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|Número de publicación
|Tipo de publicación
|Número de solicitud
|Fecha de publicación
|13 Dic 1994
|Fecha de presentación
|1 Mar 1993
|Fecha de prioridad
|1 Mar 1993
|Número de publicación
|J. Scott Buchanan, David L. Johnson
|Cesionario original
|Mobil Oil Corporation
|Exportar cita
|BiBTeX, EndNote, RefMan
|Citas de patentes (9), Otras citas (1), Citada por (43), Clasificaciones (9), Eventos legales (5)
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet
The invention relates to regeneration of spent catalyst from an FCC unit.
2. DESCRIPTION OF RELATED ART NOx, or oxides of nitrogen, in flue gas streams from FCC regenerators is a pervasive problem. FCC units process heavy feeds containing nitrogen compounds, and much of this material is eventually converted into NOx emissions, either in the FCC regenerator (if operated in full CO burn mode) or in a downstream CO boiler (if operated in partial CO burn mode). Thus all FCC units processing nitrogen containing feeds can have a NOx emissions problem due to catalyst regeneration, but the type of regeneration employed (full or partial CO burn mode) will determine whether NOx emissions appear sooner (regenerator flue gas) or later (CO boiler).
Although there may be some nitrogen fixation, or conversion of nitrogen in regenerator air to NOx, most of the NOx emissions are believed to come from oxidation of nitrogen compounds in the feed.
Several ways have been developed to deal with the problem.
1. Feed hydrotreating, to keep NOx precursors from the FCC unit.
2. Segregated cracking of fresh feed.
3. Process approaches reducing NOx formation in complete CO burn mode via regenerator modifications.
4. Catalytic approaches, using a catalyst or additive which is compatible with the FCC reactor, which suppress NOx formation or catalyze its reduction in a regenerator in complete CO burn mode.
5. Stack gas cleanup isolated from the FCC process.
The FCC process will be briefly reviewed, followed by a review of the state of the art in reducing NOx emissions. In addition, some of the factors forcing FCC operators to process worse feeds (with more nitrogen compounds) in hotter regenerators (which tends to increase NOx) in an ever more restrictive legislative environment will be discussed.
Catalytic cracking of hydrocarbons is carried out in the absence of externally added H2, in contrast to hydrocracking, in which H2 is added during the cracking step. An inventory of particulate catalyst continuously cycles between a cracking reactor and a catalyst regenerator. In FCC, hydrocarbon feed contacts catalyst in a reactor at 425°-600° C., usually 460°-560° C. The hydrocarbons crack, and deposit carbonaceous hydrocarbons or coke on the catalyst. The cracked products are separated from the coked catalyst. The coked catalyst is stripped of volatiles, usually with steam, and is then regenerated. In the catalyst regenerator, the coke is burned from the catalyst with oxygen-containing gas, usually air. Coke burns off, restoring catalyst activity and simultaneously heating the catalyst to, e.g., 500°-900° C., usually 600°-750° C. Flue gas formed by burning coke in the regenerator may be treated for removal of particulates and for conversion of carbon monoxide, after which the flue gas is normally discharged into the atmosphere.
Most FCC units now use zeolite-containing catalyst having high activity and selectivity. These catalysts are believed to work best when the amount of coke on the catalyst after regeneration is low.
Two types of FCC regenerators are now commonly used, the high efficiency regenerator and the bubbling bed type.
The high efficiency regenerator mixes recycled regenerated catalyst with spent catalyst, burns much of the coke from spent catalyst in a fast fluidized bed coke combustor, then discharges catalyst and flue gas up a dilute phase transport riser where some additional coke combustion occurs, and where most of the CO is afterburned to CO2. These regenerators are designed for complete CO combustion, and usually produce clean burned catalyst, and flue gas will very little CO, and modest amounts of NOx.
The bubbling bed regenerator maintains the catalyst as a bubbling fluidized bed, to which spent catalyst is added and from which regenerated catalyst is removed. These regenerators usually require more catalyst inventory in the regenerator, because gas/catalyst contacting is not so efficient in a bubbling fluidized bed as in a fast fluidized bed.
Many bubbling bed regenerators operate in complete CO combustion mode, i.e., the mole ratio of CO2 /CO is at least 10. Refiners try to burn CO completely within the catalyst regenerator to conserve heat and to minimize air pollution.
Among the ways suggested to decrease the amount of carbon on regenerated catalyst and to burn CO in the regenerator is to add a CO combustion promoter metal to the catalyst or to the regenerator.
Metals have been added as an integral component of the cracking catalyst and as a component of a discrete particulate additive, in which the active metal is associated with a support other than the catalyst. U.S. Pat. No. 2,647,860 proposed adding 0.1 to 1 weight percent chromic oxide to a cracking catalyst to promote combustion of CO. U.S. Pat. No. 3,808,121, taught using large-sized particles containing CO combustion-promoting metal into a cracking catalyst regenerator. The circulating particulate solids inventory, of small-sized catalyst particles, cycled between the cracking reactor and the catalyst regenerator, while the combustion-promoting particles remain in the regenerator.
U.S. Pat. Nos. 4,072,600 and 4,093,535 teach use of combustion-promoting metals such as Pt, Pd, Ir, Rh, Os, Ru and Re in cracking catalysts in concentrations of 0.01 to 50 ppm, based on total catalyst inventory. This approach is so successful that most FCC units use Pt CO combustion promoter. This reduces CO emissions, but usually increases nitrogen oxides the (NOx) content of the regenerator flue gas.
It is difficult in a catalyst regenerator to burn completely coke and CO in the regenerator without increasing the NOx content of the regenerator flue gas. Many jurisdictions have passed legislation restricting the amount of NOx that can be in a flue gas stream discharged to the atmosphere. In response to environmental concerns, much effort has been spent on finding ways to reduce NOx emissions.
The NOx problem is most acute in bubbling dense bed regenerators, perhaps due to localized high oxygen concentrations in the large bubbles of regeneration air. Even the high efficiency regenerators, with better catalyst/gas contacting, produce significant amounts of NOx, though usually only about 50-75% of the NOx produced in a bubbling dense bed regenerator cracking a similar feed.
Much of the discussion following is generic to any type of regenerator while much is specific to bubbling dense bed regenerators, which here the most severe NOx problems.
Some refiners hydrotreat feed. This is usually done more to meet sulfur specifications in various cracked products, or a SOx limitation in regenerator flue gas, rather than a NOx limitation. Hydrotreating will reduce to some extent the nitrogen compounds in FCC feed, and this will reduce NOx emissions from the regenerator.
U.S. Pat. No. 4,985,133, Sapre et al, incorporated by reference, taught that refiners processing multiple feeds could reduce NOx emissions, and improve performance in the cracking reactor, by keeping high and low nitrogen feeds segregated, and adding them to different elevations in the FCC riser.
PROCESS APPROACHES TO NOx CONTROL
Process modifications are suggested in U.S. Pat. No. 4,413,573 and 4,325,833, both directed to two-and three-stage FCC regenerators, which reduce NOx emissions.
U.S. Pat. No. 4,313,848 teaches countercurrent regeneration of spent FCC catalysts, without backmixing, to minimize NOx emissions.
U.S. Pat. No. 4,309,309 teaches the addition of a vaporizable fuel to the upper portion of a FCC regenerator to minimize NOx emissions. Oxides of nitrogen formed in the lower portion of the regenerator are reduced in the reducing atmosphere generated by burning fuel in the upper portion of the regenerator.
U.S. Pat. No. 4,542,114 taught minimizing the volume of flue gas by using oxygen rather than air in the FCC regenerator, with consequent reduction in the amount of flue gas produced.
In Green et al, U.S. Pat. No. 4,828,680, incorporated by reference, NOx emissions from an FCC unit were reduced by adding carbonaceous particles such as sponge coke or coal into the circulating inventory of cracking catalyst. The carbonaceous particles performed selectively absorbed metal contaminants in the feed and also reduced NOx emissions. Many refiners are reluctant to add coal or coke to their FCC units, and such materials also burn, and increase the heat release in the regenerator. Most refiners would prefer to reduce, rather than increase, heat release in their regenerators.
U.S. Pat. No. 4,991,521, Green and Yan, showed that a regenerator could be designed so coke on spent FCC catalyst could be used to reduce NOx emissions from an FCC regenerator. The patent shows a two stage FCC regenerator, wherein flue gas from a second stage of regeneration contacted coked catalyst. Although effective at reducing NOx emissions, this approach cannot be used in most existing regenerators.
Another process approach to reducing NOx emissions from FCC regenerators is to create a reducing atmosphere in some portion of the regenerator by segregating the CO combustion promoter. Reduction of NOx emissions in FCC regenerators was achieved in U.S. Pat. No. 4,812,430 and 4,812,431 by using a conventional CO combustion promoter (Pt) on an unconventional support which permitted the support to segregate in the regenerator. Use of large, hollow, floating spheres gave a sharp segregation of CO combustion promoter in the regenerator. Disposing the CO combustion promoter on fines, and allowing these fines to segregate near the top of a dense bed, or to be selectively recycled into the dilute phase above a dense bed, was another way to segregate the CO combustion promoter.
The work that follows is generally directed at special catalysts which promote CO afterburning, but do not promote formation of much NOx.
U.S. Pat. No. 4,300,997 and U.S. Pat. No. 4,350,615, are directed to use of Pd-Ru CO-combustion promoter. The bi-metallic CO combustion promoter is reported to convert CO to CO2, while minimizing formation of NOx.
U.S. Pat. No. 4,199,435 suggests steam treating conventional CO combustion promoter to decrease NOx formation without impairing too much the CO combustion activity of the promoter.
U. S. Pat. No. 4,235,704 suggests too much CO combustion promoter causes NOx formation, and calls for monitoring the NOx content of the flue gases, and adjusting the concentration of CO combustion promoter in the regenerator based on the amount of NOx in the flue gas. As an alternative the patentee suggests deactivating it in place, by adding lead, antimony, etc.
U.S. Pat. No. 5,002,654, Chin, incorporated by reference, taught the effectiveness of a zinc based additive in reducing NOx. Relatively small amounts of zinc oxides impregnated on a separate support having little or no cracking activity produced an additive which could circulate with the FCC equilibrium catalyst and reduce NOx incorporated by reference , taught the
U. S. Pat. No. 4,988,432 Chin incorporated by reference, taught the effectiveness of an antimony based additive at reducing NOx.
