增压双效氨水吸收制冷循环性能分析

在双效氨水吸收制冷循环的基础上,提出了一种增压双效氨水吸收制冷循环。结合Schulz氨水状态方程式,通过数学建模对该循环过程进行模拟计算。分析了增压比、制冷温度、热源温度、冷却水温度对循环性能的影响,并和双效氨水吸收制冷循环进行比较。结果表明,增压双效氨水吸收制冷循环中,增压比是非常重要的影响因素,它直接影响循环的性能系数;在其他工况参数不变的条件下,增压双效氨水吸收制冷循环有其最佳的增压比;在适当的增压比下,扩大了双效循环的应用范围,在制冷温度较低时,也可以具有较高的性能系数,而且在相同制冷温度下,降低驱动热源温度也能达到理想的循环效果,从而使本循环可利用的热源范围得以扩展。     

CO_2-NH_3复叠与NH_3制冷系统的流程参数比较

设计了典型的CO2-NH3复叠式制冷流程和NH3两级压缩制冷流程,对流程进行了模拟计算,比较了两者的关键参数,并分析了换热器的热流分布及氨系统的参数优化。结果表明:在蒸发温度-45℃的条件下,复叠式系统的压缩机总功耗、制冷剂NH3流量小于氨系统,但氨系统具有较大规模的中温制冷量,其总制冷系数COP大于复叠式系统。复叠式系统冷凝蒸发器的两相流间换热温差较小,而氨系统中间冷却器的换热温差较大。随着低压级排气压力的上升,以及中间温度的降低,氨两级压缩机的总功耗呈下降趋势。     

Bubble-point measurements in the ammonia-carbon dioxide system

The bubble-point pressures in the NH₃-CO₂ system, at complete chemical equilibrium, have been measured in the range of 130–185°c corresponding to pressures of 30–175 atm. The NH₃-CO₂ system exhibits a sharp pressure minimum; in the area of high NH₃ concentration, critical behaviour and retrograde condensation have been found. The results, as part of the NH₃-H₂O-CO₂ system, are discussed from the standpoint of chemical phase theory and are shown to be consistent with the NH₃-H₂O and CO₂-H₂O systems. The relation of these measurements to the commercial urea synthesis is also discussed.     

Physical and electrochemical properties of 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium iodide,and 1-butyl-3-methylimidazolium tetrafluoroborate

The density, viscosity, refractive index, heat capacity, heat of dilution, ionic conductivity, and electrochemical stability of 1-butyl-3-methylimidazolium bromide ([bmim][Br]), 1-butyl-3-methylimidazolium iodide ([bmim][I]), and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) were measured at room temperature or over a temperature range of 293.2 to 323.2 K. The density and refractive index values of [bmim][I] appeared to be the highest among three ionic liquids (ILs). However, the experimental viscosity values of [bmim][Br] were higher than those of [bmim][BF₄], while the heat capacities and heats of dilution of [bmim][BF₄] were higher than those of [bmim][Br]. The cyclic voltammogram of [bmim][br] and [bmim][BF₄] indicated electrochemical windows in the stability range from 2.7 V of [bmim][[Br] to 4.7 V of [bmim][BF₄].     

Experimental Verification of Separation of Ions Using Countercurrent Electrolysis in a Thin,Porous Membrane

Abstract

Countercurrent electrolysis in a porous membrane has been used to separate cations in systems LiCl-NaCl-H₂O, LiCl-CaCl₂-H₂O, LiCl-BaCl₂-H₂O, LiCl-KCl-H₂O, and LiCl-NaCl-KCl-H₂O. The experimental results confirm the relationship between the separation efficiency and the difference in ionic equivalent conductance. Furthermore, the dependence of the separation efficiency on the outflow of the enriched solution and on the convection through the membrane has been verified.     

用NRTL方程计算含离子液体体系的汽液平衡

离子液体作为环境友好溶剂在反应和分离过程中具有良好的应用前景,含离子液体体系汽液平衡的计算及模型化研究具有重要的理论和实际意义.采用非电解质溶液NRTL方程表示溶液的非理想性,关联了［bmim］［PF₆］H₂O及［C₈mim］［PF₆］H₂O二元体系的等温汽液平衡,关联误差在2%之内;预测了这些体系在其他温度下的汽液平衡,预测的总平均误差均在5%之内.通过关联不同温度下有机物在离子液体C₈H₁₄S₂O₄F₆N₃和C₉H₁₆S₂O₄F₆N₃中的无限稀释活度因子的实验数据,得到了有关NRTL方程的二元作用参数,在此基础上预测了离子液体对二元共沸体系汽液平衡的影响.结果表明,含离子液体体系的汽液平衡可以采用传统的非电解质溶液模型如NRTL方程来描述,离子液体的“盐效应”可以显著改善组分的相对挥发度甚至消除共沸现象.     

