Engineered Catalyst Based on MIL-68(Al) with High Stability for Hydrogenation of Carbon Dioxide and Carbon Monoxide at Low Temperature.

Today, the importance of decreasing and converting COx gases from the atmosphere into value-added chemicals by catalytic hydrogenation reactions has become one crucial challenge. In the current work, to facilitate the hydrogenation of COx, several mesoporous alumina catalysts with high efficiency and stability were synthesized using the MIL-68(Al) platform, a nanoporous MOF with a high surface area as a precatalyst, encapsulating nickel or nickel-iron nanoparticles (NPs). After removing the organic linker of MIL-68(Al) by calcination in air, two types of catalysts, promoted and unpromoted, were obtained with various loads of nickel and iron. A set of analyses (PXRD, BET-N2, TEM, FE-SEM, ICP-OES, EDX-map, CO2-TPD, H2-TPR, and H2-TPD) were performed to evaluate the physicochemical properties of catalysts. Based on the analysis results, the promoted catalyst had smaller particles and pores due to the effective and uniform distribution of nickel NPs. Also, H2-TPR and CO2-TPD results in samples containing Fe promoter demonstrated the facilitation of the reduction process and the adsorption and activation of CO2, respectively. The results of CO2 methanation indicated an improved catalytic performance for promoted samples, especially at low temperatures (200-300 °C), compared to unpromoted catalysts. 5Fe·15Ni@Al2O3 MIL-68(Al) catalyst displayed the best performance compared to other catalysts, with a conversion of 92.4% and selectivity of 99.6% at 350 °C and GHSV = 2500 h-1. Moreover, the 5Fe·15Ni@Al2O3 MIL-68(Al) catalyst facilitated the CO2 methanation reaction by reducing the activation energy to 42.5 kJ mol-1 compared with other reported catalysts. Both types of catalysts performed 100% hydrogenation of CO to CH4 with full selectivity at 250 °C and exhibited high stability for at least 100 h at 300 °C. Notably, such high significant catalytic performance is only achieved by the usage of the "MOFs templating strategy" due to the high surface area for the effective distribution of NPs, the strong metal-support interaction, and the formation of nickel aluminate species, preventing the sintering of NPs.

CO2 absorption/desorption rates in aqueous DEEA/MDEA and sulfolane-contained hybrid solutions: effects of physical properties and reaction rate.

The rates of CO2 absorption into fresh and regenerated aqueous solutions of N,N-diethylethanolamine (DEEA), N-methyldiethanolamine (MDEA), and their mixture with sulfolane are investigated in a batch stirred cell reactor. The data are obtained in the temperature range of 293.15-313.15 K, pressures up to 800 kPa, and different concentrations of alkanolamines and sulfolane. The diffusion coefficients and Henry's law constants for all the solutions are obtained. The absorption rate of DEEA solutions increased by increasing component concentrations and pressure, but the effects of temperature on the absorption rates of hybrid and aqueous DEEA solutions are different. Comparison of absorption rates in aqueous and hybrid solutions under the same conditions can determine the role of sulfolane as the physical solvent. It has been found that sulfolane acts as an effective absorption activator in the hybrid DEEA solutions. However, in the MDEA solutions, in all experimental conditions except for high pressure ([Formula: see text] 400 kPa) and certain MDEA concentration (20 wt%), sulfolane has a negative effect on the absorption rate. The absorption rates of regenerated aqueous DEEA solutions are in the range of 50.5-87.7% of fresh ones, while these values for the hybrid DEEA solution are in the range of 75-90.5%. These values for the aqueous and hybrid MDEA solutions are almost equal. Based on the values of Hatta number and enhancement factor, the CO2 absorption regime in the DEEA solutions is determined as the fast second-order reaction. The absorption rate can be interpreted considering the tradeoff between kinetics and thermodynamics of CO2 absorption in the aqueous and hybrid DEEA/MDEA solutions. The desorption rates in hybrid DEEA/MDEA solutions are higher than those in aqueous solutions.

Ultrasonication-assisted synthesis of 2D porous MoS2/GO nanocomposite catalysts as high-performance hydrodesulfurization catalysts of vacuum gasoil: Experimental and DFT study.