Many refiners are reluctant to add more metals to their FCC catalyst out of environment concerns. Some additives, such as zinc, may vaporize under conditions experienced in some FCC units. Adding, antimony to FCC catalyst may make disposal of spent catalyst more difficult.
Such additives also add to the cost of the FCC process, may dilute the FCC equilibrium catalyst, and may not be as effective as desired.
In U.S. No. Pat. 5,021,144, Altrichter, minimized NOx emissions downstream of a CO boiler by operating the FCC regenerator in partial CO burn mode with at least three times the amount of Pt needed to prevent afterburning. Adding Pt to the FCC catalyst reduced NOx in the CO boiler stack gas.
Considerable effort has been spent on downstream treatment of FCC flue gas. This area will be briefly reviewed.
It is known to react NOx in flue gas with NH3. NH3 is a selective reducing agent, which does not react rapidly with the excess oxygen which may be present in the flue gas. Two types of NH3 process have evolved, thermal and catalytic.
Thermal processes, such as the Exxon Thermal DeNOx process, operate as homogeneous gas-phase processes at around 1550°-1900° F. More details of such a process are disclosed by Lyon, R. K., Int. J. Chem. Kinet., 3, 315, 1976, incorporated by reference.
Catalytic systems have been developed which operate at lower temperatures, typically at 300°-850° F. These temperatures are typical of flue gas streams. Unfortunately, the catalysts used in these processes are readily fouled, or the process lines plugged, by catalyst fines which are an integral part of FCC regenerated flue gas.
U.S. Pat. No. 4,521,389 and 4,434,147 teach adding NH3 to flue gas to reduce catalytically NOx in flue gas to nitrogen.
U. S. Pat. No. 5,015,362, Chin incorporated by reference, taught contacting flue gas with sponge coke or coal, and a catalyst promoting reduction of NOx in the presence of coke or coal.
None of the approaches described is the perfect solution.
feed pretreatment is expensive, and can usually only be justified for sulfur removal. Segregated feed cracking helps significantly, but requires segregated high and low nitrogen feeds.
Process approaches, such as multi-stage or countercurrent regenerates, reduce NOx emissions but require extensive rebuilding of the FCC regenerator.
Various catalytic approaches, e.g., adding lead or antimony, to degrade the efficiency of the Pt function may help some but not meet the ever more stringent NOx emissions limits set by local governing bodies.
Stack gas cleanup methods are powerful, but the capital and operating costs are high.
We realized that a difficult situation, operating an FCC regenerator to clean the catalyst without fouling the atmosphere, was just going to get worse. FCC operators are forced to crack worse crudes because light sweet crudes cost too much or are not available. These worse feeds have more NOx precursors in them and are heavier, with large amounts of CCR or asphaltness which must be burned in the regenerator. More feed nitrogen means more NOx emissions. Heavier feeds also translate into higher regenerator temperatures which increase NOx emissions from regenerators operating in complete CO combustion mode. While some of the heat release can be deferred by shifting CO combustion to a CO boiler, such partial CO combustion in the regenerator usually produces slightly more NOx emissions from a downstream CO boiler than would be found in flue gas from the same regenerator operating in complete CO burn mode. Compounding the problem, local laws put ever more stringent limits on NOx emissions. Worse feeds, the need to operate in partial CO combustion mode in the regenerator, and tighter NOx limits combine to create conditions which could shutdown many FCC units, or require installation of expensive pre- or post- treatment steps on feed or flue gas respectively. Simple fixes, such as operating with a CO boiler and adding ammonia or urea to reduce NOx, achieve a limited reduction in NOx emissions, but require handling extra chemicals and create the chance of ammonia or urea emissions.
We did not like any of these approaches, but discovered in some of these approaches, and in some unrelated art., on H2 S conversion, a new approach. Claus units convert H2 S to elemental sulfur, and they are not related to the FCC process. They burn SO2 with H2 S at close to stoichiometric ratios to produce elemental sulfur, at temperatures of 2500° to 3000° F. Several Claus workers reported on the fate of NH3, and this work is worth a brief review.
U.S. Pat. No. 3,987,154, Lagas, which is incorporated by reference had 2 examples showing the fate of NH3. In one, 2.5% NH3 was reduced to 6-22 ppm. NH3, while in the other 3.7% NH3 was reduced to 10-40 ppm NH3. The residence time was around 0.8 seconds, and the temperature was not specified.
U.S. Pat. No. 3,970,743, Beavon, which is incorporated by reference, taught operating the first chamber at 2500°-3000° F. He reported that NH3 was stable at 1900°-2300° F. In runs at higher temperatures with excess O2, and even with oxygen lean condition, he could destroy NH3. The residence times were 0.2 -1.0 second, and were reported to "essentially completely" destroy N-compounds.
We realized we could run a regenerator in partial CO burn mode, and convert the CO and NOx in downstream processing units to less noxious species, without adding ammonia or urea, and without a catalyst, provided we did it in stages, and with special operating conditions at each stage.
We discovered that CO oxidation could convert NOx, if unusually high temperature were used and no more than stoichiometric air was present. We found that higher temperatures, far exceeding any that had ever been used in a conventional CO boiler, could destroy NOx and NOx precursors during CO combustion with sub-stoichiometric, or just stoichiometric air. We then cooled the gas, which had a very low fuel value at this point, and added more air to burn the remaining CO, with an unusually low flame temperature, and little NOx formation during this limited stage of CO combustion.
Accordingly the present invention provides a process for the catalytic cracking of a nitrogen containing hydrocarbon feed to lighter products comprising cracking said feed by contact with a supply of regenerated cracking catalyst in a fluidized catalytic cracking (FCC) reactor means operating at catalytic cracking conditions to produce a mixture of cracked products and spent cracking catalyst containing coke and nitrogen compounds; separating cracked products from said spent cracking catalyst to produce a cracked product vapor phase which is charged to a fractionation means and a spent catalyst phase; stripping spent catalyst in a stripping means to produce stripped, spent catalyst containing coke and nitrogen compounds; regenerating stripped, spent catalyst in a catalyst regeneration means by contact with oxygen or an oxygen-containing regeneration gas at catalyst regeneration conditions to produce regenerated catalyst and a flue gas stream containing less than 1.0 mole % oxygen, at least 1.0 mole % CO; and NOx and NOx precursors; recovering from said catalyst regeneration means regenerated catalyst and recycling same to said cracking reactor; adding oxygen or an oxygen containing gas to said regenerator flue gas in an amount sufficient to convert from about 50 to 100% of the CO in said flue gas to CO2 and form a flue gas and oxygen mixture; converting said NOx and NOx precursors in a NOx conversion zone operating at a NOx and NOx percursors conversion conditions including a temperature above 2200° F. and a residence time sufficient to convert at least a majority of said NOx and NOx precursors to nitrogen in said NOx conversion zone and convert at least a majority but not all of said CO to CO2 in said zone to produce to a NOx and NOx precursor depleted gas mixture having a temperature above 2200° F. and containing CO; cooling said depleted mixture below 1800° F. to produce a cooled flue gas stream containing CO; adding oxygen or an oxygen containing gas to said cooled flue gas stream in an amount sufficient to convert at least 100% of the CO contained in said cooled flue gas stream to CO2 and converting CO to CO2 in a CO conversion zone operating at a temperature below 1800° F. to produce a flue gas stream which may be discharged to the atmosphere.
In another embodiment, the present invention provides a process for the catalytic cracking of a nitrogen containing hydrocarbon feed to lighter products comprising: cracking said feed by contact with a supply of regenerated cracking catalyst in a fluidized catalytic cracking (FCC) reactor means operating at catalytic cracking conditions to produce a mixture of cracked products and spent cracking catalyst containing coke and nitrogen compounds; separating cracked products from said spent cracking catalyst to produce a cracked product vapor phase which is charged to a fractionation means and a spent catalyst phase; stripping spent catalyst in a stripping means to produce stripped, spent catalyst containing coke and nitrogen compounds; regenerating stripped, spent catalyst in a catalyst regeneration means by contact with oxygen or an oxygen- containing regeneration gas at catalyst regeneration conditions to produce regenerated catalyst and an FCC regenerator flue gas stream containing less than 0.1 mole % oxygen, at least 3.0 mole % CO and NOx and NOx precursors including HCN in an amount so that when said regenerator flue gas is burned in a conventional CO boiler at 1400°-2000° F. in an oxidizing atmosphere it would produce a CO boiler flue gas containing more than 100 ppm volume NOx ; recovering from said catalyst regeneration means regenerated catalyst and recycling same to said cracking reactor; adding oxygen or an oxygen containing gas to said regenerator flue gas in an amount sufficient to convert from 60 to 100% of the CO in said flue gas to CO2 and form a flue gas and oxygen mixture; converting said NOx and NOx precursors in A NOx conversion zone operating at a NOx and NOx precursors conversion conditions including a temperature above 2400 ° F. and a residence time sufficient to convert at least a majority of said NOx and NOx precursors to nitrogen in said NOx conversion zone and convert at least a majority but not all of said CO to CO2 in said zone to produce a NOx and NOx precursor depleted gas mixture having a temperature above 2400° F. and containing CO; cooling said depleted mixture to a temperature below 1800° F. to produce a cooled flue gas stream containing CO; adding oxygen or an oxygen containing gas to said cooled flue gas stream in an amount sufficient to convert at least 100% of the CO contained in said cooled flue gas stream to CO2 and converting CO to CO2 in a CO conversion zone operating at a temperature below 1800° F. and less than 100 ppmv CO which may be discharged to the atmosphere.
FIG. 1 (Prior Art) shows a conventional FCC regenerator with CO boiler with CO boiler.
FIG. 2 (Prior Art) shows a conventional CO boiler.
FIG. 3 (Invention) shows a modified CO boiler, with a high temperature, refractory lined NOx precursor conversion section.
FIG. 4 (Invention) shows a simplified schematic view of a CO boiler with a preferred control system.
The process of the present invention is an integral part of the catalytic cracking process. The essential elements of this process will be briefly reviewed with a review of FIG. 1.
