MC LC

CHNG: TNG QUAN V NGUYN LIU V SN PHM. .5

1.1. Gii thiu v Propylen:............................................................................5
1.1.1. Tnh cht vt l: [3]........................................................................6
1.1.2. Tnh cht ha hc: [4]....................................................................7
1.1.3. Qu trnh pht trin v cc ngun thu nhn chnh: [5]....................8
1.2. Gii thiu v Hydrogen:[6]......................................................................9
1.2.1. Tnh cht vt l: [7]........................................................................9
1.2.2. Tnh cht ha hc :[8]...................................................................10
1.2.3. ng dng v sn xut:[9].............................................................10
1.3. Sn phm Polypropylen :.......................................................................11
1.3.1. Lch s ra i:...............................................................................11
1.3.2. c tnh chung..............................................................................11
1.3.3. Cng dng....................................................................................11
1.3.4. Phn loi Polypropylen.................................................................11
1.3.5. Cu trc phn t...........................................................................13
1.3.6. Hnh thi hc................................................................................14
1.3.7. Tnh cht nhit ng hc..............................................................20
1.4. Cht xc tc...........................................................................................21
1.4.1. Lch s ra i v pht trin...........................................................21
1.4.2. Cu to, thnh phn ca cht xc tc...........................................22
1.5. L THUYT TRNG HP PROPYLENE..........................................24
1.5.1. C ch trng hp Propylene.........................................................24
1.5.2. Vn iu ha lp th v iu ha vng trong s chn monomer
27

CHNG 2: TNG QUAN V NH MY SN XUT

POLYPROPYLEN........................................................................30
CHNG 3..........................................................................................33
LA CHN CNG NGH SN XUT POLYPROPYLENE......33
3.1. Nhng qu trnh polimer ha Propylen thng dng...............................33
3.2. QUY TRNH SN XUT CHUNG......................................................33
3.2.1. Khu vc x l nguyn vt liu ban u:.......................................34
3.2.2. Khu vc polimer ha....................................................................34

3.2.3. Khu vc tch v thu hi kh..........................................................35

3.2.4. Khu vc x l cn v kh mi:....................................................35
3.2.5. Khu vc p tao ht v qui trnh x l cc ht nh........................35
3.2.6. Khu vc ng bao v ng thng:................................................35
3.3. M T V CC CNG NGH C S DNG HIN NAY.........35
3.3.1. Cng ngh pha lng......................................................................35
3.3.1.1. M t qui trnh cng ngh SPHERIPOL................................35
3.3.2. Qu trnh polymer ho..................................................................37
3.3.3. Khu vc lm kh sn phm polymer...........................................39
3.3.4. Qu trnh trn ph gia v n p..................................................39
3.3.4.1. M t cng ngh HYPOL-II..................................................39
3.3.5. Cng ngh pha kh:.......................................................................43
3.3.5.1. M t qui trnh cng ngh NOVOLEN..................................43
3.3.5.2. M t chu trnh cng ngh "UNIPOL"..................................47
3.3.5.3. M t qui trnh cng ngh ca INNOVENE..........................50
3.4. Khi qut v pht trin cng nghip Polyproplene.................................53
3.5. Gii trnh v s la chn cng ngh sn xut PP...................................53

CHNG 4: M PHNG CNG NGH SN XUT

POLYPROPYLENE BNG PHN MM HYSIC...................58
4.1. NHNG THNG S BAN U

[3.1].............................................58

4.2. TNH CC GI TR BAN U CHO QU TRNH M PHNG.....60

4.3. TNH TON QU TRNH NH M PHNG BNG PHN MM
HYSYS 66
4.3.1. Gii thiu v phn mm Hysys.....................................................66
4.3.2. Cc bc m phng s cng ngh sn xut Polypropylene.....67
4.3.2.1. Xy dng m hnh, iu kin phn ng.................................67
4.3.2.2. Xy dng thit b phn ng...................................................73
4.3.2.3. Xy dng cc thit b tch loi..............................................75
4.3.3. Kt qu thu c t qu trnh m phng......................................76

CHNG 5: TNH TON CC THIT B CHNH......................79

5.1. TNH TON KCH THC CHO THIT B CHNH.........................79
5.1.1. Cc thit b phn ng....................................................................79
5.1.2. Thit b tch loi...........................................................................79

5.1.3. Kt qu thu c t m phng.....................................................79

5.2. Cc thit b chnh...................................................................................79
5.3. Cc thit b ph khc..............................................................................80

CHNG 6: XY DNG H THNG IU KHIN CA QU

TRNH...........................................................................................85
6.1. Tng quan v h thng iu khin :.......................................................85
6.1.1. Cc nguyn tc c bn ca qu trnh iu khin...........................85
6.1.1.1. iu khin ng m..............................................................85
6.1.1.2. iu khin qu trnh..............................................................85
6.1.2. H thng iu khin phn tn DCS trong cc nh my hin i...85
6.1.3. B IU KHIN PID.................................................................86
6.1.3.1. Vai tr ca b iu khin PID................................................86
6.1.3.2. Tc ng t l P......................................................................87
6.1.3.3. Tc ng tch phn I..............................................................88
6.1.3.4. Tc ng vi phn D...............................................................89
6.1.4. La chn khu tc ng v cc thng s t trng cho PID.........90
6.1.5. H thng iu khin trong nh my sn xut POLYPROPYLEN 92
6.1.5.1. B iu khin lu lng : Gm cc thit b iu khin lu
lng :
92
6.1.5.2. B iu khin nhit : Gm cc thit b iu khin:.........93
6.1.5.3. B iu khin nng :.........................................................93
6.1.5.4. B iu khin mc :...............................................................93
6.2. Phng php iu khin mt s thng s dng vt cht bng Hysic :. .93
6.2.1. Tin hnh v hon tt m phng tnh qu trnh trao i nhit ca
dng Propylen :....................................................................................................93
6.2.2. Xy dng h thng iu khin PID cho thit b :..........................94

LI NI U
Ngy nay, khi chng ta tr thnh thnh vin chnh thc ca WTO th nn cng
nghip c nhiu c hi pht trin hn, trong ngnh Cng ngh Lc - Ha Du
c u tin pht trin hng u. l mt trong nhng ngnh mi nhn pht trin
t nc, ph hp vi tim nng Du m hin c ca nc ta.
Chnh iu ny to nhng tim nng rt ln cho mt tng lai v tn dng
nhng sn phm ha du, trong tng hp cc hp cht Polymer l ngnh ang c xu
hng pht trin mnh Vit Nam. l mt ngnh khoa hc nghin cu v vic
tng hp cc cht hu c c ng dng rng ri trong i sng bng cch tn dng
ngun nguyn liu t du m. Vic sn xut, s dng polymer ngy cng c m
rng v c quy m pht trin nhanh. c bit khi tnh hnh nguyn liu thin nhin
v ang ngy cng khan him, s tiu th cc ngun nng lng cng nh cc hp
cht ha hc c sn din ra vi tc ngy cao t ra nhng vn vi cc nh ha
hc l phi tm ra nhng hp cht thay th chng. Polypropylene cng l mt trong s
nhng polymer c s dng rng ri nht trn th gii v tnh ph dng, gi thnh
monomer thp, gi thnh sn xut thp, v cc tnh cht c a chung ca n.
Hin nay, nc ta c nhiu d n xy dng Nh my lc du v ang c
trin khai. y c coi l im ha hn cung cp ngun Propylene nguyn liu di
do. Vic xy dng nh my sn xut Polypropylene l yu cu rt cn thit v cp
bch mang tnh x hi, tnh kinh t gp phn cng vi nhp tng trng kinh t
chung cho t nc.
Vi s ra i Nh my lc du s 1 vi cng sut 6,5 triu tn/nm ti Khu
Cng Nghip Dung Qut, tnh Qung Ngi. Cn thit phi c nh my sn xut
Polypropylene a vo vn hnh ng thi.
Mt khc, trong thi i ngy nay, cng vi s pht trin khng ngng ca cc
tin b khoa hc k thut, vic ng dng cc phn mm chuyn dng vo trong cc
lnh vc k thut khc nhau cng tr nn rt ph bin. Nh c s xut hin ca cc
cng c c lc ny m vic iu khin, vn hnh cc quy trnh cng ngh ngy cng
hin i v ti u hn. Bn cnh , cc phn mm chuyn dng ny cn gip cc nh
thit k cng nh vn hnh c th tin hnh tnh ton, thit k v ti u cc thng s
ca qu trnh. chnh l nh s ra i ca cc phn mm m phng.
Cc phn mm m phng c ngha c bit quan trng i vi ngnh du kh
ni ring v cc ngnh k thut khc ni chung. N cho php ngi s dng tin hnh
cc thao tc m phng mt quy trnh c trong thc t hoc thit k mt quy trnh
mi nh c th vin d liu phong ph v chnh xc vi tng ngnh khc nhau. Mt
trong s chnh l phn mm Hysis L phn mm tnh ton chuyn dng trong cc
lnh vc cng ngh ha hc, c bit trong lnh vc lc - ha du, polymer, ha dc.
T nhng phn tch trn, em quyt nh chn ti: Tng quan cng ngh v
m phng thit k nh my sn xut Polypropylene Nng sut:
150000 Tn/nm bng phn mm Hysis.

CHNG 1
TNG QUAN V NGUYN LIU V SN
PHM
1.1. GII THIU V PROPYLENE:
Propylen (tn thng thng), c tn quc t l Propen l mt hydrocacbon
khng no, thuc h alken.
- Cng thc phn t: C3H6
- Cng thc cu to:

L ngun nguyn liu chnh sn xut Polypropylene.

Cc ngun thu nhn Propylene chnh: [1]
Ngun nguyn liu chnh sn xut Polypropylene l Propylene. Sn xut
Propylene l lnh vc sn xut quy m ln, c mc tng trng nhanh. Propylene l
nguyn liu cho nhiu sn phm ha du quan trng nhng cho n nay n vn c
coi l sn phm ph hoc sn phm ng hnh ca cc nh my lc du (NMLD) v
cc nh my sn xut Ethylene.
V c bn, ton b lng Propylene s dng cho cng nghip ha cht u
c sn xut t cc NMLD (cracking xc tc) hoc l ng sn phm ca Ethylene
trong cc nh my cracking bng hi nc. Ngoi ra, cn nhng lng Propylene
tng i nh c sn xut bng cc phng php khc nh: Tch Hyrogen khi
Propane, phn ng trao i Etylene Butene, chuyn ho t Methanol (MeOH UOP/Hydro MTO hay Lurgi MTP).
Trong mt bo co th trng ca tp ch Nghin cu th trng cng nghip
ho cht th gii thng 11-2003, th sn lng Propylene ca th gii khong 72 triu
tn trong : 61% t cracking bng hi nc (t l Propylene:Ethylene l 3,5:10 n
6,5:10); 36% t NMLD; 3% cc qu trnh cn li.

Hnh 1 : Cc ngun thu nhn Propylene[2]

1.1.1. Tnh cht vt l [3]
Propylen c cng thc phn t (C3H8), cng thc cu to CH2 = CH - CH3 l
thnh vin n gin th hai trong h Alkene. Propylen l mt cht kh, khng tan trong
nc, trong du m, dung dch Amoni ng cng nh cc cht lng phn cc nh:
Ether, Etanol, Axeton, Fufurol...Do trong phn t c lin kt , nhng tan tt trong
nhiu sn phm ha du quan trng, v l cht kh d chy n. Propylen cng l
nguyn liu khng mu, khng mi, do ngi ta thng pha thm mercaptan c
mi gn ging nh ti vo thnh phn ca n d dng nhn bit.
Sau y l cc hng s vt l c bn ca Propylen:
Khi lng phn t: 42,08 vC.
p sut ti hn: Pc = 4.7MPa.
T trng trng thi lng (15oC, 760mmHg): 0.51.
T trng trng thi hi (15oC,760mmHg): 1.49.
tan (trong nc -50oC): 0.61g/m3.
nht(20oC): 0.3cSt, (ti 20oC v 1at 8.35.10-6N.s/m2).
nht (16,7oC):8,34Pa*s.
Nhit ti hn: Tc = 92.30C.
Nhit nng chy: -185.2oC(88K).
Nhit si: -47.6oC (225.5K).
Nhit chy: 10.94 kcal/kg 25oC.

 im bc chy: -108oC.
Gii hn nng hn hp n vi khng kh: 2.0% 11,7%.
acid: 43 (44 in DMSO).
Hng s kh R= 198.
1.1.2. Tnh cht ha hc [4]
Lin kt ni i ca anken km bn vng nn trong phn ng d b t ra
to thnh lin kt vi cc nguyn t khc. V th lin kt i C=C l trung tm
phn ng gy ra nhng phn ng ha hc c trng cho anken nh phn ng cng,
phn ng trng hp v phn ng oxi ha.
Phn ng cng Hydro (Hydro ha).
Khi c mt ca cht xc tc Ni, Pt, Pd, cng vi nhit thch hp th Propylen
cng Hidro vo ni i to thnh Propan, phn ng ta nhit:
R1R2C=CR3R4 + H2

xt,to

CH2=CH-CH3 + H2

R1R2CH-CHR3R4
CH3-CH2-CH3

xt,tha).
Phn ng cng Halogen (Halogen
Clo v Brom d cng hp vi Propylen to thnh dn xut ihalogen khng
mu, do tnh cht lm mt mu dung dch Clo (Brom) nn ngi ta thng dng dung
dch nc Clo (brom) nhn bit anken:
CH2 = CH - CH3 + Cl2

ClCH2-CHCl-CH3. (1,2 diclopropan).

Phn ng cng Acid v cng nc.

Cng Acid.

Hydrogen halogenua, Acid sunfuric m c...c th cng vo Propylen.

CH2=CH-CH3 + Cl-H (kh)

CH3 CHCl - CH3.

Phn ng xy ra qua 2 giai on lin tip:

- Phn t H+-Cl- b phn ct, H+ tng tc vi lin kt to thnh
cacbocation, cn Cl - tch ra.
-

- Cacbocation l tiu phn trung gian khng bn, kt hp ngay vi anion Cl

to thnh sn phm.

Cng nc (Hidrat ha).

nhit thch hp v c xc tc Acid, Propylen c th cng hp nc:

CH2=CH2-CH3 +H-OH

CH3 - CH 2 - CH2 - OH (Propanol)

Quy tc cng hp tun theo quy tc Mac - cp nhi - cp, (Phn in tch
dng ca tc nhn cng vo cacbon mang nhiu H hn (tc l cacbon bc thp hn),
cn phn mang in tch m ca tc nhn s cng vo cacbon mang t H hn).
Phn ng trng hp.

Propylen c kh nng cng hp nhiu phn t li vi nhau to thnh nhng

phn t mch rt di v c khi lng rt ln trong iu kin nhit , p sut, xc tc
thch hp:
n CH2 = CH
CH

( - CH - CH - ) n
CH
PolyPropylen.

Phn ng trng hp l qu trnh cng hp lin tip nhiu phn t nh ging

nhau hoc tng t nhau to thnh nhng phn t rt ln gi l polymer.
Phn ng Oxi ha.
Propylen cng nh cc Hydrocacbon khc khi chy to thnh CO 2, H2O v ta
nhiu nhit.
2 C3H6 + 9 O2

6 CO2 + 6H2O.

Ngoi ra Propylen cng c kh nng lm mt mu qu tm nh nhng Anken

khc.
3C3H6 + 2KMnO4 + 4H2O

3CH3-CH(OH)-CH2OH + MnO2 + 2KOH

1.1.3. Qu trnh pht trin v cc ngun thu nhn chnh [5]

Nhng ngun thu nhn chnh ca propylen t qu trnh cracking (crackinh xc
tc hoc crackinh hi) cc hydrocacbon. Lc u qu trnh ny c thit k sn
xut nhng sn phm khc, propylen ch l sn ph khng mong mun. Qu trnh ny
sinh ra nhiu sn phm ph, hm lng Propylen sinh ra ty thuc ngun nguyn liu
v iu kin phn ng. Ngun nguyn liu chnh l du m v etan. Khi du m tr
thnh ngun nguyn liu chnh th hm lng Propylen sn xut c tng ln. S tiu
th tng ln dn n tng nghim ngt qu trnh cracking xc tc ca nh my lc
du, kt qu l tng lng sn phm Propylen. Propylen thu c t qu trnh crackinh
xc tc ca nh my lc du c lm sch bng qu trnh chng ct loi b Propan
v phn khng tinh khit khc. Propylen loi thng mi ha (xp x 95% propylen)
v loi trng hp (>99,5% Propylen) c tp cht ch yu l Propan. Propylen cng
c sn xut bng s chuyn v gia buten v etylen . Qu trnh ny c a vo
nh my lc du hoc phn xng crackinh hi tng sn phm propylen. Lc u
qu trnh ny c pht trin bi Phillip nhng by gi bn quyn l ca ABB
LUMMUS. Ngoi ra Propylen cn c sn xut bng cch kh hydro ca Propan
di tc dng ca xc tc, qu trnh ny c d on l qu trnh cung cp Propylen
chnh Trung ng. Hai qu trnh chnh ang p dng l qu trnh Catofin trc y
c pht trin bi Houdry v gi cp php bi ABB Lummus v qu trnh Oleflex
c cp php bi UOP. Kh thin nhin c th c dng nh nguyn liu cho qu
trnh sn xut PP bng cch thm qu trnh Lugri MTP vo mt nh my sn xut
methanol thng thng.
Nhn chung, v c bn, ton b lng Propylen s dng cho cng nghip ha
cht u c sn xut t cc NMLD (crackinh xc tc) hoc l ng sn phm ca
Etylen trong cc nh my crackinh bng hi. Ngoi ra cn mt lng Propylen tng

i nh c sn xut bng phng php khc nh: Tch Hydro khi Propan, phn
ng trao i Etylen Butene, chuyn ha t Methanol.
1.2. GII THIU V HYDROGENE:[6]
- Cng thc phn t : H2
- Cng thc cu to : H H
Hydrogen l kh nh nht trong tt c cc kh, c tm thy trong kh quyn
vi nng rt thp, phn ln thu c t cc qu trnh trong nh my lc du
(Reforming xc tc chim khong 70 90 % th tch ), kh thin nhin, than cc, in
phn dung dch

Hnh 2 : Phn xng thu hi Hydrogen trong Nh my lc du (PSA)

1.2.1. Tnh cht vt l: [7]
nhit thng, Hydrogen l cht kh khng mu, khng mi, khng v,
tan t trong nc (1,6 mg/l) v cc dung mi hu c, kh nng chy n cao, khng duy
tr s sng v d dng phn ng vi cc cht, hp cht ha hc khc.
Bng 1 :

Mt s tnh cht vt l ca Hydrogen

Khi lng phn t, (g/mol)

2,016

Khi lng ring th lng, (g/cm3)

0,06986

Khi lng ring th kh, (g/cm3)

0,001312

Nhit ngng t, (oC)

- 252,6

Nhit kt tinh, (oC)

-259

Nhit ti hn, (oC)

-230,82

p sut ti hn, (bar)

19,29

Gii hn chy n vi khng kh, (%V)

4,0 75

 nht 15 oC, (cP)

0,00866

Nng lng lin kt H-H, (kj/mol)

435
0,74

di lin kt, ( A )
1.2.2. Tnh cht ha hc [8]
Tnh bn nhit :

Phn t H2 c bn nhit ln, nn rt kh phn hy thnh nguyn t. Qu

trnh phn hy thu nhit nhiu.
H2 2H, H = 435 (KJ/mol)
Tnh oxy ha :
nhit thng, Hydrogen rt km hot ng nhng khi un nng kt hp
c vi nhiu nguyn t. Khi phn ng vi cht kh mnh nh cc kim loi kim,
kim th th Hydrogen th hin tnh oxy ha.
2Li

H2

2LiH

Tnh kh :

Phn ng vi Oxy

nhit thng H2 khng phn ng vi Oxy m bt u phn ng nhit

o

550 C.
2H 2 (K) +

O 2 (K) 2H 2O (K) , H = - 241,82(KJ/mol)

Khi chy vi Oxy nguyn cht lm nhit ngn la ln n 2500 oC, nn c

ng dng trong cng nghip hn, ct kim loi. Tuy nhin, nu t l thch hp 2:1 th
phn ng trn tr thnh phn ng n rt nguy him.

