Investigation of the reduction kinetics of high loaded CuO-based materials suitable for the Ca/Cu looping process

Díez-Martín, L.; Martínez, Isabel Casabona; Grasa, Gemma; Murillo, R.

doi:10.1016/j.fuel.2018.05.054

Cited by 16 publications

(8 citation statements)

References 49 publications

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“…The material was pelletized and the final particle size was in a range 0.6-2 mm to form a homogeneous bed with the sorbent and catalyst. A detailed kinetic study has been also performed elsewhere to determine oxidation and reduction kinetics of the Cu-based material under suitable conditions for the process [41,42]. It was determined that the evolution of material conversion with time can be successfully predicted by a shrinking core model under chemical reaction control and cylindrical geometry.…”

Section: Methodsmentioning

confidence: 99%

“…Momentum balance, Ergun equation [41,42] The wall-bed heat transfer coefficient (h w ) has been experimentally determined as described in the description of the rig. It has been determined as 9.5 W/m 2 K and allowed for an accurate fitting of the energy balance in the model.…”

Section: Reactor Model Descriptionmentioning

confidence: 99%

“…[53]. For the kinetics of the Cu oxidation and CuO reduction, an SCM with cylindrical geometry recently published for the material involved in this work has been considered (See Table 1, [30,42]). The amount of Ni present in bed is low (less than 2 % wt.…”

Section: Reactor Model Descriptionmentioning

confidence: 99%

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Complete Ca/Cu cycle for H2 production via CH4 sorption enhanced reforming in a Lab-Scale fixed bed reactor

Díez-Martín

López

Fernández

et al. 2018

Chemical Engineering Journal

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The three main reaction stages of a H 2 production process based on the combination of the CaO/CaCO 3 and Cu/CuO loops have been experimentally studied in a lab scale fixed bed reactor. The solid bed contained the three functional materials required to run the process, namely a commercial Ni-based catalyst, a CaO-Ca 12 Al 14 O 33 CO 2 sorbent and a CuO-Al 2 O 3 material in a proportion that resulted in a bed with 43.3 % wt. CuO, 25.6 % wt. CaO and 1.7 % wt. Ni. The system was able to convert 13.5 kg CH 4 h-1 kg Ni-1 , at 675 ºC producing a gas stream with a 93.5 % vol. H 2 at 10 bar. The Cu-based material presented high oxidation kinetics, being totally converted in a narrow reaction front with a highly diluted air stream at 10 bar. The Cu-based material presented also fast reduction kinetics and it was completely converted with a fuel gas with typical composition of a SMR stage at high temperature. A Cu/Ca molar ratio of 2 allowed for calcination efficiencies over 85 % molar basis at the CO and H 2 breakthrough , and 95 % of the CO 2 from CaCO 3 exited the reactor at CH 4 breakthrough. The experimental results have been validated with a pseudo homogeneous reactor model for the three reaction stages that *Manuscript Click here to view linked References

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Section: Methodsmentioning

confidence: 99%

Section: Reactor Model Descriptionmentioning

confidence: 99%

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Complete Ca/Cu cycle for H2 production via CH4 sorption enhanced reforming in a Lab-Scale fixed bed reactor

Díez-Martín

López

Fernández

et al. 2018

Chemical Engineering Journal

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“…On the other hand, operating temperature during calcination should be as low as possible with the aim of minimizing the amount of Cu needed in the Ca-Cu process. Typical values proposed for this reduction/calcination step fall down in the range of 850-870°C, which is enough for ensuring complete CaCO3 calcination and sufficiently fast CuO reduction kinetics under the conditions of this reduction/calcination stage (Díez-Martín et al, 2018;Fernández et al, 2016).…”

Section: Hydrogen Production Island Based On the Ca-cu Processmentioning

confidence: 99%

Techno-economic analysis of a natural gas combined cycle integrated with a Ca-Cu looping process for low CO2 emission power production

