Hydrogen production by aqueous-phase reforming of glycerol over Ni-B catalysts

A Ni-B amorphous alloy catalyst (AP Ni) was prepared and used in an aqueous-phase reforming (APR) of glycerol. Higher stability and higher selectivity towards H₂ were obtained when compared with Raney Ni. After 130 h’ on stream aqueous-phase reforming of glycerol, the amorphous Ni-B catalyst was transformed to hexagonal closed-packed (hcp) Ni crystallites. The high selectivity towards hydrogen and catalytic stability may be due to the formation of hcp Ni crystallites during reaction and the protection of B₂O₃. The AP Ni catalyst was found to be 35-50% more active in terms of the H₂ production rate and 17-31% more selective toward H₂ as compared to Raney Ni. The reforming reaction at different reaction temperature, feedstock concentration, feedstock flow rate and other biomass derivatives i.e., ethylene glycol and sorbitol, were also investigated over AP Ni catalyst.     

Hydrogen production via steam reforming of ethylene glycol over Attapulgite supported nickel catalysts

Steam reforming of ethylene glycol was investigated over Ni-based catalysts supported on Attapulgite (ATP; originating from Jiangsu (JS), Anhui, and Gansu (GS) provinces in China). N₂ adsorption–desorption, XRD, FTIR, H₂-TPR, NH₃-TPD, SEM, and TEM-EDS measurements were performed to analyze the catalyst properties. The results revealed that Ni/ATP_GS had the largest particle size (17.9 nm) and the highest reductive degree (98.0%). Consequently, Ni/ATP_GS showed the highest ethylene glycol conversion (97.2%) during the first 4 h of reaction. However, this catalyst showed the lowest H₂ yield (71.2%), possibly owing to large Ni particle sizes as well as ample surface acidic sites and acidity, leading to a high selectivity toward CH₄ (20.8%) and C₂H₄ (2.2%). In contrast, Ni/ATP_JS presented the highest H₂ yield (89.8%) owing to it having the smallest Ni particle sizes and lowest amount of surface acidic sites. Additionally, this catalyst showed the highest stability over 8 h of reaction. An examination of the spent catalysts revealed that Ni/ATP_JS possessed excellent antisintering and coking properties.     

Aqueous-phase reforming of biomass using various types of supported precious metal and raney-nickel catalysts for hydrogen production

Aqueous-phase reforming (APR) of real biomass was studied for production of hydrogen gas. Wheat straw, an abundant by-product from wheat production was used as representative lignocellulosic biomass. Wheat straw was hydrolyzed in an environmentally benign-sub critical water condition. APR experiments of wheat straw hydrolysates were performed using commercial catalysts which were made of Pt, Pd and Ru doped on carbon, activated carbon and alumina supports for production of hydrogen rich gas mixture. The activity and selectivity of two commercial raney-nickel catalysts were also monitored in terms of hydrogen production.     

Hydrogen production from sucrose via aqueous-phase reforming

Commercial sucrose was used to produce hydrogen in a combined approach of hydrogenation and aqueous phase reforming (APR). First a mixture of technical sorbitol/mannitol was produced by hydrogenating an aqueous solution of sucrose in a trickle bed reactor over 5 wt % Ru/C. The produced polyols were treated in a continuous reactor at 498 K and elevated pressure deploying a 2.5 wt % Pt/C catalyst to yield hydrogen. The highest hydrogen selectivity was 62%. No large differences were found when comparing a commercial available sorbitol to the technical sorbitol/mannitol mixture in terms of conversion levels and selectivity to the gas-phase products. This was accompanied by a similar distribution of products retained in the liquid phase. The efficiency of APR when utilizing Pt/C was found to be still insufficient for industrial implementation in terms of hydrogen production. Thus, additional efforts should be made to increase the obtained amounts of hydrogen per mole of converted sugar alcohols.     

