离子型有机多孔聚合物的制备及其烟气脱硫耦合脱碳性质

doi:10.16085/j.issn.1000-6613.2022-0689

摘要/Abstract

摘要：

高效经济地消除燃煤烟气中的SO₂和CO₂对生态环境具有重要意义，但开发具有高捕集能力、高选择性和良好稳定性的吸附剂仍然是一个挑战。本文通过靛红与芳香族单体（三蝶烯）在超酸性条件下反应得到了性质稳定的有机多孔聚合物吸附剂PPN-1，并对PPN-1季胺化以及离子交换获得离子型多孔聚合物PPN-1-OH。由于两种有机多孔吸附剂拥有合适的BET表面积、丰富的微孔孔道以及大量的富电子基团，PPN-1和PPN-1-OH对SO₂和CO₂具有很强的亲和力。尤其是离子型有机多孔聚合物PPN-1-OH显示出超高的静态吸附能力，在298K、0.1MPa下其SO₂的吸附量高达13.09mmol/g，超过了此前报道的多孔材料。基于瞬时吸附速率，理想吸附溶液理论模拟和固定床穿透实验的研究证明PPN-1-OH具有卓越的SO₂动态吸附容量和选择性。在三组分混合气体(SO₂/CO₂/N₂=0.2/9/90.8，体积比)动态固定床穿透实验中，PPN-1-OH的SO₂吸附量高达1.81mmol/g，SO₂/CO₂选择性突破211。理论分析表明PPN-1-OH微孔孔道内大量的羟基基团能显著增强骨架与SO₂之间的结合力，有效地提高吸附容量和选择性。

关键词: 吸附分离, 二氧化硫, 二氧化碳, 离子型有机多孔聚合物, 碳捕集

Abstract:

Cost-effective capture of SO₂ and CO₂ from flues gas is still an ongoing challenge to the global ecological environment. Adsorption separation technology with low energy consumption is a promising gas capture technology but porous adsorbents with high capacity, high selectivity and good stability are very scarce. Herein a stable porous organic polymer (named PPN-1) by the reaction of isatin with triptycene under superacidic condition was synthesized. The ionic porous organic polymer was achieved by quaternization of PPN-1 with methyl iodide and then treated with KOH solution for exchange of I^- with OH^- to obtain PPN-1-OH. PPN-1 and PPN-1-OH had high affinity toward SO₂ and CO₂ due to their suitable BET surface areas, considerable microporous structures and abundant electron-rich nitrogen and oxygen atoms. Interestingly, PPN-1-OH possessed an ultra-high SO₂ capture performance (13.09mmol/g) at 0.1MPa and 298K, which exceeded previous reported porous adsorbents. Moreover, an excellent SO₂ dynamic adsorption capacity of 1.81mmol/g and SO₂/CO₂ selectivity (211) in ternary gas mixture (SO₂/CO₂/N₂=0.2/9/90.8, v/v/v) was achieved in PPN-1-OH based on column breakthrough experiments. The theory simulation revealed that the introduction of hydroxyl groups into the micropore channels of PPN-1-OH could significantly enhance the interaction between SO₂ and PPN-1-OH and improved the SO₂ capture capacity and selectivity.

Key words: adsorption separation, sulfur dioxide, carbon dioxide, ionic porous organic polymer, carbon capture

中图分类号:

TQ424

陈姝晖, 伍岳, 张文祥, 王闪闪, 马和平. 离子型有机多孔聚合物的制备及其烟气脱硫耦合脱碳性质[J]. 化工进展, 2023, 42(2): 1028-1038.

CHEN Shuhui, WU Yue, ZHANG Wenxiang, WANG Shanshan, MA Heping. Preparation of ionic organic porous polymer and its coupled desulfurization and decarbonization properties in flue gas[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 1028-1038.

图/表 18

图1 PPN-1和PPN-1-OH的合成路线图

图2 PPN-1和PPN-1-OH的傅里叶变换红外光谱

图3 PPN-1和PPN-1-OH在氮气气氛下的热重分析谱图

图4 PPN-1和PPN-1-OH的77K氮气吸附脱附等温线图（实心是吸附点、空心为脱附点）

表1 PPN-1和PPN-1-OH在1.0bar时的SO2、CO2和N2吸附量

材料	SO₂吸附量/mmol·g^-1				CO₂吸附量/mmol·g^-1		N₂吸附量/mmol·g^-1
材料	273K	298K	308K	323K	273K	298K	273K	298K
PPN-1	17.01	10.38	9.64	9.37	3.99	2.68	0.27	0.18
PPN-1-OH	17.89	13.09	11.16	10.22	3.87	2.60	0.27	0.15

