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A crystalline molecular sieve having a framework structure isomorphous with zeolite beta and containing Si and Ti, but essentially no framework Al, usefully catalyzes olefin epoxidation wherein hydrogen peroxide is the oxidant.
1. A process for epoxidation of an olefin comprising contacting said olefin with hydrogen peroxide in the presence of a catalytically effective amount of a crystalline titanium-containing molecular sieve for a time and at a temperature effective to selectively form an epoxide of the olefin, wherein the crystalline titanium-containing molecular sieve is characterized by a framework structure isomorphous to zeolite beta comprised of Si and Ti, but essentially free of framework Al, corresponding to the general formula SiO2 :yTiO2 wherein y is from 0.01 to 0.25.
2. The process of claim 1 wherein the olefin is selected from ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, cyclopentene, 1-hexene, cyclohexene, vinyl cyclohexane, allyl alcohol, 1-heptene, 1-octene, and 1,3-butadiene.
3. The process of claim 1 wherein the olefin is a C2 -C10 mono-olefin.
4. The process of claim 1 wherein the temperature is from 25� C. to 150� C.
5. The process of claim 1 wherein the hydrogen peroxide is obtained by molecular oxygen oxidation of a secondary alcohol.
6. The process of claim 1 wherein said contacting is carried out in a liquid phase.
7. The process of claim 1 wherein from 0.001 to 10 grams of the crystalline titanium-containing molecular sieve per mole of olefin is utilized.
8. A process for epoxidation of a C2 -C10 aliphatic mono-olefin comprising contacting said mono-olefin with hydrogen peroxide in a liquid phase in the presence of from 0.001 to 10 grams per mole of mono-olefin of a crystalline titanium-containing molecular sieve at a temperature of from 25� C. to 120� C. for a time effective to selectivity form an epoxide of the mono-olefin, wherein the crystalline titanium-containing molecular sieve is characterized by a framework structure isomorphous to zeolite beta comprised of Si and Ti, but less than 1000 ppm framework Al, corresponding to the general formula SiO2 :yTiO2 wherein y is from 0.03 to 0.20.
9. The process of claim 8 wherein the mono-olefin is propylene.
This invention relates to methods of selectively oxidizing olefins so as to obtain products containing epoxide functional groups. In particular, the invention pertains to processes whereby a hydrogen peroxide source is reacted with an ethylenically unsaturated substrate in the presence of a relatively large pore crystalline titanium-containing molecular sieve catalyst to yield an epoxide. The catalyst is characterized by a framework structure isomorphous to zeolite beta comprised of silica and titanium, but essentially free of framework aluminum.
Many different methods for the preparation of epoxides have been developed. One such method involves the epoxidation of an olefin in a liquid phase reaction using an organic hydroperoxide as the oxidizing agent and certain solubilized transition metal compounds as catalyst. Although this approach is practiced commercially and generally provides high selectivity to epoxide, it has at least two characteristics which tend to limit process flexibility and increase production costs. The use of an organic hydroperoxide results in the generation of a co-product alcohol derived from the reacted hydroperoxide during epoxidation; approximately 1 equivalent of the co-product is obtained for each equivalent of epoxide. If no market exists for the alcohol, the co-product must either be further reacted (incurring additional processing costs) so as to convert it back to the hydroperoxide oxidant or to another compound for which a commercial demand exists. Recovery of the soluble metallic catalyst used in such a process for reuse in subsequent runs is also problematic. It would therefore be highly desirable to develop an insoluble (heterogeneous) epoxidation catalyst which has high activity and selectivity when utilized with an oxidant such as hydrogen peroxide which does not form an organic co-product. Such a catalyst would ideally be readily recoverable in active form from an epoxidation reaction mixture by filtration or similar separation techniques or be capable of being utilized in the form of a fixed bed or the like.
Workers at the Universidad Politecnica de Valencia have recently reported the synthesis of a titanium silicoaluminate isomorphous to zeolite beta (see Camblor et al., J. Chem. Soc., Chem. Commun. pp. 589-590 (1992), Camblor et al., Zeolites 13, pp. 82-87 (1993) and ES 2037596 (published Jun. 16, 1993)). Such aluminum-containing materials were found to catalyze the oxidation of alkanes to alcohols, ketones, and the like using hydrogen peroxide as the oxidant. This type of titanium silicoaluminate in unmodified (fully protonated) form is a poor catalyst for the production of epoxides from olefins, however.
We have now made the unexpected discovery that a crystalline titanium-containing molecular sieve characterized by a framework structure isomorphous to zeolite beta and comprised of Si and Ti atoms, but essentially free of framework aluminum, selectively catalyzes the epoxidation of olefins using hydrogen peroxide or a hydrogen peroxide precursor.
FIG. 1 is an X-ray powder diffraction pattern of the titanium-containing molecular sieve prepared using the procedure of Example 1.
In the process of this invention, an olefin is contacted with hydrogen peroxide or a substance capable of producing hydrogen peroxide under the reaction conditions in the presence of a catalytically effective amount of a tietanium-containing molecular sieve. The titanium-containing molecular sieve suitable for use is characterized by a framework structure isomorphous to zeolite beta. Si and Ti atoms are present in the framework structure (typically, in the form of oxides). The framework of the molecular sieve is essentially free of aluminum (Al), however, since the presence of significant amounts of Al has been found to detrimentally affect the performance of said molecular sieve as an epoxidation catalyst unless the protons associated with aluminum are substituted with ammonium, alkali metal, or alkaline earth cations. In this context, "essentially free" means that the framework structure of the molecular sieve contains less than 1000 ppm Al. Preferably, less than 500 ppm Al is present in the framework structure. The Si to Al molar ratio (Si:Al) is advantageously at least 750, more preferably at least 1000. Most preferably, less than 100 ppm Al is present.
Zeolite beta is characterized by 12-member ring pore openings and a three dimensional interconnecting channel system; its framework structure is more completely described in U.S. Pat. No. 3,308,069, Szostak, Handbook of Molecular Sieves, pp. 92-96, Higgin et al., Zeolites, 8, 446 (1986), and Treacy et al., Nature, 332, 249 (1988). The catalyst utilized in the invention thus has a fundamentally different structure than the titanium-containing molecular sieves reported in the prior art (e.g., the TS-1 catalyst described in U.S. Pat. No. 4,410,501, which has an MFI structure; the TS-2 catalyst described by Reddy et al. in Appl. Cat. 58, L1 (1990), which has a ZSM-11 structure).
In preferred embodiments, the titanium-containing molecular sieve has relatively large pores (equal to or greater than about 6 angstroms on average) and has a zeolite-type structure comprised of Si and a lesser amount of Ti. A crystallinity of greater than 75% is usually desirable. Preferably, the molar ratio of Ti:Si is from 0.1:99.9 to 20:80, with ratios in the range of 1:99 to 15:85 being especially preferred. The titanium-containing molecular sieve advantageously may have a titanium content of from 1 to 10 weight percent.
The general formula for the titanium-containing molecular sieve is preferably as follows:
SiO2 :yTiO2
wherein y is from 0.01 to 0.25 (preferably, 0.03 to 0.20).
A suitable method for the preparation of the aforedescribed titanium-containing molecular sieves involves a procedure wherein zeolite beta is dealuminated and the framework vacancies created by dealumination filled by titanium atoms. This method is preferred for use since it is relatively rapid and provides high yields of active catalyst, as compared to, for example, hydrothermal techniques which can require 1 week or more per batch and which provide lower yields of catalyst. Post-synthesis dealumination methods are well-known and include, for example, reaction or leaching with mineral acids (e.g., HCI, H2 SO4, HNO3) or chelating agents and hydrothermal or steaming treatments (possibly combined with acid leaching). See, for example, the extensive listing of publications describing zeolite dealumination methods catalogued in U.S. Pat. No. 4,576,805 (col. 8, line 62 through col. 9, line 27) and Scherzer, "The Preparation and Characterization of Aluminum-Deficient Zeolites", ACS Syrup. Ser. 248, 157-200 (1984). A particularly preferred method employs treatment of zeolite beta with a mineral acid such as nitric acid (preferably, 2 to 13 M; most preferably, concentrated nitric acid) at a temperature of from 25� C. to 150� C. for a period of time of from 5 minutes to 24 hours. Other mineral acids and carboxylic acids could alternatively be used, as described, for example, in British Pat. No. 1,061,847, European Pat. Publication No. 488,867, Kraushaar et al., Catalysis Letters 1, 81-84 (1988), Chinese Pat. No. 1,059,701 (Chem. Abst. 117:114655g), European Pat. Publication No. 95,304, and Chinese Pat. No. 1,048,835 (Chem. Abst. 115:52861 u). The beta zeolite is desirably suspended in or otherwise contacted with a relatively large volume of the nitric acid (preferably, from 10 to 1000 parts by weight nitric acid per 1 part by weight of the zeolite beta). Multiple dealuminations of this sort may be performed to effect more complete Al removal. Suitable dealumination methods of this type are described in more detail in Lami et al., Microporous Materials 1, 237-245 (1993), and European Pat. Publication No. 488,867. The dealuminated material may thereafter be contacted with a titanium source. For example, the dealuminated zeolite beta may be exposed to a volatile titanium source such as TiCl4 vapor in nitrogen for 1 to 24 hours at an elevated temperature (preferably, 250� C. to 750� C.). A liquid phase source of titanium such as (NH4)2 TiF6 (aq.) or TiF4 (aq.) may alternately be utilized to insert Ti atoms into the framework vacancies of the dealuminated zeolite beta. Methods of post-synthesis titanium incorporation into zeolite materials are described, for example, in U.S. Pat. No. 4,576,805, U.S. Pat. No. 4,828,812, and Kraushaar, et al., Catal. Lett. 1, 81-84 (1988). It may be desirable to then treat the titanium-containing molecular sieve with an ammonium salt such as ammonium nitrate, an acid solution (such as aqueous nitric acid) or the like to convert the titanium source to acid form (i.e., hydrogen or hydronium form) or to remove extra-framework aluminum. Water-washing, drying, and/or calcination may also be advantageous.
