text:
|Publication number
|Publication type
|Application number
|Publication date
|Jul 8, 2003
|Filing date
|Apr 4, 2001
|Priority date
|Apr 4, 2001
|Fee status
|Also published as
|Publication number
|Ben D. Smith, Krishniah Parimi, Richard O. Moore, Jr.
|Original Assignee
|Chevron U.S.A., Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (32), Non-Patent Citations (1), Referenced by (37), Classifications (13), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
The majority of combustible liquid fuel used in the world today is derived from crude oil. However, there are several limitations to using crude oil as a fuel source. For example, crude oil is in limited supply, includes aromatic compounds believed to cause cancer, and contains sulfur and nitrogen-containing compounds that can adversely affect the environment.
Alternative sources for developing combustible liquid fuel are desirable. One option is to convert natural gas to liquid fuel or other chemical products. The conversion of natural gas to liquid fuel typically involves converting the natural gas, which is mostly methane, to synthesis gas, or syngas, which is a mixture of carbon monoxide and hydrogen. Fischer-Tropsch synthesis is an example of a hydrocarbon synthesis that converts the syngas to higher molecular weight hydrocarbon products. An advantage of using fuels prepared from syngas is that they typically do not contain nitrogen and sulfur and generally do not contain aromatic compounds. Accordingly, they have less health and environmental impact than conventional petroleum liquids based fuels.
Fischer-Tropsch synthesis products tend to include a large amount of high molecular weight linear paraffins (wax), which can be hydrocracked to form lower molecular weight products, and optionally subjected to additional hydroprocessing steps.
Multiple catalyst beds with intermediate cooling stages are commonly used to control the extremely exothermic hydrocracking reaction. Multiple beds are used to introduce a cooling quench (typically a gas, most often a hydrogen-containing gas) and to allow re-mixing of the reactor gas and liquids to allow for more efficient catalyst utilization and smoother/safer operation. Numerous means are known for mixing the gas/gas, liquid/liquid and gas/liquid mixtures between catalysts beds, examples of which are described in U.S. Pat. No. 5,837,208 and U.S. Pat. No. 5,690,896, the contents of which are hereby incorporated by reference.
In typical hydrocracking reactions, a feed is preheated and introduced along with a significant stream of a hydrogen-containing gas at the top of the reactor. A stream of relatively cool hydrogen-containing gas is introduced between the beds to provide the desired quenching (cooling) of the exothermic hydrocracking reactions. Gas has been a preferred quench fluid because of the relative ease in distributing across the reactor cross-section, its function as a reactant in the upgrading process, and the availability at reactor conditions downstream of the plant recycle and/or make-up hydrogen compressors. A limitation of using gases as the quench fluid is its relatively low heat capacity. Additionally, the use of hydrogen requires the presence of relatively expensive recirculation pumps.
It would be advantageous to provide methods for using additional quench streams when hydrocracking FT synthesis products. The present invention provides such methods.
The present invention is directed to a method for hydroprocessing Fischer-Tropsch products. The invention in particular relates to an integrated method for producing liquid fuels from a hydrocarbon stream provided by Fischer-Tropsch synthesis. The method involves separating the Fischer-Tropsch products into a light fraction with normal boiling points below 700° F. and including predominantly C5-20 components and a heavy fraction with normal boiling points above 650° F. and including predominantly C20+ of components. The heavy fraction is subjected to hydrocracking conditions, preferably through multiple catalyst beds, to reduce the chain length. The light fraction is used as all or part of a quench fluid between each catalyst bed.
The products from the hydroprocessing reaction can be separated into at least a hydrogen-rich gas stream, a distillate product predominantly in the C5-20 range, and a bottoms stream. The bottoms stream can optionally be resubjected to the hydrocracking conditions to provide an additional light fraction, or used, for example, to prepare a lube base oil stock. When used to prepare a lube base oil stock, it can be subjected to catalytic dewaxing and/or solvent dewaxing conditions.
In one embodiment, the heavy fraction and/or the light fraction include hydrocarbons in the same range derived from other sources, for example, petroleum refining.
The FIGURE is an illustrative schematic flow diagram representing one preferred embodiment of the invention, but the invention is applicable to all appropriate refineries and/or chemical processes.
The present invention is directed to a method for hydroprocessing Fischer-Tropsch products. The invention in particular relates to an integrated method for producing liquid fuels from a hydrocarbon stream provided by Fischer-Tropsch synthesis, which in turn involves the initial conversion of a light hydrocarbon stream to syngas and conversion of the syngas to higher molecular weight hydrocarbon products.
The method involves subjecting a heavy fraction derived from a Fischer-Tropsch process to hydrocracking conditions, preferably through multiple catalyst beds, to reduce the chain length. A light fraction derived from a Fischer-Tropsch process is used as a quench fluid to remove excess heat from the hydrocracked products. In one embodiment, the light fraction may be injected between catalyst beds in the reactor. Optionally, the light fraction can be combined with the effluent from the hydrocracking beds (the "hydrocrackate") and the combined fractions hydrotreated or otherwise hydroprocessed. The heavy fraction which is used in the present process may be a stream from a Fischer-Tropsch reaction, or a fraction produced by fractionating a Fischer-Tropsch reaction product. The light fraction may also be a stream from a Fischer-Tropsch reaction, or a fraction produced by fractionating a Fischer-Tropsch reaction product
The present method is advantageous for many reasons. The light fraction quenches the high temperature hydrocracking products, minimizing or eliminating the need for hydrogen as a quench fluid, and also minimizing or eliminating the need for hydrogen recycle pumps downstream. The hydrocracking of the light fraction is minimized, relative to the case where the entire C5+ fraction from a Fischer-Tropsch synthesis is subjected to similar hydrocracking conditions. The isolation of products in the desired C5-20 range, for example, mid-distillates, can be enhanced by minimizing the hydrocracking of Fischer-Tropsch products in the C5-20 range. Further, by removing the light fraction from the feed to the hydrocracking reactor, the throughput of predominantly C20+ hydrocarbons to the reactor is increased.
The methods allow for heat exchange between the relatively high temperature hydrocracking products and the relatively cool light fraction. This heat exchange cools the hydrocracking products down to the desired hydrotreatment temperature while minimizing the need for hydrogen compressors.
In one aspect, the methods reduce the number of reactor vessels and/or hydrogen compressors/recycle pumps required for hydroprocessing in a refinery. The methods can also extend the life of the hydrocracking catalyst by minimizing contact of the C5-20 fraction with the hydrocracking catalysts.
Light Hydrocarbon Feedstock:
These feedstocks can include methane, ethane, propane, butane and mixtures thereof. In addition, carbon dioxide, carbon monoxide, ethylene, propylene and butenes may be present.
A light fraction is a fraction in which at least 75% by weight, more preferably 85% by weight, and most preferably, at least 90% by weight of the components have a boiling point in the range of between 50° and 700° F., and that includes predominantly components having carbon numbers in the range of 5 to 20, i.e. C5-20. A heavy fraction is a fraction in which at least 75% by weight, more preferably 85% by weight, and most preferably, at least 90% by weight of the components have a boiling point higher than 650° F. as determined by ASTM D2887 or other suitable methods, and that includes predominantly C20+ components. The light fraction is similarly defined.
A 650° F.+ containing product stream is a product stream that includes greater than 75% by weight 650° F.+ material, preferably greater than 85% by weight 650° F.+ material, and, most preferably, greater than 90% by weight 650° F.+ material. as determined by ASTM D2887 or other suitable methods. The 650° F.-containing product stream is similarly defined.
A hydrocarbon with the formula CnH2n+2.
A hydrocarbon with at least one carbon—carbon double bond.
A hydrocarbonaceous compound that includes at least one oxygen atom.
Distillate Fuel:
A material containing hydrocarbons with boiling points between about 60° and 800° F. The term "distillate" means that typical fuels of this type can be generated from vapor overhead streams from distilling petroleum crude. In contrast, residual fuels cannot be generated from vapor overhead streams by distilling petroleum crude, and are then a non-vaporizable remaining portion. Within the broad category of distillate fuels are specific fuels that include: naphtha, jet fuel, diesel fuel, kerosene, aviation gas, fuel oil, and blends thereof.
Diesel Fuel:
A material suitable for use in diesel engines and conforming to one of the following specifications:
ASTM D 975—"Standard Specification for Diesel Fuel Oils"
European Grade CEN 90
Japanese Fuel Standards JIS K 2204
The United States National Conference on Weights and Measures (NCWM) 1997 guidelines for premium diesel fuel The United States Engine Manufacturers Association recommended guideline for premium diesel fuel (FQP-1A)
Jet Fuel:
A material suitable for use in turbine engines for aircraft or other uses meeting one of the following specifications:
International Air Transportation Association (IATA) Guidance Materials for Aviation, 4th edition, March 2000.
Natural Gas
Natural gas is an example of a light hydrocarbon feedstock. In addition to methane, natural gas includes some heavier hydrocarbons (mostly C2-5 paraffins) and other impurities, e.g., mercaptans and other sulfur-containing compounds, carbon dioxide, nitrogen, helium, water and non-hydrocarbon acid gases. Natural gas fields also typically contain a significant amount of C5+ material, which is liquid at ambient conditions.