Hydrogen production through the aqueous phase reforming of ethylene glycol over supported Pt-based bimetallic catalysts

The catalytic activities of supported Pt-based bimetallic catalysts (Pt-M) were studied for hydrogen production via aqueous phase reforming (APR) using a 10 wt% ethylene glycol solution. The catalysts and supports used were characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption, CO chemisorption, and temperature programmed reduction (TPR) techniques. It was found that the Pt–Mn (Pt:Mn = 1:1, molar ratio) bimetallic catalyst significantly enhanced the catalytic performances such as the hydrogen yield and hydrogen production when compared with monometallic catalysts and other bimetallic catalysts that were examined. The XRD and TPR studies confirmed the interaction between the Pt and Mn species, leading to the Pt–Mn alloys supported on CMK-3. Related to the effect of the type of support, the CMK-3 support demonstrated better performance than the commercial activated carbon and alumina. Accordingly, it can be understood that the better catalytic performance of the APR reaction over Pt–Mn/CMK-3 catalyst is dependent on the alloy effect as well as the structural properties and nature of support given by the addition of the second metal.     

Hydrogen production via the glycerol steam reforming reaction over nickel supported on alumina and lanthana-alumina catalysts

In the present work, a comparative study of Ni catalysts supported on commercially available alumina and lanthana-alumina carriers was undertaken for the glycerol steam reforming reaction (GSR). The supports and/or catalysts were characterized by PZC, BET, ICP, XRD, NH₃-TPD, CO₂-TPD, TPR and SEM. Carbon deposited on the catalytic surface was characterized by SEM, TPO and Raman. Concerning the Ni/LaAl sample it can be concluded that the presence of lanthana by: (a) facilitating the active species dispersion, (b) strengthening the interactions between nickel species and support, (c) increasing of the basic sites' population and redistributing the acid ones in terms of strength and density, provides a catalyst with improved performance for the GSR reaction, in terms of activity, H₂ production and long term stability. TPO and Raman indicate that the carbon on the Ni/LaAl catalyst was mostly amorphous and was deposited mainly on the support surface. For the Ni/Al catalyst, graphitic carbon was prevalent and likely covered its active sites.     

Biogas reforming for hydrogen production over nickel and cobalt bimetallic catalysts

Ni/Co bimetallic catalysts supported by commercial γ-Al₂O₃ modified with La₂O₃ for biogas reforming were prepared by conventional incipient wetness impregnation. The catalysts were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), BET surface area and porosity analysis (BET), H₂ temperature-programmed reduction (H₂-TPR), transmission electron microscopy (TEM) and thermogravimetry coupled to differential scanning calorimetry (TG–DSC). XRD and XPS analysis revealed that a Ni/Co alloy was formed in the bimetallic catalysts. The Ni/Co ratio could be adjusted to improve pore textural properties, which enhanced the metal particle dispersion and resulted in smaller metal particle size, and thus increased the catalytic activity and resistance to carbon deposition. The activity and stability of the catalysts for biogas reforming was tested at 800 °C, ambient pressure, GHSV of 6000 ml g_cat⁻¹ h⁻¹ and a CH₄/CO₂ molar ratio of 1 without dilute gas. Experimental results showed that the catalytic activity could be closely related to the Ni/Co ratio. The bimetallic catalyst 7Ni3Co/LaAl exhibited better catalytic and anti-coking performance due to smaller metal particles, higher metal dispersion, uniform pore distribution, surface enrichment of Co, as well as the synergetic effect between Ni and Co. During a 290 h stability test over the catalyst 7Ni3Co/LaAl, the average conversion of CH₄ and CO₂, selectivity to H₂ and CO, and ratio of H₂/CO were 93.7%, 94.0%, 94.9%, 97.8%, and 0.97, respectively. The average coking rate was 0.0946 mg g_cat⁻¹ h⁻¹.     

Hydrogen generation via ethanol steam reforming over Co/HAp catalysts

The catalytic activity of calcium hydroxyapatite (HAp) supported cobalt nanoparticles in ethanol steam reforming (SRE) was investigated. Co was supported on hydrothermally prepared HAp by incipient wetness impregnation method. Co/HAp catalysts were characterized through XRD, FT-IR and Raman spectroscopy, TEM, SEM/EDS, N₂ physisorption, TG and TPR-H₂. Results showed that spinel cobalt oxide is reduced to CoO and Co and these species are responsible for catalytic activity for hydrogen production via SRE process. The main reactions over Co/HAp are incomplete steam reforming and dehydrogenation of ethanol. Reforming experiment over pre-reduced sample indicated a negative impact of H₂ treatment on hydrogen production. The best catalytic properties (${\text{Y}}_{{\text{H}}_2}$ and C_EtOH) were obtained over 5%Co/HAp catalyst.     

