有序介孔碳对低浓度气相萘的吸附特性分析

doi:10.11949/j.issn.0438-1157.20170079

摘要/Abstract

摘要：

对3种常见有序介孔碳（OMCs）吸附脱除典型气相多环芳烃——萘进行了研究。分别采用吸附等温线模型（Langmuir、Freundlich、Sips）和恒定浓度波动力学模型对吸附等温线和穿透曲进行拟合分析。采用程序升温脱附法通过失重曲线分析了吸附剂的再生性能。结果表明：Langmuir模型和Sips模型能很好地描述低浓度气相萘在OMCs上的静态吸附行为（R² > 99%），吸附量呈CMK-5 > CMK-3 > FDU-15排列。恒定浓度波动力学模型具有较高的拟合度，介孔促使3种吸附剂对萘分子具有较高的吸附扩散系数。具有微通孔结构的CMK-5和FDU-15表现出更好的再生性能。综合吸脱附动力学分析，CMK-5在3种吸附剂中表现出更好的应用潜能。

关键词: 吸附平衡, 吸附动力学, 有序介孔碳, 多环芳烃, 再生性能

Abstract:

Three kinds of ordered mesoporous carbons (OMCs) were used to remove low concentration of polycyclic aromatic hydrocarbons (PAHs)-naphthalene (Nap), by dynamic adsorption experiments. The adsorption isotherms were fitted with isotherm models (Langmuir, Freundlich, and Sips) and kinetic model based on the assumption of constant concentration wave, respectively. The regeneration performance of the adsorbents were analyzed by means of mass loss curve based on the temperature programmed desorption analysis. The results indicated that the static adsorption behavior of Nap on OMCs can be well predicted by Langmuir and Sips isotherm models (R² > 99%),and the adsorption capacity of CMK-5 (1.735 mol·kg^-1) is better than that of CMK-3 and FDU-15. The constant-pattern wave propagation model was found to well fit the breakthrough curves. And the existence of mesoporous in the adsorbents facilitated the adsorption mass transfer. With transversal micropores, CMK-5 and FDU-15 showed better regenerabilities, and the desorption activation energy follows the order:CMK-3 > CMK-5 > FDU-15. Based on the analysis of absorption and desorption kinetics, CMK-5 shows better application potential in the three kinds of adsorbents.

Key words: adsorption equilibrium, adsorption kinetics, ordered mesoporous carbons, polycyclic aromatic hydrocarbons, regenerability

中图分类号:

X511

孟苗苗, 刘应书, 李子宜, 姜理俊, 杨雄, 刘文海. 有序介孔碳对低浓度气相萘的吸附特性分析[J]. 化工学报, 2017, 68(8): 3109-3118.

MENG Miaomiao, LIU Yingshu, LI Ziyi, JIANG Lijun, YANG Xiong, LIU Wenhai. Adsorption characteristics of low concentration gaseous naphthalene on ordered mesoporous carbons[J]. CIESC Journal, 2017, 68(8): 3109-3118.

