B mn lc- ha du

Bi ging:

Cng ngh Ha du

Ti liu tham kho

1. P.Wiseman.B.Sc. Petrochemicals. Ellis Horwood Limited, 1986. 2. Alain Chauvel, Gilles Lefebvere. Petrochemical Processes 1. Gulf Publishing Company, 1989. 3. Alain Chauvel, Gilles Lefebvere. Petrochemical Processes 2. Gulf Publishing Company, 1989.

CHNG 1: M U 1.1. Cc sn phm ha du l g?

Cng ngh lc du v ch bin kh

Mt s sn phm

Cng ngh ha du

Cc hp cht hu c (95%)
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S pht trin ca cng nghip ho du.

Ngnh cng nghip ho du bt u t nm 1920 Sn xut isopropyl ancol t propylen (cng ty du m ca M) Nm 1923 mt nh my ho du u tin ra i sn xut cc dn xut ca etylen

Nhng nm 1960 ngnh cng nghip ny pht trin hu khp cc nc pht trin.

Nguyn liu cho cng nghip ho du

Thnh phn ca du m ch yu cha h ca ba hydrocacbon l ankan, xycloankan v aromatic. Trong cng nghip du m cc ankan gm ankan mch thng v nhnh c gi chung l cc parafin, cc xycloankan c gi l cc naphten ch yu l cc vng 5, 6 cnh, cc hp cht cha vng thm t bezen tr ln c gi l aromatic. Kh t nhin bao gm kh khai khc t m kh t nhin v kh du m.

Cc nguyn liu cho ho du c sn xut t qu trnh lc du bao gm:

- Kh (t phn on kh) c th tch ra cc kh C2H4, C3H6, C4H8, kh tng hp v H2. - Xng, Naphta sn xut hp cht thm. - Du ho sn xut parafin.

* S khi m t cc sn phm chnh trong lnh vc ho du vi nguyn liu l du th:

etylenglycol
NH3

DEG, TEG
DEA, TEA

O2, XT

E.O

Etanolamin O2, XT

Bt git Axit axetic

Axetaldehyt

Anhydricaxetic HCl Phn on kh (chng ct hoc cracking) H2SO4, H2O Cloroetyl Etanol Butadien C6H6, XT Polyme ho P.E Cl2 Dicloetan - HCl Vinyl clorua Etylbezen

Si tng hp

Ph gia cho xng (tetra etyl ch) Dung mi, ph gia cho xng Cao su tng hp -H2 Styren Nha P.S

C2H4

PVC

Oligome ho

Axit bo

O2 Cl2, t

Acrolein Clorua allyl

isopropanol Clorohydrin -H2 O2

ru allylic

nha Thuc n

H2O, xt Phn on kh (chng ct hoc cracking)

Ru isopropanoic

Axeton Axeton

phenol

Bis-phenol Dung mi

Nha

C3H6

C6H6, XT Cumen Dime ho, xt O2, NH3

O2

phenol isopren Nha

Nha Cao su

Iso hexen Acrynltril

Dodexylen

C6H6

Dodexylenbenzensunfonat

Cht ty ra

CO2, H2O - H2

Andehyt Butadien

n- butanol Cao su -H2

cht ho do cao su

H2O, xt Phn on kh (chng ct hoc cracking)

Ru bc hai

Metyletylxeton

Dung mi

C4H8

O2, XT HCHO, xt

Anhydric maleic Dimetylmeta dioxan Cao su

Nha HCHO, xt isopren Cao su

Butadien O2, XT C4H10 Anhydric maleic

Butadiol Butylrolacton

Nha

Polybutyltetraphtalat Axit fumaric Oxi ho Axit axetic Iso butan isobuten MTBE Axit maleic

Cc dn xut cha oxi Kh tng hp v H2

Glycol

Cht chng bng

N2

NH3

Ur

Phn m

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H2 Benzen Cl2, xt O2, xt C2H4 C3H6 Phn on Naphta

Xyclo hexan

O2

Caprolatam NaOH

Nilon

Clorobenzen Anhydric maleic Etylbenzen isopropylbenzen

phenol Nha

Nha

Styren phenol

Nha PS Axeton Nha cht ty ra

Dodexylbenzen HNO3 O2, xt Nitrobenzen Anhydrit phtalic

Dodexylbenzensunfonat Anilin Nha Dimetyl tetraphtalic cht mu

O2, xt Anhydrit tetraphtalic Toluen Nitrat ho TNT Axit benzoic p-xylen Axit tetraphtalic

Nha

E.G

PET Butadiol PBT Phenyldiamin

Xylen

o-xylen

Oxi ho Anhydrit phtalic

Polyamit Nha andehyt Nha polyeste khng no

DEG

DOP Polyuretan

11

m-xylen

Axit isophtalic

copolyeste

H2 Phn on du ho n-parafin -H2O

Du nhn n- olefin cht ho do

Cl2

Cloparafin

ankylbenzen

cht ty ra

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Tnh hnh pht trin ngnh cng nghip ho du Vit Nam (d kin n 2020). * Phn m (Ur): - Nh my m Ph M (cng sut 740.000 tn/nm) sn xut phn m t kh ng hnh v kh t nhin - Nh my m C Mau vi cng sut d kin 800.000tn /nm sn xut m t ngun nguyn liu kh Ty Nam. * Nha: - Nh my nha PP k hoch s c xy ti Dung Qut vi cng sut 150.000 tn/nm. Nh my PP xy ti khu lin hp LHD Nghi Sn vi cng sut 300.000 tn/nm. - Nh my PE d kin c xy dng trong t hp ho du pha Nam vi cng sut 500.000 tn/nm. - Nh my PVC c mt nh my sn xut PVC ca Petronas. - Nha PS d kin s xy dng vi cng sut 290.000 tn/nm.

