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M U
S pht trin ca ngnh cng ngh Ha hc trong nhng nm qua chng t du m v kh l nhng ngun nguyn liu l tng cho cng ngh tng hp hu c ha du. T du m v kh qua cc qu trnh tng hp hu c ha du rt nhiu cc hp cht hu c, cc hp cht trung gian quan trng cho cng nghip v i sng c tng hp nn. mi quc gia, vic la chn cng ngh thch hp tng hp tng hp cht da trn ngun nguyn liu u sn c nc . V d trong nhng nam 1960 1970, M, cc cng ngh tng hp hu c ha du thng da trn ngun nguyn liu ph bin l kh thin nhin; trong kh Nht v chu u cng dn chuyn sang nguyn liu u l propan/butan hoc etan. Vi nhng thnh tu t c trong lnh vc cng ngh ha hc, c bit trong lnh vc xc tc v thit b phn ng, mc d gp nhng bin ng v gi thnh nguyn liu u vo, cc cng ngh trong ngnh Cng ngh tng hp hu c - ha du vn lin tc thay i v pht trin. Ci tin v cng ngh dn n vic gim tiu th nng lng, gim tiu hao nguyn liu u v gim vn u t. Vit Nam ngnh ha du cn kh non tr ch c mt s t cc nh my nh nh my nh v ha cht Ph M(PMPC), Nh my in m Ph M, vi ngun nguyn liu v cng ngh ch yu nhp t nc ngoi. Tuy nhin k t khi nh my lc du Dung Quc i vo hot ng th ngun nguyn liu cho ngnh cng nghip ny mt phn c cung ng, gim mt phn ph thuc vo nc ngoi. Mt trong nhng sn phm cng nh nguyn liu ca ngnh ha du l cumen. N va l sn phm ca qu trnh lc du v cng va l nguyn liu tng hp nn cc hp cht hu c qua trng khc nh phenol,xylen, Vi mc ch ca n ny l tm hiu v cc tnh cht ca cumen v cc cng ngh sn xut nn chng cng nh thit k dy chuyn sn xut cumen v m phng bng phn mm Hysys. l nhim v chnh ca n ny.

PHN TNG QUAN


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I. KHI QUT V CUMEN

Cng thc phn t : C9H12 Cumen cn gi l (1-metylety)benzen hoc isopropyl benzen hay 2-phelnylpropan, l mt hydrocacbon thm v l dn xut ca benzen. Do n cng c nhng tnh cht ha l c trng.

I.1. TNH CHT VT L

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Cumen nhit thng l mt cht lng khng mu, d bt la, c mi gn ging xng v khng ha tan vo nc nhng d tan trong cc dung mi hu c nh hexan, dietyl ete, tetraclorua cacbon. Cc gi tr v tnh cht vt l ca cumen c th hin qua bng sau Bng I.1. Mt s c trng k thut ca cumen so vi cc cht khc[17]
Thng s Khi lng phn t T trng 200C Nhit nng chy Nhit si Gii n Di Trn Nhit d chp chy cc kn Gii hn tip xc (ppm; gi) hn % th tch 1,4 7,1 1,3 6,8 1,1 6,4 1,1 6,4 1,1 6,6 0,99 6,7 1,1 8,0
0

n v

benze n

Tolue n

oxylene 106,1 6 0,876 -25,2 144,4

mxylen 106,1 6 0,86 -48 139

pxylen 106,1 6 0,857 -13,3 138,4

Etyl Benze n 106,17

Cume n

vC

78,11

92,13

120,19

0,879 C C 5,53 80,1

0,867 -94,99 110,6

0,867 -94,9 136,2

0,86 -96 152,6

-11,1

4,4

17,2

25

25

15

40,6 (Cc h) 25; 8

5; 8

50; 8

100; 8

100; 8

100;8

100; 8

T bng s liu trn ta d nhn thy cumen tuy kh chy hn cc cht khc song gii hn chy li rt cao nn khi bo qun s kh khn phc tp hn. Ngoi ra so vi cc cht khc th cumen tng i c (ch km benzen) do phi ch bo m an ton trong qu trnh sn xut v s dng. I.2 . TNH CHT HA HC
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V trong cng thc cu to ca cumen c nhn benzen v gc ankyl nn cumen c y tnh cht ca c vng benzen v gc ankyl. I.2.1. Phn ng th Cunen c th xy ra phn ng th vi cc halogen cc v tr khc nhau trong phn t ty thuc vo xc tc v iu kin phn ng.

