• 자원리싸이클링
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• 제25권5호
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• pp.14-27
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• 2016

청정석탄기술 중 하나인 석탄가스화 복합발전기술의 이론적 고찰 및 주요단위공정에 사용되는 고온건식 탈황제의 연구 및 기술개발 동향을 조사하였다. 고온건식 탈황제 개발의 중요한 요소는 반응성, 내구성 및 내마모성에 있으며, 탈황제 종류는 칼슘계, 아연계, 망간계, 철계, 구리계 등이 있다. 현재 고온건식 탈황제의 경우 선진국을 중심으로 아연계 탈황제 제조기술이 가장 상용화 단계에 있으며, 국내에서도 다양한 지지체를 사용하여 가격이 저렴하고 성능이 우수한 아연계 및 비아연계 고온건식 탈황제의 상용화를 위한 연구개발이 진행 중에 있다.

• 한국에너지공학회:학술대회논문집
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• 한국에너지공학회 2000년도 추계 학술발표회 논문집
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• pp.73-77
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• 2000

A great deal of research has been carried out in the last twenty some years to develop high temperature desulfurization. For example, the efficiency of advanced power generation processes based on the integrated gasification combined cycle (IGCC) can be increased significantly with high temperature desulfurization. Much of the recent high temperature desulfurization research has concentrated on zinc-based sorbents such as zinc ferrite(ZnFe$_2$O$_4$) and zinc titanate(ZnO.xTiO$_2$) due to its thermodynamic advantage in capturing H$_2$S molecules.(omitted)

• 한국환경보건학회지
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• 제31권6호
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• pp.483-488
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• 2005

The waste seashells were used for the removal of hydrogen sulfide from a hot gas stream. The sulphidation of waste seashells with $H_{2}$S was studied in a thermogravimetric analyzer at temperature between 600 and $800^{circ}C$. The desulfurization performance of the waste seashell sorbents was experimentally tested in a fixed bed reactor system. Sulfidation experiments performed under reaction conditions similar to those at the exit of a coal gasifier showed that preparation procedure and technique, the type and the amount of seashell, and the size of the seashell affect the $H_{2}$S removal capacity of the sorbents. The pore structure of fresh and sulfided seashell sorbents was analyzed using mercury porosimetry, nitrogen adsorption, and scanning electron microscopy (SEM). Measurements of the reaction of $H_{2}$S with waste seashells show that particles smaller than 0.631 mm can achieve high conversion to CaS. According to TGA and fixed bed reactor results, temperature had influenced on $H_{2}$S removal efficiency. As desulfurization temperature increased, desulfurization efficiency increased. Also, maximum desulfurization efficiency was observed at $800^{circ}C$. Desulfurization was related to calcinations temperature.

• 한국환경보건학회지
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• 제29권3호
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• pp.86-90
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• 2003

In this study, lots of methods have been studing to utilize energy and decrease contaminated effluents. There has been great progress on IGCC (Integrated gasification combined cycle) to reduce thermal energy losses. The following results have been conducted from desulfurization experiments using waste shell to remove H$_2$S. Fixed bed desulfurization experiments, to obtain basic data for scale-up was indicated. Oyster was the best among the various sorbents, like the results of TGA. Especially, H$_2$S removal efficiency of uncalcined oyster was the highest. When use oyster as desulfurization sorbents, calcination process was not needed. Thus, high desulfurization efficiency would be expected. Fixed bed reactor experiments were indicated particle size of sorbents. These had influenced on desulfurization capacity. As smaller particle size was found better desulfurization capacity. Large capacity difference was found between 0.613 mm and 0.335 mm. But, differences between 0.335 mm and 0.241 mm was relatively small. As bed temperature increased, H$_2$S removal capacity increased. Therefore, both particle size and bed temperature should be considered to remove H$_2$S by sorbents.

