胺化改性树脂脱二硫化碳吸附剂的制备及吸附动力学

doi:10.16085/j.issn.1000-6613.2023-2129

摘要/Abstract

摘要：

以氯甲基聚苯乙烯大孔树脂为载体，二乙烯三胺为胺化剂，通过取代反应将含伯胺和仲胺的活性官能团锚定到树脂链上制得CS₂脱硫吸附剂，采用FTIR、元素分析仪、BET对改性树脂进行表征，并对吸附剂脱除苯中CS₂吸附性能进行评价，得到不同温度及不同CS₂初始浓度下的吸附穿透曲线，采用Langmuir和Freundlich模型对吸附剂吸附苯中CS₂的吸附等温线进行分析，准一级、准二级动力学模型及颗粒扩散模型对吸附动力学进行拟合。结果表明：胺化改性的聚苯乙烯树脂具有优异的选择性吸附二硫化碳性能，其在常压、318.15K、1h^-1、原料CS₂浓度为2000mg/L条件下的穿透吸附容量高达154.167mg/g。同时，该吸附剂吸附CS₂符合Langmuir模型和准二级动力学模型，吸附控制步骤为CS₂与吸附剂表面活性胺基基团的反应，而非传质过程。通过建立动态吸附过程的Y-N吸附模型，并对吸附穿透曲线进行分析验证，拟合值与实验值十分吻合。

关键词: 二硫化碳, 树脂, 脱硫, 吸附剂, 吸附动力学

Abstract:

The carbon disulfide desulfurization adsorbent was prepared by anchoring active functional groups containing primary and secondary amines onto the resin chain through substitution reaction using chloromethylpolystyrene resin as the carrier and diethylenetriamine as the aminating agent, and the modified resin adsorbent was characterized by FTIR, element analysis, and BET. Subsequently, the adsorption performance of the adsorbent for removing CS₂ from benzene was evaluated, and the adsorption breakthrough curves were obtained at different temperatures and initial concentrations of CS₂. Langmuir and Freundlich models were used to analyze the adsorption isotherms of CS₂ in benzene, and quasi first and quasi second order kinetic models, as well as particle diffusion models, were used to fit the adsorption kinetics. The results showed that the amine modified polystyrene resin had excellent selective adsorption performance for carbon disulfide, with a penetration adsorption capacity of up to 154.17mg/g at the adsorption condition of air-pressure, 318.15K, 1h^-1, 2000mg/L CS₂ in benzene. In addition, the adsorption of CS₂ by the adsorbent conforms to Langmuir model and the quasi second order kinetic model, and the adsorption control step was the reaction between CS₂ and the surface active amino group of the adsorbent, rather than the mass transfer process. By establishing a Y-N dynamic adsorption model for the adsorption process and verifying the adsorption breakthrough curve, the fitted values were in good agreement with the experimental values.

Key words: carbon disulfide, resin, desulfurization, adsorbent, adsorption kinetics

中图分类号:

TQ424

仇玉静, 刘畅, 林杰, 罗国华, 戴晓兵. 胺化改性树脂脱二硫化碳吸附剂的制备及吸附动力学[J]. 化工进展, 2024, 43(12): 7115-7124.

QIU Yujing, LIU Chang, LIN Jie, LUO Guohua, DAI Xiaobing. Preparation and adsorption kinetics of resin adsorbent modified by amine for removing carbon disulfide[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 7115-7124.

