PETROVIETNAM Can bang pha he cac loai con hydrocarbon Lfng dung du" doan kha nang tach pha long long va ap suat hdi Reid cua hon hap nhien lieu xang bio fuels TS Nguyen Huynh Dong Ths Tran Thj Kim Sie[.]
PETROVIETNAM Can bang pha he cac loai - hydrocarbon: Lfng dung du" doan kha nang tach pha long - long va ap suat hdi Reid cua hon hap nhien lieu xang bio-fuels TS Nguyen Huynh Dong Ths Tran Thj Kim Siem TrUdng Cao ddng nghe Ddu KS Nguyen Huynh Duong Tong cdng ty Khi Viet Nam Tom tat Dat van de Xu hddng san xudt cdc loai nhien lieu saeh (bioCac loai cdn hien dang duqc sUdung nhu la eau tirde fuels) cho dpng cp dot hien thudng si? dung phdi trdn xang khdng ehi [1-3], khdng ehi vi chiing cd chi eon (cdc loai con) hode ete nhtt mpt cdu tCtpha trpn [1, sd de tan cao ma sU cd mat ciia cdn nhien lieu cdn 2] Do do, cdc tinh chdt nhiet dpng hpe, dgc biet Id cdn cai thien qua trinh chay va giam dang ke chat thai CO va bdng pha cua cdc hdn hpp ndy rdt quan trpng eae oxit nito ddi vdi nhien lieu xang [4, 5] cung nhU thiet ke, md phong, toi Uu cdc qud trinh sdn xudt xang nhien lieu diesel [6, 7] Tuy nhien, viec md phdng va dU + cdc loai hope diesel, ethanol Trong bdi bdo ndy, doan can bang pha he chUa cdn va hydrocarbon dupe ehung tdi sit dung md hinh nhiet dpng Perturbed Chain xem la cUc ky khdng ly tUdng Can bang pha anh Statistical Associating Fluid Theory de md phdng cdn hudng den qua trinh san xua't, tdn chUa, phan phdi va sU bdng pha long-hoti (VLE) vd long-long (LLE) cua he dung nhien lieu ed pha trpn edn sinh hpc Trong cac qua methanol/ethanol/isopropanol + hydrocarbon ddpc trinh thiet ke edng nghe - san xua't - phdi trdn - tdn trU va xem Id rdt khong ly titdng, cdc tUotng tdc phitc tap sU dung nhien lieu cd pha trdn edn sinh hpc [8-10], viec (lien ket hydro vd phdn cite) ed he Kit qud md md phdng chinh xac eae tinh chat nhiet ddng he chUa edn phong ndy ditpc sit dung dedUdodn khd ndng tdeh pha -I- hydrocarbon la eUc ky quan trpng Mae dii cac phuong long-long vd dU dodn dp sudt hai Reid ciia xang biotrinh nhiet ddng Cubic hoac cac md hinh hoat dip Gibbs fuels Chung tdi dd tdi du cdc thdng sdmdi cho cdc loai thudng duqc sU dung edng nghiep dau nhUng tinh khiet, sit dung cho phdctng trinh PC-SAFT cac md hinh khdng the md ta chinh xac can bang pha Trong tdt ca cdc trddng hpp dupe xem xet, mo hinh eiia cac hon hpp ed lien ke't hydro hoac phan cUc Trong nhiet dpng PC-SAFT eho kit qud md phdng tdt han hoan eanh dd, su ddi ciia phuang trinh nhiet ddng ddng ki'so vdi cdc md hinh nhiet dpng dupe Ua chudng thdng ke PC-SAFT [11] eho phep md phdng theo xu sit dung cdng nghi ddu vd khi, nhU cdc phUang hudng dU doan chinh xac tinh chat nhiet ddng ciia cac trinh nhiet dpng Cubic hope md hinh hoat dp (Gibbs), hon hop phUe tap ke ea he cd lien ke't hydro va phan eUc dgc biet Id kit qud md phdng cdn bdng pha long-long Trong thdi gian gan day, nhieu tac gia da ap dung Vdi gia thiet dan gidn dupe sit dung de md phong hon edng phuang trinh nhiet ddng PC-SAFT de md hpp da cdu tit, dp sudt hai Reid ciia hon hpp nhiin lieu phdng can bang pha he khdng ly tUdng, dac biet, md hinh xang + cdc loai dupe dUdodn sit dung phUang trinh PC-SAFT Trong tdt cd cdc trUdng hpp dupe