As already noted, the degree of increase in thermal stability of the zeolite starting material produced by the process of the present invention (as indicated, for example, by the increased crystal collapse temperature measured by the differential thermal analysis method (see T. C. Daniels, Thermal Analysis, Wiley, New York (1973), pages 73-135) is highly correlated with the increase in silica/alumina ratio produced by the process. To produce significant increases in stability of a Y zeolite starting material, it is desirable to carry out the process so as to produce a product with a silica/alumina ratio of 6.0 or more, the increase in silica/alumina ratio essentially being limited by the maximum defects which can be tolerated in the product.
The zeolite starting material may be in any chemical form which permits it to react properly with the bifluoride salt solution or slurry. However, it is preferred that the starting material be in its ammonium form, since this form not only permits ready reaction with the bifluoride solution or slurry, but also leaves the product in its ammonium form, which can readily be converted by heating to its acid form, this acid form being the form which is active in the catalytic cracking process. As is well known to those skilled in molecular sieve technology, the ammonium form of a zeolite is readily prepared from the as-synthesized form of the zeolite (which contains the alkali metal or organic templating agent used in the synthesis of the zeolite) by ion-exchange with a solution of an ammonium salt.
Because it is desirable that the product of the process of the present invention be produced in its ammonium form, the preferred bifluoride salt for use in the process is ammonium bifluoride. However, other soluble bifluorides, for example sodium bifluoride and potassium bifluoride, may alternatively be used if desired. For economy and convenience, the solution or slurry of the bifluoride will normally be an aqueous solution or slurry, but we do not exclude the possibility of using non-aqueous solutions and slurries in other solvents, provided such other solvents permit the formation of bifluoride ion and the development of sufficient acidity for the process to operate in the same way as in aqueous media.
The optimum concentration of bifluoride ion in the solution or slurry used to treat the zeolite starting material varies with a large number of factors, including the specific zeolite being treated, the reaction conditions and the change desired in the silica/alumina ratio of the zeolite. Solutions having bifluoride salt concentrations of from about 10-3 moles per liter of solution up to saturation can generally be employed in the process. However, in general it is preferred that the solution or slurry contain from about 0.5 to about 10, and desirably from about 0.8 to about 10, moles per liter of bifluoride. In the case of slurries, of course, the relevant concentration of bifluoride is that of dissolved bifluoride, since any solid bifluoride suspended in the slurry has no effect until it becomes dissolved. Even very slightly soluble bifluoride salts can be slurried in a solvent, e.g., water, and used as a reagent, with the undissolved solids being readily available to replace dissolved molecular species consumed in treatment of the zeolite.
Similarly, the temperature at which the process of the present invention should be carried out varies with a large number of factors, including the specific zeolite being treated and the change desired in the silica/alumina ratio of the zeolite. Increasing the reaction temperature usually increases the reaction rate, but also tends to increase degradation of the crystal structure; as is well known to those skilled in molecular sieve technology, degradation of the crystal structure is highly undesirable, because the catalytic activity of the molecular sieve depends upon the maintenance of the microporous structure. Accordingly, the reaction temperature should be controlled to limit crystal structure degradation, and retain as high a proportion as possible of the crystallinity of the zeolite starting material. In general, it is preferred to carry out the process of the present invention at a temperature in the range of about 60° C. to about 100° C. Furthermore, it is preferred to carry out the reaction so that at least about 66, and desirably about 75, percent of the crystallinity of the zeolite starting material is retained.
Although various techniques for measuring crystallinity of zeolites are well known in the art, all references herein to numerical ratios of crystallinity are to X-ray crystallinities. Such crystallinities are calculated by comparison of the total areas under all the peaks in the X-ray powder diffraction pattern of the product of the process of the present invention with that of the zeolite starting material. The sum of the areas, in terms of arbitrary units above background, of the starting material is used as the standard and is compared with the corresponding sum of the areas in the product. When, for example, the numerical sum of the areas of the product is 85 percent of the value of the sum of the areas of the starting zeolite, then 85 percent of the crystallinity has been retained. Although there are other indicia of the crystallinity retained by the product (for example, X-ray crystallinities calculated using a) the sum of the peak heights; b) the sum of only a portion of the peak heights, as for example, five of the six strongest d-spacings, which in the case of zeolite Y correspond to the Miller Indices 331, 440, 533, 642 and 555; c) the degree of retention of surface area as measured by the well-known Brunauer-Emmet-Teller method (B-E-T). J. Am. Chem. Soc., 60.309 (1938) using nitrogen as the adsorbate; or d) the capacity for oxygen adsorption at -183° C. at 100 Torr, give similar results), as already noted, it is the comparison of total areas under the X-ray peaks which is relied upon herein.
The X-ray patterns required for calculation of X-ray crystallinities may be obtained by standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 K.sub.α and 40 ma. The diffraction pattern from the copper K.sub.α radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. X-ray patterns are obtained using flat compressed powder samples which are scanned at 2° (2Θ) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2Θ where Θ is the Bragg angle as observed on the strip chart. Areas under the diffraction peaks (after subtracting background) are obtained by standard integration techniques which will be familiar to those skilled in X-ray crystallography. Alternatively, the X-ray patterns may be obtained by use of computer based techniques using Siemens D-500 X-ray powder diffractometers with copper K.sub.α radiation and Siemens type K-805 X-ray sources, such being available from Siemens Corporation, Cherry Hill, N.J.
Since the process of the present invention involves acid attack upon aluminum and silicon in the lattice framework of the zeolite starting material, the reaction rate is pH-dependent. The reaction appears to require the dissolution of sufficient silicon to enable placement of silicon atoms in at least a large proportion of the defects created by removal of aluminum from the lattice framework. Thus, if the reaction is conducted at too high a pH little silicon will be dissolved and sufficient silicon will not be available for placement in the lattice framework, so that the product will suffer from an excess of defects. Accordingly, it is preferred that the process of the present invention be carried out at a pH not greater than about 7. Very low pH values may, however, cause too rapid a reaction between the bifluoride and the aluminum in the zeolite, with consequent excessive degradation of the crystal structure, and should hence be avoided. In general, the use of bifluoride solutions having pH values below about 3 is not recommended. The usable pH range is also limited by the acid stability of the zeolite.
It has been found that the degree of crystal degradation occurring during the process of the present invention is significantly affected by the technique used to contact the zeolite starting material with the bifluoride solution. Prolonged contact of any portion of the starting material with a solution or slurry containing a high concentration of dissolved bifluoride tends to cause excessive crystal structure degradation in that portion of the starting material, and hence should be avoided. Accordingly, it may be desirable to carry out the process by adding the bifluoride solution or slurry slowly to a mass of the zeolite starting material, with constant stirring or other form of agitation to ensure that no portion of the starting material undergoes prolonged exposure to unchanged solution or slurry.
It is readily accomplished to carry out the present process by controlling the various process parameters so that the product zeolite has a silica/alumina ratio greater than about 6.0, a defect structure factor of not more than about 0.08, and a M+ /Al ratio of at least about 0.85. Typically, the stabilized zeolite produced by the present process will have a crystal collapse temperature at least about 25 C higher than those of the zeolite starting material. The determination of the defect structure factor is made according to the procedure set forth in U.S. Pat. No. 4,503,023, issued Mar. 5, 1985, the disclosure of which is incorporated herein by reference.
The following examples were carried out to demonstrate the process of the present invention, but are given solely by way of illustrating the invention and are not intended to be limitative of the invention.
Samples of NH4 - exchanged Y zeolite having a silica/alumina ratio of 5.08 and a cation equivalent M+ /Al of 0.95 were treated with varying quantities of aqueous slurries of ammonium bifluoride, as set forth in Table 1 below. The zeolite samples were each placed in a separate vessel, and the ammonium bifluoride slurry added slowly over a period of 90 minutes, with the vessel and the slurry being maintained at 75° C. throughout this period. After the addition of the ammonium bifluoride slurry had been completed, the resultant mixture was maintained at 75° C. for a further 3 hours, after which the solid zeolite product was separated by filtration, washed with water and dried in air at room temperature.
