UNIFAC. Documentation. DDBSP Dortmund Data Bank Software Package
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1 UNIFAC Docuetato DDBSP Dortud Data Ba Software Pacage DDBST Dortud Data Ba Software & Separato Techology GbH Mare-Cure-Straße 10 D Oldeburg Tel.: Fax: support@ddbst.co
2 DDBSP- Dortud Data Ba Software Pacage Itroducto Tutoral Buldg a Syste Checg Paraeter Avalablty Calculato Isotheral Calculato over a Cocetrato Rage Calculato at Costat Copostos over a Teperature Rage Result Grd Actvty Coeffcet Dagra The Meus Appedx UNIFAC UNIFAC Page 2 of 13
3 DDBSP- Dortud Data Ba Software Pacage Itroducto Ths software allows calculatg actvty coeffcets, heats of xg ad excess heat capacty by the actvty coeffcet odels UNIFAC 1 ad odfed UNIFAC (Dortud) 2 for xtures wth up to ffty copoets. If the LLE exteso lcese s avalable t s also possble to calculate the lqud-lqud equlbru for bary ad terary systes. The software s a tegral part of the Dortud Data Ba software pacage ad uses the copoet, the group assget ad other tools fro ths pacage. The pacage therefore cludes 1. the a calculato progra (descrbed here) 2. a copoet selecto tool (descrbed CopoetMaageet.pdf ) 3. a copoet edtg tool (descrbed CopoetMaageet.pdf ) 4. a UNIFAC teracto paraeter edtor (descrbed GC Model Paraeters.pdf ) 5. a DDB cofgurato edtg tool (descrbed DDBCofgurato.pdf ) The software coes wth a lst of ore tha copoets fro the a DDB copoet lst ad approx of the have a UNIFAC group assget ad about have a group assget for odfed UNIFAC (Dortud). For ost copoets the DDB provdes CAS regstry ubers (24250), eprcal forula olecular weghts (alost all). All other copoets are applcable both ethods (e. g. salts, etals ad etal coplexes, etc.). The latest UNIFAC paraeters have bee publshed , the latest paraeter for od. UNIFAC (Dortud) have bee publshed , ad 2011 (oc lquds) 6. Most curret paraeters ca be obtaed fro the UNIFAC Cosortu. 1.1 Tutoral Ths tutoral shows all fuctos sde the a calculato software. Addtoal PDFs are avalable for edtg, addg, ad searchg copoets, as well as for odfyg/uderstadg the DDB cofgurato, ad the teracto paraeter edtor. 1 Fredeslud A., Joes R.L., Praustz J.M., Group-Cotrbuto Estato of Actvty Coeffcets Nodeal Lqud Mxtures, AIChE J., 21(6), , Wedlch U., Gehlg J., A Modfed UNIFAC Model. 1. Predcto of VLE, he, ad γ, Id. Eg. Che. Res., 26(7), , Wttg R., Loha J., Gehlg J., Vapor-Lqud Equlbra by UNIFAC Group Cotrbuto. 6. Revso ad Exteso, Id. Eg. Che. Res., 42(1), , Gehlg J., Wttg R., Loha J., Joh R., A Modfed UNIFAC (Dortud) Model. 4. Revso ad Exteso, Id. Eg. Che. Res., 41(6), , Jaob A., Gresea H., Loha J., Gehlg J., Further Developet of Modfed UNIFAC (Dortud): Revso ad Exteso 5, Id. Eg. Che. Res., 45(23), , Nebg S., Gehlg J., Predcto of phase equlbra ad excess propertes for systes wth oc lquds usg odfed UNIFAC: Typcal results ad preset status of the odfed UNIFAC atrx for oc lquds, Flud Phase Equlb., 302(1-2), , 2011 UNIFAC Page 3 of 13
4 DDBSP- Dortud Data Ba Software Pacage Buldg a Syste Fgure 1: UNIFAC graphcal user terface. A syste cotas several pure copoets. Copoets ca be added by the Add Copoet butto. It calls the stadard DDB copoet selecto pacage whch s descrbed detals a separate PDF ( Copoet Maageet, Chapter 9). The dalog allows searchg for aes, forulas, CAS regstry ubers ad ay ore crtera. Fgure 2: Copoet selecto UNIFAC Page 4 of 13
