CHNG I: QU TRNH ALKYL HA

Qu trnh alkyl ha l qu trnh a cc nhm alkyl vo vo phn t cc cht hu c hoc v c. Cc phn ng alkyl ha c gi tr thc t cao trong vic a cc nhm alkyl vo hp cht thm, izoparafin, mercaptan, sulfid, amin, cc hp cht cha lin kt ete... ngoi ra qu trnh alkyl ha l nhng giai on trung gian trong sn xut cc monome, cht ty ra...

1. C TRNG CA QU TRNH ALKYL HA

I. Phn loi cc phn ng alkyl ha S phn loi hp l nht cc qu trnh alkyl ha l da trn loi lin kt c hnh thnh.
1. Alkyl ha theo nguyn t C: cn gi l qu trnh C - alkyl ha

C - alkyl ha l th nguyn t H gn vi C bng cc nhm alkyl. CnH2n+2 + CmH2m Cn+mH2(n+m)+ 2 ArH + RCl ArR + HCl
2. Alkyl ha theo nguyn t O v S: cn gi l qu trnh O - alkyl ha v S -

alkyl ha O - alkyl ha v S - alkyl ha l cc phn ng dn n to thnh lin kt gia nhm alkyl v nguyn t O hoc S. ArOH + RCl + NaOH ArOR + NaCl + H2O

NaSH + RCl RSH + NaCl

3. Alkyl ha theo nguyn t N: cn gi l qu trnh N - alkyl ha

N - alkyl ha l th cc nguyn t H trong amoniac hoc trong amin bng cc nhm alkyl. y chnh l mt trong nhng phng php quan trng nht tng hp cc amin. ROH + NH3 RNH2 + H2O
4. Alkyl ha theo cc nguyn t khc:

Cc qu trnh Si -, Pb -, Al - alkyl ha... l con ng quan trng tng hp cc hp cht c nguyn t hoc c kim. 2 RCl + Si R2SiCl2 4 C3H7Cl + 4 NaPb (xc tc l Cu) Pb(C3H7)4 + 4 NaCl + 3 Pb Al(C2H5)3

3 C2H4 + Al + 3/2 H2 II.

Cc tc nhn alkyl ha v xc tc Cc tc nhn alkyl ha c th chia lm 3 nhm:

a) Cc hp cht khng no (olefin v acetylen), trong s ph v cc

lin kt ca cc nguyn t C. b) Dn xut Cl vi cc nguyn t Cl linh ng c kh nng th di nh hng ca cc tc nhn khc nhau. c) Ru, ete, este, oxyt olefin l cc tc nhn m trong qu trnh alkyl ha lin kt C - O s b ph v. 1. Tc nhn l olefin - xc tc v c ch Trong cc loi tc nhn th tc nhn olefin c gi thnh kh r, v vy ngi ta lun c gng s dng chng trong mi trng hp c th. Cc olefin (etylen, propylen, buten v cc olefin cao phn t) ch yu c s dng C - alkyl ha cc parafin v cc hp cht thm. Xc tc: acid proton (a.Bronsted) hoc acid phi proton (a.Lewis)

C ch: ch yu xy ra theo c ch ion qua giai on trung gian hnh thnh cacbocation. Kh nng phn ng ca cc olefin c nh gi bng mc to ra cacbocation: RCH = CH2 + H+ RC+H - CH3 Qu trnh ny chu nh hng ca s tng chiu di mch, phn nhnh

ca olefin: CH2 = CH2 < CH3 - CH = CH2 < CH3 - CH2 - CH = CH2 < (CH3)2C = CH2

 Tc nhn olefin c mch cng di, cng phn nhnh th kh nng phn ng cng ln. Ngoi ra trong rt nhiu trng hp, qu trnh alkyl ha bng olefin c th xy ra di tc dng ca cc cht khi mo phn ng chui gc, hoc tc dng ca nh sng hoc tc dng ca nhit cao. Khi cc phn t trung gian l cc gc t do v trong trng hp ny kh nng phn ng ca cc olefin c cu to khc nhau cng khng khc nhau nhiu. 2. Tc nhn l cc dn xut clo - xc tc v c ch Cc dn xut clo c xem l cc tc nhn alkyl ha tng i thng dng nht trong cc trng hp O -, S -, N - alkyl ha v tng hp phn ln cc hp cht c kim, c nguyn t; ngoi ra cn c s dng trong trng hp C - alkyl ha.