To further enhance the performance of certain titanium-containing molecular sieves prepared as described hereinabove, it may be advantageous to contact the catalyst with an ammonium, alkali metal and/or alkaline earth metal compound. Without wishing to be bound by theory, it is believed that this enhancement is attributable to the neutralization of certain metal-associated acidic sites present in the titanium-containing molecular sieve. A preferred method for accomplishing this modification is to dissolve the ammonium, alkali metal or alkaline earth metal compound in water or other suitable liquid medium; the resulting solution is then brought into intimate contact with the molecular sieve. This procedure preferably is performed at a temperature sufficiently high so as to accomplish the partial (i.e., at least 25%) or complete exchange or replacement of the ammonium, alkali metal or alkaline earth metal for the hydrogen cations of the acidic sites within a practicably short period of time (e.g., within 24 hours). For this purpose, temperatures of from about 25� C. to 150� C. will generally suffice. The concentration of ammonium, alkali metal or alkaline earth metal compound in the liquid medium may be varied as desired and will typically be from about 0.001 to 5 molar. Optimum concentrations may be readily ascertained by routine experimentation. Following the desired cation exchange, the excess liquid medium may be separated from the modified titanium-containing molecular sieve by filtration, decantation, centrifugation, or other such technique, and the modified titanium-containing molecular sieve washed (if desired) with water or other liquid substance, and then dried and/or calcined prior to use in the epoxidation process of this invention. If an ammonium compound has been utilized, calcination is preferably avoided so as to minimize any re-protonation of the catalyst.
The particular ammonium, alkali metal or alkaline earth metal compound selected for use is not critical but preferably is water-soluble and is desirably selected from ammonium, alkali metal or alkaline earth metal hydroxides and oxides (e.g., sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide), ammonium, alkali metal or alkaline earth metal carbonates (e.g., sodium carbonate, potassium carbonate), ammonium, alkali metal or alkaline earth metal bicarbonates (e.g., sodium bicarbonate, potassium bicarbonate), ammonium, alkali metal or alkaline earth metal nitrates (e.g., sodium nitrate, potassium nitrate), ammonium, alkali metal or alkaline earth metal halides (e.g., potassium chloride, sodium bromide, sodium chloride), ammonium, alkali metal or alkaline earth metal sulfates (e.g., sodium sulfate, potassium sulfate), ammonium, alkali metal or alkaline earth metal salts of carboxylic acids (e.g., sodium acetate), and the like and mixtures thereof. The counter anion in the ammonium, alkali metal or alkaline compound should be chosen such that it does not interfere with the desired epoxidation activity of the modified titanium-containing molecular sieve nor detrimentally alter its crystalline structure. For example, it has been found that under certain conditions the use of alkali metal pyrophosphates may deactivate or poison the molecular sieve catalyst.
In one embodiment of the invention, an ammonium, alkali metal, or alkaline earth-modified titanium-containing molecular sieve is generated in-situ during epoxidation through the use of an unmodified titanium-containing molecular sieve in combination with either an ammonium, alkali metal or alkaline earth compound of the type described previously or a buffer comprised of an ammonium, alkali metal or alkaline earth salt of a carboxylic acid or the like. For example, the reaction medium wherein the olefin is contacted with hydrogen peroxide may contain a NaOAc/HOAc buffer system (preferably, 0.1 to 5M) in a suitable solvent such as an alcohol (e.g., methanol). Alternatively, an alkali metal compound alone such as sodium acetate could be utilized. In a batch process, the ammonium, alkali metal or alkaline earth compound could, for example, be added by itself prior to initiation of epoxidation while in a continuous process (as when a CSTR reactor is employed) such compound could be combined with one of the feed streams containing one of the other reaction components such as the hydrogen peroxide.
The amount of catalyst employed is not critical, but should be sufficient so as to substantially accomplish the desired epoxidation reaction in a practicably short period of time. The optimum quantity of catalyst will depend upon a number of factors including reaction temperature, olefin reactivity and concentration, hydrogen peroxide concentration, type and concentration of organic solvent as well as catalyst activity. Typically, however, the amount of catalyst will be from 0.001 to 10 grams per mole of olefin. The concentration of titanium in the total epoxidation reaction mixture will generally be from about 10 to 10,000 ppm.
The catalyst may be utilized in powder, pellet, microspheric, monolithic, extruded, or any other suitable physical form. The use of a binder (co-gel) or support in combination with the titanium-containing molecular sieve may be advantageous. Supported or bound catalysts may be prepared by the methods known in the art to be effective for zeolite catalysts in general.
Illustrative binders and supports (which preferably are non-acidic in character) include silica, alumina, silica-alumina, silica-titania, silica-thoria, silica-magnesia, silica-zironia, silica-beryllia, and ternary compositions of silica with other refractory oxides. Also useful are clays such as montmorillonites, koalins, bentonites, halloysites, dickites, nacrites, and anaxites. The proportion of titanium-containing molecular sieve to binder or support may range from 99:1 to 1:99, but preferably is from 5:95 to 80:20. The catalyst may also be impregnated or admixed with a noble metal such as Pt, Pd, or the like.
The olefin substrate epoxidized in the process of this invention may be any organic compound having at least one ethylenically unsaturated functional group (i.e., a carbon-carbon double bond) and may be a cyclic, branched or straight chain olefin. The olefin may contain aryl groups (e.g,, phenyl, naphthyl). Preferably, the olefin is aliphatic in character and contains from 2 to 30 carbon atoms (i.e., a C2 -C30 olefin). The use of light (low-boiling) C2 to C10 mono-olefins is especially advantageous. More than one carbon-carbon double bond may be present in the olefin; dienes, trienes, and other polyunsaturated substrates thus may be used. The double bond may be in a terminal or internal position in the olefin or may alternatively form part of a cyclic structure (as in cyclohexene, for example). Other examples of suitable substrates include unsaturated fatty acids or fatty acid derivatives such as esters or glycerides and oligomeric or polymeric unsaturated compounds such as polybutadiene. Benzylic and styrenic olefins may also be epoxidized, although the epoxides of certain styrenic olefins such as styrene may further react or isomerize under the conditions utilized in the present invention to form aldehydes and the like.
The olefin may contain substituents other than hydrocarbon substituents such as halide, carboxylic acid, ether, hydroxy, thiol, nitro, cyano, ketone, acyl, ester, anhydride, amino, and the like.
Exemplary olefins suitable for use in the process of this invention include ethylene, propylene, the butenes (e.g., 1,2-butene, 2,3-butene, isobutylene), butadiene, the pentenes, isoprene, 1-hexene, 3-hexene, 1-heptene, 1-octene, diisobutylene, 1-nonene, 1-tetradecene, pentamyrcene, camphene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, the trimers and tetramers of propylene, styrene (and other vinyl aromatic substrates), polybutadiene, polyisoprene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, cyclododecatriene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinyl cyclohexane, vinyl cyclohexene, methallyl ketone, allyl chloride, allyl bromide, acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, crotyl chloride, methallyl chloride, the dichlorobutenes, allyl alcohol, allyl carbonate, allyl acetate, alkyl acrylates and methacrylates, diallyl maleate, dially phthalate, unsaturated triglycerides such as soybean oil, and unsaturated fatty acids, such as oleic acid, linolenic acid, linoleic acid, erucic acid, palmitoleic acid, and ricinoleic acid and their esters (including mono-, di-, and triglyceride esters) and the like.
Mixtures of olefins may be epoxidized and the resulting mixtures of epoxides either employed in mixed form or separated into the different component epoxides.
The process of this invention is especially useful for the epoxidation of C2 -C30 olefins having the general structure ##STR1## wherein R1, R2, R3, and R4 are the same or different and are selected from the group consisting of hydrogen and C1 -C20 alkyl.
The oxidizing agent employed in the process of this invention is a hydrogen peroxide source such as hydrogen peroxide (H2 O2) or a hydrogen peroxide precursor (i.e., a compound which under the epoxidation reaction conditions is capable of generating or liberating hydrogen peroxide).
The amount of hydrogen peroxide relative to the amount of olefin is not critical, but most suitably the molar ratio of hydrogen peroxide:olefin is from 100:1 to 1:100 when the olefin contains one ethylenically unsaturated group. The molar ratio of ethylenically unsaturated groups in the olefin substrate to hydrogen peroxide is more preferably in the range of from 1:10 to 10:1. One equivalent of hydrogen peroxide is theoretically required to oxidize one equivalent of a mono-unsaturated olefin substrate, but it may be desirable to employ an excess of one reactant to optimize selectivity to the epoxide. In particular, the use of a small to moderate excess (e.g., 5 to 50%) of olefin relative to hydrogen peroxide may be advantageous for certain substrates.
Although the hydrogen peroxide to be utilized as the oxidizing agent may be derived from any suitable source, a distinct practical advantage of the process of this invention is that the hydrogen peroxide may be obtained by contacting a secondary alcohol such as alpha-methyl benzyl alcohol, isopropyl alcohol, 2-butanol, or cyclohexanol with molecular oxygen under conditions effective to form an oxidant mixture comprised of secondary alcohol and hydrogen peroxide (and/or hydrogen peroxide precursors). Typically, such an oxidant mixture will also contain a ketone such as acetophenone, acetone, or cyclohexanone corresponding to the secondary alcohol (i.e., having the same carbon skeleton), minor amounts of water, and varying amounts of other active oxygen species such as organic hydroperoxides. Molecular oxygen oxidation of anthrahydroquinone, alkyl-substituted anthrahydroquinones, or water-soluble anthrahydroquinone species may also be employed to generate the hydrogen peroxide oxidant. The hydrogen peroxide may be generated in situ immediately prior to or simultaneous with epoxidation, as described, for example, in European Pat. Publication No. 526,945, Japanese Kokai No. 4-352771, Ferrini et al., "Catalytic Oxidation of Alkanes Using Titanium Silicate in the Presence of In-Situ Generated Hydrogen Peroxide", DGMK Conference on Selective Oxidations in Petrochemistry, Sep. 16-18, 1992, pp. 205-213, and European Pat. Pub. No. 469,662.
