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Study of Biomass Chemical Looping Gasification Using Interconnected Fluidized Bed with Ilmenite Oxygen Carrier
|關鍵字:||生質物;合成氣;化學迴路氣化;鈦鐵礦;內通式流體化床;biomass;syngas;chemical looping gasification;ilmenite;interconnected fluidized bed||引用:|| Z. Huang, Y. Zhang, J. Fu, L. Yu, M. Chen, S. Liu, F. He, D. Chen, G. Wei, K. Zhao, A. Zheng, Z. Zhao, H. Li (2016) Chemical looping gasification of biomass char using iron ore as an oxygen carrier, International Journal of Hydrogen Energy 41: 17871-17883.  顧洋，邱炳嶔，吳鉉智 (2013) 化學迴圈程序技術及其在節能減碳領域之應用，台灣能源期刊: 35-50。  J. D. Figueroa, T. Fout, S. Plasynski, H. McIlvried, R. D. Srivastava (2008) Advances in CO2 capture technology—the U.S. department of energy's carbon sequestration program, International Journal of Greenhouse Gas Control 2: 9-20.  朱敬平 (2011) 化學迴圈燃燒技術發展概況簡介，中興工程季刊: 63-72。  吳耿東，李宏台 (2001) 廢棄物氣化技術，工程月刊74(4): 85-96。  E. J. Anthony (2008) Solid looping cycles: a new technology for coal conversion, Industrial & Engineering Chemistry Research 47: 1747-1754.  Y. Cao, B. Casenas, W.-P. Pan (2006) Investigation of chemical looping combustion by solid fuels. 2. redox reaction kinetics and product characterization with coal, biomass, and solid waste as solid fuels and CuO as an oxygen carrier, Energy & Fuels 20: 1845-1854.  W. K. Lewis, E. R. Gilliland, W. P. Sweeney (1951) Gasification of carbon metal oxides in a fluidized power bed., Chemical Engineering Progress 47: 251-256.  F. Donat, W. Hu, S. A. Scott, J. S. Dennis (2015) Characteristics of copper-based oxygen carriers supported on calcium aluminates for chemical-looping combustion with Oxygen uncoupling (CLOU), Industrial & Engineering Chemistry Research 54: 6713-6723.  G. Huijun, S. Laihong, F. Fei, J. Shouxi (2015) Experiments on biomass gasification using chemical looping with nickel-based oxygen carrier in a 25kWth reactor, Applied Thermal Engineering 85: 52-60.  Z. Huang, F. He, Y. Feng, K. Zhao, A. Zheng, S. Chang, G. Wei, Z. Zhao, H. Li (2013) Biomass char direct chemical looping gasification using NiO-modified iron ore as an oxygen carrier, Energy & Fuels 28: 183-191.  J. Adanez, A. Abad, F. Garcia-Labiano, P. Gayan, L. F. de Diego (2012) Progress in chemical-looping combustion and reforming technologies, Progress in Energy and Combustion Science 38: 215-282.  H. Fang, L. Haibin, Z. Zengli (2009) Advancements in development of chemical-looping combustion: A review, International Journal of Chemical Engineering 2009: 1-16.  A. Lyngfelt, B. Leckner, T. Mattisson (2001) A fluidized-bed combustion process with inherent CO2 separation; application of chemical-looping combustion, Chemical Engineering Science 56: 3101-3113.  C. Linderholm, A. Abad, T. Mattisson, A. Lyngfelt (2008) 160h of chemical-looping combustion in a 10kW reactor system with a NiO-based oxygen carrier, International Journal of Greenhouse Gas Control 2: 520-530.  J. Adánez, P. Gayán, J. Celaya, L. F. de Diego, F. García-Labiano, A. Abad (2006) Chemical looping combustion in a 10 kWth prototype using a CuO/Al2O3 oxygen carrier: effect of operating conditions on methane combustion, Industrial & Engineering Chemistry Research 45: 6075-6080.  S. R. Son, S. D. Kim (2006) Chemical-looping combustion with NiO and Fe2O3 in a thermobalance and circulating fluidized bed reactor with double loops, Industrial & Engineering Chemistry Research 45: 2689-2696.  Norihisa Miyoshi, Seiichiro Toyada, K. Matsuoka (2001) Patent application publication:fluidized-bed gasification method and apparatus: US2004/0045272 A1.  