大气压等离子体射流重整CH4-CO2制合成气

采用大气压等离子体射流,以CH₄和CO^₂直接作为放电气体进行常压下重整制合成气的实验研究,考察了等离子体射流的放电特征及放电距离、放电功率、原料气配比和流量对反应的影响。结果表明,该等离子体具有放电稳定、均匀的特征。重整反应的主要产物为合成气,只有少量的H₂O和积炭生成。优化的反应条件为放电距离为9mm,CH₄和CO₂的摩尔比为4/6。当原料气流量为1000mL/min,放电功率为88.4W时,CH4和CO₂的最高转化率为分别为94.99%和87.23%。甲烷和二氧化碳的转化率随放电功率的增加而增加,随流量的增加而减少。     

大气压等离子体射流重整CH_4-CO_2制合成气

采用大气压等离子体射流,以CH4和CO2直接作为放电气体进行常压下重整制合成气的实验研究,考察了等离子体射流的放电特征及放电距离、放电功率、原料气配比和流量对反应的影响。结果表明,该等离子体具有放电稳定、均匀的特征。重整反应的主要产物为合成气,只有少量的H2O和积炭生成。优化的反应条件为放电距离为9 mm,CH4和CO2的摩尔比为4/6。当原料气流量为1 000 mL/min,放电功率为88.4 W时,CH4和CO2的最高转化率为分别为94.99%和87.23%。甲烷和二氧化碳的转化率随放电功率的增加而增加,随流量的增加而减少。     

Water splitting in low-temperature ac plasmas at atmospheric pressure

Plasma-induced water splitting at atmospheric pressure has been studied with a novel fan-type Pt reactor and several tubular-type reactors: an all-quartz reactor, a glass reactor, and three metal reactors with Pt. Ni, and Fe as electrodes. Reaction products have been analyzed by using GC (gas chromatography) and Q-MS (quadrupole mass spectrometry). Optical emission spectroscopic studies of the process have been carried out by employing a CCD (charge-coupled device) detector. Water splitting with tubular quartz and glass reactors is probably non-catalytic. However, a heterogeneous catalytic function of surface of metal electrodes has been observed. The variation of hydrogen yield (Y_H) and energy efficiency (E_e) with operational parameters such as input voltages (U_in), flow rates of carrier gas (F_He), and concentrations of water (C_W) has been examined. Plasma-induced water splitting can be described with a kinetic equation of-dC_w/dt = kC_W ^0.2. The rate constants at 3.25 kV are 2.8 × 10⁻⁴, 3.5 × 10⁻³, and 3.4 × 10⁻² mol^0.8L^−0.8 min⁻¹ for tubular glass reactor, a tubular Pt reactor, and a fan-type Pt reactor, respectively. A CSTR (continuous-stirred tank reactor) and PFR (piston-flow reactor) model have been applied to a fan-type reactor and tubular reactor, respectively. A mechanism on the basis of optical emission spectroscopic data has been obtained comprising the energy transfer from excited carrier gas species to water molecules, which split via radicals of HO^·, O^·, and H^· to form H₂ and O₂. The fan-type Pt reactors exhibit highest activity and energy efficiency among the reactors tested. Higher yields of hydrogen are achieved at higher input voltages, low flow rates, and low concentrations of water (Y_H = 78 % at U_in of 3.75 kV, F_He of 20 mL/min, and C_W of 0.86 %). The energy efficiency exhibits an opposite trend (E_e = 6.1 % at U_in of 1.25 kV, F_He of 60 mL/min and C_W of 3.1 %).     

Carbon deposition in methane reforming with carbon dioxide

Coke formation in the dry reforming of methane was studied using a thermobalance (TG) and with a catalytic microreactor in the temperature range 800–950 K. Silica-supported and lanthana-supported nickel catalysts were examined. The effects of process variables such as temperature and gas composition (He dilution, CH₄/CO₂ ratio) on the coke formation rate were determined. The reactivity of H₂ on several kinds of carbon was also investigated. The morphology of the coke was studied by scanning electron microscopy (SEM). The induction times for coke formation were significantly affected by temperature and by the CO content in the feed gas. The results of catalytic tests were consistent with the TG measurements. The behaviour of SiO₂ and La₂O₃ supported Ni catalysts agree with a mechanism in which the lanthana support plays an important role in the carbon deposition.     

Zeolite-supported Ni catalyst for methane reforming with carbon dioxide

In the present work, we compare the catalytic behaviour, in the dry reforming of methane, of Ni-based Silicalite-1 type catalyst obtained by different post-synthesis treatments. The Silicalite-1 type material, used as Ni-support, has been treated in order to observe the role of the silanol groups on the Ni impregnation, and then on the overall catalyst performance. Among the applied treatments (ionic-exchange, calcinations and silylation), the silylation is the one that allows the formation of smaller and more reducible Ni-oxide species that not only improve the methane conversion but also reduce the deactivation of the catalyst, due to the coke deposition.     

