EP2456555A1 - Method for oxidizing methane - Google Patents

Method for oxidizing methane

Info

Publication number
EP2456555A1
EP2456555A1 EP10747567A EP10747567A EP2456555A1 EP 2456555 A1 EP2456555 A1 EP 2456555A1 EP 10747567 A EP10747567 A EP 10747567A EP 10747567 A EP10747567 A EP 10747567A EP 2456555 A1 EP2456555 A1 EP 2456555A1
Authority
EP
European Patent Office
Prior art keywords
platinum
ligand
platinum complex
catalyst
aromatic
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.)
Withdrawn
Application number
EP10747567A
Other languages
German (de)
French (fr)
Inventor
Ferdi SCHÜTH
Regina Palkovits
Christian Baltes
Markus Antonietti
Arne Thomas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
Studiengesellschaft Kohle gGmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP2456555A1 publication Critical patent/EP2456555A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • 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
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • 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

Definitions

  • the present invention relates to a platinum complex and a process for the oxidation of methane to methyl sulfate in the presence of the platinum complex as a catalyst.
  • US Patent Application 2003/0120125 A1 discloses a process for the partial oxidation of lower alkanes with an oxidizing agent and a strong acid in the presence of a catalyst.
  • the catalyst consists of a metal compound from the group of platinum metals with a heteroatom-containing ligand, which can form monodentate or Bulidentatligandkomplexe with the transition metal, wherein specifically called platinum-Biacidinkomplexe.
  • the molecular catalyst is in dissolved form during the reaction (homogeneous catalysis).
  • US Patent Application 2006/0241327 A1 discloses another process for the oxidation of hydrocarbons into the corresponding hydroxy compound, in which the metal complexes of the transition metals Re, Os, Ir, Ru, W and Rh, activated as catalysts, are activated and the metal is coordinated by an oxidation resistant ligand.
  • the object of the invention described in US2006 / 0241327 was to develop a homogeneous catalyst which is present in dissolved form in the reaction.
  • Object of the present invention was to provide a catalyst for the oxidation of methane to methyl sulfate and optionally subsequent hydrolysis to methanol available, which has a high activity and are converted with which methane in a Oxiationsretress with high selectivity into the corresponding oxidation product can.
  • the catalyst should not only have a high activity and selectivity.
  • Another object was to provide a catalyst which is present in the reaction solution as a solid. The solid catalyst should also have stability over several process cycles.
  • the present invention accordingly provides a platinum complex, platinum complex, which as ligands is a network based on aromatic N-heterocycles which has at least 2 coordinative N atoms per platinum atom.
  • the platinum complex according to the invention is based on a ligand system which can be prepared by trimerization and polymerization of aromatic nitriles in the presence of a Lewis acid.
  • the ligands are thermally stable and stable even under strong oxidizing conditions.
  • the platinum complexes are good oxidation catalysts. They are present as solids and are particularly suitable as catalysts in heterogeneous catalysis in liquid and gaseous systems, since they can be separated from the reaction mixture in a simple manner.
  • the platinum complex according to the invention contains as ligands a network which can be obtained by heating mono-, di-, tri- and / or tetrasubstituted aromatics or heteroaromatics.
  • the polymerization is preferably carried out in the presence of a Lewis acid or in a solvent or solvent mixture, preferably in dimethylformamide.
  • the substituents may be selected from cyano, amino, carboxyl, alcohol, boric acid, ethers, esters, wherein, when the aromatic substituent is an ester group, the educts also contain compounds having amino groups as substituents.
  • Polybenzimidazoles can also be obtained by reacting the starting materials in the presence of the Lewis acid in a suitable solvent such as DMF.
  • the network usually forms at high temperatures, which is why the Lewis acid should be a temperature-stable Lewis acid, preferably a metal salt which is liquid at the reaction temperature.
  • ZnCl 2 has proven to be particularly suitable.
  • the reaction product may be subjected to a temperature treatment whereby partial carbonation of the product takes place.
  • the ligand preferably 1, 2-dicyanobenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 3,5-tricyanobenzene, 1, 2,4,5-tetracyanobenzene, 4,4'-dicyano- biphenyl, 4,4 "-dicyanoterphenyl, 2,4-dicyano-pyridine, 2,6-dicyano-pyridine, tris (4-cyanophenyl) amine, tris (4-cyanophenyl) benzene, tetra (4-cyanonophenyl) adamantane, 2 , 5-dicyanothiophene and 5,5'-dicyanobipyridine, and a mixture of 1, 1, 2, 2-tetraaminobiphenyl and 1, 3-dicarboxylic acid diphenyl ester or 1, 3,5-
  • Tricarboxylic acid triphenyl esters proved to be suitable.
  • the aromatic or heteroaromatic compound and the Lewis acid are generally heated to a temperature of 100 0 C to 800 0 C, preferably from 250 ° C to 750 0 C. If a metal salt is used as the Lewis acid, the reaction is preferably carried out in the melt of this metal salt.
  • the ligand may also be treated by other temperature treatments after the production, in the temperature range from 300 0 C to 900 ° C and preferably at 400 0 C to 600 0 C.
  • the aromatic or heteroaromatic compounds usually at temperature of 50 0 C to 300 ° C, preferably heated to 150 ° C to 200 0 C.
  • the preparation may also contain a temperature treatment of the resulting solid at temperatures between 150 ° C and 800 0 C, preferably between 200 ° C and 400 ° C.
  • the ligand is a network obtained by heating 1, 4-dicyanobenzene in a melt of ZnL 2 in a temperature range between 280 0 C and 730 0 C.
  • An idealized representation of the reaction is given below, wherein it is expressly pointed out that it is an idealized representation of the reaction product and indeed a variety of structural elements can be obtained. There may also be carbonized products.
  • the platinum in the platinum complex according to the invention, can be present in the oxidation states 0 or +2. It may contain, in addition to the network ligands, further ligands, such as water, methanol and / or CO.
  • the complex anion can be selected from any anions that do not adversely affect the reaction.
  • the anion is selected from the group consisting of halide, hydrogensulfate, hydrogen sulfite, sulfate, sulfite, methylsulfate, methanol, water, hydroxide, carbon monoxide, bicarbonate or carbonate, and may have the complex as further ligands.
  • a suitable platinum compound and the ligand material are reacted in a manner known per se.
  • a platinum salt for example a Alkalitetrahalogenoplatinat as heated AIIoIi 2 PtCl 4 in aqueous solution in the presence of ligand at a temperature between 40 0 C and 90 ° C over a period of one hour to 10 hours.
  • the reaction product can then be filtered off and dried.
  • the platinum complexes according to the invention are suitable as catalysts for the oxidation of methane to methyl sulfate, which can be hydrolyzed to methanol in a subsequent hydrolysis step.
  • Another object of the present invention is a process for the oxidation of methane to methyl sulfate in the presence of a platinum complex as a catalyst, which thereby characterized in that the ligand of the platinum complex is a network based on aromatic N-heterocycles which has at least two coordinative N atoms per platinum atom.
  • the reaction temperature is generally between 100 0 C and 300 0 C, preferably between 160 ° C and 250 ° C.
  • sulfuric acid SO 3 or oleum are used, preferably in the form of oleum.
  • SO 3 or oleum are used, preferably in the form of oleum.
  • the inventive method allows a simple and inexpensive oxidation of methane to methanol.
  • the catalyst can be easily removed from the reaction mixture by filtration.
  • the oxidation reaction using the catalyst according to the invention offers, for example, the possibility of promoting natural gas in smaller deposits, from which the natural gas can not be conveyed via gas lines, by means of the oxidation process according to the invention and converting it into a transportable good.
  • the Pt-bipyrimidine complex and the triazine-based material (CTF) were prepared according to
  • the autoclave was charged with 40 bar CH 4 , heated to 215 ° C, held there for 2.5 h and then cooled to room temperature. The pressure must be reduced slowly after the reaction to avoid foaming the reaction solution too much.
  • the reaction mixture was filtered through a glass frit. The recovered catalyst was washed with a little water to remove most of the remaining sulfuric acid and dried at 90 ° C. before reuse.
  • the reaction solution was added to 30 ml of water, hydrolyzed for 4 h under reflux at 160 ° C. and analyzed by HPLC. The selectivity to methanol was determined from the pressure drop in the course of the reaction and the FTIR analysis of the gas phase for the determination of by-products.
  • TON mol MeOH / molp t .
  • the platinum content of the catalysts was determined either by means of REM-EDX (Pt-CTF and K 2 PtCl 4 -CTF, Run 2-6) or the content was estimated on the basis of the amount of platinum used (K 2 PtCl 4 -CTF, first run).
  • the CTF material was characterized by nitrogen sorption, XRD, TEM and XPS analyzes and the catalysts by TEM, REM / EDX, XPS and XRD (see Figures 1 and 2).
  • TON is based on the platinum content determined from REM-EDX; [c] 65 mg catalyst; [d] 26 mg catalyst; [e] 48 mg CTF with 92 mg K 2 PtCl 4, [f] results from the second reaction with 62 mg Pt-CTF.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to platinum(II) complexes and the use of said complexes to oxidize methane to form methyl sulfate, wherein the catalyst as a ligand is a network based on aromatic N heterocycles, which network has at least 2 coordinate N atoms per platinum atom, and the complex anion is selected from a halide. The catalyst enables a selective low-temperature oxidation of methane to form methyl sulfate or methanol. The catalysts not only exhibit high activity but also can be easily separated from the reaction mixture and reused over several runs without a significant loss of activity.

