Production of hydrogen enriched syngas from municipal solid waste gasification with waste marble powder as a catalyst

Marble processing leads to the production of high amount of waste marble powder (WMP) as a byproduct, which can be a potential health risk and has hazardous impacts on the surrounding environment. However, marble is composed of calcite making it suitable for the calcium-based catalyst. Moreover, no study has been carried out to utilize this WMP in municipal solid waste (MSW) gasification process. Therefore, there is a need to address its utilization as a potential catalyst/sorbent in the gasification of municipal solid waste (MSW). A laboratory scale batch-type fixed bed reactor was used to study the effect of WMP addition on the CO₂ adsorption, steam reforming capability and char gasification in the presence of steam. Produced gas composition, gas yield, carbon conversion efficiency and tar yield were examined at different WMP to MSW ratios. Effect of temperature and steam rate varying from 700 to 900 °C and 2.5–10 ml/min respectively were also considered in this study. WMP showed a good capacity towards hydrogen enriched syngas production as well as CO₂ adsorption and tar reforming. The H₂ concentration increased significantly with an increase in the WMP to MSW mass ratio, while CO₂ decreased. A significant effect of temperature and steam rate was also observed on the produced gas composition, gas yield, and tar content. This study helps us to understand the effect of WMP addition in MSW gasification process and thus assists in the industrial application.     

Polyaniline sensitized Pt@TiO2 for visible-light-driven H2 generation

Polyaniline is a typical conducting polymer with high migration electron rate, good stability, eco-friendly properties, and high absorption coefficients for visible light. In the present study, polyaniline decorated Pt@TiO₂ for visible light-driven H₂ generation is reported for the first time. The above-mentioned nanocomposite is prepared through a simple oxidative-polymerization and characterized by infrared spectroscopy, transmission electron microscopy, X–ray diffraction, thermogravimetric analysis, and ultraviolet–visible diffuse reflectance spectra. Polyaniline modification improves the absorption of the nanocomposite in visible light region via a photosensitization effect similar to dye–sensitization but does not influence the crystal structure and size of Pt@TiO₂. The polyaniline modified Pt@TiO₂ exhibits a remarkable visible light activity (61.8 μmol h⁻¹ g⁻¹) and good stability for H₂ generation (with an average apparent quantum yield of 10.1%) with thioglycolic acid as an electron donor. This work provides new insights into using conducting polymers, including polyaniline, as a sensitizer to modify Pt@TiO₂ for visible-light hydrogen generation.     

Simulation and optimization of hydrogen production by steam reforming of natural gas for refining and petrochemical demands in Lebanon

Steam reforming of natural gas produces the majority of the world's hydrogen (H₂) and it is considered as a cost-effective method from a product yield and energy consumption point of view. In this work, we present a simulation and an optimization study of an industrial natural gas steam reforming process by using Aspen HYSYS and MATLAB software. All the parameters were optimized to successfully run a complete process including the hydrogen production zone units (reformer reactor, high temperature gas shift reactor HTS and low temperature gas shift reactor LTS) and the purification zone units (absorber and methanator). Optimum production of hydrogen (87,404 MT/year) was obtained by fixing the temperatures in the reformer and the gas shift reactors (HTS & LTS) at 900 °C, 500 °C and 200 °C respectively while maintaining a pressure of 7 atm, and a steam to carbon ratio (S/C) of 4. Moreover, ~99% of the undesired CO₂ and CO gases were removed in the purification zone and a reduction of energy consumption of 77.5% was reached in the heating and cooling units of the process.     

Nickel-loaded red mud catalyst for steam gasification of bamboo sawdust to produce hydrogen-rich syngas

Ni/red mud (RM) catalysts were prepared by wet impregnation and used in the catalytic steam gasification of bamboo sawdust (BS) to produce hydrogen-rich syngas. The system was optimized in terms of the amount of added nickel (10%), reaction temperature (800 °C), and catalyst placement (separately behind the BS). The maximum H₂ yield was 17.3% higher than that using pure RM catalyst and 43.8% higher than that of BS gasification alone, and the H₂/CO ratio in the syngas reached 7.82. This Ni/RM catalyst also retained good activity after six cycles in a double-stage fixed bed reactor. Analysis using X-ray fluorescence, X-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy, and other methods revealed that the interaction of Ni, Fe, and Mg in Ni/RM produced bimetallic compounds containing active sites, such as NiFe₂O₄, MgNiO₂, and NiO. This explains the good catalytic performance in the tar conversion during the gasification process.     

