CATALYSIS TODAY
·
2016
·
IF 4.312
Dapeng Liu,Anjie Wang,Chenguang Liu,Roel Prins
Bulk Ni 2 P and Al 2 O 3 -supported Ni 2 P were prepared at low phosphidation temperature (300 or 330 °C) from nickel nitrate, oxide, sulfate, chloride, and acetate as nickel source and ammonium and sodium hypophosphite as well as hypophosphoric acid as phosphorus source. The hypophosphite source was positioned up-flow of the nickel source in an oven and flowing N2 gas transported the phosphine formed in the decomposition of hypophosphite to the nickel compound. X-ray diffraction, N2 adsorption-desorption, thermogravimetry and differential scanning calorimetry, temperature-programmed reduction in H 2 , and transmission electron microscopy, field emission scanning electron microscopy, CO chemisorption, and solid-state 31 P nuclear magnetic resonance were used to study the bulk and supported Ni 2 P. Whereas unsupported nickel nitrate, sulfate, chloride, and oxide led to impure Ni 2 P, nickel acetate gave pure Ni 2 P. Ni 2 P/Al 2 O 3 catalysts were therefore prepared from nickel acetate and their activity was studied in the hydrodesulfurization of dibenzothiophene. Separating the hypophosphite from the nickel compound has the advantage that the phosphate formed in the disproportionation of hypophosphite does not reach the Al 2 O 3 -supported Ni compound and cannot block the pores of the support. Ni 2 P is formed by sequential reduction and phosphidation reactions and therefore its preparation demands careful adjustment of the synthesis conditions. Insufficient PH 3 leads to Ni and Ni 12 P 5 side products and too much PH 3 to Ni 5 P 4 , which all have a lower HDS activity than Ni 2 P.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2020
·
IF 7.888
Xuerong Zhou,Xiang Li,Roel Prins,Jinyin Lv,Anjie Wang,Qiang Sheng
CoP and Co 2 P were prepared by temperature-programmed reduction of the mixtures of Co(OH) 2 and H 3 PO 3 with stoichiometric P/Co ratios, but their surfaces were still enriched in phosphorus. Based on the product distributions of the hydrodesulfurization (HDS) of dibenzothiophene (DBT), 1,2,3,4-tetrahydro-dibenzothiophene (TH-DBT), and 1,2,3,4,4a,9b-hexahydro-dibenzothiophene (HH-DBT), a reaction network of DBT HDS was proposed and the mechanisms of the cleavage of different C S bonds in DBT and its hydrogenated intermediates were discussed. CoP was much more active and more nitrogen-tolerant than Co 2 P, which make it a promising HDS catalyst. The HDS reactions over CoP and Co 2 P followed a pseudo-first-order kinetics and a pseudo-zero-order kinetics, respectively. Piperidine strongly inhibited the hydrogenation/dehydrogenation reactions and the direct desulfurization of DBT, but its inhibition on the desulfurization of TH-DBT and HH-DBT were less pronounced. The active surfaces of CoP and Co 2 P in HDS reactions can be cobalt phosphosulfide phases.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Chemistry
·
2022
·
IF 5.545
Huang Meng,Huang Wenbin,Li Anqi,Yang Han,Jia Yijing,Yu Zhiqing,Xu Zhusong,Wang Xiaohan,Zhou Yasong,Wei Qiang
Experiments were carried out to research the different contents of Ga2O3 modification effects on the hydrodesulfurization (HDS) performance of 4,6-dimethyldibenzothiophene (4,6-DMDBT) catalyzed by the stepwise impregnation method. Characterization techniques such as XRD, BET, HRTEM, NH3-TPD, and Py-FTIR were performed to determine the effects of each modification of the catalyst by Ga on the properties of the prepared supports and catalysts. The catalytic effect of gallium is reflected in the fact that the empty d-orbitals of Ga elements participate in the formation of molecular orbitals in the active center and change their orbital properties, thus generating a direct desulfurization active phase suitable for complex sulfides for endpoint adsorption. The characterization results indicated that the introduction of Ga2O3 with appropriate content (2 wt.