N MN HC

MC LC
PHN I. TNG QUAN ................................................................................................................................. 2 1.Tnh cht ca nguyn liu v sn phm .................................................................................................. 2 1.1.Benzen .............................................................................................................................................. 2 1.2.Etylen ............................................................................................................................................... 7 1.3.Etylbenzen ......................................................................................................................................10 1.3.3.Ch tiu k thut ca etylbenzen thng phm ...............................................................................12 1.3.4. Qu trnh tn tr v vn chuyn etylbenzen...................................................................................13 2.Cc phng php sn xut etylbenzen ..................................................................................................14 2.1.Bn cht ha hc ............................................................................................................................14 2.2.C ch ...........................................................................................................................................17 2.3.Xc tc ...........................................................................................................................................18

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 N MN HC

Li m u Gii thiu v vai tr quan trng ca etylbenzen i vi cuc sng v cng nghip, nhu cu trong tng lai, s tng vt v nhu cu s dng etylbenzen trn th gii trong nhng nm tr li y PHN I. TNG QUAN 1.Tnh cht ca nguyn liu v sn phm Nguyn liu 1.1.Benzen Benzen l mt hydrocacbon thm, n vng, c cng thc phn t C6H6, phn t lng M= 78.11 vC. iu kin thng, benzen l cht lng khng mu, d bt chy. Benzen l cht bn nhit, hot ng ha hc, nn trong cng nghip, n thng c s dng lm nguyn liu trong ngnh cng nghip tng hp hu c ha du tng hp ra cc dn xut nh styren, phenol, xyclohexan, lm nguyn liu sn xut ra thuc tr su, cht do, nha, dc phm, cht ty ra,Benzen l mt dung mi c kh nng ha tan tt, nhng do c nhc im l rt c, nn hin nay n b thay th bi nhiu dung mi khc. SVTH: Nguyn Th Ngn Page 2

 N MN HC
M. Faraday l ngi u tin thu c benzen bng cch tch t bicarburet ca hydrogen t th nghim trn du c voi nhit phn v nguyn liu khc. A.W. Hofmann v C.Mansfield t trng cao ng ha hc Royal cng lm th nghim trn cht lng thu c t than nhit phn. H pht trin trn quy m thng mi qu trnh thu benzen v cc hp cht thm khc t nha than t nm 1840- 1850. [2] Trong giai on chin tranh th gii th II, benzen ch yu c thu t than. Nhng sau ny, khi ngnh cng nghip ha du pht trin cng vi vic nghin cu ra cc loi xc tc hiu qu th du m tr thnh ngun nguyn liu chnh sn xut ra benzen v cc hydrocacbon thm khc. 1.1.1.Tnh cht vt l ca benzen Cng thc phn t C6H6 Phn t lng M= 78.11 vC Cng thc cu to

iu kin thng, benzen l cht lng khng mu, c mi c trng. nhit thp, benzen ng rn thnh khi tinh th mu trng. Benzen l hp cht rt d bt chy, khi chy to thnh ngn la c mui. Hi benzen to thnh hn hp n vi khng kh trong khong nng rng. Benzen l dung mi khng phn cc, c kh nng ha tan trong ru etylic nhng tan rt t trong nc. Mt s thng s vt l c trng ca benzen c trnh by trong bng 1. Bng 1. Mt s thng s vt l c trng ca benzen [1] Thng s Khi lng phn t T trng 20oC n v vC Gi tr 78.11 0.879

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 N MN HC

Nhit nng chy Gii hn n trong khng kh Di Trn Nhit chp chy cc kn T trng hi (khng kh = 1) Gii hn tip xc (ppm; gi)

80.1

% th tch 1.4 7.1

o

-11.1 2.77 5; 8

1.1.2.Tnh cht ha hc ca benzen Benzen l cht ng u tin trong dy ng ng ca cc hydrocacbon thm, c c trng bi cu trc vng bn vng nh s xen ph (cng hng) ca cc orbital . Do n khng d dng tham gia phn ng cng cc tc nhn dng halogen v axit nh cc anken. Tuy nhin, benzen rt nhy vi phn ng th electrophil vi s c mt ca xc tc. Benzen l cht bn nhit, hot ng ha hc nhit trn 500oC, do cc phn ng ca benzen thng c thc hin nhit trn 500oC. V d, 600oC, di tc ng ca xc tc kim loi (st, ch, vanadium,) xy ra phn ng ngng t ca benzen to ra diphenyl v cc hp cht polyaromatic khc. Benzen kh tham gia phn ng oxy ha do n c cu trc vng bn vng, tuy nhin, trong iu kin khc nghit, n b oxy ha hon ton sinh ra kh CO2 v nc. Nu lng oxy hoc khng kh tham gia phn ng thiu, mt phn benzen b phn hy to thnh kt ta en (b hng). Nu trong phn ng m c mt xc tc (V-Mo), phn ng c thc hin pha hi trong iu kin T= 350- 450oC to ra anhydric maleic vi hiu sut khong 65- 70%,[2]. Thc hin phn ng oxy ha benzen bng khng kh trong iu kin nhit cao s thu c phenol, tuy nhin hiu sut ca phn ng thp. Mt phn ng quan trng ca benzen, m c s dng rt nhiu cng nghip, l phn ng th. Ty thuc vo iu kin phn ng m mt hay nhiu nguyn t hydro trong vng benzen c th b thay th bi gc nitro hoc gc axit sulfonic, gc amine, hydroxyl hay cc nguyn t halogen (Cl, Br) to ra cc sn phm nh phenol, nitrobenzen, clobenzen, hay axit benzen sulfonic,

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 N MN HC
Benzen c kh nng tham gia phn ng cng, phn ng oxy ha v phn ng hydro ha. Cc phn ng ny xy ra iu kin nhit v p sut cao, trong mt s trng hp cn cn s c mt ca xc tc, v d nh phn ng alkyl ha ca benzen v etylen to ra etylbenzen hay phn ng alkyl ha ca benzen v propylen to ra cumen. Phn ng hydro ha ca benzen cng rt c ngha trong cng nghip sn xut ra cyclohexan. Phn ng c th xy ra trong pha lng hoc pha hi, iu kin nhit v p sut cao. 1.1.3. Ngun cung cp nguyn liu benzen Benzen v cc cht ng ng ca n nh toluen, xylen c th c tm thy trong du th nhng vi mt lng rt nh, do , nu ch s dng cc qu trnh phn tch vt l thu hi chng t ngun ny s khng em li hiu qu kinh t cao. Hm lng aromatic, naphtenic, v parafinic cha trong du th v phn on naphtha ca du th Saudi Arabian v du th United Kingdom c ch ra trong bng 2 Bng 2. Kt qu phn tch cc phn on ca du th, [2]. Property Crude gravity, oAPI Sulfur, wt % C5 and lighter, vol % Light naphtha, yield, vol % (debutanized) T.b.p.*range, oC End point, oC Gravity, oAPI Sulfur, wt % Aromatics, vol% Naphthens, vol% Paraffins, vol % SVTH: Nguyn Th Ngn Saudi Arabian mixed 34- 34.9 1.63 1.6 13.7 C5 126 ** 132 72.5 0.02 5 5 90 71.3 0.04 3.1 30.5 66.4 75 0.03 2.4 12.3 85.3 Page 5 Thistle, U.K 37.4 0.31 3.3 13.23 31- 105 Saudi Arabian light 34.1 1.72 1.5 9.3 C5- 93 **

