TRNG I HC CNG NGHIP TP.

HCM
TRUNG TM CNG NGH HA HC
Th.s Trn Th Hng

GIO TRNH
TNG HP HU C HA DU

Thnh ph H Ch Minh 2006

1

MC LC
mc
Trang
MC LC .................................................................................................... 1
CHNG 1: NGUN NGUYN LIU . ...................................................... 4
1.1.
Parafin........................................................................................... 4
1.2.
Olefin............................................................................................. 7
1.3.
Hyrocacbon thm ..................................................................... 18
1.4.
Axetylen. ..................................................................................... 22
1.5.
Kh tng hp ............................................................................... 24
CHNG 2: CC QU TRNH C BN CA TNG HP HU C .... 31
2.1.
Qu trnh ankyl ha .................................................................... 31
2.2.
Cc qu trnh ehydro ho v hydro ho ................................... 37
2.3.
Qu trnh halogen ha ................................................................ 46
2.4.
Qu trnh oxi ha ........................................................................ 57
2.5.
Cc qu trnh thy phn, tch nc, este ha, amit ha ........... 72
2.6.
Cc qu trnh sunfat ha, sunfo ha v nitro.............................. 83
CHNG 3: TNG HP T AXETYLEN ............................................... 93
3.1.
Sn xut vinylclorua (VC) v polyvinylclorua (PVC) ................... 93
3.2.
Tng hp vinyl axetat (VA), polyvinyl axetat (PVA).................... 95
CHNG 4: TNG HP T METAN V CC PARAFIN KHC. ......... 98
4.1.
Tng hp hydrocianit t metan .................................................. 98
4.2.
Tng hp amoniac...................................................................... 98
4.3.
Tng hp metanol .................................................................... 103
4.4.
Tng hp formanehit .............................................................. 106
4.5.
O-ankyl ha bng olefin. Tng hp metyl tec-butyl ete (MTBE)109
4.6.
N-ankyl ha. Tng hp amin t ru....................................... 110
4.7.
Oxy ha naphta nh (C5 C8) .................................................. 113
4.8.
Oxy ha parafin rn thnh axit bo tng hp ........................... 114
CHNG 5: TNG HP T ETYLEN ................................................. 118
5.1.
Oxy ha etylen, tng hp oxit etylen, etylen glycol (EG).......... 119
5.2.
Oxy ha etylen. Tng hp acetanehit, vinyl acetat, axit axetic123
5.3.
Hyrat ha etylen. Tng hp etanol ......................................... 139
5.4.
Halogen ha etylen. Tng hp vinyl clorua .............................. 141
CHNG 6: TNG HP T PROPYLEN V BUTEN.147
6.1.
Oxy ha propylen. Tng hp acrolein, axit acrilic..................... 145
6.2.
Halogen ha propylen. Tng hp allyl clorua. .......................... 150
6.3.
Hydrat ha propylen. Tng hp iso-propyl ancol...................... 154
6.4.
Oxy ha n buten. Tng hp anhyric maleic (AM). .............. 155
6.5.
Oxy ha iso-buten. Tng hp metacrolein v axit metacrilic.... 156
2

CHNG 7: TNG HP T BENZEN, TOLUEN, XYLEN (BTX)......... 158

7.1.
Ankyl ha benzen thnh etyl v iso propyl benzen. .............. 158
7.2.
ehydro ho cc hp cht ankyl thm. sn xut styren ......... 161
7.3.
Oxy ha ankylbenzen. Tng hp phenol v aceton ................. 162
7.4.
Oxy ha p-xylen. Tng hp axit terephtalic .............................. 167
7.5.
Oxy ha metylbenzen. Tng hp dimetyl terephtalat ............... 172
CHNG 8: TNG HP CHT TY RA............................................ 176
8.1.
Tng hp cht hot ng b mt dng ankylsunfat ................. 176
8.2.
Tng hp cht hot ng b mt dng ankylarensunfonat...... 180
8.3.
Phn loi cht hot ng b mt (HBM) ................................ 184
8.4.
Nguyn liu sn xut cc cht ty ra ..................................... 186
8.5.
C ch ty ra.......................................................................... 194
8.6.
Mt s qui trnh cng ngh sn xut cht ty ra .................... 195
CHNG 9: TNG HP THUC TR SU ....................................... 203
9.1.
Gii thiu .................................................................................. 203
9.2.
Mt s cng ngh tng hp thuc tr su................................ 203
9.3.
ng dng ca thuc tr su..................................................... 212
9.4.
Phn loi thuc tr su............................................................. 216
TI LIU THAM KHO............................................................................ 229

CHNG 1: NGUN NGUYN LIU CA CNG NGH TNG HP

HU C HA DU.
Nguyn liu ch yu sn xut cc sn phm hu c l nhng
cht hu c ha thch than , du m, kh thin nhin. T , ngi
ta thu c hu ht cc loi nguyn liu ban u cho cc qu trnh tng
hp hu c ha du: parafin, olefin, hyrocacbon thm, axetylen v
kh tng hp.
1.1. Parafin
Hyrocacbon no c chia ra thnh nhiu nhm sau: parafin thp
phn t (C1 C5) dng ring l; parafin cao phn t (C10 C40) l hn
hp lng v rn ca nhng ng ng vi s cacbon khc nhau.
1.1.1. Parafin thp phn t
Gii thiu
Metan l cht kh kh ha lng, nhng tt c cc parafin dng kh
khc u ngng t khi lm lnh bng nc di tc dng ca p sut.
Quan trng l s khc bit v nhit si ca n-butan vi iso-butan,
ca n-pentan vi iso-pentan ln c th tch ra bng phng php
chng ct phn an.
Parafin thp phn t khng tan trong nc v cht lng phn cc,
nhng b hp th bi nhng hyrocacbon khc v cc cht hp ph rn.
Parafin thp phn t to vi khng kh nhng hn hp n nguy him.
Ngun gc chnh ca parafin thp phn t l kh thin nhin v kh
ng hnh, cng nh kh thu c t cc qu trnh ch bin du m c
s tham gia ca hyro.
tch kh du m, ngi ta c th dng cc phng php hp ph,
ngng t, chng ct. Chng ct l phng php c dng nhiu nht.
Tch parafin thp phn t
Khi tch nhng kh kh ngng t phi dng p sut cao (2 4 MPa)
v lm lnh su. Khi tch etan v metan khi nhng hyrocacbon khc
bng phng php chng ct, ngi ta thng kt hp vi hp ph
khng phi lm lnh su v kinh t hn.

C 1 + C2

izo- C4
C5

C4

Izo-C5
5

4
kh

10

C3

n-C4

C6

n-C5

Hnh 1.1. S cng ngh phn tch hn hp parafin thp phn t.

1 My nn; 2, 5, 6, 7, 8, 9 Thp chng ct phn on;
3 - Thit b ngng t; 4 - Thit b un nng; 10 - Thit b iu chnh p sut.

Ngi ta nn kh trong b nn kh (1), lm lnh bng dng nc ri

cho vo thp chng ct (2). Trong (2), C1 - C3 tch khi hyrocacbon
nng hn. Ty vo p sut v hm lng phn on C1,C2 trong kh,
lp phn hi lu trong thit b ngng t hi lu (3), ngi ta dng nc
hoc propan lm lnh. Phn on nh c chng tch trong thp
(5), lng hi lu c lm lnh bng propan. Sn phm pha trn
ca thp ny l kh kh, sn phm y ca thp ct l propan lng.
Phn on nng C4-C6 t thp (2) c iu tit n p sut
0,8Mpa. Trong thp (6), ngi ta tch phn on C4 v a chng qua
thp (7) tch ring n- butan v izo-butan vi 98% hm lng sn
phm chnh.
Cht lng trong thp (6) c iu tit n 0,3MPa v c a qua
thp (8). y, C5 c tch thnh n- pentan v izo-pentan vi 97% 98% sn phm chnh.
Metan v etan trong kh kh, c th tch ra bng cch chng ct
phn on nhit thp, lng hi lu c lm lnh bng propan,
etan lng vi p sut 4,0 - 4,5MPa. Kh thin nhin c ti 96% - 97%
CH4 nn c th dng trc tip nh metan k thut.
1.1.2. Parafin cao phn t
Gii thiu
Nhit nng chy ca parafin cao phn t tng dn theo chiu di
mch cacbon, nhit nng chy ca parafin mch thng ln hn
parafin phn nhnh tng ng. Mt im khc bit ca n-parafin l c
5

kh nng to tinh th cng hp vi cacbamit v zeolit.

Trong m bi trn, gasoil, du la c th cha n 30% n-parafin.
tch chng, ngi ta dng mt s phng php tch: phng php
kt tinh, tch bng cacbamit, tch bng zeolit.
Tch parafin cao phn t
Tch n-parafin bng zeolit
y l phng php mi, tin b, c s dng nhiu. N dng cho
bt c phn on no, cho tch n-parafin cao (80% 98%) v
sch cao (98% 99.2%). Qu trnh gm 2 giai on chnh l hp ph nparafin v gii hp ph n-parafin. Chng c th thc hin pha lng
hay pha kh nhit n 3000C 3500C v p sut khc nhau. Gii
hp ph bng p sut thp, tng nhit y nhng cht khc ra (npentan, ammoniac) hoc kt hp nhng phng php ny.
S cng ngh tch n-parafin bng zeolit c m t trn hnh 1.2.

Nguyn liu
8

8
2

NH

N2

4
Izo - parafin

n - parafin

Hnh 1.2. S cng ngh tch nparafin v iso-parafin cao phn t bng phng
php hp ph vi zeolit.
1,5 - Thit b un nng; 2 - Thit b hp ph v gii hp ph;
3,6 Sinh hn; 4,7 - Thit b tch; 8 - H thng thi kh.

Ngi ta trn vo phn on du vi kh mang (N2), gia nhit v

ha hi trong khi thit b gia nhit (1). Hn hp hi kh thu c cho
vo mt trong ba thit b hp ph (2) cha y zeolit. Ti y, xy ra
6

qu trnh hp ph n-parafin. Lm lnh hn hp thot ra sau khi hp ph

qua b lm lnh (3) ri tch phn ngng tch parafin ra khi kh
mang trong b phn ly (4). Kh mang ny li em trn vi phn on
ban u. Khi cht hp ph b parafin bo ha hon ton th chuyn hn
hp kh mang vi phn on du vo b hp ph th hai, cn trong b
th nht s xy ra qu trnh gii hp ph. Ngi ta cho vo b hp ph
th nht nhng kh gii hp ph (NH3) lm nng s b b gia nhit
(5). Sau khi gii hp ph, ngi ta lm lnh hn hp cht gii hp ph
v parafin trong b lm lnh (6) v tch chng trong thit b phn ly (7).
NH3 li quay vng vo gii hp ph. Mt trong ba thit b hp ph lm
vic giai on hp ph, cn hai thit b cn li - gii hp ph, nh th
qu trnh ng m cc dng chy u t ng.
1.2. Olefin
Olefin l hyrocacbon nguyn liu quan trng, thng thng tn ti
dng kh v lng, chng c sn xut bng nhiu phng php khc
nhau
1.2.1. Phng php nhit phn v cracking nhit
Nhit phn: l qu trnh thu nhit v lin h vi s lng sn xut
nng lng, trong qu trnh tn dng nhit ca kh nng c ngha
quan trng. Nhng s b phn phn ng hin hnh c chia theo
kh nng cung cp nhit
Cracking nhit: Cracking nhit parafin mm hoc cng dng trong
cng nghip c sn phm olefin mch thng t 5 - 20 nguyn t
cacbon. Cng ngh ca n rt ging vi nhit phn nhng sn phm
du m.
1.2.2. Phng php cracking xc tc
Cracking xc tc l qu trnh dng sn xut olefin C3 C4, trong
c isoC4. Cho n ngy nay, qu trnh ngy cng c ci tin v
hon thin, nhm mc ch nhn nhiu xng hn vi cht lng xng
ngy cng cao v nhn c c nguyn liu c cht lng tt cho cng
ngh tng hp ha du.
Qu trnh cracking xc tc thng c tin hnh iu kin cng
ngh nh sau: nhit khong 470 5500C, p sut trong vng lng
ca l phn ng P = 0.27Mpa, tc khng gian th tch truyn nguyn
liu, ty theo dy chuyn cng ngh m c th t t 1 120m3/h.m3(1
120h-1). Xc tc cracking ngy nay, thng dng ph bin l xc tc
cha zeolit mang tnh axit. Sn phm ca qu trnh l mt hn hp
phc tp ca hyrocacbon cc loi khc nhau m loi c s nguyn t
cacbon t 3 tr ln vi cu trc mch nhnh chim ch yu.
1.2.3. Tch olefin
Kh thu c t nhng qu trnh cracking v nhit phn khc nhau
7

v thnh phn (theo s liu bng 1.1). Chng c th c chia ra lm

ba nhm:
Kh cracking nhit v xc tc cha nhiu hyrocacbon C3 v C4
nhng t etylen. T kh ny, tt nht nn tch propylen v buten, cn
nhng cu t khc chuyn i nhit phn hoc dng cho mc ch khc.
Kh khi nhit phn hyrocacbon dng kh cha t phn on cao.
Nhng kh ny dng lm nguyn liu butan, t chng c th tch etylen
v propylen.
Khi nhit phn phn on du m lng thu c sn phm phn ln
l olefin C2 C4, chng c tch bng phng php chng ct hp
th. Phng php ny i khi dng tch cc sn phm kh ca qu
trnh nhit phn. Vi phng php chng ct nhit thp v c
thc hin trong nhng thit b ln hin i, phn on olefin thu c
sch hn v nng lng tiu tn cho cng on tch t hn.
Chun b kh tch
Trong kh cracking v nhit phn c nhiu tp cht cn phi lm sch
s b. Mt s trong gy n mn thit b (H2S, CO2 ), s khc kt t
li gy tt (H2O) ng ng v thit b, mt s khc c nhit si gn
vi olefin v lm bn phn on thu c (axetylen, metylaxetylen).
Ngoi ra, trong kh cn cha hi cht lng hyrocacbon m nhiu nht
l benzen, penten.
Khi lng c bn nhng hyrocacbon cao phn t v nc c
tch ra t ngay giai on nn kh u tin. Sau , giai on nn kh
bc hai v cui cng, kh c lm sch khi tp cht kt lng.
Phng php lm sch kh khi H2S v CO2 c chn ty vo nng
nhng tp cht ny. Nu nng H2S v CO2 khng ln lm, c th
ra kh bng dung dch kim. Nu khi lng chng ln, ngi ta
thng s dng phng php hp th bng etanolamin vi qu trnh
trung ha hon ton tnh axit ca kh bng kim, trong thit b lc kh.
Lm sch kh bng dung dch etanolamin da trn c s nhng
baz hu c ny to vi CO2 nhng mui bn nhit thp v b
phn ly khi gia nhit.
2HOCH2-CH2NH2 + H2S

20-400C
0

100-110 C

(HOCH2-CH2NH3)2S

Nh vy etanolamin trong thit b gii hp c th ti sinh v quay li

hp th. Ngi ta sy kh ln cui bng dietylenglycol hoc kim rn,
nhng cng c khi dng oxyt nhm hoc zeolit v chng hp ph tt
nhng cht bn.

Bng 1.1. Thnh phn sn phm cracking v nhit phn (% khi lng)
Cracking
Nhit
phn Nhit phn
Cu t
xc tc
hyrocacbon kh
hyrocacbon lng
CH4
6-7
16-18
15-20
C2H4
2,5-3,5
36-38
30-40
C2H6
6-7
26-28
5-8
C3H6
14-17
10-12
15-20
C3H8
13-15
5-6
1-3
C4H8
19-22
2-4
8-12
C4H10
20-32
1-3
C4H6
1-3
5-7
H2
0,7-0,9
1,5-2
0,9 -1,2
lm sch olefin ln axetylen, ngi ta dng phng php hyro
ha chn lc trn cht xc tc khng ng nht, phn ng ny khng
xy ra vi olefin:
P d /A l2 O 3
C H
+ H
C H
2

t mc ch ny, ngi ta cho xc tc paladi (trn cht mang) v

cht xc crom coban niken lm vic nhit 1500C 2300C. Cng
vi axetylen, mt s ien c kh nng phn ng b hyro ha, nu
mun gi chng, ngi ta ch hyro ha etylen, sau khi tch phn
on C4. Ngi ta thc hin vic lm sch ny trong phn on C2 C3
cn phi thm H2.
Phn tch cc phn on sn phm ca cracking xc tc
Tng qut dy chuyn cng ngh gm 3 phn chnh:
- Phn ng
- Ti sinh v tn dng nhit
- Phn tch sn phm
Hot ng ca dy chuyn nh sau:
Nguyn liu mi t b cha nguyn liu (1), c cho qua thit b
trao i nhit ng chm, nguyn liu mi c th c trn vi phn
on tun hon HCO (2) v cn y (3), sau cho qua l t
nguyn liu cracking (4). Nguyn liu sau khi ra khi (4) c tip
xc vi dng xc tc nng ti sinh (6) y thit b phn ng (5) v
xy ra phn ng cracking xc tc. Sau khi tch khi xc tc, dng
hi sn phm (7) c chuyn n ct chng ct phn on (13).
p sut trong thit b phn ng c khng ch bng b phn iu
chnh p sut ca ct phn on. Xc tc lm vic c cho qua
vng tch hi(cn gi l b phn ra xc tc) bng cch thi hi
nc vo.

Hnh 1.3. S cng ngh cracking xc tc vi lp xc tc tng si (FCC)

v phn tch cc phn on sn phm.
1- Bn nguyn liu; 2 Dng HCO tun hon; 3 Dng cn y;
4 L gia nhit; 5 - Thit b phn ng; 6 Dng xc tc ti sinh; 7 Dng sn phm hi;
8 Dng xc tc cc ha; 9 - Thit b ti sinh xc tc; 10 - Bung lng bi xc tc; 11 Thit b tn dng nhit; 12 - Lc in;
13 - Ct chng ct phn on; 14 - Thit b tch.

Xc tc c cha cc (8) c chuyn qua van iu khin v

khng ch bi b kim tra mc xc tc trong l phn ng v sau i
vo l ti sinh. Mc ch chnh ca ti sinh l t chy lp cc bm trn
xc tc bng oxy ca khng kh. Xc tc ti sinh c chuyn vo
ng phn ng ng sau khi c ui sch kh qua mt van l m
s hot ng ca van ny c khng ch, iu khin t ng bi b
phn iu chnh nhit ca reactor, ri sau xc tc c trnvi
nguyn liu racking v hon thnh mt chu trnh.. ng thi ngi ta
tho xc tc bn, gi ha ra v b sung xc tc mi m bo hot
tnh n nh ca xc tc theo thi gian lm vic.
10

Kh ca qu trnh chy cc v cc ht xc tc chuyn ng t pha

c vo pha long ca nh l ti sinh, c qua 2 cp cyclon
gi li cc ht xc tc v tch kh. Sau , khi kh c qua
bung lng (10) tch tip bi xc tc ri qua b phn tn dng
nhit (11), tip theo khi kh c lm sch khi bi xc tc bng
lc in (12) ri i ra ngoi theo ng khi.
Hi sn phm (7), c np vo ct chng ct phn on (13)
tch chia thnh cc sn phm khc nhau.. Xng v phn nh
hn c cho qua b phn ngng t ri vo thit b tch kh (14).
Sau khi tch kh, ta nhn c phn on C1, C2 m chng c th
dng lm kh nhin liu trong nh my. Phn on C3, C4 cha
nhiu propylen v buten c tch ra v dng lm nguyn liu cho
nh my ankyl ha v sn phm tip theo l xng kh butan
T ct phn on chnh ta cn nhn c cc phn on sn
phm nh naphta nng, LCO, v HCO. Phn HCO c th cho tun
hon li thit b phn ng (4), v cui cng l phn on du cn
c lm sch khi bn xc tc. Mt phn sn phm nh ca
thit b tch bn xc tc cng c cho tun hon vi HCO.
Tch kh t qu trnh nhit phn
Bng phng php chng ct nhit thp, c th tch c
metan, etan vi sch tng i cao.
Qu trnh phn tch kh c thc hin p sut 3MPa - 4MPa.
tch phn on metan, cn nhit t0 = -1000C, nhit ny c thit
lp nh vng lm lnh etylen, n lm vic ch khi c propylen (hoc
NH3), v propylen khi nn v lm lnh c kh nng ngng t v khi nn
n p sut khc nhau c th cho nhit t 00C - 400C. nhit
ny, kh nn etylen cng nh n p sut khc nhau m cho nhit t
(-600C) (-1000C).
Mt trong nhng s cng ngh phn chia kh khi nhit phn phn
on hyrocacbon lng c m t trn hnh 1.4.
Kh t thit b nhit phn c nn t t trong nm bc ca thit b
nn kh tuabin (1) ( trn s ch c ba mc ), sau mi bc, kh c
qua b lm lnh (2) v b phn ly (3), ti n c tch khi phn
ngng t (nc v nhng cht hu c), tch nhng hyrocacbon
nng nht, ngi ta ngn phn ngng t bc tip theo v cho quay li
b lc bc trc (trn s ch c nn bc I v II). Nh hiu ng
chng ct c thit lp v trong phn ngng sau bc I ca b nn kh
l hyrocacbon lng iu kin thng. Chng c tch ra trong kh
ha tan trong thp tch hi (4). Phn ngng t c chuyn qua phn
ch bin, cn kh quay li ng ht bc I ca b nn kh.

11

Hnh 1.4. S cng ngh tch kh trong nhit phn hydrocacbon lng.
1 My nn kh; 2, 8, 11, 18 Sinh hn; 3,12 - Thit b tch;
4, 6 Thp to hi nc; 5 - Thit b ti; 7 - Thit b sy; 13, 14, 19, 20, 21 Thp
chng ct phn on; 15 - Thit b trao i nhit; 16 - B phn cp nhit cho hi; 17 - Thit
b lm sch; 22 Van chnh p.

Sau khi nn bc ba, kh chuyn qua lm sch khi tp cht axit. Lm

sch bng dung dch kim hi luqua thit b lc m (5). Sau nn
kh n p sut 3,5 4 MPa. Phn ngng to thnh c tch ra khi
kh v sau khi qua thit b phn ly ca b nn kh bc IV, n chuyn qua
thp tch hi (6). Ti y kh ha tan c tch ra v quay li b nn
kh bc IV. Cht lng ca thp (6) gm hyrocacbon C4 C5 v tch
chng, phn ct nh cho vo thp ct (21). Ngi ta cn cho vo y
phn on tch c khi lm lnh su.
Sau khi tch hyrocacbon cao, kh chuyn t thit b sy (7) cha
y Al2O3 hoc zeolit v n b phn lm lnh su tch kh.
12

 tit kim, ngi ta lm sch s b kh tng bc nh cht lm lnh

c lch nhit khc nhau. Kh i qua hai thit b lm lnh (8) v (9)
nh vng propylen. trong b th nht, propylen ha hi khi t0 = -50C
n -150C p sut cao, cn trong b th hai th p sut khng kh
v nhit = -450C, iu tit kim c nng lng khi nn cht lm
lnh. Lm lnh tip trong b lm lnh (10) nh qu trnh ha hi phn
on etan thu c khi tch kh, v trong b lm lnh (11) nh cht lm
lnh l phn on metan. V nhng phn on kh metan v etan thot
ra t nhng b lm lnh ny c nhit thp nn ngi ta dng n
lm lnh nhng phn khc (trn s c ch r). Mt phn cu t kh
ngng t trong bung lm lnh s b. Kh c tch ra khi cht lng
trong thit b phn ly (12),nhng dng ny chuyn n nhng a tng
ng ca thp chng ct (13). Theo thnh phn hi v lng, thp ny
c gi l thp tch metan. Nhim v ca n l tch phn on metan
khi nhng hyrocacbon nng hn c thu li di thp. Metan l
cht kh kh ha lng, ngoi ra n c lm long bi H2 nh th cng
lm gim nhit ngng t ca n. Bi vy, lp lng hi lu trong
thp tch metan cn phi lm lnh tht su.Do , vic lm lnh c
thc hin nh qu trnh ha hi etylen lng t vng lnh p sut
khng kh v nhit t0 = -1000C. thay i tng phn qu trnh lm
lnh ny bng phn on metan thu c, ngi ta chn n p sut
0,5 0,6 MPa v dng n lm lnh pha trn ca thp.
Cht lng di thp tch metan (13) gm hyrocacbon C2 C4.
Mc tiu tip theo l tch C2 v C3 c thc hin trong thp chng ct
(14), c gi l thp tch etan. p dng bnh thng trong thp l 2,5
MPa, cn nhit pha trn thp gn -100C. Bi vy, lp lng hi
lu phi lm lnh nh vng lnh propylen, (propylen ha hi di p
sut c kh nng m bo nhit cn thit do qu trnh ha hi ca
n). Pha trn thp (14) thot ra l hn hp etylen v etan vi tp cht
axetylen v khi lng khng ng k metan v propylen. Phn on
ny n b phn lm sch hyro lm sch khi axetylen. Ngi ta
gia nhit n trong b trao i nhit (15) nh nhit ca dng ngc v
sau n b gia nhit hi (16). Sau , ngi ta thm vo mt lng
nh H2 v hyro ha trong thit b lm sch hyro (7) trn xc tc
khng ng nht.
Lm sch phn on lm sch bng nc trong b lm lnh (18)
v sau khi lm sch cho qua b trao i nhit (15), tip tc n c
chuyn n thp chng ct (19) gi l thp etylen. Nhim v ca n l
tch etylen v etan, v ng thi lm sch etylen khi metan v nhng
dn sut khi lm sch hyro.
Thp (19) thng lm vic p sut 2,0 2,3MPa v nhit pha
trn l 300C n -350C. Do , lm lnh phn ngng hi lu phi
13

nh qu trnh ha hi ca propylen lng t vng lnh. H2 cng tp cht

metan v etylen thot ra t pha trn th, c cho quay li giai on
nn kh ban u tng ng. Etylen lng t mt trong nhng a pha
trn thp (19) c thu li. i khi n c gi li trng thi lng v
khi chuyn n ni bo qun hoc xitec vn chuyn. Thng n
dng dng kh v c th yu cu nhng p sut khc nhau ( v d:
tng t nh phn on etan). Phn phn on etan lng t li thp
(19) b chn li v s dng lnh ca n nh m t trn.
Cht lng trong thp tch etan (14) chuyn n thp tch propan
(20). Trong thp (20), di p sut ~20 Mpa, phn on propan,
propylen c chng ct. Ngi ta lm lnh phn ngng hi lubng
nc. Ngi ta thu v bo qun phn on ny dng lng, nhng ty
vo p sut yu cu trong giai on tng hp tip theo m ngi ta
ngn v s dng lnh ca n cho nhu cu ny hoc khc. Phn
on C4 + C5 c thu hi di thp tch propan v a qua tch
thm thnh phn on buten v penten trong thp (21).
C c v tch phn on olefin
- Phn on olefin thu c khi tch kh nhit phn thng cha n
2 3% mentan v etan, cn nu khng lm lnh khi axetylen th c
n 1 2% hyrocacbon ny. Trong nhng thit b hin i, cht lng
etylen tng ng k v polyme ha n thnh polyetylen cn phi t
tinh khit ln hn 99,9%.
- Ty thuc vo ngun thu m c th thu c propylen v propan
vi t l khc nhau. Khi tch n t kh cracking, hm lng propylen ch
t 30 - 40%(v); cn khi nhit phn hyrocacbon lng, hm lng
propylen t 90 - 95%(v) propylen. Nhng cu t khc l hyrocacbon
C2 0,2 - 2,0%(v). Cn khi khng lm sch bng hyro th c 0,5
2,0%(v) metylaxetylen v propaien. Thng ngi ta dng phn on
propylen tng hp, khng cn phi lm sch thm. i vi cc qu
trnh tng hp cn hm lng propylen cao hn, tt hn l tin hnh
c c, ng thi tch mt khi lng propan bng chng ct. Khi
chng ct, trong propan c c metylaxetylen cng propaien. ngi ta
thu propylen c sch cao (99,9%) cn thit sn xut polypropylen.
- Phn on buten: Cng ty vo ngun gc thu m c th chia ra
khng ch theo hm lng tng i ca buten v butan m cn theo t
l ca nhng ng phn khc nhau ca chng, bao gm c butaien1,3.
Bng 1.2. Thnh phn cc cu t ca phn on C4 (% khi lng)
Izo-C4H8 C4H6
Qu trnh
n-C4H10 Izo-C4H10 n-C4H8
Cracking
10 - 20 35 - 50
25 - 40
5 - 10
xc tc
Nhit phn 5 - 7
1-3
20 - 25
30 - 35
30 - 40
14

Vic tch phn on C4 bng chng ct bnh thng khng th

c v ha hi ca cc cu t trong phn on rt gn nhau. V vy
phi dng nhng phng php c bit da trn c s chng ct chit
tch v qu trnh hp ph ha hc.
Khi ch bin phn on C4 ca nhit phn, tch butaien-1,3,
phng php thng dng l hp ph ha hc bng dung dch
ammoniac-acetat ng I:
C u + + (N H 3 )4 + C 4 H 6
C u + (N H 3 .C 4 H 6 + N H 3
Nhng phc ny cng vi butaien-1,3 bn hn so vi phc ca
olefin. Khi x l phn on bng dung dch cht hp ph nhit t = 100C 00C, n ch yu l butaien-1,3. Khi gia nhit n 400C, xy ra
qu trnh gii hp nhng olefin ni vi phn butaien-1,3. Ti 700C
750C, butaien-1,3 sch c tch ra, cn dung dch hp th sau khi
lm sch s quay li thit b hp ph.
Ngi ta thc hin qu trnh trong tng ngc ca thit b cng b
khuy. Mi thit b c trang b b phn ly v my bm. Dung dch
cht hp ph sch c cho vo thit b u tin, cn phn on buten
th vo thit b cui, ngi ta thit lp iu kin ti u hp th phn
on ha long bng dung dch cht hp th sch, cn ngi ta hp th
phn on c c bng dung dch bo ha.
Trong s nhng thit b hin i, ngi ta thc hin qu trnh hp
th trong mt s thp chit tch, trong phn on lng v dung dch
hp th chuyn ng ngc chiu nhau nh s chnh lch t trng
(hnh 1.5).
Cht hp th lm lnh c cho vo pha trn thit b chit tch
u tin (1) v chuyn ng t trn xung qua tt c ba thit b. Ngi
ta cho phn on C4 ban u vo on gia b chit tch th ba v n
c y ln trn nh nhng phn on nh v n c chuyn t
thit b ny qua thit b kia bng bm. Phn on C4 tch khi
butaien -1,3 (C4H10 + C4H8) c ly ra t phn trn ca b chit tch
(10) - b ny ng vai tr nh b phn ly. Dung dch bo ha t di b
chit tch (3) bm vo thp tch hi (4), ti y vi nhit t = 400C
phn olefin c chng ct. Bi v chng cha nhiu butaien -1,3 nn
chng quay li hp th pha di thp (3).
Dung dch t di thp (4) cho qua thp tch hi (5), ti y nh qu
trnh gia nhit m butaien-1,3 c gii hp, cn cht hp th ti sinh
c lm lnh trong b lm lnh (6) v quay li nhng b chit tch.
Hin nay tch butaien-1,3 ngi ta thng dng phng php
chng ct chit tch.Theo so snh, furfurol l cht chit tch c u th
hn axetonitril v N-metyl-pirolidon. Khi c chng, qu trnh khc bit
v qu trnh ha hi tng i ca butaien -1,3 v olefin tng ln nh
butaien-1,3 c th lp tc tch khi nhng cu t khc.
15

Phn ct C4

Hnh 1.5. S cng ngh tch butadien -1, 3 t phn on C4

bng phng php hp ph.
1, 3 - Thit b trch ly; 4, 5 - Thit b to hi; 6 Sinh hn;
7 - Thit b un nng; 8 - Thit b ngng t.

izo-buten c tch ra bng H2SO4 40% 60% (H2SO4 khng phn

ng vi olefin khc). Khi t n nhit thp to thnh axit
tecbutyl-sunfuric v tec-butanol, chng b phn hy n khi to thnh
izo-buten, cn to ra nhng sn phm ph l polyme izo-buten thp
phn t:
+ H 2O
(C H 3 )3 C O H

(C H 3)2 C = C H

H 2S O

-H 2S O

(C H 3)2 C O S O 2O H

S cng ngh tch phn on C4 ca qu trnh nhit phn

hydrocacbon lng, bng phng php chng ct chit tch c m t
trn hnh 1.6.
Phn on C4 cho vo phn gia thp (1), cn phn trn thp cho
axetonitril, dung dch di thp cho qua thp tch hi (2), butaien1,3 c chng ct v cht chit ly c ti sinh quay li thp (1). Hn
hp hp th butan v buten chuyn n b phn (3) tin hnh hp
thu ha hc izo-butan, sau phn cn li n thp chng ct chit
tch (4). Pha trn tch c butan ri chng ct thm thu c nbutan v izo-butan ring bit, n-buten trong thp (5) c chng ct
khi cht chit ly, cht chic ly quay li thp (4).

16

C4 H10

+C4 H8

7
iso-C4H8
CH3 CN

1
C4 H6

C4 H10
4

n- C4 H8
5

CH3 CN
8

Hnh 1.6. S cng ngh tch phn on C4

bng phng php chng ct chit tch.
1, 4 - Thp chng ct phn on; 2, 5 - Thp to hi;
3 - B phn hp ph ha hc iso-buten; 6 - Sinh hn;
7 - Thit b ngng t; 8 - B cung cp nhit.

- Phn on penten: c thnh phn rt phc tp, s liu tng ng

bng 1.3.
Bng 1.3. Thnh phn cc cu t ca phn on C5 (% khi lng)
Crackin
Cracking
Hp cht
Nhit phn Hp cht g
xc Nhit phn
xc tc
tc
n-pentan 12
26
Xyclopent 1-2
izo60
24
en
9
pentan
12
12
Pentaien 12
n-penten 16
12
Izo-pren
8-12
izoXyclo
penten
pentaien
Trong s nhng hp cht ny, izo-penten, izo-pren, izo-pentan v
xyclopentaien c ngha quan trng nht. tch xyclopentaien,
ngi ta dng phng php dime ha n:
2

CH2

CH2

Ngi ta gi phn on penten di p sut v nhit t =

100 C 1200C, tin hnh chng ct phn hyrocacbon cn li khi
nhng dime c nhit si cao. Sau depolyme ha bng cch gia
0

17

nhit n nhit t = 2000C th thu c xyclopentaien. Hyrocacbon

ny v dime ca n l nguyn liu chnh cho hng lot cc qu trnh
tng hp.
Izo-pren t phn on C5 ca nhit phn hyrocacbon lng c tch
khi chng ct chit tch kt hp vi vic chng ct tng phn nhng
tp cht v chng ct nguyn liu ca phn on, bi v hp th ha
hc bng dung dch ammoniac-ng trong trng hp ny khng hiu
qu.
1.3. Hyrocacbon thm
V gi tr, hyrocacbon thm l nguyn liu tng hp hu c
ha du, ng th 2 sau olefin. Nhit si ca nhng ng phn
xylen rt gn nhau, v chng ch c th c tch tng phn bng
chng ct tht chnh xc. P-xylen v durola nng chy nhit ln
hn ng phn ca chng, nn thng dng phng php kt tinh
tch chng. Ngi ta cn dng phng php ny tch naphtalen.
S c mt ca h lin hp lm cho hyrocacbon thm c kh
nng hp thu cao hn so vi nhng hyrocacbon khc, c bit vi
parafin v naphten. Hyrocacbon thm c kh nng ha tan ln trong
nhng cht lng phn cc nh dietylenglycol, phenol. Trong nhng
hyrocacbon khc, chng tan rt t. Chng d b hp ph bi nhng
cht hp ph rn (than hot tnh, silicagen). Nhng tnh cht ny ca
hyrocacbon thm c dng trong cng nghip tch chng bng
cch chit tch, chng ct chit tch v hp ph
Toluen v xylen c nhit bt chy thp nn nguy him chy
ca chng rt ln. S c hi ca chng vt tri hn nhng
hyrocacbon loi khc v c t trong mu ph hy tun hon mu ty
xng. Do nng cho php trong khng kh ti ni sn xut i vi
benzen l 20mg/m3
Hyrocacbon thm thu c t qu trnh thm ha cc loi khong
sn. C th l phng php nhit phn, reforming xc tc sn phm
du m, cc ha than .
1.3.1. Thm ha nhng sn phm du
Nhit phn: khi nhit phn sn phm du vi mc ch thu olefin thp
phn t, xy ra qu trnh thm ha nhng hyrocacbon mch thng.
Kt qu l trong sn phm lng ca nhit phn tch t dn mt lng
ln hyrocacbon thm.
Reforming xc tc: l mt trong s cc qu trnh quan trng ca cng
nghip ch bin du. Qu trnh ny cho php sn xut cc cu t cao
octan cho xng, cc hp cht hyrocacbon thm (BTX) cho tng hp
ha du. Ngoi ra, qu trnh cn cho php nhn c kh hyro k thut
vi gi r nht so vi cc qu trnh iu ch hyro khc. Qu trnh
reforming xc tc thng dng nguyn liu l phn on xng c tr s
18

octan thp, l phn on xng ca qu trnh chng ct trc tip t

du th, hay t phn on xng ca cracking nhit, cc ha hay
vibreking.
C th ni reforming xc tc nh mt qu trnh thm ha cc sn
phm du m. Khc vi qu trnh cracking dng xc tc aluminosilicat,
trong reforming ngi ta dng xc tc 2 chc nng. Qu trnh chuyn
ha ha hc khi reforming xc tc c xc nh bi 2 chc nng ca
xc tc. Trn tm axt xy ra phn ng ng phn ha parafin thnh
izo-parafin v naphten vng 5 cnh thnh ng ng cyclohexan; mt
khc trn tm kim loi xy ra phn ng ehyro ha to vng no, vng
thm.
1.3.2. Qu trnh cc ha than
Qu trnh cc ha b ko theo bi qu trnh chuyn ha ha hc su
phn hu c ca than. Cng nh trong nhng qu trnh ct mch nhit
nhng sn phm du m, trong qu trnh cc ha, nhng sn phm
lng v kh c to thnh t than t hn t du m. V vy, hiu
sut cc ca n rt ln (75 80%), cn sn phm lng khng ng k
(4-5%)
1.3.3. Tch v lm sch hyrocacbon thm
Hm lng ca hyrocacbon thm trong sn phm lng thu c
t nhng qu trnh thm ha khc nhau dao ng t 30 36% (nhit
phn v reforming xc tc) n 95 97% (ankyl ha benzen v nha
cc ha than ). Trong chng cn c olefin (t 2 3 n 15%), parafin
v naphten. Ngoi ra, trong sn phm cc ha c mt s hp cht ca
oxi (phenol, cumol), baz piridin, hp cht vng khng ng nht ca
lu hunh (tiofen, tiotolen, tionaphten), chng c nhit si gn vi
nhng hyrocacbon thm tng ng.
Vi sn phm thu c t phng php ankyl ha benzen v cc
ha than . Qu trnh lm sch bao gm nhng giai on c bnsau:
Tch phenol bng cch x l phn on sn phm vi dung dch
kim, ri t dung dch kim gii phng phenol bng CO2:
A rO N a + H 2 O

A rO H + N a O H
2 A rO N a + H 2 O

+ CO

2 A rO H + N a 2 C O

Giai on quan trng l lm sch hyrocacbon thm khi olefin.

i vi sn phm thu c t qu trnh cc ha than c cha t
olefin, ngi ta x l bng axit sunfuric H2SO4 90% 93%. Khi phn
olefin chuyn thnh ankylsufat v chuyn vo lp axit v phn cn li b
polyme ha.

19

RCH=CH2 + H2SO4
nRCH=CH2

toC

toC

R-CH-OSO2OH

CH3
-(CH-CH2)-n
R

Vi sn phm t qu trnh nhit phn, c cha mt lng ln olefin,

nn vic lm sch chng bng H2SO4 khng hiu qu. Khi , ngi ta
thc hin s hyro ha hn hp sn phm trn xc tc khng nh
hng n vng thm.
i vi phn on sn phm thu t s cc ha, sau khi lm sch
bng H2SO4, chng c chng ct thu c sn phm cui cng.
Nhng i vi sn phm thu c t nhit phn v reforming xc tc,
c cha rt nhiu parafin nn chng ct thng khng thc hin c.
Lc , ngi ta dng chit tch hyrocacbon thm bng dung mi
chn lc (di-, tri-, v tetra etylenglycol) v tng chn lc, ngi ta
thm vo qu trnh chit tch 5% 8% nc.
S tch hyrocacbon thm bng phng php tch chit c m
t trn hnh1.7.
Ngi ta cho phn on nguyn liu ban u vo phn di thp
chit tch (1), n c chuyn ln trn ngc dng vi cht chit ly t
pha trn thp i xung. Phn rafinat thot ra t pha trn thp c mang
theo mt lng cht chit ly, ti s dng n, ngi ta ra rafinat
trong b (2) bng nc, sau dng nh nhin liu. Cht chit ly bo
ha t di thp (1) c un nng trong b trao i nhit (3) bng
cht chit ly ti sinh nng ri chuyn n thp (4) thc hin chng
ct chit tch hyrocacbon thm khi nc. Trong thit b phn ly (5),
nc c tch ra v n li quay li thp chng ct (4), cn hn hp
hyrocacbon thm cho vo chng ct cui cng. Cht chit ly t di
thp (4), sau khi lm lnh s quay li chit tch, cn mt phn ca n
c mang i ti sinh trong thp (6) chng ct phn nc d v lm
sch khi sn phm ngng t. Mc tch hyrocacbon thm bng
phng php ny t n 93 99%.

20

Rafinat

7
H . C thm
5

nc
6

Phn ct
ban u
8
3

nha
Tc nhn trch

Hnh 1.7. S cng ngh trch tch hydrocacbon thm.

1, 4 - Thp chng ct phn on; 2 - Thp ti; 3 - B trao i nhit;
5 - Thit b tch; 6 - Ct ti sinh tc nhn trch; 7 - Thit b ngng t;
8 - B cp nhit.

tch hyrocacbon thm c vng ngng t (naphten, antraxen,

phenaltren), ngi ta dng phng php tinh th ha. T phn on
antraxen ca nha than (2700C 3500C), c nng chy cng vi
kali hyroxyt v bng thy phn, ngi ta tch c mt s cht cn
thit cho tng hp hu c l cacbazol:
+KOH
N
H

-H2O

N
K

c tnh cc phn on hyrocacbon thm

Hyrocacbon thm thu c t 2 ngun chnh l t than v t
du m. Chng khc nhau v hm lng hp cht hu c cha lu
hunh. Sn phm thu c t du m, v ngay t phn on du
nguyn liu ban u cha rt t lu hunh hoc kt qu lm sch bng
hyro tt, nn hm lng S ln trong sn phm ch cn 0,0001
0,002%; cn sn phm t qu trnh cc ha than th nhiu hn n
khong 100 ln. iu ny c ngha quan trng trong cc qu trnh c
dng xc tc vi nguyn liu l nhng hp cht thm, nu c hp cht
cha lu hunh th qu trnh nhim bn xy ra nhanh hoc phi tng
lu lng xc tc. Nhng tp cht khc l olefin (ch s brom n 0,6g
Br2/100g) v parafin ( sunfit ha khng nh hn 99%)
Benzen v toluen: ty vo ngun thu m c hm lng t 99,0 n
99,9% cht c bn.
Phn on xylen: c th c chia theo t l ng phn ca xylen v
21

hm lng etylbenzen, c nhit si gn vi xylen (136,20C). To

thnh khi phn ha nhit nguyn liu. Thnh phn v d ca phn on
xylen nh sau:
Bng 1.4. Thnh phn cc ng phn xylen ((% khi lng)
0-xylen
m-xylen
p-xylen
Etylbenzen
Xylen t ha
10-12
52-60
14-20
8-12
hc cc ha
Xylen t ha
20-24
40-45
18-20
14-46
hc du m
1.4. Axetylen.
Axetylen l cht kh khng mu, dng tinh khit c mi ete yu. N
c gii hn n trong khng kh ln, nguy him v n ca axetilen
cng gia tng do qu trnh phn hyn thnh nhng cht n gin ta
nhiu nhit. Tnh quan trng khc ca axetylen l kh nng ha tan ca
n ln hn nhiu so vi cc hyrocacbon khc.
Axetilen thu c t cc qu trnh ch bin khc nhau.
1.4.1. Ch bin axetilen i t cacbua canxi
Cacbuacanxi thu c t oxit canxi v cc trong l h quang in.
Phn ng thu nhit mnh v i hi ngun nng lng d tr ln. Khi
phn hy cacbua canxi bng nc theo phn ng ta nhit, ta thu c
axetylen
0
CaO + 3C T C CaC2 + CO

CaC2 + 2H2O

C2H2 + Ca(OH)2

T 1kg cacbua canxi k thut c cha tp cht cc, oxit canxi v

nhng cht khc, c th thu c 230 280lt axetylen. Theo l thuyt,
t 1kg cacbua canxi sch th s to thnh 380lt axetylen.
Khi phn hycacbua canxi, cn phi tun theo mt s iu kin
qu trnh thc hin bnh thng. Phn ng khng ng nht, vn tc
ca phn ng ph thuc vo kch thc ht cacbua. Khi phn ng
phi khuy trn v trn ht cacbua c th to thnh lp ngn cn qu
trnh phn hy ca cacbua v dn n qu trnh chy cc b. Cn phi
gii nhit cho sn phm u n, m bo cho axetylen khng b
polyme ha v phn hy .
Phng php kh
Nhit phn ng c ly ra do mt khi lng nc d, nh qu trnh
ha hi ca n. Ca(OH)2 thu c dng kh v n c dng ch
to vt liu xy dng
Phng php t
Nhit phn ng c gii phng bng nc d, un nng n ln
50 600C. Trong , c 1kg cacbua canxi cn gn 10kg nc. Nh th,
22

Ca(OH)2 thu c dng huyn ph trong nc, t c li cho vic tn

dng tip theo.
S cng ngh iu ch axetylen t cacbua canxi

Hnh 1.8. S cng ngh iu ch axetylen t cacbuacanxi

1 Toa cha; 2 - ng ray; 3 Thng cao v; 4, 7 Sinh hn;
5 - Thit b lng; 6 - Thit b sinh axetylen; 8, 10 Thp ti; 11 Thng cha kh t;
12 - Thit b chn la, 13 - My nn.

CaC2 c ti n trong nhng toa cha (1), chuyn ng theo

ng ray (2), ri c vo bunke ca b ti sinh (6) loi t. Sa
vi thu c trong b ti sinh khi phn ha CaC2, cho qua thit b lng
(5), c khuy lin tc nh b khuy hnh qut. B khuy ny chuyn
phn bn lng n khe mng tho trung tm. Bn vi c bm bng
bm c bit n nhng ging lng. Dung dch Ca(OH)2 trong nc, t
b lng (5), qua b lm sch (4) v nc thu hi quay tr li thng cao
v (3). Ti y, ngi ta thm mt lng nc mi b vo lng hao
ht. T thng cao v, nc chy n thit b ti sinh (6).
Axetylen to thnh trong thit b ti sinh c nhit 50 600C, n
c lm lnh trong b lm lnh (7), c tch khi phn ngng v
chuyn qua thit b lc bc thang (8) vi dng hi lu l dung dch
H2SO4. Trong (8), axetylen c gii phng khi phn d ammoniac tan
trong nc lc ti sinh v lc ngng t ti b lm lnh (7). Sau ,
chuyn n thit b lc (9) vi dng hi lu l dung dch hipoclorua natri.
Cui cng, chuyn n b lc kim (10), lm sch clo b nhim
thp hipoclorua. i vi tt c nhng dung dch hp thu th phn hi lu
c thc hin nh bm ly tm. Phn dung dch s dng, c ly
ra khi h thng mt cch nh k v thay dung dch mi. Axetylen
lm sch c thu li trong thng cha kh t (11). T y, n c
chuyn i tiu dng bng thit b nn kh (13), sau khi qua van thy lc
23

bo him hoc thit b chn la (12).

So snh nhng phng php iu ch axetylen: nhc im chnh
ca phng php cacbua thu c axetylen l chi ph nng lng
in ln cho vic thu c CaC2, nhiu giai on chuyn ha nhin liu
(CaCO3 CaO CaC2 C2H2) v vn u t trong sn sut ln. u
im ca phng php l thu c axetylen m c, lm sch n khi
tp cht khng kh. Ngoi ra, thu cacbuacanxi da trn ngun than
di do.
1.4.2. Ch bin axetilen i t hyrocacbon
Ngi ta thu c axetylen t metan v nhng parafin khc theo
phn ng thun nghch sau:
2CH4

C2H2 + 3H2

C2 H6

C2H2 + 2H2

y l nhng phn ng thu nhit, cn bng ca phn ng chuyn dch

v bn phi khi nhit t = 10000C 13000C, trong thc t t = 12000C
16000C.
Ch bin axetylen theo phng php ny tng i phc tp do xy
ra phn ng ph, ch yu l qu trnh phn hy axetylen thnh cacbon
v hyro. Phn ng ph xy ra mnh lit v t cc i ti nhit t =
12000C 16000C. Nhit ny, cng chnh l nhit phn ng chnh
t cc i.
Cng nh trong nhng trng hp khc, vic iu chnh hiu sut
phn ng bng vic rt ngn thi gian phn ng (t = 0.01giy), bng
vic gim chuyn ha ca nguyn liu xung cn 50%.
Ty theo cch cp nhit, thc hin phn ng nhit phn nhng
hyrocacbon thnh axetylen, ngi ta chia ra 4 phng php: nhit
phn ti sinh, nhit phn ng th, nhit phn cracking in, nhit phn
oxy ha.
1.5. Kh tng hp
Kh tng hp l hn hp kh gm hyro v oxit cacbon theo cc t l
th tch khc nhau t 1 :1 n 1 : 2 - 2.3.
sn xut kh tng hp, trc tin ngi ta dng than, sau dng
qu trnh chuyn ha hyrocacbon, ngi ta thc hin qu trnh ny
theo 2 phng n: dng xc tc v dng nhit.
1.5.1. Chuyn ha hyrocacbon
Hng dng xc tc
Phn ng chnh ca phng php ny l chuyn ha hyrocacbon
bng hi nc trn xc tc Ni/Al2O3 .
CH4 + H2O Ni.Al2O3 CO + 3H2

T l sn phm gia H2 : CO kh cao, trong khi s dng cho

24

tng hp hu c, t l ny rt nh, t 1 : 1 n 2 - 2.3 : 1. Cc t l nh

ny t c bng cch, hoc tin hnh chuyn ha cc hyrocacbon
lng hoc thm vo hi nc mt lng dioxit cacbon trong khi chuyn
ha
R-CH2-R + H2O
CH4 + CO2

Ni.Al2O3

Ni.Al2O3

CO + 2H2

2CO + 2H2

Cng ngh ca qu trnh gm nhiu giai on: chun b nguyn liu,

chuyn ha, ti sinh nhit, lm sch sn phm khi CO2 . Trong giai
on u, cn lu xc tc niken rt nhy vi cc hp cht cha lu
hunh. Do vy, hm lng lu hunh phi khng ch trong gii hn
1mgS/m3. Nu cc nguyn liu s dng khng p ng yu cu ny, th
phi tin hnh qu trnh loi lu hunh bng xc tc. Giai on chun b
nguyn liu cn bao gm trn kh vi hi nc v un nng s b hn
hp phn ng.
Cc thit b s dng cho qu trnh chuyn ha hyrocacbon

Hnh 1.9. Cc thit b phn ng s dng cho s chuyn ha xc tc hydrocacbon

a - L ng; b - L chuyn ha oxy

Do qu trnh thu nhit ln, cc chuyn ha hyrocacbon c thc

hin trong cc l ng (hnh 1.9a). Nguyn liu c a vo ng c
cha xc tc d th v c t nng bng kh i lu, nhit t
c ch yu bng phng php bc x nhit. Nhc im ca h
thng ny l i hi cc ng phi c chu nhit ln, mt khc th tch
hu dng ca l tng i thp v xc tc ch chim mt phn nh th
tch ca cc ng.
25

 khc phc nhc im trn, ngi ta a mt h thng khc,

trong cc phn ng thu nhit thc hin ng thi vi cc phn ng
ta nhit (hnh 1.9b). C th l qu trnh t chy mt phn
hyrocacbon khi a oxy vo s lm cho hiu ng nhit ca ton b
cc qu trnh tr nn dng.
Cc tnh ton cho thy i vi h thng ny cn a hn hp CH4 v O2
theo t l 1,0 : 0,55 trnh qu trnh n xy ra. Hn na, hn hp ny
s b lm long bi hi nc, do s hn ch ti a qu trnh n. T l
th tch gia hi nc v metan c th thp hn so vi trng hp
khng c oxy, c th l t 1 : 1 n 2,5 3,0 :1. Qu trnh ny c gi
l oxy ha, n khng i hi qu trnh gii nhit t bn trong v c th
thc hin trong cc l vi lp xc tc dy c.
Vch l c xy bng gch chu la v c v o nc lm lnh
(trong v o ny s tin hnh ti sinh hi nc). phn trn ca l, c
b phn trn, v ti y ngi ta s a hn hp CH4 + H2O v O2 +
H2O vo. B phn trn c nhim v ng nht ha hn hp ny v
trnh hin tng n hoc bc chy. Qu trnh t chy metan xy ra
nhanh hn qu trnh chuyn ha. V vy, cc lp xc tc trn cng
nhit nhanh chng t n cc i (1100 12000C), sau gim
xung cn khong 800 -9000C khi ra khi l. So vi h thng l ng, h
thng ny c nhiu u im ni bt, nht l khng cn trang b cc ng
chu nhit cao, kt cu l n gin v th tch hu dng tng ng k.
Trong thi gian di, cc thit b thng c lm vic vi p sut
gn vi p sut kh quyn, v nhng thit b loi ny hin nay vn cn
c s dng. Tuy nhin, gn y ngi ta chuyn qua cc thit b
lm vic di p sut cao, khong 2 3 MPa. Mc d iu ny lm cho
cn bng chuyn dch v pha khng mong mun, nhng n vn chng
t hng lot u th. Trc ht, do vn tc phn ng tng ln p sut
cao. Do vy, c th tng nng sut ca thit b, gim kch thc ca n.
Tip theo l c th gim cc chi ph nng lng v ti sinh nhit ca cc
kh nng.
S nguyn tc ca qu trnh chuyn ha metan (kh thin nhin) bng
phng php oxy ha di p sut cao c trnh by trn hnh 1.10.
Metan nguyn liu c lm sch khi lu hunh (nu cn). Sau ,
c nn trong my nn (1) n 2 3MPa v trn vi mt lng hi
nc v CO2 cn thit. Hn hp ny c un nng trong thit b trao
i nhit (2) n 4000C, sau c a vo thit b chuyn ha (6).
Ti y, ngi ta cng a vo hn hp kh oxy v hi nc. Thit b
chuyn ha c lm lnh lp v o, nhit ta ra s ti sinh hi nc
vi p sut 2 3MPa v hi ny c thu hi thit b thu hi hi
nc (5). Nhit ca kh i ra (800 9000C), c s dng trong ni hi
ti sinh hi (4) iu ch hi p sut. T y, hi nc thu c s
26

tip tc c s dng trong qu trnh chun b nguyn liu. Qu trnh

lm lnh c kt thc trong thit b ti nc (7), nc ny c i
lu trong sinh hn (8).

Hnh 1.10. S cng ngh oxy ha kh thin nhin di p sut cao

1 - My nn; 2, 3, 10 - Thit b trao i nhit; 4 - Ni hi ti sinh hi;
5 - Thit b thu hi hi; 6 - Thit b phn ng; 7 - Thit b ti nc lm lnh;
8 - Sinh hn; 9 - Thit b hp ph; 11 - Thit b gii hp ph;
12 - Thit b chnh p; 13 - Thit b un nng.

Hn hp kh thu c giai on ny c hm lng cc cht nh

sau (phn trm th tch): 15 45% CO, 40 75% H2, 8 15% CO2,
0,5% CH4 v 0,5 1% N2 v Ar.
Sau l giai on tch loi sn phm kh tng hp khi CO2 bng
cch cho nc hp th p sut cao; nc c cha monoetanolamin
hoc kalicacbonat. Khi un nng v gim p sut, s xy ra qu trnh
gii hp ph CO2 v dung dch hp ph c ti sinh:
CH2OHCH2NH2 + CO2
K2CO3 + CO2 + H2O

CH2OHCH2NH2.CO2

2KHCO3

Qu trnh hp ph CO2 c tin hnh trong thit b hp ph (9),

hn hp kh thu c y s a i s dng. Cn qu trnh ti sinh
dung dch hp ph c tin hnh thit b (11).
thu c 1m3 hn hp kh lm sch khi CO2,cn s dng
0,35 0,40m3 kh thin nhin, 0,2m3 oxy k thut, 0,2 0,8kg hi
nc.
Hng dng nhit
Qu trnh chuyn ha hyrocacbon nhit cao (1350 14500C)
xy ra khng c mt xc tc. Bn cht ca qu trnh ny l oxy ha
nhit khng hon ton kh metan (hoc cc phn on lng ca du
27

m), trong phn ng c bn nht l oxy ha CH4 thnh phn hn

hp CO, H2O v H2:
CH4 + CO2

CO + H2O + H 2

Ngoi ra cn to thnh mt lng CO2 do nhit phn cc

hyrocacbon C3 v C2 (bao gm c axetylen). giai on cui ca qu
trnh, s chuyn ha hyrocacbon cn li thnh CO v H2. y, s
thit lp mt cn bng gia cc oxyt cacbon, m nhit cao s c
li cho vic to thnh CO. C th nhn thy, khi axetylen b phn hys
to thnh cacbon v cacbon ny cng s b hi nc tc dng sinh
ra CO:
C + H 2O

CO + H2

Hiu sut to thnh cacbon tng ng k trong qu trnh chuyn ha

hyrocacbon lng nhit cao. Do vy hn ch n, ngi ta
thng thm mt lng hi nc vo nguyn liu ban u. Nh vy,
qu trnh ny c nhiu im ging vi qu trnh nhit phn oxy ha
metan thnh axetylen, ch khc l thi gian lu nhit phn ng
tng ln (khong 1 giy, so vi 0,001 0,01 giy). Phng trnh tng
cng ca cc phn ng chuyn ha metan v hyrocacbon lng nhit
cao nh sau:
CH4 + 0.5O2
CnH2n + 2 + 0.5O2

CO + 2H2

H = 35.6 Kj / mol
298

nCO + (n + 1)H2

Nh vy t l H2 v CO ph thuc vo nguyn liu ban u, c th

thay i c t 2 : 1 n 1 : 1. Ngoi ra, kh cn cha 2 3% (th tch)
CO2, 0,3 0,5% CH4 v nh hn hoc bng 1% N2 v Ar.
Qu trnh chuyn ha hyrocacbon nhit cao c thc hin
p sut t 2 3MPa n 10 14MPa. Thit b phn ng cho qu trnh
ny hon ton tng t nh trn H.1.8b, ch khc l trong khng c
xc tc v cc v cha xc tc. y l thit b loi rng s dng trong
cc trng hp p sut cao. Thit b c b phn cch nhit bn trong v
c v o nc bn ngoi, ng thi c trang b b phn trn
hyrocacbon v oxy m bo qu trnh ng nht ha hn hp trnh
hin tng n. u im ca qu trnh ny l cho php kh nng phn
ng n gin, khng i hi cht lng cao ca nguyn liu. Nhng u
im ny cho php kh nng ng dng rng ri ca cc qu trnh
chuyn ha nhit cao, c bit i vi cc hyrocacbon lng (ngay
c i vi mazut v du th).

28

Hnh 1.11. S cng ngh chuyn ha nhit cao ca mazut

1 - Thit b nhit; 2 - Thit b phn ng; 3 - Thit b thu hi bi than;
4 - Thit b lng; 5 - Thit b trao i nhit; 6 - Thit b chuyn ha oxit cacbon; 7 - Khi lm
sch sn phm khi CO2; 8 Sinh hn.

S cng ngh chuyn ha mazut c biu din trn hnh 1.11.

Mazut di p sut 2 3Mpa, c un nng n 500 8000C trong
thit b (1) nh s dng nhit ca cc kh chuyn ha. Thit b ny
bao gm b phn trao i nhit v ni hi (ging nh trn hnh 1.8).
Mazut sau khi t nng, c a vo b phn trn ca thit b
chuyn ha (2), ngi ta cng a vo y hn hp oxy vi hi nc.
Ti v o ca thit b ny, s ti sinh hi nc c p sut ca p sut
hi nc ban u. Kh nng i ra t thit b chuyn ha, c a tr
li thit b nhit (1) nhm tn dng nhit ca chng. Tip theo l qu
trnh tch mui than bng cch phun nc thit b (3). Nc cng vi
mui than s chy xung thit b lng (4). Ti y, ngi ta thm vo
phn on nh du m c kh nng kt t v tch mui than t nc.
Sau khi tch mui than, kh c a i tch khi CO2 theo cc
phng php nu phn trn. Trong nhiu trng hp cn thit
phi thay i t l H2 : CO trong sn phm kh theo chiu hng tng
hm lng H2. Cng vic ny c th thc hin trong khi chuyn ha
oxyt cacbon theo trnh t sau: kh c t nng trong thit b trao i
nhit (5) n 4000C, sau cho thm mt lng hi cn thit v chuyn
vo trn thit b chuyn ha (6). Ti y, trn lp xc tc lin tc (oxyt
st, crm v magie) s xy ra qu trnh chuyn ha mt phn oxyt
cacbon:
CO + H 2O

CO2 + H 2

Hn hp kh thu c y s c t l H2 : CO cn thit v tip tc

c i qua thit b trao i nhit (5), sau c lm sch khi CO2
trong khi (7) v mang i s dng.
iu ch 1000m3 hn hp CO + H2 cn 250kg mazut (hoc 380m3
29

kh thin nhin), 250 270m3 oxy v 60kg hi nc. Trong , ti thit

b nhit s ti sinh 850 900kg hi p sut cao.
1.5.2. iu ch kh tng hp bng phng php kh ha than
iu ch kh tng hp t than da trn qu trnh tc dng ca hi
nc theo phn ng thun nghch v thu nhit sau:
C + H 2O

CO + H2

Cn bng ca phn ng chuyn dch v bn phi khi nhit 10000C 11000C

Ngoi ra cn xy ra qu trnh chuyn ha ca oxit cacbon di tc dng
ca hi nc
CO + H2O

CO2 + H2

Hin nay qu trnh kh ha than thng tin hnh di p sut cao vi

mc ch nng cao nng sut thit b, p sut s dng l 2 3MPa.

30

CHNG 2: CC QU TRNH C BN TRONG CNG NGH TNG

HP HU C
2.1. Qu trnh ankyl ha
2.1.1. c tnh ca qu trnh ankyl ha
Ankyl ha l cc qu trnh a cc nhm ankyl vo phn t cc
cht hu c hoc v c. Trong thc t qu trnh ankyl ha cc olefin
nh v paraffin (iso-butan) thnh cc cu t tt cho xng, ankyl ha
benzen v ng ng to ankyl benzen v ng ng dng pha ch
xng v lm nguyn liu tng hp hu c ha du. Ngoi ra, ngi ta
cn a nhm ankyl vo hp cht mercaptan, sunfit, amin, cc hp
cht cha lin kt ether v qu trnh ankyl ha cn l giai on trung
gian trong sn xut cc monome v cc cht ty ra.
2.1.2. Phn loi phn ng
Da trn lin kt c hnh thnh
Ankyl ha theo nguyn t cacbon (C-ankyl ha):
Th nguyn t H ni vi cacbon bng nhm ankyl.
C 2H 5
+ C2H5Cl

XT

+ HCl

Cc parafin v hydrocacbon thm tham gia phn ng ny.