Characteristics and performance of the Co–CeO2 catalyst as a function of the promoter (La,Pr, and Zr) used in high temperature water gas shift reaction

The catalysts used to facilitate the water gas shift reaction (WGSR) are generally harmful to the environment. Therefore, catalysts that have high activity and stability in WGSR and do not pollute the environment need to be fabricated. Herein, three promoters (La, Pr, and Zr) are added into Co–CeO₂ (CoCe) catalyst to improve catalytic performance in a high temperature WGSR to produce high-purity hydrogen from waste-derived synthesis gas. Various techniques are employed to confirm the changes in the properties that affect the catalytic performance. The catalytic reaction is performed at a high gas hourly space velocity to screen the performance of the promoted CoCe catalysts. The CoCeZr catalyst shows the highest CO conversion (X_CO = 88% at 450 °C) due to its high Co dispersion and oxygen vacancy resulting from the addition of Zr to the CoCe catalyst; thus, it is most suitable for use in high temperature WGSR.     

Steam reforming of 1-methylnaphthalene over pure CeO2 under model coke oven gas conditions containing high H2S concentrations

Tar and H₂S are obstacles to the efficient production of H₂ from unused industrial gases and biomass gasification gases. Robust catalysts against tar and H₂S are required to produce H₂ from such resources. Herein, a stable steam reforming reaction is demonstrated over pure CeO₂ under reaction conditions consisting of ~2 vol% 1-methylnaphthalene and ~1000 ppm H₂S. The presence of H₂S significantly suppressed Ni/MgO/Al₂O₃ activity and increased carbon deposition, regardless of the steam to carbon (S/C) ratio. In contrast, the promotion or suppression of CeO₂ activity in the presence of H₂S was dependent on the S/C ratio. At S/C = 1.2, H₂S deactivated the CeO₂ catalyst and increased carbon deposition. Conversely, H₂S promoted the reforming reaction and decreased carbon deposition on CeO₂ at S/C ≥ 2.0. The results of this study clarify that pure CeO₂ exhibits outstanding and stable activity for the steam reforming reaction of 1-methylnaphthalene in the presence of H₂S by controlling the S/C of the inlet gas.     

HRT control as a strategy to enhance continuous hydrogen production from sugarcane juice under mesophilic and thermophilic conditions in AFBRs

The objective of this study was to evaluate the effects of hydraulic retention time (HRT) (8–1 h) on H₂ production from sugarcane juice (5000 mg COD L⁻¹) in mesophilic (30 °C, AFBR-30) and thermophilic (55 °C, AFBR-55) anaerobic fluidized bed reactors (AFBRs). At HRTs of 8 and 1 h in AFBR-30, the H₂ production rates were 60 and 116 mL H₂ h⁻¹ L⁻¹, the hydrogen yields were 0.60 and 0.10 mol H₂ mol⁻¹ hexose, and the highest bacterial diversities were 2.47 and 2.34, respectively. In AFBR-55, the decrease in the HRT from 8 to 1 h increased the hydrogen production rate to 501 mL H₂ h⁻¹ L⁻¹ at the HRT of 1 h. The maximum hydrogen yield of 1.52 mol H₂ mol⁻¹ hexose was observed at the HRT of 2 h and was associated with the lowest bacterial diversity (0.92) and highest bacterial dominance (0.52).     

