You are on page 1of 100

Trng i hc Bch Khoa H Ni

n tt nghip

Li m u
Ti cc nc, cng nghip ho hc pht trin t lu v n chim mt v
tr quan trng trong nn kinh t quc dn, n l mt ngnh sng cn cho cc
ngnh khc bi v n to ra ngun nguyn vt liu cho cc ngnh khc i vo sn
xut, v to ra mt gi tri kinh t rt ln. Cn ti Vit Nam do yu t lch s nn
cng nghip ha hc cn lc hu cha pht trin c v s lng ln cht lng,
gn y chnh ph Vit Nam v ang u t, i mi v trang thit b ln con
ngi nhm thc y cng nghip ha hc pht trin, ui kp cc nc trong
khu vc v trn th gii.
Cc sn phm ca ngnh cng nghip ho hc ngy cng a dng, c s
dng rng ri trong cng nghip v i sng hng ngy bi nhng u im ht
sc qi bu ca n m kh c th thay th c nh nh, bn nhit v c, hn
na gi thnh sn xut li r hn nhiu v ngun nguyn liu li di do hn so
vi cc vt liu khc.
Phenol l mt trong nhng sn phm trung gian c vai tr quan trng trong
ngnh cng nghip ho hc. T phenol chng ta c th sn xut c nhiu cc
sn phm ha hc c gi tr kinh t ln nh tng hp cc hp cht cao phn t
(nha formandehyt, si tng hp, capron, nilon). Ngoi ra phenol cn dng
sn xut thuc nhum, cc loi dc phm, thuc n, thuc tr su, sn xut cc
cht hot ng b mt, c dng lm cht ty trng, ty c. Hn na sn xut
t con ng phenol c hiu xut cao hn, r v kinh t v n gin v mt cng
ngh sn xut. V vy vic nghin cu qa trnh sn xut phenol l mt vn
sn xut ht sc quan trng.
Trong n tt nghip em c giao nhn v ti l Thit k phn
xng sn xut phenol bng con ng kim ho. Mt trong nhng phng
php ph bin m hin cc nc u p dng sn xut phenol. y l mt
ti rt hay nhng cng rt kh khn trong qa trnh nghin cu. V vy em rt
mong c s gip ca cc thy c trong b mn Cng Ngh Hu c -Ha
du trng i hc Bch khoa H Ni, c bit l s gip ca thy o Vn

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Tng cng ton th cc bn nhm to iu kin cho bn n tt nghip c


hon thin hn.
PHN I:

TNG QUAN V PHENOL

Phenol hay cn gi l hydroxyl benzen, C 6H5OH, l mt dn xut hydroxyl


ca cacbon thm, c tm ra u tin vo nm 1834 do nh ho hc F.Runge,
n l cht c s ca dy cc ng ng ca cc cht vi nhm hydroxyl lin kt
vi vng thm. Phenol m chng ta thu c l mt cht linh ng, chng ta
cng c th thu c phenol l cc sn phm trong t nhin v cc thc th sinh
vt. V d nh n l thnh phn ca lignhin. Do vy m n c th to ra bng qu
trnh thu phn. Sn phm ca qu trnh trao i cht l t 40mg/l. Cc hp cht
cao hn na to thnh trong qu trnh chng than hoc trong qa trnh cacbon
ha g nhit thp, than nu, hoc than cng v trong qu trnh chng ct
du m. u tin phenol c tch ra bng qa trnh tch t nha than v sau
ngi ta khng dng phng php ny khi n mt mt tng ln trong qa
trnh sn xut. Ngy nay cc phng php tng hp d hn nh theo con ng
axt benzen v clobenzen, Cc qu trnh tin tin hn sn xut phenol l
qu trnh Hook. N bt u t Cumen.
Phenol thu c c vai tr ng k trong cng nghip ho hc, n chnh l
vt liu ban u tng hp nhiu hp cht trung gian v cc sn phm cui
cng. N c s dng trong c cng nghip tng hp ha cht v cng nghip
tng hp hu c. Do sn lng phenol ngy cng tng cc nc v trn th
gii. Chng ta c th tham kho bng s liu sau y.
Sn lng phenol sn xut trn th gii theo cc phng php sn xut khc
nhau c trnh by bng 1.

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


Phng php
Nm
Nng sut
PP Cumen(%)
PP Toluen(%)
Nhng pp khc
(%)
T nha than

n tt nghip

Ty u

Th
gii
1973 1978 1989 1974 1989 1977 1985 1989 1989
1.14 1.48 1.45 1.25 1.9 0.28 0.4
0.6
5
87
88
93
87
98
100
99
96
8
10
7
2
2
3
2
9
2
3

Nht

Chu

Cc mc ch s dng phenol trong cng nghip c a ra bng 2.


Mc ch s dng
Nha phenol
Caprolactam
Axit adipic
Bisphennol A
Anilin
Cc sn phm khc
Lng tiu th

Ty u
1973
1984
37
33
22
12
11
18
0.954

25
22
2
18

M
1974
48

Th Gii
1973
60

15
3
13

Nht
1989
41
21

18
9
14
0.211

21
1.04

16
3
20
4.45

Trong cng nghip cht do phenol l nguyn liu iu ch nha phenol


formandehit, bis phenol A sn xut nha policacbonat v nha epoxy. Trong
cng nghip t ha hc t phenol sn xut capolactam v axit adipic l ngun
nguyn liu tng hp si poly poliamit, sn xut si tng hp capro v nilon.
Trong nng nghip t phenol c th sn xut c thuc dit c di v kch thch
sinh trng ca thc vt. Cc dn xut ca phenol nh fentaclophenol c
dng trong bn g, ch phm ca thuc st trng (chng mi v chng mt). Cc
sn phm nitro ha c dng lm thuc n (axit picric).
Phenol cn c ng dng sn xut dc liu trn c s sn xut axit
salisilic, aspirin.

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Ngoi ra phenol cn dng lm dung mi lm sch cc sn phm du,


lm sch du nhn khi cc hp cht d vng, lm sch axit sufuric trong qa
trnh sn xut nha lactam, acrilic.
Do cc ng dng a dng ca phenol rt a dng trong cng nghip v th
vic nghin cu qa trnh sn xut phenol l ht sc cn thit.

Chng I:

CC TNH CHT VT L V HO HC CA
PHENOL
I. Tnh cht vt l ca phenol
Phenol l mt hp cht hu c m c mt nhm - OH lin kt trc tip vi
nguyn t cc bon ca vng bezen.

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Phenol l mt cht rn, c cu trc l cc tinh th hnh lng tr, khng c


mu v c c tnh l c mi hi hng cay, phnol c im nng chy l 40,9 0C.
trng thi ho tan, n l cht lng linh ng, khng c mu v khng c vn
c. nhit khong 68.40C phenol c th ha tan trong nc trong mt gii
hn nht nh v ti nhit n c th ho tan ln nht. Khi lu phenol
ngoi khng kh, phenol b oxy ha mt phn nn c mu hng v b chy ra do
hp th hi nc. im kt tinh v im nng chy ca phenol thp hn rt
nhiu so vi nc. Phenol c nhit si l 182 0C. Phenol ho tan trong hu ht
cc dung mi hu c nh l cc hp cht thm, ru, xetol, axit, ete nhng li t
tan trong cc cht bo. Ni chung phenol l mt cht c gy bng nng khi ri
vo da.
Hn hp ca phenol v khong 10% khi lng ca nc c gi l dung
dch phenol, bi v n tn ti trng thi lng ti nhit phng. C th ni
rng phenol l dung dch thc nht trong cc dung dch hu c (cc hydrocacbon
thm, ru, xton, te, axit, cc hp cht halogenhydrocacbon..). Phenol to
thnh hn hp ng nht vi nc v cc cht khc, chng ta c th tham kho
bng s liu sau y.
Bng 1. Cc hn hp ng nht to thnh do phenol.
Cu t th hai

p sut, kPa

Nc

Isopropynbenzen
n-Propynbenzen
- Metylstrylen

Nguyn Vn Tin

im si, 0C

Thnh phn ca

101.3

94.5

phenol, %
9.21

78.8

90.0

8.29

39.2

75.0

7.2

16.9
101.3
101.3
101.3

56.3
149
158.5
162

5.5
2
14
7

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Cc thng s vt l v ho hc ca phenol.
Khi lng phn t

94.11

Nhit si

181.75oC

Nhit nng chy

40.9 oC

T trng tng i

0oC

1.092

20oC

1.071

50oC

1.050

T trng hi (khng kh =1)

3.24

nht tng i (ng)

Nhit ho hi

20oC

11.41 mPa.s

50oC

3.421 mPa.s

100oC

1.5

150oC

0.67 mPa.s

(182oC)

514

Hng s phn ly trong nc (20oC )


Nhit to thnh

(20oC)

Nhit dung ring

kj/kg

1.2810-10
160

Nhit chy

mPa.s

kj/kg

-32.590 kj/kg
0oC

1.256 kjkg-1k-1

20oC

1.394 kjkg-1k-1

50oC

2.244 kjkg-1k-1

100oC

2.382 kjkg-1k-1

Nhit dung ring (trng thi hi)


27oC

1.105 kjkg-1k-1

527oC

2.26 kjkg-1k-1

im chp chy
(DIN 51758)

81oC

Gii hn thp nht chy n trong khng kh

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip
1.3%V(50g/cm3)

101.3kPa

(20oC) 0.77 g/cm3

Nng bo ho trong khng kh


Nhit bc chy (DIN 51794)

5950C

Nhit t bc chy

7150C

im chp chy ca hn hp vi nc
khong > 820C

1-4% nc

> 1000C

>4.5% nc
in tr sut ( 450C )

>1.8107 .m

Hn hp vi 5% nc

4.9 106 .m

p sut hi bo ha

200C

0.02 kPa

36.10C

0.1

48.50C

0.25 kPa

58.30C

0.5

kPa

690C

kPa

84.80C

2.5

kPa

98.70C

kPa

114.50C

10

kPa

137.30C

25

kPa

1580C

50

kPa

184.50C

100

kPa

207.50C

200

kPa

247.50C

500

kPa

2830C

1000

kPa

kPa

II . Cc tnh cht ho hc ca phenol.


Trong phn t phenol c oxy s lin hp (p-) ca electron t do ca
nguyn t oxy vi cc electron ca vng bezen khin cho lin kt -O-H phn

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

cc hn so vi OH trong Alcol, y l nguyn nhn gy ra tnh axit ca phenol.


Do c hiu ng lin hp m mt e trong nhn tng ln lm cho phenol c
phn ng th electronphin cao hn benzen. Phenol c hai trung tm phn ng:
nhm hydroxyl v nhn thm.
1). Tnh axit
Phenol khng nhng tc dng c vi kim m cn tc dng c c vi
dung dch kim.
+ NaOH C6H5ONa

C6H5OH

+ H2O

Phenol c tnh axit mnh hn c nc (Ka =10 -10) nhnh yu hn axit


cacbonic ( Ka=10-5). V th khi cho phenol tc dng vi axit v c th phenol b
gii phng khi mui ca n
C6H5O-

+ H2CO3 C6H5OH + HCO3-

2). To thnh ete.


Phenol bin thnh ete khi tng tc vi alkyl halogennua trong dung dch
kim.
ArOH ArO-

ArOR + X-

3). Phn ng nitro ha .


Phenol tc dng vi axit nitric m c bin thnh 2,4,6 trinitro phenol (axit
adipic) l nguyn liu to cho thuc n.
OH

OH
+ HNO3

O2N

NO2
NO2

4). Phn ng kolbe.


Khi un natri phenolate trong dng CO2 to thnh natri salisilat

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

OH

OH
+ CO2

C=O

ONa

5). Phn ng to alcol.


Phenol phn ng vi formandehyt dng xc tc axit hay kim to thnh
monome tng hp nha phenol formaldehyt.
OH

H2SO4

+ HCHO

NaOH

OH

t0
CH2OH Polime

Phenol tng t nh l cc enol ca xyclohexadiennol, v vy h bin xeton


v enol nm cn bng to ra xetol trong trong khi xtol bo, v phenol n
c chuyn nhiu nht t dng enol.
Nguyn nhn ca s to thnh trng thi n nh l qu trnh hnh thnh h
thng vng thm. S n nh l rt ln bi v s ng gp ca o- v p- quinol
trong cu trc. Trong qu trnh hnh thnh anion phenolate, s ng gp ca cu
trc quinol c th hnh thnh cc in tch dng.
C s khc bit gia ru no v phenol. Do vy phenol to thnh mui vi
dung dch kali hydroxyt. nhit phng phenol c th to ra t mui vi
CO2. Ti nhit phng, gn vi nhit si caphenol, phenol c th chuyn
cc axit cacboxyl.axit axeton thnh cc mui ca chng v phenolate cng c
to thnh. Qu trnh ng gp ca o- v p- quinol l nguyn nhn gy ra thay i
cu tru cho php s thay th cc electrolphil trong qa trnh phn ng nh l
qa trnh clo ha, sunfua ha,
Nitrat ha, nitro ha. Qa trnh a vo hai hoc ba nhm nitro trong vng
benzen c th khng thu c thu c, bi v c im ca phenol theo hng
oxy ha. V d nh l theo sau qu trnh nitro ca clo benzen l qu trnh thay
th chnh clo bng nhm hydroxyl hoc qu trnhnitrat axit disunfophenol. Qa

Nguyn Vn Tin

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

trnh nitro ha v tr para c th to ra nhit ng bng. Phenol rt d dng


phn ng vi hp cht cacboxyl vi s c mt ca cc xc tc axit hoc cc xc
tc gc. Focmal andehit phn ng vi phenol cho ta ru hydroxylbezyl v to
ra nha trong qu trnh phn ng. Qu trnh phn ng gia axetol v phenol cho
ta sn phm kp A.
Trong qu trnh phn ng vi s c mt ca xc tc axit, xc tc ny lm
tinh khit phenol trong qu trnh tng hp phenol. Cc olefil tinh khit hoc cc
hp cht cacboxyl, oxit, c th b polyme ha to ra hp cht c khi lng
phn t ln hn. S dng xc tc H2SO4 hoc s thay i in tch ion ca cc
axit. V l do c th tch phenol mt cch d dng bng con ng chng
luyn.
Phenol rt d kt i vi mui diazo to ra hp cht c mu. Hp cht c
dng lm nhy cho qu trnh trc quang ca phenol l khi diazo 4nitroanilin. Axit Salixilic (axit 2 hydroxyl benzoic), c th c sn xut qua
trnh phn ng Kolbe Schemist t natri phenolate v cacbodioxit, bi v kali
phenolate to ra hp cht para. Qu trnh akyl ha v qu trnh alxyl ho ca
phenol c th to ra vi xc tc AlCl3.
Ete Diaryl c th trong iu kin khc nghit.
200oC/Cu
C6H5-ONa

+ Br- C6H5

C6H5 O- C6H5 +NaBr

Vi cc tc nhn oxyhoa phenol d to thnh gc t do. N c th dime ho


to thnh diphenol hoc c th oxyhoa su sc to thnh ihdoxybenzen v
quinol.V gc phenol tng i bn vng nn phenol l gc thch hp v n
c s dng lm cht c ch qu trnh oxyhoa. Vi vi mt lng nh phenol
th cc tnh cht trn c th gy kh khn cho qu trnh t oxyha Cumen.

Nguyn Vn Tin

10

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Chng II:

CC QU TRNH SN XUT PHENOL


Mt lng nh phenol (axit k thut ) c tch ring t nha v nh my
sn xut kh ha than trong pha hi c dng nguyn liu than bin tnh cao khi
luyn cc (than antraxit ) v mt s qu trnh cc bon ha nhit thp ca

Nguyn Vn Tin

11

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

than nu cng nh l sn phm ca phn xng cracking. Bng cc qu trnh ln


hn ta c th thu c bng cch oxyhoa benzen hoc toluen.
Cc phng php sn xut phenol trong cng nghip nh sau:
1. Qa trnh sunfua ho benzen v qu trnh sn xut phenol bng nhit
nhn benzensunfua trong mi trng kalihydroxyt nng chy.
2. Qa trnh clo ho benzen v thu phn clo benzen bng kali hydroxyt
nng chy.
3. Qa trnh clo ho benzen v qu trnh thu phn trong hi nc ca clobezen (Qa trnh Raschig, Raschig - Hooker, Gulf oxyclorit).
4. Qa trnh Alkyl ha vi propen to ra iso-propylben (Cumen). Qa trnh
oxy ho cumen to ra terta hydroperoxit ph hp v c chia ra thnh phenol
v axetol (qu trnh HooK).
5. Qa trnh oxy ha axit Toluen to benzoic v tip tc oxy ha deccbon
to thnh phenol.
6. ehydrogen hn hp cyclohexalnol-cyclohexaxnol. Tn ca qa trnh ch
l HooK (qa trnh oxyho cumen). C th ni qa trnh oxy ha cumen rt quan
trng trong cng nghip. Cn cc qu trnh khc c c a vo vi l do
kinh t. Trong qa trnh HooK, axetol c to thnh nh l mt sn phm ph.
Tuy nhin axetol khng gy tr ngi cho s pht trin ca qa trnh ny, bi v
axetol c gi tr kinh t rt cao trn th trng. Hin nay cc nh my mi c
xy dng u da trn qa trnh oxyha cumen.

