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.     

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.     

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.     

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.     

Effect of manifold injection of hydrogen gas in producer gas and neem biodiesel fueled CRDI dual fuel engine

The high flammability of hydrogen gas gives it a steady flow without throttling in engines while operating. Such engines also include different induction/injection methods. Hydrogen fuels are encouraging fuel for applications of diesel engines in dual fuel mode operation. Engines operating with dual fuel can replace pilot injection of liquid fuel with gaseous fuels, significantly being eco-friendly. Lower particulate matter (PM) and nitrogen oxides (NO_x) emissions are the significant advantages of operating with dual fuel.Consequently, fuels used in the present work are renewable and can generate power for different applications. Hydrogen being gaseous fuel acts as an alternative and shows fascinating use along with diesel to operate the engines with lower emissions. Such engines can also be operated either by injection or induction on compression of gaseous fuels for combustion by initiating with the pilot amount of biodiesel. Present work highlights the experimental investigation conducted on dual fuel mode operation of diesel engine using Neem Oil Methyl Ester (NeOME) and producer gas with enriched hydrogen gas combination. Experiments were performed at four different manifold hydrogen gas injection timings of TDC, 5°aTDC, 10°aTDC and 15°aTDC and three injection durations of 30°CA, 60°CA, and 90°CA. Compared to baseline operation, improvement in engine performance was evaluated in combustion and its emission characteristics. Current experimental investigations revealed that the 10°aTDC hydrogen manifold injection with 60°CA injection duration showed better performance. The BTE of diesel + PG and NeOME + PG operation was found to be 28% and 23%, respectively, and the emissions level were reduced to 25.4%, 14.6%, 54.6%, and 26.8% for CO, HC, smoke, and NO_x, respectively.     

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.     

Performance evaluation of a solarized gas turbine system integrated to a high temperature electrolyzer for hydrogen production

In this paper, the performance of a solar gas turbine (SGT) system integrated to a high temperature electrolyzer (HTE) to generate hybrid electrical power and hydrogen fuel is analyzed. The idea behind this design is to mitigate the losses in the electrical power transmission and use the enthalpy of exhaust gases released from the gas turbine (GT) to make steam for the HTE. In this context, a GT system is coupled with a solar tower including heliostat solar field and central receiver to generate electrical power. To make steam for the HTE, a flameless boiler is integrated to the SGT system applying the SGT extremely high temperature exhaust gases as the oxidizer. The results indicate that by increasing the solar receiver outlet temperature from 800 K to 1300 K, the solar share increases from 22.1% to 42.38% and the overall fuel consumption of the plant reduces from 7 kg/s to 2.7 kg/s. Furthermore, flameless mode is achievable in the boiler while the turbine inlet temperature (TIT) is maintained at the temperatures higher than 1314 K. Using constant amounts of the SGT electrical power, the HTE voltage decreases by enhancing the HTE steam temperature which result in the augmentation of the overall hydrogen production. To increase the HTE steam temperature from 950 K to 1350 K, the rate of fuel consumption in the flameless boiler increases from 0.1 m/s to 0.8 m/s; however, since the HTE hydrogen production increases from 4.24 mol/s to 16 mol/s it can be interpreted that the higher steam temperatures would be affordable. The presented hybrid system in this paper can be employed to perform more thermochemical analyses to achieve insightful understanding of the hybrid electrical power-hydrogen production systems.     

Renewable-powered hydrogen economy from Australia's perspective

This article broadly reviews the state-of-the-art technologies for hydrogen production routes, and methods of renewable integration. It outlines the main techno-economic enabler factors for Australia to transform and lead the regional energy market. Two main categories for competitive and commercial-scale hydrogen production routes in Australia are identified: 1) electrolysis powered by renewable, and 2) fossil fuel cracking via steam methane reforming (SMR) or coal gasification which must be coupled with carbon capture and sequestration (CCS). It is reported that Australia is able to competitively lower the levelized cost of hydrogen (LCOH) to a record $(1.88–2.30)/kg_H2 for SMR technologies, and $(2.02–2.47)/kg_H2 for black-coal gasification technologies. Comparatively, the LCOH via electrolysis technologies is in the range of $(4.78–5.84)/kg_H2 for the alkaline electrolysis (AE) and $(6.08–7.43)/kg_H2 for the proton exchange membrane (PEM) counterparts. Nevertheless, hydrogen production must be linked to the right infrastructure in transport-storage-conversion to demonstrate appealing business models.     

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.     

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.     

