采用CO_2天然混合制冷剂的制冷系统热力学分析

受工况条件的限制,CO2制冷系统在实际应用中往往需要采用跨临界循环,高压侧压力高达10MPa及以上。高的运行压力对系统各部件、设备的安全运行均提出更高要求,从而造成初投资增大。采用CO2混合工质,可以有效地改善纯的CO2系统存在的不足。针对三组CO2天然混合工质——R744/R290、R744/R600、R744/R600 a,在特定的工况条件下,对制冷系统进行了热力学理论分析和计算。探讨了混合工质中CO2不同质量配比、不同蒸发器出口制冷剂温度对系统制冷量、COP和冷凝压力的影响。结果表明:在相同工况下,R744/R290的冷凝压力比R744R/600高12~23%,比R744/R600 a高19~24%;R744/R290的COP值比R744/R600高33~41%,比R744/R600 a高25~32%。     

R125/R600a二元混合物的热力学性质

基于制冷剂物性计算软件NIST REFPROP 7.0及R125/R600a气液相平衡实验数据,使用MBWR状态方程结合Lemmon-Jacobsen混合物模型,对R125/R600a(50/50 mass%)混合替代工质的热力学性质进行了计算,并制作给出了其压焓图(p-h)、温熵图(T-s)和比定压热容图(c<,p>-T)及饱和性质表.最后理论计算分析了其空调制冷工况的性能,结果表明该混合工质具有与R22相当的压缩比和COP值,比R22较低的排气温度和较高的单位质量制冷量.     

混合工质用于单级压缩制冷回热循环的理论研究与分析

主要利用NIST8.0软件,针对R23/R134 a,R23/R600 a,R23/R125,R23/R14等二元混合工质在Linde-Hampson循环下进行了理论分析,设计一套可制得-60℃的单级压缩节流回热循环系统。通过对工质成分特性分析对比,研究其对循环的热力学性能的影响规律,得到了最佳制冷剂组合。     

混合制冷剂冰箱对比试验研究

本文对二元混合工质HFC152a/HCFC22、 HFC152a/HFC125在冰箱上应用的制冷循环性能进行了详细的理论计算和分析,并且对这两种混合工质灌注式替代CFC12、在最佳配比和充灌量下的冰箱主要制冷性能进行了对比试验研究。试验结果表明:在合适的配比和充灌量下混合工质冰箱制冷性能指标满足国家标准要求, HFC152a/HFC125在最佳充灌量为97 g时,试验冰箱耗电量为1.156 kW·h/24h,比CFC12节能10％,比HFC152a/HCFC22节能0.81％。因此, HFC1S2a/HFC125比HFC152a/HCFC22更适合于灌注式替代CFC12。     

R11/R134a混合工质管束外沸腾传热的EHD强化试验研究

采用EHD强化技术对R11/R134a混合工质进行管束外沸腾传热的试验研究,以试验所获得的大量数据为基础,分析了电场电压、热流密度与换热系数、强化系数之间的关系,并重点分析了不同工质组分对EHD强化效果的影响,为探索EHD强化沸腾换热的机理以及将其推广到工程应用提供了一定依据。     

R134a、R410a和R1234yf双级热泵性能对比

针对一级节流中间完全冷却双级压缩系统,建立了能量方程并编制了程序,对R134a、R410a和R1234yf热泵系统压缩机排气温度、性能COP、压缩机耗功和■损失等进行了对比。结果表明:在环境温度为-25℃时,R1234yf的制热COP可达到1.766,仅比R134a和R410a约低4%和2.9%,低压级压缩机耗功分别比R134a和R410a约低18%和20%;高压级压缩机耗功分别比R134a和R410a约低21%和22%。在一定程度上,R1234yf制冷剂可作为R134a和R410a的替代工质。     

一种冷热联供一体机的实验研究

搭建了基于自行复叠循环的冷热联供实验平台。采用二元混合制冷剂R744/R600a作为运行工质,在加注一定的比例并对不断对成分比例和充注量进行调整后,实验系统最终在冷凝侧产生55.1℃生活热水的同时,蒸发侧箱体内获得了平均温度为-30.5℃的实验结果。装置通过多次开机以及长时间的实验研究。结果表明:压缩机压比不大于6,排气温度不高于81℃,系统运行安全稳定。     

太阳能喷射制冷系统的新型替代工质优化选择研究

太阳能喷射制冷系统具有变工况间歇性工作特点,优良制冷工质特性是太阳能喷射制冷系统获得良好循环性能至关重要条件。因此,优化选择绿色环保替代工质对扩大太阳能喷射制冷系统工作温区和寻找太阳能喷射制冷系统的最佳变工况工作特性具有重要理论意义。文中在建立改进型太阳能喷射制冷系统热力学模型基础上,研究了以R161、R1234yf、R152a、R290、R134a及R600a为制冷剂的太阳能喷射制冷系统变工况热力学特性。结果表明,以R161为制冷剂的太阳能喷射制冷系统的性能系数平均(COP)值最高,其变工况循环性能明显优于R134a和R600a等制冷工质;绿色环保新型制冷剂R161是适用于喷射制冷系统变工况运行的优良替代工质。     