 N MN HC

(T.b.p: true boiling point distillation. C5 refers to C5 plus content of light naphtha) Trong cng nghip, ngun cung cp benzen cng nh cc ng ng ca n nh toluen v xylen ch yu l t sn phm ca qu trnh reforming xc tc naphtha. Mt ngun cung cp BTX quan trng khc l t qu trnh cracking xc tc, trong , cc phn on du th t c gi tr v phn cn nng c phn hy trong iu kin c xc tc to thnh cc cu t hydrocacbon nh. Naphta sn phm c tr s octan cao nh cc phn ng thm ha xy ra cng vi phn ng chnh cracking. Mt qu trnh mi khc cng c xem nh mt ngun cung cp BTX quan trng, l qu trnh Cyclar. Nguyn liu ca qu trnh ny l kh du m ha lng c thnh phn ch yu l C3, C4. Xc tc cho qu trnh l dng zeolit c kh nng xc tin phn ng dehydro ha nguyn liu, polyme ha sn phm mi hnh thnh to nn cc oligome khng no, v tip tc dehydro vng ha cc oligome ny to thnh cc hydrocacbon thm. Hiu sut benzen thu c t qu trnh ny thng ln hn qu trnh reforming xc tc. Qu trnh steam cracking naphtha ch yu nhm sn xut ra etylen, nhng cng l mt ngun cung cp ng k cc hydrocacbon thm, c bit l benzen c trong sn phm lng ca cng ngh ny. Cc hydrocacbon thm ny c sinh ra t cc phn ng cng ng vng etylen mi hnh thnh v dehydro vng ha xy ra trong qu trnh steam cracking. Hydrocacbon thm cng c th thu c t ngun khng phi du m, thc t, khong 10% [1] lng hydrocacbon thm tiu th trn th gii ngy nay c sn xut t than . y c xem l ngun cung cp benzen v cc sn phm th benzen khc ch yu t trc nm 1940 [1]. Cc hydrocacbon thm hnh thnh thc cht l sn phm ph ca qu trnh cc ha than nhit cao. 1.1.4. Qu trnh tn cha v vn chuyn benzen Benzen l cht d bt chy, d bay hi v c tnh c, do qu trnh tn tr v vn chuyn benzen cn phi tun theo qui nh nghim ngt. Nhn l mt yu t c bit quan trng i vi cc con tu ch benzen. Cc hng M nh: OSHA, EPA, DOT, NIOSH, c qui nh r v iu ny [2]. Cc qui nh v cch vn chuyn v ng tu c cp nht sa i v ban b hng nm ti CFR. Cc nc khc cng c nhng iu lut qui nh v qui trnh k thut m bo an ton kh ging so vi M. Mc d, cc qui nh c bit phi c p dng cho SVTH: Nguyn Th Ngn Page 6

 N MN HC
cc c s sn xut, phng th nghim kim tra, khu vc tn tr, qu trnh tho d hng, vn chuyn benzen, qui inh an ton c p dng nh vi mt cht lng hoc kh d bt chy v c khc. Benzen c bo qun , tn tr v vn chuyn trong cc thng hoc b cha bng thp. iu kin thng gi thch hp rt cn thit trong qu trnh bo qun benzen. Do benzen c tnh c, nn nhng ngi cng nhn khi phi lm vic tip xc vi benzen, th cn phi s dng bo h trnh benzen tip xc trc tip ln da,hay ht phi khi c cha benzen. Trong qu trnh tho, np xng cng cn phi cn thn do benzen l cht d bay hi. Khi xy ra s c chy do benzen c th dng CO2 hoc cc ha cht c kh nng cha chachy khc dp la. 1.2.Etylen Etylen bt u c s dng rng ri trong cng nghip t gia nhng nm 1940 [2], khi cc cng ty ha cht v du ca M phn tch c etylen t kh thi ca nh my lc du hay sn xut ra etylen t etan (thu c t sn phm ph ca nh my lc du v t kh t nhin). T , etylen gn nh c dng thay th hon ton acetylen trong nhiu qu trnh tng hp do tnh an ton v r hn ca etylen so vi acetylen. Etylen c sn xut ch yu t qu trnh steam cracking cc hp cht hydrocacbon hay c thu hi t kh cracking trong nh my lc du. 1.2.1.Tnh cht vt l Cng thc phn t C2H4 Phn t lng M= 28.52 vC Cng thc cu to CH2=CH2

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 N MN HC
iu kin thng, etylen l cht kh khng mu, d bt chy v c mi ngt. Mt s thng s vt l c trng ca etylen c trnh by trong bng 3.

Bng 3. Mt s thng s vt l c trng ca etylen [1] Nhit kt tinh Nhit si Nhit ti hn, Tc p sut ti hn, Pc
o o o

C C C

-169.15 -103.71 9.90 5.117

MPa

1.2.2.Tnh cht ha hc Etylen l cht ng u tin trong dy ng ng ca cc olefin, do n c cu trc n gin nht, ch gm mt lin kt i ni gia 2 nguyn t cacbon. Trong cc phn ng ha hc, etylen l cht hot ng mnh, d dng tham gia cc phn ng v to thnh t sn phm ph, y cng l mt l do etylen c gi l vua ca cc hydrocacbon. Cc phn ng quan trng ca etylen c s dng trong ngnh cng nghip: phn ng cng, phn ng alkyl ha, halogen ha, hydro formyl ha, phn ng hydrat, phn ng oligome ha, polyme ha v phn ng oxy ha. Di y l danh sch cc qu trnh cng nghip in hnh trn th gii nm 2000, s dng nguyn liu etylen [2]: Qu trnh polyme ha sn xut polyetylen c khi lng ring nh (LDPE) v polyetylen c khi lng ring nh, mch di (LLDPE). Qu trnh polyme ha sn xut polyetylen khi lng ring ln (HDPE). Cng hp clo sn xut 1,2 diclo etan. Qu trnh oxy ha sn xut etylen oxyt trn xc tc bc. Phn ng vi benzen sn xut etylbenzen, kt hp vi phn ng dehydro ha sn xut styren. Qu trnh oxy ha sn xut acetaldehyt. Qu trnh hydrat ha to ra etanol. Phn ng vi axit axetic v oxy to ra vinyl acetat. SVTH: Nguyn Th Ngn Page 8

 N MN HC
Cc qu trnh khc nh sn xut ru bc cao, olefin mch di 1.2.3. Ngun cung cp nguyn liu etylen Etylen ch yu c sn xut t qu trnh cracking hi nc (steam cracking) vi nhiu ngun nguyn liu khc nhau: t cc hydrocacbon khc nhau nh etan, propan, butan, naphta, kh ha lng (LPG) v gasoil. Ty thuc vo iu kin ca tng nc m nguyn liu s dng sn xut etylen l khc nhau, v d, M do nhu cu s dng naphta cho qu trnh reforming xc tc sn xut xng v do c ngun kh t nhin di do, nn etan l ngun nguyn liu chnh c dng cho qu trnh cracking hi sn xut etylen (52% etylen c sn xut t etan, 22% t gasoiil, 5% t naphta, cn li t cc ngun nguyn liu khc [1]). Trong khi Nht v Ty u li s dng phn on naphta thu c t qu trnh chng ct du th cho mc ch ny (71% etylen sn xut t naphta, 11% t gasoil, 11% t LPG, cn li t sn phm cracking etan [1]). Cc ngun sn xut etylen khc bao gm: dehydrat ha ru etylic (n , Brazin, Thy in, Trung Quc), cracking cc sn phm thu c t qu trnh kh ha than (Nam Phi) v chuyn ha ru metylic (hng UOP/Mobil M) 1.2.4. Qu trnh tn cha v vn chuyn etylen Mt lng ln etylen sn xut ra c tiu th ti cc c s c cng sut nh, do yu cu thit b tn cha v vn chuyn nh. Do cu trc h tng ca cc nh my ha du phc tp, m ti M v Chu u, cc h thng ng dn v cc hang cha di lng t (pressurized underground caverns) c pht trin. Cc ng ng ny c u im l n hi v c th cung cp etylen lin tc. Mt s h thng ng ng sau thng c s dng [2]: United States: Texas Louisiana Canada: Fort Saskatchewan Sarnia Great Britain: Grangemouth Carrington Sevenside Fawley Europe: Northwest Europe (Frankfurt Gelsenkirchen and Brussels Rotterdam areas) and Spain Former Soviet: Nizhnekamsk Salavat and ngk Zima trong cc ng ng, etylen thng c p sut t 4 100 MPa [2]. Nu p sut ca etylen thp hn gi tr ti hn th nhit ca n phi duy tr nhit trn 4oC trnh etylen b ha lng. Nu c mt nc trong ng, hydrate c th to thnh iu kin T< 15oC, p sut thng v c th lm tc ng ng, thit b. Etylen cng c th vn chuyn bng tu, thuyn, t, v xe ti. SVTH: Nguyn Th Ngn Page 9

 N MN HC
Etylen c tn cha di lng t iu kin p sut cao bng ng ng hoc b cha (10 MPa, [2]) v trong cc b cha c lm lnh bn ngoi. Gn y, ngi ta c s dng phng php nn v ha lng hi, cho php tn cha etylen dng lng, gim p sut trong b cha xung cn 7- 70 kPa [2]. Sn phm 1.3.Etylbenzen Etylbenzen thuc nhm hydrocacbon thm c cu to gm mt vng thm v nhnh l gc (C2H5-) nh trc tip vo vng benzen. Etylbenzen ch yu c s dng (>99%) lm nguyn liu sn xut ra mono styren (C6H5CH=CH2), mt lng nh khc (< 1%) c dng lm dung mi pha sn, hoc l cht trung gian sn xut ra dietylbenzen v acetophenone [2]. Trong sn xut cng nghip, etylbenzen ch yu c to ra bng phn ng alkyl ha benzen bng etylen. Etylbenzen c a vo sn xut trn qui m thng mi t nhng nm 1930 bi hai hng Dow Chemical M v BASF c. Trong chin tranh th gii th II, do nhu cu sn xut ra cao su styren- butadien (SBR) rt ln thc y ci tin cng ngh v m rng cng sut sn xut. Trong khong thi gian ny c rt nhiu nhng c gng ng k xy dng nhiu nh my sn xut quy m ln, a nng sut styren tng nhanh tr thnh ngnh cng nghip quan trng. Nm 1999, trn th gii, nng sut etylbenzen sn xut ra hng nm t xp x 25*106 tn [2]. 1.3.1.Tnh cht vt l Cng thc phn t C8H10 Cng thc cu to

