The degradation of phenol in Cl−-rich water by Fe(VI) was investigated using both chromatographic methods (HPLC and IC) and an on-line direct mass spectrometry (MS) analysis technique. Participation of Cl− during phenol degradation was observed through the formation of p-chlorophenol and coupled species with phenol. Though only a small concentration of Cl− was involved in the reaction, the presence of Cl− could affect the behavior of phenol substantially. With the increase of the Cl− concentration, generation of p-benzoquinone and p-chlorophenol was increased. Meanwhile, phenol in the bulk solution displayed a sharp decline followed by a gradual increase. The developed on-line MS analysis facilitated real-time monitoring of phenol changes in the reaction system. The results showed that phenol degradation by Fe(VI) with the presence of a high concentration of Cl− followed a second-order reaction process. The degradation pathway of phenol was also identified, with p-chlorophenol, p-benzoquinone, maleic acid and formic acid as the main byproducts.
The Ag@CPO-27-Ni composites were deliberately synthesized with different loading amounts of silver nano-particles in CPO-27-Ni which features unsaturated metal sites and cylindrical one-dimensional channels having a diameter of ca. 11 Å constructed by 2,5-dihydroxybenzene-1,4-dicarboxylate and Ni 2+ by a simple one-pot solvothermal method. The well-characterized composites were used as adsorbents to eliminate the aromatic S-compounds of the model oil and fluid catalytic cracking (FCC) oil at room temperature. The experimental results showed that the adsorptive desulfurization followed pseudo-second order reaction kinetics and the adsorptive desulfurization capacity of Ag@CPO-27-Ni (wherein Ag is 1.23 wt%) was notably enhanced as compared with CPO-27-Ni under the same experimental conditions. Impressively, 35 ppmw S dibenzothiophene (DBT) (or benzothiophene (BT))-containing model oil (20 g) was desulfurized to 2.01 ± 0.27 (or 4.05 ± 0.26) ppmw S by using 0.2 (or 0.5) g of the composite, respectively; the composite showed much higher selectivity factor of adsorbing DBT to naphthalene than CPO-27-Ni. The notable enhancement in adsorptive desulfurization performance is thought to be due to the interactions between Ag particles and sulfur or π-system of thiophene moiety in the S-containing compounds that consequently promote selective attraction between S-containing compounds and the composite. Besides, the composite also showed satisfactory recyclability.
To explore the hydrolysis rules of the methoxysilane coupling agents (MSCA), the Fourier transform near infrared (FTNIR) spectroscopy combined with the partial least squares (PLS) model were successfully applied to study the hydrolysis kinetics of the phenyltrimethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, (3, 3, 3-trifluoropropyl)trimethoxysilane and (1H, 1H, 2H, 2H-perfluorooctyl)trimethoxysilane in a HCl-catalyzed EtOH system. The fluorinated silicone resin was synthesized by the hydrolysis and copolycondensation reactions of the 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane and methyltrimethoxysilane. The results were listed as follows: (1) the fast scanning speed, no sampling characters of the FTNIR spectroscopy, and the data processing ability of the PLS, enabled the method to “catch” the fast changing [H 2 O] accurately in real time with the resolution of 23 s. (2) The hydrolysis reactions were second-order reactions, the measured results were in good agreement with the theoretical kinetic equations in the primeval stage. Both temperature and acidity could promote the hydrolysis reactions. The applicable pH of this method was 3 ~ 7. The rate constant of the PTMS was sensitive to the temperature. The phenyl was unfavorable while the vinyl was favorable to the hydrolysis reaction. (3) The fluorinated silicone resins could hardly be cured without catalysis when the n(PFOTMS)/(n(MTMS) + n(PFOTMS)) was higher than 75%. The steric hindrance of the bulky long-chain 1H, 1H, 2H, 2H-perfluorooctyl had nearly no affect on the hydrolysis reactions in the dilute solutions, but strongly hindered the curing processes in the sticky systems. The introduction of the F atoms brought a great rise of hydrophobicity and thermostability to the silicon resin.
危险品化学品经营许可证（带存储）