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.

Gasification of lignite from Polish coal mine to hydrogen-rich gas

The efforts of the world research activities involved in clean coal technologies development focus to a considerable extent on integrated hydrogen and power generation technologies based on coal gasification.As an alternative to combustion pro-cesses,gasification offers increased efficiency,lower negative environmental impact as well as wider application range of the main product—synthesis gas—in power generation and chemical syntheses.In order to select the most optimal lignite for the purpose of gasification,it is necessary to determine coal reactivity,the key parameter characterizing how fast the fuel reacts with the gasifying medium and controlling its process ability in thermochemical conversion to energy and/or energy carriers.This paper presents the experimental results of oxygen/steam gasification of lignite coal char in a fixed bed reactor under atmospheric pressure and at the temperature of 700,800 and 900℃;the samples come from an open pit lignite mine in the southwest of Poland.The effectiveness of the gasification process was tested in terms of the total gas and hydrogen yields,gas composition,carbon conversion rate and chars reactivity.

Experimental Study on the Method of Extracting Humic Acids from Brown Coal Using Hydrogen Peroxide

[ Objective l The study aimed to discuss the optimal conditions of extracting humic acids from brown coal using hydrogen peroxide （H202）. [ Method] Fulvic acid （FA） was prepared through oxidizing the brown coal from Qujing City, Yunnan Province using H202, and humic acids were extracted from the original brown coal and its residues respectively, then the dominate constituents of humic acids were obtained by using pH grading method, finally their chemical composition of humid acids was characterized by Fourier transform infrared spectrometry and func- tional group content analysis. [Result] The mass ratio of the brown coal and oxidant affected the yield of FA most obviously, followed by oxidization temperature and duration, while oxidant concentration had no obvious effect. The optimum conditions were determined as follows： coal-oxidant ratio was 1 ： 0.60, oxidization temperature was 45 ℃, oxidization duration was 210 min, and the concentration of hydrogen peroxide was 20%. Under the conditions, the yield of FA was up to 20.40%. Analysis of component properties indicated that the content of carboxyl and total acidic groups in FA improved obviously under the optimum conditions, and the content of active functional groups in OHA was higher than that of HA, while the domi- nate constituents of OHA needed higher pH during precipitation compared with those of HA. [ Conclusion] The research could provide a new method to prepare good humic acids using brown coal,

Characteristics of Hydrogen-rich Coals in Southern China:Implications from Organic Geochemistry and Carbon Isotopic Compositions

The organic geochemical characteristics of hydrogen-rich coal in southern China were investigated synthetically through organic geochemistry and carbon isotope analyses.The results showed that the hydrogen contents of the test samples were more than 5.0% and the H/C atomic ratios were between 0.76-1.06.Samples were found to be composed mostly of Type Ⅱ-Ⅲ℃ kerogen,consistent with good hydrocarbon-generation potential.The R_(o)(0.54-1.10%)and T_(max)(430-453℃)values imply that the hydrogen-rich coals were in low maturity to mature stages.Stable carbon isotopic ratios(δ^(13)C_(org))of the samples used varied from −24.5‰ to −23.4‰,the barkinite content ranging from 13.9% to 83.3%,indicating a predominantly terrestrial origin with marine influence during coal formation.Some organic geochemical parameters showed corresponding changes as the hydrogen content increased from 5.0% to 7.0%,however,the source inputs changed significantly when hydrogen content was greater than 6.0%.Terrestrial higher plants gradually become predominant within the coal-forming materials,whereas this dominant position is not apparent at lower hydrogen contents,which is attributable to the strong seawater effect during the hydrogen-rich coal formation process.

