WO1996038222A1 - Catalyseur et procede pour la preparation d'ammoniac - Google Patents

Catalyseur et procede pour la preparation d'ammoniac Download PDF

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Publication number
WO1996038222A1
WO1996038222A1 PCT/US1996/007948 US9607948W WO9638222A1 WO 1996038222 A1 WO1996038222 A1 WO 1996038222A1 US 9607948 W US9607948 W US 9607948W WO 9638222 A1 WO9638222 A1 WO 9638222A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
zeolite
metal ions
zeolite support
divalent
Prior art date
Application number
PCT/US1996/007948
Other languages
English (en)
Inventor
Christopher T. Fishel
Robert J. Davis
Juan M. Garces
Original Assignee
University Of Virginia Patent Foundation
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Virginia Patent Foundation, The Dow Chemical Company filed Critical University Of Virginia Patent Foundation
Priority to EP96916741A priority Critical patent/EP0840646A1/fr
Priority to BR9608749-8A priority patent/BR9608749A/pt
Priority to AU59503/96A priority patent/AU5950396A/en
Publication of WO1996038222A1 publication Critical patent/WO1996038222A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a novel supported catalyst comprising a Group VIII transition metal supported on a basic molecular sieve, for providing improved synthesis of ammonia from nitrogen and hydrogen gases and a process for using the same in preparing ammonia.
  • Such traditional ruthenium-based ammonia synthesis catalysts consist of ruthenium clusters supported on carriers like carbon and magnesium oxide.
  • ruthenium clusters supported on carriers like carbon and magnesium oxide.
  • Ozaki et al. alkali metal promotors such as potassium or cesium are often added to enhance the catalytic activity of the ruthenium.
  • McCarroll et al disclose the use of ruthenium based ammonia synthesis catalyst which contain an alkali metal and barium, all supported on a carbon support.
  • one object of this invention is to provide a catalyst which provides improved ammonia synthesis rates under industrially useful conditions.
  • a further object of the present invention is to provide an improved process for the preparation of ammonia from nitrogen and hydrogen gases.
  • a catalyst for ammonia synthesis comprising Group VIII transition metal clusters supported on a basic zeolite, which further comprises alkali metal ions and divalent metal ions, which provides markedly improved rates of reaction of N 2 and H 2 to give ammonia.
  • the present invention relates to a Group VIII transition metal/basic zeolite catalyst for the synthesis of ammonia from N 2 and H 2 .
  • the catalyst of the present invention comprises Group VIII transition metal clusters supported on a basic zeolitic support.
  • the Group VIII transition metal cluster is preferably made of Fe, Ru or Os, with Ru being most preferred.
  • the Group VIII transition metal cluster can be prepared using conventional methods (see “Catalyst Manufacture", 2nd Ed., A.B. Stiles and T.A. Koch, Marcel Dekker, New York, 1995).
  • ruthenium clusters can be formed from various ruthenium compounds, such as Ru (NH 3 ) 6 C1 3 .
  • the Group VIII metal compounds are ion exchanged or impregnated onto the zeolite, following which the resulting material is reduced, for example, by hydrogenation, thus providing the resulting clusters in an oxidation state of the corresponding metal (such as Ru°) .
  • the zeolite used in the present catalyst as a support for the Group VIII metal clusters is preferably a Faujasite-type zeolite (or Faujasitic zeolite) , such as Zeolite X, Zeolite Y, EMT, ZSM-3, ZSM-20, Zincophosphate X or SAPO-37.
  • the zeolite is a icroporous crystalline aluminosilicate, preferably having a Si:Al ratio of from 1:1 to 6:1, more preferably 1:1 to 2.5:1.
  • the catalyst of the present invention further contains Group I alkali cations and divalent metal cations.
  • the divalent metal cations can be alkaline earth ions or divalent transition metal ions. Preferably the alkaline earth ions are used, with Ba +2 being most preferred.
  • the divalent metal ions can be incorporated into the Group VIII metal/zeolite catalyst by conventional processes, such as ion exchange or impregnation. Commercially available zeolites often already contain alkali metal ions, such as Na. For example. Zeolite X is available containing Na ions and is conventionally called NaX zeolite.
  • zeolites can be used as supplied, or can first be subjected to modification, such as ion exchange or impregnation, to replace Na with another alkali metal, such as K, with the preferred alkali metals being K, Rb and Cs.
  • modification such as ion exchange or impregnation