Supercritical water gasification mechanism of polymer-containing oily sludge

In the offshore petroleum industry, polymer-containing oily sludge (PCOS) hinders oil extraction and causes tremendous hazards to the marine ecological environment. In this paper, an effective pretreatment method is proposed to break the adhesive structure of PCOS, and the experiments of supercritical water gasification are carried out under the influencing factors including residence time (5–30 min) and temperature (400–750 °C) in batch reactors. The increase of time and temperature all show great promoting effects on gas production. Polycyclic aromatic hydrocarbons, including naphthalene and phenanthrene, are considered as the main obstacles for a complete gasification. Carbon gasification efficiency (CE) reaches maximum of 95.82% at 750 °C, 23 MPa for 30 min, while naphthalene makes up 70% of the organic compounds in residual liquid products. The highest hydrogen yield of 19.79 (mol H₂/kg of PCOS) is observed in 750 °C for 25 min. A simplified reaction pathway is presented to describe the gaseous products (H₂, CO, CO₂, CH₄). Two intermediates are defined for describing the reaction process bases on the exhaustive study on organic matters in residual liquid products. The results show that the calculated data and the experimental data have a high degree of fit and tar formation reaction is finished within 10 min.     

Enhanced hydrogen storage performance of Cu3(BTC)2 in situ inserted with few-layer silicon-based nanosheets

Silicon-based nanosheets (SNS) were synthesised via a mild (60 °C) and time-saving (8 h) modified topochemical method. Then, Cu₃(BTC)₂ and SNS@Cu₃(BTC)₂ were successfully synthesised by microwave irradiation, and their characteristics and hydrogen storage performance were analysed by multiple techniques. The accordion-like SNS exhibited void spaces, a unique low buckled structure, and ultrathin, almost transparent, loosely stacked layers with a high specific surface area (362 m²/g). After in-situ synthesis with Cu₃(BTC)₂, the SNS compound achieved a high specific surface area (1526 m²/g), outstanding hydrogen storage performance (5.6 wt%), and a desirable hydrogen diffusion coefficient (10^?7). Thus, SNS doping improved the hydrogen storage performance of Cu₃(BTC)₂ by 64% through electron transfer reactions with Cu enabled by the unique composite nanostructure of SNS@Cu₃(BTC)₂. This study presents a promising method of synthesising SNS and porous composite materials for hydrogen storage.     

Determination of the potential of cyanobacterial strains for hydrogen production

Hydrogen (H₂) is a renewable, abundant, and nonpolluting source of energy. Photosynthetic organisms capture sunlight very efficiently and convert it into organic molecules. Cyanobacteria produce H₂ by breaking down organic compounds and water. In this study, biological H₂ was produced from various strains of cyanobacteria. Moreover, H₂ accumulation by Synechocystis sp. PCC 6803 was as high as 0.037 μmol/mg Chl/h within 120 h in the dark. The wild-type, filamentous, non-heterocystous cyanobacterium Desertifilum sp. IPPAS B-1220 was found to produce a maximum of 0.229 μmol/mg Chl/h in the gas phase within 166 h in the light, which was on par with the maximum yield reported in the literature. DCMU at 10 μM increased H₂ production by Desertifilum sp. IPPAS B-1220 by 1.5-fold to 0.348 μmol H₂/mg Chl/h. This is the first report on the capability of Desertifilum cyanobacterium to produce H₂.     

A strategy of mid-temperature natural gas based chemical looping reforming for hydrogen production

Steam methane reforming (SMR) needs the reaction heat at a temperature above 800 °C provided by the combustion of natural gas and suffers from adverse environmental impact and the hydrogen separated from other chemicals needs extra energy penalty. In order to avoid the expensive cost and high power consumption caused by capturing CO₂ after combustion in SMR, natural gas Chemical Looping Reforming (CLR) is proposed, where the chemical looping combustion of metal oxides replaced the direct combustion of NG to convert natural gas to hydrogen and carbon dioxide. Although CO₂ can be separated with less energy penalty when combustion, CLR still require higher temperature heat for the hydrogen production and cause the poor sintering of oxygen carriers (OC). Here, we report a high-rate hydrogen production and low-energy penalty of strategy by natural gas chemical-looping process with both metallic oxide reduction and metal oxidation coupled with steam. Fe₃O₄ is employed as an oxygen carrier. Different from the common chemical looping reforming, the double side reactions of both the reduction and oxidization enable to provide the hydrogen in the range of 500–600 °C under the atmospheric pressure. Furthermore, the CO₂ is absorbed and captured with reduction reaction simultaneously.Through the thermodynamic analysis and irreversibility analysis of hydrogen production by natural gas via chemical looping reforming at atmospheric pressure, we provide a possibility of hydrogen production from methane at moderate temperature. The reported results in this paper should be viewed as optimistic due to several idealized assumptions: Considering that the chemical looping reaction is carried out at the equilibrium temperature of 500 °C, and complete CO₂ capture can be achieved. It is assumed that the unreacted methane and hydrogen are completely separated by physical adsorption. This paper may have the potential of saving the natural gas consumption required to produce 1 m³ H₂ and reducing the cost of hydrogen production.     

