EP2276566A1

EP2276566A1 - Catalyst for the dehydroaromatisation of methane and mixtures containing methane

Info

Publication number: EP2276566A1
Application number: EP09730456A
Authority: EP
Inventors: Frank Kiesslich; Joana Coelho Tsou; Bilge Yilmaz; Sebastian Ahrens; Thomas Heidemann; Veronika Will; Christian Bechtold
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-04-08
Filing date: 2009-04-08
Publication date: 2011-01-26
Also published as: US20110124933A1; JP5656826B2; JP2011518660A; WO2009124960A1; US8742189B2

Abstract

The invention relates to a catalyst for the dehydroaromatisation of C₁-C₄-aliphates, that can be obtained by the double treatment of a zeolith from the groups MFI and MWW with mixtures containing NH₄, respectively with subsequent drying and calcining. The catalyst contains molybdenum and optionally, Cu, Ni, Fe, Co, Mn, Cr, Nb, Ta, Zr, V, Zn and/or Ga as additional elements. The invention also relates to a method for the dehydroaromatisation of a mixture containing C₁-C₄-aliphates by reacting in the presence of a catalyst.

Description

Catalyst for the dehydroaromatization of methane and methane-containing mixtures

description

The present invention relates to a catalyst for the dehydroaromatization of d-C ₄ -aliphatic, which is obtainable by treating a zeolite twice from the group MFI and MWW with NH ₄ -containing mixtures, each with subsequent drying and calcination. The catalyst contains molybdenum and optionally as further elements Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and / or Co.

Another object of the present invention is a process for the dehydroaromatization of a mixture containing Ci-C ₄ -Aliphaten by reaction in the presence of the catalyst.

Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, styrene, xylene and naphthalene are important intermediates in the chemical industry, whose demand is still increasing. As a rule, they are obtained by catalytic reforming of naphtha, which in turn is obtained from petroleum. Recent studies show that global oil reserves are more limited compared to natural gas reserves. Therefore, the production of aromatic hydrocarbons from educts that can be obtained from natural gas, is now an economically interesting alternative. The main component of natural gas is usually methane.

A possible reaction route for the production of aromatics from aliphatics is the non-oxidative dehydroaromatization (DHAM). The reaction takes place here under non-oxidative conditions, in particular with the exclusion of oxygen. In the case of DHAM, dehydrogenation and cyclization of the aliphatic compounds to the corresponding aromatics with liberation of hydrogen takes place.

For catalysis of non-oxidative dehydroaromatization, H-ZSM-5 zeolites modified with molybdenum have been found to be particularly suitable.

D. Wang et al. (Journal of Catalysis 169, (1997), pages 347 to 358) describe the non-oxidative conversion of methane to benzene over H-ZSM-5 catalysts containing 2% by weight of molybdenum. Methane conversions between 4 and 8% were achieved with benzene selectivities of approx. 60%. L. Wang et al. (Applied Catalysis A: General 152, (1997), pages 173 to 182) carried out the non-oxidative dehydroaromatization on molybdenum-containing H-ZSM-5 catalysts and investigated the influence of different pretreatment methods and the doping of the catalyst with other metals. The methane conversions were between 3 and 5% with selectivities for benzene and toluene of up to 96%. The doping with lanthanum and vanadium showed no positive effect, the doping with tungsten or zirconium proved to be advantageous.

Y. Zhang et al. (Journal of Natural Gas Chemistry 12, (2003), pages 145 to 149) investigated the effect of pretreatment of Mo / H-ZSM-5 doped with copper and used undoped on the hydroaromatization of methane. The presence of copper increased the methane conversion significantly from 7.5 to 10.5 wt .-% with constant benzene selectivity.

Y. Xu et al. (Journal of Catalysis 216, (2003), pages 386 to 395) describe in a review the problems that occur when using molybdenum-containing H-ZSM-5 catalysts for the dehydroaromatization of methane. In particular, the deactivation of the catalyst by coke deposits is a major problem. Y. Xu et al. summarize some of the possibilities described in the literature for improving the activity and stability of Mo / H-ZSM-5 catalysts by steam dealumination, dealumination by acidic solutions, or silanization.

S. Qi and W. Yang (Catalysis Today 98, (2004), pp. 639-645) report that methane conversion and selectivity to benzene on a Mo / H-ZSM-5 zeolite catalyst, and the like. can be increased by the addition of copper. Thus, the conversion of methane increases from 18 to 20% with benzene selectivities of up to about 95%. The doping also has a positive influence on the stability and the coking tendency of the catalyst.

S. Li et al. (Applied Catalysis A: General 187, (1999), pages 199 to 206) investigated the non-oxidative dehydroaromatization of methane over copper-doped Mo / H-ZSM-5 catalysts compared to the non-doped catalysts. Commercially available H-ZSM-5 zeolite was calcined, boiled in water and ion exchanged with ammonium nitrate. Subsequently, the zeolite was dried and calcined. In the case of the copper-doped zeolite, the copper ions were also deposited by ion exchange. The thus pretreated zeolite was then mechanically mixed with the appropriate amount of molybdenum oxide and calcined. By doping the catalyst with copper, the methane conversion increased from 7.4 to 10.1%, the benzene selectivity increased from 92.7 to 94.8%. The decrease in catalyst activity slowed as a result of doping with copper. BM Weckhuysen et al., (Journal of Catalysis 175, (1998) pages 338-346) examined the conversion of methane to benzene in the presence of transition metal-doped H-ZSM-5 zeolites. For this study, various pretreatments were carried out on commercially available H-ZSM-5 catalysts. The zeolites were subjected to partial or complete ion exchange by aqueous solutions containing ammonium nitrate and sodium chloride at different concentrations to obtain zeolites which are completely, only partially or not at all in the H form. The zeolites were then doped with Ga, Zn or Cr in conjunction with Ru or Pt and Mo, Cu, Zn and Fe. There were found metal conversions of 0.2 to 7.9% at benzene selectivities from 0 to almost 80%.

From the same group (BM Weckhuysen et al., Catalysis Letters 52 (1998), pages 31 to 36), a study on Mo / H-ZSM-5 catalysts on the deposited in the DHAM of methane on the coke coke. In this case, commercially available H-ZSM-5 zeolite was used as the catalyst support, which was completely converted into the H form by NH ₄ exchange and calcination and then impregnated with Mo and recalcined.

The coke deposits are a major problem for the industrial use of dehydroaromatization under non-oxidative conditions, as they reduce the activity of the catalyst in a relatively short time, resulting in short production cycles and a high regeneration requirement. In addition, the coke deposits are often accompanied by a shortened catalyst life. Also, the regeneration of the catalysts is not without problems, since for an economic process on the one hand regularly the output activities must be restored and on the other hand this must be possible over a large number of cycles.

The coke deposits also have an unfavorable effect on the material balance or the yield, since each molecule of starting material which is converted into coke is no longer available for the desired reaction to aromatics. The coke selectivities achieved hitherto in the prior art are in most cases more than 20%, based on the reacted aliphatics.

