Simple equation of state accurately predicts hydrocarbon densities Mohammad-Reza Riazi, G. Ali Mansoori University of Illinois at Chicago Chicago AS cubic equation Oo state (EOS) for hy | PW Srocsrbon systems ac curately predicts densities of 3 variety of hydrocarbons ranging frum C, to The equation is simpler than typical industrial equa tions of state currently used of T3 for density predic tions of pure Cy-Cas hyeiroe carbons and 1.7% for hyciro- carbon mixtures (C-Cu at pressures as high as 700 bar hal temperatures of LOW K. A recent article discussed uses for such equations of slate (OG), Feb. 13, p. 2), Accurate equations. of state for predicting vapor pressure and pressure-\ ob Ume-temperature (PVT) properties of hydrocarbons are vital to the design and operation of equipment in natural gas and other petro- Teum-related industries." A generalized equation tor predicting vapor pressures fof hydrocarbons was recent. | lv reported (OG), Feb. 1p. 39). A simple, new equation of state can be used for ENT calculations of light, as well as heavy, hydrocarbons with readily available input pura meters and greater accuricy than existing methods. Because of their availabilty and high accuracy tor I'VT calculations involving, hydeo carbons, the necessary input parametersarethe critical prp- erties and refractive index 8 (RK-EOS)—a simple and Equation 1 is the Redlich- | widely used EOS (see Equa- Kwong equation of state | tions and Nomenclature). In P= Thy — by - eT + DT 0 a= oars RTP, @ » = 0.0664 ATUP, ° = (109 Pincers o Pa = (abba + WAT) = (NB) s)1Knt+ 2) ° = (0.0064 ATP) B (RT) © Ln,1 + {ogelt ~ o.scexp(—1.000)T, — 111 - 0s ane 0 Ton = (2EaAT Pa) EDATalPa) o Pon = (EERATa Pa) CEEAATa o Frm = Eh 09) Ta = Mata" 1 a Pq = Talal" + TaPaF 0 Fy = et + 3) NOMENCLATURE Pressure ‘Univeral gas constant ‘Absolute teroeratre Molar vole Pe a T 5 % FR, = Molar action (see Equation 5) p= Mola Ne = Avogadro's number (6.028 x 10%) = potarzapiy 1 = Dipole moment (almost zo or nonpolar compounde) = SodunrO ight reactive index of quid a 20°C. and 1 atm R= Rone Fw = The valve of moar reaction fora reference fut (ere taken to Eermathene) for WSN Bor = 1 8 ~ Binealries ncaa by Exton? (incon Be = B fr methane (a function ofb, as defined in Equation 6) T= Citcalwenperatire Z = Compress factor %_= Critcal compressby factor this equation, “a” and “b” are constants defined as shown in Equations 2 and 3 Although’ Equation 1 is quite accurate for the gas phase, it is not accurate ‘enough for liquid systems oF for the saturated region.” Many modifications of this equation—most designed to improve its accuracy for liq uid-state calculations—have bbeen reported in the liter ture, ‘A modified RK-EOS pro- posed by Soave, named SRK, and another cubic equation by Peng and Rob- inson (PR) typically are used for hydrocarbons.** The ‘SRK and PR equations, how ever, break down for Cis and heavier hydrocarbons, In all these equations, pa- rameter “a” generally is con- sidered a function of the re- duced temperature and the acentric factor (Equation 4, while parameter “b” is kept constant. Parameter. "b,” however, is more effective for calculating liquid densi- ties because it represents the volume of molecules. For liquid systems in which the free space be- tween molecules decreases, the role of “b” becomes more important than that of a." Parameter “b” is also important for PVT predi tion of dense gases and liq- uid. For low-pressure gases, however, “b” becomes less important than “a” because the spacing between mole- cules increases and, as a re 018 Gas dural ey 12, 1993,Sa asd Table 1 | fim 6 20°C. No.of Temperature Data source | Compound ber Guempmole RY data points ange Ke renge, ber Gleteronce No) Matnane (C:) woe 460 6067 1.000135 90500 05-700 10 