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A catalyst and process for opening aliphatic cyclic hydrocarbons have been developed. The catalyst comprises a catalytic metal component, a molecular sieve and refractory inorganic oxide component. The molecular sieve is selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof. Preferred catalytic metals include platinum, palladium and rhodium. The catalyst may also contain a modifier such as niobium, titanium, or rare earth metals.
1. A process for producing acyclic paraffins from cyclic paraffins comprising contacting a feed stream comprising cyclic paraffins with a catalyst comprising a catalytic metal component, a refractory inorganic oxide component and a molecular sieve characterized in that it has an OH peak shift in its CO FTIR spectrum of less than 310 cm−1 and is selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof at ring opening conditions to convert at least a portion of the cyclic paraffins to acyclic paraffins.
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12. A catalyst for opening cyclic paraffins comprising a catalytic metal component, a molecular sieve characterized in that it has an OH peak shift in its CO FTIR spectrum of less than 310 cm−1 and a refractory inorganic oxide component, the molecular sieve selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof.
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This application is a continuation-in-part of copending application Ser. No. 10/704,485, filed Jul. 11, 2003, and which is incorporated by reference in its entirety.
This invention relates to a catalyst for the selective ring opening of cyclic naphtha which comprises a catalytic metal component, a molecular sieve and a refractory oxide component. The molecular sieve is selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof. Optionally the catalyst may contain a modifier. This invention also relates to a process for selective ring opening using the catalyst.
Olefins are used in various reactions to produce important chemical compounds. Accordingly, demand for olefins is ever increasing and therefore new processes or increased efficiencies in existing processes are required. One of the main processes used in preparing light olefins is naphtha steam cracking. It is known that the efficiency of steam cracking depends on the specific composition of the naphtha feed. Specifically it has been demonstrated that converting naphthenes to acyclic paraffins, e.g. n-paraffins significantly improves olefin yield from the steam cracker. There is, therefore, a need for an improved ring opening catalyst.
Improved ring opening catalysts are also necessary because of increasing demand for environmentally friendly products and clean burning high performance fuels. In this case naphthene rings are opened to give acyclic paraffins which in turn can be isomerized. These isomerized paraffins have improved characteristics than the corresponding naphthenes.
An increased amount of paraffins is also required in providing reformulated gasoline. Reformulated gasoline differs from the traditional product in having a lower vapor pressure, lower final boiling point, increased content of oxygenates, and lower content of olefins, benzene and aromatics.
Reduction in gasoline benzene content often has been addressed by changing the cut point between light and heavy naphtha, directing more of the potential benzene formers to isomerization instead of to reforming. No benzene is formed in isomerization, wherein benzene is converted to C6 naphthenes and C6 naphthenes are isomerized toward an equilibrium mixture of cyclohexane and methylcyclopentane or converted to paraffins through ring opening. It is believed that such C6 cyclics are preferentially adsorbed on catalyst sites relative to paraffins, and the cyclics thus have a significant effect on catalyst activity for isomerization of paraffins. Refiners thus face the problem of maintaining the performance of light-naphtha isomerization units which process an increased concentration of feedstock cyclics.
Catalysts which are useful for ring opening are known and include a high chloride platinum component dispersed on a refractory inorganic oxide which is described in U.S. Pat. No. 5,463,155. U.S. Pat. No. 5,811,624 describes a catalyst for the selective opening of 5 and 6 membered rings which consists of a transition metal catalyst selected from the group consisting of carbides, nitrides, oxycarbides, oxynitrides, and oxycarbonitrides. The transition metal is selected from the group consisting of metals from Group IVA, VA, VIA of the Periodic Table of the Elements. U.S. Pat. No. 6,235,962 B1 discloses a catalyst for ring opening which comprises a carrier consisting of alumina, a metal modifier selected from the group consisting of scandium, yttrium and lanthanum, and at least one catalytically active metal selected from the group consisting of platinum, palladium, rhodium, rhenium, iridium, ruthenium, and cobalt. U.S. Pat. No. 5,382,730 discloses a process for ring opening and isomerization of hydrocarbons where the catalyst comprises an aluminosilicate zeolite such as Zeolite Y or Zeolite Beta and a hydrogenation component. U.S. Pat. No. 5,345,026 discloses a process for conversion of cyclic hydrocarbons to non-cyclic paraffin hydrocarbons where the catalyst comprises a hydrogenation-dehydrogenation component and an acidic solid component comprising a group IVB metal oxide modified with an oxyanion of a group VIB metal. U.S. Pat. No. 3,617,511 discloses a catalyst for conversion of cyclic hydrocarbons to paraffins where the catalyst comprises rhodium or ruthenium on a halogen promoted refractory oxide. U.S. Pat. No. 6,241,876 discloses a ring opening catalyst which comprises a large pore crystalline molecular sieve component with a faujasite structure and an alpha acidity of less than one and a Group VII noble metal. US 2002/43481 A1 discloses a catalyst for naphthalene ring opening which comprises at least one Group VIII metal selected from iridium, platinum, rhodium and ruthenium on a refractory inorganic oxide substrate containing at least one of an alkali metal and alkaline earth metal. US 2002/40175 A1 discloses a naphthene ring opening catalyst comprising a Group VIII metal selected from iridium, platinum, palladium, rhodium, ruthenium and combinations thereof. With the metal being supported on the substrate comprising at least one of a Group IB, IIB, and IVA metal. Finally, U.S. Pat. No. 4,859,312 discloses a process for cracking heavy oils using a catalyst comprising a SAPO molecular sieve and a platinum or palladium component.
Applicants have developed an improved catalyst which takes cyclic paraffins such as methylcyclohexane and converts them to normal paraffins of substantially the same carbon number. The catalyst comprises a Group VIII metal such as platinum or palladium, a molecular sieve and a refractory inorganic oxide component. The molecular sieve is selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof.
As stated, this invention relates to a process and catalyst for ring opening, i.e. cleaving naphthenic rings. Accordingly, one embodiment of the invention is a process for producing acyclic paraffins from cyclic paraffins comprising contacting a feed stream comprising cyclic paraffins with a catalyst comprising a catalytic metal component, a refractory inorganic oxide component and a molecular sieve characterized in that it has an OH peak shift in its COFTIR spectrum of less than 310 cm−1 and is selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof at ring opening conditions to convert at least a portion of the cyclic paraffins to acyclic paraffins.
Another embodiment of the invention is a catalyst for opening cyclic paraffins comprising a catalytic metal component, a molecular sieve characterized in that it has an OH shift in its COFTIR spectrum of less than 310 cm−1 and a refractory inorganic oxide component, the molecular sieve selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof.
These and other objects and embodiments will become clearer after a detailed description of the invention.
One aspect of the present invention is a catalyst which is useful for opening or cleaving naphthenic rings. Ring opening as used herein refers to the breaking of one C�C bond in the ring without any further C�C bond breaks. The further breaking of C�C bonds is commonly referred to as cracking and is specifically excluded from the definition of ring opening. Accordingly, the major product of a ring opening reaction is an acyclic, e.g. normal or branched, paraffin having substantially the same molecular weight or the same number of carbon atoms as the starting cyclic paraffin or naphthene.
In order to carry out such a reaction, the catalyst of the present invention comprises a catalytic Group VIII metal component, a molecular sieve and a refractory inorganic oxide component. The function of the Group VIII metal component is to catalyze the C�C bond break, while the molecular sieve's function is to isomerize cyclohexane rings, both substituted and unsubstituted to cyclopentane rings. The refractory inorganic oxide can act as a support for the catalytic metal component and act as a binder when forming the catalyst into a shaped article. The molecular sieve is selected from the group consisting of MAPSOs, SAPOs, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-16HS and mixtures thereof. The common characteristic of these molecular sieves is that they have sufficient acidity, i.e. acid site strength, to isomerize cyclohexanes to cyclopentanes but not so much acidity that they promote cracking of the acyclic paraffins to lower molecular weight products, i.e. lower carbon number.
One way to determine the acidity of a molecular sieve is to use Fourier Transform Infra Red (FTIR) Spectroscopy, specifically carbon monoxide (CO-FTIR) spectroscopy. Carbon monoxide, when adsorbed at liquid nitrogen temperatures, has been shown to be a suitable probe for measuring relative strengths of Bronsted acid sites in molecular sieve samples. CO forms H-bonded complexes with hydroxyl groups that are easily detected by infrared spectroscopy in both the O�H and C�O stretching regions. When CO adsorbs on a hydroxyl group at liquid nitrogen temperatures, the O�H bond is strongly perturbed and the stretching band is broadened and shifted to lower frequency. The magnitude of this shift is proportional to the strength of the acidic proton. It has been found that molecular sieves with an OH peak shift with CO addition of less than 310 cm−1 and preferably less than 270 cm−1 produce the greatest amount of paraffins with carbon chain lengths equivalent to the original ring-opened naphthenes, i.e. minimal or no cracking. Of course it is understood that only those MAPSOs and SAPOs included within the scope of the invention are those that meet the above acidity criteria. Specific SAPOs included in the scope of the invention are SAPO-11, SM-3 and SAPO-34.
