Absorption characteristics,model,and molecular mechanism of hydrogen sulfide in morpholine acetate aqueous solution

The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k Pa.The total solubility of H_(2)S increased with higher temperatures,lower pressures,and reduced water content.The reaction equilibrium thermodynamic model was used to correlate the solubility data.The results indicate that the chemical reaction equilibrium constant decrease with increasing water content and temperature,whereas Henry constant increase with increasing water content and temperature.Compared with other ionic liquids,H_(2)S exhibits a higher physical absorption enthalpy and a lower chemical absorption enthalpy in[Bmmorp][Ac]aqueous solution.This suggests that[Bmmorp][Ac]has a strong physical affinity for H_(2)S and low energy requirement for desorption.Quantum chemical methods were used to investigate the molecular mechanism of H_(2)S absorption in ionic liquids.The interaction energy analysis revealed that the binding of H_(2)S with the ionic liquid in a1:2 ratio is more stable.Detailed analyses by the methods of the interaction region indicator and the atoms in molecules were conducted to the interactions between H_(2)S and the ionic liquid.

Modeling of Large-Scale Hydrogen Storage System Considering Capacity Attenuation and Analysis of Its Efficiency Characteristics

In the existing power system with a large-scale hydrogen storage system,there are problems such as low efficiency of electric-hydrogen-electricity conversion and single modeling of the hydrogen storage system.In order to improve the hydrogen utilization rate of hydrogen storage system in the process of participating in the power grid operation,and speed up the process of electric-hydrogen-electricity conversion.This article provides a detailed introduction to the mathematical and electrical models of various components of the hydrogen storage unit,and also establishes a charging and discharging efficiency model that considers the temperature and internal gas partial pressure of the hydrogen storage unit.These models are of great significance for studying and optimizing gas storage technology.Through these models,the performance of gas storage units can be better understood and improved.These studies are very helpful for improving energy storage efficiency and sustainable development.The factors affecting the charge-discharge efficiency of hydrogen storage units are analyzed.By integrating the models of each unit and considering the capacity degradation of the hydrogen storage system,we can construct an efficiency model for a large hydrogen storage system and power conversion system.In addition,the simulation models of the hydrogen production system and hydrogen consumption system were established in MATLAB/Simulink.The accuracy and effectiveness of the simulation model were proved by comparing the output voltage variation curve of the simulation with the polarization curve of the typical hydrogen production system and hydrogen consumption system.The results show that the charge-discharge efficiency of the hydrogen storage unit increases with the increase of operating temperature,and H2 and O2 partial voltage have little influence on the charge-discharge efficiency.In the process of power conversion system converter rectification operation,its efficiency decreases with the increase of temperature,while in the process of inverter operation,power conversion system efficiency increases with the increase of temperature.Combined with the efficiency of each hydrogen storage unit and power conversion system converter,the upper limit of the capacity loss of different hydrogen storage units was set.The optimal charge-discharge efficiency of the hydrogen storage system was obtained by using the Cplex solver at 36.46%and 66.34%.

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.

Solubility study of hydrogen in direct coal liquefaction solvent based on quantitative structure–property relationships model

Direct coal liquefaction(DCL)is an important and effective method of converting coal into high-valueadded chemicals and fuel oil.In DCL,heating the direct coal liquefaction solvent(DCLS)from low to high temperature and pre-hydrogenation of the DCLS are critical steps.Therefore,studying the dissolution of hydrogen in DCLS under liquefaction conditions gains importance.However,it is difficult to precisely determine hydrogen solubility only by experiments,especially under the actual DCL conditions.To address this issue,we developed a prediction model of hydrogen solubility in a single solvent based on the machine-learning quantitative structure–property relationship(ML-QSPR)methods.The results showed that the squared correlation coefficient R^(2)=0.92 and root mean square error RMSE=0.095,indicating the model’s good statistical performance.The external validation of the model also reveals excellent accuracy and predictive ability.Molecular polarization(a)is the main factor affecting the dissolution of hydrogen in DCLS.The hydrogen solubility in acyclic alkanes increases with increasing carbon number.Whereas in polycyclic aromatics,it decreases with increasing ring number,and in hydrogenated aromatics,it increases with hydrogenation degree.This work provides a new reference for the selection and proportioning of DCLS,i.e.,a solvent with higher hydrogen solubility can be added to provide active hydrogen for the reaction and thus reduce the hydrogen pressure.Besides,it brings important insight into the theoretical significance and practical value of the DCL.

