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    Preparation of α,β-ethylenically unsaturated carboxylic salts by catalytic carboxylation of alkenes
    4.
    发明授权
    Preparation of α,β-ethylenically unsaturated carboxylic salts by catalytic carboxylation of alkenes 有权
    通过烯烃的催化羧化制备α，β-烯属不饱和羧酸盐

    公开(公告)号：US08697909B2

    公开(公告)日：2014-04-15

    申请号：US13728081

    申请日：2012-12-27

    Applicant: BASF SE

    Inventor： Michael Limbach ,  Ronald Lindner ,  Michael Ludwik Lejkowski ,  Takeharu Kageyama ,  Gabriella Eva Bodizs ,  Stephan Schunk ,  Cornelia Futter ,  Jörg Rother

    IPC: C07C51/15

    CPC classification number: C07C51/41 ,  C07F15/04 ,  C07C57/04

    Abstract: In a process for preparing an alkali metal or alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a) a transition metal-alkene complex is reacted with CO2 to give a metallalactone, b) the metallalactone is reacted with a base to give an adduct of the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c) the adduct is reacted with an alkene to release the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The base is selected from alkali metal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases. The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.

    Abstract translation: 在制备α，β-烯属不饱和羧酸的碱金属或碱土金属盐的方法中，a）过渡金属 - 烯烃络合物与CO 2反应得到金属内酯，b）金属内酯与 得到α，β-烯属不饱和羧酸的碱金属或碱土金属盐与过渡金属络合物的加合物，和c）加合物与烯烃反应以释放碱金属或碱土金属 α和β-烯属不饱和羧酸的盐，并再生过渡金属 - 烯烃络合物。 碱选自碱金属或碱土金属的氢氧化物和碱金属或碱土金属的高碱性物质。 烯烃是例如乙烯。 过渡金属络合物包括例如镍和二齿P，P，P，N，P，O或P，卡宾配体，例如1,2-双（二叔丁基膦基）乙烷。

    HIGH-PRESSURE PROCESS FOR THE CARBON DIOXIDE REFORMING OF HYDROCARBONS IN THE PRESENCE OF IRIDIUM-COMPRISING ACTIVE COMPOSITIONS
    6.
    发明申请
    HIGH-PRESSURE PROCESS FOR THE CARBON DIOXIDE REFORMING OF HYDROCARBONS IN THE PRESENCE OF IRIDIUM-COMPRISING ACTIVE COMPOSITIONS 审中-公开
    在包含活性组合物的情况下，碳氢化合物二氧化碳改性的高压过程

    公开(公告)号：US20140001407A1

    公开(公告)日：2014-01-02

    申请号：US13930422

    申请日：2013-06-28

    Applicant: BASF SE

    Inventor： Andrian MILANOV ,  Ekkehard Schwab ,  Stephan Schunk ,  Guido Wasserschaff

    IPC: B01J23/63 ,  C01B3/26

    CPC classification number: B01J23/63 ,  B01J21/066 ,  B01J23/468 ,  B01J23/58 ,  B01J23/6525 ,  B01J23/6527 ,  B01J23/6562 ,  B01J23/8906 ,  B01J23/8913 ,  B01J23/892 ,  B01J35/0013 ,  B01J35/002 ,  B01J35/006 ,  B01J37/0201 ,  B01J37/0207 ,  C01B3/26 ,  C01B3/40 ,  C01B2203/0238 ,  C01B2203/1064 ,  C01B2203/1241 ,  Y02P20/142 ,  Y02P20/52

    Abstract: The invention relates to a catalytic high-pressure process for the CO2 reforming of hydrocarbons, preferably methane, in the presence of iridium-comprising active compositions and also a preferred active composition in which Ir is present in finely dispersed form on zirconium dioxide-comprising support material. The predominant proportion of the zirconium dioxide preferably has a cubic and/or tetragonal structure and the zirconium dioxide is more preferably stabilized by means of at least one doping element. In the process of the invention, reforming gas is brought into contact at a pressure of greater than 5 bar, preferably greater than 10 bar and more preferably greater than 20 bar, and a temperature which is in the range from 600 to 1200° C., preferably in the range from 850 to 1100° C. and in particular in the range from 850 to 950° C., and converted into synthesis gas. The process of the invention is carried out using a reforming gas which comprises only small amounts of water vapor or is completely free of water vapor. In the process, the formation of carbonaceous material on the catalyst is greatly suppressed while carrying out the process, as a result of which the process can be carried out over a long period of time without significant decreases in activity occurring.

