A review of recent advances in water-gas shift catalysis for hydrogen production

The water-gas shift reaction (WGSR) is an intermediate reaction in hydrocarbon reforming processes, considered one of the most important reactions for hydrogen production. Here, water and carbon monoxide molecules react to generate hydrogen and carbon dioxide. From the thermodynamics aspect, pressure does not have an impact, whereas low-temperature conditions are suitable for high hydrogen selectivity because of the exothermic nature of the WGSR reaction. The performance of this reaction can be greatly enhanced in the presence of suitable catalysts. The WGSR has been widely studied due do the industrial significance resulting in a good volume of open literature on reactor design and catalyst development. A number of review articles are also available on the fundamental aspects of the reaction, including thermodynamic analysis, reaction condition optimization, catalyst design, and deactivation studies. Over the past few decades, there has been an exceptional development of the catalyst characterization techniques such as near-ambient x-ray photoelectron spectroscopy (NA-XPS) and in situ transmission electron microscopy (in situ TEM), providing atomic level information in presence of gases at elevated temperatures. These tools have been crucial in providing nanoscale structural details and the dynamic changes during reaction conditions, which were not available before. The present review is an attempt to gather the recent progress, particularly in the past decade, on the catalysts for low-temperature WGSR and their structural properties, leading to new insights that can be used in the future for effective catalyst design. For the ease of reading, the article is divided into subsections based on metals (noble and transition metal), oxide supports, and carbon-based supports. It also aims at providing a brief overview of the reaction conditions by including a table of catalysts with synthesis methods, reaction conditions, and key observations for a quick reference. Based on our study of literature on noble metal catalysts, atomic Pt substituted Mn3O4 shows almost full CO conversion at 260 °C itself with zero methane formation. In the case of transition metals group, the inclusion of Cu in catalytic system seems to influence the CO conversion significantly, and in some cases, with CO conversion improvement by 65% at 280 °C. Moreover, mesoporous ceria as a catalyst support shows great potential with reports of full CO conversion at a low temperature of 175 °C.Other Information Published in: Emergent Materials License: https://creativecommons.org/licenses/by/4.0See article on publisher's website: http://dx.doi.org/10.1007/s42247-020-00116-y</p

High purity/recovery separation of propylene from propyne using anion pillared metal-organic framework: application of vacuum swing adsorption (VSA)

Propylene is one of the world’s most important basic olefin raw material used in the production of a vast array of polymers and other chemicals. The need for high purity grade of propylene is essential and traditionally achieved by the very energy-intensive cryogenic separation. In this study, a pillared inorganic anion SIF6 2− was used as a highly selective C3H4 due to the square grid pyrazine based structure. Single gas adsorption revealed a very high C3H4 uptake value (3.32, 3.12, 2.97 and 2.43 mmol·g −1 at 300, 320, 340 and 360 K, respectively). The values for propylene for the same temperatures were 2.73, 2.64, 2.31 and 1.84 mmol·g −1 respectively. Experimental results were obtained for the two gases fitted using Langmuir and Toth models. The former had a varied degree of representation of the system with a better presentation of the adsorption of the propylene compared to the propyne system. The Toth model regression offered a better fit of the experimental data over the entire range of pressures. The representation and fitting of the models are important to estimate the energy in the form of the isosteric heats of adsorption (Qst), which were found to be 45 and 30 kJ·Kmol−1 for propyne and propylene, respectively. A Higher Qst value reveals strong interactions between the solid and the gas. The dynamic breakthrough for binary mixtures of C3H4/C3H6 (30:70 v/v)) were established. Heavier propylene molecules were eluted first from the column compared to the lighter propyne. Vacuum swing adsorption was best suited for the application of strongly bound materials in adsorbents. A six-step cycle was used for the recovery of high purity C3H4 and C3H6. The VSA system was tested with respect to changing blowdown time and purge time as well as energy requirements. It was found that the increase in purge time had an appositive effect on C3H6 recovery but reduced productivity and recovery. Accordingly, under the experimental conditions used in this study for VSA, the purge time of 600 s was considered a suitable trade-off time for purging. Recovery up to 99%, purity of 98.5% were achieved at a purge time of 600 s. Maximum achieved purity and recovery were 97.4% and 98.5% at 100 s blowdown time. Energy and power consumption varied between 63–70 kWh/ton at the range of purge and blowdown time used. The VSA offers a trade-off and cost-effective technology for the recovery and separation of olefins and paraffin at low pressure and high purit

Solid sorbents as a retrofit technology for CO2 removal from natural gas under high pressure and temperature conditions

