This invention relates to an EUO-structural-type zeolite that comprises at least one element X that is selected from among silicon and germanium and at least one element T that is selected from among aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese. The zeolite of the invention has an X/T ratio of between 5 and 50 and an N/T ratio of between 0.010 and 0.065. This invention also relates to the use of the EUO zeolite as a catalyst in a process for conversion of hydrocarbon feedstocks and more particularly in a process for isomerization of aromatic compounds with 8 carbon atoms per molecule.

This invention relates to a new EUO-structural-type zeolite that has a specific chemical composition of its crystalline framework and a specific nitrogen ratio. The invention also relates to the use of the zeolite as a catalyst in the main processes for transformation of hydrocarbons that uses the refining of petroleum and petrochemistry. It is used in particular in the processes for isomerization of aromatic compounds with 8 carbon atoms that are also called xe2x80x9cC8-aromatic fractions.xe2x80x9d
The isomerization of xylenes of ethylbenzene or a mixture of xylenes and ethylbenzene requires the presence of an acid function and a metal of group VIII. The main purpose of the isomerization of the C8-aromatic fractions is to produce the paraxylene that is the most desired isomer because of its application particularly in the textile industry. The isomerization reaction of the C8-aromatic compounds leads to parasitic reactions that result from the opening of naphthene rings that may or may not be followed by cracking or else reactions of dismutation and/or transalkylation of the C8 aromatic compounds that generate undesirable aromatic compounds.
Catalysts for isomerization of aromatic compounds with 8 carbon atoms were already described. U.S. Pat. No. 4,723,051 and U.S. Pat. No. 4,665,258 describe, for example, optimized formulations with a mordenite zeolite base and a metal of group VIII, but they result in catalysts with which the parasitic reactions are non-negligible. These catalysts lack selectivity of paraxylene in favor of the above-mentioned parasitic reactions that constitute net losses for the desired isomerization reaction.
Other works have shown that the EUO-structural-type zeolites have improved catalytic performance levels, in particular in terms of activity, when said zeolites are used as a catalyst in the isomerization reactions of C8-aromatic fractions. In particular, European Patent Application EP-A-0 923 987 of the applicant relates to catalysts that are prepared with an EUO-structural-type zeolite that has good dispersion and good mechanical resistance of the metal of group VIII and that provide good selectivities.
The EUO-structural-type zeolites are described in the prior art (W. M. Meier and D. H. Olson, xe2x80x9cAtlas of Zeolites Structure Types,xe2x80x9d 4th Edition, 1996) and have a monodimensional microporous network, whose diameter of the pores is 4.1xc3x975.7 xc3x85 (1 xc3x85=1 angstrom=1.10xe2x88x9210 m) N. A. Briscoe et al. taught that these monodimensional channels have lateral pockets with a depth of 8.1 xc3x85 and a diameter of 6.8xc3x975.8 xc3x85 (zeolites, 8, 74, 1988).
The EUO-structural-type zeolites comprise the EU-1 zeolite, the TPZ-3 zeolite, and the ZSM-50 zeolite and generally have the following formula in anhydrous form: 0-100 XO2: 0-10 T2O3: 0-20 R2/nO: where R represents a cation of valence n, X represents silicon and/or germanium, T represents at least one element that is selected from among aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese.
In general, the methods for preparation of EUO-structural-type zeolites comprise the mixing in aqueous medium of a source of an element X, a source of an element T, a source of an alkaline metal and a nitrogen-containing organic compound that acts as a structuring agent.
The EU-1 zeolite, described in European Patent Application EP-A-0 042 226, is prepared by using as a structuring agent either the alkylated derivative of an xcex1-xcfx89 diammonium polymethylene or a degradation product of said derivative or else precursors of said derivative, whereby the structuring agent is found after synthesis in the intracrystalline pores of said zeolite (A. Moini et al, Zeolites, 14, 1994). This EU-1 zeolite preferably has an X/T ratio of between 5 and 75.
The TPZ-3 zeolite, described in European Patent Application EP-A-0 051 318, is prepared by using the same structuring agent family as the one that is employed for synthesizing the EU-1 zeolite. In particular, the use of the compound 1,6-N,N,N,Nxe2x80x2,Nxe2x80x2,Nxe2x80x2-hexamethylhexamethylene diammonium is described. This TPZ-3 zeolite preferably has an X/T ratio of between 10 and 125.
The synthesis processes that use an alkylated derivative of an xcex1-xcfx89 ammonium polymethylene as a nitrogen-containing organic compound result in obtaining zeolites, after synthesis, that generally have an N/Si ratio that is greater than 0.07.
The ZSM-50 zeolite, described in documents EP 0 159 845 and U.S. Pat. No. 4,640,829, is prepared by using as a structuring agent the dibenzyldimethylammonium derivative (DBDMA), which is contained in the intracrystalline pores of said zeolite (A. Thangaraj et al., Zeolites, 11, 1991). This zeolite has an X/T ratio that is greater than 50.
The EUO-structural-type zeolites differ essentially by the nature of the nitrogen-containing organic structuring agent that is present in the solid, after synthesis, and therefore by their respective N/T ratio.
Thus, an EUO zeolite that is obtained with the DBDMA derivative is distinguished essentially, after synthesis, from the EUO zeolites that are synthesized with the xcex1-xcfx89 diammonium polymethylene compounds, by the nature of the cation that is present in the intracrystalline pores. It is also known in the literature that the structure of an EUO zeolite, obtained with DBDMA, differs from that of an EUO zeolite that is obtained with the xcex1-xcfx89 diammonium polymethylene compounds by the arrangement of aluminum atoms within the crystalline network (W. Souverijns et al., Microporous Materials, 4, 123-130, 1995).
Whereas the family of structuring agents used for synthesizing the EU-1 and TPZ-3 zeolites seems to promote obtaining zeolites with a low Si/Al ratio, structuring agents such as the DBDMA promote obtaining zeolites with a high Si/Al ratio. Thus, U.S. Pat. No. 4,640,829 describes a method for preparation of a zeolite that has an Si/Al ratio that is greater than 125 and teaches that DBDMA is particularly effective for promoting nucleation and the growth of crystals of ZSM-50 zeolites that have a high Si/Al ratio. It is also reported that with an Si/Al ratio that is less than 125, the product that is obtained for the most part does not contain the ZSM-50 zeolite. Likewise, Rao et al. (Zeolites, 9, 483-490, 1989) described the synthesis of an EUO-structural-type zeolite with a mixture of benzyldimethylamine and benzyl chloride, precursors of dibenzyldimethylammonium chloride, whereby the zeolite that is obtained has a crystallinity rate that is better, the higher the SiAl ratio. Rao further teaches that for numerous catalytic applications, it is preferable to use zeolites that have a high Si/Al ratio.
This invention is based on the discovery of a new EUO-structural-type zeolite that comprises at least one element X that is selected from among silicon and germanium and at least one element T that is selected from among aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese. The zeolite of the invention is characterized in that it has an X/T ratio of between 5 and 50, preferably between 6 and 35, more preferably between 7 and 30, and even more preferably between 7 and 26 and in that it has an N/X ratio of between 0.010 and 0.065. The zeolite according to the invention is a new EUO-structural-type zeolite. It is differentiated from EU-1 and TPZ-3 zeolites in that it has, after synthesis, a lower N/X ratio, and it is differentiated from the ZSM-50 zeolite by its low X/T ratio. The invention also relates to the use of said zeolite as an element of a catalyst that is used in the processes for transformation of hydrocarbons and in particular in the processes for isomerization of C8-aromatic compounds.
The EUO-structural-type zeolite according to the invention that has low X/T and N/X ratios and that is used subsequently as a catalyst, combined with at least one binder, at least one metal that is selected from among the elements of group VIII, whereby said metal is preferably deposited on the binder, has improved catalytic performance levels in transformation of hydrocarbons in terms of activity, such as, for example, in isomerization of C8-aromatic compounds, i.e., mixtures that consist of xylenes and optionally ethylbenzene. In particular, it was discovered, surprisingly enough, that an EUO-structural-type zeolite that has an N/X ratio that is less than 0.065 and an X/T ratio that is less than 50 results in a more active and more selective catalyst than those with an EUO zeolite base that have an N/X ratio that is less than 0.065 and an Si/Al ratio that is greater than 50, a better activity and a better selectivity that make it possible to increase very considerably the desired yields of aromatic compounds. A catalyst with an EUO zeolite base according to the invention also makes it possible to limit the et losses constituted by the secondary products that are formed during parasitic reactions.
This invention relates to an EUO-structural-type zeolite that comprises at least one element X that is selected from among silicon and germanium and at least one element T that is selected from among aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, whereby said zeolite is characterized in that it has an X/T ratio of between 5 and 50 and an N/X ratio of between 0.010 and 0.065.
The structure of the EUO zeolite according to the invention is identified by x-ray diffractometry. Its crystallinity is calculated from the diffraction diagram by comparison with a reference EUO zeolite. The crystallinity corresponds to the ratio of the surface area of the analyzed peaks of solids to the surface area of the peaks of the reference EUO zeolite, in the diffraction angle field 2xcex8=8 to 40xc2x0. The zeolite according to this invention has a diffraction diagram in accordance with that of the EUO-structural-type zeolites, and it has a crystallinity that is greater than 80%, preferably greater than 85% and even more preferably greater than 90%.
The chemical composition of the EUO zeolite according to the invention is determined by the typical techniques of elementary analyses. In particular, the contents of elements X and T, in particular in silicon and aluminum, are determined by x-ray fluorescence. The X/T ratio, in particular the Si/Al ratio, of the EUO-structural-type zeolite of the invention is between 5 and 50, preferably between 6 and 35, more preferably between 7 and 30, and even more preferably between 7 and 26.
The nitrogen content is determined by catharometric detection after combustion and reduction. The N/X ratio, in particular the N/Si ratio, of the EUO-structural-type zeolite of the invention is between 0.010 and 0.065, preferably between 0.015 and 0.055, and even more preferably between 0.020 and 0.045.
The organic cation that acts as structuring agent and that is present in the intracrystalline pores of the zeolite is identified by nuclear magnetic resonance spectroscopy of carbon 13 at the magic angle under crossed polarization.
The EUO zeolite according to the invention is obtained, for example, according to a synthesis method that comprises the mixture in aqueous medium of at least one source of at least one element X that is selected from among silicon and germanium, at least one source of at least one element T that is selected from among aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, at least one nitrogen-containing organic compound Q or precursors corresponding to said organic compound Q and nuclei of at least one zeolitic material S of the same structural type as the EUO zeolite of the invention. The reaction of the mixture is maintained until the zeolite crystallizes.
Any nitrogen-containing organic compound Q that results in a crude synthesis zeolite that has an N/X ratio of between 0.010 and 0.065, preferably between 0.015 and 0.055 and even more preferably between 0.020 and 0.045, is suitable. Advantageously, the organic compound is the dibenzyldimethylammonium derivative or its precursors. The RMN13C spectrum of the organic compound that is present in the intracrystalline pores of the EUO-structural-type zeolite of the invention corresponds, in this case, to that of the dibenzyldimethylammonium derivative.