Description

Verfahren zur Oxidation von Methan  Process for the oxidation of methane
Die vorliegende Erfindung betrifft einen Platinkomplex sowie ein Verfahren zur Oxidation von Methan zu Methylsulfat in Gegenwart des Platinkomplexes als Katalysator. The present invention relates to a platinum complex and a process for the oxidation of methane to methyl sulfate in the presence of the platinum complex as a catalyst.
Die Entwicklung von Katalysatoren für die direkte Niedrigtemperaturoxidation von Methan zu Methanol stellt in der Katalyse eine der bedeutendsten Herausforderungen der letzten Jahrzehnte dar. Die hohe Bindungsenergie der CH3-H Bindung (435 kJ mol"1) und die starke Tendenz des Systems zur Überoxidation zu CO2 erfordert nicht nur hochaktive, sondern auch sehr selektive Katalysatoren. In der Vergangenheit befassten sich bereits zahlreiche Untersuchungen mit dieser Herausforderung. Der überwiegende Teil der Katalysatoren zeigte allerdings irreversible Bulkmetallbildung, zusammen mit entsprechend niedriger Selektivität zu Methanol. Einige überaus stabile Pd-, Au- und Hg-Komplexe erschienen zunächst sehr aussichtsreich, erreichten allerdings nur sehr niedrige Umsatzraten (Turn over frequencies - TOFs) von unter 1 h'1. Bezüglich heterogen katalysierter Prozesse wurden nahezu ausschließlich Untersuchungen weit über 2500C an basischen Oxiden, Übergangsmetalloxiden, und an in Zeolithen eingekapselten Eisenkomplexen durchgeführt. All diese Katalysatoren zeigten allerdings eine starke Tendenz zur Überoxidation des Methans zu CO2 und nur geringe Selektivität zu Methanol, sodass Methanolausbeuten von maximal 5 % erreicht werden konnten. The development of catalysts for the direct low-temperature oxidation of methane to methanol represents one of the most important challenges of the last decades in catalysis. The high binding energy of the CH 3 -H bond (435 kJ mol "1 ) and the strong tendency of the system to overoxidize CO 2 requires not only highly active catalysts, but also very selective catalysts, and in the past numerous studies have addressed this challenge, but the vast majority of the catalysts showed irreversible bulk metal formation, together with correspondingly low selectivity to methanol and Hg complexes initially appeared to be very promising, but achieved only very low turnover rates (TOFs) of less than 1 h '1. With respect to heterogeneously catalyzed processes almost exclusively investigations of more than 250 ° C. on basic oxides, transition metal oxides, and at in Zeolites encapsulated iron complexes performed. However, all these catalysts showed a strong tendency to over-oxidation of the methane to CO 2 and only low selectivity to methanol, so that methanol yields of up to 5% could be achieved.
In der US-Patentanmeldung 2003/0120125 A1 wird ein Verfahren für die partielle Oxidation von niederen Alkanen mit einem Oxidationsmittel und einer starken Säure in Gegenwart eines Katalysators offenbart. Der Katalysator besteht aus einer Metallverbindung aus der Gruppe der Platinmetalle mit einem heteroatom-haltigen Liganden, welcher Monodentat- oder Bulidentatligandkomplexe mit dem Übergangsmetall bilden kann, wobei spezifisch Platin- Biacidinkomplexe genannt werden. Der molekulare Katalysator liegt während der Reaktion in gelöster Form vor (homogene Katalyse). US Patent Application 2003/0120125 A1 discloses a process for the partial oxidation of lower alkanes with an oxidizing agent and a strong acid in the presence of a catalyst. The catalyst consists of a metal compound from the group of platinum metals with a heteroatom-containing ligand, which can form monodentate or Bulidentatligandkomplexe with the transition metal, wherein specifically called platinum-Biacidinkomplexe. The molecular catalyst is in dissolved form during the reaction (homogeneous catalysis).
In der US-Patentanmeldung 2006/0241327 A1 wird ein weiteres Verfahren zur Oxidation von Kohlenwasserstoffen in die entsprechende Hydroxyverbindung offenbart, worin als Katalysatoren aktivierte Metallkomplexe der Übergangsmetalle Re, Os, Ir, Ru, W und Rh verwendet werden und das Metall durch einen oxidationsbeständigen Liganden koordiniert ist. Der in der US2006/0241327 beschriebenen Erfindung lag die Aufgabe zugrunde, einen homogenen Katalysator zu entwickeln, der in der Reaktion in gelöster Form vorliegt. US Patent Application 2006/0241327 A1 discloses another process for the oxidation of hydrocarbons into the corresponding hydroxy compound, in which the metal complexes of the transition metals Re, Os, Ir, Ru, W and Rh, activated as catalysts, are activated and the metal is coordinated by an oxidation resistant ligand. The object of the invention described in US2006 / 0241327 was to develop a homogeneous catalyst which is present in dissolved form in the reaction.