There is therefore a need for catalysts for the non-oxidative reaction of CrC ₄ -aliphatic compounds, which have a lower tendency to coke and a higher long-term stability than the catalysts known from the prior art. The catalysts should also be easy to regenerate to allow long catalyst lifetimes. The object is achieved by a molybdenum and zeolite-containing catalyst for the dehydroaromatization of a C-C ₄ -aliphatic-containing reactant stream E, by the steps

I. treating a zeolite selected from the group consisting of MFI and MWW with an NH ₄ -containing mixture, followed by drying and calcination of the zeolite,

II. Re-treating the zeolite with an NH ₄ -containing mixture with subsequent drying of the zeolite, III. Application of molybdenum and IV. Calcination

is available.

The catalysts according to the invention are particularly suitable for the nonoxidative dehydroaromatization of C 1 -C ₄ -aliphatics, ie for the preparation of aromatic hydrocarbon compounds such as benzene and toluene from these alkanes under non-oxidative conditions. Significantly less coke deposits on the catalysts according to the invention than on the catalysts known from the prior art. As a result, on the one hand increases the service life of the catalysts, before a regeneration of the catalyst is necessary; On the other hand, the reactant stream used can be used more economically, since less starting material is converted into harmful for the catalyst and the yield-reducing coke. The low selectivity for coke is accompanied by significantly higher conversions and / or higher benzene selectivities in the catalysts according to the invention, which leads to higher overall benzene yields. Another great advantage of the catalysts of the invention is their good regenerability. Even after several reaction and regeneration cycles, the initial activity of the catalyst in the first cycle is usually regained by the regeneration.

Non-oxidative conditions in accordance with the present invention mean that the concentration of oxidizing agents such as oxygen or nitrogen oxides in the feedstream E is below 5% by weight, preferably below 1% by weight, particularly preferably below 0.1% by weight. lies. Most preferably, the mixture is free of oxygen. Also particularly preferred is a concentration of oxidizing agents in the mixture E, which is equal to or less than the concentration of oxidizing agents in the source from which the Ci-C ₄ -Aliphaten originate.

The catalysts according to the invention contain zeolites selected from the structural types MFI and MWW, more preferably ZSM-5 and MCM-22. Zeolites are aluminum silicates which are usually produced in the sodium form. In the Na form, the excess negative charge due to the exchange of 4-valent Si atoms for 3-valent Al atoms in the crystal lattice is compensated by Na ions. Instead of sodium alone, the zeolite can also contain other alkali metal and / or alkaline earth metal ions for charge balance. The synthesis of the zeolites of the structures MFI and MWW is known to the person skilled in the art. These zeolites can be prepared, for example, starting from alkali aluminate, alkali metal silicate and amorphous SiC> ₂ under hydrothermal conditions. Here, the type of channel systems formed in the zeolite can be controlled via organic template molecules, the temperature and other experimental parameters.

Step I of the process according to which the catalyst according to the invention is obtainable consists in the conversion of the zeolite into the so-called H-form. This means that the alkali and / or alkaline earth metal ions contained in the zeolite are exchanged for protons. A common and preferred process according to the present invention for converting the catalysts into the H form is a two-stage process in which the alkali metal and / or alkaline earth metal ions are first exchanged for ammonium ions. Upon heating the zeolite to about 400 to 500 ⁰ C, the ammonium ion decomposes into volatile ammonia and in the proton remaining in the zeolite.

According to the present invention, in step I of the process, after which the catalyst according to the invention is obtainable, the zeolite is treated with an NH ₄ -containing mixture. As the NH ₄ -containing component of the mixture containing NH ₄ , at least one ammonium salt selected from the group consisting of ammonium halides, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrate, ammonium acetate, ammonium phosphate, ammonium hydrogenphosphate, ammonium dihydrogenphosphate, ammonium sulfate and ammonium hydrogensulfate is used. Ammonium nitrate is preferably used as the NH ₄ -containing component.

The treatment of the zeolite with the NH ₄ -containing mixture is carried out according to the known methods suitable for the ammonium exchange of zeolites. These include, for example, soaking, dipping or spraying the zeolite with an ammonium salt solution, the solution generally being used in excess. The solvents used are preferably water or alcohols. The mixture usually contains 1 to 20 wt .-% of the NH ₄ component used. The treatment with the NH ₄ -containing mixture is usually carried out over a period of several hours and at elevated temperatures. After the action of the NH ₄ -containing mixture on the zeolite, excess mixture can be removed and the zeolite washed. Subsequently, the zeolite at 40 to 150 ⁰ C for several hours, usually dried for 4 to 20 hours. This is followed by the calcination of the zeolite at temperatures of 300 to 700 ⁰ C, preferably from 350 to 650 ⁰ C and particularly preferably from 500 to 600 ⁰ C. The duration of calcination tion is usually 2 to 24 hours, preferably 3 to 10 hours, more preferably 4 to 6 hours.

According to step II of the present process, after which the catalyst according to the invention is obtainable, the zeolite is again treated with a NH ₄ -containing mixture and then dried. The renewed treatment of the zeolite with the NH ₄ -containing mixture according to step II of the process, after which the catalyst according to the invention is obtainable, takes place according to the above description for step I.

Commercially available H-form zeolites have usually already undergone a first ammonium exchange by treatment with an NH ₄ -containing mixture and subsequent drying and calcination, ie step I of the process after which the catalyst according to the invention is obtainable has already been obtained from the manufacturer of the present invention Zeolite performed. Therefore, according to the invention, commercially available zeolites of the structure types MFI and MWW present in the H form can be used directly in step II of the process according to the invention.

According to one embodiment of the process according to which the catalyst according to the invention is obtainable, the zeolite treated again with NH ₄ -containing mixture is additionally calcined between step II and step III. Calcination takes place at the conditions specified for the calcination in step I.

According to the invention, the renewed ammonium exchange serves not only to ensure the most complete possible replacement of the alkali metal and / or alkaline earth metal ions with protons, but also causes structural changes in the zeolite. Thus, the re-treatment of the zeolite increases e.g. the Si: Al ratio, which implies a change in the ratio of Lewis acidic centers to Bronsted acidic centers. The increase of the Si: Al ratio is caused by dealumination of the zeolite. Exemplary for the changes in the zeolite by the re-treatment is also the increase in the BET area.

The catalysts of the present invention contain molybdenum. This is applied wet-chemically or dry-chemically in step IV of the method on the zeolite according to the invention.

Wet-chemically, the molybdenum is applied in the form of aqueous, organic or organic-aqueous solutions of its salts or complexes by impregnating the zeolite with the appropriate solution. As a solvent can also serve supercritical CO ₂ . The impregnation can be carried out by the incipient-wetness method, in which the porous volume of the zeolite is filled by approximately the same volume of impregnating solution and - optionally after maturation - the carrier dries. You can also work with an excess of solution, the volume of this solution is greater than the porous volume of the zeolite. In this case, the zeolite is mixed with the impregnating solution and stirred for a sufficient time. Furthermore, it is possible to spray the zeolite with a solution of the molybdenum salt. There are also other, known in the art production methods such as precipitation of molybdenum on the zeolites, spraying a solution containing a molybdenum compound, Soltränkung etc. possible. Particularly suitable molybdenum compounds are (NH ₄ ) ₆ Mo ₇ O ₂₄ , MoO ₂ , MoO ₃ , H ₂ MoO ₄ , Na ₂ MoO ₄ , (NH ₃ ) ₃ Mo (CO) ₃ and Mo (CO) ₆ . After applying the molybdenum to the zeolite, the catalyst is dried at about 80 to 130 ⁰ C usually for 4 to 20 hours in vacuo or in air.

