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M u Styrene l mt monomer thm khng no rt quan trng trong nn cng nghip ha cht. s hot ng mnh m ca nhm vinyl lm cho styrene d dng tham polymer ha v copolymer ha. S cn thit ca vic tng hp cao su styrene butadiene cung cp mt lng sn phm ln do iu ny tr nn c gi tr trong sn xut monomer vi tinh khit cao m c th to polymer cho ra nha bn, sch, mu sc, v r (PS-poly styrene ). V vy styrene l c s m rng nhanh sn phm nha v by gi l mt trong nhng laoij nha nhit do v r nht. ti ny l tng vi vic sn xut styrene bng phn ng dehydro ha trn xc tc ca ethyl benzene. Phn ng l qu trnh ta nhit vi hiu sut thp v trn xc tc th cho hiu sut cao hn. Qu trnh ny c dng sn xut gn 90% sn lng styrene trn ton th gii v ang tr thnh cng ngh sn xut duy nht.. trong bi ny chng ta s tnh ton cn bng nhit, cn bng vt cht v thit k mt vi thit b chnh trong s sn xut styrene.`

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Chng 1. Tng quan Gii thiu v styrene 1.1.1. Lch s ca styrene Styrene, hay l bit n vi ci tn khc nh phenylethylene, vinylbenzene, styrol, cinnamene, C6H5-CH=CH2, l mt monomer thm khng no rt quan trng trong cng nghip ha cht. n tn ti trong t nhin vi mt lng nh nh trong mt s loi thc vt v mt s loi thc n. Vo th k th 19, styrene c tch ra bng cch chng nha thm ca cy b . N cng c tm thy trong cy qu, ht c ph, v du lc, v n cng c tm thy trong nha than . S pht trin ca tt c cc qu trnh sn xut styrene da trn c s dehydro ha ethylbenzene th c pht hin vo nhng nm 1930. S cn thit sn xut cao su styrene-butadien trong chin tranh Th gii th 2 cung cp 1 lng ln sn phm. Sau nm 1946, lng sn phm ny tr nn c gi tr trong cng nghip sn xut monomer tinh khit cao t polymer ha sn xut nha bn, sch, mu sc v r ( polystyrene v styrene copolymer ). Trong thi bnh vic s dng nha trn c s styrene pht trin rng ri v polystyrene by gi l mt nha chu nhit r hn so vi gi thnh c s cng 1 th tch. Bn thn styrene l mt cht lng c th s dng d dng v an ton. Hot ng ca nhm vinyl lm cho styrene d dng tham gia phn ng polymer ha v copolymer ha. Khi mt cng ngh thch hp s tr nn c gi tr 1.1.2. Tnh cht vt l ca styrene 1.1. Styrene l mt cht lng khng mu vi mi c trng. Tnh cht quan trng nht ca styrene c tng kt trong bng sau. D liu tng hp trong bng th khng lun lun c nh. Hu ht trong cng ngh sn xut lm c phi da trn nhng tnh cht vt l ny.

Tnh cht

n v, gi tr thng n v, gi tr theo tiu c s dng chun quc t Dng vt l Khng mu, dng lng du Mu sc ( ASTM D 1209/ Max 10 DIN 6271) Mi Mi thm kh chu Gii hn mi 0.1 ppm 0.43 mg/m3 T khi phn t 104.14
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T trng 20oC (ASTM D 4052) im si im chy/im ng bng nht ng hc 0oC nht ng hc 20oC nht ng hc 40oC nht ng hc 100oC T trng hi (khng kh = 1) p sut hi 20oC p sut hi 50oC p sut hi 80oC dn nhit 20oC im chp chy (ABEL;theo IP 170) Nhit t bc chy iu kin bo ha trong khng kh 20oC Gii hn n trong khng kh 0.906 kg/l 906 kg/m3 145oC -310C 1.1 mm2/s 0.8 mm2/s 0.6 mm2/s 0.4 mm2/s 0.6 kPa 3.2 kPa 12.12 kPa 0.16 W/moC 31 32oC 490oC 25.6 g/cm3

1.1 cSt 0.8 cSt 0.6 cSt 0.4 cSt 3.6 6 mbar 32 mbar 121.2 mbar 1.6 x 10-3 J/(s.cm.K) VV

VV 5923 ppm (v/v) 0.9 6.8% th tch Tan trong nc Khng Tan trong nc 20oC 0.029% khi lng/th tch Tan trong nc trn b mt 0.054% khi lng/th 20oC tch o H s gin n 20 C v o Cng sut nhit 20 C V Nhit chy 25oC -1018.83 kcal/mol Nhit to thnh,Hf, kh 35.22 kcal/mol 25oC Nhit to thnh, Hf, lng 24.72 kcal/mol 20oC Nhit polime ha Hp 25oC -16.88 kcal/mol Nhit nng chy Ch s khc x 1.546 (nD 20oC)