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iu kin thng, etylbenzen (EB) l cht lng trong sut, khng mu c mi c trng ca hydrocacbon thm. EB c kh nng gy kch thch cho da, mt v gy c mc trung bnh qua ng n ung, h hp v tip xc qua da. Mt vi thng s vt l c trng ca EB c trnh by trong bng 3. Bng 3. Mt s thng s vt l c trng ca etylbenzen [1] Thng s Khi lng phn t T trng 20oC Nhit nng chy Nhit si Gii hn n trong khng kh Di Trn Nhit chp chy cc kn T trng hi (khng kh = 1) Gii hn tip xc (ppm; gi)
o o o

n v vC

Gi tr 106.17 0.867

C C

-94.9 136.2

% th tch 0.99 6,7 C 15 3.7 100;8

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1.3.2.Tnh cht ha hc Phn ng ha hc c ng dng ln nht trong sn xut cng nghip ca EB l phn ng dehydro ha sn xut styren. Phn ng ny xy ra iu kin nhit cao (600- 660 o C) trn xc tc K- oxit st. chn lc ca sn phm chnh styren t t 90- 97% [2]. Bn cnh cn c phn ng ph, dealkyl ha EB to ra sn phm benzen v toluen. Phn ng oxy ha EB bng khng kh to ra hydroperoxit (C6H5CH(OOH)CH3). Phn ng ny xy ra trong pha lng v khng c mt xc tc. Tuy nhin, do hydroperoxit l cht khng bn vng, nn nhit phn ng phi duy tr nhit thp nht c th hn ch tc phn ng phn hy. Cc phn ng ph cng c hn ch nu gim t t nhit phn ng trong sut qu trnh phn ng. cc hydroperoxit sau c cho phn ng vi propylen to ra styren v propylen oxit. Nm 1999, trn th gii, khong 15% sn lng EB c s dng sn xut ra styren v propylen oxit [2]. Cng ging nh toluen, EB c th tham gia phn ng dealkyl ha to thnh benzen trong iu kin c hoc khng c xc tc. 1.3.3.Ch tiu k thut ca etylbenzen thng phm Do etylbenzen sn xut ra c s dng ch yu tng hp styren, do , cc yu cu v thng k thut c p dng cho etylbenzen nhm m bo etylbenzen thu c c th a vo sn xut styren. Nu tinh khit ca etylbenzen khng t yu cu c th gy cn tr n qu trnh thc hin phn ng sn xut styren, s nh hng n tinh khit ca sn phm styren: Hp cht cha nguyn t halogen lm mt hot tnh xc tc ca phn ng dehydro ha v cn c kh nng gy n mn thit b phn ng. Thng th cc phn t clo hu c c mt l do ln trong sn phm etylbenzen t qu trnh alkyl ha vi xc tc AlCl3, Dietylbenzen nu c mt trong nguyn liu etylbenzen s b dehydro ha to ra sn phm l divinylbenzen. Divinylbenzen sinh ra c kh nng to lin kt ngang gia cc phn t polyme lm cho chng khng th b ha tan?? v lm gim cht lng sn phm, do trong nguyn liu etylbenzen ngi ta c quy nh hm lng dietylbenzen phi nh hn 10 ppm [2]. Th mi c a vo sn xut styren. Cc tp cht cha trong etylbenzen c th gy nh hng n tinh khit ca styren l cc cu t c khong nhit si nm gia nhit si ca etylbenzen v styren: xylen, propylbenzen, v etyltoluen. Hm lng

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cc cht ny trong etylbenzen c iu chnh p ng yu cu v tinh khit cho styren. Mt s cc ch tiu k thut c dng nh gi cht lng ca etylbenzen thng phm (cho cc nh my sn xut etylbenzen M) [2] Bng 4. Mt s thng s k thut nh gi cht lng ca etylbenzen thng phm Thng s tinh khit ca sn phm Hm lng benzen Hm lng toluen Hm lng hp cht nonaromatics Hm lng propylbenzen Hm lng dietylbenzen Hm lng hp cht cha ClHm lng lu hunh hu c T trng 15oC APHA colour 0.1Gi tr 99.5% wt 0.05- 0.3% wt 0.3 %wt 0.05%wt, max 0.02% wt, max 10 mg/kg, max 1-3 mg/kg, max 4 mg/kg, max 0.869- 0.872 15, max

(APHA-American Public Health Association, l mt loi ch s mu, c s dng nh gi tinh khit ca sn phm, ch s ny c xc nh theo tiu chun ASTM D1209, [8]). 1.3.4. Qu trnh tn tr v vn chuyn etylbenzen Etylbenzen l cht lng d bt chy, n c cha v vn chuyn bng cc container bng thp v c quy nh r rng, c th bng cc quy nh php lun v lng etylbenzen c th vn chuyn m bo an ton trong qu trnh vn chuyn (v d nh M 454 kg [2]) Cc loi cht cha chy dng bt, CO2, ha cht kh, halon, v nc (dng sng) u c th s dng dp la chy gy ra bi etylbenzen Ch thng gi hp l cng rt cn thit khi vn chuyn v tn tr etylbenzen. m bo an ton khi cn phi tip xc vi etylbenzen, ngi tip xc nn mang bao tay v knh an ton, hn ch khng etylbenzen tip xc trc tip vi da. SVTH: Nguyn Th Ngn Page 13

 N MN HC
Trong qu trnh tn tr, cn trnh khng etylbenzen gn vi nhit, la, cc cht mi la, cht giu oxy, 2.Cc phng php sn xut etylbenzen 2.1.Bn cht ha hc 2.1.1.Gii thiu chung v qu trnh alkyl ha Alkyl ha l qu trnh a nhm alkyl vo phn t hp cht hu c hoc v c. Phn ng ny c th c phn loi theo dng lin kt to thnh hoc nhm alkyl a vo phn t hp cht. a.Phn loi Phn loi theo dng lin kt to thnh gia nguyn t C vi nguyn t ca cc nguyn t khc (phng php phn loi ph bin nht), ngi ta chia qu trnh alkyl ha thnh: Alkyl ha theo nguyn t cacbon (C-alkyl ha) l th nguyn t hydro ni vi cacbon bng cc nhm alkyl. C parafin v hydrocacbon thm u c th tham gia phn ng ny CnH2n+2 + CmH2m Cn+mH2(n+m+1)

Alkyl ha theo nguyn t oxy (O- alkyl ha) v lu hunh (S- alkyl ha) l cc phn ng dn n to thnh lin kt gia nhm alkyl v nguyn t oxy hoc lu hunh

NaSH + RCl RSH + NaCl Alkyl ho theo nguyn t nit (N- alkyl ha) l s th cc nguyn t hydro trong amoniac hoc trong amin bng cc nhm alkyl.

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 N MN HC
NaSH + RCl RSH + NaCl ROH + NH3 RNH2 + H2O Phn ng alkyl ha cn c th c tin hnh ti v tr cc nguyn t ca cc nguyn t khc nh Si, Al, Pb (tng ng vi Si- alkyl ha, Al- alkyl ha, Pbalkyl ha), phn ng ny c ng dng tng hp cc hp cht c kim. 2RCl + Si R2SiCl2 4C2H5Cl + 4PbNa Pb(C2H5)4 + 4NaCl +3Pb 3C3H6 + Al + 3/2H2 Al(C3H7)3 Nu phn loi theo s khc bit v cu to ca nhm alkyl a vo phn t hp cht, ngi ta chia qu trnh alkyl ha thnh: Alkyl ha mch thng, vi nhm alkyl l mch thng (nh etyl ha, isopropyl ha)

