Pentasil-structuer zeolithic material the production and use thereof

• US 20070135637A1
• Filed: 12/02/2004
• Published: 06/14/2007
• Est. Priority Date: 12/02/2003
• Status: Active Grant

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Frauenkron, Matthias, Bosch, Marco, Muller, Ulrich
• Granted Patent: US 7,902,102 B2
• Time in Patent Office: Days
• US Class Current: 544/352
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B29B 2009/125 Micropellets, microgranules, microparticles
• CPC Class Codes: B29B 9/06 in the form of filamentary material, e.g. combined with extrusion
• CPC Class Codes: B29B 9/12 characterised by structure or composition
• CPC Class Codes: C01B 39/36 Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• CPC Class Codes: C01B 39/40 using at least one organic template directing agent
• CPC Class Codes: C07D 487/08 Bridged systems

Abstract

Zeolite material of the pentasil type has an alkali metal and alkaline earth metal content of not more than 100 ppm and a molar ratio of Si to Al of from 250 to 1500, at least 90% of the primary particles of the zeolite material being spherical and 95% by weight of the spherical primary particles having a diameter of less than or equal to 1 μm.

Claims

1. A zeolite material of the pentasil type comprising an alkali metal and alkaline earth metal content of not more than 150 ppm and a molar ratio of Si to Al of from 250 to 1500, wherein at least 90% of the primary particles of the zeolite material are spherical and at least 95% by weight of the spherical primary particles have a diameter of less than or equal to 1 μ

m.

2. The zeolite material as claimed in claim 1, wherein a portion of the zeolite material has the structure type ZSM-5.

3. The zeolite material as claimed in claim 1, wherein the alkali metal and alkaline earth metal content of the zeolite material is not more than 100 ppm.

4. The zeolite material as claimed in claim 1, wherein the diameter of the spherical primary particles is from 50 to 250 nm.

5. The zeolite material as claimed in claim 1, wherein the molar ratio of Si to Al is in the range of from 250 to 750.

6. The zeolite material as claimed in claim 1, wherein the molar ratio of Si to Al is in the range of from 350 to 600.

7. A molding containing the zeolite material according to claim 1 and at least one binder material.

8. The molding as claimed in claim 7, wherein the binder material includes SiO₂.

9. The molding as claimed in claim 7, wherein the binder material is present from 5 to 80% by weight, based on the total weight of the dried molding.

10. The molding as claimed in claim 9, having a specific surface area of at least 350 m²/g, and a pore volume of at least 0.6 ml/g.

11. The molding as claimed in claim 10, having a cutting hardness of from 2 to 15 N.

23. Use of a zeolite material according to claim 1 as a catalyst

24. The use as claimed in claim 23, wherein the catalyst is used in the synthesis of triethylenediamine.

25. A process for the preparation of triethylenediamine or of an alkyl-substituted derivative thereof by reacting at least one starting material which has a structural unit according to formula (I)

26. The process as claimed in claim 25, wherein the starting material is selected from

piperazine (PIP),

ethylenediamine (EDA) or a mixture thereof.

27. The process as claimed in claim 26, wherein the starting material is reacted in at least one solvent or diluent.

28. The process as claimed in claim 26, wherein at least a portion of the zeolite material is provided in the H form.

29. The process as claimed in claim 26, wherein the starting material is ethylenediamine, and the reaction is carried out at a temperature of from 300 to 400°

C. and a pressure of from 0.01 to 50 bar.

30. The process as claimed in claim 26, wherein the starting material is piperazine, and the reaction is carried out at a temperature of from 300 to 450°

C. and a pressure of from 0.01 to 50 bar.

31. The process as claimed in claim 26, wherein the starting material is a mixture of piperazine and ethylenediamine in water, and EDA and PIP are present in an amount of from 10 to 50% by weight based on water and in an amount of from 90 to 50% by weight based on the sum of the weights of EDA and PIP.

32. The process as claimed in claim 31, wherein the reaction is conducted at a temperature of from 290 to 400°

C. and a pressure of from 0.01 to 10 bar.

33. The process as claimed in claim 31, wherein EDA and PIP are present in a weight ratio in the range of from 1:

1 to 10;

1, calculated as the ratio of the weight of EDA to the weight of PIP.

12. A process for the preparation of a zeolite material, comprising the steps

(i) providing a mixture containing at least one SiO₂ source, at least one aluminum source and at least one template compound, wherein the mixture contains not more than 150 ppm of alkali metal and alkaline earth metal and wherein the at least one SiO₂ source and the at least one aluminum source are used in a ratio which permits the formation of a crystalline material having a molar ratio of Si to Al of from 250 to 1500;

(ii) reacting the mixture to give a mother liquor containing crystalline material, said crystalline material containing at least a portion of at least one template compound;

(iii) separating the crystalline material from the mother liquor; and

(iv) removing the at least one template compound from the crystalline material.

13. The process as claimed in claim 12, wherein a the SiO₂ source includes tetraalkoxysilane and the template compound includes at least one tetraalkylammonium hydroxide, and the mixture according to (i) additionally contains water.

14. The process as claimed in claim 13, wherein alcohol which is formed in the mixture according to (i) is distilled off prior to reacting the mixture according to (ii).

15. The process as claimed in claim 14, wherein the reacting the mixture according to (ii) is conducted at a temperature from 150 to 180°

C. in an autoclave with a reaction time of 1 to 48 hours.

16. The process as claimed in claim 12, wherein the crystalline material separated according to (iii) is dried at a temperature from 100 to 160°

C. and then calcined at a temperature from 450 to 700°

C.

17. The process as claimed in claim 12, wherein after step (iv), the zeolite material is exposed to water in an autoclave and is subsequently dried at a temperature from 80 to 160°

C. and is subsequently calcined at a temperature from 400 to 750°

C.

18. A zeolite material of the pentasil type obtainable by a process according to claim 12, said zeolite material comprising an alkali metal and alkaline earth metal content of not more than 150 ppm and a molar ratio of Si to Al in a range of from 250 to 1500, wherein at least 90% of the primary particles of the zeolite material are spherical and at least 95% by weight of the spherical primary particles have a diameter in the range of from less than or equal to 1 μ

m.

19. A process for the production of a molding, comprising the steps

(I) providing a zeolite material of the pentasil type comprising an alkali metal and alkaline earth metal content of not more than 150 ppm and a molar ratio of Si to Al of from 250 to 1500, wherein at least 90% of the primary particles of the zeolite material are spherical and at least 95% by weight of the spherical primary particles have a diameter of less than or equal to 1 μ

m and at least one binder material to form a mixture;

(II) kneading of the mixture;

(III) molding of the kneaded mixture to give at least one molding;

(IV) drying of the at least one molding; and

(V) calcining of the dried molding.

20. The process as claimed in claim 19, wherein the binder is a SiO₂-containing binder material.

21. The process as claimed in claim 19, wherein the mixture according to (I) further comprises at least one pore forming agent.

22. A molding, obtainable by a process according to claim 19.