Bai Giang Cong Nghe Hoa Dau 8128

7/31/2019 Bai Giang Cong Nghe Hoa Dau 8128

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Bi ging:

Cng ngh Ha du

B mn lc- ha du


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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 chthu 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 caetylen

Nhng nm 1960 ngnh cng nghip ny pht trin hu khp cc n-c

pht trin.


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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.


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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:


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etylenglycol

Phn onkh (ch-ngct hoccracking)

C2H4

Polyme ho

Cl2 - HCl

Oligome ho

Dicloetan Vinyl clorua

Axit bo

P.E

Etylbezen Styren Nha P.SC6H6, XT -H2

Butadien Cao su tng hp

Etanol Dung mi, ph gia cho xngH2SO4,H2O

Cloroetyl Ph gia cho xng (tetra etyl ch)HCl

Anhydricaxetic Si tng hp

Axetaldehyt

Bt git

Axit axetic

DEA, TEA

E.ONH3 EtanolaminO2, XT

PVC

O2, XT

DEG, TEG


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Phn on

kh (ch-ngct hoccracking)

C3H6

O2, NH3

Dodexylen DodexylenbenzensunfonatCht ty ra

Acrynltril Nha

Iso hexen isopren Cao su

Cumen phenol Nha

Axeton Dung mi

R-u isopropanoic Axeton Bis-phenol NhaH2O, xt

Clorohydrin Thuc nClorua allyl

Acrolein isopropanol r-u allylic nhaO2

Cl2, t

-H2 phenol

O2

C6H6, XT O2

Dime ho, xt

C6H6


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Phn onkh (ch-ngct hoccracking)

C4H8

Dimetylmeta dioxan isopren Cao su

Anhydric maleic Nha

R-u bc hai Metyletylxeton Dung miH2O, xt

Cao suButadien

Andehyt n- butanol cht ho do cao su- H

2

-H2

O2, XT

HCHO, xt

CO2, H2O

HCHO, xt

Butadien Cao su

C4H10

O2, XT Anhydric maleic Butadiol Nha

Butylrolacton

Polybutyltetraphtalat

Axit fumaric Axit maleic

Oxi ho Axit axetic

Iso butan isobuten MTBE


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Kh tnghp v H2

NH3 Ur Phn m

Cc dn xut cha oxi Glycol Cht chng bng

N2


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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 khng 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 150.000tn/nm. Nh my PP xy ti khu lin hp LHD Nghi Sn vi cng sut300.000 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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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 theotng m, th-ng -c s dng trong phng th ngim.


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Ch-ng 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.

- T-ng 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

Cut

Nhit kt tinh

(o

C)

Nhit si (oC)

Nhit ti hn

(o

C)

Gii hn n trongkhng kh ti 0,1 Mpa,

20o

C (%TT)

Gii hnd-i

Gii hntrn

Etylen -169,15 -103,71 9,90 2,75 28,6


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2.2. Sn xut etylen2.2.1. Nguyn liu

- Etan

- Propan

- Naphta

- Gas oil

- Butan (rt t )

- Cc ngun sn xut etylen khc bao gm: ehydrat ho r-u etylic (n ,

Brazin, Thu in, Trung Quc), cracking cc sn phm thu -c t qu

trnh kh ho than (Nam Phi) v chuyn ho r-u 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 tdo mi*CH3 + CH3CH3 CH4 + CH3CH2

*

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

* CH3CH3CH3 + CH3CH2

* CH3CH2CH3CH3CH2

* + CH3CH2* CH3CH2CH2CH3


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Cracking Naphta v gas oil (cho etylen nhieu nhat)

* Cracking cc ankan mch thng:

C9H20 C3H7* + C6H13

*

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

CH3CH2CH2* CH3

* + CH2=CH2

CH3CH2CH2CH2CH2CH2* CH3CH2CH2CH2

* + CH2=CH2

CH3CH2CH2CH2* CH3CH2

* + CH2=CH2

Hoc C9H20 H* + CH3CH2CH2CH2CH2CH2CH2

*CHCH3

CH3CH2CH2CH2CH2CH2CH2*CHCH3 CH3CH2CH2CH2 CH2CH2*+ CH2=CHCH3

CH3CH2CH2CH2 CH2CH2* H* + 3CH2=CH2


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* Cracking cc ankan mch nhnh:

CH2CH3 CH2CH3

CH3CH2CH2CH CH2CH2CH3 H* + CH3CH2CH2CH CH2

*CHCH3

CH2CH3 CH2CH3

CH3CH2CH2 CH CH2*CHCH3 CH3CH2CH2 CH

* + CH2=CHCH3

CH3CH2CH2*CH CH2CH3 CH3CH2* + CH2=CHCH2CH3

CH3CH2* CH2=CH2 + H

*


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* Cracking cc cycloankan

H .

*

H

* *CH2CH2 CH2 CH2 CH=CH2

.CH2CH2 CH2 CH2 CH=CH2 CH2=CH2 + *CH2CH2CH=CH2

.CH2CH2CH=CH2 H* + CH2=CHCH=CH2


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Biu din s phn b sn phm trong phn ng cracking naphta

C5+

C2H4

H2 v CH4C3H6

C4H8 v C4H10C4H6

khc nghit

Hiu sut (% KL)40

30

20

10


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Sn phm Nguyn liu

Etan Propan Naphta Gas oilH2 3,6 1,3 0,8 0,6

CH4 4,2 24,7 15,3 10,6

C2H2 0,2 0,3 0,7 0,4

C2H4 48,2 34,5 29,8 24,0

C2H6 40,0 4,4 3,8 3,2C3H4 0,3 1,1 1,0

C3H6 1,3 14,0 14,1 14,5

C3H8 10,0 0,3 0,4

1,3-C4H6 4,8 4,7

C4H8 1,6 3,7 4,2 4,5

C4H10 0,3 0,1

Xng cracking 0,9 5,9 21,0 18,4

Du nhin liu - 0,9 3,8 17,6


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b. Thi gian l-u: Thi gian l-u khong t 0,2 1,2 giy.

nh h-ng ca nhit v thi gian l-u n hiu sut to thnh etylen trong

phn ng cracking naphta.


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c. p sut hi ring phn v vai tr ca hi nc.

p sut hi ring phn ca HC gim Tc qu trnh gim

chn

lc tng

* Vai tr ca hi nc ?

* Hn ch ?


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T l hi nc ph thuc vo nguyn liu khc nhau (KLPT ca HC)

Nguyn liu Kg hi n-c/kg hydrocacbon

Etan 0,2-0,4

Propan 0,3-0,5

Naphta 0,4-0,8

Gas oil 0,8-1,0


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Cng ngh cracking hi n-c.

Cng ngh cracking hi n-c bao gm hai b phn chnh:

* B phn phn ng (vng nng): nguyn liu -c nhit phn to thnh

sn phm (phn ng cracking xy ra ti y).

* B phn tch (vng lnh): sn phm -c tch loi v tinh ch.


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S khi qu trnh cracking hi n-c.


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S ch-ng tch kh sn phm ca qu trnh cracking hi n-c Naphta.

1-thp tch metan(30-49 a); 2-thp tch etan(40-50a); 3-thit b hydro ha; 4-thp tch etan-etylen(110-120a); 5-thp tch propan(55-60 a); 6-thp tch propan-propylen(220 a trong 2 thp); 7-thp tchbutan.


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2.2.1.1. Ph-ng php hydrat ho gin tip etylen

* Phn ng v cc iu kin thc hin

a) S hnh thnh etyl axit sunfat bi qu trnh hp th etylen trong axt

sunfuric:

CH2=CH2 + H2SO4 C2H5O-SO3H

2 CH2=CH2 + H2SO4 (C2H5O)2SO2

b) Thu phn este sunfuric to etanol:C2H5O-SO3H hoc (C2H5O)2SO2 + H2O C2H5OH hoc (C2H5)2O + H2SO4


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Giai on u: p sut 20 30 atm, nhit 60-90oC.

Giai on hai: Nhit 100oC.

Hiu sut to etanol khong 90%.

Sn phm ph to thnh l dietyl ete.

Nh-c im: d gy n mn thit b.


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Thit b phnng thy phn


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Cng ngh sn xut etanol bng ph-ng php hydrat ho trc tip etylen

Sn xut Etanol bng ph-ng php hy drat ho trc tip Etylen. Cng ngh Shell

Ch-ngctsnphmn

h

Ethylene

ch-ngngp

h

Secrubbing

Stripping

ethanol

Ethanol 95%

HydroMy nn

tun hon

Hydro

Bnh tch

Kh thi

Process water

lng/khBnh tch

Hi n-c

N-cthi

Cc sn phm nhMake-up

compressor

L gia nhit

TB P

My nn

etylentun hon

Kh thi

N-c

acetaldehyde

Tbhydrohochnlc


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2.2.1.3. Tinh ch etanol khan.

* Ph-ng php c in thu -c etanol c nng 9599,9% l s dng

CaO hp th n-c nh-ng qu trnh ny khng kinh t.

* Ph-ng php ch-ng ng ph: ph-ng php ny -c thc hin vi s c mt

ca benzen p sut d-i 12 kPa s thu -c etanol c nng 95-100%,

tuy nhin ct ct phi c s a kh ln.

* Ph-ng php thm thu qua mng.

* Ph-ng php ry phn t.


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Ph-ng php ch-ng ng ph


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* Cng ngh thm thu qua mng.

Gia nhit 105oC

Cn 94-95%

Etanol99,5%

N-c thm thu qua mng

MngNg-ng t


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Ph-ng php ry phn t.S nguyn tc tch n-c ra khi etanol bng vt liu ry phn t.

H n-c/EtanolRy phn t Etanol

> 99,5%Ry phn t chan-c

Phn t n-c Phn t etanol


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S hp ph n-c bng vt liu ry phn t trong pha hi


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2.3.1. Sn xut polyetylen (PE).2.3.1.1. Gii thiu v PE.

. Polyetylen l mt trong nhng loi nha chu nhit c ng dng rng ri nht vgi thnh khng t, d gia cng nhiu hnh dng khc nhau nh- c th ko

thnh si hay rt thnh mng film mng. V vy PE -c s dng lm ti,

chai nha, ng nha, mng film, tm nha.

Trn th gii l-ng PE -c sn xut rt ln p ng nhu cu ngy cng tng.V d nm 1997, PE -c sn xut xp x 450.000 tn th -c tnh n nm 2015

l-ng PE l 1.350.000 tn, c bit l LLDPE c nhu cu tiu th cao nht.

