Preparation of ZIF-8@PEBAX/PVDF nanocomposite membrane by the combination of self-assembly and in-situ growth for removing thiophene from the model gasoline

Metal-organic frameworks(MOFs)have gained attention in the development of MOFs/polymer hybrid membranes for pervaporation.However,the agglomeration of MOFs particles and interfacial defects limit its further application.In this study,we present a novel approach to fabricate a ZIF-8@PEBAX/PVDF nanocomposite membrane for removing thiophene from the model gasoline by combination of selfassembly and in-situ growth.Firstly,a PVDF supporting membrane was modified to have a negative charge.Next,positively charged zinc ions were attracted onto the negatively charged PVDF supporting membrane through electrostatic interaction.Afterwards,the Zinc ions deposited PVDF membrane was immersed into dimethylimidazole solution to form a uniform ZIF-8 layer.Finally,the ZIF-8 layer was coated with poly(ether-block-amide)(PEBAX)using the pouring method.Experimental results showed that the separating efficiency of the ZIF-8@PEBAX/PVDF nanocomposite membrane was improved significantly compared to that of pristine PEBAX membrane.The optimal permeation flux and enrichment factor of membrane were 27.80 kg(m^(2)h)^(-1)and 6.9,respectively.

Oxidation of Thiophenes over Silica Gel in Hydrogen Peroxide/Formic Acid System

Thiophene (C4H4S) and 3-methylthiophene(3-MC4H4S) are typical thiophenenic sulfur compounds that exist in fluid catalytic cracking (FCC) gasoline. Oxidation of C4H4S and 3-MC4H4S were conducted in hydrogen peroxide (H2O2) and formic acid system over a series of silica gel loaded with metal oxide. The silica gel loaded with copper and cobalt (1:1) oxide was found very active for the model compound oxidation using H2O2/formic acid, while the silica gel unloaded with metal oxide was less active. The sulfur removal rate of thiophenes was different as solvent was changed. And the conversation of C4H4S and 3-MC4H4S was improved at higher temperature,but reduced when olefin was added. The sulfur removal rate of model sulfur compounds was enhanced when the phase transfer catalyst emulsifier polyethylene glycol octyl phenyl ether or tetrabutylammonium bromide(TBAB)in a H2O2 and formic acid system with the addition of TBAB, a bromine substitution trend appeared in the oxidation of thiophenes, suggesting the influence of TBAB.

Oxidation of Thiophenes over Silica Gel in Hydrogen Peroxide/Formic Acid System

Thiophene C4H4S and 3-methylthiophene3-MC4H4S are typical thiophenenic sulfur compounds that exist in fluid catalytic cracking FCC gasoline. Oxidation of C4H4S and 3-MC4H4S were conducted in hydrogen peroxide H2O2 and formic acid system over a series of silica gel loaded with metal oxide. The silica gel loaded with copper and cobalt 1:1 oxide was found very active for the model compound oxidation using H2O2formic acid, while the silica gel unloaded with metal oxide was less active. The sulfur removal rate of thiophenes was dif- ferent as solvent was changed. And the conversation of C4H4S and 3-MC4H4S was improved at higher temperature, but reduced when olefin was added. The sulfur removal rate of model sulfur compounds was enhanced when the phase transfer catalyst emulsifier polyethylene glycol octyl phenyl ether or tetrabutylammonium bromideTBAB was added. The sulfur removal rate of simulated gasoline containing 524μg·ml-1 sulfur reached 90%. Interestingly, in a H2O2 and formic acid system with the addition of TBAB, a bromine substitution trend appeared in the oxidation of thiophenes, suggesting the influence of TBAB.

Reactive adsorption of thiophene on Ni/ZnO adsorbent:Effect of ZnO textural structure on the desulfurization activity

To better understand the nature of reactive adsorption of thiophene on Ni/ZnO adsorbent,the effect of ZnO textural structure on the desulfurization activity was investigated.ZnO materials were synthesized by low-temperature solid-state reaction and the corresponding Ni/ZnO adsorbents were prepared by incipient impregnation method.The analysis results showed that the crystalline sizes of ZnO as-synthesized as well as the BET surface areas varied obviously with the calcination temperature.The activity evaluations indicated that the Ni/ZnO adsorbents prepared with ZnO possessed a favorable textural structure as active component exhibited good activity of removing thiophene.The evolutions of the main crystalline phases of Ni/ZnO adsorbents before and after reaction confirmed that ZnO played a crucial role in taking up S element and converting it into ZnS in the reactive adsorption process.It was concluded that ZnO with larger surface area and smaller crystal particles resulted in better desulfurization activity,which may be the main reason for the different activities of the Ni/ZnO adsorbents prepared with ZnO calcined at different temperatures.