%) promoted Ni and Mo species to disperse uniformly and doping of more Ni atoms into the MoS2 crystals, which also increased the average stacking number and the length of MoS2. As a result, more NiMoS active phases were favored to form in the system. The specific surface area and the amounts of acid sites were increased, facilitating the adsorption of reactant molecules and the HDS reactions. The HDS results also suggested the effects of Ga modification play a very important role in the catalytic performance of the corresponding catalysts. The catalyst Ga–Ni–Mo/Al2O3 exhibited the highest conversion rate towards 4,6-DMDBT HDS when the amount of Ga2O3 loading was 2 wt.% with an LHSV of 2.5 h−1 at 290°C and Ga modification also can effectively improve the direct desulfurization (DDS) route selectivity in varying degrees.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2022
·
IF 6.14
Luyao Wang,Zhe Bai,Xiangwen Zhang,Guozhu Li
Hydrodesulfurization (HDS) is an important technique that is widely adopted in the petroleum industry to remove harmful sulfur compounds for environmental protection. MoS2 is the most commonly employed HDS catalyst but tends to stack due to its high surface energy. Active MoS2 nanosheets are anticipated to be well supported for preventing aggregation and increasing accessibility. In the current study, two-dimensional Ti3C2 MXene is utilized as a novel support to controllably anchor MoS2 nanosheets for efficient HDS. The composite of Ti3C2-supported CoMoS2 (CoMoS2/Ti3C2) with a 3D interconnected network was successfully constructed by a facile, one-step hydrothermal method. Detailed characterizations showed that MoS2 nanosheets vertically grew in situ on and between the layers of Ti3C2 MXene. CoMoS2/Ti3C2 possesses a well-defined open structure with a larger specific surface area and a higher proportion of CoMoS active phase compared with unsupported CoMoS2. As catalyzed by CoMoS2/Ti3C2, the reaction rate constant was effectively increased to 2.8 times that on CoMoS2 for the HDS of dibenzothiophene. CoMoS2/Ti3C2 also showed good stability in a harsh high-temperature reaction environment.
研究领域:
材料科学
·
催化化学
·
能源化工
✓ 已验证
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2022
·
IF 5.876
Hao Zhang,Guang-Ren Qian,Hong Liu
Alumina composites containing microporous ZSM-5 (Z-5) and mesoporous ZSM-5 (MZ-5), corresponding to x ZA and x MZA, were developed by incorporating Z-5 and MZ-5 into γ - Al 2 O 3 , respectively. The two series of NiMoS/ x MZA and NiMoS/ x ZA catalysts were prepared with these two composites as supports, respectively, and were used for the simultaneous hydrodesulfurization (HDS) of thiophene (T) and benzothiophene (BT). The results show that NiMoS/ x MZA series catalysts exhibit higher HDS activity than that of NiMoS/ x ZA and NiMoS/γ-Al 2 O 3 , and the HDS activity of NiMoS/ x MZA catalysts increases with the increase of MZ-5. The high HDS activity can be mainly attributed to the synergistic effects of the efficient diffusing pore channels, high dispersion of type II NiMoS phases, suitable acidity, and moderate Mo-support interaction. Moreover, the product distribution of HDS shows that the NiMoS/ x MZA catalysts possess the dominant direct desulfurization (DDS) selectivity and the selectivity increases with the increase of MZ-5 content due to more corner sites and suitable Brønsted (B) acid sites, whereas the NiMoS/ x ZA catalysts perform more excellent hydrogenation (HYD) selectivity, and the selectivity increases with the increase of Z-5 content because of the existence of more edge sites. Based on this, the possible reaction network for T and BT hydrodesulfurization over the catalysts are proposed.
