Grafo analiti~ka metoda odre ivawa rastvorqivosti, temperature kqu~awa i temperature kondenzacije u sistemu HCl H 2 O

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1 TERMOTEHNIKA, 01, XXXVIII,, Slavko N. \uri} Fakultet tehni~kih nauka, Univerzitet u Novom Sadu, Novi Sad, Srbija Grafo analiti~ka metoda odre ivawa rastvorqivosti, temperature kqu~awa i temperature kondenzacije u sistemu HCl H O Originalni nau~ni rad Uvod U radu su prikazani dijagrami koji omogu}avaju brzo re{avawe prakti~nih in`ewerskih problema kao {to su rastvorqivost HCl u vodi, kqu~awe i kondenzacija u sistemu HCl H O. Prou~ava se i uticaj zapreminskog udela HCl i vodene pare u dimnom gasu na temperaturu kondenzacije (ta~ku rose) u sistemu HCl H O N. Pri konstantnoj vrednosti udela vodene pare u dimnom gasu i pri zapreminskom udelu HCl od ppm povi{ewe temperature kondenzacijejesporije, dabi pri ve}imzapreminskimudelimahcl ovo povi- {ewe bilo zna~ajnije. Kqu~ne re~i: dimni gasovi, hlorovodoni~na kiselina, vodena para, temperatura kondenzacije Sve ve}a upotreba HCl u hemijskoj industriji i re{avawe prakti~nih in`ewerskih problema (rastvorqivost, kqu~awe, kondenzacija, koroziono pona{awe vla`nih dimnih gasova koji sadr`e HCl) iziskuje ta~no poznavawe fizi~ko-hemijskih i termodinami~kih osobina sistema HCl H O. Za razliku od drugih binarnih sistema gas voda, sistem HCl H O pokazuje neke posebnosti koje su pre svega prouzrokovane velikim afinitetom HCl prema vodi. Podaci (tabelarni, grafi~ki) iz literature [1 14] o sistemu HCl H O su prili~no op{irni, ali i nepotpuni. Neki autori u svojim radovima pri odre ivawu temperature kondenzacije u sistemu HCl H O citiraju jedna~inu []: ln pho ln phcl ln p T dp HO ln p (1) HCl gde su T dp [K] temperatura ta~ke rose, HCl; p HO [mmhg] parcijalni pritisak vodene pare u parnoj fazi sistema HCl H O; p HCl [mmhg] parcijalni pritisak HCl u parnoj fazi sistema HCl H O. Odgovorni autor; elektronska adresa: djuricns@uns.ac.rs

2 38 TERMOTEHNIKA, 01, XXXVIII,, Podaci koji su zna~ajni za in`ewersku praksu (kqu~awe, kondenzacija, koroziono pona{awe gasova koji sadr`e HCl nastalih sagorevawem ugqa, biomase i otpadnih materijala) kori{}ewem poznatih metoda zahtevaju dugotrajna prera~unavawa. U tom pogledu u radu su razvijeni dijagrami koji omogu}avaju brzo odre ivawe rastvorqivosti HCl u vodi, kqu~awa i temperature kondenzacije u sistemu HCl-H O i u sistemu HCl H O N. Grafi~ki prikaz odnosa pritisaka u parnoj fazi sistema HCl-H O Vrednost parcijalnih pritisaka HCl i H O u parnoj (gasovitoj) fazi sistema HCl H O u zavisnosti od masenog udela HCl u te~noj fazi sistema mogu se odrediti pomo}u izraza [11]: ( A B/ T) p ,[Pa] () gde su: T [K] temperatura me{avine A, B koeficijenti ~ije su vrednosti prikazane u tabl. 1. Tablica 1. Vrednost koeficijenata A i B () u zavisnosti od masenog udela HCl u te~noj fazi sistema HCl H O[11] Maseni udeo HCl u te~noj fazi sistema H O HCl HCl H O [%] A B A B Kori{}ewem jedn. () i kori{}ewem broj~anih vrednosti koeficijenata A i B prikazanih u tabl. 1 mogu se izra~unati parcijalni pritisci p = phcl ph O,i ukupan pritiska parne faze p = phcl ph O (sl. 1 i ). Dijagrami prikazani na sl. 3 i 4 dobijeni kori{}ewem jedn. () i dijagrama prikazanih na sl. 1 i omogu}avaju direktno o~itavawe za in`ewersku praksu potrebnih podataka kao {to su: rastvorqivost, kqu~awe i kondenzacija u sistemu HCl H O. Vrednost temperature kqu~awa, temperature kondenzacije i rastvorqivosti HCl u vodi po potrebi mora biti interpolirana. Za HCl > 34% parcijalni pritisak HCl je dosta vi{i od parcijalnog pritiska H O (sl. 3). Ovo se mo`e prikazati relacijom: lim p lim( p p ) p HCl HO HO HCl 100% HCl 100% (3)

