MnCl2-CaCl2-NH3再吸附温度提升系统储能特性

吸附储热因其储热密度高、储热周期长、工作模式灵活而备受关注。基于热化学变温再吸附原理,构建了低品位热能温度提升实验系统,并采用吸附工质对MnCl₂-CaCl₂-NH₃对其升温储能特性进行了理论分析和实验研究。结果表明在储热、释热温度分别为135℃和140℃的条件下,最大储热密度和最大潜热显热比分别为614 kJ·kg^-1、0.418。在储热、释热温度分别为125℃和130℃的条件下,最大储热效率为28.57%。实验验证了热化学温度提升系统的可行性。     

热化学复合吸附储热循环的理论及实验

对一种基于固-气可逆化学反应的热化学复合吸附储热循环的储热特性以及能量品位提升性能进行了理论分析,并以MnCl₂/SrCl₂/NH₃作为工质对进行了实验研究。理论分析表明,热化学复合吸附储热循环不仅可以降低外界驱动热源的温度并保证输出热能温度稳定,而且能大幅度地提升输出热能的温度品位。在MnCl₂和SrCl₂都参与放热的实验工况下,获得的储热效率为93.31%。MnCl₂复合吸附剂的总储热密度按单位质量反应盐MnCl₂和单位质量的固化吸附剂计量分别为4393.36和3734.36 kJ·kg^-1;SrCl₂复合吸附剂的总储热密度按单位质量反应盐SrCl₂和单位质量的固化吸附剂计量分别为1947.28和1655.19 kJ·kg^-1。结果表明,热化学储热是一种相当有潜力的储热方式,可为低品位热能的高效回收利用提供强有力的技术支持。     

氯化锰/氨热化学吸附储热的特性

热化学吸附储热具有储热损失小、储热密度高、可实现冷热复合储存等优点，近年来得到了广泛的关注。本文以MnCl₂/NH₃作为吸附储热工质对，基于热化学吸附技术构建了热化学吸附储热实验平台，对MnCl₂/NH₃热化学吸附系统的储热性能进行了理论分析和实验研究。结果表明：在解吸充热温度、吸附放热温度、冷凝/蒸发温度分别为162℃、45℃和25℃的运行条件下，试验获得的吸附储热密度最大，其值为1296.36kJ/kg MnCl₂或1101.90kJ/kg固化复合吸附剂。当放热温度从45℃增大到85℃时，热化学吸附储热系统的吸附储热效率从38.98%降低至24.08%。由于传热传质、化学反应动力学等因素的影响，相同运行工况下吸附储热系统实际所获得的储热性能要低于理论值。     

太阳能热化学储能研究进展

太阳能热发电技术对缓解全球资源紧张和改善环境有广阔的应用前景,大规模高温无损储热是太阳能热发电系统的关键。本文通过对显热储能、潜热储能和热化学储能3种热能储存方式的比较,认为热化学储能方法由于储能密度高,且可长期在环境温度下无热损储存,因而为太阳能热发电中的高温热能储存提供了一种潜在的方法。并对热化学储能在太阳能热力发电的应用上进行了技术经济分析,综述了几种有前景的热化学储能体系的研究进展,总结了各种储能体系的现存问题。根据热化学储能方法在实用化过程中存在的技术经济问题,指出了热化学储能技术的未来研究方向是储能反应器的设计、能量储存/释放循环性能探究、储能体系的选择及热化学储能系统的中试放大研究等。     

Synthesis and thermal properties of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) copolymers as novel solid–solid phase‐change materials for thermal energy storage

We synthesized a series of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) (PAA‐g‐MPEG) copolymers as novel polymeric solid–solid phase‐change materials by grafting methoxypoly(ethylene glycol) (MPEG) to the main chain of poly(acrylonitrile‐co‐allyl glycidyl ether) (PAA). PAA was the skeleton, and MPEG was a functional side chain, which stored and released heat during its phase‐transition process. Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy analysis were performed to investigate the chemical structures. The crystalline morphology and crystal structures were also measured with polarized optical microscopy and X‐ray diffraction. Moreover, the thermal‐energy‐storage properties, thermal stability, and thermal reliability of the PAA‐g‐MPEG copolymers were characterized by differential scanning calorimetry and thermogravimetric analysis (TGA) methods. These analysis results indicate that the MPEG chains were successfully grafted onto PAA, and we found that the PAA‐g‐MPEG copolymers had typical solid–solid phase‐transition temperatures in the range 11–54 °C and high latent heat enthalpies between 44 and 85 J/g. In addition, the as‐prepared PAA‐g‐MPEG copolymers showed reusability and thermal reliability, as shown by the thermal cycle testing and TGA curves. Therefore, the synthesized PAA‐g‐MPEG copolymers have considerable potential for thermal energy storage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46641.     