图5 PPN-1和PPN-1-OH的孔径分布和累计孔体积（模型：NLDFT）

图6 PPN-1和PPN-1-OH对SO2、CO2和N2的吸附等温线以及与文献中材料的数据比较

图7 PPN-1和PPN-1-OH对SO2、CO2和N2的等温吸附热Qst

图8 PPN-1和PPN-1-OH在混合气中的SO2/CO2选择性以及与其他多孔材料的比较

图9 多孔材料的CO2/N2选择性比较[a] 基于单组分等温线的吸附比率得到；[b] 基于单组分等温线的亨利常数得到；其他所有CO2/N2（体积比=15∶85）混合气体中的选择性通过IAST方法在298K下计算得到

图10 PPN-1-OH和PPN-1分别对于SO2和CO2的瞬时吸附速度

图11 PPN-1-OH和PPN-1在298K下对SO2/CO2/N2（0.2/9/90.8，体积比）分离的实验穿透曲线

图12 298K潮湿和干燥条件下PPN-1-OH对SO2/CO2/N2分离的实验穿透曲线

图13 SO2/CO2的穿透选择性与IAST选择性的比较

图14 PPN-1-OH在三组分混合气中饱和后的脱附曲线

图15 相同条件下PPN-1-OH对SO2和CO2的循环吸附能力

图16 PPN-1-OH和PPN-1在298K下对CO2/N2（15/85，体积比）分离的实验穿透曲线

图17 利用Materials Studio优化了SO2@PPN-1-OH、CO2@PPN-1-OH、N2@PPN-1-OH的几何形状（虚线代表静电相互作用力，原子之间的距离单位为Å，1Å=0.1nm）