Wie bereits voranstehend beschrieben, weist die Oxidation von niederen Alkanen, wie Methan, in den entsprechenden Alkohol mehrere Schwierigkeiten auf. Aufgabe der vorliegenden Erfindung war es, einen Katalysator für die Oxidation von Methan zu Methylsulfat und ggf. sich anschließende Hydrolyse zu Methanol zur Verfügung zu stellen, der eine hohe Aktivität aufweist und mit welchem Methan in einer Oxiationsreaktion mit hoher Selektivität in das entsprechenden Oxidationsprodukt umgewandelt werden kann. Der Katalysator sollte dabei nicht nur eine hohe Aktivität und Selektivität aufweisen. Ein weitere Aufgabe bestand darin, eine Katalysator zur Verfügung zu stellen, der in der Reaktionslösung als Feststoff vorliegen. Der feste Katalysator sollte außerdem eine Stabilität über mehrere Verfahrenszyklen aufweisen. As already described above, the oxidation of lower alkanes, such as methane, in the corresponding alcohol has several difficulties. Object of the present invention was to provide a catalyst for the oxidation of methane to methyl sulfate and optionally subsequent hydrolysis to methanol available, which has a high activity and are converted with which methane in a Oxiationsreaktion with high selectivity into the corresponding oxidation product can. The catalyst should not only have a high activity and selectivity. Another object was to provide a catalyst which is present in the reaction solution as a solid. The solid catalyst should also have stability over several process cycles.
Gegenstand der vorliegenden Erfindung ist demgemäß ein Platinkomplex, Platinkomplex, welcher als Liganden ein Netzwerk auf Basis von aromatischen N-Heterocyclen ist, welches mindestens 2 koordinative N-Atome pro Platinatom aufweist. The present invention accordingly provides a platinum complex, platinum complex, which as ligands is a network based on aromatic N-heterocycles which has at least 2 coordinative N atoms per platinum atom.
Der erfindungsgemäße Platinkomplex basiert auf einem Ligandensystem, welches durch Trimerisierung und Polymerisierung aromatischer Nitrile in Gegenwart einer Lewis-Säure hergestellt werden können. Die Liganden sind thermisch stabil und auch unter stark oxidierenden Bedingungen beständig. Die Platinkomlexe sind gute Oxidationskatalysatoren. Sie liegen als Feststoffe vor und eignen sich insbesondere als Katalysatoren in der heterogenen Katalyse in flüssigen und gasförmigen Systemen, da sie aus dem Reaktionsgemisch auf einfache Weise abgetrennt werden können. The platinum complex according to the invention is based on a ligand system which can be prepared by trimerization and polymerization of aromatic nitriles in the presence of a Lewis acid. The ligands are thermally stable and stable even under strong oxidizing conditions. The platinum complexes are good oxidation catalysts. They are present as solids and are particularly suitable as catalysts in heterogeneous catalysis in liquid and gaseous systems, since they can be separated from the reaction mixture in a simple manner.
Der erfindungsgemäße Platinkomplex enthält als Liganden ein Netzwerk, welches erhältlich ist durch Erhitzen von mono-, di-, tri- und/oder tetrasubstituierten Aromaten oder Heteroaromaten. Die Polymerisation erfolgt bevorzugt in Gegenwart einer Lewis-Säure oder in einem Lösungsmittel oder Lösungsmittelgemisch, vorzugsweise in Dimethylformamid. Die Substituenten können ausgewählt sein aus Cyano, Amino, Carboxyl, Alkohol, Borsäure, Ether, Ester, wobei, wenn der aromatische Substituent eine Estergruppe ist, die Edukte auch Verbindungen mit Aminogruppen als Substituenten enthalten. Polybenzimidazole können auch durch Reaktion der Ausgangsprodukte in Gegenwart der Lewis-Säure in einem geeigneten Lösungsmittel, wie DMF, erhalten werden. Das Netzwerk bildet sich in der Regel bei hohen Temperaturen, weshalb die Lewis-Säure eine temperaturbeständige Lewis-Säure sein sollte, vorzugsweise ein bei Reaktionstemperatur flüssiges Metallsalz. ZnCI2 hat sich als besonders geeignet erwiesen. In einem Nachbehandlungsschritt kann des Reaktionsprodukt einer Temperaturbehandlung unterworfen werden, wobei eine teilweise Carbonisierung des Produktes stattfindet. Verfahren zur Herstellung der Liganden werden in P. Kuhn et al., Angew. Chem. Int. Ed., 2008, 47, 3450-3453, A. Thomas et al., J. Mater. Chem., 2008, 18, 4893-4908 und in Thomas et., Chem. Mater., Vol. 20, 3, 2008 beschrieben. The platinum complex according to the invention contains as ligands a network which can be obtained by heating mono-, di-, tri- and / or tetrasubstituted aromatics or heteroaromatics. The polymerization is preferably carried out in the presence of a Lewis acid or in a solvent or solvent mixture, preferably in dimethylformamide. The substituents may be selected from cyano, amino, carboxyl, alcohol, boric acid, ethers, esters, wherein, when the aromatic substituent is an ester group, the educts also contain compounds having amino groups as substituents. Polybenzimidazoles can also be obtained by reacting the starting materials in the presence of the Lewis acid in a suitable solvent such as DMF. The network usually forms at high temperatures, which is why the Lewis acid should be a temperature-stable Lewis acid, preferably a metal salt which is liquid at the reaction temperature. ZnCl 2 has proven to be particularly suitable. In an aftertreatment step, the reaction product may be subjected to a temperature treatment whereby partial carbonation of the product takes place. Methods of preparing the ligands are described in P. Kuhn et al., Angew. Chem. Int. Ed., 2008, 47, 3450-3453, A. Thomas et al., J. Mater. Chem., 2008, 18, 4893-4908 and in Thomas et., Chem. Mater., Vol. 20, 3, 2008.
