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    • 1. 发明授权
    • Particulate solids for catalyst supports and heat transfer materials
    • 用于催化剂载体和传热材料的颗粒状固体
    • US5476877A
    • 1995-12-19
    • US346973
    • 1994-11-29
    • LeRoy R. ClavennaStephen M. DavisRocco A. FiatoGeoffrey R. Say
    • LeRoy R. ClavennaStephen M. DavisRocco A. FiatoGeoffrey R. Say
    • B01J21/06B01J23/83C01B3/40C07C27/00
    • B01J21/066B01J23/83C01B3/40C01B2203/1052C01B2203/1064C01B2203/1082Y02P20/52
    • A particulate, precalcined low silica content zirconia, especially one stabilizer with yttria, is useful as a catalyst support or as a heat transfer solids component for conducting chemical reactions at high temperature, in oxidizing, reducing or hydrothermal conditions, especially in syn gas operations. An admixture of precalcined particulate low silica content zirconia, particularly a low silica content yttria-stabilized zirconia, is employed in a preferred embodiment as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. % with a particulate catalyst notably a nickel-on-alumina catalyst, in concentration ranging generally from about 0. 1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass in high temperature oxidizing, reducing and hydrothermal environments, notably in conducting synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.
    • 颗粒状预煅烧的低二氧化硅含量的氧化锆,特别是具有氧化钇的一种稳定剂,可用作催化剂载体或用作在高温,氧化,还原或水热条件下进行化学反应的传热固体组分,特别是在合成气操作中。 预先煅烧的颗粒状低二氧化硅含量的氧化锆,特别是低二氧化硅含量氧化钇稳定的氧化锆的混合物在优选的实施方案中用作传热固体,浓度通常为约10重量% %至约99.9wt。 %的颗粒催化剂,特别是镍 - 氧化铝催化剂,其浓度范围通常为约0.1重量% %至约90wt。 %。 这种混合物在高温氧化,还原和水热环境中特别是在进行合成气生成操作中提供特别有用的催化接触物质。 这种类型的床促进在反应气相内的连续,高效的热和质量传递。 作为床成分的传热固体的存在保持了优异的床流化特性,抑制了催化剂烧结或附聚的正常趋势; 促进床层流变的趋势。 此外,床的传热颗粒是高度耐磨性的,并且与混合物的催化剂颗粒化学相容。
    • 2. 发明授权
    • Synthesis gas from particulate catalysts, and admixtures of particulate
catalysts and heat transfer solids
    • 颗粒催化剂的合成气,颗粒催化剂和传热固体的混合物
    • US5348717A
    • 1994-09-20
    • US60332
    • 1993-05-11
    • LeRoy R. ClavennaStephen M. DavisGeoffrey R. SayRocco A. Fiato
    • LeRoy R. ClavennaStephen M. DavisGeoffrey R. SayRocco A. Fiato
    • B01J37/04C01B3/40C01B3/44C01B32/40C01B3/02C01B3/26C01B31/18
    • B01J37/04C01B3/40C01B3/44C01B31/18C01B2203/1052C01B2203/1064C01B2203/1082Y02P20/52
    • A process utilizing a particulate catalyst, or particulate catalyst admixed with particulate heat transfer solids for conducting high temperature fluidized bed syn gas operations. Hydrogen and carbon monoxide are produced from a low molecular weight hydrocarbon by contact thereof, at high temperature in the presence of oxygen, or steam and oxygen, with a fluidized bed comprising said particulate solids. In one of its forms, barium hexaluminate is employed as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. %, in admixture with a particulate catalyst containing a metal, or metals, component catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons contacted with a fluidized bed of the catalyst at high temperature hydrothermal conditions. The catalyst, suitably one having a barium hexaluminate carrier component, is employed in concentration ranging generally from about 0.1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass for conducting fluidized bed synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the catalyst having a barium hexaluminate carrier component, or barium hexaluminate heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.