图/表 16

参考文献 31

1	李怀柱. 黄原酸盐反应法脱除焦化粗苯中的二硫化碳[D]. 太原: 太原理工大学, 2012.
	LI Huaizhu. The removal of carbon disulfide in crude benzene by using xanthogenate method[D]. Taiyuan: Taiyuan University of Technology, 2012.
2	江大好, 宿亮虎, 陆殿乔, 等. 焦化粗苯的组成及其加氢精制工艺技术的开发[J]. 现代化工, 2009, 29(5): 72-75.
	JIANG Dahao, SU Lianghu, LU Dianqiao, et al. Crude benzol coking products and development of its hydro-refining technology[J]. Modern Chemical Industry, 2009, 29(5): 72-75.
3	党帅, 岳红. 粗苯深加工路线及焦化粗苯产业发展分析[J]. 煤化工, 2013, 41(2): 4-7.
	DANG Shuai, YUE Hong. Route of deep processing of crude benzol and development of the coking crude benzol industry[J]. Coal Chemical Industry, 2013, 41(2): 4-7.
4	曾丹林, 胡义, 王可苗, 等. 焦化粗苯中噻吩分离回收的研究进展[J]. 精细石油化工进展, 2012, 13(1): 45-50.
	ZENG Danlin, HU Yi, WANG Kemiao, et al. Progress on recovery of thiophene in coking crude benzene[J]. Advances in Fine Petrochemicals, 2012, 13(1): 45-50.
5	梁顺琴, 吕龙刚, 马好文, 等. 硫化物对裂解汽油一段加氢用Pd/Al₂O₃催化剂性能的影响[J]. 现代化工, 2014, 34(9): 85-87.
	LIANG Shunqin, Longgang LYU, MA Haowen, et al. Effects of sulfur compounds on performance of Pd/Al₂O₃ catalyst for first-stage hydrogenation of pyrolysis gasoline[J]. Modern Chemical Industry, 2014, 34(9): 85-87.
6	LIAO Junjie, BAO Lei, WANG Wenbo, et al. Preparation of AlCl₃/silica gel catalyst for simultaneously removing thiophene and olefins from coking benzene by inclosed grafting method[J]. Fuel Processing Technology, 2014, 117: 38-43.
7	王丽, 吴迪镛, 王树东, 等. 稀土氧化物CeO₂脱除二硫化碳的研究[J]. 中国稀土学报, 2005, 23(S1): 35-39.
	WANG Li, WU Diyong, WANG Shudong, et al. Study on removal of carbon disulfide by CeO₂ [J]. Journal of the Chinese Society of Rare Earths, 2005, 23(S1): 35-39.
8	HE Dan, YI Honghong, TANG Xiaolong, et al. Carbon disulfide hydrolysis over Fe-Cu/AC catalyst modified by cerium and lanthanum at low temperature[J]. Journal of Rare Earths, 2010, 28: 343-346.
9	王丽, 李福林, 吴迪镛, 等. 催化水解-氧化耦合一步法脱除二硫化碳的研究[J]. 燃料化学学报, 2004, 32(4): 466-470.
	WANG Li, LI Fulin, WU Diyong, et al. A novel desulfuring agent for CS₂ removal by couple processing[J]. Journal of Fuel Chemistry and Technology, 2004, 32(4): 466-470.
10	贾丽丽, 胡典明, 孔渝华. 脱除二硫化碳的研究进展[J]. 辽宁化工, 2008, 37(3): 184-186.
	JIA Lili, HU Dianming, KONG Yuhua. Development of removing carbon disulfide[J]. Liaoning Chemical Industry, 2008, 37(3): 184-186.
11	YANG Ji, JUAN Peng, SHEN Zhemin, et al. Removal of carbon disulfide (CS₂) from water via adsorption on active carbon fiber (ACF)[J]. Carbon, 2006, 44(8): 1367-1375.
12	李敏, 张智宏, 魏燕. 活性炭基π络合吸附剂的制备及其脱除二硫化碳性能[J]. 精细化工, 2016, 33(10): 1130-1134.
	LI Min, ZHANG Zhihong, WEI Yan. Preparation of π complexation adsorbent based on activated carbon and its removal performance for carbon disulfide[J]. Fine Chemicals, 2016, 33(10): 1130-1134.
13	孟令刚, 张现策, 李芹, 等. 焙烧气氛对K₂CO₃/γ-Al₂O₃吸附剂脱除异戊二烯中二硫化碳性能的影响[J]. 化工进展, 2021, 40(1): 221-226.
	MENG Linggang, ZHANG Xiance, LI Qin, et al. Effect of calcination atmosphere on K₂CO₃/γ-Al₂O₃ adsorbent for removing carbon disulfide from isoprene[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 221-226.
14	王亚宁, 熊春华, 王槐三. 树脂吸附法去除水及空气中的CS₂ [J]. 化工环保, 2006, 26(3): 174-177.
	WANG Yaning, XIONG Chunhua, WANG Huaisan. Removal of CS₂ from water and air by resin adsorption process[J]. Environmental Protection of Chemical Industry, 2006, 26(3): 174-177.
15	曲宏昌, 马佳凯, 龙超. 吸附树脂和活性炭吸附气体中二硫化碳的性能差异及成因研究[J]. 中国环境科学, 2023, 43(9): 4534-4541.
	QU Hongchang, MA Jiakai, LONG Chao. An investigation of the causes of different adsorption properties of carbon disulfide vapor in gas on polymeric resin and activated carbon[J]. China Environmental Science, 2023, 43(9): 4534-4541.
16	WANG Shuangshuang, ZHANG Liang, LONG Chao, et al. Enhanced adsorption and desorption of VOCs vapor on novel micro-mesoporous polymeric adsorbents[J]. Journal of Colloid and Interface Science, 2014, 428: 185-190.
