Micropowder and molding containing a zeolitic material containing Ti and Zn

Patent metadata

Field	Value
Publication number	US-9296715-B2
Application number	US-201314143838-A
Country	US
Kind code	B2
Filing date	Dec 30, 2013
Priority date	Feb 7, 2012
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

The present invention relates to a micropowder, wherein the particles of the micropowder have a Dv10 value of at least 2 micrometer and the micropowder comprises mesopores which have an average pore diameter in the range of from 2 to 50 nm and comprise, based on the weight of the micropowder, at least 95 weight-% of a microporous aluminum-free zeolitic material of structure type MWW containing titanium and zinc.

First claim

The invention claimed is:

1. A molding, comprising:
a microporous aluminum-free zeolitic material of structure type MWW comprising titanium and zinc (ZnTiMWW).

2. The molding of claim 1 , comprising:
a micropowder comprising, based on a weight of the micropowder, at least 95 weight-% of the microporous aluminum-free zeolitic material.

3. The molding of claim 2 ,
wherein the micropowder is a micropowder, the particles of which having a Dv10 value of at least 2 micrometer, said micropowder comprising:
mesopores having an average pore diameter (4V/A) in the range of from 2 to 50 nm as determined by Hg porosimetry according to DIN 66133, and comprising,
based on the weight of the micropowder, at least 95 weight-% of a microporous aluminum-free zeolitic material of structure type MWW comprising titanium and zinc (ZnTiMWW).

4. The molding of claim 2 , comprising:
the micropowder in an amount in the range of from 70 to 80 weight-% and
a silica binder in an amount in the range of from 30 to 20 weight-%, the micropowder together with the silica binder constituting at least 99 weight-% of the molding,
wherein the molding has a concentration of silanol groups with respect to a total number of Si atoms of at most 6%, as determined according to 29 Si MAS NMR.

5. The molding of claim 4 ,
wherein the molding has a concentration of silanol groups with respect to a total number of Si atoms of at most 3%, as determined according to 29 Si MAS NMR.

6. The molding of claim 1 , further comprising at least one binder.

7. The molding of claim 1 , comprising:
mesopores having an average pore diameter in the range of from 4 to 40 nm, as determined by Hg porosimetry according to DIN 66133.

8. The molding of claim 1 , having a crystallinity, as determined by XRD analysis, of at least (55+/−10) %.

9. The molding of claim 1 ,
wherein the molding is a strand having a circular cross-section and a diameter in the range of from 1.5 to 1.7 mm and
the molding has a crush strength of at least 5 N, the crush strength being determined by crush strength test machine Z2.5/TS1S.

10. The molding of claim 9 ,
wherein the crush strength is in the range of from 12 to 20 N.

11. The molding of claim 1 ,
wherein the 29 Si-NMR spectrum of said molding comprising six peaks of
peak 1 at −98+/− x ppm,
peak 2 at −104+/− x ppm,
peak 3 at −110+/− x ppm,
peak 4 at −113+/− x ppm,
peak 5 at −115+/− x ppm, and
peak 6 at −118+/− x ppm,

with x in any of the six peaks being 1.5,
wherein Q which is defined as
Q = 100*{[ a 1 +a 2 ]/[ a 4 +a 5 +a 6 ]}/a 3

is at most 2.5, with
[a 1 +a 2 ] being a sum of peak areas of the peaks 1 and 2,
[a 4 +a 5 +a 6 ] being a sum of peak areas of the peaks 4, 5, and 6, and
a 3 being a peak area of the peak 3.

12. The molding of claim 1 , having a water uptake in the range of from 3 to 8 weight-%.

13. The molding of claim 1 ,
wherein an infrared spectrum of said molding comprises a band in the region of (3700-3750)+/−20 cm −1 and a band in the region of (3670-3690)+/−20 cm −1 ,
wherein an intensity ratio of the band in the region of (3700-3750)+/−20 cm −1 relative to the band in the region of (3670-3690)+/−20 cm −1 is at most 1.5.

14. A method for preparing propylene oxide from propene with hydrogen peroxide as an oxidizing agent in acetonitrile as solvent in a continuous process, the method comprising:
employing the molding according to claim 1 as a catalyst,
wherein a selectivity with respect to propylene oxide relative to hydrogen peroxide after a run-time of 500 h is at least 95%.

15. The method of claim 14 ,
wherein the selectivity is at least 96%.

16. A molding, obtained by a process, comprising:
(i) providing a suspension comprising a microporous aluminum-free zeolitic material of structure type MWW comprising titanium and zinc (ZnTiMWW);
(ii) subjecting the suspension provided in (i) to spray-drying to obtain a micropowder;
(iii) optionally calcining the micropowder obtained in (ii);
(iv) sharping the micropowder obtained in (ii) or (iii) to obtain a molding; and
(v) optionally drying and/or calcining the molding obtained in (iv),
wherein the micropowder obtained in (ii) or (iii) is a micropowder the particles of which having a Dv10 value of at least 2 micrometer, the micropowder comprising mesopores having an average pore diameter (4V/A) in the range of from 2 to 50 nm as determined by Hg porosimetry according to DIN 66133, and comprising, based on a weight of the micropowder, at least 95 weight % of a microporous aluminum-free zeolitic material of structure type MWW comprising titanium and zinc (ZnTiMWW),
wherein in (ii), a spray-apparatus is used for spray-drying the suspension, the spray-apparatus being operated with a nozzle gas having a temperature in the range of from 20 to 50 ° C., and a drying gas having a temperature in the range of from 250 to 350 ° C., said nozzle gas being an inert gas, and
wherein in (iii the micropowder is calcined at a temperature in the range of from 600 to 700 ° C. for a duration in the range of from 0.5 to 6 h.

17. The molding of claim 16 ,
wherein said drying gas is an inert gas.

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Mueller Ulrich
• Teles Joaquim Henrique
• Seelig Bianca
• Kampe Philip
• Weber Markus
• Bayer Robert
• Seidel Karsten
• Resch Peter

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J35/37

  Crush or impact strength · CPC title

• B01J35/77

  Compounds characterised by their crystallite size · CPC title