Progress in thermochemical hydrogen production with the copper–chlorine cycle

Naterer, G.F.; Suppiah, S.; Stolberg, L.; Lewis, Michele A.; Wang, Z.; Rosen, Marc A.; Dinçer, İbrahim; Gabriel, Kamiel; Odukoya, A.; Secnik, E.; Easton, E. Bradley; Papangelakis, Vladimiros G.

doi:10.1016/j.ijhydene.2015.02.124

Cited by 66 publications

(32 citation statements)

References 61 publications

(40 reference statements)

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“…Canadian national laboratories (CNLs) and the University of Ontario (UOIT) have extensively investigated each step and finally demonstrated individual steps of Cu–Cl cycle . Performance of 300‐cm 2 electrolytic cell was evaluated resulting in a stable current density of 0.55 A/cm 2 at 0.7 V, and 98% of the theoretical hydrogen production rate for over 1600 hours was reported .…”

Section: Introductionmentioning

confidence: 99%

“…Canadian national laboratories (CNLs) and the University of Ontario (UOIT) have extensively investigated each step and finally demonstrated individual steps of Cu-Cl cycle. 17,[19][20][21][22] Performance of 300-cm 2 electrolytic cell was evaluated resulting in a stable current density of 0.55 A/cm 2 at 0.7 V, and 98% of the theoretical hydrogen production rate for over 1600 hours was reported. 23 Fivestep Cu-Cl cycle was also studied, and the proof of concept was demonstrated by India at lab scale with H 2 generation rate at 168 mL/h using 1 g of Cu (0.015 mol).…”

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confidence: 99%

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Investigations on the hydrolysis step of copper‐chlorine thermochemical cycle for hydrogen production

et al. 2019

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Summary Detailed investigations of CuCl2 hydrolysis step of Cu–Cl thermochemical cycle were carried out on various aspects: (a) characterization and thermal properties of reactants/products using X‐ray diffraction (XRD), thermogravimetry–mass spectrometry (TG‐MS), scanning electron microscopy (SEM), temperature‐programmed desorption (TPD), and extended X‐ray absorption fine structure (EXAFS); (b) performance evaluation of fixed bed hydrolysis; (c) parametric optimization with respect to S/Cu, flow rate (gas hourly space velocity, GHSV), reaction duration, temperature, and particle size; and (d) monitored hydrolysis using isothermal TG experiments at 360°C, 370°C, 380°C, 390°C, and 400°C to derive kinetic parameters rate constant (k) and activation energy (Ea) on the basis of the shrinking‐core model. 97% conversion to Cu2OCl2 at 17 630 h−1 of GHSV, 400°C was achieved using ball‐milled CuCl2 (BM6), as compared with that of 55% over commercial un–ball‐milled reactant, CuCl2 (UBM). Correspondingly, higher k value of 2.84 h−1 over BM6 as compared with 0.97 h−1 over UBM reactant at 400°C was achieved. Ea for hydrolysis of BM6 was 93 kJ/mol, while it was 106 kJ/mol for UBM as derived from the Arrhenius plot. A probable pathway for CuCl2 hydrolysis is proposed here. It was found to be diffusion controlled, and the particle size of reactant molecules affects the packing and diffusion length. Based on our investigations, it is very unlikely to get >99% phase pure product (Cu2OCl2). Cu2OCl2 is labile in nature and tends to transform into structurally similar and stable compounds CuO and CuCl2.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Investigations on the hydrolysis step of copper‐chlorine thermochemical cycle for hydrogen production

et al. 2019

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“…Thermochemical water splitting with a copper-chlorine (Cu-Cl) cycle is a promising process involving intermediate copper and chlorine compounds with a net input of water and heat and a net output of hydrogen and oxygen [5,6]. These chemical reactions form a closed internal loop that recycles all chemicals on a continuous basis, without emitting any greenhouse gases.…”

Section: "'%#('#"mentioning

confidence: 99%

“…The numbers of steps (3-steps, 4-steps or 5-steps) have influences on the scale-up challenges and overall cycle efficiencies. A 3-step, 4-step and 5-step cycles of Cu-Cl system for thermochemical water decomposition cycles have been studied extensively [7][8][9] but there is need for comparative studies that can aid in decision making on the most effective and efficient step cycle especially with respect to the second law efficiency of the process [5].…”

