正戊烯的Helmholtz状态方程研究

doi:10.11949/j.issn.0438-1157.20170972

摘要/Abstract

摘要：

正戊烯是重要的精细化工产品中间体和原材料，同时也是燃料添加剂，具有广泛的工业应用。正戊烯的生产和应用过程中常常涉及萃取、精馏、汽提等化工过程，而这些化工流程的设计、模拟、优化等都依赖于准确可靠的热物性数据。通过文献调研发现，目前还没有正戊烯的专用状态方程发表，因此利用文献中公开发表的实验数据开发了正戊烯的专用状态方程。该方程以Helmholtz自由能为显式、以密度和温度为自变量，适用范围为：温度从三相点到500 K，压力最高达到100 MPa，密度不超过15 mol×dm⁻³。方程计算液相区密度的不确定度为0.2%，计算临界区及气相密度的不确定度为0.5%；计算饱和蒸气压的不确定度为0.3%，计算饱和液相密度的不确定度为0.2%，计算与能量相关的物性（例如C_sat、比热容、音速、焓等）的不确定度为1%以内。所开发的正戊烯专用状态方程不仅能够准确地复现实验数据，而且具有良好的外推性。

关键词: 正戊烯, Helmholtz, 状态方程, 热力学, 热力学性质

Abstract:

To popularize the application of n-pentene in industry, such as chemical simulation, process optimization, and properties research, the equation of state for n-pentene was developed based on a body of experimental data that has been critically assessed for internal consistency and for agreement with theory in this work. The Helmholtz energy as the fundamental property with independent variables of density and temperature was used for the equation of state. The equation of state is valid from the triple-point temperature to 500 K, with pressures up to 100 MPa and densities up to 15 mol×dm^-3. Overall,the uncertainties in density range of the equation of state are 0.2% in the liquid region and 0.5% in the critical and vapor region. The uncertainty is 0.3% for the vapor pressure and 0.2% for the saturated liquid density. The uncertainties in the properties related to energy (such as heat capacity, sound speed, enthalpy and so on) are estimated to be 1%. The behavior of the equation of state is reasonable within the region of validity and at higher and lower temperatures and pressures.

Key words: n-pentene, Helmholtz, equation of state, thermodynamics, thermodynamic properties

中图分类号:

TK121

杨建, 孟现阳, 高克慧, 吴江涛. 正戊烯的Helmholtz状态方程研究[J]. 化工学报, 2018, 69(4): 1315-1323.

YANG Jian, MENG Xianyang, GAO Kehui, WU Jiangtao. Helmholtz equation of state for n-pentene[J]. CIESC Journal, 2018, 69(4): 1315-1323.

