A Putative Adverse Outcome Pathway Relevant to Carcinogenicity Induced by Sulfuric Acid in Strong Inorganic Acid Mists

Jun Hyuek Yang,Preeyaporn Koedrith,Doo Seok Kang,Nam Kook Kee,정종현,Cheol Min Lee,서영록,안연순 대한암예방학회 2019 Journal of cancer prevention Vol.24 No.3

Based on epidemiological studies, an International Agency for Research on Cancer Working Group determined that strong inorganic acid mists containing sulfuric acid are carcinogenic to human even though, sulfuric acid, per se, is not. Accumulative studies indicate that there is a link between chronic occupational exposure to sulfuric acid mists and an increased risk of laryngeal cancer. Unintended, acute exposure to sulfuric acid mists can cause corrosive damage to target tissues depending on the route of exposure. This review compares the toxicity and carcinogenicity of sulfuric acid mists compared to other strong inorganic acid mists. It also examines the routes and duration of exposure (short-term, prolonged, and long-term). In vivo evidence does not support or refute the carcinogenicity of sulfuric inorganic mists even though its co-carcinogenic or promoting potential has been considered. On the basis of existing evidence on sulfuric acid mist toxicity, we suggested a putative adverse outcome pathway (AOP) relevant to carcinogenicity caused by mists containing sulfuric acid. A possible key factor involved in sulfuric acid mist carcinogenesis is the genotoxic effects of low pH since it can increase instability in chromosomes and DNA. A putative AOP for sulfuric acid mist carcinogenicity would help generate better risk assessments and more accurate predictions regarding the risk of developing cancer due to prolonged exposure. Establishing an AOP would also be useful for future studies examining the carcinogenicity of other strong inorganic mists. (J Cancer Prev 2019;24:139-145)

Recovery of sulfuric acid aqueous solution from copper-refining sulfuric acid wastewater using nanofiltration membrane process

Yun, Taeseon,Chung, Jae Woo,Kwak, Seung-Yeop Elsevier 2018 Journal of environmental management Vol.223 No.-

<P><B>Abstract</B></P> <P>We used a nanofiltration (NF) membrane process to produce purified aqueous sulfuric acid from copper-refining sulfuric acid wastewater. Wastewater generated from a copper-refining process was used to explore the membrane performances and acid stabilities of six commercial NF membranes. A combination of permeate flux, sulfate permeation, and metal ion rejection clearly showed that two polyamide membranes and a polyacrylonitrile-based membrane achieved recovery of a purified sulfuric acid solution. Acid-stability and long-term performance tests showed that the polyamide membranes were unsuitable for copper-refining wastewater treatment because of their low acid stabilities. In contrast, the polyacrylonitrile-based composite membrane showed excellent acid stability, and gave greater than 90% metal ion rejection, with the exception of calcium ions, for 430 d. We also evaluated the recovery performance in 1 ton/d pilot-scale process using wastewater from copper-refining process; 90% metal ion rejection was achieved, with the exception of calcium ions, even at 95% recovery rate.</P> <P><B>Highlights</B></P> <P> <UL> <LI> We applied NF membranes to treatment of copper-refining sulfuric acid wastewater. </LI> <LI> Purified sulfuric acid aqueous solution was recovered from sulfuric acid wastewater. </LI> <LI> We found that a non-polyamide membrane in this study showed excellent acid stability. </LI> <LI> MPS-34 was maintained metal ion rejection greater than 90%, except Ca ion, for 430 d. </LI> <LI> The sulfuric acid recovery was also achieved in 1 ton/d pilot-scale process. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

