本文選題：HFO-1234yf + 替代工質(zhì)　； 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2015年博士論文

【摘要】：氫氟烴(HFCs)和烷烴(HCs)臭氧耗減潛能值(ODP)為0,不破壞臭氧層,是很有前景的替代工質(zhì)。但是大多數(shù)的HFCs具有較高的全球變暖的潛能值(GWP)和大氣壽命長(zhǎng)的缺點(diǎn),根據(jù)歐盟F-gas法規(guī)規(guī)定,高GWP的含氟工質(zhì)開(kāi)始被限制在新設(shè)備中使用。而HCs又具有易燃易爆的危險(xiǎn)。因此尋找新型綠色環(huán)保的替代工質(zhì)迫在眉睫。近年,霍尼韋爾和杜邦公司聯(lián)合推出了一種新型制冷劑,2,3,3,3-四氟丙烯(HFO-1234yf),其GWP1, ODP為0,以及非常短暫的大氣壽命(0.029年),被視為很有前景的環(huán)保替代工質(zhì)。但是其較低的汽化潛熱值以及微可燃性成了它單獨(dú)使用的障礙。 由于很難找到既環(huán)保又擁有優(yōu)異制冷性能的純工質(zhì),而混合工質(zhì)通過(guò)不同的組分的配比有望找到合適的替代工質(zhì)。混合工質(zhì)的熱力學(xué)性能優(yōu)劣是其能否被利用的主要因素,其中氣液相平衡(VLE)數(shù)據(jù)更是系統(tǒng)循環(huán)熱力學(xué)分析的基本參數(shù)。目前,實(shí)驗(yàn)測(cè)量是獲得氣液相平衡數(shù)據(jù)最準(zhǔn)確的方法,因此建立一套高精度測(cè)量混合工質(zhì)VLE性質(zhì)的實(shí)驗(yàn)裝置,是非常有必要的。 本文在已有制冷工質(zhì)PVT實(shí)驗(yàn)測(cè)量系統(tǒng)的基礎(chǔ)上,添加了混合工質(zhì)循環(huán)取樣系統(tǒng)、摩爾分?jǐn)?shù)測(cè)量系統(tǒng)和空氣恒溫系統(tǒng),改進(jìn)成高精度氣液相平衡實(shí)驗(yàn)裝置。通過(guò)對(duì)HFC-134a/HFC-227ea二元混合工質(zhì)氣液相平衡的實(shí)驗(yàn)測(cè)量,并與文獻(xiàn)對(duì)比,證明了本實(shí)驗(yàn)裝置測(cè)量精度高,運(yùn)行穩(wěn)定可靠。 利用搭建好的實(shí)驗(yàn)裝置,對(duì)含有新型制冷工質(zhì)HFO-1234yf的二元及三元混合工質(zhì)氣液相平衡性質(zhì)進(jìn)行實(shí)驗(yàn)研究。測(cè)量了HFC-143a/HFO-1234yf、 HFO-1234yf/HFC-152a、HFO-1234yf/HFC-227ea、HFO-1234yf/HFC-600a、HFC-161/HFO-1234yf等二元混合工質(zhì)以及TFC-134a/HFO-1234yf/HC-600a三元混合工質(zhì)的氣液相平衡性質(zhì)。得到的實(shí)驗(yàn)數(shù)據(jù)結(jié)合Peng-Robinson(PR)方程和van-der-Waals(vdW)混合法則進(jìn)行關(guān)聯(lián)計(jì)算,得到其二元相互作用系數(shù),并證明了PR方程結(jié)合vdW混合法則,適用于含HFO-1234yf I的氣液相平衡性質(zhì)計(jì)算。 課題組之前針對(duì)10種HFC與3種HC的二元交互系數(shù)建立的差值模型,作者在這13種工質(zhì)的基礎(chǔ)上加入了HFC-161和HFC-134,并引入了臨界點(diǎn)參數(shù)和偏心因子對(duì)其進(jìn)行改進(jìn),得到交互加權(quán)差值模型。交互加權(quán)差值模型計(jì)算精度要高于差值模型。收集了一些HFO-1234yf/HFC的VLE數(shù)據(jù),并關(guān)聯(lián)得到其二元相互作用系數(shù)。將交互加權(quán)差值模型推廣至HFO-1234yf,發(fā)現(xiàn)HFO-1234yf/HFC推算精度滿足工程需求,HFO-1234yf/HC推算偏差較大。考慮到碳碳雙鍵的影響,對(duì)HFO-1234yf與HC體系的相互作用系數(shù)作了修正,修正后推算精度能更好的滿足工程需求。 利用交互加權(quán)差值模型對(duì)含HFO、HFC、HC的二元混合共沸點(diǎn)進(jìn)行推算。針對(duì)HFO/HC和HFC/HC體系一共39組混合物進(jìn)行研究,結(jié)果表明39組混合物中有30組具有明顯共沸點(diǎn),9組沒(méi)有共沸點(diǎn)。 將交互加權(quán)差值模型應(yīng)用到三元混合物的氣液相平衡推算,推算結(jié)果與文獻(xiàn)給出的五組、作者自行測(cè)量的一組以及制冷熱物性數(shù)據(jù)庫(kù)軟件REFPROP提供的12組三元混合物進(jìn)行比較。除了HC-290/HC-600a/HFC-32推算壓力偏大在8.05%,其他三元混合工質(zhì)的推算壓力偏差都小于2%,而氣相組分的平均偏差也大多在0.01內(nèi)。說(shuō)明該模型能用于推算三元混合物的氣液相平衡性質(zhì)。 使用交互加權(quán)差值模型對(duì)三元混合工質(zhì)的共沸性質(zhì)進(jìn)行推算。研究由16種純工質(zhì)匹配組合成的三元混合工質(zhì)。研究的三元混合工質(zhì)只針對(duì)組成該混合物的三種工質(zhì)兩兩之間構(gòu)成的二元混合物是共沸或近共沸的,符合此條件的一共有53種。結(jié)果表明,有三組三元混合工質(zhì)存在明顯共沸性質(zhì)。其中HFC-32/HFC-125/HFC-143a三元混合工質(zhì)在溫度低于220K時(shí)才出現(xiàn)共沸點(diǎn),這個(gè)結(jié)果與文獻(xiàn)描述基本一致,表明推算結(jié)果具有很強(qiáng)的指導(dǎo)意義。