MAPSOs molecular sieves are disclosed in U.S. Pat. No. 4,758,419 which is incorporated by reference in its entirety. A preferred MAPSO is MAPSO-31. SAPO molecular sieves are disclosed in U.S. Pat. No. 4,440,871 which is incorporated by reference in its entirety and SM-3 is described in U.S. Pat. No. 4,943,424 which is incorporated by reference in its entirety. UZM-8 is described in application Ser. No. 10/395,466 while UZM-8HS is described in application Ser. No. 10/395,624; UZM-15 and UZM-15HS are described in application Ser. No. 10/395,399; UZM-16 and UZM-16HS are described in application Ser. No. 10/395,639, all of which are incorporated by reference in their entirety. These compositions will be collectively referred to as UZM zeolites. All of the UZM zeolites have a microporous crystalline structure of at least AlO2 and SiO2 tetrahedral units. UZM-8, UZM-15 and UZM-16 have a composition on an as-synthesized and anhydrous basis expressed by an empirical formula of:
E is an element selected from the group consisting of Ga, Fe, In, Cr, B, and mixtures thereof. The other variables are defined as �p� is the weighted average valence of R; �x� is the mole fraction of E, �y� is the mole ratio of Si to (Al+E) and �z� is the mole ratio of O to (Al+E). The values of �m�, �n�, �r�, �p�, �x�, �y� and �z� are presented in Table A.
These zeolites are also characterized by x-ray diffraction patterns having at least the d-spacings and relative intensities set forth in Table B (UZM-8), Table C (UZM-15) and Table D (UZM-16).
The UZM-8, UZM-15 and UZM-16 zeolites are prepared by a hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of R, aluminum, silicon and optionally M and E. The sources of aluminum include but are not limited to aluminum alkoxides, precipitated aluminas, aluminum metal, sodium aluminate, organoammonium aluminates, aluminum salts and alumina sols. Specific examples of aluminum alkoxides include, but are not limited to aluminum ortho sec-butoxide and aluminum ortho isopropoxide. Sources of silica include but are not limited to tetraethylorthosilicate, colloidal silica, precipitated silica, alkali silicates and organoammonium silicates. A special reagent consisting of an organoammonium aluminosilicate solution can also serve as the simultaneous source of Al, Si, and R. Sources of the E elements include but are not limited to alkali borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride, chromium nitrate and indium chloride. Sources of the M metals include the halide salts, nitrate salts, acetate salts, and hydroxides of the respective alkali or alkaline earth metals. R can be introduced as an organoammonium cation or an amine. When R is a quaternary ammonium cation or a quaternized alkanolammonium cation, the sources include but are not limited to the hydroxide, chloride, bromide, iodide and fluoride compounds. Specific examples include without limitation DEDMA hydroxide, ETMA hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexamethonium bromide, tetrapropylammonium hydroxide, meihyltriethylammonium hydroxide, tetramethylammonium chloride, propylethyldimethylammonium hydroxide (PEDMAOH), trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide (TMBAOH), N,N,N,N′,N′,N′-hexamethyl 1,4 butanediammonium hydroxide (DQ4), and choline chloride. The source of R may also be neutral amines, diamines, and alkanolamines that subsequently hydrolyzes to form an organoammonium cation. Specific examples are triethanolamine, triethylamine, and N,N,N′,N′ tetramethyl-1,6-hexanediamine. Preferred sources of R without limitation are ETMAOH, DEDMAOH, and HM(OH)2.
In a special case, a reagent in the form of an aluminosilicate stock solution may be used. These solutions consist of one or more organoammonium hydroxides and sources of silicon and aluminum that are processed to form a clear homogenous solution that is generally stored and used as a reagent. The reagent contains aluminosilicate species that typically don't show up in zeolite reaction mixtures derived directly from separate sources of silicon and aluminum. The reagent is generally alkali-free or contains alkali at impurity levels from the silicon, aluminum, and organoammonium hydroxide sources. One or more of these solutions may be used in a zeolite synthesis. In the case of substitution of Al by E, the corresponding metallosilicate solution may also be employed in a synthesis.
As shown above, not all the R cations can produce all of the three UZM structures. Thus the preparation of UZM-15 requires at least one first organoammonium cation having at least one organic group with at least two carbon atoms, e.g. DEDMA, ETMA, TMBA, DQ4 and PEDMA and optionally (in addition to the first organoammonium cation) a second organoammonium compound. The preparation of UZM-16 requires benzyltrimethylammonium (BZTMA) or a combination of BzTMA and at least one organoammonium cation as described above.
The reaction mixture containing reactive sources of the desired components can be described in terms of molar ratios of the oxides by the formula:
The values of the variables for the UZM-8, 15 and 16 are presented in Table E along with general and preferred reaction conditions. The reaction mixtures are reacted at the stated conditions in a sealed reaction vessel under autogenous pressure.
After crystallization is complete, the solid product is isolated from the heterogeneous mixture by means such as filtration or centrifugation, and then washed with de-ionized water and dried in air at ambient temperature up to about 100� C.
As-synthesized, the zeolites will contain some of the exchangeable or charge balancing cations in its pores. These exchangeable cations can be exchanged for other cations, or in the case of organic cations, they can be removed by heating under controlled conditions. Ion exchange involves contacting the zeolites with a solution containing the desired cation (at molar excess) at exchange conditions. Exchange conditions include a temperature of about 15� C. to about 100� C. and a time of about 20 minutes to about 50 hours. Calcination conditions include a temperature of about 300� C. to about 600� C. for a time of about 2 to about 24 hours.
A special treatment for removing organic cations which provides the ammonium form of the zeolite is ammonia calcination. Calcination in an ammonia atmosphere can decompose organic cations, presumably to a proton form that can be neutralized by ammonia to form the ammonium cation. The resulting ammonium form of the zeolite can be further ion-exchanged to any other desired form. Ammonia calcination conditions include treatment in the ammonia atmosphere at temperatures between about 250� C. and about 600� C. and more preferably between about 250� C. and about 450� C. for times of 10 minutes to 5 hours. Optionally, the treatments can be carried out in multiple steps within this temperature range such that the total time in the ammonia atmosphere does not exceed 5 hours. Above 500� C., the treatments should be brief, less than a half hour and more preferably on the order of 5-10 minutes. Extended calcination times above 500� C. can lead to unintended dealumination along with the desired ammonium ion-exchange and are unnecessarily harsh as most organoammonium templates easily decompose at lower temperatures.
The UZM-8HS, UZM-15HS and UZM-16HS zeolites are prepared from their respective parent zeolite by a number of various techniques and are represented by the empirical formula:
In formula (2), E and �x� are as defined above. M1 is at least one exchangeable cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion and mixtures thereof, a is the mole ratio of M1 to (Al+E), n is the weighted average valence of M1, y′ is the mole ratio of Si to (Al+E) and z″ is the mole ratio of O to (Al+E). The values of the variables for the three zeolites are presented below in Table F.
The value of y′ is greater than the specific value set forth in Table F to virtually pure silica. By virtually pure silica is meant that virtually all the aluminum and/or the E metals have been removed from the framework. It is well know that it is virtually impossible to remove all the aluminum and/or E metal. Numerically, a zeolite is virtually pure silica when y′ has a value of at least 3,000, preferably 10,000 and most preferably 20,000. Thus, ranges for y′ are from 3 or 6.5 or 7 to 3,000 preferably greater than 10 to about 3,000; 3 or 6.5 or 7 to 10,000 preferably greater than 10 to about 10,000 and 3 or 6.5 or 7 to 20,000 preferably greater than 10 to about 20,000.
The zeolites UZM-8HS, UZM-15HS and UZM-16HS are further characterized by an x-ray diffraction pattern having at least the d-spacings and relative intensities set forth in Tables G, H and I respectively.
The UZM-8HS, 15HS and 16HS are prepared by removing aluminum and optionally inserting silicon into the structure thereby increasing the Si/Al ratio and thus modifying the acidity and ion exchange properties of the zeolites. These treatments include: a) contacting with a fluorosilicate solution or slurry; b) calcining or steaming followed by acid extraction or ion-exchange; c) acid extraction or d) any combination of these treatments in any order.
Fluorosilicate treatment is known in the art and is described in U.S. Pat. No. 6,200,463 B1, which cites U.S. Pat. No. 4,711,770 as describing a process for treating a zeolite with a fluorosilicate salt. Both patents are incorporated by reference in their entirety. General conditions for this treatment are contacting the zeolite with a solution containing a fluorosilicate salt such as ammonium fluorosilicate (AFS) at a temperature of about 20� C. to about 90� C.
The acids which can be used in carrying out acid extraction include without limitation mineral acids, carboxylic acids and mixtures thereof. Examples of these include sulfuric acid, nitric acid, ethylenediaminetetraacetic acid (EDTA), citric acid, oxalic acid, etc. The concentration of acid which can be used is not critical but is conveniently between about 1 wt. % to about 80 wt. % acid and preferably between 5 wt. % and 40 wt. % acid. Acid extraction conditions include a temperature of about 10� C. to about 100� C. for a time of about 10 minutes to about 24 hours. Once treated with the acid, the treated UZM zeolite is isolated by means such as filtration, washed with deionized water and dried at ambient temperature up to about 100� C.
