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굴패각 소성시 해저 퇴적물과 NaCl 불순물이 소성 특성에 미치는 영향

The Effects of Marine Sediments and NaCl as Impurities on the Calcination of Oyster Shells

  • 하수현 (경북대학교 지구시스템과학부) ;
  • 김강주 (군산대학교 환경공학과) ;
  • 김석휘 (고등기술연구원, 플랜트 엔지니어링 센터) ;
  • 김영규 (경북대학교 지구시스템과학부)
  • Ha, Su Hyeon (School of Earth System Sciences, Kyungpook National University) ;
  • Kim, Kangjoo (Department of Environmental Engineering, Kunsan National University) ;
  • Kim, Seok-Hwi (Center for Plant Engineering, Institute for Advanced Engineering) ;
  • Kim, Yeongkyoo (School of Earth System Sciences, Kyungpook National University)
  • 투고 : 2019.05.31
  • 심사 : 2019.06.19
  • 발행 : 2019.06.28

초록

$SO_2$ 가스 반응제로 사용되는 석회석의 대체 가능 물질로서 가능성을 보기 위하여 굴 패각의 소성 작용이 많이 연구되고 있다. 그러나 실제 소성 시 순수한 패각만을 사용할 수 없기 때문에 일부 불순물들이 포함되며 이로 인한 소성물의 특성 변화가 예상된다. 본 연구에서는 불순물로 패각의 표면에 묻어 있는 퇴적물과 바닷물로부터 유래될 수 있는 NaCl의 함량에 따른 소성물의 표면 특성을 광물학적으로 연구하여 보았다. 패각에 묻어 있는 해양 퇴적물들은 주로 석영, 알바이트 사장석, 방해석과 더불어 소량의 각섬석과 일라이트, 녹니석, 스멕타이트 등의 점토광물로 구성되어 있었다. 이 퇴적물들을 굴패각에 0.2-4.0 wt%를 섞어서 $900^{\circ}C$에서 2시간 소성 시킨 결과 각 광물들이 이 보다 낮은 온도에서 탈수작용, 탈수산화작용 및 상변화를 겪음에도 불구하고 실제 소성물의 표면적에 미치는 영향은 거의 없었다. 그러나 NaCl의 경우 0.1 - 2.0 wt%의 양을 섞어서 같은 조건에서 소성 시켰을 때 전체적으로 소성 전의시료에 비하여 비표면적은 증가하였으나 NaCl의 양을 증가시킴에 따라 비표면적은 증가하였다가 다시 감소하는 경향을 보였다. 이는 표면의 형태변화와 밀접한 관계가 있는데 전자현미경 관찰 결과 NaCl의 양이 증가하면서 패각 표면의 모양은 겔과 비슷한 모양을 보이다 약간의 각진 더 작은 입자로 변하고 다시 겔과 같은 모습을 보인다. 결과적으로 NaCl의 경우 일부 굴패각의 용융 등 형태 변화에 영향을 주어 소성이 영향을 줄 수 있으나 그 함량에 따라서 그 영향이 다를 수 있음을 보여준다.

The calcination of oyster shells have been studied as the possible substitute for the limestone used as an absorbent of $SO_2$ gas. However, since pure shells can not be used in calcination process, some impurities are contained and the changes in the characteristics of the calcination products are expected. In this study, the surface characteristics of the calcination products are investigated by mineralogical analysis according to the contents of NaCl, which can be derived from sea water, and sediments on the surface of the shell as impurities. The marine sediments on the shells were mainly composed of quartz, albite, calcite, small amounts of amphibole and clay minerals such as ilite, chlorite and smectite. After calcination of oyster shells mixed with 0.2-4.0 wt% sediments at $900^{\circ}C$ for 2 hours, regardless of the dehydration, dehydroxylation, and phase change of these minerals at the lower temperature than this experiment, no noticeable changes were observed on the specific surface area of the calcined product. However, when mixed with 0.1 to 2.0 wt% NaCl, the specific surface area generally increases as compared with the shell sample before calcination. The specific surface area increases with increasing amount of salt, and then decreases again. This is closely related to the changes of surface morphology. As the amount of NaCl increases, the morphology of the surface is similar to that of gel. It changes into a slightly angular, smaller particle and again looks like gel with increasing amount of NaCl. Our results show that NaCl affects morphological changes probably caused by melting of some oyster shells, but may have different effects on the specific surface area of calcination product depending on the NaCl contents.

키워드

JOHGB2_2019_v52n3_223_f0001.png 이미지

Fig. 1. XRD patterns of oyster shell and marine sediment collected from oyster shells before and after calcination (Ab: albite, Am: amphibole, C: calcite, Ch: chlorite, I:illite, K: kaolinite, Q: quartz, S: smectite).

JOHGB2_2019_v52n3_223_f0002.png 이미지

Fig. 2. SEM images of calcined pure Taean oyster shell powder. (a) 3000×, (b) 15000×.

JOHGB2_2019_v52n3_223_f0003.png 이미지

Fig. 3. SEM images of calcined Taean oyster shell powder containing sediment (a) 0.2 wt% (3000×), (b) 0.6 wt% (900×), (c) 1.4 wt% (3500×), (d) 2.4 wt% (2000×), (e) 4.0 wt% (3000×), (f) 4.0 wt% (1000×).

JOHGB2_2019_v52n3_223_f0004.png 이미지

Fig. 4. SEM images of calcined Taean oyster shell powder containing NaCl (3000×) (a), (b) 0.1 wt%, (c) 0.3 wt%, (d), (e) 0.7 wt%, (f) 1.2 wt%, (g), (h) 2.0 wt%.

Table 1. Chemical composition of sediment used in this experiment (wt%)

JOHGB2_2019_v52n3_223_t0001.png 이미지

Table 2. BET surface areas of Taean oyster shells containing sediment and NaCl salt (m2/g)

JOHGB2_2019_v52n3_223_t0002.png 이미지

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