Molecular investigation into the transformation of recalcitrant dissolved organic sulfur in refinery sour water during stripping process

Refinery sour water primarily originates from the tops of towers in various units and coker condensate,and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand(COD)and organic sulfur contents.Even after the recovery of H_(2)S from the sour water by the stripping process,the effluent still contains a high concentration of dissolved organic sulfur(DOS),which can have a huge bad influence.While chemical composition of dissolved organic matter(DOM)in refinery wastewater has been extensively studied,the investigation of recalcitrant DOS from sour waters remains unclear.In the present study,chemical composition of sour water DOMs(especially DOS)was investigated using fluorescence spectroscopy(excitation-emission matrix,EEM)and mass spectrometry,including gas chromatography-mass spectrometry(GC-MS)and high-resolution Orbitrap MS.The GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process,while compounds with high hydrophilicity and humification degree were found to be more recalcitrant.The Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated compounds.However,the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms,particularly in the form of highly unsaturated and aromatic compounds.The Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates,disulfide bonds,thioethers.Understanding the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

Effect of Cycling Loaded Rare Earths on Stripping Process in P507 Extraction System

P507 （HEH [EHP]） is an important extractant for the separation of rare earth and is widely used in industry. Since the complexes of heavy rare earth ions with saponified P507 are so stable that the rare earth ions are difficult to be exchanged and stripped by H^＋ ions. Thus, the cycled extractant loads certain amount of heavy rare earth ion after stripped by acid. This amount of rare earth ions loaded in blank organic phase is named as the ＂cycling loaded rare earth ions （CLREs）＂. In the separation process of Tm^3＋, Yb^3 ＋, and Lu^3 ＋ , the amount of CLREs carl be more than 10% of the normal capacity of saponifiedorganic phase. In fact, CLREs affect the separation efficiency and decrease the purity of the products. Based on the extracting-stripping equilibrium and mass balance, the influence of different process parameters on the amount of CLREs was studied by computer simulation. The results indicate that higher acid consumption and more stripping stages are required to eliminate CLREs. For an industrial practice, however, the acid consumption and the number of stripping stage can be designed by choosing an economic process and controlling CLREs at a reasonable level.

Self-Adaptive and Electric Field-Driven Protective Layer with Anchored Lithium Deposition Enable Stable Lithium Metal Anode

Lithium metal battery has great development potential because of its lowest electrochemical potential and highest theoretical capacity.However,the uneven deposition of Li^(+)flux in the process of deposition and stripping induces the vigorous growth of lithium dendrites,which results in severely battery performance degradation and serious safety hazards.Here,the tetragonal BaTiO3 polarized by high voltage corona was used to build an artificial protective layer with uniform positive polarization direction,which enables uniform Li^(+)flux.In contrast to traditional strategies of using protective layer,which can guide the uniform deposition of lithium metal.The ferroelectric protective layer can accurately anchor the Li^(+)and achieve bottom deposition of lithium due to the automatic adjustment of the electric field.Simultaneously,the huge volume changes caused by Li^(+)migration change of the lithium metal anode during charging and discharging is functioned to excite the piezoelectric effect of the protective layer,and achieve seamless dynamic tuning of lithium deposition/stripping.This dynamic effect can accurately anchor and capture Li^(+).Finally,the layer-modified Li anode enables reversible Li plating/stripping over 1500 h at 1 mA cm^(-2)and 50℃in symmetric cells.In addition,the assembled Li-S full cell exhibits over 300 cycles with N/P≈1.35.This work provides a new perspective on the uniform Li^(+)flux at the Li-anode interface of the artificial protective layer.

Surface Analysis of Chemical Stripping Titanium Alloy Oxide Films

The chemical stripping method of titanium alloy oxide films was studied. An environment friendly solution hydrogen peroxide and sodium hydroxide without hydrofluoric acid or fluoride were used to strip the oxide films. The morphologies of the surface and cross-section of the oxide films before and after the films stripping were characterized by using scanning electron microscopy （SEM）. The microstructure and chemical compositions of the oxide films before and after the films stripping were investigated by using Raman spectroscopy （Raman） and X-ray photoelectron spectroscopy （XPS）. It was shown that the thickness of the oxide film was in the range of 5-6 μm. The oxide films were stripped for 2 to 8 min in the solution. Moreover, the effect of the stripping time on the efficiency of the film stripping was investigated, and the optimum stripping time was between 6-8 min. When the stripping solution completely dissolved the whole film, the α/β microstructure of the titanium alloy Ti-10V-2Fe-3Al was partly revealed. The stripping mechanism was discussed in terms of the dissolution of film delamination. The hydrogen peroxide had a significant effect on the dissolution of the titanium alloy anodic oxide film. The feasibility of the dissolution reaction also was evaluated.

Carbon dioxide induced degradation of diethanolamine during absorption and desorption processes

Alkanolamines are widely used in the purification of the sourgas sweetening process. During the sour gas absorption process, CO_2 significantly degrades the amine solvent and creates enormous problems for plant operation. In this work, CO_2 induced degradation of aqueous diethanolamine(DEA) solution was conducted in a 1.25 L jacketed glass reactor that functioned as an absorber and stripper at atmospheric conditions. Pure CO_2 was bubbled through the reactor until the solution became saturated. In this study, the concentrations of DEA used were in the range of concentrations between 2 mol·L^(-1) and 4 mol·L^(-1). In the degradation experiment, six generic cycles were conducted for each run. Each cycle was configured with the absorption and desorption of carbon dioxide at 55 ℃ and 100 ℃, respectively. Samples were collected after a predetermined experimental time and analyzed by ion chromatography(IC) to identify unknown ionic degradation products(DGPs). In the IC analysis, three different columns were used for anion, cation and ion exclusion systems, which are Metrosep A Supp 5150/4.0, Metrosep C Supp 4 150/4.0 and Metrosep Organic Acids, respectively. The major identified DGPs of D01 DEA2 M, D02 DEA3 M, and D03 DEA4 M are nitrite, acetate and ammonium. Phosphate product was found in the degraded amine samples which might be due to the contamination of water or chromatographic system.