Ty thuc vo iu kin phn ng m phn ng th c th xy ra cc v tr khc nhau trong phn t, khng nhng th vo vng benzen m cn c th th vo gc ankyl.

Phn ng vi axit Nitric


O N+ O-

H 2SO 4 dac HNO3 - H 2O

cumene

Nitrocumene

I.2.2 Phn ng cng


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Cumen c cha vng benzen nen cng c th tham gia phn ng cng vi Hydro to thnh isopropylxyclohexan, hoc cng x th tham gia phn ng cng vi cc halogen nh Brom, Clo,...
Pt + 3 H2

cumene

isopropylcyclohexan

I.2.3. Phn ng dehydro ha Cumen c cha gc proyl trong phn t nn cng c nhng tnh cht ha hc c trng ca ankal nh phn ng tch 1 phn t hydro to ra - Methylstyrene.
Pt, t 0

+ H2

cumene

I.2.4. Phn ng Oxiha [13] Oxy ha khng hon ton to cumenhydroperoxit

O2
OH O

cumene

cumenhydroperoxide

Tng t nh cc Hydrocacbon khc khi cumen oxyhoa hon ton to ra CO2 v nc


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to C9H12 + 12 O2 9 CO2 + 6 H2O

I.

c tnh v nh hng mi trng[1]

Theo c quan bo v mi trng Hoa K (EPA _ U.S. EnvironmentalProtection Agency) th Cumen l ha cht c c tnh thp.c tnh ca n c nh gi l 11 trong thang im l 100 vi 100 l c cao nht. nh gi ny ch yu da trn 2 yu t : mt l hm lng ti thiu ca ha cht gy nh hng n sc khe v nh gi da trn cc triu chng nh au u, mt, chng mt, ...

Cumen c phi l hp cht gy ung th ?

Theo EPA th cumen l mt hp cht c kh nng gy ung th v c xp vo phn lp D. Tuy nhin cha c nghin cu chuyn su v lu di nn cha c y d liu nh gi. Cumen phn tn vo mt trng nh qu trnh lc du vo t cc sn phm kh, ng thi cn do qu trnh bay hi trong qu trnh s dng v bo qun. Tuy nhin phn nhiu cumen phn tn vo mt trng l do qu trnh trn hay b r r vo mi trng.

Cumen trong khng kh Cumen pht tn vo khng kh s nhanh chng b phn hy di tc dng ca nh sng mt tri. Do n khng tch t nhiu trong khng kh.

Cumen trong nc Cumen khng tan trong nc do n s chuyn thnh dng kh nn s nhanh chng phn hy.

Cumen trong t Khi cumen xung t th a phn s bc hi v b phn hy sinh hc ngay b mt mt t. Do n b hp ph mnh m vi t nn kh nng gy nhim ngun nc ngm l khng cao.

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Con ngi tip xc cumen bng con ng no C nhiu nguyn nhn a cumen vo c th tuy nhin ch yu thng qua con ng h hp l chnh. Ngoi ra cn do thc phm, nc ung b nhim, thao tc khng cn thn dnh vo da,...

Cumen l cht c c th khin chng ta nhc u, chng mt, bun ng... nu liu lng cao c th gy bt tnh; tuy nhin kh nng biu hin thnh bnh l v triu chng cn ph thuc vo nhiu yu t khc nhau nh : + Liu lng tip xc + Thi gian tip xc + Tn s tip xc + Sc khe ca ngi tip xc.. Dnh vo da, Cumen c th gy kh da nu ko di c th gy v vim da. Dnh vo mt gy kh rt, nu khng x l c th gy m mt...

II.

ng dng [13]

Dng ch yu trong qu trnh sn xut Phenol, axetol & Metylstyren hoc c dng nh 1 dung mi. Sn xut Aceton

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Qu trnh oxyhoa cumen sn xut aceton c thc hin t nhng nm 1960 n nay, v l mt trong nhng phng php chnh sn xut Aceton.

Sn xut Phenol

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Phenol cng l mt trong nhng hp cht hu c quan trng dng tng hp nn cc hp cht quan trng khc. Qu trnh sn xut cng tng t nh sn xut Aceton. Dng lm dung mi Cumen c th c dng lm dung mi pha sn, men s v sn mi v sn xut acetophenol, dicumylperoxit v diiso propyl benzen.