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confidence: 99%

Comparative studies of Cu-Cl Thermochemical Water Decomposition Cyles for Hydrogen Production

et al. 2018

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This research focuses on thermodynamic analysis of the copper chlorine cycles. The cycles were simulated using Aspen Plus software. All thermodynamic data for all the chemical species were defined from literature and the reliability of other compounds in the simulation were ascertained. The 5-step Cu–Cl cycle consist of five steps; hydrolysis, decomposition, electrolysis, drying and hydrogen production. The 4-step cycle combines the hydrolysis and the drying stage of the 5-step cycle to eliminate the intermediate production and handling of copper solids. The 3-step cycle has hydrolysis, electrolysis and hydrogen production stages. Exergy and energy analysis of the cycles were conducted. The results of the exergy analysis were 59.64%, 44.74% and 78.21% while that of the energy analysis were 50%, 49% and 35% for the 5-step cycle, 4-step cycle and 3-step cycle respectively. Parametric studies were conducted and possible exergy efficiency improvement of the cycles were found to be between 59.57-59.67%, 44.32-45.67% and 23.50-82.10% for the 5-step, 4-step and 3-step respectively. The results from the parametric analysis of the simulated process could assist ongoing efforts to understand the thermodynamic losses in the cycle, to improve efficiency, increase the economic viability of the process and to facilitate eventual commercialization of the process.

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“…Because the thermal efficiency of Cu‐Cl cycles may be strongly affected by using CuCl/HCl or CuCl electrolyzers, Naterer et al showed that the CuCl/HCl electrolyzer could prevent the copper crossovers and safely produce pure hydrogen gas at low temperature. Wu et al also indicated that the 4‐step Cu‐Cl cycle using CuCl/HCl electrolyzer had a high possibility of commercialization due to the lower grade heat requirement, the less number of equipment, and the higher energy efficiency.…”

Section: Introductionmentioning

confidence: 99%

Design and energy evaluation of a stand-alone copper-chlorine (Cu-Cl) thermochemical cycle system for trigeneration of electricity, hydrogen, and oxygen

Hsu

Chen

2017

Int J Energy Res

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Summary In this article, a new stand‐alone Cu‐Cl cycle system (SACuCl) for trigeneration of electricity, hydrogen, and oxygen using a combination of a specific combined heat and power (CHP) unit and a 2‐step Cu‐Cl cycle using a CuCl/HCl electrolyzer is presented. Based on the self‐heat recuperation technology for the CHP unit and the heat integration of the Cu‐Cl cycle unit, the power efficiency of the SACuCl for 5 prescribed scenarios (case studies) is predicted to achieve about 48% at least. The SACuCl uses the technologies of the dry reforming of methane and the oxy‐fuel combustion to achieve a relatively high CO2 concentration in the flue gas, and CO2 emissions for power generation could be almost restricted by 0.418 kg/kWh. From the aspect of the electricity required for hydrogen production, it is verified that the 2‐step Cu‐Cl cycle system is superior to the conventional water electrolyzer because the CHP process supplies the heat/electricity for Cu‐Cl thermochemical reactions and a thermoelectric generator is connected to the exhaust gas for recovering the power consumption from the compressor and the CuCl/HCl electrolyzer. Finally, the heat exchanger network and the pinch technology are employed to determine the optimum heat recovery of the Cu‐Cl cycle. In case 5 analyzed for the SACuCl, the electricity required for the heat‐integrated 2‐step Cu‐Cl cycle is predicted to dramatically decrease from 4.39 to 0.452 kWh/m3 H2 and the cycle energy efficiency could be obviously increased from 23.77 to 31.97%.

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Progress in thermochemical hydrogen production with the copper–chlorine cycle

Cited by 66 publications

References 61 publications

Investigations on the hydrolysis step of copper‐chlorine thermochemical cycle for hydrogen production

Investigations on the hydrolysis step of copper‐chlorine thermochemical cycle for hydrogen production

Comparative studies of Cu-Cl Thermochemical Water Decomposition Cyles for Hydrogen Production

Design and energy evaluation of a stand-alone copper-chlorine (Cu-Cl) thermochemical cycle system for trigeneration of electricity, hydrogen, and oxygen

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