DOI QR코드

DOI QR Code

Carbonation Mechanism of Hydrated Cement Paste by Supercritical Carbon Dioxide

초임계 이산화탄소에 의한 시멘트 페이스트의 중성화 반응 메커니즘

  • Park, Jeong-Won (Department of Architectural Engineering, Pukyong National University) ;
  • Kim, Ji-Hyun (Multidisciplinary Infra-technology Research Laboratory, Pukyong National University) ;
  • Lee, Min-Hee (Department of Environmental Sciences, Pukyong National University) ;
  • Chung, Chul-Woo (Department of Architectural Engineering, Pukyong National University)
  • Received : 2018.06.05
  • Accepted : 2018.08.23
  • Published : 2018.10.20

Abstract

Recently, needs for utilization of recycled aggregate have been increasing. However, its utilization has been limited due to its high alkalinity, which mostly came from the unremoved cement paste particles that were attached at the surface of recycled aggregate. Various efforts has been made to reduce its alkalinity by using $CO_2$, but currently available methods that uses $CO_2$ generate the problem with pH recovery. Considering the fact that supercritical $CO_2$ ($scCO_2$) can provide more rapid carbonation of cement paste than by normal $CO_2$, $scCO_2$ was utilized in this work. The reaction between $scCO_2$ and hydrated cement paste has been systematically evaluated. According to the results, it was found that powder type showed higher carbonation compared to that of cube specimens. It seems the carbonation by $scCO_2$ has occurred only at the surface of the specimen, and therefore still showed some amount of $Ca(OH)_2$ calcium aluminates after reaction with $scCO_2$. With powder type specimen, all $Ca(OH)_2$ was converted into $CaCO_3$. Moreover, additional calcium that came from both calcium aluminate hydrates and calcium silicate hydrates reacted with $scCO_2$ to form $CaCO_3$. After carbonation with $scCO_2$, the powder type specimen did not show pH recovery, but cube specimens did show due to the presence of portlandite.

최근 순환골재의 활용에 관한 필요성이 증대되고 있으나, 순환골재의 강알칼리성으로 인해 다양한 문제들이 발생되고 있다. 순환골재의 강알칼리성은 대부분 골재 표면에 완전히 제거되지 못한 시멘트 페이스트에 의해 발현되는 것으로써 이를 해결하기 위해 이산화탄소를 활용하여 순환골재의 pH를 저감하기 위해 노력이 지속되어왔다. 그러나 기존의 이산화탄소를 이용한 처리 방법에 의해 중성화 처리된 순환골재는 시간이 지남에 따라 pH가 다시 회복된다는 문제점을 가지고 있다. 따라서 본 연구에서는 이러한 문제점을 해결하기 위한 방법으로 반응성이 뛰어난 초임계이산화탄소의 활용을 제안하며, 이를 위해 초임계상의 이산화탄소와 수화된 시멘트 페이스트간의 반응 메커니즘을 분석하였다. 그 결과 입자 형태 및 $scCO_2$ 주입량에 따라 중성화 반응정도가 현저하게 달라지는 것으로 나타났다. 특히 powder 형태 시험체에서 $scCO_2$ 주입량이 많은 고온 고압 상태에서 중성화 반응은 활발하게 이루어졌다. 이때 시멘트의 높은 pH를 주도하는 portlandite가 대부분 calcite와 aragonite의 형태로 변환되었으며, ettringite, hemicarbonate 및 monocarbonate와 같은 calcium aluminate 수화물 또한 안정적으로 존재하지 못하고 분해된 것으로 나타났다. 반면, 10mm 크기의 수화된 시멘트 페이스트는 $scCO_2$가 시험체 내부깊이 침투하지 못하고 표면에서만 반응하여, 반응 후에도 내부에 portlandite와 calcium aluminate 수화물이 잔존한다. 이로 인해 시간이 경과할수록 내부의 portlandite가 점차 용출되어 pH가 다시 상승하는 것으로 나타났다.