混合工质HFC134a/HCs替代R502的性能分析

针对目前R502主流替代工质R507和R404A存在的温室效应指数高、与矿物油互溶性差等缺点,提出了环保性能更好的三组近共沸混合工质R134a/R290、R134a/R1270和R134a/R290/R1270作为R502新型替代工质；并对其热物性、循环性能、安全性能和溶油性进行了计算分析。结果表明：除了压缩机排气温度偏高,这三组R134a/HCs混合工质的其它主要循环性能参数如压缩机压力比、容积制冷量和系统性能系数COP都优于R507和R404A,并且从理论上讲不存在可燃可爆的危险,同时可以与矿物油互溶,在替代R502方面更具有优势,其中R134a/R290/R1270在高热负荷下的综合性能最优良。     

二元环保型混合工质一次分凝循环性能优化

应用定循环运行压比优化方法,对采用环保型二元混合工质的单级压缩一次分凝循环,进行了-60℃温度位的循环性能数值优化。计算结果表明,影响循环COP的因素有混合工质成分(工质组元、工质浓度)和循环压力位(循环低压和循环压比),必须综合考虑进行优化。不可燃混合工质R23/R134a、R23/R227ea和R23/R236ea中,R23摩尔浓度为0.55和0.6的R23/R236ea循环在压比为7和10时,分别有最大的COP;自然混合工质R170/R290、R170/R600a和R170/R600中,R170摩尔浓度为0.65和0.7的R170/R600循环在压比为7和10时,分别有最大的COP。     

NMR analysis of diacyl peroxide decomposition in methanol in response to temperature and microwave radiation

We have studied the decomposition of benzoyl and acetyl benzoyl peroxides in methanol-d₄ in response to temperature and microwave radiation. We have shown that chemically-induced dynamic nuclear polarization (CIDNP) can be observed even when the reactions are carried out in spectrometers with high magnetic fields. In this case, spin correlation persists in geminal radical pairs involving labile acyloxyl radicals. Regardless of the method used to initiate peroxide decomposition, the same amount of products are formed. Homolysis occurs according to a chain mechanism. The contribution of induced decomposition decreases over the course of the reaction. Dissolved oxygen molecules efficiently terminate the chain, decreasing the rate of peroxide decomposition. In the case of acetyl benzoyl peroxide, the product yield depends on the initiation mechanism: for microwave irradiation, the solvent molecules are more active while dissolved oxygen is less active than in thermolysis.     

Kinetics of radical reactions involved in the gas-phase thermal decomposition of nitrobenzene

The performance of a method for analyzing complex kinetic processes is demonstrated by the example of the thermal decomposition of nitrobenzene in the gas phase. A gradual increase in the number of reactions, determination of the parameters involved, and comparison with experimental data made it possible to construct a minimum mechanism capable of describing the experimental data within the selected pressure range. The rate constants for a number of reactions of radicals with the initial reactant and reaction products were determined.     

含萘聚芳醚酮共聚物热处理后产生自由基的ESR谱

萘环摩尔含量20%的聚芳醚酮（PANEK）无规共聚物在340 ℃空气条件下发生交联反应，经过不同时间的热处理后，在室温检测热处理后产生的自由基ESR谱. 它们都有一条较强的单峰，随着热处理时间的增长，自由基ESR谱的幅度增强，将微波功率加大到200 mW, 谱线发生明显的变化，出现两条重叠在一起的谱线，说明含萘环聚芳醚酮在热处理过程中产生了两种不同的自由基. 文中模拟、讨论了热处理过程中产生的两种自由基的归属，一种是RO·自由基，另一种是萘自由基，它们都参与交联反应，RO·自由基起主要作用.     

聚甲基丙烯酸甲酯热氧化降解的化学动力学研究

使用质谱、热分析手段研究了PMMA热解反应 .结果表明 ,在氮气中 ,PMMA -CH =CH2 有两个失重阶段 ,分别对应于主链末端双键引发的断链和主链无规则断链反应 ,转折点的失重率约为 2 6 % .其中 ,第一阶段的失重速率受扩散过程控制 ,平均表观活化能E为 15 8.5kJ/mol,lnA为 2 7.6 9;第二失重阶段为 1.5级化学反应 ,平均表观活化能E为 2 14 .79kJ/mol,lnA为 4 0 .4 6 .在空气中 ,PMMA也有两个失重阶段 ,反应机理为 1级化学反应 ,转折点处的失重率约为 70 % .其中在第一失重阶段平均表观活化能E为 130 .32kJ/mol,lnA为 2 4 .81,在此阶段中 ,过氧化基团的分解反应对PMMA的失重速率有重要影响 ;在空气中第二失重阶段平均表观活化能E为 78.2 5kJ/mol,lnA为 13.97.     

