吸附剂固化的发展与固化活性炭块的试验研究

吸附剂的固化成型被认为是增大吸附式制冷系统的制冷量一个可行的方法。本文一方面综述了吸附系统中吸附剂固化的发展现状，讨论各种固化技术和方法。另一方面总结了在我们实验室所涉及的活性炭固化研究工作，给出了以块状活性炭一甲醇为吸附工质对时比较合适的固化工艺参数。     

A non-uniform temperature non-uniform pressure dynamic model of heat and mass transfer in compact adsorbent beds

This paper discusses a new dynamic two-dimensional model for the simulation of innovative consolidated-type adsorbent beds to use in adsorption energy systems. It consists of a cylindrical pipe, conveying the thermal vector fluid, coated with a layer of consolidated zeolite.The governing equations take into account with detail the transport phenomena and are solved according to advanced numerical methods in the time and space domain.A parametric analysis is carried out for the evaluation of the overall system performance sensitivity to the most meaningful parameters, such as adsorbent bed thickness, water vapour permeability and heat transfer coefficients. A critical discussion is also made about the most credited adsorbent bed arrangements, i.e., pure powder, consolidated powder and metal bound consolidated powder. It was possible to demonstrate that the adsorbent bed, of consolidated powder type, proposed by the CNR-ITAE Lab, performs better than other bed arrangements available in the literature.     

The heat and mass transfer performance of facile synthesized silica gel/carbon-fiber based consolidated composite adsorbents developed by freeze-drying method

A series of experimental investigations had been performed to analyze the heat and mass transfer performance for two novel types of silica-based consolidated composite adsorbents developed by the freeze-drying method. The first type of adsorbent is silica gel consolidated with carboxymethyl cellulose (CMC) (SC), while the other is silica gel consolidated with CMC and carbon fiber powder (SCC). Results indicate that the thermal conductivity of consolidated composite adsorbents increases with the mass proportion of carbon fiber powder, while it decreases with the increasing moisture content in the preparation process of the adsorbents. When the mass ratio of silica gel, CMC, and carbon fiber powder is 4:1:4, the highest thermal conductivity of consolidated composite adsorbent obtained from experiments reaches 1.66 W m^?1 K^?1, which is 13.4 times greater than that of pure silica gel. Furthermore, the results of macroporous properties analysis of typical samples including SC20 and SCC20 (where the 20 means that the undried samples have a water content of 20% by mass during the preparation process) show that heat transfer additives effectively improve the macroporous porosity and permeability of the consolidated composite adsorbents. The study on adsorption dynamic performance indicates that the freeze-drying method helps to improve the adsorption performance including adsorption rate and equilibrium water uptake. The experimental results also show that the mass transfer coefficient K of the two typical samples are approximately stable at 5 × 10^?3 s^?1 when the adsorption temperature is ranged between 30 and 40°C, which are almost twice the corresponding values of the samples developed by heating–drying method. Therefore, the proposed approach which is the consolidation with heat transfer additives combined with freeze-drying method is effective for simultaneously enhancing the heat and mass transfer performance of the silica gel adsorbents.     

新型吸附式制冷系统吸附床的研究进展

吸附床的传热传质性能是提高吸附式制冷效率的关键,优化吸附床的结构能够有效提高整个吸附床的传热传质效率,减少热量损失,提高系统的制冷效率（coefficient of performance, COP）和单位质量吸附剂制冷量（specific cooling power, SCP）。本文介绍了近年来几种新型吸附床的类型,综述了吸附剂侧的固化吸附剂和涂层吸附剂,以及换热器侧的新型换热器结构。最后阐述新型吸附床的未来发展方向和研究重点。     

A review on adsorption refrigeration technology and adsorption deterioration in physical adsorption systems

As one kind of environmentally friendly refrigeration, the adsorption refrigeration has attracted many attentions in resent decades. This paper introduces the researches of adsorption refrigeration systems with the commonly used working pairs, advanced adsorption cycles, heat and mass transfer enhancement and attempts of adsorption refrigeration applications. Poor heat and mass transfer problem is a bottleneck to prevent the improvements of the adsorption refrigeration technique. Two ways to enhance the heat and mass transfer are discussed in this paper. The adsorption deterioration of adsorbent, another obstacle to physical adsorption refrigeration applications, is also pointed out. And the possible reasons and the possible methods are analyzed.     

