Biomass Chemical Engineering. Effects of Catalyst CaO on Fast Pyrolysis of Pine for the Production of Bio-oils
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1 Biomass Chemical Engineering Vol. 47 No. 4 July 2013 doi /j. issn CaO * CaO CaO d CaO 30 % 50 % CaO TQ35 A Effects of Catalyst CaO on Fast Pyrolysis of Pine for the Production of Bio-oils YUAN LiangLIU Yun-quanWANG DuoZANG Yun-hao School of Energy Research Xiamen UniversityXiamen China AbstractThe effects of CaO on fast pyrolysis of pine were investigated in a small bubbling fluidized bed reactor. The generated pyrolysis vapor was condensed by three-stage coolingquench with coolant at the first stagewater cooling with shell-and-tube heat exchanger at the second stageand ice bath cooling at the last stage. The liquids obtained from each stage were named biooil 1bio-oil 2 and bio-oil 3correspondingly. It was found that with the addition of CaO to pinethe water content in bio-oils increased the heating value decreasedthe ph increasedthe content of ketones and hydrocarbons increased while phenols decreased. The bio-oils stability tests showed that phenols content increased increased to 50 % when 30 % of CaO is added esters decreased and the water content increased after the bio-oils stored for 30 days at room temperature. Key wordsfast pyrolysiscao catalystbio-oilsstability AA yuanliang87@ 126. com * yq_liu@ xmu. edu. cn
2 2 47 Williams 7 ZSM-5 Scholze 8 MnO 80 CaO ph Lin 9 CaO Wang 10 CaO kg /h CaO CaO ~ 2 mm CaO 98 % 50 μm 105 CaO 4 CaO 10 % 20 % 30 % Elementar Vario EL CHNS C % N % H % O % Fig. 1 1 The schematic diagram of biomass fast pyrolysis
3 4 CaO kg /h TA SDT-Q % /min QP2010SE GC-MS 1 ml 5 % 1 ml GC 50 3 min 4 /min min 280 NIST METTLER-TOLEDO KF-V30 ph starter 3C PH MTZW-A4 0 ~ % CaO CaO CaO 2 2 CaO CaO CO 2 CaO CaO CaO CaO E % CaO 2 CaO CaO Fig. 2 The effect of CaO addition on the pyrolysis yield 30 % 20 % CaO CaO CO 13 CaO CaO CaO CaO 400 ~ CaCO ph CaO + 2RCOOH RCOO 2 Ca + H 2 O RCOO 2 Ca CaCO 3 + RCOR 1 2
4 Table 1 1 CaO The effect of CaO addition on the major components in bio-oils CaO phenols ketones components /% alkanes esters furans CaO ph CaO ph 2 Table 2 2 CaO ph The effect of CaO addition on the content of water heating value and ph value of bio-oils CaO /% water content /MJ mol - 1 heating value ph ph value CaO % % % 2 3 CaO CaO 30 % % % % CaO H 2 O CaO 1 > 2 > 3 1 CaO 1 3 CaO CaO 2 CaO CaO ph
5 4 CaO 5 CaO 30 % CaO 1 ph 4. 4 CaO CaO Wang Lin 9-10 CaO 18 CaO CaO 3 RCOOH CaO CO 2 + RH 2. 2 CaO 30 d ph 3 3 CaO 10 % ~ 20 % CaO 30 % ~ 50 % CaO 1 3 CaO CaO Table d The change of components in bio-oils after stored for 30 days CaO components /% phenols esters furans ph 4 19 Table d ph The change of water contentheating value and ph value in bio-oils after stored for 30 days CaO /% water content /MJ mol - 1 heating value ph ph value
6 % ~ 4 % CaO ph CaO 1 2 ph CaO RCOOR + H 2 O CaO RCOOH + ROH CaO CaO 3. 2 CaO CaO < 2 < 3 1 > 2 > 3 1 > 2 > 3pH 1 > 2 > 3 1MOHAN D PITTMAN C U STEELE P H et al. Pyrolysis of wood /biomass for bio-oila critical review J. Energy Fuels OASMAA ASOLANTAUSTA Y ARPIAINEN V et al. Fast pyrolysis bio-oils from wood and agricultural residues J. Energy Fuels J Ⅲ J I J CZERNIK S BRIDGWATER A V. Overview of application of biomass fast pyrolysis oil J. Energy Fuel WILLIAMS P T NUGRANAD N. Comparison of from the pyrolysis and catalytic pyrolysis of rice husks J. Energy SCHOLZE B. Long-term stability catalytic upgrading and application of pyrolysis oils-improving the properties of a potential substitute for fossil fuels D. Hamburg University of Hamburg LIN Yu-yu ZHANG Chu ZHANG Ming-chuan et al. Deoxygenation of bio-oil during pyrolysis of biomass in the presence of CaO in a fluidizedbed reactor J. Energy & Fuels WANG Deng-hui XIAO Rui ZHANG Hui-yan et al. Comparison of catalytic pyrolysis of biomass with MCM-41 and CaO catalysts by using TGA-FTIR analysis J. Journal of Analytical and Applied Pyrolysis WESTERHOF R J M BRILMAN D W F VAN SWAAIJ W P M et al. Effect of temperature in fluidized bed fast pyrolysis of biomassoil quality assessment in test units J. Industrial & Engneering Chemistry Research CHEN Tian-ju DENG Chun-jian LIU Rong-hou. Effect of selective condensation on the characterization of bio-oil from pine sawdust fast pyrolysis using a fluidized-bed reactor J. Energy & Fuel FRANKLIN H D PETERS W A. HOWARD J B. Mineral matter effects on the rapid pyrolysis and hydropyrolysis of a bituminous coal1 Effects on yields of char tar and light gaseous volatiles J. Fuel DING Lian-hui RAHIMI P HAWKINS R et al. Naphthenic acid removal from heavy oils on alkaline earth-metal oxides and ZnO catalysts J. Applied Catalysis A General / ZHANG Ai-hua MA Qi-sheng WANG Kang-shi et al. Naphthenic acid removal from crude oil through catalytic decarboxylation on magnesium oxide J. Applied Catalysis A General LU Hong KHAN A SMIRNIOTIS P G. Relationship between structural properties and CO 2 capture performance of CaO-based sorbents obtained from different organometallic precursors J. Industrial & Engineering Chemistry Research YANG Xu-lai ZHANG Jian ZHU Xi-feng. Decomposition and calcination characteristics of calcium-enriched bio-oilj. Energy & Fuels D CZERNIK S JOHNSON D K BLACK S. Stability of wood fast pyrolysis oil J. Biomass Bioenergy /2 /3 /4 /5 /
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