• Clean Technology
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• v.16 no.3
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• pp.220-228
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• 2010

Four Keggin-type heteropolyacids, $H_nXM_{12}O_{40}$(X = P and Si, M = W and Mo) that were substituted with heteroatom and polyatom were applied to the dehydration reaction of fructose to 5-hydroxymethylfurfural (HMF). The results showed that the acid became stronger when the heteroatom and polyatom were substituted with P and W than the cases of Si and Mo, respectively. However, the amount of acidic sites increased with the decrease in the acid strength, resulting in the change of the catalytic activity of heteropolyacids in the dehydration reaction. The experimental results revealed that four different heteropolyacids produced similar amounts of HMF via the dehydration reaction of fructose due to the counterbalancing effect between the amount of active sites, which is related to the catalytic activity of heteropolyacids, and the softness of polyanion. In addition, it was observed that the prepared heteropolyacids showed good structural stability after heat treatment at $200^{\circ}C$.

• Korean Chemical Engineering Research
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• v.47 no.2
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• pp.163-168
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• 2009

Negative differential resistance(NDR) behaviors of Keggin-type and Wells-Dawson-type heteropolyacids with cation, heteroatom, and polyatom substitutions were investigated by scanning tunneling microscopy. A reliable correlation between NDR peak voltage and reduction potential of heteropolyacid catalysts was established. It was found that more reducible heteropolyacid catalyst showed NDR behavior at less negative voltage, regardless of the structural difference. Thus, NDR peak voltage of heteropolyacid catalyst could be utilized as a single correlating parameter for the reduction potential of heteropolyacid catalyst.

• Applied Chemistry for Engineering
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• v.18 no.1
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• pp.36-40
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• 2007

The study on the isomerization reaction of endo-tetrahydrodicyclopentadiene and endo-tetrahydrodi(methylcyclopentadiene) using heteropolyacid catalyst was carried out. Exo compound was prepared from endo compound through isomerization reaction. To improve the problem of aluminum chloride as an isomerization catalyst, application of heteropolyacid was attempted. In use of Keggin type heteropolyacid, catalytic activity was extremely high at cesium substitution instead of 2.5 hydrogen atoms of $H_3PW_{12}O_{40}$. Using the cesium substituted heteropolyacid, isomerization reaction rate was faster than aluminum chloride and the effect of reaction temperature and times on reactivities were compared in isomerization of tetrahydrodicyclopentadiene and tetrahydrodi(methylcyclopentadiene).

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.251-256
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• 2012

Etherification of n-butanol to di-n-Butyl Ether was carried out over Keggin $H_{3+x}PW_{12-x}Nb_xO_{40}$ (x=0, 1, 2, 3) and $H_{6+x}P_2W_{18-x}Nb_xO_{62}$ (x=0, 1, 2, 3) Wells-Dawson heteropolyacid catalysts. Niobium-substituted Keggin and Wells-Dawson heteropolyacid catalysts with different niobium content were prepared. Successful preparation of the catalysts was confirmed by FT-IR, ICP-AES, and $^{31}P$ NMR analyses. Their acid properties were determined by $NH_3$-TPD (Temperature-Programmed Desorption) measurements. Heteropolyacid catalysts showed different acid properties depending on niobium content in both series. The correlation between acid properties of heteropolyacid catalysts and catalytic activity was then established. Acidity of Keggin and Wells-Dawson heteropolyacid catalysts decreased with increasing niobium content, and conversion of n-butanol and yield for di-n-butyl ether increased with increasing acidity of the catalysts, regardless of the identity of heteropolyacid catalysts (without heteropolyacid structural sensitivity). Thus, acidity of heteropolyacid catalysts served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-Butyl Ether.

• Applied Chemistry for Engineering
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• v.2 no.4
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• pp.363-371
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• 1991

The catalytic performance and availability of heteropoly compounds for the conversion of methanol to hydrocarbons have been studied. The effects of reaction conditions such as reaction temperature, methanol partial pressure and residence time and the effects of ion-exchange of the catalysts were examined for enhancing the yield of hydrocarbons and the selectivity of low olefins. Their acid strength depended on the kind of countercation, and the yield of hydrocarbons and the selectivity for propylene to propane were closely related to the electronegativity of the corresponding countercations. In contrast to the other heteropoly compounds, the ammonium salt showed a considerably high catalytic activity and a high selectivity for paraffins to low olefins.

• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.582-588
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• 1997

Synthetic reaction of TAME, ETBE, and MTBE compounds used largely for gasoline octane number enhancer to prevent air pollution was investigated using heteropolyacid catalyst in a fixed bed flow reactor. In the synthetic reaction of TAME, ETBE and MTBE, after hetero atom being replaced with poly atom, the activity of the catalyst, $H_4SiW_{12}O_{40}$ with coordinated bond with W and an hetero atom of Si was the highest among the catalysts tested. Also the activity depended upon the metals replaced which are related to the catalyst acidity. $FeHPW_{12}O_{40}$ and $K_3PM_{o12}O_{40}$ catalysts showed high activity in TAME synthesis, while they were not effective in ETBE and MTBE synthesis. In this study catalysts showing high activity were selected and mixed with equal weight combination of $H_4SiW_{12}O_{40}$ and $Sr_2SiW_{12}O_{40}$ ;$H_4SiW_{12}O_{40}$ and $NaH_2PW_{12}O_{40}$ ; $Fe_{1.5}PW_{12}O_{40}$ and $Mg_2SiW_{12}O_{40}$ ; $Mg_2SiW_{12}O_{40}$ and $Ba_2SiW_{12}O_{40}$. The mixed heteropolyacid catalysts showed higher TBA conversion rate and better selectivity of ETBE and MTBE than the single catalysts.

• Applied Chemistry for Engineering
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• v.5 no.3
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• pp.431-437
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• 1994

The role and the formation of surface and bulk acid sites of heteropoly acids were studied by examining ethanol conversion and MTBE (methyl t-butyl ether) decomposition reaction. In ethanol dehydration diethylether was formed on the surface acid site of 12-tungstophosphoric acid, whereas ethylene was formed in the bulk acid site of the catalyst. It was revealed that water reinforced the bulk acid site of the catalyst, while organic base decreased the bulk acid function of the catalyst. The formation of acid sites of metal salts was due to hydrolysis of crystalline water and/or partial substitution of metal, and with hydrogen treatment, the acid site was reappeared. Also catalyst design as a selective oxidation catalyst was possible by controlling acid function of heteropoly acid catalyst.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2005.11a
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• pp.229-232
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• 2005

The study on the improvement of manufacturing process of RJ-4 liquid fuel that have high flash point, was carried out. In preparing of RJ-4 using commercially available MCPD, 1st, 2nd hydrogenation and isomerization reaction were enabled 1 step continuous process by combined use of heteropoly phosphoroustungstic cesium salt catalyst and 2nd stage-heat-controllable reactor. Also when heteropolyacid cesium salt was used as a isomerization catalyst instead of aluminum chloride, formation rate of exe-THDMCPD was higher, the catalyst could be easily separable from product and there was no production of waste acid, so this new reaction condition was confirmed as the environment friendly process.

• Applied Chemistry for Engineering
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• v.4 no.2
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• pp.335-341
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• 1993

In the conversion of methanol, the effect of acide property of heteropoly compounds on the catalytic activity was investigated. The pretreatment of Cu-exchanged 12-tungstophosphoric acid with hydrogen enhanced both the selectivity for propane and the conversion of methanol, and the pretreatment of Al-exchanged 12-tungstophosphoric acid with water enhanced the acid strength of the catalyst. The water added into the reactant decreased the conversion of methanol, while the pretreatment temperature did not affect it but the propylene/propane ratio. Various partially-substituted Al salts of 12-tungstophosphoric acid showed different catalytic activities depending on the degree of Al-substitution.

• Applied Chemistry for Engineering
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• v.4 no.3
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• pp.549-557
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• 1993

In the conversion of ethanol over heteropoly acids, we have studied catalytic reactivity, reaction mechanism, effect of organic bases added to reactant, and relation between acid strength of ion-exchanged catalysts and catalytic activities. The conversion of ethanol proceeded in the pseudoliquid phase of heteropoly acid. Due to this novel behavior, area increased by supporting with $SiO_2$. The reaction mechanism of ethylene production was different from that of ether production, and various partially substituted Al salts of 12-tungstophosphoric acid showed different catalytic activities.