According to the invention, the molybdenum can also be applied by dry chemical methods, for example by precipitating the gaseous Mo (CO) ₆ gaseous at elevated temperatures from the gas phase on the zeolite.

According to the invention, the catalyst contains 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-%, particularly preferably 0.5 to 10 wt .-%, each based on the total weight of the catalyst, molybdenum.

According to a preferred embodiment, the catalyst contains at least one further element selected from the group Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and Co, more preferably selected from the group Cu, Ni, Fe , Cr, Nb, Ta and Co, in particular selected from the group consisting of Cu, Ni, Fe, Nb, Ta and Co. Particularly preferred are catalysts which, in addition to molybdenum, contain Cu as a further element. In a further preferred embodiment, the catalyst contains, in addition to molybdenum as a further element, Ni. According to a further preferred embodiment, the catalyst according to the invention contains Fe as well as molybdenum as further element.

The at least one further element besides molybdenum is present in the catalyst according to the invention in a concentration of at least 0.1% by weight, based on the total weight of the catalyst. The catalysts according to the invention particularly preferably contain at least 0.2% by weight, very particularly preferably at least 0.5% by weight of at least one further element selected from Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu , Ni, Fe and Co, based on the total weight of the catalyst. The maximum amount of the further element or of the further elements contained in the catalyst according to the invention, based in each case on the total weight of the catalyst, is 10% by weight, preferably 5% by weight.

According to the invention, preference is given to catalysts which contain Cu as a further element. Likewise preferred are catalysts which contain Ni as a further element, and also catalysts which contain Fe as a further element. According to the invention, particular preference is given to catalysts which contain from 0.1 to 20% by weight of molybdenum and at least 0.1% by weight of Cu, based on the total weight of the catalyst. According to a preferred embodiment of the present invention, the Mo and Cu-containing catalysts contain MCM-22 or ZSM-5 as zeolite.

Further preferred according to the invention are catalysts which contain 0.1 to 20% by weight of Mo and at least 0.1% by weight of Ni, particularly preferably 0.1 to 20% by weight of Mo and 0.5 to 2% by weight. % Ni, in each case based on the total weight of the catalyst.

According to a preferred embodiment of the present invention, the Mo and Ni-containing catalysts contain ZSM-5 as zeolite.

According to a preferred embodiment of the present invention, the Ni and Cu containing catalysts contain ZSM-5 as zeolite.

Likewise preferred according to the invention are catalysts which contain 0.1 to 20% by weight and at least 0.1% by weight of Fe, particularly preferably 0.1 to 20% by weight and 0.5 to 20% by weight of Fe , in each case based on the total weight of the catalyst.

According to another embodiment, the catalyst according to the invention contains more than one further element selected from the group consisting of Cu, Ni, Fe, Co, Mn, Cr, Nb, Ta, Zr, V, Zn and Ga in addition to Mo.

The catalyst particularly preferably contains at least two further elements selected from the group consisting of Cu, Ni, Fe, Co, Mn, Cr, Nb, Ta, Zr, V, Zn and Ga in addition to Mo.

Particular preference is given to catalysts which contain at least 0.1% by weight of a further element selected from the group consisting of Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and Co, preferably selected from the group Fe, Co, Ni, Cu, Nb, Ta and Cr and at least 0.05 wt .-% of a second further element selected from the group Cu, Ni, Fe, Co, Cr, Nb, Ta, Zr, V, Zn and Ga, preferably selected from the group consisting of Fe, Co, Ni, Cu, Nb, Ta and Cr, in addition to molybdenum, in each case based on the total weight of the catalyst.

According to the invention, the combinations Mo, Cu, Nb are preferred; Mo, Ni, Nb; Mo, Ni, Ta; Mo, Ni, Fe; Mo, Ni, Cr and Mo, Cu, Fe.

The elements Mn, Cr, Zr, V, Zn, Ga, Cu, Ni, Fe, Nb, Ta and Co are usually applied wet-chemically to the zeolite. These elements are analogous to the for the wet-chemical deposition of molybdenum described procedures applied to the zeolite. The metal salts used here are preferably the nitrates, such as copper nitrate, nickel nitrate, iron nitrate and cobalt nitrate, but other salts known to the person skilled in the art for wet-chemical application can also be used. These include the ammonium metallates, halides, in particular chloride, acetate, alkaline carbonates, formate, tartrate, complexes with ligands such as acetylacetate, amines, amino alcohols, diols, polyols, EDTA, carboxylates such as oxalate and citrate and Hydroxycarbonsäuresalze. It is also possible to apply the elements to the support as a fine carbon dioxide powder, since it is generally believed that molybdenum carbide forms the reactive species in the catalyst upon dehydroaromatization.

If the molybdenum is applied wet-chemically in step III, the at least one further element can be applied together with the molybdenum. However, it is also possible to apply the further element and the molybdenum in succession, with drying taking place after each application. It may also be advantageous to follow a certain sequence when applying. If the catalyst contains more than one further element, the molybdenum and the other elements can also be applied together or in succession, with the zeolite being dried in each case between the different applications. Again, it may be advantageous to apply the individual elements and the molybdenum in a certain order.

If the molybdenum is applied by dry-chemical means in step III, the impregnation with the at least one further element usually takes place before step III. If more than one further element is applied, these may be applied together or in succession, with drying taking place between the individual impregnation stages. It may be advantageous to apply the individual elements in a certain order.

In a preferred embodiment of the invention, the solution with which the molybdenum and optionally the further elements are applied to the zeolite contains at least one complexing agent. Preferably, the complexing agent is selected from the group of ammonia, acetylacetonate, amines, amino alcohols, EDTA, carboxylates such as oxalate and citrate and Hydroxycarbonsäuresalze. Particular preference is given to using EDTA. The presence of the complexing agents in the impregnating solution has an advantageous effect on the catalyst activity.

Contains the catalyst according to the invention according to one of the embodiments described above, at least two further elements selected from the group

Fe, Co, Ni, Cu, Cr, Nb, Ta, Mn, Zr, V, Zn and Ga is, according to a preferred According to the present invention, the Mo is applied to the zeolite together with at least one of the further elements in the presence of a complexing agent as impregnating solution, the zeolite is subsequently dried and the second or the further elements are applied by means of an impregnating solution.

If, as described above, the catalyst according to the invention contains at least one further element in addition to molybdenum, then the catalyst can be obtained by the steps

II. Re-treating the zeolite with an NH ₄ -containing mixture with subsequent drying of the zeolite, III. Applying the molybdenum and at least one further element selected from the group Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and Co, and IV. Calcining.

After application of the Mo and optionally the other elements is carried out in step IV of the process by which the catalyst according to the invention can be produced, a calcination of the catalyst. This is carried out under the conditions described above for the calcination carried out in step I.

According to a further preferred embodiment of the present invention, the catalyst is mixed with a Si-containing binder between step I and II or between step II and III. Particularly suitable as Si-containing binders are tetraalkoxysilanes, polysiloxanes and colloidal SiO ₂ sols.

