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.

基于机理和数据混合模型的SD-WFGD系统SO_(2)浓度动态预测

为了保证燃煤电站脱硫系统SO_(2)排放浓度达到环保要求的同时实现经济运行,建立了单塔双循环湿法烟气脱硫(SD-WFGD)系统出口SO_(2)浓度混合动态预测模型。首先,分析吸收SO_(2)的化学反应过程,分别建立了吸收塔出口和浆液池(AFT塔)出口SO_(2)浓度机理模型;然后,利用变分模态分解(VMD)方法对历史运行数据和机理模型预测偏差数据进行分解,将分解后不同频率的模态分量进行重构,利用最小二乘支持向量机(LSSVM)算法训练并得到不同的模态分量模型,将不同模态分量的LSSVM模型进行加权叠加,建立了数据补偿模型;最后,将数据补偿模型输出和机理模型输出进行叠加,得到SD-WFGD系统SO_(2)浓度混合动态预测模型。结果表明:利用VMD算法将历史数据分解为不同模态,不同模态数据重构后可有效提高数据模型的预测精度;同时,将机理模型和数据模型结合,可提升模型预测能力。

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.

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.

300MW燃煤电厂ESP和WFGD对烟气汞的脱除特性

采用燃煤电厂汞形态浓度取样测试OHM标准方法,对一座300 MW燃煤电厂静电除尘器(ESP)和湿法脱硫装置(WFGD)前后烟气进行了等速取样。使用美国Leeman Labs Hydra AA全自动汞分析仪检测烟气中的汞形态浓度。采集了固体样品,包括入炉煤、底渣、ESP电场灰、脱硫剂石灰石、脱硫产物石膏等,使用意大利Milestone公司生产的DMA80全自动汞分析仪检测固体样品中的汞浓度。计算锅炉系统的汞质量平衡,获得了ESP和WFGD前后烟气的汞形态浓度和分布规律,分析讨论了影响烟气汞形态转化的各种影响因素。结果表明,燃煤烟气中气态单质汞Hg0和气态氧化汞Hg2+占到总汞量的95%。煤渣中的汞可忽略不计;ESP对颗粒态汞Hgp的脱除效率达到95%以上,但是对Hg0和Hg2+脱除率不高。ESP对烟气总汞HgT脱除效率为12.77%～17.38%;WFGD对Hg2+的脱除率达到79.93%～90.53%,但是对Hg0没有脱除效果,其含量不仅没有下降反而有少量上升,说明有部分Hg2+在WFGD中被还原成Hg0。WFGD对HgT脱除效率为9.68%～29.36%;该电厂现有污染控制设备ESP+WFGD可以脱除全部的Hgp和大部分Hg2+,但是由于部分Hg2+的还原使得HgT的脱除效率在25.38%～38.38%。综合来看,该燃煤电厂的污染物控制设备在进行除尘和脱硫的同时,对汞的脱除率并不高,与燃煤中的氯含量较低有关。

湿法烟气脱硫(WFGD)喷淋塔内烟气流场的数值模拟研究

借助商用Fluent软件,针对300MW机组湿法烟气脱硫(WFGD)系统喷淋塔内烟气流场进行了数值模拟,详细考察了几何结构尺寸和运行参数对喷淋塔内烟气流场的影响。数值模拟结果表明,喷淋塔内烟气流场总体趋势大体上一致,几何结构尺寸和运行参数对塔内烟气流场有较大影响。

WFGD工艺典型脱硫添加剂应用探讨

鉴于石灰石湿法烟气脱硫(WFGD)技术在脱硫市场的主导地位,对镁、DBA、蚁酸等3种典型脱硫添加剂的作用机理、工业应用等方面作了介绍。用理论和实践证明脱硫添加剂确实能够提高SO2的吸收率和石灰石等吸收剂的利用率,并且具有降低结垢和堵塞风险、节约安装及运行成本的功效。

蒸汽相变促进WFGD系统脱除PM_(2.5)的协同作用分析

蒸汽相变作为预处理措施能显著提高常规除尘设备对PM2.5细颗粒的脱除效率,但对于水汽含量低的原始燃煤烟气蒸汽耗量太大,限制了工程应用,而在燃煤电厂湿法烟气脱硫(WFGD)过程中,烟气降温增湿,再添加少量蒸汽就可以建立PM2.5凝结长大所需要的过饱和环境,进而实现WFGD系统对PM2.5的协同高效脱除。在分析蒸汽相变促进PM2.5脱除影响因素的基础上,结合湿法脱硫过程传热传质特性,定性分析了脱硫塔塔前、塔内和塔出口添加蒸汽对WFGD系统脱除PM2.5的促进作用,并提出具体工艺方案。

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.

WFGD水力旋流器中石灰石颗粒分级试验与数值模拟

湿法烟气脱硫装置中水力旋流器分级试验表明,进口石灰石浆液的颗粒质量浓度15%时,溢流口颗粒质量浓度达30%;溢流颗粒则集中于30μm以下;随着颗粒粒径的增大,颗粒底流口回收率也在增大,当粒径达到30μm时,回收率已经接近100%。数值模拟表明,雷诺应力湍流模型、自由表面多相流动模型和斯托克斯拉格朗日模型能很好地描述水力旋流器内复杂三维运动的石灰石颗粒分级运动和规律。采用了初始边界条件不需给分流比、也不需设定空气柱的数值方法,模拟结果显示了空气柱的形成、流体的旋流流动。模拟得到的不同粒径颗粒的分级效率与高进口质量浓度条件下的试验结果吻合较好。

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.

应用润湿剂促进WFGD系统脱除细颗粒物的性能

采用旋流板塔双碱法脱硫工艺,进行了脱硫液中分别添加聚醚硅油、Compound No.3、XHG-248润湿剂促进湿法烟气脱硫(WFGD)系统脱除细颗粒物的试验研究,考察了脱硫液气比、脱硫液温度等对润湿剂作用性能的影响,并进行了协同利用蒸汽相变原理和添加润湿剂促进细颗粒物脱除的试验。结果表明:脱硫液温度对添加润湿剂的作用效果存在显著影响,常温下试验的3种润湿剂均能不同程度促进细颗粒物的脱除,脱硫液温度为45℃时,仅有Compound No.3对细颗粒物脱除有促进作用;同时在旋流板塔盘间添加适量蒸汽和脱硫液中添加Compound No.3润湿剂,可显著促进细颗粒物的脱除,脱除效率可增至65%左右。

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.