A MOLDING COMPRISING A ZEOLITIC MATERIAL, PHOSPHOROUS, ONE OR MORE METALS AND A BINDER

Abstract

The present invention relates to a molding comprising a zeolitic material, phosphorous, one or more metals M of groups 3, 6, 10 to 14 of the periodic system of the elements, and a binder material. The molding is useful as a catalyst, in particular for preparing aromatic compounds from methanol with selectivity toward p-xylene.

Claims

1-15. (canceled)

16. A molding comprising (a) a zeolitic material; (b) phosphorous; (c) one or more metals M of groups 3, 6 and 10 to 14 of the periodic system of the elements; (d) a binder material.

17. The molding of claim 16, wherein the zeolitic material has a framework structure comprising YO.sub.2 and X.sub.2O.sub.3 wherein Y is a tetravalent element and X is a trivalent element.

18. The molding of claim 16, wherein the zeolitic material has a framework structure of framework type BEA, MFI, MWW, MOR, MTT, MTW, FER, TOL, or TON, or wherein the zeolitic material comprises, a ZSM-5 zeolitic material, a ZBM-10 zeolitic material, a ZSM-22 zeolitic material or a ZSM-11 zeolitic material.

19. The molding of claim 16, wherein zeolitic material comprises a ZBM-10 zeolitic material or a ZSM-22 zeolitic material.

20. The molding of claim 16, comprising the phosphorous, calculated as elemental phosphorous, in an amount of at least 0.1 weight-% based on the total weight of the molding.

21. The molding of claim 16, wherein the one or more metals M are one or more of Ga, Zn, Ni, Mo, La and Pt.

22. The molding of claim 16, comprising the one or more metals M, calculated as elemental M, in an amount of at least 1 weight-% based on the total weight of the molding, wherein said amount refers to the total amount of all metals M.

23. The molding of claim 16, wherein the binder material comprises one or more of graphite, silica, tetania, zirconia, alumina, and a mixed oxide of two or more of silicon, titanium and zirconium.

24. A process for preparing a molding according to claim 16, the process comprising (i) providing the zeolitic material (ii) mixing the zeolitic material provided in (i) with a source of the binder material (iii) subjecting the mixture obtained from (ii) to molding (iv) impregnating the molding obtained from (iii) with a source of the one or more metals M and a source of the phosphorous.

25. The process of claim 24, wherein the binder material is silica and the source of the binder material comprises one or more of a colloidal silica, a silica gel and a waterglass.

26. The process of claim 24, wherein according to (ii), the zeolitic material provided in (i) is mixed with a source of the binder material and a kneading agent and/or a mesopore forming agent.

27. The process of claim 24, wherein (iv) comprises (iv-1) impregnating the molding with the source of the one or more metals M (iv-2) impregnating the molding obtained from (iv-1) with the source of phosphorous.

28. The process of claim 27, wherein the impregnating of (iv-1) and (iv-2) comprises spray impregnating.

29. A molding obtained by the process according to claim 24.

30. A catalyst component for preparing one or more aromatic compounds comprising the molding according to claim 16.

Description

EXAMPLES

Reference Example 1: Measurement of the Total Pore Area

[0236] The total pore area was determined according to the method disclosed in DIN 66134:1998-02 Determination of the pore size distribution and the specific surface area of mesoporous solids by means of nitrogen sorption issued in February 1998.

Reference Example 2: Measurement of the BET Specific Surface Area

[0237] The BET specific surface area was determined according to the method disclosed in DIN ISO 9277:2010 Determination of the specific surface area of solids by gas absorption as issued on January 2014.

Reference Example 3: Measurement of the Total Intrusion Volume

[0238] The total pore area was determined by mercury intrusion in accordance with the method disclosed in DIN 66133 as issued in 1993.

