CN109621647B - A method for separating and enriching carbon dioxide - Google Patents
A method for separating and enriching carbon dioxide Download PDFInfo
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- CN109621647B CN109621647B CN201910037721.2A CN201910037721A CN109621647B CN 109621647 B CN109621647 B CN 109621647B CN 201910037721 A CN201910037721 A CN 201910037721A CN 109621647 B CN109621647 B CN 109621647B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 54
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 61
- 238000000926 separation method Methods 0.000 claims abstract description 59
- 239000012528 membrane Substances 0.000 claims abstract description 56
- 239000002608 ionic liquid Substances 0.000 claims abstract description 52
- 230000005684 electric field Effects 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910021389 graphene Inorganic materials 0.000 claims description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- -1 1-butyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 17
- 230000004907 flux Effects 0.000 description 15
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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Abstract
本发明涉及气体分离技术领域，公开了一种分离富集二氧化碳的方法，包括：在20～100℃、0.01～0.2MPa压力、强度为‑7.5～7.5V/mm的电场条件下，采用离子液体/二维片层材料气体分离膜对含有二氧化碳的混合气体进行分离富集；离子液体/二维片层材料气体分离膜的制备方法包括：(1)将二维片层材料分散在去离子水中得到二维片层材料分散液，通过真空抽滤将二维片层材料分散液抽滤到多孔基底上，得到二维片层材料膜；(2)将离子液体涂布在所述的二维片层材料膜表面，在不低于50KPa负压下保持1～8小时，得到离子液体/二维片层材料气体分离膜。本发明的方法通过对离子液体/二维片层材料气体分离膜施加电场，使得离子液体/二维片层材料气体分离膜具有非常优异的气体分离能力。
The invention relates to the technical field of gas separation, and discloses a method for separating and enriching carbon dioxide, comprising: using an ionic liquid under the electric field conditions of 20-100° C., 0.01-0.2MPa pressure, and intensity of ‑7.5-7.5V/mm The two-dimensional sheet material gas separation membrane separates and enriches the mixed gas containing carbon dioxide; the preparation method of the ionic liquid/two-dimensional sheet material gas separation membrane includes: (1) dispersing the two-dimensional sheet material in deionized water The two-dimensional sheet material dispersion is obtained, and the two-dimensional sheet material dispersion is suction-filtered onto the porous substrate by vacuum filtration to obtain a two-dimensional sheet material film; (2) the ionic liquid is coated on the two-dimensional sheet material. The surface of the sheet material membrane is kept under a negative pressure of not less than 50KPa for 1-8 hours to obtain an ionic liquid/two-dimensional sheet material gas separation membrane. The method of the present invention enables the ionic liquid/two-dimensional sheet material gas separation membrane to have very excellent gas separation capability by applying an electric field to the ionic liquid/two-dimensional sheet material gas separation membrane.
Description
技术领域technical field
本发明涉及气体分离技术领域，尤其涉及一种分离富集二氧化碳的方法。The invention relates to the technical field of gas separation, in particular to a method for separating and enriching carbon dioxide.
背景技术Background technique
气体分离膜分离气体的原理主要是基于不同气体在膜内的传输速率不同，通常可分为微孔扩散机制和溶解扩散机制。微孔扩散机制主要是利用多孔材料的孔洞或层状材料的通道来进行筛分；溶解扩散机制则是利用如一些高分子材料对不同气体具有不同溶解度和扩散系数的特性来分离和富集。The principle of gas separation by gas separation membrane is mainly based on the different transmission rates of different gases in the membrane, which can usually be divided into microporous diffusion mechanism and dissolution diffusion mechanism. The microporous diffusion mechanism mainly uses the pores of the porous material or the channels of the layered material for sieving; the dissolution diffusion mechanism uses the characteristics of some polymer materials with different solubility and diffusion coefficient for different gases to separate and enrich.
