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.

Benzene selective hydrogenation over supported Ni(nano-) particles catalysts: Catalytic and kinetics studies

This report aims to reduce the benzene in a mixture of benzene and toluene as a model reaction using catalytic hydrogenation. In this research, we developed a series of catalysts with different supports such as Ni/HMS, Ni/HZSM-5, Ni/HZSM5-HMS, Ni/Al2O3 and Ni/SiO2. Kinetic of this reaction was investigated under various hydrogen and benzene pressures. For more study, two kinetic models have also been selected and tested to describe the kinetics for this reaction. Both used models, the power law and Langmuir-Hinshelwood, provided a good fit toward the experimental data and allowed to determine the kinetic parameters. Among these catalysts, Ni/Al2O3 showed the maximum benzene conversion （99.19%） at 130℃ for benzene hydrogenation. The lowest toluene conversion was observed for Ni/SiO2. Furthermore, this catalyst presented high selectivity to benzene （75.26%） at 130℃. The catalytic performance （activity, selectivity and stability） and kinetics evaluations were shown that the Ni/SiO2 is an effective catalyst to hydrogenate benzene. It seems that the surface properties particularly pore size are effective parameter compared to other factors such as acidity and metal dispersion in this process.

Enhanced hydrogen storage kinetics of nanocrystalline and amorphous Mg_2N-type alloy by substituting Ni with Co

In order to improve the hydrogen storage kinetics of the Mg2Ni-type alloys, Ni in the alloy was partially substituted with element Co. The Mg2Ni-type Mg2Ni1-xCox （x=0, 0.1, 0.2, 0.3, 0.4） alloys were fabricated by melt-spinning technique. The structures of the as-spun alloys were characterized by XRD and TEM. The gaseous and electrochemical hydrogen storage kinetics of the alloys was measured. The results show that the substitution of Co for Ni notably enhances the glass forming ability of the Mg2Ni-type alloy. The amorphization degree of the alloys visibly increases with rising of Co content. Furthermore, the substitution of Co for Ni significantly improves the hydrogen storage kinetics of the alloys. With an increase in the amount of Co substitution from 0 to 0.4, the hydrogen absorption saturation ratio of the as-spun （15 m/s） alloy increases from 81.2% to 84.9%, the hydrogen desorption ratio from 17.60% to 64.79%, the hydrogen diffusion coefficient increases from 1.07×10-11 to 2.79×10-11 cm2/s and the limiting current density increases from 46.7 to 191.7 mA/g, respectively.

Hydrogen desorption kinetics mechanism of Mg-Ni hydride under isothermal and non-isothermal conditions

The Mg-Ni hydride was prepared by hydriding combustion synthesis under a high magnetic field. The dehydriding kinetics of the hydrides was measured under the isothermal and non-isothermal conditions. A model was applied to analyzing the kinetics behavior of Mg-Ni hydride. The calculation results show that the theoretical value and the experimental data can reach a good agreement, especially in the case of non-isothermal dehydriding. The rate-controlling step is the diffusion of hydrogen atoms in the solid solution. The sample prepared under magnetic field of 6 T under the isothermal condition can reach the best performance. The similar tendency was observed under the non-isothermal condition and the reason was discussed.

Kinetics of Hydrogen Absorption in Hydrogen Storage Alloy

Hydrogenation kinetics of MLNi3.8(Co,Mn,Al)1.2 and MLNi3.7(Co,Mn,Al)1.2Cu0.1 alloy in α + β phase at the temperatUre range of 30 ～70 ℃ has been studied. The kinetic mechanism of hydrogen absorption is not affected by initial hydrogen pressure. Temperature does not influence the rate of hydrogen absorption obviously. In the prior and later period of hydrogen absorption the rate-controlling step is chemical reaction and hydrogen diffusion in the hydride phase respectively for MLNi3.8(Co,Mn,Al)1.2 alloy. Adding Cu, the rate-controlling step changes from chemical reaction to the nucleation and growth of β phase in the prior period and the process of hydrogen absorption still controlled by diffusion in the later period.