    • 一种利用颗粒催化剂或与颗粒状传热固体混合的颗粒催化剂进行高温流化床合成气操作的方法。 氢和一氧化碳通过与低分子量烃在氧气或蒸气和氧气的存在下在高温下与其接触而产生,其中包含所述颗粒固体的流化床。 在其一种形式中,采用六铝酸钡作为传热固体,其浓度通常为约10wt。 %至约99.9wt。 %,与含有金属或金属的颗粒催化剂的混合物,催化剂用于在高温水热条件下与催化剂的流化床接触的低分子量烃生产氢气和一氧化碳。 合适地使用具有六铝酸钡载体组分的催化剂的浓度通常为约0.1重量% %至约90wt。 %。 这种混合物提供用于进行流化床合成气产生操作的特别有用的催化接触物质。 这种类型的床促进在反应气相内的连续,高效的热和质量传递。 作为床成分的具有六铝酸钡载体成分或六铝酸钡传热固体的催化剂的存在保持了优异的床流化特性,抑制了催化剂烧结或附聚的正常趋势; 促进床层流变的趋势。 此外,床的传热颗粒是高度耐磨性的,并且与混合物的催化剂颗粒化学相容。
    • 3. 发明授权
    • High surface purity heat transfer solids for high temperature fluidized
bed reactions
    • 高表面纯度的传热固体用于高温流化床反应
    • US5360778A
    • 1994-11-01
    • US60378
    • 1993-05-11
    • Stephen M. DavisLeRoy R. ClavennaGeoffrey R. SayRocco A. Fiato
    • Stephen M. DavisLeRoy R. ClavennaGeoffrey R. SayRocco A. Fiato
    • B01J8/00C01B3/44C01B13/14C01F7/02C01F7/46B01J20/02B01J20/30B01J21/02
    • C01B3/44B01J8/008C01B13/145C01F7/02C01F7/46C01P2002/85C01P2004/50C01P2004/61C01P2006/80Y02P20/52
    • High surface purity heat transfer solids are formed, suitably by washing and treating particulate refractory inorganic solids, notably alumina, which contains as impurities up to about 0.5 wt. % silicon and/or up to about 500 wppm boron, with an acid, or dilute acid solution sufficient to reduce the concentration of silicon and boron in the outer peripheral surface layer of the particles, e.g., as measured inwardly toward the center of a particle to a depth of about 50 .ANG. using X-ray photoelectron spectroscopy, to no greater than about 5 atom percent silicon and boron, preferably about 2 atom percent silicon and boron, based on the total number of cations within said outer peripheral surface layer, thereby reducing the tendency of said particles to sinter and agglomerate in the conversion of said hydrocarbon to hydrogen and carbon monoxide in a fluidized bed synthesis gas operation vis-a-vis particles otherwise similar except that the particles are not treated with the acid. The tendency of the particles to sinter and agglomerate is further reduced by the additional removal of sodium, iron, calcium, and titanium impurities from the outer peripheral surface layer of the particles. Preferably the latter named impurities, or impurities other than silicon and boron, are reduced to a concentration below about 20 atom %, more preferably to a concentration below about 15 atom %, in the outer surface layer of the particles.
