DE2006347A1 - Catalyst for the synthesis of ammonia - Google Patents
Catalyst for the synthesis of ammoniaInfo
- Publication number
- DE2006347A1 DE2006347A1 DE19702006347 DE2006347A DE2006347A1 DE 2006347 A1 DE2006347 A1 DE 2006347A1 DE 19702006347 DE19702006347 DE 19702006347 DE 2006347 A DE2006347 A DE 2006347A DE 2006347 A1 DE2006347 A1 DE 2006347A1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- alkali metal
- porphyrin
- graphite
- ammonia
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title description 26
- 229910021529 ammonia Inorganic materials 0.000 title description 13
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 title description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 20
- 150000001340 alkali metals Chemical class 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- -1 .Nikkeis Chemical compound 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052845 zircon Inorganic materials 0.000 claims 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/11—Lithium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/12—Sodium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/13—Potassium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
Description
Katalysator für die AmmoniaksyntheseCatalyst for the synthesis of ammonia
BAD ORIGINALBATH ORIGINAL
Die Erfindung betrifft einen Katalysator für eine direkte Ämmoniaksynthese aus gasförmigem Wasserstoff und Stickstoff. ' : ■ The invention relates to a catalyst for direct ammonia synthesis from gaseous hydrogen and nitrogen. ': ■
Die bisher benutzten industriellen Verfahren zur Aimnoniaksynthese sind dasHaber-Bosch-Verfahren, das Claude-Verfahren und das Mont-Cenis-Verfahren. Als wichtigster Katalysator wird bei den ersten beiden Verfahren ein Eisenoxid-Katalysator und bei dem letztgenannten Verfahren ein Cyanoferrat-Komplexsalz benutzt. Allen diesen Katalysatoren ist gerneinsam,- dass sie im wesentlichen aus Eisenverbindungen als katalytisch aktiver Komponente und gegebenenfalls aus Aktivatoren bestehen und dass sie erstr nach einer Reduktionsbehandlung eingesetzt werden sollten.The industrial processes used to date for the synthesis of Aimnoniaks are the Haber-Bosch process, the Claude process and the Mont Cenis method. As the main catalyst an iron oxide catalyst is used in the first two processes and a cyanoferrate complex salt in the latter process used. What all these catalysts have in common is that they are essentially composed of iron compounds as a catalytically active component and optionally off Activators exist and that they only take effect after a reduction treatment should be used.
Spuren von Sauerstoff oder Kohlenmonoxid wirken darüber "· hinaus auf diese Katalysatoren als Katalysatorgifte und führen zu einem Nachlassen der katalytischen Wirksamkeit,Traces of oxygen or carbon monoxide also act on these catalysts as catalyst poisons and lead to a decrease in the catalytic effectiveness,
■Die-Katalysatoren gemä-ss der Erfindung, die in ihrer Art vollkommen neu sind und eine von den bisher gebräuchlichen■ Die-catalysts according to the invention, which in their kind are completely new and one of the previously used
009832/1735009832/1735
Katalysatoren vollkommen abweichende Zusammensetzung aufweisen, üind dadurch gekennzeichnet, dass sie Komplexverbindungen mindestens eines der Alkalimetalle mit nindestens einem der Übergangsnietallphthalocy.anine, mindestens einem der Übergangsmetallporphyrine oder mit Graphit enthalten.Catalysts have completely different compositions, characterized in that they are complex compounds at least one of the alkali metals with at least one of the transition nietallphthalocy.anine, at least one contain the transition metal porphyrins or with graphite.
Diese Komplexverbindungen gehören zu. der Gruppe der Elektronen-Donator-Akzeptor-Komplexe bzw. charge-tränsfer-Komplexe, in denen die tfbergajagsmetallplithalocyanine, die übergangöinetallporphyrine und Graphit die Elektronen-Akzeptoren und die Alkalimetalle die Elektronen-Donatoren sind.These complex compounds belong to. the group of electron donor acceptor complexes or charge transfer complexes, in which the tfbergajagsmetallplithalocyanine, the transition metal porphyrins and graphite are the electron acceptors and the alkali metals are the electron donors.
Der Begriff Alkalimetalle schliesst die folgenden rietalle ein: Lithium, Natrium, Kalium, Rubidium und Cäsium.The term alkali metals includes the following rietalle a: lithium, sodium, potassium, rubidium and cesium.