3 TERMOTEHNIKA, 01, XXXVIII,, Slika 1. Zavisnost parcijalnog pritiska H O od temperature i masenog udela HCl u te~noj fazi sistema HCl H O Za HCl < 4% parcijalni pritisak HCl je dosta ni`i od parcijalnog pritiska H O (sl. 4). Ovo se mo`e prikazati relacijom: lim p lim( p p ) p HCl HO HO HCl 0% HCl 0% (4) Slika. Zavisnost parcijalnog pritiska HCl od temperature i masenog udela HCl u te~noj fazi sistema HCl H O

4 330 TERMOTEHNIKA, 01, XXXVIII,, Slika 3. Zavisnost ukupnog pritiska parne faze od parcijalnog pritiska HCl, temperature i masenog udela HCl u te~noj fazi sistema HCl H O Odre ivawe rastvorqivosti, temperature kqu~awa i temperature kondenzacije u sistemu HCl-H O Rastvorqivost, kqu~awe i kondenzacija realnih me{avina (vodeni rastvori) mogu se odrediti primenom slede}ih stavova (sl. 3i4). Stav 1. Rastvorqivost HCl u vodi odre uje se na preseku linije (pravca) ukupnog pritiska i linije temperature u sistemu HCl H O. Na primer, rastvorqivost HCl u vodi pri pritisku od Pa i50 C prema stavu 1 i sl. 4 iznosi: 5 p t Pa 50 C 399.% Slika 4. Zavisnost ukupnog pritiska parne faze od parcijalnog pritiska H O, temperature i masenog udela HCl u te~noj fazi sistema HCl H O

5 TERMOTEHNIKA, 01, XXXVIII,, Stav. Temperatura kqu~awa vodenog rastvora HCl H O odre uje se na preseku linije (pravca) ukupnog pritiska parne faze p = phcl ph O iznad rastvora i linije masenog udela HCl ili linije masenog udela H O u te~noj fazi rastvora. Na primer, neka je u te~noj fazi sistema HCl H O maseni udeo HCl = 14% a ukupan pritisak parne faze iznad rastvora p = Pa. Prema navedenom stavu interpolacijom se dobija da temperatura kqu~awa vodenog rastvora HCl H O iznosi 104 C (sl. 3). Ovo se mo`e napisati pomo}u izraza: 5 p HCl Pa 14% 104 C Stav 3. Temperatura kondenzacije u sistemu HCl H O odre uje se na preseku linije (pravca) ukupnog pritiska parne faze p = phcl ph O i linije (pravca) parcijalnog pritiska p HCl ili p HO. Na primer, neka je u parnoj fazi sistema HCl H O ukupan pritisak p = Pa, a parcijalni pritisak p HO = Pa. Prema navedenom stavu temperatura kondenzacije u sistemu HCl H O iznosi 4 C (sl. 4), ili pomo}u izraza: 5 p pho Pa Pa 4 C Primena dijagrama prikazanim na sl. 3 i 4 mo`e da se pro{iri i na odre ivawe temperature kondenzacije u sistemu HCl H O N (inertan gas). p p p p HCl H O N,[ Pa] (5) ukupan pritisak u parnoj fazi sistema HCl-H O-N gde je p N [Pa] parcijalni pritisak azota (inertnog gasa) u parnoj fazi. Parcijalni pritisci komponenata u parnoj fazi su: gde su y HCl, y Neka je: i y HO N Neka je: phcl yhcl p, Pa (6) p y p,[ Pa] (7) HO HO p y p,[ Pa] (8) N N molski udeli HCl, H O i N u parnoj fazi, [kmol/kmol]. p0 phcl ph O,[ Pa] (9) zbir parcijalnih pritisaka HCl i H O. Prema stavu 3 temperatura kondenzacije u sistemu HCl H O N odre uje se na preseku linije (pravca) pritiska i pravca parcijalnog pritiska phcl ili pravca parcijalnog pritiska (sl. 3i4)ilipomo}u izraza: p0 phcl t, (10) p0 pho t. (11) Na primer, neka su u parnoj fazi sistema HCl H O N zapreminski udeli j HCl 10% i j HO 10% i neka je ukupan pritisak parne faze p = Pa. Parcijalni pritisci komponenata u parnoj fazi su: 5 4 phcl yhcl p Pa, 5 4 pho yhop Pa, 5 p y p ( 1 y y ) p ( ) Pa N N HCl H O

