Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central is...Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.展开更多
As one of the main oxygen-containing organic products generated from the hydrothermal conversion of biomass,levulinic acid(LA)has the potential to be further upgraded.This work investigated the steam reforming(SR)proc...As one of the main oxygen-containing organic products generated from the hydrothermal conversion of biomass,levulinic acid(LA)has the potential to be further upgraded.This work investigated the steam reforming(SR)process of biomass-derived LA to produce H_(2).A series of Ni catalysts supported by various spinels were synthesized via co-precipitation and impregnation.The Ni active metal dispersed well on the NiAl_(2)O_(4)catalyst with high specific surface area,thereby exhibiting high catalytic activity.Among all the catalysts tested,15Ni/NiAl_(2)O_(4)showed the best performance for SR of LA,resulting in high carbon conversion of 96.3%,H_(2)yield of 92.8%,and H_(2)concentration of 67.9%at a reaction temperature of 800℃.Additionally,the influences of reaction temperature,steam-to-carbon ratio(S/C),and liquid hourly space velocity(LHSV)were also examined.Moreover,during the 40-h continuous SR process of LA,the 15Ni/NiAl_(2)O_(4)catalyst maintained its outstanding catalytic activity.This study provides an encouraging route for upgrading biomass-derived LA into eco-friendly and high-value fuels,thereby advancing the sustainability of the biomass refining process.展开更多
Compared to reforming reactions using hydrocarbons,ethanol steam reforming(ESR)is a sustainable alternative for hydrogen(H_(2))production since ethanol can be produced sustainably using biomass.This work explores the ...Compared to reforming reactions using hydrocarbons,ethanol steam reforming(ESR)is a sustainable alternative for hydrogen(H_(2))production since ethanol can be produced sustainably using biomass.This work explores the catalyst design strategies for preparing the Ni supported on ZSM-5 zeolite catalysts to promote ESR.Specifically,two-dimensional ZSM-5 nanosheet and conventional ZSM-5 crystal were used as the catalyst carriers and two synthesis strategies,i.e.,in situ encapsulation and wet impregnation method,were employed to prepare the catalysts.Based on the comparative characterization of the catalysts and comparative catalytic assessments,it was found that the combination of the in situ encapsulation synthesis and the ZSM-5 nanosheet carrier was the effective strategy to develop catalysts for promoting H_(2) production via ESR due to the improved mass transfer(through the 2-D structure of ZSM-5 nanosheet)and formation of confined small Ni nanoparticles(resulted via the in situ encapsulation synthesis).In addition,the resulting ZSM-5 nanosheet supported Ni catalyst also showed high Ni dispersion and high accessibility to Ni sites by the reactants,being able to improve the activity and stability of catalysts and suppress metal sintering and coking during ESR at high reaction temperatures.Thus,the Ni supported on ZSM-5 nanosheet catalyst prepared by encapsulation showed the stable performance with~88% ethanol conversion and~65% H_(2) yield achieved during a 48-h longevity test at 550-C.展开更多
Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as...Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.展开更多
Rare-earth (La, Ce, Yb) promoted Ni/γ-Al2O3 catalysts were prepared by impregnation method. Activity and carbon formation resistance of the prepared catalysts were evaluated under various reaction conditions. Catal...Rare-earth (La, Ce, Yb) promoted Ni/γ-Al2O3 catalysts were prepared by impregnation method. Activity and carbon formation resistance of the prepared catalysts were evaluated under various reaction conditions. Catalyst characterizations with TG, TPR and H2 chemisorption were carried out to investigate the promoting mechanism. Experimental results show that rare-earth promoters, especially Yb promoter, obviously improve the activity and carbon formation resistance of Ni/γ-Al2O3 catalyst, and Yb-Ni catalyst shows even higher performance than several commercial catalysts. According to the characterization results, Yb promoter enhances the interaction between the active metal and support, thus increasing the active metal's dispersion and improving its performance. Furthermore, the obvious difference in diesel conversion between Yb-Ni catalyst and others was shown in the temperature range of 450-550 °C, which would be the reason for its excellent carbon resistance.展开更多
In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-...In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.展开更多
