EXPERIMENTAL STUDIES ON A NOVEL CHEMICAL HEAT PUMP DRYER USING A GAS–SOLID REACTION

The authors have been studying Chemical Heat Pumps (CHP) from the viewpoints of energy saving and environmental impact. The CHP can store thermal energy in the form of chemical energy by an endothermic reaction, and release it at various temperature levels during heat demand periods by exo/endothermic reactions. The authors have proposed in an earlier study a novel chemical heat pump (CHP) system for environmentally-friendly effective utilization of thermal energy in drying as a chemical heat pump dryer (CHPD). In this exploratory study, we test the effectiveness of operating the proposed CHPDs experimentally. Basic experiments on the CHPDs such as hot dry air production for convective drying are performed on lab-scale CHPD apparatuses using gas–solid reactions in calcium oxide/calcium hydroxide reactant beds. The proposed CHPDs are found to produce hot air by CHP operation for drying. The temperature levels of the produced hot air and the reaction rates/conversions are as good as in the case of hot water supply system using basically same CHP operation. The cold heat for air dehumidification is also found to be generated/recovered by the same CHPD system. The generated heat amounts can be increased by changing the operating conditions although the heat recovery must be enhanced for practical application of CHPDs.     

Simplification and Energy Saving of Drying Process Based on Self-Heat Recuperation Technology

A simplified drying process based on self-heat recuperation (SHR), which can further reduce energy consumption compared to previous SHR drying processes, is proposed. The specific energy consumption (SEC) of the SHR drying process was evaluated at various air flow rates and compared with a mechanical vapor recompression (MVR) drying process with superheated steam. The results show that the SEC of SHR can be reduced from 474 to 147 kJ (kg-H₂O evaporated)^?1 by removing heat exchangers for preheating. The SEC of the simplified SHR process was only 1/16 of a conventional drying process with heat recovery and 3/5 of an MVR process. Exergy transfer of the process was also analyzed and summarized as exergy flow diagrams.     

EXPERIMENTAL STUDIES ON A NOVEL CHEMICAL HEAT PUMP DRYER USING A GAS-SOLID REACTION

The authors have been studying Chemical Heat Pumps (CHP) from the viewpoints of energy saving and environmental impact. The CHP can store thermal energy in the form of chemical energy by an endothermic reaction, and release it at various temperature levels during heat demand periods by exo/endothermic reactions. The authors have proposed in an earlier study a novel chemical heat pump (CHP) system for environmentally-friendly effective utilization of thermal energy in drying as a chemical heat pump dryer (CHPD). In this exploratory study, we test the effectiveness of operating the proposed CHPDs experimentally. Basic experiments on the CHPDs such as hot dry air production for convective drying are performed on lab-scale CHPD apparatuses using gas-solid reactions in calcium oxide/calcium hydroxide reactant beds. The proposed CHPDs are found to produce hot air by CHP operation for drying. The temperature levels of the produced hot air and the reaction rates/conversions are as good as in the case of hot water supply system using basically same CHP operation. The cold heat for air dehumidification is also found to be generated/recovered by the same CHPD system. The generated heat amounts can be increased by changing the operating conditions although the heat recovery must be enhanced for practical application of CHPDs.     

PROPOSAL FOR A NOVEL CHEMICAL HEAT PUMP DRYER

ABSTRACT

A new chemical heat pump (CHP) system for ecofriendly effective utilization of thermal energy in drying is proposed from the viewpoints of energy saving and environmental impact. CHPs can store thermal energy in the form of chemical energy by an endothermic reaction and release it at various temperature levels for heat demands by exo/endothermic reactions. CHPs have potential for heat recovery and dehumidification in the drying process by heat storage and high/law temperature heat release. In this study, we estimate the potential of the CHP application to drying systems for industrial use. Some combined systems of CHPs and dryers are proposed as chemical heat pump dryers (CHPD). The potential for commercialization of CHPDs is discussed.     