Water vapor adsorption kinetics on small and full scale zeolite coated adsorbers; A comparison

A possibility to enhance both heat and mass transfer characteristics of an adsorber heat exchanger is to apply the adsorbent directly to its surface in form of a consolidated layer. As the majority of the available publications on the effect of both coating technology and adsorbent layer thickness on the adsorption kinetics deals with small scale adsorbent samples, the results obtained can only represent the best case design of an adsorber heat exchanger. This article presents, therefore, a comparison between the adsorption kinetics of water vapour on small as well as two different full scale coated adsorber heat exchanger types with AQSOA-Z02 layers of Mitsubishi Plastics Incorporation under quasi isobaric conditions of adsorption heat pumps. The small scale coated samples have a zeolite dry mass of 200 mg and layer thicknesses of 200, 300 and 500 μm while the full scale adsorbers have a coated zeolite mass between 1.5 and 2.5 kg and layer thicknesses of 150, 200, 300, 400 and 500 μm. In the investigated adsorption heat pump module, up to 52.7 and 57.3% of the equilibrium differential water loading measured with the small scale coated substrates have been obtained after an adsorption-evaporation times of 300 and 600 s, respectively.     

Heat and mass transfer in adsorbent bed with consideration of non-equilibrium adsorption

In the solid adsorption refrigeration cycles, the actual adsorption processes are all non-equilibrium. To investigate the heat and mass transfer in adsorbent bed, mathematical model is established and solved by a numerical method. The relations between adsorption temperature, adsorption velocity, adsorption quantity, coefficient of performance (COP), specific cooling power (SCP) and time are discussed during the process of cooling the adsorbent bed. The relations between desorption temperature, desorption velocity, desorption quantity and time are discussed during the process of heating the adsorbent bed. It indicates that there is a peak value for adsorption velocity in the adsorption process and there is also a peak value for desorption velocity in the desorption process. It also shows that the changing rate of the adsorbent temperature tends to let up, and the coefficient of performance value grows nearly linearly in the adsorption process and there is a peak value of SCP in the adsorption process.     

Solar cooling using an open-cycle adsorption system with adiabatical mass transfer and external heat exchange

The viability of an open-cycle adsorption system for solar cooling using an adiabatic adsorption column with a solid adsorbent and external heat exchange is examined. Experimental investigations on a column of silica-gel have been carried out parallel to a computer simulation of a complete system. Because of the heat exchanger having a large influence to the efficiency of the system, different types of heat exchangers have been examined. Climatic data from southern Spain and central Oregon (U.S.A.) have been used for simulations. The results show that compact and simple adsorption columns can be successfully used on open-cycle adsorption systems and that high enough temperatures can be reached using solar collectors of simple construction for the regeneration of the adsorbent material.     

Heat and mass transfer during adsorption of ammonia in a cylindrical adsorbent bed: thermal performance study of a combined parabolic solar collector, water heat pipe and adsorber generator assembly

In this paper we present the study of adsorption refrigerator which use an activated carbon-pair ammonia. The ability of activated carbons to adsorb large mass of ammonia makes them ideal for use in adsorption refrigeration and pump systems. These systems have not reasonable efficiency. In order to make these systems economically viable, their size must be reduced. This implies a need for a rapid heating and cooling the adsorbent/refrigerant pair. However, the main problems to be overcome is related to the poor heat transfer in the adsorbent bed. So, it is necessary to study and understand the heat and mass transfer within the bed and to improve it. A detailed model of heat and mass transfer into the generator has been developed. For a given heat flux, temperature and adsorbed mass have been computed in every point at each step time along the adsorbed bed (generator). Experimental installation simulating an adsorption machine working within a temperature ranging from 20 to 250 °C and pressure ranging from 0 to 2.5 × 10⁶ Pa, allows for identification of the generator's equivalent thermal conductivity and internal heat transfer coefficient. These two parameters are then used to simulate thermal performance of a design whose features include the insertion of stainless steel water heat pipe (HP's) condensers into the generator. The HP's evaporator heat input is of solar origin using a compound parabolic collector (CPC). Nominal Solar coefficient of performance, COPs =14.37% obtained through both Adimensional Exergy Loss (AEL), and COP study, shows the competitiveness of the proposed design.     

Study of thermal conductivity,permeability, and adsorption performance of consolidated composite activated carbon adsorbent for refrigeration

Composite adsorbents, comprising activated carbon and expanded natural graphite, have been developed, and their thermal conductivity, permeability and adsorption performance were tested. The thermal conductivity varied with the ratio of activated carbon to expanded natural graphite. Thermal conductivity increased as the ratio of expanded graphite increased. Considering that the density of activated carbon for the composite adsorbent should not be lower than 200 kg/m³, otherwise the volumetric cooling capacity would be unacceptably low, the highest thermal conductivity obtained from experiments was 2.47 W m^?1 K^?1. The permeability was also measured, and the best result obtained was 4.378 × 10^?12 m². In order to evaluate the influence of heat and mass transfer on adsorption performance, the adsorption rate was tested using a Rubotherm magnetic suspension balance, and results showed that for the freezing conditions lower than ?10 °C the performance of granular activated carbon was better than that of solidified adsorbent because of the reduced mass transfer of ammonia at low saturated pressure. The adsorption performance of consolidated adsorbents increased rapidly when the evaporating temperature was higher than ?10 °C. When the evaporating temperature was 8 °C, the adsorption rate of consolidated adsorbent was improved by 29% if compared with that of granular adsorbent.     