The capture of CO2 under high pressure and temperature is challenging and is required in a number for industrial applications including natural gas processing. In this work, we examine the use of benchmark hybrid ultraporous materials HUMs for their potential use in CO2 adsorption processes under high-pressure conditions, with three varying temperatures (283, 298 and 318 K). NbOFFOVE-1-Ni and SIFSIX-3-Ni were the selected HUMs given their established superior CO2 capacity under low pressure (0â 1 bar). Both are microporous with highly ordered crystalline structures as compared to the mesoporous hexagonal silica (Santa Barbara Anhydrous-15 (SBA-15)). SBA-15 was previously tested for both low and high-pressure applications and can serve as a benchmark in this study. Sorbent characterization using XRD, SEM, FTIR and N2 adsorption were conducted to assure the purity and structure of the sorbents. TGA analysis were conducted to establish the thermal stability of the sorbents under various temperatures. High-pressure CO2 adsorption was conducted from 0â 35 bar using magnetic suspension balance (Rubotherm). Although the SBA-15 had the highest surface (527 m3/g) are of the three adsorbents, the CO2 adsorption capacity (0.42 mmol/g) was an order of magnitude less than the studies HUMs with SIFSIX-3-Ni having 2.6 mmol/g, NbOFFIVE-1-Ni achieving 2.5 mmol/g at 298 K. Multistage adsorption isotherms were obtained at different pressures. In addition, results indicate that electrostatics in HUMs are most effective at improving isosteric heat of adsorption Qst and CO2 uptake. Higher temperatures had negative effect on adsorption capacity for the HUMs and SBA-15 at pressures between 7- 9 bar. In SAB-15 the effect of temperature is reversed in what is known as a cross over phenomena

Moderate Temperature Treatment of Gas-Phase Volatile Organic Toluene Using NiO and NiO–TiO2 Nano-catalysts: Characterization and Kinetic Behaviors

Abstract For the first time, the potential of Ni/NiO and NiO–TiO2 nano-catalysts for the oxidation of toluene under moderate temperatures was investigated. The nano-catalysts were prepared using the solution combustion synthesis method (SCSM) and the effect of the composition of nano-catalysts, the inlet toluene concentration $$([\text{C}_{7} {\text{H}}_{8}]_{in})$$ ( [ C 7 H 8 ] in ) , the relative humidity (RH), and the temperature on the percentage of toluene conversion ($$\% {\text{TN}}_{Conv.} )$$ % TN C o n v . ) were subsequently examined. Results revealed that the nano-catalysts synthesized with a low fuel-to-metal ratio produced pure NiO, which has significant catalytic activity toward the conversion of toluene. Conversely, the high fuel-to-metal ratio generated a nano-catalysts that contains a mixture of Ni/NiO or pure Ni with low activity toward the conversion of toluene. Adding NiO to TiO2 increased the surface area of the catalyst, augmented the catalyst active sites, enhanced the oxidation of toluene, and increased CO2 selectivity ($${\text{S}}_{{{\text{CO}}_{2} }}$$ S CO 2 ). NiO and NiO–TiO2 nano-catalysts exhibited higher reaction rates, significant catalyst turnover frequency, and low activation energy. The obtained results revealed that the SCSM is a promising synthesis method for producing NiO or NiO–TiO2 nano-catalysts, which can be employed successfully for the removal of toluene from gas streams.Other Information Published in: Waste and Biomass Valorization License: https://creativecommons.org/licenses/by/4.0See article on publisher's website: http://dx.doi.org/10.1007/s12649-020-01270-4</p

Effective separation of prime olefins from gas stream using anion pillared metal organic frameworks: ideal adsorbed solution theory studies, cyclic application and stability

The separation of C3H4/C3H6 is one of the most energy intensive and challenging operations, requiring up to 100 theoretical stages, in traditional cryogenic distillation. In this investigation, the potential application of two MOFs (SIFSIX-3-Ni and NbOFFIVE-1-Ni) was tested by studying the adsorption-desorption behaviors at a range of operational temperatures (300–360 K) and pressures (1–100 kPa). Dynamic adsorption breakthrough tests were conducted and the stability and regeneration ability of the MOFs were established after eight consecutive cycles. In order to establish the engineering key parameters, the experimental data were fitted to four isotherm models (Langmuir, Freundlich, Sips and Toth) in addition to the estimation of the thermodynamic properties such as the isosteric heats of adsorption. The selectivity of the separation was tested by applying ideal adsorbed solution theory (IAST). The results revealed that SIFSIX-3-Ni is an effective adsorbent for the separation of 10/90 v/v C3H4/C3H6 under the range of experimental conditions used in this study. The maximum adsorption reported for the same combination was 3.2 mmol g−1. Breakthrough curves confirmed the suitability of this material for the separation with a 10-min gab before the lighter C3H4 is eluted from the column. The separated C3H6 was obtained with a 99.98% purity

Metal-organic frameworks as a platform for CO2 capture and chemical processes: adsorption, membrane separation, catalytic-conversion, and electrochemical reduction of CO2

The continuous rise in the atmospheric concentration of carbon dioxide gas (CO2) is of significant global concern. Several methodologies and technologies are proposed and applied by the industries to mitigate the emissions of CO2 into the atmosphere. This review article offers a large number of studies that aim to capture, convert, or reduce CO2 by using a superb porous class of materials (metal-organic frameworks, MOFs), aiming to tackle this worldwide issue. MOFs possess several remarkable features ranging from high surface area and porosity to functionality and morphology. As a result of these unique features, MOFs were selected as the main class of porous material in this review article. MOFs act as an ideal candidate for the CO2 capture process. The main approaches for capturing CO2 are pre-combustion capture, post-combustion capture, and oxy-fuel combustion capture. The applications of MOFs in the carbon capture processes were extensively overviewed. In addition, the applications of MOFs in the adsorption, membrane separation, catalytic conversion, and electrochemical reduction processes of CO2 were also studied in order to provide new practical and efficient techniques for CO2 mitigation