Reference Example 4: Determination of the Yield

[0239] The yield of p-xylene is the normalized yield and is calculated as follows:

Y.sub.product [%]=(RC.sub.product[g(C)/h]/Sum.sub.RC[g(C)/h])*100

Sum.sub.RC=(RC.sub.productFID)+(RC.sub.CO-TCD)+(RC.sub.CO2-TCD)

Normalized yield factor=100/Sum.sub.yields

Y.sub.product-norm[%]=Y.sub.product*normalized yield factor

wherein [0240] RC=rate of carbon, in gram per carbon per hour, g(C)/h [0241] Y.sub.product=yield of the product [0242] Y.sub.product-norm=normalized yield of the product [0243] Sum.sub.RC=sum of the rates of carbon [0244] Sum.sub.yield=sum of the yields [0245] RC.sub.productFID=rate of the carbon measured with the flame ionization (FID) method [0246] RC.sub.CO-TCD=rate of the carbon of CO measured with the thermal conductivity (TCD) detector [0247] RC.sub.CO2-TCD=rate of the carbon of CO.sub.2 measured with the thermal conductivity (TCD) detector

[0248] The products and methanol feed are detected at flame ionization (FID) detector, whereas CO and CO.sub.2 at a thermal conductivity (TCD) detector. FID and TCD are given next to the carbon rates. All yields are then normalized to 100.

Comparative Example 1: Preparation of a Molding Comprising a ZSM-5 Zeolitic Material Impregnated with Zn by Extrusion

[0249] a) Spray-impregnation of ZSM-5 with Zn

Starting Material

[0250]

TABLE-US-00001 ZSM-5 zeolitic material 170 g Deionized water (DI water) 110 g Zn(NO.sub.3).sub.2 6H.sub.2O 9.3 g

[0251] For impregnation, 170 g of ZSM-5 were introduced into a round bottom flask and placed in a rotary evaporator. The Zn(NO.sub.3).sub.26 H.sub.2O were dissolved in deionized water. The metal nitrate solution was introduced into a dropping funnel, and sprayed gradually onto the extrudates through a glass spray nozzle flooded with 100 l/h of N.sub.2 while rotating. On completion of addition of the metal nitrate solution, the zeolitic material was rotated further for 10 min. The impregnate zeolitic material were dried in air at 120 C. for 4 h and calcined in air at 500 C. for 5 h. Afterwards, the obtained powder was removed and dried in a forced air drying oven for 4 h at 120 C. and then calcined in the muffle furnace for 5 h at 500 C. (heating rate 2 K/ min) under air.

[0252] The obtained material had a BET specific surface area of 392 m.sup.2/g, a total intrusion volume 1.5991 mL/g and a total pore area at 68.693 m.sup.2/g. Elemental analysis of the obtained material: H<0.01 weight-%, Al 1.80 weight-%, Na<0.01 weight-%, Zn 1.1 weight-%, Si 43 weight-%. Elemental analysis of the starting material ZSM-5: H 0.02 weight-%, Al 1.80 weight-%, Na<0.01 weight-%, Zn<0.01 weight-%, Si 44 weight-%. [0253] b) Preparation of a molding by extrusion

Starting Materials:

[0254]

TABLE-US-00002 Zeolitic material of a) 140 g Ludox AS-40 (colloidal silica, 40 weight-% 87.5 g Walocel (hydroxyethyl methyl cellulose) 7 g DI water (deionized water) 73 g

[0255] The zeolitic material of a) was placed in a kneader, Walocel was added and pre-mixed for 5 min. Ludox was then added and the mixture was kneaded for 5 min. Thereafter 3 g of DI water were added and the material was kneaded for 15 min. Thereafter, the kneaded material was molded via an extrusion press (forming pressure: 120-150 bar(abs)) leading to strands having a diameter of 2.5 mm. The resulting strands were placed in a porcelain bowl in a drying oven at 120 C. for 4 h under air and then calcined in a muffle furnace at 500 C. (heating rate: 2 K/min) for 5 h under air. 168.31 g material were obtained, having a bulk density of 0.492 g/cm.sup.3.

[0256] The obtained material had a BET specific surface area of 340 m.sup.2/g, a total intrusion volume of 0.5208 mL/g and a total pore area of 74.465 m.sup.2/g. Elemental analysis of the material: H 0.01 weight-%, Al 1.5 weight-%, Na 0.04 weight-%, Si 43 weight-%, Zn 0.91 weight-%.

Example 1: Preparation of a Molding Comprising a ZSM-22 Zeolitic Material by Impregnation with Ga and P

[0257] a) Preparation of a ZSM-22 zeolitic material

Starting Materials:

[0258]

TABLE-US-00003 Solution 1: Hexamethylendiamine 70% in water 406 g Aerosil 200 185 g DI water 700 g Solution 2 Al.sub.2(SO.sub.4).sub.3 18 H.sub.2O (Aldrich 11044-2,5 kg, Lot. 20.2 g #SZBD1200V ) DI Water 270 g

Solution 1

[0259] Hexamethylendiamine was placed in a beaker of 2 I volume. DI water was added and the solution was stirred for 5 min at room temperature. Aerosil was added under stirring conditions. The stirring was continued for 2 h at room temperature. The pH of the obtained solution was 12.6.