Phn ng vi kim loi km hot ng (tr cc oxyt kim loi hot

ng t u dy in ho n Al)
CuO H 2 Cu

H 2O;

Fe3O 4 4H 2 3Fe H 2O;

Phn ng cng

Tham gia cc phn ng Hydrogen ho cc hp cht khng no, tc nhn ngt

mch cc phn ng dy chuyn to chui polymer. c bit, Hydrogen c ngha rt
ln trong cc qu trnh Hydrocracking, Hydrotreatment trong Nh my lc du.
1.2.3. ng dng v sn xut[9]
Hydrogen c tinh khit thng c s dng trong cng nghip sn xut cc
hp cht do, cc polyester v nylon (si tng hp), tng hp NH 3, HCl, CH3OH v
cng nghip hn (kt hp vi oxygen).

Gn y, ngi ta to ra c trng thi mi ca Hydrogen (Hydrogen kim

loi), khi nn di p sut 3 triu atm nhit khong - 270 oC. Hydrogen kim loi
ny l mt cht rn c dn in - nhit cao v cc tnh cht khc ca kim loi c
ng dng trong cng nghip in t, cc vt liu bn dn.
L nhin liu quan trng trong cc tu v tr, tn la v tng hp ht nhn.
Hin nay trn th gii ang hng n dng lm nhin liu chy cho ng c, pin
nhit in.V nh nn dng bm vo kh cu, phao phc v cho qun s v dn s.
1.3. SN PHM POLYPROPYLEN
1.3.1.Lch s ra i[10]
Vic pht minh ra Polypropylen din ra vo u nhng nm 1950. C nhiu
nhm cng tham gia pht minh ny: Montecatini (c s gp mt ca cc gio s
Giulio Natta ng t gii nobel 1963 vi Karl Ziegler), Nhm Ziegler.
Polypropylen hnh thnh t qu trnh trng hp
(Polymer ha) phi tr vi s c mt ca xc tc Ziegler
Natta. Polypropylen c a ra th trng ln u tin vo
nm 1957 bi cng ty Montecatini, Italia. Ngay sau , n
c sn xut hng lot ti chu u, M v Nht. Theo
dng thi gian pht trin cng sut v cht lng
Polypropylene thng mi ngy cng c ci thin.
1.3.2.c tnh chung[11]
- Tnh bn c hc cao (bn x v bn ko t), kh
cng vng, khng mm do nh PE, khng b ko gin di
do c ch to thnh si. c bit kh nng b x rch d dng khi c mt vt ct
hoc mt vt thng nh.
- Trong sut, bng b mt cao cho kh nng in n cao, nt in r.
- PP khng mu khng mi, khng v, khng c. PP chy sng vi ngn la
mu xanh nht, c dng chy do, c mi chy gn ging mi cao su.
- Chu c nhit cao hn 100 oC. Tuy nhin nhit hn dn m (thn) bao
b PP (140oC) cao so vi PE nn c th gy chy h hng mng ghp cu trc bn
ngoi, nn thng t dng PP lm lp trong cng.
- C tnh cht chng thm O2, hi nc, du m v cc kh khc.
1.3.3.Cng dng[12]
Nh c mt s tnh cht u vit hn so vi cc polymer khc nn PP c s
dng ph bin nh:
- Dng lm bao b mt lp cha ng bo qun thc phm, khng yu cu
chng oxy ha mt cch nghim ngt.
- To thnh si, dt thnh bao b ng lng thc, ng cc c s lng ln.
- PP cng c sn xut dng mng ph ngoi i vi mng nhiu lp tng
tnh chng thm kh, hi nc, to kh nng in n cao, v d x rch m bao b (do

c to sn mt vt t) v to bng cao cho bao b.

1.3.4.Phn loi Polypropylen[13]
Polypropylen l mt loi nha nhit do c sn xut bi qu trnh polimer
ha propylene. C nhng tnh cht nhit, vt l, ha hc nh mong mun khi s dng
nhit phng.
Trong cng nghip ngi ta chia Polypropylen thnh cc h ln vi cc tn
gi nh sau:
- HomoPolypropylen (Polypropylen ng th), l kt qu ca qu trnh polymer
ha ch duy nht monomer l Propylen. L loi c s dng rng ri nht trong cc
loi sn phm ca PP. N c sn xut t nhng thit b phn ng khc nhau c s
dng xc tc lin kt cc monomer li vi nhau thnh dng c cu trc khng gian
c nh. HomoPolypropylen l mt h hai pha, v n cha c vng kt tinh c v
vng khng kt tinh c (v nh hnh). Vng khng c kh nng kt tinh bao gm
c isotactic PP v atactic PP. Isotactic. PP c kh nng kt tinh chm trong vng v
nh hnh. HPP c mng tinh th t dy n mng c th hin qua im chy ca
n.
- Random CoPolypropylen (Polypropylen ng trng hp) (RCP) l kt qu ca
qu trnh ng polymer ha monomer Propylen vi cc monomer khc. Thng dung
dch kt hp comonomer Ethylene vi t l thp (7 %). a s Copolymer c cu to
khng iu ha, trong mch phn t ca chng c cc mc xch c s (monomer A v
B) khc nhau sp xp mt cch hn n v khng th tch ra cc on mch lp i lp
li mt cch tun hon. ng trng hp c cc ng dng ln trong thc t v n cho
php thay i tnh cht ca cc hp cht cao phn t trong mt gii hn rng. ng
trng hp c s dng rng ri trong cng nghip cao su tng hp. Cc polymer c
cu to khng gian c sn xut trong dy chuyn cc thit b phn ng ni tip,
thit b phn ng th nht l homopolymer v thit b th hai l copolymer.
- A A A A B A B B A-
- Copolypropylen block (Polypropylen ng trng hp khi): Khc vi cc
copolymer thng thng, trong i phn t ca chng cc n v monomer ring bit
lun phin nhau v sp xp khng theo mt trt t trong mch.
- A A A A B B B B B A A-

Hnh 3 : Hnh dng ca Polypropylene trong cng nghip[14]

1.3.5. Cu trc phn t[15]
Polypropylen l mt hp cht cao phn t c cng thc ha hc chung l:

Ba loi cu trc lp th ca polypropylene l atactic polypropylene,

syndiotactic polypropylene, isotactic polypropylene.

Isotactic polypropylene:

C cc nhm - CH3 cng nm v mt pha mt phng trong cu hnh ng phn

quang hc, dng tinh th. C tnh cht l khng tan c trong heptan si v c nhit
im chy khong 165oC.

Atactic polypropylene: C cc nhm - CH3 sp xp ngu nhin khng

theo mt quy lut no, v nh hnh v kt dnh tt.

Syndiotactic Polypropylene: C cc nhm CH3 sp xp lun phin trt

t c hai na mt phng.

Ngoi ra, nu s dng xc tc metallocene ngi ta c th tng hp c

polymer khi cha ng thi isotactic v atactic trong mch nh sau:

Hnh 4 : Cu trc ca polypropylene khi[16]

1.3.6.Hnh thi hc[17]

Tinh th hc v hin tng a hnh :

Ha hc lp th ca PP ng vai tr quan trng trong vic sp xp c kht ca
cc on mch trong vng kt tinh ca PP. Hnh 5 cho thy cc dng tn x tia X gc
rng (WAXS: wide-angle X-ray scattering) ca iPP, sPP, v aPP. Cu trc phn t iu
ha ca iPP v sPP lm cho cc on mch d dng kt tinh, iu ny to ra s khc
nhau trong tnh i xng ca n v nguyn t gia sPP v iPP. aPP khng c cu trc
phn t iu ha v khng kt tinh. iu ny dn n vic to ra mt vng tn x
khuch tn rt rng. Mch iPP c cu dng xon c trong nguyn t tinh th, nh trong
hnh 6. ng xon c lp li sau 3 mt xch monomer, vi chu k ng nht 0,65nm.
S b tr 4 vng xon c thc hin bi vic quay bn phi hoc bn tri quanh
ng tm chnh gia vi vi nghing khng ph thuc vo hng quay.

Hnh 5 : Cc kiu tn x tia X c gc rng ca iPP , sPP , aPP . Min

gch minh ho s tch bit ca phn b tn x tinh th v v
nh hnh
Dng tinh th ch yu ca iPP l dng . n v nguyn t ca dng - iPP l
n t, cha c 4 on mch v 12 mt xch monomer vi s sp xp c kht c
trng ca s sp xp xon c. Khi lng ring ca tinh th thng nm trong khong
0,936-0,946 gm/cm3. Cu dng xon ca sPP khc vi iPP, v c chu k ng nht l
0,74 nm. n v nguyn t ca dng tinh th n nh nht ca sPP l h t phng,
cha 4 on mch v 16 mt xch monomer vi vi s sp xp c kht c trng ca
s sp xp xon c. Khi lng ring ca tinh th l 0,930 gm/cm3.
C iPP v sPP u biu hin hin tng a hnh, c xu hng kt tinh thnh
dng tinh th khc ph thuc vo iu kin kt tinh. Trong iPP, dng ch yu l dng
. Cc dng khc bao gm m - , -, v cc dng trung gian. Tt c cc dng tinh th
ny u cha cu dng xon vi khong lp li 0,65 nm, nhng khc nhau trong tnh
i xng ca n v nguyn t, s kt b gia cc mch, v s hn n trong cu trc.
Dng trung gian c hnh thnh trong iu kin ti cht do nhanh, v c nhng tnh
cht quan trng, c bit khi ng dng dng mng v si. Dng trung gian bin i
nhanh thnh dng khi gia nhit. To thnh dng do a vo cc tc nhn c bit
v cc ph gia, cc iu kin kt tinh c bit, kt tinh di gradient nhit c
kim sot, v trong mt vi trng hp kt tinh di ng sut trt. Dng - c t
trng nguyn t thp hn, tc kt tinh cao hn, v im nng chy biu kin thp
so vi dng , nguyn nhn mt phn l do c trng v tinh th ca n.

Hnh 6 :

Chui vng xon ca isotactic PP

Dng - him thy dng tinh khit trong polymer ng nht thng mi dng
xc tc Ziegler-Natta di iu kin gia cng thng thng. Dng - xut hin trong
phn c khi lng phn t thp, polymer ng nht c to ra t mt vi cht xc
tc ng th (metallocene). Copolymer ngu nhin v polymer ng nht metallocene
nhit kt tinh cao, cc mu c cha nhiu on iu ha khng gian, v polymer
ng nht kt tinh p sut cao.
sPP cng th hin hin tng a hnh. Vic kt tinh ti nhit thp hn c th
dn n cu trc b khuyt tt so vi dng n v nguyn t i xng ph bin.

kt tinh:

kt tinh nm gia 0 i vi cc vt liu hon ton v nh hnh (nh aPP) v

1 i vi cc vt liu kt tinh hon ton. Cng nh vi hu ht cc polymer bn kt
tinh, kt tinh c vai tr quan trng trng vic quyt nh tnh cht ca PP. Mt s
tnh cht nh mun, gii hn chy, kh nng chng oxy v m tng ln khi tng
kt tinh. Trong iPP (v sPP) tnh khng gian nh hng n kt tinh. S phn b
tnh khng gian gia cc dy nh hng khng ch n kt tinh ti nhit phng,
m cn nh hng mt phn tnh cht nng chy (v do nh hng n kt tinh)
nhit cao. Vi cht xc tc ng th, cu trc vi m ca mch PP c th bin i
lin tc theo hng gim mc cu trc iso t iPP n aPP ri n sPP tng ng
vi s thay i kt tinh ca isotactic hoc syndiotactic. Vi cc xc tc hin hnh
th kt tinh ca sPP thp hn iPP. Ngoi vic chu nh hng ca tnh khng gian,
kt tinh ni chung tng khi gim khi lng phn t ( linh ng ca mch tng),
v tc lm lnh chm t trng thi nng chy. ng trng hp cng c s dng
iu chnh kt tinh ca polymer. Trong trng hp ny, comonomer l ngun
to ra tnh khng iu ha trong mch PP. Vic a comonomer vo lm gim kt
tinh, gim cng bn trong v nhit nng chy, v tng bn va p.

Hnh thi ht polymer:

Hnh thi ngoi quan ca cc ht bao gm: Hnh dng, kch thc, phn b
kch thc v xp. Kim sot hnh thi ht cng c lin quan n cc cng ngh c
s dng cc ht polymer c trng hp bt i xng trong qu trnh trng hp tip
theo. Cc c trng hnh thi ph thuc mnh vo cht xc tc. Cht xc tc ti to
hnh dng ca n trong polymer nhng c kch thc ln hn v kch thc ny ph
thuc vo hot ng ca n. hot ng ca xc tc c nh gi thng qua
lng polymer to ra trn 1 n v cht xc tc.

Ht polymer c cng hnh dng vi ht xc tc, mc d ng knh ca n ln

hn xp x 20-100 ln. S ln ln ca ht polymer trong sut qu trnh trng hp
c m hnh ha bi nhiu tc gi v trong nhiu ti liu. Trong m hnh nhiu ht
(multigrain), cht xc tc b phn mnh thnh cc vi ht v cc vi ht ny c phn
b bn trong cc ht polymer di tc dng ca cc lc to ra do s ln ln ca cc
lp polymer. Trong cc cht xc tc Ziegler-Natta, s phn mnh xy ra lc lng
polymer to ra rt thp, to ra b mt hot ng ln t lc bt u qu trnh trng hp.
S ln ln ca cc ht polymer l kt qu t s tch lu cc lp ca ht polymer.
1.3.7. Tnh cht nhit ng hc[18]
S nng chy.
im nng chy ca dng iPP b nh hng mnh bi tnh iu ha khng
gian. im nng chy gia tng khi tnh iu ha tng. Tom l im chy cn bng ca
tinh th han ho. Gi tr ca Tom rt nhy vi tnh iu ha khng gian. Tuy nhin, gi
tr ny ca PP 100% isotactic c th khng khc nhiu so vi T om ca iPP thng mi
c tnh iu ho cao. Mt s ti liu cho rng T om ca PP c tnh iu ha cao khong
185 188oC. Trong iu kin phn tch bnh thng, im nng chy ca cc PP
thng mi khong 160-168oC. Vic a vo cc comonomer (ethylene, butene v cc
-olefin cao hn) lm gim im nng chy, v c th lm bin mt im nng chy
khi vt liu tr thnh cao su v nh hnh. Nhit nng chy, H o, ca PP 100% tinh th
thng nm trong phm vi 148-209 J/g.
Cng nh vi iP, im nng chy ca sPP c nhy cao vi tnh iu ha
khng gian. Vi cc sPP thng mi vi cc xc tc khc nhau th s khc nhau v T om
ca cc sPP khng r rng. Tuy nhin, im nng chy quan st c ca sPP nhn
chung thp hn im nng chy ca iPP vi xc tc Ziegler-Natta di iu kin kt
tinh thc t khi c mc iu ha khng gian tng ng. S khc nhau ny
thng l 10-15oC. Vic a vo cc comonomer cng gim im nng chy ca sPP.
Nhit ho thu tinh:
Gi tr nhit ho thu tinh Tg ph thuc vo kt tinh ca polymer, KLPT
v cch thc o c s dng. Nhit ho thu tinh thng trong phm vi -13 0oC.
Cc phng php k thut khc nh phn tch c ng hc thng nhy hn vi Tg
ca iPP. Qu trnh ng trng hp vi ethylene lm gim Tg. ng trng hp vi
butene lm gim Tg t hn.
1.3.9 Tnh cht ho hc [19]
iPP tan c trong cc hydrocacbon bo v thm c im si cao nhit
cao. sPP tan c trong cc hydrocacbon bo v thm c im si thp hn v nhit
thp hn. aPP th hin tan cao nht trong 3 dng trn. bn ho hc cao ca
iPP lm cho n kh b bin mu v c s dng trong acquy xe t. iPP cn c kh
nng khng nc, bn vi nhiu axit v baz v c mnh. Ging nh cc polyolefin
khc l n b tn cng bi cc tc nhn OXH nh axit sunfuric 98% v axit clohidric
30% nhit cao ( 100oC) v axit nitric bc khi (nhit thng).

PP phn ng vi O2 bng nhiu cch khc nhau, gy ra s t mch v dn,

ng thi gim khi lng phn t. Phn ng ny cng xy ra mnh nhit cao,
nh sng. Mt lng ln cc loi cht n nh c thm vo bo v, ph thuc vo
tng ng dng.
Kh nng phn ng ca PP cng c s dng 1 cch hiu qu. V d nh x l
bng cc peoxit to nha c tnh lu bin cn thit. S hnh thnh ca cc gc t do
dc theo mch polymer, hu ht thng qua cht khi mo peoxit. Mc ch l a cc
nhm chc c cc vo mch polymer. Vic a cc nhm chc c cc vo c th
in, sn hoc dng lm tc nhn lin kt (coupling agent) trong composite nh iPP c
gia c thu tinh, hoc ci thin kh nng chng oxy ha, hoc dng lm cht n
nh trong hp kim polymer. Bc pht trin gn y trong xc tc c kim ng th
v cc xc tc c s dng kim loi chuyn tip a ra trin vng cho qu trnh trng
hp trc tip cc monomer phn cc vi ethylene v propylene.
1.3.10 Tnh cht vt l [20]
Khi lng phn t v a phn tn ca polymer c thit k to ra
nhng c tnh tt nht i vi mi qu trnh gia cng. Cc loi nha c a phn
tn hp cng c sn xut bng nhng xc tc c kim ng th. Nhng xc tc ny
cng c th sn xut iPP vi phn b iu ha khng gian gia cc mch hp v phn
c th chit ra thp. Nhng copolymer ngu nhin dng ethylene v butene nh l cc
comonomer. cng bn trong ca nhng polymer ny thp hn so vi nhng
polymer ng nht.
1.4. CHT XC TC[21]
1.4.1. Lch s ra i v pht trin
Xc tc s dng cho qu trnh ny l mt hp cht rn c cu thnh t mt
mui clorua kim loi nhm IV-VII c ho tr chuyn tip (thng l Ti) v cc hp
cht c kim ca nhm I III (thng l alkylaluminium), c pht minh vo u
nhng nm 1950 bi hai gio s Karl Ziegler (c), Giulio Natta (Italya) v ly tn l
xc tc Ziegler-Natta.
Thc ra ch duy nht xc tc Ziegler-Natta c s dng trong cng nghip.
Tuy nhin, cc nghin cu gn y (u nhng nhm 1990) lin quan n xc tc
metallocenes (cation kim loi nm gia hai anion Cyclopentadienyl) ang c y
nhanh tin b. Sn phm Polypropylene ch yu l di dng Polypropylene isotactic.
Trong lch s pht trin, cng vi qu trnh ci tin cng ngh polymer ha,
hiu nng ca cc cht xc tc v h thng xc tc cng tin trin mnh m k t khi
pht minh ra chng. By gi khng cn dng xc tc th h th nht na. V th cc
qu trnh cng ngh sn xut ngy cng n gin v sn phm polymer tt hn.
- Th h th 1, khong gia nhng nm 1960: Hiu sut xc tc cn thp, cn
phi c mt giai on ra polymer trch ly cn xc tc v Polypropylene atactic.
- Th h th 2, t nm 1965 1982, hiu sut tng gp 4 ln v tnh lp th
chn lc ca xc tc c ci thin, loi b c giai on trch ly Polypropylene
atactic nhng vn gi giai on trch ly xc tc. Thnh phn gm TiCl 3 kt hp vi

clorua Diethylaluminium (Al(C2H5)2Cl). Chiu hng cho ra sn phm Polypropylene

cao (95 98)% nhng hiu sut ca xc tc vn cn thp (4.000 10.000)g
Polypropylene/g xc tc.
- Th h th 3, a ra nm 1975 bi cng ty Mitsui Montedison: hiu sut
c ci thin hn, cho php loi b trch ly cn xc tc, nhng tnh lp th chn lc
hi thp nn c th cn n giai on trch ly Polypropylene atactic. Thnh phn gm
TiCl4 trn cht mang MgCl2 c b sung thm mt ester thm. Chng c s dng
vi Triethylaluminium (Al(C2H5)3) nh l mt xc tc kt hp v mt silane c
ci thin dng th c trng. Hiu sut xc tc (5.000 15.000)g Polypropylene /g xc
tc v khong 92% Polypropylene isotactic th c trng. Hnh dng ca polymer
khng u v s phn loi theo thnh phn (php o ht) cn rt ln xn (tn ti ng
thi cc ht mnh, mn v to ln).
- Th h th 4, a ra nhng nm 1980 bi Mitsui - Montedison v Shell
(nhng cng ty k tip khc, nh Mitsubishi Petrochemical v Sumitomo): khng cn
giai on trch ly Polypropylene atactic na. Thnh phn bao gm cc cu t nh th
h 3, nhng hnh dng (ch yu dng hnh cu) v kch thc ht c iu chnh
to iu kin d dng cho s di chuyn ca n trong thit b phn ng tng si. Hiu
sut xc tc rt cao (20.000 50.000)g Polypropylene/g xc tc, lng Polypropylene
isotactic t n (97 98)%. Cc xc tc ny vn hnh tng ng vi Al(C 2H5)3 v
cht bin hnh silane.
Bng 2 : Cc th h xc tc Ziegler Natta, thnh phn, tnh nng, hnh
thi,v yu cu ca qu trnh
Th
h

