低温一步法活性炭基脱硫剂的制备与评价

唐晓东; 陆海; 李晶晶; 周淼; 胡娜

低温一步法活性炭基脱硫剂的制备与评价

唐晓东^{1, 2, ,},
陆海^{1, 2},
李晶晶²,
周淼²,
胡娜²

1.
西南石油大学油气藏地质及开发工程国家重点实验室, 四川成都 610500
2.
西南石油大学化学化工学院, 四川成都 610500

详细信息

中图分类号: TE624.5
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- 被引次数: 0
出版历程
- 收稿日期: 2017-12-21
- 修回日期: 2018-03-20
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-05-10

Preparation and evaluation of activated carbon-based desulfurization adsorbent by one-step method at low temperature

TANG Xiao-dong^{1, 2
, ,},
LU Hai^{1, 2},
LI Jing-jing²,
ZHOU Miao²,
HU Na²

1.
State Key Laboratory of Oil and Gas Reservoir Geology and Development Engineering, Southwest Petroleum University, Chengdu 610500, China
2.
College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China

More Information

Corresponding author: TANG Xiao-dong, Tel: 15108255288, E-mail: txd3079@163.com

摘要

摘要: 以木屑为原料，在低温条件下一步法制得活性炭基吸附剂，考察了吸附剂制备条件和液-固、气-固吸附条件对吸附剂脱硫性能的影响。结果表明，吸附剂的最佳制备条件为，浸渍液与木屑质量比为1：1，浸渍液中硝酸质量分率为30%、吸附剂表面NiO负载量为5%，常温下浸渍24 h，400℃焙烧3 h。该吸附剂在0.2 g吸附剂/10 mL模拟油、温度为40℃及时间为5 h的液-固吸附脱硫的条件下，脱硫率为28.36%，吸附四次后饱和吸附硫容量可达2.34 mgS/g；在气-固吸附温度为250℃、空速为6.3 h^-1的条件下，饱和吸附硫容量为2.37 mgS/g；高温气-固吸附脱硫对吸附剂的影响表明，与脱硫前相比，吸附剂在比表面积、总孔体积、微孔体积均有明显提高，这说明气-固吸附脱硫过程同时实现了活性炭的扩孔活化。甲苯溶剂再生实验表明，经五次再生后吸附剂的再生性能均可达90%以上。
- 吸附剂 /
- 制备 /
- 二苯并噻吩 /
- 吸附 /
- 脱硫
Abstract: Activated carbon was prepared by one-step method at low temperature using sawdust as material. Effect of preparation and adsorption conditions among liquid-solid and gas-solid on desulfurization performance was discussed. The results show that the optimum preparation conditions are as follows:mass ratio of 1:1 for impregnation liquid (with HNO₃ mass fraction of 30%) and sawdust, NiO loading of 5% on surface of adsorbent, impregnation time of 24 h under room temperature and calcination time of 3 h under 400℃. Under adsorbent mass/DBT volume of 0.2 g/10 mL, liquid-solid adsorption temperature of 40℃ and adsorption time of 5 h, desulfurization efficiency can reach 28.36%. After continuous adsorption 4 times saturated adsorption sulfur capacity is up to 2.34 mgS/g. Under gas-solid adsorption temperature of 250℃ and adsorption velocity of 6.3 h^-1, adsorption sulfur capacity can reach 2.37 mgS/g. The effect of high temperature gas-solid adsorption desulfurization on adsorbent indicates that BET specific surface area, total pore volume and micropore volume of adsorbent have been improved obviously, which show that the gas-solid adsorption desulfurization process has realized the reaming activation of activated carbon simultaneously. The regeneration experiment of toluene solvent shows that the regeneration performance can reach more than 90% after 5 times cycle.
- adsorbent /
- preparation /
- dibenzothiophene /
- adsorption /
- desulfurization

HTML全文

图 1 SAC和NiO/AC的XRD谱图

Figure 1 XRD spectra of SAC and NiO/AC

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图 2 硝酸质量分率对吸附剂脱硫性能的影响

Figure 2 Effect of mass fraction of nitric acid on adsorption desulfurization performance

