RuNi/TiZr-MMO Catalysts Derived from Zr-Modified NiTi-LDH for CO-Selective Methanation.

CO-selective methanation (CO-SMET) is an efficient hydrogen-rich (H2-rich) gas purification technology for proton exchange membrane fuel cells. It is vital to develop suitable catalysts with good low-temperature activity for CO-SMET reactions. In this study, RuNi/TiZrx-mixed metal oxide (RuNi/TiZrx-MMO) catalysts with different molar ratios of Zr/Ti, derived from a Zr-promoted NiTi-layered double hydroxide (NiTi-LDH) precursor were successfully prepared using the co-precipitation and wet impregnation methods. The RuNi/TiZr0.2-MMO catalyst possesses higher catalytic performance in a lower temperature window of 180-280 °C, which can reduce the CO concentration to be below 10 ppm. The characterization results obtained from XRD, BET, SEM, TEM, XPS, TPR, and TPD suggest that the addition of ZrO2 increases the surface area of the catalyst, improves the dispersion of metallic nanoparticles, increases the reducibility of Ni species on the RuNi/TiZr0.2-MMO catalyst's surface, and enhances the adsorption and activation ability of CO, resulting in remarkable catalytic performance at lower reaction temperatures. Moreover, the RuNi/TiZr0.2-MMO catalyst demonstrated long-term catalytic stability and carbon resistance.

Fluorinated MOF-Based Hexafluoropropylene Nanotrap for Highly Efficient Purification of Octafluoropropane Electronic Specialty Gas.

High-purity octafluoropropane (C3F8) electronic specialty gas is a key chemical raw material in semiconductor and integrated circuit manufacturing industry, while selective removal of hexafluoropropylene (C3F6) impurity for C3F8 purification is essential but a challenging task. Here we report a fluorinated cage-like MOF Zn-bzc-CF3 (bzc=5-(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) for C3F6/C3F8 separation. The incorporation of -CF3 groups not only provides suitable pore aperture size for highly efficient size-exclusive C3F6/C3F8 separation, but also creates hydrophobic microenvironments, endowing Zn-bz-CF3 high chemical stability. Remarkably, Zn-bzc-CF3 exhibits high C3F6 adsorption capacity while excluding C3F8, achieving ideal molecular-sieving C3F6/C3F8 separation. Breakthrough experiments show that Zn-bzc-CF3 can efficiently separate C3F6/C3F8 mixture and high-purity C3F8 (99.9 %) can be obtained.

Systematic control technologies for gaseous pollutants from non-ferrous metallurgy.

Air pollutant emissions represent a critical challenge in the green development of the non-ferrous metallurgy industry. This work studied the emission characteristics, formation mechanisms, phase transformation and separation of typical air pollutants, such as heavy metal particles, mercury, sulfur oxides and fluoride, during non-ferrous smelting. A series of purification technologies, including optimization of the furnace throat and high-temperature discharge, were developed to collaboratively control and recover fine particles from the flue gas of heavy metal smelting processes, including copper, lead and zinc. Significant improvements have been realized in wet scrubbing technology for removing mercury, fluoride and SO2 from flue gas. Gas-liquid sulfidation technology by applying H2S was invented to recycle the acid scrubbing wastewater more efficiently and in an eco-friendly manner. Based on digital technology, a source reduction method was designed for sulfur and fluoride control during the whole aluminum electrolysis process. New desulfurization technologies were developed for catalytic reduction of the sulfur content in petroleum coke at low temperature and catalytic reduction of SO2 to elemental sulfur. This work has established the technology for coupling multi-pollutant control and resource recovery from the flue gas from non-ferrous metallurgy, which provides the scientific theoretical basis and application technology for the treatment of air pollutants in the non-ferrous metallurgy industry.

Solid-State Investigation, Storage, and Separation of Pyrophoric PH3 and P2 H4 with α-Mg Formate.

