Method for the high-throughput preparation of carbon nanotube hollow fiber membranes

Patent metadata

Field	Value
Publication number	US-10179314-B2
Application number	US-201415120637-A
Country	US
Kind code	B2
Filing date	Apr 28, 2014
Priority date	Mar 5, 2014
Publication date	Jan 15, 2019
Grant date	Jan 15, 2019

Abstract

The invention, belonging to the field of membrane technology, presents a method for the high-throughput preparation of carbon nanotube hollow fiber membranes. This method contains three major steps. Firstly, the pristine carbon nanotubes (CNTs) are added into a mixture of concentrated nitric acid and sulfuric acid, which is then heated at 40˜80° C. for 0.5˜6 hours. Secondly, the surface-functionalized CNTs and polyvinyl butyral (PVB) are dispersed and dissolved, respectively, in organic solvents at a mass ratio of 1:0.2˜1:4˜8 to form homogeneous spinning solution, which is squeezed into water as shell liquid with water as core liquid at a flow rate ratios of 0.5˜5:1 through a spinneret to form CNT/PVB hollow fibers. Finally, the dry fibers are calcinated at 600˜1000 ° C. for 1˜4 hours in absence of oxygen to produce free-standing CNT hollow fiber membranes. The method involved in this invention is simple and highly efficient without needing any templates, expensive apparatuses and chemicals. Additionally, the obtained electrically conductive CNT hollow fiber membranes feature a high porosity, high water flux and strong acid/alkali resistance.

First claim

We claim:

1. A method for the high-throughput preparation of carbon nanotube hollow fiber membranes comprises:
(1) surface modification of pristine CNTs: carbon nanotubes (CNTs) are added into a mixture of concentrated sulfuric acid and nitric acid with a volumetric ratio of sulfuric acid to nitric acid of ≤5:1, which is heated at 40˜80° C. for 0.5˜6 hours; CNTs are then recovered by filtration;
(2) wet-spinning process: the surface-functionalized CNTs and polyvinyl butyral (PVB) are dispersed and dissolved, respectively, in an organic solvents at a mass ratio of 1:0.2˜1:4˜8 to produce a homogeneous spinning solution; the spinning solution and water as shell liquid and core liquid, respectively, are squeezed at a flow rate ratio of 0.5˜5:1 into water through a spinneret to form CNT/PVB hollow fibers;
(3) calcination: the obtained fibers are dredged up from the water and dried after being washed for several times, followed by being calcinated at 600˜1000° C. for 1˜4 hours in absence of oxygen to form free-standing CNT hollow fiber membranes;
wherein the spinning solution involved in Step (2)contains polymeric additives, and the mass ratio of the polymeric additives to CNTs is ≤0.2.

2. According to claim 1 , the polymeric additives are polyacrylonitrile or poly (vinylidene fluoride) or sulfonated polyphenyleneoxide, or a mixture of several kinds of them.

3. According to claim 2 , the organic solvents involved in Step (2) are N,N-dimethyl formamide or N,N-dimethyl acetamide or N-methyl pyrrolidone, or a mixture of several kinds of them.

4. According to claim 2 , the CNTs involved in Step (1) are single-walled CNTs or double-walled CNTs or multiwalled CNTs, or a mixture of several kinds of them.

5. According to claim 1 , the organic solvents involved in Step (2) are N,N-dimethyl formamide or N,N-dimethyl acetamide or N-methyl pyrrolidone, or a mixture of several kinds of them.

6. According to claim 5 , the CNTs involved in Step (1) are single-walled CNTs or double-walled CNTs or multiwalled CNTs, or a mixture of several kinds of them.

7. According to claim 1 , the CNTs involved in Step (1) are single-walled CNTs or double-walled CNTs or multiwalled CNTs, or a mixture of several kinds of them.

Assignees

• Univ Dalian Tech

Inventors

• Quan Xie
• Wei Gaoliang
• Chen Shuo
• Yu Hongtao

Classifications

• B01D67/0079 Primary

  Manufacture of membranes comprising organic and inorganic components · CPC title

• B82B3/0009

  Forming specific nanostructures · CPC title

• B01D69/08 Primary

  Hollow fibre membranes (manufacture of hollow fibres D01D5/24, D01F1/08) · CPC title

• B01D2325/26

  Electrical properties · CPC title

• B01D71/32

  containing fluorine atoms · CPC title