Alkyl ha mch vng (v d xyclo hexyl ha): b.Tc nhn alkyl ha Tc nhn c th s dng cho qu trnh alkyl ha rt a dng. Theo lin kt b t trong qu trnh alkyl ha, ngi ta phn loi cc tc nhn alkyl ha thnh: Cc hp cht khng no (olefin, axetylen), in hnh l cc olefin, vi lin kt b t l . Loi ny c u im l gi thnh thp, c bit l olefin, v thng c s dng cho qu trnh C- alkyl ha. Cc dn xut halogen c lin kt b t l C- X (X l halogen), c bit l cc dn xut clo. y l tc nhn alkyl ha thng dng cho rt nhiu hp cht, trong cc trng hp C-, O-, S-, N- alkyl ha cng nh tng hp cc hp cht c kim. Chng c th c s dng tng hp cc alkylat hydrocacbon thm, cc ete, thioete v cc amin. Chng c s dng trong qu trnh tng hp axetoaxetic v iu ch cc tc nhn Grignard. Nhng loi ny c nhc im l gi thnh cao, v trong phn ln cc phn ng ca chng, c s hnh thnh HCl, l cht gy n mn mnh, do chng khng c s dng ph bin trong cng nghip. Hp cht cha oxy nh ru, ete, oxyt olefin c lin kt b t l C- O. Tiu biu cho loi ny, l ru v ete. Loi tc nhn ny rt thch hp cho qu trnh alkyl ha theo nguyn t C, N, O v S. Tuy nhin chng li khng c s dng ph bin trong cng nghip bng cc olefin do chng km hot ng hn v c bit, SVTH: Nguyn Th Ngn Page 15

 N MN HC
trong cc phn ng thng sinh ra nc c kh nng lm phn hy xc tc AlCl3, gy n mn thit b phn ng (khi c mt c HCl), v c th pha long tm xc tc axit. 2.1.2.C s ha hc ca phn ng alkyl ha benzen bng etylen Phn ng chnh ca qu trnh alkyl ha benzen bng etylen [6]

Do benzen l mt hydrocacbon thm hot ng. Di cc iu kin thch hp, benzen c th c th bi cc tc nhn i in t khc nhau. Khi alkyl ha, vng benzen tr nn hot ha v cc hp cht di-, tri-, polyalkyl d dng hnh thnh hn:

Tuy nhin, trong cng nghip ngi ta c th tng hiu sut to etylbenzen ln cao nht bng cch tng t l benzen/etylen n gi tr thch hp, ng thi kt hp vi vic tun hon li cc polyalkylbenzen tr li thit b phn ng cng gip lm tng hiu sut to etylbenzen nh phn ng chuyn nhm alkyl

Mt s phn ng ph:

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 N MN HC

2.2.C ch [4] Phn ng alkyl ha ni chung v phn ng alkyl ha benzen bng etylen ni ring xy ra theo c ch ion cacboni, qua cc giai on sau: Bc u tin l to ra ion cacboni:

Nu s dng tc nhn alkyl ha l dn xut halogen trn xc tc AlCl3, ion cacboni c th c sinh ra theo phn ng sau

Bc tip theo, ion cacboni tn cng vo vng bezen, sau , proton tch ra v to thnh alkylbenzen

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 N MN HC

2.3.Xc tc 2.3.1. Xc tc cho qu trnh alkyl ha Cc phn ng alkyl ha xy ra theo c ch cacbocation, do , xc tc s dng cho qu trnh phi c tnh axit, xc tin cho phn ng to ra cacbocation. Xc tc cho phn ng alkyl ha thng c chia thnh cc loi sau Xc tc l cc axit lng thng l cc axit Brnsted nh H2SO4, HF

Xc tc l axit Lewis nh AlCl3, trong trng hp ny, mt lng nh axit cha H+ thng c thm vo hn hp nh l cht ng xc tc thc y qu trnh hnh thnh cacbocation.

Xc tc d th thng c s dng cho qu trnh alkyl ha l Al2O3, Al2O3/SiO2 v cc zeolit. y l loi xc tc cha c hai tm axit Brnsted v Lewis, c kh nng xc tin qu trnh to hp cht trung gian cacbocation trong phn ng alkyl ha. V d phn ng alkyl ha bezen bng etylen trn xc tc zeolit, etylen hp ph s c proton ha tm axit Brnsted trn b mt xc tc to thnh cacbocation: Zeol O-H+ + CH2=CH2 CH3-CH2+ + Zeol OBc tip theo, cacbocation s tn cng vng benzen to thnh etylbenzen v tr li proton cho zeolit

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 N MN HC
Trong cc loi xc tc trn, nu nh cc phn ng dng Friedel Crafts pha lng c nhc im ln l xc tc c kh nng gy n mn thit b cao, do yu cu vt liu lm thit b phn ng phi l loi c bit, chu c n mn. Thm vo , sn phm alkyl ha cn c tip tc x l bng ra kim v nc loi b vt AlCl3 hoc BF3 Th xc tc rn li t ra c u th hn, c bit l zeolit, c xem l loi xc tc thch hp cho phn ng alkyl ha do chng c hot tnh cao v chn lc cao hn so vi xc tc dng aluminosilicat v nh hnh. 2.3.2. Xc tc cho phn ng alkyl ha benzen bng etylen a.Xc tc AlCl3 u im Trong cng nghip, qu trnh alkyl ha s dng xc tc ny thng c tin hnh trong pha lng, c chuyn ha cao, xong chn lc sn phm chnh thp, nn phi tun hon polyetylen thc hin phn ng chuyn nhm alkyl, nng cao hiu sut to etylbenzen. Xc tc AlCl3 c u im l c th xc tc cho phn ng chuyn nhm alkyl, do qu trnh ny c th thc hin trong cng thit b phn ng. Nhc im Loi xc tc ny c tnh n mn thit b cao, do , bn trong thit b phn ng phi c lt mt lp vt liu chu n mn hoc thnh thit b phi lm bng thy tnh. Do tc nhn phn ng v xc tc u cng pha lng, sau phn ng cn phi x l bng ra kim v nc loi b vt AlCl3. b.Xc tc rn mang trn cht mang (BF3/Al2O3) u im Loi xc tc ny c tnh n mn thp hn hn so vi xc tc AlCl3 do khng hnh thnh nn dng axit cha proton. Al2O3 + 3BF3 2AlF3 + (BOF)3 bay hi Nhc im Nhc im ca loi xc tc ny l khng cho php tin hnh alkyl ha v chuyn nhm alkyl ng thi nn c hai loi thit b c s dng cho hai qu trnh alkyl ha v chuyn nhm alkyl. c.Xc tc zeolit u im Xc tc zeolit c nh gi l loi xc tc thch hp hn c cho phn ng chuyn ha nhm alkyl, ty thuc vo kch thc mao qun ca xc tc m chn lc sn phm chnh cao. Hn na, s dng xc tc zeolit c th hn ch c s n mn thit b, do thit b c cu to n gin hn, d dng phn tch sn phm ra khi xc tc. SVTH: Nguyn Th Ngn Page 19

 N MN HC
Loi xc tc ny c th ti sinh, do khng gy nh hng n mi trng. Nhc im Xc tc zeolit c nhc im l t hn so vi cc loi xc tc trn, nhng v n c th ti sinh, cng vi nhng hiu qu m n mang li cho qu trnh nh chuyn ha cao, chn lc sn phm chnh ln, s cng ngh n gin do tit kim c chi ph sn xut, chi ph vn hnh v chi ph x l mi trng nn xc tc zeolit vn chim u th trong qu trnh sn xut etylbenzen hin nay. 2.3.3.Cc yu t nh hng n qu trnh alkyl ha C nhiu yu t nh hng n qu trnh alkyl ha, trong nh hng ca nhit , xc tc l ch yu. a.Nhit , p sut

Tng hp etylen bng phng php alkyl ha l mt qu trnh thun nghch, ta nhit (H = -114 kJ/mol [1]) v gim th tch. Do , qu trnh s xy ra thun li iu kin p sut cao v nhit thp. Tuy nhin di 600oC, cn bng phn ng dch chuyn xa sang phi. Cng vi phn ng chnh, mt s phn ng ph cng xy ra ng thi, nh alkyl ha ni tip to sn phm polyetylbenzen, tch nhm alkyl, phn b li v isome ha. p sut kh quyn, alkyl ha benzen c th thc hin 500oC. Tuy nhin, hn ch cc sn phm ph c sinh ra, qu trnh thng tin hnh nhit thp hn v c th di p sut. thc y qu trnh chuyn ha, cc h xc tc thng c s dng. nng cao hiu sut to sn phm chnh, hn ch s hnh thnh cc dn xut polyalkyl, ngi ta s dng d benzen trong vng phn ng. Phn polyalkylbenzen s c tch v a i chuyn ha chuyn nhm alkyl. Phn ng chuyn nhm alkyl ny cng din ra iu kin tng t nh qu trnh alkyl ha, v cn ty thuc vo loi xc tc s dng m c th tin hnh ngay trong thit b phn ng chnh hay thit b ring [1]. b.Xc tc Nu s dng xc tc axit rn s c nh hng ca xp, kch thc l xp, s ph hp ca kch thc phn t sn phm v ng knh l xp ca xc tc Vi xc tc lng, c th xt n yu t SVTH: Nguyn Th Ngn Page 20