    Abstract translation: 本发明涉及用于在包含铱的活性组合物存在的情况下烃，优选甲烷的CO 2重整的催化高压方法，以及其中Ir以细分散形式存在于含二氧化锆的载体上的优选活性组合物 材料。 二氧化锆的主要比例优选具有立方和/或四方结构，并且二氧化锆更优选通过至少一种掺杂元素稳定。 在本发明的方法中，重整气体在大于5巴，优选大于10巴，更优选大于20巴，压力范围为600至1200℃的压力下接触。 ，优选在850〜1100℃，特别是在850〜950℃的范围内，并转化为合成气。 本发明的方法使用只包含少量水蒸汽或完全不含水蒸气的重整气体进行。 在此过程中，在进行该方法的同时，催化剂上的碳质材料的形成受到极大的抑制，其结果是可以长时间地进行该工艺，而不发生活性的显着降低。

    Nickel hexaaluminate-containing catalyst for reforming hydrocarbons in the presence of carbon dioxide
    9.
    发明授权
    Nickel hexaaluminate-containing catalyst for reforming hydrocarbons in the presence of carbon dioxide 有权
    在二氧化碳存在下重整碳氢化镍的含六铝酸盐的催化剂

    公开(公告)号：US09475037B2

    公开(公告)日：2016-10-25

    申请号：US14771888

    申请日：2014-03-06

    Applicant: BASF SE

    Inventor： Stephan Schunk ,  Ekkehard Schwab ,  Andrian Milanov ,  Guido Wasserschaff ,  Thomas Roussiere ,  Gerhard Cox ,  Bernd Hinrichsen ,  Ulrich Floerchinger

    IPC: C01B3/38 ,  C07C1/02 ,  B01J23/00 ,  B01J23/02 ,  B01J23/08 ,  B01J21/04 ,  B01J23/83 ,  B01J37/03 ,  B01J37/04 ,  B01J37/08 ,  B01J23/755 ,  B01J23/78 ,  B01J35/00 ,  B01J35/02 ,  B01J35/10 ,  B01J37/02 ,  C01B3/40

    CPC classification number: B01J23/83 ,  B01J21/04 ,  B01J23/002 ,  B01J23/02 ,  B01J23/755 ,  B01J23/78 ,  B01J35/002 ,  B01J35/006 ,  B01J35/023 ,  B01J35/1004 ,  B01J37/0236 ,  B01J37/031 ,  B01J37/036 ,  B01J37/04 ,  B01J37/08 ,  B01J37/088 ,  C01B3/40 ,  C01B2203/0227 ,  C01B2203/0805 ,  C01B2203/1058 ,  C01B2203/1082 ,  Y02E60/324

    Abstract: The invention relates to a nickel hexaaluminate-comprising catalyst for reforming hydrocarbons, preferably methane, in the presence of carbon dioxide, which comprises hexaaluminate in a proportion in the range from 65 to 95% by weight, preferably from 70 to 90% by weight, and a crystalline, oxidic secondary phase selected from the group consisting of LaAlO3, SrAl2O4 and BaAl2O4 in the range from 5 to 35% by weight, preferably from 10 to 30% by weight. The BET surface area of the catalyst is ≧5 m2/g, preferably ≧10 m2/g. The molar nickel content of the catalyst is ≦3 mol %, preferably ≦2.5 mol % and more preferably ≦2 mol %. The interlayer cations are preferably Ba and/or Sr. The process for producing the catalyst comprises the steps: (i) production of a mixture of metal salts, preferably nitrate salts of Ni and also Sr and/or La, and a nanoparticulate aluminum source, (ii) molding and (iii) calcination. The catalyst of the invention is brought into contact with hydrocarbons, preferably methane, and CO2 in a reforming process, preferably at a temperature of >800° C. The catalyst is also distinguished by structural and preferred properties of the nickel, namely that the nickel particles mostly have a tetragonal form and the particles have a size of ≦50 nm, preferably ≦40 nm and particularly preferably ≦30 nm, and are present finely dispersed as grown-on hexaaluminate particles. The catalyst has only a very low tendency for carbonaceous deposits to be formed.