Aqueous phase reforming of polyols for hydrogen production using supported PtFe bimetallic catalysts

3-D cubic ordered mesoporous carbon (CMK-9) supported PtFe bimetallic catalysts with a range of PtFe compositions were applied to the aqueous phase reforming (APR) of polyols for hydrogen production. The catalytic performance with respect to the polyol and support used was also studied. The catalysts and supports were characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM), N₂ sorption, temperature programmed reduction (TPR), and CO chemisorption techniques. The polyols investigated include ethylene glycol (EG), glycerol, xylitol, and sorbitol. It was found that the addition of Fe to the Pt/CMK-9 catalyst significantly improved catalytic performance, with the optimum Pt:Fe ratio for APR activity being 1:3. It was also observed that, in the PtFe (1:3) system, the CMK-9 support demonstrated better catalytic performance than commercially available activated carbon or alumina. In addition, the catalytic activity of the PtFe/CMK-9 catalyst was successfully increased by both the effect of the water-gas shift reaction, promoted by Fe addition to Pt, and by the structural properties and nature of the CMK-9 support. Moreover, the PtFe (1:3)/CMK-9 catalyst showed efficient catalytic activity for different biomass derivatives (EG, glycerol, xylitol, and sorbitol), with the activity decreasing with increase in the number of carbon atoms.     

Hydrogen production by ethanol steam reforming: A study of Co- and Ce-based catalysts over FeCrAlloy monoliths

Co- and Ce-based structured catalysts deposited on FeCrAlloy monoliths have been prepared. A new two-step strategy for coating the monolith is used: (i) first, a MgAl₂O₄ spinel layer is generated on the FeCrAlloy substrate, and (ii) then, Co and Ce are incorporated in two different molar ratios by the conventional wet impregnation method. The spinel layer is formed from a solution of colloidal alumina and Mg(NO₃)₂, with an apparent viscosity of around 3300 mPa s. The results indicate that a homogeneous spinel coating with excellent adherence is obtained after two immersions and a calcination at 700 °C. Both structured catalysts are active in the steam reforming of ethanol at 650 °C. The system with a Co/Ce molar ratio of 3.7 exhibits the best performance with a high stability. A complete ethanol conversion and a hydrogen selectivity of around 95% are obtained in two reaction cycles of 36 h each with intermediate regeneration.     

Hydrogen production from catalytic supercritical water reforming of glycerol with cobalt-based catalysts

Glycerol reforming under catalytic supercritical water at temperatures in the range of 723–848 K using Co catalyst deposited on various supports including ZrO₂, yttria-stabilized zirconia (YSZ), La₂O₃, γ-Al₂O₃, and α-Al₂O₃ was investigated. An increase in operating temperature promoted the continued increase in glycerol conversion; however, carbon formation causing system operation failure was observed for γ-Al₂O₃ and α-Al₂O₃ at high operating temperatures (i.e. 748–798 K). Co supported on YSZ provided the most efficient performance for hydrogen production. 10 wt.% Co loading on YSZ support was an optimum amount to enhance the reaction. The increase in glycerol conversion and reduction of the amount of liquid products were observed for lower weight hourly space velocity (WHSV), higher operating temperature or higher cobalt loading. On Co/YSZ catalyst, glycerol conversion of 0.94 and hydrogen yield of 3.72 was obtained with WHSV of 6.45 h⁻¹at 773 K.     

Hydrogen production from glycerin by steam reforming over nickel catalysts

Increasing biodiesel production has resulted in a glut of glycerin that has led to a precipitous drop in market prices. In this study, the use of glycerin as a biorenewable substrate for hydrogen production, using a steam reforming process, has been evaluated. Production of hydrogen from glycerin is environmentally friendly because it adds value to this byproduct generated from biodiesel plants. The study focuses on nickel-based catalysts with MgO, CeO₂, and TiO₂ supports. Catalysts were characterized with thermogravimetric analysis and X-ray diffraction techniques. Maximum hydrogen yield was obtained at 650 °C with MgO supported catalysts, which corresponds to 4 mol of H₂ out of 7 mol of stoichiometric maximum.     