17	杨新玉, 史秋怡, 龙超. 吸附树脂吸附多组分VOCs的动力学特性及预测[J]. 中国环境科学, 2019, 39(5): 1830-1837.
	YANG Xinyu, SHI Qiuyi, LONG Chao. Adsorption kinetics and prediction of multicomponent VOCs on polymeric resins[J]. China Environmental Science, 2019, 39(5): 1830-1837.
18	孟启, 肖网琴, 戎志峰, 等. 二(β-氨基乙基)胺型聚苯乙烯树脂的合成和性能研究[J]. 离子交换与吸附, 2014, 30(3): 258-266.
	MENG Qi, XIAO Wangqin, RONG Zhifeng, et al. Synthesis and adsorption properties of di(β-aminoethyl) amine polystyrene resins[J]. Ion Exchange and Adsorption, 2014, 30(3): 258-266.
19	郑子苹, 沈健, 邓桂春. ZSM-5-SBA-15复合分子筛吸附脱除碱性氮动力学数学模型[J]. 精细石油化工, 2022, 39(5): 48-51.
	ZHENG Ziping, SHEN Jian, DENG Guichun. Mathematic model of adsorption denitrogenation kinetics of ZSM-5-SBA-15 composite molecular sieve[J]. Speciality Petrochemicals, 2022, 39(5): 48-51.
20	赵子科, 陈春亮, 柯盛, 等. 榴莲壳和不同炭材料对低汞溶液的吸附动力学[J]. 岩矿测试, 2022, 41(1): 90-98.
	ZHAO Zike, CHEN Chunliang, KE Sheng, et al. Adsorption kinetics of low mercury solution with durian shell and activated carbon[J]. Rock and Mineral Analysis, 2022, 41(1): 90-98.
21	刘新辙, 陈娟, 张明阳, 等. CO₂在栗子壳基碳材料上的吸附动力学及热力学研究[J]. 应用化工, 2023, 52(2): 445-450.
	LIU Xinzhe, CHEN Juan, ZHANG Mingyang, et al. Kinetics and thermodynamics of CO₂ on chestnut shell-based carbon materials[J]. Applied Chemical Industry, 2023, 52(2): 445-450.
22	孟冠华, 张林森, 刘宝河, 等. 可见光下Cu₂O/TiO₂催化臭氧氧化头孢曲松钠性能研究[J]. 过程工程学报, 2023, 23(2): 311-322.
	MENG Guanhua, ZHANG Linsen, LIU Baohe, et al. Photocatalytic ozonation of ceftriaxone sodium by Cu₂O/TiO₂ under visible light[J]. The Chinese Journal of Process Engineering, 2023, 23(2): 311-322.
23	曹仕文, 张鸿, 孟驰涵, 等. 海藻酸钠/二氧化硅杂化微球结构与吸附性能[J]. 化工进展, 2018, 37(9): 3512-3519.
	CAO Shiwen, ZHANG Hong, MENG Chihan, et al. Structure and properties of sodium alginate/silica hybrid microspheres[J]. Chemical Industry and Engineering Progress, 2018, 37(9): 3512-3519.
24	郭可心, 田佳一, 孙煜璨, 等. 磁性污泥基生物炭对Pb²⁺的吸附性能[J]. 环境工程学报, 2022, 16(5): 1416-1428.
	GUO Kexin, TIAN Jiayi, SUN Yucan, et al. Adsorption performance of magnetic sludge-derived biochar towards Pb²⁺ [J]. Chinese Journal of Environmental Engineering, 2022, 16(5): 1416-1428.
25	LI Tingting, LIU Yunguo, PENG Qingqing, et al. Removal of lead(Ⅱ) from aqueous solution with ethylenediamine-modified yeast biomass coated with magnetic chitosan microparticles: Kinetic and equilibrium modeling[J]. Chemical Engineering Journal, 2013, 214: 189-197.
26	Abuzer ÇELEKLI, Gizem İLGÜN, Hüseyin BOZKURT. Sorption equilibrium, kinetic, thermodynamic, and desorption studies of Reactive Red 120 on Chara contraria [J]. Chemical Engineering Journal, 2012, 191: 228-235.
27	ZHAO Yafei, ZHANG Bing, ZHANG Xiang, et al. Preparation of highly ordered cubic NaA zeolite from halloysite mineral for adsorption of ammonium ions[J]. Journal of Hazardous Materials, 2010, 178(1/2/3): 658-664.
28	杨静, 沈健, 石薇薇. Cu-β/SBA-15的吸附脱硫性能及吸附动力学[J]. 精细化工, 2017, 34(10): 1153-1160.
	YANG Jing, SHEN Jian, SHI Weiwei. Adsorption desulfurization and adsorption kinetics of Cu-β/SBA-15[J]. Fine Chemicals, 2017, 34(10): 1153-1160.
29	岳晓晴. 醇胺基二硫化碳储集材料的合成及制备金属硫化物的研究[D]. 呼和浩特: 内蒙古工业大学, 2019.
	YUE Xiaoqing. Study on synthesis of alcoholamine-based carbon disulfide storage materials and preparation of metal sulfides[D]. Hohhot: Inner Mongolia University of Tehchnology, 2019.
30	马佳凯, 许博文, 梁晓珊, 等. CS₂在超高交联树脂上的吸附脱附特性研究[J]. 应用化工, 2018, 47(8): 1684-1687, 1694.
	MA Jiakai, XU Bowen, LIANG Xiaoshan, et al. Adsorption and desorption behavior of carbon disulfide on hypercrosslinked resin[J]. Applied Chemical Industry, 2018, 47(8): 1684-1687, 1694.
31	霍宇辰, 靳岩, 张茜, 等. 分子筛吸附脱除2-甲基四氢呋喃中水的研究[J]. 现代化工, 2021, 41(3): 134-139.
	HUO Yuchen, JIN Yan, ZHANG Xi, et al. Study on removing water from 2-methyltetrahydrofuran by molecular sieves adsorption[J]. Modern Chemical Industry, 2021, 41(3): 134-139.