参考文献 36

[1]	WEI C, HAN Y, BANDOWE B A M, et al. Occurrence, gas/particle partitioning and carcinogenic risk of polycyclic aromatic hydrocarbons and their oxygen and nitrogen containing derivatives in Xi'an, central China[J]. Sci. Total Environ., 2015, 505:814-822.
[2]	朱利中, 沈学优, 刘勇建. 城市居民区空气中多环芳烃污染特征和来源分析[J]. 环境科学, 2001, 22(1):86-89. ZHU L Z, SHEN X Y, LIU Y J. The survey of polycyclic aromatic hydrocarbons in a habitation air in Hangzhou[J]. Environmental Science, 2001, 22(1):86-89.
[3]	余刚, 黄俊, 张彭义. 持久性有机污染物:倍受关注的全球性环境问题[J]. 环境保护, 2001, (4):37-39. YU G, HUANG J, ZHANG P Y. Persistent organic pollutants:one of the important global Environmental problems[J]. Environmental Protection, 2001, (4):37-39.
[4]	LAFONTAINE S, SCHRLAU J, BUTLER J, et al. Relative influence of trans-pacific and regional atmospheric transport of PAHs in the pacific northwest, U.S.[J]. Environ. Sci. Technol., 2015, 49(23):13807-13816.
[5]	尹雪峰, 李晓东, 陆胜勇, 等. 大型电站燃煤锅炉多环芳烃排放特性[J]. 中国电机工程学报, 2007, 27(5):1-6. YIN X F, LI X D, LU S Y, et al. The polycyclic aromatic hydrocarbons emission character in the large-scale power plant boiler[J]. Proceedings of the CSEE, 2007, 27(5):1-6.
[6]	王超, 张霖琳, 刀谞, 等. 京津冀地区城市空气颗粒物中多环芳烃的污染特征及来源[J]. 中国环境科学, 2015, 35(1):1-6. WANG C, ZHANG L L, DAO X, et al. Pollution characteristics and source identification of polycyclic aromatic hydrocarbons in airborne particulates of Beijing-Tianjin-Hebei Region, China[J]. China Environmental Science, 2015, 35(1):1-6.
[7]	李军, 张干, 祁士华. 广州市大气中多环芳烃分布特征、季节变化及其影响因素[J]. 环境科学, 2004, 25(3):7-13. LI J, ZHANG G, QI S H. Characteristics and seasonal variations and influence factors on polycyclic aromatic hydrocarbons in Guangzhou city[J]. Environmental Science, 2004, 25(3):7-13.
[8]	马万里, 李一凡, 孙德智, 等. 哈尔滨市大气气相中多环芳烃的研究[J]. 环境科学, 2009, 30(11):3167-3172. MA W L, LI Y F, SUN D Z, et al. Gaseous polycyclic aromatic hydrocarbons in Harbin air[J]. Environment Science, 2009, 30(11):3167-3172.
[9]	李敬伟, 施浩勋, 李敏, 等. 燃煤电厂飞灰PM2.5及PM2.5-10中多环芳烃分布特性研究[J]. 动力工程学报, 2015, 35(4):306-311. LI J W, SHI H X, LI M, et al. Distribution of polycyclic aromatic hydrocarbons in PM2.5 and PM2.5-10 from fly ash of coal-fired power plants[J]. Journal of Chinese Society of Power Engineering, 2015, 35(4):306-311.
[10]	周变红, 张承中, 王格慧. 西安城区大气中多环芳烃的季节变化特征及健康风险评价[J]. 环境科学学报, 2012, 32(9):2324-2331. ZHOU B H, ZHANG C Z, WANG G H. Seasonal variation and health risk assessment of atmospheric polycyclic aromatic hydrocarbons (PAHs) in the urban area of Xi'an[J]. Acta Sci. Circumst., 2012, 32(9):2324-2331.
[11]	姜岩, 张晓华, 杨颖, 等. 基于约氏不动杆菌的萘生物降解特性[J]. 化工学报, 2016, 67(9):3981-3987. JIANG Y, ZHANG X H, YANG Y, et al. Naphthalene biodegradation by Acinetobacter johnsonii[J]. CIESC Journal, 2016, 67(9):3981-3987.
[12]	齐义彬, 李红, 曹美娜, 等. 一株多环芳烃降解菌吉2及其降解能力[J]. 化工学报, 2015, 66(3):1072-1079. QI Y B, LI H, CAO M N, et al. A PAH-degrading strain JI 2 and its biodegradation potential ability[J]. CIESC Journal, 2015, 66(3):1072-1079.