xem xet, PC- nhiet ddng GC-PC-SAFT de nghj bdi Tamouza [12] va sau dddupe Nguyen Huynh etal [13,14] mdrdng edng SAFT cho kit qud dU dodn vdi sai sd tuang ddi ® PC-SAFT 2,E-t04 0,2 0,4 ^ ^0,6 , X, y Ethanol 0,f Ethanol -F benzene (g) ,E-^04 0,0 0,2 0,4 06 X, y Iso-octane 0,8 1,0 Iso-propanol -F iso-octane (h) 0,2 0,4 06 0,E X, y Iso-propanol Iso-propanol -F benzene (i) Hinh Cdn bang pha Idng-hai he cdn -F hydrocarbon So lieu thi/c nghiem cua tdng hon hgp dugc lay td: (a) [38]; (b) [39]; (c) [40]; (d) [41]; (e) [42]; (f) [43]; (g) [44]; (h) [45]; (i) [46] Cd hai phuang phap de so sanh ke't qua md phdng can bang pha VLE va LLE vdi cae md hinh nhiet ddng dUpc Ua chudng sU dung hien nay: (i) gia djnh he sd tuong tac ?i de ed the md ta diing ban chat can b3ng pha ciia hon hop (vd: diem dang phi ciia hdn hpp ethanol -F hexane) 3.2.2 Can bang pha long-long (LLE) hon hpp k|j bang gia trj zero (mo phdng dU doan) hoac (ii) toi Uu gia trj ky sU dung dU lieu thuc nghiem ciia hdn hop Can bang pha LLE dUpc xem la rat khd md ta bang cac Vdi gia tri ky = 0, PC-SAFT dU doan diing dac tinh dang phi phuong trinh nhiet ddng Ket qua md phdng bai ciia hau bet cac hdn hpp dang dupe xem xet, dieu bao dUoc so sanh vdi ket qua md phdng thu duqc chUng td dUpe kha nang dU doan cae tinh chat nhiet ddng bang cac md hinh nhiet ddng khac hien cd ciia cac he khdng ly tUdng va chi can sU dung cac thdng sd cac phan mem chuyen dung hoac tU cac cdng trinh cua eau tUtinh khiet.Trong dd, cae md hinh nhiet dpng CO dien lai yeu eau sU dung thdng sd tuang tac hon hpp k,j nghien cUu dupe dang tai tren cac tap chi ed uy tin Hinh 2(a) md ta can bSng pha LLE he methanol -F DAU KHi - S O / 1 45 HOA - CHf BifN DAU Khf pentane, ket qua md phdng dupe so sanh vdi ket ciia thu Hinh 2(d) md ta can bang pha LLE he ethanol -F dupc bdi Yarrison va Chapman [24], PC-SAT eho ket qua n-dodeeane sir dung hai he thdng so cau tir tinh khiet tdt han CK-SAFT so vdi sd lieu thUe nghiem.Tuong tU, ke't khac cho ethanol Ket qua mo phdng eho tha'y, cac qua md phdng can bang pha LLE he methanol -i- octane thdng sd mdi sir dung eho ethanol tinh khiet cho ket qua eiia Karakatsani et al [25] sU dung phuang trinh t-PPC- md phdng rat chinh xac gian pha LLE ciia he dang xet SAFT khdng cho ke't qua tdt han PC-SAFT dii Karakatsani va ca ddi vdi cac hon hpp ethanol -i- alkane khac, et al cd tinh de'n cac tUong tac phan eUc, dieu cd the dieu cho phep ke't luan rang, thong so mdi xac djnh giai thich thdng qua sU chpn lua khdng thda dang cac bai bao eho ke't qua md phdng tdt han cac thdng so cau tU tinh khiet ap dung eho CK-SAFT hoac t- thdng sd Gross va Sadowski [20] cdng bd PPC-SAFT Ket Ke't qua md phdng can bang pha LLE sUdung PC-SAFT qua md phdng LLE eiia cac hon hpp methanol/ethanol -i- hydrocarbon thu dupe bai bao tuang duang vdi ke't qua thu dupe bdi Aral et al [21 ] vdi md cung dupe so sanh vdi cac md hinh nhiet dpng dang hinh nhiet dpng "Modified Wilson" hay Matsuda va Ochi dupe Ua chudng sir dung nhU Peng-Robinson [37], Soave- [23] sU dung md hinh NRTL, nhien, cae nhdm nghien Redlich-Kwong [47], UNIFAC LLE [48] Trong da so cac eUu de nghi thay doi cac phuang trinh ndi tren mdt trudng hpp, cac md hinh nhiet