分析物	元素质量分数/%
分析物	N	C	H	S
胺化改性树脂	10.85	77.81	7.66	0

分析物	元素质量分数/%
分析物	N	C	H	S
胺化改性树脂	10.85	77.81	7.66	0

样品	BET比表面积 /m²·g^-1	孔体积 /cm³·g^-1	平均孔径 /nm
氯甲基聚苯乙烯大孔树脂	11.668	0.081	27.710
二乙烯三胺胺化改性树脂	18.901	0.098	20.699
45℃吸附饱和后的树脂	19.520	0.095	19.518

样品	BET比表面积 /m²·g^-1	孔体积 /cm³·g^-1	平均孔径 /nm
氯甲基聚苯乙烯大孔树脂	11.668	0.081	27.710
二乙烯三胺胺化改性树脂	18.901	0.098	20.699
45℃吸附饱和后的树脂	19.520	0.095	19.518

c₀/mg·L^-1	308.15K		318.15K		328.15K		338.15K
c₀/mg·L^-1	c_e/mg·L^-1	q_e/mg·g^-1	c_e/mg·L^-1	q_e/mg·g^-1	c_e/mg·L^-1	q_e/mg·g^-1	c_e/mg·L^-1	q_e/mg·g^-1
500	1.000	14.306	1.500	14.292	1.500	14.292	1.000	14.306
1000	3.295	28.575	3.536	28.568	4.051	28.554	2.564	28.596
1500	10.631	42.700	8.467	42.762	8.667	42.756	5.277	42.853
2000	24.852	56.627	18.532	56.808	22.059	56.707	14.610	56.921