If the Si-containing binders are mixed with the zeolite before step II, ie before re-treatment of the zeolite with an NH ₄ -containing mixture, prior to step II a calcination is carried out under the usual conditions. According to the invention, after the addition of the Si-containing binder, a shaping step takes place, in which the catalyst composition is processed into shaped bodies according to the processes known to the person skilled in the art. In this case, the shaping methods to be mentioned are, for example, spraying of a suspension containing the zeolite or the catalyst mass, tableting, pressing in the moist or dry state and extrusion. Two or more of these methods can also be combined. Auxiliaries such as pore formers and pasting agents or else other additives known to the person skilled in the art can be used for shaping. Possible pasting agents are compounds which improve the mixing, kneading and flow properties. In the context of the present invention, these are preferably organic, in particular hydrophilic polymers such as, for example, cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper pastes, acrylates, polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinylpyrrolidone, polyisobutylene, polytetrahydrofuran, polyglycol ethers, fatty acid compounds, wax emulsions, water or mixtures of two or more of these compounds. In the context of the present invention, pore formers which can be dispersed, suspended or emulsified in water or aqueous solvent mixtures are, for example, polyalkylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, carbohydrates, cellulose, cellulose derivatives such as, for example, methylcellulose. Cement fibers, PuIp, graphite or mixtures of two or more of these compounds. Pore formers and / or pasting agents are preferably removed after deformation by at least one suitable drying and / or calcining step from the shaped body obtained.

The geometry of the catalysts obtainable according to the invention can be, for example, spherical (hollow or full), cylindrical (hollow or full), ring, saddle, star, honeycomb or tablet shape. Furthermore, extrudates are for example in strand, Trilob, Quatrolob, star or hollow cylindrical shape in question. Furthermore, the catalyst mass to be molded can be extruded, calcined and the extrudates thus obtained can be broken and processed into chips or powders. The grit can be separated into different sieve fractions. A preferred sieve fraction has the grain size 0.25 to 0.5 mm.

According to a preferred embodiment of the invention, the catalyst is used as a shaped body or grit.

According to another preferred embodiment, the catalyst is used as a powder. The catalyst powder may contain Si-containing binder, but also be present free of Si-containing binder.

If the catalyst according to the invention contains an Si-containing binder, this is present in a concentration of 5 to 60 wt .-%, based on the total weight of the catalyst, preferably from 10 to 40 wt .-%, particularly preferably from 15 to 30 wt .-%.

Another object of the present invention is a process for preparing a molybdenum and zeolite-containing catalyst as described above comprising the steps I. treating a zeolite selected from the group consisting of MFI and MWW with an NH ₄ -containing mixture, followed by drying and calcination of the zeolite,

II. Re-treating the zeolite with an NH ₄ -containing mixture, followed by drying of the zeolite,

III. Applying the molybdenum and

IV. Calcining.

If, in addition to molybdenum, the catalyst according to the invention contains at least one further element as described above, the process according to the invention for preparing the catalyst comprises the steps

III. Applying the molybdenum and at least one further element selected from the group Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and Co, and IV. Calcining.

Likewise provided by the present invention is the use of the above-described catalyst according to the invention for the dehydroaromatization of a feedstock stream E C containing Cr C ₄ -aliphatic compounds.

It may be advantageous to activate the catalyst used for the dehydroaromatization of C 1 -C ₄ -aliphates before the actual reaction.

This activation can be carried out with a C 1 -C ₄ alkane, such as, for example, methane, ethane, propane, butane or a mixture thereof, preferably butane. The activation is carried out at a temperature of 250 to 650 ^° C., preferably at 350 to 550 ^° C., and at a pressure of 0.5 to 5 bar, preferably at 0.5 to 2 bar. Usually, the GHSV (gas hourly space velocity) at activation is 100 to 4000 h ^-1 , preferably 500 to 2000 h ^-1 .

However, it is also possible to carry out an activation by the reactant stream E thereof, the dC ₄ alkane, or a mixture, per se already contains or dC ₄ alkane, or a mixture thereof, the feed stream E is added. The activation is carried out at a temperature of 250 to 650 ^° C., preferably at 350 to 550 ^° C., and at a pressure of 0.5 to 5 bar, preferably at 0.5 to 2 bar. Usually is the GHSV (Gas Hourly Space Velocity) when activated at 100 to 4000 h ^"1 , preferably at 500 to 2000 h ^{" 1} .

In another embodiment, it is also possible to add hydrogen in addition to the CrC ₄ alkane. The activation can also be carried out only with methane as Cr C ₄ alkane.

According to a preferred embodiment of the present invention, the catalyst is activated with a H ₂ -containing gas stream which may additionally contain inert gases such as N ₂ , He, Ne and Ar.

Another object of the present invention is a process for the dehydroaromatization of a Ci-C ₄ -Aliphaten-containing Eduktstroms E by reacting the Eduktstroms E in the presence of a molybdenum and zeolite-containing catalyst as described above, by the steps

I. treating a zeolite selected from the group MFI and MWW with an NH ₄ -containing mixture, followed by drying and calcination of the zeolite, II. Re-treating the zeolite with an NH ₄ -containing mixture, followed by drying of the zeolite,

III. Applying the molybdenum,

IV. Calcining

is available.

Likewise, the process for the dehydroaromatization of a feed stream E containing CrC ₄ -aliphatic compounds by reacting the feed stream E in the presence of a catalyst containing molybdenum and zeolite as described above, by the steps

III. Applying the molybdenum and at least one further element selected from the group Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and Co, and

IV. Calcining,

is available, subject of the present invention. According to the invention, the reactant stream E contains at least one aliphatic having 1 to 4 carbon atoms. These aliphates include methane, ethane, propane, n-butane, i-butane, propene, 1- and 2-butene, and isobutene. In one embodiment of the invention, the reactant stream E comprises at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, in particular at least 90 mol%, of dC ₄ -aliphatic ,

Among the aliphatics, the saturated alkanes are particularly preferably used; the starting material stream E then preferably contains at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, more preferably at least 80 mol%, in particular at least 90 mol% % Alkanes with 1 to 4 C atoms.

Among the alkanes, methane and ethane are preferred, especially methane. According to this embodiment of the present invention, the reactant stream E preferably contains at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, more preferably at least 80 mol%, in particular at least 90 mol% methane.

Preferably, natural gas is used as the source of the Ci-C ₄ -Aliphaten. The typical composition of natural gas is as follows: 75 to 99 mol% methane, 0.01 to 15 mol% ethane, 0.01 to 10 mol% propane, up to 6 mol% butane and higher hydrocarbons, up to 30 mol% of carbon dioxide, up to 30 mol% of hydrogen sulfide, up to 15 mol% of nitrogen and up to 5 mol% of helium. The natural gas can be purified and enriched prior to use in the process according to the invention by methods known to those skilled in the art. Purification includes, for example, the removal of any hydrogen sulfide or carbon dioxide present in natural gas and other undesirable compounds in the subsequent process.

The dC contained in the feed stream E ₄ -aliphatics may also originate from other sources len, such as petroleum refining have been incurred. The dC ₄ aliphatics may also have been produced regeneratively (eg biogas) or synthetically (eg Fischer-Tropsch synthesis).

If biogas is used as the Ci-C ₄ -aliphatic source, the feed stream E may additionally contain ammonia, traces of lower alcohols and further admixtures typical of biogas.

