Y-Mn-O負載的Ni基催化劑用于乙酸自熱重整產氫

胡曉敏 陳 慧 賈玄弈 王 巧 黃利宏

(成都理工大學材料與化學化工學院，成都 610059)

Consumption of fossil fuel brings about environmental issues,e.g.,pollution and emission of greenhouse gas[1],and alternative energies thus attract extensive attentions for decades.Among the alternative energies,hydrogen is a promising candidate for its cleanness and high energy density[2].Biomass,as an abundant renewable resource,can be converted into bio-oil via fast pyrolysis,and can be processed for hydrogen production[3].Acetic acid(HAc),as a main component in bio-oil with content up to mass fraction of 33%,has been selected as a feasible hydrogen resource via reforming processes[4-5].Within reforming processes,there are steam reforming(SR),partial oxidation(CPOX)and auto-thermal reforming(ATR),while ATR shows potential for its self-heat sustainability[6-7].

In ATR of HAc(CH3COOH+1.44H2O+0.28O2→2CO2+3.44H2,ΔH=0 kJ·mol-1),nickel-based catalysts are effective for their reactivity in breaking C—C and C—H bond within acetic acid[8],but deactivation issues,like coking and sintering,hinder the process;for example,in Ca-Al layered double hydroxides-derived Ni-based catalysts for ATR reaction,as reported by Wang et al.[7],the layered double hydroxides structure promotes stability of the nickel-based catalyst,but severe coking is still observed with time-on-stream.To address these issues,additives are then introduced in Ni-based catalysts to modify their structures and electronic properties.Manganese,as a transition metal,exhibits redox ability to activate oxygen species for its multi-valances and can be effective to gasify coke precursors in ATR[9-10].As reported by Liu et al.,within a spinel Co-Mn-Ni-O catalyst,the redox cycle of Mn2+/Mn3+and Mn3+/Mn4+promotes the transfer of oxygen species in zinc-air batteries[10].However,the MnOxis easy to be sintered which results in poor thermostability in NiMn4.78O7.39±δcatalysts,as reported by An et al[11-12].To improve thermostability,yttrium can be a promising candidate[13-14];for example,nickel-based catalysts with yttrium oxide presents stable reactivity in partial oxidation of methane(POM)at a high temperature(850℃)[13-14].Besides,with the addition of manganese into perovskite structure of ABO3with nickel and yttrium(NiYO3),a perovskite-like(Ni,Mn)YO3phase can be formed,which is promising to restrain sintering and oxidation within nickel-based catalysts.

In light of above reports,a series of NiMnY catalysts were synthesized by hydrothermal method in the current work and the calcined catalysts were then tested in ATR of HAc.The characterization techniques,such as X-ray diffraction(XRD),N2adsorption-desorption test and H2-temperature-programmed reduction(H2-TPR),were carried out to explore the internal relationship within those NiMnY catalysts.To the best of the author′s acknowledge,there is no report on the perovskite-like(Ni,Mn)YO3catalysts for hydrogen production in ATR of HAc.

1 Experimental

1.1 Catalyst preparation

A series of NiMnY catalysts with mass fraction of 15% NiO were prepared by hydrothermal method.Chemicals of Y(NO3)3·6H2O,Mn(NO3)2and Ni(NO3)2·6H2O with stoichiometric ratios as listed in Table 1 were mixed with ethylene glycol monomethyl ether under vigorous stirring,then transferred into a teflon bottle in an oven and remained at 240℃for 12 h.The precipitate was then collected via centrifugation,washed with deionized water and dried at 105℃for 12 h,followed by calcined in air at 850℃for 4 h.The obtained catalysts were named as NY,NMY1-1,NMY6-1 and NM,respectively,as listed in Table 1.

Table 1 Composition,BET(Brunauer-Emmett-Teller)specific surface areas(SBET),BJH(Barrette-Joyner-Halenda)pore volume(VBJH),average pore size(DBJH)and particle sizes of the Ni-based catalysts as prepared

1.2 Catalytic performance evaluation

150 mg of catalyst was loaded in a continuousflow fixed-bed quartz tubing reactor and reduced in hydrogen at 700℃for 1 h,then a mixture of HAc/H2O/O2/N2(molar ratio of 1∶4∶0.28∶3)with GHSV(gas hourly space velocity)of 37 260 mL·g-1·h-1was introduced into the reactor for ATR test.TCD(thermal conduction detector)and FID(flame ionization detector)detectors within gas chromatography (SC-3000B,Chuanyi Instrument)were used to monitor products.The selectivity(Si)of carbon-containing products(i=CO,CO2,CH4,CH3COCH3),HAc conversion(XHAc)and hydrogen yield(YH2)were calculated by Eq.(1～3),respectively,whereFi,inorFi,outis the molar flow of i species at the inlet or outlet of the reactor,FHAc,inorFHAc,outis the molar flow of HAc at the inlet or outlet of the reactor,niis the carbon stoichiometric factor between HAc and carbon-containing products.Besides,theFH2,productrepresents the molar ratio of hydrogen in the product.

