CN108283889A - A kind of composite membrane, preparation method and the application in gas separation, purifying - Google Patents

A kind of composite membrane, preparation method and the application in gas separation, purifying Download PDF

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Publication number
CN108283889A
CN108283889A CN201710015845.1A CN201710015845A CN108283889A CN 108283889 A CN108283889 A CN 108283889A CN 201710015845 A CN201710015845 A CN 201710015845A CN 108283889 A CN108283889 A CN 108283889A
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composite membrane
porous
polymer film
organic
gas
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CN201710015845.1A
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CN108283889B (en
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陈亮
周峰
孔春龙
杜红斌
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones

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

Abstract

The present invention provides a kind of composite membranes, and using porous carrier as supporter, for supporting body surface using organic-inorganic porous material as transition zone, transition layer surface is polymer film.When the composite membrane is as applications such as gas separation, purifying, gas carries out secondary separation through after polymer film in organic-inorganic Porous transition layer, compared with polymer film, excellent permeability and higher gas-selectively can be had both, compared with traditional inorganic porous membrane, the performance that isolates and purifies of gas is improved, therefore there is preferable application prospect in industrial circles such as gas separation, purifying.

Description

A kind of composite membrane, preparation method and the application in gas separation, purifying
Technical field
Detached the present invention relates to technical field of membrane separation more particularly to a kind of composite membrane, preparation method and in gas, Application in purifying.
Background technology
Membrane separation technique is to adapt to an important isolation technics of modern industry development, relative to absorption and by changing temperature It spends to realize the traditional technology of separation, there are energy saving, the advantages such as environmental-friendly.In order to cater to the demand of industrial development, increasingly More seminar is dedicated to gas separation membrane of the development and production with excellent release energy and high throughput.
Polymer separation film due to low energy consumption, it is simple for process, be easy to automation, flexibility is strong, pollution-free and easy to operate The advantages that, the sour gas (CO in hydrogen retrieval, oxygen-enriched, rich nitrogen and natural gas2Deng) removing etc. have it is very extensive Prospects for commercial application.But in order to continue to expand application field and reduce practical operation expense, it is desirable to synthesized polymer Film has higher gas-selectively and permeability and lower operating pressure.But many studies have shown that, polymer film The gas-selectively of material can not be taken into account with permeability, and there are the Robeson upper limits, it is difficult to be provided simultaneously with high gas permeability and height Gas-selectively.In addition, traditional polymer self-supported membrane thickness is higher, reach tens microns, air transmission coefficient is relatively low, and industry is answered It generally requires to use very high pressure to improve permeability in, not only increases industrial cost, and very to equipment requirement Height, while there is certain danger.
Traditional inorganic porous membrane has higher air transmission coefficient, but gas separating property is not but high, in addition inorganic more Defect is easy tod produce in the preparation process of pore membrane, is hardly produced large stretch of continuous fine and close seperation film.
Invention content
Present situation in view of the above technology, the present invention is intended to provide a kind of composite membrane, has both higher gas permeability and gas Body selectivity can be used for gas separation, purifying.
In order to achieve the above technical purposes, the present invention using porous carrier be used as supporter, supporting body surface use it is organic- For inorganic porous material as transition zone, transition layer surface is polymer film, is integrally formed composite membrane, and structure is as shown in Figure 1, tool It has the advantages that：
(1) on the one hand porous carrier surface can substantially reduce carrier using organic-inorganic porous material as transition zone Pore size, be conducive to improve separating property can substantially reduce polymer film on the other hand relative to polymer self-supported membrane Thickness to nanometer scale, to reduce separating pressure；Also, it is combined with inorganic matter using organic matter due to transition zone Porous material, wherein contain organic structure, therefore the affinity between the polymer film on surface is stronger, improves polymer film Binding force between carrier.
(2) composite membrane as gas separation, purifying etc. in application, gas is through more in organic and inorganic after polymer film Hole transition zone carries out secondary separation and compensates for polymer film caused by there are the Robeson upper limits compared with polymer film The problem of gas-selectively and permeability can not be taken into account makes composite membrane is whole not only to have an excellent permeability, and with compared with High gas-selectively；Compared with traditional inorganic porous membrane, due to increasing the permeability and separation of polymer film, gas is improved Isolate and purify performance, therefore there is preferable application prospect in industrial circles such as gas separation, purifying.
That is, the technical solution adopted by the present invention is：A kind of composite membrane, using porous carrier as supporter, supporting body surface Using organic-inorganic porous material as transition zone, transition layer surface is polymer film.
The material of the porous carrier is unlimited, including in porous ceramics, porous metal oxide, porous organic matter etc. One or more kinds of mixing.
The structure of the porous carrier is unlimited, including tubular structure or slice structure etc..
The organic-inorganic porous material refers to the porous material that organic matter is combined with inorganic matter, wherein containing It is one or two kinds of in organic structure, including organosilicon, Organic-inorganic composite porous material and metal-organic framework materials etc. Above mixing.