In a further embodiment of the process according to the invention, it is possible to use LPG (liquid petroleum gas) as feed stream E. According to a further embodiment of the process according to the invention, it is possible to use LNG (Liquefied Natural Gas) as starting material stream E. In addition, hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen and one or more noble gases can be admixed with the reactant stream E.

According to the invention, the dehydroaromatization of Ci-C ₄ -aliphatics in the presence of the above-described inventive catalysts at temperatures of 400 to 1000 ⁰ C, preferably from 500 to 900 ⁰ C, more preferably from 600 to 800 ⁰ C, in particular from 650 to 750 ⁰ C, at a pressure of 0.5 to 100 bar, preferably at 1 to 50 bar, more preferably at 1 to 30 bar, in particular 1 to 10 bar performed. According to the present invention, the reaction is carried out at a GHSV (Gas Hourly Space Velocity) of 100 to 10,000 h ^-1 , preferably 200 to 3000 h ^-1 .

Of course, the catalysts used in the dehydroaromatization according to the invention can be regenerated with decreasing activity by customary methods known to the person skilled in the art. Particularly preferred according to the present invention is the regeneration of the catalysts with hydrogen. This can be done, for example, by adding hydrogen to the educt stream E. The ratio of reactant stream E to the hydrogen stream is usually in the range from 1: 1000 to 1: 1, preferably 1: 500 to 1: 5, but the ratio is preferably chosen such that a gas stream is used for the regeneration, which is at least 95 mol. Contains% hydrogen. However, it may also be advisable to alternately direct reactant stream E and hydrogen over the catalyst.

In particular, the catalysts according to the invention, which contain at least one further element selected from the group Cu, Ni, Fe and Co, can be easily regenerated by means of hydrogen.

The dehydroaromatization of dC ₄ -aliphatic compounds can in principle be carried out in all types of reactors known from the prior art. A suitable reactor form is the fixed bed, tube or shell and tube reactor. In these, the catalyst is as a fixed bed in a reaction tube or in a bundle of reaction tubes. Likewise, the catalysts according to the invention can be used as fluidized bed, moving bed or fluidized bed in the appropriate reactor types suitable for this purpose and the process according to the invention for dehydroaromatization can be carried out with the catalysts present in this way.

In the following, the present invention is explained in more detail by means of exemplary embodiments. A treating a zeolite with a NH ₄ -containing mixture

100 g of a commercially available ZSM-5 zeolite in H form are mixed with 100 g of ammonium nitrate and 900 g of water and heated for 2 hours in a stirred apparatus at 80 ⁰ C. After cooling, the suspension is filtered and washed with water. The filter cake is dried at 120 ⁰ C overnight.

B mixing the zeolite with a Si-containing binder and shaping

100 g of a ZSM-5 zeolite are mixed with 10 g of sodium carboxymethylcellulose and, after addition of 30 g of an Si-containing binder (Silres® MSE 100 from Wacker Silicons), kneaded for 60 minutes with the portionwise addition of about 100 ml of water. The mass thus obtained is extruded through a die having a round cross section (diameter 2 mm) and dried the extrudates obtained at 120 ⁰ C and calcined 5 hours at 500 ⁰ C. The strands thus obtained are broken and separated a sieve fraction of 0.25 to 0.5 mm, which is then used accordingly.

Examples 1 and 2:

Two different H-ZSM-5 zeolites are used to investigate the influence of NH ₄ treatment and shaping. In Table 1, the Si: Al ratios of the zeolite H-ZSM-5 PZ2-50 in the H-form without treatment with NH ₄ treatment, with NH ₄ treatment and formation of chippings and a sample, the was first processed into chips and then treated with NH ₄ , carried out in Table 2, the results for the zeolite H-ZSM-5 PZ2-25 are listed. The Si: Al ratio was determined by elemental analysis.

Table 1

Table 2

Example 3

Characterization of the microstructure

The microstructure of the untreated and NH ₄ NOs-treated H-ZSM-5 PZ2-25 zeolites was determined by means of nitrogen sorption (Quantachrom Autosorb). The nitrogen was adsorbed at -196 ° C, the Ausgastemperatur was 200 ⁰ C, the Ausgaszeit 14 hours. The pore volume (total) indicates the pore volume of all pores with a diameter below 335.47 nm. Pores with a diameter of 0 to 2 nm are regarded as micropores, pores with a diameter of 2 to 50 nm as mesopores and pores with a pore diameter> 50 nm (IU-PAC) as macroporous.

Table 3 shows the results of the characterization of the zeolite microstructure.

Table 3

Treatment with NH ₄ NOs significantly increases the BET surface area and the Si: Al ratio. The micropore volume is relatively little changed by the pretreatment, the fragmentation significantly reduces the proportion of meso and macropores. Under C to I, the impregnation of the zeolite with molybdenum and optionally other elements and the test method for the catalyst are described.

C Impregnation of the zeolite optionally pretreated after A and / or B with aqueous ammonium heptamolybdate solution (Mo solution)

100 g of optionally pretreated with NH ₄ according to A and / or B zeolite carrier are placed in a tray. Approximately 12 g of ammonium heptamolybdate tetrahydrate (> 98%, ABCR) are made up with water to the appropriate volume of water absorption (about 100 ml) of the zeolite and stirred until complete dissolution. The solution is then added with stirring to the zeolite and the mass further mixed for 15 min at room temperature. The mass is then heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 or 5 h.

D Stepwise impregnation of the optionally pretreated after A and / or B zeolite with Mo solution, drying and impregnation with aqueous, Ni, Cu, Cr or Fe-SaIz-containing solution

100 g of a (optionally pretreated with NH ₄ NO ₃ according to A and / or B) zeolite are impregnated according to C with molybdenum, but finally only dried and not calcined. The corresponding Mo-loaded zeolite is placed in a dish. For impregnation with Cu, 4.1 g of copper (II) nitrate 2.5 hydrate (> 99%, Riedel-de-Haen) with water to the appropriate volume of water absorption (about 100 ml) Zeolite filled and stirred until complete dissolution. The solution is then added with stirring to the zeolite and the mass further mixed for 15 min at room temperature. The mass is then heated in a drying oven to 120 ⁰ C, dried overnight and then 4 o- 5 hours at 500 ⁰ C calcined. If Ni is to be impregnated instead of Cu, instead of the copper (II) nitrate of 2,5-hydrate, 5.4 g of nickel (II) nitrate hexahydrate (> 99%, Riedel-de-Haen) are used as Ni. Saiz used. For impregnation with Fe, iron (III) nitrate nonahydrate (> 99%, Riedel-de-Haen) and for impregnation with Cr chromium (III) nitrate nonahydrate (> 99%, from Riedel-de-Haen) are used ,

E Stepwise impregnation of the optionally pretreated after A and / or B zeolites with an aqueous solution containing a Ni, Cu, Cr or Fe-SaIz, drying and impregnation with Mo solution

100 g of a zeolite (optionally pretreated with NH ₄ NO 3 according to A and / or B) are placed in a dish. Approximately 4.1 g of copper (II) nitrate 2.5 hydrate (> 99%, Fa. Riedel-de-Haen) are made up with water to the appropriate volume of water absorption (about 100 ml) of the zeolite and stirred until complete dissolution. If Ni is to be impregnated instead of Cu, instead of the copper (II) nitrate 2.5 hydrate, 5.4 g of nickel (II) nitrate hexahydrate (> 99%, Riedel-de-Haen) are used as Ni salt used. For nodding with Fe, iron (III) nitrate nonahydrate (> 99%, Riedel-de- Haen) and for impregnation with Cr chromium (III) nitrate nonahydrate (> 99%, Riedel-Haen ) used. The solution is then added with stirring to the zeolite and the mass further mixed for 15 min at room temperature. The mass is then heated in a drying oven to 120 ⁰ C and dried overnight, but not calcined. Subsequently, the already Cu-loaded catalyst is impregnated according to C with Mo.

