Structural/Texture Evolution During Facile Substitution of Ni into ZSM-5 Nanostructure vs. its Impregnation Dispersion Used in Selective Transformation of Methanol to Ethylene and Propylene

Author(s):  
Parisa Sadeghpour ◽  
Mohammad Haghighi ◽  
Mehrdad Esmaeili

Aim and Objective: Effect of two different modification methods for introducing Ni into ZSM-5 framework was investigated under high temperature synthesis conditions. The nickel successfully introduced into the MFI structures at different crystallization conditions to enhance the physicochemical properties and catalytic performance. Materials and Methods: A series of impregnated Ni/ZSM-5 and isomorphous substituted NiZSM-5 nanostructure catalysts were prepared hydrothermally at different high temperatures and within short times. X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray (EDX), Brunner, Emmett and Teller-Barrett, Joyner and Halenda (BET-BJH), Fourier transform infrared (FTIR) and Temperature-programmed desorption of ammonia (TPDNH3) were applied to investigate the physicochemical properties. Results: Although all the catalysts showed pure silica MFI–type nanosheets and coffin-like morphology, using the isomorphous substitution for Ni incorporation into the ZSM-5 framework led to the formation of materials with lower crystallinity, higher pore volume and stronger acidity compared to using impregnation method. Moreover, it was found that raising the hydrothermal temperature increased the crystallinity and enhanced more uniform incorporation of Ni atoms in the crystalline structure of catalysts. TPD-NH3 analysis demonstrated that high crystallization temperature and short crystallization time of NiZSM-5(350-0.5) resulted in fewer weak acid sites and medium acid strength. The MTO catalytic performance was tested in a fixed bed reactor at 460ºC and GHSV=10500 cm3 /gcat.h. A slightly different reaction pathway was proposed for the production of light olefins over impregnated Ni/ZSM-5 catalysts based on the role of NiO species. The enhanced methanol conversion for isomorphous substituted NiZSM-5 catalysts could be related to the most accessible active sites located inside the pores. Conclusion: The impregnated Ni/ZSM-5 catalyst prepared at low hydrothermal temperature showed the best catalytic performance, while the isomorphous substituted NiZSM-5 prepared at high temperature was found to be the active molecular sieve regarding the stability performance.

2013 ◽  
Vol 634-638 ◽  
pp. 696-700
Author(s):  
Lin Jiu Xiao ◽  
Peng Li ◽  
Yong Gang Sheng

A series of Ti(SO4)2/γ-Al2O3 catalysts were prepared by impregnation method and the catalytic performance of these catalysts in 1-butene oligomerization was investigated. The heat treatment temperature played great influences on the catalytic performance of these catalysts in the oligomerization. 90.1 wt.% conversion of 1-butene and 92.2 wt.% selectivity of dimers were obtained on Ti(SO4)2/γ-Al2O3(450) catalyst at 80 °C, 1.0 Mpa and LHSV=0.6 h−1. The heat treatment temperature determined the crystallinity of TiOSO4 and specific surface area of these catalysts, which affected the catalytic performance of these catalysts in 1-butene oligomerization. In addition, the physicochemical properties of these catalysts were comparatively characterized by powder X-ray diffraction (XRD), N2 isothermal adsorption-desorption techniques.


2020 ◽  
Vol 11 (4) ◽  
pp. 11592-11601

In this study, pretreatment conditions such as impregnation time and temperature and drying time and temperature for the production of the iron-cobalt-cerium catalyst with impregnation method as a first step for controlling the synthesis of a new type of three similar metal phase ratio were determined by the Taguchi method. A microtubular fixed bed reactor tested the catalysts' performance under constant conditions according to conversion. The activity and selectivity toward propylene and ethylene have been calculated. The catalyst, which impregnated at 90 °C for 4hr and dried at 120 °C for 24hr, had the best catalytic performance. According to previous studies, the catalyst calcined and the reactor test was performed in the constant and optimum condition such as calcinations in 600 °C for 6hr, reduction with H2 (flow = 30 mL.min-1) for 90 min and P~1atm and also the reaction terms was H2:CO = 1(flow H2 = 37.5 mL.min-1 and CO =37.5 mL.min-1) and p=1bar. Finally, The characterization was done by XRD, SEM, BET, and test on the precursor, optimized catalyst, and optimized catalyst after reactor tests, which all were showed the nanosized catalyst particles.


2018 ◽  
Vol 19 (1) ◽  
pp. 24-33 ◽  
Author(s):  
FAHIM FAYAZ ◽  
NGUYEN THI ANH NGA ◽  
THONG LE MINH PHAM ◽  
HUONG THI DANH ◽  
BAWADI ABDULLAH ◽  
...  