Phosphane, PH3 -a highly pyrophoric and toxic gas-is frequently contaminated with H2 and P2 H4 , which makes its handling even more dangerous. The inexpensive metal-organic framework (MOF) magnesium formate, α-[Mg(O2 CH)2 ], can adsorb up to 10 wt % of PH3 . The PH3 -loaded MOF, PH3 @α-[Mg(O2 CH)2 ], is a non-pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane. α-[Mg(O2 CH)2 ] further plays a critical role in purifying PH3 from H2 and P2 H4 : at 25 °C, H2 passes through the MOF channels without adsorption, whereas PH3 adsorbs readily and only slowly desorbs under a flow of inert gas (complete desorption time≈6 h). Diphosphane, P2 H4 , is strongly adsorbed and trapped within the MOF for at least 4 months. P2 H4 @α-[Mg(O2 CH)2 ] itself is not pyrophoric and is air- and light-stable at room temperature.

The efficiency and mechanism of humidity in alleviating CO2 inhibition on H2S adsorption to straw biochars.

Adsorption tests were conducted to clarify the impact of carbon dioxide (CO2) on hydrogen sulfide (H2S) removal to straw biochars and the role of humidity in affecting the CO2 impact. When straw biochars were dry, CO2 proved significantly detrimental to their H2S adsorption, regardless of the CO2 contents. In contrast, when adjusting the humidity of the biochars to 20%, the presence of CO2 promoted the conversion of H2S into sulfites, though still inhibited the generation of elemental sulfur, through which the original negative CO2 impact was nearly compensated. The presence of low to medium contents of CO2 even slightly improved the adsorption capacity and extended the breakthrough time. This phenomenon was ascribed to a favorable carbon surface environment for H2S dissociation and oxidation, created from the reactions of the major minerals (Ca and Mg) with CO2 and water. To sum up, the CO2 inhibition on the H2S adsorption to biochars was ascribed to the competition of CO2 for the active sites; however, humidity induced a series of CO2-participated chemical reactions between H2S and the minerals, sufficiently alleviating the CO2 inhibition. The results also highlight the necessity to recognize the most critical biochar properties or an efficient balance of crucial biochar properties in achieving an optimal H2S removal when CO2 is present in the syngas.

High Yield of CO and Synchronous S Recovery from the Conversion of CO2 and H2S in Natural Gas Based on a Novel Electrochemical Reactor.

H2S and CO2 are the main impurities in raw natural gas, which needs to be purified before use. However, the comprehensive utilization of H2S and CO2 has been ignored. Herein, we proposed a fully resource-based method to convert toxic gas H2S and greenhouse gas CO2 synchronously into CO and elemental S by using a novel electrochemical reactor. The special designs include that, in the anodic chamber, H2S was oxidized rapidly to S based on the I-/I3- cyclic redox system to avoid anode passivation. On the other hand, in the cathodic chamber, CO2 was rapidly and selectively reduced to CO based on a porous carbon gas diffusion electrode (GDE) modified with polytetrafluoroethylene and cobalt phthalocyanine (CoPc). A high Faraday efficiency (>95%) toward CO was achieved due to the enhanced mass transfer of CO2 on the GDE and the presence of the selective CoPc catalyst. The maximum energy efficiency of the system was more than 72.41% with a current density of over 50 mA/cm2, which was 12.5 times higher than what was previously reported on the H2S treatment system. The yields of S and CO were 24.94 mg·cm-2·h-1 and 19.93 mL·cm-2·h-1, respectively. A model analysis determined that the operation cost of the synchronous utilization of H2S and CO2 method was slightly lower than that of the single utilization of H2S in the existing natural gas purification technology. Overall, this paper provides efficient and simultaneous conversion of H2S and CO2 into S and CO.

Environmentally friendly automated line for recovering aluminium and lithium iron phosphate components of spent lithium-iron phosphate batteries.

