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|Número de publicación
|Tipo de publicación
|Fecha de publicación
|21 Mar 1972
|Fecha de presentación
|3 Ago 1970
|Fecha de prioridad
|3 Ago 1970
|Número de publicación
|Rosset Armand J De
|Cesionario original
|Universal Oil Prod Co
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|BiBTeX, EndNote, RefMan
|Citada por (53), Clasificaciones (24), Eventos legales (2)
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet
United States Patent Office 3,651,167 Patented Mar. 21, 1972 3,651,167 SELECTIVE HYDROGENATION OF C -ACETYLENIC HYDROCARBONS Armand J. de Rosset, Clarendon Hills, 11]., assignor to Universal Oil Products Company, Des Plaines, Ill. No Drawing. Continuation-impart of application Ser. No.
745,963, July 19, 1968. This application Aug. 3, 1970,
Ser. No. 60,656
Int. Cl. C07c 7/00 U.S. Cl. 260-681.5 8 Claims ABSTRACT OF THE DISCLOSURE Selective hydrogenation of C -acetylenes, for example ethylacetylene and/or dimethylacetylene, in admixture with butadiene, is effected in a fixed-bed system using a Group VIII noble metal component catalyst. A preferred catalyst comprises palladium in an amount of about 0.01% to about 0.2% by weight. Operating conditions include a temperature of from 35 C. to about 70 C. and a pressure in the range of about 10 p.s.i.g. to about 40 p.s.i.g. Catalyst stability is improved since the Group VIII metal components is surface-impregnated onto the porous carrier material.
RELATED APPLICATION The present application is a continuation-in-part of my copending application, Ser. No. 745,963, filed July 19, 1968, now abandoned, all the teachings of which copending application are incorporated herein by specific reference thereto. I
APPLICABILITY OF INVENTION The present invention relates to a catalytic process for etfecting the selective hydrogenation of unsautrated hydrocarbons. As utilized herein, the term selective hydrogenation connotes the simultaneous treatment of two or more unsaturated hydrocarbons having, for the most part, varying degrees of unsaturation. Specifically, the process encompassed by the present invention involves the selective hydrogenation of a C -acctylene, such as ethylacetylene and/or dimethyl acetylene, in the presence of large quantities of butadiene which may contain l-butene and/ or Z-butene, without hydrogenative degradation of the butadiene concentrate.
Butadiene, sometimes referred to as vinylethylene, is derived in large quantities from the catalytic dehydrogenation of butanes and butenes. Other principal sources of butadiene include various petroleum various petroleum refinery off-gases and the gaseous products recovered from various hydrocarbon cracking operations. The principal utility of butadiene resides in its value as a starting material to produce high molecular weight polymers. Thus, a primary use is in the production of synthetic rubber, including styrene-butadiene rubber, nitrile-butadiene rubber, buna-S rubber, and trans polybutadiene rubber. Other uses are as the starting material for adiponitrile and styrene-butadiene latex in paints. Similar utility for l-butene and 2-butene are widespread, although a primary use of these unsaturated hydrocarbons resides in the synthesis of butadiene.
When butadiene is recovered from any one of its sources, it is seldom obtained in a degree of purity required for its subsequent use in the preparation of other organic compounds. The principal. impurities are C -acetylenes,
namely ethylacetylene and dimethyl acetylene, with ethyland under particular conditions of operation which insure that little, if any, reduction in the quantity of butadiene is experienced, and selective hydrogenation of the C -acetylcne is obtained over an extended period of time as a result of increased catalyst stability.
OBJECTS AND EMBODIMENTS As hereinbefore set forth, change stocks, to which the present invention is applicable, include normally gaseous mixtures obtained from cracking operations such as naphtha pyrolysis units. In general, the pyrolysis off-gas is subjected to separation to provide an ethylene concentrate, a propylene concentrate and a butadiene concentrate. With respect to catalytic processing for the selective hydrogenation of acetylenic hydrocarbons in these various concentrates, the heavy concentration of butadiene in the last-mentioned feed stock imposes a more severe burden on a given catalytic composite than either ethylene concentrate or the propylene concentrate. This is due principally to the fact that butadiene competes more closely with the C -acetylenes for hydrogen, as contrasted to the mono -olefins, and therefore tends to shorten the effective life of the catalyst through its natural tendency to deposit polymers.
Therefore, an object of the present invention is to provide a process for the selective hydrogenation of certain unsaturated hydrocarbons without disturbing, to a significant degree, other unsaturated hydrocarbons containing a type of unsaturation different from that of the undesired hydrocarbons. A corollary objective is to hydrogenate selectively those hydrocarbons containing an acetylenic degree of unsaturation without disturbing desired diolefinic hydrocarbons in admixture therewith.
A more specific object of my invention is to hydrogenate selectively ethylacetylene in admixture with butadiene without effecting a significant loss of the latter.
Another object is to prolong the efiective life of the catalytic composite utilized in selectively hydrogenating C -acetyleues, including ethylacetylene and/or dimethyl acetylene, in the presence of large quantities of butadiene.
Still another object is to provide a new composition of matter for use in a process for olefin hydrogenation, and particularly in a process for di-olefin and acetylene hydrogenation.
Therefore, in one embodiment, the present invention affords a process for the selective hydrogenation of a C acetylene, in admixture with butadiene, without substantial hydrogenation of the butadiene, which process comprises reacting said mixture with hydrogen in an amount in excess of that required to convert said C -acetylene and less than 0.1 mole of hydrogen per mole of butadiene, at a temperature below about 70 C., in contact with a catalyst comprising an alumina carrier material, from about 0.01% to about 0.5% by weight of a surface-impregnated Group VIII noble metal and from about 0.1% to about 1.0% by weight of an alkali metal.
A specific embodiment affords a novel catalyst particle consisting essentially of alumina, from about 0.1% to about 1.0% by weight of lithium, from about 0.01% to about 0.5% by weight of a surface-impregnated Group VIII noble metal and from about 0.001% to about 0.015% by weight of a Group I-B metal selected from copper and silver.
Other embodiments of my invention reside primarily in the character of the noble metal catalyst for use in the process. These as well as other embodiments and objects will become apparent from the following detailed description.
SUMMARY OF INVENTION As hereinafter illustrated through the use of specific examples, the present invention is founded upon recognition ofthe principal cause of. catalystd eactivation while attempting the selective hydrogenation of ethylacetylenej when in admixture with butadiene. It should ,be.
noted that, while the cause of rapid catalyst deactivation is of the same general character as that arising in the selective hydrogenation of acetylenes in both ethylene and propylene concentrates, ;namely polymer formation, the difliculty which arises is compounded by the fact that both butadiene and ethylacetylene readily tend to form polymers. Whereas both ethylene and propylene form polymers, the propensity to do so, during the selective hydrogenation of acetylenic contaminants, is significantly less pronounced. In brief, hydrogenation processes, and the techniques integrated therein, which are suitable for obtaining either ethylene concentrates or propylene concentrates, do not suffice for hydrogenation of C -acetylenes to obtain a butadiene concentrate.
Hydrogenation of unsaturated hydrocarbons is generally effected at relatively severe temperatures of from 100 C. to about 200 C., and at imposed hydrogen pressures of from 200 to as high as 1000 p.s.i.g. At these operating conditions, generally utilized for the selective hydrogenation of acetylene in ethylene concentrates, the process is effected in liquid phase. With respect to the removal, or selective hydrogenation, of methylacetylene and allene from a propylene concentrate, liquid-phase operating conditions further promote the tendency of the methylacetylene and allene to undergo polymerization and copolymerization, or condensation reactions resulting in the formation of methylacetylene polymer. This polymer has been found in various preheater tubes and lines, and other attendant manifolding, as well as upon the catalytic composite disposed within the reaction zone.
I have previously found that the selective hydrogenation of methylacetylene and allene in a propylene concentrate can be successfully effected over a prolonged period of time provided the hydrogenation conditions are selected to provide a vapor phase operation. Suitable preferred operating conditions, for the selective hydrogenation of methylacetylene in a propylene concentrate, include a pressure in the range of from 50 to 175 p.s.i.g., a temperature of from 30 C. to about 75 C., and a gaseous hourly space velocity (GI-ISV) range of about 2500 to about 10,000 cubic feet of gas per cubic foot of catalyst per hour. Significantly, these ranges for the principal operating conditions do not foster acceptable results in a process for the selective hydrogenation of C -acetylenes in a butadiene concentrate. This, as hereinbefore set forth, is due primarily to the fact that butadiene competes more vigorously with the C -acetylenes for hydrogen, as contrasted to the mono-olefins, and tends to shorten catalyst life through its own natural tendency to deposit polymer.
