Phosphotungstic acid ionic liquid for efficient photocatalytic desulfurization:Synthesis,application and mechanism

An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.

Few-layered hexagonal boron nitride nanosheets stabilized Pt NPs for oxidation promoted adsorptive desulfurization of fuel oil

A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.

Synergistic catalysis of the N-hydroxyphthalimide on flower-like bimetallic metal-organic frameworks for boosting oxidative desulfurization

Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.

Fabrication of Silane and Desulfurization Ash Composite Modified Polyurethane and Its Interfacial Binding Mechanism

Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration of DA as hard segments into the PU molecular chain.The effects of DA content(φ)on the mechanical properties,thermal stability,and hydrophobicity of PU,both before and after the addition of KH550,were thoroughly examined.The results of microscopic mechanism analysis confirmed that KH550 chemically modified the surface of DA,facilitating its incorporation into the polyurethane molecular chain,thereby significantly enhancing the compatibility and dispersion of DA within the PU matrix.When the mass fraction of modified DA(MDA)reached 12%,the mechanical properties,thermal stability,and hydrophobicity of the composites were substantially improved,with the tensile strength reaching 14.9 MPa,and the contact angle measuring 100.6°.

Oxidative Desulfurization of Fuel Oil with H_(3)PO_(4)-based Deep Eutectic Solvents

A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.

Design of dual-functional protic porous ionic liquids for boosting selective extractive desulfurization

Porous ionic liquids have demonstrated excellent performance in the field of separation,attributed to their high specific surface area and efficient mass transfer.Herein,task-specific protic porous ionic liquids(PPILs)were prepared by employing a novel one-step coupling neutralization reaction strategy for extractive desulfurization.The single-extraction efficiency of PPILs reached 75.0%for dibenzothiophene.Moreover,adding aromatic hydrocarbon interferents resulted in a slight decrease in the extraction efficiency of PPILs(from 45.2%to 37.3%,37.9%,and 33.5%),indicating the excellent extraction selectivity of PPILs.The experimental measurements and density functional theory calculations reveal that the surface channels of porous structures can selectively capture dibenzothiophene by the stronger electrophilicity(Eint(HS surface channel/DBT)=-39.8 kcal mol^(-1)),and the multiple extraction sites of ion pairs can effectively enrich and transport dibenzothiophene from the oil phase into PPILs throughπ...π,C-H...πand hydrogen bonds interactions.Furthermore,this straightforward synthetic strategy can be employed in preparing porous liquids,offering new possibilities for synthesizing PPILs with tailored functionalities.

Synthesis of boron nitride nanorod and its performance as a metalfree catalyst for oxidative desulfurization of diesel fuel

In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal-free catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by heating treatment at 900℃ in nitrogen atmosphere that the characteristics of the sample were identified by the X-ray diffraction,Fourier-transform infrared spectroscopy,Raman spectroscopy,field emission scanning electron microscopy,transmission electron microscopy,atomic force microscopy,and N2 adsorption-desorption isotherms.The results of structural and morphological analysis represented that BN has been successfully synthesized.The efficacy of the main operating parameters on the process was studied by using response surface methodology based on the Box-Behnken design method.The prepared catalyst showed high efficiency in oxidative desulfurization of diesel fuel with initial sulfur content of 8040 mg·kg^(-1)S.From statistical analysis,a significant quadratic model was obtained to predict the sulfur removal as a function of efficient parameters.The maximum efficiency of 72.4%was achieved under optimized conditions at oxidant/sulfur molar ratio of 10.2,temperature of 71℃,reaction time of 113 min,and catalyst dosage of 0.36 g.Also,the reusability of the BN was studied,and the result showed little reduction in activity of the catalyst after 10 times regeneration.Moreover,a plausible mechanism was proposed for oxidation of sulfur compounds on the surface of the catalyst.The present study shows that BN materials can be selected as promising metal-free catalysts for desulfurization process.

Enhanced dealkalization of bauxite residue through calcium-activated desulfurization gypsum

A novel integrated approach to remove the free alkalis and stabilize solid-phase alkalinity by controlling the release of Ca from desulfurization gypsum was developed.The combination of recycled FeCl_(3)solution and EDTA activated desulfurization gypsum lowered the bauxite residue pH to 7.20.Moreover,it also improved the residual Ca state,with its contribution to the total exchangeable cations increased(68%-92%).Notably,the slow release of exchangeable Ca introduced through modified desulfurization gypsum induced a phase transition of the alkaline minerals.This treatment stabilized the dealkalization effect of bauxite residue via reducing its overall acid neutralization capacity in abating pH rebound.Hence,this approach can provide guidance for effectively utilizing desulfurization gypsum to achieve stable regulation of alkalinity in bauxite residue.

