掺硫介孔炭的制备及其汞脱除特性

doi:10.16085/j.issn.1000-6613.2021-1086

摘要/Abstract

摘要：

采用模板法，以MCM-41为模板剂，2-噻吩乙醇和百里香酚蓝为前体，制备了掺硫介孔炭吸附剂，在固定床汞吸附实验装置上研究了其脱汞性能，考察了前体质量比、煅烧温度、烟气温度与烟气组分（O₂、SO₂）等因素对其脱汞性能的影响，并对吸附剂的物化特性进行了表征，分析了其脱汞特性。结果表明：在前体（2-噻吩乙醇∶百里香酚蓝）质量比为6∶1、煅烧温度为900℃时制备获得的掺硫介孔炭MCM-900-1∶6的脱汞效率最高，其比表面积达932m²/g，C质量分数为81.12%，S质量分数为10.24%；MCM-900-1∶6脱汞温度区间较广，在50～150℃下脱汞效率高达90%；MCM-900-1∶6有着良好的抗SO₂干扰能力，O₂对其脱汞有一定的促进作用；随着煅烧温度上升，掺硫介孔炭的分层现象消失且变得更加规整；FTIR表明900℃煅烧后，掺硫介孔炭的C＝S取代O―H成为数量最多的官能团；XPS分析表明，掺硫介孔炭表面主要为噻吩硫与单质硫，它们对脱汞起主要作用。

关键词: 煤燃烧, 烟道气, 介孔炭, 脱汞, 二氧化硫

Abstract:

The template method was used to prepare sulfur-doped mesoporous carbon sorbents with the template agent of MCM-41 and the precursors of 2-thiophene ethanol and thymol blue. Mercury removal performance of sorbents was studied in a fixed bed experimental device and the effects of precursor mass ratio, calcination temperature, flue gas temperature and composition (O₂, SO₂) on mercury removal were investigated. The physical and chemical properties of the sorbents were characterized to analyze the mercury removal mechanism. The results showed that when the precursor (2-thiopheneethanol∶ thymol blue) mass ratio was 6?∶?1 and the calcination temperature was 900℃, the prepared MCM-900-1∶6 displayed the highest mercury removal rate. The specific surface area of the MCM-900-1∶6 was 932m²/g and the contents of C and S were 81.12% and 10.24%, respectively. The MCM-900-1∶6 had a wide temperature range of mercury removal, and the mercury removal efficiency was as high as 90% at 50—150℃. The MCM-900-1∶6 indicated a good resistance to SO₂, and O₂ somewhat promoted mercury removal. With rising calcination temperature, the layering phenomenon disappeared and the mesoporous carbon became more regular. FTIR analysis showed that after calcination at 900℃, the C＝S replaced O－H to become the most abundant functional group. XPS analysis found that the sulfur on the mesoporous carbon surface was thiophene sulfur and elemental sulfur, which played a major role in mercury removal.

Key words: coal combustion, flue gas, mesoporous carbon, mercury removal, sulfur dioxide

中图分类号:

X511

狄冠丞, 周强, 陶信, 尚瑜, 宋涛, 卢平, 徐贵玲. 掺硫介孔炭的制备及其汞脱除特性[J]. 化工进展, 2022, 41(5): 2761-2769.

DI Guancheng, ZHOU Qiang, TAO Xin, SHANG Yu, SONG Tao, LU Ping, XU Guiling. Preparation of sulfur-doped mesoporous carbon and its mercury removal[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2761-2769.

图/表 16

图1 模拟固定床汞吸附实验系统

图2 前体质量比对吸附剂汞穿透率的影响

图3 前体质量比对吸附剂汞吸附量的影响

图4 煅烧温度对吸附剂汞穿透率的影响

图5 煅烧温度对吸附剂汞吸附量的影响

图6 烟气温度对吸附剂汞穿透率的影响

图7 烟气温度对吸附剂汞吸附量的影响

图8 O2含量对吸附剂汞穿透率的影响

图9 O2含量对吸附剂汞吸附量的影响

图10 SO2浓度对吸附剂汞穿透率的影响

图11 SO2浓度对吸附剂汞吸附量的影响

图12 MCM-900-1∶6吸附剂在初始30min内的汞穿透曲线

表1 掺硫介孔炭的孔结构参数与元素分析

样品	比表面积/m²·g^-1	平均孔径/nm	总孔容积/cm³·g^-1	C质量分数/%	S质量分数/%
MCM-700-1∶6	934.351	3.517	0.821	77.94	12.24
MCM-800-1∶6	944.888	3.161	0.747	80.50	11.23
MCM-900-1∶6	932.998	3.013	0.703	81.12	10.24
MCM-900-1∶5	1066.315	3.458	0.922	70.68	8.51
MCM-900-1∶7	1009.406	3.441	0.868	67.69	8.49

