Simulation of Gas Oil Hydrotreater Heat Exchange Tube and Crystallization Prediction of NH_(4)Cl by Thermodynamic Equilibrium

The hydrotreater system heat exchanger is one of the main pieces of heat exchange equipment in petrochemical enterprises.In recent years,oil resources have shown a deterioration trend of high sulfur and high acid content,with corrosion risk being prominent in oil processing.Taking the multi-medium flow corrosion risk of the hydrotreater heat exchanger pipeline in a petrochemical enterprise as the research object,based on the parameter characteristics of corrosive NH_(3) and HCl media under a high-temperature and high-pressure environment,the ammonium salt crystallization and deposition mechanism under multi-phase flow is revealed.The thermodynamic equilibrium curve is modified based on the thermodynamic principle and fugacity coefficient variation,and the prediction model of ammonium chloride crystallization in hydrotreater heat exchanger under high temperature and high pressure is constructed according to the modification.This study uses the mixture model,the flow-thermal coupling method,and the discrete phase model method to carry out the numerical simulation of multiphase flow and the numerical prediction of particle distribution characteristics in the heat exchanger pipeline of the hydrotreater heat exchange equipment,so as to realize the quantitative prediction of the particle crystallization deposition distribution in the pipeline.The results show that with the decrease of temperature,the crystallization occurs first on both sides of the center of the tube bundle,and more crystallization occurs in the lower half of the U-shaped tube,which may seriously lead to problems such as pipe blockage and under-deposit corrosion.

Thermodynamic theory of flotation for a complex multiphase solid -liquid system and high-entropy flotation

The flotation of complex solid–liquid multiphase systems involve interactions among multiple components,the core problem facing flotation theory.Meanwhile,the combined use of multicomponent flotation reagents to improve mineral flotation has become an important issue in studies on the efficient use of refractory mineral resources.However,studying the flotation of complex solid–liquid systems is extremely difficult,and no systematic theory has been developed to date.In addition,the physical mechanism associated with combining reagents to improve the flotation effect has not been unified,which limits the development of flotation theory and the progress of flotation technology.In this study,we applied theoretical thermodynamics to a solid–liquid flotation system and used changes in the entropy and Gibbs free energy of the reagents adsorbed on the mineral surface to establish thermodynamic equilibrium equations that de-scribe interactions among various material components while also introducing adsorption equilibrium constants for the flotation reagents adsorbed on the mineral surface.The homogenization effect on the mineral surface in pulp solution was determined using the chemical potentials of the material components of the various mineral surfaces required to maintain balance.The flotation effect can be improved through synergy among multicomponent flotation reagents;its physical essence is the thermodynamic law that as the number of compon-ents of flotation reagents on the mineral surface increases,the surface adsorption entropy change increases,and the Gibbs free energy change of adsorption decreases.According to the results obtained using flotation thermodynamics theory,we established high-entropy flotation theory and a technical method in which increasing the types of flotation reagents adsorbed on the mineral surface,increasing the adsorption entropy change of the flotation reagents,decreasing the Gibbs free energy change,and improving the adsorption efficiency and stability of the flotation reagents improves refractory mineral flotation.

Experimental thermodynamic research on equilibrium between silicon alloy and SiO_2-CaO-Al_2O_3 melt

The equilibria of Al and Ca between silicon alloy and the SiO 2 Al 2O 3 CaO ternary slags were investigated using graphite crucible at 1?550?℃. With increasing Al 2O 3 and CaO content in the slags, the Al and Ca content increase respectively. The variation of the impurities are also affected by the silica content in slag which provides the oxidant during the oxidation refining process. The distributions of the impurities Al and Ca in silicon were given in terms of isoconcentration curves for Al and Ca in the ternary slags of SiO 2 Al 2O 3 CaO. The present experimental work provided available data to analyze the action of Al and Ca during oxidation refining process for silicon alloy.

Thermodynamics Behavior of Titanium for BOF Smelting Bearing Steel

When titanium element appears in bearing steel, it is very easy to create titanium nitride inclusion, which reduces the fatigue life of bearing steel. Based on the production data of bearing steel produced by BOF, it is found that the titanium takes its source in bearing steel; the factors-affecting titanium content, and the thermodynamics behavior of titanium under smelting condition were studied. The results show that the prime reasons of titanium content increment are the soluble aluminum content and the titanium oxide of slag. The comparison between the experimental data and theoretical ones shows that there is a big declination when the soluble aluminum content of steel is higher, which is caused by the nonequilibrium reaction of slag and steel. The apparent equilibrium distribution coefficient of titanium between slag and steel is Obtained by use of experimental data.