Organic structuring agent Q can be a dibenzyldimethylammonium salt, such as, for example, halide, hydroxide, sulfate, silicate or aluminate.
The dibenzyldimethylammonium salts can also be obtained from precursors. Particularly suitable precursors are benzyldimethylamine and benzyl halide or benzyl alcohol. They can be used just as they are in situ or they can be preheated together in the reaction container, preferably in solution before the addition of the other reagents necessary for the synthesis of the EUO-structural-type zeolite.
The zeolitic materials that act as nuclei are at least in part, and preferably totally, of the same structural type as that of the EUO zeolite of the invention. Advantageously, the EUO-structural-type zeolitic nuclei have an X/T ratio of between 5 and 100, where X and T are defined as above. Very preferably, the zeolite of the invention is prepared with zeolitic nuclei that comprise the same elements X and T.
The X/T ratio of said nuclei is preferably between 5 and 50. More preferably, it is between 6 and 35, and even more preferably it is between 7 and 30. Very preferably, the nuclei have the same crystalline composition as that of the EUO zeolite that is to be prepared, i.e., they have the same Si/Al ratio as that of the zeolite that is prepared.
The zeolitic materials that act as nuclei can be introduced during synthesis of the zeolite that it is desired to synthesize under several forms. Thus, the nuclei can be introduced after having undergone at least one of the stages that is selected from among the following stages: washing, drying, calcination and ion exchange. The nuclei can also be introduced in the crude synthesis form.
The zeolitic materials that act as nuclei can be introduced at any time in the preparation of the zeolite that it is desired to synthesize. The nuclei can be introduced at the same time as the sources of elements X and T, organic structuring agent Q, or the nuclei can be introduced first into the aqueous mixture or else the nuclei can be introduced after the introduction of the sources of elements X and T and the structuring agent. The nuclei are preferably introduced after homogenization at least in part from the aqueous mixture that contains the sources of elements X and T and the structuring agent. The size of the particles of zeolitic nuclei can have an influence on the synthesis process, it is suitable for selecting the nuclei that have a particle size such that the synthesis conditions are optimum. Zeolitic nuclei particle is defined as either a zeolite crystal or an aggregate of zeolite crystals where an aggregate is a unit that is formed by at least two zeolite crystals that have at least one contact point between them. Thus, at least the majority (or at least 90% by volume) of the particles of nuclei that are introduced during the preparation of the EUO zeolite have a size of between 0.001 and 500 xcexcm, preferably between 0.005 and 250 xcexcm and even more preferably between 0.005 and 200 xcexcm.
In a particular implementation that may or may not be independent of the preceding implementation, it is advantageous to add to the reaction medium at least one alkaline metal salt P. It is possible to cite, for example, strong acid radicals such as bromide, chloride, iodide, sulfate, phosphate or nitrate, or weak acid radicals such as organic acid radicals, for example citrate or acetate. This salt can accelerate the crystallization of the EUO-structural-type zeolite starting from the reaction mixture.
The reaction mixture that is used in the synthesis of the EUO-structural-type zeolite of the invention generally has the following composition, expressed in oxide form:
preferably, the reaction mixture has the following composition, expressed in oxide form:
and, even more preferably, the reaction mixture has the following composition, expressed in oxide form:
where
X is silicon and/or germanium,
T is at least one element that is selected from among aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese,
Mxe2x80x2 represents an alkaline metal,
Q represents the organic structuring agent or the precursors of said structuring agent,
S represents the zeolite nuclei that are present in crude, dried, calcined or exchanged form,
P represents the alkaline metal salt.
M and/or Q can be present in the form of hydroxides or salts of inorganic or orgnaic acids provided that the OHxe2x88x92/XO2 criterion is satisfied.
The preferred alkaline metal (M+) is sodium. Preferred element X is silicon. Preferred element T is aluminum.
The silicon source can be any one of those whose use is usually considered for the synthesis of zeolites, for example powdered solid silica, silicic acid, colloidal silica or silica in solution. Among the powder silicas that can be used, it is suitable to cite the precipitated silicas, especially those that are obtained by precipitation starting from a solution of an alkaline metal silicate, such as the xe2x80x9cZeosilxe2x80x9d or the xe2x80x9cTixosil,xe2x80x9d produced by Rhodia, the pyrogenated silicas such as the xe2x80x9cAerosilxe2x80x9d produced by Degussa and the xe2x80x9cCabosilxe2x80x9d produced by Cabot and the silica gels. Colloidal silicas of various grain sizes can be used, such as those sold under the filed trademarks xe2x80x9cLUDOXxe2x80x9d of Dupont and xe2x80x9cSYTONxe2x80x9d of Monsanto. The dissolved silicas that can be used are in particular soluble glasses or marketed silicates that contain: 0.5 to 6.0 and especially 2.0 to 4.0 mol of SiO2 per mol of alkaline metal oxide and the silicates that are obtained by dissolution of silica in an alkaline metal hydroxide, a quaternary ammonium hydroxide or a mixture of the latter.
The aluminum source is most advantageously sodium aluminate, but it can also be aluminum, an aluminum salt, for example chloride, nitrate or sulfate, an aluminum alcoholate or the alumina itself, which is preferably in a hydrated or hydratable form such as colloidal alumina, pseuodoboehmite, boehmite, gamma-alumina or the trihydrates.
It is possible to use mixtures of the sources that are cited above. Combined sources of silicon and aluminum can also be used, such as the amorphous silica-aluminas or certain clays.
The reaction mixture is usually caused to react under autogenic pressure, optionally with the addition of a gas, for example, nitrogen, at a temperature of between 85 and 250xc2x0 C. until crystals of the zeolite form, which can last from 1 minute to several months according to the composition of the reagents, the method of heating and mixing, the working temperature and the stirring. The stirring is optional, but preferable, because it shortens the reaction time.
At the end of the reaction, the solid phase is collected on a filter and washed. In that stage, the EUO zeolite according to the invention is called raw straight from synthesis and contains in its intracrystalline pores the nitrogen-containing organic structuring agent, preferably the DBDMA cation. It is then ready for the following operations such as drying, calcination and ion exchange. The zeolite of the invention, after having been subjected to calcination, is freed of nitrogen-containing organic structuring agent, but its X/T ratio remains unchanged. Of course, in calcined form, the zeolite of the invention no longer contains nitrogen.
Thus, to obtain the hydrogen form of the EUO-structural-type zeolite, it is possible to carry out an ion exchange with an acid, especially a strong mineral acid such as hydrochloric acid, sulfuric acid or nitric acid, or with a compound such as ammonium chloride, ammonium sulfate or ammonium nitrate. The ion exchange can be carried out by dilution in one or more steps with the ion exchange solution. The zeolite can be calcined before or after the ion exchange or between two ion exchange stages, preferably before the ion exchange to eliminate any included organic substance to the extent that the ion exchange is facilitated.
Generally, the cation or cations of the EUO-structural-type zeolite can be replaced by one or more of any metal cations and in particular those of groups IA, IB, IIA, IIB, IIIA, IIIB (including the rare earths), VIII (including the noble metals), just as for lead, tin and bismuth (periodic table in xe2x80x9cHandbook of Physics and Chemistry,xe2x80x9d 76th Edition). The exchange is carried out with any water-soluble salts that contain the suitable cation.
This invention also relates to the use of the zeolite of this invention as an acid solid for catalysis in the fields of refining and petrochemistry. Acid solid is defined as the zeolite that is in hydrogen form, i.e., that the crude synthesis zeolite was calcined and exchanged.
The zeolite of the invention can also be used as an adsorbent for the monitoring of pollution and as a molecular sieve for the separation. Advantageously, it is used as nuclei for the synthesis of zeolites of any structural type. When it is used as nuclei, it can be found both in its crude synthesis form and in its calcined form or in its exchanged form.
For example, when the EUO zeolite of the invention is used as a catalyst, it is in calcined form, i.e., rid of nitrogen-containing structuring agent, and it can be combined with an inorganic matrix that can be inert or catalytically active and with a metallic phase.
The inorganic matrix can be present simply as a binder to keep together the small particles of the zeolite in the various known forms of catalysts (extrudates, pellets, balls, powders) or else can be added as a diluent for imposing the degree of conversion into a process that would otherwise proceed at too quick a rate, leading to fouling of the catalyst due to excessive coke formation.
Typical inorganic matrices are in particular substrate materials for the catalysts such as silica, various forms of alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium phosphates, zirconium phosphates, kaolinic clays, bentonites, montmorillonites, sepiolite, attapulgite, fuller""s earth, synthetic porous materials such as SiO2xe2x80x94Al2O3, SiO2xe2x80x94ZrO2, SiO2xe2x80x94ThO2, SiO2xe2x80x94BeO, SiO2xe2x80x94TiO2 or any combination of these compounds.
The EUO-structural-type zeolite of the invention can also be combined with at least one other zeolite and can act as main active phase or additive.
The inorganic matrix can be a mixture of various compounds, in particular an inert phase and an active phase.
The metallic phase is introduced into only the zeolite, only the inorganic matrix or the inorganic matrix-zeolite unit by ion exchange or impregnation with cations or oxides that are selected from among the cations or oxides of the following elements: Cu, Ag, Ga, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and any other element of the periodic table.
The catalytic compositions that comprise the EUO-structural-type zeolite of the invention, in its calcined form, can be applied advantageously in the reactions of isomerization, transalkylation and dismutation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization, aromatization, cracking and hydrocracking, reforming, hydrogenation and dehydrogenation, oxidation, halogenation, amine syntheses, hydrodesulfurization and hydrodenitrification, catalytic elimination of nitrogen oxides, whereby said reactions comprise saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxidized organic compounds and organic compounds that contain nitrogen and/or sulfur, as well as organic compounds that contain other functional groups.
When said EUO zeolite is used as an acid solid in catalytic reactions, the catalyst contains:
at least one EUO-structural-type zeolite of the invention, in its calcined form, that has an X/T ratio of between 5 and 50, preferably between 6 and 35, more preferably between 7 and 30, and even more preferably between 7 and 26,
at least one metal of group VIII, preferably selected from the group that consists of palladium and platinum and even preferably platinum,
at least one binder, preferably alumina,
optionally at least one element that belongs to the group that is formed by the elements of groups IB, IIB, IIIA, IVA, VIB and VIIB, preferably selected from the group that is formed by tin and indium,
optionally sulfur.
More specifically and relative to the weight of the catalyst, the catalyst generally comprises:
1 to 90% inclusive, preferably 3 to 75% inclusive, and even more preferably 4 to 60% inclusive, by weight, of at least one EUO-structural-type zeolite of this invention, in its calcined form, comprising at least one element X that is selected from among germanium and silicon and at least one element T that is selected from the group that is formed by aluminum, iron, gallium, boron, titanium, vanadium, zirconium, molybdenum, arsenic, antimony, chromium and manganese, preferably aluminum and boron, whose atomic ratio X/T is between 5 and 50, preferably between 6 and 35, more preferably between 7 and 30 and even more preferably between 7 and 26, whereby said zeolite comes at least in part in acid form, i.e., in hydrogen H form,
0.01 to 10% inclusive, preferably 0.01 to 2% inclusive, and even more preferably 0.05 to 1.0% inclusive by weight, of at least one metal of group VIII of the periodic table, preferably selected from the group that is formed by platinum and palladium and even more preferably platinum,
optionally 0.01 to 10% inclusive, preferably 0.01 to 2% inclusive, and even more preferably between 0.05 and 1.0% inclusive, by weight, of at least one element of the group that is formed by groups IB, IIB, IIIA, IVA, VIB, and VIIB of the periodic table, preferably selected from the group that is formed by tin and indium,
optionally sulfur, whose content is such that the ratio of the number of sulfur atoms to the number of metal atoms of group VIII that are deposited is between 0.5 and 2 inclusive,
the make-up to 100% by weight of at least one binder, preferably alumina.
Any shaping method is suitable for this catalyst. It is possible to use, for example, pelletizing, extrusion or the shaping of balls. The shaping of the catalyst according to the invention is generally such that the catalyst is preferably in the form of extrudates or balls with a view to its use.
The EUO-structural-type zeolite of this invention is treated by at least one calcination stage, then subjected to at least one ion exchange in at least one NH4NO3 solution to obtain a zeolite whose content of residual alkaline element A, for example sodium, is more or less significant.
The EUO-structural-type zeolite of this invention, in its calcined form, included in the catalyst according to the invention, is at least partly, preferably virtually completely, in acid form, i.e., in hydrogen form (Hxe2x80x2), whereby the content of alkaline element, for example sodium, is preferably such that the A/T atomic ratio is less than 0.5, preferably less than 0.1, even more preferably less than 0.02.
The binder (or matrix) in the catalyst that is used in this invention generally consists of at least one element that is selected from the group that is formed by clays, magnesia, aluminas, silicas, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates and silica-aluminas. The binder is preferably an alumina.
The metals can be introduced either all the same way or by different techniques, at any time of the preparation, before or after shaping and in any order. In addition, intermediate treatments, such as, for example, a calcination and/or a reduction, can be applied between the depositions of various metals.
The preparation of the catalyst can be carried out by any method that is known to one skilled in the art. At least one element of group VIII is introduced into the zeolite or in the binder, preferably in the binder before or after shaping.
A preferred method consists in producing a mixture of the matrix and the zeolite followed by a shaping. The shaping is generally followed by a calcination, generally at a temperature of between 250xc2x0 C. and 600xc2x0 C., inclusive. At least one element of group VIII of the periodic table is introduced after this calcination, preferably by selective deposition on the binder. Said elements are deposited virtually at more than 90% inclusive entirely on the binder in a manner that is known to one skilled in the art by monitoring the parameters that are used during said deposition, such as, for example, the nature of the precursor that is used for carrying out said deposition.
At least one element of group VIII is deposited preferably in the EUO-binder zeolite mixture first shaped by any process that is known to one skilled in the art. Such a deposition is carried out, for example, by the dry impregnation technique, impregnation by excess or ion exchange. All of the precursors are suitable for the deposition of these elements. Preferably, an anion exchange will be used with the hexachloroplatinic acid and/or the hexachloropalladic acid in the presence of a competing agent, for example hydrochloric acid. In this case, the metal is virtually entirely deposited at more than 90% on the binder, and it has good dispersion and good macroscopic distribution through the catalyst grain which constitutes a preferred method for preparation.
Another preferred method for preparation of the catalyst, used in this invention, consists in kneading the EUO-zeolite, in its calcined form, in a moist matrix gel (generally obtained by mixing at least one acid and a matrix powder), for example, alumina, for a period that is necessary for obtaining good homogeneity of the paste that is thus obtained, or, for example, for about 10 minutes, then in passing the paste through a die to form extrudates. Then, after drying, for example for several hours at about 120xc2x0 C. in a drying oven and after calcination, for example for two hours at about 500xc2x0 C., at least one element, for example platinum, is deposited, for example by anion exchange with the hexachloroplatinic acid in the presence of a competing agent (for example hydrochloric acid), whereby said deposition is followed by calcination for example for about 2 hours at about 500xc2x0 C.
Optionally, at least one other element that is selected from the group that is formed by the elements of groups IB, IIB, IIIA, IVA, VIB and VIIB is added. It is possible to add the elements of group VIII and groups IB, IIB, IIIA, IVA, VIB and VIIB either separately at any stage of the preparation of said catalyst or simultaneously in at least one unit stage. When at least one element of groups IB, IIB, IIIA, IVA, VIB and VIIB is added separately, it is preferable that it be added first to the element of group VIII. All of the deposition techniques that are known to one skilled in the art and all of the precursors are suitable.
The platinum is generally introduced into the matrix in the form of hexachloroplatinic acid, but for any noble metal, ammoniated compounds with, in this case deposition of the noble metal in the zeolite, can also be used or compounds such as, for example, ammonium chloroplatinate, dicarbonyl platinum dichloride, hexahydroxyplatinic acid, palladium chloride, and palladium nitrate can be used.
In the case of platinum, it is also possible to cite, for example, tetraamine platinum II salts of formula Pt/(NH3)4X2; hexamine platinum IV salts of formula Pt(NH3)6X4; the halogenopentamine platinum IV salts of formula (PtX(NH3)5)X3; the tetrahalogenodiamine platinum IV salts of formula PtX4(NH3)2; the platinum complexes with the halogen-polyketones and the halogenated compounds of formula H(Pt(acac)2X); whereby X is a halogen that is selected from the group that is formed by chlorine, fluorine, bromine and iodine, and whereby X is preferably chlorine and acac represents the group C5H7O2 that is derived from acetylacetone.
The introduction of the noble metal of the platinum family is preferably carried out by impregnation with an aqueous or organic solution of one of the organometallic compounds that are cited above. Among the organic solvents that can be used, it is possible to cite the paraffinic, naphthenic or aromatic hydrocarbons that contain 4 to 12 carbon atoms, and the halogenated organic compounds that have, for example, 1 to 12 carbon atoms per molecule. It is possible to cite, for example, the n-heptane, methylcyclohexane, toluene and chloroform. It is also possible to use the mixtures of solvents.
The additional element, optionally introduced and selected from the group that is formed by the elements of groups IB, IIB, IIIA, IVA, VIB and VIIB, can be introduced by compounds such as, for example, chlorides, bromides and nitrates, alkyls of elements of groups IB, IIB, IIIA, IVA, VIB and VIIB, or, for example, in the case of tin and indium, alkyl-tin, nitrate and indium chloride.
This element can also be introduced in the form of at least one organic compound that is selected from the group that consists of the complexes of said element, in particular the polyketonic complexes of the metal and hydrocarbyl metals, such as the alkyls, cycloalkyls, aryls, and metal alkylaryls. In the latter case, the introduction of the metal is advantageously carried out with a solution of the organometallic compound of said metal in an organic solvent. It is also possible to use organohalogenated compounds of the metal. As compounds of the metal, it is possible to cite in particular the tetrabutyltin in the case of tin, and the triphenylindium in the case of indium.
The impregnation solvent is selected from the group that consists of the paraffinic, naphthenic or aromatic hydrocarbons that contain 4 to 12 carbon atoms per molecule and the halogenated organic compounds that contain 1 to 12 carbon atoms per molecule. It is possible to cite, for example, the n-heptane, methylcyclohexane and the chloroform. It is also possible to use mixtures of the solvents that are defined above.
The additional metal can optionally be introduced at any time of the preparation, preferably prior to the deposition of one or more metals of group VIII. If this metal is introduced before the noble metal, the compound of the metal that is used is generally selected from the group that consists of halide, nitrate, acetate, tartrate, carbonate and oxalate of metal. The introduction is then advantageously carried out in aqueous solution. It is also possible, however, to be introduced with a solution of an organometallic compound of the metal, for example, tetrabutyltin. In this case, before initiating the introduction of at least one noble metal, calcination under air is initiated.
The preparation of the catalyst generally comprises calcination, usually at a temperature of between about 250xc2x0 C. and 600xc2x0 C. inclusive, for a period of about 0.5 to 10 hours, preferably preceded by drying, for example in a drying oven, at a temperature of between the ambient temperature and 250xc2x0 C., preferably between 40 and 200xc2x0 C. Said drying stage is preferably conducted during the rise in temperature that is necessary for carrying out said calcination.
In the case where the catalyst of this invention contains sulfur, the sulfur is introduced in the calcined, shaped catalyst that contains the metal or metals cited above, either in-situ before the catalytic reaction or ex-situ. The optional sulfurization occurs after the reduction. In the case of a sulfurization in situ, the reduction, if the catalyst was not first reduced, occurs before the sulfurization. In the case of a sulfurization ex-situ, the reduction and then the sulfurization are carried out. The sulfurization is carried out in the presence of hydrogen by using any sulfurizing agent that is well known to one skilled in the art, such as, for example, the dimethyl sulfide or the hydrogen sulfide. For example, the catalyst is treated with a feedstock that contains dimethyl sulfide in the presence of hydrogen, with a concentration such that the sulfur/metal atomic ratio is 1.5. The catalyst is then kept for about 3 hours at about 400xc2x0 C. under hydrogen flow before the feedstock is injected.
The catalyst with an EUO zeolite base of the invention is very advantageously used in the reactions for isomerization of a C8-aromatic fraction that comprises, for example, either a mixture of xylene(s) or ethylbenzene, or a mixture of xylene(s) and ethylbenzene. Said process is generally used according to the following operating conditions:
a temperature of between 300xc2x0 C. and 500xc2x0 C. inclusive, preferably between 320xc2x0 C. and 450xc2x0 C. inclusive and even more preferably between 340xc2x0 C. and 430xc2x0 C. inclusive,
a partial hydrogen pressure of between 0.3 and 1.5 MPa inclusive, preferably between 0.4 and 1.2 MPa inclusive and even more preferably between 0.6 and 1.2 MPa inclusive,
a total pressure of between 0.45 and 1.9 MPa inclusive, preferably between 0.6 and 1.5 MPa inclusive,
a feed volumetric flow rate, expressed in kilograms of feedstock that is introduced per kilogram of catalyst and per hour, between 0.25 and 30 hxe2x88x921 inclusive, preferably between 1 and 25 hxe2x88x921 inclusive, and even more preferably between 2 and 15 h1hxe2x88x921 inclusive.
The invention is illustrated by the following examples.

