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.     

Comparison of sulfur–iodine and copper–chlorine thermochemical hydrogen production cycles

Sulfur–iodine and copper–chlorine water splitting cycles are promising methods of thermochemical hydrogen production. In this paper, these two cycles are compared from the perspectives of heat quantity, heat grade, thermal efficiency, related engineering challenges, and hydrogen production cost. The heat quantity and grade required by each step of the cycles are evaluated and the thermal efficiencies are approximated from the heat requirements. It is found that the overall heat requirements of the two cycles do not have significant differences and the overall efficiencies of the two cycles are similar, between 37 and 54%, depending on the portion of heat recovery. The copper–chlorine cycle has the advantage of a lower maximum temperature of 803 K, which is 300 K lower than the maximum temperature of 1123 K in the sulfur–iodine cycle. This indicates that the copper–chlorine cycle can link more readily with various heat sources, such as grade Generation IV nuclear and fossil fuel power stations. It is also reported that the copper–chlorine cycle can have fewer challenges of equipment materials and product separation. A cost analysis shows that the copper–chlorine and sulfur–iodine cycles have similar hydrogen production costs, which are lower than steam-methane reforming, and conventional and high temperature electrolysis, due to less use of electricity, no carbon related charges and no methane requirement in the thermochemical cycles.     

Comparative life cycle assessment of hydrogen and other selected fuels

A streamlined life cycle assessment (LCA) is reported of a nuclear-based copper–chlorine (Cu–Cl) hydrogen production cycle, including estimates of fossil fuel energy use and greenhouse gas (GHG) emissions. Calculations revealed that the process requires 474 kJ of fossil fuel energy per MJ of hydrogen, which is less than for other hydrogen production processes. Moreover, GHG emissions are estimated to be 27 gCO₂e per MJ of hydrogen, which is only slightly higher than the corresponding value for wind-based hydrogen production. A sensitivity analysis demonstrated that the performance of the system could be further improved at higher yields of hydrogen. Although the system significantly outperformed fossil-based gasoline and hydrogen production pathways, the integrated nuclear and thermochemical cycle still requires significant research and development before commercialization is possible.     

An exergy–cost–energy–mass analysis of a hybrid copper–chlorine thermochemical cycle for hydrogen production

An exergoeconomic assessment using exergy–cost–energy–mass (EXCEM) analysis is reported of a copper–chlorine (Cu–Cl) thermochemical water splitting cycle for hydrogen production. The quantitative relation is identified between capital costs and thermodynamic losses for devices in the cycle. A correlation detected in previous assessments, suggesting that devices in energy systems are configured so as to achieve an overall optimal design by appropriately balancing thermodynamic (exergy-based) and economic characteristics of the overall system and its components, is observed to apply for the Cu–Cl cycle. Exergetic cost allocations and various exergoeconomic performance parameters are determined for the overall cycle and its components. The results are expected to assist ongoing efforts to increase the economic viability and to reduce product costs of potential commercial versions of this process. The impacts of these results are anticipated to be significant since thermochemical water splitting with a copper–chlorine cycle is a promising process that could be linked with nuclear reactors to produce hydrogen with no greenhouse gases emissions, and thereby help mitigate numerous energy and environment concerns.     

Natural gas usage as a heat source for integrated SMR and thermochemical hydrogen production technologies

This paper investigates various usages of natural gas (NG) as an energy source for different hydrogen production technologies. A comparison is made between the different methods of hydrogen production, based on the total amount of natural gas needed to produce a specific quantity of hydrogen, carbon dioxide emissions per mole of hydrogen produced, water requirements per mole of hydrogen produced, and a cost sensitivity analysis that takes into account the fuel cost, carbon dioxide capture cost and a carbon tax. The methods examined are the copper–chlorine (Cu–Cl) thermochemical cycle, steam methane reforming (SMR) and a modified sulfur–iodine (S–I) thermochemical cycle. Also, an integrated Cu–Cl/SMR plant is examined to show the unique advantages of modifying existing SMR plants with new hydrogen production technology. The analysis shows that the thermochemical Cu–Cl cycle out-performs the other conventional methods with respect to fuel requirements, carbon dioxide emissions and total cost of production.     