Kinetics of Hydrogen Absorption in MmNi_（3．55）Co_（0．75）Mn_（0．4）Al_（0．3） Alloy

The kinetic process of MmNi3. 55Co0. 75Mn0. 4Al0. 3 alloy absorbing hydrogen in αand α+βphases at the temperature range of 22￣ 60℃ has been studied. The results show that the kinetic process is controlled by chemical reaction in the α phase and the mechanism of hydrogenation kinetics is not affected by initial hydrogen pressure. In the α+β phase region,the speed of hydrogen absorption is controlled by hydrogen diffusion in the hydride.A reaction rate equation and apparent activation energy have been obtained.

Gaseous and Electrochemical Hydrogen Storage Kinetics of As-quenched Nanocrystalline and Amorphous Mg_2Ni-type Alloys

The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox （x = 0, 0.1, 0.2, 0.3, 0.4） alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient （D） along with the limiting current density （IL） and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.

Influences of substituting Ni with M(M=Cu,Co,Mn)on gaseous and electrochemical hydrogen storage kinetics of Mg_(20)Ni_(10) alloys

In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).

Mapping the kinetics of hydrogen evolution reaction on Ag via pseudo-single-crystal scanning electrochemical cell microscopy

Elucidating the structure-activity relationship in electrocatalysis is of fundamental interest for electrochemical energy conversion and storage.However,the heterogeneity in the surface structure of electrocatalysts,including the presence of various facets,poses an analytical challenge in revealing the true structure-activity relationship because the activity is conventionally measured on ensemble,resulting in an averaged activity that cannot be unequivocally associated with a single structural motif.Scanning electrochemical cell microscopy(SECCM)[1]combined with colocalized electron backscatter diffraction(EBSD)offers a direct way to reveal the correlative local electrochemical and structural information.Herein,we measured the hydrogen evolution reaction(HER)activity on Ag and its dependence on the crystal orientation.From the combined EBSD and SECCM mapping,it is found that Ag grains closer to{111}show a higher exchange current density,while those closer to{110}show a lower Tafel slope.The Tafel slope is also found to decrease with the step density increase.The ability to measure the electrocatalytic activity under a high mass-transfer rate allows us to reveal the activity difference at a high current density(up to 200 mA/cm^(2)).The approach reported here can be expanded to other systems to reveal the nature of active sites of electrocatalysis.

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg12-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.

Improved hydrogenation properties of Mg-x(Ti_(0.9) Zr_(0.2) Mn_(1.5) Cr_(0.3))composites

Mg-x(Ti0.9 Zr0.2 Mn1.5 Cr0.3)(x=20%,30%,40%) (mass fraction) composite powders were prepared by reactive ball milling with hydrogen and their hydrogen storage properties and microstructure were investigated by XRD,SEM and pressure-composition-temperature measurement.The results show that the composites have 3.83%-5.07%hydrogen capacity at 553 K and good hydrogenation kinetics,even at room temperature.Among them,the milled Mg-30%(Ti0.9Zr0.2Mn1.5Cr0.3)composite has the highest hydrogenation kinetics as it can quickly absorb 2.1%hydrogen at 373 K,3.5%in 2 000 s at 473 K,even 3.26%in 60 s at 553 K under 3 MPa hydrogen pressure.The improved hydrogenation properties come from the catalytic effect of Ti0.9 Zr0.2 Mn1.5 Cr0.3 particles dispersed uniformly on the surface of Mg particles.

Catalytic effect comparison of TiO_(2) and La_(2)O_(3) on hydrogen storage thermodynamics and kinetics of the as-milled La-Sm-Mg-Ni-based alloy

In this investigation,mechanical grinding was applied to fabricating the Mg-based alloys La_(7)Sm_(3)Mg_(80)Ni_(10)+5 wt.%M(M=None,TiO_(2),La_(2)O_(3))(named La_(7)Sm_(3)Mg_(80)Ni_(10)-5 M(M=None,TiO_(2),La_(2)O_(3))).The result reveals that the structures of as-milled alloys consist of amorphous and nanocrystalline.The particle sizes of the added M(M=TiO_(2),La_(2)O_(3))alloys obviously diminish in comparison with the M=None specimen,suggesting that the catalysts TiO_(2)and La_(2)O_(3)can enhance the grinding efficiency.What’s more,the additives TiO_(2)and La_(2)O_(3)observably improve the activation performance and reaction kinetics of the composite.The time required by releasing 3 wt.%hydrogen at553,573 and 593 K is 988,553 and 419 s for the M=None sample,and 578,352 and 286 s for the M=TiO_(2)composite,and 594,366,301 s for the La_(2)O_(3)containing alloy,respectively.The absolute value of hydrogenation enthalpy change|△H|of the M(M=None,TiO_(2),La_(2)O_(3))alloys is 77.13,74.28 and 75.28 kJ/mol.Furthermore,the addition of catalysts reduces the hydrogen desorption activation energy(E_(a)^(de)).