Solar energy storage using chemical potential changes associated with drying of zeolites

Compact solar storage systems depend upon identification of systems which can store energy as chemical potential. Simple, noncorrosive, systems that operate at reasonably low temperatures are rare. The use of the heat of adsorption of moisture on zeolite molecular sieves is discussed here. The advantages of zeolites are high heats of adsorption (as much as 80 kJ mol⁻¹), large maximum adsorption capacity (0.2–0.3 kg H₂O/kg adsorbent) and easy control of the store following from control of heat output by regulations of flows of moist air. The disadvantages are the relatively high upper temperature required to utilize maximal storage capacities (up to 250°C) and cost. There is reason to project falling cost.

Zeolite storage is compared favourably with respect to capacity to water, stone, and heat of phase change systems. Compared to salt hydrates, acid solution, and salt solutions any capacity advantage is supplemented by low corrosion and opportunity for long term storage. Zeolites are compared favourably to alternative absorbent materials; alumina, charcoal, and silica gel.

The warm dry air output from a zeolite storage bed can be utilized not only in space heating but also in the drying of agricultural timber and fish products.     

沸石分子筛-水吸附工质对的吸附性能及导热性能

吸附工质对的吸附和传热性能是研究吸附式干燥、除湿及制冷的重要基础，由于吸附量与导热系数和吸附材料的性质、温度、压力等许多因素有关，需要通过实验来确定。该文通过对几种沸石分子筛的性能实验研究，测定了其最大吸附量、密度、吸附等压线及导热系数等一系列性能参数及其影响因素，并给出了实际循环过程中吸附床的温度、压力与吸附量之间的关系。研究表明沸石对水的吸附基本满足D—A方程，而沸石导热系数受温度以及吸附量的影响较大，随着温度及吸附量的增加而增加。     

Theoretical and experimental investigation of a constant-pressure adsorption process

This paper presents a theoretical and experimental analysis of a constant pressure adsorption process. The governing heat and mass transfer equations derived from local thermodynamic equilibrium and energy balance are solved numerically. The model is validated by comparison with experimental results. It is then used to analyze the effect of some operating and design parameters on a constant-pressure sorption process. The adsorbent thickness and heat transfer coefficient between the adsorbent and the heating/cooling fluid have the strongest influence on sorption kinetics and on the cooling capacity of adsorption systems.     

SrCl_2-NH_3化学吸附式制冷工质对吸附特性的研究

对以SrCl2 为吸附剂、NH3 为致冷剂所组成的化学吸附式制冷工质对的吸附性能进行了研究 ,得到了吸附等温线、回归出吸附等温方程并对化学吸附过程机理进行了探讨。研究结果表明 ,SrCl2 NH3 工质对的吸附制冷量大 ,适宜太阳能或低品位余热驱动 ,是性能优良的工质对。     

固体吸附式制冷强化传热研究进展

吸附床的传热强化是影响固体吸附式制冷的主要因素。简述了吸附制冷的强化传热研究进展,介绍了几种常用的吸附床强化传热方法,提出了固体吸附式制冷强化传热的研究方向。     

Experimental study of a solidified activated carbon-methanol adsorption ice maker

In this paper, the experiments are performed on an adsorption ice maker driven by waste heat, which uses up to two beds. Each bed uses methanol as refrigerant and solidified activated carbon (120 kg adsorbent totally, 60 kg adsorbent per bed) as adsorbent. This system is designed to be driven by the waste heat of a 100 kW diesel engine. The experiments show that the cooling power could be enhanced by the mass recovery process up to 11%, and the heating power could be lowered by the heat recovery process up to 30%. The optimal cooling power of this prototype is about 2.0 kW and corresponds to a specific cooling power (SCP) is about 17 W/kg with both heat and mass recoveries between two beds. Considering the optimal adsorption time is much longer than optimal desorption time at the condition of ice making, the experiments are operated on a single bed (60 kg adsorbent per bed) and the adsorption time used in experiments is two times of desorption time, then the performance of a three-bed adsorption ice maker (120 kg adsorbent totally, 40 kg adsorbent per bed) is predicted by the results of experiments on this single bed. The results of prediction show that both COP and cooling power of three-bed operation could be enhanced greatly compared to the two-bed operation; optimal SCP and COP are respectively 22 W/kg and 0.239 when mass and heat recoveries proceed between three beds. Optimal ice productivity of this three-bed system is 21 kg/h when the water temperature is 25 °C and ice temperature is −7 °C.     