1.3 Characterizations

XRD patterns were recorded via an X-ray diffractometer(Rigaku,UltimaⅣ)with a CuKαradiation source(λ=0.154 18 nm,200 mA,40 kV)from 5°to 80°.N2physisorption isotherms were recorded by using a JW-BK112 apparatus at-196℃.50 mg catalyst loaded within a TP-5076 apparatus(Xianquan Instrument)was used to perform H2-TPR experiments in a volume fraction of 5.0% H2/N2gas flow,while the signal of H2was collected by a TCD.

2 Results and discussion

2.1 Characterizations of calcinated catalysts

The XRD patterns for calcinated catalysts were recorded and showed in Fig.1.For NY catalyst without Mn,strong peaks of Y2O3appeared and the peaks of NiO were detected as well[15].For NMY1-1 with Mn(Ni0.39Mn0.61YO3.11±δ),Y2O3phase disappeared;meanwhile,there wasno Mn-containing species,and perovskite peaks of NiYO3were found with peaks shifting to lower angles,as compared with standard NiYO3phase,indicating that addition of manganese stabilized the NiYO3phase during calcination by partly replacing nickel and could form a perovskite-like(Ni,Mn)YO3phase,while nickel species were highly dispersed within the perovskite structure[16].For the NMY6-1 with more Mn,the main phase was YMn2O5,along with trace of NiO,Mn2O3and NiMn2O4.Over the NM catalyst without Y,there were spinel phases NiMn2O4/Mn3O4and trace of Mn2O3,while no obvious peak of NiO was found.

Fig.1 XRD patterns for the calcined catalysts

The calcined catalysts were further screened by nitrogen physisorption,as shown in Fig.2.For the NMY1-1 catalyst,there was typeⅡisotherm,while other three catalysts presented typeⅢ isotherms.Meanwhile,NMY1-1 showed a high specific surface area of 13 m2·g-1with a concentrated pore distribution near 2 nm,as shown in Fig.2B.

Fig.2 Adsorption-desorption equilibrium curves(A)and pore size distribution of the catalysts(B)

2.2 Characterizations of reduced catalysts

XRD patterns of the reduced catalysts were shown in Fig.3.All catalysts presented peaks of Ni0[17].Strong peaks of Y2O3were still remained within NY catalyst.The perovskite-like(Ni,Mn)YO3species in NMY1-1 was transformed into Y2O3and MnO,while highly dispersed Ni species with particle size near 22.8 nm was obtained,as shown in Table 1.Similar species were found in NMY6-1.For the NM catalyst,Mn3O4and Mn2O3were converted to MnO,and the appearance of Ni0can be ascribed to reduction of NiMn2O4species.

Fig.3 XRD patterns for the reduced catalysts

Over H2-TPR profile of NY,the peak around 382℃was ascribed to surface NiO species,while the other one was related to NiO contacted with Y2O3[15].For NMY1-1,besides the weak reduction peak of surface Ni species near 374℃,a strong peak near 658℃can be attributed to reduction of(Ni,Mn)YO3,which is consistent with species of Ni,MnO and Y2O3found by XRD[18].For NMY6-1,the broad peak around 490℃can be attributed to the continuous reduction of NiO,Mn2O3and Mn3O4(Mn2O3→Mn3O4→MnO)and the reduction of Mn4+in Y2MnO5[12,19],while the peak near 657℃can be ascribed to the reduction of spinel(NiMn2O4→NiO+MnO→Ni+MnO)[20].Over the NM catalyst,similar peaks were found for reduction of NiMn2O4near 672℃and species of NiO,Mn2O3and Mn3O4near 441℃.

Fig.4 H2-TPR profile for the calcinated catalysts

2.3 Reactivity in ATR of HAc

The catalysts were then tested in ATR of HAc at 650℃for 20 h,as shown in Fig.5.For the NY catalyst,both HAc conversion and hydrogen yield decreased overtime,and finally reached 69.6% and 1.56molH2·molHAc-1,respectively.For the NMY1-1,the HAc conversion remained stable near 100% with the hydrogen yield at 2.68molH2·molHAc-1,while only trace byproducts of methane/acetone were detected and the selectivity to hydrogen was as high as 99.1%.Over the NMY6-1 catalyst,the conversion of HAc was stable at near 100%,but the hydrogen yield was near 2.50 molH2·molHAc-1with by-product of methane near 3.5%.In contrast,for the NM catalyst,the HAc conversion and hydrogen yield decreased to 92.3% and 2.40 molH2·molHAc-1,respectively.

