Adsorption and decolorization of hydrogenated coal tar on resin-based activated carbon spheres
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摘要: 采用悬浮聚合、水蒸气活化方法制备了树脂基球状活性炭(ACS),并进行硝酸氧化改性(NACS),用于焦油加氢后油品的脱色研究。通过SEM、N2吸附-脱附、FTIR、XPS、TG等技术对所制样品ACS和NACS进行结构性质表征。结果显示,经硝酸氧化改性后,NACS样品的表面形貌和孔结构并未受到显著影响,但球状活性炭表面的含氧官能团明显增加。选取两种典型的显色化合物对苯醌(PBQ)和N,N-二仲丁基对苯二胺(DBD)配置一定浓度的模型油进行吸附脱色,考察了吸附时间、吸附温度和吸附剂用量对吸附剂性能的影响。研究表明,NACS样品展现出良好的吸附性能,在一定的吸附条件下,对DBD和PBQ的脱色率分别达到94.5%和96.6%,除了球状活性炭表面微孔提供的活性位点之外,NACS表面官能团与有色物质形成的氢键可能对吸附性能的提升起着关键作用。重复使用6次后,吸附剂对两者的脱色率仍能达到90%以上,展现出良好的可再生性能。在对真实加氢油品脱色后,脱色效果显著,验证了所制备吸附剂在实际应用中的可行性。Abstract: Resin-based activated carbon spheres (ACSs) were prepared by a combined suspension polymerization, carbonization and activation method. The ACSs were then oxidized with nitric acid (NACSs) to modify the surface properties to increase the decolorization of hydrogenated coal tar. The morphology, pore structure, elemental composition and pyrolysis kinetics of the polymer sample were characterized by SEM, N2 adsorption, FTIR, XPS and TGA. Results showed that this oxidation modification of the ACSs has little influence on their surface morphology and pore structure while the numbers of surface oxygen functional groups were remarkably increased. P-benzoquinone (DBD) and N,N-di-sec-butyl-1,4-phenylenediamine (PBQ) were selected as model color compounds for decolorization tests with ACSs and NACSs. The effects of adsorption time, temperature and amount of adsorbent on the decolorization performance were investigated. Under the same adsorption conditions, the amounts of decolorization of DBD and PBQ were 94.5% and 96.6%, respectively for NACSs while those for ACSs were much lower, indicating the outstanding adsorption performance of NACSs. Hydrogen bonds formed between surface functional groups and colored compounds may play a key role in improving the adsorption performance. Moreover, the decolorization of NACSs was still more than 90% after NACSs were recycled 6 times. The decolorization effect of NACSs for real hydrogenated coal tar was also significant and its color faded after adsorption by NACSs, confirming their feasibility for practical use.
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表 1 NACS吸附剂的再生性能
Table 1. Regeneration performance of NACS adsorbent.
Cyclicity 1 2 3 4 5 6 PBQ decolorization rate (%) 96.6 96.2 94.8 93.1 92.5 90.8 DBD decolorization rate (%) 94.5 94.3 92.3 93.4 91.1 92.4 表 2 比表面积和孔结构参数。
Table 2. Specific surface area and pore structure parameters
Sample SBET (m2 g−1) Smicro (m2 g−1) Smeso (m2 g−1) Vtotal (cm3 g−1) Vmicro (cm3 g−1) Vmeso (cm3 g−1) Pore size (nm) ACS 1075 887 116 0.54 0.41 0.09 2.00 NACS 977 829 96 0.51 0.38 0.08 1.98 表 3 XPS表征参数
Table 3. XPS characterization parameters.
Sample XPS analysis (at.%) C O N ACS 95.37 4.63 -/- NACS 83.42 14.38 2.2 表 4 XPS O1s分峰拟合参数
Table 4. O1s Peak-fitting parameters of XPS.
O1s Peak type Peak position(eV) ACS(%) NACS(%) Quinone 531.3 18.08 14.95 C=O 532.3 22.78 23.68 C―O 533.3 30.77 41.41 C―OH 534.2 28.37 19.96 表 5 ACS和NACS吸附PBQ和DBD动力学参数
Table 5. The first-order and second-order kinetics fitting Parameters for adsorption of PBQ and DBD on the ACS and NACS.