I. Qa trnh oxyha cumen (Qa trnh HooK).


Qa trnh Cumen-phenol l c s to ra hydroperoxyt cumen. Qa trnh
ny c th tch c phenol v axetol, c cng b vo nm 1994 bi nh
ha hc H.HooK v S.Lang. Sau th chin th hai qa trnh ny c ng dng
vi quy m nh. Nh my u tin c xy dng v i vo hot ng nm

Nguyn Vn Tin

12

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

1952 mang tn Dio Shawwgon ti Canada v cho sn lng khong 8000 tn


phnol trong mt nm.
Ngy nay phenol c sn xut cng chnh l nh vo qu trnh ny. Trong
cc nh my M, Canada, Italia, Nht, Ty Ban Nha, n , Mexico, Braxin,
ng u, v nc c vi sn lng t trn nm triu tn mi nm. C cc
ph gia lm ngun nguyn liu rt tt cho cc qa trnh khc v c gi tr kinh t
to ln. Vn n mn khng xy ra, v tt c cc giai on phn ng u lm
vic trong iu kin bnh thng vi hiu sut cao. iu ny quyt nh s pht
trin nhanh ca qa trnh ny.
1.C s l thuyt ca qa trnh
C hai giai on phn ng to thnh trong qa trnh sn xut phenol t
Cumen.
1.trnh oxyha Cumen vi oxy to ra Cumen hydroperoxit.
CH3
HC

CH3
CH3
+

O2

H3C

OOH

2. Qa trnh tch Cumen hydroperoxit vi s c mt ca mt s axit trung bnh


to ra phenol v axetol.
Tc oxy ha cumen bng khng kh khi khng c xc tc hay cht khi
u th rt nh, v vy qu trnh tin hnh trong nh tng nc kim (pha phn
tn l cumen) vi mt lng nh hydroperoxit cumen s gip tng tc ca
giai on khi u phn ng. Mc bin i ca ca cumen t n 30% v
vy khi tip tc tng nng oxy ha trong iu kin ca qa trnh se xy ra s
phn hu peroxit v to thnh nhng hp cht ph khc.
CH3
H3C

OOH

OH
+

Nguyn Vn Tin

13

H3C CO CH3

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Sau khi oxy ha hn hp phn ng , tch lng lp hydrocacbon ri em


i phn hu trong mi trng axit, cn nc kim em quay v phn ng oxy
ha phn hy hydroperoxit ngi ta cho axit H 2SO4 long vc lm xc tc
cho qa trnh. Di p sut khng nht thit tch hydroperoxit ra khi cumen
c ln trong hn hp .
Qa trnh phn hu hydroperoxit thnh phenol v axeton l phn ng to
nhit (255kj/ mol), khi thm H2SO4 m c ngay c mt lng khng ng k
th s thu phn xy ra iu ho.
ng thi cng vi s phn hy hydroperoxit thnh phenol v axetol qa trnh
cn to thnh cc sn phm ph l axetolphenone v metanol (c bit nhit
cao).
CH3
H3C

OH
OOH

H3 C

O
+ CH3OH

Ngoi ra phn hy hydroperoxit i khi cng xy ra s tch oxy v to


thnh ru bc ba l dimetylphenyl metanol.
CH3
H3C

CH3

OOH

H3C

OH +1/2O2

Khi c mt H2SO4 dimetylphenyl metanol d dng tch nc v bin thnh


-metylstyren (c nhit si l 165.50C).
CH3
H3C

CH3
OH

Nguyn Vn Tin

CH2
+ H2O

14

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Cc phn ng bin i s to nhiu sn phm khc khng ch gii hn


cc phng trnh trn. Hn hp em i tinh luyn tch axetol, cumen, etylstyren, phenol v cn bao gm phenol, axetolphenon v cc sn phm ngng
t c nhit si cao.
Cumen d quay li oxy ha khng c c - metylstyren bi v hp cht
khng no ny km hm phn ng to thnh hydroperoxyt. Nhng vic tch metylstyren phc tp do ngi ta thch bin i n thnh Cumen bng cch
Hydro ha c xc tc.
CH3
C

CH3
CH2
+ H2

H3C

Phn ng trn tin hmh trong pha lng vi xc tc l Ni, nhit l 100 0C
v p sut khng ln.
2. M t qa trnh.
Qa trnh oxyha Cumen vi s c mt ca khng kh hoc khng kh giu
oxy. Qa trnh ny c xy ra trong cc thit b bng thp hoc hp kim. Qa
trnh thc hin trong ba thp, n c th cao hn 20m, ngi ta thng s dng
cc thp phun c kt ni vi nhau thuy c thi gian lu phn b ti u.
Dy thp c dng ph bin trong cng nghip gm c t hai n bn ci thp
phn ng. Qa trnh phn ng c thc hin nhit khong 90oC n 120oC
v p sut khong 0.5 n 0.7Mpa. Kh thi t thit b phn ng c lm lnh
t hai bn ngng t cc cht hu c tinh khit. Nc c s dng lm mt
giai on u tin ca qa trnh v lm lnh giai on k tip.
Qa trnh oxy ha Cumen l qa trnh xc tc lu chuyn t ng, tc
ca phn ng tng vi s tng ca nng hydrroperoxit. Cc thp thp c th

Nguyn Vn Tin

15

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

c dng nhanh xc tc nh l Kimla pheta cyanua. Cc hp cht to thnh


song song vi s phn hu ca hydroperoxit. Tuy nhin chng khng c s
dng trong cng nghip.
Qa trnh phn ng l to nhit khong 800kj/kg Cumen hydroperoxit.
Nhit ca phn ng c ly ra nh qa trnh lm mt. Sn phm ph chnh ca
qa trnh. Cc sn phm c to thnh do s phn hu nhit hydroperoxit
Cumen. N xy ra trong khong nhit ln hn 130oC. Cc hp cht lu hunh
nh l sufua, di sunfua, thiol, sunfuaoxit thiophel v phenol gy c ch qa trnh
t oxy ha v n bt buc phi chuyn khi Cumen.
Hm lng oxy trong kh thi t cc thit b phn ng l khong 1 n 6 %
th tch. Nng oxy ti hn trong trong qa trnh chy ca hn hp cumennitro- oxy l vo khong 8.5% th tch vi p sut phn ng khong 0.5 n 0.6
MPa. Hi nc trong pha kh dn n h thng nh hn kh tr. Nng oxy ti
hn vo khong 1% th tch, nng ny cao hn nng trong thp. Gii hn
n ca hn hp khng kh v hi Cumen l khong 0.8 n 8.8% th tch Cumen
p sut thng. p sut 0.5 Mpa trn gii hn n 10.3% th tch Cumen. Hn
hp qa trnh oxy ha cha khong 20 n 30% hydroperoxit Cumen. Nu qa
trnh phn ng xy ra trong h thng alkali-stabol, hn hp oxy ho c ra
sch bng nc v cc mui v c trc qa trnh phn ng. Phenol c chng
luyn trong khong trng t hn hp qa trnh oxy ha ta thu c nng
hydroperoxit khong 65 n 90% trc khi tch ra.

* Qa trnh tch:
Qa trnh tch axit xc tc cho ta hydroperoxit Cumen to ra phenol v
axetol tip theo sau thit b trao i ion. Axit sunfuric c s dng lm xc tc
tt nht trong cng nghip. Cc axit khc nh l axit percloric, photphoric, ptoluen sunforic, sunfua dioxit, nh qa trnh trao i ion nn c s dng rt c
hiu qa.

Nguyn Vn Tin

16

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Qa trnh tch axit xc tc theo hai cch khc nhau. Trong pha ng th,
phn d ca axetol c thay i tch trong cc phn ng v ch cn 0.1 n
2% axit sunfuric l cho qa trnh tch.
Nhit trong qa trnh phn ng l nhit si ca hn hp Axetol v
Cmen hydroperoxit. N c xc nh bng hm lng axetol. Nhit to ra t
qa trnh phn ng ta nhit mnh ca thit b vo khong 1680 kj mi kg
hydroperoxit - cumen thu c bng qa trnh bay hi axetol t h thng ca qa
trnh phn ng.
Trong pha d th ca qa trnh phn ng hydroperoxit - cumen c tch
ti 40- 45% axit sunfuric, vi t s nng 1:5. Qa trnh trn ln c thc
hin bng bm li tm, qa trnh phn ng thc s xy ra trong qa trnh lm mt
tip theo tng di nhit n nh trong khong 50- 60 oC c duy tr
thp lm lnh ring bit. Gii hn hnh thnh sn phm ph l thi gian lu ngn
khong 45- 60s. Trong h thng lm lnh trnh hin tng n mn, c bit l
NiCl2 ngi ta s dng hp kim .
Hydroperoxit - cumen c tch ra ti mt nng cn nh hn 0.1%. Tt
c ru ;dimetyl benzyl c to thnh t sn phm ph ca ca qa trnh oxy
ha nh l ehydro to ;- metylstrylen. Loi sn phm ph sinh ra di qa trnh
tch trong iu kin c axit l 4 - cumen phenol v oxit mesityl.
* Qa trnh lm vic.
Trc khi qa trnh chng luyn ca hn hp trong qa trnh phn ng, axit
sunfuric phi c trung ha hoc tch di dng cn nu khng s gy n mn,
Sau mi chuyn ti thp lm vic v trnh hin tng ngng t ca axits
trong hn hp phn ng. S trung ha c th c to ra vi Natri hydroxyt
hoc l dung dch phenolate, pha cha mui ngm nc c PH khong 5-6, c
chia tch ra hn hp phn ng. Qa trnh phn ng su sc hn l qa trnh phn

Nguyn Vn Tin

17

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

ng axit v qa trnh trch ly ca hn hp tch v mui ngm nc i vi cc


mui trung ha nh l natri sufunate hoc nc.
Trong qa trnh lm vic chng luyn axetol th c chng u tin. N
c tinh ch trong kim v thit b lc kh, sau tip tc chng li cho sn
phm tinh khit. Cumen v ;- metyl stylen c chng luyn ly t bn cha sn
phm ca thp chng axetol th, phn cn li c chng ng ph vi nc ;metyl stylen c cha c cumen. N c tun hon li hoc chng phn on
thu c tinh khit cao v tng cht lng ca sn phm.
Phenol th c chng luyn trong thp chng phenol c lm giu bng
qa trnh chng trch ly vi nc hoc qa trnh trao i ion. Trong qa trnh
tip theo, cc cu t tinh khit gp kh khn trong qa trnh tch s c tch
bng qa trnh chng luyn. Cc oxit c ngng t to thnh cc hp cht c
nhit si cao hn.
Phenol c tch vi tinh khit cao hn 99,9% bng qa trnh chng
tip theo. C s khc bit trong qa trnh chng khc so vi qa trnh chng
miu t trn l sau khi tch axetol th bng qa trnh chng luyn, cc hydro
c cha phenol th (c cumen, ;- metyl stylen) v cc tp khc c chng qu
nhit vi cht lng chng trch ly, nh l glycol, dietylen l sn phm tinh ch t
qa trnh c im si cao hn s c chng bng qa trnh tip theo .

II. Qa trnh sn xut phenol bng phng php oxy ha Toluen.


Qa trnh sn xut phenol c pht trin u tin bi Daw (nh ho hc
ngi M ). N c duy tr cho n tn by gi, hin nay c ba nh my cng
nghip tai cc nc l M, Canada, v cc vng khc.
Sau k hoch sn xut u tin Nether Land thnh cng do DSM v to
ra cc tiu chun trong cng nghip. Viscosa (Italia) dng qa trnh oxy
ha toluen ch sn xut axit benzoic, l qa trnh sn xut trung gian cho
capolactam.

Nguyn Vn Tin

18

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Qa trnh ny tri qua hai giai on.


Trong giai on th nht toluen b oxy ha vi oxy p sut kh quyn vi
s c mt ca xc tc trong pha lng to thnh axit benzoic.
CH3

COOH
O2 kk , xt
+ H2O

Giai on th hai l axit benzoic c tch ring bng qa trnh decacxyl xc


tc vi s c mt ca oxy khng kh to ra phenol.
COOH

OH
O2 kk , xt

+ CO2

* C ch ca phn ng:
Qa trnh oxy ha toluen l xy ra theo c ch gc gm c cc
gc peroxit.
Ar-CH3 Ar-CH2 Ar-CH2-OO Ar-CH2-OOH Ar -CH2-O
Ar-CHO Ar-CO Ar-CO-OO Ar-CO-OOH Ar-CO- OAr-COOH
Nng lng hot ha ca qa trnh phn ng oxy ha to nhit ca toluen
to thnh axit benzoic l 136 kj/mol. Mt s lng ln cc sn phm gc trong
sut qa trnh phn ng dn ti hnh thnh mt lot cc sn phm ph nh l
ru benzylic (0.1%), di pheyl (0.1-0.2%), benzen andehyt (1-2%), benzyl
benzoat (1-2%) v metyl diphenyl (0.7-1%), cng thm v c l cc axit
nh focmic axetic, v cc monoxit cacbon cng c to thnh. Qa trnh oxy
ha xy ra trong pha lng nhit t 120 oC -1500C v p sut khong 0.5
Mpa vi s c mt ca xc tc Co, khong 30% toluen c chuyn ha thnh
axit benzoic. chn lc t khong 90%.
Qa trnh decacboxyl oxy ha bezoic c thc hin theo Cu (II) benzoat. N
phn ng trong pha hi to ra axit benzo Salisilic v sau phn hu to ra axit

Nguyn Vn Tin

19

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Salisilic v axit benzoic ha decacboxyl to ra phenyl benzoat. Phenyl benzoat


thu phn vi s c mt ca nc to thnh phenol v axit . Trong sut qa trnh
hnh thnh axit benolsalisilic, Cu (II) chuyn thnh Cu (I), vi s c mt ca
Cu(I) benzol Cu(I) chuyn thnh Cu(II), vi oxy khng kh tc phn ng rt
cao.
O
C
O

C
2

OH
+ Cu2+

Cu

O
C
O
O
C
OH

O
- CO2

C-O

C=O

( phenyl benzoat )
OH
+ H2O
O
C
OH
O

O
+H2O

C
OH +
OH

C=O

Nguyn Vn Tin

OH

20

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Qa trnh phn ng thc hin 220 - 2500C di p sut bnh thng, hoc
l p sut nh(khng qu 0.25Mpa ). chn lc vo khong 90 %. Sn phm
ph l benzen v cc cht c im si cao. N to thnh cn sau qa trnh phn
ng. Qa trnh phn ng l to nhit, khong 1425kj mi kg phenol c sn
xut. sn xut mi tn phenol th chng ta cn ti 1.45tn toluen, 0.3kg Co
v 3kg ng.
* Cc xc tc:
Qa trnh oxy ha Toluen i hi xc tc Co phi d tan nh l Naphten
Coban hoc bezoat vi mt lng t 100- 300 ppm.
Qa trnh decacboxyl s ho tan mui Cu(II) cho vo. Trong qa trnh phn
ng hn hp c mt khong 1-5% Cu. Ngi ta ci tin nng cao chn lc
bng cch cho thm cc mui kim loi, ch yu l cc mui magie, chng hot
ng thc y qa trnh. Do sau khi pht trin hp cht molydiom III s to
ra chn lc cao hn mui Cu (II).
im khc bit ca qa trnh mi l qa trnh ca Lumnus c s
dng. Xc tc c dng l cha Cu. Qua axit bezoic c th oxy ha trong
pha hi. N l kt qu ca qa trnh phn ng vi tc cao. chuyn ha
khong 50% v hiu sut t khong 90%. C th t c khong 1 kg phenol
trn mi lt th tch ca qa trnh phn ng. iu phn nh rng cn cha
nha l khng c to thnh. Tuy nhin xc tc phi c ti sinh thng
xuyn hn na a v qu trnh u.

III. Qa trnh sn xut bng phng php nung chy kim


vi axit sunfua ha benzen.
Qa trnh sunfua ha benzen c pht trin vo nm 1867 do hai nh
ha hc A . Wurtz v A .Kerkule c miu t bng nhng qa trnh di y.
1. Qa trnh hnh thnh axit benzensunfonic bng phn ng ca benzen vi
axit sunfuric c.

Nguyn Vn Tin

21

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


C6H6

n tt nghip

C6H5SO3H

H2SO4

+ H2O

2. Qa trnh phn ng ca axit bezenesunfoic vi natrisunfit hoc natri cacbonat


to ra natribenzensulfonat.
2 C6H5 SO3 H

Na2SO3 2C6H5SO3 Na

3. Qa trnh gia nhit benzensulfonat

+ H2O + SO2

trong natri hydroxit to ra natri

phenolat.
C6H5 SO3 Na

2 NaOH C6H5ONa

+ H2O + Na2SO3

4. Qa trnh phn ng ca natri phenolat vi sulfuadioxit hoc CO 2 to ra


phenol dng t do.
2C6H5O Na

+ H2O + SO2

2 C6H5 O H

Na2SO3

Ngoi cc sn phm trn cn xy ra cc phn ng ph:


- To thnh diphenyl xylphen.
2 C6H5 SO3 H

C6H6

2 C6H5 SO2C6H5 + H2O

H2SO4

- To thnh disunfua axit benzen.


2 C6H5 SO3 H

C6H4 (SO3H)2 + H2O

- Oxi ha hon ton benzen:


C6H6 + 15SO3

6 CO2 + 3H2O +15SO2

Qa trnh ny c s dng u tin tng hp ra phenol trong cng


nghip. Qa trnh ny tip tc c ci tin p ng yu cu cht lng thp
hn ca nguyn liu v nh lng cc sn phm ph. Dioxitsulfua hoc cacbon
oxit c gii phng trong qa trnh phn ng gia axit bezenesunfoic vi
natrisunfit hoc natri cacbonate c s dng cho giai on cui to ra
phenol. Qa trnh phn ng gia benzensulfonat vi natri hydroxit xy ra
khong nhit 320- 340 0C. Mt du qa trnh phn ng c th c tip tc
pht trin bng cc qa trnh tip theo. Gi tr ca cc qa trnh ny khi so snh

Nguyn Vn Tin

22

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

vi qa trnh cumen th n cao hn, vi hiu sut t khong trn 90 % i vi


cumen. Cc qa trnh i hi nng lng cao v gy nhim mi trng.

IV. Qa trnh sn xut phenol bng phng php clo ha benzen.


Clobenzen l mt cht d to thnh phenol khi thu phn. Do cc qa
trnh sn xut phenol trn c s hp cht ny c pht trin t lu v ang
c tin hnh rng di. Mc d n c nhiu thun li l khng hnh thnh
axetol trong qa trnh sn xut phenol t cumen nhng do vn kinh t nn
khng c p dng vo sn xut.
1. Qa trnh thu phn clobenzen bng kim.
Phng php ny c dng trong cng nghip t nm 1928 M khi
khng c nhng nhm th khc, nguyn t clo lin kt trc tip vi nhn thm
nn rt bn v vy phn ng thu phn clobenzen cn phi tin hnh trong iu
kin ht sc kht khe. Clobenzen b thu phn bng dung dch 10-12% NaOH.
C ch ca qa trnh phn ng.
C6 H5Cl + 2 NaOH

C6H5ONa

NaCl + H2O

Phenonlate ngng t vi clobenzen to sn phm ph l ete difenyl v mt lng


khng ln phenolara ocxydifenyl.
C6 H5ONa + C6H5 Cl

C6H5O C6H5

C6H5Cl

C6H5 C6H4ONa +NaCl +H2O

2C6H5OH

+ C6H5ONa + NaOH

NaCl

Ete difenyl li b thu phn


C6H5O C6H5

H2O

Kt qu nhn c l mt hn hp cn bng phenolate v ete difenyl. Hm


lng ete difenyl trong hn hp ng vi hiu sut ca n l 10% so vi clo
benzen ban u.

Nguyn Vn Tin

23

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Sn phm lng ca phn ng ly ra t ni phn ng ng xon sau khi h


thp p sut a vo thit b lng. Phn trn l ete difenyl th em i tinh luyn,
phn di l phenolate em ch bin vi axit HCl v H2SO4 hoc CO2.
C6H5ONa +

HCl

C6H5ONa + CO2 + H2O

C6H5OH

2 C6H5OH

+ NaOH
+ Na2CO3

Sau khi lng phenol th em i tinh luyn.


Sn xut phenol bng phng php thu phn kim clo benzen c th kt hp
c vi qa trnh in phn mui n v clo ha benzen. Mui n dng trong
qa trnh ch l ph. Dung dch mui n thu c sau khi phn hy phenolate
em i in phn cn kim do in phn c cha NaOH v mui n khng phn
hy dng thy phn clobenzen.
2. Qa trnh sn xut phenol bng oxy Clorua ha Gulf.
Gulf nghin cu v pht trin qa trnh oxy Clorua ha. Tuy nhin qa
trnh ny cha bao gi c s dng trong mt nh my cng nghip. Trong qa
trnh oxyClorua ha benzen, phn ng c thc hin trong pha lng 50
-1700C di p sut cn bng vi mt lng xc tc axit nitric.
Trong qa trnh Gulf, qa trnh thu phn xy ra trn xc tc cha Cu-Lantan
pht pht. Do HCl c tnh n mn cao nn vt liu i hi phi c cu trc c
bit nh l qa trnh Raschig. Vn mi trng cng phi coi trng ln hng
u.