Optimization of Heat Pump–Assisted Intermittent Drying

In the present study, heat pump–assisted drying of salak fruit was optimized by dividing the dehydration process into three distinct phases, namely, the initial, intermittent, and final stages. Drying variables considered for the optimization were the intermittent duration (X ₁), intermittent ratio (X ₂), and intermittent cycle (X ₃); the response variables studied were the total drying time (Y ₁), total heating time during intermittent drying (Y ₂), total heating time after intermittent drying (Y ₃), total color change (Y ₄), ascorbic acid content (Y ₅), and total phenolic content (Y ₆). Response surface methodology was used to determine the best combination of the drying variables that could provide the shortest drying period and premium product quality. Experimental results showed that all of the response variables were improved under the optimized intermittent drying conditions compared to the conventional method using constant drying conditions. The optimized heat pump–assisted intermittent drying reduced the drying time by 36% and improved phytochemicals retention with ascorbic acid and total phenolic content recorded at 18.4 ± 1.8 mg ascorbic acid/100 g dw and 43.3 ± 2.2 mg gallic acid equivalent (GAE)/g dw, respectively. The color change of the final product was minimum with a ΔE* value of 7.26 ± 2.03.     

SIMULATION OF HYDRATION/DEHYDRATION OF CaO/Ca(OH)2 CHEMICAL HEAT PUMP REACTOR FOR COLD/HOT HEAT GENERATION

ABSTRACT

A chemical heat pump (CHP) utilizes reversible reactions involving significant endothermic and exothermic heats of reaction in order to develop a heat pump effect by storing and releasing energy while transforming it from chemical to thermal energy and vice versa. In this paper, we present a mathematical model and its numerical solution for the heat and mass transport phenomena occurring in the reactant particle bed of the CHP for heat storage and cold/hot heat generation based on the CaO/Ca(OH)₂ reversible hydration/dehydration reaction

Transient conservation equations of mass and energy transport including chemical kinetics are solved numerically subject to appropriate boundary and initial conditions to examine the influence of the mass transfer resistance on the overall performance of this CHP configuration. These results are presented and discussed with the aim of enhancing the CHP performance in next generation reactor designs.     

Steam Dewatering of Filter Cakes in a Vertical Filter Press

Steam dewatering of filter cakes is recognized as a competitive alternative to conventional air drying and thermally assisted mechanical dewatering (TAMD). The main benefit of cake dewatering with high-pressure steam is that mechanical and thermal dewatering can be efficiently performed in a single process step. The target of this study was to determine the potential of a steam-dewatering technique for two industrial mineral suspensions. The first mineral, kaolin, was very difficult to dewater using conventional mechanical dewatering techniques, whereas the second one, ground calcium carbonate (GCC), represented only moderate resistance to filtration. The secondary objective was to compare the filterability of the original kaolin slurry with the same slurry treated with a coagulant (aluminum sulphate, Al₂(SO₄)₃ · 16H₂O). Four different kinds of experiments were performed: tests without any kind of cake dewatering, tests with air drying, tests with steam drying, and tests with both coagulation and steam drying. The obtained results show that steam dewatering is an efficient technique for achieving lower cake-moisture contents. Also, the positive influence of coagulation on the filtration capacity was found to be considerable in the case of kaolin. An approximate energy balance was created for the steam-drying process and the determined energy efficiencies were compared with those obtainable with an ideal thermal drier. The main conclusion from these comparisons is that steam drying can be effectively used instead of traditional thermal drying if the large energy losses can be reduced by proper insulation and heat recovery systems.     

Tricalcium aluminate hydration in the presence of calcium sulfite hemihydrate

This article reports on the study to evaluate the potential possibility of regulating the tricalcium aluminate (C₃A) hydration process by the addition of calcium sulfite hemihydrate. The kind and the form of hydration products were studied in the system: C₃A-CaSO₃·0.5H₂O-H₂O and C₃A-CaSO₃·0.5H₂O-Ca(OH)₂-H₂O by use of XRD, DTA and SEM/EDS methods as well as the kinetics of hydration along with chemical composition development of the liquid phase. The results thus obtained were compared to the hydration process of C₃A with the addition of natural gypsum. The results show that the reaction rate of C₃A with the addition of calcium sulfite hemihydrate differs from the analogous hydration process of C₃A in the presence of calcium sulfate dihydrate. Also, the kind of hydration products obtained in the presence of CaSO₃·0.5H₂O is different.     

