• 공업화학
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• 제17권5호
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• pp.451-457
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• 2006

$CrCl_{3}$를 $NH_{3}$와 반응시켜 약 $850^{\circ}C$에서 표면적이 높은 단일 상 CrN 촉매를 합성하였다. 열질량분석을 통해 고체상 화학변이가 발생하는 온도를 파악하였고 물질의 상을 XRD로 분석하였다. 합성물질의 표면적, 결정크기 등을 분석하였고 합성변수의 영향을 확인하였다. 합성된 질화물의 표면적은 $12{\sim}47m^2/g$이었다. 공간속도는 표면적 증가에 약하게나마 영향을 미쳤는데 반응중간생성물의 빠른 제거가 표면적을 높이는데 기여하는 것으로 파악되었다. 승온환원반응 분석 결과 CrN은 비활성화(passivation)시 거의 산화되지 않아 수소분위기에서의 환원이 거의 일어나지 않았으며 약 $700^{\circ}C$와 $950^{\circ}C$ 부근에서 결정격자 중의 질소가 $N_{2}$로 분해되었다. 공기분위기에서 10 K/min의 속도로 가열하면 $300^{\circ}C$ 이후의 온도에서 산화가 진행되어 $800^{\circ}C$ 부근에서 $Cr_{2}O_{3}$ 상이 형성되기 시작하였으며 $900^{\circ}C$에서도 완전히 산화되지 않았다. 부탄과 피리딘을 이용한 활성실험 결과 CrN 촉매는 탈수소반응에 선택적으로 높은 활성을 가졌으며 수첨탈질이나 수소분해반응 활성은 거의 없었다. 부탄의 탈수소반응에서 부피반응속도는 상용 촉매인 $Pt-Sn/Al_{2}O_{3}$보다 우수하였다.

• 한국자동차공학회논문집
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• 제22권5호
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• pp.73-83
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• 2014

CFD(computational fluid dynamics) model is developed to simulate direct injection of ammonia gas phase from ammonia transporting materials into the SCR catalyst in the exhaust pipe of the engine with solid SCR. Configurations of one-hole and four-hole nozzle, circumferential type, porous tube type, and the effect of mixer configurations which commonly used in liquid injection of AdBlue are considered for complex geometries. Mal-distribution index related to concentration of ammonia gas, flow uniformity index related to velocity distribution, and pressure drop related to flow resistance are compared for different configurations of complex geometries at the front section of SCR catalyst. These results are used to design the injection system of ammonia gas phase for solid SCR of target vehicle.

• 대한기계학회논문집B
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• 제39권11호
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• pp.843-851
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• 2015

질소산화물 저감에 사용하는 solid SCR용 고체상 암모늄 저장물질의 하나인 magnesium ammine chloride에 대한 실험실 규모에서의 제조방법과 제조한 물질의 분석연구를 수행하였다. 기저물질인 염화마그네슘에 암모니아 가스를 흡착하기 위한 실험조건의 도출을 위하여, Van't Hoff Plot으로 평형압 선도를 계산하였고, 간이반응기를 제작한 후, magnesium ammine chloride를 제조하였다. DA, IC, FT-IR, XRD, SDT 등으로 제조한 시료의 성분을 분석하였고, 제조한 시료에 수분이 존재한다는 것을 알 수 있었다. 암모니아 가스 흡착률을 증대하기 위하여 수분 제거에 적절한 새로운 실험방법을 제안하였고, 제안한 방법을 적용한 결과, 암모니아 가스의 흡착률이 대략 100%에 도달하였다.

• 한국자동차공학회논문집
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• 제21권6호
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• pp.183-194
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• 2013

Liquid urea based SCR has been used in the market to reduce NOx in the exhaust emission of the diesel engine vehicle. This system has several problems at low temperature, which are freezing below $-12^{\circ}C$, solid deposit formation in the exhaust, and difficulties in dosing system at exhaust temperature below $200^{\circ}C$. Also, it is required complicated exhaust packaging equipment and mixer due to supply uniform ammonia concentration. In order to solve these issues, solid urea, ammonium carbonate, and ammonium carbamate are selected as ammonia sources for the application of solid SCR. In this paper, basic research on reaction rate of three ammonia-transporting materials was performed. TGA (Thermogravimetric Analysis) and DTA (Differential Thermal Analysis) tests for these materials are carried out for various heating conditions. From the results, chemical kinetic parameters such as activation energy and frequency factor are obtained from the Arrhenius plot. Additionally, from test results of DSC (Differential Scanning Calorimeter) for these materials, chemical kinetic parameters using the Kissinger method are calculated. Activation energies of solid SCR from this experiment are compared with proper data of literature study, then obtained data of this experiment are used for the design of reactor and dosing system for candidate vehicle.