Hydrogen Bonds in Coal——The Influence of Coal Rank and the Recognition of a New Hydrogen Bond in Coal

By means of in situ diffuse reflectance FTIR, the IR spectra of 6 coals with different ranks were obtained from room temperature to 230 ℃. A new curve fitting method was used to recognize the different hydrogen bonds in the coals, and the influence of coal ranks on the distribution of hydrogen bonds(HBs) in the coals and their thermal stability were discussed. The results show that there is another new HB(around 2514 cm -1 ) between the -SH in mercaptans or thiophenols and the nitrogen in the pyridine like compounds in the coals, and the evidence for that was provided. The controversial band of the HB between hydroxyl and the nitrogen of the pyridine like compounds was determined in the range of 3028-2984 cm -1 , and the result is consistent with but more specific than that of Painter et al .. It was found that the stability of different HBs in the coals is influenced by both coal rank and temperature. For some HBs, the higher the coal rank, the higher the stability of them. Within the temperature range of our research, the stability of the HB between the hydroxyl and the π bond increases to some extent for some coals at temperatures higher than 110 or 140 ℃.

Trends and advances in the development of coal fly ash-based materials for application in hydrogen-rich gas production:A review

Coal fly ash(FA),a valuable industrial solid residue generated from coal combustion,is composed of various metal oxides and has a high thermal stability.Given that the coal-based energy will continue to account for a significant portion of global electricity generation in the coming years,the lack of effective management strategies exacerbates the threat of FA wastes to the surrounding environment and human health.For a sustainable development,green and renewable hydrogen economy and CO_(2)capture efforts provide appealing opportunities to valorize FA as catalysts and/or sorbents due to their appealing physicochemical properties.Hydrogen applications along with carbon neutrality are potential strategies to mitigate climate change crisis,but high processing costs(catalysts/sorbents)are challenging to realize this purpose.In this context,the utilization of FA not only enhances industrial competitiveness(by reducing manufacturing costs),but also provides ecologically friendly approaches to minimizing this solid waste.This state-of-the-art review highlights a wide-ranging outlook on the valorization of FA as catalysts and sorbents for hydrogen-rich gas production via conventional/intensified processes(CO_(2)/H_(2)O reforming,ammonia decomposition,hydride hydrolysis).The fundamental physicochemical characterizations and hazards/utilization of FA,which significantly affect the FA's utilization in various fields,are first introduced.The influence of several factors(like FA types and catalysis/sorption operation conditions)on the activity performance of FA-based materials is then discussed in detail.This critical review aims to open the window to further innovative ideas regarding the application of different FA residues in other catalytic and sorption processes.

Multi-technique integration separation frameworks after steam reforming for coal-based hydrogen generation

Coal-based H2 generation has abruptly increased in recent years.The PSA-VPSA-SC process is the matured and standard framework for H2 purification and CO_(2) capture in many existing plants,including normal and vacuum pressure swing adsorption units in series(PSA-VPSA),and shallow condensation unit(SC).However,this standard process is frequently subjected to low H2 recovery ratio and high purification cost.In this work,H2-selective and C02-selective membrane units,i.e.,HM and CO_(2) M,are attempted to support the standard process and ameliorate constraints.In the beginning,HM unit is arranged after VPSA to enhance H2 recovery from the decarbonized stream,i.e.,the PSA-VPSA-SC/HM process.As a result,H2 recovery ratio can be enhanced significantly from 83%to 98%.In the following,VPSA is replaced with CO_(2) M unit to reduce investment and operation cost,i.e.,the PSA-CO_(2) M-SC/HM process.Accordingly,the specific purification cost is diminished from 33.46 to 32.02 USD·(103 m^(3) H_(2))-1,saved by 4.3%,meanwhile the construction cost is falling back and just a little higher than that for the standard process.In the end,another CO_(2) M unit is launched before PSA,i.e.,the CO_(2) M-PSA-CO_(2) M-SC/HM process,which could unbundle CO_(2) enrichment partially from H2 purification,and then save more investment and operation cost.In comparison with the standard process,this ultimate retrofitted process can be superior in all the three crucial indices,i.e.,recovery ratio,investment,and specific purification cost.On the whole,coal-based H2 generation can be ameliorated significantly through high efficient H2-selective and CO_(2)-selective membrane units.

