scholarly journals Selective methylation of toluene using CO2 and H2 to para-xylene

2020 ◽  
Vol 6 (34) ◽  
pp. eaba5433
Author(s):  
Jiachang Zuo ◽  
Weikun Chen ◽  
Jia Liu ◽  
Xinping Duan ◽  
Linmin Ye ◽  
...  

Toluene methylation with methanol to produce xylene has been widely investigated. A simultaneous side reaction of methanol-to-olefin over zeolites is hard to avoid, resulting in an unsatisfactory methylation efficiency. Here, CO2 and H2 replace methanol in toluene methylation over a class of ZnZrOx–ZSM-5 (ZZO-Z5) dual-functional catalysts. Results demonstrate that the reactive methylation species (H3CO*; * represents a surface species) are generated more easily by CO2 hydrogenation than by methanol dehydrogenation. Catalytic performance tests on a fixed-bed reactor show that 92.4% xylene selectivity in CO-free products and 70.8% para-xylene selectivity in xylene are obtained on each optimized catalyst. Isotope effects of H2/D2 and CO2/13CO2 indicate that xylene product is substantially generated from toluene methylation rather than disproportionation. A mechanism involving generation of reactive methylation species on ZZO by CO2 hydrogenation and migration of the methylation species to Z5 pore for the toluene methylation to form xylene is proposed.

2009 ◽  
Vol 16 (03) ◽  
pp. 343-349 ◽  
Author(s):  
YUZHOU YING ◽  
KANKA FENG ◽  
ZHIGUO LV ◽  
ZHENMEI GUO ◽  
JINSHENG GAO

Nano copper-based catalysts were prepared by co-precipitation method and the performance of catalytic hydrogenation for methyl 3-hydroxypropionate (MHP) to 1, 3-propanediol (1, 3-PDO) on the nano catalysts were studied under a high-pressure microcontinuum fixed-bed reactor. The effects of structure, texture, and composition of the catalysts on the catalytic performance were investigated by characterizing the catalysts with XRD, TG–DTG, SEM, and N 2 adsorption/desorption analysis technique. The results showed that addition of promoters enhanced the activity and selectivity of copper-based catalysts, which promoted the dispersion of the active components effectively and stabilized the active center of the catalysts. Especially, the copper-based catalyst of loaded P could restrain side-reaction effectively and improve selectivity obviously, the conversion of MHP and the selectivity of 1, 3-PDO could be 91.30% and reach 90.15%, respectively.


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.


2019 ◽  
Vol 9 (1) ◽  
Author(s):  
Ahmad Asghari ◽  
Mohammadreza Khanmohammadi Khorrami ◽  
Sayed Habib Kazemi

AbstractThe present work introduces a good prospect for the development of hierarchical catalysts with excellent catalytic performance in the methanol to aromatic hydrocarbons conversion (MTA) process. Hierarchical H-ZSM5 zeolites, with a tailored pore size and different Si/Al ratios, were synthesized directly using natural kaolin clay as a low-cost silica and aluminium resource. Further explored for the direct synthesis of hierarchical HZSM-5 structures was the steam assisted conversion (SAC) with a cost-effective and green affordable saccharide source of high fructose corn syrup (HFCS), as a secondary mesopore agent. The fabricated zeolites exhibiting good crystallinity, 2D and 3D nanostructures, high specific surface area, tailored pore size, and tunable acidity. Finally, the catalyst performance in the conversion of methanol to aromatic hydrocarbons was tested in a fixed bed reactor. The synthesized H-ZSM5 catalysts exhibited superior methanol conversion (over 100 h up to 90%) and selectivity (over 85%) in the methanol conversion to aromatic hydrocarbon products.


2011 ◽  
Vol 356-360 ◽  
pp. 1528-1534
Author(s):  
Wei Fang Dong

A series of non-precious metal oxides catalysts were prepared for low-temperature selective catalytic reduction (SCR) of NOx with NH3 in a fixed bed reactor. The catalytic performance was evaluated by the removal efficiency of NOx and N2selectivity which were respectively detected by flue gas analyzer and flue gas chromatograph. Furthermore, the components of gas products from the above experiments were analysed with 2010 GC-MS. The results illustrated that the MnO2exhibited the highest NOx conversion to 95.46% and the highest selectivity of N2to 100% at temperature of 393K, then followed ZrO2, Al2O3and Fe2O3.


2015 ◽  
Vol 802 ◽  
pp. 431-436
Author(s):  
Siti Aminah Md Ali ◽  
Ku Halim Ku Hamid ◽  
Kamariah Noor Ismail

Five series of silica supported bimetallic oxide (NiCo/SiO2) catalysts have been synthesized through successive reverse co-precipitation and wet impregnation methods at different metal loadings (i.e. 80Ni20Co/SiO2,, 60Ni40Co/SiO2,50Ni50Co/SiO2,40Ni60Co/SiO2,20Ni80Co/SiO2). The catalytic performance of these catalysts were tested for the CO2methanation catalysis using microactivity fixed bed reactor. Nickel rich catalyst (80Ni20Co/SiO2) exhibited the highest catalytic activity in the CO2methanation with 47.1% of CO2conversion. Meanwhile, the CH4selectivity and yield was found to be at 99.9% and 27%, respectively.