Thermodynamic Equilibrium Diagrams of Sulphur-Chromium System

The chemical and electrochemical equilibria in the presence of gaseous phase were investigated. Many substances, which consisted of sulphur and chromium, were considered. Various thermodynamic equilibria were calculated in different pressures. Calculation results were shown as log p-1/T and E-T diagrams. These diagrams may be used to study the corrosion of chromium in sulphur-containing circumstances. The diagrams are also used to thermodynamically determine the existence area of various substances and so on.

Thermodynamic equilibrium diagram of the chlorine-titanium system

The chemical and electrochemical equilibria of the chlorine-titanium system in the presence of gaseous phase were investigated. Many species, which consisted of chlorine and titanium, were considered. Various thermodynamic equilibria were calculated in the different pressures at different temperatures. The calculated results were shown as log p-1/Tand E-T diagrams. These diagrams may be used as important tools for corrosion study and titanium production. The diagrams are also used to thermodynamically determine the existence areas of various species and so on.

Thermodynamic Calculation of Si_3N_4-SiC Phase Equilibrium

SisN4 and SiC phase stability via gas phase reactions among SiO, CO/CO2 and N2 has been calculated based on thermochemical equilibrium. The influences of carbon activity (αC), and the partial pressure of SiO (PSiO), CO (PCO) and N2 (PN2) on the Si3N4-SiC stability have been studied and the related phase diagrams have been constructed. Result shows that the lowering αC and PCO/PSiO ratio and the increasing PN2 greatly elevate the Si3N4-SiC equilibrium temperature. Some previously observed experimental results related to Si3N4 and SiC formation at different temperature from the gas phase reactions have been discussed and some guides for sintering and synthesis Of the Si3N4 materials have been proposed

Using NMR-detected hydrogen-deuterium exchange to quantify protein stability in cosolutes,under crowded conditions in vitro and in cells

We review the use of nuclear magnetic resonance(NMR)spectroscopy to assess the exchange of amide protons for deuterons(HDX)in efforts to understand how high concentration of cosolutes,especially macromolecules,affect the equilibrium thermodynamics of protein stability.HDX NMR is the only method that can routinely provide such data at the level of individual amino acids.We begin by discussing the properties of the protein systems required to yield equilibrium thermodynamic data and then review publications using osmolytes,sugars,denaturants,synthetic polymers,proteins,cytoplasm and in cells.

Surface and transport properties of Cu-Sn-Ti liquid alloys

The lack of experimental data and / or limited experimental information concerning both surface and transport properties of liquid alloys often require the prediction of these quantities. An attempt has been made to link the thermophysical properties of a ternary Cu-Sn-Ti system and its binary Cu-Sn, Cu-Ti and SnoTi subsystems with the bulk through the study of the concentration dependence of various thermodynamic, structural, surface and dynamic properties in the frame of the statistical mechanical theory in conjunction with the quasi-lattice theory （QLT）. This formalism provides valuable qualitative insight into mixing processes that occur in molten alloys.

Effects of nano-sized aluminum on detonation characteristics and metal acceleration for RDX-based aluminized explosive

