In situ carbon nanotube synthesis by the reduction of NiO/γ-Al_2O_3 catalyst in methane

The synthesis of carbon nanotubes (CNTs) via chemical vapour deposition of methane on NiO/γ-Al2O3 catalyst has been investigated.The reduction behavior of NiO/γ-Al2O3 by methane was studied using thermogravimetric (TG) and X-ray diffraction (XRD) techniques.It was found that the NiO supported on γ-Al2O3,was reduced to Ni0 in methane atmosphere in the temperature range of 710-770℃.The catalytic activity of NiO/γ-Al2O3 for CNTs synthesis by in situ chemical vapour deposition of methane during the reduction was also investigated.Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the CNTs produced at various reduction temperatures.The results indicated that the reduction temperature exhibits obvious influence on the morphology and the yield of CNTs.CNTs with the diameter of about 20 nm were obtained at reduction temperature of 750℃,and higher reduction temperature (such as 800 and 850℃) led to an increase in CNTs diameter and a decrease in CNTs yield.     

A parametric study of methane decomposition into carbon nanotubes over 8Co-2Mo/Al2O3 catalyst

The effects of reaction temperature, partial pressure of methane, catalyst weight and gas hourly space velocity (GHSV) on methane decomposition were reported. The decomposition reaction was performed in a vertical fixed-bed reactor over 8Co-2Mo/Al 2 O 3 catalyst. The experimental results show that these four process parameters studied had vital effects on carbon yield. As revealed by the electron microscopy and Raman spectroscopy analyses, the reaction temperature and GHSV governed the average diameter, the diameter distribution and the degree of graphitization of the synthesized carbon nanotubes (CNTs). Also, an evidence is presented to show that higher temperatures and higher GHSV favored the formation of better-graphitized CNTs with larger diameters.     

Effects of pretreatment and reduction on the Co/Al2O3 catalyst for CO hydrogenation

The purpose of this study was to investigate the effect of preadsorbed CO at different temperatures, calcination temperatures, the combined influence of reduction temperature and time, and pretreatment using hydrogen or syngas as reduction agents on the F-T synthesis （FTS） activity and selectivity of Co/Al2O3 catalyst. The reactivity of the carbon species at higher preadsorption temperature with H2 in TPSR decreased, whereas the carbon-containing species showed higher reactivity over Co/Al2O3 catalyst with low calcination temperature. This agreed well with the order of catalytic activity for F-T synthesis on this catalyst. The catalytic activity of the catalyst varied with reduction temperature and time remarkably. CODEX optimization gave an optimum reduction temperature of 756 K and reduction time of 6.2 h and estimated C5＋ yield perfectly. The pretreatment of Co/Al2O3 catalyst with different reduction agents （hydrogen or syngas） showed important influences on the catalytic performance. A high CO conversion and C5＋ yield were obtained on the catalyst reduced by hydrogen, whereas methane selectivity on the catalyst reduced by syngas was much higher than that on the catalyst reduced by hydrogen.     

Doping effects of manganese on the catalytic performance and structure of NiMgO catalysts for controllabe synthesis of multi-walled carbon nanotubes

Doping effects of manganese （Mn） on catalytic performance and structure evolution of NiMgO catalysts for synthesis of multi-walled carbon nanotubes （MWCNTs） from methane were investigated for the first time. Addition of Mn in NiMgO catalyst can greatly improve the MWCNTs yield. Mno.2NiMgO catalyst among the tested ones gives the highest MWCNTs yield as 2244%, which is two times higher than that of the catalyst without Mn. The structure evolution, reduction behaviors and surface chemical properties of MnNiMgO catalysts with various Mn contents were studied in detail. It was found that the stable solid solution of NiMgO2 formed in NiMgO catalyst was disturbed by the addition of Mn. Instead, another solid solution of MnMg608 is formed. More amount of Ni can be reduced and dispersed on the catalyst surface to be acted as active sites. Importantly, the changes of Ni content on the surface are correlated with the Ni particle size and the outer diameter of MWCNTs, suggesting the controllable synthesis of MWCNTs over MnNiMgO catalysts.     