Ankyl ha theo nguyn t oxy v lu hunh (O, S - alkyk ha):
Phn ng dn n s to thnh lin kt gia nhm ankyl v nguyn
t lu hunh hoc oxi.
OH

OC2H5
+ C2H5OH

XT

+ H2O

Ankyl ha theo nguyn t nit:

Phn ng th cc nguyn t H trong amoniac hoc trong amin bng
cc nhm ankyl, y l phng php tng hp amin.
ROH + NH3

XT

RNH2 + H2O

31

Ngoi ra cn c cc qu trnh ankyl ha theo nguyn t khc (Si,Pb,

Al - ankyl ha)
2RCl + Si

XT

R2SiCl2

Da trn cu to ca nhm ankyl trong sn phm c to thnh

Ankyl ha mch thng
C 2H 5
+ C2H5Cl

XT

+ HCl

Ankyl ha mch nhnh

CH - CH3
+ CH3 - CH = CH2

H+

CH3

Ankyl ha mch vng

+

Cl

XT

+ HCl

Mt s phn loi khc l da trn s khc bic v cu to ca nhm

ankyl sau khi a vo phn t hu c hoc v c. Ni bt trong phn
ny l qu trnh a nhm vinyl vo vi tc nhn ch yu l axetylen.
2.1.3. Cc tc nhn ankyl ha v xc tc
Tc nhn th chia lm 3 nhm sau:
- Cc hp cht khng no
- Dn sut clo
- Ru, ete,este,oxytetylen
Xc tc c th chia thnh nhng nhm chnh sau:
- AlCl3
- H2SO4
- HF
Khi ankyl ha benzen bng olefin c th dng xc tc khc nh
nha trao i ion hay zeolit.
H2SO4 (94 96%(kl)). Nu nng cao, tnh oxy ha mnh, to
32

nha, SO2, SO3 v nc gim hiu sut ankyllat, nu nng axit thp,
s xc tin cho qu trnh polyme ha, d to thnh cc ankyl sunfit
tng ng v khi t nng chng d phn r to thnh cc hp cht
gy n mn thit b, lm long nhanh axit sunfuric. Axit sau khi phn
ng c ti sinh bng cch phn hy nhit v cho thm cht kch hot
c bic.
HF (>87%(kl)), hn ch v trong qu trnh

sinh ra phn ng

polyme ha v nc lm gim nng HF, tuy nhin mc tiu hao

HF t hn H2SO4
HF rn v c d th ha, thao tc an ton hn v mi trng sch
hn ( hot tnh tng ng HF(l)), d tch sn phm ankyllat v
d th ha xc tc.
Xc tc AlCl3
Zeolit c rt nhiu u im thc y qu trnh nghin cu ng
dng xc tc zeolit trong tng lai cho qu trnh ankyl ha. Khi dng xc
tc ny, iu kin cng ngh cao hn (P,T) nhng t sn phm ph, d
tch xc tc v sn phm sch hn.
2.1.4. c tnh nng lng ca cc phn ng ankyl ha c bn
Cc c tnh nng lng ph thuc vo tc nhn ankyl ha v dng lin
kt b ph v trong cht ankyl ha. Mt s thng s nng lng trong
qu trnh ankyl ha c trnh by bng 2.1.
So snh cc s liu bng 2.1 c th thy, khi s dng mt loi tc
nhn ankyl ha, hiu ng nhit khi ankyl ha theo cc nguyn t khc
nhau s gim theo dy Car > C > N > O v i vi cc tc nhn ankyl
ha cng thay i theo dy sau: RCl < ROH < RCH=CH2 < Oxit etylen
acetylen.
Hiu ng nhit c bit ln khi khi c s tham gia ca etylen oxit v
acetylen, xut pht t sc cng ni ti ca vng 3 cnh v s hp thu
33

nhit cao ca cc hp cht vi lin kt ba.

Bng 2.1. c tnh nng lng ca cc phn ng ankyl ha c bn
Tc nhn ankyl ha

RCH=CH2

RCl

ROH

CH2 - CH2 - O

CH

CH

Lin kt b ph v

-H0298, Kj/mol

C - H

84 100

Caromatic H

96 104

OH

50 63

Caromatic H

34 42

OH

=0

NH

0 25

OH

0 21

NH

21 42

OH

88 104

O-H

100 - 117

2.1.5. Cc yu t nh hng n qu trnh ankyl ha

Trong s cc yu t nh hng n qu trnh ankyl ha, phi k n
cc yu t v nng ca cht tham gia phn ng, nhit , p sut
Nng tc cht tham gia phn ng c tc dng ln n qu trnh
ankyl ha, s dng tha tc nhn ankyl ha thng cng lm tng hiu
sut ca qu trnh ny.
a s cc phn ng ankyl ha l phn ng ta nhit, v nhit phn
ng cng tng ln th tc phn ng cng gim. Tc nhn ankyl ha
l cc ancol th phn ng c thc hin nhit cao hn so vi
dng tc nhn ankyl ha l dn sut halogen.
Nhit phn ng dao ng trong khong t nhit phng ln n
2000 C. Thc hin phn ng trong pha kh th c lc nhit ln n
34

4000C.
Ankyl ha vi tc nhn l ancol hay ankyl halogenua thng phn ng
c thc hin p sut v nhit cao, c lc n 37 40atm.
2.1.6. Thit b dng trong qu trnh ankyl ha hyrocacbon thm
vi xc tc AlCl3
kh
ankylat
ankylat
H2O

Tc nhn ankyl ha
Xc tc
C6H6

ankylat

H2O
Olefin +
xc tc

H2O
Benzen + olefin (RCl)
+ xc tc
a

H2O
b

benzen
c

Hnh 2.1. H thng thit b phn ng ankyl ha hyrocacbon thm vi xc tc AlCl3

a Thit b ng chm, b H thit b ni tip, c Thit b dng thp rng

Qu trnh sn xut gin on c tin hnh trong thit b phn ng c

b phn khuy v v o lm lnh (hoc dng ng xon bn trong).
Ngi ta a vo thit b phn ng benzen v AlCl3 hoc phc xc tc
(10 20% so vi th tch hn hp phn ng), sau va khuy va
cho vo olfin lng hoc dn sut clo v gi nhit n nh. Nu
chuyn qua sn xut lin tc, th trong trng hp cc tc nhn ankyl
ha lng c th tin hnh theo 2 phng php ch yu sau:
Theo phng php u, ngi ta s dng thit b dng ng (hnh a),
phn di thit b c b phn nh ha hn hp phn ng. Cc tc cht
ban u v phc xc tc c a vo phn di ca thit b, cn nh
tng to thnh s tri ln ln pha trn theo gia cc ng (c lm
35

lnh bng nc). trong thit b tch, lp hyrocacbon c tch ra khi

lp phc xc tc v sau a vo x l. Thi gian lu ca hn hp
trong thit b phi bo m kt th cphn ng.
Phng php th hai l s dng mt h ni tip gm t 2 n 4 thit b
phn ng c gn cnh khuy (hnh b). ngi ta a vo thit b phn
ng u tin cc tc cht ban u, v hn hp phn ng sau t bn
hng s chy qua thit b phn ng tip theo. Gia hai thit b ny c
mt b phn tch s b, trong phc xc tc tch ra c a tr li
thit b u tin. Khi s dng h thit b ni tip s trnh c hin
tng tiu hao xc tc ln trong sn phm. Thi gian lu ca hn hp
phn ng trong h thit b ni tip khong 50pht nhit 40 600C,
ngoi ra thi gian ny cn c xc nh bi cc iu kin gii nhit v
yu cu cn t n cn bng sao cho cc sn phm monoankyl l cao
nht.
Ankyl ha cc hyrocacbon thm bng olefin dng kh c tin hnh
trong cc thit b dng thp (hnh c), pha bn trong c chng n mn
bng cc tm chu axit. Hn hp lng c a vo thit b ti mc
van tro bn hng bao gm phc xc tc AlCl3 (20 40% th tch) v
hn hp hyrocacbon khng tan trong n. pha di ngi ta a
vo benzen khan v phn on olefin c sc qua cht lng c km
theo khuy mnh. Hn hp lng s chy qua van tro i vo b phn
tch, sau thi gian lng t nhin, lp xc tc nng hn pha di s
c a tr li thit b phn ng, cn phn sn phm ankyl ha s
c a i x l tip.
Nhit ca phn ng hu nh c thot ra bi vic lm nng cc tc
nhn v lm bc hi benzen. Hi benzen cng vi kh ca phn ng
c a qua sinh hn, ti y benzen s ngng t v s4 quay tr li
phn ng, cn kh s a i x l. Nh vy trong thit b ny, ch
36

nhit gn nh thit lp mt cc t ng v nhit s ph thuc vo

p sut cng nh lng kh thot ra (hoc ph thuc vo nng phn
on olefin ban u).
Khi lm vic vi cc phn on olefin long, thng thng phi s dng
p sut 0.5 0.6MPa, sao cho vic thu hi benzen t kh thot ra d
dng hn. Nhit trong thit b ng t khong 130 1400C, iu ny
s lm tng sn phm nha v gim hot tnh xc tc. Do vy nn gim
p sut xung cn 0.15 0.2MPa v nhit phn ng phi duy tr
1000C.
2.2. Cc qu trnh ehydro ho v hydro ho
2.2.1. Phn loi phn ng ehydro ho.
Phn ng bo ton v tr ca cc nguyn t trong mch phn t ban
u (s ehydro ha lin kt C-C, C-O, C-N)
C6H5 - C2H5 -H2

C6H5 - CH = CH2

R - CH2OH -H2

RCHO

RCH2NH2 -2H2

RCN

Phn ng bin i v tr ca cc nguyn t trong mch phn t ban

u.
n-C6H14
2

-4H2
H2

2.2.2. Phn loi phn ng hydro ho.

Phn ng cng hydro theo cc lin kt khng no.
+H2

S tc dng ca hydro km theo s tch loi nc hay cc cht

37

khng cha cacbon khc.

RCOOH + 2H2
RCOCl + H2

RCH2OH + H2O
RCHO + HCl

2.2.3. Cc s liu nhit ng

T cc s liu trong bng 2.2 cho ta thy rng, tt c phn ng hyro
ha u l phn ng ta nhit v tt nhin phn ng ehyro ha l
phn ng thu nhit. Theo tnh ton trn mt phn t kt hp vi hyro,
hiu ng nhit sinh ra cao nht i vi hp cht C=C . i vi cc h
thm th gi tr ca n nh hn so vi olefin, l do h thm c cu
trc bn vng hn. Khi hyro ha nhm cacbonyl, hiu ng nhit s
thp hn so vi lin kt C=C. trong trng hp ny, s hyro ha cc
anehit ta nhit nhiu hn (phn ng 4) hyro ha cc ceton (phn
ng 5). Qu trnh hyro ha cc nitril (phn ng 6) c hiu ng nhit
tnh trn mt mol cht kt hp vi hyro gn bng vi phn ng 1. r
rng cc quy lut ny cng c tun th i vi qu trnh ngc li l
ehyro ha. T hai phn ng hyro ha c tch loi nc (7 v 8) th
phn ng 7 c gi tr hiu ng nhit thp nht, cn phn ng 8 th cao
nht trong tt c cc phn ng hyro ha a ra. S hyro ha cc
mch theo lin kt C-C km theo s ta nhit tng i nh.
Cc qu trnh ehyro oxy ha c hiu ng nhit ph thuc vo t l
gia phn ng ehyro ha v oxy ha. Do s oxy ha thng ta
nhit, vi vic a vo mt lng oxy d c th lm tng mnh hiu
ng nhit ca phn ng tng cng. y l mt trong nhng u im
ca qu trnh ehyro oxy ha, u im ny gip loi tr s thu nhit
ca qu trnh cn phi nung nng thng xuyn hn hp phn ng.

38

Bng 2.2. Cc gi tr nng lng ca mt s phn ng hyro ha

H0298, Kj/mol

stt

Phn ng

RCH=CH2 +H2

CH

C6H6 +3H2

C6H12

RCHO +H2

RCH2OH

67 83

R2CO +H2

R2CHOH

58

RCN +2H2

RCOOH +2H2

RCH2OH

38 42

RNO2 +3H2

RNH2

439 472

-CH2-CH2- +H2

-CH3 + -CH3

42 63

8
9

RCH2CH3

CH +2H2 CH3-CH3

RCH2NH2

-H2O

-2H2O

113 - 134
311
206

134 159

2.2.4. nh hng ca cc yu t nhit ng n vic chn la cc

iu kin ca qu trnh
Trong cc qu trnh hyro ha dehydro ha thun nghch, c c
cc tc cht vi chuyn ha cao cn phi tin hnh la chn cc
iu kin nhm to ra kh nng t c trng thi cn bng thun li
nht, trng thi cn bng ny ph thuc vo cc yu t nhit ng hc.
Cc qu trnh dehyro ha nh trnh by phn trn, cn phi tin
hnh iu kin nhit tng i cao, thay i t 2000C n 600
6500C. N ph thuc vo dng tc cht ban u v phn ln c xc
nh bng c trng nhit ng hc ca phn ng. Nh s ehyro ha
ru v amin l cc phn ng c trng i vi nhm ny thng tin
hnh nhit 2000C 4000C, tng t khi iu ch cc olefin, dien
v arylolefin, th yu cu nhit t 500 6500C. iu ny cho php
39

tin hnh tt c cc qu trnh ehyro ha trong pha kh. Khi ehyro

ha, do s tch loi hyro thng lm tng th tch kh v tt nhin s
lm tng nhit chuyn ha nh p sut thp. Theo nguyn nhn ny,
i vi qu trnh ehyro ha thng chn p sut gn vi p sut kh
quyn, cn trong mt vi trng hp, ngi ta tin hnh qu trnh trong
iu kin chn khng. Nh 5950C, mc chuyn dch cn bng ca
etylbenzen thnh styren vi p sut gn bng 0.1MPa khong 40%, cn
p sut 0.01MPa th t 80%. Thay v s dng iu kin chn khng,
ngi ta thy thun li hn l pha long hn hp phn ng bng

hi

nc hay kh tr trong iu kin phn ng, t dn n lm gim p

sut hi ring phn ca cc tc cht v tng chuyn ha cn bng.
Do hyro lm dch chuyn cn bng v pha hyro ha cn cc kh khc
th cn tr s tch ra ca cc sn phm chnh, nn trong thc t
thng dng hi nc nng nhm gi p sut tng cng khong
0.1MPa.
Cc qu trnh hyro ha theo s liu nhit ng hc cho thy c kh
nng thc hin nhit thp hn v tt nhin nhit phi cho
php t c tc phn ng yu cu.Trong thc tin sn xut, nhit
dao ng t 100 n 350 4000C (ty thuc vo hot tnh xc tc v
kh nng phn ng ca tc ch ban u). mt s trng hp c
nhit tng i thp, th c th tin hnh phn ng hu nh hon
ton p sut kh quyn.. Do trong qu trnh hyro ha (tiu th hyro)
thng xy ra trng hp gim th tch, nn tng mc dch
chuyn cn bng thng hay s dng p sut (c bit khi nhit
cao).
Phng php khc tng mc dch chuyn cn bng l dng
lng d hyro so vi t l hp thc theo hpng trnh phn ng.
Phng php ny c dng rng ri hyro ha pha kh. V d khi
40

hyro ha benzen 0.1MPa, 2000C v t l mol C6H6 : H2 = 1 : 3, cho

mc chyn ha cn bng 95.7% v khi d 10 ln hyro th s tng
n 99.5%
2.2.5. Xc tc v c ch phn ng
Xc tc
Cc kim loi thuc nhm VIII v Ib cng nh hn hp ca chng.
Cc oxit kim loi (MgO, ZnO, Cr2O3, Al2O3).
Cc cht xc tc dng phc (CuO.Cr2O3, ZnO.Cr2O3, CoO.MoO3,
NiO.WO3, CoO.WO3).
Cc cht ny c bit l kim loi thng c ph trn cc cht mang
xp v b sung vo cc cht tng hot tnh nh oxit khc, kim loi
khc, chng c s dng nhng dng khc nhau t dng phn tn
nh trong pha lng n dng v nh hnh.
C ch phn ng
Cc phn ng ny thuc vo nhm phn ng ng ly theo nguyn tc
tng t nh cc phn ng oxy ha xc tc d th. S hp ph ha hc
ca cc tc cht ln trung tm cc trung tm hot ng K gi mt vai tr
quan trng, trong nh qu trnh chuyn electron cng vi s tham
gia ca cht xc tc s lm yu hay ct t hon ton lin kt ha hc
trong phn t ca cht hp hp. Nhiu phng php khc nhau cho
thy rng: khi hyro b hp hp bi cc kim loi nh qu trnh hp ph
vt l s lm yu mt phn lin kt v gy ra s phn ly ca phn t
K + H2

K ... H2

K - H ... H

+K

2K - H

Cc hyrocacbon no s b hp ph mc nh nhng cng c kh

nng phn ly theo lin kt C-H
K + RH

K - H ... R
(hay K - R .. H)

K-H+ K-R

Cc olefin, hp cht thm v phn ln acetylen cng nh ng ng

ca n u c kh nng hp ph cao, qua xy ra s ct t mt
phn hay hon ton lin kt khng no
K + CH 2 = CH2

K ... CH 2 = CH2

K - CH 2 - CH2 -

Cht xc tc oxit cng c kh nng tng t nhng kh nng cho hp

ph ha hchyro v hyrocacbon ca chng km hn cc kim loi.
Cn i vi hp cht hu c cha oxi v nit th hp ph rt tt ln cc
cht xc tc hn l ln kim loi.
S tng tc tip tc s xy ra gia 2 b phn hp ph ha hc nm
41

cc trung tm hot ng cnh nhau lp b mt hay gia phn hp

ph ha hc v hp ph vt l hay phn nh ra khi th tch phn t.
Khi trong cc qu trnh cn bng hyro ha ehyro ha u c
tnh thun nghch tng giai on c s
K - CH2 = CH2 + 2H .. K

K - CH2 - CH3 + H - K

CH3 - CH3

K
hay R- H2 = CH2 + 2K -KH

-2K

K-CH-CH3 +K

R - CH - CH2 -

-KH

-K

R - CH = CH2

Phn ng hyro ha cc hp cht cacbonyl v ehydro ha ru u

c mt s c trng. Chng c kh nng xy ra theo c ch cacbonyl
cng vi s hp ph ha hc theo lin kt C-O cng nh c ch enol
ha hp cht cacbonyl. Cc th nghim vi cc hp cht cho thy
rng nhit thp s xy ra c ch u tin, cn nhit cao th l
c ch 2
O

OH

O*

CH3 - C - CH3 + K

+H2

CH3 - C - CH3

CH3 - CH - CH3 + K

K
OH

OH

CH3 - CH - CH2 - K

CH3 - C - CH3 + K

+H2

CH3 - CH - CH3 + K

2.2.6. Tnh chn lc ca cc phn ng ehyro ha v hyro ha

Tnh chn lc ca cc phn ng ny quan trng trong hai vn sau:
Hn ch cc phn ng su hn, dn n lm gim hiu sut ca sn
phm chnh v iu chnh phn ng xy ra theo nhm chc xc nh
ca tc cht. Do , tnh chn lc ph thuc vo s pht trin ca phn
ng ni tip v song song.
Nhiu phn ng hyro ha xy ra qua hng lot cc giai on. Nh cc
axit cacboxylic, anehit, ceton s c kh mt cch ni tip thnh
ru v hyrocacbon, nitril thnh imin, amin v hyrocacbon
RCOOH +H2
_

H2O

RCN +H2

RCHO +H2

RCH = NH +H2

RCH2OH +H2
_

H2 O

RCH2NH2 +H2

RCH3
RCH3 + NH3

Trong qu trnh pht trin tip tc ca cc phn ng ny c th dn n

qu trnh hyrogen ha cc hp chh hu c vi s to thnh cc sn
phm ct mch khng mong mun
C6H6 +3H2

C6H12

+H2

C6H14 +H2

CH4, C2H6, ...

Trong tt c cc trng hp ny, i khi yu cu dng phn ng mt

giai on xc nh, tc l tin hnh hyro ha mt phn cht ban u
42

sau khi hn ch cc phn ng k tip.

Ngoi ra, trong phn t hp cht hu c, t khi cha hai hay nhiu hn
cc nhm chc c kh nng hyro ha, trong ch cn xy ra hyro
ha mt nhm trong s chng. Nh khi hyro ha axit khng no, c th
nhn c ru khng no hay axit no, t phenol nhn ru
cyclohexanol hay hyrocacbon thm
R-CH=CH - (CH2)n - CH2OH
RCH=CH - (CH2)n - COOH
C6H11OH

+3H2

C6H5OH

R - CH2 - CH2 - (CH2)n - COOH

+H2
H2O

C6H6

Trong cc qu trnh dehydro ha, cng gp cc phn ng ni tip v

song song ph gy ra bi nhit cao hn so vi hyro ha.. V d xy
ra s cracking nguyn liu, polyme ha, vng ha v dehyro ngng t
dn n c th l tch ra cc cht nha, keo lm kh hot tnh xc tc.
i vi cht xc tc thuc nhm u, tnh la chn ca phn ng s
ph thuc vo hng lot cc yu t, trong s l kh nng phn ng
tng i ca cc cht hu c hay cc nhm chc ring bit v ph
thuc vo kh nng hp ph ca chng trn b mt cht xc tc.
Thng c hai yu t u nh hng song song, i khi yu t u xy
ra trc. V d cc lin kt i ca arylolefin thng hyro ha d hn
so vi nhn thm cn anehit d hn so vi ceton. Tuy nhin c trng
hp l kh nng phn ng v hp ph thay i theo chiu ngc li.
Lc cht cho kh nng hp hp tt nht s b tch ra khi b mt
cht xc tc bi tc cht khc hay sn phm trung gian v ch to c
hyro ha mt ln.
Kh nng hp ph ca cht xc tc theo tng quan vi cc cht ny
cc nhm chc khc nhau l ch tiu quan trng, qua xc nh
cc thng s nhm tng tnh la chn ca phn ng. Cc cht xc tc
kim loi c bit l Pt, Pd, Ni khng c kh nng hp ph vi cc hp
cht v cc nhm chc c cc, v trn b mt ca chng d dng xy
ra s hp ph ca tc cht theo lin kt C-C. V vy ceton, axit
cacboxylic khng no v mt vi dn sut ca hyrocacbon thm s
hyro ha trn b mt kim loi ch yu theo lin kt C-C vi s bo
ton cc nm c cc. Ngc li cc cht xc tc oxit, c mng tinh th
phn cc nn c kh nng hp ph c bit i vi nhm phn cc ca
cc cht hu c. S kt hp nhiu nhm chc khi hp ph trn b mt
cht xc tc oxit s gy bi s nh hng theo nhm c cc, v th cc
anehit, ceton, axit cacboxylic khng no v thm, cc hp cht nit v
cc cht khc s hyro ha trn b mt cht xc tc ch yu theo nhm
43

cha cha oxi v bo ton lin kt khng no.

Khng ph thuc vo vic la chn cht xc tc cngnh cc iu kin
khc, nhit s gy nh hng mnh ln tnh c hiu ca qu trnh
hyro ha v ehyro ha. Thng thng nhit cng thp th cng
c th tin hnh phn ng theo cc nhm c kh nng phn ng ln
hn hay dng qu trnh mt giai on trung gian xc nh. Ngc li
s tng nhit to kh nng cho cc chuyn ha su hn. Tt nhin
cc phn ng cracking, ehyro ha ngng t v cc phn ng ph
khng mong mun khc c nng lng hot ha cao hn so vi qu
trnh ehyro ha v hyroha. Nh cracking n-butan, nng lng
hot ha khong 2510Kj/mol, cn ehyro ha n thnh n-buten th
ch cn 168 184Kj/mol, chnh iu ny cho thy gim nhit s tng
tnh lc chn cho qu trnh, nhng khi gim nhit th tc qu trnh
cng nh nng sut thit b phn ng cng gim. V vy, trong thc t
c th tm mt khong nhit ti u tng ng vi chi ph kinh t nh
nht.
Sau cng, trong iu kin cn bng bn, tnh la chn s ph thuc vo
thi gian tip xc, xc nh bi chuyn ha thc t ca tc cht.
chuyn ha cng gn vi cn bng th s pht trin ca cc phn ng
ni tip ca cc qu trnh hyro ha su, cracking hay ngng t dn
n s gim tnh la chn cng tng mnh. V vy i vi tng qu
trnh ehyro ha v hyro ha u c chuyn ha v thi gian tip
xc ti u. Thng thng qu trnh hyro ha tin hnh chuyn
ha cao (>90%) cn thi gian tip xc trong cc trng hp khc nhau
s thay i t %pht n vi gi. nhit cao hn ca qu trnh
ehyro ha lm phc tp bi tnh thun nghch ca phn ng th
chuyn ha i khi ch khong 40%, cn thi gian tip xc nm trong
gii hn t %giy n vi giy.
2.2.7. Thit b s dng cho phn ng ehyro ha etylbenzen.
ehydro ha ankylbenzen c th thc hin bng cc phng n
khc nhau. Mt trong s l dng thit b phn ng dng ng c
t nng bng kh t. N t c gn n profil ng nhit ca nhit
nn cho php nhn c chuyn ha cao khi tnh la chn tt.
Trong thit b ny, chi hp v kim loi v xy dng c bn cao, do
ngi ta ch to ra cc thit b khc vi lp xc tc lin tc, khng c
b mt trao i nhit.

44

Hnh 2.2. H thng thit b phn ng ehyro ha etylbenzen

a Thit b phn ng n dng on nhit,
b H thng gm 2 thit b phn ng vi qu trnh t nng trung gian,
c - Thit b phn ng vi vi lp xc tc v hi t nng cho vo tng giai on

Chng lm vic iu kin ng nhit v hn hp phn ng s c

lm ngui t t, trong hi nc ng vai tr tch ly nhit, khng cho
hn hp ngui nhanh. i vi qu trnh iu ch styren trong mt thit
b phn ng on nhit, thng chuyn ha ca etylbenzen t 40%
cng vi s thay i nhit t u n cui lp xc tc t 600
6200C n 540 5700C, hng s tc theo etylbenzen lng 0.2 0.3h1
. Nhc im ca loi ny l s lm ngui hn hp tn ti s gy ra s
dch cn bng theo hng khng mong mun v ty theo m gy ra
s thay i tc v chuyn ha.
Trong cc thit b mi, ngi ta dng kt cu h thit b phn ng gn
vi qu trnh ng nhit v ch nhiu n c tnh ca trng thi cn
bng phn ng. Mt trong s (hnh 2.2.b) c hai thit b phn ng
(hay hai lp xc tc) m sau khi c lm lnh thit b u, hn hp
s qua thit b 2 v c t bng hi nng n 600 6300C.
Thit b biu din trn hnh 2.2c c 4 lp xc tc, trong lp u tin
s c tt c etylbenzen tham gia nhng ch c mt phn hi nc. Cn
trong khong khng gia cc lp xc tc s a vo s lng hi b
sung lm tng nhit cho hn hp v trong s xy ra s pha
long hn hp dn n s lch cc thng s so vi trng thi cn bng
v lm tng tc cng nh tnh la chn ca phn ng. Trong c cu
thit b mi ny, khi gi tnh la chn cao (89 90%) s t c
chuyn ha ln (60 75%) v cng qu trnh cao (hng s tc
0.5 0.6h-1) cng nh gim hao ph ring ca hi.
45

2.3. Qu trnh halogen ha

2.3.1. Khi nim qu trnh halogen ha
Cc phn ng ha hc
Nhng dn sut halogen thu c bng 3 cch c bn: phn ng th,
phn ng kt hp v phn ng ct mch.
Halogen ha th: l s thay th nhng nguyn t hoc nhng nhm
khc bng nguyn t halogen. Phn ln trong s l thay th nguyn
t hyro.
R H + C l2

RCl + HCl

Qu trnh th c th xy ra trn nguyn t cacbon bo ha hoc khng

bo ha hoc trong nhn thm. Kh nng thay th c duy tr trong
nhng dn xut khc nhau ca hyro cacbon.
Thay mt nguyn t halogen bng mt nguyn t khc: dng thu
c nhng dn xut flo, brom, iod t nhng hp cht cha clo.
C C l4 + 2 H F

C C l2 F 2 + 2 H C l

R C l + NaBr

R Br + 2N aC l

Thay nhng nhm OH bng nguyn t halogen: c dng iu ch

mt s dn xut halogen, nh l floanhyrit axit.
ROH + HCl

R C l + H 2O
RCOCl + CO2 + HCl

R C O O H + C O C l2

Halogen ha cng: qu trnh lin kt nhng hiro halogen vi

nhng hp cht cha bo ha c ngha thc t rt ln, ging nh qu
trnh thay th. Halogen t do c kh nng lin kt vo ni C = C,
Cacbon-Cacbon trong vng thm...:
C lC H 2 - C H 2 C l

C H 2 = C H 2 + C l2
HC

C H + C l2

C 6 H 6 + 3 C l2

C l2 C H - C H C l2
C 6 H 6 C l6

Nhng hyro halogen c lin kt theo ni i v ni ba (hyro

halogen ha), cn nhng olefin tham gia vo phn ng clohyro ha:
CH2 = CH2 + HCl
HC

CH + HCl

C H 2 = C H 2 + C l2 + H 2 O

C H 3 - C H 2C l
CH2 = CHCl
C H 2C l - C H 2O H + H C l

Kh nng halogen ha kt hp i vi nhng phn ng k trn c

gi n nh nhiu hyro cacbon cha bo ha.
Trng hp c bit ca clo ha cng hp, li l qu trnh lin kt clo
46

vo nhng nguyn t nm trng thi ha tr thp nht, v d nh tng

hp phosgen t oxyt cacbon v Clo.
C O + C l2

C O C l2

Phn ng ct mch: n c ngha quan trng nht. Qu trnh

ehydro clo ha xy ra rt d dng (1), ngc li vi qu trnh kt hp
vi HCl. Do qu trnh d dng xy ra khi nhit cao trong dn xut
declo. Qu trnh declo ha (2), ngc li vi qu trnh kt hp vi clo,
v qu trnh ct mch theo ni C-C c th xy ra di tc dng ca clo nhit phn clo (3), hoc nhit cao: nhit phn (4).
(1 )

C H 2 C l - C H 2 C l + C l2
C C l3 - C C l3

(2 )

CH2 = CHCl

C C l2 = C C l2 + C l2

C C l3 - C C l3 + C l2
C C l3 - C C l2 - C C l3

(3 )

C C l4

(4 )

C C l2 = C C l2 + C C l4

Nhng tc nhn halogen ha

Nhng tc nhn halogen thng dng nht l halogen t do v
hyro halogen dng khan nc. Tt c chng u tan trong cht lng
hu c (Br2 > Cl2 > F2 v HBr > HCL > HF). iu ny rt quan trng
thc hin qu trnh halogen ha pha lng. Chng c mi gt, to
mng nhy trong mt v nu ht th phi nhng halogen t do, th ngoi
nhng tc hi trn n cn gy ngt th, c bit nguy him l F2 v HF,
chng c kh nng n mn da v m xng.
Clo thu c bng in phn dung dch NaCl (nc mui) v hyro
C l-

- e-

0 .5 C l2

H+

+ e-

0 .5 H 2

N a+ + O H-

NaO H

Kh clo thu c c nng khong 92% Cl2, c cha tp N2, O2 v

CO2. Chng c th c tch ra bng cch ha lng clo, qu trnh ha
hi ca n s cho sn phm sch.
Clorua hyro thu c khi hyro v clo tc dng nhit cao:
H2 + Cl2

2HCl

Ngi ta sn xut flo bng in phn nng chy hyrodiflorit canxi.

Cn florua hyro khng ngm nc c ch bin nh tc dng ca
axit H2SO4 trn CaF2 nng chy.
-

+ e-

-e
H+
F0 .5 H 2 C a F 2 + H 2 S O 4
C aSO 4 + 2H F
0 .5 F 2
Tt c nhng cht tham gia phn ng halogen ha u n mn thit b.
Tc ng n mn ca chng c bit tng khi c m. Bi vy, trong
nhng qu trnh clo ha, thng dng ng hoc niken lm vt liu ch
to thit b, cn khi clo ha v brom ha, ngi ta bo v v kim loi
bng vt liu ch, men hoc gm, s. Ngoi ra, cn dng c nhng loi

47

thp chuyn dng, grafit, thy tinh ch to nhng ng ng ch.

gim n mn, ngi ta phi sy nhng cht hu c v halogen.
K thut an ton trong nhng qu trnh halogen ha
Ngoi nhng vn chung v s c hi v d n ca nhng cht
ban u (hyrocabon, oxyt cacbon), khi halogen ha cn xut hin
nhng iu kin ring v k thut an ton lao ng.
Th nht: khng ch nhng cht tham gia phn ng halogen ha m
cn c nhng dn xut halogen thu c c c hi rt ln. Chng
nh hng n h thn kinh trung ng, gy ra nhng tc ng c ch
hoc m man (clorofoc, cloral), to mng nhy trong mt v nu ht th
chng (benxenflorit, cloaxeton) c th gy ngt th. Do khi halogen
ha, i hi phi c yu cu cao v kn ca thit b v qut thng gi
cho xng. Ti ni lm vic, bt buc phi c phng tin cu thng
gip u tin v mt n phng c.
Th hai: halogen t do tng t nh oxi v khng kh, l c th to
vi hyrocacbon v CO nhng hn hp n nguy him. Qu trnh t
chy chng trong oxy ta nhit nhiu v nng xc nh s dn n
n. Gii hn trn v di ca tnh d n, i vi hn hp ca parafin
thp phn t v olefin thp phn t vi clo nm trong khong 5 - 60%
(th tch) hyro cacbon. Do cn s an ton khi trn hyrocacbon vi
halogen, c bit l trong nhng phn ng pha kh nhit cao, nn
cn thit phi c cc thit b chuyn dng. Tnh nguy him v n ca
trong qu trnh sn xut cng tng v c nhng dn xut halogen cng
c kh nng to hn hp n nguy him vi khng kh. V d gii hn n
trong hn hp vi khng kh ca CH3Cl (7.6% 19.0%) ; C2H5Cl (3.8%
15.4%); C2H4Cl2 (6.2 16.0) (% th tch).
Khi tng s nguyn t halogen trong phn t, nguy him n ca hp
cht gim dn, tetra-clometan thm ch cn c dng dp la.
2.3.2. Clo ha chui gc
Tt c nhng qu trnh halogen ha, theo c ch ca chng m chia
ra lm 2 nhm: gc chui v xc tc ion. Nhm 1 gm cc phn ng
thay th nguyn t hyro trong parafin, olefin v hyrocacbon thm,
cng nh qu trnh kt hp halogen theo lin kt cacbon cacbon trong
anken, ankin v trong vng thm.
C s l thuyt ca qu trnh
C ch phn ng
Nhng qu trnh ny lin quan ti nhng phn ng chui khng
phn nhnh, qua s to thnh trung gian ca nguyn t clo v ca gc
t do.
S hnh thnh chui: Khi tin hnh clo ha theo phng php nhit
(clo ha nhit ) pha kh, qu trnh hnh thnh gc t do t c nh
s ct phn t clo di tc ng ca nhit cao, cng vi s tham gia
48

ca thnh hoc np bnh phn ng, nh qu trnh hp thu ha hc, m

lm gim nh s b gy ni Cl-Cl:
i khi clo ha nhit xy ra nhit va phi (100 200oC), nhit
ny khng ph v lin kt Cl-Cl. Gc t do trong trng hp
ny, c to thnh khi tng tc qua li ca clo v nhng cht hu c
khc:
CH2 = CH2 +Cl2 ClCH2 - C*H2 + Cl*
+Cl2
R* + HCl + Cl*
RH

Khi clo ha quang ha, qu trnh ct mch phn t clo t c nh

qu trnh hp th nng lng lng t, v d khi chiu bng chm tia
cc tm.
Cl2

hv

2Cl*

Cui cng, khi clo ha ha hc, ngi ta thm cht khi u, ngha
l cht c kh nng b phn hy thnh gc t do nhit va phi,
thng l peroxit benzoil v 2,2 azo bis (izobutylronitril). Gc t do
to thnh khi tng tc vi phn t clo nhanh chng cho gc clo:
2C6H5COO*

(C6H5COO)2

2C6H5* + 2CO2
2NC - C*(CH3)2 + N2

NC - C(CH3)2N = N - C(CH3)2 - CN
C6H*5 + Cl2

C6H5Cl + Cl*

Qu trnh pht trin chui mch: n xy ra nh s hnh thnh ca

nguyn t clo trong giai on hnh thnh chui. Khi thay th mt xch
ca chui t 2 phn ng n gin lp li:
Cl* + RH

R* + HCl

R* + Cl2

RCl + Cl*

Qu trnh kt hp vi olefin xy ra nh sau:

Cl* + C = C

Cl - C - C*

Cl - C - C* + Cl2

Cl - C - C - Cl + Cl*

Qu trnh kt hp phc tp hn theo ni Cthm-Cthm

*

Cl

Cl
+ Cl

+Cl2
-Cl*

+Cl2
-Cl*

Cl
Cl

Cl

Cl

+Cl*

Cl
Cl

Cl

Cl
Cl*

Cl

+Cl*

+Cl2
-Cl

*
Cl

Cl

Cl

Cl

Cl

Cl

Cl
Cl

Cl

Chiu di ca chui, ngha l s mt xch trong , khi clo ha nhng

49

cht tinh khit c th t ti mi ngn. Khi dng nhng cht k thut,

chui ch gm khong my trm mt xch.
Qu trnh ngt mch: Khi clo ha pha kh, thng xy ra qu trnh
t chui trn thnh hoc np bnh.
ng ch l nhng trng hp ngt mch kt hp c trng cho qu
trnh pha lng. Qu trnh t chui xy ra trn gc hyrocacbon (clo ha
hyrocacbon), trn nguyn t clo (clo ha dn xut clo) hoc trong mt
s trng hp bng cch kt hp gc.
RCH = CH2 + RCH2CH3
2Cl*

Cl2

2RCH2 - CH2*
R* + Cl*

RCH2 - CH2 - CH2 - CH2R

RCl

Cui cng, qu trnh t chui c th xy ra trong nhng cht c ch

khc nhau (phenol, hp cht lu hunh, oxi).
Nhng sn phm thu c
Bng phng php clo ha pha lng chui gc, ngi ta thu c
nhiu sn phm.
Polycloetan: 1,1,2 tricloetan Cl2CHCH2Cl l cht lng, c nhit
si 113.9OC. Ngi ta thu c n t 1,2-dicloetan ,cng s to thnh
sn phm ph 1,1,2,2 v 1,1,1,2-tetracloetan. N c dng sn
xut monome chnh l vinylidenclorua CH2 = CCl2
1,1,1tricloetan hoc metylcloroform CH3CCl3 l cht lng, c nhit
si 74,1oC, thu c t 1,1dicloeetan, vi sn phm ph l 1,1,2tricloetan v tetracloetan. N dng lm dung mi rt tt v c sn
xut vi khi lng ln. Cch khc thu c n l hyroclo ha
vinylidenclorua.
Pentacloetan: CCl3CHCl2, cht lng, c nhit si 186,80C, n
c tng hp bng cch clo ha 1,2dicloetan hoc 1,1,2,2tetracloetan. N c dng ch bin dung mi cn thit
tetracloetylen CCl=CCl2, hecxacloetan - CCl3CCl3, l tinh th (nhit
bc chy 185,60), thu c bng cch clo ha trit bt c cloetan
no. N c dng sn xut triflo-tricloetan Cl2CFCF2Cl (dung mi)
v c bit l triflocloetylen CClF=CF2 (monome) v freon.
Cloparafin c rt nhiu loi vi cng dng khc nhau. Cloparafin-1,3
cha 12 14% clo, thu c t phn on du la hoc phn on
hp hn (C12 - C16) ca du parafin, cng nh t hn hp nparafin
tch ra t nhng phn on tng ng. N l monocloalkan bc 2 vi
hn hp ng bc I v dn xut diclo. Ngi ta dng n tng hp
cht hot ng b mt loi ankylaren sunfonat.
Cloparafin lng cha t 40 n 49%, c dng lm cht ha do (c
bit i vi polyvinylclorua) v cht ph gia cho m bi trn.
Cloparafin rn cha 70-72% clo, dng lm ph da cho nha v cao su
tng chng chy cho chng.
Dn xut clo ca aren: benzylclorua C6H5CH2Cl, l cht lng, si
50

179,30C. Ngi ta thu c bng clo ha toluen vi s to thnh sn

phm ph l benzalclorua C6H5CHCl2,benzotriclorua C6H5CCl3 v
clotoluen ClC6H4CH3. Benzylclorua c ng dng trong cc qu trnh
a nhm benzyl vo nhng cht khc nh iu ch benzylxenlulo,
benzyl ete, benzyl ancol, benzyl amin, butyl bezyl phtalat (cht rt do)
v nhng cht khc.
P-xilendiclorua ClCH2C6H4CH2Cl c sn xut bng clo ha p-xilen v
dng tng hp polyme bn nhit.
Hexaclo-m v hexaclo-p-xilen Cl3C-C6H4-CCl3 l tinh th; ngi ta thu
n bng cch clo ha m- v p- xilen tng ng. N dng sn xut
dicloanhirit izo-phtalic axit [C6H4(COCl)2] (to thnh khi hyro ha
hexaclorit). Ngoi ra, hexaclo-p-xilen l dc phm cha bnh.
1,2,3,4,5,6-hexacloxyclohexan, hoc hexacloran C6H6Cl6 thu c bng
cch cng Cl2 vo benzen vi qu trnh to thnh sn phm ph heptav octa-cloxyclohexan. Sn phm k thut l hn hp 8 ng phn lp
th, trong s ch c ng phn l c hot tnh lm thuc tr su
(tinh th, nng chy 112-1130C). Hm lng ca n trong sn phm k
thut l 11-18%, bi vy ngi ta thc hin tuyn tnh ng phn ,
bng cch chit tch thu c sn phm giu hexacloran c cha
80-90%, ng phn v c gi l lindan (99% ng phn ). Nhng
ng phn cn li x l thnh triclobenzen, bng cch ehyroclo
ha. Hexacloran c dng lm thuc tr su.
iu kin ca qu trnh v cc dng thit b phn ng
Ngi ta thc hin clo ha pha lng, bng cch lm si bt clo dng
kh qua lp cht lng phn ng. Clo ha tan trong cht lng v phn
ng xy ra trong dung dch. Trong nhiu trng hp, mi trng lng
chnh l nhng tc nhn hu c, vi lng d nhiu d trnh qu trnh
clo ha su. Sn phm to thnh ngy cng tng, t trng ca hn hp
cng tng, ngi ta dng t trng kim tra mc chuyn ha. Khi
ch bin polycloparafin v hexacloxilen lng, thnh phn pha lng thay
i trong qu trnh phn ngy n khi to thnh sn phm st hoc
nng chy. Cui cng, khi ch bin polycloparafin rn v polyme clo
ha, ng nht tt hn hp, ngi ta dng dung mi (tetraclometan,
o-diclobenzen).
Trong cng nghip, ngi ta s dng tc nhn quang ha hoc ha
hc trong giai an khi u. Phng php 2 c u th l cu trc mc
xch, phn ng n gin nhng phi thm chi ph cht kch hot t tin
hn. Trong phng php 1 th cu to l phn ng phc tp hn. Tng
vn u t v chi ph nng lng in, nhng khng c chi ph vo cht
khi u, cn nhng cht tng hp khng b bn bi nhng sn phm
phn hyca n. Vic chn phng php, c xc nh da vo
nhng yu t kinh t. Ngoi t l nhng cht phn ng ban u, vic
51

chn nhit v nng cht khi u hoc cng chiu sng

cng c ngha quan trng.
Khi clo ha quang ha, vic chn nhit khng gii hn trong
khong gii hn no c, bi v n hon ton khng nh hng n vn
tc phn ng. Hn na, n thch hp hn khi lm lnh bng nc. V
vy, tng hp quang ha hexacloxyclohexan thc hin 40 600C.
Khi dng cht khi u, vic chn nhit c quy c bng vn
tc ln nht c th, ca qu trnh phn ha chng. Nhit bng 70
1000C i vi azo-bis izo-butylronitril v 100 1200C i vi peoxit
benzoil, khi c s lin h gia nhit v nng cht khi u
Do , gim lng cht khi u, ngi ta gim nhit v nng
cht khi u, nhng iu ny dn n vic gim vn tc phn ng
v tng chi ph cho giai on phn ng. V n i hi s ti u v iu
kin ca qu trnh theo tiu chun kinh t. Lng cht khi u c th
gim, nu cho vo tng phn v vo tng thi im khc nhau (khi qu
trnh tun hon) hoc l theo chiu di ca thit b phn ng (i vi
iu kin phn ng lin tc), hoc s thay i nhit theo vic chi ph
cht khi u. iu k trn xy ra vi clo ha quang ha, khi qu trnh
tng cng chiu sng v vn tc dn n vic gim chiu di chui
v tng chi ph cho nng lng in. S ti u cho c 2 trng hp ny
l cng ca qu trnh khng cao.
B phn phn ng (l tt c qu trnh clo ha pha lng), c th thc
hin lin tc v gin on. Thit b c bn (thit b clo ha) phi c
cung cp clo bng bnh kh li, thit b lm lnh thot nhit, thit b
lm lnh ngc dng hoc b tch kh trn ng thot kh (HCl),
ng ng bt buc v thit b o kim tra.
Trong phn ng clo ha trong l quang ho, lun c dng c
chiu sng phn phn ng (n thy ngn - thch anh pha trong c
bo v bng n trn hoc n ngoi chiu sng thit b phn ng
qua ca s thy tinh trong v).
S l phn ng c trng clo ha gc chui pha lng c m
t trn hnh 2.3.
S th nht (hnh 2.3.a) dng cho qu trnh tun hon v l
thp sc kh rng vi b phn lm lnh t ngoi. Qu trnh hi lu
phn phn ng qua thit b lm lnh, c thc hin bt buc (nh
bm), hoc nh qu trnh hi lu t nhin (di nh hng ca s
chnh lch t trng ca bt kh y v nng ca cht lng trong thp v
phn lnh hn khng cha kh ca cht lng trong vng hon lu).
Bng phng php ny, ngi ta thu c polycloparafin. Khi clo ha
polyme, trong dung dch c th thot nhit phn ng nh qu trnh ha
hi ca dung mi. Dung mi ny c ngng t v quay li vo l phn
ng nh b phn lm lnh ngc dng.
52

Hnh 2.3. S l phn ng clo ha gc chui pha lng

a Qu trnh tun hon vi s lm lnh bn ngoi
b Qu trnh lin tc vi s lm lnh bn trong
c - Qu trnh lin tc vi s lm lnh ngc dng

Phng n hot ng lin tc ca l phn ng c qu trnh lm lnh

khng hiu qu v s khuy trn mnh hn hp phn ng v lm gim
chn lc. V l do ny, thit b phn ng hot ng lin tc dng
dng thp sc kh vi s lm lnh bn trong (hnh 2.3b) nh nhng ng
xon (i khi nh v bc nc) v thit b ngng t ngc. Cht lng
v kh thng chuyn ng ngc dng nhau, khi gim vic
khuy trn mnh v tng chn lc, tt nht l phn nh thit b
phn ng theo chiu cao ca dy a hoc theo bc ca thit b phn
ng.
Khi clo ha vi cc cht c nhit si thp (1,1 v 1,2- diclo
etan), nhit thot ra c a ra ngoi nh qu trnh ha hi ca
nhng cht ny trong dng HCl. Trong trng hp ny, vic lm lnh
trong l khng cn thit, v vai tr ny c giao cho thit b lm lnh
ngc dng. (hnh 2.3c).
2.3.3. Clo ha xc tc theo c ch ion
Qu trnh ny l cng halogen theo ni i v ni ba, clohyro ha
olefin, phn ng hyroclo ha thay th vo nhn thm v clo ha mt
s hp cht cha O2 v N2.
Cc phn ng ha hc
Halogen ha cng hp bng halogen t do
Cng halogen theo ni i C=C
Trc y gp qu trnh cng clo vo olefin trong pha kh theo c
53

ch gc chui. Nu khi l pha lng th s tng vn tc t v xy ra

trong dung dch. C ch phn ng thay i c chng minh, nh qu
trnh vng mt ca nh sng v nh hng ca nhng cht kch hot
ha hc.
Khi cho cht phn ng ban u qua pha lng (cht lng ny thng
l sn phm phn ng), d dng xy ra qu trnh cng clo hoc brom
theo ni i:
RCH 2 = CH2 + X2

RCHX - CH2X

Phn ng ny xy ra rt nhanh, thm ch khi nhit thp, nhng

nhng xc tc loi axit khng proton lm tng tc phn ng (v d
FeCl3). C ch ca qu trnh nm trong qu trnh cng i in t vi s
to thnh phc v phc trung gian.
H 2C

Cl2

H2C

H 2C

Cl

Cl

H2C

+ FeCl3
- FeCl4

H2CCl + FeCl4
- FeCl3
H 2C

H2CCl
H2CCl

Vai tr FeCl3 c gii thch khng ch bng qu trnh tng tc giai on

chuyn phc thnh phc m cn bi s to thnh phc
Cl Cl: FeCl3.
Phn ng xc tc theo th t olefin, Cl2 v FeCl3, nhng trong
thng c c qu trnh khng xc tc theo clo bc cao hn. Kh nng
phn ng ca olefin ph thuc vo n nh ca cation trung gian v
thay i nh sau:
RCH = CH2 > CH2 = CH2 > CH2 = CHCl
Axetylen cng c kh nng cng clo:
HC

CH

Cl2

CHCl = CHCl

Cl2

CHCl2 - CHCl2

y, dng xc tc FeCl3, v do vn tc giai on 2 cao nn s to

thnh dicloetylen rt t.
Trong tt c nhng qu trnh ny, phn ng ph th H2 cng xy ra;
kt qu to thnh clorua cao phn t hn (tricloetan t etylen,
pentacloetan t axetylen) phn ng th c c ch gc - chui, khi
s hnh thnh chui c thc hin khi nhit thp nh tng tc
ca clo vi olefin:
RCH2 = CH2 + Cl2

CH2Cl - C.H2 + Cl.

ngn qu trnh ny, c th gim nhit , nhng hiu qu nht l

dng cht c ch phn ng chui v xc tc loi khng proton. Mt
trong nhng cht c ch c th dng l oxy c trong kh clo, n
c dng trong tt c nhng qu trnh nu trn. Khi cho xc tc
vo, s lm tng vn tc phn ng cng, v tng chn lc ca n.
Kt qu kt hp tc dng ca oxy v xc tc l lng sn phm t phn
ng ph th H2 khi clo ha etylen c gim t 10 n 0,5 2%.
Sn phm thu c
Sn phm thu c vi s lng ln nht l 1,2dicloetan
54

CH2ClCH2Cl (cht lng, si 83,50C). Ngi ta thu c n nh phn

ng cng clo vo etylen v c dng sn xut monome vinyclorua
CH2=CCl2, polyclorua etan v etylen (c im ca dung mi tri- v
tetracloetylen CHCl=CCl2 v CCl2=CCl2), cng nh etylendiamin
NH2CH2CH2NH2, cao su polisulfua thiocol (-CH2CH2-Sx-)n v loi sn
phm khc. 1,2 dicloetan c trong thnh phn ca mt s cht hun (dit
cn trng).
1,2-diclopropan ClCH2CHClCH3 (cht lng, si 98,60C) thu c nh
clo ha propylen. Ngi ta dng nh cht hun khi cho cao su v
tng hp cao su polysulfua.
1,2-dibrometan v 1,2dibrompropan thu c tng t nh cc
dn sut clo tng ng thu t etylen v propylen. Trc y, chng
c dng ch bin cht lng etyl (dung dch tetraetyl ch) thm vo
nguyn liu ng c lm tng ch s octan ca chng.
1,1,2tricloetan v hexacloetan gn y c tng hp hu hiu
nht khng phi theo phn ng th gc chui, m l cng c chn lc
clo vo cloolefin tng ng.
CH2 = CH2Cl + Cl2
CCl2 = CCl2 + Cl2

CH2Cl - CHCl2
CCl3 - CCl3

1,1,2,2 tetracloetan - CHCl2CHCl2 thu c bng cch clo ha

axetylen v dng sn xut dung mi tricloetan. V gi thnh axetylen
cao nn phng php ny t hiu qu v c thay bng phng php
khc hiu qu hn l ch bin etylen thnh 1,2 -dicloetan.
iu kin ca qu trnh v cc dng thit b phn ng
Nhng phn ng trn khc nhau v chn lc v vn tc, bi vy
cht phn ng ban u khng nht thit phi tinh khit. Nh th,
thng dng kh clo long cn li sau khi ha lng clo, hoc phn on
olefin c cha nhng parafin tng ng hoc cha tp cht tr (nhng
khng phi l olefin khc). Nhng vic sy kh l iu bt buc.
Thc hin qu trnh bng cch cho sc cht phn ng dng kh qua
sn phm lng, trong dung dch xy ra qu trnh tng tc. Trc y,
trnh phn ng th, ngi ta c gi nhit thp mc c th
c (300C), nhng trong trng hp ny, s thot nhit lm gim
nng sut ca l phn ng. Hin nay, ngi ta thc hin qu trnh vi
cng cao hn 700C - 1000C, cn gim qu trnh th, ngi ta
dng tc ng ca oxi v xc tc. Xc tc dng c bit l FeCl3 hoc
mu gang cho vo l phn ng to thnh FeCl3 di tc ng ca clo.
T l cht phn ng hu c v clo trong trng hp ny gn vi t
lng vi lng d nh ca olefin (~ 5%) m bo chuyn ha hon
ton clo.

55

Hnh 2.4. H thng phn ng clo ha xc tc ion trong pha kh

a - Vi s lm lnh bn ngoi; b Cng vi nhit ca s ha hi;
c Cng vi s clo ha v chng ct

Thit b phn ng cho nhng qu trnh ny c 3 loi (hnh 2.4). Trong

trng hp u, ngi ta thc hin phn ng trong thp si bt kh (s
2.4a) vi h thng lm lnh bn ngoi v ng sinh hn ngc. Ti
y, hi mang theo sn phm, ngng t tch khi kh thot ra. Phn
ngng t cho quay li thit b phn ng, cn sn phm tch t cho thot
qua ng chuyn ph v n b phn x l tip theo.
Khi iu ch cht d bay hi 1,2dicloetan, mt phn ln nhit lng
thot ra c nh thit b ngng t ngc. Hn na, thit b lm lnh
bn ngoi c th gim ht v thot nhit nh s ha hi. Nhng ci tin
tip theo l xa b ng dn ph ca sn phm v thit lp u ra t h
thng sau khi qua thit b ngng t ngc. Khi , phn ngng cn li
cho quay li thp gi nhit cn thit v mc cht lng (s
2.4b). Trong trng hp ny, xc tc khng lm bn sn phm, m cn
li trong thp v lm vic.
Cui cng, ngi ta tm ra qu trnh ng dng h thng va clo
ha va chng ct (s 2.4c). B di ca thp ng vai tr thit b
phn ng, ngi ta cho etylen v clo vo. Trong phn chng ct ca
thp, ngi ta tch 1,2-dicloetan t tricloetan, n c thu hi li trong
b di.
Ngi ta x l kh thot ra, cng nh trong trng hp clo ha gc
chui pha lng, nhng khc ch v lng HCl khng ln lm. u
tin, ngi ta hp th bng nc, sau thi HCl long ra. Sn phm
lng ca phn ng, nu cn, phi lm sch khi xc tc v mang i
chng ct.

56

2.4. Qu trnh oxi ha

2.4.1. Khi nim qu trnh oxi ha
Phn loi phn ng oxy ha
Trong ha hc hu c nh ngha phn ng oxy ha khng phi
n gin. Khc vi ha v c, phn ng oxy ha trong ha hu c
thng khng km theo qu trnh thay i ha tr ca nguyn t. Qu
trnh tham gia ca oxy vo phn t cng khng phi l c im chung
ca phn ng oxy ha, iu ny cng c th hin nhng phn ng
khc khng lin quan n qu trnh oxy ha. Ngoi ra cn c cc phn
ng oxy ha, m trong s nguyn t oxy trong phn t khng thay
i.
RCH 2OH + 0.5O2

RCHO + H2O

Nh vy trong ha hu c, qu trnh cng ngh oxy ha c xem

l qu trnh chuyn ha cc cht di tc dng ca cc tc nhn oxy
ha. Cn phi phn bit qu trnh oxy ha hon ton v cha hon
ton. Ta bit rng khi chy hon ton, cc cht s chuyn thnh CO2 v
H2O.
Trong tng hp hu c, oxy ha hon ton l qu trnh ph khng
mong mun. Ch c phn ng oxy ha khng hon ton l quan trng,
c th tng hp hu c v c th chia chng thnh 3 nhm chnh:
Oxy ha khng t mch, khi s nguyn t cacbon vn khng i
so vi hp cht ban u. Cc phn ng ny li c th tip tc chia lm
2 nhm: oxy ha theo nguyn t cacbon no trong cc parafin, naphten,
olefin, ankyl vng thm v cc dn xut ca chng c bic l ru v
anehitl
+ 0.5O2

CH3-CH2-CH(OH)-CH3

CH3-CH2-CH2-CH3

+ 0.5 O2
+ 0.5O2

CH2=CH-CH3
C6H5CH3

+O2
-H2O

CH3-CH2-CO-CH3

+ H2 O

CH2=CH-CHO + H2O
C6H5CHO +0.5O2

C6H5COOH

Nhm th hai l oxy ha theo cc lin kt i to thnh -oxyt (epoxi

ha), cc hp cht cacbonyl hay glycol.

57

+ 0.5O2

CH3-CH2-CH(OH)-CH3

CH3-CH2-CH2-CH3
+ 0.5O2
CH2=CH-CH3

CH3-CH2-CO-CH3

+ H 2O

CH2=CH-CHO + H2O

+0.5O2
+ O2
C6H5COOH
C6H5CHO
-H2O
RCOCH3
RCH=CH2 + 0.5O2

C6H5CH3

RCH=CH2 + H2O2

RCHOH-CH2OH

Oxy ha phn hy xy ra vi qu trnh ph v mi lin kt C-C. Cc

hydrocacbon v dn xut ca chng u c kh nng ny nh cc dy
parafin, naphten, olefin, hydrocacbon thm. Qu trnh phn hy s xy
ra cc lin kt C-C, C=C, Cthm - Cthm.
CH3-CH2-CH2-CH3
+2.5O2
RCH=CH-R,

+4.5O2

+2.5O2

2CH3-COOH + H2O

HOOC-(CH2)4-COOH + H2O
+2O2
C
C

RCOOH + R,COOH
OC
O

+ 2CO2 + H2O

OC

Oxy ha km theo qu trnh kt hp vi phn t ca tc nhn ban

u (oxy ha ngng t hay oxy ha kt hp)
CH2=CH2 + CH3COOH +0.5O2
CH2=CH2 + 2CH3COOH +0.5O2
2RSH

0.5O2

2RH

1.5O2

RCH3 + NH3

-H2O

CH2=CH-O-C-CH3
O

-H2O CH3-O-C-O-CH2-CH2-O-C-CH3

RSSR + H2O
ROOR + H2O
1.5O2

RCN + 3H2O

Tc nhn oxy ha v k thut an ton trong qu trnh oxy ha

Trong k thut phng th nghim v trong ha tinh vi tng hp
hu c ngi ta s dng nhiu tc nhn oxy ha nh pemanganat (
58

mi trng kim, trung tnh hay axit), dicromat, trioxit crom, peoxyt ca
vi kim loi (mangan, ch, natri). Nhng trong cng nghip tng hp ha
du v hu c, ngi ta c gng s dng cc tc nhn oxy ha r tin
v ch trong nhng trng hp ring ngi ta mi dng nhng tc nhn
c kh nng lm cho phn ng xy ra nu tc nhn oxy ha khc khng
s dng c.
Oxy phn t (dng khng kh, oxy k thut hay hn hp nit-oxy hm
lng O2 thp) l tc nhn oxy ha quan trng nht trong s cc tc
nhn. Ngi ta s dng n tin hnh phn ln cc phn ng nu
ra trn ca qu trnh oxy ha. Oxy tinh khit c tc dng oxy ha rt
mnh nhng s dng n li tn km chi ph tch oxy t khng kh.
Khi oxy ha pha kh, qu trnh hin din ca nit s gy kh khn cho
vic tch v qu trnh hon lu sn phm. Do ngi ta s dng oxy
k thut. Khi oxy ha bng khng kh tc phn ng chm nhng
c khc phc bng cch tng nhit cng nh p sut chung ngha
l tng p sut ring phn ca oxy.
Axit nitric (hay oxyt nit) l tc nhn oxy ha c s dng rng ri
sau oxy. Tc dng ca n bao gi cng km theo qu trnh nitril ha
mt t hp cht hu c v iu ny cng c thc y nu tng nng
ca n. Do nguyn nhn ny oxy ha ngi ta s dng HNO3 40
60%. HNO3 khng c s dng oxy ha cc parafin. Phn ng
tiu biu nht ca n l oxy ha phn hy cc hp cht vng hp cht
khng no. Trong nhng trng hp ny hiu sut phn ng cao hn khi
oxy ha bng oxy.
OH +4HNO3

HOOC-(CH2)4-COOH + 2N2O3 + 3H2O

HOOC-(CH2)y-CH=CH-(CH2)x-CH3

+ 4HNO3

CH3-(CH2)x-COOH + HOOC(CH2)y-COOH + 2N2O3 + 2H2O

Khi tham gia phn ng oxy ha, HNO3 s b kh n oxyt nit (NO
hay N2O3). Hiu qu kinh t ca sn phm ph thuc nhiu vo kh
nng tn dng cc oxyt ny v qu trnh ti sinh ca HNO3 khng
chuyn ha. Bi ton u tin s c gii quyt bng cch oxy ha
oxyt nit trong nc hay trong dung dch HNO3 to thnh HNO3.
N2O3 + O2 + 3H2O

2HNO3

Hp cht peroxyt m ch yu l peroxyt hydro v paraxyt axetic (cn

gn y l hydroperoxyt) c s dng nh nhng tc nhn oxy ha
trong tng hp hu c v ha du. Do tng i t tin nn ngi ta
ch s dng n trong nhng phn ng khng xy ra di tc dng oxy
phn t hay HNO3. iu ny lin quan n qu trnh epoxi ha cc hp
cht cha no:
59

-OOH + RCH=CH2

-OH + RCH-CH2O

Phn ng ca peoxyt axit vi xeton c gi tr km hn do ch yu to

thnh ru bc cao hay lacton (phn ng Baiep Vilier).
O
CH3-C

OOH

CH3-COOH +

-O

Peroxyt hydro thng thng c s dng dng dung dch 30%. N

kt hp vi axit cacboxylic to thnh peraxit theo phn ng tng t
nh phn ng este ha.
O
R-C

OH

O
+ H2O 2

R-C

OOH

+ H 2O

Ngoi ra peraxyt c th c to thnh khi oxy ha andehyt. Nh vy

peraxyt axetic c sn sut trong cng nghip bng con ng ny
cn hydroperoxyt c to thnh bng cch oxy ha hydrocacbon.
C6H5-CH-(CH3)2 + O2

C6H5-C(CH3)2
OOH

K thut an ton trong qu trnh oxy ha

Ch yu l do tc nhn oxy ha kt hp vi hp cht hu c to
hn hp n nguy him hay cc hp cht c kh nng gy n. Cc tnh
cht n ca hn hp hydrocacbon vi khng kh v cc s kiu v nhit
bt la ca hydrocacbon lng c trnh by ni dung phn
trc.
Vic a cc cht hu c khc nhau vo trong hn hp phn ng
da vo gii hn nng gy n nguy him (ru, xeton, andehyt),
trong cc gii hn ny cng ln nu s dng oxy tinh khit. i vi
cc phn ng oxy ha trong pha lng, tnh gy n nguy him s cng
ln khi p sut hi ca cc cht hu c (to ra hn hp n nguy him
vi khng kh hay oxy) cng cao.
Axit nitric v cc cht oxy ha khc cng to ra c hn hp n nguy
him vi cc cht hu c. Tnh nguy him khi c mt hydroperoxyt v
cc axit peracetic cng tng mnh do phn ng phn hy ca chng
xy ra vi qu trnh to thnh nc v acid acetic l ci phn ng ta
nhit.
H

+ 0 .5 O

H 0

298

= 9 8 ,8 K J /m o l

Qu trnh phn hy cc hp cht peroxyt k trn c xc tc bi mt

s kim loi ha tr thay i (Fe, Cu, Co, Mn, Cr) v cc mui ca chng.
V vy hydroperoxyt v nht l cc peroxyaxit c nng cao s to ra
kh nng n khi c mt cc cht hu c. iu ny cng tng t i
vi cc hp cht peroxyt khc. Vic s dng chng trong dung mi v
mt ch nhit nghim ngt s hn ch nhng khuyt im ny.
60

Kh nng n ca tc nhn oxy ha v hn hp ca chng vi cc

cht hu c l mt yu t quan trng cn ch khi thit k cc quy trnh
cng ngh thc hin phn ng oxy ha.
2.4.2. Oxi ha xc tc d th
Oxy ha vi xc tc d th c ngha to ln i vi hng lot cc qu
trnh m chng khng t kt qu tin hnh phn ng oxy ha gc
chui mch. l cc qu trnh:
Oxy ha olefin v cc dn xut ti nguyn t cacbon no lin kt i
vn c bo ton..
Qu trnh oxy ha amoni cc olefin v hydrocacbon khc iu ch
hp cht nitril
Oxy ha h thm v cc hydrocacbon khc to thnh cc anhydrit
ni ca axit di hay tetra-cacboxylic.Tng hp trc tip etylen oxit.
Xc tc d th ca qu trnh oxy ha
Nhng xc tc d th ca qu trnh oxy ha c gi tr thc tin l:
Cc kim loi Cu v Ag, trong ta thy Cu d b oxy ha hn s to
thnh lp oxit trn b mt ng vai tr tc nhn oxy ha. Cc kim loi
khc (Pt, Pd) s oxy ha hon ton n sn phm CO2 v H2O.
Oxyt ca kim loi chuyn tip nh CuO + Cu2O, V2O5 cng nh cc
oxyt khc chng khng hot ng v ch yu l oxy ha hon ton.
Hn hp oxyt v mui ca kim loi chuyn tip, c bit l vanadat
stunat, vonframat v molipdat ca km, coban v bismut ZnO.V2O5,
CoO.WO3,Bi2O3.MoO3) c th nm cc pha ring bit tng ng vi
cc oxyt v hp cht ca chng. c bic cc ferit v cromit s gy ra
qu trnh oxy ha hon ton.
Cc xc tc k trn c s dng dng phoi, li (Cu), ht mui
(V2O5 ) hay ph ln trn cc cht mang xp (Ag,CuO, mui) v thng
thng c thm cc cht tng hot khc.
C ch phn ng
Trong c ch ca phn ng oxy ha d th, qu trnh hp th ca cc
tc nhn trn b mt tip xc gi vai tr quan trng. Trn b mt cc
kim loa, oxy hp th rt nhanh, sau n thm vo lp bn trong vi
vn tc nh hn. Cc kim loi qu him s to ra cc oxyt cn vi bc
qu trnh c gii hn bi qu trnh hp th ho hc to ra qu trnh
thay i ca tnh cht ca lp di b mt. Ngi ta cho rng oxy s
hp thu khi tip xc km theo qu trnh phn ly hoc khng phn ly cc
phn t hoc kim lai cung cp in t cho oxy hp th chuyn n
sang trng thi ion- gc.
Ag + O2

Ag-O-O-.