V. Qa trnh dehydro ha dn xut Clohexanol- Cyclohexanol.


Phenol c th thu c t qa trnh ehydro ha hn hp ClohexanolCyclohexanol.
OH

Nguyn Vn Tin

24

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

+ O2
OH

n tt nghip
+

O
OH

(n+m)

+ m

+ (3n+2m)H2

Qa trnh ny c pht trin do Scientific Design, c s dng xc tc rn


ng yn v cha khong 3% Pt trn cacbon hot tnh nhit t=250-425 oC.
Xc tc ca qa trnh ehdro ha khc s dng Co v Ni.
Chng ta s dng hn hp Clohexanol- Cyclohexanol vi t l l 10:1, cn
phi s dng 1.805 tn hn hp trn sn xut c mt tn phenol ( hiu sut
t khong 97.8 % trong giai on ehydro ha. Phenol to thnh hn hp ng
ng vi Clohexanol- Cyclohexanol. V vy chng ta cn s dng qa trnh
chng trch ly tch chng ra.
Qa trnh ny khng c hiu qu kinh t nu phenol c sn xut nh l
sn phm duy nht bt u t nguyn liu l Cyclohexal. Mt s nh my nh
c xy dng Autralia bt u t nhng nm 1965. Cc nh my ny c
tho b sau do l do kinh t m thay vo l qa trnh sn xut phenol bng
phng php Cumen. Cc giai on ca qa trnh sn xut phenol rt c thun
li nu chng ta kt hp vi cc nh my ln s dng qa trnh oxy ha
Clohexan. Cu trc ca qa trnh ny ging nh qa trnh sn xut Caplactam.

VI. Qa trnh Axetol ha.


Qa trnh ny c pht trin bi Hoechst, bezen c s dng lm nguyn
liu ban u. Trong qa trnh ny benzen b oxy ha vi s c mt axt axetic
(qa trnh axetol ha ) vi xc tc Palladium. Axetylbenzen hay phenyl axetat
thu c bng qa trnh thu phn s to ra phenol v axit axetic. Qa trnh ny
cha c s dng sn xut trong cng nghip.

Nhn xt:
Nguyn Vn Tin

25

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Trong cc phng php sn xut phenol nu trn th hin nay ngi ta


s dng cc phng php chnh sau y:
- Qa trnh sn xut phenol bng phng php oxyha cumen (Qa trnh
HooK).
- Qa trnh sn xut phenol bng phng php oxy ha toluen.
- Qa trnh sn xut phenol bng phng php ehyro hn hp ClohexanolCyclohexanol.
- Qa trnh sn xut phenol bng phng php clo ha benzen.
- Qa trnh sn xut phenol bng phng php nung chy kim vi axit
sunfobenzen.
V nhiu nguyn nhn khc nhau trong ch yu l l do kinh t nn hin nay
ngi ta ch yu dng phng php oxy ha cumen v phng php oxy ha
toluen v mt s phng php khc nh phng php nng chy kim.

VII. L Do la chn phng php sn xut phenol theo phng


php kim nng chy.
Nguyn chnh sn xut phenol bng con ng kim ha l s dng
nguyn liu hydrocacbon thm, m ngun nguyn liu ny chnh l sn phm
ca qa trnh chng ct du th, qa trnh kh ho than, kh ha nhin liu lng.
C th ni ngun nguyn liu ny c tr lng rt ln, v vy vn s dng n
lm nguyn liu tng hp cc hp cht hu c khc sao cho c hiu qa l
iu ht sc quan trng. Qa trnh tng hp phenol ly ngun nguyn liu l
benzen cng khng nm ngoi mc ch . Do ngun nguyn liu di do nn
lm cho gi thnh sn phm h hn cc phng php khc. Hn na cng ngh
ca phng php c pht trin t lu, dy truyn sn xut n gin hn so
vi cc phng php khc. Kinh nghim sn xut c do chi ph u t v
sn xut l thp hn so vi cc phng php khc.

Nguyn Vn Tin

26

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Ngoi ra tng phenol bng con ng kim ha s dng ngun nguyn liu
l axit sunphuric v NaOH l hai hp cht c gi thnh r, li di do sn lng.
Hn na khi sn xut bng phng php ny chng ta c th dng sn phm
Na2SO3 sinh ra trong qa trnh sn xut lm nguyn liu tng hp phenol, do
gi thnh sn xut phenol s gim i so vi cc phng php khc.

PHN II
QU TRNH SN XUT PHENOL BNG PHNG PHP
NNG CHY KIM.
I. Khi nim chung v qa trnh sunpho ha.
Sunpho ha l qa trnh thay th mt hay nhiu nguyn t hydro trong nhn
thm bng nhm suphonic - SO3H. Sn phm

gi l axit sunphomic hay

sunphoaxit.
Trong k thut tng hp cc cht hu c trung gian, sunpho ha c ngha
hng u v c ng dng rng ri. Mt trong nhng ng dng quan trng nht
l sn xut phenol.
Tc nhn thng dng hn c l axit sunphuric vi nhng nng khc
nhau. Trong k thut thng dng loi axit nng 92-93% v monohydrat (axit
sunphoric nng 98-100%), Oleum loi 25 v 65% (khng ng rn nhit
thng). Ngoi ra cn dng mt s tc nhn sunpho ha khc nh axit
closunphuric.
Khi dng tc nhn axit sunphuric (H2SO4), c th biu din phn ng
sunpho ha bng phng trnh nh sau.
ArH

HOSO3H

Nguyn Vn Tin

ArSO3H
27

+ H2

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Sunpho ha l qa trnh thun nghch, nc to thnh trong qa trnh phn


ng va pha long tc nhn, v phn hu sunphoaxit to thnh (phn ng
desunpho ha). Nu dng oleum vi hm lng SO3 sao cho khi b nc phn
ng pha long, nng tc nhn khng thp hn 100%, c th khc phc c
bng phn ng thu phn .
1. Nhng iu kin nh hng n qa trnh sunpho ha.
Nng tc nhn l yu t quan trng nht nh hng ti qa trnh phn
ng sunpho ha . Tc phn ng sunpho ha ph thuc vo nng tc nhn
sunpho ha ( H2SO4). Khi nng tc nhn thay i, tc phn ng thay i
vi mc ln hn rt nhiu so vi mc tnh ton da theo phng trnh
ng hc bnh thng.
V = K.(ArH). (H2SO4)
V d sunpho ha 1,6 naptalin di sunphoaxit, nng axt ch tng 9 % m
tc phn ng tng 39 ln.
Lng nc to thnh trong phn ng s pha long axit, tc phn ng
gim i r rt, ti mt mc no c th coi nh dng hn. Nng axit
sunphoric, biu th bng %SO3, ti axit khng c kh nng sunpho ha tip
tc na, gi l -sunpho ha. Gi tr ca -sunpho ha ph thuc vo cc hp
cht hu c, nhit phn ng v s nhm sunpho s a vo. Hp cht cng d
Sunphu ha th gi tr ca cng thp vi cng iu kin phn ng nh nhau.
i vi cng mt cht khi nhit phn ng tng, -sunpho ha s gim.
Axit sau khi phn ng (thng c nng ) gi l axit lm vic.
sunpho ha hon ton lng nguyn liu a vo, chng ta phi tnh c
lng tc nhn cn c, da vo nng axxit lm vic (- sunpho ha ).
Chng ta c cng thc sau:quas

Nguyn Vn Tin

28

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


x =

n tt nghip

80(100 )
a

x - lng tc nhn cn c monosnpho ha 1kg hp cht hu c, kg.


a - hm lng SO3 trong tc nhn sunpho ha lc ban u, %.
T cng thc trn chng ta thy: nu hm lng SO 3 trong tc nhn sunpho ha
ban u cng cao th lng tc nhn cn thit cng gim, v s khc bit gia a
v x cng nh th lng axit cn dng cng nhiu ( v lng axit lm cng
cng ln).
Khi chn nng tc nhn, cn ch ti gii hn nng tc nhn. Nu
nng tc nhn cao qa th s xy ra cc phn ng ph (nh phn ng to
sunpho - polisunpho axit ..) va gy lng ph nguyn liu li lm cho sn phm
km tinh khit. Nng tc nhn cn nh hng ti v tr ca nhm sunpho
trong nhn thm.
* nh hng ca yu t nhit .
Nhit cng nh hng rt ln n qa trnh sunpho ha, khng nhng ti
tc ca phn ng m cn nh hng ti v tr ca nhm th trong sn phm.
Khi nhit cao qa gii hn cho php c th xy ra cc phn ng ph nh oxy
ha hp cht hu c, phn ng to sunpho.
* nh hng ca yu t xc tc.
Yu t xc tc cng nh hng ti vi tr ca nhm sunpho trong sn phm.
2. Cc phn ng ph
Khi sunpho ha c th xy ra mt s phn ng ph, khng to ra sunpho
axit. Chnh nng tc nhn v nhit vt qa gii hn cho php gy nn
cc phn ng ny. Cc phn ng ph khng nhng gy hao tn nguyn liu mt
cch v ch m cn lm gim tinh khit ca sn phm. V vy cn phi khng
ch cc iu kin phn ng sao cho khng cc phn ng ph xy ra t nht.

II. C cu v ng hc ca phn ng sunpho ha.


Nguyn Vn Tin

29

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Trc khi xt c cu phn ng chng ta xt qua v bn cht ha hc ca tc


nhn sunpho ha.
1. Bn cht ha hc ca tc nhn sunpho ha.
Axit sunphuric khan (100%) nhit thng l mt cht lin hp mc
cao, gm nhng phn nh vi mch di hnh thnh lin kt hydro. Chng ta
xt cu to ca axit sunphuric.
H

O
S

Chng ta thy c s dch chuyn in t v pha nguyn t oxy nn mt


in t nguyn t hydro gim xung, hydro c xu hng ko in t v pha
mnh. Do hnh thnh nn lin kt hydro. Nhng khi nhit tng, cc lin kt
hydro b ph v. Axit sunphuric 100% b phn li theo phng trnh sau:
H3SO4+

2H2SO4

+ HSO4-

SO3 + H3O+ + HSO4-

2 H2SO4

Bng cc phn tch ha l ngi ta nhn thy rng trong axit sunphuric
100% c 99.7- 99.8% cc phn t dng lin hp. Khi nhit tng s lin hp
s gim cn 0.2- 0.3% cc phn t phn ly. Trong dung dch axit sunphuric vi
nc axit phn ly theo phng trnh sau:
H2SO4

+ H2O

H3O+ + HSO4

Cc phn t axit sunphuric ch tn ti trong dung dch axit c nng t


75% tr ln cng b pha long axit sunphoric cng b phn li mnh theo phng
trnh trn, do lng ion bisunphat cng tng.
2. C cu phn ng sunpho ha.
Nh chng ta thy trn, thnh phn tc nhn sunpho ha tng i
phc tp, bn cht ca chng thay i khi hm lng SO 3 v H2O trong thay
i.

Nguyn Vn Tin

30

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Trong khi phn ng sunpho ha nhiu hp cht hu c c trong axit


sunphuric 100%, s b oxy ha thnh cation hu c. Cho nn khi cho hp cht
hu c tc dng vi cc tc nhn oxy ha, ta c mt hn hp c phn t khc
nhau, gm cc phn t trung ho ( SO3, H2SO4, H2S2O7), cc ion HS2O7-, HSO4-,
SO4-, H3SO4+ v cc hp cht hu c dng phn t trung ha hoc cation.
Cc tc nhn HS2O7-, HSO4-, SO4- khng th l tc nhn sunpho ha, v thc
t cho thy nhiu dung dch nhng dung dch cha nhiu ccs ion trn khng c
kh nng sunpho ha.

3. ng hc ca phn ng sunpho ha.


Phn ng sunpho ha cc hp cht thm l phn ng th electrronphin. Tc
ca phn ng sunpho ha bng oleum hay axit sunphoric c th vit :
W = K. (ArH).(SO3)
Khi phn ng vi axit sunphuric , tc sunpho ha t l nghch vi hm
lng nc.
( ArH )

W = K ( H 2O)n

III. K thut tin hnh phn ng sunpho ha.


1. Phn ng sunpho ha c tin hnh trong thit b bng thp hoc gang.
C cnh khuy, v bc hay ng xon un nng bng hi nc hay lm lnh
bng nc thng, c ng cm nhit k.
Khuy trn l yu t quan trng v khi sunpho trong phn ln cc trng
hp l d th, qunh, c khi khi phn ng dng khng linh ng (sunpho ha,
benzen, toluen.. c th dng cnh khuy bi cho) khi phn ng c nht
trung bnh (sunpho ha naphatalen thnh - naphatalen sunphoaxit) c th dng
cnh khuy hnh khung, n neo.

Nguyn Vn Tin

31

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Th t cho nguyn liu phn ng ph thuc vo nhim v v iu kin


sunpho ha. Phng php cho cc thnh phn tu thuc vo tnh cht ca
nguyn liu ban u v nhit phn ng. Phn ng sunpho ha thng c
tin hnh trong khong nhit t 30- 1800C. Nu nhit phn ng khng cao
lm ta cho axit vo thit b phn ng trc sau mi cho nguyn liu c
nghin nh vo sau (nu nguyn liu dng rn) tc trong cc phn ca
thit b u bng nhau. Nu sunpho ha nhit cao, ta un nng chy nguyn
liu rn sau mi cho axit vo.
Sau khi cho ht tc nhn phn ng v nguyn liu vo ngi ta mi nng
dn nhit ca khi phn ng ln ti nhit cn thit v gi nhit
trong
mt khong thi gian no . Kt qa ca phn ng ph thuc vo nhiu yu t,
iu cn thit l phi khng ch nhit sao cho thch hp nht( nng tc
nhn, nhit phn ng, tinh khit ca nguyn liu, thi gian phn ng khuy
trn..). C nh vy phn ng mi t hiu sut cao, cht lng sn phm tt.
2. Cc phng php tch sn phm sunpho ha.
Khi sn phm sunpho ha kt thc, cn tch sn phm (sunpho axit) khi
axit lm vic. Chng ta da vo tnh cht ca sn phm chn phng php
thch hp.
*Tch bng nc : Sau khi phn ng kt thc, ngi ta cho vo khi phn
ng mt lng nc lnh hoc nc ( gim ho tan ca sunphoaxit).
Sau s lc sn phm. Phng php ny n gin, kinh t nht. Nhng ch v
p dng c i vi nhng sunphoaxit khng tan trong nc nn phng php
ny khng c p dng rng ri.
* Phng php dng mui n : Khi cho dung dch NaCl vo khi phn ng
hoc cho vo khi phn ng c pha long bng nc, s xy ra phn ng
to mui ca sunphoaxit.

Nguyn Vn Tin

32

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

*Dng natri sunphit: Sunphoaxit s tc dng vi sunphit natri to ra mui


natri nh sau:
ArSO3H

+ Na2SO3

ArSO3Na

+ SO2 + H2O

y l phng php ph bin nht, c ng dng rng ri nht, do c


nhiu u im hn so vi cc phng php khc. Phng php p dng cho qa
trnh sn xut phenol v naphtol l chnh, v n tn dng c natri sunphit to
thnh trong qa trnh phn ng nng chy kim:
ArSO3Na

+ 2NaOH

ArONa

+ Na2SO3 + H2O

trung ho sunphoaxit theo phng trnh trn, v ngc li ph liu ca


qa trnh trn dng (SO2 v H2O) c dng axit ha phenolat:
2ArONa

+ SO2 + H2O

2 Ar OH + Na2SO3

Phng php ny khng kh khn v mt k thut tin hnh phn ng li


c th tit kim c nguyn liu.
Ngoi ra cn c nhiu phng php khc na nh phng php tch bng
soda, tch bng KCl, tch bng CaCO3.

IV. Gii thiu v Benzensunphoaxit


Benzen sunphoaxit khan C6H5SO3H l cht khng mu, kh khng bay hi,
nng chy nhit 510C, phn hu khi b un nng. Benzen sunphoaxit k
thut c mu ti, cha cc tp cht H 2SO4 v nc Benzen sunphoaxit tan trong
nc. Benzen sunphoaxit l mt axit mnh, phn ly trong nc
SO3H

SO3+ H+

Mui Natri ca benzen sunphoaxit phn ng vi kim (NaOH) nng chy


cho phenolnatri, sau axit ha cho phenolnatri. y l mt trong nhng
phng php sn xut phenol trong cng nghip benzen sunphoaxit c sn
xut theo nhng phng php khc nhau. Phng php sunpho ha trong pha

Nguyn Vn Tin

33

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

lng v phng php sunpho ha trong pha hi trong sunpho ha trong hi


t hiu qu cao hn.

V. Qa trnh thay nhm sunpho bng nhm hydroxyl theo phng


php nng chy kim.
Mt trong nhng phng php chuyn ha quan trng nht ca cc
sunphoaxit dy thm l cacspo thay th nhm sunphoaxit bng nhm hydroxyl
khi cho mui ca sunphoaxit tc dng vi hydroxyl kim loi kim dng nng
chy:
ArSO3Na

+ 2 NaOH

ArONa

+Na2SO3 + H2O

Ngy nay phng php nng chy kim l phng php ch yu tng
hp cc dn xut oxy ca dy thm.
1. C cu ca phn ng.
C cu ca phn ng.
Tc nhn nng chy kim thng dng hn c l NaOH v r hn nhiu so
cc tc nhn khc. Trong qui m sn xut nh hoc sn xut cc loi sn phm
qi , nu NaOH khng kh nng phn ng c th dng KOH. Trong mt s
trng hp ngi ta cn dng hn hp NaOH v KOH, v nhit nng chy
ca hn hp thp hn so vi nhit ca tng cu t ring bit.
Kim dng nng chy l tc nhn phn ng rt mnh. Khi tc dng vi
hp cht hu c khng no, phn t kim c xu hng kt hp theo phn t ni
i. Khi mui ca sunphoaxit phn ng vi kim nng chy, phn t kim s s
kt hp vi nhn thm, sau mi tch phn t sunphit to phenolat.
SO3Na

Nguyn Vn Tin

ONa
SO3Na
34

+ NaOH

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


+

n tt nghip

NaOH

ONa

H
+ Na2SO3

+ H2O

Sau khi axit ha pheolat ta c phenol. Nhm OH thng vc v tr


ca ca nhm SO3H.Trong thc t sn xut, song song vi qa trnh chnh - thay
nhm -SO3H bng nhm OH - bao gi cng xy ra mt s phn ng ph nh
chuyn ha sn phm kt hp to thnh hydrro cacbon v sunphat.
C th biu din cc phn ng xy ra trong qa trnh nng chy kim theo
s sau:
ArSO3Na

NaOH

ArSO3Na .NaOH

ArSO3Na .NaOH + NaOH

(1)

ArOH + Na2SO3 + H2O (2)

ArSO3Na .NaOH

ArOH

+ Na 2SO4

(3)
Phn ng th hai l phn ng chnh. Trong mt s trng hp, phn ng (3)
s khng xy ra. Tnh cht thun nghch ca qa trnh to sn phm kt hp
c chng minh bng phn ngM-sunphoaxit ca phenol khi cho Rezocxin tc
dng vi bisunphit.
2.Nhng c im ca phn ng nng chy kim.
Thng thng trong cc phn ng nng chy kim, ta thy v tr ca nhm
OH trong sn phm chnh l v tr ca nhm -SO 3Na trong hp cht ban u.
Nhng hin tng khng phi bao gi cng xy ra, nhm -OH khng phi
bao gi cng chim v tr ca nhm -SO3H. Nh chng ta bit phn ng nng
chy kim cc sunphoaxit, hoc ni chung qa trnh a nhm -OH v nhn
thm bng tc dng ca kim l phn ng th nucleophin. Ion OH - s vc v
tr c mt in t nh nht.

