PL213796B1 - Catalytic agent for low temperature decomposition of dinitrogen monoxide - Google Patents
Catalytic agent for low temperature decomposition of dinitrogen monoxideInfo
- Publication number
- PL213796B1 PL213796B1 PL385251A PL38525108A PL213796B1 PL 213796 B1 PL213796 B1 PL 213796B1 PL 385251 A PL385251 A PL 385251A PL 38525108 A PL38525108 A PL 38525108A PL 213796 B1 PL213796 B1 PL 213796B1
- Authority
- PL
- Poland
- Prior art keywords
- weight
- amount
- oxide
- catalyst
- low temperature
- Prior art date
Links
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical group [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims description 44
- 238000000354 decomposition reaction Methods 0.000 title claims description 11
- 230000003197 catalytic effect Effects 0.000 title description 2
- 229960001730 nitrous oxide Drugs 0.000 title 1
- 235000013842 nitrous oxide Nutrition 0.000 title 1
- 239000001272 nitrous oxide Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 2
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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)
Landscapes
- Catalysts (AREA)
Description
Opis wynalazkuDescription of the invention
Przedmiotem wynalazku jest katalizator do niskotemperaturowego rozkładu podtlenku azotu w gazach resztkowych z instalacji kwasu azotowego(V).The subject of the invention is a catalyst for the low-temperature decomposition of nitrous oxide in tail gases from a nitric acid plant (V).
Podtlenek azotu (N2O) tworzy się jako produkt uboczny podczas katalitycznego utleniania amoniaku w instalacjach do produkcji kwasu azotowego(V), nie ulega absorpcji w wodzie i jest emitowany z gazami resztkowymi do atmosfery. Emisja N2O może w sposób znaczący przyczyniać się do efektu cieplarnianego, ponieważ akumuluje on ciepło ok. 310 razy bardziej efektywnie, niż CO2. Ponadto może on wpływać na niszczenie warstwy ozonowej w stratosferze. Stąd też konieczne jest jego efektywne eliminowanie z gazów odlotowych zarówno w przypadku źródeł stacjonarnych, jak i mobilnych.Nitrous oxide (N2O) is formed as a by-product during the catalytic oxidation of ammonia in nitric acid (V) plants, is not absorbed in water and is emitted into the atmosphere with tail gases. N2O emissions can make a significant contribution to the greenhouse effect, as it accumulates heat approximately 310 times more efficiently than CO2. Moreover, it can contribute to the destruction of the ozone layer in the stratosphere. Hence, it is necessary to effectively eliminate it from the waste gases for both stationary and mobile sources.
Zasadniczo możliwe są dwie różne lokalizacje katalizatorów do usuwania N2O w instalacjach do produkcji kwasu azotowego(V): pierwszą jest strefa wysokotemperaturowa (800 - 940°C) w reaktorze do utleniania amoniaku, drugą - strefa niskotemperaturowa (200 - 450°C) w strumieniu gazów resztkowych.Basically, two different locations for N2O removal catalysts in nitric acid plants are possible: the first is the high temperature zone (800 - 940 ° C) in the ammonia oxidation reactor, the second is the low temperature zone (200 - 450 ° C) in the stream residual gases.
Z mechanistycznego punktu widzenia usuwanie podtlenku azotu może nastąpić zarówno na drodze selektywnej katalitycznej redukcji, jak i na drodze bezpośredniego rozkładu N2O do tlenu i azotu. Niskotemperaturowy rozkład katalityczny podtlenku azotu, obserwowany na układach, będących przedmiotem patentu, jest zdecydowanie bardziej korzystny, w porównaniu z redukcją, ze względu na brak konieczności stosowania dodatkowych substancji redukujących oraz stosunkowo niską temperaturę pracy. Ponadto, w odróżnieniu od katalizatorów pracujących w strefie wysokotemperaturowej, użycie katalizatora w strumieniu gazów odlotowych umożliwia zminimalizowanie strat związanych z ewentualnym zubożeniem mieszanki gazowej w NOx, stanowiących substrat do produkcji kwasu azotowego(V). Z drugiej strony, zastosowanie katalizatora w strefie niskich temperatur wiąże się z wymogiem wysokiej aktywności, odporności na inne składniki obecne w strumieniu gazów odlotowych, tj. tlenu i wody oraz innych tlenków azotu.Mechanistically, the removal of nitrous oxide can occur both by selective catalytic reduction and by direct decomposition of N2O into oxygen and nitrogen. Low-temperature catalytic decomposition of nitrous oxide, observed in the systems, which are the subject of the patent, is definitely more advantageous compared to the reduction, due to the lack of necessity to use additional reducing substances and the relatively low operating temperature. Moreover, unlike the catalysts working in the high-temperature zone, the use of the catalyst in the waste gas stream allows to minimize the losses related to the possible depletion of the gas mixture in NOx, which is the substrate for the production of nitric acid (V). On the other hand, the use of the catalyst in the low temperature zone requires high activity, resistance to other components present in the waste gas stream, i.e. oxygen and water and other nitrogen oxides.
