公开(公告)号：US09259712B2

公开(公告)日：2016-02-16

申请号：US13671159

申请日：2012-11-07

Applicant: BASF SE

Inventor： Ekkehard Schwab ,  Andrian Milanov ,  Stephan Schunk ,  Thomas Roussiere ,  Guido Wasserschaff ,  Andreas Strasser

IPC: B01J23/755 ,  B01J21/10 ,  C01B3/26 ,  B01J23/75 ,  B01J23/00 ,  C01B3/40 ,  B01J37/08 ,  B01J23/78 ,  B01J35/00 ,  B01J35/02 ,  B01J35/10 ,  B01J37/00 ,  B01J37/02

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.

Abstract translation: 本发明涉及用于在CO 2，水和/或氢气存在下重整烃，优选甲烷的催化剂的方法。 催化剂的生产基于含水滑石的原料与可熔金属盐的接触。 已经彼此接触的化合物被充分混合并热处理，导致易熔金属盐形成熔体。 在成型之后，对材料进行高温煅烧步骤。 金属盐熔体包含选自K，La，Fe，Co，Ni，Cu和Ce中的至少一种金属，优选为Ni。 金属盐熔体更优选包含硝酸镍六水合物。 此外，本发明涉及本发明的催化剂在CO 2，水和/或氢气存在下，在高于5巴，优选大于10巴的升高的压力下重整烃，优选甲烷的用途 ，特别优选大于20巴。 根据本发明的催化剂通过特定的优选的物理化学性质与现有技术不同。

公开(公告)号：US09566571B2

公开(公告)日：2017-02-14

申请号：US13762783

申请日：2013-02-08

Applicant: BASF SE

Inventor： Stephan Schunk ,  Andrian Milanov ,  Andreas Strasser ,  Guido Wasserschaff ,  Thomas Roussiere

IPC: B01J23/83 ,  C01B3/26 ,  B01J23/78 ,  C01B3/40 ,  B01J37/08 ,  B01J35/00 ,  B01J23/00 ,  B01J35/02 ,  B01J35/10 ,  B01J37/00 ,  B01J37/02

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 for reforming hydrocarbons. The catalyst consists of a hexaaluminate-containing phase, which consists of cobalt and at least one further element from the group consisting of La, Ba, and Sr, and an oxidic secondary phase. To prepare the catalyst, an aluminum source is brought into contact with a cobalt-containing metal salt solution, dried, and calcined. The metal salt solution additionally contains the at least one further element. The reforming of methane and carbon dioxide is great economic interest since synthesis gas produced during this process can form a raw material for the preparation of basic chemicals. In addition, the use of carbon dioxide as a starting material is important in the chemical syntheses in order to bind carbon dioxide obtained as waste product in numerous processes by a chemical route and thereby avoid emission into the atmosphere.

Abstract translation: 一种用于重整碳氢化合物的含六铝酸盐的催化剂。 该催化剂由含六铝酸盐的相组成，该相由钴和由La，Ba和Sr组成的组中的至少一种其它元素和氧化二次相组成。 为了制备催化剂，使铝源与含钴金属盐溶液接触，干燥并煅烧。 金属盐溶液另外含有至少一种其它元素。 由于在此过程中生产的合成气可以形成用于制备碱性化学品的原料，甲烷和二氧化碳的重整是非常重要的经济利益。 此外，二氧化碳作为原料的使用在化学合成中是重要的，以便通过化学途径将在废物中获得的二氧化碳结合在许多方法中，从而避免排放到大气中。

公开(公告)号：US10987660B2

公开(公告)日：2021-04-27

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 ,  B01J23/78 ,  C01B3/26 ,  C01B3/40 ,  B01J37/08 ,  B01J35/00 ,  B01J23/00 ,  B01J35/02 ,  B01J35/10 ,  B01J37/00 ,  B01J37/02

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.

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。