MWW type zeolite, method for producing same, and cracking catalyst

Patent metadata

Field	Value
Publication number	US-11485644-B2
Application number	US-201816767011-A
Country	US
Kind code	B2
Filing date	Nov 28, 2018
Priority date	Nov 28, 2017
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

Provided are the following: an MWW type zeolite which has many Brønsted acid sites when in the form of a proton type and which is highly suitable as a cracking catalyst for cumene; a method for producing same; and an application of same. The present invention provides an MWW type zeolite in which the ratio (B/A) of the peak intensity (B) attributable to tetracoordinate aluminum relative to the peak intensity (A) attributable to hexacoordinate aluminum is 2 or more in 27Al MAS NMR, when measured as an ammonium type. The present invention also provides a method for producing an MWW type zeolite, the method having a step for carrying out a hydrothermal synthesis reaction in the presence of: a seed crystal of an MWW type zeolite containing no organic structure-directing agent; and a reaction mixture containing a silica source, an alumina source, an alkali source, an organic structure-directing agent, and water. The reaction mixture satisfies the following molar ratio: X/SiO2<0.15 (here, X denotes the number of moles of the organic structure-directing agent).

First claim

The invention claimed is:

1. An MWW-type zeolite wherein a ratio (B/A) of a peak intensity (B) attributable to tetracoordinate aluminum to a peak intensity (A) attributable to hexacoordinate aluminum is 2 or more in 27 Al MAS NMR as measured from an ammonium form of the MWW-type zeolite, wherein the ratio (B/A) refers to a peak height ratio in the NMR chart, wherein the MWW-type zeolite is a calcined product after synthesis, and wherein the 27 Al MAS NMR is measured directly from the MWW-type zeolite in a case where the MWW-type zeolite is the ammonium form or measured after the MWW-type zeolite is converted into the ammonium form in a case where the MWW-type zeolite is not in the ammonium form.

2. The MWW-type zeolite according to claim 1 , wherein an amount of Brønsted acid sites with a adsorption heat of ammonia of 106 kJ/mol or more is 0.5 mmol/g or more.

3. The MWW-type zeolite according to claim 1 , wherein a micropore volume is 0.07 cm 3 /g or more and 0.2530 cm 3 /g or less.

4. The MWW-type zeolite according to claim 1 , wherein a SiO 2 /Al 2 O 3 molar ratio is 17 or more and 37 or less.

5. The MWW-type zeolite according to claim 1 , wherein when the MWW-type zeolite is subjected to X-ray diffraction measurement, a peak is observed in at least one range below:
2θ=6.4° to 7.4°, 13.5° to 14.5°, 24.1° to 25.1°, 24.7 to 25.7°, 27.1 to 28.1°, 28.0° to 29.0°, 28.6° to 29.6°, and 29.1° to 30.1°.

6. The MWW-type zeolite according to claim 1 , having a hexagonal plate-like shape.

7. A cracking catalyst for cumene, the cracking catalyst comprising the MWW-type zeolite according to claim 1 .

8. A method for producing the MWW-type zeolite according to claim 1 , the method comprising a step of carrying out hydrothermal synthesis in the presence of a seed crystal of the MWW-type zeolite containing no organic structure-directing agent, and a reaction mixture containing a silica source, an alumina source, an alkali source, an organic structure-directing agent, and water, wherein the reaction mixture satisfies a molar ratio below:
X/SiO 2 <0.15 (where X denotes the number of moles of the organic structure-directing agent).

9. The production method according to claim 8 , wherein the reaction mixture used has a composition represented by molar ratios below:
SiO 2 /Al 2 O 3 =5 or more and 200 or less;
Na 2 O/SiO 2 =0.05 or more and 0.5 or less;
H 2 O/SiO 2 =5 or more and 200 or less; and
X/SiO 2 =0.01 or more and less than 0.15 (where X denotes the number of moles of the organic structure-directing agent).

10. The production method according to claim 8 , wherein the seed crystal used has a SiO 2 /Al 2 O 3 molar ratio of 10 to 40.

11. The production method according to claim 8 , wherein the seed crystal is used in a ratio of 1% by mass or more and 50% by mass or less relative to SiO 2 in the reaction mixture.

12. The production method according to claim 8 , wherein the hydrothermal synthesis is carried out under heating at 100° C. to 180° C.

13. The production method according to claim 8 , wherein the organic structure-directing agent is hexamethyleneimine.

Assignees

• Mitsui Mining & Smelting Co Ltd
• Nat Univ Corp Tottori Univ
• Nat Univ Corp Yokohama Nat Univ

Inventors

• Kamimura Yoshihiro
• Endou Akira
• Yamazaki Yasuo
• Katada Naonobu
• Suganuma Satoshi
• Kubota Yoshihiro
• Inagaki Satoshi

Classifications

• C07C2529/70

  of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• B01J29/7038 Primary

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• C01B39/46

  Other types characterised by their X-ray diffraction pattern and their defined composition {(C01B39/023, C01B39/026, C01B39/06 take precedence)} · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title