\In accordance with the process of the present invention, the selective hydrogenation of a C -acetylene, in admixture with butadiene, is effected in vapor phase, and in contact with a catalyst containing less than 0.5% by weight of a Group VIII noble metal and athydrogenation conditions including a temperature below 70 C. As hereinafter indicated, in specific examples, the residual ethylacetylene level was lower than 60 C. than at 70 C., the higher temperature apparently accelerating the rate of polymer accumulation. Furthermore, catalysts containing 0.5% by weight of palladium gave consistently poorer results than did catalysts containing as'low as 0.1% by w'eight'of palladium. Therefore, preferred operating conditions include a temperature in the range of from about 35 C. to about 65 C., and the catalyst contains less than 0.5% by weight of a GroupVIII noble metal, and preferably from about 0.01% to about 0.2% by weight. The hydrogenation conditions further include a pressure below about 50 p.s.i.g. and a gas hourly space velocity (GHSV) less than about 1000. Lower ranges of these operating variables are preferred, and include a pressure from about 10 p.s.i.g. to about 40 p.s.i.g. and a gaseous hourly space velocity within the range of from 150 to about 800. The C -acetylene/ amount in excess of that required to convert the C -acetylenes, but less than 0.1 mole per mole of butadiene in the feed stock. Higher concentrations of hydrogen are avoided in order to limit the loss of butadienethrough conversion to a mono-olefin.
' DESORIP'IlION OFCATALYTIC COMPOSITE The hydrogenation catalytic composite, suitable for use in the present process, comprises a noble metal of Group VIII of the Periodic Table, composited with a refractory inorganic oxide carrier material. Thus, the catalytic com-v posite may contain one or more of ruthenium, rhodium, palladium, osmium, iridium, and platinum, and various compounds thereof, in a total amount less than about 0.5% by weight, calculated as the elements thereof. A particularly preferred catalytic composite comprises a metallic component from the group of platinum and palladium combined with a non-acidic refractory inorganic oxide material such as alumina. It is further preferred that the alumina be pre-treated through the addition of a non-acidacting component such asthe salts and hydroxides of alkaline metals and alkaline-earth metals, specific examples of which include lithium nitrate, lithium hydroxide, potassium nitrate, potassium hydroxide, sodium nitrate, sodium hydroxide, calcium nitrate, magnesium nitrate, etc. While the precise manner by which the catalytic composite is prepared is not an essential feature of the present invention, it is a requirement that the selected preparation scheme result in a catalyst particle in which the catalytically active Group VIM noble metal is surface-impregnated. This type of catalyst results in lower residual C acetylene values, accompanied by greater butadiene retention, than those catalysts whichhave been bulk-impregnated, or thoroughly-impregnated within and throughout the carrier material. I
Although surface impregnated catalysts have achieved an individual status in the art, and further are considered unique by those possessing expertise in the realm of catalysis, the merit thereof for the selective hydrogenation of C -acetylenes is not recognized. With respect to the selected hydrogenation catalyst, it is important to consider the adsorption-diffusion behavior of the feed components, butadiene and the C -acetylenes. As indicated by its longer chromatographicretention time, a C -acetylene, for example, ethylacetylene, is more strongly adsorbed than butadiene. Duringv the diffusion of the vaporous feed into the catalyst particles,-the ethylacetylene has the propensity and tendency to concentrate near, or at the surface and, considering a surface-impregnated catalyst, will be hydrogenated at this locus of the catalyst particle. The butadiene will be diffused to the interior cages (pores). and surfaces, but, since no catalyst promoter sites are presentgtherein, will not degrade due to-hydrogenation thereof.- To the contrary, such promoter sites are present in a thoroughly-impregnated, or uniformly-impregnated catalyst; these are not blocked by ethylacetylene, or anyother C -acetylene, and the butadiene, which diffuses into the interior of the catalyst particle, -will tend to undergo hydrogenation.
Reference is herein made to. United States Pat. Nos.
3,259,454 -(Cl.' 2-23), 3,259,589..(Cl. 252-466) and 3,388,077 (Cl; 252-466) wherein. the differentiation among various impregnated composites is clearly :delineated. Considering only the 3,259,589 patent, patentee describes surface-irnpregnation by his'FIG. l and thortive; concept. It 'should' be noted that these patents disclose" various schemes for manufacturing impregnated catalysts, any one of which can be used to prepare the catalyst of the present invention with the restriction that the final particle has the catalytically active noble metal component in a surface-impregnated state. Such a catalyst particle is typically retained on a US. No. 30 standard' screen and is passed by a US. No. 4 standard screen. Substantially all of the surface-impregnated active metal component is contained in a surface shell having a thickness not greater than 0.005 inch.
Of further interest, in regard to the character of the catalytic composite, is that the use of a copper component modifier, in addition to the Group VIII metallic component, affords a slight improvement where the lithiated alumina carrier material is thoroughly-impregnated with the Group VIII metal. To the contrary, a silver component modifier appears to be somewhat detrimental.
However, with respect to a surface-impregnated catalyst, the addition of a silver component modifier appears to afford an improvement, while the use of a copper component modifier seems to have a lesser effect. When employed as catalyst modifiers, silver is used in an amount in the range of 0.005% to about 0.015% by weight, while copper is in the range of from 0.001% to about 0.01% by weight, calculated as the elemental metals.
The addition of an alkali metal component, for example, lithium, to the catalytic composite is not intended to promote, or effect any particular reaction, but rather to attenuate undesirable catalytic activity and reactions. The alumina carrier material possesses strongly acid hydrogens at or near the surface. Such sites are conductive, as potential proton donors, to effecting carbonium ion reactions, the principal one of which is olefin polymerization. This undesirable effect is countered by replacing the strongly acid hydrogen with lithium, or potassium. The alkali metal component is preferably combined by way of an initial impregnation technique, or by a co-precipi tation method during the formation of an alumina hydrogel. In any event, the calcination of the resulting lithiated alumina should not be carried out at temperatures significantly higher than about 600 C. Elevated temperatures-Le. 900 C. to about l300 C.-will produce an alumina-lithium spine], determinable by X-ray diffraction. Further, there is no danger of the catalytic surface becoming sintered.
The catalytic composite, containing from about 0.01% to about 0.5% by weight of a Group VIII noble metal component and about 0.1% to about 1.0% by weight of an alkali metal component, both of which are calculated as if existing as the elemental metals, is placed within the reaction zone maintained at operating conditions in the aforesaid ranges. The charge stock, comprising a mixture of butadiene, ethylacetylene and possibly minor quantities of l-butene and 2butene, is admixed with a molar excess of hydrogen and introduced into the reaction zone. The thus-treated charge stock is withdrawn and recovered, analyses thereof indicating a relatively minor amount of ethylacetylene, the major proportion being butadiene with a minor degree of conversion to butene and/or butane.
' EXAMPLES The following examples are introduced for the primary purpose of further illustrating the method and utility of the present invention, but not with the intention of unduly limiting the same beyond the scope and spirit of the appended claims. Additional methods of preparing the surface-impregnated catalytic composite are integrated into these examples.
Various catalytic composites were utilized in the examples which follow. In general, the methods of preparation subscribed to the same overall scheme. The lithiated alumina was prepared by initially forming alumina spheres by the well known oil-drop method as set forth in US. Pat. No. 2,620,314 (Cl. 252-448). An impregnating solution of 18.1 grams of lithium nitrate, dissolved in 550 cc. of water, was poured over 360 grams of calcined alumina spheres, and the mixture dried in a rotatl n'g evaporator. The dried lithiated alumina carrier material was then calcined for two hours at 550 C., and ground to 20/30 mesh. Analysis indicated 0.5% by weight of lithium, calculated as the element.
Three different schemes were employed to incorporate a palladium component: 1) an aqueous solution of chloropalladic acid, in an impregnating step; (2) chloropalladic acid, in admixture with thiomalic acid; and (3) an aqueous solution of palladium nitrate. The latter impregnating solution was prepared by placing 0.473 grams of palladium wire in ml. of water and 60 ml. of concentrated nitric acid. Upon heating and the addition of one drop of a 5.0% hydrobromic acid solution, the palladium wire started to dissolve. Evaporation was elfected until the wire had completely dissolved (about 40 m1. remaining). The resulting solution was diluted to 250 ml. with water, In all preparations, the required amount of impregnating solution was poured over the lithiated alumina, evaporated to dryness, and calcined at 600 C. for a period of two to three hours. Preparations (2) and (3) above produced a surface-impregnated composite, whereas scheme (1) resulted in a composite in which the palladium was thoroughly-impregnated.
