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DOI:10.11949/0438-1157.20191532
研究论文
基于 PR 立方型状态方程普遍化温度函数的研究与评价
赵文英 1,2,李文文 2,孙晓岩 2,曹晓荣 1,项曙光 1,2
(1 齐鲁师范学院化学与化工学院,山东 济南 250200; 2 青岛科技大学过程系统工程研究所,山东 青岛 266042)
Abstract: 17 generalized alpha functions for Peng-Robinson equation of state (PR EoS) were evaluated using the
vapor pressures of 11 kinds of non-polar, weakly polar and polar compounds. The estimative abilities of the
generalized alpha functions were compared according to the average absolute deviation of each kind of compounds.
The results indicated that the vapor pressures of alkanes, aromatic hydrocarbons, gases and halogenated
hydrocarbons can be accurately predicted with Robinson-Peng (1978), Wang (2004) and Li-Yang (2011) alpha
function. However, the predictions of vapor pressures for weakly polar and polar compounds, such as alcohols,
ethers, esters, acids, and water, with Robinson-Peng (1978), Wang (2004) and Li-Yang (2011) alpha function were
less accurate than that predicted with Forero (2016) alpha function. In conclusion, the generalized alpha functions
with acentric factor and polar factor as variables are more accurate than that generalized only with acentric factor for
the prediction of vapor pressures of polar compounds, such as alcohols, acids and water.
Key words: thermodynamics properties; equation of state; Peng-Robinson; generalized alpha functions; prediction;
evaluation
收稿日期:2019-12-18 修回日期:2020-01-06
通信作者:项曙光(1963—),男,博士,教授,xsg@qust.edu.cn
第一作者:赵文英(1982—),女,博士,讲师,qdzhaowenying@163.com
基金项目:山东省重大科技创新项目工程(2018CXGC1102)
引用本文:赵文英, 李文文, 孙晓岩, 曹晓荣, 项曙光 . 基于 PR 立方型状态方程普遍化温度函数的研究与评价[J]. 化工学报, 2020, 71(3): 1234-
1245
Citation: ZHAO Wenying, LI Wenwen, SUN Xiaoyan, CAO Xiaorong, XIANG Shuguang. Research and evaluation on generalized alpha functions
based on PR EoS[J]. CIESC Journal, 2020, 71(3): 1234-1245
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引 言 限制,适用范围窄。Soave[3] 最早提出普遍化温度函
数 ,此 后 Twu 等[15]、Coquelet 等[16]、汪 萍 等[17]、Li 和
立方型状态方程是中等至高压体系纯组分蒸 Yang[18]、Forero 等[19]、Le Guennec 等[10]、Mahmoodi 等[11]
汽压和流体混合物汽液平衡及焓、熵、热容等热力 不断研究温度函数普遍化的方法,用于非极性、弱
学性质预测的重要方法。van der Waals[1] 首次提出 极性和极性物质蒸汽压的预测。
适 用 于 真 实 气 体 的 立 方 型 状 态 方 程 ,Redlich 和 本文拟在 PR EoS 的基础上,用 70 种非极性、弱
Kwong 改进 VDW EoS 引力项的形式并将引力项系
[2]
极性和极性物质对 17 种普遍化温度函数预测蒸汽
数 a 关联为 Tr 的温度函数得到 RK EoS,但对纯物
0.5
压的能力进行评价,总结普遍化温度函数的特点,
[3]
质蒸汽压的预测精度不高。Soave 发现烃类物质的 确定较好的普遍化温度函数的形式和特点,为温度
α 与(1–Tr )呈线性关系,并将系数 m 普遍化为偏
0.5 0.5
函数普遍化方法的改进提供借鉴。
心因子的函数,得到著名的 SRK EoS,提高了对非极
