The reactive adsorption desulfurization of model gasoline was carried out on Ni/ZnO-HY adsorbent.The Ni/ZnO-HY adsorbent was characterized by N2adsorption-desorption test(BET),X-ray diffractometry(XRD),and temperature-programmed reduction(TPR)analysis.The test results have demonstrated that HY-zeolite is a feasible support for Ni/ZnO components used in reactive adsorption desulfurization.The results of XRD and TPR analyses showed that most of nickel element was present as Ni2+species with only a small part existing as Ni3+species,and the Ni2+species had interactions with HY-zeolite.Under the conditions of this study,which specified a 50% ratio of HY-zeolite in the adsorbent,a Zn/Ni molar ratio of 10,and a reduction temperature of 400℃,the Ni/ZnO-HY adsorbent showed the best desulfurization performance.The sulfur capacity of Ni/ZnO-HY adsorbent could be recovered to 92.19% of the fresh one after being subjected to regeneration at 500℃,and could be maintained at 82.17% of the fresh one after 5 regeneration cycles.
Adsorptive desulfurization for removing propylmercaptan (PM) and dimethyl sulfide (DMS) over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of S per gram of adsorbent was demonstrated. The influence of loading amount of Cu (II) and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu (II) was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the v(C-S) and v(Cu-S) vibrations were detected from the Raman spectra of the Cu (II) complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M (σ) bonds.
The effect of mixed oxide support on the performance of Ni/ZnO in the reactive adsorption desulfurization(RADS) reaction was investigated in a fixed bed reactor by using thiophene as the sulfur-containing compound in the model gasoline. A series of oxide supports for Ni/ZnO were synthesized by the co-precipitation method and characterized by XRD, N_2-adsorption, TPR and NH_3-TPD techniques. It was found that the desulfurization capacity of Ni/ZnO was enhanced greatly when active components were supported on the proper mixed oxide. Ni/ZnO supported on oxides exhibited much higher desulfurization efficiency and sulfur adsorption capacity than the unsupported Ni/ZnO and the synthesized Ni/ZnO-SA adsorbent exhibited the highest efficiency for thiophene removal. The higher desulfurization activity and sulfur capacity of Ni/ZnO supported on SiO_2-Al_2O_3 with small particle size, high specific surface area and large pore volume could promote the high dispersion of active metal phase and the transfer of sulfur to ZnO with lower mass transfer resistance. γ-Al_2O_3 species could weaken the interaction of active phases and SiO_2 as well as could increase greatly the amount of weak acids. Therefore, these oxides could impose a great influence on the structure and chemical properties of the catalyst.
The systematic research about the adsorption desulfurization and competitive behavior from 1-hexene over cesium-exchanged Y zeolites has been investigated. The structural properties of the adsorbents were characterized by X-ray diffraction(XRD), N_2 sorption(BET) and thermal analysis(TGA). The effects of calcination temperature, calcination atmosphere, and adsorption temperature were studied by the dynamic and static tests. The competitive adsorption mechanisms between thiophene and 1-hexene were studied by in-situ Fourier transform infrared spectroscopy(in-situ FTIR) and temperature-programmed desorption(TPD). CsY adsorbents exhibited high selectivity for thiophene even when a large amount of olefins exist.In-situ FTIR spectra of thiophene and 1-hexene adsorption indicated that both thiophene and 1-hexene were mainly adsorbed on CsY via π-complexation. The higher desorption activated energy and higher adsorption heat of thiophene than 1-hexene obtained by thiophene-TPD and hexene-TPD has revealed that thiophene is adsorbed more strongly in CsY adsorbents than 1-hexene.
In this paper, a low-cost activated carbon(AC) was prepared from deactivated resin catalyst(DRC) for methyl tert-butyl ether(MTBE) synthesis through carbonization and subsequent steam activation treatment. The activated carbon was characterized in detail. After loading various transition metals, including Cu^(2+), Ag+, Co^(2+), Ni^(2+), Zn^(2+), and Fe^(3+) via the ultrasonic-assisted impregnation method, a series of metal-loaded adsorbents(xM-AC) were obtained and their dimethyl sulfide(DMS) adsorption performance was investigated in a batch system. Among these adsorbents, 15Cu-AC presented a superior DMS adsorption capacity equating to 58.986 mg/g due to the formation of S-M(σ) bonds between Cu^(2+) and sulfur atoms of DMS as confirmed by the Raman spectra and kinetic study.