Assessing the effect of light intensity and light wavelength spectra on the photoreduction of formic acid using a graphene oxide material

Author(s):  
Luis A. Ramos-Huerta ◽  
Lotte Laureys ◽  
Alexis G. Llanos ◽  
Patricio J. Valadés ◽  
Richard S. Ruiz ◽  
...  

AbstractPhotocatalysis has been a topic of interest in recent years for both, oxidation and reduction reactions, and although there is a broad variety of research regarding photocatalytic materials and the reaction itself, studies on reactor design and related phenomena, radiation transfer and its direct impact on reaction extent specifically, are usually neglected. From this end, the present work focuses on the elucidation of the effect of light intensity and wavelength spectra in the visible light region during the photoreduction reaction of formic acid using graphene oxide as a promising catalyst. By using formic acid, one of the main intermediaries in the photoreduction of carbon dioxide, the possibility of methanol production is evaluated without the thermodynamic constraints presented by carbon dioxide. A graphene oxide material, synthetized through a modified Hummer’s method, is assessed for the reduction of formic acid evaluating four different light sources (red, green, blue and white). An analysis of energy balances in the reaction set-up allows the determination of both the energy absorbed by the GO photocatalyst and isoactinity conditions at studied radiative operating conditions. At an isoactinity environment, the adsorption rate of formic acid and production rate of methanol are then evaluated, relating them to the absorbed energy achieved at the wavelength spectra and light intensities evaluated; IR spectroscopy is utilized to follow formic acid concentration as well as methanol production. The largest initial reaction rate (ca. 57%) relates to the use of the red wavelength at its largest intensity. Reaction rates at larger times start to be apparent being affected by adsorption, reaction and radiation conditions. The maximum conversion, 14%, is attained by using the white wavelength spectra at its lowest intensity. Thus, higher intensities will not necessarily yield higher conversions, nor the highest reaction rates. This, in turn, poses the necessity of quick, reliable assessments for whichever catalyst used in this type of reactions that leads to the correct election of operating conditions that maximize the product yield. Independent evaluation for every wavelength within the visible spectra and assessing carbon dioxide photoreduction are future steps into the elucidation of solar fuel production feasibility.

2015 ◽  
Vol 183 ◽  
pp. 197-215 ◽  
Author(s):  
Nora Meiri ◽  
Yakov Dinburg ◽  
Meital Amoyal ◽  
Viatcheslav Koukouliev ◽  
Roxana Vidruk Nehemya ◽  
...  

Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer–Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe–Al–O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.


Energies ◽  
2020 ◽  
Vol 13 (24) ◽  
pp. 6608
Author(s):  
Prapatsorn Borisut ◽  
Aroonsri Nuchitprasittichai

Methanol production via carbon dioxide (CO2) hydrogenation is a green chemical process, which can reduce CO2 emission. The operating conditions for minimum methanol production cost of three configurations were investigated in this work. An artificial neural network with Latin hypercube sampling technique was applied to construct model-represented methanol production. Price sensitivity was performed to study the impacts of the raw materials price on methanol production cost. Price sensitivity results showed that the hydrogen price has a large impact on the methanol production cost. In mathematical modeling using feedforward artificial neural networks, four different numbers of nodes were used to train artificial neural networks. The artificial neural network with eight numbers of nodes showed the most suitable configuration, which yielded the lowest percent error between the actual and predicted methanol production cost. The optimization results showed that the recommended process design among the three studied configurations was the process of methanol production with two reactors in series. The minimum methanol production cost obtained from this configuration was $888.85 per ton produced methanol, which was the lowest methanol production cost among all configurations.


2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Fereshteh Samimi ◽  
Mehrzad Feilizadeh ◽  
Seyedeh Bahareh Najibi ◽  
Mohammad Arjmand ◽  
Mohammad Reza Rahimpour

AbstractThe conversion of CO2 to methanol holds great promise, as it offers a pathway to reduce CO2 level in the atmosphere and also produce valuable components. In this study, a typical methanol synthesis plant for CO2 conversion was numerically modeled. Effect of fresh feed to plant parameters (i.e., pressure and CO2 concentration) as well as the influence of recycle ratio on the reactor performance was investigated. Hence, all essential equipment, including compressor, mixer, heat exchanger, reactor, and liquid–vapor separator were considered in the model. Then, at the best operating conditions, thermal behavior and components distribution along the length and radius of the reactor were predicted. Finally, the effect of inert gases was investigated in the methanol production process and the results were compared with the conventional route (CR), which uses natural gas for methanol synthesis. The results revealed that in the absence of inert gases and by employing a recycle stream in the process, CO2 hydrogenation leads to 13 ton/day production of methanol more than CR. While in the feedstock containing 20% inert gases, which is closer to the realistic case, methanol production rate is 45 ton/day lower than CR. These findings prospect a promising approach for the production of green methanol from carbon dioxide and hydrogen.


