47 4 2013 7 Biomass Chemical Engineering Vol. 47 No. 4 July 2013 doi10. 3969 /j. issn. 1673-5854. 2013. 04. 001 CaO * 361102 CaO 1 2 3 CaO 1 2 3 30 d CaO 30 % 50 % CaO TQ35 A 1673-5854201304 - 0001-06 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 361102China 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 1-2 3-5 6 6 2013-03 - 14 863 2012AA051801 1987 - E-mailyuanliang87@ 126. com * 1963 - E-mailyq_liu@ xmu. edu. cn
2 47 Williams 7 ZSM-5 Scholze 8 MnO 80 CaO ph Lin 9 CaO Wang 10 CaO 11-12 1 kg /h CaO CaO 1 1. 1 1 ~ 2 mm CaO 98 % 50 μm 105 CaO 4 CaO 10 % 20 % 30 % Elementar Vario EL CHNS C 49. 41 % N 6. 28 % H 0. 24 % O 44. 07 % 1. 2 1 Fig. 1 1 The schematic diagram of biomass fast pyrolysis
4 CaO 3 1 1 2 3 1. 3 500 1 kg /h TA SDT-Q600 99. 999 % 30 800 20 /min QP2010SE GC-MS 1 ml 5 % 1 ml GC 50 3 min 4 /min 280 3 min 280 NIST METTLER-TOLEDO KF-V30 ph starter 3C PH MTZW-A4 0 ~ 100 3 5 % 2 2. 1 CaO 2. 1. 1 CaO CaO 2 2 CaO CaO CO 2 CaO 2. 1. 2 CaO 1 2 3 CaO 1 1 2 3 CaO 2-2- -4-2- -4- E-2- -4-1- 70 % CaO 2 CaO 1 2 3 CaO Fig. 2 The effect of CaO addition on the pyrolysis yield 30 % 20 % CaO CaO CO 13 CaO CaO CaO 14-15 CaO 400 ~ 500 1 2 CaCO 3 16-17 ph CaO + 2RCOOH RCOO 2 Ca + H 2 O RCOO 2 Ca CaCO 3 + RCOR 1 2
4 47 1 2 3 Table 1 1 CaO The effect of CaO addition on the major components in bio-oils CaO phenols ketones components /% alkanes esters furans 0 34. 1 30. 4 2. 9 11. 9 5. 9 10 28. 9 32. 2 3. 4 9. 7 4. 7 20 28. 4 34. 3 4. 0 9. 3 5. 4 30 19. 9 38. 2 4. 6 4. 2 0. 5 0 33. 9 30. 8 3. 7 10. 2 5. 9 10 27. 7 32. 1 3. 8 9. 4 6. 1 20 27. 2 34. 9 4. 2 8. 8 3. 9 30 18. 2 37. 9 5. 5 4. 1 2. 1 0 30. 4 30. 2 4. 1 3. 8 6. 3 10 25. 6 33. 0 4. 6 3. 2 7. 9 20 23. 5 34. 5 5. 2 2. 5 7. 8 30 15. 4 38. 3 5. 9 1. 7 3. 1 2. 1. 3 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 1 2 3 CaO /% water content /MJ mol - 1 heating value ph ph value 0 13. 6 20. 6 2. 5 10 15. 7 20. 3 4. 2 20 16. 1 19. 8 4. 3 30 20. 5 19. 6 4. 4 0 22. 3 16. 5 2. 4 10 22. 5 16. 8 4. 2 20 25. 0 17. 1 4. 2 30 25. 6 17. 8 4. 2 0 27. 3 16. 1 2. 4 10 30. 9 15. 6 2. 7 20 33. 8 15. 7 2. 6 30 42. 6 14. 5 2. 6 2 CaO 1 2 3 13. 6 % 22. 3 % 27. 3 % 2 3 CaO CaO 30 % 1 2 3 20. 5 % 25. 6 % 42. 6 % CaO H 2 O CaO 1 > 2 > 3 1 CaO 1 3 CaO CaO 2 CaO CaO 1 2 3 ph 2. 5 2. 4 2. 4
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 1 2 3 Table 3 3 30 d The change of components in bio-oils after stored for 30 days CaO components /% phenols esters furans 0 35. 3 2. 0 8. 2 10 33. 5 3. 7 4. 5 20 36. 2 0 3. 3 30 29. 8 0. 2 1. 8 0 35. 2 1. 7 8. 8 10 39. 9 3. 3 2. 2 20 39. 9 3. 3 2. 2 30 27. 2 0. 1 2. 0 0 35. 0 2. 9 3. 3 10 37. 9 2. 8 7. 0 20 27. 7 1. 4 7. 9 30 20. 1 0. 3 0. 2 ph 4 19 Table 4 4 30 d ph The change of water contentheating value and ph value in bio-oils after stored for 30 days 3 1 2 3 CaO /% water content /MJ mol - 1 heating value ph ph value 0 14. 2 19. 8 2. 6 10 17. 1 19. 6 3. 3 20 17. 9 18. 9 3. 4 30 24. 2 19. 1 3. 9 0 23. 0 15. 8 2. 4 10 23. 9 16. 6 3. 5 20 27. 1 16. 3 3. 7 30 27. 9 17. 1 3. 6 0 28. 1 15. 9 2. 4 10 33. 2 15. 2 2. 4 20 36. 0 15. 3 2. 5 30 46. 5 14. 2 2. 5
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