Synthesis of ZSM-5 crystals with improved morphology

Patent metadata

Field	Value
Publication number	US-9289755-B2
Application number	US-201314063295-A
Country	US
Kind code	B2
Filing date	Oct 25, 2013
Priority date	Dec 7, 2012
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

Methods are provided for synthesizing crystals having a ZSM-5 framework structure from synthesis mixtures suitable for synthesis of ZSM-12 framework structure crystals in the absence of seed crystals with a ZSM-5 framework structure, such as in the absence of any seed crystals. For synthesis mixtures with a sufficiently high XO 2 :Y 2 O 3 ratio, seeding a synthesis mixture with ZSM-5 seed crystals can result in production of pure phase ZSM-5 crystals with a new morphology. The morphology can include rod-like primary crystallites with a length of about 0.5 μm or less that are organized/aggregated into larger secondary crystal structures. The aggregation of the primary crystallites into a secondary crystal structure can allow for an unexpectedly large mesoporous surface area for the ZSM-5 crystals.

First claim

What is claimed is:

1. A porous crystalline material having a ZSM-5 framework structure,
the crystalline material having an XO 2 :Y 2 O 3 ratio of at least about 80, where X is a tetravalent element selected from Si, Ge, Sn, or a combination thereof, and where Y is a trivalent element selected from Al, B, In, Ga, Fe, or a combination thereof;
the crystalline material having a mesopore surface area of at least about 100 m 2 /g; and
the crystalline material comprising crystals having a ZSM-5 framework structure and having a rod-like morphology, the crystals having a first crystal dimension corresponding to a crystal length, an average crystal length being about 0.1 μm to about 0.5 μm, and a second crystal dimension with an average dimension value that is about half the average crystal length or less.

2. The crystalline material of claim 1 , wherein at least 50 vol % of the crystals having a ZSM-5 framework structure are primary crystallites that form secondary crystal aggregates, the first crystal dimension of the primary crystallites in the secondary crystal aggregates being substantially aligned, the secondary crystal aggregates having an average aggregate length that is at least 5 times the average crystal length, the crystal aggregates having an average aggregate width that is at least 10 times the average dimension value of the second crystal dimension.

3. The crystalline material of claim 1 , wherein X is Si, Y is Al, and the crystals having a ZSM-5 framework structure are ZSM-5 crystals.

4. The crystalline material of claim 1 , wherein the XO 2 :Y 2 O 3 ratio is at least about 100.

5. The crystalline material of claim 1 , wherein the XO 2 :Y 2 O 3 ratio is at least about 150.

6. The crystalline material of claim 1 , wherein the mesopore surface area is at least about 120 m 2 /g.

7. The crystalline material of claim 1 , wherein the crystalline material is substantially pure, the substantially pure crystalline material comprising less than 10 wt % of crystalline material that has a framework structure different from a ZSM-5 framework structure.

8. The crystalline material of claim 1 , wherein the total surface area of the crystals having a ZSM-5 framework structure is at least about 400 m 2 /g.

9. The crystalline material of claim 1 , wherein at least a portion of the crystals having a ZSM-5 framework structure contain a structure directing agent within pores thereof.

10. A method for synthesizing a crystalline material having the framework structure of ZSM-5, comprising:
forming a synthesis mixture capable of forming crystals with a zeolite framework structure, the mixture comprising water, a tetravalent oxide (XO 2 ), an alkali or alkaline earth hydroxide, and a structure directing agent, the mixture having an XO 2 :Y 2 O 3 ratio of at least about 50, the mixture being suitable for formation of crystals having a ZSM-12 framework structure in the absence of seed crystals having a ZSM-5 framework structure;
adding from about 0.05 wt % to about 5 wt % of seed crystals having a ZSM-5 framework structure into the synthesis mixture; and
recovering substantially pure crystals having a ZSM-5 framework structure from the synthesis mixture, the crystals having a ZSM-5 framework structure having an average size of at least 0.1 μm in at least one dimension,
wherein X is a tetravalent element selected from Si, Ge, Sn, or a combination thereof, and wherein Y is a trivalent element selected from Al, B, In, Ga, Fe, or a combination thereof.

11. The method of claim 10 , wherein X is Si and Y is Al.

12. The method of claim 10 , wherein the XO 2 :Y 2 O 3 ratio in the synthesis mixture is at least about 100.

13. The method of claim 10 , wherein the recovered crystals having a ZSM-5 framework structure have a mesopore surface area of at least about 100 m 2 /g.

14. The method of claim 10 , wherein the recovered crystals having a ZSM-5 framework structure have an XO 2 :Y 2 O 3 ratio of at least about 80.

15. The method of claim 14 , wherein at least 50 vol % of the recovered crystals are primary crystallites that form secondary crystal aggregates, a first crystal dimension of the primary crystallites in the secondary crystal aggregates being substantially aligned, the first crystal dimension having an average size of at least about 0.1 μm, the secondary crystal aggregates having an average aggregate length that is at least 5 times the average crystal length, the crystal aggregates having an average aggregate width that is at least 10 times the average dimension value of the second crystal dimension.

16. The method of claim 15 , wherein the recovered crystals having a ZSM-5 framework structure have an XO 2 :Y 2 O 3 ratio of at least about 100.

17. The method of claim 10 , wherein the structure directing agent is a tetraalkyl ammonium salt.

18. The method of claim 10 , wherein the structure directing agent is a tetraethyl ammonium salt, a methyltriethyl ammonium salt, or a benzyltriethyl ammonium salt.

19. The method of claim 10 , wherein the mixture is suitable for formation of crystals having a ZSM-12 framework structure in the absence of seed crystals.

20. A method for synthesizing a material with the framework structure of ZSM-5, comprising:
forming a synthesis mixture capable of forming crystals with a zeolite framework structure, the mixture comprising water, a tetravalent oxide (XO 2 ), an alkali or alkaline earth hydroxide, and a structure directing agent, the mixture having an XO 2 :Y 2 O 3 ratio of at least about 100, the structure directing agent being suitable for formation of crystals having a ZSM-12 framework structure in the absence of seed crystals;
adding from about 0.05 wt % to about 5 wt % of seed crystals having a ZSM-5 framework structure into the synthesis mixture; and
recovering substantially pure crystals having a ZSM-5 framework structure from the synthesis mixture, the crystals having a ZSM-5 framework structure having an average size of at least 0.1 μm in at least one dimension, an XO 2 :Y 2 O 3 ratio of at least about 80, and a mesopore surface area of at least about 100 m 2 /g,
wherein X is a tetravalent element selected from Si, Ge, Sn, or a combination thereof, and wherein Y is a trivalent element selected from Al, B, In, Ga, Fe, or a combination thereof.

Assignees

• Lai Wenyih Frank
• Rollman Nicholas S
• Exxonmobil Res & Eng Co

Inventors

• Lai Wenyih Frank
• Rollman Nicholas S

Classifications

• B01J20/18 Primary

  Synthetic zeolitic molecular sieves · CPC title

• B01J29/40 Primary

  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

• C01B39/40

  using at least one organic template directing agent · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• C01B39/42

  Type ZSM-12 · CPC title