Use of coals and wastes in a co-gasification process aimed at producing hydrogen rich gas

The use of low-quality coals and flotoconcentrates is currently severely limited,and the problem of managing municipal waste from anthropogenic activities is currently a challenge.The problems of reducing carbon dioxide emissions,utilizing the energy potential of waste and increasing its recycling have an impact on the costs of electricity production.Considering the abundant streams of unused fuels,they can be considered as attractive energy materials,so environmentally-friendly and cost-effective options for their utilization should be developed.A study was conducted using steam co-gasification technology on selected coals,flotation concentrates and Refuse Derived Fuel(RDF)alternative fuel.Selected low-quality coals were combined with RDF alternative fuel in a process aimed at hydrogen production.The experiments produced gas with hydrogen concentrations ranging from 67%(vol.)to 68%(vol.)with low methane concentrations.It was observed that the addition of alternative fuels helped to increase the hydrogen concentration in syngas.Attention was paid to the catalytic ability of the metal oxides contained in the fuel blend,with particular reference to K_(2)O and Al_(2)O_(3)and TiO_(2).

Conversion of coalbed methane surrogate into hydrogen and graphene sheets using rotating gliding arc plasma

The use of atmospheric rotating gliding arc(RGA)plasma is proposed as a facile,scalable and catalyst-free approach to synthesizing hydrogen(H2)and graphene sheets from coalbed methane(CBM).CH4 is used as a CBM surrogate.Based on a previous investigation of discharge properties,product distribution and energy efficiency,the operating parameters such as CH4 concentration,applied voltage and gas flow rate can effectively affect the CH4 conversion rate,the selectivity of H2 and the properties of solid generated carbon.Nevertheless,the basic properties of RGA plasma and its role in CH4 conversion are scarcely mentioned.In the present work,a 3D RGA model,with a detailed nonequilibrium CH4/Ar plasma chemistry,is developed to validate the previous experiments on CBM conversion,aiming in particular at the distribution of H2 and other gas products.Our results demonstrate that the dynamics of RGA is derived from the joint effects of electron convection,electron migration and electron diffusion,and is prominently determined by the variation of the gas flow rate and applied voltage.Subsequently,a combined experimental and chemical kinetical simulation is performed to analyze the selectivity of gas products in an RGA reaction,taking into consideration the formation and loss pathways of crucial targeted substances(such as CH4,C2H2,H2 and H radicals)and corresponding contribution rates.Additionally,the effects of operating conditions on the properties of solid products are investigated by scanning electron microscopy(SEM)and Raman spectroscopy.The results show that increasing the applied voltage and decreasing CH4 concentration will change the solid carbon from its initial spherical structure into folded multilayer graphene sheets,while the size of the graphene sheets is slightly affected by the change in gas flow rate.

Composite Catalyst for Hydrogenation of CO_(2) Developed by CAS Shanxi Institute of Coal Chemistry

The CAS Shanxi Institute of Coal Chemistry(SICC)has developed a CO_(2) hydrogenation catalyst composed of solid solution structured composite metal oxides and zeolite.The group IIIA metal elements comprising the composite metal oxides can promote the adsorption and dissociation of H_(2) to form active hydrogen species,while the incorporation of group VIB metal elements can promote the formation of oxygen vacancies on the surface,which can be conducive to the adsorption and activation of CO_(2) along with the formation of methanol through hydrogenation of the formate/methoxyl intermediates.

Key technology and application of AB_(2) hydrogen storage alloy in fuel cell hydrogen supply system