[13]	贾燕, 尹华, 叶锦韶, 等. 假单胞菌N7的萘降解特性及其降解途径研究[J]. 环境科学, 2008, 29(3):756-762. JIA Y, YIN H, YE J C, et al. Characteristics and pathway of naphthalene degradation by pseudomonas sp.N7[J]. Environmental Science, 2008, 29(3):756-762.
[14]	黄华, 王雅雄, 唐景春, 等. 不同烧制温度下玉米秸秆生物炭的性质及对萘的吸附性能[J]. 环境科学, 2014, 35(5):1884-1890. HUANG H, WANG Y X, TANG J C, et al. Properties of maize stalk biochar produced under different pyrolysis temperatures and its sorption capability to naphthalene[J]. Environmental Science, 2014, 35(5):1884-1890.
[15]	马正月, 陈皓侃, 李文, 等. 烟气中多环芳烃吸附脱除的研究[J]. 燃料化学学报, 2004, 32(5):526-530. MA Z Y, CHEN H K, LI W, et al. Polycyclic aromatic hydrocarbons removal from hot gas by porous sorbent adsorption[J]. Journal of Fuel Chemistry and Technology, 2004, 32(5):526-530.
[16]	MASTRAL A M, GARCÍA T, CALLÉN M S, et al. Removal of naphthalene, phenanthrene, and pyrene by sorbents from hot gas[J]. Environ. Sci. Technol., 2001, 35(11):2395-2400.
[17]	MASTRAL A M, GARCIA T, CALLEN M S, et al. Assessement of phenanthrene removal from hot gas by porous carbons[J]. Energ. Fuel., 2001, 15(1):1-7.
[18]	HU X L, HANAOKA T, SAKANISHI K, et al. Removal of tar model compounds produced from biomass gasification using activated carbons[J]. Journal of the Japan Institute of Energy, 2007, 86(9):707-711.
[19]	LI Z Y, LIU Y S, YANG X, et al. Desorption of polycyclic aromatic hydrocarbons on mesoporous sorbents:thermogravimetric experiments and kinetics study[J]. Ind. Eng. Chem. Res., 2016, 55(5):1183-1191.
[20]	KOSUGE K, KUBO S, KIKUKAWA N, et al. Effect of pore structure in mesoporous silicas on VOC dynamic adsorption/desorption performance[J]. Langmuir, 2007, 23(6):3095-3102.
[21]	ARANDA A, NAVARRO M V, GARCÍA T, et al. Temperature swing adsorption of polycyclic aromatic hydrocarbons on activated carbons[J]. Ind. Eng. Chem. Res., 2007, 46(24):8193-8198.
[22]	RYOO R, JOO S H, JUN S. Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation[J]. The Journal of Physical Chemistry B, 1999, 103(37):7743-7746.
[23]	JOO S H, CHOI S J, OH I, et al. Ordered nanoporous arrays of carbon supporting high dispersions of platinum nanoparticles[J]. Nature, 2001, 412(6843):169-172.
[24]	JUN S, JOO S H, RYOO R, et al. Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure[J]. J. Am. Chem. Soc., 2000, 122(43):10712-10713.
[25]	ZHANG F, MENG Y, GU D, et al. A facile aqueous route to synthesize highly ordered mesoporous polymers and carbon frameworks with Ia3hd bicontinuous cubic structure[J]. J. Am. Chem. Soc., 2005, 127(39):5279-5288.
[26]	MENG Y, GU D, ZHANG F, et al. A family of highly ordered mesoporous polymer resin and carbon structures from organic-organic self-assembly[J]. Chem. Mater., 2006, 18(18):4447-4464.
[27]	ZHANG F, MENG Y, GU D, et al. An aqueous cooperative assembly route to synthesize ordered mesoporous carbons with controlled structures and morphology[J]. Chem. Mater., 2006, 18(22):5279-5288.
[28]	MENG Y, GU D, ZHANG F, et al. Ordered mesoporous polymers and homologous carbon frameworks:amphiphilic surfactant templating and direct transformation[J]. Angewandte Chemie, 2005, 117(43):7215-7221.