A heavy, nitrogen containing feed is charged via line 2 to riser reactor 10. Hot regenerated catalyst removed from the regenerator via line 12 vaporizes fresh feed in the base of the riser reactor, and cracks the feed. Cracked products and spent catalyst are discharged into vessel 20, and separated. Spent catalyst is stripped in a stripping means not shown in the base of vessel 20, then stripped catalyst is charged via line 14 to regenerator 30. Cracked products are removed from vessel 20 via line 26 and charged to an FCC main column, not shown.
Spent catalyst is maintained as a bubbling, dense phase fluidized bed in vessel 30. Regeneration gas, almost always air, sometimes supplemented with oxygen, is added via line 34 to the base of the regenerator. Air flow is controlled by flow control valve 95. Regenerated catalyst is removed via line 12 and recycled to the base of the riser reactor.
Flue gas is removed from the regenerator via line 36 and charged to CO boiler 50. Combustion air is added line 41, and additional fuel (if needed) added via line 51. The CO in the regenerator flue gas burns, releasing heat which is recovered using heat exchange means 60. In most refiners, boiler feed water is added via line 62 to heat exchange tubes 60 and high pressure steam recovered via line 64. The flue gas is discharged from the CO boiler via line 46 and charged to stack 98 for discharge to the atmosphere.
The process and equipment recited above are those used in many conventional FCC regenerators. Many FCC regenerators use such bubbling bed regenerators, which have more severe NOx emissions characteristics than high efficiency regenerators. Both bubbling fluid bed and fast fluid bed regenerators can run in partial CO burn mode and produce large amounts of NOx in a downstream CO boiler.
While the process of the present invention can be practiced in a conventional refinery, if the CO boiler can tolerate the high temperatures required, most refiners will prefer to install a separate NOx conversion stage upstream of, or as a first stage of, a move conventional CO boiler. CO boilers will be reviewed in more detailed below, starting with a more detailed description of a conventional CO boiler (FIG. 2), a preferred CO boiler for use in the present invention (FIG. 3) and ending with some discussion of a preferred control method (FIG. 4) .
FIG. 2 (prior art) shows a typical FCC CO boiler 250, drawn only roughly to scale. CO containing flue gas from the FCC regenerator enters via lines 236, while air is charged via a plurality of air inlet means 241 and fuel gas inlet means 251. These gases mix and burn in the radiant section 235 of the CO boiler. Heat is recovered via a plurality of heat exchange tubes 230. Additional heat is recovered in the convection section 245, downstream of the radiant section. Finally flue gasses pass through the economizer section 255 wherein additional heat is recovered from the flowing gas stream via heat exchange tubes 265. The cooled gas is discharged via line 246 to the flue gas stack. While the conventional CO boiler shown in FIG. 2 can be used in some refineries to practice the process of the present invention, most CO boilers will require some modifications, to meet metallurgical constraints and to improve NOx precursor conventional.
FIG. 3 (Invention) shows a CO boiler 350 with a NOx precursor conversion section 305 in an upstream portion. Flue gas from the FCC regenerator is added via lines 336 while air is charged via a plurality of air inlet means 341 and fuel gas inlet means 351. The FCC regenerator will be run to produce large amounts of CO and/or large amounts of fuel gas will be added. These gases mix and burn in the NOx conversion region 305, which operates at temperatures higher than those used in any FCC CO boiler, preferably at about 2700° F. Usually it will be necessary to line the CO boiler with a suitable refractory material 310, and provide a checker wall 314, which may be made of brick or other suitable material, to ensure adiabatic combustion in region 301. This high temperature operation converts most of the NOx precursors, but not necessarily all of the CO. More combustion air will usually be needed to burn the remaining CO, but we do not want to burn CO at the high temperatures of region 305, and therefore cool the gas with a heat removal means such as heat exchange tubes 325 in cooling region 315.
Secondary air is added via air addition means 342 to the CO combustion region 335 roughly corresponding to the radiant section of the prior art CO boiler. Heat is removed via a plurality of tubes 330, and gas then passes through the convective boiler section 345. Tubes 340 remove heat from the gas primarily by convective heat transfer, and the gas then passes into economizer region 355 where additional heat is removed. Gas is discharged to the stack via line 346.
FIG. 4 shows a preferred control method. FCC regenerator flue gas in line 436 enters the NO converter and CO boiler 450. Additional fuel such as fuel gas, if necessary, is added via line 451, while air or oxygen enriched air is added via line 441. The CO in the flue gas burns to form a high temperature gas mixture, with a temperature of at least 2200° F. and preferably above 2400 F. This mixture burns or is present in a high temperature zone 405, containing refractory insulation 410. Heat is removed from this gas in intermediate cooling region 415 by heat removal means 420, which will usually be a heat exchange tubes, or a dimpled jacket heat exchanger or the like. The cooled gas is then charged to a section which in hardware and metallurgy resembles the conventional CO boiler. Additional air will usually be added via line 541 and distributed via a plurality of nozzles 551. Heat is removed by radiant heat exchange means 430 lining region 435 and then by convective heat exchange means 440 in convective section 445. Flue gas is discharged via line 446 to the stack, not shown.
The air addition rate via line 441 is preferably controlled to provide just stoichiometric or substoichiometric air for the high temperature region. One way this can be done is by analyzing the composition and volume of all streams entering the device. A preferred and robust control method is shown in FIG. 4, with an oxygen sensor 72 and analyzer controller 70 operatively connected with flow control valve 443 on air line 441.
An equivalent control method is to keep the air flow in line 441 constant, and use the signal from controller 70 to adjust fuel gas flow.
More details will now be provided about various conventional and unconventional parts of our process.
Any conventional FCC feed can be used. The process of the present invention is useful for processing nitrogenous charge stocks, those containing more than 500 ppm total nitrogen compounds, and especially useful in processing stocks containing very high levels of nitrogen compounds, such as those with more than 1000 wt ppm total nitrogen compounds.
The feeds may range from the typical, such as petroleum distillates or residual stocks, either virgin or partially refined, to the atypical, such as coal oils and shale oils. The feed frequently contains recycled hydrocarbons, light and heavy cycle oils which have already been subjected to cracking.
Preferred feeds are gas oils, vacuum gas oils, atmospheric resids, and vacuum resids. The invention is most useful with feeds having an initial boiling point above about 650° F.
Commercially available FCC catalysts may be used. The catalyst preferably contains large amounts of large pore zeolite for maximum effectiveness, but such catalysts are readily available. The process will work with amorphous catalyst, but few modern FCC units use amorphous catalyst.
Preferred catalysts for use herein will usually contain at least 10 wt % large pore zeolite in a porous refractory matrix such as silica-alumina, clay, or the like. The zeolite content is preferably much higher than this, and should usually be at least 20 wt % large pore zeolite, with optimum results achieved when unusually large amounts of large pore zeolite, in excess of 30 wt %, are present in the catalyst. For best results the catalyst should contain from 30 to 60 wt % large pore zeolite.
All zeolite contents discussed herein refer to the zeolite content of the makeup catalyst, rather than the zeolite content of the equilibrium catalyst, or E-Cat. Much crystallinity is lost in the weeks and months that the catalyst spends in the harsh, steam filled environment of modern FCC regenerators, so the equilibrium catalyst will contain a much lower zeolite content by classical analytic methods. Most refiners usually refer to the zeolite content of their makeup catalyst, and the MAT (Modified Activity Test) or FAI (Fluidized Activity Index) of their equilibrium catalyst, and this specification follows this naming convention.
Conventional zeolites such as X and Y zeolites, or aluminum deficient forms of these zeolites such as dealuminized Y (DEAL Y), ultrastable Y (USY) and ultrahydrophobic Y (UHP Y) may be used as the large pore cracking catalyst. The zeolites may be stabilized with Rare Earths, e.g.,.0.1 to 10 wt % RE.
Relatively high silica zeolite containing catalysts are preferred. Catalysts containing 20-60% USY or rare earth USY (REUSY) are especially preferred.
The catalyst inventory may also contain one or more additives, either present as separate additive particles, or mixed in with each particle of the cracking catalyst. Additives can be added to enhance octane (medium pore size zeolites, sometimes called shape selective zeolites, i.e., those having a Constraint Index of 1-12, and typified by ZSM-5, and other materials having a similar crystal structure).
The FCC catalyst composition, per se, forms no part of the present invention.
Use of a Pt CO combustion promoter is neither essential nor preferred for the practice of the present invention, however, some may be present. These materials are well-known.
Additives may be used to adsorb SOx. These are believed to be primarily various forms of alumina, rare-earth oxides, and alkaline earth oxides, containing minor amounts of Pt, on the order of 0.1 to 2 ppm Pt. Additives for removal of SOx are available from several catalyst suppliers, such as Davison's "R" or Katalistiks International, Inc.'s "DESOX."
The effectiveness of these additives will be degraded some because the regenerator will be very deep in partial CO combustion mode. Some benefit will be seen, but not as much as if the regenerator were in complete CO burn mode.
The reactor operation will usually be conventional all riser cracking FCC, such as disclosed in U.S. Pat. No. 4,421,636, incorporated by reference. Typical riser cracking reaction conditions include catalyst/oil ratios of 0.5:1 to 15:1 and preferably 3:1 to 8:1, and a catalyst contact time of 0.1-50 seconds, and preferably 0.5 to 10 seconds, and most preferably about 0.75 to 5 seconds, and riser top temperatures of 900° to about 1100° , preferably 950° to 1050° F.
It is important to have good mixing of feed with catalyst in the base of the riser reactor, using conventional techniques such as adding large amounts of atomizing steam, use of multiple nozzles, use of atomizing nozzles and similar technology.
It is preferred, but not essential, to have a riser catalyst acceleration zone in the base of the riser.
It is preferred, but not essential, to have the riser reactor discharge into a closed cyclone system for rapid and efficient separation of cracked products from spent catalyst. A closed cyclone system is disclosed in U.S. Pat. No. 4,502,947 to Haddad et al, incorporated by reference, and in various journal articles and is available from the M. W. Kellogg engineering company.
