New insights into the mechanism of reactive adsorption desulfurization on Ni/ZnO catalysts:Theoretical evidence showing the existence of interfacial sulfur transfer pathway and the essential role of hydrogen

As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.

Fabrication of hierarchical porous ZnO and its performance in Ni/ZnO reactive-adsorption desulfurization

To investigate the effect of texture structure on the desulfurization performance in the Ni/ZnO reactive adsorption desulfurization（RADS） system,two kinds of ZnO porous materials with rod-shaped morphology were synthesized and their structure was characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,and N2 adsorption/desorption.The formation mechanisms of hierarchical porous ZnO（ZnO with meso and macro pores） were also studied.Their application performance was evaluated in the RADS process over Ni/ZnO absorbent.Due to the difference in structure between the two kinds of ZnO,the two ZnO based adsorbents showed different desulfurization activity.

Reactive adsorption desulfurization coupling aromatization on Ni/ZnO-Zn_6Al_2O_9 prepared by Zn_xAl_y(OH)_2(CO_3)_z·x H_2O precursor for FCC gasoline

Aiming to improve the reactive adsorption desulfurization（RADS） performances of Ni/Zn O adsorbents,ZnxAly（OH）2（CO3）z·x H2 O precursor is synthesized by coprecipitation of Zn2＋,AlO-2,and CO2-3; the Zn OZn6Al2O9 composite oxides are obtained by the calcination of ZnxAly（OH）2（CO3）z·x H2 O precursor,and the Ni/Zn O-Zn6Al2O9（6.0 wt% Ni O） adsorbents are prepared by wetness impregnation method. The phase,acid strength,acid type and quantity,morphology,and thermal properties were characterized by X-ray diffraction,temperature-programmed desorption of ammonia,pyridine-adsorbed infrared spectrum,high-resolution transmission electron microscopy,and Thermo Gravimetry-Derivative Thermo Gravimetry（TG-DTG）,respectively. The breakthrough sulfur capacities of six adsorbents are between 34.2 and 47.9 mg/gcat. The kinetic studies indicated that the active energy of RADS（49.4 k J/mol） could reach nano-sized Zn O,the particle size of is about 12.0 nm. All the excellent RADS performances can be due to the high SBET. Also,there are some extents of aromatization reactions that occur,which can be contributed to the B？nsted acid rooted in Zn6Al2O9 composite oxide,and the octane number of products can be preserved well.

Adsorption Properties and Quantum Molecular Descriptors of the Folic Acid Drug Adsorbed onto Zigzag and Armchair Single Walled Carbon Nanotubes:DFT Simulations

The adsorption behavior of folic acid onto（5,0） zigzag and（5,5） armchair carbon nanotube（SWCNT） has been investigated using B3 LYP density functional at the 6-31G＊ level. The adsorption energies,molecular orbital analysis and structural changes at the adsorption site are indicative of covalent adsorption on the zigzag SWCNT surface,while the adsorption is physical on the armchair SWCNT surface. The density of states（DOS） Plot and the quantum molecular descriptors（QMD） are witness to the significant changes in the electronic properties of SWCNT systems after the attachment of adsorbed species to the tube surface. According to the calculated results,the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.

Regenerable adsorbent for removing ammonia evolved from anaerobic reaction of animal urine

The waste gas evolved from biodegradation of animal urine contains ammonia causing environmental concerns. A new and effective method for removing ammonia from such waste gas using reactive adsorption is presented. In the process, activated carbon impregnated with H2SO4（H2SO4/C） is employed. Ammonia in the waste gas reacts with H2SO4 on the adsorbent instantaneously and completely to form （NIL）2SO4. The H2SO4/C adsorbent is high in NH3 adsorption capacity and regenerable. The NH3 removal capacity of this regenerable adsorbent is more than 30 times that of the adsorbents used normally in the industry. The spent H2SO4/C is regenerated by flowing low-pressure steam through the adsorbent bed to remove the （NH4）2SO4 from the adsorbent. The regeneration by-product is concentrated （NH4）2SO4 solution, which is a perfect liquid fertilizer for local use. Re-soaking the activated carbon with H2SO4 solution rejuvenates the activity of the adsorbent. Thus the H2SOJC can be reused repeatedly. In the mechanism of this reactive adsorption process, trace of H20 in the waste gas is a required, which lends itself to treating ammonia gas saturated with moisture from biodegradation of animal urine.

Reactive adsorption desulfurization over a Ni/ZnO adsorbent prepared by homogeneous precipitation

A high-performance Ni/ZnO adsorbent was prepared by homogeneous precipitation using urea hydro- lysis and characterized by N2 adsorption-desorption, X-ray diffraction （XRD）, and scanning electron microscope （SEM）. The adsorbent was applied to the deep desulfur- ization of gasoline and showed a high breakthrough sulful capacity and a remarkably high volume hourly space velocity. The effects of coexisting olefins in gasoline as well as adsorptive conditions on the adsorptive perfor- mance were examined. It was found that olefins in gasoline had a slightly inhibiting effect on the desulfurization performance of the adsorbent. The optimum conditions were 673 K, 1.0 Mpa with a volume hourly space velocity of 60h^-1. Under the optimum conditions, ultralow sulfur gasoline could be produced and the breakthrough sulfur capacity of the adsorbent was 360 mg-s/g-sorb for the model gasoline.

Removing carbonyl sulfide with metal-modified activated carbon

A Cu-Co-K/activated carbon （AC） adsorbent has been developed for the removal of carbonyl sulfide （COS）. The effects of COS concentration, reaction temperature and relative humidity were closely examined. A breakthrough of 33.23 mg COS .gl adsorbent at 60℃, under 30% relative humidity and in presence of 1.0% oxygen was exhibited in the Cu-Co-K/AC adsorbent prepared. Competitive adsorption studies for COS in the presence of CS2, and H2S were also conducted. TPD analysis was used to identify sulfur-containing products on the carbon surface, and the results indicated that H2S, COS and SO2 were all evident in the effluent gas generated from the exhausted Cu-Co-K/AC. Structure of the activated carbon samples has been characterized using nitrogen adsorption, and their surface chemical structures were also determined with X-ray photoelectron spectroscopy （XPS）. It turns out that the modification with Cu（OH）2CO3- CoPcS-KOH can significantly improve the COS removal capacity, forming SO2/4 species simultaneously. Regenera- tion of the spent activated carbon sorbents by thermal desorption has also been explored.