3D fluid model analysis on the generation of negative hydrogen ions for negative ion source of NBI

A radio-frequency(RF) inductively coupled negative hydrogen ion source(NHIS) has been adopted in the China Fusion Engineering Test Reactor(CFETR) to generate negative hydrogen ions.By incorporating the level-lumping method into a three-dimensional fluid model,the volume production and transportation of H^(-) in the NHIS,which consists of a cylindrical driver region and a rectangular expansion chamber,are investigated self-consistently at a large input power(40 k W) and different pressures(0.3–2.0 Pa).The results indicate that with the increase of pressure,the H^(-) density at the bottom of the expansion region first increases and then decreases.In addition,the effect of the magnetic filter is examined.It is noteworthy that a significant increase in the H^(-) density is observed when the magnetic filter is introduced.As the permanent magnets move towards the driver region,the H^(-) density decreases monotonically and the asymmetry is enhanced.This study contributes to the understanding of H-distribution under various conditions and facilitates the optimization of volume production of negative hydrogen ions in the NHIS.

Generation of input spectrum for electrolysis stack degradation test applied to wind power PEM hydrogen production

Hydrogen production by proton exchange membrane electrolysis has good fluctuation adaptability,making it suitable for hydrogen production by electrolysis in fluctuating power sources such as wind power.However,current research on the durability of proton exchange membrane electrolyzers is insufficient.Studying the typical operating conditions of wind power electrolysis for hydrogen production can provide boundary conditions for performance and degradation tests of electrolysis stacks.In this study,the operating condition spectrum of an electrolysis stack degradation test cycle was proposed.Based on the rate of change of the wind farm output power and the time-averaged peak-valley difference,a fluctuation output power sample set was formed.The characteristic quantities that played an important role in the degradation of the electrolysis stack were selected.Dimensionality reduction of the operating data was performed using principal component analysis.Clustering analysis of the data segments was completed using an improved Gaussian mixture clustering algorithm.Taking the annual output power data of wind farms in Northwest China with a sampling rate of 1 min as an example,the cyclic operating condition spectrum of the proton-exchange membrane electrolysis stack degradation test was constructed.After preliminary simulation analysis,the typical operating condition proposed in this paper effectively reflects the impact of the original curve on the performance degradation of the electrolysis stack.This study provides a method for evaluating the degradation characteristics and system efficiency of an electrolysis stack due to fluctuations in renewable energy.

Synthesis,characterization and catalytic reactivity of pentacoordinate iron dicarbonyl as a model of the [Fe]-hydrogenase active site

Two mono iron complexes Fe（CO）2PR3（NN） （R = Cy （3）, Ph （4）, NN = o-phenylenediamine dianion ligand, N2H2Ph2-） derived from the ligand substitution of Fe（CO）3hPR3 by the NN ligand were isolated and structurally characterized by single crystal X-ray diffraction. They have a similar first coordination sphere and oxidation state of the iron center as the [Fe]-hydrogenase active site, and can be a model of it IR demonstrated that the effect of the NN ligand on the coordinated CO stretch- ing frequencies was due to its excellent electron donating ability. The reversible protonation/deprotonation of the NN ligand was identified by infrared spectroscopy and density functional theory computation. The NN ligand is an effective proton acceptor as the internal base of the cysteine thiolate ligand in [Fe]-hydrogenase. The electrochemical properties of complexes 3, 4 were investigated by cyclic voltammograms. Complex 3 catalyzed the transfer hydrogenation of benzoquinone to hydroquinone effectively under mild conditions.

Hydrogen production via steam reforming of bio-oil model compounds over supported nickel catalysts

The steam reforming of four bio-oil model compounds（acetic acid,ethanol,acetone and phenol） was investigated over Ni-based catalysts supported on Al2O3 modified by Mg,Ce or Co in this paper.The activation process can improve the catalytic activity with the change of high-valence Ni（Ni2O3,NiO） to low-valence Ni（Ni,NiO）.Among these catalysts after activation,the Ce-Ni/Co catalyst showed the best catalytic activity for the steam reforming of all the four model compounds.After long-term experiment at 700°C and the S/C ratio of 9,the Ce-Ni/Co catalyst still maintained excellent stability for the steam reforming of the simulated bio-oil（mixed by the four compounds with the equal masses）.With CaO calcinated from calcium acetate as CO2 sorbent,the catalytic steam reforming experiment combined with continuous in situ CO2 adsorption was performed.With the comparison of the case without the adding of CO2 sorbent,the hydrogen concentration was dramatically improved from 74.8% to 92.3%,with the CO2 concentration obviously decreased from 19.90% to 1.88%.