0.29 kg/m3 0.54 kg/m3 0.979x10-3/oC 1.73 kJ/kg.oC -4265.64 kJ/mol 147.46 kJ/mol 103.50 kJ/mol -70.67 kJ/mol -11.0 kJ/mol V
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Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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p sut hi l mt tnh cht vt l quan trng trong vic thit k thit b chng ct Styrene . p sut hi c a trong bng sau coi l ng Nhit , oC 20 50 80 100 145.2 Phng trnh Antoine Log10P = [6.08201 1445.58/(209.43 + T)] Styrene c th trn ln vi hu ht cc dung mi hu c vi bt k t l no. N l mt dung mi tt trong tng hp cao su, nha PS, v cc polime cao phn t khc. Styrene tan c trong cc hp cht hydroxit ha tr cao nh glycol, diglycol cng nh cc mono hydroxit khc. Styrene v nc tan c vo nhau khc nhau da vo nhit (bng 1) Bng 3 : Cc tnh cht vt l khc ca styrene Nhit , oC 0 20 40 60 80 100 nht, mPas* 1.039 0.324 0.588 0.469 0.385 0.762 p sut b mt, mN/m 34.5 32.3 30.0 27.8 25.6 23.5 Nhit dung ring, Cp, Jg-1K-8 1.6367 1.6907 1.7489 p sut hi, kPa 0.6 3.2 12.2 25.7 1011.3

*mPas = -4.2488 + 1170.8T Bng 1 : S tan vo nhau ca styrene vi nc, % khi lng Nhit , oC 0 10 Nc trong styrene 0.02 0.04 Styrene trong nc 0.018 0.023
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25 50 0.07 0.12 0.032 0.045

Cu trc trong hn hp ng ph p sut iu kin tiu chun c 66% khi lng styrene v 34% khi lng nc c nhit si nh nht l 94.8oC. Thng s quan trng diu chnh trong sn xut v s dng styrene l ch s khc x v t trng Bng 2 : Ch s khc x v t trng styrene Nhit , oC Ch s khc x, nD 0 20 1.54682 25 1.54395 30 1.54108 60 100 nD = 1.55803 0.000574T 1.1.3. Tnh cht ha hc ca styrene Phn ng quan trng nht ca styrene l phn ng polymer ha thnh polystyrene nhng n cng c th tham gia phn ng co-polyme ha vi cc monomer khc. Phn ng co-polyme vi butadiene tng hp cao su buna-S l phn ng u tin dn ti s pht trin cng nghip sn xut styrene. Cc phn ng khc c miu t di y. Oxy ha styrene trong khng kh cng l 1 phn ng c bit quan trng phn ng dn ti to thnh peroxit cao phn t bng c ch gc t do. Styrene cng b oxy ha to thnh mt s hp cht khc bao gm : benzaldehyde, formaldehyde, axit formic. T trng, g/ml 0.9223 0.9050 0.9007 0.8964 0.8702 0.8355

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Styren cng c th iu ch phenyl ethanol

Styren cng c th phn ng vi ru metylic tr thnh ete

Phn ng quan trng nht ca styrene l phn ng polymer ha to thnh poly styrene
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Ngoi ra styrene c th tham gia phn ng copolymer ha vi cc monomer khc. V d vi Butadiene to thnh cao su Buna-S

1.1.4. ng dng ca styrene Styrene l mt monomer quan trng trong sn xut nha nhit do, cao su, - Khong 65% styrene c s dng sn xut polystyrene. Polystyrene th c dung sn xut nhiu sn phm thng dng nh chi, nha, vt liu gia nh, my tnh, cc thit b in t ngoi tng hp polystyrene, styrene cn c s dng tng hp polymer acrylonitrile- butadienestyren, cao su tng hp Buna-S. Nhu cu s dng styrene d tnh mi nm tng 4% - Xp x 6% styrene sn xut SBR ( styrene butadiene rubber) ng dng trong v oto, ng nc - Xp x 7% styrene sn xut SBL (styrene butadiene latex) ng dng lm thm, giy dn tng, v cc cht trong sn b mt.. - Xp x 9% styrene to thnh SAN (styrene acrylonitrile copolymer) v terpolyme ABS (acrylonitrile-butadien-styren) - Hn 7% kt hp to thnh polyester ng dng lm bn cha

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Sales
ABS POLYSTYRENE EPS SBR SBL UPR

8% 8% 6% 8%

9%

61%

1.2.