Sn xut - Methylstyren

C th s n xu t - Methylstyren t cumen b ng cch kh Cumen.


III.

Tnh hnh sn xut v s dng.[14]

V c bn gn nh ton b cumen c s dng sn xut Phenol v Aceton do vy th trng cumen gn lin vi th trng Aceton v Phenol. Cumen phc v cho mc ch thng mi ch chim khong 4% sn lng cumen trn th gii. V cumen c sn xut v chuyn ha thnh phenol v Aceton ngay ti ch. Cc nc sn xut nhiu nht trn th gii l Hoa K (xut sang c), Nht Bn (xut sang Hn Quc). i Loan cng nhp khu mt khi lng ln cumen sn xut Phenol.

Sn lng cumen ca Hoa K qua cc nm t 1984 1995 [7]

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Hnh IV.1. Sn lng cumen ca Hoa K qua cc nm 1984 1995

Ta thy t nm 1984 -1995 sn lng tng 5,3%, nm 1993-1994 tng 18%, 19941995 tng 7,8%. Tnh n u nm 2011 th trng cumen M tng i khan him do thiu ht ngun nguyn liu propylen v bo tr ca mt s nh my. Do vy vic xut khu cumen sang chu u b hn ch v chuyn sang cc ni khc c nhu cu cao hn nh chu v Nam M.

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Tnh hnh tiu th cumen trn th gii nm 2010[14]

Hnh VI.2. Biu hnh trn th hin tnh hnh tiu th cumen trn th gii nm 2010

Nhn vo biu trn cho thy Hoa K v Ty u l hai th trng tiu th cumen nhiu nht trn th gii, tip n l i Loan, Nht Bn, Trung Quc v Hn Quc. Phn cn li l cc khu vc trung v ng u, Singapo, Thi Lan, trung v Nam M, n ,... Vit Nam tnh hnh sn xut cn s khai cha thc s pht trin, ngun cumen ch yu l nhp khu.

V. Sn xut Cumen
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Cumen c sn xut phc v cho nhiu mc ch khc nhau tuy nhin ty vo mc ch m cht lng ca sn phm cng khc nhau. V.1. Nguyn Liu Nguyn liu sn xut cumen ch yu i t hai ngun chnh l benzen (C6H6) v propylen (C3H6). Nguyn liu cng tinh khit th cht lng sn phm cng cao. Thng thng th c benzen v propylen u qua ch bin nn c tinh khit rt cao ( xp x 100%). + Tnh cht ca Benzen.[17] Khi lng phn t (vC) 78.11 T trng 200C Nhit nng chy (0C) Nhit si (0C) Gii hn n trn (%v) Gii hn n di (%v) 0.789 5.53 80.1 7.1 1.4

Nhit chp chy cc kn (0C) -11 nhit thng Benzen l cht lng khng tan trong nc khng mu v c mi thm. Tuy nhin Benzen li l cht c gy ung th. Do vy trong qu trnh s dng phi lu s r r ca nguyn liu nhm gim thiu s c hi, ngoi ra cn c ngha n an ton lao ng v nguy c chy n. + Tnh cht ca propylen.[18] Khi lng phn t (vC) 42.08 Nhit nng chy (0C) Nhit si (0C) p sut hi 250C (tor) -185.2 -47.6 8690

iu kin thn propylen l cht kh khng mu, khng mi v khng c hi. Tuy nhin do l cht kh nn kh nng chy n rt ln do phi c bit ch trong qu trnh vn hnh v s dng.

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Nh vy ta thy nguyn liu s dng cho qu trnh l tng i nguy him do vy vn an ton trong sn xut phi c bit lu . Nguyn liu benzen v propylen c trn vi nhau theo t l nht nh trc khi a vo thit b phn ng. Thng thng nguyn liu c trn vi t l benzen : propylen la 6 :1 hn ch cc phn ng ph trong qu trnh ng thi to ra sn phm nhiu hn. V.2. Cc phn ng Ha hc xy ra trong qu trnh[19] Trong qu trnh xy ra nhiu phn ng khc nhau bao gm cc phn ng mong mun nh cc phn alkyl ha. Bn cnh cn c cc phn ng khng mong mun nh cc phn ng phn b li nhnh alkyl trong ni phn t (isomerisation) v chuyn nhnh alkyl gia cc phn t vi nhau ( dis-proportionation) Cc phn ng xy ra theo cc c ch khc nhau ty thuc vo iu kin phn ng v xc tc c s dng. V.2.1. Cc phn ng Alkyl ha Propylen phn ng vi Benzen (Phn ng chnh)

K = 2,8 x 107 E = 104174 kJ/kmol y l phn ng mong i nht ca ton b qu trnh.