Preparing for the transition zone is unlimited, including the methods of growth, coating, dipping.
Preferably, the thickness of the transition zone is 10nm-100 μm, more preferably 100nm-1 μm.
Preferably, the infiltration rate of the transition zone is 100barrer-1000000barrer.
The material of the polymer film is unlimited, including PS membrane, polyvinylidene fluoride film, polyimide film etc..
The methods of the preparation method of the polymer film is unlimited, including coat, impregnate.
Preferably, the thickness of the polymer film is 10nm-5 μm, more preferably 100nm-1 μm.
The present invention also provides a kind of methods preparing above-mentioned composite membrane, include the following steps：
(1) transition zone that organic-inorganic porous material is constituted is prepared in porous carrier surface；The preparation method is not Limit, including the methods of coating, growth, dipping.
(2) polymer film is prepared in transition layer surface；The preparation method is unlimited, including coating, impregnating.
Preferably, before step (1), porous carrier surface is modified using porous material, such as silica gel etc. Processing, to reduce support volume defect, keeps it more smooth.
Description of the drawings
Fig. 1 is the structural schematic diagram of composite membrane of the present invention；
Fig. 2 a are the surface SEM pictures of supporting body surface composite membrane obtained in the embodiment of the present invention 1；
Fig. 2 b are the section SEM pictures of supporting body surface composite membrane obtained in the embodiment of the present invention 1；
Fig. 3 is the gas permeability schematic diagram of supporting body surface composite membrane obtained in the embodiment of the present invention 1；
Fig. 4 is the gas permeability signal of the organic-inorganic porous film of supporting body surface obtained in comparative example 1 Figure；
Fig. 5 a are the surface SEM pictures of polyimides self-supported membrane obtained in comparative example 2；
Fig. 5 b are the section SEM pictures of polyimides self-supported membrane obtained in comparative example 2；
Fig. 6 is the gas permeability schematic diagram of polyimides self-supported membrane obtained in comparative example 2.
Specific implementation mode
The present invention will be further described with reference to the accompanying drawings and embodiments, it should be pointed out that embodiment described below It is intended to be convenient for the understanding of the present invention, without playing any restriction effect.
Reference numeral in Fig. 1 is：1- supporters, the transition zone that the organic-inorganic porous materials of 2- are constituted, 3- polymer Film.
Embodiment 1：
In the present embodiment, structure of composite membrane is as shown in Figure 1, using porous α-Al2O3Hollow ceramic fibre pipe is supporter 1, Its outer diameter is 3.5mm, internal diameter 2.5mm, average pore size 100nm；Supporting body surface is duplicature, i.e. supporting body surface was Layer 2 is crossed, it is 5 that transition zone, which is by molar ratio,:1 1,2- bis- (triethoxy silicon substrate) ethane (BTESE) and hydrochloric acid is in room temperature condition For the precursor solution of generation by organic-inorganic porous material made of dilution, sintering, drying, transition layer surface is that polyamides is sub- Amine film 3.
The preparation method of the composite membrane is as follows：
(1) preparation of precursor sol and polyimides weak solution
0.0206g concentrated hydrochloric acids, 3g deionized waters and 1.0197g absolute ethyl alcohols are mixed, hydrochloric acid mixed solution is obtained；By the salt Sour mixed liquor is added in the solution of 1g BTESE and 4.92g absolute ethyl alcohols mixing, is stirred 6 hours, is obtained at ambient temperature Precursor sol absolute ethyl alcohol is diluted 10 times, obtains diluted precursor sol by precursor sol.
It takes 2g polyimides to be dissolved in 25mL tetrachloroethanes, is sufficiently stirred to obtain polyimides at ambient temperature dilute molten Liquid.
(2) preparation of film
Include the following steps (2-1), (2-2) and (2-3)：
(2-1) modifies supporter with industrial silicone, to reduce support volume defect, keeps it more smooth,
Process A：Supporter is positioned in 140 DEG C of baking oven and preheats half an hour, then with hospital gauze by industrial silicone (ingredient is mainly SiO2And water) be evenly applied on supporter, supporter is then put in the prior tubular type for being heated to 550 DEG C In stove, high-temperature roasting 20 minutes in air.
Repeat the above process A 5 times.
(2-2) uses diluted precursor sol film：
Process B：It takes that treated that supporter is put in 130 DEG C of baking ovens preheats half an hour by (2-1), then uses hospital gauze The diluted precursor sol obtained in (1) is evenly applied to supporting body surface, then supporter is put in and has been added in advance In heat to 300 DEG C of tube furnace, roast 20 minutes in air.
Repeat the above process B 3 times.
(2-3) is filmed using polyimides weak solution：
Will through (2-2), treated that supporter both ends are shut with raw material band, it is sub- vertically at the uniform velocity to immerse the polyamides obtained in (1) 20s in amine weak solution, and equally vertically at the uniform velocity take out, then room temperature is dried for 24 hours in draught cupboard, is subsequently placed in 60 DEG C of baking ovens 6h finally dries 12h in 150 DEG C of vacuum drying ovens.
Fig. 2 a and 2b are respectively surface and the section SEM pictures of composite membrane obtained above, it can be seen that obtained compound Film is continuous, complete and fine and close film layer, and the thickness of film layer is about 100-200nm.
The gas permeability of composite membrane obtained above is as shown in figure 3, show that the composite film material shows at room temperature Go out excellent H2Preferential permeability and separation performance, H2The permeation flux of gas reaches 4.5 × 10-8mol·m-2·s-1·Pa-1, H2/ CO2Separation reached 11.6.Relative to traditional polymer film, higher flux and H are shown2/CO2Separation property Energy.
Comparative example 1：
Same as Example 1 in this comparative example, membrane material uses porous α-Al2O3Hollow ceramic fibre pipe is support Body, outer diameter 3.5mm, internal diameter 2.5mm, average pore size 100nm.As different from Example 1, supporting body surface is single Tunic, the monofilm is identical as the transition zone in embodiment 1, be by molar ratio be 5:1 1,2- bis- (triethoxy silicon substrate) second Alkane (BTESE) and hydrochloric acid are more by organic and inorganic made of dilution, sintering, drying in the precursor solution that room temperature condition generates Porous materials layer.