The charge stock was a 50/50 mole mixture of butanebutadiene contaminated by the addition of 800-900 p.p.m. of ethylacetylene. The charge stock was admixed with 2.0 mol percent hydrogen, pumped and vaporized over a charcoal bed at 100 C., and passed into the reaction zone, containing 5.0 cc. of 20/30 mesh catalyst. The pressure was 20.0 p.s.i.g., the temperature, at the inlet to the catalyst bed was either 60 C. or 70 C., and the gaseous hourly space velocity was about 700. Unless otherwise stated, these conditions were utilized throughout the examples. The charge stock had the composition shown in the following Table I; in addition, analysis indicated 885 p.p.m. of ethylacetylene.
Analyses for residual ethylacetylene were made by scrubbing the efiluent gas through alcoholic silver nitrate.
With respect to the charge stock being a 50/50 mixture of butane/butadiene, the butane was utilized to simulate the dilution of a butadiene concentrate with C -acety1ene and butylene, as would be the expected effluent from a butylene dehydrogenation process, or from a naphtha pyrolysis unit. Furthermore, the substitution of butane for butylene simplifies the analytical detection of the principal undesired reaction, the conversion of butadiene to butylene. Where a small, but significant degree of such conversion is undetected in the presence of large amounts of feed butylene, it is readily measurable where the feed contains only minor amounts of butylene. Since butylene and butane are closer to each other with respect to adsorption characteristics, than they are to acetylenic and conjugated di-olefinic hydrocarbons, the substitution of butane does not affect or mask the results. In a commercial unit, butadiene is separated from butylene by way of extractive distillation using, for example, cuprous ammonium acetate, or acetonitrile.
EXAMPLE I Two catalysts were prepared with the lithiated alumina carrier material in an impregnation technique using sufficient palladium chloride to composite therewith 0.1% and 0.5 by weight of palladium, calculated as the element. Each catalyst was used twice at the foregoing conditions; once at a temperature of 60 C. and once at 70 C. Four l0-hour tests were conducted at each temperature level with the 0.1% palladium catalyst, while two 10-hour tests at each temperature were conducted -At 60 C. and 0.5% palladium, the average residual Wt. Ethylpercent, acetylene, p.p.m.
Not only is the effect of palladium content readily apparent, but the effect of temperature is also noticeable.
acetylene was 68 p.p.m. This average increased to 161 p.p.m. when the catalyst bed inlet temperature was increased to 70 C. Similarly, at 0.1% palladium and 60 C., the average residual ethylacetylene was 51 p.p.m., while at 70 C., the average was 81 p.p.m Upon comparing residual ethylacetylene content at the different palladium concentrations, it will be noted that the lower concentration of palladium was consistently better, regardless of the temperature level. Thus, at 60 C., the 0.5% palladium catalyst reduced the ethylacetylene to an average of 68 p.p.m., whereas the 0.1% palladium catalyst reduced the ethylacetylene content to an average of 51 p.p.m.
EXAMPLE II TABLE IIL-EFFECT 0F IMPREGNATING METHOD Residual ethylacetylene, p.p.m.
Impregnating solution CPA CPA/'IMA N0 That surface impregnation, as shown by the results of the palladium nitrate (N0 and the chloropalladic acidthiomalic acid (CPA/TMA), offers additional advantages, is evident from the data in Table III. The residual ethylacetylene levels were consistently lower than those ob tained with the catalyst in which the active component is dispersed throughout the carrier material.
Another comparison of the two methods of impregnationwas made at the 0.5 palladium level and with 60 a catalyst bed, inlet temperature of 60C. The palladium chloride-impregnatedcatalyst (thorough). resulted in an etlluent having 66 p.p.m. residual ethylacetylene, while the palladium nitrate-impregnated catalyst (surface) produced an etlluent containing. 44 p.p.m. residual ethylacetylene.
EXAMPLE In with thorough impregnation was somewhat detrimental.;.: f
feasibility of adding a copperpromoter to the catalyst- The composite was prepared-by adding 4.0 ml. of -a palladiumnitrate solution (0.00189 gram of palladium per milliliter) and 4.4 ml. of. a copper .nitrate solution (0.000102 gramof copper per'milliliter) to 7.0 ml. of water. The solutionwas poured over 7.5 grams of 20/30 mesh lithiated alumina,.and evaporated to dryness. The dried composite was calcined for aperiod of two hours at a temperature of 600 C. The catalyst contained 0.1% palladium, 0.006% copper and 0.5% lithium. The catalyst was placed in a reaction zone at 20.0 p.s.i.g., 60- C. and with a GHSV of 600 to 700. After 8 hours on-stream, analysis of the gaseous efiiuent indicated a residual ethylacetylene content of 9.5 p.p.m. At the termination of 30 on-streatm hours, continuing at 60 C., the residual ethylacetylene was 33 p.p.m., the butane concentration 49.9 mol percent, and the butadiene concentration 48.0 mol percent. Both the l-butene and Z-butene concentration had increased about 0.6 mol percent. Following 78 hours of on-stream operation, the ethylacetylene concen: tration was found to be 67 p.p.m., and the butadiene concentration had increased to 51.4 mol percent. Increasing the temperature to 70 C. and above, at the inlet to the catalyst bed,.caused the residual ethylacetylene content to increase steadily over four 20-hour test periods, from 147 p.p.m. to 841 p.p.m.
Using 0.05 by weight of palladium, surface-impregnated by means of the. palladium nitrate solution, at 60 C., the residual ethylacetylene content, after 18 hours on-stream, was 32 p.p.m. This increased to 79 p.p.m. and subsequently to 244 p.p.m. with the temperature at 70. C.
Thorough impregnation of 0.1% by weight of palladium, using chloropalladic acid, modified by 0.02% by weight of lead, resulted in an ethylacetylene content of p.p.m., following 18 hours of on-stream operation- Two additional operations were effected at 60 C., 20.0 p.s.i.g. and about 600-700 GHSV, with 2.0 mol percent hydrogen in'the feedstock. Two different catalysts were utilized in amounts of 5.0 cc. These were surfaceimpregnated composites of 0.l%..palladium on the :lithiated alumina carrier material (0.5%. by weight of lithium); one catalyst contained 0.006% by weight of copper and the other, 0.01% by weight of silver. These catalysts are referred to as catalysts A and B," respectively, in the following Table IV:
Catalyst designation -Q.-.. A B
Residual ethylacetylene, p.p.m.:
Test 1 41 17 Test 2 27 o it appears from the data that results are further enhanced where the catalytic component is surface-impregnated upon the carrier material. Modifiers, preferably minor quantities of copper and silver, appear to improve the results with surface-impregnated catalysts.
The object of the operations hereinafter described was to lengthen the eifective catalyst life, or stability, before regeneration became a necessity. In. general, the tests were conducted in the manner previously described. However, two slightly different feed stocks were employed, to both of which hydrogen (about 2.0 mol percent) was of palladium, resulted in a measurable improvement, while the. silver modification 9 added through the use of a charger functioning at a pressure of 400 p.s.i.g. Analyses of the charge stocks are presented in the following Table V:
TABLE V Charge stock A B Ethylacetylene, p.p.m 800 1,090 Hydrogen, mol. percent 2. 1. 9 Propane, mol. percent Trace Trace Butanes, mol. percent 49. 9 47.8 l-Butene, mol. percent... 0.1 N11 Z-Butene, mol. percent 0. 1 0. 1
Butadiene, mol. percent..-
EXAMPLE IV A first operation was conducted utilizing charge stock A and a catalyst in which 0.1% palladium was surfaceimpregnated, followed by drying via evaporation and furnace drying at 200 C., with a second impregnation to incorporate 0.006% by weight of copper. Following a first test at 721 GHSV, and 8-hour on-stream processing, the residual ethylacetylene was 50 p.p.m. Over the next 12 hours, the GHSV was raised to 2404, all other conditions remaining the same, and the ethylacetylene content increased to 224 p.p.m. For the next hours (25 hours total), the GHSV was increased to 2650, with the result that the residual ethylacetylene content was 207 p.p.m. For the next twelve hours, the GHSV was lowered to a level of 705, and the ethylacetylene content of the gaseous eflluent decreased to 85 p.p.m., indicating that the catalyst had deactivated during the high GHSV operation.