At present,there is limited research on the application of fuel cell power generation system technology using solid hydrogen storage materials,especially in hydrogen-assisted two-wheelers.Considering the disadvantages of low hydrogen storage capacity and poor kinetics of hydrogen storage materials,our primary focus is to achieve smooth hydrogen ab-/desorption over a wide temperature range to meet the requirements of fuel cells and their integrated power generation systems.In this paper,the Ti_(0.9)Zr_(0.1)Mn_(1.45)V_(0.4)Fe_(0.15) hydrogen storage alloy was successfully prepared by arc melting.The maximum hydrogen storage capacity reaches 1.89 wt% at 318 K.The alloy has the capability to absorb 90% of hydrogen storage capacity within 50 s at 7 MPa and release 90% of hydrogen within 220 s.Comsol Multiphysics 6.0 software was used to simulate the hydrogen ab-/desorption processes of the tank.The flow rate of cooling water during hydrogen absorption varied in a gradient of(0.02 t x)m s^(-1)(x=0,0.02,0.04,0.06,0.08,0.1,0.12).Cooling water flow rate is positively correlated with the hydrogen absorption rate but negatively correlated with the cost.When the cooling rate is 0.06 m s^(-1),both simulation and experimentation have shown that the hydrogen storage tank is capable of steady hydrogen desorption for over 6 h at a flow rate of 2 L min^(-1).Based on the above conclusions,we have successfully developed a hydrogen-assisted two-wheeler with a range of 80 km and achieved regional demonstration operations in Changzhou and Shaoguan.This paper highlights the achievements of our team in the technological development of fuel cell power generation systems using solid hydrogen storage materials as hydrogen storage carriers and their application in twowheelers in recent years.

Thermodynamical Study on Production of Acetylene from Coal Pyrolysis in Hydrogen Plasma

The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show that the hydrogen concentration in the equilibrium system is very important for the acetylene production by coal conversion and the energy consumption for the production of acetylene per-kilogram strongly depends on the hydrogen concentration and the temperature.

A density functional theory study on the decomposition of aliphatic hydrocarbons and cycloalkanes during coal pyrolysis in hydrogen plasma

To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.

CFD Simulation of a Hydrogen/Argon Plasma Jet Reactor for Coal Pyrolysis

A Computational Fluid Dynamics(CFD) model was formulated for DC arc hydrogen/argon plasma jet reactors used in the process of the thermal H_2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete data, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-εequations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.

Review on the design of high-strength and hydrogen-embrittlement-resistant steels

Given the carbon peak and carbon neutrality era,there is an urgent need to develop high-strength steel with remarkable hydrogen embrittlement resistance.This is crucial in enhancing toughness and ensuring the utilization of hydrogen in emerging iron and steel materials.Simultaneously,the pursuit of enhanced metallic materials presents a cross-disciplinary scientific and engineering challenge.Developing high-strength,toughened steel with both enhanced strength and hydrogen embrittlement(HE)resistance holds significant theoretical and practical implications.This ensures secure hydrogen utilization and further carbon neutrality objectives within the iron and steel sector.Based on the design principles of high-strength steel HE resistance,this review provides a comprehensive overview of research on designing surface HE resistance and employing nanosized precipitates as intragranular hydrogen traps.It also proposes feasible recommendations and prospects for designing high-strength steel with enhanced HE resistance.

Hydrogen sulfide responsive nanoplatforms: Novel gas responsive drug delivery carriers for biomedical applications

Hydrogen sulfide(H_(2)S)is a toxic,essential gas used in various biological and physical processes and has been the subject of many targeted studies on its role as a new gas transmitter.These studies have mainly focused on the production and pharmacological side effects caused by H_(2)S.Therefore,effective strategies to remove H_(2)S has become a key research topic.Furthermore,the development of novel nanoplatforms has provided new tools for the targeted removal of H_(2)S.This paper was performed to review the association between H_(2)S anddisease,relatedH_(2)S inhibitory drugs,aswell as H_(2)S responsive nanoplatforms(HRNs).This review first analyzed the role of H_(2)S in multiple tissues and conditions.Second,common drugs used to eliminate H_(2)S,as well as their potential for combination with anticancer agents,were summarized.Not only the existing studies on HRNs,but also the inhibition H_(2)S combined with different therapeutic methods were both sorted out in this review.Furthermore,this review provided in-depth analysis of the potential of HRNs about treatment or detection in detail.Finally,potential challenges of HRNs were proposed.This study demonstrates the excellent potential of HRNs for biomedical applications.