Die Übrrgangsmetal!phthalocyanine sind z.B. die Phthalocyanine von Eisen, Nickel, Kobalt, Wolfram, Platin, Titan, Mangan, Chrom, Zirkon, Hafnium, Vanadin, Molybdän, Osmium, Palladium, Ruthenium, Rhodium und Iridium.The remaining metal phthalocyanines are, for example, the phthalocyanines of iron, nickel, cobalt, tungsten, platinum, titanium, manganese, chromium, zirconium, hafnium, vanadium, molybdenum, osmium, Palladium, ruthenium, rhodium and iridium.
Diese Übergangsmetallporphyrine sind z.B. Porphyrine von Eisen, Nickel, Kobalt, Wolfram, Platin, Iridium, Osmium, Titan, Mangan, Chrom, Zirkon, Hafnium, Vanadin, Molybdän, Wk Palladium, Ruthenium und Rhodium.These transition metal porphyrins are, for example, porphyrins of iron, nickel, cobalt, tungsten, platinum, iridium, osmium, titanium, manganese, chromium, zirconium, hafnium, vanadium, molybdenum, Wk palladium, ruthenium and rhodium.
Die Katalysatoren gemäss der Erfindung absorbieren eine beträchtliche Menge von gasförmigem Wasserstoff und Stickstoff und setzen eine Mischung von gasförmigem Wasserstoff und Stickstoff katalytisch in Ammoniak um. Eine Animonialfcbildung findet dagegen nicht statt, wenn das Gasgemisch nur über Alkalimetalle, nur übor Übergangsmetallphthalocyanine, nur über Übergangsmetallporphyrine oder nur über Graphit geleitet wird. Darüber hinaus wird an den Katalysatoren gemäss der Erfindung ebenso wie an den vorbekannten Katalysatoren der Prozess der Ainmoniakzersetzung umgekehrt. Die höchste Ammoniakausbeute wird daher bei tiefen Temperaturen und hohen Drücken, also auf der Seite hoher Gleichgewichtskonzentration an Ammoniak erzielt, The catalysts according to the invention absorb a considerable amount of gaseous hydrogen and nitrogen and put a mixture of gaseous hydrogen and nitrogen catalytically into ammonia. An animonial education does not take place, however, if the gas mixture only via alkali metals, only via transition metal phthalocyanines, is passed only over transition metal porphyrins or only over graphite. In addition, the catalysts according to of the invention as well as the process of ammonia decomposition in the previously known catalysts is reversed. the The highest ammonia yield is therefore achieved at low temperatures and high pressures, i.e. on the side with a high equilibrium concentration of ammonia,
009832/1735 bad original009832/1735 bad original
Die Katalysatoren gemass der Erfindung können "beispielsweise durch eines de?? folgenden Verfahren Iiergestellt werden:The catalysts according to the invention can "for example by one de ?? the following procedures can be established:
Ein überschuss mindestens eines der Alkalimetalle wird mit mindestens einem der Übergangsrietallphthalocyanine, mindestens einem der ÜbergangsiGetallporphyrine oder mit Graphit "bei einer Temperatur gemischt, die über dem Schmelzpunkt des Alkalimetalle^ "bzw. der Alkalimetalle liegt·An excess of at least one of the alkali metals is used at least one of the transition metal phthalocyanines, at least one of the transition metal porphyrins or with graphite "in one Mixed temperature that is above the melting point of the alkali metals ^ "or the alkali metals is ·
Bei Verwendung von Übergangsmetallphthalocynineri oder'" Über— gangSDietallporphyrinen werden das Alkalimetall "bzw· die i When using transition metal phthalocyanines or "transition dietal porphyrins, the alkali metal" or the i
Alkalimetalle und die Übergangsmetallphthalocyanine oder Übergangsmetallporphyrine auf einem Träger mit grosser Oberfläche niedergeschlagen und die so erhaltene Masse wird bei einer Temperatur oberhalb des Schmelzpunktes des Alkalimetalles bzw. der Alkalimetalle wärmebehandelt.Alkali metals and the transition metal phthalocyanines or Transition metal porphyrins deposited on a carrier with a large surface and the mass thus obtained is at a temperature above the melting point of the Alkali metal or the alkali metals heat-treated.
Die Erwähnung dieser Verfahren schliesst die Anwendung anderer Verfahren zur Herstellung von Katalysatoren gemäss der Erfindung nicht aus.The mention of these procedures concludes the application other process for the preparation of catalysts according to the invention does not stop.