F Impregnation of the optionally pretreated after A and / or B zeolite with a solution containing ammonium heptamolybdate and a salt of another element (Ni, Cu, Cr, Fe)

100 g of (optionally pretreated with NH ₄ NO ₃ according to A and / or B) zeolite are placed in a shell. Approximately 12 g of ammonium heptamolybdate tetrahydrate (> 98%, ABCR) and 4.1 g of copper (II) nitrate of 2,5-hydrate (> 99%, Riedel-de-Haen) are mixed with water to the appropriate volume of Water absorption (about 100 ml) of the zeolite filled and stirred until complete dissolution. If Ni is to be impregnated instead of Cu, instead of the copper (II) nitrate of 2,5-hydrate, 5.4 g of nickel (II) nitrate hexahydrate (> 99%, Riedel-de-Haen) are used as Ni -SaIz used. For impregnations with Fe, iron (III) nitrate nonahydrate (> 99%, Fa. Riedel-de-Haen) and for impregnation with Cr chromium (III) nitrate nonahydrate (> 99%, Fa. Riedel-de-Haen ) used. The solution is then added with stirring to the zeolite and the mass further mixed for 15 min at room temperature. The mass is then heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 or 5 h.

G Catalytic test under standard conditions

Approximately 1, 6 g of the catalyst are heated in the reactor tube (inner diameter = 4 mm) under helium atmosphere at 500 ⁰ C. At this temperature, methane is switched on and the catalyst is kept at this temperature for 30 minutes, before being brought to the reaction temperature of 700 ^° C. under methane containing 10% by volume of helium. The catalyst is then operated for about 10 h at 700 ⁰ C, 1 bar, 10 vol% He in methane and a GHSV of 500 h ^"1 operated.

After this time, an optional regeneration with H ₂ can take place. For this purpose, it is briefly inertized with helium, then at a reaction temperature of 700 ⁰ C to 740th ° C and a pressure of 1 to 5 bar pure hydrogen for 2 to 3 hours through the reactor, then again rendered inert with He and the reaction mixture at 700 ⁰ C, 1 bar, by volume% He abandoned in methane 10th

H Impregnation of optionally pretreated after A and / or B zeolites according to F, wherein the complexing agent was added to the hot aqueous impregnating solution.

I impregnation of the optionally pretreated after A and / or B zeolites according to H, drying the zeolite and further impregnation with an aqueous solution containing a Fe, Cr or Nb SaIz or Ta carbide.

Example 4: 6% by weight of Mo on H-ZSM-5 (powder) (not according to the invention)

The catalyst was prepared according to C on a commercial H-ZSM-5 (ZEOcat PZ-2/50-H, Fa. ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) and tested according to G.

Example 5: 6% by weight of Mo on H-ZSM-5 (powder) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) support was pretreated according to A. The catalyst was prepared from the thus obtained carrier according to C and tested according to G.

Example 6: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (powder) (not according to the invention)

The catalyst was prepared according to F on a commercial H-ZSM-5 (ZEOcat PZ-2/50-H, Fa. ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) and tested according to G.

Example 7: 6% by weight of Mo on H-ZSM-5 (chippings) (not according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was subjected to chipping according to B. The catalyst was prepared from the resulting grit according to C and tested according to G. Example 8: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (not according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was subjected to chipping according to B. The catalyst was prepared from the support thus obtained by F and tested according to G.

Example 9: 6% by weight of Mo on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, Fa. ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and then deformed to chippings according to B. The catalyst was prepared from the resulting grit according to C and tested according to G.

Example 10: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, Fa. ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and then deformed to chippings according to B. The catalyst was prepared from the resulting grit according to D and tested according to G.

Example 11: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, Fa. ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and then deformed to chippings according to B. The catalyst was prepared from the resulting grit according to F and tested according to G.

Example 12: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, Fa. ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and then deformed to chippings according to B. The catalyst was prepared from the resulting grit according to E and tested according to G.

Example 13: 6% by weight Mo / 1% by weight Ni on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to F, with 20 g of zeolite, about 2.4 g of the molybdate compound and about 1.06 g of nickel (II) nitrate hexahydrate (> 99%, Riedel). de-Haen) were used with about 20 ml of water. The catalyst was tested according to G.

Example 14: 6% by weight Mo / 1% by weight Cu on H-MCM-22 (chippings) (according to the invention)

A zeolite H-MCM-22 (SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and then deformed according to B to grit. The catalyst was prepared from the resulting grit according to F and tested according to G.

TABLE 4 Comparison of the catalytic performance of the catalysts from Examples 1 to 13 (zeolite: H-ZSM-5 with SiO ₂ : Al ₂ O ₃ = approx. 50)

Sales: Proportion of converted methane, based on methane used in percent

Selectivity Benzene: Percentage of benzene, based on converted methane in percent Selectivity Coke: Percentage of coke deposits, based on converted methane in percent

The catalysts according to the invention, each containing a zeolite which has been treated twice with a NH ₄ -containing solution (treatment according to A, Examples 5 and 9 to 13), show high benzene selectivities with low coke selectivities and high methane conversions.

TABLE 5 Comparison of the catalytic performance of the catalysts from Examples 1 1 (zeolite: H-ZSM-5) and 14 (zeolite: H-MCM-22)

The two catalysts of the invention differ in the zeolite used; in Example 11, a ZSM-5 zeolite, in Example 14, an MCM-22 zeolite was used. Both catalysts show extremely low coke selectivities compared to the catalysts not according to the invention shown in Table 4, wherein, when comparing with the values in Table 4, it should be taken into account that the data shown there after 7 h reaction time, those from Table 5 after 5 h Response time were recorded. The catalyst containing Mo and Cu on MCM-22 has a significantly higher selectivity for benzene and a slightly reduced selectivity to coke compared to the ZSM-5-containing catalyst.

Example 15: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to F, with 10 g of zeolite, about 1, 2 g of the molybdate compound and 0.41 g of copper (II) nitrate 2.5 hydrate (> 99%, Fa. Riedel-de-Haen) were used with about 100 ml of water. The catalyst was tested according to G.

Example 16: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to H, with 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.6 g of copper (II) nitrate 2.5 hydrate (> 99%, Fa. Riedel-de-Haen) and approx. 1, 6 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) with about 19 ml of water were used. The catalyst was tested according to G.

Example 17: 6% by weight Mo / 1% by weight Ni on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) support was pretreated according to A and B. The catalyst was prepared from the resulting grit according to F, with 20 g of zeolite, about 2.4 g of the molybdate compound and 1, 1 g of nickel (II) nitrate hexahydrate (> 99%, Fa. Riedel-de-Haen) were used with about 20 ml of water. The catalyst was tested according to G.