Solution 2

[0260] The DI water was added under stirring to Al.sub.2(SO.sub.4).sub.318 H.sub.2O.

[0261] Solution 1 was charged into an autoclave under stirring at 100 rpm and heated to 70 C. Solution 2 was then added under stirring at 220 rpm. The stirring was continued for 5 min. The stirring speed was then reduced to 100 rpm, the solution was kept under stirring at 70 C. under a constant pressure for 4 h. The solution was then heated to 150 C. under a constant pressure with stirring for 170 h. The pressure used was 3.6 bar(abs). Thereafter the suspension having pH of 12.0 was filtered off by means of a porcelain filter (blue band filter). The filter cake was washed three times with 1000 ml of DI water and dried in a forced-air drying oven at 120 C. for 4 h and then in a muffle furnace for 5 hours at 500 C. (heating rate 2 K/min) under air. 143.82 g material were obtained. The material had a BET specific surface area of 201 m.sup.2/g, a total intrusion volume at 5.3432 mL/g and a total pore area of 73.381 m.sup.2/g. Elemental analysis of the material: H 0.44 weight-%, Al 1.0 weight-%, Si 44 weight-%. [0262] b) Preparation of the molding
Starting material

TABLE-US-00004 Zeolitic material of a) 120 g Ludox AS 40 75 g Walocel 6 g DI water 180 g polyethylene oxide (PEO) (Alkox E-160) 3.6 g

[0263] 120 g of the zeolitic material of a) were placed in a kneader, Walocel was added and pre-mixed for 5 min. Ludox was then added and the mixture was kneaded for 5 min. Thereafter 150 g of DI were added and compacted within 15 minutes. PEO was then added and the mixture was kneaded for 5 min. 30 g of DI water were then added and the mixture was kneaded for 20 min. Thereafter, the kneaded material was formed (2.5 mm) via an extrusion press (forming pressure: 95-150 bar). The resulting string were placed in a porcelain bowl in a drying oven at 120 C. for 4 h and dried and then calcined in a muffle furnace at 500 C. (heating rate: 2 K/min) for 5 h under air. 142.01 g material were obtained, having a bulk density of 0.310 g/cm.sup.3.

[0264] The material had a BET specific surface area of 196 m.sup.2/g, a total intrusion volume of 1.1770 mL/g and a total pore area of 77.861 m.sup.2/g. Elemental analysis of the material: H 0.22 weight-%, Al 0.84 weight-%, Si 45 weight-%. [0265] c) Spray-impregnation with Ga of the molding

[0266] For impregnation, the 30 g of the molding of b) were introduced into a round bottom flask and placed in a rotary evaporator. 5.5 g of Ga(NO.sub.3).sub.37 H.sub.2O were dissolved in 15 g of DI water. The metal nitrate solution was introduced into a dropping funnel, and sprayed gradually onto the extrudates through a glass spray nozzle flooded with 100 l/h of N.sub.2 while rotating. On completion of addition of the metal nitrate solution, the molding were rotated further for 10 min. Afterwards, the strands were removed and dried in a forced air drying oven for 4 h at 120 C. and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air. 31.41 g material were obtained. [0267] d) Spray-impregnation with P of the molding of c) to prepare

[0268] For impregnation, 15 g of the molding of c) were introduced into a round bottom flask and placed in a rotary evaporator. 0.6 g of H.sub.3PO.sub.4 were dissolved in 8 g of DI water (phosphorous solution). The phosphorous solution was introduced into a dropping funnel, and sprayed gradually onto the molding through a glass spray nozzle flooded with 100 l/h of N.sub.2 while rotating. On completion of addition of the phosphorous solution, the extrudates were rotated further for 10 min. Afterwards, the strands were removed and dried in the forced air drying oven for 4 h at 120 C. and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air.

[0269] The material had a BET specific surface area of 196 m.sup.2/g, a total intrusion volume of 1.0834 mL/g and a total pore area of 66,669 m.sup.2/g. Elemental analysis of the material: H 0.03 weight-%, Al 0.80 weight-%, Ga 3.0 weight-%, P 0.13 weight-%, Si 43 weight-%.