性和弱极性物质蒸汽压的预测精度,但对液体体积 1 普遍化温度函数模型
的预测结果偏差较大。Peng 和 Robinson 改进 RK [4]
自 Soave[3] 提出普遍化温度函数以来,研究者不
EoS 引力项的形式并重新关联 Soave[3]温度函数的系
断改进温度函数的形式,得到上百种温度函数[14],但
数 m,得到 PR EoS,能够准确预测非极性和弱极性
普遍化的温度函数形式较少。通过整理,得到 17 种
物 质 的 蒸 汽 压 ,且 提 高 了 液 体 体 积 的 预 测 精 度 。
适用于 PR EoS 的普遍化温度函数,其中 5 种多项式
SRK 和 PR EoS 对非极性和弱极性物质蒸汽压的预
温度函数,12 种指数温度函数。5 种多项式温度函
测结果均比较准确,但对极性物质蒸汽压预测结果
的偏差较大。 数中Peng-Robinson(1976)[4]和Robinson-Peng(1978)[20]
续表
函数名称 参考文献 温度函数及参数关联式
2
Coquelet (2004) [16] 2 3
( ) é
(
a T r = ê1 + c 1 1 - T r + c 2 1 - T r
ë
) ( ) (
+c 3 1 - Tr ) ùúû
c 1 = 0.1316ω 2 + 1.4031ω + 0.3906
c 2 = -1.3127ω 2 + 0.3015ω - 0.1213
c 3 = 0.7661ω + 0.3041
2
汪萍(2004) [17] ( )
a T r = é1 + k 1 -
ë ( Tr ù
û )
k = k0 + k1 1 + ( Tr ) (0.7 - T ) as T r r ≤ 0.7
k 0 = 0.3784 + 1.5182ω - 0.2663ω + 0.0923ω 3 2
{ }
2
Li-Yang (2011) [18]
( ) (
α T r = exp k 1 1 - T r + l ln é1 + k 2 1 -
ë ) ( Tr ù
û)
l=0.81769
k 1 = 0.13280 - 0.05052ω + 0.25948ω 2
k 2 = 0.31355 + 1.86745ω - 0.52604ω 2
k 3 = 0.38856 + 1.40137ω - 0.05387ω 2 - 0.01824ω 3
( )
χ = lg P r ||
T = 0.6
+ 1.7ω + 1.552
r
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续表
函数名称 参考文献 温度函数及参数关联式
2
) ( ( )) ( ( ) ) ùúû,0 ≤ c
2 3
( )
4
é ω - 1.6645 ù
c 3 = 1.514exp êê - úú
ë 1.5474 û
2
) ( ( )) ( | c | (1 - ) ) ùúû
2 3
PR-PM2 (2017) [11] ( ) é
ë
(
α T r = exp ê2c 1 1 - T r - c 2 1 - T r +
3 1 Tr
RD = × 100% (1)
《Thermophysical Properties of Chemicals and P sat
exp
Hydrocarbons》[27]。 |
1 N P cal - P exp
sat sat
|
ARD = ∑
N 1 P sat
× 100% (2)
将物质的特性参数带入普遍化的温度函数关 exp
图1 参数普遍化温度函数对不同类别物质蒸汽压预测结果的平均相对偏差
Fig.1 ARDs of vapor pressures for different kinds of compounds with generalized alpha functions
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图2 参数普遍化温度函数对正构烷烃蒸汽压预测结果的平均相对偏差
Fig.2 ARDs of vapor pressures for normal alkanes with generalized alpha functions
图3 参数普遍化温度函数对正丁烷蒸汽压预测结果的相对偏差随对比温度变化趋势
Fig.3 RDs of generalized alpha functions on prediction of vapor pressures of n-butane with increasing reduced temperature
·1240 · 化 工 学 报 第 71 卷
图4 参数普遍化温度函数对正构醇蒸汽压预测结果的平均相对偏差
Fig.4 ARDs of vapor pressures for normal alcohols with generalized alpha functions
图5 参数普遍化温度函数对正丁醇蒸汽压预测结果的相对偏差随对比温度的变化趋势
Fig.5 RDs of generalized alpha functions on prediction of vapor pressures of n-butanol with increasing reduced temperature
第3期 www.hgxb.com.cn ·1241 ·
符 号 说 明 69-84.
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ARD ——平均相对偏差 combinations of property data that are suitable for a safe
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