C - alkyl ha: xy ra theo c ch i in t di tc dng cht xc tc l cc acid phi proton (FeCl3, AlCl3) qua giai on trung gian hnh thnh cacbocation: RCl + AlCl3 R+ Cl -AlCl3 R+ + AlCl4Kh nng phn ng ca cc alkyl clorua ph thuc vo phn cc ca lin kt C-Cl hoc vo bn cacbocation v s tng khi chiu di v mc phn nhnh ca nhm alkyl tng: CH3CH2Cl < (CH3)2CHCl < (CH3)CCl3

O -, S-, N - alkyl ha: xy ra theo c ch i nhn v khng cn xc tc RCl + :NH3 RN+H3 + Cl- RNH2 + HCl Kh nng phn ng ca cc dn xut clo c sp xp theo dy: ArCH2Cl > CH2 = CH - CH2Cl > AlkCl > ArCl v AlkCl bc I > AlkCl bc II > AlkCl bc III

Trong tng hp c kim v c nguyn t: xy ra theo c ch gc t do di tc dng ca kim loi

4 NaPb + 4 C2H5Cl 4 Pb + NaCl + 4 C2H5 4 NaCl + Pb(C2H5)4 + 3 Pb

3. Tc nhn l cc hp cht c cha O - xc tc v c ch

Cc tc nhn alkyl ha c cha O nh ru, ete, este, oxyt olefin c th dng trong cc qu trnh C -, O -, N - v S - alkyl ha; tuy nhin trn thc t ngi ta s dng ch yu l cc oxyt olefin. Qu trnh xy ra theo c ch cacbocation di tc dng ca xc tc l acid proton lm t lin kt gia nhm alkyl v oxy: ROH + H+ R - +OH2 R+ + H2O III. c tnh nng lng ca cc phn ng alkyl ha Cc c tnh nng lng ph thuc vo tc nhn alkyl ha v dng lin kt b ph v trong cht alkyl ha. Mt s thng s nng lng trong qu trnh alkyl ha c trnh by bng sau: Tc nhn alkyl ha RCH = CH2 RCl ROH CH2 - CH2 O CH CH Lin kt b ph v C - H Car - H O-H Car - H O-H N-H O-H N-H O-H O-H -Ho298 , kJ/mol 84 100 96 104 50 63 34 42 0 0 25 0 21 21 42 88 104 100 117

2. ALKYL HA THEO NGUYN T CACBON

Qu trnh C - alkyl ha ch yu xy ra vi cc hp cht thm v parafin vi nhiu nghi thc t to ln. I. Alkyl ha cc hp cht thm

1. Ha hc v c s l thuyt 1.1. Xc tc Tu thuc vo tc nhn alkyl ha m c th s dng cc xc tc khc nhau. Cc tc nhn alkyl ha hydrocacbon thm s dng ch yu trong cng nghip l cc dn xut clo v olefin. Ru t c s dng cho qu trnh alkyl ha hydrocacbon thm v c kh nng alkyl ha km hn.

Khi tc nhn l cc dn xut clo: xc tc hu hiu nht l cc acid phi proton, ph bin nht l AlCl3. Hn hp phn ng trong pha lng khi alkyl ha vi xc tc AlCl3 bao gm 2 pha: phc xc tc v lp hydrocacbon.

Khi tc nhn l olefin: thng dng xc tc l AlCl3; ngoi ra c th dng a.H2SO4, HF, H3PO4 trn cht mang, aluminosilicat, zeolit... Trong :
o Khi xc tc l a.H2SO4 hoc HF: + qu trnh pha lng

+ t = 10 40oC + p = 0,1 1 MPa

o Khi xc tc l a.H3PO4 rn:

+ qu trnh pha kh + t =225 275oC + p = 2 6 MPa

o Khi xc tc l aluminosilicat, zeolit: kh

+ qu trnh pha lng hoc pha

+ t = 200 400oC + p = 2 6 MPa Nh vy, i vi qu trnh C-alkyl ha th xc tc AlCl3 chim v tr p o v c nhiu u th.

AlCl3 trng thi rn hu nh khng tan trong hydrocacbon v xc tc rt yu cho phn ng. Tuy nhin theo mc hnh thnh HCl, AlCl3 bt u chuyn qua trng thi lng c mu sm. Cht lng ny mc d khng tan trong hydrocacbon nhng c hot tnh rt ln v do tc phn ng s tng ln. Trng thi hot ng ca AlCl3 c th chun b bng cch sc kh HCl qua h huyn ph ca AlCl3 trong hydrocacbon, khi s hnh thnh phc ca AlCl3 v HCl vi 1 n 6 phn t hydrocacbon thm, trong mt phn t ny nm trng thi cu trc c bit mang in tch dng (phc ) cn cc phn t cn li hnh thnh lp solvat:
H H . (n-1) ArH Al2Cl7
-

Nhm t c vn tc alkyl ha cao ngay t thi im bt u phn ng, phc ny thng c chun b trc ri sau a vo h phn ng. 1.2. C ch phn ng phc phn cc mnh (phc ) v hnh thnh cacbocation RCl + AlCl3 R+ Cl -AlCl3 R+ + AlCl4R + R
+

1.2.1. Khi tc nhn l dn xut Clo RCl: xc tc AlCl3 s hot ha Cl to ra

R + H+

1.2.2. Khi tc nhn l olefin: xc tc AlCl3 s kt hp vi cht ng xc tc l

HCl to ra cacbocation RCH = CH2 + HCl + AlCl3 RC+H - CH3 + AlCl4Trong trng hp ny cu to ca nhm alkyl trong sn phm c xc nh theo nguyn tc v s to thnh cacbocation bn vng nht giai on trung gian (bc III > bc II > bc I). 1.3. Cc phn ng ph Cc phn ng ph c th xy ra trong qu trnh alkyl ha hydrocacbon thm:

 Alkyl ha ni tip Nha ha Phn hy cc nhm alkyl Polyme ha olefin Phn ng alkyl ha ni tip: Khi alkyl ha cc hp cht thm vi s c mt ca xc tc bt k s xy ra s th ni tip cc nguyn t H v to thnh hn hp sn phm vi mc alkyl ha khc nhau. V d khi etyl ha C6H6 s xy ra n khi to thnh hexa etylbenzen:
C6H6
+ C2H4

C6H5 - C2H5

+ C2H4

C6H4- (C2H5)2

+ C2H4

C6H3- (C2H5)3 v.v.

Mi phn ng trong dy ny u l cc phn ng bt thun nghch. Tuy nhin khi dng xc tc Aluminosilicat hoc Zeolit iu kin tng i khc nghit hoc khi dng xc tc AlCl3 th s xy ra phn ng thun nghch vi s dch chuyn v tr ca cc nhm alkyl:
C6H4R2 + C6H6 C6H3R3 + C6H6 2 C6H5R C6H5R + C6H4R2

Kh nng dch chuyn v tr ca cc nhm alkyl c sp xp theo dy: (CH3)3C- > (CH3)2CH- > CH3 - CH2- >> CH3Cc kh nng hnh thnh sn phm ni tip:
R R R
+R
+

+ R+

+ R+

R R R R R R R R

R R

+ R+

 Phn ng nha ha Nguyn nhn l do cc vng thm ngng t nhit cao to thnh cc sn phm nh diarylalkan, triarylalkan, diarylolefin ... Nhit cng tng phn ng nha ha hnh thnh hp cht a vng s cng tng. Phn ng phn hy cc nhm alkyl Nguyn nhn l do khi iu kin phn ng khc nghit s thc y s phn hu cc nhm alkyl v to ra cc sn phm ph c mch alkyl ngn. V d: + Khi C3H6 phn ng vi C6H6 c hnh thnh sn phm C6H5-C2H5 + Khi C2H4 phn ng vi C6H6 c hnh thnh sn phm C6H5-CH3. Mch alkyl cng di cng d b phn hy. S phn hu c kh nng xy ra giai on tch cacbocation.
RC+H - CH2R RCH = CH2 + R+
+ 2 C6H6 - H+

C6H5 - CH - CH3 + C6H5R H

Phn ng polyme ha olefin Nguyn nhn l do s kt hp ni tip ca cacbocation vi olefin (trng hp cation)
CH3- C+H2
+ C2H4

CH3- (CH2)2- C+H2

+ C2H4

CH3- (CH2)4- C+H2 ....

Polyme sinh ra c khi lng phn t khng ln v c th hn ch bng lng d hydrocacbon thm v gim nng olefin trong pha lng. 2. Thit b phn ng Hin nay c 3 loai thit b phn ng lin tc alkyl ha cc hydrocacbon thm vi xc tc AlCl3.

Alkylat Alkylat C6H6 tc nhn alkyl ha Xc tc Alkylat kh

H2O olefin H2O C6H6

H2O C6H6 + olefin (hay RCl) + xc tc a

Hnh 1. Cc loi thit b phn ng alkyl ha hydrocacbon thm vi xc tc AlCl3 a. Thit b ng chm - b. H thit b ni tip - c. Thit b dng ng 3. Cng ngh alkyl ha cc hydrocacbon thm C hai hp cht alkyl vng thm tiu biu c sn xut vi sn lng ln nht l etylbenzen v iso propylbenzen. 2.1. Tng hp Etylbenzen 2.1.1. Tnh cht ca etylbenzen iu kin thng, etylbenzen l mt cht lng sng khng mu, c mi thm c trng, c nhit si 136,186oC. Etylbenzen gy bng da v mt, trong mt gii hn no cng gy c qua ng h hp v n ung, ng thi hp ph qua da. Hu ht etylbenzen (>99%) c s dng sn xut monome Styren (C6H5CH=CH2) v n l hp cht ch o m bo iu kin k thut cng nh thng mi cho qu trnh sn xut styren. y l mt monome rt quan trng trong lnh vc sn xut cht do v cao su tng hp. Ch c khong 1% etylbenzen c s dng lm dung mi pha sn hay lm hp cht trung gian sn xut dietylbenzen v acetophenol.

