Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Enhanced strains of Nb-doped BNKT-4ST piezoelectric ceramics via phase boundary and domain design

A strategy that constructs the morphotropic phase boundary and manipulates the domain structure has been used to design the component of 0.96[Bi_0.5(Na_0.84K_0.16)_0.5Ti_(1-x)Nb_xO₃]-0.04SrTiO₃ (BNKT-4ST-100xNb) to enhance the strain properties for actuator application. Non-equivalent Nb⁵⁺ donor doping modulates the phase transition from the mixture of rhombohedral and tetragonal phases to the pseudocubic phase and results in the coexistence of multiple phases. Moreover, the high-resolution TEM confirms the existence of polar nano regions that contribute to the macroscopic relaxor behaviour. The size of the domains is reduced with increasing Nb⁵⁺, resulting in an enhanced relaxor behaviour. The ferroelectric-relaxor transition temperature decreases from 85 to below 30 °C, implying a non-ergodic to ergodic relaxor transition. An improved strain of 0.56% and a giant normalized strain of 1120 pm/V were achieved for BNKT-4ST-1.5Nb, which were attributed to the unique domain structure in which nanodomains are embedded in an undistorted cubic matrix. Ferroelectric, antiferroelectric, and relaxor phases coexist. As the electric field is large enough, a reversible phase transition occurs. Furthermore, good temperature stability was obtained due to the stability of the nanodomains, and no degradation in strains was observed even after 10⁴ cycles, which may originate from the reversible phase transition and dynamic domain wall. The results show that this design strategy offers a reference way to improve the strain behaviour and that BNKT-4ST-100xNb ceramics could be a potential material for high-displacement actuator applications.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Increasing Volumetric CO2 Uptake of Hypercrosslinked Polymers through Composite Formation

To overcome the drawbacks of solid microporous materials for CO₂ capture, this proof‐of‐concept study demonstrates a low‐cost and rapid method for producing composites consisting of hypercrosslinked polymers (HCP) with a polyethyleneimine (PEI) binder. The resulting materials capture CO₂ through physical and chemical absorption simultaneously. Compared with HCP, the composites exhibit higher CO₂ uptake, higher volumetric density, and improved tolerance to water which is attributed to the PEI binder.     

耦合膜分离的新型CO2低温捕集系统性能优化

CO₂捕集作为温室气体排放控制的有效手段已成为重要研究课题。作为新兴捕集技术之一，低温CO₂捕集因产品纯度高、无附加污染等优势受到关注。然而，该技术能耗和捕集率对于气体中CO₂浓度十分敏感，对于高CO₂浓度气体可获得较高的CO₂捕集率和较低能耗水平。基于此，本文提出了耦合膜分离的新型CO₂低温捕集系统，通过膜材料选择渗透性实现待捕集气体CO₂浓度主动调控，并在最优浓度下进行CO₂低温捕集。首先基于不同传统低温捕集系统特点，对比分析了不同耦合系统模式，从而确定了最优耦合系统结构。针对最优耦合系统进行了运行参数优化，并分别基于实现系统捕集能耗最低与捕集率最高的目标，获得了膜渗透侧CO₂浓度与进气CO₂浓度间的关系式，为该耦合系统中膜组件选型提供指导。研究表明，本文提出的耦合系统捕集能耗为1.92MJ/kgCO₂，相比于传统单一低温系统捕集能耗可降低16.5%。     

柠檬酸铋合成新工艺研究

针对现有柠檬酸铋制备工艺合成时间长、能耗高、产品纯度不高等不足,介绍了一种常温下制备柠檬酸铋的新工艺。新工艺制备时间短,制备的柠檬酸铋产品质量好,合成过程产生的废水可循环利用,废气经碱液循环吸收可生产硝酸钠副产品。     

Simultaneous process optimization and heat integration based on rigorous process simulations

This paper introduces a simultaneous process optimization and heat integration approach, which can be used directly with the rigorous models in process simulators. In this approach, the overall process is optimized utilizing external derivative-free optimizers, which interact directly with the process simulation. The heat integration subproblem is formulated as an LP model and solved simultaneously during optimization of the flowsheet to update the minimum utility and heat exchanger area targets. A piecewise linear approximation for the composite curve is applied to obtain more accurate heat integration results. This paper describes the application of this simultaneous approach for three cases: a recycle process, a separation process and a power plant with carbon capture. Case study results indicate that this simultaneous approach is relatively easy to implement and achieves higher profit and lower operating cost and, in the case of the power plant example, higher net efficiency than the sequential approach.     

Numerical Investigation of the Capture of Polydisperse Particles by Charged Droplets

The capture of particles by charged droplets was simulated by considering the electrostatic interactions of droplet-droplet and droplet-particle. The results indicate that the electrostatic repulsion between droplets leads to a dynamic accumulation mode of particles. However, the droplet spacing has an insignificant effect on the capture efficiency when the electrostatic deposition predominates. The increase of droplet charge remarkably improves the capture efficiency, in which the capture of fine particles accounts for the largest proportion. Compared to the droplet charge, the droplet size shows a limited improvement in the capture efficiency. Reducing the droplet velocity prolongs the capture time instead of enhancing the capture capacity per unit time, thereby improving capture efficiency.