Hollow fiber ceramic oxygen permeation membrane with dual composite asymmetric structure and preparation method thereof

Abstract

The invention belongs to the technical field of ceramic oxygen permeation membranes and particularly relates to a preparation method for a hollow fiber ceramic oxygen permeation membrane with a dual composite asymmetric structure. The preparation method comprises the following steps of: respectively preparing a membrane casting solution A and a membrane casting solution B which are different in oxygen permeation ceramic membrane material powder content, wherein the ceramic powder content of the membrane casting solution A is higher than that of the membrane casting solution B; spinning into a coagulation bath through a triple-concentric ring hole-contained spinning jet by taking the membrane casting solution A as an inner layer material and the membrane casting solution B as an outer layer material, solidifying, and then, forming; straightening and airing a solidified and formed hollow fiber membrane precursor; and sintering at high temperature to obtain the required hollow fiber oxygen permeation membrane. Compared with the ceramic oxygen permeation membranes prepared by a conventional method, the oxygen permeation rate of the hollow fiber ceramic oxygen permeation membrane with a dual composite asymmetric structure, which is prepared by the preparation method, is increased by 5.2-22 times, wherein the inner surface and outer surface of the hollow fiber ceramic oxygen permeation membrane are porous and the middle is compact. Moreover, one-time forming and one-time sintering are adopted. The process is simple, the operation is convenient, the membrane preparation cost is low, and industrial production can be conveniently implemented.

Description

technical field [0001] The invention belongs to the technical field of ceramic oxygen-permeable membranes, and in particular relates to a hollow fiber ceramic oxygen-permeable membrane with a double-composite asymmetric structure and a preparation method thereof. Background technique [0002] Ceramic oxygen permeable membrane is an inorganic membrane made of oxygen ion-electron mixed conductive ceramic material. At high temperature (>700°C), oxygen can be transferred from the high oxygen partial pressure side to the low oxygen partial pressure side in the form of oxygen ions. One side, so as to realize the separation of oxygen. It has high oxygen permeability selectivity (up to 100% in theory), fast oxygen permeability rate (2 to 3 orders of magnitude faster than organic membrane), low cost of oxygen production (30 to 50 times lower than traditional cryogenic distillation or PSA method) %), simple process and operation (single-stage oxygen production), wide range of appl...

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Problems solved by technology

[0004] In order to further improve the oxygen transmission rate of the hollow fiber ceramic oxygen permeable membrane, catalytic modification of the membrane surface is a very effective method (CN200810016884.4; CN 200810016721.6; F.M. Figueiredo, Surface enhanced oxygen permeation in CaTi 1-x Fe x o 3-δ ceramic membranes, J. Membr. Sci. 236 (2004) 73–80; A. Leo, The enhancement of oxygen flux on Ba 0.5 Sr 0.5 co 0.8 Fe 0.2 o 3- δ (BSCF) hollow fibers using silver surface modification, J. Membr. Sci. 340 (2009) 148–153; A. Thursfield, Air separation using a catalytically modified mixed conducting ceramic hollow fiber membrane module, J. Membr. Sci. 288 (2007) 175–187), however, all of these works are to carry out catalytic loading or surface modification on one side of the hollow fiber membrane, and the main disadvantage is that catalyst loading or surface modification is an additional process , which complicates the process, which will inevitably greatly increase the production and application costs of the hollow fiber ceramic oxygen permeable membrane

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