EUO-structural-type zeolite with a low si/Al ratio and its use as catalyst for isomerization of C8-aromatic fractions


A sealable article container which comprises a flat material having a peripheral edge portion around an outer edge of the material, and binding means, the binding means being located in the peripheral edge portion. The flat material is made of a plastic film, paper sheet, cloth, netting, or mesh. The binding means is selected from the group consisting of: double-backed tape, tongue and groove strips, hook and loop sealing strips, adhesives, or the like. In operation the flat material is placed upon a surface with the binding means facing up, and an article or multiple articles being placed upon the flat material and within the binding means, and thereafter the flat material being folded upon itself so that binding means seals with binding means to form a container for the article or multiple articles.

The present invention provides a sealable article container.
Articles which are not of a standard size or multiple articles which may be of a standard size or multiple articles which are not of a standard size can pose a problem when it comes to collecting and assembling these articles into a container. An example of multiple articles which are not of a standard size is refuse.
Refuse pick up can be a difficult task. For example, for leaf or yard debris pick up, most people use a plastic garbage bag, however if someone is working alone, it is often difficult to open the bag while placing the refuse inside the bag. Some people may use a device which keeps the bag open, such as a garbage can, but then it can be difficult to extract the bag from the can once it is filled with refuse.
Devices are known that use a sheet with a cord or draw string as taught by U.S. Pat. Nos. 2,766,797, 5,092,681, 5,417,462 and 5,713,980. Other debris capturing apparatus are taught by U.S. Pat. Nos. 4,602,664, 5,524,423, 5,664,886 and 5,722,220.


An LED drive circuit that sufficiently exhibits the performance of an LED element to obtain a favorable luminance at room temperature, includes a constant-current circuit including an LED element, a constant-current output unit, and a temperature sensing element having a negative resistance-temperature coefficient. The LED element is connected to the constant-current output unit in series. The constant-current output unit is connected to the LED element in parallel. Due to changes in the resistance value of the constant-current output unit caused by changes in temperature, the value of a current passing through the LED element is increased at room temperature and the value of a current passing through the temperature sensing element is reduced at high temperature.

1. Field of the Invention
The present invention relates to an LED drive circuit and, in particular, to an LED drive circuit for driving an LED element, for example, used as the backlight of the liquid crystal screen of a cell phone, a portable game machine, or the like.
2. Description of the Related Art
An LED element is used as a lighting element, for example, in the backlight of a traffic signal or a liquid crystal display. Also, in recent years, an LED element has been used in the backlight of the liquid crystal screen of a small-size, portable apparatus, such as a cell phone or a portable game machine. As a drive circuit for an LED element in a small-size, portable apparatus as described above, there has been disclosed an LED drive circuit that includes a booster circuit for boosting the voltage by switching the output of a battery and a constant-current circuit for driving an LED element at a constant current and drives the LED element substantially at a constant current and a constant voltage (see, for example, Japanese Unexamined Patent Application Publication No. 2002-359090).
It is known that an LED element suffers thermal damage, such as brownout, due to an increase in the temperature of internal substances included in the LED element at high temperature (for example, 30° C. or more). To avoid this, it is known that the amount of a current to be passed through must be made smaller than that at room temperatures (for example, 10° C. to 30° C.). For this reason, LED element manufacturers indicate the allowable forward current for usage. For example, FIG. 5 shows one example of the allowable forward current of an LED element. According to this example, the allowable forward current is set so that it abruptly decreases as the temperature increases, as shown by a characteristic A of FIG. 5. For this reason, in a related-art LED drive circuit, a circuit is designed so that a current having a constant value that does not exceed the allowable forward current at high temperature passes through the LED element, as shown by a characteristic B of FIG. 5.
However, driving the LED element at a current having such a value means driving the LED element at a current having a value much smaller than the allowable forward current at room temperatures. Therefore, a sufficient luminance cannot be obtained. For this reason, in order to obtain a necessary luminance, multiple LED elements may need to be used. However, in the small-size, portable apparatus field where further downsizing and layer-thickness reduction are in progress, it is required to obtain a sufficient luminance with the least possible LED elements and parts thereof.


A system includes a downhole tool having multiple electric leads. The system also includes a release device that includes an outer shell configured to mechanically couple to the downhole tool, and the outer shell is configured to form a cavity that is fluidly separate from wellbore fluids contained within a wellbore while the outer shell is mechanically coupled to the downhole tool. The release device also includes a contact block configured to electrically couple to the multiple electric leads. In addition, the contact block is configured to electrically decouple from the multiple electric leads while the outer shell remains mechanically coupled to the downhole tool. Further, the contact block is configured to remain in the cavity after electrically decoupling from the plurality of electric leads.

This disclosure relates to systems and methods to release a downhole device in a wellbore, which may enable other downhole devices to continue receiving power.
This section is intended to introduce the reader to various aspects of art that may be related to various aspects of the present techniques, which are described and/or claimed below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present disclosure. Accordingly, these statements are to be read in this light, and not as admissions of any kind.
To locate and extract resources from a well, a wellbore may be drilled into a geological formation. Downhole devices, such as toolstrings and sensors, may be placed into the wellbore to obtain measurements relating to the wellbore. In some cases, several downhole devices may be connected in a string of downhole devices connected to each other. The string of downhole devices may receive electrical power from upstream power sources at the surface or from a battery located in another downhole device. Multiple electrical leads, which may include wires or other conductors, may provide the electrical power to each of the downhole devices.
In some situations, one of the downhole devices may be released into the wellbore, causing that downhole device to become mechanically and electrically decoupled from the string of downhole devices. When this happens, the electrical leads between the released downhole device and the remaining string of downhole devices may become exposed to fluid present in the wellbore, which may short electrical leads still receiving electricity. This may effectively deactivate not just the downhole device that was released, but also the remaining string of downhole devices that were not released.

Systems and methods for a release device


Provided is a gear device capable of resolving inconveniences such as abnormal wear that arises due to the relative misalignment between the internal gear pins and the external gear, and inhibiting an increase in the number of components. This gear device has an outer cylinder, internal gear pins, and a carrier. A plurality of pin grooves extending in the axial direction of the outer cylinder are formed on the inner peripheral face of the outer cylinder, and the internal gear pins are fitted in the pin grooves. The pin grooves are formed so that the length of the pin grooves becomes longer than the length of the internal gear pins. The carrier has a pair of pressing members which includes a pressing surface. The pressing surface is configured to regulate movement of the internal gear pins and an oscillating gear which includes external teeth in the axial direction.