At this point, after 37 hours total operation, regeneration was attempted by passing nitrogen over the catalyst bed at 120 C. A thirteen-hour test was run thereafter, at a GHSV of 673, and analysis showed a residual ethylacetylene content of 200 p.p.m. Obviously, nitrogenregeneration is not feasible. The catalyst was then regenerated in air at'a temperature of 120 C. and reduced with hydrogen in situ. Another thirteen-hour test was conducted to a total on-stream time of 63 hours. At this point, the analysis showed 44 p.p.m. residual ethylacetylene, clearly indicating a regenerated catalyst. Of further significance is the fact that the butadiene content increased from 47.9 mol. percent to 48.8 mol. percent and the butane content decreased from 49.9 to 49.3 mol. percent. Following this successful operation on the airregenerated catalyst, the catalyst was treated with steam at a temperature of 120 0, followed by hydrogen reduction at 150 C. At a GHSV of 683, and following a test period of 12 hours, the residual ethylacetylene had increased to 175 p.p.m. Steam regeneration appears to have detrimentally affected the catalyst.
EXAMPLE V after which the composite was calcined at 600 C. for a period of two hours. The charge stock used was B from Table V, containing 1090 p.p.m. of ethylacetylene. Eight 10 tests were effected at varying GHSVs, the results being correlated in the following Table VI:
TABLE VL-Variable gas hourly space velocity GHSV: Ethylacetylene, 1p. pm. 642 0 When these results are correlated in a graphical representation, a virtual straight-line function is indicated with ethylacetylene concentrations in the range of 75-80 p.p.m. being attained at a gaseous hourly space velocity less than 1000 cubic feet per cubic foot of catalyst per hour.
EXAMPLE VI The catalyst employed in the operation described in Example V was continued in use for an extended life test. Standard conditions were considered to be 60 C., 20.0 p.s.i.g., 2.0 mol. percent hydrogen in the feed and a GHSV in the range of 500800. Following 76 hours of operation, using charge stock B, containing 1090 p.p.m. of ethylacetylene, analysis of the gaseous efiluent indicated the concentration shown in the following Table VII:
TABLE VII Additional analyses were obtained through 126 hours of on-stream operation: at 99 hours, the ethylacetylene content was 44 p.p.m.; at 114 hours, it was 79 p.p.m. and, at 126 hours, the residual ethylacetylene content was 75 p.p.m. At this point, the catalyst was regenerated in air at a temperature of C. and reduced in hydrogen at C. A subsequent operation, after 143 hours, indicated residual ethylacetylene in an amount of 29 p.p.m.
The regeneration was then repeated, and an analysis taken at 159 hours showed 54 p.p.m. residual ethylacetylene. During the next eleven hours, the GHSV was increased to a level of 5230 with the result that the ethylacetylene content increased to 486 p.p.m., after a total of hours of on-stream operation. Without additional regenerations, and at a lower GHSV of 500-800, the operation continued to a total on-stream time of 283 hours. Spot-check analyses indicated, that, at hours, 36 p.p.m. of ethylacetylene were in the efiluent; at 196 hours, 50 p.p.m.; at 212 hours, 29 p.p.m.; at 228 hours, 52 p.p.m.; at 250 hours, 49 p.p.m.; and, at 270 hours, 51 p.p.m. The analysis at 283 hours indicated the concentrations shown in Table VIII:
TABLE VIII.Extended life test-283 hours It is significant that the catalyst bed inlet temperature was increased to 65 C. during the period from 250 to 270 hours, after which the residual ethylacetylene con tent was 51 p.p.m. From 270 to 283 hours, the termination of the operation, the temperature was increased to U 1 1' 70 "C."As' 'indicated in Table 'VIII, the residual ethylacetylene content increased to 75 p.p.m. It is evident that catalyst deactivation had commenced during the last thirteen hours of the operation, and that the process should be carriedout with a temperature less than 70 C.
Throughout the entire series of operations'thus far described, one particular item is especially evident. With but few exceptions, hydrogen consumption within the reaction zone was total and complete. This, therefore, indicated that an increase in the hydrogen content of the feed stream was called for. To obtain the higher hydrogen concentration of about 3.2 mol. percent, the charger pressure was increased to 580 p.s.i.g. from the 400 p.s.i.g. required for a 2.0 mol. percent hydrogen concentration.
EXAMPLE VII For the purpose of this particular operation, 8.5 cc. of the 20/30 mesh, 0.1% palladium catalyst, without modifiers, were used. The various test runs were conducted at 60 C. and 20 p.s.i.g., using charge stock B containing 1090 p.p.m. of ethylacetylene. Residual ethylacetylene values 'were compared at varying gaseous hourly space velocities utilizing the hydrogen content of the feedstock as a parameter, specifically 2.0 mol. percent and 3.2 mol. percent.
In the following Table IX, the results of the series of tests with 2.0% hydrogen are presented. In Table X, the results of the series at 3.2 mol. percent hydrogen are presented.
7 TABLE rx Test No 1 2 3 4 TABLE X Test N 5 6 7 8 GHSV 328 Product analysis:
Ethylaeetylene, p.p.m Butane, mol. percent 47. Butadiene 49. 1-butene-. 2. 2-butene-- 1. Hydrogen 0 OHHKBDFW A graphical correlation of the data from Tables IX and X presents two straight-line functions, distinctly separate one from the other and virtually parallel. Coupled with the data from the foregoing tables, it is clear that lower residual ethylacetylene values can be achieved with 7 higher hydrogen concentrations, and can be decreased 30-40 p.p.m. at a given GHSV.
After the end of Test 8 (in Table X), the catalyst service was 28 6 hours. The operation continued at 60 C., 20.0 p.s.i.g., varying GHSVs, and with 3.2 mol. percent hydrogen in the charge stock. The unit was shut down after a total on-stream time of 582 hours with the zfinal ethylacetylene content being only 54 p.p.m.
'EXAMPLE VIII GHSV of 580-700, using the charge stock containing 1090 p.p.m., the catalyst bed inlet temperature was varied from 35 "(3; totiOf C. TWeNe-liour test periods were 'conducted at each temp rature level, the results thereofbeing presented in the following-TableXIt t TABLE XI Temperature, C. Ethylacetylene, p.p.m. 60 62 55 77 50 69 45 64 4o 67 35 122 35 148 60 v TABLE XII Component Charge 55C. 35 0.
Ethylacetylene, p.p.rn 1,090 77 t 148 Butane, mol. percent. 46. 9 45. 1 47. 1 Butadlene 60. 0 53. 0 51. 1 l-butene. 0. 1 1. 3 1.2 Z-butene- I 0. 1 0. s 0. 6 Hydrogen 2.0 0.0 0.0
Other analyses obtained during "the 55 C. period and the second 35 C. period are indicated in the following Table XII. For convenience in comparisom'the charge stock analysis is also presented.
The foregoing specification, and particularlythe illustrative examples and the data presented therein, indicates the benefits afforded through the use of the present invention in a process for the selective hydrogenation of C; acetylenes in a butadiene concentrate. t
I claim as my invention-v 1. A process for the selective hydrogenation of a C acetylene in admixture with butadiene, without'substantial hydrogenation of the. butadiene, which comprises re acting said mixture with hydrogen in an amount in excess of that required to convert said- C -acetylene and less than 0.1 mole of hydrogen per mole of butadiene, at a temperature below about 70. C.,.in contact with a catalyst comprising an alumina carrier material, from-0.01% to about 0.5% by weight of a-surface-impregnated-Group VIII noble metal being contain edin a surface. shell having a thickness not greater than 0.005 vinch and from about 0.1% to about 1.0% by weight of-an alkali metal.
2. The process of claim 1 further characterized infthat said catalyst additionally contains from about 0.001% to about 0.015% by weight. of a Group I B metal selected from copper and silver. v 1
3. The process of claim 1 further characterized in that said mixture and hydrogen are reacted at a .ten1perat ure of from 35 C. to about 65 C.,. a.pressure from 10 p.s.i.g. to about 40 p.s.i.g. and a gas hourly space velocity less than about 1000.
4. The process of claim Zfurther characterized in that said catalyst additionally contains from about 0.001% to about 0.01% by weight of copper.
5. The process of claim l further characterized in that said catalyst additionally contains from about 0.005% to about 0.015 byweight of silver.