Die erfindungsgemässen Katalysatoren bestehen aus komplexen Verbindungen zwischen den Alkalimetallen und den Übergangsmet allphthal ο cya Hin en, den Übergangsmetallporphyrinen oder Graphit und sind nach einem der vorgenannten Verfahren herstellbar.The catalysts according to the invention consist of complexes Compounds between the alkali metals and the transition metal allphthal ο cya Hin en, the transition metal porphyrins or graphite and are according to one of the aforementioned methods manufacturable.
Zur Aktivierung der erfindungsgemässen Katalysatoren bedarf es weder des Zusatzes von Aktivatoren noch einer reduzierenden Behandlung mit Wasserstoff. Darüber hinaus nimmt <lie katalytisch© Wirksamkeit der Katalysatoren gemäss der Erfindung in Gegenwart von gasförmigem Sauerstoff nicht ab.To activate the catalysts according to the invention, neither the addition of activators nor a reducing treatment with hydrogen. Furthermore increases the efficiency of the catalytic converters according to of the invention in the presence of gaseous oxygen does not depend.
Die im folgenden mitgeteilten Ausführungsbeispiele dienen zur Verdeutlichung deE Erfindung und sind nicht begrenzend zu versieben. 009832/1735 The exemplary embodiments reported below serve to illustrate the invention and should not be sifted in a limiting manner. 009832/1735
0,5 g iyctallirch.es Natrium wurden an der Innenwand ein ο ρ gläserner, als Heaktionsgefäse dien tu den U-Rohres nierlorgesclilager, ur ^ auf diese Schicht wurden dann o,1 g Eitonphthalocyanin aufgedampft. Diese niedergeschlagenen Substanzen wurden anschliessend bei 20O0C im Vakuuir getempert, wobei sicli ein tiefgefärbter Komplex von Eisenphthalocynin-Natrium bildete. In das Reaktionsgefäss mit dem so geb?lde ten Komplex wurde eine Ki ;;·.:■ lau. g von gasförmigem Ua.jcc.rstoff und Stickstoff eingeleitet und mit einer GeßcLvrindigkeit von 12,2 ml/min umgewälzt. Dac Volumen des "ΰι,:-:'ά1ζ-systems betrug ca. 140 ml. Die nech dem BET-Veνfahreη bestimmte Oberfläche des komplexen Katalysetoz-c betixi^ ca. 1 m /g'der in einer Kühlfalle gesammelte Ammoniak mirde quantitativ mit Hilfe der Gasiiromatograpliie und Infrarotspektrometrio analysiert. Die Ergebnisse sind in Tabelle I zusammengestellt. Wenn der so erhaltene Katalysator 10 bis 20 cmllg Sauerstoff oder Kohlenmonoxid ausgesetzt wurdo, so wurde dadurch seine katalytisch^ Aktivität praktir-cli nicht verändert.0.5 g of iyctallirch.es sodium was placed on the inner wall of a glass, the U-tubes serve as heating vessels; 0.1 g of ion phthalocyanine was then evaporated onto this layer. These precipitated substances were then tempered in a vacuum at 20O 0 C, whereby a deeply colored complex of iron phthalocyanine sodium formed. A Ki ;; ·.: ■ lukewarm. g of gaseous fuel and nitrogen were introduced and circulated at a speed of 12.2 ml / min. Dac volume of the "ΰι,: -:. 'Ά1ζ- system was approximately 140 ml The nech the BET specific surface Ve ν fahreη the complex Katalysetoz-c ^ betixi about 1 m / g'der in a cold trap collected ammonia mirde Analyzed quantitatively with the aid of gas chromatography and infrared spectrometry, the results are summarized in Table I. If the catalyst obtained in this way was exposed to 10 to 20 cm / 1 g of oxygen or carbon monoxide, its catalytic activity was practically unchanged.
009.832/1735009.832 / 1735
BAD ORIGINAL BATH ORIGINAL
Beispiel 2 . " . - Example 2 . ". -
Die Katalysatoren wurden in der gleichen Weise wie in Beispiel 1 hergestellt, wobei 0,5 g der verschiedenen Alkalimetalle mit 0,2 g der verschiedenen tJbergangsmetallphbhalocyanine in der aus Tabelle II ersichtlichen Zusammenstellung umgesetzt wurden* Ebenfalls aus Tabelle II sind die Ergebnisse der unter Verwendung der entsprechenden .Katalysatoren durchgeführten Ammoniaksyfchese zu entnehmen, wobei die Oberfläche der Katalysatoren wiederkam $e ca. 1 m /g. betrug. .The catalysts were prepared in the same manner as in Example 1, 0.5 g of the various alkali metals being reacted with 0.2 g of the various transition metal phbhalocyanines in the compilation shown in Table II refer corresponding .Katalysatoren performed Ammoniaksyfchese, wherein the surface of the catalysts returned $ e about 1 m / g. fraud. .
