Greenhouse gas reduction in oil sands upgrading and extraction operations with thermochemical hydrogen production

This paper examines various methods of reducing CO₂ emissions by a thermochemical copper–chlorine (Cu–Cl) cycle of hydrogen production, for in-situ extraction and upgrading of bitumen to synthetic crude oil in Alberta’s oil sands. Particular focus is given to Canada’s SCWR (Supercritical Water-cooled Reactor) as a nuclear heat source for the Cu–Cl cycle, although other heat sources such as solar or industrial waste heat can be utilized. The feasibility of steam generation from supercritical water of a SCWR power plant is examined for bitumen extraction, as well as hydrogen production for bitumen upgrading via an integrated Cu–Cl cycle with SCWR. The heat requirements for bitumen extraction from the oil sands, and the hydrogen requirements for bitumen upgrading, are examined. A new layout of oil sands upgrading operations with integrated SCWR and a Cu–Cl cycle is presented. The reduction of CO₂ emissions due to the integrated SCWR and Cu–Cl cycle is quantitatively investigated based on the expected bitumen production capacity over the next two decades.     

Kinetics study of the copper/hydrochloric acid reaction for thermochemical hydrogen production

The exothermic reaction of hydrochloric acid with particulate copper occurs during the hydrogen production step in the thermochemical copper–chlorine water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the hydrogen conversion aspects. It is obtained that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55% and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches over 3000 W/m² when the particle shrinks to 0.1% from its initial size. The estimated Biot number varies from 0.001 to 0.1, depending on the operating conditions and the accuracy of thermophysical data of the substances. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction that models the shrinking of copper particles in the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for the estimation of the temperature of a copper particle, assumed spherical, in the radial direction on the hypothesis of large Biot numbers. For small Biot numbers, the transient heat transfer equation results in a lumped capacitance model. In all cases, the particle decomposes in about 10–20s.     

Heat extraction from supercritical water-cooled nuclear reactors for hydrogen production plants

Many current and future hydrogen production methods, such as steam methane reforming and thermochemical water splitting cycles, require large amounts of heat as the major energy input. Using nuclear heat is a promising option for reducing emissions of greenhouse gases and other pollutants, thereby helping achieve clean and sustainable future energy systems. Various heat transfer fluids are compared and evaluation criteria are proposed for the selection of a heat transfer fluid. It is determined that helium is a promising option due to it being inert and chemically stable and having good heat transfer properties. The intermediate heat exchanger for the heat extraction is analyzed and designed using the log mean temperature difference (LMTD) method with helium serving as the heat transfer fluid to extract heat from the supercritical water. It is found that if the heat extraction load is in the range of 100–330 MW_th, which approximately corresponds to a hydrogen production range of 40–125 tonnes per day, then a multi-tube and single-shell counter flow heat exchanger with a shell diameter of 0.7–1.3 m and length of 6.7 m encapsulating 420–1600 tubes of 0.025 m diameter would be appropriate according to the practical working conditions on the shell and tube sides. The analysis also shows that the diameter of the heat exchanger does not depend strongly on the heat transfer load if the load is smaller than 330 MW_th (125 tonnes H₂/day). This provides flexibility in case adjustments to the heat extraction load become necessary. However, if the heat load is larger than 330 MW_th, for example, 500 MW_th for 200 tonnes hydrogen per day, then a multi-tube and single-shell counter flow heat exchanger is not appropriate because the length-to-diameter ratio is outside of the recommended range.     

Numerical studies on heat coupling and configuration optimization in an industrial hydrogen production reformer

Steam methane reforming furnaces are the most important devices in the hydrogen production industry. The highly endothermic reaction system requires reaction tubes in the furnace to have a large heat transfer area and to be operated under high temperature and pressure conditions. In order to enhance heat transfer efficiency and protect reaction tubes, the controlling and optimization of the furnace structure have increasingly received more and more research attention. As known from the furnace structure, it is essential to couple the exothermic combustion with the endothermic reforming reactions due to the highly interactive nature of the two processes. Thus, in this paper, the combustion process in the furnace was numerically studied by using computational fluid dynamics (CFD) to model the combustion chamber, coupled with methane steam reforming reaction inside the reaction tubes, defined by a plug flow model. A set of combustion models were compared for the furnace chamber and a plug flow reaction model was employed for reforming reaction tubes, and then a heat coupling process was established. The predicted flue gas temperature distribution showed that the heat transfer in the furnace was not uniform, resulting in hot spots and heat losses on the tube wall. Therefore, structure optimization schemes were proposed. Optimization on arrangements of the tubes and the nozzles promoted the uniform distribution of flue-gas temperature and then improved heat transfer efficiency, thereby enhancing performance of the steam reforming process.     

