WO1996038222A1 - Catalyst and process for preparing ammonia - Google Patents
Catalyst and process for preparing ammonia Download PDFInfo
- 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
Links
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
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96916741A EP0840646A1 (en) | 1995-05-31 | 1996-05-31 | Catalyst and process for preparing ammonia |
BR9608749-8A BR9608749A (en) | 1995-05-31 | 1996-05-31 | "catalyst and process for preparing ammonia" |
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 (en) | 1996-12-05 |
Family
ID=23762565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/007948 WO1996038222A1 (en) | 1995-05-31 | 1996-05-31 | Catalyst and process for preparing ammonia |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0840646A1 (en) |
CN (1) | CN1186452A (en) |
AU (1) | AU5950396A (en) |
BR (1) | BR9608749A (en) |
CA (1) | CA2222806A1 (en) |
WO (1) | WO1996038222A1 (en) |
Cited By (4)
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 (en) | 2010-12-07 | 2012-06-14 | 国立大学法人東京工業大学 | Ammonia synthesis catalyst and ammonia synthesis method |
JP2015218091A (en) * | 2014-05-20 | 2015-12-07 | 株式会社Ihi | Ammonia synthesis catalyst and ammonia synthesis method |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A metal-semiconductor composite photocatalyst for photocatalytic synthesis of ammonia from nitrogen and hydrogen, preparation method and application thereof |
Citations (7)
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 (en) * | 1977-12-19 | 1979-07-12 | D Lewis | Method of producing ammonia |
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 |
-
1996
- 1996-05-31 AU AU59503/96A patent/AU5950396A/en not_active Abandoned
- 1996-05-31 CN CN96194318A patent/CN1186452A/en active Pending
- 1996-05-31 EP EP96916741A patent/EP0840646A1/en not_active Withdrawn
- 1996-05-31 CA CA002222806A patent/CA2222806A1/en not_active Abandoned
- 1996-05-31 WO PCT/US1996/007948 patent/WO1996038222A1/en not_active Application Discontinuation
- 1996-05-31 BR BR9608749-8A patent/BR9608749A/en unknown
Patent Citations (7)
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 (en) * | 1977-12-19 | 1979-07-12 | D Lewis | Method of producing ammonia |
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)
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)
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 (en) | 2010-12-07 | 2012-06-14 | 国立大学法人東京工業大学 | Ammonia synthesis catalyst and ammonia synthesis method |
US9150423B2 (en) | 2010-12-07 | 2015-10-06 | Tokyo Institute Of Technology | Ammonia synthesis catalyst and ammonia synthesis method |
JP2015218091A (en) * | 2014-05-20 | 2015-12-07 | 株式会社Ihi | Ammonia synthesis catalyst and ammonia synthesis method |
Also Published As
Publication number | Publication date |
---|---|
CA2222806A1 (en) | 1996-12-05 |
CN1186452A (en) | 1998-07-01 |
EP0840646A1 (en) | 1998-05-13 |
AU5950396A (en) | 1996-12-18 |
BR9608749A (en) | 1999-12-07 |
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