화학공학소재연구정보센터
Clean Technology, Vol.25, No.2, 107-113, June, 2019
일메나이트광의 유동층 염화반응에 대한 수치적 예측
Numerical Prediction for Fluidized Bed Chlorination Reaction of Ilmenite Ore
E-mail:
초록
2단 유동층 염화로에서 일메나이트광의 선택염화반응과 이산화티탄의 탄소염화반응의 염화도를 예측하기 위해서 shrinking core 모델과 유출률 및 입자파손을 고려한 수치 모델을 개발하였다. 입자분포를 고려하여 입자별 물질 수지와 염화반응을 반영할 수 있는 유동층 염화 반응 해석이 가능하다. 유동층 염화로의 실험값과 비교하여 약 6% 오차율의 정확성을 보였다. 입자 크기에 따라서는 입자 크기가 작을수록 염화도의 변화가 더 크게 나타났으며 염화도 1의 값에 도달하는 반응시간 차이가 약 100 min 정도로 나타났다. 온도의 변화(800 ~ 1000 ℃)에 대한 염화도의 변화는 염화도 0.9에 도달하는 반응시간이 약 10 min 차이로 크게 나타나지 않았다. 1단계 선택염화공정에서 일메나이트광의 질량감소율은 180 min 경과 시에 이론값인 0.4735 값에 근접하고, Fe 성분의 염화도는 FeCl2 또는 FeCl3로 변환되어 180 min 경과 시에는 거의 1의 값을 보인다. 2단계 탄소염화공정에서 TiO2의 염화도는 180 min 경과 시 0.98에 근접하고, 질량분율은 0.02에 도달하여 TiCl4로 변환되는 것으로 나타났다. 1단계 선택염화공정에서 TiO2는 180 min 경과 시에 98%까지 생성되었다가 연속적인 2단계 탄소염화공정에서 추가로 90 min 경과 시(총 경과 시간 270 min)에 99% TiCl4로 전환되는 것으로 나타나고, 질량감소율도 99% 이상 감소하였다.
Numerical model that considered the shrinking core model and elutriation and degradation of particles was developed to predict selective chlorination of ilmenite and carbo-chlorination of TiO2 in a two stage fluidized bed chlorination furnace. It is possible to analyze the fluidized bed chlorination reaction to be able to reflect particle distribution for mass balances and the chlorination reaction. The numerical model showed an accuracy with error less than 6% compared with fluidized bed experiments. The chlorination degree with particle size change was greater with a smaller particle size, and there was a 100 min difference to obtain a chlorination degree of 1 between 75 μm and 275 μm. This was not shown to such a great extent with variation of temperature (800 ~ 1000 ℃), and there was only a 10 min difference to obtain a chlorination degree of 0.9. In the first selective chlorination process, the mass reduction rate approached to the theoretical value of 0.4735 after 180 min, and chlorination changed the Fe component into FeCl2 or FeCl3 and showed nearly 1. In the second carbo-chlorination process, the chlorination degree of TiO2 approached 0.98 and the mass fraction reached 0.02 with conversion into TiCl4. In the first selective chlorination process, 98% of TiO2 was produced at 180 min, and this was changed into 99% of TiCl4 after an additional 90 min. Also the mass reduction rate of TiO2 was reduced to 99% in the second continuous carbo-chlorination process.
  1. Harris HM, Henderson AW, Cambel TT, "Fluidized Coke Bed Chlorination of Ilmenite,” Report, Bureau of mine, USA (1976).
  2. Chughtai AR, Harris HM, Riter JR, Metallurgical Transactions B, 8(2), 507 (1977)
  3. Neurgaonkar VG, Gokarn AN, Joseph K, J. Chem. Technol. Biotechnol., 36, 27 (1986)
  4. Luckos A, den Hoed P, Ind. Eng. Chem. Res., 43(18), 5645 (2004)
  5. Moodley S, Eric RH, Kucukkaragoz C, Kale A, Ind. Eng. Chem. Res., 43, 5645 (2004)
  6. Fouga GG, Pasquevich DM, Bohe AE, Mineral Processing and Extractive Metallurgy (Trans. Inst. min. Metall. C), 116(4), 230-238 (2007).
  7. Sohn HY, Zhou L, Chem. Eng. J., 72(1), 37 (1999)
  8. Rhee KI, Sohn HY, Metallurgical Transactions B, 21(2), 321 (1990)
  9. Niu LP, Zhang TA, Ni PY, Ouyang K, Trans. Nonferrous Met. Soc. China, 23(11), 3448 (2013)
  10. Morris AJ, Jensen F, Metallurgical Transactions B, 7(1), 89 (1976)
  11. Hahn YB, Chang KS, Metallurgical Transactions B, 29(5), 1107 (1998)
  12. Kunii D, Levenspiel O, in Fluidization Engineering, 2nd ed., Butterworth-Heinemann, Boston, MA, pp. 337-56 (1991).
  13. Homma S, Ogata S, Koga J, Matsumoto S, Chem. Eng. Sci., 60(18), 4971 (2005)
  14. Jung EJ, Metallic Material Research Group, Pohang, Korea, personal communication, Jun (2018).
  15. Van Deventer JSJ, Thermochimica Acta, 124, 205 (1988)
  16. Fouga et al., Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metal. C), 116(4), 230-238 (2007).