Determination of fuel utilisation and recirculated gas composition in dead-ended PEMFC systems

This work presents a fundamental theory and methods for understanding the gas composition dynamics in PEMFC anode fuel supply compartments operated dead-ended with recirculation. The methods are applied to measurement data obtained from a PEMFC system operated with a 1 kW short stack.We show how fuel utilisation and stack efficiency, two key factors determining how well a fuel supply system performs, are coupled through the anode gas composition.The developed methods allow determination of the anode fuel supply molar balance, giving access to the membrane crossover rates and the extent of recirculated gas exchanged to fresh fuel during a purge. A methane tracer gas is also evaluated for estimating fuel impurity enrichment ratios.The above theory and methods may be applied in modelling and experimental research activities related to defining hydrogen fuel quality standards, as well as for developing more efficient and robust PEMFC system operation strategies.     

Production of syngas from steam gasification of three different ranks of coals and related reaction kinetics

The steam gasification properties of three different ranks of coals, Shengli lignite (SL), Shenhua subbituminous coal (SH), and Tavan Tolgoi anthracite (TT), were investigated using a lab-scale fixed-bed reactor, and the thermodynamic equilibrium constant and kinetics of the reaction were analyzed. The results showed that the aromaticity and condensation of aromatic structures in SL, SH, and TT became higher, and the maturity of organic substance became lower. The steam gasification reaction showed that the syngas from low-rank SL had a high H₂/CO molar ratio, while the syngas from high-rank TT had relatively high CO content. The direct carbon gasification reactions for these three different ranks of coals were far from in equilibrium; the water gas shift reaction of SL was near equilibrium, and the degree of reaction for SL was higher than that of SH and TT. We studied a random pore model (RPM), shrinking core model (SCM), and hybrid model (HM), and the hybrid model was found to be the most suitable model of the three for fitting the steam gasification reactions of the three types of coal. It had high fitting correlation coefficient R² values (ranging from 0.9939 to 0.9990) and small average error θ values (ranging from 0.009 to 0.016). The apparent activation energy E values of SL, SH, and TT fitted by HM were 179.10, 48.14, and 63.06 kJ/mol, respectively, and the corresponding pre-exponential factor k₀ values were 3.14 × 10⁷, 1.01, and 1.22 min⁻¹, respectively. This study finds that the steam gasification of SL, SH, and TT coal samples consists of homogeneous phase reaction and shrinking core reaction.     

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.     

Hydrogen-rich syngas production by gasification of Urea-formaldehyde plastics in supercritical water

Supercritical water is a promising medium to convert plastics into hydrogen and other recyclable products efficiently. In previous research, supercritical water gasification characteristics investigations focus on thermoplastics instead of thermoset plastics due to its chemical, thermal and mechanical stability. Urea-formaldehyde (UF) plastics were selected as a typical kind of thermoset plastics for investigation in this paper and quartz tubes were used as the reactor in order to avoid the potential catalytic effect of metal reactor wall. Conversion characteristic were studied and the influence of different operating parameters such as temperature, reaction time, feedstock mass fraction and pressure were investigated respectively. The molar fraction of hydrogen could reach about 70% in 700 °C. Products in gas phase and solid phase were analyzed, and properties, chemical structures and inhibition mechanism of thermoset plastics was analyzed after comparing with polystyrene (PS) plastics. The result showed that increase of high temperature and long reaction time could promote gasification process, meanwhile the increase in the feedstock mass fraction would result in suppression of the gasification process. Finally, kinetic study of UF was carried out and the activation energy and pre-exponential factor of the Arrhenius equation were calculated as 30.09 ± 1.62 kJ/mol and 0.1199 ± 0.0049 min⁻¹, respectively.     

Preparation of gas standards for quality assurance of hydrogen fuel

This study has developed traceable standards for evaluating impurities in hydrogen fuel according to ISO 14687. Impurities in raw H₂, including sub μmol/mol levels of CO, CO₂, and CH₄, were analyzed using multiple detectors while avoiding contamination. The gravimetric standards prepared included mixtures of the following nominal concentrations: 1, 2, 3–5, 8–11, 17–23, and 47–65 μmol/mol for CO₂, CH₄ and CO, O₂, N₂, Ar, and He, respectively. The expanded uncertainty ranges were 0.8% for Ar, N₂, and He, 1% for CH₄ and CO, and 2% for CO₂ and O₂. These standards were stable, while that for CO varied by only 0.5% during a time span of three years. The prepared standards are useful for evaluating the compliance of H₂ fuel in service stations with ISO 14687 quality requirements.     