Novel bismuth ferrite‐based lead‐free ceramics with high energy and power density

In this work, a new lead‐free relaxor ferroelectric 0.60BiFeO₃‐0.34BaTiO₃‐0.06Sr(Al_0.5Nb_0.5)O₃ (BBFTO‐SAN) ceramic was prepared via the conventional solid‐state reaction method. High recoverable energy density (1.75 J/cm³) and efficiency (81%) were achieved, which is superior to some other lead‐free ceramics. Good thermal stability in a wide temperature range (30‐120°C) was also investigated in this system. Moreover, we first studied the charge‐discharge performance of bulk BFO‐based energy storage ceramics and obtained an ultra‐high power density p_D (~57 MW/cm³) as well as a large current density value of ~1353 A/cm². Consequently, all the results indicate that this ceramic is a promising lead‐free candidate for energy storage materials.     

Optimum heat storage design for solar‐driven absorption refrigerators integrated with heat exchanger networks

A methodology is presented for optimizing hybrid renewable energy‐fossil fuel systems with short‐term heat storage. The considered system is an absorption‐refrigeration (AR) cycle integrated with a heat exchanger network (HEN) requiring cooling below ambient temperature. The AR cycle can be driven by multiple energy sources including excess energy from hot process streams, renewable energy sources (solar and biofuels), and fossil fuels. A two‐step approach based on mixed integer nonlinear programming methods is used for the optimization. First, the problem of optimal energy integration in the hybrid energy system without heat storage is solved on a monthly basis by minimizing simultaneously the total annual cost and the overall greenhouse gas emissions. In the second step, the multi‐tank thermal energy storage (TES) design problem is solved. The design involves the identification of the optimal number of storage tanks, their sizes, configuration and operation policies. The TES optimization is carried out on an hourly basis while incorporating the design targets determined by the first step. © 2013 American Institute of Chemical Engineers AIChE J, 60: 909–930, 2014     

4-Temperatures Approach: Testing Thermochemical Heat Storage Materials Under Application Conditions

Thermochemical heat storage offers the possibility to achieve high thermal energy storage capacities compared to sensible and latent heat storage. To quantify this advantage, thermochemical storage systems have to be evaluated under application conditions. The proposed 4-temperatures approach delivers a first step toward a realistic testing of thermochemical working pairs. As an example, the approach is applied to testing the working pair zeolite/water under the conditions of the application of seasonal storage of solar thermal heat for domestic heating purposes.     

High temperature electrochemical heat pump using water gas shift reaction. Part I: Theoretical considerations

A new electrochemical heat pump using a combination of an electrolytic reaction at lower temperature to absorb low grade thermal energy and a thermochemical reaction at higher temperature to produce more efficient thermal energy is proposed. At a lower temperature, an endothermic reaction which cannot occur thermochemically proceeds with electrolysis. At a higher temperature, an exothermic reaction which is the reverse of the electrolysis reaction occurs thermochemically to produce high grade thermal energy. The water gas shift reaction, CO₂(g) + H₂(g) CO(g) + H₂O(g), in molten carbonate is one possible candidate for the new electrochemical heat pump and can lead to an increase in the temperature of the thermal energy from 1100 to 1200K. A heat pump system using the shift reaction is also considered theoretically.     

基于太阳能蓄热过程的甲烷二氧化碳重整研究进展

热化学储能技术因为其储能密度高、热损小、能长距离运输等优点而成为保证太阳能长久稳定供应的关键技术。本文对基于甲烷二氧化碳重整反应的太阳能热化学储热系统研究现状进行了回顾,重点讨论了甲烷重整催化剂、重整反应器以及储能系统整体的传热特性等3个方向的研究进展。指出新型高效催化剂以及反应器开发和性能测试是目前该领域的主要研究方向。发现辐射热损失、非均匀温度分布特性、辐射热流的时变波动特性,以及由此造成的能量与化学反应的不匹配限制了热化学系统能量储存效率的进一步提高,并提出催化剂的催化特性与物性/结构参数依变关系,反应器辐射吸收特性、传热传质特性和反应特性之间的相互作用机制,以及系统时变动态特性与反应物流/辐射能流的匹配关系是建立甲烷重整热化学储能系统优化设计理论亟待解决的关键问题。     

Poly(styrene‐co‐maleic anhydride)‐graft‐fatty acids as novel solid–solid PCMs for thermal energy storage