膜分离技术在应对当前由于以CO2为主的温室气体的大量排放造成的温室效应等气候变化带来的负面影响方面具有很高的利用价值，其具有环保、低能耗等优势。开发新型高效节能的分离膜成为重要的研究方向。Membrane separation technology has high utilization value in dealing with the current negative impacts of climate change such as the greenhouse effect caused by the massive emission of CO2 -based greenhouse gases, and it has the advantages of environmental protection and low energy consumption. The development of new high-efficiency and energy-saving separation membranes has become an important research direction.
聚合物薄膜作为气体分离膜早已投入商用，但聚合物薄膜所具有的通量低、稳定性差等缺点极大地限制了其应用。而二维层状材料如石墨烯、氧化石墨烯等，具有独特的纳米级通道，使气体分离膜在气体分离领域有了新的可能。氧化石墨烯具有独特的二维结构和成熟的制备工艺，由氧化石墨烯片层规则堆垛而成的氧化石墨烯薄膜在多个领域内都有很大的应用潜力，如水处理，电化学，催化，气体分离等。但是在气体分离领域，纯的氧化石墨烯薄膜的分离效率远没有达到可以实际应用的地步，因此需要进行改性。Polymer membranes have been put into commercial use as gas separation membranes for a long time, but the disadvantages of polymer membranes, such as low flux and poor stability, greatly limit their applications. Two-dimensional layered materials such as graphene, graphene oxide, etc., have unique nano-scale channels, which make gas separation membranes have new possibilities in the field of gas separation. Graphene oxide has a unique two-dimensional structure and a mature preparation process. Graphene oxide thin films formed by regular stacking of graphene oxide sheets have great application potential in many fields, such as water treatment, electrochemistry, Catalysis, gas separation, etc. However, in the field of gas separation, the separation efficiency of pure graphene oxide films is far from being practically applicable, so it needs to be modified.
离子液体是一种室温下呈液态的盐，具有蒸气压低、热稳定性和化学稳定性好等优点，且对二氧化碳有很高的溶解度，因此可以用来分离和富集二氧化碳。但将离子液体直接用来使用存在很大的局限性，因此常常将离子液体填充在多孔介质内制成复合膜来使用。Ionic liquids are salts that are liquid at room temperature and have the advantages of low vapor pressure, good thermal and chemical stability, and high solubility for carbon dioxide, so they can be used to separate and enrich carbon dioxide. However, the direct use of ionic liquids has great limitations, so ionic liquids are often filled in porous media to form composite membranes for use.
在单纯的压力差驱动下，气体分离膜对混合气体中二氧化碳的分离富集效率仍然有待提高。Driven by pure pressure difference, the separation and enrichment efficiency of gas separation membrane for carbon dioxide in mixed gas still needs to be improved.
发明内容SUMMARY OF THE INVENTION
本发明提供了一种分离富集二氧化碳的方法，对二氧化碳的分离能力和分离效率较高。The invention provides a method for separating and enriching carbon dioxide, which has high separation capacity and separation efficiency for carbon dioxide.
具体技术方案如下：The specific technical solutions are as follows:
一种分离富集二氧化碳的方法，包括：A method for separating and enriching carbon dioxide, comprising:
在20～100℃、0.01～0.2MPa压力、强度为-7.5～7.5V/mm的电场条件下，采用离子液体/二维片层材料气体分离膜对含有二氧化碳的混合气体进行分离富集；Under the electric field conditions of 20～100℃, 0.01～0.2MPa pressure and strength of -7.5～7.5V/mm, the mixed gas containing carbon dioxide was separated and enriched by ionic liquid/two-dimensional sheet material gas separation membrane;
所述离子液体/二维片层材料气体分离膜的制备方法包括：The preparation method of the ionic liquid/two-dimensional sheet material gas separation membrane includes:
(1)将二维片层材料分散在去离子水中得到二维片层材料分散液，通过真空抽滤将二维片层材料分散液抽滤到多孔基底上，得到二维片层材料膜；(1) dispersing the two-dimensional sheet material in deionized water to obtain a two-dimensional sheet material dispersion liquid, and filtering the two-dimensional sheet material dispersion liquid onto a porous substrate by vacuum filtration to obtain a two-dimensional sheet material film;
(2)将离子液体涂布在所述的二维片层材料膜表面，在不低于50KPa负压下保持1～8小时，得到离子液体/二维片层材料气体分离膜。(2) Coat the ionic liquid on the surface of the two-dimensional sheet material membrane, and keep it under a negative pressure of not less than 50KPa for 1-8 hours to obtain the ionic liquid/two-dimensional sheet material gas separation membrane.
