WO2011004239A2 - Catalyst for high temperature decomposition of nitrous oxide - Google Patents
Catalyst for high temperature decomposition of nitrous oxide Download PDFInfo
- Publication number
- WO2011004239A2 WO2011004239A2 PCT/IB2010/001656 IB2010001656W WO2011004239A2 WO 2011004239 A2 WO2011004239 A2 WO 2011004239A2 IB 2010001656 W IB2010001656 W IB 2010001656W WO 2011004239 A2 WO2011004239 A2 WO 2011004239A2
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- Prior art keywords
- weight
- catalyst
- high temperature
- nitrous oxide
- numerical value
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical group [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 19
- 239000001272 nitrous oxide Substances 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000011575 calcium Substances 0.000 abstract description 15
- -1 calcium aluminates Chemical class 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000009434 installation Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical group [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001377938 Yara Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
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- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2042—Barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2045—Calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2047—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/30—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Definitions
- the first one is based on the high temperature decomposition of nitrous oxide, in ammonium- oxidation reactor in the temperature range of 800-950 0 C, while the second one - is the low temperature decomposition, in the stream of tail gases, within the temperature of 200-450 0 C.
- Catalyst for high temperature decomposition of nitrous oxide shall exhibit the high activity and selectivity towards N 2 O (decomposition level above 90%), the lack of activity in NO decomposition and high mechanical stability, including catalyst sintering resistance.
- BASF (V. Schumacher et al., Patent WO9955621) proposed oxide catalyst of which cupric oxide constituted the active phase.
- Such a system being successfully tested in industrial installation reached the N 2 O conversion of 70-90% with the simultaneous NOx conversion below 0,5%.
- the most essential problem of its implementation may be the risk of cupric ions leaching from the catalyst and being accommodated in the final product, that is ammonium nitrate.
- the cupric ions can catalyze the ammonium nitrate spontaneous decomposition and therefore increase the risk of explosion.
- Krupp Uhde company (M. Schwefer et al., Patent WO0151415) proposed the catalyst based on zeolites doped with iron, that in laboratory conditions reached N 2 O conversion of 100%. Such systems were examined solely in tail gases stream; however they were not tested in process gases existing in ammonia-oxidizing reactor. In such reactor conditions there is the risk of zeolite dealumination and lost of its characteristic properties, as well as, the probability of NO decomposition activity.
- the catalysts' active components referring to the particular system can consist of the following ions: cobalt, iron, copper, magnesium, calcium, strontium, lanthanum, cerium and platinum.
- transition metal ions the vital issue is their leaching, that may cause serious problems with final product.
- the aim of the invention was to develop the catalyst containing the smallest amount of transition metals ions and of high sintering resistance.
- the nature of the invention is the catalyst for high temperature decomposition of nitrous oxide in the process gas mixture, for installations designed for nitric acid production on the base of aluminates characterized in that the catalyst is composed of CaO from 25 to 49 % by weight and AI 2 O 3 from 26 to 51% by weight and SiO 2 up to 26% by weight, MgO up to 10% by weight, SrO - up to 32% by weight and BaO up to 12% by weight and exists in the form of active catalytically main phase in the minimum amount of 80% of the Mayenite (calcium aluminate) structure CIF 62040- ICSD, described by the chemical formula as: where k has numerical value from 0 to 6, and n has numerical value from 0 to 7, and X stands for the following chemical elements: magnesium or strontium or barium or the mixture of them, and the remaining phase having at least one of
- Stoichiometry of the main phase that means weight ratios of the particular elements being the components of the active phase, is described by means of the chemical formula abovementioned.
- the said aluminate phases exist in solid form or as the coating on the support.
- Mayenite is the calcium aluminate of nanoporous structure, composed of nanocells of formal charge +1/3 that is equilibrated by the charge of exchangeable anions (loosely bound to the lattice structure).
- oxide ions (among other things O 2 ' , O ' and O 2" ) are generated in mayenite structure, the presence of which is the reason of the catalytic activity in high temperature decomposition reaction of nitrous oxide.
- Mayenite is the unique calcium aluminate of this type of structure among other calcium aluminates, such as: CaAI 2 O 4 , CaAI 4 Cv, Ca 3 AI 2 Oe, CaAh 2 Oig.