Lithium iron phosphate (LFP) batteries contain metals, toxic electrolytes, organic chemicals and plastics that can lead to serious safety and environmental problems when they are improperly disposed of. The published literature on recovering spent LFP batteries mainly focuses on policy-making and conceptual design. The production line of recovering spent LFP batteries and its detailed operation are rarely reported. A set of automatic line without negative impact to the environment for recycling spent LFP batteries at industrial scale was investigated in this study. It includes crushing, pneumatic separation, sieving, and poison gas treatment processes. The optimum retaining time of materials in the crusher is 3 minutes. The release rate is the highest when the load of the impact crusher is 800 g. An air current separator (ACS) was designed to separate LFP from aluminium (Al) foil and LFP powder mixture. Movement behaviour of LFP powder and Al foil in the ACS were analysed, and the optimized operation parameter (35.46 m/s) of air current speed was obtained through theoretical analysis and experiments. The weight contents of an Al foil powder collector from vibrating screen-3 and LFP powder collector from bag-type dust collector are approximately 38.7% and 52.4%, respectively. The economic cost of full manual dismantling is higher than the recovery production line. This recycling system provides a feasible method for recycling spent LFP batteries.

Recent Advances in Graphene Oxide Membranes for Gas Separation Applications.

Graphene oxide (GO) can dramatically enhance the gas separation performance of membrane technologies beyond the limits of conventional membrane materials in terms of both permeability and selectivity. Graphene oxide membranes can allow extremely high fluxes because of their ultimate thinness and unique layered structure. In addition, their high selectivity is due to the molecular sieving or diffusion effect resulting from their narrow pore size distribution or their unique surface chemistry. In the first part of this review, we briefly discuss different mechanisms of gas transport through membranes, with an emphasis on the proposed mechanisms for gas separation by GO membranes. In the second part, we review the methods for GO membrane preparation and characterization. In the third part, we provide a critical review of the literature on the application of different types of GO membranes for CO2, H2, and hydrocarbon separation. Finally, we provide recommendations for the development of high-performance GO membranes for gas separation applications.

Achieving Simultaneous CO2 and H2 S Conversion via a Coupled Solar-Driven Electrochemical Approach on Non-Precious-Metal Catalysts.

Carbon dioxide (CO2 ) and hydrogen sulfide (H2 S) are generally concomitant with methane (CH4 ) in natural gas and traditionally deemed useless or even harmful. Developing strategies that can simultaneously convert both CO2 and H2 S into value-added products is attractive; however it has not received enough attention. A solar-driven electrochemical process is demonstrated using graphene-encapsulated zinc oxide catalyst for CO2 reduction and graphene catalyst for H2 S oxidation mediated by EDTA-Fe2+ /EDTA-Fe3+ redox couples. The as-prepared solar-driven electrochemical system can realize the simultaneous conversion of CO2 and H2 S into carbon monoxide and elemental sulfur at near neutral conditions with high stability and selectivity. This conceptually provides an alternative avenue for the purification of natural gas with added economic and environmental benefits.

Topology Reconfiguration of Anion-Pillared Metal-Organic Framework from Flexibility to Rigidity for Enhanced Acetylene Separation.

Flexible metal-organic framework (MOF) adsorbents commonly encounter limitations in removing trace impurities below gate-opening threshold pressures. Topology reconfiguration can fundamentally eliminate intrinsic structural flexibility, yet remains a formidable challenge and is rarely achieved in practical applications. Herein, a solvent-mediated approach is presented to regulate the flexible CuSnF6-dpds-sql (dpds = 4,4''-dipyridyldisulfide) with sql topology into rigid CuSnF6-dpds-cds with cds topology. Notably, the cds topology is unprecedented and first obtained in anion-pillared MOF materials. As a result, rigid CuSnF6-dpds-cds exhibits enhanced C2H2 adsorption capacity of 48.61 cm3 g-1 at 0.01 bar compared to flexible CuSnF6-dpds-sql (21.06 cm3 g-1). The topology transformation also facilitates the adsorption kinetics for C2H2, exhibiting a 6.5-fold enhanced diffusion time constant (D/r2) of 1.71 × 10-3 s-1 on CuSnF6-dpds-cds than that of CuSnF6-dpds-sql (2.64 × 10-4 s-1). Multiple computational simulations reveal the structural transformations and guest-host interactions in both adsorbents. Furthermore, dynamic breakthrough experiments demonstrate that high-purity C2H4 (>99.996%) effluent with a productivity of 93.9 mmol g-1 can be directly collected from C2H2/C2H4 (1/99, v/v) gas-mixture in a single CuSnF6-dpds-cds column.

