• KEPCO Journal on Electric Power and Energy
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• v.4 no.1
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• pp.39-45
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• 2018

Ammonia Adsorbed Fly Ash (AAFA) samples produced from coal fired plants equipped with SNCR (Selective Non-Catalytic Reduction) of nitrogen oxides with urea have been chemically analyzed, and their physical and dissolution properties have been investigated. XRD results for the ammonia component in AAFA ascertained that ABS (ammonium bisulfate) and AS (ammonium sulfate) were deposited on fly ash as $SO_3$ reacted with unreacted ammonia at SNCR. SEM and EDS images showed that fine ashes on large fly ash surface of sphere type were agglomerated, due to adhesive role of ammonium salts attached fly ashes. Dissolution test results of ammonium salts absorbed on AAFA in distilled water or sea water showed that the proportion of un-ionized $NH_3$ to $NH_4{^+}$ were primarily a function of pH and temperature. Increasing pH and temperature causes an increase in the fraction of un-ionized $NH_3$. At pHs of 9.6 and 10.7, un-ionized $NH_3$ and $NH_4{^+}$ ions are present in equal amounts at distilled water and sea water, respectively.

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.490-497
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• 2006

$V_{2}O_{5}$/$TiO_{2}$ catalyst can be deactivated by ammonium salts formed by $SO_{2}$ oxidation and unreacted ammonium in presence of $SO_{2}$ in flue gas. The deactivation of catalyst by $SO_{2}$ depends on the $SO_{2}$ oxidation to $SO_{3}$. The oxidation of $SO_{2}$ is weakly affected by oxygen concentration, and strongly by the amount of vanadium loaded onto titania supports. Because unreacted ammonia is one of elements to form the ammonium salts, it is important to control the mole ratio of $NH_{3}/NOx$ in SCR. Thus the experiments about $NH_{3}/NOx$ were carried out. The reason of low activity of catalyst deactivated by ammonium salts is the change of pore volume. And TPD (Temperature Programmed Decomposition) was performed to find the decomposition of ammonium bisulfate on deactivated catalyst.

• KEPCO Journal on Electric Power and Energy
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• v.2 no.3
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• pp.437-445
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• 2016

This paper discussed the effect of ammonia concentration adsorbed on fly ash for the ammonia emission as AAFA (Ammonia Adsorbed Fly Ash) produced from coal fired plants due to operation of NOx reduction technologies was landfilled with distilled or sea water at closed and open systems, respectively. Ammonia bisulfate and sulfates adsorbed on fly ash is highly water soluble. The pH of ammonium bisulfate and sulfate solution had significant effect on ammonia odor emission. The effect of temperature on ammonia odor emission from mixture was less than pH, the rate of ammonia emission increased with increased temperature when the pH conditions were kept at constant. Since AAFA increases the pH of solution substantially, $NH_3$ in the ash can release the ammonia order unless it is present at low concentration. $NH_4{^+}$ ion is unstable in fly ash and water mixtures of high pH at open system, which is changed to nitrite or nitrate and then released as ammonia gas. The proper conditions for < 20 ppm of ammonia concentration released from the AAFAs landfilled in ash pond were explored using an open system with sea water. It was therefore proposed that optimal operation to collect AAFA of less than 168 ppm ammonia at the electrostatic precipitator were controlled to ammonia slip with less than 5 ppm at SCR/SNCR installations, and, ammonia odor released from mixture of fly ash of 168 ppm ammonia with sea water under open system has about 20 ppm.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2014.11a
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• pp.204-206
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• 2014

석탄 화력발전소에는 연소가스의 질소산화물(NOx) 저감을 위한 SCR(selective catalytic reduction)설비가 운전되고 있으며, SCR은 환원제인 암모니아($NH_3$)를 이용하여 연소가스 내에 질소산화물을 물과 질소로 분해하는 역할을 한다. 그러나, 연소가스 중의 일부 삼산화황($SO_3$)과 미반응 암모니아가 결합하여 황산암모늄염(Ammonium bisulfate; $NH_4HSO_4$)을 생성하며, 이는 후단 APH(air preheater)의 열소자에 점착된 후 분진들과 함께 성장하여 막힘을 야기한다. 막힘이 발생된 APH는 연소가스의 흐름을 방해하기 때문에 차압을 증가시키며, 이는 발전효율의 감소뿐만 아니라 급전정지를 초래한다. 이를 해결하기 위하여 $CO_2$ 드라이아이스 세정 방법을 적용하였으며, pilot-scale plant에서 실험을 수행하였다. 또한, 드라이아이스 공정변수인 분사압력과 분사시간을 제어하여 pilot-scale plant의 APH 열소자 표면에 생성되어있는 오염물질들의 제거효율을 관찰한 결과 95 %의 높은 제거효율을 보였다.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.715-720
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• 1993

Diphenylmethane (pKa=33.4), which is difficult to be oxidized in normal oxidation conditions, was oxidized to produce benzophenone at ambient temperature and atmospheric pressure by using phase transfer catalysts and solid potassium tert-butoxide as base. Quaternary salt such as benzyltriethylammonium chloride, tetrabutyl ammonium bisulfate, tetrabutylphosponium chloride, are ineffective catalysts for this reaction, but 18-crown-6 and polyethylene glycols showed catalytic activity. The conversion of diphenylmethane was increased with increasing chain length of PEG molecules when they are used as phase transfer catalysts both in equal molar and equal weight basis. The conversion of diphenylmethane was increased with the agitation speed, and aprotic solvent like DMF showed higher reaction rate compared with benzene.