- the catalyst is the ceramic material of high thermal strength and small specific surface area that makes its being sintering resistant. This material is characterized by the presence of extra-lattice exchangeable oxide ions which can contribute to the N 2 O selective decomposition reaction with no change in the NO concentration.
- the catalyst according to the invention can be applied to remove N 2 O in ammonia- oxidizing reactor for production of nitric acid.
- the subject of the invention is presented in more detail in preferable manufacturing examples:
- the mixture of 25g of CaCO 3 and 14.85 g of AI 2 O 3 was placed in agate ball mill and grinded for 6 hours.
- the homogenous powder obtained consisted of mainly oblong aggregates of the diameter up to 2 micrometers and standard length of 5-10 micrometers, and was calcined in the platinum crucible at 135O 0 C.
- the value of the specific surface measured by N 2 -BET method was 1 m 2 /g.
- the catalyst consisting of, 48.5 wt. % of CaO and 51.5 wt. % OfAI 2 O 3 was obtained.
- Phase analysis by powder diffraction method of sample material showed the presence of the calcium aluminate of the mayenite structure in the amount of 80% and the remaining phase consisted of Ca 3 AI 2 Oe, CaAI 2 O 4 and Ca 2 AUO?.
- the catalyst grains size ranged 0.5 - 10 micrometers.
- the mixture of 3.21 g of AI 2 O 3 , 1.51 g of SiO 2 and 7.57 g of CaCO 3 was prepared and grinded for 6 hours.
- the powder was calcined in the platinum crucible at 135O 0 C for 6 hours with the same temperature increase rate as in Example 1.
- the value of the specific surface measured by N 2 -BET method was 1 m 2 /g.
- the preparation obtained consisted of the following: by weight, 47.3% of CaO, 35.8% Of AI 2 O 3 , 16.9 % of SiO 2 .
- Phase analysis by powder diffraction method of sample material showed the presence of the calcium aluminate of the mayenite structure in the amount of 90% and the remaining phase consisted of Ca 3 AI 2 Oe, CaAI 2 O 4 and Ca 2 AI 4 07.
- the catalyst grains size ranged 5 - 10 micrometers.
- Phase analysis by powder diffraction method of sample material showed the presence of the calcium aluminate of the vnayenite structure in the amount of 95% and the remaining phase consisted of Ca 3 AI 2 O 6 , CaAI 2 O 4 and Ca 2 AI 4 O 7 .
- the catalyst grains size ranged 0.5 - 10 micrometers.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention provides the catalyst for high temperature decomposition of nitrous oxide in process gas mixture, for nitric acid plants, which is based on calcium aluminates. The catalyst according to the invention is composed of CaO from 25 to 49 % by weight and Al2O3 from 26 to 51% by weight and SiO2 up to 26% by weight, MgO up to 10% by weight, SrO - up to 32% by weight and BaO up to 12% by weight and exists in the form of active catalytically main phase in the minimum amount of 80% of the Mayenite structure CIF 62040-ICSD, described by the chemical formula as: Ca12-kXkAl14-nSinO33+(n/2), where k has numerical value from O to 6, and n has numerical value from O to 7, and X stands for the following chemical elements: magnesium or strontium or barium or the mixture of them, and the remaining phase having at least one of the auxiliaries components: Ca3AI2O6, CaAI2O4 and Ca2Al4O7, with the catalyst grains size 0.5 - 10 μm.
Description
CATALYST FOR HIGH TEMPERATURE DECOMPOSITION OF NITROUS OXIDE
The present invention provides the catalyst for high temperature decomposition of nitrous oxide in process gas mixture in ammonia- oxidizing reactor, particularly in nitric acid installation.
Nitrous oxide, N2O, appears as the superfluous by-product in catalytic ammonia- oxidizing reactions in installations designed to produce nitric acid, it is not absorbed in water and is emitted with tail gases into atmosphere. N2O emission can contribute significantly to the greenhouse effect. It can as well have the influence on the destruction of the ozone layer of the stratosphere. Due to the fact that the number of industrial installations in which the waste N2O is produced is relatively small, its removal is technically much easier than the reduction of CO2 emission which comes from scattered sources.
There are possible two different locations of catalysts for N2O removal in installations designed to produce nitric acid. The first one is based on the high temperature decomposition of nitrous oxide, in ammonium- oxidation reactor in the temperature range of 800-9500C, while the second one - is the low temperature decomposition, in the stream of tail gases, within the temperature of 200-4500C.