5 DDBSP- Dortud Data Ba Software Pacage 2015 The copoet lst show s the coplete lst of copoets avalable the Dortud Data Ba. It cludes also ay copoets for whch o group assgets are avalable. After a copoet has bee selected, t s added to the copoet lst. Fgure 3: Copoet lst Ths lst dsplays the DDB teral uber, a Eglsh ae, the eprcal forula, the olecular weght, ad both the group assgets for UNIFAC ad odfed UNIFAC (Dortud). If a group assget s ot gve, a.a. s wrtte. Sgle copoets ca be reoved by double-clcg the le; the coplete lst ca be cleared by clcg the Reove All butto. The syste table has a cotext eu whch allows 1. Reove all copoets 2. Reove the selected copoet 3. Copyg, prtg, ad savg the copoet lst 4. Auto-sze the colus of the table 5. Dsplay detals of the group assget Fgure 4: Group assget detals. The oral dsplay the copoet lst oly dsplays the sub groups of the copoets ad ths dalog adds forato about the a groups. UNIFAC Page 5 of 13
6 DDBSP- Dortud Data Ba Software Pacage Checg Paraeter Avalablty UNIFAC eeds the copoet specfc group assget ad teracto paraeters betwee all a groups preset the curret xture. The dalog has two pages. The frst page oly dsplays f all paraeters are avalable. Fgure 5: Paraeter avalablty The secod page gves detals about the group assget for all copoets ad all a group teractos. The exaple shows that for the gve syste UNIFAC ca be used but odfed UNIFAC (Dortud) wll fal because of a ssg teracto paraeter. UNIFAC Page 6 of 13
7 DDBSP- Dortud Data Ba Software Pacage 2015 UNIFAC Copoet Copoet Copoet Copoet 11: Ethaol Subgroups: 1 (CH3 ) 2 (CH2 ) 14 (OH ) 12: Dethyl ether Subgroups: 1 (CH3 ) 2 (CH2 ) 25 (OCH2 ) 17: Ale Subgroups: 9 (ACH ) 36 (ACNH2 ) 15: Forc acd Subgroups: 43 (HCOOH ) Lst of Ma Groups Magroups: 1 (CH2 ) 3 (ACH ) 5 (OH ) 13 (CH2O ) 17 (ACNH2 ) 20 (COOH ) Iteracto paraeters 1-3: 1 paraeter/s 1-5: 1 paraeter/s 1-13: 1 paraeter/s 1-17: 1 paraeter/s 1-20: 1 paraeter/s 3-5: 1 paraeter/s 3-13: 1 paraeter/s 3-17: 1 paraeter/s 3-20: 1 paraeter/s 5-13: 1 paraeter/s 5-17: 1 paraeter/s 5-20: 1 paraeter/s 13-17: 1 paraeter/s 13-20: 1 paraeter/s 17-20: 1 paraeter/s Syste has all paraeters avalable. od. UNIFAC (Dortud) Copoet Copoet Copoet Copoet 11: Ethaol Subgroups: 1 (CH3 ) 2 (CH2 ) 14 (OH (P) ) 12: Dethyl ether Subgroups: 2 (CH2 ) 1 (CH3 ) 25 (OCH2 ) 17: Ale Subgroups: 9 (ACH ) 36 (ACNH2 ) 15: Forc acd Subgroups: 43 (HCOOH ) Lst of Ma Groups Magroups: 1 (CH2) 3 (ACH) 5 (OH) 13 (CH2O) 17 (ACNH2) 44 (HCOOH) Iteracto paraeters 1-3: 2 paraeter/s 1-5: 3 paraeter/s 1-13: 2 paraeter/s 1-17: 3 paraeter/s 1-44: 1 paraeter/s 3-5: 3 paraeter/s 3-13: 2 paraeter/s 3-17: 3 paraeter/s 3-44: 3 paraeter/s 5-13: 3 paraeter/s 5-17: 3 paraeter/s 5-44: 0 paraeter/s 13-17: 2 paraeter/s 13-44: 1 paraeter/s 17-44: 0 paraeter/s Paraeters are ssg. UNIFAC Page 7 of 13
8 DDBSP- Dortud Data Ba Software Pacage Calculato Fgure 6: Calculato settgs Isotheral Calculato over a Cocetrato Rage Fgure 7: Calculate at costat teperature. For a costat teperature t s possble to eter copostos aually or let the progra calculate soe auto-dstrbuted coposto pots. The Set Copostos butto opes a dalog where copostos ca be created ( Create Data Pots ). I ths dalog t s possble to eter copostos drectly the data grd ad t allows creatg data pots over a coposto rage. Specal case le costat copostos or coposto ratos for sgle or few copoets are also supported. The coposto grd ca be coped to the Wdows clpboard as well as data ca be pasted fro the clpboard. Ths allows creatg ad aagg copostos outsde ths progra. Copostos ca also be saved to ad restored fro fles. Fgure 8: Coposto settgs UNIFAC Page 8 of 13