利用真空抽滤的方式将二维片层材料水溶液中的二维片层材料抽滤至多孔基底上，得到具有规则层状结构的二维片层材料薄膜，该薄膜中层间距在1纳米以下；将离子液体涂布在二维片层材料薄膜表面后，离子液体会受到毛细管力的作用，逐渐渗透到二维片层材料薄膜的片层之间，并最终被限制在其中。The two-dimensional sheet material in the two-dimensional sheet material aqueous solution is suction-filtered onto the porous substrate by means of vacuum filtration to obtain a two-dimensional sheet material film with a regular layered structure, and the interlayer spacing in the film is less than 1 nanometer; After coating the ionic liquid on the surface of the two-dimensional sheet material film, the ionic liquid will gradually penetrate between the sheets of the two-dimensional sheet material film under the action of capillary force, and finally be confined in it.
相比于氢气、甲烷和氮气，离子液体对二氧化碳具有更高的溶解度，再加上二维片层材料纳米孔道的限域作用，此时的离子液体/二维片层材料气体分离膜已经具有较好的分离能力，在电场的进一步作用下，离子液体在二维片层材料之间的结构会得到改变，从而改变离子液体对气体的溶解度和扩散系数。在电场的作用下，离子液体/二维片层材料气体分离膜对二氧化碳气体的分离效率更高。另外，通过施加不同强度的电场，可以调节离子液体的阴阳离子在二维片层材料之间的分布变化，从而可调解离子液体/二维片层材料气体分离膜的分离性能。Compared with hydrogen, methane and nitrogen, ionic liquids have higher solubility for carbon dioxide, coupled with the confinement of nano-channels of two-dimensional sheet materials, the ionic liquid/two-dimensional sheet material gas separation membrane at this time has Under the further action of the electric field, the structure of the ionic liquid between the two-dimensional sheet materials will be changed, thereby changing the solubility and diffusion coefficient of the ionic liquid to the gas. Under the action of electric field, the separation efficiency of ionic liquid/two-dimensional sheet material gas separation membrane for carbon dioxide gas is higher. In addition, by applying electric fields of different intensities, the distribution changes of the anions and cations of the ionic liquid between the two-dimensional sheet materials can be adjusted, so that the separation performance of the ionic liquid/two-dimensional sheet material gas separation membrane can be adjusted.
本发明中，电场的施加方式为：在所述的离子液体/二维片层材料气体分离膜两侧分别设置一片金属电容片，在两片金属电容片上施加直流电压。In the present invention, the electric field is applied in the following way: a metal capacitor is respectively arranged on both sides of the ionic liquid/two-dimensional sheet material gas separation membrane, and a DC voltage is applied to the two metal capacitors.
优选的，所述含有二氧化碳的混合气体为二氧化碳与氢气、甲烷和氮气中的至少一种的混合气。Preferably, the mixed gas containing carbon dioxide is a mixed gas of carbon dioxide and at least one of hydrogen, methane and nitrogen.
离子液体/二维片层材料气体分离膜对二氧化碳与氢气、甲烷和氮气的通量差别较大，所述的含有二氧化碳的混合气体为二氧化碳与氢气、甲烷和氮气中的至少一种的混合气时，离子液体/二维片层材料气体分离膜对二氧化碳的分离富集效率更高。The flux of ionic liquid/two-dimensional sheet material gas separation membrane to carbon dioxide and hydrogen, methane and nitrogen is quite different, and the mixed gas containing carbon dioxide is a mixed gas of carbon dioxide and at least one of hydrogen, methane and nitrogen When ionic liquid/two-dimensional sheet material gas separation membrane is used, the separation and enrichment efficiency of carbon dioxide is higher.