图13 掺硫介孔炭的SEM图像

图14 掺硫介孔炭的FTIR分析

图15 掺硫介孔炭吸附剂脱汞前后的S 2p图谱

参考文献 34

1	NIKSA S, FUJIWARA N. Estimating Hg emissions from coal-fired power stations in China[J]. Fuel, 2009, 88(1): 214-217.
2	GUFFEY F D, BLAND A E. Thermal pretreatment of low-ranked coal for control of mercury emissions[J]. Fuel Processing Technology, 2004, 85(6/7): 521-531.
3	WANG H, SHEN C, DUAN Y F, et al. Synergistic effect between H₂O and SO₂ on mercury removal by activated carbon in O₂/CO₂ conditions[J]. Journal of Chemical Technology and Biotechnology, 2019, 94(4): 1195-1201.
4	TANG H J, YOU W Q, WANG Z W, et al. Detrimental effects of SO₂ on gaseous mercury(‍Ⅱ) adsorption and retention by CaO-based sorbent traps: competition and heterogeneous reduction[J]. Journal of Hazardous Materials, 2020, 387: 121679.
5	ZHOU Q, DUAN Y F, CHEN M M, et al. Effect of flue gas component and ash composition on elemental mercury oxidation/adsorption by NH₄Br modified fly ash[J]. Chemical Engineering Journal, 2018, 345: 578-585.
6	PEARSON R G. Hard and soft acids and bases[J]. Journal of the American Chemical Society, 1973, 85(22): 3533-3539.
7	PEARSON R G. Acids and bases[J]. Science, 1966, 151(3707): 172-177.
8	LIU W, VIDIC R D, BROWN T D. Optimization of high temperature sulfur impregnation on activated carbon for permanent sequestration of elemental mercury vapors[J]. Environmental Science & Technology, 2000, 34(3): 483-488.
9	沈畅, 王卉, 沈昊天, 等. 烟气抗硫脱汞材料的研究进展[J]. 中南大学学报(自然科学版), 2021, 52(1): 133-143.
	SHEN Chang, WANG Hui, SHEN Haotian, et al. Research progress on flue gas mercury removal materials with SO₂ resistance[J]. Journal of Central South University (Science and Technology), 2021, 52(1): 133-143.
10	HUO Q H, WANG Y H, CHEN H J, et al. ZnS/AC sorbent derived from the high sulfur petroleum coke for mercury removal[J]. Fuel Processing Technology, 2019, 191: 36-43.
11	YAO Y X, VELPARI V, ECONOMY J. Design of sulfur treated activated carbon fibers for gas phase elemental mercury removal[J]. Fuel, 2014, 116: 560-565.
12	RUMAYOR M, DIAZ-SOMOANO M, LOPEZ-ANTON M A, et al. Mercury compounds characterization by thermal desorption[J]. Talanta, 2013, 114(3): 318-322.
13	JIA C Q. Production of sulphur and activated carbon: US 6932956[P]. 2005.
14	LI Chaomin, HOU Jian, YU Yong, et al. Ozone decomposition under the irradiation of 253.7nm in the presence of methyl bromide[J]. Journal of Environmental Sciences, 2000, 12(3): 266-269.
15	ZHUANG X, WAN Y, FENG C M, et al. Highly efficient adsorption of bulky dye molecules in wastewater on ordered mesoporous carbons[J]. Chemistry of Materials, 2009, 21(4): 706-716.
16	WANG H, LAM F L Y, HU X J, et al. Ordered mesoporous carbon as an efficient and reversible adsorbent for the adsorption of fullerenes[J]. Langmuir, 2006, 22(10): 4583-4588.
17	HARTMANN M, VINU A, CHANDRASEKAR G. Adsorption of vitamin E on mesoporous carbon molecular sieves[J]. Chemistry of Materials, 2005, 17(4): 829-833.
18	VINU A, STREB C, MURUGESAN V, et al. Adsorption of cytochrome C on new mesoporous carbon molecular sieves[J]. The Journal of Physical Chemistry B, 2003, 107(33): 8297-8299.
19	祝建中, 杨嘉, DENG Baolin. 有序介孔炭合成、改性及其对汞离子的吸附性能[J]. 新型炭材料, 2008, 23(3): 221-227.