Synergistic roles of off-peak electrolysis and thermochemical production of hydrogen from nuclear energy in Canada

Hydrogen as a clean energy carrier is frequently identified as a major solution to the environmental problem of greenhouse gases, resulting from worldwide dependence on fossil fuels. However, most of the world's hydrogen (about 96%) is currently produced from fossil fuels, which does not address the issue of greenhouse gases. Although there is a large motivation of the “hydrogen economy”, for improvement of urban air quality, energy security, and integration of intermittent renewable energy sources, CO₂ free energy sources are critical to hydrogen becoming a significant energy carrier. Two technologies, applied in tandem, have a promising potential to generate hydrogen without leading to greenhouse gas emissions: 1) electrolysis and 2) thermochemical decomposition of water. This paper will investigate their unique complementary roles to reduce costs of hydrogen production. Together they have a unique potential to serve both de-centralized hydrogen needs in periods of low-demand electricity, and centralized base-load production from a nuclear station. Thermochemical methods have a significantly higher thermal efficiency, but electrolysis can take advantage of low electricity prices during off-peak hours, as well as intermittent and de-centralized supplies like wind, solar or tidal power. By effectively linking these systems, water-based production of hydrogen can become more competitive against the predominant existing technology, SMR (steam-methane reforming).     

Exergy analysis of hydrogen production via steam methane reforming

The performance of hydrogen production via steam methane reforming (SMR) is evaluated using exergy analysis, with emphasis on exergy flows, destruction, waste, and efficiencies. A steam methane reformer model was developed using a chemical equilibrium model with detailed heat integration. A base-case system was evaluated using operating parameters from published literature. Reformer operating parameters were varied to illustrate their influence on system performance. The calculated thermal and exergy efficiencies of the base-case system are lower than those reported in literature. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions and heat transfer. A significant amount of exergy is wasted in the exhaust stream. The variation of reformer operating parameters illustrated an inverse relationship between hydrogen yield and the amount of methane required by the system. The results of this investigation demonstrate the utility of exergy analysis and provide guidance for where research and development in hydrogen production via SMR should be focused.     

Upgrading waste heat from a cement plant for thermochemical hydrogen production

A calcium oxide/steam chemical heat pump (CHP) is presented in the study as a means to upgrade waste heat from industrial processes for thermochemical hydrogen production. The CHP is used to upgrade waste heat for the decomposition of copper oxychloride (CuO.CuCl₂) in a copper–chlorine (Cu–Cl) thermochemical cycle. A formulation is presented for high temperature steam electrolysis and thermochemical splitting of water using waste heat of a cement plant. Numerical models are presented for verifying the availability of energy for potential waste heat upgrading in cement plants. The optimal hydration and decomposition temperatures for the calcium oxide/steam reversible reaction of 485 K and 565 K respectively are obtained for the combined heat pump and thermochemical cycle. The coefficient of performance and overall efficiency of 4.6 and 47.8% respectively are presented and discussed for the CHP and hydrogen production from the cement plant.     

Development of an integrated thermochemical cycle-based hydrogen production and effective utilization

In this study, an assessment of a renewable energy-based hybrid sulfur-bromine cycle for hydrogen fuel production and effective utilization is performed since the present era requires lots of hydrogen for fueling many systems. Hydrogen, produced by the hybrid sulfur-bromine cycle, is supplied to the combustion subsystems by blending with natural gas for residential use. Solar and wind energy sources are potentially considered as renewable energies for green hydrogen production. Also, a drying unit is included with an incineration subsystem. A desalination unit is also integrated to produce freshwater for the community. In this way, electricity, heat, and clean water required both for the community and the subsystems are supplied. The integrated system is then assessed in terms of energy and exergy efficiencies. Here, 0.233 kg/s of natural gas and hydrogen blend and 1.338 kg/s of biomass are provided to the system. The energy and exergy efficiencies of the overall system are determined to be 64.43% and 32.24%.     