Thnh phn

Hiu sut, kg Ch s
PP/g xc tc* isotactic

Kim
sot
hnh
thi

Yu cu
qu trnh

1 -TiCl3.0.33AlCl3+AlEt2Cl

0.8-1.2

90-94

Khng
th

Kh tro v
loi b
phn
atactic

1 -TiCl3+AlEt2Cl

3-5 (10-15)

94-97

C th

Kh tro

90-95

C th

1 TiCl4/ester/MgCl2+AlR3/est 5-10(15-30)
er

Loi b
phn
atactic

1 TiCl4/diester/MgCl2+AlEt3/
silane

95-99

C th

Khng cn

95-99

C th

Khng cn

1 TiCl4/diether/MgCl2 +AlEt3 25-35(70120 )

10-25(30-60)

1.4.2. Cu to, thnh phn ca cht xc tc

Trong cng nghip, xc tc Ziegler-Natta thng c s dng di dng cc
ht nh hnh cu (xem hnh 8).
H xc tc ph bin dng trong cng nghip ch bin polymer l xc tc
Ziegler-Natta gm 2 hp phn chnh:
- Cht xc tc: Halogen ca cc kim loi chuyn tip nhm IV v nhm VIII
nh: TiCl3, TiCl4, TiCl2,Ti(OR)4, TiI4, VCl4, VOCl3, VCl3, ZrCl4
- Cht tr xc tc: Hydrid, ankyl, aryl ca cc nguyn t nhm I, IV nh:
Al(C2H5)3, Al(i-C4H9)3, Al(n-C6H13)3, C4H9Li, (C2H5)2Zn
Hin nay th h th 4 ca xc tc Ziegler-Natta c thnh phn chnh l TiCl 4
dng vai tr xc tc trn cht mang MgCl 2, Al(C2H5)3 (TEAL) l cht tr xc tc,
chng c phn tn trong du khong v m nhn. Xc tc ny cho hiu sut v
chn lc cao. Bng vic thay i t l cc hp phn xc tc, la chn ch cng ngh
m ngi ta c th sn xut cc polymer c cu trc khng gian khc nhau.
Ngi ta s dng Hydrogen tt mch phn ng to ra sn phm c phn
b hp.Trong phn ng polymer to Polypropylene. Ph thuc kh nng nh hng
ca nhm metyl, c 3 dng mch PP khc nhau. Bng vic thay i t l cc hp phn
xc tc, la chn ch cng ngh m ngi ta c th sn xut cc polymer c cu
trc khng gian isotactic c gi tr kinh t cao.

Hnh 7 : Ht xc tc ZieglerNatta (a) v ht polymer tng

ng (b)
Bng 3 :

Thnh phn chnh ca cc loi xc tc Ziegler-Natta

Kim loi nhm I III

Al(C2H5)3

Kim loi chuyn tip

TiCl4

Cht thm vo
H2

Al(C2H5)2Cl

,, TiCl3/cht mang

Al(C2H5)Cl2

MgCl2

(i-C4H9)3Al

VCl3, VoCl3, V(AcAc)3

R-OH (Phenol)

(C2H5)2Mg

Titanocene dichloride
Ti(OiBu)4

R3N, R2O, R3P

(C2H5)2Zn
(C2H5)4Pb

(Mo, Cr, Zr, W, Mn, Ni)

O2, H2O

Aryl esters
HMPA, DMF

Cng thc cu to ca Xc tc Ziegler-Natta th h 2, 3 v 4 nh sau :

Hnh 8 : Cng thc cu to ca Xc tc Ziegler-Natta th h 2, 3

v 4

Hnh 9 : Cu trc khng gian -TiCl4

1.5. L THUYT TRNG HP PROPYLENE [22]
Trng hp l phn ng kt hp mt s ln phn t (monomer) m khng tch ra
cc sn phm ph. Nh vy phn ng xy ra khng c s bin i no v thnh phn
nguyn t ca cht tham gia phn ng.
Trong nhng nm gn y, mt phng php rt ph bin l phng php trng
hp anion phi tr c mt xc tc Ziegler Natta (phng php ny c s dng
trong tng hp cng nghip cc polymer iu ho lp th). in hnh nht l hp cht
gm TiCl4 v Al(C2H5)3 (th h 4). V cc dn xut nhm alkyl c tnh cht nhn in
t, Ti l kim loi chuyn tip c tnh cht cho in t nn chng d dng to lin kt
phi tr. Cc xc tc phc ny khng tan v cu to ca chng cho n nay vn cha
c xc nh c th.
Nhng trn c s nghin cu cu to xc tc phc tan, ngi ta cho rng n l
mt phc lng kim loi, trong nhm alkyl phi tham gia lin kt phi tr (a).
Phn ng theo c ch polymer ha phi tr di xc tc dng bimetallic.
1.5.1.C ch trng hp Propylene

Tc Rp ca bc ln mch u tin monomer thnh polymer vi xc tc

Ziegler-Natta c biu din bi cng thc:
RP = kP[C*][M]
Trong kp l hng s ln mch; [C *] l nng ca trung tm hot ng;
[ M] l nng ca monomer.
Tc trng hp tng cng thay i theo thi gian. Sau giai on tng tc
thng l s suy gim tc v cui cng l trng thi dng. S gim dn tc
thng l do s thay i nng ca cc v tr hot ng. Tc lc u tng c th
l do qu trnh hot ha lm xut hin cc hot ng trung tm mi. S gim hot tnh,
th hin r rng nht trong xc tc c cht mang, l do s thay i c v s lng v
bn cht ha hc ca cc trung tm.
Tc trng hp chung ca giai on ln mch u tin chu nh hng ca
xc tc v cc iu kin trng hp. Nhng nh hng l do cu trc ho hc v vt
l ca cht xc tc cng nh bn cht ca cht hot ho. Cc tham s quan trng bao
gm t l gia cht xc tc v cht hot ho, v nng ca chng, nng H 2, nhit

, tc khuy trn. Nhng nh hng ny thay i theo mi trng trng hp; tc

l, cht pha long hoc monomer trong pha lng hay pha kh.
Vic xc nh nng lng hot ho ca phn ng pht trin mch v thi gian
sng trung bnh ca mch polymer khng chc chn. Nng lng hot ho ca phn
ng pht trin mch ca cc xc tc trn c s TiCl 3 l 23 kJ/mol (5.5 kcal /mol). Thi
gian sng trung bnh ca mch polymer vi cc xc tc trn c s TiCl 3 c cc gi tr
ca 360 - 600 s v 160s ti 70OC vi 2 ti liu khc nhau v 5s i vi cc cht xc tc
s dng cht mang MgCl2 ti 45OC.
Mt thi gian ngn sau khi khm ph cht xc tc Ziegler Natta, ngi ta cho
rng s ln mch c thc hin bi s chn monomer vo trong lin kt Ti - C ca
cht xc tc. Lin kt ny c coi l b phn cc, vi phn in tch m thuc v
nguyn t C.
Vi n lc a ra m hnh nhm gii thch hp l s ln mch ca polymer,
nhiu gi thuyt c a ra. Trong cun sch ca Boor ni v xc tc Ziegler
Natta, ng xem xt k lng cc ti liu v ch ra 4 c ch chnh cho pht trin
mch. 4 c ch ny da trn vic m t trung tm ni m s ln mch xy ra:
(1) lin kt kim loi chuyn tip carbon.
(2) lin kt kim loi ca cht hot ho carbon.
(3) trung tm gc.
(4) trung tm anion.
Trong s 4 c ch ny, phn ln cc nghin cu c khuynh hng ng h m
hnh trung tm kim loi chuyn tip - C. S dng xc tc ng th (Cp 2TiEt2) lm
m hnh, Breslow v Newburg cho rng s pht trin mch xy ra ti trung tm lin
kt Ti C. Khng lu sau , Cossee m rng khi nim ny thnh mt c ch phc
tp hn cho cc xc tc c cht mang, trong ng chng minh bng cc tnh ton
orbital phn t.
S chn momomer xy ra thng qua bc u tin l s phi tr monomer vi
kim loi chuyn tip to phc . Vic to phc ny lm lin kt Ti-C yu i, v cui
cng l s chn monomer vo gia cc kim loi chuyn tip v nguyn t C. Bi v 2
v tr ny khng tng ng trong mng li tinh th ca xc tc nn v tr trng v
dy polymer s trao i v tr. Qa trnh lp i lp li nh vy. Trn c s l thuyt v
orbital phn t, mt s gii thch bn nh lng v c ch ny c a ra trn c
s gi thuyt lin kt kim loi C b yu trong qu trnh hnh thnh phc olefin trong
trng hp cc ion kim loi c t 0-3 electron d (nh trong Ti,V, Cr). C ch ny c
gi l c ch n kim loi; n ch cn s tham gia ca kim loi chuyn tip, vai tr ca
hp cht nhm l to ra trung tm hot ng bng cch ankyl ho nguyn t titan. Tuy
nhin hp cht nhm nhm cng c vai tr trong qu trnh ln mch do thc th
chng minh vi cc alkyl nhm khc nhau s nh hng n tnh nng ca xc tc.

Hnh 10 : Propylene phi tr vi titan v sau chn vo mch Ti-polymer

Mt s nh nghin cu tin rng kim loi hot ng (Al) tham gia trc tip
trong vic nh hng cho monomer n, trong trng hp h thng ny c coi
l 1 v tr lng kim loi. Tuy nhin, Boor lp lun thuyt phc rng do kch thc
ca Polypropylene xon nn khng c khng gian ti v tr hot ng cho Al tham
gia. V tr ca Titannium chim gn 0.16 nm2 (ng knh gn bng 0.45nm) v din
tch tit din ngang ca polypropylene xon khong 0.35 nm 2 (ng knh 0,7nm). V
vy Ti v Al lin kt vi nhau bng cu ni Clo l khng th v do nhm khng
tham gia trc tip vo vic nh hng cho monomer n. Ngi ta ngh rng
nh hng khc nhau ca cc ankyl nhm n vi cu trc ca polymer v trng lng
phn t l do cch m cc ankyl nhm to ra b mt titan chloride. Nhng khc bit
trong vi lp th ca polymer v khi lng phn t c th l do cht hot ho c th
to ra cc v tr isotactic khc nhau.
1.5.2. Vn iu ha lp th v iu ha vng trong s chn monomer
i vi cc -olefin, 1 s vn lin quan n s phi tr v s chn monomer
cn phi c xem xt. Cch m monomer chn vo mch polymer quyt nh vi cu
to ca polymer v v vy quyt nh cc tnh cht ca polymer. C phi nhm methyl
trong propylene nm cui mch hay mt i? Khi kim loi phi tr vi mch polymer
th v tr ca nhm methyl trong phn t propylene so vi v tr phi tr l nh th no,
cis hay trans?
C 2 c ch v vng i vi s chn ca cc - olefin c 2 nguyn t carbon
lin kt i l bc 1 v bc 2. Trong s chn bc 1 th u khng c nhm th (CH 2)
ca monomer gn vi trung tm titan. Kiu ny cn c gi l chn - 1,2. Trong s
chn bc 2 th u c nhm th ca monomer gn vi titanium. Trng hp ny cn
c gi l chn - 2,1.

Cc d liu th nghim cho thy rng khi sn xut polypropylene isotactic th

kiu chn bc 1 chim u th. iu ny c chng minh thng qua vic phn tch
nhm cui v pht hin cc nhm isopropyl nm cui mch sau khi chuyn mch
bng H2. Tnh chn lc vng (the regioselectivity) ca cc xc tc Ziegler- Natta rt
cao. Polypropylene syndiotactic c th c iu ch bng trng hp propylene
nhit thp v s dng cht xc tc vanai. Trong trng hp ny c ch chn bc 2
xy ra.

i vi s chn iu ha khng gian (Stereoregular insertion) c 2 kiu cn

xem xt l s chn kiu cis v kiu trans. Trong trng hp iosotactic v c syndiotactic
th xy ra c ch cis. Cc cu trc ha hc lp th c to ra t phn ng cng cis v
trans vo lin kt i ca ca cis (1-d1) v trans -(1-d1) propylene to ra
polypropylene isotactic nh sau:

Hnh 11 :

Qu trnh hnh thnh Polypropylene isotactic

Hai c ch chnh c cho l quyt nh n tnh ho hc lp th ca s chn

monomer vo theo kiu isotactic l cu trc bt i xng ca cc v tr hot ng v
nguyn t cacbon bt i xng ca monomer c chn vo sau cng. Ngi ta

chng minh bng thc nghim rng yu t iu chnh l trung tm hot ng vi cu

trc bt i xng. C ch ny thch hp vi cc xc tc Ziegler-Natta. Trong TiCl 3
mi nguyn t Ti c 6 nguyn t Clo ti cc nh ca mt bt din quanh. 6 nguyn t
Cl ny sau to phc vng cng, bng cc cp, vi 3 nguyn t Ti khc. iu ny
to nn hai cu trc i hnh nh sau:

Hnh 12 :

Cu trc i hnh ca xc tc

CHNG 2

[23]

TNG QUAN V NH MY SN XUT

POLYPROPYLEN
D n Nh my sn xut Polypropylen c xy dng trn din tch 15 ha
thuc pha ty nam KCN Dung Qut, gn khu vc b cha trung gian ca Nh my lc
du. Mc du chiu di cc ng ng cng ngh v cc tuyn ng k thut khc tng
khong 20%, a im ny vn c xem nh l phng n ti u xt v tin gii
phng mt bng v vn u t cho D n T hp nh thu thc hin d n do Huyndai
Engineering ng u, khi lng cng vic do PV Engineering thc hin c tnh ln
ti 12 triu USD.
Nh my d kin s i vo hot ng vo nm 2010 vi cng sut ch bin c
t 150.000 tn sn phm/nm. Nguyn liu ca nh my Polypropylen ch yu ly t
ngun Propylen t phn xng thu hi Propylen ca nh my lc du Dung Qut,
ch bin thnh ht nha PP t tiu chun khu vc v quc t, s dng rng ri trong
cc cng nghip v phc v i sng con ngi, phc v sn xut cc mt hng nha
dn dng, cng nghip t..
Cng ngh Hypol II c ng dng cho nh my l mt trong nhng cng ngh
tin tin nht hin nay trn th gii, m bo sn xut ra cc sn phm cht lng cao
cng nh p ng yu cu ca th trng trong v ngoi nc. c bit, trn th gii
hin c khong 21 nh my sn xut Polypropylen s dng cng ngh Hypol II, trong
khu vc ng Nam c 5 nh my.
Cng sut c s: 150 ngn tn nguyn liu propylen/nm.
Di cng sut hot ng ca Phn xng: 50%-100% cng sut thit k.
Phn xng s hot ng 8000 gi/nm.
Phn polymer ho bao gm: mt l phn ng sn xut polymer ng th
(homopolymers) v polymer ngu nhin (random copolymers) trong tng lai. Mt
bng Phn xng c dnh sn ch lp t thit b phn ng copolymer trong tng
lai.
100% sn phm u ra c n p qua mt dy chuyn n.
Sn phm: di dng vin PP (homopolymer) sng mu v bn nhit.
Xc tc hiu sut cao, tiu th ti a c bit t 0,033 n 0,05 kg trn 01 tn
sn phm.
Cc hng mc ca Phn xng:

Khu vc cha v chun b xc tc.

Khu vc polymer ho v sn xut bt polymer ng th (homopolymer).

(tnh n vic sn xut copolymer trong tng lai).

Khu vc gia cng sn phm PP (to vin).

Khu vc ng sn phm vo cc ti 25 kg v bc ln gi vn chuyn.

Khu vc t ng ng hng.

Sil v kho cha ng u ho v cha sn phm PP.

Khu cha sn phm, bao gm c h thng x l v bo qun t ng.

Thit b sn xut mng PE sn xut ti, bao gm c vic in ni nhn

Thit b sn xut mng PE co gin ng gi sn phm.

H thng x thot khn cp.

hiu.

H thng x l nc thi cc b (cht lng nc thi c x l cho

php thi trc tip vo giai on x l sinh hc ca phn x xng x l nc thi ca
Nh my lc du x l tip).

H thng bo chy v cu ho t ng.

Khu vc x l nhit cht thi lng.

Phng iu khin vi h thng DCS v ESD.

CC CNG TRNH PH TR:

Bo co u t d n PP ny c pht trin vi s tch hp ti a Phn xng
PP vi Nh my lc du v s dng cc cng trnh ph tr ngoi hng ro Nh my
lc du cho cc nhu cu ca Phn xng PP.
Phn xng PP c cung cp in, hi nc, nc lm mt, nc kh khong,
kh nh my, kh iu khin, kh nhin liu v cc tin ch khc t cc h thng ph tr
ca Nh my lc du. Nu cn thit h thng ny s c m rng trong tng lai theo
tnh ton v nhu cu ca Phn xng PP.
Ngoi ra h thng uc ca Nh my lc du cng s c s dng cho Phn
xng PP.
Da trn cc yu t trn, Phn xng PP s bao gm cc cng trnh ph tr sau:

Trm tch kh Nit v Oxy, h thng ng chai Oxy.

Thit b tip nhn Nit cao p.

Kho cha propylen trung gian v cc bm.

Propylen t phn xng thu hi propylen ca Nh my lc du s c s dng

lm nguyn liu cho Phn xng PP. Ngoi ra, propylen dng tng hp polymer cng
s c nhp t bn ngoi.
Propylen c nhp t cng ca Nh my Lc du s c dn ti kho cha
trung gian hnh cu qua ng ng xut v h thng bnh xut/ nhp theo chiu ngc
li.

Propylen c cung cp t cng ti cc b cha hnh cu qua cc ng ng

xut bng cc bm t trn tu.
Da trn kch thc ng v tc vn chuyn c chp nhn, lu lng
propylen qua ng ng s bng 10% cng sut cc bm ti khu b cha sn phm.
V th trong trng hp propylen c nhp lin tc th cc bm c bit s
c b tr ti khu vc b cha sn phm.
Trng hp propylen c nhp khng lin tc th cc bm t ti khu vc b
cha sn phm c th c s dng. Trong trng hp ny cc bm s hot ng
khng ti 90% cng sut v s khng thit thc xt theo quan im kinh t.