    • 适当地通过洗涤和处理颗粒耐火无机固体,特别是氧化铝来形成高表面纯度的热传递固体,其含有高达约0.5wt。 %硅和/或高达约500wppm的硼,与酸或稀酸溶液相比足以降低颗粒外周表面层中硅和硼的浓度,例如向内朝向颗粒中心测量 基于所述外周表面层中的阳离子总数,使用X射线光电子能谱测量至约50AHZ的深度,不大于约5原子%的硅和硼,优选约2原子%的硅和硼,由此 降低了所述颗粒在流化床合成气操作中将所述烃转化为氢气和一氧化碳的过程中所述颗粒烧结和附聚的倾向,除了颗粒不用酸处理之外,颗粒否则相似。 通过从颗粒的外周表面层另外去除钠,铁,钙和钛杂质,进一步降低了颗粒烧结和附聚的倾向。 优选地,后者称为杂质或除了硅和硼之外的杂质,在颗粒的外表面层中被还原成低于约20原子%,更优选低于约15原子%的浓度。
    • 5. 发明授权
    • High surface purity heat transfer solids for high temperature fluidized
bed reactions
    • 高表面纯度的传热固体用于高温流化床反应
    • US5496531A
    • 1996-03-05
    • US276071
    • 1994-07-15
    • Stephen M. DavisLeRoy R. ClavennaGeoffrey R. SayRocco A. Fiato
    • Stephen M. DavisLeRoy R. ClavennaGeoffrey R. SayRocco A. Fiato
    • B01J8/00C01B3/44C01B13/14C01F7/02C01F7/46C01B3/02C01B3/26C01B31/18
    • C01B3/44B01J8/008C01B13/145C01F7/02C01F7/46C01P2002/85C01P2004/50C01P2004/61C01P2006/80Y02P20/52
    • High surface purity heat transfer solids are formed, suitably by washing and treating particulate refractory inorganic solids, notably alumina, which contains as impurities up to about 0.5 wt. % silicon and/or up to about 500 wppm boron, with an acid, or dilute acid solution sufficient to reduce the concentration of silicon and boron in the outer peripheral surface layer of the particles, e.g., as measured inwardly toward the center of a particle to a depth of about 50 .ANG. using X-ray photoelectron spectroscopy, to no greater than about 5 atom percent silicon and boron, preferably about 2 atom percent silicon and boron, based on the total number of cations within said outer peripheral surface layer, thereby reducing the tendency of said particles to sinter and agglomerate in the conversion of said hydrocarbon to hydrogen and carbon monoxide in a fluidized bed synthesis gas operation vis-a-vis particles otherwise similar except that the particles are not treated with the acid. The tendency of the particles to sinter and agglomerate is further reduced by the additional removal of sodium, iron, calcium, and titanium impurities from the outer peripheral surface layer of the particles. Preferably the latter named impurities, or impurities other than silicon and boron, are reduced to a concentration below about 20 atom %, more preferably to a concentration below about 15 atom %, in the outer surface layer of the particles.
    • 适当地通过洗涤和处理颗粒耐火无机固体,特别是氧化铝来形成高表面纯度的热传递固体,其含有高达约0.5wt。 %硅和/或高达约500wppm的硼,与酸或稀酸溶液相比足以降低颗粒外周表面层中硅和硼的浓度,例如向内朝向颗粒中心测量 基于所述外周表面层中的阳离子总数,使用X射线光电子能谱测量至约50AHZ的深度,不大于约5原子%的硅和硼,优选约2原子%的硅和硼,由此 降低了所述颗粒在流化床合成气操作中将所述烃转化为氢气和一氧化碳的过程中所述颗粒烧结和附聚的倾向,除了颗粒不用酸处理之外,颗粒否则相似。 通过从颗粒的外周表面层另外去除钠,铁,钙和钛杂质,进一步降低了颗粒烧结和附聚的倾向。 优选地,后者称为杂质或除了硅和硼之外的杂质,在颗粒的外表面层中被还原成低于约20原子%,更优选低于约15原子%的浓度。
    • 6. 发明授权
    • Particulate solids for catalyst supports and heat transfer materials
    • 用于催化剂载体和传热材料的颗粒状固体
    • US5395813A
    • 1995-03-07
    • US60334
    • 1993-05-11
    • LeRoy R. ClavennaStephen M. DavisRocco A. FiatoGeoffrey R. Say
    • LeRoy R. ClavennaStephen M. DavisRocco A. FiatoGeoffrey R. Say
    • B01J21/06B01J23/83C01B3/40B01J23/10B01J23/74B01J35/02
    • B01J21/066B01J23/83C01B3/40C01B2203/1052C01B2203/1064C01B2203/1082Y02P20/52
    • A particulate, precalcined low silica content zirconia, especially one stabilized with yttria, is useful as a catalyst support or as a heat transfer solids component for conducting chemical reactions at high temperature, in oxidizing, reducing or hydrothermal conditions, especially in syn gas operations. An admixture of precalcined particulate low silica content zirconia, particularly a low silica content yttria-stabilized zirconia, is employed in a preferred embodiment as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. %, with a particulate catalyst, notably a nickel-on-alumina catalyst, in concentration ranging generally from about 0.1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass in high temperature oxidizing, reducing and hydrothermal environments, notably in conducting synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.