The place to apply the high temperature catalyst in an ammonium-oxidation reactor is in the space immediately below the catalytic R-Rh gauze. Implementation of the catalyst being the subject matter of the patent does not require any significant modifications of the existing nitric acid installations, therefore its implementation does not generate substantial costs.
Catalyst for high temperature decomposition of nitrous oxide shall exhibit the high activity and selectivity towards N2O (decomposition level above 90%), the lack of activity in NO decomposition and high mechanical stability, including catalyst sintering resistance.
The academic literature provides little examples of high temperature catalytic decomposition of nitrous oxide in installation designed to produce nitric acid. However, many catalytic systems which may be successfully adopted or are adopted already have been studied.
Johnson Matthey (S. A. Axon et al., Patent WO04096702A2) developed the perovskite-based catalyst
that was applied in nitric acid pressure systems. It is however supposed that in the temperature inside the reactor exceeding 8000C, the structure and activity of the said catalyst may show insufficient stability.
BASF (V. Schumacher et al., Patent WO9955621) proposed oxide catalyst of which cupric oxide constituted the active phase. Such a system being successfully tested in industrial installation reached the N2O conversion of 70-90% with the simultaneous NOx conversion below 0,5%. The most essential problem of its implementation may be the risk of cupric ions leaching from the catalyst and being accommodated in the final product, that is ammonium nitrate. In turn, the cupric ions can catalyze the ammonium nitrate spontaneous decomposition and therefore increase the risk of explosion.
Another system (O. Nirisen et. al., Patent WO0202230) is the spinel phase CeO2- supported catalyst (NH-1) produced by Yara company. It was successfully implemented in a medium size installation designed to produce nitric acid in Porsgrunn and also in other similar installations. The said catalyst was characterized by high stability, high conversion of N2O and low losses of NOx.
Hermsdorfer Institute (W. Burckhardt et al., Patent WO0013789) proposed perovskite and spinel active phases deposited on magnesium oxide. This kind of materials presented nearly 100% decomposition of N2O at 8000C, however due to the presence of MgO the stability of the catalyst structure was doubtful for industrial purposes.
Steinmueler (M. Klein et al., Patent WO9907638) discovered a complex system in which the catalyst or combination of the catalysts had not only to remove N2O but also to oxidize N2O to NO. The tests carried out by BASF company that took out the patent, did not prove the effectiveness of the system.
Grande Paroisse company (B.Neveu et a., Patent WO9964139) reported the invention based on the catalytic system composed of mixed oxides such as ZrO2 and Al2θ3 impregnated with zirconium salts. According to the inventors, at 85O0C the decomposition degree of N2O amounted between 78 - 99% with 15% of N2O being
converted to NO. The catalyst was examined only in contact with tail gases but not with process gases of the same composition as in ammonia- oxidizing reactor; therefore the results can not be regarded as trustworthy.
Krupp Uhde company (M. Schwefer et al., Patent WO0151415) proposed the catalyst based on zeolites doped with iron, that in laboratory conditions reached N2O conversion of 100%. Such systems were examined solely in tail gases stream; however they were not tested in process gases existing in ammonia-oxidizing reactor. In such reactor conditions there is the risk of zeolite dealumination and lost of its characteristic properties, as well as, the probability of NO decomposition activity.
M. Santiago and J. Perez - Ramirez (M. Santiago et al.Environ. Sci Technol., 41, (2007), 1704) examined systems based on the hexaaluminates ABAM 1019 (A=La1 Ba, B=Mn, Fe, Ni), which show high stability and high activity toward N2O decomposition. The said substances were tested in gas mixture similar to that as in ammonia-oxidizing reactor. The authors of the invention stated that the examined systems would be a promising alternative for commercial catalysts: 002AIOVCeO2 and LaOeCe02CoO3.
The catalytic systems described above showed sufficient initial activity in N2O decomposition reaction but due to the severe conditions of the process only a small amount of thecatalysts represented the required stability. A great part of the said catalysts s proved unstable because of leaching of the active component, or losing their activity as a result of the reactions between the component phases (J. Perez - Ramirez et ai, /Appl. Catal. B, 44, (2003), 117-151).
According to the literature, the catalysts' active components referring to the particular system can consist of the following ions: cobalt, iron, copper, magnesium, calcium, strontium, lanthanum, cerium and platinum. In the case of transition metal ions the vital issue is their leaching, that may cause serious problems with final product.