Effect of integration of mechanical ball milling and flue gas desulfurization gypsum on dealkalization of bauxite residue

The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and microtopography.The results showed a significant decrease in Na_(2)O content(>30 wt.%)of FGD gypsum-treated bauxite residue after 30 min of mechanical ball milling.Mechanical ball milling resulted in differentiation of the elemental distribution,modification of the minerals in crystalline structure,and promotion in the dissolution of alkaline minerals,thus enhancing the acid neutralization capacity of bauxite residue.5 wt.%FGD gypsum combined with 30 min mechanical ball milling was optimal for the dealkalization of bauxite residue.

Simultaneous desulfurization and denitrification of sintering flue gas via composite absorbent

Experiments on simultaneous absorption of SO_2 and NO_X from sintering flue gas via a composite absorbent NaClO_2/NaClO were carried out. The effects of various operating parameters such as NaClO_2 concentration(ms), NaClO concentration(mp), molar ratio of NaClO_2/NaClO(M), solution temperature(TR), initial solution pH, gas flow(Vg) and inlet concentration of SO_2(CS) and NO(CN) on the removal efficiencies of SO_2 and NO were discussed. The optimal experimental conditions were determined to be initial solution pH = 6, TR=55 °C and M = 1.3 under which the average efficiencies of desulfurization and denitrification could reach99.7% and 90.8%, respectively. Moreover, according to the analysis of reaction products, it was found that adding NaClO to NaClO_2 aqueous solution is favorable for the generation of ClO_2 and Cl_2 which have significant effect on desulfurization and denitrification. Finally, engineering experiments were performed and obtained good results demonstrating that this method is practicable and promising.

Experimental study on the simultaneous desulfurization and denitrification by duct injection

The highly active absorbent with oxidization based on fly ash, lime and additive was prepared. Experiments of simultaneous desulfurization and denitrification were carried out using fixture bed and duct injection. The influencial factors for the absorptive capacity of the absorbent were studied. The absorptive capacities of 120.7 mg for SO 2 and 43.7 mg for NOx were achieved at a Ca/(S+N) molar ratio 1.2, respectively, corresponding removal efficiencies of 87% and 76%, while spent absorbent appeared in the form of dry powder. The optimal temperature and humidity of flue gas treated with this process were shown to be approximately 50℃, and 5% respectively. The mechanism of removal for SO 2 and NOx was investigated. In comparison with traditional dry FGD, this process appears to have lower cost, less complicated configuration and simpler disposal of used absorbent. The valuable references can be provided for industrial application by this process. The foreground of application will be vast in China and in the world.

Simultaneous desulfurization and denitrification of flue gas by pre-ozonation combined with ammonia absorption

A process of simultaneous desulfurization and denitrification of flue gas was conducted in this study.The flue gas containing 200 mg·m^-3NO,1000-4000 mg·m^-3SO(2,)3%-9%O(2)and 10%-20%CO(2)was first oxidized b(y)O3 and then absorbed by ammonia in a bubbling reactor.Increasing the ammonia concentration or the SO2 content in flue gas can promote the absorption of NOx and extend the effective absorption time.On the contrary,both increasing the absorbent temperature or the O(2)content shorten the effective absorption time of NO((x.))The change of solution pH had substantial influence on NOx absorption.In the presence of CO(2)the NOx removal efficiency reached 89.2%when the absorbent temperature was raised to 60℃and the effective absorption time can be maintained for 8 h,which attribute to the buffering effect in the absorbent.Besides,both the addition of Na(2)S2 O3 and urea can promote the NOx removal efficiency when the absorbent temperature is 25℃and the addition of Na(2)S2 O3 had achieved better results.The advantage of adding Na(2)S2 O3 became less evident at higher absorbent temperature and coexistence of CO(2.)In all experiments,SO(2)removal efficiency was always above 99%,and it was basically not affected by the above factors.

Tentative Study on a New Way of Simultaneous Desulfurization and Denitrification

Thiobacillus denitrificans, a kind of autotrophic facultative bacteria, can oxidize sulfide into elemental sulfur or sulfate when nitrate was adopted as its electron accepter and carbon dioxide as its carbon resource under anoxic or anaerobic environment. In this way, nitrate is converted into nitrogen. In addition, ThiobaciWus denitrificans can accumulate sulfur extracellularly. In this study, in a process of simultaneous desulfurization and denitrification, a strain of Thiobacillus denitriificans is employed as sulfur-producer in the treatment of wastewater containing sulfide and nitrate. The key factors affecting this process are investigated through batch tests. The experimental results indicate that the sulfide concentration and the ratio of sulfide to nitrate (S2-/NO3-) in the influent are the key factors, and their suitable values are suggested to be 5/3 and no more than 300mg·L-1, respectively, in order to achieve high conversion of sulfur.

Spectroscopic Characterization of Mo-Co-S and Mo-Fe-S Complexes-derived Catalysts for Desulfurization and Denitrification

The characteristic studies, by means of LR, UV-Vis and XPS spectroscopies, of the preparation process of Mo-Co-S and Mo-Fe-S catalysts for HDS and HDN, derived from (NH4)2MoS4-CoCl2 and (NH4)2MoS4-FeCl2 complexes supported on γ-Al2O3, respectively, indicate that the catalytically essential moiety on the surface of the catalysts is dominantly some sulfido-bimetallic species with such a structural unit (M' =Co or Fe), and both Co and Fe, served as promoters, can donate electrons to Mo probably via bridging-S. The nature of active-sites and the mechanism of promotion are discussed according to the results.