优选的，所述的二维片层材料分散液中，二维片层材料的质量百分比浓度为0.02～0.2％。Preferably, in the two-dimensional sheet material dispersion liquid, the mass percentage concentration of the two-dimensional sheet material is 0.02-0.2%.
优选的，所述的二维片层材料为氧化石墨烯、二硫化钼和二硫化钨中的至少一种；进一步优选的，所述的二维片层材料为氧化石墨烯。氧化石墨烯具有独特的纳米级通道，具有较好的选择性。Preferably, the two-dimensional sheet material is at least one of graphene oxide, molybdenum disulfide and tungsten disulfide; further preferably, the two-dimensional sheet material is graphene oxide. Graphene oxide has unique nanoscale channels with good selectivity.
优选的，所述的离子液体为1-丁基-3-甲基咪唑四氟硼酸盐([BMIM][BF4])。该离子液体对二氧化碳的选择性较高，成本较低。Preferably, the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]). The ionic liquid has high selectivity to carbon dioxide and low cost.
随着膜厚度增加，气体的通量有所下降，但二氧化碳的分离比有所上升，但当膜厚达到一定厚度后，通量和分离比基本不变。膜中离子液体的含量越高，通量会有所下降，但二氧化碳的分离比会增加。With the increase of membrane thickness, the gas flux decreased, but the separation ratio of carbon dioxide increased, but when the membrane thickness reached a certain thickness, the flux and separation ratio remained basically unchanged. The higher the content of ionic liquid in the membrane, the flux will decrease somewhat, but the separation ratio of carbon dioxide will increase.
优选的，所述的离子液体/二维片层材料气体分离膜的厚度为50～1500nm；离子液体/二维片层材料气体分离膜中，离子液体的质量百分比为50～80％。Preferably, the thickness of the ionic liquid/two-dimensional sheet material gas separation membrane is 50-1500 nm; in the ionic liquid/two-dimensional sheet material gas separation membrane, the mass percentage of ionic liquid is 50-80%.
优选的，所述的多孔基底为聚碳酸酯多孔膜或无机氧化铝多孔膜。聚碳酸酯多孔膜或无机氧化铝多孔膜机械强度大，可为离子液体/二维片层材料复合层提供较稳定的支撑。Preferably, the porous substrate is a polycarbonate porous membrane or an inorganic alumina porous membrane. Polycarbonate porous membranes or inorganic alumina porous membranes have high mechanical strength and can provide a relatively stable support for the ionic liquid/two-dimensional sheet material composite layer.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
(1)离子液体/二维片层材料气体分离膜中，以二维片层材料作为支撑基底，具有良好的稳定性，同时可将离子液体限制在二维片层材料的层隙中，限域下的离子液体相较液相的离子液体，对气体的分离性能有了一定提高；(1) In the ionic liquid/two-dimensional sheet material gas separation membrane, the two-dimensional sheet material is used as the supporting substrate, which has good stability, and at the same time, the ionic liquid can be confined in the interlayer gap of the two-dimensional sheet material. Compared with the ionic liquid in the liquid phase, the ionic liquid in the domain has a certain improvement in the separation performance of the gas;
(2)通过电场改变离子液体的阴阳离子在二维片层材料之间的分布，从而改变离子液体对气体的溶解度和扩散系数，增强离子液体/二维片层材料气体分离膜对二氧化碳的分离富集能力，使得离子液体/二维片层材料气体分离膜具有非常优异的气体分离能力。(2) Change the distribution of the anions and cations of the ionic liquid between the two-dimensional sheet materials by the electric field, thereby changing the solubility and diffusion coefficient of the ionic liquid to the gas, and enhancing the separation of carbon dioxide by the ionic liquid/two-dimensional sheet material gas separation membrane The enrichment ability makes the ionic liquid/two-dimensional sheet material gas separation membrane have very excellent gas separation ability.
