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 equilibrium of bismuth hydrometallurgyin chloride and nitrate solutions

Simultaneous equilibrium was applied to the thermodynamic analysis and calculation of Bi（Ⅲ）-X（Cl-, NO-3）-H2O systems, based on which the diagrams of the logarithm of equilibrium concentration of Bi（Ⅲ） of series precipitation vs pH value of these two systems at 25 ℃ were obtained, and the pH ranges of the stable zones of various precipitations were analyzed and determined. In Bi（Ⅲ）-Cl--H2O system, the variations of c0(Bi3+) and （c0（Cl-）） have little effect on the equilibria of Bi（OH）3-solution and BiOOH-solution, but has great influence on the （equilibrium） of BiOCl-solution. However, in Bi（Ⅲ）-NO-3-H2O system, the variations of c0(Bi3+) and c0（NO-3） have little effect on equilibria of Bi（OH）3-solution, BiOOH-solution and Bi2O3-solution. When pH value is high, Bi2O3 is the thermodynamic stable phase, its stable zone is the widest, almost including the stable zones of BiOCl or （BiONO3,） （Bi（OH）3） and BiOOH. Bi（OH）3 cannot be obtained from Bi（Ⅲ）-Cl--H2O system, even strong alkaline media. Bi2O3 can be obtained from the solution directly, and highly pure BiOCl or BiONO3 can also be obtained through strictly controlling pH value.

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 equilibrium diagram of CaCl_2-Ca(OH)_2-H_2O system

The lg c-pH diagram of the CaCl2-Ca（OH）2-H2O system and its two subsystems at 298.15 K are constructed according to the theory of thermodynamic equilibrium. The interaction characteristics between the solubility of CaCl2 and Ca（OH）e can be found out from the diagrams. CaCl26H2O （s）, Ca（OH）2（s） and solution coexist when the pH value of solution is about 10.8. CaC12 with the minimum solubility of 1 682.4 g/L is in equilibrium with solution when the pH value is lower than 9.4, and Ca（OH）2 with the minimum solubility of 2.749 g/L is in equilibrium with solution at the pH value over 12.1, which provides a theoretical basis for the treatment and reuse of calcium chloride mother liquor for collocating lime cream which is the precipitant in the process of synthesizing magnesium hydroxide.

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.

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.

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.

The Non—local Thermodynamical Equilibrium Effects on Opacity

Based on the detailed configuration accounting (DCA) model, a method is developed to include the resonant photoionization and the excitation-autoionization in the non-local thermodynamical equilibrium (NLTE) average atom (AA) model. Using this new model, the mean charge states and the opacity are calculated for NLTE high- plasmas and compared with other results. The agreement with AA model is poor at low electron density. The present results agree well with those of DCA model within 10%. The calculations show that the NLTE effects on opacity are strong.

Experimental measurement and thermodynamic modeling of binary and ternary solid–liquid phase equilibrium for the systems formed by L-arabinose,D-xylose and water

Solid–liquid phase equilibrium data for binary(L-arabinose–water) and(D-xylose–water) systems at temperatures from(269.85–298.05) K and ternary(L-arabinose–D-xylose–water) system at temperatures of 273.85 K,278.85 K and 284.45 K were measured at atmospheric pressure.The ternary phase diagrams of the systems were constructed on the base of the measured solubility.Two pure solid phases were formed at given temperatures,including pure L-arabinose and pure D-xylose,which were con firmed and determined by the method of Schreinemakers' wet residue.At the same temperature,the crystallization region of L-arabinose was larger than D-xylose's.The acquired solubility data were then correlated using the NRTL model,Wilson model and Xu model.The calculated solubility with the three models agreed well with the experimental values.

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

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.

