Copper Chlorine Research Articles

Thermodynamic performance assessment of the four-step copper-chlorine cycle in hydrogen production and compression

Rapidly increasing global energy demands requires sustainable alternatives to conventional fossil fuels. Hydrogen emerges as a promising energy carrier due to its high energy density and minimal environmental impact, mainly when produced via thermochemical cycles like the Copper Chlorine (CuCl), which makes use of low-grade waste thermal energy for hydrogen production in an environmentally friendly manner. This study integrates hydrogen production using the Cu-Cl cycle and hydrogen compression systems crucial for establishing robust hydrogen infrastructure. Following hydrogen generation, the study examines the thermodynamic analysis of compressing hydrogen to higher pressures. Parametric variations in compression, including inlet and outlet pressures and the number of stages, are analyzed to optimize energy efficiency and exergy performance. Energy efficiency of around 47.05% is obtained for the 4-step Cu-Cl cycle. The integrated step showed a notably high exergy efficiency of 98.48%. Other key findings include a 35% increase in energy efficiency with five compression stages for an inlet pressure increment from 15 to 30 bars, and a 12% efficiency decrease when varying outlet pressure from 500 to 800 bars. Exergy efficiency shows a 17% improvement with increased compression stages under constant inlet pressure but a 4% decline when varying outlet pressure with a five-stage configuration. These findings highlight the critical role of efficient compression systems in enhancing hydrogen storage and distribution for sustainable energy applications.

Thermal spray coatings for molten salt facing structural parts and enabling opportunities for thermochemical cycle electrolysis

AbstractThermochemical water splitting stands out as the most efficient techniques to produce hydrogen through electrolysis at a high temperature, relying on a series of chemical reactions within a loop. However, achieving a durable thermochemical cycle system poses a significant challenge, particularly in manufacturing suitable coating materials for reaction vessels and pipes capable of enduring highly corrosive conditions created by high‐temperature molten salts. The review summarizes thermally sprayed coatings (deposited on structural materials) that can withstand thermochemical cycle corrosive environments, geared towards nuclear thermochemical copper–chlorine (CuCl) cycles. An assessment was conducted to explore material composition and selection (structure–property relations), single and multi‐layer coating manufacturing, as well as corrosion environment and testing methods. The aim was to identify the critical areas for research and development in utilizing the feedstock materials and thermal spray coating techniques for applications in molten salt thermochemical applications, as well as use lessons learnt from other application areas (e.g., nuclear reaction vessels, boilers, waste incinerators, and aero engine gas‐turbine) where other types of molten salt and temperature are expected. Assessment indicated that very limited sets of coating‐substrate system with metallic interlayer is likely to survive high temperature corrosive environment for extended period of testing. However, within the known means and methods, as well as application of advanced thermal spray manufacturing processes could be a way forward to have sustainable coating‐substrate assembly with extended lifetime. Spraying multi‐layered coating (nano‐structured or micro‐structured powder materials) along with the application of modern suspension or solution based thermal spray techniques are considered to result in dense microstructures with improved resistance to high temperature thermochemical environment.

Insights into the effect of operating parameters and hydrodynamics on hydrolysis reaction in Copper–Chlorine thermochemical water splitting cycle for hydrogen production: Modelling and experimental validation

Copper–Chlorine (Cu–Cl) thermochemical cycle is being explored as one of the promising technologies for large scale production of clean hydrogen from water using nuclear or renewable energy. In this method, water splitting is achieved through a series of reactions in a loop producing only hydrogen and oxygen with complete recycle of all the intermediate copper and chlorine compounds. The first step of the cycle is the hydrolysis reaction wherein steam reacts with solid CuCl2 to form solid Cu2OCl2 (copper oxychloride) and HCl gas. The products enter the subsequent steps of the cycle and are recycled back to complete the loop. Multiple side reactions in the hydrolysis step result in reduced yield and loss of chemicals from the cycle. Efficient reactor design and optimal operating conditions of hydrolysis reactor is imperative towards achieving sustained closed loop operation and reducing the energy demand of Cu–Cl cycle. This paper presents a mathematical model for the simulation of hydrolysis reaction in a bubbling fluidized bed reactor. The one-dimensional model is developed based on modified two-phase theory of fluidization and is coupled with kinetics of multiple side reactions to investigate the effect of operating parameters and hydrodynamics on the conversion and yield of Cu2OCl2. The model results are validated with experimental data in 50 mm and 100 mm semi-batch fluidized bed reactors. The developed model clearly brings out the effect of different process parameters for process optimization and scale-up of the hydrolysis reactor for efficient integration in the cycle.