W literaturze naukowej można znaleźć wiele doniesień na temat katalitycznego rozkładu podtlenku azotu. Dotyczą one badań na wielu różnych układach: metalicznych, tlenkowych oraz mieszanych (F. Kapteijn et al./Appl. Catal. B 9 (1996) 25). Pośród układów tlenkowych obok prostych tlenków badane były tlenki złożone o zróżnicowanej strukturze, m.in. perowskity, spinele, zeolity, pochodne hydrotalkitów.There are many reports in the scientific literature on the catalytic decomposition of nitrous oxide. They concern research on many different systems: metallic, oxide and mixed (F. Kapteijn et al. / Appl. Catal. B 9 (1996) 25). Among the oxide systems, apart from simple oxides, complex oxides of various structures were investigated, e.g. perovskites, spinels, zeolites, hydrotalcite derivatives.
Prowadzone były także badania na układach modelowych, takich jak Co3O4, MgO, CaO (A. Scagnalli et al./Surf. Sci. 600 (2006) 386-394; A. Satsuma et al./J. Mol. Catal. A 155 (2000) 81-88). Na podstawie doniesień literaturowych stwierdzić można, iż aktywnymi składnikami katalizatorów w zależności od układu mogą być jony kobaltu, żelaza, niklu, cynku, miedzi, manganu, magnezu, wapnia, chromu (N. Russo et al./Cat. Today 119 (2007) 228-232; T. Goto et al./React. Kinet. Catal. Lett. 69 2 (2000) 375-378)). W przypadku układów modelowych efekty promocyjne potwierdzono dotychczas dla takich dopantów jak potas, sód. bar, cer (L. Xue et al./Appl. Catal. B 75 (2007) 167-174; Ch. Ohnishi et al./Catal. Today 120 (2007) 145-150; L. Xue et al./Catal. Today 126 (2007) 449-455).Studies were also carried out on model systems such as Co3O4, MgO, CaO (A. Scagnalli et al. / Surf. Sci. 600 (2006) 386-394; A. Satsuma et al. / J. Mol. Catal. A 155. (2000) 81-88). Based on literature reports, it can be concluded that the active components of catalysts, depending on the system, may be ions of cobalt, iron, nickel, zinc, copper, manganese, magnesium, calcium, chromium (N. Russo et al. / Cat. Today 119 (2007) 228-232; T. Goto et al. React. Kinet. Catal. Lett. 69 2 (2000) 375-378)). In the case of model systems, the promotional effects have so far been confirmed for such dopants as potassium and sodium. bar, cerium (L. Xue et al. / Appl. Catal. B 75 (2007) 167-174; Ch. Ohnishi et al. / Catal. Today 120 (2007) 145-150; L. Xue et al. / Catal. Today 126 (2007) 449-455).
Problem katalitycznego rozkładu N2O jest również przedmiotem wielu prac teoretycznych. Aktualnie prowadzone obliczenia bazują jednak na bardzo uproszczonych modelach powierzchni metali i tlenków (B.-Z. Sun et al. / Applied Surface Science 253 (2007) 7501-7505; A. Spis, H. Miettinen/ J. Phys. Chem. B.102 (1998) 2555; A. Delabie. K. Pierloot/J. Phys. Chem. A, 106 (2002) 5679-5685). Ze względu na ograniczone moce obliczeniowe komputerów możliwe było badanie tylko wybranych ścieżek energetycznych rozkładu N2O, zaniedbując wiele istotnych parametrów procesu rzeczywistego (T, p), niezbędnych do opracowania katalizatora aktywnego w warunkach przemysłowych.The problem of catalytic decomposition of N2O is also the subject of much theoretical work. The currently performed calculations, however, are based on very simplified models of the surface of metals and oxides (B.-Z. Sun et al. / Applied Surface Science 253 (2007) 7501-7505; A. Spis, H. Miettinen / J. Phys. Chem. B 102 (1998) 2555; A. Delabie. K. Pierloot / J. Phys. Chem. A, 106 (2002) 5679-5685). Due to the limited computing power of computers, it was possible to study only selected energy paths of N2O decomposition, neglecting many important parameters of the real process (T, p), necessary for the development of an active catalyst in industrial conditions.