Agri-food waste biosorbents for volatile organic compounds removal from air and industrial gases - A review.

Approximately 1.3 billion metric tons of agricultural and food waste is produced annually, highlighting the need for appropriate processing and management strategies. This paper provides an exhaustive overview of the utilization of agri-food waste as a biosorbents for the elimination of volatile organic compounds (VOCs) from gaseous streams. The review paper underscores the critical role of waste management in the context of a circular economy, wherein waste is not viewed as a final product, but rather as a valuable resource for innovative processes. This perspective is consistent with the principles of resource efficiency and sustainability. Various types of waste have been described as effective biosorbents, and methods for biosorbents preparation have been discussed, including thermal treatment, surface activation, and doping with nitrogen, phosphorus, and sulfur atoms. This review further investigates the applications of these biosorbents in adsorbing VOCs from gaseous streams and elucidates the primary mechanisms governing the adsorption process. Additionally, this study sheds light on methods of biosorbents regeneration, which is a key aspect of practical applications. The paper concludes with a critical commentary and discussion of future perspectives in this field, emphasizing the need for more research and innovation in waste management to fully realize the potential of a circular economy. This review serves as a valuable resource for researchers and practitioners interested in the potential use of agri-food waste biosorbents for VOCs removal, marking a significant first step toward considering these aspects together.

Improving agglomeration efficiency of aerosols with sizes less than 2.5 µm by generation of vortex streams in inhomogeneous ultrasonic field.

In this paper a new approach to increase the agglomeration efficiency of finely dispersed aerosols by generating toroidal vortex streams in inhomogeneous ultrasonic field is proposed and studied. From the obtained experimental results (for two types of emitters) it could be established that the toroidal vortex streams generated in an inhomogeneous ultrasonic field provide an increase of the agglomeration efficiency when exposed to a gas-dispersed flow injected into the agglomeration chamber at a speed of up to 0.2 m/s. Further increase of the injected flow velocity leads to disruption of the structure of the generated vortex streams and agglomeration efficiency decreases. In the course of the analysis, it was found that the efficiency of agglomeration by toroidal vortex streams increases in direct proportion to the increase of the sound pressure level up to 165 dB. After that, no further increase in agglomeration efficiency is observed. By analyzing the agglomeration efficiency depending on particle size, it was possible to verify that the efficiency of agglomeration in comparison with agglomeration in a homogeneous ultrasonic field for droplets with a size of 0.2 … 0.6 µm is increased by 25 %, for 1.8 µm droplets by 20 %; and for droplets larger than 2.5 µm, the increase in efficiency is no more than 17 %.

Fundamental properties and sustainable applications of the natural zeolite clinoptilolite.

This review explores a set of sustainable applications of clinoptilolite, a natural zeolite abundant around the world in different localities. Thanks to its physico-chemical properties this material is extremely versatile for several applications, ranging from environmental catalysis and CO2 removal to industrial and agricultural wastewater purification, aquaculture, animal feeding, and food industry but also medical applications and energy storage systems. Due to the presence of cations in its framework, it is possible to tune the material's features making it suitable for adsorbing specific compounds. Thus, this review aims to provide insight into developing new technologies based on the use of this material that is sustainable, not harmful for humans and animals, naturally abundant, and above all cost-effective. Furthermore, it is intended to promote the use of natural materials in various areas with a view to sustainability and to reduce as far as possible the use of chemicals or other materials whose synthesis process can have a polluting effect on the environment.

A review of cellulose-based derivatives polymers in fabrication of gas separation membranes: Recent developments and challenges.

Due to low-cost, sustainability and good mechanical stability, cellulose-based materials are frequently used in fabrication of polymeric gas separation membrane as potential carbohydrate polymers to substitute traditional petrochemical-based materials. In this review, the performance of cellulose-based polymeric membranes i.e. cellulose acetate, cellulose diacetate, cellulose triacetate, ethyl cellulose and carboxymethyl cellulose in the separation of different gases were investigated. This review paper provides the main features and advantages in the fabrication of cellulose-based gas separation membranes. The influence of the functionalization of cellulose on gas separation and permeability performance of related membranes is considered. Influence of different modification procedures such as blending with polymers, nanomaterials and ionic liquids on the gas separation ability of cellulose-based membranes were reviewed. Moreover, a brief inquiry of the potential of cellulose-based gas separation membranes for industrial applications, by examining the performance of different cellulose derivatives and identifying potential strategies for membrane modification and optimization are given, along with the current restrictions and the future perspectives are discussed.

