• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 춘계학술대회
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• pp.589-593
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• 2007

재생 가능한 자원인 동식물성 기름을 원료로 제조되는 수송용 연료 바이오디젤은 낮은 대기오염물질 배출과 $CO_2$ Neutral 특성으로 환경친화적인 연료로 인정을 받으며 전세계적으로 그 생산량이 급격히 증가하고 있다. 대부분의 상용화 공정은 염기촉매를 이용한 전이에스테르화 반응에 근거하고 있으며 높은 생산성을 위해 연속 공정을 채택하고 있다. 원료유 중의 유리지방산(free fatty acid, FFA)은 염기 촉매와 반응하여 지방산염(Soap)과 수분을 생성하며 반응촉매의 투입양을 증가시카고 반응 후에 글리세롤과 지방산 메틸에스테르와의 분리를 어렵게 만든다. 높은 수율과 후속공정의 부하를 줄이기 위해서는 식물성 원료유 중의 FFA는 고체 산촉매 하에서 메탄올과 에스테르화 반응시켜 전환 제거되어야 한다. 본 연구에서는 고체산 촉매인 Amberlyst-15을 충전한 4단 PBR(Packed Bed Reactor, 충전율 60%(v/v))에서 반응시간과 반응온도에 따른 대두원유의 전처리 효율을 조사하였으며 최적 전처리 조건을 도출하였다. 최적 전처리 조건에서 대두원유는 초기 산가 1.6에서 0.4-0.6으로 연속 전처리할 수 있었다. 본 연구에서는 연속 흐름 반응기인 PFR(Plug Flow Reactor)와 4단 CSTR(Continuous Stirred Tank Reactor)에서 균질계 촉매인 KOH 존재하에 대두유와 메탄올과의 전이에스테르화 반응 특성을 조사하였으며 각 연속 반응시스템에서 최적 운전 조건을 도출하였다. PFR 반응기에서 반응온도, 반응시간, 반응물 흐름방향, static mixer(SM) 개수에 따른 반응특성을 조사한 결과, PFR에서의 최적 반응조건은 하향류 흐름 방향과 3개의 SM를 설치한 조건에서 반응시간 5.8분, 반응온도 90$^{\cdot}C$, 메탄올:오일 몰비 9:1, KOH 농도 0.8%로 도출되었다. CSTR 반응기에서는 반응온도와 체류시간에 따른 반응특성을 조사하였으며 최적반응 조건으로 반응온도 80$^{\cdot}C$, 메탄올/오일 몰비 9:1, KOH 농도 0.8%, 체류시간 18.4분, 교반속도 250rpm로 조사되었다.

• Journal of Microbiology and Biotechnology
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• 제4권3호
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• pp.204-209
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• 1994

The synthesis of N-(benzyloxycarbonyl)-L-aspartyl-L-phenylalanine methylester (Z-APM), a precursor of aspartame, from N-(benzyloxycarbonyl)-L-aspartic acid (Z-Asp) and L-phenylalanine methylester hydrochlolide($L-PM\cdot HCI$) was investigated in a saturated-ethylacetate single phase system using immobilized thermolysin. Among the various supports tested, glyceryl-CPG was found to be most efficient for retaining enzyme activity. The enzyme immobilized onto glyceryl-CPG also showed the highest activity for Z-APM synthesis in saturated ethyl acetate. Z-APM conversion yield in saturated ethylacetate was half of that obtained in an ethyl acetate-buffer two-phase system under the same reaction conditions. However, as the mole ratio of $L-PM \cdot HCI$ to Z-Asp was increased to 4.0, the conversion yield reached 95 %. When continuous synthesis of Z-APM was canied out in a plug flow reactor (PFR) with 80 mM of L-PMㆍHCI and 20 mM of Z-Asp in saturated ethylacetate (pH 5.5), more than 95 % of Z-Asp was converted to Z-APM with a space velocity of 1.16 $hr^{-1} at 40^{\circ}C$. Although the operational stability in PFR was reduced rapidly, more than 80% of initial activity was maintained in CSTR even after a week of operation.