Nano-sized aluminum(Nano-Al)powders hold promise in enhancing the total energy of explosives and the metal acceleration ability at the same time.However,the near-detonation zone effects of reaction between Nano-Al with detonation products remain unclear.In this study,the overall reaction process of 170 nm Al with RDX explosive and its effect on detonation characteristics,detonation reaction zone,and the metal acceleration ability were comprehensively investigated through a variety of experiments such as the detonation velocity test,detonation pressure test,explosive/window interface velocity test and confined plate push test using high-resolution laser interferometry.Lithium fluoride(LiF),which has an inert behavior during the explosion,was used as a control to compare the contribution of the reaction of aluminum.A thermochemical approach that took into account the reactivity of aluminum and ensuing detonation products was adopted to calculate the additional energy release by afterburn.Combining the numerical simulations based on the calculated afterburn energy and experimental results,the parameters in the detonation equation of state describing the Nano-Al reaction characteristics were calibrated.This study found that when the 170 nm Al content is from 0%to 15%,every 5%increase of aluminum resulted in about a 1.3%decrease in detonation velocity.Manganin pressure gauge measurement showed no significant enhancement in detonation pressure.The detonation reaction time and reaction zone length of RDX/Al/wax/80/15/5 explosive is 64 ns and 0.47 mm,which is respectively 14%and 8%higher than that of RDX/wax/95/5 explosive(57 ns and 0.39 mm).Explosive/window interface velocity curves show that 170 nm Al mainly reacted with the RDX detonation products after the detonation front.For the recording time of about 10 ms throughout the plate push test duration,the maximum plate velocity and plate acceleration time accelerated by RDX/Al/wax/80/15/5 explosive is 12%and 2.9 ms higher than that of RDX/LiF/wax/80/15/5,respectively,indicating that the aluminum reaction energy significantly increased the metal acceleration time and ability of the explosive.Numerical simulations with JWLM explosive equation of state show that when the detonation products expanded to 2 times the initial volume,over 80%of the aluminum had reacted,implying very high reactivity.These results are significant in attaining a clear understanding of the reaction mechanism of Nano-Al in the development of aluminized explosives.

Tuning combined steam and dry reforming of methane for “metgas”production: A thermodynamic approach and state-of-the-art catalysts

Nowadays,combined steam and dry reforming of methane(CSDRM)is viewed as a new alternative for the production of high-quality syngas(termed as"metgas",H2:CO of 2.0)suitable for subsequent synthesis of methanol,considered as a promising renewable energy vector to substitute fossil fuel resources.Adequate operation conditions(molar feed composition,temperature and pressure)are required for the sole production of"metgas"while achieving high CH4,CO2 and H2O conversion levels.In this work,thermodynamic equilibrium analysis of CSDRM has been performed using Gibbs free energy minimization where;(i)the effect of temperature(range:200-1000℃),(ii)feed composition(stoichiometric ratio as compared to a feed under excess steam or excess carbon dioxide),(iii)pressure(range:1-20 bar)and,(iv)the presence of a gaseous diluent on coke yields,reactivity levels and selectivity towards"metgas"were investigated.Running CSDRM at a temperature of at least 800℃,a pressure of 1 bar and under a feed composition where CO2-H2O/CH4 is around 1.0,are optimum conditions for the theoretical production of"metgas"while minimizing C(S)formation for longer experimental catalytic runs.A second part of this work presents a review of the recent progresses in the design of(principally)Ni-based catalysts along with some mechanistic and kinetic modeling aspects for the targeted CSDRM reaction.As compared to noble metals,their high availability,low cost and good intrinsic activity levels are main reasons for increasing research dedications in understanding deactivation potentials and providing amelioration strategies for further development.Deactivation causes and main orientations towards designing deactivationresistant supported Ni nanoparticles are clearly addressed and analyzed.Reported procedures based on salient catalytic features(i.e.,acidity/basicity character,redox properties,oxygen mobility,metal-support interaction)and recently employed innovative tactics(such as confinement within mesoporous systems,stabilization through core shell structures or on carbide surfaces)are highlighted and their impact on Ni0reactivity and stability are discussed.The final aspect of this review encloses the major directions and trends for improving synthesis/preparation designs of Ni-based catalysts for the sake of upgrading their usage into industrially oriented combined reforming operations.

Behavior and control of chlorine in dyestuff residue incineration

Dyestuffresidue, a type of hazardous waste, is incinerated in the tubular furnace, and thermodynamic equilibrium model is used to calculate and analyze the chlorine behavior. The HCI emission and its effects on the behaviors of heavy metals are studied. Meanwhile, the effects of three dechlorine reagents are predicted at a high temperature. Results show that HCI emission is dependent on incineration temperature. The HCl evaporated mainly derives from the organic chlorine. Under the working condition of 500-- 900℃, the main products of rig, Pb, Cu, Ni, Zn, and Mn in reaction with HCl are HgCl2 （g）, PbCl4（g）, PbCI2 （g）, （CuCl）3 （g）, NiCl2 （s）, NiCl2 （g）, ZnCl2 （s）, ZnCl2 （g）, Zn （g）, MnCl2 （s）, and MnCl2 （g）, respectively. Among the three dechlorine reagents, CaCO3 is optimal to remove chlorine at high temperature, little of HCl is released below 800℃, whereas Fe3O4 is unstable at high temperature.