  • the alkali metal containing zeolite is then subjected to modification with divalent cations, such as alkaline earth metal ions, by ion exchange or a combination of ion exchange and impregnation.
  • the Group VIII metal can be incorporated into the zeolite using conventional techniques to form the metal clusters and provide the Group VIII/M* 2 /basic zeolite catalyst. While the above sequence of steps can be used to prepare the present catalyst, the steps can be performed in any order, to provide incorporation of the divalent metal ions and the Group VIII metal clusters, to provide the catalyst of the present invention which is active for the production of ammonia from N 2 and H 2 .
  • the Group VIII metal based catalyst of the present invention provides its advantages in reaction rate upon incorporation of even minute quantities of Group VIII metal into the basic zeolite.
  • the loading be in the range of 0.1 to 10%, most preferably in the range of 1-5% by weight, based on the amount of zeolite.
  • the preferred loading is in the range of 0.1 to 2.0%.
  • the divalent metal ions also provide their advantages even upon incorporation of very small quantities into the catalyst.
  • the molar ratio of divalent metal ions to alkali metal ions is in the range from 0.01 to 100, most preferably from 10 to 100.
  • the catalyst of the present invention is contacted with N 2 and H 2 gas in a N 2 :H 2 molar ratio of from 10:1 to 1:10, preferably from 1:3 to 1:6.
  • the reaction is performed at a temperature and pressure sufficient to provide excellent yield per unit time.
  • the temperature of ammonia synthesis is from 200-600°C and the pressure is from atmospheric to 400 atmospheres.
  • reaction time or weight hourly space velocity (g feed/g catalyst/hour)
  • g feed/g catalyst/hour is adjusted to achieve the desired yield of ammonia (i.e., longer contact gives more ammonia and vice versa)
  • the reaction can be performed either batchwise or continuously.
  • NaX zeolite (15 g) from Union Carbide (elemental analysis: Si - 20.48%, Al - 16.55%, Na - 12.6%) was ion- exchanged with 0.936 g of Ru(NH 3 ) 6 Cl 3 in 300 mL of distilled,
  • Example 2 Ru/KX First, NaX zeolite from Union Carbide (elemental analysis: Si - 20.48%, Al - 16.55%, Na - 12.67%) was ion- exchanged three times with 1 molL" 1 aqueous KN0 3 (75, 230 and 350 mL, respectively) and dried to produce KX zeolite. 15 g of KX zeolite was ion exchanged with 0.936 g of Ru(NH 3 ) 6 Cl 3 in 1.2 L of water. The resulting solids were filtered, dried and reduced in flowing H 2 at 723 K. The reduced solid was then impregnated with 310 L of a 0.2 molal aqueous solution of KOH and dried. Elemental analysis: Ru - 2.04%, Si - 19.70%, Al - 13.03%, Na - 0.58%, K - 16.08%.
  • Example 4 Ru/BaX 1.22 g of sample in example 2 (before impregnation with KOH) were ion-exchanged two times with l molL "1 aqueous barium acetate solutions (10 and 15 mL) , filtered and dried. The resulting solids were impregnated with 50 mL of a 0.2 molal aqueous solution of Ba(OH) z . Elemental analysis: Ru - 2.05%, Si - 13.12%, Al - 9.48%, K - 1.32%, Ba - 24.4%.
  • NaX zeolite from Union Carbide (elemental analysis: Si - 20.48%, Al - 16.55%, Na - 12.67%) was ion- exchanged three times with 1 molL "1 of aqueous KN0 3 and dried to produce KX zeolite. 17.68 g of KX zeolite were ion exchanged with 1.1048 g of Ru(NH 3 ) 6 Cl 3 in water. The resulting solids were filtered, dried and reduced in flowing H 2 at 723 K. 3.285 g of the solids were ion-exchanged two times with 1 molL" 1 aqueous barium acetate solutions (10 and 10 mL) , filtered and dried.
  • the Ba-containing Ru catalyst was more active for ammonia synthesis than catalysts containing alkali cations (Na, K, Cs) without Ba.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Cette invention se rapporte à un catalyseur pour la synthèse d'ammoniac à partir de N2 et de H2, qui contient: un support en zéolite basique; des grappes de métaux du groupe VIII maintenues sur le support en zéolite basique; et des ions de métaux alcalins et divalents incorporés dans le support en zéolite; ainsi qu'à un procédé pour produire de l'amoniac au moyen d'un tel catalyseur.
PCT/US1996/007948 1995-05-31 1996-05-31 Catalyseur et procede pour la preparation d'ammoniac WO1996038222A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96916741A EP0840646A1 (fr) 1995-05-31 1996-05-31 Catalyseur et procede pour la preparation d'ammoniac
BR9608749-8A BR9608749A (pt) 1995-05-31 1996-05-31 "catalisador e processo para preparar amÈnia"
AU59503/96A AU5950396A (en) 1995-05-31 1996-05-31 Catalyst and process for preparing ammonia