Improved Hydrogen Storage Kinetics of Nanocrystalline and Amorphous Mg-Nd-Ni-Cubased Mg_2Ni-type Alloys by Adding Nd

In order to improve the gaseous and electrochemical hydrogen storage kinetics of the M2Nitype alloy, the elements Cu and Nd were added in the alloy. The nanocrystalline and amorphous Mg2Ni-type alloys with the composition of（Mg24Ni10Cu2）100-xNdx（x = 0, 5, 10, 15, 20） were prepared by melt spinning technology. The effects of Nd content on the structures and hydrogen storage kinetics of the alloys were investigated. The characterization by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and scanning electron microscopy（SEM） reveals that all the as-cast alloys hold multiphase structures, containing Mg2Ni-type major phase as well as some secondary phases Mg6Ni, Nd5Mg41, and Nd Ni, whose amounts clearly grow with increasing Nd content. Furthermore, the as-spun Nd-free alloy displays an entire nanocrystalline structure, whereas the as-spun Nd-added alloys hold a mixed structure of nanocrystalline and amorphous structure and the amorphization degree of the alloys visibly increases with the rising of the Nd content, suggesting that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. The measurement of the hydrogen storage kinetics indicates that the addition of Nd significantly improves the gaseous and electrochemical hydrogen storage kinetics of the alloys. The addition of Nd enhances the diffusion ability of hydrogen atoms in the alloy, but it impairs the charge-transfer reaction on the surface of the alloy electrode, which makes the high rate discharge ability（HRD） of the alloy electrode fi rst mount up and then go down with the growing of Nd content.

Effect of ternary transition metal sulfide FeNi_(2)S_(4)on hydrogen storage performance of MgH_(2)

Hydrogen storage is a key link in hydrogen economy,where solid-state hydrogen storage is considered as the most promising approach because it can meet the requirement of high density and safety.Thereinto,magnesium-based materials(MgH_(2))are currently deemed as an attractive candidate due to the potentially high hydrogen storage density(7.6 wt%),however,the stable thermodynamics and slow kinetics limit the practical application.In this study,we design a ternary transition metal sulfide FeNi_(2)S_(4)with a hollow balloon structure as a catalyst of MgH_(2)to address the above issues by constructing a MgH_(2)/Mg_(2)NiH_(4)-MgS/Fe system.Notably,the dehydrogenation/hydrogenation of MgH_(2)has been significantly improved due to the synergistic catalysis of active species of Mg_(2)Ni/Mg_(2)NiH_(4),MgS and Fe originated from the MgH_(2)-FeNi_(2)S_(4)composite.The hydrogen absorption capacity of the MgH_(2)-FeNi_(2)S_(4)composite reaches to 4.02 wt%at 373 K for 1 h,a sharp contrast to the milled-MgH_(2)(0.67 wt%).In terms of dehydrogenation process,the initial dehydrogenation temperature of the composite is 80 K lower than that of the milled-MgH_(2),and the dehydrogenation activation energy decreases by 95.7 kJ·mol-1 compared with the milled-MgH_(2)(161.2 kJ·mol^(-1)).This method provides a new strategy for improving the dehydrogenation/hydrogenation performance of the MgH_(2)material.

