Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.

A projected Newton algorithm based on chemically allowed interval for chemical equilibrium computations

The chemical equilibrium equations utilized in reactive transport modeling are complex and nonlinear,and are typically solved using the Newton-Raphson method.Although this algorithm is known for its quadratic convergence near the solution,it is less effective far from the solution,especially for ill-conditioned problems.In such cases,the algorithm may fail to converge or require excessive iterations.To address these limitations,a projected Newton method is introduced to incorporate the concept of projection.This method constrains the Newton step by utilizing a chemically allowed interval that generates feasible descending iterations.Moreover,we utilize the positive continuous fraction method as a preconditioning technique,providing reliable initial values for solving the algorithms.The numerical results are compared with those derived using the regular Newton-Raphson method,the Newton-Raphson method based on chemically allowed interval updating rules,and the bounded variable least squares method in six different test cases.The numerical results highlight the robustness and efficacy of the proposed algorithm.

A theoretical method for solving shock relations coupled with chemical equilibrium and its applications

In this study,a theoretical method is proposed to solve shock relations coupled with chemical equilibrium.Not only shock waves in dissociated flows but also detonation waves in combustive mixtures can be solved.The global iterative solving process is specially designed to mimic the physical and chemical process in reactive shock waves to ensure good stability and fast convergence in the proposed method.Within each global step,the single-variable equations of normal and oblique shock relations are derived and solved with the Newton iteration method to reduce the complexity of the problems,and the minimization of free energy method of NASA(National Aeronautics and Space Administration)is adopted to solve equilibrium compositions.It is demonstrated that the convergent process is stable and very close to the real chemical-kinetic process,and high accuracy is achieved in the solutions of normal and oblique reactive shock waves.Moreover,the proposed theoretical method has also been applied to many problems associated with reactive shocks,including the stability of oblique detonation wave,bow detonation over a sphere,and shock reflection in dissociated air.The great importance of using chemical equilibrium to theoretically predict the theoretical range of the wedge angle for a standing oblique detonation wave(the standing window of the oblique detonation wave),the stand-off distance of bow detonation wave and the transition criterion of shock reflection in dissociated air with high accuracy have been addressed.

Chemical equilibrium constants of rare earth nitrates and tri-n-butyl phosphate complex formation

Mixed rare earth nitrates （REi（NO3）3） in the aqueous solution was mixed with tri-n-butyl phosphate （TBP, （n-C4H9O）3PO） dissolved in kerosene for the formation of their corresponding complexes （REi（NO3）3·ni（n-C4H9O）3PO） at 303 K. The effects of initial concentrations of both TBP and mixed rare earth nitrates on the equilibrium constants of their complex formations were investigated. The complexes were formed almost immediately after mixing. The simultaneous formations reached their chemical equilibria within a few minutes by shaking the mixture at 200 r/min. The chemical equilibrium constants of the complex formations were independent of the initial TBP concentrations. However, they were decreased by reducing the concentration of REi（NO3）3. All equilibrium constants of the simultaneous complex formations were less than 0.7, while the average molar ratio of TBP to REi（NO3）3 of the complexes varied between 1.0 and 1.6. The chemical equilibrium constant for the formation of La（NO3）3·（n-C4H9O）3PO was 0.09, while that of Dy（NO3）3·（n-C4H9O）3PO was 0.68. The ascending sequence of chemical equilibrium constants for the simultaneous formations was La, Ce, Pr, Nd, Eu, Y, Sm, Gd, and Dy.

The chemical stability of heavy metals in a natural water system

A comprehensive investigation of heavy metal pollutants in Xiangjiang river was accomplished to evaluate their chemical stability through three different ways: (1) Chemical speciation by direct measurements; (2) Chemical equilibrium model simulation; (3) Sediment extraction experiments. All the results demonstrated that the directly bioavailable fraction was in a very limited amount. The metal bound to organic ligands, adsorbed particles and precipitated species presented a buffer for solution species. The majority of metals occured in the residues as solid particulates. It was inferred that the heavy metal pollutants in this aquatic system exhibited a high chemical stability. The critical limits of discharging load and pH values were suggested.

Measurement and model of density,viscosity,and hydrogen sulfide solubility in ferric chloride/trioctylmethylammonium chloride ionic liquid

The density and viscosity of ferric chloride/trioctylmethylammonium chloride ionic liquid(rFeCl_(3)/[A336]Cl)with different molar ratios(r=0.1-0.8)of FeCl_(3) to[A336]Cl were measured at temperatures from 313.15 to 358.15 K and atmospheric pressure.The density and viscosity data were fitted by the relevant temperature variation equations,respectively.The variation of density and viscosity with temperature and r was obtained.The solubility of rFeCl_(3)/[A336]Cl to H_2S was measured at temperatures from 318.15 to 348.15 K and pressures from 0 to 150 kPa.The effects of temperature,pressure,and r on the solubility of H_(2)S were discussed.The reaction equilibrium thermodynamic model(RETM)was used to fit the H_(2)S solubility data,and the average relative error was less than 1.3%,indicating that the model can relate the solubility data well.And Henry's constant and chemical reaction equilibrium constant were obtained by the RETM fitting.The relationships of Henry's constant and chemical reaction equilibrium constant with temperature and r were analyzed.

