Optimizing Hydrogen Production: Influence of Promoters in Methane Decomposition on Titania-Modified-Zirconia Supported Fe Catalyst.

This study addresses the pivotal challenge of hydrogen production through methane decomposition, offering a pathway to achieving clean energy goals. Investigating the utilization of titania-modified zirconia dual redox supports (10TiZr) in iron or doped iron-based catalysts for the CH4 decomposition reaction, our research involves a thorough characterization process. This includes analyses of the surface area porosity, X-ray diffraction, Raman-infrared spectroscopy, and temperature-programmed reduction/oxidation. The observed sustained enhancement in catalytic activity over extended durations suggests the in situ formation of catalytically active sites. The introduction of Co or Ni into the 30Fe/10TiZr catalyst leads to the generation of a higher density of reducible species. Furthermore, the Ni-promoted 30Fe/10TiZr catalyst exhibits a lower crystallinity, indicating superior dispersion. Notably, the cobalt-promoted 30Fe/10TiZr catalyst achieves over 80% CH4 conversion and H2 yield within 3 h. Additionally, the Ni-promoted 30Fe/10TiZr catalyst attains a remarkable 87% CH4 conversion and 82% H2 yield after 3 h of the continuous process.

Hydrogen Production via Methane Decomposition over Alumina Doped with Titanium Oxide-Supported Iron Catalyst for Various Calcination Temperatures.

The decomposition of methane has been chosen as an alternative method for producing hydrogen. In this study, 20 % Fe was used as the active metal part of the catalyst. To better comprehend the impact of the supporting catalytic properties, alumina and titania-alumina composite were investigated as supports. Iron-based catalysts were prepared by impregnation method and then calcined at different temperatures (300 °C, 500 °C, and 800 °C). The catalysts were examined at 800 °C under atmospheric pressure with a 15 mL/min total flow rate and 2 : 1 CH4 to N2 feed ratio. The textural and morphological characteristics of the fresh calcined and spent catalysts were investigated. The catalytic activity and stability data demonstrated that Fe supported over TiO2-Al2O3 calcined at 500 °C performed the best of all evaluated catalysts with a more than 80 % hydrogen yield. The Raman spectra result showed that graphitic carbon was produced for all used titanium dioxide catalysts. Moreover, according to transmission electron microscopy (TEM) results, the carbon deposited on the catalysts' surface is carbon nanotubes (CNT).

Alumina-Magnesia-Supported Ni for Hydrogen Production via the Dry Reforming of Methane: A Cost-Effective Catalyst System.

5Ni/MgO and 5Ni/γAl2O3 are pronounced in the line of cheap catalyst systems for the dry reforming of methane. However, the lower reducibility of 5Ni/MgO and the significant coke deposition over 5Ni/γAl2O3 limit their applicability as potential DRM catalysts. The mixing capacity of MgO and Al2O3 may overcome these limitations without increasing the catalyst cost. Herein, a 5Ni/xMg(100 - x)Al (x = 0, 20, 30, 60, 70, and 100 wt. %) catalyst system is prepared, investigated, and characterized with X-ray diffraction, surface area and porosity measurements, H2-temperature programmed reduction, UV-Vis-IR spectroscopy, Raman spectroscopy, thermogravimetry, and transmission electron microscopy. Upon the addition of 20 wt. % MgO into the Al2O3 support, 5Ni/20Mg80Al is expanded and carries both stable Ni sites (derived through the reduction of NiAl2O4) and a variety of CO2-interacting species. CH4 decomposition at Ni sites and the potential oxidation of carbon deposits by CO2-interacting species over 5Ni/20Mg80Al results in a higher 61% H2-yield (against ~55% H2-yield over 5Ni/γAl2O3) with an excellent carbon-resistant property. In the major magnesia support system, the 5Ni/60Mg40Al catalyst carries stable Ni sites derived from MgNiO2 and "strongly interacted NiO-species". The H2-yield over the 5Ni/60Mg40Al catalyst moves to 71%, even against a high coke deposition, indicating fine tuning between the carbon formation and diffusion rates. Ni dispersed over magnesia-alumina with weight ratios of 7/3 and 3/7 exhibit good resistance to coke. Weight ratios of 2/8 and 7/3 contain an adequate amount of reducible and CO2-interactive species responsible for producing over 60% of H2-yield. Weight ratio 6/4 has a proper coke diffusion mechanism in addition to achieving a maximum of 71% H2-yield.

Understanding Coke Deposition Vis-à-Vis DRM Activity over Magnesia-Alumina Supported Ni-Fe, Ni-Co, Ni-Ce, and Ni-Sr Catalysts.

