• Transactions of the Korean hydrogen and new energy society
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• v.15 no.4
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• pp.301-308
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• 2004

The methane reforming with $CO_2$ and steam for manufacture of synthesis gas over $Ni/ZrO_2$ catalyst was investigated. Mixed reforming carried out $CO_2$ dry reforming with $O_2$ and steam for development of DME process in pilot plant. To improve a catalyst deactivation by coke formation, the mixed reforming added carbon dioxide and steam as a oxidizer of the methane reforming was suggested. The result of experiments over commercial catalyst in $CO_2$ dry reforming has shown that the catalyst activity decrease rapidly after 20 hours. In case of $NiO-MgO/Al_2O_3$ catalyst, the deactivation of 20 percent after 30 hours was occurred. The activity of Ni/C catalyst still was not decreased dramatically after 100 hours. The effect of $H_2$ reforming with steam over $Ni/CO_2$ catalyst obtained the optimal conversion of methane and carbon dioxide, and could be produced synthesis gas at ratio of $H_2/CO$ under 1.5.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.55-58
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• 2007

To check the feasibility of SMART (Steam Methane Advanced Reforming Technology)system, an experimental investigation was conducted. A fluidized bed reactor of diameter 0.052 m was operated cyclically up to the $10^{th}$ cycle, alternating between reforming and regeneration conditions. FCR-4 catalyst was used as the reforming catalyst and calcined limestone (domestic, from Danyang) was used as the $CO_2$ absorbent. Hydrogen concentration of 98.2% on a dry basis was reached at $650^{\circ}C$ for the first cycle. This value is much higher than $H_2$ concentration of 73.6% in the reformer of conventional SMR (steam methane reforming) system. However, the hydrogen concentration decreased because the $CO_2$ capture capacity decreased as the number of cycles increased.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.143-143
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• 2010

GTL(Gas-to-Liquids)공정 중 합성가스 제조공정(Reforming Process)인 ATR(Auto-Thermal Reforming), SCR(Steam Carbon Reforming), POx(Partial Oxidation)의 시뮬레이션 연구를 수행하였다. Reforming 공정에서 생산된 합성가스는 GTL 합성유 제조공정인 FT(Fischer-Thropsch) 반응기로 주입되며, 합성유 생산에 최적의 효율을 보이는 H2/CO 비(합성가스에 포함된 반응물비)는 2.0으로 알려져 있다. FT공정은 합성가스를 원료로 고온 및 고압 반응을 거쳐 GTL 공정의 최종 생산품인 FT합성유를 제조하는 공정이다. 본 연구에서는 FT공정 효율 극대화를 위해 reforming 공정에서 생성되는 합성가스 내 H2/CO의 비를 2로 수렴토록 모사조건을 설정하였으며, 상기 조건을 만족하는 reforming 공정들의 운전 온도 및 feed 조성을 분석하고 비교하고자 한다. 현재 GTL 플랜트관련 산업계에 적용 혹은 주 연구대상인 reforming 공정으로는 ATR, SCR, POx 공정이 있다. ATR 공정은 $850{\sim}1100^{\circ}C$에서 메탄, 스팀 및 산소를 원료로 활용하여 H2 및 CO를 생산하는 공정으로 발열/흡열 반응이 상존하여 에너지 비용이 낮지만 공정구조 상 열회수설비 및 ASU(Air Separation Unit)이 필요하기에 CAPEX(초기설비 설치비용)가 높은 편이다. SCR공정은 CH4, Steam 및 CO2를 연료로 하기에 이산화탄소가 일정부분 포함된 가스전에도 적용이 가능하나 공정 운전 중 지속적으로 외부에서 열을 공급해야 하기에 에너지 투입비용이 높은편이며, 탄소침적의 문제가 있어 대용량 플랜트에는 적합하지 않다. POx공정은 약 $1,500^{\circ}C$의 고온에서 CH4가 O2에 의해 부분 산화되는 방식으로 촉매가 필요없어 설비비가 타 공정에 비해 저렴하나 생산가스의 H2/CO비가 다소 낮아 전체적인 GTL 공정효율이 저하되는 단점이 있다. 상기 세 공정은 GTL 산업계에서 실증 및 효율증대를 위해 주로 연구되는 공정이기에 본 연구의 분석대상으로 설정하였다. 본 연구에서는 상용공정모사기인 Aspen Plus를 활용하여 reforming 공정별로 FT합성공정의 최적 조건(H2/CO=2)을 만족하는 합성가스 생산조건 분석 및 비교를 수행할 예정이다. 운전조건인 공정 운전온도 및 feed 가스조성 등을 모사하기 위해 합성가스 reforming 공정을 모델링하고 공급유량 및 압력 등의 운전변수는 GTL국책과제 1단계 연구수행 결과를 토대로 선정하고자 한다. GTL공정의 경우, 설비의 운전조건이나 연료가스의 구성 및 유량에 따라 적합한 reforming 공정이 다르기에 본 시뮬레이션 결과를 향후 GTL 플랜트 공정모델 설계시 reforming 공정선정에 참고자료로 활용하고자 한다.

• Bulletin of the Korean Chemical Society
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• v.24 no.11
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• pp.1623-1626
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• 2003

The dependency of the rate of $CO_2$ reforming of methane on the catalyst loading and the reactor size was examined at a fixed temperature of $750\;^{\circ}C$ and a fixed GHSV of 18000 mL(STP)/$g_{cat}.h$. The conversion of methane in $CO_2$reforming decreased with increase in the reactor size. The catalyst was severely deactivated with increase in the catalyst amount. The amount of carbonaceous species combustible below $550\;^{\circ}C$, determined by TPO experiments with the used catalyst samples increased with increase in the catalyst amount, which was again confirmed by XRD and TEM experiments. The increase of the carbonaceous species combustible below $550\;^{\circ}C$ may be due to the suppression of the reverse Boudouard reaction, since the $CO_2$ reforming of methane, a highly endothermic reaction, resulted in lowering the reaction temperature.