Exergetic life cycle assessment of a hydrogen production process

Exergetic life cycle assessment (ExLCA) is applied with life cycle assessment (LCA) to a hydrogen production process. This comparative environmental study examines a nuclear-based hydrogen production via thermochemical water splitting using a copper–chlorine cycle. LCA, which is an analytical tool to identify, quantify and decrease the overall environmental impact of a system or a product, is extended to ExLCA. Exergy efficiencies and air pollution emissions are evaluated for all process steps, including the uranium processing, nuclear and hydrogen production plants. LCA results are presented in four categories: acidification potential, eutrophication potential, global warming potential and ozone depletion potential. A parametric study is performed for various plant lifetimes. The ExLCA results indicate that the greatest irreversibility is caused by uranium processing. The primary contributor of the life cycle irreversibility of the nuclear-based hydrogen production process is fuel (uranium) processing, for which the exergy efficiency is 26.7% and the exergy destruction is 2916.3 MJ. The lowest global warming potential per megajoule exergy of hydrogen is 5.65 g CO₂-eq achieved a plant capacity of 125,000 kg H₂/day. The corresponding value for a plant capacity of 62,500 kg H₂/day is 5.75 g CO₂-eq.     

Advances in hydrogen production by thermochemical water decomposition: A review

Hydrogen demand as an energy currency is anticipated to rise significantly in the future, with the emergence of a hydrogen economy. Hydrogen production is a key component of a hydrogen economy. Several production processes are commercially available, while others are under development including thermochemical water decomposition, which has numerous advantages over other hydrogen production processes. Recent advances in hydrogen production by thermochemical water decomposition are reviewed here. Hydrogen production from non-fossil energy sources such as nuclear and solar is emphasized, as are efforts to lower the temperatures required in thermochemical cycles so as to expand the range of potential heat supplies. Limiting efficiencies are explained and the need to apply exergy analysis is illustrated. The copper–chlorine thermochemical cycle is considered as a case study. It is concluded that developments of improved processes for hydrogen production via thermochemical water decomposition are likely to continue, thermochemical hydrogen production using such non-fossil energy will likely become commercial, and improved efficiencies are expected to be obtained with advanced methodologies like exergy analysis. Although numerous advances have been made on sulphur–iodine cycles, the copper–chlorine cycle has significant potential due to its requirement for process heat at lower temperatures than most other thermochemical processes.     

Recent Canadian advances in nuclear-based hydrogen production and the thermochemical Cu–Cl cycle

This paper presents recent Canadian advances in nuclear-based production of hydrogen by electrolysis and the thermochemical copper–chlorine (Cu–Cl) cycle. This includes individual process and reactor developments within the Cu–Cl cycle, thermochemical properties, advanced materials, controls, safety, reliability, economic analysis of electrolysis at off-peak hours, and integrating hydrogen plants with Canada's nuclear power plants. These enabling technologies are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production from the next generation of nuclear reactors.     

Life cycle energy and environmental analysis of a microgrid power pavilion

Microgrids—generating systems incorporating multiple distributed generator sets linked together to provide local electricity and heat—are one possible alterative to the existing centralized energy system. Potential advantages of microgrids include flexibility in fuel supply options, the ability to limit emissions of greenhouse gases, and energy efficiency improvements through combined heat and power (CHP) applications. As a case study in microgrid performance, this analysis uses a life cycle assessment approach to evaluate the energy and emissions performance of the NextEnergy microgrid Power Pavilion in Detroit, Michigan and a reference conventional system. The microgrid includes generator sets fueled by solar energy, hydrogen, and natural gas. Hydrogen fuel is sourced from both a natural gas steam reforming operation and as a by‐product of a chlorine production operation. The chlorine plant receives electricity exclusively from a hydropower generating station. Results indicate that the use of this microgrid offers a total energy reduction potential of up to 38%, while reductions in non‐renewable energy use could reach 51%. Similarly, emissions of CO₂, a key global warming gas, can be reduced by as much as 60% relative to conventional heat and power systems. Hydrogen fuels are shown to provide a net energy and emissions benefit relative to natural gas only when sourced primarily from the chlorine plant. Copyright © 2006 John Wiley & Sons, Ltd.     

