EP1334067A1 - Method for the production of form-selective catalysts and use thereof - Google Patents

Method for the production of form-selective catalysts and use thereof

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Publication number
EP1334067A1
EP1334067A1 EP01988696A EP01988696A EP1334067A1 EP 1334067 A1 EP1334067 A1 EP 1334067A1 EP 01988696 A EP01988696 A EP 01988696A EP 01988696 A EP01988696 A EP 01988696A EP 1334067 A1 EP1334067 A1 EP 1334067A1
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EP
European Patent Office
Prior art keywords
use
characterized
catalysts
zeolite
according
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.)
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Application number
EP01988696A
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German (de)
French (fr)
Inventor
Mark Duda
Steffen Hasenzahl
Carsten Jost
Elias Klemm
Adolf KÜHNLE
Andreas Reitzmann
Karsten Seelbach
Uwe Tanger
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Evonik Degussa GmbH
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Evonik Degussa GmbH
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Publication date
Priority to DE10053085 priority Critical
Priority to DE10053085 priority
Priority to DE10139316A priority patent/DE10139316A1/en
Priority to DE10139316 priority
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to PCT/EP2001/011806 priority patent/WO2002034672A1/en
Publication of EP1334067A1 publication Critical patent/EP1334067A1/en
Application status is Withdrawn legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/061Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/60Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a method for the production of zeolite catalysts, containing transition group metals, by means of hydrothermal synthesis with subsequent calcification, characterised in that the transition group metal is used in the form of carbonyl, isonitrile or cyano complexes in the hydrothermal syntheses. Said catalysts can be used as denoxification catalysts, or for the oxidation of organic compounds.

Description

A process for the production of shape selective catalysts and their use

The invention relates to a method for producing shape selective catalysts based on zeolites or mesoporous silicates by incorporation of catalytically active metal oxides as a non-lattice species in the channel and cavity structure as well as the use of the catalysts thus prepared

Zeolites have won in the past in the field of catalysis research and in applied catalysis increasingly important [Kerr, GT (1989): Scientific American in 1989 (9), 94].

So have zeolites over other catalysts numerous benefits

They have a crystalline structure and thus a well-defined arrangement of the SiO - and Alθ4 tetrahedra This results in a good reproducibility in the

manufacturing

They have a shape selectivity, which means that only those molecules can be implemented that are smaller than the pore diameter of the zeolites

- A targeted incorporation of acid centers in the intracrystalline surface is possible directly in the synthesis and / or by subsequent ion exchange

Above 300 ° C some zeolites have acid strength in the range dei mineral acids

- catalytically active metal ions can be uniformly duich afford ion exchange or impregnation on the surface or in the Kristallgerust Install a subsequent reduction to pure metal is possible - zeolite catalysts are to at least 600 ° C thermally stable, sometimes even as BER and legenerierbar by burning off carbon storage Bettingen

Further, both zeolites and mesoporous silicates as well as their catalytic were

Effectiveness of Sheldon et al in Angew. Chein. 1997, 109, 1190 to 1211 described in detail There are also so-called "ship in a bottle" complexes or "Zeozyme" explained These are inclusions of metal complexes in large pores, called Supei kaiigen As metal complexes are oxidation-stable ligands such as phthalocyanines, Polypyiidine and aromatic used This Schiff base is usually so proceed that the complex is assembled in the pores of supercage by diffusing the ligands This phthalocyanines, polypyridines or aromatic Schiff bases have a catalytic effect, but are sensitive to Et stop the catalytic action to higher temperatures they may not, for example are thermally destroyed

Zeolite catalysts, the metals and / or metal oxides contained in the crystal lattice, are known To describe US 5,756,861 and US 5,672,777 a ZSM-5 zeolite for the oxidation of benzenes

In EP 0889018 is also doped with Fe 2 O 3 zeolite catalyst disclosed very low levels of catalytically active iron additves in zeolites, US 5,110,995.

Typically, the foreign metals grazing in the synthesis of the zeolite in the form of soluble salts such as nitrates added and incorporated by hydrothermal crystallization at high temperatures in the crystal composite of the Si / Al grating This results in the substitution of an Si atom to form a Bronsted acidic center may arise

Generally be in the incorporation of metal ions into the crystal lattice Bronsted acid sites so-produced, while in the deposition of metal oxides, for example in the channel structure of the zeolite, so-called Lewis acid sites are formed

This acid character led by TPDA- analyzes, ie temperature-programmed desorption of ammonia, determine An illustration of this methodology is found in Berndt et al., Microporous Materials, s (1994) 197-204, Elsevier Science BV, Amsterdam.