It is preferred but not essential, to strip rapidly the catalyst just as it exits the riser, and upstream of the conventional catalyst stripper. Stripper cyclones disclosed in U.S. Pat. No. 4,173,527, Schatz and Heffley, incorporated herein by reference, may be used.
It is preferred, but not essential, to use a hot catalyst stripper. Hot strippers heat spent catalyst by adding some hot, regenerated catalyst to spent catalyst. Suitable hot stripper designs are shown in U.S. Pat. No. 3,821,103, Owen et al, incorporated herein by reference. If hot stripping is used, a catalyst cooler may be used to cool the heated catalyst before it is sent to the catalyst regenerator. A preferred hot stripper and catalyst cooler is shown in U.S. Pat. No. 4,820,404, Owen, incorporated by reference.
Conventional FCC steam stripping conditions can be used, with the spent catalyst having essentially the same temperature as the riser outlet, and with 0.5 to 5% stripping gas, preferably steam, added to strip spent catalyst.
The FCC reactor and stripper conditions, per se, can be conventional.
The process and apparatus of the present invention can use conventional bubbling dense bed FCC regenerators or high efficiency regenerators. Bubbling bed regenerators will be considered first. In these units much of the regeneration gas, usually it is air, passes through the bed in the form of bubbles. These pass through the bed, but contact it poorly.
These units operate with large amounts of catalyst, because the bubbling bed regenerators are not very efficient at burning coke, hence a large inventory and long residence time in the regenerator were needed to get clean burned catalyst.
The carbon on regenerated catalyst can be conventional, typically less than 0.3 wt % coke, and more preferably less than 0.15 wt % coke, and most preferably even less. By coke we mean not only carbon, but minor amounts of hydrogen associated with the coke, and perhaps even very minor amounts of unstripped heavy hydrocarbons which remain on catalyst. Expressed as wt % carbon, the numbers are essentially the same, but 5 to 10% less.
Although the carbon on regenerated catalyst can be the same as that produced by conventional FCC regenerators, the flue gas preferably contains large amounts of CO. Usually the flue gas will contain more than 1.0 mole % CO, and preferably more than 2 or 3 mole % CO, and most preferably more than 5 mole % CO. Many existing FCC regenerators, especially those designed to run with CO boilers, produce flue gas with 6 to perhaps 9 or 10 mole % CO. Expressed as CO2 :CO ratios, the flue gas preferably contains from about a 1:1 ratio to a 10:1 ratio, and most preferably from about 3:1 to 1:1. This minimizes heat release in the FCC regenerator, increases the coke burning capacity of the regenerator, and maximizes the fuel value of this gas. Preferably the FCC regenerator is run so that when stoichiometric or 90% of stoichiometric air is added to the regenerator flue gas the flame temperature will be at least 2200° F., and more preferably at least 2400° F.
Because the regenerator will be deep in partial CO burn, there will not usually be much free oxygen in the flue gas, almost always less than 1.0 mole %, and typically from 0.1 mole % to none. This is because any oxygen available will rapidly react to extinction at these conditions.
The NOx /CO conversion zone operates in two distinct regions, a high temperature zone and a low temperature zone. The high temperature zone must remove most of the NOx or NOx precursors and inherently removes 80-90 +% of the CO present, although it does not have to remove this much CO. The low temperature zone must remove enough CO to meet local flue gas emissions limits. There is usually not much CO left in the stream at this point, so CO afterburning inherently forms very little NOx. Each zone will be discussed in more detail below.
This zone, region 305 in FIG. 3, and 405 in FIG. 4, must operate at a temperature above 2200° F., preferably above 2250° F., more preferably above 2300° . The zone is essentially free of catalyst. Optimum results will usually be achieved when the temperature is 2400° to 2900° F., with higher temperature operation possible but not preferred because of metallurgical limits and because many refractory linings start decomposing at temperatures above 3000°-3100° F. Temperature alone does not define this zone, adequate residence time must also be permitted to achieve the desired conversion of NOx and its precursors to nitrogen. Usually a residence of 0.1 to 10 seconds will suffice. Most units will operate with 0.5 to 5 seconds of gas residence time, and about 1 or 2 seconds of gas residence time is preferred. There is a trade-off between time and temperature, and higher temperatures permit successful operation with shorter residence times.
Preferably the outlet of the high temperature zone comprises a "checker wall" a porous barrier which allows gas to pass from the high temperature zone to the contiguous intermediate cooling zone, while retarding radiant heat loss from the high temperature zone. The use of a porous wall will also prevent gas recirculation from the cooling zone to the high temperature zone.
Use of a porous wall at the high temperature zone outlet facilitates several preferred methods of introducing gaseous reactants. Rapid and through mixing of gaseous reactants is very important. Two preferred ways of achieving rapid mixing are introducing the gases through a multiplicity of interspersed nozzles and tangential, high velocity injection. Introducing some or all of the gases at a velocity of 50 to 300 fps, in a direction tangential to an inside wall of the higher temperature chamber will create a swirling or cyclonic circulation pattern which promotes gas mixing.
The gas leaving the high temperature zone should be cooled before additional air is added to complete CO combustion. If CO combustion were completed with excess air at the high temperatures in the NOx conversion zone, then there would be a considerable amount of NOx formed during CO combustion, much of it due to nitrogen fixation.
Preferably heat transfer tubes or dimpled heat exchange surfaces line the walls downstream of the high temperature NOx conversion zone. This heat transfer can produce high pressure steam and cool the gas. Sufficient heat should be removed by radiant or convective heat exchange, so the gas leaving this zone has a temperature below 2000° F., preferably from 1400°-1900° F., and most preferably 1500°-1800° F. This is usually higher than the flue gas temperature from a conventional single stage regenerator, whether bubbling bed or high efficiency, operating in either full or partial CO burn mode.
The low temperature, or CO conversion zone region 335 and 435 in FIGS. 3 and 4 is preferably contiguous with, and an extension of, the NOx conversion zone and intermediate cooler. It may also be a separate vessel, and in many refineries will be the old CO boiler. The temperature in the low temperature zone will usually be within about 100° F. of the gas leaving the intermediate cooler. The CO conversion zone temperature may range from 1400° to 2000° F., and preferably from 1500° to 1800° F.
The gas entering the CO conversion zone will typically have the following composition:
______________________________________ Suitable Preferred Optimum______________________________________O2, mole % LT 1% LT 0.1% 0CO, mole % 0-10 0.1-8 0.5NOx, ppmv 0-100 0.1-50 0.5-10______________________________________
Where NOx refers both to oxides of the nitrogen and nitrogen compounds such as NH3 which oxidize to form NOx,
Enough air will be added to supply at least the amount required by stoichiometry to burn all the CO in the entering gas stream. Preferably modest amount of excess air is added to help drive the reaction to completion. Preferably there is rapid and thorough mixing of the added air. Thus enough air, or O2, or O2 enriched air will be added to produce a flue gas containing some free O2. Typical flue gas streams leaving the low temperature section will have the following composition:
______________________________________ Suitable Preferred Optimum______________________________________O2, mole % 0-5 0.05-2 0.1-1CO, ppmv LT 1000 LT 500 LT 100NOx, ppmv 0-100 0.1-50 0.5-10______________________________________
Again NOx refers to oxides of nitrogen and its precursors. Ideally the NOx level will change very little, or increase a modest amount in the CO conversion zone. This low production of NOx can be attributed to several factors: the destruction of most of the NOx precursors upstream of the CO conversion zone, and the low flame temperatures associated with burning CO streams containing little CO.
Usually it will be preferred to monitor frequently or continuously the CO content of the regenerator flue gas and the free oxygen content just downstream of the high temperature zone. For safety, it will usually be beneficial to measure CO and NOx content of the flue gas stream being discharged to the stack, as well as the oxygen content. For reliability, we prefer a zirconia-based, solid-state oxygen activity analyzer for at least the high temperature service, e.g., sensor 72.
Careful control of the oxygen concentration is believed to be very important. It there is more than a stoichiometric amount of oxygen this may produce a lot of NOx. If there is less oxygen present, an amount far below stoichiometric then it may be hard to drive NH3 conversion to completion.
The high temperature zone should be sized large enough so the desired conversion of NOx can occur. The CO conversion is rapid at these conditions and additional CO conversion may take place downstream. NOx conversion will usually be limiting, and in most units about 1 second of vapor residence time in the high temperature zone and some portion of the high temperature heat recovery zone near exchangers 120 will be sufficient.
The intermediate flue gas product from the high temperature combustion zone may be a unique material. It can have less than 100 ppm NOx, essentially no free oxygen or at most about 0.1 to 0.2 mole % O2, less than 3 or 4 mole % CO, and a temperature above that of any conventional single stage FCC regenerator. Preferably it has less than 50 ppm NOx, no free oxygen, less than 2% CO, and a temperature above 2200° F. In contrast, flue gas streams from conventional regenerators are always cooler, and always have more NOx or NOx precursors. Flue gas streams from conventional CO burners have excess oxygen, and much more NOx.
The intermediate flue gas product has a great deal of thermal energy, because of its high temperature, but little fuel value. The CO remaining can be burned with modest amounts of air, without forming much NOx, for two reasons. First, most NOx precursors were destroyed in the high temperature zone. Second, the low heating value of the flue gas produces low flame temperatures, so remaining NOx precursors will never see the high temperatures and high oxygen concentrations needed to form NOx . Also, the flame temperature will be too low to form appreciable amounts of NOx by thermal reaction of N2 with O2.
