Optimizing the sulfur-resistance and activity of perovskite oxygen carrier for chemical looping dry reforming of methane

Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.

Effect of cobalt and its adding sequence on the catalytic performance of MoO_3/Al_2O_3 toward sulfur-resistant methanation

The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method and characterized by N2-adsorption, X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The conversions of CO for Mo-Co/Al, Co-Mo/Al and CoMo/Al catalysts were 59.7%, 54.3% and 53.9%, respectively. Among these catalysts, the Mo-Co/Al catalyst prepared stepwisely by impregnating Mo precursor firstly showed the best catalytic performance. Meanwhile, the conversions of CO were 48.9% for Mo/Al catalyst and 10.5% for Co/Al catalyst. The addition of cobalt species could improve the catalytic activity of Mo/Al catalyst. The N2-adsorption results showed that Co-Mo/Al catalyst had the smallest specific surface area among these catalysts. CoMoO4species in CoMo/Al catalyst were detected with XRD, TPR and LRS. Moreover, crystal MoS2which was reported to be less active than amorphous MoS2was found in both Co-Mo/Al and CoMo/Al catalysts. Mo-Co/Al catalyst showed the best catalytic performance as it had an appropriate surface structure, i.e., no crystal MoS2and very little CoMoO4species.

Sulfur-resistant methanation over MoO_3/CeO_2–ZrO_2 catalyst: Influence of Ce-addition methods

In this paper, Ce_(0.2)Zr_(0.8)O_2 composite supports were prepared by different Ce-addition methods including impregnation of cerium(CeZr-imp), impregnation of citric acid and cerium(CeZr-CA) simultaneously and deposition precipitation method(CeZr-DP), respectively. The as-prepared supports were applied to prepare 10 wt% MoO_3/Ce_(0.2)Zr_(0.8)O_2 catalysts for sulfur-resistant methanation. The N_2 adsorption/desorption,X-ray diffraction(XRD), Raman spectroscopy(RS), X-ray photoelectron(XPS), temperature-programmed reduction by hydrogen(H_2-TPR) were undertaken to get textural properties, morphological information and structures of the catalysts. The results showed that Mo O_3 was highly dispersed on the surface of these three supports and Ce was mostly of coexisted in Ce^(4+)/Ce^(3+) redox pairs. Compared with Mo/CeZrimp, the CO conversion increased by 10% and 15% for Mo/CeZr-CA and Mo/CeZr-DP, respectively. This was mainly attributed to the larger specific surface area, Ce^(3+) concentration and content of active MoS_2 on the surface of catalysts.

Effects of CeO2 preparation methods on the catalytic performance of MoO3/CeO2 toward sulfur-resistant methanation

CeOsupports were prepared by calcination or precipitation method and 5% MoO/CeOcatalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO/CeOcatalysts toward sulfur-resistant methanation was investigated. The results showed that the Mo/Ce-1 catalysts with CeOsupport prepared by calcination method exhibited the best sulfur-resistant methanation activity and stability with CO conversion as high as 75% while the Mo/Ce-3 catalysts the poorest. The supports and catalysts were characterized by N-adsorption–desorption, temperature-programmed reduction（TPR）, X-ray diffraction（XRD）, Raman spectroscopy（RS） and scanning electron microscope（SEM）. The results indicated that the saturated monolayer loading MoOon Ce-3 support was lower than 5% and there were some crystalline MoOparticles on the surface of the Mo/Ce-3. The preparation method of CeOhad a big influence on the specific surface area, the crystalline of CeO, and the catalytic performance of the corresponding Mo-based catalyst for sulfur-resistant methanation.