dpng co dien khdng the each dae biet va phii hpp de md phdng can bang pha LLE md ta ehinh xac LLE ciia he methanol/ethanol -i- he methanol -¥ alkane, han nUa, hp sUdung he sd tuang tac bydrocarbon, ea doi vdi UNIFAC LLE [48], la md hinh hon hpp kjj phu thupc vao nhiet dp, dieu han ehe kha nhiet dpng dupe phat trien dac biet cho md phong can nang ngoai suy ciia md hinh va ke't qua chi diing vdi bang pha LLE khoang nhiet dp ma he sd ky da dupe hieu chinh 345 296 305 335 i 291 5-295 286 285 281 315 bar - PC-SAFT SRK kij = 0,04 UNIFAC LLE 275 276 305 295 +! 265 0,2 04 0,6 X, y Methanol 0,f Methanol -F pentane (a) 0,0 0,2 04 0,6 0,8 X, y Methanol 0,0 1,0 Methanol -F hexane (b) 324 319 314 309 304 299294 ?89 X, y Ethanol Ethanol -F dodecane (d) Ethanol -F n-tetradecane (e) 1,0 04 0,6 0,8 X, y Methanol Methanol -F octane (c) 329 - Gross va Sadowski - PC-SAFT 0,2 - — UNIFAC-LLE / rtffS^^ PC-SAFT * g i ^ = * * ' ^ ftk ^1 %\ A/ /&, ]i ' I 0,40 0,60 X, y Ethanol Ethanol -F n-hexadecane (f) Hinh Cdn bang pha long-long he con-^ hydrocarbon So lieu thi/c nghiem lay ti/: (a) [49]; (b) [50]; (c) [51]; (d) [52]; (e) [52]; [23, 52, 53] Ket qud md phdng vdi PC-SAFT dugc so sdnh vdi ket qud thu dugc sd dung cdc mdhinh nhiet dgng dang dugc U dung cdc phdn mem cdng nghe nhUSRK[47]; UNIFAC-LLE [48] 1^ 46 DAU KHi - s o4/201 PETROVIETNAM Nhu vay, ehiing tdi ed the ke't luan rang, eae t h d n g sd nhdm tac gia Hatzioannidis et al [55] sU dung m d hinh eau tir tinh khiet mdi duqc xac djnh cho eae loai cdn nhiet ddng UNIFAC de hieu ehinh ap suat hai Reid ciia bai bao eho ke't qua t d t hon cac t h d n g sd dupe edng hdn hop xang, nhdm tac gia cung da ket luan, UNIFAC bd bdi cae nhdm tac gia khac va cac m d hinh nhiet dpng khdng the sU dung de dU doan ehi tieu chat lupng CO dien, ne'u cac m d hinh khdng tinh chi tiet cae lUe ciia hdn hop xang - cac loai cdn vi sai sd so vdi sd lieu thUc tuang tac lien ket hydro gay thi khdng the md ta nghiem la tUOng ddi Idn, nhdm tac gia eung dUa bien chinh xac can bang pha LLE eiia he eae loai cdn -F luan UNIFAC khdng tinh den cac tUOng tac lien ket hydroearbon, n h u cac p h u a n g trinh nhiet ddng dang hydro gay Pumphrey et al [56] da sUdung eae m d hinh Cubic hoac m d hinh boat dp (Gibbs) nhiet ddng Margules [57]; VanLaar [58]; Wilson [59] de m d phdng va d u doan ap suat hoi Reid ciia hdn hop xang Ket qua m d phdng can bang pha LLE ciia he cac loai cdn -F hydrocarbon thu dUpc bai bao dang khdng ehi -F cac loai cdn, nhdm tac gia da gia thiet xem hon hop xang khdng ehi -F cac loai cdn nhU la hdn hpp dupe ap dung m d rdng de m d phdng d u doan hien tupng ciia hai eau tU gia, cac thdng sd ciia m d hinh nhiet ddng tach pha eiia he xang reformat - cae loai cdn - nude, ket duqc xac djnh thdng qua mdt sd diem ap suat thpc qua se dupc Ung d u n g de dU doan kha nang tach nghiem dupe ciia hon hop, vdi gia thiet n h d m tac pha giOa cac hpp chat cd tinh chat khae n h u cac gia da ket luan, ehi ed m d hinh Wilson cho ket qua m d loai edn - hydrocarbon cd xang (dU doan nhiet dp, phdng vdi ke't qua dang tin cay vi m d hinh cho phep ap suat va phan ciia cac phdi lieu phdi trdn xang md phdng cac he rat khdng ly tUdng Hinh & so sanh ma tai dd