The flue gas going up the stack will have unusually low levels of both NOx and CO and may have unusually low oxygen levels as well. The NOx and CO levels should be below 100 ppm. Preferably NOx and CO are each below 50 ppm. Oxygen levels can be low because little CO combustion, in the conventional sense, is needed in the radiant section of the CO boiler, yet the flue gas is hot enough, typically above 1400° F. to permit efficient use of such oxygen as is added. The process tolerates operation of enough air to give 1 or 2 % oxygen in flue gas going up the stack, but this consumes a lot of energy in running the air blower and sends a lot of energy up the stack in the form of hot air. We believe satisfactory operation may be achieved with as little as 0.5 mole %, or even less than 0.2 mole % oxygen in the flue gas, discharged to the atmosphere.
It is possible to operate the process of the present invention without any added fuel for the CO boiler at one extreme, and with almost no CO in the FCC regenerator flue gas at another extreme. Even though it is possible to operate without any fuel gas added, many operators will prefer to add modest amounts of fuel gas just to help stabilize combustion and ensure that the CO boiler will continue to operate despite any upsets that may occur in the FCC unit.
The low fuel gas case will be considered first. Flue gas temperatures will rise about 110° F. for each 1 vol % CO in combusted. Many FCC regenerators run at temperatures (flue gas leaving the final stage of cyclone equipment) of 1250° to 1400° F, so operation with 8 or 9 mole % CO, perhaps with some or extensive air preheat, will achieve the temperatures needed in the high temperature zone.
For a flue gas with about 8 mole % CO, at a temperature of about 1400° F., with combustion air preheated to a high temperature (which will be difficult to do) the adiabatic flame temperature will be about 2450° F.
For a flue gas with about 9 mole % CO, starting at 1300° F, the adiabatic flame temperature will be about 2480° F., which is just barely enough to be within a good operating range for a reasonable gas residence time, on the order of about 1 second.
Thus a regenerator flue gas with large amounts of CO can burn in the high temperature, or NOx conversion zone, to form the temperatures need for NOx conversion, with little or no fuel gas added.
High fuel gas cases will now be considered. If the FCC regenerator produces little CO, i.e., is in almost complete CO combustion mode but still contains 1 or 2% CO, then large amounts of fuel gas will be needed to achieve the desired NOx conversion temperature. Large amounts of fuel gas may be needed even when the flue gas contains 6% CO, if the flue gas is not hot and/or air preheat is not available for the CO boiler.
An FCC regenerator flue gas with 6 mole % CO, at 1050° F., (a common temperature downstream of refiners with power recovery units, or turbine expanders), with fuel gas and added air supplied at 100° F. will require 8.7 moles of methane and 102 moles of air per 100 moles of FCC fluegas to produce a target flame temperature of 2800° F. In this case the fuel gas supplies about 80% of the heat needed to reach 2800° F. In many refineries significant amounts of fuel gas will be needed. This will be easy to cost justify if high pressure steam is valuable and/or fuel gas or some other fuel source is cheap.
The process of the present invention can be readily used in existing bubbling bed or fast fluidized bed FCC regenerators with only minor hardware changes. A CO boiler will be needed, but many FCC units have these, or will be forced to add them to deal with heavier feeds.
The process works well because we convert most of the NOx and its precursors in the high temperature zone at conditions which are substoichiometric or approach stoichiometric. We take advantage of thermodynamics, which indicates that the equilibrium concentrations of both NOx and reduced species go towards zero in the presence of a stoichiometric amount of oxygen. We accelerate the rates of all relevant reactions so the system approaches equilibrium in the high temperature zone. This also removes most of the CO. The low temperature zone removes the last traces of CO, but at a lower temperature, from a flue gas with such a low heating value that neither nitrogen fixation nor high flame temperatures occur.
The process of the present invention will effectively reduce NOx. Although there will be a large capital expense involved in building the high temperature section, this section will produce large amounts of high pressure steam which can be used to generate electricity or drive equipment in the refinery, and effectively offset the construction cost and the cost of any added fuel gas.
Our process does not require adding ammonia or urea or similar compounds which create the potential of a discharge of hazardous or nuisance materials. Instead, the process seems to rely on a variety of NOx precursors inherently generated in an FCC regenerator operating in partial CO burn mode, such as modest amounts of HCN and NH3.
Our process does not require any catalyst, and can tolerate the presence of large amounts of catalyst and fines which would plug many catalytic approaches to NOx control.
|Patente citada
|Fecha de presentación
|Fecha de publicación
|16 Mar 1973
|18 Feb 1975
|Exxon Research Engineering Co
|Method for removing the oxides of nitrogen as air contaminants
|1 Feb 1973
|25 Mar 1975
|Zink Co John
|Process for disposal of oxides of nitrogen
|16 Sep 1974
|20 Jul 1976
|Ralph M. Parsons Company
|Process for the production of sulfur from mixtures of hydrogen sulfide and fixed nitrogen compounds
|7 Oct 1974
|19 Oct 1976
|Comprimo B.V.
|Process for removal of hydrogen sulphide and ammonia from gaseous streams
|7 Ago 1974
|26 Sep 1978
|Agency Of Industrial Science & Technology
|Method of combustion for depressing nitrogen oxide discharge
|1 Mar 1979
|13 Ene 1981
|John Zink Company
|Disposal of oxides of nitrogen and heat recovery in a single self-contained structure
|16 Feb 1982
|20 Sep 1983
|Mcgill Incorporated
|Process for reduction of oxides of nitrogen
|15 Ago 1983
|28 May 1985
|Mcgill Incorporated
|Process of conversion for disposal of chemically bound nitrogen in industrial waste gas streams
|24 Abr 1992
|31 Ago 1993
|Shell Oil Company
|Method of removing NH3 and HCN from and FCC regenerator off gas
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|17 Abr 1995
|20 Ago 1996
|Sol Bleiweis
|Process for production and use of deactivated gaseous atomic nitrogen for post combustion gas nitric oxide emissions control
|30 Ago 1995
|6 Ene 1998
|Mobil Oil Corporation
|FCC regenerator NOx reduction by homogeneous and catalytic conversion
|30 Ago 1995
|10 Feb 1998
|Mobil Oil Corporation
|FCC NOx reduction by turbulent/laminar thermal conversion
|30 Ago 1995
|3 Nov 1998
|Mobil Oil Corporation
|FCC regenerator in partial CO burn with downstream air addition
|21 Mar 2001
|17 Jun 2003
|The Boc Group, Inc.
|Reactor modifications for NOx reduction from a fluid catalytic cracking regeneration vessel
|15 Abr 2004
|4 Dic 2007
|W.R. Grace & Co. -Conn.
|Compositions and processes for reducing NOx emissions during fluid catalytic cracking
|21 Dic 2005
|30 Dic 2008
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|Reduction of CO and NOx in regenerator flue gas
|6 Jun 2003
|3 Mar 2009
|Basf Catalysts, Llc
|Catalyst additives for the removal of NH3 and HCN
|7 Nov 2008
|5 Ene 2010
|W.R. Grace & Co.-Conn.
|Compositions and processes for reducing NOx emissions during fluid catalytic cracking
|23 Feb 2006
|24 Ago 2010
|W. R. Grace & Co.-Conn.
|Method for controlling NOx emissions in the FCCU
|29 Sep 2005
|15 Mar 2011
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|24 Mar 2006
|5 Abr 2011
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|Compositions and processes for reducing NOx emissions during fluid catalytic cracking
|22 Feb 2008
|6 Mar 2012
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|6 May 2011
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|9 Abr 2010
|31 Dic 2013
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|Systems and methods for regenerating a spent catalyst
|9 Abr 2010
|31 Dic 2013
|Kellogg Brown & Root Llc
|Systems and methods for regenerating a spent catalyst
|1 May 2003
|8 Ene 2004
|Exxonmobil Research And Engineering Company
|Process for reducing NOx in waste gas streams using chlorine dioxide
|1 May 2003
|8 Ene 2004
|Exxonmobil Research And Engineering Company
|Process for reducing NOx in waste gas streams using sodium chlorite
|1 May 2003
|5 Feb 2004
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|Oxidation of NOx's with sodium chlorite in combination with a thermal NOx removal process
|1 May 2003
|5 Feb 2004
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|Selective non-catalytic reduction of NOx
|1 May 2003
|8 Jul 2004
|Exxonmobil Research And Engineering Company
|Oxidation of NOx's with chlorine dioxide in combination with a thermal NOx removal process
|6 Jun 2003
|9 Dic 2004
|Mingting Xu
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|21 Abr 2004
|30 Dic 2004
|Mcgregor Duane R.
|Reduction of NOx in low CO partial-burn operation using full burn regenerator additives
|14 Sep 2005
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|George Yaluris
|Reduction of gas phase reduced nitrogen species in partial burn FCC processes
|29 Sep 2005
|2 Feb 2006
|George Yaluris
|Reduction of gas phase reduced nitrogen species in partial burn FCC processes
|13 Feb 2006
|7 Sep 2006
|Barckholtz Timothy A
|Reduction of NOx in fluid catalytic cracking regenerator off-gas streams
|13 Feb 2006
|7 Sep 2006
|Hurst Boyd E
|Selective non-catalytic reduction of NOx
|13 Feb 2006
|19 Oct 2006
|Barckholtz Timothy A
|Non-catalytic reduction and oxidation process for the removal of NOx
|21 Dic 2005
|21 Jun 2007
|Lee Rosen
|Reduction of CO and NOx in regenerator flue gas
|23 Feb 2006
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|George Yaluris
|Method for Controlling Nox Emissions in the Fccu
|20 Jul 2007
|22 Ene 2009
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|High-performance cracker
|6 May 2009
|10 Sep 2009
|George Yaluris
|Reduction of gas phase reduced nitrogen species in partial burn FCC processes
|25 Ago 2011
|Kuang-Tsai Wu
|Reduction of co and nox in full burn regenerator flue gas
|13 Oct 2011
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|Systems and Methods for Regenerating A Spent Catalyst
|13 Oct 2011
|Kellogg Brown & Root Llc
|Systems and Methods for Regenerating A Spent Catalyst
|15 Dic 2006
|1 Ago 2012
|Reduction of co and nox in regenerator flue gas
|15 Dic 2006
|29 Oct 2014
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|Reduction of CO and NOx in regenerator flue gas
|9 Ago 1996
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|Mobil Oil Corporation
|Fcc regenerator in partial co burn with downstream air addition
|8 Ago 1996
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|Mobil Oil Corporation
|FCC REGENERATOR NOx REDUCTION BY HOMOGENEOUS AND CATALYTIC CONVERSION
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|Fcc nox reduction by turbulent/laminar thermal conversion
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|Clasificación de EE.UU.
|208/113, 423/236, 423/235, 502/41, 423/237, 502/38
|Clasificación internacional
|Clasificación cooperativa
|Clasificación europea
|1 Mar 1993
Owner name: MOBIL OIL CORPORATION, VIRGINIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BUCHANAN, J. SCOTT;JOHNSON, DAVID L.;REEL/FRAME:006489/0240;SIGNING DATES FROM 19930212 TO 19930217
|23 Feb 1998
|Fee payment
Year of fee payment: 4
|30 May 2002
|Fee payment
Year of fee payment: 8
|27 May 2004
Owner name: EXXONMOBIL RESEARCH & ENGINEERING CO., NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:EXXONMOBIL CHEMICAL PATENTS INC.;REEL/FRAME:014669/0736
Effective date: 20031008
|24 May 2006
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Year of fee payment: 12