As an eccentrically oscillating gear device for driving members configuring a robot; that is, robot members and the like, conventionally known is a gear device with a built-in main bearing which supports an external load that is applied to the robot members. With this kind of gear device, as described in Japanese Patent Application Publication No. 2005-47006, a carrier is rotatably mounted inside a cylindrical case via a pair of main bearings. A plurality of pin teeth are provided to an inner peripheral face of the cylindrical case. The pin teeth are sandwiched between the pair of main bearings aligned in an axial direction and their movement in the axial direction is thereby regulated. The pin teeth are pin-shaped members. An internal gear is configured as a result of the pin teeth being disposed at regular intervals on the inner peripheral face of the cylindrical case. The pin teeth can engage with external teeth of an oscillating gear which oscillates and rotates in conjunction with the rotation of the crank shaft. With the configuration of this gear device, since the pair of main bearings is housed in a case of the gear device, the robot members can be used by being respectively fixed to the case of the gear device and a carrier, and the main bearing is not required on the side of the robot member.
Here, when a pair of robot members is rotatably coupled to each other via the main bearing provided outside the gear device, the main bearing for receiving the external load of the robot members can be omitted in the gear device. With a gear device that does not have such a main bearing built therein, for example, as with the gear device described in Japanese Examined Utility Model Application Publication No. H4-29988, movement of the internal gear pins in the axial direction is regulated by providing a pair of snap rings to both upper and lower ends of the internal gear pins on the inside of the cylindrical case. Meanwhile, movement of the oscillating gear in the axial direction is regulated by the carrier as with conventional technology.
With a gear device that does not have such a main bearing built therein, variation in the assembly width of the main bearing outside the gear device that occurs due to dimensional errors of components is absorbed by the movement of the relative position of the internal gear pins and the oscillating gear.
With the gear device described in Japanese Examined Utility Model Application Publication No. H4-29988, since movement of the oscillating gear in the axial direction is regulated by the carrier, and movement of the internal gear pins in the axial direction is regulated by a snap ring on the side of the case, variation in the assembly width of the main bearing provided independently from the gear device is absorbed based on the movement of the relative position of the internal gear pins and the oscillating gear. Thus, when the relative shift amount of the internal gear pins and the oscillating gear in the axial direction is large, the contact width and the contact area of the internal gear pins and the oscillating gear will decrease and, consequently, there is a possibility that early breakage such as abnormal wear may occur (for example, refer to the internal gear pin 103 and the oscillating gear 106 shown in FIG. 7).
Moreover, since a pair of snap rings is provided in order to regulate the movement of the internal gear pins in the axial direction, the number of components of the gear device will increase.


The liquid dispenser comprises a ratchet assembly, a rotor assembly, a reservoir assembly, and a drive mechanism. The reservoir assembly includes a reservoir and a reservoir tube; and the rotor assembly includes a drive gear and at least one compression element. The ratchet assembly includes a pawl configured to engage the drive gear when the drive mechanism is actuated. Optionally, the liquid dispenser includes a venting assembly and/or a dose control assembly. The venting assembly automatically vents the reservoir when the reservoir is mounted in the liquid dispenser. The dose control assembly allows the user to control the distance the drive mechanism may be actuated and thereby control the amount of liquid that is dispensed. The liquid dispenser of the invention provides accurate control over the amount of liquid that is dispensed as well as ease in replacing the reservoir.

In a standard liquid dispenser, a liquid is pumped by one of many means. Particularly for liquids containing a coarse grit material, the method of pumping is with a diaphragm pump, tube pump (where the tube is compressed to seal then push fluid out), and piston pumps.
In some situations, accurate measurement of liquids is desirable when dispensing the liquids. Too little liquid may be insufficient to sanitize the object receiving the liquid. Too much liquid is wasteful and increases cost. Standard liquid dispensers do not provide an accurate means of controlling the amount of liquid that is dispensed. In diaphragm and tube pumps, the pumps swell as they are being compressed which allows some of the fluid in the pump to remain, resulting in pumps that are inefficient at controlling the volume of fluid. Even with dosage control mechanisms, the pumps cannot consistently deliver an appropriate amount of liquid. Piston pumps do not effectively deliver grit soaps because the piston/cylinder assembly wears unpredictably and may leak or not pump efficiently.
Finally, bag-in-box type fluid reservoirs, which have some form of plastic liner and cardboard exterior package (bag-in-box), do not evacuate efficiently because the bag can fold on itself and trap fluid not allowing it to be pumped from the bag.


A fundus imaging system includes: an image sensor array, where the image sensor array includes monochrome photodiodes and global shutter control, an illumination unit with one or more light-emitting diodes that have one or more dies, a computing system including a processor and memory, one or more lenses, one or more reflective mirrors, and a display. In an example method of use, a clinician positions a patient, initiates a focal adjustment, initiates a retinal imaging process, and the same or a different clinician views the image. In some embodiments, the imaging system is configured to analyze the image and identify detected physical attributes in the image relating to the diagnosis and treatment of diabetic retinopathy.

People with type 1 or type 2 diabetes can develop eye disease as a result of having diabetes. One of the most common diabetic eye diseases is diabetic retinopathy, which is damage to the blood vessels of the light-sensitive tissue at the back of the eye, known as the retina. Eye exams can produce images of the back of the eye and trained medical professionals use those images to diagnose and treat diabetic retinopathy.
Many of the current methods used to produce the images of the back of the eye, known as a fundus, suffer from various deficiencies, often producing imperfect images that can complicate the diagnostic procedure. Traditional imaging techniques use a Bayer-patterned color filter array imaging sensor. Such techniques have low sensitivity and the resulting image often suffers demosaic artifacts caused by low color resolution. Additionally, many of the current methods require the dilation of the patient's eyes, which is uncomfortable and inconvenient.


An atomic layer deposition method includes positioning a plurality of semiconductor wafers into an atomic layer deposition chamber. Deposition precursor is emitted from individual gas inlets associated with individual of the wafers received within the chamber effective to form a respective monolayer onto said individual wafers received within the chamber. After forming the monolayer, purge gas is emitted from individual gas inlets associated with individual of the wafers received within the chamber. An atomic layer deposition tool includes a subatmospheric load chamber, a subatmospheric transfer chamber and a plurality of atomic layer deposition chambers. Other aspects and implementations are disclosed.

Semiconductor processing in the fabrication of integrated circuitry typically includes the deposition of layers on semiconductor substrates. One such method is atomic layer deposition (ALD), which involves the deposition of successive monolayers over a substrate within a deposition chamber typically maintained at subatmospheric pressure. With typical ALD, successive monoatomic layers are adsorbed to a substrate and/or reacted with the outer layer on the substrate, typically by the successive feeding of different deposition precursors to the substrate surface.
An exemplary ALD method includes feeding a single vaporized precursor to a deposition chamber effective to form a first monolayer over a substrate received therein. Thereafter, the flow of the first deposition precursor is ceased and an inert purge gas is flowed through the chamber effective to remove any remaining first precursor which is not adhering to the substrate from the chamber. Subsequently, a second vapor deposition precursor, different from the first, is flowed to the chamber effective to form a second monolayer on/with the first monolayer. The second monolayer might react with the first monolayer. Additional precursors can form successive monolayers, or the above process can be repeated until a desired thickness and composition layer has been formed over the substrate.
Present ALD tools and methods include both single wafer depositions and multiple wafer depositions. Single wafer ALD systems suffer from inherent limitations of throughput due to slow deposition rate of the process and in single wafer processing. Multiple wafer depositions employ furnace-type tools which typically retain 200 or more wafers therein for deposition. Accordingly, such have very large reactor volumes typically requiring very long deposition precursor pulse times, as well as purge gas pulse times, which can negate a significant part of the throughput gain in processing multiple wafers at a time. Further, such large reactor volumes create inherent cleaning problems and short cleaning intervals to prevent the peeling of material from the sidewalls of the furnaces which can deposit on the wafers.
While the invention was motivated in addressing the above issues and improving upon the above-described drawbacks, it is in no way so limited. The invention is only limited by the accompanying claims as literally worded (without interpretative or other limiting reference to the above background art description, remaining portions of the specification, or the drawings), and in accordance with the doctrine of equivalents.

This patent is subject to a terminal disclaimer.

Atomic layer deposition methods and atomic layer deposition tools


A cathode mixture, a non-aqueous electrolyte secondary battery, and manufacture method thereof are provided. The cathode mixture for a non-aqueous electrolyte secondary battery includes: a cathode active material having an olivine type crystal structure; and an inorganic oxide which does not contribute to charge and discharge. A particle diameter A of the cathode active material lies within a range from 0.1 μm or more to 0.5 μm or less. There is a relation of A>B between the particle diameter A of the cathode active material and a particle diameter B of the inorganic oxide.

