高性能AlPO4-14分子筛膜的制备及气体分离性能

doi:10.7503/cjcu20190255

摘要/Abstract

摘要：

制备了高性能的AlPO₄-14分子筛膜. 首先通过控制反应溶胶中水和模板剂的含量制备了形貌均一的AlPO₄-14分子筛, 分子筛的尺寸为15~18 mm; 然后采用晶种法即在反应凝胶中加入分子筛作为晶种进一步调控分子筛的大小, 使得AlPO₄-14分子筛的尺寸从15~18 mm减小到2~3 mm, 得到形貌均一的纯相片状晶体, 同时有效缩短了制备时间; 最后以多孔管状莫来石为支撑体, 采用二次生长法制备AlPO₄-14分子筛膜. 考察了2种不同大小的晶种对膜形貌和性能的影响, 发现以大尺寸的分子筛(15~18 mm)作为晶种制备的分子筛膜的分离层存在较多缺陷, 而采用小尺寸的晶种(2~3 mm)制备的膜层较均一致密. AlPO₄-14分子筛膜经高温脱除模板剂后仍然保持着纯相的AlPO₄-14晶型, 表明二次生长法促进了AlPO₄-14晶体在膜层中的生长且使其具有更高的结晶度和热稳定性. 在25 ℃, 100 kPa下, AlPO₄-14分子筛膜对H₂/CH₄, CO₂/CH₄和H₂/CF₄的理想分离因子分别为28, 40和1047, 且H₂和CO₂的渗透速率分别为6.3×10 ^-7和9×10 ^-7 mol·(m ²·s·Pa) ^-1; 对等摩尔CO₂/CH₄混合气体的分离因子为81.5, 且CO₂的渗透速率为8.8×10 ^-7 mol·(m ²·s·Pa) ^-1.

关键词: 磷酸铝分子筛, AlPO₄-14分子筛膜, 晶种法, 二次生长法, CO₂/CH₄分离

Abstract:

The AlPO₄-14 molecular sieve membrane with high separation performance was prepared. Firstly, the uniform AlPO₄-14 zeolite with the size of 15—18 mm was obtained by controlling the amount of water and template in the reaction sols of zeolite. Then, the AlPO₄-14 zeolite size was further regulated through a seed method by adding the AlPO₄-14 zeolite seeds into the reaction sols, through which not only the zeolite size was reduced from 15—18 mm to 2—3 mm with uniform plate-like morphology, but also the synthesis time was effectively shortened. Lastly, AlPO₄-14 zeolite membranes were fabricated on mullite supports via a secondary growth method, and two different sizes of zeolite seeds(large size: 15—18 mm, small size: 2—3 mm) were used to explore the effect of seeds size on membrane morphology and separation performance. Results revealed that the separation layers of the resulting membranes prepared from large-sized seeds showed many defects, while the membranes prepared from small-sized seeds were more uniform and defect-free. Besides, the AlPO₄-14 zeolite membranes kept its own crystal structure after template removal at 425 ℃, indicating that the se-condary growth method promoted the growth of AlPO₄-14 crystals in the membrane and endowed membrane with high crystallinity and thermal stability. The best AlPO₄-14 zeolite membrane displayed H₂ permeance of 6.3×10 ^-7 mol·(m ²·s·Pa) ^-1 and CO₂ permeance of 9×10 ^-7 mol·(m ²·s·Pa) ^-1 with ideal selectivities of 28, 40 and 1047 for H₂/CH₄, CO₂/CH₄ and H₂/CF₄, respectively; for the equimolar CO₂/CH₄ mixture separation, the selectivity was as high as 81.5 with CO₂ permeance of 8.8×10 ^-7 mol·(m ²·s·Pa) ^-1 at 25 ℃ and 100 kPa pressure drop.

Key words: Aluminophosphate molecular sieve, AlPO₄-14 zeolite membrane, Seed method, Secondary growth method, CO₂/CH₄ separation

中图分类号:

O611

TrendMD:

邵国泉,朱惠,马伟,闫攀,马继龙. 高性能AlPO₄-14分子筛膜的制备及气体分离性能. 高等学校化学学报, 2019, 40(11): 2265.

SHAO Guoquan,ZHU Hui,MA Wei,YAN Pan,MA Jilong. Synthesis of High-performance AlPO₄-14 Zeolite Membranes for Gas Separation ^†. Chem. J. Chinese Universities, 2019, 40(11): 2265.

图/表 11

Scheme 1 Schematic illustration of the synthesis of AlPO4-14 zeolite membranes

Fig.1 Schematic diagram of gas permeation setup 1. Stop valve; 2. mass flow controller; 3. pressure gauge; 4. oven; 5. membrane cell; 6. rubber O-ring; 7. membrane; 8. back pressure valve; 9. bubble film meter; 10. gas sampler; 11. gas chromatograph.

Table 1 Effect of composition of sols on AlPO4-14 zeolite

Sample	n(Al₂O₃)/mol	n(P₂O₅)/mol	n(C₃H₉N)/mol	n(H₂O)/mol
S1	1	1	1	45
S2	1	1	1.5	45
S3	1	1	1	70
S4	1	1	1	100

Fig.2 SEM images of AlPO4-14 zeolite prepared from different sols (A) S1; (B) S2; (C) S3; (D) S4.

Table 2 Preparation of AlPO4-14 zeolite by the secondary growth

Sample^*	n(Al₂O₃)/mol	n(P₂O₅)/mol	n(C₃H₉N)/mol	n(H₂O)/mol
SS2	1	1	1.5	45
SS3	1	1	1	70
S3-24 h	1	1	1	70

Fig.3 SEM images of AlPO4-14 zeolite prepared by the secondary growth (A),(B) SS2; (C) SS3; (D) S3-24 h.

Fig.4 XRD patterns of AlPO4-14 powders and membranes a. as-synthesized AlPO4-14 powders SS2; b. as-synthesized AlPO4-14 membrane M-SS2; c. calcined AlPO4-14 membrane M-SS2.

Fig.5 SEM images of calcined AlPO4-14 membranes (A) Surface section of M-S2;(B) cross section of M-S2;(C) surface section of M-SS2;(D) cross section of M-SS2.

Fig.6 Single-gas permeances of different gases through AlPO4-14 membrane M-SS2 at 25 ℃ The inset shows the ideal selectivities for H2 and CO2 over other gases.

Fig.7 Temperature dependence of selectivity and permeance through the AlPO4-14 membrane M-SS2 in an equimolar CO2/CH4 mixture The solid symbols represent the data in mixtures and the open ones represent the data in single gas.

Fig.8 Comparison of AlPO4-14 membrane with other membranes Present upper bound for polymeric membranes from Robeson plot(2008)[23], zeolite T[24], DDR[25], AlPO-18[5,6,26] and SAPO-34[27,28], 1 Barrer=3.348×10-16 mol·(m·Pa·S)-1.

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高性能AlPO₄-14分子筛膜的制备及气体分离性能

Synthesis of High-performance AlPO₄-14 Zeolite Membranes for Gas Separation ^†

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