Comportement electrochimique d'oxocarbones et d'aci-reductones en relation avec le transport d'electrons dans les processus biologiques—VII. Reduction de l'acide rhodizonique en milieu aqueux acide

The hypothesis of an ECE1 mechanism may justify the electrochemical behavior observed for the reduction of dihydrated rhodizonic acid. In a first step, RDZ, 2H₂O is irreversibly reduced via a two-electron process without preceding dehydration. The following chemical step is an acid-catalysed dehydration of the monohydrated intermediate species and produces 1,4-tetrahydroxybenzoquinone (THQ) which is reduced via a two-electron process at a potential less negative than RDZ, 2H₂O. According to the hypothesis of an ECE1 mechanism a value of k = k′ (H⁺) with k′ = 145 ± 7 s^?1 is found for the rate constant of the chemical step. The monohydrated intermediate species is reducible via a two-electron process, and without preceding dehydration, at a potential more negative than RDZ, 2H₂O.     

Energy Conversion and Temperature Dependence in Ozone Generator Using Pulsed Discharge in Oxygen

A detailed reaction kinetic model consisting of 10 species and 63 reactions is developed to investigate the energy conversion and temperature dependence in an ozone generator using oxygen pulsed discharge. The energy conversion ratios of total electric energy converted into reaction heat, heat carried by gas and heat loss to ambient, namely η_reaction, η_gas and η_loss, are obtained for the first time. The ratio of reaction heat η_reaction decreases substantially with increasing specific energy and inlet gas temperature, which represents how much energy is utilized effectively to synthesize ozone. Correspondingly, η_loss and η_gas increase gradually. η_reaction declines from 55.4% to 27.7% at inlet gas temperature of 298 K when specific energy changes from 0.06 J/cm³ to 0.78 J/cm³. The detailed reaction pathway including the degree of transformation among species for ozone formation is also obtained via kinetics simulation. Meanwhile, sensitivity analysis and rate-of-production analysis for the four most important species O₃, O, O(1D) and O₂(b¹∑) obtained from the reaction pathway are executed to understand quantitatively the temperature dependence of sensitivity coefficient and production rate for each individual reaction. The production rate of ozone via the most important ozone generation reaction O+O₂+O₂ = > O₃+O₂ increases linearly with the increase of gas temperature, as well as the destruction rates of ozone via the most important ozone decomposition reactions O₃+O₃ = > O₂+O₂+O₂ and O₃ + O = > O₂(b¹∑)+O₂.     

The structural origin of enhanced energy harvesting performance in piezoelectric perovskite

Energy harvesting, which can translate the wasted vibration energy into electric energy, is now a hot topic in the field of new energy, and the key point is to design high power piezoelectric ceramic according with the requirements of low-frequency vibration energy harvesting. In this study, high quality Co-modified 0.2Pb(Zn_1/3Nb_2/3)O₃–0·8Pb(Zr_0·50Ti_0·50)O₃ (PZN–PZT+Co) ceramics have been prepared by the two-stage method, and the energy harvesting characteristics were investigated. The results showed that the hierarchical nanodomain structure boosts the strong piezoelectric activity, leading to the high energy harvesting performance. The PZN–PZT+Co ceramic sintered at 1000 °C exhibits an excellent d₃₃ × g₃₃ value of 14080 × 10^?15 m²/N, which are much larger than that of commercial PZT-based ceramics. In the mode of the cantilever-type energy harvester, the output voltage and energy density of 33 V, 4.4 μW/mm³ were obtained at a low resonance frequency of 85 Hz and acceleration of 10 m/s², showing potential application in piezoelectric energy harvester.     

