Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins

    公开(公告)号:US06730812B2

    公开(公告)日:2004-05-04

    申请号:US10358552

    申请日:2003-02-05

    IPC分类号: C07F954

    摘要: The present invention provides a method of preparing a phosphonium salt of the formula [R1R2R3P—CR4R5R6]X, comprising ball-milling a phosphine of the formula R1R2R3P with a compound of the formula XCR4R5R6; a method of preparing a phosphorus ylide of the formula R1R2R3P═CR4R5, comprising ball-milling a phosphonium salt of the formula [R1R2R3P—HCR4R5]X in the presence of a base; and a method of preparing an olefin of the formula R4R5C═CR7H or R4R5C═CR7R8, comprising ball-milling a phosphorus ylide of the formula R1R2R3P═CR4R5 with a compound of the formula R7C(O)H or R7C(O)R8. The inventive method produces phosphonium salts and phosphorus ylides by mechanical processing solid reagents under solvent-free conditions. The advantages of the present invention over conventional solution methods, include: (1) extremely high selectivity; (2) high yields; (3) low processing temperatures; (4) simple and scalable reactions using commercially available equipment; and (5) the complete elimination of solvents from the reaction.

    Method of production of pure hydrogen near room temperature from aluminum-based hydride materials
    2.
    发明授权
    Method of production of pure hydrogen near room temperature from aluminum-based hydride materials 失效
    从铝基氢化物材料在室温附近生产纯氢的方法

    公开(公告)号:US06773692B2

    公开(公告)日:2004-08-10

    申请号:US10167556

    申请日:2002-06-12

    IPC分类号: C01B304

    摘要: The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel.

    摘要翻译: 本发明提供了一种从氢化物基固体材料生产纯氢气的成本有效的方法。 氢化物基固体材料在催化剂的存在下机械加工以获得纯的气态氢。 与以前的方法不同,可以在不加热的情况下从固体材料获得氢,并且在加工期间不加入溶剂。 所描述的氢气生产方法对于消耗纯气态氢作为燃料的能量转化和生产技术是有用的。

    Active magnetic refrigerants based on Gd-Si-Ge material and
refrigeration apparatus and process
    3.
    发明授权
    Active magnetic refrigerants based on Gd-Si-Ge material and refrigeration apparatus and process 失效
    基于Gd-Si-Ge材料的主动磁性制冷剂及制冷装置及工艺

    公开(公告)号:US5743095A

    公开(公告)日:1998-04-28

    申请号:US753064

    申请日:1996-11-19

    IPC分类号: F25B21/00 H01F1/01

    摘要: Active magnetic regenerator and method using Gd.sub.5 (Si.sub.x Ge.sub.1-x).sub.4, where x is equal to or less than 0.5, as a magnetic refrigerant that exhibits a reversible ferromagnetic/antiferromagnetic or ferromagnetic-II/ferromagnetic-I first order phase transition and extraordinary magneto-thermal properties, such as a giant magnetocaloric effect, that renders the refrigerant more efficient and useful than existing magnetic refrigerants for commercialization of magnetic regenerators. The reversible first order phase transition is tunable from approximately 30 K to approximately 290 K (near room temperature) and above by compositional adjustments. The active magnetic regenerator and method can function for refrigerating, air conditioning, and liquefying low temperature cryogens with significantly improved efficiency and operating temperature range from approximately 10 K to 300 K and above. Also an active magnetic regenerator and method using Gd.sub.5 (Si.sub.x Ge.sub.1-x).sub.4, where x is equal to or greater than 0.5, as a magnetic heater/refrigerant that exhibits a reversible ferromagnetic/paramagnetic second order phase transition with large magneto-thermal properties, such as a large magnetocaloric effect that permits the commercialization of a magnetic heat pump and/or refrigerant. This second order phase transition is tunable from approximately 280 K (near room temperature) to approximately 350 K by composition adjustments. The active magnetic regenerator and method can function for low level heating for climate control for buildings, homes and automobile, and chemical processing.

    摘要翻译: 主动磁再生器和使用Gd5(SixGe1-x)4的方法,其中x等于或小于0.5,作为表现出可逆铁磁/反铁磁性或铁磁性II /铁磁体I一阶相变和非凡磁体的磁性制冷剂 - 诸如巨磁电效应的热特性,其使制冷剂比现有的用于磁性再生器商业化的磁性制冷剂更有效和有用。 可逆的一阶相变可以通过组合调整从大约30K到大约290K(接近室温)可调。 主动式蓄热器和方法可以在制冷,空调和液化低温制冷剂方面发挥作用,其效率和工作温度范围从大约10K到300K以上。 作为磁化加热器/制冷剂,使用Gd5(SixGe1-x)4,其中x等于或大于0.5的主动磁性再生器和方法也表现出具有大的磁热特性的可逆铁磁/顺磁二阶相变, 例如允许磁热泵和/或制冷剂商业化的大的磁热效应。 该二阶相变可通过组合调整从约280K(近室温)调节至约350K。 主动式蓄热器和方法可用于建筑物,家庭和汽车以及化学处理的低温加热用于气候控制。

