text:
|Publication number
|Publication type
|Application number
|Publication date
|Jan 13, 1981
|Filing date
|Aug 4, 1978
|Priority date
|Aug 4, 1978
|Publication number
|Joseph X. McDermott
|Original Assignee
|Halcon Research And Development Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (1), Referenced by (15), Classifications (8), Legal Events (1)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a division of application Ser. No. 822,290 filed Aug. 5, 1977 now U.S. Pat. No. 4,151,116.
This invention relates to the preparation of maleic anhydride by the catalytic molecular oxygen oxidation of butane and is more particularly concerned with an improved catalyst for use in carrying out that oxidation.
Maleic anhydride is of significant commercial interest throughout the world, and is extensively used in the manufacture of alkyd resins. It is also a versatile intermediate for chemical syntheses. Consequently, large quantities of maleic anhydride are produced each year to satisfy these needs. The production of maleic anhydride by the catalytic oxidation of benzene and butene is well known and the principal method currently employed for manufacturing maleic anhydride is by the air oxidation of benzene in the presence of certain heavy metal oxide catalysts. Comparatively little attention has been given to the use of saturated aliphatic hydrocarbons, e.g. butane, as feedstocks for the preparation of maleic anhydride. This is due, in part at least, to the fact that butane is more difficult to oxidize than benzene or butene, often resulting in low conversions to maleic anhydride. Although catalysts for the oxidation of saturated aliphatic hydrocarbons such as butane are known, the yields of the desired maleic anhydride product over the known catalyst are, in most cases, insufficiently high to make such butane competitive with benzene as a feedstock.
In general, catalysts proposed for the oxidation of butane to maleic anhydride have been based upon vanadium and phosphorus. Thus, the use of a vanadium-phosphorus complex catalyst to oxidize butane to maleic anhydride is described in Bergman et al, U.S. Pat. No. 3,293,268. This catalyst, however, requires an operating temperature greater than 500� C. and, in general, reported yields are relatively low and not commercially attractive. In order to improve the effectiveness of vanadium-phosphorus catalysts, it has been proposed to incorporate various additives, frequently referred to as "activators", "stabilizers", "promoters", and the like. For example, Freerks et al U.S. Pat. No. 3,832,359 proposes the addition of iron to phosphorus and vanadium, and Raffelson U.S. Pat. No. 3,867,411 further modifies the iron-modified phosphorus vanadium catalyst by the addition of chromium. Boghosian U.S. Pat. No. 3,862,146 adds to phosphorus and vanadium a catalyst activator which is zinc, bismuth, copper or lithium. In British Pat. No. 1,475,309, it is proposed to increase the effectiveness of a phosphorus-vanadium catalyst by adding an activator which is cobalt or nickel. British Pat. No. 1,460,971 is concerned with a catalyst in which the added component is titanium, zirconium, hafnium or silicon. More recently, Young et al U.S. Pat. No. 3,888,886 discloses phosphorus-vanadium catalysts modified with various transition metals having varying effectiveness, the more active being chromium, iron, hafnium, zirconium, cerium and lanthanum. Although other metals are disclosed, they are characterized as having little or no activity. These metals include manganese, zinc, ruthenium, molybdenum, tin, titanium, antimony, thorium and praseodymium.
While these various additives do bring about some improvement in the phosphorus-vanadium catalyst suitable for oxidizing butane to maleic anhydride, there remains much room for improvement, particularly from the standpoint of high conversions and yields.
It is accordingly an object of this invention to provide an improved catalyst based upon phosphorus and vanadium.
It is a further object of the invention to provide a catalyst of the character indicated which is of particular effectiveness in the oxidation of butane to maleic anhydride.
It is a still further object of the invention to provide a promoted phosphorus-vanadium catalyst which makes possible improved yields and high conversions in the oxidation of butane to maleic anhydride.
Another object of the invention is to provide a process for the catalytic oxidation of butane to maleic anhydride with improved yields and improved selectivities.
These and other objectives are realized in accordance with the present invention by a catalyst comprising a substrate containing phosphorus and vanadium, and optionally containing a promoting or activating additive, and a promoter deposited upon the substrate after the substrate has been formed, i.e. a "post-deposited" promoter. More particularly, the catalyst of this invention comprises a pre-formed substrate containing phosphorus and vanadium, and a post-deposited promoter which is typically magnesium, calcium, scandium, yttrium, lanthanum, uranium, cerium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gallium, indium, silicon, germanium, tin, bismuth, antimony or tellurium. When an additive or activator is incorporated in the substrate, it is typically titanium, zinc, hafnium, lithium, magnesium, calcium, iron, cobalt, nickel, copper, tin, bismuth, uranium, the rare earth metals (particularly cerium and lanthanum), chromium, cadmium or aluminum.
The term "substrate" is used to designate a catalyst composition which has been prepared in any convenient manner, e.g. by any of the processes well known to the art, and has been dried and activated and can, in itself, serve as a catalyst in the oxidation of butane to produce maleic anhydride. This preformed catalytically active substrate is, however, in accordance with the invention, treated so that it is significantly more effective as a catalyst by having a promoter applied to its surface, e.g. by treating it with a solution or dispersion containing the promoting element, so that the substrate is post-coated or post-impregnated with the promoting element. In accordance with the invention, one or more of the promoting elements may be post-deposited upon the substrate, and this post-deposition may take place in one or more treating steps, e.g. one of the promoting elements may be applied in a first step, and the other of the promoting elements may be applied in a second step. As will be apparent from the above listing of typical additives and typical promoters, the catalyst of the invention may contain the same element as an integral component of the substrate and serving as an activating additive, hereinafter referred to simply as an "activator", and also as a post-deposited promoter. Usually, however, the activator integrally incorporated in the substrate and the post-deposited or "surface" promoter are different.
Best results are obtained in accordance with the invention when the phosphorus and vanadium are present in the substrate in the atomic ratio of 0.9:1 to 0.5:1, preferably 1:1 to 1.3:1, although other ratios may be employed. Generally, the ratio of phosphorus to vanadium is at least 1 to 1, and not more than 1.25 to 1. The amount of the integrally incorporated activator in the substrate, expressed as an atomic ratio in relation to V, is variable over a wide range, but generally it lies in the range of 0.01 to 0.3 atom per atom of vanadium in the substrate. Preferably, however, the amount of activator is 0.01 to 0.15 atom per atom of vanadium, and most preferably, 0.03 to 0.08 atom per V atom.
Similarly, the amount of post-deposited promoter may vary over a large range, but preferably it is at least 0.001 atom per atom of vanadium in the substrate. Typically, the amount of promoter will lie within the range of 0.001-0.2 atom per atom of vanadium, and preferably the amount will be in the range of 0.01-0.06 atom per V atom.
When the atomic amount of vanadium in the substrate is taken as 1, the amount of integrally-incorporated activator will typically be 0.01 to 0.3, preferably 0.01 to 0.15, and most preferably 0.03 to 0.08, whereas the amount of post-deposited promoter will typically be 0.001 to 0.2, preferably 0.01 to 0.06.
The catalyst of this invention can be prepared in any convenient manner, e.g. using techniques already known by persons skilled in the art. The following procedures, however, have been found to be particularly suitable and to yield catalysts of favorable activity. It will be understood, however, that the invention is not limited to catalyst prepared by these particular methods of preparation. Thus, the substrate of the catalyst is preferably prepared by forming a solution of a vanadium compound, a phosphorus compound, and if used, a compound of the activator metal in an appropriate solvent, concentrated hydrochloric acid being particularly suitable as a solvent for the substrate components.
If the substrate is to be used in non-supported form, e.g. in the form of a pellet or other shape, the solution is evaporated to dryness and the resulting finely divided particles are pelletized or formed into other shapes in conventional manner.
On the other hand, if the substrate is to be in supported form, the aqueous acidic solution is deposited upon a support or carrier and dried. The drying of the solution by evaporation of its aqueous content is readily effected merely by heating it in air or in an inert atmosphere, e.g. in nitrogen at 90� to 200� C., typically about 100� C. until dried. Thereafter, the dried composition, either in supported form or as a powder, or after forming, is activated by calcination, preferably in air, at a temperature of at least about 300� C. Preferably, the catalyst is activated before forming. Alternatively, activation can be accomplished with oxygen or in an inert atmosphere, e.g. with nitrogen, argon, or other inert gas.
The phosphorus, vanadium and optional activator components of the substrate can be incorporated in any convenient form, depending upon the particular solvent being used to place them in solution, as will be well understood by persons skilled in the art. While hydrochloric acid, e.g. in concentrated form or in constant boiling form, is the preferred solvent, other solvents can be readily used, depending upon the form of the compound being employed. For example, polar organic solvents such as alcohols, amides, e.g. formamide, and the like can be used.
Thus, suitable phosphorus compounds include phosphoric acids, such as metaphosphoric acid, orthophosphoric acid, triphosphoric acid and pyrophosphoric acid; phosphorus oxides, such as phosphorus pentoxide; phosphorus halides and oxyhalides, such as phosphorus oxyiodide, phosphorus pentachloride and phosphorus oxybromide; phosphorus salts such as mono-, di- and tri-ammonium phosphates, and organophosphorus compounds such as ethyl phosphate and methyl phosphate. However, phosphoric acids, such as orthophosphoric acid, and phosphorus pentoxide are preferred.