Adsorbent Adsorbate Pseudo-first
order kineticPseudo-second
order kineticK1 qe R2 K2 qe R2 ACS PBQ 0.037 12.39 0.9984 0.00537 11.35 0.9790 DBD 0.019 8.86 0.9981 0.00748 9.26 0.9811 NACS PBQ 0.009 16.10 0.9972 0.00297 14.70 0.9923 DBD 0.013 13.40 0.9985 0.00412 10.43 0.9890 -
[1] Yuan Y, Li D, Zhang L N, et al. Development, status, and prospects of coal tar hydrogenation technology[J]. Energy Technology,2016,4(11):1338-1348. doi: 10.1002/ente.201600184 [2] Li D, Niu M, Yang Z, et al. Effect of phosphorus modification on the coal tar hydrogenation activity of the Ni–Mo/γ-Al2O3 catalyst[J]. Reaction Kinetics, Mechanisms and Catalysis,2018,125(1 [3] 姚春雷, 全辉, 张忠清, 等. 中、低温煤焦油加氢生产清洁燃料油技术[J]. 化工进展,2013,32(3):501-507.Yao C L, Quan H, Zhang Z Q, et al. Hydrogenation technology of medium and low temperature coal tar to produce clean fuel oil[J]. Chemical Industry Progress,2013,32(3):501-507. [4] 高枝荣, 刘道胜, 廖克俭, 等. 离子液体改进汽油安定性的初步研究[J]. 辽宁化工,2003,32(11):482-485. doi: 10.3969/j.issn.1004-0935.2003.11.008Gao Z R, Liu D S, Liao K J, et al. Preliminary study on ionic liquids to improve gasoline stability[J]. Liaoning Chemical Industry,2003,32(11):482-485. doi: 10.3969/j.issn.1004-0935.2003.11.008 [5] Baia L V, Souza W C, De Souza R J F, 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. [6] 李沛博. 催化裂化汽油颜色问题的研究[D]. 硕士学位论文, 中国石油大学, 2010.Li P B. Research on the color of FCC gasoline[D]. Master's thesis, China University of Petroleum, 2010. [7] Leresche F, Lucie Ludvíková, Heger D, et al. Quenching of an aniline radical cation by dissolved organic matter and phenols: a laser flash photolysis study[J]. Environmental Science & Technology,2020 [8] E L Walters, D L Yabroff, H B Minor, et al. Correlation of predicted and observed storage stability of cracked gasoline[J]. Industrial & Engineering Chemistry,1948,40(3):423-428. [9] Masoud Almarri, Xiaoliang Ma, Chunshan Song. Selective adsorption for removal of nitrogen compounds from liquid hydrocarbon streams over carbon and alumina-based adsorbents[J]. Ind Eng Chem Res,2009,48(2):951-960. [10] M Maes, M Trekels, M Boulhout, et al. Selective removal of N-heterocyclic aromatic contaminants from fuels by lewis acidic metal-organic frameworks[J]. Angew Chem Int Ed Engl,2011,50(18):4210-4214. doi: 10.1002/anie.201100050 [11] Yosuke Sano, Ki-Hyouk Choi, Yozo Korai, et al. Selection and further activation of activated carbons for removal of nitrogen species in gas oil as a pretreatment for its deep hydrodesulfurization[J]. Energy & Fuels,2004,18(3):644-651. [12] Jie W, Lin H W, Xu H, et al. Physicochemical studies of adsorptive denitrogenation by oxidized activated carbons[J]. Industrial & Engineering Chemistry Research,2017,56(17):5033-5041. [13] Wen J, Zhao D D, Lu Y Y, et al. Simultaneous desulfurization and denitrogenation of model fuels by polyethylene glycol-modified resorcinol/formaldehyde resin-derived carbon spheres[J]. Korean Journal of Chemical Engineering,2019,36(7):1131-1139. [14] 王建龙, 张长明, 李开喜, 等. 一种可控孔结构的树脂基球状活性炭的制备方法: 中国, 201410139231.0[P], 2014-04-09.Wang J L, Zhang C M, Li K X, et al. Preparation method of resin-based spherical activated carbon with controllable pore structure: China, 201410139231.0[P], 2014-04-09. [15] 刘成波, 李发生, 韩梅, 等. 