    Abstract translation: 本发明涉及一种在二氧化碳存在下重整碳氢化合物（优选甲烷）的含六铝酸镍催化剂，其包含65重量％至95重量％，优选70至90重量％的六铝酸盐， 以及选自5至35重量％，优选10至30重量％范围内的LaAlO 3，SrAl 2 O 4和BaAl 2 O 4的结晶，氧化的第二相。 催化剂的BET表面积为≥5m2 / g，优选≥10m2 / g。 催化剂的摩尔镍含量为≤3mol％，优选≤2.5mol％，更优选≤2mol％。 层间阳离子优选为Ba和/或Sr.制备催化剂的方法包括以下步骤：（i）制备金属盐，优选Ni和Sr和/或La的硝酸盐以及纳米颗粒铝源的混合物 ，（ii）成型和（iii）煅烧。 本发明的催化剂在重整过程中优选与烃，优选甲烷和CO 2接触，优选在800℃以上的温度下。催化剂的特征还在于镍的结构和优选性质，即镍 颗粒大多具有四方晶格，并且颗粒的尺寸为≤50nm，优选≤40nm，特别优选≤30nm，并且作为生长六铝酸盐颗粒细分散存在。 催化剂仅形成碳沉积物的非常低的趋势。

    Preparation of a,B-Ethylenically Unsaturated Carboxylic Salts By Catalytic Carboxylation Of Alkenes
    10.
    发明申请
    Preparation of a,B-Ethylenically Unsaturated Carboxylic Salts By Catalytic Carboxylation Of Alkenes 有权
    通过催化羧基化制备乙烯不饱和羧酸盐

    公开(公告)号：US20130172616A1

    公开(公告)日：2013-07-04

    申请号：US13728081

    申请日：2012-12-27

    Applicant: BASF SE

    Inventor： Michael Limbach ,  Ronald Lindner ,  Michael Ludwik Lejkowski ,  Takeharu Kageyama ,  Gabriella Eva Bodizs ,  Stephan Schunk ,  Cornelia Futter ,  Jörg Rother

    IPC: C07C51/41

    CPC classification number: C07C51/41 ,  C07F15/04 ,  C07C57/04

    Abstract: In a process for preparing an alkali metal or alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a) a transition metal-alkene complex is reacted with CO2 to give a metallalactone, b) the metallalactone is reacted with a base to give an adduct of the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c) the adduct is reacted with an alkene to release the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The base is selected from alkali metal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases. The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.

    Abstract translation: 在制备α，β-烯属不饱和羧酸的碱金属或碱土金属盐的方法中，a）过渡金属 - 烯烃配合物与CO 2反应得到金属内酯，b）金属内酯与碱 得到α，β-烯键式不饱和羧酸的碱金属或碱土金属盐与过渡金属配合物的加合物，和c）加合物与烯烃反应以释放碱金属或碱土金属盐的碱金属或碱土金属盐 α，β-烯键式不饱和羧酸，并再生过渡金属 - 烯烃络合物。 碱选自碱金属或碱土金属的氢氧化物和碱金属或碱土金属的高碱性物质。 烯烃是例如乙烯。 过渡金属络合物包括例如镍和二齿P，P，P，N，P，O或P，卡宾配体，例如1,2-双（二叔丁基膦基）乙烷。

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