Podsumowując doniesienia literaturowe można stwierdzić, że odpowiednio zmodyfikowany tlenek o strukturze spinelu, zawierający jony kobaltu, może stanowić dobry układ wyjściowy do uzyskania katalizatora pracującego w warunkach przemysłowych. Jednak wadą dotychczasowych rozwiązań było, iż problemem rozkładu N2O na ww. katalizatorach zajmowano się w warunkach laboratoryjnych, co najprawdopodobniej leży u podstaw braku opracowania katalizatora do rozkładu podtlenku azotu odpowiednio aktywnego w niskiej temperaturze.Summarizing the literature reports, it can be stated that an appropriately modified oxide with a spinel structure, containing cobalt ions, can be a good starting system for obtaining a catalyst operating in industrial conditions. However, the disadvantage of the existing solutions was that the problem of decomposition of N2O into the above-mentioned Catalysts were dealt with in laboratory conditions, which is most likely the reason why a catalyst was not developed to decompose nitrous oxide adequately active at low temperature.
Istota wynalazku charakteryzuje się tym, że zawiera (w przeliczeniu na proste tlenki): tlenek kobaltu w ilości 45-99,97% wagowych, tlenek niklu w ilości 0,01-30% wagowych, tlenek cynku w ilości 0,01-20% wagowych jako zasadnicze składniki strukturalne oraz promotory aktywności w postaci metali alkalicznych takich jak Na i/lub K w ilości 0,01-5% wagowych i ułatwiające formowanie tlenki metali ziem alkalicznych takich jak Ca i/lub Mg w ilości 0,01-5% wagowych.The essence of the invention is characterized by the fact that it contains (expressed as simple oxides): cobalt oxide in the amount of 45-99.97% by weight, nickel oxide in the amount of 0.01-30% by weight, zinc oxide in the amount of 0.01-20% by weight as basic structural components and activity promoters in the form of alkali metals such as Na and / or K in an amount of 0.01-5% by weight and facilitating the formation of alkaline earth metal oxides such as Ca and / or Mg in an amount of 0.01-5% by weight.
PL 213 796 B1PL 213 796 B1
Korzystnie jest gdy wprowadzane na etapie syntezy jony kobaltu, niklu i cynku tworzą tlenkowy roztwór stały o strukturze spinelu (Co3O4).Preferably, the cobalt, nickel and zinc ions introduced at the synthesis stage form an oxide solid solution with a spinel structure (Co3O4).
Podczas prowadzonych badań z zastosowaniem kompleksowego podejścia, z równoczesnym użyciem wielu promotorów aktywności, odpornych na składniki gazów resztkowych, i dodatków polepszających właściwości mechaniczne, nieoczekiwanie okazało się, że możliwe jest opracowanie aktywnego katalizatora do niskotemperaturowego rozkładu podtlenku azotu w gazach resztkowych z instalacji kwasu azotowego(V), w którym głównymi składnikami aktywnymi są jony kobaltu, niklu i cynku. Okazało się również, że dodatek promotorów w postaci metali alkalicznych, takich jak sód i potas, zwiększa aktywność katalizatora a metali ziem alkalicznych, takich jak magnez i wapń, ułatwia jego formowanie oraz zapewnia odpowiednią strukturę i wytrzymałość.During the research carried out using a comprehensive approach, with the simultaneous use of many activity promoters, resistant to tail gas components, and additives improving mechanical properties, it was surprisingly found that it was possible to develop an active catalyst for low-temperature decomposition of nitrous oxide in tail gases from nitric acid installations ( V), in which the main active ingredients are cobalt, nickel and zinc ions. It also turned out that the addition of alkali metal promoters such as sodium and potassium increases the activity of the catalyst and alkaline earth metals such as magnesium and calcium facilitate its formation and provide adequate structure and strength.
