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Patent US4481106 - Hydrocarbon treating process - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA process is disclosed for treating hydrocarbon streams such as naphtha by the oxidation of mercaptans into disulfide compounds which remain in the hydrocarbon stream. The conversion is effected during passage of the hydrocarbon and an aqueous stream downward through a cylindrical mass of liquid-liquid...http://www.google.com/patents/US4481106?utm_source=gb-gplus-sharePatent US4481106 - Hydrocarbon treating processAdvanced Patent SearchPublication numberUS4481106 APublication typeGrantApplication numberUS 06/558,243Publication dateNov 6, 1984Filing dateDec 5, 1983Priority dateDec 5, 1983Fee statusPaidAlso published asCA1209514A1, DE3470056D1, EP0145439A2, EP0145439A3, EP0145439B1Publication number06558243, 558243, US 4481106 A, US 4481106A, US-A-4481106, US4481106 A, US4481106AInventorsThomas A. VerachtertOriginal AssigneeUop Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (15), Non-Patent Citations (2), Referenced by (10), Classifications (9), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetHydrocarbon treating processUS 4481106 AAbstract A process is disclosed for treating hydrocarbon streams such as naphtha by the oxidation of mercaptans into disulfide compounds which remain in the hydrocarbon stream. The conversion is effected during passage of the hydrocarbon and an aqueous stream downward through a cylindrical mass of liquid-liquid contact material. The liquids then flow through a cylindrical screen into an annular separation zone which surrounds a lower part of the contact material. After decantation in the separation zone, the aqueous material, which preferably contains the oxidation catalyst, is recycled.
I claim as my invention: 1. A process for sweetening hydrocarbon streams to reduce the concentration of mercaptan compounds contained therein which comprises the steps of:(a) forming a reaction zone charge stream by admixing a liquid phase hydrocarbon feed stream which comprises a mercaptan with an oxygen supply stream and with a liquid phase first aqueous stream which comprises an alkaline reagent and soluble oxidation catalyst; (b) passing the reaction zone charge stream downward through a fixed mass of contact material located within a vertically oriented vessel at oxidation-promoting conditions, the mass of contact material extending from an upper portion of the vessel downward to at least the lowermost quarter of the vessel; (c) separating the liquids flowing downward through the mass of contact material in the lowermost quarter of the vessel by a method which comprises withdrawing the liquids through a vertical porous wall into an annular separation zone which is located in the lower portion of the vessel and surrounds the lower portion of the mass of contact material, and decanting the liquids into a hydrocarbon phase comprising disulfide compounds which rises into an open-bottomed covered volume, which is located above the porous wall and separated by impervious upper and side walls from the mass of contact material, and an aqueous phase comprising the alkaline reagent which settles to the bottom of the vessel; (d) withdrawing a treated hydrocarbon product stream from the open-bottomed volume, and withdrawing a second aqueous stream from the lower portion of the vessel; and (e) employing at least a portion of the second aqueous stream as the previously referred to first aqueous stream. 2. The process of claim 1 further characterized in that the hydrocarbon feed stream has an initial boiling point below about 430
3. The process of claim 2 further characterized in that the oxidation catalyst comprises a phthalocyanine compound.
4. The process of claim 3 further characterized in that the mass of contact material comprises a bed of relatively inert solid particulate material.
5. The process of claim 4 further characterized in that the annular separation zone does not contain solid particulate material.
6. The process of claim 5 further characterized in that the solid particulate material comprises a charcoal.
7. The process of claim 6 further characterized in that the flow rate of the aqueous stream is less than 15 volume percent of the flow rate of the feed stream.
8. A process for reducing the concentration of mercaptan compounds in a hydrocarbon stream which comprises the steps of:(a) contacting a liquid phase hydrocarbon feed stream which comprises mercaptans, a liquid phase first aqueous stream which comprises an alkaline reagent, and an oxygen supply stream in the presence of an oxidation catalyst in a fixed bed of contact material maintained at oxidation-promoting conditions and located within a vertically aligned vessel, the liquids flowing cocurrently downward through the bed of contact material from an upper portion of the vessel to a point in the lower one-third of the vessel; (b) separating the liquids which have passed downward through the bed of contact material by a method which comprises passing at least the hydrocarbonaceous portion of the liquids horizontally through a porous vertical screen encircling a lower portion of the bed of contact material into a quiescent separation zone located in the bottom one-third of the vessel with the liquids dividing into an aqueous phase and a less dense hydrocarbon phase, which is collected in an open-bottomed chamber forming the top of the separation zone; (c) withdrawing a treated hydrocarbon product stream comprising disulfide compounds from the separation zone; (d) withdrawing a second aqueous stream at a point in the vessel below the open-bottomed chamber; and, (e) recycling at least a portion of the second aqueous stream into the vessel for use as the previously referred to liquid phase first aqueous stream. 9. The process of claim 8 further characterized in that an oxidation catalyst is present in the aqueous stream.
10. The process of claim 7 further characterized in that the catalyst comprises a phthalocyanine compound.
11. The process of claim 10 further characterized in that the catalyst comprises a metal phthalocyanine compound.
12. The process of claim 11 further characterized in that the bed of contact material comprises charcoal.
13. The process of claim 12 further characterized in that the separation zone has an annular shape and is located between the inner surface of the vessel and a cylindrical wall, with the lower portion of the cylindrical wall being formed by said porous screen and an upper portion of the cylindrical wall being imperforate.
14. The process of claim 13 further characterized in that a cylindrical volume within the cylindrical wall is filled with contact material, and the bed of contact material continues upward above the separation zone.
15. The process of claim 14 further characterized in that the hydrocarbon feed stream has an initial boiling point below about 430
16. The process of claim 15 further characterized in that the oxygen supply stream is air and is charged to the process at a rate below the remaining gas solution capacity of the hydrocarbon feed stream.
FIELD OF THE INVENTION The invention relates to a mineral oil treating process referred to as sweetening. In this process, mercaptans present in a liquid hydrocarbon stream are oxidized to disulfide compounds which remain in the hydrocarbon stream. The invention therefore relates to processes for treating hydrocarbon streams such as naphtha or kerosene as are performed in petroleum refineries. The invention specifically concerns the method and apparatus used to bring the hydrocarbon stream and a circulating aqueous stream into contact and to then separate the hydrocarbonaceous and aqueous phases.