The Effect of Nb Loading on Catalytic Properties of Ni/Ce0.75Zr0.25O2 Catalyst for Methane Partial Oxidation

In this study,the effect of Nb loading on the catalytic activity of Ce_(0.75)Zr_(0.25)O_2-supported Ni catalysts was studied for methane partial oxidation.The catalysts were characterized by BET,H_2 chemisorption,XRD,TPR,TEM and tested for methane partial oxidation to syngas in the temperature range of 400-800℃at atmospheric pressure.The results showed that the activity of methane partial oxidation on the catalysts was apparently dependent on Nb loading.It seemed that the addition of Nb lowered the catalytic activity for methane partial oxidation and increased the extent of carbon deposition. This might be due to the strong interaction between NiO and Nb-modified support and reduction of surface oxygen reducibility.     

Effect of synthesis solution pH of Co/γ-Al_2O_3 catalyst on its catalytic properties for methane conversion to syngas

The cobalt nanoparticles over γ-Al_2O_3 support were prepared via chemical reduction of CoCl_2·6H_2O using NaBH_4 with various values of pH in the range of 11. 92-13. 80. Synthesized catalysts were studied through X-ray diffraction( XRD),N_2 adsorption/desorption( BET),H_2-temperature programmed reduction( H_2-TPR),H_2-chemisorption,O_2 pulse titration and temperature programmed oxidation( TPO) methods. Obtained results exhibited the synthesis solution pH showed a significant influence on the activity and selectivity in partial oxidation of methane reaction. The methane conversion,CO selectivity and H_2 yield were enhanced by increasing of the synthesis solution pH. Compared to other catalysts,the catalyst that synthesized at pH of 13.80,showed a superior ability in syngas production with a H_2/CO ratio of near 2 and also a proper stability against deactivation during the partial oxidation of methane.     

Solar chemical looping reforming of methane combined with isothermal H_2O/CO_2 splitting using ceria oxygen carrier for syngas production

The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO_2/CeO_(2-δ)) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and methane to syngas in the temperature range 900–1050 °C. Experiments were carried out with different ceria shapes via two-step redox cycling composed of endothermic partial reduction of ceria with methane and complete exothermic re-oxidation of reduced ceria with H_2 O/CO_2 at the same operating temperature, thereby demonstrating the capability to operate the cycle isothermally. A parametric study considering different ceria macrostructure variants(ceria packed powder, ceria packed powder mixed with inert Al_2 O_3 particles, and ceria reticulated porous foam) and operating parameters(methane flow-rate, reduction temperature, or sintering temperature) was conducted in order to unravel their impact on the bed-averaged oxygen non-stoichiometry(δ), syngas yield, methane conversion, and solar reactor performance. The ceria cycling stability was also experimentally investigated to demonstrate repeatable syngas production by alternating the flow between CH_4 and H_2 O(or CO_2). A decrease in sintering temperature of the ceria foam was beneficial for increasing syngas selectivity, methane conversion,and reactor performance. Increasing both CH_4 concentration and reduction temperature enhanced δ with the maximum value up to 0.41 but concomitantly favored CH_4 cracking reaction. The ceria reticulated porous foam showed better performance in terms of effective heat transfer, due to volumetric absorption of concentrated solar radiation and uniform heating with lower solar power consumption, thereby promoting the solar-to-fuel energy conversion efficiency that reached up to 5.60%. The energy upgrade factor achieved during cycle was up to 1.19. Stable patterns in the δ and syngas yield for consecutive cycles with the ceria foam validated material performance stability.     

Syngas production by combined carbon dioxide reforming and partial oxidation of methane over Ni/α-Al2O3 catalysts

Ni/α-Al2O3 catalysts were found to be active in the temperature range 600~900 ℃ for both CO2 reforming and partial oxidation of methane. The effects of Ni loading, reaction temperature and feed gas ratio for the combination of CO2 reforming and partial oxidation of CH4 over Ni/α-Al2O3 were investigated. Catalysts of xwt%Ni/α-Al2O3 (x = 2.5, 5, 8 and 12) were prepared by wet impregnating the calcined support with a solution of nickel nitrate. XRD patterns and activity tests have verified that the 5wt%Ni/α-Al2O3 was the most active catalyst, as compared with the other prepared catalyst samples. An increase of the Ni loading to more than 5 wt% led to a reduction in the Ni dispersion. In addition, by combining the endothermic carbon dioxide reforming reaction with the exothermic partial oxidation reaction, the loss of catalyst activity with time on stream was reduced with the amount of oxygen added to the feed.     