Representative of vanadium compounds which can be employed are vanadium oxides, such as vanadium pentoxide and vanadium trioxide; vanadium halides and oxyhalides, such as vanadium trichloride, vanadium tribromide, vanadyl chloride, vanadyl trichloride, vanadyl dichloride, vanadyl bromide, vanadyl dibromide and vanadyl tribromide; vanadium-containing acids such as metavanadic acid and pyrovanadic acid; and vanadium salts, both organic and inorganic, such as ammonium metavanadate, vanadium sulfate, vanadium phosphate, vanadyl formate, vanadyl acetoacetonate and vanadyl oxalate. Vanadium pentoxide is, however, preferred.
Similarly, a wide variety of compounds can be employed to introduce the activator element into the substrate. These activator compounds, however, should be at least partially soluble in the solvent medium used in the particular preparation in order to be best suited for combination with the phosphorus and vanadium components of the substrate. Typical compounds of titanium, which is the preferred activator, include titanium halides, such as titanium dichloride, titanium trichloride, titanium tetrachloride, titanium dibromide, titanium tribromide, titanium tetrabromide, titanium diiodide, titanium triiodide, titanium tetraiodide, and titanium tetrafluoride; titanium salts such as titanium phosphates and titanium sulfates; and organic titanium compounds, e.g. alkyl titanates such as methyl titanate, ethyl titanate, isopropyl titanate and butyl titanate; and aryl titanates such as phenoxy titanium trichloride and phenyl titanate.
Corresponding compounds of the other activators are suitably used, the above-specified compounds of titanium merely being illustrative of the forms in which all of the activator elements may be incorporated.
When two activators are to be incorporated, it is, of course, possible to combine them in one compound, and similarly, the titanium compound may include another metal which has no apparent effect upon the catalytic activity of the substrate. Typical of such compounds are potassium fluorotitanate, inorganic titanates such as alkali metal titanates, alkaline earth metal titanates, aluminum titanate and lead titanate. In like manner, the activator metal may be included in the compound supplying the phosphorus or vanadium component of the substrate, e.g. iron or zinc or copper phosphate. It is preferred, however, that each component be added in the form of a compound which does not introduce another metal into the composition.
The promoters to be post-deposited upon the substrate in accordance with this invention are preferably applied to the substrate in a form which does not attack the substrate. Water, for example, does tend to have an adverse action and it is preferred, therefore, to employ an organic solvent. Any organic solvent such as an ether, e.g. dibutyl ether or tetrahydrofuran, an alcohol, e.g. isopropyl alcohol, a ketone, e.g. methylethyl ketone, a carboxylic acid, e.g. acetic acid, a nitrogen-containing compound, e.g. formamide and ethylene diamine, and the like can be used. The invention is thus in no way limited to the use of any particular solvent, but tetrahydrofuran and formamide are preferred. The promoter should, therefore, be in a form which is at least partially soluble in the solvent to be used. Typically, the promoter will be in the form of a salt, e.g. an inorganic salt such as chloride, bromide or iodide, or an organic salt such as a formate or acetate. When, for example, zinc is to be used as the promoter, it is preferably used in the form of zinc chloride, zinc bromide, zinc iodide, zinc formate or zinc acetate. When any of the other promoter metals are to be post-deposited upon the substrate, they are also preferably used in the form of the above-recited salts. It has also been found that the addition of a small amount of a phosphoric acid, e.g. orthophosphoric acid, or a boric acid, e.g. ortho boric acid, has a favorable effect upon the activity of the promoter. The amount of phosphoric or boric acid is typically 0.01 to 0.10 mol per mol (expressed as P or B) based on the V in the substrate, or expressed another way, 0.3 to 3 atoms per atom of promoter metal in the promoter solution.
As previously mentioned, the substrate is formed by combining the phosphorus component, the vanadium component and, if used, the activator component in a solution and then evaporating the solution to dryness to form a dry particulate mass or, if the substrate is to be supported, the solution is applied to the support or carrier particles and thereafter evaporated to dryness to provide support or carrier particles coated or impregnated with the catalytic components of the substrate. Although it is not essential from the standpoint of the invention, it is desirable that a substantial portion, e.g. at least about 50% of the vanadium be in the tetravalent form. As a result of having been in solution in concentrated hydrochloric acid, the vanadium will ordinarily be mostly in the tetravalent state. The same is true when another acid with reducing properties, such as oxalic acid, is the acidifying agent in the aqueous solution, instead of hydrochloric acid or other hydrohalic acid. While concentrated acidic solutions are preferred, more dilute solutions may also be used. Unacidified water can be used as the solvent, and in this case, it is preferable to include in the solution an organic reducing agent such as an aldehyde or an amine.
Following the drying of the solution containing the substrate components, the dried particulate mass is preferably formed into a shape suitable for use in a butane oxidation reactor, e.g. the particles can be pelletized or prilled or tabletted or otherwise formed into structures. As previously mentioned, the particles are preferably activated, as described below, before they are shaped. Methods for shaping catalyst particles are well known in the art and form no part of the present invention. Typically, the particles to be shaped are wetted with enough water to form viscous putty, and there are suitably added a lubricant such as stearic acid and a binder such as polyvinyl alcohol. The moist viscous mass is then shaped by extrusion or pelletting, or otherwise, in conventional manner as will be obvious to persons skilled in the art.
When the substrate is to be supported on a carrier, any of the carriers known in the art may be employed, including silica gel, silica alumina, silica, kieselguhr, alundum, fuller's earth, pumice, silicon carbide, asbestos, and the like, the carrier suitably being inert to the solution containing the substrate components, which is applied to the carrier and resistant to the conditions encountered in the catalytic oxidation of butane. The carrier or support preferably has a low surface area, e.g. from about 0.01 to 10 square meters per gram. The amount of substrate components deposited on the carrier should be sufficient substantially to coat the surface of the carrier. For use in a fixed-bed reactor installation, the size of the coated or impregnated carrier will preferably be from about 21/2 to about 10 mesh. The carriers may be of a variety of shapes, the preferred shape being cylindrical or spherical. The size of the catalyst particles used in fluidized bed reactors is quite small, however, usually varying from about 10 to about 150 microns, and in such systems the substrate normally will not be provided with a carrier but will be formed into the desired particle size after drying from solution. The carrier is coated by spraying the substrate solution upon it or by tumbling it in the solution while heating it to evaporate the water.
The dried substrate, whether in its initial particulate form which may be first subdivided, e.g. for use in a fluid-bed reactor or in its shaped form, e.g. as pellets, or in supported form, is then "activated" in the manner previously mentioned by heating it at an elevated temperature, e.g. at least about 300� C. in the presence of oxygen suitably in the form of air on in an inert atmosphere, preferably for a period of 30 to 300 minutes. If the activation is effected in an air or oxygen atmosphere, care should be taken to keep the temperature below 500� C. in order to avoid undue oxidation of tetravalent vanadium to pentavalent vanadium in order that an appreciable portion of the vanadium in the activated substrate will still be present in the tetravalent form.
In accordance with the invention, the activated substrate is now coated or impregnated with the desired promoter. The procedure for applying the promoter to the substrate is in no way critical and procedures such as used in coating a carrier may be used. Typically, the promoter solution may be used in a volume equal to the void space of the substrate and, when added to the substrate, the solution may be imbibed by the substrate pores. Alternatively, the substrate may be immersed in an excess volume of promoter solution, then removed and allowed to drain. The concentration of promoter in the solution is selected so that the desired quantity of promoter is retained by the catalyst. In a third method, the promoter solution is sprayed upon the particles or shapes of substrate, which are tumbled to achieve uniformity. The thus-treated substrate is then dried and activated in the manner described above in connection with making a supported substrate. If desired, activation can be effected in the reactor in which the catalyst composition of the invention is to be employed, i.e. by so-called in situ activation. In this case, the catalyst is charged to the reactor and a butane-air mixture is passed through it at temperatures of 350� to 450� C. for 2 to 12 hours.
Butane is oxidized in the presence of the above-described catalyst of this invention in any conventional manner, and the catalyst is useful in both fluid-bed reactors and in fixed-tube reactors and the conditions of operation of such reactors are well known to persons skilled in the art. Typically, the oxidation of butane to maleic anhydride is carried out by means of air or other molecular oxygen-containing gases such as mixtures of carbon dioxide and oxygen or mixtures of nitrogen or steam with air or oxygen. Air is preferred. The oxidation is carried out at temperatures of 350� to 500� C., preferably 400�-475� C. Preferably the concentration of butane in the feed will be 1.0 to 1.6 volume % with O2 above 10 volume %, and 1.5 to 5% with O2 below 0.10 volume %, and space velocities of 1000 to 4000 hr-1 are preferably employed in fixed-bed reactions and 500 to 2000 hr-1 in fluidized-bed operations. The reaction may be carried out at atmospheric, sub-atmospheric or super-atmospheric pressure, but substantially atmospheric pressure is preferred. Typically, the reaction pressure is about 1 to 7 atmospheres absolute. As previously mentioned, the reaction can be carried out in any reactor suitable for effecting vapor-phase oxidation reactions, but preferably the fixed catalyst bed is employed. The catalyst-containing tubes of such reactors can vary in diameter from, for example 0.25 inch to 1.5 inches and the length can vary from, for example, 6 inches to 10 feet or more. It is desirable to have the surfaces of the reactors at relatively constant temperature, and some medium to conduct heat from the reactors is desirable to aid temperature control. Such media include Woods metal, molten sulfur, mercury, molten lead and eutectic salt baths. A metal block reactor whereby the metals surrounding the tube act as a temperature regulating body can also be used. The reactor or reaction tubes can be formed from any convenient material, typically stainless steel or carbon steel.