The preparation method of the monofilm is as follows：
(1) preparation of precursor sol
The preparation method of the precursor sol and step are identical with method in embodiment 1, which equally uses Absolute ethyl alcohol dilutes 10 times, obtains diluted precursor sol.
(2) preparation of film
Include the following steps (2-1) and (2-2)：
(2-1) modifies supporter with industrial silicone：
Process A：Supporter is positioned in 140 DEG C of baking oven and preheats half an hour, then with hospital gauze by industrial silicone It is evenly applied on supporter, then supporter is put in and is heated in 550 DEG C of tube furnace in advance, high-temperature roasting in air 20 minutes.
Repeat the above process A 5 times.
(2-2) uses diluted precursor sol film：
Process B：It takes that treated that supporter is put in 130 DEG C of baking ovens preheats half an hour by (2-1), then uses hospital gauze The diluted precursor sol obtained in (1) is evenly applied to supporting body surface, then supporter is put in and has been added in advance In heat to 300 DEG C of tube furnace, roast 20 minutes in air.
Repeat the above process B 3 times.
The gas permeability of film layer obtained above is as shown in figure 4, result shows the membrane material to H2Permeation flux It is 9.0 × 10-7mol·m-2·s-1·Pa-1, but H2/CO2Separation only have 4.1, though it can thus be seen that the membrane material So there is higher gas infiltration capacity, but gas-selectively is bad, is unfavorable for gas separation application.
Comparative example 2：
In this comparative example, membrane material is the polyimide film of self-supporting, that is, without supporter, and only polyamides is sub- Amine film layer.
The preparation method of the polyimide film of the self-supporting is as follows：
(1) preparation of polyimides weak solution
It takes 2g polyimides to be dissolved in 25mL tetrachloroethanes, is sufficiently stirred to obtain polyimides at ambient temperature dilute molten Liquid.
(2) preparation of film
Polyimides weak solution is poured on clean, smooth and horizontal glass plate, with the blade applicator for being highly 0.3mm Carry out knifing；Then room temperature is dried for 24 hours in draught cupboard, is subsequently placed in 60 DEG C of baking ovens dry 6h, is finally dried in 150 DEG C of vacuum Dry 12h in case.
Fig. 5 a and 5b are respectively surface and the section SEM pictures of polyimide film obtained above, can from SEM pictures Go out, which is continuous, complete and fine and close film layer, and the thickness of film layer is about 40-50 μm, and thickness is much larger than implementation Composite film thickness in example 1.
The gas permeability of polyimide film obtained above is as shown in Figure 6, it can be seen that membrane material table at room temperature Reveal excellent H2Preferential permeability and separation performance, H2/CO2Separation up to 7.2, but H2The permeation flux very little of gas, only It needs to impose severe pressure when having 50.3barrer, therefore detaching gas on a large scale in the industry, it is compared with Example 1, right Film strength and toughness reguirements higher, use cost bigger are unfavorable for sustainable development.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that described in having gone up only For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of this statement, Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of composite membrane, it is characterized in that：Using porous carrier as supporter, supporting body surface uses organic-inorganic porous material It is polymer film that material, which is used as transition zone, transition layer surface,.
2. composite membrane as described in claim 1, it is characterized in that：The material of the porous carrier includes porous ceramics, porous One or more kinds of mixing in metal oxide, porous organic matter；
Preferably, the structure of the porous carrier is tubular structure or slice structure.
3. composite membrane as described in claim 1, it is characterized in that：The organic-inorganic porous material includes organosilicon, has The inorganic composite porous material of machine-and metal-organic framework materials.
4. composite membrane as described in claim 1, it is characterized in that：The preparation method of the transition zone include growth, coating with Dipping.
5. composite membrane as described in claim 1, it is characterized in that：The thickness of the transition zone is 10nm-100 μm, preferably 100nm-1μm。
6. composite membrane as described in claim 1, it is characterized in that：The material of the polymer film includes PS membrane, gathers inclined fluorine One or more kinds of mixing in vinyl film, polyimide film.
7. composite membrane as described in claim 1, it is characterized in that：The preparation method of the polymer film includes coating and leaching Stain.
8. composite membrane as described in claim 1, it is characterized in that：The thickness of the polymer film is 10nm-5 μm, preferably 100nm-1μm。
9. the preparation method of the composite membrane as described in any claim in claim 1 to 8, it is characterized in that：Including walking as follows Suddenly：
(1) transition zone that organic-inorganic porous material is constituted is prepared in porous carrier surface；
(2) polymer film is prepared in transition layer surface.
10. application of the composite membrane in gas separation, purifying as described in any claim in claim 1 to 8.
CN201710015845.1A 2017-01-10 2017-01-10 Composite membrane, preparation method thereof and application thereof in gas separation and purification Active CN108283889B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109370671A (en) * 2018-11-20 2019-02-22 杭州勃扬能源设备有限公司 A kind of oil field gas separating technology
CN111111464A (en) * 2020-01-06 2020-05-08 南京荷风智能科技有限公司 Structural design and preparation method of ultrahigh carbon dioxide gas selective separation composite membrane
CN113663540A (en) * 2021-10-20 2021-11-19 湖南叶之能科技有限公司 Carbon dioxide separation membrane and application thereof
CN114515517A (en) * 2022-02-22 2022-05-20 华中科技大学 Polymer composite membrane for in-situ growth of MOF (Metal organic framework) middle layer in low-temperature water phase, preparation and application
CN114588789A (en) * 2020-12-04 2022-06-07 中国石油化工股份有限公司 Membrane material for denitrification of natural gas and preparation method thereof
CN114602331A (en) * 2020-12-07 2022-06-10 宁波市电力设计院有限公司 Preparation method and application of polymer-based composite membrane