The methane, and optionally ethane and/or other hydrocarbons, can be isolated and used to generate syngas. Various other impurities can be readily separated. Inert impurities such as nitrogen and helium can be tolerated. The methane in the natural gas can be isolated, for example in a demethanizer, and then de-sulfurized and sent to a syngas generator.
Methane (and/or ethane and heavier hydrocarbons) can be sent through a conventional syngas generator to provide synthesis gas. Typically, synthesis gas contains hydrogen and carbon monoxide, and may include minor amounts of carbon dioxide, water, unconverted light hydrocarbon feedstock and various other impurities. The presence of sulfur, nitrogen, halogen, selenium, phosphorus and arsenic contaminants in the syngas is undesirable. For this reason, it is preferred to remove sulfur and other contaminants from the feed before performing the Fischer-Tropsch chemistry or other hydrocarbon synthesis. Means for removing these contaminants are well known to those of skill in the art. For example, ZnO guard beds are preferred for removing sulfur impurities. Means for removing other contaminants are well known to those of skill in the art.
Fischer-Tropsch Synthesis
Catalysts and conditions for performing Fischer-Tropsch synthesis are well known to those of skill in the art, and are described, for example, in EP 0 921 184 A11, the contents of which are hereby incorporated by reference in their entirety. In the Fischer-Tropsch synthesis process, liquid and gaseous hydrocarbons are formed by contacting a synthesis gas (syngas) comprising a mixture of H2 and CO with a Fischer-Tropsch catalyst under suitable temperature and pressure reactive conditions. The Fischer-Tropsch reaction is typically conducted at temperatures of about from 300° to 700° F. (149 to 371° C.) preferably about from 400° to 550° F. (204° to 228° C.); pressures of about from 10 to 600 psia, (0.7 to 41 bars) preferably 30 to 300 psia, (2 to 21 bars) and catalyst space velocities of about from 100 to 10,000 cc/g/hr., preferably 300 to 3,000 cc/g/hr.
The products may range from C1 to C200+ with a majority in the C5-C100+ range. The reaction can be conducted in a variety of reactor types for example, fixed bed reactors containing one or more catalyst beds, slurry reactors, fluidized bed reactors, or a combination of different type reactors. Such reaction processes and reactors are well known and documented in the literature. Slurry Fischer-Tropsch processes, which is a preferred process in the practice of the invention, utilize superior heat (and mass) transfer characteristics for the strongly exothermic synthesis reaction and are able to produce relatively high molecular weight, paraffinic hydrocarbons when using a cobalt catalyst. In a slurry process, a syngas comprising a mixture of H2 and CO is bubbled up as a third phase through a slurry in a reactor which comprises a particulate Fischer-Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in a slurry liquid comprising hydrocarbon products of the synthesis reaction which are liquid at the reaction conditions. The mole ratio of the hydrogen to the carbon monoxide may broadly range from about 0.5 to 4, but is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5. A particularly preferred Fischer-Tropsch process is taught in EP0609079, also completed incorporated herein by reference for all purposes.
Suitable Fischer-Tropsch catalysts comprise on or more Group VIII catalytic metals such as Fe, Ni, Co, Ru and Re. Additionally, a suitable catalyst may contain a promoter. Thus, a preferred Fischer-Tropsch catalyst comprises effective amounts of cobalt and one or more of Re, Ru, Pt, Fe, Ni, Th, Zr, Hf, U, Mg and La on a suitable inorganic support material, preferably one which comprises one or more refractory metal oxides. In general, the amount of cobalt present in the catalyst is between about 1 and about 50 weight percent of the total catalyst composition. The catalysts can also contain basic oxide promoters such as ThO2, La2O3, MgO, and TiO2, promoters such as ZrO2, noble metals (Pt, Pd, Ru, Rh, Os, Ir), coinage metals (Cu, Ag, Au), and other transition metals such as Fe, Mn, Ni, and Re. Support materials including alumina, silica, magnesia and titania or mixtures thereof may be used. Preferred supports for cobalt containing catalysts comprise titania. Useful catalysts and their preparation are known and illustrative, but nonlimiting examples may be found, for example, in U.S. Pat. No. 4,568,663.
Product Isolation from Fischer-Tropsch Synthesis
The products from Fischer-Tropsch reactions performed in slurry bed reactors generally include a light reaction product and a waxy reaction product. The light reaction product (a predominantly C5-C20 fraction, commonly termed the "condensate fraction") includes hydrocarbons boiling below about 700° F. (e.g., tail gases through middle distillates), with decreasing amounts up to about C30. The waxy reaction product (a predominantly C20+ fraction, commonly termed the "wax fraction") includes hydrocarbons boiling above about 600° F. (e.g., vacuum gas oil through heavy paraffins), with decreasing amounts down to C10. Both the light reaction product and the waxy product are substantially paraffinic. The waxy product generally comprises greater than 70% normal paraffins, and often greater than 80% normal paraffins. The light reaction product comprises paraffinic products with a significant proportion of alcohols and olefins. In some cases, the light reaction product may comprise as much as 50%, and even higher, alcohols and olefins.
Additional Hydrocarbon Streams
The light and heavy fractions described above can optionally be combined with hydrocarbons from other streams, for example, streams from petroleum refining. The light fractions can be combined, for example, with similar fractions obtained from the fractional distillation of crude oil. The heavy fractions can be combined, for example, with waxy crude oils, crude oils and/or slack waxes from petroleum deoiling and dewaxing operations.
Optional Treatment of the Light Fraction Before Use as a Quench Fluid
The light fraction typically includes a mixture of hydrocarbons, including mono-olefins and alcohols. The mono-olefins are typically present in an amount of at least about 5.0 wt % of the lighter fraction. The alcohols are usually present in an amount typically of at least about 0.5 wt % or more.
The pressurized fraction can be mixed with a hydrogen-containing gas stream, in those embodiments where the quench fluid is a combination of a hydrogen-containing gas and the light fraction. When the fraction is heated upon combination with the heated hydrocracking stream, the olefins may form heavy molecular weight products, such as polymers. Adding even a small amount (i.e., less than about 500 SCFB) of hydrogen-containing gas to the fraction before it is heated by the hydrocrackate prevents or minimizes formation of the undesirable heavier molecular weight products.
The source of hydrogen can be virtually any hydrogen-containing gas that does not include significant amounts of impurities that would adversely affect the hydrotreatment catalysts. In particular, the hydrogen-containing gas includes sufficient amounts of hydrogen to achieve the desired effect, and may include other gases that are not harmful to the formation of desired end products and that do not promote or accelerate fouling of the downstream catalysts and hydrotreatment equipment. Examples of possible hydrogen-containing gases include hydrogen gas and syngas. The hydrogen can be from a hydrogen plant, recycle gas in a hydroprocessing unit and the like. Alternately, the hydrogen-containing gas may be a portion of the hydrogen used for hydrocracking the wax fraction.
After the hydrogen-containing gas is introduced into the fraction, the fraction can be pre-heated, if necessary, in a heat exchanger. The methods of heating the fractions in the heat exchangers can include any methods known to practitioners in the art. For example, a shell and tube heat exchanger may be used, wherein a heated substance, such as steam or a reaction product from elsewhere in the method, is fed through an outer shell, providing heat to the fraction in an inner tube, thus heating the fraction and cooling the heated substance in the shell. Alternately, the fraction may be heated directly by passing through a heated tube, wherein the heat may be supplied by electricity, combustion, or any other source known to practitioners in the art.
Hydroprocessing Reactors
Hydrocracking generally refers to breaking down the high molecular weight components of hydrocarbon feed to form other, lower molecular weight products. Hydrotreatment hydrogenates double bonds, reduces oxygenates to paraffins, and desulfurizes and denitrifies hydrocarbon feeds. Hydroisomerization converts at least a portion of the linear paraffins into isoparaffins.
In hydrocracking reactions, pressures and temperatures are often close to the limit the reactors can handle. Multiple catalyst beds with intermediate cooling stages are typically used to control the extremely exothermic hydrocracking reaction. The hydrotreating and hydrocracking reactions begin as soon as the feed contacts the catalyst. Because the reactions are exothermic, the temperature of the reaction mixture increases and the catalyst beds heat up as the mixture passes through the beds and the reactions proceed. In order to limit the temperature rise and control the reaction rate, a quench fluid is introduced into the catalytic reaction zone within the reactor, generally between the catalyst beds.
Ideally, there is less than a 100° F. temperature rise in each bed, preferably less than about 50° F. per bed, with cooling stages used to bring the temperature back to a manageable level. The heated effluent from each bed is mixed with the quench fluid in a suitable mixing device (sometimes referred to as an inter-bed redistributor or a mixer/distributor) to cool the effluent sufficiently so that it can be sent through the next catalyst bed.