2.1.2. Cng ngh Hin nay hu ht etylbenzen sn xut trong thng mi u t qu trnh alkyl ha benzen bng etylen. S sn xut etylbenzen tiu th 50% lng benzen trn th gii. Qu trnh alkyl ha ny c tin hnh ch yu theo 2 phng php: - Tin hnh trong pha lng vi xc tc AlCl3 - Tin hnh trong pha hi vi xc tc rn tng c nh Phn ng : y l phn ng ta nhit mnh C6H6 + C2H4 a. Qu trnh pha lng T nhng nm 1930, cng ngh alkyl ha pha lng vi xc tc AlCl3 c a vo s dng vi nhng c tnh u vit. Nhiu cng ngh pht trin da trn s ci tin qui trnh cng ngh ban u ny, tuy nhin n hin nay qui trnh ca Monsanto s dng xc tc AlCl3 l qui trnh thng mi hin i nht. Qu trnh alkyl ha benzen bng etylen trn xc tc AlCl3 l mt phn ng ta nhit xy ra rt nhanh v phn ln to thnh etylbenzen. Ngoi xc tc AlCl 3 cn c nhiu xc tc acid Lewis khc c s dng nh AlBr 3, FeCl3, BF3. Ngoi ra ngi ta cn a vo nhng cht kch ng halogen nh etylclorua hay hidroclorua c tnh cht kch ng xc tc, lm gim lng AlCl3 cn thit. C ch hot ng ca h xc tc AlCl3 - HCl nh sau: C2H4 + HCl + AlCl3 C6H6 + C2H5+ + AlCl4C6H6 - C2H5+ - AlCl4 C2H5+ + AlCl4C6H6 - C2H5+ - AlCl4C6H5 - C2H5 + AlCl3 + HCl C6H5 - C2H5 -H0298 = 114 kJ/mol

* iu kin vn hnh phn xng:

Nguyn liu benzen phi sy kh trc khi s dng (< 30 ppm H2O) Nhit t = 160 180oC tng ng vi p sut tuyt i p = 1.106 Pa iu chnh t s = benzen/nhm etyl = 2 2,5 hiu sut thu sn phm ti a

VVH 2 Thu hi nhit ta ra sn xut hi nc p sut thp nhm gim nhit phn ng, gip cn bng dch chuyn theo chiu thun * S cng ngh: Hnh 2
AlCl3 EB hi lu Kh thi NH3

N2

h
C6H6

h
H2O C6H6 hi lu

g
mui thi

d e

EB th i lm tinh Poly etylbenzen hi lu

C2H4 C2H5Cl trong C6H6

Hnh 2: Qu trnh alkyl ha sn xut Etylbenzen vi pha lng ng th a. thp kh nc - b. Thit b phn ng alkyl ha - c. Thng chun b xc tc d. Thit b chuyn v alkyl - e. Thit b bay hi - f. Thit b ra kh thi g. Thit b tch lng - h. H thng trung ha - i. Thit b to hi p sut thp * Thuyt minh: Benzen c lm kh thp tch nc (a) ri a qua h thng lm sch kh thi (f), sau trn vi dng xc tc v etylbenzen hi lu n t thng cha xc tc (c) cng vo thit b phn ng alkyl ha (b). Etylen v cht kch ng c a vo thit b phn ng t di ln qua b phn phn phi. Dng lng i ra khi thit b phn ng c trn vi dng poly alkylbenzen hi lu i vo thit b chuyn v alkyl (d). So vi cng ngh trc y, cng ngh ny poly

alkylbenzen khng c hi lu trc tip v thit b phn ng do s hi lu vi mt lng ln vi nng xc tc thp s lm ngng phn ng alkyl ha. Ngi ta s dng mt thit b chuyn v alkyl ring (d), trong thit b ny nhit cng thp hn nhiu so vi thit b alkyl ha (b) qu trnh thu etylbenzen t nng sut cao hn. Sau khi ra khi thit b chuyn v alkyl (d), dng c a n mt thp tch, ti y kh i ra nh cn dng lng c lm lnh v a vo thng lng (g). Ti (g) pha nng lng ra khi pha lng c tch ra mt phn hi lu li qu trnh , cn phn lng nh c a qua h thng cc ct phn tch lm sch (h). i vi qu trnh ng th, tt c xc tc u vn cn trong dung dch, sn phm c ra bng nc v amoniac. Dng alkylat th tip tc a qua b phn tinh ch thu etylbenzen tinh khit. Qu trnh tinh ch thu etylbenzen tinh khit c thc hin trong 3 ct chng tch: Benzen khng phn ng c thu hi nh ct chng ct u tin, dng y ct 1 c a qua ct chng ct 2. ct 2, etylbenzen c chng tch ra khi phn poly alkylbenzen nng hn, y ct 2 c a qua ct cui cng. nh ct 2 thu c etylbenzen vi tinh khit ln hn 99% (c th t 99,8%) Ti ct 3, chng ct poly alkyl bng stripping v cho hi lu v u qu trnh, nhng hp cht cn hay du cha ch yu l cc hp cht thm a vng c s dng lm nhin liu. b. Qu trnh pha hi Cng ngh alkyl ha trong pha kh c thc hin t u nhng nm 1930 nhng vo thi gian ny cng ngh alkyl ha trong pha kh khng th cnh tranh ni vi cng ngh alkyl ha trn xc tc AlCl3 trong pha lng. * Nm 1960 c qui trnh Alkar c pht trin bi UOP da trn xc tc BF3: u im:

+ s dng nguyn liu c t etylen (810 %mol), c th s dng dng kh t l cc v cc sn phm a dng khc ca nh my lc du. + sn phm c tinh khit cao Nhc im: mt lng rt nh nc (>1 mg/kg) s lm thu phn xc tc BF3 gy n mn thit b, do cn loi b nc cng nh cc hp cht cha S, O trong nguyn liu trc khi a vo qui trnh. iu kin vn hnh: + nguyn liu: benzen kh, etylen v BF3 + p sut cao: 25 35 bars + nhit thit b phn ng thp : 100 150oC + etylen/benzen = 0,15 0,2 + nhit thit b chuyn v alkyl = 180 230oC Kt qu thu etylbenzen c nng 99,9%. * Nm 1970, cng ngh ca Mobil - Badger xut hin v c cng nhn l cng ngh alkyl ha trong pha hi thnh cng nht vi xc tc zeolit tng hp ZSM-5. u im: + h xc tc d th nhiu thun li + sn phm c tinh khit cao Nhc im: qu trnh cho hiu qu kinh t khng cao bng cng ngh alkyl ha trong pha lng. iu kin vn hnh: + nguyn liu t etylen: 15% + xc tc ZSM-5 hot tnh cao + p sut = 20 30 bars + nhit = 400 450oC

+ c 2 thit b phn ng hot ng thay phin: 1 thit b hot ng v 1 thit b ti sinh xc tc gip qu trnh hot ng lin tc c. Cng ngh sn xut etylbenzen mi hin nay: Hin nay cng ngh xc tc zeolit, pha lng, tng xc tc c nh ca Lummus/UOP l cng ngh sn xut etylbenzen hin i nht c nhiu u im. Cng ngh ca qui trnh cng da trn qui trnh alkyl ha trong pha lng c bn nu trn, im ng ch l xc tc s dng l xc tc zeolit khng n mn v khng c hi, c th ti sinh ngay trong thit b phn ng hay em i ti sinh mt c s khc; v vy s ny khng cn h thng ra v trung ha sn phm. u im: + p ng yu cu v sn lng d dng + tinh khit sn phm cao > 99% (m); sn phm ph xylen rt t, trnh c s kh khn trong vic phn tch tn nhiu kinh ph, thch hp dng lm nguyn liu sn xut Styren. + tiu th nguyn liu t + chi ph u t thp + vn hnh an ton, d dng + hiu sut 99,5% S cng ngh: hnh 3
Etylbenzen

Etylen, benzen mi v benzen hi lu t nh thp tch benzen (3) c a vo thit b phn ng alkyl ha (1) vi xc tc zeolit, phn ng xy ra to thnh hn hp alkylat. Dng sn phm c a qua thp tch benzen d v poly etylbenzen (3), mt phn cho hi lu v thit b chuyn v alkyl (2) to etylbenzen b sung, mt
3 4 2

poly etylbenzen v sn phm nng c a qua thp phn tch (4), nh thp (4) hi lu v thit b chuyn v (2), y thp (5) thu sn phm nng lm nhin liu t.
1

thu etylbenzen, phn y (4) a qua thp tch (5) thu poly etylbenzen nh cho

C2H4 C6H6

C6H6 hi lu Phn nng

phn c a v u qu trnh (1). Ti thp tch (3), phn y gm etylbenzen,

Hnh 3: Cng ngh xc tc pha lng, zeolit, tng xc tc c nh Lummus/UOP 1. Thit b phn ng alkyl ha - 2. Thit b chuyn v alkyl - 3. Thp tch benzen 4. Thp tch Etylbenzen - 5. Thp tch poly etylbenzen 2.2. Tng hp isopropylbenzen Isopropylbenzen C6H5-CH(CH3)2 cn c tn gi khc l Cumol, iu kin thng tn ti dng lng c ts = 152,5oC. ng dng: + t isopropylbenzen s thu c mt monome quan trng trong lnh vc cao su tng hp l -metylstyren C6H5-C(CH3)=CH2 + t isopropylbenzen tng hp isopropylphenyl hydroperoxyt (cn gi l hydroperoxyt cumol) C6H5-C(CH3)2-OOH v t y tng hp phenol v aceton.
CH3 - CH - CH3
+ O2

OOH CH3 - C - CH3

+ H+

OH + CH3 - CO - CH3

Sn xut : iso propylbenzen c th c sn xut tng t nh etylbenzen II. Alkyl ha parafin

Qu trnh alkyl ha parafin c ng dng sn xut cc nhin liu ch s octan cao cho ng c v hin ang l qu trnh thng dng nht nhiu nc trn th gii. Trong phm vi Cng ngh Ha du, qu trnh alkyl ha tp trung ch yu sn xut isooctan vi sn phm chnh l 2,2,4-trimetylpentan. y l cu t chun c RON = 100 dng trong php th xc nh ch s octan ca xng nhin liu. Phn ng: i - C4H10 + n - C 4 H8 i - C8H18

