脱除苯中二硫化碳吸附剂的制备及其吸附性能

doi:10.16085/j.issn.1000-6613.2024-0631

摘要/Abstract

摘要：

采用氯甲基聚苯乙烯大孔树脂（D201）作为接枝载体，通过接枝有机胺类物质制得胺化改性的树脂脱硫吸附剂，并用于脱除苯中微量CS₂；对有机胺类型、洗涤方式、树脂与有机胺质量比等制备条件以及吸附温度、吸附空速、原料CS₂浓度等工艺条件对吸附剂吸附性能的影响进行了考察；采用BET、有机元素分析仪、傅里叶变换红外光谱（FTIR）对吸附剂进行了表征，并对吸附机理进行了分析。研究表明：胺化改性树脂的吸附过程是通过表面伯胺及仲胺基官能团与CS₂反应生成硫代酸，硫代酸不稳定分解生成异硫酸氰酯，继而生成硫脲而被选择吸附下来。在吸附温度为45℃、常压、体积空速为1h^-1、进料CS₂浓度为2000mg/L的条件下，采用D201接枝乙二胺制得的D201-EDA吸附剂的穿透吸附容量和饱和吸附容量分别高达183.33mg/g和200.78mg/g。

关键词: 聚苯乙烯树脂, 有机胺, 脱硫吸附剂, 苯, 二硫化碳

Abstract:

Resin desulfurization adsorbent was prepared by grafting organic amines on chloromethyl polystyrene macroporous resin (D201) for removing trace CS₂ in benzene. Effects of preparation method including amine type, washing method and mass ratio of resin to amine on the adsorption performance were studied. Besides, relations between performance and absorption conditions such as temperature, space velocity and CS₂ concentration of raw material were also investigated. Adsorption mechanism of the absorbent was revealed by the results from BET, organic element analyzer and Fourier transform infrared spectroscopy (FTIR). It was shown that thioic acid was initially generated by CS₂and primary-amine and secondary-amine functional groups on the absorbent. Then, it converted to cyanide isosulfate and finally to thiourea as thioic acid was unstable. As a result, trace CS₂ in benzene was removed. The D201-EDA adsorbent prepared by grafting ethylenediamine on D201 exhibited excellent penetration adsorption capacity and saturated adsorption capacity of 183.33mg/g and 200.78mg/g, respectively, when it conducted at 45℃ under atmospheric pressure with volume space velocity of 1h^-1 and feed CS₂ concentration of 2000mg/L.

Key words: polystyrene resin, organic amines, desulfurization adsorbent, benzene, carbon disulfide

中图分类号:

TQ424

仇玉静, 刘畅, 罗国华, 董森, 李建华. 脱除苯中二硫化碳吸附剂的制备及其吸附性能[J]. 化工进展, 2025, 44(4): 2374-2382.

QIU Yujing, LIU Chang, LUO Guohua, DONG Sen, LI Jianhua. Preparation and adsorption performance of adsorbents for removing carbon disulfide from benzene[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2374-2382.

