FR2515064A1 - Rhodium, iridium or cobalt complexes - with substd. phenanthroline or bi:pyridyl ligand, useful as shift conversion catalyst - Google Patents
Rhodium, iridium or cobalt complexes - with substd. phenanthroline or bi:pyridyl ligand, useful as shift conversion catalyst Download PDFInfo
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- FR2515064A1 FR2515064A1 FR8119910A FR8119910A FR2515064A1 FR 2515064 A1 FR2515064 A1 FR 2515064A1 FR 8119910 A FR8119910 A FR 8119910A FR 8119910 A FR8119910 A FR 8119910A FR 2515064 A1 FR2515064 A1 FR 2515064A1
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- phenanthroline
- ligand
- iridium
- rhodium
- complexes
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- 239000003446 ligand Substances 0.000 title claims abstract description 22
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 16
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 11
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 title claims description 26
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims description 14
- 239000010948 rhodium Substances 0.000 title claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims description 12
- 150000001868 cobalt Chemical class 0.000 title claims description 3
- 125000004076 pyridyl group Chemical group 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 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
- -1 sulfonate radical Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 150000005041 phenanthrolines Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 244000070969 koal Species 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0013—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group without a metal-carbon linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
La présente invention concerne la réaction de conversion du gaz à l'eau et plus particulièrement les catalyseurs destinés à favoriser la production d'hydrogène. The present invention relates to the gas to water conversion reaction and more particularly to catalysts intended to promote the production of hydrogen.
La réaction de conversion du gaz à l'eau correspond à l'équilibre suivant :
The gas to water conversion reaction corresponds to the following equilibrium:
I1 s'agit d'un procédé intéressant pour préparer l'hydrogène à partir de l'eau, ou bien pour augmenter la proportion d'hydrogène dans le gaz de synthèse qui est utilisé notamment dans les réactions de méthanation et les synthèses de Fischer et Tropsch. It is an interesting process for preparing hydrogen from water, or else for increasing the proportion of hydrogen in the synthesis gas which is used in particular in methanation reactions and Fischer syntheses and Tropsch.
La mise en oeuvre de cette réaction pose certains problèmes. En effet, la constante d'équilibre de cette réaction de conversion croît lorsque la température décroît ; ctest pourquoi des taux de conversion élevés en hydrogène ne peuvent être obtenus qu'à basse température. Dans ces conditions, il est nécessaire de disposer de catalyseurs très actifs afin d'obtenir des taux de conversion satisfaisants tout en conservant des vitesses de réaction acceptables. The implementation of this reaction poses certain problems. Indeed, the equilibrium constant of this conversion reaction increases when the temperature decreases; This is why high conversion rates to hydrogen can only be obtained at low temperatures. Under these conditions, it is necessary to have very active catalysts in order to obtain satisfactory conversion rates while maintaining acceptable reaction rates.
Ainsi, bien que la réaction soit thermodynamiquement favorable (AG 298 = - 4,76 Koal pour
H2O liquide), elle nécessite des températures et des pressions élevées pour de dérouler à des vitesses acceptahles en présence de catalyseurs hétérogènes.Thus, although the reaction is thermodynamically favorable (AG 298 = - 4.76 Koal for
Liquid H2O), it requires high temperatures and pressures to unwind at acceptable speeds in the presence of heterogeneous catalysts.
Récemment, on a commencé à développer des catalyseurs homogènes, parmi lesquels des métaux carbonyles utilisés en conditions fortement acides ou alcalines ou bien des complexes de phosphine et de platine, de rhodium ou de nickel. Recently, we have started to develop homogeneous catalysts, among which carbonyl metals used under strongly acid or alkaline conditions or else complexes of phosphine and platinum, rhodium or nickel.
Toutefois, aucun de ces catalyseurs ne donnant parfaitement satisfaction, il est intéressant d'en proposer de nouveaux susceptibles d'améliorer encore les performances du procédé. However, none of these catalysts being entirely satisfactory, it is advantageous to propose new ones capable of further improving the performance of the process.
C'est pourquoi la présente invention propose de nouveaux complexes utiles notamment comme catalyseurs dans la conversion du gaz à l'eau, caractérisés en ce qu'ils comportent un complexe du rhodium, de l'iridium ou du cobalt avec, à titre de ligand, un dérivé de la phénanthroline ou de la bipyridine portant au moins un substituant en or des atomes d'azote du ligand et éventuellement au moins un substituant hydrophile. This is why the present invention provides new complexes useful in particular as catalysts in the conversion of gas to water, characterized in that they comprise a complex of rhodium, iridium or cobalt with, as ligand , a phenanthroline or bipyridine derivative carrying at least one gold substituent of the nitrogen atoms of the ligand and optionally at least one hydrophilic substituent.