2Ag-O-.

Tng t nh vy, qu trnh hp th ho hc oxy c thc hin trn

cc oxyt v mui, qu trnh hp th s din ra theo ion ca kim loi
chuyn tip, ion ny c oxy ha n trng thi c ha tr cao nht.
61

Cc hydrocacbon hp th trn cc kim loi tng i yu v thun

nghch. Chng hp th trn xc tc oxyt hoc mui mnh hn, trong
cc electron cn thit to lin kt s nm phn t olefin.
Phn t olefin ny s chuyn sang trng thi gc ion nh qu trnh hp
thu ho hc.
M

(n + 1 )

+ C H 2= C H -C H 3

n+

- C H 2 - C H + .- C H 3

Ion kim loi khi s b kh thnh mt trong cc dng ha tr thp. Khi

c qu trnh tng tc ng thi gia oxy v hydrocacbon, cc ion kim
loi thng nm cc trng tha ho tr khc nhau, kt qu l ha tr
kim loi thng l mt phn s. Nh ion vanadi khi oxy ho naphtalen
bng khng kh th c ha tr trung bnh ~4,3 so vi 5 trong V2O5 . R
rng l trng thi ion kim loi xc nh bi cc tnh cht oxy ha kh ca
mi trng v ph thuc vo t l ca oxy v hydrocacbon cng nh
qu trnh c mt ca hi nc Khi trong thi gian u ca qu
trnh cc xc tc s chuyn t t sang trng thi n nh cc iu kn
ca phn ng, v qu trnh thay i cc iu kin ny s lm thay i
hot tnh v tnh chn lc ca xc tc.
C hai dng c ch ch yu ca qu trnh oxy ha bng xc tc d
th. Mt l hydrocacbon s hp th ln b mt ca cht xc tc. Lc
u qu trnh hp th xy ra theo gc ion ca oxy, sau tng tc vi
n to thnh sn phm oxy ho. V d in hnh nht l qu trnh tng
hp etylenoxyt.
*

Ag-OO + CH2=CH2

Ag-OO-CH2-CH2

O
Ag-O + CH2-CH2
*

Ngi ta cho rng cc sn phm oxy ha hon ton s nhn c t

etylen v Ag-O; iu ny tng ng vi kh nng la chn ca qu
trnh (85%)
6AgO* + 7CH2=CH2

O
6CH2-CH2 + 2CO2 + 2H2O

Mt v d ca c ch ny l qu trnh oxy ha benzen thnh anhidrit

maleic xy ra sau khi to sn phm trung gian quinon.
M+OO* +
- M+OO*

O=

M+OO* .

+O2 M+OO

HC
+
2O
2
=O
- CO2, - H2O HC

OO*

CO
O
CO

C ch ph bin khc ca qu trnh oxy ho xc tc d th gi l oxy

ho kh. Trong c ch ny hydrocacbon hp thu trn ion kim loa s b
oxy ho bi oxy c trn mng xc tc, kim loi khi c kh sang
trng thi c ha tr thp hn v sau n tng tc vi oxy chuyn
v dng ban u.
62

2KO + CH2=CH-CH3
2K + O2

2K + CH2=CH-CHO + H2O

2KO

C ch ny c trng i vi qu trnh oxy ho olefin v metyl

benzen. N c xc minh bng d kin sau: cc sn phm c th to
thnh trn xc tc khng cha oxy cn gian on oxy ho hydrocacbon
v xc tc c th tin hnh mt cch ring bit.
Hai c ch nu trn c th coi l nhng trng hp bin: c c c ch
trung gian. Kh c th hnh dung mt cch chnh xc c ch trung gian
ny v cho ti nay vn cha xc nh c cu to b mt ca sn
phm trn b mt cng nh vai tr ca chng trong qu trnh oxy ha.
Qu trnh c ch cc phn ng song song ca qu trnh oxy ha hon
ton da vo qu trnh thay i t s gia cc tc nhn thng khng
c tnh kh thi m ch c nhit mi gi vai tr quyt nh i vi iu
ny. Nng lng hot ha ca phn ng oxy ho hon ton t 21 42
KJ/mol.
C th nhn thy nu tnh ton cc chi ph hon lu cc
hydrocacbon cha chuyn ha trong tng qu trnh s tn ti mt mc
chuyn ha ti u c xc nh bi cc ch tiu kinh t. cc iu
kin nh nhau mc chuyn ha c iu chnh bng 2 phng
php: thi gian tip xc hoc dng thiu oxy.
Tt nhin xc tc v phng php tng hp n gi vai tr quan
trng. Vic b sung cc hot cht bin tnh hay s dng hn hp oxyt
v mui u to kh nng thay i mnh hot tnh v tnh la chn. V
d mt s cht phn xc tc (halogen, selen) khi kh hot tnh ca bc
trong qu trnh oxy ho etylen, s lm tng lu chn ca qu trnh
oxy ha. Cc oxyt ca molipden v bismut (Si2O3 :MoO3 =1:2) l cc
xc tc chn lc cho qu trnh oxy ha d th propylen cht mang, kch
thc ht xc tc, xp... l cc yu t gy ra nh hng ln. Do kh
nng oxy ha tip tc cc cht chnh v tc cao ca phn ng ha
hc trn b mt cht xc tc nn qu trnh chuyn qu trnh vo vng
khuch tn trong l iu khng mong mun. V vy cc cht xc tc
c s dng vi cc ht khng ln v l hi tng i ln.
H thng thit b phn ng oxy ha xc tc d th
Cc phn ng oxy ha ny thng tin hnh di p sut kh quyn
nhng ngy cng c nhiu cng ngh trong qu trnh oxy ha xc
tc d th c tin hnh di p sut 0.3 2 MPa. iu ny cho php
tng cng nng sut qu trnh, gim kch thc thit b v d dng
cho qu trnh tch hydrocacbon khng chuyn ha cng nh sn phm
to thnh. Nhit qu trnh khc nhau s thay i t 250 3000C n
450 5000C. Do tnh n nguy him ca hn hp hydrocacbon vi oxy
nn ngi ta a vo mt vi phng php sau thot khi vng
63

nng nguy him: oxy ha bng kh hon lu c b sung khng kh

bn ngoi hay oxy nng olefin thp (3 5% th tch), oxy ha vi
hydrocacbon d bng mt oxy k thut c pha long bng hi nc.
Mt trong cc vn c bn thc hin qu trnh oxy ha pha kh
l kt cu ca thit b phn ng sao cho m bo qu trnh gii nhit v
loi tr vng nhit cc b. Do h s dn nhit t kh ti thnh thit b
khng ln nn bi ton ny phc tp hn nhiu so vi qu trnh oxy ha
trong pha lng. Vn tng cng b mt trao i nhit s c ngha
ln v nh s tn dng c nhiu nhit phn ng to hi nc.
Do ch tiu kinh t ca qu trnh oxy ha cao nn cc thit b ng p
thng khng s dng trong qu trnh ny. Ngi ta thng s dng
nht l thit b dng ng vi lp cht xc tc c nh nm trong cc ng
v cc lm lnh qua khong trng bi cht lm ngui (hnh 2.5a).
Cc ng c ng knh 10 25mm s to ra kh nng gii nhit v xc
lp qu trnh cn bng nhit theo tit din ngang, s dng tt vng
th tch cht xc tc chim ch, ngi ta a vo thit b cc tc nhn
c un nng s b. Phng php tt nht gii nhit thot ra l
dng nhit un nng nc ngng trong khong trng gia cc ng
ti sinh li hi nc hay p sut ph thuc vo nhit . i lc ngi
ta s dng qu trnh lm lnh bng cht mang nhit (qu trnh nng
chy ca mui...), qua nc ngng t un si v hi to ra trong
qu trnh cng ngh s c lm ngui tr li.
Cc u im ca thit b dng ng l n gin v cu to v qu trnh
bo qun, bo dng cng nh thay th cc chi tit ring c kh nng
lm tng la chn, nhc im ca thit b ny l khng ng
u ca nhit trong lp xc tc, phn trm th tch c ch tng i
nh, kt qu l qu trnh hao ph kim loi ln.
i vi nhiu qu trnh oxy ha ngi ta s dng cc thit b phn
ng vi lp xc tc d th kh lng (hnh 2.5b). Chng ging vi cc thit
b ca qu trnh cracking xc tc trc y, ch khc l thi gian s
dng xc tc lu hn v y lng cc v nha ha t hn. Xc tc
c s dng dng vi cu.
Cc tc nhn c th a vo di dng lnh, cn cht xc tc c s
dng dng vi cu c bn ha.
Trong thit b phn ng thng c b tr nhng mng li phn b,
cc ng lm lnh (trong ng hn hp c ti sinh) v cc xyclon
thu li cc ht bay theo kh. Trong thit b ny vn gii nhit c
gii quyt mt cch l tng l duy tr cn bng nhit nhng s xy ra
qu trnh phi trn nghch lm gim tnh la chn ca qu trnh.
hn ch nhc im ny ngi ta s dng thit b c lp phn
on xc tc gi lng m trong ngoi cc mng phn b c s cn
c mt vi mng chia th tch phn ng thnh nhiu khoang ring bit
64

(hnh 2.5c). C th gim qu trnh phi trn nghch bng cch s dng
dng xc tc i ln cng vi kh trong cc thit b phn ng (hnh 3.1d).
ng phn ng c lm lnh bng nc trong v o. Xc tc c
tch trong thit b tch hay xyclon v c a tr v theo ng ng
vo phn di ca thit b phn ng. Trong thit b biu din trn hnh
2.5d th iu kin trao i nhit bt li hn thit b trn hnh 2.5c do din
tch trao i nhit t hn. Tuy nhin thit b phn ng tng t c th
c thc hin dng cc ng kt hp v qu trnh lm lnh xy ra
gia cc ng.
Khi chn vt liu ch to thit b i vi qu trnh oxy ha pha kh cn
phi quan tm n qu trnh n mn khng ch do cc axit cacboxylic
m c do hn hp CO2 vi hi nc to thnh trong phn ng. Ngoi
ra mt vi kim loi v cc oxit ca chng c th xc tc cc phn ng
khng mong mun ca qu trnh oxy ha hon ton. V vy tt c thit
b phn ng cho thng c ch to t thp hp kim.
Hn hp
ban u

Sn phm

Sn phm

Sn phm

hi
hi

hi

hi
nc

nc

nc
Sn phm

(a)

Hn hp
ban u

Hn hp
ban u

Hn hp
ban u
nc

(b)

(c)

(d)

Hnh 2.5. H thng thit b phn ng oxy ha xc tc d th

a Thit b dng ng vi lp xc tc c nh,
b Thit b vi lp xc gi lng,
c Thit b vi phn on lp xc tc gi lng,
d Thit b dng xc tc i ln

2.4.3. Oxy ha ng th.

C ch to thnh cc sn phm oxy ha ng th
Khi oxy ha hydrocacbon s to thnh hng lot cc sn phm:
hydropeoxyt, ru, xeton, anehit, axit cacboxylic, este v mt vi hp
cht a chc phc tp hn. Phn t hot ng trung gian l cc gc vi
ha tr t do trn nguyn t C (R.) hay trn nguyn t oxy (ROO,
RCOO)
Hydroperoxyt:
L sn phm phn t bc nht ca qu trnh oxy ha hydrocacbon.
Chng c to thnh nh sau:
65

ROO*

R* + O 2

ROOH + R*

ROO* + RH

Phn ng tng tc ca gc peroxyt vi hydrocacbon (phn ng sau

s xc nh cu to ca hydroperoxyt to thnh v cc sn phm k tip
ca qu trnh oxy ha. Trong cc trng hp ny kh nng phn ng
ca cc nguyn t hydro vn tun theo cc quy lut chung cho cc
phn ng gc v c xc nh bi bn tng i ca gc trung
gian R*. Do , v tr thun li cho qu trnh tn cng ca cc phn t
khi oxy ha hp cht alkylaren l v tr C so vi vng thm ca mch
nhnh alkyl cn i vi olefin l v tr allyl. Ngoi ra i vi tt c hp
cht hydro v tr nguyn t C khc nhau l: cacbon bc 3 > cacbon
bc 2 > cacbon bc 1.
Hydroperoxyt l nhng hp cht khng bn, d dng chuyn ha
thnh sn phm khc khi oxy ha. V vy nng ca chng trong hn
hp phn ng thng thp, nht l trong cc phn ng oxy ha c xc
tc hay nhit cao. Hydroperoxyt bc 1 l sn phm km bn nht
(RCH2-OOH hay ArCH2OOH cn hydroperoxyt bc 3 th tng i bn
nh: (CH3)3COOH; C6H5-C(CH3)2OOH l cc sn phm cng nghip.
Cc hp cht bc 2 tng i bn l hydroperoxyt ca xycloankan C8C12, olefin v hp cht alkylaren.
Ru v hp cht cacbonyl:
L cc sn phm th cp ca qu trnh oxy ha hydrocacbon. Ru
nhn c nhiu khi oxy ha parafin v naphten nhng khng to
thnh c t hp cht alkylaren. Theo s ca San Hebek-Pritskov,
cc sn phm ny s to thnh khi oxy ha thng qua giai on
hydroperoxyt:
Ankan

+O2

Hydroperoxyt

Ancol
Xeton

+ O2

Hydroperoxyt s phn hy di tc dng ca nhit cao hay oxy

ha c xc tc to ra ru v hp cht cacbonyl. Qu trnh phn hy
ny c th xy ra theo c ch phn t, tuy nhin trong qu trnh oxy ha
th cc sn phm c to thnh ch yu theo c ch mch:
ROH + RO*

ROOH + R.
RO* + RH

ROH + R*

Xeton c to ra t hydroperoxyt bc 2 qua giai on gc

hydroperoxyt trung gian:
R2CHOOH + HO*

-H2O

R2C*OOH

R2C=O + HO*

Hydroperoxyt bc 3 trong qu trnh chuyn ha mch s to ra ru v

66

xeton nh qu trnh ct kin kt cacbon-cacbon:

R3COOH + R*

-H2O

R3C*=O

R2C=O + R*

ROH + R3C*=O

Ru chuyn thnh xeton cng theo c ch mch trong hn hp

phn ng v din ra nh sau:
R2CHOH

+ROO*
-ROOH

R2C*OH

+O2

R2COH
OO*

+RH
R2COH
-R*
OOH

R2C=O + H2O2

Ni
chung l c ch phn ng xem xt ch yu xy ra i vi oxy ha
khng c xc tc trong pha lng nht bnh thng. Cn khi oxy
ha nhit cao v pha kh th tt c sn phm s to thnh qua gc
peroxyt ch khng phi qua hydroperoxyt. Trong , xy ra qu trnh
ct t mch mi lin kt C-C v to ra ru alehyd:
HCHO + CH3CH2O*

CH3-CH2-CH2OO*

+C3H8
-C*3H7 HCHO + C2H5OH

CH3-CHO-CH3O* +C*3H8 CH3CHO + CH3OH

-C 3H7

CH3-CH-CH3
OO*

Hin nay ngay c vi qu trnh oxy ha pha lng, cc gc peroxyt gi

vai tr ln trong vic to thnh sn phm. V d, cc hp cht cacbonyl
c th iu ch t peroxyl nh sau:
R 2C*

R2CH
OO*

R2C=O + HO*

OOH

Khi xc tc bng mui ca kim loi c tnh chuyn i ha tr s to ra

phc vi cc gc peroxyt. Cc phc ny s chuyn ha trong mi
trng nh hng ca ion trung tm khi oxy ha n thnh trng thi c
ha tr cao nht.
R2CHOO* + Co(OAc)2

R2CHOO*Co(OAc)2

R2C=O + HOCo(OAc)2 NNh

ru v hp cht cacbonyl c th iu ch khi oxy ha pha lng

khng nhng ni tip theo hydroperoxyt m cn song song vi chng.
Axit cacboxylic:
Axit cacboxylic c to thnh khi oxy ha hydrocacbon vi qu
trnh bo ton mch C hoc l c t lin kt C-C. Kh nng u tin
ch xy ra khi chuyn ha hydroperoxyt bc 1 v d nhin l ch i vi
qu trnh oxy ha ca nhm metyl trong hp cht alkylaren qua giai
on trung gian anehit:
ArCH3

+O2

ArCH2OOH

-H2O

ArCHO

+O2

ArCOOH

Khi oxy ha parafin v naphten, axit cacboxylic s c to thnh

cng vi qu trnh ct t mch cacbon. Rt c th xeton l cc sn
67

phm c hnh thnh trc khi sinh ra axit. Chng d b oxy ha hn

so vi hydrocacbon tng ng v ch yu nguyn t C bn cnh
nhm cacboxylic to ra gc xetoperoxyt v xetohydroperoxyt
sau s xy ra qu trnh t lin kt C-C, v d:
ArCH3

+O2

-H2O

ArCH2OOH

ArCHO

+O2

ArCOOH

Cc axit bo thp phn t v axit bo thm trong cc iu kin nh

nhng thng bn vi qu trnh oxy ha tip tc.
Anehit l cc hp cht d b oxy ha. V vy khi oxy ha
hydrocacbon trong pha lng, anehit hoc l c to ra mt lng
nh, hoc l chng khng hin din trong cc sn phm ca phn ng.
i vi qu trnh oxy ha chui gc, anehit s to ra cc gc axyl trung
gian hay peroxyaxyl trung gian v peroxyaxit:
RC*=O + O2

RCOOO*

RCOOO* + RCHO

RCOOOH + RC*=O

Peroxyaxit c kh nng kt hp vi cc alehyd to ra hp cht

peroxit
m trong trng hp oxy ha axetanehit gi l
axetanehitperaxetat (2 hydroxyetylperaxetat).
CH3COOOH + CH3CHO

CH3-C-O-O-CH-CH3
O

OH

Cn bng ca phn ng ny nhit thp s dch chuyn nhiu v

phi v trong trng hp ny nu khng c hay c 1 lng t xc tc th
peraxetat s tr thnh sn phm cui cng ca qu trnh oxy ha. Khi
nung nng vi mui kim loi c tnh chuyn i ha tr, peraxetat s b
phn hy nhanh s to ra 2 phn t axit cacboxylic. Trong cc iu kin
trn, qu trnh to thnh peraxetat khng mnh v phn ng oxy ha
anehit s c thc hin bi axit peraxetic:
CH3COOOH + CH3CHO

2CH3COOH

Ngoi peroxyaxit v axit cacboxylic th sn phm khc ca qu trnh

oxy ha anehit l anhydric. Qu trnh to thnh cc anhydric l nh s
dng xc tc hn hp (mui Co hay Mn vi mui Cu) v p sut O2 cc
b thp. Mt trong cc c ch c kh nng ca qu trnh to ra anhydric
l qu trnh chuyn ha ca gc axyl trong mi trng nh hng ca
nguyn t Cu:
R-C*=O + Cu(OOCR)2

R-C*.Cu(OOCR)2
O

(RCO)2O + CuOOCR

Sau khi iu ch, mui Cu ha tr 1 s li oxy ha peroxyaxit thnh

trng thi c ha tr cao hn.
Tnh chn lc ca qu trnh oxy ha ng th
Tnh chn lc ph thuc vo qu trnh pht trin cc phn ng song
song hay ni tip khi to thnh cc sn phm chnh v ph. Cc phn
68

ng song song c th xy ra bi 2 yu t phn ng theo cc nguyn t

cacbon khc nhau trong phn t ca tc nhnban u hoc l qu trnh
to thnh song song cc cht vi cc nhm chc khc nhau. Phn ng
u tin s ph thuc vo kh nng phn ng tng i ca cc
nguyn t hydro khc nhau trong qu trnh tn cng vo chng bi gc
peroxyt hay cc gc cha oxy khc. Trong mi quan h ny qu trnh
oxy ha gc - mch s c c trng bi tnh chn lc tng ng cao
ph thuc vo hot ng yu ca cc gc peroxyt. V d kh nng
phn ng ca nguyn t H nm v tr cacbon bc 3, 2, 1 s theo t l
100 : 1. iu ny cho php khi tng hp tec-pentylhydroperoxyt vi qu
trnh hin din trong phn t izo-pentan c 3 dng nguyn t hydro
hoc iu ch cc sn phm chuyn ha ch yu theo v tr cacbon bc
2 khi oxy ha n-parafin.
Qu trnh to thnh song song cc cht vi nhm chc khc nhau (v
d to thnh ru v xeton t hydrocacbon hay axit cacboxylic v
anhydric t anehit) nhiu khi c th iu chnh bng cch la chn cc
thng s tng ng ca qu trnh. Chng hn, hiu sut tng i ca
ru v xeton s xc nh bng t l tc ca cc giai on c s:
R* + O2

k1

ROO* + RH

ROO*
k2

ROOH + R*
+R*(k3)
ROH + RO*

ROOH
*

+ROO (k4)

ROOH + R,OH + HO*

Cc phn ng ny xc nh t l sau y ca cc nng gc t do

v hiu sut to thnh ru, xeton:
[R*] / [ROO*] = k2 [RH] / k1 [O2]
D [ROH] / d [xeton] = k3 [R*] / k4 [ROO*] = k2k3 [RH] / k1k4 [O2]
Nh vy hiu sut ca ru c th tng nu gim p sut ring phn
ca O2 khi oxy ha pha kh. i vi qu trnh oxy ha anehit s dn
n qu trnh tng hiu sut anhydric do cc axit cacboxylic.
Qu trnh chuyn ha ni tip ng vai tr quan trng i vi qu
trnh oxy ha gc - mch. Ngoi cc sn phm xem xt trn c th
nhn c oxyxeton, dixeton, axit oxy v xetocacboxylic, este, lacton,...
cui cng c th s gp qu trnh oxy ha hon ton cho ti CO2.
Phng php ch yu lm gim tc dng ca phn ng ph ny l iu
chnh mc chuyn ha. Theo tt c cc qu trnh oxy ha gc mch c chia thnh 2 nhm:
Cc qu trnh xy ra nhm iu ch ch yu cc cht bn vi qu
trnh oxy ha tip tc (axit bo thp phn t v axit thm). Lc mc
chuyn ha khng gi vai tr ch yu trong vic tnh chn lc mc
69

d n c th nh hng ln cc ch tiu khc (lm chm phn ng, lm

kt ta xc tc). Trong trng hp ny mc chuyn ha c th l
khc nhau (thng t 95 99%) cn cc cht trung gian c th a tr
li oxy ha cng vi tc nhn khng chuyn ha.
Cc qu trnh trn hng vo ch yu tng hp cc hp cht
trung gian c kh nng phn r hay oxy ha tip tc (hydropexoxyt,
ru, xeton, axit bo cao phn t). V vy mc chuyn ha gi vai
tr rt quan trng v n c khng ch trong khong t 5 30%.
y cn phi thc hin qu trnh ti sinh v hon lu tc nhn khng
chuyn ha v cc qu trnh ny cn c ti u ha bng gin biu
din qu trnh ph thuc ca tnh chn lc vo mc chuyn ha.
Nhit l yu t gy nh hng ln n tnh chn lc v c qu
trnh khc bit v nng lng hot ha ca cc giai on qu trnh.
Nng lng hot ha phn ng ph thng cao, v vy u th ca n
s tng cng vi qu trnh tng nhit cn tnh chn lc th gim. Nh
vy mi mt qu trnh u c mt vng nhit ti u xc nh bi t l
thch hp gic tc oxy ha v tnh chn lc.
H thng thit b phn ng oxy ha
Phn ln cc qu trnh oxy ha u tin hnh trong pha lng bng
cch sc khng kh (i khi l O2 k thut) qua tc nhn hu c ban
u, s t t tch t cc sn phm ca phn ng. Nu la chn
nhit da vo cng v tnh chn lc ca qu trnh th p sut s
c chn sao cho hn hp phn ng tn ti trng thi lng.
i vi thit b cng nghip, thng s dng nht l cc thp sc kh
chiu cao t 10 15m v ng knh 2 3m, trong vi trng hp
chng c th c phn thnh nhiu on bi cc mm chp hay li
nm ngang hoc l chng c ni vi nhau to thnh h gm nhiu
giai on ni tip nhau. Do axit cacboxylic n mn c thp thng
nn ch to thit b phi s dng thm Al, Titan hay mt vi hp kim
ca thp bn vi tc dng ca axit hu c.
iu quan trng nht l phng php loi mt lng ln nhit ta ra.
C mt s h thng vi c cu trao i bn trong v do lm c cu
thit b thm phc tp. lm n gin hn kt cu thit b thng cho
b phn trao i nhit nm bn ngoi v cht lng hon lu s chy
qua n. Tin li hn ht l dng nhit nung nng hydrocacbon ban
u hay dung dch c ngng t kh thot ra qua bnh ngng v a
tr v thit b phn ng. Tt nhin trong 1 s c cu mi lm c
nhit cao 1500C th nhit phn ng s dng sn sut hi nc
cn p sut c dng phn chia mt phn hn hp hay lm
lnh,...
Trn hnh 2.6a biu din thit b in hnh cho qu trnh oxy ha gin
on vi b phn lm lnh t bn ngoi v cht lng hon lu qua
70

sinh hn nc. Qu trnh hon lu c th tin hnh theo phng php

ngc dng do t trng ca cht lng khc nhau trong thp v trong
c cu hon lu. Tc nhn ban u s cho vo thit b khi chm dt
nguyn cng trc v c nung nng n nhit cn thit (trong
thi gian ny nc trong b phn lm lnh s chuyn thnh hi) sau
bt u a khng kh vo. Cc c cu phn phi trong thit b thng
dng ng chm, sng hay mm li.
S tin hnh lin tc ca qu trnh 1 thp sc duy nht s c th
thc hin khi iu ch cc sn phm bn vi qu trnh oxy ha tip tc
(axit axetic, cc axit thm). Trong trng hp ny cht oxy ha v
khng kh c a trc tip vo phn di thit b phn ng cn sn
phm thi thu hi pha trn (hnh 2.6b). Vic loi nhit ta ra s c
tin hnh bng bt k phng php no nu trn nhng trn hnh s
khng biu din cu to trong ca b phn lm ngui.
Nu chn lc ca phn ng ph thuc mnh vo mc chuyn
ha ca tc nhn ban u th vic s dng 1 thp sc duy nht s
khng thun li i vi qu trnh lin tc do qu trnh trn ln mnh ca
cht lng.
Trn hnh 2.6c biu din cascad ca cc thp sc: hn hp phn
ng lng s ln lt chy t thp ny sang thp khc cn khng kh th
c cho vo tng thp mt. y trnh by phng php tch nhit
bng cch dng nhit lm bay hi hydrocacbon hay dung dch. Hi
ca chng s c ngng t trong bnh ngng nm pha di mi
thp v qu trnh ngng t xy ra trong thit b phn ng.
Trn hnh 2.6d biu din mt dng thit b phn ng lin tc khc cho
qu trnh oxy ha l thp mm. Trong , cht lng s chy t trn
xung di, t mm mt sang mm khc cn khng kh th chuyn
ng ngc li t di ln trn. i vi b phn lm lnh dng ng
xon c b tr trong lp cht lng trn mi mm v nc s chy
bn trong ng. Ngoi ra c th t b phn lm lnh ngoi, khi
cht lng trn mi mm s chy qua tng b phn lm ngui ring.
Trong tt c cc thit b phn ng ch gin on v lin tc, cc
qu trnh oxy ha s c iu chnh bng cch thay i tc a
vo cc tc nhn oxy ha v cc tc nhn hu c ban u. Nhit
thng c o ti mt vi im trn chiu cao thit b phn ng cn
hn hp phn ng th c ly mang i phn tch sau mt thi nht
nh.
i vi qu trnh oxy ha pha lng cn phi loi tr qu trnh to
thnh hn hp n nguy him cc b tc l cn c qu trnh pha kh
thng xuyn trong phn trn ca thp sc v khong khng trn mi
thp mm trong thit b phn ng hnh 2.6d. iu ny t c nh
mc chuyn ha cao ca O2 kt hp vi p sut chn da vo
71

cc cu t d bay hi ca tc nhn hu c ban u. i khi trong

khong khng trn cht lng ngi ta cho thm vo kh N2. Ni chung
i vi qu trnh sn sut d gy qu trnh chy n (oxy ha parafin) th
cn phi b tr thm cc phng tin phng chng qu trnh chy
trnh thit hi.

Hnh 2.6. H thng thit b phn ng oxy ha

a Thit b phn ng dng thp lm vic gin on vi b phn lm ngui t ngoi, b
Thit b phn ng dng thp lm vic lin tc vi b phn lm ngui t trong, c Cascad
ca cc thp vi b phn lm lnh hi, d Thp mm

2.5. Cc qu trnh thy phn, tch nc, este ha, amit ha

Cc qu trnh thy phn cng hp nc, tch nc, este ha v amit
ha ng vai tr rt quan trng trong cng nghip tng hp hu c c
bn v tng hp ha du. Bng cch thy phn cc cht bo, xenlulo v
72

hydratcacbon t lu ngi ta sn xut x phng, glyxerin, etanol v

cc sn phm qu gi khc. Trong lnh vc tng hp hu c, cc qu
trnh trn c s dng ch yu tng hp cc ru C2 C5, phenol,
ete, - oxit , cc cht khng no khc nhau, cc axit hu c v dn xut
ca chng (nh este, anhyrit, nitril, amit) v cc hp cht khc.
2.5.1. Thy phn
Thy phn c gi l cc phn ng th hoc trao i kp xy ra di
tc dng ca nc hoc kim. Thy phn c th c phn chia thnh
cc phn ng lm t cc lin kt C-Cl, C-O, C-N, ...Trong i vi
cc dn sut cha clo, ngoi vic thy phn vi s th nguyn t clo
ROH + Cl-

R-Cl + OH-

C th xy ra qu trnh tch loi HCl to thnh cc hp cht khng no

hoc oxit
RCH = CH2 + Cl- + H2O

RCHCl - CH3 + OHRCHOH - CH2Cl + OH-

RCH - CH2 + Cl- + H2O

O

Cc dn sut clo thng c s dng nh cc hp cht trung gian vi

mc ch bin i chng tip tc bng cch thy phn hay tch HCl
trong mi trng kim. u tin ngi ta a vo hyrocacbon cc
nguyn t clo c linh ng cao v sau tin hnh tc dng ln dn
sut clo ny cc tc nhn thy phn. Bng con ng ny, trong cng
gnhip ngi ta sn xut mt s ru, phenol, cloolefin, oxit
C ch phn ng
Thy phn v tch loi HCl trong mi trng kim thuc loi cc phn
ng th i nhn v tch loi. Trong phn ln cc trng hp chng xy
ra theo c ch lng phn t. Khi thy phn giai on quyt nh l s
tn cng ca tc nhn thy phn vo nguyn t cacbon cha nguyn t
clo v bn ca lin kt mi c tng ln theo mc t lin kt
c (c ch SN2)
RCH2Cl + OH-

RCH2 ... Cl

RCH2OH + Cl-

OH

Cn khi tch HCl, s tn cng ca ion OH- nhm vo nguyn t hyro

ni vi nguyn t cacbon nm v tr (c ch E2)
-

RCH2 - CH2Cl + OH

RCH ... CH2 ...Cl

RCH=CH2 + H2O + Cl-

H ... OH

Cng tng t nh vy, trong phn ng vi clohyrin s nhanh chng

73

thit lp cn bng kim axit

ClCH2 - CH2 - OH + OH-

H2O + ClCH2 - CH2O-

V ion ancolxi mi c sinh ra s bin i ni phn t, trong lin

kt c s yu i v lin kt s tng ln tng ng v bn
-

ClCH2 - CH2O-

Cl- + H2C - CH2

Cl .. H2C - CH2
O

Nu s dng dung dch Na2CO3 thy phn th qu trnh c thc

hin bng cc ion hyroxy to ra khi thy phn xoa, nhng ngoi ra
cn c s tham gia ca cc ion CO32- v HCO3-. C ch thy phn vi
s tham gia cc ion trn th hin bng s to thnh cc sn phm
cacbonat trung gian sau khi phn r s cho cc ancol
RCl + CO32-

R .. Cl
OCO2

ClCH2 - CH2 - OH + OH-

2-Cl-

RO - C - O- +H2O

ROH + HCO3-

O
H2O + ClCH2 - CH2O-

Tnh la chn ca qu trnh v cc phng php iu chnh

Tnh la chn ca qu trnh v cc phng php iu chnh nh thy
trn, di tc dng ca kim n cc dn sut clo s ng thi xy ra
hai phn ng: th v tch loi v trong trng hp c th ngi ta ch
cn mt trong hai phn ng. T l hai sn phm th v tch loi ph
thuc vo nhit , tnh cht ca mi trng phn ng ( pH) v cc
yu t khc, nhng trong thc t phng php c hiu qu nht thay
i t l trn l s la chn tc nhn thy phn. Xem xt cc phn ng
ny, chng ta thy trong qu trnh th th tc nhn thy phn tn cng
vo nguyn t cacbon v n mang tnh i nhn, cn trong phn ng
tch loi, khi lin kt vi nguyn t hyro n li mang tnh kim. Nh
vy khi mun qu trnh th xy ra ch nn s dng tc nhn l kim yu
v c tnh i nhn cao (v d Na2CO3), cn tch HCl phi s dng
tc nhn kim mnh v tnh i nhn thp (v d NaOH hay Ca(OH)2).
Trong phn ng tch HCl t cc dn sut clo cn c th xy ra qu
trnh ph: hyro c th tch ra t cacbon khc nhau, dn n s to
thnh nhng ng phn olefin khc nhau, v d:
+OH- CH = CCl + H O + Cl2
2
2
ClCH2 - CH - Cl2

CHCl = CHCl + H2O + ClHng phn ng chnh c xc nh theo qui tc zaixep

74

Cn ch l trong trng hp tch HCl, phn ng c th xy ra mc

su hn vi s hnh thnh cc dn sut acetilen
CH2Cl - CHCl2

-HCl

CH2 = CCl2

-HCl

CH

CCl

Hoc thy phn cc oxit sinh ra glycol

HOCH2 - CH2Cl

-HCl

H2C - CH2 +H2O

HOCH2 - CH2OH

gim ti a phn ng ph trn cn phi gim nng ca sn phm

chnh trong hn hp phn ng bng cch chng ct lin tc. iu ny
c th c thc hin trong thc t v nhit si ca sn phm chnh
thng thp hn so vi nhit si ca cc cht ban u tham gia
phn ng v hn na n thng to hn hp ng ph vi nc.
Trong trng hp thy phn bng nc th sn phm ph ca cc qu
trnh bin i tip tc l ete. S to thnh ete c th gii thch nh sau:
sn phm ban u ca phn ng l ru se tham gia nhanh chng vo
qu trnh trao i axit baz vi kim to thnh ancolgolat c kh
nng tc dng vi cc dn sut clo
RCl + OHROH + OHRCl + RO-

ROH + ClRO- + H2O

ROR + Cl-

Nh vy tnh la chn s gim khi c s tch t ru trong mi trng

phn ng.
Trong trng hp thy phn bng cc kim mnh, tnh la chn s
gim rt nhanh v cc ion ancolat c hot tnh cao hn so vi cc ion
hyroxy.
Khi thy phn bng xoa, nu da vo c ch xem xt trn, c th
thy phn ng vi cc ion cacbonat ch to ra ru, cn ete ch c th
sinh ra trong phn ng vi ru hay vi ion ancolat c hnh thnh t
ion hyroxy l sn phm ca qu trnh thy phn xoa.
C th kt lun rng thy phn theo phn ng th nn tin hnh trong
mi trng xoa, khi s hn ch qu trnh tch HCl, ng thi gim
ti a sn phm ph ete. Mt t l mol ti u gia dn xut clo v nc
c la chn trn c s tnh ton kinh t khi so snh tnh la chn vi
chi ph nng lng cn thit tch nc (thng thng t l ti u
ny dao ng trong khong nng dung dch ru trong nc t 1
1.5mol/l)/ Yu t cui cng tng tnh la chn l qu trnh thy phn
thng c tin hnh trn nhng thit b gn vi thit b tch l tng
Khc vi nhng vn trnh by trn, trong qu trnh thy phn cc
75

dn sut clo ca cc vng thm, do hot tnh ca chng thp v khng

c kh nng tch HCl, v th phn ng c tin hnh trong mi trng
kim mnh. Trong trng hp ny, s to thnh sn phm ph ete
khng ng vai tr quan trng v nhit cao ca phn ng, cc ete
diaril s b nc thy phn quay tr li phn ng
ArCl +OH

-HCl

ArOAr +H2O

ArO- +ArCl
-Cl

ArOH

-2H

2ArO-

Do vy khi thy phn dn sut clo ca aril cn phi dng lng kim ln
gp hai ln v sn phm cui cng khng phi l phenol m l phenolat.
2.5.2. Qu trnh hp nc v tch nc
Khc vi thy phn, phn ng cng nc dn n vic kt hp phn t
nc vo ni i C=C, ni ba gia cacbon vi cacbon.
RCHOHCH3

RCH = CH2 + H2O

CH

CH3CHO

CH + H2O

Hoc ni ba gia cacbon v nit (CN)

RCN + H2O

RCONH2

Mt s phn ng cng nc l qu trnh thun nghch v phn ng theo

chiu nghch ca s cng nc l tch nc. S tch nc c th xy
ra ni hoc ngoi phn t
2ROH + H2O

ROR + H2O

Xc tc v c ch phn ng
Cc phn ng nu trn u thuc nhm phn ng c hot ha bng
xc tc axit. Cc xc tc in hnh ca qu trnh hp nc l cc axit
proton tng i mnh: axit photphoric c hp ph trn ch mang
axit vonframonic, cationit sunfua phenolCn tch nc, ngi ta
s dng axit photphoric trn cht mang oxit nhm, axit sunfuric trn cht
mang mui photphat (CaHPO4) Vai tr ca cht xc tc trong phn
ng hp nc c th hin bng s proton ha olefin qua giai on
to thnh cc phc v trung gian. Cn trong qu trnh tch loi
nc th phn ng xy ra theo chiu ngc li
+
RCH=CH2 +H RCH=CH2

RCH+CH3 +H2O RCH-CH3

+

H+

OH2

-H+

RCH-CH3
OH

Cn lu l trong qu trnh tch nc ngoi phn t, ion cacboni khng

tch proton ra m n kt hp vi phn t ru khc
R
RCH+-CH3 + RCH-CH3
OH

H3C

R
CH O+H

H3C

CH O + H+

76

S hp nc ca olefin theo c ch i in t s lun theo quy lut

Maccopnhicop v kh nng phn ng ca chng c th sp xp nh
sau:
Iso buten > n-buten > propylen > etylen.
Tt nhin t l kh nng phn ng ca cc olefin trong dytrn s thay
i cc iu kin phn ng khc nhau v xc tc khc nhau.
Cn bng cng tch nc t ph thuc vo cu to ca olefin v ru,
v vy dy kh nng phn ng ca olefin s tng ng vi kh nng
phn ng ca ru khi tch nc:
Bc 3 > bc 2 > bc nht
Cc phn ng ph v tnh la chn ca qu trnh
Khi cng nc vo olefin th song song vi phn ng chnh cn xy ra
qu trnh oligome ha cc olefin v s to thnh dn sut ete. Tt c
cc qu trnh u qua giai on trung gian hnh thnh ion cacbonic v
c th biu din tng qut nh sau
H2O

+R+ (k1)
-H+

R+ + olefin

(k3)

ROH

+R+ (k2)
-H+

ROR

oligome

i vi cc trng thi ca h phn ng nm xa trng thi cn bng c

th vit phng trnh vi phn tnh la chn sau:
k2 [ ROH ]
1
d [ ROH ]
k1 H2O
ROH =
=
k3
d [Olefin] 1 + [Olefin]
k1 [ H 2O]

T phng trnh trn cho thy tnh la chn tng khi c mt lng
nc d so vi olefin v ru sinh ra. Ru c hot tnh cao hn so
vi nc (k2/k1 >1), v vy cn phi tin hnh phn ng sao cho lun c
mt lng nc d ln so vi ru (15 : 1). Hiu sut ca oligome
ha ph thuc vo kh nng ca olefin tham gia phn ng trng hp.
S to thnh polyme c th khng ch khng nhng bng cch thay i
t l nc v olefin m cn c th bng cch gim nhit , v phn ng
trng hp olefin cn nng lng hot ha ln hn so vi phn ng
cng nc. Cn lu rng khi phn ng gn vi trng thi cn bng th
vn tc qu trnh cng nc v tnh la chn s gim, iu ny gy kh
khn khi tin hnh phn ng n chuyn ha gn vi trng thi cn
bng. i vi tng olefin c th v tng xc tc c th c mt iu kin
ti u (t l cc cu to, mc chuyn ha, nhit ) t c
hiu sut qu trnh v tnh la chn cao nht.
i vi qu trnh tch nc ca ancol c th biu din theo s phn
ng sau
77

ROH

+H+

R+

-H2O

OLEFIN
ROR + H+

ROH + OLEFIN

S tch nc ni phn t c nng lng hot ha cao hn so vi s

to thnh ete, do vy s tch nc to ni i cn phi tin hnh
nhit cao, p sut thp v nng ancol thp.
Trn y cn cha cp n mt phn ng ph m trong khng t
trng hp n c th xy ra, l s to thnh anehit hoc ceton
CH3 - CH2OH

+H2

CH3 - CHO

Phn ng trn c th xy ra vi s c mt ca cc ch mang xc tc

cng nh cc xc tc dng oxit kim loi, cn xc tc phc proton khng
tham gia vo phn ng trn.
Thit b s dng cho qu trnh hp nc ca etylen v propylen
Kh thi

Kh thi
H2O
Hn hp
ban u

Sn phm

H2SO4

H2O

H2O

H2O

H2O

H2O

Hn hp
ban u

H2O
Sn phm

Hnh 2.7. Thit b s dng cho qu trnh hp nc ca etylen v propylen

a Thit b hp thu vi h thng a quay, b- thit b hp thu hot ng lin tc

Trong trng hp hp ph etylen v propylen vi H2SO4 c th s dng

2 loi thit b. dng th nht (hnh 2.7a) l mt thit b hp ph t nm
ngang, c b phn khuy dng a gn vi mt trc, khong 1/3 khng
gian thit b c cha H2SO4 v khi cc a quay s to sng H2SO4.
Do vy, tng c b mt tip xc vi olefin. Nhit sinh ra trong phn
ng s c ti ra bng v o nc. thit b ny lm vic gin on,
nhng nu s dng mt chm lin tc cc thit b trn th s c mt
qui trnh sn xut lin tc.
So vi thit b hp thu nm ngang, th thit b hp thu dng thp ng
vi khong 20 25 a c cha nc bn trn c kh nng hot
ng lin tc v l mt s ci tin ng k. Trn mi a, trong lng cht
78

lng n c chm ng nc lnh i qua hp thu nhit phn ng.

a trn cng ca thp, ngi ta cho H2SO4 vi nng cn thit i
vo, cn di y thp s l hn hp sn phm sau phn ng c
tho ra. Etylen (hoc propylen) c a vo thp t pha di, i
ngc vi dng cht lng v ra khi thp phn ng di dng kh thi
phn nh thp.
Nh vy giai on u s thu c sn phm di dng sunfat v
chng c tip tc thy phn giai on sau. Ch lng sau giai on
u s c lm long bng nc v t nng bng hi nc. qua giai
on lng v chng ct tip tc s thu c etanol nng 90%, cn
nng axit sunfurit s vo khong 40 50%.
2.5.3. Qu trnh este ha
Phn ng este ha c th xem nh phn ng nghch ca qu trnh thy
phn cc este
RCOOH + R'OH

RCOOR' + H2O

C ch phn ng
Trong s cc phng php iu ch este th phng php n gin
nht v thng dng nht l phn ng loi nc gia axit v ancol. y
l mt phn ng thun nghch (v l phn ng gnhch ca phn ng
thy phn este), v phn ng chuyn dch v pha phi (v hng
to ra este ) th cn phi c axit proton (H+) lm xc tc.
Kt qu nhiu cng trnh nghin cu cho thy mch cacbon trong phn
t axit cacboxylic (R-COOH) khng c nh hng g ln n vic OHca phn t nc loi ra ly u, t phn t no (axit hay ancol),
ngc li bc cacbon trong phn t ancol c tc dng quyt nh n
c ch phn ng l dy ni s ct ra u, v tr no, phn t nc
loi ra theo kiu no, ly OH t axit hay ancol. y cn phn bit 2
trng hp.
Este ha ancol bc mt v bc hai vi axit
C hai gi thuyt a ra gii thch qu trnh to thnh ca phn ng
ny
Gi thuyt th nht cho rng di tc dng ca xc tc axit, proton gn
vo nhm OH ca cacboxyl v hnh thnh nn ion cacboxoni (I), tip
ion ny loi ra mt phn t nc to cation axyl (II), phn t ancol
gn vo ion axyl to thnh este c proton ha (III), cui cng vi s
ti to proton, este c hnh thnh.

79

O
nhanh
cham

R-C-OH + H+

cham
nhanh

R-C-O+H
(I)

R-C+ + H2O

nhanh
cham

R-C+ + O-R,

R-C

(II)

O
(II)

nhanh
nhanh

OR
H

(III)

R-C-OR + H+

Gi thuyt khc c minh ha nh sau:

Di tc dng ca xc tc axit, proton gn vo cacbonyl ca nhm
cacboxyl to ra ion hyrat axyl (1), cng lc i in t oxy thuc
nhm OH ca ancol tn cng vo ion dng axyl (I) hnh thnh nn
ion ca este c proton ha (2), cui cng ion ny loi nc v
proton sinh ra este
O

O
nhanh
nhanh

R-C-OH + H+

R-C+

R-C+- OH
(1)

HOR,
cham
nhanh

nhanh
nhanh

OH
R-C - OH
R, O

OH
nhanh
cham

(2)

H
,

R-C-OR + H

RO

Tuy c hai gi thuyt v c ch phn ng k trn c khc nhau v qu

trnh hnh thnh cc ion trung gian nhng u c chung kt lun l
hyroxy ca phn t nc loi ra ly t OH ca axit. Bng vic gn
ng v O17 ngi ta d dng nhn thy c iu ny.
Este ha ancol bc 3 vi axit
Cc kho st cho thy khi este ha ancol bc ba vi axit th phn t
nc loi ra khng ly OH ca axit cacboxylic m ly OH ca phn t
ancol. Qu trnh c gii thch theo nh sau: trong trng hp ny
proton ca axit xc tc khng gn vo oxy ca phn t axit cacboxylic
m li gn vo oxy ca cn bc ba to ra ion oxoni(I), do tc dng
y in t ca 3 nhm ankyl m mt phn t nc c loi ra v to
thnh ion cacboni (II), ion ny tc dng vi phn t axit cacboxylic
sinh ra ion oxoni (III), cui cng bng vic ti to proton sinh ra este (IV)

80

CH3

CH3

CH3
OH + H+

nhanh
nhanh

CH3 - C - OH
(I)

CH3
RCOOH

nhanh
nhanh

(III)
C (CH3)3

cham CH - C+
+ H2O
3
nhanh
(II)
CH3

O
R - C - OH

CH3

CH3

nhanh
nhanh

R - C - O - C(CH3)3 + H+
(IV)

Cc yu t nh hng n qu trnh este ha

C nhiu yu t nh hng n qu trnh este ha, trong ng ch
nht l cc yu t sau:
Este ha l mt phn ng thun nghch
RCOOH + R'OH

RCOOR' + H2O

Mi phn ng c th c mt h s cn bng ring. Hng s cn bng

c tnh bng cng thc
K = Ceste.Cnc / Caxit.Cancol
Gi tr K cng ln th kh nng chuyn ha thnh este cng cao. Vi
cng thc K ny ta c th tnh c nng ca este to ra trong phn
ng nu ta s dng rt tha mt trong hai thnh phn ca cht tham
gia phn ng (ancol hoc axit)
nh hng ca cu trc ancol ti vn tc este ha v nng
este ti im cn bng
Vic kho st c tinhnh gia axit acetic vi cc ancol khc nhau
nhit 1550C, nng t l mol gia cc cht tham gia phn ng l 1 :
1 mol. S liu c o thi im 1 gi (c trng cho vn tc phn
ng) v 100 200 gi (c trng cho im cn bng ca phn ng).
Kt qu kho st ca Mensuki (1987) cho thy, trong s cc ancol kho
st, metanol c vn tc phn ng ln nht v nng este t c ti
thi im cn bng cng cao nht. Cc ancol bc nht, cc ancol no c
vn tc phn ng v h s cn bng cao hn cc ancol bc hai hoc
khng no tng ng. Cc ancol bc ba c vb tc este ha b nht.
Tm li, ancol cng c nhiu mch nhnh v mch nhnh cng gn
nhm OH th vn tc este ha cng gim, nng este ti im cn
bng cng thp
nh hng ca cu trc axit ti vn tc este ha v nng este
ti im cn bng
Cng tng t nh ancol, Mensuki kho st kh nng este ha ca
mt s axit c cu trch khc nhau vi ancol iso-propylic 1500C. Kt
81

qu cho thy tc dng mch nhnh v no ha ca mch cacbon khng

chi phi hon ton theo quy lut nh trong trng hp mch cacbon
ca ancol. Tc este ha v gi tr nng este ti im cn bng
khng t l vi nhau. Mi quan h ny c m t bng sau:
Bng 2.3. nh hng ca cu trc axit ti vn tc este ha v nng
este ti im cn bng
Khi lng este to thnh (%mol)
STT Tn axit
K
Sau 1gi
Sau 100 200gi
1
Formic
61.69
64.23
3.22
2
Axetic
44.36
67.38
4.27
3
Propionic
41.18
68.70
4.82
4
n-butyric
33.25
69.52
5.20
5
i-butyric
29.03
69.51
5.20
6
Metyletylaxetic
21.50
73.73
7.88
7
Trimetylacetic
8.28
72.65
7.06
8
Dimetyletylacetic 3.45
74.15
8.23
9
Phenylacetic
48.82
73.87
7.99
10
Phenylpropyonic 40.26
72.02
7.60
11
Cinamic
11.55
74.61
8.63
12
Benzoic
8.62
72.57
7.00
13
p-toluenic
6.64
76.52
10.62
Xc tc
Cc axit proton c tc dng xc tin nahnh qu trnh este ha nhng
bn thn n khng chi phi ng k n th cn bng ca phn ng, c
ngha l n khng lm thay i gi tr nng este ti thi im cn
bng. Cc xc tc hay s dng l H2SO4 m c v HCl khan nc.
Tc dng ca nhit
Cng nh nhiu phn ng khc, nhit c tc dng lm tng tc phn
ng este ha (c nng ln 100C th tc phn ng tng gp i). Tt
nhin mc tng nhit ca phn ng ny ch cho php n gii
hn si ca ancol. Ngoi ra, mun nng tip nhit th phi dng n
thit b cao p. Thng thng hay dng xc tc axit thc hin vic
nng nhit cho phn ng.
Cc phng php dch chuyn th cn bng ca phn ng este
ha
C 2 phng php dch chuyn th cn bng lm tng nng
este;
82

Tng nng mt trong hai cht tham gia phn ng. Vn ny d

dng thc hin c v hay dng ancol tha nhiu ln so vi axit.
Loi ra ngoi phn ng mt trong hai cht to thnh (este hoc nc).
Vy loi nc hoc este ra bng cch no?
Loi nc ra khi phn ng
Nu c thnh phn axit ln ancol dng trong phn ng este ha u l
nhng cht c si cao hn nc th vic loi nc ra n gin
chng ct li ko, c th dng kh tr sc vo tng cng vic loi
nc.
Nu thnh phn axit c si cao v thn hphn ancol li c si
thp hn nc th ta dng anco vi khi lng tha nhiu v kin tc
chng ct ko ra. Ancol ra ko theo c nc cng ra v tt c ancol (tr
metanol) u to hn hp ng ph vi nc.
Ct nc ra khi phn ng nh vic cho thm mt dung mi tr khng
ha tan vi nc to hn hp si ng ph 3 cu t (ternary
azeotropic) (nc cn dung mi) c nhit si thp hn nhit
ca nc v ct chng ra khi hn hp phn ng nhit ny.Hn
hp hi tch ra c ngng t v lm al5nh tch thnh 2 pha, pha
nc loi ra ngoi, pha hu c cha ancol dn ngc tr li vo bnh
phn ng este ha. Cc dung mi tr hay c s dng l benzen,
toluen, cloroform, dicloetan, tetracloruacacbon
Ct loi este ra khi phn ng
Vic ct loi este ra khi hn hp phn ng cng c tin hnh bng
nhiu cch nhng c bn nht vn l bng hai phng php sau:
Trng hp n gin nht l khi este to thnh c si thp nht
trong s cc cht c trong phn ng v khng to thnh hn hp ng
ph vi bt k mt cht no c trong hn hp , trong trng hp ny
ht va tin hnh phn ng va ct loi este ra.
Trng hp khc i khi cng xy ra l este to thnh cng c si
thp nht nhng este ny li to vi cc thnh phn khc mt hn hp
ng ph 2 hay 3 cu t, v vy khi hn hp hi ct ra c ngng t v
lm lnh s phn pha tch ly este.
2.5.4. Qu trnh amit ha
Tng t nh vy, phn ng amit ha c s dng iu ch cc
amit, c th xem l phn ng nghch ca qu trnh thy phn cc amit
Ngoi ra cn c cc qu trnh xy ra ng thi, v d thy phn v este
ha, tch nc v este ha, amit ha v tch HCl, amit ha v este
ha.
2.6. Cc qu trnh sunfat ha, sunfo ha v nitro
Sunfat ha c gi l cc phn ng to thnh este ca axit sunfuric c
tn l cc ankynsunfat ROSO2OH, cn khi sunfo ha, ngi ta s thu
83

c cc sunfonic axit (RSO2OH hoc ArSO2OH) cng nh cc dn

xut ca cc axit ny, trong nguyn t lu hunh lin kt trc tip
vi nguyn t cacbon. Nitro ha l qu trnh c s dng tng hp
cc hp cht nitro (RNO2 hoc ArNO2) trong nguyn t nit cng ni
trc tip vi cacbon, khc vi cc
nitro este dng RONO2.

2.6.1. Qu trnh sunfat ha

Sunfat ha ru
S sunfat ha ru ch yu c s dng iu ch cc cht hot
ng b mt (HBM) dng ankylsunfat. S sunfat ha c th thc hin
di tc dng ca axit sunfuric, closunfonic, amidosunfuric hoc trioxit
lu hunh.
C ch phn ng sunfat ha ru bng axit sunfuric ni chung ging
vi cc phn ng este ha. y axit va ng vai tr l tc nhn
phn ng, ng thi l xc tc cho qu trnh. Phn ng xy ra nh s
t lin kt S-O, do vy cc nhm ankyl khng b isome ha.
H2SO 4

+ H+

H2O+ - SO2OH

+ ROH
- H 2O

RHO+ - SO2OH

ROSO2OH

Khi sun fat ha s to ra hng lot sn phm ph. V d ru tch nc

to thnh olefin. Di tc dng oxy ha ca axit sunfuric c th sinh ra
anehit hoc xeton. Nhng cht ny s d b nha ha hoc trng
ngng (khi tng hp cc cht HBM th sn phm s c mu ti v
gim cht lng sn phm). V s to thnh olefin v cc hp cht
cacbonyl s gia tng nhit cao, do vy cn phi khng ch nhit
phn ng trong khong 20 400C hn ch ti a cc phn ng ph.
Ngoi ra khng nn s dng oleum lm tc nhn sunfat ha.
C khi sunfat ha ru nu s dng cc tc nhn sunfat ha khc th
qu trnh s tr thnh bt thun nghch, v d di tc dng ca axit
amidosunfonic, phn ng xy ra nh sau:
H2NSO2OH + ROH

ROSO2ONH4

Axit amidosunfonic c kh nng sunfat ha tng i km, phn ng

ca n vi ru ch xy ra nhit 100 -1250C. Do axit ny c gi
thnh cao nn ngi ta ch s dng n trong nhng trng hp c
bit, nht l cc tc nhn sunfat ha khc to ra mt hn hp sn phm
bao gm nhiu cu t
Hin nay axit closunfuric c s dng rng ri lm tc nhn sunfat
ha. Tng t nh cc cloanhyric, n c kh nng phn ng cao,
phn ng xy ra vi vn tc ngay nhit phng. C s ca qu
trnh l s tn cng ca phn t ru vo nguyn t lu hunh

84

ClSO2OH + ROH

...