The extent of dealumination obtained from acid extraction depends on the cation form of the starting UZM as well as the acid concentration and the time and temperature over which the extraction is conducted. For example, if organic cations are present in the starting UZM zeolite, the extent of dealumination will be slight compared to a UZM zeolite in which the organic cations have been removed. This may be preferred if it is desired to have dealumination just at the surface of the UZM zeolite. As stated above, convenient ways of removing the organic cations include calcination, ammonia calcination, steaming and ion exchange. Calcination, ammonia calcination and ion exchange conditions are as set forth above. Steaming conditions include a temperature of about 400� C. to about 850� C. with from about 1% to about 100% steam for a time of about 10 minutes to about 48 hours and preferably a temperature of about 500� C. to about 600� C., steam concentration of about 5 to about 50% and a time of about 1 to about 2 hours.
It should be pointed out that both calcination and steaming treatments not only remove organic cations, but can also dealuminate the zeolite. Thus, alternate embodiments for dealumination include: a calcination treatment followed by acid extraction and steaming followed by acid extraction. A further embodiment for dealumination comprises calcining or steaming the starting UZM-16 zeolite followed by an ion-exchange treatment. Of course an acid extraction can be carried out concurrently with, before or after the ion exchange.
The ion exchange conditions are the same as set forth above, namely a temperature of about 15� C. to about 100� C. and a time of about 20 minutes to about 50 hours. Ion exchange can be carried out with a solution comprising a cation (M1′) selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, hydrogen ion, ammonium ion, and mixtures thereof. By carrying out this ion exchange, the M1 cation is exchanged for a secondary or different M1′ cation. In a preferred embodiment, the UZM-16HS composition after the steaming or calcining steps is contacted with an ion exchange solution comprising an ammonium salt. Examples of ammonium salts include but are not limited to ammonium nitrate, ammonium chloride, ammonium bromide, and ammonium acetate. The ammonium ion containing solution can optionally contain a mineral acid such as but not limited to nitric, hydrochloric, sulfuric and mixtures thereof. The concentration of the mineral acid is that amount necessary to give a ratio of H+ to NH4 + of 0 to 1. This ammonium ion exchange aids in removing any debris present in the pores after the steaming and/or calcination treatments.
It is apparent from the foregoing that, with respect to effective process conditions, it is desirable that the integrity of the zeolite crystal structure be substantially maintained throughout the dealumination process, and that the zeolite retains at least 50%, preferably at least 70% and more preferably at least 90% of its original crystallinity. A convenient technique for assessing the crystallinity of the products relative to the crystallinity of the starting material is the comparison of the relative intensities of the d-spacing of their respective X-ray powder diffraction patterns. The sum of the peak intensities, in arbitrary units above the background, of the starting material is used as the standard and is compared with the corresponding peak intensities of the products. When, for example, the numerical sum of the peak heights of the molecular sieve product is 85 percent of the value of the sum of the peak intensities of the starting zeolite, then 85 percent of the crystallinity has been retained. In practice it is common to utilize only a portion of the peaks for this purpose, as for example, five or six of the strongest peaks. Other indications of the retention of crystallinity are surface area and adsorption capacity. These tests may be preferred when the substituted metal significantly changes, e.g., increases, the absorption of x-rays by the sample or when peaks experience substantial shifts such as in the dealumination process.
After having undergone any of the dealumination treatments as described above, the UZM zeolite is usually dried and can be used as discussed below. The properties of the modified UZM zeolite can be further modified by one or more additional treatment. These treatments include steaming, calcining or ion exchanging and can be carried out individually or in any combination. Some of these combinations include but are not limited to:
The dealumination treatment described above can be combined in any order to provide zeolites useful in the invention although not necessarily with equivalent result. It should be pointed out that the particular sequence of treatments, e.g., AFS, acid extraction, steaming, calcining, etc can be repeated as many times as necessary to obtain the desired properties. Of course one treatment can be repeated while not repeating other treatments, e.g., repeating the AFS two or more times before carrying out steaming or calcining; etc. Finally, the sequence and/or repetition of treatments will determine the properties of the final UZM-8HS, 15HS or 16HS composition.
In specifying the proportions of the molecular sieve starting material or adsorption properties of the molecular sieve product and the like herein, the �anhydrous state� of the molecular sieve will be intended unless otherwise stated. The term �anhydrous state� is employed herein to refer to a molecular sieve substantially devoid of both physically adsorbed and chemically adsorbed water.
A second component of the catalyst of the invention is a catalytic metal component. The catalytic metal component is selected from the metals of Group VIII (Groups 8, 9 and 10 of the IUPAC designation) of the Periodic Table of the Elements and preferably from the noble metals. The group of noble metals are ruthenium, rhodium, palladium, platinum, iridium and osmium. Preferred catalytic metals are platinum, palladium, rhodium ruthenium, iridium and mixtures thereof.
The catalytic metal component can be deposited either on the molecular sieve or on a refractory inorganic oxide component. Inorganic oxides which can be used are any of those well known in the art and include but are not limited to aluminas, silica/alumina, silica, titania, calcium oxide and magnesium oxide, clays and zirconia. In order to avoid confusion it is pointed out that the term silica/alumina does not mean a physical mixture of silica and alumina but means an acidic and amorphous material that has bee cogelled or coprecipitated. The term is well known in the art, see e.g. U.S. Pat. No. 3,909,450; U.S. Pat. No. 3,274,124 and U.S. Pat. No. 4,988,659. The aluminas which can be used include gamma alumina, theta alumina, delta and alpha alumina.
The catalytic metal component is deposited onto either the molecular sieve or inorganic oxide by means well known in the art such as spray impregnation or evaporative impregnation. Both spray or evaporative impregnation use a solution containing a decomposable compound of the desired metal. By decomposable is meant that upon heating the compound decomposes to provide the catalytic metal or catalytic metal oxide. Non-limiting examples of decomposable compounds which can be used include chloroplatinic acid, palladic acid, chloroiridic acid, rhodium trichloride, ruthenium tetrachloride, osmium trichloride, iron chloride, cobalt chloride, nickel chloride, iron nitrate, cobalt nitrate, nickel nitrate, rhodium nitrate, ammonium chloroplatinate, platinum tetrachloride hydrate, palladium chloride, palladium nitrate, tetraamine platinum chloride and tetraamminepalladium (II) chloride. The solvent which is used to prepare the solution is usually water although organic solvents such as alcohols, dimethyl formamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF) and amines, e.g., pyridine can be used.
Spray impregnation involves taking a small volume of the solution and spraying it over the support (molecular sieve or oxide) while the support is moving. When the spraying is over, the wetted support can be transferred to other apparatus for drying or finishing steps.
One particular method of evaporative impregnation involves the use of a steam-jacketed rotary dryer. In this method the support is immersed in the impregnating solution which has been placed in the dryer and the support is tumbled by the rotating motion of the dryer. Evaporation of the solution in contact with the tumbling support is expedited by applying steam to the dryer jacket. The impregnated support is then dried at a temperature of about 60� C. to about 300� C. and then calcined at a temperature of about 300� C. to about 850� C. for a time of about 30 minutes to about 8 hours to give the calcined catalyst.
When the molecular sieve is the support, the catalytic metal component can also be deposited thereon by ion-exchange. Ion-exchange is carried out by contacting the molecular sieve with a solution containing a compound of the desired metal at ion-exchange conditions which include a temperature of about 20� C. to about 100� C. for a time from about 5 minutes to about 6 hours.
When the catalytic metal component is deposited on the refractory inorganic oxide component, the catalyst comprises separate particles. One configuration is a loose mixture of the two particles (refractory oxide and molecular sieve particles) or the particles are mixed and then formed into shaped articles such as cylinders, pellets, pills, spheres, irregularly shaped particles, etc. Methods of preparing such shaped articles are well known in the art. In the case where the catalytic metal is deposited on the molecular sieve, then the inorganic oxide acts as a binder so that the resultant mixture can be formed into any of the shapes described above.
In another embodiment, the molecular sieve and inorganic oxide are first mixed and formed into a shaped article and then the catalytic metal is deposited onto the composite article by any of the means described above. In this case, the catalytic metal is believed to be deposited on both the inorganic oxide and molecular sieve supports. Regardless of how and where the catalytic metal is deposited, it is present in the final catalyst in an amount from about 0.01 to about 10 weight percent of the catalyst expressed as the metal. It should also be pointed out that the metal component can be present on the catalyst in its elemental (zero valent) state or as the oxide.
The catalyst may optionally contain a modifier which modifies the activity of the catalytic metal. The modifier is selected from the group consisting of titanium, niobium, rare earth elements, tin, rhenium, zinc, germanium and mixtures thereof. Preferred rare earth elements are cerium, ytterbium, lanthanum, dysprosium and mixtures thereof. The modifier component is deposited by the same techniques as described above for the catalytic metals. Further, the modifier can be deposited on the support before, after or simultaneously with the catalytic metal, although not necessarily with equivalent results. It is preferred to deposit the modifier with the catalytic metal. The amount of modifier can vary substantially but is usually in the range of about 0.1 to about 50 wt. %, preferably about 1 to about 10 wt. % of the catalyst as the element.