Nguyn Vn Tin

35

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Mt in t ti nguyn t cacbon lin kt vi nhm -SO 3H c b gim i


do nh hng cm ng ca nguyn t S mang in in tch dng trong nhm
-SO3H. Cho nn trong nhiu trng hp, nhm -OH s vo v tr ca ca nhm
-SO3H.
Song mt in t ti nhng nguyn t cacbon khng lin kt vi nhm
-SO3H cng c th gim xung do nh hng ca cc nhm th khc. Cho nn
nhm -OH cng c th phn ng vi cc nguyn t cacbon nhm ny.
Cc iu kin phn ng nh nhit , nng tc nhn, loi tc nhn c
quyt nh bi hot ng ca nhm -SO 3H. Tt nhin nu nhm -SO3H cng
hot ng, phn ng s cng d dng hn. Nhm -SO 3H trong benzen sunphoaxit
l nhm km hot ng nn phn ng i hi nhit cao, trn 3000C.
Vy khi bit bn cht ca sunphoaxit, chng ta c th tin hnh phn ng
mt cch tng i d dng, la chn c cc iu kin phn ng thch hp.

3. K thut tin hnh phn ng.


a) Nguyn liu.
Hai tc nhn ch yu trong phn ng nng chy kim l mui ca
sunphoaxit (sunphonat) v kim. t hiu sut cao v cht lng ca sn
phm tt cn tinh ch cc tc nhn khi cc tp cht gy tn hi cho qa trnh
phn ng.
Sunphoaxit tham gia phn ng dng mui - suphonat. Lng tp cht v
c (nh NaCl, Na2SO4) trong khng c qa 10% trng lng sunphonat.
Cc tp cahats v c khng tan trong kim nng chy, to thnh cc, gim
linh ng ca khi phn ng dn n qa nhit cc b v c th xy ra hin chy

Nguyn Vn Tin

36

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

khi phn ng khi nhit thnh thit b tng cao trn 300 0C. axit ca mui
sunpho cng c hi i vi phn ng v phi tn kim trung ho axit, mt
khc phn ng trung ho li to thnh cc mui v c, nh hng khng tt ti
phn ng. Trong kim (NaOH v KOH) thng c tp cht clorat d gy phn
ng oxy ha. V vy cn phi tch cc tp cht trc khi a vo phn ng.
b) Cc iu kin phn ng.
Theo phng trnh phn ng phi dng 2 mol NaOH cho mt nhm -SO 3H.
Nhng trong thc tin sn xut cng nh trong phng th nghim u phi cho
d NaOH t 3 n 4 mol v c th cao hn na. gim tiu hao kim cn chn
sunphoaxit c cht lng cao, chn thit b phn ng thch hp v khng ch cc
iu kin phn ng theo ng cc yu cu.
tng linh ng ca khi phn ng v gim nhit ca khi phn
ng c th cho thm t t 5-10% nc. Khi nhit ca khi phn ng s t
270 -2800C. Nc to thnh trong phn ng s lm cho khi phn ng linh ng
hn.
Sunphonat c a vo tng m dng bt hay dung dch bo ha trong
nc. Nu dng sunphonat dng dung dch phn ng s d dng hn, khng
to bt, khng c bi.
Sau khi cho tt c sunphonat vo, va khuy trn va nng nhit ca
khi phn ng ln ti mc cn thit, gi nhit ca khi phn ng trong mt
thi gian. Trong khi phn ng cha phenolat, sunphit v kim d.
c) Cc phng php nng chy kim.
Phn ng nng chy kim c th tin hnh trong iu kin p sut thng.
Thit b phn ng c ch to bng gang, y cong, c cnh khuy. c t
nng bng kh l, than, bng du, hoc t nng bng in. Trong qa trnh phn
ng thit b c y np kn, c ca cho nguyn liu vo. Trong k thut
phng php nng chy kim c p dng rng ri nht.

VI. Qa trnh sn xut phenol.


Nguyn Vn Tin

37

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Qa trnh sn xut phenol bng phng php nng chy kim th hin qua
cc giai on phn ng sau y:
1. Qa trnh hnh thnh axit benzensunfonic bng phn ng ca benzen vi
axit sunfuric c.
C6H6

H2SO4

C6H5SO3H

+ H2 O

2. Qa trnh phn ng ca axit bezensunfoic vi natrisunfit hoc natri cacbonat


to ra natribenzensulfonat.
2 C6H5 SO3 H

Na2SO3 2C6H5SO3 Na

3. Qa trnh gia nhit benzensulfonat

+ H2O + SO2

trong natri hydroxit to ra natri

phenolat.
C6H5 SO3 Na

2 NaOH C6H5O Na

+ H2O + Na2SO3

4. Qa trnh phn ng ca natri phenolat vi sulfuadioxit hoc CO 2 to ra


phenol dng t do.
2C6H5ONa

+ H2O + SO2 2 C6H5 O H

Na2SO3

Trc y ngi ta trung ho benzen sunphoaxit bng Na 2SO3 v axit ha


phenolat bng H2SO4. Sau ny ngi ta tn dng ph liu ca cc giai on khc
nhau Na2SO3 , SO2 , H2O trung ha benzen sunphoaxit v axit ha phenolat.
S dy truyn sn xut phenol theo phng php kim nng chy c trnh
by theo s sn xut trang bn.

Thuyt minh s dy truyn sn xut.


1. Ch thch s sn xut .
1

- Thit b si (ni hi).

- Thit b qa nhit ca hi benzen.

- Thp sunpho ha.

4 v 13 - Thit b ngng.
5 v 11 - Thit b lng.

Nguyn Vn Tin

38

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

- Thp trung ho.

- Ni nung chy kim

- Thit b dt tt

- My lc ly tm.

10

- Thp phn hu phenolat.

12

- Thit b luyn chn khng.

14

- Bnh cha cc sn phm tinh luyn.

2. Qa trnh hot ng ca thp.


Benzen mi v benzen thu hi c a lin tc vo thit b bc hi benzen 1.
Thit b c un nng bng hi nc p sut 7 - 8 at. Hi benzen to thnh
c un qa nhit trong thit b 2, sau vo phn di ca thp sunpho ha
3. Thp c ti bng H2SO4. Khi chy theo cc a H2SO4 s phn ng vi
benzen to thnh benzen sunphoaxit , t li di y thp. Hi benzen cn d
sau phn ng v hi nc phn ng c ngng t trong thit b 4 v lng trong
thit b 5. Benzen thu hi c a tr li phn ng.
Benzen sunphoaxit vo phn trn ca thp trung ha 6. Ngi ta cho
Na2SO3 lin tc vo thp. Khi i t trn xung theo nhng tng hnh nn,
C6H5SO3Na s tc dng vi Na2SO3 to dung dch c C6H5SO3Na v kh SO2.
Kh SO2 sang thp axit ha phenolat C 6H5SO3Na sang thit b chy kim 7
cha NaOH nng
chy. Nng nhit khi phn ng ln 330 0C gi nhit ny trong khong
thi gian t 6 - 9 gi. Hn hp nng chy gm khong 40% C 6H5ONa, 45%
Na2SO3, cn li l Na2SO4 v nguyn liu d c a sang thit b dp tt cha
sn Na2SO3. Trong thit b dp tt, C6H5ONa tan trong dung dch, Na2SO3 tch
khi dung dch dng tinh th. Bng thit b quay ly tm chng ta tch c
dung dch C6H5ONa v Na2SO3 ra khi tinh th Na2SO3. Tinh th Na2SO3 c
a sang giai on trung ho benzen sunphoaxit trong thit b 6 phenolat c
axit ha thnh phenol. Sau lng v tch phenol khi dung dch Na2SO4.

Nguyn Vn Tin

39

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Phenol c nhit si cao nn phi chng ct trong chn khng bng hi


nc 7-8 at. Hi sn phm cho qua thit b ngng t, c a vo thng cha.
trnh hin tng phenol kt tinh lm tc ng ng, ngi ta cho nc nng
chy qua thit b ngng t. Chng phenol th ta c ln lt cc sn phm nh
sau:
- Nc phenol dng trong giai on dp tt khi kim nng chy cng vi
dung dch sunphatnatri.
- Phenol k thut thu c sau khi chng ct li hai ln na ta c phenol
tinh khit.
- Nha phenol dng lm cht ty trng v cht ty c.

PHN III:

TNH TON
CHNG I:

TNH CN BNG VT CHT TRONG CC QA


TRNH SN XUT

Nguyn Vn Tin

40

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Cc s liu u vo ca qa trnh sn xut


Nng ca cc nguyn liu
Nng sut ca nh my l 55.000 tn/nm.
Benzen k thut gm 96% benzen v 4% nc.
Ly d 1,06 mol so vi t l phn ng
Sunfit natri 82%, 14% nc v 1% tp cht.
NaOH 85%, ly d 20% so vi t l phn ng.
SO2 ly phn ng trung ho.
Hiu xut ca cc qa trnh phn ng nh sau.
- Hiu xut ca qa trnh sunfo ha

: 96%

- Hiu xut ca qa trnh trung ha l

: 100%

- Hiu xut ca qa trnh nung chy kim : 95%


- Hiu xut ca qa trnh dp tt

: 99%

- Hiu xut ca qa trnh lc

: 98%

- Hiu xut ca qa trnh axit ha

: 99,5 %

- Hiu xut ca qa trnh lng

: 99 %

- Hiu xut ca qa trnh chng ct

: 97%

- Hiu xut chung ca cc qa trnh

: 85,5%

Trong qa trnh sn xut mt nm phi c mt thi gian sa cha v bo


qun nht nh,vi s ngy ngh l 25 ngy. Do s ngy lm vic trong mt
nm l 340 ngy. T chng ta c th tnh c phenol sn xut c trong
mt gi l:
55000.10 3
= 6740,196 (kg/h)
340.24

Lng phenol sn xut trong mt gi

I. Tnh cn bng vt cht cho qa trnh sunpho ha.


Cc phn ng xy ra trong qa trnh sunpho ha:
C6H6

Nguyn Vn Tin

H2SO4

C6H5SO3H
41

+ H2O

(1)

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


C6H5SO3H

C6H5SO3H

H2SO4
C6H6

n tt nghip
C6H4(SO3H)2

+ H2O (2)

C6H5 - SO2 - C6H5 + H2O

(3)

Vy lng benzen tinh khit cn sn xut c 6740,196 kg phenol trong


mt gi l:
78.6740,196
= 5592,928 (kg/h)
94

Vi hiu xut ca qa trnh tnh theo benzen l 85,5% nn lng benzen tinh
khit cho qa trnh l :
5592,928.100
= 6541,436 (kg/h)
85,5

= 83,86 ( kmol/h)
Lng benzen k thut gm 96% v 4% l nc.
6541,436.100
= 6813,99 (kg/h)
96

= 87,36 (kmol/h)
+ Lng H2SO4 a vo thit b.
Lng H2SO4 tinh khit c tnh theo phn ng (1) nh sau:
87,36.98 = 8561,28 (kg/h)
Nhng trong thc t lng H2SO4 a vo d 1,06 mol so vi t l phn ng.
Do lng H2SO4 tinh khit l 8561,28 + (1,06.98) = 8665,16 (kg/h)
Lng axit H2SO4 k thut gm 98% v 2% tp cht:
8665,16.100
= 8842 (kg / h)
98

Lng tp cht vo thit b.


Lng tp cht c trong benzen
6813,99.0,04 = 272,56 (kg/h)
Lng tp cht c trong axit H2SO4
8842.0,02 = 176,84 (kg/h)
Nh vy tng lng tp cht c trong nguyn liu l :

Nguyn Vn Tin

42

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

272,56 + 176,84 = 449,4 (kg/h)


Lng vt cht ra khi thit b
Sn phm chnh ca qa trnh sunpho ha l benzen sunpho axit. Ngoi ra
cn c mt s sn phm ph ch yu khc nh Benzen disunphua axit, di phenyl,
v mt t nguyn liu. Theo gi thuyt th hiu xut ca qa trnh sunpho ha l
96%. Vy lng C6H6 chuyn ho thnh benzen sunpho axit l:
6541,436.0,96 = 6279,78 (kg/h)
Lng H2SO4 cn c l
6279,78 .98
= 7889,98 (kg/h)
78

Lng C6H5SO3H thu c l :


6279,78.158
= 12720,58 (kg/h)
78

Lng H2O thu c l :


6279,78.18
= 1449,18 (kg/h)
78

T phng trnh (1) v (2) ta c phng trnh tng hp sau:


C6H6

2 HO SO3H C6H4(SO3H)2

+ 2 H2O (4)

Phn ng to Benzen disunpho axit xy ra kh khn hn. Trn thc t


lng benzen tiu tn cho phn ng ny chim khong 1% nguyn liu cho vo.
Nn lng benzen tiu tn cho qa trnh ny l :
6541,436.0,01 = 65,414 (kg/h)
Theo phn ng (4) ta c th tnh c:
Lng H2SO4 tiu tn cho qa trnh ny l:
65,414.196
= 164,37 (kg/h)
78

Lng C6H4(SO3H)2 to thnh trong qa trnh ny l:

Nguyn Vn Tin

43

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

65,414.238
= 199,6 (kg/h)
78

Lng H2O to thnh trong qa trnh ny l:


65,414.36
= 32,707 (kg/h)
78

Vy lng H2SO4 tiu tn cho qa trnh ny l:

164,37 (kg/h)

Lng C6H4(SO3H)2 to thnh trong qa trnh ny l: 119,6 (kg/h)


Lng H2O to thnh trong qa trnh ny l:

32,707 (kg/h)

T phn ng (1) v (3) ta c phn ng (5)


2C6H6 + 2HO - SO3H

C6H5 - SO2 - C6H5 + 2H2O (5)

Trong thc t lng benzen tiu tn cho qa trnh ny khong 1% lng nguyn
liu nn lng benzen tiu tn cho qa trnh ny l:
6541,436.0,01 = 65,414 (kg/h)
Theo phn ng (5) ta c th tnh c:
Lng H2SO4 tiu tn cho qa trnh ny l:
65,414.98
= 41,09 (kg/h)
156

Lng C6H5 - SO2 - C6H5 to thnh cho qa trnh ny l


65,414.218
= 91,41 (kg/h)
156

Lng H2O to thnh trong qa trnh ny l


65,414.36
= 15,1 (kg/h)
156

Nh vy lng benzen tinh khit d trong qa trnh ny l


6541,436 - (6279,78 + 65,414 + 65,414) = 130,828 (kg/h)
Vy lng benzen k thut cn d tng ng l
130,828.100
= 132,15 (kg/h)
99

Lng H2SO4 tinh khit d trong qa trnh l


8665,16 - (7889,98 + 164,37 + 41,09) = 569,72 (kg/h)

Nguyn Vn Tin

44

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Vy lng H2SO4 k thut d tng ng l


569,72 .100
= 581,35 (kg/h)
98

Lng nc to thnh trong qa trnh ny l


1449,18 + 32,707 + 15,1 = 1496,99 (kg/h)
T qa trnh tnh ton trn cho qa trnh sunpho ha ta thu c bng cn bng
vt cht sau.
Lng nguyn

Kg / h

Lng sn phm ra

Kg / h

liu vo
C6H6
H2SO4
Tp cht

6541,436
8665,16
449,4

Tng lng vo

15655,996

C6H5SO3H
C6H4(SO3H)2
C6H5 - SO2 - C6H5
H2O
C6H6 d
H2SO4 d
Tp cht
Tng lng ra

12720,58
199,6
91,41
1496,99
130,828
569,72
449,4
15658,528

II. Tnh cn bng cho qa trnh trung ho.


Cc sn phm ra khi qa trnh sunpho ha s vo thit b trung ha gm c
cc sn phm sau: benzen sunpho axit, benzen disunpho axit, di phenyl,
sunphonat v mt phn H2SO4 d, khong 10% lng axit khng phn ng v
bng

0,1.569,72 = 56,972 (kg/h)

Cc phn ng xy ra trong qa trnh trung ha l


2 C6H5SO3H + Na2SO3 2 C6H5SO3Na

+ H2O + SO2 (6)

C6H4(SO3H)2 + Na2SO3 C6H4(SO3Na)2 + H2O + SO2


H2SO4 + Na2SO3

Na2SO4 + H2O + SO2

(7)

(8)

Lng H2SO4 dng cho qa trnh trung ho c tnh nh sau.