Foreign metal atoms, which are incorporated during the synthesis of the zeolite in the Kristallveibund, these Gittei burst vei blank and can be stored in the cavities of the Zeolithstruktui The so eihaltenen metal centers have a high catalytic activity, for example to the oxidation of benzenes in calcining the Katalysatoimasse Phenoldeuvaten (Panov et al., Appl. Cat. A 141, 1996, 185-192 and Panov et al., Cat. Today 41, 1998, 365-385) This learning thei mixing induced change of impurity metals of lattice sites to cavities in the embedded Metallzenti s is thus the catalytic activity of the catalyst is a crucial step to improve the catalytic action should as much as possible, not localized metal centers to be created at the lattice sites of the zeolite

The task was to develop a zeolite catalyst which is thermally stable, catalytically active metals, metal complexes and / or metal oxides in the manner of a "ship in a bottle" - may be used containing the complex and for the oxidation of organic substrates

Surprisingly, it was found that the introduced via carbonyl, cyano and / or isonitrile metals these may be incorporated into the channel and Flohlraumstaiktur a zeolite so that, firstly, obtain a catalytic effect, on the other hand, however, at most a low or no Bronsted acidity , for B is generated by the incorporation of metal ions into the Gittergerust,

It was also surprising that by this absence of Bronsted acidity of the tendency to coke and a concomitant loss of activity drastically decline addition, it was surprising that metals, metal complexes and / or metal oxides may be included in a manner in a zeolite that no bleeding of these substances takes place

was also surprising that a high amount of metal ions in the channel structure and thus a high catalytic activity immediately after the synthesis was present As mentioned at the outset, must usually be moved by the calcining process metal ions only to migrate from lattice sites in the voids of the zeolite, the present invention is therefore a process for the Hei position of transition group metal-containing zeolite catalysts by hydrothermal synthesis with subsequent calcination, which is characterized in that the sub-group metals in the form of complexes of the general formula

[Metal z (CO) (CN) b (CNR) JX) "(Y) c r ° as" 'with z> 1, R = alkyl chain having 1 to 10 carbon atoms, a, b, c, d and e = 0 or an integer, where a, b, c, d and e may be the same or different and the sum of a, b, c, d and e> 1, n = 0 or a negative or positive integer, and X and Y represent a volatile component be incorporated in the hydrothermal synthesis of the zeolite catalysts

Further subject of the invention is the use of zeolite catalysts inventively produced in process for the oxidation of organic substrates (eg benzene to phenol or generally for the hydroxylation of aromatic compounds), catalyst as a denitrification (for example in automotive catalytic converters and power plants) and in fuel cells

The inventive synthesis of the secondary group metal-containing zeolite catalysts is analogous to the known hydrothermal method for preparing zeolites, for example described in US 4,410,501, US 3,702,886, US 5,055,623 or by Ione et al. in Usp. Khimii, 56 (3) 1987, 393 ff.

The inventive Verfahl s for the preparation of transition group metal-containing zeolite catalysts by hydrothermal synthesis with subsequent calcination, characterized by the fact that the subgroup metals in the form of complexes of the general formula

[Metal z (CO) a (CN) "(CNR) J; X) (Y) c] n 1 n - o ° d" e c r r n "■ (I) with z> 1,

R = alkyl group having 1 to 10 carbon atoms, preferably a branched or unbranched alkyl chain having from 1 to 10, particularly preferably from I to 3 carbon atoms, a, b, c, d and e = 0 or an integer, wherein a, b, c, d and e may be the same or different and the sum of a, b, c, d and e> 1, n = 0 or a negative or positive integer, and

X and Y is a volatile component, such as for example water or ammonia represent in the hydrothermal synthesis of the zeolite catalysts are introduced, the transition group metals can be so mixed as pure carbonyl, cyano and / or isonitrile, as mixed complexes, or with other volatile ligands carbonyl, cyano, or isonitrile in the hydrothermal synthesis of the zeolite catalysts are introduced are examples of such complexes for example NH 4 [Fe (CO) 4 (CN)], Fe (CO) 4 (CNR), Fe (CNR) 4 (CN) 2, wherein R, may be preferably a methyl or ethyl group, an alkyl group

The catalysts inventively produced preferably have pores with a diameter below 15 Angstroms, more preferably a pore diameter of 4-7 Angstroms, a preferred structural form are zeolites or MFI-type ZSM-5, MEL or ZSM-11 as well as ferrierite and beta