The catalyst described above is used in a process where cyclic paraffins are opened or cleaved to acyclic paraffins. The feeds which can be used in the ring opening process are any of those which comprise C5-C6 aliphatic rings, i.e. naphthenic rings. Depending on the source feeds can contain from about 15% to about 55% naphthenes.
The feedstream is contacted with the catalyst at ring opening conditions which include a temperature of about 200� C. to about 600� C. with a range of about 375� C. to about 415� C. bein preferred, a pressure of about atmospheric to about 20,684 kPag (3000 psig) preferably from about 3447 kPa (500 psig) to about 13790 kPa (2000 psig) and most preferably from about 4826 kPa (700 psig) and about 6205 (900 psig), a liquid hourly space velocity of about 0.1 to about 30 hr−1, preferably about 2 to about 10 hr−1 and most preferably from about 4 to about 6 hr−1 and H2/HC (hydrocarbon) molar ratio from about 0.1 to about 30, preferably from about 1 to about 10 and most preferably from about 5 to about 7.
The following examples are presented in illustration of this invention and are not intended as undue limitations on the generally broad scope of the invention as set out in the appended claims.
Aluminum tri-sec-butoxide (95%), 46.32 g, was added to 626.31 g diethyldimethylammonium hydroxide (20%) and dissolved with vigorous stirring. To this mixture, 142.5 g precipitated silica, Ultrasil� VNSP3 (85% SiO2), was added with continuous stirring. In a separate beaker, 21.47 g TMACl (97%) and 5.22 g NaCl were dissolved in 58.18 g de-ionized H2O. This solution was then added to the previous reaction mixture. The resulting mixture was homogenized for 20 min and the final reaction mixture was then distributed among several autoclaves including one 0.6L stainless steel stirred autoclave. The 0.6L autoclave was heated to and held at 150� C. for 120 hr. after which the solids were collected by centrifugation, washed with de-ionized water and dried at 95� C.
The products isolated from the 0.6L reaction exhibited an x-ray diffraction pattern consistent with the characteristic lines for the zeolite designated UZM-15. A sample of the UZM-15 (60 g) was then mixed with 120 ml of 1.57 M HCl solution and heated to 95� C. for 1 hour to remove a good portion of organic templates. The slurry was then filtered while still hot and washed with 500 ml of de-ionized H2O. The filter cake was air dried overnight, treated with HCl as described above, washed using two 500 ml portions of de-ionized H2O and dried at 95� C.
Extrudates of 70 wt. % zeolite (UZM-15) and 30% alumina were prepared by first mulling 19.1 grams of Condea SB� alumina with 29.0 grams of 20% HNO3. The HCl extracted UZM-15 (37.0 grams), Solka Floc (1.5 grams) extrusion aid and additional de-ionized H2O were then added to the peptized alumina and mulled for additional time until a consistent dough texture was obtained. The dough was then pushed through a die plate with 1/16 inch diameter holes to form green extrudate, which was then activated first in N2 and then air at 500� C. for 2 hours. This catalyst was identified as sample A.
An aluminosilicate reaction mixture was prepared by adding 35.2 grams of Al(Osec-Bu)3 (95+%) to 927.5 grams BzTMAOH (40%), and then stirring for 20 minutes, followed by the slow addition of 416.5 grams of colloidal silica (LUDOX� AS-40, 40% SiO2). The resulting mixture was then reacted in an autoclave at 125� C. for 120 hours. The solid product was recovered and washed, and showed an x-ray pattern consistent with that of UZM-16. The powder was then calcined at 500� C. and then NH4NO3 exchanged, filtered, washed with de-ionized H2O and dried at 90� C. The catalyst comprising 70 wt. % UZM-16 and 30 wt. % Al2O3 was prepared using a procedure similar to that described in Example 1. This catalyst was identified as sample B.
An aluminosilicate reaction mixture was prepared in the following manner. Al(Osec-Bu)3 (97%), 804.4 g, was added to 7330 g of DEDMAOH, (20% aq) with vigorous stirring. To this mixture, 2530 g precipitated silica, (Ultrasil� VN SP3, 89% SiO2) was added with continuous mixing. A solution of 127 g NaOH in 3115 g deionized H2O was prepared and added to the previous mixture and homogenized for 30 min. The resulting mixture was reacted in an autoclave at 150� C. for 185 hours. The solid product was collected by filtration, washed with de-ionized water, and dried at 95� C. The product was identified as UZM-8 by powder x-ray diffraction analysis. The zeolite was first NH4NO3 exchanged to remove sodium, then prepared into a catalyst of 70 wt. % UZM-8 and 30 wt. % A1203 using a procedure similar to that described in Example 1. This catalyst was identified as sample C.
An aluminosilicate reaction mixture was prepared in the following manner. Al(Osec-Bu)3 (97%), 66.51 g, was added to 918.29 g of DEDMAOH, (20% aq) with vigorous stirring. To this mixture, 208.95 g precipitated silica, (Ultrasil� VN SP3, 89% SiO2) was added with continuous mixing. A solution of 37.2 g Na2SO4 in 169.05 g deionized H2O was prepared and added to the previous mixture and homogenized for 10 min. A 1.7 g portion of UZM-8 seed was added to the mixture, followed by an additional 20 min of mixing. A 1077.3 g portion of this final reaction mixture was transferred to a 2-L Teflon-lined autoclave. The autoclave was placed in an oven set at 150� C. and the mixture was reacted quiescently for 10 days. The solid product was collected by filtration, washed with de-ionized water, and dried at 95� C. The product was identified as UZM-8 by powder x-ray diffraction analysis. The zeolite was first NH4NO3 exchanged to remove sodium, then prepared into a catalyst of 70 wt. % UZM-8 and 30 wt. % Al2O3 using a procedure similar to that described in Example 1. This catalyst was identified as sample D.
In a container 219.3 g of alumina were mixed with 12.9 g of HNO3 (70%) and to this peptized mixture there were added 109.6 g of alumina, 84.3 g of SM-3 molecular sieve (prepared according to U.S. Pat. No. 4,943,424), 1.5 g of methacel A4M and 197.4 g water. The resulting dough was mixed for 35 minutes and then extruded through a 1/16 inch (0.16 cm) die. The extrudates were dried at 300� C. for 1 hour and then 550� C. for 2 hours in flowing air. This catalyst was identified as sample E.
A catalyst containing SAPO-11 and alumina was prepared per Example 5. The SAPO-11 was prepared according to U.S. Pat. No. 4,440,871. This catalyst was identified as sample F.
Platinum was dispersed on samples A to F by taking 8.35 g of each sample and contacting it with 15 ml of a solution containing 2.97 cc chloroplatinic acid (28.08 mg Pt/ml) and 0.569 ml HCl (37%) in a rotary evaporator. The solution was impregnated at 100� C. and the impregnated base was calcined at 525� C. in flowing air (3600 cc/min) and 45 cc/min HCl for 30 minutes. The calcined catalyst was reduced in flowing hydrogen 3000 cc/min H2 at 500� C. for 1 hour. The amount of platinum on the finished catalyst was found to be about 1 wt. %. The catalysts were labeled catalysts A to F respectively.
Catalysts A to F were tested for methylcyclohexane ring opening activity and selectivity as follows. In on Incolloy� tube reactor there were placed 3 g of 40-60 mesh crushed extrudates of each sample. The reactor was heated using an infrared furnace. Inert spacers were placed before the catalyst bed to minimize dead volume and pre-heat the feed. The feed consisted of methylcyclohexane (>98% purity) which was mixed with hydrogen carrier gas (>99% pure) in a heated mixing chamber and then flowed through the catalyst bed at a weight hourly space velocity of 5 hr−1. Measurements were taken at various temperatures and a pressure of 5516 kPa (800 psi). The reactor effluent was analyzed by an on-line gas chromatograph and the results are presented in the Table below.
Catalysts A to F were also analyzed by CO-FTIR spectroscopy to determine their acid strength. The relative strengths of the Br�nsted acid sites for this set of catalysts were measured using CO adsorption at low temperature (�90K). The samples were pretreated to 550� C. in helium flow and then cooled to �90K and exposed to successive 0.5 cc doses of 0.1% CO in helium. The frequency shifts of the bridging hydroxyl groups after exposure to CO were determined by subtracting the FTIR spectrum recorded before CO exposure. The resulting difference spectra clearly show the resulting band shifts. The results of these measurements are also presented in the Table below.
An optimum ring-opening catalyst produces C7 paraffins at high MCH conversion. Therefore, good ring-opening catalysts are highly selective to C7 paraffins while minimizing loss of C7 products to lower molecular weight components through cracking. Catalysts E and F are the most selective to C7 paraffins at high MCH conversion while minimizing further cracking. This is possible because the acid strength of the molecular sieve component allows much ring isomerization but is weak enough to prevent further molecular weight reduction. This desirable acidity strength is characterized by the OH Band shift of <270 cm−1. Catalyst D also produces high conversion of MCH at temperatures similar to that used for Catalysts E and F but gives poor selectivity to the desired C7 paraffins. This catalyst has much stronger acidity as characterized by a shift in the OH Band of >310 cm-1 and this causes extensive cracking to C6-products. Therefore, the acid strength desired allows processing of MCH feed at temperatures high enough to produce C7 paraffins while minimizing cracking.