Electricity and hydrogen production by integrating two kinds of fuel cells with copper chlorine thermo-chemical cycle

An innovative cogeneration system based on a solid oxide fuel cell (SOFC) and copper chlorine cycle is being investigated. Instead of directly making electricity by any thermodynamic cycle or thermoelectric generator, the waste heat from SOFC should be used to make hydrogen through the copper-chlorine cycle (Cu–Cl). A portable polymer exchange membrane fuel cell (PEMFC) has been suggested due to its compatibility with portable and non-portable applications. The obtained results reveal that increasing the current density of SOFC results in higher methane consumption, output power, overpotentials, and hydrogen production. Furthermore, temperature variation does not have as much influence on power generation and efficiency as current density, where the system efficiency, when operating at 0.7 A/cm2 and SOFC operating temperature of 900–1200 K, varies between 40.4 % and 46.3 %. Regarding the methane flow rate, as it increases, the output power increases as well, but the efficiency falls. The system's greatest power output is 677.5 kW and occurs at a methane flow rate of 2.13 mol/s, although the system efficiency is just 39.7 % at that point. Most importantly, SOFC generates nearly 65 % of the total power, while PEMFC generates around 35 %. Therefore, the percentage of additional power that PEMFC can produce is around 55 %.

A review of the integration of the copper-chlorine cycle with other systems for hydrogen production

There are different methods for hydrogen production, among which thermo-chemical cycles are particularly important. One of the most common thermochemical cycles is the copper-chlorine cycle. In this cycle, the water electrolysis process takes place during a thermo-chemical reaction, and copper chlorine is used as a thermochemical reaction intermediate. This cycle requires two factors to produce hydrogen: A heat source with a temperature of about 520 oC and electricity. For this reason, it is possible to use the hot waste gases of industries or parabolic through collector and heliostat field to provide its heat. To supply electricity for this cycle, various alternatives from the power grid and wind turbine to heat recovery in cycles that use low-temperature energy sources are considered. In this article, the integration of the copper-chlorine cycle with power generation systems has been discussed and investigated from the perspective of energy, exergy, and economics. This review is divided into two general parts using renewable and non-renewable resources. At the beginning of this article, various methods of hydrogen production focusing on the copper-chlorine cycle have been briefly discussed. In the following, the way this cycle works is explained along with energy, exergy, and economic equations, and the research done in this direction is explained. Finally, a strategy for how to integrate the copper-chlorine cycle with other systems is described. Studying this article, in addition to giving a better attitude in the field of integrating this cycle with other plants, is similar to a guideline for using the cycle along with other systems for better productivity. The conducted investigations showed that the recovery of hot industrial exhaust gas as a source of heat for the Cu-Cl cycle has a high potential for saving energy consumption and reducing environmental pollutants. To produce the required electricity, it is recommended to use cycles that work with a low-temperature energy source, such as the organic Rankine cycle and Kalina cycles. Also, if renewable energy sources are used, it is recommended to use parabolic through collectors and heliostats to produce the required heat. As in the case of non-renewable energy sources, cycles with low-temperature energy sources can be used.