ed hien tUpng tach pha), hien t u p n g tach pha ket qua m d phdng sU dung m d hinh Wilson va PC-SAFT, ciia nhien lieu xang bio-cac loai cdn anh hudng de'n cac chiing ta cd the thay Wilson cho ket qiia m d phdng chinh tinh chat ciia xang t h u a n g pham n h u chi sd octane, ap xac tai diem 100% methanol/iso-propanol vi eae t h d n g sd suat hai va mUc dp lan nUdc vao san pham qua ciia cau tU gia (dac trUng cho hdn hpp xang khdng chi trinh tdn chUa, dac biet la trudng hpp cae loai edn cd chUa cdn) sU dung md hinh Wilson dUpe tdi Uu dupc trpn vao xang bio-fuels vdi ham lUpng > 5% the tieh sUdung sd lieu thUe nghiem ciia hdn hpp bao g d m sd lieu thUe nghiem ciia cdn tinh khiet ma nhdm tac gia da 3.2.3 Dudodn dp sudt hai Reid hdn hop xang khdng chi cd chda cdc loai Xang khdng chi la hdn hpp bao g d m hang tram hop chat khae nhau, moi hop chat cd nhiet dp sdi khac va cd cac tUOng tac giUa cac phan tU khac nhau, dac biet la cae hpp chat phan eUc va cd lien ke't hydro n h u eae hpp chat cdn se tao tinh chat hda ly rat khac chiing dupe hda trdn vdi Trong 16 ehi tieu chat lUpng ciia xang sinh hpc E5 [54] dang lUu hanh tren thj trUdng Viet Nam hien thi chi tieu ap suat hai Reid ciia xang la chi tieu ea ban ve tinh chat hda ly dac trUng eho mUc bay hai eiia cac cau tU nhe ed xang, anh hUdng den tinh nang boat d d n g ciia bd che hda khi, qua trinh chay va dae biet la qua trinh khdi d d n g eiia ddng co thdi tiet lanh hoac anh hudng de'n su van hanh lien tuc eiia ddng co thdi tiet he Ap suat hoi Reid dupe dinh nghia la ap suat hai ciia hon hpp dupe tai nhiet dp 37,8''C dupe va khdng sU dung sd lieu thue nghiem eiia cau tU tinh khiet da dupe kiem duyet dp tin cay, vi du nhU co sd dU lieu DIPPR, cd nghia la cac thdng sd xac dinh eho m d hinh Wilson thu duqc khdng the sU dung de m d phdng ngoai suy cho cac hdn hop xang khdng chi -F cdn khae, day ehinh la diem yeu ciia gia thiet Vdi mue dich Ung dung phuang trinh nhiet ddng PCSAFT vao d u doan sUthay ddi ap suat hoi Reid ciia hon hpp xang khdng chi -F eae loai cdn ham lUong eiia cac loai edn ed xang thay ddi, chiing tdi gia thiet cd the md phdng hon hpp xang khdng ehi nhU la hdn hpp ciia cac hydrocarbon: butane-hexane-iso-oetane-cyclohexane va benzene, moi hpp chat se dae trung cho tinh chat ehung eiia lan lupt cac n h d m hydrocarbon n-paraffins-iso- paraffins-naphthenes-aromatics n h u nhdm tac gia Doz et al [60] hay Alkandary et al [61] da gia djnh m d phdng hon hpp xang reformat Theo gia thiet nay, ehiing tdi lua Cd nhieu n h d m tac gia khae nghien cUu ve chpn phuang phap xay d u n g m d hinh nhiet ddng d u md phdng dU doan ap suat hai Reid cua hon hop nhien doan tinh chat nhiet ddng ciia hdn hop tU cac tinh chat lieu xang da dUa eae gia djnh khae nhau, dd ed nhiet dpng ciia eau tU tinh khiet, dieu se tang kha DAU KHi - SO 4/2011 47 HOA - C H f BifN DAU KHI nang dU doan/ngoai suy eiia md hinh Oe md phdng n-paraffins se dupe dac trung bang cau tir la butane va du doan sU thay ddi ap suat hai ciia hdn hpp xang hexane, mue dieh la de hieu chinh ap suat hai eiia hon khdng chi -F cac loai edn, chiing tdi gia djnh ap suat hop du doan bdi PC-SAFT va dU lieu thUc nghiem hoi ciia hon hpp xang khdng ehi -F cac loai ehi thay - Odi vdi loai nhien lieu Gasoline C, 0, E, sd lieu ddi phan Idn la cac tUOng tac khong ly tUdng giUa thuc nghiem khdng liet ke chi tiet phan cac hpp eae hp hydrocarbon va cac loai cdn, nhU vay, mdt chat nhu nhien lieu A & B, chimg tdi gia thiet phan PC-SAFT da cd the md phdng tdt can bang pha cac he gia ciia hon hpp xang khdng chi md hinh PC-SAFT edn -F hydrocarbon, chiing tdi hy vpng, vdi gia thuye't se dupe xac djnh thong qua ap suat hai ciia hon hpp xang nay, PC-SAFT vdi cae thdng sd cau tir tinh khiet tdi uu khdng chi (ap suat hai ciia hon hpp xang + 0% cae loai thu dupe se dU doan duqc ap suat hai eiia hon hpp eon) va diem thUe nghiem ap suat hai hon hop tai phUe tap phan ciia cae loai cdn thap nhat Theo nhu khao sat eiia nhdm tac gia, sd lieu thUe Nhu vay, phan gia djnh ciia hon hpp xang nghiem edng bo tren cac tap chi khoa hpc lien quan den khdng chi Gasoline A & B md phdng md hinh chil de la rat ban che Sau xem xet va so sanh cac PC-SAFT duqc xac djnh sir dung nhat diem thUc danh gia ve mUe dp chinh xac ciia cae dU lieu thUe nghiem ap suat hai ciia xang khdng chi -F 0% ethanol Doi nghiem, hdn hpp xang khdng ehi-Fcdn dupe gpi ten lan vdi hon hpp xang Gasoline C, D, E, phan gia djnh lupt la Gasoline A, Gasoline B, Gasoline C, Gasoline D, ciia hdn hop dupe xac dinh dUa tren diem thUe nghiem Gasoline E dUpc chpn de nghien eUu, kiem tra kha nang la: ap suat hai ciia xang -F 0% cac loai cdn va diem ap suat md phdng dudoan eiia PC-SAFT dupe tai phan ciia cac loai cdn thap nhat Tat ea cae ket qua thu dupe cdn lai la ke't qua dU doan thu dupe Bang thdng ke phan cac hpp chat khac vdi PC-SAFT dupe dac trUng bdi cac nhdm hydrocarbon ed tinh chat khac va cd ehi sd cacbon khae doi Cd the tha'y rang, ddi vdi tat ca hon hpp xang khdng vdi hai loai nhien lieu Gasoline A va Gasoline B Odi vdi ehi + cae loai edn, them 5% the tieh cae loai eon vao loai nhien lieu cdn lai, phan eu the khdng hdn hpp xang, ap suat xang tang len dang ke Sau do, dupe cdng bd nen chiing tdi da tien hanh eae gia djnh ham lupng cac loai edn them vao xang >10%, ap suat hai nhu sau: ciia xang lai cd xu hudng giam, hien tUpng cd the giai - Odi vdi loai nhien lieu A va B, phan gia dinh thich xua't hien diem dang phi ciia hon hpp cac loai hon hpp xang dupe md phdng PC-SAFT se dupe xac cdn -F hydrocarbon lam tang ap suat hai va giam nhiet dp djnh gan diing vdi sd lieu phan tich Rieng ddi vdi nhdm soi hon hpp Bang Thdnh phdn mole trung binh cCia xang khdng chi Gasoline A vd Gasoline B, dugc tinh theo nhdm hydrocarbon vd chi sd cacbon (mol%) Gasoline A n-Paraffins Gasoline B Naphthenes Aromatics n-Paraffins - 2,2 0,9 5,1 c 4,4 - - Cs 6,5 9,4 1,1 Q 1,1 4,6 0,9 Cy Cn - Tong 12 Cs c, C,o I 48 i-Paraffins DAU KHi s o 4/201 Naphthenes Aromatics - - 2,7 0,4 - 5,7 5,1 i-Paraffins 2,1 - 8,3 4,5 5,7 7,1 7,3 31,4 1,8 10,2 1,2 42,8 4,6 0,5 - 14,1 - - 0,7 0,2 - - - - 47,7 3,8 32,6 13,9 57,4 17,2 8,8 PETROVIETNAM 6.E-^04 5.E+04 1.E-F05 ; ^ ^ 1.E-I-05 -^ ^ t •" " n "TT • L T U ' ITLT 8,E+04 -=-4,E-i-04 /^ -kf^'^ TT , E - F 3,E+04 2,E+04 > • Gasoline A O Gasoline B PC-SAFT 1,E+04 4.E+04 - ^ 2.E+04-( a Exp Data _ Wilson O.E+OO O.E+00 10% 0% 20% " ' " ^^^' 20% % 60% 80% 