In the current paper, dry(CO2)-reforming of glycerol, a new reforming route, was carried out over alumina(Al2O3)-supported, non-promoted and lanthanum-promoted nickel(Ni) catalysts. Both sets of catalysts were synthes...In the current paper, dry(CO2)-reforming of glycerol, a new reforming route, was carried out over alumina(Al2O3)-supported, non-promoted and lanthanum-promoted nickel(Ni) catalysts. Both sets of catalysts were synthesized via a wet co-impregnation procedure. Physicochemical characterization of the catalysts showed that the promoted catalyst possessed smaller metal crystallite size, hence higher metal dispersion compared to the virgin Ni/Al2O3catalyst. This was also corroborated by the surface images captured by the FESEM analysis. From temperature-programmed calcination analysis, the derivative weight profiles revealed two peaks, which represent a water elimination peak at a temperature range of 373 to 473 K followed by nickel nitrate decomposition from 473 to 573 K. In addition, BET surface area measurements gave 85.0 m2 g-1for the non-promoted Ni catalyst, whilst the promoted catalysts showed an average of 1% to 6% improvement depending on the La loadings. Significantly, reaction studies at 873 K showed that glycerol dry reforming successfully produced H2. The 2%La-Ni/Al2O3catalyst, which possessed the largest BET surface area, gave an optimum H2generation(9.70%) at a glycerol conversion of 24.5%.展开更多
The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via...The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.展开更多
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 ca...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%.展开更多
Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried ...Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2(molar ratio)=1:3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.展开更多
Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS a...Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.展开更多
Supercritical water gasification is a promising technology for wet biomass utilization.In this paper,Ni and other metal catalysts were synthesized by wet impregnation.The stability and catalytic activities of Ni catal...Supercritical water gasification is a promising technology for wet biomass utilization.In this paper,Ni and other metal catalysts were synthesized by wet impregnation.The stability and catalytic activities of Ni catalysts were evaluated.Firstly,catalytic activities of Ni,Fe,Cu catalysts supported on MgO were tested using wheat straw as raw material in a batch reactor at 723 K and water density of 0.07 cm^(3)/g.Experimental results showed that the order of metal catalyst activity for hydrogen generation was Ni/MgO>Fe/MgO>Cu/MgO.Secondly,the influence of different supports on Ni catalysts performance was investigated.The results showed that the order of the Ni catalysts’activity with different supports was Ni/MgO>Ni/ZnO>Ni/Al_(2)O_(3)>Ni/ZrO_(2).Finally,the effects of Ni loading and the amount of Ni catalyst addition on hydrogen production,and the stability of Ni/MgO catalyst were studied.It was found that serious deactivation of Ni catalyst in the process of supercritical water gasification took place.Even if carbon deposited on the catalyst surface was removed by high temperature calcination and the catalyst was reduced with hydrogen,the activity of used catalyst was only partially restored.展开更多
Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It...Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.展开更多
The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic ...The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.展开更多
A series of Ni/AlMCM-41 catalysts with different nickel contents was prepared via the incipient wetness impregnation method. The effects of the nickel content on the structure, acidity and metal function of the cataly...A series of Ni/AlMCM-41 catalysts with different nickel contents was prepared via the incipient wetness impregnation method. The effects of the nickel content on the structure, acidity and metal function of the catalysts were studied by using different techniques. In the test of n-dodecane hydroconversion, it was found that the metal and acid functions were well balanced over a 2.0%Ni(mass fraction)/AlMCM-41 catalyst, which gave the maximal isomerization selectivity and a homolytic cleavage products.展开更多
Novel Ni(II)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethyl...Novel Ni(II)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linear α-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers〉C4. The activity of 3b-MAO complex is 6.3×10^7 g/(molNi.h) at 50 ℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors.展开更多
Trace amounts of noble metal-doped Ni/Mg(AI)O catalysts were pre- pared starting from Mg-Al hydrotalcites (HTs) and tested in daily start-up and shut-down (DSS) operation of steam reforming (SR) of methane or ...Trace amounts of noble metal-doped Ni/Mg(AI)O catalysts were pre- pared starting from Mg-Al hydrotalcites (HTs) and tested in daily start-up and shut-down (DSS) operation of steam reforming (SR) of methane or partial oxidation (PO) of propane. Although Ni/Mg(Al)O catalysts prepared from Mg(Ni)-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg(Al)O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a "memory effect" of HTs. Moreover, the noble metal-doped Ni/Mg(Al)O catalysts exhibited "intelligent" catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2+ in Mg(Ni,Al)O periclase to Ni^0 assisted by hydrogen spillover from Pt (or Pt-Ni alloy). The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg(Al)O periclase crystal; surface Ni^0 was oxidized to Ni2+ by steam and incorporated into Mg(Ni2+,Al)O periclase, whereas the Ni2+ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a "green" preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.展开更多
Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the s...Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the surface acid-base properties of catalysts by introduction of alkali metal (Na, K) oxides inhibits the carbonization and as a result, improves the operational stability of these catalysts. An effect of promotion of nickel-alumina based composite doped by lanthanum oxide is found. This effect, caused by an additional route for the CO2 activation on Ni-La2O3/Al2O3/cordierite catalyst, is displayed in increase of methane conversion under conditions of an oxidant excess.展开更多
Ni/α-Al2O3 catalysts were found to be active in the temperature range 600 ~ 900℃ for both CO2 reforming and partial oxidation of methane.The effects of Ni loading,reaction temperature and feed gas ratio for the com...Ni/α-Al2O3 catalysts were found to be active in the temperature range 600 ~ 900℃ for both CO2 reforming and partial oxidation of methane.The effects of Ni loading,reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated.Catalysts of xwt%Ni/α-Al2O3(x=2.5,5,8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate.XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst,as compared with the other prepared catalyst samples.An increase of the Ni loading to more than 5wt% led to a reduction in the Ni dispersion.In addition,by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction,the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.展开更多
A series of monolithic Ni/CeO_2-ZrO_2/γ-Al_2O_3 catalysts for the POM reaction were prepared. The activity test shows that the catalyst has the best performance when CeO_2-ZrO_2 content is 8 wt%.The synergistic actio...A series of monolithic Ni/CeO_2-ZrO_2/γ-Al_2O_3 catalysts for the POM reaction were prepared. The activity test shows that the catalyst has the best performance when CeO_2-ZrO_2 content is 8 wt%.The synergistic actions between CeO_2-ZrO_2 and γ-Al_2O_3 improve highly catalytic activity by increasing CH_4 conversion, H_2 and CO selectivity. XPS analysis of the used catalyst indicates that there coexist Ce^(4+) and Ce^(3+).展开更多
文摘Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
基金State Key Laboratory of Clean Energy Utilization(Open Fund Project No.ZJUCEU2021004).
文摘As one of the main oxygen-containing organic products generated from the hydrothermal conversion of biomass,levulinic acid(LA)has the potential to be further upgraded.This work investigated the steam reforming(SR)process of biomass-derived LA to produce H_(2).A series of Ni catalysts supported by various spinels were synthesized via co-precipitation and impregnation.The Ni active metal dispersed well on the NiAl_(2)O_(4)catalyst with high specific surface area,thereby exhibiting high catalytic activity.Among all the catalysts tested,15Ni/NiAl_(2)O_(4)showed the best performance for SR of LA,resulting in high carbon conversion of 96.3%,H_(2)yield of 92.8%,and H_(2)concentration of 67.9%at a reaction temperature of 800℃.Additionally,the influences of reaction temperature,steam-to-carbon ratio(S/C),and liquid hourly space velocity(LHSV)were also examined.Moreover,during the 40-h continuous SR process of LA,the 15Ni/NiAl_(2)O_(4)catalyst maintained its outstanding catalytic activity.This study provides an encouraging route for upgrading biomass-derived LA into eco-friendly and high-value fuels,thereby advancing the sustainability of the biomass refining process.
基金funding from the European Union's Horizon 2020 Research and Innovation Program(872102)P.S.thanks the Science Achievement Scholarship of Thailand(SAST)for her research secondment at The University of Manchester.Y.J.thanks the National Natural Science Foundation of China(22378407)for funding.
文摘Compared to reforming reactions using hydrocarbons,ethanol steam reforming(ESR)is a sustainable alternative for hydrogen(H_(2))production since ethanol can be produced sustainably using biomass.This work explores the catalyst design strategies for preparing the Ni supported on ZSM-5 zeolite catalysts to promote ESR.Specifically,two-dimensional ZSM-5 nanosheet and conventional ZSM-5 crystal were used as the catalyst carriers and two synthesis strategies,i.e.,in situ encapsulation and wet impregnation method,were employed to prepare the catalysts.Based on the comparative characterization of the catalysts and comparative catalytic assessments,it was found that the combination of the in situ encapsulation synthesis and the ZSM-5 nanosheet carrier was the effective strategy to develop catalysts for promoting H_(2) production via ESR due to the improved mass transfer(through the 2-D structure of ZSM-5 nanosheet)and formation of confined small Ni nanoparticles(resulted via the in situ encapsulation synthesis).In addition,the resulting ZSM-5 nanosheet supported Ni catalyst also showed high Ni dispersion and high accessibility to Ni sites by the reactants,being able to improve the activity and stability of catalysts and suppress metal sintering and coking during ESR at high reaction temperatures.Thus,the Ni supported on ZSM-5 nanosheet catalyst prepared by encapsulation showed the stable performance with~88% ethanol conversion and~65% H_(2) yield achieved during a 48-h longevity test at 550-C.
