Gas phase dehydration of glycerol catalyzed by rutile TiO_2-supported heteropolyacids

Lingqin Shen,Aili Wang,Hengbo Yin,Yonghai Feng,Longbao Yu,Tingshun Jiang,Yutang Shen,Zhanao Wu,박은덕 한국공업화학회 2011 Journal of Industrial and Engineering Chemistry Vol.17 No.3

Gas phase dehydration of glycerol catalyzed by the rutile TiO2-supported heteropolyacids was investigated. The TiO_2-supported heteropolyacid catalysts were prepared by the incipient wetness impregnation method using silicotungstic, phosphotungstic, and phosphomolybdic acids as active compounds. The as-prepared catalysts were characterized by X-ray diffraction, infrared spectroscopy,temperature programmed desorption of ammonia, and surface area measurement. The heteropolyacids supported by rutile TiO_2 were crystallites. The catalytic activity of the catalysts in the gas phase dehydration of glycerol was significantly affected by the type and loading of heteropolyacids. TiO_2-supported silicotungstic acid (20 wt.%) catalyst showed the highest catalytic activity with an acrolein selectivity of 80 mol% at a conversion of glycerol of 99% and a reaction temperature of 280 8C under ambient pressure. The possible reaction route in the gas phase dehydration of glycerol catalyzed by the TiO_2-supported heteropolyacid catalysts was also discussed briefly.

Articles : Design of Heteropoly Compound-Imbedded Polymer Film Catalysts And Their Application

( Wha Young Lee ),( In Kyu Song ),( Jong Koog Lee ),( Gyo Ik Park ),( Seong Soo Lim ) 한국화학공학회 1997 Korean Journal of Chemical Engineering Vol.14 No.6

Heteropolyacid-imbedded polymer film catalysts were applied for the vapor-phase catalytic reaction. Thin film catalysts were prepared by membrane technology using homogeneous heteropolyacid-polymer solutions. It was found that heteropolyacid was finely and uniformly dispersed throughout the polymer matrix. Heteropolyacid catalyst could be designed by this method to enhance acid or oxidation catalysis. Future aspects of the film catalyst were also described in this work.

Research Papers : A Composite Catalytic Polymer Membrane Reactor Using Heteropolyacid-Blended Polymer Membrane

( Jun Seon Choi ),( In Kyu Song ),( Wha Young Lee ) 한국화학공학회 2000 Korean Journal of Chemical Engineering Vol.17 No.3

Keggin형 H3+xPW12-xNbxO40 (x=0, 1, 2, 3) 및 Wells-Dawson형 H6+xP2W18-xNbxO62 (x=0, 1, 2, 3) 헤테로폴리산 촉매를 이용한 n-Butanol로부터 Din-Butyl Ether의 제조

김정권 ( Jeong Kwon Kim ),최정호 ( Jung Ho Choi ),이종협 ( Jong Heop Yi ),송인규 ( In Kyu Song ) 한국화학공학회 2012 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.50 No.2

Etherification of n-butanol to din-Butyl Ether was carried out over Keggin H3+xPW12-xNbxO40 (x=0, 1, 2, 3) and H6+xP2W18-xNbxO62 (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 31P NMR analyses. Their acid properties were determined by NH3-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 din-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 din-Butyl Ether.

Review on oxidative desulfurization of fuel by supported heteropolyacid catalysts

Jiarong Li,Zhi Yang,Siwen Li,Qiping Jin,Jianshe Zhao 한국공업화학회 2020 Journal of Industrial and Engineering Chemistry Vol.82 No.-

Desulfurization of fuel has been an important issue in fuel refining process. Hydrodesulfurization, as atraditional and commercial desulfurization technique for removing sulfur compounds, has been widelyresearched for decades. But as the environmental policy implemented on fuel becoming stricter, it ismore difficult to remove organic sulfur compounds by hydrodesulfurization technology. Therefore, nonhydrodesulfurizationtechnologies developed rapidly in recent years. Among all novel desulfurizationtechnologies, oxidative desulfurization (ODS) functions best with its mild reaction condition and efficientdesulfurization capacity. Heteropolyacid (HPA) has been intensively investigated because the HPA hasdiscrete ionic structure and high proton mobility, which makes it extremely promising in catalysis. As aresult, HPA has been applied in a variety of synthetically selective transformations of organic substancesand the ODS is one of them. However, HPA have shortcomings such as their high solubility in polarsolvents and low specific surface area. To overcome these problems, many works have been done tocombine heteropolyacids with other materials. The main derivatives of HPA used in ODS are supportedheteropolyacid, phase transfer heteropolyacid catalyst and polyoxometalate based ionic liquid. Thecatalytic activity and reusability of HPA are substantially increased after modification. The works onheteropolyaicds for ODS from 2010 to 2019 will be summarized in this review.