Potential methods for geothermal-based hydrogen production

In this study, four potential methods are identified for geothermal-based hydrogen production, namely, (i) directly from the geothermal steam, (ii) through conventional water electrolysis using the electricity generated from geothermal power plant, (iii) using both geothermal heat and electricity for high temperature steam electrolysis and/or hybrid processes, (iv) using the heat available from geothermal resource in thermochemical processes to disassociate water into hydrogen and oxygen. Here we focus on relatively low-temperature thermochemical and hybrid cycles, due to their greater application possibility, and examine them as a potential option for hydrogen production using geothermal heat. We also present a brief thermodynamic analysis to assess their performance through energy and exergy efficiencies for comparison purposes. The results show that these cycles have good potential and become attractive due to the overall system efficiencies over 50%. The copper–chlorine cycle is identified as a highly promising cycle for geothermal hydrogen production. Furthermore, three types of industrial electrolysis methods, which are generally considered for hydrogen production currently, are also discussed and compared with the above mentioned cycles.     

Multiphase reactor scale-up for Cu–Cl thermochemical hydrogen production

This paper examines selected design issues associated with reactor scale-up in the thermochemical copper–chlorine (Cu–Cl) cycle of hydrogen production. The thermochemical cycle decomposes water into oxygen and hydrogen, through intermediate copper and chlorine compounds. In this paper, emphasis is focused on the hydrogen, oxygen and hydrolysis reactors. A sedimentation cell for copper separation and HCl gas absorption tower are discussed for the thermochemical hydrogen reactor. A molten salt reactor is investigated for decomposition of an intermediate compound, copper oxychloride (CuO·Cl₂), into oxygen gas and molten cuprous chloride. Scale-up design issues are examined for handling three phases within the molten salt reactor, i.e., solid copper oxychloride particles, liquid (melting salt) and exiting gas (oxygen). Also, different variations of hydrolysis reactions are compared, including 5, 3 and 2-step Cu–Cl cycles that utilize reactive spray drying, instead of separate drying and hydrolysis processes. The spray drying involves evaporation of aqueous feed by mixing the spray and drying streams. Results are presented for the required capacities of feed materials for the multiphase reactors, steam and heat requirements, and other key design parameters for reactor scale-up to a pilot-scale capacity.     

Future fuel cell and internal combustion engine automobile technologies: A 25-year life cycle and fleet impact assessment

Hydrogen fuel cell (FC) vehicles are receiving increasing attention as a potential powerful technology to reduce the transportation sector's dependence on petroleum and substantially decrease emissions of greenhouse gases (GHGs) at the same time. This paper projects energy use and GHG emissions from different FC vehicle configurations and compares these values to the projected characteristics of similarly sized and performing gasoline and diesel fueled automobiles on a life cycle, well to wheels and cradle to grave basis. Our analysis suggests that for the next 20 or more years, new internal combustion engine (ICE) hybrid drive train vehicles can achieve similar levels of reduction in energy use and GHG emissions compared to hydrogen FC vehicles, if the hydrogen is derived from natural gas. The fleet impact of more fuel-efficient vehicles depends on the time it takes for new technology to (i) become competitive, (ii) increase its share of the new vehicles produced, and finally (iii) penetrate significantly into the vehicle fleet. Since the lead times for bringing improved ICE vehicle technology into production are the shortest, its impact on vehicle fleet energy use and emissions could be significant in 20–30 years, about half the time required for hydrogen FC vehicles to have a similar impact. Full emission reduction potential of FC vehicles can only be achieved when hydrogen is derived from zero or very low-carbon releasing production processes on a large scale—an option that further increases the impact leadtime. Thus, a comprehensive short- and long-term strategy for reducing automobile energy use and emissions should include both the continuous improvement of ICE vehicles and simultaneous research and development of hydrogen FC cars.     