Maleic anhydride prepared by using the catalyst of this invention can be recovered by any number of means well known to those skilled in the art. For example, the maleic anhydride can be recovered by direct condensation, or by absorption in suitable media, e.g. water with subsequent separation, dehydration and purification.
The following examples will serve to provide a fuller understanding of the invention, but it is to be understood that these examples are given for illustrative purposes only, and are not to be interpreted as limiting the invention in any way. In the examples, the terms "conversion", "selectivity" and "yield" have their conventional meanings in this art, viz ##EQU1##
A substrate containing phosphorus and vanadium is prepared by refluxing 500 grams of V2 O5 in 6500 cc of concentrated hydrochloric acid until the V2 O5 dissolves and the vanadium is now apparently predominantly in the form of VOCl2. Then 730 grams of 85% phosphoric acid is added and the resulting mixture refluxed in 4 hours. The final solution is then evaporated to dryness by heating in a glass vessel for approximately 5 hours at up to 200� C. The resulting dry solid is activated by heating it to 400� C. for four hours in a furnace in the presence of a continuous stream of air. The resulting powder is then formed into granules of approximately 14-18 mesh size by mixing the powder with a 4% aqueous polyvinyl alcohol solution and shaping, drying it at 110� C. and reactivating by heating at 400� C. for 2 hours in the presence of air. The substrate thus produced has a P/V atomic ratio of 1.15:1. This product is designated as substrate A.
Example I is repeated except that 41 grams of titanium tetrachloride is added to the solution obtained by refluxing the V2 O5 prior to addition of the phosphoric acid. The resulting substrate has a P/V/Ti atomic ratio of 1.15:1:0.04 and is designated as substrate B. Example I is again repeated except that 62 grams of titanium tetrachloride is added. The resulting substrate has a P/V/Ti atomic ratio of 1.15:1:0.06 and is designated as substrate C.
Substrate A is then treated to deposit zinc upon its surface in accordance with this invention by adding a solution of zinc chloride in formamide (10 ml) to 50 grams of the substrate A granules. The solution volume is just sufficient to fill the internal porosity of the granules and the thus-treated granules are then heated to 400� C. for 2 hours in a continuous stream of air to activate them. In this manner there are prepared three catalysts containing post-deposited zinc in the atomic ratios, per atom of V in the substrate, of 0.01, 0.03 to 0.12.
Example III is repeated except that instead of the zinc chloride solution, there is used in one case 0.8 cc of 85% phosphoric acid, and in another case, 8.6 grams phosphomolybdic acid in 10 cc of formamide. There are thus produced two catalysts, one of which contains post-deposited phosphorus in the atomic ratio of 0.05 per atom of V in the substrate, and the other of which contains post-deposited phosphorus and molybdenum in the atomic ratio of 0.01 P and 0.12 Mo per atom of V in the substrate.
Example III is repeated except that substrate B is used and the amount of zinc chloride used is such that the resulting catalyst contains post-deposited zinc in the atomic proportion of 0.04 per atom of V in the substrate.
Following the procedures of Examples III and IV but using substrate C, there are produced a series of catalysts containing various metals in various quantities post-deposited upon the substrate, some in combination with phosphorus and, in one case, in combination with boron, which is added in the form of a formamide solution of boric acid. The identity and amounts of the promoters are tabulated in Table 1.
Substrates A and B as well as the several catalysts comprising substrates A and B with post-deposited promoters prepared in Examples III, IV and V are evaluated for their activity in the oxidation of butane. For these evaluations there is used a 3/8" U-tube reactor immersed in a salt bath. In each case the charge or bed of the catalyst to be tested is 50 ml (approximately 40 g.) and the reaction is carried out at atmospheric pressure. A mixture of 1.5 volume % of n-butane in air is passed over the catalyst bed at a space velocity of 1200 hr-1. The salt bath temperature is held at approximately 450� C. for about eight hours to achieve additional activation, and selectivity and conversion to maleic anhydride are then determined over the range of 380� C. to 500� C. The results of these conversions are set forth in Table 1 below. In this table the first column identifies the substrate, and the second column identifies the post-deposited promoters and indicates the atomic quantity of the promoter per atom of V in the substrate. The third column shows the temperature in �C. at which 80 mol % conversion of butane is achieved. The fourth column shows the mol % selectivity to maleic anhydride at 80 mol % conversion and the last column lists the maximum weight percent yield of maleic anhydride.
TABLE 1______________________________________ Maleic AnhydrideSubstrate Promoters T80 S80 Yield______________________________________A none 500 47 65B none 470 47 68C none 460 47 68A .01 Zn 455 53 76A .03 Zn 455 55 77A .12 Zn 450 53 73A .05 P 485 48 70A .12 P--Mo 480 40 50B .04 Zn 460 53 76C .04 Li .05 P 455 47 65C .04 Na .05 P 460 48 72C .04 Mg 420 47 68C .04 Mg .05 P 415 58 83C .03 Al 410 55 80C .04 Al 405 58 85C .06 Al 430 43 60C .04 Al .05 P 435 53 76C .04 Ca .05 P 415 56 80C .04 Cr 410 54 80C .04 Mn 410 52 80C .04 Fe 410 53 80C .04 Co 410 48 70C .04 Ni 410 52 75C .04 Cu 425 50 70C .04 Zn 420 58 84C .03 Zn .05 P 420 62 88C .04 Zn .05 B 415 55 82C .03 Ga 420 53 78C .04 Ge .05 P 420 56 82C .04 Cd .05 P 450 45 70C .04 In .05 P 415 60 86C .04 Sn .05 P 420 53 76C .03 La .05 P 415 56 80C .04 U 425 48 68C .04 Ce 430 61 87C .04 Te 415 55 81C .04 Sb 430 55 80C .03 Bi 440 48 72C .03 Ga .02 Sb 415 57 85C .04 Zn .02 Sb 415 61 92C .03 Si 430 53 75C .03 Sc 420 52 77C .03 Y 420 52 77______________________________________
In order to compare the effect of a substrate having a surface-deposited promoter metal in accordance with the invention against a substrate having the same metal integrally incorporated in the substrate, several of the promoter metals listed in Table 1 are incorporated in the making of a substrate to provide substrates corresponding to substrates A and C, but, in addition, containing the integrally-incorporated metal. Thus, Example 1 is repeated several times and, in each case, there is incorporated in the solution a soluble salt respectively of magnesium, cadmium, manganese, iron, lanthanum, zinc and aluminum in an amount to provide an atomic ratio of 0.2 per atom of V. In like manner, Example II is repeated several times, and in each case, there is incorporated in the solution a soluble salt, respectively, of cadmium, tin, zinc and copper. In the case of tin and copper, the amounts of these metals used is in the atomic ratio of 0.04 per atom of V, corresponding to the amount of titanium in the substrate. In the case of cadmium and tin, these elements are used in the atomic ratio of 0.08 per atom of V, and the amount of titanium is also 0.08 per atom of V. Table 2 below lists the several catalyst compositions made as described above and shows the results of the tests for activity in oxidizing butane to maleic anhydride carried out in the manner described in Example VII.
TABLE 2______________________________________ Maleic AnhydrideCatalyst T80 S80 Yield______________________________________P/V/Mg 470 20 30P/V/Cd 480 40 60P/V/Co 450 45 65P/V/Mn 460 35 55P/V/Fe 500 20 40P/V/La 430 20 40P/V/Zn 460 52 75P/V/Al 460 30 50P/V/Ti/Cd 430 30 50P/V/Ti/Sn 450 40 60P/V/Ti/Zn 430 51 75P/V/Ti/Cu 455 45 70______________________________________
|Cited Patent
|Filing date
|Publication date
|Apr 17, 1974
|Jun 10, 1975
|Mobil Oil Corp
|Oxidation of alkanes to maleic anhydride using promoted vanadium-phosphorus catalyst
|Citing Patent
|Filing date
|Publication date
|Feb 16, 1982
|Feb 1, 1983
|E. I. Du Pont De Nemours And Company
|Vapor phase oxidation of n-butane to maleic anhydride
|Sep 22, 1982
|Apr 10, 1984
|E. I. Du Pont De Nemours And Company
|Catalyst for vapor phase oxidation of n-butane to maleic anhydride
|Sep 20, 1982
|Jun 26, 1984
|Monsanto Company
|Process for the manufacture of maleic anhydride
|Dec 22, 1983
|Oct 29, 1985
|E. I. Du Pont De Nemours And Company
|Process for making tetrahydrofuran and 1,4-butanediol using Pd/Re hydrogenation catalyst
|Jun 4, 1985
|Sep 2, 1986
|E. I. Du Pont De Nemours And Company
|Pd/Re hydrogenation catalyst for making tetrahydrofuran and 1,4-butanediol
|Jan 18, 1985
|May 26, 1987
|E. I. Du Pont De Nemours And Company
|Improved vapor phase catalytic oxidation of butane to maleic anhydride
|Oct 30, 1985
|Jan 31, 1989
|The Standard Oil Company
|Novel fixed-bed vanadium phosphate catalyst systems
|Jun 24, 1988
|Jul 4, 1989
|Amoco Corpration
|Process for the manufacture of maleic
|Aug 26, 1988
|Jun 4, 1991
|E.I. Du Pont De Nemours And Company
|Vapor phase catalytic oxidation of butane to maleic anhydride
|Dec 8, 1992
|Nov 15, 1994
|Huntsman Specialty Chemicals Corporation
|Catalysis for the production of maleic anhydride containing vanadium-phosphorus oxide with selected promoter elements
|Oct 2, 1995
|Aug 31, 1999
|Huntsman Petrochemical Corporation
|Molybdenum-modified vanadium-phosphorus oxide catalysts for the production of maleic anhydride
|Jan 16, 2001
|Jun 7, 2005
|E.I. Du Pont De Nemours And Company
|Vanadium-phosphorus oxide catalysts with promoter reagents
|Jan 16, 2001
|Feb 20, 2003
|Kostantinos Kourtakis
|Vanadium-phosphorus oxide catalysts with promoter reagents
|Jul 21, 2006
|Sep 18, 2008
|Basf Aktiengesellschaft
|Catalyst and Methods for Producing Maleic Anhydride
|May 19, 2009
|May 19, 2011
|Smith Ii Thomas S
|Mildly alkaline thin inorganic corrosion protective coating for metal substrates
|U.S. Classification
|549/259, 549/260
|International Classification
|Cooperative Classification
|European Classification
|Apr 17, 1987
Owner name: SCIENTIFIC DESIGN COMPANY, INC., A CORP. OF DE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HALCON SD GROUP, INC.;REEL/FRAME:004695/0962
Effective date: 19870415


