CN110787659A - Preparation method of polyether block amide and amino modified multi-walled carbon nanotube doped mixed film - Google Patents

Preparation method of polyether block amide and amino modified multi-walled carbon nanotube doped mixed film Download PDF

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CN110787659A
CN110787659A CN201910970481.1A CN201910970481A CN110787659A CN 110787659 A CN110787659 A CN 110787659A CN 201910970481 A CN201910970481 A CN 201910970481A CN 110787659 A CN110787659 A CN 110787659A
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membrane
solvent
mixed matrix
mwnts
pebax
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宋春风
穆扎德
李润
张泽洲
曹良臣
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a polyether block amide and amino modified multi-walled carbon nanotube doped mixed matrix membrane (Pebax/MWNTs-NH)2) The preparation method mainly comprises the following steps: 1) dissolving Pebax/MWNTs-NH by using solvent2Preparing mixed matrix membrane solution, and preparing the mixed matrix membrane by adopting a wet phase conversion technology. Dissolving the MWNTs-NH dried in vacuum with NMP (95 wt%) solvent2And stirring for 60 min. Then performing ultrasonic treatment at 27 deg.CWave treatment for 30 min. Purifying with isopropanol-washed Pebax 1657(5 wt.%), adding into the prepared solvent, and refluxing at 120 deg.C for 3 hr; 2) the prepared mixed matrix solution is used for preparing a membrane, the matrix solution is injected into a model, the solvent is evaporated and dried for 6 hours at 70 ℃, then the membrane is dried overnight at 50 ℃ in a vacuum environment, and the prepared membrane is placed into n-hexane for soaking. Compared with the method for preparing the mixed matrix membrane by using ethanol/water (70/30 wt%) as a solvent, the method can effectively improve the permeability and selectivity of the mixed matrix membrane by using the solvent (NMP) with relatively large molecular weight.