Table 1 gives details of the proportions of the reactants employed in the production of the stabilized zeolites, while Table 2 gives details of the properties of the stabilized zeolites themselves. In Table 2, there are given the X-ray crystallinity (calculated as described above), the unit cell dimension, the infra-red asymmetric and symmetric stretching frequencies, the absolute absorbance at 3710 cm-1 and the crystal collapse temperature (determined as per the Daniels book mentioned above, at a temperature increase of 20° C. per minute). The respective products were tested in n-butane cracking and their activity values (kA) compared in Table 2 with those of the starting zeolite, following procedures established by Rastelli et al as published in the "Canadian Journal of Chemical Engineering"; 60, 44-49; 1982. Also given in Table 2 are the defect structure factors, z, for the various products.
The asymmetric stretching frequencies given in Table 2 are, as is well-known to those skilled in the zeolite art, related to the silica/alumina ratio of the product, the asymmetric stretching frequency increasing with the silica/alumina ratio. Thus, these asymmetric stretching frequencies are a measure of the degree of dealumination of the zeolite framework effected by the process of the present invention. The silica/alumina ratios given in Table 2 were obtained by chemical analysis. From the data in Table 2, it will be seen that, with increasing amounts of bifluoride treatment, the chemically-measured silica/alumina ratio increases, as does the asymmetric stretching band frequency.
The symmetric stretching frequencies given in Table 2 are, as is well-known to those skilled in the zeolite art, related to whether silicon resubstitution takes place. It is known that simple dealumination of a zeolite produces little or no change in the symmetric stretching frequency. If, however, substitution of silicon into vacancies in the lattice framework occurs, the unit cell dimension decreases and the symmetric stretching band frequency increases. From the data in Table 2, it will be seen that, with increasing amounts of bifluoride treatment, the chemically-measured silica/alumina ratio increases (as already mentioned), and the symmetric stretching band frequency increases with the resultant increase in silica/alumina ratio.
The unit cell dimensions given in Table 2 (which were taken on fully-hydrated specimens of the zeolites) are a further measure of the extent to which resubstitution of silicon into the framework occurs during the process of the present invention. It is known that the unit cell dimension of a fully-hydrated zeolite is related to its silica/alumina ratio, the unit cell dimension decreasing with increasing silica/alumina ratio. However, simple dealumination of a zeolite produces little or no change in the unit cell dimension, whereas a framework into which silica has been resubstituted does undergo a decrease in unit cell dimension. It should be noted that the unit cell dimension is related to framework silica/alumina ratio, and unlike chemical analysis is little affected by aluminum which may be present in non-framework forms (such as within the pores of the framework).
An increase in catalytic activity (with increasing SiO2 /Al2 O3 as measured by the activity values obtained from the n-butane cracking test is expected. Increased activity is typical of zeolites with increased stability due to a higher SiO2 Al2 O3 in the framework and maintenance of acid (NH4 +) ion exchange capacity as measured by the cation ratio to aluminum M+ /Al.
TABLE 1______________________________________ Example No 1 2 3 4 5 6______________________________________Zeolite (gm.) 493 493 500 100 100 100Zeolite conc., 16.7 16.7 16.6 16.6 16.6 16.6(wt. percent)NH.sub.4 HF.sub.2 52.8 69.3 119.3 40.8 51.6 59.1(gm.)NH.sub.4 HF.sub.2 10.0 12.2 16.6 20 20 20(wt. percent)NH.sub.4 HF.sub.2 0.926 1.215 2.092 0.715 0.905 1.036(moles)Aluminum in 2.106 2.106 2.136 0.427 0.427 0.427zeolite(moles)F/Al (atomic 0.879 1.157 1.958 3.345 4.235 4.851ratio)Slurry pH -- -- 7 7 7 7(after diges-tion)______________________________________
TABLE 2__________________________________________________________________________ Example No. Starting NH.sub.4 -Y 1 2 3 4 5 6 zeolite__________________________________________________________________________Chemical analysis;(wt. percent or molar ratio)Na.sub.2 O 2.5 2.2 2.0 1.6 1.3 1.0 2.3(NH.sub.4).sub.2 O 8.9 7.9 7.0 6.9 5.9 5.4 9.9Al.sub.2 O.sub.3 22.5 19.8 18.2 17.8 14.5 12.9 21.9SiO.sub.2 74.4 69.5 70.8 81.6 76.9 79.2 65.2F.sub.2 0.21 0.02 0.02 0.03 .11 0.10 0.0Na.sup.+ /Al 0.18 0.18 0.18 0.15 0.14 0.13 0.18NH.sub.4.sup.+ /Al 0.77 0.78 0.75 0.76 0.80 0.82 0.89M.sup.+ /Al 0.95 0.96 0.93 0.91 0.94 0.95 1.07SiO.sub.2 /Al.sub.2 O.sub.3 5.61 5.97 6.60 7.79 9.00 10.38 5.08X-ray analysisCrystallinity (%) 106 104 96 97 82 75 100Unit cell (A) 24.674 24.660 24.622 24.570 24.540 24.510 24.714Infra-red analysisAsym. str. (cm.sup.-1) 1026 1027 1033 1041 1049 1053 1019Sym. str. (cm.sup. -1) 790 790 795 802 807 810 787Abs. absorbance 0.062 0.062 0.073 0.146 0.145 0.179 0.050at 3710 cm.sup.-1Defect Structure 0.026 0.026 0.031 0.062 0.062 0.076 0.021Factor (z)Crystal collapse 917 920 968 1016 1052 1076 878temperature (°C.)n-butane cracking, -- -- 1.5 4.5 4.5 4.7 1.7(rate constant k.sub.A.__________________________________________________________________________
The data given in Tables 1 and 2 fully support the statements made earlier in this application regarding the advantageous results achieved by the process of the present invention, and the mechanism by which the reaction between the zeolite and the bifluoride is believed to occur.
It will be seen from the data in Tables 1 and 2 that the process of the present invention produces very significant increases in the silica/alumina ratio of the zeolite starting material, although this increase in the silica/alumina ratio is less than that achieved by the use of the same fluorine/aluminum ratio in the Breck and Skeels process. Although the process of the present invention does cause some increase in the defect structure factor of the zeolite starting material, calculation shows that this increase in the defect structure factor is much lower than would be expected if the increase in silica/alumina ratio of the zeolite were solely due to simple dealumination, i.e., simple removal of aluminum from the zeolite without any resubstitution of silicon into the defect sites left behind where the aluminum has been extracted.
The unit cell dimensions and the symmetric stretching frequencies given in Table 2 also confirm that silicon resubstitution occurs during the process of the present invention. As previously noted, simple dealumination does not produce large changes in the unit cell dimension, whereas the significant decreases in unit cell dimension and the significant increases in symmetric stretching frequency achieved in the foregoing Examples are entirely consistent with silicon resubstitution into defects produced by dealumination of the zeolite. Moreover, without silicon resubstitution, it is difficult to explain the large increases in crystal collapse temperatures, since simple dealumination would be expected to produce decreases in the crystal collapse temperature.
Accordingly, it will be seen from the data in Table 2 that the process of the present invention can achieve large increases in the silica/alumina ratio of a zeolite without excessive increases in the defect structure factor and while still leaving the zeolite with a substantial ion-exchange capacity (as shown by the M+ /Al ratios in Table 2). Maintenance of the ion-exchange capacity utilizes all of the potential acidity in the zeolite resulting in greater catalytic activity. Furthermore, the process of the present invention has been shown to produce major increases in the crystal collapse temperature of the zeolite; such an increase in the crystal collapse temperature is commercially useful since it permits the zeolite to be used in reactions occurring at higher reaction temperatures.
To show that the advantageous results obtained by the process of the present invention, as illustrated in Examples 1-6, are not obtained by treatment of the zeolite with solutions of simple fluorides, the same Y zeolite as in Examples 1-6 was fluoride-treated in the same manner as in those Examples, but using solutions containing various amounts of ammonium fluoride rather than ammonium bifluoride. The results are given in Tables 3 and 4 below, which set forth exactly the same parameters as Tables 1 and 2 respectively. For convenience, the values for the starting zeolite given in Table 2 above are repeated in Table 4 below.
