WO2001049603A1 - Catalyseur destine a l'oxydation selective de l'ammoniac en monoxyde d'azote au moyen d'oxygene moleculaire - Google Patents

Catalyseur destine a l'oxydation selective de l'ammoniac en monoxyde d'azote au moyen d'oxygene moleculaire Download PDF

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Publication number
WO2001049603A1
WO2001049603A1 PCT/PL2000/000096 PL0000096W WO0149603A1 WO 2001049603 A1 WO2001049603 A1 WO 2001049603A1 PL 0000096 W PL0000096 W PL 0000096W WO 0149603 A1 WO0149603 A1 WO 0149603A1
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WIPO (PCT)
Prior art keywords
weight
catalyst
mno
mgo
ammonia
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PCT/PL2000/000096
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English (en)
Inventor
Krzysztof Jurczyk
Original Assignee
Zakł
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Publication date
Application filed by Zakł filed Critical Zakł
Priority to AU19039/01A priority Critical patent/AU1903901A/en
Publication of WO2001049603A1 publication Critical patent/WO2001049603A1/fr

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    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese

Definitions

  • the present invention relates to a catalyst for selective oxidation of ammonia with molecular oxygen to nitrogen monoxide.
  • Nitrogen monoxide N 2 0 is obtained in two basic chemical processes: by thermal decomposition of a mixture of ammonium nitrate and ammonium sulfate, and by selective oxidation of ammonia with molecular oxygen in the presence of catalysts. Oxidation of ammonia with molecular oxygen may proceed in a following manner:
  • reaction 3 the most privileged reaction is that of complete oxidation of ammonia to nitrogen and water (reaction 3) which is characterized by both the greatest changes in enthalpy ⁇ H and the free
  • the catalyst for the process of ammonia oxidation with molecular oxygen to nitrogen monoxide is known from the patent application WO 98/25698, and it comprises 5,0- 35% of MnO_, 4,5-30,0% of Bi 2 0 3 , and 35,0-90,5% of A1_0,.
  • Nature of the invention consists m a catalyst for selective oxidation of ammonia with molecular oxygen to nitrogen monoxide, obtained as a result of hydrothermal treatment of a gelatine mixture obtained by precipitation of metal hydroxide forms from solutions of their salts, which catalyst is a mixed system of manganese, magnesium or aluminium or zinc or calcium oxides or mixture thereof, and cerium oxide doted with an activator m amount of 0- 0,5%.
  • compositions of the catalyst are also preferred:
  • the mixed system od manganese, magnesium and cerium oxides is most preferably doted with an activator in the form of Ag + , Cu + , Co 2+ , Fe , Cu 2+ , Bi 2 ⁇ PY' Pd 2 RuY NbY Sn 2" , NY, Co 3+ , Cr 3+ , Fe 3+ , La 3+ , Nb 3 ⁇ Ti + , Zr 4 + , Si 4 ⁇ , Sn 4 ⁇ , Sb 4" , V 5+ , and Mo + ions.
  • an activator in the form of Ag + , Cu + , Co 2+ , Fe , Cu 2+ , Bi 2 ⁇ PY' Pd 2 RuY NbY Sn 2" , NY, Co 3+ , Cr 3+ , Fe 3+ , La 3+ , Nb 3 ⁇ Ti + , Zr 4 + , Si 4 ⁇ , Sn 4 ⁇ , Sb 4" , V 5+ , and Mo + ions.
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 6,44 g of NaOH (0,161 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 3 to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 80°C with no breaking vigorously stirring, and next filtered and washed with demineralized water.
  • the gel obtained was dried at a temperature 100°C for 12 hours, followed by calcination process in an air stream for 6 hours at a temperature 500°C.
  • the catalyst was obtained of molecular formula MnO.MgO.0, lCe 2 0 3 , which contained:
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 12,6 g of NaOH (0,315 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 84°C with no breaking vigorously stirring, and next it was proceeded as in Example I.
  • the catalyst was obtained of molecular formula Mn0.2MgO.0, 5Ce 2 0 3 which contained:
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 16,8 g of NaOH (0,42 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 3 to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 82°C with no breaking vigorously stirring, and next it was proceeded as in Example 1.
  • the catalyst was obtained of molecular formula Mn0.2MgO.Ce 2 0 3 , which contained:
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 9,24 g of NaOH (0,231 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 o to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 82°C with no breaking vigorously stirring, and next it was proceeded as in Example 1.
  • the catalyst was obtained of molecular formula Mn0.2MgO.0, lCe 2 0 3 , which contained:
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 15,4 g of NaOH (0,385 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 3 to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 82°C with no breaking vigorously stirring, and next it was proceeded as in Example 1.
  • the catalyst was obtained of molecular formula MnO.Al0 3 .0, 5Cej0 3/ which contained:
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 12,6 g of NaOH (0,315 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 3 to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 83°C with no breaking vigorously stirring, and next it was proceeded as in Example I .
  • the catalyst was obtained of molecular formula Mn0.2CaO.0, 5Ce 2 0 3 , which contained:
  • the solution obtained was added dropwise for 1 hour with vigorously stirring to the solution containing 12,6 g of NaOH (0,315 mole NaOH) in 200 ml of demineralized water, followed by correction of pH-value of the mixture with nitric acid HN0 3 to approximately 9.
  • the gelatine mixture was heated for 15 hours at a temperature 85°C with no breaking vigorously stirring, and next it was proceeded as in Example I.
  • the catalyst was obtained of molecular formula Mn0.2ZnO.0, 5Ce 2 0 3 , which contained: 17,8% by weight of MnO, 40,9% by weight of ZnO, and 41,3% by weight o f Ce 2 0 3 .
  • Test for catalyst activity were performed in a flow reactor with a fixed catalyst bed. Catalyst volume was 0,5 ml, and the particle diameter was in the range of 0,25-0,5 mm. Just prior to use, the catalyst was activated for 5 hours at a temperature 500°C.
  • the required product of the reaction of oxidation of ammonia on the inventive catalyst is nitrogen monoxide. It is known from the reaction scheme that the optimal molar ratio of ammonia to oxygen is 1 to 1.
  • Catalysts composed as in Examples I to IV were tested in the process of oxidation of ammonia with air oxygen, in a mixture of 17,5% of ammonia and 82,5% of air containing 17,5% of oxygen and 65% of nitrogen.
  • Catalysts of compositions as given in Examples I to IV were also tested in the reaction of selective oxidation of ammonia with pure molecular oxygen in a gaseous stream containing 10% of ammonia and 90% of oxygen at catalyst charging (GHSV) 6000 hY Testing results are given in Table III.
  • Oxidation of ammonia with molecular oxygen on catalysts of compositions as given in Examples I to IV results in formation of nitrogen monoxide as a main reaction product. Nitrogen is the only additional reaction product, whereas formation of other oxides such as NO or N0 2 is not observed under these conditions.
  • Total conversion of ammonia is 100% for all catalysts under given conditions of the reaction, whereas selectivity with respect to N 2 0 increases as a reaction temperature increases, and for catalysts of compositions as given in Examples I to III it reaches 100% at a temperature 230°C.
  • the best catalyst for the reaction of selective oxidation of ammonia with molecular oxygen to nitrogen monoxide under given conditions is that of composition as given in Example II.
  • the inventive catalyst has high activity in the reaction of selective oxidation of ammonia with molecular oxygen to nitrogen monoxide. While selecting corresponding conditions for carrying out the process, it is possible to obtain 100% ammonia conversion with 100%-selectivity with respect to nitrogen monoxide.
  • the calatyst is active and high selective with respect to N 2 0 at temperatures 140- 240°C and maintains stable activity during the whole time of performing the process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention concerne un catalyseur constitué d'un système d'oxyde mixte préparé par oxydation hydrothermale d'un mélange de gélatine obtenu par précipitation de formes d'hydroxyde métallique à partir de solutions de leurs sels. Ce système contient du manganèse, des oxydes de magnésium, d'aluminium, de zinc, de calcium ou un de leurs mélanges, ainsi que de l'oxyde de cérium pourvu de 0 à 0,5 % d'un activateur. Le catalyseur de l'invention, peut s'utiliser dans des processus d'oxydation sélective de l'ammoniac avec de l'oxygène moléculaire. Ce catalyseur est actif et hautement sélectif vis-à-vis du N2O à des températures comprises entre 140 et 240 °C, et conserve son activité stable au cours de la totalité du processus.
PCT/PL2000/000096 1999-12-29 2000-12-13 Catalyseur destine a l'oxydation selective de l'ammoniac en monoxyde d'azote au moyen d'oxygene moleculaire WO2001049603A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU19039/01A AU1903901A (en) 1999-12-29 2000-12-13 Catalyst for selective oxidation of ammonia with molecular oxygen to nitrogen monoxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
USP337596 1999-12-29
PL33759699A PL337596A1 (en) 1999-12-29 1999-12-29 Catalyst for selectively oxidising ammonia to nitrous oxide by means of molecular oxygen