The sub-group metals are introduced in the form of the inventive complexes of the formula I, that is for example in the form of cyano complexes, isonitrile and / or carbonyl via a so-called template synthesis in the catalyst after calcination, which takes place preferably at temperatures above 500 ° C, is finely dispersed metal oxide in the channel or cavity structure of the zeolite zuαick This metal oxide can be leduziert if necessary, by hydrogen to the elemental metal Preferably, however, the metal oxides formed through the calcination process can be used

The complexes inventively used according to the formula I should on one hand be water soluble, the transition group metals are preferred on the other hand remain stable in an alkaline medium, therefore in the form of the stable in an alkaline environment carbonyl or cyano complexes incorporated in the hydrothermal synthesis of zeolite catalysts in this case cyanocomplexes is a by the calcination entfernbaies cation preferred, especially an ammonium compound (JNTH) is used herein Gamdsatzlich all kinds are suitable from Nebengruppenmetallcyanokomplexen, preferred are those having 6 coordination sites, for example with an octahedral structure with 4 coordination sites, for example with planaier or tetrahedral structure, particularly preferably are those based on the metals vanadium, chromium, molybdenum, tungsten, manganese, titanium, zirconium, hafnium, Technelium, rhenium, iron, ruthenium, osmium, copper, cobalt, rhodium, nickel, iridium, palladium, platinum, gallium, silver and / or gold, are very particularly preferred Ammoniumtetracyanomckelat, Ammomumtetracyanopalladat, Ammoniumtetracyanαplatinat, Ammoniumhexacyanoruthenat, Ammoniumhexacyanoplatinat, Ammoniumhexacyanocobal-tat, Ammoniumhexacyanochromat and Ammoniumhexacyanoferrat Also suitable are mixed complexes of these metals with the general structural formula [metal (CN) 3 X] 11 ", wherein X is a volatile component such as represents water or ammonia

In the carbonyl both mononuclear such as polynuclear carbonyls different structure of the above metals are suitable, here preferably iron pentacarbonyl are also suitable Carbonylmetallatanionen the general structural formula lSΗ 4 [metal (CO) ""], here particularly Ammoniumtetracarbonylferrat

Also, the isonitrile complexes can be used pure or as mixed complexes of metals accordance with the invention claimed according to formula I

Is used as catalytically active subgroup metal iron, this inventively for example can be given as Ammoniumhexacyanoferrat into the reaction mixture, the iron can be present in both two- and / or trivalent form, it is also possible to use other stable complexes such or B in hot water soluble in alkaline medium iron carbonyls, e.g. iron pentacarbonyl B to admit

Of course, be certain metals that are less capable of forming acidic sites, such as B, the Ti present in the 4 subgroup of the periodic system, problems with installing Thus, a conventional titanium silicalite, the z B according to US Patent 4,410,501 from a hydrolyzable titanium compound such as TiCl 4, TiOCl 2, tetraalkoxytitanium, preferably tetraethoxytitanium, as well as from tetraethyl orthosilicate, and tetrapropyl ammonium hydroxide is prepared accordance with the invention are modified with at Ammoniumhexacyanoferi or iron carbonyls, whereby it also is well suited for applications erfmdungs- gemaßen

The acidity of the Katalysatoien can duich the Kalzinienmgsprozess duich Odei subsequent hydrothermal treatment with a water vapor-containing gas at a

be changed temperature between 300 and 950 ° C, but also by the incorporation of certain metals In the hydrothermal treatment with steam, the zeolite catalyst at a temperature of 300 to 950 ° C, preferably 450 to 800 ° C with a gas of 1 to 100 mol%, preferably contains from 10 to 100 mol% and very particularly preferably from 50 to 99 mol% steam treated Suitable methods are found for example in WO 95/27560 (1995) or in DE 196 34 406 ( 1996) such treatment may further increase the Lewis acidity

By the use of trivalent metals, such as aluminum, for example triisobutylaluminum, if needed, acid strength of the catalyst can be accurately adjusted, if little or almost no presence of acid centers, in particular of Bronsted acid sites is required, as for example in oxidation reactions, it is advisable when the present accordance with the Kalzinieamg molar ratio of SiO 2 Al 2 O 3 more than 1 10 "2 amounts More preferably, the catalyst contains according to the invention, no aluminum

Catalysts 10 "D to 1 3 x 10" 2 are preferably prepared by the inventive method with a molar ratio of SiO 2 to the subgroup metals of 1 was obtained (based on the calcined catalyst), it may be advantageous if the molaien conditions are in the narrower areas, such B of 1 10 "4 to 1 5 x 10" 2, or from 1 10 "^ to 1 10" 2 These conditions apply to SiO 2 to the transition group metal or Nebengruppenmetalloxid In the case of iron as a transition group metal amounts to a molar ratio of SiO 2 to Fe 2 O ^ preferably between 1 10 "5 (minimum) to 1 1.5 x 10" 2 (maximum), preferably between 1 10 "4 (minimal) to 1 10" 2 (maximum), more preferably between 1 0, 6 x lO ^ (minimal) to 1 0.9 x 10 "3 (maximum)