The present application relates to a cathode mixture, a non-aqueous electrolyte secondary battery, and its manufacturing method. More particularly, the invention relates to a non-aqueous electrolyte secondary battery using a cathode active material having an olivine type crystal structure.
In recent years, many portable electronic apparatuses such as camera integrated type VTR (Video Tape Recorder), cellular phone, laptop computer, and the like have been put into practical use and their miniaturization and light weights have been realized. Studies and developments to improve an energy density are vigorously being progressed with respect to batteries, particularly, secondary batteries as portable power sources of those electronic apparatuses. According to a lithium ion secondary battery among batteries using a non-aqueous electrolytic solution, since a larger energy density is obtained as compared with that of a lead battery or a nickel cadmium battery as an electrolytic solution secondary battery of an aqueous solution system in the related art, an expectation degree is large and their market is remarkably growing.
Particularly, in recent years, since features such as light weight and high energy density of the lithium ion secondary battery are suitable for uses of an electric automobile and a hybrid electric automobile, an examination to realize a large size and a high power of such a battery is vigorously being progressed.
In the lithium ion secondary battery for a general use or the like, generally, lithium cobalt acid LiCoO2 is mainly used as a cathode active material. However, there is a problem on a price and a supply amount from a viewpoint of an estimated amount of deposits of lithium cobalt acid. Therefore, such a tendency that a reasonable material in which anxiety about the supply amount is small is used is predicted.
Under such a situation, lithium iron phosphate LiFePO4 using reasonable iron whose production amount is large is highlighted. However, according to lithium iron phosphate, since an insertion/desorption reaction of lithium at the time of battery charge and discharge is slower and an electric resistance is larger as compared with those of lithium cobalt acid used in the related art, there is such a problem that in the charge and discharge of a large current, it is difficult to obtain a sufficient charge/discharge capacitance in association with an increase in overvoltage.
With respect to such a problem, various countermeasures have been taken and, for example, the following methods (1) to (4) have been proposed.
(1) A particle diameter of an active material is reduced and a specific surface area is increased.
(2) A conductive assistant such as carbon or the like is held on the particle surface of the active material.
(3) When a cathode mixture is manufactured, carbon black, fibrous carbon, or the like is added.
(4) An adhesive force of component members is improved by using a binder having a large binding force.
Specifically speaking, the above methods (1) to (4) have been disclosed in following Patent Documents 1 to 4.
Patent Document 1: JP-A-2002-110162
Patent Document 2: JP-A-2001-110414
Patent Document 3: JP-A-2003-36889
Patent Document 4: JP-A-2005-251554
(1) In Patent Document 1, there has been disclosed such a technique that a particle diameter of the primary particle of lithium iron phosphate is limited to 3.1 μm or less and the specific surface area of the cathode active material is sufficiently increased, thereby increasing an electronic conductivity in the cathode.
(2) In Patent Documents 2 and 3, such a technique that a conductive microparticle is held on the particle surface of lithium iron phosphate and the active material is improved, thereby raising the charge/discharge capacitance in the charge/discharge of the large current has been disclosed.
(3) To reduce the electric resistance of the cathode, powdered carbon such as carbon black, flake carbon such as graphite, or fibrous carbon is generally mixed.
(4) In Patent Document 4, there has been disclosed such a technique that by using a binder having a large binding force, an adhesion between the cathode active material and the conductive assistant, an adhesion between the cathode active material and a collector, and an adhesion between the collector and the conductive assistant are improved, thereby improving characteristics at the time of the large-current charge/discharge.
The electric resistance of the cathode decreases by the foregoing methods of (1) to (4). However, to adapt to the battery for a high-power application which is used in the electric automobile, a hybrid automobile, or the like, according to lithium iron phosphate having the olivine type crystal structure, it is still difficult to obtain sufficient output characteristics as compared with those of lithium cobalt acid having a stratified structure or those of lithium manganese acid having a spinel structure.
It is also understood that if the foregoing methods of (1) and (3) are used, another problem in which life characteristics deteriorate at a high temperature also occurs.

Cathode mixture, non-aqueous electrolyte secondary battery, and its manufacturing method


A needle fill valve, in which a bearer is set on the top of a body, the bearer is covered on an upper cover, a front cavity is set on the front side of the bearer, an inner cavity is set on the location corresponding to the front cavity for placing the annular gasket of the sealing plate wrapped a sealing valve pad, and the purpose of fixing the sealing valve pad for preventing being disengaged from the annular gasket is achieved by fastening an upper fixed seat and a lower fixed seat.

1. Field of the Invention
The present invention relates to a needle fill valve and, more particularly, to a needle fill valve for preventing the valve pad from being disengaged from the needle fill valve of the sealing plate, to thereby ensure proper operation of water inflowing and water sealing and extend the service life.
2. Brief Description of the Related Art
The known technology of the needle fill valve, such as the cited references U.S. Pat. No. 4,180,096, U.S. Pat. No. 3,895,645, U.S. Pat. No. 4,345,619, U.S. Pat. No. 4,240,606 etc., the related technology has been implemented for several years, the structure of this type of fill valve is quite mature substantially. However, the only drawback is that the valve pad 12 may be disengaged easily in the part of the sealing plate 1 (as shown in FIG. 1 and FIG. 2), the problem is due to the combination method of the annular gasket 11 of the sealing plate 1 and the valve pad 12. Since the annular gasket 11 is embedded into the inner groove 122 on the inner side of the inner flange 121 on the top of the valve pad 12, the valve pad 12 made from rubber material may easily cause elastic fatigue at the embedded place after moving up and down under long-term pressure, the valve pad 12 may not be tight around the circumference of the annular gasket 11 and may disengaged from the annular gasket 11, so that the operation of water inflowing and water sealing of the fill valve is out of control.


Instant messaging contacts received at a contact center are directed to a conference with other such contacts before being allocated to an agent. In this way, customers of the contact center are entertained while waiting and have the ability to resolve one another's problems, thereby reducing the load on the contact center's agents. In another aspect, automated instant messaging scripts interact with the customer to elucidate the nature of the customer contact before directing the contact to a human agent.

Modern contact centers are equipped to handle contacts of various different media types, including voice and video telephony, emails and IM contacts. In a conventional contact center, IM contacts are handled by an IM server of the contact center which generally operates in an analogous manner to the call server or switch of the contact center in handling voice calls.
Thus, instant messaging contacts received from external parties (customers) generate a contact entity in the management systems of the contact center. That contact entity, which can be represented by a token or file, or by an object in object oriented systems, is prioritised and allocated to an agent or, if no agent is available, placed in a queue. Queuing may be organised with queues for particular skillsets. For example, the IM contact may be made to an IM address of the contact center which is associated with a particular skillset or which is associated with, for example, a particular language. In this way, a contact can be queued for an agent who is likely to be equipped to deal with the customer in question. When the contact reaches the top of its queue, it is allocated to the next available agent, and the IM server creates an IM session between the agent and the customer associated with the contact, following which the agent and customer can "chat" with one another using IM message exchanges.
Treating IM messages in this way, using the model of voice calls, does not allow the contact center provider to offer any unique services in respect of IM customers.

Managing instant messenger contacts at a contact center


There is disclosed a process for forming a photocathode having high quantum yield which comprises the first step of making a number of fine concavities and convexities in a surface of a substrate finished substantially in a mirror; the second step of blunting the fine concavities and convexities; and the third step of coating a photoelectron emissive material on the surface of the substrate.

1. Field of the Invention
This invention relates to a photoemitting device and a process for forming a photocathode, which is used in forming the photocathode of, e.g., semitransparent photomultipliers (PMT).
2. Related Background Art
It is known that the photocathode emits photoelectrons outside of a photoelectron emissive material in response to incident radiation. An important consideration with the formation of the photocathode is improvement of the so-called quantum yield. The photocathode is conventionally formed by applying Sb and an alkali metal, such as, K (potassium), Cs (caesium) or others, to a glass substrate finished as a mirror. The resultant photocathode has 25 to 27% in terms of quantum yield.
The level of the quantum yield directly affects the photosensitivity of a PMT with a photocathode. Due to this fact, conventionally there have been proposed some techniques for improving the photoelectron emission efficiency. To give examples, Y. Yajima et al. have proposed in Japanese Patent Laid-Open Publication (JPLO) 37561/1974 a photocathode having an electrically conductive substance coated selectively on the coating of an optical fiber plate. Y. Watase has proposed in (JPLO) 92079/1975 a technique for forming a stepped photocathode. Gordon Peter et al. have proposed in British Patent Application No. 6701/66 a technique for forming a number of prism elements on a glass plate to improve quantum yield. J. G. Edritz et al. have proposed in U.S. Pat. No. 406183 a technique for forming rectangular concavities and convexities in a glass plate to improve photoelectron emission efficiency. In addition to these techniques, various studies have been made without being able to attain a satisfactory level.

Photoelectron emitting device having a photocathode made of photoelectric material


A fuel composition for a fuel injected diesel engine, a method for improving performance of fuel injectors and a method for cleaning fuel injectors for a diesel engine. The fuel composition includes a major amount of fuel and a minor effective amount of a reaction product of (i) a hydrocarbyl substituted compound containing at least one tertiary amino group and (ii) a halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof, wherein the reaction product as made is substantially devoid of free anion species.

It has long been desired to maximize fuel economy, power and driveability in diesel fuel powered vehicles while enhancing acceleration, reducing emissions, and preventing hesitation. While it is known to enhance gasoline powered engine performance by employing dispersants to keep valves and fuel injectors clean in port fuel injection engines, such gasoline dispersants are not necessarily effective fuel injected diesel engines. The reasons for this unpredictability lie in the many differences between the fuel compositions that are suitable for such engines.
Additionally, new engine technologies require more effective additives to keep the engines running smoothly. Additives are required to keep the fuel injectors clean or clean up fouled injectors for spark and compression type engines. Engines are also being designed to run on alternative renewable fuels. Such renewal fuels may include fatty acid esters and other biofuels which are known to cause deposit formation in the fuel supply systems for the engines. Such deposits may reduce or completely bock fuel flow, leading to undesirable engine performance.
Some additives, such as quaternary ammonium salts that have cations and anions bonded through ionic bonding, have been used in fuels but may have reduced solubility in the fuels and may form deposits in the fuels under certain conditions of fuel storage or engine operation. Also, such quaternary ammonium salts may not be effective for use in fuels containing components derived from renewable sources. Accordingly, there continues to be a need for fuel additives that are effective in cleaning up fuel injector or supply systems and maintaining the fuel injectors operating at their peak efficiency.
Also, low sulfur diesel fuels and ultra low sulfur diesel fuels are now common in the marketplace for such engines. A "low sulfur" diesel fuel means a fuel having a sulfur content of 50 ppm by weight or less based on a total weight of the fuel. An "ultra low sulfur" diesel fuel (ULSD) means a fuel having a sulfur content of 15 ppm by weight or less based on a total weight of the fuel. Low sulfur diesel fuels tend to form more deposits in diesel engines than conventional fuels, for example, because of the need for additional friction modifiers and/or corrosion inhibitors in the low sulfur diesel fuels.
In accordance with the disclosure, exemplary embodiments provide a diesel fuel composition for an internal combustion engine comprising, a method for improving performance of fuel injectors, and a method for cleaning fuel injectors for an internal combustion engine. The fuel composition includes a major amount of fuel and a minor effective amount of a reaction product of (i) a hydrocarbyl substituted compound containing at least one tertiary amino group and (ii) at least on halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof, wherein the reaction product as made is substantially devoid of free anion species.
Another embodiment of the disclosure provides a method of improving the injector performance of a fuel injected diesel engine. The method includes operating the engine on a fuel composition comprising a major amount of fuel and from about 5 to about 200 ppm by weight based on a total weight of the fuel of a reaction product of (i) a hydrocarbyl substituted compound containing at least one tertiary amino group and (ii) at least one halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof, wherein the reaction product as made is substantially devoid of free anion species. The reaction product present in the fuel is effective to improve the injector performance of the engine by at least about 80% when measured according to a CEC F98-08 DW10 test.
A further embodiment of the disclosure provides a method of operating a fuel injected diesel engine. The method includes combusting in the engine a fuel composition comprising a major amount of fuel and from about 5 to about 500 ppm by weight based on a total weight of the fuel of a reaction product of (i) a hydrocarbyl substituted compound containing at least one tertiary amino group and (ii) at least one halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof, wherein the reaction product as made is substantially devoid of free anion species.
Another embodiment of the disclosure provides an additive concentrate for a fuel for use in an injected diesel fuel engine. The additive concentrate includes a reaction product of (i) a hydrocarbyl substituted compound containing at least one tertiary amino group and (ii) at least one halogen substituted C2-C8 carboxylic acid, ester, amide, or salt thereof, wherein the reaction product as made is substantially devoid of free anion species; and at least one component selected from the group consisting of diluents, compatibilizers, corrosion inhibitors, cold flow improvers (CFPP additive), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition accelerators, and cyclomatic manganese tricarbonyl compounds.
An advantage of the fuel additive described herein is that the additive may not only reduce the amount of deposits forming on fuel injectors, but the additive may also be effective to clean up dirty fuel injectors sufficient to provide improved power recovery to the engine.
Additional embodiments and advantages of the disclosure will be set forth in part in the detailed description which follows, and/or can be learned by practice of the disclosure. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.