ROH
Cl...SO2OH

Cl- + RHO+SO2OH

HCl + ROSO2OH

Hiu sut phn ng kh cao, gn 100%. Nu tng nhit v c bit

l khi sunfat ha ru bc 2 th hiu sut to thnh dn xut clo s tng
ln.
ROH + HCl

RCl + H2O

Phn ng ny c th khng ch nu gim nhit v tch nhanh HCl

ra khi mi trng phn ng
Gn y ngi ta rt quan tm n vic s dng trioxit lu hunh lm
tc nhn sunfat ha. N c tnh i in t rt cao do cn mt orbitan
trng, v vy rt d kt hp vi nguyn t oxi ca ru to thnh phc,
phc ny s chuyn thnh ankynsunfonic axit
RO+H
:

ROH + SO3

ROSO2OH

SO2O-

Phn ng xy ra vi vn tc rt ln, gn hn ngay tc khc v ch yy

ph thuc vo s khuych tn ca kh SO3 trong ru. Tuy nhin do
phn ng ta nhit mnh nn d dn n hin tng qu nhit cc b
v to thnh cc sn phm ph (olefin, hp cht cacbonyl, nha).
hn ch phn ng ph cn c bin php ti nhit hu hiu v trnh cc
hin tng lm qu nhit cc b nh lm long SO3 bng cc kh tr,
khuy trn mnh hay tin hnh phn ng trn mng
Sunfat ha olefin
S sunfat ha c cp n khi xem xt phng php tch isobuten t phn on C4 v s hp nc ca olefin di tc dng axit
sunfuric. thc hin phn ng ny ch c th s dng tc nhn sunfat
ha l axit sunfuric v cc tc nhn khc hoc l hot tnh km, hoc to
ra nhng sn phm khc.
Olefin di tc dng ca axit sunfuric s to ra cc hp cht sau y:
mono v diankylsunfat, polime olefin. Nu trong axit c nc s c th
sinh ra ru v ete. Phn ng i qua giai on to thnh cacbuacation
trung gian:
RCH=CH2
+ RCH+CH3
- H+

+H+

+ H2SO4

RCH+CH3

+
CH3
+ H2 O
R(CH3)CHOH + RCH
+
+
H
-H
+
+ RCH=CH2
R2C4H6 + RCH CH3
+
-H
- H+

R(CH3)CHOSO2OH

R(CH3)CH 2SO4

R(CH3)CH

2O

POLIME

Ngoi ra, s to thnh ru v ete cn do cc phn ng thun nghch

nh thy phn hoc ancol phn mono v diankylsunfat. Cc cht ny c
85

kh nng ankyl ha rt cao:

R2SO4 + H2O

ROSO2OH + ROH

R2SO4 + ROH

ROSO2OH + ROR

+ H2 O
+ ROH

H2SO4 + 2ROH
H2SO4 + 2ROR

Trong hn hp sn phm cn c mt cc sn phm oxi ha v nha (do

s trng ngng). V sn phm chnh l monoankylsunfat nn trong thc
t ngi ta lun s dng t l mol gia olefin v axit sunfuric l 1 : 1.
hn ch cc phn ng trng hp olen, nha ha v to thnh
diankylsunfat hc ete th nng ca H2SO4 pah3i khng ch trong
khong 92 93% v tin hnh phn ng 0 400C
S kt hp axit sunfuric v olefin xy ra theo qui lut macopnhicop, do
vy t n-olefin s thu c ankylsunfat bc 2. Chng ta bit rng cc
cation c kh nng isome ha rt nhanh chng vi s chuyn v ion
hyro, tuy nhin vn gi nguyn khung cacbon. V vy cc n-olefin cao
phn t s to ra mt hn hp cc ankylsunfat bc 2 vi cc v tr nhm
sunfoeste khc nhau.
2.6.2. Qu trnh sunfo ha
Ha hc v c s l thuyt
tin hnh sunfo ha cc hp cht thm, ngi ta s dng ch
yu l axit sunfuric, oleum v SO3.
Sunfo ha di tc dng ca axit sunfuric l qu trnh thun nghch
ArH + H2SO4

ArSO2OH + H 2O

Xy ra vi s ta nhit mnh (mt phn nhit ny do nc sinh ra lm

long axit sunfuric). Do vy, hiu ng nhit ca phn ng ph thuc
nhiu vo nng ban u ca axit v c gi tr khong 146 KJ/mol.
Cn bng thng dch chuyn v pha bn phi iu kin thng,
nhng nu tng nhit v ng thi chng ct hyrocacbon, i khi
s xy ra phn ng theo chiu ngc li, v ngi ta li dng iu ny
tch cc ng phn ankylbenzen.
Sunfo ha l phn ng th i in t in hnh i vi cc vng
thm. Phn ng b km hm do nc c trong axit ban u cng nh
nc sinh ra trong phn ng, v phng trnh ng hc c th biu
din nh sau:
r = k [ArH] / [H2O]2
Ngi ta cho rng, tc nhn tn cng trc tip vo nhn thm l
SO2+OH
HSO-4 + S+O2OH + H2O

HSO-4 + H3SO+4

2H2SO4
+

+ S O2OH

SO2OH
H

SO2OH

S to thnh cc sn phm ph trong qu trnh sunfo ha rt t, ph

86

thuc ch yu vo kh nng oxy ha ca axit sunfuric.

nh hng ca nhm th trong vng thm trong phn ng sunfo ha
cng tng t nh cc phn ng th i in t khc. Tnh chn lc v
nh hng nhm sunfo trong phn ng ny c gi tr trung bnh. Nhm
sunfo trong vng thm c tnh ht in t cao, do vy lm gim kh
nng sunfo ha tip tc v rt kh a nhm sunfo th hai vo vng
thm di tc dng ca axit sunfuric.
Do tnh thun nghch ca qu trnh v gim hot tnh mnh ca
axit b lm long bi nc sinh ra, phn ng sunfo ha thng kt thc
nng nht nh ca axit. Hin tng ny c c trng bng gi
tr ca phn ng. Gi tr c tnh bng nng ca SO3 trong axit
tc dng cho n khi phn ng khng cn tip tc c na (v d
cho sunfo ha benzen l 64, naphtalen l 56 v nitrobenzen l 82). Khi
bit v nng SO3 trong axit ban u (a) c th tnh c lng axit
cn thit sunfo ha 1 mol hp cht thm theo cng thc:
x = 80 (100 ) / (a )
Trong 80 l khi lng phn t ca SO3. Cng thc ny cho thy
mun gim lng H2SO4 tiu hao v gim lng axit s dng, cn
tng nng axit ban u. V d, khi sunfo ha benzen ( =64) bng
axit m c a = 75 th lng axit ti thiu cn dng l 262g, cn nu
nng nng axit ln 100% (a = 81,7) th cn dng 162g. Trong hai
trng hp ny, lng axit s dng l 182g v 82g.
Qu trnh sunfo ha bng axit sunfuric thng phi tin hnh nhit
cao (80 -1000C), do axit ny c kh nng sunfo ha khng cao. Hn
hp phn ng bao gm hai pha, v phn ng din ra trong pha axit, yu
t khuy trn khng gy nh hng ln nh cc phn ng khc.
Phn ng ny ca oleum vi cc hp cht thm xy ra qua hai giai
on. Giai on th nht l s tc dng ca phn d SO3 trong oleum:
ArH + H2SO4.SO3

ArSO2OH + H2SO4

Phn ng ny l khng thun nghch v ta nhit mnh, hiu ng nhit

ph thuc vo nng ca oleum v c gi tr 180 KJ/mol i vi oleum
20%. Giai on tip theo l s tham gia ca axit sunfuric.
Qu trnh sunfo ha bng SO3 c biu din nh sau:
ArH + SO3

ArSO2OH

y cng l phn ng khng thun nghch v mt trong nhng phn

ng ta nhit mnh nht trong tng hp hu c (H0298= -217 KJ/mol).
C ch giai on u ca qu trnh sunfo ha cc hyrdocacbon thm
vo hyrocacbon qua cc phc - v trung gian:
+SO3

SO3

SO2OH

SO2OH

87

Phn ng c bc nht theo ArH v SO3 v xy ra gn nh tc thi. Do

trong qu trnh d th, vn tc ph thuc vo cc yu t khuch tn
v vo mc khuy trn, gii nhit.
Khc vi qu trnh sunfo ha bng axit sunfuric v oleum, vi tc
nhn SO3 gy ra mt s ln cc phn ng ph. Kh nng hot ng
ha hc ca cc hp cht ny thng dn n vic to thnh nhm
sunfo th hai trong vng thm theo s ca cc qu trnh ni tip sau:
C 6H 6

+SO3

C6H5SO2OH

+SO3

m - C6H4(SO2OH)2

iu ny c s dng trong tng hp m-benzen disunfonic axit ( t

y s iu ch c rezocxin). , giai on u thc hin vi
H2SO4, cn giai on sau di tc dng ca oleum.
Khi sunfo ha bng oleum v SO3 s sinh ra mt lng sunfon:
2ArH + 2SO3

ArSO2Ar + H2SO4

Phn ng ny xy ra mnh, c bit trong trng hp sunfo ha

benzen, cn i vi cc akylbenzen khc th yu hn.
Mt phn ng ph khc l to thnh cc anhyrit sunfonic axit:
2ArSO2OH + 2SO3

(ArSO2)2O + H2SO4

Lng anhyrit tng khi SO3 d nhiu.

Cc phn ng ph trn y, cng nh cc qu trnh oxy ha v phn
hy cc nhm ankyl di tc dng ca SO3, s c hn ch nu chn
c t l cc cu t ban u tham gia phn ng hp l, phng php
khuy trn thch hp v c bit l ch nhit ti u (trong cc
phn ng sunfo ha bng oleum v SO3 nhit c th thay i t -100
n 40 - 600C).
H thng thit b phn ng sunfat ha v sunfo ha
Cc thit b phn ng c trnh by trn hnh 2.8 (a, b, c, d). Nh
trn hnh 2.8b, ngi ta s dng thit b vi cnh khuy tuabin, lm lnh
bng h thng ng xon v v o. Bn trong thit b, nh cnh khuy
hnh tr quay s gip cho qu trnh quay trn v gii nhit tt. Hoc trn
hnh 2.8c l thit b vi ng xoay c gn cc thanh kim loi bn ngoi
to iu kn khuy trn tt nht. Cn thit b trn hnh 2.8d, ngi ta
to ra cc chm ng v phn ng xy ra trong khong khng gian gia
cc ng (cn gi l thit b dng mng).

88

Hnh 2.8. H thng thit b phn ng sunfat ha v sunfo ha

a Thit b dng a, b Thit b cnh khuy tuapin, c - Thit b ng xoay, d Thit b phn
ng trn mng

2.6.3. Nitro ha
Nhm nitro c th c a vo cc hp cht hu c bng nhiu
phng php khc nhau, ph thuc vo bn cht ca hyrocacbon ban
u. Cc phng php sau y c ng dng rng ri trong sn xut
cng nghip nitro ha nhn thm v nitro ha hyrocacbon no.
Nitro ha cc hp cht thm
C ch phn ng
Qu trnh nitro ha cc hp cht thm ch yu c thc hin bng
hn hp axit nitric v sunfuric. Axit th hai va ng vai tr l cht
xc tc, tc nhn ht nc, ng thi to iu kin s dng axit trit
hn. Trong hn hp nitro ha, s xy ra qu trnh tc dng ca axit dn
n to thnh tc nhn nitro ha hot ng rt mnh l ion nitroni N+O2,
ion ny s tn cng nhn thm:
HNO3 + H2SO4
+N+O2

H2O+ - NO2 + O-SO2OH

NO2
H

N+O2 + HOSO2O- + H2O

NO2
+ H+

nh hng ca nhm th n kh nng phn ng ca vng thm,

cng nh s nh hng v tr ca nhm NO2 cng tun theo cc qui
lut chung ca phn ng th i in t trong vng thm. Do nh hng
ca nhm NO2 trong nhn thm rt ln, nn vn tc ca cc giai on
nitro ha tip theo gim i r rt so vi giai on trc [(kn//kn-1)<<1]. V
vy phn ng c th c thc hin vi hiu sut rt cao i vi cc
sn phm c mc th khc nhau (mono, di hoc trinitro) nu chn
iu kin nhit v tc nhn nitro ha hp l. V d, khi nitro ha
89

toluen, u tin iu kin mm (400C) s to thnh mononitrotoluen

(hn hp 58 59% ng phn orto, 4-5% meta v 36-39% para). Cc
ng phn ny iu kin nhit cao (70 800C) s cho cc
dinitrotoluen (hn hp ng phn 2,4 v 2,6), cui cng l trinitrotoluen.
iu kin ca phn ng v chn lc ca phn ng
iu kin ca phn ng, c xc nh bng nhit v kh nng
nitro ha ca hn hp axit HNO3 v H2SO4, v ph thuc vo kh nng
phn ng ca hp cht thm. Kh nng nitro ha ca hn hp axit ban
u c quyt nh bi t l nng H2SO4, HNO3 v nc. Ngi ta
nh gi kh nng ny bng i lng hot nitro ha (k hiu NF):
NF = CH2SO4. 140 / (140 -CHNO3)
Trong cng thc ny phn s c trng cho mc tng nng ca
axit sunfuric, sau khi ton b lng HNO3 tiu hao v sinh ra mt
lng nc tng ng:
140 /(140 CHNO3) = 100 / [100 (CHNO3 / 63)] = 100 / (100
0.714CHNO3)
Trong 18 v 63 l khi lng phn t ca nc v HNO3.
Nh vy, gi tr NF chnh l nng ca H2SO4 sau phn ng, vi iu
kin tiu hao ht HNO3. i vi mi loi hp cht thm, u c gi tr
NF ti hn. Gi tr ny s cng cao nu kh nng phn ng ca hp
cht cng thp. Trong thc t, thng ngi ta s dng mt lng t
HNO3 d nhm tng mc nitro ha v tng chuyn ha ca
hyrocacbon. Tt nhin, khi mc tiu hao ca HNO3 s nh hn
100%. V d, trong trng hp nitro ha toluen, gi tr NF giai on
u phi l 70, giai on th hai l 82, cn cc giai on tng ng l
96; 90; v 50 60%. Tng ng nh vy, benzen cng b nitro ha
thnh nitrobenzen (NF = 70; 65 700C). Sau l m-dinitrobenzen (NF
= 88; 80 900C).
Nitro ha cc hp cht thm l phn ng khng thun nghch v ta
nhit mnh (=151KJ cho nhm nitro). Cng nh trong trng hp sunfo
ha, hiu ng nhit cao mt phn do qu trnh lm long hn hp nitro
ha bi nc sinh ra, v nhit lng ny ph thuc vo nng ca
axit sunfuric.
H thng thit b phn ng nitro ha hyrocacbon thm
Khi nitro ha hyrocacbon v cc dn sut clo, hn hp phn ng
bao gm hai cht lng khng trn ln vi nhau. trnh hin tng
nhit cc b v cc phn ng ph oxy ha , cn phi khuy trn v lm
lnh tt. Qu trnh thng c tin hnh trong h thng cc thit b
phn ng ni tip c gn h thng khuy. Sau mi thit b phn ng l
thit b tch phn tch pha hyrocacbon khi hn hp nitro ha. Hn
hp nitro ha mi (hoc hyrocacbon), c a vo thit b phn ng
cui cng. Ti y, iu kin nhit cao s s dng c ton b
90

hn hp nitro ha. Lng axit cn li, sau thit b cui ny s a tr li

cc thit b phn ng trc n (hnh 2.9).
ArH

2
H2SO4 + HNO3
2
1

ArNO2

H 2O

1
H2O
1
H2O

Hnh 2.9. H thng thit b phn ng nitro ha cc hp cht thm.

1 - Thit b phn ng nitro ha; 2 - Thit b lc; 3 - Bm.

Cc dn sut nitro vng thm ng vai tr rt quan trng trong

cng nghip cc cht n v l cc cht trung gian tng hp cc amin
(anilin t nitrobenzen, toludin t mononitrotoluen,m-phenylendiamin v
m-tolulendiamin t dinitrotoluen).
Nitrophenol thng c iu ch qua giai on sunfo ha ( v cc
phenol rt d b oxy ha bi axit nitric):
C6H5OH

+ H2SO4
+ HNO3
HOC6H4SO2OH
-H2O
-HSO4

HOC6H4NO2

Nitro phenol c ng dng rng ri trong tng hp hu c, trong sn

xut hng lot thuc tr su hot tnh cao.
Nitro ha parafin
C ch phn ng
Phn ng xy ra theo c ch gc t do. Cc gc t do sinh ra l sn
phm ca s phn r axit nitric v cc gc ny tc dng vi
hyrocacbon to ra gc t do th cp
HONO2
HO* + NO2*

HO* + RH

R* + H2O

R* + HNO2
RH + NO2*
Dioxit nit sinh ra t s phn r HNO3 hoc trc tip l tc nhn nitro
ha u c kh nng phn ng vi hyrocacbon, ly i mt nguyn t
hyro (do NO2 c mt in t n c). Phn ng c bn ca s nitro
91

ha xy ra bng con ng tc dng gia cc gc t do vi NO2

RNO2
R* + NO2*
chn lc ca phn ng
Khi nitro ha parafin, cng tng t nh khi clo ha, nhm nitro s i
vo v tr bt k trong hyrocacbon thay th nguyn t hyro. Kh nng
phn ng ca hyrocacbon cng thay i theo dy: Bc 3 > bc 2 > bc
2.Nhm nitro c mt trong mch hyrocacbon cn tr rt ln s th tip
theo.
Phn ng ph khng mong mun trong qu trnh ny l oxy ha parafin
bng xit nitric hoc dioxitnit. DO vy hiu sut nitro ha tnh theo axit
nitric tng i thp, thng ch 50 80%. Cc sn phm ca s oxy
ha c th l anehit, ceton, axit cacboxylic. Ngoi ra, do s kh ca
tc nhn nitro ha s hnh thnh cc oxit nit ha tr thp, thm ch l
nit.
S oxy ha c thc y khi tng nhit , v vy i vi mi
hyrocacbon c mt nhit ti u m hiu sut nitro ha l cao
nht. Khi nitro ha bng NO2 th nhit ti u ny thung gim so vi
khi s dng HNO3.
Trong s cc qu trnh nitro ha pah kh, c gi tr cng gnhip hn c
l qu trnh nitro ha propan bng HNO3 40 70%. Nhit ti u 400
4500C, thi gian tip xc 0.5 2giy, p sut 0.5 1Mpa, t l mol
gia HNO3 v propan l 1 : 5. Hn hp sn phm cha 25%
nitrometan...
Nitro parafin l nhng cht lng khng mu, c mi c trng. Chng
c s dng ngy cng nhiu lm dung mi v nhng cht trung gian
cho tng ho hu c.

92

CHNG 3: SN PHM T AXETYLEN

T nguyn liu axetylen, bng qu trnh halogen ha, vinyl ha...
C th tng hp ra kh nhiu cht quan trng trong cng nghip tng
hp hu c - ha du.
3.1. Sn xut vinylclorua (VC) v polyvinylclorua (PVC)
3.1.1. C s l thuyt
Phn ng cng HCl vo hyrocacbon nhm axetylen c trng cho
lin kt ni ba
CH CH + HCl

CH2=CHCl

H0298 = -112,4Kj/mol

Theo ta nhit ca mnh, n vt tri hn 2 ln so vi phn ng

hyroclo ha olefin. Khi gim nhit , cn bng ca phn ng chuyn
dch v bn phi. Hng s cn bng khi to thnh vinyl clorua bng
8.104 2000C v 7.102 3000C.
Cng HCl vo axetylen xy ra lin tip to thnh vinyl clorua v 1, 1
diclo etan
CH

CH

+ HCl

C H 2= C H C l

+ HCl

C H 3 - C H C l2

V vy, khi hyroclo ha axetylen v nhng ng ng ca n c

thc hin khi c xc tc chn lc, xc tc lm tng vn tc giai on
u tin. Xc tc cho phn ng ny l mui Hg2+ v Cu+. Trong s
nhng mui Hg2+, ngi ta dng thy ngn clorua HgCl2. Ngoi nhng
phn ng c bn, n cn tng vn tc ca c phn ng hydrat ha
axetylen to thnh axetanehit. Do nguyn nhn ny, cng nh qu
trnh mt hot tnh ca thy ngn clorua trong dung dch HCl, ngi ta
dng n trong pha kh, nhit 150 - 2000C. Axetanehit v 1,1
dicloetan cng c to thnh, nhng hiu sut cui cng khng vt
qu 1%.
i vi hyroclo ha pha lng, tt nht l dng mui Cu+, v n khng
b mt hot tnh v t lm tng vn tc cng nc ca axetylen. Xc tc
l
Cu2Cl2
trong
HCl.
Khi c Cu2Cl2, qu trnh ph dime ha axetylen cng tng, to thnh
vinyl axetylen
2C H

CH

CH

C -C H = C H

gim phn ng ny, cn s dng HCl nng cao. Khi u qu

trnh khng ngng tng cng axit, tc l clorua hyro vo, b li
lng hao ht ca n vo vic hyroclo ha.
Tc ng xc tc ca mui thy ngn v ng vo phn ng hyroclo
ha, c gii thch bng vic to thnh nhng phc phi hp. Trong
, axetylen b kch hot v tc dng vi anion clo v cht trung gian thu
c trng thi chuyn i vi lin kt kim loi cacbon hoc nhng cht
kim loi hu c, nhanh chng b phn hy bi axit
93

CH
CH

+ M

CH
CH

.M

+ C l-

C H 2 ..C l
C H ...M

CHCl
CHM

+ H+
- M

CHCl
CH2

3.1.2. Cng ngh tng hp VC

Tng hp vinylclorua l qu trnh xc tc d th pha kh. Xc tc
c chun b l than hot tnh, c tm bng dung dch clorua thy
ngn, sau sy li. Trong xc tc thu c, c cha 10% (khi lng)
HgCl2. V c hi ca HgCl2 ln v qu trnh d n ca axetylen, cn
c yu cu cht ch v k thut bo him v an ton lao ng.
Hn hp axetylen v clorua hyro cho qua vng phn ng c cha
y xc tc rn. Cht ban u phi kh, khng xy ra qu trnh to
thnh axetanehit qu nhiu v khng to s n mn qu mc cho thit
b, HCl c t l d so vi axetylen (5 10%) lm tng mc chuyn
ha axetylen. Nhit ti u khong 1600C 1800C. Khi , qu trnh
xy ra nhanh v ng thi khng xy ra s li cun HgCl2 nhiu
(HgCl2 c ha hi cao). Khi HgCl2 hao ht dn v gim hot tnh,
ngi ta tng nhit n 2000C 2200C.
Do ta nhit cao, ngi ta thc hin qu trnh trong thit b hnh
ng c xc tc v hn hp kh chuyn ng, cn trong khong cch
gia cc ng l nc lm lnh hon lu. Cht lm lnh l cht truyn
nhit hu c, hoc nc.
S cng ngh sn xut th hin trn hnh 3.1.
Axetylen lm sch, cho qua chn la (1) v sy nh qu trnh
ngng t phn m trong thit b lm lnh nc mui (2) v sau , bng
kim rn trong thp (3). Trong b khuy (4), n c trn vi HCl kh
v cho vo thit b phn ng hnh ng (5). Mc chuyn ha ca
axetylen l 97 98%, kh phn ng c 93% vinylclorua, 5% HCl, 0.5
1% axetylen v 3% axetanehit v 1, 1 diclo etan. Chng ko theo
mnh hi HgCl2 v HCl tip theo trong thit b lc kh (7), (8), (9) bng
HCl 20% nc v kim hon lu. Sau , sy kh trong ng sinh hn
nc mui (10) v nn trong b nn kh (11) n 0.7 0.8MPa. Hn
hp sau , c tch trong thp chng ct (12), (13), tch phn cn
rn trc (1,1- diclo etan), cn sau l phn nh (axetylen,
axetanehit).
Sn phm thu c vinylclorua (VC), kh khng mu, ngng t
nhit -13.90C. L mt monome quan trng, dng nhiu tng hp
vt liu polyme khc nhau. Khi polyime ha c peoxit, vinylclorua to ra
polyvinylclorua (PVC)
nCH2=CHCl

T0C

-CH2-CH2 n
Cl

94

Hnh 3.1. S cng ngh iu ch vinylclorua bng phng php

hydroclo ha axetylen.
1 - Thit b chn la; 2, 6, 10 Sinh hn; 3 Thp sy; 4 - Thit b trn khuy; 5 - Thit
b phn ng; 7, 9 - Thit b lc kh; 11 my nn; 12, 13 Thp chng ct phn on;
14 - Thit b tch; 15 - Thit b hi lu; 16 - Ni un.

3.2. Tng hp vinyl axetat (VA), polyvinyl axetat (PVA)

3.2.1. C s l thuyt ca qu trnh vinyl ha
Vinyl ha tc l a nhm vinyl vo cc hp cht khc nhau, c th
c thc hin bng cc phng php trc tip v gin tip. Cc
phng php trc tip da trn phn ng ca cc cht vi axetylen v
c chia lm 2 nhm: vinyl ha di tc dng ca xc tc l cc mui
kim loi chuyn tip nh (Zn, Cu) v vinyl ha di tc dng ca xc
tc kim.
Vinyl ha di tc dng ca xc tc kim loi chuyn tip dng
tng hp vinyl axetat. Nhm cc qu trnh ny tng t nh qu trnh
hp nc v hyroclo ha axetylen nhm tng hp axetanehit v vinyl
95

clorua. Bng con ng ny, trong cng nghip ngi ta sn xut vinyl
axetat, vinyl axetylen v acrylonytril
Tuy vy, cng nh trong tng hp cc cht khc, xut hin nhng
phng php mi, thay th cho nguyn liu ban u l axetylen tng
i t tin, c th i t olefin.
3.2.2. Cng ngh tng hp VA
Tng hp vinyl axetat bng cch cho axetylen tc dng vi axit
axetic. Xc tc cho phn ng ny l axetat km trn cht mang l than
hot tnh. Qu trnh ny, c thc hin trong pha kh nhit 170
2200C. C ch ca phn ng bao gm cc giai on hp ph ha hc
axetylen to thnh phc vi ion km, sau l qu trnh tn cng ca
phn t axetylen c hot ha bng ion axetat v cui cng l tc
dng ca axit axetic:
Zn
Zn

2+

C 2H

( O A c ) -2

A cO H

Zn

2+

2+

( O A c ) -2
Z n +O A c[C H = C H O A c ]

CH CH

( O A c ) -2

C H 2= C H O A c

Vinylaxetat c kh nng kt hp tip tc vi axit axetic to thnh

etylendiaxetat. Do vy, s xut hin mt h phn ng song song - ni
tip.
CH CH

HO Ac

C H 2 = C H O A c H O A c C H 3 -C H (O A c )2

Giai on u xy ra vi vn tc ln hn nhiu so vi giai on th

2. Tuy nhin, vn cn phi c mt lng d axetylen so vi axit axetic
hn ch ti a qu trnh to thnh etylendiaxetat. Mt sn phm ph
khc ca qu trnh l axetanehit, c to thnh bi qu trnh thy
phn axetylen. Ngoi ra, cn c to thnh mt lng axeton sinh ra do
qu trnh xeton ha axit
2C H

C O O H

C H

-C O -C H

+ C O

+ H

Tt nhin, cn xy ra qu trnh trng hp ca mt s cht trong h

phn ng, kt qu l to thnh cc hp cht nha. trnh qu trnh
pht trin mnh ca cc phn ng ph, tng nng sut ca thit b
phn ng, cn gi chuyn ha ca axit axetic mc thp khong
60%. Khi , hiu sut vinyl axetat s t 95 98% tnh theo axit axetic
v 92 95% tnh theo axetylen.
Trong sn xut cng nghip, t l mol gia axetylen v axit axetic t
3.5 : 1 n 5:1. Xc tc c chun b, bng cch tm axetat km ln
than hot tnh, sau sy kh. Xc tc iu ch bng phng php ny
cha 30% axetat km v c hot tnh cao nhit 1800C. Sau mt
thi gian di hot ng, hot tnh ca n s gim dn, do mt lng
nha bm trn b mt. V vy, cn phi nng nhit t t ln 210
96

2200C.
Qu trnh phn ng, c thc hin p sut kh quyn, trong thit
b dng ng chm v lm lnh bng nc ngng t. Khi , s ti sinh
c hi nc v s dng hi nc ny nng nhit ca phn ng.
C mt s hng nghin cu mi, ngh s dng thit b vi lp xc
tc gi lng.
S cng ngh ca qu trnh c biu th trn hnh 2.4.

Hnh 3.2. S cng ngh tng hp vinylaxetat t axetylen

1 - Thit b trao i nhit; 2 - Thit b phn ng; 3 - Thit b ngng t lm lnh;
4 - H thng lc; 5 - Khi chng ct; 6 - Thit b nn kh.

Hn hp cc cht ban u c t nng trong thit b trao i nhit

(1) v sau c a n thit b phn ng (2). Hn hp i ra t thit
b phn ng (2), s c lm lnh lin tc, u tin l trong thit b trao
i nhit (1), sau l trong h thng lm lnh bng nc (3). Ti y,
cc cht lng s ngng t. Phn axetylen cha chuyn ha, s c
a tr li, chun b cho hn hp phn ng ban u. Cn phn lng
thu c, s chuyn qua h thng chng ct (5). Ti y, s thu c
phn on nh, vinyl axetat, axit axetic (c a v phn ng) v
etylidenaxetat. Cn khng bay hi s mang i t.

97

CHNG 4: TNG HP TRN C S METAN V CC PARAFIN

KHC.
Kh t nhin v kh ng hnh vi cu t chnh l metan c dng lm
nhin liu v nguyn liu tng hp cc sn phm c gi tr kinh t.
Kh sau khi c ch ch bin v phn tch cho cc sn phm kh ring
bit: metan, etan, propan, butan v phn on cc hydrocacbon cao
hn. Phn tch kh cha phi l mc ch cui cng ca qu trnh ch
bin kh. Cng on c ngha nht l bng cc qu trnh cng ngh
ha hc vi cc h xc tc c bit chuyn ha metan thnh cc sn
phm c gi tr kinh t cao.
Hin nay, t kh t nhin v kh ng hnh ngi ta tng hp c
hng trm sn phm khc nhau c gi tr phc v cho i sng v cc
ngnh kinh t khc. Bng cc qu trnh chuyn ha trc tip v gin
tip t metan ta thu c etan, etylen, kh tng hp, metanol, amoniac,
axetylen l cc nguyn liu quan trng cho cng ngh tng hp ha
du, . Etylen dng sn xut polyetylen (PE), propan dng sn xut
etylen v propylen, polypropylen (PP), polyvinyl clorua (PVC), isobutan dng iu ch iso-buten v cao su butyl khng thm kh
4.1. Tng hp hydrocianit t metan
Axit cianit (HCN) l mt cht lng rt c, nhit si 25.70C. Axit ny
v mt s mui ca n c ng dng rng ri iu ch cc nitril,
clocyan, cyanuaclorua, acetoncyanhyrin, hoc s dng trong k ngh
pin hoc tch cc kim loi qu t qung. Phng php hin i tng
hp axit cianit l oxy ha amoni metan
CH4 + NH3 + 1.5O2

HCN + 3H2O

Phn ng din ra gn nh tc thi 10000C trn xc tc Pt Re. Hn

hp ban u gm metan, amoniac v oxy khng kh vi t l th tch 1.1
: 1.0 : 1.5 c a vo thit b phn ng c cha cc lp xc tc di
dng li an t dy hp kim mng. Cc sn phm ph l CO v CO2
(do s oxy ha metan) ; H2 v N2 (do s phn hy amoniac). Hiu sut
HCN vo khong 80%.
Ngi ta cho rng c ch ca phn ng ny da trn s hp ph ha
hc cc gc t do N*, N*HOH, :NOH. Rt c th cc cht trung gian
c hnh thnh l metylamin, metylenimin CH2 = NH.
4.2. Tng hp amoniac
Hu ht tt c amoniac trn th gii c sn xut bng phn ng ca
nit v hydro c xc tcv hu ht hydro dng tng hp amoniac
c sn xut bng qu trnh reforming hi nc hydrocacbon ( dng
lng v sng kh) hoc than . Ngun cung cp nit ch yu t qu
trnh ha lng khng kh hoc c th nhn c nit t qu trnh ch
bin kh t nhin v kh ng hnh.
98

4.2.1. Thnh phn xc tc cho qu trnh

Thnh phn xc tc cho qu trnh tng hp amoniac rt a dng. Xc
tc tt nht v kinh t nht hin nay l xc tc c st dng oxit FeO,
Fe2O3, Fe3O4, trong dng Fe3O4 c hot tnh cao nht. Ngoi ra cn
c cc ph gia tng bn nhit v tng n nh cu trc nh Al2O3,
TiO2khi tng hm lng Al2O3, bn nhit v bn c ca xc tc
tng, tuy nhin lung Al2O3 nhiu gy kh khn cho vn ti sinh xc
tc v cn tr s nh hp th NH3 trn b mt xc tc. Ngoi Al2O3, cn
c mt s oxit khc cng c tc dng n nh cu trc ca xc tc, mc
n nh cu trc ca chng c sp xp theo th t sau:
Al2O3 > TiO2 > Cr2O3 > MgO = CaO > SiO2 > BeO
Cc oxit kim loi kim c tc dng tng cng trao i in t hot ha
qu trnh trung gian, do tng hot tnh xc tc lm vic p sut
cao, ng thi to iu kin nh NH3 tt hn v tng kh nng chu ng
c vi H2S. Ngoi ra cc oxit t him nh Sm2O3, HoO3, Fr2O3 cng
gp phn tng hot tnh xc tc. Trong qu trnh hot ha, cc oxit ny
b kh thnh kim loi v to hp kim vi st.
4.2.2. Qu trnh tng hp amoniac i t kh t nhin
C nhiu ngun nguyn liu khc nhau c s dng cho qu trnh
tng hp amoniac nh than, du nng naphta, kh t nhin, kh ng
hnh. Vi cc nguyn liu khc nhau, chi ph u t c bn v tiu tn
nng lng cho mt s nh my sn xut amoniac 1000tn/ngy c
a ra trong bng so snh di y ( nu ly s liu cho kh t nhin l
n v)
Bng 4.1. So snh sn xut amoniac t cc nguyn liu khc khau
Kh t nhin Naphta
Du nng Than
u t c bn
1.00
1.18
1.50
2.00
Tiu hao nng
1.00
1.05
1.11
1.45
lng
T s liu so snh trn bng 4.1 thy rng, chi ph u t c bn cng
nh tiu hao nng lng cho nh my sn xut amoniac i t kh t
nhin l thp nht
Qu trnh tng hp amoniac i t kh t nhin bao gm 3 giai on:
chuyn ha kh t nhin thnh kh tng hp, bng qu trnh reforming
hi nc v oxy ha mt phn
CH4 + H2O
CH4 + 1/2O2

CO + 3H2
CO + 2H2

Loi b CO v CO2 v chng gy ng c xc tc. Ngi ta thc hin

vic loi b CO bng cch: u tin chuyn CO thnh CO2 bng hi
99

nc theo phn ng:

CO + H2O

CO 2 + H2

Sau CO2 s c loi b bng ra nc, hp th bng dung dch

cacbonat v etanolamin
Khi hm lng CO cn li nh, ngi ta tin hnh tinh ch kh nh
qu trnh metan ha, loi b cc oxit CO, CO2 n mc nh hn
10ppm
CO + 3H2

CH4 + H2O

Giai on tng hp amoniac

N2 + 3H 2

2NH3 + Q

Ty theo iu kin p sut ngi ta chia lm 3 qu trnh:

Qu trnh tng hp p sut thp (10 15MPa)
Qu trnh tng hp p sut trung bnh (25 50MPa)
Qu trnh tng hp p sut thp (60 100MPa)
chuyn ha hn hp t 14 20% qua b phn tch nh lm lnh
NH3, cn kh cha phn ng a qua my nn kh tun hon, tr li
thit b tng hp
Mt s s tng hp in hnh

Hnh 4.1. Cc s tng hp amoniac

1 thit b chuyn ha amoniac, 2 thit b ngng t thu hi amoniac,
3 thit b ngng t amoniac ti nhit mi trng,
4 my nn kh nguyn liu, 5 my nn kh tun hon

100

Nu kh mi hon ton, khng c cc cht gy ng c xc tc nh

nc, CO2, c th trc tip a vo thit b chuyn ha (hnh 4.1). Sau
khi kh ra khi thit b tng hp, NH3 c ngng t bng cch lm lnh
v kh tun hon c a vo my nn tun hon. S ny i din
cho s sp xp thch hp nht theo quan im nng lng cc tiu. Kt
qu l NH3 thp nht u vo v cao nht cho ngng t.
Khi kh nguyn liu mi cha nhiu nc hoc CO2, th cn phi hp
th hon ton nh ngng t NH3. iu ny yu cu giai on ngng t
c t mt phn hoc ton phn gia u a kh mi vo v thit b
chuyn ha. S sp xp ny c bt li l nng NH3 gim xung do
ha tan vo kh mi. Ngoi ra, nhit ngng t tng ng nng
NH3 cn bng u vo cao hn i vi thit b chuyn ha. Hnh 4.1b
l s n gin nht. S ny c bt li l NH3 sn xut ra pha
kh phi c nn cng kh tun hon trong my nn tun hon
Trong s hnh 4.1c thng s dng my nn kiu 4 k, vi s b tr
nh vy, thc hin nn tun hon ngay sau khi ngng t v tch NH3.
C th s dng khng kh hoc nc lm lnh kh tun hon ngay
trc khi trn vi kh mi (trc khi ha tan kh tun hon), v th gim
c tiu hao nng lng cho lm lnh
Chia lm lnh thnh 2 bc cho ngng t NH3, s c li khi kh tun hon
c nn cng kh mi. Qu trnh ny c s dng c bit l vi p
sut tng hp ln hn 25Mpa. p sut ny, phn ln NH3 to thnh
c th c ha lng nh lm lnh bng nc hoc khng kh nh s
trn hnh 4.1d.
V thit b, thp tng hp l thit b quan trng nht trong ton b h
thng tng hp NH3. Cu to ca thp cn vng chc, m bo lm
vic lu di, khng nguy him v qu trnh thc hin p sut rt cao.
Kim loi dng ch to thp phi c bn cao, nu khng hydro v
amoniac cha trong hn hp kh nhit cao s c tc dng vi kim
loi lm gim phm cht ca n.
Thp tng hp l thp hng tr bng thp, chiu dy t 176 200mm,
cao t 12 30m, ng knh t 1 1.4m. Thp c c thng ng.
Phn trn v di thp c ni vi nhau bng ghi thp v mt bch.
S khc nhau v cu to ca thp ch yu l khc v kch thc v v
cu to m bn trong. Vi loi thp lm vic p sut trung bnh th
phn trn t hp ng xc tc, phn di l b phn truyn nhit. V
thp c lp cch nhit loi tr kh nng xut hin truyn nhit cng
bc thnh v m ch xu hin hiu s nhit gia b mt bn trong
v bn ngoi thp. Xc tc c t trn ghi, phn phi u n
nhit trong lp xc tc ngi ta t 2 ng truyn nhit.
Hn hp nit v hydro a vo thp tng hp t trn xung di qua
101

khng gian gia v thp v hp ng xc tc, ri c t nng trong

b phn truyn nhit phn di. Sau hn hp i vo ng trung tm
chuyn ln phn trn ca hp ng xc tc qua ng truyn nhit 2 lp
ri mi vo lp xc tc, li qua b phn truyn nhit v i ra khi thp
tng hp.
Thi gian s dng ca xc tc ty thuc vo sch ca kh, thng l
2nm. tng thi gian s dng ca xc tc c th dng thm lp xc
tc tng cng vic lc sch kh khi cc tp cht CO, CO2, O2.
Trong thp xc tc b sung ny c th dng loi xc tc Ni-Cr nhit
300-3500C, ti s xy ra cc phn ng:
CO + 3H2
CO2 + 4H2O
2H2 + O2

CH4 + H2O
CH4 + 2H2O
2H2O

Hi nc hnh thnh s tch ra thp ngng t bng nc

Hnh 4.2. S cng ngh tng hp chuyn ha kh thin nhin

102

Trc y trong cng nghip ngi ta c xu hng tng lng sn

phm NH3, gim gi thnh bng cch gim chi ph v xy dng c bn.
Trong cng nghip, nit c ly t khng kh r tin, gim c chi
ph v nguyn liu ng thi ci thin iu kin lao ng trong nh my,
v n gin ha s k thut bng cch hon thin cc phng php
lm sch kh. Dng bin php chuyn ha CO nhit thp, sau
metan ha CO cn li s n gin qu trnh lm sch kh, gim c
chi ph v giai on chun b hn hp nit hydro. Yu cu t l cc ct
t trong hn hp phn ng N2:H2 l 1:3. Hng pht trin ca cng
nghip hin nay, l s dng nhng thit b c nng sut cao, dng
nhng xc tc c hot tnh v chn lc cao, c tnh chu nhim c
cao v lm vic nhit thp. c bit l s dng xc tc kiu tng
si tng kh nng tip xc ca hn hp kh phn ng vi xc tc.
chuyn ha hn hp t 14 20%. Qua b phn tch nh lm lnh
NH3, ngng t khi cha phn ng qua my nn kh tun hon tr li
thit b phn ng
4.3. Tng hp metanol
4.3.1. C s l thuyt
Hin nay, metanol c sn xut trong cng nghip ch yu bng
phng php chuyn ha t kh tng hp. Da theo p sut tin hnh,
Ngi ta phn loi qu trnh tng hp nh sau :
Qu trnh p sut cao: 25 30Mpa
Qu trnh p sut trung bnh: 10 - 25Mpa
Qu trnh p sut thp: 5 - 10Mpa
Qu trnh p sut thp c u im c bn l vn u t v gi thnh
sn phm thp, c th linh hot la chn quy m ca nh my. V vy,
hin nay trn th gii hu ht cc nh my tng hp metanol theo cng
ngh s dng p sut thp.
Phn ng to thnh metanol l phn ng xc tc d th in hnh, c
th c m t bng c ch hp ph - nh hp ph. Bn cht cc trung
tm hot ng ca xc tc Cu-ZnO-Al2O3 trong cng nghip vn ang
c nghin cu. Thnh phn kh nguyn liu, c bit l t l CO2 v
H2O ng vai tr quan trng trong vic xc nh hot tnh v chn lc
ca xc tc.
Al2O3 tn ti dng v nh hnh. Chc nng ca Al2O3 trong xc tc
Cu-ZnO-Al2O3 bao gm : chng li s kt dnh ca ht ng mn, n
nh s phn tn cao ca h xc tc Cu-ZnO, to thnh cc hc trng
trn b mt bng cc kt hp Al2O3 vo mng li ca Cu. Ngoi ra
Al2O3 ng vai r quan trng l cht hot ha cu trc cho xc tc CuZnO bng cch ci tin bn c v bn lu di ca xc tc.
103

4.3.2. Xc tc cho qu trnh tng hp p sut thp

Xc tc c cha kim loi ng c hot tnh hn km oxit v crom oxit.
bn nhit tng ln vi xc tc Cu-ZnO c b sung Al2O3 v n
c dng cho s chuyn ha kh tng hp tinh khit thnh metanol. V
hot tnh ca xc tc cao nn phn ng c thc hin nhit
khong 2200C 2300c ti p sut 5Mpa.
C mt s tp cht lm nh hng n hot tnh v chn lc ca xc
tc. Xc tc cha ng rt nhy vi cc tp cht trong kh tng hp.
Cc hp cht ca lu hunh, clo gy ng c h xc tc, dng xc tc
cha ZnO s hn ch c tc hi ca hp cht lu hunh, v lu
hunh s chuyn thnh hp cht ZnS. Sau khi b gim hot tnh, xc tc
vn c th hp ph c mt lng ln lu hunh bo v lp xc
tc sau khi b ng c. Cc tp cht khc trong kh tng hp nh hp
cht silicon, niken cacbonyl hoc st cacbonyl cng lm cho xc tc b
mt hot tnh.
Xc tc cng c th b mt hot tnh do b phn hy nhit nu s dng
thnh phn kh tun hon khng hp l, iu chnh nhit khng ng
hoc np qu nhiu xc tc ban u gy hin tng qu nhit cc b.
4.3.3. S tng hp metanol di p sut thp
Cng ngh ca hng Lurgi Oil gas Chemical GMBH (c)
S tng hp metanol di p sut thp ca hng Lurgi Oil gas
c biu din trn hnh 3.2.
Cng ngh sn xut metanol vi quy m ln t kh thin nhin v kh
ng hnh gm 2 giai on chnh :
Giai on 1: qu trnh reforming t hp chuyn ha hydrocacbon
thnh kh tng hp.
Giai on 2: qu trnh chuyn ha kh tng hp thnh metanol p
sut thp.
Nguyn liu sau khi c gia nhit s b, tch lu hunh, sau
chia lm 2 dng. Mt dng c bo ha hi nc, tip tc c gia
nhit v dn ti thit b chuyn ha s cp bng qu trnh reforming
hi nc. Hn hp kh sau khi chuyn ha mt phn trong thit b
s cp c p sut cao c trn vi dng nguyn liu cn li v a
vo thit b chuyn ha th cp. Ti y, hn hp kh c chuyn
ha p sut 3.5Mpa v nhit 9600C nh qu trnh reforming t
nhin c b sung dng oxy. Nhit lng ca kh tng hp v kh thi
ca qu trnh c s dng cho thit b pht sinh hi nc, gia nhit
s b cho hn hp nguyn liu ban u, un nng cho cc thp
chng ct. Sau khi lm lnh bng khng kh hoc nc, kh tng hp
c nn n p sut 8Mpa trc khi a sang thit b tng hp
metanol. Trong thit b tng hp metanol, xc tc ng c t trong
104

cc ng thng ng, nc si qu nhit c dn bn ngoi. Phn

ng xy ra trong iu kin gn nh ng nhit. Nhit phn ng
c iu khin chnh xc bng p sut ca hi nc. iu kin phn
ng ng nhit v xc tc c chn lc cao cho php hn ch cc
sn phm ph to thnh mc thp nht.

Hnh 4.3 S cng ngh sn xut metanol t kh thin nhin

v kh ng hnh

Hn hp sau phn ng, sau khi lm lnh c a sang thp

tch. Kh cha chuyn ha c my nn a tr li thit b tng hp
105

trn vi nguyn liu mi.

Metanol tch khi hn hp kh c a sang chng ct nhn sn
phm metanol tinh khit.
Qu trnh ny ph hp vi yu cu cn thi c th chuyn cc nh
my sn xut amoniac thnh nh my sn xut metanol khi c nhu
cu ti ch.
4.4. Tng hp formanehit
Formanehit l cht kh khng mu ( trng thi khng cha nc)
v c mi hng cay, nhit ngng t 190C 0.1 MPa. Khi bo qun
d b polyme ha v t khi xut hin dng polyme rn l paraformanehit
(paraform) v d b depolyme ha. Paraform l polyme mch thng vi
mc xch c bn l oxy metylen (s lng chng t (8 100)
nHCHO + H2O

H-O-CH2-OH
n

Phn ln formanehit sn xut dng dung dch 37% gi l formalin.

Trong , formanehit nm dng hyrat HCHO.H2O v polyme thp
phn t (polyoxy metylenglycol). km hm qu trnh polyme ha su
v kt ta formalin, thng b sung thm t 7 12% khi lng
metanol lm cht n nh
Formanehit c sn xut vi qui m ln v dng sn xut hng
lot cc polyme (phenol, uremelaminoformanehit, polyformanehit) v
dng lm cht trung gian tng hp izo-pren, pentaerytrit,
hexametylen tetramin (urotropin) v cc cht c gi tr khc.
4.4.1. Oxy ha metanol thnh formanehit
y l phng php mi, pht minh cch y khng lu v ng
dng trong cng nghip. N c tin hnh vi lng d khng kh
350 4000C v p sut kh quyn, bng cht xc tc l oxyt Fe, Mo
[dng rn l MoO3 trong Fe2(MoO4)3]; lm vic theo c ch oxy ha kh vi qu trnh tham gia ca oxy. Qu trnh ni bt, bi chuyn
ha metanol (99%) v tnh chn lc (95 96%), cng nh ta nhit
mnh, nn thng dng cc thit b phn ng mm, c lm ngui
bi cc cht mang nhit thch hp. nhiu c cu thit b khc nhau,
qu trnh lm lnh s to ra hi p sut n 3MPa. Mc d vn u t
v lng kim loi dng ch to thit b ln, cn nng sut thit b nh,
nhng qu trnh oxy ha metanol thnh formanehit vn c ng
dng rng ri do t tiu hao nguyn liu, chuyn ha ca metanol cao
v hiu qu v sn xut nng lng ca qu trnh ln.
4.4.2. ehyro ha v oxy ha ng thi metanol
ehyro ha ru bc 1 nh metanol km thun li hn so vi ru
bc 2 theo cc iu kin ca trng thi cn bng v tnh la chn ca
phn ng. Do nguyn nhn ny, cng nh do tnh thu nhit ca qu
106

trnh m ngi ta tin hnh ng thi ehyro oxy ha metanol.

CH3OH

HCHO + H2

CH3OH + O2

H0 = 85 KJ/mol

298

HCHO + H2O

H0 = -156,3 KJ/mol

298

C th la chn t l ca phn ng ny, sao cho phn ng tng cng

l ta nhit v lc c th trnh tht thot nhit ra mi trng ngoi.
Ngi ta dng n nng hn hp ban u ln n nhit cn thit.
Trong thc t, khi iu ch formanehit, th kt qu trn s nhn c
khi qu trnh ti`n hnh theo t l phn ng 55% l oxy ha v 45% l
ehyro ha, v lc qu trnh c th tin hnh trong thit b on
nhit khng c b mt trao i nhit.
Khi tng hp formanehit, ngoi cc phn ng c bn cn xy ra cc
qu trnh ph nh oxy ha su, ehyro ha su v hyro ha dn n
to thnh oxit cacbon, axit formic, nc v metan...
CH3OH
CH3OH

+0.5O2
HCHO
+H2O
-H2

CH3OH + H2

HCHO

+O2
-H2

HCOOH

+O2

CO2 + H2O

CO

CH4 + H2O

Qu trnh ehyro ha tin hnh vi s thiu oxy. V vy, phn ng

oxy ha su hn s khng pht trin mnh. Cng do , qu trnh
ehyro ha c kch hot bi oxy s xy ra nhanh hn tt c cc
phn ng ph nu trn v khng chm nh ehyro ha cc ru bc
1 khc. iu ny cho php thc hin cc phn ng nhit cao hn
(500 6000C), tc ln v thi gian tip xc t 0,01 0,03s. Hiu
sut formanehit trn nguyn liu t 80 85% khi chuyn ha ca
metanol 85 90%. Cht xc tc ca qu trnh tng hp formanehit
bng phng php ny l Cu kim loi ( dng li hay phoi) hay Ag
ph trn Al2O3. Cht xc tc sau cng s cho hiu qu cao nht v dng
rng ri trong cng nghip.
4.4.3. S cng nghip sn xut formanehit
Metanol cha 10 12% nc t thng cao v (1) chy lin tc vo
thit b un si (2). Trong , khng kh c a qua c cu phn phi
lm sch khi bi v cc cht bn khc. Khng kh c sc qua lp
nc metanol pha di thit b un si. Trong 1 lt ca hn hp hi
to thnh cn cha ~0,5 g metanol. Vic t c thnh phn nh trn
l rt quan trng hn ch qu trnh n v qu trnh xy ra bnh
thng. V vy, cng vic ca h thng un si l hon ton t ng
gi thng xuyn hn hp trng thi lng vi nhit 48 500C, nh
107

vy m bo ch nhit cn thit v chuyn ha trong thit b

phn ng on nhit.

Hnh 4.4. S cng ngh sn xut formalin.

1 Thng cao v; 2 - Thit b un si; 3 - Thit b trao i nhit;
4 - Thit b phn ng; 5, 8 - Thit b lm lnh; 6 Thp hp th;
7 - Thit b lc kh; 9 Thng cha.

Hn hp hi khng kh qua tm chn nm pha trn thit b un si,

tip theo l thit b nhit (3) v qua thit b phn ng (4) c cha cht
xc tc. Cc kh phn ng, lp tc s di chuyn vo thit b lm lnh
(5) (nm k bn di thit b phn ng), xy ra qu trnh lm ngui
nhanh hn hp v cn tr qu trnh phn hy formanehit. Trong cc
s khc, qu trnh lm ngui thc hin bng nc, khi thit b
lnh gi vai tr ti sinh hi vi p sut thp, trung bnh v thm ch l
cao. Hi nhn c (hay nc qu nhit) s dng lm qu nhit hn
hp tham gia vo thit b qu nhit (3) v dng lm cc tc nhn nhit
ca thit b un si (2).
Cc kh phn ng lm ngui, s a qua thp hp th (6) dng
thp mm, cht lng trn mm c lm ngui bng thit b lnh t
trong hay ngoi (trn s khng biu din). Tc nhn hp th l
nc c ti vi s lng c xc nh, y nhn c
formalin 36 37%. Giai on hp th v phn tch cc sn phm c th
thc hin bng hai phng php khc nhau.
Mt trong chng l ti thp hp th s hp th formanehit cng nh
metanol cha phn ng nm trong sn phm, vi s lng t
n nh formanehit.Trong trng hp ny mm trn cng cht hp th
c lm lnh bng dung dch nc mui, cn thp (7) ch dng lc
kh. Cn nu mun nhn c formalin khng c metanol (i khi yu
cu cho cc mc ch khc nhau) th cn c c cu tch metanol.
phng php th hai l trong thp hp th s hp th ch yu
108

formanehit, khi thp lc kh (7) s s dng hp th metanol.

Metanol ny, s chng ct ra khi nc v a v giai on phn ng.
Trong c hai trng hp, formalin t y thit b hp th (6), c lm
ngui trong thit b lnh (8 ) v cha vo thng cha (9).
4.5. O-ankyl ha bng olefin. Tng hp metyl tec-butyl ete (MTBE)
4.5.1. C s l thuyt
Qu trnh ny gn y tr nn rt quan trng trong tng hp MTBE l
mt thnh phn c ch s ortan cao i vi cc nhin liu ng c. N
c tng hp t metanol v iso-buten khi c mt xc tc axit
(CH3)2=CH2

H+

(CH3)3C+ +CH3OH (CH3)3 - O+- CH3

H

-H+

(CH3)3C - O - CH3

Phn ng xy ra vi s ta nhit v cn bng ca n chuyn dch v

bn phi khi tng p sut v gim nhit . Xc tc hu hiu nht l cc
nha trao i ion 50 1000C. Khi c th s dng cc phn on
buten ( tch loi butadien - 1, 3) lm nguyn liu cho phn ng
4.5.2. S cng ngh sn xut MTBE
S cng ngh sn xut MTBE c th hin trn hnh 4.5
CH3OH
4
C4

8
3

9
2

11
6
6
5
10

Hnh 4.5. S cng ngh sn xut MTBE

1,2 Thit b phn ng, 3 ct tch s b, 4 Thit b chng phn on,
5 H thng un nng, 6 van chnh p, 7, 11 Ct chng phn on,
8 Bm, 9 Ct trch ly, 10 H thng trao i nhit.

Phn on buten khng cha butadien 1, 3, metanol mi v metanol

109

ti sinh sau phn ng c a vo h thit b phn ng bao gm 2 ct

1 v 2 lin tip nhau. ct phn ng 1 c lp xc tc di ng v ti y
phi tin hnh lm lnh, trong khi ti ct th 2, phn ng xy ra
khng cn lm lnh vi lp xc tc cationit c nh. Hn hp phn ng
sua s i vo ct chng tch 3 c km theo ct chng phn on 4
v h thng un nng 5. Ti y s tch phn on nh (hydrocacbon
C4 v mt t metanol)ra khi phn on nng (MTBE v metanol). Phn
on nng tip tc c chng ct thp chng 7, sn phm y ca
thp ny l MTBE, cn metanol i ra t pha trn s c a tr li
phn ng. Phn on nh thu c thp 3 c ra bng nc
trong thp trch ly 9 tch metanol ra khi hydrocacbon C4. Trong
phn on C4 ny c th c mt mt lng nh nc v sn phm ph
dimetyl ete, chng s c tch ra bng chng ct (trn s khng
biu din cng on ny). Phn trch ly cha metanol t pha di thp
9 c un nng trong thit b trao i nhit 10, sau chng tch
metanol trong thp 11. Phn nc cn li t pha di thp 11 c
lm lnh trong thit b trao i nhit 10, sau li c s dng trch
ly metanol.
Qu trnh c thc hin vi mt lng d nh metanol so vi isobuten vi mc ch iu ch phn on C4 c cha butan v n-buten vi
khi lng tp cht rt nh l iso-buten.
4.6. N-ankyl ha. Tng hp amin t ru
4.6.1. C s l thuyt
ankyl ha amoniac hoc amin theo nguyn t nit ngi ta thng
s dng tc nhn ankyl ha l cc dn sut clo hay ru.
S tc dng ca ru vi amoniac to thnh amin theo phng trnh
sau:
ROH + NH3

RNH2 + H2O

V l qu trnh ta nhit, khng thun nghch

V d i vi phn ng gia metanol v amoniac, s thay i nng
lng Gibbs th hin bng h thc G = -5600 + 0.9T
Nng lng ny cho thy, hng s cn bng ca phn ng c gi tr
kh cao mi hnit cho php. Khc vi metanol, phenol tc dng
vi amoniac theo qu trnh thun nghch
ArOH + NH3

ArNH2 + H2O

Cc qu trnh c gi tr cao trong sn xut cng nghip l khi s dng

xc tc dng axit v tin hnh trong pha kh 350 4500C. Thng
thng cc xc tc l oxit nhm, aluminosilicat, photphat nhm,
photphat amoni. Tc dng ca xc tc d th dc th hin s hot
ha lin kt C-O trong ru do s hp ph ha hc trn cc tm axit
ca chng
110

RO+H2 + NH3
- H2 O

ROH + H+

R+NH3

RNH2 + H+

Tuy nhin cc xc tc ny cng c kh nng thc y qu trnh tch

nc ca ru dn n s to thnh ete v olefin
2ROH

ROR + H2O

R - CH2 - CH2 - OH

R - CH = CH2 + H2O

Ete sinh ra cng c kh nng ankyl ha amoniac v amin, cn s to

thnh olefin l qu trnh ph khng mong mun. Phn ng to thnh
olefin c th hn ch mc cao khi s dng lng d amoniac, lc
ny tc phn ng ankyl ha s tng nhanh v gim tc tch
nc. Bng cch ny c th tng hp cc amin ngay hki s dng cc
ru bc nht cao phn t l nhng ru thng c khuynh hng
tch nc
Phn ng ca amoniac vi ru, cng nh vi cc dn sut clo l qu
trnh n tip song song km theo s th lin tip cc nguyn t hyro
ca nit, kt qu l sinh ra hn hp amin bc nh1t, bc 2 v bc 3.
NH3 + ROH
- H2O

RNH2 + ROH
- H2O

RNH2 + ROH
- H2O

R3 N

V trong trng hp ny, t l hng s vn tc ca cc giai on ni tip

cho thy khng thun li cho vic iu ch amin bc nht v amoniac l
baz v tc nhn i nhn yu hn. Tuy nhin, di tc dng ca cc
xc tc trn c th xy ra s chuyn v ca cc nhm ankyl, ging nh
trong trng hp ankyl ha cc hp cht vng thm di tc dng ca
xc tc AlCl3. V d metyl amin sau khi chuyn v s l hn hp bao
gm 33%NH3, 31%CH3NH3, 32% (CH3)2NH2 V 4% (CH3)3N. Trimetyl
amin s to ra vi amoniac 4 sn phm. Nh vy, s xy ra cc phn
ng thun gnhch ankyl ha li cc amin,nh hng mnh n thnh
phn sn phm. Trong t l cn bng cao hn nhiu so vi t l ng
hc v c li trong vic tng hp amin bc nht.
2RNH2
2R2NH

R2NH + NH3
RNH2 + R3N

Mc d di cc iu kin thc t cn bng khng hon ton t c,

vn c th s dng mt lng d amoniac, iu ny cho php chi ph
hon lu n. Hn na, nu sn phm mong mun ca qu trnh, v d
l amin bc 2, th khi a tr li phn ng amin bc nht v bc 3 s c
th loi tr phn ng sinh ra chng tc l hng phn ng theo chiu
mong mun. Khi trong hn hp phn ng s thit lp nng khng
i ca cc sn phm ph tng ng vi cc iu kin cn bng vn
tc phn ng.
111

Qu trnh ankyl ha amoniac bng ru c s dng torng sn xut

cng nghip vi qui m ln iu ch cc amin mch thng thp phn
t.
4.6.2. Tng hp metyl amin
Metyl amin (CH3NH2), nhit ngng t -6.80C, trn hp vi nc bt
k t l no, vi khng kh chng to hn hp d n, l cht c. L hp
cht trung gian trong tng hp hu c.
Tng hp amin c thc hin trong pha kh 380 4500C v 2
5Mpa. p sut cn s dng tng nng sut, gim kch thc thit b
v hn ch qu trnh ph tch nc ca ru. Xc tc c s dng l
oxit nhm hot ha hay aluminosilicat, i khi c thm cc cht tng
hot. y l mt phn ng in hnh xc tc d th, v hiu ng nhit
khng ln ca phn ng cho php s dng thit b phn ng ng p,
vi lp xc tc lin tc c nh. T l mol gia amoniac v ru (
metanol) l 4 : 1, ngoi ra cc amin bc nht, bc hai, bc ba c th thu
c bt k t l mol no nu chng ta a v hon lu phn ny hay
phn khc mi loi amin (thng thng l trimetyl amin). Phn amoniac
d, ru cha phn ng v ete cng c hon lu tr li cho phn
ng.
S cng ngh sn xut metyl amin c biu din trn hnh 4.6

Hnh 4.6. S cng ngh sn xut metyl amin

1 Thit b trn, 2 Thit b trao i hnit, 3 Thit b phn ng,
4, 8 Thp chng ct, 9 B phn hi lu, 10 Thit b un nng,
11 Bm, 12 van chnh p

112

Lng metanol v amoniac mi cng vi lng hon lu c trn ln

p sut 2 5Mpa 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
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 nhit 2 v sau mang 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 cao sao cho thu c on hi lu lm
lnh bng nc. Trc ht trong thp chng 4, ngi ta chng tch
amoniac v n c a tr li 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 trimetyl amin (TMA) rt cao so vi
cc amin khc). Mt phn nh lng TMA chng tch ra c xem nh
l thnh phm, nhng phn ch yu l a tr li phn ng. Hai amin
cn li c nhit si khc on thp chng 6 v 7. mi sn phm
ny ly ra t nh thp c th xem nh l thnh phm hoc a tr li
phn ng tip tc. thp chng cui cng s 8 s chng ct metanol
khi nc, v metanol c quay tr li phn ng. Hiu sut tt c cc
amin l 95%
Trong tng hp etylamin, ngi ta cng s dng qui trnh cng ngh
tng t nh trn, ch khc bit l amin ny c nhit si cch bit
hn (16,5; 55.9; 89.5) nn c th tch ra bng chng ct phn on
bnh thng. Trong trng hp ny, sn phm ph l etylen, n c th
tch ra khi ngng t hn hp trc giai on chng tch amoniac.
4.7. Oxy ha naphta nh (C5 C8)
4.7.1. C s l thuyt
Khi oxy ha n-parafin, s ct mch xy ra ch yu theo cc mi lin kt
gia cc nguyn t cacbon bc 2.
S oxy ha n-butan thc hin bi khng kh to ra dung dch axit axetic
iu kin 160 1900C v 6Mpa khng c xc tc hay c mt mui Co
hay Mn. Qu trnh ny kh a vo sn xut l do s phc tp ca s
phn tch hn hp a cu t ca cc sn phm to thnh. Phng
php c s dng rng l oxy ha cc phn on nh r hn n-butan
(C5 C8). N cha hn hp n-parafin v iso-parafin nn s lm cho tin
trnh phn ng cng nh thnh phn sn phm rt phc tp. Tuy vy
cc sn phm c th chia thnh 2 nhm: axit (formic, axetic,
propionic) v cc cht trung gian (ru, xeton). Nhm sau cng
thng d bay hi (to ra hn hp ng ph vi nc) v iU ny cho
php tch cc cht trung gian ra khi axit v a chng tham gia tr li
qu trnh oxy ha. T phn on axit s tch c cc axit formic,
acetic, propionic, sucxinic, hiu sut ca chng tnh trn 100kg xng
113

tng ng: 20, 70 75, 10 15, 5 10kg.