A parametric study on isobaric adsorption process in a closed adsorbent bed

A numerical study on heat and mass transfer in an annular adsorbent bed filled with adsorbent granules for an isobaric adsorption process is performed. In order to reduce the number of independent parameters that influences heat and mass transfer in the bed, the governing equations and related initial and boundary conditions for the problem are non-dimensionalized and this yields two dimensionless parameters as G and Γ. The G dimensionless parameter is the ratio of heat of adsorption to sensible heat stored by adsorbent particle and Γ parameter compares mass diffusion within the adsorbent particle and heat diffusion in the radial direction of the adsorbent bed. The obtained results show that the total dimensionless time for an adsorption process can be reduced by increasing of Γ value. The total dimensionless time is independent from G for low values of Γ (i.e. Γ = 10^− 5). The results also show that the instantaneous equilibrium model can provide accurate results only for an adsorbent bed with a low value of Γ (i.e. Γ = 10^− 5). The present study is performed for Γ values from 10^− 5 to 1 and G value from 1 to 100.     

Comparative study on adsorbent characteristics for adsorption thermal energy storage system

The adsorption performance of the thermal energy storage (TES) system changes depending on the material properties of the adsorbent itself, but the change of the hardware structure can also substantially change the adsorption characteristics. In this study, a laboratory‐scale adsorption‐based TES system was constructed, and the adsorption performance of three adsorbents was evaluated in the same system to compare the adsorption performance between adsorbents. The adsorption characteristics of silica gel, zeolite 13X, and 4A, which are the most preferred adsorbents in the physical adsorption‐based TES system, were selected for evaluation. Experiments with each adsorbent were performed, including heat recovery to evaluate the heat transfer effect and the amount of heat recoverable in the actual TES system. Experimental results have identified several key characteristics of the adsorption and performance of each adsorbent in the TES system, as well as operating parameters that determine the influence of adsorption performance on the TES system. The actual energy storage density of the adsorbent is affected not only by the enthalpy of adsorption of the material itself but also by other factors. These factors include the difference in thermal conductivity that causes a difference in temperature distribution and the magnitude of mass transfer resistance due to the shape of the adsorbent particle and the actual TES system reactor structure. If the reaction heat generated during the adsorption reaction cannot be effectively released, the adsorption performance is significantly lowered due to the increased temperature of the reactor inside. This phenomenon was commonly observed in adsorbents examined in the present study. The uptake amount, X [g/g], was increased by allowing the inside of the reactor to be maintained at a lower temperature through heat recovery. In case of silica gel, the temperature rise during adsorption reaction is not high due to the difference of isotherm characteristics compared with zeolites, but it is possible to absorb more amount of adsorbate and to recover heat for a longer time. The energy storage density is affected by the temperature increase effect and the uptake amount of adsorbate during the adsorption reaction. The experimental results show that the energy storage density of zeolite 13X is 15% and 28.7% higher than that of silica gel and 4A, respectively, and the temperature rise due to heat generation during adsorption reaction is also high, which is advantageous in adsorption TES system performance.     

A three-dimensional non-equilibrium model for an intermittent adsorption cooling system

Intermittent adsorption cycles, driven by low temperature heat, like solar heat, instead of electricity or natural gas, can achieve substantial fossil energy savings. In this paper, the mathematical model for the coupled heat and mass transfer in the adsorber of an intermittent adsorption cooling system is set up. The model includes four submodels: heat transfer in heating/cooling fluids, heat transfer in the metal tube, heat transfer in the fins, and heat and mass transfer in the adsorbent. The model for the heat and mass transfer in the adsorbent is a three-dimensional non-equilibrium model which takes into account both the internal and the external mass transfer resistance in the adsorbent. An experiment has been done to validate the model. With some modifications, the model can be used in system optimization and design of adsorption cycles driven by solar energy or waste heat.     

基于平行流铝扁管吸附床传热性能的模拟研究

吸附床是吸附式制冷系统的关键部件。吸附床的换热能力对吸附式制冷系统的各项性能有显著影响。文章针对应用于吸附床的传统换热器和扁管换热器的不足之处,设计出一种新型平行流铝扁管吸附床,并建立了该吸附床的二维传热模型,以温度随时间的变化情况为分析指标,分析翅片的间距、高度、厚度,以及吸附剂体积分数等因素对吸附床传热性能的影响,从而优化调整吸附床的结构,提高其换热性能。分析结果表明:当翅片高度约为70 mm时,吸附床的换热能力达到峰值;当翅片厚度大于1.5 mm时,翅片厚度的增加对吸附床传热性能的影响比较微弱;当吸附剂体积分数由0.25逐渐增大至0.45时,吸附剂的等效传热系数约增加了50%。