参考文献 44

[1]	李金芝, 龙军, 赵毅, 等. 1-戊烯骨架异构反应的热力学分析[J]. 石油学报(石油加工), 2013, 29(6):929-935. LI J Z, LONG J, ZHAO Y, et al. Thermodynamic analysis of 1-pentene skeletal isomerization reaction[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2013, 29(6):929-935.
[2]	张冬梅, 傅建松. 1-戊烯分离的流程模拟和优化[J]. 石油化工技术与经济, 2009, 25(5):14-19. ZHANG D M, FU J S. Process simulation and optimization for 1-pentene isolation[J]. Technology & Economics in Petrochemicals, 2009, 25(5):14-19.
[3]	CLAPEYRON E. Memoire sur la puissance motrice de la chaleur[J]. Journal de I'Ecole Polytechnique, 1834, XIV:153-190.
[4]	PENG D Y, ROBINSON D B. A new two-constant equation of state[J]. Industrial & Engineering Chemistry Fundamentals, 1976, 15(1):59-64.
[5]	SOAVE G. Equilibrium constants from a modified Redlich-Kwong equation of state[J]. Chemical Engineering Science, 1972, 27:1197-1203.
[6]	KAMERLINGH ONNES H. Expression of the Equation of State of Gases and Liquids by Means of Series[M]. Netherlands:Springer, 1991.
[7]	KEENAN J H, KEYES F G, HILL P G, et al. Thermodynamic Properties of Water Including Vapor, Liquid, and Solid Phases[M]. New York:John Wiley & Sons Interscience, 1969.
[8]	SCHMIDT R, WAGNER W. A new form of the equation of state for pure substances and its application to oxygen[J]. Fluid Phase Equilibria, 1985, 19:175-200.
[9]	JACOBSEN R T, STEWAR R B, JAHANGIRI M. A thermodynamic property formulation for nitrogen from the freezing line to 2000 K at pressures to 1000 MPa[J]. Journal of Physical and Chemical Reference Data, 1986, 7:503-511.
[10]	MARIA E M, MARK O M, ERIC W L. Thermodynamic properties of trans-1-chloro-3,3,3-trifluoropropene (R1233zd (E)):vapor pressure, (p, ρ, T) behavior, and speed of sound measurements, and equation of state[J]. Journal of Chemical and Engineering Data, 2015, 60(8):2477-2489.
[11]	GAO K H, WU J T, ZHANG P, et al. A Helmholtz energy equation of state for sulfur dioxide[J]. Journal of Chemical and Engineering Data, 2016, 61(8):2859-2872.
[12]	VESPIGNIANI G R. Concerning the critical constants of some organic substances[J]. Gazzetta Chimical Italiana, 1903, 33:73-78.
[13]	DAY H O, NICHOLSON D E, FELSING W A. The vapor pressures and some related quantities of 1-pentene from 0 to 200℃[J]. Journal of the American Chemical Society, 1948, 70:1784-1785.
[14]	AMBROSE D, COX J D, TOWNSEND R. The critical temperatures of forty organic compounds[J]. Trans. Faraday Society, 1960, 56:1452-1459.
[15]	MOUSA A H N, KAY W B, KREGLEWSKI A. The critical constants of binary mixtures of certain perfluoro-compounds with alkanes[J]. Journal of Chemical Thermodynamics, 1972, 4:301-311.
[16]	WOLFE D, KAY W B, TEJA A S. Phase equilibria in the n-pentane +1-pentene system(1):Critical states[J]. Journal of Chemical and Engineering Data, 1983, 28(3):322-324.
[17]	GUDE M T, ROSENTHAL D J, TEJA A S. The critical properties of 1-alkenes from 1-pentene to 1-dodecene[J]. Fluid Phase Equilibria, 1991, 70(1):55-64.
[18]	马沛生, 马友光, 张建侯. 四个有机化合物临界参数的测定[J]. 高校化学工程学报, 1991, 5:175-181. MA P S, MA Y G, ZHANG J H. Determination of the critical parameters of four organic compounds[J]. Journal of Chemical Engineering of Chinese Universities, 1991, 5:175-181.
[19]	SHERRILL M L, MAYER K E, WALTER G F. Addition of hydrogen bromide to 1-pentene and 1-heptene[J]. Journal of the American Chemical Society, 1934, 56:926-930.
[20]	FOETHR E G, FENSKE M R. Magnetooptic rotation of hydrocarbons[J]. Industrial & Engineering Chemistry, 1949, 41(9):1956-1966.
[21]	SCOTT D W, WADDINGTON G, SMITH J C, et al. Thermodynamic properties of three isomeric pentenes[J]. Journal of the American Chemical Society, 1949, 71(8):2767-2773.
[22]	STRYJEK R, GORAL M, ORACZ P, et al. Vapour-liquid equilibrium in C5-hydrocarbons-(beta)-methoxypropionitryle systems[J]. Bull. Acad. Polon. Sci., Ser. Sci. Chim., 1978, 26:689-700.
[23]	MAHER P J, SMITH B D. Vapor-liquid equilibrium data for binary systems of chlorobenzene with acetone, acetonitrile, ethyl acetate, ethylbenzene, methanol and 1-pentene[J]. Journal of Chemical and Engineering Data, 1979, 24:363-377.
