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.

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.

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.

Desulfurization characteristics of slaked lime and regulation optimization of circulating fluidized bed flue gas desulfurization process--A combined experimental and numerical simulation study

Circulating fluidized bed flue gas desulfurization(CFB-FGD) process has been widely applied in recent years. However, high cost caused by the use of high-quality slaked lime and difficult operation due to the complex flow field are two issues which have received great attention. Accordingly, a laboratory-scale fluidized bed reactor was constructed to investigate the effects of physical properties and external conditions on desulfurization performance of slaked lime, and the conclusions were tried out in an industrial-scale CFB-FGD tower. After that, a numerical model of the tower was established based on computational particle fluid dynamics(CPFD) and two-film theory. After comparison and validation with actual operation data, the effects of operating parameters on gas-solid distribution and desulfurization characteristics were investigated. The results of experiments and industrial trials showed that the use of slaked lime with a calcium hydroxide content of approximately 80% and particle size greater than 40 μm could significantly reduce the cost of desulfurizer. Simulation results showed that the flow field in the desulfurization tower was skewed under the influence of circulating ash. We obtained optimal operating conditions of 7.5 kg·s^(-1)for the atomized water flow, 70 kg·s^(-1)for circulating ash flow, and 0.56 kg·s^(-1)for slaked lime flow, with desulfurization efficiency reaching 98.19% and the exit flue gas meeting the ultraclean emission and safety requirements. All parameters selected in the simulation were based on engineering examples and had certain application reference significance.

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.

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°.

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.

Two-Stage Approach for Targeted Knowledge Transfer in Self-Knowledge Distillation

Knowledge distillation(KD) enhances student network generalization by transferring dark knowledge from a complex teacher network. To optimize computational expenditure and memory utilization, self-knowledge distillation(SKD) extracts dark knowledge from the model itself rather than an external teacher network. However, previous SKD methods performed distillation indiscriminately on full datasets, overlooking the analysis of representative samples. In this work, we present a novel two-stage approach to providing targeted knowledge on specific samples, named two-stage approach self-knowledge distillation(TOAST). We first soften the hard targets using class medoids generated based on logit vectors per class. Then, we iteratively distill the under-trained data with past predictions of half the batch size. The two-stage knowledge is linearly combined, efficiently enhancing model performance. Extensive experiments conducted on five backbone architectures show our method is model-agnostic and achieves the best generalization performance.Besides, TOAST is strongly compatible with existing augmentation-based regularization methods. Our method also obtains a speedup of up to 2.95x compared with a recent state-of-the-art method.

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.

Solar-assisted two-stage catalytic membrane reactor for coupling CO_(2) splitting with methane oxidation reaction

A two-stage catalytic membrane reactor(CMR)that couples CO_(2) splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane.The asymmetric membrane comprises a dense SrFe_(0.9)Ta_(0.1)O_(3-σ)(SFT)separation layer and a porous Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Cu_(0.1)O_(3-σ)(SFTC)catalytic layer.In thefirst stage reactor,a CO_(2) splitting reaction(CDS:2CO_(2)→2CO+O_(2))occurs at the SFTC catalytic layer.Subsequently,the O_(2) product is selectively extracted through the SFT separation layer to the permeated side for the methane combustion reaction(MCR),which provides an extremely low oxygen partial pressure to enhance the oxygen extraction.In the second stage,a Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Ni_(0.1)O_(3-σ)(SFTN)catalyst is employed to reform the products derived from MCR.The two-stage CMR design results in a remarkable 35.4%CO_(2) conversion for CDS at 900℃.The two-stage CMR was extended to a hollowfiber configuration combining with solar irradiation.The solar-assisted two-stage CMR can operate stably for over 50 h with a high hydrogen yield of 18.1 mL min^(-1) cm^(-2).These results provide a novel strategy for reducing CO_(2) emissions,suggesting potential avenues for the design of the high-performance CMRs and catalysts based on perovskite oxides in the future.

Two-Stage Optimal Scheduling of Community Integrated Energy System

From the perspective of a community energy operator,a two-stage optimal scheduling model of a community integrated energy system is proposed by integrating information on controllable loads.The day-ahead scheduling analyzes whether various controllable loads participate in the optimization and investigates the impact of their responses on the operating economy of the community integrated energy system(IES)before and after;the intra-day scheduling proposes a two-stage rolling optimization model based on the day-ahead scheduling scheme,taking into account the fluctuation of wind turbine output and load within a short period of time and according to the different response rates of heat and cooling power,and solves the adjusted output of each controllable device.The simulation results show that the optimal scheduling of controllable loads effectively reduces the comprehensive operating costs of community IES;the two-stage optimal scheduling model can meet the energy demand of customers while effectively and timely suppressing the random fluctuations on both sides of the source and load during the intra-day stage,realizing the economic and smooth operation of IES.

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.