S oxy ha xng tin hnh khng c xc tc hay c xc tc 170
2000C v 5 Mpa. V cc sn phm chnh bn vi s oxy ha tip theo
nn thit b phn ng thng l thp sc kh dng n gin, trong
nhit ta ra s dng bay hi xng v cc sn phm trung gian ca
s oxy ha (hnh 3) Hn hp phn ng s a qua thp 2 chng
ct xng cha chuyn ha v cc cht trung gian a tr v thit b
phn ng. Cht lng y thp ny s mang i tch cc axit.
Thnh cng ca qui trnh nu khng ch th hin s n gin ha
giai on phn tch cc sn phm m cn lm tng hiu qu s dng
nng lng ca h thng. Khng kh d cng vi hi ca cc cht hu
c pha trn thit b phn ng s cho qua thit b ti sinh hi 3. Sau
nhit ca kh c s dng trong phn trao i nhit 4 nung nng
nc, cn p sut kh trong b phn gim p 6 s thay i, nh th m
b phn lm ngui 5 t kh s ngng t c phn cn d ca hi
xng. Phn ngng t ny s a tr v thp 1 oxy ha.
4.7.2. S oxy ha phn on nh ca xng (C5 C8)

Hnh 4.7. S oxy ha phn on nh ca xng (C5 C8)

1 Thp phn ng, 2 Thp chgn phn on, 3 - Thit b ti sinh hi,
4 Trao i nhit, 5 Lm ngui, 6 My gim p, 7 Bm, 8 Tch ly,
9 - Ni un.

4.8. Oxy ha parafin rn thnh axit bo tng hp

4.8.1. C s l thuyt
Do chiu di mch ln nn s nhn c hn hp rt phc tp cha
114

nhiu cc sn phm khc nhau. S tn cng vo phn t hydrocacbon

c th theo bt k v tr nguyn t cacbon bc 2 no. Cc sn phm oxy
ha khng hon ton nh l xeton v ru. Khi oxy ha parafin rn C30,
cc axit nhn c khong 60% gm cc phn on C10 C20 k c
cc axit C1 C4 cng nh C5 C9 hay l cao hn (ln hn 20 nguyn
t cacbon). c tnh ni bt ca axit bo cao no l kh nng oxy ha
thnh oxyaxit v lactonxetoaxit v axit dicacboxylic. Cc tp cht ny
lm gim lng axit chnh do cn phi hn ch mc chuyn ha
ca tc cht ban u v nhit ca qu trnh.
Khi oxy ha parafin cha hydrocacbon vi s nguyn t cacbon trung
bnh khong 30, hiu sut axit cacboxylic t 80%. Hn hp to thnh
ca cc axit c phn t lng khc nhau c thnh phn nh sau:
Bng 4.2. Thnh phn sn phm ca s oxy ha parafin C30
Axit

C1 C4 C5 C6

Thnh phn
5 - 10
(%)

3-5

C7 C9

C10
C15

8 - 10

25 - 28

C17
C20

>C20

15 - 20 20 - 25

nu x phng ngi ta s dng phn on C10 C20, trong phn

on C10 C16 i vi x phng bt, cn C16 C20 l i vi x phng
bnh. Cc axit khng tan trong nc (C7 C9) c s dng iu
ch cc ru tng ng ( bng phng php cng hydro0 v cng
sn xut cc cht ha do v du m bi trn (di dng este vi ru
a nguyn t). cc axit thp ha tan trong nc (C1 C4) hu nh
khng s dng v loi ra cng vi nc ra. Cn cc axit cao phn t
(>C20) th mt phn ng dng ch to x phng bnh. Trong phn
cn d t schng ct, ngoi cc cht k trn cn cha axit
dicacboxylic.
T cc sn phm khc to thnh khi oxy ha parafin, th sn phm ch
nht l ru. Chng c th tch ra (sau khi loi este v nc axit
bng dung dch H2O - kim) di dng este ca axit boric. Trong s cc
ru ny c cha 8 10% cc parafin nguyn liu ban u. Cc ru
c 8 26 nguyn t cacbon trong phn t ch yu l ru bc nht (65
70%). Chng c s dng thnh cng tng hp cc cht hot
ng b mt dng ankylsunfat.
S oxy ha parafin c th tin hnh 150 1700C khng cn xc tc
nhng lc s nhn c cc axit c cht lung thp. V vy qu
trnh c tnh chn lc hn khi s dng cc cht xc tc c a vo
dng nc penmanganat kali, mt vi mui mangan, peroxit mangan
hay hn hp nhn c khi ti sinh mangan t cht oxy ha. Cc cht
k trn thng khng tan trong parafin v vy lc u (khong 2 gi)
cn gi nhit 125 1300C iu chnh s hnh thnh xc tc
115

ng th (mui mangan ca axit cacboxylic no), nkhi hot tnh ca

xc tc s tng . Hydroxit ca natri hay kali hay mui ca cc kim loi
ny vi axit h c cng tng ng k hot tnh ca xc tc, c bit t
l Mn2+ : K+ = 1: 1 s l t l ti u.
Tc oxy ha parafin pha lng ph thuc vo cc yu t nh nng
cht xc tc, nhit , p sut ring phn ca O2, tc ca cht
oxy ha kh v thm ch vo kch thc ming l m qua khi sc vo
hn hp phn ng. Trong cng nghip, nng ch xc tc c gii
hn t 0.2 0.3% (% khi lng). Khi tng nhit , tc ca qu
trnh s tng. Mc chuyn ha t 30 35% 800C sau 110 gi,
1000C sau 38 gi v 1100C sau 24 gi. Cng vi s tng nhit s
to kh nng dch chuyn phn ng vo vng khuych tn, v th
ngha quan trng s nhn c. Cc yu t k trn nh hng khng
ch n tc phn ng m cn n thnh phn cc cht to thnh,
hiu sut v cht lng phn on chnh ca cc axit bo cao phn t.
Nh trong ch chuyn tip v khuych tn th hm lng ca hp
cht oxy ha mc ti a tng mnh nn s lm gim cht lng ca
cc axit chnh.
Da vo s nh hng ca cc yu t ny, ngi ta tm ra qui trnh
oxy ha parafin c xc tc pha lng vi cc ch tiu sau y: Mc
chuyn ha khng ln hn 30% - 35%, s oxy ha thc hin p sut
kh quyn khi c khng kh sc vo thp phn ng qua c cu phn
phi cha mt s lng va cc l (1 2mm). Vic dng lng
tha khng kh s to kh nng xo trn mnh hn hp phn ng.
Trong cc iu kin ny v vi s lng xc tc mangan nu trn,
s oxy ha parafin s tin hnh trong khong t 15 20 gi.
4.8.2. S qui trnh cng ngh oxy ha parafin rn
S qui trnh cng ngh c biu din trn hnh 4.8.

116

Hnh 4.8. S cng ngh oxy ha parafin rn

1 Bnh khuy trn, 2 Thp oxy ha, 3, 6 Thp ra, 4 Bnh nung,
5 Bnh lng, 7, 8 - Thit b x phng ha, 9 - B phn trao i nhit,
10 - Ni hp, 11 L nung , 12, 13, 16 - B phn tch, 14, 15 - Thit b khuy, 17 - B phn
lm ngui, 18 Bm, 19 Van iu p

Parafin nhp liu v sn phm t giai on phn tch (l phn

cha x phng ha I) theo t l 1 : 2 cng nh cht xc tc s trn ln
trong thit b 1. Sau s a qua thp 2 tin hnh s oxy ha gin
on. Trong thp c cha nhm hay than hot tnh v cc ng nung
nng hay lm ngui, thit b lm ngui t ngoi nhn nhit ta ra
cng nh c cu phn tn a khng kh vo. Kh trn thp s
qua thp 3 v ra bng nc nhm hp th cc axit thp phn t, k
c lm sch ra khi tp cht nh s nung nng trong l nung 4 v
thi ra ngoi kh quyn.
Cht oxy ha sau khi thc hin phn ng v lm ngui xung 80
0
90 C s a qua b phn lng 5, y s tch xc tc v ti sinh xc
tc. Trong thp 6 nh nc chy v t thp 3 s tch c cc axit
thp phn t ha tan trong nc. Sau phn cn li s x l bng
xoa thit b x phng ha 7 chuyn axit t do thnh mui v bng
dung dch kim trong thit b x phng ha 8, ti y xy ra thy phn
cc este v lacton
117

2RCOOH + Na2CO3
RCOOR, + NaOH

2RCOONa + CO2 + H2O

RCOONa + R,OH

S x phng ha cc cht kh thy phn thc hin di p sut

2Mpa trong b phn trao i nhit 9 v ni hp 10 1800C. Trong ni
hp s tch c dung dch nc mui ca axit cacboxylic ra khi phn
cha x phng ha I, phn ny c a tr v chun b hn hp ban
u. Tt nhin phn cn li trong ni hp 1 0 vn cn cha mt t cht
cha x phng ha v chng s c chng tch nhit cao
lm tng cht lng ca axit. thc hin qu trnh ny, cn nung
nng trong l nung xon 11 ln n 320 3400C v tit lu hn hp khi
tch cc cht d bay hi trong b tch 12. Sau hi s c ngng
t trong thit b trao i nhit v c phn tch thnh 2 pha trong thit
b tch 13: pha nc v pha hu c. Pha hu c ny gi l phn cha
x phng ha II v chng c a tr li s oxy ha hay tch ru
X phng t thit b 12 s ha tan vo trong nc thit b trn 14 v
c x l bng H2SO4 trong thit b 15 hay mang tch dung dch trong
thit b tch 16 ra khi axit t do. Cc axit t do ny s c chng
trong cc thp chng phn on (trn s khng biu din) 1.33Pa
gm nhiu phn on axit C5 C6, C7 C9, C10 C16, C17 C20. phn
cn li chnh l axit >C20 v axit dicacboxylic.
Qu trnh va kho st oxy ha parafin rn thnh cc axit bo cao
phn t ni chung vn cn cc nhc im c bn nh: sn lng
thp, qu trnh gin on, to ra nhiu sn phm ph. S khc phc
cc nhc im ny nh vo cc bin php nh a ra s lin tc
v to kh nng s dng ti a cc ph phm (cc axit cacboxylic thp
phn t, axit dicacboxylc, ).

118

CHNG 5: TNG HP TRN C S ETYLEN

5.1. Oxy ha etylen, tng hp oxit etylen
5.1.1. C s l thuyt
Etylen oxit l cht lng (t0s = 10,70C), trn ln hon ton vi nc, to
vi khng kh hn hp n nguy him trong gii hn 3 80% (th tch)
v c c tnh cao. Etylen oxit l mt trong nhng sn phm trung gian
rt quan trng. N c sn xut vi qui m ln v ng dng trong
hng lot qu trnh tng hp hu c nh tng hp etylen glycol, etanol
amin,
Phng n u tin tng hp etylen oxit l clo ha etylen qua giai on
trung gian etylen clohydrin
Tuy nhin do s tiu hao clo v kim nhiu, ng thi to ra mt lng
ln mui nn phng php ny b loi b. Phng php sn xut
etylen oxit hin nay l oxy ha etylen.
Mc d trong phn t etylen khng c nguyn t cacbon no, s oxy ha
ca n ph thuc vo cc thng s qu trnh v xc tc c th xy ra
theo nhiu hng. Bo ton chn xc tc nng cao tnh chn lc
theo hng to thnh oxit etylen c gii quyt t nhng nm 30.
Xc tc ny chnh l bc kimloi trn cc cht mang khc nhau, lm
vic nhit va phi khong 200 3000C, nhit cao hn xc
tc s thc y phn ng oxy ha hon ton etylen, cn nhit thp
hn th hot tnh km. Trn c s xc tc bc, trong s tt c cc phn
ng c kh nng xy ra th hng ch o ca qu trnh vn l to
thnh oxit etylen v oxy ha hon ton etylen, cn s to thnh
acetanehit do s ng phn ha oxit rt khng ng k. Ngi ta
chng minh c rng, CO2 c th c sinh ra t etylen hoc etylen
oxit, trong vn tc qu trnh oxy ha -oxit tng i ln v iu ny
lm cho tnh la chn gim khi tng chuyn ha ca etylen
CO + H2O

CH2 = CH2

+ O2

CH2 - CH2

+ O2

CO2 + H2O

C hng lot ngh bin tnh xc tc bc oxy ha etylen. C th s

dng nhiu loi cht mang khc nhau nh silicagen, oxit nhm, hn hp
silicagen v oxit nhm, cacbua silic, Cc ph gia v cht tng hot
xc tc l antimor, bismut, perixit bari. Trong thc t ngi ta thm vo
khong 0.01 0.02 (phn trm khi lng) dicloetan ( cht gim hot
tnh xc tc) tng tnh la chn ln 5%.
Nhit nh hng mnh n la chn, s oxy ha hon ton c
nng lng hot ha cao hn v vy vi chuyn ha ca etylen l
khng i th tnh la chn s gim khi tng nhit . Ngi ta kho st
v nhn thy nhit ti u l trong khong 220 2800C v vic gim
nhit tuy c li cho s tng tnh la chn nhng li gim nng sut
119

ca xc tc. Mu thun ny c th gii quyt bng cch s dng p

sut 1 3Mpa v p sut khng nh hng n tnh la chn nhng li
gip cho s hp th etylen oxit t hn hp hk phn ng d dng hn
Do s nh hng kh ln ca chuyn ha etylen n tnh la chn
nn thit b phn ng thch hp nht l dng ng c lm lnh bng
hi nc ngng t di p sut hoc bng cht ti nhit trung gian.
Vic s dng cc thit b phn ng vi tng xc tc gi lng khng thu
c kt qu cao nn hng ny b loi b.
5.1.2. Oxy ha etylen bng khng kh. Tng hp etylen oxit
y l phng n cng ngh u tin tng hp etylen oxit v n
nay vn cn gi tr thc t cao. S cng ngh ca phng php ny
c trnh by trn hnh 5.1.
S oxy ha c thc hin lin tip trong 2 thit b phn ng dng ng
2 v 5. Vi mt giai on trung gian hp ph etylen oxit t hn hp
phn ng sau bc oxy ha u tin. iu ny cho php gim s oxy
ha tip tc oxit khi tng chuyn ha ca etylen, ngha l tng
chn lc ca qu trnh. Ngoi ra, iu ny cn cho php thc hin s
tun hon kh giai on u oxy ha v do s dng trit hn
etylen, oxy v gim kh nng n ca hn hp nh s lm long bng
nit v dioxit cacbon.

Hnh 5.1. S cng ngh oxy ha etylen bng khng kh

1, 4 B phn trao i nhit, 2, 5 Thit b phn ng, 3, 6 Thit b hp ph, 7 my nn

Khng kh sch v etylen trc khi a vo giai on u c

trn vi kh hon lu ca giai on ny. Kh t pha trn thit b hp
ph 3 c t nng s b trong b phn trao i nhit 1 bng kh t
thit b phn ng 2. Hn hp i vo thit b 2 c cha 4 6% (th tch)
120

etylen, 6 8% (th tch) oxi, 8 10% (th tch) dioxit cacbon, cn li l

nit v cc thnh phn tr trong etylen. Thi gian tip xc trong thit b
2 l 1 4s v chuyn ha ca etylen t 30 40%. Kh ra khi thi
b c cha 1,5% (th tch) oxit etylen. Nhit ca kh c tn dng trong
thit b trao i nhit 1 v sau khi lm lnh s b c chuyn qua thit
b hp ph 3, ti y etylen oxit c nc hp ph. Kh i ra t thit b
3 c chia lm 2 dng, phn chnh c a tr li thit b oxy ha,
phn cn li c a qua oxy ha tip qua b trao i nhit 4 v vo
thit b phn ng 5.
V kh sau giai on 2 c thi vo kh quyn nn trong thit b
phn ng 5 phi chn ch sao cho thu c lng ti a etylen oxit,
tc l mc chuyn ha etylen cc i v tt nhin tnh la chn c
gim i. Kh ca giai on 2 cng ging nh giai on 1, c a qua
b phn trao i nhit 4, sau l thit b hp th 6 thu etylen oxit.
Dung dch etylen oxit v CO2 t hai thit b 3 v 6 c kt hp li v
x l tip tc thu sn phm. Hiu sut etylen oxit l 60% tnh theo
etylen, la chn khong 65% v chuyn h tng cng ca etylen
khong 90%.
Trong cc dy chuyn cng ngh mi, ngi ta tin hnh tun hon
mi hn hp kh giai on 2 v nu cng sut ln th tin hnh qu
trnh 3 giai on oxy ha. Khi c th nng hiu sut etylen oxit ln
65%.
5.2. Cng ngh tng hp trn c s oxit. Tng hp etylen
glycol (EG) t oxit etylen
5.2.1. Thit b phn ng
Xt v c tnh cng ngh, cc qu trnh sn xut trn c s etylen v
propylen oxit c th chia thnh 3 loi:
1. Phn ng c thc hin khi cu t th 2 d rt nhiu (tc l thiu
oxit), nh sn xut etylen v propylen glycol, dietylenglycol,
xenlulozol. Nhit sinh ca phn ng c lng d hp thu, do vy
nhit ca phn ng thc hin ch tng khong 40 500C. iu ny
cho php thc hin qu trnh iu kin ng p v ng th, tc l c
th chun b trc dung dch oxit trong nc hoc trong ru.
gi cho hn hp phn ng trong trng thi lng nhit 150 2000C
cn p sut 2MPa.
i vi qu trnh ny ngi ta s dng thit b dng ng hot ng lin
tc (hnh 5.2a) v khng c b mt truyn nhit. Thi gian tip xc trong
tng hp glycol l 20 30pht, tuy nhin tnh la chn tng i thp.
tng nng sut v hiu sut ca qu trnh ngi ta s dng xc tc
axit photphoric v tin hnh phn ng trong thit b dng ng chm
(hnh 5.2b). loi ny, tnh la chn tng ng k
121

2.
Cc phn ng trong t l mol gia oxit vi tc nhn khc t
1 : (4 5) n (2 3) : 1 nh oxyetyl ha amin, tioglycol v tioete,
ankylen cacbonat s ta nhit mnh. Do vy cn c b phn ti nhit
trnh hin tng nhit cc b. Dng thit b in hnh cho cc qu
trnh ny l ng chm (hnh 5.2b) hoc lm lnh pha bn ngoi bng
sinh hn (hnh 5.2c). Thit b hnh 5.2b cn lm vic di p sut cao
hn hp phn ng trong trng thi lng. Cn trong thit b hnh c cn
phi c s i lu tt. Thit b ny ch s dng trong nhng trng hp
khi cc s chuyn ha lin tip khng ng vai tr quan trng. y
sn phm ca phn ng s ng vai tr mi trng v ngi ta sc vo
n cc kh nh etylenglycol, CO2, H2S. Nc s c s dng ti
nhit cho phn ng.
3. Cc phn ng trong t l mol gia oxit vi cu t th 2 ln
hn 3 : 1 (tng hp polyglycol v cc cht hot ng b mt khng ion).
Trong trng hp ny, nhit ca phn ng mnh n mc m vn
gii nhit tr nn quan trng nht, do s tng nhit s lm gim cht
lng sn phm. Mt thi gian di ngi ta s dng cc loi thit b
phn ng gin on, trong ngi ta sc kh oxit qua hn hp
phn ng lng (loi hnh 5.2c) hoc trong thit b c b phn khuy v
lm lnh bn trong. Do c s c qunh hn hp phn ng khi s nhm
ankylenoxit a vo phn t tng ln, v vy hiu qu sc kh rt yu v
thi gian phn ng phi ko di t 8 15gi. Gn y c mt phng
n khc cho thit b gin on (hnh 5.2d) l tin hnh phn tn hn
hp lng trong kh oxit, nh vy tng ng k b mt tip xc ca
cc pha v gim thi gian phn ng cn 1.5 3gi. Cc cht lng di
y c nn v phun vo khong khng c cha oxit qua cc u
phun

122

Hnh 5.2. Cc loi thit b phn ng ca qu trnh oxyankyl ha

a Thit b ng p, b - ng chm, c vi b phn i lu cht lng thng qua sinh hn,
d hot ng gin on vi h thng phun cht lng

5.2.2. Tng hp EG
etylenglycol l mt cht lng khng mu (t0s = 1970C), c nht tng
i cao, ha tan tt trong nc. Trong cng nghip mt lng ln
etylenglycol dng sn xut cc cht bi trn di dng hn hp vi
nc khng b ng cng nhit thp v lm lnh cc ng c
trong nhng ma ng gi lnh. Etylen glycol cn c s dng
tng hp cc polyme v cc vt liu cao phn t nh
polyetylenterephtalat (PET), nha polyeste khng no, polyuretan, cc
loi nha ankytT EG c th tng hp ra etylenglycoldinitrat sn
xut cc cht n v thuc sng cng nh mono v diacetat etylenglycol
l nhng dung mi rt hu hiu.
phng php quan trng nht trong cng nghip sn xut EG l thy
phn etylenoxit 170 2000C, khng c xc tc vi lng nc d 15
ln. Mt s tc gi ngh thc hin qu trnh ny nhng iu kin
nh hn vi xc tc l axit photphoric.
Trn hnh biu 5.3 biu din s cng ngh tng hp EG (s ny
cng p dng c cho tng hp propylenglycol)
Qu trnh tin hnh khng c xc tc nhit 160 2000C vi p
sut gi cho hn hp phn ng trong trng thi lng. Hn hp ban
u c chun b bng cch trn nu7o1c mo v nc ngng t cng
vi etylen oxit, nng khong 12 14% tc l tng t vi t l nc /
123

eytylen oxit l 15. Hn hp ny c trn ln trong tht b 1, sau

un nng bng hi nc trong thit b 2 n nhit 130 1500C v
a vo thit b phn ng 3. Hn hp i qua ng dn gia thit b
xung di v trong qu trnh ny c un nng nh nhit ca hn
hp phn ng c sn trong thit b. Khi s xy ra phn ng v to
thnh sn phm. Ngoi etylenglycol, di v trietylenglycol, cc sn phm
ph l acetanehit (do s ng phn ha ca etylen oxit) v cc sn
phm khc. Khi ra khi thit b phn ng, cht lng c nhit 2000C,
gim p sut n p sut kh quyn. Khi mt phn nc s bc hi,
cn cht lng c lm lnh xung 105 1100C
Hn hp sau i vo thit b 4, ti y giai on u tin ca qu trnh
c c nhiu giai on, trong giai on sau lm vic chn khng
cao hn so vi giai on trc (n 133Pa) v c un nng nh hi
nu7o1c to ra ca giai on trc (trn s ch th hin 2 giai on c
c thit b 4 v 5). Sn phm y ca 5 l cht lng tip tc chng
tch nc trong chn khng trogn thit b chng ct phn on 7. ton
b cc phn nc ngng t c kt hp li v a tr li chun b
hn hp ban u cho phn ng. Hn hp cc glycol t thit b 7 c
a vo ct chng ct chn khng 8, trong s thu c EG tng
i tinh khit, sn phm y cn li bao gm di v trietylenglycol.

Hnh 5.3. S cng ngh tng hp etylenglycol (EG)

1 Thit b trn, 2 Thit b un nng bng hi nc, 3 Thit b phn ng,
4, 5 Thit b c c, 6 Thit b ngng t, 7, 8 Ct chng ct phn don,
9 Van chnh p, 10 B hi lu, 11 Thit b un nng, 12 - Bm

124

5.3. Oxy ha etylen. Tng hp acetanehit, vinyl acetat, axit axetic

5.3.1. C s l thuyt
Tng hp cc hp cht cacbonyl t olefin da trn c s mt phn ng
c bit n t lu, l s tc dng ca lcorua paladi vi olefin,
trong paladi b kh n mc thp nht
CH2 = CH2 + PdCl2 + H2O

CH3CHO + Pd + 2HCl

Nu a vo hn hp phn ng thm mt lng oxy s xy ra s oxy

ha paladi, nhng rt chm. Cng lao ca cc tc gi qui trnh ny
ch h thit lp h oxy ha - kh, trong paladi rt nhanh chng b
oxy ha, tc l paladi c ti sinh tr v dng hot ng. Cc tc gi
nhn thy, nu thm vo h phn ng mt lng mui ng II, n s
oxy ha paladi tr v ng I, ng I rt d b oxy ha bng oxy thnh
ng II, ni cch khc mui ng ng vai tr cht mang oxy cho paladi
Pd + 2Cu2+

Pd2+ + 2Cu+
2Cu2+ + H2O

2Cu+ + 0.5O2 + 2H+

C hai phn ng ny xy ra tng i mnh lit trong mi trng axit,

trong clorua paladi nm dng H2PdCl4
C ch ca phn ng bao gm cc giai on to thnh phc trung gian
t clorua paladi, olefin v nc v s chuyn ha ni phn t ca phc
ny. S c ch phn ng nh sau:
CH2 = CH2 + [PdCl4]2-

CH2 = CH2

+ H2 O
- Cl-

[Cl3Pd]+ H2 O
- H3 O

CH2

CH2

CH2 = CH2
[Cl2Pd - OH]-

CH2 = CH2
Cl2Pd...OH2

- Cl-

CH2 - CH2
ClPd OH

Cl2Pd

OH

H
Cl

H2C

CH

Pd

OH

- Pd

CH3 - CH+ClOH

CH3 - C-H + HCl

O

Kh nng phn ng ca olefin trong qu trnh ny thay i theo dy c

trng cho trng hp s dng xc tc phc kim loi
Bng 5.1. Kh nng phn ng ca mt s olefin
olefin
CH2 = CH2 CH3 CH = CH2
CH3 CH2 CH = CH2
Kh nng
1.00
0.33
0.25
phn ng
125

S oxy ha xy ra trn nguyn t cacbon t hydro nht, do vy

acetanehit ch to thnh t etylen, cn t cc olefin khc s to thnh
ceton. Ngoi cc ng ng ca etylen, cc cylco olefin, cc ankyl vng
thm c cha ni i mch nhnh cng c th tham gia phn ng oxy
ha ny.
Cc sn phm ph c th l anehit, v d t propylen s thu c
anehit propionic do s tn cng vo nguyn t cacbon . Ngoi ra do
tc dng clo ha ca clorua ng c th to thnh cloceton (hm lng
sn phm ph ny tng khi khi hm lng cc mui ng v axit ca
dung dch tng ln). Hiu sut cloceton c th t n 10 30% trong
oxy ha n-buten. Do vy cn phi c cc bin php gim sn phm ny
hoc c hng tch v s dng n
iu ch acetanehit bng oxy ha etylen trn h xc tc PdCl2.CuCl2
t hiu sut n 95%, cao hn hn cc phng php khc, li i t
ngun nguyn liu r tin hn so vi axetylen v ch c mt giai on.
Bng 5.2. So snh cc ch tiu kinh t ca 3 phng php iu ch
acetanehit
Phng php
Gi thnh (%)
Chi ph u t (%)
Cng
hp
nc
vi
100
100
acetylen
T etylen qua etanol
85 95
60 - 70
Oxy ha etylen
55 - 60
45 - 55
Nh vy c th thy phng php oxy ha etylen gn nh chim u
th tuyt i so vi cc phng php khc v hin nay n loi b
cc phng php ny trong cng nghip sn xut acetanehit
5.3.2. Tng hp acetanehit bng con ng oxy ha etylen
Trong qu trnh ny, iu quan trng l t c s tng ng gia
cc vn tc oxy ha etylen trn PdCl2, oxy ha paladi dng kh bng
CuCl2 v oxy ha Cu2Cl2 bng oxy. Giai on chm nht l oxy ha
Cu2Cl2, do vy dung dch xc tc cn phi cha lng d mui ng. V
d cc kt qu kh quan t c vi cc dung dch axit yu cha 0.3
0.5% PdCl2 v 10 25% CuCl2 c thm mt lng khong 2 3%
acetat ng iu chnh pH. Vi dung dch ny, cc phn ng u xy
ra tng i mng lit 100 1300C v p sut 0.3 1Mpa.
Thit b phn ng l dng thp sc kh lm bng thp titan hoc cc vt
liu chu axit khc. Thit b khng c b phn trao i nhit v nhit sinh
ra trong phn ng c s dng trc tip un nng tc cht mi
hoc lm bc hi. C 2 phng n cng ngh l mt giai on v 2 giai
on.
Trong phng n hai giai on, s oxy ha etylen bng dung dch xc
126

Khng kh

tc v ti sinh xc tc bng khng kh c thc hin trong 2 thit b

khc nhau ( hnh 5.4)

Hnh 5.4. S cng ngh tng hp acetanehit hai giai on

1 Thit b phn ng, 2 Thit b ti sinh xc tc, 3, Thp bc hi,
4 Bm, 5 Van chnh p

Ngi ta a vo thit b phn ng 1 etylen v dung dch xc tc

ti sinh v phn ng din ra vi chuyn ha gn nh hon ton ca
etylen iu kin nhit 100 1150C v 0.8 0.9 Mpa. Dung dch
acetanehit thu c s a qua thit b chnh p v vo b phn bc
hi 3. Ti y s chng tch acetanehit v cc kh tan. Dung dch cn
li thp bc hi, bng bm c nn n 1Mpa v a qua thit b ti
sinh 2. Ngi ta thi khng kh vo thit b ti sinh 2 oxy ha kim
loi, sau dung dch ti sinh c hi lu li thit b 1. u im
ca phng n cng ngh ny l rt an ton (v khng c s trn ln
etylen vi khng kh) v s dng khng kh lm tc nhn oxy ha.
Phng n mt giai on kt hp 2 qu trnh oxy ha etylen v ti
sinh xc tc trong mt thit b phn ng. Nhm trnh to thnh hn hp
n, qu trnh c thc hin vi lng d etylen v sau a lng
ny v phn ng tip tc. iu ny bt but phi s dng tc nhn oxy
ha l oxy k thut v oxy c chuyn ha hon ton trong thit b
phn ng. (hnh 5.5)
Ngi ta a vo thit b phn ng dng thp sc rng c cha
dung dch xc tc oxy ha etylen (etylen hon lu v etylen b sung).
Thp phn ng lm vic mc cht lng c nh, iu kin p sut
P = 0.3MPa v 1300C. Lng etylen d s thi acetanehit mi sinh ra
khi dung dch v nh vy s trnh c cc phn ng ph. Cng vi
127

acetanehit s bc hi mt lng nc, nc ny s ngng t trong

sinh hn 3 v sau a tr li thit b phn ng
Hn hp kh hi nc c a vo thit b hp ph 4, ti y
acetanehit s c nc hp thu. Phn kh cn li bao gm etylen,
lng nh oxy v cc tp cht tr khc c a tr li phn ng
thng qua thit b nn kh 2. Dung dch acetanehit trong nc t y
thit b 4 c a qua thit b bc hi 5, ti y s tch cc khi ha tan
v cc tp cht bay hi. Sau trong ct 6 di dng ngng t s thu
c acetanehit, cn phn ln sn phm lng y c cha cc sn
phm ph kh bay hi (anehit crotonic) c a tr li b phn
hp ph sau khi lm lnh
So vi phng n 2 giai on, phng n 1 giai on i hi chi
ph u t thp hn, t tiu hao nng lng hn, tuy nhin li s dng
oxy t tin hn khng kh. V vy cc ch tiu kinh t ca 2 phng
php ny tng ng vi nhau v trong thc t u c p dng.

Hnh 5.5. s cng ngh tng hp acetanehit mt giai on

1 Thit b phn ng, 2 my nn tun hon, 3, 7 Sinh hn,
4 Thp hp th, 5 Thp b chi, 6 Ct chng ct, 8 Thit b tch,
9 Thit b ngng t.

5.3.3. Tng hp axit axetic

C ch phn ng
Qu trnh oxy ha axetanehit to thnh axit axetic, xy ra theo
c ch to gc t do. Trong , sinh ra sn phm trung gian l axit
peaxetic (phng trnh 3).

128

CH3-C-H+ R*

(1)

CH3-C* + RH
O

CH3-C* + O2

CH3-C-OO*

(2)

CH3-C-OO*+ CH3-C-H

O
(3)

CH3-C-OOH + CH3-C*

Axit peaxetic sau c th phn ng vi axetanehit to thnh

axetanehit monopeaxetat (AMP). AMP phn hy nhanh chng to
thnh axit axetic, nh qu trnh chuyn v ca gc hirit trong phn ng
Baeyer-Villiger. Ngoi ra, cn xy ra qu trnh chuyn dch gc metyl
to metyl format:
O
CH3-C-OOH +
OH C
3
CH3-C
C
O-O

OH C
3
CH3-C
C
O-O

O
CH3-C-H

OH
H
OH

OH

O
CH3-C

C
O-

CH3-O

O
OH C
3
CH3-C
C
O-O

CH3-C-OH + CH3-O-C-H
OH

O
CH3-C

O-

+ CH3-C

OH
OH

O
2CH3-C-OH

Qu trnh chuyn dch ca nhm anlkyl tr nn d dng hn nhiu,

i vi cc anehit cao hn, c bit l nu c nhnh v tr .Giai
on ngt mch, trc tin xy ra theo hng phn ng lng t, ca
cc gc axetylperoxy, to sn phm trung gian l tetraoxit:
O
CH3-C-OO*

CH3-C
O-O-O-O

C-CH3

O
2CH3-C-O* + O2

129

O
CH3-C-O*

C*H3 + CO2

2CH3O* + O2

2CH3-OO*

2C*H3 + 2O2

CH3OH + HCHO + O2
2CH3O* + RH

CH3OH + R*

Phn ng trn, l ngun gc sinh ra hu ht cc sn phm ph ca

qu trnh oxy ha axetanehit nh: CO, CH3OH, HCHO v HCOOH. S
oxy ha khng c xc tc, c th lm gim hiu ng cung cp cho qu
trnh chuyn ha axetanehit, dn n lm gim ti thiu nng
CH3CHO cn duy tr trong mi trng phn ng. N cng gi cho nng
cc gc axetyl peroxyt n nh mc thp, bng cch thc y phn
ng (3). Trong phn ng khng c xc tc, cn c bit ch ngn
chn nng ca AMP t ti gii hn n.
Cc phn ng phn hy gc t do, c th tr nn quan trng nhit
cao hoc khi nng oxy thp:
O
CH3-C*

C*H3 + CO

Tc ca phn ng ecacbonyl ha tng khi tng nhit , tuy nhin

n ch tr nn quan trng, khi oxy khng lc sch cc gc axetyl
(phng trnh 2).
Cc yu t nh hng n qu trnh
nh hng ca nguyn liu axetanehit
Do CH3CHO d b bin i thnh paraehit. V vy, m lm cho sn
phm ca qu trnh khng tinh khit, c ln nhiu tp cht, gy kh
khn cho vic tinh ch v lm sch sn phm, hiu qu khng cao.
Cng mt iu kin oxy ha v xc tc, axetanehit c th b bin i
thnh nhiu sn phm khc nhau:
CH3CHO + 0.5O2

CH3COOH

2CH3CHO + 1.5O2

CH3COOCH3 + H2O + CO2

3CH3CHO + O2

CH3CH(OCOCH3)2 + H2O

3CH3CHO + 3O2

HCOOH + 2CH3COOH + H2O + CO2

3CH3CHO + 5O2

4CO2 + 4H2O

khc ph cc hin tng ny, ta phi khng ch nghim ngt ch

oxy ha, dng xc tc thch hp v s dng axetanehit > 99%,
khng qu 1% paraehit v anehit crotonic.
130

Mt khc, hm lng ca axetanehit c nh hng n qu trnh

to thnh axit peraxetic, nu hm lng axetanehit trong thit b oxy
ha tng ln qu mc, th lng peraxit to thnh gim xung, cn nu
gim hm lng CH3CHO, th lm tng lng peraxit trong vng phn
ng, v giai on 1 to peraxit nhanh hn giai on 2. iu ny, dn
n s tch t axit peraxetic, s khng c li cho qu trnh v d gy n.
V vy, cn phi khng ch lm lng axetanehit thch hp khi cho
vo.
Oxy
Vn tc oxy ha khng ph thuc vo nng oxy m ch ph thuc
vo tc ha tan kh O2 vo khi lng (yu t khuych tn khi chuyn
oxy t pha kh v pha lng).
nh hng ca xc tc
Xc tc s dng cho qu trnh oxy ha CH3CHO, c tc dng lm
tng tc phn ng v hng phn ng theo chiu to sn phm
chnh v m bo qu trnh chy qua tt c giai on vi vn tc nh
nhau.
Cc xc tc nh axetat ca st, ng, coban u lm tng nhanh
qu trnh oxy ha axetanehit thnh axit peraxetic, nhng lm chm tc
ca giai on to thnh anhyrit. Do , mt khi lng axit
peraxetic tch t li trong thit b phn ng dn n ting n.
Mt khc, khi s dng hn hp axetat ca (ng,coban) lm xc tc
v tin hnh trong mi trng dung mi l etyl axetat, th c th nhn
c axit axetic cng vi anhyrit axetic, v hiu sut anhyrit axetic
ln hn, do etyl axetat c kh nng to hn hp ng ph vi nc, lm
tch nc ra khi qu trnh. iu ny chng t, hiu sut sn phm
chnh, ph thuc vo bn cht ca xc tc.
Hin nay, xc tc tt nht cho qu trnh l axetat mangan v xc tc
hn hp ca axetat (mangan coban), cho hiu sut sn phm chnh
cao, khc phc c nhc im ca cc xc tc k trn, c kh
nng ti sinh axit peraxetic. c bit l hn hp xc tc ca axetat
(mangan coban) c hot v chn lc cao, do c s t hp
tng tr ln nhau.Hm lng xc tc c mt trong khi phn ng, c
nh hng n vn tc oxy ha. Khi tng nng xc tc th tc
phn ng khng tng hoc tng rt chm. Gii hn nh l 0,05 n
0,1% trng lng.
nh hng ca nhit
Nhit l yu t quan trng, nh hng n qu trnh oxy ha
axetanehit. Nhit nh hng n nng axit peaxetic, tc l nh
hng n vn tc oxy ha. Khi tng nhit s thc y c cc giai
on phn ng, c bit l phn ng phn hy axit peaxetic. Qu trnh
oxy ha pha lng axetanehit thng c tin hnh trong khong
131

nhit 60 800C. Nu nhit thp hn s dn ti qu trnh tch t

hp cht axit peaxetic trong phn ng v pht sinh hin tng n. Nu
nhit tng cao qu, tuy lm tng tc phn ng chnh, song cng
thc y cc phn ng ph, c bit l phn ng oxy ha hon ton
axetanehit, do chng d bay hi, ng thi gy nguy him, v hi
axetanehit bay ln to vi oxy hn hp n trong gii hn rng. Do ,
vic tng nhit li phi i km vi vic tng p sut. duy tr nhit
trong thit b trong khong nh vy, ngi ta phi gii nhit phn
ng bng cch tin hnh oxy ha trong thit b dng thp, trong thp c
t cc ng xon lm lnh.
nh hng ca p sut
Ni chung, p sut t nh hng n qu trnh. Tuy nhin, do
axetanehit l cht lng rt d bay hi, m iu kin lm vic i hi
phi tin hnh trong pha lng, nn trn thc t ngi ta thng thc
hin qu trnh p sut 3 4 at, gi cho axetanehit trng thi
lng ti nhit phn ng (60 750C). Nu s dng p sut cao qu,
s gy tn km cho vic ch to thit b.
nh hng ca lng nc
Lng nc trong thit b phn ng c nh hng ti hiu sut thu
sn phm. Khi lng nc gim,dn n tng qu trnh to thnh ca
sn phm ph anhyrit axetic, ng thi hiu sut ca sn phm chnh
gim, do vn tc ca phn ng thy phn anhyrit axetic gim. Khi
lng nc tng, th hm lng axit peraxetic tng v hiu sut sn
phm chnh tng, tuy nhin nu lng nc tng qu, s lm pha long
sn phm, gy kh khn cho qu trnh tinh ch sau ny.
Dy chuyn cng ngh tng hp axit axetic
Dung dch xc tc c chun b trong thit b (1), bng cch ha tan
axetat mangan trong axit axetic. Dung dch ny, cho qua thng cha
trung gian (2 ) cng vi axetanehit c lm lnh bng nc mui
t b cha axetanehit (3), nh bm (20) np p sut 4t vo pha y
thp oxy ha (4). Thp ny, bn trong c ch to bng nhm hoc
thp hp kim khng g (Cr Ni Mo). Oxy k thut c a vo (4)
n (5) dc theo chiu cao ca ct thp, qua ng phn phi c bit.
Ct thp c np y cht lng n gn phn m rng. Cht lng
chuyn ng cng ln cao, nng axit axetic cng tng, nng
axetanehit cng gim. Trong qu trnh oxy ha, y ct thp c duy
tr nhit 600C v p sut 3,8 4at, cn trn nh ct thp, gi
nhit v p sut tng ng l 750C v 2,8 3at. Vic khng ch
nghim ngt ch nhit , c ngha ht sc quan trng, bi v nu
nhit thp hn khong 60 700C, th s dn ti qu trnh tch t
peaxit axetic, cn nu nhit cao hn, s thc y phn ng ph, c
bit l phn ng oxy ha hon ton axetanehit. pha long hn hp
132

hi gy n, (tc trnh qu trnh tch t peaxit axetic v qu trnh tng

hp ca hn hp hi axetanehit v oxy gy n) ngi ta cho nit lin
tc vo phn trn cng ca ct thp.
Hn hp hi v kh i ra t ct oxy ha (4), c a sang thit b
ngng t lm lnh (5), ti y c nhit 20 300C nn hi axit axetic,
axetanehit v hi nc c ngng t. Phn dung dch ngng t
trong ha tan phn ln axetanehit cha phn ng, sau c
tch ring khi hi trong thit b phn ly (6) v c a tr li y ct
thp oxy ha. Hi tch ra, c ra trong thp ra (7) bng nc
tch ht phn axetanehit d v axit axetic, ri thi ra ngoi tri.
Axit axetic th, ly lin tc t phn n rng ca ct thp oxy ha (4),
qua mng cnh sn, a sang thp tinh ch (8), ti y cc hp cht
c nhit si thp (tc l cc sn phm d bay hi) b ui ra. Hi ca
chng c ngng t trong thit b hi lu (10), mt phn ngng t
c hi lu v (8), phn cn li qua thit b ngng t lm lnh (11), ri
vo b phn thu gom (12 ) v a i x l tip. Axit axetic tch khi
cc tp cht c nhit si thp, (phn ln y ct (8)) c a lin
tc vo thit b un si (13), ri vo thp (14) chng ct ln 2, ti y
nhit 1250C, axit axetic bay hi tch khi xc tc, paraanehit, axit
crotonic v cc sn phm b ha nha khc. Hi axit axetic, c
ngng t trong thit b ngng t hi lu (15), mt phn axit axetic tch
ra a tr li ti trong thp (14), mt lng no ly cho vo (1)
chun b dung dch xc tc, cn phn ln a i lm sch khi tp
cht trong thit b phn ng (16). y, axit axetic c lm sch bng
KMnO4 oxy ha cc tp cht cha trong n.
tch axetat mangan to thnh, ngi ta cho bay hi axit axetic
mt ln na trong b phn un bc hi (17) nhit 120 1250C, hi
i ra c a vo thp m (18) lc sch hi axit axetic mt ln
na, ri qua ngng t thit b ngng t (19), a tip sang thit b
phn ly (6). Axit axetic sch (sn phm tinh khit) c gi l axit axetic
thng phm, mt phn nh lng axit ny a tr li thp (18). Trong
phng php ny, thu c 1tn axit axetic cn 0,78 0,8tn
CH3CHO, 240m3 oxy k thut v 9kg KMnO4.

133

Hnh 5.6. S cng ngh tng hp axit axetic bng phng php oxy ha axetanehit
trong pha lng.
1 - Thit b chun b xc tc lng; 2 Thng cha trung gian; 3 - B cha axetanehit; 4
Thp oxy ha; 5, 11 - Thit b ngng t lm lnh; 6 - Thit b phn ly; 7 - B lc kh; 8, 14
Thp thu hi; 9, 13 - Thit b un si; 10, 15, 19 - Thit b ngng t hi lu; 12 - B phn
thu gom axit; 16 - Thit b phn ng; 17 - B phn bc hi; 18 Thp m; 20 Bm.

Tng hp ng thi axit axetic v anhyrit axetic

Phn trc ni rng trong cc iu kin xc nh khi oxy ha
anehit th song song vi axit cacboxylic cng nhn c anhyrit.
CH3COOH

+O2

CH3CHO

+O2

0.5(CH3CO)2O + 0.5H2O

Do khi to thnh anhyrit, khng km hm c qu trnh tch nc,

nn gy ra kh nng thy phn n thnh axit. Mt trong cc iu kin
tng hp ng thi anhyrit v axit l tch loi nhanh nc. lm
c iu ny, ngi ta s dng cc cht ph ng ph (etylaxetat,
diizopropyl ete), nhng v sau ngi ta xc nh l c th khng cn
chng. Lc , cc yu t chnh iu chnh hiu sut gia axit v
134

anhyrit s c to ra bi:
Thnh phn ca cht xc tc ng th, c th l hn hp mui Co
hay Mn vi cc mui Cu (Co + Cu; Mn +Cu) theo t l tng ng 1 : (1
3) hay thm ch l dng nng ca n ln trong dung dch phn ng
ny. S dng cht oxy ha l khng kh long (7 9%) phn th tch
O2, v tin hnh qu trnh oxy ha trong vng khuch tn (s lm gim
nng ca axit trong pha lng v lm tng nng cc gc t do CH3C*=O m thng qua n to ra anhyrit).
Trong cc iu kin ny, t l gia axit v anhyrit to thnh c th thay
i n (3 5) : (75).
Phng php oxy ha trc tip axetanehit, thnh hn hp anhyrit
axetic v axit axetic kinh t hn, trong nhn c 2 sn phm c gi
tr.
tng hp ng thi, ngi ta s dng 2 phng php. Trong
trng hp u, qu trnh c tin hnh trong thp sc kh vi mi
trng l etylaxetat, 50 700C v P = 0,4Mpa. S oxy ha c gy
ra bi khng kh (khng phi bi oxy) vi xc tc to ra t axetat ca
Cu,Co theo t l 10:1 hay 2:1, dung mi, axetanehit. Dung dch xc tc
c a lin tc vo thp oxy ha, cn khng kh th sc qua hn hp
phn ng. Hi thot ra cng vi khng kh, c ngng t trong thit b
ngng t hon lu, nc s tch ra, cn etylaxetat th a tr v thp,
Axetanehit d bay hi, s c hp th bng nc t kh, sau ti
sinh n b phn chng k tip. Hn hp phn ng thu t thp oxy
ha, ,c mang i phn tch tch hn hp dung mi vi nc v
axetanehit cha chuyn ha. Sau , trong cc thp khc s tip
tc chng tch ln lt axit axetic, anhyrit axetic, cn dung dch cht
xc tc th a tr li giai on oxy ha.
i vi phng php 2, qu trnh oxy ha thc hin 55 600C
khng c dng dung mi ha tan cc cht xc tc, vi tc nhn oxy
ha l khng kh ngho oxy (7 9% th tch oxy). Trong thit b phn
ng dng thp c cha cc ng xon lm lnh, ngi ta a vo hn
hp khng kh cng vi dng kh tun hon cha hi axetanehit. Hn
hp phn ng gm ch yu l axit axetic, anhyrit axetic cng vi cht
xc tc ha tan trong n. c im ni bt ca phng php ny l a
vo thit b phn ng mt lng ln kh, qua c cu phn phi kh c
bit, nhm to ra kh nng xo trn mnh cht lng. Cc sn phm
c tch ra ( dng hi) cng vi kh bay ln, cn dung dch cht xc
tc nm li trong thit b phn ng v lm vic tip trong chu k sau, v
hu nh n khng b mt hot tnh xc tc.
S cng ngh tng hp ng thi axit axetic v anhyrit axetic biu
din trn hnh 5.6
135

Hnh 5.7. S cng ngh tng hp ng thi axit axetic v anhyric axetic.
1 - My nn khng kh; 2 - Thit b phn ng; 3, 4 - Thit b ngng t;
5 - Thit b bo ha; 6 My nn kh; 7 Thit b lc kh; 8 - Thit b hp th;
9 - Thit b trao i nhit; 10, 16 Thp chng ct phn on;
11, 14, 17 - Thit b ngng t hi lu; 12 - Bn cha; 13 Thp sy;
15 - Thit b phn ly; 18 - Ni un.

Khng kh tinh khit ban u, c nn trong my nn khng kh (1),

di p sut ln hn p sut kh quyn khng nhiu v c trn vi
kh hi lu, c cha hi axetanehit. Hn hp va thu nhn (7
9%(v)O2, 25 30%(v) axetanehit, 1%(v) axit axetic, cn li l N2), s
cho vp thit b phn ng (2) qua mng li phn phi v sc qua dung
dch cht xc tc, sau n li theo hi ca cc sn phm. Hn hp kh
hi c lm lnh tc thi bng nc, trong thit b ngng t (3) v hi
lu phn ngng t v thit b phn ng, trong thit b cc cht c
duy tr thng xuyn dng lng. Sau , tin hnh lm ngui tip tc
trong thit b ngng t (4) v thit b bo ha (5), ti 5 nh axetanehit
a cho vo v do axetanehit c un si, cn cc sn phm th
c ngng t t kh.
Hn hp hi kh pha trn thit b bo ha (5) qua my nn kh,
c a tr v phi vi khng kh nhp liu, v sau a vo thit
b phn ng. Tt nhin, phn kh d c th loi b khi h thng
136

khng lm long qu mc hn hp phn ng. Kh tch ra ny cha

phn ln axetanehit c ra trong thit b lc kh (7), bng lng nh
axit axetic ( hp th hi anhyrit axetic), v sau ra trong thp hp
th (8) bng nc thu hi ton b axetanehit. T dung dch nhn
c trong thp chng phn on (10) cng vi thit b ngng t hi
lu nc mui (11), s ti sinh c axetanehit, v sau a tr v
thit b bo ha (5) v thit b thc hin phn ng. Khng kh sau khi
lm vic, s a v kh quyn qua thp hp th (8).
Phn ngng t sau thit b bo ha (5) v thit b lc kh (7), s chy
vo bn cha (12). Sn phm th ny cha 58 60% (phn khi
lng) anhyrit axetic, 28 - 30% (phn khi lng) axit axetic, 9 10%
(phn khi lng) nc, 1 2% (phn khi lng) etylliden axetat v
mt lng nh axetanehit, formanehit. Do kh nng thy phn cao
ca anhyrit axetic (c bit nhit cao) trong phng php 1, nn
ngi ta tin hnh chng ng ph nc cng vi etylaxetat trong thp
(13), vi thit b ngng t hi lu (14) v thit b phn ly (15), sau , t
hn hp sn phm thp (16), s tch c etylaxetat v a tr v
thp (13). Axit axetic v anhyrit axetic nhn c dng tinh khit,sau
khi chng phn on tip tc ( trn s khng biu din). Hiu sut
sn phm t 95% theo l thuyt.
5.3.4. Tng hp vinylaxetat t etylen (phng php axetoxy ho)
c im ca qu trnh
Cc tnh cht, ng dng v iu ch vinylaxetat (VA) t axetylen
c xem xt phn trc. Do vic s dng nguyn liu axetylen t
tin, nn phng php ny, c thay th bng phng php oxy
ha kt hp etylen vi axit axetic:
C H 2 = C H 2 + C H 3 C O O H + 0 .5 O 2

C H 2= C H -O C O C H 3 + H 2O

Phn ng xy ra trn xc tc paladi. Nu qu trnh tc dng xy ra

khng phi trong mi trng nc, m trong mi trng axit axetic th
cacbuacation trung gian s c cu to CH3-C+H-OCO-CH3 v c th kt
hp khng nhng vi phn t axit axetic th hai to ra
etylidendiaxetat, m cn tch proton to thnh vinylaxetat

C H 2 = C H -O C O C H 3

C H 3 -C + H -O C O C H 3

+ C H 3C O O H
+H

C H 3 -C H -(O C O C H 3 ) 2

Qu trnh pha lng ny, c thc hin vi xc tc PdCl2.CuCl2 trong

mi trng axit axetic c thm axetat-natri hoc clorua liti. Ngoi
etylidendiaxetat, cc sn phm ph c th l n-buten (do qu trnh dime
ha ca etylen) v axetanehit. Do trong phn ng c sinh ra nc, nn
qu trnh tch t ca nc, s to iu kin thun li cho s hnh thnh
axetanehit. Nu gi mt t l no c nh gia axit axetic v nc
th c th kt hp tng hp vinylaxetat v axetanehit. Do hiu sut sn
137

phm thp v mc n mn cao, nn qu trnh pha lng c thay

th bng qu trnh pha kh v hin ang c ng dng rng ri.
Tng hp VA trong pha kh c thc hin vi xc tc d th (Pd trn
SiO2, Al2O3 hoc aluminosilicat vi ph gia axetat natri) c cha mt
lng mui ng thc hin chc nng cht mang thc y qu trnh
oxy ha Pd thnh ha tr 2:
P d + 0 .5 O 2
P d 2+ + H 2O + 2C H 3C O O +
P d + C H 2= C H O C O C H 3 + 2 H
P d 2+ + C H 2= C H 2 + C H 3C O O H
Qu trnh tin hnh nhit 170 1800C v p sut 0,5 1MPa
bng cch cho hn hp tc nhn qua lp xc tc d th. Tc nhn oxy
ha s dng l oxy. Hn hp ban u bao gm etylen, hi axit axetic v
oxy vi t l th tch ~ 8 : 4 : 1, v chuyn ha ca chng sau khi qua
mt thit b phn ng ln lt l 10, 20 v 60 70%. la chn theo
vinylaxetat t 91 92%, sn phm ph ch yu l CO2 v lng cc
hp cht cn li chim khong 1%.
S cng ngh tng hp vinylaxetat t etylen
S cng ngh tng hp vinylaxetat t etylen trong pha kh c biu
din trn hnh 5.7.

Hnh 5.8. S cng ngh tng hp vinylaxetat t etylen trong pha kh

1 Thit b t nng hii, 2 phn ng, 3 B thi kh, 4 Sinh hn, 5, 6 Thp ti, 7
My nn, 8 B phn tch CO2, 9 H thng chng ct phn on, 10 Thit b ngng t,
11 B cp nhit, 12 Bm, 13 van chnh p.

Hn hp etylen mi b sung v etylen hi lu, cng vi axit axetic

c un nng trong thit b phn ng dng ng (2), vi lp xc tc c
nh. Hn hp phn ng, sau c lm lnh trong sinh hn (4) v
138

ra kh trong cc thp ti (5), (6) bng axetic v nc thu hi

vinylaxetat v axit axetic. Phn ln kh sau khi ra, c a tr li
phn ng thng qua my nn (7), cn mt phn nh i vo b phn
tch CO2. Sn phm y ca (5) v (6) s a vo cng on chng
tch ct chng phn on (9).
Vinyl axetat l cht lng, nhit si 720C, to vi khng kh hn
hp n. y l mt trong nhng monome quan trng, khi trng hp s
to thnh polyvinylaxetat:
-C H 2 -C H - n

OCOCH3

Polyme ny c tnh bm dnh cao v c ng dng trong sn xut keo

dn v vecni. Khi thy phn polyvinylaxetat, s thu c mt polyme rt
thng dng khc, l polyvinylancol
-C H 2 -C H - n

OH

polyvinylancol c s dng lm cht nh ha v cht tng nht cho

cc dung dch nc. Thy phn mt phn polyvinylaxetat s thu c
polyme d to mng v c th dng lm vi gi da. Ngoi ra, cc
copolyme ca vinylaxetat vi vinylclorua v cc monome khc cng
c ng dng rng ri trong k thut.
5.4. Hyrat ha etylen. Tng hp etanol
5.4.1. C s l thuyt
khc phc nhc im c bn ca phng php cng nc vi xc
tc H2SO4 qua giai on to thnh ankylsunfat, ngi ta tm ra
phng php cng nc vo olefin mt giai on: kt hp phn t
nc trc tip vo ni i vi s c mt ca cc xc tc axit khc.
Ngoi ra phng php thy phn trc tip cn c u im v mt cng
ngh (qu trnh ch tin hnh qua mt giai on, khng cn thit b ti
sinh H2SO4), hiu sut to thnh ancol cao hn (=95%) v s n mn
thit b t hn.
Xc tc thng dng nht thy phn trc tip olefin l axit photphoric
tm trn cht mang (silicagen xp, aluminosilicat). S la chn cc
thng s k thut da vo nhng ch tiu kinh t, nht l gim tiu hao
nng lng trong qu trnh to hi v s dng li lng cc cht cha
tham gia vo phn ng. Nhit cao y gy cc nh hng tri
ngc nhau n cn bng phn ng v tc ca n. Ngoi ra nng
nhit cn thc y s polime ha olefin v lm cho H3PO4 d tch ra
khi cht mang. V vy s cng nc vo etylen nn tin hnh nhit
260 3000C v gi nng cn thit ca axit photphoric trn
139

cht mang phi cn p sut hi nc khong 2.5 3Mpa. tng

chuyn ha ca hi nc, tng nng ca ru, ni cch khc
gim chi ph v nng lng ngi ta dng mt lng d etylen (1.4 1.6 : 1). Khi s dng etylen vi lng d ny cn p sut 7 8Mpa, khi
chuyn ha ca etylen trng thi cn bng l 8 10%. Tuy vy
trong thc t, chuyn ha ch t khong 4% v iu ny cho php
qui trnh lm vic vn tc th tch cao (200/h) v hiu sut ca xc tc
tnh theo ru (180 220kg/m3.h), etanol thu c c nng 15%.
S lm long olefin bng hn hp tr s khng c li cho cn bng v
vn tc phn ng. V vy khc vi qu trnh cng nc bng xc tc
H2SO4, y i hi olefin a vo phn ng phi c nng cao (97
99%). Tt nhin sau nhiu vng tun han hn hp cc khi tr c
tch t nhiu, nhng phi b sung thm mt lng olefin sao cho nng
ti thiu ca n phi t 85%.
Phn ng c tin hnh trong thit b hot ng lin tc c cu to
nh mt ng thp ng knh 1.5m, chiu cao 10m, bn trong ng
c ph mt lp ng trnh s n mn ca axit photphoric. Xc
tc c a vo ng v cha trn cc ng nh hnh nn. Hn hp
olefin v hi nc sau khi un nng n nhit thch hp s i vo t
pha trn thp, chy qua cc lp xc tc v i ra thp t pha di. Do
chuyn ha ca olefin kh thp v nhit phn ng khng ln nn
khng cn thit b lm lnh trong thp.
Trong qu trnh lm vic, axit photphoric t t ra khi cht mang, do vy
sau khong 400 500h hot ng, xc tc s mt hot tnh, ti sinh
xc tc c th tip tc tm ln b mt n mt lng axit photphoric mi,
tuy nhin sau mt thi gian di hot ng trn b mt cht mang s c
nhng vng b nha ha, v bn thn zeolit cng tr nn qu gin. Xc
tc mi c th chun b bng cch tm ln cht mang axit photphoric
nng 60 65%, sau sy nhit 1000C. Xc tc s cha
khong 35% axit photphoric t do.
S cng ngh tng hp etanol
Do chuyn ha ca cc cu t thp, nhit v p sut cao, nn
trong qu trnh cng nc vn tun hon cc tc cht v tit kim
nng lng c ngha c bit quan trng. Cho n nay cc s
cng ngh ang hot ng rt khc bit nhau, ch yu ngun gc ca
hi nc cho phn tn v mc tinh khit ca sn phm.
Hi nc vi cc thng s cn thit c to thnh t ngun nng
lng khc hoc c sinh ra ngay trong thit b hp th v c tun
hon nhiu ln.

140

5.4.2. S cng ngh qu trnh tng hp etanol

Hnh 5.9. S cng ngh tng hp etanol

1, 2 My nn, 3 L t dng ng, 4 Thit b trao i nhit, 5 Thit b phn ng, 6
Thit b tch mui, 7 Thit b lnh, 8, 10 Thit b phn tch, 9 Thit b hp th, 11 Ct
tch phn on nh, 12 Ct tch etanol, 13 Thit b lc nc tun hon bng phng
php trao i ion, 14 My bm,
15 Van tit lu, 16 Thit b ngng t.

5.5. Halogen ha etylen. Tng hp vinyl clorua

5.5.1. c im ca qu trnh
Phng php cn bng theo clo sn xut vinyl clorua t etylen l
phng php quan trng trong cc qu trnh clooxy ho. N l s kt
hp ca ba qu trnh:
- Cng hp trc tip clo vo etylen to thnh 1,2 dicloetan.
- ehyroclo ha nhit 1,2 dicloetan thnh clorua vinyl.
- Clooxy ha etylen thnh 1,2 dicloetan vi qu trnh tham gia ca HCl
to ra khi ehyroclo ha.
CH2=CH2 + 2HCl
ClCH2-CH2-Cl

ClCH2-CH2-Cl
CH2=CHCl + 2HCl

CH2=CH2 + 2HCl + 0.5O2

ClCH2-CH2-Cl + H2O

CH2=CH2 + 2HCl + 0.5O2

CH2=CHCl + 2H2O

141

Qu trnh tng hp t etylen, clo v oxy, s nhn c clorua vinyl.

Trong , clo c s dng hon ton v khng to thnh HCl. Phng
php ny, khng cn s dng axetylen t tin, gi thnh monome
nhn c gim t 25 30% so vi phng php hyroclo ha
axetylen.V vy, hin nay n l phng php kinh t nht tng hp
vinyl clorua.
5.5.2. S cng ngh tng V.C theo phng php t hp
S cng ngh tng V.C theo phng php t hp c biu din
trn hnh 5.9.
Phn ng cng hp clo trc tip vo etylen thnh 1,2 dicloetan
thc hin trong thp clo ha (1). y, clo v etylen c cho vo qua
cc li sc kh tng ng. Trong thp, mc cht lng lun thay i,
xc tc (FeCl3) ha tan trong cht lng ny. Nhit phn ng lm bay hi
1,2 dicloetan, hi ca n thot ln pha trn v ngng t trong thit b
lm lnh ngng t (2). Phn ngng chy xung bn cha (3). T y,
mt phn ca n cho hi lu tr v thp ( gi ch nhit bnh
thng cho phn ng v mc cht lng khng i), cn phn cn li th
mang i chng ct phn on. Trong bn cha (3), t phn ngng s
tch c cc kh cn li, cc kh ny, c th c lm lnh b sung
bng dung dch mui trong thit b lm lnh (2), hn ch qu trnh
mt mt 1,2 dicloetan. Kh thot ra t thit b lm lnh ny, c
mang i lm sch v sau thi vo kh quyn.
Giai on oxyclo ha tin hnh trong thit b phn ng (5) vi lp xc
tc gi lng, di p sut 0,5MPa nhit 260 2800C. Kh etylen
hi lu v clorua hyro, c trn s b trong ng, sau l trong thit
b trn (4), oxy k thut s b sung vo thit b ny. Cn phi khuy trn
m bo t c thnh phn hn hp cn thit, trnh gy n cho
qu trnh lm vic. Trong thit b phn ng (5), nhit ta ra c lm
bay hi nc ngng, v s thu hi c hi nc qu nhit. Hi ny
li c s dng cho h thng thit b ny.
Cc kh phn ng bao gm etylen cha chuyn ha, oxy v clorua
hyro cng nh hi 1,2 dicloetan v tp cht kh tr s c lm lnh
trong thit b lm lnh (6) bng hn hp nc v 1,2 dicloetan hi lu
t thit b lm lnh (7). Mt phn hn hp hi, kh lm lnh c tinh
ch ra khi HCl v CO2 trong thit b lc kh t chy bng kim (9) v
s c lm lnh ln cui trong thit b phn ly (11), sau hi lu kh
tun hon (hn hp etylen, oxy v cc cht tr) v qu trnh oxyclo ha
nh my nn (13).
Phn ngng t thit b phn ly (11), chuyn sang thit b phn ly (12).
y, s tch c phn nng hn l 1,2 dicloetan ra khi nc. N
c s dng pha long cht kim dng lm sch kh trong thit b
lc kh (9).
142

Hnh 5.10. S cng ngh tng hp vinylclorua theo phng php t hp.
1 - Thit b clo ha; 2, 7, 10 - Thit b lm lnh; 3 - Bn cha; 4 - Thit b trn;
5 - Thit b phn ng; 6, 20 - Thit b lm lnh, khuy trn trc tip;
8 Bm hon lu; 9 - Thit b lc kh; 11, 12 - Thit b phn ly; 13 My nn;
16, 21, 22 Thp chng ct; 17 - Thit b nh lng; 18 Bm; 9 - Bung t; 13 Van
tit lu.