TABLE 3______________________________________ Example No. 7 8 9 10______________________________________Zeolite (gm.) 500 500 739 739Zeolite conc. 16.6 16.6 20.2 24.0(wt. percent)NH.sub.4 F (gm.) 54.56 154.6 390.4 495.4NH.sub.4 F 15.4 17 44 50(wt. percent)NH.sub.4 F (moles) 1.473 4.174 10.539 13.376Aluminum in zeolite 2.136 2.136 3.157 3.157(moles)F/Al (atomic ratio) 0.690 1.954 3.338 4.237______________________________________
TABLE 4______________________________________ Example No. Starting NH.sub.4 -Y 7 8 9 10 Zeolite______________________________________Chemical analysis (wt. percent or molar ratio)Na.sub.2 O 2.4 2.2 2.0 1.5 2.3(NH.sub.4).sub.2 O 8.7 7.6 8.0 6.6 9.9Al.sub.2 O.sub.3 21.4 20.0 17.9 15.2 21.9SiO.sub.2 67.5 69.2 71.4 75.7 65.2F.sub.2 0.01 0.09 1.80 0.26 0.0Na.sup.+ /Al 0.19 0.18 0.18 0.16 0.18NH.sub.4 /Al 0.79 0.75 0.87 0.85 0.89M.sup.+ /Al 0.98 0.93 1.05 1.01 1.07SiO.sub.2 /Al.sub.2 O.sub.3 5.34 5.87 6.78 8.43 5.08X-ray analysisCrystallinity (%) 106 80 68 68 100Unit cell (A) 24.695 24.680 24.684 24.661 24.714Infra-red analysisAsym. stretch 1023 1026 1030 1036 1019(cm.sup.-1)Sym. stretch (cm.sup.-1) 788 789 780 790 787Absolute 0.062 0.059 0.101 0.312 0.050absorbanceat 3710 cm.sup.-1Defect Structure 0.026 0.025 0.043 0.132 0.021Factor (z)Crystal collapse 877 909 810 940 878temperature (°C.)______________________________________
It will be seen, by comparing Tables 3 and 4 with Tables 1 and 2, that the advantages achieved using the bifluoride treatment process of the present invention are not achieved by similar processes using simple fluorides. The increase in silica/alumina ratio effected with the simple fluoride was somewhat less than with bifluoride; for example, whereas the product of Example 5 had a silica/alumina ratio of 9.00, the corresponding product produced with the simple fluoride in Example 9 had a silica/alumina ratio of 8.43. More significantly, the product of Example 9 showed much greater crystal degradation, having an X-ray crystallinity of only 68 percent, as opposed to the 82 percent achieved in Example 5. In addition, the product of Example 9 had a much greater defect structure factor, 0.132, as opposed to the factor of 0.062 found in Example 5. Finally, the product of Example 9 showed a lower asymmetric stretching frequency (1036 cm-1 versus 1049 cm- 1 in Example 5), a lower symmetric stretching frequency (790 cm-1 versus 807 cm-1 in Example 5), a larger unit cell dimension (24.661 A versus 24.540 in Example 5), and a much lower crystal collapse temperature (940° C. versus 1076° C. in Example 5).
The results obtained in the experiments using ammonium fluoride are entirely consistent with the view that the simple fluoride causes a dealumination of the zeolite, but does not cause dissolution of silicon therefrom, and thus is unable to effect resubstitution of silicon into the defects caused by the removal of aluminum atoms. Thus, unlike bifluoride, simple fluorides cause greater degradation of the crystal structure and leave a product with a high defect structure and a relatively low crystal collapse temperature. Such products obtained by simple fluoride are ill-adapted for use in cracking and hydrocracking catalysts.
To illustrate the differences between the stabilized zeolites produced by the process of the present invention, samples of an NaY zeolite similar to that used in Example 1 were treated by various prior art stabilization processes, namely:
Example 11: Ultrastable Y zeolite (see U.S. Pat. No. 3,449,070);
Example 12: EDTA-extracted Y zeolite (see Kerr, J. Phys. Chem., 72: 2594 1968);
Example 13: Acetylacetone-treated Y (see U.S. Pat. No. 3,640,681); and
Example 14: LZ-210, prepared as described above.
Table 5 below shows most of the same parameters of the resultant products as in Tables 2 and 4 above; apart from Example 11, which cannot be raised to a silica/alumina ratio of 9, the treatment conditions in each case were chosen to produce a product with a silica/alumina ratio of approximately 9.
For comparison, Table 5 includes data from Example 5, as well as data for a bifluoride treated NH4 Y, the NaY zeolite starting material and for the ammonium-exchanged form of this zeolite.
TABLE 5__________________________________________________________________________ Example No. 11 12 13 14 NaY NH4Y 5 U.S.-Y EDTA Y AcAc Y LZ-210__________________________________________________________________________SiO.sub.2 Al.sub.2 O.sub.3 4.84 4.88 9.00 5.15 9.50 8.59 9.50M.sup.+ /Al 1.0 0.98 0.94 0.01 1.0 0.85 0.99X-ray analysisCrystallinity (%) 100 100 82 07 68 62 99Unit cell (A) 24.689 24.677 24.540 24.282 24.652 24.58 24.52Infra-red analysisAsym. str. (cm.sup.-1) 1018 1014 1049 1080 1033 1037 1046Sym. str. (cm.sup.-1) 791 786 807 837 794 792 812Abs. Absorbance 0.000 0.007 0.145 0.150 0.330 0.446 0.045at 3710 cm.sup.-1Defect Str. 0.000 0.003 0.062 0.064 0.140 0.189 0.019Factor (z)Crystal collapse 940 875 1052 1004 980 996 1061Temperature, (°C.)__________________________________________________________________________
From the data in Table 5, it will be seen that only LZ-210 has parameter values similar to those of the product of Example 5. Except for LZ-210, the other prior art products have much lower crystal collapse temperatures, and (except for ultrastable Y), lower symmetric stretching frequencies and higher defect structure factors. Ultrastable Y, which has all the properties indicative of a framework rich in SiO2, has an extremely low cation equivalent, which would make this material substantially less acidic in a catalytic environment.
The data in Table 5 are consistent with the view that only the LZ-210 process and the process of the present invention achieve silicon substitution into the lattice framework while maintaining cation exchange capacity, whereas the processes used to produce ultrastable Y, EDTA Y and AcAc Y do not.
The zeolite products of the present process, particularly those resulting from the use of zeolite Y as the starting material are useful in the same manner as zeolite compositions generally. They are useful as hydrocarbon conversion catalysts or catalyst bases, particularly in cracking and hydrocracking reactions.
Catalytic cracking and hydrocracking with the catalysts of the present invention can be conducted in any conventional manner. Suitable catalytic cracking conditions include a temperature ranging from about 400° F. to about 1300° F. and a pressure ranging from about subatmospheric to several atmospheres, typically from about atmospheric to about 100 psig. The process may be carried out in a fixed bed, moving bed, ebullating bed, slurry, transferline, riser reactor or fluidized bed operation. The catalyst of the present invention can be used to convert any of the conventional hydrocarbon feeds used in catalytic cracking, that is, it can be used to crack naphthas, gas oil and residual oils having a high content of metal contaminants. Because of its high thermal stability, it is especially suited for cracking hydrocarbons boiling in the gas oil range, i.e., hydrocarbon oils having an atmospheric pressure boiling point ranging from about 420° to about 1100° F. to naphthas, to yield products having a lower boiling point than the initial feed.
In the hydrocracking catalysts, the stabilized zeolites will typically be employed in conjunction with a hydrogenation component of the type which are commonly employed in hydrocracking catalysts. The hydrogenation component is generally selected from the group of hydrogenation catalysts consisting of one or more metals of Group VIB and Group VIII, including the salts, complexes and solutions containing such. The preferred hydrogenation catalyst is selected from the groups of Group VIII metals, these salts and complexes thereof and is most preferably selected as a salt or complex of at least one noble metal of platinum, palladium, rhodium, iridium and mixtures thereof, and/or at least one base metal of nickel, molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof. As recognized in the art, the noble and base metals will not generally be employed in the same catalyst system; in particular, in the preferred high activity, high octane variant of the present invention, the hydrogenation component desirably comprises one or more base metals. The hydrogenation component is present in an effective amount to provide the hydrogenation function of the hydrocracking catalyst and for noble metals is generally present in an amount between about 0.05% and about 1.5% by weight based on the total weight of the hydrocracking catalyst including the weight of any binder or matrix material which may be present, as hereinafter discussed, although effective amounts outside this range may be employed. Although effective amounts in excess of 1.5 percent by weight may be employed, the preferred effective amount of hydrogenation component is between about 0.3% and about 1.2% by weight. When the hydrogenation catalyst is a base metal(s) the effective amount will generally be between about 5% and about 30% percent by weight or more of the base metal oxide(s) based on the total weight of the hydrocracking catalyst.