附图说明Description of drawings
图1为实施例1制备的氧化石墨烯薄膜的扫描电镜图，其中(a)为表面扫描电镜图，(b)为断面扫描电镜图；Fig. 1 is the scanning electron microscope image of the graphene oxide film prepared by embodiment 1, wherein (a) is the surface scanning electron microscope image, (b) is the cross-sectional scanning electron microscope image;
图2为实施例1制备的离子液体/氧化石墨烯薄膜的扫描电镜图，其中(a)为表面扫描电镜图，(b)为断面扫描电镜图；Fig. 2 is the SEM image of the ionic liquid/graphene oxide film prepared by Example 1, wherein (a) is a surface SEM image, and (b) is a cross-sectional SEM image;
图3为实施例4制备的离子液体/氧化石墨烯薄膜的扫描电镜图，其中(a)为表面扫描电镜图，(b)为断面扫描电镜图。3 is a scanning electron microscope image of the ionic liquid/graphene oxide film prepared in Example 4, wherein (a) is a surface SEM image, and (b) is a cross-sectional SEM image.
具体实施方式Detailed ways
实施例1Example 1
(1)室温下，配置氧化石墨烯质量百分比浓度为0.02％的氧化石墨烯水溶液，将0.5ml溶液在85KPa负压下抽滤至无机氧化铝多孔膜上，膜的直径为25mm，孔径200nm，制得76nm厚的氧化石墨烯薄膜；(1) At room temperature, a graphene oxide aqueous solution with a graphene oxide mass percentage concentration of 0.02% was configured, and 0.5 ml of the solution was suction-filtered onto an inorganic alumina porous membrane under a negative pressure of 85KPa. The diameter of the membrane was 25 mm and the pore diameter was 200 nm. A graphene oxide film with a thickness of 76 nm was obtained;
如图1所示，氧化石墨烯薄膜表面有细长的褶皱，断面有规则的层状结构。As shown in Figure 1, the surface of the graphene oxide film has slender wrinkles, and the cross-section has a regular layered structure.
(2)然后，在氧化石墨烯薄膜表面涂布0.05ml[BMIM][BF4]，保持在50KPa负压下2小时，制得170nm厚的[BMIM][BF4]/氧化石墨烯气体分离膜，其中氧化石墨烯和[BMIM][BF4]的质量比为0.39。(2) Then, coat 0.05 ml of [BMIM][BF 4 ] on the surface of the graphene oxide film and keep it under a negative pressure of 50KPa for 2 hours to obtain a 170 nm thick [BMIM][BF 4 ]/graphene oxide gas separation film with a mass ratio of graphene oxide and [BMIM][BF 4 ] of 0.39.
如图2所示。在加了离子液体之后，氧化石墨烯薄膜表面的褶皱变的短粗，断面的层状结构也消失了，且膜厚明显增大。as shown in
在室温、0.06MPa压力、强度为-2.5V/mm的电场条件下，测量该分离膜对二氧化碳、氢气、甲烷和氮气的通量，得到二氧化碳和氢气、二氧化碳和甲烷、二氧化碳和氮气的通量比值分别为14、67、85。Under the conditions of room temperature, 0.06MPa pressure and -2.5V/mm electric field, the flux of the separation membrane to carbon dioxide, hydrogen, methane and nitrogen was measured, and the fluxes of carbon dioxide and hydrogen, carbon dioxide and methane, carbon dioxide and nitrogen were obtained. The ratios are 14, 67, and 85, respectively.
对比例1Comparative Example 1
在室温、0.06MPa压力的条件下，测量实施例1制得的[BMIM][BF4]/氧化石墨烯气体分离膜对二氧化碳、氢气、甲烷和氮气的通量，得到二氧化碳和氢气、二氧化碳和甲烷、二氧化碳和氮气的通量比值分别为12、39、66。Under the conditions of room temperature and 0.06MPa pressure, the fluxes of the [BMIM][BF 4 ]/graphene oxide gas separation membrane prepared in Example 1 to carbon dioxide, hydrogen, methane and nitrogen were measured to obtain carbon dioxide and hydrogen, carbon dioxide and The flux ratios of methane, carbon dioxide, and nitrogen are 12, 39, and 66, respectively.