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图 3 NiO负载量对吸附剂脱硫性能的影响

Figure 3 Effect of NiO loading on adsorption desulfurization performance

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图 4 浸渍时间对吸附剂脱硫性能的影响

Figure 4 Effect of impregnation time on adsorption desulfurization performance

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图 5 焙烧时间对吸附剂脱硫性能的影响

Figure 5 Effect of calcination time on adsorption desulfurization performance

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图 6 吸附温度对吸附剂脱硫性能的影响

Figure 6 Effect of adsorption temperature on adsorption desulfurization performance

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图 7 吸附时间对吸附剂脱硫性能的影响

Figure 7 Effect of adsorption time on adsorption desulfurization performance

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图 8 液-固吸附脱硫饱和硫容量的测定

Figure 8 Determination of saturated sulfur capacity in liquid-solid adsorption desulfurization

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图 9 吸附温度对气-固吸附脱硫性能的影响

Figure 9 Effect of adsorption temperature on gas-solid adsorption desulfurization performance

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图 10 空速对气-固吸附脱硫性能的影响

Figure 10 Effect of space velocity on gas-solid adsorption desulfurization performance

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图 11 活性炭样品吸附脱硫前后SEM照片

Figure 11 SEM image of the activated carbon before and after adsorption desulfurization

(a): SAC; (b): NiO/AC; (c): ANiO/AC

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图 12 再生次数对吸附剂吸附硫容量的影响

Figure 12 Effect of regeneration times on adsorption sulfur capacity of the adsorbent

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表 1 波尔滴定法测定不同活性炭样品的表面含氧官能团

Table 1 Boehm titration oxygen-containing functional groups on the surface among different activated carbon samples

Sample	Surface acidic functional group w/(mmol·g^-1)
Sample	carboxyl	lactone	phenolic hydroxyl	total
SAC	0.2902	0.2009	0.2324	0.7435
NiO/AC(0)	0.3413	0.2310	0.2517	0.8240
NiO/AC(10%)	0.4905	0.3009	0.3908	1.1822
NiO/AC(20%)	0.5712	0.3316	0.4349	1.3377
NiO/AC(30%)	0.6814	0.3508	0.4422	1.4744
NiO/AC(40%)	0.7508	0.3735	0.4628	1.5871
remarks: the data in brackets after NiO/AC in column samples represent the mass fraction of nitric acid in the impregnating solution

下载: 导出CSV

表 2 活性炭样品的孔结构特征

Table 2 Specific surface area and pore structure parameters of the activated carbon

Sample	Surface area A/(m²·g^-1)	Micropore volume v/(cm³·g^-1)	Total pore volume v/(cm³·g^-1)
SAC	70.99	0.047	0.060
NiO/AC	48.42	0.045	0.062
ANiO/AC	106.89	0.078	0.098

下载: 导出CSV

参考文献(22)