The quench fluid includes the light fraction and optionally other fluids, for example, (pressurized) hydrogen gas. The hydrogen gas is typically introduced at around 150° F. or above, which is extremely cold relative to the reactant temperatures (typically between 650° and 750° F.). When multiple catalyst beds are used, the quench fluid is used in the intermediate cooling stages. After the final hydrocracking bed, rather than quenching the hydrocrackate in an intermediate bed, it can be combined with the quench fluid and the combined fractions hydrotreated.
Reactor internals between the catalysts beds are designed to ensure both a thorough mixing of the reactants with the quench fluid and a good distribution of vapor and liquid flowing to the next catalyst bed. Good distribution of the reactants prevents hot spots and excessive naphtha and gas make, and maximizes catalyst life. This is particularly important where the heavy fraction includes an appreciable amount of olefins, which makes it highly reactive. Poor distribution and mixing can result in non-selective cracking of the wax to light gas. Examples of suitable mixing devices are described, for example, in U.S. Pat. No. 5,837,208, U.S. Pat. No. 5,690,896, U.S. Pat. No. 5,462,719 and U.S. Pat. No. 5,484,578, the contents of which are hereby incorporated by reference. A preferred mixing device is described in U.S. Pat. No. 5,690,896.
The reactor includes a means for introducing the light fraction to the inter-bed redistributors so that they can be used as (all or part of) a quenching fluid. Preferably, the fraction is introduced as a liquid rather than a gas, to better absorb heat from the heated hydrocrackate. The redistributors are generally placed between catalyst beds, for redistributing the fluids passing from catalyst bed to catalyst bed, and the fluids optionally added to the redistributor (e.g. a hydrogen containing gas or a liquid stream) from outside the reactor. Redistributors are well known in the art (e.g. U.S. Pat. No. 5,690,896).
Preferably, the reactor is a downflow reactor that includes at least two catalyst beds, with inter-bed redistributors between the beds. The top bed(s) include a hydrocracking catalyst and, optionally, one or more beds include a hydroisomerization and/or hydrotreatment catalyst.
In one embodiment, the products of the hydrocracking reaction can be removed between beds, with continuing reaction of the remaining stream in subsequent beds. U.S. Pat. No. 3,172,836 discloses a liquid/vapor separation zone located between two catalyst beds for withdrawing a gaseous fraction and a liquid fraction from a first catalyst bed. Such techniques can be used if desired to isolate products. However, since the products of the hydrocracking reaction are typically gaseous at the reaction temperature, the residence time of the gaseous products on the catalyst beds is sufficiently low, and further hydrocracking of the product would be expected to be minimal, so product isolation is not required.
The catalysts and conditions for performing hydrocracking, hydroisomerization and hydrotreating reactions are discussed in more detail below.
The heavy fractions described above can be hydrocracked using conditions well known to those of skill in the art. In a preferred embodiment, hydrocracking conditions involve passing a feed stream, such as the heavy fraction, through a plurality of hydrocracking catalyst beds under conditions of elevated temperature and/or pressure. The plurality of catalyst beds may function to remove impurities such as any metals and other solids which may be present, and/or to crack or convert the feedstock. Hydrocracking is a process of breaking longer carbon chain molecules into smaller ones. It can be effected by contacting the particular fraction or combination of fractions, with hydrogen in the presence of a suitable hydrocracking catalyst at hydrocracking conditions, including temperatures in the range of about from 600° to 900° F. (316° to 482° C.) preferably 650° to 850° F. (343° to 454° C.) and pressures in the range about from 200 to 4000 psia (13-272 atm) preferably 500 to 3000 psia (34-204 atm) using space velocities based on the hydrocarbon feedstock of about 0.1 to 10 hr−1 preferably 0.25 to 5 hr−1. In general, hydrocracking catalysts include a cracking component and a hydrogenation component on an oxide support material or binder. The cracking component may include an amorphous cracking component and/or a zeolite, such as a Y-type zeolite, an ultrastable Y-type zeolite or a dealuminated zeolite. A suitable amorphous cracking component is silica-alumina.
The hydrogenation component of the catalyst particles is selected from those elements known to provide catalytic hydrogenation activity. At least one metal component selected from the Group VIII (IUPAC notation) elements and/or from the Group VI (IUPAC notation) elements are generally chosen. Group VI elements include chromium, molybdenum and tungsten. Group VIII elements include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The amount(s) of hydrogenation component(s) in the catalyst suitable range from about 0.5% to about 10% by weight of Group VIII metal component(s) and from about 5% to about 25% by weight of Group VI metal component(s), calculated as metal oxide(s) per 100 parts by weight of total catalyst, where the percentages by weight are based on the weight of the catalyst before sulfiding. The hydrogenation components in the catalyst may be in the oxidic and/or the sulfidic form. If a combination of at least a Group VI and a Group VIII metal component is present as (mixed) oxides, it will be subjected to a sulfiding treatment prior to proper use in hydrocracking. Suitably, the catalyst includes one or more components of nickel and/or cobalt and one or more components of molybdenum and/or tungsten and one or more components of platinum and/or palladium. Catalysts containing nickel and molybdenum, nickel and tungsten, platinum and/or palladium are particularly preferred.
The hydrocracking particles used herein may be prepared, for example, by blending or co-mulling active sources of hydrogenation metals with a binder. Examples of suitable binders include silica, alumina, clays, zirconia, titania, magnesia and silica-alumina. Preference is given to the use of alumina as a binder. Other components, such as phosphorous, may be added as desired to tailor the catalyst particles for a desired application. The blended components are then shaped, such as by extrusion, dried and calcined at temperatures up to 1200° F. (649° C.) to produce the finished catalyst particles. Alternatively, equally suitable methods for preparing the amorphous catalyst particles include preparing oxide binder particles, for example, by extrusion, drying and calcining, followed by depositing the hydrogenation metals on the oxide particles, using methods such as impregnation. The catalyst particles, containing the hydrogenation metals, are preferably then further dried and calcined before use as a hydrocracking catalyst.
Preferred catalyst systems include one or more of zeolite Y, zeolite ultrastable Y, SAPO-11, SAPO-31, SAPO-37, SAPO-41, ZSM-5, ZSM-11, ZSM-48, and SSZ-32.
In one embodiment, the hydrocracked products are hydroisomerized to provide branching, thus lowering the pour point. Optionally, the light fraction can be hydroisomerized before being used as a quench fluid or after the hydrocracking is complete. Catalysts useful for isomerization processes are generally bifunctional catalysts that include a dehydrogenation/hydrogenation component, an acidic component.
The hydroisomerization catalyst(s) can be prepared using well known methods, e.g., impregnation with an aqueous salt, incipient wetness technique, followed by drying at about 125°-150° C. for 1-24 hours, calcination at about 300°-500° C. for about 1-6 hours, reduction by treatment with a hydrogen or a hydrogen-containing gas, and, if desired, sulfiding by treatment with a sulfur-containing gas, e.g., H2S at elevated temperatures. If sulfided, the catalyst will then have about 0.01 to 10 wt % sulfur. The metals can be composited or added to the catalyst either serially, in any order, or by co-impregnation of two or more metals. Additional details regarding preferred components of the hydroisomerization catalysts are described below.
Dehydrogenation/Hydrogenation Component
The dehydrogenation/hydrogenation component is preferably a Group VIII metal, more preferably a Group VIII non-noble metal, or a Group VI metal. Preferred metals include nickel, platinum, palladium, cobalt and mixtures thereof. The Group VIII metal is usually present in catalytically effective amounts, that is, ranging from 0.5 to 20 wt %. Preferably, a Group VI metal is incorporated into the catalyst, e.g., molybdenum, in amounts of about 1-20 wt %.
Acidic Component
Examples of suitable acid components include crystalline zeolites, catalyst supports such as halogenated alumina components or silica-alumina components, and amorphous metal oxides. Such paraffin isomerization catalysts are well known in the art. The acid component may be a catalyst support with which the catalytic metal or metals are composited. Preferably, the acidic component is a zeolite or a silica-alumina support, where the silica/alumina ratio (SAR) is less than 1 (wt./wt.).
Preferred supports include silica, alumina, silica-alumina, silica-alumina-phosphates, titania, zirconia, vanadia and other Group III, IV, V or VI oxides, as well as Y sieves, such as ultra stable Y sieves. Preferred supports include alumina and silica-alumina, more preferably silica-alumina where the silica concentration of the bulk support is less than about 50 wt %, preferably less than about 35 wt %, more preferably 15-30 wt %. When alumina is used as the support, small amounts of chlorine or fluorine may be incorporated into the support to provide the acid functionality.
A preferred supported catalyst has surface areas in the range of about 180-400 m2/gm, preferably 230-350 m2/gm, and a pore volume of 0.3 to 1.0 ml/gm, preferably 0.35 to 0.75 ml/gm, a bulk density of about 0.5-1.0 g/ml, and a side crushing strength of about 0.8 to 3.5 kg/mm.
The preparation of preferred amorphous silica-alumina microspheres for use as supports is described in Ryland, Lloyd B., Tamele, M. W., and Wilson, J. N., Cracking Catalysts Catalysis, Volume VII, Ed. Paul H. Emmett, Reinhold Publishing Corporation, New York, (1960).
