CN110559871B

CN110559871B - Transfer promoting film

Info

Publication number: CN110559871B
Application number: CN201810578629.2A
Authority: CN
Inventors: 丁晓莉; 李晓峰; 王鑫兰; 赵红永; 张玉忠; 王琪; 李泓
Original assignee: Tianjin Polytechnic University
Current assignee: Tianjin Polytechnic University
Priority date: 2018-06-06
Filing date: 2018-06-06
Publication date: 2022-05-24
Anticipated expiration: 2038-06-06
Also published as: CN110559871A

Abstract

The invention relates to the field of macromolecules, in particular to a membrane technology and a nanotechnology, and particularly relates to a transfer-promoting membrane.

Description

Transfer promoting film

Technical Field

The invention relates to a high molecular technology, a nanotechnology and a membrane separation technology, in particular to a separation membrane with a transfer promotion function.

Background

The membrane separation technology is one of six high and new technologies in the world at present, and becomes the basis of an important high and new technology and a sustainable development technology for solving the problems of current energy, resources, environmental pollution and the like. The membrane technology has been regarded as a high-tech technology that has been developed preferentially in the 21 st century in western developed countries such as the united states and japan, and has been widely used in many fields such as separation, concentration, and purification of substances. Due to the problems of global warming and the like, energy conservation and emission reduction are not slow. The separation membrane technology is a hot spot due to the advantage of low energy consumption. Separation membranes are the core of gas membrane separation technology. The polymer membrane has the advantages of mature membrane forming technology and the like, but is limited by the upper limit of Robinson, so that the polymer membrane is difficult to have high gas permeability and separation performance at the same time. While inorganic materials are not limited by the upper limit of robinson, inorganic membranes are expensive and the production technology is not mature, making it difficult to produce large-scale defect-free gas separation membranes. Blending the matrix membrane and the facilitated transport membrane is the primary method to solve this problem. In particular, the promotion of the transfer membrane is an important way to increase the separation factor. The delivery-promoting membrane refers to a membrane which contains functional groups or structural units capable of undergoing reversible chemical reactions with target components in the membrane, and the reversible chemical reactions are used for enhancing the delivery of the target components in the membrane. Currently, there are two main types of facilitated transport membranes: a supported liquid membrane (moving carrier membrane) and a fixed carrier membrane. The supported liquid membrane has the problems of easy carrier loss, instability, short service life and the like; although the fixed carrier film solves the problem of carrier loss, the carrier is fixed on the polymer film, so that the fluidity is poor, and the permeability and the selectivity are low.

Disclosure of Invention

The invention aims to provide a transfer-promoting membrane, which encapsulates a carrier in polymer nano microspheres and is combined with other polymers to prepare a blended matrix membrane.

The carrier is in liquid form, and can be a carrier which is in liquid form per se, or can be a carrier-containing solution, a carrier-containing suspension, a carrier-containing microemulsion, a carrier-containing emulsion, that is, the transfer-promoting film provided by the invention is essentially a liquid film. The liquid carrier is encapsulated within the polymer microspheres. The particle size of the polymer microsphere is 5-1000 nm. Because the liquid carrier is encapsulated in the polymer microspheres, the carrier is not easy to lose in use, and the problem of short service life of the supported liquid film can be solved.

The microsphere for encapsulating the carrier is made of a polymer material, wherein the polymer material is selected from at least one of polysulfones, polyether sulfones, polyimides, silicone rubbers, polycarbonates, celluloses, chitosan, polyether imides, polyester carbonates, polyethylene oxides, polypyrrolidone, polyetheramides, polyamides, polyethylenes, polystyrenes, polyethers, polypropylenes, polyether ketones, polyether ether ketones, polyaryl ethers, polydiisocyanates, polyurethanes, polyesters, polycarbodiimides, copolymers containing the repeating units, and graft and blend polymers containing the polymers.

The polymer matrix is selected from at least one of polysulfones, polyether sulfones, polyimides, silicone rubbers, polycarbonates, celluloses, chitosan, polyether imides, polyester carbonates, polyethylene oxides, polypyrrolidone, polyetheramides, polyamides, polyethylenes, polystyrenes, polyethers, polypropylenes, polyether ketones, polyether ether ketones, polyaryl ethers, polyisocyanates, polyurethanes, polyesters, polycarbodiimides, and copolymers, grafts and blend polymers containing the above repeating units. In fact, the polymer matrix and the polymeric microspheres may employ any one polymer or a mixture of polymers.