一种热泵循环工质与R22的可用能对比分析

目前在制冷、热泵系统中广泛使用的循环工质R22由于具有较大的GWP值和ODP值,所以终将被淘汰。针对工质R22的替代研究,本文提出了一种新型的非共沸混合工质R290／R600a／R123(50％／10％／40％),并在小型试验台上做了热泵工况的试验分析。将该工质在各工况下的试验结论与相应工况下R22的试验结论进行对比分析后发现该工质的可用能分析优于R22的研究结论。     

基于ReaxFF模拟的正戊烷热分解机理研究

采用密度泛函理论和ReaxFF力场对正戊烷的热分解机理进行研究,分析了热分解的起始反应路径、温度对热分解的影响,并对正戊烷热分解进行了一级动力学研究。结果表明正戊烷热分解的起始反应主要分为两类:一类为碳碳单键断裂,另一类为碳氢键断裂,其中C2-C3键断裂是主要的起始反应路径。正戊烷热分解的主要产物为氢气、甲烷、乙烷、乙烯、乙炔、丙烷和丙烯。经过一级动力学计算得到表观活化能和指前因子分别为224.4 kJ·mol^-1和3.1324×10^14 s^-1。     

快速电子辐照F-40残存自由基热衰减的ESR研究

空气中辐照F-40样品中残存的链侧过氧自由基没有链端过氧自由基稳定.这些自由基的热衰减呈明显二级反应特征.反应表观活化能与指前因子这两个对反应速率常数起着相反影响的动力学参数之间存在着动力学补偿效应,表明自由基热衰减是同时在不同活性中心上进行的复杂反应.     

A theoretical kinetics study on low-temperature oxidation of n-C4H9 radicals

The low-temperature oxidation mechanism of n?butyl radicals (n-C₄H₉) has been investigated by high level quantum chemical calculations coupled with the Rice–Ramsperger–Kassel–Marcus/Master Equation (RRKM/ME) theory. The potential energy surfaces (PES) were explored at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants were computed and fitted in modified Arrhenius parameters. The major reaction channels were discussed to more deeply understand the competing relationships between chain branching, chain propagation and termination reactions. The results show that the 1,5 H-shift reaction is more competitive than the 1,6 H-shift and 1,4 H-shift for isomerization reactions of n?butyl peroxy radicals, and the concerted HO₂ elimination channel to form butene becomes more important at high temperatures. Furthermore, based on our calculations, a revised kinetic model was developed to describe n-butane oxidation. Good consistency between model predictions and experimental data was shown. This study enhances our understanding of the combustion mechanism of n-butane and can be used as a reliable reference for mechanistic understanding of larger alkanes.     

Effect of ozone addition and ozonolysis reaction on the detonation properties of C2H4/O2/Ar mixtures

Ozone is one of the strongest oxidizers and can be used to enhance detonation. Detonation enhancement by ozone addition is usually attributed to the ozone decomposition reaction which produces reactive atomic oxygen and thereby accelerates the chain branching reaction. Recently, ozonolysis reaction has been found to be another mechanism to enhance combustion for unsaturated hydrocarbons at low temperatures. In this study, the effects of ozone addition and ozonolysis reaction on steady detonation structure and transient detonation initiation and propagation processes in C₂H₄/O₂/O₃/Ar mixtures are examined through simulations considering detailed chemistry. Specifically, the homogeneous ignition process, the ZND detonation structure, the transient direct detonation initiation, and pulsating instability of one-dimensional detonation propagation are investigated. It is found that the homogenous ignition process consists of two stages and the first stage is caused by ozonolysis reactions which consume O₃ and produces CH₂O as well as H and OH radicals. The ozonolysis reaction and ozone decomposition reaction can both reduce the induction length though they have little influence on the Chapman–Jouguet (CJ) detonation speed. The supercritical, critical and subcritical regimes for direct detonation initiation are identified by continuously decreasing the initiation energy or changing the amount of ozone addition. It is found that direct detonation initiation becomes easier at larger amount of ozone addition and/or larger reaction progress variable. This is interpreted based on the change of the induction length of the ZND detonation structure. Furthermore, it is demonstrated that the ozonolysis reaction can reduce pulsating instability and make the one-dimensional detonation propagation more stable. This is mainly due to the reduction in activation energy caused by ozone addition and/or ozonolysis reaction. This work shows that both ozone decomposition reaction and ozonolysis reaction can enhance detonation for unsaturated hydrocarbon fuels.