Recent advance in low concentration volatile organic compounds adsorption and concentration materials

doi:10.16085/j.issn.1000-6613.2020-1514

Abstract

Abstract:

There is an urgent need but it is still a significant challenge to eliminate volatile organic compounds (VOCs) due to its serious threat to environment. This review summarized the treatment for low-concentration VOCs elimination with large air flow and focused on the adsorption and catalytic combustion treatment. Actually, there is a very large total amount of VOCs emission for low-concentration VOCs with large air flow. The VOCs concentration technology should be the effective way for reducing the cost during the VOCs treatment process, which could improve the VOCs concentration and decrease the air flow. And the development of high-performance VOCs adsorption materials is the key to VOCs concentration technology. This review introduced the properties of activated carbon, molecular sieve and other important adsorption materials in detail. Moreover, the principle of adsorption of VOCs and the effects of adsorption material properties and VOCs types on the adsorption result were also discussed. The application of activated carbon concentration-catalytic combustion technology and molecular sieve runner concentration-catalytic combustion technology in the treatment of low concentration VOCs with large air flow are prospected.

Key words: VOCs, active carbon, molecular sieves, adsorption concentration, catalytic combustion

摘要：

由于挥发性有机物（VOCs）会对环境造成严重的危害，因此VOCs的处理一直备受人们的关注，但发展高效的VOCs处理技术仍然存在严峻的挑战。本文针对大风量、低浓度VOCs的处理展开了综述，重点围绕吸附、催化燃烧处理展开讨论。对于大风量的低浓度VOCs，虽然浓度较低但VOCs排放量非常巨大。通过VOCs浓缩技术，提高浓度减少风量成为降低VOCs处理成本的有效途径。其中，发展高性能VOCs吸附材料是VOCs浓缩技术的关键。阐明了活性炭、分子筛等重要吸附材料的性质及其吸附VOCs的原理，并对吸附材料性质和VOCs种类对吸附效果的影响进行了探讨。展望了活性炭浓缩-催化燃烧技术和分子筛转轮浓缩-催化燃烧技术在大风量的低浓度VOCs处理中的应用前景。

关键词: 挥发性有机物, 活性炭, 分子筛, 吸附浓缩, 催化燃烧

CLC Number:

TQ09

Xingyue LENG, Caihong HU, Weiyue WANG, Dandan LI, Jian CHEN, Mengfei LUO. Recent advance in low concentration volatile organic compounds adsorption and concentration materials[J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 336-345.

冷星月, 胡彩虹, 王炜月, 李丹丹, 陈建, 罗孟飞. 低浓度挥发性有机物吸附浓缩材料的研究进展[J]. 化工进展, 2020, 39(S2): 336-345.