Effects of toluene on thiophene adsorption over NaY and Ce(IV)Y zeolites

Zeolites NaY and Ce（IV）Y were employed as adsorbents to remove organic sulfur compounds from model gasoline （MG） solutions with and without toluene in static adsorption experiments at room temperature （RT） and atmospheric pressure. The adsorbents were characterized by XRD, XRF and pyridine infrared spectrum （IR）. The adsorption experiments show that the desulfurization performance of Ce（IV）Y is much better than that of NaY. The sulfur removal over both NaY and Ce（IV）Y decreases with the increase of toluene concentration in MG, however, the decline tendency on Ce（IV）Y is smooth, and it is steep on NaY. FT-IR spectra of thiophene adsorption indicate that thiophene molecules are mainly adsorbed on NaY via π electron interaction, but on Ce（IV）Y, in addition to the π electron interaction, both Ce^4＋-S direct interaction and protonation of thiophene also play important roles. Toluene molecules are adsorbed on NaY also via π electron interaction. Although the amount of Bronsted acid sites is increased due to the introduction of Ce^4＋ ions into NaY zeolite, it is not found to influence the adsorption mode of toluene over Ce（IV）Y. Compared with NaY zeolite, the improved desulfurization performance over Ce（IV）Y for removing organic sulfur compounds from MG solution, especially those containing large amount of aromatics, may be ascribed to the direct Ce（IV）-S interaction, which is much resistant to the influence resulted from toluene adsorption.

Kinetics and Mechanism of the Photo-oxidation of Thiophene by O_2 Adsorbed on Molecular Sieves

Photochemical oxidation of thiophene in n-octane/water extraction system using O2 as oxidant was studied. The reaction mechanism ofthiophene oxidation was proposed. Results obtained here can be used as the reference for the oxidative desulfurization of gasoline because thiophene is one of the main components containing sulfur in fluid catalytic cracking gasoline. Thiophene dissolved in n-octane was photodecomposed and removed into the water phase at ambient temperature and atmospheric pressure. A 500 W high-pressure mercury lamp （main wave length 365 nm, 0.22 kW/m） was used as light source for irradiation, and air was introduced by a gas pump to supply O2. Thiophene can be photo-oxidized to sulfone, oxalic acid, SO4^2-, and CO2. The desulfurization yield of thiophene in n-octane is 58.9% under photo-irradiation for 5 h under the conditions of air flow at 150 mL/min and V（water）：V（n-octane）=1：1. It can be improved to 92.3% by adding 0.15 g zeoliteartificial into 100 mL reaction system, which is the adsorbent for O2 and thiophene. And under such conditions, the photo-oxidation kinetics of thiophene with O2/zeoliteartificial is first-order with an apparent rate constant of 0.5047 h^-1 and a half-time of 1.37 h. The sulfur content can be depressed from 800 μL/L to less than 62 μL/L.

Molecular Simulation Study on Interaction of Thiophene Sulfides with Transition Metals

The computer molecular simulation technique was applied to study the chemisorption of thiophene and tetramethylthiophene as the model sulfides on the simple oxides and complex oxides of some transition metals as the catalytic materials. The study disclosed that the thiophene sulfides could enter into chemisorption with metal oxides such as VO, ZnO, NiO and Zn-Al-spinel. This interaction could lead to thiophene molecular structure deformation to be in an activated adsorption state, which could help to promote the conversion of thiophene sulfides in the course of catalytic cracking. The VO with a valence of 2 could provide relatively strong selective adsorption sites for the conversion of thiophene sulfides to apparently transform the molecular structures and electron cloud states of such heterocyclic sulfur compounds such as thiophene and tetramethylthiophene into an activated adsorption state. The effect of this interaction was more pronounced with respect to tetramethylthiophene.