La nature des substituants hydrophiles n'est pas déterminante dans l'activiste des complexes selon l'invention car la fonction essentielle de ces substituants est d'assurer la solubilisation du ligand en phase aqueuse. Parmi es substituants hydrophiles, il faut citer en particulier les sulfonates. The nature of the hydrophilic substituents is not decisive in the activist of the complexes according to the invention because the essential function of these substituents is to ensure the solubilization of the ligand in the aqueous phase. Among the hydrophilic substituents, mention should be made in particular of sulfonates.
De même, si la présence des substituants en a des atones d'azote du ligand est indispensable, ils peuvent être variés, leur fonction étant probablement d'empêcher la formation d'une structure planaire stable dans le chélate que l'on observe avec des dérivés non substitués en a de 1 'azote. Likewise, if the presence of the substituents in a atones of nitrogen of the ligand is essential, they can be varied, their function probably being to prevent the formation of a stable planar structure in the chelate which is observed with unsubstituted derivatives of nitrogen.
Parmi les dérivés de la phénanthroline particulièrement intéressants å mettre en oeuvre, il faut citer les composés de formule
dans lesquels R représente un radical alcoyle inférieur en C1 à C5 et M représente un cation d'un métal de préférence alcalin tel que le sodium ou le potassium, en particulier la 2,9-diméthyl-4,7-di(p-phényl-sulfonate de sodium)-l,lO-phénanthroline.Among the phenanthroline derivatives which are particularly advantageous to use, mention should be made of the compounds of formula
in which R represents a lower C1 to C5 alkyl radical and M represents a cation of a preferably alkali metal such as sodium or potassium, in particular 2,9-dimethyl-4,7-di (p-phenyl -sodium sulfonate) -l, lO-phenanthroline.
Parmi les dérivés de bipyridine utilisables, il faut mentionner les composés de formule
dans lesquels R représente un radical alcoyle inférieur en C1 à C5 et M, comme précédemment, représente le cation d'un métal, en particulier d'un métal alcalin tel que le sodium ou le potassium.Among the bipyridine derivatives which can be used, mention must be made of the compounds of formula
in which R represents a lower C1 to C5 alkyl radical and M, as before, represents the cation of a metal, in particular of an alkali metal such as sodium or potassium.
Les complexes selon la présente invention peuvent être préparés par mise en présence dans un solvant d'un sel de rhodium, d'iridium ou de cobalt et de l'agent complexant dérivé de la phénanthroline ou de la bipyridine. The complexes according to the present invention can be prepared by bringing together in a solvent a rhodium, iridium or cobalt salt and the complexing agent derived from phenanthroline or from bipyridine.
De préférence, ces complexes sont préparés in situ dans un milieu aqueux servant de solvant. Preferably, these complexes are prepared in situ in an aqueous medium serving as a solvent.
Bien entendu, il est possible d'utiliser à titre de solvant des solutions aqueuses contenant d'autres solvants miscibles à l'eau tels que les alcools, en proportions variables, par exemple l'éthoxyéthanol. Of course, it is possible to use as solvent aqueous solutions containing other water-miscible solvents such as alcohols, in variable proportions, for example ethoxyethanol.
Les quantités respectives de sel de rhodium, d'iridium ou de cobalt par rapport aux quantités d'agent complexant peuvent varier dans une large mesure. Toutefois, le rapport ligand/métal exerçant une influence importante sur l'activité du complexe obtenu, on utilise en général un rapport molaire ligand/métal compris entre 1 et 3, et de préférence un rapport ligand/métal voisin de 2 pour les complexes de rhodium et de 1 pour les complexes d'iridium. The respective amounts of rhodium salt, iridium or cobalt relative to the amounts of complexing agent can vary to a large extent. However, the ligand / metal ratio exerting a significant influence on the activity of the complex obtained, a ligand / metal molar ratio of between 1 and 3 is generally used, and preferably a ligand / metal ratio close to 2 for the complexes of rhodium and 1 for iridium complexes.
A la différence des catalyseurs mis en oeuvre dans la technique antérieure, on constate que les catalyseurs selon la présente invention, en particulier les catalyseurs à l'iridium, sont actifs dans une gamme assez étendue de pH au voisinage de la neutralité, ainsi les catalyseurs selon l'invention a base d'iridium présentent une activité importante pour des pH compris entre 6 et 10. Unlike the catalysts used in the prior art, it can be seen that the catalysts according to the present invention, in particular the iridium catalysts, are active in a fairly wide range of pH in the vicinity of neutrality, thus the catalysts according to the invention based on iridium have significant activity for pH values between 6 and 10.