Keywords

References

  1. Gil SW. Long-term master planning for environment- friendly process and recycling promotion of Construction Wastes. Journal of the Korean Recycled Construction Resources Institute. 2006 Dec;2(2):8-12.
  2. Lee WP, Lee CH. The use of recycled aggregate and recycled products revitalization. Journal of the Korean Recycled Construction Resources Institute. 2014 Dec;9(4):18-28.
  3. Hong SW, Park S, Ahn YS. A research on the efficient way and the analysis of the actual condition for recycling waste concrete discharged as construction waste. Journal of the Architectural Institute of Korea Structure & Construction. 2004 Feb;20(2):97-104.
  4. Hong SR, Kim HS, Kwak EG, Park SG, Kim JM. Characteristics of recycled fine aggregate by sodium carbonated water. Journal of the Korean Recycled Construction Resources Institute. 2011 Jun;6(2):97-102.
  5. Song TH, Lee JC, Lee SH. A study on the pH characteristic of recycle aggregate according to test methods and elapsed time. Journal of the Korean Recycled Construction Resources Institute. 2011 Sep;6(3):61-8.
  6. Choi JG, Lee GC. Study on performance of pH reducing agent applied for wet process of recycled aggregate. Journal of the Korean Recycled Construction Resources Institute. 2015 Dec;3(4):366-73. https://doi.org/10.14190/JRCR.2015.3.4.366
  7. Han CG, Han MC, Han SY. Reduction of pH of recycled fine aggregate due to natural and artificial treatment method. Journal of the Korean Recycled Construction Resources Institute. 2011 Mar;6(1):103-10.
  8. Han MC, Han DY. Study on pH reducing method of recycled fine aggregate for embanking or covering. Journal of the Korea Institute of Building Construction. 2017 Feb;17(1):23-30. https://doi.org/10.5345/JKIBC.2017.17.1.023
  9. Chae SC, Jang YN, Ryu KW. Mineral carbonation as a sequestration method of CO2. Journal of the Geological Society of Korea. 2009 Oct;45(5):527-55.
  10. Han MC, Han DY. Study on pH reducing method of recycled fine aggregate for embanking or covering. Journal of the Korea Institute of Building Construction. 2017 Feb;17(1):23-30. https://doi.org/10.5345/JKIBC.2017.17.1.023
  11. Lee IS, Bok YJ, Hong SR, Kim JM. An experimental study for reduction pH of recycled aggregate. Proceedings of The Korea Concrete Institute; 2012 Nov 7-9; Muju, Korea. Seoul (Korea): The Korea Concrete Institute; 2012. p. 819-20.
  12. Kim DM, Kim MJ. Mineral carbonation using industrial waste. Journal of Korea Society of Waste Management. 2015 Jun;32(4):317-28. https://doi.org/10.9786/kswm.2015.32.4.317
  13. Park JY, Baek KB, Lee MH, Chung CW, Wang SK. The use of the surface roughness value to quantify the extent of supercritical CO2 involved geochemical reaction at a $CO_2$ sequestration Site. Applied Science. 2017 Jun;7(6):572-98. https://doi.org/10.3390/app7060572
  14. Kang HM, Baek KB, Wang SK, Park JY, Lee MH. Study on the dissolution of sandstones in gyeongsang basin and the calculation of their dissolution coefficients under $CO_2$ injection condition. Economic and Environmental Geology. 2012 Nov;45(6):661-72. https://doi.org/10.9719/EEG.2012.45.6.661
  15. Park JY, Lee MH, Wang SK. Study on the geochemical weathering process of sandstones and mudstones in pohang basin at $CO_2$ storage condition. Economic and Environmental Geology. 2013 Jun;46(3):221-34. https://doi.org/10.9719/EEG.2013.46.3.221
  16. Gupta S, Saltanov E, Mokry SJ, Pioro I, Trevani L, McGillivray D. Developing empirical heat-transfer correlations for supercritical $CO_2$ flowing in vertical bare tubes. Nuclear Engineering and Design. 2013 Aug;261:116-31.
  17. Park ED, Wang SK, Lee MH. Experimental study on the geochemical and mineralogical alterations in a supercritical $CO_2$-groundwater-zeolite sample reaction system. Economic and Environmental Geology. 2014 Jun;47(4):421-30. https://doi.org/10.9719/EEG.2014.47.4.421
  18. Jung HB, Um WY. Experimental study of potential wellbore cement carbonation by various phases of carbon dioxide during geologic carbon sequestration. Applied Geochemistry. 2013 Apr;35:161-72. https://doi.org/10.1016/j.apgeochem.2013.04.007
  19. Yeo SD. Supercritical fluid technology. 1st ed. Daegu: cheongmungag; 2013. 20 p.
  20. Mindess S, Young JF, Darwin D. Concrete. 2nd ed. New Jersey: Pearson Education; 2003. 8 p.
  21. Zhang T, Cheeseman CR, Vandeperre LJ. Development of low pH cement systems forming magnesium silicate hydrate (MSH). Cement and Concrete Research. 2011 Apr;41(4):139-42.
  22. Baur I, Keller P, Mavrocordatos D, Wehrli B, Johnson CA. Dissolution-precipitation behaviour of ettringite, monosulfate, and calcium silicate hydrate. Cement and Concrete Research. 2004 Feb;34(2):341-8. https://doi.org/10.1016/j.cemconres.2003.08.016
  23. Taylor HFW. Cement Chemistry. 2nd rev. ed. London: Thomas Telford; 1997. 114 p.