La-promoted and unpromoted 10%Co/Al2O3 catalysts were synthesized using wet a impregnation method and evaluated in a quartz fixed-bed reactor at different CO2:C2H5OH ratios of 2.5:1-1:2.5 and a reaction temperature of 973 K under atmospheric pressure. X-ray diffraction measurements detected the presence of Co3O4 and CoAl2O4 phases on the surface of both promoted and unpromoted catalysts. BET surface area of promoted and unpromoted 10%Co/Al2O3 catalysts was about 143.09 and 136.04 m2.g-1, respectively. The La promoter facilitated Co3O4 reduction, improved the degree of reduction from 86 to 98% and increased metal dispersion from 9.11% to 16.64%. The La-promoted catalyst appeared to be a better catalyst in terms of catalytic activity and product yield regardless of reactant partial pressure. Both C2H5OH and CO2 conversions improved significantly with an increase in CO2 partial pressure from 20 to 50 kPa for both catalysts whilst a decline in catalytic performance was observed with rising C2H5OH partial pressure. La addition improved C2H5OH and CO2 conversions up to about 74.22% and 33.80%, respectively. ABSTRAK: Penggalak-La dan bukan penggalak-La mangkin 10%Co/Al2O3 dihasilkan menggunakan kaedah impregnasi basah dan dinilai dalam reaktor alas-tetap quarza pada pelbagai nisbah CO2:C2H5OH sebanyak 2.5:1-1:2.5 dan suhu tindak balas sebanyak 973 K di bawah tekanan atmosfera. Hasil daripada ukuran pembelauan X-ray, didapati terdapat kehadiran fasa Co3O4 dan CoAl2O4 pada permukaan kedua-dua mangkin penggalak dan bukan penggalak. Permukaan kawasan BET pada penggalak dan bukan penggalak mangkin 10%Co/Al2O3 adalah masing-masing sebanyak 143.09 dan 136.04 m2.g-1. Penggalak-La membantu dalam pengurangan Co3O4,membaiki peratus penurunan daripada 86 kepada 98% dan menambah penyebaran logam daripada 9.11% kepada 16.64%. Mangkin penggalak-La dilihat sebagai mangkin terbaik dari segi aktiviti pemangkinan dan hasil pengeluaran, biarpun pada tekanan separa reaktan. Kedua-dua penukaran C2H5OH dan CO2 meningkat dengan ketara dengan kenaikan separa tekanan CO2 daripada 20 kepada 50 kPa bagi kedua-dua pemangkin, sementara penurunan dalam aktiviti pemangkinan dilihat dengan kenaikan tekanan separa C2H5OH. Penambahan La meningkatkan penukaran C2H5OH dan CO2, masing-masing sebanyak 74.22% dan 33.80%.


Author(s):  
Radwa A. El-Salamony ◽  
Sara A. El-Sharaky ◽  
Seham A. Al-Temtamy ◽  
Ahmed M. Al-Sabagh ◽  
Hamada M. Killa

Abstract Recently, because of the increasing demand for natural gas and the reduction of greenhouse gases, interests have focused on producing synthetic natural gas (SNG), which is suggested as an important future energy carrier. Hydrogenation of CO2, the so-called methanation reaction, is a suitable technique for the fixation of CO2. Nickel supported on yttrium oxide and promoted with cobalt were prepared by the wet-impregnation method respectively and characterized using SBET, XRD, FTIR, XPS, TPR, and HRTEM/EDX. CO2 hydrogenation over the Ni/Y2O3 catalyst was examined and compared with Co–Ni/Y2O3 catalysts, Co% = 10 and 15 wt/wt. The catalytic test was conducted with the use of a fixed-bed reactor under atmospheric pressure. The catalytic performance temperature was 350 °C with a supply of H2:CO2 molar ratio of 4 and a total flow rate of 200 mL/min. The CH4 yield was reached 67%, and CO2 conversion extended 48.5% with CO traces over 10Co–Ni/Y2O3 catalyst. This encourages the direct methanation reaction mechanism. However, the reaction mechanism over Ni/Y2O3 catalyst shows different behaviors rather than that over bi-metal catalysts, whereas the steam reforming of methane reaction was arisen associated with methane consumption besides increase in H2 and CO formation; at the same temperature reaction.


Energies ◽  
2021 ◽  
Vol 14 (11) ◽  
pp. 3347
Author(s):  
Arslan Mazhar ◽  
Asif Hussain Khoja ◽  
Abul Kalam Azad ◽  
Faisal Mushtaq ◽  
Salman Raza Naqvi ◽  
...  