Zur Herstellung des Liganden haben sich vorzugsweise 1 ,2-Dicyanobenzol, 1 ,3- Dicyanobenzol, 1 ,4-Dicyanobenzol, 1 ,3,5-Tricyanobenzol, 1 ,2,4,5-Tetracyanobenzol, 4,4'- Dicyano-biphenyl, 4,4"-Dicyanoterphenyl, 2,4-Dicyano-pyridin, 2,6-Dicyano-pyridin, Tris(4- cyanophenyl)amin, Tris(4-cyanophenyl)benzol, Tetra(4-cyanonphenyl)adamantan, 2,5- Dicyanothiophen und 5,5'-Dicyanobipyridin sowie ein Gemisch aus 1 ,1-, 2,2- - Tetraaminobiphenyl und 1 ,3-Dicarbonsäurediphenylester oder 1 ,3,5-For the preparation of the ligand, preferably 1, 2-dicyanobenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 3,5-tricyanobenzene, 1, 2,4,5-tetracyanobenzene, 4,4'-dicyano- biphenyl, 4,4 "-dicyanoterphenyl, 2,4-dicyano-pyridine, 2,6-dicyano-pyridine, tris (4-cyanophenyl) amine, tris (4-cyanophenyl) benzene, tetra (4-cyanonophenyl) adamantane, 2 , 5-dicyanothiophene and 5,5'-dicyanobipyridine, and a mixture of 1, 1, 2, 2-tetraaminobiphenyl and 1, 3-dicarboxylic acid diphenyl ester or 1, 3,5-
Tricarbonsäuretriphenylester als geeignet erwiesen. Tricarboxylic acid triphenyl esters proved to be suitable.
Zur Herstellung des Liganden werden die aromatische bzw. heteroaromatische Verbindung und die Lewis-Säure in der Regel auf eine Temperatur von 1000C bis 8000C, vorzugsweise von 250°C bis 7500C, erhitzt. Wird ein Metallsalz als Lewis-Säure verwendet, erfolgt die Reaktion vorzugsweise in der Schmelze dieses Metallsalzes. Der Ligand kann außerdem durch weitere Temperaturbehandlungen nach der Herstellung, im Temperaturbereich von 3000C bis 900°C und vorzugsweise bei 4000C bis 6000C behandelt werden. Bei Herstellung in einem Lösungsmittel oder Lösungsmittelgemisch, vorzugsweise in Dimethylformamid, werden die aromatischen oder heteroaromatischen Verbindungen in der Regel auf Temperatur von 500C bis 300°C, vorzugsweise auf 150°C bis 2000C erhitzt. Die Herstellung kann außerdem eine Temperaturbehandlung des erhaltenen Feststoffes bei Temperaturen zwischen 150°C und 8000C, vorzugsweise zwischen 200°C und 400°C enthalten. For the preparation of the ligand, the aromatic or heteroaromatic compound and the Lewis acid are generally heated to a temperature of 100 0 C to 800 0 C, preferably from 250 ° C to 750 0 C. If a metal salt is used as the Lewis acid, the reaction is preferably carried out in the melt of this metal salt. The ligand may also be treated by other temperature treatments after the production, in the temperature range from 300 0 C to 900 ° C and preferably at 400 0 C to 600 0 C. When prepared in a solvent or solvent mixture, preferably in dimethylformamide, the aromatic or heteroaromatic compounds usually at temperature of 50 0 C to 300 ° C, preferably heated to 150 ° C to 200 0 C. The preparation may also contain a temperature treatment of the resulting solid at temperatures between 150 ° C and 800 0 C, preferably between 200 ° C and 400 ° C.
In einer bevorzugten Ausführungsform ist der Ligand ein Netzwerk welches erhalten wird durch Erhitzen von 1 ,4-Dicyanobenzol in einer Schmelze von ZnL2 in einem Temperaturbereich zwischen 2800C und 7300C durchgeführt. Eine idealisierte Darstellung der Reaktion ist im Folgenden wiedergegeben, wobei ausdrücklich darauf hingewiesen wird, dass es sich um eine idealisierte Darstellung des Reaktionsproduktes handelt und tatsächlich eine Vielzahl von Strukturelementen erhalten werden können. Es können auch carbonisierte Produkte vorliegen. In a preferred embodiment, the ligand is a network obtained by heating 1, 4-dicyanobenzene in a melt of ZnL 2 in a temperature range between 280 0 C and 730 0 C. An idealized representation of the reaction is given below, wherein it is expressly pointed out that it is an idealized representation of the reaction product and indeed a variety of structural elements can be obtained. There may also be carbonized products.
Tπmer CTF Pt-CTF/ K2PtCI4-CTF Tπmer CTF Pt-CTF / K 2 PtCl 4 -CTF
Im erfindungsgemäßen Platinkomplex kann das Platin in den Oxidationsstufen 0 oder +2 vorliegen. Es kann neben den Netzwerk-Liganden noch weitere Liganden enthalten, wie Wasser, Methanol und/oder CO. Wenn Platin in der Oxidationsstufe +2 vorliegt, kann das Komplexanion aus beliebigen Anionen ausgewählt werden, die die Reaktion nicht negativ beeinflussen. Vorzugsweise wird das Anion ausgewählt aus der Gruppe bestehend aus Halogenid, Hydrogensulfat, Hydrogensulfit, Sulfat, Sulfit, Methylsulfat, Methanol, Wasser, Hydroxid, Kohlenmonoxid, Hydrogencarbonat oder Carbonat, und der Komplex als weitere Liganden aufweisen kann. In the platinum complex according to the invention, the platinum can be present in the oxidation states 0 or +2. It may contain, in addition to the network ligands, further ligands, such as water, methanol and / or CO. When platinum is in the +2 oxidation state, the complex anion can be selected from any anions that do not adversely affect the reaction. Preferably, the anion is selected from the group consisting of halide, hydrogensulfate, hydrogen sulfite, sulfate, sulfite, methylsulfate, methanol, water, hydroxide, carbon monoxide, bicarbonate or carbonate, and may have the complex as further ligands.