Cumen phn ng Alkyl ha vi propylen.

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K = 2,32 x 109 E = 146742 kJ/kmol Sau khi sn phm c to ra phn ng trn th tip tc b alkyl ha to para- diisopropyl benzen (p-DIPB) l sn phm khng mong mun, phn ng ny gy hi cho qu trnh, nu xy ra mnh th hiu sut thu c khng cao. Do hn ch n ta cn tng hm lng benzen trong nguyn liu u hn ch v thc hin phn ng phn b li p-DIPB. V.2.2. Cc phn ng ng phn ha Trong phn t cc sn phm thu c c mt hoc nhiu nhnh khc nhau nn chng c th chuyn ha qua li ln nhau. y cng l loi phn ng khng mong mun xy ra trong qu trnh. N t chu nh hng ca p sut, nng cht tham gia.

Chng hn phn ng ng phn ha p-DIPB m-DIPB

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V.2.3. Cc phn ng chuyn ha gc Alkyl

Phn ng gia hai phn t cumen

Phn ng ny rt c hi , v n lm chuyn ha mt phn sn phm thnh cc cht khc. Nhn vo phn trnh phn ng ta c th thm benzen vo hn ch s phn hy ca sn phm. Phn ng phn deankyl ha Ch yu l chuyn mt nhnh ankyl t DIPB sang phn t benzen. y l phn ng ngc vi phn ng alkyl ha v rt c ngha trong qu trnh nhm phn hy bt cc sn phm nng.

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Phn ng ngng t to cc

Cc Ngoi cc phn n trn cn c th xy ra cc phn ng khc nh trng hp propylen, no ha propylen, no ha benzen,...

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VI. C ch phn ng alkyl ha benzen bng propylen [20] Ty thuc vo iu kin phn ng v xc tc s dng m c ch phn ng c th khc nhau, song bn cht ca qu trnh vn l xc tc xit, c th l HCl, AlCl3, HF, H3PO4 c,... ngy nay ngi ta dng Zeolit t hiu qu cao hn. Phn ng ny xy ra theo c ch th electrophin nh sau Chng hn ta dng xc tc l hn hp HCl v AlCl3 VI.1. S hnh thnh ion electrophin Di tc dng ca i lc ca ion H+ do axit phn ly ra cng vi hiu ng siu lin hp trong phn t propylen nn H+ s cng vo C c bc thp hn. Nh vy ion to ra mi c bn cao.

Kt qu to ra ion mang in tch dng gia v ion Cl-

Cl- + AlCl3 AlCl4VI.2. C ch th electrophin


Giai on 1

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Giai on 2

VII. Xc tc cho qu trnh [21] Cng ging nh nhng qu trnh alkyl ha khc th xc tc c s dng xc tc phn ng ankyl ha benzen bng propylen cng c bn cht l cc axit. S pht trin ca xc tc ko theo s pht trin ca cng ngh, c bit sau chin tranh th gii th 2 cng ngh alkyl ha c s pht trin vt bc. u tin s dng cc xc tc pha lng nh cc axit HCl, H2SO4, H3PO4, HF, AlCl3,... n giai on axit mang trn cht mang. Ngy nay vi s pht trin ca khoa hc k thut, cht xc tc c dng thng l Zeolic vi cc loi khc nhau, ch yu l 5 loi sau : -Zeolic, Zeolic Y, ZSM - 12, MCM - 22 v Mordenit. Zeolic vi tinh cht u vit nh th rn, bn vi nhit, c b mt ring ln v chn lc cao l nhng yu t gip nng cao hiu qu ca qu trnh. Ngoi ra n cn c bn ha l cao, d ti sinh v mt mt t nn ngy cng c a chung. Yu t quyt nh n cht lng ca xc tc l b mt ring, ng knh l xp, v bn ha l. Ngoi ra cht lng ca xc tc cn ph thuc rt nhiu vo cch x l ch to xc tc m mi hng c mt quy trnh ring.