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The Defence of Europe: Britain and Poland Facing New Challenges In the East
Chatham House
10 St James's Square, London SW1Y 4LE
Friday, 28 November 2014
11:30 - 12:30
Poland's agenda in the European Union and the New Pact for Europe
(key-note address by Minister Grzegorz Schetyna)
Monday, 1st December 2014
16:00 - 18:00
Hotel Regent
Belwederska Street 23, Warsaw
Citizens rich with resources
2nd Meeting of the Working Group
30 October 2014
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How does 'going global' come about?
6 October 2014
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Europe's new leaders in a world of crises
8 September 2014
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Citizens rich with resources
1st Meeting of the Working Group
10 June 2014
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The 7th Polish-British Round Table
5-6 June 2014
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Get the latest demosEUROPA news:
Study on "How does 'going global' come about?"
Could foreign policy be used as a tool of economic and political modernisation? Could EU act as a possible 'multiplier' of Member States' global influence? What circumstances and 'critical junctures' encourage countries to globalise their foreign policy? How have Poland, Spain and Sweden coped with the challenge of finding a 'golden mean' between their regional and global interests?
These and other questions have been a focus of a new study, edited by Paweł Zerka et al., on How does 'going global' come about?. The study was conducted by demosEUROPA-Centre for European Strategy (Poland), FRIDE(Spain) and Global Utmaning (Sweden).
The report analyses the dynamics between the processes of democratic and market-oriented transition on the one hand, and the globalization of foreign policy on the other. Its authors argue that there is no automatic spillover between the three phenomena. Nevertheless, if modernisation is not reduced to institutional change only but is conceptualised broadly in terms of corresponding identity change in a society, then globalisation of foreign policy inevitably constitutes a part of such modernisation.
The study was co-financed by the Department of Public and Cultural Diplomacy of the Ministry of Foreign Affairs of Poland within the framework of the Cooperation in the field of public diplomacy 2014 grants.
To read the study, click here.
Study on "The Political Economy of EU-LAC Relations after the 2008 Crisis"
The global economic crisis of 2008 has had a significant influence on the economic and political dynamics of relations between the EU and Latin America and the Caribbean. These impacts have been a focus of a new study on The Political Economy of EU-LAC Relations after the 2008 Crisis, co-authored and edited byPaweł Zerka, Head of Program in demosEUROPA-Centre for European Strategy.
The report offers scenarios and a range of recommendations for the development of EU-LAC relations over the next years. In the authors' view, three processes will affect the interest and willingness of the EU and LAC countries to deepen or broaden their relationship. They include the development of world commodity prices; the fate of the EU's global activism during the new institutional cycle as well as the development of major trade and investment initiatives, especially the TTIP and TPP.
The study was conducted by demosEUROPA - Centre for European Strategy together with Fundación de Investigaciones Económicas Latinoamericanas of Argentina (www.fiel.org), thanks to the support of the EU-LAC Foundation (eulacfoundation.org). The project is the winner of the EU-LAC Foundation's first Open Call for Research Projects.
The study is available in English and in Spanish
Convergence must return onto the EU agenda
Paweł Świeboda
As the new European Commission settles in, its most important task should be to restart the convergence process in the European Union. Economically, convergence had stopped both with respect to the South and, somewhat less so, the East as well. Instead, there are massive pressures of fragmentation, from the banking sector to the free movement of labour. There is fragmentation between the EU and its citizens, economic fragmentation between Europe's economies, fragmentation between states and national societies and, finally, social and political fragmentation within member states. Read more...
TTIPing point
The case for concluding a new transatlantic deal on trade and investment has never been stronger. The EU has entered a period of near-stagnation while the emerging markets, receptive customers for EU exports in the past, have markedly slowed down. Every injection of fresh dynamic would be priceless and TTIP's contribution to growth can be meaningful. And yet the belief that the agreement can be worked out before the end of the Obama presidency in 2016 is increasingly seen as a sign of unsubstantiated optimism. The doomsayers need a firm and resolute response. Read more...
Świeboda on Strategic Europe's question: Has the EU Already Lost Britain? Carnegie Europe
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Świeboda: "An unforeseen Brussels Takeover" for New Eastern Europe
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"TTIPing point" by Paweł Świeboda republished by British Influence
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Świeboda: "Central Europe ten years after: punching above weight in the EU?" CIDOB website
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Świeboda: "CEE countries: From industrial dinosaurs to world-class growth rates" for FT
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Cieński: "Central Europe should help entice eastern Europe into the EU" for FT
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Blusz on Polish proposals on EU energy union for OE1 ORF.at
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Hinc on Poland working on its energy mix and COP19
Hinc on shale gas
Financial Times
Świeboda "Euro Zone Debt Battle"
demosEUROPA`s project "Citizens rich in resources" is carried out within "Citizens For Democracy" program and supported by the EOG Funds.

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|By PR Newswire
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|December 10, 2012 02:39 AM EST
GURGAON, India, December 10, 2012 /PRNewswire/ --
Drishti's Ameyo Helps Open Mind Acquire Scalability and Future Readiness Through Improved Customer Interaction Management
Open Mind, as any growing startup in business outsourcing providers, seek to cater to a huge number of clients by delivering the best call centre services. In this business backdrop, technology is one of the key factors to consider when ramping up. Open Mind therefore, looked forward for a solution that could fulfill it's business requirements. These needs have been taken care of by Drishti's Ameyo.
(Logo: http://photos.prnewswire.com/prnh/20120625/IND10048699)
Open Mind sought for a solution that would diminish downtime and enhance productivity and efficiency. The advanced IVR of Ameyo has enabled the firm to reach out to more customers and deliver them with quality service. Open Mind being dynamic in it's business operations, sought for scalability and future proof solution that has been provided to it through Ameyo. Open Mind, that pegs itself as a versatile business outsourcing provider, has been outsourced by Bharti Walmart to run their internal HR helpdesk. AMEYO primarily was implemented for this elite campaign by Open Mind.
As Naveen Gulati, CEO, Open Mind Services Limited, opines, "Since we are a business process outsourcing provider, our client requirements constantly change. We were seeking for a scalable and future proof solution that creates room for this to happen without any hiccups. Ameyo has helped us in this approach to our business, as it enabled us reach more customers through it's Advanced IVR which was customized by AMEYO to meet our dynamic business needs. With this feature, the customers have been able to connect to the agents based on their queries which has helped us minimise downtime and elevate productivity as well as efficiency. We have also managed to streamline our core HR process of Bharti Walmart, which would not have been feasible without Ameyo."
Sachin Bhatia, VP-Business Development, Drishti-Soft further adds, "Businesses require a technology that can provide process optimisation while matching their rapid growth. We wanted an intelligent integration to Ameyo which could size down downtime and enhance scalability and future proof solution. This has enabled our clients, time and over again, to meet their business requirements and we have been in a position to capitalize on this opportunity and expand our presence throughout the domestic market."
About Open Mind Services Limited:
Open Mind is a back office, lead generation, helpdesk, vendor management, and call centre service company offering a one stop outsourcing solution to all your knowledge processing needs. Open Mind is a leading KPO company in India having capabilities to meet any outsourcing demand.
About AMEYO:
AMEYO is the flagship solution from Drishti for complete CIM. It has been designed to add value to the businesses and pave way for a structured growth. AMEYO customers enjoy significant increase in efficiency levels, reduction in operational costs, flexibility, consistent user experience and a demonstrable ROI.
About Drishti:
Drishti offers communications solutions that empower more than enterprises and contact centers to dynamically manage business processes, interactions, workforce and service levels on emerging unified communications (IP Telephony, Unified Messaging, Conferencing, Presence Management, and Application Collaboration), SOA (Service Oriented Architecture), and SaaS (Software as a Service).
Primary Media Contact: Vijayendra Raj, [email protected], 91-124-4771023
High-performing enterprise Software Quality Assurance (SQA) teams validate systems that are ready for use - getting most actively involved as components integrate and form complete systems. These teams catch and report on defects, making sure the customer gets the best software possible. SQA teams have leveraged automation and virtualization to execute more thorough testing in less time - bringing Dev and Ops together, ensuring production readiness. Does the emergence of DevOps mean the end of E...
Nov. 25, 2014 11:30 PM EST Reads: 1,298
Scott Jenson leads a project called The Physical Web within the Chrome team at Google. Project members are working to take the scalability and openness of the web and use it to talk to the exponentially exploding range of smart devices. Nearly every company today working on the IoT comes up with the same basic solution: use my server and you'll be fine. But if we really believe there will be trillions of these devices, that just can't scale. We need a system that is open a scalable and by using ...
Nov. 25, 2014 09:30 PM EST Reads: 1,477
The Internet of Things is tied together with a thin strand that is known as time. Coincidentally, at the core of nearly all data analytics is a timestamp. When working with time series data there are a few core principles that everyone should consider, especially across datasets where time is the common boundary. In his session at Internet of @ThingsExpo, Jim Scott, Director of Enterprise Strategy & Architecture at MapR Technologies, discussed single-value, geo-spatial, and log time series dat...