Figures/Tables 13

References 14

15	FÉREY G, MELLOT-DRANIEKS C, SERRE C, et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science, 2005, 309(5743): 2040-2042.
16	MORRIS W, DOONAN C J, YAGHI O M. Postsynthetic modification of a metal-organic framework for stabilization of a hemiaminal and ammonia uptake[J]. Inorganic Chemistry, 2011, 50(15): 6853-6855.
17	CHAE H K, SIBERIO-PÉREZ D Y, KIM J, et al. A route to high surface area, porosity and inclusion of large molecules in crystals[J]. Nature, 2004, 427(6974): 523-527.
18	YANG K, XUE F, SUN Q, et al. Adsorption of volatile organic compounds by metal-organic frameworks MOF-177[J]. Journal of Environmental Chemical Engineering, 2013, 1(4): 713-718.
19	YANG K, SUN Q, XUE F, et al. Adsorption of volatile organic compounds by metal-organic frameworks MIL-101: influence of molecular size and shape[J]. Journal of Hazardous Materials, 2011, 195: 124-131.
20	商连弟, 王宗兰, 揣效忠, 等. 八种晶型氧化铝的研制与鉴别[J]. 化学世界, 1994(7): 346-350.
	SHANG Liandi, WANG Zonglan, CHUAI Xiaozhong, et al. Development and identification of eight crystal forms of alumina[J]. Chemical Word, 1994(7): 346-350.
21	刘纪江, 隋红, 王泽利, 等. 极性VOCs组分在硅胶上的吸脱附性质研究[J]. 现代化工, 2018, 38(12): 181-185.
	LIU Jijiang, Hong SUI, WANG Zeli, et al. Adsorption and desorption properties of polar VOCs on silica gel[J]. Moden Chemical Industry, 2018, 38(12): 181-185．
22	王稚真, 卢晗锋, 张波, 等. 水蒸气对改性椰壳活性炭吸附VOCs的影响[J]. 环境工程学报, 2010, 4(11): 2566-2570.
1	SING K. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity[J]. Pure & Applied Chemistry, 1982, 57(4): 603-619.
2	白洪亮. 活性炭吸附法脱除低浓度苯系物的研究[D]. 大连: 大连理工大学, 2006.
22	WANG Zhizhen, LU Hanfeng, ZHANG Bo, et al. Effect of water vapor on adsorption of VOCs by modified cocoanut activated carbon[J]. Chinese Journal of Environmental, 2010, 4(11): 2566-2570.
23	高华生, 汪大翚, 叶芸春, 等. 空气湿度对低浓度有机蒸气在活性炭上吸附平衡的影响[J]. 环境科学学报, 2002(2): 194-198.
	GAO Huasheng, WANG Dahui, YE Yunchun, et al. The influence of atmospheric humidity on the adsorption capacity of activated carbon for low-concentration VOCs[J]. Acta Science Circumstantiae, 2002(2): 194-198.
24	刘玉洁, 闫伦靖, 白永辉, 等. Y型分子筛介孔改性的研究进展[J]. 化工进展, 2018, 37(2): 569-575.
	LIU Yujie, YAN Lunjing, BAI Yonghui, et al. Research progress of mesopore-modification of Y zeolites[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 569-575.
25	黄海凤, 戎文娟, 顾勇义, 等. ZSM-5沸石分子筛吸附-脱附VOCs的性能研究[J]. 环境科学学报, 2014, 34(12): 3144-3151.
	HUANG Haifeng, RONG Wenjuan, GU Yongyi, et al. Adsorption and desorption of VOCs on the ZSM-5 zeolite[J]. Acta Scientiae Circumstantiae, 2014, 34(12): 3144-3151.
26	AL-JANABI N, HILL P, TORRENTE-MURCIANO L. Mapping the Cu-BTC metal-organic framework (HKUST-1) stability envelope in the presence of water vapour for CO₂ adsorption from flue gases[J]. Chemical Engineering Journal, 2015, 281: 669-677.
27	XIAN S, YU Y, XIAN J, et al. Competitive adsorption of water vapor with VOCs dichloroethane,ethylace -tate and benzene on MIL-101(Cr) in humid atmosphere[J]. RSC Advances, 2014, 2015(3): 1827-1834.
28	周春何, 卢晗锋, 曾立, 等. 沸石分子筛和活性炭吸附/脱附甲苯性能对比[J]. 环境污染与防治, 2009, 31(4): 38-41, 44.