Turning glycerol surplus into renewable syngas through glycerol steam reforming over a sol-gel Ni–Mo2C-Al2O3 catalyst

In this work, a sol-gel Ni–Mo₂C–Al₂O₃ catalyst is employed for the first time in the glycerol steam reforming for syngas production. Catalyst stability and activity are investigated in the temperature range of 550 °C–700 °C and time on stream up to 30 h. As reaction temperature increases, from 550 °C to 700 °C, H₂ yield boosts from 22% to 60%. The stability test, carried out at milder conditions (600 °C and Gas-Hourly Space-Velocity (GHSV) of 50,000 mL h⁻¹.g_cat⁻¹), shows high catalyst stability, up to 30 h, with final conversion, H₂ yield, and H₂/CO ratio of 95%, 53% and 1.95, respectively. Both virgin and spent catalysts have been characterized by a multitude of techniques, e.g., Atomic-Absorption spectroscopy, Raman spectroscopy, N₂-adsorption-desorption, and Transmission Electron Microscopy (TEM), among others. Regarding the spent catalysts, carbon deposits’ morphology becomes more graphitic as the reaction temperature increases, and the total coke formation is mitigated by increasing reaction temperature and lowering GHSV.     

Biomass gasification coupled with producer gas cleaning,bottling and HTS catalyst treatment for H2-rich gas production

The aim of the present study is to demonstrate the production of hydrogen-rich fuel gas from J. curcas residue cake. A comprehensive experimental study for the production of hydrogen rich fuel gas from J. curcas residue cake via downdraft gasification followed by high temperature water gas shift catalytic treatment has been carried out. The gasification experiments are performed at different equivalence ratios and performance of the process is reported in terms of producer gas composition & its calorific value, gas production rate and cold gas efficiency. The producer gas is cleaned of tar and particulate matters by passing it through venturi scrubber followed by sand bed filter. The clean producer gas is then compressed at 0.6 MPa and bottled into a gas cylinder. The bottled producer gas and a simulated mixture of producer gas are then subjected to high temperature shift (HTS) catalytic treatment for hydrogen enriched gas production. The effect of three different operating parameters GHSV, steam to CO ratio and reactor temperature on the product gas composition and CO conversion is reported. From the experimental study it is found that, the presence of oxygen in the bottled producer gas has affected the catalyst activity. Moreover, higher concentration of oxygen concentration in the bottled producer gas leads to the instantaneous deactivation of the HTS catalyst.     

Catalyst modification strategies to enhance the catalyst activity and stability during steam reforming of acetic acid for hydrogen production

A high energy content (∼122 MJ/kg H₂) and presence of hydrogen-bearing compounds abundance in nature make hydrogen forth runner candidate to fulfill future energy requirements. Biomass being abundant and carbon neutral is one of the promising source of hydrogen production. In addition, it also addresses agricultural waste disposal problems and will bring down our dependency on fossil fuel for energy requirements. Biomass-derived bio-oil can be an efficient way for hydrogen production. Acetic acid is the major component of bio-oil and has been extensively studied by the researchers round the globe as a test component of bio-oil for hydrogen generation. Hydrogen can be generated from acetic acid via catalytic steam reforming process which is thermodynamically feasible. A number of nickel-based catalysts have been reported. However, the coke deposition during reforming remains a major challenge. In this review, we have investigated all possible reactions during acetic acid steam reforming (AASR), which can cause coke deposition over the catalyst surface. Different operating parameters such as temperature and steam to carbon feed ratio affect not only the product distribution but also the carbon formation during the reaction. Present review elaborates effects of preparation methods, active metal catalyst including bimetallic catalysts, type of support and microstructure of catalysts on coke resistance behavior and catalyst stability during reforming reactions. The present study also focuses on the effects of a combination of a variety of alkali and alkaline earth metals (AAEM) promoters on coke deposition. Effect of specially designed reactors and the addition of oxygen on carbon deposition during AASR have also been analyzed. This review based on the available literature focuses mainly on the catalyst deactivation because of coke deposition, and possible strategies to minimize catalyst deactivation during AASR.     