Techno economic analysis of efficient and environmentally friendly methods for hydrogen, power, and heat production using chemical looping combustion integrating plastic waste gasification and thermochemical copper chlorine cycles

Fossil fuels harm the environment and deplete resources. This study presents eco-friendly systems producing power, hydrogen, and heat with minimal pollution. Non-fossil sources like plastic waste solve waste issues and provide valuable energy. Thermochemical water splitting is another clean method for sustainable hydrogen production. The proposed systems employ chemical looping combustion in conjunction with PWG (plastic waste gasification) and thermochemical cycle of Cu–Cl (copper-chlorine), leveraging thermal integration between the CLC (chemical looping combustion) and subsequent processes. Comprehensive process simulations using Aspen Plus have been conducted for systems. The results indicated that the most desirable operational conditions for CLC occur when the molar ratio of oxygen carrier to fuel is 2.6. Under these conditions, there is no methane present in the fuel reactor products. Additionally, the thermal and exergy efficiencies of the CLC-PWG and CLC-CuCl cycles are determined to be 77.08/67.62 % and 66.11/61.1 % respectively, and the most irreversibility component for both systems is associated with the air reactor, with a value of 375 kW. Moreover, the hydrogen production rate in the CLC-PWG cycle is higher than in the CLC-CuCl cycle, with 105.6 kg/h compared to 34.6 kg/h, and the estimated lower minimum sale price for hydrogen is 2.8 USD/kg for CLC-PWG.

Molten salt heat exchanger design for the thermolysis reactor in the Cu–Cl cycle of hydrogen production

The thermochemical copper–chlorine (Cu–Cl) cycle is known as a promising method for producing clean hydrogen. Due to the high-temperature environment of the thermolysis reactor, there are commercialization challenges with regard to the heat exchanger design. In this study, a new design for the heat exchanger used in the thermolysis reactor of a 4-step Cu–Cl cycle is presented, aiming to achieve the required temperature distribution of 430 °C–550 °C. A design methodology is developed for the heat exchanger along with an iterative algorithm for the sizing problem. The final design of this study has decreased the T* (representative of the temperature range) by 51 % compared to the previous designs, with the improvement techniques resulting in increasing the heat exchanger effectiveness and thermal performance factor by 15 % and 138 % and decreasing average TD (representative of the temperature dispersal) by 61 %. The achieved operating temperature ranges from 431.3 °C to 539.0 °C.

Thermodynamic assessment of thermochemical cycle for hydrogen production based on water decomposition with binary copper chlorine couple

Thermodynamic assessment of thermochemical cycle for hydrogen production based on water decomposition with binary copper chlorine couple

Facile Synthesis of Efficient Copper Chlorine‐In‐Glass for White Light‐Emitting Diode and Anticounterfeiting

Copper halides have attracted extensive interest because of the merits of environmental friendliness, low lost, and superior optoelectronic properties. However, the stability issue heavily hinders their commercial application. Herein, the successful synthesis of copper chlorine in glass using melting‐quenching method under vacuum condition is reported. By introducing CuCl into the glass matrix (CuCl@glass), the as‐fabricated samples emit white or yellow light, which depends on the ratios of CuCl:glass. The maximum values of the photoluminescence quantum yield are found to be 37% and 26%, respectively. With the addition of CsCl, CsCu2Cl3, and Cs3Cu2Cl5 phases form in the glass, leading to the phosphor‐in‐glass which emits green light. A maximum luminous yield of 74% is achieved. Based on the synthesized samples, light‐emitting diodes are successfully prepared by the remote packaging technology, and the utilization of the as‐obtained composites for anticounterfeiting application is realized. Herein, an effective approach for the preparation of lead‐free halide perovskite@glass composites is provided, opening up potential commercial applications.

Waste heat recovery potential in the thermochemical copper–chlorine cycle for hydrogen production: Development of an efficient and cost-effective heat exchanger network

With the finite nature of fossil fuel resources and related environmental issues, it is necessary to replace fossil-fuel-based hydrogen production methods with more sustainable ones. For the clean production of hydrogen, the copper-chlorine (Cu–Cl) thermochemical cycle is a favorable choice. However, internal waste heat recovery of the cycle is essential to improve the efficacy of the system. In this paper, the waste heat recovery potential of the four-step Cu–Cl cycle is investigated, to support the design of a new cost-effective and high-performance heat exchanger network. Pinch analysis is executed to find the optimum rates of cold and hot utilities for this cycle. Three heat exchanger network cases are investigated which include case 1, without heat recovery; case 2, with 16 heat exchangers; and case 3, with 11 heat exchangers. The effect of varying design parameters on the energy system's efficiency and cost-related parameters are also explored here. Based on the pinch analysis results, the minimum heating and cooling and the maximum recoverable heat, on a normalized basis, are 333.3 kJ/mol H2, 76.9 kJ/mol H2, and 134.4 kJ/mol H2, respectively. Moreover, for cases 1, 2, and 3 the thermal efficiencies are calculated as 33.3%, 41.1%, and 40.5%, respectively. Additionally, it is observed that, when the thermal energy of the cycle is supplied from a solar power tower plant, the levelized cost of hydrogen for case 1 is 9.6 $/kg H2, for case 2 is 7.9 $/kg H2, and for case 3 is 7.8 $/kg H2.

