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硼掺杂DDR分子筛膜的制备与CO2/H2分离性能

作者：周诗航，李静博，张玉亭

单位：南京工业大学化工学院材料化学工程国家重点实验室，南京 211816

关键词： DDR分子筛膜； CO2/H2分离；硼掺杂；四硼酸钠；中空纤维

DOI号： 10.16159/j.cnki.issn1007-8924.2025.06.006

分类号： TQ028.1

出版年,卷(期):页码： 2025,45(6):53-60

摘要：

DDR分子筛膜因孔径适当、热化学稳定性好等优势在CO2气体分离领域受到关注，但是用于CO2/H2分离仍然存在选择性较低的不足。为了提高DDR分子筛膜的CO2/H2分离性能，本研究以四硼酸钠为硼源，采用二次生长法在四通道Al2O3中空纤维载体表面制备了硼掺杂DDR（B-DDR）分子筛膜。XRD、BET比表面积和FTIR等表征结果都证实了B原子成功掺入DDR分子筛骨架。CO2吸附结果表明硼掺杂提升了DDR分子筛的CO2吸附量。当膜合成液中四硼酸钠物质的量比为0.2时，制备的B0.8-DDR分子筛膜用于298 K等物质的量CO2/H2混合气分离，CO2渗透性为3.60×10-8 mol/(m2·s·Pa)，同时分离选择性为15.60，是DDR分子筛膜分离选择性（5.91）的2倍多。降低温度和增加进料压力都有利于提高B-DDR分子筛膜的分离选择性，当CO2进料浓度为50%(体积分数)时，膜的分离选择性最高。此外，B0.8-DDR分子筛膜在水汽环境中仍然保持稳定的CO2/H2分离性能，表明其具有良好的耐水汽稳定性。

DDR zeolite membrane has been attractive in CO2 separation because of its suitable pore size and good thermochemical stability. However, it has limited selectivity in CO2/H2 separation. To address this issue, boron-doped DDR (B-DDR) zeolite membranes were synthesized on four-channel α-Al2O3 hollow fibers by secondary growth using sodium tetraborate as the boron source. The successful doping of B atoms in DDR zeolite framework was confirmed by XRD, BET surface area and FTIR results. The CO2 adsorption results demonstrated that the doping of B atoms improved the CO2 adsorption amount of DDR zeolite. When the molar ratio of sodium tetraborate in precursor was 0.2, the CO2 permeance of the resultant membrane (B0.8-DDR membrane) in the separation of equimolar CO2/H2 mixed gas at 298 K was 3.60×10-8 mol/(m2·s·Pa). The CO2/H2 selectivity of the membrane was 15.60, which was more than twice of that of the DDR zeolite membrane (5.91). Lowering temperature or increasing feed pressure was beneficial for improving separation selectivity of the B-DDR membrane. The maximum CO2/H2 selectivity was achieved when the CO2 feed concentration was 50% (volume fraction). In addition, the membrane maintained stable separation performance under humid environment, indicating the good tolerance of the membrane to water vapor.

基金项目：

国家自然科学基金面上项目（22378192）

作者简介：

周诗航（2004-），男，江苏连云港人，研究方向为分子筛膜制备与分离.

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