The key reason for SO_(2) formation during the production of a residue hydrogenation catalyst support was identified and subsequent emission reduction solutions were then investigated and verified systematically.The r...The key reason for SO_(2) formation during the production of a residue hydrogenation catalyst support was identified and subsequent emission reduction solutions were then investigated and verified systematically.The results demonstrated that carbon-containing organic materials,including sesbania powder and cellulose,did not completely decompose over the temperature range of 350−600℃during the heating stage of the calcination process,but rather underwent a condensation reaction within the same temperature range to form carbon-containing species with a lower ratio of hydrogen to carbon and a higher condensation degree,which promoted the decomposition of sulfate to form SO_(2).Systematic experimental work revealed that three different measures,i.e.,applying the staged calcination method,reducing the heating rate,and increasing the air flow rate,during the calcination process could all achieve the effect of reducing SO_(2) emissions.展开更多
Metalloporphyrins have devastating effects on the deep processing and efficient utilization of petroleum resources. Various porphyrins are derived from porphin by substitution at the β, meso, or both positions. Herei...Metalloporphyrins have devastating effects on the deep processing and efficient utilization of petroleum resources. Various porphyrins are derived from porphin by substitution at the β, meso, or both positions. Herein, we focus on the interaction between nickel(Ⅱ) and the porphyrin skeleton. Five different density functionals were selected for determining a reliable approach to simulate porphyrin-nickel(Ⅱ) complexes. At D4h symmetry, the 10b1g, 15a1g, 4e1g and 9b2g were dominated by the 3d character of nickel. Compared with pure density functional, the hybrid functional gave larger highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) gap, and the higher HOMO-LUMO gap also corresponded to a higher excitation energy. The characteristic Soret and Q bands modeled by timedependent density functional theory(TDDFT) calculations matched well with experimental results, and the absorption was discussed in detail with natural transition orbitals(NTO) analysis. Furthermore, the binding character of nickel(Ⅱ) with various substituted porphyrins were calculated at perdew-burke-ernzerhof(PBE) level, showed that the geometry and complexation behavior of porphyrin-nickel(Ⅱ) complexes could be significantly tuned by different substituents. The symmetry of the complex was reduced and the skeleton ring get distortion when introducing different substituents. Compared with ETIO porphyrin, the introduction of phenyl on the β position can expand the conjugated system and promote the covalent character of Ni-N bond.展开更多
基金support from the China Petrochemical Corporation(Sinopec Group 121043-2).
文摘The key reason for SO_(2) formation during the production of a residue hydrogenation catalyst support was identified and subsequent emission reduction solutions were then investigated and verified systematically.The results demonstrated that carbon-containing organic materials,including sesbania powder and cellulose,did not completely decompose over the temperature range of 350−600℃during the heating stage of the calcination process,but rather underwent a condensation reaction within the same temperature range to form carbon-containing species with a lower ratio of hydrogen to carbon and a higher condensation degree,which promoted the decomposition of sulfate to form SO_(2).Systematic experimental work revealed that three different measures,i.e.,applying the staged calcination method,reducing the heating rate,and increasing the air flow rate,during the calcination process could all achieve the effect of reducing SO_(2) emissions.
基金supported by National Key R & D program of China (No.2021YFA1501204)Contract Projects of China Petroleum & Chemical Corporation (SINOPEC Corp.) (grant number 123017grant number 121043-2)。
文摘Metalloporphyrins have devastating effects on the deep processing and efficient utilization of petroleum resources. Various porphyrins are derived from porphin by substitution at the β, meso, or both positions. Herein, we focus on the interaction between nickel(Ⅱ) and the porphyrin skeleton. Five different density functionals were selected for determining a reliable approach to simulate porphyrin-nickel(Ⅱ) complexes. At D4h symmetry, the 10b1g, 15a1g, 4e1g and 9b2g were dominated by the 3d character of nickel. Compared with pure density functional, the hybrid functional gave larger highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) gap, and the higher HOMO-LUMO gap also corresponded to a higher excitation energy. The characteristic Soret and Q bands modeled by timedependent density functional theory(TDDFT) calculations matched well with experimental results, and the absorption was discussed in detail with natural transition orbitals(NTO) analysis. Furthermore, the binding character of nickel(Ⅱ) with various substituted porphyrins were calculated at perdew-burke-ernzerhof(PBE) level, showed that the geometry and complexation behavior of porphyrin-nickel(Ⅱ) complexes could be significantly tuned by different substituents. The symmetry of the complex was reduced and the skeleton ring get distortion when introducing different substituents. Compared with ETIO porphyrin, the introduction of phenyl on the β position can expand the conjugated system and promote the covalent character of Ni-N bond.
