WO2012069526A1

WO2012069526A1 - Method for producing supported zsm-5 zeolites

Info

Publication number: WO2012069526A1
Application number: PCT/EP2011/070782
Authority: WO
Inventors: Götz BURGFELS; Manfred Frauenrath; Friedrich Schmidt
Original assignee: Süd-Chemie AG
Priority date: 2010-11-23
Filing date: 2011-11-23
Publication date: 2012-05-31
Also published as: DE102010052258A1

Abstract

The invention relates to a method for producing immobilized zeolite catalysts, and catalysts which may be produced by such a method, and the use of the catalysts in the conversion of methanol or other oxygen-containing compounds into olefins, in particular propylene, having a high propylene selectivity and stability.

Description

Process for the preparation of supported ZSM-5 zeolites

The invention relates to a process for the preparation of

immobilized zeolite catalysts. Furthermore, the invention relates to catalysts which can be prepared by such a method, as well as the use of the catalysts in the conversion of methanol or other oxygen-containing compounds in

Olefins, especially propylene, with high propylene selectivity and stability.

Background of the invention

Catalysts with ZSM-5 structure (MFI type) are i.a. from the

US 3,702,886 and DE-A-28 22 725 are known. Therein are selected from an aluminum source, a silicon source, an alkali source, a template, e.g. a tetrapropylammonium compound, and water produces aluminosilicate crystallites the size of which is, i.a. through the

Crystallization temperature and the concentration of the template is controlled as a nucleating agent.

In DE-A-24 05 909 ZSM-5 zeolites are described as catalysts for hydrocarbon conversion. In these catalysts, the aluminosilicate primary crystallites are combined with binders to form agglomerates.

In US Pat. No. 4,283,583, catalytically active zeolites coated on inert carriers are converted to aromatic compounds

Hydrocarbons used in alkylaryl hydrocarbons.

Monolithic catalyst supports consisting of a ceramic support and a catalytically active material applied thereto, e.g. a zeolite are also disclosed in USRE34853.

U.S. Patents 4,058,576, 4,025,575 and 4,471,150

describe processes in which methanol, optionally after prior partial conversion to dimethyl ether over a ZSM-5 type crystalline zeolite to olefins. The propylene content in the olefin mixture is at best about 34% by weight. In particular US Pat. No. 4,058,576 indicates that the propylene selectivity increases with decreasing contact time.

In the process described in DE 40 09 459 for the production of lower olefins using a special crystalline, non-agglomerated ZSM-5 aluminosilicate under certain

Conditions propylene selectivities are achieved up to about 48%.

EP 0 369 364 and EP 1 424 128 also describe the use of ZSM-5 zeolites as catalysts in processes for the conversion of methanol to olefins, e.g. Methanol-to-propylene (MTP). By using aluminosilicate primary crystallites having an average particle size in the range between 0.01 and 0.1 μm, EP 1 424 128 achieves conversions with improved propylene selectivity (up to 36.1% by weight of propylene).

Nevertheless, the propylene selectivity of ZSM-5 type MTP catalysts with values consistently below 50% in the single pass in the fixed bed reactor is relatively low and makes a complex recycling operation necessary in industrial use. Particularly in the context of the ever increasing demand for propylene and polypropylene, inter alia in the plastics processing industry, economic processes are as high as possible

Propylene selectivity and yield of greatest interest. When using expensive catalysts, the highest possible conversion per amount of catalyst is also sought.

Summary of the invention

The present invention solves this problem by immobilizing active zeolite catalysts with ZSM-5 structure on active or inactive surfaces. The immobilization causes a shortening of the residence time of the educts and a shortening of the diffusion paths on the catalyst surfaces and thus an increase in the

Propylene selectivity. The shorter residence time is also used for Avoiding or reducing the undesired formation phase in hydride transfer reactions, in the recycled naphthenes to undesirable aromatics and propylene to undesirable propane

react. By avoiding aromatics formation, the coking tendency is suppressed and the life, i. increases the stability of the catalyst.

The catalysts used in the process of the invention are characterized in particular by a high selectivity with respect to the conversion of methanol into propylene.

Detailed description of the invention

The process for producing the immobilized ZSM-5 zeolite catalysts is carried out by coating support materials with the active zeolite catalyst. The individual starting materials and process steps are explained in more detail below.