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y l mt xc tc thng dng trong sn xut cumen

Hnh VII.1. Cu trc ba chiu ca xc tc -Zeolic

Cng mt cng ngh nhng xc tc s dng khc nhau th hiu qu ca qu trnh cng khc nhau. Chng hn nh chn lc ca cc Zeolic khc nhau nn sn phm thu c cng khc nhau.
Bng VII.1 chn lc ca cc Zeolic khc nhau i vi propylen trong tng hp cumen

-Zeolic 99.87%

Mordenit 98.61%

MCM - 22 98.74%

Zeolic Y 98.30%

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Bng VII.2. chn lc, phn b nhnh ca DIPB v chuyn ha propylen cc nhit khc nhau vi cc Zeolic khc nhau

VIII. Hiu ng nhit [21] Mt vn kh quan trng trong thit k thit b phn ng l phi m bo kh nng tn dng nhit ca cc phn ng ankyl ha Lu rng nhit phi m bo cho s bay hi ca benzen. Nu thit b phn ng on nhit th c th tng nhit cch thay i t l benzen v propylen u vo.Nu t l ny thp th s kch ng qu trnh tng nhit v nu t l ny qu cao thi nhit s gim xung. Do vy nu t l ny qu thp d gy qu nhit v ngc li nu t l ny cao th chn lc tng ln nhng vic ti ch sn phm rt phc tp v nh hng n bay hi ca benzen.

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C th thit k l phn ng vi cht ti nhit c th nng cng nh h nhit khi cn cng c xem l mt gii php.

Hnh VII.2. Biu tng nhit on nhit theo t l B/P


Ta thy nhit cng cao th s gia tng nhit cng nhanh. 1600C th nhit s tng nhit on nhit cng nhanh.

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Hnh VII.. Biu th hin chn lc theo t l B/P nhit 1800C v 2200C 2200C th chn lc ca xc tc cao hon r rt v ch yu cu t l B/P nh hn so vi 1800C.

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IX. Cng ngh sn xut Trn th gii hin c rt nhiu cng ngh khc nhau sn xut cumen; song ty thuc vo tng iu kin v ngun nguyn liu khc nhau m chn cng ngh ph hp. IX.1. Cng ngh Q-Max ca UOP[19] Qu trnh Q-Max nhm mc ch chuyn hn hp ca Benzen v Propylen thnh cumen cht lng cao v s dng xc tc Zeolic. Q-Max c c im ni bc l hiu sut cao, sn phm cht lng cao, t cht thi rn gim u t chi ph hot ng v thn thin vi mi trng. Q-Max c pht trin bi UOP s dng xc tc QZ-2000/QZ-2001 l mt bin th ca -Zeolic.

Hnh IX.1. S cng ngh Q-Max ca UOP

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IX.2. Thuyt minh dy chuyn Q-Max l mt qu trnh sn xut cumen hiu sut cao v cht lng tt.

Xc tc QZ-2000 c s dng trong qu trnh hot ng vi tc dng ca benzen thp. Nh vy chi ph u t c gim kh nhiu. QZ-2000 khng n mn v hot tnh cao. So vi cc cng ngh khc cng da trn xc tc Zeolic th Q-Max l mt cng ngh tuyt vi. Cung cp sn phm cht lng cao v n nh, tp cht c trong nguyn liu cng t b nh hng. Quy trnh cng ngh hin th trn hnh IX.1,xc tc trong thit b phn ng Alkyl ha c chia thnh 4 lp xp trong l. Benzen mi c a vo phn trn ca thp tch propan loi b nc ri a n thit b phn ng alkyl ha nh.Thp phn ng ankyl ha lm vic nhit khong 3000C - 4000C v p sut l 25atm v t l Benzen/propylen l 6 : 1. Ti y xy ra cc phn ng ankyl ha to cumen ng thi cng xy ra cc phn ng ph khc. Sn phm ly ra y bao gm cumen, benzen d, DIPB, ... mt phn c a sang thit b Reboiler un si li v cho tr li thp cnh sn gia cc ngn xc tc sau khi trn vi propylen mi.Phn cn li ca y c thu hi benzen s b hi lu li nh ri chuyn sang thp tch Propan. Thp tch Propan c nhim v chnh l tch Propan v nc ra khi dng sn phm v nguyn liu. ng thi b sung ngun Benzen mi cng vi lng Benzen cha phn ng ly ra phn trn thp cng vi benzen ti to chuyn sang thp ankyl ha. Phn y thp gm hn hp cc sn phm nh y thp ankyl ha nhng tch phn ln benzen v c chuyn sang thp thu hi benzen th. Ti thp ny khng c phn ng no xy ra nhng mc ch thu hi hi benzen. nh thp l hi benzen c a li thp ankyl ha cng vi benzen thp tch propan v c thp Ankyl ha. y cng vn l cc sn phm nh ban u tuy nhin y benzen c tch ra tng i sch. Sn phm tip i sang thp tch cumen. Ti y cumen c tch ra nh thp, cn cc phn nng i sang thp tch DIPB, y phn nng c ly ra y thp cn DIPB c hi lu li thp chuyn ha Alkyl tin hnh phn ng chuyn ha alkyl.