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109370671A (en) * 2018-11-20 2019-02-22 杭州勃扬能源设备有限公司 A kind of oil field gas separating technology
CN111111464A (en) * 2020-01-06 2020-05-08 南京荷风智能科技有限公司 Structural design and preparation method of ultrahigh carbon dioxide gas selective separation composite membrane
CN111111464B (en) * 2020-01-06 2021-12-17 南京荷风智能科技有限公司 Structural design and preparation method of ultrahigh carbon dioxide gas selective separation composite membrane
CN114588789A (en) * 2020-12-04 2022-06-07 中国石油化工股份有限公司 Membrane material for denitrification of natural gas and preparation method thereof
CN114588789B (en) * 2020-12-04 2024-04-19 中国石油化工股份有限公司 Membrane material for denitrification of natural gas and preparation method thereof
CN114602331A (en) * 2020-12-07 2022-06-10 宁波市电力设计院有限公司 Preparation method and application of polymer-based composite membrane
CN114602331B (en) * 2020-12-07 2023-11-17 宁波市电力设计院有限公司 Preparation method and application of polymer-based composite film
CN113663540A (en) * 2021-10-20 2021-11-19 湖南叶之能科技有限公司 Carbon dioxide separation membrane and application thereof
CN113663540B (en) * 2021-10-20 2022-01-18 湖南叶之能科技有限公司 Carbon dioxide separation membrane and application thereof
CN114515517A (en) * 2022-02-22 2022-05-20 华中科技大学 Polymer composite membrane for in-situ growth of MOF (Metal organic framework) middle layer in low-temperature water phase, preparation and application

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