低浓度挥发性有机物吸附浓缩材料的研究进展

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

摘要/Abstract

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

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

中图分类号:

TQ09

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.

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.

图/表 13

图1 吸附等温线类型[1]Ⅰ—微孔吸附；Ⅱ—大孔或非多孔固体吸附；Ⅲ—大孔分子的多层吸附；Ⅳ，Ⅴ—介孔吸附，压力过大会出现吸附滞后；Ⅵ—非极性物质在表面均匀的非多孔吸附相上的多层吸附

图2 吸附带的移动和穿透曲线[2]

图3 甲苯、乙酸乙酯在五种分子筛上的穿透曲线[3]（吸附条件：常压、温度35℃±2℃，湿度RH=60%，初始浓度500mg/m3，空速5000h-1）

图4 不同分子筛上甲苯的脱附曲线[4]（脱附条件：VOCs初始浓度125mg/m3，升温速率2℃/min，空速5000h-1）

图5 不同分子筛的结构示意图[10]

表1 吸附剂结构性质及吸附性能[8]

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

图6 分子筛孔径与部分VOCs气体分子大小比较[11]

图7 经典MOFs材料的结构示意图[12-16]

表2 典型MOFs吸附材料的结构性质

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

表3 3种硅胶吸附材料的结构性质及吸附性能[21]

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

图8 ZSM-5-300分子筛上不同浓度混合VOCs的穿透曲线[3]（吸附条件：常压，温度35℃±2℃，相对湿度RH=60%，初始浓度65mg/m3、125mg/m3、250mg/m3，空速5000h-1）

图9 活性炭吸附浓缩-催化燃烧工艺流程图1—预处理器；2—固定吸附床；3—主风机；4—脱附风机；5—催化燃烧床；6—补冷风机；7—烟囱

图10 沸石轮转吸附浓缩-催化燃烧工艺流程图

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