As an active zeolite, a ZSM-5 type H zeolite has proved to be particularly suitable, as described for example in the

EP 1 424 128, the disclosure of which is hereby by

Reference is fully included. The (atomic)

Molar ratio Si: Al in the H-zeolite is usually 10 - 400: 1, preferably 25 -300: 1, more preferably

40-200: 1 and most preferably 75-130: 1. Usually, the H-zeolite is in the form of agglomerates of primary crystallites. The primary crystallites have a mean diameter in the

Range from 0, 005 to 1 μιη, preferably from 0.01 to 0.1 \ im and particularly preferably from 0.015 to 0.05 \ im. The size of the agglomerates is not particularly limited, preferably

Primary crystallites to agglomerates with a mean size of 0.5 to 500 \ im combined. The determination of

Primary crystallite size is as described in EP 1 424 128. The BET surface area of the H-zeolite is preferably 300 to 600 m ² / g, determined according to DIN 66 131.

The powdery H-zeolite is dried and optionally subjected to an intermediate calcination. Subsequently, the H-zeolite, after optional slurrying with water, mixed with a binder and an adhesive. The binder and adhesive added H-zeolite is then brought into contact with the carrier material in a suitable coater.

As binders, inorganic oxides, preferably

Alumina, magnesia, titania, zinc oxide, niobium oxide,

Zirconia or silica, as well as mixtures thereof, as well as amorphous aluminosilicates and non-oxidic binders such as

Example aluminum phosphates, aluminum nitrate can be used

Particularly preferred is the use of finely divided

Alumina binder, which is preferably obtained by hydrolysis of Aluminiumtrialkylen or Aluminiumalkoholaten, or is used in the form of peptisable alumina hydrate. Very particular preference is given to peptisable as a binder

Alumina hydrate used. More preferably, at least 95% of the particles of the peptisable alumina hydrate (based on the average diameter) -S 55 μιη.

Specific examples of binders include i.a. Aluminum nitrate,

Alumina and alumina hydrate, especially finely divided alumina (such as Pural SB®, manufactured by Sasol),

water-soluble, highly dispersed and pure alumina hydrate (boehmite) (such as Disperal P2®, manufacturer Sasol), and colloidally dispersed alumina hydrate (such as Alumina Sol ™ AS-200 manufacturer Nissan Chemical), preferably Disperal P2® or Alumina Sol ™ AS-200 , Due to the even distribution of

Alumina in the solvent is particularly high

dispersed alumina hydrate and colloidally dispersed

Alumina hydrate for use in the process of the present invention. In addition, it has been found that supported catalysts obtained with the aid of these binders show particularly good mechanical stability.

As adhesives are preferably copolymers, such as

Vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate or vinyl acetate / ethylene copolymers, in particular vinyl acetate / ethylene Copolymers, preferably used in the form of an aqueous dispersion. Particularly preferred is the use of a

plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer. Preferably, dispersions with a

Solid content in the range of 35 to 62 wt .-% used.

In principle, all suitable support materials which are customary in the prior art can be used as support material, such as, for example,

Microstructured reactors, ceramic supports, metallic supports, support alloys, carbon supports, etc. Examples of

Microstructure reactors are e.g. Heat exchanger surfaces,

Flow tubes or networks with macroporous structures. Ceramic carriers are e.g. Oxide ceramics, silicon oxides, aluminum oxides,

Aluminosilicates, cordierite, etc. Particularly preferred are the

Aluminas and aluminosilicates carriers. Metallic supports, such as e.g. Aluminum, nickel, tin, zinc, etc., as well

Carrier alloys, such as nickel-containing stainless steels, can be used with or without washcoat. The carbon carriers used are, for example, activated carbon, carbon black, graphite or carbide.

The support materials can be used in a variety of forms, e.g. as metallic or ceramic honeycomb body or

Monoliths, corrugated sheets, metallic or ceramic foams,

metallic or ceramic spheres and hollow spheres, tablets,

Extrudates, rings, granules, etc.

Particularly preferred support materials are aluminas and / or aluminosilicates. These are preferably in spherical or

Tablet form, in particular in spherical form before. Specific examples thereof are e.g. DD443 beads (CHALCO / SALCO 126®), CTR T126 tablets (Süd-Chemie AG), Alumina beads 2.5 / 210 (Sasol) and K-306 aluminosilicate beads (Süd-Chemie AG).