The catalytic conversion of CH4 and CO2 into H2-rich syngas is known as the dry reforming of methane (DRM). The dissociation of CH4 over active sites, coupled with the oxidation or polymerization of CH4-x (x = 1-4), plays a crucial role in determining in determining the DRM product yield and coke deposition. Herein, a series of bimetallic-supported catalysts are prepared by the dispersion of Ni-M (M = Ce, Co, Fe, and Sr) over 60 wt% MgO-40 wt% Al2O3 (60Mg40Al) support. Catalysts are tested for DRM and characterized with XRD, surface area and porosity, temperature-programmed reduction/desorption, UV-VIS-Raman spectroscopy, and thermogravimetry. 2.5Ni2.5Sr/60Mg40Al and 2.5Ni2.5Fe/60Mg40Al, and 2.5Ni2.5Ce/60Mg40Al and 2.5Ni2.5Co/60Mg40Al have similar CO2 interaction profiles. The 2.5Ni2.5Sr/60Mg40Al catalyst nurtures inert-type coke, whereas 2.5Ni2.5Fe/60Mg40Al accelerates the deposition of huge coke, which results in catalytic inferiority. The higher activity over 2.5Ni2.5Ce/60Mg40Al is due to the instant lattice oxygen-endowing capacity for oxidizing coke. Retaining a high DRM activity (54% H2-yield) up to 24 h even against a huge coke deposition (weight loss 46%) over 2.5Ni2.5Co/60Mg40Al is due to the timely diffusion of coke far from the active sites or the mounting of active sites over the carbon nanotube.

Methane Decomposition to Hydrogen Over Zirconia-Supported Fe Catalysts-Effects of the Modified Support.

Methane decomposition is a promising route to synthesize COx -free hydrogen and carbon nanomaterials (CNMs ). In this work, the impregnation method was employed for the preparation of the catalysts. Systematic investigations on the activity and stability of Fe-based catalysts were carried out in a packed-bed micro-activity reactor at 800 °C with a feed gas flow rate of 18 mL/min. The effect of doping Y2 O3 , MgO, SiO2 and TiO2 over ZrO2 on the catalytic performance was also studied. BET revealed that the specific surface areas and pore volumes are increased after SiO2 , TiO2 , and Y2 O3 are added to ZrO2 while MgO had a negative impact and hence a little decrease in specific surface area is observed. The catalytic activity results showed that the Fe-based catalyst supported over TiO2 -doped ZrO2 that is, Fe-TiZr, demonstrated the highest activity and stability, with a maximum methane conversion of 81.3 % during 180 min time-on-stream. At 800 °C, a maximum initial methane conversion of 73 %, 38 %, 64 %, and 69 % and a final carbon yield of 121 wt. %, 55 wt. %, 354 wt. %, and 174 wt. % was achieved using Fe-MgZr, Fe-SiZr, Fe-TiZr and Fe-YZr catalysts, respectively. Moreover, bulk deposition of uniform carbon nanotubes with a high degree of graphitization and different diameters was observed over the catalysts.

Effect of Holmium Oxide Loading on Nickel Catalyst Supported on Yttria-Stabilized Zirconia in Methane Dry Reforming.

The carbon dioxide reforming of methane has attracted attention from researchers owing to its possibility of both mitigating the hazards of reactants and producing useful chemical intermediates. In this framework, the activity of the nickel-based catalysts, supported by yttria-stabilized zirconia and promoted with holmium oxide (Ho2O3), was assessed in carbon dioxide reforming of methane at 800 °C. The catalysts were characterized by N2-physisorption, H2 temperature-programmed reduction, temperature-programmed desorption of CO2, X-ray diffraction, scanning electron microscopy (SEM) together with energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) techniques. The effect of holmium oxide weight percent loading (0.0, 1.0, 2.0, 3,0, 4.0, and 5.0 wt %) was examined owing to its impact on the developed catalysts. The optimum loading of Ho2O3 was found to be 4.0 wt %, where the methane and carbon dioxide conversions were 85 and 91%, respectively. The nitrogen adsorption-desorption isotherms specified the mesoporous aspect of the catalysts, while the SEM images displayed a morphology of agglomerated, porous particles. The TEM images of the spent catalyst displayed the formation of multiwalled carbon nanotubes. TGA of the 4.0 wt % of Ho2O3 catalyst, experimented over 7-hour time-on-stream, displayed little weight loss (<14.0 wt %) owing to carbon formation, indicating the good resistance of the catalyst to carbon accumulation due to the enhancing ability of Ho2O3 and its adjustment of the support.

Modification of CeNi0.9Zr0.1O3 Perovskite Catalyst by Partially Substituting Yttrium with Zirconia in Dry Reforming of Methane.