柠檬酸用量对碳纳米管制备的影响

Carbon nanotubes (CNTs) were prepared by chemical vapor catalytic deposition using the catalyst prepared by citric acid complexometry. The effect of the dosage of citric acid on the CNTs yield and morphologywas studied. The transmission electron microscopy and X-ray diffraction were used to characterize CNTs morphology and crystal structures of the catalysts, respectively. The results show that the dosage of citric acid can greatly affect the CNTs yield and morphology: the CNTs have a high yield about 1 345.8% (1 h) at a 2∶1 molar ratio of citric acid and metal ion, and the obtained CNTs diameter is relatively narrow distributed (25～30 nm); when themolar ratio of citric acidto metal ion is 3∶1, the CNTs yield is about 407.2% (1 h), and the obtained CNTs diameter is relatively wide distributed (25～50 nm), moreover, the CNTs is more rough than that obtained with 2∶1 molar ratio of citric acid to metal ion.     

Effect of Ni Loading and Reaction Conditions on Partial Oxidation of Methane to Syngas

The partial oxidation of methane to synthesis gas is studied in this paper over Ni/Al2O3 catalysts under atmospheric pressure. The effects of Ni loading on the activity and stability of catalysts with 5 mm α-Al2O3 and θ-Al2O3 pellets as supports were measured in a continuous fixed bed reactor. It is found that the optimum Ni loading is 10%. And the effect of reaction conditions on partial oxidation of methane is also studied. The methane conversion and CO selectivity increase with the increase of the reaction temperature and the space velocity on 10%Ni/α-Al2O3 catalysts. The best CH4/O2 mole ratio is 2 for CO selectivity, and the optimum space velocity is 5.4x105 h-1.     

Preparation of Carbon Nanotubes with High Yield and Narrow Diameter Distribution from C2H2 over LaCu0.2Ni0.8Ox

Carbon nanotubes (CNTs) were prepared by decomposition of C2H2 over newly developed LaCu0.2Ni0.8Ox in the temperature range from 600 to 850℃. The effect of the reaction temperature on the yield of CNTs was investigated in detail. At 680℃,the yield of CNTs reaches 17g/g.catal, or so. The morphology of CNTs was examined by TEM. The diameter of CNTs rangs from 9 nm to 14 nm.     

Comparing the deactivation behaviour of Co/CNT and Co/γ-Al2O3 nano catalysts in Fischer-Tropsch synthesis

An extensive study of Fischer-Tropsch (FT) synthesis on cobalt nano particles supported on γ-alumina and carbon nanotubes (CNTs) catalysts is reported.20 wt% of cobalt is loaded on the supports by impregnation method.The deactivation of the two catalysts was studied at 220 C,2 MPa and 2.7 L/h feed flow rate using a fixed bed micro-reactor.The calcined fresh and used catalysts were characterized extensively and different sources of catalyst deactivation were identified.Formation of cobalt-support mixed oxides in the form of xCoO yAl2O3 and cobalt aluminates formation were the main sources of the Co/γ-Al2O3 catalyst deactivation.However sintering and cluster growth of cobalt nano particles are the main sources of the Co/CNTs catalyst deactivation.In the case of the Co/γ-Al2O3 catalyst,after 720 h on stream of continuous FT synthesis the average cobalt nano particles diameter increased from 15.9 to 18.4 nm,whereas,under the same reaction conditions the average cobalt nano particles diameter of the Co/CNTs increased from 11.2 to 17.8 nm.Although,the initial FT activity of the Co/CNTs was 26% higher than that of the Co/γ-Al2O3,the FT activity over the Co/CNTs after 720 h on stream decreased by 49% and that over the Co/γ-Al2O3 by 32%.For the Co/γ-Al2O3 catalyst 6.7% of total activity loss and for the Co/CNTs catalyst 11.6% of total activity loss cannot be recovered after regeneration of the catalyst at the same conditions of the first regeneration step.It is concluded that using CNTs as cobalt catalyst support is beneficial in carbon utilization as compared to γ-Al2O3 support,but the Co/CNTs catalyst is more susceptible for deactivation.     