100% % Methanol in GasollneC 0% 30% % Ethanol in Gasoline Hinh Ap sudt hdi Reid cua hdn hgp xdng khdng chi Gasoline A vd Gasoline B them ethanol Sd lieu thUc nghiem (chdm trdng) dugc lay ti/ref [62] DUdng lien Id ket qud di/dodn thu dugc si/ diing phuang trinh PC-SAFT •PC-SAFT ' Margules Hinh Ap sudt hai Reid cua hon hgp xdng khdng chi Gasoline C them methanol Sd lieu thi/c nghiem (chdm trdng) dugc lay tU ref [56] Ket qud dUdodn thu dugc bdng phuang trinh PC-SAFT dugc so sdnh vdi kit qud dudodn thu dugc sit dung cdc md hinh nhiet dgng khde IVIargules [57]; VanLaar [58] Wilson [11] 8.E+04 6.E-F04 •r H ° u LT •ra'4.E-i-04 D 2.E+04 > o^ 2.E-F04 Exp Data 1,E+04 •PC-SAFT 0,E+00 O.E+00 0% 20% 40% 60% % 100% % Ethanol in GasolineD Hinh Ap sudt hai Reid cua hon hgp xdng khdng chi Gasoline D them ethanol So lieu thi/c nghiem (chdm trdng) dugc lay td ref [56] so sdnh vdi ket qud dit dodn thu dugc bdng phugng trinh PC-SAFT • Exp, Data PC-SAFT - -Wilson 0% 20% 40% 60% 80% 100% % Iso-propanol in GasolineE Hinh Ap sudt hai Reid cua hon hgp xdng khdng chi Gasoline E them iso-propanol Sd lieu thuc nghiem (chdm trdng) dUgc Idytirref [56] Ket qud di/dodn thu dugc bdng phuang trinh PCSAFT dugc so sdnh vdi ket qud du dodn thu dugc si/dung phuang trinh Wilson [59] Ke't qua d u d o a n ap suat hoi Reid ciia hdn hop xang ethanol), dieu ed the giai thich thdng qua sU khae khdng chi -F cae loai cdn sU dung phuang trinh PC-SAFT ve phan eiia cac hop chat t h o m cd hon dupe the hien tren cac hinh ve - 6, ed the nhan tha'y ke't hpp nhien lieu That vay, ddi vdi nhien lieu Gasoline B, qua d u doan thu duqc la t u a n g ddi chinh xac vdi sai sd ndng dp cac chat t h a m cd hon hop chi chiem 8,8% tuong ddi cho da sd cac trUdng hpp la < 5% ddi vdi nhien lieu Gasoline A, phan hap chat t h o m chie'm den 32,6% ThUe nghiem cho thay, Hinh m d ta ket qua dU doan ap suat hoi Reid ciia cac hap chat t h o m khdng phai la cac chat cd lien ket nhien lieu xang sinh hpc chUa edn (Gasoline A & B) Odi hydro (auto association) nhung chiing lai ed lien ket vdi hon hpp nhien lieu Gasoline B, PC-SAFT eho ket qua hydro cheo (cross-association) vdi cac hop chat cd lien ket du doan kha ehinh xac so vdi sd lieu thUe nghiem ca hydro, vi du nhU cac loai cdn; ehinh lien ket hydro cheo d ndng dp ethanol cao (25%), nhien ddi vdi nhien lieu da lam eho ap suat hai ciia hon hop giam xudng Gasoline A, PC-SAFT cho ket qua dU doan vdi sai sd ndng dd eiia cae hop chat t h o m ed hdn hap xang khoang 6% so vdi sd lieu thUe nghiem (d ndng dp 25% khdng chi -F edn tang len OAU KHi - SO 4/2011 49 HOA - CHf BifN DAU KHI Cd the liet ke mdt sd cdng trinh nghien cUu thUe mUc dp chinh xac eiia cac so lieu thUe n g h i e m dUpc n g h i e m cung nhU t i n h toan m d p h d n g sir d u n g phan ddi vdi n h d m nhien lieu C, 0, E, nhUng viec dat sd lieu m e m Gaussian da chUng m i n h dUpc nang l u a n g lien ke't thUe n g h i e m t u a n g Ung se rat can thie't de ed the so sanh, hydro cheo giUa hop chat t h a m -F cae loai cdn la t u a n g danh gia mUc dp chinh xac & kha nang dU doan ap suat ddi Idn neu so sanh vdi nang lUpng lien ke't hydro ciia hai Reid eae loai nhien lieu xang pha eiia PC-SAFT cdn t i n h khiet Brinkley