公开(公告)号：US20170354956A1

公开(公告)日：2017-12-14

申请号：US15521018

申请日：2015-10-23

Applicant: BASF SE

Inventor： Rene KOENIG ,  Wieland KOBAN ,  Andrian MILANOV ,  Ekkehard SCHWAB ,  Stephan A SCHUNK ,  Carlos LIZANDARA ,  Guido WASSERSCHAFF

IPC: B01J23/83 ,  B01J37/08 ,  B01J37/04 ,  C01G51/00 ,  C01B3/02

CPC classification number: B01J23/83 ,  B01J23/002 ,  B01J23/78 ,  B01J35/0013 ,  B01J35/023 ,  B01J35/1014 ,  B01J35/1019 ,  B01J35/1038 ,  B01J35/1042 ,  B01J35/1061 ,  B01J37/04 ,  B01J37/086 ,  B01J37/088 ,  B01J37/349 ,  B01J2523/00 ,  C01B3/02 ,  C01B3/40 ,  C01B2203/0238 ,  C01F7/02 ,  C01F7/16 ,  C01F17/0025 ,  C01G51/006 ,  C01G51/70 ,  C01P2002/60 ,  C01P2006/11 ,  C01P2006/12 ,  C01P2006/14 ,  C01P2006/16 ,  Y02P20/142 ,  Y02P20/52 ,  B01J2523/31 ,  B01J2523/3706 ,  B01J2523/845

Abstract: The invention relates to a process for preparing aluminates of the general formula (I) A1BxAl12-xO19-y where A is at least one element from the group consisting of Sr, Ba and La, B is at least one element from the group consisting of Mn, Fe, Co, Ni, Rh, Cu and Zn, x=0.05-1.0, y is a value determined by the oxidation states of the other elements, which comprises the steps (i) provision of one or more solutions or suspensions comprising precursor compounds of the elements A and B and also a precursor compound of aluminum in a solvent, (ii) conversion of the solutions or suspensions or the solutions into an aerosol, (iii) introduction of the aerosol into a directly or indirectly heated pyrolysis zone, (iv) carrying out of the pyrolysis and (v) separation of the resulting particles comprising hexaaluminate of the general formula (I) from the pyrolysis gas.

公开(公告)号：US20160207031A1

公开(公告)日：2016-07-21

申请号：US15000141

申请日：2016-01-19

Applicant: BASF SE

Inventor： Ekkehard SCHWAB ,  Andrian MILANOV ,  Stephan SCHUNK ,  Thomas ROUSSIERE ,  Guido WASSERSCHAFF ,  Andreas STRASSER

IPC: B01J23/78 ,  B01J35/02 ,  B01J23/00

CPC classification number: B01J23/78 ,  B01J23/005 ,  B01J35/0013 ,  B01J35/002 ,  B01J35/0026 ,  B01J35/006 ,  B01J35/023 ,  B01J35/1014 ,  B01J35/1019 ,  B01J35/1061 ,  B01J35/1066 ,  B01J35/1071 ,  B01J35/109 ,  B01J35/1095 ,  B01J37/0009 ,  B01J37/0201 ,  B01J37/08 ,  C01B3/40 ,  C01B2203/0233 ,  C01B2203/0238 ,  C01B2203/1058 ,  Y02P20/142 ,  Y02P20/52

Abstract: The present invention relates to a process for producing a catalyst for the reforming of hydrocarbons, preferably methane, in the presence of CO2, water and/or hydrogen. The production of the catalyst is based on contacting of a hydrotalcite-comprising starting material with a fusible metal salt. The compounds which have been brought into contact with one another are intimately mixed and treated thermally, resulting in the fusible metal salt forming a melt. After molding, the material is subjected to a high-temperature calcination step. The metal salt melt comprises at least one metal selected from the group consisting of K, La, Fe, Co, Ni, Cu and Ce, preferably Ni. The metal salt melt more preferably comprises nickel nitrate hexahydrate. In addition, the invention relates to the use of the catalyst of the invention for the reforming of hydrocarbons, preferably methane, in the presence of CO2, water and/or hydrogen at elevated pressures which are greater than 5 bar, preferably greater than 10 bar, particularly preferably greater than 20 bar. The catalyst according to the invention is distinguished from the prior art by particular, preferred physicochemical properties.