Modeling of the effect of hydrogen injection on blast furnace operation and carbon dioxide emissions

The effect of hydrogen injection on blast furnace operation and carbon dioxide emissions was simulated using a 1D steady-state zonal model.The maximum hydrogen injection rate was evaluated on the basis of the simulation of the vertical temperature pattern in the blast furnace with a focus on the thermal reserve zone.The effects of blast temperature and oxygen enrichment were also examined to estimate coke replacement ratio,productivity,hydrogen utilization efficiency,and carbon dioxide emission reduction.For blast temperature of 1200℃,the maximum hydrogen injection rate was 19.0 and 28.3 kg of H_(2)/t of hot metal(HM)for oxygen enrichment of 2vol%and 12vol%,respectively.Results showed a coke replacement ratio of 3-4 kg of coke/kg of H_(2),direct CO_(2) emission reduction of 10.2%-17.8%,and increased productivity by up to 13.7%depending on oxygen enrichment level.Increasing blast temperature further reduced the direct CO_(2) emissions.Hydrogen utilization degree reached the maximum of 0.52-0.54 H_(2)O/(H_(2)O+H_(2)).The decarbonization potential of hydrogen injection was estimated in the range from 9.4 t of CO_(2)/t of H_(2) to 9.7 t of CO_(2)/t of H_(2).For economic feasibility,hydrogen injection requires revolutionary progress in terms of low-cost H_(2) generation unless the technological change is motivated by the carbon emission cost.Hydrogen injection may unfavorably affect the radial temperature pattern of the raceway,which could be addressed by adopting appropriate injection techniques.

Kinetic Model of LCO Selective Hydrogenation on NiMoW/Al_(2)O_(3) Catalyst

In order to investigate the hydrofining process of LCO for producing aromatics and gasoline,the selective hydrogenation of polycyclic aromatic hydrocarbons(PAHs),a major component of light cycle oil(LCO),was studied using a NiMoW/Al_(2)O_(3)catalyst.Based on the study of the reversible hydrogenation reaction,PAHs in the selective hydrogenation process could be effectively simulated by the modeled CH and CH_(2) groups,and the hydrodesulfurization and hydrodenitrogenation kinetic models could be further established in this process.The results showed that the kinetic models developed could fit the experimental data effectively and predict the content of S,N,and aromatics in the selective hydrogenation products of LCO.

Low-order harmonic generation of hydrogen molecular ion in laser field studied by the two-state model

The low-order harmonic generation of hydrogen molecular ion interacting with a linearly polarized laser field has been investigated theoretically by using a simple two-state model. The validity of the two-state model is carefully examined by comparing the harmonic spectra of hydrogen molecular ion obtained from this model with those from the three-dimensional time-dependent Schr¨odinger equation. When combined with the Morlet transform of quantum time-frequency spectrum,the two-state model can be used to study the dynamical origin of the low-order harmonic generation of hydrogen molecular ion driven by low-frequency pulses. In addition, some interesting structures of the time profiles for low order harmonics are obtained.

Flexibility improvement evaluation of hydrogen storage based on electricity-hydrogen coupled energy model

To achieve carbon neutrality by 2060,decarbonization in the energy sector is crucial.Hydrogen is expected to be vital for achieving the aim of carbon neutrality for two reasons:use of power-to-hydrogen(P2H)can avoid carbon emissions from hydrogen production,which is traditionally performed using fossil fuels;Hydrogen from P2H can be stored for long durations in large scales and then delivered as industrial raw material or fed back to the power system depending on the demand.In this study,we focus on the analysis and evaluation of hydrogen value in terms of improvement in the flexibility of the energy system,particularly that derived from hydrogen storage.An electricity-hydrogen coupled energy model is proposed to realize the hourly-level operation simulation and capacity planning optimization aiming at the lowest cost of energy.Based on this model and considering Northwest China as the region of study,the potential of improvement in the flexibility of hydrogen storage is determined through optimization calculations in a series of study cases with various hydrogen demand levels.The results of the quantitative calculations prove that effective hydrogen storage can improve the system flexibility by promoting the energy demand balance over a long term,contributing toward reducing the investment cost of both generators and battery storage and thus the total energy cost.This advantage can be further improved when the hydrogen demand rises.However,a cost reduction by 20%is required for hydrogen-related technologies to initiate hydrogen storage as long-term energy storage for power systems.This study provides a suggestion and reference for the advancement and planning of hydrogen storage development in regions with rich sources of renewable energy.

Shell and shrinking core kinetics model of Mg-based hydrogen storage alloys

The kinetics equation of the Mg-based hydrogen storage alloys (Mg-Ni-MO) was established by the shell and shrinking core model. The total coefficients of the kinetics equation of the hydrogen absorption and desorption process with shell diffusion as the controlling step were determined by semi-empirical and semi-theoretical methods, and the apparent activation energy of the hydrogen absorption process was obtained. The calculation results can well accord with the experimental data, and can well forecast the hydrogen storage capacity and absorption rate at different times. By using the kinetics equation, the effects of temperature and pressure on the hydrogen storage process can also be well understood. The kinetics equation is helpful for the design of the hydrogen storage container.