In this study, a novel, simple, high yield, and scalable method is proposed to synthesize highly porous MoS2/graphene oxide (M-GO) nanocomposites by reacting the GO and co-exfoliation of bulky MoS2 in the presence of polyvinyl pyrrolidone (PVP) under different condition of ultrasonication. Also, the effect of ultrasonic output power on the particle size distribution of metal cluster on the surface of nanocatalysts is studied. It is found that the use of the ultrasonication method can reduce the particle size and increase the specific surface area of M-GO nanocomposite catalysts which leads to HDS activity is increased. These nanocomposite catalysts are characterized by XRD, Raman spectroscopy, SEM, STEM, HR-TEM, AFM, XPS, ICP, BET surface, TPR and TPD techniques. The effects of physicochemical properties of the M-GO nanocomposites on the hydrodesulfurization (HDS) reactions of vacuum gas oil (VGO) has been also studied. Catalytic activities of MoS2-GO nanocomposite are investigated by different operating conditions. M9-GO nanocatalyst with high surface area (324 m2/g) and large pore size (110.3 Å), have the best catalytic performance (99.95%) compared with Co-Mo/γAl2O3 (97.91%). Density functional theory (DFT) calculations were also used to elucidate the HDS mechanism over the M-GO catalyst. It is found that the GO substrate can stabilize MoS2 layers through weak van der Waals interactions between carbon atoms of the GO and S atoms of MoS2. At both Mo- and S-edges, the direct desulfurization (DDS) is found as the main reaction pathway for the hydrodesulfurization of DBT molecules.

Catalytic activity of synthesized 2D MoS2/graphene nanohybrids for the hydrodesulfurization of SRLGO: experimental and DFT study.

Hydrodesulfurization (HDS) of straight run light gas oil (SRLGO) using novel highly active two-dimensional (2D) MoS2/graphene (G) nanohybrid catalysts is a precursor technology for the production of clean heavy fuel. The aim of this research is the synthesis of 2D MoS2/G nanohybrid catalysts by use of exfoliation method from commercial bulky MoS2 and graphite using hydrothermal ball milling system, which is a low-cost, high-yield, and scalable method. These nanohybrid catalysts were characterized by XRD, Raman spectroscopy, XPS, SEM, TEM, STEM, ICP, BET surface, TPR, and TPD techniques. Also, catalytic activities of 2D MoS2/G nanohybrid catalysts were evaluated under different operating conditions such as temperature, pressure, LHSV, and H2/Feed (SRLGO) ratio in the HDS reaction. The conversion of the HDS of SRLGO with 14000 ppm sulfur showed a considerably higher activity of 2D MoS2/G nanohybrid catalyst (99.95% HDS efficiency) compared with the Co-Mo/γAl2O3 as a commercial catalyst (90% HDS efficiency) in the operation condition (340 °C, 40 bars, LHSV: 1 h-1and H2/oil: 600 NL L-1) which is economically valuable. Using density functional theory calculations, the detailed mechanism of the HDS process over MoS2/G catalyst was explored. It was found that sulfur coverage on the Mo edge of MoS2 plays an important role in the hydrogenation of sulfur components.

Experimental studies on high-quality bio-oil production via pyrolysis of Azolla by the use of a three metallic/modified pyrochar catalyst.

In this study, the potential of the pyrolysis method to overcome the negative effects of Azolla-filiculoides in infected areas was thoroughly investigated. Non-catalytic pyrolysis experiments were conducted at a temperature range of 400-700 °C. The highest possible bio-oil yield (35 wt%) was attained at 500 °C. To achieve the best chemical composition of bio-oil and higher amount of synthesis gas the catalytic pyrolysis were conducted in a dual-bed quartz reactor at the optimum temperature (500 °C). Although, all three catalysts (pyro-char, modified pyro-char (MPC), and Mg-Ni-Mo/MPC) showed almost an impressive performance in promotion of the common reactions, Mg-Ni-Mo/MPC catalyst have illustrated the stunning results by increasing the percentage of furan compounds from 5.25% to 33.07%, and decreasing the acid compounds from 25.56% to 9.09%. Using GC-MS and GC-FID liquid and gaseous products were fully analyzed. The carbon-based catalysts were also evaluated via FTIR, FESEM, EDX, and BET analyses.