As the silicon component in the let λ ^ of the invention in particular find out a tetraalkyl orthosilicate such Teti aethylorthosilikat B, any other silicate in colloidal form, or a silicate of an alkali salt using organic base may be a tetraalkylammonium hydroxide, such as for example, be Tetrapropylammomumhydioxid

The preparation method of the Gaindgeaistes of the catalysts is described in U.S. Patent 4,410,501

The transition metal can ei flndungsgemass given as Ammomumhexacyanometallat or Ammoniumtetracyanometallat into the reaction mixture, it is also possible to use other stable complexes such B or in hot water in an alkaline medium soluble carbonyls use, however, are unsuitable all connections that do not form stable complexes - especially in an alkaline medium - represent such B Ubergangsmetallcitrate and Ubergangsmetallacetylacetonate because they are permanently installed in the Gittergeaist and - create strong acid sites - especially if they are not quadrivalent

If an excess of Ammoniumhexacyano- or Ammoniumtetracyanometallaten or metal carbonyls used, they are in addition to storage on non-lattice sites and on the surface of the zeolite as oxides deposited This is not adversely usually in individual cases may even incur a one of additional catalytic effect

Naturally it catalysts accordance with the invention produced also in membranes with pore diameters below 2000 Angstrom use at pore diameters of 50 to 1000 Angstrom are especially ultrafiltration membranes concerned If the catalysts are used in the production of nano-filtration membranes, the pore diameter of between 5 and 50 Angstroms varies at a pore diameter of about 5 angstroms, these membranes are also suitable for gas separation membrane applications is in connection with a particular use in batteries or fuel cells a possible use of the Nebengaippenmetall-containing zeolite catalyst in the fuel cell is therefore quite possible

The catalysts inventively produced can be used in a wide range of applications in industrial chemistry used as lsomerisieaingsreaktionen, hydrogenation reactions, Dehydrieireaktionen, alkylation reactions, disproportionation reactions, alcohol production from olefins, epoxidation, coupling reactions, substitution reactions, cycloaddition and Cycloreversionsreaktionen, ether, Roholcracking, hydrocracking, Fischer-Tropsch synthesis of alcohols Odei hydrocarbons, synthesis of methanol from synthesis gas or methane, but insbesondre for Oxidationsieaktionen of organic substrates with atmospheric oxygen, hydrogen peroxide, organic peroxides or nitrous oxide is particularly preferred to use the inventive Nebengruppenmetall--containing zeolite catalyst for the oxidation of organic substrates, in particular for the preparation of substituted and unsubstituted hydroxyaromatics The novel Nebengaippenmetall-sustainably en zeolite catalysts which can be particularly as a catalyst for the production of phenol from benzene, of cresol from toluene, from substituted with more methyl groups phenol from the corresponding benzene derivative of trimethylphenol and trimethylhydroquinone from trimethylbenzene, nitro phenol from nitrobenzene by substituted with halogen phenol use of halogen-substituted benzene or aminophenol from aminobenzene

Likewise, the inventive zeolite catalysts can be used as catalysts in the production of multiply hydroxylated substituted and unsubstituted benzenes as catechols, hydroquinones, pyrogallol and phloroglucinol Furthermore repeatedly alkylsubstuierte benzenes are hydroxylated Thus, using the novel zeolite catalysts eg trimethylbenzene can on in this way to give trimethylphenol or trimethylhydroquinone be oxidized in this way, by using the Nebengaippenmetall-containing zeolite Katalysatoi s tocopherols are manufactured this is for example a route to synthesize α-tocopherol (vitamin e) and it follows that the inventive catalyst as a catalyst can be used in the preparation of α-tocopherol

Preferably, moreover, the manufacture of propylene oxide, starting from propene and hydrogen peroxide, or nitrous oxide, this catalyst can be used both in the liquid phase and in the gas phase carried out also for this method is dei inventive zeolite

Another Einsatzmoglichkeit the catalysts inventively produced is as denitrification catalyst in power plants and in exhaust systems of internal combustion engines, such B aftfahrzeugen in Ki or unwanted by Salpetersaureanlagen to remove! Nitrogen oxides (NO