Fuel additive for improved performance in fuel injected engines


Methods, systems, and computer-readable storage media for tuning behavior of a machine learning (ML) model by providing an alternative loss function used during training of a ML model, the alternative loss function enhancing reliability of the ML model, calibrating the confidence of the ML model after training, and reducing risk in downstream tasks by providing a mapping between the confidence of the ML model to the expected accuracy of the ML model.

In general, machine learning includes training a machine learning (ML) model that receives input and provides some output. Machine learning can be used in a variety of problem spaces. An example problem space includes autonomous systems that are tasked with matching items of one entity to items of another entity. Examples include, without limitation, matching questions to answers, people to products, bank statements to invoices, and bank statements to customer accounts.
In use, a ML model outputs a confidence score with a prediction. The confidence score indicates the confidence in the accuracy of the prediction made by the ML model. Higher confidence scores imply higher confidence from the ML model. This interpretation is important not only for users reviewing the ML model, but also for any other algorithms or systems that act upon the output of the ML model. For example, in a downstream task that uses the output of an upstream ML model, a downstream ML model may take the confidences of the upstream ML model into account in performing the downstream task.
In some instances, a ML model can be considered overly confident, if the ML model provides relatively high confidence scores for all predictions it outputs. If the (upstream) ML model is overly confident, confusion can result in downstream systems. Hence it is imperative for a model to output reliable confidence scores associated with its predictions.

Calibrating reliability of multi-label classification neural networks


A method and a system of cleaning and flushing a beverage dispensing system comprising a sealable pressure chamber for receiving a collapsible keg containing a beverage and a dispensing valve, comprises: providing a first cartridge containing a cleaning fluid, positioning the first cartridge in the pressure chamber and pressurizing the pressure chamber, opening the dispensing valve and dispensing the cleaning fluid from the dispensing valve, and causing the cleaning fluid to flow from the first cartridge through the dispensing line and being dispensed from the dispensing valve, disconnecting the first cartridge after the emptying of the cleaning fluid from the first cartridge, and removing the first cartridge, providing a second cartridge containing a flushing fluid, positioning the second cartridge in the pressure chamber and pressurizing the pressure chamber, and repeating the steps (iii)-(v) while using the second cartridge instead of the first cartridge.

Beverage dispensing systems are typically used in beverage dispensing establishments for efficiently dispensing large quantities of beverage. Typically, beverage dispensing systems are used to dispense carbonated alcoholic beverages such as draught beer and cider. However, also non-alcoholic beverages such as soda and non-carbonates beverage such as wine and fruit juice may be dispensed using a beverage dispensing system. Beverage dispensing systems are mostly for professional users such as in establishments like bars, restaurants and hotels, however, increasingly also for private users such as in private homes.
Professional beverage dispensing systems typically dispense beverage provided in large beverage kegs. Such beverage kegs may hold 20-50 liters of beverage for a professional beverage dispensing system for allowing typically 50-100 beverage dispensing operations before needing to exchange beverage keg. In the past, beverage kegs were made of solid materials such as steel and re-filled a number of times. In-between each filling the beverage kegs would have to be carefully cleaned, which has proven to be very costly. Insufficient cleaning may lead to unhygienic beverage kegs, which may in turn lead to health problems for the beverage consumer. More recent beverage kegs are made collapsible for single use only due to the above hygiene concern. An example of such a beverage dispensing system using collapsible beverage kegs is the DraughtMaster™ system provided by the applicant company. Such beverage dispensing systems using collapsible beverage kegs typically have the beverage keg installed in a pressure chamber. When dispensing beverage from the beverage dispensing system, a pressure fluid is allowed to enter the pressure chamber. When dispensing beverage from the beverage keg, the pressure fluid acts on the beverage keg and the beverage keg collapses. The volume of the beverage keg is reduced corresponding to the amount of dispensed beverage. The collapsible beverage kegs are preferably made of flexible and disposable material such as plastic.
When performing a dispensing operation the force of the pressure forces the beverage out of the beverage container and into a dispensing line. The dispensing line leads to a dispensing device typically having a dispensing valve and a handle for allowing an operator to control the dispensing valve. The operator, such as a bartender or barmaid, uses the dispensing device to control the rate of dispensing. After each beverage dispensing operation, some amount of residual beverage will inevitably be left in the dispensing line and in the dispensing device. After a certain amount of time a layer of residual beverage may be formed inside the dispensing line and dispensing device. Such layers of residual beverage may solidify and eventually clog the dispensing line and/or the dispensing device, which will interrupt the beverage dispensing operation. However, well before clogging the dispensing line and/or device, the residual beverage will pose a hygienic problem. The dispensing line and the dispensing device constitute areas where bacterial growth may be accelerated due to the presence of beverage, the large surface area in comparison to the beverage volume, the lack of sufficient cooling and the close proximity to the outside. Bacterial growth due to lack of hygiene in the dispensing line and the dispensing device may constitute a health problem for the beverage consumer. Therefore there is a need for technologies for cleaning the dispensing line and the dispensing device after a certain period of time or alternatively after a certain number of dispensing operations.
The above problem may for private users be solved by using a disposable dispensing line and dispensing device intended for single use only. For a professional user a single use dispensing line and dispensing device would mean that the operator would have to reinstall the dispensing line and dispensing device regularly, possibly several times a day. Frequent installation, which would require considerably more time, compared to having the dispensing line and dispensing device permanently installed in the establishment. Some establishments may have the pressure chamber in a different location, such as in the basement below the actual dispensing location, which would require even larger effort for changing the dispensing line. In such establishments the tapping device itself will typically be made of non-disposable materials for the reason of good appearance.
In published PCT application WO 2009/024147 claiming priority from European patent application 07388059.3 filed on the 20 Aug. 2007, a beverage distribution system having a separate rinsing line has been described. By using a specially designed dispensing valve, alternative rinsing fluid or beverage may enter the dispensing line. Rinsing fluid is provided from a separate pressurized reservoir. The dispensing valve includes safety features for avoiding mixing rinsing fluid and beverage. This solution to the above problem would, however, need additional investments and would not be suitable for already present establishments.
In WO 2007/076584A2 an automatic home multi beer dispensing apparatus is described. The above publication briefly describes that a cleaning cartridge may be used for cleaning the beverage dispensing apparatus. However, the publication does not describe any further details how the cleaning is performed.

Apparatus and method for cleaning and flushing a beverage dispensing system


The present invention discloses the use of [R]-3-(2-deoxy-.beta.-D-erythropentofuranosyl)-3,6,7,8-tetrahydroimidazo-[ 4,5-d][1,3]diazepin-8-ol, also commonly known as pentostatin, or a pharmaceutically acceptable salt thereof, or a pharmaceutical composition comprised of such compounds, in the prophylactic or affirmative treatment of cerebral and cardiovascular disorders such as cerebral and myocardial ischemia. The invention also discloses the administration of pentostatin along with adenosine in the prophylactic or affirmative treatment of cerebral and cardiovascular disorders.

