WO1999064352A1 - Procede catalytique d'oxydation de l'ammoniac et systeme de catalyse - Google Patents

Procede catalytique d'oxydation de l'ammoniac et systeme de catalyse Download PDF

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Publication number
WO1999064352A1
WO1999064352A1 PCT/GB1999/001478 GB9901478W WO9964352A1 WO 1999064352 A1 WO1999064352 A1 WO 1999064352A1 GB 9901478 W GB9901478 W GB 9901478W WO 9964352 A1 WO9964352 A1 WO 9964352A1
Authority
WO
WIPO (PCT)
Prior art keywords
cobalt
catalyst
gauzes
ammonia
bed
Prior art date
Application number
PCT/GB1999/001478
Other languages
English (en)
Inventor
Bernard John Crewdson
Andrew Mark Ward
Original Assignee
Imperial Chemical Industries Plc
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 Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to AU38387/99A priority Critical patent/AU3838799A/en
Publication of WO1999064352A1 publication Critical patent/WO1999064352A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24—Nitric oxide (NO)
    • C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
    • C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
    • B01J35/58—

Definitions

  • This invention relates to a catalytic process and in particular to a process for the oxidation of ammonia
  • Ammonia oxidation is widely employed in the manufacture of nitric acid and hydrogen cyanide
  • nitric acid ammonia is oxidised with air to nitric oxide
  • hydrogen cyanide a mixture of ammonia and methane (often as natural gas) is oxidised with air
  • the gas mixture is passed at an elevated temperature over a catalyst to effect the oxidation
  • the oxidic cobalt-containing catalysts appear to be more sensitive to poisoning by sulphur compounds than the conventional noble metal catalysts As a result of the poisoning, the oxidic cobalt-containing catalysts lose their activity Sulphur compounds, such as sulphur dioxide or hydrogen sulphide, may be present in small proportions in the air employed for the ammonia oxidation Under the conditions prevailing in ammonia oxidation processes, such sulphur compounds, if not already in the form of sulphur dioxide, are oxidised to sulphur dioxide.
  • Sulphur compounds such as sulphur dioxide or hydrogen sulphide
  • the noble metal gauzes may be formed by weaving or knitting or otherwise forming noble metal wires or filaments into a mesh like structure
  • the noble metal is preferably platinum, particularly alloyed with rhodium
  • the oxidic cobalt-containing catalyst is preferably a particulate composition containing oxides of cobalt and other metals, particularly rare earths, especially cerium and/or lanthanum, and as described in the aforesaid WO 9828073 the oxides are preferably in combined form so that less than 30% by weight of the cobalt is present as free cobalt oxides
  • the cobalt-containing catalyst thus preferably contains at least one mixed oxide phase containing cobalt and yttrium and/or at least one rare earth element
  • the catalyst comprises oxides of cobalt and two or more rare earth elements
  • the catalyst may also contain free rare earth oxides and/or one or more mixed oxide phases containing two or more rare earth elements
  • the rare earth to cobalt atomic ratio is 0 8 to 1 2, particularly 1 0 to 1 2
  • less than 25% (by atoms) of the cobalt is present as free cobalt oxides, and in particular it is preferred that less than 15% (by atoms) of the
  • the catalyst contains, in addition to cobalt, oxides of at least one element selected from yttrium, cerium, lanthanum, neodymium, and praseodymium
  • oxides of at least one element selected from yttrium, cerium, lanthanum, neodymium, and praseodymium Preferably a mixture of at least one variable valency element Vv selected from cerium and praseodymium and at least one non-variable valency element Vn selected from yttrium and the non-variable valency rare earth elements such as lanthanum or neodymium is employed
  • the atomic proportions of variable valency element Vv to non-variable valency element Vn is in the range 0 to 1 , particularly 0 to 0 3
  • most of the cobalt is present as a Perovskite phase MCo0 3 , where M represents yttrium and/or a rare earth Where there are two or more elements
  • the catalyst may be in a form wherein the amount of oxygen is non-stoichiomet ⁇ c This arises from the variable valency of cobalt and also of any variable valency rare earth present as part, or all, of the yttrium and/or rare earth
  • the process of the invention may be operated at temperatures of 800-1000°C, particularly 850-950 c C, pressures of 1 to 20 bar abs , with ammonia in air concentrations of 5-15%, often about 10%, by volume
  • the invention is illustrated by the following examples
  • Example 1 (comparative) 5 layers of new un-worked Pt / Rh gauze (95%/5% by weight) were cut to give a stack of 25mm diameter catalyst discs which were placed on top of a fine stainless steel mesh, in turn supported on an alumina monolith, in a 25mm ID quartz reactor tube Thermocouples were provided to measure the temperature of the feed to the reactor and the catalyst temperature A mixture of 10% by volume oxygen, 1% by volume argon and 89% by volume helium were fed, at a rate of 35 litres (at STP) per minute together with 1 84 litres (at STP) per minute of gaseous ammonia, to a preheater and then passed over the catalyst bed The temperature of the feed gas was increased from ambient at a rate of about 20°C per minute to a maximum of about 425°C The temperature was then held at this maximum for 20 minutes and then decreased at about 20°C per minute until the reaction ceased A mass spectrometer was used to analyse the composition of the product gases, with Ar
  • Example 2 (comparative) A cobalt/lanthanum/ce ⁇ um catalyst was prepared by co-precipitation at a pH of 6-7 and at a temperature of 50-60°C from a solution of cobalt, lanthanum and cerium nitrates in the molar ratios of 5 cobalt to 4 lanthanum to 1 cerium, using ammonium carbonate as a precipitant in the presence of oxalic acid
  • the resultant slurry was aged for 1 hour and then filtered and the filter cake washed to an ammonium nitrate concentration of below 0 06% by weight
  • the filter cake was then dried at 120°C and then calcined at 500°C for 6 hours
  • the calcined powder was then pelleted and the resultant pellets fired at 900 ⁇ C for 6 hours
  • the fired pellets had a diameter and height of about 3 mm
  • Example 1 The test procedure of Example 1 was repeated using a 31 mm deep bed of the pellets (mass 38 445g) in place of the Pt/Rh catalyst gauzes The results of this experiment are shown in the following tables
  • Example 1 As in Example 1 , the test was repeated to simulate conditioning of the catalyst. The results are shown in the following tables.
  • Example 2 The test procedure of Example 1 was repeated using a composite catalyst of a single platinum/rhodium gauze followed by a 31 mm depth bed of a fresh sample of the pellets as used in Example 2. The results are shown in the following tables.
  • the composite catalyst has a good selectivity to nitric oxide and a low (good) selectivity to nitrous oxide