6. A catalyst particle consisting essentially of alumina, from about 0.1% to about 1.0% by weight of lithium, from about 0.01% to about 0.5 by weight of a surfaceimpregnated Group VIII noble metal being contained in a surface shell having a thickness not greater than 0.005 inch-and from about 0.001% to about 0.15% by weight of a Group I-B metal selected from'copper and silver.
7. The catalyst of claim 6'further characterized in tha said Group VIII noble metal is platinum.
8. The catalyst of claim 6 further characterized in tha said Group VIII noble metal is palladium.
(References on following page) References Cited UNITED STATES PATENTS OTHER REFERENCES Rieche et al., Hydrogenation of Vinylacetylene,
Fleming 260 6 15 Drennstoife-Chemie 42(6), pp. 177-185, June 1961. Kroni et a1. 208255 Kesmfr 260 681 5 5 DELBERT E. GANTZ, Pnmary Examlner Schneider et a1. 26O--6 81.5 V. OK-EE'FE, Assistant Examiner 'Poons et a1. 260-68115 Kronig et a1. 260-6815 X- Clark 260--677 m 474 De Rosset 260-677 'Nettesheim 260-6815 R Ottmori 26068'1.5 R
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|Clasificación internacional
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|Clasificación europea
|27 Abr 1989
Owner name: UOP, A GENERAL PARTNERSHIP OF NY, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UOP INC.;REEL/FRAME:005077/0005
Effective date: 19880822
|21 Sep 1988
Owner name: UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD;REEL/FRAME:005006/0782
Effective date: 19880916


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Its like getting hired to play keyboards in a major touring band after being the one-man-band for a successful regional act.
Its a bigger single responsibility, but with a whole lot fewer overall ones.
Of course, Steve Hamilton had help in making the Spruce Grove Saints an AJHL powerhouse in recent seasons, but being general manager and head coach (and a lot of everything else) for a smaller franchise is a time-consuming task, even if the WHL presents a steeper learning curve.
Its also similar to a minor-pro head coach catching on as an assistant in the NHL. When the Edmonton Oil Kings overhauled its coaching staff entering its fourth year as a WHL franchise, Hamilton was the chosen one as the right-hand-man to new head coach Derek Laxdal.
As his rookie season in the Dub comes to a regular-season close, Hamilton says its been all good, on and off the ice.
Ive really enjoyed the transition, Hamilton said this week, ahead of this Friday-Saturday home-and-home set with the Red Deer Rebels, a likely preview of a first-round playoff series. Its been a new challenge, a new group of players.
Weve got back to that teaching element of the game, where were taking a younger team and looking to move forward.
It has been on a personal note a big change in terms of what my job description looks like. Im solely responsible for my duties as an assistant coach rather than all the intricacies that go with being the general manager and head coach and recruiter and all the things that go on at that level.
And Ive found it much easier on the family life, if Im being totally honest. Ive got three young kids, and at the end of the day, as much as I still am thinking about hockey, the to-do list seems not as great. So its probably a healthier balance for me, for sure.
He is, of course, referring to a hockey to-do list, not a honey-do list.
Moving his base of operations a few kilometres east has had its benefits for Hamilton as a coach and family man, but what about the hockey?
I think the biggest thing you notice in the Western league level is that the high-end guys are extremely high end. They are legitimate pro prospects some of these guys guys that are a year, half-year from playing at an NHL level.
You notice, too, with these guys, its a hockey-first mentality. And it should be. This is the dream they want to pursue and were in the business of developing good young hockey players and good young men.
He wasnt implying that aspect was otherwise in the AJ, its the time-frame thats different.
I think that the window of time in the Alberta Junior Hockey League is a little bit more broad, because guys are looking to extend themselves through school and open that window time up to four or five years, versus the one, two, three years these guys are looking at.
Not a lot of changes, really. The game is still the game. And its the same age group, but there are subtleties, for sure.

subset: commoncrawl


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How to Figure Out Crochet Stitch Multiples to Change Patterns
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Am I turning into a twihard? First, I became an instant fan of Robert Pattinson after meeting him for the "Remember Me" press junket (check out my fun one-on-one interview with Pattinson right here).
Now, I'm giddy like a tween upon seeing the new trailer for "The Twilight Saga: Eclipse." Why? Because I love Dakota Fanning from the second film, and there's a little subplot revelation about her in the trailer, and I also love Bryce Dallas Howard who replaced Rachele Lefevre as the vengeful vampire Victoria, and there's a great revelatory shot of her in the trailer as well.
So I squealed after watching the trailer, and I want to share it with you! The third installment is from director David Slade ("30 Days of Night") and is set to open June 30th.
My only problem? Never been a big fan of screenwriter Melissa Rosenberg, I thought her scripts did not give justice to the first two installments, but, the third may be the best among the three, or heck, among the four (or five, if Summit moves with plans to divide the last film in two)!
For now ogle at the world of "Twilight" and yes, there's another shirtless Jacob (Taylor Lautner) in there, and a seemingly darker Bella (Kristen Stewart).
Call me intrigued!
[ 23 comments ] ( 1137 views ) | permalink | ( 3 / 1015 )
As we reported last month, Eric Bana is set to play Saoirse Ronan's dad in the upcoming action thriller "Hanna." Ronan is set to play a teenage assassin for her "Atonement" director Joe Wright.
Now, Focus informed me that Academy Award winner Cate Blanchett has joined the cast and production will begin filming in Europe next week! Also joining the cast is Niels Arestrup who recently won the César Award (Frances Academy Award equivalent) for Best Supporting Actor for "A Prophet" ["Un Prophète"].
Focus also shared the top secret plot:
Hanna (to be played by Ms. Ronan) is a teenage girl. Uniquely, she has the strength, the stamina, and the smarts of a solider; these come from being raised by her father (Mr. Bana), an ex-CIA man, in the wilds of Sweden. Living a life unlike any other teenager, her upbringing and training have been one and the same, all geared to making her the perfect assassin. The turning point in her adolescence is a sharp one; sent into the world by her father on a mission, Hanna journeys stealthily across Europe while eluding agents dispatched after her by a ruthless intelligence operative with secrets of her own (Ms. Blanchett). As she nears her ultimate target, Hanna faces startling revelations about her existence and unexpected questions about her humanity.
Oh this is so freaking intriguing. It reads like a comic book! I love it already! And I love the cast and the director!
Here's more from Focus:
Seth Lochhead wrote the initial screenplay and has written subsequent drafts, as have David Farr, Joe Penhall, and Mr. Wright. Academy Award nominee Leslie Holleran (Chocolat) is producing Hanna with the team of Marty Adelstein and Scott Nemes (who are in post-production on The Experiment). Barbara A. Hall, who executive-produced Focus Academy Award-winning Milk, encores in that capacity on Hanna. Focus senior vice president, European production Teresa Moneo is supervising Hanna for president of production John Lyons. European locations for Hannas filming will include Finland, Bavaria, Morocco, and Berlin (the latter in part at Studio Babelsberg).
Mr. James Schamus, Focus CEO said, Were so pleased to reunite with Saoirse and Joe for Hanna Focus biggest production yet. With Saoirse taking on such a demanding role opposite Cate and Eric, this movie will be not only breathlessly exciting but also emotionally affecting.
I agree! I can't wait for this movie!
[ 30 comments ] ( 1268 views ) | permalink | ( 3 / 1059 )
J. Edgar Hoover's life will get the Clint Eastwood treatment in a new project being developed by Brian Grazer and Imagine Entertainment.
According to EW.com, "Milk" screenwriter, Dustin Lance Black," has written the script that follows "Hoovers career, from the founding of the FBI in 1935 to his long tenure as director of the crime-fighting organization that lasted until 1972 when he died. Should Eastwood decide to make it his next film, he will produce it with Grazer through his Malpaso Productions."
There's no studio attached to the project yet, although it was originally set up at Universal. But Eastwood has a longstanding relationship with Warner Bros., so this Hoover project may end up at the WB.
Since the script is written by Black, I'm wondering if Hoover's homosexual activities and relationship will be included! They better!
[ 23 comments ] ( 1271 views ) | permalink | ( 3 / 1041 )
The legendary Robert De Niro is set to play football legend Vince Lombardi in the new biopic "Lombardi."
ESPN Films has attached Academy Award winner Eric Roth ("Forrest Gump") to write the script. According to ESPN.com, ESPN Films, Andell Entertainment and the NFL, will tackle Lombardi's illustrious career in football, starting in 1959 when he took over the Green Bay Packers, then the worst team in the NFL. Under Lombardi's direction, the team went on to become champions.