Effect of boron addition on the MoO_3/CeO_2–Al_2O_3 catalyst in the sulfur-resistant methanation

The effect of boron on the performance of MoO_3/CeO_2–Al_2O_3 catalysts, which were prepared with impregnation method, was investigated. The catalysts were characterized with N_2 adsorption–desorption, XRD, H_2-TPR, and NH_3-TPD, and were tested in sulfur-resistant methanation. The results indicated that the MoO_3/CeO_2–Al_2O_3 catalysts modified by boron showed higher catalytic performance in sulfur-resistant methanation. The CO conversion increased from 47% to 62% with 0.5 wt% boron content. When the content of boron was under 0.5 wt%, the results suggested there was an increase in the amorphous form of MoO_3 caused by the generation of weak and intermediate acid sites, which had weakened the interaction between the active components and supports. While, the catalyst added 2.0 wt% boron showed the strong acid sites and the largest crystalline size resulting in the uneven distribution of ceria.

Optimization of Co-precipitation Condition for Preparing Molybdenum-Based Sulfur-Resistant Methanation Catalysts

In this study, the e ects of ZrO 2 carrier precursors, MoO 3 loading, and washing treatment on the catalytic performance of M o O 3 /ZrO 2 toward sulfur-resistant methanation were investigated. All the catalysts were prepared by co-precipitation method and further characterized by N 2 adsorption desorption, H 2 -temperature-programmed reduction, X-ray di raction, Raman spectroscopy and transmission electron microscopy. The prepared MoO 3 /ZrO 2 catalysts were tested in a continuous- ow pressurized xed bed reactor for CO methanation. The results revealed that the carrier precursors, MoO3 loading, and wash- ing treatment a ected not only the crystalline phase of Mo species but also the grain size of ZrO 2 carrier and consequently in uenced the MoO 3 /ZrO 2 activity toward sulfur-resistant methanation. The 25 wt% M oO 3 /ZrO 2 catalyst prepared using Zr(NO 3 ) 4 5H 2 O as the precursor and treated by water washing displayed the best activity for sulfur-resistant methanation due to its greater number of octahedral Mo species and smaller ZrO 2 grain size.

Pt supported on Zn modified silicalite-1 zeolite as a catalyst for n-hexane aromatization

Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.

Effect of a promoter on the methanation activity of a Mo-based sulfur-resistant catalyst

The effect of adding Co, Ni or La on the methanation activity of a Mo-based sulfur-resistant catalyst was investigated. As promoters, Co, Ni and La all improved the methanation activity of a 15% MOO3/ A1203 catalyst but to different extents. Similar improvements were also found when Co, Ni or La was added to a 15% MoO3/25%-CeO2-A1203 catalyst. The promotion effects of Co and Ni were better than that of La. However, the catalytic methanation activity deteriorated the most with time for the Ni-promoted catalyst. The used catalysts were analyzed by nitrogen adsorption measurement, X-ray diffraction and X-ray photoelectron spectroscopy.

Promotional effect of phosphorylation on CeSn_(0.8)W_(0.6)O_x/TiAl_(0.2)Si_(0.1)O_y for NH_3-SCR of NO from marine diesel exhaust

A series of phosphorylation and blank CeSn_（0.8）W_（0.6）O_x/TiAl_（0.2）Si_（0.1）O_y catalysts prepared by extrusion molding were tested for NH_3-SCR of NO, and were characterized by techniques of X-ray diffraction（XRD）, Brumauer-Emmett-Teller（N_2-BET）, environmental scanning electron microscope（ESEM）, temperature programmed reduction（H_2-TPR） and temperature programmed desorption（NH_3-TPD）. Effects of phosphorylation on catalytic activity and sulfur-resisting performance of the CeSn_（0.8）W_（0.6）O_x/TiAl_（0.2）Si_（0.1）O_y for NH_3-SCR of NO were mainly studied. Results showed that the phosphorylation improved the catalytic activity and sulfur-resisting performance in an active temperature window of 300–440 °C, and the phosphorylation catalyst with 0.4 wt.% H_3PO_4 exhibited the best catalytic performance and the strongest sulfur-resisting performance. Analysis showed that the phosphorylation increased specific surface area, enhanced the surface acidity and improved redox properties.