INFORMATION DISCLOSURE The sweetening of sour petroleum fractions is a well developed commercial process which is employed in almost all petroleum refineries. In this process, mercaptans present in the feed hydrocarbon stream are converted to disulfide compounds which remain in the hydrocarbon stream. Sweetening processes therefore do not remove sulfur from the hydrocarbon feed stream but convert it to an acceptable form. The sweetening process involves the admixture of an oxygen supply stream, typically air, into the hydrocarbon stream to supply the required oxygen. An oxidation catalyst is also employed in the process. The oxidation catalyst may be a part of a solid composite or may be dispersed or dissolved in an aqueous alkaline solution. A commonly employed oxidation catalyst comprises a metal phthalocyanine compound. This preferred catalyst is described in U.S. Pat. No. 2,882,224. This reference is also relevant for its teaching of general processing conditions and methods. The process flow of a similar sweetening process is shown in U.S. Pat. No. 2,988,500. A sweetening process using a different catalyst system is disclosed in U.S. Pat. No. 3,923,645.
The process flow of two commercial sweetening processes is shown at page 124 of the April, 1982 issue of Hydrocarbon Processing. When a significant amount of the alkaline aqueous solution, commonly referred to as caustic, is employed on a continuous basis, the aqueous solution and the hydrocarbon stream are first passed through a reaction vessel containing a fixed bed of contacting material. The aqueous liquid is then normally separated from the hydrocarbon stream in a separate settling vessel. In the second process flow, a very small amount of the aqueous solution is charged to the reaction vessel. The aqueous solution is then withdrawn from the bottom of the reaction vessel. U.S. Pat. No. 4,019,869 illustrates an apparatus which may be used in the latter process. It is also pertinent for showing a cylindrical particle bed resting on a horizontal support as the contacting zone. It is believed that heretofore this type of particle bed configuration was employed in commercial sweetening processes.
U.S. Pat. No. 4,392,947 is pertinent for its disclosure that sweetening processes may be performed having the liquids flowing upward, downward or in radial flow through the particle bed of the reaction zone.
BRIEF SUMMARY OF THE INVENTION The invention provides a sweetening process which is characterized by the performance of both the contacting step and the separation step in a single unitary vessel. In addition, the vessel has a simple and therefore low cost design. A distinguishing point of the new process is that the particle bed extends downward into a separation area, with a smaller diameter bottom portion of the particle bed being surrounded by a cylindrical wall having a lower porous section.
One embodiment of the invention may be characterized as a process for reducing the concentration of mercaptan compounds in a hydrocarbon stream which comprises the steps of contacting a liquid phase hydrocarbon feed stream which comprises mercaptans, a liquid phase first aqueous stream which comprises an alkaline reagent, and an oxygen supply stream in the presence of an oxidation catalyst in a fixed bed of contact material maintained at oxidation-promoting conditions and located within a vertically aligned vessel, the liquids flowing cocurrently downward through the bed of contact material from an upper portion of the vessel to a point in the lower one-third of the vessel; separating the liquids which have passed downward through the bed of contact material by a method which comprises passing at least the hydrocarbonaceous portion of the liquids horizontally through a porous vertical screen encircling a lower portion of the bed of contact material into a quiescent separation zone located in the bottom one-third of the vessel with the liquids dividing into an aqueous phase and a less dense hydrocarbon phase, which is collected in an open-bottomed chamber forming the top of the separation zone; withdrawing a treated hydrocarbon product stream comprising disulfide compounds from the separation zone; withdrawing a second aqueous stream at a point in the vessel below the open-bottomed chamber; and passing at least a portion of the aqueous recycle stream into the vessel for use as the previously referred to liquid phase aqueous stream.
BRIEF DESCRIPTION OF THE DRAWING The drawing is a simplified illustration of a sweetening process in which a feed stream of naphtha carried by line 1 is treated by the conversion of mercaptans present in the feed stream to disulfide compounds. This drawing of the preferred embodiment of the process has been simplified by the deletion of much of the apparatus customarily employed on a process of this nature such as temperature and pressure control systems, flow control valves, recycle pumps, etc. which are not required to illustrate the performance of the subject process. This presentation of specific embodiments of the invention is not intended to preclude from the scope of the subject invention those other embodiments set out herein or reasonable and expected modifications to those embodiments.
Referring now to the drawing, the sour naphtha feed stream from line 1 is admixed with an aqueous alkaline solution referred to herein as caustic carried by line 2. The admixture of naphtha and caustic is transported through line 3. Air from line 4, the preferred oxygen source, is admixed into a liquid flowing through line 3 with the air becoming totally dissolved within the liquid phase material. The thus-admixed liquid phase reactants enter the vertical vessel 5 at an upper point above a fixed bed of contact material 6. The liquids with the dissolved oxygen flow downward through the contacting material. The contacting material may support a suitable oxidation catalyst to promote the desired conversion of the mercaptans. However, it is preferred that the catalyst is dissolved in the caustic. A circular imperforate support ring 9 located in a lower half of the vessel causes the bed of particulate material to taper to a smaller diameter cross-section. A cylindrical imperforate wall 7 extends downward from the lower edge of the ring 9 to thereby confine the particulate material to a smaller cylindrical volume in the center of the vessel. Below the wall 7, the bed of particulate material is confined to the same cylindrical shape by a porous screen 8. The cylinder formed by the wall 7 and screen 8 defines an annular void volume located between the outer surface of the wall 7 and screen 8 and the inner surface of the vessel. This volume is referred to herein as the annular separation zone.