The longstanding drama between Lombardi and Dallas Cowboys coach Tom Landry will also be featured. No actor has been hired yet to play Landry.
Right now, ESPN Films is on the hunt for a director, and "Lombardi" is set to open nationwide the weekend before the 2012 Super Bowl.
[ 23 comments ] ( 1292 views ) | permalink | ( 3 / 1113 )
I've said it before and I'll say it again, I'm now a fan of Robert Pattinson. He was sweet and shy in person, and he had such honest vulnerability.
When I interviewed him for "Remember Me," we talked about:
*** His involvement with the film (apparently, they offered him "Remember Me" prior to the first "Twilight" -- after "Twilight" came out, he could have easily said no to "Remember Me," but the actor was true to his words, and he really loved the script!)
*** His character, Tyler
*** Working with Ruby Jerins
*** How he identifies with the character
(To read my movie review of "Remember Me," click here)
Here's more info on "Remember Me" from Yahoo:
Tyler, a rebellious young man in New York City, has a strained relationship with his father ever since tragedy separated their family. Tyler didn't think anyone could possibly understand what he was going through until the day he met Ally through an unusual twist of fate. Love was the last thing on his mind, but as her spirit unexpectedly heals and inspires him, he begins to fall for her. Through their... See Full Description
Genres: Drama and Romance
Running Time: 1 hr. 53 min.
Release Date: March 12th, 2010 (wide)
MPAA Rating: PG-13 for violence, sexual content, language and smoking.
Summit Entertainment, LLC
Cast and Credits
Starring: Robert Pattinson, Emilie de Ravin, Chris Cooper, Lena Olin, Tate Ellington
Directed by: Allen Coulter
Produced by: Carol Cuddy, Robert Pattinson, Nick Osborne
[ 22 comments ] ( 1116 views ) | permalink | ( 3 / 1196 )


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Prophetic Aaron Baddeley had the right attitude all along at Oakmont; Now it's him vs. Tiger at U.S. Open
OAKMONT, Pa. - Looking back on all the players I've spoken with this week, either one-on-one or in a reporter mob (usually around Rory Sabbatini, Zach Johnson or Ian Poulter), one thing has been evidently clear:
Those who came in with the mindset that the tournament was about them, and not the "dangerous" or "unfair" U.S.G.A. and Oakmont are doing well.
Those who were sniping at the course from the beginning of the week aren't contenders.
I had a minute with 54-hole leader Aaron Baddeley as he was on the practice green Wednesday before his tournament began. This is the first time I'm looking back on the audio since I spoke with him and I'm surprised at how prophetic it is as we enter Sunday.
Can Oakmont yield a first-time major winner?
"I do, yeah. There's a lot of top players in the top 30 in the world that haven't won a major, and I think they're good enough to win a major, so I think they can, yeah."
On whether that first-timer could be him:
"I feel like if I play well, and play like I know I can, I'll be coming down the backside on on Sunday with an opportunity."
Mickelson hurt his wrist, David Howell just withdrew as well…are players being extra cautious about hitting out of the rough this week?
"I can see if you came up and practiced for hours and hours, just hitting it out of the rough, I can see how you could get a sore wrist or hurt yourself.
"But if you're not doing it all the time, but hitting it in the fairways and not in the rough, you'll be fine."
Think about guys like Sergio Garcia, Rory Sabbatini, Phil Mickelson, and even lately Zach Johnson - guys who always seemed to put the course ahead of their game this week. They're either fighting for scraps in the $7 million purse or they're already at home.
Baddeley has a good head on his shoulders. His demeanor has been very humble and confident all week. He's not getting baited into talking about the golf course. He knows it's up to him.
Tiger is the favorite of course, but don't expect Baddeley to roll over tomorrow. The trophy may stay down under.
My commentary has just been posted on WorldGolf.com about all of Oakmont's wimps.
Stay tuned for full coverage tomorrow…
|« Low scores, high humidity early at Oakmont as Tiger & Baddeley set to duel at U.S. Open
|Defending U.S. Open and Oakmont champ Ernie Els likes Bubba Watson's chances, but Tiger is in control »


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A quick thought on hot spot policing and agglomeration economies
Over on Slate, Matt Yglesias, one of the nation's leading voices on urban economic issues, notes that "hot spot" policing, or sending more police to specific high crime areas, actually seems to reduce crime and not just displace it, contrary to the expectations of some. This is one of the findings in Frank Zimring's fantastic book on crime in New York City, The City That Became Safe, which discusses how crime fell in New York faster and for longer than it did anywhere else in the country (you probably know about the murder rate, but here's an amazing fact: auto theft fell by 94% from 1990 to today! AOL dial-up usage hasn't fallen that far from its peak!). One of the answers Zimring gives is that the police focused resources on specific problems, particularly outdoor drug markets.
Yglesias notes that, while it makes sense that "hot spot" policing would just displace open air drug markets to other places, it does not. He doesn't offer a theory why. Here's one – drug markets feature heavy gains from agglomeration. For those of you who don't know, agglomeration economics is the field that studies why economic behavior tends to clump together in cities, despite higher rents (Here's the great Ed Glaeser, who with Paul Krugman, is the best known scholar in the field, explaining the basic types of gains from agglomeration). Two agglomeration based stories can help explain why open-air drug markets exist and why disrupting them may reduce overall crime. The agreement among dealers to locate in a specific place creates market depth, which allows consumers to pick among them, getting gains from specialization (different dealers may have access to different types of drugs, or drugs of different qualities and prices) and insurance (buyers know someone will sell them drugs in a big market, as opposed to counting on the reliability of a single drug dealer if they go to his corner). And there is surely a great deal of learning among drug dealers, about how to avoid cops, how to deal with tweaking clients and the like. And there are some economies of scale in providing common services, like security. When a drug market gets displaced, the assumption that some other place will just pop up in equal size ignores that it is difficult to coordinate all of these people to show up in some other park (there isn't a drug dealer trade group to house these negotiations, after all). There are reasons to co-locate but coordinating everyone to move to one place is just really hard.
As Dan Rodriguez and I show in our piece The Location Market, the type of thinking that led people to believe shutting down open-air drug markets would have no effect pervades urban economic policy. For instance, one of the central arguments for the congressional Height Act, which limits the height of buildings in Washington D.C., is that, if there are no skyscrapers in downtown DC, economic activity will move spread easily from K Street to Cleveland Park or Anacostia. But it doesn't – restricting supply just causes rents just go up downtown, which is now one of the most expensive office markets in the country. The reason is that lobbyists want to be near other lobbyists. Co-location provides easy access to "upstream and downstream linkages" (from restaurants set up for deal making to access to a deep market for temps) and most importantly information spillovers or learning from peers (As Rodriguez and I write, "A lobbyist talking to another lobbyist about congressional procedure is producing information spillovers that will improve the listener's productivity at work. A lobbyist talking about congressional procedure to just about anyone else is a bore.")
Effectively, the reason hot spot drug policing might work is the same reason the Height Act is bad. Real estate is all about location, location, location.


text:
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About Me
Generating Harmony
I'm a lover of life. I try to place emphasis on experience over materialism. I love to laugh and to give and am constantly trying to make my ego a less dominant part of my life. I'm currently just resettling into the US after 7.5 years traveling the world, learning from all its fascinating people and cultures.
The purpose of my life is to compassionately allay suffering in as many people as possible. One of the best ways to do this is by being an excellent listener and by meditating and/or doing yoga as frequently as possible. In this way anyone can enter, even if briefly, into enlightenment and realize their connection to all people, all things, all life.
Why I'm on Couchsurfing
I joined 2 years into a 7.5 year journey around the world. After staying with so many people and learning about their cultures I have now resettled in the US and have opened my home to surfers.
I've had nothing but wonderful experiences all around the world. Being invited to stay with people in their homes is one of the best things life has to offer.
I've "officially" surfed with people in Finland, the United Arab Emirates, Russia, Malaysia, U.S.A., Brazil, Mexico, England, Poland, San Marino, Italy, Malta, The Gambia, Botswana, South Africa, Mozambique, Burundi, Rwanda, Sao Tome and Principe, Singapore, and many others.
Meditation (Vipassana), Yoga (Sivananda Hatha), Music (I'm a drummer), Travel Photography, Reading (I minored in literature in University), Film (grew up in Park City Utah, home of the Sundance Film Festival), Travel (obviously), sport.