参考文献 40

1	JIANG Xiao, NIE Xiaowa, GUO Xinwen, et al. Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis[J]. Chemical Reviews, 2020, 120(15): 7984-8034.
2	LUCAS Francisco W S, Gary GRIM R, TACEY Sean A, et al. Electrochemical routes for the valorization of biomass-derived feedstocks: From chemistry to application[J]. ACS Energy Letters, 2021, 6(4): 1205-1270.
3	NOVOTNIK Breda, NANDY Arpita, VENKATESAN Senthil Velan, et al. Can fossil fuel energy be recovered and used without any CO₂ emissions to the atmosphere?[J]. Reviews in Environmental Science and Bio/Technology, 2020, 19(1): 217-240.
4	LIU Songtao, HAO Hongke, JIA Wenbo, et al. Effects of ultralow-emission retrofitting on mercury emission from a coal-fired power plant[J]. Energy & Fuels, 2020, 34(6): 7502-7508.
5	ZHANG Yan, ZHANG Peixin, YU Weikang, et al. Highly selective and reversible sulfur dioxide adsorption on a microporous metal-organic framework via polar sites[J]. ACS Applied Materials & Interfaces, 2019, 11(11): 10680-10688.
6	HASHEMI Ali, PAJOUM SHARIATI Farshid, SOHANI Elnaz, et al. CO₂ biofixation by Synechococcus elongatus from the power plant flue gas under various light-dark cycles[J]. Clean Technologies and Environmental Policy, 2020, 22(8): 1735-1743.
7	LI Xiaosen, ZHAN Hao, XU Chungang, et al. Effects of tetrabutyl-(ammonium/phosphonium) salts on clathrate hydrate capture of CO₂ from simulated flue gas[J]. Energy & Fuels, 2012, 26(4): 2518-2527.
8	SHEKHAH Osama, BELMABKHOUT Youssef, CHEN Zhijie, et al. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture[J]. Nature Communications, 2014, 5: 4228.
9	WANG Yuxuan, ZHANG Qian, HE Kebin, et al. Sulfate-nitrate-ammonium aerosols over China: Response to 2000—2015 emission changes of sulfur dioxide, nitrogen oxides, and ammonia[J]. Atmospheric Chemistry and Physics, 2013, 13: 2635-2652.
10	HAN Xue, YANG Sihai, Martin SCHRÖDER. Porous metal-organic frameworks as emerging sorbents for clean air[J]. Nature Reviews Chemistry, 2019, 3(2): 108-118.
11	Jonghun LIM, CHOI Yeongryeol, KIM Geonyeol, et al. Modeling of the wet flue gas desulfurization system to utilize low-grade limestone[J]. Korean Journal of Chemical Engineering, 2020, 37(12): 2085-2093.
12	YANG Lifeng, QIAN Siheng, WANG Xiaobing, et al. Energy-efficient separation alternatives: Metal-organic frameworks and membranes for hydrocarbon separation[J]. Chemical Society Reviews, 2020, 49(15): 5359-5406.
13	WANG Jun, ZHANG Yan, ZHANG Peixin, et al. Optimizing pore space for flexible-robust metal-organic framework to boost trace acetylene removal[J]. Journal of the American Chemical Society, 2020, 142(21): 9744-9751.
14	XIAO Jing, SONG Chunshan, MA Xiaoliang, et al. Effects of aromatics, diesel additives, nitrogen compounds, and moisture on adsorptive desulfurization of diesel fuel over activated carbon[J]. Industrial & Engineering Chemistry Research, 2012, 51(8): 3436-3443.
15	YI Honghong, WANG Zhixiang, LIU Haiyan, et al. Adsorption of SO₂, NO, and CO₂ on activated carbons: equilibrium and thermodynamics[J]. Journal of Chemical & Engineering Data, 2014, 59(5): 1556-1563.
16	CHEN Xi, SHEN Benxian, SUN Hui, et al. Ion-exchange modified zeolites X for selective adsorption desulfurization from Claus tail gas: Experimental and computational investigations[J]. Microporous and Mesoporous Materials, 2018, 261: 227-236.
17	LIAO Junjie, ZHANG Yunfei, FAN Lijun, et al. Insight into the acid sites over modified NaY zeolite and their adsorption mechanisms for thiophene and benzene[J]. Industrial & Engineering Chemistry Research, 2019, 58(11): 4572-4580.
18	HUO Quan, LI Jianshu, QI Xiaoran, et al. Cu, Zn-embedded MOF-derived bimetallic porous carbon for adsorption desulfurization[J]. Chemical Engineering Journal, 2019, 378: 122106.
19	CHEN Fuqiang, LAI Dan, GUO Lidong, et al. Deep desulfurization with record SO₂ adsorption on the metal-organic frameworks[J]. Journal of the American Chemical Society, 2021, 143(24): 9040-9047.
20	GRAPE Erik Svensson, Gabriel FLORES J, HIDALGO Tania, et al. A robust and biocompatible bismuth ellagate MOF synthesized under green ambient conditions[J]. Journal of the American Chemical Society, 2020, 142(39): 16795-16804.
21	SUO Xian, YU Ying, QIAN Siheng, et al. Tailoring the pore size and chemistry of ionic ultramicroporous polymers for trace sulfur dioxide capture with high capacity and selectivity[J]. Angewandte Chemie International Edition, 2021, 60(13): 6986-6991.
22	BRANDT Philipp, NUHNEN Alexander, LANGE Marcus, et al. Metal-organic frameworks with potential application for SO₂ separation and flue gas desulfurization[J]. ACS Applied Materials & Interfaces, 2019, 11(19): 17350-17358.
23	MA Heping, LIU Bailing, LI Bin, et al. Cationic covalent organic frameworks: A simple platform of anionic exchange for porosity tuning and proton conduction[J]. Journal of the American Chemical Society, 2016, 138(18): 5897-5903.
24	RAMEZANIPOUR PENCHAH Hamid, GHAEMI Ahad, GANADZADEH GILANI Hossein. Benzene-based hyper-cross-linked polymer with enhanced adsorption capacity for CO₂ capture[J]. Energy & Fuels, 2019, 33(12): 12578-12586.
25	LI Lina, CAI Kun, WANG Pengyuan, et al. Construction of sole benzene ring porous aromatic frameworks and their high adsorption properties[J]. ACS Applied Materials & Interfaces, 2015, 7(1): 201-208.
26	CHEN Tongfan, ZHANG Wenxiang, LI Bin, et al. Adsorptive separation of aromatic compounds from alkanes by π-π interactions in a carbazole-based conjugated microporous polymer[J]. ACS Applied Materials & Interfaces, 2020, 12(50): 56385-56392.
27	FU Yu, WANG Zhiqiang, LI Sizhe, et al. Functionalized covalent triazine frameworks for effective CO₂ and SO₂ removal[J]. ACS Applied Materials & Interfaces, 2018, 10(42): 36002-36009.
28	RABBANI Mohammad Gulam, ISLAMOGLU Timur, EL-KADERI Hani M. Benzothiazole-and benzoxazole-linked porous polymers for carbon dioxide storage and separation[J]. Journal of Materials Chemistry A, 2017, 5(1): 258-265.
29	WU Linbo, AN Dong, DONG Jie, et al. Preparation and SO₂ absorption/desorption properties of crosslinked poly(1,1,3,3-tetramethylguanidine acrylate) porous particles[J]. Macromolecular Rapid Communications, 2006, 27(22): 1949-1954.
30	DENG Hua, YI Honghong, TANG Xiaolong, et al. Adsorption equilibrium for sulfur dioxide, nitric oxide, carbon dioxide, nitrogen on 13X and 5A zeolites[J]. Chemical Engineering Journal, 2012, 188: 77-85.
31	CUI Xili, YANG Qiwei, YANG Lifeng, et al. Ultrahigh and selective SO₂ uptake in inorganic anion-pillared hybrid porous materials[J]. Advanced Materials, 2017, 29(28): 1606929.
32	CARTER Joseph H, HAN Xue, MOREAU Florian Y, et al. Exceptional adsorption and binding of sulfur dioxide in a robust zirconium-based metal-organic framework[J]. Journal of the American Chemical Society, 2018, 140(46): 15564-15567.
33	YANG Sihai, LIU Leifeng, SUN Junliang, et al. Irreversible network transformation in a dynamic porous host catalyzed by sulfur dioxide[J]. Journal of the American Chemical Society, 2013, 135(13): 4954-4957.
34	LI Guiyang, WANG Zhonggang. Microporous polyimides with uniform pores for adsorption and separation of CO₂ gas and organic vapors[J]. Macromolecules, 2013, 46(8): 3058-3066.
35	SEKIZKARDES Ali Kemal, ALTARAWNEH Suha, KAHVECI Zafer, et al. Highly selective CO₂ capture by triazine-based benzimidazole-linked polymers[J]. Macromolecules, 2014, 47(23): 8328-8334.
36	ARAB Pezhman, RABBANI Mohammad Gulam, SEKIZKARDES Ali Kemal, et al. Copper(I)-catalyzed synthesis of nanoporous azo-linked polymers: Impact of textural properties on gas storage and selective carbon dioxide capture[J]. Chemistry of Materials, 2014, 26(3): 1385-1392.
37	Aysu YURDUŞEN, Yuda YÜRÜM. A controlled synthesis strategy to enhance the CO₂ adsorption capacity of MIL-88B type MOF crystallites by the crucial role of narrow micropores[J]. Industrial & Engineering Chemistry Research, 2019, 58(31): 14058-14072.
38	CMARIK Gregory E, KIM Min, COHEN Seth M, et al. Tuning the adsorption properties of UiO-66 via ligand functionalization[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2012, 28(44): 15606-15613.
39	SMITH Gemma L, EYLEY Jennifer E, HAN Xue, et al. Reversible coordinative binding and separation of sulfur dioxide in a robust metal-organic framework with open copper sites[J]. Nature Materials, 2019, 18(12): 1358-1365.
40	SAVAGE Mathew, CHENG Yongqiang, EASUN Timothy L, et al. Selective adsorption of sulfur dioxide in a robust metal-organic framework material[J]. Advanced Materials, 2016, 28(39): 8705-8711.

