Method for preparing defect-free DDR molecular sieve membrane

Patent metadata

Field	Value
Publication number	US-11278846-B2
Application number	US-201716470230-A
Country	US
Kind code	B2
Filing date	Jun 9, 2017
Priority date	Dec 16, 2016
Publication date	Mar 22, 2022
Grant date	Mar 22, 2022

Abstract

Provided is a method for preparing a defect-free DDR molecular sieve membrane. Sigma-1 molecular sieve is used as an inducing seed crystal to prepare and obtain a continuous and compact DDR molecular sieve membrane on the surface of a porous ceramic support. An ozone atmosphere or an external field assisted technology is used to remove a template in the pores of the molecular sieve membrane at a low temperature. The invention avoids the formation of intercrystal defects and cracks, an activated DDR molecular sieve membrane has a good selectivity for separating CO2, and the membrane preparation time is significantly reduced.

First claim

What is claimed is:

1. A method for preparing a defect-free DDR zeolite membrane, comprising the following steps:
Step 1 preparing a support loaded with seed crystals: adding Sigma-1 seed crystals into water to prepare a seed crystal suspension, and applying the seed crystal suspension on the surface of the porous support to obtain seed crystals;
Step 2 synthesizing a DDR zeolite membrane: mixing and aging amantadine (ADA), silica source, ethylenediamine (EN) and water as a synthesis liquid; and adding the support loaded with seed crystal into the synthesis liquid for hydrothermal synthesis to generate a DDR zeolite membrane;
Step 3 activating DDR zeolite membrane: treating the synthesized DDR zeolite membrane in an ozone atmosphere or by an external field assisted technology to remove the template ADA, thus obtaining the defect-free DDR zeolite membrane,
wherein the aging parameters in the step 2 are as follows: aging at 20-120° C. for 1-10 h; the molar ratio of ADA, silica source, EN and water is: ADA/SiO 2 =0.01-0.2, EN/ADA=8-32, H 2 O/ADA=20-50; and the parameters of hydrothermal synthesis step are: synthesizing at 130-170° C. for 12 h-4 d.

2. The method for preparing a defect-free DDR zeolite membrane according to claim 1 , wherein the mass concentration of the Sigma-1 seed crystal in water is 0.2-2%; and the time for applying the seed crystal suspension is 5-50 s in the step 1.

3. The method for preparing a defect-free DDR zeolite membrane according to claim 1 , wherein the Sigma-1 zeolite used in the step 1 can be directly obtained by hydrothermal synthesis or treated by a high-energy ball milling method.

4. The method for preparing a defect-free DDR zeolite membrane according to claim 1 , wherein the porous support used in the step 1 is a flat plate, tubular or hollow fiber support.

5. The method for preparing a defect-free DDR zeolite membrane according to claim 1 , wherein the method for applying the seed crystal suspension may be selected from one or more of the following methods: spin coating, wiping coating, dip coating or vacuum pumping in the step 1.

6. The method for preparing a defect-free DDR zeolite membrane according to claim 1 , wherein the as-synthesized DDR zeolite membrane is treated in an ozone atmosphere or by an external field assisted technology for 10-100 h at 20-300° C., with the heating rate being 0.5-2° C./min in the step 3.

7. The method for preparing a defect-free DDR zeolite membrane according to claim 1 , wherein the external field assisted technology is selected from one or more of the following methods: ultraviolet irradiation, microwave digestion or Fenton reaction in the step 3.

8. The method for preparing a defect-free DDR zeolite membrane according to claim 7 , wherein the ultraviolet irradiation intensity is 50-600 mW/cm 2 ; the digestion solution used in the microwave digestion is a mixed solution of nitric acid and hydrogen peroxide, the power of the microwave digestion instrument is 500-2000 W, and the digestion temperature is 90-250° C.; the Fenton reagent in the Fenton reaction is a mixed solution of ferrous sulfate solution and hydrogen peroxide; wherein FeSO 4 .7H 2 O is added into the reaction solution, and the Fe 2+ concentration is controlled to be 4.0-15.0 mmol/L and the H 2 O 2 mass concentration is controlled to be 1.0-10.0%.

Assignees

• Nanjing University Of Technology

Inventors

• Gu Xuehong
• Wang Lin
• Zhang Chun

Classifications

• B01D2323/081

  Heating · CPC title

• B01D69/108

  Inorganic support material · CPC title

• B01D71/0281

  Zeolites · CPC title

• B01D53/229

  Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption) · CPC title

• C01B37/02 Primary

  Crystalline silica-polymorphs, e.g. silicalites {dealuminated aluminosilicate zeolites} · CPC title