Thermodynamic analysis of combined reforming process using Gibbs energy minimization method: In view of solid carbon formation

Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.

Infrared spectroscopic study on chemical and phase equilibrium in triethylammonium acetate

Protic ionic liquid (PIL) triethylammonium acetate was prepared by mixing equimolar amounts of acetic acid and triethylamine, and then studied using the combination of the Attenuated Total Reflection Fourier Transform Infrared spectroscopy, in-situ infrared spectroscopy, pH, and conductivity titration measurements. It was found that the equimolar synthesized triethylammonium acetate was separated into two layers, which suggesting that there were both chemical and phase equilibrium in this solution. Molecular species could be directly observed in the IR spectra over the range of 1200-1800 cm-1 and also checked by 1H NMR. Based on analysis, the upper layer was rich in amine with little acid and PIL, and the down layer was rich in PIL with residual acetic acid and amine. And single PIL-rich layer could be separated into two layers again when the mole ratio of newly added triethyamine to the theoretical produced triethylammonium acetate reached 0.12.

Necessary and Sufficient Conditions for Reactive Azeotropes in Multi-reaction Mixtures in Terms of Elemental Composition

Necessary and sufficient conditions for azeotropy in reactive mixtures are derived in terms of elemental composition, which shows that in the space of elemental compositions, they take the same functional form as the conditions for azeotropy in non-reactive mixtures. The production of methyl tert-butyl ether (MTBE) is taken as an example. It is found that there are a 'pseudo' intermediate-boiling ternary reactive azeotrope at p = 101.325kPa and two 'real' ternary reactive azeotropes at p = 101.325 Pa. The introduced elemental compositions also reduce the dimensionality of the phase diagrams and provide a natural set of variables for visualization of phase behavior.

Area Method Analysis and Thermodynamic Behavior of Nonmetallic Micro-Inclusions in Casting Slab of GCr15 Bearing Steel

The distribution and characteristics of nonmetallic micro-inclusions of GCr15 bearing steel were explored through metallographic area method in virtue of tracer method and electronic microscope.The results show that the micro-inclusions,of which the average value is 0.032%,are mainly the compounds formed via the adsorption/aggregation of multielement deoxidized compounds and secondarily deoxidized products on tundish liquid level.The micro-inclusions of diameters from 0 to 5 μm are 92.5% in total,which basically determines the characteristics of inclusions distribution in casting slab.The inclusions of diameters more than 10 μm only account for less than 1% in total,which have little influence on steel quality.The relationship between equilibrium compositions of the first deoxidation products and molten steel compositions was also calculated based on thermodynamic theory.

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.

Comparative Study of Decomposition of CCl_4 in Different Atmosphere Thermal Plasmas

Decomposition of carbon tetrachloride was studied theoretically in the most commonly used thermal plasma atmosphere such as H2, N2, O2 and water steam. A code developed by the National Aeronautics and Space Administration （NASA） was adopted to calculate the chemical equilibrium distribution and energy consumption of the decomposition of CC;4 in the H2, N2, O2 and water steam atmosphere thermal plasma respectively, with a temperature range of 500 K to 5000 K. In the neutral condition （H2, N2, atmosphere） formation of solid carbon was observed and in the oxygen-atmosphere （O2 and water steam） solid carbon formation disappeared through controlling the ratio of C/O. This indicates that the formation of polycyclic aromatic hydrocarbons （PAHs） is impossible theoretically. The energy consumption in the N2 atmosphere was much higher than that in the H2, O2 and water steam atmosphere at 1500 K.

Calculation of Combustion Products by the New Iteration Method of Non-linear Equations

For a specific combustion problem involving calculations of several species at the equilibrium state, it is simpler to write a general computer program and calculate the combustion concentration. Original work describes, an adaptation of Newton-Raphson method was used for solving the highly nonlinear system of equations describing the formation of equilibrium products in reacting of fuel-additive-air mixtures. This study also shows what possible of the results. In this paper, to be present the efficient numerical algorithms for. solving the combustion problem, to be used nonlinear equations based on the iteration method and high order of the Taylor series. The modified Adomian decomposition method was applied to construct the numerical algorithms. Some numerical illustrations are given to show the efficiency of algorithms. Comparisons of results by the new Matlab routines and previous routines, the result data indicate that the new Matlab routines are reliable, typical deviations from previous results are less than 0.05%.