PE c hai loi: LDPE (low desity PE) c tnh mm do v HDPE (high density

PE) cng, khng linh hot.


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I 2R*

R* + CH2=CH2 RCH2-CH2*

RCH2CH2* + nCH2=CH2 R-(CH2)n-CH2

*

R-(CH2)n-CH2* + R-(CH2)n-CH2

* R-(CH2)2n+1CH2R

R-(CH2)n-CH2CH3 + R-(CH2)n-CH=CH2

LDPE -c to thnh nh phn ng polime ho etylen theo c ch gc.

-Nhit phn ng: 100- 200oC

-p sut cao: 100-135 atm

- Cht khi u th-ng -c s dng l oxy hoc peoxit hu c.

-C ch phn ng nh- sau:


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HDPE -c sn xut s iu kin p sut thp trong thit b phn ng tng si

nh phn ng polime ho c xc tc Ziegler

( l xc tc c cha nhm alkylat v kim loi chuyn tip)

- Phn ng xy ra nhit khong 100oC.

- p sut khong 20 atm

- Phn ng tin hnh trong dung mi tr hexan trong pha kh.

CH3

Cl CH2 C2H5(C2H5)2 TiCl2 + Al(C2H5)2Cl Ti Al

Cl CH2 Cl

CH3


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- C ch phn ng xy ra trn tm kim loi xc tc nh- sau:

Phn ng khng c qu trnh chuyn mch v to ra polime c khi l-ng phn

t rt ln.

CH3 CH3CH2 CH2

Ti Al +Ti AlCH2 CH2

CH2= CH2 CH3-CH2-

+CH2 CH3

CH3 CH3CH2 Al CH2

Ti+ CH2-CH3 Ti AlCH2- CH2 CH2

CH2- CH2- CH3


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Cng ngh sn xut HDPE ca hng Union Carbide Unipol

(1) Thit b phn ng(2) Bm nn li tm mt giai on(3) Thit b trao i nhit(4) Bn cha.


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2.2.3. Sn xut Etylen oxit (EO).

Etylen oxit c t trng d204=0,8697, nhit si 10,7oC.

ng dng: - sn xut etanolamin.

Sn xut etylenglycol.

Cht SAS khng ion.

-c sn xut bng hai ph-ng php:

- Oxi ho gin tip etylen bng clohydrin to hp cht trung gian etylen clohydrin.

- Oxi ho trc tip etylen bng oxi nguyn cht hoc oxi khng kh.2.2.3.1. Ph-ng php oxi ho gin tip.

Phn ng chnh:

CH2=CH2 CH2 - CH2 + HCl

Cl OH100oC Ca(OH)2

CH2- CH2 + CaCl2O

Cl2/H2O

10- 50oC


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2.2.3.2. Ph-ng php oxi ho trc tip.

* Phn ng:

C ch thc hin phn ng trn xc tc kim loi:

CH2=CH2 + 1/2O2 CH2 - CH2 Ho

298=-105 kJ/molO

CH2=CH2 + 3O2 2CO2 + 2H2O Ho

298=- 135 kJ/mol

CH2=CH2 + 5/2O2 2CO2 + 2H2O Ho298=- 1225 kJ/mol

250 330oC

Ag

5 M + 5 O2 5 MO24MO2 + 4 [CH2=CH2]hp 4 CH2 - CH2 + 4 MO

O4MO + [CH2=CH2]hp 2CO + 2H2O + 4M

2CO + MO2 2CO2 + M

5 CH2=CH2 + 5 O2 4 CH2- CH2 + 2CO2 + 2H2O

O


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* Nguyn liu:

Nguyn liu etylen s dng sn xut EO phi sch (cha axetylen, hp

cht cha l-u hunh, CO khng qu 2ppm mi loi).

Tc nhn oxi ho: Oxi khng kh hoc oxi nguyn cht .

* iu kin vn hnh:

Nhit phn ng l 260-290oC

p sut vn hnh t 1-3 Mpa

Thi gian l-u t 1-4 giy.

Tc phn ng: v=[etylen].[O2]

Nng etylen d-i 3% V


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* Sn xut cng nghip:

Trong cng nghip, EO -c sn xut trong nh my c s dng thit b

phn ng thm xc tc c nh, tun hon etylen ch-a chuyn ho, quy

trnh cng ngh gm hai phn chnh: tng hp EO v b phn tinh ch sn

phm.

Cng ngh sn xut:

+ Cng ngh s dng khng kh (Distillers IG Farben, Scientific Design,

Union Carbide)

+ Cng ngh s dng oxi nguyn cht (Chemische Werke-Huls, Japan

Catalytic, Scientific Design th h hai, Shell, SNAM Progetti).

Mt c im cn l-u cho c hai cng ngh ny l vn tn nhit cho

phn ng duy tr nhit phn ng mc ti -u nht.


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* Cng ngh sn xut EO bng oxi nguyn cht:

- iu kin vn hnh: Hn hp phn ng gm etylen +Oxi + metan + cht c ch.

Nhit phn ng: 250-270oC.

p sut trong l phn ng: 1,2 MPa .

Thit b hydro ho 20 a.

Thit b lm sch sn phm 50 a.


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*

Sn xut Etylen Oxit bng oxi khng kh. Cng ngh Scientific Design

Khng kh

Ethylene

hpphscp

Nhhpph

Thpl

oin-c

tchphnnng

Kh thi

Nhhpph

Thptinhchsnphm

cht c ch

Ethylene glycol

thu hi

scp

thitbphnng

Thitbphnng

thcp

Hpphthcp

absorption

N-c

my nn

Kh thi

Ethylene glycolthu hi

Cc sn phm nng

Etylen oxit

Cc sn phm nhproducts

my nn

Cng ngh Scientific Design sn xut E.O bng oxi khng kh.

KK

EG


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2.2.4. Sn xut Etylen glycol (EG).

E.G -c sn xut ch yu i t E.O bng qu trnh hydrat ho.

Ngoi ra cn c mt s ph-ng php khc sn xut E.G i t cc ngun nguyn liu khc

nhau nh-:

- Thu phn clohydrin etylen vi s c mt ca natri bicacbonat. Ph-ng php ny c in

v khng cn -c ng dng:

CH2 = CH2 + HClO HOCH2-CH2ClHOCH2-CH2Cl + NaHCO3 + H2O HOCH2-CH2OH + CO2 + H2O + NaCl

CH2-CH2 + H2O HOCH2-CH2OH Ho

298=-75 kJ/mol.O

2.2.4.1. Gii thiu chung.Monoetylen glycol th-ng -c gi l glycol. EG c t trng d204 =1,115,

nhit si: 197oC.EG c nhiu ng dng: - Cht chng bng (>33%)

- Polyetylen tetraphtalat (48%).- Nha polyeste khng no (19%)


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- CH2=CH2 + CH3OH + 1/2 O2 CH3COOCH2-CH2COOCH3 + H2O

Ho298=-125 kJ/mol

CH3COOCH2-CH2COOCH3 + 2H2O HOCH2-CH2OH + 2CH3COOH

Ho298=-17 kJ/mol

- Ph-ng php tng hp EG mt giai on i t nguyn liu etylen, Xc tc

-c s dng c cha ion talic trong dung dch HCl:

CH2 = CH2 + H2O + 1/2O2 HOCH2-CH2OH

HCHO + CO + H2O HOCH2-CH2COOHHOCH2-CH2COOH + CH3OH HOCH2-COOCH3 + H2O

HOCH2-COOCH3 + H2O HOCH2-CH2OH + CH3COOH

- Ph-ng php da trn qu trnh cacbonyl ho formaldehyt thnh axitglycolic, sau este ho axit ny to hydrin metyl axetat, thu phn este:

- Ph-ng php axetoxyl ho etylen thnh diaxetat sau thu phnto glycol:


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- Ph-ng php hydro ho n-butyl oxalat thnh EG v n-butyl ancol. Butyl oxalat-c to bi qu trnh oxi cacbonyl ho n- butanol trong pha lng.

- Ph-ng php i t kh tng hp c s dng cht xc tc cha phc ca rodi

cacbonyl, k thut ny -c pht trin bi cng ty Union Carbide:

2CO + 3H2

HOCH2

-CH2

OH- p sut:140 340 MPa- Nhit : 125 130oC.

- Sn phm ph:metyl format, metanol, n-c.

2n-C4H9OH + 2CO + 1/2O2 (n- C4H9COO)2 + H2O

Sau , phn ng hydro ho d-i s c mt ca xc tc ng v

crom trong pha lng:

(n- C4H9COO)2 + 4H2 HOCH2-CH2OH + 2n-C4H9OH

Pd

200oC

3MPa


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2.2.4.2. Cng ngh v iu kin vn hnh sn xutEG bng ph-ng php hydrat ho EO.

* iu kin vn hnh:- Nguyn liu E.O ban u -c pha long bng hn

hp n-c vi oxit vi t l 20 25/1- Thit b phn ng hot ng p sut 1,5 Mpa v

nhit u vo 150oC, nhit u ra 200-210oC.- Cht xc tc: H+

- Thi gian l-u: 45 pht n 1 gi.

- chn lc cc sn phm nh- sau: 88,5% mol EG,10,5% mol DEG, 0,5% mol TEG.

a er recyce


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Sn xut Etylen glycol bng ph-ng php hydrat ho Etylen oxit

Monoethyleneglycol

Denhydration

Diethyleneglycol

Triethyleneglycolsepa

ration

Vacoum

Fourthstage

Thirdstage

Secondstage

First:stage

Dilution

separation

Heavy

products

Condensates

Hydration

Ethylenne oxide

Water

separation

VacoumVacoumVacoum

Triethylene glycol

Diethylene glycol

Monoethylene glycol

Cm thit b bay hi


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2.2.5. Sn xut vinyl axetat t etylen.

2.2.5.1. Gii thiu chung

Vinyl axetat (VA) l cht lng khng mu, c t trng d204=0,935, nhit nng chy =

- 100,2oC, nhit si = 72,7oC.

ng dng: - Lm nguyn liu u sn xut PVA c tinh khit cao

- Poly vinyl ancol (phn ng thu phn cc nhm chc trong PVA).

Vinyl axetat -c sn xut cng nghip bng hai ph-ng php chnh:-

- Ph-ng php c in l cng hp gia axit axetic vi axetylen xy ra trong pha kh.

- Ph-ng php ngy nay -c s dng l thc hin qu trnh phn ng gia etylen v axit

axetic vi s c mt ca oxi. Ph-ng php ny -c ng dng nhiu ti M, Nht v mt

s n-c Ty u.


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2.2.6.2. Cc qu trnh sn xut VA.

