用于高湿度废气中甲苯吸附净化的疏水型ZSM-5分子筛的合成及其吸附性能研究

doi:10.11949/0438-1157.20191253

摘要/Abstract

摘要：

采用水热原位法合成了不同硅铝比的ZSM-5分子筛，研究了硅铝比对ZSM-5分子筛结构和疏水性的影响。以典型的挥发性有机物甲苯为对象，在动态吸附实验装置上评价了ZSM-5分子筛吸附有机物的性能，并拟合了甲苯在疏水ZSM-5上的吸附等温线方程。结果表明，高硅铝比ZSM-5具有良好的疏水性，其静态水吸附容量为0.014 g·g^-1，在高湿度条件下，甲苯浓度为1800 mg·m^-3，GHSV为25000 ml·h^-1·g^-1，温度为35℃，甲苯穿透吸附容量为0.041 g·g^-1，甲苯饱和吸附容量为0.075 g·g^-1。吸附等温线的拟合显示，甲苯在疏水ZSM-5分子筛上的吸附符合Langmuir-Freundlich复合模型。

关键词: 疏水, ZSM-5, 水热原位法, 甲苯, 吸附等温线

Abstract:

ZSM-5 zeolites with different Si/Al ratios were synthesized by hydrothermal in situ method. The effect of Si/Al ratio on the structure and hydrophobicity of ZSM-5 was studied. The adsorption performance of ZSM-5 zeolites for toluene was investigated on a dynamic adsorption experimental device, and the adsorption isotherm equation of toluene on hydrophobic ZSM-5 was studied. The results show that the high-silicon ZSM-5 has good hydrophobicity, and its static water adsorption capacity is 0.014 g·g^-1. Under high humidity conditions, the toluene concentration of 1800 mg·m^-3, the GHSV of 25000 ml·h^-1·g^-1and the temperature of 35℃, the breakthrough adsorption capacity of the synthesized ZSM-5 for toluene is 0.041 g·g^-1, and the toluene saturated adsorption capacity is 0.075 g·g^-1. The fitting of the adsorption isotherm showed that the adsorption of toluene on the hydrophobic ZSM-5 zeolites was in accordance with the Langmuir-Freundlich model.

Key words: hydrophobic, ZSM-5, hydrothermal in situ, toluene, adsorption isotherm

中图分类号:

X 511

高君安, 王伟, 张傑, 雷志刚, 史东军, 曲令多. 用于高湿度废气中甲苯吸附净化的疏水型ZSM-5分子筛的合成及其吸附性能研究[J]. 化工学报, 2020, 71(1): 337-343.

Jun an GAO, Wei WANG, Jie ZHANG, Zhigang LEI, Dongjun SHI, Lingduo QU. Study on synthesis and adsorption performance of hydrophobic ZSM-5 zeolites for removal of toluene in high-humidity exhaust gas[J]. CIESC Journal, 2020, 71(1): 337-343.

图/表 9

表2 不同硅铝比的ZSM-5对甲苯的吸附性能

Table 2 Adsorption performance of ZSM-5 for toluene with different silicon to aluminum ratio

样品	RH=0			RH=60%
样品	q _甲苯/(g·g^-1)	穿透时间/min	穿透吸附量/(g·g^-1)	q _甲苯/(g·g^-1)	q _水/(g·g^-1)	穿透时间/min	穿透吸附量/(g·g^-1)
ZSM-5-50	0.058	46	0.016	0.011	0.037	28	0.008
ZSM-5（300）	0.071	76	0.031	0.069	0.001	71	0.029
ZSM-5（500）	0.077	82	0.042	0.075	0.001	79	0.041

图1 不同硅铝比ZSM-5的XRD谱图 (合成条件：H2O∶SiO2=40，NaOH∶SiO2=0.1，正丁胺∶SiO2=0.4，晶化温度150℃，晶化时间48 h)

Fig.1 XRD patterns of ZSM-5 with different SiO2∶Al2O3 ratios

表1 不同投料硅铝比合成ZSM-5的结构性质

Table 1 Structural properties of synthesized ZSM-5 with different SiO2∶Al2O3 ratios

样品	S _BET/(m²·g^-1)	S _micro/(m²·g^-1)	平均孔径/nm	相对结晶度/%	实际硅铝比	投料转化率/%
ZSM-5-50	377.4	102.1	1.94	100	50	—
ZSM-5(100)	377.1	110.3	1.96	98	66.7	66.7
ZSM-5(300)	384.9	142.8	2.32	110	225	75.3
ZSM-5(500)	379.6	149.2	2.36	103	356	71.2
ZSM-5(800)	368.2	98.7	2.12	78.1	435	54.3
ZSM-5(1000)	364.7	97.1	2.11	76.3	538	53.8