If desired, a solvent may additionally be present during the epoxidation process of this invention in order to dissolve the reactants other than the titanium-containing molecular sieve catalyst, to provide better temperature control, or to favorably influence the epoxidation rates and selectivities. The solvent, if present, may comprise from 1 to 99 weight percent of the total epoxidation reaction mixture and is preferably selected such that it is a liquid at the epoxidation reaction temperature. Organic compounds having boiling points at atmospheric pressure of from about 25� C. to 300� C. are generally preferred for use. Excess olefin may serve as a solvent or diluent. Illustrative examples of other suitable solvents include, but are not limited to, ketones (e.g., acetone, methyl ethyl ketone, acetophenone), ethers (e.g., tetrahydrofuran, butyl ether), nitriles (e.g., acetonitrile), aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, and alcohols (e.g., methanol, ethanol, isopropyl alcohol, t-butyl alcohol, alpha-methyl benzyl alcohol, cyclohexanol). An important practical advantage of the present invention is that it may readily be practiced using bulkier alcohol solvents such as alpha-methyl benzyl alcohol, whereas poor results are obtained with such solvents when other titanium-containing molecular sieves such as TS-1 are utilized as catalyst. This flexibility minimizes the problems which might otherwise be encountered when trying to separate the epoxide product from the epoxidation reaction mixture. Quantitative removal of methanol, for example, from a relatively light epoxide such as propylene oxide is difficult due to the similarity in their boiling points. More than one type of solvent may be utilized. Water may also be employed as a solvent or diluent; surprisingly, the process of the invention proceeds with minimal hydrolysis even when a significant quantity of water is present in the epoxidation reaction mixture. Biphasic as well as monophasic reaction systems thus are possible using the present invention.
The reaction temperature is not critical, but should be sufficient to accomplish substantial conversion of the olefin to epoxide within a reasonably short period of time. It is generally advantageous to carry out the reaction to achieve as high a hydrogen peroxide conversion as possible, preferably at least 50%, more preferably at least 90% most preferably at least 95%, consistent with reasonable selectivities. The optimum reaction temperature will be influenced by catalyst activity, olefin reactivity, reactant concentrations, and type of solvent employed, among other factors, but typically will be in a range of from about 0� C. to 150� C. (more preferably, from about 25� C. to 120� C.). Reaction or residence times of from about 1 minute to 48 hours (more desirably, from about 10 minutes to 8 hours) will typically be appropriate, depending upon the above-identified variables. Although subatmospheric pressures can be employed, the reaction is preferably (especially when the boiling point of the olefin is below the epoxidation reaction temperature) performed at atmospheric pressure or at elevated pressure (typically, between 1 and 100 atmospheres). Generally, it will be desirable to pressurize the epoxidation vessel sufficiently maintain the reaction components as a liquid phase mixture. Most (i.e., over 50%) of the olefin should preferably be present in the liquid phase.
The process of this invention may be carried out in a batch, continuous, or semi-continuous manner using any appropriate type of reaction vessel or apparatus such as a fixed bed, transport bed, fluidized bed, stirred slurry, or CSTR reactor in a monophase or biphase system. Known methods for conducting metal-catalyzed epoxidations of olefins using hydrogen peroxide will generally also be suitable for use in this process. Thus, the reactants may be combined all at once or sequentially. For example, the hydrogen peroxide or hydrogen peroxide precursor may be added incrementally to the reaction zone. The hydrogen peroxide could also be generated in situ within the same reactor zone where epoxidation is taking place. Once the epoxidation has been carried out to the desired degree of conversion, the epoxide product may be separated and recovered from the reaction mixture using any appropriate technique such as fractional distillation, extractive distillation, liquid-liquid extraction, crystallization, or the like. After separating from the epoxidation reaction mixture by any suitable method such as filtration, the recovered catalyst may be economically re-used in subsequent epoxidations. Where the catalyst is deployed in the form of a fixed bed, the epoxidation product withdrawn as a stream from the epoxidation zone will be essentially catalyst free with the catalyst being retained within the epoxidation zone. In certain embodiments of the instant process where the epoxide is being produced on a continuous basis, it may be desirable to periodically or constantly regenerate all or a portion of the used titanium-containing molecular sieve catalyst in order to maintain optimum activity and selectivity. Suitable regeneration techniques include, for example, treating the catalyst with solvent, calcining the catalyst, and/or contacting the catalyst with an ammonium, alkali metal or alkaline earth compound. Any unreacted olefin or hydrogen peroxide may be similarly separated and recycled. Alternatively, the unreacted hydrogen peroxide (especially if present at concentrations too low to permit economic recovery) could be thermally or chemically decomposed into non-peroxy species such as water and oxygen, for example. In certain embodiments of the process where the hydrogen peroxide is generated by molecular oxygen oxidation of a secondary alcohol, the crude epoxidation reaction mixture will also contain a secondary alcohol and a ketone corresponding to the secondary alcohol. After separation of the epoxide from the secondary alcohol and the corresponding ketone, the ketone may be converted back to secondary alcohol by hydrogenation. For example, the ketone may be reacted with hydrogen in the presence of a transition metal hydrogenation catalyst such as a Raney nickel, copper chromite, ruthenium, or supported palladium catalyst. Hydrogenation reactions of this type are well known to those skilled in the art. The secondary alcohol may also be dehydrated using known methods to yield valuable alkenyl products such as styrene.
The titanium-containing molecular sieve described herein, in addition to being a useful epoxidation catalyst, also has utility as an ion exchanger, a shape-selective separation medium, or a catalyst for other hydrocarbon conversion processes, including, for example: cracking, selectoforming, hydrogenation, dehydrogenation, oligomerization, alkylation, isomerization, dehydration, hydroxylation of olefins or aromatics, alkane oxidation, reforming, disproportionation, methanation, and the like. The molecular sieve of this invention is particularly useful for catalyzing the same reactions wherein titanium silicalites (also referred to as titanium silicates) have heretofore been employed. Illustrative applications of this type are as follows:
a) A process for the manufacture of a ketone oxime which comprises reacting a ketone such as cyclohexanone with ammonia and hydrogen peroxide in the liquid phase at a temperature of from 25� C. to 150� C. in the presence of a catalytically effective amount of the titanium-containing molecular sieve. Reactions of this type are well known in the art and suitable conditions for carrying out such a synthetic transformation in the presence of a titanium silicalite catalyst are described, for example, in U.S. Pat. No. 4,745,221, Roffia et al., "Cyclohexanone Ammoximation: A Breakthrough in the 6-Caprolactam Production Process", in New Developments in Selective Oxidation, Centi et al, eds., pp. 43-52 (1990), Roffia et al., "A New Process for Cyclohexanonoxime", La Chimica and L'Industria 72, pp. 598-603 (1990), U.S. Pat. Nos. 4,894,478, 5,041,652, 4,794,198, Reddy et al., "Ammoximation of Cyclohexanone Over a Titanium Silicate Molecular Sieve", J. Mol. Cat. 69, 383-392 (1991), European Pat. Pub. No. 496,385, European Pat. Pub. No. 384,390, and U.S. Pat. No. 4,968,842, (the teachings of the foregoing publications are incorporated herein by reference in their entirety).
(b) A process for oxidizing a paraffinic compound (i.e., a saturated hydrocarbon) comprising reacting the paraffinic compound at a temperature of from 25� C. to 200� C. with hydrogen peroxide in the presence of a catalytically effective amount of the titanium-containing molecular sieve. Reactions of this type are well known in the art and suitable conditions for carrying out such a synthetic transformation in the presence of a titanium silicalite are described, for example, in Huybrechts et al., Nature 345,240 (1990), Clerici, Appl. Catal. 68, 249 (1991), and Tatsumi et al., J. Chem. Soc. Chem. Commun. 476 (1990), Huybrechts et al., Catalysis Letters 8, 237-244 (1991 ), the teachings of which are incorporated herein by reference in their entirety.
(c) A process for hydroxylating an aromatic hydrocarbon (e.g., phenol) comprising reacting the aromatic compound at a temperature of from 50� to 150� C. with hydrogen peroxide in the presence of a catalytically effective amount of the titanium-containing molecular sieve to form a phenolic compound (e.g., cresol). Reactions of this type are well known in the art and suitable conditions for carrying out such a synthetic transformation in the presence of a titanium silicalite catalyst are described, for example, in U.S. Pat. No. 4,396,783, Romano et al., "Selective Oxidation with Ti-silicalite", La Chimica L'Industria 72, 610-616 (1990), Reddy et al., Applied Catalysis 58, L1-L4 (1990),
(d) A process for isomerizing an aryl-substituted epoxide to the corresponding beta-phenyl aldehydes comprising contacting the aryl-substituted epoxide with a catalytically effective amount of the titanium-containing molecular sieve at a temperature of from 25� C. to 150� C. See, for example, U.S. Pat. No. 4,495,371 (incorporated herein by reference in its entirety).
(e) A process for oxidizing a vinyl benzene compound to the corresponding beta-phenyl aldehyde comprising reacting the vinyl benzene compound with hydrogen peroxide at a temperature of from 20� C. to 150� C. in the presence of the titanium-containing molecular sieve. See, for example, U.S. Pat. No. 4,609,765 (incorporated herein by reference in its entirety).