황산ㆍ염산 이용 범죄 사례와 황산ㆍ염산 관리 실태에 관한 연구

이상인 한국사회안전범죄정보학회 2017 한국범죄정보연구 Vol.3 No.2

본 논문은 치명적인 화학물질인 황산(H2SO4)과 염산(HCl)을 이용한 범죄가 우리사회의 사회 적 위험성을 증대시키고 피해자 개인에게 얼마나 심각한 문제인지 문헌연구와 사건․사례중심으 로 기술하고자 한다. 그 동안 황산·염산으로 인한 범죄가 꾸준히 발생하였다. 1999년 대구에서 벌 어진 태완(당시6세)에 대한 황산테러가 그 대표적인 사건으로 그 후에도 매년 수 건 이상씩 발생 하고 있다. 그럼에도 불구하고 황산·염산을 이용한 범죄를 근본적으로 예방하기 위한 사회적 공 론은 별로 일어나지 않았다. 이는 사회적 관심의 부족일 수도 있고, 황산·염산의 유통과 사용을 국가가 통제하기에 매우 어렵다는 반증일 수 도 있다. 이에 본 논문은 황산(H2SO4)과 염산(HCl)의 소비자와 판매자 관계, 유통 실태 등을 살펴보고 개선점을 모색하여 황산을 이용한 범죄의 예방과 대처에 기여하고자 한다. The purpose of this thesis is to definitize severe problems for our community and individual victims caused by crimes using sulfuric acid(H2SO4)·hydrochloric acid(HCl). These problems will be examined with documentary researches and case studies. Until now, crime cases using sulfuric acid(H2SO4)·hydrochloric acid(HCl) constantly have happened. In Daegu, 1999, Tae wan Kim(6 years old) has fallen victim to a terror attack with sulfuric acid. After this notorious case, crime cases using sulfuric acid are keep happening every year. However, there have not been many public discussions for radical prevention. This may because not only lack of social concern, but also difficulty of government regulation works for use and distribution of sulfuric acid. Eventually, this thesis will contribute to prevention and action against crime using sulfuric acid·hydrochloric acid by examine real condition of sulfuric acid distribution and relationship between its consumers and retailers.

황산ㆍ염산 이용 범죄 사례와 황산ㆍ염산 관리 실태에 관한 연구

이상인 한국사회안전범죄정보학회 2016 한국범죄정보연구 Vol.2 No.2

본 논문은 치명적인 화학물질인 황산(H2SO4)과 염산(HCl)을 이용한 범죄가 우리사회의 사회 적 위험성을 증대시키고 피해자 개인에게 얼마나 심각한 문제인지 문헌연구와 사건․사례중심으 로 기술하고자 한다. 그 동안 황산·염산으로 인한 범죄가 꾸준히 발생하였다. 1999년 대구에서 벌 어진 태완(당시6세)에 대한 황산테러가 그 대표적인 사건으로 그 후에도 매년 수 건 이상씩 발생 하고 있다. 그럼에도 불구하고 황산·염산을 이용한 범죄를 근본적으로 예방하기 위한 사회적 공 론은 별로 일어나지 않았다. 이는 사회적 관심의 부족일 수도 있고, 황산·염산의 유통과 사용을 국가가 통제하기에 매우 어렵다는 반증일 수 도 있다. 이에 본 논문은 황산(H2SO4)과 염산(HCl)의 소비자와 판매자 관계, 유통 실태 등을 살펴보고 개선점을 모색하여 황산을 이용한 범죄의 예방과 대처에 기여하고자 한다. The purpose of this thesis is to definitize severe problems for our community and individual victims caused by crimes using sulfuric acid(H2SO4)·hydrochloric acid(HCl). These problems will be examined with documentary researches and case studies. Until now, crime cases using sulfuric acid(H2SO4)·hydrochloric acid(HCl) constantly have happened. In Daegu, 1999, Tae wan Kim(6 years old) has fallen victim to a terror attack with sulfuric acid. After this notorious case, crime cases using sulfuric acid are keep happening every year. However, there have not been many public discussions for radical prevention. This may because not only lack of social concern, but also difficulty of government regulation works for use and distribution of sulfuric acid. Eventually, this thesis will contribute to prevention and action against crime using sulfuric acid·hydrochloric acid by examine real condition of sulfuric acid distribution and relationship between its consumers and retailers.

황산/글루코스 용액으로부터 전기투석에 의한 황산 분리

이세훈 ( Se-hoon Lee ),김영숙 ( Young-sook Kim ),추천호 ( Cheun-ho Chu ),나일채 ( Il-chai Na ),오용환 ( Yong-hwan Oh ),박권필 ( Kwon-pil Park ) 한국화학공학회 2017 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.55 No.1

Recovery of sulfuric acid is very important after biomass converted to sugar by acid hydrolysis. In this work, the separation of sulfuric acid from sulfuric acid/glucose solution was studied by electrodiaysis. Three chamber method, which requires both anion membrane and cation membrane, is the most commonly used in the electrodialysis process, but two chamber method using only an anion membrane was the focus of this study. Sulfuric acid was perfectly separated from a mixture of 10~30 wt% glucose and 1~3 M sulfuric acid by electrodialysis using two chamber method. The separation rate of sulfuric acid lineary increased with higher current density when the affect of diffusion and convection of the membrane was small. Without electric energy, 45% of sulfuric acid was separated by diffusion and convection only.