As the liquids flow downward through the contacting material of the smaller diameter cylindrical section, they begin to separate into discrete aqueous and hydrocarbon phases. The aqueous liquid is collected in the bottom of the vessel 5 as an aqueous phase having an upper interface 14, with the hydrocarbonaceous liquid phase located above this level. The descending liquids eventually flow outward horizontally through the porous wall 8 into the annular separation zone. The hydrocarbons rise upward into the open-bottomed collection chamber located at the top of the annular separation zone. The treated naphtha is withdrawn from this open-bottomed volume through line 10 as the product stream of the process. The aqueous material is withdrawn through line 2 for recycling. Small portions of the caustic may be periodically removed or added through line 11 to maintain the desired caustic purity and concentration. In the embodiment of the subject process in which the alkaline aqueous solution is only added on an intermittent basis or at a very small rate, the aqueous material may be withdrawn from the bottom of the vessel 5 through line 13. A vent line 12 may be provided at the top of the outer vessel 5 with the withdrawal of any separate gas phase which forms within the vessel.
DETAILED DESCRIPTION Most normally liquid hydrocarbon fractions produced in a petroleum refinery contain some sulfur compounds unless the hydrocarbon fraction has been subject to very extensive desulfurization procedures. The sulfur concentration in these fractions may be relatively low due to upstream refining operations such as hydrotreating. In many instances, such low total sulfur concentrations are acceptable in products such as motor fuel naphtha, kerosene or diesel fuel. However, the concentration of certain sulfur compounds must be very low to meet product specifications for these products. Specifically, the concentration of acidic and malodorous mercaptan compounds must be very low. The total removal of all sulfur-containing compounds can be very expensive. Therefore, it is a common practice to convert small amounts of mercaptan compounds to disulfide compounds, which because of their low vapor pressure and nonacidic nature, are tolerable in the hydrocarbon product, rather than to attempt to totally remove all sulfur compounds. This treating process is referred to as sweetening as it converts a "sour" smelling feedstock into a "sweet" smelling product, sometimes referred to as a "Doctor sweet" product owing to the "doctored" product passing a simple qualitative test indicating the absence of mercaptan compounds.
Sweetening is widely employed commercially as a low cost method of lowering the mercaptan content of normally liquid hydrocarbon products. In a typical commercial sweetening unit, the feed hydrocarbon is admixed with a gaseous oxygen supply stream and passed through a catalytic oxidation zone in which the mercaptans are oxidized to the corresponding disulfides. This reaction has also been referred to as oxidative condensation. Air is normally employed as the oxygen supply stream due to the greater cost of more highly concentrated oxygen-containing gases. An excess of oxygen above that required for the stoichiometric oxidation of the mercaptans is added to the hydrocarbon stream to promote the oxidation reaction.
An alkaline solution commonly referred to as caustic is also admixed into the hydrocarbon stream. This is either on a continuous or periodic basis. In those processes in which the alkaline solution is used on a continuous basis, it is necessary to obtain a degree of surface contact and admixture of the two phases. The passage of the hydrocarbon and aqueous caustic through the contacting zone can result in sufficient admixture of these two liquid phases to form a difficult to separate dispersion. It is highly undesirable, in almost all situations, for any of the aqueous material to remain in the hydrocarbon phase. The dispersion can be separated if a sufficient retention time is provided in a settling zone. Such zones however increase the cost of the process. It is an objective of the subject invention to provide a treating process which achieves sufficient contact of the aqueous and hydrocarbon phases but does not require the use of a separate large capacity separation vessel. It is also an objective of the subject invention to reduce the equipment costs and complexity of a sweetening process.
The subject process can be applied to the sweetening of any of various relatively light hydrocarbon fractions including naphtha and kerosene. Light straight run, light coker naphthas or similar fluid catalytically cracked products are specific examples of the preferred feed materials, which contain a mixture of hydrocarbons having boiling points under about 430 shale, etc. In the subject process, the admixture of the feed hydrocarbon and the alkaline solution, which is described in more detail below, are passed downward in a fixed bed of contacting material. The liquid is spread across the upper surface of the bed by a distributor. The upper portion, at least the upper one-half, of the bed of contacting material preferably has a cylindrical shape conforming to the inner surface of the process vessel. The liquids travel downward through the contacting material with the desired oxidative condensation of the mercaptans converting them into disulfide compounds. The disulfide compounds become dissolved in the hydrocarbon stream. At a point in the lower portion of the vessel, preferably in the lower one-third of the vessel, the two liquid phases are separated. This separation is performed at least in part within the contacting material. The separation begins when the vertical velocity of the liquids decreases because liquid is allowed to flow horizontally into a quiescent separation zone.
The separation zone is separated from the other portions of the vessel at the same level by at least one perforate panel or screen. This screen allows the free flow of liquid into the separation zone while preventing the entrance of contacting material. The hydrocarbons flow into the separation zone, and then flow upward due to the presence of a hydrocarbon outlet at the top of the separation zone. To accomplish this, the upper portion of the separation zone must be enclosed by a shroud or similar covering which can trap the less dense hydrocarbons. This forms an open-bottomed chamber at the top of the separation zone. This chamber must be sufficiently open at the bottom to allow the entrance of the hydrocarbons and to allow the denser aqueous alkaline solution to settle to the bottom of the vessel. Preferably, the separation zone is completely devoid of contacting material and extends downward to the bottom inner surface of the vessel.
The separation zone can be constructed with a number of different shapes. It could therefore have a rectangular cross-section and comprise a box-like structure centrally located in the bottom portion of the vessel. When viewed from above, the box-like structure could have a narrow rectangular cross-section extending across the entire distance between the inner surfaces of the vessel's outer wall. It is greatly preferred that the separation zone has the form of an annulus which surrounds a cylindrical bed of the contacting material. This cylindrical bed is preferably a continuation of the cylindrical contacting bed and extends downward through the vessel as shown in the drawing. It is also preferred that the annulus is located next to the inner surface of the outer vessel. This requires the use of only one porous wall and facilitates the withdrawal of liquid(s) directly through the vessel wall without the use of collection devices or connecting lines located within the vessel. Alternatively, an annular separation zone could be located radially inward from the outer wall of the vessel and have two cylindrical porous wall sections. The contacting material would then be present in an annular bed surrounding the separation zone in addition to being present as a cylindrical bed within the innermost wall of the annulus. The total cross-sectional area of the separation zone is less than 25 percent, and more preferably less than 20 percent, of the total cross-sectional area of the vessel on a horizontal section. It is therefore preferred that the remaining 75-plus percent of the cross-section of the vessel is filled with the contacting material.