Process design of a thermochemical cycle for hydrogen production compatible with nuclear fusion heat sources

We quantitatively design a hydrogen-producing copper–chlorine thermochemical cycle that is thermally combinable with nuclear fusion reactors. The mass and heat balances throughout the cycle, including the hydrolysis, pyrolysis, and electrolysis reaction processes, accompanied by multiple separation steps, are numerically investigated. Through the process design, the feasibility of the practical operation of the hydrogen production cycle is presented, and the thermal and electric power required for the operation is evaluated. As we first design a process with straightforward employment of the exact reaction condition from an earlier experimental study of the electrolysis process, the heat required for the condensation of CuCl2 solution is found enormous. By modifying the process condition with an increased electrolyte concentration, to reduce the amount of H2O to be evaporated in the CuCl2 condensation, the total heat for the cycle significantly decreases from 1270 GJ·h−1 (20.3 MJ·mol-H2−1) to 204 GJ·h−1 (3.26 MJ·mol-H2−1). This value is still larger than the heat required for hydrogen production by H2O electrolysis, 48.2 GJ·h−1 (0.772 MJ·mol-H2−1), but an extrapolation towards the saturated CuCl concentration achieves 46.0 GJ·h−1 (0.736 MJ·mol-H2−1). For energy-cost performance improvement of the thermochemical cycle, the development of the electrolytic cell operable with a high concentration of CuCl aqueous solution is thus found to be of primary effectiveness.

Evaluation and comparison of hydrogen production potential of the LIFE fusion reactor by using copper–chlorine (Cu–Cl), cobalt–chlorine (Co–Cl) and sulfur–iodine (S–I) cycles

In this paper, the hydrogen production and neutronic analysis of the Laser Inertial Confinement Fusion-Fission Engine (LIFE) fusion reactor have been analyzed. The potential of hydrogen production from unit integrated of the reactor with three different hydrogen production methods which has copper-chlorine (Cu–Cl) cycle, cobalt-chlorine (Co–Cl) cycle and sulfur-iodine (S–I) cycle have been investigated. Neutronic performance analysis for various parameters was calculated statically by using Monte Carlo N-Particle Nuclear Code and determined optimum reactor operation conditions. The hydrogen production potential for all conditions was investigated as statically. And also, the production potential with determining optimum conditions was performed over operation plant. Tristructural isotropic (TRISO) coated thorium carbide (ThC) was used as fuel of LIFE fusion reactor. Natural lithium and FLiNaBe (LiF + NaF + BeF2) were used first and second coolant, respectively. In the statistical analysis, effects of ThC fuel ratio, 1st and 2nd coolant zone thicknesses were examined. As a consequence of the neutronic analysis, tritium breeding values and energy multiplication values (M) was attained and according to M values, hydrogen production amount, required thermal power and thermal power ratios were acquired. Among the used hydrogen production methods, Cu–Cl cycle produced the highest hydrogen amount, while the Co–Cl cycle has the lowest H2 amount. At the end of the reactor operation time for determining optimum conditions, the produced hydrogen amounts are 9.00, 4.80 and 7.36 kg/s for Cu–Cl, Co–Cl and S–I cycles, respectively.