图2 不同投料SiO2∶Al2O3合成ZSM-5的SEM图

Fig.2 SEM images of synthesis of ZSM-5 with different adding SiO2∶Al2O3 ratios

图3 硅铝比对ZSM-5疏水性的影响

Fig.3 Effect of SiO2/Al2O3 ratio on hydrophobicity of ZSM-5

图4 湿度对ZSM-5疏水性的影响

Fig.4 Effect of humidity on hydrophobicity of ZSM-5

图5 不同硅铝比ZSM-5脱附甲苯的TG曲线 ★为ZSM-5脱附峰温度95℃；▽，▼分别为ZSM-5（300）脱附峰温度83℃，192℃；◇，◆ 分别为ZSM-5（500）脱附峰温度78℃，190℃

Fig.5 TG curve of different SiO2/Al2O3 ZSM-5 for toluene desorption

图6 ZSM-5甲苯吸附等温线

Fig.6 Toluene adsorption isotherm of ZSM-5

表3 等温吸附模型拟合的相关参数

Table 3 Related parameters of isothermal adsorption model fitting

ZSM-5	Langmuir			Freundlich			Langmuir-Freundlich
ZSM-5	q _m/(mg·g^-1)	K _L×10⁵	R ²	n	K _F	R ²	q _m/(mg·g^-1)	K _a×10^-5	n	R ²
ZSM-5(300)	185.3	5.431	0.971	1.812	0.415	0.972	303.5	1.672	0.711	0.975
ZSM-5(500)	156.9	8.313	0.973	2.136	0.818	0.951	154.6	154.8	7.868	0.979