R. Korbee, O. C. Snip, J. C. Schouten, C. M. Van den Bleek (1994) Rate of solids and gas transfer via an orifice between partially and completely fluidized beds, Chemical Engineering Science 49: 5819-5832.  A. Abad, T. Mattisson, A. Lyngfelt, M. Ryden (2006) Chemical-looping combustion in a 300 W continuously operating reactor system using a manganese-based oxygen carrier, Fuel 85: 1174-1185.  M. M. Tijani, A. Aqsha, N. Mahinpey (2017) Synthesis and study of metal-based oxygen carriers (Cu, Co, Fe, Ni) and their interaction with supported metal oxides (Al2O3, CeO2, TiO2 , ZrO2 ) in a chemical looping combustion system, Energy 138: 873-882.  Z. Huang, F. He, H. Zhu, D. Chen, K. Zhao, G. Wei, Y. Feng, A. Zheng, Z. Zhao, H. Li (2015) Thermodynamic analysis and thermogravimetric investigation on chemical looping gasification of biomass char under different atmospheres with Fe2O3 oxygen carrier, Applied Energy 157: 546-553.  J. Bessières, A. Bessières, J. J. Heizmann (1980) Iron oxide reduction kinetics by hydrogen, International Journal of Hydrogen Energy 5: 585-595.||摘要:||
本研究使用高150 cm，每格6 cm見方大小之四格內通式流體化床熱模試驗系統配合鈦鐵礦載氧體進行生質物(雜木造粒)氣化實驗，探討流體化氣速及反應溫度對於氣化合成氣組成之影響。首先使用熱重分析儀對不同質量配比的鈦鐵礦與活性碳進行反應性測試，結果顯示鈦鐵礦與活性碳質量比7:3時反應性最佳。接著以高解析X光繞射儀檢測F2O3反應前後狀態變化，鈦鐵礦於900oC氮氣環境下Fe2O3會有狀態變化，還原成Fe3O4，當混入生質物會使Fe2O3更進一步還原成FeO，但皆無法於通入空氣的20分鐘內回復原本之F2O3狀態。
The overall objective of this study is to study the syngas production from biomass chemical looping gasification using ilmenite as the oxygen carrier. The study was divided into two parts. In the first part, some fundamental studies regarding the properties of ilmenite were performed. First, the thermos-gravimetric analyzer was used to test the reactivity of different compositions of ilmenite and activated carbon. The results showed that best reactivity of ilmenite can be resulted when mass ratio of ilmenite to activated has the value of 7:3. Secondly, the ilmenite particles which reacted with biomass under difference conditions were analyzed by the X-ray diffractometer to identify the crystalline phase structures. It was found that ilmenite was reduced from Fe2O3 to Fe3O4 under nitrogen atmosphere at 900oC. When it is mixed with biomass, Fe2O3 was further reduced to FeO. However, it could not return to the original state within 20 minutes under air atmosphere at 900°C.
In the second part of the study, a 20 kWth interconnected fluidized bed with a height of 150 cm and four 6cm×6cm compartments was employed to carry out the biomass chemical looping gasification. From the biomass gasification experiment results, it can be found that biomass cracking reaction in the fuel reactor at 750~800°C would dominantly consume the energy. At this temperature range, gasification reaction was difficult to occur. With gasification temperature at 900°C, it was found that better gasification performance can be obtained.
For the capability of oxygen carrier oxidation in air reactor, the experiment results indicated that some solid carbon particles circulated with oxygen carriers into the air reactor and was oxidized to form CO2 for temperature at 700°C. Although O2 concentration decreases at 750 and 800°C, the CO2 concentration is not increased. It was speculated that ilmenite was oxidized and returned to the oxidation state in the fuel reactor at 900°C so that the composition of the syngas collected at reaction was similar to air.
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