A critical review on integrated system design of solar thermochemical water-splitting cycle for hydrogen production

The development of clean hydrogen production methods is important for large-scale hydrogen production applications. The solar thermochemical water-splitting cycle is a promising method that uses the heat provided by solar collectors for clean, efficient, and large-scale hydrogen production. This review summarizes state-of-the-art concentrated solar thermal, thermal storage, and thermochemical water-splitting cycle technologies that can be used for system integration from the perspective of integrated design. Possible schemes for combining these three technologies are also presented. The key issues of the solar copper-chlorine (Cu–Cl) and sulfur-iodine (S–I) cycles, which are the most-studied cycles, have been summarized from system composition, operation strategy, thermal and economic performance, and multi-scenario applications. Moreover, existing design ideas, schemes, and performances of solar thermochemical water-splitting cycles are summarized. The energy efficiency of the solar thermochemical water-splitting cycle is 15–30%. The costs of the solar Cu–Cl and S–I hydrogen production systems are 1.63–9.47 $/kg H₂ and 5.41–10.40 $/kg H₂, respectively. This work also discusses the future challenges for system integration and offers an essential reference and guidance for building a clean, efficient, and large-scale hydrogen production system.     

Assessment of CO2 capture options from various points in steam methane reforming for hydrogen production

Steam methane reforming (SMR) is currently the main hydrogen production process in industry, but it has high emissions of CO₂, at almost 7 kg CO₂/kg H₂ on average, and is responsible for about 3% of global industrial sector CO₂ emissions. Here, the results are reported of an investigation of the effect of steam-to-carbon ratio (S/C) on CO₂ capture criteria from various locations in the process, i.e. synthesis gas stream (location 1), pressure swing adsorber (PSA) tail gas (location 2), and furnace flue gases (location 3). The CO₂ capture criteria considered in this study are CO₂ partial pressure, CO₂ concentration, and CO₂ mass ratio compared to the final exhaust stream, which is furnace flue gases. The CO₂ capture number (N_cc) is proposed as measure of capture favourability, defined as the product of the three above capture criteria. A weighting of unity is used for each criterion. The best S/C ratio, in terms of providing better capture option, is determined. CO₂ removal from synthesis gas after the shift unit is found to be the best location for CO₂ capture due to its high partial pressure of CO₂. However, furnace flue gases, containing almost 50% of the CO₂ in produced in the process, are of great significance environmentally. Consequently, the effects of oxygen enrichment of the furnace feed are investigated, and it is found that this measure improves the CO₂ capture conditions for lower S/C ratios. Consequently, for an S/C ratio of 2.5, CO₂ capture from a flue gas stream is competitive with two other locations provided higher weighting factors are considered for the full presence of CO₂ in the flue gases stream. Considering carbon removal from flue gases, the ratio of hydrogen production rate and N_cc increases with rising reformer temperature.     

Thermodynamic performance assessment of boron based thermochemical water splitting cycle for renewable hydrogen production

The present study is related with the thermodynamic performance assessment of renewable hydrogen production through Boron thermochemical water splitting cycle. Therefore, all step efficiencies and overall cycle efficiency are calculated based on complete reaction. Additionally, a parametric study is conducted to determine the effect of the reference environment temperature on the overall cycle efficiency. In this regard, exergy efficiencies, exergy destruction rates and also inlet and outlet exergy rates of the cycle are calculated and presented for various reference temperatures. The exergy efficiency of the cycle is calculated as 0.4393 based on complete reaction and occurs at 298 K. This study has shown that Boron thermochemical water splitting cycle has a great potential due to cycle performance. As a result, Boron based thermochemical water splitting cycle can help achieve better environment and sustainability due to high exergetic efficiency. By the way, economic and technical issues of the storage and transportation of the hydrogen can find a proper solution if the hydrogen production reaction of the Boron thermochemical water splitting cycle takes place on-board of a vehicle.     

CFD simulation with detailed chemistry of steam reforming of methane for hydrogen production in an integrated micro-reactor

micro-reactor has drawn more and more attention in recent years due to the process intensification on basic transport phenomena in micro-channels, which would often lead to the improved reactor performance. Steam reforming of methane (SRM) in micro-reactor has great potential to realize a low-cost, compact process for hydrogen production via an evident shortening of reaction time from seconds to milliseconds. This work focuses on the detailed modeling and simulation of a micro-reactor design for SRM reaction with the integration of a micro-channel for Rh-catalyzed endothermic reaction, a micro-channel for Pt-catalyzed exothermic reaction and a wall in between with Rh or Pt-catalyst coated layer. The elementary reaction kinetics for SRM process is adopted in the CFD model, while the combustion channel is described by global reaction kinetics. The model predictions were quantitatively validated by the experimental data in the literature. For the extremely fast reactions in both channels, the simulations indicated the significance of the heat conduction ability of the reactor wall as well as the interplay between the exothermic and endothermic reactions (e.g., the flow rate ratio of fuel gas to reforming gas). The characteristic width of 0.5 mm is considered to be a suitable channel size to balance the trade-off between the heat transfer behavior in micro-channels and the easy fabrication of micro-channels.     

