低温一步法活性炭基脱硫剂的制备与评价
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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 m L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 mg S/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 mg S/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。
Activated carbon was prepared by one-step method at lowtemperature using sawdust as material.Effect of preparation and adsorption conditions among liquid-solid and gas-solid on desulfurization performance was discussed. The results showthat the optimum preparation conditions are as follows: mass ratio of 1 ∶ 1 for impregnation liquid( with HNO3 mass fraction of 30%) and sawdust,Ni O 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 m L,liquid-solid adsorption temperature of 40 ℃ and adsorption time of5 h,desulfurization efficiency can reach 28.36%. After continuous adsorption 4 times saturated adsorption sulfur capacity is up to 2. 34 mg S/g. Under gas-solid adsorption temperature of 250 ℃ and adsorption velocity of 6. 3 h-1,adsorption sulfur capacity can reach 2. 37 mg S/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 showthat 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.
Activated carbon was prepared by one-step method at lowtemperature using sawdust as material.Effect of preparation and adsorption conditions among liquid-solid and gas-solid on desulfurization performance was discussed. The results showthat the optimum preparation conditions are as follows: mass ratio of 1 ∶ 1 for impregnation liquid( with HNO3 mass fraction of 30%) and sawdust,Ni O 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 m L,liquid-solid adsorption temperature of 40 ℃ and adsorption time of5 h,desulfurization efficiency can reach 28.36%. After continuous adsorption 4 times saturated adsorption sulfur capacity is up to 2. 34 mg S/g. Under gas-solid adsorption temperature of 250 ℃ and adsorption velocity of 6. 3 h-1,adsorption sulfur capacity can reach 2. 37 mg S/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 showthat 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.
引文
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[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.(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.)
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[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 Taiw an Inst Chem E,2016,60:460-468.
[9]MENG X,HUANG H,WENG H,SHI L.Ni/Zn O-based adsorbents supported on Al2O3,Si O2,Ti O2,Zr O2:A comparison for desulfurization of model gasoline by reactive adsorption[J].Bull korean Chem Soc,2012,33(10):3213-3217.
[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.
[11]KHAN N A,JHUNG S H.Low-temperature loading of Cu+species over porous metal-organic framew orks(M OFs)and adsorptive desulfurization w ith Cu+-loaded M OFs[J].J Hazard M ater,2012,237/238(17):180-5.
[12]FATYNOWICZ H,KACZMARCZYK J,KUA·Z Y'N SKI M.Preparation and characterization of activated carbons from biomass materialgiant knotw eed(Reynoutria sachalinensis)[J].Open Chem,2015,13(1):1150-1156.
[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.
[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.(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.)
[15]程凯鹏.Ce O2/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 Ce O2/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.
[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.(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.)
[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.
[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.(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.)
[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.(YU Mo-xin,LI Zhong,XIA Qi-bin,WANG Shu-wen.Adsorption desulfurization for dibenzothiophene over active carbon based adsorbents w ith different metal ions[J].Functional materials,2006,37(11):1816-1818.)
[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.(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.)
[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.(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.)
[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.(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.)
[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.(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.)
[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.(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.)
[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.(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.)
[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 Taiw an Inst Chem E,2016,60:460-468.
[9]MENG X,HUANG H,WENG H,SHI L.Ni/Zn O-based adsorbents supported on Al2O3,Si O2,Ti O2,Zr O2:A comparison for desulfurization of model gasoline by reactive adsorption[J].Bull korean Chem Soc,2012,33(10):3213-3217.
[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.
[11]KHAN N A,JHUNG S H.Low-temperature loading of Cu+species over porous metal-organic framew orks(M OFs)and adsorptive desulfurization w ith Cu+-loaded M OFs[J].J Hazard M ater,2012,237/238(17):180-5.
[12]FATYNOWICZ H,KACZMARCZYK J,KUA·Z Y'N SKI M.Preparation and characterization of activated carbons from biomass materialgiant knotw eed(Reynoutria sachalinensis)[J].Open Chem,2015,13(1):1150-1156.
[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.
[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.(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.)
[15]程凯鹏.Ce O2/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 Ce O2/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.
[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.(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.)
[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.
[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.(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.)
[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.(YU Mo-xin,LI Zhong,XIA Qi-bin,WANG Shu-wen.Adsorption desulfurization for dibenzothiophene over active carbon based adsorbents w ith different metal ions[J].Functional materials,2006,37(11):1816-1818.)