A. Qu trnh phn ng trong pha lng:

Phn ng chnh

O O

CH2=CH2 + CH3- C OH + PdCl2 CH2=CH-O-C-CH3 + 2HCl + Pd

Pd + 2CuCl2 PdCl2 + 2CuCl

2CuCl + 2HCl + 1/2O2 2CuCl2 + H2O

- Xc tc cho qu trnh: Xc tc c cha mui ng vi vai tr l h oxi ho

kh. Thnh phn xc tc nh- sau: Pd2+ = 3.10-4 M (0,03g/l), Cu2+ = 0,08 M

(5g/l). Nng Cl- cho Pd dng ho tan. Thit b phn ng lm bng

Titan trnh n mn (do lm vic trong mi tr-ng axit c cha Cl-).


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Sn phm ph axetaldehit do phn ng ca etylen vi n-c hoc phn ng

thu phn VA.

CH2=CH2 + H2O + PdCl2 CH3CHO + Pd + HCl

CH3COOCH=CH2 CH2=CHOH (khng bn) CH3CHOH2O

- Thi gian l-u trong thit b phn ng di v nhit cao cng to iu kin

thun li cho s to thnh sn phm ph axetaldehit. Cc sn phm ph khc

bao gm: etyliden diaxetat (CH3CH(O2CCH3)2, CO2, dn xut clo...


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- u im:?

- Nh-c im:?


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B. Qu trnh sn xut VA trong pha kh

* Phn ng:

O OCH2=CH2 + CH3-C OH + 1/2 O2 CH2=CH-O-C-CH3 + H2O

Ho298 = - 180 kJ/mol

* iu kin phn ng:

- Nhit :160-180oC- p sut 0,8 Mpa.

- Cht xc tc: xc tc trn c s kim loi Pd/-Al.

- T l nguyn liu vo bao gm kh nguyn liu etylen l 50% V, 15% V

axit axetic, 6%V oxi v 29% V cc kh tr.


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* Cng ngh sn xut VA t etylen trong pha kh


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2.2.6. Sn xut etyldiclorua (EDC), vinyl cloruamonome (VCM) v PVC.

2.2.6.1. Sn xut etyldiclorua (EDC).

Etyldiclorua l cht lng khng mu, d bay hi, bn iu kin nhit

v p sut tiu chun.

T trng: d204 = 1,253

Nhit nng chy: - 35,5oC

Nhit si: 83,7oC.

Ph-ng php sn xut: EDC -c sn xut bng phn ng clo ho etylen.

ng dng:- Lm nguyn liu cho qu trnh tng hp VCM (> 90%)

- Lm hp phn cho ph gia chng kch n

- Lm dung mi cha clo...


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* iu kin phn ng v ng hc.

CH2=CH2 + Cl2 CH2Cl-CH2Cl Ho298= - 185 kJ/mol.

- Phn ng thc hin trong pha lng hoc pha kh d-i s c mt ca cht xc tctrn c s mui clorua ca kim loi (FeCl3 v CaCl2 ).

- Phn ng -c thc hin trong vng nhit 50 90oC:

+ Nu thu EDC th lng, phn ng thc hin nhit 50 60oC+ Nu thu EDC th kh th phn ng thc hin nhit 85-90oC

-p sut: 0,3-0,5 Mpa.

-C ch phn ng xy ra trn c s s phn cc ca xc tc FeCl3:

FeCl3 + Cl2 FeCl4-..Cl-

FeCl4-..Cl- + CH2=CH2 FeCl3 + CH2Cl-CH2Cl


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* Cng ngh sn xut EDC t etylen, thu sn phm pha lng

* C h t EDC t t l th h h kh


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* Cng ngh sn xut EDC t etylen, thu sn phm pha kh

FeCl3

Cng ngh sn xut EDC bng ph-ng php oxi clo ha etylen xc tc tng si.


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g g g p g p p y g


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Cng ngh sn xut EDC bng ph-ng php oxi clo ha etylen xc tc thm c nh.


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2.2.6.2. Sn xut vinyl clorua (VC).

Mt s tnh cht ca VC:

d204=0,9834, tnc= -153,8oC, ts= - 13,4

oC.

VC l cht kh khng mu iu kin tiu chun.

VC l cht c, to hn hp n vi khng kh (gii hn n t 3,6 n 26%

TT/TT).

Cc ph-ng php sn xut VC trong cng nghip:

- Cng HCl vo axetylen .

- Cng Cl2 vo etylen, sau nhit phn EDC to thnh VC v HCl.

- Kt hp s dng etylen v axetylen trnh s to thnh HCl.

- Oxiclo ho etylen, c th lin hp vi qu trnh clo ho (v qu trnh ny s

dng mt ngun HCl ln).


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A. Sn xut VC bng ph-ng php nhit phn EDC.

*Cc iu kin chuyn ho:

Qu trnh -c thc hin da trn phn ng phn hu thu nhit sau:

CH2Cl-CH2Cl CH2 = CH2Cl + HCl Ho298= + 70 kJ/mol.

Phn ng bt u xy ra 300oC, p sut kh quyn, nh-ng phn ng t -c

tc cao 400oC 550oC. Phn ng xy ra theo c ch gc nh- sau:

(a) Khi mo: CH2Cl-CH2Cl CH2Cl- CH2* + Cl*

(b) Pht trin mch: Cl* + CH2Cl-CH2Cl CH2Cl-*CHCl + HCl

CH2Cl-*CHCl CH2 = CH2Cl + Cl

*

(c) t mch: Cl*

+ CH2Cl- CH2*

CH2 = CH2Cl + HCl

- Cht xc tin: clo, brom, iot, tetraclocacbon hoc oxi.

C h t VC b h- h hit h EDC


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Cng ngh sn xut VC bng ph-ng php nhit phn EDC

215oC

500o

C

20

a

60

a

15a

70-75

a

25

a

,7kPa

20-25

a

HCl tun hon

Thitblmm

t


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83

Bi tp:

1. Sinh vin t xy dng s khi qu trnhlin hp clo ho etylen, nhit phn EDC voxiclo ho etylen.

2. Thuyt minh s cng ngh sn xut VCbng ph-ng php lin hp.


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B. Sn xut VC bng qu trnh lin hp.

* Lin hp clo ho etylen v hydroclo ho axetylen.

* Lin hp nhit phn EDC v hydroclo ho axetylen


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* Lin hp oxiclo ho etylen

Qu trnh ny bao gm s chuyn ho HCl (to thnh trong qu trnh nhit phn

EDC) thnh Clo nh- sau:

2HCl + 1/2O2 Cl2 + H2O Ho298= - 57 kJ/mol.

Qu trnh da trn cc phn ng sau:

C2H4 + Cl2 CH2Cl- CH2Cl (1)

2 CH2Cl- CH2Cl 2 CH2 = CHCl + HCl (2)C2H4 + 2HCl + 1/2O2 CH2Cl- CH2Cl + H2O (3)

Phn ng tng cng:

2 C2H4 + Cl2 + 1/2O2 2 CH2 = CHCl + H2O

u im ca ph-ng php: - Tiu tn t nng l-ng- S dng sn phm ph HCl

- Khng dng axetylen

- Chi ph r hn.


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Sn xut VC bng qu trnh lin hp

2 2 6 2 Sn xut Polyvinyl clorua (PVC)


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2.2.6.2. Sn xut Polyvinyl clorua (PVC).

A. Gii thiu chung.

PVC l mt loi nha c tnh c l tt, c bn s dng cao, chng lo

ho tt, d to mu sc, kh bt chy. Tuy nhin tnh mm do v bn

nhit thp.

Nhu cu s dng:

Th gii: Nhu cu s dng nha PVC tng mnh vo cui thp k 90 t 26

triu tn/ nm,

Vit Nam: Nm 2000 tiu th khong 150.000 tn bt PVC, trong n-c sn

xut p ng -c 40% nhu cu cn 60% nhp khu.

D kin n nm 2010 nhu cu bt PVC l 400.000 tn nm.


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Hin nay, n-c ta c 4 nh my sn xut PVC bao gm:

- Lin doanh Vit Nam Thi Lan TPC Vina sn xut 100.000 tn bt

PVC/nm.

- Lin doanh Vit Nam Malaysia Ph M sn xut 200.000 tn bt

PVC/nm.

- Lin doanh Vit Nam Thi Lan (Vit Thi) sn xut 15.000 tn bt

PVC/nm.- Atofina 100% vn ca Php sn xut 15.000 tn PVC/nm.

Cc ph-ng php sn xut PVC:

- Trng hp VCM bng ph-ng php huyn ph.

- Trng hp VCM bng ph-ng php nh t-ng.

- Trng hp VCM bng ph-ng php khi.

- Trng hp VCM bng ph-ng php dung dch.


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B. Phn ng v iu kin ng hc:

n CH2=CHCl [-CH2-CHCl-]nC ch:I 2 I*

I* + CH2=CHCl I-CH2-*CHCl

R-CH2-*CHCl +n CH2=CHCl R-[CH2- CHCl]n- CH2-

*CHCl2 R-[CH2- CHCl]n- CH2-

*CHCl R-[CH2- CHCl]n- CH=CHCl +

R-[CH2- CHCl]n- CH2- CH2 ClHoc R-[CH2- CHCl]n- CH2- CHCl-CHCl-CH2[CHCl-CH2]-R


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B. Cc ph-ng php trng hp VCM sn xut PVC.

B1. Trng hp VCM bng ph-ng php khi.

Phn ng tin hnh nhit 40 70oC v p sut 5 12 bar

* u im: D thc hin

* Nh-c im: Trng hp khi kh tch nhit cho phn ng do d xy ra vng

qu nhit cc b.


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C ch hnh thnh cc ht PVC trong phn ng polyme ho VCM bng ph-ngphp khi:

Kch th-c ht chuynho (%)

Git VCM

Cc ht PVC-VCM utin

Tp hp cc ht PVC-

VCM

Ht PVC cui cng

0

200Ao

0,1-0,2 m

2 10 m

0

2

3- 10

90


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S cng ngh sn xut PVC bng ph-ng php khi


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B2. Trng hp VCM trong dung dch.

- Qu trnh trng hp ng th: polyme/dung mi:

> Qu trnh ny ko di

> i hi l-ng dung mi ln, c tinh khit cao.

t -c s dngtrong cng nghip

B3. Trng hp VCM bng ph-ng php nh t-ng:

Latex

PVC khVCM, H2O

Cht nh ho

PVC khLatex

VCMH2O

VCMPVCH2O

VCMPVCH2O

PVCH2O

PVCH2O

H2OCht khi mo Ht nha

VCMthu hi

Khngkhnng

Khngkh +hin-c

PVC

VCMH2O

VCMPVCH2O

Nht-ng

Vihuynph

Monome ho tanCht khi mo

PVC

PVC loi

Chun b Polyme ho Vn chuyn tn tr lm kh nghin to ng gi


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B4. Trng hp VCM bng ph-ng php huyn ph.

