Solidothermal synthesis of a boron-containing zeolite with an MWW framework structure

Patent metadata

Field	Value
Publication number	US-12157674-B2
Application number	US-202117480364-A
Country	US
Kind code	B2
Filing date	Sep 21, 2021
Priority date	Sep 6, 2016
Publication date	Dec 3, 2024
Grant date	Dec 3, 2024

Abstract

The present invention relates to a process for the production of a zeolitic material having an MWW framework structure comprising YO 2 and B 2 O 3 , wherein Y stands for a tetravalent element, said process comprising
(i) preparing a mixture comprising one or more sources for YO 2 , one or more sources for B 2 O 3 , one or more organotemplates, and seed crystals, (ii) crystallizing the mixture obtained in (i) for obtaining a layered precursor of the MWW framework structure, (iii) calcining the layered precursor obtained in (ii) for obtaining the zeolitic material having an MWW framework structure,

wherein the one or more organotemplates have the formula (I)

R 1 R 2 R 3 N  (I)
wherein R 1 is (C 5 -C 8 )cycloalkyl, and wherein R 2 and R 3 are independently from each other H or alkyl, and wherein the mixture prepared in (i) and crystallized in (ii) contains 35 wt.-% or less of H 2 O based on 100 wt.-% of YO 2 contained in the mixture prepared in (i) and crystallized in (ii), as well as to a synthetic boron-containing zeolite which is obtainable and/or obtained according to the inventive process and to its use.

First claim

The invention claimed is:

1. A process for producing a zeolitic material having an MWW framework structure comprising YO 2 and B 2 O 3 , wherein Y stands for a tetravalent element, the process comprising:
(i) mixing one or more sources for YO 2 , one or more sources for B 2 O 3 , one or more organotemplates, and seed crystals, to obtain a mixture;
(ii) crystallizing the mixture to obtain a layered precursor of the MWW framework structure; and
(iii) calcining the layered precursor to obtain the zeolitic material having the MWW framework structure,
wherein:
the one or more organotemplates have the formula (I)
R 1 R 2 R 3 N  (I)

R 1 is (C 5 -C 8 )cycloalkyl,
R 2 and R 3 are independently from each other H or alkyl; and
the mixture and the layered precursor comprise 35 wt.-% or less of H 2 O based on
100 wt.-% of YO 2 contained in the mixture and the layered precursor.

2. The process of claim 1 , wherein the mixture and the layered precursor comprise 5 wt.-% or less of fluoride calculated as the element and based on 100 wt.-% of YO 2 .

3. The process of claim 1 , wherein the mixture and the layered precursor comprise 5 wt.-% or less of P and/or Al calculated as the respective element and based on 100 wt.-% of YO 2 .

4. The process of claim 1 , wherein the layered precursor is selected from the group consisting of B-MCM-22(P), B-ERB-1(P), B-ITQ-1(P), B-PSH-3(P), B-SSZ-25(P), and mixtures of two or more thereof.

5. The process of claim 1 , wherein the zeolitic material having the MWW framework structure is selected from the group consisting of B-MCM-22, B-ERB-1, B-ITQ-1, B-PSH-3, B-SSZ-25, and mixtures of two or more thereof.

6. The process of claim 1 , wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof.

7. The process of claim 1 , wherein apart from organotemplate optionally contained in the seed crystals, the mixture does not contain piperidine or hexamethyleneimine.

8. The process of claim 1 , wherein the crystallization is conducted under autogenous pressure.

9. The process of claim 1 , wherein after the crystallizing and prior to the calcining, the process further comprises
(a) isolating the layered precursor, to obtain an isolated layered precursor;
(b) optionally washing the isolated layered precursor, to obtain a washed layered precursor;
(c) optionally drying the isolated layered precursor or the washed layered precursor, to obtain a dried layered precursor;
(d) optionally subjecting the layered precursor, the isolated layered precursor, or the washed layered precursor, or the dried layered precursor to ion exchange, to obtain an ion exchanged layered precursor; and
(e) optionally subjecting the isolated layered precursor, or the washed layered precursor, or the dried layered precursor, or the ion exchanged layered precursor to isomorphous substitution.

10. The process of claim 9 , wherein the isomorphous substitution is performed such that boron in the framework structure of the isolated layered precursor, the dried layered precursor, or the ion exchanged layered precursor is isomorphously substituted against one or more trivalent and/or tetravalent elements.

11. The process of claim 1 , wherein the calcination is carried out at a temperature of from 300 to 900° C.

12. The process of claim 1 , further comprising, after the calcining:
(iv) deboronating the zeolitic material having the MWW framework structure with a liquid solvent system, thereby obtaining a deboronated zeolitic material having an MWW framework structure.

13. The process of claim 12 , wherein the deboronation is carried out at a temperature of from 50 to 125° C.

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Müller Ulrich
• Maurer Stefan
• Dai Yu
• Xiao Feng-Shou
• Meng Xiangju
• Wang Yeqing

Classifications

• C01B39/12

  the replacing atoms being {at least} boron atoms · CPC title

• B01J29/7038

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

• C01P2002/86

  by NMR- or ESR-data · CPC title

• C01P2002/72

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

• B01J2229/183

  in framework positions · CPC title