Cc phng php sn xut styrene 1.2.1. Qu trnh dehydro ha ethylbenzene trc tip

Qu trnh dehydro ha chia lm 2 dng: on nhit v ng nhit. Cng ngh c 2 dng: c xc tc v khng c xc tc. - Cng ngh khng c xc tc: Nhit phn ng khong 700-800oC chuyn ha 20-30% Hiu sut sn phm 50-60% - Cng ngh c xc tc Nhit phn ng c 600oC p sut ring phn hydrocacbon thp chuyn ha, chn lc cao (c 90%) Xc tc cho qu trnh dehydro ha thng thng l Kali-cht xc tin phn ng trn st oxit. c s dng rng ri nht l h xc tc bao gm st oxit, Kali cacbonat, v mt vi cc oxit kim laoij b tr khc. V d oxit kim loi b tr bao gm cc oxit ca cc kim loi Cr, Mo, Ce, V.
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Cc c im khc ca xc tc nh hnh dng kch thc th cng rt quan trng. theo l thuyt kch thc xc tc cng nh th cng lm tng t l phn ng bi beeg mt ring ca n ln hn rt nhiu so vi xc tc c ch thc ln hn. Tuy nhin n c bt tin l lm tng gim p t thit b phn ng. A. Dehydro ha on nhit

Qu trnh ny c ng dng rng ri nht trong cng nghip, c pht trin theo cc giai on sau: Mt thit b phn ng lm vic p sut 0.15-0.2MPa, chuyn ha 40% Hai thit b phn ng t ni tip ti u t l gia chn lc v chuyn ha, p sut nh mt h thit b phn ng, chuyn ha t c 45-55% Trong lp xc tc, nhit phn ng gim 1oC khi chuyn ha 1%. Do vy thu c chuyn ha cao, phi thm 1 lng ng k hi nc nhit cao. Tuy nhin khi nhit trn 610oC, etylbenzen v styrene to thnh b cracking. khc phc hin tng ny, cn tin hnh phn ng trong iu kin p sut thp dch chuyn phn ng theo hng mong mun. Trong trng hp th 2, p sut gim theo chiu dy ca lp xc tc, v vy thit b phn ng phi c thit k c bit ( thng s dng thit b xuyn tm hay dc trc). thit b phn ng loi xuyn tm ph hp ch to thit b phn ng cng sut ln. Etyl benzene mi v Etylbenzen tun hon c bc hi trn vi 10% hi nc gia nhit n 530-550oC v a vo thit b phn ng. 90% lng hi nc cn li c gia nhit n 800oC a vo thit b phn ng nng nhit phn ng ln 650oC, phn ng dehydro ha bt u xy ra nhit ny. Kh sn phm ra khi thit b phn ng c nhit 590-600oC c lm lnh nhanh chng trong thit b ti bng nc, nhit ca kh sn phm c dung sn xut hi nc p sut trung bnh, sau kh sn phm c tip tc lm lnh trong thit b trao i nhit bng khng kh Sn phm sau khi c lm lnh v ngng t c c vo thit b lng to 3 pha (a) Pha kh giu hydro, CO, CO2, hydrocacbon nh sau khi c nn, ha lng phn on nng, c s dng lm nhin liu.
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(b) Pha nc giu hydrocacbon thm c a vo thp tch, benzene v toluene c hi lu (c) Pha hu c ch yu cha styrene v etylbenzen c a sang b phn tch. B. Dehydro ha ng nhit V mt cng ngh, qu trnh ny thc hin kh hn on nhit v phi s dng thit b phn ng loi ng chm vi dng trao i nhit tun hon ngoi ng. Tuy nhin qu trnh ny c u im nhit nguyn liu u thp hn, t s hi nc/nguyn liu u thp hn qu trnh on nhit Qu trnh s dng kh khi lm cht ti nhit. X l sn phm dehydro Sn phm dehydro ha cha 50% styrene c a vo 4 thp chng ct ln lt thc hin cc nhim v sau: Thu styrene th thp th nht ( 70 a ) Do etylbenzen v styrene c nhit si rt gn nhau v styrene c khuynh hng d dng trng hp ( ngay c iu kin chn khng ), nn qu trnh tch styrene th ra khi etybenzen phi c thc hin trong cc iu kin sau - S a ln (60-70 a) v ch s hi lu cao ( >6) - Thc hin trong iu kin chn khng ( 7-30 kPa) gim nhit y thp xung di 108oC v tng bay hi tng i - C mt cht c ch trng hp ( lu hunh hoc dinitrophenol ) - gim p trong thit b ngng t v trong cc a thp Tinh ch styrene thu styrene thng phm: thp tinh ch styrene khi vt ca etylbenzen v hydrocacbon nng i hi iu kin mm hn: 20 a, nhit nh thp 50oC, y thp 105oC tng ng vi p sut 10 v 20kPa, c s dng cht c ch. Styrene thu c c sch 99.97%-99.98%. Thu hi etylbenzen cha phn ng, tun hon li thit b dehydro ha ( 60 a ): qu trnh thc hin trong thp chng p sut kh quyn vi nhit y thp 140oC. X l phn on nh: tch benzene v toluene trong thp chng p sut kh quyn, nhit y thp 115oC ( 20 a ), benzene c tun hon li thit b alkyl ha