Conversion of fossil and biomass fuels to electric power and transportation fuels by high efficiency integrated plasma fuel cell (IPFC) energy cycle

The IPFC is a high efficiency energy cycle, which converts fossil and biomass fuel to electricity and co-product hydrogen and liquid transportation fuels (gasoline and diesel). The cycle consists of two basic units, a hydrogen plasma black reactor (HPBR) which converts the carbonaceous fuel feedstock to elemental carbon and hydrogen and CO gas. The carbon is used as fuel in a direct carbon fuel cell (DCFC), which generates electricity, a small part of which is used to power the plasma reactor. The gases are cleaned and water gas shifted for either hydrogen or syngas formation. The hydrogen is separated for production or the syngas is catalytically converted in a Fischer–Tropsch (F–T) reactor to gasoline and/or diesel fuel. Based on the demonstrated efficiencies of each of the component reactors, the overall IPFC thermal efficiency for electricity and hydrogen or transportation fuel is estimated to vary from 70 to 90% depending on the feedstock and the co-product gas or liquid fuel produced. The CO₂ emissions are proportionately reduced and are in concentrated streams directly ready for sequestration. Preliminary cost estimates indicate that IPFC is highly competitive with respect to conventional integrated combined cycle plants (NGCC and IGCC) for production of electricity and hydrogen and transportation fuels.     

Progress of international hydrogen production network for the thermochemical Cu–Cl cycle

This paper presents recent advances by an international team which is developing the thermochemical copper–chlorine (Cu–Cl) cycle for hydrogen production. Development of the Cu–Cl cycle has been pursued by several countries within the framework of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. Due to its lower temperature requirements in comparison with other thermochemical cycles, the Cu–Cl cycle is particularly well matched with Canada's Generation IV reactor, SCWR (Super-Critical Water Reactor), as well as other heat sources such as solar energy or industrial waste heat. In this paper, recent developments of the Cu–Cl cycle are presented, specifically involving unit operation experiments, corrosion resistant materials and system integration.     

A preliminary life cycle assessment of PEM fuel cell powered automobiles

This paper provides a preliminary life cycle assessment (LCA) of polymer electrolyte membrane (PEM) fuel cell powered automobile. Life cycle of PEM fuel cell automobile not only includes operation of the vehicle on the road but also include production and distribution of both the vehicle and the fuel (e.g. hydrogen) during the vehicle’s entire lifetime. Assessment is based on the published data available in the literature. The two characteristics of the life cycle, which were assessed, are energy consumption and greenhouse gases (GHGs) emissions. Greenhouse gases (GHGs) emissions considered in the present assessment are CO₂ and CH₄. In addition, conventional internal combustion engine (ICE) automobile is also assessed based on similar characteristics for comparison with PEM fuel cell automobile. It is found that the energy utilized to generate the hydrogen during fuel cycle for the PEM automobile is about 3.5 times higher than the energy utilized to generate the gasoline during its fuel cycle. However, the overall life cycle energy consumption of PEM fuel cell automobile is about 2.3 times less than that of ICE automobile. Similarly, the GHGs emissions of PEMFC automobile are about 8.5 times higher than ICE automobile during the fuel cycle, but the overall life cycle GHGs emissions are about 2.6 times lower than ICE automobile.     

Exploring the competitiveness of hydrogen-fueled gas turbines in future energy systems

Hydrogen is currently receiving attention as a possible cross-sectoral energy carrier with the potential to enable emission reductions in several sectors, including hard-to-abate sectors. In this work, a techno-economic optimization model is used to evaluate the competitiveness of time-shifting of electricity generation using electrolyzers, hydrogen storage and gas turbines fueled with hydrogen as part of the transition from the current electricity system to future electricity systems in Years 2030, 2040 and 2050. The model incorporates an emissions cap to ensure a gradual decline in carbon dioxide (CO₂) levels, targeting near-zero CO₂ emissions by Year 2050, and this includes 15 European countries.The results show that hydrogen gas turbines have an important role to play in shifting electricity generation and providing capacity when carbon emissions are constrained to very low levels in Year 2050. The level of competitiveness is, however, considerably lower in energy systems that still allow significant levels of CO₂ emissions, e.g., in Year 2030. For Years 2040 and 2050, the results indicate investments mainly in gas turbines that are partly fueled with hydrogen, with 30–77 vol.-% hydrogen in biogas, although some investments in exclusively hydrogen-fueled gas turbines are also envisioned. Both open cycle and combined cycle gas turbines (CCGT) receive investments, and the operational patterns show that also CCGTs have a frequent cyclical operation, whereby most of the start-stop cycles are less than 20 h in duration.     