Elnane fc) se 488 39180 Tay S070 01-700, u Propane (Ca Sea fos ist 2358130, Be700 01:70, 2 Etryone (C34) poe Soe 1030 50899 00-800 9400 3 Isobutane (ccs) 4002368 per 2888 10700 07-700 Butane (cs) 132 380 foxes 38093 130-700 01-700 18 Morane (nC) sors Son boo = 42500 26-1000 1500 3 Gyethorere (GoM. 5535 07 Brym = Ase ao fe01o00 1500 8 Benzone (Cats) Soe fag boise 3788 10 Sto-1o00 1500 5 Toluene (Ch Se to Brom 4430 He 3301000 1300 8 meta (rc) 503 bra ShSse 4348 foo 3001000 1-500, 8 P-Oetane (ns) Se |S soir S008 ko 2011000 500 6 2geTomatybenane Gn) kd BS zr Sere 340 0001800 8 ieo-atane} | eetoptane rc 2 stos are 24554 Ages as 303973 $0500 2 PNonane (Cx Sue ao Geo 628 30337 50500 a | Urdecane iC.) sas 97 Sis Fes aS 303373 S000 at | mindecane in‘) sro 72 four 883530 Sear) 50800 a | tHeptadecane (0 m0 | ke Soe 858530 Bes373 Sos a | Sesosana Inca) vero Nth aie aes 20 387) So800 a | nttecontane ret gazo ‘er viz 20232 arasra 50500 a MTetracontane tu) ero 8a tere nee 223873 50800 a Table 2 Compound Experimental AKA SAK PR New AK, SAK & PR New Morrone 0288 03% —(osor oss 00. 90 Etnane 0266 3% (0307 Os oo 0.0203 Propane Saar Oa © baer aaa oo. 9.028 Etnyone 0376 033 = (0307s 90 0.0208 Feodetane 0.383 03 © O3or are 00. 232 Butane oar 3s = 307 Oars 89. 9.0920 eHorane 0.360 033 ©0307 ae 00 100 Gyetnocane 037 033 03078 oo 8.0301 Stncone oan 03 © 03078 00. 0302 Toluene 8 e4 33 O30, oo. O32, sHeptane 0.363 33 © O30 (Oo 80. oars nOcane 0259 Ox = aor Ose 89. Soret onan 0333 bao, oa 80 oot ne O33 © O30 aa? ry oor ne 0200 33 © «b307 Oat 80. oon nee 9230 033 © oso, oar 90. 0.0950 ne 9220 3303070259 89. 8.0080 mao! = am Sta OR Sy 00 0189 tate 5 | sult, the attraction energy De a 225 Temethypentane 0 i Nooane & R-Undecane 38 tnecane x Mopiadoeane » | etcosane 2 etnacontane bo hnTewacontane » Overat hy 12, 1985 #04 6 Gas Jura ® BUBss. Brbubouoncoeenonhece ze ge prevails.® In the new RK- EOS modification presented here, “a” is kept constant while “b” is modified using the molecular theories of perturbations and refractive index. Molar refraction (Rn), which represents the vol- lume occupied by molecules per unit mole, is defined by Equation 5. Because “b” and “Ra” have the same physical meaning, it can be conclud- ed that "b” must be a func- tion of Ry Asa result, Equa tion 3 can be replaced with Equation 6—a general ex- pression for “bn terms of Rj, and temperature. ‘Equation 7 is obtained foratte | tions is given in Tables 2 and 3. In these tables, “New” refers to calculations using Equations 1, 6, and 7. ate ples = Aetrooce ‘Table 2 shows the predic- 28 1s 162~—~*9~SCR tions for Z., (dP/4V)i.. and ° 23080 oo (PAV), for various hy- a op gtk drocarbons. According to i“ Boo ae ar Table 2, the new equation u i predicts the critical com- 9 o: 02M ak ; 8 05 192 159, $2007 pressibility factor of hydro- 8 ose Ea carbons much more accu- Nerane 1 nievadscare 3 2 Bl owe ae rately than the other equa- trae + prheradocane 3 {8 8 MS we tions. Matane ' “rocosare 3 22 2 ik The errors of predicting hare” neeasane 8 os ORS ESB the first and second deriva- Nethane|bopane decay a a ve S88 tives of pressure, with re- ; Mati eine at v7 21 2838 38 __| | spect to volume, at the criti- i) 20 Msgs || cal_point, however, are slightly increased compared to the other equations of B, based on dense fluid data | methane using the RK, SRK, | ments for a simple reference | state (Table 2). for CC, compounds. This | and PR equations of state for | fluid for hydrocarbon sys- | Table 3 shows a summary equation satisfies the condi | 135 data points of methane | tems. of results for density calcula- tion B = Tat R’ = 1. Both | at 90-500 K. and 0.7-700 bar. | Table 1 presents the val- | tions using the four equa- “p" and “n” in Equation 7 | The percentage average | ues of Re (taken from TRC | tions of state on more than vary with temperature, but | absolute deviation (AAD) of | tables) and R', plus critical | 1,700 data points. The pro- Ry is nearly independent of | the density calculations us- | properties and liquid and | posed equation achieves an temperature, ing the RK equation is 0.9%. | vapor PVT data for the 20 | average error for density In deriving Equation 7. it | The AAD for the SRK and | hydrocarbons used in this | predictions of hydrocarbon was assumed that, at any | PR equations are 1.0% and | study, which range from C, | systems, from methane to n- given temperature, the devi- | 4.5%, respectively. The RK- | to Cy.* tetracontane (n-Cu), of ation of B from unity is pro- | EOS is therefore used as the | A summary of the com- | 1.33%, for pressures as high portional to the deviation of | reference EOS because it | parison of the new EOS with | as 700 bar. from unity. For all com- | best satisfies the require- | the RK, SRK, and PR equa- | According to Tables 2 and pounds, B is less than unity 3, this new’ modification of and, a3 a fluid becomes the RK-EOS is superior to ‘more complex, the value of the other equations of state B decreases. for all the hydrocarbons studied. The proposed equa- Application to mixtares tion is also simple and more Equations 1, 2, 6, and 7 accurate than any other con- can be applied to mixtures of ventional cubic equations known composition using currently used, the van der Waals one-fluid A bank of density data for mixing rules." This tech- || | ™ & some binary and ternary hy- nique produces Equations &, was Grocarbon mixtures has been Sand 10 collected frm the literature In these relations, summa- (Table 4)."°?° The proposed tions are ever all compo. EOS, along with. Equations atl ‘oe am nents of the mixture and Xs 8-13 for mixture properties, the mole fraction of compo was evaluated using this nents i and j. Equations 1, Mansoor data base. Results are given 12, and 13 are used to repre- én i cole! and nc pci in Table 4. sent the interaction ofthe | | thus Rin oman el intra sciing For the 17 binary and ter terms Tey, Pri, and R'y. In || properties, chiactrteation of petroleum fractions, tanspo! pe nary mixtures used in this Equations 11-13, the term ky |] pent mht mg nd Unt evaluation, the new EOS is the interaction parameter || Riz! witng exec profes of hema enginering at gives an average absolute which, for simplicity, is con- | | Megimmeriy of Mimo a! Oncag, te wa frmery an sist deviation of 1.8%, which is sidered zero in these calcuia- || Snes in crea engin Here mene of ACHES ACS. ond far better than the other tions. the Scenic Research Society of North America equations tested. The Peng- . Ali Mann prfor of chemi engining ot he Robinson equation, for ex- LUnierity of lines, Ohcag. He ts» postdetora ew af Rice ample, gives an error of For methane—the refer- || Unnwnaty. Houton, fom 1960 to 197. Mast hs ten 6.1% for these mixtures ence fluid here—the RK- ‘consultant to the United Nations, Argonne National Laboratory, U.S. Note that the last set of EOS is more accurate than || Deere! of Commer, cn ras che pc tnt data in Table 4s taken from most other equations of || QUA. mene haa PHD from the Unter of the mixture of methane, pro- state. This is demonstrated | | the Ueenty of Tokran, alm chemislenginering pane, and ndecane at the by calculating density of critical state. Equation 4 was 10 (08 Gas dural uy 12,1983used for the evaluations shown in Table 4 because the exponential term in Equation 6 disappears, even for mixtures at the critical state ‘A major advantage of the new EOS is that, when it is applied to mixtures of undefined petroleum fractions and direct experimental data are available for molecular weight, refractive index, and density at 20°C. there is no need. to calculate the mixture molar refrac tion. In such cases, acentric factors may not be calculated accurstely Acknowledgment This research is supporte:! in part by Gas Research Institute Contract No. 5090-260-2085, Campbell, JM, Gas Conditioniny and Pro ‘essing, Campbell Petroleum Sees, Val 1, Norman, Oks. 1 2 Walmintor, WC and Loe, Bl Apy ied Hydro tarbon Thermniynamsicy, Volt Gulf Pubs lishing Co, Houston, 1986. 