text: The 1995 Super Bowl halftime show was cheesy to the max – and yet also kind of awesome. The Disney-produced affair was meant to promote a new Indiana Jones ride at Disneyland, so they got a Harrison Ford fill-in to act out an over-the-top action sequence. But it was Patti LaBelle, dressed as a bedazzled Egyptian princess and belting out "Release Yourself" – followed by Tony Bennett swooping in to croon "Caravan" – that turned this performance from shtick to superb.

subset: commoncrawl


text:
Workers' compensation programs in many states have adopted more restrictive eligibility rules and lower cash benefits in recent decades. Medical benefits have become more important in workers' compensation since the 1980s, but now face challenges from the implementation of ObamaCare. The Social Security Disability Insurance program has grown much more rapidly than workers' compensation as a source of support for disabled workers. Do these developments threaten the future of workers' compensation?
An annual favorite, join in this discussion of the leading cases and current, potentially problematic issues facing workers' compensation practitioners.
This session will examine the underlying effects of mild traumatic brain injury, treatment of both medical and psychological conditions and the path to recovery.
In recognition of the 100th Anniversary of the Workers' Compensation Act, this year's session will focus on the act as it has evolved since 1915.
Learn how to effectively reduce your workers' compensation costs. During this session, information will be provided on job description/job analysis/essential functions. Discussion will include the differences between the three and whether or not one is needed. This session will also include information concerning post offers/pre-employment screens and how they can help. Education on injury prevention, does it work and how to obtain "no loss time" will be provided. Communication: Who should I talk to and what they need to know?
What post offer/pre-employment tests are allowed? This session will discuss the obligations and restrictions for use of the information collected.
This session will provide the physicians' perspective of the use of narcotics for work injuries and detox. The physicians will also discuss the ethical considerations when prescribing, monitoring and withdrawing injured workers from narcotics.
Continuation of part 1.
These experienced large and small employers will address topics such as educating the workforce, before-injury training, post-injury treatments, their part in the claims management process, modified duty, return to work, working with the adjuster, communications with the insurance carriers and panel providers.
Join this session to discover how alternative methods for treating chronic pain have evolved over the last 100 years. The speakers will discuss these alternative methods for treating chronic pain due to work-related injuries from 1915 to present.
This session will discuss the timeline of significant developments and events through interviews with a variety of experts.
Primer on employers' liability portion of the workers' compensation policy. Discuss the impact of the recent Supreme Court case, Tooey vs. AK Steel Corporation.
When a family is suddenly faced with a workplace injury or fatality, the emotional and financial impact can be long-term and overwhelming. The surviving parent often struggles to pay for just the necessities such as food, clothing, and a home. Dreams of a college education for his or her children may be suddenly out of reach. That's where you and Kids' Chance of Pennsylvania can help! Kids' Chance provides scholarships for college and vocational education to children of Pennsylvania workers who have been killed or seriously injured in a work-related accident. Join us for breakfast and learn how you can become involved in Kids' Chance and ultimately, how you can impact the educational goals of children who may not otherwise have a chance.
Hear what this leading expert has to say about the fascinating surveillance products and techniques used in today's digital world.
An educational and motivational workshop that utilizes a sports analogy for aging and living by walking you through your "Four Quarters of Life." This workshop provides knowledge and motivation to make a plan of action that will benefit personal well-being. Mr. Everest will discuss the importance of integrating lifestyle, workers' compensation and safety. He will also address the Affordable Care Act's provisions regarding wellness programs and how employers can implement them.
Pennsylvania's workers' compensation system is relatively unique among large states in the stability of its performance over time. This session examines that stability and the reasons why. Dr. Richard Victor will use WCRI data to show Pennsylvania's uniqueness among large states. Mr. Bruce Hockman and Mr. Tim Wisecarver will draw upon their diverse and rich experience in Pennsylvania's system to suggest how such stability was achieved and sustained.
Topics will include the exclusive remedy of the act, jurisdiction, notice, statute of limitations, employment relationship and course and scope of employment.
While the popular use of social media has increased exponentially over the course of the past 10 years, its impact upon the law and litigation remains in its early stages. The program showcases ethical dilemmas faced by showing several vignettes including: counsel's knowledge of a client removing content off a social media page; an adjuster "friending" a party in litigation; when and if social media content viewed/printed must be turned over to the other side in discovery; and the use of social media at a hearing.
These speakers will present a brief historical review of vocational rehabilitation in Pennsylvania workers' compensation and where we are today.
Back by popular demand! These panelists will discuss the interface between workers' compensation and the Americans with Disabilities Act (ADA), the Family Medical Leave Act (FMLA), Title VII (Workplace Harassment and Discrimination) and return-to-work programs. Topics will cover how long ADA lasts, employer/employee responsibilities with regard to FMLA and issues relating to separation of employment, including COBRA.
Panelists will provide an overview of the purpose and key provisions of the Workers' Compensation Act, review the many insurance and self-insurance options available and provide employers with useful information to consider in choosing the right coverage option for their business.
Previously offered as WC 101, Workers' Compensation Judge, David Torrey, provides a basic overview of workers' compensation in Pennsylvania, including a discussion on its history, basic entitlements, wage loss, course of employment and disability/partial disability.
This session will discuss the requirements and timeline for filing a fee review at the first level. This session will also address new features/changes in WCAIS with regard to Fee Review.
Test your workers' compensation knowledge. This fun and informative session will take the attendees through the nuances of workers' compensation in Pennsylvania.
A discussion of specific claims processes from the moment of injury until the final adjudication from both the injured worker's and the employer's point of view.
This session will provide information on the process to contest an initial administrative fee review determination. Also, getting started: Learn the underlying regulatory requirements of billing, payments and challenges.
Workers' compensation judges will offer their perspectives on the litigation and mediation processes. Suitable for all parties to a workers' compensation claim. The judges will discuss WCAIS, fee review appeals, medical evidence, witness credibility, surveillance, and more.
In this session, the panel will present the top 10 litigation processes dos and don'ts, which make for a positive litigation experience.


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Item Size: M Weight:59Kg/130.1Lbs Height:161cm/63.4in Bust:36B Waist:70cm/27.6in Hips:99cm/39.0in Overall Fit:True to Size
Great for spring, summer and even fall! As pictured. Runs a bit short, overall very cute dress.
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Linkin Park-Underground 11-2011-HB
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Linkin Park-Underground 11-2011-HB (Size: 58.43 MB)
Artist: Linkin Park
Album: Underground 11
Label: Machine Shop Marketing / Warner Brothers
Genre: Crossover
Street Date: 2011-11-15
Quality: 235 kbps / 44.1kHz / Joint Stereo
Encoder: Lame 3.98.4 -V0
Size: 61.25 MB
Time: 34:12 min
1. YO (MTM Demo) 2:44
2. Slip (1998 Unreleased Hybrid Theory Demo) 3:30
3. Soundtrack (Meteora Demo) 3:15
4. In The End (Demo) 3:52
5. Program (Meteora Demo) 3:31
6. Bang Three (What I've Done Original Demo) 3:29
7. Robot Boy (Test Mix, Optional Vocal Take) 4:31
8. Broken Foot (Meteora Demo) 2:43
9. Esaul (A Place For My Head Demo) 3:09
10. Blue (1998 Unreleased Hybrid Theory Demo) 3:28
Here is the 11th annual Linkin Park fan club CD. This one features some great demos from the early days of the band when they were known as Hybrid Theory just after Chester joined. Other stand outs include some early demos
of In The End and Esaul (A Place For My Head Demo) which have been highly sought after by die hard Linkin Park fans. The song Blue also features a vocal melody that would later be re-written and become the chorus for the hit single Crawling.
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There are many reason, both serious and comical, to dress in our Priest Adult Costume. This costume comes complete with a typical long black robe with long sleeves. Also included in this costume is a traditional white priest collar. This is a biblical costume that can be worn as a humorous Halloween party costume. Or, wear it after you become certified by the internet to pronounce a couple man and wife. You can also decide to wear this traditional Priest Adult Costume as a humorous Halloween party costume. This would pair well with lots of different religious/biblical costumes if you're dressing up with other people, too! Add some accessories like rosary beads and you'll be an official priest! A priest is the one to preach during church, and the same person you confess all of your sins.
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Following my last post on Dana Tanamachi, I have developed a growing interest in chalk typography. Having given it a go at Lolly's wedding, I have to admit that it is rather difficult! So when I saw a bookcover done by Miss.Tanamachi in the gorgeous Book Lounge this weekend, I googled Chalk Type. She definitely dominates the art! But I found a lovely recipe print by Leanda of One Little Bird (done digitally, but I love the use of type), and a chalk alphabet by the always awesome, Jessica Hische.
Dana's design: The Art of Fielding By Chad Harbach
One Little Bird Studio's Cherry Pie Recipe
Jessica Hische's Chalk Alphabet
I'm delightfully busy at the moment but check back soon for some new 'themed posts'. Over and out*


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|J. M. SYNGE (Frontispiece)
From an oil painting by James Paterson, R.S.A., 1913. Appearing as portrait No. 9 in Appendix B of this book, and reproduced for the first time by courtesy of the Artist. With autograph signature "Yours cordialy -- J. M. Synge:"
(Title-page, also front outside page of family tree) To face page
Where J. M. Synge stayed when a boy. Now the property of the late Mr. E. M. Synge's heirs. From a hitherto unpublished photograph by Miss M. B. Synge ( August, 1904). The lady on the left is Miss Emily Synge, who built the cottage.
From a hitherto unpublished photograph taken by Mr. E. M. Stephens (Synge's nephew), circa 1897. By courtesy of Mr. E. M. Stephens and Mr. E. H. Synge. ("Ben" is the dog referred to in Synge's unreprinted Wicklow sketch, An Autumn Night in the Hills, published in "The Gael" ( New York), April, 1913, p. 117.)
From a hitherto unpublished snapshot taken by Pan Karel Mušek ( July, 1906). By courtesy of Pan Karel Mulek.
From a pen-and-ink sketch by his father, Mr. John B. Yeats, R.H.A. The frontispiece to "Mosada" ( 1886). Reproduced by kind permission of Mr. T. W. Rolleston. ("Mosada," a dramatic poem by W. B. Yeats, first appeared under Mr. Rolleston's Editorship in the Dublin University Review for June, 1886, and was immediately reprinted as a booklet or brochure. It has not been included in Mr. Yeats's Collected Works, and the above portrait, which appeared only in the booklet, is now exceedingly scarce.)
From a hitherto unreproduced photograph taken by James Paterson, R.S.A., in 1908 (together with the published photograph appearing as portrait No. 8 in Appendix B of this book). By courtesy of Mr. James Paterson.