• Journal of the Korean Society of Combustion
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• v.13 no.4
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• pp.47-53
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• 2008

The reaction mechanism of methane dry reforming has been investigated using an arc-jet reactor. The effects of input power, $CO_2/CH_4$ and added $O_2$ were investigated by product analysis, including CO, $H_2$, $C_{2}H_{Y}$ and $C_{3}H_{Y}$ as well as $CH_4$ and $CO_2$. In the process, input electrical power activated the reactions between $CH_4$ and $CO_2$ significantly. The increased feed ratio of the $CO_2$ to $CH_4$ in the dry reforming does not affect to the $CH_4$ conversion. but we could observe increase in CO selectivity together with decreasing $H_2$ generation. Added oxygen can also increase not only CO selectivity but also $CH_4$ conversion. However, hydrogen selectivity was decreased significantly due to a increased $H_{2}O$ formation.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.1
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• pp.3-12
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• 2002

In this study, it achieved life cycle assessment to estimate environmental performance for naphtha steam reforming that account for the production over 50% of total hydrogen output. Although hydrogen dosen't emit air emissions, especially, $CO_2$, a large of $CO_2$ is emitted in hydrogen production process. In the result of this study, it ascertained the truth that $CO_2$ is emitted at the rate of $6.3kg/kgH_2$ and that result from steam reforming reaction and use of fossil fuel in hydrogen manufacturing process. Above all, 57% of total $CO_2$ emissions is emitted in process of steam reforming of naphtha and so it knew that the principle of steam reforming is key issue in aspect to environment. Also, it compared hydrogen by fuel of fuel cell vehicle with gasoline fuel of general gasoline vehicle to analyze relative environment of hydrogen for fossil fuel during the life cycle. As the result, it might be difficult in improvement of environment because $CO_2$ emissions during the hydrogen manufacturing process is nearly the same with that during the use of gasoline.

• Korean Journal of Chemical Engineering
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• v.35 no.11
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• pp.2191-2197
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• 2018

To remove tar and produce environment-friendly $H_2$, one of the promising routes is the sorption-enhanced steam reforming (SESR) process, in which the $CO_2$ sorbent is a key element. We prepared the $CO_2$ sorbents with $Ca_{12}Al_{14}O_{33}$ as carrier with various methods. Their characterizations were examined, and the sample prepared by solgel (SG) method showed the strongest CaO and $Ca_{12}Al_{14}O_{33}$ phases and the most excellent pore structure among all the samples. Then, a thermogravimetric experiment was conducted, and the results showed that the sample prepared by sol-gel (SG) method had the best $CO_2$ adsorption capacity and excellent long-term cyclic stability. Finally, the sorbent was used into the steam reforming experiments of tar. Under the action of the sorbent, the reforming reaction was enhanced in-situ, with the $H_2$ yield and concentration improved obviously, and especially, $H_2$ concentration can reach over 98.85%.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.4
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• pp.382-390
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• 2007

To check the feasibility of SMART(Steam Methane Advanced Reforming Technology) system, an experimental investigation was performed. A fluidized bed reactor of diameter 0.052m was operated cyclically up to 10th cycle, alternating between reforming and regeneration conditions. FCR-4 catalyst was used as the reforming catalyst and calcined limestone(domestic, from Danyang) was used as the $CO_2$ absorbent. Hydrogen concentration of 98.2% on a dry basis was reached at $650^{\circ}C$ for the first cycle. This value is much higher than $H_2$ concentration of 73.6% in the reformer of conventional SMR (steam methane reforming) condition. The hydrogen concentration decreased because the $CO_2$ capture capacity decreased as the number of cycles increased. However, the average hydrogen concentration at 10th cycle was 82.5% and this value is also higher than that of SMR. Based on these results, we could conclude that the SMART system can replace SMR system to generate pure hydrogen without HTS (high tempeature shift), LTS (low temperature shift) and $CO_2$ separation process.

• Journal of Korean Society for Atmospheric Environment
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• v.26 no.6
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• pp.683-689
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• 2010

Reforming of methane with carbon dioxide has been carried out using a bipolar pulse driven elongated arc reactor operating at atmospheric pressure and non-equilibrium regime. This plasma reactor is driven by two kinds of power supply, characterized by different voltage-current characteristics under the same operating power and frequency. Varying the $CO_2/CH_4$ ratio and the discharge power, the conversion rate, yield, and reforming efficiency for the two power supplies are investigated in conjunction with the static and dynamic behaviors of voltage and current. It is found that not only the values of voltage and current but also their shapes give an influence on the reforming performances. Finally, a better electrical operation regime for the efficient plasma reforming is proposed based on the relationship between the voltage-current characteristics and the reforming performance.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.2017-2020
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• 2005

The supported bimetallic Co-containing catalysts promoted by the different amount of noble metal (Pd) have been studied in the dry reforming of methane. The activity, selectivity, stability and resistance to the carbon deposition of Co-Pd/$Al_2O_3$ catalysts depend on both the catalyst composition and process conditions. It has been observed that the Co-Pd/$Al_2O_3$ catalysts produce the various oxygenates from $CO_2$ + $CH_4$ at moderate pressures.