V hiu xut ca qa trnh trung ho l 100% nn lng C6H5SO3H c
chuyn ha l:

12720,58.1 = 12720,58 (kg/h)

Theo phn ng (6) lng Na2SO3 cn thit cho phn ng (6) l:

Nguyn Vn Tin

45

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

12720,58.126
= 5072,13 (kg/h)
316

Lng C6H5SO3Na to thnh:

12720,58.360
= 14491,8 (kg/h)
316

Lng H2O to thnh l:

12720,58.18
= 724,59 (kg/h)
316

Lng SO2 to thnh l:

12720,58.64
= 2576,32 (kg/h)
316

Do qa trnh chuyn ha C6H4(SO3H)2 t hiu xut 100% do lng


C6H4(SO3H)2 thu c l 199,6 (kg/h)
Theo phn ng (7) ta tnh c
Lng Na2SO3 cn thit l:

199,6.126
= 105,67 (kg/h)
238

Lng C6H4(SO3Na)2 to thnh l:

199,6.282
= 236,5 (kg/h)
238

Lng H2O to thnh l:

199,6.18
= 15,09 (kg/h)
238

Lng SO2 to thnh l:

199,6.64
= 53,67 (kg/h)
238

Theo phng trnh phn ng (8) ta c


Lng Na2SO3 cn thit l :

512,748.126
= 659,247 (kg/h)
98

Vy lng Na2SO4 thu c l:

512,748142
= 742,961 (kg/h)
98

Vy lng H2O thu c l:

512,748.18
= 94,178 (kg/h)
98

Vy lng SO2 thu c l:

512,748.64
= 334,856 (kg/h)
98

Tng lng Na2SO3 cn l: 5072,13 + 105,67 + 659,247 = 5837,047 (kg/h)


Thc t lng Na2SO3 ly d 20% nn lng Na2SO3 cn dng l
1,2.5837,047 = 7004,456 (kg/h)

Nguyn Vn Tin

46

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Lng Na2SO3 k thut 82% cn dng l:

7004,456 .100
= 8542,02 (kg/ h)
82

Lng C6H5SO3H cha chuyn ha l


12720,58 - 12720,58 = 0 (kg/h)
Lng C6H4(SO3H)2 cha chuyn ha l = 0 (kg/h)
Lng Na2SO3 d l 7004,456 - 5837,047 = 1167,409 (kg/h)
Tng lng H2O thu c l:
724,59 + 15,09 + 94,178 = 833,858 (kg/ h)
Lng Na2SO3 k thut d tng ng l

1167,049.100
= 1423,67 (kg/h)
82

Tng lng SO 2 thu c l:


2576,32 + 53,67 + 334,856 = 2964,846 (kg/h)
T s liu tnh ton phn trn chng ta c bng cn bng vt cht cho qa trnh
trung ho.
Lng vo
C6H5SO3H
C6H4(SO3H)2
Na2SO3
H2SO4

Kg / h
12720,58
199,6
7004,456
569,72

Tng vo

20494,356

Sn phm ra
C6H5SO3Na
C6H4(SO3Na)2
Na2SO4
H2O
SO2
Na2SO3 d
C6H5SO3H d
C6H4(SO3H)2 d
H2SO4 d
Tng ra

Kg / h
14491,8
236,5
742,961
833,858
2964,846
1167,409
0
0
56,972
20494,346

III. Tnh cn bng cho qa trnh nung chy kim.


Cc phn ng xy ra trong qa trnh nung chy kim
2 C6H5SO3Na

+ 2NaOH

2 C6H5ONa + Na2SO3 + SO2 + H2O (9)

C6H5-SO2- C6H5 + 4NaOH + 0,5 O2 2C6H5ONa + Na2SO3 + 2H2O (10)


C6H5 - SO2 - C6H5 + 2 NaOH

Nguyn Vn Tin

47

C6H5 - C6H5 + Na2SO3 +H2O (11)

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C6H4(ONa)2 + 2Na2SO3 +2H2O (12)

C6H4(SO3Na)2 + 4NaOH

Ngoi ra nhit cao cn xy ra mt s phn ng nh sau:


2 C6H5ONa

+ 0,5O2 NaO-C6H4- C6H4- ONa + H2O

C6H5ONa + C6H5ONa

C6H5-O- C6H5 + Na2SO3

(13)
(14)

C6H5S Na + 1,5 O2

C6H5SO3Na

(15)

Tnh lng vt cht vo thit b


V hiu xut ca qa trnh nung chy kim l 95% nn lng C 6H5SO3Na
chuyn ha thnh C6H5SO3Na l
14491,8.95
= 13767,21 (kg/h)
100

Theo phn ng (9) chng ta c th tnh c


Lng NaOH cn c l

13767,21.40
= 3059,38 (kg/h)
180

Lng C6H5ONa to thnh l

13767,21. 116
= 8872,202 (kg/h)
180

Lng Na2SO3 to thnh l

13767,21.126
= 4818,523 (kg/h)
360

Lng S2O to thnh l

3856,292.64
= 2447,504 (kg/h)
360

Lng H2O to thnh l

13767,21.18
= 688,360 (kg/h)
360

Diphenyl sunpho tham gia phn ng to ra 2 sn phm l phenolat v


dephenyl.Trong 60% Diphenyl sunpho to thnh phenolat (10), cn 40%
phn ng to thnh diphenyl (11).
Vy lng diphenyl sunfo tham gia (10) l

91,41.60
= 54,846 (kg/h)
100

Vy lng diphenyl sunfo tham gia (11) l

91,41.40
= 36,564 (kg/h)
100

Theo phng trnh phn ng (10) ta c :


Vy lng NaOH cn c l

Nguyn Vn Tin

54,846.160
= 40,254 (kg/h)
218
48

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Vy lng O2 cn c l

54,846.16
= 4,025 (kg/h)
218

Vy lng Na2SO3 to ra l

54,846.126
= 31,7 (kg/h)
218

Vy lng H2O to ra l

54,846.36
= 9,057 (kg/h)
218

Vy lng phenolat to thnh l

54,846.232
= 58,368 (kg/h)
218

Theo phn ng (11) ta c


Lng diphenyl to thnh trong phn ng (11) l

36,564.154
= 25,829 (kg/h)
218

Lng NaOH cn thit cho phn ng l

36,564.80
= 13,418 (kg/h)
218

Lng Na2SO3 to thnh l

36,564.126
= 21,133 (kg/h)
218

Lng H2O to thnh l

36,564.18
= 3,019
218

(kg/h)

Theo phn ng (12) ta c


Lng C6H4(SO3Na)2 vo thit b l 236,5 (kg/h)
Lng NaOH cn thit cho phn ng ny l

236,5 .160
= 134,184 (kg/h)
282
236,5 .154
= 129,152 (kg/h)
282

Lng C6H4(ONa)2 to ra
Lng Na2SO3 to thnh l

236,5 .252
= 211,34 (kg/h)
282

Lng H2O to thnh l

236,5 .36
= 30,191
282

(kg/ h)

Theo phn ng (13) ta c


Lng C6H5ONa tham gia phn ng (13) l
(8872,202 + 58,368).0,002 = 17,861 (kg/h)
17,861.16
= 1,232
232

Lng O2 cn l:

Nguyn Vn Tin

49

(kg/h)

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Lng NaO-C6H4-C6H4-ONa to thnh l:

17,861.230
= 17,707 (kg/h)
232

Lng H2O to thnh l

17,861.18
= 1,386
232

(kg/h)

Phn ng (14)
Lng C6H5ONa tham gia phn ng (14) l
(8872,202 + 58,368).0,009 = 80,375 (kg/h)
Lng (C6H5 )2O to ra l

80,375.170
= 58,895 (kg/h)
232

Lng Na2SO3 to thnh l

80,375.126
= 43,652 (kg/h)
232

Theo phng trnh phn ng (15) :


Lng C6H5SO3Na tham gia (15) l: 14491,8 - 13767,21 = 724,59 (kg/h)
Lng C6H5SNa to ra l

724,59.132
= 531,366
180

(kg/h)

Lng O2 to thnh l

724,59.48
= 193,224
180

(kg/h)

Vy ta c lng vo thit b l
C6H5SO3Na = 14491,8 (kg/h)
C6H5 - SO2-C6H5 = 91,41 (kg/h)
C6H4(SO3Na)2 = 236,5 (kg/h)
NaOH = 3059,38 + 40,254 + 13,418 + 134,184 = 3247,236 (kg/h)
M NaOH ly d so vi phn ng 20% nn lng NaOH thc t cn dng l :
3247,236.1,2 = 3896,683
vy lng NaOH k thut l

(kg/h)

3896,683.100
= 4584,333 (kg/h)
85

Lng NaOH d l

3896,683 - 3247,236 = 649,447 (kg/h)

Lng O2

4,025 + 1,232 = 5,257 (kg/h)

Lng tp cht vo l

449,4

Tng lng vo l

19171,05 (kg/h)

Nguyn Vn Tin

(kg/h)

50

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Lng ra khi thit b l


C6H5ONa = (8872,202 + 58,368) - (17,861 + 80,375) = 8832,334 (kg/h)
Tng lng Na2SO3 to ra l
4818,523 + 31,7 + 21,133 + 211,34 + 43,652 = 5126,348 (kg/h)
Tng lng H2O to ra trong qu trnh nung chy kim l
688,360 + 9,057 + 3,019 + 30,191 + 1,386 = 732,013 (kg/h)
T qa trnh tnh ton trn chng ta c th lp c bng cn bng vt cht cho
qa trnh ny.
Lng vo
C6H5SO3Na
C6H4(SO3Na)2
C6H5-SO2- C6H5
NaOH
Tp cht
Lng O2

Kg / h
14491,8
236,5
91,41
3896,683
449,4
5,257

Tng lng vo

19171,05

Sn phm ra
Kg / h
C6H5ONa
8832,334
Na2SO3
5126,348
H2O
732,013
C6H5-O- C6H5
58,895
C6H5- C6H5
25,829
C6H4(ONa)2
129,152
NaO-C6H4-C6H4-ONa
17,707
C6H5S Na
531,366
NaOH d
649,447
SO2
2447,504
Tp cht
449,4
O2
187,967
Tng sn phm ra
19177,962

IV. Qa trnh dp tt.


Ton b lng hn hp thu c sau qa trnh nng chy kim c cha
khong 40% phenolat, 45 % natri sunphit, phn cn li l natri sunphit cht
khng tham gia phn ng v phenolat cao c a sang thit b lm ngui gi
l thit b dp tt. chnh l qa trnh dp tt.
Theo u bi hiu xut ca qa trnh dp tt l 99%. Do sau qa trnh
dp tt chng ta thu c lng phenolat l

Nguyn Vn Tin

51

8832,334.99
= 8744,01 (kg/h)
100

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

V. Qa trnh lc.
Hn hp sau khi thu c lm ngui n nhit khong 40-50 0C khi ta tin
hnh qa trnh lc. Theo u bi hiu xut ca qa trnh t 98%. Do sau qa
8744,01.98
= 8569,13 (kg/h)
100

trnh lc ta thu c phenolat l

Trong cha mt lng nh gm C6H5-O- C6H5 , C6H5- C6H5 , C6H4(ONa)2 ,


C6H5S Na, Na2SO4, NaO-C6H4-C6H4-ONa v mt s tp cht khc. Sau qa trnh
lc tp cht ch cn li khong 60% so vi lng tp cht lc ban u.
Lng C6H5-O- C6H5

cn li l 0,6 .58,895 = 35,337 (kg/h)

Lng C6H5- C6H5

cn li l 0,6 .25,829 = 15,497 (kg/h)

Lng C6H4(ONa)2

cn li l 0,6 .129,152 = 77,491 (kg/h)

Lng C6H5S Na

cn li l 0,6 .531,366 = 318,82 (kg/h)

Lng Na2SO3

cn li l 0,6 .5126,348 = 3031,985 (kg/h)

Lng NaO-C6H4-C6H4-ONa cn li l 0,6 . 17,707 = 10,624 (kg/h)


Lng tp cht cn li l

0,6 . 449,4 = 269,64 (kg/h)

VI. Tnh ton cn bng cho qa trnh axit ha.


Sau qa trnh lc chng ta tip tc a sang qa trnh axit ha. Cc phn ng
xy ra trong qa trnh axit ha nh sau:
Phn ng chnh xy ra l .
2 C6H5ONa + H2O + SO2

2 C6H5OH + Na2SO3

(16)

Phn ng ph xy ra l.
C6H4(ONa)2 + H2O + SO2
2 C6H5S Na

+ H2O + SO2

NaO-C6H4-C6H4-ONa + H2O + SO2

C6H4(OH)2

+ Na2SO3

2 C6H5S H

+ Na2SO3

(17)
(18)

OH - (C6H4) OH + Na2SO3 (19)

Tnh lng vo thit b axit ha


Tnh lng phenol to thnh

Nguyn Vn Tin

52

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Theo u bi hiu xut ca qa trnh axit ha l 99,5 % nn lng phenolat


chuyn ha theo phn ng (16) l

8569,13.99,5
= 8526,284 (kg/h)
100

Lng SO2 cn thit cho phn ng l

8526,284.64
= 2352,078
232
8526,284.18
= 661,522
232

(kg/h)

8526,284.188
= 6909,23
232

(kg/h)

Lng H2O cn thit cho phn ng l


Lng C6H5OH to thnh l

(kg/h)

8526,284.126
= 4630,654
232

Lng Na2SO3 to thnh l

(kg/h)

Theo phn ng (17) ta c


Lng SO2 cn c l

77,491.64
= 32,204
154

(kg/h)

Lng H2O cn c l

77,491.18
= 9,057
154

(kg/h)

Lng C6H4(OH)2 to thnh l

77,491.110
= 55,35 (kg/h)
154

Lng Na2SO3 to thnh l

77,491.126
= 63,402 (kg/h)
154

Theo phn ng (18) ta c


Lng SO2 cn c l
Lng H2O cn c l

318,82 .64
= 77,289
264

(kg/h)

318,82.18
= 21,738
264

(kg/h)

Lng C6H5S H to thnh l

318,82.220
= 265,683 (kg/h)
264

Lng Na2SO3 to thnh l

318,82.126
= 152,164 (kg/h)
264

Theo phn ng (19) ta c

Nguyn Vn Tin

53

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Lng SO2 cn c l

10,624 .64
= 2,956
230

(kg/h)

Lng H2O cn c l

10,624 .18
= 0,831
230

(kg/h)

Lng OH - (C6H4)2 - OH to thnh l


Lng Na2SO3 to thnh l

10,624 .186
= 8,591 (kg/h)
230

10,624 .126
= 5,820
230

(kg/h)

Lng SO2 a vo ly t giai on trung ha l: 2964,846 (kg/h)


Tng lng SO2 tiu tn l:
2352,078 + 32,204 + 77,289 + 2,956 = 2464,527 (kg/h)
Vy lng SO2 cn d l:

2964,846 - 2464,527 = 500,319

Lng C6H5ONa chuyn ha l: 8526,284


Lng C6H5ONa cn d l:

(kg/h)

(kg/h)

8569,13 - 8526,284 = 42,846 (kg/h)

Tng lng H2O tiu tn l:


661,522 + 9,057 + 21,738 + 0,831 = 693,148 (kg/h)
Tng lng Na2SO3 to thnh l:
4630,654 + 63,402 + 152,164 + 5,820 = 4852,04 (kg/h)

T qa trnh tnh ton phn trn chng ta c th lp c bng cn bng vt


cht cho qa trnh ny.
Lng vo

Nguyn Vn Tin

Kg / h

Sn phm ra
54

Kg / h

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


C6H5ONa
SO2
H2O
C6H4(ONa)2
C6H5S Na
NaO-C6H4-C6H4-ONa
C6H5-O- C6H5
C6H5- C6H5
Na2SO3
Tp cht

8526,284
2964,846
693,148
77,491
318,82
10,624
35,337
15,497
3075,808
269,64

Tng lng vo

15987,495

n tt nghip
C6H5OH
Na2SO3
C6H4(OH)2
C6H5S H
OH -(C6H4)2- OH
C6H5ONa d
SO2 d
Na2SO3
C6H5- C6H5
C6H5-O- C6H5
Tp cht
Tng lng ra

6909,23
4852,04
55,35
265,683
8,591
42,846
500,319
3031,985
15,497
35,337
269,64
15986,518

VII. Qa trnh lng.


Hn hp phenol v cht nhn c sau qa trnh axit ha c a i lng,
tch cc tp cht khi chng ta thu c phenol th. Hiu sut ca qa trnh
ny l 99% .Vy phenol nhn c sau qa trnh ny l
6909,23.0,99 = 6840,138

(kg/h)

VIII. Qa trnh chng ct.


Phenol th sau qa trnh lng c a vo thp chng ct thu c phenol
tinh khit. Theo u bi hiu sut ca qa trnh chng ct l 97%. Do lng
phenol thu c sau qa trnh ny l
6840,138.0,97 = 6634,933 (kg/h)

Kt lun
Sau qa trnh tnh ton chng ta c th rt c cc lng nguyn liu cho qa
trnh sn xut phenol vi nng sut 55.000 tn/nm c th hin qua bng s
liu sau.
Lng nguyn liu
C6H6 99%
H2SO4 98 %

Nguyn Vn Tin

Kg / h
6813,99
8842

Ghi ch
Lng k thut
Lng k thut, ly d
55

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


Na2SO3 82%
NaOH 85%
SO2
H2O

CHNG II:

n tt nghip

8480,044

1,06 mol so vi phn ng


Lng k thut, ly d

4584,333

20% so vi phn ng
Lng k thut, ly d

2964,846
693,148

15% so vi phn ng
Ly qu trnh trung ho

TNH CN BNG NHIT LNG TRONG CC


QA TRNH SN XUT

I. Cn bng nhit lng ca qa trnh sunpho ha


- Nhit u vo ca hn hp 25 0 C
- Nhit u ra ca sn phm l 150 0C

Nguyn Vn Tin

56

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Nguyn liu C6H6 v H2SO4


Phng trnh cn bng nhit lng
Q1 + Q2 = Q3 + Q4 + Q5
Q1 Nhit lng do nguyn liu mang vo, Kcal / h
Q3 Nhit lng do phn ng ta ra, Kcal / h
Q2 Nhit lng do sn phm mang ra, Kcal / h
Q4 Nhit lng mt mt ra mi trng, Kcal / h
Q5 --Nhit do tc nhn lm lnh, Kcal / h
1. Nhit lng do nguyn liu mang vo.
Q1 = G1. C1. T1 + G2. C2. T2
Trong
T1 l nhit u vo ca hn hp, bng 250C.
G1 l lng C6H6 v G1 = 6813,99 (kg/h)
C1 l nhit dung ring ca C6H6 , C1 = 0,38 Kcal / kg.
G2 l lng H2SO4 , G2= 8842 (kg/h)
C2 l nhit dung ring ca H2SO4 ,C1 = 0,35 Kcal / kg.
T2=T1
Vy Q1 = 6813,99.0,38.25 + 8842.0,35.25
=142100,405 (Kcal/h) = 142100,405.4,187 = 594974,395 (kj/h)
2. Nhit lng do sn phm mang ra.
+ Nhit lng do C6H5SO3H mang ra
q1 = C1 . m1 . t1
C1- l nhit dung ring ca C6H5SO3H, Kcal / kg.
t1- l nhit ca sn phm ra, t1 = 150 0C
m1- lng C6H5SO3H,

m1 = 12720,58 (kg/h)

Nhit dung ring ca hp cht C6H5SO3H c xc nh nh sau


M .C =n1.C1 + n2.C2
Trong

Nguyn Vn Tin

57

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

M khi lng mol ca hp cht


C l nhit dung ring ca hp cht ha hc, J/kg.
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J/ kg nguyn t.
Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
158. C = 6.11700 + 6.18000 + 31000 + 3.25100
C = 1800,633 ( J / kg.)
Vy q1 = 12720,58. 1800,633. 150 = 3435764419 (J/h)
= 3435764,419 (kj/h)
+ Nhit lng do H2O mang ra
q2 = C2 . m2 . t2
C2- l nhit dung ring ca H2O, Kcal / kg.
t2- l nhit ca H2O ra , t2 = 150 0C
m2- lng H2O , m2 = 1496,99 (kg/h)
C2 = 0,476 . 4,18 .103 J / kg.
q2 = 0,476 . 4,18 .103 . 150. 1496,99

= 446779659 (J/h)
= 446779,659 (kj/h)

+ Nhit lng do benzen d mang ra


q3 = C3 . m3 . t3
Trong
C3- l nhit dung ring ca benzen, Kcal / kg.
t3- l nhit ca benzen , t3 = 150 0C
m3- lng benzen, m3 =130,828 (Kg / h)

Nguyn Vn Tin

58

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C3 = 0,38 . 4,18 .103 J / kg.