The average diameter of the carrier balls is preferably 1 to 10 mm, particularly preferably 1.5 to 7 mm, in particular 2 to 5 mm. Tablets are preferably used in comparable orders of magnitude. It is further preferred if the tablets have a

Diameter (D) in the range of 1 to 10 mm, more preferably of 1.5 to 7 mm, in particular from 2 to 5 mm, and a height (H) in the range of 1 to 10 mm, more preferably from 1.5 to 7 mm, in particular from 2 to 5 mm, wherein the ratio D H is preferably in the range of 0.7 to 1.5, in particular in the range of 0.9 to 1.1. The use of carrier beads or tablets of the specified minimum size is particularly advantageous to a decrease in the selectivity and activity in the

In contrast, conversion processes such as the methanol-to-olefin (CMO) and methanol-to-propylene (MTP) processes of the present invention are to be avoided. If the size of the carrier pellets does not exceed the stated upper limit of the preferred ranges, this will result in improved performance mechanical stability of the

supported catalysts.

As a coater, the relevant coating devices of the prior art can be used. Preferably, the

Use of an air coater or a Hüttlin coater, in particular an air coater of Innoj et Herbert Hüttlin, Germany.

The proportions of H zeolite, binder, adhesive and carrier are preferably selected so that the final supported ZSM-5 zeolite has optimum activity and stability, and

is completely immobilized. Preferably, in the finished catalyst, the zeolite mass is from 20 to 40% by weight, preferably from 25 to 35% by weight and especially about 30% by weight, based on the total mass of zeolite, binder and carrier. The binder is in the finished

Catalyst in an amount of 5 to 20 wt .-%, preferably 8 to 15 wt .-% and in particular about 10 wt .-% before, based on the zeolite mass. The adhesive is used in an amount of 5 to 25% by weight, preferably 10 to 20% by weight, and more preferably about 15% by weight, based on the zeolite mass. When calculating the required quantities of starting materials different

Factors such as spray loss, loss on ignition (GV) etc., so that the starting materials usually have to be used in higher amounts than calculated for the finished product. The residence time of the charge in the coater is not particularly limited. As a rule, it is about 1 to 3 hours depending on the carrier material used. The coated support is then dried and optionally calcined.

The finished supported zeolite can be used advantageously in methanol-to-olefin (CMO) or methanol-to-propylene (MTP) process or generally for the conversion of oxygen-containing compounds to olefins, where it is characterized by its high propylene selectivity especially for MTP method is suitable.

The invention is not limited by the following

Examples explained in more detail. Although these examples describe specific embodiments of the invention, they are only illustrative of the invention and should not be construed as limiting the invention in any way. Again

Numerous changes may be made to those skilled in the art without departing from the scope of the invention as defined by the appended claims.

Examples

The following binders were used in the examples: aluminum nitrate, Pural SB® (manufacturer Sasol, finely divided alumina binder), Disperal P2® (manufacturer Sasol, water-soluble, highly dispersed and pure alumina hydrate (boehmite)) and Alumina Sol ™ AS-200 (manufacturer Nissan Chemical, colloidally dispersed alumina hydrate, hereinafter abbreviated as Alumina Sol ™).

The adhesive used was one

plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer.

The following carriers were used: aluminum oxides and / or aluminosilicates in spherical or tablet form. Specific examples thereof include DD443 beads (CHALCO, diameter: 3 - 5 mm), CTR T126 tablets (Süd-Chemie AG, tablet diameter: 4.5 mm; 4.5 mm), Alumina balls 2.5 / 210 (Sasol, diameter: 2.5 mm) and

306 aluminosilicate spheres (Süd-Chemie AG, diameter: 5 mm)

The coating was carried out in an Innojet Aircoater 025® from

Innojet Herbert Hüttlin, Germany.

example 1

53 g of ZSM-5 H zeolite powder were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature (RT, about 20 ° C.). While stirring, 53 grams of Alumina-Sol ™ binder were added to the suspension. Subsequently, 16 g of the adhesive were added with stirring and the suspension was stirred for a further 60 minutes at room temperature.

Into an Innojet Aircoater 025®, 100 g of Sasol alumina balls were filled. The coating process was started and the beads were coated with the suspension for about 2.0 hours. For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 70

Extract air temperature (° C): 29

Spray air (bar): 1.0

Process air (%): 38 to 42

Spray rate (%): 75

Subsequently, the balls were dried for 20 minutes at 90 ° C in a Retsch TG200® in the fluidized bed. There were 173 g of coated Sasol alumina spheres, which in a

Air circulation high temperature oven from RT with l ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. With l ° C / min, the balls were cooled to RT. 162 g of coated spheres were obtained after calcination.