Hydrogen production by iso-octane steam reforming over Cu catalysts supported on rare earth oxides (REOs)

The present work aims to investigate the steam reforming (SR) of liquid hydrocarbons toward hydrogen production, employing iso-octane as gasoline surrogate, over Cu catalysts supported on rare earth oxides (REOs). An extensive characterization study, involving X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR), is undertaken to correlate the structural, morphological and surface properties of catalysts with their reforming performance. Several parameters related to the effect of operation temperature (600–800 °C), steam/carbon ratio (1–3) and Cu loading (0–25 wt%) on the catalytic performance are investigated. The results reveal that the best performance is obtained over the Cu/CeO₂ catalysts at a steam/carbon ratio of 3; H₂ yields as high as ∼55% are obtained at the expense of CH₄ and higher hydrocarbons. Concerning the influence of oxide carries on reforming efficiency the following order, in terms of H₂ yield, is recorded: CeO₂ ? Nd₂O₃ > Gd₂O₃ > Sm₂O₃ ≈ Pr₆O₁₁ ≈ La₂O₃. However, a notable deterioration of Cu/CeO₂ catalyst is observed in long term stability tests, ascribed to carbon deposition and catalyst sintering.     

Pathways of ethanol steam reforming over ceria-supported catalysts

Ceria-supported Pt, Ir and Co catalysts are prepared herein by the deposition–precipitation method and investigated for their suitability in the steam reforming of ethanol (SRE) at a temperature range of 250–500 °C. SRE is tested in a fixed-bed reactor under an H₂O/EtOH molar ratio of 13 and 20,000 h⁻¹ GHSV. Possible pathways are proposed according to the assigned temperature window to understand the different catalysts attributed to specific reaction pathways. The Pt/CeO₂ catalyst shows the best carbon–carbon bond-breaking ability and the lowest complete ethanol conversion temperature of 300 °C. Acetone steam reforming over the Ir/CeO₂ catalyst at 400 °C promotes a hydrogen yield of up to 5.3. Lower reaction temperatures for the water–gas shift and acetone steam reforming are in evidence for the Co/CeO₂ catalyst, whereas the carbon deposition causes its deactivation at temperature over 500 °C.     

Biogas reforming over bimetallic PdNi catalysts supported on phosphorus-modified alumina

A series of bimetallic PdNi catalysts supported on alumina modified with different amounts of phosphorus (0.5-5 wt%) were prepared. The effect of phosphorus content on the structure, surface properties and catalytic behavior of supported PdNi catalysts in biogas reforming was studied. The physicochemical properties of the samples were characterized by using different techniques: N₂ adsorption-desorption isotherms, X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia (TPD), thermogravimetric and differential thermal analysis (TG/DTA) and scanning transmission electron microscopy (STEM). The catalytic properties of the catalysts were evaluated in the reaction of reforming of methane with CO₂. It was shown that increasing the P content (≥1 wt%) leads to agglomeration of the metal Ni particles, as well as to increase of the total acidity of the catalysts. Within bimetallic system, the PdNi catalyst with 0.5 wt% phosphorus showed the best performance and stability caused by the presence of highly dispersed nickel particles on the catalyst surface due to the strong interaction between supported species and alumina.     

Hydrogen production by autothermal reforming of methane over NiPd catalysts: Effect of support composition and preparation mode

NiPd/Ce_0.5Zr_0.5O₂/Al₂O₃ and NiPd/La₂O₃/Ce_0.5Zr_0.5O₂/Al₂O₃ catalysts were prepared by incipient wetness co-impregnation method or sequential impregnation method for autothermal reforming of methane (ATR of CH₄). The influence of the preparation mode, Ce_0.5Zr_0.5O₂ and La₂O₃ additives on the physicochemical properties of NiPd supported catalysts and the effect on their activity to produce hydrogen by ATR of CH₄ were investigated. Characterization of fresh and spent Ni-based catalysts by X-ray fluorescence spectroscopy, N₂ adsorption, X-ray diffraction, H₂ temperature-programmed reduction, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were performed. It was demonstrated that support composition determines NiO dispersion as well as reducibility of Ni species through different strength of Ni-support interaction. The preparation method modifies the phase composition and catalyst ability for reduction. The catalyst evolution under reaction conditions was studied. The NiO (∼15 nm) and NiPd alloy (∼18 nm) phases were observed in the spent catalysts. It was found that the Ni^o/NiO ratio can be regulated by support composition and preparation mode of catalysts. It is demonstrated that studied catalysts provide high methane conversion of 90–100%, CO yield of 55–85% and H₂ yield of 55–75% in ATR of CH₄ at 750–950 °C. The optimal composition and preparation method of catalyst were selected. The best ATR of CH₄ performance is provided by 10 Ni_0.5Pd/10Ce_0.5Zr_0.5O₂/Al₂O₃ catalyst prepared by Pd/Ni sequential impregnation method that can be associated with peculiarity of NiPd particles structure and the optimal ratio between NiO species with different ability for reduction.     