Hydrogen production by the Cu–Cl thermochemical cycle: Investigation of the key step of hydrolysing CuCl2 to Cu2OCl2 and HCl using a spray reactor

One of the most challenging steps in the thermochemical Cu–Cl cycle for the production of hydrogen is the hydrolysis of CuCl₂ into Cu₂OCl₂ and HCl while avoiding the need for excess water and the undesired thermolysis reaction, which gives CuCl and Cl₂. Argonne National Laboratory has designed a spray reactor where an aqueous solution of CuCl₂ is atomized into a heated zone, into which steam/Ar are injected in co- or counter-current flow. The solid products of the reaction were analyzed by XRD and SEM. With a pneumatic nebulizer, the counter-current flow design gave high yields of Cu₂OCl₂ compared to the co-current flow design, but some CuCl₂ remained unreacted in both designs. With an ultrasonic nozzle, essentially 100% yields of Cu₂OCl₂ were obtained. Some CuCl was present in the products with both types of atomizers but this is believed to be due to decomposition of Cu₂OCl₂ rather than CuCl₂. Analyses of gaseous products from the hydrolysis reactions in a fixed bed were conducted at the Commissariat à L'Energie Atomique using ultraviolet-visible spectrometry and conductivity. At a reaction temperature of 390 °C, the desired HCl was formed while no Cl₂ was detected until the bed temperature was above 400 °C.     

Hydrolysis of CuCl2 in the Cu–Cl thermochemical cycle for hydrogen production: Experimental studies using a spray reactor with an ultrasonic atomizer

The Cu–Cl thermochemical cycle is being developed as a hydrogen production method. Prior proof-of-concept experimental work has shown that the chemistry is viable while preliminary modeling has shown that the efficiency and cost of hydrogen production have the potential to meet DOE's targets. However, the mechanisms of CuCl₂ hydrolysis, an important step in the Cu–Cl cycle, are not fully understood. Although the stoichiometry of the hydrolysis reaction, 2CuCl₂ + H₂O ↔ Cu₂OCl₂ + 2HCl, indicates a necessary steam-to-CuCl₂ molar ratio of 0.5, a ratio as high as 23 has been typically required to obtain near 100% conversion of the CuCl₂ to the desired products at atmospheric pressure. It is highly desirable to conduct this reaction with less excess steam to improve the process efficiency. Per Le Chatelier's Principle and according to the available equilibrium-based model, the needed amount of steam can be decreased by conducting the hydrolysis reaction at a reduced pressure. In the present work, the experimental setup was modified to allow CuCl₂ hydrolysis in the pressure range of 0.4–1 atm. Chemical and XRD analyses of the product compositions revealed the optimal steam-to-CuCl₂ molar ratio to be 20–23 at 1 atm pressure. The experiments at 0.4 atm and 0.7 atm showed that it is possible to lower the steam-to-CuCl₂ molar ratio to 15, while still obtaining good yields of the desired products. An important effect of running the reaction at reduced pressure is the significant decrease of CuCl concentration in the solid products, which was not predicted by prior modeling. Possible explanations based on kinetics and residence times are suggested.     

Exergoenvironmental analysis of a steam methane reforming process for hydrogen production

Steam methane reforming (SMR) is one of the most promising processes for hydrogen production. Several studies have demonstrated its advantages from the economic viewpoint. Nowadays process development is based on technical and economical aspects; however, in the near future, the environmental impact will play a significant role in the design of such processes. In this paper, an SMR process is studied from the viewpoint of overall environmental impact, using an exergoenvironmental analysis. This analysis presents the combination of exergy analysis and life cycle assessment. Components where chemical reactions occur are the most important plant components from the exergoenvironmental point of view, because, in general, there is a high environmental impact associated with these components. This is mainly caused by the exergy destruction within the components, and this in turn is mainly due to the chemical reactions. The obtained results show that the largest potential for reducing the overall environmental impact is associated with the combustion reactor, the steam reformer, the hydrogen separation unit and the major heat exchangers. The environmental impact in these components can mainly be reduced by improving their exergetic efficiency. A sensitivity analysis for some important exergoenvironmental variables is also presented in the paper.     