The porous wall(s) of the separation zone are preferably made from a rigid self-supporting metal screen. This screen can be fabricated by welding parallel face rods to perpendicular support or connecting rods. The face rods should have a flat protruding surface which faces inward toward the contacting material. This material can be purchased from the Johnson Division of UOP Inc., New Brighton, Minn. The cylindrical screen preferably extends downward to the point at which it reaches the inner surface of the outer vessel. The remaining interior walls of the separation zone are formed of imperforate metal sheeting such as 1/4-inch carbon steel. It is preferred that the bed of contacting material is supported by the eliptical bottom head of the vessel. A separate perforate screen at the bottom of the vessel is used to prevent the contacting material from passing out with drain liquid. As an aid to practicing the subject process, it may be observed that in a rather small but commercial scale design, the outer vessel had a 6-foot inner diameter and contained an 8-foot high bed of contacting material. The separation zone was annular as in the drawing. The imperforate cylindrical wall was about 12 inches in height and the porous cylindrical wall was about 22 inches in height. As the alkaline aqueous solution was to be injected at a very low rate in this instance, the outlet port for the aqueous material was at the bottom of the vessel. If a substantial amount (more than 2 vol. %) of aqueous liquid is passed into the vessel with the hydrocarbons, the outlet for the aqueous liquid preferably communicates with the internal volume of the separation zone at a point below the top of the porous wall.
The subject process may be characterized as a method for treating hydrocarbon streams which comprises the steps of forming a liquid-phase reaction zone charge stream by admixing a liquid phase hydrocarbon feed stream which comprises a mercaptan with a liquid phase first aqueous stream which comprises an alkaline reagent and a soluble oxidation catalyst and with an oxygen supply stream; passing the reaction zone charge stream downward through a fixed mass of contact material located within a vertically oriented vessel at oxidation-promoting conditions, the mass of contact material extending from an upper portion of the vessel downward to at least the lowermost quarter of the vessel; separating the liquids flowing downward through the mass of contact material in the lowermost quarter of the vessel by a method which comprises withdrawing the liquids through a vertical porous wall into an annular separation zone which is located in the lower portion of the vessel and surrounds the lower portion of the mass of contact material, and decanting the liquids into a hydrocarbon phase comprising disulfide compounds which rises into an open-bottomed covered volume, which is located above the porous wall and separated by impervious upper and side walls from the mass of contact material, and an aqueous phase comprising the alkaline reagent which settles to the bottom of the vessel; withdrawing a treated hydrocarbon product stream from the open-bottomed volume, and withdrawing a second stream of aqueous liquid from the lower portion of the vessel; and employing at least a portion of the second aqueous stream as the previously referred to first aqueous stream.
A mercaptan oxidation catalyst is employed in the subject process. This catalyst may be supported on a bed of inert solids retained within the oxidation zone or may be dispersed or dissolved in the aqueous alkaline solution. The use of catalyst present in a circulating aqueous solution has the advantage of allowing quick replacement of the catalyst should this be necessary. The catalyst may also be present in both a supported and a dissolved form. Any commercially suitable mercaptan oxidation catalyst can be employed. For instance, U.S. Pat. No. 3,923,645 describes a catalyst comprising a metal compound of tetrapyridinoporphyrazine which is preferably retained on an inert granular support. The preferred catalyst is a metallic phthalocyanine such as described in the previously cited references and in U.S. Pat. Nos. 2,853,432, 3,445,380, 3,574,093 and 4,098,681. The metal of the metallic phthalocyanine may be titanium, zinc, iron, manganese, etc. but is preferably either cobalt or vanadium, with cobalt being especially preferred. The metal phthalocyanine is preferably employed as a derivative compound. The commercially available sulfonated compounds such as cobalt phthalocyanine monosulfonate or cobalt phthalocyanine disulfonate are preferred, although other mono-, di-, tri-, and tetra-sulfo derivatives could be employed. Other derivatives including carboxylated derivatives, as prepared by the action of trichloroacetic acid on the metal phthalocyanine, can also be used if desired in the subject process.
When the catalyst is used in its supported form, an inert absorbent carrier material is employed. This material may be in the form of tablets, extrudates, spheres, or randomly shaped naturally occurring pieces. An 8 clays and silicates or refractory inorganic oxides may be used as the support material. The support may therefore be formed from diatomaceous earth, kieselguhr, kaolin, alumina, zirconia, etc. It is especially preferred that the catalyst comprises a carbon-containing support, particularly charcoals which have been thermally and/or chemically treated to yield a highly porous structure similar to activated carbon. The active catalytic material may be added to the support in any suitable manner, as by impregnation by dipping, followed by drying. The catalyst may also be formed in-situ within the oxidation zone as described in the cited references. The finished catalyst preferably contains from about 0.1 to about 10 wt. % of a metal phthalocyanine. The solid or supported catalyst may comprise the only contact material which fills the central portion of the vessel or may be admixed with other solids.
In the preferred form of the sweetening process, an aqueous alkaline solution is admixed with the sour feed stream and air and the admixture is then passed through a fixed bed of the oxidation catalyst. The preferred alkaline reagent comprises a solution of an alkaline metal hydroxide such as sodium hydroxide, commonly referred to as caustic, or potassium hydroxide. Sodium hydroxide can be used in concentrations of from about 1 to 40 wt. %, with a preferred concentration range being from about 1 to about 25 wt. %. Any other suitable alkaline material may be employed if desired. The preferred rate at which the alkaline solution is passed into the vessel will depend on such factors as the composition of the feed. The flow rate of the alkaline solution may be as high as 15 vol. percent of the feed hydrocarbon. Alternatively, only small amounts may be charged on an intermittent basis to maintain catalyst activity. The rate of oxygen addition is set based on the mercaptan content of the sour feed hydrocarbon stream. The rate of oxygen addition is preferably greater than the amount required to oxidize all of the mercaptans contained in the feed stream, with oxygen feed rates of about 110 to about 220% of the stoichiometrically required amount being preferred.