(f) A process for synthesizing an N, N-dialkyl hydroxylamine comprising reacting the corresponding secondary dialkyl amine with hydrogen peroxide in the presence of the titanium-containing molecular sieve. See, for example, U.S. Pat. No. 4,918,194 (incorporated herein by reference in its entirety).
(g) A process for oxidizing an aliphatic alcohol comprising reacting the aliphatic alcohol with hydrogen peroxide in the presence of the titanium-containing molecular sieve at a temperature of from 25� C. to 150� C. to form the corresponding ketone or aldehyde of said aliphatic alcohol. See, for example, U.S. Pat. No. 4,480,135 (incorporated herein by reference in its entirety).
(h) A process for synthesizing a glycol monoalkyl ether comprising reacting an olefin, an aliphatic alcohol, and hydrogen peroxide in the presence of the titanium-containing molecular sieve at a temperature of from 25� C. to 150� C. See, for example, U.S. Pat. No. 4,476,327 (incorporated herein by reference in its entirety).
From the foregoing description, one skilled in the art can readily ascertain the essential characteristics of this invention, and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages, conditions, and embodiments.
The following examples further illustrate the process of this invention, but are not limitative of the invention in any manner whatsoever.
This example demonstrates the preparation of a titanium-containing molecular sieve in accordance with the present invention and its utility an olefin epoxidation catalyst.
Calcined zeolite beta (5 g; Conteka 41-89-001 ) having a SiO2 :Al2 O3 ratio of 24 is added to 500 ml of 13N nitric acid. The resulting suspension is heated at 80� C. for four hours with stirring. The suspended solids are recovered by filtration and retreated twice in the same manner with fresh portions of 13N nitric acid. After recovering by filtration, the solids are washed well with deionized water, and dried at 95� C. overnight to provide a dealuminated zeolite beta having a Si/Al molar ratio of 940.
The dealuminated zeolite beta is added to a fitted quartz tube. The tube is loaded vertically in a furnace and a slow (100 cc/min) nitrogen flow initiated. The sample is heated at 400� C., then heated at 600� C. and the nitrogen flow increased to 300 cc/min. Once the temperature has stabilized at 600� C., the sample is treated with titanium tetrachloride for eight hours by sparging the nitrogen feed through a warmed (40� C.) TiCl4 solution. After this time, TiCl4 treatment is discontinued and nitrogen flow through the sample continued at 600� C. for an additional hour. The sample is cooled to room temperature overnight with continuous nitrogen flow. The cooled sample is treated with a 1M aqueous solution of ammonium nitrate at 80� C. for four hours. The sample is recovered by filtration, washed well with water, dried at 95� C. and then calcined at 550� C. for 6 hours to yield a titanium-containing molecular sieve having a very low level of aluminum. Raman spectroscopy and 29 Si and 27 Al MAS NMR also confirmed that near complete dealumination takes place and that titanium is inserted into the framework of the zeolite. The x-ray powder diffraction pattern of the titanium-containing molecular sieve is shown in FIG. 1 and summarized in Table II. From 27 Al MAS NMR, it is estimated that less than 100 ppm aluminum is present.
The titanium-continuing molecular sieve thus obtained is evaluated as a catalyst for the hydrogen peroxide epoxidation of 1-hexane using the following conditions: 60� C., 12.2 g methanol (solvent), 16.5 mmol 1-hexene, 4.5 mmol hydrogen peroxide, 0.10 g catalyst.
The results of this evaluation are shown in Table I. Example 1-A shows that good epoxide selectivity can be achieved without modification of the catalyst with Group IA or Group IIA cations, due (it is believed) to the extremely low aluminum content of the catalyst. The activity of the catalyst was quite high, with over 90% conversion of hydrogen peroxide being attained in just one hour. When the catalyst was washed with 0.5% sodium acetate (Example 1-B), a somewhat lower initial rate of hydrogen peroxide reaction was observed together with improved selectivity. Example 1-C demonstrates that the titanium-containing molecular sieve which has been treated with sodium acetate also performs quite satisfactorily if alpha-methyl benzyl alcohol rather than methanol is used as a solvent for epoxidation. In contrast, titanium silicalite having a TS-1 structure exhibited little activity in an alpha-methyl benzyl alcohol medium (Example 1-D).
TABLE I__________________________________________________________________________ H2 O2 Hexene Catalyst Time, Conversion Epoxide Glycol Ether Conversion, Epoxide/GlycolExampleSolvent Treatment hr % Selectivity, %a Selectivity, %a % Ether__________________________________________________________________________ Ratio1-A methanol none 1 93 58 1.7 19 3 6 96 52 (+17% other) 31 1 3 (+39% Other)1-B methanol 0.5% 1 68 75 5 16 15 NaOAc 6 97 63 19 23 41-C alpha methyl 0.5% 1 98 68 <2 18.4 >50benzyl alcohol NaOAc1-Dcalpha methyl --(b) 1 no reaction -- -- -- --benzyl alcohol__________________________________________________________________________ a based on hydrogen peroxide (b)TS1 catalyst (U.S. Pat. No. 4,410,501) c comparative example
TABLE II______________________________________d(angstroms) Relative Intensity______________________________________11.50 vs 6.57 mw 6.05 mw 4.13 w 3.95 s 3.51 mw 3.28 mw 3.24 mw 3,19 w 3.02 w 2.68 w 2.48 w 2.08 w 1.69 w______________________________________ d = interplanar distance vs = very strong s = strong mw = medium weak w = weak
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Url: http://blogs.msdn.com/peterlau/archive/2008/08/...
I just got back from the Silverlight 2 Firestarter in New York City. I had a great time. We have a good turn-out and great discussions about the technology. The Microsoft guys that set this up were just great, especially Peter Laudati who organized the whole thing and made my short trip up there really simple and fun.
For the attendees of the talks, here's a link to the example project I built for you:
What has twenty-five years in software development taught me? Find out in my new eBook!
2001-2013 © Shawn Wildermuth. ALL Rights Reserved.

subset: commoncrawl


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"I was elated to see that I was a winner alongside such stylish women," she says.
Delhi's Most Stylish 2013 gala event will be held later this month, and among these ten women, you can pick your favourite by voting. Here's a look at the ladies, along with their voting codes. To vote, sms DMS<Space>Code to 54242 Koel Puriecode: w04The actor and TV anchor can give any fashion maverick a run for their money. Bandage dresses, one-shoulder sheaths, rompers and stylish accessories — she knows how to make her stylish choices work.
Indrani Dasguptacode: w07The gorgeous model exudes dollops of charm and has an enviable style sense. She's known for taking fashion risks and combines designer separates innovatively, like her print on print ensembles, making her a true style diva. Her statement accessories also set the leggy beauty apart.
Shweta Nandacode: w03Shweta's style has evolved over the years and that's what puts her ahead of the fashion curve. From chic, couture dresses to formal separates and ornate ethnic wear, the philanthropist knows how to ace various styles.
Sara Pilotcode: w02She's known for her elegant simplicity, innate charm and classy, fashionable sartorial picks. Mostly spotted in ethnic wear, the philanthropist makes quite a statement in her designer saris, and frill-less jewellery and makeup.
Ambika Anandcode: w06From sky-high heels and on-trend dresses — including sheaths, shifts, shirt dresses, jumpsuits, asymmetric gowns — there is nothing the TV anchor can't carry off with elan. Her style is immaculate — from camera-ready hair and makeup to designer outfits.
Sonalika Sahaycode: w09Whether she is stepping out for work or for a Page 3 party, the model is as full of poised elegance as she is on the ramp. Sonalika also has the perfect body to rock anything she sports and is always ahead in terms of latest trends.
Roshni Nadarcode: w10Roshni has a distinctive style of her own to flaunt. It may be simple and minimalistic, but she is able to make an impressive, lasting impact. The industrialist often goes for formal suits, smart casual separates and designer salwar kameez.
Kanika Salujacode: w08The designer's individuality is manifested through her style. Custom-made metal inputs are a staple for Kanika, who is not afraid to experiment, and incorporates them in her outfits. Her buzzed cut and trademark lipstick make her stand out.
Nira Singhcode: w05The restaurateur is known for adding oodles of oomph to the food world. Nira's daily style is ultra fashionable and her everyday outfit picks include sophisticated dresses, high-waist skirts and fashionably put-together separates.


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About the Collection:Slip into trend-right style and luxurious warmth with Australian sheepskin footwear and cold weather fashion accessories from EMU. For more than 15 years, EMU has passionately produced the world's finest premium sheepskin and Merino wool products.
About The Guest:
On-air guest Liz Hall is vice president of sales for EMU and has nearly 3 decades of experience in the retail fashion and accessories industries. Join Liz and discover the fashionable, functional style of EMU genuine sheepskin footwear & accessories.


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Is It Now 'Uncool' To Major In The Humanities?
In the following article by Stanford University News, Dean Larry Kramer urges prospective law students to resist the temptation to continuously keep all options open. Cynthia Haven reports:
Follow your bliss and take a few chances, say Stanford deans of business, law, medicine and education. Sometimes it looks like "you have been building your CVs since you were 4 years old," added law school's Larry Kramer.
As the world looks to science and technology for its future, is an art or literature major toxic? Is it poison, particularly, if you intend to go on to law school, business school, med school or even education? Or even if you plan to be employed at all?
In hard economic times, humanities must justify their worth. And four Stanford deans gathered Tuesday to defend the humanities in the face of declining interest and enrollment in those subjects.
Law school Dean Larry Kramer, business school Dean Garth Saloner, education Dean Deborah Stipek, and Charles Prober, senior associate dean for medical education, spoke to Stanford sophomores Tuesday at an event moderated by Harry Elam, vice provost for undergraduate education.