Toluene steam reforming over nickel based catalysts

Steam reforming of toluene (SRT) has been studied initially in eight nickel-based catalysts where nickel (10 wt%) was incorporated in different supports (olivine, Al2O3, MgO, LDH, ZrO₂, CeO₂ and natural sepiolite) by the incipient wetness impregnation method. Among them, nickel catalyst based on sepiolite exhibited a promising catalytic performance, with a high conversion of toluene (16%), high selectivity to hydrogen (68.4%) and low production of undesired by-products (CO, CH₄, ethylene and benzene) at low temperature (500 °C). On the other hand, the incorporation of Ni in the sepiolitic material by precipitation (PP) has been considered as alternative method to the incipient wetness impregnation method (IWI). PP method allowed to prepare a Ni-based catalyst with a very high activity (conversion of toluene ~100%), high selectivity to hydrogen (73%) and lower production of undesirable by-products (5% CO, 2% CH₄ and 0% C₆H₆) at 575 °C. In addition, catalytic deactivation due to coke deposition and nickel sinterization was clearly lower for the catalyst synthesized by PP. Characterization by different physicochemical techniques (XRD, TEM, BET surface area, ICP-OES, TPR and EA) showed that PP method allowed to obtain a sepiolite-based catalyst containing Ni with larger external surface area and smaller, highly dispersed and easily reducible Ni metal particles. The results here discussed show that the Ni incorporation method has a clear influence in the preparation of nickel catalyst supported on sepiolite with improved catalytic performance in the steam reforming of toluene.     

Hydrogen production by auto-thermal reforming of ethanol over nickel catalyst supported on mesoporous yttria-stabilized zirconia

Mesoporous yttria-stabilized zirconia (YSZ-X) supports with different Y/Zr molar ratio (X) were prepared by a sol–gel method. 20 wt% Ni catalysts supported on YSZ-X (X = 0, 0.1, 0.2, and 0.3) were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. The effect of Y/Zr molar ratio (X) on the catalytic performance of Ni/YSZ-X (X = 0, 0.1, 0.2, and 0.3) catalysts was investigated. Hydrogen selectivity and by-product distributions over the catalysts were different depending on the Y/Zr molar ratio (X). Hydrogen selectivity over Ni/YSZ-X (X = 0, 0.1, 0.2, and 0.3) catalysts showed a volcano-shaped curve with respect to Y/Zr molar ratio (X). Among the catalysts tested, Ni/YSZ-0.1 showed the best catalytic performance and the lowest carbon deposition in hydrogen production by auto-thermal reforming of ethanol. High reducibility and excellent structural stability of Ni/YSZ-0.1 catalyst were responsible for its superior catalytic performance.     

Hydrogen production by steam reforming of ethanol over Co/CeO2 catalysts: Effect of cobalt content

The Co/CeO₂ catalysts obtained by co-precipitation method were used in the steam reforming of ethanol (SRE). The influence of cobalt active phase content (15–29 wt%), the reaction temperature (420–600 °C) and H₂O/EtOH molar ratio (12/1 and 6/1) were examined. The physicochemical characterization revealed that the cobalt content of the catalyst influences the metal-support interaction which results in catalyst performance in SRE process. The differences between catalytic properties of the Co/CeO₂ catalysts with different metal loading in SRE process decayed at 500 °C for H₂O/EtOH = 12/1. The best performance among the tested catalysts showed the 29Co/CeO₂ catalyst with the highest cobalt content, exhibiting the highest ethanol conversion, selectivity to two most desirable products and the lowest selectivity to by-products in comparison with catalysts containing smaller amount of metal. Its catalytic properties results probably from its unique physicochemical properties, i.e this catalyst contains large amount of cobalt but the metal crystallites are relatively small. Regardless cobalt content, an increase in the water-to-ethanol molar ratio in the feed increased the concentration of hydrogen an carbon dioxide and decreased formation of carbon monoxide, acetone, aldehyde and ethylene.