Ultra-stable Ni catalysts for methane reforming by carbon dioxide

Methane reforming by carbon dioxide has been studied over ultra-stable Ni catalysts. The catalyst was characterized by XRD, IR and TEM and temperature programmed hydrogenation. The nickel–magnesia solid solution catalyst containing low nickel has shown excellent stability (>3000 h) and no carbon deposition in the methane reforming by carbon dioxide. It was also found that the small nickel metal particle interaction with support surface is effective for the inhibition of carbon formation.     

Effect of metal oxides on the reforming of methane with carbon dioxide

The effect of basic and rare earth metal oxides on the stability of nickel-based catalysts for the CO₂ reforming of CH₄ has been studied. The addition of metal oxides increased the stability of Ni-based catalysts and reversed the values of the reaction orders with respect to both CH₄ and CO₂. In the presence of metal oxides, the values of the reaction orders with respect to CO₂ partial pressure followed the same trend of catalyst stability.     

Catalytic reforming of methane by carbon dioxide over nickel-exchanged zeolite catalysts

A series of nickel-exchanged catalysts based on ZSM-5, USY, and Mordenite zeolites has been prepared by the ionic exchange method. The NiZeol catalysts have been characterized by XRD and BET. The exchange levels and nickel contents of the catalysts have been determined by chemical analysis. The acidity of the zeolite supports has been investigated using NH₃ adsorption microcalorimetry. The number of acidic sites was found to decrease according to the following sequence: HUSY > HZSM-5 > HMOR. The temperature programmed reduction studies showed that the most reducible catalyst is NiZSM-5. The Ni-exchanged zeolites presented good catalytic performance in the methane reforming by CO₂. At a temperature of 650°C, CH₄ conversions of 71 and 54% were achieved on NiUSY and NiZSM-5 respectively. At 400°C, CO₂ FTIR adsorption has shown that CO₂ decomposes into CO and oxygen on NiZSM-5 which explains its reactivity at such a low temperature, while no decomposition of this probe molecule was observed on the NiUSY catalyst. The catalytic performance was found to vary in the following sequence at 650°C: NiUSY > NiZSM-5 > NiMOR. Moreover, the catalytic performances were found to depend strongly on the CO₂/CH₄ ratio in the feed and were markedly improved for CO₂/CH₄ greater than 1.     

Optimization of equilibrium carbon dioxide methane reforming parameters by the Gibbs free energy minimization method

The thermodynamic equilibrium in the carbon dioxide conversion of methane is studied by Gibbs energy minimization. The curves that represent the dependences of the degree of coke formation, the content of methane and carbon dioxide in syngas, and the syngas module on the CO₂/CH₄ mole ratio in the initial mixture and on temperature at various pressures, are plotted. The regions in which the CO₂/CH₄ mole ratio is optimal for carbon dioxide conversion and no coke formation occurs, and which are characterized by a minimal content of methane and carbon dioxide in syngas, are revealed.     

Promotional effect of cerium on nickel-containing mesoporous silica for carbon dioxide reforming of methane

A series of Ce-promoted 6.7%Ni-containing mesoporous silica(Ce-Ni-Si O2)with varying Ce content(0.5%–4.8%)was prepared using the evaporation-induced self-assembly method.The characterization results showed that Ce and Ni species were homogeneously incorporated into the mesoporous silica matrix.The catalytic properties of these samples in the dry reforming of methane reaction revealed that the catalysts(e.g.,1.2%Ce-Ni-Si O2)containing highly dispersed small Ni particles exhibited excellent catalytic activity and long-term stability,which is attributed to the anchoring effect of the Ce and its ability to increase surface oxygen species concentration.     

水热法制备Ni-Sm/SiC催化剂甲烷二氧化碳重整性能的研究

通过水热法制备了Ni-Sm/SiC催化剂（Ni的含量固定为9%,钐的含量固定为5%）。采用XRD、BET、ICP、H₂-TPR、TG-DTA和TEM等技术对催化剂进行表征。对催化剂在甲烷二氧化碳重整反应中的催化活性、不同镍前驱体的影响、催化剂的积炭行为进行了研究。研究结果表明,水热法制备的Ni-Sm/SiC催化剂有着优异的催化活性、稳定性和抗积炭能力。不同镍前驱体对催化剂的性能没有影响。     

Convenient synthesis of ethylene carbonates from carbon dioxide and 1,2-diols at atmospheric pressure of carbon dioxide

An efficient and convenient synthesis of ethylene carbonates was achieved by the reaction of carbon dioxide with 1,2-diols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), followed by treatment with 1-bromobutane. This DBU-promoted transformation proceeded at an atmospheric pressure of carbon dioxide at 25 °C and gave ethylene carbonates in good yields.     

Development of Cu foam-based Ni catalyst for solar thermal reforming of methane with carbon dioxide

Using solar energy to produce syngas via the endothermic reforming of methane has been extensively investigated at the laboratory- and pilot plant-scales as a promising method of storing solar energy. One of the challenges to scaling up this process in a tubular reformer is to improve the reactor's performance, which is limited by mass and heat transfer issues. High thermal conductivity Cu foam was therefore used as a substrate to improve the catalyst's thermal conductivity during solar reforming. We also developed a method to coat the foam with the catalytically active component NiMg_3AlO_x. The Cu foam-based NiMg_3AlO_x performs better than catalysts supported on SiSiC foam, which is currently used as a substrate for solar-reforming catalysts, at high gas hourly space velocity(≥400,000 mL/(g·h)) or at low reaction temperatures(≤ 720 °C). The presence of a γ-Al_2O_3 intermediate layer improves the adhesion between the catalyst and substrate as well as the catalytic activity.     