The conditions used in the hydrocracking process of the present invention are substantially similar to those used in prior art hydrocracking processes, which are well known to those skilled in the petroleum refining art. The hydrocarbon feedstock to be charged to the hydrocracking unit typically boils above about 300° F. (410° C.), preferably between about 350° and 1200° F. (between about 177° and about 649° C.) and more preferably between about 420° and about 900° F. (between about 216° and about 482° C.). The hydrocarbon feedstock may be derived from many sources including catalytic cracking processes, coking processes, fractionators from crude oil, hydroprocessing, pyrolysis processes and others. When operating a hydrocracking process to maximize gasoline production, the typical feedstock currently in commercial use has an end boiling point not greater than about 800° F. (427° C.). Typically, a light catalytic cycle oil, or a light virgin gas oil, or mixtures thereof, boiling in the range of from about 300. to 800° F. (149° to 427° C.) is employed as the feedstock. The feedstock may be pre-treated in a hydrotreater to reduce the content of organic compounds which contain sulfur and/or nitrogen. The feedstock may have a significant sulfur content, present as hydrogen sulfide, ranging from 0.1 to 3 weight percent, and nitrogen content, present as ammonia, in an amount up to 4000 parts per million, or even more. Temperature, space velocity, and other process variables may be adjusted to compensate for the effects of nitrogen on the hydrocracking catalyst activity.
The feedstock is contacted in the hydrocracking reaction zone with the hydrocracking catalyst in the presence of hydrogen-containing gas. Hydrogen is consumed in the hydrocracking process and an excess of hydrogen is typically maintained in the reaction zone. Advantageously, a hydrogen-to-oil (feedstock) ratio of at least 1,000 standard cubic feet per barrel of feed (SCFB) (28.3 standard m3 per barrel) is employed.
The hydrocracking reaction zone is typically operated under conditions of elevated temperature and pressure. The total hydrocracking pressure usually is between about 400 and about 4,000 pounds per square inch gauge (psig.) (between about 2.76 and about 27.6 MPa.), and preferably between about 500 and 2000 psig. (between about 3.45 and 13.8 MPa.). The hydrocracking reaction is exothermic and a temperature rise occurs across the catalyst bed. Therefore, the inlet temperature to the hydrocracking reaction zone may be 10° to 40° F. (5.6. to 22.2° C.) lower than the exit temperature. The average hydrocracking catalyst bed temperature is usually between about 450° and 800° F. (between about 232° and 427° C.), depending upon the presence or absence of ammonia and the age of the catalyst; however, in view of the fact that the preferred catalysts of the present invention possess significantly greater activity than catalysts of the prior art, in some cases it may be possible to reduce the hydrocracking catalyst bed temperature by an amount commensurate with the increased activity of the catalysts of the invention. The liquid hourly space velocity (LHSV) typically is between 0.2 and 5 volumes of feedstock per hour per volume of catalyst, and preferably between 0.25 and 4.
Our copending application, Serial No. 408,579, filed Sept. 18, 1989, now abandoned, discloses additional details concerning the use of the products of the present invention in cracking and hydrocracking. The disclosure of that application is incorporated herein in its entirely by reference.
|Zitiertes Patent
|10. Juni 1940
|12. Okt. 1943
|Velsicol Corp
|Catalytic material
|30. März 1966
|3. Febr. 1970
|Mobil Oil Corp
|Hydrothermally stable catalysts of high activity and methods for their preparation
|27. Febr. 1969
|20. Juli 1971
|Grace W R & Co
|Method of increasing the thermal stability of crystalline zeolites
|12. Nov. 1973
|20. Jan. 1976
|W. R. Grace & Co.
|Method of increasing the thermal stability of crystalline zeolites
|26. März 1985
|24. Juni 1986
|Mobil Oil Corporation
|Activation of zeolites
|14. Okt. 1988
|24. Juli 1990
|Mobil Oil Corporation
|Activation of zeolites
|Zitiert von Patent
|21. Dez. 1992
|16. Nov. 1993
|Insertion of silicon into the crystal framework of a zeolite
|1. Juni 1994
|14. Febr. 1995
|Catalysts & Chemicals Industries Co., Ltd.
|Modified crystalline aluminosilicate zeolites and process for their preparation
|19. Aug. 1997
|3. Aug. 1999
|Exxon Chemical Patents, Inc.
|Fluorination of synthesized molecular sieve catalysts for increased selectivity to ethylene during conversion of oxygenates to olefins
|10. Febr. 1999
|6. Febr. 2001
|Concordia University
|Thermally stable modified ZSM-5 zeolite materials with micro porosities and method of making same
|30. Dez. 1998
|26. März 2002
|Mobil Oil Corporation
|Noble metal containing low acidic hydrocracking catalysts
|3. Juni 2010
|28. Juni 2012
|University Of Manchester
|Modified Zeolites and their Use in the Recycling of Plactics Waste
|8. Juli 2015
|14. Jan. 2016
|Centre National De La Recherche Scientifique
|Method for the preparation of synthetic crystalline zeolite materials with enhanced pore volume
|9. Juli 2014
|14. Jan. 2016
|Centre National De La Recherche Scientifique
|Method for the preparation of synthetic crystalline zeolite materials with enhanced total pore volume
|Internationale Klassifikation
|Europäische Klassifikation
|3. Okt. 1991
Owner name: UOP,, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SKEELS, GARY W.;CHAPMAN-SNYDER, DIANE M.;FLANIGEN, EDITH M.;REEL/FRAME:005861/0493
Effective date: 19901210
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Owner name: UOP, ILLINOIS
Free format text: RE-RECORD TO CORRECT AN ASSIGNMENT PREVIOUSLY RECORDED ON REEL 6487, FRAME 413.;ASSIGNOR:SKEELS, GARY W.;REEL/FRAME:006668/0665
Effective date: 19921218
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text:
Press Release: IMF Approves Emergency Assistance for Honduras
December 7, 1998
The International Monetary Fund (IMF) today approved Honduras' request for emergency financial assistance related to natural disasters. The assistance, equivalent to SDR 47.5 million (about US$66 million), will support the government's economic recovery program and associated relief and rehabilitation efforts in the aftermath of Hurricane Mitch.
On the eve of Hurricane Mitch, prospects for the Honduran economy were good, based on progress over the past two years in achieving faster real GDP growth, lowering inflation, and reducing fiscal imbalances. Private sector confidence was on the upswing based on these achievements, on advances in the area of privatization and reforms in the tax system and the financial sector. Also contributing to the upswing were indications that the government was close to agreeing on a new program of stabilization and broad-based reforms supported under the Enhanced Structural Adjustment Facility (ESAF)1 that would also facilitate additional concessional loans from the World Bank and the Inter American Development Bank (IADB), and normalize relations with creditors.
The devastation caused by the hurricane has been unprecedented in terms of losses of life, personal property, infrastructure, and the economy. Current estimates indicate that the number of deaths was close to 5,500, about 8,000 people were missing, nearly 2 million people were displaced, and several towns and villages had been destroyed. Also, several roads and bridges were made impassable, most schools, and several hospitals and administrative centers were closed, and basic public services have been devastated. First approximations by the authorities indicate losses of inventories and fixed assets--including infrastructure--amounting to about 40 percent of GDP. Real GDP is estimated to fall to 3 percent in 1998 and turn negative in 1999, compared with pre-hurricane projections of real GDP growth of about 5-6 percent a year.
The authorities' prompt response to the crisis has focused on addressing--with substantial help from the international community--the immediate priorities of providing food, shelter, and health care to the homeless and displaced persons; taking measures to preserve public health; repairing essential infrastructure and beginning clean-up and reconstruction work. At the same time, the authorities are beginning to adopt measures aimed at limiting the effects of the disaster on inflation and interest rates, and setting the stage for economic recovery. A revised central government budget for 1999 is being formulated to take account of the changed outlook for government revenue and the new spending requirements, while every effort will be made to limit domestic financing in part by reallocating spending to emergency needs.