VOCs absorption from gas streams using deep eutectic solvents - A review.

Volatile organic compounds (VOCs) are one of the most severe atmospheric pollutants. They are mainly emitted into the atmosphere from anthropogenic sources such as automobile exhaust, incomplete fuel combustion, and various industrial processes. VOCs not only cause hazards to human health or the environment but also adversely affect industrial installation components due to their specific properties, i.e., corrosive and reactivity. Therefore, much attention is being paid to developing new methods for capturing VOCs from gaseous streams, i.e., air, process streams, waste streams, or gaseous fuels. Among the available technologies, absorption based on deep eutectic solvents (DES) is widely studied as a green alternative to other commercial processes. This literature review presents a critical summary of the achievements in capturing individual VOCs using DES. The types of used DES and their physicochemical properties affecting absorption efficiency, available methods for evaluating the effectiveness of new technologies, and the possibility of regeneration of DES are described. In addition, critical comments on the new gas purification methods and future perspectives are included.

Multivariate Metal-Organic Frameworks Prepared by Simultaneous Metal/Ligand Exchange for Enhanced C2-C3 Selective Recovery from Natural Gas.

Recovering light alkanes from natural gas is a critical but challenging process in petrochemical production. Herein, we propose a postmodification strategy via simultaneous metal/ligand exchange to prepare multivariate metal-organic frameworks with enhanced capacity and selectivity of ethane (C2H6) and propane (C3H8) for their recovery from natural gas with methane (CH4) as the primary component. By utilizing the Kuratowski-type secondary building unit of CFA-1 as a scaffold, namely, {Zn5(OAc)4}6+, the Zn2+ metal ions and OAc- ligands were simultaneously exchanged by other transition metal ions and halogen ligands under mild conditions. Inspiringly, this postmodification treatment can give rise to improved capacity for C2H6 and C3H8 without a noticeable increase in CH4 uptake, and consequently, it resulted in significantly enhanced selectivity toward C2H6/CH4 and C3H8/CH4. In particular, by adjusting the species and amount of the modulator, the optimal sample CFA-1-NiCl2-2.3 demonstrated the maximum capacities of C2H6 (5.00 mmol/g) and C3H8 (8.59 mmol/g), increased by 29 and 32% compared to that of CFA-1. Moreover, this compound exhibited excellent separation performance toward C2H6/CH4 and C3H8/CH4, with high uptake ratios of 6.9 and 11.9 at 298 K and 1 bar, respectively, superior to the performance of a majority of the reported MOFs. Molecular simulations were applied to unravel the improved separation mechanism of CFA-1-NiCl2-2.3 toward C2H6/CH4 and C3H8/CH4. Furthermore, remarkable thermal/chemical robustness, moderate isosteric heat, and fully reproducible breakthrough experiments were confirmed on CFA-1-NiCl2-2.3, indicating its great potential for light alkane recovery from natural gas.

3D porous polymers for selective removal of CO2 and H2 storage: experimental and computational studies.

In this article, newly designed 3D porous polymers with tuned porosity were synthesized by the polycondensation of tetrakis (4-aminophenyl) methane with pyrrole to form M1 polymer and with phenazine to form M2 polymer. The polymerization reaction used p-formaldehyde as a linker and nitric acid as a catalyst. The newly designed 3D porous polymers showed permanent porosity with a BET surface area of 575 m2/g for M1 and 389 m2/g for M2. The structure and thermal stability were investigated by solid 13C-NMR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). The performance of the synthesized polymers toward CO2 and H2 was evaluated, demonstrating adsorption capacities of 1.85 mmol/g and 2.10 mmol/g for CO2 by M1 and M2, respectively. The importance of the synthesized polymers lies in their selectivity for CO2 capture, with CO2/N2 selectivity of 43 and 51 for M1 and M2, respectively. M1 and M2 polymers showed their capability for hydrogen storage with a capacity of 66 cm3/g (0.6 wt%) and 87 cm3/g (0.8 wt%), respectively, at 1 bar and 77 K. Molecular dynamics (MD) simulations using the grand canonical Monte Carlo (GCMC) method revealed the presence of considerable microporosity on M2, making it highly selective to CO2. The exceptional removal capabilities, combined with the high thermal stability and microporosity, enable M2 to be a potential material for flue gas purification and hydrogen storage.