• 한국수소및신에너지학회논문집
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• 제13권2호
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• pp.119-126
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• 2002

The methanol partial oxidation using commercial $CuO/ZnO/Al_2O_3$ catalysts in a plug flow reactor was studied in the temperature range of $200{\sim}250^{\circ}C$ at atmospheric pressure, It was achieved the high activities by Cu-based catalysts and the selectivity of $CO_2$/$H_2$ was 100% when $O_2$ was fully convened. The reactivity changes and their hysteresis with increasing/decreasing temperatures were observed due to the chemical state differences between the oxidation and the reduction on the Cu surface, It was suggested as the two-step reaction: the complete oxidation and the following steam reforming for methanol, which was indicated by the distributions of final products vs. the residence time. In addition, the complete oxidation step was shown to be extremely fast and the total reaction rate can be controlled by the steam reforming reaction.

• 한국수소및신에너지학회논문집
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• 제13권3호
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• pp.214-223
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• 2002

Kinetic and effectiveness factors for methanol steam reforming using commercial copper-containing catalysts in a plug flow reactor were investigated over the temperature ranges of $180-250^{\circ}C$ at atmospheric pressure. The selectivity of $CO_2$/$H_2$ was almost 100%, and CO products were not observed under reaction conditions employed in this work. It was indicated that $CO_2$ was directly produced and CO was formed via the reverse water gas shift reaction after methanol steam reforming. The intrinsic kinetics for such reactions were well described by the Langmuir-Hinshelwood model based on the dual-site mechanism. The six parameters in this model, including the activation energy of 103kJ/mol, were estimated from diffusion-free data. The significant effect of internal diffusion was observed for temperature higher than $230^{\circ}C$ or particle sizes larger than 0.36mm. In the diflusion-limited case, this model combined with internal effectiveness factors was also found to be good agreement with experimental data.

• 한국환경과학회지
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• 제22권10호
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• pp.1263-1271
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• 2013

Graphene oxide (GO)-titania composites have emerged as an attractive heterogeneous photocatalyst that can enhance the photocatalytic activity of $TiO_2$ nanoparticles owing to their potential interaction of electronic and adsorption natures. Accordingly, $TiO_2$-GO mixtures were synthesized in this study using a simple chemical mixing process, and their heterogeneous photocatalytic activities were investigated to determine the degradation of airborne organic pollutants (benzene, ethyl benzene, and o-xylene (BEX)) under different operational conditions. The Fourier transform infrared spectroscopy results demonstrated the presence of GO for the $TiO_2$-GO composites. The average efficiencies of the $TiO_2$-GO mixtures for the decomposition of each component of BEX determined during the 3-h photocatalytic processes were 26%, 92%, and 96%, respectively, whereas the average efficiencies of the unmodified $TiO_2$ powder were 3%, 8%, and 10%, respectively. Furthermore, the degradation efficiency of the unmodified $TiO_2$ powder for all target compounds decreased during the 3-h photocatalytic processes, suggesting a potential deactivation even during such a short time period. Two operational conditions (air flow entering into the air-cleaning devices and the indoor pollution levels) were found to be important factors for the photocatalytic decomposition of BEX molecules. Taken together, these results show that a $TiO_2$-GO mixture can be applied effectively for the purification of airborne organic pollutants when the operating conditions are optimized.

• 한국수소및신에너지학회논문집
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• 제33권6호
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• pp.786-794
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• 2022

Green ammonia is a promising renewable energy carrier. Green ammonia can be used in various energy conversion devices (e.g., engine, fuel cell, etc.). Ammonia has to be fed with hydrogen for start-up and failure protection of some energy conversion devices. Ammonia can be converted into hydrogen by decomposition and partial oxidation. Especially, partial oxidation has the advantages of fast start-up, thermally self-sustaining operation and compact size. In this paper, thermodynamics, start-up and operation characteristics of ammonia partial oxidation were investigated. O₂/NH₃ ratio, ammonia flow rate and catalyst volume were varied as operation parameters. In thermodynamic analysis, ammonia conversion was maximized in the O₂/NH₃ range from 0.10 to 0.15. Ammonia partial oxidation reactor was successfully started using 12 V glow plug. At 0.13 of O₂/HN₃ ratio and 10 LPM of ammonia flow rate, ammonia partial oxidation reactor showed 90% of ammonia conversion over commercial Ru catalyst. In addition, Increasing O₂/NH₃ ratio from 0.10 to 0.13 was more effective for high ammonia conversion than increasing catalyst volume at 0.10 of O₂/NH₃.