The use of a packed bed contacting zone is required in all variations of the subject process to provide quiescent admixture of the reactants for a definite residence time. A small amount of mechanical devices such as perforated plates or channeled mixers can also be used in conjunction with the contacting bed, but the use of apparatus other than an inlet distributor is not preferred. Contact times in the oxidation zone are generally chosen to be equivalent to a liquid hourly space velocity based on hydrocarbon charge of about 1 to 70 or more. A contacting time within the fixed bed in excess of 1 minute is desired. The sweetening process is generally performed at ambient (atmospheric) or slightly elevated temperatures. A temperature above about 50 300 critical but is generally elevated to the extent necessary to prevent vaporization of the hydrocarbons and to achieve the solution of added oxygen and nitrogen into the hydrocarbons. The oxidation zone may be successfully operated at low pressures including atmospheric pressure. However, the subject process is directed to hydrocarbons having significant mercaptan contents and which therefore require substantially elevated pressures to achieve the desired gas solubility. For this reason, an elevated pressure above 150 psig is preferred. Higher pressures up to 1000 psig or more can be employed, but increase the cost of the process and are not preferred unless required to promote liquid phase conditions.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2176806 *Jan 24, 1938Oct 17, 1939Skelly Oil CoMethod and apparatus for contacting immiscible liquidsUS2729591 *Jun 20, 1952Jan 3, 1956British Petroleum CoSweetening of petroleum oils containing mercaptans with alkali and oxygen and then with alkali, a solutizer and oxygenUS2882224 *Feb 13, 1958Apr 14, 1959Universal Oil Prod CoProcess for sweetening sour hydrocarbon distillates with metal phthalocyanine catalyst in the presence of alkali and airUS2988500 *Mar 13, 1959Jun 13, 1961Universal Oil Prod CoTreatment of hydrocarbon distillatesUS3413215 *May 16, 1966Nov 26, 1968Universal Oil Prod CoOxidation of mercapto compoundsUS3445380 *Jul 7, 1967May 20, 1969Universal Oil Prod CoTreating sour hydrocarbon distillates containing mercapto compounds and acidic,surface-active materialsUS3547354 *Sep 6, 1968Dec 15, 1970Continental Oil CoGas flow diffuserUS3574093 *Jan 22, 1969Apr 6, 1971Universal Oil Prod CoCombination process for treatment of hydrocarbon streams containing mercapto compoundsUS3923645 *Sep 7, 1973Dec 2, 1975Ashland Oil IncMethod for oxidizing mercaptans occurring in petroleum refining streamsUS4019869 *Nov 10, 1975Apr 26, 1977Uop Inc.Combination reactor-separator apparatusUS4081354 *Oct 29, 1976Mar 28, 1978Uop Inc.Liquid-liquid extraction processUS4142964 *Jun 1, 1978Mar 6, 1979Uop Inc.Process for treating a sour petroleum distillateUS4248694 *May 17, 1979Feb 3, 1981Uop Inc.Process for treating a sour petroleum distillateUS4392947 *Sep 30, 1981Jul 12, 1983Mobil Oil CorporationIntegrated refining processCA625756A *Aug 15, 1961Universal Oil Prod CoProcess for sweetening sour hydrocarbon distillates* Cited by examinerNon-Patent CitationsReference1Hydrocarbon Processing, Apr. 1982, p. 124, "Merox".2 *Hydrocarbon Processing, Apr. 1982, p. 124, Merox .* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4604261 *Jun 29, 1984Aug 5, 1986Mobil Oil CorporationHydroprocessing reactor for catalytically dewaxing liquid petroleum feedstocksUS4675100 *May 30, 1985Jun 23, 1987Merichem CompanyTreatment of sour hydrocarbon distillateUS4746494 *Jul 21, 1986May 24, 1988Merichem CompanyTreatment of sour hydrocarbon distillateUS5264187 *Sep 3, 1991Nov 23, 1993Phillips Petroleum CompanyTreatment of hydrocarbonsUS5741415 *Sep 27, 1994Apr 21, 1998Chevron U.S.A. Inc.Method for the demercaptanization of petroleum distillatesUS5858212 *Jul 3, 1996Jan 12, 1999Interglobal Desulfuruzations Systems, Inc.Desulfurization and hydrocarbon quality enhancement processUS5961819 *Feb 9, 1998Oct 5, 1999Merichem CompanyTreatment of sour hydrocarbon distillate with continuous recausticizationUS7223332Oct 21, 2003May 29, 2007Uop LlcReactor and process for mercaptan oxidation and separation in the same vesselUS7445702 *Oct 30, 2003Nov 4, 2008Johnson Matthey PlcDesulphurisationWO2011114352A2Mar 16, 2011Sep 22, 2011Indian Oil Corporation LimitedProcess for selective removal of mercaptan from aviation turbine fuel (atf)* Cited by examinerClassifications U.S. Classification208/206, 422/239, 422/211, 208/203International ClassificationC10G27/04, C10G27/06, C10G17/00Cooperative ClassificationC10G27/06European ClassificationC10G27/06Legal EventsDateCodeEventDescriptionMay 6, 1996FPAYFee paymentYear of fee payment: 12May 1, 1992FPAYFee paymentYear of fee payment: 8Apr 27, 1989ASAssignmentOwner name: UOP, A GENERAL PARTNERSHIP OF NY, ILLINOISFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UOP INC.;REEL/FRAME:005077/0005Effective date: 19880822Sep 21, 1988ASAssignmentOwner name: UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIPFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD;REEL/FRAME:005006/0782Effective date: 19880916Apr 20, 1988FPAYFee paymentYear of fee payment: 4Jun 25, 1984ASAssignmentOwner name: UOP INC., DES PLAINES, IL A CORP OF DEFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:VERACHTERT, THOMAS A.;REEL/FRAME:004272/0584Effective date: 19831129RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google


text:
DREAM Act defeat reveals failed strategy
In Los Angeles, Leslie Perez, left, and Grecia Mondragon watch TV coverage of the Senate vote. (Jason Redmond)
On Saturday, that strategy was in ruins after Senate Democrats could muster only 55 votes in support of the Development, Relief and Education for Alien Minors (DREAM) Act, a measure that would have created a pathway to citizenship for undocumented immigrants who were brought to the United States as children. Under Senate rules, Democrats needed 60 votes to overcome Republican opposition to the bill. The House of Representatives had passed the measure this month, 216 to 198.