[Abstract]:The ozone depletion potential (ODP) of hydrofluorocarbons (HFCs) and alkanes (HCs) is 0. It is a promising substitute for ozone layer without destroying the ozone layer. However, most HFCs has the disadvantages of high global warming potential (GWP) and long atmospheric life. According to EU F-gas regulation, high GWP fluorochemicals are started to be used in new equipment. And HCs It is also in danger of flammable and explosive. Therefore, it is imminent to find a new green alternative. In recent years, Honeywell and DuPont Co have jointly launched a new refrigerant, 2,3,3,3- tetrafluoropropene (HFO-1234yf), its GWP1, ODP is 0, and a very short atmosphere life (0.029 years), which is considered as a promising alternative to environmental protection. However, its lower vaporization latent heat and its micro flammability become obstacles to its use alone.
Because it is difficult to find the pure refrigerant with both environmental protection and excellent refrigeration performance, the mixture is expected to find a suitable substitute by the ratio of different components. The thermodynamic performance of the mixture is the main factor for its utilization, and the gas liquid equilibrium (VLE) data is the basic parameter of the thermodynamic analysis of the system cycle. At present, the experimental measurement is the most accurate method to obtain the gas liquid phase equilibrium data. Therefore, it is very necessary to establish a set of high precision experimental device for measuring the VLE properties of the mixed refrigerant.
On the basis of the existing PVT experimental measurement system of refrigerant refrigerants, the mixed refrigerant circulation sampling system, the mole fraction measurement system and the air constant temperature system are added to improve the high precision gas-liquid equilibrium experimental device. Through the experimental measurement of the gas-liquid equilibrium of the HFC-134a/HFC-227ea two element mixture, it is proved by comparison with the literature. The measuring precision is high and the operation is stable and reliable.
The experimental study on the gas-liquid equilibrium properties of two and three elements mixed refrigerants with a new refrigerant HFO-1234yf was carried out by a set of experimental equipment. The two element mixed refrigerants, such as HFC-143a/HFO-1234yf, HFO-1234yf/HFC-152a, HFO-1234yf/HFC-227ea, HFO-1234yf/HFC-600a, HFC-161/ HFO-1234yf, and so on were measured. The gas-liquid equilibrium properties of the 0A three element mixture are obtained by the experimental data combined with the Peng-Robinson (PR) Fang Chenghe van-der-Waals (vdW) mixing rule, and the binary interaction coefficient is obtained. It is proved that the PR equation is combined with the vdW mixing rule and is suitable for the calculation of the gas-liquid equilibrium properties containing HFO-1234yf I.