Example 2 50 g of H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature. While stirring, 50 grams of Alumina-Sol ™ binder were added to the suspension. Thereafter, with stirring, 15 g of the adhesive were added and the suspension stirred for a further 60 minutes at room temperature.

Supply air temperature (° C): 90

Exhaust air temperature (° C): 34

Spray air (bar): 1.0

Process air (%): 37 to 40

Spray rate (%): 75

Subsequently, the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. 162g of coated Sasol alumina beads were obtained. 83 g of the coated spheres were in a recirculating high temperature oven of RT at l ° C / min. heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 6 ° C / min, the spheres were cooled to RT. There were obtained 79 g of coated spheres after calcination.

Example 3

37 g of H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature. While stirring, the suspension was mixed with 37 g of Alumina-Sol ™ binder. Thereafter, with stirring, 11 g of the adhesive were added and the suspension stirred for a further 60 minutes at room temperature. An Innojet Aircoater 025® was filled with 70 g of K-306 aluminosilicate beads. The coating process was started and the beads were coated with the suspension for about 2.0 hours. For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 80

Exhaust air temperature (° C): 49

Spray air (bar): 1.0

Process air (%): 50 to 57

Spray rate (%): 75

Subsequently, the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. There were obtained 115 g of coated K-306 aluminosilicates spheres, which in a

Air circulation high temperature oven from RT with l ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. With l ° C / min, the balls were cooled to RT. 110 g of coated spheres were obtained after calcination.

Example 4

58 g of H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 600 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature. While stirring, 58 grams of Alumina-Sol ™ binder were added to the suspension. Thereafter, with stirring, 17 g of the adhesive were added and the

Suspension stirred for a further 60 minutes at room temperature.

An Innojet Aircoater 025® was filled with 115 g of CTR-T126 tablets. The coating process was started and the beads were coated with the suspension for about 2.5 hours. For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 90

Extract air temperature (° C): 55 Spray air (bar): 1.0

Process air (%): 45 to 48

Spray rate (%): 80

The tablets were not dried after coating. 188 g of coated CTR-T126 tablets were obtained. 10.8 g of the tablets were placed in a recirculating high-temperature oven of RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. heated to 550 ° C. At 550 ° C the balls were calcined for 5h. At 1 ° C./min, the tablets were cooled to RT. There were 10.2 g coated tablets after the

Calcination obtained.

Example 5

80 g of H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 1000 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature. While stirring, the suspension was mixed with 80 g of Alumina-Sol ™ binder. Thereafter, with stirring, 24 g of the adhesive were added and the

Suspension stirred for a further 60 minutes at room temperature.

An Innojet Aircoater 025® was filled with 150g DD443 balls. The coating process was started and the beads were coated with the suspension for about 3.5 hours.

For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 90

Exhaust air temperature (° C): 57

Spray air (bar): 1.0

Process air (%): 44 to 45

Spray rate (%): 80

The balls were not dried after coating. 250 g of coated DD443 beads were obtained. 10.4g of the balls were placed in a recirculating high temperature RT oven at 1 ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. heated to 550 ° C. At 550 ° C, the balls became 5 hours calcined. With l ° C / min, the balls were cooled to RT. 9.7 g of coated spheres were obtained after calcination.

Example 6

50 g of H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature. While stirring, the suspension was mixed with 7 g of Disperal P2® binder. Thereafter, 15 g of the adhesive were added with stirring and the

Suspension stirred for a further 60 minutes at room temperature.

Supply air temperature (° C): 90

Exhaust air temperature (° C): 38

Spray air (bar): 1, 0

Process air (%): 38 to 40

Spray rate (%): 75

Subsequently, the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. 164 g of coated Sasol-Alumina beads were obtained, which were heated in a high-temperature circulating oven from RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. to 550 ° C

were heated up. At 550 ° C, the balls were calcined for 5 hours. With l ° C / min, the balls were cooled to RT. 159 g of coated spheres were obtained after calcination.

Example 7

75 g of ZSM-5 H zeolite powder were weighed in a beaker, slurried with about 500 ml of deionized water (conductivity <20 S / cm) and stirred briefly at room temperature. Under Stirring was added to the suspension with 10 g of Disperal P2® binder. Thereafter, with stirring, 22 g of the adhesive were added and the

Suspension stirred for a further 60 minutes at room temperature.