Les exemples ci-après sont destinés à illustrer d'autres caractéristiques et avantages de la présente invention. The examples below are intended to illustrate other characteristics and advantages of the present invention.
Dans ce qui va suivre, on utilise les abréviations suivantes - 4,7-di(p-phénylsulfonate de sodium)-l,10-phénanthroline
phen-S
(composé de formule I dans laquelle R = H et M = Na) - 4,7-di(p-phénylsulfonate de sodium)-2,9-dimethyl-
1,10-phénanthroline :
2,9-dmphen-s
(compose de formule I dans laquelle R = CH3 et M = Na)
Le composé phen-S ne fait pas partie de la présente invention et n'est utilisé u'à titre comparatif.In the following, the following abbreviations are used - 4,7-di (sodium p-phenylsulfonate) -1,10-phenanthroline
phen-S
(compound of formula I in which R = H and M = Na) - 4,7-di (sodium p-phenylsulfonate) -2,9-dimethyl-
1,10-phenanthroline:
2.9-dmphen-s
(composed of formula I in which R = CH3 and M = Na)
The phen-S compound is not part of the present invention and is used only for comparison.
Exemple 1
Préparation du chélate d'iridium et de la 2,9-dmphen-s
On dissout 10 micromoles de IrCl313H20 et 10 micromoles de 2,9-dmphen-S dans 10 ml d'un tampon phosphate de sodium (1M, pH 5,4).Example 1
Preparation of iridium chelate and 2,9-dmphen-s
10 micromoles of IrCl313H20 and 10 micromoles of 2,9-dmphen-S are dissolved in 10 ml of sodium phosphate buffer (1M, pH 5.4).
Le mélange ainsi obtenu est chauffé à 1000C sous agitation magnétique (300 tr/min.), sous argon, pendant 3 heures. The mixture thus obtained is heated to 1000C with magnetic stirring (300 rpm), under argon, for 3 hours.
On obtient ainsi une solution aqueuse d'un complexe selon la présente invention. An aqueous solution of a complex according to the present invention is thus obtained.
Afin de mettre en évidence les propriétés de ce complexe, on introduit dans le récipient pendant 15 min. de l'oxyde de carbone (pureté supérieure à 99,995 %), après quoi l'ouverture d'admission est fermée. In order to demonstrate the properties of this complex, it is introduced into the container for 15 min. carbon monoxide (purity greater than 99.995%), after which the intake opening is closed.
Le volume interne de l'appareil est de 330 ml, la pression interne est égalisée avec la pression atmosphérique au moyen d'une valve à mercure. The internal volume of the device is 330 ml, the internal pressure is equalized with atmospheric pressure by means of a mercury valve.
Le gaz obtenu est analysé par chromatographie en phase vapeur, sa composition étant déterminée en fonction du temps. The gas obtained is analyzed by vapor phase chromatography, its composition being determined as a function of time.
La production moyenne mesurée est de 15 moles de H2/mole de catalyseur heure. The average production measured is 15 moles of H2 / mole of catalyst hour.
Exemples 2 à 11
Afin de mettre en évidence les propriétés avantageuses du complexe selon la présente invention on réalise différents complexes selon l'invention ainsi que des complexes de comparaison en utilisant le procédé décrit a l'exemple 1.Examples 2 to 11
In order to demonstrate the advantageous properties of the complex according to the present invention, various complexes according to the invention are produced as well as comparison complexes using the process described in Example 1.
Les essais des catalyseurs sont conduits à 1000C à pH 5,4, la pression étant de 1 atm. de CO comme cela est décrit dans l'exemple 1. The catalyst tests are carried out at 1000C at pH 5.4, the pressure being 1 atm. CO as described in Example 1.
Dans chaque expérience, la quantité de métal utilisée est de lO.micromoles. In each experiment, the amount of metal used is 10 micromoles.