Co/TiO2–MgAl2O4 was investigated in a fixed bed reactor for the dry reforming of methane (DRM) process. Co/TiO2–MgAl2O4 was prepared by modified co-precipitation, followed by the hydrothermal method. The active metal Co was loaded via the wetness impregnation method. The prepared catalyst was characterized by XRD, SEM, TGA, and FTIR. The performance of Co/TiO2–MgAl2O4 for the DRM process was investigated in a reactor with a temperature of 750 °C, a feed ratio (CO2/CH4) of 1, a catalyst loading of 0.5 g, and a feed flow rate of 20 mL min−1. The effect of support interaction with metal and the composite were studied for catalytic activity, the composite showing significantly improved results. Moreover, among the tested Co loadings, 5 wt% Co over the TiO2–MgAl2O4 composite shows the best catalytic performance. The 5%Co/TiO2–MgAl2O4 improved the CH4 and CO2 conversion by up to 70% and 80%, respectively, while the selectivity of H2 and CO improved to 43% and 46.5%, respectively. The achieved H2/CO ratio of 0.9 was due to the excess amount of CO produced because of the higher conversion rate of CO2 and the surface carbon reaction with oxygen species. Furthermore, in a time on stream (TOS) test, the catalyst exhibited 75 h of stability with significant catalytic activity. Catalyst potential lies in catalyst stability and performance results, thus encouraging the further investigation and use of the catalyst for the long-run DRM process.


Catalysts ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 553
Author(s):  
Mansurbek Urol ugli Abdullaev ◽  
Sungjune Lee ◽  
Tae-Wan Kim ◽  
Chul-Ung Kim

Among the zeolitic catalysts for the ethylene-to-propylene (ETP) reaction, the SSZ-13 zeolite shows the highest catalytic activity based on both its suitable pore architecture and tunable acidity. In this study, in order to improve the propylene selectivity further, the surface of the SSZ-13 zeolite was modified with various amounts of tungsten oxide ranging from 1 wt% to 15 wt% via a simple incipient wetness impregnation method. The prepared catalysts were characterized with several analysis techniques, specifically, powder X-ray diffraction (PXRD), Raman spectroscopy, temperature-programmed reduction of hydrogen (H2-TPR), temperature-programmed desorption of ammonia (NH3-TPD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and N2 sorption, and their catalytic activities were investigated in a fixed-bed reactor system. The tungsten oxide-modified SSZ-13 catalysts demonstrated significantly improved propylene selectivity and yield compared to the parent H-SSZ-13 catalyst. For the tungsten oxide loading, 10 wt% loading showed the highest propylene yield of 64.9 wt%, which was 6.5 wt% higher than the pristine H-SSZ-13 catalyst. This can be related to not only the milder and decreased strong acid sites but also the diffusion restriction of bulky byproducts, as supported by scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDS) observation.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Longfei Lin ◽  
Mengtian Fan ◽  
Alena M. Sheveleva ◽  
Xue Han ◽  
Zhimou Tang ◽  
...  

AbstractOptimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.


2011 ◽  
Vol 347-353 ◽  
pp. 3681-3684 ◽  
Author(s):  
Young Ho Kim ◽  
Su Gyung Lee ◽  
Byoung Kwan Yoo ◽  
Han Sol Je ◽  
Chu Sik Park

A SAPO-34 catalyst is well known to be one of the best catalysts for DME to olefins (DTO) reaction. Main products of the reaction were light olefins such as ethylene, propylene and butenes. However, the main problem is rapid deactivation of the SAPO-34 catalyst due to coke deposition during DTO reaction. In this study, various SAPO-34/ZrO2 catalysts added with ZrO2 were prepared for improving the lifetime and their physicochemical properties have been characterized by XRD and SEM. The DTO reaction over various SAPO-34/ZrO2 catalysts was carried out using a fixed bed reactor. All SAPO-34/ZrO2 catalysts showed similar activity and selectivity in the DTO reaction. The SAPO-34(9wt%)/ZrO2 catalyst was showed the best performance for the catalyst lifetime.


Catalysts ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 541 ◽  
Author(s):  
Haiping Xiao ◽  
Chaozong Dou ◽  
Hao Shi ◽  
Jinlin Ge ◽  
Li Cai

A series of poisoned catalysts with various forms and contents of sodium salts (Na2SO4 and Na2S2O7) were prepared using the wet impregnation method. The influence of sodium salts poisoned catalysts on SO2 oxidation and NO reduction was investigated. The chemical and physical features of the catalysts were characterized via NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FT-IR). The results showed that sodium salts poisoned catalysts led to a decrease in the denitration efficiency. The 3.6% Na2SO4 poisoned catalyst was the most severely deactivated with denitration efficiency of only 50.97% at 350 °C. The introduction of SO42− and S2O72− created new Brønsted acid sites, which facilitated the adsorption of NH3 and NO reduction. The sodium salts poisoned catalysts significantly increased the conversion of SO2–SO3. 3.6%Na2S2O7 poisoned catalyst had the strongest effect on SO2 oxidation and the catalyst achieved a maximum SO2–SO3-conversion of 1.44% at 410 °C. Characterization results showed sodium salts poisoned catalysts consumed the active ingredient and lowered the V4+/V5+ ratio, which suppressed catalytic performance. However, they increased the content of chemically adsorbed oxygen and the strength of V5+=O bonds, which promoted SO2 oxidation.


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