CHNG 3
LA CHN CNG NGH SN XUT
POLYPROPYLENE
3.1. NHNG QU TRNH POLIMER HA PROPYLEN THNG DNG [24]
- Qu trnh polymer ha trong dung dch Hydrocacbon (hexan, heptan..)
nhng iu kin nhit , p sut, nhit polimer lu gi trong dung dch, qu
trnh ny ban u c s dng nhng thc t hin nay khng cn v rt tn km.
- Qu trnh polymer ha th huyn ph trong dung mi ging nh phng
php trn, nhng p sut v nhit thp hn. Polymer khng lu gi c trong
dung dch. Qu trnh ny hin nay vn cn ph bin.
- Qu trnh polymer ha th huyn ph, trong propylen lng c s dng
nh l dung mi. Qu trnh ny hin nay s dng ph bin trong cng nghip tng hp
polypropylen.
- Qu trnh polymer ha trong pha kh trong cc thit b c cnh khuy, hoc
gi lng. Qu trnh ny t c s dng v thit b cng knh phc tp.
- Polymer lai ha gi polymer ha trong pha lng (Propylen lng) v trong pha
hi: Qu trnh x ra trong mt hay nhiu thit b phn ng, qu trnh ny hin nay
c s dng rt ph bin, chng cho php sn xut c tt c cc loi Polypropylen
(co-homopolymer), polymer chui hay khi.
3.2. QUY TRNH SN XUT CHUNG[25]
Nhn chung sn xut Polypropylene c th tm tt theo s sau:

Hnh 13 :

Qui trnh sn xut chung

3.2.1.Khu vc x l nguyn vt liu ban u:

Phi qua giai on loi b cc tp cht, cht gy ng c i vi xc tc.

Qu trnh lm sch bao gm qu trnh hp th trn ry phn t (H2O, Ru,

CO2) v trn AL2O3 hot tnh x l, vi cc oxyt kim loi (nh PbO) by cc
cht c cha lu hunh.
3.2.2. Khu vc polimer ha
Cc mono comonomer, Hydrogen v cc cu t trong h thng xc tc c
np liu lin tc vo thit b phn ng. Phn ng trong qu trnh polymer ha l phn
ng ta nhit.
- Cc qu trnh trng hp ng th ( to ra cc homopolymer ) din ra trong mt
hay hai thit b phn ng cng loi.
- Cc qu trnh ng trng hp (to ra cc copolymer) gm mt giai on
polymer ha ng th tip tc cho phn to chui trong thit b phn ng pha kh.
3.2.3. Khu vc tch v thu hi kh
Sn phm polymer ra khi thit b phn ng vn cn ln hydrocacbon khng
phn ng. Do vy cn phi loi b nhng hydrocacbon ny ra khi dng sn phm v
thu hi monomer cha phn ng li qu trnh.
3.2.4. Khu vc x l cn v kh mi:
Polymer t khu vc tch c a n khu vc x ly cn v kh mi. Cc
qui trnh x l ny ng thi loi b cc monomer cn, ph v cu trc h xc tc
( mt hot tnh) v gii hn hm lng cc thnh phn to mi (oligomer, alcol) n t
qu trnh thy phn mt s cc cu t ca h xc tc
Chng thng bao gm mt thit b trao i nhit lm nng li bt polymer
v vic ny c thc hin nh tng tc vi dng N2 nng hay hi nc.
3.2.5. Khu vc p tao ht v qui trnh x l cc ht nh
Bt polymer v ph gia (cht chng oxy ho, tc nhn chng lng) chun
b c np vo thng nguyn liu my p. Trong my p hn hp ny s tri qua cc
qu trnh tan chy, ng nht keo ha, lc v to thnh ht. Qu trnh to ht c thc
hin trong mi trng nc.
S to ht l cn thit, bi v mt phn nh ca sn phm thu c di dng
ht bi. Cc ht nh c to nn bi nhng con dao gt xp ngang khun ko c
nhng chm vo trong dng nc chy vi lu lng v nhit c iu chnh.
Nc m bo lm mt nhanh cc ht nh v trnh c s bm dnh ca chng. Vic
tch nc c thc hin nh qu trnh ly tm ri sau l i sy kh. Cc ht nh
sau c lu gi trong cc sil trc khi ng gi kt thc.
3.2.6. Khu vc ng bao v ng thng:
Sn phm polypropylen c ng gi v nh lng vo cc bao b lp mng
co - polypropylen, sau c a kho cha bng xe nng.

3.3. M T V CC CNG NGH C S DNG HIN NAY[26]

3.3.1. Cng ngh pha lng
3.3.1.1. M t qui trnh cng ngh SPHERIPOL
Cng ngh Spheripol c h tr bi mt t chc R&D mnh nht trong cng
nghip v trn th gii. Basell sng ch loi xc tc tuyt ho v vn tip tc ci
hon v pht trin trong qu trnh vn hnh. Khng nh cc nh sn xut PP khc
chuyn s dng loi xc tc Metallocen, Basell chim v th mnh vi h xc tc
Ziegler-Natta. Vi s lin kt gia Tagor v Montell thnh lp Basell, loi xc tc
Metallocen cng c tng cng mnh bi Tagor. Cng ngh Spheripol c th sn
xut rt nhiu chng loi sn phm nh l phn ng a nng ca Nh bn quyn. L
Cng ty dn u th gii v tng cng sut, Basell chim u th trong vic gieo mm
cho ngnh cng nghip sn xut nha cho th trng v s dng mt s nguyn liu
np mi cho nh my.

Hnh 14 :

S sn xut PP theo cng ngh Spheripol

Trong chu trnh cng ngh ca Basell, hn hp ng nht ca cc ht PP c

lun chuyn bn trong l phn ng dng vng. Khi sn xut copolymer ngu nhin
(random copolymer) hoc terpolymer, Etylen hoc Buten-1 c a vo l phn ng
vi mt lng nh. Chu trnh ny to ra hm lng cht rn rt cao (> 50% khi
lng), gii phng nhit rt tt (do tun hon nc trong v bc ca l phn ng) v
khng ch nhit rt tt (khng c im nng). Polymer to thnh chy lin tc ra
khi l phn ng, qua mt thit b gia nhit v c dn ti thp kh kh cp 1.

Propylen khng tham gia phn ng c thu hi t thp kh kh, ngng t v bm tr

li l phn ng.
sn xut copolymer nn (impact copolymer) loi thng v loi c bit,
polymer t l phn ng u tin c np vo l phn ng pha kh tng si lp t
ngay sau (hn hp phn ng s khng c dn vo l phn ng ny nu ch sn
xut homopolymer v random copolymer). Trong l phn ng pha kh khi cho Etylen
tip tc c polymer ho vi homopolymer sinh ra t l phn ng u tin s to ra
cht nha n hi (cao su Etylen/Propylen). S m rng cc l rng bn trong cc ht
polymer mt cch k lng s to nn cc pha cao su khng b kt dnh v khng ng
ng, lm hng qui trnh vn hnh.
Trng thi lng c duy tr bi s hi lu thch hp ca kh phn ng: nhit
phn ng ca kh hi lu c gii phng bi thit b lm lnh, trc khi kh lnh
c dn tr li vo y ca l phn ng th cp. Loi l phn ng pha kh ny c
hiu sut cao do duy tr c s chuyn ng hn lon lm tng khuych tn v
phn ng ca monomer cng nh c kh nng gii phng nhit mt cch hiu qu.
Mun sn xut mt s copolymer c bit, to thnh bi 2 hm lng etylen khc
nhau cn phi s dng l phn ng pha kh th 2.
u im ca cng ngh ca Basell:
Basell mang nhn hiu ln v l Nh bn quyn PP tiu im trong s cc Nh
bn quyn tim nng.
C nhiu kinh nghim nht
Basell l ngi dn dt cho s tng trng PP trong qu kh v trong tng
lai.
Basell rt thnh cng trong pht trin xc tc cng nh cc loi sn phm PP.
Phn xng xy dng theo cng ngh Spheripol bao gm nhng b phn sau:
Khu vc o lng, chun b xc tc rn v ng xc tc
ng xc tc 1, l cht cho in t (electron Donor) di dng lng ng
trong cc bnh cha c chuyn ti b. y c pha vi du Hydrocarbon cn
ong c chnh xc. Dung dch Donor c bm nh lng bm vo xc tc to
tin tip xc.
ng xc tc 2 (TEAL) m c 100%, cha trong cc cylinder c
vo b. T y, TEAL c np vo thit b hot ho xc tc (tin tip xc) bng bm
nh lng.
Du Hydrocarbon v m c x vo b c hm nng, pha trn v sau
c chuyn n thit b to bn xc tc m y thnh phn xc tc rn c np
vo bnh bi ti nng. Xc tc rn phn tn trong du Hydrocarbon, b sung thm m
nhit nh sn, khuy lin tc, ngui n nh bn. Duy tr nhit thp
trong khi cn ong bn chuyn sang thit b hot ho xc tc.
Khu vc hot ho xc tc

Qu trnh hot ho xc tc ca thit b bao gm 2 giai on. Trc tin, bn xc

tc c trn vi ng xc tc trong thng tin tip xc. Sau , hn hp xc tc hot
ho s c trn ln vi nguyn liu propylen lnh v c lu gi trong mt thi
gian ngn trong l phn ng m Propylen s c np thm tin hnh phn
ng tin trng hp (prepolymerization) trong mi trng nhit thp. Tin trng hp
c tc dng kim sot hnh thi cu trc ca polymer bi cc iu kin phn ng n
ho ca giai on trng hp u tin.
Khu vc polymer ho
Qu trnh polymer ho c thc hin trong pha lng v trong l phn ng
dng vng. Bn xc tc c dn ti l phn ng vi s b sung thm Propylen v H 2
( khng ch cn bng phn t lng). iu kin hot ng ca l phn ng:
p sut

4,5 MPa

Nhit

80 0C

Thi gian phn ng

1,5 gi

Mt phn propylen c trng hp trong khi phn cn li dng lng c s

dng nh cht pha long polymer rn. Bm hi lu lun c gi vn tc cao
bo m hn hp lun c ng nht.trong l phn ng.
T trng ca hn hp cc cht tham gia phn ng lun c duy tr mc 5055% t trng ca polymer. Trong trng hp sn xut random copolymer hoc
terpolymer s np thm etylen (v/hoc Butan-1) vo l phn ng vi t l ph hp.
Nhit phn ng c gii phng trong thit b trao i nhit bi nc hi lu trong o
bc ca thit b phn ng.
Spheripol chp nhn kh nng cung cp H2, kim sot cu trc polymer, linh
hot trong qu trnh lm mt v kim sot chnh xc cht lng cc chng loi sn
phm.
Polymer c x lin tc t l phn ng qua ng ng bc hi bay hi
monomer trong khi c dn ti thng cha (p sut thng 15-18 barg).
Khu vc kh kh v x l bng hi nc
Trong trng hp sn xut homopolymer, random copolymer hoc terpolymer
th sn phm polymer c thu gom y bnh cha v c lc p sut tng
ng p sut kh quyn tch monomer khng tham gia phn ng.
Dng monomer c nn v c a v thit b thu hi propylen.
Mc kh kh cao v nhit ca dng sn phm cao to hiu qu cao cho
thit b x l bng hi nc v thit b n p polymer.
Bt polymer c thot ra bi trng lc ti thit b x l bng hi nc. Ti
, hi nc c bm vo ui monomer khng tham gia phn ng, propan v
kh hot ho xc tc cn st li sau phn ng cng nh nng cao cht lng sn phm
Hi nc c ngng t v x ra cng sau khi c dn qua thit b lm sch.

 Khu vc ng trng hp d pha (heterophasic copolymerization), kh

kh v sc Etylen (la chn)
Khi sn xut copolymer nn, d pha (impact copolymer), qu trnh polymer ho
phi c tin hnh qua 2 giai on. Trong trng hp ny, homopolymer to thnh
c dn ti l phn ng pha kh th nht
Trong l phn ng pha kh, pha cao su etylen-propylen oc b sung vo
homopolymer. Sn phm c tng cng rn cao.
L phn ng pha kh th nht:
Pha cao su c to thnh trong l phn ng thng ng sau khi np
homopolymer. Polymer c ho lng nh kh phn ng c hi lu.
Tc kh b mt vo khong 0,7 m/s. L phn ng pha kh hot ng trong
iu kin:
p sut:

14 barg

Nhit :

80/90 0C

Thi gian phn ng:

0,3 gi

T trng trung bnh ca tng phn ng:

300/350 kg/m3

Copolymer to thnh c x ra t y l (c kim sot).

Thit b sc Etylen.
Polymer c dn ti thit b x l bng hi nc v lm kh. Dng vt cht t
thit b lc c nn , lm lnh v sau np vo thit b sc Etylen . Dng kh giu
Etylen thot ra t nh c hi lu v . Dng sn phm t y c chuyn ti thp
tch..
Khu vc lm kh sn phm polymer
Sn phm polymer t t khu vc thp x l bng hi nc c a n b
phn lm kh ui nc b mt bng dng Nit nng. Nit t c dn ti thp
tch bt v nc ngng t trc khi c hi lu tr li thp lm kh.
Polymer kh c chuyn ti sil c lu gi trong mi trng Nit.
Khu vc thu hi propylen
Propylen khng tham gia phn ng v propan t thng cng vi dng x t
my nn (trng hp sn xut homopolymer v random copolymer) c dn ti thit
b thu hi propylen tch bt polymer cn st li ra khi dng hi lu.
Dng propylen hi lu c thu gom trong b propylen, B ny cng tip nhn
propylen mi.
Khu vc trn ph gia v n p
Polymer t thit bi xy kh c vn chuyn bi dng Nit n sil trung gian
trn nh b phn n p.

Bt polymer c x lin tc t sil y qua my o lu lng v van x ti b

phn n p.
Ph gia (lng v rn hoc rn dng khi) c cn ong linh hot theo
mun v a vo thit b n p. Trong my p polymer v ph gia c ng nht,
keo ho, p v to ht trong mi trng nc.
Cc ht sn phm c dn ti thit b xy kh tch nc v sau c
sng qua. Cc ht sn phm polymer t yu cu c vn chuyn bng khng kh ti
thng cha trn u v lu tr trong sil. Nc kh khong c thu gom trong b
v c bm li vo my n p bng bm sau khi lc v lm lnh.
3.3.1.2. M t cng ngh HYPOL-II
Cng ngh Hypol ca MITSUI c nh hng sn xut PP c bit, trong
bao gm copolymer c nn cao. Chui l phn ng a chc nng c vn u t cao
hn cc l phn ng n gin khc. Cng ngh ny tng i mi v c MITSUI p
dng v xy nh my ln Nht.

Hnh 15 :

S sn xut PP theo cng ngh Hypol II

Cng ngh Hypol bao gm nhng khu vc chnh sau:

Khu vc chun b nguyn liu
Propylen cp polymer (99.6% khi lng) c bm t b cha trung gian
vo khu vc chun b nguyn liu. Trong khu vc ny, propylen c lm kh qua lp
ry phn t loi nc v c x l bng xc tc kh vt COS. Vic x l ny l
cn thit do xc tc polymer ho rt nhy cm vi mt s tp cht trong nguyn liu.
ng xc tc (TEAL nng cao, khong 100%) v cht bin tnh cha trong
bnh cha ca nh cung cp c np vo cc thng cha v c ong nh lng
vo b phn hot ho xc tc.

Xc tc Ti-Mg rn HY-HS (hiu sut cao- chn la cao) th h 4 ng trong

cc thng cha t kho ho phm c dn n khu vc chun b xc tc v cn ong.
Xc tc Ti-Mg rn s c phn tn trong hn hp du khong v m nhn (cht lm
c) v c ong inh lng vo b phn hot ho xc tc.
Du khong c x t cc thng cha vo thng du nguyn liu. T thng
ny, du khong c dng ra v loi kh ng ng dn TEAL v c dng
cho b c v bc v my khuy. Du khong t b ny c a n b phn cn
ong v chun b xc tc.
M nhn t cc thng cha cng c a vo b ni trn v c cung cp
cho b phn o lng v chun b xc tc.
Ph gia kh hot tnh xc tc v kh kh khi du ra c cho vo hai thng
cha nguyn liu. T thng cha th nht ph gia c a n thp ra propylen
thp p v thit b tip nhn du bo ho (rich oil) v t thng cha th hai ph gia
c a ti ng c bo n dng x bn PP trong propylen t l phn ng sang
thit b tch cao p.
Khu vc polymer ho
Trong b phn hot ho xc tc, xc tc phn tn trong du v m c pha
trn vi cht ng xc tc v cht bin tnh v sau c pha trn thm vi mt
lng nh propylen lng thc hin qu trnh polymer ho s b trong l phn ng
dng vng.
Qu trnh polymer ho din ra trong pha lng hai l phn ng dng vng ni
tip nhau. Cc thit b phn ng c cng th tch v vn hnh cng iu kin nh
sau:
p sut:

khong 4.5 MPa

Nhit :

800C

Thi gian lu:

khong 1,5 gi

Bm trc vt c lp t y l phn ng. Bm tun hon hn hp phn ng

to iu kin phn b nhit c u khp chiu di ca l phn ng.
Nhit ca l phn ng c gii phng bng nc kh khong tun hon trong
v bc ca l.
Kh cha hydro c a vo thit b thu hi hydro (hm lng ti 99,5% th
tch) v c nn trc khi dn vo ng cung cp propylen ti u vo ca l phn
ng.
Propylen lng t thng cha propylen v hydro c a vo c hai l phn
ng. Mt phn propylen s b ho hi u vo ca l khng ch p sut trong
thng n nh dng (surge drum). Thng c tc dng lm y cc l phn ng v trnh
dao ng p sut trong l.
Hn hp t khu vc hot ha xc tc c bm vo dng propylen v ch c
dn vo l phn ng th nht.

Bn polymer t l phn ng th nht c a trc tip vo l phn ng th

hai hon thin qu trnh polymer ho. Bn PP t l phn ng th hai c x ra qua
ng ng bo n n thit b tch cao p tch polymer ra khi propylen tun hon.
Kh kh v thu hi propylen
Thit b tch cao p dng tch polymer ra khi propylen tun hon.
Polymer t thit b tch c a n b phn lc loi kh, sau c x
l bng hi nc. Ph gia n nh ho c bm vo polymer trc khi x l bng hi
nc.
Kh thot t nh ca thit b lc c a vo thp ra, ti du ra loi b
nhng ht mn khi kh tun hon. Ph gia c bit s c b sung vo du loi b
vt TEAL.
Khi b bo ho polymer, du ra s c thay th bng du mi. Du c c
bm ra ngoi thu hi.
Kh thot ra t thit b ra c nn v trn vi kh x t thit b tch cao p v
a ti thp thu hi propylen. Hi i ra t nh thp c ngng t v tun hon li
thp vi vai tr dng hi lu. Propylen sau khi thu hi c thu gom vo thng cha,
thng ny cng l ni nhn propylen tinh khit. Propylen t thng cha ny c a
vo cc thit b phn ng polymer ho. Phn y ca thp thu hi propylen c a
n thit b lc polymer qua ng ng bo n.
X l bng hi nc v xy kh polymer
Nh trng lc, polymer thot khi thit b lc, sau c dn n khu vc x
l polymer bng hi, ti , xc tc cn st li b kh hot tnh v cc hydrocacbon
cn li cng c loi trc tip bng hi nc. Hn hp hi v kh c a n thit
b sc nc.
Nc ngng t v hydrocacbon do hi nc li cun c a n thit b
tch. Phn lng t thit b tch c hi lu li thp sc. Pha hi v kh kt hp vi
monomer nh ca thp sc c dn ti my nn. Pha hi v kh c lm lnh i
ra khi my nn hoc c dn ti uc t hoc c tun hon li qu trnh cng
ngh sau khi xy kh. Cht lng hu c c tch t thit b nn (cc oligome) c
x ra cc thng cha.
Polymer t t b phn x l bng hi noc c xy kh bi Nit sau
c. Polymer kh c dn n cc sil (sil) bng h thng vn chuyn Nit kn.
Nit t t khu vc xy kh polymer s c ra v lm lnh trong thp sc,
sau c dn tr li khu vc xy kh bng qut gi v l gia nhit s b.
Nc c a vo thp sc ra Nit. Nc ngng t v vt polymer c
x t y ca thp sc n b thu gom nc thi.
Qu trnh n p, to ht, ng nht ho v tng cha
Polymer t sil c cn ong v a n thit b pha trn. Cc ph gia lng v
rn cng c o lng v a vo thit b pha trn mt cch lin tc. PP v cc ph

gia t thit b pha trn c a vo my n p. Khi cn, cc ph gia nng chy cng
c a vo my n p.
Trong my n p, polymer v cc ph gia c ng nht ho, to gel v lc.
Qu trnh to ht c thc hin my to ht di nc. Cc ht c a
n thit b phn tch nh nc tun hon (nc kh khong) v sau a ti
thit b lm kh. Cc ht kh theo trng lc i ti thit b phn loi. Cc ht polymer
t tiu chun c a ti trng nguyn liu, tip theo ti qu trnh ng nht ho v
sil bng dng khng kh. Cc ht khng t tiu chun c tp trung trong
container.
Nc tch ra t polymer c tp trung trong phuy cha v tun hon qua thit
b lm lnh tr li thit b to ht.
Qu trnh ng nht ho polymer v cha trong sil nhm to ra cc m
polymer ng th. Cc qu trnh ny c vai tr l qu trnh m gia giai on sn
xut v ng gi. Dung tch b cha c th lu tr sn phm trong vng ti a 5 ngy.
Sn phm PP thng mi c ng gi t ng vo ti PE 25 kg. Cc ti PE
c chuyn n nh kho bng xe nng.
3.3.2.Cng ngh pha kh:
3.3.2.1. M t qui trnh cng ngh NOVOLEN
ABB Lumus c cng ngh pha kh khc, cng ngh Novolen. Cng ngh ny
ang t thnh qu Arp Xt v Nam Phi. L phn ng thng ng v my khuy
cho php thay i chng loi sn phm nhanh hn l phn ng tng si. Khi ABB v
Equistar mua cng ngh ca Tagor, cng ngh ny c h tr thm bi cng ngh
ca Equistar. Nhn chung, cc phn xng ca BASF/Tagor trc kia nh hn cc
phn xng ca UNIPOL do my khuy c hc chim ch nhiu hn.

