scholarly journals Effect of In-Situ Dehydration on Activity and Stability of Cu–Ni–K2O/Diatomite as Catalyst for Direct Synthesis of Dimethyl Carbonate

Catalysts ◽  
2018 ◽  
Vol 8 (9) ◽  
pp. 343 ◽  
Author(s):  
Dongmei Han ◽  
Yong Chen ◽  
Shuanjin Wang ◽  
Min Xiao ◽  
Yixin Lu ◽  
...  

An in-situ dehydrating system built in a continuous flow fixed-bed bubbling reactor for direct synthesis of dimethyl carbonate (DMC) was designed. 3A molecular sieve (MS) was selected as the ideal dehydrating agent and the water trapping efficiency was studied. The effect of dehydrating agent/catalyst ratio, the dehydrating temperature and pressure, as well as the space velocity on the direct DMC synthesis catalyzed by K2O-promoted Cu–Ni was further investigated. These results demonstrated that 3A MS could effectively dehydrate the reaction system at the optimal conditions of 120 °C and 1.0 MPa with gas space velocity (GHSV) of 600 h−1, thereby greatly shifting the reaction equilibrium toward high DMC yield. Higher DMC yield of 13% was achieved compared with undehydrated reaction. Moreover, the catalyst can be highly stabilized by 3A MS dehydration with stable performs over 22 h.

Author(s):  
Guanyi Chen ◽  
Qiang Li ◽  
Xiaoyang Lv ◽  
Na Deng ◽  
Lifei Jiao

Biomass is quite abundant in the world, particularly in some countries like China. China has large quantities of straw and/or stalk-origin biomass resources and the attention is currently being paid to the exploitation of these resources to produce energy products via different technical solutions, among of which pyrolysis of biomass to produce hydrogen-rich gas is very promising as hydrogen is a very clear energy carrier. In this work, pyrolysis of rice straw, corn stalk and sawdust was carried out in a two-stage reactor (the first-stage reactor is a conventional fixed-bed pyrolyser, and the second-stage reactor is a catalytic fixed bed) to produce hydrogen-rich gas. The effect of catalytic bed on the pyrolysis behaviour have been investigated, with the emphasis on final product particularly hydrogen. The operation of the catalytic reactor appears significant in promoting biomass pyrolysis towards the production of gaseous products, especially hydrogen. At 750°C of the pyrolyser with rice straw as fuel, the use of the catalytic bed leads to the increases of gas yield from 0.41 Nm3/kg to 0.50 Nm3/kg, approximately 22% increase, and of H2 concentration from 33.79% to 50.80% in volume, approximately 50.3% increase, respectively. Compared with calcined dolomite, fresh nickel-based catalyst shows stronger catalytic effect on the pyrolysis of rice straw as its use in the catalytic bed results in the increase of gas yield from 0.41 Nm3/kg to 0.56 Nm3/kg, approximately 36.6% increase, and the increase of H2 concentration from 33.79% to 59.55% in volume, approximately 76.2% increase. Furthermore, two catalysts follow the same trend for the pyrolysis of corn stalk and sawdust. At temperature of 815°C, catalysts also follow the same trend. Catalytic bed can significantly reduce the level of tar which is carried out with the producer gas, to less than 1% of original level. Catalyst load or gas space velocity (hourly) has the influence on the gas yield and H2 concentration. 30% of load, i.e. gas space velocity (hourly) 0.9 × 104 h−1, appears reasonable. Beyond that, gas yield and H2 concentration remain almost unchanged.


2018 ◽  
Vol 913 ◽  
pp. 900-906
Author(s):  
Dong Zhu Ma ◽  
Jian Li ◽  
Di Yin ◽  
Yuan Huang ◽  
Rui Min Wang ◽  
...  

Mo-V-Ti catalysts of low temperature denitrification were prepared by dipping method. In order to study the activity of selective catalytic reduction, the catalyst was placed in a fixed bed reactor. Industrial flue gas was simulated with cylinder gas. The experimental condition is NO: 500ppm, NH3:500ppm, O2:8%, SO2:100ppm, N2: equilibrium gas, space velocity: 36000h-1. Results indicate that the catalyst prepared by dipping method had good denitrification activity and sulfur resistance at low temperature. The optimum ratio of catalyst was 3V2O5-6MoO3-91TiO2 (wt %). The conversion efficiency of NO was 80~93%, and the conversion efficiency of SO2 was less than 1% at 180~260 °C.


