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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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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 C
6
H
6
, 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.
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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 C
6
H
6

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 n v Gi tr
Khi lng phn t vC 78.11
T trng 20
o
C 0.879
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Nhit nng chy
o
C 80.1
Gii hn n trong khng kh
Di
Trn
% th tch
1.4
7.1
Nhit chp chy cc kn
o
C -11.1
T trng hi (khng kh = 1) 2.77
Gii hn tip xc (ppm; gi) 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 500
o
C, do cc phn
ng ca benzen thng c thc hin nhit trn 500
o
C. V d, 600
o
C, 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 CO
2
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- 450
o
C 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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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 Saudi Arabian mixed Thistle, U.K Saudi Arabian light
Crude gravity,
o
API 34- 34.9 37.4 34.1
Sulfur, wt % 1.63 0.31 1.72
C
5
and lighter, vol % 1.6 3.3 1.5
Light naphtha, yield,
vol % (debutanized)
13.7 13.23 9.3
T.b.p.*range,
o
C C
5
126 ** 31- 105 C
5
- 93 **
End point,
o
C 132
Gravity,
o
API 72.5 71.3 75
Sulfur, wt % 0.02 0.04 0.03
Aromatics, vol% 5 3.1 2.4
Naphthens, vol% 5 30.5 12.3
Paraffins, vol % 90 66.4 85.3
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(T.b.p: true boiling point distillation.
C
5
refers to C
5
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 C
3
, C
4
. 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
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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 CO
2
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 C
2
H
4
Phn t lng M= 28.52 vC
Cng thc cu to CH
2
=CH
2

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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
o
C -169.15
Nhit si
o
C -103.71
Nhit ti hn, T
c
o
C 9.90
p sut ti hn, P
c
MPa 5.117

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.
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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 4
o
C
trnh etylen b ha lng. Nu c mt nc trong ng, hydrate c th to thnh iu kin
T< 15
o
C, 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.
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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 (C
2
H
5
-) nh trc tip vo vng benzen.
Etylbenzen ch yu c s dng (>99%) lm nguyn liu sn xut ra mono
styren (C
6
H
5
CH=CH
2
), 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*10
6
tn [2].
1.3.1.Tnh cht vt l
Cng thc phn t C
8
H
10

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 n v Gi tr
Khi lng phn t vC 106.17
T trng 20
o
C 0.867
Nhit nng chy
o
C -94.9
Nhit si
o
C 136.2
Gii hn n trong khng kh
Di
Trn
% th tch
0.99
6,7
Nhit chp chy cc kn
o
C 15
T trng hi (khng kh = 1) 3.7
Gii hn tip xc (ppm; gi) 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 (C
6
H
5
CH(OOH)CH
3
).
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 AlCl
3,

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 Gi tr
tinh khit ca sn phm
99.5% wt
Hm lng benzen
0.05- 0.3% wt
Hm lng toluen
0.1- 0.3 %wt
Hm lng hp cht nonaromatics
0.05%wt, max
Hm lng propylbenzen
0.02% wt, max
Hm lng dietylbenzen
10 mg/kg, max
Hm lng hp cht cha Cl
-

1-3 mg/kg, max
Hm lng lu hunh hu c
4 mg/kg, max
T trng 15
o
C
0.869- 0.872
APHA colour
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, CO
2
, 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.
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SVTH: Nguyn Th Ngn Page 14

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
C
n
H
2n+2
+ C
m
H
2m
C
n+m
H
2(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.

N MN HC


SVTH: Nguyn Th Ngn Page 15

NaSH + RCl RSH + NaCl
ROH + NH
3
RNH
2
+ H
2
O

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, Pb-
alkyl ha), phn ng ny c ng dng tng hp cc hp cht c kim.
2RCl + Si R
2
SiCl
2
4C
2
H
5
Cl + 4PbNa Pb(C
2
H
5
)
4
+ 4NaCl +3Pb
3C
3
H
6
+ Al + 3/2H
2
Al(C
3
H
7
)
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,
N MN HC


SVTH: Nguyn Th Ngn Page 16

trong cc phn ng thng sinh ra nc c kh nng lm phn hy xc tc
AlCl
3,
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:
N MN HC