2019 ◽  
Vol 142 (6) ◽  
Author(s):  
A. Hasan ◽  
I. Dincer

Abstract One of the main solutions to climate change is to harness energy from renewable and clean resources. A novel ocean thermal energy conversion (OTEC) system is proposed for the production of methanol; cooling and power is developed and energetically analyzed. In this proposed trigeneration system, a two-stage Rankine cycle that operates on the inherent temperature difference along the depth of the ocean is used for power production, along with an electrolytic cation exchange membrane (ECEM) reactor for carbon dioxide and hydrogen production to feed the methanol production system. The carbon dioxide is sourced from the deep cold seawater, where the concentrations are found to be the highest. The proposed system performance is modeled and simulated on the Aspen Plus, where the performance of the proposed system is assessed under various operating conditions. The results of this study shows that the maximum net power output of the cycle is found to be 51.5 GW, with a fixed rate of district cooling of 69.0 GW. The maximum methanol production rate was found to be 1.36 kg/s at the power input of 51.5 GW. The system is tested under three different operation cases, to fully assess its viability. It should be noted that in all three cases district cooling is included as a product of the system. Case 1: ECEM reactor operates at its current efficiency with fuel production, Case 2: ECEM reactor operates at proton exchange membrane (PEM) efficiency, and Case 3: Only power was produced with no fuel. The maximum overall energy efficiency of the cycle was found to be 8.0, 8.6, and 7.3% for Cases 1, 2, and 3, respectively.


2014 ◽  
Vol 906 ◽  
pp. 118-124
Author(s):  
Cheng Tung Chou ◽  
Yu Jie Huang ◽  
Hong Sung Yang

Global warming has become more and more serious, which is caused by greenhouse gases. Cutting down the emission of CO2 has already become one of the major research target in the world. This study is numerically investigating Thermal Swing Sorption Enhanced Reaction Process on water gas shift (WGS) reaction by Na2O-promoted alumina. According to Le Chateliers law, the forward reaction rates and conversion can be increased by removing some products selected. Therefore, this concept can be used to generate product of high-purity hydrogen. The purified H2 can be sent to gas turbine for generating electrical power or can be used for other energy source. Carbon dioxide can also be recovered and sequestrated to reduce greenhouse gas effects. The method of lines is utilized in simulation, combined with upwind differences, cubic spline approximation and LSODE of ODEPACK software to solve the problem. The concentration, temperature, and adsorption quantity in the bed are integrated with respect to time by LSODE of ODEPACK software. The simulation is stopped when the system reaches a cyclic steady state. In this study, we first simulate breakthrough curve of Na2O-promoted alumina cited from literatures to prove the accuracy of simulation program. The optimal operating conditions of the WGS TSA (temperature swing adsorption) single-bed six-process is obtained by varying operating variables, such as feed time and rinse time. Furthermore, WGS TSA single-bed six-process could achieve 99.89% purity of H2 (dry-basis) as the top product and 90.95% purity and 98.22% recovery of CO2 (dry-basis) as the bottom product.


2018 ◽  
Vol 27 ◽  
pp. 107-114 ◽  
Author(s):  
Santosh Kumar ◽  
Rajesh K. Yadav ◽  
Kirpa Ram ◽  
António Aguiar ◽  
Joonseok Koh ◽  
...  

1998 ◽  
Vol 3 (3) ◽  
Author(s):  
María I. Cabrera ◽  
Orlando M. Alfano ◽  
Alberto E. Cassano

AbstractQuantum efficiencies of the photocatalytic decomposition of trichloroethylene employing a suspension of titanium dioxide in water and polychromatic radiation have been investigated. Aldrich, Degussa P25 and Hombikat 100 titanium dioxides were studied using an approach that permits the correct evaluation of the true absorbed UV radiation. Computed results using initial reaction rates show that differences in efficiencies among the different varieties of titanium dioxides are not very dramatic. However, reaction conversion after several hours of identical operating conditions favors the use of the Aldrich catalyst. Quantum efficiencies show an important dependence with the initial reactant concentration, the irradiation intensity and the catalyst loading. Under some operating conditions, quantum efficiencies as high as 50 % were measured.


2014 ◽  
Vol 39 (29) ◽  
pp. 16506-16512 ◽  
Author(s):  
Hak-Yoon Kim ◽  
Insoo Choi ◽  
Sang Hyun Ahn ◽  
Seung Jun Hwang ◽  
Sung Jong Yoo ◽  
...  

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