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Oh Canada – you are feverishly preparing for the most eagerly anticipated sightseeing trip of the year. In exactly one day, William and Kate, aka the Duke and Duchess of Cambridge, will arrive in (according to the Government of Canada's very formal and complete itinerary) the National Capital Region.
We know a lot about the royal couple, but do they know much about you, Canada? I will speak to you as though you are a person, Canada. I expect you have prepared big, fat, boring briefing books for the royal couple, and that isn't fair, because those statistics are overwhelming. Keep it simple – make each city on the tour "come alive" in three simple phrases.
I will help you. More
Okay, think about how much the most expensive vacation you've ever taken has cost. Now double that… More
In a move that could radically change how Canada deals with prostitution, the Ontario Court of Appeals is hearing a case this week that could effectively legalize The Oldest Profession throughout the country, making all Canadian sex workers safer in the process. More
If I didn't know better, I'd say that the Canadian guy in this video got wasted and stumbled out into the street where he found a hot dog vendor, then decided to take those hot dogs and put everything he could think of in and around them in order to make a sandwich. More
A new beer bearing the incredibly appropriate name Utopias will be making its debut in Ontario next month. The beer, is brewed with a mix of different malts and a hint of maple syrup. It has a 27 percent alcohol … More

subset: commoncrawl


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Visit AILA's Advocacy Action Center
Make sure you're there this June to take advantage of an information-filled CLE program with over 170 substantive sessionsRegister Now
AILA Doc No. 13081303 | Dated August 13, 2013 | File Size: 131 KDownload the Document
Updates and facts on California's AB 1159, entitled the Immigration Reform Act, from the AILA California Chapters (Southern CA, Northern CA, Santa Clara Valley, and San Diego chapters), including a legislative history, advocacy update, lobbying, and an action plan.
[[To print the PDF on this page please use the print function in the PDF reader.]]
Cite as AILA Doc. No. 13081303.Open the Document
American Immigration Lawyers Association
1331 G Street NW, Suite 300
Washington, DC 20005
Copyright © 1993-2016
American Immigration Lawyers Association.


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Financial Assistance
An education at Luther College represents an intellectual and financial investment for both the Luther student and his or her family. Luther, as a college committed to Christian liberal arts education, recognizes a responsibility to provide students not only with a quality intellectual environment, but also with financial assistance when needed.
Luther believes that persons qualifying for admission should not be denied the privilege of attending this college because of limited financial resources. The college has, therefore, developed a program of financial planning and assistance to help students meet the cost of their education.


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Well met at this site, where you can find the most popular ringtones for your mobile phone. Today we have a ringtone of "Du bist es" by Kategorie C as well as 116 other ringtones by Kategorie C. "Du bist es" is a real hit from the "Deutsche Jungs" album that was recorded by Kategorie C at their studios together with other 8 tracks. You can listen to all 7 Kategorie C – "Du bist es" ringtone variations available here and download it for free in a click. You can also take a glance at other 1 albums produced by Kategorie C for all time. "Du bist es" is referred to Hooligan, and we can offer you a huge amount of Hooligan ringtones absolutely for free. And finally, we have collected lyrics for this track and you can view it here as well. So feel free to browse, listen, download ringtones at Audiko.net. Make your phone sound cool!
Kategorie C Du bist es Ringtone
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25 Self(ie)-Obsessed Celebrities: Look at Us!!!!!
Who doesn't love a good selfie, right?
Granted, Katy Perry says selfies are a disease - but, really, selfies are a sign of modern times. Or of the end of times. One of the two.
Who doesn't love a good selfie, right?
Granted, Katy Perry says selfies are a disease - but, really, selfies are a sign of modern times. Or of the end of times. One of the two.
During Game 5 of the Indiana Pacers vs. Miami Heat Eastern Conference finals last night, Lance Stephenson pulled out all the stops to keep his team from being eliminated.
First, he bizarrely attempted to sneak into a Miami huddle, then the Pacers guard pulled a maneuver that will live on in the annals of NBA history:
Think you are the biggest LeBron James fan on the planet?
Think again.
LeBron James shared a personal message to his father - who he's never seen or met - on Instagram this week, and it's not what you would expect. At all.
In discussing his life with GQ, James opened up about how the specific circumstances of his single-parent upbringing helped make him the man he is.
LeBron James' kids DESTROYED a Nerf hoop with an alley-oop slam dunk on Christmas, and dad was so proud, he shared the highlight on Instagram.
The basketball star's sons, 6-year-old Bryce and 9-year-old LeBron Jr. (a.k.a. "Bronny") certainly seem to have inherited some of their father's talent.
LeBron James and Savannah Brinson are newly married and enjoying their honeymoon in Rome, which the NBA star has been documenting on Instagram.
Savannah Brinson and LeBron James have tied the knot.
The couple, parents of two sons and sweethearts for the past 12 (!) years since, finally made it official at the Grand Del Mar hotel in San Diego, Calif.
Has LeBron James gobbled up Reggie Bush's alleged sloppy seconds?
According to a Bossip report, the basketball superstar exchanged some racy text messages with the model after spotting her at a Miami nightclub this month, although it's unclear if any bodily fluids were exchanged between the two.
LeBron James is apparently channeling his inner Jay-Z this offseason.
The Miami Heat star released a teaser on Instagram of himself rapping, and his rendition of Hov's "N--gas in Paris" is not the worst thing ever.
Drake was denied entry to the Miami Heat locker room yesterday evening in amusing fashion, but made up for the slight later by partying with the team.
The Heat finished off the visiting San Antonio Spurs in Game 7 Thursday, then polished off MANY bottles of champagne late into the South Beach night.
LeBron James is a four-time NBA MVP who dropped 32 pounds on the San Antonio Spurs last night as his Miami Heat evened the NBA Finals at two games.
But Chael Sonnen is unimpressed.
LeBron James' insane block on Tiago Splitter during last night's NBA Finals contest was the unquestioned highlight of the Miami Heat's Game 2 blowout.


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The San Francisco Wine Trading Company is more than just your local wine store. Since 1976 we have helped our customers make informed choices about wine purchasMore
$5 mil. - $10 mil.in Revenue
10 - 20EmployeesContact people at this company
250 Taraval StreetSan FranciscoCalifornia94116United Statesview map
(415) 731-6222
ProPub_Iteration_NT.411[02] SEIDXWK-22


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The Brooklyn Filmmaker's Collective, or BFC, was founded by filmmakers Landon Van Soest and Jeremy Levine. It's now a five-year-old informal but tightly knit group of about fifty local filmmakers who meet weekly to critique work that they have total creative control over.
Read the PostCurators of Creative Control, Brooklyn Filmmakers Collective is Building an Informal Peer Economy


text: The show that Barack and Michelle Obama attended on Saturday evening is benefiting nicely from presidential publicity. The number of advance tickets sold yesterday for Joe Turner's Come and Gone was triple that of the previous Sunday. Now the Obamas just need to attend a new show every week and Broadway will be back in business in no time. [NYP]


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Guns N' Roses frontman Axl Rose has endorsed US President Barack Obama, sort of.
Rose expressed his support for Obama during an interview on "Jimmy Kimmel Live" on Wednesday night, which was the rock star's first live televised appearance in 20 years, US Weekly reported.
During the interview to promote the band's upcoming residency at the Hard Rock Hotel and Casino in Las Vegas, an unusually jovial Rose discussed Halloween, his favorite bands, his pre-rock life as a manager of the Tower Video store on Sunset Boulevard and his tardiness, the Los Angeles Times reported.
Rose also expressed his support for Obama in the upcoming presidential election, even though he has never "really voted," the Wall Street Journal reported.
"Well, I'm in California, and it usually leans Democratic, and that's usually where I'm leaning anyway. And that's usually where I'm leaning anyway," Rose said.
"I would lean Democrat. I would lean Obama."
The full interview with Rose has been posted below.