1. Ha hc v c s l thuyt

Nguyn liu: iso butan Tc nhn alkyl ha : n- buten Xc tc: HF khan hay H2SO4 94 96% (m) hay AlCl3 Ch cng ngh: tu thuc vo loi xc tc s dng

Xc tc l H2SO4:

t = 4 10oC p = 3 4 at tx = 20 30 pht

Xc tc l HF :

t = 20 35oC p = 6 8 at tx = 10 20 pht

Xc tc l AlCl3:

t = 50 60oC p = tng i dng

C ch: phn ng xy ra theo c ch cacbocation o Ban u olefin tham gia to ion cacboni: CH2=CH - CH2CH3 + H+ CH3-CH +-CH2CH3

o Sau , cacbocation bc hai c to thnh do km bn hn so vi ion

bc ba nn s trao i ion H+ vi i-parafin; v cacbocation bc ba ter3 3 3 3 3 butylcation hnh2 thnh tip tc 3tc dng vi olefin 2ban2 u:

CH CH+CH CH

+ (CH ) CH

CH CH CH CH CH3

+ (CH3)3C+

(CH3)3C+ + CH3CH=CHCH3

CH3 - C - CH - CH+ - CH3 CH3 CH3

o Cacbocation mi to thnh d b chuyn v ni phn t vi s di

chuyn v tr ca H v cc nhm CH 3- v cui cng, cc cacbocation ny tc dng vi iso-butan s to ra hn hp cc iso-octan v ter butylcation: (2 bc ny c biu din chung nh sau)
CH3 CH3 CH3 CH3 CH3 - C - CH+ - CH CH3 CH3 CH3 CH3 CH3 - C+ - CH - CH CH3 CH3 - C - CH - CH+ - CH3 CH3 CH3 CH3 CH3 - C CH3 CH3 CH3 C+ - CH2 CH3 CH3 (CH3)3CH (CH3)3C+ CH3 CH3 - C - CH2 - CH CH3 CH3 2,2,4-trimetylpentan CH3 CH3 CH3 - CH - CH - CH CH3 2,3,4-trimetylpentan CH3 CH3 CH3 2,2,3-trimetylpentan CH3 CH3 CH3 - C+ - C - CH2 CH3 CH3 CH3 CH3 CH3 - CH - C - CH2 CH3 CH3 2,3,3-trimetylpentan CH3

CH3 - C - CH - CH2

Cation (CH3)3C+ ny thc y qu trnh theo c ch chui ion. Thnh phn cc isome ph thuc vo bn ca cc cacbocation trung gian v vn tc phn ng trao i ca chng vi i-butan.

 Cc phn ng ph: o Phn ng alkyl ha ni tip - song song Cc sn phm trung gian iso octylcation cng c kh nng phn ng vi cc olefin to ra cc parafin cao phn t :
C8H17+ + C4H8 C12H25+
+ (CH3)3CH

C12H26

+ (CH3)3C+

o Phn ng phn hu Trong cc alkylat thu c bao gi cng c mt cc parafin thp v cao phn t vi s nguyn t Cacbon khng l bi s so vi s nguyn t cacbon trong nguyn liu ban u. V d, khi alkyl ha i-butan bng cc buten th alkylat cha 610% hydrocacbon C5 - C7 v 510% hydrocacbon C9 hoc cao hn. o Phn ng trng hp Phn ng ny xy ra do s trng hp cation ca olefin hnh thnh cc polyme thp phn t c cha ni i.
2 C4H8
+ H+

C8H16

+ C4H8

C12H24 ....

T l gia i-parafin v olefin: Khi s dng lng d i-parafin so vi olefin s hn ch ton b cc phn ng ph v c nh hng tt n hiu sut alkylat, tng hm lng sn phm mong mun, tng ch s octan ca sn phm v gim tiu hao xc tc. Tuy vy cng khng nn dng lng d qu ln i-parafin v khi chi ph ti sinh sau phn ng s rt cao. T l mol ti u trong trng hp ny gia i-parafin v olefin l t 4:1 n 6:1. Thit b phn ng Hn hp phn ng l h hai pha c phn tn vo nhau nh cnh khuy hay h thng bm phn tn.