IX.2. Cng ngh ca Dow Kellogg


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Hnh IX.2. S cng ngh sn xut cumen ca Dow-Kellogg Ch thch : R-1 Thit b phn ng Alkyl ha R-2 Thit b chuyn ha Alkyl C-1 Ct tch propan C-2 Ct tch Benzen C- 3 Ct tch Cunene C-4 Ct tch DIPB

Thuyt minh dy chuyn: V c bn s cng ngh ca Dow-Kellogg ging nh ca UOP tuy nhin c s khc nhau ch yu thit b phn ng v np nguyn liu cho qu trnh. y nguyn liu gm Benzen mi v Propylen mi c nng ln nhit phn ng cng vi Benzen tun hon cng i vo thit b trn dng trn thnh mt trc khi i vo thp phn ng nh. Ti y xy ra cc phn ng chnh ca qu trnh nhit khong 1600C 2400C, p sut 25 30bar, t l nguyn liu Benzen/propylen = 5:1. Cng ngh ny do khng c hi lu sn phm nn cht lng thp, sn phm cha nhiu kh,...

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IX.2. Cng ngh ca UOP c in[17]

Hnh IX.3. Cng ngh UOP alkyl ha benzen bng Propylen sn xut cumen Xc tc s dng mt trong cc loi sau : + AlCl3 tin hnh 100C 950C + H3PO4 c hoc khng c cht xc tin mang trn cht rn. + Bentonit c hot ha axit cho php tin hnh phn ng 700C 1050C + Aluminosilicat, s dng dng tng t xc tc Cracking, lm vic 200 C. Vi quy m cng nghip, axit Photphoric (thng l SPA) l loi xc tc ch yu c s dng trong qu trnh tng hp cumen. Trong cc nh my s dng cng ngh nay, cc tc nhn phn ng c lu chuyn hoc t trn xung di (k thut c) hoc t di ln trn (k thut mi). Nguyn liu propylen c tinh khit 92% khi lng b sung thm Propan tun hon to thnh hn hp vi t l mol 1/1 dng vo ca thit b phn ng. Ti y, Benzen mi tun hon cng c trn vi
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n Tt Nghip
hn hp nguyn liu sao cho t l mol Benzen/propylen t 8/1 n 10/1 hn ch s to thnh cc polyalkyl benzen v cc polyme. Hn hp nguyn liu c gia nhit v dn vo nh ca thit b phn ng c cha cc lp m xc tc H3PO4/kizengua c xc tin bng BF3 (theo cng ngh UOP) lm vic 1900C 2000C v 3,5 4 MPa. Tc LHSV tnh theo benzen l 1,5. Propan c cha mt lng nh nc (300ppm) c dn vo gia cc lp m xc tc kim sot nhit phn ng. Sn phm phn ng sau khi c chn lc, propan c phn tch trong thit b kh propan v tun hon mt phn tr li thit b phn ng. Benzen d c tinh khit 99%khi lng thu hi trong cc thp chng ct 30 a. Cumen sn phm s cha khong 1200ppm tp cht ( 0,02% etylbenzen, 0,05% n-propylbenzen, 0,05% butulbenzen). Hiu sut qu trnh theo Benzen l 96% n 97%, v tnh theo Propylen l 91% n 92%. X. Sn phm XI. Thit b phn ng

Sinh Vin : Trng Vn Nam Lp HDK52QN Trang 27

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