SVTH: Nguyn Th Ngn Page 17


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 AlCl
3
, 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


N MN HC


SVTH: Nguyn Th Ngn Page 18

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 H
2
SO
4
, HF

Xc tc l axit Lewis nh AlCl
3
, 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 Al
2
O
3,
Al
2
O
3
/SiO
2

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
+
+ CH
2
=CH
2
CH
3
-CH
2
+
+ Zeol O
-

Bc tip theo, cacbocation s tn cng vng benzen to thnh etylbenzen v tr li
proton cho zeolit


N MN HC


SVTH: Nguyn Th Ngn Page 19

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 AlCl
3
hoc BF
3

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 AlCl
3

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 AlCl
3
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 AlCl
3
.
b.Xc tc rn mang trn cht mang (BF
3
/Al
2
O
3
)
u im
Loi xc tc ny c tnh n mn thp hn hn so vi xc tc AlCl
3
do khng hnh
thnh nn dng axit cha proton.
Al
2
O
3
+ 3BF
3
2AlF
3
+ (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.
N MN HC


SVTH: Nguyn Th Ngn Page 20

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 600
o
C, 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 500
o
C. 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
N MN HC


SVTH: Nguyn Th Ngn Page 21

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 AlCl
3

Cng ngh pha lng s dng xc tc AlCl
3
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 AlCl
3
/HCl,
tuy nhin, gim nguy c n mn thit b, ngi ta thng s dng cht khi mo l
etylenclorua: AlCl
3
/C
2
H
5
Cl. Trn thc t, xc tc thng c chun b dng phc
, t ha tan trong hydrocacbon: 25- 30% AlCl
3
+ 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- 110
o
C, tch nhit bng bay hi
benzen.
N MN HC


SVTH: Nguyn Th Ngn Page 22

Th h cng ngh th hai: P= 1 MPa, 160- 180
o
C, 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 AlCl
3
bng cch trn pha hu c vi amonia thay cho NaOH [2]
Cc cng ngh s dng xc tc AlCl
3

Cng ngh Mosanto ci tin

Hnh 1. Cng ngh alkyl ha pha lng Mosanto ci tin vi xc tc AlCl
3
(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
N MN HC


SVTH: Nguyn Th Ngn Page 23

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 N
2

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 N
2
, 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 AlCl
3
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 AlCl
3
,
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: BF
3
/Al
2
O
3

iu kin cng ngh
Thit b alkyl ha: thit b on nhit, nhit dng vo 120-130
o
C,
P= 3.5MPa, m xc tc Al
2
O
3
c nh, BF
3
a vo cng dng
nguyn liu benzen.
Thit b chuyn nhm alkyl: thit b on nhit, T= 200- 210
o
C, P=
3.5MPa.
Cng ngh Alkar
S cng ngh



N MN HC


SVTH: Nguyn Th Ngn Page 24

P-11
Sn phm monoalkyl
Polyalkylbenzen tun hon
Benzen tun hon
Nn tun hon
Kh cha
olefin
Benzen
Mi
Thit b
Phn ng
Thit b
Phn ng
Tun hon benzen
Thp tch
Sn phm
Gia nhit
Gia nhit

Hnh 2. Cng ngh alkyl ha pha lng Alkar UOP sn xut etylbenzen

Thuyt minh
Hai dng nguyn liu benzen ( c trn vi BF
3
) v dng kh cha etylen i vo
thit b phn ng, phn ng xy ra trong pha lng, trn lp xc tc c nh AlCl
3
.
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 BF
3
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
N MN HC


SVTH: Nguyn Th Ngn Page 25

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.
N MN HC


SVTH: Nguyn Th Ngn Page 26

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

N MN HC


SVTH: Nguyn Th Ngn Page 27



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 AlCl
3
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.
N MN HC


SVTH: Nguyn Th Ngn Page 28

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 C
8
+

C
9
< 100 ppm.
2.4.2.Cng ngh alkyl ha pha hi

N MN HC


SVTH: Nguyn Th Ngn Page 29

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- 450
o
C, 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
N MN HC