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Lu hunh v nitrophenol c s dng lm cht c ch trng hp cho qu trnh chng ct styrene, cn tert-butyl-4-catecho hoc hydroquinone c s dng lm cht c ch trong qu trnh bo qun styrene. 1.2.2. Qa trnh styrene propylene oxit Con ng sn xut thng mi styrene gm qu trnh ng sn xut propylene oxit bc u tin l oxi ha trong khng kh ethyl benzene 1300oC v 0.2MPa. Phn ng ny to thnh ethyl benzene hydro peroxide (EBHP). Anpha-methyl benzyl ancol (MBA) v acetophenone (ACP) cng c th c to thnh. chuyn ha trong bc ny khong 13%. chn lc ca ethyl benzene thnh EBHP xp x 90% v chn lc thnh MBA v ACP 5 7%

C6H5C2H5 + O2 C6H5CH(OOH)CH3 EBHP C6H5C2H5 + O2 C6H5CH(CH3)OH MBA C6H5C2H5 + x O2 C6H5CO(CH3) + AXIT ACP EBHP sau phn ng vi propylene trong s c mt ca xc tc kim loi to thnh propylene oxit (PO v MBA). Kim loi Mo hoc xc tc d th pha lng Titan c s dng 110oC v 4MPa cho chuyn ha ca EBHP gn nh hon ton vi chn lc thnh PO 70 85% v chn lc thnh MBA ln hn 70%. C6H5CH(OOH)CH3 + C3H6 C3H6O + C6H5CH(CH3)OH PO ci thin hiu xut, ACP c hydro ha to thnh MBA trong pha lng 90 150oC v 8MPa. Xc tc l hn hp ca ZnO v CuO xp x 90% ACP b chuyn ha vi chn lc MBA 92%. C6H5CO(CH3) + H2 C6H5CH(CH3)OH Cui cng MBA b dehydrat ha thnh styrene 250oC vi xc tc thch hp (thng l Al2O3).
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C6H5CH(CH3)OH C6H5CH = CH2 + H2O Qu trnh ny c s dng rng ri trong cc hng Halcon, Arco, v Shell. Kt qu t l styrene/PO khong 2.5. Khong 15% sn phm styrene cung ng trn th gii c sn xut bi qu trnh. Hnh 1. Qu trnh styrene-propylene oxit

ACP : acetophoenone EB : ethyl benzene EBHP : ethyl benzene hydro peroxide MBA : methylbemzyl alcohol PO : propylene oxit, SM : styrene monomer 1.2.3. Qu trnh styrene t Butadiene Con ng khc to thnh styrene m c nghin cu bt u vi dime ha 1,3 butadien thnh 4-vinylcyclohexene.
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2C4H6 C6H9CH = CH2 VCH Phn ng ta nhit v c th tin hnh trong iu kin nhit hoc xc tc. Qu trnh nhit yu cu nhit 140oC v p sut 4MPa. Qa trnh nhit thch hp s dng butadiene tinh khit. Hiu sut to thnh VCH khong 90%. Qua trnh xc tc da trn hn hp nitrosyl halide-Fe, xy ra iu kin 0 800oC v 1 1.30MPa. Qu trnh ny c th ly nhin liu t dng C4 nguyn cht t phn on naphta hoc gas-oil t phn on cracking hi hoc butadiene nguyn cht C6H9CH = CH2 C6H5CH2CH3C6H5CH = CH2 Con ng sn xut styrene ny th cha thu ht c kinh t nhng trong tng lai c th lm c iu ny. 1.2.4. Qu trnh Styrene t toluene : C nhiu thc nghim tm ra con ng sn xut styrene i t toluene. Toluen th c gi tr, n th thng r hn t nht 15% so vi benzene v n khng c tuy nhin khng c qu trnh no c th tr nn hon ton. Hng Monsanto s dng rng ri qu trnh ny sn xut Styrene bt u vi oxi ha trong khng kh Toluene thnh Stilbene. 2C6H5CH3 + O2 C6H5CH = CHC6H5 + H2O H = -15.99 KJg-1 mol-1 tng ny th rt th v nhng ti ny b t b Mt con ng khc c nghin cu l alkyl ha toluene vi methanol 450 C trn xc tc Zeolite. Methanol v toluene d c tun hon. Hn hp styrene/etylbenzen c tch bng chng ct phn on v dehydro ha.[1]
o

1.3.