Viscous Behavior of Imidazolium-Based Ionic Liquids

The viscosity of four imidazolium-based ionic liquids is analyzed as a function of pressure and temperature. Experimental measurements were carried out using an electromagnetic moving piston viscometer in the 303–353 K and 0.1–70 MPa ranges on synthesized ultrapure samples, and compared with available literature data. Molecular dynamics simulations were used to analyze the fluids’ dynamic properties from a nanoscopic viewpoint, with special attention paid to self-diffusion coefficients and dynamic viscosity. Simulated properties are in excellent agreement with experimental results in spite of the glasslike dynamics of some of the studied fluids

Phenol degradation by powdered metal ion modified titanium dioxide photocatalysts

Conventional water purification and disinfection generally involve potentially hazardous substances, some of which known to be carcinogenic in nature. Titanium dioxide photocatalytic processes provide an effective route to destroy hazardous organic contaminants. This present work explores the possibility of the removal of organic pollutants (phenol) by the application of TiO2 based photocatalysts. The production of series of metal ions doped or undoped TiO2 were carried out via a sol-gel method and a wet impregnation method. Undoped TiO2 and Cu doped TiO2 showed considerable phenol degradation. The efficiency of photocatalytic reaction largely depends on the photocatalysts and the methods of preparation the photocatalysts. The doping of Fe, Mn, and humic acid at 1.0 M% via sol-gel methods were detrimental for phenol degradation. The inhibitory effect of initial phenol concentration on initial phenol degradation rate reveals that photocatalytic decomposition of phenol follows pseudo zero order reaction kinetics. A concentration of > 1 g/L TiO2 and Cu doped TiO2 is required for the effective degradation of 50 mg/L of phenol at neutral pH. The rise in OH- at a higher pH values provides more hydroxyl radicals which are beneficial of phenol degradation. However, the competition among phenoxide ion. Cl- and OH- for the limited number of reactive sites on TiO2 will be a negative influence in the generation of hydroxyl radical. The dependence of phenol degradation rate on the light intensity was observed, which also implies that direct sunlight can be a substitute for the UV lamps and that photocatalytic treatment of organic pollutants using this technique shows some promise. (C) 2012 Elsevier B.V. All rights reserved

Gas Hydrate Inhibition: A Review of the Role of Ionic Liquids

Ionic liquids (ILs) are popular designer green chemicals with great potential for use in diverse energy-related applications. Apart from the well-known low vapor pressure, the physical properties of ILs, such as hydrogen-bond-forming capacity, physical state, shape, and size, can be fine-tuned for specific applications. Natural gas hydrates are easily formed in gas pipelines and pose potential problems to the oil and natural gas industry, particularly during deep-sea exploration and production. This review summarizes the recent advances in IL research as dual-function gas hydrate inhibitors. Almost all of the available thermodynamic and kinetic inhibition data in the presence of ILs have been systematically reviewed to evaluate the efficiency of ILs in gas hydrate inhibition, compared to other conventional thermodynamic and kinetic gas hydrate inhibitors. The principles of natural gas hydrate formation, types of gas hydrates and their inhibitors, apparatuses and methods used, reported experimental data, and theoretical methods are thoroughly and critically discussed. The studies in this field will facilitate the design of advanced ILs for energy savings through the development of efficient low-dosage gas hydrate inhibitors

Dynamic simulation of lead(II) metal adsorption from water on activated carbons in a packed-bed column

In this work, lead(II) adsorption on activated carbons, tire-derived activated carbon (TAC), and commercial activated carbon (CAC), in a packed-bed column, was simulated using the Aspen Adsorption® V11 flowsheet simulator. The simulator was used to model the fixed-bed adsorption column and to establish the breakthrough curves by varying the initial concentration of lead(II) ions (500 mg/L, 1000 mg/L, 2000 mg/L, and 3000 mg/L), the bed height (0.2 m, 0.3 m, 0.4 m, 0.5 m, and 0.6 m), and the flow rate (9.88 × 10−4 m3/s, 1.98 × 10−3 m3/s, 2.96 × 10−3 m3/s, 3.95 × 10−3 m3/s, and 4.94 × 10−3 m3/s), at constant temperature and pressure of 25 °C and 3 bar, respectively. At the optimum conditions of 500 mg/L lead(II) concentration, 0.6 m bed height, and 9.88 × 10−4 m3/s flow rate, the breakthrough times were 488 s and 23 s for TAC and CAC, respectively. Under the same conditions, the adsorption capacity obtained at t0.5 was 114.26 mg/g for TAC and 7.72 mg/g for CAC. The simulation results indicate the potential of TAC for the adsorption of lead(II) in comparison to CAC.Other Information Published in: Biomass Conversion and Biorefinery License: https://creativecommons.org/licenses/by/4.0See article on publisher's website: http://dx.doi.org/10.1007/s13399-022-03079-8</p