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Allston Trading, LLC, is a premier market maker in worldwide financial exchanges. We trade hundreds of different stocks, bonds, futures, options and other finanMore
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(312) 663-7111(312) 663-8841Fax
ProPub_Iteration_NT.411[05] SEIDXWK-23


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The Winchester Regional Airport is a 450 plus acre, all weather, 24-hour general aviation airport with a full ILS approach system, 5,500' grooved asphalt runway.
Conveniently located southeast of the interchange for State Routes 50/522 and Interstate 81 at the Top of Virginia.
Located 45 nautical miles from Dulles International Airport and 90 minutes from downtown Washington, DC, with full ILS approach system.
Winchester Aviation is located midfield in the GA terminal building and provides fuel and line services.
For more information contact Winchester Aviation at 540-662-5786 or email firstname.lastname@example.com
Whether you are arriving for business or pleasure, we look forward to serving you!
491 Airport Road
Winchester, Virginia 22602
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I Remember Me
|Release Date: November 09, 2001
|Running Time: 74 mins.
|MPAA Rating: None
|Box Office: $4,039.00
|Genre: Documentary
Blake Edwards
Michelle Akers
Stephen Paganetti
Kim A Snyder
All Cast & Crew >>
Summary:Six years ago, director Kim Snyder was suddenly struck with flu-like symptoms so severe that she was bedridden for nearly a year. To this day, she has not fully recovered. Her mysterious illness, which baffled doctors, was finally diagnosed as Chronic Fatigue Syndrome. This film, motivated by Snyder's own need for answers, is both an intimate look at her struggle with a debilitating condition and an informative investigation that brings much-needed clarity to this widely misunderstood affliction. While medical experts offer differing opinions on the disease's origin and cause, sufferers of CFS (including film director Blake Edwards, Olympic gold medalist Michelle Akers, and high school senio... Full Summary >>


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Playboy: Hot teacher, 1
Advertising Agency: Neogama/BBH, São Paulo, Brazil
Executive Creative Director: Alexandre Gama
Creative Directors: Márcio Ribas, Wilson Mateos
Art Director: Max Geraldo
Copywriter: Patrícia Leme
Photographer: Bruno Cals
Digital Retouch: Daniel Leão, Alessandra Perez
10 comments
Take away the makeup and costume and you have an average girl. Not impressed with campaign either.
I think, therefore... yeah.
But aren't you glad makeup and costumes exist? Totally not impressed with the campaign, but love costumes and makeup on chix.
I think the main problem is that the promo itself is messed up. I mean, after looking at the ad, I'm wishing I could win a year's subscription or a trip to the mansion or something. And what do they offer me? Scooters, notebooks and videogames? What the hell do those prizes have to do with Playboy? And more importantly, is this what I shaved my balls for?
playboy wouldn't use these women, or they'd pose them properly if they did. i could see maxim doing this, but playboy sits a little higher than this.


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I like to play World of Warcraft on my minimum specs pc. But just two days ago if I try to open the game I get an error message saying that: "This application has failed to start because WowInitcode.dll was not found. Re-installing the application may fix this problem."
Can anyone tell me what is WowInitcode.dll? Why is this WowInitcode.dll required to play game cause I have never come accross this strange file before? Thank you


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Mobile Site You Are Here > PFR Home > Players > J > Phillip James > News Archive
News: s-r blog:How to Tell If Your Team Just Drafted a QB Bust
Phillip Ray James
Position: G
Height: 6-2 Weight: 265 lbs.
Born: December 3, 1964 in Atlanta, TX
High School: Jack YatesCollege: Southern (school history)
Weighted Career AV (100-95-...): 2 (11632nd overall since 1950)
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Innovation is needed to ensure the durability of the shipbuilding sector in Europe and to strengthen the competitive position of European equipment manufacturers, ship owners and operators.
The shipbuilding sector in Europe employs over 500.000 people in some 300 shipbuilding and ship repair yards. The European marine equipment sector represents a market share around 36% of the estimated worldwide total value. A quarter of the world's tonnage (9,000 merchant vessels) sail under EU flags employing some 184,000 people, while inland shipping employs 43.000 people.
Research priorities
- Competitiveness of shipyards, including equipment:
- Innovative vessel concepts
- Improved manufacturing tools and techniques
- Design tools for structure reliability and improved hydrodynamics
- Use of new materials and combination of materials
- New materials for ship equipment and engines
- Coating processes
- Competitive ship operations
- Integrated navigation systems and decision support systems
- E-maritime
- Ship-shore interfaces
- Fast and reliable inspection techniques
- Improved life-cycle, including sustainable ship dismantling
- Sustainable repair techniques
- Safe and clean dismantling processes
- Life-cycle assessment methods
- See also
- European Commission – DG Competition
- European Commission – DG Transport
- European Commission – DG Enterprise
- International Maritime Organisation
- WATERBORNETP Technology Platform


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"Seattle! Emerald City, indeed..." Seattle by gilescorey
Seattle Travel Guide: 3,209 reviews and 7,970 photos
I have a friend in the Broadway cast of "Shrek! The Musical", and decided to pop up to Seattle for the previews, rather than do the long journey to NYC from Los Angeles.
Hey, I'd never been to Seattle and this seemed like the ideal long weekend.
I spent two nights in two different hotels, and the rest of the time crashing in Queen Anne.
Without a doubt, Seattle is a city on the rise.
Downtown is rife with cranes, condo conversions, boutiques, returning young professionals, and fleeting images of the destitute being forced out of the central city. Where Seattle has an advantage over similarly sized cities is in it's compact geography. Downtown's rebirth provides an anchor to surrounding neighborhoods that feel remarkably integrated to the city as a whole - regardless of the 5 Freeway gap and the abominable Alaskan Way elevated roadway.
Expand mass transit, take down Alaskan Way(in the works) and cap the freeway with parkland(my suggestion), and few cities will be able to compete on livability and scenic superiority. From the waterfront to the hilly neighborhoods ringing the core, Seattle will be an urban model.
Unfortunately, I'm not the only person aware of Seattle's potential. I was shocked by how expensive Seattle is: the housing prices, rental and otherwise, are astronomical. The dining, and entertainment scenes don't yet justify such high demands, but I'd wager developers see the future of Seattle in the same way I do. Thus, housing is outrageous, already.
- Pros:Ocean, lakes, hills, and...oh, yeah, some coffee shops.
- Cons:public transit lacking, expensive stays, quiet nightlife
- In a nutshell:A hip city on the rise, with an impressive quality of life.
Reviews (8)
This is a great slice of coziness with good pub grub in my fave Seattle neighborhood, Ballard. It's easy to find, being... more travel advice
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Newegg.com - A great place to buy computers, computer parts, electronics, software, accessories, and DVDs online. With great prices, fast shipping, and top-rated customer service - once you know, you Newegg.
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Newegg.com - Computer Parts, Laptops, Electronics, HDTVs, Digital Cameras and More!
Sold and Shipped by BuyVPC.com
Create cool effects on black dark and white paper with the Crayola Washable Gel Markers - 8-Pack! Great colors for drawing and doodling! You can also use washable gel markers on glossy paper poster boards wrapping paper and more! These washable markers are formulated to easily wash from skin and most children's clothing. From its earliest beginnings, Crayola has been about color. They came into being when cousins Edwin Binney and C. Harold Smith took over Edwin's father's pigment business in 1885. More than 120 years later, color - along with creativity, learning and most of all, fun - is the hallmark of the Crayola company who stands out as the premiere name in crayons, markers and paint for kids.
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This article has not yet passed wikiHow's quality review process. Learn more
Edit Article
How to Act Like You Know It All
Knowing it all is impossible but if you would like to act like you do then you may try out a few steps mentioned here. The 'I know it all attitude' helps when you are dealing with harsh people who belittle you each time they catch you not knowing something. If this is the concern, you may still get help from these pointers to make you appear smarter. Read on.
CloseThis article has not yet passed wikiHow's quality review process. Learn more
CloseThis article has not yet passed wikiHow's quality review process. Learn more
1Know the difference. Acting like you know something is different from acting like you know everything. Depending upon what you are looking to achieve, you may choose your stand.
- Knowing it all could be applied in front of people who know very little.
- Because they have no other option but to believe you as they do not know much.
- Knowing as much as you need could be used with any and everyone alike.
- Knowing it all could be applied in front of people who know very little.
2Before entering the game of projecting that you know it all. Predict what will be discussed in the group so you go prepared. You could predict based on what makes them pick a topic to discuss or who brings up topics. Even if you can't predict a topic, you could read about some things to be able to add your input somewhere in the conversation.
3Make yourself heard. When entering the conversation say "Oh I heard about that it was on TV! I think it was a documentary I was watching, it was actually very fascinating". You must involve yourself in the conversation by:
- Nod pensively.
- Smiling and being in sync with the group in terms of expression.
- Looking critical as in thinking critically about what has been discussed by then.
- Make sure your posture is not slouchy, so that you look interested about the conversation.
- Don't sit, nod or smile only because it will make you look monotonous or uninterested instead say something like, "Oh really, that is amazing, I didn't know something like that happened!"
4When feeling confused. If you end up feeling absolutely clueless, fold your hands. Folding hands makes one look unapproachable. Even if someone wants to ask you something they may not because you are not looking approachable. You may also look away, fold your legs, look at your phone or start reading a book.
5At the end of the conversation say "It was very interesting and enlightening." You may suggest another topic or topics for further discussions so you appear bright.
Community Q&A
Ask a Question
- Don't be be too upfront, or pretend too much which will make them ask you too many things.
- Ignore the topic, say that you know it all and that you are interested in talking about greater things.
- Do not get carried away, as it comes off as a lie once you're asked a question. Apologize for not knowing just this one and that you know other things better.
- If you want, find out more about the topic and indulge in the conversation once again to exhibit your knowledge of the subject.
- When others speak, listen to them and paraphrase them in your on words to sound like you expressed it.
- Knowing what is discussed about might be important. Hence it is being discussed. If it is not important, you may stir clear of it to avoid any embarrassments or wasting time on trivial things.
Article Info
Categories: Conversation Skills | Articles in Quality Review
Thanks to all authors for creating a page that has been read 432 times.
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Electric Toyota Supercar Aims to Set EV Lap Record at Nordschleife
We love electric vehicles (EV), but personally we can't get enough of EV supercars. Now comes news that Toyota Motorsport GmbH (TMG) will be attempting to make Nürburgring history on August 29th with its very own EV supercar. The TMG supercar uses two
Read more >