Kramer said the decline was part of broader, shifting cultural tends. When he attended college, he said, it was "completely uncool" to major in something other than the humanities – for example, to major in science or engineering.
The shift started in the 1980s, he said, with an increased focus on economic development and personal wealth.
When Elam asked how the humanities had affected the deans' own educational experience, Kramer said he began taking law courses under duress, because "my mother was so on my back to do something," while he was trying to be a writer.
"I thought I was OK. I wasn't," he said.
One of his experimental law courses, taught by former U.S. Attorney General Edward Levi, "essentially started with a debate about 'might makes right'" – winding from Socrates to Roe v. Wade, with Rousseau, Locke, and Hobbes in between, bringing together the worlds of philosophy, education, business.
Kramer was sold. He became Levi's assistant.
Kramer said the law school favors applicants who are "the most interesting, most inquisitive, most ambitious," but that one skill from the humanities is imperative:
"Writing skills are absolutely critical," he said. "That's true for any profession."
Kramer said the law school applications were "humbling on paper" compared with his own cohort years ago. However, it often appears as if "you have been building your CVs since you were 4 years old" and that "the route to success is to collect as many gold stars as you can and keep your options open."
Kramer said it was a "horrible" recipe for life.
"At some point you do have to make choices," he said. "It's scary to me how many times the choice has been made by the choices not made."


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Build Your Royalty Free Music Library
When you buy royalty free music from SmartSound, it's always available for you to customize and download directly from our web site or by installing it on your workstation for access with our Sonicfire Pro software.
Save Time With Our Patented Software
Our Professional Soundtrack Creation Technology automatically delivers professional music edits instantly. Adjusting the length, arrangement and instrumentation of every SmartSound track is instantaneous and 100% professional!
Be More Creative
SmartSound technology (Sonicfire Pro) allows you to express your creativity far beyond regular royalty free music. Since our music is totally customizable for length, mood and instrument mix, you can create over 20 million different soundtracks to find that perfect fit for your project.
Impress Your Audience
Our royalty free music library is comprised of a hand-picked and professionally curated collection of music. Our music comes from top musicians, film composers, indie bands and independent artists. No sifting through thousands of crowd-sourced tracks. Every SmartSound track is a winner!
Use Legal Music
SmartSound offers one of the most generous worry-free music licenses in the industry. Put SmartSound in your (or your clients) productions and play it anywhere for any amount of time at no additional cost. (*If you need to manufacture more than 10,000 pieces of physical media, you'll need to contact us for approval...that's it!)
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Sonicfire Pro Full Edition Tutorials
Purchasing & Downloading Music with Sonicfire Pro 5.8
Professor: Larry Jordan | Class Time: 9 minutes 42 seconds
In this tutorial, Larry Jordan outlines the new account integration features of Sonicfire Pro 5.8, and demonstrates how this new version helps you purchase and install music from our site much more easily. It also covers reinstalling existing purchases from within the Sonicfire Pro interface. This new version also includes a brand new music album, "Core Evolution".
Professor: Larry Jordan | Class Time: 8 minutes 02 seconds
Larry Jordan takes you on a tour of the powerful timeline-based interface of the Sonicfire Pro 5. Learn your way around the different windows: Timeline, Properties, VU Meters, Bin/Spotting, and Video. Larry also gets started with a project so you can see the basic functionality.
Using Mood Mapping
Professor: Larry Jordan | Class Time: 7 minutes 15 seconds
Larry Jordan shows you how to use the Mood Mapping feature of Sonicfire Pro 5 to adjust the music to fit the changing moods of your production. With SmartSound's huge library of Multi-Layer Music, the Mood Mapping feature gives you access to up to 9 separate instrument layers. Open with Drum and Bass, Duck for Dialog and close with a Full Mix for the action sequence. You'll also learn how to use the new Hit Files feature to emphasize key events in your video. No other music library offers this level of creativity.
Custom Length Music
Professor: Larry Jordan | Class Time: 8 minutes 10 seconds
Larry Jordan shows you how to use the Custom Length feature of Sonicfire Pro 5 to adjust the music to fit the changing moods of your production. This capability alone will save you hours of editing without having to compromise an ounce of quality. Since SmartSound is real music played by real musicians, not just midi or synthesizer music, this is like having your own personal music editor on hand anytime you need it. When you just can't cut the scene to the music SmartSound's Custom Length features come to the rescue, allowing you to keep the integrity of your video and your story.
Using the Spotting Feature
Professor: Larry Jordan | Class Time: 8 minutes 49 seconds
In this video Larry Jordan demonstrates the Spotting feature in Sonicfire Pro.
Timing Control
Professor: Larry Jordan | Class Time: 5 minutes 55 seconds
Larry Jordan demonstrates the awesome Timing Control feature in Sonicfire Pro 5. This feature allows you to move the beats of the music to match the events in your video.
Exporting Music and Using Smart Recall
Professor: Larry Jordan | Class Time: 6 minutes 21 seconds
Larry Jordan shows you how to get music from Sonicfire Pro 5 into your video or audio projects. A built in Sent To option sends the music right into your project making it the fastest way to get customized music into your timeline. Advanced options like exporting instruments as separate layers is useful for later customizing and surround sound mixes. The Smart Recall feature is also demonstrated to show how music files from Sonicfire Pro can be edited later without the need for saving project files.
Setting the Configuration Options
Professor: Larry Jordan | Class Time: 5 minutes 27 seconds
Larry Jordan helps you understand the configuration options of SmartSound Sonicfire Pro 5.
Customize Music and Lyrics Using SmartSound Vocal Music
Professor: Larry Jordan | Class Time: 9 minutes 57 seconds
In this tutorial, Larry Jordan creates a heartfelt video with Artbeats footage and shows you how to use the New SmartSound Music with Vocals to create a great music background complete with appropriate lyrics. He is using Sonicfire Pro 5 software and SmartSound's Voxation Series, Multi-Layer Music with Vocals. Search for music based on lyrics, change the arrangement so the lyrics match your video and even mix out instrument and lyrics that you don't want at any time in the timeline. SmartSound has the largest royalty-free music library available for immediate purchase and download.
Creating Sound Effects from Instrument Layers
Professor: Larry Jordan | Class Time: 4 minutes 56 seconds
In this tutorial, Larry Jordan shows you how to use Sonicfire Pro and SmartSound Multi-Layer music to create a sound effect or sound design element from part of an instrument layer. The SmartSound Multi-Layer Music offers incredible creativity and flexibility for making music fit perfectly to all of your productions. This is truly the most creative royalty-free music library available in the world...watch these tutorials and you'll agree.
Changing the Music Arrangement with Timing Control
Professor: Larry Jordan | Class Time: 4 minutes 31 seconds
The nature of royalty free music has been seriously limiting before SmartSound. Since the music wasn't made for your production it was complicated to edit and fit with the theme of your video. The SmartSound Music library smashes those problems to pieces and offers you a simple way to make each track a perfect fit to every project. This video shows you how to use the incredible Timing Control feature to change the arrangement of the music to better fit the pacing and timing of your video. Sometimes library music will change and develop out of sync with your story. Watch how Sonicfire Pro gives you the control to make the most creative productions ever.
How to Crossfade in Sonicfire Pro
Professor: Larry Jordan | Class Time: 1 minutes 50 seconds
This video tutorial shows you a quick tip for using Sonicfire Pro to easily crossfade to audio tracks. Now, the SmartSound technology edits SmartSound music so precisely that you will rarely need this feature for SmartSound music track. Nevertheless, this will work with SmartSound tracks as well as your own audio clips. Crossfading is a very useful feature that is simple to do in Sonicfire Pro.


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Abuse, whether emotional or physical, is never okay. Unfortunately, some women experience abuse from a partner. Abuse crosses all racial, ethnic and economic lines. Abuse often gets worse during pregnancy. Almost 1 in 6 pregnant women have been abused by a partner.
Abuse can come in many forms. An abusive partner may cause emotional pain by calling you names or constantly blaming you for something you haven't done. An abuser may try to control your behavior by not allowing you to see your family and friends, or by always telling you what you should be doing. Emotional abuse may lead you to feel scared or depressed, eat unhealthy foods, or pick up bad habits such as smoking or drinking.
An abusive partner may try to hurt your body. This physical abuse can include hitting, slapping, kicking, choking, pushing or even pulling your hair. Sometimes, an abuser will aim these blows at a pregnant woman's belly. This kind of violence not only can harm you, but it also can put your unborn baby in grave danger. During pregnancy, physical abuse can lead to miscarriage and vaginal bleeding. It can cause your baby to be born too soon, have low birthweight or physical injuries.
For many families, pregnancy can bring about feelings of stress, which is normal. But it's not okay for your partner to react violently to stress. Some partners become abusive during pregnancy because they feel:
It's common for couples to argue now and then. But violence and emotional abuse are different from the minor conflicts that couples have.
Ask yourself:
If you answered "Yes" to any of these questions, you may be in an unhealthy relationship.
Recognize that you are in an abusive relationship. Once you realize this, you've made the first step towards help. There are lots of things you can do.
Tell someone you trust. This can be a friend, a clergy member, a health care provider or counselor. Once you've confided in them, they might be able to put you in touch with a crisis hotline, domestic violence program, legal-aid service, or a shelter or safe haven for abused women.
Have a plan for your safety. This can include:
Remember: No one deserves to be physically or emotionally abused. Recognize the signs of abuse and seek help. You might feel very scared at the thought of leaving, but you've got to do it. You and your baby's life depends on it.
Georgetown University's Maternal and Child Health Library - domestic violence and abuse information.