Catalysts ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 537 ◽  
Author(s):  
Yanyong Liu

Al-modified hexagonal mesoporous silica (HMS) materials were synthesized using dodecylamine as a template according to the methods reported in the literature. FT-IR spectra proved that Al3+ ions entered in the HMS framework in Al-HMS (prepared by sol-gel reaction) but Al3+ ions existed in the extra-framework in Al/HMS (prepared by post-modification). NH3-TPD indicated that either Al-HMS or Al/HMS had solid acid sites on the surface, and the acidic strength of Al/HMS was stronger than that of Al-HMS. For ethylene oligomerization at 200 °C under 1 MPa, Ni/Al-HMS showed an ethylene conversion of 96.3%, which was much higher than that over Ni/Al/HMS (45.6%). The selectivity for C4H8, C6H12, C8H16, and C8+ was 37.7%, 24.5%, 24.0%, and 9.1% for ethylene oligomerization over Ni/Al-HMS, respectively. Ni/Al-MCM-41, which has been reported as an effective catalyst for ethylene oligomerization in the literature, showed a high ethylene conversion (95.2%) similar to that of Ni/Al-HMS in this study. However, the selectivity for C8H16 over Ni/Al-MCM-41 (16.3%) was lower than that over Ni/Al-HMS (24.0%) in the ethylene oligomerization. For ethanol dehydration at 300 °C under 1 MPa, a commercial H-ZSM-5 catalyst showed a high ethylene yield (91.2%) after reaction for 24 h using a feed containing 90 wt.% ethanol and 10 wt.% water. In this study, a two-step process containing two fixed-bed reactors and one cold trap was designed to achieve the direct synthesis of higher olefins from bio-ethanol. The cold trap was used to collect the water formed from ethanol dehydration. By using H-ZSM-5 as a catalyst for ethanol dehydration in the first reactor and using Ni/Al-HMS as a catalyst for ethylene oligomerization in the second reactor, higher olefins were continuously formed by feeding a mixture containing 90 wt.% ethanol and 10 wt.% water. The yields of higher olefins did not decrease after reaction for 8 h in the two-step reaction system.


Nano Research ◽  
2021 ◽  
Author(s):  
Yongdong Chen ◽  
Yue Li ◽  
Wei Chen ◽  
Wen Wu Xu ◽  
Zhong-kang Han ◽  
...  

AbstractWe evaluated bismuth doped cerium oxide catalysts for the continuous synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the absence of a dehydrating agent. BixCe1−xOδ nanocomposites of various compositions (x = 0.06–0.24) were coated on a ceramic honeycomb and their structural and catalytic properties were examined. The incorporation of Bi species into the CeO2 lattice facilitated controlling of the surface population of oxygen vacancies, which is shown to play a crucial role in the mechanism of this reaction and is an important parameter for the design of ceria-based catalysts. The DMC production rate of the BixCe1−xOδ catalysts was found to be strongly enhanced with increasing Ov concentration. The concentration of oxygen vacancies exhibited a maximum for Bi0.12Ce0.88Oδ, which afforded the highest DMC production rate. Long-term tests showed stable activity and selectivity of this catalyst over 45 h on-stream at 140 °C and a gas-hourly space velocity of 2,880 mL·gcat−1·h−1. In-situ modulation excitation diffuse reflection Fourier transform infrared spectroscopy and first-principle calculations indicate that the DMC synthesis occurs through reaction of a bidentate carbonate intermediate with the activated methoxy (−OCH3) species. The activation of CO2 to form the bidentate carbonate intermediate on the oxygen vacancy sites is identified as highest energy barrier in the reaction pathway and thus is likely the rate-determining step.