Description

Preparation method of polyether block amide and amino modified multi-walled carbon nanotube doped mixed film
Technical Field
The invention relates to the technical field of membrane separation, in particular to a method for preparing Pebax/MWNTs-NH for separating gas by embedding an amino-modified multi-walled carbon nanotube into the surface of Pebax2A method of mixing a matrix membrane.
Background
Membrane separation is based on the relative permeability of a polymer membrane to different gases. When containing CO2When the industrial waste gas passes through the membrane separator, CO2Selectively absorbing into membrane, diffusing to low pressure side to form permeate gas, and leaving gas without permeate gas as retained gas at high pressure side as retentate gas to remove CO2. The membrane separation technology has the advantages of low investment, low energy consumption, compact equipment, convenient maintenance and the like, and is generally concerned as a carbon dioxide capture technology.
Gas separation by selective transport through polymer membranes is one of the fastest growing branches of membrane technology. However, the existing polymer membrane materials are not enough to fully utilize the application opportunities of industrial scale; the increase in permeability is at the expense of selectivity and vice versa. A novel membrane material with potential application prospect is a mixed matrix material consisting of a polymer with uniform interpenetration and an inorganic particle matrix. The separation performance of the synthesized Mixed Matrix Membranes (MMMs) is expected to be significantly improved with little loss of membrane elasticity compared to the original polymer membranes. However, the mixed matrix membrane is easy to generate defects on the membrane surface due to the addition of inorganic particles, so that the selectivity of the membrane is influenced.
The invention provides a Pebax/MWNTs-NH for gas separation2Process for the preparation of a mixed matrix film, in which polyvinyl alcohol (ether-block-amide) is a thermoplastic elastomerThe product name is Pebax, which is a promising CO2Separating the material. In recent years, Carbon Nanotubes (CNTs) have attracted much attention due to their excellent mechanical properties and rapid transport of gases. The method for preparing the mixed matrix membrane for separating carbon dioxide by taking polyvinyl alcohol and carbon nano tubes as materials has a great deal of research and has wide application prospect. On the other hand, the Pebax and MWNTs-NH are increased by adopting the large molecular volume PAN2Solubility, and preparing a mixed matrix membrane with better separation performance.
Disclosure of Invention
The invention aims to provide a Pebax/MWNTs-NH for gas separation2A method for preparing a mixed matrix membrane. Selecting reasonable solvent and concentration thereof to prepare high-performance CO2And (3) testing the selectivity and permeability of the separated mixed matrix membrane under different conditions, and observing the membrane characterization and an influence mechanism thereof by observing a scanning electron microscope.
The technical scheme of the invention is a preparation method of a mixed plasma membrane doped with polyether block amide and amino modified multi-walled carbon nanotubes, which comprises the following steps:
1) materials: pebax MH 1657; amino modified multi-walled carbon nanotube (MWNTs-NH)2) (ii) a Methylpyrrolidone (95 wt.% NMP);
2) preparation of mixed matrix membrane: preparing mixed matrix membrane by wet phase conversion technique, dissolving MWNTs-NH dried in vacuum with NMP (95 wt%) solvent2And stirring for 60 min. Then, the mixture is subjected to ultrasonic treatment at 27 ℃ for 30 min. Purifying with isopropanol-washed Pebax 1657(5 wt.%), adding into the prepared solvent, and refluxing at 120 deg.C for 3 hr;
preparing membrane with the above mixed matrix solution, injecting the matrix solution into a mold, evaporating and drying at 70 deg.C for 6 hr, drying at 50 deg.C under vacuum for one night, soaking the prepared membrane in n-hexane, and storing
3) The separation performance of the membranes was measured at different temperatures and pressures.
The solvent in step 2) is preferably NMP (95 wt%) solvent.
The Pebax 1657 concentration in said step 2) is preferably 5 wt.%.
MWNTs-NH in the mixed solution in the step 2)2The mass fraction is preferably 6%.
Compared with the prior art, the invention has the advantages that:
the technique adopts different solvents to finish Pebax/MWNTs-NH2Preparation of mixed matrix membrane. Preparation of Pedax/MWNTs-NH by Using Methylpyrrolidone (NMP) as solvent2The matrix membrane was mixed. The use of a solvent with a relatively large molecular mass (NMP) effectively increases the permeability and selectivity of the mixed matrix membrane compared to the mixed matrix membrane prepared using ethanol/water (70/30% wt%) as the solvent. The permeability test result is improved by 327 percent and is adjusted by 375 percent relative to the original membrane permeability. Through comparison of final test results, the Pebax/MWNTs-NH is prepared by using NMP with larger relative molecular mass as a solvent2A mixed matrix membrane having more excellent separation characteristics.
Drawings
FIG. 1 shows a comparison of separation characteristics of mixed matrix membranes prepared with different solvents;
FIG. 2 NMP solvent, 6% MWNTs-NH2And 3% MWNTs-NH2A graph of selectivity changes at different temperatures;
FIG. 3 NMP solvent, 6% MWNTs-NH2And 3% MWNTs-NH2Permeability change plots at different temperatures;
FIG. 4 Pebax/MWNTs-NH2Scanning Electron Microscope (SEM) image of mixed base film:
(a)3wt.％MWCNTs-NH2(b)6wt.％MWCNTs-NH2(c)6wt.％MWCNTs-NH2(Ethanol/water)。
Detailed Description
The invention is further illustrated by the following specific examples and the accompanying drawings. The examples are intended to better enable those skilled in the art to better understand the present invention and are not intended to limit the present invention in any way.
The technical scheme of the invention is that the invention is a Pebax/MWNTs-NH for gas separation2The preparation method of the mixed matrix membrane comprises the following steps:
1) materials: pebax MH 1657; amino modified multi-walled carbon nanotube (MWNTs-NH)2) (ii) a Methylpyrrolidone (NMP);
2) preparation of mixed matrix membrane: the mixed matrix membrane is prepared by adopting a wet phase conversion technology. Dissolving the MWNTs-NH dried in vacuum with NMP (95 wt%) solvent2And stirring for 60 min. Then, the mixture is subjected to ultrasonic treatment at 27 ℃ for 30 min. Purifying with isopropanol-washed Pebax 1657(5 wt.%), adding into the prepared solvent, and refluxing at 120 deg.C for 3 hr;
3) preparing membrane with the above mixed matrix solution, injecting the matrix solution into a mold, evaporating and drying at 70 deg.C for 6 hr, drying at 50 deg.C under vacuum for one night, soaking the prepared membrane in n-hexane
Example 1 comparison of separation Performance of membranes prepared with different solvents
1) Dissolving MWNTs-NH dried in vacuum with ethanol/water (70/30 wt%) as solvent2And stirring for 60 min. Then, the mixture is subjected to ultrasonic treatment at 27 ℃ for 30 min. Purifying with isopropanol-washed Pebax 1657(5 wt.%), adding into the prepared solvent, and refluxing at 120 deg.C for 3 hr;
2) preparing a membrane by using the prepared mixed matrix solution, injecting the matrix solution into a model, evaporating and drying the solvent for 6 hours at 70 ℃, then drying the solvent overnight at 50 ℃ in a vacuum environment, and soaking the prepared membrane in n-hexane;
3) NMP (95 wt%) as a solvent, and the above procedure was repeated to prepare a separation membrane.
4) Determination of the separation Performance of two separation membranes
In this embodiment, the separation performance, permeability and selectivity of the mixed matrix membrane prepared by using different solvents are compared, and analysis and comparison show that the separation performance of the mixed matrix membrane prepared by using NMP as a solvent is significantly higher than that of the mixed matrix membrane prepared by using ethanol/water as a solvent, as shown in fig. 1.
Example 2 different Mass concentrations of MWNTs-NH2Research on analysis and optimization of separation performance of matrix membrane
Adding MWNTs-NH with different contents2Separately, 6% MWNTs-NH was produced2And 3% MWNTs-NH2The matrix membrane was mixed. Two different mixed matrix membranes were subjected to separability and permeability measurements.
In the implementation, the separation performance, permeability and selectivity of the mixed matrix membrane are compared under different conditions, and the analysis and comparison show that the mixed matrix membrane has 6 percent of MWNTs-NH2The separation characteristic of the mixed matrix membrane is better than that of 3 percent MWNTs-NH2The mixed matrix membrane has the separation performance, the gas permeation effect is best when the mixed matrix membrane is operated at the temperature of 60 ℃, and the membrane selectivity is best when the temperature is 45 ℃, as shown in figures 2 and 3.
FIG. 4 Pebax/MWNTs-NH2Scanning Electron Microscope (SEM) image of mixed base film:
(a)3wt.％MWCNTs-NH2(b)6wt.％MWCNTs-NH2(c)6wt.％MWCNTs-NH2(Ethanol/water)。