As soon as the immediate priorities have been addressed, the authorities are determined to resume discussions aimed at finalizing an economic program that could be supported under the ESAF and that is focused on the consolidation of macroeconomic stability, on increasing prospects for private investment, and on deepening structural reforms to address constraints to growth.
Honduras joined the IMF on December 27, 1945, and its quota2 is SDR 95.0 million (about US$133 million). Honduras' outstanding use of IMF financing currently totals SDR 33 million (about US$45 million).
1 The ESAF is a concessional IMF facility for assisting eligible members that are undertaking economic reform programs to strengthen their balance of payments and improve their growth prospects. ESAF loans carry an interest rate of 0.5 percent a year and are repayable over 10 years with a 5½-year grace period.
2 A member's quota in the IMF determines, in particular, the amount of its subscription, its voting weight, its access to IMF financing, and its share in the allocation of SDRs.
|Public Affairs
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text:
Mentor's Role
MSRI takes the mentoring of Postdocs very seriously. Mentors and Postdocs are paired at the beginning of each semester, and mentors are urged to meet regularly with their partners. We distribute the following suggestions for topics of discussion to both parties, and monitor the progress of the relationship to help ensure that each postdoc receives the level of mentoring he or she desires and needs.
Establishing a research plan:
- Designated weekly meeting
- A discussion at the beginning of the semester about the project(s) the PdF is pursuing and ideas about how to choose projects
- Introductions to senior researchers in the PdF's area
- Advice on how to write a paper well (point to literature on this subject); give feedback on paper drafts
- Advice about publication (e.g. how quickly to publish a thesis, choosing and dealing with journals, etc.)
- NSF grant proposal writing; feedback on proposal drafts, from beginning to submission
Planning for professional development:
- Advice on writing a CV and a research and teaching statements
- Advice on preparing for interviews
- Advice on how to give a good talk
- Have the PdF give a colloquium talk and critique the talk afterward; also advise on giving talks at national meetings, etc.
- Discussion on how to address the various aspects of an academic career (proportion of research/teaching/service at various stage of one's career; etc.)
We will ask for a quarterly report from mentor and PdF on their experience and progress. The report will need to address the above points.
In addition to individual mentoring that each PdF will recieve at his or her institution, there will be a 3-day workshop at AIM.
The 3-day, June 20-22, workshop "Careers in Academia"
will focus on preparing each participant for a successful career
as a mathematician at a college or university.
Applications are open to postdocs who currently hold an
appointment which will end in 2012 or 2013. AIM will
cover all participant expenses. More information,
and an application form, are available at


text:
The 7 Signs to Watch for in a Deadly Stroke
Strokes can happen to anyone in any age group. It is most prevalent in senior citizens due to many age related health issues. A stroke can be life threatening. We must stay vigilant for any signs of stroke in our loved ones and ourselves.
A stroke can happen very quickly or can be preceded by small TIA's (Transient Ischemic Attacks) or mini strokes. With a TIA, the symptoms may appear similar to a stroke, but pass quickly. Usually disappearing within a half hour. They don't leave outward signs of damage. Having said that, it is important to understand, a TIA can be a precursor to a major stroke. It is vital not to ignore the symptoms. A TIA should be reason to get to a doctor quickly.
The most common cause of stroke is high blood pressure. High blood pressure should not be taken lightly. It is important to see a doctor and control our blood pressure with weight loss and medications.
Another cause of strokes is Atrial Fibrillation. This is a condition where the upper chambers of the heart quiver instead of producing a strong muscular contraction of the upper part of the heart. The heart suffering from "afib" isn't pumping the blood around the body correctly, leaving an opportunity for the blood to pool causing a clot. This clot can become dislodge and flow with the blood stream until it lodges in the brain causing a stroke. A person experiencing AF has 7 times the chance of stroke. A person with chronic AF can be given blood thinning drugs such as Coumadin or Plavix.
It is important when suffering a stroke, the patient should immediately be transported to an emergency room of a hospital. This person should never try to drive themselves to the hospital. If a person suffers a stroke, it is imperative for them to be treated within the first 3 hours of onset. Most strokes can be reversed if treated within this time period.
Since this is such a life threatening situation, what are the stroke indicators we should be watching for? How will we know if a stroke is happening?
1. Ask them to smile. Watch to see if their smile droops on one side. Sometimes, Bell's Palsy, which is not a stroke can cause paralysis in facial muscles. It's not a stroke, but only a doctor can tell for certain. Don't risk it….seek an emergency room stat!
2. It can come dress as a speech problem. All of a sudden they aren't making any sense, or they can find the words for common everyday things. Ask the person to say a simple sentence, such as "it's raining outside". If this simple sentence isn't spoken coherently, time for transport to an ER.
3. You may notice a change in their face. Their eye or lip may, suddenly, droop on one side of their body. Be watchful for sudden numbness or weakness of the face, arm, or leg, especially if it happens on one side of the body. Ask your loved one to raise both arms, at the same time. Since a stroke can cause weakness or paralysis on either side, one arm may not want to raise with the other.
4. Ask them to stick our their tongue. If the tongue is crooked or goes to one side or the other, it could indicate stroke.
5. Your loved one may experience a sudden onset or complain about feeling dizzy. They may have a loss of balance or coordination. Many times, a stroke can be cloaked in the guise of a fall or a near fall. The person can have a small stroke and loses their balance. Most often, they don't know why they fell. Dad's strokes were always preceded with bouts of dizziness.
6. Watch for a sudden change in vision. Complaints of blurriness and/or difficulty seeing out of either or both eyes.
7. A loved one may complain about a severe headache for no known reason. Don't give your loved one an aspirin. If the stroke is from a hemorrhage instead of a clot, giving an aspirin will only make the bleed in the brain worse and can cause permanent damage. Only an MRI can determine the cause and location of a stroke.
Strokes can effect people differently. When Dad had one of his strokes, he lost bladder control. Before we noticed any of the other symptoms, we noticed he had wet the chair.
I know emergency room visits aren't any fun. I have sat for many, many hours in the ER with each one of my beloved aging senior citizens. It can take hours to receive the results of test. ER visits seem to be unavoidable as our loved ones age.
Strokes can happen quickly. Sometimes, it's difficult to know if your loved one has experienced a stroke. It's always best to keep in mind, as the old quote says, "it is better to be safe than sorry!" A good rule of thumb is, if you don't know, then go.
Want to find out more? Click here!
Related articles
- What are the Warning Signs of a Stroke? (donthaveastroke.com)
- Will blood thinning therapy reduce my risk of stroke? (zocdoc.com)
- Mini-stroke "doubles heart attack risk" (news.bioscholar.com)
- Mini-stroke doubles risk of heart attack (eurekalert.org)
- Something different- Warning signs of a stroke (xeniagreekmuslimah.wordpress.com)
- Management of atrial fibrillation based on guidelines – part II (cardiophile.org)
- What is a Stroke (donthaveastroke.com)
- 'Mini Strokes' Linked to Doubled Heart Attack Risk: Study (health.usnews.com)
One Response to "The 7 Signs to Watch for in a Deadly Stroke"
yeah it's really nice to told about this blog, that who's Person helps to suffering from Stroke Problem…..
To Know more details about Stroke Symptom visit this website


text:
Vachetta leather that only gets better with time
de bray backpack
Product Actions
This bag is made with vachetta leather — a natural, vegetable tanned leather that's intentionally left unfinished, allowing its natural oils to surface over time. The natural colourway will darken and develop a beautiful patina with wear and light exposure.
This versatile design gives you three ways to wear it: as a backpack, on your shoulder or by hand. It's finished with brass hardware that's been distressed to give it a vintage feel.
- Interior slip pocket
- Interior loop closure for added structure and security
- Adjustable straps
- Includes dust bag
- 12'' high x 11.25'' wide x 6.25'' deep
- Model is 5'10.5/179cm wearing a size O/S
- Content: 100% leather
- Care: Professional leather cleaner
- Imported


text:
Two Questions For Na Nachs
Rabbi Avraham Chaim Bloomenstiel commenting on Based On "A Childish Prank" - Na Nach Nachma:
I ask with complete temimus and without wanting to provoke anything untoward, but would one of the commentators from the Na Nach contingency please offer point-by-point answers to these questions:
1) In the Na Nach velt, is there a generally accepted halachic authority that people go to? If so, then who is it? If not, then who do Na Nachs go to with she'elos?