紫外-可见分光光度法用于染料废水絮凝脱色效果测定的研究[J]. 中国环境监测,2001,17(3):22-24.Liu C B, Li F F, Han M, et al. Study on the determination of the effect of flocculation and decolorization of dye wastewater by ultraviolet-visible spectrophotometry[J]. China Environmental Monitoring,2001,17(3):22-24. [16] Zhang C M, Song W, Zhang X H, et al. characterization and evaluation of resin-based carbon spheres modified by oxygen functional groups for gaseous elemental mercury capture[J]. Journal of Materials Science,2018,53(13):9429-9448. doi: 10.1007/s10853-018-2231-6 [17] M E de Oliveira Ferreira, B G Vaz, C E Borba, et al. Modified activated carbon as a promising adsorbent for quinoline removal[J]. Microporous and Mesoporous Materials,2019,277:208-216. doi: 10.1016/j.micromeso.2018.10.034 [18] Li Na, Masoud Almarri, Ma Xiao-liang, et al. The role of surface oxygen-containing functional groups in liquid-phase adsorptive denitrogenation by activated carbon[J]. New Carbon Materials,2011,26(6):470-478. [19] Yao Y Y, Wang L, Sun L J, et al. Efficient removal of dyes using heterogeneous fenton catalysts based on activated carbon fibers with enhanced activity[J]. Chemical Engineering Science,2013,101:424-431. doi: 10.1016/j.ces.2013.06.009 [20] 肖剑. 褐煤中含氧和含氮化合物的分析及其模型化合物于水的氢键作用[D]. 硕士学位论文, 中国矿业大学, 2017.Xiao J. Analysis of oxygen and nitrogen compounds in lignite and hydrogen bonding of model compounds in water[D]. Master's Thesis, China University of Mining and Technology, 2017. [21] Li W S, Liu J, et al. Removal of basic nitrogen compounds from fuel oil with [C4mim] Br/ZnCl2 ionic liquid[J]. Petroleum Science and Technology,2017,35(13):1364-1369. doi: 10.1080/10916466.2017.1331241 [22] Eloussaief M, Chakroun S, Kallel N, et al. Efficiency of clay materials collected from Ain Jeloula (Central Tunisia) in sunflower oil decolorization[J]. Euro-Mediterranean Journal for Environmental Integration,2020,5(2 [23] 郑温锐, 傅尧, 刘磊, 等. 尿素及硫脲与羰基化合物间的氢键相互作用[J]. 物理化学学报,2007,23(7):1018-1024. doi: 10.1016/S1872-1508(07)60057-6Zheng W R, Fu Y, Liu L, et al. Hydrogen bond interaction between urea and thiourea and carbonyl compounds[J]. Acta Phys Chim Sin,2007,23(7):1018-1024. doi: 10.1016/S1872-1508(07)60057-6 [24] 王越. 碱基与氨基酸二肽之间的氢键相互作用[D]. 硕士学位论文, 辽宁师范大学, 2013.Wang Y. Hydrogen bond interaction between bases and amino acid dipeptides[D]. Master's degree thesis, Liaoning Normal University, 2013. [25] Abdi G, Ashokkumar M, Alizadeh A. Ultrasound-assisted oxidative-adsorptive desulfurization using highly acidic graphene oxide as a catalyst-adsorbent[J]. Fuel,2017,210(15):639-645. [26] Zhang X F, Wang Z G, Feng Y, et al. Adsorptive desulfurization from the model fuels by functionalized UiO-66(Zr)[J]. Fuel,2018,234:256-262. doi: 10.1016/j.fuel.2018.07.035 [27] 姜永恒. 络合物的形成对对苯醌的费米共振的影响[D]. 博士学位论文, 吉林大学, 2011.Jiang Y H. The influence of complex formation on the Fermi resonance of p-benzoquinone[D]. Doctoral Dissertation, Jilin University, 2011. [28] 李国亭, 康恒嘉, 赵宝龙, 等. 玉米秸秆生物炭对水中对苯醌的吸附性能研究[J]. 华北水利大学学报,2020,41(4):74-79.Li G T, Kang H J, Zhao B L, et al. Study on adsorption performance of corn stover biochar for p-benzoquinone in water[J]. Journal of North China University of Water Resources,2020,41(4):74-79.