Feasibility of an innovative integrated process of simultaneous desulfurization and denitrification for high strength wastewater

An anaerobic expanding-bed reactor was adopted to investigate the feasibility of an innovative integrated process of simultaneous desulfurization and denitrification （SDD） for high strength wastewater. In the reactor, heterotrophic bacteria （including sulfate reducing bacterium and denitrifying bacteria） and autotrophic bacteria （ including Thiobacillus denitrificans） cooperated together by incubating and enriching functional bac- teria on different carriers in the anaerobic activated sludge. Synthetic wastewater with high concentrations of sulfate and nitrate was employed. The experimental resuhs showed that the removal efficiency of sulfate and nitrate was above 85% , elemental sulfur was observed while nitrate was absent in effluent. The balance of sulfur, nitrogen and electron was discussed respectively, which indicated that the integrated SDD process could be actualized. These resuhs might provide a guidance to further investigate the key factors affecting the integrated SDD process and to improve the efficiency of desulfurization and denitrification in wastewater treatment.

Titanium-rich TS-1 zeolite for highly efficient oxidative desulfurization

The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.

Integration of Desulfurization and Lithium-Sulfur Batteries Enabled by Amino-Functionalized Porous Carbon Nanofibers

Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.

Simultaneous nitrification and autotrophic denitrification in fluidized bed reactors using pyrite and elemental sulfur as electron donors

In this study, simultaneous nitrification and autotrophic denitrification (SNAD) with either elemental sulfur or pyrite were investigated in fluidized bed reactors in mesophilic conditions. The reactor performance was evaluated at different ammonium (12-40 mg/L of NH4+-N), nitrate (35-45 mg/L of NO3--N), and dissolved oxygen (DO) (0.1-1.5 mg/L) concentrations, with a hydraulic retention time of 12 h. The pyrite reactor supported the SNAD process with a maximum nitrogen removal efficiency of 139.5 mg/(L·d) when the DO concentration was in the range of 0.8-1.5 mg/L. This range, however, limited the denitrification efficiency of the reactor, which decreased from 90.0% ± 5.3% in phases II-V to 67.9% ± 7.2% in phases VI and VII. Sulfate precipitated as iron sulfate (FeSO4/Fe2(SO4)3) and sodium sulfate (Na2SO4) minerals during the experiment. The sulfur reactor did not respond well to nitrification with a low and unstable ammonium removal efficiency, while denitrification occurred with a nitrate removal efficiency of 97.8%. In the pyrite system, the nitrifying bacterium Nitrosomonas sp. was present, and its relative abundance increased from 0.1% to 1.1%, while the autotrophic denitrifying genera Terrimonas, Ferruginibacter, and Denitratimonas dominated the community. Thiobacillus, Sulfurovum, and Trichlorobacter were the most abundant genera in the sulfur reactor during the entire experiment.

A Model for Predicting the Erosion Rate Induced by the Use of a Selective Catalytic Reduction Denitrification Technology in Cement Kilns Flue Gas

Selective catalytic reduction(SCR)is a technology by which nitrogen oxides are converted with the aid of a catalyst into diatomic nitrogen and water.It is known that the catalyst can be easily eroded if a cement kiln with a high-dust content is considered.To understand this process,numerical simulations have been carried out considering a single catalyst channel in order to study the collision and erosion of fly ash and catalysts at meso scale.Based on a response surface methodology,the effects of five factors on the erosion rate have been studied,namely,the catalyst particle velocity,the particle size,the particle concentration,the incidence angle and the catalyst porosity.The results show that the influence of particle velocity,particle size and particle concentration is statistically significant and the particle size and incidence angle have a significant effect on the erosion rate.A quadratic polynomial prediction model for the erosion rate of honeycomb catalysts in cement kiln SCR reactors is finally proposed to support the future optimization of these systems.

Experimental study on simultaneous desulfurization and denitrifi- cation based on highly active absorbent

Simultaneous removal of SO2 and NO from flue gas by the highly active absorbent prepared from fly ash, lime and a few oxidizing manganese compound additive was studied using a flue gas circulating fluidized bed （CFB） under different experimental conditions. The effects influencing the removal effiencies were discussed. The optimal flue gas temperature, flue gas humidity, gas velocity of CFB and Ca/（S＋N） molar ratio with this process were approximately 110℃, 6%, 1.8 m/s and 1.05, respectively. Removal efficiencies of 92.3% for SO2 and 60.88% for NO were obtained under the optimal experimental conditions. While the spent absorbent appeared in the form of dry powder, the mechanism of removal for SO2 and NO based on the highly active absorbent was investigated by a scanning electron microscope （SEM）, a X-ray energy spectrometer and the chemical analysis methods. The valuable references can be provided for industrial application by the process. The foreground of application will be vast in China and in the world.