The aim of the invention was to develop the catalyst containing the smallest amount of transition metals ions and of high sintering resistance.
The nature of the invention is the catalyst for high temperature decomposition of nitrous oxide in the process gas mixture, for installations designed for nitric acid production on the base of aluminates characterized in that the catalyst is composed of CaO from 25 to 49 % by weight and AI2O3 from 26 to 51% by weight and SiO2 up to 26% by weight, MgO up to 10% by weight, SrO - up to 32% by weight and BaO up to 12% by weight and exists in the form of active catalytically main phase in the minimum amount of 80% of the Mayenite (calcium aluminate) structure CIF 62040- ICSD, described by the chemical formula as:
where k has numerical value from 0 to 6, and n has numerical value from 0 to 7, and X stands for the following chemical elements: magnesium or strontium or barium or the mixture of them, and the remaining phase having at least one of the auxiliaries components: Ca3AI2O6, CaAI2O4 and Ca2AI4O7, with the catalyst grains size 0.5 - 10 μm.
Stoichiometry of the main phase, that means weight ratios of the particular elements being the components of the active phase, is described by means of the chemical formula abovementioned. The said aluminate phases exist in solid form or as the coating on the support.
Mayenite is the calcium aluminate of nanoporous structure, composed of nanocells of formal charge +1/3 that is equilibrated by the charge of exchangeable anions (loosely bound to the lattice structure). The applied laboratory synthesis revealed that oxide ions (among other things O2 ', O' and O2") are generated in mayenite structure, the presence of which is the reason of the catalytic activity in high temperature decomposition reaction of nitrous oxide. Mayenite is the unique calcium aluminate of this type of structure among other calcium aluminates, such as: CaAI2O4, CaAI4Cv, Ca3AI2Oe, CaAh2Oig.
The catalyst is the ceramic material of high thermal strength and small specific surface area that makes its being sintering resistant. This material is characterized by the presence of extra-lattice exchangeable oxide ions which can contribute to the N2O selective decomposition reaction with no change in the NO concentration.
The catalyst according to the invention can be applied to remove N2O in ammonia- oxidizing reactor for production of nitric acid.
The subject of the invention, is presented in more detail in preferable manufacturing examples:
Example 1
The mixture of 25g of CaCO3 and 14.85 g of AI2O3 was placed in agate ball mill and grinded for 6 hours. The homogenous powder obtained consisted of mainly oblong aggregates of the diameter up to 2 micrometers and standard length of 5-10 micrometers, and was calcined in the platinum crucible at 135O0C. The value of the specific surface measured by N2-BET method was 1 m2/g.
Due to the method described above the catalyst consisting of, 48.5 wt. % of CaO and 51.5 wt. % OfAI2O3 was obtained. Phase analysis by powder diffraction method of sample material showed the presence of the calcium aluminate of the mayenite structure in the amount of 80% and the remaining phase consisted of Ca3AI2Oe, CaAI2O4 and Ca2AUO?. The catalyst grains size ranged 0.5 - 10 micrometers.
Example 2.
The mixture of 3.21 g of AI2O3, 1.51 g of SiO2 and 7.57 g of CaCO3 was prepared and grinded for 6 hours. Similarly to Example 1, the powder was calcined in the platinum crucible at 135O0C for 6 hours with the same temperature increase rate as in Example 1. The value of the specific surface measured by N2-BET method was 1 m2/g. The preparation obtained consisted of the following: by weight, 47.3% of CaO, 35.8% Of AI2O3, 16.9 % of SiO2. Phase analysis by powder diffraction method of sample material showed the presence of the calcium aluminate of the mayenite structure in the amount of 90% and the remaining phase consisted of Ca3AI2Oe, CaAI2O4 and Ca2AI407. The catalyst grains size ranged 5 - 10 micrometers.
Example 3.
The three different mixtures were placed in separate agate balls mill and grinded for 6 hours. The first mixture consisted of: 14.85 g of AI2O3, 22g of CaCO3 and 0.81g of MgO, the second consisted of: 14.85g of AI2O3, 22g of CaCO3 and 2.95g of SrCO3, the third one consisted of: 14.85g of AI2O3, 22g of CaCO3 and 3.95g of BaCO3 Similarly to Example 1, the powders were calcined in the platinum crucible at 13500C
for 6 hours with the same temperature increase rate as in Example 1. The value of the specific surface measured by N2-BET method was 1 m2/g.
