MFI with unusual morphology

Patent metadata

Field	Value
Publication number	US-9725327-B2
Application number	US-201314440946-A
Country	US
Kind code	B2
Filing date	Nov 14, 2013
Priority date	Nov 28, 2012
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

A method of making a crystalline molecular sieve of MFI framework type, preferably ZSM-5, from a synthesis mixture comprising at least one source of tetravalent element (Y), at least one source of trivalent element (X), at least one source of alkali metal hydroxide (MOH), at least one structure directing; (R) and water, said synthesis mixture having the following molar composition: YO 2 , (p)X 2 O 3 : (q) MOH: (r) R: (s) H 2 O, wherein (p) is from 0.005 to 0.025, (q) is from 0.05 to 0.5, (r) is from 0.05 to 0.15 and (s) is from 35 to 45, wherein the ratio of the largest dimension (L) to the smallest dimension (S) of each crystal of the molecular sieve product is at least 5, and the smallest dimension (S) is from 20 nm to 200 nm.

First claim

We claim:

1. A method of making a crystalline molecular sieve of MFI framework type, said method comprising the steps of:
(a) providing a synthesis mixture comprising at least one source of tetravalent element (Y), at least one source of trivalent element (X), at least one source of alkali metal hydroxide (MOH), at least one structure directing agent (R) and water, said synthesis mixture having the following molar composition (expressed in terms of oxide):
YO 2 :( p )X 2 O 3 :( q )MOH:( r )R:( s )H 2 O

wherein (p) is in the range from 0.005 to 0.025, (q) is in the range from 0.05 to 0.5, (r) is in the range from 0.05 to 0.15, (s) is in the range from 35 to 45; and wherein said structure directing agent (R) is a compound having a cation of the general formula R 1 R 2 R 3 N + (CH 2 ) n N + R 4 R 5 R 6 A − with n equal to 4, 5 or 6, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently representing an alkyl group having 1 to 4 carbon atoms, and A − representing a hydroxide or a halide ion, wherein said tetravalent element is silicon, and said silicon is in the form of a fumed silica or a precipitated silica; and
(b) treating said synthesis mixture under crystallization conditions to form crystals of molecular sieve of MFI framework type, wherein the ratio of the largest dimension (L) to the smallest dimension (S) of each crystal is at least 5, and the smallest dimension (S) is from 20 nm to 200 nm, wherein said crystallization conditions comprise a temperature in the range of 90 to 200° C. applied for 24 to 240 hours.

2. The method of claim 1 , wherein (p) is in the range from 0.008 to 0.025.

3. The method of claim 1 , wherein (q) is in the range from 0.2 to 0.4.

4. The method of claim 1 , wherein (r) is in the range from 0.08 to 0.1.

5. The method of claim 1 , wherein (s) is in the range from 39 to 41.

6. The method of claim 1 , wherein said trivalent element is aluminum, boron, gallium or a mixture thereof.

7. The method of claim 1 , wherein said alkali metal (M) is sodium.

8. The method of claim 1 , wherein n equals 5.

9. The method of claim 1 , wherein R 1 to R 6 independently represent methyl or ethyl.

10. The method of claim 1 , wherein said structure directing agent (R) is a N,N,N,N′,N′,N′-hexaethylpentane diammonium halide.

11. The method of claim 1 , wherein said crystallization conditions comprise a temperature in the range of 155° C. to 185° C.

12. The method of claim 1 , wherein said synthesis mixture further comprises seed crystals.

13. The method of claim 1 , wherein said crystalline molecular sieve of MFI framework type is ZSM-5.

14. A crystalline molecular sieve of MFI framework type comprising silicon and aluminum and having a platelet morphology, wherein the ratio of the largest dimension (L) to the smallest dimension (S) of each crystal is at least 5, and the smallest dimension (S) is in the range from 20 nm to 200 nm,
wherein said crystalline molecular sieve made by the method comprising the steps of:
(a) providing a synthesis mixture comprising at least one source of tetravalent element (Y), at least one source of trivalent element (X), at least one source of alkali metal hydroxide (MOH), at least one structure directing agent (R) and water, said synthesis mixture having the following molar composition (expressed in terms of oxide):
YO 2 :( p )X 2 O 3 :( q )MOH:( r )R:( s )H 2 O

wherein (p) is in the range from 0.005 to 0.025, (q) is in the range from 0.05 to 0.5, (r) is in the range from 0.05 to 0.15, (s) is in the range from 35 to 45; and wherein said structure directing agent (R) is a compound having a cation of the general formula R 1 R 2 R 3 N + (CH 2 ) n N + R 4 R 5 R 6 A − with n equal to 4, 5 or 6, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently representing an alkyl group having 1 to 4 carbon atoms, and A − representing a hydroxide or a halide ion, wherein said tetravalent element is silicon, and said silicon is in the form of a fumed silica or a precipitated silica; and
(b) treating said synthesis mixture under crystallization conditions to form crystals of molecular sieve of MFI framework type, wherein the ratio of the largest dimension (L) to the smallest dimension (S) of each crystal is at least 5, and the smallest dimension (S) is from 20 nm to 200 nm, wherein said crystallization conditions comprise a temperature in the range of 90 to 200° C. applied for 24 to 240 hours.

15. The crystalline molecular sieve of claim 14 , wherein having a molar ratio of silicon to aluminum in the range from 15:1 to 70:1.

16. The crystalline molecular sieve of claim 15 , wherein said crystalline molecular sieve of MFI framework type is ZSM-5.

17. A process for hydrocarbon conversion comprising the step of contacting a hydrocarbon feedstock under hydrocarbon conversion conditions with the crystalline molecular sieve of MFI framework type of claim 14 .

18. The process of claim 17 , wherein said crystalline molecular sieve of MFI framework type is ZSM-5.

Assignees

• Exxonmobil Chemical Patents Inc
• Mertens Machteld Maria Wilfried
• Anthonis Marc H
• Bons Antonie Jan
• Engels Brita
• Mortier Wilfried Jozef
• Cheng Jane Chi-Ya

Inventors

• Mertens Machteld Maria Wilfried
• Anthonis Marc H
• Bons Antonie Jan
• Engels Brita
• Mortier Wilfried Jozef
• Cheng Jane Chi-Ya

Classifications

• B01J29/40

  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 title

• B01J20/18

  Synthetic zeolitic molecular sieves · CPC title

• C07C2529/44

  Noble metals · CPC title

• C07C2529/46

  Iron group metals or copper · CPC title

• C01B39/40 Primary

  using at least one organic template directing agent · CPC title