A solid–solid phase change material (S‐SPCM) can store and release a specific amount of latent heat during its phase transition. In this regard, poly(styrene‐co‐maleic anhydride) (SMA)‐graft‐fatty acids (FA) copolymers were synthesized as novel S‐SPCMs for thermal energy storage (TES). The chemical structures of the SMA‐g‐FA copolymers were characterized by proton nuclear magnetic resonance (¹H NMR) and Fourier transform infrared (FT‐IR) spectroscopy techniques. The phase transformations of the copolymers form crystalline phase to amorphous phase were monitored using polarized optical microscopy (POM). The latent heat TES (LHTES) properties, thermal cycling reliability, and thermal stability of the S‐SPCMs were investigated by differential scanning calorimetry and thermogravimetric analysis methods. The SMA‐g‐FA copolymers produced as S‐SPCMs showed solid–solid phase transitions at about 40°C–60 °C range and had latent heat storage and release ability between 84 and 127 J/g, respectively. The S‐SPCMs had stable chemical structures and reliable LHTES characteristics even after 5,000 thermal cycling. They had reasonable thermal conductivity value changed in the range of 0.15–0.19 W/mK. Furthermore, it was concluded that the SMA‐g‐FA copolymers can be considered as promising S‐SPCMs for TES utilizations. POLYM. ENG. SCI., 59:E337–E347, 2019. © 2019 Society of Plastics Engineers     

A sustainable bio-adsorbent for thermal energy storage for space heating applications

Thermal energy storage is an emerging technology that allows the storage of heat when it is available, which can be used later. One of the available technologies for thermal energy storage is the adsorption of moisture from air by adsorbents. Several adsorbents have been studied in the literature for this application, but there is a need for a sustainable adsorbent that can be eco-friendly, cost effective, and available for scale-up for commercialization of the technology. The current paper focused on the synthesis of a flax shives-based composite (equal weight percent of flax shives and salt hydrates) prepared by the impregnation method and its application in thermal energy storage. The composite showed durability, stability, and reasonable energy storage density with a very low cost per unit of energy. The structural characterization of the hybrid was performed by scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX). The thermal energy storage density, as well as the charging/discharging characteristics were measured using a laboratory-scale thermal energy storage apparatus. The flax/CaCl₂/LiCl hybrid showed reasonable energy storage density at 74 kWh/m³ for 50% inlet relative humidity after regeneration at 120°C. Although the energy storage density was not high, the flax/CaCl₂ composite was found to be the most cost-effective material, as it showed the lowest cost per energy stored at 0.98 CAD/kWh at 50% relative humidity (RH) after regeneration at 120°C.     

Conceptual design of ammonia‐based energy storage system: System design and time‐invariant performance

Chemicals‐based energy storage is promising for integrating intermittent renewables on the utility scale. High round‐trip efficiency, low cost, and considerable flexibility are desirable. To this end, an ammonia‐based energy storage system is proposed. It utilizes a pressurized reversible solid‐oxide fuel cell for power conversion, coupled with external ammonia synthesis and decomposition processes and a steam power cycle. A coupled refrigeration cycle is utilized to recycle nitrogen completely. Pure oxygen, produced as a side‐product in electrochemical water splitting, is used to drive the fuel cell. A first‐principle process model extended by detailed cost calculation is used for process optimization. In this work, the performance of a 100 MW system under time‐invariant operation is studied. The system can achieve a round‐trip efficiency as high as 72%. The lowest levelized cost of delivered energy is obtained at 0.24 $/kWh, which is comparable to that of pumped hydro and compressed air energy storage systems. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1620–1637, 2017     

Design of mixed energy‐integrated batch process networks by Pseudo‐direct approach

In this article, a novel framework for the design of mixed (combined direct and indirect) integration for batch process systems is presented. The framework is based on the concept of pseudo‐direct energy integration (PDEI) which reformulates indirect integration as direct integration using pseudo‐process streams. Two algorithms are presented to achieve energy integration for batch processes operating cyclically (in a campaign mode). The first algorithm targets maximization of energy recovery and overcomes the limitations of some of the existing contributions for design of mixed integrated systems. The second algorithm provides a network reduction methodology to generate a cadre of integrated designs while exploring the trade‐off between capital (number of heat exchangers and storage units) and operating costs (utility consumption). The proposed framework is illustrated using a benchmark example of two hot and two cold streams. © 2017 American Institute of Chemical Engineers AIChE J, 63: 55–67, 2018     

A power plant for integrated waste energy recovery from liquid air energy storage and liquefied natural gas