Example 18: 6% by weight Mo / 1% by weight Ni on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to H, with 20 g of zeolite, about 2.4 g of the molybdate compound, 1, 1 g of nickel (II) nitrate hexahydrate (> 99%, Fa. Riedel-de-Haen) and about 1, 6 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) with about 20 ml of water were used. The catalyst was tested according to G.

TABLE 6 Comparison of the catalytic performance of the catalysts from Examples 15 to 18 (influence of complexing agent, zeolite: H-ZSM-5 with SiO ₂ : Al ₂ O ₃ = approx. 25: 1)

The addition of the complexing agent EDTA in the impregnation of the catalysts with the metals Mo and Cu or Ni causes a significant increase in the Benzolselektivitäten

Example 19: 6% by weight of Mo on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) support was pretreated according to A and B. The catalyst was prepared from the resulting grit according to C, with 15 g of zeolite and about 1, 8 g of the molybdate compound with about 15 ml of water were used. The catalyst was tested according to G.

Example 20: 6% by weight Mo / 1% by weight Fe on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to D, using 15 g of zeolite and about 1, 8 g of the molybdate compound with about 17 ml of water were used. The catalyst was tested according to G. The mass was heated in a drying oven to 120 ⁰ C and dried overnight. Then about 1, 2 g of iron (III) nitrate nonahydrate (> 99%, Fa. Riedel-de-Haen) dissolved in a further 17 ml of water, the solution was then added with stirring to the zeolite and the mass 15 minutes. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 21: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to F, with 100 g of zeolite, about 12 g of the molybdate compound and 4.1 g of copper (II) nitrate 2.5 hydrate (> 99%, Riedel-de Haen) were used with about 100 ml of water. The catalyst was tested according to G.

Example 22: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to H, with 15 g of zeolite, about 1, 8 g of the molybdate compound and 0.6 g of copper (II) nitrate 2.5 hydrate (> 99%, Fa. Riedel). de-Haen) and About 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 17 ml of hot water. The catalyst was tested according to G.

Example 23: 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings, NH ₃ ) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to H, with 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.6 g of copper (II) nitrate 2.5 hydrate (> 99%, Fa. Riedel-de-Haen) were used with about 17 ml of a 25% aqueous ammonia solution. The catalyst was tested according to G.

Example 24: 6% by weight Mo / 1% by weight Cu / 1% by weight Fe on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to I, with 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.6 g of copper (II) nitrate 2.5 hydrate (> 99%, Fa. Riedel-de-Haen) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 17 ml of hot water. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Thereafter, about 1.2 g of iron (III) nitrate nonahydrate (> 99%, Riedel-de- Haen) were dissolved in a further 17 ml of water, the solution was then added to the zeolite with stirring and the Mass 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 25: 6% by weight Mo / 1% by weight Ni on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit corresponding to H, with 50 g of zeolite, about 5.9 g of the molybdate compound, 2.7 g of nickel (II) nitrate hexahydrate (> 99%, Riedel-de Haen) and about 4.1 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Aldrich) were used with about 17 ml of hot water. The catalyst was tested according to G. Example 26: 6% by weight Mo / 0.5% by weight Fe on H-ZSM-5 (chippings) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) support was pretreated according to A and then shaped into chips according to B. The catalyst was prepared from the thus obtained grit according to D. About 15 g of the chippings were impregnated with about 1.8 g of ammonium heptamolybdate tetrahydrate (> 99%, from Aldrich) in about 17 ml of water. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Thereafter, about 0.6 g of iron (III) nitrate nonahydrate (> 99%, Riedel-de-Haen) was dissolved in a further ca.17 ml of water, the solution was then added with stirring to the zeolite and the Mass 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 27: 6% by weight Mo / 1% by weight Cr on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to D, using 15 g of zeolite and about 1, 8 g of the molybdate compound with about 17 ml of water were used. The mass was heated in a drying oven to 120 ⁰ C and dried overnight. Then about 1, 3 g of chromium (III) nitrate nonahydrate (> 99%, Fa. Riedel-de-Haen) dissolved in a further 17 ml of water, the solution was then added with stirring to the zeolite and the mass 15 minute further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 28: 6% by weight Mo / 1% by weight Ni / 0.5% by weight Fe on H-ZSM-5 (chippings,

EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to I, initially 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.8 g of nickel (II) nitrate hexahydrate (> 99%, Fa. Riedel-de-Haen ) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 17 ml of hot water. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Thereafter, about 0.6 g of iron (III) nitrate nonahydrate (> 99%, Riedel-de-Haen) was dissolved in a further ca.17 ml of water, the solution was then added with stirring to the zeolite and the Mass 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 29: 6% by weight Mo / 1% by weight Ni / 1% by weight Fe on H-ZSM-5 (chippings,

EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to I, initially 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.8 g of nickel (II) nitrate hexahydrate (> 99%, Fa. Riedel-de-Haen ) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 17 ml of hot water. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Thereafter, about 1.2 g of iron (III) nitrate nonahydrate (> 99%, Riedel-de-Haen) were dissolved in a further ca.17 ml of water, the solution was then added to the zeolite with stirring and the Mass 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 30: 6% by weight Mo / 1% by weight Ni / 1% by weight Cr on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/25-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to I, initially 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.8 g of nickel (II) nitrate hexahydrate (> 99%, Fa. Riedel-de-Haen ) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 17 ml of hot water. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Then about 1, 3 g of chromium (III) nitrate nonahydrate (> 99%, Fa. Riedel-de-Haen) dissolved in a further ca 17 ml of water, the solution was then added with stirring to the zeolite and the mass 15 minute further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 31: 6% by weight Mo / 1% by weight Cu / 0.5% by weight Nb on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat H-ZSM-5 PZ-2/25-H, ZEOCHEM, SiO ₂ : Al ₂ O ₃ = about 25 mol / mol) support was pretreated according to A and B. The catalyst was 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.6 g of copper (II) nitrate pentahemihydrate (> 99%, Fa. Riedel-de-Haen) and ca 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, from Aldrich) were used with about 17 ml of hot water. The hot solution was added to the zeolite with stirring and the mass was stirred for 15 min. further mixed at room temperature. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Subsequently, about 0.3 g of ammonium nitrate (V) oxalate (> 99%, from Aldrich) were dissolved in a further ca. 13 ml of water, the solution was then added to the zeolite with stirring and the mixture was stirred for 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

TABLE 7 Catalytic Performance of the Catalysts of Examples 19 to 31 after 10 h Reaction Time (Zeolite: H-ZSM5 with SiO ₂ : Al ₂ O ₃ = approx. 25: 1)

Selectivity naphthalene: fraction of naphthalene, based on converted methane in percent

Benzene yield: Proportion of benzene, based on methane used

The presence of a complexing agent in the impregnation of the zeolites pretreated according to A and B with the catalytically active metals (Examples 22 and 23) causes a further increase in methane conversions and benzene yields in comparison to the catalyst which was impregnated with the metals without complexing agent (Example 21) ). This confirms the results shown in Table 6.