 N MN HC
Nhit phn ng: nu tng nhit , nht ca tc nhn v ca xc tc gim, to iu kin khuy trn tt hn. Song khi nhit cao, cc phn ng ph nh polyme ha v oxy ha tng do tc hai phn ng ny mnh hn alkyl ha, v th chn lc ca qu trnh gim xung, do vy phi tin hnh nhit thp. Nng axit: nu nng axit cao, s xc tin cho phn ng alkyl ha xy ra mnh, do to ra nhiu ion cacboni, tuy nhin, sn phm chnh etylbenzen li c chn lc thp, do to ra nhiu sn phm ph polyetylbenzen. Hn na, nu nng axit cao s gy n mn mnh cho thit b phn ng. Tuy nhin, nu s dng xc tc axit long, qu chnh vn chuyn H+ kh khn, dn n gim tc phn ng. 2.4.Dy chuyn v iu kin cng ngh Trong nhng nm gn y, cng ngh sn xut etylbenzen v styren pht trin tp chung vo vn ti u ha cng ngh nng cp xc tc v ci tin thit b. Mt s cng ngh hin i hin nay nh cng ngh EBOne ca hng Lummus/UOP; cng ngh EBMax ca hng Mobil-Badger c nhiu im tng ng, u s dng thit b alkyl ha v thit b chuyn nhm alkyl trong qu trnh. Cng ngh CDTech ca hng Lummus kt hp hai qu trnh phn ng v chng tch trong cng mt thit b. Cng ngh ny cho php s dng nguyn liu etylen c tinh khit thp nh etylen ly t sn phm kh ca qu trnh FCC do gim c gi thnh ca nguyn liu. 2.4.1.Cng ngh alkyl ha pha lng a. Cng ngh alkyl ha pha lng s dng xc tc AlCl3 Cng ngh pha lng s dng xc tc AlCl3 sn xut khong 85% tng sn lng etylbenzen trn th gii [1]. iu kin vn hnh Xc tc: h xc tc ch yu c s dng trong cng ngh ny l h AlCl3/HCl, tuy nhin, gim nguy c n mn thit b, ngi ta thng s dng cht khi mo l etylenclorua: AlCl3/C2H5Cl. Trn thc t, xc tc thng c chun b dng phc , t ha tan trong hydrocacbon: 25- 30% AlCl3 + 45- 50% khi lng benzen/etylbenzen+ 25% hydrocacbon phn t lng ln. iu kin cng ngh Th h cng ngh u tin: P= 0.15 MPa, 80- 110oC, tch nhit bng bay hi benzen. SVTH: Nguyn Th Ngn Page 21

 N MN HC
Th h cng ngh th hai: P= 1 MPa, 160- 180oC, tch nhit bng tun hon sn phm lm lnh ngoi. T l nguyn liu benzen/etylen = 2-2.5. Thnh phn dng sn phm: 41- 43% etylbenzen, 38-40% benzen, 12-14% dietylbenzen, 2-3% trietylbenzen, 1.5-2% polyetylbenzen, 1.5-2 % cc loi khc. Cng ngh s dng xc tc trong pha lng cn c mt nhc im, l qu trnh kh xc tc ha tan trong sn phm. CdF Chimie tm ra bin php thu hi trit hn AlCl3 bng cch trn pha hu c vi amonia thay cho NaOH [2] Cc cng ngh s dng xc tc AlCl3 Cng ngh Mosanto ci tin

Hnh 1. Cng ngh alkyl ha pha lng Mosanto ci tin vi xc tc AlCl3 (a): thit b lm kh benzen (b): thit b phn ng alkyl ha (c): thng chun b xc tc (d): thit b phn ng chuyn nhm alkyl (e): thit b x nhanh (f): thit b ra kh thu hi benzen (g): thit b lng (h): h thng trung ha xc tc Thuyt minh

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 N MN HC

Dng benzen mi v benzen tun hon sau khi qua thp lm kh (a), thit b ra kh thu hi benzen (f) th c a vo thit b phn ng. Dng etylen cng vi etylenclorua c a vo thit b thit b phn ng. Trn nh thp, ngi ta c a thm dng kh N2 vo, c tc dng iu chnh p sut trong thit b phn ng. Dng sn phm sau phn ng, mt phn c a ln thp tch kh (f), phn cn li tip tc i vo thit b phn ng chuyn nhm alkyl (d), cng vi polyetylbenzen tip tc phn ng vi bezen sinh ra etylbenzen. i sang thp x nhanh e, kh c tch ra khi dng sn phm c thnh phn ch yu l N2, dng sn phm i ra y tip tc sang thit b lng (g), h thng trung ha xc tc (h) bng dung dch ammonia. Cui cng ta thu c sn phm etylbenzen c tinh khit cao. u im: hn ch c lng xc tc AlCl3 cn phi s dng, do gim thiu c s n mn, tit kim c chi ph x l xc tc sau phn ng. Hng ny tm ra c rng, khi tng nhit , v iu chnh lng etylen thm vo, s gim c lng AlCl3, do s gim bt s phc tp trong qu trnh phn tch xc tc sau phn ng.

b.Cng ngh alkyl ha pha lng s dng xc tc rn mang trn cht mang Nguyn liu: kh cracking (etylen chim khong 8-10% th tch) Xc tc: BF3/Al2O3 iu kin cng ngh Thit b alkyl ha: thit b on nhit, nhit dng vo 120-130 oC, P= 3.5MPa, m xc tc Al2O3 c nh, BF3 a vo cng dng nguyn liu benzen. Thit b chuyn nhm alkyl: thit b on nhit, T= 200- 210oC, P= 3.5MPa. Cng ngh Alkar S cng ngh

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Nn tun hon

Gia nhit Kh cha olefin

Benzen Mi
P-11

Thit b Phn ng

Sn phm monoalkyl

Tun hon benzen Thit b Phn ng

Thp tch Sn phm

Gia nhit

Benzen tun hon

Polyalkylbenzen tun hon

Hnh 2. Cng ngh alkyl ha pha lng Alkar UOP sn xut etylbenzen Thuyt minh Hai dng nguyn liu benzen ( c trn vi BF3) v dng kh cha etylen i vo thit b phn ng, phn ng xy ra trong pha lng, trn lp xc tc c nh AlCl3. chuyn ha ca phn ng gii hn t 25-30%, trnh ta nhit ln, hn ch to ra nhiu sn phm ph. Nhit ca phn ng cng c tch ra nh qu trnh tun hon, lm lnh bn ngoi. Ti thit b tun hon benzen, pha nh giu benzen v BF3 i ra nh thp , c ngng t v sau c tun hon tr li thit b phn ng (bao gm c thit b alkyl ha v thit b chuyn nhm alkyl). Dng sn phm i ra y thp ny c a sang thp chng ct tch sn phm. Dng sn phm nng cha cc cu t polyetylbenzen i ra y thp c a n thit b chuyn nhm alkyl phn ng vi benzen v to etylbenzen. c.Cng ngh s dng xc tc zeolit trong pha lng Cng ngh alkyl ha thc hin trong pha lng trn xc tc zeolit bt u c thng mi ha nm 1990, nh my u tin c xy dng Nippon SM ti Oita, Nht Bn, v c ng k bn quyn bi hng ABB Lummus Global v Unocal. Cng ngh SVTH: Nguyn Th Ngn Page 24

 N MN HC
ny s dng loi xc tc zeolit Y siu n nh, v gn y hn l xc tc zeolit beta. Mt cng ngh alkyl ha khc cng cho php sn xut etylbenzen trong pha lng, l cng ngh EBMax c pht trin bi hng Mobil-Badger da trn xc tc ca hng Mobil: MCM-22. Nh my s dng cng ngh ny c xy dng u tin Chiba Styrene Monomer Corp, Nht Bn. n cui nm 1999, c tt c 12 nh my alkyl ha benzen bng etylen c xy dng s dng cng ngh alkyl ha trong pha lng [2]. Tuy t c nhng u im ni bt t hai cng ngh alkyl ha trong pha lng, xong cng ngh alkyl ha trong pha hi ca hng Mobil/Badger ra i, cho php s dng nguyn liu etylen c tinh khit thp cho php tit kim hn v chi ph u t, v li thu c sn phm c cht lng cao hn so vi nhng cng ngh i trc, s dng etylen tinh khit lm nguyn liu. Cng ngh Lummus/UOP EBOne

Hnh 3: S cng ngh Lummus/UOP EBOne qu trnh alkyl ha benzen bng etylen (1): thit b phn ng alkyl ha (2): thit b phn ng chuyn nhm alkyl (3): thp chng tch benzen (4): thp chng tch sn phm etylbenzen (5): thp chng tch sn phm polyetylbenzen. SVTH: Nguyn Th Ngn Page 25