Using a hybrid-like supported catalyst to improve green fuel production through hydrothermal liquefaction of Scenedesmus obliquus microalgae.

Hydrothermal liquefaction of Scenedesmus obliquus has been optimized in a micro reactor using response surface methodology. Temperature, residence time and feedstock concentration were studied through central composite design to verify the optimized conditions leading to the highest yield of bio-crude and energy recovery. Based on the non-catalytic studies, temperature, feedstock concentration, and their interaction were respectively determined as the most effective variables. In order to improve the quality of produced bio-crude, the one step upgrading procedure was carried out in the presence of synthesized heterogeneous catalysts including Ni/AC, Ni/AC-CeO2 nanorods and Ni/CeO2 nanorods. Although, it was found that, more or less, all the catalysts were able to improve the bio-crude yield and quality based on their specific characteristics, however using Ni/AC-CeO2 hybrid like nanorods, not only the bio-crude yield would be improved by more than 9% but also the bio-crude could be upgraded to a green bio-based fuel.

Preparation of amine functionalized reduced graphene oxide/methyl diethanolamine nanofluid and its application for improving the CO2 and H2S absorption.

A novel approach was examined by addition of amine-modified reduced graphene oxide (rGO) to amine solutions in order to enhance the CO2 absorption capacity of amine solutions. Amine functionalized reduced graphene oxide (rGO)/methyl diethanolamine (MDEA) nanofluid was prepared for absorption of acid gases (CO2, H2S). GO was synthesized via a modified hummer method and functionalized through solvothermal method. As-synthesized NH2-rGO was characterized by XRD, BET, SEM, FTIR, EDX and XPS analysis to determine the structure. NH2-rGO was dispersed in MDEA and displayed excellent stability verified by zeta potential analysis. NH2-rGO/MDEA nanofluid showed high absorption capacity toward CO2 and H2S. The absorption capacity of the solution for CO2 and H2S was promoted up to 16.2% and 17.7%, respectively. Solubility results showed a reverse relationship with increasing temperature. Comparison of solubility data revealed that introducing 0.1 wt% NH2-rGO to 40 wt% had a greater enhancement relative to introducing 0.1 wt% GO to the same solution.

Pyrolysis of marine biomass to produce bio-oil and its upgrading using a novel multi-metal catalyst prepared from the spent car catalytic converter.

In order to reduce the economic and environmental consequences caused by spent car catalyst, we herein report for the first time a novel promising multi-metal catalyst prepared from spent car catalytic converters to upgrade the pyrolysis bio-oils. The physico-chemical properties of prepared catalyst were characterized by XRD, EDS, FESEM, and FT-IR analyses. The thermal stability of the multi-metal catalyst was studied with TGA. To investigate the activity of the catalyst, Conversion of Cladophora glomerata (C. glomerata) into bio-products was carried out via a fixed bed reactor with and without catalyst at the temperature of 500°C. Although the catalyst didn't catalyze the gasification reaction, bio-oil was upgraded over the catalyst. The main effect of the catalyst on the bio-oil components is deoxygenating of nitrogen compounds and promotion the ketonization reaction, which converts acid to ketone and declines the corrosive nature of bio-oil.

Catalytic upgrading of bio-products derived from pyrolysis of red macroalgae Gracilaria gracilis with a promising novel micro/mesoporous catalyst.

Conversion of Gracilaria gracilis (G. gracilis) into bio-products was carried out via pyrolysis at different temperatures to determine its potential for phenol-rich bio-oil. Co-Mo supported on zeolites (HZSM-5), mesoporous (HMS) catalysts and their composites (ZH) were investigated and compared to each other on catalytic pyrolysis processes. In non-catalytic tests, the maximum weight percentage of bio-oil was 42wt% at 500°C and had the maximum amount of phenol (6.28wt%). in the catalytic tests by ZH composites; the addition of zeolite content in the structure of composites significantly decreased total concentrations of acetic acid and formic acid from 9.56 to 8.12wt% and slightly decreased phenol and furfural concentrations from 6.65 and 6.98 to 5.88 and 5.49wt%, respectively. Furthermore, the best selectivity for hydrogen yield (6.08mmol/g macroalgae) and lowest amount of acetic acid (5.4wt%) was observed for CoMo/ZH-20 catalyst, that is synthesized by 20wt% of zeolite.