Trng hp VCM bng ph-ng php huyn ph l ph-ng php -c s

dng rng ri nht trong cng nghip sn xut PVC v c nhiu -u im

sau:

- Sn phm to thnh dng ht, bi d gia cng.

- Vn tc trng hp ln.

- Nhit phn ng thp.

- Khng xy ra hin t-ng qu nhit cc b.


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C ch hnh thnh cc ht PVC trong phn ng polyme ho VCM bng ph-ngphp huyn ph:

Kch th-c ht chuynho (%)

Git VCM

Cc ht PVC/VCM utin

Tp hp cc htPVC/VCM

Ht PVC cui cng

0

0,1 0,2 m

1 3 m

2 10 m

0

1 5

3 10

80 - 90


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Cng ngh sn xut PVC bng ph-ng php huyn ph

- iu kin vn hnh ca nh my:

Nguyn liu chnh:VCMmi

VCMtun hon

VCM N-c loikhong Tc nhn tohuyn ph

Th cp S cp

Cht khimo

Polyvinyl ancol Polyvinyl axetat

2NaOH + H2O2 = Na2O2 + 2H2O

Na2O2 + C2H5OCOCl C2H5OCO-OONa + NaCl

C2H5OCO-OONa + C2H5OCOCl C2H5OCO-OO-OCOC2H5 + NaCl

C2H5OCO-OO-OCOC2H5 2C2H5OCOO*

* C ch hnh thnh cht khi mo:


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. S cng ngh sn xut PVC bng ph-ng php huyn ph

VCM

Thi b h


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Thit b phn ng

(1) Thit b phn ng

(2) My khuy xon co dng i ln

(3) My khuy m neo

(4) Thit b ng-ng t

ng-c dng

(5) Thit b lc gii t

(6) Mc PVC ti a

(7) Van x ra

(8) Ca x

Ch 3


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Ch-ng 3.

Sn xut cc hp cht t propylenCH3-CH=CH2

Propylen

Propylen oxit

Axit acrylic

Acrylonitril

Nha PP

Si polyacrylat

Propylen glycol10%

13%

46%

Cumen

R-u

Axeton

3 1 S t l it (PO)


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3.1. Sn xut propylen oxit (PO).

Propylen oxit l cht lng c ts= 35 oC, nhit t

nc= -112oC, t trng d20

4= 0,830

PO c nhiu ng dng nh-ng ng dng quan trng nht l -c s dng lm

nguyn liu sn xut polyuretan (chim 60%) v nha polyeste (20%).

Cc ph-ng php sn xut PO:

- Qu trnh clohydrin ho propylen

- Qu trnh in ho

- Qu trnh oxi ho trc tip.

- Qu trnh oxi ho s dng peroxit.

3.1.2. Cc ph-ng php tng hp P.O v c im ca phn ng


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p g p p g p p g

3.1.2.1. Qu trnh clohydrin ho propylen sn xut PO.

* Phn ng v iu kin ng hc.

Qu trnh ny t-ng t nh- qu trnh sn xut EO. Cc phn ng

chnh xy ra nh- sau:

Cl2 + H2O ClOH + HCl

CH3 -CHOH-CH2Cl (90%)CH3-CH=CH2 + HOCl

CH3 -CHCl-CH2OH (10%)

2CH3CHOHCH2Cl + NaOH CH3CH CH2 + NaCl + H2OO

Phn ng to propylen clohydrin to nhit vi Ho298 =-225 kJ/mol

Phn ng vi NaOH thu nhit nh Ho298 =5 kJ/mol.

S cng ngh sn xut PO bng qu trnh clohydrin propylen


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Sn xut PO bng ph-ng php oxi ho c s dng peroxit.

Phn ng chnh nh- sau

CH3-CH=CH2 + ROOH (hoc R-CO-OOH) CH3-CH - CH2 + ROHO

(hoc RCOOH)

Khi mo: RH + A R* + AHPht trin mch: R* + O2 RO2

*

RO2* + RH ROOH + R*

Ngt mch: 2R* R-R

R

*

+ RO2*

ROOR2RO2* Sn phm khng hot ng

* Phn ng oxi ho isobutan to t-butyl hydroperoxit v t-butyl ancol.


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iu kin phn ng:

- Nhit 110 130oC

-

p sut 3 3,5 Mpa-Thi gian l-u khong 7 gi cho mt l-ng isobutan chuyn ho l 35%.

- T l oxi v isobutan d-i 8%, m bo mc ngoi gii hn chy n d-i.* Phn ng epoxi ho propylen:

iu kin phn ng:

- Phn ng ny xy ra trong pha lng

- Xc tc: dung dch molipden naphtenat 5% KL.

- Thit b phn ng nhiu giai on

- Nhit : 110oC

- p sut 3 -4 Mpa

-t l peroxit/ancol/propylen l 1/1/3

- Thi gian l-u 0,51 gi/1 giai on, tng thi gian l-u l 2,5 gi.

- ch n l c ro len oxit v ancol t 85.

S cng ngh sn xut PO bng qu trnh oxi ho propylen s dng peoxit


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S cng ngh sn xut PO bng qu trnh oxi ho propylen s dng peoxit

O2

Chun b nguyn liu

100oC

C3

PO th

PO


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3.1.2.5. Sn xut PO bng ph-ng php oxi ho c s dng cc


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g p g p p gperaxit v hydroperoxit (cng ngh Daicel).

Cng ngh hai giai on: Giai on th nht: qu trnh oxi ho axetaldehit trong etyl axetat bng oxi

to peraxit: - Phn ng xy ra nhit phng

- p sut 2,5-4 MPa

- Xc tc axit.

Giai on hai: epoxi ho propylen:

- Nhit 50oC

- p sut 0,9-1,2 Mpa

- Thi gian l-u 2 3 gi

- chuyn ho axit peraxetic l 97 -98%

- Hiu sut to PO l 92%.

S cng ngh sn xut PO bng qu trnh oxi ho propylen s dng peraxitCng ngh Daicel


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Cng ngh Daicel

3 2 S t P l l (P P)


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3.2. Sn xut Polypropylen (P.P)

Polypropylen l nha chu nhit

Nhu cu tiu th tiu th PP ng th ba, sau PVC.

PP -c tng hp bng phn ng polyme ho theo nhiu c ch khc nhau:

- C ch gc: cho PP c cu trc atactic chu nhit km

- C ch khng gian: cho PP c cu trc isotactic chu nhit tt

Xc tc cho qu trnh l xc tc Ziegler- Natta c hot tnh cao, c tnh chn lc lp

th.

Cc ph-ng php sn xut PP:

- Sn xut PP trong pha kh

- Sn xut PP trong pha lng

-CH-CH2-

CH3 n


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- C ch phn ng xy ra trn tm kim loi xc tc nh- sau:

Phn ng khng c qu trnh chuyn mch v to ra polime c khi l-ng phn

t rt ln.

CH3

CH3CH2 CH2

Ti Al +Ti AlCH2 CH2

CH3-CH= CH2 CH3 CH3-+CH- -CH2 CH3

CH3 CH3CH2 Al CH2Ti+ CH2-CH3 Ti Al

CH2- CH CH2CH3 CH- CH2- CH3

CH3

S cng ngh sn xu P.P trong pha kh.


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(1), (5) Thit b phn ng (3), (7) Thit b trao i nhit(2), (6) My nn (4), (8) Bn cha sn phm

Propylen/etylen

i phn loi vhon thin sp


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u im ca cng ngh pha kh ?

S cng ngh sn xu P.P trong pha lng.


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(1) Thit b phn ng dng ng (3) Thit b phn ng copolime ho pha kh(2), (4) H thng tch to p hai cp (5) Thp stripping

etylen

Hi n-c, etylen,propylen, sp nh


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u im ca cng ngh pha lng ?

3.3. Sn xut CumenCH3 CH3CH


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3.3.1. Gii thiu chung

Cumen (isopropylbenzen) l cht lng, tan trongnhiu dung mi hu c, khng ho tan trong n-c.

Ph-ng php chnh sn xut cumen l qu trnh

ankyl ho benzen vi propylen.. Cc cht xc tc cho qu trnh:

- Vi cc qu trnh alkyl ho ng th: axit Bronsted

nh- HF, H2SO4..., axit Lewis nh- AlCl3+ HCl- Vi cc qu trnh alkyl ho d th: Al2O3,

Al2O3/SiO2 v cc zeolit

C

3.3.2. Qu trnh alkyl ho benzen bng propylen sn xut cumen.


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3.3.2.1. Phn ng v iu kin vn hnh.

Cng ngh phn ng trong pha lng: - Nhit v p sut thp (50oC, 5 atm),

- Cht xc tc: axit sunfuric.

Cng ngh trong pha kh: - Nhit 250oC

- p sut 40 atm

- Cht xc tc: axit photphoric.

* Phn ng chnh xy ra nh- sau:

CH3-CH=CH2 +

H+

C

H3C CH3

* Cht xc tc -c s dng c th l:

- AlCl3, tin hnh 10-95oC.

- H3PO4, c hoc khng c cht xc tin mang trn cht mang rn.

- Bentonit -c hot ho axit, cho php tin hnh phn ng 70-105oC.

- Aluminosilicat, s dng dng t-ng t xc tc cracking, lm vic 200oC.

3.3.2.2. Cng ngh sn xut cumen bng ph-ng php alkyl ho bezen.


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119=1

bezen/propylen = 8/1 10/1

30

a

* c im cng ngh


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Yu cu i vi cumen th-ng phm: c cha hm l-ng cc tp cht

< 1200ppm (0,02% etylbenzen, 0,05% n-propylbenzen, 0,05% butylbenzen).

Hiu sut qu trnh tnh theo benzen l 96-97% v tnh theo propylen l 91-92%.

Ngoi ra, thu hi thm cumen, mt s cng ngh c thm b phn transankyl

ho nhm chuyn diisopropylbenzen v benzen thnh cumen theo phn ng sau:

CH(CH3)2

CH(CH3)2 +

CH(CH3)2

2

Nhit phn ng: 180 250oC

p sut: 2 MPa

T l benzen/diisopropyl benzen = 5/10.