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Best Restaurants in Myrtle Beach
Posted Nov 26th 2010 10:10 AMUpdated Jan 21st 2011 01:29 PM
Best Myrtle Beach Restaurant: Fine Dining Category
Just up the road from the beach on Kings Highway, the Aspen Grille has taken fine diners' taste buds by storm since owner and chef Curry Martin took the reins in 2009. Focusing on melding fine steak and seafood dishes with traditional Southern flair, the folks at Aspen Grille really know how to prepare and serve a meal. The restaurant is open seven days a week from June to August, so summer vacationers need not worry about going, only to find it closed. Looking at the menu reveals prices that you would expect out of a fine dining establishment, but such thoughts disappear once the food actually arrives. The delectable fried green tomatoes are an essential appetizer to any meal and go well with a medium body red wine. And with an extensive wine list, you're sure to find something pleasing. Enjoy a perfectly cooked prime ribeye or the seared sea scallops while listening to live jazz and piano music. All of the food comes with excellent service and helpful wait staff, soundly putting Aspen Grille on the map of best restaurants in Myrtle Beach.
Aspen Grille: 5101 North Kings Hwy., Myrtle Beach, SC 29577 (843) 449-9191
Best Myrtle Beach Restaurant: Moderate Category
The Baja Grill and Bar has only been open since June 2010, but it's already made a grand splash in the Myrtle Beach community. Nestled behind a Kings Highway gas station, you might miss this place if you drive by too quickly. However, it's relatively close to some of the more affordable hotels in Myrtle Beach, and it's easy to walk to.
The colorful and clean décor lends to the atmosphere without making it seem too pretentious or busy. The bar is welcoming, and the bartenders seem to make a genuine effort to help you out. Once you get to the menu, you may realize that it's somewhat simple, but this isn't uncommon with new businesses. In Baja's case, it works to their advantage. The talented chef O'Shell can focus on cooking up some of the best Southwest dishes you've ever tasted. Locals rave about the fish tacos and dirt cheap happy hour specials, and most are impressed by the consistent quality of all the food. With that kind of quality and few dishes over $10, Baja Grill and Bar is definitely one of the best restaurants in Myrtle Beach.
Baja Grill and Bar: 504 16th Avenue North, Myrtle Beach, SC 29577 (843) 213-1551
Best Myrtle Beach Restaurant: Budget Category
"The inside is less than desirable but the BBQ is amazing," said Justin on UrbanSpoon.com of Little Pigs Bar-B-Q in Myrtle Beach. You may be hesitant to accept those kind of words when considering a restaurant, but you definitely should reconsider. Serving up delicious barbecue for several years, Little Pigs knows how to consistently serve up good eats without all the glamor and very little damage to your wallet. Little Pigs has your typical side dishes to go along with the barbecue pork, including baked beans, coleslaw, and potato salad. While the hush puppies are merely ok, the crispy onion rings are well worth a look. Go with the classic $6.69 pork sandwich plate with two sides of your choosing. You can even carry out half-pounds and pounds of their delicious barbecue pork for serving up your own way. And as with most any barbecue, the sauce is an extremely important component. But don't worry: Little Pigs has a variety of sauces the locals rave about. With all the fanfare - despite the look - it's easy to see why Little Pigs is one of the best restaurants in Myrtle Beach.
Little Pigs Bar-B-Q: 6102 Frontage Rd., Myrtle Beach, SC 29577 (843) 692-9774
Photo by Sam Chan from Flickr
More Articles You Might Like
- Best Waterfront Restaurants in Myrtle Beach [AOL Travel]
- How to Complain Effectively When Traveling (Video) [FoxNews Travel]
- Top 20 Hottest Destinations of 2011 (Amazing Photos!) [National Geographic]
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People around the country will be staying up late for the chance to see something no human has ever seen before, the Camelo p ardalis meteor shower.
Once the sun sets you might start to see signs of an unparal l eled meteor shower.
That's what drove Luis Medina to the Headlands International Dark Sky Park for the weekend.
"Just having that many meteors in one spot , all at once seems like just a beautiful thing," Medina said.
Medina came from downstate to take pictures of the spectacle. Because the park has one of the clearest views in the state.
"T his is something you can see with the naked eye , you don't know need to know where it's coming from , you just need the dark s ky and a place to lay back and look," Mary Stewart Adams, Dark Sky Park Program Director said.
I t's called the Camelopardalis or the more common name, the True North Meteor Shower.
A stronomers say this event was birthed from a comet first spotted back in 2004.
"W hat's happening when we have a meteor shower is that the Earth is moving to the path of stuff that is left behind when a comet comes through our system," Adams said.
T he best time to see the shower will likely around 3 a.m. and to view it you must be looking east.
"T he predictions are getting pretty wild , upwards of 200 meteors an hour," said Adams. "Some are saying even saying between 400 to 1,000 and that's unparalleled. Whether or not that happens will just have to wait and see."
I f you're lucky you might be able to spot another rare sight.
"S ome of the predictions are if we are seeing meteors showers, if you have a telescope trained on the moon , some of them might be hitting the moon as well , which would be spectacular to see ,"said Adams.
I f you'd like to see the True North Meteor Shower the Headlands International Dark Sky Park is holding a viewing event Saturday morning.
Participants will be gathering near the entrance of the park at 3 a . m.


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A Kingston Centre member and active variable star observer. Chilton Prize 1979. Chant Medal 1986.
(1952-) A longtime unattached member of the Society, and organizer of the 1989 General Assembly.
The Royal Astronomical
Society of Canada
203-4920 Dundas Street West
Toronto ON M9A 1B7
Phone: 1-888-924-7272
Phone: (416) 924-7973
Fax: (416) 924-2911
Contact Us


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Helen Ford Wallace: Parties, Etc.: Sept. 2
Volunteer recruitment: A volunteer recruitment party for 300 Oklahoma City young professionals was held by The Arts Council of OKC at the Farmers Public Market. The party was themed "First Date With The Arts Council."
Invitation: A colorful invitation stated "I've seen you around at rooftop happy hours, volunteering on your days off and networking with other young professionals & I've got to say … I like your style." It added, "Worried about the commitment involved in this potential relationship? No need to fret: I promise to lay it all out on the table — quite literally … hopes & dreams. You & Me … Bringing the arts & the community together."
Entertainment: Live music was from Urban Addiction, and Performances by OKC Improv was the entertainment.
Success story: Executive Director Peter Dolese spoke about the yearly Arts Council events and more than 200 new volunteers signed up to help with the Festival of the Arts, Opening Night and Oklahoma City Storytelling Festival.
Food: Food was provided by VZD's, Deep Fork Catering, Tapwerks, Ale House & Cafe, Brown's Bakery, Texadelphia and Schlotzsky's.
Seen: Britnee Bryles, Brent Skarky, Travis Mason, Trent Lawson, Tony Lacy, Kati Christ, Daniel Adams and Anita Baker.
Party: A wine, cheese and recipe shower was given for Anne Heatly. Hostesses were Patty Anthony, Joanie Holmboe, Peggy Duncan, Pat Northwood and Jamie Taylor in the Taylor home.
Gift: 100 guests filled a recipe box with 100 recipes for the bride-to-be and hostesses gave her a recipe box with her new monogram. All the recipes were on matching monogrammed cards. They also gave her an apron, cookbooks, cooking utensils which were used in the centerpiece, along with blue hydrangeas and white lily of the valley.
Wedding: Anne Heatly and Jeff McQueen will be married this month.
Seen: Marianne Rooney, Roberta Roush, Cindy Rapp, Susan Love, Kim Joseph, Alison Calhoon, Susan Drake, Kingsley Burke, Mary Sims, Janie Law, Nancy Law and Jane Christiansen.
Occasion: Dorothy and John Kelly were honorees at a 50th anniversary brunch given by Jane Kelly and Brent Brewer in Jane Kelly's home.
Fun facts: The Kellys have been in the bridal business in Oklahoma City for 33 years, and Dorothy Kelly, from New Orleans, was queen of a Mardi Gras Ball that had the theme "A Royal Wedding." The couple were married in New Orleans.
Guests: Among the guests were family members and friends including Jill Kelly Elliott, Jimmy Elliott, Anna and Emma Elliott, Jack Ablett, Barbara and Patrick Kelly, Abby and Joseph Kelly, John Kelly, Lenell Kelly Gilbert, Kim Angle, Kathleen Strain, Sherri Alexander.
Decor: The seated brunch featured gold lame brocade tablecloths, gold chairs, gold-rimmed glasses and votive candles and bouquets of white hydrangeas.
Menu: Champagne mimosas were served to the guests and the brunch menu included filets, layered salad, potato casserole and Jane's famous white chocolate creme Brule.
Gift: The children gave their parents a turquoise chandelier.
Event: Carol and Gary Sander were hosts for the first Oklahoma Senior Follies Friend-Raiser. Speakers were Bobbie Burbridge Lane, founder and producer of the Follies, Carol Sander and Linda Piro, co-chairmen, Follies Friends. It was announced that the kickoff meeting for volunteer members and prospective members will be Oct. 3. Also the Oklahoma Senior Follies for 2013 will be June 14-16. The group is the volunteer organization of the Oklahoma Senior Follies.
Tables/menu: Bouquets of roses, lilies and daisies were on the tables and wine, tea, soft drinks and cheese and hors d'oeuvres were served.
Seen: Lou Ann Rice, Kerry Robertson, Jane Hall, Liz and Stan Alexander, Lolly Anderson, Suzie and Jim Fentriss, Jay Edwards, Terry Runnels, Virginia Wright, Jim Franklin, Betty Catching, Charlotte and Jim Franklin and Barbara Hensley.
Event: The Edmond Women's Club met to learn about the inaugural ambassador program in the home of Leigh Thompson. Fifteen high school girls were selected for the program and will complete 10 hours of community service projects with EWC members in the Edmond community. The students are from Edmond North, Edmond Santa Fe, Edmond Memorial and Deer Creek schools.
Purpose: The mission of the program is to educate and motivate young leaders for active roles in the community.


