Ceramic membrane technology for molecule-range separation

Patent metadata

Field	Value
Publication number	US-12496557-B2
Application number	US-202117924298-A
Country	US
Kind code	B2
Filing date	May 12, 2021
Priority date	May 12, 2020
Publication date	Dec 16, 2025
Grant date	Dec 16, 2025

Abstract

A method of producing a silicalite membrane, which includes heating an aqueous solution that includes a dopant precursor and structure-directing template agents to form silicalite seeds incorporated with a dopant, depositing a buffer layer on a ceramic substrate prior to depositing the silicalite seeds on the buffer layer, contacting the ceramic substrate with a solution including the silicalite seeds to form a silicalite layer from the silicalite seeds on the ceramic substrate, and removing the structure-directing template agents to form the silicalite membrane, where the silicalite layer includes silicalite crystals incorporated with a dopant and each of the silicalite crystals has a hollow structure which forms the pores of the silicalite layer. The silicalite membrane includes a ceramic substrate having a buffer layer formed thereon, and a silicalite layer formed on the buffer layer, where the silicalite layer includes silicalite crystals incorporated with a dopant.

First claim

The invention claimed is:

1 . A method of producing a silicalite membrane, the method comprising:
heating an aqueous solution comprising a dopant precursor and structure-directing template agents to form silicalite seeds incorporated with a dopant, wherein the dopant precursor comprises cerium nitrate hexahydrate, tin chloride pentahydrate, cobalt (II) nitrate hexahydrate, gallium trichloride, indium acetate, yttrium trichloride, or a mixture thereof; depositing a buffer layer on a ceramic substrate prior to depositing the silicalite seeds on the buffer layer; contacting the ceramic substrate with a solution comprising the silicalite seeds to form a silicalite layer from the silicalite seeds on the ceramic substrate; and removing the structure-directing template agents to form the silicalite membrane, wherein the silicalite layer comprises silicalite crystals incorporated with a dopant and each of the silicalite crystals has a hollow structure which forms the pores of the silicalite layer.

2 . The method of claim 1 , wherein heating the aqueous solution comprises mixing the structure-directing template agents in water, wherein the structure-directing template agents comprise tetrapropylammonium hydroxide and tetraethyl orthosilicate.

3 . The method of claim 1 , wherein heating the aqueous solution comprises:
mixing the dopant precursor and the structure-directing template agents to form the aqueous solution; and subjecting the aqueous solution to hydrothermal treatment at a temperature of 100° C. to 200° C. to form the silicalite seeds and then cooling the aqueous solution comprising the silicalite seeds.

4 . The method of claim 1 , further comprising:
centrifuging the aqueous solution comprising the silicalite seeds to retrieve the silicalite seeds; adding water to the silicalite seeds; repeating the centrifuging and the adding of water until a liquid suspension comprising the silicalite seeds and having a pH of 7 to 8 is attained; drying the liquid suspension; and grinding the silicalite seeds and then calcinating the silicalite seeds at 500° C. to 600° C.

5 . The method of claim 1 , wherein depositing the buffer layer comprises:
heating an acidic solution comprising tetraethyl orthosilicate and an alcohol and then cooling the acidic solution; mixing a surfactant with an extract of the acidic solution, wherein the surfactant comprises hexadecyltrimethylammonium bromide; and heating the surfactant and the extract of acidic solution to form a buffer layer solution.

6 . The method of claim 1 , wherein the ceramic substrate comprises zeolite, aluminum oxide, titanium oxide, zirconium oxide, or a mixture thereof.

7 . The method of claim 1 , wherein depositing the buffer layer comprises:
sealing both ends of the ceramic substrate, wherein the ceramic substrate has a tubular configuration; immersing the ceramic substrate in the buffer layer solution; removing the ceramic substrate at a speed of 1 mm/s to 5 mm/s from the buffer layer solution; and calcinating the ceramic substrate having the buffer layer solution thereon at 400° C. to 600° C. to have the buffer layer deposited on the ceramic substrate.

8 . The method of claim 7 , wherein immersing the ceramic substrate in the buffer layer solution comprises immersing the ceramic substrate in the buffer layer solution for at least 1 minute.

9 . The method of claim 1 , wherein contacting the ceramic substrate with the solution comprising the silicalite seeds comprises:
sealing both ends of the ceramic substrate having the buffer layer deposited thereon; immersing the ceramic substrate having the buffer layer deposited thereon in the solution comprising the silicalite seeds; removing the ceramic substrate having the buffer layer deposited thereon from the solution comprising the silicalite seeds at a speed of 1 mm/s to 5 mm/s; drying the ceramic substrate having the silicalite seeds deposited thereon; and repeating the immersing, the removing and the drying steps one or more times.

10 . The method of claim 9 , wherein immersing the ceramic substrate having the buffer layer deposited thereon in the solution comprising the silicalite seeds comprises immersing the ceramic substrate having the buffer layer deposited thereon in the solution comprising the silicalite seeds for at least 1 minute.

11 . The method of claim 1 , further comprising:
providing a growth solution comprising silicalite seeds; immersing the ceramic substrate having the silicalite seeds deposited thereon in the growth solution; and subjecting the ceramic substrate immersed in the growth solution to hydrothermal treatment at a temperature of 100° C. to 200° C. to grow the silicalite seeds on the ceramic substrate.

12 . The method of claim 11 , wherein providing the growth solution comprises mixing tetrapropylammonium hydroxide and tetraethyl orthosilicate with the dopant precursor in water to form the growth solution.

13 . The method of claim 1 , wherein removing the structure-directing template agents comprises calcinating the ceramic substrate having the silicalite seeds deposited thereon at a temperature of 500° C. to 600° C.

Assignees

• Agency Science Tech & Res

Inventors

• Dong Xuecheng
• Saw Eng Toon
• Ang Kun Liang
• He Wei

Classifications

• B01D71/0281

  Zeolites · CPC title

• B01D69/10

  Supported membranes; Membrane supports · CPC title

• B01D2323/48

  Influencing the pH · CPC title

• B01D2323/24

  Use of template or surface directing agents [SDA] · CPC title

• B01D69/04

  Tubular membranes · CPC title