Q3 =

0,38 . 4,187.103 . 150. 130,828 = 31171,079. 103 (j/ h )


=31171,079 (kj/h)

+ Nhit lng do H2SO4 d mang ra


q4 = C4 . m4 . t4
Trong
C4- l nhit dung ring ca H2SO4 d , Kcal / kg.
t3- l nhit ca H2SO4 , t4 = 150 0C
m4- lng H2SO4 d, m4 =569,72 (kg/h)
C4 = 0,35 . 4,18 .103 J / kg.
q4 =

0,35 . 4,18 .103 . 150. 569,72 = 125025,054. 103 (J/h)


=125025,054 (kj/h)

Vy tng nhit lng do sn phm mang ra l


Q3 = q1 + q2 + q3 + q4 = 3435764,419 + 446779,659 +31171,079 + 125025,054
=4038740,211 (kj/h) = 964590,449 (kcal/h)
3. Nhit lng do phn ng ta ra.
Cc phn ng to nhit
+ Phn ng to nhit th nht
C6H6 + HO-SO3H C6H5SO3H + H2O (1)
H1 Hiu ng nhit ca phn ng (1)
H1 = ( ni .ci ) u - (ni .ci )cui
H1 = 3 C[ C=C] + 3 C[ C-C] + 6 C[ C-H] + 2 C[ S=O] +2 C[ H-O] -3 C[ C=C] - 3 C[ C-C]
- C[ S-S] - 2 C[ S=O] - C[ H-O] - 2C[ H-O] - 5C[ C-H]
Tra bng ta c
C[ C=C] =101,2 (Kcal / mol)

C[ S=O] = 92,2

C[ C-H] = 85,6

C[ C-S] = 54( Kcal / mol)

C[ C=S] =

62,8

( Kcal / mol )
(Kcal / mol)

Nguyn Vn Tin

( Kcal / mol)

C[ H-O] = 110( Kcal / mol)


59

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Vy H1 =-78,4 (Kcal / mol)


S mol C6H6 tham gia phn ng (1) l 83,864 (kmol/h)
q1= 83,864.103.78,4

= 6574981,826 (Kcal/h)
= 27529448,9 (kj/h)

+ Phn ng to nhit th hai


HO-SO3H + C6H5SO3H C6H4(SO3H)2 + H2O (2)
H2 Hiu ng nhit ca phn ng (1)
H2 = ( ni .ci ) u - (ni .ci )cui
H2 = C[ C=C] + C[ C-H]

- C[ C-C] - C[ C-S]

Tra bng ta c
C[ C=C] =101,2 Kcal / mol

C[ S=O] = 92,2

C[ C-H] = 85,6

Kcal / mol

C[ C-S] = 54

C[ C=S] =

Kcal / mol

C[ H-O] = 110

62,8

Kcal / mol
Kcal / mol
Kcal / mol

Vy H1 =-70 Kcal / mol


S mol H 2SO4 tham gia phn ng (2) l
119,6.98
= 49,247 (kg/h) = 0,503 (kmol/h)
238

q2 = 503.70 = 35210 (Kcal/h) = 147424,27 (kj/h)

+ Phn ng to nhit th ba
C6H6 + C6H5SO3H C6H5-SO2- C6H5

+ H2O (3)

H3 Hiu ng nhit ca phn ng (3)


H3 = ( ni .ci ) u - (ni .ci )cui
H3 = C[ C-H] - C[ H-O]
Tra bng ta c
C[ C=C] =101,2 Kcal / mol

Nguyn Vn Tin

C[ S=O] = 92,2
60

Kcal / mol

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C[ C-H] = 85,6

Kcal / mol

C[ C-S] = 54

C[ C=S] =

Kcal / mol

C[ H-O] = 110

62,8

Kcal / mol
Kcal / mol

Vy H3 = 24,4 Kcal / mol


S mol C6H6 tham gia phn ng (3) l 0,419 (kmol/h)
q3 =

419. 24,4 = 10223,6 (Kcal/h) = 42806,213 (kj/h)

Vy tng nhit lng do phn ng to ra l


Q2 = qi = 27529448,9 + 147424,27 + 42806,213 =27719679,38 (Kj/h)

4. Nhit lng mt mt ra mi trng xung quanh.


Coi nhit lng mt mt ra mi trng xunh quanh l 5 % lng nhit cp vo
Q4 = 0, 05 .Q1 = 29748,719 (Kj/h) = 7105,02 (kcal/h)
5. Nhit lng mt do tc nhn lm lnh.
Nhit lng do tc nhn lm lnh c xc nh theo cng thc sau:
QLL = Q5 = Q1 + Q2 - ( Q3 + Q4 )
QLL = Q5 = (142100,405 + 6620415,424) - (964590,449 + 7105,02)
=5790820,36 (Kj/h)

T qa trnh tnh ton trn chng ta c th lp c bng cn bng nhit lng


cho qa trnh sunpho ha.
Lng nhit vo
Kj / h
NL do nguyn 142100,405

Nhit lng ra
Kj / h
Nhit lng do sn 964590,449

liu mang vo
Nhit do phn 6620415,424

phm mang ra
Nhit lng mt mt ra 7105,02

ng

mi trng xunh quanh


Nhit do tc nhn lm 5790820,36

Nguyn Vn Tin

61

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


Tng

n tt nghip

lnh
nhit 6.762.515,829 Tng nhit lng mang 6.762.515,829

lng vo

ra

II. Tnh cn bng nhit lng cho qa trnh nng chy kim
- Nhit u vo ca hn hp 25 0 C
- Nhit u ra ca sn phm l 330 0C
n gin chng ta coi nguyn liu phn ng gm C 6H5SO3 Na v NaOH,
chng ta c phn ng sau:
C6H5SO3 Na + 2 NaOH C6H5ONa + Na2SO3 + H2O
Phng trnh cn bng nhit lng
Q1 + Q2 = Q3 + Q4 +Q5
Trong
Q1 Nhit lng do nguyn liu mang vo, Kcal / h
Q2 Nhit lng do phn phn ta ra, Kcal / h
Q4 Nhit lng do sn phm mang ra, Kcal / h
Q3 Nhit lng mt mt ra mi trng, Kcal / h
Q5 --Nhit do tc nhn lm lnh, Kcal / h

1. Nhit lng do nguyn liu mang vo.


Q1 = G1. C1. T1 + G2. C2. T2
Trong
T1 l nhit u vo ca C6H5SO3Na , bng 250C.
G1 l lng C6H5SO3Na v G1 =14491,8 ( kg/h)
C1 l nhit dung ring ca C6H5SO3Na
G2 l lng NaOH , G2 = 3832,146 (kg/h)
C2 l nhit dung ring ca NaOH , Kcal / kg.

Nguyn Vn Tin

62

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Nhit dung ring ca C6H5SO3Na c xc nh theo cng thc sau


M . C = n1. C1 + n. C2 +.
Trong
M l khi lng mol ca hp cht C6H5SO3Na
C l nhit dung ring ca C6H5SO3Na
n1, n2 l s nguyn t ca cc nguyn t trong C6H5SO3Na
C1,C2 l nhit dung ring ca cc nguyn t tng ng, J / kg .
Tra bng ta c cc s liu sau
CC =11700 J / kg .nguyn t .
CH = 18000 J / kg .nguyn t .
CS = 31000 J / kg .nguyn t .
CO =25100 J / kg .nguyn t .
CNa =33500 J / kg .nguyn t .
Thay cc gi tr trn vo cng thc chng ta c
180 . C = 6. 11700 + 5. 18000 +31000 + 3. 25100 + 33500
C = 1666,667 J / kg .
Nhit dung ring ca NaOH tnh nh sau
40 . C = 33500 + 25100 + 18000
CNaOH = 1915 J / kg .
Q1 = 14491,8.1666,667.25 + 3832,146.1915.25 = 787289,1105 (KJ/h)
=188031,791 (kcal/h)
2. Nhit lng do sn phm mang ra.
+ Nhit lng do C6H5ONa mang ra
q1 = C1 . m1 . t1
C1- l nhit dung ring ca C6H5ONa, Kcal / kg.
t1- l nhit ca sn phm ra, t1 = 330 0C
m1- lng C6H5ONa , m1= 8832,334 (kg/h)
Nhit dung ring ca hp cht C6H5ONa c xc nh nh sau

Nguyn Vn Tin

63

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

M .C =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H5ONa
C l nhit dung ring ca C6H5ONa , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
116. C = 6.11700 + 5.18000 + 25100 + 33500
C = 1886,207 (J / kg.)
Vy q1 = 8832,334. 1886,207 . 330 = 549767137,2 (J/h)
= 549767,1372 (kj/h) = 131303,352 (kcal/h)
+ Nhit lng do Na2SO3 mang ra
q2 = C2 . m2 . t2
C2- l nhit dung ring ca Na2SO3 , Kcal / kg.
t2- l nhit ca Na2SO3 mang ra, t1 = 330 0C
m2- lng Na2SO3 , m2 = 5041,642 (kg/h)
Nhit dung ring ca hp cht Na2SO3 c xc nh nh sau
M .C =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht Na2SO3
C l nhit dung ring ca Na2SO3 , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .

Nguyn Vn Tin

64

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Tra bng ta c CC = 11700 J / kg nguyn t .


CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
126. C = 25100 + 31000 + 2. 33500
C = 976,984 ( J / kg.)
Vy q2 = 976,984.5041,642. 330 = 1625449177 (J/h)
= 1625449,177 (kj/h) = 388213,321 (kcal/h)
+ Nhit lng do H2O mang ra
q3 = C3 . m3 . t3
C3- l nhit dung ring ca H2O , C3 = 0,476 (kcal / kg.)
T3- l nhit ca mang H2O ra, t3 = 330 0C
m3- lng H2O , m3 = 719,912( Kg / h)
q3 = 0,476.719,912. 330 = 113083,777 (kcal/h)
= 473481,774 (kj/h)
+ Nhit lng do SO2 mang ra
q4 = C4 . m4 . t4
C4- l nhit dung ring ca SO2 , C4 = 1268,75 (J / kg.)
T4- l nhit ca SO2 mang ra, t4 = 330 0C
m4- lng , m4 = 2447,504 (kg/h)
q4 = 2447,504.1268,75 . 330 = 1024739,331 (kJ / h ) = 244743,093 (kcal/h)
Vy tng nhit lng do sn phm mang ra l : Q3 =
549767,137 + 1625449,177 + 473481,774 + 1024739,331 = 877343,544 (kcal/h)
3. Nhit lng do phn ng ta ra.
Cc phn ng to nhit
+ Phn ng to nhit th nht

Nguyn Vn Tin

65

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

2C6H5SO3Na + 2 NaOH 2 C6H5ONa + Na2SO3

+ H2O + SO2 (1)

H1 Hiu ng nhit ca phn ng (1)


H1 = ( ni .ci ) u - (ni .ci )cui
H1 = 3 C[ C=C] + 3 C[ C-C] + 5 C[ C-H] + C[ S-C] +2 C[ S=O] + C[ O- Na] + 2 C[ Na- O]
+C[ H-O] - 3C[ C-C] - 5 C[ C-H] - C[ Na-O] - 3C[ C=C] - C[ C-O] - 2 C[ O -Na] - 2C[ O-H]
Tra bng ta c
C[ C=C] =101,2 Kcal / mol

C[ S=O] = 92,2

C[ C-H] = 85,6

Kcal / mol

C[ C-S] = 54

C[ C=S] =

Kcal / mol

C[ H-O] = 110

62,8

Kcal / mol
Kcal / mol
Kcal / mol

Vy H1 =163 Kcal / mol


S mol C6H5SO3Na tham gia phn ng (1) l
(14491,8/180) = 80,51 (kmol/h)
q1= 80510.163=13123130 (Kcal/h) =54946545,31 (kj/h)
+ Phn ng to nhit th hai
C6H5-SO2- C6H5 + 4 NaOH + 0,5 O2 2 C6H5ONa + Na2SO3 + 2 H2O (2)
H2 Hiu ng nhit ca phn ng (2)
H2 = ( ni .ci ) u - (ni .ci )cui
H2 = C[ S=O] + 0,5 C[ C=O]
Tra bng ta c
C[ C=C] =101,2 Kcal / mol

C[ S=O] = 92,2

C[ C-H] = 85,6

Kcal / mol

C[ C-S] = 54

C[ C=S] =

Kcal / mol

C[ H-O] = 110

62,8

Kcal / mol
Kcal / mol
Kcal / mol

Vy H1 = 92,2 + 0,5 . 117,2 =150,8 (Kcal / mol )


S mol C6H5-SO2- C6H5 tham gia phn ng (2) l 0,419 (kmol/h)
q2 =

0,419.103 .150, 8 = 63185,2 (Kcal/h) = 264556,432 (kj/h)

+ Phn ng to nhit th ba

Nguyn Vn Tin

66

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C6H4(SO3Na)2 + 4 NaOH C6H4(ONa)2 + Na2SO3 + H2O (3)


H3 Hiu ng nhit ca phn ng (3)
H3 = ( ni .ci ) u - (ni .ci )cui
H3 = 2 C[ S=O] =2 . 92,2 = 184,4 kcal / mol
Vy H3 = 184,4 Kcal / mol
S mol C6H4(SO3Na)2 tham gia phn ng (3) l 0,503 ( kmol / h)
q3 = 503.184,4 = 92753,2 (Kcal/h) = 388357,648 (kj/h)
Vy tng nhit lng do phn ng to ra l
Q2 = qi = q1 +q2 + q3 =13123130 + 63185,2 + 92753,2 = 13279068,4 (Kcal/h)

4. Nhit lng mt mt ra mi trng xung quanh.


Coi nhit lng mt mt ra mi trng xunh quanh l 5 % lng nhit cp vo
Q4 = 0, 05 .Q1 =9401,589 (Kcal/h)
5. Nhit lng mt do tc nhn lm lnh.
Nhit lng do tc nhn lm lnh c xc nh theo cng thc sau:
QLL = Q5 = Q1 + Q2 - ( Q3 + Q4 )
QLL = Q5 = (188031,791 + 13279068,4) - (877343,544 + 9401,589)
=12580355,06 (Kcal/h)
T qa trnh tnh ton trn chng ta c th lp c bng cn bng nhit lng
cho qa trnh nng chy kim
Lng nhit vo
Kcal / h
Nl do nguyn liu 188031,791

Nhit lng ra
Kcal / h
Nhit lng do sn phm 877343,544

mang vo
Nhit do phn ng 13279068,4

mang ra
Nhit lng mt mt ra 9401,589

to ra

mi trng xunh quanh


Nhit do tc nhn lm 12580355,06

Nguyn Vn Tin

67

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


Tng

nhit

n tt nghip

lnh
lng 13.467.100,19 Tng nhit lng mang ra 13.467.100,19

vo

III. Cn bng nhit lng ca qa trnh axit ha


- Nhit u vo ca hn hp 40 0 C
- Nhit u ra ca sn phm l 25 0C
Phng trnh cn bng nhit lng
Q1 + Q2 = Q3 + Q4 + Q5
Q1 Nhit lng do nguyn liu mang vo, Kcal / h
Q2 Nhit lng do phn phn ta ra, Kcal / h
Q3 Nhit lng do sn phm mang ra, Kcal / h
Q4 Nhit lng mt mt ra mi trng, Kcal / h
Q5 --Nhit do tc nhn lm lnh, Kcal / h
1. Nhit lng do nguyn liu mang vo.
- Nhit lng do C6H5ONa mang vo
q1 = G1. C1. T1
Trong
T1 l nhit u vo ca C6H5ONa , bng 400C.
G1 l lng C6H5ONa v G1 = 8526,284 (Kg/h)
C1 l nhit dung ring ca C6H5ONa , C1 = 1886,21 J / kg.
q1 = 8526,284. 1886,21 . 40 = 643294,485 (kj/h) = 153640,908 (kcal/h)
- Nhit lng do SO2 mang vo
q2= G2. C2. t2
Trong
t1 l nhit u vo ca SO2 , bng 400C.
G2 l lng SO2 v G2 = 2943,336 (Kg/h)

Nguyn Vn Tin

68

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C2 l nhit dung ring ca SO2 nhit dung ring ca n c tnh theo cng thc
sau y:
10-3 . CP = a +b.T - cT-2
Vi a=12,78 .10-1 , b=2,671.10-4 , c=3,183 . 10-4
Vy CP =1532,704 J / kg .
q2 = 2943,336. 1532,704 . 40 = 180450,514 (kj/h) = 43097,806 (kcal/h)
- Nhit lng do nc mang vo
q3 = G3. C3. t3
Trong
t3 l nhit u vo ca H2O , bng 400C.
G3 l lng H2O v G3 = 689,518 (kg/h)
C3 l nhit dung ring ca H2O 400C , C3 = 101 Kcal / kg .
Q3 = 689,518.101.40 = 2785652,72 (kcal/h)
- Nhit lng do C6H4(ONa)2 mang vo
q4 = G4. C4. t4
Trong
T4 l nhit u vo ca C6H4(ONa)2 , bng 400C.
G4 l lng C6H4(ONa)2

v G4 = 46,433 (kg/h)

C4 l nhit dung ring ca C6H4(ONa)2 400C


Nhit dung ring ca C6H4(ONa)2 c xc nh theo cng thc sau
M .C4 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H4(ONa)2
C l nhit dung ring ca C6H4(ONa)2 , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Tra bng ta c CC = 11700 J / kg nguyn t .

Nguyn Vn Tin

69

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
154. C4 = 6.11700 + 4.18000 +2. 25100 + 2.33500
C4 = 1684,41 J / kg.
Vy q4 = 46,433.1684,41.40 = 3128,488 (kJ/h) = 747,191 (kcal/h)
- Nhit lng do C6H5S Na mang vo
q5 = G5. C5. t5
Trong
t5 l nhit u vo ca C6H5S Na, bng 400C.
G5 l lng C6H5S Na v G5 = 318,82 (kg/h)
C5 l nhit dung ring ca C6H5S Na 400C
Nhit dung ring ca C6H5S Na c xc nh theo cng thc sau
M .C5 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H5S Na
C l nhit dung ring ca C6H5S Na, J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
132. C5 = 6.11700 + 5.18000 +31000 + 33500
C5 = 1702,27 J / kg.
Vy q5 = 318,82.1702,27. 40 = 21708,708 (kJ/h) = 5184,788 (kcal/h)

Nguyn Vn Tin

70

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

- Nhit lng do NaO- (C6H4)2-ONa mang vo


q6 = G6. C6. t6
Trong
T6 l nhit u vo ca , bng 400C.
G6 l lng NaO- (C6H4)2-ONa v G6 = 10,624 (kg/h)
C6 l nhit dung ring ca NaO- (C6H4)2-ONa 400C
Nhit dung ring ca NaO- (C6H4)2-ONa c xc nh theo cng thc sau
M .C6 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht NaO- (C6H4)2-ONa
C6 l nhit dung ring ca NaO- (C6H4)2-ONa , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
230. C6 = 12.11700 + 8.18000 +2. 25100 + 2.33500
C6 = 1746,087 (J / kg.)
Vy q6 = 10,624.1746,087.40 = 742,017 (kJ/h) = 177,219 (kcal/h)
- Nhit lng do C6H5-O- C6H5

mang vo

q7 = G7. C7. t7
Trong :
t7 l nhit u vo ca C6H5-O- C6H5 , bng 400C.
G7 l lng C6H5-O- C6H5 v G7 =35,337 (kg/h)
C7 l nhit dung ring ca C6H5-O- C6H5 400C

Nguyn Vn Tin

71

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Nhit dung ring ca C6H5-O- C6H5 c xc nh theo cng thc sau


M .C7 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H5-O- C6H5
C7 l nhit dung ring ca C6H5-O- C6H5 , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
120. C7 = 12.11700 + 10.18000 + 25100
C7 = 2032,353 J / kg.
Vy q7 = 35,337. 2032,353.40 = 2872,690 (kJ/h) = 686,097 (kcal/h)
- Nhit lng do C6H5- C6H5 mang vo
q8= G8. C8. t8
Trong
t8 l nhit u vo ca C6H5- C6H5 , bng 400C.
G8 l lng C6H5- C6H5 v G8 = 15,497 (kg/h)
C8 l nhit dung ring ca C6H5- C6H5 400C
Nhit dung ring ca C6H5- C6H5 c xc nh theo cng thc sau
M .C8 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H5- C6H5
C8 l nhit dung ring ca C6H5- C6H5 , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht

Nguyn Vn Tin

72

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .


Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c
154. C8 = 12.11700 + 10.18000
C8 =

2080,52 J / kg.

Vy q8 = 15,497. 2080,52. 40 = 1289,673 (kJ/h) = 308,018 (kcal/h)


- Nhit lng do Na2SO3 mang vo
q9= G9. C9. t9
Trong
t9 l nhit u vo ca Na2SO3, bng 400C.
G9 l lng Na2SO3 v G9 = 3024,985 (kg/h)
C9 l nhit dung ring ca Na2SO3 400C
Nhit dung ring ca

Na2SO3 c xc nh theo cng thc sau

M .C9 =n1.C1 + n2.C2


Trong
M khi lng mol ca hp cht Na2SO3
C9 l nhit dung ring ca Na2SO3, J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Tra bng ta c CC = 11700 J / kg nguyn t .
CH = 18000 J / kg nguyn t .
CS = 31000 J / kg nguyn t .
CO = 25100 J / kg nguyn t .
Thay vo ta c:

Nguyn Vn Tin

73

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

142 . C9 = 2. 33500 +31000 + 3. 25100


C9 = 1220,423 ( J / kg.)
Vy q9 = 40.1220,423.3024,985 = 147670,45 (kJ/h) = 35268,796 (kcal/h)
T qa trnh trn chng ta tnh c tng lng nhit do nguyn liu mang vo
l:
Q1 = qi = 153640,908 + 43097,806 + 2785652,72 + 747,191 + 5184,788 +
177,219 + 686,097 + 308,018 + 35268,796 = 3024763,453 (kcal/h)
2. Nhit lng do phn ng ta ra.
Cc phn ng to nhit
Vi hiu xut ca qa trnh l 99,5% nn b qua cc phn ng ph, phn ng
xy ra theo phng trnh sau
2 C6H5ONa + SO2 + H2O 2C6H5OH + Na2SO3

(1)

H1 Hiu ng nhit ca phn ng (1)


H1 = ( ni .ci ) u - (ni .ci )cui
H1 = 6 C[ C=C] + 6 C[ C-C] + 2 C[ O-Na] +2 C[ C-O] + 10 C[ C- H] + 2 C[ S= O]
+2 C[ H-O] - 6C[ C=C] - 6 C[ C=C] +2 C[ Na-O] + 2 C[ C-O] + 10C[ C-H] - C[ S=O]
-2 C[ O-H] -2 C[ S-O]
Tra bng ta c
C[ C=C] =101,2 Kcal / mol

C[ S=O] = 92,2

Kcal / mol

C[ C-H] = 85,6

Kcal / mol

C[ C-S] = 54

Kcal / mol

C[ C-C] = 62,8

Kcal / mol

C[ H-O] = 110

Kcal / mol

C[ C-O] = 75

Kcal / mol

C[ S-O] = 55,6

Kcal / mol

Vy H1 = 92,2 -2 . 55,6 = -19 Kcal / mol


S mol C6H5ONa tham gia phn ng (1) l 73,502 (kmol/h)
Q2= 73,502.19 = 1396,546 (Kcal/h)

Nguyn Vn Tin

74

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

3. Nhit lng do sn phm mang ra.


+ Nhit lng do C6H5OH mang ra
q1 = C1 . m1 . t1
C1- l nhit dung ring ca C6H5OH, Kcal / kg.
t1- l nhit ca sn phm C6H5OH ra, t1 = 25 0C
m1- lng C6H5OH , m1= 6909,23 (Kg/h)
Nhit dung ring ca hp cht C6H5OH c xc nh nh sau
M .C =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H5OH
C l nhit dung ring ca C6H5OH , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Thay vo ta c
94. C1 = 6.11700 + 6.18000 + 25100
C1 = 2162,266 J / kg.
Vy q1 = 6909,23.2162,266.25 =373489827,9 (J/h) = 89202,252 (Kcal/h)
+ Nhit lng do Na2SO3 mang ra
q2 = C2 . m2 . t2
C2- l nhit dung ring ca Na2SO3, Kcal / kg.
t2- l nhit ca sn phm ra, t2 = 25 0C
m2- lng Na2SO3 , m2 =4826,629 (Kg/h)
Nhit dung ring ca hp cht Na2SO3 c xc nh nh sau
M .C 2 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht Na2SO3
C2 l nhit dung ring ca Na2SO3 , J / kg .

Nguyn Vn Tin

75

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

n1, n2 s nguyn t cc nguyn t trong hp cht


C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Thay vo ta c
C2 = 1375,4 J / kg .
Vy q2 = 4826,629.1375,4.25 =16596368,2 (j/h) =39637,84 (Kcal/h)
+ Nhit lng do C6H4(OH)2 mang ra
q3 = C3 . m3 . t3
C3- l nhit dung ring ca C6H4(OH)2 , Kcal / kg.
t3- l nhit ca C6H4(OH)2 sn phm ra, t3 = 25 0C
m3- lng C6H4(OH)2 , m3=33,166 (Kg/h)
Nhit dung ring ca hp cht C6H4(OH)2 c xc nh nh sau
M .C3 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H4(OH)2
C3 l nhit dung ring ca C6H4(OH)2 , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Thay vo ta c
13. C3 = 6.11700 + 6.18000 + 2. 25100
C3 = 2021,239 J / kg.
Vy q3 = 33,166.2021,239.25 = 1675910,317 (Kcal/h)
+ Nhit lng do OH -(C6H4)2- OH mang ra
q4 = C4 . m4 . t4
C4- l nhit dung ring ca OH -(C6H4)2- OH , Kcal / kg.
t4- l nhit ca sn phm ra, t4 = 25 0C
m4- lng OH -(C6H4)2- OH , m4 = 8,591 (Kg / h)
Nhit dung ring ca hp cht OH -(C6H4)2- OH c xc nh nh sau

Nguyn Vn Tin

76

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

M .C3 =n1.C1 + n2.C2


Trong
M khi lng mol ca hp cht OH -(C6H4)2- OH
C4 l nhit dung ring ca OH -(C6H4)2- OH , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung rintg ca cc nguyn t tng ng, J / kg nguyn t .
Thay vo ta c
186. C4 = 12.11700 + 10.18000 + 2. 25100
C4 = 1992,473 J / kg.
Vy q4 = 8,591.1992,473.25 = 427933,388 (j/h) =102,205 (Kcal/h)
+ Nhit lng do C6H5S H mang ra
q5 = C5 . m5 . t5
C3- l nhit dung ring ca C6H5S H, Kcal / kg.
t5- l nhit ca C6H5S H sn phm ra, t5 = 25 0C
m5- lng C6H5S H, m5 = 265,683 (Kg/h)
Nhit dung ring ca hp cht C6H5S H c xc nh nh sau
M .C5 =n1.C1 + n2.C2
Trong
M khi lng mol ca hp cht C6H5S H
C5 l nhit dung ring ca C6H5S H , J / kg .
n1, n2 s nguyn t cc nguyn t trong hp cht
C1,C2 Nhit dung ring ca cc nguyn t tng ng, J / kg nguyn t .
tra bng ta c :
Cc =11700 j/kg nguyn t , CH = 18000 j/kg nguyn t ,
Co = 25100 j/kg nguyn t , CNa = 33500 j/kg nguyn t .
110 C5 = 6.11700 + 6.18000 + 31000

Nguyn Vn Tin

77

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C5 =1901,818 (j/kg )
C5 =1901,818 (J / kg.)
Vy q5 = 1901,818.265,683.25 =12632017,79 (j/h) = 3016,961 (Kcal/h)
+ Nhit lng do C6H5ONa d mang ra
q6 = C6 . m6 . t6
C6- l nhit dung ring ca C6H5ONa, Kcal / kg.
t6- l nhit ca sn phm C6H5ONa ra, t6 = 25 0C
m6- lng C6H5ONa, m6 = 42,846 (Kg/h)
Nhit dung ring ca hp cht C6H5ONa c xc nh nh sau
M .C6 =n1.C1 + n2.C2
Trong :

M - khi lng mol ca hp cht C6H5ONa


C6 - l nhit dung ring ca C6H5ONa, J / kg .
n1, n2 - s nguyn t cc nguyn t trong hp cht

C1,C2 - Nhit dung rintg ca cc nguyn t tng ng, J/kg nguyn t .

Thay vo ta c
C6 = 1886,21 (J / kg.)
Vy q6 = 42,846. 1886,21 . 25 = 2020,413 (kj/h) = 482,544 (Kcal/h)
+ Nhit lng do SO2 mang ra
q7 = C7 . m7 . t7
C7- l nhit dung ring ca SO2 , Kcal / kg.
t7- l nhit ca SO2 sn phm ra, t7 = 25 0C
m7- lng SO2, m7 = 491,716 ( Kg / h)
C7 = 1536,204 (J / kg.)
q7 = 491,716.1536,204.25 = 18884,402 (kj/h) = 4510,246 (kcal/h)
+ Nhit lng do Na2SO3 mang ra

Nguyn Vn Tin

78

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

q8 = C8 . m8 . t8
C8- l nhit dung ring ca Na2SO3 , Kcal / kg.
t8- l nhit ca sn phm Na2SO3 ra, t8 = 25 0C
m8- lng Na2SO3, m8= 3024,985 (kg/h)
C8 = 1375,4 (j/kg .)
q8 = 3024,985. 1375,4 .25 = 104014,109 (kj/h) = 24842,156 (kcal/h)
+ Nhit lng do C6H5- C6H5 mang ra
q9 = C9 . m9 . t9
C9- l nhit dung ring ca C6H5-O- C6H5 , Kcal / kg.
t9- l nhit ca sn phm C6H5-O- C6H5 ra, t9 = 25 0C
m9- lng C6H5-O- C6H5 , m9 = 15,497 (kg/h)
C9 = 1536,204 (J / kg.)
q9 = 15,497.1536,204.25 = 595,163 (kj/h) = 142,146 (kcal/h)
Vy tng nhit lng mang ra l : Q3 = 1837846,667 (kcal/h)

4. Nhit lng mt mt ra mi trng xung quanh.


Nhit lng tht thot ra mi trng xung quanh chng ta coi gn bng 5 %
nhit lng do nguyn liu cung cp vo
Q4 =0,05 Q1 = 3024763,453.0,05 = 151238,173 (kcal/h)
5. Nhit lng mt do tc nhn lm lnh.
Nhit lng do tc nhn lm lnh c xc nh theo cng thc sau:
QLL = Q5 = Q1 + Q2 - ( Q3 + Q4 )
QLL=Q5=
3024763,453 + 1396,546 - (1837846,667 + 151238,173) = 1037075,159 (Kcal/h)
T qa trnh tnh ton trn chng ta c th lp c bng cn bng nhit lng
cho qa trnh axit ha .
Lng nhit vo
Kcal / h
Nl do nguyn liu 3024763,453

Nhit lng ra
Kcal / h
Nhit lng do sn phm 1837846,667

mang vo

mang ra

Nguyn Vn Tin

79

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


Nhit do phn ng

Tng

nhit

1396,546

n tt nghip
Nhit lng mt mt ra

151238,173

mi trng xunh quanh


Nhit do tc nhn lm

1037075,159

lnh
lng 3.026.159,999 Tng nhit lng mang ra

3.026.159,999

vo

CHNG III :

TNH TON THIT B CHNH


I. Tnh th tch lm vic ca thit b chnh:
Tra bng ta c:
- Khi lng ring ca benzen C6H6 :
= 880 g/l
- Khi lng ring ca axit sunfuric H2SO4:
= 1832 g/l
- Lu lng benzen a vo thit b:
V1 =

6541,436 .10 3
= 7433,45 (l/h)
880

- Lu lng axit sunfuric a vo thit b l:


V1 =

8665,16 .10 3
= 4729,89 (l/h)
1832

- Vy th tch hn hp nguyn liu i vo thit b l:


Vhh = V1 + V2 = 7433,45 + 4729,89 = 12163,34 (l/h)
- Chn th tch thit b:
Vhh = 70 80% Vthit b
Vthit b = 12163,34.

100
= 17376,2 (l/h) = 17,376 (m3/h)
70

Mt khc Vthit b = S.H

Nguyn Vn Tin

80

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


Trong :

n tt nghip

S: Tit din ca thp, m2


H: Chiu cao thit b, m
D: ng knh ca thp, m
S=

D 2
Chn D = 1,6 m
4

Chiu cao thit b l: H = 6 m

II. Tnh ton c kh mt s chi tit ch yu ca thit b:


1. Tnh chiu dy thn thp.
Dt.P

S = 2[ ]. P + C ,m
Trong :
- Dt: ng knh trong ca thp, m
- : H s bn ca thnh hnh tr theo phng dc
- C: H s b xung so n mn v dung sai v chiu dy, m
- P: p sut thit b, N/m2
- P = Pmt + Ph
- Pmt: p sut lm vic ca thit b Pmt = 1.106, N/m2
- Ph: p sut thu tnh ca nc, Ph = .g.H, N/m2
Vi g: Gia tc trng trng, g = 9,81 m/s2
H: Chiu cao ct cht lng, H = 4m
S: Khi lng ring ca cht lng, kg/m3
= 1356 kg/m3
Ph = .g.H = 1356.9,81.4
Ph = 5,32.104 N/m2
Ph = 1.106 + 5,32.104 = 1,05.106 N/m2
Tra bng ta c: = 0,95
C = C1 + C2 + C3

Nguyn Vn Tin

81

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

C1: B xung do n mn, C1 = 1 mm


C2: B xung do bo mn, C2 = 0
C3: Dung sai v chiu dy C3 = 0,8 mm
- ng sut ca thp CT3 theo gii hn bn ko:
k

- [k] = n . (N/m2)
k
Tra bng : nk =2,6 H s an ton
= 1, h s iu chnh
Suy ra:

450.10 6
.1 = 173,08.10 6 (N/m2)
[k] =
2,6

- ng sut cho php tnh theo gii hn chy:


c

[k = n . ] (N/m2)
c
Tra bng

nc = 1,5 : h s an ton
= 1, h s iu chnh

Suy ra:

270.10 6
.1 = 180.10 6 (N/m2)
[k] =
1,5

Ta ly gi tr nh hn trong hai kt qu va tnh c ca ng sut tnh ton:


[k] = 173,08.106 (N/m2)

Ta ly
V

[ k ]
137,08.10 6
. =
.0,95 = 153,53 > 50
p
1,071.10 6

Do c th b qua i lng P mu s trong cng thc tnh chiu dy:


Dt.P

S = 2[ ]. + C
k
k
161,05.10 6
+ 1,8.10 3 = 6,9.10 3 ,m
S=
6
2.173,08.10 .0,95

Chn S = 8 mm
Chn y v np elip ca thit b c cng kch c:
Sy = Snp = 8 mm

Nguyn Vn Tin

82

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


S = 8 mm

hb = 400 mm

Dt = 1600 mm

h = 40 mm

n tt nghip

2. Tnh ng knh ng dn sn phm v nguyn liu.


d=

V
,m
0,785.

Trong : : Tc trung bnh , chn = 0,2 m/s


V: Lu lng th tch hn hp, V = 4,27 m3/h = 1,18.10-3 m3/h
d=

1,18.10 3
= 0,0867 m = 86,7 mm
0,785.0,2

Chn d = 100 mm
Chn ng knh ng a nguyn liu vo l 100 mm.
Chn ng knh ng hi l 100 mm.
3. Chn bch ni thit b.
Chn bch ca np v thn, thn - thn, thn - y cng mt kiu bch v cng
mt kch c.
Chn kiu bch lin vi thit b lm bng thp.
Tra bng ta c cc thng s v bch:
P = 1.106 N/m2
Dt = 1600 mm

D = 1810 mm
Db = 17400 mm

D1 = 1675 mm
D0 = 1619 mm

Bu lng db = M20
Z = 52 ci

Chn mt bch lp ghp cc ng dn vo thn hoc y v np. Chn loi bch


lin bng kim loi en kiu 1 ni cc b phn ca thit b.
Bng: S liu v bch
P = 1.106

Dy

N/m2
1,0

mm
100

Dn ,mm
108

Kch hc ni
Dt ,mm
D ,mm
205
170

Dl ,mm
148

Bu lng
Db
Z
M16 4

H
mm
22

III. Cu to ca chp v ng chy chuyn.


- Chn ng knh ca ng hi, m

Nguyn Vn Tin

83

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

dh = 66 mm = 0,066 m
- S chp trn a c tnh:
n = 0,1.

D2
d h2

Trong :
D: ng knh trong ca thp, D = 1,6 m
B mt t do ca a, Ft do = 0,1
n = 0,1.

1,6 2
= 58,7 chp
0,66 2

Quy chun s chp l n = 66 chp


ng knh ca chp:
dch = d h2 + (d h + 2. ch ) 2
: Chiu dy ca chp, chn = 3 mm
dch = 66 2 + (66 + 2.3) 2
dch = 97,67 mm (chn dch = 100 mm)
Chiu cao ca chp pha trn ng dn hi.
Hh = 0,25.dh = 0,25.0,066 = 0,0165 m
Ly hh = 0,02 m = 20 mm
* ng knh ng chy chuyn.
d=

4.G
,m
3600. . .w.z

G: Lu lng lng trung bnh i trong thp, kg/h


: Khi lng ring ca lng, kg/m3
w: Tc cht lng trong ng chy chuyn w = 0,1 m/s
z: S ng chy chuyn z = 1
G = 6541,436 kg/h
= (880 + 1832)/2 = 1356 kg/m3

Nguyn Vn Tin

84

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Vy ng knh ng chy chuyn:


d=

4.6541,436
= 0,13 ,m
3600.3,14.1356,0,1.1

Khong cch t mt a n chn chp.


Trong thc t thng ly s = 5 mm
Chiu cao mc cht lng trn khe chp
Trong thc t hl = 30 mm
Chiu cao ca khe chp
Ly b = 0,072 m = 72 mm
S lng khe h mi chp
i=

(d ch h )
c
4b

c: Khong cch gia cc khe, chn c = 4 mm


b: Chiu cao ca khe chp, mm
dch: ng knh chp, mm
dh: ng knh ng hi, mm
i=


66 2
= 66,6 mm
.100
4
4.72

Chn i = 66 khe chp


Chiu rng ca khe chp, mm
a=

d h2 3,14.66 2
.
=
= 0,72 mm
4 bi
4.72.66

Chn a = 1 mm
Khong cch t a n chn ng chy chuyn. Ly S = 5 mm
Khong cch t tm ng chy chuyn n tm chp gn nht.
T=

d ch
d
+ 2. + c + l l
2
2

Ll : Khong cch nh nht gia chp v ng chy chuyn


Chn ll = 75 mm

Nguyn Vn Tin

85

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Ta c:
T=

100
120
+ 2.3 +
+ 75 = 191 mm
2
2

Chn T = 190 mm
Chiu cao ca chp: ly l = 90 mm
Chiu cao ca ng dn hi trn a
Lh = 1 - - hh = 90 - 3 - 20 = 67 mm
Chn Lh = 65 mm

Phn IV:

TNH TON KINH T V XY DNG


Chng I:

XY DNG
I. Gii thiu:
Phn xng sn xut phenol i t benzen, vi nng sut 55.000 tn/nm c
thit k v xy dng nm trong khu lin hp lc du Dung Qut - Qung Ngi.
Tng mt bng c din tch l: 10.000 m2.
S cng nhn lm vic trong phn xng l 20 ngi.
Phn xng sn xut phenol c xy dng ti Dung Qut - Qung Ngi l do
cc yu t thun li sau:
- Nguyn liu (Benzen) sn xut Phenol c ly trc tip ngay ti khu lin
hp lc du.
- Chi ph cho vic vn chuyn s gim rt nhiu, em li li nhun cao (chim
40-60%) gi thnh sn phm).
- Vic s dng kh thi, ph phm c tp trung, do t nh hng n vn
mi sinh cng nh chi ph cho qu trnh s l cc ph thi .