Wind-powered 250 kW electrolyzer for dynamic hydrogen production: A pilot study

Alkaline water electrolysis is the most promising approach for the industrial production of green hydrogen. This study investigates the dynamic operational characteristics of an industrial-scale alkaline electrolyzer with a rated hydrogen production of 50 m³/h. Strategies for system control and equipment improvement in dynamic-mode alkaline electrolytic hydrogen production are discussed. The electrolyzer can operate over a 30%–100% rated power load, thereby facilitating high-purity (>99.5%) H₂ production, competitive DC energy efficiency (4.01–4.51 kW h/Nm³ H₂, i.e., 73.1%–65.0% LHV), and good gas–liquid fluid balance. A safe H₂ content of 2% in O₂ (50% LFL) can be guaranteed by adjusting the system pressure. In transient operation, the electrolyzer can realize minute-level power and pressure modulation with high accuracy. The results confirm that the proposed alkaline electrolyzer can absorb highly fluctuating energy output from renewables because of its capability to operate in a dynamic mode.     

Preparation and improvement of nickel catalyst supported ordered mesoporous spherical silica for thermocatalytic decomposition of methane

The thermocatalytic alteration of CH₄ into highly pure hydrogen and filaments of carbon was investigated on a series of Ni-catalysts with various contents (25, 40, 55, and 70 wt%) supported mesoporous spherical SiO₂. The silica with ordered structure and high specific surface area (1136 m²/g) was synthesized using the Stöber technique with TEOS as a silica precursor and CTAB as the template in a simple synthesis system of aqueous-phase. This technique led to the preparation of mesoporous spherical silica. The prepared samples were characterized using BET, TPR, XRD, TPO, and SEM analyses. The prepared catalysts with different nickel loading showed the BET surface area ranging from 225.0 to 725.7 m²/g. These results indicated that an increase in nickel content decreases the surface area and leads to a subsequent collapse of a pore structure. SEM analysis confirmed a spherical nanostructure of catalysts and revealed that with the increase in loading of Ni, the particle size enlarged, because of the agglomeration of the particles. The results implied that the high methane conversion of 54% obtained over the 55 wt% Ni/SiO₂ at 575 °C and this sample had higher stability at lower reaction temperature than the other prepared catalysts, slowly deactivation was observed for this catalyst at a period of 300 min of time on stream.     

Producing hydrogen from the fermentation of cheese whey and glycerol as cosubstrates in an anaerobic fluidized bed reactor

This study aimed to evaluate the effect of the organic loading rate (OLR) (60, 90, and 120 g Chemical Oxygen Demand (COD). L^?1. d^?1) on hydrogen production from cheese whey and glycerol fermentation as cosubstrates (50% cheese whey and 50% glycerol on a COD basis) in a thermophilic fluidized bed reactor (55 °C). The increase in the OLR to 90 gCOD.L^?1. d^?1 favored the hydrogen production rate (HPR) (3.9 L H₂. L^?1. d^?1) and hydrogen yield (HY) (1.7 mmol H₂. gCOD^?1_app) concomitant with the production of butyric and acetic acids. Employing 16S rRNA gene sequencing, the highest hydrogen production was related to the detection of Thermoanaerobacterium (34.9%), Pseudomonas (14.5%), and Clostridium (4.7%). Conversely, at 120 gCOD.L^?1. d^?1, HPR and HY decreased to 2.5 L H₂. L^?1. d^?1 and 0.8 mmol H₂. gCOD^?1_app, respectively, due to lactic acid production that was related to the genera Thermoanaerobacterium (50.91%) and Tumebacillus (23.56%). Cofermentation favored hydrogen production at higher OLRs than cheese whey single fermentation.     

