外国特許コード F200010030
整理番号 AF40-05WO
掲載日 2020年1月31日
出願国 世界知的所有権機関(WIPO)
国際出願番号 2019JP018225
国際公開番号 WO 2019216304
国際出願日 令和元年5月7日(2019.5.7)
国際公開日 令和元年11月14日(2019.11.14)
  • 特願2018-089516 (2018.5.7) JP
  • 2018JP34515 (2018.9.18) WO
  • 特願2019-059200 (2019.3.26) JP
発明の概要(英語) The present invention is a composite oxide including a metal element represented by the composition of general formula (6), wherein the composite oxide comprises an oxide of A and an oxide of X in a mixed state. General formula (6): AnXy (in general formula (6), A represents an element selected from the group consisting of Sc, Y, and lanthanoids(III); X represents an element selected from the group consisting of Ca, Sr, and Ba; n is 0 < n < 1; y is 0 < y < 1; and n + y = 1). The present invention is also a metal-supported material characterized in that cobalt particles are supported on the aforementioned composite oxide.
従来技術、競合技術の概要(英語) BACKGROUND ART
Ammonia, in the chemical industry is an important raw material of the modern. 80% Or more of ammonia production, agricultural product for the production of chemical fertilizers are used. Further, ammonia, hydrogen energy garnered much attention as a carrier. Which is connected, (1) the content of hydrogen (17.6wt %), (2) high energy density (12.8GJ/m3), (3) when decomposed to produce hydrogen and carbon dioxide is generated from this. Renewable energy such as wind power or solar energy efficiently can be produced if the ammonia, the energy and food crisis associated with the global problem is mitigated.
Current, is used to produce ammonia Haber, the Bosch method, and a large consumption of energy, the amount thereof is about 1-2% of the world's energy consumption occupies. In this method, the energy consumption of about 60% is recovered and, as the enthalpy of the ammonia is ensured. However, the majority of the remainder of the energy, during the production of hydrogen from natural gas, ammonia synthesis, and are lost during the separation. Hard bar, Bosch ammonia synthesis method is a very high temperature and pressure (450°C>) and so on (20mpa>), the large amount of energy used in the method are required to be reduced. Global energy consumption is suppressed, the Haber, the Bosch method used in a mild condition than the iron-based catalysts (lower temperatures and pressures) can be synthesized under ammonia catalyst is required.
In recent years, the order of 1mpa (10 atm) under low pressure conditions has been known a method of producing ammonia. Ruthenium catalyst is used in the production of ammonia, is generally supported on a carrier. For example, to Patent Document 1, ruthenium is supported on the carrier is used as the rare earth oxide, the amount of ruthenium can be reduced, and the reaction temperature can be lowered is disclosed. However, Patent Document 1 in the manufacturing method of the ammonia, the ammonia in the case of manufacturing the lower pressure conditions of the ammonia is not satisfactory in yield. Therefore, the inventors of the present invention, the reduced La0.5Ce0.5O1.75 at 650°C and developed by a ruthenium catalyst carrier, excellent characteristics under a low pressure condition was reported (Non-Patent Document 4).
Patent Document 1, Non-Patent Document 4 and in addition, a variety of rare earth oxide carrier carrying the catalyst with ruthenium ammonia synthesis has been disclosed in various patents. As a typical example, JP-2-4, can be cited non-patent document 1-3. Patent Document 2 and Patent Document 4 is a lanthanoid oxide, praseodymium oxide is disclosed in Patent Document 3, Non-Patent Document 1 is a Ce oxide, has been disclosed as a carrier. Is the non-patent document 2, Ru, Ce, La hydroxide coprecipitation, drying, was activated, the catalyst of Ru/CeO2-La2O3 disclosed system.
Patent Document 1, 2, 4, including non-patent document 1 is in the literature of the prior art, the ruthenium catalyst used in the synthesis of ammonia on the surface of carrier particles can be present as Ru is described. If present as particles, have an average diameter greater than 5nm of the report (see Non-Patent Document 2), and, less than 2nm (Non-Patent Document 4) report. In addition, in Patent Document 3, and Ru the Nest shell structure has been described. On the other hand, the carrier will be, in non-patent document 3, supported Ru (La) - M-O Y (M is, Ca, Sr, Ba) when the ammonia synthesis activity of the catalyst, supported on a carrier before Ru for oxide, the sintering temperature of the oxide carrier and a large specific surface area is 450°C, the firing temperature was increased up to 650°C decrease in specific surface area of the carrier has been described. Also, in view of the high cost of Ru, Ru in the transition metal compound other than the carrier, for example Co supported on a catalyst for ammonia synthesis also has been proposed (for example, Non-Patent Document 5, Non-Patent Document 6 reference). However, in non-patent document 6, supported on the cobalt and barium oxide are disclosed in the Co-BaO/C, ammonia synthesis activity is low. Also, in non-patent document 5, rather than the metal oxide is calcium amide using a (Co/Ba-Ca 2 (NH2) )), 1mpa Co catalyst carried on the ammonia in the yield, a catalyst is supported on the Ru does not.
A catalyst for synthesizing the obtained synthetic activity is generally high. Is developed with respect to the ruthenium catalyst for ammonia synthesis, allow a higher yield of the high activity is continuously demanded. 1 Moles of nitrogen and 3 to 2 moles of ammonia from the hydrogen to be synthesized in the reaction equilibrium, the chemical equilibrium on the pressure conditions of the ammonia in order to improve the yield should be convenient. Therefore, instead of the 1mpa reaction, the reaction at a pressure greater than 1mpa ammonia may be considered to improve the yield. However, the ruthenium catalyst for ammonia synthesis of known, active catalyst poisoning by the hydrogen tends to decrease. Existing Ru-based catalyst is, the Haber, the Bosch method under low pressure conditions than high ammonia synthesis activity often for the purposes of aiming, high pressure conditions to improve the yield and is not suitable.
In addition, the catalyst is loaded into the synthesis reactor used must be periodically replaced, easy handling thereof can also be obtained. With respect to the ruthenium catalyst for ammonia synthesis, it is possible to improve ease of handling are also a continuing need.
  • 出願人(英語)
  • ※2012年7月以前掲載分については米国以外のすべての指定国
  • 発明者(英語)
  • NAGAOKA Katsutoshi
  • OGURA Yuta
  • SATO Katsutoshi
参考情報 (研究プロジェクト等) CREST Creation of Innovative Core Technology for Manufacture and Use of Energy Carriers from Renewable Energy AREA