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"Dominican Republic" Top 5 Page for this destination Dominican Republic by micas_pt
Dominican Republic Travel Guide: 3,022 reviews and 6,817 photos
Reviews (42)
In Higuey it is worth mentioning the Cathedral, the city's main must see. Seen from the outside the Cathedral looks like... more travel advice
Higuey is a city situated somewhat near Punta Caña, and it is the capital of La Altagracia Province. We ventured on a... more travel advice
This family, as many others, also grows their own coffee. When coffee beans are mature they put them into to oven to... more travel advice
Cocoa "fruit" grows from the trees. In this photo you can see that they grow in a different way, .. .well, I found it... more travel advice
Shopping (5)See All The prices
Transportation (3)See All Bus
Local Customs (8)See All Currency
Comments (64)
Great beaches, but it's good that you also explored the interior of the island. If C.C. were alive today I think his PR advisors would tell him to use the Portuguese version of his name, Cristovão Colombo, because it sounds much more seafaring.
Micas, fantastic page with loads of sun here. I think I could also live with an average temperature of 26 ºC and 13 hours of sun, although I do need some snow in winter for cross country skiing.
comprehensive page on a relaxing location + I could do with some of this
May be going to DR for 5 days in February with my sister and know nothing about it so visited your wonderful pages. Thanks so much for valuable information.
Very helpful DR tips !! Getting ready to go there next month and am very excited after seeing your pages! Well done !!
Congratulations on being a featured memeber. Great pages on Dominican. We were there in 1989 when Hurricane Hugo struck the area.
I'm glad you had fun in my country and that you experienced some of the culture :)
Hello & thank for you for sharing your great tips & photos! I very much enjoyed reading your pages. Where was the last country you travelled to? I went to Scotland this summer and absolutely loved it! Greetings from the desert / Jess :-)
We are considering a visit here. Thanks for the great tips and photos!
I had no idea the Dominican Republic was so pretty!
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- Top 5 Page for this destination Portugal Intro, 97 reviews, 95 photos
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- Bratislava Intro, 32 reviews, 32 photos


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Little Fuzzball by juddpattersonWatch
©2009-2016 juddpatterson
This cute little fuzzball was exploring the beach back in May 2008...it is only a week old and about 2.5" tall. I did research involving Snowy Plovers in Utah, but this was my closest encounter with the tiny chicks. They are so brave as they run around catching insects.
Oh my, it looks so funny! >3<
Oh. My. God. Cuteness overload!! Excellent capture
Looks like Snowy Plovers need to get more sleep.
Wow, that thing is tiny - and comical-looking too, because of the oversized head. A nice capture of a cute little creature.
The white gives a sense of heavenly feel and fragility.
Beautiful focus, really nicely taken Judd
This is really awesome. No SP's by me, but we have piping plovers, and the chicks look nearly identical to this one. Absolutely flawless, I love this shot.
So fragile.
Cool! Did you blur the ground in the front in Photoshop? Or did you take the picture that way?
No blurring in Photoshop...just OOF from the very shallow depth of field from a long lens and extension tube (to decrease the close-focusing distance).
So adorable *.*'
Wonderful! So cute
that is adorable!
absolutely great photo
Adorable, I've always wanted to know what a baby Plovers looked like
That's cute, so tiny with long legs.
Wow, this is incredible, I love the composition, and the great detail in its fur.
Oh My that cute!!!! Wow, I love the colour and what you got in focus!! great shot!!!
You should swing by my Gallery some time, I would love to hear what you think of my stuff, no pressure!
You should swing by my Gallery some time, I would love to hear what you think of my stuff, no pressure!
Man, what a great photo!
I love these understated shots, the white on white composition is truly beautiful.
I love these understated shots, the white on white composition is truly beautiful.
I like how there isn't much contrast between the bird and it's surroundings (I'd usually say differently for wildlife!). All the white makes it such a soft image. The focus is perfect.
incredible capture, spot on focus!
ahahah amazing!!!
What a cutie!!!! !!! Great picture of it!!
That's so cute and TINY! Great close-up shot.
Aww, it's so cute.


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At least three people were killed and others were injured Saturday when Hamas and Israel disregarded a pledged cease-fire and resumed strikes on both sides of the Gaza border. The chief of the Israel Defense Forces called a meeting of military officials to determine the next course of action.
TEL AVIV, Israel — Despite a pledged cease-fire agreement between Hamas and Israel, strikes resumed on both sides of the Gaza border on Saturday, killing at least three Palestinian men and a 6-year-old boy in Gaza, and wounding an Israeli man in Sderot, officials said.
Signaling the seriousness of the renewed fighting, the chief of the Israel Defense Forces called an urgent meeting of senior military officials during the Sabbath to "determine the next course of action," according to a military spokeswoman, speaking on the condition of anonymity in line with regulations.
On Saturday afternoon, the armed wing of Hamas, known as the Qassam Brigades, promised to continue firing rockets in response to the Israeli airstrikes. "If the last round of confrontation … was not enough to deter the occupation," it said in a statement, "we are ready to break its arrogance, stop its crimes and respond to its aggression." But a few hours later, Israel's Channel 2 news reported that a new Hamas cease-fire would begin Saturday night.
The renewed fighting comes just after the fifth anniversary of Hamas' taking of full control of the Gaza Strip, and amid an internal struggle for leadership of the party. Until last week, Hamas had largely adhered to an informal cease-fire for more than a year, though other militant Palestinian factions had frequently fired rockets into southern Israel. This latest flare-up began Monday with the killing of an Israeli construction worker building a fence along the border with Egypt.
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Israeli military officials said 24 rockets fired from Gaza hit southern Israel on Saturday, part of a weeklong barrage of more than 150; 10 were intercepted.
A school and factory were among the sites hit, as officials urged residents to stay indoors.
Israel struck two Hamas sites in the northern Gaza Strip and one in the south on Saturday .A military spokeswoman said two suspected terrorists "about to launch rockets at Israel" were directly targeted in separate attacks.
Palestinian officials said the first attack killed Khaled al-Buri, who was affiliated with the Popular Resistance Committees, a group loyal to Hamas that claimed responsibility for firing dozens of rockets and missiles into Israel in recent days. The second attack was apparently aimed at a motorbike rider in Gaza City. But witnesses said he escaped unharmed, while the rocket hit an apartment building, sending bricks onto the street that killed Osama Ali, 42, and wounded 10 others.
And Saturday morning in the southern Gaza town of Khan Yunis, witnesses said, an Israeli artillery shell killed Ali al-Shawaf, 6, and wounded his father, who died later in the day.
Lt. Col. Avital Leibovich of the Israeli military said on Twitter that the boy had died in an explosion of Palestinian ordnance.