图/表 15

参考文献 30

1	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.
2	唐晓东, 谯勤, 李晶晶, 等. 裂解C₅脱有机硫实验研究[J]. 石油学报(石油加工), 2014, 30(4): 650-655.
	TANG Xiaodong, QIAO Qin, LI Jingjing, et al. Experimental study on organic sulfide removal from refinery C₅ fraction[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2014, 30(4): 650-655.
3	刘俊, 刘春友, 程晓宇, 等. 脱除裂解碳五中二硫化碳的应用研究[J]. 化工设计通讯, 2020, 46(11): 51-52.
	LIU Jun, LIU Chunyou, CHENG Xiaoyu, et al. Applied research on removing carbon disulfide from cracked carbon five[J]. Chemical Engineering Design Communications, 2020, 46(11): 51-52.
4	曹志涛, 王健, 赵晶, 等. 分子筛吸附脱硫生产清洁燃料[J]. 齐鲁石油化工, 2016, 44(4): 331-334.
	CAO Zhitao, WANG Jian, ZHAO Jing, et al. Molecular sieve adsorptive desulfurization technology for production of clean fuel[J]. Qilu Petrochemical Technology, 2016, 44(4): 331-334.
5	WANG Yuhe, YANG Ralph T, HEINZEL John M. Desulfurization of jet fuel JP-5 light fraction by MCM-41 and SBA-15 supported cuprous oxide for fuel cell applications[J]. Industrial & Engineering Chemistry Research, 2009, 48(1): 142-147.
6	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.
7	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.
8	金健, 张智宏, 白鸿帆. γ-Fe₂O₃/AC脱硫剂的制备及低温脱除CS₂性能[J]. 化工进展, 2018, 37(11): 4397-4404.
	JIN Jian, ZHANG Zhihong, BAI Hongfan. Preparation and performance of γ-Fe₂O₃/AC desulfurizer at low temperature for CS₂ removal[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4397-4404.
9	LU Weigang, SCULLEY Julian P, YUAN Daqiang, et al. Carbon dioxide capture from air using amine-grafted porous polymer networks[J]. Journal of Physical Chemistry C, 2013, 117(8): 4057-4061.
10	Michael MCGUIRK C, SIEGELMAN Rebecca L, DRISDELL Walter S, et al. Cooperative adsorption of carbon disulfide in diamine-appended metal-organic frameworks[J]. Nature Communications, 2018, 9(1): 5133.
11	杨元法, 曾朝霞, 卢茂玲, 等. 乙二胺改性氯球负载Pd(0)配合物催化剂对Heck芳基化反应的催化性能[J]. 石油化工, 2005, 34(10): 970-973.
	YANG Yuanfa, ZENG Zhaoxia, LU Maoling, et al. Performance of Pd(0) complex catalyst supported on ethylenediamine modified-chloromethylpolystyrene for Heck arylation[J]. Petrochemical Technology, 2005, 34(10): 970-973.
12	赵丽华. N,N'-二异丙基碳二亚胺的合成[J]. 山东化工, 2006, 35(3): 1-2, 4.
	ZHAO Lihua. Synthesis of N,N'-diisopropylcarbodiimide[J]. Shandong Chemical Industry, 2006, 35(3): 1-2, 4.
13	申艳玲, 杨云峰, 高保娇, 等. 制备氯甲基化聚苯乙烯交联微球的新方法[J]. 高等学校化学学报, 2007, 28(3): 580-583.
	SHEN Yanling, YANG Yunfeng, GAO Baojiao, et al. New method of preparing chloromethylated crosslinking polystyrene microspheres[J]. Chemical Journal of Chinese Universities, 2007, 28(3): 580-583.
14	罗许英, 陈兰. 佛尔哈德法测定复杂物料中氯[J]. 湖南有色金属, 2019, 35(1): 70-72.
	LUO Xuying, CHEN Lan. Determination of chlorine in complex materials by volhard method[J]. Hunan Nonferrous Metals, 2019, 35(1): 70-72.
15	蒋龙飞, 彭磊, 于萍, 等. 5A分子筛分离工业异己烷中低含量正己烷[J]. 能源化工, 2016, 37(3): 57-62.
	JIANG Longfei, PENG Lei, YU Ping, et al. Separate small amounts of n-hexane from industrial isohexane on 5A molecular sieves[J]. Energy Chemical Industry, 2016, 37(3): 57-62.
16	朱文祥, 梁客, 王昊, 等. 反复淬冷烃类水蒸气转化Z417催化剂的构效研究[J]. 齐鲁石油化工, 2023, 51(4): 261-265.
	ZHU Wenxiang, LIANG Ke, WANG Hao, et al. Structure-activity study of Z417 catalyst with repeatedly quenching treatment for hydrocarbon steam conversion[J]. Qilu Petrochemical Technology, 2023, 51(4): 261-265.
17	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.
18	PENG Bingxian, LI Xinrui, MA Zhen, et al. Release of fluorine and chlorine during increase of phosphate rock grade by calcination and digestion[J]. Environmental Pollution, 2021, 270: 116321.
19	JIANG Hongming, LI C, CHEN Luyou, et al. Dechlorination performance of chemical looping conversion using red mud as an oxygen carrier[J]. Energy & Fuels, 2022, 36(17): 9616-9627.
20	丁梦祎, 任祺恺, 罗婧盈, 等. 植酸改性木粉制备及其吸附性能研究[J]. 北京林业大学学报, 2022, 44(2): 131-140.
	DING Mengyi, REN Qikai, LUO Jingying, et al. Preparation and adsorption property of phytic acid modified wood flour[J]. Journal of Beijing Forestry University, 2022, 44(2): 131-140.
21	何炳林, 周勤馨. 交联聚N-(乙烯苄基)乙二胺的合成(Ⅱ)[J]. 高分子通讯, 1982(3): 213-218.
	HE Binglin, ZHOU Qinxin. The synthesis of the crossljnked poly-N-(vinylbenzyl)ethylenediamine (Ⅱ)[J]. Acta Polymerica Sinica, 1982(3): 213-218.
22	YANG Yan, FU Jiaju, ZHANG Yun, et al. Molecular engineering for bottom-up construction of high-performance non-precious-metal electrocatalysts with well-defined active sites[J]. The Journal of Physical Chemistry C, 2021, 125(41): 22397-22420.
23	WANG Zhen, LIU Jing, YANG Yingju, et al. Molecular mechanistic nature of elemental mercury oxidation by surface oxygens over the Co₃O₄ catalyst[J]. The Journal of Physical Chemistry C, 2020, 124(8): 4605-4612.
24	杨子腾, 张丰润泽, 张艺夕, 等. RAFT水溶液聚合制备调驱用凝胶分散体及其性能评价[J]. 油田化学, 2022, 39(3): 418-424.
	YANG Ziteng, ZHANG Fengrunze, ZHANG Yixi, et al. Preparation and performance evaluation of gel dispersion for profile-controlling and flooding by aqueous RAFT polymerization[J]. Oilfield Chemistry, 2022, 39(3): 418-424.
25	钱多, 苏文恩, 刘致远, 等. 大豆蛋白金纳米簇“关-开”型荧光探针检测炭疽杆菌生物标志物DPA[J]. 光谱学与光谱分析, 2023, 43(6): 1815-1820.
	QIAN Duo, SU Wenen, LIU Zhiyuan, et al. Soy protein gold nanocluster as an “off-on” fluorescent probe for the detection of bacillus anthracis biomarkers DPA[J]. Spectroscopy and Spectral Analysis, 2023, 43(6): 1815-1820.
26	TAVAKOL Hossein, MAHMOUDI Amir, RANJBARI Mohammad-Amin. Synthesis of di- and tri-substituted thiourea derivatives in water using choline chloride-urea catalyst[J]. Journal of Sulfur Chemistry, 2019, 40(2): 113-123.
27	BHOSLE Siddhanath D, JADHAV Krishna A, ITAGE Shivanand V, et al. Zn catalyzed a simple and convenient method for thiourea synthesis[J]. Journal of Sulfur Chemistry, 2023, 44(2): 186-200.
28	DING Chaochao, WANG Shaoli, SHENG Yaoguang, et al. One-step construction of unsymmetrical thioureas and oxazolidinethiones from amines and carbon disulfide via a cascade reaction sequence[J]. RSC Advances, 2019, 9(46): 26768-26772.
29	李合平, 常帅军, 宋士杰, 等. 对称性硫脲的绿色合成工艺[J]. 精细化工, 2023, 40(6): 1386-1392.
	LI Heping, CHANG Shuaijun, SONG Shijie, et al. Green synthesis of symmetric thiourea compounds[J]. Fine Chemicals, 2023, 40(6): 1386-1392.
30	GARCÍA-VALENZUELA J A. Simple thiourea hydrolysis or intermediate complex mechanism? Taking up the formation of metal sulfides from metal-thiourea alkaline solutions[J]. Comments on Inorganic Chemistry, 2017, 37(2): 99-115.

