Synthesis of ZSM-58 crystals with improved diffusivity for use in gas separations

Patent metadata

Field	Value
Publication number	US-9573116-B2
Application number	US-201414573177-A
Country	US
Kind code	B2
Filing date	Dec 17, 2014
Priority date	Dec 30, 2013
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

Methods are provided for synthesizing ZSM-58 crystals with an improved morphology and/or an improved size distribution. By controlling the conditions during synthesis of the ZSM-58 crystals, crystals of a useful size with a narrow size distribution can be generated. Steaming the H-form DDR framework type crystals at a temperature from 426±° C. to 1100±° C. for a time period from about 30 minutes to about 48 hours can attain one or more of the following properties: a CH4 diffusivity of no more than 95% of the CH4 diffusivity of the unsteamed H-form DDR framework type crystals; an N2 BET surface area from 85% to 110% of the surface area of unsteamed H-form DDR framework type crystals; and an equilibrium CO2 sorption capacity from 80% to 105% of the equilibrium CO2 sorption capacity of unsteamed H-form DDR framework type crystals.

First claim

What is claimed is:

1. A method for synthesizing a DDR framework type zeolite, comprising:
forming a reaction mixture capable of forming crystalline DDR framework type material, the mixture comprising water, a silicon oxide, an alkali or alkaline earth hydroxide, and a methyltropinium salt structure directing agent, the mixture having a ratio of silicon oxide to hydroxide of about 0.01 to about 1.0, a ratio of silicon oxide to alkali and alkaline earth metal of about 0.01 to about 2.0, a ratio of silicon oxide to structure directing agent of about 0.01 to about 2.0, and at least about 0.05 wt % of seeds relative to the weight of the mixture;
recovering DDR framework type crystals from the reaction mixture;
converting the recovered DDR framework type crystals to their H-form, wherein the H-form DDR framework type crystals have an N 2 BET surface area and a methane diffusivity; and
steaming the H-form DDR framework type crystals at a temperature from 426° C. to 1100° C. for a time period from about 30 minutes to about 48 hours, so as to attain one or more of the following properties:
a CH 4 diffusivity of no more than 95% of the CH 4 diffusivity of otherwise identical but unsteamed H-form DDR framework type crystals;
an N 2 BET surface area from 85% to 110% of the N 2 BET surface area of otherwise identical but unsteamed H-form DDR framework type crystals;
following a pre-treatment at about 100° C., an equilibrium CO 2 sorption capacity from 80% to 105% of the equilibrium CO 2 sorption capacity of otherwise identical pre-treated but unsteamed H-form DDR framework type crystals; and
following a pre-treatment at about 400° C., an equilibrium CO 2 sorption capacity from 80% to 105% of the equilibrium CO 2 sorption capacity of otherwise identical pre-treated but unsteamed H-form DDR framework type crystals.

2. The method of claim 1 , wherein the reaction mixture has a ratio of water to silicon oxide from about 12 to about 25 and a ratio of silicon oxide to structure directing agent of about 0.01 to about 1.0, and wherein the recovered DDR framework-type crystals have an axis ratio of 1.1 or less, the axis ratio being a ratio of a vertex-to-vertex distance and an edge-to-edge distance, a depth dimension being less than the vertex-to-vertex distance and the edge-to-edge distance.

3. The method of claim 2 , wherein the axis ratio is 1.05 or less.

4. The method of claim 2 , wherein less than 10 volume percent of the ZSM-58 crystals have a characteristic size of about 5 μm or less.

5. The method of claim 2 , wherein the reaction mixture further comprises from about 0.05 wt % to about 5.0 wt % seed crystals based on the total weight of the reaction mixture.

6. The method of claim 2 , wherein the structure directing agent is methyltropinium chloride and the DDR framework type crystals substantially comprise ZSM-58.

7. The method of claim 2 , wherein the reaction mixture is maintained at a temperature of about 120° C. to about 175° C. during formation of the DDR framework type crystals.

8. The method of claim 2 , wherein a ratio of the depth dimension to the edge-to-edge distance is about 0.9 or less.

9. The method of claim 1 , wherein the reaction mixture has a ratio of silicon oxide to alkali or alkaline earth metal of about 0.01 to about 1.0, and wherein the recovered DDR framework-type crystals have a unimodal volume versus crystal size distribution where less than 10 volume percent of the DDR framework type crystals have a characteristic size of about 5 μm or less, a crystal size for a peak in the volume versus crystal size distribution is about 15 μm to about 40 μm, and a peak height in the volume versus crystal size plot with a 1 μm bin width is at least about 10 volume percent.

10. The method of claim 9 , wherein the mixture comprises from about 0.05 wt % to about 1.0 wt % of seeds relative to the weight of the mixture.

11. The method of claim 9 , wherein the structure directing agent is methyltropinium chloride and the DDR framework type crystals substantially comprise ZSM-58.

12. The method of claim 9 , wherein the reaction mixture is maintained at a temperature of about 120° C. to about 175° C. during formation of the DDR framework type crystals.

13. The method of claim 9 , wherein a ratio of the depth dimension to the edge-to-edge distance is about 0.9 or less.

14. The method of claim 9 , wherein the reaction mixture has a ratio of water to silicon oxide of about 12 to about 25.

15. The method of claim 9 , wherein the unimodal volume versus crystal size distribution further comprises a volume versus crystal size distribution where the difference between crystal sizes at volumes corresponding to half of the peak height is about the crystal size for the peak or less.

16. The method of claim 9 , wherein the recovered DDR framework type crystals have an axis ratio of 1.1 or less, the axis ratio being a ratio of a vertex-to-vertex distance and an edge-to-edge distance, a depth dimension being less than the vertex-to-vertex distance and the edge-to-edge distance.

17. The method of claim 1 , wherein the reaction mixture further comprises an alumina source.

18. The method of claim 17 , wherein the reaction mixture has a SiO 2 :Al 2 O 3 ratio of at least 3000.

19. The method of claim 1 , wherein the steaming is done in a rotary calciner at a temperature from 900° C. to 1100° C. in an atmosphere comprising from about 35 vol % to about 65 vol % steam to attain a methane diffusivity of at most 6.0E-13 m 2 /s.

Assignees

• Johnson Ivy D
• Beutel Tilman W
• Ravikovitch Peter I
• Deckman Harry W
• Johnson Jack W
• Beeckman Jean W
• Fassbender Natalie A
• Hrycenko Nadya A
• Smiley Randolph J
• Exxonmobil Res & Eng Co

Inventors

• Johnson Ivy D
• Beutel Tilman W
• Ravikovitch Peter I
• Deckman Harry W
• Johnson Jack W
• Beeckman Jean W
• Fassbender Natalie A
• Hrycenko Nadya A
• Smiley Randolph J

Classifications

• B01J20/30

  Processes for preparing, regenerating, or reactivating · CPC title

• B01J20/3085

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

• B01J20/282

  Porous sorbents (ion exchange B01J39/00 - B01J41/00) · CPC title

• B01J2220/80

  Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography · CPC title

• B01J20/186

  Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity · CPC title