143

1,2 dicloetan thu nhn khi oxyclo ha c bo ha bng nc,

nn n cn phi x l tip theo trong thp sy (14) vi qu trnh h tr
ca ni un (15), thit b lm lnh ngng t (2) v thit b phn ly (12).
Sau khi c hai dng 1,2 dicloetan t cc giai on clo ha trc tip v
oxyclo ha khng b chuyn ha khi nhit phn, s c phi trn vi
nhau. Trong thp chng phn on (16), s chng tch c 1,2
dicloetan ra khi cc clorua bc cao v n s c thu hi trong thit b
nh lng (17) vi tinh khit cao. Qu trnh nhit phn 1,2
dicloetan thnh clorua vinyl v HCl tin hnh trong bung t ng (19)
p sut 1,5 2 MPa v nhit 5000C. Cc kh phn ng, c lm
lnh trong thit b lm lnh (20) bi 1,2 dicloetan tun hon v sau
l trong thit b lm lnh ngng t (20) bi nc. Tip theo, hn hp s
tham gia vo thp chng ct phn on (21) vi qu trnh h tr ca ni
un, thit b lnh ngng t v thit b phn ly (11). p sut trong thp
cho php ngng t HCl di dng dung dch v tin hnh tinh ch sn
phm tinh khit ra khi HCl . Kh HCl ny, c chuyn sang qu trnh
oxyclo ha. Cht lng y thp (21) gm clorua vinyl v 1,2
dicloetan cha chuyn ha c a qua thp (22), lm vic di p
sut bo m ngng t clorua vinyl v chng tch n ra khi 1,2
dicloetan cha chuyn ha. 1,2 dicloetan ny, c hi lu tr v qu
trnh chng ct phn on.
Clorua vinyl nhn c c hm lng tinh khit 99,9% v y l mt
iu thun li cho qu trnh polyme ha tip theo.

144

CHNG 6: TNG HP TRN C S PROPYLEN

6.1. Oxy ha propylen. Tng hp acrolein, axit acrilic (oxy ha theo
nguyn t cacbon no)
Ngi ta iu ch acrolein v axit acrylic bng phng php ny
CH2 = CH - CH3

+ O2
- H2O

CH2 = CH - CHO

+ 0.5O2

CH2 = CH - COOH

Acrolein l cht lng c mi kh chu (nhit si 52.50C). N tan tt

trong nc v to thnh hn hp ng ph. Khi bo qun lu v nung
nng acrolein d dng b trng ngng thnh polyme vng hay thng. V
vy khi x l ngi ta phi thm vo cc cht c ch v cc ph gia.
Acrolein c s dng iu ch axit acrilic v este ca n vi ru
alinlic, glyxerin tng hp v cc sn phm khc, trong s c
metionyn CH3SCH2CH2CH(NH2)COOH l cht quan trng trong thnh
phn thc n ca cc loi lng v.
i vi axit acrylic v este ca n, ngi ta iu ch chng t
acetanehit v axit cianhyrdic (HCN), sau t acrylonytril nhng do
nguyn liu t tin, v to thnh axit sunfuric v amonisunfat nn
ngi ta thay bng phng php oxy ha trc tip propylen.
6.1.1. c im qu trnh oxy ha propylen iu ch acrolein
Qu trnh ny km theo s to thnh cc sn phm ph: acetanehit,
aceton, axit acetic v acrylic, CO v CO2. Cng nh cc qu trnh oxy
ha xc tc d th, oxit cacbon thng c to thnh khng ch t
acrolein m c phn ng oxy ha song song trc tip propylen.
tin hnh chn lc qu trnh, iu quan trng l cn phi c cc xc
tc nh hng phn ng oxy ha to thnh acrolein. Mt trong cc xc
tc l oxit ng (I) ph trn cc cht mang (0.1 1.5%Cu2O trong
bt, cacbuasilic hay Al2O3) hay thm ch thit b ng ng. Sau ny
ngi ta tm ra cc xc tc t molipdat bismut (Bi2O3 . MoO3)v phot
pho molipdat bismut (BI2O3.MoO3.P2O5) c cha cc cht tng hot (oxit
v ng). Khi thi gian tip xc ngn v nhit thp, bng cc cht
xc tc ny chn lc cao cn thit s t c. Nh bng oxit ng
(I) thi gian tip xc l 0.5h 370 4000C hay 2h 320 3500C. Nu
s dng molipdat th nhit cao hn (400 500C) trong thi gian tip
xc 1 2h. Cc thng s ny s ph thuc vo p sut s dng mc
no v thay i t 0.1 1Mpa. Thnh phn hn hp ban u khng
c vt qu gii hn nng gy n nguy him. V vy trong thit b
phn ng ngi ta thng a vo hn hp mt lng hi nc (25
50% th tch), hi nc cng gp phn lm tng la chn do n gip
cho qu trnh gii hp ph acrolein.
Ngi ta s dng oxy k thut hay khng kh lm tc nhn oxy ha.
Khng kh r hn oxy k thut nhng n lm long hn hp kh v gy
145

kh khn cho s tch loi v hon lu cc cht. T l propylen v oxy

(khng kh) trong hn hp ban u c th khc nhau: c nhng thit b
lm vic vi lng d propylen (42 44% th tch C3H6, 8 10% th
tch oxy, 46 50% th tch nc), ngc li cng c mt s thit b lm
vic vi lng d oxy hay khng kh (7 8% th tch C3H6, 67% th
tch oxy, 25% th tch nc). R rng trong trng hp u cn phi c
s i lu propylen khng chuyn ha, iu ny gii thch ti sao ngi
ta khng s dng khng kh m phi s dng oxy. Mc chuyn ha
theo tc cht thay i t 60 100% cn la chn 70 90%.
Phn ng c tin hnh trong cc thit b khc nhau nhng thng s
dng thit b v ng vi lp xc tc c nh c lm lnh bng mui
nng chy. Hn hp nng chy c tun hon qua ni xupde tn
dng ph liu ng thi ti sinh hi p sut cao. Cc kh phn ng sau
di chuyn qua thit b hp ph, y cc sn phm ca s oxy ha
c hp th bng nc v nhn c dung dch acrolein nng 1.5
2%, trong dung dch ny c cha acetanehit v aceton v mt lng
nh anehit propionic. Acetanehit d dng tch ra bng chng ct
phn on cn tch acrolein ra khi anehit propionic c nhit si
gn vi n (490C) ngi ta s dng qu trnh trch ly bng nc.
Acrolein thu c cha 99% cht chnh vi tp cht l nc v anehit
propionic.
6.1.2. Oxy ha acrolein. Tng hp axit acrylic
oxy ha acrolein thnh axit acrylic ngi ta cng s dng cc cht
xc tc l oxit bismut molipden vi cc cht ph tr khc (Te, Co, P)
nhng iu kin phn ng du dng hn: nhit 200 3000C vi thi
gian tip xc 0.5 2h. Khi la chn ca qu trnh ln hn 90% s
to ra cc sn phm ph l CO2, axit axetic.
tin hnh trong cng nghip thun tin, ngi ta thng kt hp s
oxy ha propylen thnh acrolein v oxy ha acrolein thnh axit acrylic.
Lc u ngi ta tin hnh qu trnh mt giai on oxy ha trc tip
propylen thnh axit acrylic trong cng mt thit b phn ng gim vn
u t. Hiu sut ca axit acrylic khi t khng cao (<70%). V vy
s phi hp gia 2 giai on vi cc iu kin ti u khc nhau khng
th lm tng la chn cho c qu trnh
Hin nay qu trnh 2 giai on thng c s dng nhiu nht
(hnh) Trong thit b phn ng 1 ca giai on u tin ngi ta a
vo hn hp 4 7% th tch propylen, 50 70% th tch khng kh v
25 40% th tch hn hp nc. Trong xy ra ch yu qu trnh oxy
ha propylen thnh acrolein 300 4000C. cc kh phn ng khng
c phn tch m chuyn sang thit b phn ng 3 ca giai on 2,
y nhit l 250 -3000C v xy ra s oxy ha acrolein thnh axit
acrylic. C 2 thit b phn ng u l thit b dng ng vi lp xc tc
146

n nh v c lm lnh nh qu trnh lm nng chy mui. Nhit ca

mui nng chy ny c dng to ra hi nc trong thit b 2. Cc
kh phn ng sau thit b 3 c x l bng nc trong thit b hp thu
4, y s hp thu axit acrylic cn kh th thi ra ngoi.
Dung dch nc nhn c cha 20 -30% khi lng axit acrylic v
mt t axit acetic. tch sn phm chnh ngi ta s dng qu trnh
trch (trn s khng biu din) bng mt lng dung mi hu c c
nhit si thp va . Dung mi ny s c chng ra khi hn hp
trch v a tr v qu trnh trch, cn khi chng ct phn on cn li
s nhn c axit acrylic v acetic. Hiu sut axit acrylic t 80 85%
theo propylen.
C3H6
Khng kh

hi

hi
3

hi

4
H2O

H2O

H2O
Sn
phm

Hnh 6.1. S hai giai on oxy ha propylen thnh axit acrylic

1 Thit b phn ng giai on 1, 2 Thit b tn dng ph liu, 3 Thit b phn ng giai
on 2, 4 Thit b hp th.

6.1.3. Oxy ha amoni propylen. Tng hp acrilonitril

Acrylonitril l mt cht lng (nhit si 77.30C), tan hn ch
trong nc (7.3% ti 200C) v to vi nc mt hn hp ng ph bao
gm 12.5% nc v si 70.70C. Acrylonitril to vi khng kh mt hn
hp n trong gii hn 3.0 17.0% (th tch). Hp cht ny c s
dng ch yu di dng monome trong sn xut si tng hp
polyacrylonitril (nitron), copolyme vi metacrylat (acrylon). Vi vinyl
clorua (Vinom N), sn xut cht do copolyme vi styren v cao su tng
hp ABS. Ngoi ra acrylonitril cn l sn phm trung gian trong tng
hp cc acrylat v acrylamit
Phng php sn xut cng nghip u tin ca acrylonitril l i t
etylen oxit v HCN, sau ny ngi ta chuyn qua nguyn liu acetylen
147

v HCN
C hai phng php trn u tr nn lc hu do xut hin phng
php oxy ha amoni da trn nguyn liu r tin propylen
Oxy ha amoni propylen
Trc y xc tc cho qu trnh molipdat bismut (Bi2O3 : MoO3 = 1 : 2).
Sau ngi ta thm cht hot ha xc tc l P2O5. Hin nay c nhiu
loi xc tc khc nhau vi nhiu thnh phn rt a dng nh
vanadimolipdat bismut, uran antimortrn cc cht mang nh SiO2,
Al2O3
Cc xc tc ny u lm vic theo c ch oxy ha - kh v vn tc
phn ng ch ph thuc vo p sut ring ca propylen ( r = k.pC3H6),
chng t giai on chm nht ca qu trnh l s tc dng ca propylen
vi tm hot ng ca xc tc.
Cc sn phm ph ca qu trnh oxy ha amoni l HCN, CH3CN v mt
lng nh HCHO v CH3CHO (to thnh do oxy ha phn hy
propylen) cng nh CO2. Trc y ngi ta cho rng nitril c hnh
thnh qua giai on trung gian anehit, hin nay chng minh c
rng chng c to thnh song song vi nhau. S phn ng
chuyn ha propylen trong qu trnh oxy ha amoni c th biu din
nh sau:
+ O2, + NH3

CH2 = CH - CH3

+ O2

+ O2

CH2 = CH - CHO
+ NH3
CH2 = CHCN

+ O2, + NH3

+ O2
CH3 - CHO + HCHO

CO2

+ NH3
CH3CN

+ NH3
HCN

Nh vy dioxit cacbon c to thnh bi s oxy ha tt c cc cu t

c trong hn hp v ch yu t propylen. Khc vi propylen v anehit,
oxy ha hon ton nitril xy ra vi vn tc nh, v vy tnh la chn s t
ph thuc vo mc chuyn ha.
Qu trnh oxy ha amoni propylen trc y c thc hin trong thit
b phn ng dng ng vi tng xc tc c nh, sau ngi ta chuyn
qua thit b vi tng xc tc gi lng. iu ny cho php iu chnh nhit
tt hn, loi b c vn n ca hn hp v khng phi pha
long bng hi nc. S oxy ha xy ra di tc dng ca khng kh
vi t l (th tch) C3H6 : NH3 : O2 = 1 : (0.9 1.1) : (1.8 2.4). iu quan
trng l phi m bo trong hn hp i ra t thit b phn ng c mt
148

mt lng NH3 cha chuyn ha v trong trng hp ngc li hiu

sut to thnh anehit v CO2 s tng ln. Ngoi cng cn dng mt
lng d oxi v cng vi propylen v amoniac, n m bo tnh cht
oxy ha kh ca mi trng phn ng, to iu kin tng tnh la chn
ca xc tc.
Qu trnh oxy ha amoni propylen thng c thc hin nhit
370 5000C, 0.2 1.4Mpa, iu kin ti u c th l 420 4700C v
0.2Mpa, thi gian tip xc khong 6s, chuyn ha t 80%. Trong
phn on propylen c th cha 5 40% propan, do vy lm gim gi
thnh ca n. la chn theo acrylonitril cc iu kin trn l 80
85%, ngoi ra nu c to thnh axit cianic v acetonnitril th chng cng
c xut xng di dng thng phm. Do vy gi thnh ca sn
phm chnh acrylonitril cng s gim. nhng cng ngh khc nhau,
lng HCN v acetonnitril l 50 200 v 25 100kg/1tn acrylonitril.
Mt trong nhng s cng ngh sn xut acrylonitril c biu din
trn hnh 6.2.
Kh

H2SO4
H2 O
(h)

7
5

4
8

(NH4)2SO4

H2O
(l)
3

16

1
C3H6
2
NH3
(l)

11
H2O
(h)
10

15

12
14

HCN
13

Etylen glycol
+ nc
H2O
(l)

17
CH3CN

Hnh 6.2. S cng ngh sn xut acrylonitril

1, 2 Thit b bc hi, 3 Thit b phn ng, 4 Ni hi, 5, 6 Thit b hp th, 7 Sinh
hn, 8 Thit b trao i nhit, 9 Ct bay hi, 10, 15 Ct chng ct phn on, 11 Ct
trch ly, 12, 14 Thit b tch, 13 Ct sy ng ph, 16 - Thit b trao i nhit nhgng t,

149

17 Thit b un nng.

Amoniac lng v phn on propylen c bc hi trong thit b 1

v 2 vi s c mt ca etylenglycol (EG) v nc; hn hp nc c
lm lnh xung nhit thp v hi lnh c ti s dng. Amoniac
kh, phn on propylen v khng kh vi t l thch hp c a vo
thit b phn ng 3 vi lp xc tc gi lng. Thit b ny c lm ngui
bi hi nc ngng t. Nh nhit ca phn ng s ti sinh hi p sut
cao s dng ngay trong qu trnh chng tch sn phm. Kh nng i ra
t thit b phn ng c qua ni hi 4 ti sinh hi p sut trung
bnh.
Kh phn ng lm lnh mt phn trc tin c lm shc
khi NH3 trong thit b 5, ti y dung dch sunfat amoni trong axit
sunfuric c tun hon lin tc. Sau mt thi gian s dng, dung dch
ny c ti sinh v kt tinh, s thu li c khong 400kg
(NH4)2SO4/1tn acrylonitril. Tip tc t trong kh trong thit b hp thu 6,
nc s hp thu acrylonitril, axit cianit v acetonnitril. Cn hk thi t
thit b ph thuc vo thnh phn m c th t chy iu ch hi
nc hoc thi ra kh quyn.
Phn dung dch nc t di y thit b 6 c a qua un nng ti
thit b trao i nhit 8, sau cho bc hi ti thit b 9, ti y ngi ta
chng tch cc sn phm khi nc. Nc chng tch c s a v
tr li thit b 6, cn hn hp sn phm tip tc x l.
Thng thng t hn hp sn phm ngi ta tch HCN c nhit
si thp nht trc tin trong ct chng ct phn on 10 trong chn
khng. Sau t sn phm y ca thp 11, ngi ta chng tch hn
hp ng ph ca acrylonitril vi nc, cn li l dung dch nc ca
acetonnitril v cc tp cht nh cyanohydrinformanehit c to thnh
do HCN tc dng vi anehit. Dung dch ny c tch thnh 2 lp
nc v lp hu c trong thit b 12, lp nc s c a tr li thp
11.
Dung dch acrylonitril vi nc c sy trong thp 13 c gn b phn
tch 14 tch nc v acrylonitril. Nc s a hi lu v thp 11 (v
cn cha mt lng acrylonitril). Acrylonitril kh s tip tc c lm
sch ti tinh khit cn thit trong cc thp 13 v 15. Ti mt s on
thc sn phm, trnh s trng hp ca sn phm, ngi ta thm vo
mt lng cht c ch.
6.2. Halogen ha propylen. Tng hp allyl clorua.
Allyl clorua CH2=CHCH2Cl v metalyl clorua CH2=C(CH3)CH2Cl l
cht lng si 450C v 72,20C. Cht u c dng a nhm allyl
vo nhng cht khc nhau (tng hp ete c nhm allyl, allylamino,
allylsacaro v c bit sn xut epiclohyrin CH2ClCH-CHO, l
nguyn liu chnh trong tng hp nha epoxy v glixerin.
150

6.2.1. iu kin ca qu trnh v cc loi thit b phn ng

Bt chp s vng mt hoc qu trnh tc ng c ch yu ca oxi,
trong clo ha pha lng, tt c phi dng clo thu c khi ha hi clo
lng. V vy, khi hi lu phn hyrocacbon cha phn ng, tp cht tr
ca kh clo phn ly, to iu kin nhanh chng tch t chng li n gii
hn khng cho php.
iu quan trng l phi chn nhit v t l cht phn ng. Khi tng
hp allyl v metalylclorua, l sn phm chnh c cha mt nguyn t
clo, do qu trnh thc hin vi d hyrocabon, nhng khng qu ln,
bi v diclorua cng c th dng c. Nu t l mol hyrocacbon vi
clo l 5:1 khi tng hp allylclorua v 2:1 khi iu ch metalylclorua, hiu
sut nhng dn sut clo ny t ti 80%, khi lng hyrocacbon
c tch ra v cho quay ra tr li phn ng. Khi sn xut allylclorua,
vic chn nhit c quy nh bng chn lc cao ca qu trnh
thay th so vi phn ng cng v phn ng xy ra khng nhiu, qu
trnh thc hin 150 2000C. Cui cng, tng hp diclobuten thc hin
nhit gn 3000C v d butaien -1,3.
Khi clo ha metan th sn phm chnh thng l metalenclorua,
cloruaform, tetraclometan hoc hn hp ca chng. Khi metylenclorua
l sn phm chnh, t l mol ca metan vi clo l ~ 4:1. Clo ha nhit
metan thc hin 500 5500C, cn bng nhit cng vi s c mt xc
tc th 350 4000C.
Clo ha trong pha kh lun c thc hin p sut khng kh v
lin tc cho hn hp cht phn ng qua thit b clo ha. Cng on
quan trng l trn nhng cht ban u, phi m bo c c hn hp
ng nht ngay tc khc. Do , phi c thit b trn c bit v d nh
loi tip tuyn, n c dng xoy mnh v khuy u hn hp.
Cc thit b phn ng cho clo ha pha kh c 3 loi chnh (hnh
4.4). c im chung ca chng l lp bo v v thp, (khi tc dng
ca nhit cao v n mn) bng lp lt l bng s . Tc dng cui
cng ca n l dng nhit ca phn ng t nng hn hp n nhit
cn thit v ta nhit vo mi trng xung quanh. Khi , ty vo
cn bng nhit ca qu trnh m cho lng cht phn ng lm lnh vo
thit b clo ha, (khi tng hp polyclorua metan, hiu ng nhit ca phn
ng rt ln) hoc gia nhit s b ( thu c alylclorua).
Trong trng hp u ca clo ha nhit, ngi ta dng thit b clo
ha loi 4.4a, trong cht phn ng lnh c gia nhit nhanh nh
vi phun nng ng vai tr bnh tr nhit. Khi clo ha nhit xc tc cng
tin hnh nh vy nh nhng cu t nung nng ca lp xc tc gi
lng hoc nh cht truyn nhit (4.4b). Khi , tng hp cc qu
trnh ta nhit mnh nh policlorua metan, qu trnh iu chnh nhit
c th nh s phun CCl4 lng. Trong tt c cc trng hp u c s
151

khuy trn hn hp theo chiu dc rt mnh. Tng hp allylclorua, phn

ng c th bt u xy ra khi khuy trn, v ngi ta dng thit b clo
ha dng ng rng vi chiu cao so vi ng knh rt ln (4.4c).
Thi gian lu trong nhng qu trnh clo ha khc nhau thay i trong
khong 0,1 2 giy.

Hnh 6.3. Thit b phn ng clo ha trong pha kh.

a - Thit b phn ng vi tc nhn nhit rn
b - Thit b phn ng vi lp ti nhit gi lng
c - Thit b phn ng vi s un nng s b hn hp.

6.2.2. S cng ngh ca qu trnh

S cng ngh clo ha pha kh gm nhng giai on nh clo
ha pha lng. Chun b cht phn ng gm ha hi clo lng, t nng
s b clo dng kh, sy cht phn ng vi nhau v vi lng hon lu.
Trong trng hp allylclorua v metalylclorua, ngi ta ha hi v t
nng hyrocacbon ban u n nhit cn thit.
Sau phn ng, lm sch hn hp khi HCl, tch nhng cht hi lu v
sn phm chnh. thc hin nguyn cng on ny, ngi ta dng 2
s c bn.
1. Khi kh ngng t sn phm (nh khi tng hp metylenclorua trong
lng d CH4 ln). u tin, ngi ta lm sch tt c hn hp khi HCl
v thu c HCl 30%, sau nn li, sy, tch phn kh hi lu v
chng ct sn phm lng.
2. Khi c kh nng d dng ngng t sn phm, u tin, ngi ta tch
chng khi phn hi lu v HCl, sau chng ct. Hn hp kh c
lm sch khi HCl, cn phn hi lu cho sy v cho quay li phn ng.
152

C3H6 + HCl
H2O

11

H 2O

H2O
9
HCl
2

10

NaOH

Cl2
(h)

1
7
17
14

6
12

3
Mui
than

Clorit

19

15 16

C3H6 (l)
13

18

Hnh 6.4. S cng ngh sn xut allylclorua.

1 - Thit b ha hi; 2 - Thit b gia nhit; 3 -L ng; 4 - Thit b clo ha;
5 - cyclon; 6, 17 - Sinh hn lm lnh; 7 - Thp tch hi ngng t;
8, 9, 12, 16 - Thit b tch; 14 - Thit b ngng t; 15 - Thit b sy hp ph;
18 - My nn kh; 19 - Van tit lu.

S cng ngh sn xut allylclorua c m t trn hnh 6.4.

Clo lng ha hi trong thit b (1) v c gia nhit s b trong thit
b gia nhit (2), sau chng qua lu lng k v vo thit b clo ha
(4). t nng propylen n 3500C trong l ng (3) v n i n pha trn
ca thit b clo ha, ng vai tr tc nhn trn. Hn hp phn ng
nng cho qua xyclon (5) tch cc v mui than, qua thit b lm lnh
(6) c th thu hi nng lng, sau vo thp tch hi ngng t (7).
Vi propylen lng, nh qu trnh ha hi ca n, m kh c lm lnh
v tt c dn xut clo c ngng t hon ton.
Propylen v HCl t pha trn thp (7), chuyn n hp th clorua
hyro thu c HCl m c. Theo hnh v, c s hp th dng
mng trong thit b v ng grafit (8), trong nhit hp thu c ly nh
nc v nh th thu c HCl c nng cao nht. Trong mi ngn
ca thit b hp th (8), kh v nc (hoc HCl) chuyn ng thng t
trn xung, nhng ng thi n c dng ngc do qu trnh cho nc
vo thit b hp th cui (theo ng kh) v cho axit long vo thit b
u. Sau khi qua thit b phn ly th 2, ngi ta lm lnh thm tch
153

khi HCl trong thit b lc kh kim (11), cn propylen cha phn ng

c nn trong thit b nn kh (18) n p sut 1,5 2,0MPa.
Lm lnh propylen trong ng sinh hn (17) v tch nc ngng t
trong b phn ly (16). Sau , kh cho qua sy v vo b hp ph (15)
cha Al2O3 (hiu lc ca cht sy l 2 3 chu k lm vic, trong
thc hin lin tc qu trnh hp ph, thi, gii hp ph bng kh nng v
li thi). Phn propylen kh trong trng thi kh c tit lu, n n l
ng (3) v t y i n phn ng. Khi lng cn li c ngng t
trong thit b (14) v c thu hi trong b (13). S tit lu propylen
lng xy ra, trong n c lm lnh v mt phn c ha hi.
Nhng hi ny cng kh t b (13), hp vi propylen i n phn ng,
v propylen lng ti cho thp (7).
Phn on propylen sch, ty thuc vo p sut ca n, trng thi
kt t v mc sy, c th cho vo nhng im khc nhau ca s
cng ngh. Cho phn on lng kh vo b (13) di p sut. Khi hon
lu, trong kh tch t nhng tp cht tr v trnh qu trnh ha long
nhiu ln, ngi ta cho thot ra mt lng kh vo ng kh nhin liu.
Hn hp dn xut clo t di thp (7) chuyn n chng ct (trong s
khng c). Khi allylclorua c tch khi clopropylen v diclorua
c nhit si cao hn, chng thu c dng sn phm k thut tinh
khit.
6.3. Hydrat ha propylen. Tng hp iso-propyl ancol
6.3.1. C s l thuyt
Cc phng php cng nc trc tip vo propylen tng i a dng
hn so vi trng hp etylen, trong c th k n phng php
cng hp pha kh vi xc tc axit photphoric (cng tng t nh
etylen). V kh nng phn ng ca propylen cao hn nn nhit phn
ng ch cn khong 2000C v p sut c th gim xung cn 2 3Mpa.
trnh vic sinh ra mt lng diisopropyl ete cn phi khng ch
chuyn ha ca hi nc khong 4 5%, nh vy sau khi phn ng s
thu c dung dch ru 15 20%. Ngc li, chuyn ha ca
propylen c th cao hn nhiu bng cch iu chnh thnh phn hn
hp phn ng ban u: trong sn xut isopropyl ancol, khc vi trng
hp cng nc vo etylen, ngi ta s dng mt lng d hi nc v
a chuyn ha ca propylen n 10 12%. Do vy cc ch tiu
kinh t - k thut trong sn xut y s cao hn so vi trng hp
etylen v nht l so vi phng php xc tc H2SO4.
Ngoi ra cn c phng php cng hp propylen pha lng vi xc tc
l cc sunfuacationit (l sn phm ng trng hp gia styren vi
divinyl benzen c sunfua ha, kch thc cationit 0.2 0.9mm). Xc
tc ny bt u hot ha s cng nc ca propylen nhit t =
130 1500C. p sut 6 10Mpa, t l mol H2O : C3H6 = (12.5 - 15) :
154

1, chuyn ha ca propylen t 75 80%, thi gian lm vic ca xc

tc l 8 thng.
6.3.2. H thng thit b phn ng
Phn ng c tin hnh ti mt thp vi 4 lp xc tc (hnh 6.5), trong
kh propylen, nc c i trc tip t trn xung qua cc lp
cationit. iu khin nhit phn ng gia cc lp xc tc, ngi
ta tin hnh cho thm mt lng nc
C3H6

H2O

Sn phm

Hnh 6.5. Thp phn ng cng hp nc vi propylen vi xc tc axit sunfuacationit

Mt phng php pha lng khc da trn c s xc tc axit poly

wonframic, nhit 240 2700C, p sut 15 20Mpa, chuyn ha
propylen t 60 70%, tnh la chn theo isopropyl ancol l 98%.
6.4.

Oxy ha n buten. Tng hp anhyric maleic (AM).

AM trc y ch yu c sn xut theo phng php oxy ha xc

tc d th benzen, trong qu trnh ph duy nht l to thnh CO2..

155

CO
+O2

CH

O +O2

CH
+O2

CO2

CO

S oxy ha tip AM xy ra tng i chm, do vy qu trnh tin hnh

n chuyn ha gn nh hon ton ca benzen.
Xc tc hu hiu nht cho s oxy ha benzen l hn hp oxit vanadi v
molipden trn cht mang Al2O3. Xc tc thng c bin tnh vi cc
oxit photpho, titan, bo. Vng nhit ti u l 350 4000C, hiu sut
AM 70 75%. Cng ngh sn xut AM ch khc cng ngh sn xut AP
(chng 7) giai on tch sn phm. Sau khi lm lnh, khong 50%
AM c ngng t trong thit b ngng t hoc trong cc cyclon. Lng
AM cn li s c nc hp thu to thnh dung dch 40% ca axit
maleic. Dung dch ny mang i c c v tch nc bng chng ct
ng ph. AM thu c sua mang i chng ct phn on nhm iu
ch AM tinh khit.
S chuyn ha nh sau:
+ O2

CH2 = CH - CH2 - CH3 - H CH2 = CH - CH = CH2

2
+ O2

CH3 - CH = CH - CH3

+ O2

CH3 - CH = CH - CHO

CH2
CH2

+ O2

CH2
CH2
CO
CH

CH
CO

Ngoi ra, cn to metylvinyl ceton, cc sn phm phn hy oxy ha

(acetnehit, formanehit, axitformic, acrolein) v CO2. Tnh la chn ca
qu trnh ny khng cao, ch khong 50%. Xc tc tt nht l V2O5 vi
ph gia photphat. Nhit phn ng: 440 5000C.
Ngoi nguyn liu n-buten, ngi ta cn ngh s dng cc cht sau
y lm nguyn liu: hn hp buten v butan, iso-buten hoc butadien,
cc hyrocacbon C5 v fufurol.
6.5. Oxy ha iso-buten. Tng hp metacrolein v axit metacrilic
Metacrolien c ng dng gii hn, v vy qu trnh c th s dng
156

ch yu tng hp axit metacrilic. N cng bao gm 2 giai on.

CH3
CH2 = C - CH3

CH3
+ O2
- H2O

CH2 = C - CHO

+0.5O2

CH3
CH2 = C - COOH

Giai on u tng t nh iu ch acrolein (chng 5), cng

to ra cc sn phm ph tng t nhng xy ra vi la chn nh
hn. tin hnh phn ng ngi ta s dng cht xc tc cha nhiu
cu t trn c s molipden c b sung cc oxit Bi, Co, Ni, Te, V, Sb, Fe,
P s oxy ha thc hin 350 4500C v p sut kh quyn khi pha
long hn hp iso-buten v khng kh bng hi nc. Mc chuyn
ha ca iso-buten c th t n 70 90%. Kt qu cn tt hn khi oxy
ha hn hp iso v n-buten, khi iso-buten u7o5c oxy ha thnh
metacrolein cn n-buten va oxy ha va dehydro ha thnh butadien
1,3.
CH2 = CH - CH2 - CH3

+ 0.5O2
- H2O

CH2 = CH - CH = CH2

3900C v thi gian tip xc l 4h s t c mc chuyn ha ca

olefin l 96 98%, khi la chn theo metacrolein l 80 90% v
theo butadien 1,3 l 90%.
Giai on th hai l oxy ha metacrolien thnh axit metacrilic, giai
on ny kh thc hin hn vi phn ng oxy ha acrolein. Trong c
hai trng hp u khng s dng s oxy ha gc mch do s trng
hp anehit khng no.Ngi ta s dng xc tc ng v bc trong qu
trnh tin hnh pha lng, s oxy ha bng cc peroxit axit v cc
phng php khc. Nhng thng hay s dng nht trong sn xut l
qu trnh oxy ha pha kh bng xc tc d th t chn lc cao.
Mt trong s l xc tc oxit photphat molipden vi ph gia l cc oxit
Te v Sb, cc ion NH4+, kim loi kim v kim th. 250 3500C, p
sut kh quyn v mc chuyn ha ca metacrolein l 80 90% s
t c chn lc theo axit metacrilic l 70 80%.
Phng php va trnh by iu ch axit metacrilic hin nay c
s dng nhiu trong cng nghip. N rt trin vng trong kinh t k
thut, v vy cn phi thay dn cc phng php khc sn xut axit
metacrylic v este ca n bng phng php ny.

157

Chng 7: TNG HP TRN C S BENZEN, TOLUEN, XYLEN

(BTX)
7.1. Ankyl ha benzen thnh etyl v iso propyl benzen.
Ankyl ha cc hp cht thm
7.1.1. c im ca qu trnh
Khi ankyl ha cc hp cht thm vi vi s c mt ca xc tc
bt k s xy ra s th ni tip cc nguyn t hydro v to thnh hn
hp sn phm vi mc ankyl ha khc nhau.
Ngoi phn ng chnh trn, c th xy ra phn ng ph nh phn ng
phn hy, nha ha nhm ankyl v polyme ha olefin, s nha ha s
tng mnh nhit cao v s phn hy nhng nhm ankyl to thnh
nhng sn phm ph c mch ankyl ngn hn nhng iu kin khc
nghit.
Qu trnh cng ngh ankyl ha benzen gm 2 giai on c bn: Giai
on khuch tn olefin qua lp xc tc v giai on ankyl ha
giai on 1, vn tc qu trnh ph thuc ch yu vo p sut, vo
s khuy trn gia olefin v xc tc v vo hot tnh ca olefin, cn yu
t nhit khng nh hng nhiu v nng lng hot ha ca qu
trnh nh. Giai on ny l giai on chm nht quyt nh vn tc ca
ton b qu trnh tng. Cn s ankyl ha li ph thuc ch yu vo
nhit v nng lng hot ha vo khong 63 KJ/mol.
Trong qu trnh, xc tc dn b gim hoat tnh do c xy ra mt s
phn ng ph, tch t sn phm ph c kh nng lin kt bn vng vi
xc tc (AlCl3) hoc to ra nhng phc kh cho proton.
Nhng cht ny thng l polyankylbenzen (nhit thp) v cc
vng a nhn, nha (nhit cao), v vy phi chn nhit phn ng
t c hiu sut ti a v s tiu hao xc tc t nht (tng hp ete
v iso-propylbenzen, chn T=1000C, khi tng hp dy ankyl di hn,
chn nhit hn ch s phn hy hay s a t vng v nha ha
158

(30 - 500C)
C hai phn ng ankyl v ankyl ha li u gim dn khi hot tnh
xc tc gim, mc gim ca phn ng ankyl li ln hn nn trong
phn ng s c mt lng polyankylbenzen cha kp tham gia phn
ng thun nghch, v vy ta phi gim nhp liu.
Bn cnh cc yu t trn th nguyn liu phi sy kh loi nc cn
tc nhn olefin c th chp nhn c v hm m
Xc tc clorua nhm a vo phn ng di dng phc xc tc lng.
Phc ny c chun b trong thit b c khuy v un nng nh theo
phng trnh phn ng sau:

2Al + 6C6H6 + 7HCl

(C6H6)6.Al2Cl6.HCl

7.1.2. Thit b ankyl ha v s cng ngh

Hnh 7.1. Cc loi thit b phn ng ankyl ha hydrocacbon thm

a Thit b ng chm, b H ni thit b ni tip, c Thit b dng ng

Thit b dng ng:

Tc cht vi xc tc c a vo t bn di, khuy to nh
tng tri ln trn v c lm lngh bng nc, sau phn ng h hp
c a qua thit b tch lp (phc xc tc v ankyllat), phi m bo
thi gian lu kt thc phn ng.
159

H ni tip gm 2-4 thit b phn ng:

Cc cht ban u c a vo thit b phn ng u tin , sau
hn hp phn ng s c chuyn n thit b k tip t bn hng,
gia 2 thit b c b phn tch s b, T=40-600C, thi gian lu ph
thuc vo cc iu kin gii nhit v yu cu cn t n cn bng
sn phm ankyllat l cao nht.
Thit b dng ng pha trong c cc tm chng n mn chu axit:
Hn hp tc cht a vo ti mc van tro bn hng, sau phn
ng hn hp phn ng s i qua van tro i vo b phn tch (lng
theo phng php trng lc).Nhit ca phn ng lm nng tc nhn v
lm bc hi benzen. Hi benzen cn ln trong sn phm kh c cho
quay tr li qua thit b sinh hn
Trong qu trnh ch nhit c thit lp t ng v nhit ph
thuc vo p sut v nng phn on olefin
Dy chuyn cng ngh sn xut etyl v iso propyl benzen.

Hnh 7.2. S cng ngh sn xut etyl v iso-propyl benzen

1 Bm; 2 B phn trao i nhit; 3 Ct sy benzen; 4, 10 Thit b ngng t; 5
B phn tch; 6 Thit b iu ch phc xc tc; 7 Thit b un nng; 8 Bn cha; 9
Thit b ankyl ha; 11 B phn tch kh; 12, 16 Thit b tch; 13 Thit b hp ph; 14

160

Thit b ti nc; 15 Sinh hn; 17, 18 Ct ra

7.2. ehydro ho cc hp cht ankyl thm sn xut styren v

ng ng.
7.2.1. Phn ng
C6H5 - C2H5 -H2

C6H5 - CH = CH2

Khi ehydro ha cc ankylbenzen trn cht xc tc ny thng

xy ra hng lot cc phn ng ph. Nh t etylbenzen to thnh
benzen v toluen, cn khi dehydro ha iso-propyl benzen th to ra cc
cht ph l etylbenzen, styren, toluen v benzen. Tng t dehydro
ha

dietylbenzen

to

ra

etylbenzenstyren,

etyltoluen,

metylstyrenDo nguyn nhn ny nn trong khi nhn c ngoi H2

cn cha metan, etan, etylen v oxit cacbon.
C6H6
r2
C6H5 - C2H5
r3

r1
r-1

r4
C6H5 - CH = CH2 + H2

C6H5 - CH3

r5

7.2.2. H thng thit b phn ng v s cng ngh

Hnh 7.3. H thng thit b phn ng ehyro ha etylbenzen

a Thit b phn ng n dng on nhit, b H 2 thit b phn ng vi qu trnh t nng

trung gian hn hp, c Thit b phn ng vi cc lp xc tc v hi nng cho vo tng giai

161

on.

S cng ngh sn xut styren

13
kh

Etyl benzen

6
7

styren

Hi nc

8
2
5

10

11

12

Nc
ngng

14

Khng kh
Etyl benzen
B nng

Hnh 7.4. S cng ngh sn xut styren

1 L ng; 2 Ni hi; 3, 4 Thit b trao i nhit; 5 Thit b phn ng; 6
Sinh hn; 7, 8 Thit b tch; 9, 12 Ct chng; 13 Thit b hi lu; 14
Thit b un nng.
7.3. Oxy ha ankylbenzen thnh hyroperoxit. Tng hp phenol
v aceton
Qu trnh sn xut hyroperoxit u tin mang tnh cht cng nghip
c tin hnh vo nm 1949 Lin X tng hp phenol v aceton.
Phng php ny c Xergev, Crugialov v Udris pht minh theo
phng php tng hp Cumol
OOH
C6H5 - CH - (CH3)2

+O2

C6H5 - C - (CH3)2

+H+

C6H5OH + CH3 - CO - CH3

Mt vi hyroperoxit c s dng nh l cc cht kch thch s trng

hp v trong mt thi gian gn y, gi tr ca chng cng tng ln nh
162

s pht minh ca qu trnh mi epoxi ha olefin.

7.3.1. iu ch cc hyroperoxit
Trong cng nghip hyroperoxit iso-propylbenzen (cumol) c iu
ch vi sn lng ln nht
Khi oxy ha hyrocacbon, cc peroxit s c to thnh theo c ch
gc mch ( trnh by chng 2). Cc cht c ch (phenol, olefin,
cc cht cha lu hunh) s km hm mnh n qu trnh, gy ra hin
tng gin on cm ng. V vy hyrocacbon ban u cn thit phi
lm sch k loi cc tp cht khng mong mun.
Khi iu ch hyroperoxit thng to thnh cc sn phm ph, ch yu
l ru v mt t xeton. Nh khi oxy ha ios-propyl toluen s nhn c
dimetylfenylcacbinol v aceton phenol, trong ru l sn phm k
tip ca s chuyn ha hyroperoxit cn ceton th s to thnh song
song vi n t gc peroxit
+ C6H5 - CH - (CH3)2

OO*

OOH

OH

C6H5 - C - (CH3)2

C6H5 - C - (CH3)2

C6H5 - C - (CH3)2
C6H5 - CO - CH3 + CH3O*
CH3O*

CH3OH

HCHO

HCOOH

CO2

Tng t nh vy khi oxy ha etylbenzen s nhn c metylfenyl

cacbinol C6H5HCOHCH3 v acetonfenon, t iso-butan s iu ch c
tec-butanol, aceton v metanol. Khi oxy ha m - v p-isopropyl toluen th
gnoi sn phm chnh l hyroperoxit (CH3)2CH-C6H4-CH2OOH v cc
sn phm ca s phn hy n tc l lm gim tnh chn lc. i vi s
oxy ha m - hay p-diisopropyl benzen s nhn c mt cch ni tip
mono v di hyroperoxit
OOH

OOH

OOH

(CH3)2-CH-C6H4-CH-(CH3)2 +O2 (CH3)2-CH-C6H4-C-(CH3)2 +O2 (CH3)2 + C-C6H4-C-(CH3)2

163

Khi s to thnh mt lng ln cc sn phm ph: ru, ceton v

diceton v cetonhyroperoxit
S tng cng tnh chn lc theo hyroperoxit s c kh nng nu
gim nhit v mc chuyn ha, cc thng s ny s c chn
theo phng php ti u ty thuc vo yu t kinh t ca qu trnh.
Nh khi oxy ha cc hyrocacbon thm (c nhnh ankyl) th chn nhit
t 100 1200C, cn khi oxy ha iso-butan t 120 1500C. Cn phi
gim nhit theo mc tch t hyroperoxit lm chm tc
phn hy n. hn ch s chuyn ha tip tc ca hyroperoxit th
phi gii hn mc chuyn ha t 10 30% (i vi etylbenzen), cn
i vi qu trnh iu ch dihyroperoxit ca di isopropylbenzen d
xy ra s tng mc chuyn ha ln 50 60%
iu ch hyroperoxit ca ankylaren, phn ln s dng cc thit b
phn ng dng thp mm hay cascad ca cc thp oxy ha. S oxy
ha c tin hnh bi khng kh p sut t 0.3 0.5MPa i vi
isopropylbenzen v t 5 8MPa i vi isobutan ( trng hp sau p
sut dng gi hn hp trng thi lng v lm gim s li cun cc
cht cng vi kh thot ra). Dung dch hyroperoxit v cc sn phm
ph nhn c trong hyrocacbon ban u thng tch hay ngng t
bng cch chgn tch hyrocacbon. Khi iu ch hyroperoxit ca
ankylaren, lm gim iu ny, ngi ta s dng va chn
khng su. lm gim thi gian lu li ca axit nhit cao v lm
gim s phn hy ca n th thng tin hnh chng tch hyrocacbon
trong cc thit b dng mng mng.
7.3.2. S phn hy hydroperoxit
Ngoi c ch gc t do, s phn hy hyroperoxit ca ankylaren cn c
kh nng xy ra di nh hng ca xc tc axit hay kim. Khi c mt
mt lng nh axit mnh (0.1% H2SO4), cc hyroperoxit s b phn
164

hy thnh phenol v cc hp cht cacbonyl. Phn ng din ra theo c

ch phc tp dng ion vi cht trung gian l cc cation.
OO+H2

OOH
C6H5 - C - (CH3)2

+H+

O+

C6H5 - C - (CH3)2 -H2O C6H5 - C - (CH3)2

Cation to thnh s chuyn v cng vi s dch chuyn ca nhm

phenyl n nguyn t oxi v s chuyn ha tip tc.Kt qu ca qu
trnh ny s nhn c phenol v aceton
O+

O+ H2

C6H5 - O - C+(CH3)2 +H2O C H - O - C - (CH )

6 5
3 2

C6H5 - C - (CH3)2
H OH

C6H5OH + (CH3)2CO + H+

C6H5 - O+ - C - (CH3)2

i vi cu to khc ca nhm ankyl bc hai s to thnh ng ng

ca aceton (metyletyl ceton) cn t hyroperoxit ca n-ankylbenzen th
to ra acetanehit v ng ng ca n.
Cc sn phm ph ca s oxy ha c xem nh l tp cht i vi
hyroperoxit (c bit l ankylfenylcacbinol) cng rt nhy vi xc tc
axit. V d khi phn hy hyroperoxit etylbenzen th dimetylphenyl
cacbinol s b tch nc to thnh metyl styren v ankyl ha to
thnh 2-hyroxy phenyl, 2 phenylpropan (cumylphenol). Ngoi ra mt
phn metyl styren s b dime ha
OH
C6H5 - C - (CH3)2

+H+

O+ H2
C6H5 - C - (CH3)2
-H

+H2O
CH3

C6H5 - C = CH2

C6H5 - C+ - (CH3)2
+H+

Dimer

C6H5 - C+ - (CH3)2
+ C6H5OH C H - C - (CH ) - C H OH
6 5
3 2
6 4

V cng s nhn c mt lng nh nha c cu trc phc tp hn.

165

Khi nng axit

v nhit cao s to ra kh nng chuyn ha

acetonphenol v aceton bi xc tc axit. V d nh theo phn ng

ngng t andol vi s tch loi nc sau .
2CH3 - CO - CH3

OH
CH3 - CO - CH2 - C - (CH3)2

- H2 O

CH3 - CO - CH = C - (CH3)2

S cng ngh tng hp phenol v aceton theo phng php Cumol

Hnh 7.5. S cng ngh tng hp phenol v aceton theo phng php Cumol
1 Thp phn ng, 2 Thit b lm lnh, 3 Thp ra, 4 h thng trao i nhit, 5
Thng cha, 6, 8, 11 Thp chng ct phn on, 7 H thng phn hy hyroperoxit
bng axit, 12 Phn ly, 13 B phn tch,

166

14 B phn un si, 15 van tit lu, 16 Bm.

7.4. Oxy ha p-xylen. Tng hp axit terephtalic

7.4.1. Phn ng v cc yu t nh hng n chn lc ca phn
ng
Axit terephtalic c cng thc phn t: C6H4(COOH)2, l tinh th,
nhit thng hoa 3000C. So vi cc axit dicacboxylic ca qu trnh
isome ha v ca benzen, n ha tan km hn trong nc v cc cht
lng hu c. Axit terephtalic v ete dimetyl ca n (dimetylterephtalat)
gi vai tr quan trng trong sn xut si tng hp labxan (tecilen), l
sn phm trng ngng ca n vi etylenglycol. iu ch axit
terephtalic, ngi ta s dng nguyn liu l p-xylen. Do p-xylen c gi
thnh tng i cao, nn ngi ta thay n bng hng lot phng
php tng hp axit terephtalic t toluen. Mt phng php bao gm:
iu ch n-toluilanehit v oxy ha n thnh axit.
C6H5 - CH3

+CO(HF.BF3)

CH3 - C6H4 - CHO

+O2

HOOC - C6H4 - COOH

Trong phng php khc, ngi ta thc hin phn ng chuyn khng
cn i mui ca axit thm 400 4500C vi xc tc l cacbonat, oxit
hay mui hu c cadimi:
2C6H 5 - COOK

KOOC - C 6H4 - COOK + C6H6

Cc phng php nghin cu trong kh quyn, xc nh rng cc

qu trnh ny xy ra theo c ch phn tch CO2 v cacboxyl ha k tip
nhn thm, nh kh nng gy ra hiu ng cm ng m ca ion
cacboxylat.
COO+CO2

H
OOC

COO-

-H+

OOC

COO-

V vy, qu trnh s tin hnh thun li hn di p sut CO2 (0.3

1MPa).
Bng phng php ny, t toluen qua axit benzoic v mui ca n, c
167

th iu ch axit terephtalic. Tuy nhin, phng n u phng php

khng c s dng do 2 khuyt im: hn hp nm trng thi rn,
nn khng thun li cho vic vn chuyn cng nh cc cng vic khc
v cn dng mt lng kim ln ( to mui) v axit sunfuric ( tch
axit terephtalic t do), m dng ph phm kh s dng l sunfat kali.
Trong thi gian gn y, a ra cc thng tin v s khc phc cc
nhc im ny: qu trnh thc hin di dng huyn ph (mui c
huyn ph ha trong dimetylterephtalat), nhu vy d vn chuyn. Cn
iu ch benzoat kali v tch axit terephtalic t do, s s dng phn
ng trao i mui
2C6H5 COOH + KOOC - C6H4 - COOK

HOOC - C6H4 - COOH + 2C6H4COOK

Do cc khuyt im ca phng php oxy ha nhiu giai on di v

polimetyl ca hp cht thm, thnh cc axit di hay policacboxylic va
xem trn, nn cn tin hnh nghin cu phng php mt giai on.
Kt qu tm ra mt vi phng n tng hp vi c im chung l
s dng axit axetic lm dung mi
Trong nhm u ca phng php, ngi ta s dng cc cht kch
thch cho qu trnh oxy ha (axetanehit, metyletylxeton, paraanehit)
v axetat coban lm xc tc. Cc cht kch thch s c oxy ha
cng vi hyrocacbon thm to axit axetic. Vai tr ca chng cng th
hin mnh nu gi coban ha tr 3 nh vo s oxy ha Co2+ bi cc
axit peroxit trung gian to thnh. Cc phng n khc ca qu trnh mt
giai on vi xc tc l Co hay Co Mn v c kch thch bng cht
ph l cc bromua c bit l NaBr cng c s dng rt rng ri.
Qu trnh nghin cu oxy ha xylen khi c s tham gia ca cht xc tc
bromua kim loi cho thy rng, qu trnh c th xy ra theo 2 giai
on khc nhau. Lc u ch oxy ha c 1 nhm metyl v ch sau khi
s dng ht xilen t do th mi bt u chuyn ha axit cacboxylic,
168

trong giai on 2 chm hn giai on 1. Do qu trnh din ra theo

c ch tng ng sau:
+O2
+O2
CH3 - C6H4 - CHO
CH3 - C6H4 - COOH
-H2O
+O2
HOOC - C6H4 - COOH
OHC - C6H4 - COOH

CH3 - C6H4 - CH3

+O2
-H2O

C ch tc dng ca cc cht xc tc bromua kim loi vn thng cha

r rng. Ngi ta cho rng, khi oxy ha cc cht khc nhau vi s c
mt ca chng th trt t ca cc phn ng theo cc tc nhn ban u
v cc cu t ca cht xc tc rt khc nhau. Ban u, t cc bromua
s to ra bromua hyro, c oxy ha thnh brom t do v tham gia
vo giai on sinh mch:
NaBr + CH3 - COOH

HBr + CH3 - COONa

HOO. + Br.

HBr + O2
Br. + ArCH3

HBr + ArC.H2,...

Theo nhn xt ca nhiu kin khc nhau u ng rng, cht xc

tc ch th hin chc nng dng mui chuyn v c Co ha tr 3, lc
brom s mang tnh cht ca gc t do cn hyrocacbon s tham gia
phn ng da vo s chuyn v ca electron qua ion bromua;
Co3+(AcO-)3

+Br-, -AcO-

Br-Co3+(AcO-)2

Br....Co2+ + ArCH3

Co2+

Br.

Br....Co2+(AcO-)2
Co2+ + ArC.H2 + HBr

ArCH3

V vy, nh hng lm mt hot tnh ca cc nhm cacboxylic khng

xy ra mc mnh, nh i vi xc tc thng khng c mt cc
cht kch thch bromua.
Phng php mt giai on, oxy ha xilen thnh axit dicacboxilic c
dng rng trong cng nghip v thm ch cn loi tr cc qu trnh tng
hp nhiu giai on axit terephtalic. Qu trnh oxy ha cc xilen thc
169

hin bng khng kh trong dung dch axit axetic 125 2750C v p
sut n 4MPa. Thit b phn ng s dng l loi thp sc kh hay cc
thit b c cnh khuy; nhit ta ra c dng un si hyrocacbon,
nc v axit axetic. Axit axetic v cht xc tc sau khi tch ra khi cc
sn phm li a tr v tin hnh qu trnh oxy ha. Do nc to ra s
lm gim tc phn ng nn cn phi loi ra khi axit axetic ti sinh.
7.4.2. S cng ngh tng hp axit terephtalic
2

Kh

1
4

H2O

K.kh
8
8
p-xylen

Hnh 7.6. S cng ngh tng hp axit terephtalic 1 giai on

1- Thit b phn ng; 2 - Thit b ngng t; 3 - Thit b tch; 4 - Thit b ly tm;
5 Thp chng ct phn on; 6 - Ni ti sinh axit axetic; 7 - Thit b phn ly;
8 - Ni un; 9 Bm.

Trn hnh 7.6 biu din s cng ngh iu ch axit terephtalic

1 giai on bng qu trnh oxy ha p-xylen. Trong thit b phn ng (1),
ngi ta a vo p-xylen, khng kh, axit axetic ti sinh v cht xc tc
170

( trnh lm tht thot 2 cu t sau cng, ngi ta cho dung dch nhp
liu ca cht xc tc vo axit axetic trn s khng biu din). Nhit
phn ng dng un si axit axetic v nc, cn hi th c ngng t
trong thit b ngng t (2). Phn ngng c tch ra khi khng kh
trong thit b tch (3) v hi lu v thit b phn ng.
Hn hp phn ng l dung dch huyn ph ca axit terephtalic
trong dung mi. Dch huyn ph ny c lc trong thit b li tm (4),
trong axit terephtalic c ra bng axit axetic nhp liu v mang i
tinh ch li. T dch lc, ngi ta chng tch nc trong thp chng
phn on (5), cn y thp s thu c axit axetic cng vi cht xc
tc ha tan trong n v a tr v thit b phn ng (1). Trong dch axit,
khi hi lu nhiu ln cc tp cht nha c tch ly, v vy phn axit
cn a vo thp (6) ti sinh. Axit axetic chng tch ra khi phn
nng v hi lu tr v thit b phn ng (1). Cn phn nng c th b
hay ti sinh li coban trong n.
i vi axit terephtalic iu ch bng phng php 1 giai on,
th cn a i tinh ch c bit tch ra khi p-cacboxylbenzanehit.
thc hin iu ny, ngi ta s dng phng php hyro ha dung
dch nc huyn ph nhit v p sut cao, Khi , cc tp cht s
tr thnh cc hp cht ha tan mnh (cac oxyaxit) v chuyn vo trong
pha nc.
Tt hn l nn tinh ch axit terephtalic bng cch este ha n thnh
dimetylterephtalat v kt tinh li cht ny.
7.4.3. Phn ng este ha axit terephtalic
Si polyeste c hnh thnh trn c s ca phn ng este ha axit 2
chc v ru 2 chc. Axit 2 chc thng dng ph bin tng hp
si polyeste l axit terephtalic.
Si polyeste c rt nhiu ng dng. Mt trong nhng ng dng quan
trng i t monome ban u axit terephtalic l iu ch t lapxan.
171

T lapxan l loi t trng gn ging nh si len nhng bn hn len rt

nhiu. Vi dt t t lapxan bn vi nhit , nh sng, axit, kim, cht
oxy ha. iu ch t lapxan bng phn ng trng ngng gia axit
terephtalic v etylenglycol
HO
n
O

O
+ n H O -C H 2 -C H 2-O H
OH

x t, t 0 C

-(C O -

-C O -O -C 2 H 4-O )n + H 2 O

7.5. Oxy ha metylbenzen trong mi trng ca cc tc cht ban

u. Tng hp dimetyl terephtalat
Phng php truyn thng oxy ha trong pha lng ca cc
cht ban u cng c s dng i vi cc hp cht thm. Cc cht
xc tc c hiu qu vi n l cc mui coban tan. S oxy ha thc hin
bi khng kh di p sut cn gi hn hp trng thi lng. cc
axit thm th bn vi s oxy ha tip tc. V vy thit b phn ng
oxy ha lin tc c th dng l thp sc kh i gin c b tr thm c
cu gii nhit phn ng.
Nu toluen c oxy ha thnh axit benzoic tu7ong i n gin v
trong cc iu kin mm (nhit 1000C 1500C v p sut khng cao)
th s oxy ha cc xilen hay tng qut l cc polymetylbenzen bng oxy
phn t vi xc tc l mui thng xy ra ch to thnh cc axit
monocacboxylic. Nh t p-xilen iu ch p-toluilic axit, t m-xilen iu
ch m-tolulic axit
iu ny c gii thch l do nhm cacbonyl ca axit tolulic lm gim
mnh hot tnh ca nhm metyl gy cn tr s oxy ha ca n. Trong
cc iu kin mnh hn (260 2800C v p sut =7Mpa) c th oxy
ha nhm metyl th hai nhng hiu sut ca axit dicacboxylic ch nm
trong khong 40 60%.
Tuy nhin ngi ta nhn thy rng, nu chuyn nhm cacboxylic thnh
este s gim tc dng kh hot tnh ca nhm cacboxylic. Trn c s
ny tm ra qu trnh 4 giai on iu ch dimetyl terephtalat bao
gm: oxy ha p-xylen thnh p-toluilic axit, este ha axit ny bng
metanol, oxy ha este ca axit toluilic thnh monoeste ca axit
terephtalic v este ha thnh dimetyl terephtalat.
Khi iu ch cc axit polycacboxylic th s lng cc giai on s tng,
ng thi vic phn tch sn phm s cng cng phc tp. V vy
ngi ta tin hnh s oxy ha ban u bng khng kh v sau l
di tc dng ca axit nitric.
Cht xc tc dng ha tan trong hyrocacbon ca mui kim loi
172

(rezinat, naphtenat coban hay mui coban v cc axit to ra trong qu

trnh oxy ha) c s dng vi hm lng 0.05 0.2%. Nhit cn
thit oxy ha xy ra vi vn tc cao thng thng nm trong gii hn
t 120 2000C, i khi nhit c chn da vo tnh tan ca axit
trong hn hp sn phm. trng hp oxy ha bng khng kh, vi
nhit 120 2000C, th gi hn hp phn ng dng lng cn c
p sut cao ( thng thng khong 0.2 n 1 2MPa). Lc phn
nhit ta ra dng lm si nc to thnh v hydrocacbon.
Hiu sut ca axit thm thng gn bng 90%. Cc sn phm ph do
s oxy ha su hn nhm metyl ca hp cht thm l axit formic v
CO2. Ngoi ra cn to cc sn phm ph do s oxy ha khng hon
ton, nh khi oxy ha p-xilen s cho p-cacboxyl benzanehit to cho
polyme c mu.
i vi phng php 4 giai on trnh by phn trc iu ch
dimetylterephtalat t p-xilen c th trong mt thit b phn ng thc hin
cc giai on oxy ha p-xilen v metyl p-toluilat. Trong mt thit b este
ha s tin hnh c hai phn ng este ha p-toluilic axit v
monometylterephtalat. iu ny cho php tng ha tan ca axit trong
hn hp phn ng v gim s lng giai on v s lng cc thit b
v tin hnh s phn chia cc sn phm ch sau giai on este ha.

Hnh 7.7. S cng ngh sn xut dimetylterephtalat

173

1 Thp oxy ha, 2 Bnh ngng, 3, 13, 15 Thng cha, 4 Bm, 5 Van tit lu, 6
B phn un si, 7 Thit b este ha, 8 Thp ra, 9 Ngng t, 10, 12 Thp chng
phn on, 11, 14 Bnh ngng tch, 16, 18 Bnh phn ng khuy, 17, 19 My li tm,
20 B phn tch, 21 Ni un.

S xy ha hn hp p-xilen v metyl p- toluilat (t l 1 : 2) tin hnh

trong thp sc kh 1 vi cc ng xon lm lnh 140 1800C v 0.6
1MPa. Khng kh sau khi lm sch hki cc tp cht v nn n p sut
lm vic, s a vo pha di thp qua ng phn phi. Khi sc qua
hn hp phn ng, khng kh s li theo hn xilen, k ngng t
thit b lm lnh 2 v a tr v thit b phn ng ban u. Xilen cn li
t khng kh bay ra s c thu hi nh than hot tnh (trn s
khng biu din). i vi qu trnh gin on, s oxy ha s kt thc
khi nng tha ca p-xilen trong hn hp phn ng l 1% v mc
chuyn ha ca metylp-toluilat khong 50%. Cht oxy ha cha 20
25% axit toluic, 30% este ca n vi metanol, 11 15% axit terephtalic,
20 25% monoeste ca n cng nh mt lng nh dimetylterephtalat
v cc tp cht nha. Do s c mt trong p-xilen ban u cc tp cht
ca s isome ha n v etylbezen trong cht oxy ha s to ra axit
phtalic, iso-phtalic v benzoic c este ca chng.
Hn hp phn ng chy vo thng cha trung gian 3, k nh
bm p lc 4 s chuyn lin tc vo thp este ha 7 pha trn. Thp
este c cha nhiu mm chp xuyn l v cht lng s chy xung pha
di thp. Cn dng hi ca ru metylic to ra nh nung nng ru
thit b un si 6 th chuyn ng theo chiu ngc li. Nh vo nhit
cp t dng hi, phn ng este ha xy ra nhit 2500C v p sut
2.5 MPa. Hi ru a vo vi lng d s li cun nc sinh ra trong
phn ng lm chuyn dch cn bng v pha to thnh sn phm este
ha. Hn hp metanol v nc thot ra t thit b 7 c ngng t
hon ton trong bnh ngng t 9 v t y metanol c ti sinh bng
chng ct.
Hn hp este nhn t y thp 7 c tit ku v a vo thp
chng ct chn khng vi p sut d 133gPa. Ban u trong thit b
bc hi 8, gni ta tch c hn hp este khi cc tp cht nha km
bay hi v a qua thp chng phn on 10. y phn chng nh
nhn c chnh l metylp-toluilat c a tr v thp, cn phn cn
li c cho chy v bn cha 13 v t y mang i thc hin qu
trnh oxy ha. Cc este ca axit dicacboxylic t y thp 10 tip tc
c chng ct phn on chn khng thp m s 12, ti y cu
t dimetylterephtalat d bay hi nht c tch ra khi hn hp cc
este dimetyl ca cc axit dicacboxylic ng hpn khc (isophtalic). K
trong thit b ngng t phn tch 14, este s ngng t v hon lu
mt phn v thp cn sn phm d th chy vo bn cha 15. Phn
cht cn li y thp 12 vn cha mt lng tng i ln
174

dimetylterephtalat nn ng mang i kt tinh nh dung dch metanol,

cc iso-phtalic th ha tan tt trong metanol nhng dimetylterephtalat th
khng v u7o5c tch ra khi chng dng tinh th (trn s khng
biu din)
lm sch ln cui ra khi cc sn phm ph v nhn c
dimetylterephtalat c tinh khit cao (99,9%), sn phm th t bn
cha 15 s c kt tinh 2 3 ln nh dung dch metanol.
Dimetylterephtalat ha tan vo metanol 1000C trong ni hp 16, 18,
sau c ra, ly tm, lc trong cc thit b li tm 17, 19. Khi dung
dch qua lc nhn c t giai on sau cng s c s dng nh l
cht ha tan i vi giai on trc, cn dung dch lc t giai on 1 th
cho vo thit b nung nng, un si 6 v sau thc hin phn ng
este ha. Hiu sut tng cng ca dimetylterephtalat k c lng mt
mt t khong 85 90%.