Preferred dewaxing/hydroisomerization catalysts include SAPO-11, SAPO-31, SAPO-41, SSZ-32 and/or ZSM-5.
During hydrotreating, oxygen, and any sulfur and nitrogen present in the feed is reduced to low levels. Aromatics and olefins are also reduced. Hydrotreating catalysts and reaction conditions are selected to minimize cracking reactions, which reduce the yield of the most desulfided fuel product.
Hydrotreating conditions include a reaction temperature between 400°-900° F. (204°-482° C.), preferably 650°-850° F. (343°-454° C.); a pressure between 500 to 5000 psig (pounds per square inch gauge) (3.5-34.6 MPa), preferably 1000 to 3000 psig (7.0-20.8 MPa); a feed rate (LHSV) of 0.5 hr−1 to 20 hr1 (v/v); and overall hydrogen consumption 300 to 2000 scf per barrel of liquid hydrocarbon feed (53.4-356 m3 H2/m3 feed). The hydrotreating catalyst for the beds will typically be a composite of a Group VI metal or compound thereof, and a Group VIII metal or compound thereof supported on a porous refractory base such as alumina. Examples of hydrotreating catalysts are alumina supported cobalt—molybdenum, nickel sulfide, nickel-tungsten, cobalt-tungsten and nickel-molybdenum. Typically such hydrotreating catalysts are presulfided.
The hydrocrackate described above can be hydrotreated. Optionally, the light fractions can also be hydrotreated, either before they are used in the quench fluid or after the hydrocracking is complete. In the latter, the hydrocrackate and the quench fluid can be combined and hydrotreated together. In this manner, the quench fluid can cool the heated hydrocrackate before the hydrotreatment reaction. In a specific embodiment, the hydrotreatment catalyst beds are located below the hydrocracking catalyst beds. In a separate embodiment of the present process, the hydrotreatment is performed in one or more catalyst beds in a different reaction than that which includes the hydrocracking catalyst beds.
Catalysts useful for hydrotreatment are well known in the art. See, for example, U.S. Pat. Nos. 4,347,121 and 4,810,357 for general descriptions of hydrotreating catalysts and conditions. Suitable catalysts include noble metals from Group VIIIA, such as platinum or palladium on an alumina or siliceous matrix, and Group VIIIA and Group VIB metals, such as nickel-molybdenum or nickel-tin on an alumina or siliceous matrix. U.S. Pat. No. 3,852,207 describes suitable noble metal catalysts and mild hydrotreating conditions. Other suitable catalysts are described, for example, in U.S. Pat. Nos. 4,157,294 and 3,904,513. The contents of these patents are hereby incorporated by reference.
The non-noble (such as nickel-molybdenum) hydrogenation metal is usually present in the final catalyst composition as an oxide or, more preferably, as a sulfide, when such compounds are readily formed from the particular metal involved. Preferred non-noble metal catalyst compositions contain in excess of about 5 weight percent, preferably about 5 to about 40 wt %, molybdenum and/or tungsten, and at least about 0.5, preferably about 1 to about 15 wt % of nickel and/or cobalt determined as the corresponding oxides. The noble metal (such as platinum) catalyst contains in excess of about 0.01 percent metal, preferably between about 0.1 and about 1.0 percent metal. Combinations of noble metals may also be used, such as mixtures of platinum and palladium.
In a preferred embodiment, the hydrotreatment reactor includes a plurality of catalyst beds, wherein one or more beds may function to remove impurities such as any metals and other solids which may be present, one or more additional beds may function to crack or convert the feedstock, and one or more other beds may function to hydrotreat the oxygenates and olefins in the condensate and/or wax fraction.
Method Steps
The heavy fraction is hydrocracked through the beds of the hydrocracking catalyst, with cooling between the beds. The light fraction is used as all or a part of the quench fluid in inter-bed redistributors to cool the effluent from each hydrocracking catalyst bed. Preferably, the light fraction is a liquid, not a gas at the temperature at which it is combined with the effluent from the hydrocracking beds, so that the liquid adsorbs more heat from the heated effluent. After the hydrocracking is complete, the effluent from the last hydrocracking bed can be combined with the light fraction and the combined fractions subjected to hydrotreatment conditions.
The products from the hydrotreatment reaction are preferably separated into at least two fractions, a light fraction and a bottoms fraction. The light fraction can be subjected to distillation, catalytic isomerization and/or various additional method steps to provide gasoline, diesel fuel, jet fuel and the like, as known to practitioners in the art. The bottoms fraction can optionally be recycled to the hydrocracking reactor to provide an additional light fraction. Alternatively, the fraction can be subject to distillation, catalytic isomerization, dewaxing and/or various additional method steps to provide lube base oil stocks, as known to practitioners in the art.
Preferred dewaxing catalysts include SAPO-11, SAPO-31, SAPO-41, SSZ-32, and ZSM-5. Alternatively, or in addition, the fraction can be subjected to solvent dewaxing conditions, as such are known in the art. Such conditions typically involve using solvents such as methylethyl ketone and toluene, where addition of such solvents or solvent mixtures at an appropriate temperature results in the precipitation of wax from the bottoms fraction. The precipitated wax can then be readily removed using means well known to those of skill in the art.
The method described herein will be readily understood by referring to the particularly preferred embodiment in the flow diagram in the accompanying FIGURE. In the FIGURE, a syngas feed (5) is sent to a Fischer-Tropsch synthesis process (10) and the products of a Fischer-Trospch synthesis are separated into at least a light (15) and a heavy fraction (20). The heavy fraction is sent to a hydrocracking reactor (25) with a plurality of hydrocracking catalyst beds (30) and a plurality of inter-bed redistributors (35). The light fraction is used as all or part of the quench fluid (40) in the redistributors. After the hydrocracking reaction is complete, the products are optionally passed through one or more hydrotreatment beds (45). The products from the hydrotreatment reaction (50) are split into various fractions, including a light product (55) and a bottoms product (60). The bottoms product may be recycled (65) to the hydrocracking reactor.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.
|Cited Patent
|Filing date
|Publication date
|May 1, 1963
|Apr 26, 1966
|Standard Oil Co
|Combination process of hydrocracking and isomerization of hydrocarbons with the addition of olefins in the isomerization zone
|Jun 2, 1969
|Nov 2, 1971
|Chevron Res
|Catalytic hydrocracking process
|Nov 19, 1976
|May 30, 1978
|Mario Iona
|Process for producing low density low-sulfur crude oil
|May 30, 1978
|Nov 6, 1979
|The Lummus Company
|Hydrotreating of pyrolysis gasoline
|Apr 23, 1979
|Jul 8, 1980
|Mobil Oil Corporation
|Catalytic conversion of hydrocarbons
|Jan 20, 1984
|Oct 7, 1986
|Chevron Research Company
|Method for contacting solids-containing feeds in a layered bed reactor
|May 9, 1988
|Jul 25, 1989
|Mobil Oil Corporation
|Integrated hydroprocessing scheme for production of premium quality distillates and lubricants
|Jul 22, 1993
|Jan 3, 1995
|Exxon Research And Engineering Company
|Distillate fuel production from Fischer-Tropsch wax
|Aug 22, 1994
|Apr 25, 1995
|Mobil Oil Corporation
|Production of low sulfur distillate fuel
|Aug 3, 1994
|Feb 18, 1997
|Mobil Oil Corporation
|Hydrocarbon upgrading process
|May 5, 1995
|Nov 25, 1997
|Chevron U.S.A. Inc.
|Distributor assembly for multi-bed down-flow catalytic reactors
|Aug 23, 1996
|Jun 23, 1998
|Exxon Research And Engineering Company
|Integrated staged catalytic cracking and hydroprocessing process (JHT-9614)
|Apr 8, 1997
|Nov 17, 1998
|Hydroprocessing reactor mixer/distributor
|Mar 8, 1995
|Dec 22, 1998
|Idemitsu Kosan Co., Ltd.
|Method of refining crude oil
|Jan 8, 1999
|Aug 1, 2000
|Chevron U.S.A. Inc.
|Hydrocracking/hydrotreating process without intermediate product removal
|Jun 9, 1997
|Aug 15, 2000
|Petroleo Brasileiro S.A.-Petrobras
|Process for producing lube base oils of high viscosity index and diesel oil of high cetaned number
|Jan 8, 1999
|Jan 30, 2001
|Chevron U.S.A. Inc.
|Residuum hydrotreating/hydrocracking with common hydrogen supply
|Jan 8, 1999
|Mar 13, 2001
|Chevron U.S.A. Inc.
|Process for reverse gas flow in hydroprocessing reactor systems
|Aug 13, 1999
|Apr 3, 2001
|Exxon Research And Engineering Company
|Use of 13C NMR spectroscopy to produce optimum fischer-tropsch diesel fuels and blend stocks
|Jan 8, 1999
|May 1, 2001
|Chevron U.S.A. Inc.