Furthermore, these catalysts can be used in fuel cells, insbesondre for coating the electrodes, used in the latter case, one can use, for example ammonium hexacyanoplatinat which to atomic after storage as an oxide in the channel and cavity structure of a zeolite with eg hydrogen, very finely divided platinum reduced can be

The example of the oxidation of benzene to phenol to a catalyst according to the invention the shape selectivity and activity of the catalyst was the one hand, checks the other hand, was investigated as an oxidizing agent by the use of nitrous oxide, such as nitrogen oxides behave in this case

Surprisingly, the synthesis of phenol from benzene was prepared with a accordance with the invention, the shape-selective catalyst with a high selectivity possible the activity of the catalyst remained over the entire review phase obtained The dinitrogen monoxide is decomposed into pure nitrogen and oxidative oxygen

The use of the catalysts inventively produced in process for the oxidation of organic substrates for example of benzene or benzene derivatives can be carried out by a catalytic oxidation of the substrate with a nitrous oxide-containing gas at temperatures between 100 - 800 ° C, preferably 300 - carried out 500 ° C. the method is particularly suitable for the preparation of phenol from benzene

Commonly used Larger experimental reactors have for this reaction tube reactors for example an internal diameter of 0.05 m and a length of about 3.0 meters but also often commercially available differential recycle reactors (see examples) For Patfungen laboratory scale in use

For nitrous oxide different sources are considered, the catalytic decomposition of ammonium nitrate at 100-160 ° C with manganese, copper, lead, bismuth, cobalt and nickel catalysts so that the gas does not deliver a mixture of nitrous oxide, nitrogen oxide and nitrogen dioxide, can be used directly for the oxidation of benzene somewhat better the oxidation of ammonia with oxygen to platinum or Wismutoxidkatalysatoren at 200-500 ° C and the reaction of nitric oxide with carbon monoxide on platinum catalysts are in the first case, however, as a by-product water, in the second case the dinitrogen monoxide carbon dioxide produced in this way can not be used directly for the oxidation of benzene may Similarly, the resulting nitrous oxide can not be used directly for the oxidation at the Adipinsaureherstellung but must be subjected to a separate purification step would interfere particular in the Exhaust oxygen contained and the NOx

Recently, however, new processes for the production of nitrous oxide has been developed, which start in principle from ammonia and oxygen in the air so that nitrous oxide einsteht cost example is the direct production of nitrous oxide (N 2 O) in Chem. Systems 98 / 99S14 (1999 shown) comprising

The gas nitrous oxide-containing may contain inert gases such as nitrogen and rare gases, but also ammonia and water vapor and traces of other oxides of nitrogen or air may be present

Of course, in the production of phenol and its derivatives starting from benzene or the corresponding benzene derivatives to increase the selectivity and the turnover and the microwave technology for use come phenol and its derivatives can be stimulated to rotate by microwaves and are thus particularly easy solved by the catalyst

Examples:

1. Preparation of the catalysts Variant I

340-350 g of the respective starting mixture (see recipes) 25% sodium-ammonium Tetrapiopyl be in a glass flask under the exclusion of air to 615 g hydroxidlosung in water was stirred for l hour is then carefully in Vei run of 5

heated hours uniformly to 90 ° C and the thus released alcohol expelled Thereafter, the volume of 1 150 g of distilled water is added and the homogeneous liquid placed in a flask equipped with a stirrer autoclave The mixture is heated to 175 ° C and under stirring constantly its own pressure for a time of 10 days left then it is cooled, the solid is filtered off and washed with hot distilled water mehiere times Thereafter, the product is completely dried, heated at a heating rate of 0.5 ° C / min and then for 6 hours at

calcined 550 ° C under Luftatmo sphere

The activity of the catalyst is determined by GC based on the measured turnover The BET surface areas are all between 400 and 600 m 2 / g, average pore dei bulk is about 5-7 Angstroms, as determined by Horvath and Kawazoe

(J. Che. Eng. Jpn. 16, 1983, 470 ff.)

Catalyst not of the invention

Starting mixture tetraethyl 340.22 g

Iron (IlI) citrate, monohydrate 6J3 g

Mean Porengioße about 5.5 Angstroms BET surface area 470 m 2 / g

Analysis of the final product (wt -%) SiO 2 98 12%

Fe 2 O, 1.86%

Catalyst not of the invention

starting mixture

Tetraethyl 340.22 g

Iron (III) acetylacetonate 8.22 g

Average pore size about 5.5 Angstiom

BET surface area 480 nr / g of the final product analysis (wt -%) SiO 2 98 12%

Fe 2 O 3 1.85%

1.3 catalyst accordance with the invention,

starting mixture

Tetraethyl 340.22 g

Ammoniumhexacyanoferrat 6, 19 g

Average pore size about 5.5 Angstroms

BET surface area 470 m 2 / g

Analysis of the final product (wt -%) SiO 2 98.12% Fe 2 O 3 1.87%

1.4 catalyst according to the invention

starting mixture

Tetraethyl 340.22 g of iron pentacarbonyl 4.56 g

Mi ttleie pore size about 5.5 Angstroms BET Obet flat 450 m 2 / g

Analysis of the final product (wt -%)