Hnh 16 :

S sn xut PP theo cng ngh Novolen

Propylen, etylen v bt k monomer no khc c a vo l phn ng vi s

c mt ca H2 nhm kim sot trng lng phn t. iu kin phn ng (nhit , p
sut v hm lng cht tham gia phn ng) c t sn theo yu cu. Phn ng mang
tnh cht to nhit v l phn ng c lm lnh bi thit b trao i nhit m kh
phn ng ho lng c trn vi nguyn liu np mi v c bm vo l phn ng.
S bay hi nhanh ca cc cht lng trong tng polymer bo m ti a s trao i
nhit.
Bt polymer c x ra t l phn ng v c tch p sut kh quyn.
Mnmer khng tham gia phn ng c tch khi bt v c nnm sau hoc c
hi lu hoc c dn ti u thit b sn xut olefin. Polymer c dn bng Nit ti
bnh tch propylen, sau c chuyn ti Sil v to ht vi s b sung ph gia.
u im ca cng ngh Novolen:
Thay i chng loi nhanh hn cng ngh ca Dow
Sn phm c s dng nhiu lnh vc
L phn ng nh lm gim thi gian lu ca nguyn liu tham gia phn ng
C iu kin thun li m phn vi ABB Lumus trong vic la chn nh
thu EPC.
Nhc im ca cng ngh ny l l phn ng khuy c hc, khng bo m
vn hnh an ton khi cc thit b c kh b hng hc.
Cng ngh UNIPOL gm c cc khu vc sau:
Khu vc lm sch nguyn liu
ng xc tc hm lng cao TEAL (xp x 100%) v cht bin tnh Donor
c dn t phuy cha ca nh cung cp ti cc thng cha nguyn liu v c ong
nh lng n thit b phn ng polymer ho.
Atmer 163 ph gia kh hot ho xc tc cng nh cc ph gia lng hoc un
nng chy cha trong cc thng cng-ten-n (thng, v.v) ca nh cung cp c
dn n thng cha nguyn liu v t phun vo thit b n p bng cc bm nh
lng. Cc cht ph gia phi un nng chy c gia nhit trc n nhit nng
chy trc khi cung cp ti thng nguyn liu, v ti cc thng ny cng c x l
nhit (gia nhit, bo n) m bo ph gia dng lng.
Dung dch lng propylen loi tinh khit polymer (99.6% khi lng) t b cha
trung gian c bm n b phn lm sch nguyn liu. Trong qu trnh ny, propylen
c lm kh bng cc ry phn t v x l xc tc vt COS cn st li.
Nit t trm tch Nit/xy c x l tch vt xy, nc. C hai cp p
sut cung cp Nit cho Phn xng PP, mt phn Nit c cung cp n cc thit b
tiu th Nit p sut thp, phn cn li c nn ti xp x 100 barg v cp ti thng
iu p cung cp cho l phn ng khi cn thit.

 Khu vc polymer ho v ui kh khi sn phm polymer

Xc tc Ziegler-Natta th h th t PTK4 c dn t cc thng cha ca nh
cung cp n b phn chun b xc tc, c cn ong v a n thit b phn ng.
Propylen tinh khit c a vo thit b phn ng t thng ng c trang b
cc thit b khuy c kh. ng xc tc, cht bin tnh v kh cha hydro nn c dn
ti dng vo ca thit b phn ng. Qu trnh polymer ho propylen din ra lin tc
trong thit b phn ng di cc iu kin sau:
p sut:

xp x 2.2 n 3.0 Mpa;

Nhit :

65 n 90 0C;

Thi gian phn ng:

xp x 1.0 n 1.2 gi.

Nhit ca phn ng polymer ho c gii phng bi vic bm hi lu cc

monomer. Monomer c hi lu t nh thit b phn ng, qua cc cyclon v thit b
lc, mt phn ngng t ti thit b ngng t bng nc v c thu li ti thit b phn
tch. Mt phn nh ca kh hi lu t nh thit b phn ng c thi qua cyclon n
h thng uc t ca Nh my lc du ui cc kh tr.
Monomer lng t thit b phn tch c bm tr li nh thp ti v tr
monomer ho hi v lm lnh lp polymer.
Bt polymer v phn monomer tch ra c ly ra tun hon t nh l phn
ng n thng x qua van x. S tch monomer khi sn phm polymer c thc
hin trong thng x. Cc monomer tch ra c a ti thit b thu hi monomer qua
cc cyclon v thit b lc.
Bt polymer t thng x c dn ti thng lm sch bng hai u quay. Trong
thng lm sch, cc monomer cn st li (ch yu l propylen) c ly ra bi dng
Nit. Lm sch bt sn phm trnh hydrocarbon tch t trong h thng vn chuyn
bt sn phm. Kh thi ca thng lm sch c a ti mt mng tch m
monomer c tch khi Nit. Nit c hi lu li thng x cn monomer tch ra
c a ti thit b thu hi monomer.
Bt polymer t thng lm sch c vn chuyn bng Nit ti cc thp cha
(Sil).
Bt polymer c thu gom trong hai sil. Mt sil c s dng nh mt thp
m trong trng hp thit b n p ngng hot ng, v thp cn li dng trong
trng hp khi thay i chng loi polymer.
Bt polymer t cc sil c a i p.
Peroxide (mt ph gia dng lm gim khi lng phn t polymer) cha
trong cc chai c a n cc thng nguyn liu, sau c bm nh lng vo
thit b p.

Khu vc gia cng sn phm

u cp dng trc vt cung cp bt polymer t sil n thng nguyn liu p

bng thit b o nh lng, bt c trn vi cc ph gia rn v to ht. Mt u
cp iu khin vic cp ph gia to ht t thng nguyn liu n thng nguyn liu p.
Cc cht ph gia rn c cp t mt phu cp ti hai thit b trn song song,
t c cp ti thng nguyn liu p. H thng trn song song c s dng
thay i nhanh cht ph gia trong trng hp thay i chng loi sn phm polymer.
Cc cht ph gia lng v ph gia un nng chy, atmer v peroxide c bm
nh lng trc tip vo thit b p.
Bt polymer v cc cht ph gia c lm nng chy, ng th ho, to gel v
c lc trong thit b p.
Mt lng nh nc kh khong c bm vo thit b p kh hot tnh xc
tc.
Cc cht ph du cn li (nc, sn phm ph c trng lng phn t thp, Nit,
propylen) c tch khi polymer nng chy trong thit b p nh chn khng.
To ht c thc hin trong mi trng nc.
Cc ht polymer c nc kh khong tun hon dn ti thit b phn tch
nc, sau i n thit b xy kh bng kh.
Nc tch ra c gom li trong mt thng cha, sau c bm ti thit thi
to ht qua cc thit b lm lnh.
Cc ht polymer t thit b lm kh c a ti thit b phn loi ht. Cc ht
tiu chun c vn chuyn bng kh n b phn kh mi, cc ht khng tiu
chun c cha trong cc cng-ten-n.
Khu vc kh mi, thit b chn khng, thng trn v thng cha.
Cc ht polymer t thit b lm kh, c tch khi kh vn chuyn bng cc
cyclon, sau c cp n thit b kh mi bng cc u cp trc vt. Nit c
cung cp gia cc u cp v l do an ton.
Cc cht ph du v c mi c ui khi cc ht polymer trong thit b kh
mi nh Nit v hi nc. V bc hi nc ca thit b kh mi c tc dng trnh
ngng t hi. Hi c cung cp ti thit b chn khng t nh ca thit b kh mi.
Cc ht polymer t y ca thit b kh mi c a ti thit b lm lnh bng
khng kh nh u cp trc vt, n c lm lnh trc tip bng khng kh. Cc
ht c lm lnh c a ti sng rung, phn tch t y c phn tch v
a tr li dng chnh. Cc ht polymer tiu chun t thng cha trung gian c
vn chuyn bng kh n cc thp trn.
Thit b chn khng dng kh mi v kh kh ti cc thit b p. Hi t thit
b kh mi, v phn ln hi t thit b n p c ho lng bng cch nn v lm
lnh, phn hi cn li t thit b p c tch trong thit b phn tch v c dn ti
uc t.

Hi ho lng c a ti thit b phn pha, nc c tch khi

monomer v a ti b phn x l. Monomer c gom trong b cha cht thi hu
c v c bm i t ngay lp tc.
Ht polymer c trn trong 02 thp trn to cc m polymer ng nht.
Sil ht polymer c s dng nh phn m gia b phn sn xut v b phn
ng gi. Cng sut b cho php cha ti a 5 ngy sn phm.
Thit b thu hi propylen hi lu
Kh thi t b phn tch kh khi polymer c a n thp kh hot tnh
TEAL, TEAL c kh hot tnh v tch i bi cht hp th hi lu. Cht hp
th sau c s dng lm nhin liu t.
Kh ra t nh thp c kh hot tnh c my nn a ti thit b kh
tan ly ra phn on ct propan/propylen.
Hi nh thp tch tan c ngng t mt phn trong thit b ngng t nc
ri a n thit b phn tch, c phn tch thnh pha hi dn ti uc t, v
pha lng hi lu li thp tch tan.
Sn phm y thp tch tan c a n thit b tch propan / propylen.
Propylen v phn kh nh nh thp qua thit b nhn c nn v lm lnh sau
kh ngng c gom trong thng hi lu phn tch. Mt phn kh ngng c a
tr li thit b phn tch v phn cn li (propylen thu hi) c a n b phn lm
sch nguyn liu.
Sn phm y thit b tch c em i t.
3.3.2.2. M t chu trnh cng ngh "UNIPOL"
Cng ngh Unipol ca Dow t thnh tu sut 10 nm qua trong vic cung
cp bn quyn cng ngh mi sn xut PP. Cng ngh Unipol hon ton s dng pha
kh tng si. Shell (SHAC) l Hng u tin pht minh v sn xut loi xuc tc hot
tnh cao, nhng hin nay Dow chim gi bn quyn ny. Dow tp trung pht
trin loi xc tc Metallocen sn xut PP. Unipol c bit n bi hng lot cc
sn phm nha vi cc tnh cht khc nhau v im chy mm v rn. Tuy nhin,
cng ngh ny khng tht s thch hp i vi nhng nh sn xut PP khi mun thay
i nhanh v linh hot cc loi sn phm trong dy chuyn sn xut ca mnh.

Hnh 17 :

S sn xut PP theo cng ngh Unipol

u im ca cng ngh Dow:

Dow mang nhn hiu ln chu u v chu
Ph bn quyn thp
Di sn phm rng.
Khu vc lm sch nguyn liu
Nguyn liu ca qu trnh trng hp l propylen lng (99,6% khi lng) t b
cha trung gian c bm ti b phn lm sch nguyn liu. Ti y, propylen c
lm kh qua thit b ry phn t tch b H 2O v x l xc tc loi vt COS.
Cng on ny cn phi c bi v tt c cc xc tc ca qu trnh polymer ho rt nhy
vi cc tp cht sn c trong nguyn liu.
Hn hp kh cha H2 t Nh my lc du c a ti thit b PSA lm sch
t n tinh khit ca hm lng H2 l 99,9% mol, sau c nn v a ti khu
vc phn ng.
Kh N2 t trm tch N2/O2 c x l loi b hm lng nh (phn triu) cc
tp cht O2, H2O v cc phn t phn cc khc, sau c nn v cung cp ti thit
b phn ng, kh N2 p sut thp c s dng cho cc qu trnh khc.
Xc tc Ziegler-Natta th h 3 v 4 trn nn Titan (nhm xc tc SHAC 200 v
300) dng bn ln trong du khong, ng xc tc - TEAL m c (nng xp x
100%) v donor - cht bin tnh t cc thng cha tng ng trong kho cha ho cht
c np ti cc thng cha trung gian phn xng t c iu khin chnh
xc lu lng cn thit ti vng phn ng.
Khu vc phn ng

H thng phn ng bao gm thit b phn ng gi lng, my nn kh tun hon

v thit b lm lnh kh tun hon.
Propylen, H2, xc tc, ng ng xc tc v cht bin tnh c a v thit b
phn ng, ti y qu trnh polymer ho s xy ra di cc iu kin sau:
- p sut

3,5

- Nhit

60-70 0C.

- Thi gian phn ng

1,25

MPa.
gi.

My nn tun hon thi dng kh phn ng i qua lp xc tc trong thit b

phn ng m bo phn ng tng si v ly i nhit to trong qu trnh phn ng.
Nhit phn ng c tch ra bi dng kh tun hon c lm lnh bng nc lnh
qua thit b trao i nhit dng ng-tm do tun hon propylen lm lnh v ngng t
mt phn. Lp tng si m bo s cn bng ca trao i cht v nhit. Sn phm
polymer c kch c ht phn tn ng nht.
Phn ng polymer ho c th c ngt nu cn thit bng vic phun vo l
phn ng dng "kh trit tiu" CO (kill gas).
Bt polymer c tho ra khi thit b phn ng qua h thng tho sn phm
nh cao ca lp tng si. Sn phm s c x l tch monomer ln trong dng
sn phm khi cho qua lin tip cc khoang tch c p sut khc nhau v sau c
tip tc a ti h thng tinh ch sn phm.
Khu vc tch v thu hi kh
Sn phm polymer ra khi thit b phn ng vn cn cha ln hydrocarbon
khng phn ng. Nhng hydrocarbon ny c thi tch ra khi dng sn phm v
tun hon tr li chu trnh cng ngh.
Polymer c a ti thit b tch, ti y dng N 2 tun hon c thi ngc
v cun theo cc hydrocarbon khng phn ng.
Kh thi i ra t nh ca thit b tch c a ti h thng thu hi kh qua
thit b lc. Trong h thng ny kh c nn v lm lnh ngng t cc monomer.
Dng kh nh khng ln hydrocabon ngng t c thi ra uc t. Hydrocabon
ngng t c a ti thp tch n gin tch s b. Dng nh thp giu propylen
c tun hon tr li khu vc phn ng, dng y thp giu propan c th c tun
hon tr li khu vc phn ng hoc s dng lm nhin liu.
Bt polymer t thit b tch c vn chuyn bng bng ti ti thp lm sch
sn phm loi b nhng monomer v xc tc mt hot tnh cn st li.
Kh N2 sch c a vo t pha y ca thp thi tch ht hydrocarbon ra
khi polymer. Kh N2 c cha mt lng nh cc hydrocarbon c a ti thit b
tch Nit/Hydrocabon thu hi tip tc dng ny. Mt lng nh hi nc c a
vo t pha y ca thp kh ht hot tnh ca xc tc v cht ng xc tc cn li.
Bt polymer sau lm sch c a ti b phn b sung ph gia v gia cng.
Khu vc x l cc cht ph gia

Cc thit b ph tr c cung cp bo qun c hai loi ph gia rn v lng.

Cc ph gia dng rn c np vo h thng to ht dng hn hp tng th
(mastermix). Mastermix c lm tng m qua vic tch ra mt lng nh t dng sn
phm chnh. Dng ny c dn ti bnh bc nc v chuyn ng tng si vi N 2 v
c lm lnh thun li cho qu trnh trn vi ph gia rn. Theo trng lc dng
polymer lnh t chy xung thit b trn nm ngang kiu di xon. Ph gia rn c
np vo bng bin php th cng v c trn ln vi polymer. Dng mastermix to
thnh c a ti thng nguyn liu ca my n p.
Ph gia lng t chy t thng cha ti b cha bi trng lc v c bm ti
thng nguyn liu ca my n p.
Khu vc p v to ht
Bt polymer v ph gia x l c np vo thng nguyn liu ca my n
p. Trong my n p, hn hp s tan chy, ng nht, keo ho, lc v to thnh ht.
Qu trnh to ht c thc hin trong mi trng nc.
Ht polymer c vn chuyn bi dng tun hon ca nc kh khong ti
thit b tch nc v ht polymer.
Nc tch ra c thu gom vo thng cha v c bm tun hon tr li thit
b to ht.
Dng ht polymer t thit b tch c a vo thit b phn loi ht. Nhng
ht t kch thc tiu chun c vn chuyn bng khng kh ti qu trnh trn v
c lu cha trong sil. Nhng ht khng t tiu chun c thu gom vo thng
cha. Cc thp trn ht polymer c trang b nhm trn u v ng nht cc m sn
phm.
Khu vc ng bao v ng thng
Sn phm PP thng mi c ng vo cc bao PE loi 25kg. Cc bao c
nh lng v ng gi bi lp mng co PE sau c a vo kho cha bng xe
nng..
(incineration).
3.3.2.3. M t qui trnh cng ngh ca INNOVENE
Cng ngh Innovene ca BP s dng l phn ng pha kh nm ngang vi my
khuy. Cng ngh ny cho thay i nhanh chng chng loi sn phm PP. BP c h
xc tc ring. Cng ngh Innovene cho ra c rt nhiu loi sn phm, t
homopolymer n copolymer nn. L phn ng th cp c ln ging l s cp
c s dng sn xut copolymer nn. Vi cng ngh ny c th vn hnh ng
thi 2 dy chuyn c lp sn xut PP. Cc nh sn xut PP M thng chuyn t
cc cng ngh khc sang cng ngh tng t vi Innovene khi mun tng cng sut
sn xut copolymer nn.

Hnh 18 : S sn xut PP theo cng ngh Innovene

u im ca cng ngh Innovene
- Thit k n gin nhng hiu qu
- Chuyn chng loi sn phm rt nhanh v t sn phm khng t cht
lng.
- Vn u t v chi ph vn hnh thp
- D dng nng cng sut theo nhu cu
- S dng mt h xc tc cho tt c cc loi sn phm
- Thi gian thay i chng loi sn phm ngn
- Sn phm rn chc, cht lng cao, s dng nhiu mc ch v c trin
vng pht trin tt.
Phn b phn t lng ca nha PP sn xut theo cng ngh Innovene rt hp,
v vy c cht lng cao. Tuy nhin, nhc im ca cng ngh ny l cho ra sn
phm BOPP cht lng khng tt, hn na, ngun cung cp xc tc li b ph thuc,
khng t sn xut c.
Khu vc Np xc tc
Cng ngh s dng xc tc Ti-Mg CSTR th h th 4 dng bn trong du
khong cha trong cc cng-ten-n ca nh cung cp c a n t kho cha ho
phm ca Nh my lc du v vo thng nguyn liu, t c nh lng ti
thit b phn ng. Cht ng xc tc TEAL nng cao (xp x 100%) v cht bin
tnh c bm nh lng vo thit b phn ng trc tip t cc thng ca nh cung
cp.

