DE102010052258A1 - Process for the preparation of supported ZSM-5 zeolites - Google Patents

Abstract

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

Description

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 process, as well as the use of the catalysts in the conversion of methanol or other oxygen-containing compounds into olefins, in particular propylene, with high propylene selectivity and stability.

Background of the invention

Catalysts with ZSM-5 structure (MFI type) are among others from the US 3,702,886 and the DE-A-28 22 725 known. Therein are from an aluminum source, a silicon source, an alkali source, a template, z. As a tetrapropylammonium compound, and water produced aluminosilicate crystallites whose size is controlled, inter alia, by the crystallization temperature and the concentration of the template as a nucleating agent.

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

In the US 4,283,583 For example, catalytically active zeolites coated on inert supports are used to convert aromatic hydrocarbons to alkylaryl hydrocarbons. Monolithic catalyst support consisting of a ceramic support and a catalytically active material applied thereto, such. A zeolite, are also disclosed in USRE34853.

The U.S. Patents 4,058,576 . 4 025 575 and 4,471,150 describe processes in which methanol is optionally converted to olefins after prior partial conversion to dimethyl ether over a crystalline zeolite of type ZSM-5. The propylene content in the olefin mixture is at best about 34% by weight.

In the in the DE 40 09 459 , described processes for the production of lower olefins using a special crystalline, non-agglomerated ZSM-5-aluminosilicate under certain conditions, propylene selectivities up to about 48% can be achieved.

The EP 0 369 364 and the EP 1 424 128 also describe the use of ZSM-5 zeolites as catalysts in processes for converting methanol to olefins, e.g. For example, methanol-to-propylene (MTP). By using aluminosilicate primary crystallites having an average particle size in the range between 0.01 and 0.1 microns in the EP 1 424 128 Conversions with improved propylene selectivity (up to 36.1 wt .-% propylene) achieved.

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 view of the ever increasing demand for propylene and polypropylene, inter alia in the plastics processing industry, economic processes with the highest possible propylene selectivity and yield are of great 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 also serves to avoid or reduce the undesirable formation phase in hydride transfer reactions in which recycled naphthenes react to undesired aromatics and propylene to undesired propane. By avoiding or reducing the formation of aromatics, the coking tendency is suppressed and the service life, d. H. 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 is described, the disclosure of which is hereby fully incorporated by reference. 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 an average diameter in the range of 0.005 to 1 .mu.m, preferably from 0.01 to 0.1 .mu.m and particularly preferably from 0.015 to 0.05 .mu.m. The size of the agglomerates is not particularly limited, preferably primary crystallites are combined into agglomerates having a mean size of 0.5 to 500 microns. The determination of the Primärkristallitgröße takes place as in the EP 1 424 128 described. The BET surface area of the H-zeolite is preferably 300 to 600 m ² / g, determined by 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 it is possible to use inorganic oxides, preferably aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, niobium oxide, zirconium oxide or silicon oxide, and mixtures thereof, as well as amorphous aluminosilicates and non-oxidic binders such as aluminum phosphates, aluminum nitrate. Particular preference is given to the use of finely divided aluminum oxide Binder, which is preferably obtained by hydrolysis of aluminum trialkyls or aluminum alcoholates, or in the form of peptisable alumina hydrate. Very particular preference is given to using peptisable alumina hydrate as binder. More preferably, at least 95% of the particles of the peptisable alumina hydrate (based on the average diameter) ≤ 55 microns.

Specific examples of binder include aluminum nitrate, alumina and alumina hydrate, especially aluminum oxide fine particles (such. As Pural SB ^®, manufacturer Sasol), water-soluble, highly dispersed and pure aluminum oxide hydrate (boehmite) (such. As Disperal P2 ^®, Manufacturer Sasol) and colloidally dispersed hydrated aluminum oxide (such as. for example, Alumina Sol ^TM aS-200 made by Nissan Chemical), preferably Disperal P2 ^® or Alumina Sol aS-200 ^TM.

Copolymers, such as vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate or vinyl acetate / ethylene copolymers, in particular vinyl acetate / ethylene copolymers, preferably in the form of an aqueous dispersion, are preferably used as adhesives. Particularly preferred is the use of a plasticizer-free, aqueous. Dispersion of a vinyl acetate-ethylene copolymer. Preferably, dispersions are used having a solids content in the range of 35 to 62 wt .-%.

As a carrier material, in principle, all suitable carrier materials customary in the prior art can be used, such as. As microstructured reactors, ceramic supports, metallic supports, support alloys, carbon support, etc. Examples of microstructured reactors are z. B. heat exchanger surfaces, flow tubes or networks with macroporous structures. Ceramic carriers are z. As oxide ceramics, silicon oxides, aluminum oxides, aluminosilicates, cordierite, etc. Particularly preferred are the aluminum oxides and aluminosilicates carrier. Metallic carriers, such as. As aluminum, nickel, tin, zinc, etc., as well as carrier alloys, such as. As nickel-containing stainless steels, can be used with or without washcoat. Activated carbon, carbon black, graphite or carbide serve as carbon carriers, for example.