Liquefied natural gas(LNG)is regarded as one of the cleanest fossil fuel and has experienced significant developments in recent years.The liquefaction process of natural gas is energy-intensive,while the regasification of LNG gives out a huge amount of waste energy since plenty of high grade cold energy(-160℃)from LNG is released to sea water directly in most cases,and also sometimes LNG is burned for regasification.On the other hand,liquid air energy storage(LAES)is an emerging energy storage tech-nology for applications such as peak load shifting of power grids,which generates 30％-40％of compres-sion heat(～200℃).Such heat could lead to energy waste if not recovered and used.The recovery of the compression heat is technically feasible but requires additional capital investment,which may not always be economically attractive.Therefore,we propose a power plant for recovering the waste cryo-genic energy from LNG regasification and compression heat from the LAES.The challenge for such a power plant is the wide working temperature range between the low-temperature exergy source(-160℃)and heat source(～200℃).Nitrogen and argon are proposed as the working fluids to address the challenge.Thermodynamic analyses are carried out and the results show that the power plant could achieve a thermal efficiency of 27％and 19％and an exergy efficiency of 40％and 28％for nitrogen and argon,respectively.Here,with the nitrogen as working fluid undergoes a complete Brayton Cycle,while the argon based power plant goes through a combined Brayton and Rankine Cycle.Besides,the economic analysis shows that the payback period of this proposed system is only 2.2 years,utilizing the excess heat from a 5 MW/40MWh LAES system.The findings suggest that the waste energy based power plant could be co-located with the LNG terminal and LAES plant,providing additional power output and reducing energy waste.     

Large recoverable energy density with excellent thermal stability in Mn‐modified NaNbO3‐CaZrO3 lead‐free thin films

Effect of Mn dopant on energy storage properties in lead‐free NaNbO₃?0.04CaZrO₃ (NNCZ) thin films was investigated. The leakage current was largely suppressed, whereas dielectric constant, breakdown fields, and the difference between maximum polarization and remnant polarization were improved significantly by Mn doping, resulting in a large enhancement of energy storage performance. A large recoverable energy storage density of ~19.64 J/cm³ and an excellent thermal stability (from 30 to 160°C) were simultaneously achieved in the NNCZ thin film with 1 mol% Mn addition. Our results ascertain the great potential of NNCZ lead‐free thin films for the applications in energy storage devices over a wide temperature range.     

Blackened calcium-based composite particles and their apparent kinetics features for solar thermochemical energy storage

The calcium looping (CaL) thermochemical thermal energy storage is one of the best high-temperature heat storage schemes for 3th concentrating solar power (CSP) photothermal power. However, the application of this technology is greatly hindered by the low solar absorption capability and the poor cyclic stability of CaCO₃/CaO-based material. In this article, the solar absorbing capability of CaCO₃ particles is enhanced by doping Mn-Fe oxides, meanwhile, awns of setaria faberis (ASF) and microcrystalline cellulose (MCC) are used as bio-templates to generate pores inside the particles. The pore-making process promotes the cyclic stability and carbonation kinetic features of the composite particles simultaneously. The test results show that the proposed particles possess adequate anti-crushing strength, high cyclic stability, high solar absorption, and high carbonation rate. In addition, the apparent carbonation kinetic features of the composite porous particles are studied with the influencing factors such as CO₂ partial pressure, reaction temperature, and particle morphology taken into consideration. A kinetic equation involving these parameters is developed with the thermogravimetry data of the prepared samples. By employing this kinetic function, the carbonation reaction of the prepared particles inside the carbonator becomes predictable, which is of great significance for the design and regulation of the carbonator achieving highly stable thermal output from the CaL thermochemical heat storage system.     

Heat Transfer from Immersed Vertical Cylinders in Gas‐Liquid and Gas‐Liquid‐Solid Fluidized Beds

The heat transfer coefficient, h, was measured using a cylindrical heater vertically immersed in liquid‐solid and gas‐liquid‐solid fluidized beds. The gas used was air and the liquids used were water and 0.7 and 1.5 wt‐% carboxymethylcellulose (CMC) aqueous solutions. The fluidized particles were sieved glass beads with 0.25, 0.5, 1.1, 2.6, and 5.2 mm average diameters. We tried to obtain unified dimensionless correlations for the cylinder surface‐to‐liquid heat transfer coefficients in the liquid‐solid and gas‐liquid‐solid fluidized beds. In the first approach, the heat transfer coefficients were successfully correlated in a unified formula in terms of a modified j_H‐factor and the modified liquid Reynolds number considering the effect of spatial expansion for the fluidized bed within an error of 36.1 %. In the second approach, the heat transfer coefficients were also correlated in a unified formula in terms of the dimensionless quantities, Nu/Pr^1/3, and the specific power group including energy dissipation rate per unit mass of liquid, E^1/3D^4/3/ν_l, within a smaller error of 24.7 %. It is also confirmed that a good analogy exists between the surface‐to‐liquid heat transfer and mass transfer on the immersed cylinder in the liquid‐solid and gas‐liquid‐solid fluidization systems.     

吸附式制冷新技术

固体吸附式制冷技术是充分利用低品位热能的一种有效手段 ,本文结合国际上吸附制冷研究的最新动态以及作者实验研究成果 ,对吸附式制冷系统及其在能量综合利用中的一些新技术进行了总结及探讨 .