参考文献 30

1	Das A , Das N , Naskar M K , et al . Influence of process parameters on the formation of silicalite-1 zeolite particles[J]. Ceramics International, 2009, 35(5): 1799-1806.
2	Cundy C S , Cox P A . The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time[J]. Chemical Reviews, 2003, 103(3): 663-702.
3	Kim K J , Kang C S , You Y J , et al . Adsorption-desorption characteristics of VOCs over impregnated activated carbons[J]. Catalysis Today, 2006, 111(3/4): 223-228.
4	Kresge C T , Leonowivz M E , Roth W J , et al . Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992, 359(6397): 710-712.
5	Long C , Yu W , Li A . Adsorption of n-hexane vapor by macroporous and hypercrosslinked polymeric resins: equilibrium and breakthrough analysis[J]. Chemical Engineering Journal, 2013, 221: 105-110.
6	宫振宇, 王明华, 凌江华, 等 . 由粉煤灰制备的分子筛静态水吸附性能测定[J]. 材料与冶金学报, 2012, 11(3): 228-233.
	Gong Z Y , Wang M H , Ling J H , et al . Determination of static water adsorption properties of molecular sieves prepared from flyash[J]. Journal of Materials and Metallurgy, 2012, 11(3): 228-233.
7	Cheng Y , Wang L J , Li J S , et al . Preparation and characterization of nanosized ZSM-5 zeolites in the absence of organic template[J]. Materials Letters, 2005, 59(27): 3427-3430.
8	Zhu X , Wu L , Magusin P C , et al . On the synthesis of highly acidic nanolayered ZSM-5[J]. Journal of Catalysis, 2015, 327: 10-21.
9	Baia L V , Souza W C , Souza R J , et al . Removal of sulfur and nitrogen compounds from diesel oil by adsorption using clays as adsorbents[J]. Energy & Fuels, 2017, 31(11): 11731-11742.
10	Soltanali S , Halladj R , Rashidi A , et al . Mixed templates application in ZSM-5 nanoparticles synthesis: effect on the size, crystallinity, and surface area[J]. Advanced Powder Technology, 2014, 25(6): 1767-1771.
11	Lei W , Xu Y P , Wang Y , et al . Structure-directing role of amines in the ionothermal synthesis[J]. Journal of the American Chemical Society, 2006, 128(23): 7432.
12	Nikolajsen K , Minsker L K , Renken A . Structured fixed-bed adsorber based on zeolite/sintered metal fibre for low concentration VOC removal[J]. Chemical Engineering Research and Design, 2006, 84(7): 562-568.
13	Wu C Y , Chung T W , Yang T C K , et al . Dynamic determination of the concentration of volatile alcohols in a fixed bed of zeolite 13X by FT-IR[J]. Journal of Hazardous Materials, 2006, 137(2): 893-898.
14	徐如人 . 分子筛与多孔材料化学[M]. 北京: 科学出版社, 2004: 567-570.
	Xu R R . Molecular Sieve and Porous Material Chemistry[M]. Beijing: Science Press, 2004: 567-570.
15	Yamamoto T , Kataoka S , Ohmori T . Characterization of carbon cryogel microspheres as adsorbents for VOC[J]. Journal of Hazardous Materials, 2010, 177(1/2/3): 331-335.
16	Liu K , Flora T T . Effect of the nitrogen heterocyclic compounds on hydrodesulfurization using in situ hydrogen and a dispersed Mo-catalyst[J]. Catalyst Today, 2010, 149(1): 28-34.
17	Tao X , Zhou Y , Wei Q , et al . Inhibition effects of nitrogen compounds on deep hydrodesulfurization of straight-run gas oil over a NiW/Al₂O₃ catalyst[J]. Fuel, 2017, 188: 401-409.
18	Wen J , Lin H F , Han X , et al . Physicochemical studies of adsorptive denitrogenation by oxidized activated carbons[J]. Industrial & Engineering Chemistry Research, 2017, 56(17): 5033-5041.
19	Tan P , Xie X Y , Liu X Q , et al . Fabrication of magnetically responsive HKUST-1/Fe₃O₄ composites by dry gel conversion for deep desulfurization and denitrogenation[J]. Journal of Hazardous Materials, 2017, 321: 344-352.
20	化学工业部上海化工研究院 . 分子筛静态水吸附测定方法：GB/T 6287—1986 [S]. 北京：中国标准出版社，1986.
	Shanghai Institute of Chemical Industry, Ministry of Chemical Industry . Method for determination of zeolites static water adsorption: GB/T 6287—1986 [S]. Beijing: Standards Press of China, 1986.
21	黄海凤, 褚翔, 卢晗锋, 等 . 两种介孔分子筛动态吸附VOCs的研究[J]. 中国环境科学, 2010, 30( 4): 442-447.
	Huang H F , Chu X , Lu H F , et al . Study on dynamic adsorption of VOCs by two mesoporous molecular sieves[J]. Chinese Environmental Science, 2010, 30(4): 442-447.
22	Xie L , Favre-Reguillon A , Wang X X , et al . Selective adsorption of neutral nitrogen compounds from fuel using ion-exchange resins [J]. Journal of Chemical & Engineering Data, 2010, 55(11): 4849-4853.
23	Chitanda J M , Misra P , Abedi A , et al . Synthesis and characterization of functionalized poly(glycidyl methacrylate)-based particles for the selective removal of nitrogen compounds from light gas oil： effect of linker length [J]. Energy & Fuels, 2015, 29(3): 1881-1891.
24	Soares J C , Soares A C , Pereira P A R , et al . Adsorption according to the Langmuir-Freundlich model is the detection mechanism of the antigen p53 for early diagnosis of cancer [J]. Physical Chemistry Chemical Physics, 2016, 18(12): 8412-8418.
25	Tang K , Hong X . Preparation and characterization of Co-MCM-41 and its adsorption removing basic nitrogen compounds from FCC diesel oil[J]. Energy & Fuels, 2016, 30(6): 4619-4624.
26	Lliyas A , Zahedi N M H , Eic M , et al . Control of hydrocarbon cold start emissions: a search for potential adsorbents[J]. Microporous and Mesoporous Materials, 2007, 102(1/2/3): 171-177.
27	Guillemot M , Mijoin J , Mignard S , et a1 . Volatile organic compounds (VOCs) removal over dual functional adsorbent/catalyst system[J]. Applied Catalysis B, 2007, 75(3/4): 249-255.
28	Pires J , Carvalho A . Adsorption of volatile organic compounds in Y zeolites and pillared clays[J]. Microporous and Mesoporous Materials, 2001, 43(3): 277-287.
29	Serrano D P , Calleja G , Botas J A , et a1 . Characterization of adsorptive and hydrophobic properties of silicalite-1, ZSM-5, TS-1 and beta zeolites by TPD techniques[J]. Separation and Purification Technology, 2007, 54(1): 1-9.
30	Ng K C , Chua H T , Chung C Y , et al . Experimental investigation of the silica gel-water adsorption isotherm characteristics[J]. Applied Thermal Engineering, 2001, 21(16): 1631-1642.

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