	ZHU Jianzhong, YANG Jia, DENG Baolin. Synthesis, modification, and characterization of ordered mesoporous carbons for aqueous mercury ion removal[J]. New Carbon Materials, 2008, 23(3): 221-227.
20	YE J Q, ZHAO H Q, SONG W, et al. Enhanced electronic conductivity and sodium-ion adsorption in N/S co-doped ordered mesoporous carbon for high-performance sodium-ion battery anode[J]. Journal of Power Sources, 2019, 412: 606-614.
21	GU Z M, DENG B L, YANG J. Synthesis and evaluation of iron-containing ordered mesoporous carbon (FeOMC) for arsenic adsorption[J]. Microporous and Mesoporous Materials, 2007, 102(1/2/3): 265-273.
22	WU R P, YE Q, WU K, et al. Adsorption performance of CMK-3 and C-FDU-15 in NO removal at low temperature[J]. Journal of Environmental Sciences, 2020, 87(1): 289-298.
23	SHIN Y, FRYXELL G, UM W, et al. Sulfur-functionalized mesoporous carbon[J]. Advanced Functional Materials, 2007, 17(15): 2897-2901.
24	PENG C Y, HE M, CHEN B B, et al. Magnetic sulfur-doped porous carbon for preconcentration of trace mercury in environmental water prior to ICP-MS detection[J]. Analyst, 2017, 142(23): 4570-4579.
25	周强.改性吸附剂喷射脱汞的实验及机理研究[D]. 南京: 东南大学，2016.
	ZHOU Qiang. Experimental and mechanism researches of in-duct mercury removal by modified sorbent injection[D]. Nanjing: Southeast University, 2016.
26	王晨平. SO₂活化改性高硫石油焦吸附剂的脱汞特性研究[D]. 南京: 东南大学, 2017.
	WANG Chenping. Study on the mercury removal characteristics of SO₂ activated modified high-sulfur petroleum coke adsorbent[D]. Nanjing: Southeast University, 2017.
27	STAVROPOULOS G G, SAMARAS P, SAKELLAROPOULOS G P. Effect of activated carbons modification on porosity, surface structure and phenol adsorption[J]. Journal of Hazardous Materials, 2008, 151(2/3): 414-421.
28	WEI Y Y, YU D Q, TONG S T, et al. Effects of H₂SO₄ and O₂on Hg⁰ uptake capacity and reversibility of sulfur-impregnated activated carbon under dynamic conditions[J]. Environmental Science and Technology, 2015, 49(3): 1706-1712.
29	李娜. 载硫活性炭的汞吸附与再生特性研究[D]. 南京: 东南大学, 2019.
	LI Na. Study on the mercury adsorption and regeneration characteristics of sulfur-loaded activated carbon[D]. Nanjing: Southeast University, 2019.
30	SUN P, ZHANG B, ZENG X B, et al. Deep study on effects of activated carbon’s oxygen functional groups for elemental mercury adsorption using temperature programmed desorption method[J]. Fuel, 2017, 200: 100-106.
31	SHAO H Z, LIU X W, ZHOU Z J, et al. Elemental mercury removal using a novel KI modified bentonite supported by starch sorbent[J]. Chemical Engineering Journal, 2016, 291: 306-316.
32	XIA Y D, ZHU Y Q, TANG Y. Preparation of sulfur-doped microporous carbons for the storage of hydrogen and carbon dioxide[J]. Carbon, 2012, 50(15): 5543-5553.
33	吕维阳, 刘盛余, 能子礼超, 等. 载硫活性炭脱除天然气中单质汞的研究[J]. 中国环境科学, 2016, 36(2): 382-389.
	Weiyang LYU, LIU Shengyu, NENGZI Lichao, et al. Remove elemental mercury by sulfur-impregnated activated carbon in natural gas[J]. China Environmental Science, 2016, 36(2): 382-389.
34	洪亚光, 段钰锋, 朱纯, 等. 硫改性椰壳活性炭管道喷射脱汞实验研究[J]. 东南大学学报(自然科学版), 2015, 45(3): 521-525.
	HONG Yaguang, DUAN Yufeng, ZHU Chun, et al. Experimental study on mercury adsorption of S-impregnated coconut shell activated carbon by duct injection[J]. Journal of Southeast University (Natural Science Edition), 2015, 45(3): 521-525.

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