SVTH: Nguyn Th Ngn Page 30

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).
N MN HC


SVTH: Nguyn Th Ngn Page 31

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
AlCl
3
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 AlCl
3
:
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 AlCl
3
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.
N MN HC


SVTH: Nguyn Th Ngn Page 32

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 (400-450
o
C), 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
Cng ngh
EBMax/Mobil-
Badger
Cng ngh
EBOne
Lummus-UOP
Nng sut ca qu trnh
99.7% 99.7%
tinh khit ca etylbenzen, %wt
99.9 99.95- 99.99%
Hm lng tp cht trong sn phm,
ppm
10
(xylen)
100
(C
8
+ C
9
)
10
(xylen)
Vn u t, US$
(500,000 tpy, ISBL Gulf Coast)

17
triu $
(ISBL Gulf Coast,
US $/mtpy)
30-45
Nguyn liu(tnh trn mt tn sn phm etylbenzen
Etylen, kg
265 265 265
Benzen, kg
738 739 738
in, kWh
20
Nc lm lnh,m
3

3
N MN HC


SVTH: Nguyn Th Ngn Page 33

Hi nc , mton (xut khu)
1.3 Hi cao p tiu th 980 kg
Sn xut hi nc p sut
thp v p sut trung bnh:
1390 kg

Du nng, 10
6
kcal
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
Hng Badger c cp
bn quyn cho 47 cng ngh
sn xut etylbenzen s dng
xc tc zeolit, vi tng nng
sut sn phm t khong
22 triu tn mi nm, v
vt qu khong 17 triu
tn mi nm so vi nng
sut ng k bn quyn.
Trn th gii, cng ngh
EBOne ca hng ny
c la chn cho hn 35
d n, v trong s c 22
nh my hin ang vn
hnh. Nng sut sn phm
t t 65,000 n 1,250,000
tn mi nm.
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.


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
N MN HC


SVTH: Nguyn Th Ngn Page 34

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 T
p
< 270
o
C 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
N MN HC


SVTH: Nguyn Th Ngn Page 35

(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.
N MN HC


SVTH: Nguyn Th Ngn Page 36

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 (50
o
C, 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)
N MN HC


SVTH: Nguyn Th Ngn Page 37

i vo tit b gia nhit (heater 1) ln nhit phn ng 219
o
C 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
o
C
P = 40 atm
Lu lng nguyn liu i vo thp, lu lng mol = 3.651*10
4
kmol/h
T l mol benzen/ etylen = 8/1
Thit b lm vic ch on nhit.
N MN HC


SVTH: Nguyn Th Ngn Page 38

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

N MN HC


SVTH: Nguyn Th Ngn Page 39


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, 77.94
o
C. 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
N MN HC


SVTH: Nguyn Th Ngn Page 40


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.
N MN HC


SVTH: Nguyn Th Ngn Page 41

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 nh thp y thp
Nhit ,
o
C 78.7 137.2
p sut, kPa 102 110



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

N MN HC


SVTH: Nguyn Th Ngn Page 42


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 nh thp y thp
Nhit ,
o
C 146 210
p sut, kPa 101.5 110

N MN HC


SVTH: Nguyn Th Ngn Page 43


Hnh . iu kin lm vic ca thp chng tch etylbenzen


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


SVTH: Nguyn Th Ngn Page 44

3. M phng ng

a.Kt qu m phng ng

N MN HC


SVTH: Nguyn Th Ngn Page 45



(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 Etylbenzen (EB)
Benzen Dietylbenzen (DEB)
Benzen tun hon Benzen prod


Qu trnh
tng hp
etylbenzen
N MN HC


SVTH: Nguyn Th Ngn Page 46

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 Q
thu
= tng Q
ta
Trong hnh l kt qu tnh ton cn bng nng lng bng cng c Property Balane
Utility ca Hysys:

N MN HC


SVTH: Nguyn Th Ngn Page 47


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
N MN HC


SVTH: Nguyn Th Ngn Page 48

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-Production-
Technology-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-one-
ethylbenzene-process.html (EBZ-600)
18. http://www.docin.com/p-60294786.html (EBZ-800)