研究领域:
催化化学
·
能源化工
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2019
·
IF 4.175
Bolong Jiang,Tianhan Zhu,Hua Song,Feng Li
The Fe-doped Ni 2 P/Fe-SBA-15 was prepared by the temperature programmed reduction method at a relative low temperature of 673 K. The effect of Fe on the catalytic performance for benzofuran (BF) hydrodeoxygenation (HDO) and dibenzothiophene (DBT) hydrodesulfurization (HDS) were investigated. The catalysts were characterized by means of X-ray diffraction (XRD), N 2 adsorption-desorption, inductively coupled plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption of ammonia (NH 3 -TPD), and transmission electron microscope (TEM) and CO uptakes. The results indicate the incorporation of Fe into SBA-15 contributes to the exposure of smaller Ni 2 P particles (5.6 nm) with an uniform dispersion, along with enhancement of weak and medium acid strengths . Compared with Ni 2 P/SBA-15, the Fe-doped Ni 2 P/Fe-SBA-15 exhibited a much higher BF conversion of 91.7% with an improved total deoxygenated product yield of 83.3%. The excellent HDO performance of Ni 2 P/Fe-SBA-15 can be ascribed to the exposure of highly-dispersed smaller Ni 2 P particles. Meanwhile, the improved dehydration of 2-EtPh to EB and the high deoxygenated product selectivity can be attributed to the enhanced acidity. As compared to the Ni 2 P/SBA-15, the Fe-doped Ni 2 P/Fe-SBA-15 showed a higher DBT HDS activity of 96.3% with the BP formation at a great proportion of 90.3%, indicating that DBT was mainly transformed through the desulfurization pathway during HDS.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
·
2019
·Vol. 9
·期 5
·448
·
IF 3.444
Meng Li,Jinhe Song,Fan Yue,Fan Pan,Wei Yan,Zelin Hua,Long Li,Zhuhong Yang,Licheng Li,Guangming Wen,Kongguo Wu
Mesoporous TiO2containing different potassium content was prepared from potassium titanate by mediating the pH value of the ion exchange, which was used as catalytic support to load NiMo for hydrodesulfurization of dibenzothiophene. The as-prepared samples were characterized by X-ray diffraction, N2physical adsorption/desorption, temperature-programmed reduction, scanning electron microscope/energy dispersive X-ray mapping analysis, high resolution transmission electron microscopy, and pyridine-adsorbed Fourier transform infrared spectroscopy. The characterization results showed that NiO and MoO3were well dispersed on mesoporous TiO2with varying potassium content. A crystal NiMoO4phase was formed on the TiO2with relatively high potassium content, which could decrease the reduction temperature of oxidized active species. The evaluation results from the hydrodesulfurization displayed that as the potassium content of the catalyst increased, the dibenzothiophene conversion firstly increased and then slightly decreased when potassium content exceeded 6.41 wt %. By contrast, the direct desulfurization selectivity could continuously increase along with the potassium content of catalyst. Furthermore, the change in direct desulfurization selectivity of a TiO2-supported NiMo catalyst was independent of the reaction condition. The mesoporous TiO2-supported NiMo catalyst incorporated with potassium could have near both 100% of dibenzothiophene and 100% of direct desulfurization selectivity. According to the structure–performance relationship discussion, the incorporation of potassium species could benefit the formation of more sulfided active species on mesoporous TiO2. Moreover, excessive free potassium species may poison the active sites of the hydrogenation pathway. Both factors determined the characteristics of complete hydrodesulfurization of dibenzothiophene via a direct desulfurization pathway for potassium-incorporated mesoporous TiO2supported NiMo catalysts.Keywords:TiO2;potassium;hydrodesulfurization;dibenzothiophene;direct desulfurization;selectivity
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
RSC Advances
·
2018
·Vol. 8
·期 48
·27565-27573
·
IF 2.936
Qian Meng,Peng Du,Bo Wang,Aijun Duan,Chunming Xu,Zhen Zhao,Cong Liu,Di Hu,Yuyang Li,Chengkun Xiao
Zirconium modified mesoporous materials were successfully synthesized by different methods including direct synthesis and post synthesis (grafting and impregnating). Meanwhile, the corresponding catalysts were prepared. A series of techniques, including small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and pyridine adsorption Fourier-transform infrared (Py-IR), were used to characterize the properties of supports and catalysts. The results of SASX and TEM characterization proved that all the modified materials retained the well-ordered mesoporous structure from the FDU-12 material. N2 adsorption–desorption results showed that the Zr-FDU-12 material obtained by direct synthesis (Zr-in-F) possessed higher specific surface area (709 m2 g−1), pore volume (0.65 cm3 g−1) and larger pore size (18.7 nm) than the Zr-FDU-12 materials obtained by the post synthesis. According to the characterization result of UV-Vis, Zr-in-F exhibited better dispersion of Zr species than materials obtained by the post synthesis. It was found that the incorporation of Zr species not only increased acidities but also enhanced the sulfidities of the Mo species. All the catalysts were evaluated for their activities in the hydrodesulfurization of dibenzothiophene, and the NiMo/Zr-in-F catalyst exhibited the best catalytic performance (97.3%), attributed to its higher specific surface area, larger pore size, higher sulfidity, and more acidic sites.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2016
