Process for the synthesis of IZM-2 zeolite in the presence of a template, 1,6-bis(methylpiperidinium)hexane dihydroxide

Patent metadata

Field	Value
Publication number	US-10865116-B2
Application number	US-201815933848-A
Country	US
Kind code	B2
Filing date	Mar 23, 2018
Priority date	Mar 24, 2017
Publication date	Dec 15, 2020
Grant date	Dec 15, 2020

Abstract

A novel process is described for the preparation of a microporous crystalline solid, known as IZM-2 microporous solid or IZM-2 zeolite. This novel process consists of carrying out the synthesis of IZM-2 zeolite by conversion/transformation of a zeolite with structure type FAU in a fluorinated medium under hydrothermal conditions. In particular, said novel process consists of carrying out the synthesis of an IZM-2 zeolite in a fluorinated medium starting from a zeolite with structure type FAU used as the source of silicon and aluminium and a specific organic molecule or template comprising two quaternary ammonium functions, namely 1,6-bis(methylpiperidinium)hexane dihydroxide.

First claim

The invention claimed is:

1. A process for preparing an IZM-2 zeolite, comprising at least the following steps:
i) mixing, in an aqueous medium,
at least one zeolite with structure type FAU having a molar ratio SiO 2(fau) /Al 2 O 3 (fau) of greater than or equal to 30,
at least one nitrogen-containing organic compound R, R being 1,6-bis(methylpiperidinium)hexane dihydroxide, and
at least one source of at least one fluoride anion,
optionally at least one additional source of an oxide XO2, wherein the molar ratio XO2/SiO2 (fau) is in the range of 0 to 4,
the mixture having the following molar composition:

(XO 2 + SiO 2 (fau) )/Al 2 O 3 (fau)
in the range 30 to 600,

H 2 O/(XO 2 + SiO 2 (fau) )
in the range 1 to 100,

R/(XO 2 + SiO 2 (fau) )
in the range 0.01 to 0.6, and

BF/(XO 2 + SiO 2 (fau) )
in the range 0.005 to 0.75,

in which
X is one or more tetravalent element(s) selected from the group consisting of the following elements: silicon, germanium, and titanium,
SiO 2(fau) being the quantity of SiO 2 supplied by the FAU zeolite,
Al 2 O 3 (fau) being the quantity of Al 2 O 3 supplied by the FAU zeolite, and
BF is a fluorine salt, in which B is a cation selected from the cations NH4+, Na+, K+ and Li+, or is hydrofluoric acid in an aqueous solution, and
ii) hydrothermal treatment of said mixture obtained from step i) at a temperature in the range of 120° C. to 200° C. for a period in the range of 1 day to 10 days, until said 1ZM-2 zeolite has been formed.

2. The process as claimed in claim 1 , in which said zeolite with structure type FAU is Y zeolite.

3. The process as claimed in claim 1 , in which the source BF of at least one anion is NH 4 F in aqueous solution.

4. The process as claimed in claim 1 , in which X is silicon.

5. The process as claimed in claim 1 , in which the additional source of an oxide XO 2 is added in the mixing step i), wherein the molar ratio XO 2 /SiO 2 (FAU) is in the range of 0 to 3.

6. The process as claimed in claim 1 , in which the reaction mixture obtained in step i) has the following molar composition:

(XO 2 + SiO 2 (FAU) )/Al 2 O 3 (FAU)
in the range 30 to 600,

H 2 O/(XO 2 + SiO 2 (FAU) )
in the range 10 to 70,

R/(XO 2 + SiO 2 (FAU) )
in the range 0.05 to 0.45, and

BF/(XO 2 + SiO 2 (FAU) )
in the range 0.01 to 0.65.

7. The process as claimed in claim 1 , in which the reaction mixture obtained in step i) has the following molar composition:

(XO 2 + SiO 2 (FAU) )/Al 2 O 3 (FAU)
in the range 80 to 450,

H 2 O/(XO 2 + SiO 2 (FAU) )
in the range 15 to 55

R/(XO 2 + SiO 2 (FAU) )
in the range 0.085 to 0.4, and

BF/(XO 2 + SiO 2 (FAU) )
in the range 0.02 to 0.55.

8. The process as claimed in claim 1 , in which the mixture of step i) also contains at least one source of at least one alkali metal and/or alkaline-earth metal M with valency n, wherein n is a whole number greater than or equal to 1, and M is lithium, potassium, sodium, magnesium or calcium or a mixture thereof.

9. The process as claimed in claim 1 , in which the hydrothermal treatment step ii) is carried out at a temperature in the range of 120° C. to 195° C.

10. The process as claimed in claim 1 , in which the hydrothermal treatment step ii) is carried out for a period in the range of 2 days to 11 days.

11. The process as claimed in claim 1 , in which the additional source of an oxide XO 2 is added in the mixing step i).

12. The process as claimed in claim 1 , wherein X is silicon.

13. The process as claimed in claim 1 , wherein BF is a fluorine salt, in which B is a cation selected from the cations NH 4 + , Na + , K + and Li + , in an aqueous solution.

14. The process as claimed in claim 1 , wherein BF is hydrofluoric acid in an aqueous solution.

15. The process as claimed in claim 1 , wherein the at least one zeolite with structure type FAU has a molar ratio SiO 2(FAU) /Al 2 O 3(FAU) of 30 to 100.

16. The process as claimed in claim 1 , wherein the at least one zeolite with structure type FAU has a molar ratio SiO 2(FAU) /Al 2 O 3(FAU) of 80.

Assignees

• Ifp Energies Now

Inventors

• Martinez Franco Raquel
• Bats Nicolas

Classifications

• C01F11/02

  Oxides or hydroxides (production of lime C04B2/00) · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• C01P2002/72

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

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• C01B39/04 Primary

  using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound · CPC title