Cc cht np c np vi t l c kim sot t sn xut sn phm vi

sn lng v cht lng mong mun.

Khu vc Polymer ha

Nguyn liu propylen c lm sch, xc tc, ng xc tc, cht bin tnh,

kh cha hydro (92,27% mol) p sut cao t Nh my lc du c a vo thit b
phn ng vi my khuy c hc. Trong thit b phn ng, ht polymer c to ra lin
tc nh qu trnh polymer ha pha kh trong cc iu kin sau:
- p sut:

2.0 MPa

- Nhit :

70 0C

- Thi gianphn ng:

1.4-1.5 gi

Cc phn t phn ng c khuy u trong thit b v c thi gian lu bng

nhau, do nhn c sn phm ng nht.
Hi monomer (propylen) bay ra nh l phn ng c trn vi monomer c
thu hi sau khi c lm mt v ngng t trong thit b trao i nhit c a vo
thit b phn tch, ti y chng c trn vi propylen mi t b phn lm sch
propylen .
Propylen lng t y thit b tch c bm tun hon li nh thit b phn
ng. Nhit phn ng c ly ra nh lm bay hi mt phn propylen lng ny. loi
nhng cht tr, mt phn propylen lng c a ra ngoi ti u x ca bm. Dng
cht lng c iu khin t c mt s chnh nhit trong thit b phn ng.
Kh tun hon thot ra t nh thit b tch kt hp vi hydro c bm vo
y thit b phn ng.
Qu trnh polymer ha c th c ngng li nh bm kh CO (kill gas) khi cn
thit.

Khu vc Kh hot tnh bt polymer

Bt polymer ng th (homopolymer) thot ra t l phn ng c cha cc

hydrocacbon khng tham gia phn ng. Nh gim p sut trong thit b tch nn
nhng hydrocacbon ny c tch ra khi sn phm homopolymer, sau chng c
nn v bm tun hon li thit b phn ng.
Bt polymer ra khi thit b tch vn cha monomer (dng hp ph). Chnh v
vy chng cn c lm sch ti ct sc ra (Purge Column). Nit t c bm vo
y ct cun monomer ny cng xc tc, cht ng xc tc khi bt polymer.
Kh thot ra khi u ct sc ra c a vo h thng thu hi kh tch
monomer, hi lu li thit b phn ng.
Bt polymer ra khi ct sc ra c trn vi ph gia sau a sang b phn
p to ht.

Khu vc Hon thin sn phm

Bt polymer t ct sc ra c a ti thit b p bng u trc vt qua h

thng o lng trn cng vi lng xc nh cht ph gia rn v lng. Trong thit
b p, chng b nng chy, ng th ho, to gel, lc v to ht.
Qu trnh to ht c tin hnh trong mi trng nc.
Ht polymer c a ra khi my p v c vn chuyn bng nc kh
khong n thit b phn tch tch polymer v nc.
Nc sau khi tch c gom vo b v bm tun hon ti h thng to ht.
Ht polymer sau khi ra khi thit b tch c a sang b phn loi. Sn phm
t cht lng c a sang thp trn nh dng khng kh, ph phm a sang thng
cha khc.

Khu vc Thp trn

Nhng ht polymer c trn ti 3 thp trn thu hi polymer ng nht.

B phn Sil

Thp ny c s dng nh phn m gia khu vc sn xut v dy truyn

ng gi. Nhng thp ny c th cha c sn phm sn xut trong vng 5 ngy.

Khu vc ng gi

PP thng phm c ng gi vo nhng bao PE 25 kg, cc bao ny c

ng thng v ct cht bng mng PE co dn v a n nh kho bng xe nng.
Nhng bao v mng PE co dn c sn xut ti Phn xng PP.

Khu vc Lm sch propylen

Propylen lng tyinh khit polymer ho (99,6% khi lng) t b cha trung
gian c bm sang khu lm sch propylen. Ti y propylen c xy kh bng ry
phn t.
Kh vt COS v tt c cc xc tc polymer ha u rt nhy cm vi COS v
cc cht nhim trong nguyn liu..
3.4. KHI QUT V PHT PHT
POLYPROPYPROPYLENE [27]

TRIN

CNG

NGHIP

Cng nghip sn xut PP thng mi tn ti hn bn mi nm nay.

Cng ty Montecatini a ra cng ngh sn xut PP thng mi u tin vo
nm 1957. l qu trnh polymer ho dung dch bn (xng c s dng lm mi
trng pha long) xy ra nhit 55-60oC, p sut 1MPa vi s c mt ca xc tc
Ziegler-Natta th h mt (gm cc hp cht c kim, ch yu l (C2H5)3Al, v TiCl3. S
dng 1g xc tc sn xut gn 1 kg PP.
Vo nhng nm thp k 60 cc cng ty khc nhau ci bin cng ngh sn
sut PP da trn qu trnh Montecatini. Cc cng ngh s dng xc tc th h mt vn
c p dng rng ri.

Vo nm 1985 th phn ca cng ngh sn xut PP s dng xc tc th h mt

chim 42% M (trong tng s 2,6 MMTA), 79% Nht (trong tng s 1,35 MMTA)
v 71% Ty u (trong tng s 2,3 MMTA).
Cng ngh ny c nhng nhc im chnh sau:
Xc tc cn c phn hu sau qu trnh polymer ho do nhy cm cao
ca propylen i vi xc tc;
Cn loi b cc hp cht Atatic khi polymer (hm lng c th ln n
20%);
Chi ph sn xut cao so vi cc qu trnh sn xut cht do chu nhit khc
do phi u t b sung cc thit b gim hot ho xc tc.
Mc d vy, th phn ca cng ngh sn xut PP dung dch bn l 31% tng
sn phm PP trn ton th gii vo nm 1990 v 20% vo nm 1999.
Vo nhng nm 1970-1983 cc xc tc lp th hiu qu cao th h hai v ba
c a ra (hiu sut ca xc tc ln lt l 10-15 v 20-30 kg PP i vi 1g cht xc
tc). Nhng xc tc ny gm TiCl4 trn cht mang MgCl2 cng vi alkyl ca nhm v
cc ph gia hu c cho s iu khin tnh ng cu ca polymer.
n gia thp k 80 cc cng ty khc nhau ci tin cc cng ngh da trn
nhng xc tc . Polymer ho s dng xc tc hiu qu cao c a dng cho c 2
loi l phn ng pha kh v pha bn.
3.5. GII TRNH V S LA CHN CNG NGH SN XUT PP [28]
Hai yu t quan trng la chn cng ngh sn xut PP l h vt cht/c kh
v h xc tc. Xc tc ng vai tr quan trng hn.
C 3 loi cng ngh chnh sn xut homopolymer v random copolymer: L
phn ng dng vng mi trng bn, l phn ng c my khuy lin tc mi trng
bn v l phn ng pha kh. Trong trng hp sn xut copolymer nn phi b sung
thm mt l phn ng pha kh (thm ch c th phi b sung thm hai l).
PP c sn xut di 3 th loi: isotactic, syndiotactic v atactic. Cu trc
phn t ca isotactic PP l sp xp nhm metyl v mt pha ca phn t trong khi
syndiotactic PP phn nhm metyl u sang 2 pha. Isotactic PP rn, chu lc ko cng
tt v c bn ho hc tt nh c cu trc tinh th cao. Syndiotactic PP kh sn xut
hn v c tinh th thp hn. Mt s syndiotactic PP c sn xut vi s c mt
ca xc tc metallocen. Atactic PP kh bn trn th trng v loi sn phm ny mm
ging nh cht n hi. Atactic PP thng c to thnh trong khi sn xut isotactic
PP v b loi ra hoc c bn cho nhng nhu cu c bit hoc c t b. Cng
ngh sn xut isotactic PP c p dng rng ri t nhng nm 1980.
Thay i trong cng ngh sn xut PP tp trung ch yu trong pht trin xc tc
hiu sut cao v chn la cao. Loi xc tc ny c s dng gim bt s to
thnh ca atactic PP v trnh phi kh cn xc tc.

Homopolymer PP c rn cao, trong sut v c t trng thp (0,9 0,906

g/cm3), bn vng ho hc v bn nhit. Tuy nhin, homopolymer c chu nn thp,
c bit l nhit thp. Copolymer c sn xut khc phc nhc im ny.
S dng xc tc metallocen trong sn xut PP c pht trin nh trong sn
xut PE. Vi loi xc tc ny cn lu ci thin cc nhc im sau:
- Nha c im chy mm thp
- Kt hp vi comonomer mi nh hexen-1
- trong sut ca sn phm
- Kh nng sn xut nha c tnh cht mong mun (im chy mm..) khng
cn s dng k thut CR (l phn ng tun hon).
Exxon Mobil v Basell hp tc vi nhau pht trin sn xut PP s dng
xc tc metallocen. Exxon Mobil ch trng pht trin sn xut si trong khi Basell
pht trin sn xut nha c. ATOFINA cng l cng ty pht trin s dng metallocen
mnh.
Cc nh bn quyn chnh hin nay bao gm:
- Basell Spheripol

L phn ng dng vng

- Dow Unipol

L phn ng pha kh

- BP Innovene

L phn ng pha kh

- ABB Lumus Novolen

L phn ng pha kh

- Mitsui Hypol

L phn ng dng vng

- Sumitomo

L phn ng pha kh

Cng ngh polymer ho pha bn c s dng rng ri. l cng ngh

SPHERIPOL ca cng ty Basell v HYPOL/HYPOL-II ca cng ty MITSUI. Polymer
ho xy ra trong cc l phn ng dng vng vi bm tun hon ca hn hp phn ng.
Cc cng ngh pha kh dc s dng khc nhau vi thit k hnh dng ca l
phn ng v thit b khuy nh sau:
i vi cng ngh UNIPOL ca cng ty Union Carbide, qa trnh polymer
ho xy ra trong l phn ng tng si khng c thit b khuy;
i vi cng ngh NOVOLEN ca cng ty BASF (hin nay l ca ABB),
qa trnh polymer ho xy ra trong l phn ng thng ng c thit b khuy c hc;
i vi cng ngh INNOVENE ca cng ty BP, qa trnh polymer ho xy
ra trong l phn ng nm ngang c thit b khuy c hc.
Cng ngh UNIPOL tng si l cng ngh pha kh c tnh u vit nht do iu
kin trao i nhit v vt cht tt hn. Kh nng to ra cc vng nng nh hn so vi
cng ngh khuy v do lm tng cht lng sn phm polymer.

Trong nm 2000, cng ngh sn xut PP trn th gii hu nh khng c thay

i ln. Tuy nhin cc nh sn xut PP ci tin dn h xc tc v chu trnh cng ngh
nng cao tnh cnh tranh, cht lng sn phm v m rng chng loi sn phm.
Mt s thnh tu t c do ci thin chy mm ca cc homopolymer.
Tt c nhng nh sn xut PP ln c th sn xut tt c cc chng loi
homopolymer trn th trng vi tnh nng khc nhau.
nh gi v la chn ng nh cung cp bn quyn, di y l bng tp
hp cc s liu v cng ngh ca cc nh cung cp bn quyn bao gm:
Tnh nng k thut ca qu trnh polymer ho
c tnh, gi thnh ca xc tc v ho cht
Tnh cht ca thit b
Tiu th nguyn liu, xc tc, ph gia v nng lng ph tr sn xut mt
tn PP
Cht lng ca sn phm polymer
Lng cht rn, lng, kh thi
Cng ngh HYPOLL II cho php sn xut nhiu loi sn phm hn vi cc ch
tiu khc nhau v tnh nng a dng hn
So snh vi cc cng ngh khc c xem xt trong nghin cu kh thi ny,
cng nghHYPOLL II c nhng u vit sau v mt chi ph u t v vn hnh:
Th tch ca ton b thit b phn ng c s dng hiu qu trong qu trnh
polymer ho pha lng, trong khi khu vc phn tch tch polymer khi monomer
tun hon l cn thit i vi cng ngh pha kh. iu ny loi b kh nng nhim bn
sn phm khi x khi thit b phn ng do khng c b mt tip xc trong th tch
phn ng
Hiu sut trao i nhit trong thit b phn ng dng vng cao hn so vi
trong pha kh do thit b phn ng dng vng cho php tc trao i nhit cao hn
cng nh vic loi b nhit tha t cc ht polymer ho cn bng hn. iu ny lm
nhit phn ng n nh v d iu khin hn (khng c cc"im t nhit")
Cc c tnh thit k ca thit b phn ng dng vng lp m bo tnh linh
hot khi tng cng sut ca phn xng PP. Vic tng cng sut trong trng hp
polymer ho pha kh i hi cc nghin cu thit k ngt ngho hn do c cc yu cu
nghim ngt hn i vi thit k ca thit b phn ng v gii hn v trng trao i
nhit
Vic iu khin dng nng chy v s ng th trong thit b phn ng dng
vng lp c hiu qu hn so vi thit b phn ng dng tng si hoc lp khuy trn
ngang/dc do cc ng xc tc v hydro c a vo dng tun hon c s khuy
trn mnh (polymer trong monomer lng). iu ny to ra iu kin polymer ho n
nh v ng th

 Cng ngh cn to iu kin cho vic thay i nhanh chng loi sn phm
m khng tng chi ph vn hnh. Bnh thng cc nh my s dng cng ngh c th
sn xut 15 n 18 cp sn phm trong mt thng. T l sn phm khng t tiu
chun trong trng hp sn xut homopolymer khong 0.2% (sn phm khng t
cht lng cng c th bn c)
Do hot tnh cao ca xc tc, vi hiu sut polymer cao, hm lng cn xc
tc cn li trong polymer (v ko theo l hm lng kim loi) l rt thp. iu ny dn
n sn phm c mu tt hn (vng nht). Hn na, vic x l bt polymer bng hi
nc trc tip lm gim hm lng cc cu t ho tan v khng bn trong polymer.
iu ny dn n sn phm PP c cht lng cao dng c trong cng ngh y t v
thc phm
Trong trng hp ng dng xc tc hnh thi hc c khng ch, vic sn xut
bt polymer vi ht c kch thc t 0.3 n 5 mm c th thc hin c m khng
cn thay i cu hnh phn xng do kch thc ht khng nh hng n hiu sut
tng si trong thit b phn ng dng vng lp. Mi loi xc tc to ra cc polymer vi
phn b kch thc ht trong khong hp v hnh thi polymer ng nht. Bt polymer
hnh cu c lm t PP vi tc chy rt cao hoc rt thp c th c dng vi
ph gia dng khng to ht i vi cc ng dng p n
Cng ngh " c tin cy v kh nng vn hnh cao so vi cng ngh pha
kh. iu ny a n nhng kt qu sau: cc my nn pitng c tin cy thp khng
c s dng trong qu trnh polymer ho pha lng, hnh thi c khng ch ca
polymer v cc c tnh ca qu trnh to iu kin cho qu trnh vn chuyn polymer
rn d dng, cc gii hn ca qu trnh do hin tng "im qu nhit", "th tch cht",
sn phm b nht khng xut hin trong tt c cc qu trnh x l
Trn c s , ngh s dng cng ngh Hypol II sn xut PP .

CHNG 4
M PHNG CNG NGH SN XUT
POLYPROPYLENE BNG PHN MM
HYSIS
4.1. Nhng thng s ban u: [29]
- Cng sut ca nh my

: 150.000 (tn/nm);

- Di cng sut hot ng ca nh my : (50 100)% cng sut thit k;

- Nh my hot ng

: 8000 (gi / nm);

- Xc tc hiu sut cao, tiu th ti a t (0,033 0,05) kg/tn sn phm;

Yu cu c tnh k thut ca nguyn liu Propylen

Nguyn liu propylen t phn xng thu hi propylen (PRU) ca Nh my lc
du s c chuyn n phn xng PP bng ng ng. Phn propylen nhp s c
chuyn n cc b cha t ti khu b cha sn phm ca Nh my . Cc c tnh v
iu kin bin ca nguyn liu c ch ra di y:
p sut

26 kg/cm2g

Nhit

Mi trng

Trng thi:
Bng 4 :

Lng
Thnh phn ca nguyn liu t nh my lc du
Tinh khit

Propylen, % th tch, ti thiu

99,5

Hyr, phn triu th tch, ti a

20

Loi

0,5

Nit, Mtan, phn triu th tch, ti a

100

Etan, phn triu th tch, ti a

200

C4, C5, Hydrocarbon no, phn triu

th tch, ti a

200

Etylen, phn triu th tch, ti a

100

Buten, phn triu th tch, ti a

100

Penten, phn triu th tch, ti a

10

c t:
Acetylen, phn triu th tch, ti a

Metylacetylen, phn triu th tch, ti a

Propadien, phn triu th tch, ti a

Butadien, phn triu th tch, ti a

50

C6-C12, phn triu th tch, ti a

20

xy, phn triu th tch, ti a

CO, phn triu th tch, ti a

0,03

COS, phn triu th tch, ti a

0,02

Lu hunh tng s, phn triu khi lng ti

a,

Metanol, phn triu th tch, ti a

Isopropanol, phn triu th tch, ti a

15

Nc, phn triu khi lng, ti a

Asen, phn triu th tch, ti a

0,03

Phosphin, phn triu th tch, ti a

0,03

Ammonia, phn triu khi lng, ti a

Cyclopentadien, phn triu th tch, ti a

0,05

t tnh k thut kh cha Hydrogen:

Kh cha hydro t phn xng Reforming ca Nh my lc du c a n

phn xng PP c c tnh k thut nh sau:
p sut:

50 kg/cm2g

Nhit :

Mi trng

Trng thi:

Kh

Bng 5 :

Thnh phn ca kh cha hydro

Tinh khit

Hyr, % th tch, ti thiu

99,5

Nit, Metan, , % th tch, ti thiu

ti 0,5

c t:
CO, phn triu th tch, ti a

0,5

CO2, phn triu th tch, ti a

xy, phn triu th tch, ti a

Nc, mg/Nm3, ti a

Lu hunh tng th, phn triu khi lng, ti a

Thu ngn (t in phn), mg/Nm3, ti a

Acetylen (t cracking), phn triu th tch, ti a

10

Ammonia (t n/m m), phn triu khi lng, ti a

4.2. TNH CC GI TR BAN U CHO QU TRNH M PHNG

(Thc t nh my c h thng iu khin lu lng tng dng nhng trong
m phng tnh ta phi tnh ton cc s liu ban u a vo m phng)
Gi thit : Dng sn phm ra trong mi thit b phn ng hu nh khng cha
hydro.
Lng tiu th xc tc thp nht trong 1 h
chuyn ha Propylen tng : 50 %
Bng 6 : chuyn ha ca Propylen v Hydro trong tng thit b phn ng

TBP preR

TBP R1

TBP R2

C% H2

100%

C% C3H6

5%

C% H2

100%

C% C3H6

50%

C% H2

100%

C% C3H6

40%

Lng Propylene nguyn liu thng mi ban u ( make-up) l:

F = 150000 ( Tn )
Lu lng khi lng Propylene nguyn liu thng mi ( make-up) l
F Propylene make-up =

150000 *10 3
= 18750 ( kg/h )
8000

Lu lng khi lng Propylene hi lu l

F Propylene hi lu = 18750 ( kg/h) ( v hiu sut P t 50% )
Tng lng Propylen a vo u qu trnh l
F Propylene = F Propylene make-up + F Propylene hi lu = 37500 ( kg/h )
Tng lng Propylen tinh khit a vo u qu trnh l
F Propylene =

37500 * 99,5
= 37312.5 ( kg/h )
100

Gi :
X : Tng lng propylene a vo u qu trnh ( propylene make-up
v dng propylen hi lu)
X 1 lng propylene vo thit b ha trn xc tc trc khi vo thit b
PreR
X2 l lng propylene vo trc tip thit b preR
X3 l lng propylene vo trc tip thit b R1
X4 l lng propylene vo trc tip thit b R2
X1 + X2 + X3 + X4 = 37312.5 ( kg / h)