1972 ◽  
Vol 25 (5) ◽  
pp. 1003 ◽  
Author(s):  
I Dainis

Several routes to 1-formylmethyl-2-methylpyridinium bromide have been investigated. Chichibabin cyclization of this salt to indolizine fails because the reaction system favours an intermolecular aldol condensation. A general one-step synthesis of acyl-and diacyl-indolizines from 1-(β-oxo)-alkyl-2-alkyl- and 1-(β-oxo)alkyl-2-benzyl-pyridinium salts is described. This synthesis, as effected by the anhydride of a weak aliphatic acid and its sodium salt, also gives isomeric products and these have provided a mechanistic reaction scheme of three competing pathways. 1-Acyl-2,3-disubstituted and 3-acyl-1,2-disubstituted indolizines are formed from the relevant salts by Chichibabin cyclization and subsequent in situ acylation. 1-Acetonyl-2-methylpyridinium bromide gives useful yields of 3-acyl-and 1,3-di-acyl-indolizines by this pathway and also via 1-acetonyl-2-acetylmethylene-l,2-dihydropyridine. The reaction of the corresponding 1-phenacyl salt involves acylated intermediates of type (14) and (15), and has provided evidence for the rearrangement of the diacylmethylides (15) to acylmethines (14). A facile thermal cyclization of 2-phenylpyridinium diphenacylmethylide to 3-benzoyl-1,2-diphenylindolizine is reported.


2017 ◽  
Vol 68 (7) ◽  
pp. 1496-1500
Author(s):  
Rami Doukeh ◽  
Mihaela Bombos ◽  
Ancuta Trifoi ◽  
Minodora Pasare ◽  
Ionut Banu ◽  
...  

Hydrodesulphurization of dimethyldisulphide was performed on Ni-Co-Mo /�-Al2O3 catalyst. The catalyst was characterized by determining the adsorption isotherms, the pore size distribution and the acid strength. Experiments were carried out on a laboratory echipament in continuous system using a fixed bed catalytic reactor at 50-100�C, pressure from 10 barr to 50 barr, the liquid hourly space velocity from 1h-1 to 4h-1 and the molar ratio H2 / dimethyldisulphide 60/1. A simplified kinetic model based on the Langmuir�Hinshelwood theory, for the dimethyldisulphide hydrodesulfurization process of dimethyldisulphide has been proposed. The results show the good accuracy of the model.


Catalysts ◽  
2021 ◽  
Vol 11 (1) ◽  
pp. 110
Author(s):  
Yuanqing Liu ◽  
Chau T. Q. Mai ◽  
Flora T. T. Ng

The glycerol hydrogenolysis to produce 1,2-propanediol without using externally supplied hydrogen was investigated using methanol present in crude glycerol to provide in situ hydrogen via its steam reforming reaction. This paper focuses on the promoting effect of Pd on the reactivity of a Cu/Zn/Al2O3 catalyst. Adding 2 wt% Pd onto a Cu/ZnO/Al2O3 catalyst significantly improved the selectivity to 1,2-propanediol from 63.0% to 82.4% and the glycerol conversion from 70.2% to 99.4%. This enhancement on the catalytic activity by Pd is mainly due to the improved hydrogenation of acetol, which is the intermediate formed during the glycerol dehydration. The rapid hydrogenation of acetol can shift the reaction equilibrium of glycerol dehydration forward resulting in a higher glycerol conversion. The improved reducibility of the catalyst by Pd allows the catalyst to be reduced in situ during the reaction preventing any loss of catalyst activity due to any potential oxidation of the catalyst. The catalyst was slightly deactivated when it was firstly recycled resulting in a 5.4% loss of glycerol conversion due to the aggregation of Cu and the deactivation became less noticeable upon further recycling.


Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 3844
Author(s):  
Lijuan Li ◽  
Bingdong Li ◽  
Liwei Feng ◽  
Xiaoqiu Zhang ◽  
Yuqian Zhang ◽  
...  

In this work, Au-modified F-TiO2 is developed as a simple and efficient photocatalyst for H2O2 production under ultraviolet light. The Au/F-TiO2 photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H2O2 synthesis, as in a pure TiO2 reaction system. The F− modification inhibits the H2O2 decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H2O2 production. We compared the activity of TiO2 with F− modification and without F− modification in the presence of Au, and found that the H2O2 production rate over Au/F-TiO2 reaches four times that of Au/TiO2. In situ electron spin resonance studies have shown that H2O2 is produced by stepwise single-electron oxygen reduction on the Au/F-TiO2 photocatalyst.


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