Preparation of Nano-CuO and Its Removal Performance of H2S at Room Temperature
Fen LI1,*(), Tao LEI1, Ying YANG1, Yan-ping ZHANG2, Jin WEI1, Guang-hui YANG1
1 College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, China 2 School of Civil Engineering, Hebei University of Technology, Tianjin 300401, China
Nano-CuO was prepared by methods of liquid-phase precipitation and solid state reaction. The structure of nano-CuO was analyzed by XRD, XPS, TEM and BET techniques, and the effect of the structure of nano-CuO on the removing performance of H2S was also studied. The results indicate that various crystal size nano-CuO can be prepared by changing preparation process parameters. The desulfurization performance of nano-CuO decreases significantly with the increases of crystal size. The nano-CuO with the crystal size of 9.3 nm exhibits the best desulfurization performance, and the breakthrough time of H2S can reach 270 min. A small amount cluster caused by small crystal size has a little impact on the desulfurization activity of nano-CuO. However, the appearance of oxygen vacancies on the copper oxide surface and the decrease of electron cloud density around the copper are beneficial to the improving of desulfurization performance of nano-CuO. When the specific surface area is a little different,the effect on the desulfurization activity of nano-CuO is not obvious. But the removal of H2S can be improved when the irregular pore formed by grain accumulation distribution is narrow, and the open and contraction pore structures exist at the same time.
ZHOU Ting, XIN Jin-hao, PENG Liang, et al Removal of hydrogen sulfide gas by biological activated carbon fiber and bio-membrance[J]. Chinese Journal of Environmental Engineering, 2012, 6 (9): 3243- 3247.
HOU Xiang-lin, GAO Yin-ben, CHEN Song-ying High temperature H2S removal over various metal oxides[J]. Environmental Engineering, 1997, 15 (3): 30- 32.
3
LI Z J, FLYTZANI-STEPHANOPOULOS M Cu-Cr-O and Cu-Ce-O regenerable oxide sorbents for hot gas desulfurization[J]. Industrial & Engineering Chemistry Research, 1997, 36 (1): 187- 196.
4
PINEDA M, PALACIOS J M, ALONSO L Performance of zinc oxide based sorbents for hot coal gas desulfurization in multicycle tests in fixed-bed reactor[J]. Fuel, 2000, 79 (8): 885- 895.
5
ALONSO L, PALACIOS J M, GARCIA E, et al Characterization of Mn and Cu oxides as regenerable sorbents for hot coal gas desulfurization[J]. Fuel Processing Technology, 2000, 62 (1): 31- 44.
6
LEE H S, KIM J Y, YU J K, et al A study of desulfurization ability and activation energy for CuO-AgO sorbents[J]. Korean Journal of Chemical Engineering, 2005, 22 (6): 889- 893.
7
BU X P, YING Y J, ZHANG C Q, et al Research improvement in Zn-based sorbent for hot gas desulfurization[J]. Powder Technology, 2008, 180 (1-2): 253- 258.
8
KO T H, CHU H, CHAUNG L K The sorption of hydrogen sulfide from hot syngas by metal oxides over supports[J]. Chemosphere, 2005, 58 (4): 467- 474.
9
KARVAN O, ATAKUL H Investigation of CuO/mesoporous SBA-15 sorbents for hot gas desulfurization[J]. Fuel Processing Technology, 2008, 89 (9): 908- 915.
10
KARVAN O, SIRKECIOGLU A, ATAKUL H Investigation of nano-CuO/mesoporous SiO2 materials as hot gas desulphurization sorbents[J]. Fuel Processing Technology, 2009, 90 (12): 1452- 1458.
11
DHAGE P, SAMOKHVALOV A, REPALA D, et al Copper-promoted ZnO/SiO2 regenerable sorbents for the room temperature removal of H2S from reformate gas streams[J]. Industrial & Engineering Chemistry Research, 2010, 49 (18): 8388- 8396.
12
YANG H Y, TATARCHUK B Novel-doped zinc oxide sorbents for low temperature regenerable desulfurization applications[J]. AICHE Journal, 2010, 56 (11): 2898- 2904.
13
CUI H, TUM S Q, REESE M A Removal of sulfur compounds from utility pipelined synthetic natural gas using modified activated carbons[J]. Catalysis Today, 2009, 139 (4): 274- 279.
14
KIM H T, JUN K W, KIM S M, et al Co-precipitated Cu/ZnO/Al2O3 sorbent for removal of odorants t-butylmercaptan (TBM) and tetrahydrothiophene (THT) from natural gas[J]. Energy and Fuels, 2006, 20 (5): 2170- 2173.
15
BAE J W, KANG S H, MURALI D G, et al Effect of Al2O3 content on the adsorptive properties of Cu/ZnO/ Al2O3 for removal of odorant sulfur compounds[J]. International Journal of Hydrogen Energy, 2009, 34 (20): 8733- 8740.
LI Fen, ZHANG Yan-ping, YANG Ying, et al Structure of activated carbon supported with nano-ZnO and its removal performance of H2S at room temperature[J]. Journal of the Chinese Ceramic Society, 2012, 40 (6): 800- 805.
YAN Bo, WANG Xin, SHAO Chun-hong, et al CuO nanoparticles preparation and desulfurization performance at normal temperature[J]. Chinese Journal of Inorganic Chemistry, 2007, 23 (11): 1869- 1874.
SHI Zhen-tai Determination of sulfur content in silver concentrates by combustion-acid-base titrimetry[J]. [J]. Gansu Metallurgy, 2008, 30 (2): 73- 84.
19
YI H H, YU Q F, TANG X L, et al Phosphine adsorption removal from yellow phosphorus tail gas over CuO-ZnO-La2O3/activated carbon[J]. Industrial & Engineering Chemistry Research, 2011, 50 (7): 3960- 3965.
ZHANG Yue, ZHANG Lei, DENG Ji-guang, et al Hydrothermal fabrication and catalytic performance of single-crystalline La2-xSrxCuO4(x=0, 1) with specific morphologies for methane oxidation[J]. Chinese Journal of Catalysis, 2009, 30 (4): 347- 350.
21
KIM J, KIM W, YONG K J. CuO/ZnO heterostructured nanorods: photochemical dynthesis and the mechanism of HS gas sensing[J] Journal of Physical Chemistry C, 2012, 116(29): 15682-15691.
22
WU Q, YAKSHINSKIY B V, MADEY T E Adsorption and decomposition of H2S on UO2 (001)[J]. Surface Science, 2003, 523, 1- 11.
GAN Xiao-rong, XUE Fang-hong, HUANG Hao, et al Preparation and characterization of SiC/C nano-composites[J]. Journal of Materials Engineering, 2014, (2): 75- 80.
CHEN Bin, PANG Hou-jun, ZHANG Xiu-qing, et al Porosity of Fe3Al intermetallic porous materials[J]. Materials for Mechanical Engineering, 2008, 32 (5): 33- 37.
2015, Vol. 43 
), 雷涛1, 杨莹1, 张彦平2, 魏进1, 杨光辉1