Two-Stage Planning of Distributed Power Supply and Energy Storage Capacity Considering Hierarchical Partition Control of Distribution Network with Source-Load-Storage

Aiming at the consumption problems caused by the high proportion of renewable energy being connected to the distribution network,it also aims to improve the power supply reliability of the power system and reduce the operating costs of the power system.This paper proposes a two-stage planning method for distributed generation and energy storage systems that considers the hierarchical partitioning of source-storage-load.Firstly,an electrical distance structural index that comprehensively considers active power output and reactive power output is proposed to divide the distributed generation voltage regulation domain and determine the access location and number of distributed power sources.Secondly,a two-stage planning is carried out based on the zoning results.In the phase 1 distribution network-zoning optimization layer,the network loss is minimized so that the node voltage in the area does not exceed the limit,and the distributed generation configuration results are initially determined;in phase 2,the partition-node optimization layer is planned with the goal of economic optimization,and the distance-based improved ant lion algorithm is used to solve the problem to obtain the optimal distributed generation and energy storage systemconfiguration.Finally,the IEEE33 node systemwas used for simulation.The results showed that the voltage quality was significantly improved after optimization,and the overall revenue increased by about 20.6%,verifying the effectiveness of the two-stage planning.

Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization

A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.

Ultra-deep oxidative desulfurization of fuel with H_2O_2 catalyzed by phosphomolybdic acid supported on silica

A highly active catalyst of phosphomolybdic acid ~HPMo） was prepared and applied in the catalytic oxidative desulfurization （CODS） system. The catalyst was characterized by FT-IR, XRD, XPS and superconducting NMR. The influences of rn（catalyst）/m（oil）, V（H202）fV（oil）, reaction temperature and reaction time on the fractional conversion of benzothiophene （BT） and dibenzothiophene （DBT） were investigated. GC-MS and micra-coulometric methods were employed to investigate the reaction. The catalyst has high desulfurization activity in the removal of BT and DBT under mild conditions. The recycling experiments indicated that DBT and BT removal could still reach 95.2% and 95.7% after 10 cycles.

Mssbauer spectroscopic characterization of ferrites as adsorbents for reactive adsorption desulfurization

Sulfur in transportation fuels is a major source of air pollution. New strategies for the desulfurization of fuels have been explored to meet the urgent need to produce cleaner gasoline. Adsorptive desulfurization（ADS） is one of the most promising complementary and alternative methods. Herein,nanocrystalline ferrite adsorbents were synthesized from metal nitrates and urea using a microwave assisted combustion method. A series of ADS experiments were performed using a fixed‐bed reactor to evaluate the ADS reactivity over the ferrites, which was found to have the order MgFe2O4〉NiFe2O4〉CuZnFe2O4〉ZnFe2O4〉CoFe2O4. This effect is explained by the fact that the low degree of alloying of Mg‐Fe and the doped Mg increased the interaction between Fe and S compounds,leading to a significant improvement in the desulfurization capability of the adsorbent.Additionally, Mg can dramatically promote the decomposition of thiophene. X‐ray diffraction and Mosbauer spectroscopy were used to characterize the fresh, regenerated, and sulfided adsorbents.Although the ferrite adsorbents were partially sulfided to bimetallic sulfides during the adsorption process, they were successfully regenerated after calcining at 500 °C in air.

An interacting multiple model-based two-stage Kalman filter for vehicle positioning

To address the problem that a general augmented state Kalman filter or a two-stage Kalman filter cannot achieve satisfactory positioning performance when facing uncertain noise of the micro-electro-mechanical system（MEMS） inertial sensors, a novel interacting multiple model-based two-stage Kalman filter（IMM-TSKF） is proposed to adapt to the uncertain inertial sensor noise. Three bias filters are developed based on different noise characteristics to cover a wide range of noise levels. Then, an accurate estimation of biases is calculated by the interacting multiple model algorithm to correct the bias-free filter. Thus, the vehicle positioning system can achieve good performance when suffering from uncertain inertial sensor noise. The experimental results indicate that the average position error of the proposed IMMTSKF is 25% lower than that of the general TSKF.

Production of Light Olefins from Biosyngas by Two-stage Catalytic Conversion Process via Dimethyl Ether

NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas （H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%） with low H/C ratio of 1.0 was used as feed gas.

Measuring particle size distribution and total number in the activation chamber of desulfurization system by PIV

Application of particle image velocity (PIV) techniques for measuringparticle size distribution and total number in an activation chamber of desulfurization system isintroduced. Watersheld algorithm is used to choose the suitable initial gray level threshold whichis used to change the gray level images taken by PIV to black and white ones, then every particle inan image is isolated totally. For every isolating particle, its contour is tracked by the edgeenhancement filter function and kept by Freeman s chain code. Based on a set of particle s chincode, its size and size distribution are calculated and sorted. Finally, the experimental data ofcalcium particles and water drops, separately injected into the activation chamber, and the erroranalysis of data are given out.