Novel MWCNT-Support for Co-Mo Sulfide Catalyst in HDS of Thiophene and HDN of Pyrrole

With home-made multi-walled carbon nanotubes （MWCNTs, simplified as CNTs in later text） as support, CNT-supported Co-Mo-S catalysts, denoted as x%（mass percentage）MoiCoj/CNTs, were prepared. Their catalytic performance for thiophene hydrodesulfurization （HDS） and pyrrole hydrodenitrification （HDN） reactions was studied, and compared with the reference system sup- ported by AC. Over the 7.24%Mo3Co1/CNTs catalyst at reaction condition of 1.5 MPa, 613 K, C4H4S/H2=3.7/96.3（molar ratio） and GHSV≈8000 mlswP/（g-cat.h）, the specific HDS activity of thiophene reached 3.29 mmolc4H4S/（s.molMo）, which was 1.32 times as high as that （2.49 mmolc4H4S/（s.molMo）） of the AC-based counterpart, and was 2.47 times as high as that （1.33 mmolc4H4S/（s-molMo）） of the catalysts supported by AC with the respective optimal MoaCol-loading amount, 16.90%Mo3Co1/AC. Analogous reaction-chemical behaviours were also observed in the case of pyrrole HDN. It was experimentally found that using the CNTs in place of AC as support of the catalyst caused little change in the apparent activation energy for the thiophene HDS or pyrrole HDN reaction, but led to a significant increase in the concentration of catalytically active Mo-species （Mo^4＋） at the surface of the functioning catalyst. On the other hand, H2-TPD measurements revealed that the CNT-supported catalyst could reversibly adsorb a greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to about 673 K. This unique feature would help to generate microenvironments with higher stationarystate concentration of active hydrogen-adspecies at the surface of the functioning catalyst. Both factors mentioned above were favorable to increasing the rate of thiophene HDS and pyrrole HDN reactions.

Synthesis of New Schiff Bases Containing Thiophene Moiety

Seven new Schiff bases, which are 4,4,4-trifluo-ro-1-(2-thienyl)-1-butanone-3-Z, Z =-thioseraicarbazone (a); -thiocarbohydrazone (b),-benzoic hydrazone (c), -( o-hydroxyphenyl) imine (d) ,-nicotinic hydrazone (e),-salicylic hydrazone (f), and -(p-fluoro-m-chlorophenyl) imine (g), have been synthesized by reaction of 4, 4, 4-trifluoro-1-(2-thienyl)-1,3-butanedione (TFTBD) with corresponding hy-drazides or anilines, acetic acid or p-toluence sulfonic acid as catalyst, and characterized by Elemental analysis, IR, UV-Vis,1H NMR and MS. The MS spectra confirmed that the -C3=O condensed with primary amino group. Tauto-merism of the compounds is discussed.

Sulfur promoted n-π^(*)electron transitions in thiophene-doped g-C_(3)N_(4)for enhanced photocatalytic activity

Expanding the optical absorption range of photocatalysts is still a key endeavor in graphitic carbon nitride(g-C_(3)N_(4))studies.Here,we report on a novel thiophene group extending the optical property,which is assigned to n-π^(*)electronic transitions involving the two lone pairs on sulfur(TLPS).The as-prepared samples,denoted as CN-ThAx(where x indicates the amount of ThA added,mg),showed an additional absorption above 500 nm as compared to pristine g-C_(3)N_(4).Further,the thiophene group enhanced charge carrier separation to suppress e‒/h+pair recombination.The experimental results suggest that the thiophene group can obstruct the polymerization of melem to generate a large plane,thus exposing the lone electron pairs on the sulfur.The photocatalytic activity was evaluated in the decomposition of bisphenol A and H2 evolution.Compared with g-C_(3)N_(4),the optimized CN-ThA_(30) sample led to a 6.6-and 2-fold enhancement of the degradation and H2 generation rates,respectively.The CN-ThA_(30) sample allowed for synchronous H2 production and BPA decomposition.