(a)

Tnh :
Xt c qu trnh :
Lng propylen phn ng l ; =

37312.5 * 50
= 18656.25 ( kg/h)
100

P :
2500 C3H6
105200
X
18656.25

H2

2.016

PP
105200.016

X*2.016/105200

X*105200.016/105200

0.358

18656.608

Lng PP sn xut c trong 1 h : 18656.608

Lng hydro tiu tn trong 1 h : 0.358
Lng xc tc tiu th trong 1 h :

(kg/h)
(kg/h)

(kg/h)

(kg/h)

18656.608 * 0.033
1000

= 0.616 (kg/h)

Lng propylen cn li : = 37312.5 - 18656.25 = 18656.25 (kg/h)

Xt trong tng thit b phn ng :
chuyn ha ca propylen ti PreR l 5%
lng propylen tham gia phn ng ti PreR l : 5% ( X1 + X2 )
chuyn ha ca propylen ti R1 l 50%
lng propylen tham gia phn ng ti R1 l : 50%( 95% ( X1 + X2 ) + X3)
chuyn ha ca propylen ti R2 l 40%
lng propylen tham gia phn ng ti R2 l : 40% (50% (95% ( X1 + X2 ) +
X3) + X4 )
Lng propylen cn li l : 60%(50%( 95 %( X1 + X2 ) + X3) + X4)
=18656.25 ( b )
Tng lng propylen phn ng l : 5% ( X1 + X2 ) + 50 % ( 95%( X1 +
X2 ) + X3) +40% ( 50% (95% ( X1 + X2 ) + X3) + X4 ) = 18656.25 ( c )

Gi s lng propylen vo thit b trn trc khi vo thit b PreR l :

X1 = 1000 (kg/h)

(d)

T ( a ), ( b ), ( c ), ( d ) gii h phng trinh ta c

X2 = 4035.043 (kg/h)
X3 = 6845.017 (kg/h)
X4 = 25437.47

(kg/h)

V tinh khit ca Propylen l 99.5 % nn

Lu Lng propylene thc vo thit b ha trn xc tc trc khi vo thit
b PreR :
Fpro1 =

1000 (kg/h)

Lu lng propylene thc vo trc tip thit b preR :

Fpro2 =

4035.043 (kg/h)

Lu lng propylene thc vo trc tip thit b R1 :

Fpro3 =

6845.017 (kg/h)

Lu lng propylene thc vo trc tip thit b R2 :

Fpro4 =

6845.017 (kg/h)

Lng propylen tham gia phn ng ti PreR l : 251.752

Lng propylen tham gia phn ng ti R1 l : 5814.154
Lng propylen tham gia phn ng ti R2 l :

12500.638

Ti thit b PreR:
P:
2500 C3H6

105200

H2

2.016

105200.016

X*2.016/105200

251.752

PP
X*105200.016/105200

0.00482

251.757

(kg/h)
(kg/h)

Ti thit b R1:
P:
2500 C3H6
105200
X
5814.154

H2
2.016
X*2.016/105200
0.11142

PP
105200.016
X*105200.016/105200 (kg/h)
5814.265

(kg/h)

Ti thit b R2:
P:
2500 C3H6

105200
X
15200.638

H2

PP

2.016

105200.016

X*2.016/105200

X*105200.016/105200 (kg/h)

0.23956

12055.877

(kg/h)

Lng PP trong thit b PreR : 251.757 (kg/h)

Lng PP trong thit b R1: 251.757 + 5814.265 = 6066.022

(kg/h)

Lng PP trong thit b R2: 6066.022 + 12055.877 = 18658.606 (kg/h)

Lng hydro ( tinh khit )vo thit b preR l : 0.0482 ( kg/h)
Lng hydro vo thit b R1 l : 0.11142 ( kg/h)
Lng hydro vo thit b R2 l : 0.23956 ( kg/h)
V tinh khit ca hydro l 99.5 % nn ta c :
Lu lng hydro thc vo thit b preR l : 0.0485 ( kg/h)
Lu lng hydro thc vo thit b R1 l : 0.11198( kg/h)
Lu lng hydro thcvo thit b R2 l : 0.24076 ( kg/h)
Tng Lng hydro a vo l : 0.358 ( kg/h)
Bng cn bng vt cht cc dng vo ra ca cc thit b :
( v qua bm v tb trao i nhit thnh phn v lu lng cc dng vt cht
xem nh khng i nn ta ch lp bng cho cc thit b PreR, R1, R2, tb tch )

Bng 7 :

Bng cn bng vt cht ca thit b PreR

Thit b PreR
Vo (kg/h)

Ra(kg/h)

Propylen

5009

4758

Hydro

0,005

Catalyst

0,62

0,62

Propan ln trong Propylen

25,2

25,2

1,5.10-5

1,5.10-5

Metan ln trong H2

N2 ln trong H2
PP
Tng

Bng 8 :

1.10-5

1.10-5

252

5036

5036

Bng cn bng vt cht ca thit b R1

Thit b R1
Vo (kg/h)

Ra(kg/h)

11569

5755

Hydro

0,11

Catalyst

0,62

0,62

Propan ln trong Propylen

59,6

59,6

Metan ln trong H2

3,5.10-4

3,5.10-4

N2 ln trong H2

2,34.10-4

2,34.10-4

PP

251.7

6066

Tng

11881

11881

Propylen

Bng 9 :

Bng cn bng vt cht ca thit b R2

Thit b R2
Vo (kg/h)

Ra(kg/h)

Propylen

31065

18564

Hydro

0,24

Catalyst

0,62

0,62

Propan ln trong Propylen

187,4

187,4

Metan ln trong H2

1,07.10-3

1,07.10-3

N2 ln trong H2

7,15.10-4

7,15.10-4

PP

6066

18656

Tng

37319

37409

Bng 10 :

Bng cn bng vt cht ca thit b tch PP

Thit b tch PP
Ra (kg/h)
Vo (kg/h)

nh( kg/h)

y(kg/h)

Propylen

18564

18564

Hydro

Catalyst

0,616

0,616

Propan ln trong Propylen

187

187

Metan ln trong H2

7,15.10-4

7,15.10-4

N2 ln trong H2

7,15.10-4

7,15.10-4

PP

18656

18656

Tng

37409

18752

18656

4.3. TNH TON QU TRNH NH M PHNG BNG PHN MM

HYSYS[30]
p ng nhu cu ngy cng ln cc sn phm du m c v s lng v cht
lng, chng ta phi khng ngng ci tin v cng ngh v phng php sn xut. V
vy, cc cng trnh nghin cu khoa hc, cc d n thit k c tin hnh, v cng
vi s pht trin vt bc ca ngnh cng ngh thng tin, vi nhng my tnh tc
cao, cc h iu hnh siu vit, cc lp trnh vin gp phn to ln cho s ra i ca
cc phn mm m phng.
Trc y ln k hoch cho mt d n i hi rt nhiu thi gian, v kh
nng thc hin d n l kh c th khng th bit trc c. Nhng khi cc phn
mm m phng ra i, th cng vic tr nn nh nhng i rt nhiu, chng ta c th
m phng hot ng ca cc nh my trong cc ch vn hnh khc nhau, thay i
cc thng s lm vic ca bt k n v hot ng no m khng nh hng n qu

trnh hot ng chung ca nh my. Ngoi ra, vi nhng tnh nng ca cc phn mm
m phng ta c th thit k c cc d n khc nhau, tm c phng n ti u,
nhanh, cho kt qu kh quan v t hiu qu kinh t, quan trng hn na l p dng
c cho hu ht cc lnh vc ca ngnh du kh v cc ngnh cng ngh ho hc,
m bo c tnh kh thi cho nhng k hoch ln s c thc hin trong tng lai.
Mt s phn mm m phng:
- Simsci (PRO//II).
- Hyprotech (HYSIM, HYSYS, HTFS, STX/ACX, BDK).
- Bryan research & engineering (PROSIM, TSWEET).
- Winsim (DESIGN II for Windows).
- IDEAS Simulation.
- Simulator 42.
- RSI.
- Chemstations.
4.3.1. Gii thiu v phn mm Hysys
Hysys l phn mm chuyn dng dng tnh ton v m phng cng ngh
c dng cho ch bin du v kh, trong cc qu trnh x l v ch bin kh c
s dng nhiu nht.
Hysys chy trn Windows l phin bn mi ca Hysim, phn mm ny trc
y dng trn h iu hnh MS.Dos.
Hysys l sn phm ca cng ty Hyprotech - Canada thuc cng ty AEA
Technologie Engineering Software - Hyprotech Ltd. L mt phn mm c kh nng
tnh ton a dng, cho kt qu c chnh xc cao, ng thi cung cp nhiu thut
ton s dng, tr gip trong qu trnh tnh ton cng ngh, kho st cc thng s trong
qu trnh thit k nh my ch bin kh. Ngoi th vin c sn, Hysys cho php ngi
s dng to cc th vin ring rt thun tin cho vic s dng. Ngoi ra Hysys cn c
kh nng t ng tnh ton cc thng s cn li nu thit lp thng tin. y chnh l
im mnh ca Hysys gip ngi s dng trnh nhng sai st v ng thi c th s
dng nhng d liu ban u khc nhau.
Hysys c thit k s dng cho hai trng thi m phng:

Steady Mode: Trng thi tnh, s dng thit k cng ngh cho mt qu

trnh.

Dynamic Mode: Trng thi ng, m phng thit b hay quy trnh
trng thi ang vn hnh lin tc, kho st s thay i cc p ng ca h thng theo
s thay i ca mt vi thng s.

4.3.2. Cc bc m phng s cng ngh sn xut Polypropylene

4.3.2.1.

Xy dng m hnh, iu kin phn ng

Xy dng mt qu trnh m phng mi bng cch kch chut vo New. Kch

chut vo nt Add trong hp thoi Simulation Basis Manager m ra hp thoi Fluid
Pacakge chn m hnh nhit ng l: UNIQUAC Peng Robinson

Hnh 19 :

Chn m hnh nhit ng cho qu trnh

Trong phn Components ta chn cc cu t cho trong qu trnh.

Hnh 20 : Chn cu t trong th vin Hysys cho qu trnh

Ring i vi cu t Polypropylene, trong th vin Hysys khng c, do vy ta
phi xy dng mt cu t gi. Cc bc lm nh sau:
Chn Hypothetical, click vo Quick Create A Solid Hypov t tn l PP.
Double Click vo PP, a vo mt s d liu cn thit nh: Khi lng phn t, khi
lng ring, %C, %H, nhit phn ng. Sau Click Estimate Unknown Props
Hysys t ng tm nhng d liu cn li

Hnh 21 : Xy dng cu t gi cho qu trnh

Hnh 22 :

Qu trnh xy dng cu t gi PP

Trong phn Rxns, Add cc cu t phn ng v phng trnh phn ng bng

cch click chn Simulation Basis Mgr, xut hin phn Reactions (nhng phng
trnh phn ng) trong hp thoi Simulation Basis Manager, sau click vo Add
comps chn cc cu t tham gia trong phng trnh phn ng ho hc bng cch
click chut vo Add This Group of Component, tip tc chn nt Add Rxn xc
lp loi phng trnh phn ng xy ra trong thit b, y chn phng trnh phn
ng dng chuyn ho (Conversion) v chn Add reaction xut hp thoi Conversion
Reaction: Rxn 1, sau chn cc cu t tham gia trong phng trnh phn ng v
nhp cc h s t lng (Stoich Coeffs) ca phng trnh phn ng. Trong phn Basis
chn cu t Hydrogen ( chuyn ho theo Hydrogen). Xong ng tt c cc hp hi
thoi, click vo Enter Simulation Environment (vo mi trng m phng) trong
hp hi thoi Simulation Basis Manager.

Hnh 23 :

Xy dng phng trnh phn ng cho qu trnh

Hnh 24 : Xc nh cu t v h s t lng cho phn ng

Hnh 25 :

Xc nh chuyn ha ca phn ng

Trn thanh cng c Case (Main) chn dng vt cht Material Stream (Hnh
mi tn mu xanh). Click vo hnh mi tn gi chut v ko t trn nn cn xy
dng, Double click vo hnh mi tn va xy dng nhp cc thng s cho dng
nh: Tn dng, nhit , p sut, lu lng ca dng trong phn Conditions.

Hnh 26 :

Xc lp nhit , p sut, lu lng cho dng

Hnh 27 : Xc lp thnh phn cho tng cu t trong dng

Trong phn composition ta nhp thnh phn ( phn mol hoc phn khi lng )
ca cc cu t trong dng nguyn liu. Khi dng chuyn sang mu xanh m l
thc hin ng qu trnh.
Cc dng vt cht cho Hydrogen v Xc tc cng c xy dng tng t.
4.3.2.2. Xy dng thit b phn ng
Trn thanh cng c Case (Main) Click vo Conversion Reaction. Double
click vo thit b nhp tn cho dng nguyn liu vo, dng sn phm ra, dng nhit
- trong phn Connections
Conversion
Reaction

Hnh 28 :
cho TBP

Xy dng cc dng vo ra v cc thuc tnh

Trong phn Parameters xc nh cc iu kin, thng s hot ng ca thp

nh s pha, tn tht p sut, th tch thit b, cung cp nhit hay lm lnh

Hnh 29 :

Xc lp cc iu kin v thng s cho TBP

Tip theo, Click vo Reactions, xc lp loi phn ng v phng

trnh phn ng xy ra trong thit b.

Hnh 30 : Xc lp cc iu kin phn ng xy ra trong TBP

Trong phn Rating, xc lp thit b loi hnh cu hay tr, kiu ng hay nm
ngang (hnh 3.13)
n y, v c bn thit lp c cc iu kin cng nh thng s k thut
cn thit cho mt thit b phn ng. Trong s cng ngh Spheripol, c ba thit b
phn ng v cc bc thc hin tng t nhau.

Hnh 31 : Chn loi trong TBP chuyn ho

4.3.2.3.

Xy dng cc thit b tch loi

Trong s cng ngh Hypol II thit b tch dng kh ra khi sn phm

Polypropylene (HPS) l thit b lc dng ti. Kh thu c phn nh a i thu hi
Propylene tun hon li qu trnh. Sn phm thu c y.
Trn thanh cng c Case (Main) Click vo Solid Ops Baghouse Filter.
Double click vo thit b nhp tn cho dng nguyn liu vo, dng sn phm ra, trong phn Connections ( hnh 3.14); Trong phn Parameters nhp tn tht p sut cho
cc ti ( hnh )
Baghouse Filter

Hnh 32 :
cho thit b tch

Xy dng cc dng vo ra v cc thuc tnh

Hnh 33 :

Xc lp tn tht p sut trong cc ti

Sau khi thc hin xong cc thao tc xy dng trn, ta c mt s m phng

chung cho dy chuyn sn xut ca phn xng Polypropylene nh hnh sau

Hnh 34 :
TNG QUAN S M PHNG DY
CHUYN SN XUT POLYPROPYLENE THEO CNG NGH
Hypol II
4.3.3. Kt qu thu c t qu trnh m phng
Sau khi chy m phng, thu c kt qu cn bng vt cht ca qu trnh nh
sau:

Bng 11 :

Cn bng vt cht ca cc thit b

Thit b PreR
Vo (kg/h)

Ra(kg/h)

Propylen

5029

4778

Hydro

0,05

Catalyst

0,77

0,77

Propan ln trong Propylen

25,28

25,28

Metan ln trong H2

1,44.10-4

1,44.10-4

N2 ln trong H2

9,6.10-5

9,6.10-5

PP

251,6

Tng

5056

5056

Thit b R1
Vo (kg/h)

Ra (kg/h)

Propylen

11614

5799

Hydro

0.066

Catalyst

0,77

0,77

Propan ln trong Propylen

59,68

59.68

Metan ln trong H2

3,44.10-4

3,44.10-4

N2 ln trong H2

2,26.10-4

2,26.10-4

PP

252

6066

Tng

11926

11926

Thit b R2
Vo (kg/h)
Propylen

Ra(kg/h)

31237

18647

0,24373

Catalyst

0,77

0,77

Propan ln trong Propylen

187,5

187,5

Metan ln trong H2

1,074.10-3

1,074.10-3

N2 ln trong H2

7,16.10-4

7,16.10-4

PP

6066

18656

Tng

37491

37491

Hydro

Thit b tch PP
Ra(kg/h)
Vo (kg/h)

nh( kg/h)

y(kg/h)

Propylen

18647

18647

Hydro

Catalyst

0,77

0,77

Propan ln trong Propylen

187,5

187,5

Metan ln trong H2

7,16.10-4

7,16.10-4

N2 ln trong H2

7,16.10-4

7,16.10-4

PP

18656

18656

Tng

37491

18835

18656

Bng 12 :

Bng tng kt cc dng vo ra ca qu trnh m phng

Nhit

Lu

sut

lng

(oC)

(bar)

(kg/h)

Propylene

26

25

Hydrogen

26

Xc tc

Nhit lng

Phn

(kJ/h)

hi

18750

3,931.106

49,03

0,359

4,318

10

25

0,778

-3307

Polypropylene

84,35

34,28

1866

-1,225.108

Propylene hi lu

84,35

34,28

1884

8793.106

Nc lm mt thit b preRvo

13,33

1,5

1,959.106

-3,108.1010

Nc lm mt thit b R1 vo

26

1,5

8,275.104

-3,127.108

Nc lm mt thit b R2 vo

26

1,5

3,176.105

-5,021.109

H2O lm lnh Pro vo tb trn

2200

-3,497.107

Hi H2O gia nhit Pro vo R1

151

2,7

293

-3,849.106

Hi H2O gia nhit Pro vo R2

151

2,7

730

9,598.106

Hi nc ha hi Pro

151

2,7

2400

-3,155.107

CHNG 5
TNH TON CC THIT B CHNH
5.1. TNH TON KCH THC CHO THIT B CHNH
5.1.1. Cc thit b phn ng
Trong Hysys khng h tr vic t ng tnh ton th tch thit b phn ng khi
m phng trng thi tnh (vi thp chng ct th c) m ch h tr vic tnh ton cc
gi tr cn li nh ng knh, b dy v thit b,khi xc lp mt gi tr th tch
no .
Theo tnh cht ca qu trnh nh: Phn ng pha lng, xc tc c ho trn
trong dng vt cht, cho nn khi tnh ton gi tr kch thc cc thit b phn ng phi
thng qua cc gi tr nh: Lu lng th tch thc (F v) v thi gian lu (TR) ca lu
cht trong thit b phn ng.
Cc gi tr t Hysys nh sau:
TBP
Fv (m3/h)

preR

R1

R2

9,75

2299

75,97

Theo yu cu cng ngh, cc thit b phn ng PreR, R1, R2 c thi gian lu

ln lt l 6, 1.25h, 0.75h.
Vy th tch hot ng ca cc thit b phn ng l:
V (m3) = Fv* TR
TBP

preR

R1

R2

V (m3)

0,975

28,74

56,976

5.1.2. Thit b tch loi

i vi thit b loi kh Propylen v rn Polypropylen vi lu lng 246.4
(m3/h) th Hysic c th tnh ton c tt c cc thng s v kch thc thit b.
5.1.3. Kt qu thu c t m phng
Sau khi ta tnh ton c cc gi tr th tch ca cc thit b ni trn. Tin hnh
chy Hysys hiu chnh cc kch thc trn mang tnh kinh t hn v cc kch thc
v bm, thit b trao i nhit cng c xc lp. Ta c kt qu sau:

TBP

preR

R1

R2

V (m3)

0,975

28,74

56,976

ng knh (m)

0,939

2,9

3,643

Chiu cao (m)

1,408

4,35

5,465

i vi thit b tch loi vi lu lng 246.4 (m3/h) ta c kt qu nh sau:

Thit b tch PP
Thi gian lu (h)

25.74

S ngn

Din tch 1 ngn (m2)

14,2

Tng din tch (m2)

14,2

ng kch ht (mm)

Din tch ti (m2 )

1,48

ng knh ti (m)

0,3

S ti / ngn

78

Tc dng kh(m/s)

0,005

Bc ti(m)

0,02

5.2. CC THIT B PH KHC

Cc my bm
C 3 my bm k hiu ln lt P-100, P-101, dng bm dng Propylene
nguyn liu, v xc tc.Vi tng p qua cc bm l 11 bar. Khi chy Hysic ta thu
c cc thng s k thut ca bm nh sau.
Thit b

P-100

P-101

Nng sut (m3/s)

73,4

38,5.10-5

p sut ton phn (m)

219,8

55,56

Cng sut ton phn (kcal/h)

2573

0,135

Hiu sut bm ( %)

75

75

Tc quay ca bm(rpm)

1800

1800

NPSH

279

126

Thit b trao i nhit

Thit b trao i nhit E-01 lm lnh dng propylene trc khi vo thit
b trn xc tc trc khi vo thit b tin phn ng (PreR);

Thit b trao i nhit E-02, gia nht dng propylen trc khi i vo thit
b phn ng th nht ( R1 );

Thit b trao i nhit E-03, gia nhit dng propylene trc khi vo thit
b phn ng th hai ( R2 )

Thit b trao i nhit E-04, ha hi propylene lng cha phn ng trc

khi vo thit b tch;
Khi tin hnh m phng ta bit c lu lng ca dng nc lm lnh v lm
nng dng propylene qua cc thit b trao i nhit E-01, E-02, E-03, E-04 ln lt l
2200 (kg/h), 292.7(kg/h), 730(kg/h), 134720(kg/h). Ta tin hnh thit k tnh ton
cc thng s thit b trao i nhit nh sau:
Trn thanh cng c Case (Main) Click vo Heat exchanger. Double click vo
thit b nhp tn cho dng nguyn liu vo, dng sn phm ra, dng nhit - trong
phn Connections.
Dng vt cht i trong ng l dng Propylen, dng i ngoi ng l dng nc
gia nhit (Chn dng vt cht i trong ng hay ngoi ng ph thuc nhiu yu t: nhit
, loi lu cht Nhng thng thng dng i trong ng l dng lnh, dng i ngoi
ng l dng nng).