2017 ◽  
Vol 751 ◽  
pp. 512-517 ◽  
Author(s):  
Supranee Lao-Ubol ◽  
Phunthinee Somwongsa ◽  
Pracha Laoauyporn ◽  
Pasinee Panith ◽  
Siriporn Larpkiattaworn ◽  
...  

Five different types of silica catalyst (SBA-15, SBA-15-PO3H2, and three different Si/Al ratio of commercial zeolites (30, 80 and 280) were used to study the transformation of methanol to hydrocarbon (MTH). The aim of this study was to investigate the effect of pore diameter and acidity in the structure of silica catalysts on the process performances in terms of methanol conversion and hydrocarbon selectivity. The mesoporous silica catalysts were prepared by co-condensation method. The catalysts samples were characterized by GC-MS, XRD, BET, and NH3-TPD techniques. The catalytic performance of synthesized and commercial catalysts for MTH process was evaluated using a homemade fixed bed reactor at temperature (300°C). It was found that the liquid hydrocarbon product provided by zeolite catalysts is aromatic hydrocarbons-rich. High Si/Al zeolites with larger pore size lead to higher selectivity and yield to paraffins (C1-C7). In contrast to commercial zeolite catalyst, SBA-15 and its modification with phosphorus species showed no conversion under studied condition. These results indicate that both pore diameter and acidity influence the product distribution in methanol to hydrocarbon process.


2011 ◽  
Vol 236-238 ◽  
pp. 1067-1072
Author(s):  
Li Ping Liu ◽  
Xiao Jian Ma ◽  
Peng Zhang ◽  
Ya Nan Liu

Hydrogen production by ethanol steam reforming over Ni-Cu/ZnO catalyst in the temperatures range of 250-550°C was studied on a fixed bed reactor. The effects of reaction temperature and water/ethanol molar ratio on hydrogen production were investigated. The structure and surface characteristics of the catalyst were measured by scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential thermal analyzer (TG-DSC). The results show that the Ni-Cu/ZnO catalyst has good catalytic performance with higher hydrogen yield of 4.87molH2/molEtOH reacted. A comparison of hydrogen production from ethanol steam reforming over Ni-Cu/ZnO catalyst with over a commercial catalyst was made in this paper.


Catalysts ◽  
2019 ◽  
Vol 9 (9) ◽  
pp. 752 ◽  
Author(s):  
Yingquan Wu ◽  
Li Tan ◽  
Tao Zhang ◽  
Hongjuan Xie ◽  
Guohui Yang ◽  
...  

Two types of amorphous ZrO2 (am-ZrO2) catalysts were prepared by different co-precipitation/reflux digestion methods (with ethylenediamine and ammonia as the precipitant respectively). Then, copper and potassium were introduced for modifying ZrO2 via an impregnation method to enhance the catalytic performance. The obtained catalysts were further characterized by means of Brunauer-Emmett-Teller surface areas (BET), X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), and In situ diffuse reflectance infrared spectroscopy (in situ DRIFTS). CO hydrogenation experiments were performed in a fixed-bed reactor for isobutanol synthesis. Great differences were observed on the distribution of alcohols over the two types of ZrO2 catalysts, which were promoted with the same content of Cu and K. The selectivity of isobutanol on K-CuZrO2 (ammonia as precipitant, A-KCZ) was three times higher than that on K-CuZrO2 (ethylenediamine as precipitant, E-KCZ). The characterization results indicated that the A-KCZ catalyst supplied more active hydroxyls (isolated hydroxyls) for anchoring and dispersing Cu. More importantly, it was found that bicarbonate species were formed, which were ascribed as important C1 species for isobutanol formation on the A-KCZ catalyst surface. These C1 intermediates had relatively stronger adsorption strength than those adsorbed on the E-KCZ catalyst, indicating that the bicarbonate species on the A-KCZ catalyst had a longer residence time for further carbon chain growth. Therefore, the selectivity of isobutanol was greatly enhanced. These findings would extend the horizontal of direct alcohols synthesis from syngas.


2014 ◽  
Vol 962-965 ◽  
pp. 751-754 ◽  
Author(s):  
Wang Feng ◽  
Bai Ting ◽  
Duan Chao ◽  
Wen Ting Qu ◽  
Xi Ling Liu ◽  
...  

The catalytic performance on HZSM-5/SAPO-34 catalyst in ethanol to propylene was tested in continuous-flow fixed-bed reactor. Coke on HZSM-5/SAPO-34 catalyst for ethanol to propylene was studied by O2-TPO, N2isothermal adsorption–desorption and NH3-TPD.The result showed that the strong and medium acid sites were the active centers of coke deposition; Coke mainly deposited in mesoporous and some coke blocked microporous orifice; In the initial stage of reaction, the high yield of propylene may be benefited from coke deposition, which adjusted the acidity and structure of HZSM-5/SAPO-34.


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