C hai loi thit b phn ng s dng khc nhau bi phng php gii nhit: o Loi lm lnh bn trong bi amoniac lng (hoc propan): phn ng c thc hin trong thit b alkyl ha c gn my khuy cng sut ln v cc ng lm lnh. Trong cc ng ny tc nhn gii nhit s bc hi nh nhit sinh ra ca phn ng . Hi ca n s c ngng t sau v tr v trng thi lng ban u.
o Loi lm lnh bng cch cho bc hi lng i-butan d : phng php

ny hiu qu hn nh iu khin nhit d dng hn. Loi thit b ny c chia thnh nhiu khoang nh bi cc vch ngn, mi khoang u c b phn khuy ring bit. Buten c a vo tng khoang mt cch ring r, do vy thc t nng ca n l rt nh, iu ny cho php hn ch cc phn ng ph. Cn a.H2SO4 v i-C4H10 c a vo khoang th nht bn tri, sau nh tng s chy t t qua vch ngn vo khoang th hai v tip tc nh vy. Khoang p cui s lm nhim v tch acid khi hydrocacbon, v acid ny c a tr li phn ng alkyl ha. Hn hp hydrocacbon sau khi qua vch ngn cui cng s c a i x l tip. 2. Cng ngh S cng ngh alkyl ha i-butan bng n-buten c trnh by nh sau:
3 5 11 12

Ngi ta a vo khoang u ca thit b phn ng (4) i-butan lng, a.H2SO4 C3H8 (lng mi cng lng hi lu), cn n-buten c a vo tng khoang ring r.
11 Do 1 nhit ca phn ng sinh ra mt phn i-butan s b bay hi. Hi ny s i vo 6

bnh cha (2), ng vai tr va l bnh tch va l bnh trn. Kh t bnh ny c tip nhn lin tc bi my nn (1) (nn n p sut 0,6 MPa) v ngng t ti thit b 10
2 13 ngng t (3). Trong thit b chnh p sut (5) p sut c gim xung khong 0,2

C4H10

MPa, ti y mt phn i-butan c bay hi v tch ra trong bnh cha (2). T (2) ibutan lng li c a tr li thit b alkylNaOH ha. 7
alkylat n-C4H8 H2SO4 H2SO4 8 9 4 13

Hnh 4: S cng ngh alkyl ha i-butan bng n-buten 1- My nn; 2- Bnh cha; 3,12- Thit b ngng t; 4- Thit b phn ng; 5- Thit b chnh p sut; 6- Thit b tch propan; 7,9- Thit b tch; 8- Thit b trung ha;10- Thit b tch butan; 11- Thit b trao i nhit; 13- Thit b un nng Trong qu trnh hot ng lin tc trong i-butan s xut hin propan do phn hu cc hydrocacbon hay hin din ngay trong nguyn liu ban u. Do vy trong chu trnh lm lnh i-butan c mt cng on tch propan bng ct chng phn on (6). Ngi ta a vo mt phn i-butan hi lu sau sinh hn (3) v i-butan c lm sch khi propan s quay tr v bnh cha (2). Hn hp i ra t khoang cui thit b alkyl ha (4) c cha i-butan d, octan, hydrocacbon C5 - C7 v cc hydrocacbon cao phn t khc. Hn hp ny c a vo thit b tch (7) tch phn acid cn li. Acid c a tr li thit b alkyl ha, tuy nhin mt phn ny s c thi ra ngoi, s b vo mt lng acid mi. Lp hydrocacbon t thit b tch (7) c trung ha bng dung dch 10% trong

thit b (8) sau tch ra khi lp nc trong thit b tch (9). Hn hp hydrocacbon trung tnh c a i chng ct ti ct chng phn on (10). Ti ct ny phn on i-butan mi c a vo. Mt phn i-butan c a tr li thp chng (10), cn phn ln s a qua thng cha (2) v t y i vo thit b phn ng. Nh vy s thc hin mt chu trnh vn chuyn ca i-butan. T sn phm y ct chng (10) s thu c alkylat sn phm.

3. ALKYL HA THEO NGUYN T OXY, LU HUNH V NIT

Cc qu trnh O- alkyl ha , S- alkyl ha v N- alkyl ha l cc phng php c bn tng hp cc hp cht vi lin kt ete, mercaptan v amin. I. O-alkyl ha Trong s cc qu trnh O-alkyl ha c 2 qu trnh c ng dng trong sn xut cng nghip: alkyl ha ru v phenol bng cc dn xut Clo; alkyl ha ru bng olefin. Trong qu trnh alkyl ha ru bng olefin c s dng rng ri sn xut cc ete MTBE (metyl ter-butyl ete); ETBE (etyl ter-butyl ete) v TAME (ter-amyl metyl ete). y l cc ph gia tng ch s octan cho xng thay th cho nc ch. (Phn ny s c hc theo chng Ete ha - Mn Cc qu trnh chuyn ha ha hc) II. S-alkyl ha y l qu trnh c bn tng hp cc Mercaptan, chng hn nh:

Etylmercaptan - nguyn liu trong sn xut mt loi thuc tr su ni ting l Mercaptophos, c tng hp t qu trnh alkyl ha Hydrosulfid natri bng dn xut Clo l Etylclorua:
C2H5Cl + NaSH C2H5SH + NaCl

Etylmercaptan, Pentylmercaptan c s dng lm cht to mi cho kh t dn dng. Pentylmercaptan c tng hp t qu trnh alkyl ha bng Clopentan:
C5H11Cl + NaSH C5H11SH + NaCl