CO2跨临界双级压缩制冷循环的热力学分析

Two-stage vapor compression refrigeration cycle was accomplished with an intercooler.The state of the refrigerant vapor leaving the intercooler affects the system performance.The thermodynamic analysis of the trans-critical two-stage refrigeration cycle using CO₂ as the refrigerant was made with a condensing temperature of 35℃.When the intercooler operated at about the geometric mean of the evaporating and condensing pressures,compared with the single stage cycle,the coefficient of performance（COP）of the two-stage cycle was improved.As the degree of superheating of the CO₂ vapor leaving the intercooler increased,the COP of the two-stage system decreased.     

The performance of two adsorption ice making test units using activated carbon and a carbon composite as adsorbents

The available adsorption working pairs applied to adsorption refrigeration system, which utilize activated carbon as adsorbent, are mainly activated carbon-methanol, activated carbon-ammonia, and composite adsorbent-ammonia. The adsorption properties and refrigeration application of these three types of adsorption working pairs are investigated. For the physical adsorbents, consolidated activated carbon showed best heat transfer performance, and activated carbon-methanol showed the best adsorption property because of the large refrigerant amount that can be adsorbed. For the composite adsorbents, the consolidated composite adsorbent with mass ratio of 4:1 between CaCl₂ and activated carbon, showed the highest cooling density when compared to the granular composite adsorbent and to the merely chemical adsorbent. The physical adsorption icemaker that employs consolidated activated carbon-methanol as working pair had the optimum coefficient of refrigeration performance (COP), volume cooling power density (SCP_v) and specific cooling power per kilogram adsorbent (SCP) of 0.125, 9.25 kW/m³ and 32.6 W/kg, respectively. The composite adsorption system that employs the consolidated composite adsorbent had a maximum COP, SCP_v and SCP of 0.35, 52.68 kW/m³ and 493.2 W/kg, respectively, for ice making mode. These results are improved by 1.8, 4.7 and 14 times, respectively, when compared to the results of the physical adsorption icemaker.     

Crystallography and equilibrium solubility for ammonium and potassium orthophosphites and hypophosphites

The composition and solubility properties of eight ammonium and potassium orthophosphites and hypophosphites were determined to evaluate the potential of these classes of materials for increasing the plant nutrient content of liquid fertilizers. Phase relationships for the systems (NH₄)₂O-P₂O₃-H₂O, K₂O-P₂O₃-H₂O, (NH₄)₂O-P₂O-H₂O, and K₂O-P₂O-H₂O were determined along with the crystallographic properties (X-ray and optical) of the solid phases. Toxicity and phosphite response was tested in greenhouse experiments for the compounds.     

Influence of operating temperature on CO<Subscript>2</Subscript>-NH<Subscript>3</Subscript> reaction in an aqueous solution

Although aqueous ammonia solution has been focused on the removal of CO₂ from flue gas, there have been very few reports regarding the underlying analysis of the reaction between CO₂ and NH₃. In this work, we explored the reaction of CO₂-NH₃-H₂O system at various operating temperatures: 40 °C, 20 °C, and 5 °C. The CO₂ removal efficiency and the loss of ammonia were influenced by the operating temperatures. Also, infrared spectroscopy measurement was used in order to understand the formation mechanism of ion species in absorbent, such as NH₂COO⁻, HCO₃⁻, CO₃²⁻, and NH₄⁺, during CO₂, NH₃, and H₂O reaction. The reactions of CO₂-NH₃-H₂O system at 20 °C and 40 °C have similar reaction routes. However, a different reaction route was observed at 5 °C compared to the other operating temperatures, showing the solid products of ammonium bicarbonates, relatively. The CO₂ removal efficiency and the formation of carbamate and bicarbonate were strongly influenced by the operating temperatures. In particular, the analysis of the formation carbamate and bicarbonate by infrared spectroscopy measurement provides useful information on the reaction mechanism of CO₂ in an aqueous ammonia solution.     

Clean recycling of zinc from blast furnace dust with ammonium acetate as complexing agents

Blast furnace dust (BFD) from ironmaking and steelmaking process is important secondary sources of zinc and other valuable metals. To realize recycling utilization of zinc secondary resource, a clean zinc production process using NH₃-CH₃COONH₄-H₂O as leaching agent has been developed. It was found that the addition of CH₃COONH₄ to NH₃-H₂O system promotes the zinc extraction, and 77.79% (8.23g/L) of Zn could be dissolved. The leaching process is controlled by the diffusion and interface transfer, and the corresponding activation energy E_a is 22.32 kJ/mol. The results of Fourier transforming infrared spectrum (FT-IR) and Electrospray ionization mass spectrometry (ESI-MS) analysis showed that zinc can combine with the carboxylate anion to form Zn-complexes.     