va Gupta [63] sir d u n g p h u a n g phap Spectrocopy FTIR va khang d j n h nang lupng Ket luan lien ke't cheo eiia 1-hexanol-Ftoluene, Thexanol-Fm- Trong bai bao nay, cac t h d n g sd hoan toan mdi dupe xylene, cyclohexanol -F toluene la tuong ddi Idn va cd anh xac djnh eho cac hop chat phUe tap, eae t h d n g sd mdi hudng de'n can bang nhiet ddng ciia hdn hpp; n h d m tac dupc xac djnh dUa tren cac can cU vat ly, dac biet la nang gia cung da tinh toan m d phdng Ab initio va dUa ke't luan lupng ciia lien ke't hydro t h u duqc cho cac loai edn cd gia nang lupng lien ke't hydro cheo ethanol -F toluene la - 6,6 trj rat gan vdi gia trj dat thUe n g h i e m Odi vdi cae hon kJ/ moi (795 K); ethanol -F m-xylene la - 7,1 kJ/ moi (854 K) hop cdn -F hydrocarbon, eae t h d n g sd m d i t h u dupe eho Tuong t u , nghien cUu ve lien ket hydro cheo giua methanol va ethanol eho ke't qua m d p h d n g can bang methanol + benzene s U d u n g p h u o n g phap enthalpy pha hdn hop t d t hon ke't qua t h u dUpe bdi Gross va hdn hpp, Wormald va Sow/den [64] da xac djnh dupe nang Sadowski lupng lien ket hydro cheo ciia hon hpp la - 13 kJ/ moi Karakatsani et al [25] (1563 K), nang lupng tUong ddi Idn so vdi nang lUpng lien ket hydro ciia methanol - methanol (1817 K); nang lupng lien ket cheo ciia hon hpp ethanol - benzene dupc la - 14 kJ/ moi (1684 K) [65] Anh hudng ciia hien tupng lien ket hydro cheo giUa cac hop chat: cdn t h o m (aromatic alcohol) -F hpp chat t h o m -F nude da dupe nghien cUu m d phdng sU dung GC-PPC-SAFT bdi Nguyen Huynh et al [15, 66] va nhdm tac gia da di den ket luan: neu nang lupng lien ket hydro cheo dupc tinh den mdt each ehi tiet md hinh nhiet dpng, thdng sd tuang tac hdn hop ky se cd y nghia vat ly hon, dp hda tan vdi ndng dp < 10"^ eung se dupe m d phdng mdt each chinh xac han, nhien can can nhae ve yeu eau mUc dp chinh xac ke't qua m d phdng va dp phUe tap eiia md hinh nhiet ddng sir dung [20] hay Yarrison va Chapman [24] hay Vdi sai sd t u a n g ddi t h u duqc t r o n g gidi ban tU - 5% so vdi sd lieu thUe n g h i e m sU d u n g nhat thdng sd t u a n g tac hon hpp - k h d n g phu thude vao nhiet dp Oae biet doi vdi can bang pha LLE, PC-SAFT cho ke't qua t d t hon dang ke so vdi cac m d hinh nhiet d d n g dang dupe Ua c h u d n g sU d u n g t r o n g cdng nghiep dau n h u cae m d hinh nhiet d p n g Cubic hoac m d hinh boat dp Gibbs i PC-SAFT cung cho ket qua dU doan chinh xac can bang pha m d ta su phan bd eiia cae loai edn pha hydrocarbon, dU lieu cd vai t r d rat quan t r p n g cdng nghe san xua't nhien lieu sinh hpe cd chUa cdn Vdi gia thuye't d a n gian ap d u n g de m d ta ap suat hoi Reid eiia hon hop xang k h d n g ehi, PC-SAFT cho ket qua dU doan sU thay doi ap suat hai Reid hdn h o p xang khdng Odi vdi cac hon hop nhien lieu Gasoline C, va E, chi-cac loai edn cho da so cac t r u d n g hpp dupe xem xet chiing tdi gia djnh phan cae loai hydrocarbon cd vdi sai sd t u o n g ddi t r o n g khoang 5% so vdi sd lieu thUe hdn hop xang dupe xac djnh t h d n g qua diem thUe nghiem ciia hdn hpp n h u gia thiet d tren, vdi gia thie't nay, ham lupng cac hop chat t h a m cd t r o n g hdn hap xang gia djnh thu duqc < 15% moi, t r u d