Thermodynamic behaviors of Cu in interaction with chlorine, sulfur, phosphorus and minerals during sewage sludge co-incineration

Thermodynamic equilibrium calculations were performed to reveal effects of interactions among Cl, S, P and other minerals on Cu migration. Our results showed that HCl（g）, SO2（g） and （P2O5）2（g） were released from the sewage sludge co-incineration. Cl was found to weaken adsorption of Cu by Al2O3, CaO and Fe2O3, while S de- layed reactions of Fe2O3 and Al2O3 with Cu, with P having no effect on reactions between the minerals and Cu. Among the coupled systems ofCl, S and P, the co-existences of Cl and S, and Cl, S and P were determined to inhibit Cu volatilization, and the co-existence of Cl and P had an enhancing effect Cu migration was affected only by S in the S and P system. With the SiO2, CaO and Al2O3 system, both Cl alone and Cl and P led to failed reactions be- tween the minerals and Cu. In the systems of S, S and Cl, S and P, and S, Cl and P, the migration behavior of Cu was mainly affected by S at low temperatures and by Cl at high temperatures, whereas P had no effect on Cu mi- gration during the entire nrocess.

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.

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.

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.

Kinetics Study on O2 Adsorption and OHad Desorption at Pt（111）, Its Implication to Oxygen Reduction Reaction Kinetics

Kinetics of dissociative O2 adsorption, OHad desorption, and oxygen reduction reaction （ORR） at Pt（111） electrode in 0.1 mol/L HClO4 has been investigated. Reversible OHad adsorption/desorption occurs at potentials from 0.6 V to 1.0 V （vs. RHE） with the exchange current density of ca. 50 mA/cm^2 at 0.8 V, the fast kinetics of OHad desorption indicates that it should not be the rate determining step for ORR. In the kineticor kinetic-mass transport mix controlled potential region, ORR current at constant potential displays slight decrease with reaction time. ORR current in the positive-going potential scan is slightly larger than that in the subsequent negative-going scan with electrode rotation speed （〉800 r/min） and slow potential scan rate （〈100 mV/s）. The open circuit potential of Pt/0.1 mol/L HClO4 interface increases promptly from 0.9 V to 1.0 V after switch from O2 free- to O2-saturated solution. The increase of open circuit potential as well as ORR current decays under potential control due to the accumulation of OHad from dissociative adsorption of O2. It indicates that at Pt（111） the net rate for O2 decomposition to OHad is slightly faster than that for OHad removal, one cannot simply use the assumption of rate determining step to discuss ORR kinetics. Instead, the ORR kinetics is determined by both the kinetics for O2 decomposition to OHad as well as the thermo-equilibrium of OHad＋H^＋＋e→←H2O.

Theoretical simulation and experimental study of hydrolysis separation of SbCl_3 in complexation-precipitation system

The theoretical simulation and verified experiments on metal separation in a Sb^3＋-OH^--Cl^-complexation-precipitation system involving hydrolysis-precipitation reactions of SbOCl, Sb4O5Cl2and Sb2O3were carried out. The equilibrium concentration of [Sb^3＋]Twas obtained by calculation and verified by experiments. The precipitates SbOCl,Sb4O5Cl2and Sb2O3were analyzed through the equilibrium concentration of Sb^3＋in the solution and the ΔrGΘmof transformation reactions of these materials. It is found that the concentration of [Sb^3＋]Tin verified experiments was larger than the theoretical value, where the theoretical minimum concentration of [Sb^3＋]Twas 10^-10.92mol/L at pH value of 4.6 and the minimum concentration obtained from the verified experiment was about 10^-3.8mol/L at pH value of 5.1. Different precipitates can be obtained atcertain pH. The SbOCl cannot be obtained both in theoretic calculations and in verified experiments, while the Sb8O11Cl2-H2O was generated in the experiment.

Industrial catalysis:Strategies to enhance selectivity

Precise control of catalytic selectivity is a key concept of green chemistry,and also an important driving force for the sustainable development of catalytic industry.Selectivity not only determines the atomic economy of the catalytic process,but also affects the energy consumption of subsequent separation process.The objective of this review is to illustrate successful catalyst design strategies to enhance selectivity,by using several important catalytic cases of petroleum refining and petrochemicals.These industrial applications and cutting-edge research cases mainly use the strategies of coupling,decoupling or confinement of adsorption sites and active sites to tune the diffusion barrier and activation energy barrier in different routes,so as to improve the selectivity of catalyst.Based on the preliminary understanding of selectivity improvement,it is necessary to systematically investigate the selective catalytic processes using combination of multiple strategies,thereby realizing the design of highly selective catalyst over reasonable time scales and space scales.

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.