|Hydrocracking and hydrotreating
|Dec 16, 1999
|Aug 14, 2001
|Exxon Research And Engineering Company
|Synthetic diesel fuel and process for its production
|Oct 17, 1995
|Oct 2, 2001
|Exxon Research And Engineering Company
|Synthetic diesel fuel and process for its production
|Feb 13, 1998
|Oct 9, 2001
|Mobil Oil Corporation
|Hydroprocessing reactor and process with gas and liquid quench
|Title not available
|Dec 16, 1988
|Jun 21, 1989
|Exxon Research And Engineering Company
|Process for the hydroisomerization/hydrocracking of fischer-tropsch waxes to produce syncrude and upgraded hydrocarbon products
|Jan 27, 1994
|Aug 3, 1994
|Sasol Chemical Industries (Proprietary) Limited
|Process for producing liquid and, optionally gaseous products from gaseous reactants
|Dec 1, 1998
|Jun 9, 1999
|Schümann Sasol (South Africa), (Proprietary) Ltd.
|Production of lubricant base oils
|Jul 5, 1996
|Feb 6, 1997
|Exxon Research & Engineering Company
|Supported ni-cu hydroconversion catalyst
|Feb 3, 1999
|Aug 19, 1999
|Mobil Oil Corporation
|Hydroprocessing reactor and process with liquid quench
|Jan 8, 1999
|Sep 23, 1999
|Chevron U.S.A. Inc.
|Integrated hydroconversion process with reverse hydrogen flow
|Sep 17, 1999
|Apr 13, 2000
|Sasol Technology (Pty) Ltd
|Process for producing middle distillates and middle distillates produced by that process
|Jan 18, 2001
|Aug 9, 2001
|Exxonmobil Research And Engineering Company
|Quenching dewaxing reactor with heavy dewaxate recycle
|U.S. patent application 09/227,783 entitled "Hydrocracking and Hydrotreating Separate Refinery Streams", Cash and Dahlberg.
|Citing Patent
|Filing date
|Publication date
|Feb 25, 2003
|Oct 23, 2007
|Shell Oil Company
|Process to prepare a catalytically dewaxed gas oil or gas oil blending component
|Mar 17, 2004
|Apr 8, 2008
|Conocophillips Company
|Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons
|Jul 28, 2004
|Jun 10, 2008
|Conocophillips Company
|Optimized preheating of hydrogen/hydrocarbon feed streams
|Jun 26, 2002
|Sep 23, 2008
|Eni S.P.A.
|Process for the production of paraffinic middle distillates
|Mar 9, 2010
|Chevron U.S.A. Inc.
|Hydraulic fluid compositions and preparation thereof
|Jun 4, 2008
|Apr 26, 2011
|Chevron U.S.A., Inc.
|Gear oil compositions, methods of making and using thereof
|Nov 5, 2003
|Mar 20, 2012
|Chevron U.S.A. Inc.
|Integrated process for the production of lubricating base oils and liquid fuels from Fischer-Tropsch materials using split feed hydroprocessing
|Sep 25, 2008
|Dec 3, 2013
|Japan Oil, Gas And Metals National Corporation
|Method of manufacturing diesel fuel base stock and diesel fuel base stock thereof
|Sep 25, 2008
|May 27, 2014
|Japan Oil, Gas And Metals National Corporation
|Method of manufacturing diesel fuel
|Nov 5, 2003
|Oct 14, 2004
|Maureen Ward
|RD114-based retroviral packaging cell line and related compositions and methods
|Jun 26, 2002
|Oct 21, 2004
|Vincenzo Calemma
|Process for the production of paraffinic middle distillates
|Feb 25, 2003
|Apr 28, 2005
|Clark Richard H.
|Process to prepare a catalytically dewaxed gas oil or gas oil blending component
|Mar 17, 2004
|Sep 22, 2005
|Conocophillips Company
|Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons
|Jul 28, 2004
|Feb 2, 2006
|Witte Gregory M
|Optimized preheating of hydrogen/hydrocarbon feed streams
|Aug 28, 2007
|Dec 20, 2007
|Chevron Corporation
|Hydraulic Fluid Compositions and Preparation Thereof
|Aug 28, 2007
|Feb 7, 2008
|Chevron Usa Inc.
|Hydraulic Fluid Compositions and Preparation Thereof
|Oct 31, 2007
|Mar 6, 2008
|Chevron U.S.A. Inc.
|Engine oil compositions and preparation thereof
|Dec 20, 2005
|Oct 16, 2008
|The Petroleum Oil And Gas Corporation Of South Africa (Pty) Ltd
|Synthetically Derived Illuminating and Heating Paraffin Oil
|Jul 31, 2007
|Feb 5, 2009
|Chevron U.S.A. Inc.
|Metalworking Fluid Compositions and Preparation Thereof
|Jul 31, 2007
|Feb 5, 2009
|Chevron U.S.A. Inc.
|Electrical Insulating Oil Compositions and Preparation Thereof
|Jul 31, 2007
|Feb 5, 2009
|Chevron U.S.A. Inc.
|Metalworking Fluid Compositions and Preparation Thereof
|Jul 31, 2007
|Feb 5, 2009
|Chevron U.S.A. Inc.
|Medicinal Oil Compositions, Preparations, and Applications Thereof
|Aug 28, 2007
|Mar 5, 2009
|Chevron U.S.A. Inc.
|Gear oil composition, methods of making and using thereof
|Jun 4, 2008
|Mar 5, 2009
|Chevron U.S.A. Inc.
|Gear Oil Compositions, Methods of Making and Using Thereof
|Jun 4, 2008
|Mar 5, 2009
|Chevron U.S.A. Inc.
|Gear Oil Compositions, Methods of Making and Using Thereof
|Oct 31, 2007
|Apr 2, 2009
|Chevron U.S.A. Inc.
|Tractor hydraulic fluid compositions and preparation thereof
|Feb 15, 2008
|Apr 2, 2009
|Chevron U.S.A. Inc.
|Lubricating grease composition and preparation
|Jun 4, 2008
|Jun 25, 2009
|Chevron U.S.A. Inc.
|Power Transmission Fluid Compositions and Preparation Thereof
|Jul 16, 2009
|Chevron U.S.A. Inc.
|Compressor Lubricant Compositions and Preparation Thereof
|Dec 3, 2009
|Chevron U.S.A. Inc.
|Gear oil compositions, methods of making and using thereof
|Sep 16, 2010
|Instituto Mexicano Del Petroleo
|Hydroprocessing of heavy hydrocarbons using liquid quench streams
|Jul 23, 2009
|Oct 7, 2010
|Konica Minolta Business Technologies, Inc.
|Sep 25, 2008
|Dec 2, 2010
|Yuichi Tanaka
|Method of manufacturing diesel fuel
|Jun 15, 2010
|Feb 3, 2011
|Chevron U.S.A. Inc.
|Distillate production in a hydrocarbon synthesis process.
|Oct 13, 2004
|Jun 9, 2005
|Chevron U.S.A. Inc.
|Process for the upgrading of the products of fischer-tropsch processes
|Oct 13, 2004
|Mar 23, 2006
|Chevron Usa Inc
|Process for the upgrading of the products of fischer-tropsch processes
|Jun 8, 2015
|Dec 30, 2015
|Baker Hughes Incorporated
|Additives for olefin plant quenching fluid ph control
|U.S. Classification
|208/59, 208/80, 208/950, 208/58, 208/97, 208/93
|International Classification
|Cooperative Classification
|European Classification
|Apr 4, 2001
Owner name: CHEVRON U.S.A. INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MOORE, RICHARD O., JR.;REEL/FRAME:011685/0815
Effective date: 20010321
|Mar 28, 2002
Owner name: CHEVRON U.S.A. INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SMITH, BEN D.;PARIMI, KRISHNIAH;MOORE, RICHARD O. JR.;REEL/FRAME:013015/0869;SIGNING DATES FROM 20020311 TO 20020312
|Dec 18, 2006
|Fee payment
Year of fee payment: 4
|Dec 28, 2010
|Fee payment
Year of fee payment: 8
|Dec 29, 2014
|Fee payment
Year of fee payment: 12


text:
July 28-30, ODC Theater presents the world premiere of RAWdance's Double Exposure in its fully-realized form. This project breaks all the rules of traditional creative roles, with 16 choreographers and two dancers. Performed by RAWdance's Co-Artistic Directors, Ryan T. Smith and Wendy Rein, the piece is comprised of 12 duets created by some of the most intriguing and esteemed choreographers making work along the West Coast today. More info here.
We're hiring! RAWdance is seeking its first General Manager. The 30hr/week General Manager will be joining the two Co-Artistic Directors in overseeing the company's regular operations, projects and productions, and long-term planning. Full description and application info here!

subset: commoncrawl


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The IPL advantage
Sir — When it comes to the big moments, India wins hands down (as it did on Sunday), to go down in the record books as winners of the final edition of the Champions Trophy.