• 한국자동차공학회논문집
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• 제20권6호
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• pp.73-82
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• 2012

The main and side reactions of the three selective catalytic reduction (SCR) reactions with ammonia over a vanadium-based catalyst have been investigated using synthetic gas mixtures in the temperature range of $170{\sim}590^{\circ}C$. The three SCR reactions are standard SCR with pure NO, fast SCR with an equimolar mixture of NO and $NO_2$, and $NO_2$ SCR with pure $NO_2$. Vanadium based catalyst has no significant activity in NO oxidation to $NO_2$, while it has high activity for $NO_2$ decomposition at high temperatures. The selective catalytic oxidation of ammonia and the formation of nitrous oxide compete with the SCR reactions at the high temperatures. Water strongly inhibits the selective catalytic oxidation of ammonia and the formation of nitrous oxide, thus increasing the selectivity of the SCR reactions. However, the presence of water inhibits the SCR activity, most pronounced at low temperatures. In this study, the experimental results are analyzed by means of a dynamic one-dimensional isothermal heterogeneous plug-flow reactor (PFR) model according to the Eley-Rideal mechanism.

• 한국자동차공학회논문집
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• 제20권5호
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• pp.71-80
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• 2012

To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

• Applied Biological Chemistry
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• 제28권4호
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• pp.233-238
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• 1985

Glucoamylase를 $ZrO_2$로 피복된 96% porous glass에 azo-linkage를 형성시켜 결합하게 한후, 2.5% glutaraldehyde로 처리하여 효소를 고정화시켰다. 효소기질로는 용해도가 높고 점도가 낮은 30% enzyme thinned cornstarch (dextrose equivalent 값 : 24)를 사용하여 plug flow-column reactor에서 연속반응시켰다. 반응 최적 pH는 수용성효소의 5.0보다 alkaline 쪽으로 기울어져 7.0으로 나타났고, 고정화반응에 따라 열안정성이 높아지고 $40{\sim}60^{\circ}C$에서 최적 온도범위를 가리키며, Km값은 수용성 효소의 1.25mM보다 낮은 1.04mM값을 보여 주었다. 따라서, pH 7.0, $45^{\circ}C$에서 160시간 동안 corn starch를 기질로 효소반응을 시켜 glucose 90.3%, maltose 8.0%인 DE값 94.0인 전분당분해산물을 획득할 수 있었다.

• 유기물자원화
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• 제14권4호
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• pp.113-120
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• 2006

음식물류 폐기물 자원화과정에서 발생하는 폐수는 BOD 20,000~150,000mg/L이며, 매립금지로 적정수준까지 처리되어야 한다. 그러나 기존의 폐수처리시설에 의해서는 10일 이하로 처리하기가 불가능하다. (주)에코데이는 높은 산소전달효율, 높은 미생물(MLVSS) 유지와 유기물 농도 모두가 상향류의 PFR흐름을 갖는 ER-1 반응기를 이용하여 2~4일 이내로 처리할 수 있는 기술을 개발하였다. 하루 20톤의 음식물을 퇴비화 하는 H군 음식물 자원화시설에 Pilot plant를 설치하고, 자원화 과정에서 발생하는 고농도폐수(평균 BOD 64,431mg/L)와 저농도폐수(평균 BOD 16,500mg/L)에 대해 6개월간 실험하였다. 저농도폐수의 처리를 위해서 ER-1(HRT 2.5d)과 후단에 고도처리공정을 적용하였으며, 이때 전체공정에서 제거되는 유기물의 대부분이 ER-1을 통해 제거되었다. 저농도폐수 Pilot plant의 처리효율은 BOD 99%, COD 98%, SS 99%, T-N 97%, T-P 96%이다. 고농도 폐수 처리공정은 ER-1을 직렬로 배치하여 2단계 ER-1(1차 HRT 2.5d, 2차 HRT 1.5d) 후 고액분리를 통해 하수연계(BOD 2,000mg/L 이하)로 계획하였다. Pilot 실험결과 고농도 폐수에 대해서도 BOD 97%, COD 84%, SS 98%, T-N 66%, T-P 95%의 안정적인 처리효율을 얻을 수 있었다. 고농도 폐수처리시에 생물반응기의 냉각시설 없이 고온($50^{\circ}C$)으로 운전되었으나, 온도 조절 부분을 개선한다면 더 높은 효율을 기대할 수 있을 것으로 판단된다.