Search Results (6)

Nickel (Ni) catalysts have numerous applications in the chemical industry, but they are susceptible to sulfurization, with their sulfurized structures and underlying formation mechanisms remaining unclear. Herein, density functional theory (DFT) combined with the particle swarm optimization (PSO) algorithm is employed to investigate the low-energy structures and formation mechanisms of sulfide phases on Ni(111) surfaces, especially under high-sulfur-coverage conditions where traditional DFT calculations fail to reach convergence. Using ($\sqrt{3}\times \sqrt{3}$ ) Ni(111) slab models, we identify a sulfurization limit, finding that each pair of deposited sulfur atoms can sulfurize one layer of three Ni atoms at most (Ni:S = 3:2), with additional sulfur atoms penetrating deeper layers until saturation. Under typical reactive adsorption desulfurization conditions, the ab initio thermodynamics analysis indicates that Ni₃S₂ is the most stable sulfide phase, consistent with sulfur K-edge XANES data. Unsaturated phases, including Ni₃S, Ni₂S, and Ni₉S₅, represent intermediate states towards saturation, potentially explaining the diverse Ni sulfide compositions observed in experiments. Full article

Production of renewable fuels from gasification is based on catalytic processes. Deep desulfurization is required to avoid the poisoning of the catalysts. It means the removal of H₂S but also of organic sulfur species. Conventional cleaning consists of a several-step complex approach comprising catalytic hydro-treating followed by H₂S removal. In this work, a single-stage process using a zinc and nickel oxide sorbent has been investigated for the removal of organic sulfur species present in syngas. The process is called reactive adsorption and comes from the refinery industry. The challenge investigated by CIEMAT was to prove for the first time that the concept is also valid for syngas. We have studied the process at a lab scale. Thiophene and benzothiophene, two of the main syngas organic sulfur compounds, were selected as target species to remove. The experimental study comprised the analysis of the effect of temperature (250–450 °C), pressure (1–10 bar), space velocity (2000–3500 h⁻¹), tar components (toluene), sulfur species (H₂S), and syngas components (H₂, CO, and full syngas CO/CO₂/CH₄/H₂). Operating conditions for removal of thiophene and benzothiophene were determined. Increasing pressure and temperature had a positive effect, and full conversion was achieved at 450 °C, 10 bar and 3500 h⁻¹, accompanied by simultaneous hydrogen sulfide capture by the sorbent in accordance with the reactive adsorption desulfurization (RADS) process. Space velocity and hydrogen content in the syngas had little effect on desulfurization. Thiophene conversions from 39% to 75% were obtained when feeding synthetic syngas mimicking different compositions, spanning from air to steam-oxygen-blown gasification. Toluene, as a model tar component present in syngas, did not strongly affect the removal of thiophene and benzothiophene. H₂S inhibited their conversion, falling, respectively, to 2% and 69% at 350 °C and 30% and 80% at 400 °C under full syngas blends. Full article

Four industrial wastes, i.e., blast furnace slag, steel slag, desulfurization ash, and phosphoric acid sludge, were used to prepare a low-carbon binder, metallurgical slag-based cementitious material (MSCM). The feasibility of solidification/stabilization of municipal solid waste incineration (MSWI) fly ashes by MSCM were evaluated, and the immobilization mechanisms of heavy metals were proposed. The MSCM paste achieved 28-day strength of 35.2 MPa, showing its high-hydration reactivity. While the fly ash content was as high as 80 wt.%, the 28-day strength of MSCM-fly ash blocks reached 2.2 MPa, and the leaching concentrations of Pb, Zn, Cr, and Hg were much lower than the limit values of the Chinese landfill standard (GB 16889-2008). The immobilization rates of each heavy metal reached 98.75–99.99%, while four kinds of MSWI fly ashes were solidified by MSWI at fly ash content of 60 wt.%. The 28-day strength of binder-fly ash blocks had an increase of 104.92–127.96% by using MSCM to replace ordinary Portland cement (OPC). Correspondingly, the lower leachability of heavy metals was achieved by using MSCM compared to OPC. The mechanisms of solidification/stabilization treatment of MSWI fly ash by MSCM were investigated by XRD, SEM, and TG-DSC. Numerous hydrates, such as calcium silicate hydrate (C-S-H), ettringite (AFt), and Friedel’s salt, were observed in hardened MSCM-fly ash pastes. Heavy metals from both MSWI fly ash and MSCM could be effectively immobilized via adsorption, cation exchange, precipitation, and physical encapsulation. Full article

Its relatively low cost and high surface area makes activated carbon an ideal adsorbent candidate for H₂S removal. However, physical adsorption of H₂S is not very effective; therefore, methods to facilitate reactive H₂S oxidation on carbons are of interest. The performance of H₂S removal of non-impregnated, impregnated, and doped activated carbon in low-temperature syngas was evaluated in fixed-bed breakthrough tests. The importance of oxygen content and relative humidity was established for reactive H₂S removal. Impregnates especially improved the adsorption rate compared to non-impregnated carbons. Non-impregnated carbons could however retain a high capture capacity with sufficient contact time. In a relative performance test, the best performance was achieved by doped activated carbon, 320 mg g⁻¹. Ammonia in syngas was found to significantly improve the adsorption rate of non-impregnated activated carbon. A small quantity of ammonia was consumed by the carbon bed, suggesting that ammonia is a reactant. Finally, to validate ammonia-enhanced desulfurization, bench-scale experiments were performed in biomass-based gasification syngas. The results show that when the ammonia concentration in syngas was in the tens of ppm range, 40–160 ppm H₂S oxidation proceeded rapidly. Ammonia-enhanced oxidation allows utilization of cheaper non-impregnated activated carbons by in situ improvement of the adsorption kinetics. Ammonia enhancement is therefore established as a viable method for achieving high-capacity H₂S removal with unmodified activated carbons. Full article

The reactive adsorption desulfurization (RADS) of a model gasoline n-hexane containing thiophene was carried out with a NiO/ZnO-Al₂O₃-SiO₂ adsorbent in N₂ and H₂, respectively. A declining RADS trend has been observed in N₂, without the presence of H₂, indicating that NiO is sulfurized and exhibits activity for RADS. TPR and XPS results presented NiO in the adsorbent is hard to be reduced because of the powerful interaction between NiO and the support. The sulfurization of NiO into NiSx is a primary condition for the RADS process, the same as the presulfurization of hydrotreating catalyst, while metallic Ni is an intermediate reduction product of NiSx. Results of a low RADS temperature at 300 °C, much lower than the reduction temperature of NiO, suggest that NiO plays an important role. Based on assumption of NiO as the main active component, the RADS could reduce the reaction temperature and energy consumption significantly. The participation of hydrogen and n-hexane in pretreatment conducted at 420 °C contributes to the activation of adsorbent. Also, these methods of pretreatment improved the desulfurization performance under the reaction temperature of 300 °C. Full article

Biochar from the liquefaction of pig manure was used as a precursor of H₂S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl₂ in two different ratios of char to an activation agent (1:1 and 1:2) was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 mg/g H₂S. Sulfur was the predominant product of reactive adsorption. Its deposition in the pore system and blockage of the most active pores ceased the materials’ activity. The presence of the catalytic phase was necessary but not sufficient to guarantee good performance. The developed porosity, which can store oxidation products in the resulting composite, is essential for the good performance of the desulfurization process. The surface of the composite with nanographite showed the highest catalytic activity, similar to that of the commercial Midas^® carbon catalyst. The results obtained indicate that a high quality reactive adsorbent/catalyst for H₂S removal can be obtained from pig manure liquefaction wastes. Full article