Destiny's child, MS Dhoni, can't be stopped — not by mortals, at least, or so it seems! Team India captain Dhoni's hat-trick is complete: The inaugural World T20 in 2007, the 2011 World Cup and, now, the Champions Trophy.
The match had, of course, been reduced to a T20 affair and the advantage was with Dhoni and his men, thanks to the Indian Premier League experience. Come to think of it, the IPL does have its pluse.
- Indian politicians should take lessons from Britain 27 Jun 2016 | Madhu Agrawal
- Respecting referendum 27 Jun 2016 | NR Ramachandran
- Facing consequences 27 Jun 2016 | Bal Govind
- Way forward 27 Jun 2016 | KS Jayatheertha
- Great loss 27 Jun 2016 | Ramesh G Jethwani
- ISRO has made us proud, but there is much to do 25 Jun 2016 | Gaurav Singhal
- Brexit blues 25 Jun 2016 | R Narayanan
- Historic adventure 25 Jun 2016 | Hansraj Bhat
- Commendable job 25 Jun 2016 | Vinod C Dixit
- Who's benefit? 25 Jun 2016 | G David Milton
Parallel education: Road beyond DU
26 Jun 2016 | Ananya Borgohain and Shraddha Singh
When Delhi University announces its first cut-off list for undergraduate courses, predictably thousands of students will be rejected. Where do they go now when the frontiers they aspire for a successful future lead them to a dead end, ask ANANYA BORGOHAIN and SHRADDHA SINGH While Delhi University (DU) will release its first cut-off list for undergraduate courses on June 30, its St Stephen's College had announced its own list last week...
C'garh Govt to monitor projects using advanced software
27 Jun 2016 | Staff Reporter | Raipur
The Chhattisgarh Government will be utilising 'Centralised Project Management Software System' (CPMS) for automation of Project Monitoring, Controlling and Reporting task for key projects undertaken in the State. Notably, the Government is investing significantly in the State to build physical Infrastructure — Highways, Bridges, Water & Electrical distribution system etc...
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How can a 48-member NSG be an elite group? It's got members like New Zealand, Ireland...These people who have no nuclear programme of any kind.
I had a great time working with Jackie Chan. He is the most humble and grounded person I have ever met. He is a true legend.
I do not understand why the British Government needs until October to decide whether to send the divorce letter to Brussels


text:
AP, Photo by Evan Agostini/Invision
NEW YORK — Barbra Streisand was full of Brooklyn pride as she belted out well-known tunes with passion during a concert at the newly built Barclays Center.
Thursday night's three-hour show was Streisand's return to her hometown, where she's also performing Saturday on her "Back to Brooklyn" tour.
The 70-year-old told the crowd of 18,000 that the last time she performed solo in the New York City borough was "on somebody's stoop on Pulaski Street" as an 8-year-old.
She entered the stage in a shimmery black blazer and long skirt, holding her hands close to the microphone as she hit the right notes on more than two dozen songs, including "People," ''Evergreen" and "The Way We Were."
"Hello Brooklyn," she yelled. "Who said you can't come home again, right? Just Thomas Wolfe."
A video from "summer 1979" played on a large screen as people from Streisand's neighborhood talked about the singer, commenting on her talents, demeanor, family and even her nose.
"Purely a reflection of Brooklyn," one woman said. As the clip closed another woman said: "Come back to Brooklyn and give us a concert."
"It might have taken me 33 years, but I'm finally here," she said to the crowd.
"I left Brooklyn to pursue my dreams. Brooklyn quite never left me," she said at another time.
Streisand played with the audience, often telling jokes and taking in the many screams of "I love you, Barbra!"
The icon looked to the front row at a fan wearing one of her T-Shirts.
"You buy it in the shop? It's cheaper online," she said, as people laughed. She looked to another in the crowd: "You look like Dick Cheney. See this is what happens when I see the audience, it's not good."
The stage beamed with purple lights, as an orchestra of 30-plus played in a pit where small blue lights were strung around them.
Streisand performed sitting and standing, as a small table stood next to her where flowers and a mug with chicken soup were placed (she said she woke up with a cold).
Ahead of her performance fans submitted questions to Streisand, who answered several of them onstage. One asked if she was aware that contemporary singers lip sync.
"I've heard about that. I could never do it because I'm so bad at it. So I have to apologize because I have to sing live," she said as the audience roared.
That question was followed with: "I'd love to know what you think of Mitt Romney's promise to fire Big Bird."
"I love Big Bird and I hope no one tells Romney how to get to Sesame Street or Pennsylvania Avenue," she said as the crowd cheered even louder. "He's a good actor. He's a good actor. A chameleon."
That wasn't Streisand's only political moment. The Barack Obama supporter said she taped Thursday night's vice presidential debates and couldn't "wait to go home to watch."
"I'm not going to tell you who to vote for, but ... if you believe in affordable health care and women's rights ... if you want to move forward and not back, you know who to vote for," she said.
Streisand was joined onstage by trumpeter Chris Botti, Italian operatic trio Il Volo and her 45-year-old son Jason Gould, asking him before they sang a duet: "Do you need anything, like, a sweater? You need some chicken soup?"
He earned a standing ovation as his mother looked on, gasping "Oh my God."
She remembered late singer Donna Summer by performing their duet "No More Tears (Enough Is Enough)." She also paid tribute to her late friend — composer Marvin Hamlisch — as she sang "The Way We Were," saying "this is for you" before giving a rousing rendition of the tune.
When she performed "You're the Top," Streisand changed the lyrics, namedropping fellow Brooklynite Jay-Z, who performed eight shows at the Barclays Center last week. She sang lyrics like: "You're a Brooklyn Net, on a private jet" and "it's an accent you can't drop."
Follow Mesfin Fekadu on Twitter at http://www.twitter.com/musicmesfin
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On February 24, 2012, Wanderlust opens in American theaters. This is not a promotional Phriday for this movie: Something Awful has no stake in its success, though it features former Phriday star Alan Alda, B-movie "scream queen" Jennifer Aniston and Kansas City's sweetheart Paul Rudd. But its whimsical poster caught the eye of forums member Dissapointed Owl, who invited the SA Goons to place its carefree stars in outrageous situations. The thread got off to a shaky start, and at times things looked bleak, but then it became quite mirthful, and people learned valuable lessons about patience and not taking things too seriously. I'm sure this pretty much mirrors the story arc that main characters George (Rudd) and Linda (Aniston) will follow on February 24, when Wanderlust, co-written by beloved Veronica Mars bit player Ken Marino, becomes the must-see feel-good free-love hit of 2012!
Darth Brooks
Boats! They're great. But what should we name them? Let's find out...
We clear up the BREXIT for confused Americans wondering why the global economy is collapsing this time.
Game of Thrones Unaffected By UK's EU Referendum
The Loser: show up in roller skates
Insanely twisted and messed up stick figure families... holy sh*t...
Photoshop Phriday showcases the tremendous image manipulation talents of the Something Awful Forum Goons. Each week they tackle a new theme, parodying movies, video games, comics, history, and anything else you can think of. If you want in on the action, join us on the Something Awful Forums!
Copyright ©2016 Rich "Lowtax" Kyanka & Something Awful LLC.


text:
Posted: 5/22/2012Provided by Citysearch -
Very dry burgers. Service was lousy.....
Today:11:30 am - 11:00 pm
Tomorrow:5:00 pm - 10:00 pm
800 W Olympic Blvd,
Los Angeles, CA 90015
(213) 748-9700
Regular Hours
Primary Phone: (213) 744-1677
Phone: (213) 744-1677
Wolfgang Puck Catering
Wolfgang Puck Bar And Grill
Wolfgang Puck Catering & Evnts
Cuisine: American
Price Range : Average
Posted: 5/22/2012Provided by Citysearch -
Very dry burgers. Service was lousy.....
Posted: 2/12/2012
this was some of the worse service I have ever had were out of first two choices then tried over charging
Posted: 6/29/2009Provided by Citysearch -
I went to Wolfgang Puck Bar & Grill on Saturday night with three friends. From the beginning, we had a pretty good experience. Despite the long line, we were seated promptly because we made a reservation prior to our visit. Although not extremely friendly, our waitress was good about taking our drink and food orders in a timely manner. In terms of the taste of our food, it was what can be expected from Wolfgang Puck?an interesting array of flavor combinations. I ordered the ricotta gnocchi with fennel sausage Bolognese. The gnocchi was pillowy soft and the sauce was well-seasoned. One thing I would look out for are portion sizes. It really varies depending on the dish you get. Some of the pastas are larger than others, and the fish dishes are on the smaller size compared to other restaurants. Also, the price of the bill can add up if you go with multiple courses. Overall it was a good experience, especially because the night we went there, Wolfgang Puck himself was there!
645 W 9th St Ralph's #0022 Grocery, Los Angeles, CA
800 W Olympic Blvd, Los Angeles, CA
845 S Figueroa St Smart & Final #484 Grocery, Los Angeles, CA
1020 S Figueroa St, Los Angeles, CA
735 S Figueroa St Target #2776 Grocery, Los Angeles, CA
800 W Olympic Blvd, Los Angeles, CA 90015
(213) 748-9700


text:
Thanks for visiting the website and see you in town shortly. Don't forget to have a look at our Lublin Travel Guide!