Understanding the dehydrogenation properties of Mg(0001)/MgH_(2)(110)interface from first principles

Magnesium hydride is one of the most promising solid-state hydrogen storage materials for on-board application.Hydrogen desorption from MgH_(2) is accompanied by the formation of the Mg/MgH_(2) interfaces,which may play a key role in the further dehydrogenation process.In this work,first-principles calculations have been used to understand the dehydrogenation properties of the Mg(0001)/MgH_(2)(110) interface.It is found that the Mg(0001)/MgH_(2)(110) interface can weaken the Mg-H bond.The removal energies for hydrogen atoms in the interface zone are significantly lower compared to those of bulk MgH_(2).In terms of H mobility,hydrogen diffusion within the interface as well as into the Mg matrix is considered.The calculated energy barriers reveal that the migration of hydrogen atoms in the interface zone is easier than that in the bulk MgH_(2).Based on the hydrogen removal energies and diffusion barriers,we conclude that the formation of the Mg(0001)/MgH_(2)(110) interface facilitates the dehydrogenation process of magnesium hydride.

Asymmetric orbital hybridization in Zn-doped antiperovskite Cu_(1-x)Zn_(x)NMn_(3)enables highly efficient electrocatalytic hydrogen production

Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.

Improved hydrogen storage kinetics of MgH_(2) using TiFe_(0.92)Mn_(0.04)Co_(0.04) with in-situ generated α-Fe as catalyst

While TiFe alloy has recently attracted attention as the efficient catalyst to enhance de/hydrogenation rates of Mg/MgH_(2),the difficulty of its activation characteristics has hindered further improvement of reaction kinetics.Herein,we report that the TiFe_(0.92)Mn_(0.04)Co_(0.04) catalyst can overcome the abovementioned challenges.The synthesized MgH_(2)-30 wt% TiFe_(0.92)Mn_(0.04)Co_(0.04) can release 4.5 wt%of hydrogen in 16 min at 250℃,three times as fast as MgH_(2).The activation energy of dehydrogenation was as low as 84.6 kJ mol^(-1),which is 46.8%reduced from pure MgH_(2).No clear degradation of reaction rates and hydrogen storage capacity was observed for at least 30 cycles.Structural studies reveal that TiFe_(0.92)Mn_(0.04)Co_(0.04) partially decomposes to in-situ generatedα-Fe particles dispersed on TiFe_(0.92)Mn_(0.04)Co_(0.04).The presence ofα-Fe reduces the formation of an oxide layer on TiFe_(0.92)Mn_(0.04)Co_(0.04),enabling the activation processes.At the same time,the hydrogen incorporation capabilities of TiFe_(0.92)Mn_(0.04)Co_(0.04) can provide more hydrogen diffusion paths,which promote hydrogen dissociation and diffusion.These discoveries demonstrate the advanced nature and importance of combining the in-situ generatedα-Fe with TiFe_(0.92)Mn_(0.04)Co_(0.04).It provides a new strategy for designing highly efficient and stable catalysts for Mg-based hydrogen storage materials.

Hydrogen Permeation Characteristics of Pd-CuMembrane in Plasma Membrane Reactor

Hydrogen is an alternative energy source that has the potential to replace fossil fuels.One of the hydrogen applications is as a material for Polymer Electrolyte Membrane Fuel Cells(PEMFC)in fuel cell vehicles.High-purity hydrogen can be obtained using a hydrogen separation membrane to prevent unwanted contaminants from potentially harming the PEMFC components.In this study,we fabricated a plasma membrane reactor and investigated the permeation performance of a hydrogen separation membrane in a plasma membrane reactor utilizing atmospheric pressure plasma.The result showed the hydrogen permeation rate increasing with time as reactor temperature is increased through joule heating.By decreasing the gap length of the reactor from 2 to 1 mm,the hydrogen permeation rate increases by up to 40%.The hydrogen permeation rate increases by 30%when pressure is applied to the plasma membrane reactor by up to 100 kPa.