Approximately 400,000 coronary artery bypass graft (CABG) procedures are conducted annually in the United States. The frequency of the most debilitating problems (such as myocardial infarction, postoperative low cardiac output syndrome, and stroke) are estimated to be in the range of 5-10%, whereas modest cardiac dysfunction and cognitive disorders may have frequencies of 50-60%. Unfortunately it is difficult to obtain a precise fix on the frequency of heart and CNS related complications in surgeries with cardiopulmonary bypass because the definitions of "complications" vary and there may be a tendency to miss significant problems when they are assessed retrospectively rather than observed prospectively. Even if estimates as low as 5% are correct, this percentage represents 20,000 patients that will be able to benefit from improved protection during a CABG operation. A potentially more important factor that could influence the complication rates now and in the future may be the changing demographics of the surgical populations. Since patients undergoing CABG procedures are tending to be older and higher risk individuals as the general population ages, it appears likely that the frequency of serious complications will increase.
During CAGB operations, the heart and lungs are isolated from the rest of the circulatory system which is supported by a cardiopulmonary bypass pump. Hypothermia, cardioplegia and other means of protecting the heart or brain are used routinely in CABG procedures, but ischemia remains a significant and serious risk that can lead to myocardial infarction, prolonged postoperative dysfunction, stroke, or cognitive disorders.
Adenosine receptor activation is an important part of ischemic events. Swain et al., Circulation Research, 1982, 51:102-105; Holmes et al., U.S. Pat. No. 4,575,498 (issued Mar. 11, 1986); and Mitsos et al., Pharmacology, 1985, 31:121-131. Techniques that would increase extracellular levels of adenosine or adenosine analogs at specific times during a pathological event such as ischemia, that would increase these compounds without complex side effects, would therefore be of considerable therapeutic use. One reason for lower levels of adenosine has to do with the presence of the enzyme, adenosine deaminase, in the ischemic area.
Several methods exist for increasing the activation of adenosine receptors. One method is the systemic administration of adenosine. Unfortunately, the systemic administration of adenosine or adenosine analogs tends to reduce blood pressure and induce bradycardia. Therefore, another mechanism of increasing adenosine levels only in the ischemic area is necessary, this would permit increased adenosine levels to be selectively targeted to cells that would benefit most from them.
One alternate mechanism for increasing adenosine levels is to inhibit adenosine deaminase. U.S. Pat. No. 4,912,092 issued Mar. 27, 1990 to Gruber discloses methods for increasing extracellular concentrations of adenosine for the prophylactic or affirmative treatment of diseases of the cardiac and vascular systems involving administering to a patient purine nucleoside and purine nucleoside-related analogs which increase extracellular adenosine concentration. Examples of compounds useful in the invention include compounds broadly classified as purine nucleosides and related analogs, such as AICA riboside, in various pro-forms. The Gruber reference also discloses that pentostatin is a potent inhibitor of the enzyme adenosine deaminase that enhances the effect of the purine nucleoside in elevating adenosine concentrations for a bodily condition. One of the bodily conditions the compounds may be administered to include seizure activity, arrhythmias, or a condition resulting in decreased blood flow. The disclosure of the Gruber reference is hereby incorporated by reference.
World Patent Application 87/05807 to H. E. Gruber, claims a method of treating an animal body for diseases associated with restricted blood flow comprising the administration of purine nucleosides, which may be AICA riboside. The application also claims the use of 2'-deoxycoformycin to enhance the effect of said purine nucleosides. The application is related to U.S. Pat. No. 4,912,092 issued to H. E. Gruber on Mar. 27, 1990 which is discussed above.
U.S. Pat. No. 4,713,372 issued Dec. 15, 1987 to Schaumberg discloses the administration of pentostatin to inhibit adenosine deaminase in order to combat viruses. The patent does not disclose the use of pentostatin to prophylactically or affirmatively treat cerebral and cardiovascular disorders.
The literature contains reports on the effects of adenosine deaminase inhibitors which were used to enhance or maintain local adenosine levels in the heart and brain. For example, pentostatin and erythro-9 (2-hydroxy-3-nonyl) adenine (EHNA) improved functional and metabolic recovery after global ischemia in isolated rabbit (Bolling SF, Bies LE, Bore El, Gallagher KP, Augmenting intracellular adenosine improves myocardial recovery, J Thorac Cardiovasc Surg 99: 469-474, 1990) and rat hearts (Dhasmana JP, Digerness SB, Geckle JM, Ng TC, Glickson JD, Blackstone EH: Effect of adenosine deaminase inhibitors on the heart's functional and biochemical recovery from ischemia: A study utilizing the isolated rat heart adapted to 31-P nuclear magnetic resonance. J Cardiovasc Pharm 5: 1040-1047, 1983). In the brain, inhibition of adenosine deaminase lead to accumulation of interstitial adenosine in rats (Sciotti VM, Van Wylen DGL: Increases in interstitial adenosine and cerebral blood flow with inhibition of adenosine kinase and adenosine deaminase. J Cereb Blood Flow Metab 13: 201-207, 1993) and pentostatin (0.5 mg/kg, corresponding approximately to 3.0 mg/m.sup.2 in humans) has been demonstrated to have beneficial effects in rat and gerbil models of cerebral ischemia or hypoxia (Phillis JW, O'Regan MH, Walter GA: Effects of deoxycoformycin on adenosine, inosine, hypoxanthine, xanthine, and uric acid release from the hypoxemic rat cerebral cortex. J Cereb Blood Flow Metab 8: 733-741, 1988; Phillis JW, O'Regan MH: Deoxycoformycin antagonizes ischemia-induced neuronal degeneration. Brain Res Bull 22: 537- 540, 1989; Phillis JW, Walter GA, Simpson RE: Brain adenosine and transmitter amino acid release from the ischemic rat cerebral cortex: Effects of the adenosine deaminase inhibitor deoxycoformycin. J Neurochem 56: 644-650, 1991). In one report, however, in rat model of transient forebrain ischemia, no beneficial effects of pentostatin were observed (Delaney SM, Sutherland GR, Peeling J, Geiger JD: Failure of 2'-deoxycoformycin to protect against transient forebrain ischemia in rat. Neuroscience Letters 149: 31-34, 1993).
[R]-3-(2-deoxy-.beta.-D-erythropentofuranosyl)-3,6,7,8-tetrahydroimidazo[4, 5-d][1,3]diazepin-8-ol, 2'-deoxycoformycin or pentostatin, is described in U.S. Pat. No. 3,923,785. The compound is disclosed there as having in vitro and in vivo activity against DNA viruses such as herpes and vaccinia. A method for purifying pentostatin is disclosed in copending U.S. application Ser. No. 07/738,715 filed Jul. 31, 1991. The patent and patent application are hereby incorporated by reference.
There is no disclosure in the above references to suggest the methods of the present invention for increasing extracellular adenosine concentration to allow adenosine receptor activation in ischemic areas, thus treating cerebral and cardiovascular disorders such as myocardial and cerebral ischemia.

Method of treating cerebral and cardiovascular disorders employing [R]3-(2-deoxy-.beta.-D-erythro-pentofuranosyl)-3,6,7,8-tetrahydroimidaz 0-[4,5-d][1,3]diazepin-8-ol


A plurality of images (I, J) of an object (M) when viewed from different viewpoints are taken in. One of the images is set as a standard image (I), and the other image is set as a reference image (J). One-dimensional pixel data strings with a predetermined width (W) are cut out from the standard image (I) and the reference image (J) along epipolar lines (EP1, EP2) calculated from a camera parameter (CPR) and the reference point (p). Calculating a phase-only correlation function from the cut one-dimensional pixel data strings will obtain a correlation peak position (Pa1). A positional shift amount (d) from the correlation peak position (Pa1) is obtained. A search is made for a corresponding point (q) corresponding to the reference point (p) based on this position shift amount (d).

Conventionally, searching for corresponding points in a plurality of images of an object when viewed from different viewpoints has been regarded as an important technique in various fields such as image sensing, image/video signal processing, and computer vision. In these fields, a pixel-accuracy matching technique is often used. Recently, however, there have been increasing demands for a subpixel-accuracy matching technique.
For example, a subpixel-accuracy matching algorithm is indispensable to achieve a sufficient three-dimensional measurement accuracy in a stereo vision system with a short baseline length. In addition, a subpixel-accuracy matching algorithm is also important for a video resolution enhancement technique based on a super-resolution technique. For this reason, for example, the stereoscopic image measuring apparatus disclosed in reference 1 (Japanese Patent Laid-Open No. 10-132534) meets the requirement for subpixel-accuracy matching by searching for corresponding points in a plurality of images of an object when viewed from different viewpoints using a two-dimensional phase-only correlation method.
FIG. 20 is a schematic view of an image input unit in the stereoscopic image measuring apparatus disclosed in reference 1 described above. Referring to FIG. 20, reference numeral 1 denotes a first camera; and 2, a second camera. Reference symbol M denotes an object (human face). The cameras 1 and 2 are arranged side by side in the horizontal direction with the distance between lenses LN1 and LN2 being represented by L. For easy understanding, FIG. 20 shows the cameras 1 and 2 viewed from above and the object M viewed from the side.
This stereoscopic image measuring apparatus captures an image of the object M as an input image I by the camera 1 and divides the image data of the input image I into m×n local regions I(i, j). The apparatus then cuts out the local region I(i, j) from the image data of the input image I, and obtains Fourier image data (input Fourier image data) by performing two-dimensional discrete Fourier transform (DFT) for the image data of the cut local region I(i, j).
The apparatus also captures an image of the object M as a reference image J by the camera 2 and obtains Fourier image data (reference Fourier image data) by performing two-dimensional discrete Fourier transform for the image data of the reference image J.
The apparatus then combines the obtained input Fourier image data and the reference Fourier image data, normalizes the amplitude component of the combined Fourier image data (composite Fourier image data), and performs two-dimensional discrete Fourier transform (or two-dimensional discrete inverse Fourier transform) again.
The apparatus obtains the intensity (amplitude) of the correlation component of each pixel in a predetermined correlation component area from the composite Fourier image data having undergone this two-dimensional discrete Fourier transform, and sets, as a position Pa1 of a correlation peak, the position of a pixel having the highest intensity in the correlation component area.
In this case, a distance A from a center P0 of the correlation component area to the position Pa1 of the correlation peak indicates the shift amount between the local region I(i, j) in the image data of the input image I and a given region (corresponding region) in corresponding image data in the image data of the reference image J. The position of an image in the local region I(i, j) in the input image I shifts from an image in the corresponding region in the reference image J due to parallax. This shift appears as a shift amount A.
Based on this shift amount A, the apparatus matches the center point (reference point) of the local region I(i, j) in the input image with the center point (corresponding point) of the corresponding region in the reference image J, and calculates a distance R from each camera to the corresponding point (reference point) of the object M according to equation (1) based on the triangulation principle. Note that in equation (1), f is the distance from the center of a lens LN (LN1, LN2) to the image capturing position, and L is the inter-lens distance.R=f·L/A  (1)

Corresponding point searching method and three-dimensional position measuring method

National University Corporation Tohoku University