[1]	沈俭一, 石国军.燃料油深度加氢脱硫催化剂的研究进展[J].石油化工, 2008, 37(11):1111-1120. doi: 10.3321/j.issn:1000-8144.2008.11.001 SHEN Jian-yi, SHI Guo-jun. Research progress of catalysts for fuel deep hydrodesulfurization[J]. Petrochem Technol, 2008, 37(11):1111-1120 doi: 10.3321/j.issn:1000-8144.2008.11.001
[2]	李文秀, 崔安磊, 范俊刚, 孙向乐, 张志刚.载铜球形活性炭的制备及其吸附脱硫性能的研究[J].燃料化学学报, 2013, 41(5):613-618. http://www.ccspublishing.org.cn/article/id/100032910 LI Wen-xiu, CUI An-lei, FAN Jun-gang, SUN Xiang-le, ZHANG Zhi-gang. Preparation and study on adsorption desulfurization performance over copper loaded spherical activated carbon[J]. J Fuel Chem Technol, 2013, 41(5):613-618. http://www.ccspublishing.org.cn/article/id/100032910
[3]	李秀萍, 赵荣祥, 苏勋建, 艾东.磷钨酸功能化氮化碳的制备及其氧化脱硫研究[J].燃料化学学报, 2015, 43(7):870-875. http://www.ccspublishing.org.cn/article/id/100033374 LI Xiu-ping, ZHAO Rong-xiang, SU Xun-jian, AI Dong. Preparation and study on oxidation desulfurization over phosphotungstic acid functionalized carbon nitride[J]. J Fuel Chem Technol, 2015, 43(7):870-875. http://www.ccspublishing.org.cn/article/id/100033374
[4]	王建龙, 赵地顺, 周二鹏, 董芝.吡啶类离子液体在汽油萃取脱硫中的应用研究[J].燃料化学学报, 2007, 35(3):293-296. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200703008 WANG Jian-long, ZHAO Di-shun, ZHOU Er-peng, DONG Zhi. Application of pyridinium ionic liquids in desulfurization of gasoline extraction[J]. J Fuel Chem Technol, 2007, 35(3):293-296. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200703008
[5]	唐晓东, 袁娇阳, 李晶晶, 张永汾, 胡涛.吡啶离子液体催化作用下的FCC汽油烷基化脱硫[J].燃料化学学报, 2015, 43(4):442-448. http://www.ccspublishing.org.cn/article/id/100033317 TANG Xiao-dong, YUAN Jiao-yang, LI Jing-jing, ZHANG Yong-fen, HU Tao. Alkylation desulfurization of FCC gasoline catalyzed by pyridine ionic liquids[J]. J Fuel Chem Technol, 2015, 43(4):442-448. http://www.ccspublishing.org.cn/article/id/100033317
[6]	张存, 王峰, 潘小玉, 刘晓勤.酸性离子液体萃取-氧化模拟油品脱硫研究[J].燃料化学学报, 2011, 39(9):689-693. http://d.wanfangdata.com.cn/Periodical_rlhxxb201109009.aspx ZHANG Cun, WANG Feng, PAN Xiao-yu, LIU Xiao-qin. Study on desulfurization performance for model fuel by acid ionic liquid extraction-oxidation[J]. J Fuel Chem Technol, 2011, 39(9):689-693. http://d.wanfangdata.com.cn/Periodical_rlhxxb201109009.aspx
[7]	唐晓东, 李林, 曾雪玲, 赖先熔.汽油活性炭基脱硫吸附剂的制备与评价[J].燃料化学学报, 2009, 37(5):629-634. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX200905023.htm TANG Xiao-dong, LI Lin, ZEGN Xue-ling, LAI Xian-rong. Preparation and evaluation of gasoline adsorption desulfurization over activated carbon based adsorbent[J]. J Fuel Chem Technol, 2009, 37(5):629-634. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX200905023.htm
[8]	SALEH T A, DANMALIKI G I. Influence of acidic and basic treatments of activated carbon derived from waste rubber tires on adsorptive desulfurization of thiophenes[J]. J Taiwan Inst Chem E, 2016, 60:460-468. doi: 10.1016/j.jtice.2015.11.008
[9]	MENG X, HUANG H, WENG H, SHI L. Ni/ZnO-based adsorbents supported on Al₂O₃, SiO₂, TiO₂, ZrO₂:A comparison for desulfurization of model gasoline by reactive adsorption[J]. Bull korean Chem Soc, 2012, 33(10):3213-3217. doi: 10.5012/bkcs.2012.33.10.3213
[10]	SENTORUN-SHALABY C, SAHA SK, MA X, SONG C. Mesoporous-molecular-sieve-supported nickel sorbents for adsorptive desulfurization of commercial ultra-low-sulfur diesel fuel[J]. Appl Catal B:Environ, 2011, 101(3/4):718-726. http://canli.dicp.ac.cn/Gruop Seminars Pdf/20110327ylzhang.pdf