Performance analysis of an adsorption refrigerator using activated carbon in a compound adsorbent

To improve the performance of the adsorption refrigeration of CaCl₂-ammonia adsorption system, activated carbon has been distributed uniformly in the mass of CaCl₂, thereby helping to enhance mass transfer and uplift the cooling power density. A multifunctional heat pipe adsorption refrigerator, in which activated carbon-CaCl₂ is used as compound adsorbent and ammonia as refrigerant, is designed. Water and acetone are used as working liquids for the heat pipe. This paper presents a study on the adsorption refrigeration performances of this adsorption refrigerator under two different working conditions, ice-maker for fishing boat driven by the waste heat from exhaust gases, and solar ice-maker driven by solar water heating. The obtained average SCP (specific cooling power) and the COP (coefficient of performance) of the refrigerator were measured to be 770.4 W/kg and 0.39 at about −20 °C of evaporating temperature for the former working condition, and they were 161.2 W/kg and 0.12 at about −15 °C of evaporating temperature for the later working condition.     

Global phase behavior of imidazolium ionic liquids and compressed 1,1,1,2‐tetrafluoroethane (R‐134a)

Novel processes involving ionic liquids with refrigerant gases have recently been developed. Here, the complete global phase behavior has been measured for the refrigerant gas, 1,1,1,2‐tetrafluoroethane (R‐134a) and 1‐n‐alkyl‐3‐methyl‐imidazolium ionic liquids with the anions hexafluorophosphate [PF₆], tetrafluoroborate [BF₄] and bis(trifluoromethylsulfonyl)imide [Tf₂N] from ～0°C to 105°C and to 33 MPa. All of the systems studied were Type V from the classification scheme of Scott‐van Konynenburg with regions of vapor‐liquid equilibrium, miscible/critical regions, vapor‐liquid‐liquid equilibrium, and upper and lower critical endpoints (UCEP and LCEP). The effect of the alkyl chain length has been investigated, for ethyl‐([EMIm]), n‐butyl‐([BMIm]), and n‐hexyl‐([HMIm]). With increasing chain length, the temperature of the lower critical end points increases and pressure at the mixture critical points decrease. With a common cation, the temperature of the LCEP increased and the mixture critical point pressures decreased in the order of [BF₄], [PF₆], and [Tf₂N]. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

Preparation of high energy fuel JP-10 by acidity-adjustable chloroaluminate ionic liquid catalyst

The isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) to its exo-isomer (JP-10) has been investigated by using chloroaluminate ionic liquids (ILs) as catalysts. The catalyst activity and selectivity could be optimized by varying the mole fraction of AlCl₃ in the IL. Undesirable by-products derived from side-reactions such as skeletal rearrangement, alkylation, cracking, and dimerization could be minimized by appropriate catalyst design and adjustment of the reaction conditions. The catalyst system was further optimized by selecting 1-butyl-3-methylimidazolium chloride as the basic IL and adding 0.60-0.65 mole fraction of AlCl₃ as the promoter. Using the optimized catalyst system, the isomerization of endo-THDCPD to exo-THDCPD proceeded at a fast rate at 50 °C with 98.9% conversion and 100% selectivity. The catalyst longevity has been demonstrated by recycling the IL several times without a noticeable reduction in catalytic activity.     

高温气体与过冷液直接接触凝结制冷循环的性能分析

提出制冷压缩机排出的高温高压制冷剂气体与制冷剂过冷液体直接接触凝结换热的新型制冷循环,结合自然工质氨的热力特性,分析直接接触凝结制冷循环的热力性能,并与常规双级压缩和单级压缩制冷循环的性能进行对比,得出：随着主循环饱和液温度的升高,直接接触凝结制冷循环的性能系数先增大后减小存在最大值,冷凝器散热量先减小后增大存在最小值,流过蒸发器的制冷剂质量流量逐渐增大。在相同蒸发温度和冷凝温度下,当过冷液体的过冷度为20℃时,较常规双级压缩制冷循环,直接接触凝结制冷循环的性能系数提高4.92%,冷凝器散热量减少6.65%,蒸发器的制冷剂质量流量减少7.2%～7.9%;当过冷液体的过冷度为5℃时,较常规单级压缩制冷循环,直接接触凝结制冷循环的性能系数提高6.52%,冷凝器散热量减少3.32%,蒸发器的制冷剂质量流量减少8.58%～8.91%。结果表明氨直接接触凝结制冷循环较常规制冷循环具有明显的优势。     

SO2 Absorption/Desorption Characteristics of Two Novel Phosphate Ionic Liquids

Two kinds of phosphate ionic liquids were synthesized and their SO₂ absorption performance was investigated. It was found that both ionic liquids could readily absorb SO₂, and the absorption capacity could reach 2.8 and 2.7 mol SO₂ per mole ILs, respectively, at ambient temperature and under normal pressure. Moreover, the cycle of SO₂ absorption and desorption from ionic liquids was repeated for four times and no change in the absorption capacity was observed. FT-IR spectrum and ¹H NMR were used to characterize the microstructure of SO₂-absorbed ILs and ILs, analysis showed that both ionic liquids absorbed SO₂ purely by physical absorption. Comparing with the previous reported ionic liquids such as [Bmim][PF6] and [Emim][BF4], the synthesized ionic liquids showed higher absorption capacity, due to the anion based phosphate (O?P?O) with the free electrons on the oxygen interacting with the Lewis acidic sulfur of SO₂, and then showing a great affinity for SO₂.     