SιO 2 98, 13%

Fe 2 O 3 1.87%

1.5 catalyst accordance with the invention starting mixture

Tetraethyl 7.94 g

334.60 g of aluminum hydroxide, 0.09 g of tetraethylorthosilicate

Ammoniumhexacyanoplatinat 1, 11 g Mean pore size about 6.5 Angstroms BET surface area 480 m 2 / g

Analysis of the final product (wt -%) TiO 2 2.78%

SiO 2 96.50%

Al 2 O 3 0.06%

PtO 2 0.65%

1.6 catalyst according to the invention

starting mixture

Tetraethyl 334.60 g of aluminum hydroxide 1.34 g

Ammoniumtetracyanopalladat, trihydrate 6.44 g

Average pore size about 6.0 Angstroms BET surface area 470 m 2 / g

Analysis of the final product (wt -%) SiO 2 96.50%

Al 2 O 3 0.87%

PdO 2.62%

Production of phenol with the catalysts according to 1.3 and 1.4 of benzene and nitrous oxide (N 2 O)

Fui these laboratory experiments, a commercially available differential circulation reactor (volume 3 1) is used Here, in the reaction chamber of the differential loop reactor 10 g

The fixed catalyst Reaktionsiaum may by an electrical heating on wall

be adjusted reaction temperatures of 300 to 500 ° C below the catalyst within the reaction chamber, a rapidly rotating turbine is mounted which sucks the reaction mixture at high speed and over an outboard tube in the inlet of the reactor jerk felt by this procedure as can at Diffüsionslimitierungen the catalyst surface be excluded in this circuit line can defined amounts of benzene, N 2 O and an inert gas such as nitrogen, inlet in any ratios, and are continuously discharged Usually volumetric flow rate of 500 Nml / min with a ratio of inert gas / N 2 O / benzene set of 19 3 1 Gaseous samples from this cycle are injected directly into a gas chromatograph to analyze the composition of the reaction mixture, the reactor is used in this manner as a continuously operated stirred tank, the volume flow in the internal circuit is to Größ orders of magnitude higher than the continuously supplied amount of gas, the reaction time can be arbitrarily selected, being established after a few hours Konstanz

3. results

(Composition of the oxidizing agent 100 vol .-% N 2 O)

4. Preparation of the catalysts, Variant II 450 g dei starting mixture feed in a glass flask with exclusion of air untei

800 g of 25% Tetiapiopylammoniumhydioxidlosung m Wassei for 1 hour geaihrt is then gently heated in the course of 5 hours uniformly to 90 ° C and the thus released alcohol ausgetneben Thereafter, wnd the volume with 1500 g of distilled water added and the homogeneous fluid into a optionally equipped with a stirrer autoclave the mixture is heated to 175 ° C and under the autogenous pressure for a time of 10 days left is then cooled under constant stirring, the solid is filtered off and washed with hot distilled water several times Afterwards the product is completely dried heated at a heating rate of 0.5 ° C / min and then calcined for 6 hours at 550 ° C under air atmosphere

The BET surface areas of the prepared compounds be about 450 m 2 / g, the average of the pore size is 0.55 nm The determination is made by Horvath and

Kawazoe (... J. Chem Eng Jpn 16, 1983, 470 ff) The analytical values ​​of the final products are in wt -% indicated

The activity of the catalyst is determined by GC based on the measured benzene sales

Examples of the composition of the starting mixtures

Component for silicon tetraalkyl orthosilicates, for example tetraethyl orthosilicate

Component for 4-value subgroup metals Metalltetrahalogenide, metal oxyhalides, Metalltetraalkoxyverbindungen, eg titanium tetraethylate, Zirkoniumis- opropylat

Component for aluminum aluminum, triisobutyl aluminum component for iron acetylacetonate (not of the invention), ferric citrate (not according to the invention) of iron nitrate (not eifmdungsgemass) Ammoniumhexacyanofei rat (according to the invention), iron pentacarbonyl (Inventive)

Catalyst not according to the invention, the preparation according to US-5J 10995, Example 18 Analysis of the final product (wt -%) 99.47 SiO 2