Before the task group set up the difference model of 10 HFC and 3 kinds of HC, the author added HFC-161 and HFC-134 on the basis of these 13 types of working fluids, and introduced the critical point parameter and eccentricity factor to improve it, and got the interactive weighted difference model. The calculation precision of the interactive weighted difference model was higher than the difference model. Some HFO-1234yf/HFC VLE data are obtained, and their binary interaction coefficients are correlated. The interaction weighted difference model is extended to HFO-1234yf. It is found that the precision of HFO-1234yf/HFC calculation satisfies the engineering requirement, and the deviation of HFO-1234yf/HC calculation is large. Considering the effect of carbon carbon double bonds, the interaction coefficient of HFO-1234yf and HC system is amended, The revised calculation accuracy can better meet the engineering requirements.
The two element mixed azeotrope containing HFO, HFC and HC was calculated by using the interactive weighted difference model. A total of 39 groups of mixtures in the HFO/HC and HFC/HC systems were studied. The results showed that there were 30 groups of obvious azeotrope in the 39 groups and the 9 groups had no azeotrope.
The interaction weighted difference model is applied to the calculation of the gas-liquid equilibrium of the three element mixture. The calculated results are compared with the five groups given by the literature, and compared with the 12 groups of three yuan mixture provided by the author, as well as the refrigerating thermal physical database software REFPROP. In addition to the HC-290/HC-600a/ HFC-32 calculation, the pressure is 8.05%, and the other three yuan mixture is mixed. The calculated pressure deviations of the working fluid are less than 2% and the average deviation of the gas component is mostly within 0.01. It shows that the model can be used to calculate the gas-liquid equilibrium properties of the three element mixture.
An interaction weighted difference model is used to calculate the azeotropic properties of the three element mixed refrigerants. A mixture of three elements composed of 16 kinds of pure refrigerants is studied. The study's three element mixture is only for the azeotrope or near azeotrope composed of three components of the three refrigerant consisting of the mixture, which is 53 of this condition. The results show that there are obvious azeotropic properties of three groups of three element mixed refrigerants. The azeotrope of HFC-32/HFC-125/HFC-143a three element mixture occurs when the temperature is lower than 220K. This result is basically consistent with the literature description, indicating that the calculated results are of great guiding significance.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TB61

【參考文獻(xiàn)】

相關(guān)期刊論文 前4條

1 周偉;公茂瓊;洪輝;吳劍鋒;;二元相互作用系數(shù)推算方法的發(fā)展[J];低溫工程;2006年01期

2 李振花;劉新剛;馬新賓;王保偉;王勝平;許根慧;;甲醇、碳酸二甲酯、草酸二甲酯二元體系汽液平衡測(cè)定與關(guān)聯(lián)[J];化學(xué)工程;2006年02期

3 汪訓(xùn)昌;;《蒙特利爾議定書(shū)》締約方第19次會(huì)議第XIX/6號(hào)決定及相關(guān)決議的解讀與述評(píng)[J];暖通空調(diào);2009年01期

4 李嵩;;F-Gas新法規(guī):不可小覷的影響力——訪歐盟委員會(huì)官員Cornelius Rhein[J];制冷與空調(diào);2014年05期

，

本文編號(hào)：1892561