3. Mall ER. and Yarborough, L thon of slate for Ztactor calc ons Fume 18, 197%, p. 2, 4 Soave, G.,“Egulum Constosts trom a ‘Mui Redhich Kwong quate of State,” \ new equa oc. (Chem Eng. Seis Vol. 22, 1972, 9. 5. Peng. D.¥und Robinson, D.B."'\ new to tomslant uation of sate” Ind. Png Chern Fundam. Vol 18,1976, p. 50 6.Hale TM and Aanaooh, GA. Molecular teed Study of Fluids, Advance~ in Chemis try Sens, Vol. 2, American Chemisal Soc fy, Washington D.C. 198% 7 Hinchleldees 10. Curton, CP and. Bird RB. Molecular Theory of Gates ind Liquids, John Wiley & Sons Inc. 1964, p-BSEI Mall. ed Thermdynam's Research Texan ARM University Stem, 1986 1. G.A., Mixing Rates tr Cuble Equa won uf State. Amencan ‘Chetnical ‘Socety Symposium Series 30), Pat IS, ashington Bee to, pp aN 10. Goodwin, B.D "The Thermoph sical Prop: eres of Methane from 0 to 50) K at Pres Stress 200 Ban," National Bur of Stan dlrds, NBS Tech, Note 53, Apo 1974 1, Godwin, RD” Rover. HIM and. Stay Ce. “Thermophysial Proper of Ethane trom 90 to a0 Kat Pressures 1 700 Bar National Bares of Standards, NBS. Tech Note 6, Angst 197% 12. Goodwin, RD and Haynes, WM. “Ther: ‘mophysical Properties of Propany from 88 to TK Kat Prestute 60-70 MP” Natonal Boreas of Standards, NBS Mon. graph pn 1982 I.MeCarty) RID. and Jacabsen, RT. “An Equation of State for Hand Ethvleve" Nation TRC. Thermodynamic Tt KR sl Barca of Standards, NBS Tox} Ste TOSS, july tos 4 Goadivin, RID, and Haynes, WM, "Ther ‘mophesical Properties of lobule from 114 TW Kat Droseutes by 30 MP. National Boreas vf Standards, NBS Tech Note IOS Famine 1982 15. Haves, WML. and Gaadwin, £D. °Thee rmopihvsical Properties Noval” Butane from 136 to 700 K at Presures 07 MPa, ational Bureau of Standards, 8S Mono raph 169, Apel 182, In Kimura, F., and Benson, GC, Faces Vol lumen of Binary Mixtures of 18 pane with Heaane lamers." } Chem: Eng. ‘Dats, Yl 2A pp. APM, ly 12,1980 #048 Gas Journal 17. Chevalier, LE, Petrino, Pl, 18. Qin. A. Hoffman, DE 19.Pun,S.. and Kohn, J TECHNOLOGY and Gaston: Bonhomme, YH, "Viscosity and Density of Some Aliphatic, Cyclic. and Aromatic Hydro- carbons Binary Liquid Mixtures"). Chem, | 21 Eng. Data, Vol 38.1990, pp. 206-12, ‘and Munk, P, “Ex ess Volume of Mintures of Alkanes ith ‘Aromatic Hydrocarbons,” J. Chem. Eng. Data, Vol. 37, 1992, pp. 61-45. Sold Liquid Vapor | 23, Equilibrium in the Methane-n-Eicosane and Ethanesn-Eicosane Binary Systeme," Chem: Eng. Data, Vol 15, 1970. pp. 572-74 Phase Behavior in the Methane-Propane Decane Systems.” J. Chem. Eng. Data, Va 15, 1970, pp. 7582 Doolittle, RK, "Speciic Volumes of Normal ‘Alkanes," J. Chem. & Eng, Data, Vol 9 1964, pp. 25-8, 22 Whiton CH, “Elfect of physical properties {estimation on equation of sate predicons, SPE], December 198, pp. 58556 Advances in Thermodynamics, Vol 1, LG. Chom and G.A. Mansoon, editors, "C;+ Fraction Characterization Taylor & Francis Publ Co, Bristol, Pa. 988 20, Wiese, HC, Reamer, Hi, and Sage, BH. Phase Equilibria in Hydrocarbon Systems Let's face it. Time is money. And lf your equipment isn’t working as hard or fast as it could be, you're losing ground. Kim Hotstart Oil Circulating Heating Systems offer many operational advantages. FOR ENGINES, oil temperature can be kept warm for easy starting and greatly reduced wear. 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