1.2.5. La chn qu trnh Ha hc ca qu trnh dehydro ha etylbenzen to styrene

Qu trnh dehydro ha ethylbenzen xy ra trong thit b phn ng. Phn ng chnh l phn ng dehydro ha, phn ng ny tng th tch v thu nhit mnh. Do , hi nc a vo cp nhit cho phn ng. Trong s cng ngh mi, cc nh cng ngh a vo thit b phn ng oxi hoc khng kh nhm thc hin phn ng H2 + 0.5 O2 H2O v y l phn ng ta nhit rt mnh, nhit ny s ng vai tr thc y phn ng dehydro ha xy ra.
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Tuy nhin qu trnh dehydro ha ethyl benzene thnh styrene cng i km l rt nhiu phn ng ph khc: to benzene, toluene, CH4, C2H4, CO, CO2, Nhng vi cc cng ngh tin tin th hiu sut to thnh styrene vn cao hn 60%.

Di y l cc phn ng chnh trong qu trnh dehydro ha ethybenzen 1 2 3 4 5 6 Phn ng C6H5C2H3C6H5CHCH2 + H2 C6H5C2H3C6H6 + C2H4 C6H5C2H3 + H2C6H5CH3+CH4 2H2O + C2H42CO +4H2 H2O + CH4CO+3H2 H2O + COCO2 + H2 Ai 8.32x103 4.29x109 6.13x102 3.95x102 1.42x102 5.82x1012 Eix10-5 (J.mol-1) 0.909 2.80 0.915 1.04 0.675 0.736

Cc yu t nh hng n qu trnh dehydro ha iu kin chun s dng cho phn ng dehydro ha vi xc tc st Nhit 620oC T l phn mol nguyn liu H2O/EB=11:1 p sut ring phn ca N2: 0.432bar nh hng ca nhit . Hnh di y th hin nh hng ca nhit v tc khng gian np liu ti chuyn ha ca etylbenzen thnh styrene ti cc nhit khc nhau. Theo thc nghim th chuyn ha ca etylbenzen thnh styrene l 80.4%, 85% v 88% ti 600oC, 620oC, 640oC tng ng

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Ta thy rng, mc d khi tng nhit , chuyn ha c tng nhng chn lc ca styrene li gim xung. Tc l ta cn tm nhit thch hp t
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chuyn ha thch hp, xong cng phi c chn lc cao trnh gy ra phn ng ph gy kh khn cho qu trnh tinh ch nh hng ca t l nguyn liu H2O/EB Theo cc s liu nghin cu, vi loi phn ng dehydro ha EB thnh styrene s dng xc tc st, t l H2O/EB thng dung l 11 mol/mol v 7 mol/mol. Nu t l H2O/EB tang s khng l tng chuyn ha ca etylbenzen v chn lc ca styrene. Tuy nhin nh hng ca t l nguyn liu H2O/EB ti chn lc styrene , khi tng nhit th chn lc styrene gim i. iu ny l l do chnh dn ti tng t l phn ng to sn phm ph.

Trong phn ng dehydro ha, ngoi thc hin phn ng dehydro ho thu nhit, ta cn phi gia nhit phn ng bng cch s dng hi qu nhit. Nh vy vic tm ra mt t l thch hp cho phn ng l mt iu cn thit. Vi s cng ngh Lummus/UOP thng minh, s dng qu trnh t H2 vi O2 cung cp nhit cho phn ng. Tuy nhin ta vn xt ti nh hng ca t l H2O/EB ti chuyn ha ca phn ng. Vic tm t l H2O/EB thch hp l rt cn thit. 1.4. Cc cng ngh sn xut styrene theo phng php dehydro ha etylbenzen