Publications (1)

Publication Number Publication Date
WO2001049603A1 true WO2001049603A1 (fr) 2001-07-12

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PL (1) PL337596A1 (fr)
WO (1) WO2001049603A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100473612C (zh) * 2005-12-14 2009-04-01 中国科学院大连化学物理研究所 一种合成革废水回用方法
DE102013004341A1 (de) * 2013-03-14 2014-09-18 Thyssenkrupp Uhde Gmbh Verfahren zur Oxidation von Ammoniak und dafür geeignete Anlage

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1236819A (en) * 1967-08-21 1971-06-23 Inst Nawozow Sztucznych Improvements in or relating to the production of nitrogen oxide
US3780126A (en) * 1971-03-26 1973-12-18 Petro Tex Chem Corp Oxidative dehydrogenation in the presence of crystalline,provoskite type manganese compounds
US4124687A (en) * 1976-08-05 1978-11-07 University Of Southern California Process for the oxidation of ammonia to nitrous oxide
US4719387A (en) * 1985-11-13 1988-01-12 Thorn Emi Plc Infra-red phosphors and fluorescent lamp containing the same
EP0562567A1 (fr) * 1992-03-23 1993-09-29 Haldor Topsoe A/S Catalyseur pour l'oxidation d'ammoniac
DE4406276A1 (de) * 1993-02-26 1994-09-22 Kyocera Corp Elektrisch leitendes Keramikmaterial und unter dessen Verwendung hergestellte Brennstoffzelle
US5849659A (en) * 1996-04-05 1998-12-15 Daihatsu Motor Co., Ltd. Exhaust gas purifying catalyst
US5976476A (en) * 1995-01-13 1999-11-02 Rhodia Chimie Catalytic composition comprising a mixture of cerium oxide with manganese, iron or praseodymium oxide, process for its preparation and its use in automobile afterburning catalysis

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1236819A (en) * 1967-08-21 1971-06-23 Inst Nawozow Sztucznych Improvements in or relating to the production of nitrogen oxide
US3780126A (en) * 1971-03-26 1973-12-18 Petro Tex Chem Corp Oxidative dehydrogenation in the presence of crystalline,provoskite type manganese compounds
US4124687A (en) * 1976-08-05 1978-11-07 University Of Southern California Process for the oxidation of ammonia to nitrous oxide
US4719387A (en) * 1985-11-13 1988-01-12 Thorn Emi Plc Infra-red phosphors and fluorescent lamp containing the same
EP0562567A1 (fr) * 1992-03-23 1993-09-29 Haldor Topsoe A/S Catalyseur pour l'oxidation d'ammoniac
DE4406276A1 (de) * 1993-02-26 1994-09-22 Kyocera Corp Elektrisch leitendes Keramikmaterial und unter dessen Verwendung hergestellte Brennstoffzelle
US5976476A (en) * 1995-01-13 1999-11-02 Rhodia Chimie Catalytic composition comprising a mixture of cerium oxide with manganese, iron or praseodymium oxide, process for its preparation and its use in automobile afterburning catalysis
US5849659A (en) * 1996-04-05 1998-12-15 Daihatsu Motor Co., Ltd. Exhaust gas purifying catalyst

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100473612C (zh) * 2005-12-14 2009-04-01 中国科学院大连化学物理研究所 一种合成革废水回用方法
DE102013004341A1 (de) * 2013-03-14 2014-09-18 Thyssenkrupp Uhde Gmbh Verfahren zur Oxidation von Ammoniak und dafür geeignete Anlage
WO2014139678A1 (fr) * 2013-03-14 2014-09-18 Thyssenkrupp Industrial Solutions Ag Procédé d'oxydation d'ammoniac et installation y relative
CN105209382A (zh) * 2013-03-14 2015-12-30 蒂森克虏伯工业解决方案股份公司 用于氧化氨的方法及适用于该方法的系统
RU2646643C2 (ru) * 2013-03-14 2018-03-06 Тюссенкрупп Индастриал Солюшнс Аг Способ окисления аммиака и система, подходящая для его осуществления
US10414654B2 (en) 2013-03-14 2019-09-17 Thyssenkrupp Industrial Solutions Ag Method for oxidizing ammonia and system suitable therefor
CN105209382B (zh) * 2013-03-14 2020-01-10 蒂森克虏伯工业解决方案股份公司 用于氧化氨的方法及适用于该方法的系统
US11820653B2 (en) 2013-03-14 2023-11-21 Thyssenkrupp Industrial Solutions Ag Method for oxidizing ammonia and system suitable therefor

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