A Frequency-Response Study on Sorption of Thiophene and Benzene on NiY Zeolite

The adsorption behavior of thiophene and benzene on NiY zeolite has been investigated by the frequency response(FR) method.The FR spectra of thiophene and benzene on NiY zeolite were recorded at 302-335 K in a pressure range of 26.6-266 Pa.The results showed that adsorption was found to be the rate-controlling process for the thiophene/NiY zeolite system,and there were two different adsorption processes.Two kinds of adsorption models have been proposed,namely:the S-M interaction(low frequency adsorption) and the π-complexation(high frequency adsorption).High frequency adsorption obeyed the Langmuir model.By combining the FR method and Langmuir model,the adsorption site of high frequency adsorption process at 302 K and 335 K was 3.172 mmol/g and 2.974 mmol/g,respectively,and on the combined adsorption isotherms,the adsorption site of the low frequency adsorption process at 302 K and 335 K was 0.308 mmol/gand 0.436 mmol/g,respectively.The low frequency adsorption process(S-M interaction) was the main adsorption process.The diffusion process was the rate-controlling process for the benzene-NiY zeolite system.

Photocatalytic Oxidation Kinetics of Thiophene with Nano-F^-/Fe^(3+)/TiO_2

Photocatalytic oxidation kinetics of thiophene in n-octane/water extraction system was studied with fluorine and ferric ion codoped nano-TiO_2(nano-F^-/Fe^(3+)/TiO_2) powders used as the photocatalyst.Effects of initial concentration of thiophene and additional dosage of F^-/Fe^(3+)/TiO_2 on the reaction rate constant and half-life were investigated.The results showed that the appropriately added dosage of F^-/Fe^(3+)/TiO_2 was 0.1 g in the 100-mL reaction system and the photooxidative kinetics of thiophene in the presence of F^-/Fe^(3+)/TiO_2 catalyst was of first-order with a rate constant of 0.6508 h^(-1) and a half-life of 1.0651 h.The desulfurization rate of thiophene was 98.1%in 5 h and the sulfur content could be reduced from 800 ppm to 15 ppm.The reaction rate constant increased with a decreasing initial concentration of thiophene.

Reactive Adsorption of Thiophene on ZnNi/Diatomite-Pseudo-Boehmite Adsorbents

The thiophene removal ability of the synthesized ZnNi/diatomite-pseudo-boehmite adsorbent was tested in a lab- scale fixed-bed reaction system. X-ray diffractograms （XRD） were used to characterize the adsorbent samples. The effects of Zn/Ni molar ratio, various model fuels and regeneration patterns on the RADS tests were studied. The adsorption mecha- nism was investigated by XRD and MS analyses. The results indicted that thiophene in the model fuel was first decomposed on the surface Ni of the adsorbent to form Ni3S2 while the hydrocarbon portion of the molecule was released back into the process stream, followed by reduction of Ni3S2 to form H2S in the presence of H2, and then HzS is stored in the adsorbent accompanied by the conversion of ZnO into ZnS.

DFT Study of Thiophene Adsorption on the Pd(111) and Pt(111) Surfaces

Thiophene adsorption on the（111） surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecular plane of thiophene ring is distorted with C=C bond being elongated to 1.450 and C–C bond being shortened to 1.347 ,and the C–H bonds tilt 13.91～44.05o away from this plane.Furthermore,analysis on population and density of states verified the calculated adsorption geometries.Finally,charge analysis suggests that thiophene molecule is an electron acceptor,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.

Superparamagnetic Supported Catalyst H_3PW_(12)O_40/γ-Fe_2O_3 for Alkylation of Thiophene with Olefine

The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from lighl fractions by distillation. A series of superparamagnetic supported catalysts, used for alkylation of thiophene with 1-octene, were prepared by loading H3PW12040 （HPW） onto commercially available nanoparticles γ-Fe2O3 through incipient wet impregnation method. The catalysts were characterized by X-ray diffraction （XRD）, Fourier transform infra-red （FT-IR）, thermo gravimetric analysis （TG）, N2-adsorption and vibrating sample magnetometer （VSM）. The physicochemical characterization reveals that 7-Fe203 could be accommodated to immobilize and disperse HPW. Moreover, possessing high magnetization of 26.1 A.mZ.kg-1 and with mesoporous structure with specific surface area of 35.9 m2·g^-1, the 40% （by mass） HPW loading catalyst is considered the proper catalyst for olefinic alkylation of thiophenic sulfur （OATS） and can be separated in an external magnetic field. The catalytic activity was investigated in the alkylation reaction of thiophene with 1-octene, and the conversion of thiophene is up to 46% at 160 ℃ in 3 h. The 40% （by mass） H3PW12O40/γ-Fe2O3 catalyst can be reused 6 times without too much loss of activit and keeps its property of superparamagnetism.