[1]	杨寒月, 孔令真, 陈家庆, 孙欢, 宋家恺, 王思诚, 孔标. 微气泡型下向流管式气液接触器脱碳性能[J]. 化工进展, 2023, 42(S1): 197-204.
[2]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[3]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[4]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[7]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[8]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[9]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[10]	刘毅, 房强, 钟达忠, 赵强, 李晋平. Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原[J]. 化工进展, 2023, 42(8): 4136-4142.
[11]	黄玉飞, 李子怡, 黄杨强, 金波, 罗潇, 梁志武. 光催化CO₂和CH₄重整催化剂研究进展[J]. 化工进展, 2023, 42(8): 4247-4263.
[12]	娄宝辉, 吴贤豪, 张驰, 陈臻, 冯向东. 纳米流体用于二氧化碳吸收分离研究进展[J]. 化工进展, 2023, 42(7): 3802-3815.
[13]	白亚迪, 邓帅, 赵睿恺, 赵力, 杨英霞. 变温吸附碳捕集机组标准化测试方案探讨及性能实验[J]. 化工进展, 2023, 42(7): 3834-3846.
[14]	张雪伟, 黄亚继, 许月阳, 程好强, 朱志成, 李金壘, 丁雪宇, 王圣, 张荣初. 碱性吸附剂对燃煤烟气中SO₃的吸附特性[J]. 化工进展, 2023, 42(7): 3855-3864.
[15]	吕超, 张习文, 金理健, 杨林军. 新型两相吸收剂-离子液体系统高效捕获CO₂[J]. 化工进展, 2023, 42(6): 3226-3232.