Example 2: Synthesis of a Molding Comprising the Zeolitic Material ZBM-10 Comprising Impregnation with Ga and P

[0270] a) Preparation of a ZBM-10 zeolitic material

Starting Materials:

[0271]

TABLE-US-00005 Solution 1 Hexamethylendiamine 70% in water 456 g Aerosil 200 185 g DI water 700 g Solution 2 Al.sub.2(SO.sub.4).sub.3 18 H.sub.2O (Aldrich 11044-2,5kg, 20.2 g Lot. #SZBD1200V) DI water 270 g

Solution 1

[0272] Hexamethylendiamine was placed in a beaker of 2 l volume. Water was added and the solution was stirred for 5 min at room temperature. Aerosil was added under stirring conditions. The stirring was continued for 2 h at room temperature. The pH of the solution was 12.88.

Solution 2

[0273] The DI water was added under stirring to Al.sub.2(SO.sub.4).sub.318 H.sub.2O.

[0274] Solution 1 was charged into an autoclave with stirring at 200 rpm and heated to 70 C. Solution 2 was then added under stirring at 220 rpm. The stirring was continued for 5 min. The solution was kept under stirring at 70 C. under a constant pressure for 4 h. The solution was then heated to 150 C. under a constant pressure under stirring for 170 h. Afterwards, the suspension having a pH of 12.31 was filtered off by means of a porcelain filter (blue band filter). The filter cake was washed three times with 1000 ml of DI water and dried in a forced-air drying oven at 120 C. for 4 h and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air. 187.75 g material were obtained. The material had a BET specific surface area of 347 m.sup.2 /g. Elemental analysis of the material: H 0.14 weight-%, Al 0.91 weight-%, Si 44 weight-%. [0275] b) Preparation of the molding

Starting Materials:

[0276]

TABLE-US-00006 Zeolitic material of a) 100 g Ludox AS 40 62.5 g Walocel 6 g DI water 75 g polyethylene oxide (PEO) (Alkox E-160) 3 g

[0277] 100 g of the zeolitic material of a) were placed in the kneader, Walocel was added and pre-mixed for 5 min. Ludox was then added and the mixture was kneaded for 5 min. Thereafter 50 g of DI water were added and the mixture was compacted within 15 min. 3.6 g of PEO were then added and the mixture was kneaded for 5 min. 25 g of DI water were then added and the mixture was kneaded for 5 min. Thereafter, the kneaded material was molded with an extrusion press (2.5 mm; forming pressure: 95-150 bar). The resulting strands were placed in a porcelain bowl in a drying oven at 120 C. for 4 h and dried and then calcined in a muffle furnace at 500 C. (heating rate: 2 K/min) for 5 h under air. 114.44 g material were obtained, having a bulk density of 0.443 g/cm.sup.3. The material had a BET surface area of 310 m.sup.2/g, a total intrusion volume of 0.6432 mL/g and a total pore area of 37.627 m.sup.2/g. Elemental analysis of the material: H 0.03 weight-%, Al 0.72 weight-%, Si 45 weight-%. [0278] c) Spray-impregnation with Ga of the molding of b)

[0279] For impregnation, 30 g of the molding of b) were introduced into a round bottom flask and placed in a rotary evaporator. The 5.5 g of Ga(NO.sub.3).sub.37 H.sub.2O were dissolved in 15 g of DI water. The metal nitrate solution was introduced into a dropping funnel, and sprayed gradually onto the extrudates through a glass spray nozzle flooded with 100 l/h of N.sub.2 while rotating. On completion of addition of the metal nitrate solution, the molding were rotated further for 10 min.

[0280] Afterwards, they strands were removed and dried in a forced air drying oven 4 h at 120 C. and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air. 31.20 g material were obtained. [0281] d) Spray-impregnation with P of the molding of c) to prepare the molding of the title

[0282] For impregnation, 16.15 g of the molding of c) were introduced into a round bottom flask and placed in a rotary evaporator. 0.66 g of H.sub.3PO.sub.4 were dissolved in 8 g of DI water (phosphorous solution). The phosphorous solution was introduced into a dropping funnel, and sprayed gradually onto the molding through a glass spray nozzle flooded with 100 l/h of N.sub.2 while rotating. On completion of addition of the phosphorous solution, the molding was rotated further for 10 min.