Trn ton th gii, cc hng cng ngh ch yu s dng phng php dehydro ha sn xut styren. Do , trong n thit k em s la chn cng ngh dehydro ha ethyl benzene sn xut styrene
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Cc cng ngh dehydro ha ethybenzen trn th gii ch yu thuc v cc hng Lummus/UOP, Fina/Badger, BASF, Lurgi v ta c th phn loi cc cng ngh dehydro ha thnh styrene theo cc hng thit k hoc theo ch cng ngh : on nhit hay ng nhit Kiu cng ngh Dehydro ha ethyl benzene o on nhit, hi gia nhit o on nhit, hi gia nhit o on nhit, hi gia nhit ( classic) o on nhit, gia nhit bng oxi ha (smart) o on nhit, gia nhit bng oxi ha (styro-plus) o ng nhit, gia nhit bng mui nng chy o ng nhit, gia nhit bng kh nng ng sn xut Styren v Propylen oxit Hng bn quyn Dow Fina/Badger Lummus Crest/Monsanto/UOP Lummus Crest/Monsanto/UOP UOP Montedison/DWE/Lurgi BASF Arco Shell

1.4.1. Cng ngh dehydro ha ca Lummus UOP a. Cng ngh c in ( classic)

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1. 2. 3. 4. 5. 6. 7. 8. 9.

Thit b dehydro ha ethyl benzen Thp tch s b Thit b nn kh Thp tch ethyl benzen/styren Thp chng tch thu hi ethylbenzen Thp tch benzen/toluen Thp tinh ch styren Thit b lm lnh Thit b trao i nhit

Thuyt minh dy chuyn cng ngh S cng ngh Classic ca UOP c ng dng rng ri trn ton th gii. nh my u tin c xy dng nm 1972 v k t hn 50 d n c cp php. V cho ti nm 2004 th c hn 40 nh my c xy dng v a vo sn xut thng mi.
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Cng ngh s ng l cng ngh on nhit, c gia nhit phn ng bng hi qu nhit ( nhit khong 700-850oC). Nhit phn ng khong 600oC v p sut thp. Etylbenzen nguyn liu c a cng vi dng etylbenzen tun hon vo thit b phn ng. ng thi, dng hi nc sau khi c nng nhit ti nhit cao cng c a vo thit b phn ng dehydro ha chuyn etylbenzen thnh styren. Vi cng ngh ny, sau mt thit b phn ng chuyn ha c th t c t 40-50%, v nu qua thit b th 2 th chuyn ha s t 60-75%. Thit b phn ng dng trong dy chuyn cng ngh ca UOP l thit b xuyn tm. Dng sn phm, gm ch yu l nc, styren, cc sn phm ph nh kh CH4, C2H4, etylbenzen d, toluen, benzen, v cc sn phm nng khc s c a qua thit b lm lnh, nhit ca hn hp s gim xung. tip , dng sn phm s c a vo thp tch s b 2, ti y kh s c tch ra v a n thit b nn kh 3, cn phn ngng s c thi i, lng sn phm chnh s c a qua thp tch 4. Trong thp tch 4 nhit vn cn cao nn ta phi a vo mt lng cht c ch trnh vic cc phn ng polyme ha styren din ra, nhm hn ch ti a cc sn phm nng. vi cng ngh ny ca UOP, thp tch 4 s tch styren ra khi hn hp cc sn phm nh hn, ch yu l tch ra khi etylben d, benzen ra khi toluen. Dng nh thp 4 s c a qua thp tch 5,thp tch ny s c a tr li tun hon, trn cng vi dng nguyn liu etylbenzen a vo thit b phn ng. cn dng benzen, toluen c a vo thp tch benzen/toluen. Dng sn phm y thp 4 ch yu l styren v cc sn phm trng hp khc c vo thp chng tch 7, ti y styren c tinh ch ti nng yu cu ( thng nng mol tinh khit ca styren t 99.85%) Nhng im ni bt ca cng ngh classic-UOP Thit b phn ng xuyn tm, on nhit tinh khit ca sn phm monome styren ln chuyn ha etylbenzen cao (70%) chn lc chuyn ha etylbenzen thnh styren ln hn 97% mol, do tiu th nguyn liu etylbenzen ban u thp gim p trong thit b thp, iu ny cho php thit b phn ng hot ng p sut chn khng cao, do cht lng sn phm cao hn v cng gim nguyn liu u vo
Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Thit b phn ng xuyn tm c gim p nh nht v th p sut lm vic cng thp hn, kt qu tiu th EB cng gim v vic hnh thnh sn phm ph Tit kim nng lng t thu hi nhit b. Cng ngh thng minh ( Smart process)

1. 2. 3. 4. 5. 6. 7. 8. 9.