황산용액에 의한 제강분진 중 중금속의 용출효과

정래윤 ( Rae Youn Jeong ),이현표 ( Hyun Pyo Lee ),이진휘 ( Jin Hui Lee ) 한국유화학회 2010 한국응용과학기술학회지 Vol.27 No.4

Elution effect was studied by the reactions between Electric arc furnace(EAF)dust and cone. or dil. sulfuric acid for the purpose of recoverying of the useful metals afterwards. The methods of mixing with acids and EAF dust for the elutions were depend on the ratios of acid/EAF dust. Experimental results showed that increased the ratios of sulfuric acids, decreased the elution effects are on the Zn, Fe and Mn, and conc. sulfuric acid showed higher elution effects than dil. sulfuric acids for the all metals. But in case of Pb, dil. sulfuric acid showed higher elution effects than cone. sulfuric acids conversely. Furthermore, the reason of the extreamly low quantities of eluted Pb is caused by the low solubilities by sulfuric acids compared to the other metals, as the results of the insoluble Pb is removed by the process of filtering.

황산용액에 의한 제강분진 중 중금속의 용출효과

정래윤(Rae Youn Jeong),이현표(Hyun Pyo Lee),이진휘(Jin Hui Lee) 한국유화학회 2009 한국응용과학기술학회지 Vol.27 No.4

Elution effect was studied by the reactions between Electric arc furnace(EAF)dust and conc. or dil. sulfuric acid for the purpose of recoverying of the useful metals afterwards. The methods of mixing with acids and EAF dust for the elutions were depend on the ratios of acid/EAF dust. Experimental results showed that increased the ratios of sulfuric acids, decreased the elution effects are on the Zn, Fe and Mn, and conc. sulfuric acid showed higher elution effects than dil. sulfuric acids for the all metals. But in case of Pb, dil. sulfuric acid showed higher elution effects than conc. sulfuric acids conversely. Furthermore, the reason of the extreamly low quantities of eluted Pb is caused by the low solubilities by sulfuric acids compared to the other metals, as the results of the insoluble Pb is removed by the process of filtering.

Production of Sulfuric Acid and Ammonia Water from Ammonium Sulfate Using Electrodialysis with Bipolar Membrane and Ammonia Stripping

Yeon Kyeong-Ho,Song Jung-Hoon,Shim Bong-Sup,Moon Seung-Hyeon The Membrane Society of Korea 2005 Korean Membrane Journal Vol.7 No.1

The feasibility of producing sulfuric acid and ammonia water from ammonium sulfate was investigated by an integrated process including ammonia stripping (AS) and electrodialysis with bipolar membrane (EDBM). It was suggested that the production of sulfuric acid using ammonia stripping-electrodialysis with bipolar membrane (ASEDBM) was effective in obtaining high concentration of sulfuric acid compared with EDBM alone. AS was carried out over pH 11 and within the range of temperatures, $20^{\circ}C{\~}60^{\circ}C$. Sodium sulfate obtained using AS was used as the feed solution of EDBM. The recovery of ammonia increased from $40\%$ to $80\%$ at $60^{\circ}C$ due to the increased mobility of ammonium ion. A pilot-scale EDBM system, which is composed of two compartments and 10 cell pairs with an effective membrane area of $200 cm^2$ per cell, was used for the recovery of sulfuric acid. The performance was examined in the range of 0.1 M${\~}$1.0 M concentration of concentrate compartment and of $25 mA/cm^2{\~}62.5 mA/cm^2$ of current density. The maximum current efficiency of $64.9\%$ was obtained at 0.1 M sulfuric acid because the diffusion rate at the anion exchange membrane decreased as the sulfuric acid of the concentrate compartment decreased. It was possible to obtain the 2.5 M of sulfuric acid in the $62.5 mA/cm^2$ with a power consumption of 13.0 kWh/ton, while the concentration of sulfuric acid was proportional to the current density below the limiting current density (LCD). Thus, the integrating process of AS-EDBM enables to recover sulfuric acid from the wastewaters containing ammonium sulfate.