MANTRA Club Sand Island Monument Bazylia Restaurant Wroclaw Town Hall Monument Pycha Micha Restaurant Brasserie 27 Restaurant Jas i Malgosia Tenement Monument Szczytnicki Park Have fun Cube Shop Wroclaw University of Economics Education Olszewskiego128 Restaurant 4 Pory Roku Restaurant
You can also email us your enquiries. We aim to respond to enquiries within 24 hours (excl. weekends). We work hard to make our website perfect, so we always appreciate notifications of broken links etc.


text:
Mercure Brighton Seafront Hotel4
149 King's Road, Brighton, BN1 2PP
Price FromView Rooms
- Good
- 32 guest reviews
"Hotel was lovely, very central. Staff were very helpful and friendly, room was very good and clean...."
"We booked this hotel for my parents-in-law 65th wedding anniversary after visiting and being kindly shown around by a smashing chap. It wasn..."
"We stayed in the superior sea view room on the first floor with balcony and two double doors which was lovely. The room was big and spacious..."
"We had a room on the Mews which was really quiet - something we do not often experience in Brighton. Room also had a window which makes a re..."
"Friendly staff. However, I requested breakfast and late check-out but my room was not on the breakfast list and my room key stopped working..."
About the hotel
Built in 1864, the hotel landed a great spot on the seafront. Sweep down the original Regency staircase for international dishes in the Brasserie Restaurant overlooking the sea. Outside, stroll along Brighton Pier, go boutique shopping in The Lanes and marvel at the Indian-inspired Royal Pavilion, all just one mile from the hotel.
Brighton's beach and promenade are directly opposite Mercure Brighton Seafront Hotel. Brighton railway station, with direct connections to London, is a mile away. We have a limited number of car parking spaces, they are first come first served and are chargeable at £25. 00 per night. This hotel is now completely non-smoking. WIFI is free to all guests throughout the hotel.
Read MoreLess
Facilities Show/hide
- Main
- Hotel Non-Smoking Throughout , Disabled Facilities
- Hotel services
- 24 Hour Reception , 24 Hour Room Service , Limited room service for hot food , Laundry/Valet Service , Wake Up Call Available
- Other
- Wedding Licence , Porter
- Parking (charges may apply)
- Car parking available onsite
- Business
- Wi-Fi Available , In-room Broadband , In-room Modem Hook up , Wi-Fi Available In Public Areas , Private dining services
- Dining
- Restaurant , Lounge Menu , Bar
- In room entertainment
- TV , [Channels] News , [Channels] Movies (Pay Per View) , [Channels] Music , [Channels] Childrens , Radio
- In room facilities
- Tea/Coffee making facilities in each room , Hairdryer in each room , Telephone In Each Room
- Accessibility
- Disabled Access Public Areas , Disabled Access Bedrooms , Wheelchair Access , Wheelchair Access To Reception , Wheelchair Access To Restaurant , Wheelchair Access To Bar , Wheelchair Access To Conference Rooms , Wheelchair Access To Leisure Facilities , Wheelchair Access To Disabled Car Parking Spaces
Useful Info Show/hide
- From 14:00 hours
- Until 10:00 hours
- The price shown is based on the occupancy and dates you have searched for. Prices and availability are subject to change based on the arrival date, number of nights and occupancy searched for. All prices are inclusive of all local taxes.
- Pets are not allowed
Customer Reviews
Our reviews are from genuine LateRooms.com customers. We verify that the customer has stayed before leaving a review.
44% would recommend it to a friend
Customer service
Food quality
Room quality
Lovely hotel
Hotel was lovely, very central.
Staff were very helpful and friendly, room was very good and clean.
Read More Less
Sadly disappointed
We booked this hotel for my parents-in-law 65th wedding anniversary after visiting and being kindly shown around by a smashing chap.
It wasn't cheap (pretty much London rates) but we felt confident that it would be worthwhile because of the lift facilities and mobility challenged awareness. We arrived to find that our stay was room only despite booking B & B through Late Rooms. The reception staff basically just shrugged and said nothing they could do. The lift was a nightmare to make work and in fact once we just gave up and had to step by step get our elderly parents down the stairs. The room locks sometimes wouldn't unlock but again a lovely member of staff showed us a 'trick' to reboot the electronics. That evening we decided to eat in the restaurant and after nearly an hour and a half gave up and complained at reception. Others in the dining room had been waiting even longer and then we were told by a hugely embarrassed waitress that almost half the menu was unavailable. Actually when the meal arrived it was VERY good. The following day (Sunday) my wife and I came down to the car for a relaxing drink after a hard morning pushing wheelchairs to find no bar staff for 20 minutes. Then a chap arrived and couldn't serve us alcohol "unless you have a beer!" (?) A couple of ladies had ordered a cream tea and were laughing about getting no milk for the tea, no butter or jam for the scones. Really!. In the end we felt that we had to confront the manager on Monday morning, bringing down an electronic copy of our booking showing we DID book B & B. After a 20 minute session the manager did waive the parking charge (that would have been another £50) and agreed that we did not need to pay for breakfasts. This weekend was a shambles. Lovely staff who were badly managed (too typical we are finding). At £150 a night we would expect our original issue with the booking to have been taken up by the Hotel, not have to mess about trying to prove our own case. It turned out the barman was sick (SO SAY SO!). The chef that evening was an agency chef. (Not our problem and no excuse for leaving one waitress carrying the wrath of all the clients). The electronics at the hotel obviously need sorting out not just shrugged at. Such a shame because the rooms were lovely, clean, excellent beds and pillows. Breakfast was very nice and the basic staff faultless and did all they could to be helpful but this hotel needs managing properly and a sort out. You want to charge this level of money you have to provide the service!
Read More Less


text:
In C# .NET 2.0, property Application.OpenForms only returns visible forms. How to get all forms in application including hidden forms. Thanks.
Notes: C# .NET 2.0, Windows Form.
Apparently, according to one of the posts here there is a bug in Windows Forms that makes forms dissapear from the
I might add that you could maintain your own Forms collection and get a reference to it there, or that you might just maintain a reference to it for the operations that you are performing for the life of that


text:
Resorts in Taipei
Search for resorts in Taipei
Last minute Taipei deals
- The Tango Hotel Taipei FuHsingfrom $114
- Leofoo Residencesfrom $173$91
- The Landis Taipeifrom $290$139
- Grace Hotelfrom $141$57
- UINN TRAVEL - Hostelfrom $19$8
Trending now in Taipei
- Most bookedEvergreen Resort Hotel (Jiaosi)
282 people looked at this hotel in the last hour
Most recent review
"My boyfriend and I enjoyed every moment during our 3-night stay in the hotel. We even cancelled one day of our planned trip just to spend time and enjoy the facilities in the hotel. Exceed expectation: extra large king bed, exceptionally spacious room, well kept in-room and hotel facilities which..."
A Traveller, Jun 2016, HK
176 people looked at this hotel in the last hour
Most recent review
"All of the staffs providing the excellent service. Incredible experience."
A Traveller, May 2016, HK
133 people looked at this hotel in the last hour
Most recent review
"Overall it's quite nice but improvement can be made in its food both at breakfast and dinner."
A Traveller, Apr 2016, US
104 people looked at this hotel in the last hour
Most recent review
"This resort was better than I expected. Although a little pricey, the facilities were great, including indoor and outdoor saunas, 2 restaurants, shops and walking trails. Breakfast was very good, and included a large selection of Asian and Western dishes. Parking is available on-premises quite cl..."
A Traveller, Dec 2015, AU
95 people looked at this hotel in the last hour
Most recent review
"Stayed a night with a family. Staffs were super helpful and nice. We definitely had a great time. We arrived late but the hotel allowed us to check out 1 hour later, which was super nice! Two things though - the room that I stayed smelled pretty bad - someone must have smoked in the room. I tried..."
A Traveller, Dec 2014, US
42 people looked at this hotel in the last hour
Most recent review
"it's ok, if thr check out time can be delay to 1 or 12 is better, since we got our flight on 4, and the area is nothing to ealk around, so we jist can go to aieport earlier and havr lunch there."
A Traveller, Apr 2015, HK
35 people looked at this hotel in the last hour
Most recent review
"1st time visit. Good, nice and quiet place to visit. Service, staffs are friendly. Room condition ( door, bath) can be improved based on the rate it charges. Overall wise, it's above avg. place to stay."