Ionic liquids for CO2 capture—Development and progress

Innovative off-the-shelf CO₂ capture approaches are burgeoning in the literature, among which, ionic liquids seem to have been omitted in the recent Intergovernmental Panel on Climate Change (IPCC) survey. Ionic liquids (ILs), because of their tunable properties, wide liquid range, reasonable thermal stability, and negligible vapor pressure, are emerging as promising candidates rivaling with conventional amine scrubbing. Due to substantial solubility, room-temperature ionic liquids (RTILs) are quite useful for CO₂ separation from flue gases. Their absorption capacity can be greatly enhanced by functionalization with an amine moiety but with concurrent increase in viscosity making process handling difficult. However this downside can be overcome by making use of supported ionic-liquid membranes (SILMs), especially where high pressures and temperatures are involved. Moreover, due to negligible loss of ionic liquids during recycling, these technologies will also decrease the CO₂ capture cost to a reasonable extent when employed on industrial scale. There is also need to look deeply into the noxious behavior of these unique species. Nevertheless, the flexibility in synthetic structure of ionic liquids may make them opportunistic in CO₂ capture scenarios.     

Triethylsulfonium Bistriflimide as the Reaction Medium in Catalyzed and Uncatalyzed Cycloaddition [4 + 2]

Triethylsulfonium bistriflimide, [S_2.2.2][NTf₂], has been tested and compared with other ionic liquids and molecular solvents as a medium in Diels–Alder reaction between cyclopentadiene and dimethyl maleate. Triflates and chlorides of different metals have been combined with [S_2.2.2][NTf₂] and the catalytic activity of the systems formed have been determined. The effect of concentration of the catalysts in sulfonium ionic liquid and reactants on the yield and endo:exo ratio has been established. The representative catalyst—Yb(OTf)₃·xH₂O in [S_2.2.2][NTf₂] has been examined in the reaction of cyclopentadiene with various dienophiles. The use of sulfonium ionic liquids permitted recycling the catalysts. For the best four catalytic systems, the products have been isolated.     

Improvement in CO2 absorption and reduction of absorbent loss in aqueous NH3/triethanolamine/2-amino-2-methyl-1-propanol blends

Changes in the CO₂ absorption rates and capacities of the absorbent 2-amino-2-methyl-1-propanol (AMP), blended with NH₃ and other additives, were investigated toward performance improvement. The NH₃-blended absorbent removed CO₂ more efficiently than the AMP absorbent alone. However, absorbent loss through NH₃ evaporation was observed under these conditions. A second absorbent, the tertiary amine triethanolamine (TEA), which has a low vapor pressure, was selected and blended with the NH₃/AMP system to reduce NH₃ evaporation. Its effects on NH₃ loss and the absorption rate and capacity of the NH₃/AMP system were investigated, and the optimum blending ratios were determined. In addition, the absorbent blend at the optimum blending ratio was compared to AMP alone and the commercially available absorbent monoethanolamine at the same weight ratio. The thermal stabilities of the absorbents, under conditions used in the CO₂ absorption process, were compared by thermogravimetric analysis.     

Gas drying with ionic liquids

The gas drying technology with ionic liquids (ILs) was systematically studied ranging from the molecular level to industrial scale. The COSMO‐RS model was first used to screen the suitable IL and provide theoretical insights at the molecular level. Toward CO₂ gas dehydration, we measured the CO₂ solubility in single [EMIM][Tf₂N] and in the [EMIM][Tf₂N] + H₂O mixture, as well as the vapor‐liquid equilibrium (VLE) of [EMIM][Tf₂N] + H₂O system, to justify the applicability of UNIFAC model. Based on the thermodynamic study, the rigorous equilibrium (EQ) stage mathematical model was established for process simulation. The gas drying experiment with IL was also performed and the water content in gas product can be reduced to 375 ppm. It was confirmed that a less flow rate of absorbent, a higher CO₂ recovery ratio and a much lower energy consumption can be achieved with IL than with the conventional triethylene glycol (TEG). © 2017 American Institute of Chemical Engineers AIChE J, 64: 606–619, 2018