2) How does the Na Nach approach understand the Rebbe's well known statement (I believe it is found in Sichos ha-Ran) : "Do whatever you want with my teachings, just don't touch one word of the Shulchan Aruch!" ?


text:
Sunrise on Sunday -- 75 degrees and not a breath of wind. Lake George's water was still in the high 70s, its slick surface littered with leftovers from the night's midge hatch. Mullet were flipping randomly about, and at Black Point, the first shrimpers were already tossing nets.
Two commercial crabbers had started to work their pots and a number of bass boats were shooting down the river. And we -- brother in law Rich Rautio and I -- were trying to put our last gator tag to good use.
Now, the point of the forgoing is that the past weekend on the river resembled mid-August far more than late October.
The shrimp are still there, big ones, too. The mullet, while they are moving and showing roe, hadn't turned into a steady stream toward the ocean and the fishermen were still catching a little of everything.
In fact, my other brother in law, Frank Streeter, fished a bass tournament out of Palatka on Saturday and reported that he caught a flounder about 10 miles south of the State Road 17 bridge on a rattle trap.
At this point, just to keep the family happy, I should also mention that he won the tournament.
Farther north in the river there were plenty of croakers to be had along with numerous reds.
And speaking of reds, one of our commercial crabbers working near Green Cove Springs reported seeing a school of big reds being chased by two dolphin in the same way that dolphin chase mullet.
First time I've heard of reds being targeted by dolphin, even though I've had dolphin chase off a school of trout a time or two.
Closer to the ocean the flounder run is just getting better and better. Our commercial gigger, forced to hook and line fish as his motor went on the fritz, had a cooler full of large ones on Sunday. He also released a number of reds.
And if the various Internet reports are any indication, those targeting reds are being well rewarded for their efforts.
Out on the beaches, pompano, the leading edge of the fall southerly migration, have shown up in the last few days. The fisherman with the pompano also had some very nice whiting on both his trips.
It's also worth noting that the commercial shrimpers are starting to see more whiting in their nets. The whiting move south with the falling water temperatures along with the pompano.
From the local wrecks there has been one very consistent report -- short red snapper. Short snapper have been a recurring theme for the last few weeks on the internet reports.
It is worth noting that the tenor of those making the reports, even though they sounded a bit frustrated at not getting limit of keepers, was that the future looks bright for the spring snapper bite. Frustrated optimism, that's a fisherman for you.
In addition to the genuines, and this comes form a number of commercial boats, the vermilions fired off over the weekend.
Plenty of them in the 2-pound class too. Grouper on the other hand were somewhat rare even though there were plenty of reports of shorts in close.
Finally the trolling scene produced a little of everything, wahoo, sails, dolphin, kings, just a full array of what's available.
There was even one internet report, along with a picture or two, of a couple of swords caught and released by a boat drifting the stream out of St. Augustine.
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The third day of the Ulsan PWA World Cup started with extremely light winds in the morning, however, over the course of the morning the wind swung cross-shore and the conditions started to look much more promising. The wind continued to tease the competitors over the duration of the day, but extremely gusty winds put a spanner in the works and no heats could be completed today. After a long day on hold the sailors were eventually released at 5pm.
With the sailors playing the waiting game we caught up with Josh Angulo (Angulo / Gun Sails) - who was involved in one of the most talked about incidents of day two.
PWA: What are your thoughts on the whole incident with Cedric Bordes (Tabou / Gaastra) yesterday?
JA: "From yesterday to today things are pretty different. It often happens in racing that in the heat of the moment you get pretty upset with whatever has been going on, but it's no big deal. He (Bordes) Bordes hit me, it wasn't malicious and he didn't try to do it. It definitely cost me some places and at an event like this where we aren't guaranteed lots of races every place matters. I let him know what I thought, so he knows and I know he didn't mean to, so it's all good.
PWA: In the close season you moved back to Gun Sails, are you feeling happy with your setup?
JA: "For sure I am, I've got really good gear as everybody obviously does. Every year it's getting more and more competitive, but I feel that over the course of the year with the different conditions that I'll be able to do well, as my gear works so well over a wide range of conditions, which I think is really important. I'm fired up and just having fun and definitely once again very blessed to be hanging here on the beach windsurfing."
PWA: Which equipment were you on yesterday?
JA: "I rode my 9.5m and 8.7m with both my large and medium board combined with a few different fins. I was switching around quite a bit as the conditions were quite variable."
PWA: Aims for the season?
JA: "My aims are always to win. I always believe that I can beat pretty much anyone in the world on a windsurf board because that's what I've been doing all my life. I also understand that it takes a lot of dedication, so I try to allot more and more time for windsurfing, since I do have the support from my sponsors to do it and I still believe that I can win. I definitely wouldn't be here if I thought I'm only gonna get tenth or twelfth or something you know. I'm aiming for the top."
PWA: Are you still located in Boston? And do you get to windsurf much in Boston?
JA: "Yep I just flew here from there! I do, and right now it's the time of year when it's just starting to warm up. I also did a couple of training trips to Maui before this event, as I can do so much more specific testing, easily in Maui and crucially with the right people. So now I'll be able to do maintenance windsurfing in Boston."
PWA: Thanks Josh and good luck for the remainder of the event.
The forecast for tomorrow is predicting wind from the opposite direction in the morning, so with this in mind the skippers' meeting has been called for 08:30am with the action commencing from 9am. Once again, you'll be able to watch all the action unfold as it happens by tuning into the PWA TV, which can be found @ https://www.pwaworldtour.com/index.php?id=1622
Scope The Action
For information on all the entrants, and to keep up to date with every piece of the action, navigate to www.pwaworldtour.com
Here you can use our:
• Live streaming service
• Live ticker service for heat-by-heat bulletins • Check live elimination ladders
• View results
• Read daily news summaries
• Browse awesome action photo galleries
There's also a dedicated event website which can be found @ http://www.pwaulsan.com
Or for more information, please contact the PWA office via firstname.lastname@example.com


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Key Votes
HB 6342 - Attorney General Candidate Qualifications - Key Vote
Connecticut Key Votes
Gregg Haddad voted Yea (Passage) on this Legislation.
Read statements Gregg Haddad made in this general time period.
Stage Details
Legislation - Bill Passed (House) (91-51) - May 18, 2011(Key vote)
Title: Attorney General Candidate Qualifications
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Vote to pass a bill that amends the eligibility requirements for candidates seeking the position of Attorney General.
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Legislation - Introduced (House) - Feb. 14, 2011
Title: Attorney General Candidate Qualifications
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text: Hi guys I've been using the Legend 17 in the mojo set-up and am curious about how the 18 would differ in the mojo. Playability, Spin, Durability, Power. I can guess but would rather hear someone's first hand experice. Did you have to use a different tension for one vs. the other? Thanks


text:
Okay I wanted to post this in it's own thread so it can be as big as possible. Sheets posted the hand history here:
Here is the animated version. Nice win sir!
<OBJECT id=trainingApp_rj2 codeBase=http://fpdownload.macromedia.com/pub/shockwave/cabs/flash/swflash.cab#version=7,0,0,0 height=420 width=560 align=middle><PARAM NAME="allowScriptAccess" VALUE="sameDomain"><PARAM NAME="movie" VALUE="http://www.pokerxfactor.com/swf/trainingApp_rj2.swf?xmlHandID=1522&fn=&hn= 1&mh=1&sc=1"><PARAM NAME="quality" VALUE="high"><PARAM NAME="bgcolor" VALUE="#cccccc"> <embed src="http://www.pokerxfactor.com/swf/trainingApp_rj2.swf?xmlHandID=1522&fn=&hn=1&mh=1&s c=1" quality="high" bgcolor="#cccccc" width="560" height="420" name="trainingApp_rj2" align="middle" allowScriptAccess="sameDomain" type="application/x-shockwave-flash" pluginspage="http://www.macromedia.com/go/getflashplayer" /></OBJECT>
Click here to view a larger version.
how does that software work? you input your HH and it gives you a video? does it work on all sites?
That software is cool and Sheets is awesome obv.