Enhancement of Energy Efficiency of a Chemical Heat Pump-Assisted Convective Dryer

In earlier studies we have shown by simulation and experimental studies that the proposed chemical heat pump (CHP) unit can be used to recover waste heat from dryers and reuse it by storing and releasing heat with upgrading the temperature or by dehumidification. However, the final thermal energy production efficiency of the CHP for drying was found to be low. In this paper we present experimental results to demonstrate the potential for improved heat-recovery/storage and the heat-release/production of hot dry air for batch drying applications using the heat enhancement mode of the CHP. A new laboratory scale experimental CHP dryer system was built utilizing the calcium oxide/calcium hydroxide hydration/dehydration reversible reaction. The aim of this study is to improve the efficiencies of the heat recovery from heat source in the heat-storage step and the hot dry air production in the heat-release step of the CHP for heating up the air to around 100°C. The results of this experimental study utilizing a new reactor design showed that the shallow reactor/heat exchanger could accomplish 94% chemical heat storage and produce 100°C air at better than 75% efficiency for the reaction heat by controlling the preheating condition. The reaction conversion reached 90% in these experiments. The proposed CHP-assisted convective dryer system is found to be energy-efficient over a wide temperature range of industrial interest.     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Potential of integrating Na2SO4 · 10H2O pellets in solar drying system

In the current study, evolution of thermophysical properties of red chilli dried in a mixed mode solar dryer that integrates sodium sulfate decahydrate (Na₂SO₄?·?10H₂O) and sodium chloride (NaCl) as thermal storage were presented. Solar drying with Na₂SO₄?·?10H₂O reduced the drying time by 26.7 and 39%, compared to the drying time with or without NaCl. Dimensional shrinkage was gradual with a nonlinear exponential shape for the whole drying conditions. The evolution of the bulk and particle densities decreased while the porosity of the seed increased with time. The coefficient of heat and mass transfer varied from 0.0036???0.035?W/m²?K to 6.09?×?10^?9???6.2?×?10^?8?m/s, respectively. The thermal conductivity, specific heat capacity, and thermal diffusivity ranged from 0.0568 to 0.1093?W/m?K, 1,072 to 2218.7?J/kg?K, and 4.7?×?10^?5 to 5.13?×?10^?5?m²/s, respectively.     

Zr K-edge XAS study on ZrO<Subscript>2</Subscript>-pillared aluminosilicate

The ZrO₂-pillared clay with high acidic property has been prepared by reacting 1 wt% colloidal suspension of Na⁺-montmorillonite with 1 N aqueous solution of ZrOCl₂·8H₂O and by subsequent heating. The evolution of local structure around zirconium of the intercalant stabilized in-between aluminosilicate layers upon intercalating, drying, and pillaring condition has been systematically studied by X-ray absorption spectroscopy, and compared to those of reference compounds such as ZrO₂, and ZrOCl₂ · 8H₂O and its 1 N aqueous solution. The intercalated zirconium species was identified as the Zr-tetramer, [Zr₄(OH)₁₄(H₂O)₁₀]²⁺, with an average molecular volume of 10 × 10 Å² and a thickness of 4.5 Å. Also it becomes more condensed upon drying and eventually transforms to a zirconium oxide pillar upon calcination.     

Dissolution mechanism of colemanite in sulphuric acid solutions

Boron compounds are very important raw materials in many branches of industry and their uses have been increasing and expanding continuously. Colemanite, one of the most common boron minerals, has a monoclinic crystal structure with a chemical formula of 2CaO·3B₂O₃·5H₂O and is used usually in the production of boric acid. The present study concerns and investigation of the dissolution mechanism of colemanite in H₂SO₄ solution and the effect of acid concentration, the effect of SO₄⁻² ion on the dissolution process, using H₂SO₄, HCI+H₂SO₄ and H₂SO₄+Na₂SO₄ solutions. The analysis of the experimental data shows that increasing H₃O⁺ acid concentration increased the dissolution rate, but increasing SO₄⁻² concentration reduced dissolution rate because of the precipitation of a solid film of CaSO₄ and CaSO₄·H₂O.     

