Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide by Heteropolyacid/Metal Oxide Catalysts

2007 ◽  
Vol 119 ◽  
pp. 287-290 ◽  
Author(s):  
Kyung Won La ◽  
Min Hye Youn ◽  
Jin Suk Chung ◽  
Sung Hyeon Baeck ◽  
In Kyu Song
Keyword(s):  
Carbon Dioxide ◽  
Metal Oxide ◽  
Dimethyl Carbonate ◽  
Batch Reactor ◽  
Direct Synthesis ◽  
Sol Gel ◽  
Catalytic Performance ◽  
Acid Sites ◽  
Pure Ceo2 ◽  
Autoclave Reactor

CexTi1-xO2 and H3PW12O40/CexTi1-xO2 catalysts were prepared by sol-gel method, and they were applied to the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in a batch reactor. The reaction was carried out in an autoclave reactor at 170oC and 5 MPa. It was found that CexTi1-xO2 exhibited a higher catalytic performance than pure CeO2 and TiO2. The catalytic performance of CexTi1-xO2 was the maximum when x=0.1. It was also revealed that H3PW12O40/CexTi1-xO2 catalysts showed a remarkably enhanced catalytic performance than the corresponding CexTi1-xO2 catalysts. The amount of DMC produced by 15 wt% H3PW12O40/ Ce0.1Ti0.9O2 catalyst was six times higher than that produced by Ce0.1Ti0.9O2 catalyst. It is concluded that both Brönsted acid sites provided by H3PW12O40 and base sites in CexTi1-xO2 played an important role in improving the catalytic performance of H3PW12O40/CexTi1-xO2.

scholarly journals Glycerol Hydrogenolysis to 1,2-Propanediol over Novel Cu/ZrO2 Catalysts

Catalysts ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 72
Author(s):  
Giuseppina Luciani ◽  
Giovanna Ruoppolo ◽  
Gianluca Landi ◽  
Valentina Gargiulo ◽  
Michela Alfè ◽  
...  
Keyword(s):  
Batch Reactor ◽  
Metal Organic Framework ◽  
Sol Gel ◽  
Catalytic Performance ◽  
Acid Sites ◽  
Weak Acid ◽  
Copper Deposition ◽  
Biodiesel Production ◽  
Preparation Methods ◽  
Glycerol Hydrogenolysis

Glycerol is the main by-product of biodiesel production; its upgrading to more valuable products is a demanding issue. Hydrogenolysis to 1,2-propanediol is one of the most interesting processes among the possible upgrading routes. In this study, we propose novel copper/zirconia catalysts prepared by advanced preparation methods, including copper deposition via metal–organic framework (MOF) and support preparation via the sol–gel route. The catalysts were characterized by N2 physisorption, X-ray diffraction, Scanning Electron Microscopy, H2-TPR and NH3-TPD analyses and tested in a commercial batch reactor. The catalyst prepared by copper deposition via MOF decomposition onto commercial zirconia showed the best catalytic performance, reaching 75% yield. The improved catalytic performance was assigned to a proper combination of redox and acid properties. In particular, a non-negligible fraction of cuprous oxide and of weak acid sites seems fundamental to preferentially activate the selective pathway. In particular, these features avoid the overhydrogenolysis of 1,2-propanediol to 1-propanol and enhance glycerol dehydration to hydroxyacetone and the successive hydrogenation of hydroxyacetone to 1,2-propanediol.

Direct Synthesis of DMC from CO2 and CH3OH over CexZr 1-x-0.1Y 0.1 O2 Catalysts

2011 ◽  
Vol 287-290 ◽  
pp. 1632-1635 ◽  
Author(s):  
Zhi Fang Zhang ◽  
Rui Bing Wang ◽  
Xiang Rong Ma
Keyword(s):  
Solid Solution ◽  
Catalytic Activity ◽  
Solid Solutions ◽  
Dimethyl Carbonate ◽  
Direct Synthesis ◽  
Sol Gel ◽  
Catalytic Performance ◽  
Solid Solution Series ◽  
Calcination Temperatures ◽  
Bimodal Pore Structure

The solid solution series CexZr(1-x-0.1)Y0.1O2 with various x values was prepared by the citric acid sol-gel method, using cerium and zirconium nitrides as precursors, respectively.The characterization results of the XRD, N2 sorption measurements indicated that the physical properties of the solid solutions were significantly affected by the x values in CexZr(1-x-0.1)Y0.1O2 and the calcination temperatures. These solid solutions can be used as catalyst for the direct synthesis of dimethyl carbonate from CH3OH and CO2. Results indicated that the catalytic activity for DMC synthesis was influenced by the structure of the solid solutions and the x values in CexZr(1-x-0.1)Y0.1O2. The optimized Ce0.5Zr0.4Y0.1O2 with bimodal pore structure exhibited higher catalytic performance to DMC synthesis.

scholarly journals Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

2019 ◽  
pp. 88-99 ◽  
Author(s):  
Oscar Felipe Arbeláez-Pérez ◽  
Sara Dominguez Cardozo ◽  
Andrés Felipe Orrego-Romero ◽  
Aida Luz Villa Holguin ◽  
Felipe Bustamante Londoño
Keyword(s):  
Carbon Dioxide ◽  
Catalytic Activity ◽  
Activated Carbon ◽  
Gas Phase ◽  
Dimethyl Carbonate ◽  
Direct Synthesis ◽  
Dispersion Analysis ◽  
Molar Ratio ◽  
Rate Determining Step ◽  
Carbonate Formation