The irony of the DREAM Act's failure is that it had strong bipartisan support at the start of the administration, and advocates thought it could generate momentum for more policy changes.
But as the country's mood shifted on illegal immigration, support among Republicans and some Democratic senators evaporated, with many decrying it as a backdoor amnesty for lawbreakers.
Sen. Jeff Sessions (R-Ala.), who led Republican opposition to the measure, said: "This is an amnesty bill because it provides every possible benefit, including citizenship, to those who are in the country illegally."
Virtually no one thinks an immigration overhaul is possible in the next two years, given the views of many members of the incoming Republican majority in the House.
Now many immigrant-rights supporters are second-guessing Obama's efforts to woo Republicans by ramping up deportations.
"It is a strategy which has borne no fruits whatsoever," Gutierrez said. "This administration has unilaterally led the march on enforcement, yet the other side has not given one modicum of compromise."
"If you really want to bring Republicans to the table," he added, "so long as they are getting everything they want, every piece of enforcement, why, why would they come to the table?"
At a recent press briefing, Homeland Security Secretary Janet Napolitano denied that the administration had increased deportations to bring Republicans to the bargaining table.
"I don't view it as a quid pro quo," Napolitano said. "We enforce the law because we took an oath to enforce the law."

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Tau Pathology in Parkinson's Disease. - PubMed - NCBI
1 selected item: 30333786
Front Neurol. 2018 Oct 2;9:809. doi: 10.3389/fneur.2018.00809. eCollection 2018.
Tau Pathology in Parkinson's Disease.
Zhang X1, Gao F1, Wang D1, Li C1, Fu Y1, He W1, Zhang J1.
Tau protein-a member of the microtubule-associated protein family-is a key protein involved in many neurodegenerative diseases. Tau pathology in neurodegenerative diseases is characterized by pathological tau aggregation in neurofibrillary tangles (NFTs). Diseases with this typical pathological feature are called tauopathies. Parkinson's disease (PD) was not initially considered to be a typical tauopathy. However, recent studies have demonstrated increasing evidence of tau pathology in PD. A genome-wide association (GWA) study indicated a potential association between tauopathy and sporadic PD. The aggregation and deposition of tau were also observed in ~50% of PD brains, and it seems to be transported from neuron to neuron. The aggregation of NFTs, the abnormal hyperphosphorylation of tau protein, and the interaction between tau and alpha-synuclein may all contribute to the cell death and poor axonal transport observed in PD and Parkinsonism.
Parkinson's disease (PD); alpha-synuclien; hyperphosphorylation; tau protein; tauopathy
30333786
PMC6176019
10.3389/fneur.2018.00809
Tauopathy in PD. Tau proteins are integrated with microtubules and stabilize microtubules in physiological condition. However, when tau proteins are hyperphosphorylated, they begin to disintegrate from microtubules, causing neuronal dysfunction. Hyperphosphorylated tau proteins prone to assemble together to form oligomers and develop into filamentous neurofibrillary tangles (NFTs). Hyperphosphorylated tau proteins also interact with α-synuclein to promote aggregation and fibrilization each other, and subsequently cause the formation of lewy bodies and axonal transport dysfunction.
Front Neurol. 2018;9:809.

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Quantitative anatomic measures and comorbid medical illness in late-life major depression. - PubMed - NCBI
AbstractFormatSummarySummary (text)AbstractAbstract (text)MEDLINEXMLPMID ListApplySend to:Choose DestinationFileClipboardCollectionsE-mailOrderMy BibliographyCitation managerFormatSummary (text)Abstract (text)MEDLINEXMLPMID ListCSVCreate File1 selected item: 9169241FormatSummarySummary (text)AbstractAbstract (text)MEDLINEXMLPMID ListMeSH and Other DataE-mailSubjectAdditional textE-mailDidn't get the message? Find out why...Add to ClipboardAdd to CollectionsOrder articlesAdd to My BibliographyGenerate a file for use with external citation management software.Create File
See comment in PubMed Commons belowAm J Geriatr Psychiatry. 1997 Winter;5(1):15-25.Quantitative anatomic measures and comorbid medical illness in late-life major depression.Kumar A1, Miller D, Ewbank D, Yousem D, Newberg A, Samuels S, Cowell P, Gottlieb G.Author information1Department of Psychiatry (Section of Geriatric Psychiatry), University of Pennsylvania School of Medicine, Philadelphia, USA.AbstractThe authors examined the individual and relative roles of atrophy, comorbid medical illness, and cerebrovascular risk factors in the pathogenesis of late-life major depressive disorder (MDD). They used magnetic resonance imaging techniques to study 28 subjects with late-life MDD, 29 healthy control subjects, and 34 subjects with probable dementia of the Alzheimer type (DAT). Depressed subjects showed increases in cerebrospinal fluid volumes comparable to the DAT group but significantly different from control subjects. High-intensity signals, but not measures of atrophy correlated significantly with cerebrovascular risk factor scores. A logistic regression revealed that both brain atrophy and medical illness are associated with an increased risk of developing MDD. Data suggest that both atrophy and comorbid medical illness increase the likelihood of developing MDD in late life.PMID: 9169241 [PubMed - indexed for MEDLINE] SharePublication Types, MeSH Terms, Grant SupportPublication TypesResearch Support, Non-U.S. Gov'tResearch Support, U.S. Gov't, P.H.S.MeSH TermsAgedAged, 80 and overAlzheimer Disease/diagnosis*Alzheimer Disease/epidemiologyAlzheimer Disease/psychologyAtrophyBrain/pathology*Cerebral Ventricles/pathologyCerebrospinal Fluid/physiologyCerebrovascular Disorders/diagnosisCerebrovascular Disorders/epidemiologyCerebrovascular Disorders/psychologyComorbidityDepressive Disorder/diagnosis*Depressive Disorder/epidemiologyDepressive Disorder/psychologyHumansMagnetic Resonance Imaging*Mental Status ScheduleNeurocognitive Disorders/diagnosis*Neurocognitive Disorders/epidemiologyNeurocognitive Disorders/psychologyNeuropsychological TestsReference ValuesGrant SupportKO1 AG 0058/AG/NIA NIH HHS/United StatesMH-52129/MH/NIMH NIH HHS/United StatesLinkOut - more resourcesFull Text SourcesOvid Technologies, Inc.Other Literature SourcesCOS Scholar UniverseMedicalDepression - Genetic AllianceMajor depressive disorder - Genetic AllianceAlzheimer's Disease - MedlinePlus Health InformationMRI Scans - MedlinePlus Health InformationPubMed Commons home