In these examples, there is a marked increase in benzene selectivities and benzene yields in the presence of at least one other metal besides Mo in the catalyst. The presence of two further elements besides Mo in the catalyst causes a marked increase in the benzene yield in comparison to the catalysts, which each contain only one of the further elements. Example 32: 6% by weight Mo / 1% by weight Ni / 0.5% by weight Nb on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to I, initially 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.8 g of nickel (II) nitrate hexahydrate (> 99%, Fa. Riedel-de-Haen ) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 10 ml of hot water. The hot solution was added to the zeolite with stirring and the mass was stirred for 15 min. further mixed at room temperature. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Subsequently, about 0.3 g of ammonium niobate (V) oxalate (> 99%, from Aldrich) were dissolved in a further ca.13 ml of water, the solution was then added with stirring to the zeolite and the mixture was stirred for 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 33: 6% by weight Mo / 1% by weight Cu / 0.5% by weight Nb on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and B. The catalyst was prepared from the resulting grit according to I, initially 15 g of zeolite, about 1, 8 g of the molybdate compound, 0.6 g of copper (II) nitrate pentahemihydrate (> 99%, Fa. Riedel -de-Haen ) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 17 ml of hot water. The hot solution was added to the zeolite with stirring and the mass was stirred for 15 min. further mixed at room temperature. The mass thus obtained was heated in a drying oven at 120 ⁰ C and dried overnight. Subsequently, about 0.3 g of ammonium niobate (V) oxalate (> 99%, from Aldrich) were dissolved in a further ca.13 ml of water, the solution was then added with stirring to the zeolite and the mixture was stirred for 15 min. further mixed at room temperature. The mass was heated in a drying oven to 120 ⁰ C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Example 34: 6% by weight Mo / 1% by weight Ni / 0.5% by weight Ta on H-ZSM-5 (chippings, EDTA) (according to the invention)

A commercial H-ZSM-5 (ZEOcat PZ-2/50-H, ZEOCHEM Co., SiO ₂ : Al ₂ O ₃ = about 50 mol / mol) carrier was pretreated according to A and B. 15 g of the resulting precipitate was first dry-mixed with about 0.1 g of tantalum (IV) carbide (Aldrich). Of the Catalyst was prepared from the mixture of grit and tantalum (IV) carbide corresponding to I, whereby about 1. 8 g of the molybdate compound, 0.8 g of nickel (II) nitrate hexahydrate (> 99%, Riedel-de Haen) and about 1, 2 g of ethylenediaminetetraacetic acid (EDTA,> 99.9%, Fa. Aldrich) were used with about 10 ml of hot water. The hot solution was added to the zeolite with stirring and the mass was stirred for 15 min. further mixed at room temperature. The mass thus obtained was heated in a drying oven to 120 0C, dried overnight and then calcined at 500 ⁰ C for 4 h. The catalyst was tested according to G.

Table 8: Catalytic performance of the catalysts from Examples 32 to 34 after 10 h reaction time (zeolite: H-ZSM5 with SiO ₂ ) Al ₂ O ₃ = about 50: 1)

By adding Nb or Ta to a catalyst of the invention containing Ni and Mo, improved benzene yields are achieved, as well as the addition of Nb to a catalyst of the invention containing Cu and Mo.

Example 35 Catalytic Test with Hydrogen Regeneration

Approximately 1.6 g of the catalyst from Example 32 are first tested in the reactor tube (internal diameter = 4 mm) for 6 hours according to G. After about 6 h is rendered inert with helium and the temperature raised to 740 ⁰ C and the pressure to p (total) = 5 bar. Thereafter, the mixture is regenerated for 4 h with pure H ₂ , passed back to 700 ⁰ C and 1 bar under helium and then started a new reaction cycle of 6 h (T = 700 ⁰ C, p (tot) = 1 bar, about 90 vol -% CH _4, 10% by volume of He, GHSV = 500 h ^"1) This procedure was repeated several times the results are summarized in Table 9. the values given relate in each case to the time 6 hours after the start of the cycle... , Table 9: Regenerability with hydrogen: Catalytic performance of the catalyst from Example 35, each after 6 h reaction time

Claims

claims

1. Molybdenum and zeolite-containing catalyst for the dehydroaromatization of a C-ι-C ₄ -aliphatic-containing Eduktstroms E, available through the steps

I treating a zeolite selected from the group of MFI and MWW having an NH ₄ -containing mixture, with subsequent drying and calcining of the zeolite,

II re-treating the zeolite with an NH ₄ -containing mixture, followed by drying of the zeolite,

III application of molybdenum and

IV calcining.

2. A catalyst according to claim 1, characterized in that as NH ₄ -containing component of the NH ₄ -containing mixture in steps I and II are each at least one

Ammonium salt selected from the group ammonium halides, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfate and ammonium hydrogen sulfate, is used.

3. A catalyst according to claim 1 or 2, characterized in that is used as NH ₄ -containing component of the NH ₄ -containing mixture in steps I and II ammonium nitrate.

4. Catalyst according to one of claims 1 to 3, characterized in that the catalyst contains 0.1 to 20 wt .-%, based on the total weight of the catalyst, Mo.

5. Catalyst according to one of claims 1 to 4, characterized in that the catalyst is at least one further element selected from the group Cu, Ni,

Fe, Co, Mn, Cr, Nb, Ta, Zr, V, Zn and Ga.

6. Catalyst according to one of claims 1 to 5, characterized in that the catalyst contains at least two further elements selected from the group Cu, Ni, Fe, Co, Mn, Cr, Nb, Ta, Zr, V, Zn and Ga.

7. A catalyst according to any one of claims 1 to 6, characterized in that the catalyst is at least 0.1 wt .-%, based on the total weight of the catalyst, of at least one further element selected from the group Cu, Ni, Fe, Co, Mn , Cr, Nb, Ta, Zr, V, Zn and Ga.

8. Catalyst according to one of claims 1 to 7, characterized in that the catalyst is at least 0.1 wt .-% of a further element selected from the group Mn, Cr, Nb, Ta, Zr, V, Zn, Ga, Cu, Ni, Fe and Co and at least 0.05 wt .-% of a second further element selected from the group consisting of Cu, Ni, Fe, Co, Cr, Zr, V, Zn and Ga, in each case based on the total weight of the catalyst.

9. Catalyst according to one of claims 1 to 8, characterized in that the solution, with which the molybdenum and optionally the further elements are applied to the zeolite, contains at least one complexing agent.

10. A catalyst according to any one of claims 1 to 9, characterized in that the catalyst between step I and II or step II and III is mixed with a Si-containing binder.

1 1. A catalyst according to any one of claims 1 to 10, characterized in that the catalyst is used as a chippings or molded body.

12. A catalyst according to any one of claims 1 to 10, characterized in that the catalyst is used as a powder.

13. A process for the preparation of a molybdenum and zeolite-containing catalyst according to any one of claims 1 to 12 comprising the steps

I treating a zeolite selected from the group consisting of MFI and MWW with an NH ₄ -containing mixture, followed by drying and calcination of the zeolite,

Re-treating the zeolite with an NH ₄ -containing mixture with subsequent drying of the zeolite, III applying the molybdenum and

IV calcining.

H. Use of a catalyst according to one of claims 1 to 12 for the dehydro-aromatization of a C-C ₄ -aliphatic-containing starting material stream E.

15. A process for the dehydroaromatization of a CrC ₄ -aliphatic-containing educt current E by reacting the reactant stream E in the presence of a catalyst according to one of claims 1 to 12.