Europium recovery process by means of polymeric nanoparticles functionalized with acrylic acid,curcumin and fumaramide

Polymeric nanoparticles of poly(methyl methacrylate)were obtained by emulsion polymerization techniques in a proce ss of two stages.The particles were functionalized with acrylic acid,curcumin,and fumaramide and three series of polymeric particles were obtained.The incorporation of functional groups was confirmed by Fourier transform-infrared spectrosocopy(FT-IR)and ultraviolet-visible(UV-Vis)methods.The spherical morphology of particles with an average diameter of 100 nm was observed by scartning electron microscopy(SEM).The polymeric materials were used for recovery of[Eu]from synthetic solutions.The nanoparticles show excellent chelation capacity to trap rare-earth ions,because they recover more than 85%of[Eu]at pH of 2.The images of SEM after extraction process show arrays between particles with larger average particle sizes to 1.5 um.In addition,the particles have a good stripping capacity,exceeding 50%of it,maintaining their homogeneity in morphology and good stability in dispersion for the recovery and stripping processes.A pseudo-second model order is obtained for the extraction and stripping processes while the best results of stripping process are obtained at pH of 6.

Porous polymer electrolytes for long-cycle stable quasi-solid-state magnesium batteries

The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.

HEAT TRANSFER ANALYSIS DURING ROLLING OF THIN SLAB IN CSP

A mathematical model has been built to numerically predict the thermal history of thin slab during CSP （compact strip process） rolling. To estimate the temperature distribution in the slab mare accurately, the mathematical model combines heat transfer in the slab, in the roll, and at the roll-slab interface during bite. The numerical results agree with on-site running data, which proves the reliabili~, of the mathematical model. The results show that roll chilling has a significant effect on the temperature distribution in the slab.

Improving flangeability of multiphase steel by increasing microstructural homogeneity

Multiphase microstructure significantly increases the strength,usually at the expense of flangeability because of lacking microstructure homogeneity.To further improve the strength-flangeability of multiphase steel,the microstructural homogeneity was advanced by adjusting the hard martensite/austenite(M/A)islands.The strength-flangeability was measured via uniaxial tensile tests and hole expansion tests.Their microstructures were characterized using a scanning electron microscope equipped with an electron backscatter diffraction detector and a transmission electron microscope.Nanoindentation tests were supplementally used to quantitatively reveal the microstructural homogeneity of the steels.Results show that the adjusted multiphase steel achieves an excellent ultimate tensile strength(~800 MPa)and flangeability(~135%hole expansion ratio).A promising homogeneous multiphase microstructure was obtained by controlling undercooled austenite transformed at about 600℃.This microstructure consists of soft polygonal ferrite,blocky bainitic ferrite,and hard M/A islands.The volume fraction of M/A islands is around 5%,and the average size is less than l pm.Detailed nanoindentation analysis indicated that the participation of M/A islands impressively influenced the microstructural homogeneity.Weakened strain partition and better mechanical compatibility were present in the adjusted multiphase steel since the plasticity initiation started late,which resulted in a positive flangeability.Moreover,avoiding M/A islands distributed in the chain along the rolling direction on the matrix hindered the possibility of voids coalescing into cracks and stabilized the flanging performance.

In-situ observation and analysis of solidified structure evolution of S50C steel in soaking furnace

The evolution of solidified structure of S50C steel during heat treatment in compact strip production process was studied through an ultra-high-temperature confocal scanning laser microscope.It was found that the solidified structure consisted of dendritic crystals with secondary dendrite arm spacing ranging in 32-120μm,where carbon segregation was evident,and the dendrite arms wereα-Fe.The insignificant change was observed at a soaking temperature of 1180℃,whereas at 1300℃,the finer structure firstly disappeared,and then,the coarsening decreased,indicating that carbon tended to be homogenized.Therefore,the microsegregation was improved at 1300℃for 15 min.The phase transformation ofα-Fe→γ-Fe enhanced the carbon diffusion,and the evolution of the equivalent radius req was controlled by carbon diffusion.The diffusion coefficient of carbon(D=15μm2/s)was determined by using the inverse problem method.

Effects of design parameters and tension on behavior of a coil using finite element analysis

During the thin strip coiling process, it is necessary to use a sleeve with a mandrel to prevent excessive deformation of the strip. Stress distribution in the sleeve and in the strip is an important factor that determines the quality of the coil. However, owing to the accumulation of high pressure, it is difficult to determine the stress distribution through experimentation. Thus, stress analysis of the strip coiling process was conducted. Finite element analysis was used to investigate the effects of the weight of the strip and the mandrel on the stress distribution and stress concentration near the starting point of the coil. The radial stress was predicted for a coil with a stacked thickness of 384 mm, which corresponds to a strip length of 1486 m, using the stress analysis model developed in a preceding research. A method was presented to reduce the weight and radial stress of a strip coil. It was found that the deformation of the sleeve can be reduced by decreasing the gap between the mandrel segments. The thickness of the sleeve can be reduced from 120 to 106 mm using the stress analysis results. Furthermore, coiling tension can be reduced by 44% compared to the existing value considering the interlayer slip of the strip coil.