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- In relation to this article, we declare that there is no conflict of interest.
- Publication history
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Received May 12, 2026
Revised June 10, 2026
Accepted June 10, 2026
Available online June 16, 2026
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This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/bync/3.0) which permits
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물 반응성 물질인 TiCl₄ 와 SiCl₄ 의 HCl 확산 영향범위에 대한 정량적 평가 연구
A Quantitative Study on the Dispersion Impact Range of HCl Generated from Water-Reactive Substances (TiCl4 and SiCl4)
https://doi.org/10.9713/kcer.2026.64.3.105172
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Abstract
물 반응성 화학물질은 누출 시 대기 중 수분과 반응하여 염화수소 (HCl)와 같은 독성 가스를 생성한다는 점에서 일반적 화학사고와 구별되는 고유한 위험성을 지닌다 . 본 연구에서는 동일한 수분 반응 메커니즘 (HCl 몰 비 1:4)을 공유 하면서도 증기압에서 약 20배의 차이가 나는 사염화티타늄(TiCl4, 증기압 1.3 kPa)과 사염화규소(SiCl4 , 증기압 26.7 kPa)를 대상으로, ALOHA·KORA·PHAST 세 가지 확산 평가 프로그램을 이용한 HCl 확산 영향범위를 비교 ·분석하였다. 시뮬레이션은 15 m3 상압저장탱크 기준 , IOGP 434-01에서 제시하는 4종의 누출공(5, 22, 87, 150 mm)과 방류벽 유무 조건을 조합한 총 48개 케이스로 수행하였다. PHAST에는 TiCl4 와 SiCl4 가 물질 데이터베이스에 등록되어 있지 않아, ALOHA로 Pool Diameter를 산출하고 EPA 증발률 산정식으로 증발량을 계산한 후 몰 비 환산을 거쳐 HCl 생성량을 PHAST에 직접 입력하는 간접 워크플로우를 구성하였다. 방류벽이 없는 조건의 ERPG-2 기준 SiCl 확산 영향범위는 TiCl4 대비 KORA에서 5.0~7.1배, PHAST에서 2.4~3.8배 넓게 나타났다. 프로그램 간 비교에서는 KORA가 소규모 누출(5~22 mm)에서 PHAST 대비 1.25~3.46배 과대평가하였으나, TiCl4 대규모 누출 (87~150 mm)에서는 PHAST보다 33~37% 좁은 예측 역전 현상이 관찰되었다. 방류벽 설치 시 22 mm 이상 누출공에서 약 23~91%의 저감효과를 보였다.
Water-reactive chemicals pose unique hazards because they generate toxic gases through exothermic reactions with atmospheric moisture upon release. This study selected titanium tetrachloride (TiCl4, vapor pressure 1.3 kPa) and silicon tetrachloride (SiCl4, vapor pressure 26.7 kPa) as comparison targets, which share an identical hydrolysis mechanism producing HCl at a 1:4 molar ratio but differ approximately 20-fold in vapor pressure. Using three dispersion assessment programs (ALOHA, KORA, and PHAST), the HCl dispersion distances were compared and analyzed under identical atmospheric storage tank leak scenarios. A total of 48 simulation cases were conducted combining a 15 m3 atmospheric tank, four leak hole sizes (5, 22, 87, 150 mm per IOGP 434-01), and with/without dike conditions. Since TiCl4 and SiCl4 are not registered in the PHAST substance database, a novel workflow was constructed: Pool Diameter was obtained via ALOHA, evaporation rates were calculated using the EPA Evaporation Rate Equation, HCl generation rates were converted by molar ratios, and the results were directly input into PHAST. Results showed that, under no-dike conditions at ERPG-2 level, the dispersion distance of SiCl4 was approximately 2.4 to 7.1 times wider than that of TiCl4 depending on leak hole size. In the inter-program comparison, KORA produced 1.25 to 3.46 times wider ranges than PHAST for small leaks (5~22 mm), while a prediction reversal was observed for large TiCl4 leaks (87~150 mm) where PHAST exceeded KORA. Dike installation reduced ERPG-2 dispersion distances by approximately 23~91% for leak holes of 22 mm and above.
Keywords
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