An Innojet Aircoater 025® was filled with 150g DD443 balls. The coating process was started and the beads were coated with the suspension for about 2.5 hours.

For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 90

Exhaust air temperature (° C): 51

Spray air (bar): 1.0

Process air (%): 43 to 44

Spray rate (%): 75

Subsequently, the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. There were 238 g of coated DD443 spheres, which in a

Air circulation high temperature oven from RT with l ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. With l ° C / min, the balls were cooled to RT. There were obtained 227 g of coated spheres after calcination.

Example 8

50 g of deionized water was placed in a 250 ml beaker and 50 g of ZSM-5 H zeolite powder were added with stirring. The suspension was subsequently stirred at room temperature for a further 10 minutes. While stirring, 7 g of Pural SB® powder were added and the suspension was stirred for a further 10 minutes. Then, 0.2 g of acetic acid (99 to 100% by weight) was added dropwise. A sudden increase in viscosity was observed. The suspension was then transferred to a 1000 ml beaker and made up to a volume of 500 ml with deionized water. The suspension was stirred at RT overnight. Thereafter, with stirring, 15 g of the adhesive were added and the suspension for a further 60 minutes

Room temperature stirred. Into an Innojet Aircoater 025®, 100 g of Sasol alumina balls were filled. The coating process was started and the beads were coated with the suspension for about 1.5 hours. For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 90

Exhaust air temperature (° C): 38

Spray air (bar): 1.0

Process air (%): 38 to 42

Spray rate (%): 75

Subsequently, the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. There were obtained 155 g of coated Sasol alumina beads, which are in a

Air circulation high temperature oven from RT with l ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. With l ° C / min, the balls were cooled to RT. 147 g of coated spheres were obtained after calcination.

Example 9

Room temperature stirred. Into an Innojet Aircoater 025® 100 g of DD443 balls were filled. The coating process was started and the beads were coated with the suspension for about 2 hours. For this purpose, the following parameters were set for coating:

Supply air temperature (° C): 90

Extract air temperature (° C): 55

Spray air (bar): 1.0

Process air (%): 45 to 46

Spray rate (%): 75

Subsequently, the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. There were 152 g of coated DD443 spheres, which in a

Air circulation high temperature oven from RT with l ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. With l ° C / min, the balls were cooled to RT. 146 g of coated spheres were obtained after calcination.

Examples 10 to 12

34 g of ZSM-5 H zeolite powder and 26 g of aluminum nitrate binder were weighed into a beaker and made up to 600 ml with deionized water and stirred briefly at room temperature.

Thereafter, with stirring, 11 g of the adhesive was added. The

Suspension flocculated after the adhesive addition. The suspension was stirred at RT overnight, but the suspension continued to flocculate, so the experiment was stopped.

Drop test to determine the adhesion of supported H-zeolite spheres and tablets

Under a vertically mounted plastic tube with a length of 2000 mm and an inner diameter of 16.9 mm as a downpipe was using a height-adjustable platform (Laborboy) a PTFE watch glass with a diameter of 150 mm as a collecting vessel up to 10 mm at the lower end of the pipe introduced. With the help of one in the top At the end of the funnel, the supported catalyst to be tested was allowed to fall through the tube. After the impact in the watch glass, the catalyst was combined with any

Splinters transferred into a porcelain dish and examined the test specimen optically for integrity or flaking. From each catalyst, a total of 10 drop tests were performed. The

Results are summarized in the table below.

Table 1

nb *: flocculation of the binder, therefore neither coating nor drop tests possible

As can be seen from Table 1, all are used

Aluminas as binders for coating the

Support materials. Of these, both Alumina Sol ™ and Disperal P2® have proved to be particularly suitable binders for the

Production of zeolite catalysts proved. In particular spheres, especially Sasol alumina spheres, K306 aluminosilicate spheres and D443 spheres are considered as carriers, while in

Tablets even when using the considered to be particularly suitable Alumina Sol ™ as a binder edge chipping occurs. Test for determining the abrasion of shaped bodies in a steel drum according to ASTM method (D4058-96)

A representative sample of the supported catalysts 1, 3 and 5 to 7 was taken in an amount of about 50 to 100 g each. The sample was freed of adhering dust with a 1 mm sieve. In this case, the longer movement of the sample was kept as low as possible in order to avoid the abrasion and thus the influence on the result. The pre-screened sample was dried for 3 hours at 120 ° C in a drying oven. The cooling to room temperature was then carried out in a desiccator with desiccant over 30 min.