Thit b dehydro ha ethyl benzen Thp tch s b Thit b nn kh Thp tch ethyl benzen/styren Thp chng tch thu hi ethylbenzen Thp tch benzen/toluen Thp tinh ch styren Thit b lm lnh Thit b trao i nhit

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Cng ngh ny tng i ging vi cng ngh Classic process. im khc bit ln nht gia hai cng ngh l vic ci tin thit b phn ng. Nu nh cng ngh classic, lng hi nc cn dung kh nhiu vi mc ch chnh l cung cp nhit cho phn ng, do phn ng on nhit, th cng ngh smart, thit b phn ng chnh bao gm 2 loi xc tc khc nhau. Xc tc dehydro cho ph n ng dehydro ha etylbenzen, cn xc t oxy ha ti n hnh phn ng t chy hydro trong oxy (khng kh), cung cp nhit cho phn ng. Do , trong s cng ngh smart, c them ng a khng kh vo trong thit b phn ng. Nh ta bit phn ng dehydro ha l phn ng thu nhit mnh, vic tin hnh oxy ha hydro nhm mc ch chnh l cung cp nhit cho etylbenzen tng chuyn ha, ngoi ra vic gim nng hydro cng gp phn chuyn dch phn ng to styrene, tng chn lc cho phn ng. Nhng im ni bt ca cng ngh Smart Lummus/UOP Trn th gii c 3 nh my p dng cng ngh mi ny Ci tin t cng ngh Classic Lummus/UOP. Do cng ngh ny cng c c nhng u im ca cng ngh Classic chuyn ha ca etylbenzen thnh styrene cao hn cng ngh Classic (trn 80%) Gim lng hi qu nhit cn dung v h thng cung cp hi qu nhit n gin hn Thi gian hot ng ca xc tc oxy ha v xc tc dehydro ha t 18-24 thng Khng cn gia nhit trung gian do tin hnh oxy ha gia nhit cho phn ng

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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1.4.2. Cng ngh dehydro ha ca Fina/Badger ( M)

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Phn s cng ngh ca Fina/Badger cng tng t nh cng ngh ca UOP. Tuy nhin, cu to thit b phn ng dehydro ha v thnh phn xc tc khc nhau. Ngoi ra cc thp chng tch ca Fina khc so vi UOP, trc tin l thp tch benzene v toluene ra khi hn hp sn phm, tip n l thp tch etylbenzen ra khi styrene v thp tinh ch cui cng tch styrene ra khi phn nng. Nhng im ni bt ca cng ngh dehydro ha ca Fina/Badger Thit b phn ng xuyn tm on nhit Cng ngh c p dng ti hn 40 c s sn xut styrene trn th gii, vi cng sut thit k t 32-78 nghn tn/nm chn lc phn ng to thnh styrene t trn 975, hiu sut chuyn ha etylbenzen thng thng 60-75%. Nhit nng c b sung gin tip bng cc phng php thng thng, hoc b sung trc tip theo cng ngh gia nhit trc tip ca Shell Oil tinh khit ca sn phm styrene thng t 99.9-99.95% 1.4.3. Cng ngh dehydro ha ca BASF

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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y l cng ngh ng nhit ca BASF sn xut styrene. Vi cng ngh ny, thit b phn ng dng ng chum, c gi ng nhit bi kh thi ( kh khi-flue gas). Nhit phn ng khong 600-700oC, xc tc bn quyn ca BASF. Dng etylbenzen ban u c trn vi dng hi nc, sau c gia nhit bng kh khi ln 2, tip c nng nhit ln bng cch trao i nhit vi dng sn phm styrene ra khi thit b phn ng, v cui cng c trao i nhit vi kh khi ln 1, ti y, nhit ca kh khong 630oC. Sn phm styrene s c a vo thp tch, kh thi i cn styrene th tip tc c a i tinh ch. c im ca thit b phn ng ng nhit Thit b phn ng ng chm, hng=2.4 4 m, ng knh ng 10-20cm, xc tc c in y trong ng T l hi nc/etylbenzen = 1:1 Hiu sut ca phn ng 92-94% Nng sut thit b nh ( cc i khong 22000 tn/nm) 1.4.4. Cng ngh dehydro ha ca DOW Chemical Company

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1. 2. 3. 4. 5. 6.