A Traveller, Jan 2016, US
32 people looked at this hotel in the last hour
32 people looked at this hotel in the last hour
- Pacific Hot Spring & Beach Resort Green Bay
No Guest Reviews yet
21 people looked at this hotel in the last hour
Map of resorts in Taipei
- Taipei 101
- Shilin Night Market
- Sun Yat-Sen Memorial Hall
- Yangmingshan National Park
- National Taiwan University
- Taipei Arena
- Longshan Temple
- Beitou Hot Springs Museum
- Taipei Sogo
- Jaoho Night Market
- Fulong Beach
- Chiang Kai-shek Memorial Hall
- Yong Kang Street
- Grand Hotel
- TaipeiEYE
- Taipei 228 Memorial Park
- National Chengchi University
- Ningxia Night Market
- Taipei World Trade Center Nangang Exhibition Hall
- Wulai Waterfalls
Taipei Resorts
Browse Hotels.com's picks for the best Taipei resorts with first class service and luxury from all over the world. The beautiful Taipei has the best resorts offering luxury, elegance for total relaxation by the ocean. On this page you can find and book Taipei resorts with the best deals and discounts, and if you still can't find a deal that fits your travel budget, you can search further and find the season featuring resort deals near Taipei.
Hotels.com always has the best prices on Taipei resorts located near the most paradisiac locations and exciting attractions. Whether you are going to the beach on vacation or for a wedding or other celebration, make sure you easily book your Taipei resort online, receive your itinerary and confirmation message in your email and prepare to enjoy a your stay in Taipei.
Check our latest Hotels.com genuine guest reviews on Taipei hotel resorts and compare to Expedia.com and Trip Advisor reviews so you can choose a hotel that will give you the most pleasant stay experience with no undesirable surprises.
Remember when you book a Taipei resorts with Hotels.com you win a hotel or resort night stay with the Welcome Rewards Program – For every 10 nights you stay in any resort, you can earn 1 free night*. So even a quickly weekend getaway in Taipei can get you a free night. Book your Taipei resort now with Hotels.com.
Taipei travel guides
Taipei Travel Tips - Helpful hints and advice on local destination information
Taipei is one of the safest Asian capitals for visitors, with little in the way of violent crime and...
Taipei Shopping Guide - Find where and what to shop and buy
Known as the 'Emporium without End', Taipei has endless shopping options and the best of it located ...
Taipei Entertainment Guide - For fun, recreation, and relaxation
Taipei has entertainment options in all areas, from a decent nightlife scene to the arts, nature hik...


text:
Posted: 7/6/2015
I was in this place in the early 90's! It was hell!!! They refused to allow me to speak to my mother for 6 months! I was only 10 years old. It was not my mothers fault. They attempted to get custody of me by not informing my mother of the hearing. Thank god she had an attorney! The judge allowed me to return home. I understand some children need to be taken from their parents but I wasn't one of them. My mother didn't even know where I was until I slipped away one day at Wal-mart (where we were forced to sell stale candy for "fundraising") and called her. The house father Brother Westfall would beat the children with a huge wooden paddle if they disobeyed. These children were broken and abused and that was the last thing they needed. They had their own private school on premises which did not provide an adequate education. The learning material was only about God and Jesus. I was nearly held back a grade when I went back to regular school because of this. If you have any compassion for children, DO NOT SEND THEM HERE!!!


text:
List all words ending with awardee
Only the word awardee was found, nothing longer.
Some random words: jnana ilea toil vocable aoudad jealous feal
This is not a dictionary, it's a word game wordfinder.
- Help and FAQ - Examples - Home
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text:
Concord Yellow Cab
Oakley, CA
Toll-free: 1-800-TAXI-USA | Local: 925.779.9292
Need a ride? Take Concord Yellow Cab for a welcoming, affordable, and memorable trip. Request a ride and get picked up by a reliable Oakley driver in minutes.AMEX CARD WEB BOOKING DELIVERY Was this driver helpful? Yes No | Write a review
Antioch Livery Yellow Cab
Oakley, CA
Toll-free: 1-800-TAXI-USA | Local: 925.755.4100
Antioch Livery Yellow Cab offers efficient, reliable Oakley taxi service to meet the travel needs of residents, visitors, and corporate clients. Call them for trips to the airport, sightseeing tours, or medical visits and shopping.WEB BOOKING CORPORATE WHEELCHAIRS Was this driver helpful? Yes No | Write a review
The taxi and transportation companies that 1-800-TAXI-USA refers to by telephone, the web or otherwise, are independent companies that are not owned or operated by 1-800-TAXI-USA. Because it does not own or operate any of these companies, 1-800-TAXI-USA expressly disclaims any and all liability to anyone related to the services provided by any of these companies. The information provided by 1-800-TAXI-USA is provided by these companies, but 1-800-TAXI-USA does not guarantee it to be accurate or complete. Users must independently verify all information regarding these companies.


text:
I know Dec. 15 to April 15 is the high season and peak travel time.
What would be other good months to visit Anguilla in addition to that timeframe. We do not want to go during the winter.
Thanks for your help.
Recent ActivityView all Caribbean Islands activity »
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- 7 Cat Island (Fernandez Bay Village) Trip Report
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- 9 Which Caribbean Island Should I Visit?
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Anguilla - Best Months to Visit
I know Dec. 15 to April 15 is the high season and peak travel time.
Report Abuse
Hi Lois. We went in late May/early June and had great weather. I would not hesitate to go during that time again.
I would say in general though that the month of May would be a great time to go.
Report Abuse
December 15 to April 15 is Peak Season in The Caribbean because that's when most people from the colder areas want to go someplace where it is warm and sunny not necessarilly because it is the best time to visit a particular island. You can visit Anguilla almost any time of and encounter good weather. In fact, early spring and summer are great times to visit as the island is not as crowded (not that Anguilla gets very crowded in Peak Season) and hotel rates are lower. The only time you'll find it less desirable to visit would be from late August through October 31 as many resorts and restaurants close during that time because it is peak hurricane season.
Sign in to comment.


text:
Pembroke New Hampshire Golf Courses
|Plausawa Valley Country Club
Featured Golf Course Review:
|Plausawa Valley Country Club -- challenging
|Review by: Nelson Dionne
|The course consists of two very different nines, one 40 yrs, other 15 years old. The front is situated on farmland and is relatively open with water on five holes. The greens are large and receive shots well. The back nine meanders through wood and has the Saucook river coming into play on three holes. This part of the course depends on good shot-making as the course is narrower and requires shooting to exact areas of the greens, due to undulations and levels, The course features a treat to your eyes and is a pleasure to play, even if your score is not up to par. Generally, an enjoyable course to play.
|From NH
Golf Courses: Additional Golf Course Reviews:
|Pine Valley Golf Links -- bad
|Review by: Bob Tob
|this course is a waste of time. it is usually in poor conditions. There are many other courses in the area woth your time, such as Hickory Hill or Scottish Highlands.
|From Bobville, MA USA


text:
Uzbekistan took the upper hand in the first leg of their FIFA World Cup Asian play-off after claiming a 1-1 draw in Jordan.
Server Djeparov's equaliser in the 35th minute gave the Uzbeks a crucial away goal after Mossab Al-Laham had handed the hosts the lead.
The stakes were high on Friday, with the winner of the two-legged Asian clash set to continue their bid to qualify for the World Cup.
Either Uzbekistan or Jordan will then play-off, again over two legs, against the fifth-placed South American team, with the winner set to reach next year's tournament in Brazil.
Jordan entered the fixture on the back of an outstanding home record that had seen them win 10 of their last 11 fixtures, with the other being a draw.
In that run, they beat Asian heavyweights Japan and Australia, and spirits were high within the Jordan camp after they took the lead.
Al-Laham was the scorer, firing Jordan into a 30th-minute lead as he finished a neat passing move well.
Uzbekistan quickly pegged them back, though, as Djeparov's third goal in his last five matches for his country proved crucial.
Djeparov linked well with Jasur Khasanov in the build-up before scoring with his left foot.
Jordan coach Hossam Hassan brought attackers Odai Al-Saify and Abdallah Deeb off the bench in the second half as they searched for a winner, but their efforts were in vain.
The draw was an excellent result for Uzbekistan, who – armed with an away goal – will feel confident about the second leg, to be held in Tashkent on Tuesday.
|Amer Shafi'
|Anas Bani Yassen
|Oday Zahran
|Mohammad Ali
|Mohammad Al Dumeiri
|Saeed Al Murjan
|Shadi Abu Hashhash
|Hassan Abdel Fattah
|Khalil Baniateyah
|Ahmad Hayel Ibrahim
|Mus'ab Al Laham
|Coach: Hossam Hassan
|M. Zukhurov
|A. Ismailov
|V. Denisov
|Y. Krimets
|I. Inomov
|S. Djeparov
|T. Kapadze
|O. Akhmedov
|J. O. Hasanov
|S. Tursunov
|B. Nasimov
|Coach: M. Qosimov
for Shadi Abu Hashhash 46'
for Hassan Abdel Fattah 60'
for Saeed Al Murjan 79'
for Y. Krimets 40'
for B. Nasimov 65'
for S. Tursunov 88'
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|Europe ´vastly underrated´ Italy - Buffon
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|Spain not up to required level - Pique
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|Rooney intends to continue with England
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|Hodgson had to go after humiliating England exit
|´It is embarrassing to go out´ - Rooney
|England pathetic and disgraceful - the world reacts to Hodgson departure
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