[0283] Afterwards, the impregnated strands were removed and dried in a forced air drying oven for 4 h at 120 C. and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air. 16.28 g material were obtained.

[0284] The material had a BET specific surface area of 300 m.sup.2/g. Elemental analysis of the material: H 0.01 weight-%, Al 0.69 weight-%, Ga 2.7 weight-%, P 1.1 weight-%, Si 42 weight-%.

Example 3: Preparation of a Molding Comprising a ZBM-10 Zeolitic Material Comprising Impregnation with Zn and P

[0285] a) Preparation of a ZBM-10 zeolitic material

[0286] A ZBM-10 zeolitic material was provided, prepared as described in Example 2 a) above. [0287] b) Preparation of the molding

[0288] A molding comprising the ZBM-10 zeolitic material of a) was prepared as described in Example 2 b) above. [0289] c) Spray-impregnation with Zn of the molding of b)

[0290] For impregnation, 30 g of the molding of b) were introduced into a round bottom flask and placed in a rotary evaporator. 3.2 g of Zn(OAc).sub.22 H.sub.2O were dissolved in 15 g of DI water. The metal nitrate solution was introduced into a dropping funnel, and sprayed gradually for 5 min onto the molding through a glass spray nozzle flooded with 100 I/h of N.sub.2 while rotating. On completion of addition of the metal nitrate solution, the moldings were rotated further for 15 min.

[0291] Afterwards, they strands were removed and dried in a forced air drying oven 4 h at 120 C. and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air. 11.18 g material were obtained. [0292] d) Spray-impregnation with P of the molding of a) to prepare the molding of the title

[0293] For impregnation, 16.54 g of the molding of c) were introduced into a round bottom flask and placed in a rotary evaporator. 0.66 g of H.sub.3PO.sub.4 were dissolved in 10 g of DI water (phosphorous solution). The phosphorous solution was introduced into a dropping funnel, and sprayed gradually onto the molding through a glass spray nozzle flooded with 100 l/h of N.sub.2 while rotating. On completion of addition of the phosphorous solution, the molding was rotated further for 10 min. Afterwards, the strands were removed and dried in a forced air drying oven at 120 C. and then calcined in a muffle furnace for 5 h at 500 C. (heating rate 2 K/min) under air. 16.68 g material were obtained. The material had a BET specific surface area of 277 m.sup.2 /g. Elemental analysis of the material: H 0.01 weight-%, Al 0.69 weight-%, Zn 2.8 weight-%, P 1.0 weight-%, Si 43 weight-%.

Example 4: General procedure for preparing p-xylene from methanol

[0294] a) Start-up

[0295] The catalyst (molding) was heated in a gas stream (nitrogen 90 volume-%, Argon 10 volume-%) to the reaction temperature followed by a dwell time of 2 h. [0296] b) Reaction

[0297] 0.5 ml of catalyst were loaded into a fixed bed reactor. The catalyst of a) was exposed to multiple reaction/regeneration cycles. In the first (MTX1), second (MTX2) and third (MTX3) reaction cycle, the reaction temperature was set to 450 C. and the reactor pressure at the outlet to 5 bar(abs). The gaseous hourly space velocity (GHSV) was 1,000 h.sup.1. The volume ratios of the individual gases at the reactor inlet were MeOH/Ar/N.sub.2=52 volume-%/10 volume-%/38 volume-%.

[0298] The testing was repeated at different values of the GHSV (gas hourly space velocity) of 1,550 h.sup.1 and 2100 h.sup.1. [0299] c) Regeneration

[0300] The regeneration was carried out by purging for 1 h with nitrogen and heating at a temperature of 550 C. in nitrogen flow. Afterwards, the flow was switched to 8 volume-% of oxygen in nitrogen. At the reactor outlet, the pressure was 5 bar(abs). The flow was continued until no CO and CO.sub.2 were detectable. It followed a dwell time of 1 h. Thereafter the temperature of the nitrogen flow was brought to the reaction temperature and the reaction was carried out.

Example 4.1: Preparing p-xylene from methanol using the molding of Example 1 as the catalyst at a GHSV of 1000 h.SUP.1

[0301] The general process disclosed in Example 4 was carried out with 0.5 mL of the catalyst of Example 1 at a GHSV of 1000 h.sup.1. The p-xylene yield was measured at the third cycle of reaction (MTX3). The data are reported in Table 1.