Katalizatory o różnych składach testowano w reaktorze kwarcowym, przez który przepuszczano mieszaninę podtlenku azotu i helu lub gazy resztkowe z pilotowej instalacji kwasu azotowego(V). Skład gazów resztkowych jest identyczny z występującym w przemysłowej instalacji kwasu azotowego. Badania w mieszaninie 5% podtlenku azotu w helu prowadzono w przepływowym reaktorze kwarcowym ze spiekiem, w zakresie temperatur od temperatury otoczenia do 450°C. Skład mieszaniny poreakcyjnej badano przy użyciu spektrometru masowego, mierząc ciśnienia parcjalne podtlenku azotu oraz produktów jego rozkładu: tlenu i azotu. Stwierdzono, że w temperaturze 300°C stopień rozkładu podtlenku azotu wynosi 95%, przy czym jedynymi produktami rozkładu były azot i tlen cząsteczkowy. W gazach resztkowych o składzie: 917 ppm NOx, 874 ppm N2O, 0,40% obj. H2O, 0,68% obj. O2,Catalysts of various compositions were tested in a quartz reactor through which a mixture of nitrous oxide and helium or residual gases from a pilot nitric acid plant (V) was passed. The composition of the residual gases is identical to that of an industrial nitric acid plant. Tests in the mixture of 5% nitrous oxide in helium were carried out in a flow quartz reactor with a sinter, in the temperature range from ambient temperature to 450 ° C. The composition of the post-reaction mixture was investigated using a mass spectrometer, measuring the partial pressures of nitrous oxide and its decomposition products: oxygen and nitrogen. The degree of decomposition of nitrous oxide was found to be 95% at 300 ° C, with nitrogen and molecular oxygen being the only decomposition products. In the residual gases with the following composition: 917 ppm NOx, 874 ppm N2O, 0.40 vol. H2O, 0.68 vol.% O2,
N2-reszta, badania prowadzono w temperaturze 400°C i przy obciążeniu katalizatora (GHSV) ok. -1N2-remainder, the tests were carried out at a temperature of 400 ° C and with a catalyst load (GHSV) of approx. -1
29000 h-1. Skład gazów przed i po złożu katalizatora oznaczano za pomocą analizatora FT-IR. Stwierdzono, że przy wyżej wymienionych parametrach stopień rozkładu N2O wynosi 99%.29,000 h -1 . The gas composition before and after the catalyst bed was determined using a FT-IR analyzer. The degree of N2O decomposition was found to be 99% with the above-mentioned parameters.
P r z y k ł a dP r z k ł a d
W naczyniu o pojemności 800 cm3 rozpuszczono w 30 cm3 wody destylowanej 12,73 g sześciowodnego azotanu kobaltu(II), 3,63 g sześciowodnego azotanu niklu(II), 1,24 g sześciowodnego azotanu cynku(II) oraz 0,49 g czterowodnego azotanu wapnia(ll), tak, aby sumaryczne stężenie kationów w roztworze wynosiło ok. 2M. Uzyskany roztwór mieszano przy użyciu mieszadła magnetycznego, dodając równocześnie odczynnik strącający w postaci 15%-ego roztworu K2CO3. Czynność tę prowadzono aż do osiągnięcia pH roztworu mieszczącego się w zakresie 9,0-9,5. Powstały osad przetrzymywano w roztworze macierzystym przez 15 h w temperaturze otoczenia, po czym osad odsączono i przemywano, aż do uzyskania pH przesączu równego 7,0-7,5. Uzyskany w ten sposób prekursor suszono w temperaturze 120°C, a następnie kalcynowano w temperaturze 400-450°C.In a vessel with a capacity of 800 cm 3, 12.73 g of cobalt (II) nitrate hexahydrate, 3.63 g of nickel (II) nitrate hexahydrate, 1.24 g of zinc (II) nitrate hexahydrate and 0.49 g of zinc (II) nitrate hexahydrate were dissolved in 30 cm 3 of distilled water. g of calcium nitrate tetrahydrate (II), so that the total concentration of cations in the solution was about 2M. The resulting solution was stirred with a magnetic stirrer while adding the precipitating reagent as a 15% K2CO3 solution. This operation was carried out until the pH of the solution was in the range 9.0-9.5. The resulting precipitate was kept in the mother liquor for 15 h at ambient temperature, then the precipitate was filtered off and washed until the filtrate had a pH of 7.0-7.5. The thus obtained precursor was dried at a temperature of 120 ° C and then calcined at a temperature of 400-450 ° C.
Otrzymano katalizator zawierający w przeliczeniu na tlenki 70,00% wagowych Co3O4, 21,00% wagowych Ni2O3, 7,00% wagowych ZnO, 1,9% wagowych CaO oraz 0,1% wagowych K2O.A catalyst was obtained containing, based on the oxides, 70.00% by weight of Co3O4, 21.00% by weight of Ni2O3, 7.00% by weight of ZnO, 1.9% by weight of CaO and 0.1% by weight of K2O.