	ZHOU Chunhe, LU Hanfeng, ZENG Li, et al. Relative performance of zeolites and activated carbon in gaseous phase adsorption and desorption of toluene[J]. Environmental Pollution & Control, 2009, 31(4): 38-41, 44.
29	张智, 马修卫, 李津津, 等. 中高温环境下VOCs在活性炭上的吸附性能研究[J]. 化工学报, 2019, 70(12): 4811-4820.
	ZHANG Zhi, MA Xiuwei, LI Jingjing, et al. Study on adsorption capacity of VOCs on activated carbon at medium-high temperature[J]. CIESC Journal, 2019, 70(12): 4811-4820.
30	梁欣欣, 卜龙利, 刘嘉栋, 等. 分子筛负载型吸附剂对典型VOCs的吸附行为特性[J]. 环境工程学报, 2016, 10(6): 3152-3160.
	LIANG Xinxin, BU Longli, LIU Jiadong, et al. Adsorption characteristics of typical VOCs on Cu-Mn-Ce/ZSM adsorbent fixed-bed[J]. Chinese Journal of Environmental Engieering, 2016, 10(6): 3152-3160.
31	罗宏慧, 朱质彬, 申永浩. 活性炭共吸附现象对有机蒸气穿透容量的影响[J]. 哈尔滨工业大学学报, 1997(5): 104-107.
	LUO Honghui, ZHU Zhibin, SHENG Yonghao, et al. The effect of activated carbon co-adsorption on organic vapor breakthrough capacity[J]. Journal of Harbin Institute of Technology, 1997(5): 104-107.
32	VAHDAT N. Theoretical study of the performance of activated carbon in the presence of binary vapor mixtures[J]. Carbon, 1997, 35(10): 1544-1557.
33	王海林, 张国宁, 聂磊, 等. 我国工业VOCs减排控制与管理对策研究[J]. 环境科学, 2011, 32(12): 3462-3468.
	WANG Hailin, ZHANG Guoning, NIE Lei, et al. Study on control and management for industrial volatile organic compounds ( VOCs) in china[J]. Environmental Science, 2011, 32 (12): 3462-3468.
34	席劲瑛, 武俊良, 胡洪营, 等. 工业VOCs气体处理技术应用状况调查分析[J]. 中国环境科学, 2012, 32(11): 1955-1960.
	XI Jingyin, WU Junliang, HU Hongying, et al. Application status of industrial VOCs gas treatment techniques[J]. China Environmental Science, 2012, 32(11): 1955-1960.
35	许伟, 刘军利, 孙康. 活性炭吸附法在挥发性有机物治理中的应用研究进展[J]. 化工进展, 2016, 35(4): 1223-1229.
	XU Wei, LIU Junli, SUN Kang, et al. Application progresses in the treatment of volatile organic compounds by adsorption on activated carbon[J]. Chemical Industry and Engineering Progress, 2016, 35(4): 1223-1229.
36	李蕾, 王学华, 王浩, 等. 吸附浓缩-催化燃烧工艺处理低浓度大风量有机废气[J]. 环境工程学报, 2015, 9(11): 5555-5561.
	LI Lei, WANG Xuehua, WANG Hao, et al. Adsorption and catalytic combustion for volatile organic compoundswith large flow and low concentration[J]. Chinese Journal of Environmental Engineering, 2015, 9(11): 5555-5561.
37	巩远辉, 王燕, 蔡旺锋, 等. 吸附浓缩-蓄热催化燃烧工艺过程研究[J]. 现代化工, 2019, 39(5): 202-206.
	GONG Yuanhui, WANG Yan, CAI Wangfeng, et al. Study on adsorption concentration-regenerative catalytic combustion process[J]. Modern Chemical Industry, 2019, 39(5): 202-206.
38	TOSHIO Y, KAZUYA A, MAKOTO S, et al. Development of new hybrid VOCs treatment process using activated carbon and electrically heated alumite catalyst[J]. Journal of Chemical Engineering of Japan, 2013, 46(12): 802-810.
39	董霓, 林艳军, 崔玉东. 治理VOCs的新工艺-沸石转轮吸附浓缩+催化燃烧[J]. 环境与发展, 2017, 29(7): 118-119.
	DONG Ni, LIN Yanjun, CUI Yudong, et al. A new process for controlling VOCs-Zeolite runner adsorption concentration + catalytic combustion[J]. Environment and Development, 2017, 29(7): 118-119.