Effect of ZrO2 on the performance of Co–CeO2 catalysts for hydrogen production from waste-derived synthesis gas using high-temperature water gas shift reaction

In this study, highly active and stable CeO₂, ZrO₂, and Zr_(1-x)Ce_(x)O₂-supported Co catalysts were prepared using the co-precipitation method for the high-temperature water gas shift reaction to produce hydrogen from waste-derived synthesis gas. The physicochemical properties of the catalysts were investigated by carrying out Brunauer-Emmet-Teller, X-ray diffraction, CO-chemisorption, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and H₂-temperature-programmed reduction measurements. With an increase in the ZrO₂ content, the surface area and reducibility of the catalysts increased, while the interaction between Co and the support and the dispersion of Co deteriorated. The Co–Zr_0.4Ce_0·6O₂ and Co–Zr_0.6Ce_0·4O₂ catalysts showed higher oxygen storage capacity than that of the others because of the distortion of the CeO₂ structure due to the substitution of Ce⁴⁺ by Zr⁴⁺. The Co–Zr_0.6Ce_0·4O₂ catalyst with high reducibility and oxygen storage capacity exhibited the best catalytic performance and stability among all the catalysts investigated in this study.     

Steam reforming of acetic acid for hydrogenproduction: Catalytic performances of Ni and Co supported on Ce0·75Zr0·25O2 catalysts

The catalytic steam reforming of acetic acid over both Ni/ and Co/Ce_0·75Zr_0·25O₂ (CZO) catalysts in the temperature range of 450–650 °C and steam-to-carbon molar ratios of 3–9 was studied. It was found that the complete acetic acid conversion was achieved for all the conditions investigated. Nevertheless, the C–C bond cleavage conversion was attained less than the acetic acid conversion at a given condition due to carbon deposition on the catalyst. However, hydrogen yield was obtained in the same trend as C–C bond cleavage conversion as well. The results revealed that the CZO as an active support prefers to promote the ketonization reaction to the C-C bond cleavage reaction at a lower temperature, and vice versa at a higher temperature. The Ni/CZO catalyst exhibits higher C–C bond cleavage conversion than the Co/CZO catalyst particularly at 650 °C whereas the Co/CZO catalyst is more active for ketonization reaction at low temperatures. However, as an increase in reaction temperature, the Co/CZO catalyst promotes ketonization reaction more pronouncedly toward aldol-condensation reaction thus giving rise to the carbon deposition. The results deduced from the effect of space velocity on the activity and product distribution suggested that the steam reforming of acetic acid over Ni/CZO catalyst is dominated by decomposition of acetic acid, while that of Co/CZO catalyst by ketonization reaction.     

Transition metal/carbon nanoparticle composite catalysts as platinum substitutes for bioelectrochemical hydrogen production using microbial electrolysis cells

Various metal nanoparticle catalysts supported on Vulcan XC-72 and carbon-nanomaterial-based catalysts were fabricated and compared and assessed as substitutes of platinum in microbial electrolysis cells (MECs). The metal-nanoparticle-loaded cathodes exhibited relatively better hydrogen production and electrochemical properties than cathodes coated with carbon nanoparticles (CNPs) and carbon nanotubes (CNTs) did. Catalysts containing Pt (alone or mixed with other metals) most effectively produced hydrogen in terms of overall conversion efficiency, followed by Ni alone or combined with other metals in the order: Pt/C (80.6%) > PtNi/C (76.8%) > PtCu/C (72.6%) > Ni/C (73.0%) > Cu/C (65.8%) > CNPs (47.0%) > CNTs (38.9%) > plain carbon felt (38.7%). Further, in terms of long-term catalytic stability, Ni-based catalysts degraded to a lesser extent over time than did the Cu/C catalyst (which showed the maximum degradation). Overall, the hydrogen generation efficiency, catalyst stability, and current density of the Ni-based catalysts were almost comparable to those of Pt catalysts. Thus, Ni is an effective and inexpensive alternative to Pt catalysts for hydrogen production by MECs.