• 자원리싸이클링
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• 제24권5호
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• pp.3-14
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• 2015

청정석탄발전기술 중 하나인 순환유동층보일러(CFBC) 기술의 고도화에 따라 국내외 로내탈황 기술개발 현황과 국내외 유동층보일러용 석회석의 탈황특성 연구현황을 조사하였다. 석회석계 탈황제는 고온탈황특성이 우수한 원소 중 하나로 $850-950^{\circ}C$ 내외에서 최적의 탈황특성을 가지고 있다. 그리고, 탈황시험방법에 따라 흡수제 표면의 격막의 확산반응, 입자의 크기, 기공의 수량, 크기 및 구조에 의한 탈황공정의 효율성을 결정할 수 있다. 2015년 이후 대형 순환유동층형발전소의 본격적인 가동에 따라 석회석의 광상학적, 결정학적 특성 및 소성특성과 연계된 추가적인 연구가 필요한 것으로 사료된다.

• Korean Chemical Engineering Research
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• 제57권2호
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• pp.283-288
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• 2019

Catalytic removal of sulfur compounds from heavy naphtha (HN) was investigated using a combination of an oxidation process using hydrogen peroxide and an adsorption process using granulated activated carbon (GAC) and white eggshell (WES). This study investigated the impact of changing several operating parameters on the desulfurization efficiency. Specifically, the volume ratio of $H_2O_2$ to HN (0.01~0.05), agitation speed ($U_{speed}$) of the water bath shaker ($100-500{\pm}1rpm$), pH of sulfur solution (1~5), amount of adsorbent (0.1~2.5 g), desulfurization temperature ($25{\sim}85{\pm}1^{\circ}C$) and contact time (10~180 minutes) were examined. The results indicate that the desulfurization efficiency resulting from catalytic and adsorption processes of GAC is better than that of WES for oxidation and removing sulfur compounds from HN due to its high surface area. The desulfurization efficiency depends strongly on all investigated operating parameters. The maximum removal efficiency of GAC and WES achieved by this study was 86 and 65, respectively.

• Korean Chemical Engineering Research
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• 제50권3호
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• pp.492-498
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• 2012

본 연구에서는 고온고압 건식탈황장치를 이용하여 고체순환량과 탈황반응기 내의 공극률에 대한 수력학적특성을 파악하고, 아연계 탈황제의 고온고압 조건에서 탈황반응온도에 대한 반응특성 및 연속운전을 통한 탈황 효율을 분석하였다. 실험에 사용된 고온고압건식탈황장치는 고속유동층 형태의 탈황반응기(내경: 0.015 m, 높이: 6.2 m), 기포유동층 형태의 재생반응기(내경: 0.053 m, 높이: 1.6 m), 가스의 역흐름을 방지하는 loop-seal, 두 반응기 후단에 압력컨트롤밸브로 구성되어있다. 수력학 특성으로는 고체순환밸브 개구비, 탈황반응기 가스 유속, 탈황반응기 온도 변화에 따른 고체순환량과 각 조건에서의 고속유동층 형태의 탈황반응기 높이에 따른 공극률 분포를 알아보았다. 고체순환량은 동일한 유속조건, 동일한 고체순환밸브 개구비에서 탈황반응기 온도가 상온일 때보다 $300^{\circ}C$와 $550^{\circ}C$일 때 감소하였으며 $300^{\circ}C$와 $550^{\circ}C$ 조건에서는 큰 차이가 없었다. 탈황반응기내의 공극률은 고체순환밸브 개구비가 10~20%로 고체순환량이 적은 경우 고속유동층 형태의 공극률 분포를 보이고, 30~40%로 고체순환량이 많아지는 경우 탈황반응기 하부에서 turbulent 형태의 공극률의 분포를 나타냈다. 아연계 탈황제의 탈황반응온도에 따른 반응특성은 시스템 압력 20 atm, 연속 반응 조건에서 탈황 온도를 변화시키면서 살펴보았다. 일정한 고체순환 조건에서 탈황온도 $450^{\circ}C$ 이하에서 탈황 효율 저하가 시작되는 것을 확인하였으며, 높은 탈황 효율을 유지시키기 위하여 10시간 연속운전에서는 탈황 반응 온도를 $500^{\circ}C$로 설정하여 실험하였다. 실험 결과, 10시간 연속운전을 통해, 유입 $H_2S$ 농도 5,000 ppmv 조건에서 탈황 반응기 후단 $H_2S$ 농도는 UV분석기(Radas2)와 검지관(GASTEC)의 검출한계인 1 ppmv 이하를 유지하여 $H_2S$ 제거 효율 99.99% 이상을 달성하였다.