[29]	LIU Y S, LI Z Y, XIONG Y, et al. Performance of mesoporous silicas (MCM-41 and SBA-15) and carbon (CMK-3) in the removal of gas-phase naphthalene:adsorption capacity, rate and regenerability[J]. RSC Advances, 2016, 6(25):21193-21203.
[30]	LI Z Y, LIU Y S, YANG X, et al. Performance of mesoporous silicas and carbon in adsorptive removal of phenanthrene as a typical gaseous polycyclic aromatic hydrocarbon[J]. Micropor. Mesopor. Mat., 2017, 239:9-18.
[31]	杨权, 刘应书, 李子宜, 等. 萘在介孔分子筛MCM-41与SBA-15上的吸附特性研究[J]. 燃料化学学报, 2015, 43(12):1482-1488. YANG Q, LIU Y S, LI Z Y, et al. Study on the adsorption behaviours of naphthalene on MCM-41 and SBA-15 mesoporous molecular sieves[J]. J. Fuel Chem. Technol., 2015, 43(12):1482-1488.
[32]	DELLE SITE A. The vapor pressure of environmentally significant organic chemicals:a review of methods and data at ambient temperature[J]. J. Phys. Chem. Ref. Data, 1997, 26(1):157.
[33]	CHERN J, CHIEN Y. Adsorption isotherms of benzoic acid onto activated carbon and breakthrough curves in fixed-bed columns[J]. Ind. Eng. Chem. Res., 2001, 40(17):3775-3780.
[34]	PENG X, HU X, FU D, et al. Adsorption removal of acid black 1 from aqueous solution using ordered mesoporous carbon[J]. Appl. Surf. Sci., 2014, 294:71-80.
[35]	PENG X, HU F, HUANG J, et al. Preparation of a graphitic ordered mesoporous carbon and its application in sorption of ciprofloxacin:kinetics, isotherm, adsorption mechanisms studies[J]. Micropor. Mesopor. Mat., 2016, 228:196-206.
[36]	LIN D H, JIANG Y X, CHEN S R, et al. Preparation of Pt nanoparticles supported on ordered mesoporous carbon FDU-15 for electrocatalytic oxidation of CO and methanol[J]. Electrochimica Acta, 2012, 67:127-132.carbon[J]. MicroporMesopor Mat. 2017, 239: 9-18.
[31]	杨权,刘应书,李子宜,等. 萘在介孔分子筛 MCM-41与 SBA-15 上的吸附特性研究[J]. 燃料化学学报. 2015, 43(12): 1482-1488.YANG Q, LIU Y S, LI Z Y, et al. Study on the adsorption behaviours of naphthalene on MCM-41 and SBA-15 mesoporous molecular sieves[J], J. Fuel Chem. Technol. 2015, 43(12): 1482-1488.
[32]	DELLE SITE A. The vapor pressure of environmentally significant organic chemicals: areview of methods and data at ambient temperature[J]. J Phys Chem Ref Data. 1997, 26(1): 157.
[33]	CHERN J, CHIEN Y. Adsorption isotherms of benzoic acid onto activated carbon and breakthrough curves in fixed-bed columns[J]. IndEngChem Res. 2001, 40(17): 3775-3780.
[34]	PENG X, HU X, FU D, et al. Adsorption removal of acid black 1 from aqueous solution using ordered mesoporous carbon[J]. Appl Surf Sci. 2014, 294: 71-80.
[35]	PENG X, HU F, HUANG J, et al. Preparation of a graphitic ordered mesoporous carbon and its application in sorption of ciprofloxacin: kinetics, isotherm, adsorption mechanisms studies[J]. MicroporMesopor Mat. 2016, 228: 196-206.
[36]	Lin D H, Jiang Y X, Chen S R, et al. Preparation of Pt nanoparticles supported on ordered mesoporous carbon FDU-15 for electrocatalytic oxidation of CO and methanol[J]. ElectrochimicaActa, 2012, 67: 127-132.