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44388595A 1995-05-31 1995-05-31
US08/443,885 1995-05-31

Publications (1)

Publication Number Publication Date
WO1996038222A1 true WO1996038222A1 (fr) 1996-12-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/007948 WO1996038222A1 (fr) 1995-05-31 1996-05-31 Catalyseur et procede pour la preparation d'ammoniac

Country Status (6)

Country Link
EP (1) EP0840646A1 (fr)
CN (1) CN1186452A (fr)
AU (1) AU5950396A (fr)
BR (1) BR9608749A (fr)
CA (1) CA2222806A1 (fr)
WO (1) WO1996038222A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6235676B1 (en) 1999-03-15 2001-05-22 Haldor Topsoe A/S Process for the preparation of ammonia and ammonia synthesis catalyst
US6559093B2 (en) 2000-07-06 2003-05-06 Haldor Topsoe A/S Process for catalytic ammonia production-preparation and recovery of ammonia synthesis catalyst
WO2012077658A1 (fr) 2010-12-07 2012-06-14 国立大学法人東京工業大学 Catalyseur de synthèse d'ammoniac et procédé de synthèse d'ammoniac
JP2015218091A (ja) * 2014-05-20 2015-12-07 株式会社Ihi アンモニア合成触媒およびアンモニア合成方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110252376A (zh) * 2019-07-01 2019-09-20 吉林大学 一种光催化氮气和氢气合成氨气的金属-半导体复合光催化剂、制备方法及其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3253887A (en) * 1962-08-03 1966-05-31 Exxon Research Engineering Co Ammonia synthesis catalyst and process
US3770658A (en) * 1970-06-22 1973-11-06 Gasoline Co Ltd Ammonia synthesis catalyst
US4142993A (en) * 1977-12-07 1979-03-06 The Research Council Of Alberta Transition metal catalyst
WO1979000407A1 (fr) * 1977-12-19 1979-07-12 D Lewis Methode de production d'ammoniac
US4348370A (en) * 1980-01-08 1982-09-07 Phillips Petroleum Company Ammonia synthesis with catalyst derived by heating on a support a salt selected from alkali metal, alkaline earth metal, iron and cobalt hexacyanocobaltates and hexacyanoruthenates
US4600571A (en) * 1983-03-18 1986-07-15 The British Petroleum Company P.L.C. Catalysts and their use in ammonia production
US5304601A (en) * 1990-04-09 1994-04-19 Societe Nationale Elf Aquitaine Catalysts based on a faujasite and its application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3253887A (en) * 1962-08-03 1966-05-31 Exxon Research Engineering Co Ammonia synthesis catalyst and process
US3770658A (en) * 1970-06-22 1973-11-06 Gasoline Co Ltd Ammonia synthesis catalyst
US4142993A (en) * 1977-12-07 1979-03-06 The Research Council Of Alberta Transition metal catalyst
WO1979000407A1 (fr) * 1977-12-19 1979-07-12 D Lewis Methode de production d'ammoniac
US4348370A (en) * 1980-01-08 1982-09-07 Phillips Petroleum Company Ammonia synthesis with catalyst derived by heating on a support a salt selected from alkali metal, alkaline earth metal, iron and cobalt hexacyanocobaltates and hexacyanoruthenates
US4600571A (en) * 1983-03-18 1986-07-15 The British Petroleum Company P.L.C. Catalysts and their use in ammonia production
US5304601A (en) * 1990-04-09 1994-04-19 Societe Nationale Elf Aquitaine Catalysts based on a faujasite and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF CATALYSIS, Vol. 141, No. 1, May 1993, CISNEROS et al., "Characterization and Ammonia Synthesis Activity of Ruthenium Zeolite Catalysts", pages 191-205. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6235676B1 (en) 1999-03-15 2001-05-22 Haldor Topsoe A/S Process for the preparation of ammonia and ammonia synthesis catalyst
US6559093B2 (en) 2000-07-06 2003-05-06 Haldor Topsoe A/S Process for catalytic ammonia production-preparation and recovery of ammonia synthesis catalyst
US6673732B2 (en) 2000-07-06 2004-01-06 Haldor Topsoe A/S Process for catalytic ammonia production—preparation and recovery of ammonia synthesis catalyst
WO2012077658A1 (fr) 2010-12-07 2012-06-14 国立大学法人東京工業大学 Catalyseur de synthèse d'ammoniac et procédé de synthèse d'ammoniac
US9150423B2 (en) 2010-12-07 2015-10-06 Tokyo Institute Of Technology Ammonia synthesis catalyst and ammonia synthesis method
JP2015218091A (ja) * 2014-05-20 2015-12-07 株式会社Ihi アンモニア合成触媒およびアンモニア合成方法

Also Published As

Publication number Publication date
BR9608749A (pt) 1999-12-07
AU5950396A (en) 1996-12-18
EP0840646A1 (fr) 1998-05-13
CA2222806A1 (fr) 1996-12-05
CN1186452A (zh) 1998-07-01

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