Energy and exergy analyses of magnesium-chlorine (Mg-Cl) thermochemical cycle

In this paper, we conduct energy and exergy analyses of the magnesium-chlorine (Mg-Cl) thermochemical cycle for hydrogen production and examine the respective cycle energy and exergy efficiencies. We also undertake a parametric study to investigate how the overall cycle performance is affected by changing the reference environment temperature and operating conditions. The results show that Mg-Cl cycle offers a good potential due to its high energy and exergy efficiencies as 63.63% and 34.86%, respectively, based upon the conditions and parameters considered. In this regard, Mg-Cl cycle appears to be a promising low temperature thermochemical cycle. It may, therefore, compete with other low temperature thermochemical and hybrid cycles such as the copper–chlorine cycle.     

Life cycle assessment of various hydrogen production methods

A comprehensive life cycle assessment (LCA) is reported for five methods of hydrogen production, namely steam reforming of natural gas, coal gasification, water electrolysis via wind and solar electrolysis, and thermochemical water splitting with a Cu–Cl cycle. Carbon dioxide equivalent emissions and energy equivalents of each method are quantified and compared. A case study is presented for a hydrogen fueling station in Toronto, Canada, and nearby hydrogen resources close to the fueling station. In terms of carbon dioxide equivalent emissions, thermochemical water splitting with the Cu–Cl cycle is found to be advantageous over the other methods, followed by wind and solar electrolysis. In terms of hydrogen production capacities, natural gas steam reforming, coal gasification and thermochemical water splitting with the Cu–Cl cycle methods are found to be advantageous over the renewable energy methods.     

Global warming potential of the sulfur–iodine process using life cycle assessment methodology

A life cycle assessment (LCA) of one proposed method of hydrogen production – thermochemical water-splitting using the sulfur–iodine cycle couple with a very high-temperature nuclear reactor – is presented in this paper. Thermochemical water-splitting theoretically offers a higher overall efficiency than high-temperature electrolysis of water because heat from the nuclear reactor is provided directly to the hydrogen generation process, instead of using the intermediate step of generating electricity. The primary heat source for the S–I cycle is an advanced nuclear reactor operating at temperatures corresponding to those required by the sulfur–iodine process. This LCA examines the environmental impact of the combined advanced nuclear and hydrogen generation plants and focuses on quantifying the emissions of carbon dioxide per kilogram of hydrogen produced. The results are presented in terms of global warming potential (GWP). The GWP of the system is 2500 g carbon dioxide-equivalent (CO₂-eq) per kilogram of hydrogen produced. The GWP of this process is approximately one-sixth of that for hydrogen production by steam reforming of natural gas, and is comparable to producing hydrogen from wind- or hydro-electric conventional electrolysis.     

Canada’s program on nuclear hydrogen production and the thermochemical Cu–Cl cycle

This paper presents an overview of the status of Canada’s program on nuclear hydrogen production and the thermochemical copper–chlorine (Cu–Cl) cycle. Enabling technologies for the Cu–Cl cycle are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. Particular emphasis in this paper is given to hydrogen production with Canada’s Super-Critical Water Reactor, SCWR. Recent advances towards an integrated lab-scale Cu–Cl cycle are discussed, including experimentation, modeling, simulation, advanced materials, thermochemistry, safety, reliability and economics. In addition, electrolysis during off-peak hours, and the processes of integrating hydrogen plants with Canada’s nuclear plants are presented.