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* X si tng hp (PET):PVN ang hp tc vi Vinatex trin khai d n. * Cc sn phm t hp cht thm (BTX): - nh hng cc sn phm ny t Lin hp Lc Ho du Nghi Sn v t hp Ho du pha Nam lm nguyn liu sn xut PET, PS, LAB - Sn xut LAB ( cht ty ra), dung mi cc loi, metanol t kh, mui than (cacbon black).

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Cng ngh
Cc qu trnh lin tc (continuous processing): nguyn liu lin tc c a vo v sn phm lin tc c ly ra. Cng ngh gin on (batch processing) c thc hin theo tng m, thng c s dng trong phng th ngim.

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Chng 2. Sn xut Etylen v cc hp cht t etylen

2.1. Gii thiu chung.
Etylen c s dng nhiu nht trong ngnh tng hp hu c v ho du v:

- Cu to n gin, hot tnh cao. - Tng i r tin. - D sn xut t cc hydrocacbon khc bng qu trnh steam cracking vi hiu sut cao. - Cc phn ng i t nguyn liu etylen to thnh t sn phm ph hn so vi phn ng i t cc olefin khc.
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Tnh cht vt l ca etylen

Cu t

Nhit Nhit Nhit kt tinh si (oC) ti hn (oC) (oC)

Gii hn n trong khng kh ti 0,1 Mpa, 20oC (%TT) Gii di hn Gii trn 2,75 hn

Etylen

-169,15

-103,71

9,90

28,6

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2.2. Sn xut etylen 2.2.1. Nguyn liu

Etan Propan Naphta Gas oil Butan (rt t )

- Cc ngun sn xut etylen khc bao gm: ehydrat ho ru etylic (n , Brazin, Thu in, Trung Quc), cracking cc sn phm thu c t qu trnh kh ho than (Nam Phi) v chuyn ho ru metylic (hng UOP/Mobil-M).
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- Nht v Ty u 71% etylen c sn xut t naphta, 11% t gasoil - M: 52% etylen c sn xut t etan, 22% t gasoil, 5% t naphta, cn li t cc ngun khc

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2.1.2. Phn ng
Cc phn ng cracking th cp * Cracking etan:
CH3CH3 2*CH3 Gc t do va to thnh hp th mt nguyn t H ca etan to gc t do mi *CH + CH CH CH4 + CH3CH2* 3 3 3 CH3CH2* H* + CH2=CH2 (1) Nguyn t H va to thnh kt hp vi mt nguyn t H ca etan: H* + CH3CH3 H2 + CH3CH2* (2) (1) v (2) l phn ng pht trin mch. - Tt mch: H. + CH3CH2* CH3CH3 CH + CH CH * CH3CH2CH3 3 3 2 CH3CH2* + CH3CH2* CH3CH2CH2CH3
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* Cracking propan

CH3CH2CH3 CH3* + *CH2CH3 , gc etyl c th t lin kt H-C v tr nh etan to mt nguyn t H v phn t etylen *C H + CH hoc C H C3H8 + CH3* hoc C2H5* hoc H* 3 7 4 2 6 hoc H2 C3H8 H* + C3H7 CH3CH2CH2* (bn) CH3 *CHCH3 CH3 *CHCH3 CH3* + CH2=CH2

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Cracking Naphta v gas oil

* Cracking cc ankan mch thng:

(cho etylen nhieu nhat)

C9H20 CH3CH2CH2*

C3H7* + C6H13* CH3* + CH2=CH2 CH3CH2CH2CH2* + CH2=CH2 CH3CH2* + CH2=CH2 H* + CH3CH2CH2CH2CH2CH2CH2 *CHCH3
CH3CH2CH2CH2 CH2CH2*+ CH2=CHCH3

Cc gc hnh thnh tip tc b ct lin kt C-C v tr :

CH3CH2CH2CH2CH2CH2* CH3CH2CH2CH2* Hoc C9H20

CH3CH2CH2CH2CH2CH2CH2 *CHCH3

CH3CH2CH2CH2 CH2CH2*

H* + 3CH2=CH2
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* Cracking cc ankan mch nhnh:

CH2CH3 CH3CH2CH2CH CH2CH2CH3 CH2CH3 CH3CH2CH2 CH CH2 *CHCH3 CH3CH2CH2*CH CH2CH3 CH3CH2* CH2=CH2 + H*

CH2CH3 H* + CH3CH2CH2CH CH2 *CHCH3 CH2CH3 CH3CH2CH2 CH* + CH2=CHCH3 CH3CH2* + CH2=CHCH2CH3

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* Cracking cc cycloankan H * H *
*CH 2CH2

CH2 CH2 CH=CH2 CH2=CH2 + *CH2CH2CH=CH2

.CH

2CH2

CH2 CH2 CH=CH2

.CH

2CH2CH=CH2

H* + CH2=CHCH=CH2
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