9 DDBSP- Dortud Data Ba Software Pacage 2015 The uber of possble data pots s lted to Specal copostos ca be costat copostos for sgle copoets or specal coposto ratos (specfed by teger values le 4 ad 5 four a 4 / 5 rato) for a lst of copoets. Fgure 9: Specal copostos Calculato at Costat Copostos over a Teperature Rage Fgure 10: Calculato settg for costat copostos. Ths calculato type allows the specfcato of a sgle coposto le ad a teperature rage. The coposto ca be etered as ole fractos ad as weght fractos. 1.2 Result Grd Fgure 11: Result grd The result grd shows all gve copostos ad the wated teperatures frst followed by the calculated actvty coeffcets, the heat of xg ad the excess heat capacty. UNIFAC Page 9 of 13
10 DDBSP- Dortud Data Ba Software Pacage 2015 Fgure 12: Result grd wth LLE Calculato If the LLE calculato s actve the tal cocetratos are treated as feed. The result grd wll the be exteded by two phase colus for each copoet ad two actvty coeffcet/he/cpe colus for the secod phase. The addtoal colus wll be preset eve f o LLE was foud. The table ca be saved as Mcrosoft Excel ( xls ) fle or coped to the Wdows clpboard. 1.3 Actvty Coeffcet Dagra I case of the calculato at a fxed sgle coposto at dfferet teperatures a dagra wth the teperature-depedet actvty coeffcets s dsplayed. Fgure 10: Teperature depedet actvty coeffcets. 1.4 The Meus UNIFAC Page 10 of 13
11 DDBSP- Dortud Data Ba Software Pacage 2015 Copoet lsts are fles cotag raw data set ubers. These fle have the exteso stl. The syste grd ca also be saved as a coa separated fle whch ca be loaded spread sheet progras. The syste grd (copoet lst) ca be coped ad prted. Copoets starts the Copoet Edtor (descrbed CopoetMaageet.pdf ) Show Hts actvates addtoal hts for ay tes o the for. Iteracto Paraeter Matrx starts the paraeter edtor (descrbed GC Model Paraeters.pdf ) DDB Cofgurato starts the cofgurato progra (descrbed DDBCofgurato.pdf ) UNIFAC Page 11 of 13
12 DDBSP- Dortud Data Ba Software Pacage Appedx 2.1 UNIFAC The UNIFAC group cotrbuto odel 7 has bee developed to estate the real vapor-lqud equlbru behavor. I a group cotrbuto odel the xture s ot see as a xture of copoets but as a xture of groups. The large advatage s that the uber of structural groups s uch saller (dozes) tha the uber of copoets (llos). Ths eas that t s possble to calculate ost systes of coercal terest wth very few group forato. UNIFAC s based o the UNIQUAC equato. Therefore actvty coeffcets are calculated fro two ters, l l C R l The cobatoral part s calculated the sae aer as UNIQUAC,. wth l C 1V lv V 5q 1 F V l F V r r x ad F q q x. For the calculato of the cobatoral part oly the relatve va der Waals volue r ad surface q together wth the ole fractos x are eeded. The va der Waals volue ad surface ca be calculated fro group volues ad surfaces, () ( ) r R ( ) q Q wth as the uber of structural groups of type the olecule. The resdual part has to be calculated fro the group actvty coeffcets, R ( l ) l l The cocetrato depedecy of the group actvty coeffcets the xture (ad the pure copoet () ) ust be calculated aalogy to the UNIQUAC equato, ( ). 7 Gehlg J.,Kolbe B., Therodya, Verlag Chee, Wehe (1987) UNIFAC Page 12 of 13
13 DDBSP- Dortud Data Ba Software Pacage 2015 UNIFAC Page 13 of 13 Q l 1 l. The surface cotrbuto ad the ole fracto X of the group s defed by X Q X Q x x X, ad the paraeter s defed as T a e wth a as group teracto paraeters betwee the groups ad. Modfed UNIFAC (Dortud) uses teperature-depedet teracto paraeters: T T c T T b T a e 2
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