洗涤方式	树脂种类	穿透时间/h	穿透吸附容量/mg·g^-1	饱和吸附容量/mg·g^-1	N质量分数/%	Cl质量分数/%
水洗	D201-EDA	42.00	175.00	202.99	12.31	15.10
碱洗	D201-EDA	44.00	183.33	200.78	12.92	0

洗涤方式	树脂种类	穿透时间/h	穿透吸附容量/mg·g^-1	饱和吸附容量/mg·g^-1	N质量分数/%	Cl质量分数/%
水洗	D201-EDA	42.00	175.00	202.99	12.31	15.10
碱洗	D201-EDA	44.00	183.33	200.78	12.92	0

有机胺种类	吸附剂	穿透时间/h	穿透吸附容量/mg·g^-1	饱和吸附容量/mg·g^-1	N质量分数/%
DETA	D201-DETA	42.50	177.08	191.57	12.48
EDA	D201-EDA	44.00	183.33	200.78	12.92

有机胺种类	吸附剂	穿透时间/h	穿透吸附容量/mg·g^-1	饱和吸附容量/mg·g^-1	N质量分数/%
DETA	D201-DETA	42.50	177.08	191.57	12.48
EDA	D201-EDA	44.00	183.33	200.78	12.92

胺化原料配比m(D201)∶m(EDA)	吸附剂	穿透时间/h	穿透吸附容量/mg·g^-1	饱和吸附容量/mg·g^-1	N质量分数/%
1∶1	D201-EDA	41.00	170.83	183.58	12.04
1∶2	D201-EDA	44.00	183.33	200.78	12.92
1∶3	D201-EDA	40.00	166.67	179.08	11.75
1∶4	D201-EDA	40.00	166.67	180.40	11.75
1∶6	D201-EDA	39.00	162.50	176.21	11.46