Methane Dry Reforming is one of the means of producing syngas. CeNi0.9Zr0.1O3 catalyst and its modification with yttrium were investigated for CO2 reforming of methane. The experiment was performed at 800 °C to examine the effect of yttrium loading on catalyst activity, stability, and H2/CO ratio. The catalyst activity increased with an increase in yttrium loading with CeNi0.9Zr0.01Y0.09O3 catalyst demonstrating the best activity with CH4 conversion >85% and CO2 conversion >90% while the stability increased with increases in zirconium loading. The specific surface area of samples ranged from 1−9 m2/g with a pore size of 12−29 nm. The samples all showed type IV isotherms. The XRD peaks confirmed the formation of a monoclinic phase of zirconium and the well-crystallized structure of the perovskite catalyst. The Temperature Program Reduction analysis (TPR) showed a peak at low-temperature region for the yttrium doped catalyst while the un-modified perovskite catalyst (CeNi0.9Zr0.1O3) showed a slight shift to a moderate temperature region in the TPR profile. The Thermogravimetric analysis (TGA) curve showed a weight loss step in the range of 500−700 °C, with CeNi0.9Zr0.1O3 having the least carbon with a weight loss of 20%.

Hydrogen production from CO2 reforming of methane using zirconia supported nickel catalyst.

The use of hydrogen as an alternative fuel is an attractive and promising technology as it contributes to the reduction of environmentally harmful gases. Finding environmentally friendly cheap active metal-based catalysts for H2 rich syngas via dry reforming of methane (DRM) for industrial applications has posed a challenge. In this paper, H2 production via CO2 reforming of methane was investigated over 5Ni/ZrO2 catalysts. The catalytic performance of all prepared catalysts was evaluated in a microtubular fixed bed reactor under similar reaction conditions (i.e., activation temperature at 700 °C, feed flow rate of 70 ml min-1, reaction temperature 700 °C for 440 min reaction time) of CO2 reforming of methane. Different characterization techniques such as; BET, CO2-TPD, TGA, XRPD, Raman, and TEM, were used. The study of the textural properties of catalysts established that the BET of pristine catalyst (5NiZr) was enhanced by the addition of modifiers and promoters. A bimodal TPR distribution in the reduction temperature range of 250-550 °C was recorded. In the CO2-TPD analysis, the strength of basicity came in this order: 5Ni15YZr > 5Ni10YZr > 5Ni5YZr > 5NiZr > 5Ni20YZr. The investigation of catalyst modifiers (MgO and Y2O3) resulted in the Y2O3 modifier improving the activity and catalytic performance better than MgO, which generated a hydrogen yield of 22%. 15% Y2O3 modifier loading gave the highest H2 yield 53% in the phase of different loadings of yttria. The study of the influence of promoters (Cs, Ga, and Sr) revealed that the catalytic performance of 5Ni15YZr catalysts promoted with Sr towards the H2 yield enhanced the activity to 62%. The promoted catalysts displayed lower carbon deposition compared to the unpromoted catalyst, which provided 25.6 wt% weight loss.

Yttria Modified ZrO2 Supported Ni Catalysts for CO2 Reforming of Methane: The Role of Ce Promoter.

Yttria modified zirconia (YZ) supported on 5 wt % of Ni-based catalysts promoted with ceria (1-3 wt %) were prepared by the impregnation process to investigate their performance for dry reforming of methane. The reforming reactions, conducted at 700 °C and at atmospheric pressure using a CO2/CH4/N2 fixed feed ratio of 3/3/1, with a total flow rate of 70 mL/min, revealed that the ceria-promoted catalysts (xCe-Ni-YZ; x = 1-3 wt %) enhanced the CH4 and CO2 conversions as compared to the reference catalyst (Ni-YZ). A CO2 conversion of 85% was exhibited by the 3Ce-Ni-YZ catalyst. Despite increased conversions, xCe-Ni-YZ catalysts showed more amounts of carbon deposition as evidenced by the values of TGA, and hence were found to be less stable as compared to the reference Ni-YZ catalyst. The used and fresh catalysts were characterized by BET, H2-TPR, XRD, TEM, Raman, TPD, and TGA. TEM images displayed nanoparticle sizes of Ni in the fresh catalysts, while carbon filaments were formed on the spent catalysts. The CO2-TPD, H2-TPR, and BET results revealed the existence of only weak and moderate basic sites, the increase of total hydrogen consumption, and the surface area values with the addition of the Ce promoter, respectively. The TGA analysis showed that the Ce promoter increased the carbon deposition, while the Raman results indicated the dominance of crystallinity due to the graphitized carbon.