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MONO: an alternative for the .NET framework - CodeProject 12,747,708 members (41,305 online)
Vertyg016-Mar-06 8:41 Really nice work, i would like to know is there any compiler/designer for mono under windows except SharpDevelop, I`m asking this because I can`t desing forms when i create mono project inside SharpDevelop or I will have to use glade ?Thanks! Last Visit: 31-Dec-99 19:00 Last Update: 19-Feb-17 17:58Refresh12 Next »

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Patent US6649841 - Corrugated coaxial cable with high velocity of propagation - Google Patents
A corrugated coaxial cable including a core with at least one inner conductor and a highly expanded polymeric foam dielectric surrounding the inner conductor. This coaxial cable has a corrugated outer conductor closely encapsulating the foam dielectric. The corrugated coax cable is dimensioned to provide...http://www.google.com/patents/US6649841?utm_source=gb-gplus-sharePatent US6649841 - Corrugated coaxial cable with high velocity of propagation
Publication number US6649841 B2
Application number US 09/990,105
Also published as CN1241290C, CN1359166A, DE60122268D1, DE60122268T2, EP1211697A2, EP1211697A3, EP1211697B1, US20020096354
Publication number 09990105, 990105, US 6649841 B2, US 6649841B2, US-B2-6649841, US6649841 B2, US6649841B2
Inventors Vijay K. Chopra, Hugh R. Nudd, James A. Krabec
Patent Citations (28), Referenced by (4), Classifications (10), Legal Events (12)
Corrugated coaxial cable with high velocity of propagation
US 6649841 B2
1. A coaxial cable comprising
an inner conductor,
a foamed polymeric dielectric surrounding said inner conductor and having a density below 0.17 g/cm3, and
a corrugated outer conductor surrounding said dielectric and dimensioned to create a ratio of the actual length of said outer conductor to its linear length such that the cable has a velocity of propagation greater than 90% of the speed of light, the corrugations in said outer conductor forming troughs and crests with the troughs engaging said dielectric.
2. The coaxial cable of claim 1 which has a bend life of at least 30 reverse bends on the minimum bend radius.
providing an inner conductor;
surrounding the inner conductor with a foamed polymeric dielectric, the foamed dielectric having a density below 0.17 g/cm3; and
surrounding the foamed polymeric dielectric with a corrugated outer conductor, the outer conductor forming troughs and crest with the troughs engaging the dielectric, the ratio of the actual length of the outer conductor to its linear length being selected to provide the cable with a velocity of propagation greater than 90% of the speed of light.
11. The method of claim 10, wherein the coaxial cable has a bend life of at least 30 reverse bends on the minimum bend radius.
Velocity 91%
Bend life 30
Crush strength 100 lbs per linear inch.
US3309455 Sep 21, 1964 Mar 14, 1967 Dow Chemical Co Coaxial cable with insulating conductor supporting layers bonded to the conductors
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US4758685 * Nov 24, 1986 Jul 19, 1988 Flexco Microwave, Inc. Flexible coaxial cable and method of making same
US4894488 Feb 10, 1989 Jan 16, 1990 Comm/Scope, Inc. High frequency signal cable with improved electrical dissipation factor and method of producing same
US5110998 Jan 30, 1991 May 5, 1992 E. I. Du Pont De Nemours And Company High speed insulated conductors
US5210377 * Jan 29, 1992 May 11, 1993 W. L. Gore & Associates, Inc. Coaxial electric signal cable having a composite porous insulation
US5235299 * Mar 20, 1992 Aug 10, 1993 Filotex Low loss coaxial cable
US5239134 Jul 17, 1992 Aug 24, 1993 Flexco Microwave, Inc. Method of making a flexible coaxial cable and resultant cable
US5274712 Mar 9, 1992 Dec 28, 1993 Lindsay David S High resistivity inner shields for audio cables and circuits
US5286924 Sep 22, 1992 Feb 15, 1994 Minnesota Mining And Manufacturing Company Mass terminable cable
US5393929 Nov 23, 1993 Feb 28, 1995 Junkosha Co. Ltd. Electrical insulation and articles thereof
US5521331 May 4, 1995 May 28, 1996 Elite Technology Group, Llc Shielded electric cable
US5831215 * Jul 26, 1995 Nov 3, 1998 Alcatel Kabel Ag & Co. High frequency coaxial cable
US5926949 May 29, 1997 Jul 27, 1999 Commscope, Inc. Of North Carolina Method of making coaxial cable
US5959245 May 29, 1997 Sep 28, 1999 Commscope, Inc. Of North Carolina Coaxial cable
US6037545 Sep 23, 1997 Mar 14, 2000 Commscope, Inc. Of North Carolina Coaxial cable
US6137058 Apr 21, 1999 Oct 24, 2000 Commscope, Inc. Of North Carolina Coaxial cable
DE3204761A1 * Feb 11, 1982 Aug 18, 1983 Kabelmetal Electro Gmbh Coaxial high-frequency cable
WO1998013834A1 Sep 22, 1997 Apr 2, 1998 Commscope, Inc. Of North Carolina Coaxial cable and method of making same
US8017867 * Oct 13, 2008 Sep 13, 2011 Ls Cable & System Ltd. Highly foamed coaxial cable
US20030221860 * Apr 8, 2003 Dec 4, 2003 Van Der Burgt Martin Jay Non-halogenated non-cross-linked axially arranged cable
US20080242754 * Jun 10, 2008 Oct 2, 2008 National Research Council Of Canada Low loss foam composition and cable having low loss foam layer
US20100212935 * Oct 13, 2008 Aug 26, 2010 Ls Cable Ltd. Highly foamed coaxial cable
U.S. Classification 174/102.00R, 174/102.00D
International Classification H01P3/06, H01B11/18
Cooperative Classification H01B11/1839, H01B11/1878, H01B11/1808
European Classification H01B11/18B, H01B11/18D2, H01B11/18J
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHOPRA, VIJAY K.;NUDD, HUGH R.;KRABEC, JAMES A.;REEL/FRAME:014328/0750

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BBB Business Profile | Hair World | Reviews and Complaints
Home > Louisiana > Baton Rouge > Hair Products > Hair World
2126 O'Neal Lane

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× × × × × × Tim Brauhn
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You might think the Geneva Conventions protect civilians, or that the Red Cross does. Think again. - The Washington Post
Protesters demonstrate against the U.S. military intervention in Afghanistan outside the White House on Wednesday after the weekend’s airstrike that his a Doctors without Borders hospital in the Afghan city Kunduz. (Mandel Ngan/AFP/Getty Images)
By Margit Bussman and
Does international humanitarian law work to protect civilians on the ground? You might well wonder, especially if you’re aware that Syria, Iraq, Sudan and Nigeria – whose recent wars have all involved terrible civilian carnage — have all signed the Fourth Geneva Convention, which requires that civilians be protected during wartime.