40	王家德, 郑亮巍, 朱润晔, 等. 改性13X沸石蜂窝转轮对甲苯的吸附性能研究[J]. 环境科学, 2013, 34(12): 4684-4688.
	WANG Jiade, DENG Liangwei, ZHU Runye, et al. Removal of toluene from waste gas by honeycomb adsorption rotor with modified 13X molecular sieves[J]. Environmental Science, 2013, 34 (12): 4684-4688.
41	王毅. 沸石转轮+RTO工艺在低浓度VOCs废气治理中的应用[J]. 浙江化工, 2020, 51(2): 36-40.
	WANG Yi. Application of zeolite runner + RTO process in low-concentration VOCs waste gas treatment[J]. Zhejiang Chemical Industry, 2020, 51(2): 36-40.
2	BAI Hongliang. Removal of low concentration BTEX with adsorption method by using activated carbon[D]. Dalian: Dalian University of Technology, 2006.
3	罗小会. 负载分子筛蜂窝状陶瓷对VOCs吸脱附性能研究[D]. 杭州: 浙江师范大学, 2019.
	LUO Xiaohui. Adsorption and desorption properties of VOCs on molecular sieve-supported honeycome[D]. Hangzhou: Zhejiang Normal University, 2019.
4	罗小会, 张文霞, 宋宇鹏, 等. 负载分子筛的蜂窝状陶瓷对VOCs的吸脱附性能[J]. 环境工程, 2019, 37(S1): 169-174.
	LUO Xiaohui, ZHANG Wenxia, SONG Yupeng, et al. Adsorption and desorption properties of VOCs on honeycome ceramics loaded with molecular sieve[J]. Envoronmental Engineering, 2019, 37(S1): 169-174.
5	钱薇, 张浩哲, 陈超宇, 等. 活性炭和分子筛吸附VOCs的研究进展[J]. 化工生产与技术, 2019, 25(3): 19-23.
	QIAN Wei, ZHANG Haozhe, CHEN Chaoyu,et al. Research progress on the adsorption of VOCs by activated carbon and molecular sieves[J]. Chemical Production and Technology, 2019, 25(3): 19-23.
6	张本镔, 刘运权, 叶跃元. 活性炭制备及其活化机理研究进展[J]. 现代化工, 2014, 34(3): 34-39.
	ZHANG Benbing, LIU Yunquan, YE Yueyuan. Progress in preparation of activated carbon and its activation mechanism[J]. Moden Chemical Industy, 2014, 34(3): 34-39.
7	LILLO-RÓDENAS M, CAZORLA-AMORÓS D, LINARES-SOLANO A. Behaviour of activated carbons with different pore size distributions and surface oxygen groups for benzene and toluene adsorption at low concentrations[J]. Carbon, 2005, 43(8): 1758-1767.
8	岳旭, 王胜, 刘旭, 等. 不同吸附剂上动态吸附-脱附挥发性有机气体性能研究[J]. 燃料化学学报, 2020, 48(1): 120-128.
	YU Xu, WANG Sheng, LIU Xu, et al. Dynamic adsorption and desorption of volatile organic compounds on different adsorbents[J]. Journal of Fuel Chemistry and Technology, 2020, 48(1): 120-128.
9	BARRER R M. Zeolites and their synthesis[J]. Zeolites, 1981, 1(3): 130-140.
10	周燕芳. 分子筛VOCs吸附性能及其工业化应用研究[D]. 杭州: 浙江大学, 2019.
	ZHOU Yanfang. Adsorption performance and industrial application of zeolites for VOCs[D]. Hangzhou: Zhejiang University, 2019.
11	吕双春, 葛云丽, 赵倩, 等. 高硅分子筛的合成及其在VOCs吸附去除领域的应用[J]. 环境化学, 2017, 36(7): 1492-1505.
	Shuangchun LYU, GE Yunli, ZHAO Qian, et al. Synthesis of high silica molecular sieves and their application in VOCs adsorption removal[J]. Environmental chemistry, 2017, 36(7): 1492-1505.
12	LI H, EDDAOUDI M, YAGHIO M, et al. Design and synthesis of an exceptionally stable and highly porous metalorganic framework[J]. Nature, 1999, 402(6759): 276-279.
13	PARK K S, NI Z, CÔTÉ A P, et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks[J]. Proc. Natl. Acad. Sci. USA, 2006, 103(27): 10186-10191.
14	DENG H, GRUNDER S, CORDOVA K E, et al. Large-pore apertures in a series of metal-organic frame works[J]. Science, 2012, 336(6084): 1018-1023.