• 에너지공학
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• 제7권1호
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• pp.73-80
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• 1998

Zinc titanate 탈황제를 제조하여 연료가스의 고온탈황에 사용된 탈황제의 재생에 대해서 연구하였다. 준비된 탈황제의 Zn/Ti 몰비는 1.5이고 반응기는 내경 1 cm와 3 cm의 석영관 고정층반응기들을 사용하였다. 고온에서 zinc titanate 탈황제의 재생은 발열반응을 수반하여 탈황제의 물성을 저하시킨다. 따라서 zinc titanate 탈황제의 가장 적합한 재생조건을 선정하기 위해서 반응온도, 산소함량, 유량변화, steam 함량 등을 변화시키면서 재생반응을 실험하였다. 탈황-재생의 실험동안 H2S와 SO2의 파과곡선을 구하였다. 또한 반응실험 전후의 탈황제의 물성을 SEM, XRD, Hg-porosimetry 및 BET로 분석하였다. 이런 결과들로부터 zinc titanate 탈황제에 가장 적합한 재생조건은 $650^{\circ}C$, O2 함？ 5%, steam 함량 10% 이상이라는 결론을 얻었다.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.225-230
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• 2013

A new heteropolyanion-based ionic ($[Hmim]_5PMo_{10}V_2O_{40}$) was synthesized by the reaction of molybdovanadophosphoric acid ($H_5PMo_{10}O_{40}$) with N-methylimidazole. [$[Hmim]_5PMo_{10}V_2O_{40}$ showed a high catalytic activity in the oxidative desulfurization of sulfur-containing compounds in 1-methylimidazolium tetrafluoroborate ($[Hmim]BF_4$) ionic liquid using 30% aqueous $H_2O_2$ as the oxidant. The catalytic system was of high activity, simplified workup and flexible recyclability. The catalytic oxidation reactivity of sulfur-containing compounds decreased in the order dibenzothiophene (DBT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The influences of various parameters including reaction time (t) and temperature (T), catalyst dosage, and oxidant to sulfur molar ratio n(O)/n(S) on the desulfurization of model oil were investigated in details. 99.1% of DBT conversion in the model oil was achieved at atmospheric pressure under the optimal conditions: n(O)/n(S) = 4:1, $60^{\circ}C$, 100 min and molar ratio of catalyst to sulfur of 0.062. The ionic liquid can be recycled six times without significant decrease in activity.

• Computers and Concrete
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• 제16권2호
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• pp.261-274
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• 2015

This study established the standard recommended values and expansion fracture threshold values for the content of steel slag in controlled low-strength materials (CLSM) to ensure the appropriate use of steel slag aggregates and the prevention of abnormal expansion. The steel slags used in this study included basic oxygen furnace (BOF) slag and desulfurization slag (DS), which replaced 5-50% of natural river sand by weight in cement mixtures. The steel slag mortars were tested by high-temperature ($100^{\circ}C$) curing for 96 h and autoclave expansion. The results showed that the effects of the steel slag content varied based on the free lime (f-CaO) content. No more than 30% of the natural river sand should be replaced with steel slag to avoid fracture failure. The expansion fracture threshold value was 0.10%, above which there was a risk of potential failure. Based on the scanning electron microscopy (SEM) analysis, the high-temperature catalysis resulted in the immediate extrusion of peripheral hydration products from the calcium hydroxide crystals, leading to a local stress concentration and, eventually, deformation and cracking.