Preparation of Cellulose Nanocrystals via a Mild Mixed Acid Hydrolysis with High Yield and High Thermal Stability

Zhufan Zou,Xianghao Yang,Hongxiang Xie,Hongyan Lan,Yang Cheng,Jiahui Shen,Youngsoo Bae,Chuanling Si 강원대학교 산림과학연구소 2018 강원대학교 산림과학연구소 학술대회 Vol.2018 No.09

Cellulose nanocrystals (CNCs) are mainly produced by traditional mineral acid hydrolysis, such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc., which usually causes some problems such as corrosion of equipment, inability of acid recovery, large amounts of water usage, and over-degradation of cellulose. In this work, a green and sustainable approach for the preparation of CNCs was developed by using a mixed acid hydrolysis of oxalic acid and sulfuric acid. The acid ratio, reaction temperature, and reaction time were investigated in detail. It was discovered that a high yield up to 85 % was achieved by this mixed acid with a ratio of 5:1:4 for sulfuric acid: oxalic acid: H2O respectively at 95 oC for 2 h. Results showed that the resultant CNCs have a narrow particle size of 416±35 nm (based on dynamic light scattering). TEM characterization showed the CNCs was perfect whisker morphology. Also, the obtained CNCs exhibited superior dispersion stability in water due to the introduction of carboxyl group on the surface of CNCs by oxalate esterification. Thermogravimetric analyses revealed that the resultant CNCs showed a much higher thermal stability (315 °C) than the traditional sulfuric acid hydrolyzed CNCs. In addition, over 90% of oxalic acid could be recovered by a simple recrystallization step. Thus, the present work demonstrated an efficient and green preparation method of CNCs with high yield and high thermal stability.

열 피로에 미치는 알루미늄 양극산화 제조방법의 융합연구

강수영 한국융합학회 2016 한국융합학회논문지 Vol.7 No.5

알루미늄의 양극산화는 황산법, 수산법과 황산과 수산을 활용한 혼산법 등이 있다. 산업체에서 만들어 지는 양극산화는 황산법으로 전해액속의 황산농도가 15 ∼ 20 wt %이다. 연질 양극산화피막을 생성할 경우는 전해 액의 온도가 20∼30℃ 범위에서 생산되고 있으며, 생산 전압은 직류전압으로 13∼15 V 이내가 가장 많이 사용된다. 경질 양극산화피막을 생성할 경우는 전해액의 온도가 0 ∼ -5 ℃에서 생산되어지고 있다. 본 연구에서는 황산법과 수산법을 이용하여 50㎛ 두께의 양극산화피막(알루미나)를 제작하였다. 황산법과 수산법에 의해 시편을 제조하여 열 피로시험을 수행하였다. 황산법과 수산법의 균열발생온도는 500℃와 600℃이었다. 황산법의 균열발생온도는 수 산법의 균열발생온도보다 낮았다. 시험결과 수산법의 열 피로는 황산법의 열 피로 특성보다 좋았다. 그 이유를 알루 미늄과 알루미나의 열팽창계수와 제조온도로 설명하였다. 고온에서 사용되는 양극산화제품의 제조방법을 여기서의 융합 연구를 통해 제안 가능하게 되었다. Anodic oxidation of aluminum has a sulfuric acid method and a oxalic acid method. Sulfuric acid concentration of the sulfuric acid method is 15∼20 wt%. In the case of soft anodizing used in the 20 ∼30 ℃ range, and voltage is the most used within a DC voltage 13∼15V. In the case of hard anodizing used in the 0 ∼ -5 ℃ range. An aluminum oxide layer is made using sulfuric acid and oxalic acid. In this study, thermal fatigue of aluminum oxide layer which is made using sulfuric acid and oxalic acid is compared. Crack generating temperature of a sulfuric acid method and a oxalic acid method is 500℃ and 600℃. Thermal fatigue of aluminum oxide layer which is made using oxalic acid is better than thermal fatigue of aluminum oxide layer which is made using sulfuric acid. The characteristic of thermal fatigue can be explained by using thermal expansion coefficient of Al and Al2O3 and manufacturing temperature on Al anodizing. It was made possible through the convergent study to propose the manufacturing method of the anodic oxidation product used at a high temperature.