·Vol. 7
·期 2
·466-480
·
IF 5.287
Sijia Liu,Xin Liang,Jie Zhang,Biaohua Chen
Two different kinds of γ-Al2O3 precursors: stick-like ammonium aluminum carbonate hydroxide and willow leaf-like boehmite could be selectively synthesized via a facile hydrothermal method by just adjusting reaction temperature. After heat treatment, γ-Al2O3 with two different morphologies (stick-like and willow leaf-like) were synthesized and used as supports for CoMo hydrodesulfurization catalysts. Fourier transform infrared spectroscopy of pyridine adsorption and NH3-temperature-programmed desorption showed that stick-like γ-Al2O3 (ACH) and willow leaf-like γ-Al2O3 (AOH) exhibited a lower Lewis acidity than commercial γ-Al2O3. X-ray diffraction indicated that CoMo oxidic catalysts supported on ACH and AOH contained more β-CoMoO4 phase. X-ray photoelectron spectroscopy and high resolution transmission electron microscopy revealed that after presulfurization, more CoMoS active sites and multilayered (Co)MoS2 slabs formed on ACH and AOH supports, thereby creating catalysts with a higher hydrodesulfurization activity in the hydrodesulfurization of thiophene and 4,6-dimethyldibenzothiophene.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2021
·
IF 7.033
Antony Rajendran,Tian-You Cui,Hong-Xia Fan,Meng-Yu Wang,Wen-Ying Li
A straightforward hydrothermal synthesis of NiMoS active phases loaded on SBA-15 was attempted. We initially prepared a catalyst by impregnating metal precursors sequentially onto SBA-15 and the subsequent hydrothermal treatment with sublimed sulfur. To obtain the one-pot catalyst, we performed the hydrothermal treatment of a mechanical mixture containing metal precursors, sublimed sulfur, and SBA-15. The catalysts were characterized by powder X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, N 2 adsorption-desorption study, and high-resolution transmission emission spectroscopy . Compared to impregnation-assisted synthesis, the one-pot synthesis promoted the generation of dispersed shorter MoS 2 slabs with desirable average stacking number, i.e., increased number of edge and rim sites. Therefore, the one-pot catalyst enabled the ultra-deep sulfur removal (~100%) in the dibenzothiophene hydrodesulfurization . Unlike Ni(acac) 2 , the utilization of Ni(NO 3 ) 2 inhibits the sulfidation of molybdenum and the dispersion of MoS 2 layers, decreasing the hydrodesulfurization activity. The one-pot catalyst was able to achieve ~80% sulfur removal even after six consecutive catalytic runs under batch reactor conditions (320 °C, 6 MPa (H 2 ), 500 ppmw S, 100 mg (m cat )) due to the persistent stability of NiMoS active phases.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2020
·Vol. 10
·期 17
·6065-6075
·
IF 5.721
Jundong Xu,Chenglong Wen,Shuisen He,Yu Fan
This article presents novel decyltrimethylammonium bromide-dispersed Ni–Mo sulfide (DTMA-NiMo) as a precursor for preparing an efficient NiMoS/γ-Al2O3 hydrodesulfurization (HDS) catalyst. The as-synthesized DTMA-NiMo is a sulfide containing both long-chain quaternary ammonium and Ni–Mo–S elements. The proposed method not only significantly improves the dispersion of Mo species but also greatly promotes the incorporation of Ni into MoS2 slabs, leading to an increase in the number of NiMoS phases. As a result, the DTMA-NiMo-based NiMoS/γ-Al2O3 catalyst exhibits much higher activity for the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT) and fluid catalytic cracking (FCC) diesel than NiMoS/γ-Al2O3 catalysts prepared by the co-impregnation and tetrapropylammonium bromide (TPAB)-assisted methods. This novel strategy sheds a light on the facile and low-cost preparation of superior NiMoS phases without sulfidation treatment.
研究领域:
化学工程
·
催化材料
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2018
·
IF 4.908
Wenwu Zhou,Yanan Zhang,Xiujuan Tao,Yasong Zhou,Qiang Wei,Sijia Ding
The effects of gallium (Ga) modification on mesoporous Al 2 O 3 (MA) were studied, focusing on the morphology changes of the active phases and the application as catalyst support for catalytic performances for dibenzothiophene (DBT) hydrodesulfurization (HDS). MA samples with wide mesopore size distribution (MA-W), double mesopore size distribution (MA-D) and single mesopore size distribution (MA-S) were synthesized from the boehmite sol–gel via a hydrothermal synthesis method. The synthesized MA-S sample was modified with Ga 2 O 3 , and the corresponding sulfide NiMo supported catalysts were prepared. The as-synthesized samples were characterized by XRD, N 2 physisorption, NH 3 -TPD, H 2 -TPR, HRTEM and XPS. Superior catalytic performance was observed over the NiMo/MA-S-2Ga catalyst due to the moderate interaction between the active metals and the supports; the superior morphology for Ni promoted MoS 2 crystals, the highest sulfidation degree, the largest proportion of the NiMoS phase and the enhanced hydrogenation activity caused by the introduction of Ga species.
研究领域:
催化材料
·
化学工程
·
能源化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）