The support materials can be used in a variety of forms, for. As metallic or ceramic honeycomb or monoliths, corrugated sheets, metallic or ceramic foams, metallic or ceramic balls 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. Specific examples of this are, for. B. DD443 balls (CHALCO / SALCO 126 ^®), CTR T126 tablets (Süd-Chemie AG), Alumina Spheres 2.5 / 210 (Sasol), and K-306 aluminosilicate spheres (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 from 1 to 10 mm, more preferably from 1.5 to 7 mm, in particular from 2 to 5 mm, and a height (H) in the range from 1 to 10 mm , particularly 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 0.7-1.5, in particular in the range of 0.9-1.1 ,

As a coater, the relevant coating devices of the prior art can be used. Preference is given to the use of an air coater or a Hüttlin coater, in particular an air coater from Innojet Herbert Hüttlin, Germany.

The proportions of H zeolite, binder, adhesive and carrier are preferably chosen so that the final supported ZSM-5 zeolite has optimal activity and stability and is fully 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, various factors must be taken into account, such as: Loss of spray, 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) processes or in general for the conversion of oxygen-containing compounds to olefins, wherein it is characterized by its high propylene selectivity especially suitable for MTP procedures.

The invention is further illustrated by the following non-limiting examples. 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. As one of ordinary skill in the art appreciates, numerous changes may be made thereto without departing from the scope of the invention as defined by the appended claims.

Examples

In the examples, the following binders were used aluminum nitrate, Pural SB ^® (manufacturer Sasol, finely divided alumina binder), Disperal P2 ^® (manufacturer Sasol, water-soluble, highly dispersed and pure aluminum oxide hydrate (boehmite)) and Alumina Sol ^™ AS-200 (manufactured by Nissan Chemical, collodially dispersed alumina hydrate).

The adhesive used was a 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 of this are, for. B. DD443 beads (CHALCO), CTR T126 tablets (Süd-Chemie AG), Alumina beads 2.5 / 210 (Sasol) and K-306 aluminosilicate beads (Süd-Chemie AG)

The coating was performed in a Innojet Aircoater 025 ^® by Herbert Innojet 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 μS / 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.

100 g of Sasol-alumina spheres were ^® in a Innojet Aircoater 025 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 beads were dried for 20 minutes at 90 ° C in a Retsch TG200 ^® in the fluidized bed. 173 g of coated Sasol alumina spheres were obtained, which were heated in a high-temperature circulating oven of RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. at 300 ° C, then from 300 ° C at 1 ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres 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 μS / 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.

100 g of Sasol-alumina spheres were ^® in a Innojet Aircoater 025 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): 90
Exhaust air temperature (° C): 34
Spray air (bar): 1.0
Process air (%): 37 to 40
Spray rate (%): 75

Subsequently, the beads were dried for 60 minutes at 90 ° C in a Retsch TG200 ^® in the fluidized bed. 162 g of coated Sasol alumina beads were obtained. 83 g of the coated spheres were placed in a recirculating high temperature RT oven at 1 ° 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 μS / 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.

70 g-306 were ^® in K a Innojet Aircoater 025 filled aluminosilicates balls. 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 beads 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 recirculating air oven of RT at 1 ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. at 300 ° C, then from 300 ° C at 1 ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres 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 μS / cm) and stirred briefly at room temperature. While stirring, 58 grams of Alumina-Sol ^™ binder were added to the suspension.

Thereafter, 17 g of the adhesive were added with stirring and the suspension stirred for a further 60 minutes at room temperature.

115 g CTR-T126 tablets were ^® in a Innojet Aircoater 025 filled. 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 RT oven at 1 ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. at 300 ° C, then from 300 ° C at 1 ° C / min. heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the tablets were cooled to RT. 10.2 g of coated tablets were obtained after calcination.

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 μS / 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.

150 g DD443 balls were ^® in a Innojet Aircoater 025 filled. 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. 10.4 g 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. at 300 ° C, then from 300 ° C at 1 ° C / min. heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres 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 μS / cm) and stirred briefly at room temperature. While stirring the suspension with 7 g of Disperal P2 was added ^® -Binder. Thereafter, with stirring, 15 g of the adhesive were added and the suspension stirred for a further 60 minutes at room temperature.

100 g of Sasol-alumina spheres were ^® in a Innojet Aircoater 025 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): 90
Exhaust air temperature (° C): 38
Spray air (bar): 1.0
Process air (%): 38 to 40
Spray rate (%): 75

Subsequently, the beads were dried for 60 minutes at 90 ° C in a Retsch TG200 ^® in the fluidized bed. 164 g of coated Sasol alumina spheres 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. at 300 ° C, then from 300 ° C at 1 ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres were cooled to RT. 159 g of coated spheres were obtained after calcination.

Example 7

75 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 μS / cm) and stirred briefly at room temperature. While stirring the suspension with 10 g of Disperal P2 was added ^® -Binder. Thereafter, with stirring, 22 g of the adhesive were added and the suspension stirred for a further 60 minutes at room temperature.