CO2 adsorption and CO2/CH4 separation using fibrous amine-containing adsorbents: isothermal, kinetic, and thermodynamic behaviours.

A series of fibrous aminated adsorbents for CO2 adsorption were prepared by covalent incorporation of poly (glycidyl methacrylate) (PGMA) by graft copolymerization of GMA onto electron beam (EB) irradiated polyethylenepolypropylene (PE/PP) fibrous sheets and subsequent amination with ethylenediamine (EDA), diethylenetriamine (DETA), or tetraethylenepentamine (TEPA). The physico-chemical properties of the adsorbents were evaluated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) analysis. All the adsorbents displayed typic primary and secondary amine features combined with a decrease in both of crystallinity and surface area of PE/PP, and such a decrease was higher in adsorbents with longer aliphatic chain of the amine. Of all adsorbents, TEPA-containing fibres showed the highest CO2 adsorption capacity and thus was further investigated for CO2 capture from CO2/CH4 mixtures of different gas ratios under various pressures and temperatures. The selectivity of CO2 over CH4 and equilibrium isotherms, kinetics, and thermodynamics of the adsorption on the fibrous aminated adsorbent were all investigated. The Sips model was found to best fit the isotherm of CO2 adsorption suggesting the presence of a combination of monolayer and multilayer adsorptions. The adsorption kinetic data was found to best fit Elovich model reflecting chemisorption. The ΔG°, ΔS°, and ΔH° showed positive values suggesting that the adsorption of CO2 on the present fibrous adsorbent was non-spontaneous with an increase in randomness implying that the process was endothermic. Overall, it can be suggested that PE/PP-g-PGMA/TEPA adsorbent has a strong potential for separation of CO2 from NG.

Influence of operating parameters on cake formation in pilot scale pulse-jet bag filter.

Bag filters are commonly used for fine particles removal in off-gas purification. There dust laden gas pervades through permeable filter media starting at a lower pressure drop limit leaving dust (called filter cake) on the filter media. The filter cakeformation is influenced by many factors including filtration velocity, dust concentration, pressure drop limits, and filter media resistance. Effect of the stated parameters is investigated experimentally in a pilot scale pulse-jet bag filter test facility where lime stone dust is separated from air at ambient conditions. Results reveal that filtration velocity significantly affects filter pressure drop as well as cake properties; cake density and specific cake resistance. Cake density is slightly affected by dust concentration. Specific resistance of filter cake increases with velocity, slightly affected by dust concentration, changes inversely with the upper pressure drop limit and decreases over a prolonged use (aging). Specific resistance of filter media is independent of upper pressure drop limit and increases linearly over a prolonged use.

The effect of operating conditions on resistance parameters of filter media and limestone dust cake for uniformly loaded needle felts in a pilot scale test facility at ambient conditions.

Resistance parameters are essential for the prediction of pressure drop in bag filters. The reported values for limestone dust differ in magnitude and also depend on operating parameters. In this work, experimental data is provided from a pilot scale pulse-jet regenerated bag filter test facility for three types of needle felts using air and limestone dust at ambient conditions. Results reveal that specific resistance of filter media is independent of velocity while the specific resistance of filter cake increases linearly with filtration velocity. Residual pressure drop is almost constant, independent of upper pressure drop limit. The cake resistance at constant velocity fits to a second degree polynomial whereas it increases linearly with the velocity. A linear relation is reported here for all the cases. The resistance of filter cake decreases at higher upper pressure drop limit.