Hydrogen storage thermodynamics and kinetics of as-cast Ce-Mg-Ni-based alloy

The reaction kinetics of alloys based on magnesium are known to be greatly improved by the partial substitution of Mg with rare earths and transition metals,particularly Ni.The enhanced superficial hydrogen dissociation rate,the weakened Mg-H bond and the lower activation energy following element replacement are thought to be related to the better performance.The experimental alloys Ce5Mg_(95-x)Ni_(x)(x=5,10,15)were smelted by the vacuum induction melting.The phase transformation and structural evolution of experimental alloys before and after reaction with hydrogen were char-acterized by X-ray diffraction,scanning electron microscopy and transmission electron microscopy.The cast specimens contain CeMg_(12),Mg and Mg_(2)Ni phases,and the increase in Ni content results in an obvious growth of Mg_(2)Ni phase.The isothermal and non-isothermal hydrogenation and dehydrogenation kinetics of the experimental specimens were investi-gated using the Sievert apparatus,differential scanning calorimetry and thermal gravimetric analyzer.The activation energy may be calculated using the Arrhenius and Kissinger equations.The experimental alloys have been shown to have good activation properties,with a reversible hydriding and dehydriding capacities of around 5.0 wt.%in the first cycle.The initial dehydrogenation temperature of MgH_(2) decreases from 557.5 to 537.7 K with changing Ni content from 5 to 15 at.%.The dehydrogenation activation energy also reduces from 77.09 to 62.96 kJ/mol,which explains the improved hydrogen storage performance caused by Ni substitution.It can be shown that the impact of Ni on the decomposition enthalpy of MgH_(2) is quite modest,with the absolute enthalpy(ΔHr)only decreasing from 78.48 to 76.15 kJ/mol.

Phase evolution,hydrogen storage thermodynamics,and kinetics of ternary Mg_(98)Ho_(1.5)Fe_(0.5) alloy

Rare earth elements and transition metals have been found to improve the hydrogen storage characteristics of magnesium-based alloys.This study investigated the Mg-Ho-Fe(MHF) ternary alloy prepared using the vacuum induction melting technique.X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),pressure-composition-temperature(PCT),and differential scanning calorimetry(DSC) were used to analyze the alloy's phase transitions,microstructure,thermodynamics,and kinetic properties.The results reveal that the Mg_(98)Ho_(1.5)Fe_(0.5) alloy forms a solid solution with Ho and Fe in the magnesium matrix.Upon hydrogen absorption,the activated alloy transforms into a mixture of Mg/MgH_(2) phases and nanoscale HoH_(2) phases.Notably,only the MgH_(2) phase decomposes during hydrogen desorption,while the HoH_(2) phase remains unchanged,exhibiting a positive catalytic effect.The alloy demonstrates excellent hydrogen absorption kinetics,achieving a capacity of 5.56 wt% H_(2) within 10 min at 360℃,owing to the combined catalytic effects of Ho and Fe.The activation energy for hydrogen desorption is found to be 135.87 kJ/mol,which is lower than that of the activation energies of pure MgH_(2) and MgFe alloys,indicating an enhancement in desorption kinetics.Moreover,the enthalpy and entropy changes for hydrogen absorption and desorption are determined to be-70.51 kJ/mol H_(2),-125.62 J/(K·mol) H_(2),72.83 kJ/mol H_(2),and 128.95 J/(K·mol) H_(2),respectively.Furthermore,it is worth noting that the thermodynamic properties of the alloy are improved due to the catalytic effect of Ho and Fe.

Remarkable low-temperature hydrogen cycling kinetics of Mg enabled by VH_(x) nanoparticles

Nanoscaled catalysts have attracted much more attention due to their more abundant active sites and better dispersion than their bulky counterparts.In this work,VH_(x) nanoparticles smaller than 10 nm in average size are successfully synthesized by a simple solid-state ball milling coupled with THF washing process,which are proved to be highly effective in enhancing the hydrogen absorption/desorption kinetics of MgH_(2) at moderate temperatures.The nano-VH_(x)-modified MgH_(2) releases hydrogen from 182℃,which is 88℃ lower than additive-free MgH_(2).The release of hydrogen amounts to 6.3 wt%H within 10 min at 230℃ and 5.6 wt%H after 30 min at 215℃ with initial vacuum.More importantly,the dehydro-genated MgH_(2)+10 wt.%nano-VH_(x) rapidly absorbs 5.2 wt%H within 3 min at 50℃ under 50 bar H_(2).It even takes up 4.3 wt%H within 30 min at room temperature(25℃)under 10 bar H_(2),exhibiting supe-rior hydrogenation kinetics to most of the previous reports.Mechanistic analyzes disclose the reversible transformation between V and V-H species during the hydrogen desorption-absorption process.The ho-mogeneously distributed V-based species is believed to act as hydrogen pump and nucleation sites for MgH_(2) and Mg,respectively,thus triggering fast hydrogenation/dehydrogenation kinetics.