Pc » Phthalocyanin ·.Pc »phthalocyanine ·.
* ■ Das Volumen des Heaktionssystems beträgt ca· 100 ml ** » Das Volumen des Reaktionssystems beträgt ca. 210 ml* ■ The volume of the heating system is approx. 100 ml ** »The volume of the reaction system is approx. 210 ml
009832/1735 .*" °HIGINAL 009832/1735. * "° HIGINAL
0,5 g metallisches Matrium und 0,2 g Eiseuphfclialocyaniri wurden auf 0,1 g Aktivkohle mit einer Oberfläche von ca. 600 Hi4Vg niedergeschlagen und zum Katalysator umgesetzt. Die Ergebnisse der mit diesem Katalysator durchgeführten Ammoniaksyntbese sind in Tabelle IET dargestellt. Das Volumen des Reaktionssystems betrug ca. 140 ml.0.5 g metallic matrium and 0.2 g Eiseuphfclialocyaniri were deposited on 0.1 g activated charcoal with a surface of about 600 Hi 4 µg and converted to the catalyst. The results of the ammonia synthesis carried out with this catalyst are shown in Table IET. The volume of the reaction system was about 140 ml.
Die Katalysatoren wux'den in der gleichen Weise wie in Beispiel 1 beschrieben dargestellt, wobei 0,5 g metallisches Natrium und 0,2 g Übergangsmetall-Tetraphenylporphin in der aus Tabelle IV ersichtlichen Zusammensetzung umgesetzt wurden. Die Ergebnisse der mit den so dargestellten Katalysatoren durchgeführten Ammoniaksynthese sind in Tabelle IV zusammengestellt· Das Volumen des Reaktionssystems betrug ca. 140 ml .The catalysts wux'den in the same way as in example 1, with 0.5 g of metallic sodium and 0.2 g of transition metal tetraphenylporphine in the from Table IV apparent composition were implemented. The results of the catalysts shown in this way ammonia synthesis carried out are shown in Table IV. The volume of the reaction system was approx. 140 ml.
009832/1735009832/1735
--
Katalysator Partial— drucit desCatalyst partial pressure des
' eingeleiteten Gases ' introduced gas
-(cmtQg)- (cmtQg)
Reaktionstemperatur Reaction temperature
Or·Or
Ammoniak ausbeute nach 20Ammonia yield after 20
tundenhours
:(mT unter ITormalbedingungen) : (mT under ITormal conditions)
Na-OlFe (Hl)-tetraphenyl- porphinNa-OlFe (Hl) -tetraphenyl- porphine
Na-Oirin (IIT)-tetraplienyl— porphinNa-Oirin (IIT) -tetraplienyl- porphine
1010
JOJO
3030th
110 240110 240
240240
0,20.2
8,28.2
0,80.8
0,01 0,410.01 0.41
0,040.04
Ein Graphit-Alkalimetall-Komplex-Katalysator wurde durch tTir-retzen von ca. 2 g Graphitpulver mit ca. 2 g AlkalimetallA graphite alkali metal complex catalyst was made by tTir-retting of approx. 2 g of graphite powder with approx. 2 g of alkali metal
im Vakuum "beiin a vacuum "
O/O/
einem gläsernen U-Rohr erhalten.a glass U-tube.
In dem auf einer bestimmten Temperatur gehaltenen Eeaktionsgefäss wird ein Wasserstoff-Stickstoff-Gemisch mit einer Geschwindigkeit von Ί2 ml/min umgewälzt. Das Volumen des TJmwäl ζ systems "beträgt; ca. 114- ml. Die Oberfläche des Komplexes, die mit Hilfe der BET-Methode unter Verwendung von Stickstoff bestimmt wrde, betrug ca. 5OO m /g.In the reaction vessel kept at a certain temperature a hydrogen-nitrogen mixture is circulated at a rate of Ί2 ml / min. The volume of the TJmwäl ζ systems "is approx. 114 ml. The surface of the complex, which is determined with the aid of the BET method using Nitrogen was determined, was approx. 500 m / g.