L gia nhit Thit b dehydro ha etylbenzen Thit b trao i nhit Thit b lm lnh Thp tch 3 pha My nn

Thuyt minh dy chuyn cng ngh Etylebenzen nguyn liu trn vi etylbenzen tun ton v dng hi nc nng nhit , sau c a qua thit b trao i nhit vi dng sn phm ra ca thp phn ng. B tr 2 thp phn ng ni tip, thit b phn ng dng xuyn tm on nhit xc tc c trong thp phn ng. Dng sn phm qua thit b phn ng th nht c nng nhit nh dng hi qu nhit, do phn ng dehydro ha l phn ng thu nhit mnh. Qu trnh trao i nhit m bo cho nhit dng vo thit b phn ng 2 t yu cu. Sau thit b phn ng th 2, dng sn phm c a qua thit b trao i nhit, nu nhit vn cn cao th c qua thit b lm lnh, sau a vo thp tch 3 pha, pha nc ngng t di cng, kh nh
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thoy ra trn cng, cn li ly sn phm ch yu styrene. a dng sn phm ny qua cc thit b chng tch cao cho t nng yu cu 1.4.5. La chn cng ngh Qua qu trnh phn tch cng ngh dehydro ha em xin chn cng ngh on nhit ng vi thit b phn ng xuyn tm theo cng ngh ca UOP. V phc v cho vic thit k m phng s cng ngh, em chn cng ngh Classic ca UOP v n c rt nhiu u im ng thi s cng n gin, khng phc tp, khng tn nhiu nhin liu

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Chng 2: Thuyt minh dy chuyn cng ngh Lummus/UOP classic sn xut styrene.

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D n mang tnh thng mi u tin da trn cng ngh Lummus/Monsanto m sau ny tr thnh cng ngh Lummus/UOP th c a ra nm 1972. T hn 50 ti c cp giy php vi hn 40 d n thng mi c a ra cho n nm 2004. Qu trnh Lummus/UOP Classic SM

1. Thit b dehydro ha ethyl benzen 2. Thp tch s b 3. Thit b nn kh


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4. 5. 6. 7. 8. 9. Thp tch ethyl benzen/styren Thp chng tch thu hi ethylbenzen Thp tch benzen/toluen Thp tinh ch styren Thit b lm lnh Thit b trao i nhit

Etylbenze (EB) sch v tun hon trn vi nhau v trn vi hi nc trc khi c a vo thit b dehydro ha. Dng sn phm, gm ch yu l nc, styren, cc sn phm ph nh kh CH4, C2H4, etylbenzen d, toluen, benzen, v cc sn phm nng khc s c a qua thit b lm lnh, nhit ca hn hp s gim xung. tip , dng sn phm s c a vo thp tch s b 2, ti y kh s c tch ra v a n thit b nn kh 3, cn phn ngng s c thi i, lng sn phm chnh s c a qua thp tch 4. Trong thp tch 4 nhit vn cn cao nn ta phi a vo mt lng cht c ch trnh vic cc phn ng polyme ha styren din ra, nhm hn ch ti a cc sn phm nng. vi cng ngh ny ca UOP, thp tch 4 s tch styren ra khi hn hp cc sn phm nh hn, ch yu l tch ra khi etylben d, benzen ra khi toluen. Dng nh thp 4 s c a qua thp tch 5,thp tch ny s c a tr li tun hon, trn cng vi dng nguyn liu etylbenzen a vo thit b phn ng. cn dng benzen, toluen c a vo thp tch benzen/toluen. Dng sn phm y thp 4 ch yu l styren v cc sn phm trng hp khc c vo thp chng tch 7, ti y styren c tinh ch ti nng yu cu ( thng nng mol tinh khit ca styren t 99.85%) Thit b chnh ca qu trnh dehydro ha trong cng ngh Lummus/UOP Classic SM l 1 ni hi, 2 thit b phn ng dehydro ha ( thit b phn ng xuyn tm ) v nhiu thit b trao i nhit ( hnh ). Thit b c thit k vi gim p nh nht t thit b dehydro ha n thit b nn kh thi. Hi i vo l t v c s dng gia nhit li cho thit b phn ng dehydro ha th 2. Hn hp phn ng c gi nhit li trong mt b trao i nhit c thit k c bit c t bn caanhj thit b phn ng th 2. Hi lnh ra khi thit b trao i nhit th c a vo ni hi gia nhit li trc khi i vo thit b phn ng dehydro ha th nht. hi ra khi ni hi c nhit trong khong t 700oC n 850oC t c nhit h phn ng mong mun trong thit b phn ng th 1. Hi khi ra khi l hi c trn vi EB v hi s cp. giai on sau th s dng hi p sut trung bnh hoc p sut thp. Dng hi ny c hai nh hng n xc tc:
Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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Gim lng cc to thnh t phn ng cracking v reforming xy ra ng thi vi phn ng dehydro

Thit k dy chuyn sn xut Styrene bng phng ph|p dehydro ha etylbenzen [Type text]

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