But who couldn't have won that thing with all the pocket pairs, quads etc that he got in only 37 hands. Unbelievable cards.
Anyways...no disrespect..just a comment.
Great job mind
vn sheets, and thanks again mindwise for the animation!
I really like where you've taken this so far. However, if you plan on making more animations similar to this though, might I suggest that you choose a different sit n go. No offense to sheets or anything, but that looked like a rather easy win. It would be great to be able to see a win that really challenges sheets. For example, I would really LOVE to see a sit n go where sheets plays a short stack on the bubble, something along those lines. Not that I didn't appreciate this animation. We all know sheets has mad skillz, I would just love to see him show them off. Thanks!
Sick. Everytime he picked up a big hand the other players bet for him. You have to love that action. Very well played.
Nice final four hands
K3 flop 2 pair
105 turn 2 pair - river boat ...
nice finishing move ...
Extra sick... even your 4 handed 8/5 off-suit hand that you DIDN'T play would've resulted in a full-house. :) How's that for RESULTS ORIENTED???
BTW -- it's obv that Lee reserves the "Extra Power Boost" button for sheets only.
Agreed, you really know how to play your quads...but how could a Sit and Go master such as yourself not know your Q5s in the BB would have turned into Queens full?!? J/K Great game and posting your hand histories (and mindwise's software) is MUCH appreciated.
Not to sound ungrateful, but I agree with whoever said a different SnG would be nice. This doesn't show anything as far as strategy, it's just him getting a bunch of good hole cards and great flops for them. I'm pretty sure a novice could have won this SnG with those cards, but at the same time, those other players didn't seem very good.
That aside, this is pretty sweet mindwise. Great work putting this up, hopefully P5's will have a few more of these to come. This is infinitely better than reading through the hand histories, and could be used as a great teaching tool. Really cool to watch. Many props for posting this.
Was it just me, or where your 2 oppenents in the final 3 the worst 2 players at the table....??
Cool post. Thanks for doing this also. As somebody that only play's SNG this
is a great learning tool from a great player. Sheets can I ask you one thing. I
think it was at the 75/150 level you folded to you in SB you folded 10 7 suited.
Was just wondering why?? Good game.
Sheets, if you have time: I was surprised to see how conservatively you played in a few situations. The one that comes to mind is the A10 hand where you checked it down and ended up splitting with a weaker ace.
Was it because the maniacs were just knocking each other out right and left so you really didn't have to manufacture any plays?
Thanks as always for sharing!
**Edit the 10 7 soooted hand also occured to me as it was in position, but given how active the table was, I can easily guess it wasn't worth making a stab there.
I think Sheets's original post was kind of in jest - how to win a sng in 37 hands, check me out I'm sweet. So to those people criticising the choice of SNG, I don't think he intended it to be a training tool. . . with that said, how about a full HH of an MTT win using Mindwise's software?
Hey everyone, thanks for the comments. Currently, if you join at PokerXFactor.com (it's free), you can upload a single hand and it is animated automatically.
Right now we don't have a way for people to upload entire tournaments. We had to hand edit this one for sheets and we hand edited the quiz I posted earlier:
We're going to have some big announcements about the next phase of the site in February. Stay tuned.
The PokerXFactor hand viewer currently works with Ultimate Bet, Party, Paradise, Full Tilt, and Stars. We still find bugs in the hand histories and I suspect it will take a long time to get them all out. For example, Poker Stars hand histories for SNGs, it turns out, were different from their hand histories for MTT. Things like that.
I really want to thank sheets for sharing. Content is king guys. I, for one, have never seen a SNG won so fast.
Thank you for posting that up. I watched it after I read the original post.. verry good hand selections man. even though you made it look easy and everyone says it would be too easy. I think that you held your composure well and only played select hands and tore them apart.
Awesome post, Sheets you are the man..
Haha I love the choice of Sit and Gos comments. if Sheets always got these hands in these situations he would win every sunday tournament in 35 minutes.
Man this software is cool mindwise - thank you for posting. But I gotta know - Did you name the software after Weapon X?
Yeah except everyone seemed to get nutty good cards - looked like Royal Hold Em there for while. Good job extracting on the quads sheets!
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Notation basée sur
20 Avis
4,8 sur août 26, 2016
Exactly what we expected and then some! Went out of their way to help us out and was so accommodating! Highly recommend Bear Paw Adventure.
Réponse du propriétaire
Thank you for staying with us and for your comments. It is really rewarding to see our guests enjoy the Alaska Kenai Pennsula and our lodging at Bear Paw Adventure.
- John (innkeeper)
4,0 sur février 22, 2015
Six of us, including my sister and her husband from Minnesota, stayed in the "Wise Old Hunter" in the summer of 2014. We were amazed at the beauty of the cabin and very pleased with the comfort and accommodations. I have family members coming from Texas and Mississippi this summer and have already booked the same cabin as I',m sure they will love it as much as we did.
5 sur septembre 14, 2014
Couldn't have been happier with the accommodations at Bear Paw Adventure. We (5 of us) stayed in the Wise Old Hunter Lodge for several nights on a July trip. It had all the comforts of home in a beautiful Anchor Point location. The Homer Spit right down the road is a great place to visit - the scenery is awesome. John was instrumental in helping us to plan our excursions -- salmon fishing, fjords cruising, hiking, etc. After the salmon adventure, we grilled our salmon for dinner on the grill outside. Best fish ever. The kitchen was well stocked with silverware, dishes, pots, etc. We even had games to play in the evenings! John is super nice and was so helpful. Recommend this place to everyone!
4,6 sur août 20, 2014
I was going to be in the Ninilchik/Anchor Point area and would be done too late to drive home, so booked the Moose cabin. A friend, her daughter and I found this cabin to be charming and oh so comfortable! The cabin was clean and cozy, very welcoming after a day at the fair. John was very accommodating, and although we never saw him, we appreciated his thorough directions and anticipation of our needs. I would definitely recommend this lodging!
5 sur août 11, 2014
We just returned from a fishing trip to Alaska and, once again, stayed in the Moose Lodge for eight nights. We love this cabin. It is so comfortable and convenient to fishing at Anchor Point and for trips into Homer. Everything about this cabin feels so homey after a long day of halibut fishing in Cooke Inlet. We love the fact that we can grill our fresh catch each day. Added bonus this time was seeing a Mama Moose and her two babies feeding right outside our bedroom window. We had all the comforts of home at an affordable price. We will definitely be back!! Charlie and Linda
Réponse du propriétaire
We're happy that you had a great stay in the area and in the Moose Cabin. This spring, when I was working in Moose Cabin I saw a Cow laying down in the grass near the front of the porch. She looked like she was in labor and I got my camcorder and got all set to record the event. It looked like the baby moose would be born any minute as she appeared to be in hard labor. But then, after about a half hour, she got up and started feeding – I suppose she delivered sometime later. I'm thinking that may be the Cow and two calves that you saw.
- John Ogle (innkeeper)
4,4 sur août 08, 2014
This cabin was beautiful and well equipped with everything our family of 8 needed. We loved the Captain Cook and Alaska deco. The craftsmanship on the interior doors and railing was beautiful to see.
5 sur juillet 29, 2014
We stayed at other cabins in our tour of AK and the entire experience with Bear Paw Adventure was by far the best! The reservations were easy, the follow up customer service to ensure we were happy and they beautiful and very clean cabin really stood out. I would highly recommend Bear Paw Adventures to anyone and look forward to my return trip in the near future :)
5 sur juillet 27, 2014
We absolutely loved our stay. The cabin was private, charming, and immaculate. The location was perfect for enjoying outside activities or just relaxing. It was like a home away from home. We would not hesitate to go there again. Just wish we could have stayed longer. Dominic & Lisa
4,8 sur juillet 25, 2014
Very nice cabin with all you need and more. We like very much. It was the best accommodation during our summer vacation in Alaska
4,0 sur juillet 21, 2014
Our family had such a wonderful time staying at the Bear Den cabin. It was spacious, clean, and had a great yard. We will deffinitely stay again.
5 sur juillet 21, 2014
Stayed 2 nights in the Moose Cabin. Very impressive facility, nice and roomy. The only negative I would say was the shower, water pressure was very low but it worked, other than that the rest of the facility was beyond what I expected. Would definitely stay there again when in the area.
