• Korean Membrane Journal
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• v.6 no.1
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• pp.10-15
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• 2004

We developed a water-selective ceramic composite membrane for use as a dehydration membrane reactor for dimethylether (DME) synthesis from methanol. The membranes were modified on the porous stainless steel support by the sol-gel method accompanied by a suction process. The improved membrane modification process was effective in increasing the vapour permselectivity by removal of defects and pinholes. The optimized alumina/silica composite membrane exhibited a water permeance of 1.14${\times}$10$^{-7}$ mol/$m^2$.sec.Pa and a water/methanol selectivity of 8.4 at permeation temperature of 25$0^{\circ}C$. The catalytic reaction for DME synthesis from methanol using the membrane was performed at 23$0^{\circ}C$, and the reaction conversion was compared with that of the conventional fixed-bed reactor. The reaction conversion of the membrane reactor was much higher than that of the conventional fixed-bed reactor. The reaction conversion of the membrane reactor and the conventional fixed-bed reactor was 82.5 and 68.0%, respectively. This improvement of reaction efficiency can last if the water vapour produced in the reaction zone is removed continuously.

• Korean Chemical Engineering Research
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• v.49 no.2
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• pp.155-160
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• 2011

Dimethyl ether draws an attention as a green fuel in recent years. In this study, we investigated dehydration of methanol to produce DME using solid-acid catalysts, a series of zeolite. We found that ceria took a role of promoting the reaction conversion as well as selectivity of DME formation as a cocatalyst to the zeolite catalyst. We varied Si/Al ratio and ceria percentage on the surface of the catalyst to get high performance catalyst. ZSM5-30 with 5 wt% ceria on the surface was found to have excellent DME selectivity and to be little influenced by water content in methanol feed. We proposed a reaction model and obtained kinetic parameters for the DME formation using the catalyst based on experimental results using a microreactor.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1628-1632
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• 2010

Porous ${\eta}-Al_2O_3$ was synthesized by modified sol-gel method using ionic liquid as a templating material. The addition of ionic liquid assisted to increase the surface area of alumina. However, the acidity of aluminas prepared with ionic liquids was hardly affected regardless the change of its structural properties. Among the ionic liquids used in this study, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][$PF_6$]) was the most effective ionic liquid to produce porous ${\eta}-Al_2O_3$ particles. The catalytic performance of these aluminas has been investigated in dehydration of methanol to produce dimethyl ether. The alumina prepared with [Bmim][$PF_6$] outperformed the other aluminas except ${\eta}-Al_2O_3$ without modification in this reaction.

• Journal of Hydrogen and New Energy
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• v.15 no.4
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• pp.283-290
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• 2004

The single-step process for conversion of syngas to DME give higher conversion than the syngas-to-methanol process. This arises because of a synergy among the three simultaneous reaction, methanol synthesis, methanol dehydration and water gas shift reaction, in the process. we would find the optimal condition of the process which these advantages. The optimal condition of DME synthesis reaction over a commercial $Cu/Zn/Al_2O_3$ catalyst and Hybrid catalyst in a fixed bed reactor. The syngas-to-dimethyl ether conversion was examined on various reaction condition (Temperature 473~553K, $H_2/CO$ ratio 1~3, Pressure 30'50atm, GHSV 1000~4000).

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.566-572
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• 2007

Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

• Korean Journal of Soil Science and Fertilizer
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• v.48 no.3
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• pp.180-188
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• 2015

To investigate the tendency of $Li^+$ exchange from polar organic solvents, $Li^+$-ion exchange into zeolite Y (Si/Al = 1.56) was attempted by undried methanol (crystal 1) and formamide (crystal 2) solvent. Two single crystals of Na-Y were treated with 0.1 M LiNO3 in each of the two solvents at 323 K, followed by vacuum dehydration at 723 K. Their structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd{\bar{3}}m$, at 100(1) K. In both structures, $Li^+$ for $Na^+$ ions filled preferentially sites I' and II. The remaining $Na^+$ ions occupied sites I', II, and III' in both structures, in additional to above sites, and $Na^+$ ions occupied site I in crystal 2. While the 68 % exchange of $Li^+$ for $Na^+$ was achieved from undried methanol, only 40 % exchange was observed from undried formamide, indicating that the undried methanol was more effective than undried formamide as solvent for $Li^+$ exchange under the conditions employed.