Hydrothermal gasification of Cladophora glomerata macroalgae over its hydrochar as a catalyst for hydrogen-rich gas production.

A tubular batch micro-reactor system was used for hydrothermal gasification (HTG) of Cladophora glomerata (C. glomerata) as green macroalgae found in the southern coast of the Caspian Sea, Iran. Non-catalytic tests were performed to determine the optimum condition for hydrogen production. Hydrochar, as a solid residue of non-catalytic HTG was characterized by BET, FESEM, and ICP-OES methods to determine its physiochemical properties. Surface area and pore volume of C. glomerata increased drastically after HTG. Also, the aqueous products were identified and quantified by GC-MS and GC-FID methods. Hydrochar was loaded to the reactor to determine its catalytic effect on HTG. HTG was promoted by inorganic compounds in the hydrochar and its porosity. The maximum hydrogen yield of 9.63mmol/g was observed in the presence of algal hydrochar with the weight ratio of 0.4 to feedstock. Also, acids production was inhibited while phenol production was promoted in the presence of hydrochar.

Promotion of hydrogen-rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora glomerata via pyrolysis over its bio-char.

Conversion of Cladophora glomerata (C. glomerata) as a Caspian Sea's green macroalgae into gaseous, liquid and solid products was carried out via pyrolysis at different temperatures to determine its potential for bio-oil and hydrogen-rich gas production for further industrial utilization. Non-catalytic tests were performed to determine the optimum condition for bio-oil production. The highest portion of bio-oil was retrieved at 500°C. The catalytic test was performed using the bio-char derived at 500°C as a catalyst. Effect of the addition of the algal bio-char on the composition of the bio-oil and also gaseous products was investigated. Pyrolysis derived bio-char was characterized by BET, FESEM and ICP method to show its surface area, porosity, and presence of inorganic metals on its surface, respectively. Phenols were increased from 8.5 to 20.76area% by the addition of bio-char. Moreover, the hydrogen concentration and hydrogen selectivity were also enhanced by the factors of 1.37, 1.59 respectively.

Hydrogen production via supercritical water gasification of bagasse using Ni-Cu/γ-Al2O3 nano-catalysts.

Biomass gasification in supercritical water media is a promising method for the production of hydrogen. In this research, Cu-promoted Ni/γ-Al2O3 nano-catalysts were prepared with 2.5-30 wt% Ni and 0.6-7.5 wt% Cu loadings via the microemulsion method. Nano-catalysts were characterized by inductively coupled plasma (ICP), Brunauer Emmett Teller (BET) technique, X-Ray Diffraction (XRD), H2 chemisorption and Transmission Electron Microscopy (TEM) technique, as well as Carbon-Hydrogen-Nitrogen-Sulfur (CHNS) analysis was carried out for elemental analysis of bagasse. Nano-catalysts were assessed in a batch micro-reactor under 400°C and 240 bar. The microemulsion method decreased the catalyst average particle size and increased the percentage dispersion and reduction of the catalysts. The total gas yield increased with an increase in Ni and Cu loadings up to 20 wt% Ni and 5 wt% Cu and then started to decrease. Using the microemulsion technique for the preparation of Ni-Cu/γ-Al2O3 nano-catalyst, increased the hydrogen yield to 11.76 (mmol of H2/g of bagasse), CO yield to 2.67 (mmol of CO/g of bagasse) and light gaseous hydrocarbons to 0.6 (mmol of light gaseous hydrocarbons/g of bagasse). Promotion of Ni/γ-Al2O3 with copper increased the mole fraction of hydrogen in the final gasification products to 58.1 mol%.