n g h a p PC-SAFT cho ke't qua md phdng vdi sai sd chap nhan duqc, < 5% so vdi sd lieu thuc nghiem.Tuy nhien can nhan manh rang, PC-SAFT dU doan ap suat hoi eiia hon hpp tai diem thuc nghiem tuang Ung vdi phan 100% cac loai cdn (cdn tinh khiet) vdi sai sd khoang 15-17%, nhUng sd lieu t r o n g cac tai lieu t h a m khao cd sai khac vdi ea sd dU lieu DIPPR [19] la 15 - % Chinh dieu gay sU sai khac giUa sd lieu thUe nghiem va ket qua dU doan vdi PC- n g h i e m Vdi ke't qua nghien eUu hien tai, PC-SAFT cd the dupe sU d u n g de dU doan ap suat hai Reid ciia hon hpp xang khdng chi -F cac loai cdn vdi ham lupng hpp chat t h a m < 20% moi hoac ham lupng eae loai cdn < 25% moi Chiing tdi hy vpng, neu cac t u a n g tac ciia m o m e n t dipolar cd phan tir cdn va m o m e n t quadrupolar cd cac hpp chat t h a m va dac biet la nang lUpng tUOng tac cac lien ket hydro cheo giua cac loai va hpp chat thorn dupe tinh de'n ehi tiet t r o n g m d hinh nhiet d d n g se lam tang kha nang dU doan ciia PC-SAFT t r o n g khoan gidi ban Idn han ve ndng dp cac chat cd t r o n g hon hpp Can bang pha ciia he ehUa cae loai edn dac biet la SAFT cac t h d n g sd cau tir tinh khiet dupe xac djnh dUa ethanol - hydrocarbon - MTBE/ETBE - xang khdng chi - tren co sd d u lieu DIPPR Chung tdi khdng khang dinh ve nudc dang duqc n h d m tac gia n g h i e n cUu DAU KHi - SO 4/2011 PETROVIETNAM Tai lieu tham Ichao vapour-liquid Demirbas, M.F.Balat, M, 2006 Energy and [Management, 47, Conversion [Molecular [Modeling Applications, 2371-2381 and liquid-liquid and equilibria Simulation Physico-Chemlcal of for Industrial Properties and Processes, [March 22-23,2010, Wuerzburg/ Germany, Oral H a n s e n , A.C., Z h a n g , Q.Lyne, Bioresource P.Q.L, 0 Technology, 96, 277-285 IVIanagement, Conversion and 17 http://www.proslm.net/en/newsletter/en Reviews, 9, 535-555 15 2008 Energy Conversion and [Management, 49, 3155-3162 1990, Ind Eng Chem Res., 29, 2284-2294 19 DIPPR, 2002 Design Institute for Physical Property Data, Thermophyslcal Properties Database L a p u e r t a , M, 0 A r m a s , O.Herreros, J.M., fuel, 87, 25-31 20 Gross, J.Sadowski, G, 2002 Ind Eng Chem Res., Cardona, C.A.Sanchez, O.J, 2007 Bioresource Technology, 98, 2415-2457 B a l a t , M B a l a t , 2009.06 pcsaft.html 18 Huang, S.H.Radosz, M, R a k o p o u l o s , D.C., R a k o p o u l o s , C O , Kakaras, E.G, M, 0 , & Engineering Chemistry Research, 47(21), 8063- 8082 44,1547-1561 E.C.Giakoumis, Workshop 16 Tan, S.P, A d i d h a r m a , H.Radosz, Industrial Niven, R.K, 2005 Renewable and Sustainable Energy 86(11), (www.wp-ttp.dk/pdf/lnt Energy, 233-241 A l - 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l i q u i d e et liqu i d e - v a p e u r de melanges e o n t e n a n t des molecules oxygenees multifonctionnelles, in Technical report of 49 Haarhaus, U.Schneider, G.M., 1988 The Journal of DAUKHi - s o 4/2011 French Petroleum Institute, IFR ... tUdng va eua phan / m, ''"x \ w, — ?w, — ~-1'' m, "hard-sphere" x,va m,lan lucft la phan mole va sd "segments" ciia cau tU / a '' " la ham phan b d cap ciia "segments" ciia cau tU / Thanh phan "hardsphere"... can bang pha he methanol -i- hydrocarbon va hinh nhiet dong l