Impact of severe plastic deformation on kinetics and thermodynamics of hydrogen storage in magnesium and its alloys

Magnesium and its alloys are the most investigated materials for solid-state hydrogen storage in the form of metal hydrides,but there are still unresolved problems with the kinetics and thermodynamics of hydrogenation and dehydrogenation of this group of materials.Severe plastic deformation(SPD)methods,such as equal-channel angular pressing(ECAP),high-pressure torsion(HPT),intensive rolling,and fast forging,have been widely used to enhance the activation,air resistance,and hydrogenation/dehydrogenation kinetics of Mg-based hydrogen storage materials by introducing ultrafine/nanoscale grains and crystal lattice defects.These severely deformed materials,particularly in the presence of alloying additives or second-phase nanoparticles,can show not only fast hydrogen absorption/desorption kinetics but also good cycling stability.It was shown that some materials that are apparently inert to hydrogen can absorb hydrogen after SPD processing.Moreover,the SPD methods were effectively used for hydrogen binding-energy engineering and synthesizing new magnesium alloys with low thermodynamic stability for reversible low/room-temperature hydrogen storage,such as nanoglasses,high-entropy alloys,and metastable phases including the high-pressureγ-MgH2 polymorph.This work reviews recent advances in the development of Mg-based hydrogen storage materials by SPD processing and discusses their potential in future applications.

Effects of La substitution on microstructure and hydrogen storage properties of Ti−Fe−Mn-based alloy prepared through melt spinning

The as-spun Ti_(1−x)La_(x)Fe_(0.8)Mn_(0.2)(x=0,0.01,0.03,0.06,0.09,molar fraction)alloys were prepared by melt spinning.The effects of La substitution for Ti on the microstructure,hydrogen storage kinetics and thermodynamics of TiFe-type Ti−Fe−Mn-based alloy were investigated.The as-spun alloys hold the TiFe single phase,which transforms to TiFeH_(0.06),TiFeH,and TiFeH_(2) hydrides after hydrogenation.La substitution promotes the formation of micro-defects(such as dislocations and grain boundaries)in the alloys,thus facilitating hydrogen diffusion.In addition,the hydrogen storage kinetics properties are improved after introducing La element.With the rise of La content,the hydrogen storage capacity decreases firstly and then increases,but the absolute value of hydriding enthalpy change(|ΔH|)increases firstly and then reduces.When x=0.01,the maximum value of|ΔH|is obtained to be(25.23±0.50)kJ/mol for hydriding,and the alloy has the maximum hydrogen absorption capacity of(1.80±0.04)wt.%under the conditions of 323 K and 3 MPa.

Integration strategies of hydrogen network in a refinery based on operational optimization of hydrotreating units

Inferior crude oil and fuel oil upgrading lead to escalating increase of hydrogen consumption in refineries.It is imperative to reduce the hydrogen consumption for energy-saving operations of refineries.An integration strategy of hydrogen network and an operational optimization model of hydrotreating(HDT)units are proposed based on the characteristics of reaction kinetics of HDT units.By solving the proposed model,the operating conditions of HDT units are optimized,and the parameters of hydrogen sinks are determined by coupling hydrodesulfurization(HDS),hydrodenitrification(HDN)and aromatic hydrogenation(HDA)kinetics.An example case of a refinery with annual processing capacity of eight million tons is adopted to demonstrate the feasibility of the proposed optimization strategies and the model.Results show that HDS,HDN and HDA reactions are the major source of hydrogen consumption in the refinery.The total hydrogen consumption can be reduced by 18.9%by applying conventional hydrogen network optimization model.When the hydrogen network is optimized after the operational optimization of HDT units is performed,the hydrogen consumption is reduced by28.2%.When the benefit of the fuel gas recovery is further considered,the total annual cost of hydrogen network can be reduced by 3.21×10~7CNY·a^(-1),decreased by 11.9%.Therefore,the operational optimization of the HDT units in refineries should be imposed to determine the parameters of hydrogen sinks base on the characteristics of reaction kinetics of the hydrogenation processes before the optimization of the hydrogen network is performed through the source-sink matching methods.