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Deadly storms rip through Midwest, South
POSTED: 3:29 PM Apr 15 2013 UPDATED: 5:28 AM Apr 13 2013
Text Size:
Powerful storms swept across the country this week, dumping snow in the north central and northeastern U.S., torrential rain in the Ohio and Mississippi valleys and even spawned tornadoes in the South. Take a look at images of the damage.
The views expressed are not those of this site, this station or its affiliated companies. By posting your comments you agree to accept our terms of use.


text: Posted 3 May 2010 that's right, make light of it, but stuff like that happens in part because people are made fun of in general, rejected, and feel like they're all alone. i was just using an extreme example to make a point. that's exactly the kind of response i'd expect from folks like you though. make everything into a joke and an insult. what exactly happened in your life to make you that way? you should figure that out and fix it so you don't pass on your depression to others with your words and actions. Share this post Link to post Share on other sites


text: NEW YORK, NY - FEBRUARY 13: Alan Anderson #6 of the Toronto Raptors celebrates at the buzzer after the game against the New York Knicks on February 13, 2013 at Madison Square Garden in New York City. The Toronto Raptors defeated the New York Knicks 92-88. NOTE TO USER: User expressly acknowledges and agrees that, by downloading and/or using this photograph, user is consenting to the terms and conditions of the Getty Images License Agreement. (Photo by Elsa/Getty Images)


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The Drive Home - SATA Comes To Brownsville
Suspicious Fire Rips Through Edinburg Mansion
Flames tore through the Edinburg mansion once owned by the late singer-songwriter Joan (ho-AHN) Sebastian overnight, and investigators say it appears someone set the fire. Firefighters were called a little after midnight and found the house on Brandi Lane engulfed in flames. Fire crews fought for more than an hour to put out the blaze. […]
California Lawmakers Vote To Allow HIV-Infected Organ Transplant
(AP) – California Gov. Jerry Brown plans to sign emergency legislation that would allow a man with HIV to receive part of his HIV-positive husband's liver before the surgery becomes too dangerous, possibly within weeks. The state Legislature rushed to approve the measure Friday. Brown spokeswoman Deborah Hoffman said the governor will sign the bill […]
(AP) – Brazilian police say they have identified and issued arrest warrants for four of the more than 30 men being investigated in the gang rape of a teenage girl. The case came to light after attackers posted pictures and videos of the assault on the unconscious teen on Twitter, and has shocked people across […]


text: I have downladed a game virtua tennis and the file is in mdf format. I have extracted the files from that file in another folder using power iso and installed the game. The game demands dvd to be inserted in order to play the game. As i have downloaded the game from internet i dont have any dvd. Secondly, if however, i write that file on dvd, my laptop doesnt have dvd rom. Tell me what should i do to play the game.


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Robo-Chicks Win!!! by Robo-Chicks - 6 months ago
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Udderly Good Times by Emma - 9 months ago
"Pictured here are 17 of 20 family members who had an "Udderly Good Time" visiting a friend's Cattle Ranch outside of Savannah, GA. We surprised the hosts of the weekend with the shirts and they we..."View full details
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220.127.116.11.J A Z Z by RIM Summer Intensive 2015 - 10 months ago
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C3VBP by C3VBP - 11 months ago
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Melanoma Walk Campen's Clan by Jamie - 12 months ago
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SHAM"RR"OCK ECLIPSE by SAVANNAH RUFF RYDERS - about 1 year ago
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Team Mona by Mona - about 1 year ago
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We decided to book Rushton Hall Stableyard Spa for our spa day as we had previously enjoyed afternoon tea in the courtyard in the summer. We were greeted with warm friendly faces and shown around when we arrived.
We slipped into our robes that were provided in our locker with a clean towel and slippers, and then caught up with the girls over a cup of tea in the peaceful lounge area, and waited for our treatments to start.
I enjoyed a relaxing full body massage and facial. The therapist was polite and friendly, and listened and advised me on all my skincare concerns. After 2hours I felt like I was in heaven- the heated beds, candles and mood lighting really made it extra special.
After floating out of the treatment room we got changed and headed down to the main hall for our delicious 2 course lunch. We even treated ourselves to a few glasses of champagne!!
With our tummy's full we made our way back to the spa and enjoyed a leisurely swim in the beautiful pool and went in the sauna and spa pools. We then had our luxury manicures and pedicures and fell asleep on the loungers by the poolside while our polish dried.
We finished our day with another glass of the champagne and treated ourselves to some lovely products.
Unfortunately I was too relaxed on the day to use the gym but I was very impressed with the equipment and am now thinking of becoming a member.
We really enjoyed our day and I would recommend the spa to anyone that wants a more personal spa experience!!
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STARmeterSEE RANK
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Frederick Volpe (1865–1932)
Frederick Volpe was born on July 31, 1865 in Liverpool, England. He was an actor, known for The Adventures of Mr. Pickwick (1921), The Wrong Mr. Perkins (1931) and Les cloches de Corneville (1917). He died on March 6, 1932 in London, England. See full bio »
Born:in Liverpool, England, UK
Died:(age 66) in London, England, UK


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The New Politics of Education
DURING THE DECADE AFTER 1965, political pressures converged on schools and universities in ways that undermined their authority to direct their own affairs. New responsibilities were assigned to educational institutions, even as effective authority was dispersed widely among students, faculty, unions, courts, state and federal regulatory agencies, state legislatures, Congress, the judiciary, and special interest groups. Educational administrators found themselves in the midst of unfamiliar power struggles. In colleges and universities, students demanded enlarged powers over the curriculum and the structure of governance; the courts and federal civil rights agencies required adherence to affirmative action programs to increase the representation of minorities and women on the faculty; faculties organized into unions; Congress, the courts, federal agencies, and state legislatures devised burdensome and costly new mandates. In elementary and secondary schools, almost no area of administrative discretion was left uncontested: students demanded new rights and freedoms; teachers' unions asserted a new militancy; political-action groups complained about books in the classrooms and libraries, for reasons of sexism, racism, or immorality; the courts ordered the busing of students in many communities, as well as reassignment of faculty, to achieve racial integration; Con


text:
Fixed PriceDelivery by December 5, 2012
I need a simple PHP script that:
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I should be able to call this script from a URL and provide an image through a GET request and get an image in return from the script that has the overlay.
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"Kathmandu, revisited" Top 5 Page for this destination Kathmandu by PierreZA
Kathmandu Travel Guide: 960 reviews and 2,769 photos
The early evening was cold and dark when we stood outside the airport waiting for our transport to Thamel. After a few minutes we were offered hotels, treks, excursions etc by the many touts around the airport. This was my first visit to Kathmandu and I was looking forward to explore a new city and country.
The first evening we met up with South African friends who are living and working in the Middle East. They have been to Nepal many, many times. We met at the Four Seasons Restaurant. During the first few hours of my stay in Kathmandu I experienced the very busy streets of Thamel, friendly waiters, power black outs, good food, South African wine, touts etc.
We stayed at Kathmandu Guesthouse, which is in the middle of Thamel. On arrival we had to move to a different hotel for the first night as they had a problem with a group of guests who needed to stay an extra night. At least we were upgraded fro the rest of our stay.
Despite being winter (December), it was not that cold and during the day it was possible to walk around in T-shirts. Although the days were a bit short, it was not a problem and I would visit during December again.
So, I just returned from my second visit to Kathmandu (March 2011) - and had a great time! This is such a magical, special city. Experiencing Holi in Kathmandu was a great bonus - the local people are great.
I would like to thank Songsong, my guide during this visit - for making it even better than the first visit!
There is a lot to do and see in Kathmandu. The ancient buildings in Durbar Square and the surroundings are one of the highlights.
Experience Buddism and Hinduism, almost intermingled. Visit Swayambhunath where the Monkey Temple sits high overlooking Kathmandu.
Even more impressive is the huge Stupa at Bodnath. Here you will see many Tibetans, monasteries, shops selling a wide variety, Buddhist monks etc.
The Hindu Temple at Pashupatnath gives a good idea of the Hinduism in Kathmandu. It is here where you will see the huge fires for the cremations on the banks of the Baghmati river.
Thamel with its many restaurants, bars, hotels, touts, taxis, shops etc is touristy, but fantastic.
Patan is almost part of Kathmandu, and you city you have to visit.
An amazing Durbar Square and other beautiful sights.
I enjoyed walking around, meeting the very friendly people, getting to know how they experience the city and learning what living in Kathmandu is about.
I would like to return to this great city. It is unfortunate that here are so many young people from Nepal wanting to leave the country for better opportunities. I do hope they will return to this wonderful city and country.
It is very easy to do day trips to great places in the Kathmandu Valley using the city as a base.
Bakhtapur is a must visit! It has become a bit expensive, but the money is used to keep this UNESCO world heritage city in a great condition.
Reviews (29)
You can buy in Kathmandu Good variety found in Kathmandu at good prices Can find what you need Do bring a torch light... more travel advice
Changu is in the Bhaptapur District. The main attraction is the Changu Narayan Temple. Some structures dates back to... more travel advice
What a great time I had in Kathmandu with the Holi Festival. It is a public holiday and people are just enjoying... more travel advice
What a great time I had in Kathmandu with the Holi Festival. It is a public holiday and people are just enjoying... more travel advice
Transportation (5)See All Emirates connecting with Flydubai
Restaurants (2)See All A good variety, including Nepali dishes
Shopping (3)See All Clothing
Nightlife (1)Meet locals and relax
Hotels (2)See All Not that good
Been to Kathmandu?Share your travels with the world!
Comments (9)
wow pierre you liked kathmandu, i love SA especially-cape town, garden route and durban in SA ...comming soon..
~ Hello, Pierre! Great trip! The capital is impressive indeed..... Thanks for sharing!~
Interesting page with a lot of useful info.
I would love to visit Kathmandu and when I do plan a trip I'll certainly come back to your informative tips. The Buddha Bar sounds great :-) Good hotel and shopping advice too - thanks!
Nice new additional tip,Pierre!
You did a great job in discovering Nepal. I have enjoyed your tips and photos.
Hi Pierre. Great page. Looks like an interesting place to visit. Greetings, Klaus
Hi Pierre, I enjoyed reading your informative tips. Best. Laszlo
Pierre, thank you for visiting my Kathmandu page of my visit of almost 20 years ago. Keep me informed when you have built your page. I am interested in your recent experiences.
PierreZA's Related Pages
Kathmandu Travel Guide
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- "Kathmandu The Ancient City - Dream Destination."
- "Kathmandu"
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- "Kathmandu, revisited"
- "Kathamandu:A cultural heritage city"
- "The himalayan country"
- See All...
- Things to Do in Kathmandu
- Hotels in Kathmandu
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- Warnings and Dangers in Kathmandu
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This indicator measures the extent to which the workforce in a state is employed
in high-technology industries. High-technology industries are identified as
those with at least twice the share of employment of the all-industries average,
in both research and development in all technology occupations.
State economies with a high value for this indicator are probably well positioned
to take advantage of new technological advances because they have a relatively
larger pool of experienced high-technology workers. Because of a recent shift
in the industrial classification system, this indicator covers only 1998–2000.
National Science Board
National Science Foundation, Division of Science Resources Statistics
Science and Engineering Indicators 2004
Arlington, VA (NSB 04-01)
[May 2004]