0.52 Fe 2 O? Odei mass ratio

1.0 Si0 2 5.31 10 "3 Fe 2 O 3 or 1.0 molar ratio SiO 2 210" 3 Fe 2 O 3

Catalyst not according to the invention, the preparation according to US-5J10995, Example 38 Analysis of the final product (wt -%) 98.0 SiO 2

1.67 Al 2 O 3 0.31 Fe 2 O 3 mass ratio or l, 2 0SiO 3.1 10 "3 Fe 2 O 3 or SiO 2 molar ratio of 1.0 10" 2 A1 2 O 3 l, 210 "3 Fe 2 O 3

Katalysatoi, not according to the invention, according to US-5J Heistellung 10995, Example 42 Analysis of the final product (wt -%) 98.26 SιO 2 1.66 Al 2 O.

0.07 Fe 2 O 3 or Si0 2 Massenveihaltnis 1.0 1.69 10 "2 A1 2 O 3 7.410" Fe 2 O 4, or molaies ratio l, 0SiO 2 10 "2 A1 2 O 3 2.810" 4 Fe 2 O,

Catalyst not according to the invention, according Heistellung ß US 5, 110995, Example 47 Analysis of the final product (wt -%) TiO 2 1.42 97.19 SiO

1.23 Al 2 O 3 Fe 2 O 3 or 0J5 mass ratio l, 46 10 "2 TiO 2

1.0 SiO 2 1.27 10 "2 A1 2 O 3

15.4 10 "4 Fe 2 O 3 molar ratio or

1.1 10 "2 1.0 TiO 2 SiO 2

7.5 10 "3 A1 2 O 3 5.8 10" 4 Fe 2 O 3

Catalyst not according to the invention, the preparation according to US-5J 10995, Example 48 Analysis of the final product wt ~%) 2.57 TiO 2

96.9 SiO 2 0.51 Fe 2 O 3 or mass ratio 2.6 10 "2 TiO 2 SiO 2 1.0 5.3 10" Fe 2 O, or molar ratio 2 10 "2 TiO 2 1.0 Si0 2 2 10 "3 Fe 2 O 3

Catalyst such as 4 1, but prepared with appropriate amounts of Ammoniumhexacyanofei rat (according to the invention)

Katalysatoi such as 4 5 but made with appropriate amounts of Ammoniumhexacyanoferrat (Inventive) catalyst not according to the invention, made with iron acetylacetonate

Analysis of the final product (wt -%) 98 14 SiO 2

1.85 Fe 2 O 3 or SiO 2 mass ratio of 1.0

18.87 10 "3 Fe 2 O 3 molar ratio or

1.0 SiO 2

7J 10 "3 Fe 2 O 3

Catalyst not according to the invention, made with iron acetylacetonate

Analysis of the final product (wt -%) 2.82 TiO 2

96.46 SiO 2

0.07 Al 2 O 3 0.64 Fe 2 O 3 or mass ratio

2.92 10 "2 TiO 2

1.0 SiO 2

7.29 10 "4 Al 2 O 3 6.64 10 '3 Fe 2 O 3 molar ratio or

2.2 10 "2 TiO 2 l, 0 SiO 2

4.3 10 "4 A1 2 O, 2.5 10" 3 Fe 2 O.

Catalyst not according to the invention, prepared with ferric citrate analysis of the final product (wt -%) 1, 6 TiO 2

96.5 SiO 2 l, 83 Al 2 O 3

0.024 Fe 2 O. Odei mass ratio 1.65 10 "TiO 2, SiO 2 1.0 1,89JO" 2 A1 2 O 3 2.48 J0 "4 Fe 2 O 3 molar ratio or l, 2J0" 2 TiO 2

1.0 SiO 2 1,1JO "2 A1 2 O 3 9.3 J0" 5 Fe 2 O 3

4J catalyst such as 1: 4.8, prepared with appropriate amounts of Ammoniumhexacyanoferrat (Inventive)

4J2 catalyst such as 4.9, prepared with appropriate amounts of ammonium hexacyanoferrate (Inventive)

4J3 4J0 as catalyst, prepared with appropriate amounts of iron pentacarbonyl (Inventive)

5. Preparation of phenol with the catalysts of Examples 4J to 4J3 of benzene and nitrous oxide

It has been described, the same test arrangement as under 2), is used. When N 2 O gas-containing pure N 2 O was used.

