Cyanide gas is highly toxic and volatile and is among the most typical toxic and harmful pollutants to human health and the environment found in industrial waste gas. In the military context, cyanide gas has been used as a systemic toxic agent. In this paper, we review cyanide gas elimination methods, focusing on adsorption and catalysis approaches. The research progress on materials capable of affecting cyanide gas adsorption and catalytic degradation is discussed in depth, and the advantages and disadvantages of various materials are summarized. Finally, suggestions are provided for future research directions with respect to cyanide gas elimination materials.
NH3 is a typical alkaline gaseous pollutant widely derived from industrial production and poses great risks to humans and other biota. Metal-organic frameworks (MOFs) have excellent adsorption capacities relative to materials traditionally used to adsorb NH3. However, in practice, applications of MOFs as adsorbents are restricted because of its powder form. We prepared a polyamide (PA) macroporous polyester substrate using an emulsion template method and modified the surface with polyethylenimine (PEI) to improve the MOF growth efficiency on the substrate. The difficulty of loading the MOF because of the fast nucleation rate inside the PA macroporous polyester substrate was solved using a stepwise impregnation layer-by-layer (LBL) growth method, and a PA-PEI-MOF303(Al) hierarchical pore composite that very efficiently adsorbed NH3 was successfully prepared. The PA-PEI-MOF303(Al) adsorption capacity for NH3 was 16.07 mmol·g−1 at 298 K and 100 kPa, and the PA-PEI-MOF303(Al) could be regenerated repeatedly under vacuum at 423 K. The NH3 adsorption mechanism was investigated by in situ Fourier transform infrared spectroscopy and by performing two-dimensional correlation analysis. Unlike for the MOF303(Al) powder, the formation of multi-site hydrogen bonds between Al–O–Al/C–OH, N–H, –OH, C=O, and NH3 in PA-PEI-MOF303(Al) was found to be an important reason for efficient NH3 adsorption. This study will provide a reference for the preparation of other MOF-polymer composites.
Granular activated carbon (GAC) has proven to be an effective adsorbent for removing the chemical warfare agent sarin (GB) and simulants like Dimethyl methylphosphonate (DMMP). However, it comes with certain limitations, including inadequate contact efficiency, notable mass transfer resistance, and lower bed utilization efficiency. This study synthesized steel fiber-entrapped activated carbon composites (SFEACs), which exhibited a maximum adsorption capacity of 285.3 mg/g at 303 K. Compared with the packed bed (PB) filled with GAC, while the adsorption capacity of SFEACS decreased, there was a substantial increase in the adsorption mass transfer rate. These SFEACs were combined with GAC to create a structural fixed bed (SFB), which demonstrated excellent performance in DMMP removal. Under identical experimental conditions, the DMMP breakthrough curve of SFB exhibited a steeper profile compared to the packed bed (PB) filled with GAC at the same bed height, and the breakthrough time against DMMP vapor could be extended by 13.8%. Furthermore, the adsorption rate constant of the Yoon-Nelson model increased by more than 17.6%, and the unused bed length, according to the Wheeler–Jonas model, decreased by more than 14%.
Cyanogen chloride (CNCl) is highly toxic and volatile, and it is difficult to effectively remove via porous substances such as activated carbon due to the weak interaction between CNCl and the adsorbent surface. Developing a highly effective elimination material against CNCl is of great importance in military chemical protection. In this work, a new metal-organic framework (MOF) CuBTC@PA-PEI (polyacrylate-polyethyleneimine) composite was prepared and exhibited excellent CNCl elimination performance in the breakthrough tests. PEI was used for the functionalization of PA with amino groups, which is beneficial to anchor with metal ions of MOF. Afterward, the growth of MOF occurred on the surface and in the pores of the matrix by molecular self-assembly via our newly proposed stepwise impregnation layer-by-layer growth method. Breakthrough tests were performed to evaluate the elimination performance of the composites against CNCl. Compared with the pristine CuBTC powder, the CuBTC@PA-PEI composite exhibited better adsorption capacity and a longer breakthrough time. By compounding with the PA matrix, a hierarchically porous structure of CuBTC@PA-PEI composite was constructed, which provides a solution to the mass transfer problem of pure microporous MOF materials. It also solves the problems of MOF molding and lays a foundation for the practical application of MOF.