150 g DD443 balls were ^® in a Innojet Aircoater 025 filled. 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 beads were dried for 60 minutes at 90 ° C in a Retsch TG200 ^® in the fluidized bed. 238 g of coated DD443 spheres were obtained, which were heated in a high-temperature circulating-air oven from RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. at 300 ° C, then from 300 ° C at 1 ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres 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. With stirring 7 g Pural-SB ^® powder were added and the suspension was stirred an additional 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 stirred for a further 60 minutes at room temperature.

100 g of Sasol-alumina spheres were ^® in a Innojet Aircoater 025 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 beads were dried for 60 minutes at 90 ° C in a Retsch TG200 ^® in the fluidized bed. 155 g of coated Sasol alumina beads were obtained, which were heated in a high-temperature circulating-air oven from RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. at 300 ° C, then from 300 ° C at 1 ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres were cooled to RT. 147 g of coated spheres were obtained after calcination.

Example 9

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 then added for a further 10 minutes Room temperature stirred. With stirring 7 g Pural-SB ^® powder were added and the suspension was stirred an additional 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 stirred for a further 60 minutes at room temperature.

100 g DD443 balls were ^® in a Innojet Aircoater 025 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 beads were dried for 60 minutes at 90 ° C in a Retsch TG200 ^® in the fluidized bed. 152 g of coated DD443 spheres were obtained, which were heated in a high-temperature circulating air oven from RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. at 300 ° C, then from 300 ° C at 1 ° C / min. were heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 1 ° C / min, the spheres 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 addition of the adhesive. The suspension was stirred at RT overnight, but the suspension continued to flocculate, so the experiment was stopped.

Drop test for determining the adhesion of supported H-zeolite spheres and tablets

Under a vertically mounted plastic pipe 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 aid of a funnel inserted into the upper tube end, the supported catalyst to be tested was allowed to fall through the tube. After the impact in the watch glass, the catalyst was transferred together with any spalling in a porcelain dish and the test specimen optically examined 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 catalyst binder carrier spalling 1 Alumina Sol ^TM Sasol alumina balls No 2 Alumina Sol ^TM Sasol alumina balls No 3 Alumina Sol ^TM K-306-aluminosilicate spheres No 4 Alumina Sol ^TM CTR-T126 tablets edge chipping 5 Alumina Sol ^TM DD443 balls No 6 Disperal.RTM P2 ^® Sasol alumina balls No 7 Disperal.RTM P2 ^® DD443 balls Yes 8th Pural SB ^® Sasol alumina balls Yes 9 Pural SB ^® DD443 balls Yes 10 aluminum nitrate nb * nb * 11 aluminum nitrate nb * nb * 12 aluminum nitrate nb * nb * nb *: flocculation of the binder, therefore neither coating nor drop tests possible

As can be seen from Table 1, all the aluminas used are suitable as binders for coating the support materials. Of these, both Alumina Sol ^™ and Disperal P2 ^® have been found to be particularly suitable binder for the manufacture of zeolite catalysts. In particular, spheres, especially Sasol-alumina spheres, K306 aluminosilicate spheres and D443 spheres, are considered as carriers, while in tablets, edge splitting occurs even when using the Alumina Sol ^{™, which is} considered to be particularly suitable as binder.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 3702886 [0002]
• DE 2822725 A [0002]
• DE 2405909 A [0003]
• US 4283583 [0004]
• US 4058576 [0005]
• US 4025575 [0005]
• US 4471150 [0005]
• DE 4009459 [0006]
• EP 0369364 [0007]
• EP 1424128 [0007, 0007, 0012, 0012]

Cited non-patent literature

• DIN 66 131 [0012]

Claims (14)

A process for preparing a supported zeolite catalyst, the process comprising the steps of: a) mixing a ZSM-5 type H zeolite with a binder and an adhesive, b) coating a support material with the mixture from step a) c) drying and optionally calcining the coated support material from step b). A process according to claim 1, wherein the H zeolite is composed of primary crystallites or agglomerates of primary crystallites having an average particle diameter in the range of 0.005 to 1 μm, preferably 0.01 to 0.1 μm and particularly preferably 0.015 to 0.05 μm. A 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 finely divided alumina obtained, in particular, by hydrolysis of aluminum trialkyls or aluminum alcoholates, or peptisable alumina hydrate, more preferably peptisable alumina hydrate. The method of claim 4, wherein at least 95% of the particles of the peptizable alumina hydrate, based on the mean diameter, is ≤ 55 μm. Method according to one of claims 1 to 5, wherein the adhesive is selected from copolymers, in particular vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate and vinyl acetate / ethylene copolymers, preferably vinyl acetate / ethylene copolymers, preferably in the form an aqueous dispersion, most preferably a plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer is. Method according to 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. Method according to one of the preceding claims, wherein the carrier material is in the form of spheres or tablets. A method according to claim 8, wherein the carrier material is 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. 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. Catalyst according to claim 7 or 8, wherein the zeolite mass is 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. Use of a catalyst according to claim 10 or 12, in a process for the conversion of methanol to olefin, in particular to propylene. Process for the preparation of olefins, in particular of propylene, of methanol or other oxygenated compounds using a catalyst according to any one of claims 10 to 12.