Prospective production of fructose and single cell protein from date palm waste

BACKGROUND: Fructose and single cell protein are important products for the food market. Abundant amounts of low-grade dates worldwide are annually wasted. In this study, highly concentrated fructose syrups and single cell protein were obtained through selective fermentation of date extracts by Saccharomyces cerevisiae. RESULTS: The effect of air flow (0.1, 0.5, 0.75, 1, 1.25 and 1.5 vvm) and pH (4.5, 4.8, 5, 5.3 and 5.6) was investigated. Higher air flow led to lower fructose yield. The optimum cell mass production of 10 g/L was achieved at air flow of 1.25 vvm with the fructose yield of 91%. Similar cell mass production was obtained in the range pH of 5.0­5.6, while less cell mass was obtained at pH less than 5. Controlling the pH at 4.5, 5.0 and 5.3 failed to improve the production of cell mass which were 5.6, 5.9 and 5.4 g/L respectively; however, better fructose yield was obtained. CONCLUSIONS: Extension of the modified Gompertz enabled excellent predictions of the cell mass, fructose production and fructose fraction. The proposed model was also successfully validated against data from literatures. Thus, the model will be useful for wide application of biological processes.

Promotional effect of magnesium oxide for a stable nickel-based catalyst in dry reforming of methane.

The generation of synthesis gas (hydrogen and carbon monoxide mixture) from two global warming gases of carbon dioxide and methane via dry reforming is environmentally crucial and for the chemical industry as well. Herein, magnesium-promoted NiO supported on mesoporous zirconia, 5Ni/xMg-ZrO2 (x = 0, 3, 5, 7 wt%) were prepared by wet impregnation method and then were tested for syngas production via dry reforming of methane. The reaction temperature at 800 °C was found more catalytically active than that at 700 °C due to the endothermic feature of reaction which promotes efficient CH4 catalytic decomposition over Ni and Ni-Zr interface as confirmed by CH4-TSPR experiment. NiO-MgO solid solution interacted with ZrO2 support was found crucial and the reason for high CH4 and CO2 conversions. The highest catalyst stability of the 5Ni/3Mg-ZrO2 catalyst was explained by the ability of CO2 to partially oxidize the carbon deposit over the surface of the catalyst. A mole ratio of hydrogen to carbon monoxide near unity (H2/CO ~ 1) was obtained over 5Ni/ZrO2 and 5Ni/5Mg-ZrO2, implying the important role of basic sites. Our approach opens doors for designing cheap and stable dry reforming catalysts from two potent greenhouse gases which could be of great interest for many industrial applications, including syngas production and other value-added chemicals.

Kinetic modeling of the simultaneous production of ethanol and fructose by Saccharomyces cerevisiae

Background: Ethanol and fructose are two important industrial products that enjoy many uses. In this contribution, their production via selective fermentation of date extract using Saccharomyces cerevisiae was studied. Scaling up the process for possible commercialization was investigated in three fermentors with working volume ratio of 1:40:400. Results: Higher ethanol concentration was obtained in the larger fermentor due to conversion of fructose. Fructose yields in the 0.5-L, 7.5-L and 80-L fermentors were 99, 92 and 90%, respectively. Good fitting was obtained with the modified Monod kinetics; however, a better fit of cell mass was obtained with the modified Ghose­Tyagi model which accounts for ethanol inhibition. Conclusions: The modified Gompertz model was expanded to facilitate prediction of products' formation and fructose fractions in all three fermentors. Such expansion will be beneficial in industrial applications.

Selectivity of layered double hydroxides and their derivative mixed metal oxides as sorbents of hydrogen sulfide.

In the context of finding high efficient sorbent materials for removing hydrogen sulfide (H2S) from air stream, a screening study was performed to find the best combination of metals for the synthesis of layered double hydroxides (LDHs) and their derivative mixed metal oxides. Based on selectivity of 998 natural mineral species of sulfur-containing compounds, Cu(2+), Ni(2+) and Zn(2+) were selected as divalent metals, and Fe(3+), Al(3+) and Cr(3+) as trivalent metals to synthesis the LDHs sorbents. 10 LDHs materials and their calcined mixed metal oxides, Ni(0.66)Al(0.34), Cu(0.35)Ni(0.32)Al(0.33), Zn(0.66)Al(0.34), Cu(0.36)Zn(0.32)Al(0.32), Ni(0.64)Fe(0.36), Cu(0.35)Ni(0.31)Fe(0.34), Ni(0.66)Cr(0.34), Cu(0.35)Ni(0.31)Cr(0.34), Zn(0.66)Cr(0.34), Cu(0.33)Zn(0.32)Cr(0.35) were synthesized, characterized chemically and physically, and then tested using breakthrough test to determine their sulfur uptake. Ni(0.64)Fe(0.36) mixed metal oxides was found to have the best uptake of hydrogen sulfide (136 mg H2S/g). Regeneration of spent Ni(0.64)Fe(0.36) mixed metal oxides was studied using two different mixture solutions, NaCl/NaOH and acetate-buffer/NaCl/NaOH. The latter mixture successfully desorbed the sulfur from the Ni0.64Fe0.36 sorbent for 2 cycles of regeneration/sorption.