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。

公开(公告)号：US20160311684A1

公开(公告)日：2016-10-27

申请号：US15105464

申请日：2014-12-15

Applicant: BASF SE

Inventor： Andrian MILANOV ,  Ekkehard SCHWAB ,  Heiko URTEL ,  Stephan SCHUNK ,  Guido WASSERSCHAFF

IPC: C01B3/40 ,  C01B3/38

CPC classification number: C01B3/40 ,  B01J23/005 ,  B01J23/007 ,  B01J23/63 ,  B01J23/78 ,  B01J23/83 ,  B01J35/0006 ,  B01J35/1038 ,  B01J37/0018 ,  B01J37/0201 ,  B01J37/023 ,  B01J37/08 ,  B01J37/32 ,  C01B3/382 ,  C01B2203/0233 ,  C01B2203/0238 ,  C01B2203/061 ,  C01B2203/062 ,  C01B2203/1052 ,  C01B2203/1058 ,  C01B2203/1064 ,  C01B2203/1082 ,  C01B2203/1241 ,  C01B2203/1247 ,  C01B2203/141 ,  C01B2203/142 ,  C01B2203/148 ,  Y02P20/52

Abstract: A method of reforming mixtures of hydrocarbons, preferably methane, and carbon dioxide, wherein the method comprises at least two stages. In a first stage, a reactant gas is contacted with a precious metal catalyst and converted to a first product gas (also referred to hereinafter as product gas 1). In a second stage, the first product gas obtained in the first stage is contacted with a non-precious metal catalyst and converted to a second product gas (also referred to hereinafter as product gas 2). The process can also include adding gases to the product gas 1 obtained in the first stage. The practice of the process can minimize the formation of coke on the catalyst in an efficient manner. The combination of a first stage with a precious metal catalyst and at least one second stage with non-precious metal catalyst allows considerable amounts of costly precious metals to be saved.

Abstract translation: 一种重整碳氢化合物，优选甲烷和二氧化碳的混合物的方法，其中该方法包括至少两个阶段。 在第一阶段中，使反应气体与贵金属催化剂接触并转化为第一产物气体（以下也称为产物气体1）。 在第二阶段中，将第一阶段获得的第一产物气体与非贵金属催化剂接触并转化为第二产物气体（以下也称为产物气体2）。 该方法还可以包括向在第一阶段获得的产物气体1中加入气体。 该方法的实践可以以有效的方式最小化催化剂上焦炭的形成。 第一阶段与贵金属催化剂的组合和至少一个第二阶段与非贵金属催化剂的组合允许节省大量昂贵的贵金属。

公开(公告)号：US20160008791A1

公开(公告)日：2016-01-14

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: B01J23/83 ,  B01J35/02 ,  C01B3/40 ,  B01J37/04 ,  B01J37/02 ,  B01J37/08 ,  B01J23/78 ,  B01J35/10

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3％，优选为1％，2.5％，更优选为2％。 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形，并且颗粒的尺寸为＆lt; nlE; 50nm，优选为＆lt; lE; 40nm，特别优选为＆lt; NE; 30nm，并且作为生长的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。

公开(公告)号：US20170080407A1

公开(公告)日：2017-03-23

申请号：US15126217

申请日：2015-03-11

Applicant: BASF SE

Inventor： Stephan A. SCHUNK ,  Ekkehard SCHWAB ,  Andrian MILANOV ,  Guido WASSERSCHAFF ,  Thomas ROUSSIERE ,  Andreas STRASSER ,  Carlos LIZANDARA ,  Nussloch MUELLER