Nov. 25, 2014 09:30 PM EST Reads: 1,522
"Verizon offers public cloud, virtual private cloud as well as private cloud on-premises - many different alternatives. Verizon's deep knowledge in applications and the fact that we are responsible for applications that make call outs to other systems. Those systems and those resources may not be in Verizon Cloud, we understand at the end of the day it's going to be federated," explained Anne Plese, Senior Consultant, Cloud Product Marketing at Verizon Enterprise, in this SYS-CON.tv interview at...
Nov. 25, 2014 09:00 PM EST Reads: 1,602
"For the past 4 years we have been working mainly to export. For the last 3 or 4 years the main market was Russia. In the past year we have been working to expand our footprint in Europe and the United States," explained Andris Gailitis, CEO of DEAC, in this SYS-CON.tv interview at Cloud Expo, held Nov 4–6, 2014, at the Santa Clara Convention Center in Santa Clara, CA.
Nov. 25, 2014 08:15 PM EST Reads: 1,463
P2P RTC will impact the landscape of communications, shifting from traditional telephony style communications models to OTT (Over-The-Top) cloud assisted & PaaS (Platform as a Service) communication services. The P2P shift will impact many areas of our lives, from mobile communication, human interactive web services, RTC and telephony infrastructure, user federation, security and privacy implications, business costs, and scalability. In his session at @ThingsExpo, Robin Raymond, Chief Architect...
Nov. 25, 2014 08:00 PM EST Reads: 1,651
The Domain Name Service (DNS) is one of the most important components in networking infrastructure, enabling users and services to access applications by translating URLs (names) into IP addresses (numbers). Because every icon and URL and all embedded content on a website requires a DNS lookup loading complex sites necessitates hundreds of DNS queries. In addition, as more internet-enabled 'Things' get connected, people will rely on DNS to name and find their fridges, toasters and toilets. Acco...
Nov. 25, 2014 07:00 PM EST Reads: 1,535
The term culture has had a polarizing effect among DevOps supporters. Some propose that culture change is critical for success with DevOps, but are remiss to define culture. Some talk about a DevOps culture but then reference activities that could lead to culture change and there are those that talk about culture change as a set of behaviors that need to be adopted by those in IT. There is no question that businesses successful in adopting a DevOps mindset have seen departmental culture change, ...
Nov. 25, 2014 07:00 PM EST Reads: 1,217
"Cloud consumption is something we envision at Solgenia. That is trying to let the cloud spread to the user as a consumption, as utility computing. We want to allow the people to just pay for what they use, not a subscription model," explained Ermanno Bonifazi, CEO & Founder of Solgenia, in this SYS-CON.tv interview at Cloud Expo, held Nov 4–6, 2014, at the Santa Clara Convention Center in Santa Clara, CA.
Nov. 25, 2014 06:15 PM EST Reads: 1,347
Enthusiasm for the Internet of Things has reached an all-time high. In 2013 alone, venture capitalists spent more than $1 billion dollars investing in the IoT space. With "smart" appliances and devices, IoT covers wearable smart devices, cloud services to hardware companies. Nest, a Google company, detects temperatures inside homes and automatically adjusts it by tracking its user's habit. These technologies are quickly developing and with it come challenges such as bridging infrastructure gaps,...
Nov. 25, 2014 04:30 PM EST Reads: 1,538
SYS-CON Media announced that Centrify, a provider of unified identity management across cloud, mobile and data center environments that delivers single sign-on (SSO) for users and a simplified identity infrastructure for IT, has launched an ad campaign on Cloud Computing Journal. The ads focus on security: how an organization can successfully control privilege for all of the organization's identities to mitigate identity-related risk without slowing down the business, and how Centrify provides ...
Nov. 24, 2014 11:00 PM EST Reads: 1,431
SAP is delivering break-through innovation combined with fantastic user experience powered by the market-leading in-memory technology, SAP HANA. In his General Session at 15th Cloud Expo, Thorsten Leiduck, VP ISVs & Digital Commerce, SAP, discussed how SAP and partners provide cloud and hybrid cloud solutions as well as real-time Big Data offerings that help companies of all sizes and industries run better. SAP launched an application challenge to award the most innovative SAP HANA and SAP HANA...
Nov. 24, 2014 09:30 PM EST Reads: 1,388
"SAP had made a big transition into the cloud as we believe it has significant value for our customers, drives innovation and is easy to consume. When you look at the SAP portfolio, SAP HANA is the underlying platform and it powers all of our platforms and all of our analytics," explained Thorsten Leiduck, VP ISVs & Digital Commerce at SAP, in this SYS-CON.tv interview at 15th Cloud Expo, held Nov 4-6, 2014, at the Santa Clara Convention Center in Santa Clara, CA.
Nov. 24, 2014 09:15 PM EST Reads: 1,372
"We help companies that are using a lot of Software as a Service. We help companies manage and gain visibility into what people are using inside the company and decide to secure them or use standards to lock down or to embrace the adoption of SaaS inside the company," explained Scott Kriz, Co-founder and CEO of Bitium, in this SYS-CON.tv interview at 15th Cloud Expo, held Nov 4–6, 2014, at the Santa Clara Convention Center in Santa Clara, CA.
Nov. 24, 2014 07:15 PM EST Reads: 1,421
Explosive growth in connected devices. Enormous amounts of data for collection and analysis. Critical use of data for split-second decision making and actionable information. All three are factors in making the Internet of Things a reality. Yet, any one factor would have an IT organization pondering its infrastructure strategy. How should your organization enhance its IT framework to enable an Internet of Things implementation? In his session at Internet of @ThingsExpo, James Kirkland, Chief Ar...
Nov. 24, 2014 07:00 PM EST Reads: 2,003
SAP is delivering break-through innovation combined with fantastic user experience powered by the market-leading in-memory technology, SAP HANA. In his General Session at 15th Cloud Expo, Thorsten Leiduck, VP ISVs & Digital Commerce, SAP, discussed how SAP and partners provide cloud and hybrid cloud solutions as well as real-time Big Data offerings that help companies of all sizes and industries run better. SAP launched an application challenge to award the most innovative SAP HANA and SAP HANA...
Nov. 24, 2014 06:30 PM EST Reads: 1,430
Bit6 today issued a challenge to the technology community implementing Web Real Time Communication (WebRTC). To leap beyond WebRTC's significant limitations and fully leverage its underlying value to accelerate innovation, application developers need to consider the entire communications ecosystem.
Nov. 24, 2014 12:00 PM EST Reads: 1,725
The definition of IoT is not new, in fact it's been around for over a decade. What has changed is the public's awareness that the technology we use on a daily basis has caught up on the vision of an always on, always connected world. If you look into the details of what comprises the IoT, you'll see that it includes everything from cloud computing, Big Data analytics, "Things," Web communication, applications, network, storage, etc. It is essentially including everything connected online from ha...
Nov. 24, 2014 11:00 AM EST Reads: 2,094
Cloud Expo 2014 TV commercials will feature @ThingsExpo, which was launched in June, 2014 at New York City's Javits Center as the largest 'Internet of Things' event in the world.
Nov. 24, 2014 09:00 AM EST Reads: 1,948
SYS-CON Events announced today that Windstream, a leading provider of advanced network and cloud communications, has been named "Silver Sponsor" of SYS-CON's 16th International Cloud Expo®, which will take place on June 9–11, 2015, at the Javits Center in New York, NY. Windstream (Nasdaq: WIN), a FORTUNE 500 and S&P 500 company, is a leading provider of advanced network communications, including cloud computing and managed services, to businesses nationwide. The company also offers broadband, p...
Nov. 23, 2014 07:30 PM EST Reads: 2,129


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Being a frequent traveler to be Disney World parks and getting ready for our first Disney cruise in January '15 we loved these books. (My grandkids are reading them also). Read morePublished 25 days ago by Bill Dowis
Ridley Pearson has done it again. Another great book made to amaze. I can't wait to buy the next book.Published 1 month ago by ALM Miller
My 14 year old son loved it and can't wait to get the new one.Published 1 month ago by Julie Ann Harris
Bought this series for my daughter, ended up addicted to it myself love these books!Published 3 months ago by J. Broering
I am reading this series at night to my son. I love it more than him I think because he falls asleep. It is action packed and fun to read. Read morePublished 3 months ago by neanea


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The subsidiary has overtaken the parent company, as a new study from Piper Jaffray found that the most important social network for teens in the spring of 2014 is Instagram, which passed both Facebook and Twitter to claim the top spot.
Piper Jaffray
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Content Marketing 101
Almost 60% of businesses use some form of content marketing. Starting December 8, get hands-on content marketing training in our online boot camp! Through an interactive series of webcasts, content and marketing experts will teach you how to create, distribute, and measure the success of your brand's content. Register now!