text:
: Discontinued:
Pokémon Shiny Gold!
View Single Post
October 4th, 2008 (4:42 AM).
The chase is about to begin...
Join Date: Apr 2008
Location: Lisbon, Portugal
Nature: Quirky
Posts: 103
Originally Posted by
I love this idea! My problem is I can't seem to save my progress. In the beginning, it says the 1MB circuit board is not installed. And when I try to save, it gives me a save error and tells me to exchange the backup memory. So how do I do that? Is it a problem with the ROM?
I even tried saving a battery file with the VBA, and that didn't work either.
In VBA: Options>Emulator>Save>Flash 128k
should work
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text:
- ParaguayFoodFunding via Fundación Paraguaya
Divino Niño...ParaguayClothingFunding via Fundación Paraguaya
Un Nuevo Am...ParaguayRetailFunding via Fundación Paraguaya
Kuña Guapa Group
Hermelinda owns a small grocery store. She reports that she has many customers from her neighborhood and surrounding areas and there is a lot of demand for all kinds of products. She says that she would like to expand her store so that her business can keep on growing and her customers can be more comfortable. She says that everything she does is for the well-being of her family and of those who depend on her.
She requests this loan in order to purchase goods such as foodstuffs, beverages, etc. to stock up her store. She thanks the Fundación for the opportunity she is given, because getting the loan will be a big help.
La señora Hermelinda tiene una despensa, comenta que tiene muchos clientes que son de su barrio y de zonas aledañas, tiene mucha demanda de todo tipo de productos. Comenta que le gustaría ampliar su local para poder seguir creciendo y de esa forma también ofrecer mayor comodidad a sus clientes. Dice que todo lo que hace es por el bien de su familia y por aquellos que de ella dependen.
Ella solicita el crédito para la compra de mercaderías, como ser comestibles, bebidas, y otros para el abastecimiento de su local. Agradece a la Fundación por la oportunidad que le da, ya que de obtener el crédito, este le será de mucha ayuda.
Additional Information
About Fundación ParaguayaFundación Paraguaya is a financially self-sustaining social enterprise that promotes entrepreneurship in urban and rural areas through microfinance, education programs, and more. Its focus on agriculture has helped many farmers boost their crop yields. And a number of other borrowers have taken out loans to start and grow social businesses that have helped deliver eyeglasses, medicines and other helpful services in their local communities.
This is a Group Loan
In a group loan, each member of the group receives an individual loan but is part of a larger group of individuals. The group is there to provide support to the members and to provide a system of peer pressure, but groups may or may not be formally bound by a group guarantee. In cases where there is a group guarantee, members of the group are responsible for paying back the loans of their fellow group members in the case of delinquency or default.
Kiva's Field Partners typically feature one borrower from a group. The loan description, sector, and other attributes for a group loan profile are determined by the featured borrower's loan. The other members of the group are not required to use their loans for the same purpose.
About Paraguay
52View loans »
Success!! The loan was 100% repaid
- Repayment Term
- 6 months (Additional Information)
- Repayment Schedule
- Monthly
- Pre-Disbursed:
- Jul 22, 2011
- Listed
- Sep 3, 2011
- Currency Exchange Loss:
- Covered
- Ended:
- Dec 15, 2011


text: I previously have an vigorous DP-DVI adapter session here. After that I discover out that Infinity requirements Windows Vista or 7 to run. However I still own on a windows xp cd and I have I am using this many other with the same. I am also in to software programming so I need to use multiple computer so that I can get better control of the software that are installed on that system. BUT somehow I am not been able to set up this as I dont have this any knowledge about that.


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Suspicious package leads to Conway elementary school evacuation | News
CONWAY, Ark. (KTHV) - An elementary school in Conway was evacuated due to a suspicious package donated to the school Monday.
The package, a black backpack, was donated to Marguerite Vann Elementary by an unknown man. We're told after the man left, the principal opened the backpack, and noticed suspicious wiring attached to it.
"This backpack and the wires that they saw was a part of hook-up, that you can use to hook-up your MP3 player or music-listening devices. These wires were made into this backpack," says Latresha Woodruff with the Conway Police Department.
So, as it turned out, new technology prompted the evacuation. As far as the person who donated the backpack, it is still unknown at this point.
Woodruff says it's understandable why school officials acted in the manner, as it is better to safe.
The students were evacuated for an hour and 45 minutes.


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Only had an hour today. WRI's up a hill. check. Limp home. check.
Rode in to work today. Legs felt really, really good. Only took 30 minutes or so, but Z5 didn't feel like Z5. This is a good sign for races this weekend.
2 hours
Well - two deep tissue massages in a week, 7 days of 6,000+ calories, a playlist full of Disturbed and Godsmack, two eager spotters and 10/10 motivation tells me I try to squat 655 tomorrow morning.
Wish I was posting about a group ride but alas...
"if you ride it the way it's meant to be ridden there's no way any wife is less of a ***** than a bicycle." - gstein
2 hours zone 1.5 yesterday.
About to go home, do an hour w/3x sets of crit intervals, and clean up my bike. I'm currently 75% leaning towards driving over to Tallahassee in the morning, paying my $28, and getting my ass handed to me in the p/1/2 road race. But it'd be a great test to see how I've done in going from zero to something in the past two months before racing starts up.
Oh yeah, my allergies are killing me.
Putting the Duh in Floriduh.
1:20 of Z1 HR - endurance power. A little sore from yesterday's work, but not too bad. I'm stinky and need a shower.
A quick ride through a local very hilly park with teammates. No real structure, except to light it up on the climbs and see how it goes. PRs across the board, which is nice, but I need to get faster still. First race in four weeks.
The Honest Bicycle Program - Heady talk about bikes, bike racing, bike racers and bike riding. standarddouble.com/whbp
Openers on the bike path down by the river.
Cyclists of the world, unite! You have nothing to lube but your chains!
Watch out for Matt.
45 minutes on the commute into work this morning with temps about 20F, 1:45 on the way home with 35F. I'm still cold, I haven't quite figured out how to keep my toes warm.
Work has been nuts this week so my ride time has been effectively zero. Haven't touched a bike since Sunday.
Doing this tonight. Because basemiles.
i will be there for sure.
i havent stopped riding. still commuting 25 miles a day and still doin a lot of long rides.
i just havent had any structure until the last few weeks.
frostbite is usually a really good benchmark for me as it usually works out as the end of my base period and the beginning of build, so its a good indicator, but this year its gonne be ugly.
Last "real" training day on the bike was in spring 2011. 2 years off, lots of running and a shoulder surgery later (thanks mountain biking), I'm on the road to racing again. I'll officially be back on the bike in May after I finish a spring of running (training legs). Spent the last week unseizing a seat post in my Blue RC8, buying a new FSA zero set back and ordering a new headset for the RC8 that hasn't been ridden in 2 years. Hope to be joining the fray in the Arizona November with some sense of fitness, hoping to make another RAAM attempt in 2014.
At least I get sun year round while staring at the Blandscape of Arizona.
Envision, Energize, Enable
Cool badhat, see you out there, if it's not blowing >30.
I'm trying to get psyched for 1:30 of tempo + some v02Max intervals.... it's 28 degrees out there, brr.
3 hour hammer fest at the Shootout. This ride makes the last Cat5 Crits I have been in recovery rides.
Welcome back!
Putting the Duh in Floriduh.


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Afraid to drive/purchase this vehicle since timing belt should have been replaced at 60k mi and no has 91k. Knowing the belt could snap at anytime and cause major repairs and expense. But if we are going to replace the timing belt, should the water pump be replaced at the same time, and are there any other belts that should be replaced while it is undergoing this service. Thank you.
by jhawkins in Deltona, FL on July 10, 2013


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Eugene Richards
Nelida Bagley helps to lift her son, former Sgt. Jose Pequeno of the New Hampshire National Guard, from his bed at the West Roxbury VA Medical Center on March 21, 2008 in West Roxbury, Massachusetts.
Thirty-four-year-old Pequeno, the chief of police of Sugar Hill, New Hampshire, lost forty percent of his brain after a grenade exploded in his Humvee while on patrol in Ramadi, Iraq on
March 1, 2006.