    Dual stage active magnetic regenerator and method
    5.
    发明授权
    Dual stage active magnetic regenerator and method 失效
    双级主动式蓄热器及方法

    公开(公告)号:US5887449A

    公开(公告)日:1999-03-30

    申请号:US881836

    申请日:1997-06-25

    IPC分类号: F25B21/00 H01F1/01

    摘要: A dual stage active magnetic regenerator refrigerator as well as method using the Joule-Brayton thermodynamic cycle includes a high temperature stage refrigerant comprising DyAl.sub.2 or (Dy.sub.1-x Er.sub.x)Al.sub.2 where x is selected to be greater than 0 and less than about 0.3 in combination with a low temperature stage comprising (Dy.sub.1-x Er.sub.x)Al.sub.2 where x is selected to be greater than about 0.5 and less than 1 to provide significantly improved refrigeration efficiency in the liquefaction of gaseous hydrogen.

    摘要翻译: 双级主动式蓄冷器冷冻机以及使用焦耳 - 布莱顿热力循环的方法包括包含DyAl 2或(Dy 1-x Er x)Al 2的高温级制冷剂,其中x选择为大于0且小于约0.3, 包括(Dy1-xErx)Al2的低温阶段,其中x被选择为大于约0.5且小于1,以提供气态氢液化中显着提高的制冷效率。

    Preparation of R5X4 materials by carbothermic processing
    9.
    发明申请
    Preparation of R5X4 materials by carbothermic processing 审中-公开
    通过碳热处理制备R5X4材料

    公开(公告)号:US20120315182A1

    公开(公告)日:2012-12-13

    申请号:US13506434

    申请日:2012-04-18

    IPC分类号: C22B59/00 H01F1/01

    摘要: A method for preparing R5X4 alloy materials where R is a rare earth element selected from one or more of La, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, Sc, and Y and X represents a non-rare earth alloying element such as silicon, germanium, tin, lead, gallium, indium and mixtures thereof. The method involves carbothermically reducing amounts of a rare earth element-containing oxide, an alloying element-containing oxide and/or alloying element in elemental or alloy form, and carbon at elevated temperature to form an R5X4 alloy material, which is melted, solidified, and optionally heat treated. Such a method provides an economical and efficient technique of configuring magnetic refrigerant, magnetostrictive and magnetoresistive alloys and products.

    摘要翻译: 一种制备R5X4合金材料的方法,其中R是选自La,Ce,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Lu,Sc和Y中的一种或多种的稀土元素,X和X表示 非稀土合金元素如硅,锗,锡,铅,镓,铟及其混合物。 该方法包括在元素或合金形式的碳纳米管中减少含稀土元素的氧化物,含合金元素的氧化物和/或合金元素的量,并在升高的温度下形成碳,以形成熔融固化的R 5 X 4合金材料, 并任选地进行热处理。 这种方法提供了一种经济有效的配置磁性制冷剂,磁致伸缩和磁阻合金和产品的技术。

    Method of making active magnetic refrigerant, colossal magnetostriction and giant magnetoresistive materials based on Gd-Si-Ge alloys
    10.
    发明授权
    Method of making active magnetic refrigerant, colossal magnetostriction and giant magnetoresistive materials based on Gd-Si-Ge alloys 失效
    基于Gd-Si-Ge合金制备主动磁致冷剂,巨磁致伸缩和巨磁阻材料的方法

    公开(公告)号:US06589366B1

    公开(公告)日:2003-07-08

    申请号:US09793822

    申请日:2001-02-23

    IPC分类号: H01F1053

    摘要: Method of making an active magnetic refrigerant represented by Gd5(SixGe1−x)4 alloy for 0≦x≦1.0 comprising placing amounts of the commercially pure Gd, Si, and Ge charge components in a crucible, heating the charge contents under subambient pressure to a melting temperature of the alloy for a time sufficient to homogenize the alloy and oxidize carbon with oxygen present in the Gd charge component to reduce carbon, rapidly solidifying the alloy in the crucible, and heat treating the solidified alloy at a temperature below the melting temperature for a time effective to homogenize a microstructure of the solidified material, and then cooling sufficiently fast to prevent the eutectoid decomposition and improve magnetocaloric and/or the magnetostrictive and/or the magnetoresistive properties thereof.

    摘要翻译: 制备由Gd5(SixGe1-x)4合金表示的0 <= x <= 1.0的活性磁性制冷剂的方法,包括将商业纯的Gd,Si和Ge电荷组分的量放置在坩埚中,加热次级 压力达到合金的熔融时间足以使合金均匀化并且存在于Gd电荷组分中的氧氧化碳以减少碳,迅速凝固坩埚中的合金,并在低于该温度的温度下热处理该固化的合金 熔融温度有效均匀化固化材料的微观结构,然后充分快速冷却以防止共析分解并改善磁热和/或磁致伸缩和/或磁阻特性。