The mass ratio of the polymer matrix to the polymer microspheres encapsulating the carrier is as follows: 10: 90 to 95: 5.

The invention has the following advantages: the carrier is in a liquid form, which is beneficial to mass transfer; the carrier is encapsulated in the microsphere, so that the loss of the carrier can be avoided while the mobility of the carrier is maintained; the encapsulated microspheres and the polymer matrix are both prepared from polymers, and the compatibility problem generated during organic/inorganic blending can be avoided.

Drawings

The attached drawing is a schematic diagram of a transfer-promoting membrane fixed with a liquid carrier

Detailed Description

Example 1

Preparing an aqueous solution containing 0.5 wt% of polyethylene glycol diacrylate, 5 wt% of polyethylene glycol acrylate, 0.5 wt% of tetraethylenepentamine and 0.6 wt% of polyamide-amine dendrimer, preparing the aqueous solution, toluene and ethanol into a microemulsion, adding 0.3 wt% of benzoyl peroxide (calculated according to the mass of toluene) to react for 4 hours, and adding 30 wt% of polysulfone (calculated according to the mass of toluene). And (4) defoaming after the polysulfone is completely dissolved. Scraping a flat membrane on the polysulfone porous support membrane, and then putting the flat membrane into water to be solidified into a membrane. And (5) cleaning, drying and testing. CO at 25 deg.C and 5atm₂Flux 25000GPU, CO₂/O₂The separation factor was 800.

Example 2

Preparing an aqueous solution containing 0.3 wt% of pentaerythritol triacrylate, 5 wt% of polyethylene glycol acrylate, 0.5 wt% of tetraethylenepentamine and 0.5 wt% of Co (Salen), preparing the aqueous solution, toluene and ethanol into a microemulsion, adding 0.3 wt% of benzoyl peroxide (calculated by the mass of toluene) to react for 4 hours, and adding 35 wt% of polyether sulfone (calculated by the mass of toluene). And (4) defoaming after the polyether sulfone is completely dissolved. Spinning with the mixed solution to obtain hollow fiber membrane at 25 deg.C and 5atm₂Flux 500GPU, O₂/N₂The separation factor was 40.

Example 3

Preparing an aqueous solution containing 1 wt% of copper sulfate and 0.12 wt% of m-phenylenediamine, and preparing the aqueous solution, n-hexane and isopropanol into microemulsion according to the mass ratio of 0.3: 0.25: 0.45; dissolving a certain amount of trimesoyl chloride (0.1 percent of the mass of the normal hexane in the microemulsion) in the microemulsion for reactionAfter 5min, a certain amount of silicon rubber, a catalyst and a cross-linking agent are added, and after uniform stirring, a film is poured. The flat membrane obtained at 25 deg.C and 5atm is prepared from₂H₄Flux 1000GPU, C₂H₄/C₂H₆The separation factor was 800.

The above two examples do not indicate a limited scope of application of the patent. Any person skilled in the art can easily apply the teachings of the patent to any other possible system, such as a combination of inorganic microspheres and an inorganic matrix, a combination of inorganic microspheres and an organic matrix, a combination of organic microspheres and an inorganic matrix, etc.

Claims

1. A method for preparing a facilitated transport membrane, comprising: preparing an aqueous solution containing 0.5 wt% of polyethylene glycol diacrylate, 5 wt% of polyethylene glycol acrylate, 0.5 wt% of tetraethylenepentamine and 0.6 wt% of polyamide-amine dendrimer, preparing the aqueous solution, toluene and ethanol into microemulsion, adding 0.3 wt% of benzoyl peroxide according to the mass of the toluene, reacting for 4 hours, and adding 30 wt% of polysulfone according to the mass of the toluene; defoaming after the polysulfone is completely dissolved; scraping a flat membrane on the polysulfone porous support membrane, and then putting the flat membrane into water to be solidified into a membrane.