Zur Herstellung des erfindungsgemäßen Platinkomlexes werden eine geeignete Platinverbindung und das Ligandenmaterial in an sich bekannter Weise umgesetzt. In einer möglichen Ausführungsform werden ein Platinsalz, beispielsweise ein Alkalitetrahalogenoplatinat, wie AIIoIi2PtCI4 in wässriger Lösung in Gegenwart des Liganden bei einer Temperatur zwischen 400C und 90°C über einen Zeitraum von einer Stunde bis 10 Stunden erhitzt. Das Reaktionsprodukt kann anschließend abfiltriert und getrocknet werden. Für den Einsatz als Katalysator ist es auch möglich, die Ausgangsverbindungen, d.h. den Liganden und die Platinverbindungen direkt in das Reaktionsgemisch zu geben, die Komplexverbindung bildet sich dann in situ. To prepare the platinum complex according to the invention, a suitable platinum compound and the ligand material are reacted in a manner known per se. In one possible embodiment, a platinum salt, for example a Alkalitetrahalogenoplatinat as heated AIIoIi 2 PtCl 4 in aqueous solution in the presence of ligand at a temperature between 40 0 C and 90 ° C over a period of one hour to 10 hours. The reaction product can then be filtered off and dried. For use as a catalyst, it is also possible to add the starting compounds, ie the ligands and the platinum compounds, directly into the reaction mixture, the complex compound then being formed in situ.
Die erfindungsgemäßen Platinkomplexe eignen sich als Katalysatoren zur Oxidation von Methan zu Methylsulfat welches in einem nachfolgenden Hydrolyseschritt zu Methanol hydrolisiert werden kann. The platinum complexes according to the invention are suitable as catalysts for the oxidation of methane to methyl sulfate, which can be hydrolyzed to methanol in a subsequent hydrolysis step.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Oxidation von Methan zu Methylsulfat in Gegenwart eines Platinkomplexes als Katalysator, welches dadurch gekennzeichnet ist, dass der Ligand des Platinkomplexes ein Netzwerk auf Basis von aromatischen N-Heterocyclen ist, welches mindestens zwei koordinative N-Atome pro Platinatom aufweist. Another object of the present invention is a process for the oxidation of methane to methyl sulfate in the presence of a platinum complex as a catalyst, which thereby characterized in that the ligand of the platinum complex is a network based on aromatic N-heterocycles which has at least two coordinative N atoms per platinum atom.
Durch den Einsatz des erfindungsgemäßen Katalysators ist eine Tieftemperaturoxidation von Methan zu Methanol als Endprodukt möglich. Die Reaktionstemperatur liegt in der Regel zwischen 1000C und 3000C, vorzugsweise zwischen 160°C und 250°C. By using the catalyst according to the invention, a low-temperature oxidation of methane to methanol as the end product is possible. The reaction temperature is generally between 100 0 C and 300 0 C, preferably between 160 ° C and 250 ° C.
Als Oxidationsmittel werden Schwefelsäure, SO3 oder Oleum verwendet, vorzugsweise in Form von Oleum. Die Reaktion läuft in den nachfolgend dargestellten Einzelschritten ab: As the oxidizing agent sulfuric acid, SO 3 or oleum are used, preferably in the form of oleum. The reaction takes place in the individual steps shown below:
CH4 + H2 SO4 + SO3 → CH3OSO3H + H2O + SO2 (a) CH 4 + H 2 SO 4 + SO 3 → CH 3 OSO 3 H + H 2 O + SO 2 (a)
CH3OSO3H + H2O → CH3OH + H2S O4 (b) CH 3 OSO 3 H + H 2 O → CH 3 OH + H 2 SO 4 (b)
SO2 + 1Z2 O2 → SO3 (c) SO 2 + 1 Z 2 O 2 → SO 3 (c)
Σ CH4 + 1Z2 O2 → CH3OH (d) Σ CH 4 + 1 Z 2 O 2 → CH 3 OH (d)
Das erfindungsgemäße Verfahren ermöglicht eine einfache und kostengünstige Oxidation von Methan zu Methanol. Der Katalysator lässt sich auf einfache Weise, wie durch Filtration aus dem Reaktionsgemisch entfernen. Die Oxidationsreaktion unter Einsatz des erfindungsgemäßen Katalysators bietet beispielsweise die Möglichkeit, Erdgas in kleineren Vorkommen, aus denen das Erdgas nicht über Gasleitungen gefördert werden kann, mittels des erfindungsgemäßen Oxidationsverfahrens zu fördern und in ein transportierbares Gut umzuwandeln. The inventive method allows a simple and inexpensive oxidation of methane to methanol. The catalyst can be easily removed from the reaction mixture by filtration. The oxidation reaction using the catalyst according to the invention offers, for example, the possibility of promoting natural gas in smaller deposits, from which the natural gas can not be conveyed via gas lines, by means of the oxidation process according to the invention and converting it into a transportable good.
Beispiele Examples
Herstellung der Liqanden:  Production of Liqanden:
Der Pt-Bipyrimidin-Komplex und das Triazin-basierte Material (CTF) wurden gemäß The Pt-bipyrimidine complex and the triazine-based material (CTF) were prepared according to
Literaturvorschriften, J. H. Lunsford, Catal. Today 2000, 63, 165-174 und M. Baerns, J. R. H.Literatures, J.H. Lunsford, Catal. Today 2000, 63, 165-174 and M. Baerns, J.R.H.
Ross in Perspectives in Catalysis (Hrsg.: J. A. Thomas, K. I. Zamaraev), Blackwell, 1992 hergestellt. Ross in Perspectives in Catalysis (Ed .: J.A. Thomas, K.I. Zamaraev), Blackwell, 1992.
Herstellung des Platinkomplexes: Production of the platinum complex:
Zur Herstellung des Platinkomplexes wurden 170 mg CTF und 340 mg K2PtCI4 bei 600C für 4 h in Wasser umgesetzt, filtriert, mit Wasser gewaschen und über Nacht bei 90°C getrocknet. Oxidation von Methan Die katalytischen Versuche wurden in einem 50 ml Edelstahlautoklaven mit Tefloneinsatz durchgeführt. In einer typischen Reaktion wurde der Autoklav mit 15ml Oleum (30 % SO3) und 50 - 70 mg Katalysator befüllt, verschlossen und mit Argon mehrfach gespült. Im Fall von K2PtCI4-CTF wurden 92 mg CTF und 48 mg K2PtCI4 zum Oleum in den Autoklaven gegeben. Für die eigentliche Reaktion wurde der Autoklav mit 40 bar CH4 beaufschlagt, auf 215°C aufgeheizt, dort 2,5 h gehalten und anschließend auf Raumtemperatur abgekühlt. Der Druck muss im Anschluss an die Reaktion langsam reduziert werden, um zu vermeiden, dass die Reaktionslösung zu stark schäumt. Im Fall der festen Katalysatoren wurde das Reaktionsgemisch über eine Glassfritte filtriert. Der wiedergewonnene Katalysator wurde mit etwas Wasser gewaschen, um den überwiegenden Teil verbleibender Schwefelsäure zu entfernen und vor dem Wiedereinsatz bei 900C getrocknet. Die Reaktionslösung wurde in 30 ml Wasser gegeben, für 4 h unter Rückfluss bei 1600C hydrolysiert und mittels HPLC analysiert. Die Selektivität zu Methanol wurde aus dem Druckabfall im Reaktionsverlauf und der FTIR- Analyse der Gasphase zur Bestimmung von Nebenprodukten ermittelt. In jedem Recyclingschritt des festen Katalysators konnten etwa 5 - 10 wt.% des Katalysatormaterials nicht wiedergewonnen werden, sie verblieben auf der Fritte. Dieser Effekt wurde bei der Berechnung der katalytischen Aktivität berücksichtigt. Die Tum over numbers (TONs) wurden auf der Basis des molaren Verhältnisses von Methanol und Platingehalt des Katalysators als TON = molMeOH/molpt bestimmt. Der Platingehalt der Katalysatoren wurde entweder mittels REM-EDX ermittelt (Pt-CTF und K2PtCI4-CTF, Lauf 2-6) oder der Gehalt wurde auf der Basis der eingesetzten Platinmenge abgeschätzt (K2PtCI4-CTF, erster Lauf). Das CTF-Material wurde mittels Stickstoffsorption, XRD, TEM und XPS-Analysen und die Katalysatoren mittels TEM, REM/ EDX, XPS und XRD charakterisiert (s. Figuren 1 und 2). For the preparation of the platinum complex CTF 170 mg and 340 mg of K 2 PtCl 4 were at 60 0 C for 4 h reacted in water, filtered, washed with water and dried overnight at 90 ° C. Oxidation of methane The catalytic tests were carried out in a 50 ml stainless steel autoclave with Teflon insert. In a typical reaction, the autoclave was filled with 15 ml of oleum (30% SO 3 ) and 50-70 mg of catalyst, sealed and rinsed several times with argon. In the case of K 2 PtCl 4 -CTF, 92 mg of CTF and 48 mg of K 2 PtCl 4 were added to the oleum in the autoclave. For the actual reaction, the autoclave was charged with 40 bar CH 4 , heated to 215 ° C, held there for 2.5 h and then cooled to room temperature. The pressure must be reduced slowly after the reaction to avoid foaming the reaction solution too much. In the case of solid catalysts, the reaction mixture was filtered through a glass frit. The recovered catalyst was washed with a little water to remove most of the remaining sulfuric acid and dried at 90 ° C. before reuse. The reaction solution was added to 30 ml of water, hydrolyzed for 4 h under reflux at 160 ° C. and analyzed by HPLC. The selectivity to methanol was determined from the pressure drop in the course of the reaction and the FTIR analysis of the gas phase for the determination of by-products. In each recycling step of the solid catalyst, about 5-10 wt% of the catalyst material could not be recovered, remaining on the frit. This effect was taken into account in the calculation of the catalytic activity. The TONs were determined on the basis of the molar ratio of methanol and platinum content of the catalyst as TON = mol MeOH / molp t . The platinum content of the catalysts was determined either by means of REM-EDX (Pt-CTF and K 2 PtCl 4 -CTF, Run 2-6) or the content was estimated on the basis of the amount of platinum used (K 2 PtCl 4 -CTF, first run). , The CTF material was characterized by nitrogen sorption, XRD, TEM and XPS analyzes and the catalysts by TEM, REM / EDX, XPS and XRD (see Figures 1 and 2).
Tabelle 1. Katalytische Aktivität des molekularen Periana Katalysators und der festen Pt- und K2PtCI4-CFT Katalysatoren in der Methanoxidation. Table 1. Catalytic activity of the molecular Periana catalyst and the solid Pt and K 2 PtCl 4 -CFT catalysts in methane oxidation.
Katalysator'31 Endkonz. Methanol/ mol L"1 TON[b] Catalyst '31 end conc. Methanol / mol L "1 TON [b]
Katalysator aus 1.65 158  Catalyst from 1.65 158
US7,368,598 [cl US7,368,598 [cl
Katalysator aus 1.49 355  Catalyst from 1.49 355
US7,368,598 (dl US7,368,598 (dl
K2PtCI4-CTF[eI 1.54 201 K 2 PtCl 4 -CTF [eI 1.54 201
Pt-CTF[fl 1.80 246 Pt-CTF [fl 1.80 246
[a] Reaktionsbedingungen: 15ml H2SO4 (30%SO3), 40 bar CH4 Druck (25°C), 2,5 h bei 215°C;[a] Reaction conditions: 15 mL H 2 SO 4 (30% SO 3 ), 40 bar CH 4 pressure (25 ° C), 2.5 h at 215 ° C;
[b] TON basiert auf dem Platingehalt ermittelt aus REM-EDX; [c] 65 mg Katalysator; [d] 26 mg Katalysator; [e] 48 mg CTF mit 92 mg K2PtCI4, [f] Ergebnisse aus der zweiten Reaktion mit 62 mg Pt-CTF. [b] TON is based on the platinum content determined from REM-EDX; [c] 65 mg catalyst; [d] 26 mg catalyst; [e] 48 mg CTF with 92 mg K 2 PtCl 4, [f] results from the second reaction with 62 mg Pt-CTF.
Abbildung 1. Katalytische Aktivität von (a) Pt-CTF und (b) K2PtCI4-CFT in der direkten Oxidation von Methan zu Methanol über mehrere Recyclingschritte. Figure 1. Catalytic activity of (a) Pt-CTF and (b) K 2 PtCl 4 -CFT in the direct oxidation of methane to methanol over several recycling steps.
(a) (b) (a) (b)
5 Lauf 6 Lauf 5 run 6 run