Martínez

Martini

Riva

et al. 2019

International Journal of Greenhouse Gas Control

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A techno-economic analysis of a natural gas combined cycle integrated with a pre-combustion CO2 capture process based on the Ca/Cu process is carried out. A throughout calculation of the balances of the whole power plant has been done, including the results obtained from a 1-D pseudo homogenous model for the fixed bed reactors that compose the Ca/Cu process. Moreover, a methodology developed by the authors is here presented for calculating the cost of the electricity produced and of the CO2 avoided. This methodology has been used for performing the economic analysis of the Ca/Cu based power plant and to optimize Ca/Cu reactors size and pressure drops in critical heat exchangers. An electricity cost of 82.6 €/MWh has been obtained for the Ca/Cu based power plant, which is 2.2 €/MWh below the benchmark power plant based on Auto Thermal Reformer and MDEA absorption process for CO2 capture. The improved performance of the Ca/Cu based power plant in terms of electric efficiency and reduced capital cost expenditure are the reasons for such reduced electricity costs. Moreover, a lower cost of CO2 avoided is also obtained for the Ca/Cu plant with respect to the benchmark (80.75 €/tCO2 vs. 85.38 €/tCO2), which features 89% of CO2 capture efficiency.

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“…They found that a Cu/Ca molar ratio of 1.8 enabled both the CuO reduction and sorbent regeneration reaction fronts to advance jointly, reaching a maximum temperature in the bed of about 1143 K. Tan et al [19] synthesised a NiO/CuO composite and experimentally tested its catalytic activity for H2 production. Diez-Martin et al [20] experimentally investigated the reduction reaction kinetics with hydrogen, carbon monoxide and methane of two high-load CuO-based materials with different supports for Ca/Cu looping processes. They found that the reduction reaction was kinetically controlled for the Al2O3-supported material, while the internal diffusion resistance becomes predominant for the MgAl2O4-supported one.…”

Section: Sorption-enhanced Steam Methane Reforming (Se-smr) Representmentioning

confidence: 99%

Feasibility of CaO/CuO/NiO sorption-enhanced steam methane reforming integrated with solid-oxide fuel cell for near-zero-CO2 emissions cogeneration system

et al. 2018

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In this article, a process for sorption-enhanced steam methane reforming in an adiabatic fixedbed reactor coupled with a solid oxide fuel cell (SOFC) is evaluated using a 1D numerical reactor model combined with a simplified fuel cell simulation. A novel material comprising CaO/CuO/Al2O3(NiO) pellets is considered. Three operating stages are considered in the proposed system, namely (i) CaO carbonation/reforming, (ii) Cu and Ni oxidation, and (iii) CaCO3 calcination/CuO and NiO reduction. The operating conditions that enable cyclic operation of these stages and the strategy needed to switch between each stage are evaluated. Under the adopted control strategy, methane conversion was about 95%, whilst H2 yield and purity were around 3.2 molH2 molCH4-1 and 90%, respectively. Moreover, a concentrated CO2 stream ready for storage was obtained. By using a portion of the produced H2 to make the process self-sufficient from an energy standpoint, an equivalent H2 yield and a reforming efficiency of about 2.8 molH2 molCH4-1 and 84% were achieved, respectively. With respect to SOFC integration, net power and thermal energy generation of around 11 kW and 6 kW, respectively, can be achieved. With respect to the chemical energy of the inlet methane, the net electrical and thermal efficiencies of the considered process are 56% and 30%, respectively, i.e., the overall efficiency of the entire system is 86%. The proposed cogeneration system showed better thermodynamic, environmental and economic performances than those of conventional systems, with an investment pay-back period of 2.2 years in the worst-case scenario. The levelised cost of electricity, of heat and total power were about 0.096 € kWh-1 , 0.19 € kWh-1 , and 0.065 € kWh-1 , respectively, while the CO2 emissions were avoided at no cost.

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Investigation of the reduction kinetics of high loaded CuO-based materials suitable for the Ca/Cu looping process

Cited by 16 publications

References 49 publications

Complete Ca/Cu cycle for H2 production via CH4 sorption enhanced reforming in a Lab-Scale fixed bed reactor

Complete Ca/Cu cycle for H2 production via CH4 sorption enhanced reforming in a Lab-Scale fixed bed reactor

Techno-economic analysis of a natural gas combined cycle integrated with a Ca-Cu looping process for low CO2 emission power production

Feasibility of CaO/CuO/NiO sorption-enhanced steam methane reforming integrated with solid-oxide fuel cell for near-zero-CO2 emissions cogeneration system

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