基金supported by National Natural Science Foundation of China(51876080)the Program for Taishan Scholars of Shandong Province Government,the Agricultural Innovation Program of Shandong Province(SD2019NJ015)+1 种基金the Research and Development program of Shandong Basan Graphite New Material Plant,National Natural Science Foundation of China(52076097)Key projects for inter-governmental cooperation in international science,technology and innovation(2018YFE0127500).
文摘Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.
基金supported by the National Natural Science Foundation of China (No. 20776016 and 21006005)
文摘Rare-earth (La, Ce, Yb) promoted Ni/γ-Al2O3 catalysts were prepared by impregnation method. Activity and carbon formation resistance of the prepared catalysts were evaluated under various reaction conditions. Catalyst characterizations with TG, TPR and H2 chemisorption were carried out to investigate the promoting mechanism. Experimental results show that rare-earth promoters, especially Yb promoter, obviously improve the activity and carbon formation resistance of Ni/γ-Al2O3 catalyst, and Yb-Ni catalyst shows even higher performance than several commercial catalysts. According to the characterization results, Yb promoter enhances the interaction between the active metal and support, thus increasing the active metal's dispersion and improving its performance. Furthermore, the obvious difference in diesel conversion between Yb-Ni catalyst and others was shown in the temperature range of 450-550 °C, which would be the reason for its excellent carbon resistance.
基金supported by the National Natural Science Foundation of China (21567016, 21566022, 21263015)the Natural Science Foundation of Jiangxi Province (20151BBE50006, 20151BAB203024)the Education Department of Jiangxi Province (KJLD14005, GJJ150016)
文摘In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.
文摘In the current paper, dry(CO2)-reforming of glycerol, a new reforming route, was carried out over alumina(Al2O3)-supported, non-promoted and lanthanum-promoted nickel(Ni) catalysts. Both sets of catalysts were synthesized via a wet co-impregnation procedure. Physicochemical characterization of the catalysts showed that the promoted catalyst possessed smaller metal crystallite size, hence higher metal dispersion compared to the virgin Ni/Al2O3catalyst. This was also corroborated by the surface images captured by the FESEM analysis. From temperature-programmed calcination analysis, the derivative weight profiles revealed two peaks, which represent a water elimination peak at a temperature range of 373 to 473 K followed by nickel nitrate decomposition from 473 to 573 K. In addition, BET surface area measurements gave 85.0 m2 g-1for the non-promoted Ni catalyst, whilst the promoted catalysts showed an average of 1% to 6% improvement depending on the La loadings. Significantly, reaction studies at 873 K showed that glycerol dry reforming successfully produced H2. The 2%La-Ni/Al2O3catalyst, which possessed the largest BET surface area, gave an optimum H2generation(9.70%) at a glycerol conversion of 24.5%.
基金supported by the Hundred Talents Program of the Chinese Academy of Sciences (CAS),State Key Laboratory of Multiphase Complex Systems of China (No.MPCS-2009-C-01)the National Key Technology R&D Program of China (No.2010BAC66B01)the Knowledge Innovation Program of the CAS (No.KGCX2-YW-396)
文摘The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.
基金supported by the National Natural Science Foundation of China(No.51274066,51304048)the National Key Technology R&D Program of China(No.2013BAA03B03)the National Science Foundation for Post-doctoral Scientists of China(No.2013M541240)
文摘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%.
基金financially supported by Independent Research Subject from Ministry of Science and Technology of China(No.2008BWZ005)
文摘Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2(molar ratio)=1:3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.
基金The Executive Programme for Cooperation between Italy and India (Prot.No.MAE01054762017)。
文摘Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.
基金This work is currently supported by the Key Project of Chinese National Programs for Research and Development(No.2016YFB0600102)National Nature Science Foundation of China(No.51676158)Shaanxi Science&Technology Co-ordination&Innovation Project(No.2016KTZDGY08-02).