Multi-objective optimization of an experimental integrated thermochemical cycle of hydrogen production with an artificial neural network

In this study, an experimental lab-scale copper-chlorine (Cu–Cl) cycle of hydrogen production is examined and optimized in terms of exergy efficiency and operational costs of produced hydrogen. The integrated process is modeled and simulated in Aspen Plus incorporating the reaction kinetic parameters with a sensitivity analysis of a range of operating conditions. An artificial neural network (ANN) method with machine learning is used to generate a mathematical function that is optimized based on a multi-objective genetic algorithm (MOGA) method. A sensitivity analysis of variations of each design parameter for both the objective functions and the effectiveness of exergy performance relative to operational costs of produced hydrogen is demonstrated. The sensitivity analysis and optimization results are presented and discussed.     

The progress in water gas shift and steam reforming hydrogen production technologies – A review

Hydrogen has been widely considered a clean fuel of the future, with the highest mass based energy density of known fuels. Water gas shift (WGS) and steam reforming (SR) are the major reactions used for hydrogen production, and improved catalysts are essential to the future of the WGS and SR processes. Much progress in the different aspects of these fields has been made recently, which includes approaches to preparation and characterization, doping and promotion, as well as evaluation of catalysts, especially nanocatalysts. Significant improvements have been realized in increasing the stability of the catalysts, the overall conversion of raw materials, and the hydrogen production selectivity. This review aims to introduce these hydrogen production processes, to present developments in these areas, and discusses recent improvements that have made noteworthy impacts.     

A review on reforming bio-ethanol for hydrogen production

Bio-ethanol is a prosperous renewable energy carrier mainly produced from biomass fermentation. Reforming of bio-ethanol provides a promising method for hydrogen production from renewable resources. Besides operating conditions, the use of catalysts plays a crucial role in hydrogen production through ethanol reforming. Rh and Ni are so far the best and the most commonly used catalysts for ethanol steam reforming towards hydrogen production. The selection of proper support for catalyst and the methods of catalyst preparation significantly affect the activity of catalysts. In terms of hydrogen production and long-term stability, MgO, ZnO, _CeO2${\mathrm{CeO}}_2$, and _La2O3${\mathrm{La}}_2{\mathrm{O}}_3$ are suitable supports for Rh and Ni due to their basic characteristics, which favor ethanol dehydrogenation but inhibit dehydration. As Rh and Ni are inactive for water gas shift reaction (WGSR), the development of bimetallic catalysts, alloy catalysts, and double-bed reactors is promising to enhance hydrogen production and long-term catalyst stability. Autothermal reforming of bio-ethanol has the advantages of lesser external heat input and long-term stability. Its overall efficiency needs to be further enhanced, as part of the ethanol feedstock is used to provide low-grade thermal energy. Development of millisecond-contact time reactor provides a low-cost and effective way to reform bio-ethanol and hydrocarbons for fuel upgrading. Despite its early R&D stage, bio-ethanol reforming for hydrogen production shows promises for its future fuel cell applications.     

Thermodynamic analysis and optimization of an integrated solar thermochemical hydrogen production system

In this study, thermodynamic analysis of solar-based hydrogen production via copper-chlorine (Cu–Cl) thermochemical water splitting cycle is presented. The integrated system utilizes air as the heat transfer fluid of a cavity-pressurized solar power tower to supply heat to the Cu–Cl cycle reactors and heat exchangers. To achieve continuous operation of the system, phase change material based on eutectic fluoride salt is used as the thermal energy storage medium. A heat recovery system is also proposed to use the potential waste heat of the Cu–Cl cycle to produce electricity and steam. The system components are investigated thoroughly and system hotspots, exergy destructions and overall system performance are evaluated. The effects of varying major input parameters on the overall system performance are also investigated. For the baseline, the integrated system produces 343.01 kg/h of hydrogen, 41.68 MW of electricity and 11.39 kg/s of steam. Overall system energy and exergy efficiencies are 45.07% and 49.04%, respectively. Using Genetic Algorithm (GA), an optimization is performed to evaluate the maximum amount of produced hydrogen. The optimization results show that by selecting appropriate input parameters, hydrogen production rate of 491.26 kg/h is achieved.