Comparative Example 4.1: Preparing P-Xylene from Methanol Using the Molding of Comparative Example 1 as the Catalyst at a GHSV of 1000 h.SUP.1

[0302] The general process disclosed in Example 4 was carried out with 0.5 mL of the catalyst of Comparative Example 1 at a GHSV of 1000 h.sup.1. The p-xylene yield was measured at the third cycle of reaction (MTX3). The data are reported in Table 1.

TABLE-US-00007 TABLE 1 Molding GHSV/h.sup.1 TOS/h .sup.a) p-xylene yield/% E 4.1 1000 117.87 9.19 C.E 4.1 1000 118.68 5.40 .sup.a) TOS = Time on stream

Example 4.2: Preparing P-Xylene from Methanol at a GHSV of 1550 h.SUP.1

Example 4.2.1: Molding of Example 2 as the Catalyst

[0303] The general process disclosed in Example 4 was carried out with 0.5 mL of the molding of Example 2 at a GHSV of 1550 h.sup.1. The p-xylene yield was measured at the third cycle of reaction. The data are reported in Table 2.

Example 4.2.2: Molding of Example 3 as the Catalyst

[0304] The general process disclosed in Example 4 was carried out with 0.5 mL of the molding of Example 3 at a GHSV of 1550 h.sup.1. The p-xylene yield was measured at the third cycle of reaction. The data are reported in Table 2.

Comparative Example 4.2: Preparing P-Xylene from Methanol Using the Molding of Comparative Example 1 as the Catalyst at a GHSV of 1550 h.SUP.1

[0305] The general process disclosed in Example 4 was carried out with 0.5 mL of the molding of Comparative Example 1 at a GHSV of 1550 h.sup.1. The p-xylene yield was measured at the third cycle of reaction (MTX3). The data are reported in Table 2.

TABLE-US-00008 TABLE 2 Catalyst GHSV/h.sup.1 TOS.sup.a)/h p-xylene yield% E 4.2.1 1550 176.6 5.09 E 4.2.2 1550 181.2 8.77 C.E 4.2 1550 140.79 4.31 C.E 4.2 1550 152.8 4.67 C.E 4.2 1550 170.38 3.81 .sup.a)TOS = Time on stream

Example 4.3: Preparing P-Xylene from Methanol at a GHSV of 2100 h.SUP.1

Example 4.3.1: Molding of Example 2 as the Catalyst

[0306] The general process disclosed in Example 4 was carried out with 0.5 mL of the molding of Example 2 at a GHSV of 2100 h.sup.1. The p-xylene yield was measured at the second cycle of reaction. The data are reported in Table 3.

Example 4.3.2: Molding of Example 3 as Catalyst

[0307] The general process disclosed in Example 4 was carried out with 0.5 mL of the catalyst of Example 3 at a GHSV of 2100 h.sup.1. The p-xylene yield was measured at the first cycle of reaction. The data are reported in Table 3.

Comparative Example 4.3: Preparing P-Xylene from Methanol Using the Molding of Comparative Example 1 as Catalyst at a GHSV of 2100 h.SUP.1

[0308] The general process disclosed in Example 4 was carried out with 0.5 mL of the molding of Comparative Example 1 at a GHSV of 2100 h.sup.1. The p-xylene yield was measured at the first cycle of reaction (MTX3). The data are reported in Table 3.

TABLE-US-00009 TABLE 3 Catalyst GHSV/h.sup.1 p-xylene yield/% E 4.3.1 2100 9.00 E 4.3.2 2100 6.04 C E 4.3 2100 5.78

[0309] As may be taken from the results shown in Tables 1 to 3, it has surprisingly been found that the impregnation of extrudates containing ZBM or ZSM zeolitic material with P and a trivalent element such as Ga and Zn leads to an increase of the p-xylene yield with respect to the ZSM-5 zeolitic material which is first impregnated with Zn and then extrudated. Thus, as may be taken from Tables 1 to 3, the moldings of the invention display a relatively high yield with respect to a ZSM-5 zeolitic material impregnated with Zn and extrudated.

CITED PRIOR ART

[0310] U.S. Pat. No. 4,401,636 [0311] Journal of Catalysis, Vol. 147, Issue 2, June 1994, pages 482-493, Synthesis and Characterization of ZSM-22 Zeolites and Their Catalytic Behaviour in 1-Butene Isomerization Reactions [0312] U.S. 2014/0135556 A1