Les résultats-qui sont rassemblés dans le tableau 1 sont donnés en nombre de mole. de H2 par nombre de mole de catalseur : nH2/not et en nombre de mole de H2/nombre de mole de catalyseur.heure: nH2/ncat.h, TANLEAU I ligand Temps total nH2/ncat nH2/ncat.n
Exemple Sel du métal (tapport molaire de chauffage (heure-1)
ligand/métal) (heure) 2 RhCl3.3H2O - 14 0,5 0,04 3 RhCl3.3H2O phen-S (2) 18,5 1,1 0,06 4 RhCl3.3H2O 2,9-dmphen-S (1) 16,4 178 10,8 5 RhCl3.3H2O 2,9-dmphen-S (2) 16,4 382 23,3 6 RhCl3.3H2O 2,9-dmphen-S (3) 16,4 224 13,7 7 IrCl3.3H2O - 18,2 2,6 0,15 8 IrCl3.3H2O phen-S (1) 18,5 1,1 0,06 9 IrCl3.3H2O 2,9-dmphen-S (1) 19 290 15 10 IrCl3.3H2O 2,9-dmphen-S (2) 18,3 172 9,4 11 IrCl3.3H2O 2,9-dmphen-S (3) 18,1 196 10,8
En général, le mélange réactionnel devient bleu foncé pour les complexes d'iridium après quelques minutes lorsque l'on iZecte l'oxyde de carbone dans le récipient.The results which are collated in Table 1 are given in number of moles. of H2 by number of moles of catalyst: nH2 / not and in number of moles of H2 / number of moles of catalyst. time: nH2 / ncat.h, TANLEAU I ligand Total time nH2 / ncat nH2 / ncat.n
Example Metal salt (molar heating ratio (hour-1)
ligand / metal) (hour) 2 RhCl3.3H2O - 14 0.5 0.04 3 RhCl3.3H2O phen-S (2) 18.5 1.1 0.06 4 RhCl3.3H2O 2.9-dmphen-S ( 1) 16.4 178 10.8 5 RhCl3.3H2O 2.9-dmphen-S (2) 16.4 382 23.3 6 RhCl3.3H2O 2.9-dmphen-S (3) 16.4 224 13, 7 7 IrCl3.3H2O - 18.2 2.6 0.15 8 IrCl3.3H2O phen-S (1) 18.5 1.1 0.06 9 IrCl3.3H2O 2.9-dmphen-S (1) 19 290 15 10 IrCl3.3H2O 2.9-dmphen-S (2) 18.3 172 9.4 11 IrCl3.3H2O 2.9-dmphen-S (3) 18.1 196 10.8
In general, the reaction mixture turns dark blue for the iridium complexes after a few minutes when the carbon monoxide is detected in the container.
Lorsque l'on part de systèmes catalytiques préparés in situ en mélangeant RhCl3.3H20 et la quantité désirée du ligand (exemples 3 à 6) le mélange devient-marron, puis un précipité noir apparaît. When starting from catalytic systems prepared in situ by mixing RhCl3.3H20 and the desired amount of ligand (examples 3 to 6) the mixture becomes brown, then a black precipitate appears.
I1 semble que cela corresponde à des produits fortement insolubles qui sont peut-être des complexes mono- ou dihydriques, bien que les études spectroscopiques ne démontrent pas de façon très nette la présence de tels composés. It appears to correspond to highly insoluble products which are perhaps mono- or dihydric complexes, although spectroscopic studies do not very clearly demonstrate the presence of such compounds.
Le catalyseur préparé à partir du chlorure d'iridium et d'un équivalent de 2,9-diméthylphénanthroline dans un mélange éthoxyéthanol/eau (4/1) s'est révélé etre le catalyseur le-plus efficace avec une production de 100 moles d'hydrogène par mole de catalyseur et par heure en opérant a 1000C, aucune précipitation n ' est observée et le système produit jusqu't 1 000 moles d'hydrogène pour l'iridium présent à l'origine. The catalyst prepared from iridium chloride and an equivalent of 2,9-dimethylphenanthroline in an ethoxyethanol / water mixture (4/1) has proved to be the most effective catalyst with a production of 100 moles of hydrogen per mole of catalyst and per hour operating at 1000C, no precipitation is observed and the system produces up to 1000 moles of hydrogen for the iridium originally present.
Il faut remarquer un effet assez important du pH sur l'activité des catalyseurs, en particulier sur les catalyseurs à base de rhodium. En effet, les catalyseurs à base d'iridium paraissent assez peu sensibles au pH et donnent des résultats satisfaisants dans la fourchette de 6 à 10. Comme la formation de
C02 est accélérée en milieu basique et que la formation de H2 est favorisée par un bas pH, l'influence du pH pour les complexes de rhodium dont l'optimum se situe entre 5 et 6 et l'efficacité de ces composés autour de la neutralité sont une indication que la cinétique d'oxydation de l'oxyde de carbone et la libération d'H2 sont très importantes.It should be noted that the pH has a fairly significant effect on the activity of the catalysts, in particular on rhodium-based catalysts. Indeed, the iridium-based catalysts appear to be relatively insensitive to pH and give satisfactory results in the range of 6 to 10. As the formation of
C02 is accelerated in basic medium and that the formation of H2 is favored by a low pH, the influence of pH for rhodium complexes whose optimum is between 5 and 6 and the effectiveness of these compounds around neutrality are an indication that the oxidation kinetics of carbon monoxide and the release of H2 are very important.