Heat transfer characteristics and design aspects of thermolysis reactor in copper-chlorine thermochemical water splitting cycle

Thermolysis of copper oxychloride is the highest temperature reaction step of Copper–Chlorine cycle which forms cuprous chloride and oxygen gas as products. In the present study, important design aspects of thermolysis reactor have been investigated experimentally and a mathematical model has been developed to understand the effect of critical parameters on conversion. Experiments were conducted in tubular reactors with three different diameters of 25 mm, 50 mm and 100 mm to study the effect of reactor geometry on heat transfer and conversion. Modelling of batch thermolysis reactor has been carried out using governing heat transport equations coupled with reaction kinetics and validated against experimental data. As per the experimental and modelling results, enhancement in conversion could be achieved with increasing aspect ratio and heat transfer. The studies provide clear insights into the design and scale-up of thermolysis reactor to address the issues of low conversion observed during the multi-step thermal decomposition reaction.

Analysis of copper chlorine electrolysis for large-scale hydrogen production

Nuclear hydrogen production is experiencing an unprecedented momentum worldwide, in response to the increasing demand for clean large-scale hydrogen production in line with the outcomes of the UN Conference of the Parties (COP26). A seamless integration of several innovative nuclear designs including Small Modular Reactors with steam Rankine cycle and the cogeneration of Hydrogen using thermochemical water-splitting cycles (e.g., the Cu–Cl cycle) is possible for a complete solution of hydrogen, oxygen, and electric power generation. In this paper, a process and flow sheet for large-scale hydrogen production by CuCl electrolysis at 50 tonnes per day is proposed and analyzed. The scaled-up process and flow sheet is based on lab-scale experience with 50 l/h hydrogen generation. Pressurized Cu–Cl electrolysis and basic electrolysis are reported to support the scaling up parameters, assumptions, and considerations. Based on determined sizing parameters and energy analysis, the Cu–Cl cycle consumes substantially less primary energy (thermal) than water electrolysis, which makes it a serious competitor, despite its obvious higher investment cost in the hardware.

Simulation and modeling of copper-chlorine cycle, molten carbonate fuel cell alongside a heat recovery system named regenerative steam cycle and electric heater with the incorporation of PID controller in MATLAB/SIMULINK

MCFC (molten carbonate fuel cell) is a relatively new kind of fuel cell that may be utilized in both local and large-scale energy distribution and generating systems. MCFCs are largely regarded as a viable source of renewable energy. Making an MCFC is a time-consuming and costly process. Mathematical modeling and efficiency simulations are essential to appropriately maximize its performance. Regenerative cycle, copper-chlorine cycle, and electric heater with PID controller is also studied to integrate them with MCFC to increase the efficiency of the overall system. Copper–Chlorine cycle is integrated to provide a stable stream of hydrogen and oxygen for the fuel cell. The Molten Carbonate fuel cell of stack 100 generates 1.203 MW of power at Voltage of 1.2 V each. Waste Heat recovery system is installed named regenerative Steam cycle which produces 2.94 MW of power. The total efficiency of system is 57% and the total extracted power is 4.143 MW. MATLAB/Simulink R2020a is used for modeling of multigeneration system with use of Engineering Equation Solver.

A Review on Recent Progress in the Integrated Green Hydrogen Production Processes

The thermochemical water-splitting method is a promising technology for efficiently converting renewable thermal energy sources into green hydrogen. This technique is primarily based on recirculating an active material, capable of experiencing multiple reduction-oxidation (redox) steps through an integrated cycle to convert water into separate streams of hydrogen and oxygen. The thermochemical cycles are divided into two main categories according to their operating temperatures, namely low-temperature cycles (<1100 °C) and high-temperature cycles (<1100 °C). The copper chlorine cycle offers relatively higher efficiency and lower costs for hydrogen production among the low-temperature processes. In contrast, the zinc oxide and ferrite cycles show great potential for developing large-scale high-temperature cycles. Although, several challenges, such as energy storage capacity, durability, cost-effectiveness, etc., should be addressed before scaling up these technologies into commercial plants for hydrogen production. This review critically examines various aspects of the most promising thermochemical water-splitting cycles, with a particular focus on their capabilities to produce green hydrogen with high performance, redox pairs stability, and the technology maturity and readiness for commercial use.