Recently some, in particular political scientist James Morrow, have suggested that ratifying the Laws of War renders both democracies and autocracies complying with the obligation to reduce civilian suffering in interstate conflicts.
Similar questions have dogged the International Committee of the Red Cross (ICRC) with regard to civil war, which is nowadays the dominant form of war. The ICRC has a special status as a humanitarian watchdog, expected to promote respect for international humanitarian law, beyond its role offering healthcare and other basic assistance for soldiers and victims of conflict.
Journalist Philip Gourevitch, among others, has asked whether the ICRC actually does serve as guardian of humanitarian law and prevents civilian casualties during times of civil war, as is its reputation and charge.
As part of a project on civilian victimization in civil wars, we looked to see whether the signatory states held up their commitment to spare the innocents who were not fighting. We conducted an empirical analysis for the years from 1989 to 2004 for 72 countries based on data on the number of civilian victims in civil wars. Information about the state parties’ year of ratification to the treaties related to international humanitarian law and the ICRC’s on-site presence and activities were extracted from the ICRC’s website and the ICRC annual reports.
Unfortunately, what we found suggests that international humanitarian law is of doubtful effectiveness—and that the ICRC is failing as a watchdog for international humanitarian law.
1. International humanitarian laws weaken over time
The effectiveness of international rules decreases slowly with the number of years that have passed since the ratification. We observe more and not less civilian victims, although the number is not very high.
In other words, as each nation’s signing of the Geneva Convention fades further into history, we can expect its number of civilian killings to increase. The modus operandi of the ICRC promises the opposite: Armies will become more accustomed to the treaties over time, getting better at distinguishing between combatants and civilians.
Instead, we conclude that the norms will be forgotten if governments are not regularly reminded of their importance.
2. Rebel forces ignore international humanitarian law
Second, we find that international rules especially fail to reach rebel forces and that the use of force among rebel groups also increases with the years since the ratification of the two treaties. But rebel groups might be particularly interested in cooperating with an international actor and thus improving their legitimacy.
The ICRC could work to encourage rebels fighting corrupt and dictatorial governments that are sanctioned by the United Nations to abide by international humanitarian rules. We do not have evidence for this, but the civil war in Syria suggests that legitimizing the moderates early on during a conflict might make a difference.
3. Having the ICRC around does not reduce civilian deaths
Many believe that simply having the Red Cross onsite will serve as a reminder of international humanitarian law and persuade troop commanders and soldiers to internalize the international norms. But when we compared civil war countries in which the ICRC had established a delegation with countries in which the ICRC was not permanently present neither the on-site, we found that neither having them on site nor their seminars on international humanitarian law reduced attacks on civilians.
Teaching military and police forces to not attack and mistreat civilians is an honorable idea. But it just might not be enough in restraining soldiers.
4. When the ICRC asks forces to spare civilians, it is ignored.
The ICRC usually sees itself as a neutral medical force patching up combatants. On rare occasions, it does publicly condemn and appeal to feuding troops to moderate their violence and spare the innocent. We counted press statements and reports when the ICRC publicly voiced concern and protested against the atrocities.
In fact, we found that the ICRC tends to issue such statements only after a massacre has already taken place. For instance, when we studied the Bosnian civil war, we examined the timing of the use of force and the public diplomacy in the form of “naming and shaming” the disputants. The ICRC voiced its concerns 13 times, 11 times quite mildly.
The ICRC reacts to international humanitarian law abuses. But its public condemnations do not reduce the carnage in the weeks that follow.
Does the law of armed conflict and proactive measures by the ICRC deter violence against civilians during civil wars? Our findings suggest they do not. This may be sobering for those who believe that international agreements will end needless suffering during war.
But our findings do not necessarily suggest that the world should entirely abandon the Laws of War and related international norms. Rather, such agreements may need better sanctioning mechanisms.
The individual risk of being a victim of political violence more generally has decreased significantly in recent decades . The current civil wars in Syria or Iraq threaten to jeopardize this improvement. More proactive ICRC policymaking and an International Humanitarian Law with teeth could reduce civilian suffering.
Margit Bussmann teaches international politics at the University of Greifswald. Gerald Schneider teaches international politics at the University of Konstanz, Germany. This post is drawn from their publication “A Porous Humanitarian Shield: The Laws of War, the Red Cross, and the Killing of Civilians,” Review of International Organizations.