• 한국자동차공학회논문집
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• 제22권4호
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• pp.152-159
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• 2014

Urea solution as a reductant of SCR has been widely used to reduce NOx emissions from diesel engine. But it has lots of problems which are freezing at low temperature due to liquid state, deposition of solid formation in the exhaust, dosing device, and complex package such as mixers for uniform concentration of ammonia. In order to overcome these obstacle, ammonium carbonate which is one of solid ammonium materials to produce ammonia gas directly by sublimation process is considered. Simple reactor with visible widow was designed to predict equilibrium temperature and pressure of ammonium carbonate. To simulate real operation conditions under automobile environment, several cycles of heating and cooling condition were settled, two different re-solidification materials were extracted from the reactor and visible window. Analytical study is performed to characterize these unknown materials by XRD(X-Ray Diffraction), FT-IR(Fourier Transform Infrared Spectroscopy), and EA(Elemental Analyzer). From analytical results, re-solidification materials from heating and cooling cycles are very similar to original material of ammonium carbonate.

• 한국자동차공학회논문집
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• 제23권2호
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• pp.199-207
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• 2015

Solid materials of ammonia sources with SCR have been considered for the application of lean NOx reduction in automobile industry, to overcome complex problems of liquid urea based SCR. These solid materials produce ammonia gas directly with proper heating and can be packaged by compact size, because of high volumetric ammonia density. Among ammonium salts and metal ammine chlorides, calcium ammine chloride was focused on this paper due to low decomposition temperature. In order to make calcium ammine chloride in lab-scale, simple reactor and glove box was designed and built with ammonium gas tank, regulator, and sensors. Basic test conditions of charging ammonia gas to anhydrous calcium chloride are chosen from equilibrium vapor pressure by Van't Hoff plot based on thermodynamic properties of materials. Synthetic method of calcium ammine chloride were studied for different durations, temperatures, and pressures with proper ammonia gas charged, as a respect of ammonia gas adsorption rate(%) from simple weight calculations which were confirmed by IC. Also, lab-made calcium ammine chloride were analyzed by TGA and DSC to clarify decomposition step in the equations of chemical reaction. To understand material characteristics for lab-made calcium ammine chloride, DA, XRD and FT-IR analysis were performed with published data of literature. From analytical results, water content in lab-made calcium ammine chloride can be discovered and new test procedures of water removal were proposed.

• 대한기계학회논문집B
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• 제41권10호
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• pp.639-647
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• 2017

Solid SCR에 사용 가능한 암모니아 저장물질의 하나인 암모니움 카바메이트는 열 분해시 이산화탄소 가스와 암모니아 가스를 생성하며, 분해 온도인 $60^{\circ}C$ 이하에서 암모니움 염으로 재결합되는 단점이 있다. 이러한 재결합 현상을 극복하기 위하여, 희석기체인 압축공기를 이용하여 기초가시화 실험을 수행하였다. 또한, 재결합 현상을 계량화하기 위하여, 재결합 물질의 무게변화를 측정하기 위한 간단한 장치를 만들어 자동차환경에서 사용되는 SUS재질의 3가지 관경에 크기에 대한 상관관계를 검토하였다. 아크릴 튜브로 제작된 온도조절이 가능한 가시화 실험장치에, 암모니아 가스, 이산화탄소 가스, 희석기 체인 질소 가스를 공급하며, 재결합 방지를 위한 온도, 압력, 희석유량과의 관계를 고찰하고, Chapman-Enskog Theory에서 파생된 Diffusivity를 사용하여 재결합 조건을 유추할 수 있는 지표로 사용하고자 한다.