6 33 TERMOTEHNIKA, 01, XXXVIII,, iznosi: Zbir parcijalnih pritisaka HCl i H O iznosi: p0 phcl ph O Pa Prema izrazu (10) temperatura kondenzacije u sistemu HCl H O N (sl. 3) p phcl Pa Pa 64 C Do istog rezultata se dolazi kori{}ewem izraza (11) i sl. 4: p pho Pa Pa 64 C. Prema ovom postupku odre uju se vrednosti kondenzacije (ta~ka rose) u sistemu HCl H O N i za druge vrednosti zapreminskih udela HCl i vodene pare u parnoj fazi sistema (sl. 5). Slika 5. Zavisnost temperature kondenzacije u sistemu HCl H O N od zapreminskog udela HCl i vodene pare pri konstantnom pritisku od Pa Komparacija rezultata Rastvorqivost, temperatura kqu~awa i temperatura kondenzacije me{avina HCl H O i HCl H O N dobijena primenom dijagrama (sl. 3, 4 i 5) testirana je pore- ewem rezultata drugih istra`iva~a (tabl. ). Rezultati dobijeni primenom dijagrama prikazanih u ovom radu dobro se sla`u sa podacima iz literature [, 1 14]. Zakqu~ak Dijagrami prikazani u ovom radu omogu}avaju brzo re{avawe prakti~nih in`ewerskih problema kao {to su: rastvorqivost, kqu~awe, kondenzacija i korozivno pona{awe vla`nih dimnih gasova koji sadr`e HCl. Pokuzuje se uticaj zapreminskog udela HCl i vodene pare u dimnom gasu na temperaturu kondenzacije u

7 TERMOTEHNIKA, 01, XXXVIII,, Tablica. Komparacija rezultata temperature kondenzacije u sistemu HCl H O i HCl H O N kori{}ewem dijagrama prikazanih u radu sa podacima iz literature Parcijalni pritisci komponenata u parnoj fazi [Pa] Ukupan pritisak parne faze [Pa] p HO p HCl p N p Primena dijagrama prikazanih na sl. 3, 4 i 5 Ta~ka rose [ C] Literatura [1 14] Ta~ka rose [ C] Jedna~ina (1) Literatura [] Ta~ka rose [ C] 1333, , ,0 0166, sistemu HCl H O i u sistemu HCl H O N. Pokazano je da je pri konstantnoj vrednosti udela vodene pare u dimnom gasu i pri zapreminskom udelu HCl od ppm povi{ewe temperature kondenzacije sporije, da bi pri ve}im zapreminskim udelima HCl ovo povi{ewe bilo zna~ajnije. Rezultati prora~una rastvorqivosti, temperature kqu~awa i temperature kondenzacije u sistemu HCl H O i u sistemu HCl H O N u skladu su sa rezultatima drugih istra`iva~a i merewa u praksi i mogu predstavqati polaznu osnovu u fazi projektovawa i dizajnirawa postrojewa za sagorevawe biomase i drugih otpadnih materijala koji sadr`e HCl. Oznake p pritisak, [Pa] p HCl parcijalni pritisak HCl u parnoj fazi, [Pa] p H parcijalni pritisak vodene pare, [Pa] O p N parcijalni pritisak azota (inertnog gasa) u parnoj fazi, [Pa] T dp temperatura ta~ke rose, [K] t temperaura, [ºC] HCl zapreminski udeo HCl u parnoj fazi, [ppm] HCl maseni udeo HCl u te~noj fazi, [%] H O zapreminski udeo H O u parnoj fazi, [%] y HCl molski udeo HCl u parnoj fazi, [kmolkmol 1 ] y molski udeo vodene pare u parnoj fazi, H O [kmolkmol 1 ] y N molski udeo N u parnoj fazi, [kmolkmol 1 ] Literatura [1] Verhoff, F. H., Banchero, J. T., Predicting Dew Points of Flue Gases, Chem. Eng. Prog., 78 (1974), 8, 71-7 [] Kiang, Y-H., Predicting Dew Points of Acid Gases, Chem. Eng., 88 (1981), 3, 17 [3] Perry, R. H., Chilton, C. H., Chemical Engineers Handbook, 5 th ed., McGraw- Hill, New Jork, USA, 1973