70M Facebook Shares To Hit The Market, Including 41.35M From Mark Zuckerberg
Another 70 million Facebook shares will hit the market, as the social network announced an underwritten registered public offering of class-A common stock, with 27,004,761 coming from the company itself and another 42,995,239 from certain stockholders, including 41,350,000 from Co-Founder and CEO Mark Zuckerberg.
STUDY: Teens Like Facebook More Than Twitter
Teenagers are using all kinds of social networks nowadays — Tumblr, Pinterest, Facebook, Twitter — but they're not really flocking to one exclusively. It seems like every month, a study shows that teens favor one social media site over another. Now a new study from Piper Jaffray claims that Facebook has beaten Twitter as the hot social network du jour.


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A super yummy treat that I normally only make for childrens parties, but is always a hit with the adults too and am always asked for the recipe.
No oven needed. Quick and easy, but super tasty.
Mix together melted butter, crushed biscuits and sweetend condensed milk. Lay flat and place lolly's in the middle and then shape into a log and roll in coconut. Refrigerate until firm and then slice into rounds.
Can be frozen.
an alternative mthod is Melt butter in medium saucepan, stir in condensed milk. Remove from heat to cool slightly and stir in biscuits. Then repeat the log making and lolly adding as above
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Moscato, Sparkling Whites and Rose are the best wines to pair with Lolly Cake.
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We offer fresh cut bank instrument for lease/sale, such as BG, SBLC, MTN, Bank Bonds, Bank Draft, T strips and others. Leased Instruments can be obtained at minimal expense to the borrower compared to other banking options. This offer is opened to both those and corporate bodies. Description of Instrument: 1.Instrument: Bank Guarantee (BG)/SBLC 2.Total Face Value: MINIMUM 1MILLION EURO/USD - MAXIMUM 100BILLION EURO/USD 3.Issuing Bank: HSBC London or AA rated Bank in Western Europe or USA. 4.Term: One Year, One Month 5.Leasing Price: 5% of Face Value plus 0.5% Lessor agent [Closed] & X% Lessee agent (open) 6.Style of speaking: SWIFT TO SWIFT 7.Payment: WIRE TRANSFER 8.Hard Copy: Bonded Courier surrounded by 7 We are RWA ready to close leasing with any interested client in few banking days, if interested do not hesitate to contact us via banking days Our BG/SBLC Financing can help you get your project funded, loan financing by providing you with yearly renewable leased bank instruments. We work directly with issuing bank lease providers, this Instrument can be monetized on your behalf for 100% funding: For further details contact us with the below information. Contact : Khan.kamal Email: email@example.com Skype ID: kamal.lease Intermediaries/Consultants/Brokers are welcome to bring their clients are 100% protected. In complete confidence, we will work together for the benefits of all parties involved.
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it's fine for a business trip but wouldn't stay there otherwise. The rooms are fine but there is limited room service and amenities. You could always walk next door to the sister hotel but then you might as well just stay there. However if you are on a budget, the rooms at country lodge are quite a lot bigger than the economy ones at Fairmount.
- Official Description (provided by the hotel):
- Country lodge- Nairobi's most popular limited service hotel(bed and breakfast). It has eighty four rooms designed for the business traveller with unbeatable rates that offers true value for money without compromising on service delivery and comfort. Our room rates include bed, breakfast, wifi and all taxes. Located in Nairobi's upper hill, the hotel provides a peaceful, quiet and safe environment. ... more less
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We would like to buy the DVD with the Chowpatty "Simple Temple" video made by Arjuna Parker. Is it possible? Who should we contact for this? Otherwise, is it possible to receive the complete video (compatible with Mac) to our e.mail address?
Thank you very much. ( email@example.com )
Vasudeva Datta das and Sri Lalita dasi (from "Movimento ISKCON" Italian Newsletter)


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Lung Transplants
Phoenix hosptial gets $19M gift to create thoracic transplant center
The only Arizona hospital performing lung transplants recently received its largest-ever donation — a $19 million gift to create a new center for thoracic medicine.
UA medical dean at center of dispute will move to a newly created job
The dean of the University of Arizona's College of Medicine in Tucson, who is at the center of a fierce dispute with a top surgeon, is leaving his job for a new one at UA.
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Town Square
Today: Three cities hold gun buyback
Original post made on Feb 21, 2013
Read the full story here Web Link posted Thursday, February 21, 2013, 8:47 AM
Comments (2)
a resident of Atherton: West Atherton
on Feb 21, 2013 at 12:54 pm
Pennies on the dollar are paid to these citizens. Unwanted firearms can be sold at a gun dealier on consignment and get the fair market value. I wonder how many antique and curio firearms actually make it to the 'destryoer' department. Since no questions are asked, how will the Feds who keep a record of every legal firearm sale know it was destroyed? If gang violence wants to be curbed, enforce over crowding, put more policy on patrol instead of incident management.
a resident of Menlo Park: Linfield Oaks
on Feb 22, 2013 at 3:20 pm
Well, said, Brad. If you really are interested in getting rid of firearm, check out Calguns. There is a active wanted section on that website. Fair, market prices.
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David Griffin said he sees Andrew Wiggins as "a big two-guard" on Friday, which has some execs believing Cavs may look to move Dion Waiters.
This also explains the Cavs' strong interest in Trevor Ariza. They view Andrew Wiggins as a SG, and want Ariza to slide in and start at SF.
via Alex Kennedy of Basketball Insiders
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Pleasing the Goddess
Apr 12, 2013
Immersed in the thought of the deity, they forget their identity. Barriers of all kinds, including language, break away, merging the 'Komarams' into the oneness of 'Bhagavathy' at the Kodungalloor Bharani festival. Photos: H. Vibhu
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Latest News
Featured Posts
- Top 10 Things You Need to Know About Obama's New Immigration Policies
- Firm Proves Citizenship of Client Facing Deportation
- Video from Forum at Carroll College on LR-121, Montana's Anti-Immigrant Law
- Governor Brian Schweitzer's Thoughts on Immigration
- Interview on PoliticktickBOOM, a local Podcast.
- Firm Prevents Deportation of Father of Two Developmentally Disabled Children
- Why the term "anchor babies" is offensive and inaccurate.
- How U.S. Immigration Laws Impact LGBTIQ Families
- My Response to "What part of 'illegal' don't you understand?"
- Shahid Haque-Hausrath Wins Neil Haight Pro Bono Award
- Feature on Shahid Haque-Hausrath in the Helena Independent Record
- No Human Being is Illegal: Why use of the term "illegal alien" is inaccurate, offensive, and should be eliminated from our public discourse.


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Vegetarian Thanksgiving: Skyping the Holiday Meal
November 21, 2014
Dr. Nancy Reau on five things everyone should know about prevention and treatment of hepatitis B.
Notable research studies on hepatitis B.
Talking points for patients and physicians.
Dr. Marion Peters on the challenge of treating hepatitis B.
An effective vaccine against hepatitis B is available, but high-risk populations must be targeted, and treated.
People with pancreatic cancer are more likely than those without the disease to have been infected with the hepatitis B virus, a study has shown for the first time. The finding suggests that hepatitis B -- already known to cause liver cancer in some patients -- may also increase the risk of...
Talking points for patients and physicians.
Dr. Jay H. Hoofnagle on new therapies for hepatitis C.
Current therapies can be individualized to cure chronic hepatitis C in 40 to 80 percent of cases.
Nevada health officials said Thursday that they had identified 77 new cases of hepatitis C among patients treated at a Las Vegas endoscopy practice, in one of the country's largest outbreaks of the liver disease. The officials had previously identified seven cases of the disease linked to the...


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Joan Jonas: Reanimation, with Jason Moran
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Search Result
Search Tags: Prince George
Md. may increase speed limit on ICC
Maryland is reviewing a study that says the speed limit on the highway could be raised to 60 mph.
Tags: Intercounty Connector, Ari Ashe, montgomery county, speed increase,
Prince George's County wins with Redskins
If the Redskins come out on top in Sunday night's game against the Dallas Cowboys, so will Prince George's County.
Tags: Tom Himler, tax revenue, tourism, sports industry, redskins,
One week later, UMd. student still missing
Prince George's County police are asking for help finding a missing 20-year-old man.
Tags: University of Maryland, missing,
Man shot, killed while holding toddler
Police in Prince George's County say that a Seat Pleasant man who was shot and killed Wednesday morning was targeted.
Tags: police, Crime, fatal shooting,
Pedestrian killed in Prince George's crash; separate fatal in Balt. Co.
A man was struck and killed by a car Thursday morning while walking along a sidewalk in Fort Washington, police say.
Tags: fatal crash, pedestrian hit,
Pr. George's teacher accused of sex with student
A teacher in Prince George's County has been charged with having sex with a student.
Tags: sex offense,
Boil water advisory lifted for Largo neighborhood
The boil water advisory issued by the Washington Suburban Sanitary Commission on Thursday, Nov. 22 was lifted on Saturday, Nov. 24 at 9:15 p.m.
Tags: Boil water advisory,
Pr. George's bill calls for employee robbery training
Prince George's County is proposing a bill that would force convenience stores and gas stations to train their employees on what to do during a robbery.
Tags: robberies, The Washington Examiner,
Tape shows incident between officers, UMd. student (VIDEO)
Two Prince George's County police officers, both members of the department's special operations division, are charged with first- and second- degree assault and misconduct in office.