    • 颗粒状预煅烧的低二氧化硅含量的氧化锆,特别是用氧化钇稳定的氧化锆,可用作催化剂载体或用作在高温,氧化,还原或水热条件下进行化学反应的传热固体组分,特别是在合成气操作中。 预先煅烧的颗粒状低二氧化硅含量的氧化锆,特别是低二氧化硅含量氧化钇稳定的氧化锆的混合物在优选的实施方案中用作传热固体,浓度通常为约10重量% %至约99.9wt。 %的颗粒催化剂,特别是镍 - 氧化铝催化剂,其浓度通常为约0.1wt。 %至约90wt。 %。 这种混合物在高温氧化,还原和水热环境中特别是在进行合成气生成操作中提供特别有用的催化接触物质。 这种类型的床促进在反应气相内的连续,高效的热和质量传递。 作为床成分的传热固体的存在保持了优异的床流化特性,抑制了催化剂烧结或附聚的正常趋势; 促进床层流变的趋势。 此外,床的传热颗粒是高度耐磨性的,并且与混合物的催化剂颗粒化学相容。
    • 10. 发明授权
    • Process for the reactivation of nickel-alumina catalysts
    • 镍 - 氧化铝催化剂再活化方法
    • US5356845A
    • 1994-10-18
    • US60333
    • 1993-05-11
    • LeRoy R. ClavennaStephen M. DavisBrent E. Beasley
    • LeRoy R. ClavennaStephen M. DavisBrent E. Beasley
    • B01J23/94B01J38/06C01B3/40C01B3/44B01J38/72B01J21/20C10J3/46
    • B01J23/94B01J38/06C01B3/40C01B3/44C01B2203/1052Y02P20/52Y02P20/584Y10S502/516
    • A process for the reactivation, or rejuvenation of a nickel-alumina catalyst employed in the production of a gas comprised of an admixture of hydrogen and carbon monoxide, or synthesis gas, by the conversion, in a reactor, or reaction zone, of light hydrocarbons in a fluidized bed of the catalyst at elevated temperature, in the presence of steam and oxygen. Catalyst reactivation is accomplished by withdrawing a portion of the catalyst from the fluidized bed of the reactor and treating the catalyst in an oxidation zone at temperature sufficient to oxidize and convert the nickel component of the catalyst to nickel aluminate and disperse said nickel aluminate within the alumina support, and then recycling the treated catalyst to the reactor, or reaction zone, to reactivate and increase the activity of the catalyst. The catalyst, on reduction in the reactor, or reaction zone, is provided an additional boost in activity by washing, treating or contacting the catalyst from the elevated temperature oxidation zone with an acid sufficient to remove trace impurities without removing any substantial amount of the nickel aluminate, and without forming a residue on the catalyst surface. The normal tendency of the catalyst to agglomerate at reaction conditions is also reduced by the acid treatment.
    • 一种用于生产由氢和一氧化碳的混合气体组成的气体或通过在反应器或反应区中转化的轻烃的合成气的镍 - 氧化铝催化剂的再活化或再生的方法 在催化剂的流化床中,在升高的温度下,在蒸汽和氧气的存在下。 催化剂再活化是通过从反应器的流化床中取出一部分催化剂并在氧化区中处理催化剂,该温度足以氧化并将催化剂的镍组分转化为铝酸镍,并将所述铝酸镍分散在氧化铝 支撑物,然后将经处理的催化剂再循环到反应器或反应区,以重新活化并增加催化剂的活性。 催化剂在还原反应器或反应区中的活性通过从高温氧化区洗涤,处理或接触催化剂而提供额外的活性提高,该酸足以除去痕量杂质而不除去任何相当大量的镍 铝酸盐,并且不在催化剂表面上形成残余物。 催化剂在反应条件下凝聚的正常趋势也通过酸处理降低。