175

CHNG 8: TNG HP CHT TY RA

Gii thiu
T lu, con ngi bit dng mt s dung dch ty ra t to ly,
nh dng nc tro ngm ty du m, dng nc b kt gi u
v git ty. Ngy nay, do nhu cu v cht ty ra rt ln, m cht ty
ra nh x phng li c ch to t xt v cc loi du thc vt nh
du da, du m... Cc loi du ny nn dng lm thc phm cho con
ngi. Do , phi tm cc cht ty ra thay th r tin hn, tt hn.
Da trn c s phn tch trn, ngi ta thy rng c th dng nhng
cht hoc hn hp cc cht c tnh ty v tnh hp ph ty ra. Do
, h dng cc cht hu c c tnh hp ph v cht to bt, mang
i kim ha thnh mui kim. Khi phn tn trong nc n va c tnh
ty, va c tnh hp ph, ng thi cho thm cht ph gia h tr 2
tnh cht trn. Cc ankylsunfat, ankansunfonat v arensunfonat l
nhng cht hot ng b mt thng dng, chng c tng hp t cc
qu trnh sunfat ha, sunfo ha, sunfoclo ha v sunfooxy ha.
8.1. Tng hp cht hot ng b mt dng ankylsunfat
Cc cht HBM dng ankylsunfat c th chia thnh 3 nhm chnh:
Cc ankylsunfat bc nht c tng hp t ru bc nht mch
thng. Nhng ru ny, c th l cc sn phm ca qu trnh thy
phn axit bo thin nhin, (v d ru laurilic C12H23OH, miristilic
C14H29OH) hoc c tng hp bng cch hyro ha cc axit bo cao
phn t, thu c trong qu trnh oxy ha parafin hoc tng hp oxo.
Cc ankylsunfat bc hai (cn gi l typol) c tng hp t H2SO4
v olefin mch thng ( olefin thu c trong qu trnh crachking nhit
parafin hoc tng hp c nhm), hoc t ru bc hai thu c bng
phng php oxy ha trc tip parafin mm. Cc nhm sunfoeste trong
phn t typol nm nguyn t cacbon bc hai bt k, do vy nguyn
liu tng hp chng ngoi olefin cn c n olefin vi ni i nm
gia mch thu c bng cch ehyro ha parafin mm.
Este sunfat c tng hp bng sunfat ha cc sn phm ca qu
trnh kt hp 2-3 mol etylenoxit vi ru hoc ankylphenol:
RO H

+nCH2 - CH2 -O

R - (OCH2CH2 -)nOH

SO3

R - (OCH2CH2 -)nOSO2OH

Cc tnh cht HBM ca ankylsunfat ph thuc vo cu to v chiu di

nhm ankyl cng nh v tr ca nhm sunfat. Cc tnh cht ny s gim
mnh nu c qu trnh phn nhnh ca mch cacbon. Do vy, trong
tng hp cc cht HBM ngi ta thng s dng cc ru v olefin
mch thng. Ngoi ra, cn mt nguyn nhn na l qu trnh phn
nhnh mch cacbon s lm gim kh nng phn hy sinh ha ca cc
cht HBM.
176

Kh nng ty ra mnh nht quan st c nhng ankylsunfat vi

nhm sunfoeste cui mch (tc l cacbon bc nht), v tnh ty ra
s gim theo s di chuyn ca nhm ny gia mch. V d vi pentadexylsunfat C15H31OSO2Ona, s nh hng v tr sunfoeste n kh
nng ty ra nh sau:
Bng 8.1. nh hng v tr sunfoeste n kh nng ty ra
S nguyn t C vi nhm OSO2ONa

Kh nng ty ra (%)

120 100 80 50 30

Kh nng ty ra cao nht cho nhng ankylsunfat bc nht t c

khi mch hyrocacbon cha 12-16 nguyn t cacbon, cn i vi
ankylsunfat bc hai gi tr ny l 15-18. Trong trng hp 1-ankylsunfat
kh nng ty ra thay i nh sau:
Bng 8.2. Kh nng thay i tnh ty ra ca 1-ankylsunfat
S lng b nguyn t cacbon

11

13

15

17

19

Kh nng ty ra (%)

20

40

120 140 130

C th thy rng tng hp cc cht ty ra dng ankylsunfat nn

s dng cc ru bc nht l olefin C12 C18 mch thng.
Xt theo cc tnh nng ty ra th cc ankylsunfat bc nht c xem l
cc cht HBM tt nht, sau l cc ankylsunfat bc hai. Trong cng
nghip cc cht ty ra, ankylsunfat c sn xut di dng hn hp
lng (hm lng cht HBM l 20 40%) hay dng bt. Chng c
s dng lm bt git qun o, vi, len ...
8.1.1. Sunfat ha bng axit sunfuric
Qu trnh sunfat ha ru v olefin bng H2SO4, tng hp cht
ty ra c nhiu im ging nhau. C hai phn ng c tin hnh
nhit thp (0 400C), c khuy trn mnh v gii nhit nhanh. Khi
thc hin quy trnh gin on, ngi ta s dng thit b phn ng c
cnh khuy v cho t t axit vo ru hoc olefin. Khi phn ng xy ra,
hn hp s tr nn st, do cn tr qu trnh khuy v lm lnh. Cn
nu thc hin qui trnh sn xut lin tc th s dng cc thit b ni tip
c cnh khuy.
Trong qu trnh sunfat ha ru, hn hp thu c ch yu cha
ankylsunfuric axit, ngoi ra cn c axit v ru cha tham gia phn
ng. Cn trong sunfat ha olefin, ngoi sn phm chnh cn c olefin
cha tham gia phn ng, mt lng diankylsunfuric axit, ete v polime.
S khi x l hn hp ny c trnh by trn hnh 8.1.
Hn hp c trung ha bng kim m c khi th hai, ti y
nhit khng c php qu 600C, v xy ra cc phn ng sau:
177

ROSO2OH + NaOH

ROSO2ONa + H2O

ROSO2ONa + ROH
R2SO4 + NaOH
Ngoi ra, lng axit d s tr thnh sunfatnatri. Ngi ta phn tch
hn hp ny khi 3 bng cch dng ru (etanol hoc isopropanol)
trch ly cc cht hu c, cn li l sunfatnatri (n c tch ra nh l
cht thi). Sau , dung dch ru cha cc cht hu c c lm
long bng nc v ti khi (4) c trch ly bng xng tch cc
cht hu c ban u cha tham gia phn ng, v tch cc sn phm
ph. Hn hp trch ly s c x l trong khi (5) bng cch chng ct
xng, phn cn li s c a tr v qu trnh sunfat ha. Cn dung
dch cc ankylsunfat trong nc - ru t khi (4) c chuyn qua
khi (6 ) chng ct ru, phn dung dch nc cn li s i vo khi
(7), ti y ankylsunfat c trn hp vi cc cu t khc nhau nh
phosphat, soda, cacbonxylmetyl xenlulo, cht ty... to thnh cht
ty ra. Sau hn hp ny s c sy trong khi (8) v nghin,
ng gi trong khi (9).
Nu sn xut cc cht ty ra cht lng thp, theo qui trnh n
gin th c th khng cn cc khi 3, 4, 5 v 6. Hn hp sau khi trung
ha, s trc tip i vo cng on trn, hay trc c th tin hnh
chng ct cc cht hu c bng hi nc. Cht ty ra sn xut theo
qui trnh ny s cha nhiu mui sunfatnatri.

Hnh 8.1. S cc qu trnh chnh sn xut CHBM dng ankylsunfat

1 - Sunfat ha; 2 -Trung ha; 3 - Tch sunfatnatri; 4 - Trch ly; 5 - Ti sinh xng v tch
cc cu t cha phn ng; 6 - Ti sinh ru; 7 - Trn hp; 8 - sy; 9 - nghin v ng gi.

178

Nhng nhc im ca qui trnh trn c th k n l: tn dng

khng ht nguyn liu ban u, thi ra nhiu sunfatnatri, cng ngh
tng i phc tp khi phi sn xut cht ty ra cht lng cao. Do
vy, hin nay phng php ny c thay th bng cc cng ngh
tin tin hn.
8.1.1. Sunfat ha ru bng axit closunfuric
Tnh u vit ca phng php ny, l qu trnh phn ng bt thun
nghch, vn tc phn ng cao, cho php t l s dng ng lng ca
cc cu t ban u v hiu sut chuyn ha thnh ankylsunfat gn nh
t gi tr l thuyt. Ngoi ra, gn nh khng c sn phm ph, duy nht
ch c kh HCl sinh ra, nhng rt d thu c li di dng dung dch
20 30%. Sn phm duy nht ca phn ng ny l ankylsunfuric axit,
iu ny cho php n gin ha ti a giai on x l sn phm, ng
thi c th tng hp cht ty ra thnh phm c cht lng cao, khng
ln mui v c. Vi nhng u th trn y, hin nay phng php
sunfat ha ny ang c ng dng rng ri.
Mt trong nhng c im ca phng php sunfat ha ru bng
closunfuric axit l qu trnh to thnh kh HCl, i khi kh loi ht do hn
hp tr nn st. Ngi ta ngh nhiu bin php loi b HCl nh s
dng dung mi, chn khng..., nhng bin php hu hiu nht l tin
hnh phn ng trong thit b to cho cht lng c b mt ring ln.
S mt loi thit b ny c trnh by trn hnh 5.2.a. Trong thit b
dng a ny, c lp h thng ng xon gii nhit v cnh khuy. Ti
tm a, ngi ta cho closunfuric axit v ru vo, ti y mt phn cc
cu t s tc dng vi nhau. Sau , ngi ta cho hn hp chy qua k
h gia a vi thnh ni phn ng (thnh ni phn ng c lm lnh
bng v o nc). Nh vy, trn thnh ni phn ng, qu trnh s tip
tc v kt thc, ng thi kh HCl c thot ra d dng hn. Hn hp
thu c s i vo b phn trung ha. Nh vy theo phng php ny
ch cn s dng cc khi 1, 2, 7, 8 v 9 trn hnh 5.1, ng thi thm
mt khi thu hi HCl.
8.1.2. Sunfat ha ru bng SO3
Phng php ny cng c nhiu u im tng t khi s dng
closunfuric axit. Ngoi ra, gi thnh ca SO3 r hn so vi closunfuric
axit, ng thi khng sinh ra kh HCl. Do vy, c th ni y l phng
php tin tin nht v hin nay chng ang thay th cc phng php
khc trong sn xut cng ngh.
Cc kh khn ch yu khi thc hin phng php sunfat ha ru
bng SO3 l vn tc phn ng rt ln, ta nhit mnh, d dn ti
hin tng nhit cc b, thc y cc phn ng ph v sn phm c
mu ti. hn ch cc kh khn trn, ngi ta khc ph bng cch
lm long kh SO3 bng khng kh n nng th tch 4 7%. Ti
179

nhng nh my sn xut theo phng php ny vi cng sut ln,

ngi ta kt hp thm thit b oxy ha SO2 (kh SO2 thu c t cc
nh my luyn kim mu).

Hnh 8.2. S cng ngh sn xut cht ty ra trn c s ankylsunfat.

1 - Thit b phn ng; 2 - Thit b lc; 3 - Thit b hp th; 4, 6 - Thit b trung ha; 5 Thit b lm lnh; 7 - Thit b trn; 8 - Thit b sy phun;
9 cyclon; 10 Bng ti; 11 Bm.

S cng ngh sn xut cht ty ra trn c s ankylsunfat c

th hin trn hnh 8.2.
Ru, khng kh v kh SO3 c a lin tc vo thit b dng
mng (1). Kh thot ra t thit b ny c tch bi thit b tch (2), sau
hp thu ti thit b (3) lm sch khi kh SO3. Ankylsunfuric axit
c a qua trung ha ti thit b (4), c km theo b phn lm lnh
(5), ti y nhit khng vt qu 600C. Tip theo ti thit b (6),
ngi ta tin hnh trung ha chnh xc, tc l hn hp qua thit b ny
s c pH = 7 (c kim tra bng pH k). Hn hp sau khi trung ha s
c a vo thit b trn (7), y ngi ta thm cc cht ph gia
nh phosphat, soda, cht ty, cacboxymetyl xenlulo to thnh cht
ty ra. Hn hp thu c s bm vo thit b sy phun (8). Cc ht
rn s thu hi xyclon (9). Bt git thnh phm t thit b (8), (9) c
truyn qua cng on ng gi theo bng.
8.2. Tng hp cht hot ng b mt dng ankylarensunfonat
Cc cht hot ng b mt ny c nhm ankyl ni vi nhn thm (phn
k nc) v phn a nc l nhm sunfonat SO2ONa. Chng c
chia thnh hai loi: Sunfonat du m v Sunfonat tng hp
180

8.2.1. Sunfonat du m
c tng hp bng sunfo ha cc phn on du m c cha
hyrocacbon ankylaromatic.
Cc ankylarensunfonat du m c iu ch khi x l cc phn
on du m khc nhau bng oelum. i khi chng c to thnh
ngu nhin khi dearomatic ha cc m bi trn bng oleum. Cc
hyrocacbon ankylaromatic c trong du m rt khc bit v cu to
(chiu di v s nhm ankyl, s nhn thm), do vy cc sunfonat thu
nhn t chng l mt hn hp tng i phc tp, ph thuc vo khi
lng phn t trung bnh ca m ban u m cc sunfo axit thu c
c th tan trong nc hoc trong du.
Cc sunfonat du m c tnh hot ng b mt thp hn so vi cc loi
tng hp nhng chng c gi thnh r hn. Chng c mi (do cc tp
cht trong m) v c mu (i khi c mu en), do vy chng c s
dng mt cch hn ch lm cht ty ra. ng dng ch yu ca cc
sunfonat ny l dng lm cc cht tng nht cho du m, cht nh
ha hoc ng t trong cng nghip du m, cc tc nhn to bt...
8.2.2. Sunfonat tng hp
Cc ankylarensunfonat tng hp (cn gi l sunfonol) l cc cht ty
ra ch yu (chim gn 50% tng sn lng cc cht ty ra cc loi).
Sn phm ni ting u tin ca dng ny l Nekal, c tng hp t
naphtalen, x l bng isopropanol (hoc isobuttanol) v axit sunfuric.
Axit sunfuric ng thi thc hin hai chc nng l xc tc cho qu trnh
ankyl ha v tc nhn sunfo ho, trong s c hai nhm ankyl tham
gia vo nhn thm:
C 10H 8 + 2ROH + H2SO 4

R2C 10H 5SO 2OH + 3H2O

Do hot tnh b mt ca cc sn phm dng Nekal tng i thp,

ngi ta nghin cu kh nng tng hp cc cht HBM t benzen
bng cch ankyl ha v sunfo ha n. Cc kt qu cho thy, cc tnh
cht HBM ca ankylarensunfonat ph thuc rt nhiu vo cu to ca
nhm ankyl. V d, nu nhm phenylsunfonat v tr 1 v nhm ankyl c
cu to mch thng th cc tnh cht ty ra cc i t c khi nhm
ankyl cha 11 -14 nguyn t cacbon. V tr ca nhm phenylsunfonat
vi mch hyrocacbon thng ca nhm ankyl th cc ng phn 2 v 3
c tnh cht ty ra tt nht, cn khi nhm th chuyn v gia mch th
tnh ty ra cng b gim.
T cc s liu trn nhn thy, tng hp ankylarensunfonat nn s
dng ankylnenzen vi nhm ankyl C10-C16, tt nht l C11-C14 . Do vn
phn hysinh ha, cc nhm ankyl cng t phn nhnh cng tt, cn
vic s dng dodexyl benzensunfonat (DBSA) tng hp t tetrame ca
propylen, b hy b nhiu nc. Hin nay, ngun nhm ankyl ch
yu c khai thc t cc phn on du hi ca du parafin hoc cc
181

parafin mm tch ra t cc phn on thu c t ure hay zeolit; ngoi

ra c th s dng n-olefin vi ni i cui mch hoc gia mch thu
c trong qu trnh cracking parafin cng hay ehyro ha parafin
mm. Khi s dng parafin, ton b qu trnh bao gm: clo ha, ankyl
ha benzen, bng ankylclorua, sunfo ha v trung ha. Nu s dng
olefin lm nguyn liu th qu trnh s l ankyl ha, sunfo ha v trung
ha

+ C l2 R C l + C 6 H 6 R C H H 2 S O 4 R C H S O O H N a O H R C H S O O N a
6 4 2
6 5 -H O
6 4 2
RH
2
O
H
H
C
l
2
- HCl
RCH = CH2

C 6H 6

R R ,,C H - C 6 H 5

SO3

R , R ,, C H - C 6 H 4 S O 2 O H

NaO H
-H 2 O

R ,R ,,C H - C 6 H 4 S O 2 O N a

Sn phm thu c l mt hn hp cc sunfonat cha cc nhm ankyl

c di khc nhau. Ngoi ra, do qu trnh isome ha di nh hng
ca AlCl3 s to ra cc cht trong nhm phenylsunfonat gn vi cc
nguyn t cacbon bc 2 ca nhm ankyl.
Ankylarensunfonat l nhng cht tinh th rn. Khi nhm ankyl c
phn nhnh th cc cht ny tan tt trong nc. Khi chiu di nhm
ankyl tng, phn nhnh t, s lm gim kh nng ha tan trong nc
v ru. Cc cht ny hu nh khng mu khng mi. Chng c s
dng tng hp cc bt git qun o, vi, len,
S cng ngh ca phng php ny khng khc bit nhiu so
vi qu trnh sunfat ha ru. Qui trnh cng ngh n gin ha
c th hin trn hnh 8.3. Ti khi (1), ngi ta thc hin qu trnh
oxy ha SO2 thnh SO3 bng oxy khng kh. Sn phm thu c sau
khi lm lnh v ngng t sinh hn (2), c cha trong thng cha
(3) l dung dch ca SO3 nng 10 15% trong SO2 lng. Dung dch
ny cng vi dung dch hyrocacbon trong SO2 c a vo thit b
phn ng (4). Hn hp cht lng i ra khi thit b (4) cn cha khong
5 7% SO2. tch lng SO2 ny, ngi ta tin hnh un nng v
sau cho bc hi thit b bc hi (5). Cht lng cn li i vo thng
cha (7) v sau a i x l tip tc (trung ha, trn, sy, ng gi).
Phn SO2 bc hi thit b (5) c a tr li khi (1).

182

SO2
O2

ArH
1
4

5
2
3

Hnh 8.3..S cng ngh ca qu trnh sunfo ha

1 - Khi oxy ha SO2 thnh SO3; 2 Sinh hn; 3, 7 Thng cha;
4 - Thit b phn ng; 5 - Thit b bc hi; 6 - H thng gia nhit.

Hnh 8.4 l s cng ngh xut CHBM dng ankansunfonat bng

phng php sunfoclo ha quang ha. Hot ng ca dy chuyn
nh sau :
Clo nhn c bng phng php bc hi clo lng, c trn vi
SO2 (lng SO2 ly d khong 5% so vi clo) v a vo pha di
ca thit b phn ng (1), cc cht kh ny s sc vo lp cht lng
cha trong thit b ny. Ngi ta cng a vo thp phn ng (1),
lng parafin mi cng vi parafin thu hi sau phn ng. Nhit ca
phn ng c gii phng bng sinh hn (2), hn hp phn ng i qua
sinh hn ny bng h thng bm (3). Kh thi i ra t thit b (1) bao
gm HCl v SO2 cha phn ng. Cc kh ny c a vo lm sch
khi (4).
Hn hp thit b (1) s chy t bn hng qua thit b thi khng kh
(5). Ti y, lng HCl v SO2 tan trong hn hp s c loi b bi
lung khng kh. Tip theo hn hp c trung ha bng dung dch
kim 1000C trong thit b (6), lng trong thit b (7). Lp trn l
phn hyrocacbon cha chuyn ha v mt lng nh ankylclorua,
phn ny c a hi lu li phn ng bng bm (8). Lp di
183

c lm lnh trong thit b (9) n 5 100C v tch trong thit b (10).

Phn sn phm c tip tc x l, bng cch pha long vi nc n
20% trong thit b trn (11) v ty trng trong thp (12). Giai on cui
cng l c chn khng thu nhn ankansunfonat di dng dung dch
trong nc vi nng 60%.
Kh thoat

H2O
Axit HCl
4
9

10

12

Cl2

Nc
muoi

NaOH

SO2
RH

kh

7
Khng kh
6
Cl2
H2O
8

Hnh 8.4. S cng ngh sn xut CHBM dng ankansunfonat bng phng php
sunfoclo ha quang ha.
1 - Thp phn ng ; 2, 9 - Sinh hn ; 3, 8 - Bm ; 4 - Khi thu kh HCl v lm sch kh thi ;
5 - Thit b thi khng kh ; 6 - Thit b trung ha ; 7, 10 - Thit b tch ; 11 - Thit b trn ;
12 - Thp ty trng.

8.3. Phn loi cht hot ng b mt (HBM)

8.3.1. Cht hot ng b mt nonionic (NI)
C kh nng HBM khng cao. m du vi da, ly du t. Lm bn
bt, to nh tt. C kh nng phn gii sinh hc. t chu nh hng ca
nc cng v pH ca mi trng, tuy nhin c kh nng to phc vi
mt s ion kim loi nng trong nc....
Hin nay tng hp chng, phng php c dng ph bin nht
l qu trnh etoxy ha t ru bo vi oxyt etylen: Cng thc chung: RO-(CH2-CH2-O-)nH.
Cc ru bo ny c ngun gc thin nhin nh du thc vt, m
ng vt thng qua phn ng H2 ha cc axit bo tng ng:
VD: n - CH3 - (CH2)13 - COOH + H2

n - CH3 - (CH2)13 - CH2OH

Hoc bng con ng t ru tng hp: bng cch cho olefin-1

184

phn ng vi H2SO4, ri thy phn (thu c ru bc 2). Trong

thng mi, loi ny c tn gi: tecitol 15-s-7, union caride 15-s-9...
Cht hot ng b mt nonionic c phn loi thnh cc dng c
bn sau:
Copolimer c cng thc chung: HO-(OE)n-(OP)m-(OE)n-H, hoc HO(OP)n-(OE)m-(EP)n-H. T s PO/OE c th thay i: 4 - 1 hoc 9 - 1.
Trng lng phn t thp nht: 2000vC, thng dng nht hin nay l
loi n = 2 v m = 30, chng to bt km nn dng ph bin trong cc
sn phm ty ra chuyn dng cho my: my ra chn, my git,
khng gy hi cho mi trng, c tnh yu. Tuy nhin dng lng
khng ln v kh nng phn hy sinh hc chm.
Cc oxyt amin, ankyl amin, ru amit, polyglycerol ete, polyglucosit
(APG)... Nhm ny c tnh cht ni tri l rt n nh vi cht ty c clo,
nc javel, cht oxy ha... thng dng lm tc nhn nn, tng tnh n
nh bt, lm st, to nh nh x c cho sn phm ... c bit d b
phn hy sinh hc, l oxit amin, ankyl amin, ankylmonoetanolamit,
polyglycerol ete, anlkyl polyglucosit (APG), sunfonat Betain,
ankylaminopropylsunfo betain, betain etoxy ha.
8.3.2. Cht HBM anionic
C kh nng HBM mnh nht so vi cc loi khc. Lm tc ng
ty ra chnh trong khi phi liu. Kh nng ly du cao. To bt to
nhng km bn... B th ng ha (mt kh nng ty ra trong nc
cng, cng tm thi, cc ion kim loi nng (Fe3+, Cu2+...)
Cht HBM anionic rt a dng v t rt lu con ngi bit s
dng trong cng vic git gi. Chia lm hai loi chnh:
C ngun gc thin nhin:
chnh l sn phm t phn ng x phng ha ca cc estec axit
bo vi glyxerin (du c, du da, du nnh, du lc, du cao su... m
heo, m cu, m b, m hi cu, m c voi...)
C ngun gc t du m:
Thng qua phn ng ankyl ha, sunfo ha cc dn xut anlkyl, aryl,
ankylbenzen sunfonic.
Parafin sunfonate (SAS): hin nay cc SAS cha c s dng cho
bt git v gi thnh cn cao. Do c kh nng phn hy sinh hc tt nn
rt c khuyn khch s dng.
PAS: l cht HBM dng este do phn ng gia ru bo v oleum
SO3.
8.3.3. Cht HBM cationic
C kh nng HBM khng cao. L cht HBM c nhm i nc l ion
dng, ion dng thng thng l cc dn xut ca mui amin bc
bn ca clo.
m du vi da, ty du t, khng dng vi mc ch to bt. Lm bn
185

bt, to nh tt... C kh nng phn gii sinh hc km, hin nay ngi
ta dng clorua ditearyl diamin amoni bc bn v kh nng phn gii sinh
hc tt hn.
Tng lai trn th trng, s c cc cationic dng nhm chc este d
phn gii sinh hc hn cho mi trng, v gim kh nng gy d ng
khi s dng. Ch yu lm trit tiu tnh in cho tc, vi si... nn lng
dng rt t.
8.3.4. Cht HBM lng tnh
C kh nng HBM khng cao, l cht HBM c cc nhm lng
cc va tch in m va tch in dng (amin, este). pH thp
chng l cht HBM cationic v l anionic pH cao. C kh nng phn
hy sinh hc. Lng dng khong 0,2% -1% trong cc sn phm ty
ra.
Phn loi
Trong nhm cc cht HBM lng tnh, hin nay cc dn xut t
betain c s dng rng ri nht. Chng gm cc nhm chnh sau:
Ankylamino propyl betain,
Khi R l gc lauryl th c tnh ty ra rt tt, kh nng to bt mnh,
khng l kh da, du cho da... hin nay trn th trng thng thy phi
trong: du gi, sa tm, nc ra chn... vi tn gi: cocoamino propyl
betain (CAPB).
8.4. Nguyn liu sn xut cc cht ty ra
8.4.1. Axit doexy benzen sunforic
Tnh cht l hc
oexy benzen sunfo axit, vit tc l DBSA, c cng thc phn t l:
C12H25C6H4SO3H
L cht lng mu en nu nn gi l kem en. C nht cao, c phn
t lng M = 326 vC, t trng d = 1,05. nhit thng c hi SO3
bay ra nn c mi hc v gy c hi cho c quan h hp.
Khi gp nc c hin tng vn cc li v rt kh tan, tan t khi khuy
mnh.
Khi ri vo da lm kh da, lu lm bng nh. Trn th trng bn
DBSA c hm lng 96% n 98% cn t 1 n 2% l H2SO4, t 1 n
2% l cht cha b sunfo ha.
iu ch
Trong cng nghip, ngi ta iu ch DBSA bng cch sunfo ha
oexy benzen.
C 12H 25C 6H5

SO3

C12H25C6H4SO3H

Trong qu trnh sn xut, ngi ta sc SO3 t di thp i ln. Cn

oexy benzen th ti t trn xung. tng din tch tip xc, nn
dng m xp trong thp, vic ny lm tng hiu sut to DBSA.
Trong qu trnh sunfo ha, cn mt lng SO3 ha tan vo DBSA, do
186

 DBSA cn mt lng SO3 mang theo trong sn phm v cng cn

mt phn cc cht cha b sunfo ha.
ng dng v bo qun
DBSA c s dng lm cht to bt trong cng nghip sn xut
cc cht ty ra, DBSA c dng sn xut DBSNa l cht ty ra
chnh. Ngoi ra, DBSA cn c dng trong cng ngh tuyn khong.
DBSA c nhp t nc ngoi cha trong thng kn. ni kh
ro v mt. Kho cha DBSA khng c gn la, phi m bo quy tc
phng chng chy v DBSA d chy. Khi dng xong phi y kn v n
c hi c SO3 bay ra. Kho cha v ni sn xut phi thong.
Khi s dng trnh DBSA bm vo da, vo mt, cn c khu trang,
gng tay cao su, knh bo h, giy, m
Khng DBSA ra nn v n c v rt trn s b t ng. Khi b
cn thu gom vo bn thu hi v phi lm sch nn, bng thm mn
ca qut dn i.
Khng cc ha cht khc ln vo kho DBSA. Khi b DBSA bm vo
da cn ra ngay bng nc vi chy ri ra bng x phng cho sch.
8.4.2. Natri hyroxit - NaOH

Tnh cht l hc
Natri hyroxit l cht rn, tinh th c mu trng c t trng d = 2,13,
phn t lng M=40 vC. Trong khng kh rt d ht m chy ra. Tan
nhiu trong nc, 200C tan 109 gam/100g H2O v 1000C
347gam/100g H2O. Nng chy 3180C v si 13880C.
Dung dch xt c tnh n da nn cn gi l xt n da. B xt bm vo da
lu gy bng nng, do ta phi ra ngay bng dng nc chy, ri
ra bng x phng cho k, nhiu ln.
iu ch
Trong cng nghip, ngi ta iu ch xt bng nhiu phng php.
Nhng hin nay phng php in phn dung dch mui n c dng
nhiu nht.
Nguyn tc ca phng php ny l dng dng in mt chiu in
phn dung dch mui n, gia hai in cc c mng ngn. trong dung
dch phn ly ra cc ion.
NaCl

Na+

Cl-

V nc cng phn ly t
H2O

H+

OH-

Ti cc dng:
ion Cl- v ion OH- ti, nhng ch c ion Cl- phng in (nhng in t
vo in cc dng).
Cl- - e
=
Cl0
2Cl0 =Cl2
2Cl- -2e =
Ti cc m
187

ion Na+ v ion H+ ti. Nhng ch c ion H+ l phng in (nhn in t

t in cc m).
H+ + e
=
H0
2H0 =H2
2H+ + 2e =
Cn dung dch c cc ion Na+ v OH- chnh l dung dch xt, dung dch
chy ra cn mang theo mui cha b in phn. Ngi ta mang c c
ri lm lnh cho mui kt tinh, mang i tch mui ra, cn dung dch xt
thu c mang i s dng trong cng nghip.
S d phi c mng ngn gia hai in cc l trnh cho clo bay
sang cc m, tc dng vi xt to nc javen v lm cho hiu sut in
phn gim.
ng dng v bo qun
Xt l mt trong cc ha cht c bn nht. N c ng dng rt
nhiu trong cng ngh giy, cng ngh sn xut cht ty ra, cng
ngh nhum ty vi, cng ngh sn xut thy tinh lng...
Xt sn xut ni a l dung dch xt, c cha vo cc thng bng
st. Xt nhp ngoi l xt rn, cng ng vo thng st. Thng cha
xt phi kn v d ht m, chy ra.
Khi s dng xt, ngi cng nhn nht thit phi eo bo h lao ng
t qun o, ng, gng tay, khu trang kn ...
Khi b xt bm vo da phi ra ngay bng vi nc chy, ri ra bng
x phng tht k.
Kho cha xt phi kh thong, h thng in phi cao, cng tc phi
bn ngoi phng kho. Trnh h cc ng dy in trong cc kho
ha cht nht l kho xt, v in d b r ra do m.
8.4.3. Natri cacbonat - Na2CO3

Tnh cht l hc
Natri cacbonnat cn gi l sa, l cht rn, tinh th mu trng, c t
trng d = 2.53, phn t lng M = 106 vC. Nhit nng chy l
8510C. Khi un nng cao hn na n b phn hy.
Sa d tan trong nc, 200C tan l 21,5g/100g H2O, 1000C tan l
45,5g/100g H2O. Trong khng kh m n d ht nc v chy ra.
Trn th trng soa phi c hm lng nh sau: Na2CO3 99% cc
cht khng tan 0,1%. Mu trng v khng c mi.
iu ch
Trong cng nghip iu ch soa hin nay dng phng php
solvay. Nguyn tc ca phng php l dng nc mui bo ha hp
th NH3 v CO2 to thnh natri bicacbonat kt ta.
NaClH + NH3 + CO2 + H2O

NaHCO3 + NH4ClH

Sau lc ly NaHCO3 ri em nung c soa

188

NaHCO3

t0

NaCO3 + CO2 + H2O

Kh CO2 c thu quay tr li cng on trc.

Amon clorua NH4Cl c ti s dng NH3, quay tr li cng on
u bng nc vi tc dng trong thp ti sinh NH3 theo phn ng:
Ca(OH)2 + 2NH4Cl

CaCl2 + 2NH3 + H2O

ng dng v bo qun
Soa dng rt nhiu trong cng ngh ch bin thc phm, cng
ngh nhum, ch to cht ty ra, trong cng nghip thy tinh dng
soa lm cht tr dung. Trong dc phm ch to natri bicacbonat
lm thuc kh toan cho au d dy
Soa cng l ha cht c bn c dng rt nhiu.
Soa phi ng trong bao kn, thng kn; kho soa phi kh ro
v thong mt. Soa cng n da nn khi s dng cn c trang b bo
h lao ng.
8.4.4. Natri silicat - Na2SiO3
Tnh cht l hc
Natrisilicat l cht rn tinh th trong sut, t trng d=2,4. Phn t
lng M=124 vc, c nhit nng chy l 1080C.
Natrisilicat d ht nc. Ngm nc thnh cng thc nc l:
Na2SiO3.9H2O. Tan nhiu trong nc nng, t tan trong nc lnh.
Trong cng nghip dng natrisilicat khong 39%. Gi l thy tinh lng
c quy chun nh sau:
Hm lng nc 60%
Hm lng Na2O 10%
Moun silicat t 2,4 n 2,8
T trng d=1,383
Cht khng tan 0,5%
iu ch
Trong cng nghip iu ch thy tinh lng bng cch cho ct tc
dng vi dung dch xt trong thng st c un nng. Trong ct ch
yu l SiO2 tc dng vi xt theo phng trnh phn ng
t
SiO2 + NaOH 0
Na2SiO3 + H2O
Sau em lc ly dung dch thy tinh lng ng vo thng phuy.
ng dng v bo qun
Thy tinh lng c dng trong cng ngh sn xut x phng, bt
git, kem git, trong cng ngh sn xut keo dn v trong cng ngh
sn xut xi mng. Lm cht kt tinh xy cc l chu axit
Thy tinh lng bo qun trong cc thng phuy kn. Khi b ra nn phi
dn i ht.
Khi s dng cn trang b qun o bo h lao ng.
189

8.4.5. Natritripoly photphat - Na5P3O10

Tnh cht l hc
Tripoli photphat natri l cht kt tinh, tinh th nh dng bt mu
trng. T trng d=0,8. Phn t lng M=368 vC. Thnh phn quy ra
P2O5=57,6% v Na2O=42,2%. D tan trong nc: 200C tan
25,8g/100g H2O 1000C tan 40,26g/100g H2O. D ht m chy ra. N
tn ti hai dng th hnh: l dng hyrat ha chm v dng hyrat ha
nhanh. Trong thc t hai dng ny ln ln vi nhau.
Trn th trng c hai loi natri tripoly photphat c cc tiu chun sau:
Bng 8.3. Bng tiu chun natri tripolyphotphat
loi 2
Ch tiu
Loi 1
m

1%

P2O5

55%

pH (dd 1%)

9 -10

2%
47,5%
9 -10

Cht khng tan

0,1%
0,25%
iu ch
Trong cng nghip, ngi ta iu ch tripoly photphat natri bng
cch trung ha axit photphoric bng xt n pH = 9 10 phn ng xy
ra cc nc
NaOH + H3PO4
NaOH + NaH2PO4

NaH2PO4 + H2O
Na2HPO4 + H2O

Sau em c c, kt tinh ri em sy kt ta kh,ta c sn phm

l Na5P3O10. nh my Supe photphat Lm Thao - Vnh Ph sn
xut c natri tripoly photphat.
ng dng v bo qun
Natri tripolyphotphat c dng ch yu trong cng ngh sn xut
cc cht ty ra. N c tc dng thm t, ty nh v thy phn ra
NaOH. N cn lm mt tc hi ca nc cng, nc l. Do , lm cho
bt git, kem git dng c vng nc l v nc cng.
Natri tripolyphotphat c ng trong ti kn, v n d ht m chy ra.
N dng bt, nh d b gi cun nn khi dng phi c khu trang ko
ht phi c hi cho ng h hp, phi dng knh bo h. Dng xong
cn tha phi bao gi k.
8.4.6. Natrisunfat - Na2SO4
Tnh cht l hc
Natri sunphat l cht kt tinh mu trng c v ng cht ca ion SO42, t trng d = 2,7, phn t lng M = 142 vC. Nhit nng chy l
190

88.50C. Tan nhiu trong nc. 290C tan 19,4g/100g H2O. 100oC
tan 42,5g/100g H2O. N d ht m chy ra. Natri sunfat cn dng
ngm nc c cng thc l: Na2SO4.10H2O. C t trng d=1,73 v
phn t lng M=322 vc
Trn th trng bn natri sunfat c hai loi theo cc ch tiu sau
Bng 8.4. Bng tiu chun natri sunfat
Ch tiu
Loi 1
Loi 2
6%
m
2%
Na2SO4

98%

NH4Cl

NaCl

0,2%

90%
1%
1,5%

Bt dng ti khng ng cc. Mu trng ng. Khng c mi khai.

iu ch
Trong cng nghip iu ch natri sunfat t mui n v amon sunfat
2NaCl + (NH4)2SO4

Na2SO4 + 2NH4Cl

Phn ng tin hnh nhit 1030C, c kt ta huyn ph Na2SO4,

mang i lc c kt ta Na2SO4, cn dung dch cha NH4Cl cng mt
t NaCl, Na2SO4 v (NH4) 2SO4 tan trong dch c mang i lm ngui,
NH4Cl kt tinh c lc ra; nc ci (dung dch lc) li c a quay
tr li sn xut v trong nc ci cn
(NH4) 2SO4, NaCl, NH4Cl v Na2SO4.
ng dng v bo qun
Natri sunfat c dng nhiu trong k thut sn xut thy tinh, sn
xut giy, trong cng ngh lnh v trong sn xut cc cht ty ra.
Trong cng ngh sn xut cht ty ra, n c tc dng lm tng hot
tnh ca cht ty ra DBSNa, lm cht n h gi trnh sn phm.
Bo qun natri sunfat trong cc bao kn bng nha PVC. Kho cha phi
kh ro v thong.
Khi s dng cn trang b qun o bo h, khng c ra nn nh
v n ht m gy m, n mn cc dng kim loi, ngm vo btng v
ph hy.
8.4.7. Hyro peroxit - H2O2 (nc oxy gi)
Tnh cht l hc
Dung dch hyro peoxit khng mu, c mi hc v c tnh c. a
ra nh sng c bt kh bay ra, do b nh sng kch thch n t phn hy
to ra oxy bay ln v nc.
191

Hyro peoxit tan nhiu trong nc, dung dch c c th lm bng da,
nhit cao cng t phn hy to nc v oxi.
iu ch hyro peoxit
Ngi ta cho axit pesunpuric thy phn bng nc
H2S2O8 + 2H2O

2H2SO4 + H2O2

Sau chng ct ngng t c H2O2 trong dung dch

ng dng v bo qun.
Hyro peoxit c dng nhiu trong cng ngh ty trng cc ch
phm, bng, vi trong y hc dng st trng cc vt thng, ra
cc vt thng su.
Bo qun hyro peoxit: cha trong bnh thy tinh, hoc bnh nha kn
c mu ngn nh sng. ni nhit thp. Trnh gn ni
cha cht chy v nh vy s gy chy ta nhit, lm H2O2 b phn hy
ra oxy cung cp cho qu trnh chy mnh lit hn.
Khi s dng cn eo gng tay cao su, khu trang v qun o bo h lao
ng.
Khi b hyro peoxit ln da phi ra ngay bng nc vi chy.
8.4.8. Natri tetraborat - Na2B4O7
Tnh cht l hc
Natri tetraborat l cht kt tinh mu trng khng mi. C t trng
d=2,37, phn t lng l M=201vc. Nng chy 7410C. t tan trong
nc lnh, tan nhiu trong nc nng
Natri tetraborat ngm nc c tinh th mu c, cng thc tng ng:
Na2B4O7.10H2O, phn t lng M = 381vc.
Trn th trng natri tetraborat phi bo m cc ch tiu sau:
Tinh th trng, cng khng mi
Na2B4O7.10H2O c hm lng 99%
Cht khng tan 0.1%
pH ca dung dch 1% l 9 10.
iu ch
Trong t nhin nguyn t Bo tn ti 3 dng: axit Boric H3BO3,
tetraborat ngm nc Na2B4O7.10H2O v qung asarit MgHBO3. Ngi
ta cng iu ch t 3 loi qung trn.
ng dng v bo qun:
Natri tetraborat dng nhiu trong y hc st trng, trong cng ngh
thuc da dng chng thi, st khun. Trong sn xut men trn st
trng men, trong cng ngh thy tinh dng lm cht tr dung.
Trong cng ngh cht ty ra lm cht dit khun, chng hi cho qun
o v ty ra.
Natri tetraborat bo qun trong ti, hp kn, ni kh ro. Trnh tip
xc vi cc ha cht khc; khi s dng phi dng bo h, khu trang
v gng tay.
192

8.4.9. Natri cacboxy metylxenlulo

K hiu CMC, Cng thc: R O - CH2 COO Na
Tnh cht l hc
L cht bt trng ng khng mi. N phn tn trong nc to thnh
h keo l cht hot ng v hp ph rt tt.
Bng 8.5. Ch tiu CMC phi t trn th trng
m
10%
nht dung dch 1%
6 30 CPS
pH dung dch 1%
7 10
Hm lng cht hot ng
50 60%
Cng dng v bo qun
Natri cacboxy metylxenlulo dng lm cht nh ha. Tng kh nng
phn tn trong cng ngh sn, keo, mc in, h si vi.
Dng trong cht ty ra, tng kh nng phn tn to keo, chng phn
lp cho kem git, ngn cn cht bn bm tr li qun o khi git, tr
gip cho cht ty ra.
CMC cha trong bao kn trnh m. Khng tip xc vi ha cht
khc, khng gn la.
Khi s dng phi dng bo h, khu trang v gng tay.
8.4.10.
Natri clorua (NaCl)
Tnh cht vt l
L cht rn kt tinh, tinh th hnh khi lp phng mu trng khng
mu c v mn, t trng d = 2,16, phn t lng M = 58,5vc.
Nng chy 8000C, si 1440C. Tan nhiu trong nc. 200C tan
36g / 100gH2O, 1000C tan 39,1g/100g H2O. Trong khng kh n d
ht m chy ra.
ng dng v bo qun
Mui l nguyn liu dng nhiu trong cng nghip ha cht.
Trong i sng mui l gia v, trong kem git n c kh nng tng tnh
ty ra ng thi l cht n.
Mui c bo qun trong kho kh ro, ng trong bao kn, kho cha
mui khng nn cc dy in trn, cc cm cng tc u phi
ngoi kho.
Khi s dng cn c gng tay cao su trnh tip xc, v n khng n da
nhng lm kh ho da tay.
8.4.11.
Cht ty hunh quang
Cht ty hunh quang c tnh cht hp ph tia sng t ngoi, phn
x tia sng xanh. Do , khi n bm ln vi lm cho vi c nh sng
xanh, lm ngi ta c cm gic sch, sng p. Chng l cc cht hu
c nh; Tynofan, Kavafort, lececofort, k hiu chung l FWA.
Ty theo tng loi, m khi s dng ta phi chn cho thch hp; c loi
dng cho si bng, c loi dng cho vi nilon, c loi dng trong nc
193

nng, c loi dng trong nc lnh.

Tuy nhin, cc cht hunh quang c nhc im l bm trn vi ri b
nh sng phn hy, do dng nhiu ngy vi s b vng du. Do ,
cng tht hn ch khi s dng.
8.4.12.
Cht thm
Cht thm c tng hp t cc cht hu c hoc chit t cc du
thc vt c mi thm. Trong cng ngh cht ty ra v ha m phm,
cht thm c dng nhiu khi dng n lu li mi thm trn vi
lm cho ngi ta c cm gic thm mt sch.
Cc cht thm c yu cu sau:
C mi thm c trng
Sn phm dng lng tinh khit
Mu vng nht hoc da cam
T trng d = 10,5
Gi thnh h.
Trong thc t cc cht thm rt t tin, vy ta s dng v qun l
chng hp l. Tnh cht ca chng l: D bay hi, c mi thm c
trng, d chy to CO2 v H2O v ta nhiu nhit. C cht c tnh
kch thch khu gic gy kh chu, do khi s dng phi ng liu
lng. C cht dng c trong thc phm, c cht cm dng . Vy
phi s dng ng theo qui nh.
8.5. C ch ty ra.
8.5.1. Cc cht bn trong qun o dng
Trong qun o v dng c cc cht bn, cn ty ra git sch i,
cc cht bn c th chia lm cc loi sau:
Cc cht v c, mui khong, bi.
Cc cht hu c nh m, cc axit hu c, cc t bo cht ca da
ngi, ght cu bn.
Cc vi khun nm mc, cc k sinh trng, vi trng.
Tt c cc cht bn cn c ty ra sch.
8.5.2. Qu trnh ty ra
Khi ha tan cc cht ty ra vo nc, cc cht s ha tan, phn tn
u trong nc, mt s cht thy phn mt phn nh:
DBSNa + H2O
Na2CHO3 + H2O
Na5P3O10 + 2H2O

DBSA + NaOH2
NaOH + NaHCO3
2Na2HPO4 + NaH2PO4

Na2HPO4 + H2O

NaOH + NaH2PO4

Na2SiO3 + 2H2O

2NaOH + H2SiO3

V H2SiO3 cng vi CMC to thnh h keo c tnh hp ph. DBSNa v

BDSA hot ng b mt d to bt khi khuy trn.
194

Cc cht Na2SO4, mui n NaCl s tan vo nc h tr cho qu trnh

ty ra.
Khi ta ngm qun o dng vo dung dch trn, qu trnh xy ra nh
sau. Trc tin cc cht ngm vo si vi lm si vi trng ln. Tip
theo l xt (do cc cht thy phn ra) tc dng vi cc cht bo, cc
axit hu c to thnh cc cht d tan. ng thi cc cht c kh nng
hp ph cc cht bn v lc ny cc cht c tnh dit nm, dit khun,
dit k sinh trng tiu dit cc cht bn .
h tr cho qu trnh xy ra nhanh, ta phi khuy trn (v, ch xt).
Nu c iu kin dng nc nng ty ra, v phn ng hu c c
tc chm nn ta phi ngm. Thi gian di nht l 2 gi.
Cc phn ng ty cht bo, axit hu c c th biu din nh sau:
Ty cht bo
CH2 - OOC - R
3NaOH + CH - OOC - R
CH2 - OOC - R

CH2 - OH
CH - OH + 3RCOONa
CH2 - OH

Ty cc axit hu c
R, - COO - H + NaOH

R, - COONa + H2O

Cui cng ta dng nc ra sch cc dng qun o. Ta phi ra

lm nhiu ln cc cht bn cng cc cht ty ra tri i ht sau
em phi kh.
Trong tng lai ngi ta dng cc cht ty ra vi sinh. ngha l ngi
ta khng dng cht ty ra theo c ch ha hc: xt phn ng vi cc
hu c nh lu nay, m dng vi sinh vt dng men vi sinh phn hy
cc cht bn to thnh cc cht d tan trong nc. Phi hp vi cc
cht hp ph lm sch dng cn ty ra. Trn th gii, nhiu
nc tin tin dng phng php vi sinh ty ra, n u im trnh
nhim mi trng, lng s dng chuyn ch t. Nhng c nhc
im l qu trnh ty ra chm, i hi c thi gian v phn ng vi sinh
c tc chm.
Hin nay cng ngh sn xut cc cht ty ra ca Vit Nam ch yu l
cc sn phm bt git, kem git v cc sn phm tng t. Chng ta
s ln lt nghin cu cc cng ngh .
8.6. Mt s qui trnh cng ngh sn xut cht ty ra
8.6.1. Sn xut cht ty ra dng bt
Vic sn xut nhng bt git truyn thng c chia lm ba giai
on chnh:
Sn xut mt hn hp cht chu c nhit cao, sau c
phun thi thnh bt.
Ta c c bt c bn, sau khi ngui c gia thm vo
nhng thnh phn nhy cm hn.
195

 Sau c bt hon chnh, mang i ng gi.

Chun b mt hn hp kem nho v phun sy.
Hn hp c c bng cch thm vo hn hp nguyn liu nh
photphat hoc zeolit, cacbonat, sunfat, cht hot ng b mt, polyme,
cht ty quang.
Mt s lu cn phi c thc hin, chng hn cc axit bo (axit
sunfonic cn phi c trung ha ring trong mt my trn khc trc
khi c a vo trong kem nho. Hn hp ny c khuy trn mnh
c qu trnh ng nht tt, xong a vo mt my trn th hai m
thi gian lu li y c kim tra, cho php hyrat ha cc mui v c
(sunfatnatri, cacbonat v tripolyphosphat natri t nhin ).
Bng cch bm vi p sut cao, hn hp c a qua nhng vi
phun c ng knh nht nh trn nc thp v ri trong mt lung
khng kh nng ngc dng (khong 4000C).
T c nhng ht nh (500 700um) bt cn bn. Bt cn bn ny
c ngui li t t sau khi c chuyn ra ngoi kh tri, sau
c tn tr trong cyclon.

Cc hp phn khc
B?t
n?n

Kem nho
Khng kh 3000C

Bt thnh
phm

ng gi

Hnh 8.5. S tng qut sn xut bt git.

8.6.2. Sn xut sn phm ty ra dng lng

Phn ln thuc git dng nc c iu ch bng nhng bn trn
c my khuy trn. n gin ha, chng ti ly v d thit k ch to
nhng sn phm ty ra lng khng lin. Tuy nhin mi thit k khc
nhau v cc bm (dng chuyn c ct v khng ct), nhng thng
trung gian trn trc cc hn hp, nhng my khuy trn (vi nhng
cnh khuy hoc nhng tuabin c tc thay i, nhng mt khng
196

gy chy) Nhng trong tng th, cc thit k trn cn bn khng khc

nhau nhiu.
Axit
sunfonic

NaOH

NI

Nc kh khng

LES

Du thm,
phm mu

Thng trn

Hnh 8.6. S snxut sn phm ty ra dng lng

Sn xut cc sn phm ty ra dng lng ra chn bt

Sn xut sn phm lng ra chn bng tay rt n gin.
C th s ha nh sau:
Lu trong qu trnh:
9 Khuy chm trong giai on trung ha.
9 pH phi trung tnh trc khi cho vo cht hot ng b mt NI
(cht HBM khng n nh trong mi trng axit).
9 Kim tra nhn: qu trnh gia thm mt lng mui ln s gy
ra khng t v nhn ca sn phm. Xu nht l hin tng
tch lp nhng hp cht hu c, sn phm c sa nhit
qu cao. Cc cht c hng nc c th c thm trc tip vo
nc trc khi thm nhng cht khc vo. Chc nng ca cc
cht hng nc khng phi ch iu chnh nhn m cn
nh hng n im c.
9 Qu trnh dng cc cht bo qun

197

Sn xut cc du gi
Vic sn xut du gi c th n gin, mi nh sn xut c b
quyt ca mnh vi nhng phng thc ch bin rt khc nhau, nhng
nhn chung phng php thng dng nht l: iu ch nhng hn
hp pha nc trong nhng my trn ph (chng hn nh tng c
EGMS hoc EGDS, du thm + polyme + cht bo qun). Sau a
thm cht hot ng b mt (v d LES) vo nc nng trong bn
chnh, trong khi khuy trn mnh. Cn lu rng LES 80% c th tr
nn rt qunh khi a vo dung dch, dn n qu trnh to nhng khi
kh tan. Cn a n vo bn trn vi nc nh mt bm c mt t sut
ct cao. S thm vo nhng hn hp pha sn theo trnh t xc nh r,
ph hp vi tng nguyn liu c s n nh tt ca sn phm cui
cng. Gia thm nhng cht thnh phn nhy cm khi hn hp ngui
li vi nhit di 300C v CAPB - cht ng hot ng b mt phi
c thm vo khi ngui.
Tt c nhng cht thnh phn ngoi tr cht bo qun, du thm,
cc tc nhn tr liu (chng gu) c cho thm vo nc ct nhit
65 740C. Hn hp ny c khuy trn trong 15 pht. Sau dung
dch c lm ngui 490C, k n thm nhng thnh phn cht khc
198

vo nh cht bo qun, du thm, nhng tc nhn chng gu.... hn

hp sau c lm ngui tip tc n 380C v khuy vi t sut ct
cao trong 2 pht.
Cn ch , thit b sn xut phi khng b nhim khun (nh trong
trng hp cc cht lm mm vi). Trang b nh xng v cc nguyn
liu (c bit mu v nc) phi tn trng iu kin y.
8.6.3. Sn xut x phng
Cc cng vic ty trng v ty mi ban u
Ngi ta c th lm trng v ty mi cc loi du hn hp trc hoc
sau khi trn.
Qu trnh ty trng v ty mi cho php loi tr khi du nhng cht i
nhim c trong du (caroten, mu, mucin, dip lc t...), cng nh
nhng tp cht t bn ngoi (nc, r st, bi...)
Sn xut x phng bng phng php trung ha axit bo
Phng thc ny gm ba cng on:
iu ch cc axit bo.
Chng ct cc axit bo.
Trung ha cc axit bo.
iu ch cc axit bo
Mt ct phn tch nhn t trn l nc v bn di l cht bo.
Trong phn di ca ct, cht bo (vi t trng km) c khuynh hng
i ln trn bng cch xuyn qua hn hp nc/ glyxerin pha bn trn
ca ct.
Ngc li, trong phn trn, nc (t trng ln) i xung xuyn qua cht
bo
Chng ct axit bo
Chng ct cho php loi tr nhng cht rt d bay hi/ mi (<5%)
Chng ct chnh loi tr cht bo, cng nh cc axit bo bin
cht hoc polyme ha (5% v hn)
Trung ha cc axit bo
Qu trnh trung ha cc axit bo thng c thc hin trong mt vng
phn ng. Ngi ta a vo my trn c t sut ct cao: Mt hn hp
axit bo chng ct 1000C; dung dch xt m c 900C; nc cha
mui, glyxerin v cc cht bo qun. Hn hp ny c bm vo vng
di p sut (5atm) khong 1400C.
Ta c hn hp x phng / nc ( v d: 76/24) sau c sy kh.

199

Hnh 8.7. S iu ch axit bo

Sy kh x phng nho
X phng nho c c (bng cch iu ch trn hay cch khc) c
sy trong mt thit b bc hi chn khng, c c x phng kh
chn 12 14% nc.
Hon tt x phng.
Thun li v kinh t cho cc nh my s dng trc tip nhng vy hoc
nui x phng, v sn xut x phng cn bn cht lng, rt tn km v
cn nhiu kinh ph. Tr li qu trnh iu ch x phng, sau khi sy kh,
tip tc a qua cng on tn tr x phng hon tt trong cyclon,
cung cp lin tc x phng vo my ng gi.
Khi ch to x phng bnh, cc 200 300kg, vy x phng c trn
vi cht mu, du thm trong mt my n, xong a vo mt dy trc
ln bng thp quay vi tc khc nhau v ngc chiu, mc ch
y l to mn v loi tr mi ht x cng trn x phng. Cc my
cn c lm lnh bng nc (v qu trnh cn lm tng nhit ca
x phng).
Mt my n th 2, cho php ci tin qu trnh ng nht ca hn hp,
n thng lp ghp vi mt b phn chn khng ( loi bt kh). B
200

phn c rt chn khng cui cng, c hnh chp kn vi mt tm c

c tm gia, t y cho ta mt thanh x phng lin tc, di, sn
sng ct v dp thnh cc.
Sau , thanh x phng c ct thnh bnh c chiu di nh, k
c dp di p lc trong nhng khun c lm lnh, trnh
x phng dnh vo khun. Qu trnh dp khun to ra mt lng x
phng tha, lng ny c a tr li vo u dy chuyn sn xut
n li. Lu lng n, dp khong 200 300 cc x phng / pht.
Sau cc cc x phng c bc bng mt ba cng bo v x
phng khi h hi khi vn chuyn, sau c bao giy trang tr. Sau
cng chng c gom li v ng kin. Hnh 8.8 m t ton b s
dy chuyn hon tt x phng.

B
ng

t
i

Dao
ct

Nc lm lnh

My trn

My dp

Dm bng x phng

Bng ti

Cn

Phng chn khng

Van xoay c
thng cha

Bnh
x hng

Trc cn
Hnh 8.8. S hon tt sn xut x phng

8.6.4. Sn xut kem nh rng

Phng thc sn xut kem nh rng c cha hai tc nhn chng su
rng bao gm: mt my trn chnh v nhng thng ph, trong c th
pha ch nhng hn hp trung gian.
Ha tan florua trong 30 lt nc tinh khit trong mt thng inox 200 lt.
Ngi ta a hn hp ny qua mt thng inox khc bng cch bm.
Dung dch ny l dung dch A.
Trong thng 200 lt khc, tip tc ha tan hn hp saccharinat natri v
benzoat natri trong 100 lt nc tinh khit. y l dung dch B.
Ngi ta bm dung dch B vo my trn chnh qua b lc. Cho my trn
201

hot ng trong thi gian cn thit c c mt hn hp ng nht.

Cho thm lauryl sunfatnatri, vi pht sau cho tip carraghenat natri v
dung dch A, sau cng l du thm, trong ngi ta ha trc
parahyroxybenzoat metyl.
Cho my chy trong 30 pht cho n khi c c mt qu trnh ng
nht hon ton.
Bt kh c loi ti b phn chn khng trong 15 pht.
Sau kem c lc, lm ng nht v tr vo thng.
S dy chuyn sn xut kem nh rng c biu din trn hnh
8.9.

Hnh 8.8. Dy chuyn cng ngh sn xut kem nh rng

202

CHNG 9: TNG HP THUC TR SU

9.1. Gii thiu
Thuc bo v thc vt l nhng hp cht c c ngun gc t nhin
hoc tng hp ha hc, c dng phng v tr su bnh, c di,
chuthi cy trng v nng sn. Thuc bo v thc vt gm nhiu
nhm khc nhau, gi theo tn nhm sinh vt hi, nh thuc tr su
dng tr su hi, thuc tr bnh dng tr bnh cyTr mt s
trng hp, cn ni chung mi nhm thuc ch c tc dng i vi sinh
vt gy hi thuc nhm .
Thuc tr su c tng hp bng nhiu cch khc nhau, trong
nhng thuc tr su cha clo v brom (hexacloxyclohexan, nhng axit
v phenol ca dn xut clo) c tng hp bng qu trnh halogen ha.
9.2. Mt s cng ngh tng hp thuc tr su
9.2.1. Halogen ha cc hp cht cha oxy v nit

Hyrohalogen ha cc ru
L qu trnh th nhm OH bng cc nguyn t clo hay brom, phn
ng thun nghch ta nhit sau:
CH3OH + HX

CH3X + H2O

Trong trng hp i vi cc ru bc 3, bc 2 v bc 1 cao phn t,

c th tin hnh phn ng trong pha lng khng cn xc tc. C ch
ca phn ng bao gm qu trnh proton ha ru v qu trnh th cc
nhm +OH2 k tip.
ROH + HX

RO+H2 + X-

RX + H2O

cc trng hp khc, c bit i vi cc ru thp phn t bc

1, th cn phi c xc tc gi vai tr l cht mang nc dch chuyn
cn bng sang phi. Nh iu ch bromua etyl ngi ta s dng axit
sunfuric c. Axit ny c tc dng ti sinh ng thi HBr t bromua
natri:
C2H5OH + NaBr + H2SO4

C2H5Br + NaHSO4 + H2O

i vi cc qu trnh pha lng, ngi ta thng s dng dung dch

ZnCl2 bo ha trong axit clohyric, cn i vi pha kh ngi ta dng
ZnCl2 trn cc cht mang xp.
Sn phm c s lng nhiu nht nhn c bng phng php clo
ha cc ru l clometan CH3Cl. N c tin hnh t HCl khan v
metanol trong pha kh vi xc tc d th (ZnCl2 trn silicagen hay
bt). Ti 200 - 3500C, dch chuyn cn bng sang phi ngi ta dng
mt lng d khong 20 50% HCl. Phn ng tin hnh trong thit b
ng on nhit vi lp xc tc c nh. Cc sn phm trong phn ng
bao gm: cc tc nhn cha chuyn ha, CH3Cl, H2O v sn phm ph
dimetyl ete, s c lm ngui; khi t chng axit clohyric v
metanol s ngng t. Metanol c chng ct v hon lu tr v phn
203

ng. Hn hp kh to thnh s tinh ch ra khi dimetyl ete bng axit

m c, k tip l trung ha, sy v ngng t. i vi qu trnh tng
hp clometan, phng php ny hiu qu kinh t hn l clo ha metan.
Clo ha cc ru - andehyt v xeton
Trong qu trnh clo ha ru bng clo t do, u tin xy ra s oxy
ha ru thnh anehit hay xeton, sau th xy ra qu trnh th lin
tip cc nguyn t hyro trong nhm ankyl bng clo.
C2H5OH

+Cl2
-2HCl

CH2CHO

+Cl2
-2HCl

CH2ClCHO

+Cl2
-2HCl

CHCl2CHO

+Cl2
-2HCl

CCl3CHO

Nu anehit hay xeton l tc nhn ban u, th phn ng ch xy ra

qu trnh th cc nguyn t hyro gn trn nguyn t cacbon, nm
cnh nhm cacbonyl. Tc clo ha hp cht carbonyl t l thun vi
nng ca chng, khng ph thuc vo nng clo v s c tng
cng bi cc axit trong mt phn c axit HCl to thnh.
CH3CHO

+H+

CH3CH=O+H

+H+

CH2=CHOH

+Cl2
-2HCl

ClCH2CHO

Trong s cc sn phm ca qu trnh clo ha ru, anehit, xeton th

1,1,3-triclo axeton v hexaclo axeton l nhng cht c gi tr thp, cn
sn phm quan trng nht l cloral CCl3CHO. Cht lng ny (ts= 97,80C)
c s dng sn xut hng lot thuc tr su qu him, c bit l
tricloaxetat natri v clorofoc.
Trong cng nghip, n c iu ch nh qu trnh clo ha etanol,
trong giai on u tin xy ra vi tc cao, cn giai on kt thc
th tng i chm. V vy, i vi qu trnh gin on cn phi tng t
t nhit t 40 n 80 900C. Cn i vi qu trnh tng hp lin tc
th tin hnh trong cascad cha hai thp sc kh vi dng lng v kh
ngc chiu nhau (hnh 9.1).

Hnh 9.1. S cng ngh sn xut Cloral

204

Trong thp u tin (1) nh qu trnh lm lnh, nhit c gi t

55 650C, cn ru v hn hp clo vi HCl c cho vo h thng
cui thp (2). Cht lng cha hn hp cc cloaxetanehit, axetal v
polyaxetal ca chng s chy sang thp th (2) lm vic 900C. y,
clo v nc c a vo, vai tr ca nc l thy phn axetal to
iu kin s dng ru hon ton hn.
Sn phm nhn c sau thp (2) l hn hp cloral-hyrat, polyaxetal ca cloral v cc dn xut dicloaxetanehit tng ng. N c
x l bng axit sunfuric m c, khi cc hyrat v axetal b phn
hy to thnh cloral t do.
CCl3CH(OH)2 + H2SO4

CCl3CHO + H2SO4.H2O

Cloral c tch ra khi axit sunfuric v mang i chng ct, khi chng
ct phn on nh cha dicloaxetanehit s c hi lu tr v qu
trnh clo ha. Sn phm nhn c c tinh khit 97 98%.
Cloral di tc dng ca kim b phn hy to thnh clorofoc v mui
ca axit formic.
CCl3CHO + NaOH

CHCl3 + HCOONa

Trc y trnh by phng php c bn iu ch clorofoc t

etanol v hypocloriccanxi nhng by gi phng php ny hu nh
khng cn c quan tm na.
Tng hp cc dn xut axit
Cc axit clocacboxylic mch thng, thng c iu ch nh qu
trnh clo ha cc axit cacboxylic, phn ng ny c xc tc bi cc
cht PCl3, clorua lu hunh, to kh nng chuyn axit cacboxylic thnh
anhyrit v cloanhhyrit, cc sn phm ny cng l cc cht xc tc. S
nh hng ca chng vi clo v cc axit clocacboxylic, s xy ra khi
phn hy cc anhhyrit.
CH3 - COCl
+HCl

+Cl2
-HCl

ClCH2 - COCl

CH3COOH
-HCl

ClCH2 - CO - O - CO - CH3

ClCH2 - COOH + CH3 - COCl

Phn ng cng dn n qu trnh to thnh cc sn phm thay th

lin tip nguyn t hyro, trn nguyn t cacbon nm cnh nhm
cacboxylic.
Thnh phn cc sn phm, nh thng l s c iu chnh khi thay
i t l ca clo v axit carboxylic. Phn ng xy ra khi sc kh clo vo
hn hp axit lng v xc tc nhit tng t t n 150 1700C.
Axit monocloaxetic ClCH2COOH (l cht tinh th) nhn c nh qu
trnh clo ha axit axetic vi anhyrit axetic l cht xc tc. N c sn
xut di dng axit t do thay mui natri, v dng sn xut cc cht
dit c dng clophenoxyaxetat. ArOCH2COONa cng nh cacboxy
metyl xenluloxen CH3COONa.
205

Axit tricloaxetat CCl3COOH di dng mui natri n l thuc dit c .