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Ronna & Beverly
Friday, November 30 2012
UCB Franklin
5919 Franklin Ave., Los Angeles, CA 90028
with Elizabeth Reaser (Twilight) & Shannon Woodward (Raising Hope)
×1 ticket = $5
(paid at the box office)
"Pick of the List" - Los Angeles Times
"Weekend Pick" - LA.com
"Comedy Pick" -Metromix
"Theater Pick" - Los Angeles Magazine
"To Do" -defamer.com
"Count on it all getting over-the-top outrageous." - NBC Los Angeles
Just a few things you need to be aware of...
Be On-Time
Get there 15 minutes early or your seat may be lost.
Know Where to Go
We have a few different locations, make sure you are going to the right one.
No Refunds or Exchanges
ALL purchases are final. Please don't ask for a refund.
Lineup May Change
The performers listed may not all be present.
One moment....


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Job openings in November 2010
January 12, 2011
There were 3.2 million job openings on the last day of November. The job openings rate was essentially unchanged over the month at 2.4 percent.
Since the most recent series trough in July 2009, the number of job openings has risen by 0.9 million, or 39 percent. This trough immediately followed the end of the recession in June 2009 (as designated by the National Bureau of Economic Research).
Even with the gains since July 2009, the number of job openings in November remained 1.1 million below the 4.4 million openings when the recession began in December 2007.
These data are from the BLS Job Openings and Labor Turnover Survey, and are seasonally adjusted. More information can be found in "Job Openings and Labor Turnover — November 2010" (HTML) (PDF), news release USDL-11-0015.
Bureau of Labor Statistics, U.S. Department of Labor, The Economics Daily, Job openings in November 2010 on the Internet at http://www.bls.gov/opub/ted/2011/ted_20110112.htm (visited May 30, 2016).
Recent editions of Spotlight on Statistics
Employment and Wages in Healthcare Occupations
Healthcare occupations are a significant percentage of U.S. employment. Some of the largest and highest paying occupations are in healthcare. This Spotlight examines employment and wages for healthcare occupations.
Fifty years of looking at changes in peoples lives
Longitudinal surveys help us understand long-term changes, such as how events that happened when a person was in high school affect labor market success as an adult.
- A look at pay at the top, the bottom, and in between
The Spotlight examines how earnings and wages have changed over time and how they differ within a geographic area, industry, or occupation.


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Arthritis Health Center
News Related to Arthritis
2 in 5 Rheumatoid Arthritis Patients Sedentary
Jan. 26, 2012 -- More than 40% of U.S. adults with rheumatoid arthritis get no exercise, according to a study published in the journal Arthritis Care & Research. RA, which affects 1.3 million adults, is a painful condition that causes joints to be swollen, stiff, and damaged. Inactivity puts RA patiRead Full Article
Enriched Milk May Ease Gout
Jan. 23, 2012 -- Drinking a daily dose of enriched skim milk may help reduce gout flare-ups. A new study shows that people who drank an enriched skim milk shake made from powdered milk and additional dairy components had fewer gout attacks and less painful symptoms. Previous research has already shoRead Full Article
Knee, Hip Replacements Carry Blood Clot Risk
Jan. 17, 2012 -- Doctors have long known that dangerous blood clots can occur after joint replacement surgery of the knees or hips. Now, a new analysis puts numbers on the risk. About 1 in 100 patients who undergo knee replacement surgery and 1 in 200 patients who have hip replacement surgery will dRead Full Article
Exercise, Talk Therapy by Phone May Help Relieve Fibromyalgia Pain
Jan. 12, 2012 -- Exercise and/or talking with a therapist on the phone once a week may significantly reduce chronic pain, a new study shows. About 20% to 40% of adults report experiencing chronic pain, Seth Berkowitz, MD, and Mitchell Katz, MD, of the Los Angeles County Department of Health ServicesRead Full Article
Drug Already on Market May Be a Boon to Gout Patients
Jan. 5, 2012 -- A drug already on the market for some rare conditions may be able to help many people with the far more common condition of gout. More than 6 million Americans have experienced gout, an excruciatingly painful form of arthritis that comes on suddenly, leaving sufferers miserable and oRead Full Article
Knee Arthritis: Very Low-Calorie Diet May Help
Dec. 21, 2011 -- Obesity is a major risk factor for knee osteoarthritis, and although weight loss is often recommended to reduce painful pressure on joints, not all patients succeed in shedding extra pounds. Osteoarthritis -- sometimes called "wear and tear" arthritis -- is frequently related to ageRead Full Article
Study: Bone Drugs May Increase Longevity of Replaced Joints
Dec. 6, 2011 -- New research may help hip and knee replacements last longer in patients who take commonly prescribed bone-loss drugs. Joint replacement surgeries help millions live with less pain, but many people who have them eventually need repeat procedures when the implants loosen over time. NowRead Full Article
Artificial Hips: Newer Might Not Be Better
Nov. 29, 2011 -- Traditional hip implants might be safer and last longer than some new ones, an FDA-funded study finds. It's among the first studies to compare outcomes in people who got different kinds of artificial hip implants with different materials. When researchers evaluated total hip-replaceRead Full Article
Exercise May Improve Memory in Fibromyalgia Patients
Nov. 17, 2011 -- Exercise improved pain and memory in women with fibromyalgia, even without medication, suggests a new study. Researchers found that regular aerobic exercise decreased activity in memory and pain control areas of the brain. "The decreased brain activity ... suggests that the brain isRead Full Article
Women Under 50 With RA at Higher Fracture Risk
Nov. 11, 2011 (Chicago) -- Women under 50 with rheumatoid arthritis (RA) are more than twice as likely to break a bone as those without the condition, a large study shows. While it's known that rheumatoid arthritis is associated with a higher rate of fractures in older men and women, "there is an inRead Full Article


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London A Cappella Festival 2016 offered an opportunity to experience the very best vocal talent from across the globe. Welcoming international headliners and industry experts in a star-studded line-up, the festival schedule was bursting with sold out performances, workshops, showcases, talks and free interactive events.
'Whether you're into jazz, choral, contemporary or even beatbox, London's three day A Cappella Festival's lineup is looking pretty damn tempting.' Glamour Magazine
'However you spell it, a cappella is huge right night. This festival which is now in its seventh year explores the potential of the unaccompanied human voice through genre-spanning concerts, workshops, talks and interactive events.' Time Out
'The London A Cappella Festival brightons up dull and cold January very year at Kings Place in London.' BBC Radio 3, The Choir


text: Just my opinion but I wouldn't base my resort choice on the location (as in if it's closest to MK). All resorts have transportation that take you to all the parks. I've stayed at Animal Kingdom Lodge which is furthest from MK but once you get on the bus it doesnt' seem that long. Pick a place based on your budget & your personal taste in style & theming. There are so many great ones! You may want to do a midline priced resort (moderate) & that way not so much of your money is going for room & you'll have more to spend on shopping or food or doing other activities. You really should research the resorts perhaps on this site & look at lots of pictures so you can get an idea. They all have wonderful pools too!


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Leslie Neale
Actor Leslie Neale Movies / Films:Uncle Sam (1996) Gremlins 2: The New Batch (1990) aka Gremlins 2 (1990)
Reviewed Movies Starring Leslie Neale
Uncle Sam (1996)
Master Sergeant Sam Harper (David "Shark" Fralick), an honorable Desert Storm hero is accidentally killed by "friendly fire" while fighting in Kuwait. Tragically, this one time hero…
Gremlins 2 - The New Batch (1990)
Billy Peltzer and Kate Beringer move to New York City and meet up with their Mogwai friend, Gizmo, when a series of accidents creates a new generation of diverse gremlins. Billy, Kate, and Gizmo must…


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: [Discussion]
What would you like to see in a Pokémon fangame?
View Single Post
September 19th, 2012 (6:40 AM).
Egg: It's going to hatch soon!
Join Date: Aug 2012
Location: Italy
Gender: Male
Nature: Lax
Posts: 18
What i would like to see from a pokemon game is something unique in the first place. If i just have to play a normal pokemon game, i could just play the original ones. I would like for example a good story or strange gameplay mechanics.
I don't really care if there aren't all the 649 pokemon or all the characters from the previous games. I'd like less, but better done, because i always see big projects and i know most of them won't be finished or they'll be rushed. Good luck to everyone who is making a fan game!
This is my signature!
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Hotel supply furniture is manufacturer and exporter of whole hotel room furniture. Highly experienced in supplying furniture for hotels, apartments, resorts, office and all kind contract furniture. Our warehouse placed in Indonesia ( central java, Jepara ) Worldwide export since 1993.
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