Abstract

L'invention porte sur un procédé d'oxydation d'ammoniac consistant à faire passer un mélange d'ammoniac et d'air à haute température dans un catalyseur fait d'une ou plusieurs toiles métalliques de fils élémentaires d'au moins un métal noble, puis à faire passer le mélange de gaz résultant sur un lit de particules de catalyseur contenant de l'oxyde de cobalt.
PCT/GB1999/001478 1998-06-09 1999-05-11 Procede catalytique d'oxydation de l'ammoniac et systeme de catalyse WO1999064352A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38387/99A AU3838799A (en) 1998-06-09 1999-05-11 Catalytic process for the oxidation of ammonia and catalyst assembly

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9812276.5 1998-06-09
GBGB9812276.5A GB9812276D0 (en) 1998-06-09 1998-06-09 Catalytic process

Publications (1)

Publication Number Publication Date
WO1999064352A1 true WO1999064352A1 (fr) 1999-12-16

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/001478 WO1999064352A1 (fr) 1998-06-09 1999-05-11 Procede catalytique d'oxydation de l'ammoniac et systeme de catalyse

Country Status (3)

Country Link
AU (1) AU3838799A (fr)
GB (1) GB9812276D0 (fr)
WO (1) WO1999064352A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1341603A1 (fr) * 2000-12-14 2003-09-10 The University of Hong Kong Methodes et appareil d'oxydation de molecules de glucose
WO2004096702A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Conception de charge de catalyseur amelioree
WO2004096703A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
US6931591B1 (en) 1999-10-15 2005-08-16 Saepio Technologies, Inc. Publishing layout wizard
EP2352583A1 (fr) * 2008-10-20 2011-08-10 Johnson Matthey PLC Unité de confinement d un catalyseur
US8132097B2 (en) 1999-10-15 2012-03-06 Saepio Technologies, Inc. Computer-implemented system for creating a publication and method thereof
WO2012110780A1 (fr) 2011-02-14 2012-08-23 Johnson Matthey Public Limited Company Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CS206957B1 (cs) * 1979-09-20 1981-07-31 Jan Vosolsobe Způsob výroby oxidu dusnatého oxidací amoniaku