3.4. Hydroformyl ho propylen sn xut r-u


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3.4. Hydroformyl ho propylen sn xut r-ubutylic (phn ng tng hp Oxo)

3.4.1. c im ca phn ng v iu kin ng hc.

Phn ng ca propylen cho sn phm l butyladehyt v isobutyladehyt:

Ho298

= - 125 kJ/mol

T l to thnh hai sn phm butyraldehyt/isobutyraldehyt = 4/1.

2CH3 - CH=CH2 +2CO + 2H2

CH3 -(CH2)2-CHO

(CH3)2CH-CHO

3.4.3. Cng ngh hydroformyl ho propylen sn xut r-u butanol.


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* iu kin vn hnh:

- Nhit : 110 180oC

- p sut 20 35 Mpa

- T l mol CO/H2 =1/1 1/1,2

- Thi gian l-u: 1 5 pht

- L-ng xc tc s dng: 0,2 1% KL so vi propylen.

- Tng t l n-/iso: tng t l n-/iso ln 9/1, hng Shell s dng xc tc coban hydrocacbonyl th

bng phosphin (Hco(CO)3P(n-C4H9)3). Phn ng -c thc hin nhit 180

200oC v p sut 510 Mpa. Tuy nhin, hot tnh ca h xc tc ny cn thp v c

xu h-ng to iu kin thun li cho cc phn ng ph hydro ho olefin v aldehyt hn

l xc tc thng th-ng.

Hng Union Carbide pht trin h xc tc bin tnh cacbonyl rodi bng

triphenylphosphin v to ra t l sn phm mch thng ln hn nhiu (n-/iso =10/1)

trong iu kin phn ng rt mm (nhit 60 120oC, p sut 0,1 -5 Mpa).


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Hn hp cc n- v iso-aldehyt -c hydro ho thnh cc r-u t-ng ng.

CH3 -(CH2)2-CHO

(CH3)2CH-CHO

CH3 -(CH2)2-CH2OH

(CH3)2CH-CH2OH

H2/Ni

H2/Ni

Nhit : 150 200o

Cp sut 5 10 Mpa,

Cht xc tc: ng hoc niken

S cng ngh sn xut butanol


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CO/H2=1/1-1/2 Cxt Co

* c im qu trnh:


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125

* c im qu trnh:

ng sn phm isobutylaldehyt c t ng dng vn gy

tr ngi v kinh t cho qu trnh. ngh mt cng nghc c phn x-ng cracking xc tc isobutylaldehyt vtun hon cc sn phm cracking ny (propylen, CO,H2).

Nu hydro -c thay th bng hi n-c, c th thu -csn phm c cha 88% n-butanol v 12%isobutanol.Phn ng chnh:

H thng lm vic 100oC v 1,5Mpa, c mt cht xctc pentacacbonyl st, butyl-pyrolidon v n-c.

CH3-CH=CH2 + 3CO + 2H2O C4H9OH + 2CO2 Ho298 = - 240 kJ/mol

3.5. Sn xut Axit Acrylic


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126

y

Axit acrylic -c s dng nh- mt cht trung gian cho cc qu trnh tng

hp cc este phn t l-ng thp, cc etyl, butyl v 2-etyl hexyl acrylat

Cc ph-ng php chnh sn xut axit acrylic:

- Oxi ho propylen pha hi tin hnh qua hai giai on, trong giai

on trung gian to acrolein.- Thu phn etylen cyanhydrin.

- Ph-ng php polyme ho -propiolacton thu -c nh qu trnh phn ng

gia formaldehyt vi ceten.

- Ph-ng php oxi cacbonyl ho etylen.


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* c im ca qu trnh ?


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128

q

* Qu trnh oxi ho propylen:


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129

* Qu trnh oxi ho propylen:

- Cht xc tc: CuO/SiO2

hoc Al2

O3

. hn hpca cc oxit bismut, kali, coban, st, niken,thic telu, vonfram...cc axit molipdic hocsilicomolipdic.

- Nhit : 300 350o

C- p sut: 0,1 0,3 Mpa

- T l mol n-c/propylen khong 4/5

- T l oxi/propylen khong 2/1

- chuyn ho mt ln t 90 95%

-Hiu sut acrolein l 80 90% mol.

* Qu trnh chuyn ho acrolein:


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130

* Qu trnh chuyn ho acrolein:

- Xc tc trn c s hn hp ca cc oxitmolipden v vanadi tm thm mt s hp chtca vonfram, ng, crom, telu, asen....

- Nhit : 250 280oC

- p sut: 0,1 0,2 Mpa- T l mol n-c/acrolein khong 5/7

- T l oxi/acrolein khong 2/1.

- chuyn ho mt ln t 95 97%

- Hiu sut mol axit acrylic trn 90% tnh theoacrolein


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131

* iu kin cng ngh:

Xc tc c tr-ng da trn c s oxit molipden.

Cc thit b phn ng l h ng chm c dng mui nng chy tun hon

gia cc ng tch nhit cho phn ng, m bo kim sot nhit hiu

qu v tn dng nhit sn xut hi p sut thp. Xc tc -c phn phi trn lp m cng ng u cng tt, m bo s

ng nht v p sut, tc dng, chuyn ho... v v c tui th ca

xc tc.

Cc tc nhn phn ng di chuyn t trn xung d-i qua lp xc tc, pha

trn lp xc tc -c ph mt lp cht rn tr gia nhit cho nguyn liu.

S cng ngh sn xut axit acrylic bng qu trnh oxi ho propylen


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132

90%TT

4-5%TTpropylen30 40% TT n-c

55-65% TT khng kh

Sp giu axit acrylic

70oC 70oC

hydroquinol

3.6. Sn xut axeton


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133

Axeton l cht lng c t trng d204 = 0,790, tnc=-94,6oC, ts=56,1

oC

ng dng: - Sn xut cc hp cht nh- diaxeto ancol, hexylen glycol,

metylisobutylcacbinol, metylisobutyl xeton (bng phn ng ng-ng t

aldol), Bis phenol A, Metylmetacrylat, lm dung mi...

Ph-ng php sn xut:

- Dehydro ho isopropanol, l-ng axeton -c sn xut theo ph-ng php ny

chim 1/3 tng l-ng axeton sn xut trn th gii.

- Oxi ho cumen to hydroperoxit sau phn tch thnh phenol v axeton.

- Oxi ho trc tip hn hp propan v butan hay phn on naphta cho hn

hp cc sn phm trong c axeton (cng ngh BPl chemicals).

- ng oxi ho propylen v isobutan thnh propylen oxit v t-butyl ancol vthu axeton nh- mt sn phm ph (cng ngh ARCO chemical).

- Oxi ho isopropanol thnh axeton v hydroperoxit, cng ngh Shell.

- Oxi ho trc tip propylen bng oxi khng kh d-i s c mt ca phc, cng

ngh ca Wacker/Hoechst.


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Phn ng tng ca ton b qu trnh:


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135

CH3-CH=CH2 + 1/2 O2 CH3-CO-CH3 Ho298 = - 255 kJ/mol

* c im phn ng:

- Tc phn ng t l thun vi s hnh thnh phc gia propylen v clorua

paladi-Phn ng oxi ho propylen thc hin :

+ Nhit : 90 120C

+ p sut thp 0,9 1,2 Mpa

+ Xc tc -c ti sinh trong cng iu kin.

chuyn ho mt ln t 98 99%

Hiu sut t 92 94% mol.


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136

120oC

50

o

C

Propylen

99,5%

3.7. Sn xut AcrylonitrilCH =CH CN


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137

CH2=CH-CN

Acrylonitril: d204= 0,806, tnc= - 83,5oC, ts=77,3

oC

ng dng:

- Sn xut cao su nitril v cao su Buna N

- Copolyme ca butadien v acrylontril

- Sn xut si tng hp, nha, cht do

- Cc hp cht hu c trung gian.

. Cc ph-ng php sn xut:

- Ph-ng php ammoxi ho propylen, cng ngh ny -c pht trin bi cng tySohio vi s ci tin h xc tc s dng.

- Cng hp hydrocyan vo etylen oxit to cyanhydrin, sau ehydrat to acrylonitril.

- - Thc hin phn ng gia hydro cyan vi axetylen

- - Dehydrat ho sn phm lactonitril ca qu trnh phn ng gia axetaldehyt vihydro cyan.

- - Ammoxi ho propylen bng NO2

3.7.2.2. Sn xut acrylonitril bng ph-ng php ammoxi ho propylen.

* Nguyn tc qu trnh:


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138

g y q

CH2=CH-CH3 + 3/2O2 CH2=CH

-CN + 3H2O

Ho298 = - 515 kJ/mol

Phn ng ny xy ra qua giai on to hp cht trung gian acrolein nh- sau:

CH2=CH-CH3 + O2 CH2=CH

-CHO + H2O

CH2=CH-CHO + NH3 CH2=CH

-CH=NH + H2O

CH2=CH-CH=NH + 1/2O2

CH2=CH-CN + H2O

2 CH2=CH-CH3 + 3O2 + 3NH3 3CH3CN + 6H2O

CH2=CH-CH3 + 3O2 + 3NH3 3HCN + 6H2O

CH2=CH-CH3 + 3O2 3CO + 3H2O

2CH2=CH-CH3 + 9O2

6CO2 + 6H2O

Mt s phn ng ph:

* Cht xc tc cho qu trnh:


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139

H xc tc u tin: Bismut photpho molipdat

H xc tc th hai: Antimo v uran (xc tc 21) H xc tc th ba: St v bismut phtpho molipdat tm Co, Ni v K (h xc tc

41). H xctc ny nng hiu sut ca qu trnh ln 10 35%.

H xc tc th t- ra i (xc tc 49) p ng yu cu v tnh bn c hc.

Cng ngh hai giai on:- Trong giai on u: xc tc trn c s oxit ca selen v ng.

- Trong giai on th hai: xc tc MoO3 v cc hp cht khc.

. Cng ngh mt giai on: xc tc oxit molipden c s dng cht xc tin NaOH

hoc coban molipden v oxit telu kt hp vi oxit antimo v thic.. Ngy nay: h xc tc trn c s coban, st v molipden.

. Mi nht l h xc tc tm antimon v st (k hiu NS733A hay xc tc 13)

* Cng ngh sn xut acrylonitril:

- Cng ngh thc hin trong pha kh.


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140

Cng ngh thc hin trong pha kh.

- H thit b phn ng xc tc tng si:

+ u im:thun li cho qu trnh tn nhit cho phn ng, ng u ho nhit

mi tr-ng phn ng, gip cho vic kim sot nhit tt hn do lm tng hiu

qu lm vic ca cht xc tc (cng ngh Sohio, Montedison/UOP, Nitto...).