 N MN HC

Thuyt minh Trong cng ngh Lummus/UOP EBOne, qu trnh alkyl ha benzen bng etylen c thc hin trong pha lng, trn xc tc zeolit ca hng UOP. Nguyn liu etylen c tinh khit t 70-100% c th lm nguyn liu cho qu trnh. Benzen v etylen phn ng vi nhau trn xc tc zeolit trong thit b xc tc c nh. Bn trong thit b phn ng, ngi ta xc tc thnh nhiu tng, etylen c chia thnh nhiu dng v a vo thit b ti mi tng xc tc, etylen i ln, tip xc v phn ng vi benzen. Phn ng ta nhit mnh, do , vic chia xc tc thnh nhiu tng khng ch gip cho qu trnh phn b tc nhn phn ng c u hn, tng s tip xc trn b mt xc tc m cn c tc dng tch nhit ca phn ng, trnh tch nhit cc b. Benzen cha phn ng c thu hi t dng sn phm nh ca thp s 3, dng sn phm etylbenzen cng c thu hi t dng sn phm nh ca thp s 4. Sn phm ph, polyetylbenzen c tch ra khi sn phm chnh v c thu hi t dng sn phm nh ca thp s 5 v c tun hon li thit b phn ng s 2 thc hin phn ng chuyn nhm alkyl vi benzen v sinh ra etylbenzen, dng sn phm y ca thp 5 thng l phn cn nng, c th c s dng lm nhin liu t. Xc tc s dng trong cng ngh ny l xc tc zeolit, do hn ch c ti a s n mn thit b. qu trnh vn hnh iu kin m du, nn cho php thit b trong qu trnh c th ch to bng thp cacbon. Thi gian lm vic ca xc tc c th ko di t 2-6 nm, sau , xc tc c th c ti sinh hon ton. Sn phm chnh etylbenzen thu c c tinh khit cao ( 99,9 %wt) nn rt thch hp s dng lm nguyn liu sn xut styren, hm lng xylen ln trong sn phm nh hn 10ppm. Hiu sut chung ca qu trnh l khong 99.7%. Cng ngh Mobil badger EBMax

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Hnh 4 : s cng ngh alkyl ha pha lng Mobil Badger EBMax sn xut etylbenzen Thuyt minh: cng ngh Badger EBMax sn xut etylbenzen t nguyn liu benzen v etylen tinh khit hoc etylen/etan trn loi xc tc c bit ca ExxonMobil cho c hai qu trnh alkyl ha v chuyn ha nhm alkyl. Cng ngh ny c th c s dng xy dng ln phn xng sn xut etylbenzen hoc c dng nng cp cng ngh c: cng ngh pha hi, hay chuyn t cng ngh s dng xc tc AlCl3 sang xc tc zeolit. Thit b phn ng alkyl ha (1) v thit b phn ng chuyn ha nhm alkyl (2) c trc rng, bn trong l lp xc tc c nh. Phn ng c th c thc hin trong pha lng hoc pha hn hp lng hi, etylen phn ng vi benzen trong thit b alkyl ha (1) to ra etylbenzen v mt lng nh poly etylbenzen. Trong thit chuyn ha alkyl 2, polyetylbenzen c phn ng vi benzen to ra etylbenzen trn xc tc chuyn nhm alkyl ca ExxonMobil. Dng sn phm ra khi thit b 1, 2 c a vo thp benzen (3) thu hi benzen cha phn ng.

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Nguyn liu benzen mi, cng vi mt lng nh dng i ln t thp 3 c a vo thp 4 l thp light column loi b cc tp cht nh, dng sn phm ra y thp 4 c a tr li thp 3 Dng benzen mi v mt lng nh dng hi i ln t thp thu hi benzen i vo lm nguyn liu cho thp 4 loi b cc tp cht. sn phm y ra khi thp ny c tun hon tr li thp thp tch benzen (3). Dng sn phm y ra khi (3) c a vo thp thch etylbenzen (5) tch sn phm etylbenzen. Dng ra y thp 5 cha ch yu l cc polyetylbenzen, c a vo thp 6 tch cc hp cht diphenyl ra khi cc polyetylbenzen, sau , polyetylbenzen c a tr li thp 2 thc hin phn ng chuyn nhm alkyl vi benzen, sn phm nng ra khi y thp 6 c th c s dng lm nhin liu t. Xc tc: thi gian lm vic ca xc tc cho qu trnh alkyl ha v chuyn nhm alkyl l 4 nm. Cc thit b ca qu trnh c th lm ton b bng thp cacbon. Vn u t ca qu trnh c gim khi xc tc c hot tnh v chn lc cao, v c kh nng xc tc cho c 2 qu trnh alkyl ha v chuyn nhm alkyl vn hnh iu kin d t benzen. Cht lng sn phm tinh khit ca sn phm 99.95- 99.99% wt Hm lng C8+ C9 < 100 ppm. 2.4.2.Cng ngh alkyl ha pha hi

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 N MN HC

a. Cng ngh Mobilbadger

Hnh 5: cng ngh alkyl ha pha hi Mobil-Badger sn xut etylbenzen (a): thit b gia nhit s b (b): thit b phn ng alkyl ha (c): thp thu hi benzen (d): thp thu hi etylbenzen (e): thp thu hi poly etylbenzen (f): thit b phn ng th cp (g): thp n nh. Xc tc: zeolit ZSM-5 ca hng Mobil. Thit b alkyl ha vn hnh trong iu kin T= 350- 450oC, P= 1- 3 MPa. Thuyt minh Cng ngh alkyl ha bezen trong pha hi, trn xc tc zeolit c th vn hnh vi dng nguyn liu etylen c tinh khit thp, c bit c th s dng dng sn phm kh ca qu trnh FCC. Nguyn liu etylen c a vo thit b alkyl ha ti mi tng xc tc, tip xc v phn ng vi benzen a sang t thp thu hi benzen (c). Dng sn phm ra khi thit b phn ng alkyl ha tip tc c a sang cc thp tch benzen, etylbenzen, polyetylbenzen. Benzen cha tham gia phn ng c tch ra thp chng tch benzen (c), sau c tun hon tr li thit b phn ng. Etylbenzen SVTH: Nguyn Th Ngn Page 29

 N MN HC
c ly ra t nh ca thp chng tch etylbenzen th hai (d), dng sn phm i ra t y ca thp ny cha ch yu l cc polyetylbenzen v cc cn nng khc nh diphenylmetan, diphenyletan, tip tc c a sang thp chng th 3 (e) thu hi polyetylbenzen v a sang thit b phn ng th cp (f) thc hin phn ng chuyn nhm alkyl vi benzen. Trong thp ny, iu kin p sut thp hn, nhit cao hn (so vi thit b alkyl ha) cc hp cht alkylbenzen c mnh nhnh di b ct mch alkyl, cc polyalkyl benzen th tham gia phn ng chuyn nhm sinh ra etylbenzen. Thi gian lm vic ca xc tc ko di t 18- 24 thng, ph thuc vo iu kin vn hnh. Sau khong thi gian ny, xc tc b mt hot tnh do s to thnh cc bm trn b mt xc tc, qu trnh ti sinh xc tc c th ko di khong 36h. b. Cng ngh CD Tech pha hn hp

Hnh 6: s cng ngh alkyl ha pha hn hp CDtech sn xut etylbenzen Thit b alkyl ha (1) vn hnh nh mt thp chng. Phn ng alkyl ha v qu trnh chng ct cng xy ra bn trong thp vi s c mt ca xc tc zeolit. Etylen v benzen cha phn ng ra khi nh thp c ngng t v lm nguyn liu cho thit b phn ng 2, thit b ny cng c xc tc zeolit. Dng ra khi y thit b 1 gm c etylbenzen, polyetylbenzen v cn nng (flux oil). SVTH: Nguyn Th Ngn Page 30