The catalytic activity for dimethyl carbonate formation from carbon dioxide and methanol over mono and bimetallic Cu:Ni supported on activated carbon is presented. Bimetallic catalysts exhibit higher catalytic activity than the monometallic samples, being Cu:Ni-2:1 (molar ratio) the best catalyst; X-Ray diffraction, transmission electron microscopy, and metal dispersion analysis provided insight into the improved activity. In situ FT-IR experiments were conducted to investigate the mechanism of formation of dimethyl carbonate from methanol and carbon dioxide over Cu-Ni:2-1. The kinetics of the direct synthesis of dimethyl carbonate in gas phase over Cu:Ni-2:1 supported on activated carbon catalyst was experimentally investigated at 12 bar and temperatures between 90 oC and 130 oC, varying the partial pressures of CO2 and methanol. Experimental kinetic data were consistent with a Langmuir–Hinshelwood model that included carbon dioxide and methanol adsorption on catalyst actives sites (Cu, Ni and Cu-Ni), and the reaction of adsorbed CO2 with methoxi species as the rate determining step. The estimated apparent activation energy was 94.2 kJ mol-1.

scholarly journals The Role of Nitrate on the Sol-Gel Spread Self-Combustion Process and Its Effect on the NH3-SCR Activity of Magnetic Iron-Based Catalyst

Catalysts ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 314
Author(s):  
Xing Ning ◽  
Zhi-bo Xiong ◽  
Bin Yang ◽  
Wei Lu ◽  
Shui-mu Wu
Keyword(s):  
Nitric Acid ◽  
Citric Acid ◽  
Sol Gel ◽  
Nox Reduction ◽  
Combustion Process ◽  
Catalytic Performance ◽  
Metal Nitrate ◽  
Acid Sites ◽  
Complexing Agent ◽  
Nh3 Scr

Sol-gel spread self-combustion is the burning of the complexing agent in dried gel and the oxidant. Meanwhile, high temperature takes place during the combustion process, which is harmful to the pore structure of the catalyst. The nitrate from metal nitrate precursors as an oxidant could participate in the spread of the self-combustion process. Therefore, the influence of nitrate from metal nitrate on the spread self-combustion of an iron–cerium–tungsten citric acid gel and its catalytic performance of NOx reduction were investigated by removing nitrate via the dissolution of washing co-precipitation with citric acid and re-introducing nitric acid into the former solution. It was found that the removal of nitrate contributes to enhancing the NH3–SCR activity of the magnetic mixed oxide catalyst. The NOx reduction efficiency was close to 100% for Fe85Ce10W5–CP–CA at 250 °C while the highest was only 80% for the others. The results of thermal analysis demonstrate that the spread self-combustion process of citric acid dried gel is enhanced by re-introducing nitric acid into the citric acid dissolved solution when compared with the removal of nitrate. In addition, the removal of nitrate helps in the formation of γ-Fe2O3 crystallite in the catalyst, refining the particle size of the catalyst and increasing its pore volume. The removal of nitrate also contributes to the formation of Lewis acid sites and Brønsted acid sites on the surface of the catalyst compared with the re-introduction of nitric acid. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) demonstrates that both Eley–Rideal (E–R) and Langmuir–Hinshelwood (L–H) mechanisms exist over Fe85Ce10W5–CP–CA at 250 °C with E–R as its main mechanism.

Direct Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over CeO2(X)–ZnO(1−X) Nano-Catalysts

2013 ◽  
Vol 13 (12) ◽  
pp. 8116-8120 ◽  
Author(s):  
Ki Hyuk Kang ◽  
Wangrae Joe ◽  
Chang Hoon Lee ◽  
Mieock Kim ◽  
Dong Baek Kim ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Dimethyl Carbonate ◽  
Direct Synthesis ◽  
Nano Catalysts

Synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by Perchlorated Zirconia (HClO4/ZrO2) nanoparticles as a novel solid acid catalyst

2018 ◽  
Vol 2 (2) ◽  
Author(s):  
Seyed Yousef Mosavian
Keyword(s):  
Solid Acid ◽  
Condensation Reaction ◽  
Solid Acid Catalyst ◽  
Sol Gel ◽  
Acid Catalyst ◽  
Catalytic Performance ◽  
Acid Sites ◽  
Zro2 Nanoparticles ◽  
Calcination Temperatures ◽  
Aldehydes And Ketones

Zirconia was synthesized in nanosize by sol-gel method and perchlorated zirconia (HClO4/ZrO2) with various calcination temperatures were prepared and characterized by XRD, FTIR and SEM techniques. The catalyst acidity characters, including the acidicstrength and the total number of acid sites were determined by potentiometric titration. The catalytic performance experiments show that the HClO4/ZrO2 with calcination temperature of 300 °C has the best catalytic activity. 2,3-Dihydroquinazolin-4(1H)-ones wereprepared in good to excellent yields via condensation reaction of oaminobenzamide and various types of aldehydes and ketones in the presence of HClO4/ZrO2 nanoparticles as an efficient solid acid catalyst. The catalyst is reusable with moderate loss in activity.

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