Investigation of a new integrated energy system with thermochemical hydrogen production cycle and desalination

This study presents design, development and analysis of a novel integrated energy system based on renewable geothermal energy source with a Copper Chlorine (CuCl) thermochemical cycle for hydrogen production production and a multistage desalination subsystem for freshwater production. In the proposed system, five useful outputs are effectively generated, such as heat for space heating, electricity, freshwater, hot water and hydrogen. CuCl thermochemical cycle is used for hydrogen production. The need for achieving high-temperature levels for the thermochemical cycle is met by a CuCl cascaded heat pump configuration in the system. The presented system is further analyzed and assessed thermodynamically through energy and exergy approaches. A case study is conducted for the city of Vancouver, Canada. Some parametric studies are also performed to observe the effects of different ambient and working conditions for the overall system and subsystems. According to conducted thermodynamic analysis, 42.06% energy and 49.65% exergy efficiencies are obtained for the overall system. The total exergy destruction rate for the overall system components is determined to be 46.56 MW. In the CuCl-Mercury cascaded heat pump configuration, the coefficient of performance values are obtained as 1.557 for energy and 1.128 for exergy.

RESEARCH OF PHYSICO-CHEMICAL REGULARITIES OF ENVIRONMENTALLY SAFE TECHNOLOGY FOR EXTRACTION OF METALS FROM DUMP SLAG

Pollution of the environment with metals such as lead, nickel, copper, titanium, and zinc is a worldwide public problem, as evidenced by the elevated levels in the blood of people living in polluted areas. The physicochemical analysis of the initial waste slags determined the phase and mineralogical features, as well as the elemental composition of the waste slags of lead production and refractory clays of the Sairam district of the Turkestan region. Thermodynamic studies of the calculation of the Gibbs energy of possible reactions of joint chlorinating roasting of non-ferrous and refractory metals have established the probability of reactions involving lead oxides, and nickel oxides in the presence of aluminum oxides, iron, and calcium chloride. An analysis of the obtained calculated data of the Gibbs energy showed that only in the high-temperature region is possible the joint chlorination of copper and nickel oxides in the presence of aluminum oxide, and in the presence of iron oxide, thermodynamic reaction 6 is likely. Mathematical planning of the experiment determined the technological parameters of the process, ensuring the extraction of nickel up to 94% when firing a mixture of slag and clay at 87-8%.

Rubidium copper chloride scintillator for X-ray imaging screen

Metal halide-based perovskite materials have received great attention in scintillating applications because they can emit strong visible light when interacting with X-ray particles. Here, we report a scintillator based on rubidium copper chlorine incorporated in the polydimethylsiloxane matrix. The scintillator shows a bright violet emission under ultraviolet and ionizing radiation. The temperature-dependent photoluminescence and radioluminescence shows maximum thermal enhancement at 80°C and 60°C, respectively. Moreover, the first X-ray image from this material reveals the detailed information of the object captured by a commercially available digital camera, indicating a potent scintillator for creating X-ray imaging screens.

Energy, exergy, and exergoenvironmental assessment of the coupled electrochemical copper-chlorine with the Goswami cycles

ABSTRACT A novel hybrid combination of the copper–chlorine (Cu–Cl) thermochemical cycle and the Goswami cycle is planned for electrical, cooling, and hydrogen production. In this cycle, geothermal (renewable energy) and natural gas (nonrenewable energy) are used to provide the energy requirements of this multigeneration system. The natural gas in this cycle is used to comply the requirement of the temperature limit for the reaction of the Cu–Cl cycle. This miultigernration system is investigated versus energy, exergy, and exergoenvironmental aspects. The results of this analysis represent this proposed system produces 259.2 tons of hydrogen, 7.82 MWh of electrical energy, and 13.1 MWh of cooling energy over the year. The exergy efficiency for the Cuexergy efficiencyCl, Goswami cycle, and the whole cycle is obtained as 75.8%, 28.7%, and 13.9%, respectively. Moreover, the exergoenvironmental analysis reveals this factor for the Cu–Cl and Goswami cycles is calculated as 0.61 and 1.24, respectively, and for the whole system is equal to 0.68.