 N MN HC
Polyetylbenzen c tch ra v a tr li thit b phn ng 3 thc hin phn ng chuyn ha alkyl vi benzen to ra etylbenzen trn xc tc zeolit.Thit b phn ng c thit k vn hnh lin tc trong vng t 3 n 6 thng, iu kin nhit thp, do cho php thit k bng cc thit b bng vt liu thp cacbon. u im ca cng ngh: cho php sn xut ra etylbenzen c tinh khit cao bng phn ng alkyl ha benzen vi tc nhn etylen s dng cng ngh chng ct xc tc (CD). Thit b phn ng CD c cu trc c bit, bn trong lp xc tc zeolit, c th s dng nguyn liu etylen tinh khit t 10-100% [5] do cho php tit kim c chi ph u t. Nng sut v cht lng sn phm: c hai qu trnh alkyl ha v chuyn ha nhm alkyl u c chn lc cao, to t sn phm ph, etylbenzen thu c c tinh khit trn 99.9%wt [5], rt thch hp lm nguyn liu sn xut styren. Xylen ln trong sn phm c hm lng thp (<10 ppm [5]). Hiu sut chung ca qu trnh th t c 99.7% [5]. 3.So snh v la chn cng ngh 3.1.So snh cng ngh Cng ngh alkyl ha benzen bng etylen thc hin trong pha lng, s dng xc tc AlCl3 tuy ra i sm nht v t c nhng thnh tu khng th ph nhn, song vi nhng hn ch khng th khc phc c ca n, th trong cc nh my hin i ngy nay, cng ngh ny tr thnh lc hu v khng cn c la chn na, m thay vo l cng ngh alkyl ha trong pha hi hoc pha lng nhng vi xc tc zeolit. Mt s nhc im ca cng ngh alkyl ha trong pha lng s dng xc tc AlCl3: Xc tc c kh nng gy n mn thit b cao, do vt liu c s dng ch to thit b phn ng cng nh cc thit b ph tr lin quan n xc tc u phi s dng loi vt liu khng b n mn. Nguyn liu cho qu trnh alkyl ha trn xc tc AlCl3 cn phi c tch nc n gii hn cho php do nc cn ln trong nguyn liu c th gy phn hy xc tc v n mn thit b. Xc tc v tc nhn phn ng l ng pha lng, do cn c thm bc trung ha xc tc tch b hon ton xc tc ra khi sn phm sau phn ng, do s cng ngh cng knh. Do xc tc khng th ti sinh ti s dng nn cn phi c thm bc x l xc tc hn ch nhng nh hng ca n n mi trng Ngy nay, khi mt nh my sn xut etylbenzen mi c xy dng th cng ngh sn xut trong pha hi, hoc pha lng trn xc tc zeolit thng c quan tm n u tin, do tnh kinh t v ti u v cht lng sn phm ca n. SVTH: Nguyn Th Ngn Page 31

 N MN HC
Tuy nhin, gia cng ngh pha hi v pha lng cng c nhng im khc bit Trong cng ngh alkyl ha trong pha hi, thit b phn ng thng vn hnh iu kin nhit cao hn so vi pha lng (400-450oC), nhit , xc tc d b mt hot tnh hn do cc bm hoc b phn hy nhit. Phn ng alkyl ha trong pha lng, etylen thng phn ng ht, do hn ch s dng thit b thu hi khi sau phn ng nn tit kim c chi ph u t. Nu hiu sut sn phm etylbenzen thu c trong alkyl ha pha lng l khong 99.7% th hiu sut etylbenzen trong alkyl ha pha hi ch l 98% [14]. Sn phm thu c ca qu trnh alkyl ha trong pha lng c tinh khit 99.95% [14], v khng ln xylen do rt thch hp lm nguyn liu sn xut styren. la chn c cng ngh ph hp, cc nh sn xut khng ch quan tm n cht lng sn phm to ra, m cc yu t v hiu qu, chi ph u t ban u, cng nh chi ph vn hnh trong qu trnh sn xut cng rt c ch . Di y l bng so snh chi ph sn xut ca mt s cng ngh tiu biu: Bng 5. Chi ph sn xut ca mt s cng ngh sn xut etylbenzen[5] Cng ngh CDTech Nng sut ca qu trnh tinh khit ca etylbenzen, %wt Hm lng tp cht trong sn phm, ppm Vn u t, US$ (500,000 tpy, ISBL Gulf Coast) 99.7% 99.9 10 (xylen) 17 triu $ 99.95- 99.99% 100 (C8 + C9) 10 (xylen) (ISBL Gulf Coast, US $/mtpy) 30-45 Cng ngh EBMax/MobilBadger Cng ngh EBOne Lummus-UOP 99.7%

Nguyn liu(tnh trn mt tn sn phm etylbenzen Etylen, kg Benzen, kg in, kWh Nc lm lnh,m3 SVTH: Nguyn Th Ngn 265 738 20 3 Page 32 265 739 265 738

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Hi cao p tiu th 980 kg Sn xut hi nc p sut thp v p sut trung bnh: 1390 kg

Hi nc , mton (xut khu)

1.3

Du nng, 106kcal

0.6

Bng 6. Th phn ca mt s hng sn xut etylbenzen trn th gii [5] Badger Licensing LLC Lummus Technology & UOP LLC Lummus/Cdtech/Lummus technology and Chemical Research & Licensing Trn th gii, hin nay c khong 4 nh my vn hnh sn xut vi cng sut t 140,000 850,000 tn sn phm mi nm.

Trn th gii, cng ngh Hng Badger c cp EBOne ca hng ny bn quyn cho 47 cng ngh sn xut etylbenzen s dng c la chn cho hn 35 xc tc zeolit, vi tng nng d n, v trong s c 22 nh my hin ang vn sut sn phm t khong hnh. Nng sut sn phm 22 triu tn mi nm, v t t 65,000 n 1,250,000 vt qu khong 17 triu tn mi nm. tn mi nm so vi nng sut ng k bn quyn.

3.2.La chn cng ngh T nhng u nhc im phn tch trn, em la chn cng ngh alkyl ha trong pha lng vi mt s c im sau. Cng ngh thuc bn quyn ca hng UOP & ABB Lummus Global Th phn trn th gii: hin ti c 16 nh my sn xut etylbenzen ang s dng cng ngh ny [14]. Nguyn liu: etylen v benzen Cht lng sn phm: etylbenzen thu c c tinh khit 99.95%wt. Xc tc: zeolit Vt liu ch to thit b: thp cacbon

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 N MN HC
Nhng n lc c thc hin nhm hn ch ti a s to thnh sn phm ph bng cch thay i iu kin phn ng Tp < 270oC ph hp vi iu kin lm vic ca xc tc zeolit. Qu trnh da trn cng ngh c pht trin bi hng UOP & ABB Lummus Global. a.C s ha hc ca qu trnh Etylbenzen c sinh ra trong phn ng alkyl ha benzen bng etylen trn xc tc zeolit. Phn ng alkyl ha lin tip cng xy ra vi mc thp to ra dietylbenzen Benzen + etylen etylbenzen Etylbenzen + etylen dietylbenzen b.M t qu trnh

Hnh 7. S cng ngh alkyl ha trong pha lng ca hng UOP & ABB Lummus Global (H-1) thit b gia nhit (R-1) thit b phn ng alkyl ha SVTH: Nguyn Th Ngn Page 34

 N MN HC

(C-1) thit b lm lnh (L-1) thp tch kh sau phn ng (T-1) thp chng tch benzen (T-2) thp chng tch sn phm etylbenzen Benzen c alkyl ha bng etylen to ra sn phm benzen alkylat. Hn hp sau phn ng c a vo thp chng ct thu hi benzen (T-1) v tch ly sn phm etylbenzen c tinh khit cao (T-2). Do qu trnh to ra sn phm etylbenzen c hiu sut cao nn khng cn s dng thit b chuyn nhm alkyl v khng cn tun hon li dietylbenzen. Phn ng alkyl ha c thc hin pha lng trong thit b phn ng dng ng chm, vi xc tc zeolit t trong cc ng, thit b vn hnh ch on nhit. Nguyn liu etylen (c th cn ln etan) c trn vi benzen theo t l xc nh, c gia nhit n nhit phn ng ri i vo thit b alkyl ha. Hn hp sn phm sau khi i vo thit b lm lnh sang thit b tch kh, kh etan ln trong nguyn liu etylen c tch ra nh thp, ra y thp l hn hp sn phm lng, tip tc i sang thp chng tch benzen. Ti thp ny, benzen i ra nh thp c tun hon tr li thp phn ng. Dng i ra y thp cha etylbenzen, dietylbenzen v mt lng nh benzen tip tc sang thp chng tch sn phm etylbenzen (T-2). Sn phm etylbenzen c ly ra nh T-2 c tinh khit cao, c th s dng trc tip lm nguyn liu sn xut styren.

PHN II. M PHNG CNG NGH BNG PHN MM HYSYS 1.Gii thiu v phn mm hysys M phng li cc cng ngh sn xut l thc hin m hnh ha li s cng ngh trn my tnh, vi qui m nh hn cho php cc k s c th d dng nm bt c cng ngh. Vic m phng thng c thc hin trn cc phn mm chuyn dng, khng ch c kh nng thit k, tnh ton qu trnh m cn c th vn hnh (m phng ng) qu trnh theo cc thng s thit k gip cc k s d dng kim sot c qu trnh trc khi vn hnh trong thc t. Do , vic thc hin m phng l rt cn thit trong qu trnh nghin cu, thit k v a vo xy dng thc t mt qu trnh cng ngh.