Phase analysis by powder diffraction method of sample material showed the presence of the calcium aluminate of the vnayenite structure in the amount of 95% and the remaining phase consisted of Ca3AI2O6, CaAI2O4 and Ca2AI4O7. The catalyst grains size ranged 0.5 - 10 micrometers.
Claims
1. The catalyst for high temperature decomposition of nitrous oxide in process gas mixture of nitric acid plants, characterized in that the catalyst is based on aluminates wherein the catalyst is composed of CaO from 25 to 49 % by weight and AI2O3 from 26 to 51% by weight and SiO2 up to 26% by weight, MgO up to 10% by weight, SrO - up to 32% by weight and BaO up to 12% by weight and exists in the form of active catalytically main phase in the minimum amount of 80% of the mayenite structure CIF 62040-ICSD, described by the chemical formula as: 
where k has numerical value from 0 to 6, and n has numerical value from 0 to 7, and X stands for the following chemical elements: magnesium or strontium or barium or the mixture of them, and the remaining phase having at least one of the auxiliaries components: Ca3AI2O6, CaAI2O4 and Ca2AI4Cv1 with the catalyst grains size 0.5 - 10 μm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL388518A PL388518A1 (en) | 2009-07-10 | 2009-07-10 | Catalyst for high-temperature decomposition of nitrous oxide |
| PLP-388518 | 2009-07-10 |
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| WO2011004239A2 true WO2011004239A2 (en) | 2011-01-13 |
| WO2011004239A3 WO2011004239A3 (en) | 2011-05-05 |
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| PL (1) | PL388518A1 (en) |
| WO (1) | WO2011004239A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130108459A1 (en) * | 2011-10-28 | 2013-05-02 | General Electric Company | Mold compositions and methods for casting titanium and titanium aluminide alloys |
| EP2898946A4 (en) * | 2012-09-20 | 2016-04-27 | Tokyo Inst Tech | Hydrogen generation catalyst and method for producing hydrogen |
| US9511417B2 (en) | 2013-11-26 | 2016-12-06 | General Electric Company | Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
| CN106512997A (en) * | 2016-10-13 | 2017-03-22 | 北京石油化工学院 | Industrial catalyst for direct catalytic decomposition of N2O, and preparation method thereof |
| US9802243B2 (en) | 2012-02-29 | 2017-10-31 | General Electric Company | Methods for casting titanium and titanium aluminide alloys |
| WO2020030204A1 (en) | 2018-08-07 | 2020-02-13 | Vysoká Škola Báňská - Technická Univerzita Ostrava | Method of preparation of a catalyst for the removal of nitrous oxide from waste industrial gases and the catalyst prepared by this method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130108459A1 (en) * | 2011-10-28 | 2013-05-02 | General Electric Company | Mold compositions and methods for casting titanium and titanium aluminide alloys |
| CN103889614A (en) * | 2011-10-28 | 2014-06-25 | 通用电气公司 | Mold compositions and methods for casting titanium and titanium aluminide alloys |
| US8858697B2 (en) * | 2011-10-28 | 2014-10-14 | General Electric Company | Mold compositions |
| US9095893B2 (en) | 2011-10-28 | 2015-08-04 | General Electric Company | Methods for casting titanium and titanium aluminide alloys |
| US9802243B2 (en) | 2012-02-29 | 2017-10-31 | General Electric Company | Methods for casting titanium and titanium aluminide alloys |
| EP2898946A4 (en) * | 2012-09-20 | 2016-04-27 | Tokyo Inst Tech | Hydrogen generation catalyst and method for producing hydrogen |
| US9511417B2 (en) | 2013-11-26 | 2016-12-06 | General Electric Company | Silicon carbide-containing mold and facecoat compositions and methods for casting titanium and titanium aluminide alloys |
| CN106512997A (en) * | 2016-10-13 | 2017-03-22 | 北京石油化工学院 | Industrial catalyst for direct catalytic decomposition of N2O, and preparation method thereof |
| WO2020030204A1 (en) | 2018-08-07 | 2020-02-13 | Vysoká Škola Báňská - Technická Univerzita Ostrava | Method of preparation of a catalyst for the removal of nitrous oxide from waste industrial gases and the catalyst prepared by this method |
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| WO2011004239A3 (en) | 2011-05-05 |
| PL388518A1 (en) | 2011-01-17 |
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