National domestic violence hotline: (800) 799-SAFE (7233), (800) 787-3224 TTY
Last reviewed October 2008
It's best to wait until after having your baby to get one. Here's why: Hepatitis B, a dangerous liver infection, and HIV/AIDS are two of many diseases that can be passed along through bodily fluids. This means you can catch these diseases if you get a tattoo from someone who uses a dirty needle. And you can pass these diseases along to your baby during pregnancy.
We don't know how tattoo dyes and inks affect a developing baby. Small amounts of chemicals that might be harmless to an adult can have a much bigger impact on a growing baby.
Most healthcare providers will give an epidural to a woman with a tattoo on her lower back. But they may decide not to if the tattoo is recent and fresh. If you have a tattoo on your back and are considering getting an epidural for pain relief during childbirth, find out what the hospital's policy is before you're admitted.
Some spa treatments are safe. Others may be more painful than usual. And some - like mud baths - are a bad idea while you're pregnant.
Any spa treatments that raise your body temperature (like mud baths, hot wax and seaweed wraps) are almost always unsafe during pregnancy. Steam rooms, hot tubs, and saunas also raise your body temperature. They can make you dehydrated and overheated. This can be dangerous for you and your baby. Avoid these treatments while you're pregnant.
Be careful with skin treatments like facials and body scrubs. During pregnancy, your skin changes a lot and may be extra sensitive. Before you cover your whole body with a product, test it on a small area of skin to be sure it doesn't irritate.
Getting your eyebrows done and having your bikini line waxed are usually safe during pregnancy, but they may feel more painful to your sensitive skin.


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In a perfect world, every alarm clock, phone and radio would play 'K For Kelson' every morning in a bid to wake up the nation into a joyous sunshine-filled wonder state. It's just that edifying.
Bibio – K is for Kelson (taken from 'Mind Bokeh')
The song is taken from Bibio's excellent new album Mind Bokeh out on Warp Records. Listen to the whole thing here.
Listen back to the Nialler9 TXFM radio show or listen live every Thursday night at 10pm on 1052 TXFM.Listen to Nialler9 as a playlist


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America's Dream HomeWorks, Inc.
by paulstriger, Window Shopper
- Created: February 12, 2013, 3:21 am
- Updated: February 13, 2013, 4:28 pm
Hello, I am glad to have found this blog and look forward to learning a great deal from it as well as contribute to the valuable discussions here. With many years in the Home Improvement and General Contracting business, America's Dream HomeWorks has a wealth of experiences to share. As a medium sized business owner, I am proud to be a part of this community. Please all feel free to ask questions in any of my core knowledge areas: home improvement and contracting, information technology and internet marketing. Thank you, Mark Chernioglo America's Dream HomeWorks (This post was edited to remove a link. Please review our Community Best Practices for more information about how best to participate in our online discussions. Thank you.)
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By: Marcia Keppy
Imagine sitting down at your computer and with a few clicks, finding yourself a few hundred -- or even thousand -- dollars richer. No, I'm not talking about Internet gambling or a get-rich-quick scheme. This money is totally legal. In fact, it's already yours, you just have to make claim to it. Sounds too good to be true, I know, but there are billions of dollars out there just waiting to be claimed by ordinary people just like you and me.
Where does this money come from? It might be a long forgotten bank account that you left behind when you moved, or a relative's insurance policy that was never cashed. It may be a bond you purchased under your maiden name and forgot about. When these funds sit idle for a certain number of years, financial institutions are required to turn the money over to the state.
Same thing goes for things left in safe deposit boxes. When they've sat untouched for a number years the contents go to the state. But what's the state going to do with Grandma's wedding ring? Actually, many states auction off the property – think eBay – and then hold the money until they can find the owner.
Imagine it, the government looking for you – to GIVE you money! What a concept! If the government is holding onto money that could be sitting in your bank account or wallet, you'll probably want to know where it is, and how to get it back.
Each state has various ways of trying to connect people with their lost assets. Every year, generally in April, there will be an insert in newspapers listing the latest names added to the list of lost owners. Some states set up displays at public events, libraries and fairs. Others work with local lawmakers to try and get the word out. But the quickest, easiest way to find out if you have any unclaimed assets is to search an online database.
Most states have their own database that you can access by going to the state's Website. A wonderful resource for anyone looking for unclaimed property is www.missingmoney.com, a site run by the National Association of Unclaimed Property Administrators. It contains a wealth of information on abandoned property, and contact information for each state. It also allows you to do a nationwide search through links to each individual state, and it's all free.
For those that can't or don't want to take on the task themselves, there are companies that will do the searching for you. Sometimes called heir finders or asset locators, the firms help reunite owners with their property for a fee. Beware, however, that legitimate companies will never ask for payment before the property is returned to the rightful owner and whatever they charge should be a percentage of the money to be returned, not a flat fee. And before signing anything, have the company identify the property and verify that it's yours.
Once you've located your own abandoned property, spread the word. There are billions of dollars out there just waiting to be claimed.


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We didn't need another Black Sabbath album, but we should celebrate that we have one. Its existence — and the reunion of ¾ of the band's original lineup — defies conventional wisdom and improbable circumstances.
It started in 1979: Sabbath was in shambles. Never Say Die! was met with indifference by fans and critics; meanwhile, the band fired Ozzy Osbourne for excessive substance abuse during the ensuing tour, the culmination of an already testy friendship between Osbourne and guitarist Tony Iommi. The former would lead an erratic-yet-successful solo career for the next three decades, while the latter kept Black Sabbath alive until 1995 (though it was more of a husk of its former self).
The two eventually reconciled their differences and reunited Sabbath for Ozzfest and some studio sessions with producer Rick Rubin in 2001. But no new material came of it, as the band members' conflicting schedules cut the sessions short. Soon after, MTV's The Osbournes became a phenomenon, and the band went on hiatus.
Ten years passed before Black Sabbath decided to reunite one last time. "It's now or never," Iommi said. "We get along great. Everything's good." Rubin was brought back as producer, and 13 began to take shape. However — just like last time — the dominoes began to fall. Tony Iommi was diagnosed with cancer, drummer Bill Ward left because of a contract dispute, and Ozzy suffered a much publicized drug relapse and near divorce. How do you write and record an album with all that shit happening?
Answer: Channel it through the music. It's hard not to connect 13 to the context of its tumultuous recording process. With Rage Against the Machine's Brad Wilk replacing Ward, Black Sabbath takes a trip back to its doom-metal glory days — back when the songs really meant something. 13 doesn't arbitrarily reach for that vintage sound; rather, it's what came out of the band while age, health issues, and temptation bore down on them. These are songs fueled by contempt.
"Is this the end of the beginning/ Or the beginning of the end?" Ozzy asks during the album's introductory verse. Although "The End of the Beginning" is about a cyborg clone, the placement of that opening couplet acts as a mood setter. A similar question of fate is asked on the following track, "God is Dead?", a definitive depiction of this revived Sabbath. Iommi strikes a minor scale and meanders in these dark notes until the song's surging chorus: "The blood runs free, the rain turns red/ Give me the wine, you keep the bread." Sabbath hasn't sounded this heavy since 1975's Sabotage. "Zeitgeist" throws it back to their more psychedelic dabblings, as Ozzy's voice is put through a wah effect. It bears an uncanny resemblance to Paranoid's "Planet Caravan".
13 occasionally tries too hard to recall the old Sabbath and, as a result, lacks personality. "Damaged Soul" plods to a bluesy rhythm, breaks into a guitar solo, and repeats this pattern; it's totally listenable, just not very exciting or original. "Age of Reason" contains an infectious bridge ("These times are heavy/ And you're all alone"), though the rest of the song clings to a mundane riff. That's the risk with Iommi; he tends to lock into a groove, which can be a blessing or a curse depending on the guitar line he's settled on. Rick Rubin deserves praise for staying out of the band's way during the recording process: Iommi's guitar tone is blissfully doomy, just as it was on 2009 Dio-collab The Devil You Know. However, Rubin also deserves disparagement for the way he mixed the audio levels, which are crushed by distortion and compression. Otherwise well-recorded songs are blemished, an affliction all too pervasive in the modern music industry.
Despite the volume, 13 is a return to form — if a somewhat obvious one — and an example of perseverance. Ozzy gives a strong performance despite an aging voice, Geezer Butler's lyrics are as pessimistic as ever, and Iommi conjures the tones of old. Given all the distractions surrounding the record's release, it's shocking how well everything fits together. For a record 13 years in the making, 13 is worth the wait.
Essential Tracks: "God is Dead?", "Zeitgeist"
Feature artwork by Virginia McCarthy:
Purchase this artwork (via Society6): Print || iPhone Case || iPhone Skin


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Letter: The reverse message
Mark Generales, Bonita Springs
The reverse message
Lee Memorial Health System and CEO Jim Nathan are spending big bucks buying full-page ads in local papers to hype "health-care expansion" — getting the state Legislature to take money from the U.S. government to expand coverage.
I was stunned that anyone would make this kind of comment: "Florida can receive billions of dollars we have already sent to Washington."
Please tell me Lee Memorial's board is more responsible than this? The U.S. government borrows 50 cents of every single dollar it spends. Nathan and his hospital chain want to tap into this gross overspending.
We have too many examples of federal programs that pay the first two to three years and leave local governments holding an expensive bag we can't afford: Trains from Tampa to Orlando, 100,000 cops, etc. The last thing we need is a local quasi-government entity jumping on this bandwagon for its own purposes, no matter how noble.
I agree with one thing in the ad: call your state representative and Sen. Garrett Richter.
Call, but do as I did. Tell them no. You don't want them taking federal money.
We can't afford these schemes anymore.
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Kevin Scott Hamilton
A Kingsport man contracted to sell Snap-On equipment has been arrested after allegedly failing to compensate the company for nearly $100,000 in merchandise.