8 334 TERMOTEHNIKA, 01, XXXVIII,, [4] Weast, R. C., Handbook of Chemistry and Physics, 69 th ed., CRC Press, Boca Raton, Fla., USA, Inc. pg B67, 1988 [5] Land, E., The Theory of Acid Deposition and its Application to the Dew Point Meter, Journal of the Institute of Fuel, (1977), [6] Pierce, R. R., Estimating Acid Dewpoints in Stack Gases, Chem. Eng., 84 (1977), 8, [7] Massuci, M., Clegg, S. L., Brimblecombe, P., Equilibrium Partial Pressures, Thermodynamics Properties of Aqueous and solid Phase, and C1 Produstion from Aqueous HCl and HNO 3 and Their Mixtures, J. Phys. Chem., 103 (1999), 1, [8] Kao, J. T. F., Vapor-Liquid Equilibrium of Water-Hydrogen Chloride Systems, J. Che. Eng. Data, 15 (1970), 3, [9] Fritz, J. J., Fuget, C. R., Vapor Pressure of Aqueous Hydrogen Chloride Solurions, 0 to 50 C, Ind. Eng.Chem., 1 (1956), 1,10-1 [10] Huijbregts, W. M. M., Leferink, R., Latest Advances in the Understanding of Acid Dew Point Corrosion: Corrosion and Stress Corrosion Cracking in Combustion Gas Condensates, Anti-Corrosion Methods and Materials, 51 (004), 3, [11] ***, Chemical Engineers Handbook (Eds.R. H., Perry, C. H. Chilton), 7 th ed., McGraww- -Hill, New York, USA, 1997 [1] Schmidt, A., Uber Das System Chlorwasserstoff/Waser, Chem. Ing. Techn., 5 (1953), 8/9, [13] ***, Verien Deutsche Ingenieure (VDI 3451), Anlagen, zur Herstellung und Verarbeitung von Chlorwasserstoff, Dusseldorf, Germany, 1979, 4-1 [14] Magasiner, N., Backend Corrosion in Bagase-Coal Fired Boilers with Particular Reference o Co-Generation, Proc S Afr Sug Technol Ass, 010 (010), 83, 4-443

9 TERMOTEHNIKA, 01, XXXVIII,, Abstract Grapho-Analytical Method for Determining Solubility, Boiling Point and Dew Point Temperature in the System HCl-H O by Slavko N. DJURI] Faculty of Technical Sciences, University of Novi Sad, Novi Sad, Serbia In this paper i have shown diagrams which enable quick solution to practical engineering problems like solubility of HCl in water, boiling, and dew point temperature in the system HCl-H O. I have also investigated the influence of volume fraction of HCl and water vapour in flue gas to the condensation temperature (dew point) in the system HCl-H O-N. At constant value of water vapour fraction in flue gas and at volume fraction HCl of ppm, the increase in dew point temperature is slower, whereas with bigger volume fractions of HCl this increse would be more significant. Key words: flue gases, hydrochloric acid, water vapour, dew point temperature Corresponding author; djuricns@uns.ac.rs Rad primqen: 7. februara 013. Rad revidiran: 8. marta 013. Rad prihva}en: 5. marta 013.

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