Claims (3)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL385251A PL213796B1 (en) | 2008-05-21 | 2008-05-21 | Catalytic agent for low temperature decomposition of dinitrogen monoxide |
| PCT/PL2009/000050 WO2009142520A1 (en) | 2008-05-21 | 2009-05-19 | Catalyst for low-temperature decomposition of dinitrogen oxide and a process for the preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL385251A PL213796B1 (en) | 2008-05-21 | 2008-05-21 | Catalytic agent for low temperature decomposition of dinitrogen monoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL385251A1 PL385251A1 (en) | 2009-11-23 |
| PL213796B1 true PL213796B1 (en) | 2013-05-31 |
Family
ID=42987324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL385251A PL213796B1 (en) | 2008-05-21 | 2008-05-21 | Catalytic agent for low temperature decomposition of dinitrogen monoxide |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL213796B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3078419A1 (en) | 2015-03-13 | 2016-10-12 | Instytut Nawozów Sztucznych | Supported co-zn spinel catalyst for the abatement of nitrogen(i) oxide emissions especially from nitric acid plants and a method for its manufacture |
-
2008
- 2008-05-21 PL PL385251A patent/PL213796B1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3078419A1 (en) | 2015-03-13 | 2016-10-12 | Instytut Nawozów Sztucznych | Supported co-zn spinel catalyst for the abatement of nitrogen(i) oxide emissions especially from nitric acid plants and a method for its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| PL385251A1 (en) | 2009-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2009142520A1 (en) | Catalyst for low-temperature decomposition of dinitrogen oxide and a process for the preparation thereof | |
| Zhou et al. | Manganese doped CeO2-ZrO2 catalyst for elemental mercury oxidation at low temperature | |
| CN101920213B (en) | Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof | |
| CN101664690A (en) | Catalyst and preparation method and application thereof | |
| CN101745394A (en) | Catalyst used for decomposing N2O and preparation method and application thereof | |
| CN105363451A (en) | A high-efficiency catalyst for decomposing N2O, its preparation method and application | |
| Yu et al. | Apparent activation energies and reaction rates of N2O decomposition via different routes over Co3O4 | |
| Konsolakis et al. | N2O decomposition over doubly-promoted Pt (K)/Al2O3–(CeO2–La2O3) structured catalysts: on the combined effects of promotion and feed composition | |
| CN107983354B (en) | A kind of preparation method of anti-alkali poisoning copper-based spinel low-temperature denitration catalyst | |
| Duan et al. | Improving the H2O/SO2 tolerance of Nd-modified Mn-Fe/FA through tailing the micro-environment of active sites in low-temperature NH3-SCR | |
| CN101664694A (en) | Catalyst for decomposition of N2O and preparation method and application thereof | |
| Liu et al. | Efficient MnFeW/Ti catalyst for simultaneous removal of NO and Hg0 in flue gas at low temperature: Effect of NO on Hg0 oxidation and reaction mechanism | |
| Tran et al. | In-situ catalytic abatement of NOx during fluidized bed combustion—A literature study | |
| Zhang et al. | Sulfate-modified Ce-Ti on the low-temperature selective catalytic reduction: Influence on the reaction pathway | |
| Li et al. | Study on NH3-SCR performance and mechanism of Mn supported SO42−-CeCO3F-CePO4 catalysts | |
| Wei-yi et al. | Reaction mechanism of NOx removal from flue gas with pyrolusite slurry | |
| Liu et al. | Operando IR and in situ XAFS-DRIFTS studies on selective catalytic reduction of N2O by CH4 in NO-and NH3-containing atmospheres | |
| CN103170344A (en) | Catalyst for low-temperature SCR (Selective Catalytic Reduction) denitration and preparation method of catalyst | |
| CN111939922B (en) | Catalyst for catalyzing hydrogen peroxide to oxidize NO, preparation method and application thereof | |
| CN100528345C (en) | Denitration catalyst, and preparation method | |
| Liu et al. | Simultaneous removal of NO and N2O in the presence of NH3 and CH4 on Fe-zeolites | |
| Inayat et al. | Decomposition of N2O at low temperature over Co3O4 prepared by different methods | |
| CN105749959A (en) | High-silica molecular sieve catalyst used for nitrous oxide decomposition | |
| CN102864008B (en) | Composite oxide oxygen carrier and preparation method and application thereof | |
| CN116571251B (en) | Highly water-resistant and sulfur-resistant manganese-based catalyst and preparation method thereof |