Claims

Patentansprüche claims
1. Platinkomplex, welcher als Liganden ein Netzwerk auf Basis von aromatischen N- Heterocyclen ist, welches mindestens 2 koordinative N-Atome pro Platinatom aufweist. 1. Platinum complex, which is a ligand on a network based on aromatic N-heterocycles, which has at least 2 coordinative N atoms per platinum atom.
2. Platinkomplex nach Anspruch 1 , dadurch gekennzeichnet, dass der Ligand ein Netzwerk ist, welcher erhältlich ist durch Erhitzen von mono-, di-, tri- oder tetra-substiuierten Aromaten oder Heteroaromaten, wobei die Substituenten ausgewählt sind aus Cyano, Amino, Carboxyl, Alkohol, Borsäure, Ether, Ester, wobei, wenn der aromatische Substituent eine Estergruppe ist, die Edukte auch Verbindungen mit Aminogruppen als Substituenten enthalten, in Gegenwart einer Lewis-Säure. 2. platinum complex according to claim 1, characterized in that the ligand is a network which is obtainable by heating mono-, di-, tri- or tetra-substituted aromatics or heteroaromatics, wherein the substituents are selected from cyano, amino, carboxyl , Alcohol, boric acid, ethers, esters, wherein, when the aromatic substituent is an ester group, the starting materials also contain compounds having amino groups as substituents, in the presence of a Lewis acid.
3. Platinkomplex nach Anspruch 2, dadurch gekennzeichnet, dass die Lewis-Säure ZnCI2 ist. 3. platinum complex according to claim 2, characterized in that the Lewis acid ZnCl 2 is.
4. Platinkomplex nach Anspruch 2 oder 3, dadurch gekennzeichnet, dass der substituierte Aromat oder Heteroaromat ausgewählt ist aus 1 ,2-Dicyanobenzol, 1 ,3-Dicyanobenzol, 1 ,4-Dicyanobenzol, 1 ,3,5-Tricyanobenzol, 1 ,2,4,5-Tetracyanobenzol, 4,4'-Dicyano- biphenyl, 4,4"-Dicyanoterphenyl, 2,6-Dicyano-pyridin, 2,4-Dicyano-pyridin, Tris(4- cyanophenyl)amin, Tris(4-cyanophenyl)benzol, Tetra(4-cyanonphenyl)adamantan, 2,5- Dicyanothiophen, 5,5'-Dicyanobipyridin und einem Gemisch aus 1 ,1 '-, 2,2'- 3,3'- Tetraaminobiphenyl und 1 ,3-Dicarbonsäurediphenylester oder 1 ,3,5- Tricarbonsäuretriphenylester. 4. platinum complex according to claim 2 or 3, characterized in that the substituted aromatic or heteroaromatic is selected from 1, 2-dicyanobenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 3,5-tricyanobenzene, 1, 2 , 4,5-tetracyanobenzene, 4,4'-dicyano-biphenyl, 4,4 "-dicyanoterphenyl, 2,6-dicyano-pyridine, 2,4-dicyano-pyridine, tris (4-cyanophenyl) amine, tris (4 -cyanophenyl) benzene, tetra (4-cyanonphenyl) adamantane, 2,5-dicyanothiophene, 5,5'-dicyanobipyridine and a mixture of 1,1 ', 2,2'-3,3'-tetraaminobiphenyl and 1, 3 Dicarboxylic acid diphenyl ester or 1,3,5-tricarboxylic acid triphenyl ester.
5. Platinkomplex nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass das Platin in den Oxidationsstufen O oder +2 vorliegt und, wenn es in der Oxidationsstufe +2 vorliegt, das Komplexanion ausgewählt ist aus der Gruppe bestehend aus Halogenid, Hydrogensulfat, Hydrogensulfit, Sulfat, Sulfit, Methylsulfat, Methanol, Wasser, Hydroxid, Kohlenmonoxid, Hydrogencarbonat oder Carbonat, und der Komplex als weitere Liganden Wasser, Methanol und/oder CO aufweisen kann. 5. platinum complex according to one of claims 2 to 4, characterized in that the platinum is present in the oxidation state O or +2 and, if it is in the oxidation state +2, the complex anion is selected from the group consisting of halide, hydrogen sulfate, hydrogen sulfite , Sulfate, sulfite, methylsulfate, methanol, water, hydroxide, carbon monoxide, bicarbonate or carbonate, and the complex may have, as further ligands, water, methanol and / or CO.
6. Platinkomplex nach einem der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass der substituierte Aromat oder Heteroaromat in Gegenwart der Lewis-Säure auf eine Temperatur von 1500C bis 5000C, vorzugsweise von 200°C bis 4200C, erhitzt wird. 6. platinum complex according to one of claims 2 to 5, characterized in that the substituted aromatic or heteroaromatic in the presence of the Lewis acid to a temperature of 150 0 C to 500 0 C, preferably from 200 ° C to 420 0 C, heated ,
7. Verfahren zur Herstellung eines Platinkomplexes nach einem der Ansprüche 1 bis 6, eine Platinverbindung und der Ligand in wässriger Lösung erhitzt werden, dadurch gekennzeichnet, dass der Ligand ein Netzwerk auf Basis von aromatischen N- Heterocyclen ist, welches mindestens 2 koordinative N-Atome pro Platinatom aufweist. 7. A process for preparing a platinum complex according to any one of claims 1 to 6, a platinum compound and the ligand are heated in aqueous solution, characterized in that the ligand is a network based on aromatic N-heterocycles which at least 2 coordinate N atoms per platinum atom.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Platinverbindung ein Dialkalitetrahalogenoplatinat, vorzugsweise Alkali2PtCI4 ist. 8. The method according to claim 7, characterized in that the platinum compound is a Dialkalitetrahalogenoplatinat, preferably alkali 2 PtCl 4 .
9. Verfahren nach Anspruch 7 oder Anspruch 8, dadurch gekennzeichnet, dass es bei einer Temperatur zwischen 400C und 90°C über einen Zeitraum von einer Stunde bis 10 Stunden erhitzt wird. 9. The method according to claim 7 or claim 8, characterized in that it is heated at a temperature between 40 0 C and 90 ° C over a period of one hour to 10 hours.
10. Verwendung des Platinkomplexes nach Anspruch 1 als Reaktionskatalysator in der Oxidation von Methan zu Methylsulfat mit SO3. 10. Use of the platinum complex according to claim 1 as a reaction catalyst in the oxidation of methane to methyl sulfate with SO 3 .
11. Verfahren zur Oxidation von Methan zu Methylsulfat in Gegenwart eines Platinkomplexes als Katalysator, dadurch gekennzeichnet, dass der Ligand des Platinkomplexes ein Netzwerk auf Basis von aromatischen N-Heterocyclen ist, welches mindestens 2 koordinative N-Atome pro Platinatom aufweist. 11. A process for the oxidation of methane to methyl sulfate in the presence of a platinum complex as a catalyst, characterized in that the ligand of the platinum complex is a network based on aromatic N-heterocycles having at least 2 coordinate N atoms per platinum atom.
12. Verfahren nach Anspruch 11 , dadurch gekennzeichnet, dass der Katalysator während der Reaktion in situ hergestellt wird durch Zugeben einer Platinverbindung und Ligand zum Reaktionsgemisch. 12. The method according to claim 11, characterized in that the catalyst is prepared in situ during the reaction by adding a platinum compound and ligand to the reaction mixture.
13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass das Methylsulfat zu Methanol hydrolysiert wird. 13. The method according to claim 11 or 12, characterized in that the methyl sulfate is hydrolyzed to methanol.
14. Verfahren nach einem der Anspruch 11 bis 13, dadurch gekennzeichnet, dass als Oxidationsmittel H2SO4, SO3 oder Oleumverwendet wird. 14. The method according to any one of claim 11 to 13, characterized in that as the oxidizing agent H 2 SO 4 , SO 3 or oleum is used.
EP10747567A 2009-07-24 2010-07-07 Method for oxidizing methane Withdrawn EP2456555A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009034685A DE102009034685A1 (en) 2009-07-24 2009-07-24 Process for the oxidation of methane
PCT/DE2010/000788 WO2011009429A1 (en) 2009-07-24 2010-07-07 Method for oxidizing methane