文摘Supercritical water gasification is a promising technology for wet biomass utilization.In this paper,Ni and other metal catalysts were synthesized by wet impregnation.The stability and catalytic activities of Ni catalysts were evaluated.Firstly,catalytic activities of Ni,Fe,Cu catalysts supported on MgO were tested using wheat straw as raw material in a batch reactor at 723 K and water density of 0.07 cm^(3)/g.Experimental results showed that the order of metal catalyst activity for hydrogen generation was Ni/MgO>Fe/MgO>Cu/MgO.Secondly,the influence of different supports on Ni catalysts performance was investigated.The results showed that the order of the Ni catalysts’activity with different supports was Ni/MgO>Ni/ZnO>Ni/Al_(2)O_(3)>Ni/ZrO_(2).Finally,the effects of Ni loading and the amount of Ni catalyst addition on hydrogen production,and the stability of Ni/MgO catalyst were studied.It was found that serious deactivation of Ni catalyst in the process of supercritical water gasification took place.Even if carbon deposited on the catalyst surface was removed by high temperature calcination and the catalyst was reduced with hydrogen,the activity of used catalyst was only partially restored.
文摘Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.
基金Supported by the 973project of China(G2 0 0 0 0 2 6 4 )
文摘The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.
基金the Funds for the National Key Fundamental Research and Developm ent Projects of China (No.G19990 2 2 4 0 2 )
文摘A series of Ni/AlMCM-41 catalysts with different nickel contents was prepared via the incipient wetness impregnation method. The effects of the nickel content on the structure, acidity and metal function of the catalysts were studied by using different techniques. In the test of n-dodecane hydroconversion, it was found that the metal and acid functions were well balanced over a 2.0%Ni(mass fraction)/AlMCM-41 catalyst, which gave the maximal isomerization selectivity and a homolytic cleavage products.
基金This work is supported by PetroChina Company Limited (No.030414-01)
文摘Novel Ni(II)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linear α-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers〉C4. The activity of 3b-MAO complex is 6.3×10^7 g/(molNi.h) at 50 ℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors.
基金supported by the New Energy and Industrial Technology Development Organization (NEDO),Japan
文摘Trace amounts of noble metal-doped Ni/Mg(AI)O catalysts were pre- pared starting from Mg-Al hydrotalcites (HTs) and tested in daily start-up and shut-down (DSS) operation of steam reforming (SR) of methane or partial oxidation (PO) of propane. Although Ni/Mg(Al)O catalysts prepared from Mg(Ni)-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg(Al)O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a "memory effect" of HTs. Moreover, the noble metal-doped Ni/Mg(Al)O catalysts exhibited "intelligent" catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2+ in Mg(Ni,Al)O periclase to Ni^0 assisted by hydrogen spillover from Pt (or Pt-Ni alloy). The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg(Al)O periclase crystal; surface Ni^0 was oxidized to Ni2+ by steam and incorporated into Mg(Ni2+,Al)O periclase, whereas the Ni2+ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a "green" preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.
文摘Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the surface acid-base properties of catalysts by introduction of alkali metal (Na, K) oxides inhibits the carbonization and as a result, improves the operational stability of these catalysts. An effect of promotion of nickel-alumina based composite doped by lanthanum oxide is found. This effect, caused by an additional route for the CO2 activation on Ni-La2O3/Al2O3/cordierite catalyst, is displayed in increase of methane conversion under conditions of an oxidant excess.
文摘Ni/α-Al2O3 catalysts were found to be active in the temperature range 600 ~ 900℃ for both CO2 reforming and partial oxidation of methane.The effects of Ni loading,reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated.Catalysts of xwt%Ni/α-Al2O3(x=2.5,5,8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate.XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst,as compared with the other prepared catalyst samples.An increase of the Ni loading to more than 5wt% led to a reduction in the Ni dispersion.In addition,by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction,the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.
文摘A series of monolithic Ni/CeO_2-ZrO_2/γ-Al_2O_3 catalysts for the POM reaction were prepared. The activity test shows that the catalyst has the best performance when CeO_2-ZrO_2 content is 8 wt%.The synergistic actions between CeO_2-ZrO_2 and γ-Al_2O_3 improve highly catalytic activity by increasing CH_4 conversion, H_2 and CO selectivity. XPS analysis of the used catalyst indicates that there coexist Ce^(4+) and Ce^(3+).