Contribution to the hydration of expansive cement on the basis of metakaolinite

The study of hydration of expansive cement prepared from 64% portland cement clinker, 23% metakaolinite and 13% CaSO₄.2H₂O is described. It was found that in the course of a 10-day hydration period, all the gypsum entered the reaction with the formation of ettringite. In 7–10 days, after the termination of the expansion processes, typical stalk-like crystals were transformed into leaf-shaped or other formations. Ettringite was identified even after 4 months of hydration. Monosulphate (3CaO.Al₂O₃.CaSO₄.12H₂O) was found in none of the investigated high-expansion cement paste samples.     

Gaseous Carbon Dioxide as the Heat and Mass Transfer Medium in Drying

Using available correlations for heat transfer, a comparative analysis of drying rates in CO₂ and in air was performed for several basic types of dryers. Higher heat transfer rates were found for dryers with active hydrodynamics, which translates into shorter drying time for materials dried in the first drying period. These results were validated by experiments on drying wheat kernels fluidized by air and by CO₂. Shorter drying times by about 20% were confirmed for CO₂, which offers energy savings of about 3% of the heat input to the dryer. Additional energy savings of 4% of the heat load can be expected for drying at temperatures below 100°C because of the lower wet-bulb temperature for CO₂ than that for air. The potential for CO₂ abatement was evaluated based on a case study for drying of distillers' spent grain.     

Mineralogical and engineering characteristics of dry flue gas desulfurization products

Fifty-nine coal combustion products were collected from coal-fired power plants using various dry flue gas desulfurization (FGD) processes to remove SO₂. X-ray diffraction analyses revealed duct injection and spray dryer processes created products that primarily contained Ca(OH)₂ (portlandite) and CaSO₃·0.5H₂O (hannebachite). Most samples from the lime injection multistage burners process contained significant amounts of CaO (lime), CaSO₄ (anhydrite), and CaCO₃ (calcite). Bed ashes from the fluidized bed process were often dominated by CaSO₄ but also contained CaCO₃, CaO (lime), and MgO (periclase). Cyclone ashes were similar in composition to the bed ashes but contained more unspent sorbent and CaSO₄ and less MgO. Fly ash in all samples ranged from 10 to 79 wt%. Samples usually exhibited two distinct swelling episodes. One occurred immediately after water was applied due to hydration reactions, especially the conversion of CaO to Ca(OH)₂ and CaSO₄ to CaSO₄·2H₂O (gypsum). The second began between 10 and 50 d later and involved formation of the mineral ettringite (Ca₆[Al (OH)₆](SO₄)₃·26H₂O). The final pH after 112 d ranged from 10.0 to 12.1. If samples are incubated under ‘closed’ (i.e. incomplete recarbonation with atmospheric CO₂) and alkaline weathering conditions, gypsum and portlandite are initially formed followed by the conversion of the gypsum to ettringite. Closed, alkaline conditions typically can occur when FGD products are placed in confined settings such as a road embankment or buried as a discrete layer as occurs in some surface mine reclamation projects.     

Simulation of Compression Heat Pump Cycles Using NH3/H2O Mixtures to Estimate Their Working Domains

A computer-aided process design methodology is used to determine the limits of NH₃/H₂O mixtures in different heat pump cycles from 20 °C to 150 °C. The evaluation is based on a defined parameter set consisting of the coefficient of performance, total heat transfer area and volumetric heat capacity. Simple cycles with two heat flows were chosen to meet good process integration capabilities. The results are shown in a sink outlet/temperature lift matrix considering current technical limits. R1366mzz(Z) in a standard compression cycle with internal heat exchanger serves as a benchmark. To provide temperatures up to 150 °C the lift of the heat pump has to increase to about 80 K of which only the wet compressions cycle with NH₃/H₂O is capable of. The working domains of NH₃/H₂O and R1366mzz(Z) are similar, when a two-stage compression for NH₃/H₂O is applied.