Nguyn Vn Tin

86

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

II. Cc yu cu i vi a im xy dng.
1. Yu cu chung.
* a im xy dng phi ph hp vi qui hoch lnh th, qui hoch vng, qui
hoch cm kinh t cng nghip c cc cp c thm quyn ph duyt.
* Phn xng phi gn vi ngun cung cp nguyn liu cho sn xut v gn ni
tiu th sn phm.
* Ph hp v tn dng ti a h thng giao thng quc gia, h thng mng li
cung cp in.
* Phi chn a im xy dng gn vi ni cung cp vt liu xy dng, ch
n kh nng cung ng cng nhn cho xy dng cng nh vn hnh nh my sau
ny.
2. Yu cu v k thut xy dng.
Khu t phi c kch thc v hnh dng thun li cho vic xy dng trc mt
cng nh vic m rng nh my trong tng lai.
Khu t phi cao ro, trnh ngp lc trong ma ma l.
Khu t phi tng i bng phng v c dc tu nhin tt nht l 0,5 - 1%
hn ch kinh ph cho san lp mt bng (chim 10 - 15% gi tr cng trnh)
Khu t c chn khng c nm trn cc vng c m khong sn hoc a
cht khng n nh.
Cng khu t xy dng l 1,5 - 2,5 kg/cm 2. Nn xy dng trn nn t st,
st pha ct... gim chi ph gia c nn mng.
Cn ch n mi quan h gia khu dn c th v khu cng nghip. Phi m
bo ti mc cn thit vn mi sinh.

III. Tng mt bng nh my.


1. Cc hng mc cng trnh
STT
1
2

Tn cng trnh
Cng tin v nh n
Khu hnh chnh

Nguyn Vn Tin

Chiu di, m Chiu rng, m Din tch, m2


24
12
288
24
12
288
87

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni


3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

Nh xe
Nh bo v
Phng ho nghim
Phng k thut
Phng iu khin
Nh sn xut
Kho thnh phm
Khu x l nc thi
Khu m rng sn xut
Kho nguyn liu
Nh cu ho
Khu sn xut hi nc
Trm cp nc
Trm bin p
Nh xe chuyn dng
Di cy xanh phn cch
Nh xe
Tng din tch sn xut

n tt nghip
36
4*6
9
9
9
48
18
18
48
18
12
24
6
6
12

12
4*6
6
6
6
15
12
12
18
12
9
12
6
6
12

648
96
54
54
54
720
216
216
864
216
54
108
36
36
144

18

162
4272

2. Nguyn tc thit k.
Da vo nguyn tc phn vng v da vo c im sn xut ca phn xng
m tng mt bng c phn ra lm 4 vng chnh sau:
- Khu hnh chnh.
- Khu sn xut v kho tng.
- Khu nng lng ph tr.H thng giao thng v khun vin
Khu hnh chnh, hi trng, cng tin, nh n, trm y t c b tr pha trc
nh my.
Khu sn xut v kho tng gm nh sn xut Phenol, kho thnh phm, kho cha
nguyn liu, phng th nghim, phng k thut v phng iu khin trung tm.
Khu nng lng ph tr gm tr bin th, nh phng chy cha chy, trm cp
nc.
H thng giao thng v cng vin, ng giao thng vi chiu rng 6m c b
tr sao cho cc qu trnh vn chuyn, i li, phng chy thun tin. Nguyn tc
phn vng c cc u khuyt im sau:

Nguyn Vn Tin

88

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

* u im:
- D qun l theo tng b phn, theo cc khu vc, theo cc giai on khc nhau
ca qu trnh sn xut.
- Vi nguyn tc ny s thch hp vi nhng phn xng c cc giai on khc
nhau.
- H thng giao thng c b tr d dng hn.
- Thun li cho vic m rng v pht trin nh my trong tng lai.
- c bit ph hp vi c im xy dng nc ta.
* Nhc im:
- Dy truyn sn xut phi ko di.
- H thng ng ng, ng giao thng tng.
- H s xy dng, h s s dng t.

IV. Ch tiu kinh t:


H s xy dng:

Kxd = 28%

H s s dng :

Ksd = 65%

Trong :
Kxd =

( A + B).100%
F

Ksd =

( A + B + C ).100%
F

F Din tch ton nh my, F= 15.000 m2


A Din tch t xy dng, A = 6410 m2
B Din tch t l thin, B = 3100 m2
C Din tch ca ng b, va h...., C = 3500 m2

V. Kt cu cc cng trnh xy dng.


1. Nh hnh chnh, nh iu khin trung tm, nh sinh hot, cng tin, hi trng,
nh y t c thit k nh sau:

Nguyn Vn Tin

89

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Nh xy dng cp 4 mi dc v hai pha, lp bng fibroximng c cc ct


bin bng b tng ct thp.
Kch thc ct l: 300x300x3600 mm.
Ct gia c cc kch thc: 300x4400x4200 mm.
Dng mng n di ct c cc kch thc l:
Bng: Kch thc mng nh.
Tit din ct
300x300

C1
800

D1
800

C
1300

d
1300

H
600

2. Nh sn xut.
- Chiu di nh 48m, chia lm 8 bc ct, mi bc ct 6m.
- Chiu cao nh l 10m.
- Ct c kt cu bng b tng ct thp kch thc phn di vai ct l
400x600x6200 mm, phn trn vai ct c kch thc l 400x400x3200 mm.
- Kt cu mng dng n di ct c dm mng kch thc 250x400x5900.
- Dm hai mi (dc v hai pha) c i = 1-15; L = 12m.
- Dm mi khung thp lp ghp.
3. Kt cu cc cng trnh ph tr nh trm bin th, nh bo v...
Kt cu ca mi bng b tng ct thp, tng bao quanh dy 220 mm, tng
ngn dy 110 mm. Nn ximng ct si c lt gch hoa.

VI. Giao thng v khu khun vin.


ng giao thng trong nh my c di nha ng, c chiu rng 6m,
chia lm hai ln chnh, ni cc khu sn xut vi nhau m bo mt giao thng
vn chuyn cc nguyn vt liu cng nh sn phm d dng.
Hai bn ng v xung quanh cc cng trnh c trng cy m bo cnh quan
v gi mi sinh trong lnh.

VII. Yu cu khi xy dng nh my.


Nguyn Vn Tin

90

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

- Vn hng u l vic xy dng dy chuyn cng ngh trnh ct nhau chng


cho ln nhau.
- Thit b gn gng, an ton, nh sn xut xy ng qui cch v thit k ra,
m bo cho qu trnh lm vic khong 30 nm.
- B phn cu ho b tr cc v tr thun tin nht.
- Cc b phn x l kh thi, nc thi... phi t cui hng gi (cui nh my)
m bo mi sinh trong khu vc nh my.
- B tr cc ng cp nhin liu, nguyn liu cho phn xng phi thun tin
hp l v an ton cho vic phng chy n.

Nguyn Vn Tin

91

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Chng 2:

KINH T
Trong nn kinh t th rng ngy nay, vic xc nh cc ch tiu kinh t c
mt ngha rt quan trng, m bo v kinh t th s duy tr c s hot ng
cng nh c nhiu kh nng m rng qui m sn xut trong tng lai.
Bn lun n ny xin a ra phng hng hch ton kinh t cho phn xng sn
xut Phenol. Vi cc s liu gi thit, do c th khng c st vi thc t.

I. Vn u t cho phn xng.


1. Vn u t c nh.
Vn u t c nh = vn u t cho xy dng + Vn u t thit b.
a. Vn u t cho xy dng nh xng:
Trong ton b phn xng, tt c cc mt bng u tri nha, thit k theo kiu
l thin - bn l thin.
Ngoi nh sn xut chnh cn phi xy nhiu cng trnh ph tr nh: Nh hnh
chnh, hi trng...
Tng din tch nh my l: 20.000 m2
Gi thit vic xy dng phn xng cn: 300 triu ng.
Gi thit tin cng nhn xy dng l: 100 triu ng.
Vn u t cho nh xng l: 300 + 100 = 400 triu ng

Nguyn Vn Tin

92

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

b. Vn u t thit b:
Gi thit u t cho thit b l 600 triu ng.
Vn u t = 400 + 600 = 1.000 triu ng.
2. Vn u t lu ng.
S vng quay trong nm = 1.
Doanh thu = Gi sn phm*Sn lng.
Gi thit gi bn l: 5 triu ng/tn.
Doanh thu: 20.000*5.000.000 = 100.000 triu ng
Vn u t lu ng l: 100.000/l = 100.000 triu ng.
3. Vn u t ban u.
1.000 + 100.000 = 101000 triu ng

II. Hoch ton chi ph khc.


1. Tnh ton nguyn liu trc tip l: 50.000 triu ng
- Tng u t nguyn liu trc tip l: 50.000 triu ng
- Cho 1 n v sn phm: 50.000/20.000 = 2,5 triu ng
- in : Tng cng sut my mc thit b l 2000 kW/h
in tiu th trong mt nm: 2.000x24x355 = 17.040.000 kW/h.
- in sinh hot: 3.030 kw/h.355 = 10.650 k/h
Chi ph s dung in trong mt nm:
(17.040.000 + 10.650).1200 = 20.460,78 triu ng
2. Lng cng nhn.
- Lng bnh qun: 3 triu ng/ngi/thng
- Tng qu lng cho mt nm: 3*20*12 = 720 triu ng.
- Tr lng cho mt n v sn phm: 720/20.000 = 0,36 triu ng
- Trch 19% theo lng tr bo him x hi, y t...
- Trong mt nm: 720*0,19 = 136,8 triu ng.
- Tr ph cp c hi: 10% theo lng

Nguyn Vn Tin

93

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

- Trong mt nm: 720*0,1 = 72 triu ng


- Cho mt n v sn phm: 72/20.000 = 0,0036 triu ng.
3. Chi ph chung cho phn xng.
- Khu hao ti sn c nh bao gm:
+ Khu hao thit b: 10%*600*0,1 = 60 triu ng
+ Khu hao vn u t nh xng 5%: 400*0,05 = 20 triu ng
Khu hao ti sn c nh: 60 +20 = 80 triu ng
Khu hao ti sn c nh cho mt n v sn phm:
80/20.000 = 0,004 triu ng
- Tng chi ph khc chim 20% ti sn khu hao c nh.
Tng gi thnh = Chi ph sn cut chung + Chi ph tiu th + Chi ph
qun l doanh nghip.
Bng: Tng gi thnh
Chi ph

Tnh cho mt n v sn phm

Tnh cho c nm

(Triu ng)
3,57424
0,07149
0,07149
3,71722

(Triu ng)
71485,58
1429,7116
1429,7116
74345,0032

Chi ph sn xut chung


Chi ph doanh nghip
Chi ph tiu th
Tng gi thnh

III. Gi thnh v li nhun.


1. Xc nh gi bn.
Gi thnh sn phm 5.000.000 ng/tn.
2. Li nhun.
a- Doanh thu: 100.000 triu ng.
b- Thu VAT (10%)
Thu VAT u ra = 10% doanh thu +10% in
Thu VAT u ra = 0,1*100.000 + 0,1*20460,78
Thu VAT u ra = 12046,078 triu ng

Nguyn Vn Tin

94

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Thu VAT u vo = 0,1*50.000 triu ng = 5.000 triu ng


Thu VAT

= u ra - u vo
= 12.046,078 - 5000 = 7.046,078 triu ng

c- Li nhun.
Li nhun

= Doanh thu - (Gi ton b + Thu VAT)


= 100.000 - (74.301,38 + 7.046,078) = 18608,9188 triu ng.

Bng: Lp phng n cho mt tn sn phm 8 tng sn lng.


Khon mc

Chi ph cho mt n

Chi ph cho ton b

v sn phm (triu

sn lng (triu ng)

ng)
Chi ph nguyn liu trc tip
Tng nguyn liu

2,5

50000

in
Chi ph nhn cng

1,023

20460,78

Lng

0,036

720

Trch 19%

0,00684

136,8

10% c hi
Chi ph chung phn xng

0,0036

72

Khu hao ti sn c nh

0,004

80

Chi ph khc

0,0008

16

Chi ph qun l doanh nghip

0,07149

1429,7116

Chi ph tiu th

0,07149

1429,7116

Gi thnh ton b

3,71722

74345,0032

5000

100000

Thu VAT

0,3523

7046,078

Thu vn

0,011

219,244

Li nhun

0,93045

18608,9188

Gi bn d kin

IV. Xc nh hiu qu kinh t v thi gian thu hi vn.


Nguyn Vn Tin

95

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

* Hiu qu kinh t ca vn u t.
E = L nhun nm/vn u t =
V

18608,9188
= 18%
101000
101000

Thi gian thu hi vn = LN + CFC = 18608,9188 + 96 = 5,4 nm


V: Vn u t ban u, triu ng
LN: Li nhun hng nm, triu ng
CFC: Chi ph chung cho phn xng, triu ng
PHN V:

AN TON LAO DNG


T chc an ton v bo h lao ng trong nh my l mt cng vic khng
th tch ri khi sn xut. Bo v tt sc kho lao ng cho ngi sn xut cho
php y mnh sc sn xut nng cao nng sut lao ng.
Nguyn nh xy ra tai nn lao ng:
- thng do cc nguyn nhn chnh sau khi do k thut, do t chc giao
nhn), do v sinh cng nghip.
- Trong nh my ch bin du m b nhim ch yu bi kh hydrocarbon
(hydrocarbon mch thng c tnh c hn hydrocarbon mch nhnh,
hydrocarbon vng c hn mch thng).
- nh hng bi cc kh ph tr nh kh CO2, H2S
Khi nghin cu tc hi ca ho cht v bi ngi ta a ra nng cc hp
cht c hi cho php ti a nh sau:
Hp cht
Nng mg/l
Xng - dung mi
< 0.3
H2S
0,01
Bi
2
SO2
0,01
......
chng bi cn thit phi s dng cc bin php ti thiu sau:

Nguyn Vn Tin

96

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

- C kh ho, t ng ho qu trnh sn xut hn ch tc dng ca cc


hp cht c hi.
- Bao kn thit b
- Thay i phng php cng ngh lm sch
- Thng gi ht bi
- Bo m v sinh cong nghip
Cc bin php cn thit phng chng chy n :
Thay khu sn xut nguy him bng khu t nguy him.
C kh ho, t ng ho cc qu trnh sn xut c tnh cht nguy him
m bo an ton.
Thit b bo m kn hn ch hi, kh chy thot ra xung quanh khu sn
xut.
Loi tr kh nng pht sinh mi la ti nhng ni c lin quan n chy n.
Kh nng to nng nguy him ca cc cht chy.
Ti nhng ni c th gy chy n cn t bin cm, dng c cha chy
nhng ni d thy v thun tin thao tc.
Xy dng i ng cha chy chuyn nghip v nghip d thng xuyn
kim tra din tp.
Khi c s c chy n xy ra tu tnh cht nguy him ca ni to chy cn
phi cp tc thi hnh cc bin php k thut cn thit nhng ni ln cn nh
ngng cng tc, ct in, pht tn hiu cp cu cha chy.
Trn y ch l mt s bin php ti thiu trong cng tc phng chng chy
n, bo h lao ng trong nh my, xong cn thit phi tuyn truyn mi ngi
thc hin tt bin php phng nga m bo an ton cho qu trnh sn xut.

Nguyn Vn Tin

97

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Kt lun
Qua qu trnh thit k cong ngh sn xut Phenol, bn n thc hin
nhng phn sau:
Nu cc phng php sn xut Phenol trong cng nghip
Tnh cht ca phng php sn xut Phenol qua benzen sunfo axit
C ch phn ng sunfo ho v nng chy kim.
Tnh cht ca nguyn liu v sn phm.
Dy chuyn sn xut Phenol
Cn bng vt cht.
Cn bng nhit lng.
Tnh ton thit b chnh.
Mt bng phn xng sn xut Phenol.
Tnh ton kinh t
Nghin cu qa trnh sn xut phenol l iu ht sc quan trng v th n
c thc hin t lu v a vo sn xut. Do kinh nghim v cng ngh
sn xut c nhiu nn qa trnh nghin cu to cho em nhiu thun li. Sau
mt thi gian nghin cu v c s hng dn nhit tnh ca thy GS.TS o
Vn Tng em hon thnh n mn hc, m bo c tnh chnh xc v
thi gian qui nh. Em xin chn thnh cm n thy v cng ton th cc bn
gip em trong qa trnh nghin cu.

Nguyn Vn Tin

98

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

Nhng do thi gian v trnh c hn nn khng th trnh khi nhng sai st


trong bn n tt nghip ny. V vy em rt mong c s ng gp kin ca
cc thy cng tt c cc bn
Ngi thc hin
Nguyn Vn Tin
Lp HD 2 - K44

Ti liu tham kho


1.Phan Minh Tn Tng hp hu c ha du, TP H Ch Minh 1999
2. HBK H Ni K thut tng hp hu c ,1979
3. HBK H Ni- K thut tng cc cht trong trung gian,1976
4. HBK H Ni ,S tay qa trnh v thit b ha hc. Tp 1, tp 2, NXB khoa
hc k thut,1976
5. HBK H Ni , S tay Ha l , NXB khoa hc k thut, 1977
6. Nguyn Mu Quyn, Ha Hc V c, Nh xut bn khoa hc k thut,1999
7.Tp th tc gi,H Cng Xinh, Nguyn Th Thanh, Ha Hu c, Tp 3 ,1997
9. HBK thnh ph H Ch Minh. S tay tm tt i lng ho l, 1990
10, Vng nh Nhn. S tay tm tt ca k s ho cht, 1961
11. Barbara Elvers, Stephen Hawkins.
Ullmans Encyclopedia of industrial chemistry, Vol A19, 1991
12. Wolfgang Gerhartz.
Ullmans Encyclopedia of industrial chemistry, Vol A3, 1985
13. Barbara Elvers, Stephen Hawkins.
Ullmans Encyclopedia of industrial chemistry, Vol A20, 1992
14. Barbara Elvers, Stephen Hawkins, Michael Ravenscroft.
Ullmans Encyclopedia of industrial chemistry, Vol A13, 1989

Nguyn Vn Tin

99

Lp Ha Du 2 - K44

Trng i hc Bch Khoa H Ni

n tt nghip

15. Hydrocacbon Processing, February - 1999


16. Hydrocacbon Processing, October - 1998
17. Hydrocacbon Processing, March - 1997
18. Hood, Horace. United States Patent, July 4, 1995

Nguyn Vn Tin

100

Lp Ha Du 2 - K44

You might also like