吸附剂	结构性质				饱和吸附量/mg·g^-1
吸附剂	BET/m²·g^-1	微孔面积/m²·g^-1	总孔容/m³·g^-1	平均孔径/nm	正己烷	甲苯	乙酸乙酯
5A	449.2	303.6	0.248	0.552	99.41	9.56	18.9
13X	635.3	574.2	0.310	0.793～1.093	128.70	196.52	221.07
NaY	582.9	506.0	0.318	0.755～1.093	110.53	153.28	172.69
ZSM-5(27)	287.6	226.4	0.202	0.612～1.686	77.01	48.63	146.60
ZSM-5(300)	345.7	284.3	0.226	0.522～0.913	94.59	58.83	166.80
Hβ	377.7	151.9	0.347	0.642～1.198	71.64	97.14	123.01
MCM-41	1053.8	—	0.952	4.093	12.95	58.30	151.5
AC	1720.8	1191.4	1.23	0.501～5.688	200.07	305.66	229.48

吸附剂	结构性质				饱和吸附量/mg·g^-1
吸附剂	BET/m²·g^-1	微孔面积/m²·g^-1	总孔容/m³·g^-1	平均孔径/nm	正己烷	甲苯	乙酸乙酯
5A	449.2	303.6	0.248	0.552	99.41	9.56	18.9
13X	635.3	574.2	0.310	0.793～1.093	128.70	196.52	221.07
NaY	582.9	506.0	0.318	0.755～1.093	110.53	153.28	172.69
ZSM-5(27)	287.6	226.4	0.202	0.612～1.686	77.01	48.63	146.60
ZSM-5(300)	345.7	284.3	0.226	0.522～0.913	94.59	58.83	166.80
Hβ	377.7	151.9	0.347	0.642～1.198	71.64	97.14	123.01
MCM-41	1053.8	—	0.952	4.093	12.95	58.30	151.5
AC	1720.8	1191.4	1.23	0.501～5.688	200.07	305.66	229.48

MOFs	Langmuir比表面积 /m²·g^-1	总孔容 /cm³·g^-1	平均孔径 /nm
MOF-5^[12]	3917	1.55	0.86
ZIF-8^[13]	1947	11.6	0.66
IRMOF-74-I to XI^[14]	1350～2510	—	1.4～9.8
MIL-101^[15]	5900	1.70	2.9～3.4
MOF-177^[18]	4170	1.11	0.94

MOFs	Langmuir比表面积 /m²·g^-1	总孔容 /cm³·g^-1	平均孔径 /nm
MOF-5^[12]	3917	1.55	0.86
ZIF-8^[13]	1947	11.6	0.66
IRMOF-74-I to XI^[14]	1350～2510	—	1.4～9.8
MIL-101^[15]	5900	1.70	2.9～3.4
MOF-177^[18]	4170	1.11	0.94

硅胶样品	结构性质			吸附量/mg·g^-1
硅胶样品	BET/m²·g^-1	平均孔径/nm	总孔容/cm³·g^-1	丙酮	乙酸乙酯
1^#硅胶	766	2.2	0.44	118.9	254.1
2^#硅胶	513	4.9	0.77	86.0	219.3
3^#硅胶	380	7.0	0.85	57.9	142.4