+ Nh-c im: bn c hc ca cht xc tc gim.- H thit b thm xc tc c nh:

+ u im: ko di tnh bn c hc ca xc tc

+ Nh-c im: gradien nhit ln, ph hu xc tc nhanh chng do di chuyn ca

cc pha hot ng v s hao mn ca xc tc.

- Vi thi gian l-u 215 giy, tui th ca xc tc c th ko di t 1-3 nm, v c

th di hn vi cc h xc tc tin tin.

* iu kin phn ng:


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141

- V nguyn tc: Phn ng ammoxi ho propylen xy ra vi l-ng d- amoniac v oxi

so vi h s t l-ng.

- tinh khit ca nguyn liu u vo:

+ Propylen >90% KL

+ Amoniac: 99,5% KL.

- Thnh phn nguyn liu cho cc cng ngh s dng cht xc tc khc nhau:

Xc tc Thnh phn

Propylen Amoniac Khng kh Hi n-c

Sohio 1 1,5 2 10 20 2 4

Sohio 1 1,05 1,2 10 15 -

PCUK/Distillers 1 1,1 1,2 12 - 15 -

Kinh nghim: Hiu sut acrylonitril tng theo t l NH3/propylen.


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142

Thc t t l NH3/propylen =1 hoc 0,8.

Nhit phn ng trong khong 400 500oC

p sut d-i 0,3 MPa.

T l mol acrylonitril/axetonitril tng ln nhanh chng khi nhit trn 400oC v

t cc i khong 470 480oC.

* Tin hnh phn ng:

chuyn ho mt ln ca amoniac t trn 95% (trong cng ngh xc tc tng


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143

si) v xp x 85% (trong cng ngh thm xc tc c nh).

chn lc, hay hiu sut to acrylonitril rt nhy vi cc loi xc tc v iukin phn ng khc nhau

Thi gian l-u: trn 1 giy.

Hiu sut qu trnh c th t n 72 75% mol i vi h xc tc tin tin

nht, thc hin trong cc thit b xc tc tng si v gn 78% trong cc thit bthm xc tc c nh.

Nhiu loi sn phm ph cng hnh thnh vi t l ln nh- axetonitril, HCN...

axetonitril th-ng -c chuyn ho thnh acrylonitril theo phn ng s dng

xc tc trn c s KBr mang trn cht mang nh- sau:

Hydrocyanua -c s dng cho qu trnh tng hp axit metacrylic, methionin...

Tuy nhin, trong nhiu tr-ng hp, trnh nhim v m bo an ton, HCN

-c t b.

CH3CN + CH4 + O2 + H 2O CH2=CH-CN + CO2 + CO + H2

hnh phn sn phm ca qu trnh ammoxi ho propylen sn xut acrylonitril (% TT)

Cng ngh xc tcTng si Thm c nh


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Cng ngh xc tc

Xc tc Sohio 41 Nitto 13 PCUK/Distillers

Thnh phn sn phmAcrylonitril 5,2 5,3 4,3

Hydrocyanua 1,8 1,1 1,0

Axetonitril 0,7 0,1 0,3

Cacbon monoxit 1,0 0,8 0,5

Cacbon dioxit 1,6 2,9 1,2Cc hp cht nitril - - Rt t

Cc sn phm nng Rt t Rt t -

Propan 0,8 0,8 0,6

Propylen 0,5 0,2 0,3

N-c 26,3 25,2 33,6

Amoniac 0,2 1,0 1,1

Oxi 2,2 1,8 4,0

Nit 59,7 60,8 53,1

Tng 100,0 100,0 100,0

Cng ngh ammoxi ho propylen xc tc tng si (cng ngh Sohio):


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145

95%

ChiucaotngXT

Cng ngh ammoxi ho propylen thm xc tc c nh


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146

40-45a

45-50a

60-65a

N-c

25-30a

50-60a

3.8. Sn xut isopren t propylen.


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147

Isopren (ts=34oC, d204=0,681) l monome cho qu trnh tng hp polyme

cis-1,4 polyisopren (cao su t nhin c cha 85% thnh phn ng phn

ny) c gi tr kinh t cao.

Isopren c th -c chit t phn on C5 ca qu trnh cracking hi n-cv -c tng hp bng nhiu ph-ng php khc nhau:

Ph-ng php dehydro ho isopentan (cng ngh Houdry vad UOP).

Ph-ng php dehydro ho isoamylen (cng ngh Shell).

Ph-ng php sn xut isopren i t propylen, cng ngh ca Goodyear

Scientific Design.

CH2=C-CH=CH2

CH3

* Qu trnh cng ngh sn xut isopren t propylen.

Qu trnh sn xut isopren t propylen -c tin hnh theo ba b-c sau:


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148

Q p p py

(a) Qu trnh Dime ho:

2CH3-CH=CH2 CH2=C-CH2-CH2-CH3

CH3

CH3-C=CH-CH2-CH3

CH3

CH2=C-CH2-CH2-CH3

CH3

CH2= C -CH=CH2 + CH4

CH3

CH3-C=CH-CH2-CH3

CH3

(b) Qu trnh isome ho:

(c) Qu trnh cracking:

H0289=63 kJ/mol

H0289=-6 kJ/mol

H0289=96 kJ/mol

* iu kin tin hnh: Qu trnh dime ho:


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Qu trnh dime ho:- Cht xc tc tripropyl nhm

- Nhit 150 200oC- p sut 20 MPa.- Thi gian l-u:15 pht- chn lc: 90-95%- chuyn ho mt ln t 60-95%.

. Qu trnh isome ho:

- cht xc tc: axit photphoric- Nhit 150-300oC- Thit b phn ng thm xc tc c nh.- chn lc phn t t 98 99%- chuyn ho mt ln 85%.

. Qu trnh cracking:

- Nhit 650-700oC- Cht khi mo gc t do (HBr hoc peroxit) v hi n-c.- Thi gian l-u:1/10 giy.

Cng ngh sx isopren t propylen


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150


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Bng 4.1 . Nhit si ca cc cu t trong phn on C4


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152

Hydrocacbon Nhit si (oC)

isobutan - 11,7

isobuten - 6,9

1- buten - 6,3

Butadien - 4,4

n-butan - 0,5

trans-2-buten - 0,9

cis-2-buten 3,7

4.2. Sn xut Butadien.CH2=CH-CH=CH2

t =- 4 413oC d204=0 621


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ts= 4,413 C, d 4=0,621

* Cc ph-ng php sn xut butadien:

Butadien

Axetylen v formadehyt

Axetaldehyt

Etanol dehydro ho v dehydrat ho

Phn on C4

(cracking hi n-c)

n-buten v n-butan

4.2.1. Cc ph-ng php sn xut butadienbng qu trnh dehydro ho


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bng qu trnh dehydro ho.

4.2.1.1. Dehydro ho trc tip c xc tc.

Qu trnh -c tin hnh trn nguyn liu ban u l buten hoc

butan, nu nguyn liu u l butan, qu trnh thc hin qua hai giai on

thng qua giai on trung gian to buten.

n-C4H8 CH2=CHCH=CH2 + H2

n-C4H10CH

2=CHCH=CH

2+ 2H

2

* Dehydro ho buten c xc tc.

A i ki h h


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155

A. iu kin vn hnh:

Nguyn liu phn on C4 -c x l t -c nng buten thchhp(70-95%KL).

Qu trnh dehydro ho buten xy ra theo phn ng sau:

Ho298=124 kJ/mol

Sn xut butadien trong cng nghip:

- Cht xc tc:Fe2O3/Cr2O3, Fe2O3/Cr2O3 , Ni v Ca photphat, Fe2O3/Bauxit

- Nhit > 600oC.- p sut: 0,1-0,2 MPa

- Hi n-c.

CH2=CH-CH2-CH3

CH3-CH=CH-CH3

CH2=CH-CH=CH2 + H2

X Sh ll 105 Sh ll 205 D B Philli 1490

Bng 4.2. iu kin vn hnh qu trnh dehydro ho buten sn xut butadientrn cc xc tc khc nhau:


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156

6206206006200,150,160,15109125300202627807576115

Xc tc

iu kin

Shell 105Fe2O3/Cr2O3

Shell 205Fe2O3/Cr2O3

Dow BNi v Ca

photphat

Phillips 1490Fe2O3/Bauxit

Nhit (oC) 680 680 680 680

p sut (MPa) - 0,18 0,20 0,18

Hi n-c/buten(mol/mol)

18/1 8/1 20/1 12/1

Th tch dng(h-1)

- 500 125-175 300-400

chuyn homt ln (%)

20-30 26-28 > 45 27-33

chn lcbutadien (%) 80-70 75-73 90 76-69

Thi gian ti sinhxc tc

1 gi n 7ngy

1-24 gi 15-30 pht Khng

B. S cng ngh dehydro ho buten sn xut butadien.


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* Dehydro ho butan c xc tc.

A iu kin phn ng:


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158

A. iu kin phn ng:

Qu trnh xy ra theo phn ng sau:

CH3-CH2-CH2-CH3

CH3-CH2

-CH=CH2

+ H2CH3-CH=CH-CH3

CH3-CH2-CH=CH2

CH3-CH=CH-CH3

CH2=CH-CH=CH2 + H2

Ho298=127 kJ/mol

Ho298=124 kJ/mol

- Nhit phn ng: 550 - 700oC.

-p sut: < 0,1MPa

- chuyn ho: 57,7% (phn ng u).15,9% (phn ng th hai).

- Cht xc tc: oxit nhm v crom.


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iu kin vn hnh

Nhit 590oC


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160

Nhit 590oC

p sut 0,2 MPa

Th tch dng 700 h-1

chuyn ho mt ln 30%

L-ng ry phn t s dng 80%(KL)

- Thit b phn ng ng chm, lm vic lun phin.

- Nguyn liu ban u cha 98% n-C4 -c lm kh.

- Qu trnh ti sinh cht xc tc thc hin p sut 0,7 MPa vi dng khcha 2 - 3% oxi.

* Cng ngh catadien Hoydry (Air Products).

iu kin vn hnh:


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Nguyn liu: > 95% n-C4.

Nhit : 600- 675oC.

p sut:15 -70 kPa.

Cht xc tc: nhm hot tnh cha 18-20%oxit crom.

Th tch dng: 300 h-1.

chuyn ho mt ln: 50 - 60%.

- iu kin vn hnh:

S cng ngh qu trnh dehydro ho butan sn xut butadien.