IPC: B01J23/83 ,  B01J35/10 ,  C10G2/00 ,  B01J23/00 ,  C01B3/40

CPC classification number: B01J23/83 ,  B01J21/04 ,  B01J23/002 ,  B01J23/89 ,  B01J23/894 ,  B01J35/1009 ,  C01B3/40 ,  C01B2203/0233 ,  C01B2203/0238 ,  C01B2203/0244 ,  C01B2203/0261 ,  C01B2203/062 ,  C01B2203/1047 ,  C01B2203/1052 ,  C01B2203/1058 ,  C01B2203/1076 ,  C01B2203/1235 ,  C01B2203/1241 ,  C10G2/50 ,  Y02P20/52

Abstract: The invention relates to a process for producing a catalyst for the high-temperature processes (i) carbon dioxide hydrogenation, (ii) combined high-temperature carbon dioxide hydrogenation and reforming and/or (iii) reforming of hydrocarbon-comprising compounds and/or carbon dioxide and the use of the catalyst of the invention in the reforming and/or hydrogenation of hydrocarbons, preferably methane, and/or of carbon dioxide. To produce the catalyst, an aluminum source, which preferably comprises a water-soluble precursor source, is brought into contact with an yttrium-comprising metal salt solution, dried and calcined. The metal salt solution comprises, in addition to the yttrium species, at least one element from the group consisting of cobalt, copper, nickel, iron and zinc.

公开(公告)号：US20140191449A1

公开(公告)日：2014-07-10

申请号：US14139098

申请日：2013-12-23

Applicant: BASF SE

Inventor： Stephan SCHUNK ,  Andrian MILANOV ,  Andreas STRASSER ,  Guido WASSERSCHAFF ,  Thomas ROUSSIERE

IPC: B01J23/83

CPC classification number: B01J23/83 ,  B01J23/002 ,  B01J23/78 ,  B01J35/0006 ,  B01J35/002 ,  B01J35/023 ,  B01J35/1009 ,  B01J35/1014 ,  B01J37/0027 ,  B01J37/0036 ,  B01J37/0072 ,  B01J37/0201 ,  B01J37/08 ,  C01B3/26 ,  C01B3/40 ,  C01B2203/0238 ,  C01B2203/1041 ,  C01B2203/1052 ,  C01B2203/1241 ,  Y02A50/2327 ,  Y02P20/142 ,  Y02P20/52

Abstract: A hexaaluminate-containing catalyst containing a hexaaluminate-containing phase which includes cobalt and at least one further element of La, Ba or Sr. The catalyst contains 2 to 15 mol % Co, 70 to 90 mol % Al, and 2 to 25 mol % of the further element of La, Ba or Sr. In addition to the hexaaluminate-containing phase, the catalyst can include 0 to 50% by weight of an oxidic secondary phase. The process of preparing the catalyst includes contacting an aluminum oxide source with cobalt species and at least with an element from the group of La, Ba and Sr. The molded and dried material is preferably calcined at a temperature greater than or equal to 800° C. In the reforming process for reacting hydrocarbons in the presence of CO2, the catalyst is used at a process temperature of greater than 700° C., with the process pressure being greater than 5 bar.

Abstract translation: 包含含六铝酸盐相的含六铝酸盐的催化剂，其包含钴和至少一种La，Ba或Sr的另一元素。所述催化剂含有2至15mol％的Co，70至90mol％的Al和2至25mol％ 的La，Ba或Sr的另外的元素。除了含有六铝酸盐的相以外，催化剂可以包括0至50重量％的氧化二次相。 制备催化剂的方法包括使氧化铝源与钴物质接触，并且至少与La，Ba和Sr的元素接触。模制和干燥的材料优选在大于或等于800℃的温度下煅烧 在CO 2存在下使烃类反应的重整过程中，催化剂在大于700℃的工艺温度下使用，工艺压力大于5巴。