Investigation of Highly Designable Dented Structures in HP Model with Hydrogen Bond Energy

Some highly designable protein structures have dented on the surface of their native structures, and are not full compactly folded. According to hydrophobic-polar （HP） model the most designable structures are full compactly folded. To investigate the designability of the dented structures, we introduce the hydrogen bond energy in the secondary structures by using the secondary-structure-favored HP model proposed by Ou-yang etc. The result shows that the average designability increases with the strength of the hydrogen bond. The designabilities of the structures with same dented shape increase exponentially with the number of secondary structure sites. The dented structures can have the highest designabilities for a certain value of hydrogen bond energy density.

Establishment of mitral regurgitation swine model and study the change of hydrogen sulfide system

Objective To establish the mitral regurgitation swine model and study the change of hydrogen sulfide(H2S)system in chronic heart failure model.Methods Miniature pigs were randomly divided into two groups,the control group(n=6)and mitral regurgitation group(n=6).Chronic heart failure models were established by pulling mitral chordal through a small incision extracorporeal.

Numerical simulation of hydrogen arcjet thruster with coupled sheath model

In the present work,a complete 2D chemical and thermal non-equilibrium numerical model coupled with a relatively simple sheath model is developed for hydrogen arcjet thruster.Conduction heat transfer in the anode wall is also included in the model.The operating voltages predicted by the model are compared with those in the literature and are found to be in close agreement.Power distributions for the various operating conditions are obtained,anode radiation loss primarily determines the thruster efficiency.Higher thruster efficiency was found to be associated with longer arc length.At cathode ion diffusion contribution dominates except at low input current where thermo-field electron current is dominant.

Micro-Modelling Approach to Predict the Influence of Hydrogen Pressure on Short Crack Behaviour

A micromechanical model, based on the FEA (finite element analysis), was developed to estimate the influence of hydrogen pressure on short crack behaviour. Morphology of voids has important connotations in the development of the model. Stress intensity factor was calculated for different crack geometries under hydrogen pressure. The analysis indicates that the form factor of a crack emerging from a round void will be less affected by trapped hydrogen pressure-compared to an elongated void. This analysis reinforces the beneficial effect of inclusion shape control in reducing significantly the detrimental effect of hydrogen.

Modeling hydrogen exchange of proteins by a multiscale method

We proposed a practical way for mapping the results of coarse-grained molecular simulations to the observables in hydrogen change experiments.By combining an atomic-interaction based coarse-grained model with an all-atom structure reconstruction algorithm,we reproduced the experimental hydrogen exchange data with reasonable accuracy using molecular dynamics simulations.We also showed that the coarse-grained model can be further improved by imposing experimental restraints from hydrogen exchange data via an iterative optimization strategy.These results suggest that it is feasible to develop an integrative molecular simulation scheme by incorporating the hydrogen exchange data into the coarse-grained molecular dynamics simulations and therefore help to overcome the accuracy bottleneck of coarse-grained models.

Exploring the contribution of oxygen reduction reaction to Mg corrosion by modeling assisted local analysis

Oxygen reduction reaction(ORR)has been disclosed in recent studies as a significant secondary cathodic process during magnesium corrosion.This work elaborates on the contribution of ORR to the total corrosion process of pure Mg at different impurity levels in NaCl electrolyte with the assistance of local techniques.A finite element based numerical model taking into account the contribution of ORR during the corrosion of the Mg test materials has been designed in this study considering the local oxygen concentration.Respective computational simulations were calibrated based on the experimental data and evaluated accordingly.Finally,the simultaneous monitoring of local concentration of H_(2) and O_(2),and the combined modeling study reveal the relation between ORR and hydrogen evolution reaction.

Spectroscopic Characterization, Molecular Modeling and DFT/TD-DFT/PCM Calculations of Novel Hydrogen-Bonded Charge Transfer Complex between Chloranilic Acid and 2-Amino-4,6-Dimethylpyridine

A charge transfer hydrogen bonded complex between the electron donor (proton acceptor) 2-amino-4,6-dimethylpyridine with the electron acceptor (proton donor) chloranilic acid has been synthesized and studied experimentally and theoretically. The stability constant recorded high values indicating the high stability of the formed complex. In chloroform, ethanol, methanol and acetonitrile were found the stoichiometric ratio 1:1. The solid complex was prepared and characterized by different spectroscopy techniques. FTIR, 1H and 13C NMR studies supported the presence of proton and charge transfers in the formed complex. Complemented with experimental results, molecular modelling using the density functional theory (DFT) calculations was carried out in the gas, chloroform and methanol phases where the existence of charge and hydrogen transfers. Finally, a good consistency between experimental and theoretical calculations was found confirming that the applied basis set is the suitable one for the system under investigation.