• Prospectives of Industrial Chemistry
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• v.22 no.5
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• pp.25-40
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• 2019

전 세계적으로 환경문제를 해결하기 위한 방안으로 환경규제를 강화시키며 특히 다양한 대기오염 물질 중 최근 큰 이슈인 초미세먼지 저감을 위해 전구물질로 알려진 질소산화물을 제어하기 위한 다양한 기술개발이 가속화되고 있다. 특히, 다양한 처리기술 중에 기술적·경제적인 이점을 갖춘 선택적 촉매환원법(selective catalytic reduction, SCR) 기술을 통하여 질소산화물 제거를 위해 암모니아를 환원제로 반응에 참여시켜 인체에 무해한 H₂O, N₂로 전환하는 기술이 대표적이다. 최근 전 세계적으로 다양한 산업군에서 질소산화물이 배출되고 있으며, 점오염원뿐만이 아니라 비점오염원(mobile sources)에 대한 규제가 강화되고 있다. 디젤엔진이 장착된 선박 배가스 처리장치 내 SCR 기술이 주목을 받고 있으며, NH₃-SCR에 사용되는 촉매는 주로 VO_x/TiO₂, VO_x/W/TiO₂ 촉매가 대표적이다. 한편 선박 디젤엔진에 사용되는 연료에 따라 연소배가스 특성이 다르다. 이러한 연료가 연소됨에 따라 SO₂, SO₃가 발생되고 환원제인 NH₃와 결합하여 황산암모늄염((NH₄)₂SO₄), ABS (ammonium bisulfate, NH₄HSO₄)과 같은 염을 형성시켜 탈질촉매의 비활성화 문제가 발생된다. 이러한 비활성화 물질이 침적된 탈질촉매를 재활성화 시키기 위하여 열 산화를 통해 재생시키고 있다. 이처럼 선박용 SCR 촉매는 강화되는 배출규제 및 엔진기술의 발달로 저감되는 운전 온도에 대비하여 저온 활성 재생이 가능한 고활성, 고내구성 촉매기술 개발이 필요하다.

• Asian Journal of Atmospheric Environment
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• v.6 no.4
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• pp.288-303
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• 2012

In this study, real time measurements of particle number size distribution in urban Gwangju, coastal Taean, and industrial Yeosu in Korea were conducted in 2008 to understand the occurrence of ultrafine particle (UFP) (<100 nm) events, the variation of its concentration among different sampling sites, and UFP formation pathways. Also, to investigate seasonal and long-term variation of the UFP number concentration, data were collected for the period of 5 years (2007, 2008, 2010, 2011, and 2012) in urban Gwangju. Photochemical and combustion events were found to be responsible for the formation of UFP in the urban Gwangju site, whereas only photochemical event led to the formation of UFP in the coastal Taean site. The highest UFP concentration was found in industrial Yeosu (the average UFP number fractions were 79, 59 and 58% in Yeosu, Gwangju, and Taean, respectively), suggesting that high amount of gas pollutants (e.g., $NO_2$, $SO_2$, and volatile organic carbon (VOC)) emitted from industries and their photochemical reaction contributed for the elevated UFP concentration in the industrial Yeosu site. The UFP fraction also showed a seasonal variation with the peak value in spring (61.5, 54.5, 50.5, and 40.7% in spring, fall, summer, and winter, respectively) at urban Gwangju. Annual average UFP number concentrations in urban Gwangju were $5.53{\times}10^3\;cm^{-3}$, $4.68{\times}10^3\;cm^{-3}$, $5.32{\times}10^3\;cm^{-3}$, $3.99{\times}10^3\;cm^{-3}$, and $2.16{\times}10^3\;cm^{-3}$ in the year 2007, 2008, 2010, 2011, and 2012, respectively. Comparison of the annual average UFP number concentration with urban sites in other countries showed that the UFP concentrations of the Korean sites were lower than those in other urban cities, probably due to lower source strength in the current site. TEM/EDS analysis for the size-selected UFPs showed that the UFPs were classified into various types having different chemical species. Carbonaceous particles were observed in both combustion (soot and organics) and photochemical events (sulfate and organics). In the photochemical event, an internal mixture of organic species and ammonium sulfate/bisulfate was identified. Also, internal mixtures of aged Na-rich and organic species, aged Ca-rich particles, and doughnut shaped K-containing particles with elemental composition of a strong C with minor O, S, and K-likely to be originated from biomass burning nearby agricultural area, were observed. In addition, fly ash particles were also observed in the combustion event, not in the photochemical event.

• Applied Chemistry for Engineering
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• v.34 no.4
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• pp.357-364
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• 2023

Selective catalytic reduction (SCR) is the most effective method for reducing nitrogen oxide emissions, but the operating temperature range of V₂O₅-WO₃/TiO₂ catalysts is narrow (300~400℃). In this study, a new catalyst with an operating temperature range of 200~450℃ was developed. The catalyst poison, ammonium bisulfate, generated during the SCR process can be removed by heating above 350℃. To increase the number of active sites and promote the dispersion of active materials, titanium isopropoxide (TTIP) treatment was performed on the TiO₂ support with various TTIP/TiO₂ mass ratios. Among them, the 5 wt% TTIP loaded catalyst showed improved performance due to higher thermal stability caused by high W dispersion and the formation of V⁵⁺. In addition, the 5 wt% TTIP-loaded catalyst prepared by a one-step co-precipitation method showed greater V-OH and W-OH dispersion and enhanced interactions in contrast to conventional methods, resulting in higher catalytic activity at lower temperatures. This review article aims to provide an accessible explanation for researchers investigating how to improve the surface properties of TiO2 catalysts using TTIP.