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.

Thermodynamics of the Single-Step Synthesis of Dimethyl Ether from Syngas

A detailed thermodynamic analysis of single-step synthesis of dimethyl ether (DME) from syngas has been performed. From experiments and theoretical calculations, a suitable thermodynamic model based on Reid抯 thermodynamic data and the Soave-Redlich-Kwong equation of state was determined. Using this model, a careful analysis of direct synthesis of dimethyl ether from syngas was carried out. Reaction syn-ergy in the synthesis can greatly improve CO conversion and DME yield. Lower temperatures and higher pressures favor higher CO conversion and DME yield. Compared to methanol synthesis, however, the tem-perature has a smaller effect on the reaction. The direct synthesis of dimethyl ether can exploit CO-rich syngas efficiently due to the maximum DME yield obtained at H2/(CO+CO2) mole ratio =1. A small amount of CO2 in the reactant mixture has little effect on the reaction. Under conditions of H2/(CO+CO2) feedstock, water in the system can improve the reaction performance.

Theoretical limiting concentration for mineralization of trichloromethane and dichloromethane in aqueous solutions by AOPs

It is widely stated that most organic contaminants could be completely mineralized by Advanced Oxidation Processes(AOPs). This statement means that the concentration of the organic contaminant at equilibrium(limiting concentration,LC)is low enough to be neglected.However,for environmental safety,especially drinking water safety,this statement needs to be verified from chemical engineering thermodynamic analysis.In this paper,trichloromethane(CHCl3)and dichloromethane(CH2Cl2) are selected as the model systems,and the equilibrium concentration(theoretical limiting concentration,TLC)for the mineralization of chlorinated methanes in aqueous solutions at the different initial concentrations of chlorinated methanes,pH values and·OH concentrations by AOPs are investigated by thermodynamic analysis.The results in this paper show that the TLC for the mineralization of CHCl3 and CH2Cl2 with·OH increases with increasing initial concentrations of CHCl3 and CH2Cl2,decreases with increasing concentration of·OH,and the TLC for the mineralization of CHCl3 decreases with increasing pH values except that the pH value changes from 3.0 to 3.5.For the mineralization of CH2Cl2 with·OH,at the concentrations of·OH obtained from the literature,there is no obvious change of the TLC with pH values,while as the concentrations of·OH increase by 10 and 100 times,the TLC decreases with the increasing pH values from 2.0 to 3.0 and from 3.5 to 4.5,and increases with the increasing pH values from 3.0 to 3.5 and from 4.5 to 5.0.The investigations in this paper imply that high concentration of·OH,a bit higher pH values(4.0–5.0)in acid environment and low initial concentrations of the organic contaminants are beneficial for the complete mineralization of chlorinated methanes by AOPs.

Determination of activity interaction parameters of Nb in Fe-C-Nb melts at 1873 K

The interaction parameters of Nb in Fe-C-Nb melts at 1873 K were measured using the chemical equilibrium method.The Fe-C melts were equilibrated with the CaO-MgO-Al_(2)O_(3)-NbO_(2) slags under a controlled oxygen potential for 24 h.In addition to acting as the protective gas,argon was adopted to control the oxygen potential.Based on the data obtained in the experiments,the activity interaction parameters were obtained by the multiple linear regression method.The first-order interaction parameters e_(Nb)^(C)and e_(Nb)^(Nb)are determined to be−0.035 and−0.134,respectively.The second-order interaction parameters r_(Nb)^(C),r_(Nb)^(Nb,C),and r_(Nb)……(Nb)are determined to be 0.011,−0.0063,and 0.0023,respectively.The thermodynamic data obtained are more reliable than those in previous publications for the Fe-C-Nb system when the Nb content range was 0.92-4.62 wt.%.

Dissolution Modeling and Experimental Measurement of CaS-H20 Binary System

CaS formed during the retorting process of oil shale has a hazardous influence on surface water quality. Interaction of retorted oil shale with water generates highly alkaline leachate with a high content of sulfur due to the CaS component. A theoretical model describing the behavior of solid calcium sulfide in contact with water was developed. The model was consistent with the measurements showing change in dissolution behavior when solid CaS remained in the solution. Experimental measurements of pH and concentrations of ions were carried out in oxy- gen-free water at 25 ~C using CaS concentrations from 24.2-131.5 mgoL-1 （0.335--1.823 mmol/L）. Analysis of pH and concentrations of ions in the solution and calculations by the developed model showed that the solubility of CaS was estimated as 125.0 mg·L 1 （1.733 mmol/L）, and therefore the solubility product of CaS is 3.41×10^-10 （mo·L^-1）^2 at a temperature of 25℃.