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Hin nay trong lnh vc cng ngh ha hc c rt nhiu phn mm m phng nh PRO/II, Dynsim (Simsci), HYSIM, HYSYS,trong ph bin nht l Pro II, Dynsim (Simsci) v Hysys (Aspen Tech). Khng ch l mt cng c m phng mnh, hu ch trong vic nghin cu tnh ton thit k cng ngh, hysys p ng c cc yu cu cng ngh nn tng c bn cho m hnh ha v m phng cc qu trnh cng ngh t khai thc ti ch bin trong cc nh my x l kh,n cc qu trnh cng ngh lc ha du v cng ngh ha hc. Hysys cn c u im l thn thin, d s dng v vn m bo tin cy, do vy m hin nay hysys c s dng rt ph bin trong cc qu trnh nghin cu v thit k. 2.Kt qu m phng phn xng sn xut etylbenzen

Hnh 8.S cng ngh sn xut etylbenzen m phng bng hysys Thuyt minh Dng nguyn liu etylen (50oC, 1 atm) c ln 7% etan c nn ln p sut 4060 atm ti my nn (compressor) sau i vo thit b trn vi dng nguyn liu benzen (gm dng benzen mi v benzen tun hon) c tng p ln 4060 atm bng bm (P) SVTH: Nguyn Th Ngn Page 36

 N MN HC
i vo tit b gia nhit (heater 1) ln nhit phn ng 219oC trc khi vo thit b phn ng. Trong cng ngh, nguyn liu benzen v etylen c s dng vi t l benzen/etylen l 8/1 hn ch s to thnh sn phm ph dietylbenzen. Trong s m phng bng hysys, t l ny c khng ch bng cng c Set m bo cho dng nguyn liu trc khi vo thit b phn ng lun duy tr t l benzen/etylen l 8/1. Trong thit b phn ng, benzen tham gia phn ng alkyl ha vi etylen, chuyn ha ca qu trnh t 100% (tnh theo etylen, v chuyn ha l 12.5% nu tnh theo benzen), chn lc ca sn phm chnh etylbenzen t ti 99.7% do hot tnh v chn lc cao ca xc tc nn khng cn phi s dng thit b chuyn nhm alkyl. Dng sn phm ra khi thit b phn ng i vo thit b lm lnh (cooler) v van gim p n p sut thng (V3) ri i vo thp chng tch kh ra khi hn hp sn phm ca qu trnh. Kh c tch ra l etan (ln trong nguyn liu etylen ban u) c tch ra hon ton nh thp (light column), dng sn phm i ra y thp, tip tc sang thp chng tch benzen cha phn ng (benzen column). Dng benzen thu c nh thp c tun hon ton b tr li qa trnh. Dng sn phm i ra y thp benzen column cha ch yu l etylbenzen v dietylbenzen tip tc c a sang thp chng cui cng tch ly sn phm etylbenzen. Sn phm etylbenzen thu c nh thp c tinh khit rt cao (99.94% mol tng ng vi 99.95%wt) v khng ln xylen nn c th s dng trc tip lm nguyn liu cho qu trnh sn xut styren. Cc thng s cng ngh a.Nguyn liu u vo Phn xng hot ng vi cng sut 80,000 tn/nm, tng ng vi 80,000,000 kg/8000h = 10,000 kg/h b. Thit b phn ng alkyl ha: iu kin lm vic ca thit b phn ng T= 219 oC P = 40 atm Lu lng nguyn liu i vo thp, lu lng mol = 3.651*104 kmol/h T l mol benzen/ etylen = 8/1 Thit b lm vic ch on nhit.

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Vi iu kin lm vic trn, cho php phn ng xy ra trong pha lng, chuyn ha ca phn ng chnh, phn ng alkyl ha benzen bng etylen tnh theo etylen t 99.7%, cn li 0.3% chuyn ha tnh theo etylen to ra sn phm ph l dietylbenzen.

Hnh .iu kin lm vic ca thit b phn ng alkyl ha

Hnh . chuyn ha ca cc phn ng trong thit b alkyl ha

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Hnh .Thnh phn hn hp sn phm sau phn ng b.Thp chng tch kh sau phn ng y l mt thp chng c nhim v phn tch kh ra khi hn hp sau phn ng, hot ng p sut thng 101.3 kPa, 77.94oC. Thp ny c nhim v phn tch hon ton kh etan c ln trong hn hp sn phm sau phn ng ra khi hn hp.

Hnh . thp chng tch kh sau phn ng

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Hnh . iu kin lm vic ca thp chng tch kh sau phn ng

Hnh . Thnh phn ca hn hp sn phm trc v sau khi ra khi thp chng tch kh c.Thp chng thu hi benzen Nhim v ca thp l phn tch ti a lng benzen cha tham gia phn ng cn ln trong hn hp sn phm, tun hon tr li thit b phn ng.

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V cu to, thp c 19 a, iu kin lm vic nh v y thp c ch ra trong bng

Bng . iu kin lm vic ca thp chng thu hi benzen iu kin lm vic Nhit , oC p sut, kPa nh thp 78.7 102 y thp 137.2 110

Hnh . iu kin lm vic ca thp chng thu hi benzen

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Hnh . Thnh phn sn phm trc v sau khi ra khi thp chng. d.Thp chng thu hi sn phm etylbenzen Thp chng thu hi sn phm etylbenzen c nhim v phn tch sn phm etylbenzen ra khi sn phm nng dietylbenzen, nhm thu c etylbenzen c tinh khit cao (trn 99.95%wt [14]) Thp chng ny c 24 a, vn hnh iu kin c ch ra trong bng Bng . iu kin lm vic ca thp chng thu hi sn phm etylbenzen iu kin lm vic Nhit , oC p sut, kPa nh thp 146 101.5 y thp 210 110

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Hnh . iu kin lm vic ca thp chng tch etylbenzen

Hnh . Thnh phn sn phm trc v sau khi ra khi thp chng

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3. M phng ng

a.Kt qu m phng ng

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(ETYLBENZEN-dyn4(2)) 4. Tnh ton cn bng vt cht ca qu trnh 4.1.Tnh ton cn bng vt cht Cng sut ca phn xng sn xut etylbenzen : 80,000 tn/nm tng ng vi 10,000 kg etylbenzen sn xut c trong mi gi. Theo nh lut cn bng vt cht, th tng dng ra bng tng dng vo:

Inert Etylen Benzen Benzen tun hon

Qu trnh tng hp etylbenzen

Etylbenzen (EB) Dietylbenzen (DEB) Benzen prod

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S dng cng c Property Balane Utility tnh ton cn bng vt cht cho qu trnh, kt qu c ch ra trong hnh 9

Hnh . kt qu tnh ton cn bng vt cht ca qu trnh bng Hysys 4.2.Tnh ton cn bng nng lng Theo nh lut cn bng nng lng, th: tng Qthu = tng Qta Trong hnh l kt qu tnh ton cn bng nng lng bng cng c Property Balane Utility ca Hysys:

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Hnh . kt qu tnh ton cn bng nng lng ca qu trnh bng Hysys 5. Cu to thit b phn ng chnh Kt lun TI LIU THAM KHO. 1. Phm Thanh Huyn, Nguyn Hng Lin, Cng ngh tng hp hu c Ha du, NXB KHKT, 2006. 2. Ullmanns encyclopedia of Industrial Chemistry 2007. 3. PGS.TS. inh Th Ng, Ha hc du m & kh, NXB KHKT, 2009. 4. Sami Matar, Lewis F. Hatch,Chemistry of petrochemical process, Gulf Publishing Company, Houston, Texas, 2000. 5. G.Margaret Wells, Handbook of Petrochemicals and Process, Gower Pub, Co, 2010. 6. TS.Nguyn Hng Lin, Bi ging Cng ngh Tng hp Hp cht trung gian,2008. 7. http://www.chemsystems.com/about/cs/news/items/PERP%200708_4_StyreneEB. cfm 8. http://www.plantasquimicas.com/Procesunit/etilbenceno.htm 9. http://www.hunterlab.com/appnotes/an11_96br3.pdf SVTH: Nguyn Th Ngn Page 47

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10. http://www.tandfonline.com/doi/abs/10.1081/LFT-200053893#preview (xc tc) 11. http://www.freepatentsonline.com/5493065.html (MCM-49) 12. http://www.pnas.org/content/96/7/3471.full 13. http://www.scribd.com/doc/55878104/Styrene-Ethylbenzene-ProductionTechnology-Plant-Cost-Supply-Demand-Trade 14. http://www.scribd.com/doc/24119003/Ethyl-Benzene-Project-Report 15. Nguyn Th Minh Hin, Hysys trong m phng cng ngh ha hc, NXB KHKT, 2010. 16. William L. Luyben, Plantwide dynamic simulators in chemical processing and control, Marcel Dekker, Inc, 2002. 17. http://www.icis.com/Articles/1999/06/28/83276/shell-opts-for-lummusuop-eb-oneethylbenzene-process.html (EBZ-600) 18. http://www.docin.com/p-60294786.html (EBZ-800)

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