Keggin형 헤테로폴리산에 의한 과당의 5-하이드록시메틸퍼퓨랄로의 전환을 위한 탈수반응

백자연(Jayeon Baek),윤형진(Hyeong Jin Yun),김남동(Nam Dong Kim),최영보(Youngbo Choi),이종협(Jongheop Yi) 한국청정기술학회 2010 청정기술 Vol.16 No.3

과당(fructose)로부터 간단한 공정을 통하여 바이오디젤보다 우수한 청정에너지 연료로 알려진 5-하이드록시메틸퍼퓨랄(HMF)을 제조하는 청정공정을 개발하였다. 이 연구에서는 중심원소와 배위원소가 치환된 네 종류의 헤테로폴리산 HnXM12O40 (중심원소 X = P, Si, 배위원소 M = W, Mo.)을 과당으로부터 HMF로 전환하는 탈수반응에 적용하고, 그 반응활성을 비교하였다. 헤테로폴리산의 산 세기는 중심원소가 P, 배위원소가 W일 때 더 높았으며 산 점의 수는 이와 반대되는 경향을 보였다. 과당의 HMF로의 탈수반응은 헤테로폴리산의 산 특성과 음이온의 연성(softness)과 밀접한 관련이 있으며, 촉매 활성점과 전환율이 상쇄작용하여 네 종류의 헤테로폴리산 촉매는 서로 비슷한 활성을 보였다. 또한 반응에 사용된 헤테로폴리산을 반응온도보다 높은 200℃에서 열처리한 후에도 그 결정구조가 유지되는 것을 확인하였으며, 이를 통하여 헤테로폴리산의 반응활성이 안정적으로 유지됨을 확인할 수 있었다. Four Keggin-type heteropolyacids, HnXM12O40(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 activityof heteropolyacids, and the softness of polyanion. In addition, it was observed that the prepared heteropolyacids showed good structural stability after heat treatment at 200℃.

Amino-anchored sulfonic acid-functionalized heteropolyacid ionic liquid: A highly selective and recyclable catalyst for the Baeyer-Villiger oxidation of cyclohexanone

Xiangshan Li,Yong Zhu,Dachuan Xia,Zhanke Wang,Guangxu Zhang 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.127 No.-

A novel amino-anchored sulfonic acid functional heteropolyacid ionic liquid ([NHSO]3PW12O40) wasdesigned, synthesized and used as a catalyst in the Baeyer-Villiger (BV) oxidation of cyclohexanone tosynthetic e-caprolactone (e-CL). The catalyst was well characterized by FT-IR, XRD, 1H NMR, XPS, TGDTAand SEM analysis methods, which showed that the tungsten phosphate anion (PW12O403) was successfullymodified from the sulphonate-functionalised IL precursor NHSO and formed a new hydrogenbond between the introduced –NH2 group and PW12O403. The combined effect of ionic bonds and hydrogenbonds contributed to the good stability of the catalyst. Catalyst activity evaluation experiments confirmedthat [NHSO]3PW12O40 exhibited superior performances such as a cyclohexanone conversion of86% and e-CL yield and selectivity of 82% and 95%, respectively. Furthermore, [NHSO]3PW12O40 couldbe recovered by simple treatment and the activity of the catalyst did not decrease significantly after fivereplicae experiments. In addition, the reaction kinetics and mechanism of the catalyst were investigatedand a simple validation was given in conjunction with the bond energy changes of the catalyst during thereaction. The innovative of the green, stable and high-performance functionalised heteropolyacid IL catalystprovides a new solution for the efficient production of e-CL.