Numerical Study on the Acetylene Concentration in the Hydrogen-Carbon System in a Hydrogen Plasma Torch

Effects of the hydrogen/carbon mole ratio and pyrolysis gas pressure on the acetylene concentration in the hydrogen-carbon system in a plasma torch were numerically calculated by using the chemical thermodynamic equilibrium method of Gibbs free energy. The calculated results indicate that the hydrogen concentration and the pyrolysis gas pressure play crucial roles in acetylene formation. Appropriately abundant hydrogen, with a mole ratio of hydrogen to carbon about 1 or 2, and a relatively high pyrolysis gas pressure can enhance the acetylene concentration. In the experiment, a compromised project consisting of an appropriate hydrogen flow rate and a feasible high pyrolysis gas pressure needs to be carried out to increase the acetylene concentration from coal pyrolysis in the hydrogen plasma torch.

Variation and optimization of acid-dissolved aluminum content in stainless steel

As a key step in secondary refining, the deoxidation process in clean stainless steel production is widely researched by many scholars. In this study, vacuum oxygen decarburization（VOD） deoxidation refining in a 40-t electric arc furnace ＋ VOD ＋ ingot casting process was analyzed and optimized on the basis of Al deoxidation of stainless steel and thermodynamic equilibrium reactions between the slag and steel. Under good stirring conditions in VOD, the deoxidation reaction reaches equilibrium rapidly, and the oxygen activity in the bulk steel is controlled by the slag composition and Al content. A basicity of 3–5 and an Al content greater than 0.015wt% in the melt resulted in an oxygen content less than 0.0006wt%. In addition, the dissolved oxygen content decreased slightly when the Al content in the steel was greater than 0.02wt%. Because of the equilibrium of the Si–O reaction between the slag and steel, the activity of SiO2 will increase while the Si content increases; thus, the Si content should be lowered to enable the formation of a high-basicity slag. A high-basicity, low-Al2O3 slag and an increased Si content will reduce the Al consumption caused by SiO2 reduction.

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.

Co-Generation of C_2 Hydrocarbons and Synthesis Gases from Methane and Carbon Dioxide: a Thermodynamic Analysis

This paper deals with thermodynamic chemical equilibrium analysis using the method of direct minimization of Gibbs free energy for all possible CH4 and CO2 reactions. The effects of CO2/CH4 feed ratio, reaction temperature, and system pressure on equilibrium composition, conversion, selectivity and yield were studied. In addition, carbon and no carbon formation regions were also considered at various reaction temperatures and CO2/CH4 feed ratios in the reaction system at equilibrium. It was found that the reaction temperature above 1100 K and CO2/CH4 ratio=1 were favourable for synthesis gas production with H2/CO ratio unity, while carbon dioxide oxidative coupling of methane （CO2 OCM） reaction to produce ethane and ethylene is less favourable thermodynamically. Numerical results indicated that the no carbon formation region was at temperatures above 1000 K and CO2/CH4 ratio larger than 1.

Effects of Vanadium on Structure and Tensile Properties of Tempcore Steel Bars

Thermomechanical processing is a metallurgical operation to produce high-strength steel bars (rebars), through combining plastic deformation with thermal processes like heat treatment, water quenching, heating, and cooling at various rates into a single process. Ribbed reinforcing steel bars (rebars) are used for the reinforcement of concrete structures. Tempcore is a unique process to produce high-yield-strength rebars from mild steel without addition of a high weight percentage of costly alloying elements. The strength of rebar originates from the formation of a surface layer consisting of quenched and tempered martensite that surrounds a core composed of ferrite and pearlite. The economic advantages of this process are significant in comparison to those processes requiring alloying elements or further metal working to improve the mechanical properties. However, when there is a limitation in the water-cooling capacity, the required volume fraction of the martensite layer can’t be accomplished particularly when rolling bigger diameters of 32 mm - 40 mm at a higher rolling speed to maintain high productivity. Accordingly, a small addition of microalloying elements vanadium or niobium could be used in combination with Tempcore process to obtain high-strength steel rebars. In this contribution, 0.06 weight percentage of vanadium is added to the Tempcore treated rebars to satisfy ASTM A 706 Standard of Rebar Grade 80 PSI [550 MPa]. In order to decrease the trials in the steel plant floor, thermodynamics equilibrium calculations are predicted by Thermo-Calc, CCT, TTT diagrams are calculated by JMat Pro and the kinetics evolution of the vanadium carbonitrides precipitates are predicted by the computational database Mat Calc. High yield strength and tensile strength are obtained due to the effect of fine dispersions of nanometer-scale vanadium carbonitrides precipitates inspected by transmission electron microscope.