Effect of calcination temperature on structure and performance of Ni/TiO2-SiO2 catalyst for CO2 reforming of methane

The influence of calcination temperature on the structure and catalytic behavior of Ni/TiO2-SiO2 catalyst, for CO2 reforming of methane to synthesis gas under atmospheric pressure, was investigated. The results showed that the Ni/TiO2-SiO2 catalyst calcined at 700 ℃ had high and stable activity while the catalysts calcined at 550 and 850 ℃ had low and unstable activity. Depending on the calcination temperature, one, two, or three of the following Ni-containing species, NiO, Ni2.44Ti0.72Si0.07O4, and NiTiO3 were identified by combining the temperature programmed reduction （TPR） and X-ray diffraction （XRD） results. Their reducibility decreased in the sequence： NiO〉Ni2.44Ti0.72Si0.07O4〉NiTiO3. It suggests that high and stable activities observed over the Ni/TiO2-SiO2 catalyst calcined at 700 ~C were induced by the formation of Ni2.44Ti0.72Si0.07O4 and smaller NiO species crystallite size.     

Utilization of compressed natural gas for the production of carbon nanotubes

The present work aims at utilizing compressed natural gas (CNG) as carbon source for the synthesis of carbon nanotubes (CNTs) over CoOMoO/Al2O3 catalyst via catalytic chemical vapor deposition (CCVD) method. The as-produced carbonaceous product was characterized by thermal gravimetric analyzer (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The experimental finding shows that CNTs were successfully produced from CNG while carbon nanofibers (CNFs) were formed as the side products. In addition, the catalytic activity and lifetime were found sustained and prolonged, as compared with using high purity methane as carbon source. The present study suggests an alternative route which can effectively produce CNTs and CNFs using low cost CNG.     

Methane Decomposition into Carbon Fibers over Coprecipitated Nickel-Based Catalysts

Decomposition of methane in the presence of coprecipitated nickel-based catalysts to produce carbon fibers was investigated. The reaction was studied in the temperature range of 773 K to 1073 K. At 1023 K, the catalytic activities of three catalysts kept high at the initial period and then decreased with the reaction time. The lifetimes of Ni-Cu-Al and Ni-La-Al catalysts are longer than that of Ni-Al catalyst. With three catalysts, the yield of carbon fibers was very low at 773 K. The yield of carbon fibers for Ni-La-Al catalyst was more than those for Ni-Al and Ni-Cu-Al catalysts. For Ni-La-Al catalyst, the elevation of temperature from 873 K up to 1073 K led gradually to an increase in the yield of carbon fibers. XRD studies on the Ni-La-Al catalyst indicate that La2NiO4 was formed. The formation of La2NiO4 is responsible for the increase in the catalytic lifetime and the yield of carbon fibers synthesized on Ni-La-Al at 773 1073 K. Carbon fibers synthesized on Ni-Al catalyst are thin, long carbon nanotubes. There are bamboo-shaped carbon fibers synthesized on Ni-Cu-Al catalyst. Carbon fibers synthesized on Ni-La-Al catalyst have large hollow core, thin wall and good graphitization.     

CNTs tuning and vertical alignment in anodic aluminium oxide membrane

Anodic aluminium oxide (AAOM) membranes were used for template growth of carbon nanotubes (CNT) inside their pores by chemical vapour deposition (CVD) of different hydrocarbons, in the absence of transition metal catalyst. A composite material, containing one nanotube for each channel, having the same length as the membrane thickness and the external diameter close to the diameter of the membrane holes, was obtained. Yield, selectivity, and quality of CNTs in terms of diameter (up to very thin CNT), carbon order, length, arrangement (i.e. number of tubes for each channel), purity, that are critical requisites for several applications were optimized by investigating the effect of changing the hydrocarbon feedstock gas, also in the presence of hydrogen. The samples produced using methane as a feedstock have a well ordered structure. The role of the alumina channels surface during the CNT growth has been investigated and its catalytic activity has been proved for the first time.     