Removal of Thiophene from Benzene from Coal Source by Liquid Adsorption on Modified ZSM-5 Synthetic Zeolite

The use of a modified ZSM-5 molecular sieve to remove thiophene from benzene was demonstrated. Adsorption equilibrium experiments were carried out in an enclosed vessel in which a known amount of zeolite was contacted with 20-40 ml of benzene-thiophene solution. The solutions were analyzed by gas chromatography with flame photometric detector. Thiophene was not physically adsorbed on a single molecular layer but mainly adsorbed chemically onto the modified ZSM-5 zeolite adsorbent.

Study on Reaction of Thiophene Compounds and Olefins for Deep Desulfurization of Gasoline

The HY,Hβ,HZSM-5,and SAPO-11 zeolites were investigated in the alkylation reaction of thiophene and olefins.As a result,some sulfur-containing impurities could be converted to higher molecular weight components with their boiling point being in the range of diesel fraction.HZSM-5 had the highest activity and selectivity of desulfurization.At the same time,extensive oligomerization of olefins was not found and coke yield was very low,which could lead to high yield of gasoline products.The main reaction mechanism verifies that the second order alkylation reaction can be carried out on the outer surface and/or pores of the catalyst.The catalytic performance of the HZSM-5 catalyst which is poisoned by 2,4-dimethylquinoline during alkylation to form larger molecules of sulfur compounds is obviously weakened due to the decrease of the acid sites on the outer surface and at the mouth of pores.

Hydrodesulfurization of Thiophene on Ni,Mo-supported MCM-41 Catalysts

MoO 3 and NiO supported MCM 41 and AlMCM 41 catalysts were prepared. The XRD and N 2 adsorption/desorption results show that MoO 3 was more readily dispersed on the supports than NiO. The activities of the catalysts for thiophene hydrodesulfurization are strongly affected by the block of the unidimensional mesoporous channels with oxide crystallites and/or extra framework impurities. Mo supported MCM 41 catalysts are more active for hydrodesulfurization than Ni and Ni, Mo supported MCM 41 catalysts.

NMR Parameters and Vibrational Investigation of 2-Dicyanovinyl-5-(4-ethoxyphenyl) thiophene by ab initio HF and DFT Calculations

Optimized geometry and harmonic vibrational frequency of 2-dicyanovinyl-5-（4- ethoxyphenyl）thiophene （C16Hj2N2OS） are calculated at the HF/6-31＋＋G（d,p） and B3LYP/6- 311 ＋＋G（d,p） levels. Mulliken charges in the ground state are also calculated. The research shows the presence of intermolecular interaction in the title compound. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. A detailed interpretation of the infrared spectra of the title compound is reported. The theoretical spectrograms for IR spectra of the title compound have been constructed, The isotropic chemical shift computed by 13C and 1H NMR analyses also shows good agreement with the experimental observations.

An asymmetric membrane of polyimide 6FDA-BDAF and its pervaporation desulfurization for n-heptane/thiophene mixtures

Polyimide（PI） is a type of important membrane material. A soluble polymer was synthesized from 4,4′-（hexafluoroisopropylidene） diphthalic anhydride（6FDA） and 2,2-bis[4-（4-aminophenoxy） phenyl] hexafluoropropane（BDAF） by the two-step polymerization method. The polymer was proved to be polyimide 6FDA-BDAF by the Fourier transform infrared（FT-IR）, the 1H-NMR and ^（19）F-NMR spectra. An asymmetric membrane was prepared with the synthesized polyimide 6FDA-BDAF, it was porous in the 50 μm height bulk and dense in a 3–5 μm height surface. The membrane was used to separate n-heptane/thiophene mixtures by pervaporation with sulfur（S） contents from 50 to 900 μg g^（–1）. The total flux was enlarged from 7.96 to 37.61 kg m^（–2） h^（–1） with temperature increasing from 50 to 90°C. The membrane＇s enrichments factor for thiophene were about 3.13 and dependent on the experimental conditions. The experimental results demonstrated that polyimide 6FDA-BDAF would be a potential membrane material for desulfurization and controlled release of the S-containing fertilizer.