Fig.5 Reactivity of(a)NY,(b)NMY1-1,(c)NMY6-1 and(d)NM catalysts in ATR of HAc

Effect of temperature was further estimated over the NMY1-1 catalyst,as seen in Fig.6.At 400℃,the HAc conversion was only 48.6% with a low hydrogen yield(0.39molH2·molHAc-1),while the selectivity to acetone was as high as 34.1%,indicating ketonization of HAc happened via CH3CO*+CH3*→CH3COCH3[15].As the temperature went up,the hydrogen yield and HAc conversion both increased.The conversion of acetic acid reached near 100% with a high hydrogen production near 2.7molH2·molHAc-1was recorded at 650 ℃ .However,as the temperature further increasing to 700℃,the hydrogen production slightly decreased because of the increase of CO/CO2via reverse watergas shift reaction.Therefore,650℃can be a suitable temperature for ATR of HAc within the NMY1-1 catalyst.

Fig.6 Effect of temperature over NMY1-1

2.4 Characterizations of spent catalysts

To investigate the structure variation during ATR test,XRD was carried out over the spent catalysts,as shown in Fig.7.For the spent NY catalyst,strong peaks of Y2O3remained with a Ni0particle size at 37.1 nm,which was slightly increased from 30.6 nm in the fresh catalyst and can be due to the weak interaction within NY.For NMY1-1,the structure phases of Ni/MnO/Y2O3remained stable,and the smallest particle size at 27.6 nm for metallic nickel among these spent catalysts was observed,as listed in Table 1.As compared to NMY1-1,the strength of MnO became stronger over NMY6-1,and a Ni0particlesizeat40.7nmwasrecorded.Besides,the main phase was still MnO over spent NM catalyst,with a Ni0particle size at 32.9 nm.

Fig.7 XRD patterns for the spent catalysts

2.5 Discussion

In case of the NY catalyst without Mn,there was weak interaction between Ni and Y2O3,and during the ATR reaction,the particle size of metallic nickel increased from 30.6 to 37.1 nm,resulted in sintering and deactivation for hydrogen production.For the NMY1-1 catalyst,perovskite-like(Ni,Mn)YO3structure was formed and promoted dispersion of nickel species.With the addition of yttrium,the thermostability of catalyst was enhanced,while the reduction characteristic and interaction of nickel and support were tuned.After reduced in hydrogen at 700℃,the(Ni,Mn)YO3transformed into thermostable species of Ni-Y-Mn-O with strong interaction among Ni,Y2O3and MnO,while metallic nickel with the smallest particle size within the four catalysts(27.6 nm)was recorded;therefore,a high hydrogen yield near 2.7molH2·molHAc-1was obtained and remained stable without deactivation,suggesting that the Mn and Y species in(Ni,Mn)YO3constrained sintering and oxidation.As comparison,over NMY6-1 catalyst,a large Ni0particle size near 39.9 nm was found,and a hydrogen yield near 2.5molH2·molHAc-1was recorded with a high selectivity to methane near 3.5% in ATR,as shown in Fig.5c.For the NM catalyst,Ni species mainly existed in spinel NiMn2O4phase and were partly reduced in hydrogen at 700℃,while a low surface area near 5 m2·g-1was found as well,resulting in less active sites to convert acetic acid and produce hydrogen,and a low hydrogen yield was then recorded near 2.4molH2·molHAc-1.

3 Conclusions

A series of NiMnY catalysts were prepared by hydrothermal method,and tested in ATR of HAc for hydrogen production.Over NMY1-1 catalyst,the incorporation of manganese led to the formation of perovskite-like(Ni,Mn)YO3species,which modify the interaction of(Ni,Mn)YO3and inhibit the sintering of nickel.Meanwhile,the addition of manganese accelerates the conversion of carbon precursor while the thermostability of catalyst is enhanced with the incorporation of yttrium.After reduction in hydrogen,the(Ni,Mn)YO3phase converted into MnO and Y2O3,along with the highly dispersed nickel nanoparticles,providing more active sites to convert HAc and generate hydrogen.Thus,a high and stable catalytic performance in ATR of HAc was obtained with HAc conversion near 100% and hydrogen yield of 2.68molH2·molHAc-1.