Claims

claims:
1. A process for the preparation of transition group metal-containing zeolite catalysts by
Hydrothermal synthesis with subsequent calcination, characterized in that the sub-group metals in the form of complexes of the general formula
[Metalι z (CO) a (CN) b (CNR) c (X) d (Y) J n "odθ1" - with z> 1,
R = alkyl chain having 1 to 10 carbon atoms, a, b, c, d and e = 0 or an integer, where a, b, c, d and e may be the same or different and the sum of a, b, c, d and e> 1, n = 0 or a negative or positive integer, and
X and Y represent a volatile component be incorporated in the hydrothermal synthesis of the zeolite catalysts
2 A method according to Anspaich 1, characterized in that the sub-group metals in the form of pure or mixed carbonyl, cyano, or isonitrile complexes are introduced in the hydrothermal synthesis of the zeolite catalysts
3. A process according to any one of claims 1 to 2, characterized in that the transition group metals are introduced in the form of the stable in an alkaline environment carbonyl or cyano complexes in dei hydrothermal synthesis of zeolite catalysts
4 A method according to any one of claims 1 to 3, characterized in that as Nebengaippen etal vanadium, chromium, molybdenum, tungsten, manganese, titanium,
is zirconium, hafnium, technetium, rhenium, iron, ruthenium, osmium, copper, cobalt, rhodium, iridium, nickel, palladium, silver, gallium, gold and / or platinum is used Process according to one of the address 1 to 4, characterized in that is used as carbonyl iron pentacarbonyl or Ammoniumtetracarbonylferrat
Method according to one of the address 1 to 4, characterized in that platinate as a cyano-complex Ammoniumtetracyanonickelat, Ammoniumtetracyanopalladat, Ammoniumtetracyanoplatinat, Ammoniumhexacyanoruthenat, Ammoniumhexacyano-, Ammoniumhexacyanocobaltat, or Ammoniumhexacyanochromat
Ammoniumhexacyanoferrat is used
Method according to one of the address 1 to 6, characterized in that the molar ratio of SiO 2 to Al 2 O of the calcined zeolite catalyst 10 "2 amounts to a maximum of l
A method according to any one of claims 1 to 7, characterized in that the molar ratio of SiO 2 to the subgroup metals of the calcined zeolite
The catalyst is between 1 10 "3 4 to 1 x 10" 2 is
A method according to any one of claims 1 to 8, characterized in that the zeolite Katalysatoi a hydrothermal treatment is subjected to water vapor, wherein the zeolite catalyst at a temperature between 300-950 ° C with a gas, 1 - 100 mol% contains water vapor, is treated
Use of the Nebengaippenmetall-containing zeolite catalyst prepared according to the addresses 1 to 9, for the oxidation of organic substrates
Use of the Nebengaippenmetall-containing zeolite Katalysatois, hei detected according to the addresses 1 to 9, for the preparation of substituted and unsubstituted hydroxyaromatics
Use of the Nebengaippenmetall-containing zeolite catalyst prepared according to claims 1 to 9, for preparing phenol from benzene, of cresol from toluene, from substituted with more methyl groups phenol from the corresponding benzene derivative of trimethylphenol and trimethylhydroquinone from trimethylbenzene, of nitrophenol from nitrobenzene, substituted by halogen with phenol from halogen substituted benzene or aminophenol from aminobenzene
Use of the transition group metal-containing zeolite catalyst prepared according to the addresses 1 to 9, zm production of catechol, resorcinol, hydroquinone, pyrogallol or phloroglucinol
Use of the transition group metal-containing zeolite catalyst prepared according to the addresses 1 to 9, for Flerstellung of tocopherols
Use of the transition group metal-containing zeolite catalyst prepared according to claims 1 to 9, peroxide to produce propylene oxide from propene with hydrogen, or with nitrous oxide
Use of the transition group metal-containing zeolite catalyst prepared according to the addresses 1 to 9, as a denitrification catalyst
Use of the transition group metal-containing zeolite catalyst prepared according to the addresses 1 to 9, in the fuel cell
EP01988696A 2000-10-26 2001-10-12 Method for the production of form-selective catalysts and use thereof Withdrawn EP1334067A1 (en)

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DE10139316 2001-08-09
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US9630899B1 (en) * 2015-10-26 2017-04-25 Chang Chun Plastics Co. Ltd. Process for producing hydroquinone and derivates

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US4699894A (en) * 1985-04-17 1987-10-13 Chevron Research Company Highly active and highly selective aromatization catalyst
DE19829515A1 (en) * 1998-07-02 2000-02-10 Kowalak Stanislav Metal-modified zeolite catalyst for the hydroxylation of aromatics with nitrous oxide, obtained by treatment of zeolite with gaseous metal salt, e.g. iron-III chloride, followed by calcination at high temperature

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