Zeolite membrane complex, method of producing zeolite membrane complex, and hydrothermal synthesis apparatus

Patent metadata

Field	Value
Publication number	US-11865499-B2
Application number	US-202117177402-A
Country	US
Kind code	B2
Filing date	Feb 17, 2021
Priority date	Feb 21, 2020
Publication date	Jan 9, 2024
Grant date	Jan 9, 2024

Abstract

A zeolite membrane complex includes a longitudinal support member having at least one through hole extending along its length and a zeolite membrane on an inner peripheral surface of the through hole or over an outer peripheral surface of the support, from one end portion of the support to the other end portion thereof. Among constituent elements of the zeolite membrane except oxygen, an element with the highest percentage is a main element, and when the concentration of the main element is measured at three portions defined by dividing the support into three equal parts in the longitudinal direction, the concentration of the main element gradually decreases from the one end portion toward the other end portion, and the ratio of the concentration of the main element at the other end portion to that at the one end portion is 0.90 or more.

First claim

The invention claimed is:

1. A zeolite membrane complex, comprising:
a support which is a longitudinal member having a length of 50 cm or more and has at least one through hole extending in a longitudinal direction; and
a zeolite membrane provided over an inner peripheral surface of said at least one through hole in said support or over an outer peripheral surface of said support, from one end portion of said support in said longitudinal direction to the other end portion thereof,
wherein among constituent elements of said zeolite membrane except oxygen, an element with the highest percentage is assumed as a main element, and in a case where the concentration of said main element of said zeolite membrane is measured at three portions defined by dividing said support into three equal parts in said longitudinal direction, said concentration of said main element gradually decreases from a portion on said one end portion side toward a portion on said other end portion side, and the ratio of said concentration of said main element at said portion on said other end portion side to that at said portion on said one end portion side is 0.90 or more and 0.983 or less.

2. A zeolite membrane complex, comprising:
a support which is a longitudinal member having a length of 50 cm or more and has at least one through hole extending in a longitudinal direction; and
a zeolite membrane provided over an inner peripheral surface of said at least one through hole in said support or over an outer peripheral surface of said support, from one end portion of said support in said longitudinal direction to the other end portion thereof,
wherein among constituent elements of said zeolite membrane except oxygen, an element with the highest percentage is assumed as a main element, and in a case where the concentration of said main element of said zeolite membrane is measured at a plurality of measurement points including respective points on three portions defined by dividing said support into three equal parts in said longitudinal direction, among concentrations of said main element at said plurality of measurement points, a concentration having the maximum absolute value of a difference from an average value of all the concentrations is specified, and an overall evaluation value obtained by dividing the absolute value of the difference of said concentration from said average value by said average value is 3% or more and 15% or less.

3. The zeolite membrane complex according to claim 2 , wherein
a plurality of through holes are provided in said support along a radial direction from a central axis extending in said longitudinal direction and said zeolite membrane is provided on inner peripheral surfaces of said plurality of through holes, and
two or more measurement points set on said inner peripheral surfaces of two or more through holes, respectively, at a predetermined position in said longitudinal direction among said plurality of through holes, are included in said plurality of measurement points.

4. The zeolite membrane complex according to claim 2 , wherein
a single through hole extending in said longitudinal direction is provided in said support and said zeolite membrane is provided on said outer peripheral surface of said support, and
two or more measurement points set on said outer peripheral surface along a circumferential direction at a predetermined position in said longitudinal direction are included in said plurality of measurement points.

5. The zeolite membrane complex according to claim 3 , wherein
among concentrations of said main element at said two or more measurement points, a concentration having the maximum absolute value of a difference from an average value of the concentrations is specified and a partial evaluation value obtained by dividing the absolute value of the difference of said concentration from said average value by said average value is 10% or less.

6. The zeolite membrane complex according to claim 1 , wherein
the thickness of said zeolite membrane is not larger than 5 μm.

7. The zeolite membrane complex according to claim 2 , wherein
the thickness of said zeolite membrane is not larger than 5 μm.

8. A method of producing a zeolite membrane complex according to claim 1 , comprising:
a) preparing a longitudinal support having a length of 50 cm or more; and
b) forming a zeolite membrane on said support by immersing said support in a starting material solution for zeolite membrane formation and performing hydrothermal synthesis,
wherein while said starting material solution is heated at a predetermined synthesis temperature in said hydrothermal synthesis, the temperature gradient of said starting material solution between respective positions facing one side and the other side of said support in a longitudinal direction ranges from 0.1 to 10° C./m.

9. The method of producing a zeolite membrane complex according to claim 8 , wherein
until said starting material solution is heated to said synthesis temperature in said hydrothermal synthesis, the temperature gradient of said starting material solution between said respective positions facing said one side and said other side of said support is not higher than 10° C./m.

10. The method of producing a zeolite membrane complex according to claim 8 , wherein
the ratio of the mass of said starting material solution to the area of a region of said support in which said zeolite membrane is formed ranges from 1 to 15 kg/m 2 .

11. The method of producing a zeolite membrane complex according to claim 8 , wherein
said support is held so that said longitudinal direction is a substantially vertical direction in said hydrothermal synthesis.

12. A method of producing a zeolite membrane complex according to claim 2 , comprising:
a) preparing a longitudinal support having a length of 50 cm or more; and
b) forming a zeolite membrane on said support by immersing said support in a starting material solution for zeolite membrane formation and performing hydrothermal synthesis,
wherein while said starting material solution is heated at a predetermined synthesis temperature in said hydrothermal synthesis, the temperature gradient of said starting material solution between respective positions facing one side and the other side of said support in a longitudinal direction ranges from 0.1 to 10° C./m.

13. The method of producing a zeolite membrane complex according to claim 12 , wherein
until said starting material solution is heated to said synthesis temperature in said hydrothermal synthesis, the temperature gradient of said starting material solution between said respective positions facing said one side and said other side of said support is not higher than 10° C./m.

14. The method of producing a zeolite membrane complex according to claim 12 , wherein
the ratio of the mass of said starting material solution to the area of a region of said support in which said zeolite membrane is formed ranges from 1 to 15 kg/m 2 .

15. The method of producing a zeolite membrane complex according to claim 12 , wherein
said support is held so that said longitudinal direction is a substantially vertical direction in said hydrothermal synthesis.

Assignees

• Ngk Insulators Ltd

Inventors

• Miyahara Makoto
• Noda Kenichi

Classifications

• B01D69/10

  Supported membranes; Membrane supports · CPC title

• B01D71/0281 Primary

  Zeolites · CPC title

• B01D71/028 Primary

  Molecular sieves (carbon B01D71/021) · CPC title

• B01D67/0051

  by controlled crystallisation, e,.g. hydrothermal growth · CPC title

• B01D69/02

  characterised by their properties · CPC title