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Music, Movies, and Books
Movies: Manon of the Spring (French), Bubble (American), Amelie (French), Team America World Police (American Satire), Monty Python and The Holy Grail (Brittish), Citizen Cane (American), Black Swan (American).
One Amazing Thing I've Done
I have periodically been able to enjoy private and even shared moments of enlightenment, where mind stops and greater consciousness rises up. AMAZING!
Teach, Learn, Share
MY BLOG: silverlining909.blogspot.com
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Never allow your cat to eat Stargazer Lilly flowers (they are toxic to the kidneys and can kill) or your dog to eat raisins (same thing).
Countries I've Visited
Albania, American Samoa, Andorra, Antigua and Barbuda, Argentina, Armenia, Australia, Austria, Azerbaijan, Bahamas, Bahrain, Bangladesh, Barbados, Belarus, Belgium, Belize, Benin, Bolivia, Bosnia and Herzegovina, Botswana, Brazil, Brunei Darussalam, Bulgaria, Burkina Faso, Burundi, Cabo Verde, Cambodia, Cameroon, Canada, Chile, China, Colombia, Congo, Costa Rica, Croatia, Cuba, Cyprus, Czech Republic, Côte d'Ivoire, Denmark, Djibouti, Dominica, Dominican Republic, Ecuador, Egypt, El Salvador, Equatorial Guinea, Estonia, Ethiopia, Fiji, Finland, France, Gabon, Gambia, Georgia, Germany, Ghana, Greece, Grenada, Guatemala, Guinea, Guinea-Bissau, Guyana, Haiti, Honduras, Hungary, Iceland, India, Indonesia, Ireland, Israel, Italy, Jamaica, Japan, Jordan, Kazakhstan, Kenya, Kosovo, Kuwait, Kyrgyzstan, Laos, Latvia, Lebanon, Lesotho, Liechtenstein, Lithuania, Luxembourg, Macedonia, Madagascar, Malawi, Malaysia, Mali, Malta, Mauritania, Mauritius, Mexico, Moldova, Monaco, Mongolia, Montenegro, Morocco, Mozambique, Myanmar, Namibia, Nepal, Netherlands, New Zealand, Nicaragua, Niger, Norway, Oman, Panama, Papua New Guinea, Paraguay, Peru, Philippines, Poland, Portugal, Qatar, Romania, Russian Federation, Rwanda, Réunion, Saint Kitts and Nevis, Saint Lucia, Saint Vincent and the Grenadines, Samoa, San Marino, Sao Tome and Principe, Senegal, Serbia, Seychelles, Singapore, Slovakia, Slovenia, Solomon Islands, South Africa, South Korea, Spain, Sri Lanka, Sudan, Suriname, Swaziland, Sweden, Switzerland, Syrian Arab Republic, Taiwan, Tajikistan, Tanzania, Thailand, Timor-Leste (East Timor), Togo, Tonga, Trinidad and Tobago, Tunisia, Turkey, Turkmenistan, Uganda, Ukraine, United Arab Emirates, United Kingdom, United States, Uzbekistan, Vanuatu, Vatican City State, Venezuela, Viet Nam, Western Sahara, Yemen, Zambia, Zimbabwe
Countries I've Lived In
France, United States


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MGM and Columbia's ROBOCOP Set to Begin Production in Toronto
Production is set to begin on Saturday, September 15 in Toronto on Metro-Goldwyn-Mayer Pictures' and Columbia Pictures' ROBOCOP, directed by Jose Padilha. The film stars Joel Kinnaman,Gary Oldman, Michael Keaton, and Samuel L. Jackson, as well as Abbie Cornish, Jackie Earle Haley, Michael K. Williams, Jay Baruchel, Jennifer Ehle, and Marianne Jean-Baptiste. The screenplay is by Josh Zetumer and Nick Schenk, based on the 1987 motion picture written by Edward Neumeier & Michael Miner. The film is produced by Marc Abraham and Eric Newman, with Bill Carraro serving as executive producer. The film will be released in the US on August 9, 2013.
In RoboCop, the year is 2028 and multinational conglomerate OmniCorp is at the center of robot technology. Their drones are winning American wars around the globe and now they want to bring this technology to the home front. Alex Murphy(Kinnaman) is a loving husband, father and good cop doing his best to stem the tide of crime and corruption in Detroit. After he is critically injured in the line of duty, OmniCorp utilizes their remarkable science of robotics to save Alex's life. He returns to the streets of his beloved city with amazing new abilities, but with issues a regular man has never had to face before.
Commenting on the announcement, Padilha said, "It's exciting to think that we're going to be starting production on RoboCop. I have a dream cast and an incredibly creative production team, and we are all supremely dedicated, working together to make a movie that will not only live alongside the first film but also break new ground, be relevant for modern audiences, and stand on its own."
Lula Carvalho is the Director of Photography. The production designer is Martin Whist. The editor is Daniel Rezende. Costume Designer is April Ferry. VFX Supervisor is James E. Price.
About Metro-Goldwyn-Mayer Studios Inc.
Metro-Goldwyn-Mayer Studios Inc. ("MGM") is a leading entertainment company focused on the production and distribution of films and television content globally. The company owns one of the world's deepest libraries of premium film and television programming. In addition, MGM has ownership interests in domestic and international television channels, including MGM-branded channels. For more information, visit www.mgm.com.
About Sony Pictures
Sony Pictures Entertainment (SPE) is a subsidiary of Sony Corporation of America, a subsidiary of Tokyo-based Sony Corporation. SPE's global operations encompass motion picture production and distribution; television production and distribution; home entertainment acquisition and distribution; a global channel network; digital content creation and distribution; operation of studio facilities; development of new entertainment products, services and technologies; and distribution of entertainment in 159 countries. For additional information, go to http://www.sonypictures.com/


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3 Tasting Notes
This is a great tea for upset stomachs. If not brewed perfectly though it can be too weak or very overpowering. This tea has a great lemon ginger balance. If brewed for too long however, the ginger becomes overwhelming and can burn the throat. Overall an excellent tea.
190 °F / 87 °C 5 min, 30 sec
This tea was not what I had expected. The Caramel title is misleading. It has a more vanilla cinnamon taste to it. It is caramel in color so perhaps that is where they got the game.
Despite this, I enjoyed it. It has some good qualities but the lengthy ingredient list is disturbing. Not an everyday tea for me, but for every now and then I think it will be okay.
175 °F / 79 °C 7 min, 45 sec


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Expertise and development
As ESA is a leading space science and technology organisation, the vast majority of its jobs lie within the engineering and scientific disciplines.
ESA's success however, is also a result of a resilient management infrastructure supporting its technical core. Jobs with ESA therefore cover all five of the following professional areas:
- Management
- Engineering
- Science
- Management support
- Administrative and technical services
Space related technologies evolve rapidly. This is why we are particularly committed to the continuous development of our staff members to help them develop their full professional potential and allow them to achieve their personal career goals. ESA, therefore, offers a vast range of professional training and development opportunities in the areas of engineering, management techniques and leadership, information technology, personal development, administration and safety, in addition to language training in a number of European languages. All these training programmes are designed to take into account the needs of individual staff members while addressing the Agency's priorities.
One of the key ways in which ESA expresses its commitment to your development is through the Internal University. It is not an institution in the traditional sense — an academy with fixed premises — but rather an innovative forum for learning and development that will help you enhance knowledge and skills essential to the success of ESA as a single but multifaceted entity.
Training activities are complemented by ESA's cost-sharing approach to higher education. Staff interested in acquiring post-graduate qualifications of direct relevance to their current or future career aspirations at ESA, can apply for tuition assistance. In addition, there are some limited opportunities for scholarships to specific space-related university programmes. These training activities do not automatically constitute a guarantee or an entitlement to a change in terms of grading.
Career management within ESA does however permit upward progression and also supports lateral job movements and changes in responsibility.