Vic thay th ba nguyn t clo vo trong phn t axit axetic l mt iu
rt kh. V vy, axit tricloaxetic c iu ch trong cng nghip nh
qu trnh oxy ha cloral bng axit nitric:
CCl3CHO + 2HNO3

CCl3COOH + H2O + NO + NO2

Axit diclopropionic CH3CCl2COOH c iu ch bng qu trnh clo ha

axit propionic vi xc tc PCl3 v phenol. di dng mui natri n l
thuc dit c c s dng rng ri.
Cloxian ClCN (cht kh c mi gt; nhit ngng t 12,60) l
cloanhyrit ca axit xianit (HOCN), trong mi trng kim s thy phn
thnh dng mui ca n. Trong mi trng nc trung tnh n bn, cn
khi c mt ca axit s b polyme ha. Trong cng nghip, n c iu
ch nh qu trnh clo ha bng axit mnh trong mi trng nc.
Cl2 + HCN

ClCN + HCl

Cloxian l cu t d bay hi nht trong hn hp v n c chng ct

lin tc ra khi hn hp phn ng, sau l ngng t v sy kh, do
tp cht nc s gy ra qu trnh polyme ha n khi bo qun. Cloxian
s dng sn xut xianua clorua bng phng php vng ha trime
vi xc tc l cc axit.
Xianua clorua (cht tinh ch, t0nc=1460C) c iu ch theo phn ng
ny trong pha kh hay lng. Nu l pha kh th qu trnh xy ra 4000C
trong thit b phn ng dng ng vi cht xc tc l than hot tnh, cn
i vi pha lng ngi ta s dng xc tc l axit clohydric hay clorua
st 3000 v 4MPa. Xianua clorua s dng ch yu tng hp cc
thuc dit c dng triazin (ximazin, propazin).
Clo ha theo nguyn t nit
Cng tng t nh cc phn ng, trong clo lin kt vi cc
nguyn t cacbon (clo ha theo nguynt t cacbon) m chng ta gp
trn. Tuy nhin, n c im khc bit l dn n qu trnh to thnh
lin kt N-Cl (clo ha theo nguyn t nit). Cc axit amic l nhng cht
c kh nng ny, trong khi clo ha chng s nhn c cc cloamit .
Chng cha cc nguyn t clo hot ng v s dng ph bin rng ri
lm cht ty trng v st trng mnh. Cc cloamit ca axit
arysunfonic l cht c gi tr ln nht.
Cc monocloamin B v T l mui mononatri ca cc monocloamit
benzen hay toluen synfomic axit. Chng nhn c khi clobenzen hay
clotoluen sunfemit tng tc vi hyrocloricnatri. Cc monocloamin to
thnh s c kt tinh v thu nhn dng tinh khit. Chng ha tan
trong nc v s dng di dng dung dch nc 0,5 5%.
Cc dicloamin B v T l dicloamic ca benzen hay toluen sunfomic axit.
Chng c iu ch bng cch clo ha dung dch huyn ph nc v
cc sunfamic hay cc dung dch kim ca sunfamic:
206

Cc dicloamin kt ta di dng tinh th, sau chng c lc v sy

kh. Chng khng ha tan trong nc v s dng di dng dung dch
vi cc dung mi hu c.
Carbamic CO(NH2)2 v melamin cng cho kh nng clo ha theo
nguyn t nit. Khi clo ha, t melemin s nhn c hexaclomelamin
l cht c hm lng clo hot ng cao, n cng c s dng hiu
qu lm thuc st trng.
9.2.2. Tng hp thuc tr su h cacbamat (mui ca axit
cacbamic)
Tng hp cht trung gian metyl iso-cyanat (MIC)
Metyl iso-cyanat l mt cht trung gian iu ch mt s thuc tr su
nhm cacbamat.
MIC l mt cht c hi, d bay hi, d chy v c tc ng nh mt
loi hi cay d vi mt lng nng tht nh.
MIC l mt iso-cyanat hu c c to thnh bi phn ng gia 1
cyanat kim loi v mt tc nhn metyl ha v metyl iso-cyanat c to
thnh bi phn ng ca sodium cyanat (SDC) v dimetyl sunfat (DMS).
Qua phn ng, nhm metyl ca dimetyl sunfat c chuyn ha thnh
iso-cyanat.
Phn ng din ra nh sau:
CH3)2SO4 + 2NaOCN

xt

2CH3NCO + Na2SO4

Phn ng ny c th m t tng bc chi tit:

ehyrat (loi nc)
SDC, cht xc tc v dung mi c np vo bn phn ng MIC v gia
nhit n nhit thch hp.
m cha trong nguyn liu c tch khi nguyn liu th cng vi
mt phn dung mi bng s chng ct n gin di p sut km (
m phi c loi tr trc khi tin hnh phn ng to MIC v nc d
dng tc dng vi MIC to thnh cc dn xut ure v cacbon dioxit
2CH3NCO + H2O

CH 3NHCONHCH3 + CO2

Phn ng ny xy ra chm nhng do pht sinh nhit, vn tc phn ng

v p sut c gia tng mt cch nhanh chng.
Hi dung mi c cha m c ngng t ti my ngng t v chy v
bn tip nhn dung mi (solvent receiver). Ti bn ny, do s khc bit
v trng lng ring nn nc tch khi dung mi d dng v dung mi
tch nc c dng li cho m k tip.
Phn ng MIC
Sau bc loi nc, dimetyl l phn ng ta nhit v nhy vi nhit .
Do tc nh git khng i v nhit ca phn ng phi c
iu khin cn thn.
207

MIC to thnh cng vi s nh git ca DMS cng thi im c

np vo ct nhi (MIC packing column). Hu ht dung mi b bay hi
cng vi MIC c ngng t khu vc ngng t di o sut thp ca
ct nhi v hon lu v bn phn ng. MIC c tinh khit thp cha
mt phn dung mi c tinh khit ha bi s cn bng pha khi i
ngang qua phn trn ca ct nhi.
Khi s nh git ca DMS hon tt, mt lng nh nguyn liu th
(DMS, SDC) v MIC hon lu vn cn nm li trong cc bn phn ng
v ct nhi.
Trong sut phn ng MIC, nhit nh ca ct nhi c kim sot
mt cch khng i bi h thng kim sot t ng. Sau khi xong giai
on nh git DMS, giai on ti gia nhit c tin hnh bi s gia
tng nhit ca bn phn ng to phn ng cho s nguyn liu
cha phn ng ht v thu hi MIC tn ng. iu kin vn hnh s ti
nhit tng t nh giai on nh git DMS.
Sau 3 gi v khi khng cn MIC chy vo bn tip nhn MIC, phn ng
hon tt.
S thu hi dung mi
Sau khi phn ng MIC hon tt, dung mi cha sn phm ph v cht
xc tc vn cn ng li trong bn phn ng MIC. Dung mi tn ng
c thu hi bi s chng ct p sut chn khng v c s dng li
cho m k tip. thu hi dung mi, bn phn ng nng nhit p
sut 200mmHg/chn khng tuyt i. Dung mi c lm bay hi,
ngng t v chy vo bn tip nhn dung mi
Sau khi thu hi dung mi, DMS, nhng sn phm ph v mt phn
dung mi vn cn ng li trong bn phn ng ha tan cc cht v
c, sau dung dch nc thi c chuyn n bn ra dung mi c
cnh khuy trn. Np thm nc vo bn ra dung mi v khuy trn
thi gian cht v c ha tan mt cch hon ton.
Sau khi kt thc s khuy trn, nc thi c cung ng n bn tch
ly dung mi v y phn ln dung mi c tch khi nc thi do
s khc bit trng lng ring. Dung mi tch ra c chuyn n bn
cha dung mi thu hi, cn nc thi c chuyn n thit b x l
nc thi.
9.2.3. Tng hp thuc tr su butyl phenol metylcyanat (BPMC)
BPMC l mt loi thuc tr su gc cacbamat, c s dng ngn
chn su c thn v su c l. BPMC c tng hp t phn ng
gia MIC vi orto-sec-butyl phenol (OSBP). Tc phn ng rt nhy
vi nhit .
Phn ng c m t nh sau:
208

O H

OH
CH3NCO +

O-C-N-CH3

CH-CH2-CH3

CH-CH2-CH3

CH3

CH3

S khi sn xut BPMC

M t qui trnh tng hp BPMC

OSBP v cht xc tc c np vo bn phn ng cacbamat. Phn
ng khi u bng s thm vo tng git MIC. Nhit phn ng phi
c khng ch cn thn bng cch kim sot lin tc lng MIC cho
vo. Pht ng sinh nhit v vy vic lm lnh nh dng hi lu trong h
thng ng xon v lp v o bn ngoi loi tr nhit phn ng.
Sau khi kt thc s nh git MIC, iu kin phn ng phi c duy tr
khng i km theo s khuy trn lin tc sut 2 gi mt s OSBP
cn li phn ng vi MIC mc ti a. Khi phn ng c hon tt
(da trn kt qu phn tch mu), hn hp sn phm c cung cp
n thit b tinh ch BPMC (BPMC stripper).
Tinh luyn BPMC
209

Sn phm cha mt lng nh MIC cha phn ng v cht xc tc

c a n b phn x l v MIC cng cht xc tc c kh hon
ton BPMC c tinh khit cao.
Khng kh nng v kh ( 600C) c phun qua thit b tinh ch BPMC
loi i cht cha phn ng, BPMC c bm a vo thit b tinh
ch v tip xc vi khng kh bc ln qua ct nhi ca phn trn thit b
stripper. Khng kh v MIC cha phn ng tch ra c chuyn qua b
phn ngng sng (demister) lp t trong b phn tch (separator)
ca thit b stripper.
Kh ph thi cha khng kh v MIC c cung cp n thp lc kh
(gas scrubber) v MIC b phn hy do tip xc vi dung dch sodium
natrihyroxit (NaOH) c trong thp lc v kh c chuyn n thn ng
khi ni hi.
Khi s phn tch mu t BPMC stripper t yu cu v nhng c tnh
sn phm, BPMC c ng kin thnh phm.
9.2.4. Tng hp thuc tr su cacbofuran
Cacbofuran l loi thuc ph bin s dng tr su, mc, dit tuyn
trng trong cy c, trong t. N cng c th p dng cho t trng trt
v h cy c l. Cacbofuran cho thy r hot tnh phn cn tha li vn
tt v phn tn nhanh chng trong t. N tht l tng s dng
thch hp cho nhng v ma nh la, ng, c ci, lc, thuc l, bng
vi v cc loi rau
Cacbofuran c tng hp bng phn ng gia MIC v 7-OH (2,3dihydro-2,2-dimetyl-7-hydroxy benzofuran).
Phn ng din ra nh sau:
HO

CH3
OH

CH3-N-C-O

CH3

CH3

XT

CH3NCO +
MIC

CH3

7-OH

CACBOFURAN

Sau khi phn ng tng hp cacbofuran hon tt, cht phn ng, hn
hp cacbofuran v dung mi c tch ly bi my ly tm.
Bt c lc, c sy kh trong my sy v ng thng t 97%
cacbofuran. Cacbofuran (97%) c trn vi ph gia v cht n theo
cng thc pha ch thch hp v c nghin thnh bt mn bng my
nghin t kch thc <325 mesh.
S khi qu trnh tng hp cacbofuran

210

M t tm tt qui trnh tng hp cacbofuran

7-OH, dung mi v cht xc tc c np vo bn phn ng v nh
git MIC bt u phn ng. V tc phn ng rt nhy vi s thay
i nhit nn tc nh git MIC c kim sot cht ch v t
ng. Nhit phn ng c kim sot nh s lm lnh tun hon
ca h thng ng xon v lp v bc ngoi.
Sau khi hon tt vic nh git MIC, phi duy tr iu kin phn ng
khng i vi s khuy trn trong 2 gi. Khi phn ng hon tt (qua
vic phn tch mu), sn phm phn ng c bm vo bn n nh v
c lm lnh bng phng php tun hon vi etylen glycol kt
tinh cacbofuran trong dung mi.
S ly tm v thu hi dung mi
Huyn ph cacbofuran trong bn kt tinh c cung cp vo my ly tm
theo nguyn tc trng lng mt cch nh k. Hot ng ly tm c
thc hin di s kim sot tun hon tng m mt.
Sau khi lc, vng lc cacbofuran c co bng dao trong my ly tm
v c x xung my sy. Phn dung mi lc i ngang qua vi lc v
c dn vo bn cha dung mi thu hi v c a vo chu trnh k
tip. Sau vi chu k n c tinh ch phn tp cht c t phn ng
cacbamat bng cch gia nhit n nhit thch ng
Dung mi tinh ch c chuyn vo bn cha dung mi mi v
phn cn li di y bn chng ct dung mi c a vo thng
211

cha x l di dng ph thi.

Qu trnh sy
Bt cacbofuran c lc bi my ly tm cha mt lng nh dung mi.
Trong khi cnh khuy ca my sy quay u, mt lng nh dung mi
b bay hi v c ngng t li bi b gom t dung mi (solvent trap),
cn vng cacbofuran c trn ng nht.
Sau 2 gi sy kh, cacbofuran c tinh khit cao (97%) c ng
thng sn xut cacbonfuran 75%.
S nh dng cacbofuran
Cn c vo s phn tch tinh khit ca cacbofuran cng nghip,
cacbonfuran c cn chnh xc theo cng thc pha ch thch hp v
trn vi mt lng ng ca cht ph gia v cht n. Cacbofuran
cn ng v cht ph gia c a vo ngn cp liu v hn hp c
trn u trong my trn th nht (s cp)
Hn hp ng nht c cung cp n my nghin t b phn cp liu
kiu vt xon, bt c nghin mn bi p lc kh nn cao. Trong qu
trnh nghin, hn hp c truyn ti i v tp trung trong cyclon v
thit b lc kiu ti (bag filter). Bt sn phm mn c chuyn n v
trn li trong my trn th 2 (th cp).
Sn phm hon tt c ng vo thng
Cacbofuran c tnh c hi cao, v th nhng cng c sn xut
cacbofuran phi m bo khng thot bi ra ngoi.
9.3. ng dng ca thuc tr su
Thuc tr su (insecticide) dng tr cn trng gy hi. Mt s loi
thuc tr su cn c hiu lc tr nhn hi cy trng. Tc ng ca
thuc tr su i vi cn trng gn ging nh i vi nhn hi.
9.3.1. Tc ng ca thuc tr su

Xm nhp ca thuc tr su vo c th cn trng

Thuc tr su c c tnh thm thu qua v c th cn trng gi l
thuc tr su tip xc (contactinsecticide). Cc loi thuc tr su tip
xc c kh nng ha tan trong lipit v lipoprotein, v ha tan ny
cng cao hiu lc tip xc ca thuc cng mnh. Lp biu b trn v
ca c th cn trng (epicuticula) cha lipit v nhng cht ging
colestecin, l nhng cht ha tan c nhiu hp cht thuc tr su
hu c. Song thuc khng qua c lp biu b ngoi, (exocuticula) do
v cng (protein thuc da) v cng rt kh qua lp biu b trong
(endocuticula) m thnh phn ch yu l kitin. Song hai lp biu b ny
khng bao gi ph ton b c th cn trng, m c ch l nhng on
da mm nh cc on khp u, ngc, bn chn, chn lng, ru, c
quan cm gic. Thuc xm nhp qua ch da mm ny v qua cc tuyn
tit dch vo lp h b v mng y (hypodermis), ri t vo t bo
212

thn kinh, t bo mu v c truyn i khp c th thng qua h tun

hon. Cc ch phm cha dung mi hu c thm thu qua lp biu b
mnh hn cc dng ch phm khng cha dung mi hu c. Dung mi
hu c trong ch phm c kh nng ha tan cht bo, thm t nhanh
qua lp biu b trn, hot cht trong ch phm li dng ha tan nn
d thm thu qua vt cn hn. Do vy, thuc tr su tip xc dng
sa hoc dung dch hiu lc tr su mnh hn dng khc.
Thuc xm nhp qua ng tiu ha
Loi thuc tr su tc ng qua ng tiu ha gi l thuc v c
(stomach insecticide). Qua ming vo ng rut cng vi thc n,
thuc c hp th ch yu on rut gia qua bao rut peritrophit,
ri khuch tn qua lp biu b rut vo t bo thn kinh, mu v c
truyn i khp c th. Mt lng nh thuc cng c th thm thu qua
thnh rut trc vo thnh rut sau v c gi li , nht l vng
t bo tuyn rectum ca rut sau. Qu trnh ng ha v bi tit thc n
tin trin cng chm, cht c lu li trong rut lu, lng cht c xm
nhp vo c th cng ln. Tuy nhin mt phn cht c b phn gii do
tc ng ca men tiu ha v pH ca dch rut.
Thuc xm nhp qua ng h hp
Nhng loi thuc ngoi tc ng qua ng tip xc, v c cn gy
hiu lc qua ng h hp, do mt phn thuc bin thnh th kh gi l
thuc c tc dng xng hi (fumigant action). Cht c xm nhp qua l
th c th cn trng v t qua h thng kh qun v vi kh qun vo
t chc t bo, thng qua qu trnh thng hi (ch yu kh qun) v
khuch tn ( vi kh qun). Thuc xm nhp qua ng h hp gy c
nhanh v mnh hn so vi xm nhp qua ng rut v qua v c th
cn trng, bi thuc tc ng ngay ti t bo thn kinh. Cng h
hp cn trng cng mnh thuc cng xm nhp nhanh.
9.3.2. Qu trnh gy c ca thuc tr su
Hot ng sng ca cn trng rt tinh vi, phc tp v c to nn
bi qu trnh trao i cht v nng lng vi s iu khin ca h thn
kinh. H thn kinh iu ha mi hot ng ca c th, l cu ni c
quan cm gic vi c quan khc trong c th, cu thnh nn qu trnh
hot ng nhp nhng trong h thng sng. Mt trong chui hot ng
sng ny b tc ng bi cht c, th cn bng trong h b ph v,
hot ng sng b ngng tr v c th cn trng b t vong.
Qu trnh gy c ca thuc ln hu c v cacbamat
Cc cht c ln hu c v cacbamat c ch hot tnh men
colinettecazo (CHE) lm cho qu trnh dn truyn kch thch thn kinh b
t lit. S c ch ny ca ln hu c gi l photphoril ha v ca
cacbamat gi l cacbamil ha men CHE. Qu trnh dn truyn kch thch
thn kinh, lin quan cht ch ti vic gii phng ra u mt dy thn
213

kinh cht dn truyn kch thch thn kinh l axetylcolin (cn gi l cht
mi gii hoc cht trung gian). Axetycolin lm nhim v dn truyn xung
qua khe xinap ca t bo thn kinh, ri li c thy phn thnh colin
v axetat. Axetylcolin l ete ca axit axetic v colin, sinh tng hp nh
men colinettecazo. Trong t bo no, Axetylcolin c thy phn nh
men colinettecazo c hiu gi l Axetylcolinettecazo. Men ny rt nhy
cm i vi s c ch ca thuc ln hu c v cacbamat. Cc ettecazo
khc trong t bo no cng thy phn axetylcolin nhng chm hn v
gi l pseudocolinettecazo. Tng quan cn bng sinh tng hp
axetylcolin (v qu trnh gii phng ra n t cc lin kt protit) vi qu
trnh thy phn axetylcolin bng men colinettecazo, c ngha ln i
vi s dn kch thch thn kinh. Khi men CHE b c ch, th cn bng
dn truyn kch thch thn kinh b ph v v b t lit hon ton. Mt
khc axetylcolin khng c thy phn nn tch ly li vi lng ln,
gy hin tng qu kch thch thn kinh lm cho dy thn kinh tn
thng v t on. Song photphoril ha v cacbamit ha men CHE l
qu trnh thun nghch. Men CHE khng b ph hy v thay i hot tnh
sinh hc khi c gii phng ra khi cht c ch ln hu c v
cacbamat. Cn trng trng c ln hu c, ngoi biu hin t lit thn
kinh cn b ri lon trao i nc nh ng dch trong xoang ph tng
v xut huyt qua ming. Qua trng lng c th b gim ti 1/3.
thuc ln hu c c cc kiu cu trc photphat (1), photpho-amidat (2),
photphonat(3),
photphorothionat(4),photphorothiolat(5),
hotphorothiolothionat (6), photphonothionat (7), photphonothiolothionat
(8).
Kiu cu trc P=S c i lc lin kt men CHE yu hn P=O. Trong c
th cn trng v ng vt nng cu trc P=S c chuyn thnh cu
trc P=O di tc dng ca men oxy ha kh (men h xitocrom v men
nhm SH)
Do vy thuc ln hu c c cu trc photphat (TEPP. DDVP,
phosphamidon, EPN, dibrom. Phosdrin,...) hiu lc khi im cao hn
kiu cu trc thiono v thiolo (malathion, dimethoat, gusathion,
diazinon,...)
2.2.1 Qu trnh gy c ca thuc dimetylaminopropandithiol
(DAPD):
Cc hp cht dimetyl amino propan dithiol nh cartap, bensultap l
nhng hp cht ng ng (analogue) hoc tin cht tr dch hi
(propesticide) ca hp cht c nereistoxin t nhin. DAPD khng c
ch men CHE nhng li c ch hot tnh ca th quan (receptor) mng
sau xinap t bo thn kinh trung ng, lm t lit qu trnh dn truyn
kch thch thn kinh, c ch tc ng ny ging c ch gy c Nicotin.
Qu trnh gy c ca thuc clo hu c, pyrethroit v
214

oxihyrocacbon (nh trebon)

L nhng cht c i vi t bo thn kinh. T bo thn kinh ch huy
hot ng sng ca c th, thng qua phn x v c dn truyn di
hnh thc xung in qua qu trnh pht sinh lin tc in th hot ng,
trong in th trc l nguyn nhn cho in th sau v in th u
sinh ra do tc nhn kch thch. Ngi ta cho rng, qu trnh chuyn vn
ion K+ v Na+ qua mng l nguyn nhn ca s pht sinh in th hot
ng dn truyn hot ng xung. Thuc trebon (ethofenprox), DDT,
DMDT, perthane, dicofol, TDE, chloropropylat,... lm t lit dn truyn
xung trn si trc t bo thn kinh (axon), ch yu l h thn kinh
ngoi bin, thng qua phn ng lin kt vi mng si trc m nhng
cht tham gia phn ng l thnh phn protein, lipit v men ca mng.
S lin kt phc cht pht trin nhanh nhit thp (di 250C).
nhit cao, (trn 250C) qu trnh ny xy ra chm hoc khng xy ra.
Theo narahashi (1971) hu qu ca phn ng lin kt thuc vi thnh
phn cht ca mng cn tr vic vn chuyn ion v c ch hp th
ion Na+, K+ ca mng, gy nn hin tng mt phn cc ko di v
khng hnh thnh c in th hot ng ca mng si trc. DDT v
cc hp cht clo hu c cn c ch hot tnh men c hiu atpazo v
mt s men khc nhng khng c ch men CHE. Cn trng trng c
trebon, DDT v cc hp cht tng t DDT, th hin trng thi nhim
c thn kinh vn ng v cm gic nh run ry, co git, t lit cc chi
v t vong. Thuc HCH gy c t bo thn kinh v t bo hu ht c
quan ni quan, qua c ch phn chia nhn t bo trung k, dn n
hin tng a bi th, tc l xut hin t bo nhiu nhn khng ng
nht. Cn trng b nhim c HCH lc u b kch ng vn ng, v
sau co git, lit chi, cnh b dui thng ngang. Cc hp cht pyrethroit
c th gy hin tng mt cc v qua c ch hnh thnh in th
hot ng ca t bo thn kinh hoc c ch hp th ion Na+v K+ ca
mng t bo, c ch truyn xung t thn kinh ngoi bin ti thn kinh
trung ng.
Cc hp cht c ch trao i cht v trao i nng lng
Trao i cht v trao i chuyn ha nng lng trong c th sng
c lin quan vi nhau. Khng c trao i chuyn ha nng lng th
khng c trao i cht, v hot ng sng ca h thng sng i hi c
qu trnh tiu hao nng lng, v c ly t cc hp cht hu c
di dng thc n thng qua chui h hp m. l qu trnh oxy ha
sinh hc din ra di nhiu bc vi s tham gia ca cc men. Cc
hp cht asen, rotenon v xianua (HCN), gy tc ng n s h hp
m qua c ch hot tnh men h hp nh: men hyrogenazo (xc tc
tch v vn chuyn nguyn t hyro t c cht n ubiquinon), men
xitocrom b, c1, c v men oxidaza (xc tc vn chuyn in t n oxy,
215

hot ha oxy phn t). Asen c ch hot tnh men piruvat

ehidrogenazo v men -xetoglutarat ehyrogenazo, lm tch ly axit
xetonic, do ngn cn qu trnh oxi ha kh piruvat hnh thnh
axetyl-CoA l nguyn liu ca chu trnh Krebs.
Cc hp cht c ch sinh trng v pht trin cn trng (IGR):
C th cn trng c hai nhm hooc mn ecdizon (hooc mn lt xc)
v juvenil (hooc mn tr) iu ha sinh trng, pht dc v bin thi
ca cn trng. Ecdizon c tng hp cc tuyn ni tit, di tc
ng ca hoocmn no v c tt c cc pha pht trin, v trc khi
cn trng lt xc hm lng ecdizon trong huyt tng tng, nhng li
gim khi lp v xut hin du hiu lt xc. Juvenil ch xut hin giai
on u trng v bin mt giai on nhng v trng thnh. Juvenil b
c ch hot tnh hoc ngay c nng juvenil qu cao trong huyt
tng, u lm cho trng pht trin khng bnh thng (khng n c
hoc u trng b cht sau khi n), u trng khng ha nhng,.... mt s
cc hp cht c ch sinh trng v pht trin cn trng l nhng hooc
mn ecdizon v juvenil nhn to, khi c su hp th vo c th s
lm tng hm lng trong huyt tng gy mt cn bng sinh l do
ph v qu trnh bin thi ca cn trng.
Mt s hp cht khc c ch trc tip tng hp kitin, do ph v qu
trnh lt xc ca cn trng.
Cn trng c v rt chc v th tch li khng thay i sau khi
hnh thnh nn chng, phi thay v mi qua mi ln pht trin gi l lt
xc. V hp cht kitin (poliaxetylglicoamin) l thnh phn quan trng ca
v c th nn qu trnh tng hp kitin quyt nh ti vic lt xc ca cn
trng. Khng c qu trnh tng hp kitin th s lt xc khng th xy ra,
v do qu trnh pht trin c th u trng b ngng tr. Xc tc cho
s tng hp kitin l men kitin-UDPN-axetyl gluco aminyl transferazo
(kitin-UDPN-axetyl):UDPN-axetylglicoamikitin.
Hp cht c ch sinh trng v pht trin cn trng nu trn, c ch
sinh tng hp kitin bng cch lin kt vi men kitin-UDPN-axetyl, lm
mt hot tnh ca men ny; kch thch hot ng men phenoloxidazo v
kitinazo, a n s ngn cn hnh thnh lp cuticula mi; c ch hot
tnh men chuyn ha cht ecdizon, gy tch t cht ecdizon, c tc dng
kch thch qu trnh hot ng men kitinazo, lm cho kitin khng tch t
c. Ngi ta cn cho rng, hp cht iu khin sinh trng cn
trng, c ch sinh tng hp ADN trong t bo m non ca lp biu b
m phn bng, cng lm cho u trng khng lt xc c.
9.4. Phn loi thuc tr su
9.4.1. Thuc tr su cha clo

a s hu ht hp cht tr su clo hu c bn vng trong mi

trng sng nn b cm s dng nhiu ni trn th gii.
216

Camphechlor
(toxaphen, Clotecpen, polychlorcamphen) l hn hp camphen clo
ha cha 67 69% clo, tc dng qua ng rut, tr c nhiu loi
su ming nhai hi thc vt, thuc nhm c I, LD50 per os: 80
90mg/kg, LD50 dermal: 780 1.075mg/kg, rt c i vi c.
DDT (gesarol, neocid)
Diclodiphenyl tricloetan, tc dng tip xc v v c, thuc nhm c
II, LD50 per os: 113 118mg/kg, LD50 dermal: 2.510mg/kg.
3.1.1. Lindan (gama-BHC, gama-HCH, gama-666)
Gama 1,2,3,4,5,6 hexacocyclohexan, tc dng v c, xng hi,
tip xc, tr c nhiu loi su hi thc vt, thuc nhm c II, LD50
per os: 88 125mg/kg, LD50 dermal: 1000mg/kg; ADI 24 gi: 0,01
mg/kg; MRK: 0,01 10 mg/kg (to, nho, rau ly c, du m thc vt
0,5mg/kg, sa v sn phm ch bin t sa 0,01 mg/kg; khoai ty 0,05,
tht 0,1, ng cc 0,2, cc nng sn khc 1,0 10 mg/kg); PHI: 7 15
ngy (chu u), 21 30 ngy (M, c), thuc c vi ong v c.
Methoxychlor (metox, DMDT)
1,1,1-triclo-2,2-bis (4-methoxiphenyl) etan, tc dng tip xc, v c,
tr nhiu loi su hi thc vt v cn trng y t, th y, t bn vng hn
trong mi trng sng, thuc nhm c IV, LD50 per os:6.000mg/kg.
Perthane
1,1 diclo 2,2 bis (4 - etyl phenyl) etan, tc dng tip xc, tr
nhiu loi su ming nhai v chch ht. Thuc nhm c IV, LD50 per
os:8170 mg/kg.
Hp cht nhm cloxicloien
Clodane (chlordane): thuc tc ng qua ng rut, tip xc v
xng hi: rt bn vng trong mi trng sng, dng ch yu tr mi,
LD50 per os:457 - 590 mg/kg, LD50 dermal: 200 - 2000 mg/kg, ADI: 0,001
mg/kg, thuc c kch thch t bo ung th.
Heptaclo (heptachlor): thuc c tc dng v c, tip xc v xng hi,
dng tr kin, mi, mt. Ngy nay, t c dng cho cy trng. LD50 per
os:147 - 220 mg/kg, LD50 dermal: 2000 mg/kg, ADI: 0,0005 mg/kg.
Aldrin tc dng qua ng rut, tip xc v xng hi, ngy nay ch yu
dng tr mi. Trong mi trng sng, aldrin chuyn ha thnh
dieldrin. LD50 per os:38 - 67 mg/kg (rut), 50-80mg/kg (th), LD50
dermal: 98 mg/kg, ADI: 0,0001 mg/kg. (aldrin + dieldrin).
Endrin tc dng tip xc, v c hiu lc ko di, LD50 per os:10 - 12
mg/kg, LD50 dermal: 60 - 120 mg/kg.
9.4.2. Thuc ln hu c

Thuc nhm thuc tr su ln hu c c nhiu hp cht, trong c

hp cht rt c. Xt trong thc t nc ta, t c kh nng p dng
nn chng ti khng cp ti nhng hp cht ln hu c c c
217

cp tnh qu cao (thuc nhm c I) v nhng hp cht b cm s

dng Vit Nam.
Chlorpyrifos
Tn gi khc: lorsban, dursban, sanpyriphos...
Tn ha hc: 0,0-dietyl O 3,5,6 triclo 2
pyridyphotphorothioat.
Cng thc ha hc:C9H11Cl3NO3PS
Phn t lng: 350.62
c tnh: dng tinh th khng mu, tan rt t trong nc, tan tt trong
benzen, axeton, xilen, thuc nhm c II, LD50 per os:135 - 163 mg/kg,
LD50 dermal: 2000 mg/kg. ADI: 0,01mg/kg, MRT: cam, chanh 0.3 mg/kg,
hoa qu khc 0,2 mg/kg, rau 0,05 mg/kg, PHI: 14 21 ngy, thuc c
i vi c v ong mt.
S dng: chlorpyrifos c tc dng tip xc, v c v xng hi. Thuc
tr c nhiu loi su ming nhai v chch ht hi la, rau, mu cy
cng nghip, cy n qu, hoa v cy cnh, tr cn trng y t v th y,
liu s dng t 500 -1000g a.i/ha. Chlorpyrifos c gia cng thnh cc
dng sa (20 48%), bt thm nc (25%). Chlorpyrifos cn c ch
bin hn hp (hoc dng hn hp)vi cypermethrin, dimethoat,
diflubenzuron,....
Chlorpyrifos methyl
Tn gi khc: reldan, pyriban M...
Tn ha hc: 0,0DimetylO -3,5,6 triclo 2- pyridylphotphoro
thioat.
Cng thc ha hc: C7H7Cl3NO3PS
Phn t lng: 322,5.
c tnh: thuc dng tinh th, tan t trong nc, tan tt trong axeton,
metylic,hexan: thuc nhm c III. LD50 per os: >3000 mg/kg, LD50
dermal: 2000 - 3700 mg/kg. ADI: 0,01mg/kg, MRL: ng cc 5,0mg/kg,
hoa, qu, c chua 0.5mg/kg, ch, go v cc nng sn khc 0,1 mg/kg,
PHI: (xem chlorpyrifos). Thuc rt c i vi c v ong mt.
S dng: chlorpyrifos methyl tc dng v c, tip xc v xng hi.
Thuc c dng tr nhiu loi su hi la, rau , mu, cy n qu, cy
cng nghip, hoa, cy cnh, cn trng y t, th y, phun x l su, mt,
nhn hi. Thuc c gia cng thnh dng sa 50%, dng ohun bt
2%, dng phun m, liu s dng t 500 1000g a.i/ha. Chlorpyrifos
methyl thng c dng hn hp vi cypermethrin, fenobucarb,
permethrin.
Diazinon
Tn gi khc:basudin, kayazinon, dianon, diazol...
Tn ha hc: 0,0dietyl0,2iso-propyl6metylpyrimidin4yl
photphorothioat.
218

Cng thc ha hc: C12H21N2O3PS

Phn t lng: 304,3
c tnh: Dng dung dch, khng mu, tan trong axeton, benzen,
xyclohexan, toluen, xylen, tan t trong nc, khng n mn kim loi;
thuc nhm c II v III (dng ch phm), LD50 per os: 300-400mg/kg,
LD50 dermal: 2.150mg/kg. ADI: 0,002mg/kg, MRL: ng cc 0,1, rau qu
0,50,7, tht 0,7mg/kg (FAO). Mt s nc quy nh MRL 0,3 i vi
rau, qu v 0,05 mg/kg i vi cc sn phm khc; PHI: cy n qu, rau
14 20 ngy, c ci 42 ngy, c rt 60 ngy. Thuc c i vi c v
ong mt.
S dng: Diazinon c tc dng tip xc, v c, xng hi v thm
su, diazinon tr c nhiu loi su ming nhai v chch ht hi rau,
mu, cy n qu, cy cng nghip; lng dng t 500-1000g a.i/ha.
Diazinon c gia cng thnh cc dng ht cha 5 v 10% diazinon
dng 10-20kg/ha tr su c thn la, hi thn u , hnh, tr su n
la. C cc ch phm dng sa 40%,50%,60%. Loi sa 50% dng 1-2
lt/ha, tr su n l, su chch ht l la, rau, u dng 1 lt/ha, tr
su c thn la 1,5lt/ha. nng 0,1-0,2% diazinon sa 50% dng
phun cho cy n qu, ch, bng, ma tr rp, nhn , ry xanh.
Diazinon sa v bt cn c dng tr b cht, rp, mt v mt s loi
cn trng y t v th y.
Dimethoate
Tn gi khc: Bi 58, Rogor, Roxion, Bitox...
Tn ha hc: 0,0-dimetyl-S-metyl-cacbomoyl-metylphotphorodithioat.
Cng thc ha hc: C5H12NO3PS2
Phn t lng: 229,2
c tnh: thuc k thut (96-98%) dng tinh th mu trng ng, tan t
trong nc (25g/lt), tan trong ru (300g/kg), benzen, Clorofom, toluen;
tng i bn pH t 2-7, thy phn nhanh trong mi trng kim,
n mn st; thuc nhm c II. LD50 per os: 250-680mg/kg, LD50
dermal: 600-1.200mg/kg; ADI: 0,002mg/kg, MRL: rau n qu, n c 0,5
10, rau n l 0,1. ng cc 0,05, c chua, du ty 1,0, sn phm khc
0,004mg/kg; PHI: rau 7-10 ngy, ng cc 21 ngy, ng, la, cy n qu,
khoai ty 14 ngy. Thuc c i vi c v ong mt.
S dng: l loi thuc tr su ni hp c tc dng tip xc, v c,
dng tr cn trng v nhn hi cy trng, lng s dng 300-700g
a.i/ha. C nhiu dng ch phm nh sa 20, 40, 50, 60%, bt thm
nc 20%, dng ht 5%, dng hn hp dimethoate + permethrin;
dimethoate + fenvalerat; dimethoate + cypermethrin; dimethoate sa
40-50% dng pha nc 0,05 0,15% tr rp mui (aphis), nhn , rp
sp, ry xanh, b xt, b tr,, mui hi rau, u , bng, ma, ch, thuc
l v cy n qu.
219

Ethoprophos
Tn gi khc: ethoprop, mocap, prophos...
Tn ha hc: O-etyl-S,S-dipropylphotphoro-dithioat.
Cng thc ha hc: C8H19O2PS2
Phn t lng: 242,3
c tnh: thuc k thut th lng, vng nht, tan t trong nc
(750mg/lt), tan trong hu ht cc loi dung mi hu c, bn trong mi
trng nc trung tnh v axit nh, thy phn nhanh trong mi trng
kim (pH>9); thuc nhm c I (dng sa 15 v 20%) v II (dng ht
10%); LD50 per os: 62mg/kg, LD50 dermal: 2.4mg/kg (chut), 26mg/kg
(th); MRL: da, lc, ng, khoai ty, khoai lang, bp ci, u
0,2mg/kg. Thuc c i vi c v ong mt.
S dng: ethoprophos c tc dng tip xc nhanh, mnh nhng
khng c hiu lc xng hi v ni thp, dng tr su (1,6-6,6kg
a.i/ha) v tr tuyn trng hi r cy trng (6-10 kg a.i/ha). Ethoprophos
c gia cng thnh dng ht 5% (Mocap 5G), 10% (Mocap 10G), 15
v 20% (Mocap 15G, 20G). dng sa 6EC (Mocap 6EC=6
pounds/gallon=720g
a.i/lt),
sa
4EC
(Mocap
4EC=
4
pounds/gallon=480g
a.i/lt)
v
sa
2EC
(Mocap
4EC=2
pounds/gallon=240g a.i/lt). Tr tuyn trng hi chui dng 25-40g
Mocap 10G/gc chui, tr su hi chui (Cosmopolites sp) dng
30g/gc. Tr tuyn trng hi thuc l dng 0.5-1g a.i/m2 t vn m,
tr tuyn trng hi da dng 60-100kh Mocap 10G/ha (x l ton b
din tch),tr b hung nu hi ch bn 10g Mocap 6EC/ha, tr tuyn
trng h tiu bn 30g Mocap 10G/gc.
Fenamifos
Tn gi khc: nemacur
Tn ha hc: etyl-4-metylthio-m-polylisop-ropyl-photphoamidat.
Cng thc ha hc: C13H22NO3PS
Phn t lng: 303,4
c tnh: thuc k thut dng tinh th khng mu, bn trong mi
trng trung tnh, tan trong hu ht trong mi trng trung tnh, tan
trong hu ht cc dung mi hu c (tr ete du ha v ligroin), tan t
trong nc (700mg/lt),khng n mn kim loi; thuc nhm c I: LD50
per os: 15.3-19.4mg/kg (c ti kiu ghi 5mg/kg), LD50 dermal: 500mg/kg,
ADI: 0,003mg/kg; MRL: khoai ty, c chua 0,2, chui, nho, c ph ht
0,1, sn phm khc 0,05mg/kg. Thuc c i vi c.
S dng: l loi thuc ni nhp c hiu lc cao i vi tuyn trng,
su hi r v su sinh sng di t. Thuc tr c cc loi tuyn
trng ni v ngoi k sinh, tuyn trng sng t do, tuyn trng nang,
tuyn trng nt sn. liu dng 5-20kg a.i/ha; x l theo vt (rng 3045cm) 7-40g a.i/100m2, x l nhng cy con vo trong dung dch thuc
220

100 400mg/lit trong 5 30 pht. C th dnbg tr su v tuyn trng

cho chui, la m, la nc, caphe, cam, chanh...
Loi ch phm Nermacur sa 40% pha vi nc 0.1% phun hoc ti,
loi ht 5 10% dng rc vo gc cy hoc vo t tr tuyn trng,
b hung nu, mi hi ch, chui h tiu,... liu lng 20 40g nermacur
10g/gc, bn u vo t trong phm vi mc r.
9.4.3. Thuc cacbamat
Bendiocarb
Tn gi khc: Seedox, Garvox...
Tn ha hc: 2,2dimetyl-1,3benzodioxol4metyl cacbamat.
Cng thc ha hc: C11H13NO4
Phn t lng: 223,2
c tnh: dng tinh th, tan t trong nc, tan trong axeton,
cloroform, dioxan, bn vng trong nhit v nh sng, trong dung dch
chua nh, trong mi trng kim thy phn mnh hn trong mi trng
axit, khng n mn kim loi, thuc nhm c II; LD50per os: 40
45mg/kg. Thuc c i vi ong v mt.
S dng: Bendiocarb c tc dng tip xc, v c hiu lc ni hp
yu hn. Dng tr cn trng y t, su mt hi kho (v thuc t gy mi
kh chu v khng n mn vt liu bng kim loi), tr cn trng sinh
sng di t, phun tr su hi rau mu v cy n qu. Thuc c
ch bin nhiu dng khc nhau, trong c cc dng hn hp vi
Thiram, captan, Fosetyl aluminium (Aliette) dng tm ht ging,
hn hp vi PBO v Pyrethrin tr cn trng y t.
Cacbaryl
Tn gi khc: Sevin, cacbamec...
Tn ha hc: 1 naphtylmetylcacbamat.
Cng thc ha hc: C12H11NO2
Phn t lng: 201,2
c tnh: thuc k thut (>99%) dng bt, tan t trong nc (0.1%),
tan trong dimetylformamit (30 40%), dimetylsunfonit, axeton (20
30%), Clohexxan (20 30%), bn vng trong nhit v trong mi
trng trung tnh v axit nh, khng n mn kim loi. Cacbarryl 80SP
thuc nhm c II, ch phm c nng cao hn thuc nhm c I,
ch phm c nng thp hn thuc nhm c III, : LD50 per os: 246
850 mg/kg: rau qu 1.0 1.5mg/kg, cam, chui 0.5mg/kg...
S dng: cacbaryl tc dng tip xc, v c v thm su vo m t
bo, thuc c thi gian tc dng ko di, dng tr cn trng v nhn hi
rau mu, cy cng nghip. Thuc c gia cng thnh nhng dng bt
thm nc%, 80%, 85%, dng bt 5 10%, dng hn hp vi Rotenon,
Diazinon, vi thuc tr nm Maneb...Loi bt thm nc 85% dng mt
kg ch phm/ha tr b xt hi, ry xanh, 1.5 1.8 kg ch phm/ha tr
221

su xanh hi rau, nhn hi cam, 0.5kg/ha tr rp hi rau, ng.

Methomyl
Tn gi khc: Lannate, Nudrin, sathomyl...
Tn ha hc: S metyl N [(metyl cacbamoy) oxi] thioaxetimidat.
Cng htc ha hc: C5H10N2O2S
Phn t lng: 162,21.
c tnh: thuc k thut dng tinh th, mu trng tan trong nc
57g/lit, tan trong etanol 42g/100g v metanol 100g/100g, thuc nhm
c I qua ng tip xc v nhm c IV qua ng tip xc , LD per
os: 17 24 mg/kg, LD50 derman: 5880 mg/kg, ADI: 0.03 mg/kg, PHI: 7
15 ngy, MRL: 2mg/kg i vi x lch, 1mg/kg nho v cc loi qu
khc, 0.2 0.5 mg/kg cc sn phm ng thc vt khc.
S dng: methoxy l loi thuc tr su ni hp, tip xc v v c, c
hiu lc vi nhn , dng tr nhiu loi su hi rau, u, cy n qu
nh su t, su xanh, su xm, su c qu, rp cc loi. Methomyl
c ch bin thnh cc loi bt thm nc 90% dng 250g
1000g/ha, dng dung dch 24 29% dng 0.3l 1.0l/ha.
9.4.4. Thuc pyrethroit.

T xa xa, con ngi dng bt hai loi hoa cc tr cn trng

v nhn hi hoa mu. l hoa cc chrysanthemum cinerariaeforlium
v C.roseum c cha 6 este ca axit cyclopropan cacboxylic rt c i
vi cn trng v nhn hi l pyrethrin I, cinerin I, jasmolin I c tn chung
l crysanthematv pyrethrin II, cinerin II, jasmolin II v gi chung l
pyrethrat. Trong hoa cc tr su (kh) cc este pyrethrin chim 73% v
c ch bin thnh dng bt 45 55% hoc 25% c trn ln vi cht
tng hiu PBO dng tr cn trng y t v th y, tr su mt hi kho v
phun cho cy trng. Di tc ng ca nh sng, cc este pyrethrin
phn gii v mt hiu lc rt nhanh chng, pyrethrin thuc nhm c III,
LD50 per os: 273 2370 mg/kg, LD50 derman: 1500mg/kg, ADI:
0.04mg/kg, PHI: khng qui nh. thuc rt c i vi c, c nhng c
tc dng xua ui i vi ong mt.
Nghin cu c im ca cc este ciClopropan cacboxilat t nhin,
c bic l cu trc ha hc ca pyrethrin c u im hn cc este
pyrethrin t nhin. Nhng dn xut gi l pyrethroit. Hin nay c trn
30 hp cht pyrethroit dng tr cn trng v nhn hi thc vt, nhiu
nht l Acrinathrin, Alphamethrin, Cyfluthrin, Cyhalothrin, Cypermethrin,
Deltamethrin, Fenvalerat, fenpropathrin, Flucythrinat, Permethrin...Nhm
thuc pyrethroit c nhng c im sau:
Lng hot cht s dng trn n v din tch thp, c khi ch 8
10g/ha nn lm gim ng k lng cht c ri trn mi trng sinh
thi.
C tc dng chn lc cao, t c hi hn i vi thin ch c ch, tr
222

c chung su chng thuc ln, clo v cacbamat, tuy nhin hin

tng su chng pyrethroit, ln, clo hu c v cacbamat cng xy ra.
Pyrethroit ha tan nhanh trong lipit v lipoprotein nn tc dng tip
xc mnh, nhng cho n nay cha c loi thuc pyrethroit ni hp v
gy tc dng xng hi mnh. Thuc gy hin tng chong c nhanh
(knock down effect), kch thch cy pht trin v c tc dng xua
ui mt s loi cn trng.
c cp tnh i vi ngi v ng vt mu nng thp hn so vi
nhiu hp cht ln hu c, chng phn hy trong c th sng v trong
mi trng, nhng thuc rt c i vi c v cc loi ng vt thy
sinh v hiu lc thp i vi su c thn la.
Cc hp cht pyrethroit c cu trc ha hc lp th rt phc tp, c
nhiu cu hnh khc nhau, to nhiu ng phn lp th v hiu lc tr
su ca mi ng phn lp th c th khc nhau (xem bng 6.1). Cn
c vo hiu lc tr su v qu trnh tc ng phi hp gia cc ng
phn lp th m ngi ta c th s dng n hoc hn hp cc ng
phn.
Cc hp cht cyfluthrin
Cyfluthrin
Tn gi khc: baythroit, solfac...
Tn ha hc: (RS)--cyano-4-flo-3-phenoxibenzyl (1RS, 3RS: 1RS,
3SR)-3-(2,2- diclovinyl)-2,2-dimetyl cyclopropan cacboxylat
Cng thc ha hc: C22H18Cl2FNO3
Phn t lng: 434,3
c tnh: thuc k thut dng nho, mu vng tan rt t trong nc,
tan trong nhiu dung mi hu c, cha 4 cp ng phn vi t l: 2327% I (R)--cyano-4-flo-3-phenoxibenzyl (1R)-cis-3-(2,2-diClovinyl)
2,2- dimetylxiClopropancacboxylat
+ (S) , (1S)-cis, 32-36% III(R) (1R) trans -+(S), (1S)-trans v
21 25% cp ng phn IV (S) , (1R) trans -+ (R) (1S) trans.
Thuc nhm c II, LD50 per os: 600mg/kg, LD50 dermat: 5000mg/kg;
ADI: 0,02mg/kg. Thuc c i vi ong mt.
S dng: thuc tc dng tip xc v v c, hiu lc khi im nhanh
v ko di, tr c nhiu loi su hi rau, qu, bng, ay, ma, su
mt hi kho v nng sn bo qu, cn trng y t v th y. Thuc c
ch bin thnh dng dung dch 2,5% v 5%, dng bt thm nc ULV,
dng ht, dng 25-30g a.i/ha tr su t, su khoang, rp, su xm hi
rau, mu, 40-60g a.i/ha tr su xanh, su hng, rp hi bng, su o
hi ay, lc, cufluthrin c th hn hp c vi hu ht cc loi thuc
tr su v tr bnh (tr thuc tr nhn azocyClotin).
Beta cyfluthrin
Tn gi khc: bulldock
223

Tn ha hc: (RS)--cyano-4-flo-3-phenoxibenzyl (1RS, 3RS: 1RS,

3SR)-3-(2,2- diclovinyl)-2,2-dimetyl cyclopropan cacboxylat.
Cng thc ha hc: C22H18Cl2FNO3
Phn t lng: 434,3
c tnh: thuc k thut dng tinh th khng mi, mu nh, tan t
trong nc, tan trong nhiu dung mi hu c, l hn hp ca 4 cp
ng phn: 2% cp ng phn I, 30-40%II, 3%III v 53-67%IV, thuc
nhm c II, LD50 per os: 500mg/kg, LD50 dermat: >5000mg/kg; ADI:
0,02mg/kg. c i vi ong mt.
S dng: dng tr nhiu loi su hi cn trng, nng sn bo qun,
cn trng y t, th y, c bit thuc c hiu lc cao i vi chu chu,
liu s dng 25-30g a.i/ha.
Cc hp cht cyhalothrin
Cyhalothrin
Tn gi khc: cyhalon, grenada.
Tn ha hc: (RS)--cyano-3-phenoxibenzyl (z)-(1RS, 3RS)-(2-clo3,3,3- triflopropenyl))-2,2-dimetyl cyclopropan cacboxylat
Cng thc ha hc: C22H19ClF3NO3
Phn t lng: 449,9
c tnh: thuc nguyn cht k thut c tinh khit 90% (trong
95% l ng phn C:S), th du mu vng nu, khng tan trong nc,
tan trong hu ht cc dung mi hu c. Thuc nhm c II. LD50 per os:
114-166mg/kg, LD50 dermat: 1000-2500mg/kg; ADI: 0,02mg/kg.
S dng: tc dng tip xc v v c, hiu lc khi im nhanh, ko
di, dng tr su cho hoa, cy cnh, tr cn trng y t v th y, c bit
thuc c hiu qu cao i vi cc loi chy rn, ve, bt.
9.4.5. Thuc dimethyl amino propan dithiol (DAPD)

Bensultap
Tn gi khc: bancol, victenon
Tn ha hc:S,S-2-dimetylaminotrimetylen-di (benzenthiosunfonat)
Cng thc ha hc: : C17H21NO3S4
Phn t lng: 431,6
c tnh: thuc k thut dng tinh th mu vng nht, tan rt t trong
nc, tan nhiu trong dung mi hu c nh axeton, clorofoc, bn trong
mi trng axit nh (pH<5), nhng thy phn trong mi trng trung
tnh v kim, thuc nhm c III, LD50 per os: 484 (chut nht) 1120mg/kg (chut cng), LD50 dermat: >2000mg/kg, t c i vi ong
v c.
S dng: l hp cht ng ng (tin cht thuc tr dch hi) ca
cht c t nhin nereistoxin, tc dng tip xc v v c, c ph tc
ng rt rng, c bit c hiu lc cao i vi su b cnh cng v
cnh phn hi la (c thn, cun l) rau, mu, cy n qu, cy cng
224

nghip, tr c su t chng thuc ln, cacbamat v pyrethroit. thuc

ch bin thnh dng bt thm nc, ht lng dng 0,25-1,5 kg
a.i/ha.
Cartap v cartaphyrochloride
Tn gi khc: padan (cartaphidroClorua)
Tn ha hc:
+ cartap: S,S (2-dimetylaminotrimetylen)-bis (thiocacbamat)
+ cartaphyrochloride: cartapmonohidroClorua.
Cng thc ha hc:
+cartap: C7H15N3O2S2
+cartaphyrochloride: C7H16ClN3O2S2
Phn t lng:
+cartap: 237.3
+cartaphyrochloride: 273.8
c tnh: cartaphyrochloride k thut (>97%) dng tinh th khng
mu, tan trong nc (200g/l 250C), cn etylic v metylic, khng ha
tan trong benzen, axeton, hexan, bn trong mi trng axit, thy phn
trong mi trng trung tnh v kim, ht m mnh, khng n mn kim
loi. Thuc nhm c II. LD50 per os: 325-345mg/kg, LD50 dermat:
1000mg/kg; ADI: 0,1mg/kg, MRL: ch en 20, hoa bia 5, ci ba91p 0,2,
go, ng cc, khoai ty 0,1, sn phm khc 0,05mg/kg, PHI: 14 ngy,
c vi c, c trung bnh i vi ong mt.
S dng: cartaphyrochloride tc dng ni hp, v c v tip xc,
hiu lc xng hi yu; thuc khng git cht su ngay nhng gy tc
ng chn n, lm su ngng n ngay v cht bi tc ng ca thuc
v i. Thuc c ph tc ng rt rng, tr c nhiu loi su hi la,
rau, mu, cy n qu, cy cng nghip, cy lm nghip.
Cartaphyrochloride c ngun gc sinh hc, c tnh mi trng thp
nn phm vi s dng rt rng ri. Thuc c gia cng thnh dng bt
tan trong nc (SP) 255, 50%, 95%, 98%, dng ht (G) 4%,10%. tr
su c thn la dng 0,6 1,5 kg a.i/ha, ry xanh ui en 0,4 - 0,5
kg a,i/ha, xu cun l 0,5-0,6, b tr 0,4-0,5, b xt hi, b xt gai, su t,
su khoang, su xanh 0,5-0,8, su ba ba, rp hi rau 0,4-0,5, b xt
mui, ry xanh 0,5-0,8, b cnh t, su xp l ch 0,4-0,8 kg, su v
ba hi cam, chanh 0,4-1,0kh a.i/ha, thuc c th hn hp vi nhiu
loi thuc tr bnh v tr su khc s dng.
9.4.6. Thuc c ch sinh trng v pht trin cn trng (IGR)
Cc loi thuc c c ch c ch qu trnh sinh trng v pht trin
cn trng cn c gi l thuc iu ha sinh trng cn trng (jnsect
growth regulator, vit tt l IGR) c s dng t nhng nm 80 tr
su chng thuc ln, clo hu c, cacbamat v pyrethroit. Tuy nhin,
hin tng su chng thuc IGR cng pht trin nhanh. Nhm thuc
225

IGR c c im:
IGR gy hiu lc chm nhng ko di, nhiu hp cht ch c tc
dng i vi pha u trng hoc u trng, nhng, trng m khng c
hiu lc trc tip i vi pha trng thnh.
IGR tc dng chn lc cao, t gy hi k sinh c ch, t c i vi
ngi, ng vt mu nng v mi sinh.
Thuc tc ng qua tip xc, ng tiu ha v ni hp.
Buproferin
Tn gi khc: applaud
Tn
ha
hc:
2-tec-butylimino-3-iso-propyl-5-phenyl-3,4,5,6tetrahiro-2H-1,3,5-triadiazin-4 -ure.
Cng thc ha hc: C16H23N3OS
Phn t lng: 305,4
c tnh: thuc nguyn cht 98%, dng tinh th, khng mu hoc
vng nht, tan rt t trong nc, tan trong nhiu dung mi hu c, bn
vng trong dung dch axit, kim nhit cao v nh sng. thuc nhm
c III. LD50 per os: 2198-2355mg/kg, LD50 dermat: >5000mg/kg. PHI:
la m, da chut, c chua, c 1 ngy, la, ch, (thuc sa) 7 ngy
cam, chanh, bi 14 ngy, la (thuc ht) 21 ngy. Thuc c i vi
c, khng c i vi ong mt.
S dng: buproferin c ch tng hp kitin, ph v th cn bng sinh
hc hooc mn ecdizon, dit tr u trng v gy tc ng trng thnh
trng ung. Thuc c s dng tr nhiu loi su hi nh ry nu
hi la (0,05-0,25 kg a.i/ha, ry lng trng hi la (0,125-0,5kg a.i/ha),
ry xanh hi ch, u (0,25-0,5kg a.i/ha), rui hi rau (0,125-0,25kh
a.i/ha), cc loi rp hi cy n qu (0,5-1,0kg a.i/ha), b xt hi la
(0,01kg a.i/ha), b xt hi cy n qu (1,0kg a.i/ha). Buprofezin c gia
cng thnh dng bt thm nc 25%, dng dung dch huyn ph m
c 40%, dng ht 2% buprofezin c dng 30-40kg ch phm/ha
tr ry nu hi la. Khi ri thuc cn gi nc trong rung lin tc trong
3 ngy vi mc nc khong 3 cm. Loi ch phm 25WP cha 25%
buprofezin c dng pha vi nc nng 0,1% tr ry xanh
hi ch, su v rp hi du (thuc rt t c i vi tm), tr rui v
nhn hi c. thuc c pha vi nc nng 0,05-0,1% tr rp
v rui hi da chut, c chua, ry xanh ui en hi la. Loi thuc
hn hp cha 5% buprofezin v 20% isoprocarb c dng vi lng
250-500g a.i/ha tr ry nu v b xt hi la, ry xanh hi lc, ry
xanh v b xt mui hi ch, ry bng trng hi c ph. Thuc
buprofezin tc ng n su hi chm. Thuc khng dit c ry
trng thnh (nu khng hn hp vi isoprocarb), v sau 3-7 ngy tc
dng dit ry non ca thuc mi th hin r v hiu lc ca thuc ko
di t 21-25 ngy.
226

Chlorfluazuron
Tn gi khc: atabron
Tn ha hc: 1- [3,5-dico-4-(3-clo-5-triflometyl-2-pyridyloxi)-phenyl]3-(2,6-diflobenzoyl) ure.
Cng thc ha hc: C20H9Cl3F5N3O3
Phn t lng :540,66
c tnh: thuc nguyn cht k thut 94% dng tinh th, khng
tan trong nc, tan t trong mt s dung mi hu c nh axeton (55g/l),
Clorofom (30g/l), xiClohexanon (110g/l), bn vng di tc ng ca
nhit nh sng v trong dung dch thy phn. Thuc nhm c III,
LD50 per os: >8500mg/kg, LD50 dermat: 1000mg/kg. Thuc rt t c i
vi c v ong mt.
S dng: Chlorfluazuron c ch tng hp kitin, u trng, nhng b t
vong do khng xy ra qu trnh lt xc. Thuc tc ng qua ng rut
v tip xc, dng tr u trng, cn i vi su trng thnh thuc c
kh nng lm cho trng ra bi ung. Thuc c gia cng thnh dng
sa 50g a.i/ha, dng hn hp vi profenofos, Ethiofencarb. tr su
xanh, su khoang, su hng hi bng dng 50-250g a.i/ha; tr b
u di hi bng (anthonomus) dng 50-150g a.i/ha; tr su c
thn ng dng 15-100g a.i/ha; tr su khoang hi rau pha ch phm
5% (5EC) vi nc nng 0,05-0,1% ri phu t u ln l rau.
9.4.7. Cc nhm thuc tr su ha hc khc.

Diafenthiuron
Tn gi khc: pegasus, polo
Tn ha hc: 1-tec-butyl-3-(2,6-diisopropyl-4-phenoxiphenyl) thioure.
Cng thc ha hc: C23H32N2OS
Phn t lng: 384,6
c tnh: thuc k thut bt khng mu, tan rt t trong nc, tan
trong nhiu dung mi hu c nh axeton, toluen, bn vng trong mi
trng nc, khng kh v nh sng. Thuc nhm c III, LD50 per os:
2068mg/kg, LD50 dermat: > 2000mg/kg, ADI:0.003mg/kg, thuc c i
vi ong mt, t c hn i vi c.
S dng: Diafenthiuron c ch h hp ca t bo cn trng v nhn,
thuc tc dng qua tip xc v v c, dit tr trng thnh u trng v
c tc dng i vi pha trng. Diafenthiuron c dng tr cn trng v
nhn hi cy n qu, rau, ch, bng, hoa v cy cnh. Thuc rt t c
i vi cc loi k sinh c ch. Diafenthiuron c ch bin thnh dng
dung dch huyn ph c, dng bt thm nc (250SC, 500SC, 50WP)
hoc dng hn hp vi fenoxycarb (dicare 37,5 WG).
Ethofenprox
Tn gi khc: trebon, etofenprox
Tn ha hc: 2-(4-ethoxiphenyl)-2-metylpropyl-3-phenoxibenzyl ete
227

Cng thc ha hc: C25H28O3

Phn t lng: 376,49
c tnh: thuc nguyn cht th rn (230C) hoc th lng (40,10C),
tan rt t trong nc, tan trong nhiu dung mi hu c, bn trong dung
dch axit v kim, rt t c i vi ngi, ng vt mu nng v k sinh
c ch. Etofenprox thuc nhm c IV. LD50 per os: 21.44042.880mg/kg, LD50 dermat: 2140mg/kg.ADI: 0,03mg/kg, PHI: da chut
1 ngy, bp ci 3 ngy, tng 7 ngy, la, cy n qu 14 ngy.
Thuc c i vi c v rt t c i vi ong mt.
S dng: Ethofenprox gy c qua ng tip xc v ng rut,
tr c nhiu loi su hi, k c nhng chng su chng thuc clo,
ln hu c v cacbamat; nhng khng c hiu lc tr nhn .
Ethofenprox c gia cng thnh dng sa, bt thm nc. Cc ch
phm trebon 10EC, 20EC, 30EC cha 10%, 20% v 30% Ethofenprox.
thuc c dng vi lng 50-100g a.i/ha tr ry nu, ry xanh, su
cm l hi la, ry xanh, b cnh t hi ch, su hi thng. liu
lng 100-200g a.i/ha thuc tr c su xanh, su hng, rp v b
u di hi bng, rp v su cn l ng, rp v su xanh hi thuc l.
Thuc pha vi nc nng 10-20g a.i/100 lt nc tr rp, su
v ba, b xt, su n l hi cy n qu. Ch phm Ethofenprox hn
hp vi pyridaphenthion (20% pyridaphenthion + 10% Ethofenprox) v
ch phm hn hp Ethofenprox (5%) + dimethoat (15%) c tn difentox
c dng t 150-300g a.i/ha tr cc loi ry hi la, ch, b xt hi, b
xt xanh hi la,mu, cy n qu

228

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