Hnh 35 : Xy dng thit b trao i nhit

Trong phn Parameters chn cch thc trao i nhit (Heat Exchanger
Model )l trong phm vi m phng tnh (Steady state rating). Nhp tn tht p sut
cho dng i trong ng v ngoi ng.

Hnh 36 : Xc lp tn tht p sut trong thit b trao i nhit

Trong phn Worksheet nhp lu lng hi thp p trao i nhit.

Hnh 37 : Xc lp lu lng hi thp p

Ta hon tt vic nhp thng s cho thit b trao i nhit. Hysic t tnh cc
thng s kch thc thit b. Tng t ta thit k cc thit b trao i nhit cn li.
Bng 13 :
Thit b

Thng s kch thc thit b.

E - 01

E - 02

Loi ( TEMA)

E - 03

E- 04

AES

ng knh v thit b, mm

197

796

2554

1091

S ng

30

160

480

320

B tr ng

Kiu tam gic

ng knh ngoi ng, mm

18

20

24

20

ng knh trong ca ng,

mm

14

16

18

16

Chiu di ng, m

B mt trao i nhit (m2)

10

60

217

80

S pass ng

Bc ng, mm

20

50

100

50

Tn tht p ngoi ng, KPa

200

200

500

500

Tn tht p trong ng

300

400

2000

3000

CHNG 6
XY DNG H THNG IU KHIN
CA QU TRNH[31]
6.1. TNG QUAN V H THNG IU KHIN
Trong ngnh iu khin t ng c hai loi chnh l iu khin c kh nng
ng hoc m (discrete control) v iu khin qu trnh (process control).
6.1.1. Cc nguyn tc c bn ca qu trnh iu khin
6.1.1.1. iu khin ng m
iu khin ng m l h thng iu khin t ng thng c s dng cho
cc nh my lp rp. Trong ngnh cng nghip ho hc ni chung cng nh trong
ngnh cng ngh lc du v ch bin kh ni ring, iu khin ng m tuy khng ph
bin nhng cng l khng th thiu v c vai tr quan trng, c bit trong cc ng
dng start up, shutdown, an ton nh my.
Nhng u vo, u ra ca loi iu khin ny ch mt trong hai trng thi
ng hay m (on hay off). Phng php iu khin ca loi ny l logic, vi cng OR,
AND, NAND vv....Cch y 40 nm b iu khin ca loi ny l mt h thng rle
v rle thi gian t trong t bng. Vi s pht trin ca ngnh in t, b iu khin
c kh nng lp trnh PLC (Programmable Logic Control) ra i lm cho h thng rle
tr nn li thi.
6.1.1.2.

iu khin qu trnh

Trong cc nh my lc du, ho du, ch bin kh, ngi ta s dng ch yu

loi iu khin ny. Qu trnh sn xut l lin tc, cc thng s iu khin bao gm
nhit , p sut, mc cht lng, lu lng, pH, nng vv...
Thit b u vo thng l t cc b chuyn i tn hiu cho ra tn hiu tng t
dng chun nh 4-20 mA hoc 3-15 psig. Thit b u ra thng thng l cc van iu
khin. Phng php iu khin thng l thut ton iu khin t l (Proportional),
tch phn (Integral) v vi phn (Differential) vit tt l PID. [3]
6.1.2. H thng iu khin phn tn DCS trong cc nh my hin i
Do t th c nhiu phn xng nm phn tn trong mt din tch ln v c rt
nhiu u vo v u ra ng vi tng phn xng nn hu ht cc nh my lc du
hin nay u s dng h thng iu khin phn tn DCS (Distributed Control System).
H thng c cu thnh bi nhiu h thng nh hn nm phn tn mi phn xng,
mi h thng nh ny c nhim v m bo qu trnh iu khin phn xng m n
m nhim, n chu s qun l ca cc h thng ch bn trn, c th nhn hoc cung
cp tn hiu vi cc h thng ch. Bn thn cc h thng phn tn ny s qun l trc
tip cc thit b ti hin trng nh van, cm bin, m t...
Tp hp tt c cc d liu t cc h thng phn tn tng phn xng s c
gi ln cc h thng cp cao hn, cc h thng ny thng c tp trung phng

iu khin trung tm ca nh my, ni m cc k s vn hnh v nh qun l trc tip

a ra nhng quyt nh v ch hot ng ca nh my.
Ra i t gia nhng nm 70, h thng iu khin phn tn DCS mang n
mt cuc cch mng thc s cho phng iu khin trung tm ca cc nh my lc du
bng cch s ho nhng vng iu khin v biu din thng tin ca qu trnh ln mn
hnh iu khin.

Hnh 38 :

M hnh h thng iu khin DCS

Nhng li th m DCS mang li c th k ra nh

m bo an ton cao trong qu trnh hot ng.

Lu tr cc thng tin trong qu trnh hot ng phc v cho cng tc

thng k, nghin cu, hoch nh chin lc.

Cung cp ci nhn tng qut nht v hot ng ca nh my.

Cc module tnh ton cho php trin khai cc chin lc iu khin

nhm mc ch ti u hiu qu cng ngh v hiu qu kinh t.

Giao din thn thin vi ngi vn hnh bng ngn ng v hnh nh...

6.1.3.B IU KHIN PID

6.1.3.1.

Vai tr ca b iu khin PID

Tn gi PID l ch vit tt ca ba thnh phn gm khu khuych i P

(Proportional), khu tch phn I (Integral) v khu vi phn D (Differential).
S hot ng ca khu PID nh sau:

Hnh 39 :

S hot ng ca khu PID

B iu khin PID c s dng kh rng ri iu khin i tng

theo nguyn l hi tip, c bit l trong ngnh cng nghip qu trnh, trong ni bt
nht l lnh vc du kh. L do b iu khin ny c s dng rng ri l tnh n
gin v cu trc ca n ln nguyn l lm vic. B iu khin PID c nhim v a sai
lch e(t) gia gi tr t SP v gi tr thc t PV v khng sao cho qu trnh qu
tho mn cc yu cu c bn v cht lng.
B iu kin PID c m t bng m hnh vo ra theo phng trnh sau
1
u(t) = kp[ e(t) + T
i

e(t )dt + Td
0

de(t )
]
dt

Trong
Kp l h s khuych i, t trng cho khu t l.
Ti l hng s tch phn, t trng cho khu tch phn.
Td l hng s vi phn, t trng cho khu vi phn.
y l ba thng s t trng cho b iu khin PID.
Cht lng h thng ph thuc vo ba thng s ny. Mun c h thng c cht
lng nh mong mun th phi phn tch i tng ri trn c s chn cc thng s
Kp, Ti, Td cho ph hp
6.1.4. La chn khu tc ng v cc thng s t trng cho PID
Nhim v ca vic thit k b iu khin PID cho mt qu trnh c th l

La chn khu tc ng

Tnh ton cc thng s t trng cho tng khu

Khng phi bao gi cng dng c ba khu ny trong mt vng iu khin.

Thng thng tc ng P + I c dng iu khin cc thng s thay i
nhanh nh iu khin mc, iu khin p sut, iu khin lu lng.
Tc ng P+I +D c dng iu khin cc thng s thay i chm nh iu
khin nhit , iu khin pH, iu khin nng .
Vic la chn cc thng s t trng cho mi khu thng thng c cn c
vo hm truyn ca qu trnh.

Ngy nay c mt s b iu khin hin i c th t ng la chn cc khu

iu khin v k c vic thit t cc thng s t trng cho tng khu.
Bng sau trnh by kinh nghim la chn khu iu kin v cc thng s c
trng cho mi khu ng vi tng qu trnh c th ng dng trong m phng ng ca
phn mm HysysDynamic
Bng 14 :

Khong kinh nghim cc khu ca PID[32]

Qa trnh

Kp

Ti (pht)

Td (pht)
0-5

iu khin nhit

2-10

2-10

iu khin p sut

2-10

2-10

Khng s dng

iu khin mc (khu P)

Khng s dng

Khng s dng

iu khin mc (khu PI)

2-10

1-5

Khng s dng

0.4-0.65

0.05-0.25

Khng s dng

iu khin lu lng

Trn y l bn qu trnh iu khin c bn, tt c cc vng iu khin trong

thc t u l s cu thnh ca cc thnh phn trn. Khu PID rt t c s dng
trong thc t iu khin qu trnh, hu ht tt c cc qu trnh u c th iu khin
c bng khu PI nu la chn ng cc thng s t trng.
6.1.5. H thng iu khin trong nh my sn xut POLYPROPYLEN
H thng iu khin ca nh my rt phc tp. Gm c cc b iu khin nhit
, p sut, nng , khi lng ring, lu lngC th biu din theo s sau.

Hnh 40 : S h thng iu khin trong nh my sn xut PP

6.1.5.1.

B iu khin lu lng : Gm cc thit b iu khin lu lng :

Dng nguyn liu Propylen
Dng nguyn liu hydro
Dng Xc tc
Cc dng Propylen vo cc thit b trao i nhit.
Dng nc lm lnh, nc gia nhit.

6.1.5.2. B iu khin nhit

Gm cc thit b iu khin :
Nhit cc dng Propylen ra khi thit b trao i nhit.
Nhit cc thit b phn ng
Nhit dng Polypropylen Propylen ra khi thit b ha hi
Propylen.
6.1.5.3. B iu khin nng
Thit b iu khin nng hydro trong dng Propylen.

iu khin nng Propylen trong thit b phn ng thng qua iu

khin chuyn ha ca phn ng ( thc t iu khin khi lng ring ca h nh
tng ca cc thit b phn ng )
6.1.5.4. B iu khin mc
Thit b iu khin mc PP trong thit b tch.
Thit b iu khin tc dng kh Propylen ra khi thit b
6.2. PHNG PHP IU KHIN MT S THNG S DNG VT CHT
BNG HYSIS
( y ta ch ly mt v d v cch iu khin cc thng s dng vt cht qua
thit b trao i nhit )
C th ta xt qu trnh v phng php iu khin nhit dng Propylen ra
khi thit b trao i nhit trc khi vo thit b phn ng th hai ( R2 )
Gm c cc bc sau :
6.2.1. Tin hnh v hon tt m phng tnh qu trnh trao i nhit ca dng
Propylen :

Hnh 41 : Thit b trao i nhit

6.2.2. Xy dng h thng iu khin PID cho thit b :
Gm c cc thit b iu khin nh sau :
FIC-100 : Thit b iu khin lu lng hi thp p vo thit b trao i
nhit thng qua m van VLV-101.
FIC-101 : Thit b iu khin lu lng dng Propylen vo thit b trao i
nhit thng qua iu khin m van VLV-100.

 TIC-100 : Thit b iu khin nhit dng Propylen ra khi thit b trao

i nhit thng qua iu khin m van VLV-101.

Hnh 42 : H thng iu khin thit b trao i nhit

Cch thc thit lp mt thit b iu khin:
Trn thanh cng c Case (Main) Click vo Control Ops PID Controller.
Double click vo thit b nhp cc thng s iu khin.

Hnh 43 : Xy dng h thng iu khin

Trong phn Connections ti mc Process Variable Source chn bin iu
khin l nhit dng PRO11 nh sau

Hnh 44 : Xc lp bin iu khin

Ti mc Output Target Object chn i tng thay i (l m van VLV102).
Trong phn Parameters in cc thng s Kc, Ti, Td, khong gi tr nhit ti
thiu, ti a.
Tng t ta thit lp cc thit b iu khin cn li FIC-100, FIC-101. Sau khi
xy dng h thng cc thit b iu khin ta kch chut vo nt Dynamics Assistant
trn thanh cng c v chn Make Change Finish.
Sau vo Tool Chn Databook (hoc Ctrl D), Ti mc Variables insert
cc dng vt cht nh sau :

Hnh 45 : Qu trnh iu khin

Ti mc Strip Chats ta nh du tick vo cc mc chn v kch vo Strip
Charts hin th ng biu din s thay i nhit , lu lng khi cc bin cn
li thay i.
Cui cng kch vo nt Intergrator active trn thanh cng c (hoc vo
Simulation Intergrator) chuyn qua trng thi m phng ng. Ta xem nh
hon tt vic m phng ng ca mt thit b. Tng t ta c th m phng ng s
thay i cc thng s ca tt c cc thit b cn li.

Hnh 46 : H thng iu khin thit b trao i nhit

Tng t ta c th tin hnh m phng ng xy dng h thng iu khin
cc thit b cn li. V s liu cn cha chnh xc so vi thc t nn cha th m
phng ng ton b nh my cng mt lc m ch c th xy dng h thng iu khin
ca tng thit b v tng khu vc trong nh my.

Ti liu tham kho ca Chng I

[1] http://UOP.com/products/UOP Propylene Recovery Unit.
Th Ngha, Tnh hnh v trin vng pht trin ngnh Ha du trn th gii, Tp
Ch Cng Nghip Ho Cht, s 08 2003, [http://www.vinachem.com.vn/.
[2] http://www.airliquide.com/en/business/products/Propylene.
[3] http://en.wikipedia.org/wiki/Propylene.
[4] Ngi dch Nguyn c Chung, Ho Hc Hu C Hin i. NXB Khoa hc v
K thut, 1981.
GS.TS. Phan Minh Tn, Tng hp hu c v Ho du, tp I. NXB - HQG
TP.H Ch Minh.
[5] Handbook-Propylene Polymers.pdf.
[6] http://www.airliquide.com/en/business/products/Hydrogen.
[7], [ 8 ], [ 9 ] Hong Nhm, Ho hc v c, tp I. Nh xut bn Gio dc, 2000.
[10] Handbook-Propylene Polymers.
[11], [12] http://en.wikipedia.org/wiki/Polypropylene.
[13] Jean Maire BCHET Polypropylnes.
[14] http://www.pslc.ws/mactest/pp.htm.
[15] Jean Maire BCHET Polypropylnes.
[16] http://www.polysurfacesbookstore.com/keyword/id=Polypropylene.
[17], [18], [19], [20]

Handbook-Propylene Polymers.pdf.

[21] Ngi dch Phm Duy Phc Cng ngh sn xut polypropylene v qui trnh vn
hnh nh my- Trng cao ng dy ngh Vng Tu.
[22] Handbook-Propylene Polymers.pdf.

[23] Chng 4-Ti liu nghin cu tin kh thi d n xy dng phn xng
Polypropylene ca PetroVietnam.
[24] Jean Maire BCHET Polypropylnes.
[25], [26], [27], [28], [29] Chng 4-Ti liu nghin cu tin kh thi d n xy dng
phn xng Polypropylene ca PetroVietnam.
[30] Ti liu tham kho ca phn mm Hysys
http://www.simsci.com/
http://www.hyprotech.com/
http://www.ideas-simulation.com/
[31] Tng quan v h thng iu khin trong nh my lc du ca Nguyn nh Lm.
[32] Ti liu tham kho ca phn mm Hysys (Hysys v2.4.1.3870 Add. Ons /training /
PDFs/training /Current /DS+PC7).

KT LUN
Qua gn bn thng tm hiu, phn tch v tin hnh m phng, n nay ti
hon thnh nhim v n c giao vi ti Tng quan cng ngh v thit k
m phng phn xng sn xut Polypropylene ca nh my lc du Dung Qut
bng phn mm Hysic.

Nhn chung ti ny gii quyt c mt s vn sau.

Tng quan cc cng ngh sn xut Polypropylene.

So snh, la chn v ngh quy trnh cng ngh thch hp.

Nm bt c cc Phng php tip cn v s dng phn mm Hysys trong

m phng cng ngh sn xut, c bit l m phng thit b phn ng v cc cu t
gi.

Tnh ton, thit k cc thng s k thut ca cc thit b trong phn xng.

Xy dng h thng iu khin v iu khin cc thng s ca cc dng vt

cht v cc thit b.

Nhng hn ch ca ti:
ti cn mi m v bn thn cn thiu nhiu kin thc thc t.

Cc s liu cha thc t do Vit Nam cha c Nh my sn xut

Polypropylen.
V s liu cn cha chnh xc so vi thc t nn cha th m phng ng
ton b nh my cng mt lc
Cc thit b trong Hysic tnh ton khng st vi thc t. Do chnh xc
khng cao.

Hng pht trin ca ti

Tnh thit k mt bng, cc cng trnh ph tr v tnh kinh t cho ton nh

my.
Pht trin m phng cho h nhiu monomer (comonomer), m rng cho cc
qu trnh trng hp khc.

M phng ng cng lc ton b phn xng khi cc thng s thay i.

Ti u ho thit k qu trnh sn xut cc polymer t cc olefine.

Tuy nhin do thi gian c hn v kh nng cn hn ch nn trong n ny em

cha tm hiu k ht cc ng dng ca phm mm Hysys, cha tm hiu c quy
trnh cng ngh ca xng ph tr cng nh cha tnh ton cc thng s vn hnh ti
u, cha tnh thit k cho tt c cc thit b ca s m phng xng sn xut
Polypropylen.
Vic hon thnh n tt nghip gip em n li nhiu kin thc m thy c
truyn t. Tip cn v tm hiu phn mm mi gip em tch ly c nhiu k
nng trong vic s dng phn mm m phng v tnh ton cng ngh ca qu trnh.
Qua n ny em thy rng phn mm Hysys l phn mm c ng dng rt
quan trng trong lnh vc du kh, thng qua n ngi m phng nh cm thy ang
lm vic vi cc thit b trong thc t.
Tuy nhin. khi i vo thc t cng vic ny l mt cng trnh s, nm
ngoi phm vi n tt nghip. Hn na, do hn ch v kin thc v thi gian, nn
n ca em khng trnh khi nhng sai st. Knh mong nhn c s ph bnh, gp
ca qu thy c v cc bn ti ngy cng c hon thin.
Em xin chn thnh cm n qu thy c trong Trng, Khoa Ho, Ngnh
Cng ngh Ha hc - Du v Kh ca Trng HBK- H Nng, c bit l Thy
TS. Nguyn nh Lm dnh nhiu thi gian hng dn tn tnh, gip em thc hin
v hon thnh n tt nghip ny.