多壁碳纳米管包裹Fe3C单晶纳米线的初步研究

Multi-walled carbon nanotubes were fabricated by chemical vapor deposition with acetylene as carbon source and titanate modified palygorskite as catalyst at high temperature. A part of as-grown nanotubes was partially filled with foreign material in the shape of nanowire by transmission electron microscopy (TEM) observations. The en-capsulated nanowires was single crystalline iron carbide upon selected area electron diffraction(SAED)patterns and X-ray energy dispersive spectrum (EDS) results. Thermal gravimetric analyses (TGA) on the as-grown samples indicated that the yield of carbon nanotubes was largest at 750℃ and the content of amorphous carbon decreased with increasing temperature. Furthermore， the growth mechanism was discussed on the experimental results in the paper.     

微波等离子体化学气相沉积法低温制备直纳米碳管膜

Among the three main methods for the synthesis of carbon nanotubes (CNTs)， chemical vapor deposition (CVD) has received a great deal of attention since CNTs can be synthesized at significantly low temperature. Plasma chemical vapor deposition methods can synthesize CNTs at lower temperature than thermal CVD. But in the usual catalytic growth of CNTs by CVD， CNTs are often tangled together and have some defects. These will limit the property research and potential applications. How to synthesize the straight CNTs at low temperature becomes a challenging issue. In this letter， straight carbon nanotube (CNT) films were achieved by microwave plasma chemical vapor deposition (MWPCVD) catalyzed by round Fe-Co-Ni alloy particles on Ni substrate at 610℃. It was found that， in our experimental condition， the uniform growth rate along the circumference of round alloy particles plays a very important role in the growth of straight CNT films. And because the substrate is conducting， the straight CNT films grown at low temperature may have the benefit for property research and offer the possibility to use them in the future applications.     

Low-temperature utilization of CO2 and CH4 by combining partial oxidation with reforming of methane over Ru-based catalysts

Combination of partial oxidation of methane (POM) with carbon dioxide reforming of methane (CRM) has been studied over Ru-based catalysts at 550 ℃. POM, CRM and combined reaction were performed over 8wt%Ru/γ-Al2O3 and the results show that both POM and CRM contribute to the combined reaction, between which POM plays a more important role. Moreover, the addition of Ce to Ru-based catalyst results in an improvement in the activity and CO selectivity under the adopted reaction conditions. The Ce-doped catalyst was characterized by N2 adsorption-desorption, SEM, XRD, TPR, XPS and in situ DRIFTS. The mechanism has been studied by in situ DRIFTS together with the temperature distribution of catalyst bed. The mechanism of the combined reaction is more complicated and it is the combination of POM and CRM mechanisms in nature. The present paper provides a new catalytic system to activate CH4 and CO2 at a rather low temperature.     

COx-Free Hydrogen and Carbon Nanofibers Produced from Direct Decomposition of Methane on Nickel-Based Catalysts

Direct decomposition of methane was carried out using a fixed-bed reactor at 700℃for the production of COx-free hydrogen and carbon nanofibers. The catalytic performance of NiO-M/SiO2 catalysts (where M=AgO, CoO, CuO, FeO, MnOx and MoO) in methane decomposition was investigated. The experimental results indicate that among the tested catalysts, NiO/SiO2 promoted with CuO give the highest hydrogen yield. In addition, the examination of the most suitable catalyst support, including Al2O3, CeO2, La2O3, SiO2, and TiO2, shows that the decomposition of methane over NiO-CuO favors SiO2 support. Furthermore, the optimum ratio of NiO to CuO on SiO2 support for methane decomposition was determined. The experimental results show that the optimum weight ratio of NiO to CuO fell at 8:2 (w/w) since the highest yield of hydrogen was obtained over this catalyst.