[11]	KHAN N A, JHUNG S H. Low-temperature loading of Cu⁺ species over porous metal-organic frameworks (MOFs) and adsorptive desulfurization with Cu⁺-loaded MOFs[J]. J Hazard Mater, 2012, 237/238(17):180-5. http://www.doc88.com/p-9989446071241.html
[12]	FAŁTYNOWICZ H, KACZMARCZYK J, KUŁA Ż Y ŃSKI M. Preparation and characterization of activated carbons from biomass material-giant knotweed (Reynoutria sachalinensis)[J]. Open Chem, 2015, 13(1):1150-1156. http://cn.bing.com/academic/profile?id=62208c87c78a8da5f36913061f6a0fc7&encoded=0&v=paper_preview&mkt=zh-cn
[13]	CAO B, SHEN W, LIU Y. Adsorption desulphurization of gasoline by silver loaded onto modified activated carbons[J]. Adsorption Technology, 2008, 26(4):225-231. doi: 10.1260/026361708786934451
[14]	查庆芳, 高南星, 李兆丰, 卓海波, 张玉贞.石油焦系活性炭的吸附脱硫[J].燃料化学学报, 2007, 35(2):192-197. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200702012 ZHA Qing-fang, GAO Nan-xing, LI Zhao-feng, ZHUO Hai-bo, ZHANG Yu-zhen. Adsorption desulfurization by activated carbon from petroleum coke[J]. J Fuel Chem Technol, 2007, 35(2):192-197. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=rlhxxb200702012
[15]	程凯鹏. CeO₂/AC和Ag/AC燃油脱硫吸附剂的制备及性能研究[D]. 开封: 河南大学, 2016. CHENG Kai-peng. Study on preparation and performance for adsorption desulfurization over CeO₂/AC and Ag/AC adsorbents[D]. Kaifeng: Henan University, 2016.
[16]	LEI M, TONG S T, YU W. Discussion on the Boehm titration method used in analysis of surface oxygen functional groups on activated carbon[J]. Carbon Techniques, 2011, 30(2):17-19. http://www.sid.ir/En/Journal/Reference.aspx?ID=434725
[17]	何小超, 郑经堂, 于维钊.燃油活性炭吸附深度脱硫的机理及研究进展[J].炼油技术与工程, 2007, 37(7):8-12. http://d.old.wanfangdata.com.cn/Periodical/lysj200707003 HE Xiao-chao, ZHENG Jing-tang, YU Wei-zhao. Mechanism and research progress of deep adsorption desulfurization over fuel activated carbon[J]. Pet Ref Eng, 2007, 37(7):8-12. http://d.old.wanfangdata.com.cn/Periodical/lysj200707003
[18]	SHEN W, LI Z, LIU Y. Surface chemical functional groups modification of porous carbon[J]. Recent Patents on Chemical Engineering, 2008, 1(1):27-40. doi: 10.2174/2211334710801010027
[19]	米尼奥维奇.硝酸盐岩石快速全分析[M].北京:科学出版社, 1956. Miniovich. Rapid Total Analysis of Nitrate Rock[M]. Beijing:Science Press, 1956.
[20]	张微, 葛庆杰, 徐恒泳.镍前驱体对非负载型镍催化剂上甲烷分解活性的影响[J].催化学报, 2010, 31(11):1358-1362. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=cuihuaxb201011009 ZHANG Hui, GE Qing-jie, XU Heng-yong. Effect of precursors on methane decomposition activity on non-loaded nickel catalysts[J]. J Catal, 2010, 31(11):1358-1362. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=cuihuaxb201011009
[21]	王振永. 活性炭基脱硫剂FCC汽油吸附脱硫性能评价及物化性质表征[D]. 青岛: 中国海洋大学, 2007. WANG Zhen-yong. Adsorption desulfurization process of FCC gasoline and characterization physicochemical properties for activated carbon adsorbents[D]. Qingdao: Ocean University of China, 2007.
[22]	余谟鑫, 李忠, 夏启斌, 王书文.表面负载不同金属离子的活性炭吸附二苯并噻吩[J].功能材料, 2006, 37(11):1816-1818. doi: 10.3321/j.issn:1001-9731.2006.11.039 YU Mo-xin, LI Zhong, XIA Qi-bin, WANG Shu-wen. Adsorption desulfurization for dibenzothiophene over active carbon based adsorbents with different metal ions[J]. Functional materials, 2006, 37(11):1816-1818. doi: 10.3321/j.issn:1001-9731.2006.11.039