Claims (4)

1. the preparation method of the mixed film doped with the polyether block amide and the amino modified multi-walled carbon nanotube is characterized by comprising the following steps of:
1)1) materials: pebax MH 1657; amino modified multi-walled carbon nanotube (MWNTs-NH)2) (ii) a Methylpyrrolidone (95 wt.% NMP);
2) preparation of mixed matrix membrane: the mixed matrix membrane is prepared by adopting a wet phase conversion technology. Dissolving the MWNTs-NH dried in vacuum with NMP (95 wt%) solvent2And stirring for 60 min. Then, the mixture is subjected to ultrasonic treatment at 27 ℃ for 30 min. Purifying with isopropanol-washed Pebax 1657(5 wt.%), adding into the prepared solvent, and refluxing at 120 deg.C for 3 hr;
preparing membrane with the above mixed matrix solution, injecting the matrix solution into a mold, evaporating and drying at 70 deg.C for 6 hr, drying at 50 deg.C under vacuum for one night, soaking the prepared membrane in n-hexane, and storing
3) The separation performance of the membranes was measured at different temperatures and pressures.
2. The method according to claim 1, wherein the solvent in step 2) is preferably NMP (95 wt%) solvent.
3. The method of claim 1, wherein the Pebax 1657 concentration in step 2) is preferably 5 wt.%.
4. The method according to claim 1, wherein the mixed solution of step 2) contains MWNTs-NH2The mass fraction is preferably 6%.
CN201910970481.1A 2019-10-13 2019-10-13 Preparation method of polyether block amide and amino modified multi-walled carbon nanotube doped mixed film Pending CN110787659A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080312349A1 (en) * 2007-02-22 2008-12-18 General Electric Company Method of making and using membrane
CN103406034A (en) * 2013-07-30 2013-11-27 浙江国泰密封材料股份有限公司 Preparation method of polyether block amide microporous film for film distillation process
CN104689730A (en) * 2013-12-04 2015-06-10 中国科学院大连化学物理研究所 Preparation method and application of mixed matrix membrane with thermoplastic elastomer as matrix
US9095821B1 (en) * 2010-10-26 2015-08-04 Nagare Membranes, Llc Non-reactive process for fixing nanotubes in a membrane in through-passage orientation
CN107930418A (en) * 2017-11-23 2018-04-20 南京九思高科技有限公司 A kind of organic-inorganic sandwich diaphragm and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080312349A1 (en) * 2007-02-22 2008-12-18 General Electric Company Method of making and using membrane
US9095821B1 (en) * 2010-10-26 2015-08-04 Nagare Membranes, Llc Non-reactive process for fixing nanotubes in a membrane in through-passage orientation
CN103406034A (en) * 2013-07-30 2013-11-27 浙江国泰密封材料股份有限公司 Preparation method of polyether block amide microporous film for film distillation process
CN104689730A (en) * 2013-12-04 2015-06-10 中国科学院大连化学物理研究所 Preparation method and application of mixed matrix membrane with thermoplastic elastomer as matrix
CN107930418A (en) * 2017-11-23 2018-04-20 南京九思高科技有限公司 A kind of organic-inorganic sandwich diaphragm and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DAN ZHAO等: "Gas separation properties of poly(amide-6-b-ethyleneoxide)/amino modified multi-walled carbon nanotubes mixed matrix membranes", 《JOURNAL OF MEMBRANE SCIENCE》 *
MOJGAN ISANEJAD等: ""Pebax membrane for CO2/CH4 separation: Effects of various solvents on morphology and performance"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *

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Application publication date: 20200214