Kevin Scott Hamilton, 41, of 5110 Springview St., was charged Wednesday with felony embezzlement and theft over $60,000. According to police and court records Hamilton is the owner of Hamilton Equipment Solutions, LLC, located at 116 Regional Park Drive.
A manager for Snap-On Equipment in Conway, Ariz., contacted Kingsport police on May 14. He allegedly stated that Hamilton, a contracted sales representative, had ordered various pieces of equipment delivered to his business since February of 2011.
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Last week I was having an informal conversation with some colleagues who also happened to be from a consulting business (but not IP or legal consulting). Over an excellent pub lunch on a rainy London day, we got to talking about IP (naturally enough when I'm involved in a conversation) and its role for consultants. The question came up about the importance of intellectual property for consulting firms, as this line of work almost always involves transferring any formal IP rights to the client. I thought that IP could play a strong role, but needed some time to further develop my thoughts (hence this post).
The consulting business in a nutshell:
- Clients pay for applied knowledge that achieves some sort of result (new sales, restructuring management, IP strategy, reports, training, etc);
- Consultants create or transfer the knowledge requested by the client (often in person or through reports);
- The client then requires the rights to the knowledge (licence or assignment of copyright in reports, licensing of know-how, etc) so it can actually use what the consultant produced to achieve its goals.
So that's more or less it: Consultants have a bank of knowledge and skills that clients then pay to use on specific matters. They certainly create knowledge (and IP), but then have to turn around and transfer it (in whole or by licence) to their clients
As a formal matter, the concepts of foreground IP and background IP come into play here. Generally, background IP consists of the core skills and knowledge (and their legal protections) that consultants can apply to any client. Foreground IP consists of all knowledge generated around this particular client's specific problem and often will be exclusively licensed to that client. There is a technical legal discussion here that I want to acknowledge but move past: I'm not concerned at the moment with how you structure the legal aspects of the consultant/client relationship but rather on the core of IP and consulting.
So what stays at the core — inside the consulting business — that can be protected by IP and used to build the business?
ConsultingPulse has been thinking about the same problem, and in an interview with Paul Collins of Equiteq LLP highlights what I also see as key reason to take this issue seriously:
[Y]ou must demonstrate that your services are built upon intellectual property that belongs to the firm, rather than just the combination of the individual skills of your consultants.
Without this, Paul points out that consulting firms will find difficulty in getting higher valuations upon sale or merger. I'd also add that building up the structure around the firm (as opposed to the individuals) will also lead to higher revenues along the way. But these points address why consultants should build up an IP structure around the firm but not what they should build it on.
I think that the answer is to:
- write it down – get as much information about the practice area out of the consultants heads;
- manage it – use tools to manage that knowledge effectively, such as using a wiki or other Knowledge Management (KM) tools; and finally
- protect it – examine all the ways that you can protect that knowledge as an asset of the firm.
The answer to the last point may be through IP such as copyright, database rights, trade secrets, and even patents or through other means such as employment law (non-compete agreements) or simple physical security (need to know access backed up by encryption and access controls).
IP and building value is of course a major theme of this blog, but in light of Andrew's post last week about the IP consulting services market I have a final parting thought. As legal consultants, we need to combine best practices from both law firms and from management consulting firms. I think many IP services tend to come at their business from a law firm perspective, and tend to ignore some of the key intelligence from the consulting community. As we all hopefully grow together (and grow the market for our services), I'd like to see more from the consulting perspective as part of the conversation.


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An air-cooled ignition lead for use with aircraft engines to conduct high voltage ignition pulses between an exciter and an igniter. The ignition lead includes a center conductor covered by an insulation jacket for electrical isolation. Radially spaced outwardly from the insulation jacket is a flexible conduit that has sufficient structural integrity to resist collapsing inwardly. The insulation jacket and conduit define an airflow path therebetween that is used for conducting air through the lead. An innerbraid is located over and supported by an outer surface of the flexible conduit, and this location of the innerbraid prevents it from collapsing over time and obstructing the airflow passage that extends on the inner side of the flexible conduit. The innerbraid can be used as a return path conductor that provides a return current path and/or EMI shielding. Covering the innerbraid is an outerbraid to protect the lead against external damage.
1. A fluid-cooled ignition lead, comprising:
a center conductor for conducting high voltage ignition pulses;
an insulation jacket surrounding said center conductor;
a flexible conduit surrounding said insulation jacket and being spaced from said jacket such that said ignition lead includes a fluid passage located between said insulation jacket and said conduit;
a low-resistance return path conductor comprising a plurality of low resistance metal wires located radially outwardly of said flexible conduit; and
a protective covering surrounding said return path conductor.
2. The ignition lead of
3. The ignition lead of
4. The ignition lead of
5. The ignition lead of
6. The ignition lead of
7. The ignition lead of
8. The ignition lead of
9. A fluid-cooled ignition lead, comprising:
a center conductor;
an insulating sleeve covering said center conductor and having an outer surface;
a non-collapsible conduit surrounding said insulating sleeve, said conduit having an inner surface and being spaced from said insulating sleeve, whereby said inner surface of said conduit and said outer surface of said insulating sleeve together define a fluid passage therebetween, said fluid passage extending radially from said insulating sleeve to said conduit and extending axially along a length of said insulating sleeve, whereby fluid flowing through said fluid passage is in direct contact with said insulating sleeve and said conduit;
a return path conductor located radially outwardly of said conduit; and
an outerbraid covering said return path conductor and providing an abrasion-resistant outer surface of said ignition lead, wherein said return path conductor has a lower electrical resistance than said outerbraid.
10. The ignition lead of
11. The ignition lead of
12. The ignition lead of
13. The ignition lead of
14. The ignition lead of
15. The ignition lead of
16. An air-cooled ignition lead for use with an ignition system and a sparking device, comprising:
an elongated center conductor for conducting high voltage ignition pulses between the ignition system and sparking device;
an insulation jacket coaxially surrounding said center conductor and having an outer cylindrical surface;
a flexible conduit coaxially surrounding said insulation jacket and having an inner cylindrical surface;
an airflow passage for allowing air to flow within said ignition lead, said airflow passage being located coaxially between said insulation jacket and said flexible conduit, with said airflow passage having an annular cross-sectional shape and extending radially from said insulation jacket for a distance of between 2 mm and 11 mm;
a copper-cored innerbraid coaxially surrounding said flexible conduit; and
a nickel-based outerbraid coaxially surrounding said innerbraid;
wherein said airflow passage is bounded on a radially-inward side by said insulation jacket outer cylindrical surface and on a radially-outward side by said flexible conduit inner cylindrical surface, such that air flowing in said airflow passage is in direct contact with said insulation jacket outer cylindrical surface to thereby remove heat from said insulation jacket.
17. In a fluid-cooled ignition lead having an insulated center conductor and an outer covering assembly radially spaced from said insulated center conductor by a fluid passage, said outer covering assembly comprising an innerbraid, a flexible conduit, and an outer protective covering surrounding said conduit, innerbraid, and insulated center conductor,
wherein the improvement comprises said innerbraid being located between said flexible conduit and said protective covering, and said flexible conduit defining in part said fluid passage.
The present invention relates generally to ignition leads used with reciprocating and gas turbine engines and, more particularly, to air-cooled ignition leads used in such engines.
An ignition lead is a high voltage cable (typically 2–25 kV) used to deliver high voltage ignition pulses from an ignition system to some type of ignition device, which in turn uses the ignition pulses to generate sparks for igniting a fuel/air mixture. Most ignition leads include elastomeric components, such as grommet seals or wire insulation, for electrical isolation and improving the performance and/or durability of the ignition lead under high voltage conditions. Though helpful for these purposes, the ignition leads are typically subjected to high temperatures that can degrade and even damage the elastomeric components. If exposed to excessive temperatures for prolonged periods of time, it is possible for the elastomeric components to experience thermal degradation and breakdown of their dielectric strength. Thus, it is known in the art to provide cooling passages in the ignition leads for lowering operating temperatures, and more particularly, for reducing the heat to which the elastomeric components are exposed.
An example of a prior art air-cooled ignition lead 10 is shown in
According to one aspect of the present invention, there is provided a fluid-cooled ignition lead having a center conductor, an insulation jacket, a fluid passage, a non-collapsible conduit, a return path conductor, and an outerbraid, wherein the return path conductor is located radially outwardly of the conduit between the conduit and the outerbraid.
In accordance with another aspect of the invention, there is provided a fluid-cooled ignition lead having an insulated center conductor, a conduit radially spaced outwardly from the insulated center conductor to thereby define a fluid passage between an outer surface of the insulated center conductor and an inner surface of the conduit. The ignition lead includes a return path conductor located outside of the conduit between the conduit and an outerbraid or other protective covering.
A preferred exemplary embodiment of the invention will hereinafter be described in conjunction with the appended drawings, wherein like designations denote like elements, and wherein:
Referring now to
Center conductor 102 conducts the high voltage ignition pulse provided by the ignition system, and can be comprised of either a solid core or stranded wire. In the case of a stranded wire, center conductor 102 is formed from a number of smaller gauge wires wrapped in a compact pattern such that a series of small spaces or voids are formed therebetween. Preferably, there are anywhere between 10 and 50 strands of 10 to 20 gauge wire which comprise center conductor 102. In the case of a solid core embodiment, center conductor 102 preferably includes a single wire having a uniform circular cross-section.
Insulation jacket 104 is a non-conductive sleeve or tubular sheath-like covering that coaxially surrounds center conductor 102 such that it prevents the center conductor from being inadvertently contacted and electrically shorted. In a preferred embodiment, the insulation jacket 104 has an outer diameter in the range of 3 mm to 7 mm and is comprised of an elastomeric or PTFE-based material that preferably allows any moisture trapped therein to escape.