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Welcome to Free Bi Pix - Stories Saturday, November 18 2017 @ 11:03 PM CST
- Saturday, April 12 2008 @ 12:42 AM CDT
- Contributed by: bell
- Views: 13,021
Well, after I sucked my brother's cock in the barn it wasn't long before I was wanting it inside of me. It was about four months later. I loved being licked and having his tongue in my pussy but I wanted that long hard piece of meat in me. So we were out in the barn and I brought a blanket to lay on. We started out doing the 69 and taking care of each other. I was even more excited and creamed his face faster. I slowly was sucking his cock and kissing it with small kisses and rubbing my face with his precum. Then I went down fast and hard on his cock then he came in my mouth. Then this time we laid beside of each other. I reached over and kissed him. Then we made out like boyfriend and girlfriend. I felt his hand in my pussy and pressed my tits in his chest. Then he began sucking them. I was moving my hips faster. Fucking his hand then he slowly put the cock in me. I was breathing faster and then as he sucked my tit he pumped me and I felt his warm cream going in me. I was riding him like a cowgirl. I leaned down and kissed him hard on his mouth. The cream flowed from me and he licked it up. I couldn't believe my virginity was gone. I didn't know what to do for a moment. Then I primed his cock again and climbed on for a ride of my life until my cum met his. He fucked me again but this time I felt the cock in my ass. I sat up and he massaged my tits with his hands coming around to the front. I was moaning to my delight when the barn door opened and my dad walked in. He saw us and smiled. Then said," don't stop now, I like watching this stuff." So we continued and we came together. I loved the feeling of him inside me. I looked up and saw my dad long and hard in front of me. I looked at my brother and he just shrugged his shoulders. My dad looked down and said, "hey, little slut swallow my cock." I realized he was drunk. But I decided it looked huge and I wanted to try. My brother decided to load his cock in dad's ass while I pumped him. I started licking him and kissing the head. Then slurping his head like it was an ice cream cone. Then I put the cone in my mouth pumping it in motion with my brother and he put a load in my mouth. He passed out and I laid on top of him and my brother guided the cock in me and I rode him. Then I laid on top of him and slept. My dad woke up with a start finding his daughter nude on top of him and his nude son at his back. He asked what we had done. I told him , " you had me suck your cock, then I rode it and brother pumped your ass with his cock." He looked surprised then rolled me over and started fucking me while kissing my tits. He said," might as well enjoy it." Then when we were finished I watched him insert that big thick cock in my brother. We met in the barn at least once a week. I love sucking cock and even more having it fill me. I love it when they both do it at the same time. I know they feel each other but at least I am included.
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Friday, May 23, 2008 | 2 a.m.
Sun Archives
- Immigrants boost economy — but how much? (4-14-2008)
- Vegas Exodus (4-06-2008)
- LV industries worry flow of immigrants will dry up (6-07-2007)
If Nevada's undocumented workers left tomorrow, the state would lose tens of thousands of jobs and billions of dollars, according to the first report to quantify the impact.
The study, from the Houston-based Americans for Immigration Reform, estimates 45,000 jobs would be lost over time and $9.6 billion would no longer circulate through Nevada's economy each year.
The report is particularly timely because something like the posited scenario — losing tens of thousands of workers — may well be occurring in the Las Vegas Valley. In an April 6 story, the Sun reported that an estimated 60 percent to 80 percent of the valley's residential construction workers are illegal immigrants. With the downturn in the new housing market, tens of thousands of immigrants have lost jobs and are no longer feeding as much money into the local economy. Many are leaving the area.
Because these workers live and work under the radar, economists did not foresee the effects of their lost wages and spending on state revenue; some say more accurate information could have helped the state plan better and avoid some of its current shortfalls.
Nearly two years ago, Assemblyman Moises Denis, D-Las Vegas, unsuccessfully called for a study calculating the effect of illegal immigrants on Nevada's economy. He says the Texas group's effort is "a good start."
The report's conclusions about Nevada "don't surprise me," Denis says. "I don't think it's inflated."
A colleague of his, state Sen. Bob Beers, isn't so sure. "What's missing," Beers says, "is an attempt to quantify the costs to society and government" of the illegal immigrant population. He points to the school system as an example, with its large population of students learning English as a second language.
The Perryman Group, a Texas company with 30 years in economic research, conducted the study. Ray Perryman, the company's president, says his report does try to account for the costs Beers cites.
Perryman allows that his outfit doesn't have access to each state's tax or social service records, but says he uses data gathered in other studies, including one the state of Texas did, for a model that includes those costs. The report estimates that Nevada in 2007 had 130,000 undocumented immigrants in its workforce, or 9 percent of its total number of workers, the fourth-highest percentage in the nation behind Arizona, California and Texas.
The study says the United States would eventually lose 2.8 million jobs and $551 billion in annual spending without undocumented workers — not only the jobs held by those workers but jobs lost in other industries as losses rippled through the economy. The state and national figures cited take into account adjustments the economy would make, over time, in the absence of illegal immigrants, the report's authors say.
Maureen Kilkenny, a professor in the resource economics department at the University of Nevada, Reno, wonders whether Perryman's work doesn't reflect the interests of the businesses in the group, Americans for Immigration Reform, which paid Perryman to do the work.
She says the report doesn't factor into its calculations the difference between wages offered undocumented workers in sectors such as construction and services and what would be paid to legal workers in those sectors.
"The study looks only at the interests of employers ... who can get away with hiring workers at a lower cost," Kilkenny says.
Beers, somewhat similarly, thinks the study is an example of "when you start on a mission to conclude something, you usually get there."
Beto Cardenas, counsel to the Houston-based group and spokesman for the report, says its conclusions are based on facts, and that he welcomes similar studies with different conclusions. Perryman says his group's reputation precedes this report and that he "started with a blank piece of a paper and went from there."
The study took about six months and cost about $100,000, Perryman says.
Denis says Nevada needs to have its own version. "We need to be worried in Nevada how we handle this issue. We depend on these workers and ... if we don't have an opportunity to bring in more workers in the future, it is going to have an impact."


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Service transformation is vital to local government faced with ever-decreasing budgets. But, argues Gary Bell of Civica, too much time has been focused on simply moving services online at the expense of enabling services across all channels.
Welfare reform and a lack of genuinely affordable housing have combined to create the perfect vehicle for driving people out of a secure home. No wonder homelessness is rising. By Mark Cantrell.
The Social Value Act came into force in 2013 in a bid to ensure that social, economic and environmental benefits were considered when commissioning public services. Gemma Waring of procurement specialist Millstream examines how local government can make it work in practice to get the maximum benefits for communities.
Improving the representation of women at the top of local government has proven painfully slow – and a recent report even warned that sexism remains "commonplace" in town halls. What needs to change? Jody Goldsworthy, senior partner at public sector executive recruitment firm GatenbySanderson, takes a look.
What's on the table for local authorities when considering prioritising budgets and service delivery? Tiffany Cloynes and Rebecca Hazeldine of Geldards take a look.
Public sector websites are failing accessibility testing - here's how they can improve. By Hilary Stephenson.
Those who promote outsourcing must have a realistic appreciation of how dramatically it reduces the practical ability of a public authority to maintain proper control of service provision, says Richard Clayton QC.
Debra Maxwell, CEO of CRM Solutions at Arvato UK & Ireland, argues that automation holds the key to creating the efficiencies and savings that councils need to help protect frontline services in the years ahead.
Phil Greenwood, director at Iron Mountain, explains why sharing is not always caring in local government.
Natural capital accounts are an emerging concept in measuring the holistic impact of investment. But what are they? Bram Miller and Samathan Deacon of Ramboll Environ take a look.
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A MAN who hid from police in an airing cupboard has been cleared of possessing heroin and crack cocaine with intent to supply.
Devon Nelson, of Rose Hill, Oxford, faced four counts of possessing heroin and crack cocaine with intent to supply on May 21 and November 10 last year.
Richard Moss, prosecuting, told a jury at Oxford Crown Court police officers had linked the defendant to two stashes of drugs in Rose Hill, Oxford, and Ashhurst Way, Oxford.
But yesterday a jury found Nelson not guilty of all four counts against him following four hours and 18 minutes of deliberating.
During the trial he was asked by his barrister Lucy Tapper why he had hidden under a pile of clothes in an airing cupboard, where drugs were also found behind a boiler, when police raided the Ashhurst Way property.
Nelson told her this was because he was afraid of having an "intimate" search by police.
He told the jury: "When they see me they do it to me, all the time."
Also questioned as to why his DNA was on the child's sock which the drugs in Rose Hill were hidden in, he said it must have been from playing with the children of friends.
He said: "I don't know, all I'm saying is friends come there with kids and I love kids."
Nelson told police and maintained throughout the trial that he had nothing to do with either batch of drugs.


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The Internet has delivered yet again, with this GIF serving as a perfect summation of what has happened thus far in a Western Conference Finals in which the Spears lead Oklahoma City 2-0 after victories of 17 and 35 points. (Note: It might take a bit to load up, but trust us: It's worth it.)
Post-assist finger point: Deadspin, via unknown source.