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4.2.1.2. Dehydro ho bng tc nhn oxi hot ng.


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163

Ph-ng php ny -c thc hin bng hai qu trnh khc nhau:

Ti sinh cht xc tc HI bng oxi.

Dehydro ho bng oxi vi s hnh thnh n-c, qu trnh ny xy ra theo phn

ng sau:

C4H8 + 1/2O2 C4H6 + H2O

Ho

298= - 115 -130 kJ/mol(Tu thuc vo sn phm iso)

* iu kin vn hnh:

Nhit phn ng: 400 600oC


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Nhit phn ng: 400- 600oC.

p sut: 0,15 MPa.

Cht xc tc trn c s mui ca bismut molipdat v

photphat c b sung thm mt s kim loi chuyn

tip khc.

T l oxi/buten = 1.

T l hi n-c/buten l 30- 50.

chuyn ho mt ln t > 60%.

chn lc butadien l 95%.

s cng ngh sn xut butadien bng qu trnh dehydro hos dng tc nhn oxi.


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166

* u im ?

4.3. Mt s ng dng ca Butadien


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167

Sn xut cao su tng hp

cao su styren-butadien (SBR).

cao su nitril

Polybutadien

C

C

H

H

H

C

H

C

H

C

H

C

H

H

H

C

H

HC C

HH

C

H

C

H

C

H

H

H

cis-1,4 polybutadienNguyn liu tng hp

hu cSn xut Cloropren

Sn xut Adiponitril

4.3.2. Sn xut Cloropren (2-clo 1,3-butadien)CH2=CH - CCl = CH2

59 4 C d20 0 9585


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ts= 59,4oC, d204= 0,9585

Qu trnh xy ra theo cc b-c sau:

(a) Clo ho butadien:

(b) Isome ho 1,4-diclo 2-buten:

(c) Dehydro ho 3,4-diclo 1-buten:

CH2=CH-CH=CH2

ClCH2-CH=CH-CH2ClCl2

300oC CH2=CH-CHCl-CH2Cl

CuCl

100oC

ClCH2-CH=CH-CH2Cl CH2=CH-CHCl-CH2Cl

CH2=CH - CCl = CH2 + NaCl + H2O+15%NaOH

100oC

CH2=CH-CHCl-CH2Cl

Tnh cht ca cloropren th-ng phm -c sn xut t butadien


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Cc tnh cht n v Gi tr

2-clo butadien % KL min 98,5

1-clorobutadien % KL max 1,0

3,4-diclo 1-buten ppm max 100

Cc dime ppm max 100

Cc andehyt (nh-axetaldehyt) ppm max 1000

Cc peroxit ppm max 1

* iu kin vn hnh.

A. Qu trnh clo ho:


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170

Q

Thc hin trong pha kh. Nhit 250-350oC (thch hp nht l khong 300oC)

p sut kh quyn.

T l butadien/ clo: 3- 6/1.

Tc th tch dng: 1000 h-1.

chn lc i vi butadien: 90%.

chuyn ho mt ln: 15%.

B. Qu trnh isome ho:

Cht xc tc: CuCl trong dung mi hu c (nh-


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171

. Cht xc tc: CuCl trong dung mi hu c (nh--

picoline).

Nhit : 105-125oC.

p sut chn khng (20 kPa).

Cht c ch (phenothiazine).

chuyn ho mt ln i vi 1,4-diclo 2-buten l

khong 80%.

chn lc i vi 3,4-isome >75%.

C. Qu trnh dehydro ho:

Nhit : 80 -110oC


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172

Nhit : 80 110 C.

p sut kh quyn. Dung dch NaOH (5- 15%).

Cht c ch (axit picric).

Cc sn phm ph: 1-iclobutadien, diclo 2-buten, polyme, natriclorua v cc mono clobuten (1-clo 1-buten, 2-clo 2- buten, 2-clo

1-buten).

Thi gian l-u l 1 - 3 gi (Nu qu trnh khng s dng cht xc

tc).

chn lc > 95%.

chuyn ho mt ln gn 95%.

S cng ngh sn xut cloropren t butadien.


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173

Butadien/clo=3-6/1

95oC

75oC

65a,

-60oC


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174

ch-ng 5

Sn xut cc hp cht t BTX

5.1. Gii thiu chung

5.1.1. Ngun cung cp nguyn liu BTX


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175

g g p g y

Cc ho than nhit cao.

Reforming xc tc.

Xng nhit phn ca qu trnh cracking cc phn on ca qu trnh lc du

nh- naphta, gas oil.

Kh du m ho lng (ch yu l C3, C4).

Cracking hi n-c phn on naphta.

5.1.2. c tr-ng k thut ca nguyn liu.

Tnh cht nv

Benzen Toluen o-xylen m-xylen p-xylen


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v

Khi l-ng phnt vC 78,11 92,13 106,16 106,16 106,16

T trng 20oC 0,879 0,867 0,876 0,857 0,857

Nhit nngchy

oC 5,53 -94,99 -25,2 -13,3 -13,3

Nhit sio

C 80,1 110,6 144,4 138,4 138,4Gii hn chyntrong khngkh:D-iTrn

% thtch

1,47,1

1,36,8

1,16,4

1,16,6

1,16,6

Nhit chpchy cc kn

oC -11,1 4,4 17,2 25 25

T trng hi 2,77 3,14 3,7 3,7 3,7

Gii hn tip xc(ppm; gi)

5; 8 50; 8 100; 8 100; 8 100; 8

5.1.1.1. Reforming xc tc

* V d v mt vi phn ng ho hc:

(a) Phn ng dehydro ho cyclohexan v ng ng:


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(a) Phn ng dehydro ho cyclohexan v ng ng:

(b) Phn ng dehydroisome ho cc ng ng ca cyclopentan:

(c) Phn ng dehydro vng ho cc parafin:

CH3

CH3

+ 3H2

CH3

CH3

+ 3H2

CH3

CH3

+ 4H2C7H16

* Phn tch sn phm:


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178

5.1.1.2. Xng nhit phn

Thnh phn ca xng nhit phn c cha cc hydrocacbon thm vi t l cao cc


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179

Thnh phn ca xng nhit phn c cha cc hydrocacbon thm vi t l cao, cc

anken, dien, ankan v cycloankan

Bng 5.1:S phn b sn phm hydrocacbon thm thu -c t reformat v x ngnhit phn.

Reformat Xng nhit phn

Benzen 11 54

Toluen 55 31

Cc hp cht thm C8 34 15

5.1.1.3.Cc hp cht thm C8.


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180

Bng 5.2: T l cc hp cht C8 thm trong reformat v x ng nhit phn.

Hp phn T l hp phn (% KL) Nhit

si (o

C)

Nhit

nng chy(oC)reformat Xng nhitphn

o-xylen 24 12 144 -25

m-xylen 40 25 139 -48

p-xylen 19 10 138 13

Etylbenzen 17 53 136 -95


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Mt s qu trnh chuyn ha xylen trong hn hp C8 thm.

CH3 CH3 CH3 CH3 CH

* Isome ha (chuyn ha m-xylen thnhp-xylen):


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182

CH3

CH3

3

CH3

H

H+

CH3

CH3

H+

CH3

CH3

H

+

CH3

CH3

H

+

Ch-ngct

Tchp-xylen

C8 thm

o-xylen

p-xylen

Isome ho

Hnh 5.3. S khi phn x-ng tch xylen vi giai on isome ho

* Hydrodealkyl ha v phn b li: CH3

+ H2 +CH4

2 C6H5CH3 C6H6 + C6H4(CH3)2

5.2. Sn xut Phenol

d204=1,072, ts=41oC, tnc=182

oC

OH

* Mt s ng dng ca phenol:


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183

g g p

- Trong cng nghip ho cht: axit adipic, anilin

- Sn xut cc monome nh- Bis phenol A, caprolactam), nha phenolic.

* Cc ph-ng php sn xut phenol:

(a) Qu trnh sufonat ho benzen v sau thu phn to phenol.

(b) Qu trnh oxiclo ho benzen trong pha kh.

(c) Qu trnh oxiclo ho cyclohexan trong pha lng, sau dehydro ho c xc tc

to phenol.

(d) Qu trnh oxi ho cumen bng hydroperoxit to phenol v axeton (ph-ng php

cumen).

(e) Qu trnh oxi ho toluen.

(f) Axetoxyl ho benzen.

5.2.1. Sn xut phenol bng ph-ng php oxiclo ho benzen.

* Cng ngh Hooker Raschig:


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* Cng ngh Hooker Raschig:

Cc phn ng xy ra trong cng ngh nh- sau:

iu kin vn hnh:

- Giai on u tin (qu trnh oxi clo ho ):

. Nhit : 230 - 270oC.

. Cht xc tc: trn c s mui ng clorua v st clorua -c mang trn cht

mang tr.

. chuyn ho mt ln -c gii hn trong khong 10 -15% mol.

. chuyn ho tnh theo axit clohydric: 98 %.

C6H6 + HCl + 1/2O2(kk) C 6H5Cl + H2O

C6H5Cl + H2O C6H5OH + HCl

Ho298 = - 220 kJ/mol

Ho298 = - 12 kJ/mol

- Giai on th hai: qu trnh tinh ch mono clorobenzen bng ch-ng

ct.


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185

- Giai on th ba (thu phn monoclobenzen):

. Nhit 450 -500oC

. T l hi n-c/ monoclobenzen: 1/1 (tnh theo khi l-ng).

. Cht xc tc tricanxi photphat hoc silicagel

. chuyn ho ca qu trnh: 10 - 15%.

. Hiu sut: 85 -95% mol.

- Giai on cui cng: qu trnh tinh ch sn phm phenol bng

ph-ng php chit

. S cng ngh sn xut phenol bng qu trnh oxiclo ho benzen.Cng ngh Hooker/Raschig

Benzen


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Monoclobenzen, n-c

Mt s c im ca cng ngh ?


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187

5.2.2 Sn xut phenol bng qu trnh CumenA. Oxi ho cumen thnh hydroperoxit:

* Nguyn tc qu trnh:

C H CH(CH ) + O C H COOH(CH ) Ho = 112 kJ/mol


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C6H5 - CH(CH3)2 + O2 C6H5 - COOH(CH3)2 H 298= - 112 kJ/mol

Qu trnh oxi ho cumen thnh hydroperoxit -c thc hin bng hai ph-ng php

chnh: - Cng ngh nh t-ng(cng ngh c):

. pH=8 10,5.

. Cht nh ho: natri stearat.

