• Resources Recycling
• /
• v.7 no.2
• /
• pp.9-15
• /
• 1998

Recovery af molybdenum in spent desulfuriring catalyst of petrochemical industries was studied from MfGnatc solulion which is a resultant of firstly remvercd vanadium by wet processes. In order to separate and recover molybdenum from upper mentioned rafinatz solution containing several mctal ions, such as molybdenum (1,100 ppm), vanadium (150 ppm), aluminium (19 ppm), and nickel (33 ppm), either adsorption technique by chelate resin or solvent extr~ction by tertiary amine as extractant was applied. In case of adsorption method, palyamine type chelate resin showed the highest selectivily far molybdenum ion up lo 60 ddm' of ancentration aftcr eluting with 3.0 rnolld~n' of NH,OH. On the othcr hand. molybdenum ion wa cffectlvely cxtractcd in Ule whole ranges of equilibrilrm pR by solvent extraction method with 10 ~01%-alamine 336 which was pretreated with 2N-HCI

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.246.1-246.1
• /
• 2010

본 연구는 바이오가스의 에너지효율성을 높이기 위한 연구로서 바이오가스 정제공정과 초저온액화공정을 통하여 액화바이오메탄을 생산하는 바이오가스 고질화기술개발 연구이다. 바이오가스 정제공정은 탈황, 제습, 흡착, 압축, $CO_2/CH_4$ 분리공정으로 구성하고, 초저온액화공정은 열교환기, $CO_2$ 제거설비, 질소냉매 공급공정으로 구성하여 혐기성소화조에서 발생하는 바이오가스($CH_4$ 농도: 60~65%, $H_2S$: 1,500~2,500ppm)를 $200Nm^3/hr$의 유량으로 인입시켜 액화바이오메탄을 생산하였다. 연구결과, 탈황공정에서는 가성소다 세정법을 이용하여 1,500~2,500ppm으로 인입되는 $H_2S$를 100ppm 이하로 제거한 후, 흡착법을 이용하여 $H_2S$를 완전히 제거하였다. 바이오가스에 포화된 수분은 냉각제습과 흡착제습공정을 통해 Dew point $-70{\sim}-90^{\circ}C$까지 제거하여 안정적으로 $CO_2/CH_4$ 분리공정에 인입시켰다. $CO_2/CH_4$ 분리공정은 흡착방식을 적용하여 $CH_4$ 순도가 95% 이상인 바이오메탄을 생산하였으며, 이때 메탄 회수율은 약 87%이였다. $CO_2$가 분리된 바이오메탄은 초저온액화공정을 이용하여 액화바이오메탄으로 전환시켰다. 이때 초저온액화공정은 Reverse Brayton cycle로 구성하였으며, 냉매로는 질소를 사용하였다. 액화바이오메탄의 생산은 바이오메탄을 등엔트로피과정인 단열팽창을 통하여 $-155{\sim}-159^{\circ}C$의 초저온으로 냉각되는 질소냉매와 열교환기에서 열교환시켜 이루어졌으며 그 생산량은 $3.46m^3$/day(1bar, $-161^{\circ}C$)이었다.

• Applied Chemistry for Engineering
• /
• v.9 no.2
• /
• pp.278-285
• /
• 1998

In a fixed bed reactor, adsorption capacity of $SO_2$ in simulated flue gases was investigated with NMO(natural manganese ore), composed of various metal oxides, iron ore and $CuO/{\gamma}-Al_2O_3$ as adsorbents. The experiment carried out in a fluidized bed reactor with variables such as gas velocity, temperature and particle size. Iron ore was excluded in the fluidized bed reactor experiment for the lower adsorption capacity. The adsorption of $SO_2$ in metal oxide is a typical chemisorption because the adsorption capacity of all adsorbents increased with temperature. The effect of particle size on the adsorption capacity was varied with the ratio, $U_o/U_{mf}$ and the difference of $U_o-U_{mf}$. $U_o$ is the gas velocity, $U_{mf}$ is the minimum fluidization gas velocity. $U_o/U_{mf}$ and $U_o-U_{mf}$ explain the behavior of the gas and solids in the fluidized bed reactor. From the performance equation of the fluidized bed reactor, kinetic reaction rate constants were obtained by the non-linear least square method. The adsorption capacity of NMO proved the potential use of $SO_2$ adsorbents.

• Clean Technology
• /
• v.3 no.1
• /
• pp.106-113
• /
• 1997

The objectives of this study were to investigate the characteristics of limestone calcination and sulfation in a fluidized bed reactor with bed temperature and air velocity. The experimental results were presented as follows ; First, the bed temperature had a great influence on the calcination and the sulphur retention of limestone and paper sludge. In paper sludge, the optimum conditions in calcination and desulfurization temperature was at $800^{\circ}C$ and in natural limestone, that was at $850^{\circ}C$ or $900^{\circ}C$. Second, as air velocity increased, the specific surface area of particles decreased. But the difference of surface area according to air velocity was not too large. The specific surface area of paper sludge was larger than that of natural limestone. Third, as air velocity increased, the absorbed amount of sulfur dioxide decreased. And the absorbed amount of sulfur dioxide by paper sludge was larger than that of by natural limestone. Therefore, we knew that paper sludge was excellent absorbent and bed temperature had a great important variable on the calcination and sulphur retention in a fluidized bed.