Ngoi ra cn mt vi mercaptan khc c ng dng trong tng hp cc cht ty ra khng ion, hay trong qu trnh tng hp cao su nhn to.... III. N- alkyl ha

 alkyl ha ammoniac hoc amin theo nguyn t nit, ngi ta s dng tc nhn alkyl ha l cc dn xut Clo v ru, trong gn y ru c s dng nhiu hn, bi v cc dn xut Clo t tin hn. Cc amin ph bin nht l Metylamin CH3NH2 (ts - 70C), Dimetylamin (CH3)2NH (ts = 70C), Trimetylamin (CH3)3 N (ts = 40C), Etylamin C2H5NH2 (ts = 150C), Dietylamin (C2H5)2NH (ts = 560C), Trietylamin (C2H5)3N (ts = 900C), ... Tt c cc hp cht ny u c th trn hp vi nc bt k t l no; vi khng kh chng to thnh hn hp d n v cng nh cc amin khc chng l nhng cht rt c. Chng c dng lm nguyn liu lng cho cc ng c tn la (nh Metylamin, Etylamin); c dng lm dung mi hp th cho cc qu trnh x l kh acid; c dng lm hp cht trung gian trong tng hp hu c... 1. Ha hc v c s qu trnh S tc dng ca ru vi ammoniac v amin theo phng trnh: ROH + NH3 RNH2 + H2O

y l qu trnh to nhit v khng thun nghch. Ch cng ngh: cc qu trnh c gi tr cao trong sn xut cng nghip khi thc hin : Pha kh

Nhit : 350 450oC Xc tc: xc tc dng acid nh Oxyt nhm Al2O3; aluminosilicat; ....

C ch: tc dng ca xc tc d th c th hin s hot ha lin kt C-O trong ru do s hp ph ha hc trn cc tm acid ca chng:
ROH + H+ RO+H2
+ NH3 - H2O

RN+H3

RNH2 + H+

Phn ng ph: o Phn ng dehydrat:

2 ROH ROR + H2O RCH2 - CH2OH RCH=CH2 + H2O

(1) (2)

o Phn ng alkyl ha ha ni tip - song song: phn ng ca ammoniac vi ru, cng nh vi cc dn xut Clo l qu trnh ni tip - song song km theo s th lin tip cc nguyn t H ca ammoniac. Kt qu l sinh ra hn hp amin bc nht, bc hai v bc ba.
NH3
+ ROH - H2O

RNH2

+ ROH - H2O

R2NH

+ ROH - H2O

o Phn ng chuyn v cc nhm alkyl:

2 RNH2 R2NH + NH3 RNH2 + R3N 2 R2NH

2. Cng ngh:

S cng ngh sn xut Metylamin c biu din nh sau:

CH3OH

NH3 (l) CH3OH 1 2

NH3 (k)

TMA

MMA

DMA

4 10 11

5 10 11

6 10 11

7 10 11

hi nc

nc thi

Hnh 5: S cng ngh sn xut metylamin 1- Thit b trn ; 2- Thit b trao i nhit ; 3- Thit b phn ng ; 4 8- Thp chng ; 9- B hi lu ; 10- Thit b un nng ; 11- Van chnh p Lng Metanol v ammoniac mi cng vi lng hi lu c trn ln p sut 2 5 MPa trong thit b trn (1) v a vo thit b trao i nhit (2). Ti y

chng c bc hi v un nng bng hn hp kh phn ng. Trong thit b phn ng (3) s xy ra cc phn ng c m t nh trn v to thnh cc amin chuyn ha gn nh hon ton ca Metanol. Cc kh nng s cung cp nhit ca mnh cho hn hp ban u trong thit b trao i nhit (2) v sau em i x l tip tc. Cc sn phm thu c s phn tch bng chng ct phn on, mi giai on s thit lp p sut sao cho thu c on hi lu lm lnh bng nc. Trc ht trong thp chng (4) ngi ta chng tch ammoniac v n c a li thit b phn ng. Sn phm y c a qua thp chng (5) v chng ct cng vi nc (do s c mt ca nc lm cho bc hi tng i ca trimetylamin (TMA) tr nn rt cao so vi cc metylamin khc). Mt lng nh TMA chng tch ra c xem l thnh phm nhng phn ch yu c hon lu li thit b phn ng. Hai amin cn li c nhit si khc bit ln hn (-70C v 70C) s c tch ra bng chng tch phn on thp chng (6) v (7). Mi sn phm ny ly ra t nh thp c th xem nh l thnh phm hoc tr li phn ng tip tc. thp chng cui cng (8) s chng tch Metanol khi nc v meetanol c quay tr li thit b phn ng. Hiu sut cc amin l 95% *Trong tng hp Etylamin ngi ta cng s dng qui trnh cng ngh nh trn. Ch khc bit l cc amin ny c nhit si khc bit ln (15 0C, 560C v 900C) nn c th tch ra bng chng ct phn on bnh thng. Trong trng hp ny cn xut hin sn phm ph l Etylen, n c th tch ra khi ngng t hn hp trc giai on chng tch ammoniac).