实施例2Example 2
在室温、0.06MPa压力、强度为2.5V/mm的电场条件下，测量实施例1制得的分离膜对二氧化碳、氢气、甲烷和氮气的通量，得到二氧化碳和氢气、二氧化碳和甲烷、二氧化碳和氮气的通量比值分别为20、72、132。Under the electric field conditions of room temperature, 0.06MPa pressure, and intensity of 2.5V/mm, the fluxes of the separation membrane prepared in Example 1 to carbon dioxide, hydrogen, methane and nitrogen were measured to obtain carbon dioxide and hydrogen, carbon dioxide and methane, carbon dioxide and The flux ratios of nitrogen were 20, 72, and 132, respectively.
实施例3Example 3
在室温、0.06MPa压力、强度为5V/mm的电场条件下，测量实施例1制得的分离膜对二氧化碳、氢气、甲烷和氮气的通量，得到二氧化碳和氢气、二氧化碳和甲烷、二氧化碳和氮气的通量比值分别为33、192、405。Under the conditions of room temperature, 0.06MPa pressure and electric field strength of 5V/mm, the fluxes of the separation membrane prepared in Example 1 to carbon dioxide, hydrogen, methane and nitrogen were measured to obtain carbon dioxide and hydrogen, carbon dioxide and methane, carbon dioxide and nitrogen. The flux ratios were 33, 192, and 405, respectively.
实施例4Example 4
(1)室温下，配置氧化石墨烯质量百分比浓度为0.02％的氧化石墨烯水溶液，将0.8ml溶液在85KPa负压下抽滤至无机氧化铝多孔膜上，膜的直径为25mm，孔径200nm，制得125nm厚的氧化石墨烯薄膜；(1) At room temperature, a graphene oxide aqueous solution with a graphene oxide mass percentage concentration of 0.02% was configured, and 0.8 ml of the solution was suction-filtered onto an inorganic alumina porous membrane under a negative pressure of 85KPa. The diameter of the membrane was 25 mm and the pore diameter was 200 nm. A graphene oxide film with a thickness of 125 nm was obtained;
(2)然后，在氧化石墨烯薄膜表面涂布0.08ml[BMIM][BF4]，制得280nm厚的[BMIM][BF4]/氧化石墨烯气体分离膜，其中氧化石墨烯和[BMIM][BF4]的质量比为0.45。(2) Then, 0.08 ml of [BMIM][BF 4 ] was coated on the surface of the graphene oxide film to obtain a [BMIM][BF 4 ]/graphene oxide gas separation membrane with a thickness of 280 nm, wherein graphene oxide and [BMIM ][BF 4 ] has a mass ratio of 0.45.
该[BMIM][BF4]/氧化石墨烯气体分离膜的表面和断面的结构如图3所示。The structure of the surface and cross-section of the [BMIM][BF 4 ]/graphene oxide gas separation membrane is shown in FIG. 3 .
在室温、0.06MPa、强度为5V/mm的电场条件下，测量该分离膜对二氧化碳、氢气、甲烷和氮气的通量，得到二氧化碳和氢气、二氧化碳和甲烷、二氧化碳和氮气的通量比值分别为39、238、479。Under the electric field conditions of room temperature, 0.06MPa and 5V/mm intensity, the fluxes of the separation membrane to carbon dioxide, hydrogen, methane and nitrogen were measured, and the flux ratios of carbon dioxide and hydrogen, carbon dioxide and methane, and carbon dioxide and nitrogen were obtained, respectively: 39, 238, 479.
以上所述的实施例对本发明的技术方案和有益效果进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充和等同替换等，均应包含在本发明的保护范围之内。The above-mentioned embodiments describe the technical solutions and beneficial effects of the present invention in detail. It should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention. Any modifications, additions and equivalent replacements made should be included within the protection scope of the present invention.
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