• Applied Chemistry for Engineering
• /
• v.10 no.2
• /
• pp.231-236
• /
• 1999

Several series of morphologically controlled $MoO_3$/$SiO_2$ catalysts were prepared, characterized, and tested for hydrodesulfurization (HDS) of dibenzothiophene (DBT) activity. Molybdenum surface loaded with 4.0 atoms $Mo/nm^2$ was prepared as sintered hexagonal and sintered orthorhombic, as well as a novel "well dispersed hexagonal" phase. Characterization by XRD, Raman, and $O_2$ chemisorption results reveals that the dispersion of $MoO_3$ over silica depends on the final $MoO_3$ phase in the order of; sintered hexagonal < sintered orthorhombic < dispersed hexagonal phase. Temperature programmed reduction (TPR) results show that both bulk and dispersed microcrystalline of $MoO_3$ reduce to $MoO_2$ at $650^{\circ}C$ and to Mo metal at $1000^{\circ}C$. HDS of DBT was performed in a differential reactor at 30 atm over the temperature range $350{\sim}500^{\circ}C$. Activity of $MoO_3$/$SiO_2$ toward HDS of DBT is proportional to dispersion.

• Clean Technology
• /
• v.13 no.4
• /
• pp.266-273
• /
• 2007

The adsorption properties of the activated carbon-based adsorbents were studied to remove COS emitted from $SO_2$ catalytic reduction process on the integrated gasification combined cycle (IGCC) system in this work. Transition metal supported catalysts and mixed metal oxide catalysts were used for the $SO_2$ catalytic reduction. The mechanism of COS produced from the $SO_2$ reduction and the COS concentration s according to the reaction temperature were investigated. In this study, an activated carbon and a modified activated carbon doped with KOH were used to remove the very low concentration of COS effectively. The adsorption rate and the breakthrough time of COS were measured by a thermo gravity analyzer (TGA, Cahn Balance) and a fixed bed flow reactor equipped with GC-pulsed flammable photometric detector (PFPD), respectively. It was confirmed that the COS breakthrough time of the activated carbon doped with KOH was longer than that of an activated carbon. In conclusion, the modified-activated carbon having a high surface area showed a high adsorption rate of COS produced from the $SO_2$ reduction.

• Clean Technology
• /
• v.13 no.1 s.36
• /
• pp.64-71
• /
• 2007

The selection of a suitable adsorbent for removing organic sulfur compounds tetrahydrothiophene (THT) and t-butylmercaptan (TBM) from natural gas has been carried out. The saturation adsorption capacity for the sulfur compounds were determined by pulse adsorption method for a group of nanoporous materials, including Na-Y, Na-ZSM-5, Na,K-ET(A)S-10, Na-Mordenite, Na,K-Clinoptitolite, Ti/MCM-41, Ti/SBA-15 and amorphous titanosilicates. Among the materials tested, Na-Y and Na,K-ET(A)S-10 zeolites showed high adsorptive capacities for THT and TBM. The saturation capacity for THT on Na,K-ETS-10 was comparable with that on Na-Y zeolite, which is well known as an effective adsorbent. The capacity and adsorptivity for THT and TBM on Na,K-ETAS-10 were improved by an increase in crystallinity of Na,K-ETAS-10. An investigation of the competitive adsorption between THT and TBM from the breakthrough test using a simulated natural gas indicates that Na,K-ETS-10 selectively adsorbs THT. The breakthrough capacity for THT on Na,K-ETS-10 was 1.19 mmol/g. The results show that the high adsorption performance of Na.K-ETS-10 and Na,K-ETAS-10 is due to the highly exchanged cations in the zeolitic structure which exhibit the strong electrostatic interactions with organic sulfur compounds and their wide pore nature.

• Journal of Korean Society of Environmental Engineers
• /
• v.32 no.2
• /
• pp.201-208
• /
• 2010

The $SO_2$ and $NO_x$ removal with an activated coke catalyst was conducted by a two-stage reaction which first $SO_2$ was oxidized to $H_2SO_4$ and then $NO_x$ was reduced to $N_2$. But if unreacted sulfur dioxide entered in the second stage, the $NO_x$ reduction was hindered by the reaction with ammonia. In this study, experimental investigations by using lab-scale column apparatus on the product and the reactivity of $SO_2$ with ammonia over coke catalyst which was activated with sulfuric acid was carried out through ultimate analysis DTA, TGA and SEM of catalyst before and after the reaction. Also, the effect of reaction emperature on the reactivity of $SO_2$ with ammonia was determined by means of breakthrough curves with time. The obtained results from this study were summarized as following; Activated cokes were decreased carbon component and increased oxygen and sulfur components in comparison with original cokes. The products over coke catalyst were faced fine crystal of $(NH_4)_2SO_4$, which results in the pressure loss of reacting system. The order of general reactivity in terms of the reaction temperature after breakthrough for $SO_2$ was found to be $150^{\circ}C$ > $200^{\circ}C$ > $100^{\circ}C$. This was related to adsorption amounts of ammonia on the activated cokes.