A steel drum (diameter 254 mm, length 152 mm, with baffle of 50 mm height and 3 mm wall thickness) was cleaned with a hairbrush. The dried and pretreated sample was weighed to an accuracy of 0.01 g and transferred to the drum. The steel drum was closed with a lid and placed on a

Roll mill laid. The steel drum was rotated at 60 +/- 5 revolutions per minute. After a total of 1800 revolutions, the rotation of the steel drum was stopped. A rubber mallet was tapped several times on the steel drum to collect the fines on the bottom of the steel drum. The lid was removed and the contents placed on a 1 mm sieve. The remaining fines from the lid and cylinder were brushed off with a hair brush and also placed on the sieve. The fines were sieved by gentle shaking.

The sieve residue (supported catalyst) was dried for 3 h at 120 ° C in a drying oven. The cooling to room temperature was then carried out in a desiccator with desiccant over 30 min. The dried sieve residue was weighed to an accuracy of 0.01 g.

The abrasion in% by weight was calculated according to the following formula:

Abrasion = - - x l00%

A A = initial weight, ie amount of dried supported catalyst used

B = weight, i. Amount of dried supported catalyst after rotation

The results of the abrasion test are summarized in the table below.

Table 2

As shown in Table 2, the use of Alumina Sol ™ compared to Disperal P2® leads to supported catalysts with the lowest abrasion values. In combination with a smaller one

Ball diameter can be the binding effect even better.

Alumina Sol ™ is therefore considered to be a particularly suitable binder for the preparation of supported zeolite catalysts.

Claims

A process for the preparation of a supported zeolite catalyst, the process comprising the steps of:

a) mixing a ZSM-5 type H zeolite with a

Binder and a glue,

b) coating a support material with the mixture from step a)

c) drying and optionally calcining the coated support material from step b).

2. The method according to claim 1, wherein the H-zeolite of primary crystallites or agglomerates of primary crystallites having an average particle diameter in the range of 0, 005 to 1 μιη, preferably 0.01 to 0.1 \ im and particularly preferably from 0.015 to 0, 05 \ im is built.

3. The method according to claim 1 or 2, wherein the binder is selected from the group consisting of inorganic oxides, preferably aluminum oxides.

A process according to claim 3, wherein the binder is alumina, in particular peptisable alumina hydrate or finely divided alumina, preferably peptisable alumina hydrate or finely divided alumina obtained by hydrolysis of aluminum trialkyls or aluminum alcoholates, and more preferably peptisable alumina hydrate acts.

5. The method according to claim 4, wherein at least 95% of the particles of the peptisable alumina hydrate, based on the average diameter, ^ 55 μιη.

6. The method according to any one of claims 1 to 5, wherein the adhesive is selected from copolymers, in particular from

Vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene copolymers, preferably vinyl acetate / ethylene copolymers, preferably in the form of an aqueous dispersion, completely particularly preferred is a plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer.

7. The method according to any one of the preceding claims, wherein the carrier material is selected from the group consisting of microstructured reactors, ceramic carriers, metallic carriers, carrier alloys and carbon carriers, in particular ceramic carrier, preferably alumina or aluminosilicate.

8. The method according to any one of the preceding claims, wherein the carrier material is in the form of spheres or tablets.

9. The method according to claim 8, wherein the carrier material in the form of spheres having a diameter of 1 to 10 mm, preferably 1.5 to 7 mm and in particular 2 to 5 mm is present.

10. A catalyst obtainable by a process according to any one of claims 1 to 9.

A catalyst according to claim 10 for use in the conversion of methanol to olefin, especially propylene.

12. A catalyst according to claim 7 or 8, wherein the

Zeolite mass 20 to 40 wt .-%, preferably 25 to 35 wt .-%, in particular about 30 wt .-%, based on the total mass of

Zeolite, binder and support in the catalyst.

13. Use of a catalyst according to claim 10 or 12, in a process for the conversion of methanol to olefin,

in particular to propylene.

14. A process for the preparation of olefins, in particular of propylene, from methanol or other oxygen-containing compounds using a catalyst according to any one of claims 10 bi