• Clean Technology
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• v.19 no.1
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• pp.13-21
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• 2013

The hydrogenolysis of cellulose into polyols was examined over Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts containing different Cs fractions. The surface area and Pt dispersion of Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts were found to increase with Cs content. Similar polyol yields were obtained over Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalysts irrespective of their Cs content. The catalytic activity of Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ was comparable to that of Ni/W/SBA-15 and combined catalytic systems such as Pt/AC+$H_3PW_{12}O_{40}$ and Pt/AC + $Cs_{3.0}PW_{12}O_{40}$. Some polyanion species were found to leach from the Pt/$Cs_xH_{3-x}PW_{12}O_{40}$ catalyst during the course of the reaction.

• Journal of the Korean Chemical Society
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• v.52 no.1
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• pp.23-29
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• 2008

Simple Keggin type tungsten and molybdenum heteropoly acids, H3PW12O40 and H3PMo12O40, were usedas water-tolerant catalysts for the oxidation of alcohols with 34% hydrogen peroxide in normal drinking water. Accordingto our findings, H3PW12O40 may be used as a simple, effective, and cheap catalyst for this type of transformation in nor-mal drinking water with excelent yields. Efects of diferent solvents at 25-80oC and changing concentration of catalystand substrate on the reaction progress were also studied.

• Applied Chemistry for Engineering
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• v.8 no.2
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• pp.211-219
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• 1997

Liquid or gas phase alkylation of isobutane with 1-butene for i-octane production was carried out over Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$. Pretreatment temperature of the catalyst played an important role on the catalytic activity of heteropoly acids in the liquid phase alkylation. Cation-exchanged $H_3PW_{12}O_{40}$ showed a better total yield and i-octane selectivity than the mother acid in the liquid phase alkylation, and $(NH_4)_{2.5}H_{0.5}PW_{12}O_{40}$ was more efficient than $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ in terms of i-octane selectivity. It was found that the acidic property (deactivation of acid sites) of the catalyst was closely related to the catalytic activity of Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$ in the gas phase alkylation. $C_5-C_7$ were mainly formed in the early stage of gas phase alkylation due to the strong acidic property of the catalyst, whereas $C_8$ and $+C_9$ were mainly produced as the reaction proceeded due to the deactivation of acid sites. $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ showed the highest total yield in the gas phase alkylation among the catalysts examined.

• 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.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1665-1666
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• 2009

• Korean Journal of Chemical Engineering
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• v.35 no.11
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• pp.2172-2184
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• 2018

The production of isophthalic acid (IPA) from the oxidation of m-xylene (MX) by air is catalyzed by $H_3PW_{12}O_{40}$ (HPW) loaded on carbon and cobalt. We used $H_2O_2$ solution to oxidize the carbon to improve the catalytic activity of HPW@C catalyst. Experiments reveal that the best carbon sample is obtained by calcining the carbon at $700^{\circ}C$ for 4 h after being impregnated in the 3.75% $H_2O_2$ solution at $40^{\circ}C$ for 7 h. The surface characterization displays that the $H_2O_2$ modification leads to an increase in the acidic groups and a reduction in the basic groups on the carbon surface. The catalytic capability of the HPW@C catalyst depends on its surface chemical characteristics and physical property. The acidic groups play a more important part than the physical property. The MX conversion after 180 min reaction acquired by the HPW@C catalysts prepared from the activated carbon modified in the best condition is 3.81% over that obtained by the HPW@C catalysts prepared from the original carbon. The IPA produced by the former is 46.2% over that produced by the latter.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.87-98
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• 2018

The production of IPA from the oxidation of MX is completed under the catalysis of $H_3PW_{12}O_{40}$ (HPW) loaded on carbon and cobalt. Oxalic acid is tried to modify the carbon to upgrade the catalytic activity of HPW@C catalyst. The experiments show that the best carbon is acquired by carbonizing the carbon at $450^{\circ}C$ for 2 h in $N_2$ after being soaked in a $0.20mol\;l^{-1}$ oxalic acid solution for 16 h. The IPA produced by the HPW@C catalysts prepared with the carbon modified is 58.9% over that obtained by the catalysts prepared with the original carbon.

• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.14-18
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• 2011

Esterification of methacrylic acid with ethylene glycol was carried out over Heteropolyacids [HPA: $H_4SiW_{12}O_{40}$ (STA) and $H_3PW_{12}O_{40}$ (PTA)] supported on ZSM-5. For comparison, the same reaction was carried out over unsupported HPA, $H_2SO_4$, $BF_3$ and PTSA. Among the catalysts studied, HPA showed better activity compared to $H_2SO_4$, $BF_3$ and PTSA. Catalytic activity was compared with HPA supported ZSM-5 catalysts. Typical results indicated that 30 wt% PTA supported on ZSM-5 showed nearly the same activity as that of bulk PTA. It was found that the reaction follows first order kinetics with respect to methacrylic acid. The reaction products were identified by $^1H$-NMR and FT-IR.

• 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.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).