化工学报 ›› 2024, Vol. 75 ›› Issue (4): 1607-1615.DOI: 10.11949/0438-1157.20231199
张凯博(), 沈佳新, 李玉霞, 谈朋, 刘晓勤, 孙林兵()
收稿日期:
2023-11-21
修回日期:
2024-01-07
出版日期:
2024-04-25
发布日期:
2024-06-06
通讯作者:
孙林兵
作者简介:
张凯博(1999—),女,硕士研究生,202261204303@njtech.edu.cn
基金资助:
Kaibo ZHANG(), Jiaxin SHEN, Yuxia LI, Peng TAN, Xiaoqin LIU, Linbing SUN()
Received:
2023-11-21
Revised:
2024-01-07
Online:
2024-04-25
Published:
2024-06-06
Contact:
Linbing SUN
摘要:
乙烯(C2H4)和乙烷(C2H6)物理性质相似,其高效分离具有挑战性。利用Cu(Ⅰ)活性位与C2H4间的π络合作用,Cu(Ⅰ)基吸附剂能在温和条件下选择性地分离C2H4和C2H6,显著降低传统低温精馏分离过程的能耗。Cu(Ⅰ)由Cu(Ⅱ)还原制得,但Cu(Ⅱ)还原的不可控、能耗高且Cu(Ⅰ)收率低一直是Cu(Ⅰ)基吸附剂应用的障碍。采用选择性还原策略(SRS)成功在Y型沸石中选择性地构筑了Cu(Ⅰ)活性位,实现了温和条件下C2H4/C2H6的吸附分离。利用甲醛(HCHO)蒸气扩散传递,与沸石中的Cu(Ⅱ)反应,实现了低温(140℃)下Cu(Ⅰ)的选择性构筑;制得的Cu(Ⅰ)Y具有优异的C2H4/C2H6吸附分离性能,Cu(Ⅰ)Y的选择性达16.3,远高于Cu(Ⅱ)Y的3.2。机理研究表明,HCHO与Y沸石中的Cu(Ⅱ)发生氧化还原反应,在得到Cu(Ⅰ)的同时生成CO2和H2O。
中图分类号:
张凯博, 沈佳新, 李玉霞, 谈朋, 刘晓勤, 孙林兵. Y沸石中Cu(Ⅰ)的可控构筑及其乙烯/乙烷吸附分离性能研究[J]. 化工学报, 2024, 75(4): 1607-1615.
Kaibo ZHANG, Jiaxin SHEN, Yuxia LI, Peng TAN, Xiaoqin LIU, Linbing SUN. Controllable construction of Cu(Ⅰ) in Y zeolite for adsorptive separation of ethylene/ethane[J]. CIESC Journal, 2024, 75(4): 1607-1615.
Sample | Temperature/℃ | SBET/(m2·g-1) | Vp/(cm3·g-1) |
---|---|---|---|
Cu(Ⅱ)Y | — | 818 | 0.36 |
Cu(Ⅰ)Y | 130 | 735 | 0.34 |
140 | 722 | 0.34 | |
150 | 638 | 0.30 |
表1 Cu(Ⅱ)Y和不同温度还原的Cu(Ⅰ)Y的结构性质
Table 1 Textural properties of Cu(Ⅱ) Y and Cu(Ⅰ)Y reduced under different temperatures
Sample | Temperature/℃ | SBET/(m2·g-1) | Vp/(cm3·g-1) |
---|---|---|---|
Cu(Ⅱ)Y | — | 818 | 0.36 |
Cu(Ⅰ)Y | 130 | 735 | 0.34 |
140 | 722 | 0.34 | |
150 | 638 | 0.30 |
图5 298 K下C2H4和C2H6在NaY、Cu(Ⅱ)Y和不同温度还原的Cu(Ⅰ)Y上的吸附等温线
Fig.5 Adsorption isotherms of C2H4 and C2H6 at 298 K on NaY, Cu(Ⅱ)Y and Cu(Ⅰ)Y reduced under different temperatures
Adsorbent | Adsorbate | qc/(mmol·g-1) | Kc/bar-1 | qi/(mmol·g-1) | Ki/bar-1 | R2 |
---|---|---|---|---|---|---|
Cu(Ⅱ)Y | C2H4 | 1.05214 | 37.06038 | 3.23794 | 0.96605 | 0.99996 |
C2H6 | 3.10002 | 0.71273 | 3.10002 | 0.71272 | 0.99758 | |
Cu(Ⅰ)Y | C2H4 | 1.54610 | 121.0418 | 3.95748 | 1.54104 | 0.99959 |
C2H6 | 1.93954 | 1.21846 | 1.93954 | 1.21854 | 0.99859 |
表2 吸附等温线模拟参数
Table 2 Fitting parameters derived from isothermal data
Adsorbent | Adsorbate | qc/(mmol·g-1) | Kc/bar-1 | qi/(mmol·g-1) | Ki/bar-1 | R2 |
---|---|---|---|---|---|---|
Cu(Ⅱ)Y | C2H4 | 1.05214 | 37.06038 | 3.23794 | 0.96605 | 0.99996 |
C2H6 | 3.10002 | 0.71273 | 3.10002 | 0.71272 | 0.99758 | |
Cu(Ⅰ)Y | C2H4 | 1.54610 | 121.0418 | 3.95748 | 1.54104 | 0.99959 |
C2H6 | 1.93954 | 1.21846 | 1.93954 | 1.21854 | 0.99859 |
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