Esterification of Methacrylic acid with Ethylene glycol over Heteropolyacid supported on ZSM-5

A. Prabhakarn,J. A. Fereiro,Ch. Subrahmanyam 대한화학회 2011 대한화학회지 Vol.55 No.1

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.

Heteropolyacid supported on Zr-Beta zeolite as an active catalyst for one-pot transformation of furfural to γ-valerolactone

Winoto, Haryo Pandu,Fikri, Zuhroni Ali,Ha, Jeong-Myeong,Park, Young-Kwon,Lee, Hyunjoo,Suh, Dong Jin,Jae, Jungho Elsevier 2019 Applied Catalysis B Vol.241 No.-

<P><B>Abstract</B></P> <P>A novel bifunctional catalyst that enables an efficient one-pot conversion of furfural into γ-valerolactone (GVL) has been developed by anchoring heteropolyacid (HPA) on Zr-Beta zeolite. The catalysts were prepared by a post-synthesis procedure, which consists of the dealumination of Al-Beta, incorporation of Zr into the beta framework through solid-state ion-exchange and impregnation of the HPA. Zr-Beta is used as a Lewis acid catalyst to catalyze the transfer hydrogenation of furfural and levulinic acid/ester using 2-propanol as a hydrogen donor. To deal with the inability of Zr-Beta to catalyze the hydrolytic ring-opening of furans toward GVL, phosphotungstic acid (HPW) and silicotungstic acid (HSiW) were introduced to the Zr-Beta as BrØnsted acid sites. The characterization of the catalysts using XRD, UV–vis and XPS as well as TPD of ammonia and FT-IR spectroscopy of the adsorbed pyridine revealed that the HPA/Zr-Beta possesses both isolated Lewis and BrØnsted acid sites. When they were applied to the one-pot cascade conversion of furfural, the initial activity of the HPA/Zr-Beta toward GVL production were 2–3 times greater than that for Zr-Beta due to the enhanced hydrolytic ring-opening of the furans promoted by the added BrØnsted acidity. Especially, HPW loaded Zr-Beta demonstrated a remarkable GVL yield of ∼70% at 433 K after 24 h due to its high thermal stability and stronger BrØnsted acidity, and its activity far surpasses that of the conventional Sn-Al-Beta zeolite (∼40%). Overall, this study demonstrates that an incorporation of HPA into Lewis acid Sn- or Zr-Beta zeolites is an effective strategy to create isolated Lewis and BrØnsted acid sites within a single catalyst, thereby allowing the selective cascade catalysis for the cost-effective production of high-value chemicals.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Heteropolytungstae (HPW)-loaded Zr-Beta is synthesized via a simple post-synthesis method. </LI> <LI> The method consists of dealumination of Al-Beta followed by sequential incorporation of Zr and HPW. </LI> <LI> HPW/Zr-Beta zeolite possesses both isolated Lewis and Brønsted acid sites. </LI> <LI> Transfer hydrogenation and ring-opening reactions is effectively combined using a single catalyst. </LI> <LI> One-pot cascade conversion of furfural to GVL with a high yield (∼70%) is achieved. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Direct preparation of dichloropropanol from glycerol and hydrochloric acid gas using heteropolyacid (HPA) catalyst by heterogeneous gas phase reaction

Sun Ho Song,Dong Ryul Park,Sung Yul Woo,Won Seob Song,Myong Suk Kwon,송인규 한국공업화학회 2010 Journal of Industrial and Engineering Chemistry Vol.16 No.5

Direct preparation of dichloropropanol (DCP) from glycerol and hydrochloric acid gas was carried out in a heterogeneous gas phase reactor using H3PMo12XWXO40 (X = 0, 3, 6, 9, and 12), H4SiW12O40, and H4SiMo12O40 heteropolyacid (HPA) catalysts. Acid property of the HPA catalyst was determined by NH3-TPD measurement in order to correlate the catalytic activity with the acid property of the catalyst. Acid strength of the HPA catalyst played a key role in determining the catalytic performance in the reaction. Yield for DCP increased with increasing acid strength of the catalyst. Among the catalysts tested,H3PW12O40 with the highest acid strength showed the highest yield for DCP. 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.