Des exemples du tableau 1 il ressort que les complexes de phénanthroline portant en a des atomes d'azote, c'est-à-dire en position 2 et 9, des substituants méthyles sont environ 300 fois plus efficaces que les dérivés de phénanthroline correspondants non méthylés. From the examples in Table 1, it can be seen that the phenanthroline complexes having nitrogen atoms, that is to say in positions 2 and 9, methyl substituents are approximately 300 times more effective than the corresponding non-phenanthroline derivatives. methylated.
Bien que le Demandeur ne désire pas être limité par une quelconque explication scientifique, on pense que les complexes de phénanthroline non substitués peuvent adopter une configuration plane carrée, alors que les dérivés de phénanthroline substitués peuvent -fa-;oriser les complexes mono-chélatés ou une géométrie non planaire. La stabilisation d'une géométrie planaire carrée par des dérivés de phénanthroline non substitués peut expliquer la faible activité des complexes correspondants. Although the Applicant does not wish to be limited by any scientific explanation, it is believed that the unsubstituted phenanthroline complexes can adopt a square planar configuration, while the substituted phenanthroline derivatives can - orize the mono-chelate complexes or non-planar geometry. The stabilization of a square planar geometry by unsubstituted phenanthroline derivatives may explain the low activity of the corresponding complexes.
Du tableau 1 il ressort également que le rapport molaire entre le métal et le ligand a une influence importante sur l'activité catalytique du système, à la fois pour le rhodium et pour l'iridium. Table 1 also shows that the molar ratio between the metal and the ligand has an important influence on the catalytic activity of the system, both for rhodium and for iridium.
Sur la figure ci-annexée,qui donne la production d'hydrogène en mole/mole de catalyseur.heure en fonction du rapport mole de ligand/mole de métal, il ressort que les catalyseurs les plus actifs comportent deux équivalents du dérivé de phénanthroline pour le rhodium alors que les catalyseurs les plus efficaces A 11 iridium sont obtenus en faisant réagir une mole de ligand par mole de métal. In the appended figure, which gives the production of hydrogen in mole / mole of catalyst. Hour as a function of the mole of ligand / mole of metal ratio, it appears that the most active catalysts comprise two equivalents of the phenanthroline derivative for rhodium whereas the most efficient catalysts for iridium are obtained by reacting one mole of ligand per mole of metal.
Dans le cas où il n'est pas utilise d'agent chélatant, comme par exemple dans les expériences 1 et 6, on observe une précipitation de métal qui est due à la réduction du sel de départ par l'oxyde de carbone. In the case where a chelating agent is not used, as for example in experiments 1 and 6, a precipitation of metal is observed which is due to the reduction of the starting salt by carbon monoxide.
Les catalyseurs les plus efficaces sont stables dans les conditions expérimentales et l'activité de ces systèmes est constante pendant un grand nombre de jours. The most efficient catalysts are stable under experimental conditions and the activity of these systems is constant for a large number of days.
En outre, les spectres électroniques des solutions de départ du mélange réactionnel,après formation d'environ 100 moles d'hydrogène pour le rhodium, sont identiques aux spectres de départ. Ainsi, bien que la comparaison avec d'autres catalyseurs de conversion du gaz à l'eau déjà décrits soit difficile car les conditions opératoires sont dans tous les cas très différentes, les présents catalyseurs semblent etre parmi les systèmes les plus actifs. En outre ils couvrent une assez large bande de pH autour de la neutralité, zone dans laquelle les systèmes catalytiques connus précédemment semblaient présenter peu d'activité. In addition, the electron spectra of the starting solutions of the reaction mixture, after formation of approximately 100 moles of hydrogen for rhodium, are identical to the starting spectra. Thus, although the comparison with other catalysts for the conversion of gas to water already described is difficult because the operating conditions are in all cases very different, the present catalysts seem to be among the most active systems. In addition, they cover a fairly wide pH band around neutrality, an area in which the previously known catalytic systems seemed to exhibit little activity.
Claims (10)
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CN114657381A (en) * | 2022-03-17 | 2022-06-24 | 金川集团股份有限公司 | Method for recovering rhodium from acetylacetonatocarbonyltriphenylphosphine rhodium production waste liquid |
CN114657381B (en) * | 2022-03-17 | 2023-10-31 | 金川集团股份有限公司 | Method for recovering rhodium from waste liquid of production of rhodium acetylacetonate triphenylphosphine carbonyl |
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