[24]	MAHER P J, SMITH B D. Vapor-liquid equilibrium data for binary systems of aniline with acetone, acetonitrile, chlorobenzene, methanol, and 1-pentene[J]. Journal of Chemical and Engineering Data, 1980, 25:61-88.
[25]	BRUSTMAN S. Isothermal vapor-liquid equilibrium and excess enthalpy data for the binary systems diethyl ether + ethyl tertbutyl ether, 1-pentene + methyl acetate, and propene +2-propanol[J]. Journal of Chemical and Engineering Data, 1999, 44:383-387.
[26]	OSCARSON J L, LUNDELL S O, CUNNINGHAM J R. Phase equilibria for ten binary systems[J]. AIChE Symposium Series, 1987, 83:1-17.
[27]	FISCHER K, GMETHLING J. Vapor-liquid equilibria, activity coefficients at infinite dilution and heats of mixing for mixtures of n-methyl-2-pyrrolidone with C5 or C6 hydrocarbons and for hydrocarbon mixtures[J]. Fluid Phase Equilibria, 1996, 119:113-130.
[28]	VERRAZZI A, KIKIC I, GARBERS P, et al. Vapor-liquid equilibrium in binary systems ethanol + C4 and C5 hydrocarbons[J]. Journal of Chemical and Engineering Data, 1998, 43:949-953.
[29]	BENSON S W. Micromethod for identification of volatile liqiuds:vapor pressures of cyclopentane and the pentenes[J]. Analytical Chemistry, 1941, 13:502-504.
[30]	DAY H O, FELING W A. The compresibility of 1-pentene[J]. Journal of the American Chemical Society, 1951, 73:4839-4840.
[31]	KIREEV B N. Determination of the density of olefins along the saturation line[J]. Nauchn. Tr. Kursk. Gos. Pedagog. Inst., 1974, 23:40-52.
[32]	LANDOLT H, JAHN H. The molecular refraction of several simple organic compounds for rays of infinitely great wave length[J]. Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics, 1892, 271:289-297.
[33]	杨建. n-pentene、n-hexene及n-heptene的密度研究及Helmholtz状态方程开发[D]. 西安:西安交通大学, 2016. YANG J. Density measurements and Helmholtz equations of state for n-pentene, n-hexene and n-heptene[D]. Xi'an:Xi'an Jiaotong University, 2016.
[34]	SHERRILL M L, WALTER G F. Preparation and physical constants of 2-methyl-1-butene[J]. Journal of the American Chemical Society, 1936, 58:742-748.
[35]	VANARKEL A E, MEERBURG P, HANDEL C R. The dipole moment of cylanes[J]. Recueil des Travaux Chimiques des Pays-Bas, 1942, 61:767-779.
[36]	GERDING H, VAN DER VET A P. Raman spectra of the seven isomeric pentenes and quantitative analysis of two mixtures by means of the Raman effect[J]. Recueil des Travaux Chimiques des Pays-Bas, 1946, 64:257-271.
[37]	OGORODNIKOV S K, KOGAN V B, NEMTSOV M S. Liquid-vapor equilibria in binary systems of methanol and hydrocarbons[J]. Zhurnal Prikladnoi Khimii, 1960, 33:2685-2693.
[38]	GORIN Y A, GALKINA G I, MAKASHINA A N, et al. Catalytic dehydrogenation of normal pentenes and isopentenes and of their mixtures diluted with steam[J]. Zhurnal Prikladnoi Khimii, 1966, 39:1577-1583.
[39]	EIDUS Y T, NUZITSKⅡ V, YUNG P Y. Carbonylation of 1-pentene and 3-methyl-1-butehe by carbon monoxide in the presence of hydrates of boron trifluoride[J]. Russian Chemical Bulletin, 1970, 46:1673-1685.
[40]	FRENKEL M, CHIRICO R D, DIKY V, et al. NIST ThermoData Engine[DB]. Gaithersburg:National Institute of Standards and Technology, 2010.
[41]	AKHMEDOV A G, EFENDIEV M F, MIRZOEV B M. Temperature dependence of the heat capacity of liquid alkenes[J]. Russian Chemical Bulletin, 1987, 30:62-76.
[42]	TODD S S, OLIVER G D, HUFFMAN H M. The heat capacities heats of fusion and entropies of the six pentenes[J]. Journal of the American Chemical Society, 1947, 69:1519-1529.
[43]	MESSERLY J F, TODD S S, FINKE H L, et al. Heat capacities of 1-pentene (10 K to 320 K), cis-2-hexene (10 K to 330 K), 1-nonene (10 K to 400 K) and 1-hexadecene (10 K to 400 K)[J]. Journal of Chemical Thermodynamics, 1990, 22:1107-1128.
[44]	TAKEDA K, YAMAMURO O, OGUNI M, et al. Calorimetric study on structural relaxation of 1-pentene in vapor-deposited and liquid-quenched glassy states[J]. Journal of Physical Chemistry, 1995, 99:1602-1607.