Pr. George's Co. offers free SAT tests
The Prince George's County Public Schools will offer free SAT tests to seniors in October. The reading, writing and math exams are offered on a school day.
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The Verrazano-Narrows Bridge is one of the coolest mega-structure in New York. It was opened in 1964. It was the longest suspension bridge then. The bridge stretched from the Fort Hamilton in Brooklyn to the Fort Wadsworth in Salen Island. It was named after a European Navigator Giovanni da Verrazzano. He is the first European navigator who arrived New York in 1524. The Verrazano-Narrows Bridge has 12 usable lanes, 6 of its lanes are located at the upper deck and the other 6 lanes are at the lower or the inner section of the bridge.
Nikon D300
25.0 f/16.0 (EV+1.67) ISO200
Unforgettable night photo-shoot trip with Lina
great shot
Wonderful night capture!!!
wonderful capture Svet..looks great!!!
well done Svetlana.
Fantastic night capture love the lighting in this Lana.
Great work Svetlana. Love it. Don.
LARGER VIEW is the only way to look at this image, I only comment on the very best from people on this site, this is just brilliance.
I am flattered, thanks Lee:)))
– Svetlana Sewell
WOW Lana, this is absolutely beautiful, loving seeing NY through your lens.


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Posts tagged music-on-electric-guitar
NintendoWare Weekly: Spin Master, WiiWare demos, Tetris Party Live
After the last few years, we don't know how to react to the kind of wealth on the Wii and DSi Shops today. It's too much to process all at once. WiiWare demos are back, offering a chance to check out Bit.Trip Fate, ThruSpace, And Yet It Moves and Jett Rocket with no financial outlay. There's a new...
Breaking News
Dying Light cancelled on Xbox 360, PS3
Featured Stories
Get a closer look at final retail Amiibos
Posted on Nov 22nd 2014 9:00AM
Barely Related: Star-Lord's dance-off, comet sounds
Posted on Nov 21st 2014 8:30PM
Games we love and hate
Posted on Nov 21st 2014 3:00PM


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Chael Sonnen breaks down the what is sure to live up to expectations fight between 145 champ Jose Aldo and top contender Chad Mendes in a very well thought out video interview. In their first fight at UFC 142 Mendes ... Read More »
Category Archives: MMAFeed Subscription<
Video – Christy Mack update courtesy of Jenna Jameson
So now Christy Mack's beating by War Machine has made it to the talking points of Headline News. Jenna Jameson stopped by to update Dr. Drew and the country on how the adult film star is doing as she recovers ... Read More »
Ronda's legs star in Expendables 3 premiere video, Seagal on why he's not on cast
We all love Ronda Rousey and a good action flick that's a given. Ronda is a co-star in the new Expendables movie, Expendables 3. The entire cast has grown since the first movie. This go around they have added Antonio ... Read More »
New star emerging in the WWE, superstars tweet about it
With the signing of the hottest free agent, Prince Devitt, the WWE has secured another positive addition to the future success of a slowly recovering company. Everyone knows the difficulties that the WWE Network has been facing. Slow growth, insufficient ... Read More »
CAPTURED!! | Countdown: War Machine capture watch (Updated 8/15/14 – 5:22 p.m. CT)
It's only a matter of time until War Machine (Jon Koppenhaver) is caught for his alleged involvement in a domestic abuse case against porn star Christy Mack. After it was announced a $10,000 bounty was offered for information leading to ... Read More »
'Dog The Bounty Hunter' gives War Machine ultimatum: 'Turn yourself in or I'm coming after you'
You can run but you can't hide. Not from this guy. "Dog The Bounty Hunter" (Duane "Dog" Chapman) don't play son. This is the guy who travels around the country showing bondsmen how to track down criminals who jump bail. ... Read More »
John 'Doomsday' Howard has a message for War Machine 'aka Bitch Machine'
UFC fighter John "Doomsday" Howard has a message for fellow welterweight War Machine (aka Jon Koppenhaver) after hearing about his alleged attack on ex-girlfriend Christy Mack. Via Instagram: "Got to get this off my chest dont Care about the consequences ... Read More »
Replay – ProWMMA Now! Radio Episode 77 featuring Lauren Murphy, Ashley Cummins and JJ Aldrich
Popular MMA Internet Radio with Pro MMA Now Radio on BlogTalkRadio Back after a break last week, ProWMMA Now! returned last night with four guests. Invicta 8 goes down in just 4 weeks. Set to fight on the card ... Read More »
Christy Mack posts photos and statement regarding alleged attack from War Machine
It's innocent until proven guilty in this country but it's not looking good for former UFC and Bellator fighter War Machine (aka Jon Koppenhaver). Christy Mack has now posted photos and issued a full statement regarding an alleged attack that ... Read More »
Randy Couture talks with Larry King about The Expendables series, MMA and more
MMA legend and The Expendables 3 star Randy Couture sat down with Larry King on "Larry King Now" to talk about his movie career, MMA and more. The two went from talking about his role in The Expendables series to ... Read More »
Rumor Control: Source tells us Brock is "likely to make UFC return" in 2 years
So I will call a long time friend of mine "Rumor Man" for the sake of this article and at the request of his anonymity. A recent verified rumor by Rumor Man was the release of Alberto Del Rio and ... Read More »
The 10 best entrance themes in WWE History Part 1
There are many memorable moments in the WWF/WWE. Some of them for the wrong reasons, Mae Young giving birth to a hand, and some are unforgettable for all of the right ones, Shawn Michaels comes flying to the ring in ... Read More »
Video- Amanda Bell knocks out Marina Shafir
The Four Horsewomen featherweight Marina Shafir (1-1) took to the cage tonight in her sophomore showing as a professional. Talk has been Shafir was eyeing a fight eventually with Cris Cyborg Justino but she would have to win her fight ... Read More »
War Machine takes to Twitter, "I'm not a bad guy"
The police are still searching for War Machine following the allegations of assault on what is believed to be porn star girlfriend Christy Mack and another subject. He's been released from Bellator, facing charges and more than likely heading back ... Read More »
Jenna Jameson: I know Christy Mack 'has the guts to press charges on War Machine'
On Friday it was reported that War Machine (aka Jon Koppenhaver) had been released from his contract with Bellator due to allegations of domestic abuse in Las Vegas that sent two individuals to the hospital, including one described as his ... Read More »
Bellator fires War Machine after alleged altercation sends 'significant other' to hospital
After three appearances inside the Bellator cage, War Machine (aka Jon Koppenhaver) is out of a job. The 32-year-old TUF 6 veteran was released by the promotion after news surfaced Friday (via TMZ) that he was wanted by Las Vegas ... Read More »
Breaking: main event WWE star released, Magazine canceled, senior VP fired
We have been covering all of the WWE network woes and personnel cuts since the juggernaut pro wrestling company's financial mess started to pick up last year. They recently released beloved long time employee timekeeper Mark Yeaton. Mark's release has been ... Read More »
Chael Sonnen is a gangster, ignores NSAC threats about Metamoris
Never let it be said that Chael Sonnen is afraid of anything. After failing drug tests for banned substances he was forced out of his impending fight with Wanderlei Silva and suspended from combat-sports for quite a while. Enter the ... Read More »
No Sonnen for Wand, now wants Hendo for trilogy
Wanderlei spoke to the media in Brazil to call out Pride standout and fellow MMA legend Dan Henderson now that nemesis Chael Sonnen can no longer compete due to failed drug tests. Dan knocked out Wanderlei in 2007 and won the Pride Welterweight ... Read More »
Definitive Collection: Street Fighter 2, Martial Arts and Church Editions
I love this. I laugh at every piece of these videos. In the world of religious drama there are some incredible set pieces like the resurrection, sermon on the mount, and Noah's ark. Then, well then there are these guys ... Read More »
Way back Wednesday: Keith Hackney puts on nut shot clinic at UFC 4
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The Top 10 In Action Sports
015 Action Sports You Should Try On Your Gap Year
02This Crazy Dude Climbed Up A 900ft Chimney – With No Ropes!
03Did Dan Atherton And Red Bull Just Create The Toughest Downhill Track Ever?
04Parkour Porn: This Naked London Photo Shoot Will Leave You Stunned
05£214 Million Is About To Be Pumped Into British Cycling...
06GoPro Are Launching Their Own Drone... And It Will Be Cheaper Than You Think
07Bored Of Commuting? Next Year You Could Be Able To Get To Work By Trampoline
0810 Mountain Bike Inventions That Seemed Like A Good Idea At The Time
09Want To Be A Better Skater? These Scientific Secrets Will Help You On Your Way
10It Has Killed Five People, But This Monster Wave Looks Pretty Different Beneath The Surface…
VoulVoul Racing Team: Day and Evening Ride
A Mountain Biking video by tchoucaton - 7,113 views
Here is my last video shot in the south of France with the Voulvoul Racing Team riders and some of their friends. During the day, they were practising downhill and in the evening you can see them riding on a BMX track. More informations: http://www.tchouktv.com/ and http://www.voulvoul-racing.com/
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