Energy efficient hydrogen drying and purification for fuel cell vehicles

High-purity standards are required for hydrogen used in fuel cell vehicles. The relative abundance of contaminants is highly influenced by the production pathway. Hydrogen obtained from water electrolysis presents three main pollutants: Nitrogen, Oxygen and Water. Herein, the engineering and implementation of removal techniques in a commercial 50 kW alkaline electrolyzer are reported. The full system was characterized with various analytical techniques including gas chromatography and mass spectrometry. A reduction of contaminant levels compatible with ISO 14687:2019 standard was achieved. From cold start, 100 min of operation are required to reach the desired nitrogen levels. Oxygen was removed in one step with a catalytic converter. Drying of hydrogen was achieved by using an innovative vacuum assisted pressure swing adsorption system. Sub-ppm levels of water are obtained with a power consumption of only 0.5 kWh/kg H₂ and 98.4% of product recovery.     

Review of hydrogen economy in Malaysia and its way forward

Heavy fossil fuels consumption has raised concerns over the energy security and climate change while hydrogen is regarded as the fuel of future to decarbonize global energy use. Hydrogen is commonly used as feedstocks in chemical industries and has a wide range of energy applications such as vehicle fuel, boiler fuel, and energy storage. However, the development of hydrogen energy in Malaysia is sluggish despite the predefined targets in hydrogen roadmap. This paper aims to study the future directions of hydrogen economy in Malaysia considering a variety of hydrogen applications. The potential approaches for hydrogen production, storage, distribution and application in Malaysia have been reviewed and the challenges of hydrogen economy are discussed. A conceptual framework for the accomplishment of hydrogen economy has been proposed where renewable hydrogen could penetrate Malaysia market in three phases. In the first phase, the market should aim to utilize the hydrogen as feedstock for chemical industries. Once the hydrogen production side is matured in the second phase, hydrogen should be used as fuel in internal combustion engines or burners. In the final phase hydrogen should be used as fuel for automobiles (using fuel cell), fuel-cell combined heat and power (CHP) and as energy storage.     

A comparison of ignition characteristics of slurry fuels prepared using coal processing waste and finely divided coal

The scientific novelty of the research is that for the first time differences in the conditions and characteristics of the ignition and burning of droplets of slurries prepared on the basis of coals and waste from their enrichment have been established. The practical significance of the research results is that they illustrate the prospects of utilization of the numerous coal enrichment wastes by combustion in the composition of aqueous slurries with the generation of a rather large amount of energy and a relatively small negative environmental impact. The most significant characteristics were compared: the limiting (minimum) temperature; the ignition delay times; the maximum combustion temperature; the concentration of the main gas anthropogenic emissions. It has been found that fuel mixtures prepared from wet waste of coal flotation are characterized by higher inertia and ignition temperatures compared to slurries with high-quality coal dust. However, the established differences considering the availability and low cost of filter cakes illustrate the prospects of waste derived fuel combustion. The combustion heat of the investigated slurries based on coal and filter cake with addition of petroleum products differs by no more than 5–30%. The average difference between the duration of ignition for fuel droplets based on dust and filter cake of coking and low-caking coals is about 20%. At that the addition of waste turbine oil (10% wt.) into the filter cake reduces the duration of ignition by 12–25% and the ignition temperature – by 10–15 °C without a significant increase in anthropogenic gas emissions. The difference between the minimum ignition temperatures of coal and waste coal based slurries was from 10 °C to 80 °C. On environmental and economic indicators, coal waste is more attractive than coal.     

Pollutant emissions,performance and combustion behaviour assessment of an Si gas engine fuelled with Lcv gas containing carbon monoxide and hydrogen diluted by nitrogen

This paper includes the experimental test data of an SI engine fuelled with simulated LCV gas (Low Calorific Value), which resembles synthesis gas in composition. The LCV gas was simulated by a mixture of carbon monoxide, hydrogen and nitrogen. During the experiment, the lower heating value of the LCV gas was altered by dilution with nitrogen. A single-cylinder Honda GX270 engine was adopted in the experiment to assess the impact of LCV gas on the system performance. This engine is typically used to power various machines and for electrical energy production in small generator sets. A modified engine was connected to an electric generator, which was loaded with an electric resistor. Engine operation was controlled using a microprocessor controller. All tests were performed at constant engine speed (3000 rpm). The engine was working at wide-open throttle for all mixtures. All mixtures were burned at stoichiometric conditions and with fixed value of ignition timing (30 deg bTDC). The indicated performance of the SI engine was evaluated based on the in-cylinder pressure measurements. No significant impact on the main internal parameters of the tested SI engine fuelled with simulated LCV gas diluted by nitrogen was observed. The experimental tests showed that the combustion duration increased for the mixtures with higher content of inert gas. Increase in the LHV raised the specific emissions of NO_x and decreased specific emissions of CO and HC.     

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.