Publications (1)

Publication Number Publication Date
EP2456555A1 true EP2456555A1 (en) 2012-05-30

Family

ID=42732098

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10747567A Withdrawn EP2456555A1 (en) 2009-07-24 2010-07-07 Method for oxidizing methane

Country Status (5)

Country Link
US (1) US20120130071A1 (en)
EP (1) EP2456555A1 (en)
DE (1) DE102009034685A1 (en)
RU (1) RU2012106429A (en)
WO (1) WO2011009429A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015229123A (en) * 2014-06-03 2015-12-21 国立大学法人九州工業大学 Metal supporting material, method for producing the same, and method for producing catalyst
EP3190157B1 (en) * 2014-09-01 2019-08-07 The University of Tokyo Conductive hybrid material including covalent organic structure
CN104525258B (en) * 2015-01-07 2016-06-29 福州大学 A kind of covalent triazine organic polymer visible light catalyst and preparation thereof and application
CN111569942B (en) * 2020-06-02 2022-02-15 南昌航空大学 Covalent triazine organic framework composite photocatalyst with surface confinement monodisperse Pt nanoparticles and preparation method and application thereof
CN113058644B (en) * 2021-03-19 2022-08-26 山东大学 Catalyst for catalyzing oxidative dehydrogenation and hydrogenation of organic compounds and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050333A1 (en) * 1996-04-24 1998-11-12 Catalytica, Inc. Ligated platinum group metal catalyst complex and improved process for catalytically converting alkanes to esters and derivatives thereof
US7368598B2 (en) 2004-07-19 2008-05-06 University Of South California Process for converting methane to acetic acid
US20060171845A1 (en) * 2005-01-31 2006-08-03 Dakota Technologies, Inc. Sensors for measuring analytes
EA200701792A1 (en) 2005-02-24 2008-02-28 Рой А. Периана NEW CATALYTIC SYSTEMS FOR CONVERSING HYDROCARBONS TO FUNCTIONALIZED PRODUCTS

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011009429A1 *

Also Published As

Publication number Publication date
US20120130071A1 (en) 2012-05-24
RU2012106429A (en) 2013-08-27
WO2011009429A1 (en) 2011-01-27
DE102009034685A1 (en) 2011-03-31

Similar Documents

Publication Publication Date Title
EP2456555A1 (en) Method for oxidizing methane
DE69920379T2 (en) Palladium-ceria supported catalyst and process for producing methanol
DE2526046A1 (en) PROCESS FOR THE PRODUCTION OF CARBONIC ACIDS FROM ORGANIC HALOGENIDES
CH712355B1 (en) Synthesis of 2,2'-bipyridyl using supported metal and bimetallic nanoparticle catalysts.
WO2006058535A2 (en) Novel n-heterocyclic platinum and palladium carbene complexes, production and use thereof for the partial oxidation of hydrocarbons
WO2012107032A1 (en) Process for producing a catalyst comprising at least one transition metal on a nitrogen-modified porous carbon support
WO2010025921A1 (en) Method and reaction system for obtaining hydrogen
WO2017060243A1 (en) Method for producing ruthenium/iron/carbon carrier catalysts
DE3134747A1 (en) METHOD FOR PRODUCING AETHANOL
DE2325331A1 (en) PROCESS FOR THE PRODUCTION OF PYROSULPHATES
EP0668101A1 (en) Ruthenium catalysts, their preparation and their use in the preparation of cycloaliphatic polyamines
DE60010867T2 (en) METHOD AND COMPOSITION FOR HYDROXYLATING AROMATIC COMPOUNDS
DE2061538C3 (en) Process for the preparation of cobalt (III) -bis-salicylaldehydethylene diiminate complexes
DE3504732A1 (en) METHOD FOR PRODUCING A MIXTURE OF PHOSPHORNITRIDE CHLORIDE OLIGOMERS
DE2061709B2 (en) METHOD FOR PRODUCING N-METHYLANILINE
DE1493746B2 (en) 2- (p-Aminobenzoyloxy) -3-methylnaphtho-1,4-hydroquinone and process for its preparation
DE1543925A1 (en) Process for the preparation of vicinal episulfides
DE2365001C3 (en) Process for the preparation of methanol and a catalyst for its implementation
EP3081528A1 (en) Method for release of hydrogen from the adduct of ammonia and borane and use of transition metal free multidentate catalysts for release of hydrogen from the adduct of ammonia and borane
DE950911C (en) Process for the production of solid polymerization products of hydrocyanic acid
DE2403411C2 (en) Process for the production of ketones by oxidation of olefinically unsaturated compounds
EP2102102B1 (en) Method for removing no and n<sb>2</sb>o from gas mixtures
DE4018245A1 (en) METHOD FOR PRODUCING SULFONATED ANTHRANILE ACIDS
DE2724189B2 (en) Process for the production of ethylene glycol
DE1543079B1 (en) Process for the production of acetic acid

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120127

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20140207

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140821