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CS206957B1 (cs) * 1979-09-20 1981-07-31 Jan Vosolsobe Způsob výroby oxidu dusnatého oxidací amoniaku

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
CHEM. PRUM. (1990), 40(2), 59-61 *
CHEMICAL ABSTRACTS, vol. 101, no. 10, 3 September 1984, Columbus, Ohio, US; abstract no. 75244, VOSOLSOBE, JAN ET AL: "Nitrogen oxide prepared by ammonia oxidation" XP002112834 *
CHEMICAL ABSTRACTS, vol. 113, no. 2, 9 July 1990, Columbus, Ohio, US; abstract no. 8873, JUROVCAK, ONDREJ ET AL: "Use of platinum-free catalyst AMOX [for ammonia oxidation] in the production of nitric acid" XP002112836 *
CHEMICAL ABSTRACTS, vol. 114, no. 12, 25 March 1991, Columbus, Ohio, US; abstract no. 105129, LI, XIAOBAO ET AL: "Study of porous plate catalysts containing mixed oxides of heavier rare earths [and cobalt] for ammonia oxidation in nitric acid manufacture. II. Comparison of the reactivity of mixed oxide catalysts containing lighter and heavier rare earths" XP002112835 *
CHEMICAL ABSTRACTS, vol. 114, no. 20, 20 May 1991, Columbus, Ohio, US; abstract no. 188430, KARAVAEV, M. M. ET AL: "Pilot-scale testing of non-platinum catalysts for ammonia oxidation" XP002112833 *
CHEMICAL ABSTRACTS, vol. 114, no. 8, 25 February 1991, Columbus, Ohio, US; abstract no. 65212, KARAVAEV, M. M. ET AL: "Ammonia oxidation in the presence of a catalytic system with a nonplatinu oxide catalyst" XP002112837 *
CUIHUA XUEBAO (1990), 11(6), 498-501 *
KHIM. PROM-ST. (MOSCOW) (1990), (11), 669-72 *
KHIM. PROM-ST. (MOSCOW) (1991), (1), 32-5 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6931591B1 (en) 1999-10-15 2005-08-16 Saepio Technologies, Inc. Publishing layout wizard
US8132097B2 (en) 1999-10-15 2012-03-06 Saepio Technologies, Inc. Computer-implemented system for creating a publication and method thereof
EP1341603A4 (fr) * 2000-12-14 2004-11-24 Univ Hong Kong Methodes et appareil d'oxydation de molecules de glucose
EP1341603A1 (fr) * 2000-12-14 2003-09-10 The University of Hong Kong Methodes et appareil d'oxydation de molecules de glucose
WO2004096702A3 (fr) * 2003-04-29 2005-01-20 Johnson Matthey Plc Conception de charge de catalyseur amelioree
WO2004096703A3 (fr) * 2003-04-29 2005-01-20 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
WO2004096703A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
JP2006525215A (ja) * 2003-04-29 2006-11-09 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 改良された触媒充填設計物
CN100363252C (zh) * 2003-04-29 2008-01-23 约翰森·马瑟公开有限公司 氨氧化方法
AU2004234120B2 (en) * 2003-04-29 2009-01-08 Johnson Matthey Plc Improved catalyst charge design
WO2004096702A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Conception de charge de catalyseur amelioree
US8178068B2 (en) 2003-04-29 2012-05-15 Johnson Matthey Plc Catalyst charge design
EP2352583A1 (fr) * 2008-10-20 2011-08-10 Johnson Matthey PLC Unité de confinement d un catalyseur
US8394353B2 (en) 2008-10-20 2013-03-12 Johnson Matthey Plc Catalyst containment unit
WO2012110780A1 (fr) 2011-02-14 2012-08-23 Johnson Matthey Public Limited Company Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac

Also Published As

Publication number Publication date
AU3838799A (en) 1999-12-30
GB9812276D0 (en) 1998-08-05

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