Réponse du propriétaire
Thank you very much for the review and we are happy you enjoyed your stay. We are looking forward to your next visit. Also, thank you for the comment about the shower water pressure. At this time, we are revising our water system to better serve our guests. During this upgrade, the drilled water well that supplies the Moose Cabin and the Wise Old Hunter Lodge is also supplying water to the Bear Den Vacation Home. You may have noticed that we are drilling an additional well near the Bear Den. Once the new well is complete and in service we should have much better water pressure in all buildings.
- John (innkeeper)
5 sur juillet 20, 2014
My family and I stayed at the Captain Cook Cabin in July. This cabin is absolutely amazing! The cabin was beautiful with many special details and was extremely clean. We used the kitchen which had everything we needed to prepare meals. We especially loved grilling and eating on the porch. We spent 2 weeks in Alaska, and we all agreed that the Captain Cook Cabin was by far our favorite place we stayed. Our only regret was that we only stayed for 2 nights. We hope to visit Alaska again, and when we do, we will be staying here again!
4,2 sur juillet 20, 2014
This is the place to stay. John has all the answers about the area and the cabins are just wonderful . Cabins have everything for your stay and big grocery store is close bye. Wee seen Moose and a lot of birds there. Used the grill for dinners. You won't be disappointed.
4,6 sur juillet 20, 2014
This was our second time that we stayed at Bear Paw in Anchor Point. We were looking for a clean comfortable place close to town with a nice kitchen. Bear Paw meets and exceeds this expectation. My wife and I stayed at the Moose cabin. It has a large, well-equipped kitchen, great room combination that is stocked with all the cooking essentials. All you have to bring is your food. The Moose cabin is a large log cabin that is beautiful decorated. The dining area has large windows from where we have observed a grazing moose. It has a small bedroom with two twin size beds. There are two additional twin size beds in the adjacent hallway. The bathroom has a shower stall which served us perfectly. John, the inn-keeper is very helpful and will make your stay smooth and memorable. We will return next year and have already reserved the Moose cabin for our stay in Anchor Point. This is a safe quiet place located on Sterling Highway. Wulf & Heide from Virginia
5 sur juillet 19, 2014
My wife and I spent a week at Bear Paw Adventure and the place was awesome. The only regret we had was we had to leave! If you want peace and quiet and be close to everything the area has to offer this is the place to go. John was a great help in booking salmon and halibut fishing and a place to take my fish to ship back home. I was worried that the airlines would loose my fishing equipment so I sent it Fed Ex and it was there waiting for me when we arrived. The cabin was way bigger than we needed, the grill and deck are awesome! It is just a short drive to the beach, fishing or Homer. We hope to get the whole family together and spend time up at Bear Paw Adventures in the near future!
5 sur juillet 19, 2014
There was a group of six that stayed here while on a fishing trip. Couldn't be better!
4,6 sur juillet 19, 2014
Weve stayed at many cabins but this cabin was exceptional. Everything down to the details was amazing. Location great as well. The best place i have ever stayed. Amazing memories. Hope to be back next year.
4,8 sur juillet 19, 2014
My family visited from Idaho this past summer and going to Homer was a must. However, finding decent lodging at an affordable rate can be difficult for a family of 8. That is until I stumbled upon the Bear Paw Adventure website! It was perfect, close enough to town but far enough away for us to have family time. The personnel were more than accommodating and the cabin was very clean. Nice to have a home cooked meal while there! And plenty of activities to do at the cabin!
5 sur juillet 19, 2014
We live in Anchorage AK, and when family from California were in town, we decided to take them to a real Alaskan lodge experience, and chose Bear Paw Adventure. We stayed in the Wise Old Hunter lodge, and it was Just Perfect. Our guests absolutely ate it all up. We took a day trip over to nearby Homer, a scenic boar harbor town. Bear Paw Adventure had excellent facilities; clean, and plenty of food items in the pantry for the things we forgot to bring along. Pots and pans were all in great shape, and we had a grand time. Will go there again without hesitation should family drop in again.
5 sur juillet 18, 2014
The cabins are 1st rate, very beautifully built, Like being home, Our stays have always been awesome. The fishing is great, my last halibut was 144 lbs. This is the only place I would ever stay,


text:
Many people are still convinced that Big Charity in New Orleans should be saved and restored to use as a Charity Hospital and LSU teaching facility. And the arguments for it keep getting better.
The folks in favor of it were originally mainly preservation proponents who cringe at the thought of moving or destroying some 167 historic homes in the area where LSU and Veterans Administration are currently planning to build brand new hospitals just uptown from the Big Charity site. In so doing, they would abandon the former sites of Veterans Hospital and Big Charity, both of which were extensively damaged during Hurricane Katrina.
The new location was supposed to link them and thus save by combining some of the facilities needed at each hospital. But The Veterans Administration is ready to go ahead with its project and have its hospital in use by 2012. LSU does not have money for its project yet so it will not be completed until later, which eliminates the savings benefit of combining facilities.
The preservationists argue that Big Charity is structurally sound and could be turned into a modern hospital and teaching facility sooner and at less cost than rebuilding the structure elsewhere by clearing the new area and starting from scratch. Whats more, the new Veterans Hospital could still be located on part of the nearby site where the new hospitals were planned and the site of the old Veterans hospital could be saved for future expansion of LSU and Charity.
It seems that the preservationists have gained a step with the delay of the LSU project but they still need a clear-cut outlook on the benefit of preserving Big Charity and putting it to use again for what it was intended to be. If they can do that, most of the people would join them in their preservation and money saving efforts if such be the case. And we would keep the classic art deco structure we all relate to the medical profession of Louisiana. It seems that would be preferable to relegating it to condominiums or tearing it down, heaven forbid.
As much as we hate studies that delay projects, we think this one needs a final summation of the plusses and minuses of how to provide the area with charity and veterans hospitals and teaching facilities best with the least disruption possible to our historic infrastructure.


text:
Too old for Abercrombie!
Abercrombie & Fitch is one of the most popular clothing brands among high school and college students in the United States. Just walk into any classroom on a college campus, and you'll see what I mean. Heck, even I used to wear A&F stuff 15 years ago when I was in school.
But now, I can't even walk into an A&F store without feeling hopelessly out of place. From the decor to the music to the teen shoppers, it's clear that at 35, I'm way too old for Abercrombie. I'm not exactly geriatric, but still… I think the store is definitely aimed at people who don't have to worry about jobs, mortgages, or applying for disability insurance.
This is actually kind of an awakening for me. The two other main clothing stores I used to shop at as a high school or college student were The Gap and J.Crew — both of which I'm still perfectly comfortable shopping at today. These stores have more classic styles that adults my age can still pull off, which certainly can't be said about A&F.
Personally, I don't think anyone over 28 should bother wearing Abercrombie anymore. Do you agree with this?


text:
KAI RYSSDAL: Gamblers looking for a change of venue will soon have another choice. Manchester, in the north of England, has been chosen as the home for the U.K.'s first super-casino. It'll have the works: roulette, card tables and unlimited slot machines. Manchester figures it's hit the jackpot. But critics say Britain's taking a dangerous gamble. From London, Marketplace's Stephen Beard reports.
STEPHEN BEARD: Britain has never seen anything like it — 1,200 slot machines, each with a payout up to $2 million. For the first time in the U.K. a casino will be glitzy, with live entertainment. In Parliament, the minister Tessa Jowell told her critics the country isn't heading down the road to ruin.
TESSA JOWELL: Las Vegas is not coming to Great Britain. British casinos will be subject to new controls which will be the strictest in the world.
The supercasino will be in a rundown part of Manchester and will create 3,000 much-needed jobs, says City Council boss Richard Leese.
RICHARD LEESE: It's going to be to be a real boost to the regeneration of what is one of the most deprived areas of the country. And we're now really looking forward to taking this forward.
But Justin Williams, a reformed gambling addict, doesn't share that enthusiasm for the supercasino — or for the other 16 smaller new-style casinos around Britain also announced today.
JUSTIN WILLIAMS: We're making gambling more accessible to more vulnerable people. And gambling is just as addictive as an addiction to a substance.
The government says it'll be watching the new casinos carefully to monitor the economic and the social effects.
In London, this is Stephen Beard for Marketplace.