Impact of Atmospheric Transmittance and NLTE Correction on Simulation of High Spectral Infrared Atmospheric Sounder onboard FY-3E

With the launch of the first civilian early-morning orbit satellite Fengyun-3E(FY-3E),higher demands are placed on the accuracy of radiative transfer simulations for hyperspectral infrared data.Therefore,several key issues are investigated in the paper.First,the accuracy of the fast atmospheric transmittance model implemented in the Advanced Research and Modeling System(ARMS)has been evaluated with both the line-by-line radiative transfer model(LBLRTM)and the actual satellite observations.The results indicate that the biases are generally less than 0.25 K when compared to the LBLRTM,while below 1.0 K for the majority of the channels when compared to the observations.However,during both comparisons,significant biases are observed in certain channels.The accuracy of Hyperspectral Infrared Atmospheric Sounder-II(HIRAS-II)onboard FY-3E is comparable to,and even superior to that of the Cross-track Infrared Sounder(CrIS)onboard NOAA-20.Furthermore,apodization is a crucial step in the processing of hyperspectral data in that the apodization function is utilized as the instrument channel spectral response function to produce the satellite channel-averaged transmittance.To further explore the difference between the apodized and unapodized simulations,Sinc function is adopted in the fast transmittance model.It is found that the use of Sinc function can make the simulations fit the original satellite observations better.When simulating with apodized observations,the use of Sinc function exhibits larger deviations compared to the Hamming function.Moreover,a correction module is applied to minimize the impact of Non-Local Thermodynamic Equilibrium(NLTE)in the shortwave infrared band.It is verified that the implementation of the NLTE correction model leads to a significant reduction in the bias between the simulation and observation for this band.

An experimental and thermodynamic equilibrium investigation of the Pb,Zn,Cr,Cu,Mn and Ni partitioning during sewage sludge incineration

The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals（Pb, Zn, Cr, Cu, Mn and Ni） during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the Fact Sage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb 〉 Zn 〉 Cr 〉 Cu 〉 Mn 〉 Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni.With increasing combustion temperature, the presence of organic-Cl（PVC） and inorganic-Cl（NaCl） improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However,the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed Pb SiO4 and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl2, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl2, Pb（ClO4）2and Pb Cl2O4.

Liquid vaporization under thermodynamic phase non-equilibrium condition at the gas-liquid interface

Liquid vaporization under thermodynamic phase non-equilibrium condition at the gas-liquid interface is investigated over a wide range of fluid state typical of many liquid-fueled energy conversion systems. The validity of the phase-equilibrium assumption commonly used in the existing study of liquid vaporization is examined using molecular dynamics theories. The interfacial mass flow rates on both sides of the liquid surface are compared to the net vaporization rate through an order-of-magnitude analysis.Results indicated that the phase-equilibrium assumption holds valid at relatively high pressures and low temperatures,and for droplets with relatively large initial diameters(for example,larger than 10 μm for vaporizing oxygen droplets in gaseous hydrogen in the pressure range from 10 atm to the oxygen critical state). Droplet vaporization under superheated conditions is also explored using classical binary homogeneous nucleation theory,in conjunction with a real-fluid equation of state. It is found that the bubble nucleation rate is very sensitive to changes in saturation ratio and pressure;it increases by several orders of magnitude when either the saturation ratio or the pressure is slightly increased. The kinetic limit of saturation ratio decreases with increasing pressure,leading to reduced difference between saturation and superheat conditions. As a result,the influence of nonequilibrium conditions on droplet vaporization is lower at a higher pressure.