009832/17009832/17
BAD ORIGINALBATH ORIGINAL
Das Reaktionsprodukte, der Ammoniak, wurde in eine.n al;; K'*:.lfalle dienenden und im 'Jmwälasystem eingebauten glHserner! U-Rohr, das mit flüssigem Stickstoff gekühlt wurde, aufgefangen, und anschliessend mit Hilfe der Infrarot spektrometrie und der Gar.chromatographie analysiert. Die Ergebnisse sind in Tobelle Y wiedergegeben.The reaction product, the ammonia, was converted into a.n al ;; K '*: lfalle serving and in the' Jmwälasystem built in glass! U-tube, which has been cooled with liquid nitrogen, is collected and then analyzed with the aid of infrared spectrometry and Garchromatographie. The results are given in Tobelle Y.
Durch die Gegenwart vcn Sauerstoff und Kohlenmonoxid vrurdr? die Aktivität· des Komplexes praktisch kaum verändert.Due to the presence of oxygen and carbon monoxide the activity of the complex hardly changed at all.
Katalysator Tartialdruck des eingeleiteten Catalyst partial pressure des initiated
GasesGas
( cmllg )(cmllg)
Reaktionstemperatur Reaction temperature
ο,ο,
Ammoniakausbeute nach 12 S bun den (ml unler Normalbodingungen) Ammonia yield after 12 buns (ml unler Normal conditions)
-',- ',
5 beschriebenen Weise wurde5 was described
In der gleichen wie in Beispiel
der Katalysator aus einem Gramm eim: π Alkalinictalles und
zwei Gramm Graphit hergestellt. Die Ergebnisse der mit diesen
•Katalysatoren durchgeführten Amineninksynth.esο sind ih Tabelle
VI zusammengestellt. Die Oberfläche des Katalysators betrug ca. 20 m /g und das Volumcr. dos Reaktionssycteir.n betrug ca.
510 ml.In the same as in example
The catalyst is made from one gram of eim : π Alkalinictalles and two grams of graphite. The results of the Amineninksynth.esο carried out with these catalysts are summarized in Table VI. The surface of the catalyst was approx. 20 m / g and the volume. dos reaction sycteir.n was approx. 510 ml.
009832/1735009832/1735
ORIGINALORIGINAL
3 2NH / N
3 2
BAD ORIGJNÄLBAD ORIGJNÄL
00 9832/17 3500 9832/17 35
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP894169 | 1969-02-06 | ||
JP894069 | 1969-02-06 |
Publications (3)
Publication Number | Publication Date |
---|---|
DE2006347A1 true DE2006347A1 (en) | 1970-08-06 |
DE2006347B2 DE2006347B2 (en) | 1973-09-20 |
DE2006347C3 DE2006347C3 (en) | 1974-10-31 |
Family
ID=26343569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2006347A Expired DE2006347C3 (en) | 1969-02-06 | 1970-02-04 | Process for the preparation of a catalyst |
Country Status (4)
Country | Link |
---|---|
BE (1) | BE745624A (en) |
DE (1) | DE2006347C3 (en) |
FR (1) | FR2030339A1 (en) |
GB (1) | GB1288546A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0066103A1 (en) * | 1981-05-29 | 1982-12-08 | Eckert, Heiner, dr. | Process for the reduction of reducible groups, and its application |
US4800188A (en) * | 1987-03-20 | 1989-01-24 | Hoechst Celanese Corp. | Method for supporting metalloporphyrins on polybenzimidazole porous articles |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8827123D0 (en) * | 1988-11-21 | 1988-12-29 | Atomic Energy Authority Uk | Supported oxidation catalyst |
-
1970
- 1970-02-03 GB GB1288546D patent/GB1288546A/en not_active Expired
- 1970-02-04 DE DE2006347A patent/DE2006347C3/en not_active Expired
- 1970-02-05 FR FR7004140A patent/FR2030339A1/fr not_active Withdrawn
- 1970-02-06 BE BE745624D patent/BE745624A/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0066103A1 (en) * | 1981-05-29 | 1982-12-08 | Eckert, Heiner, dr. | Process for the reduction of reducible groups, and its application |
US4800188A (en) * | 1987-03-20 | 1989-01-24 | Hoechst Celanese Corp. | Method for supporting metalloporphyrins on polybenzimidazole porous articles |
Also Published As
Publication number | Publication date |
---|---|
FR2030339A1 (en) | 1970-11-13 |
GB1288546A (en) | 1972-09-13 |
DE2006347C3 (en) | 1974-10-31 |
DE2006347B2 (en) | 1973-09-20 |
BE745624A (en) | 1970-07-16 |
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