Electrosynthesis of cyclic carbonates from epoxides and atmospheric pressure carbon dioxide

The use of CO(2) for the preparation of value-added compounds has dramatically increased due to increased global warming concerns. We herein report an electrochemical cell containing a copper cathode and a magnesium anode that effectively converts epoxides and carbon dioxide to cyclic carbonates under mild electrochemical conditions at atmospheric pressure.     

Highly efficient chemical fixations of carbon dioxide and carbon disulfide by cycloaddition to aziridine under atmospheric pressure

Cycloaddition of aziridine with carbon dioxide was successfully catalyzed by alkali metal halide or tetraalkylammonium halide to give the corresponding 5-membered cyclic urethane, 1,3-oxazolidin-2-one, selectively. The reaction can be performed at ambient temperature under atmospheric pressure. Analoguous reaction of aziridine with carbon disulfide also successfully gave the corresponding 5-membered cyclic dithiourethane, 1,3-thioxazolidine-2-thione.     

The effect of alkaline earth metal oxide on nickel catalyst for carbon dioxide reforming of methane

A study on the effect of alkaline earth metal oxide on the activity and stability of nickel catalyst for carbon dioxide reforming of methane was performed. When CaO, SrO, and BaO were used as supports, there was no difference in catalytic activity between the catalysts made by coprecipitation and impregnation. However, when MgO was used as a support, the catalyst prepared by coprecipitation showed superior activity than that made by impregnation. The higher activity of the catalyst made by coprecipitation was due to the formation of solid solution consisting of nickel and magnesium. The formation of the solid solution enhanced the dispersion of nickel and the resistance to coke formation.     

Nickel catalysts supported on MgO with different specific surface area for carbon dioxide reforming of methane

In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO₂, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO₂ exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 °C were mainly activated carbon species.     

Template in situ inducing dispersion of nickel on SBA-15 for methane reforming with carbon dioxide

Highly dispersed Ni/SBA-15 catalysts were prepared via template extraction with varying different extraction times (Ni/S-x, x = 0.5, 3.5, 6.5 h) for methane reforming with carbon dioxide. Based on the various characterization results and initial activity evaluation, Ni/S-3.5 h catalyst showed the best catalytic performance. Compared with the catalyst prepared via template calcination (Ni-S), Ni/S-3.5 h catalyst held steady with CH₄ and CO₂ conversions while those of the Ni-S catalyst respectively decreased by 15 and 11% during the long-term stability test at 700 °C for 50 h. As TEM and TG–DSC results confirmed, Ni particles in spent Ni/S-3.5 h catalyst stayed well-dispersed with size slightly increasing from an initial 3.9–4.1 nm and nearly no carbon deposition was observed. On the contrary, Ni-S catalyst was subjected to sintered metal particles (increased from 11.6 to 18 nm) and formed carbon fibers. The prominent resistance to sintering and coking over stable Ni/S-3.5 h catalyst was attributed to the high dispersion and strengthened metal-support interaction induced via the residual in situ templates.     

Carbon dioxide and methane adsorption at high pressure on activated carbon materials

Granular and monolith carbon materials were prepared from African palm shell by chemical activation with H₃PO₄, ZnCl₂ and CaCl₂ aqueous solutions of different concentrations. Adsorption capacity of carbon dioxide and methane were measured at 298 K and 4,500 kPa, and also of CO₂ at 273 K and 100 kPa, in a volumetric adsorption equipment. Correlations between the textural properties of the materials and the adsorption capacity for both gases were obtained from the experimental data. The results obtained show that the adsorption capacity of CO₂ and CH₄ increases with surface area, total pore volume and micropore volume of the activated carbons. Maximum adsorption values were: 5.77 mmol CO₂ g^?1 at 273 K and 100 kPa, and 17.44 mmol CO₂ g^?1 and 7.61 mmol CH₄ g^?1 both at 298 K and 4,500 kPa.     

纳米ZrO2的合成对负载Ni催化剂的CH4/CO2重整反应的影响

采用共沉淀法、醇热合成法和干法分别合成了纳米ZrO2（ZrO2 CP、ZrO2 ET和ZrO2 S）,用XRD、 BET、SEM等对其结构和表面性质进行表征,以CH4/CO2重整为探针反应研究了不同方法合成的纳米ZrO2负载Ni催化剂的催化性能,并与载体的物化性质进行了关联。实验结果表明,以干法合成的纳米介孔ZrO2 S具有较大的比表面积（133m2/g）和较好的孔径分布(4.9nm),Ni/ZrO2 S催化剂在CH4/CO2重整反应中表现出较好的催化性能。