• Journal of the Korean Magnetic Resonance Society
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• v.1 no.2
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• pp.126-140
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• 1997

Mesoporous MCM-41 gallosilicate material was synthesized through shifting through shifting gallosilicate polymer equilibrium towards a MCM-41 phase by addition of acid. The location of Cu(II) exchanged into MCM-41 and its interaction with various adsorbate molecules were investigated by electron spin responance and electron spin echo modulation spectroscopies. It was found that in the fresh hydrated material, Cu(II) is octahedrally coordinated to six water molecules. This species is located in a cylindrical channel and rotates rapidly at room temperature. Evacuation at room temperature removes three of these water molecules, leaving the Cu (II) coordinated to three water molecules and anchored to oxygens in the channel wall. Dehydration at 45$0^{\circ}C$ produces one Cu (II) species located in the inner surface of a channel as evidenced by broadening of its ESR lines by oxygen. Adsorption of polar molecules such as water, methanol and ammonia on dehydrated CuNa-MCM-41 gallosilicate material causes changes in the ESR spectrum of Cu (II), indicating the complex formation with these adsorbates. Cu (II) forms a complex with six molecules of methanol as evidenced by an isotropic room temperature ESR signal and ESEM data like upon water adsorption. Cu(II) also forms a complex containing four molecules of ammonia based on resolved nitrogen superhyperfine interaction.

• Journal of the Korean Chemical Society
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• v.25 no.2
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• pp.97-102
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• 1981

The conversion of methanol to hydrocarbons has been studied over synthetic ZSM-5 zeolite catalyst having high silica to alumina ratio. The conversion products were olefins, paraffins, cycloparaffins, and aromatics, and the catalyst showed especially high selectivity toward the formation of aromatics. The catalyst showed the shape-selectivity and the size of molecules in the product was limited approximately to the size of 1,3,5-trimethylbenzene. Hydrogen form(HZSM-5) was more active, indicating reactions following the dehydration of methanol seemed to be mainly catalyzed by acid sites. Comparison of the reaction characteristics and acid site distribution of the ZSM-5 catalyst with those of mordenite and faujasite type catalysts suggests that cross-linked pore channel structure and the strong acidity of the ZSM-5 catalyst are primarily responsible for the selective formation of aromatics over this catalyst.

• Journal of Hydrogen and New Energy
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• v.23 no.5
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• pp.559-571
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• 2012

Dimethyl ether (DME) is a new clean fuel as an environmentally-benign energy resource. DME can be manufactured from various energy sources including natural gas, coal, and biomass. In addition to its environmentally friendly properties, DME has similar characteristics to those of LPG. The aim of this article is to represent the development of new DME process with KOGAS's own technologies. KOGAS has investigated and developed new innovative DME synthesis process from synthesis gas in gaseous phase fixed bed reactor. DME has been traditionally produced by the dehydration of methanol which is produced from syngas, a product of natural gas reforming. This traditional process is thus called the two-step method of preparing DME. However, DME can also be manufactured directly from syngas (single-step). The single-step method needs only one reactor for the synthesis of DME, instead of two for the two-step process. It can also alleviate the thermodynamic limitations associated with the synthesis of methanol, by converting the produced methanol into DME, thereby potentially enhancing the overall conversion of syngas into DME. KOGAS had launched the 10 ton/day DME demonstration plant project in 2004 at Incheon KOGAS LNG terminal. In the mid of 2008, KOGAS had finished the construction of this plant and has successively finished the demonstration plant operation. And since 2008, we have established the basic design of commercial plant which can produce 3,000 ton/day DME.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.178.1-178.1
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• 2011

DME is generally expected to be used as a promising clean alternative fuel to diesel fuel. DME is not natural product but a synthetic product that is produced either through the dehydration of methanol or a direct synthetic from syngas. As DME has no carbon-carbon bond in its molecular structure and is an oxygenate fuel, it's combustion essentially generates no soot. DME has such cetane number of 55~60 that it can be used as a diesel engine fuel. However, DME has low lubricity but a proven method to solve the poor lubricity is by adding lubricity improver. Therefore, the aim of this study is to develop lubricity improver of DME as a transport fuel in Korea. In this study, we investigated a possibility of fatty acid ester compounds as a candidate to improve DME lubricity as compared with current lubricity improver of diesel. We also evaluated quality characteristics, storage stability of DME with lubricity additives.