• Clean Technology
• /
• v.15 no.1
• /
• pp.60-66
• /
• 2009

Adsorptive removal of tetrahydrothiophene (THT) and tert-butylmercaptan (TBM) that were widely used sulfur odorants in pipeline natural gas was studied using various ion-exchanged NaY zeolites at ambient temperature and atmospheric pressure. In order to improve the adsorption ability, ion exchange was performed on NaY zeolites with alkali metal cations of $Li^+,\;Na^+,\;K^+$ and transition metal cations of $Cu^{2+},\;Ni^{2+},\;Co^{2+},\;Ag^+$. Among the adsorbents tested, Cu-NaY and Ag-NaY showed good adsorption capacities for THT and TBM. These good behaviors of removal of sulfur compound for Cu-NaY and Ag-NaY zeolites probably was influenced by their acidity. The adsorption capacity for THT and TBM on the best adsorbent Cu-NaY-0.5, which was ion exchanged with 0.5 M copper nitrate solution, was 1.85 and 0.78 mmol-S/g at breakthrough, respectively. It was the best sulfur capacity so far in removing organic sulfur compounds from fuel gas by adsorption on zeolites. While the desorption activation energy of TBM on the Cu-NaY-0.5 was higher than NaY zeolite, the difference of THT desorption activation energy between two zeolites was comparatively small.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.224.2-224.2
• /
• 2010

연료개질기는 연료전지 시스템의 핵심 구성요소 중의 하나로 도시가스로부터 수소를 생산하는 역할을 담당한다. 연료개질기는 주로 탈황, 수증기 개질, 수성가스 전이, 선택적 산화 반응의 4단계로 구성되어 있으며 이 중 상온 탈황부분을 제외한 나머지 부분은 일체화 설계를 통해 제작된다. 탈황의 경우 도시가스에 포함된 부취제인 황화합물를 제거하여 후단에 위치한 촉매층이 황에 의해 피독되는 것을 막는 역할을 하며 주로 상온흡착식 탈황제를 사용한다. 황이 제거된 도시가스는 물과 함께 연료개질기로 도입되어 수증기 개질반응을 통하여 수소, 일산화탄소, 이산화탄소 및 소량의 메탄과 미반응 수증기로 구성된 개질가스로 전환된다. 이후의 수성가스 전이반응에서는 일산화탄소가 물과 반응하여 수소 생산량을 늘리며 동시에 일산화탄소의 농도를 낮추게 된다. 또한 고분자 전해질 연료전지에 공급되는 개질가스는 선택적 산화반응을 통하여 일산화탄소의 농도를 10ppm이하로 유지하게 된다. 이러한 기능의 연료개질기 개발의 주요 이슈로는 컴팩트화 및 고효율화이며 이 두가지 요소를 고려하여 연료개질기를 설계하여야 한다. 연료전지 시스템의 전체부피를 줄이기 위한 노력의 일환으로 연료개질기의 컴팩트화가 요구되는데 가정용 연료전지 기술 선진국인 일본 제품의 경우 $1Nm^3/h$급 연료개질기의 부피는 20L정도로 알려져 있다. 또한 연료전지 시스템의 효율은 연료개질기의 개질효율과 연료전지 스택의 발전효율의 곱으로 계산되기 때문에 연료개질기의 연료개질 효율은 전체 시스템의 효율에 직접적으로 영향을 미치게 된다. 한국에너지기술연구원에서는 수소생산량 기준 $1Nm^3/h$급 연료개질기의 개발을 완료하였으며 크기 및 효율면에서 선진국 제품과 비교하여 동등 또는 우위의 수준을 달성하였다. 연료개질기 내부의 혼합 및 분배 구조를 개선하고 각 촉매층의 최적 배치를 통해 연료개질기의 부피를 최소화 하였으며 연료개질기 내부에서 고온부위와 저온부위 사이의 최적 열교환을 통해 열효율을 극대화 시켰다. 현재 개발된 $1Nm^3/h$급 개질기의 단열 후 부피는 13.5L 그리고 단독운전 시 열효율은 80%(LHV)로 측정되었다. 또한 $1Nm^3/h$급의 연료개질기의 스케일-업 설계를 통하여 수소생산량 3, $5Nm^3/h$ 규모의 연료개질기를 개발하였으며 성능평가가 진행 중이다.