Airflow passage 106 coaxially surrounds insulation jacket 104 and provides a cooling channel for air to flow around the jacket and acts as a heat sink for removing unwanted heat imparted to it from the aircraft engine or other nearby sources. In the particular embodiment shown here, airflow passage 106 is an elongated tubular passageway or channel having an annular cross-sectional shape, however, the cross-sectional shape could be generally oval, elliptical, rectangular, triangular, etc. The enveloping nature of airflow passage 106, with respect to insulation jacket 104, improves the thermal dynamics between these two components, as the entire outer surface of the insulation jacket is in direct thermal contact with the airflow passage. According to a preferred embodiment, airflow passage 106 has a radial dimension X, which=[(inner diameter of conduit 108−outer diameter of jacket 104)/2], and is preferably between 2 mm and 11 mm.
Alternatively, airflow passage 106 could be a fluid passage that allows a fluid, either a liquid or a gas, to flow therethrough. In either case, the liquid or gas is in fluid contact with both an inlet and outlet (neither of which are shown) such that new fluid may enter the fluid passage via the inlet, flow around and gather heat emanating through insulation jacket 104, and then exit the outlet as hotter fluid. Examples of inlets and outlets include, but are certainly not limited to, tapered sleeves, openings, bosses, valves, manifolds, etc., and could include those terminal connections conforming to SAE/ARP standard 670, types 1–4. Because the ignition lead of this invention can be utilized with one of a number of inlets and outlets and is not linked to any one particular design, and because such inlets and outlets are known in the art, a further explanation of them has been omitted.
Flexible conduit 108 provides air-cooled ignition lead 10 with some structural integrity such that it is flexible, yet non-collapsible. By "non-collapsible", it is meant that conduit 108 will not collapse inwardly except under an applied force that is substantially in excess of that normally encountered by the ignition lead when used in its intended environment. According to a preferred embodiment, flexible conduit 108 is a tubular structure that defines the outer extent of airflow passage 106 and prevents the air flowing through the ignition lead from escaping outwardly through the conduit. Preferably, the flexible conduit 108 is formed from a Nickel-iron (Ni—Fe) material which can include other constituent elements and which can be in the form of an alloy or as nickel-cladded iron. Other metals and compounds can be used as long as they provide sufficient structural integrity to render the conduit non-collapsible. The airflow passage 106 terminates radially outwardly at an inner cylindrical surface of flexible conduit 108 which according to a preferred embodiment has an inner diameter that is between 10 mm–30 mm.
Innerbraid 110 is a low resistance, sleeve-like component that provides a low resistance return path for the ignition lead. This braided return path conductor is useful for providing EMI shielding and/or as a return path for ignition pulse current supplied via the center conductor, as will be appreciated by those skilled in the art. In a preferred embodiment, innerbraid 110 is a braid of nickel-plated copper wire that coaxially surrounds flexible conduit 108 in tight contact therewith. Outerbraid or overbraid 112, while potentially useful also as a ground path, is a protective covering made from nickel wire that surrounds the other components of ignition lead 100 and that is used primarily to provide external protection of the innerbraid and other components from damage such as abrasion. Experience has shown that without an outerbraid, engine vibration and other operating conditions can cause rubbing or abrasion by clamps or other fastening devices that hold the ignition lead in place.
In use, air-cooled ignition lead 100 is connected between an ignition system such as an exciter (not shown) and a sparking device such as an igniter (not shown), such that the exciter provides the igniter with high voltage ignition pulses via the ignition lead. As the temperature of the ignition lead rises due to heat from the engine and/or other nearby sources, air flowing through airflow passage 106 acts as a heat sink and removes the heat, thereby helping to protect the insulation jacket 104. The heated airflow is then transported to some type of outlet which vents the hot air to the atmosphere, such that the overall temperature of ignition lead 100 can be kept to an acceptable level. Of course, in the case of a fluid flow passage carrying a liquid coolant, the imparted heat would be removed from the liquid coolant in a manner similar to that used by a radiator, and the cooled liquid would then be recirculated through the fluid passage.
It is to be understood that the foregoing description is not a definition of the invention itself, but is a description of one or more preferred exemplary embodiments of the invention. The invention is not limited to the particular embodiment(s) disclosed herein, but rather is defined solely by the claims below. Furthermore, the statements contained in the foregoing description relate to particular embodiments and are not to be construed as limitations on the scope of the invention or on the definition of terms used in the claims, except where a term or phrase is expressly defined above or where the statement specifically refers to "the invention." Various other embodiments and various changes and modifications to the disclosed embodiment(s) will become apparent to those skilled in the art. All such other embodiments, changes, and modifications are intended to come within the scope of the appended claims.
As used in this specification and claims, the terms "for example" and "such as," and the verbs "comprising," "having," "including," and their other verb forms, when used in conjunction with a listing of one or more components or other items, are each to be construed as open-ended, meaning that that the listing is not to be considered as excluding other, additional components or items. Other terms are to be construed using their broadest reasonable meaning unless they are used in a context that requires a different interpretation.
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ALBUQUERQUE, N.M.-New Mexico State men's basketball head coach Marvin Menzies and volleyball head coach Mike Jordan hosted kids clinics for Laguna elementary students, Saturday, May 15 in Albuquerque, N.M., and Route 66 Casino sponsored the event.
"We had a great time,"
Each coach brought staff personnel and players along to teach skills to the almost 100 kids that participated in the clinics.
"I was impressed with the turnout of the local kids," Menzies said. "They had a lot of desire to learn and have fun, which makes for a good clinic. We look forward to returning to the area in the near future for additional events."


text: http://www.theasfl.com/asfl2/Fantasy_Games/Premier_League_Pickem/ I originally jumped in here to promote my Premier League Pickem game above, and would still like to welcome anyone interested. 3 points for the correct result 1 point for a correct team score +1 more point for a perfect game (both scores, and subsequently the result) Forgive me if this board is only for the Premier League's game and these subsequent leagues. But, in that case... When I noticed the message board drafts going on, I realized I may be able to offer my services. I run the entire website of the game linked above. The title is the All-Sports Fantasy League and subsequently, I run a number of fantasy games. Currently about half the games are handled by Yahoo! and half are handled on the website as I work toward moving more games from Yahoo! to the website. [Not important, just back story] There are also subsections of the website for All-Star, Keeper & Money Leagues (of the four major North American leagues). Originally, I used message board drafts to offer a slow draft format for people that couldn't otherwise agree on a draft time, but have since created an application. I should be able to modify it for use with these leagues next season if desired, with some help. Here's an example slow draft from Fantasy Baseball in 2010: http://www.theasfl.com/asfl2/Money_Leagues/Drafts/Baseball/test.php and a guide to the draft's features: http://www.theasfl.com/asfl2/Money_Leagues/Drafts/draftguide.php Aside from the features, the system sends email alerts when a pick comes up and confirmation when any action is done to the system. The help I'd need is someone creating an excel file of the players available and the needed pieces of data for each of them as well as setting up the information on managers in any league using the application. Beyond that, I'd simply need to have the time to do it tweak the system files. If those involving in running the drafts are interested, let me know. Sorry I didn't discover these in time for this season.


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|23 in.
|8 in.
|8 in.
|1.9 lbs.
|Shipping Weight:
|1.9 lbs.
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Comments about Hammer Dust Collection System for Drilling and Chiseling:
Allowed me to focus on drilling holes for a liquidfreeze type concrete bustup job instead of manually managing the dust. Got at least 95% of all the dust from couple dozen 1 1/2 " holes without any cleanup post-drilling. In my case I had to drill about 90% througha six inch plus thick slab repeatedly while avoiding punching all the way thru. The adapters I had available with my shop vacuum were not ideal but even through about ten feet of hose, the suction through this dust collector worked great to keep the holes and surrounding area clean. If you have ever used a hammer drill to drill big holes, you already know there is a lot of dust, and some of it is surprisingly fine. Not a replacement for a well fit respiration mask, but definitely helps reduce released dust to a minimum.


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Buto.tv API
Buto.tv is a service for uploading, managing and measuring online video. The service is directed at content creators and video sharing sites. The Buto.tv API provides a RESTful interface to your video collections, playlists, meta-data and user accounts.
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Jamie Carragher called for improvements to be made at both ends of the pitch after a defensive lapse cost Liverpool a result in Moscow against Anzhi Makhachkala on Thursday night.
Carragher pulled on the captain's armband in Steven Gerrard's absence and led the likes of Adam Morgan, Jon Flanagan and debutant Conor Coady out at the Lokomotiv Stadium.
And while he was proud of the performances of the youngsters who featured in the 1-0 loss, the veteran defender insisted the Reds must become more clinical in front of goal and in their defensive duties if they are to progress this season.
"We made a mistake just before half-time and at this level, when you're seconds away from the break, you cannot make mistakes like that," he said.
"We've got to be more clinical. And that's not just in relation to Thursday night and in the Europa League, it applies to the season overall.
"The loss to Anzhi was a big learning curve. Not just for the young players but for myself. That's European football for you though - you have to be very clinical at both ends of the pitch.
"But I thought we did okay. I thought the young lads did well. Anzhi are a team that has been assembled at quite a cost and they have a few top players in their side. So for the young players to come here and perform the way they did, I think we deserved something from the game."
The result alters the complexion of Group A and places the Reds in joint second place, level with Young Boys, a point behind Anzhi and two ahead of Udinese.
"We have got to make sure we win our home game against Young Boys," said Carragher. "If we do that, then that will put us in a great position [to qualify from the group] and then it will depend how Anzhi and Udinese do in their game.
"Ideally, we don't want to have to go to Udinese needing to win but if we have to go there to get a point I think we would certainly take [the draw] now."
Tagged: carragher , jamie carragher
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