. Nhit 80 120o

C. T l n-c/cumen = 2 5/1.

. Oxi nguyn cht (p sut 0,1 MPa) hoc khng kh (p sut 0,5-0,7 MPa).

- Cng ngh oxi ho trong pha ng th (cng ngh pht trin sau):

. Nhit trong khong 115 130oC.

. C ch gc t do.

- Cc sn phm ph: axit formic, axit axetic, axetonphenol, 2-phenyl 2-propanol, -

metyl styren, polyme, hydroxyl axeton...

- chuyn ho :20-25%.

- -

B. Qu trnh phn hu hydroperoxit:

* Nguyn tc qu trnh:


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* iu kin vn hnh:

- Nhit : 70-80oC.

- p sut thp (0,1-0,2 MPa).

- Thit b phn ng c cnh khuy- Cht xc tc: axit sunfonic, nha trao i ion... (0,2-1% KL).

- Thi gian l-u khong 20-30 pht

- Hn hp phn ng -c pha long vi cc sn phm ca qu trnh phn ng nh-

axeton hoc phenol.

- chn lc sn phm phenol t 94-95% mol

- Mt s sn phm ph ca qu trnh:

C6

H5

-COOH(CH3

)2

C6H

5- OH + CH

3-CO-CH

3

Ho

298= - 253 kJ/mol

S cng ngh sn xut phenol bng ph-ng php Cumen.


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5.3. Sn xut Styren i t benzen

ts=142,5oC, d204=0,906

Benzen Etylbenzen Styren+ Etylen Dehydro ho


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192

5.3.1. Qu trnh etyl ho benzen sn xut etylbenzen.

C6H6 + C2H4 C6H5-C2H5 Ho

298= - 114 kJ/mol.

- Nhit < 600oC

-Cht xc tc: axit Lewis nh- AlCl3 (qu trnh pha lng) hoc zeolit (qutrnh pha kh) .

Benzen Etylbenzen Styren

5.3.2. Qu trnh dehydro ho etylbenzen.

A. iu kin phn ng:

C H CH CH C C C 5 k / l


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C6H5-CH2-CH3 C6H5-CH=CH2 + H2 H

o298= 125 kJ/mol.

-Nhit : 550 - 650oC

-p sut 0,1 - 0,3 Mpa (vi cng ngh c) v d-i 0,1 Mpa (vi cng ngh

mi).

- Cc h xc tc : cu t hot ng (Fe2O3), cht n nh (Cr2O3, MgO,

Al2O3...), cht c ch to cc (K2O...), cht khi mo (CuO, V2O5, AgO...),

cht kt dnh (canxi aluminat...).

- T l hi n-c/etylbenzen : 1-1,2 (vi iu kin ng nhit) v 1,6-2,5

(trong tr-ng hp on nhit).

B. Qu trnh cng ngh.

(a).Dehydro ho on nhit.


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Mt thit b phn ng n lm vic iu kin p sut 0,15 - 0,2 Mpa,

chuyn ho t 40%.

H thng hai thit b phn ng t ni tip nhau ti -u t l chn lc v

chuyn ho, lm vic p sut 0,15 - 0,2 Mpa, chuyn ho t 45 - 55%.

H thng lm vic p sut thp, chuyn ho t trn 60%.


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(b). Dehydro ho ng nhit.


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196

thit b phn ng loi ng chm

-u im: nhit nguyn liu u vo thp hn, t l hi n-c/nguyn liu

u thp hn so vi qu trnh on nhit.

iu kin vn hnh v hiu sut trung bnh ca cng ngh nh- sau:

Nhit nguyn liu u vo: 580oC

Nhit dng cht ti nhit: u vo: 750oC

u ra: 630oC

T l hi n-c: 1,1- 1,2

chuyn ho mt ln: 60% chn lc: 92 - 94% mol.

S sn xut styren bng qu trnh dehydro ho etybenzen


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5.4. Sn xut alkylbenzen mch thng (LAB)

5.4.1. Gii thiu v nguyn liu v sn phm


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LAB l sn phm ca qu trnh alkyl ho benzen, -c s dng snxut tc nhn ty ra phn hu sinh hc anion.

Tc nhn alkyl ho c th l mono olefin C12-C14 mch thng hoc mono

cloankan.

V d phn ng alkyl ho benzen s dng tc nhn alkyl ho l -olefin

mch thng:

+ RCH = CH2

R- CH- CH3

H+

5.4.2. Cng ngh sn xut LAB.

Cng ngh sn xut LAB t nguyn liu ban u l benzen v


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Cng ngh sn xut LAB t nguyn liu ban u l benzen v

ankan gm hai giai on:

- Giai on 1: Dehydro ho n-parafin to mono olefin (-olefin).

Qu trnh ny thc hin p sut thp.

- Giai on 2: ankyl ho benzen bng tc nhn -olefin. Qu trnh

ny s dng cht xc tc HF, phn ng thc hin trong pha

lng nhit 40-70oC.

Cng ngh sn xut LAB(1). Thit b phn ng ehydro ho

(2). Thit b tch lng/kh

(3). Thit b chuyn ho diolefin

(4). Thit b stripping

(5). Thit b phn ng ankyl ho

(6), (7). Thit b ch-ng ct

(8). Tinh ch sn phm.


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Dng giumono olefin

5.5. Sn xut Caprolactamd204=1,02, ts=140

oC, tnc=69,3oC

(CH2)5

NH

C = O* Cc ph-ng php sn xut caprolactam:


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201

Xyclohexan Phenol Toluen

Xyclohexanol

Xyclohexanon

Xyclohexanonoxim Caprolacton

Axit benzoic

Axithexahydrobenzoic

Caprolactam

* Cc ph-ng php sn xut caprolactam:

5.5.1. Qu trnh sn xut caprolactam t toluen.

5.5.1.1. Giai on oxi ho toluen thnh axit benzoic.

CH3

+ 3/ O

COOH


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202

+ 3/2O2 + H2O

-Nhit : 160 - 170oC

- p sut: 0,8 - 1 MPa.

- chuyn ho mt ln : 20 - 40%.

- chn lc axit benzoic 93% mol.5.5.1.2. Giai on hydro ho axit benzoic thnh hexahydrobenzoic:

-Nhit : 170oC

- p sut: 1-1,5 MPa

- Cht xc t c: Pd

5.5.1.3. Giai on chuyn ho hexahydrobenzoic thnh caprolactam.

(CH2)5

NH

C = O

COOH

+ HNOSO4 + H2SO4 + H2SO4 + CO2

COOH

+ 3 H2

COOH

Cng ngh Snia/ Viscosa sn xut Caprolactam t toluen


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(1). Thit b phn ng oxi ho.(2). Thp tch toluen.(3). Thit b phn ng hydro ho.(4). Thit b phn ng nitrosyl sunfat ho.

(5). Thit b ra sn phm bng n-c.(6). Thit b trung ho sn phm.(7). Thit b chit sn phm lactam.(8). Thit b tinh ch sn phm.

5.6. Sn xut anhydrit phtalic(AP).

5.6.1. c tnh k thut v ng dng ca sn phm.

d204=1,527, tnc= 131oC, nhit thng hoa: 284,5oC d-i p sut 101,3 kPa.


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204

4 , , nc , g , p ,

Bng 5.2: Mt s c tnh k thut ca AP.

Cc ch tiu tnh cht n v Gi tr

tinh khit % KL min 99

Nhit nng chyo

C 131Axit phtalic ppm max 1 000

Axit maleic ppm max 3 000

Axit benzoic ppm max 1 000

Naphtoquinon ppm max 2

Kh nng ho tan trong benzen 1g/20g 25oC Tan hon ton

* ng dng chnh :

- Dng sn xut diankyl phtalat lm cht ho do cho cc polyme tng hp(nh- PVC) thng qua phn ng vi cc ancol

O


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OC

CO

O

CO2C8H17

CO2C8H17

+ C8H17OH + H2O

- Sn xut polyeste khng bo ho, ng dng trong cng ngh to si thu tinh.

COOC

O O

OCH2CHO

CH3

CHCOOCCH=

O O

- Sn xut nha ankyl.

5.6.2. Cc ph-ng php sn xut anhydrit phtalic:

oxi honaphtalen

o-xylen.


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cng nghpha lng

cng nghpha kh

5.6.2.2. Oxi ho o-xylen trong pha kh.

CH3

CH3

+ 3O2C

C

O

O

O + 3H2O H

o298= - 1780 kJ/mol.

- Nhit 380-400oC

- Cht xc tc: V2O5-TiO2/Si.

Sn xut AP bng qu trnh oxi ho o-xylen. Cng ngh thm xc tc c nh


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5.7. Sn xut dimetyl terephtalat v axit terephtalic.

Axit terephtalic: nhit thng hoa 300oC, d-i p sut 101,3 kPa.

Dimetyl terephtalat (d25 1 28): t 141oC t 284oC d-i iu kin p sut kh quyn


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Dimetyl terephtalat (d254=1,28): tnc= 141oC, ts= 284

oC, d-i iu kin p sut kh quyn.

5.7.2. Sn xut dimetyl terephtalat v axit terephtalic tp-xylen.

5.7.2.1. Cng ngh Witten.

A. Nguyn tc:

- Giai on oxi ho bng khng kh p-xylen thnh axit p-toluic:

C6H4 - (CH3)2 + 3/2O2 (CH3)C6H4 - COOH + H2O Ho298= - 690 kJ/mol

- Giai on este ho axitp-toluic bng metanol thnhp-metyl toluate:

Ho298= - 30 kJ/mol- Giai on oxi ho nhm metyl cn li thnh metyl terephtalat:

CH3 - C6H4 - COO - CH3 + 3/2O2 HOOC- C6H4 - COO - CH3 + H2O

Ho298= - 675 kJ/mol- Giai on este ho thnh dimetyl terephtalat:

HOOC- C6H4 - COO - CH3 + CH3OH H3C- OOC- C6H4 - COO - CH3 + H2O

Ho298= - 30 kJ/mol

(CH3)C6H4 - COOH + CH3OH CH3 - C6H4 - COO - CH3 + H2O

Sn xut dimetyl terephtalat t p-xylen bng qu trnh oxi ho v este ho.Cng ngh Witten


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209

250oC

20

a

DTP

5.7.2.2. Cng ngh Amoco:

A. Nguyn tc:

p Xylen -c oxi ho trong dung dch axit axetic bng oxi khng kh:


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p-Xylen -c oxi ho trong dung dch axit axetic bng oxi khng kh:

- Nhit khong 175 - 230oC.

- p sut 1,5 - 3 MPa.

- H xc tc gm axetat coban v mangan.

- Cht khi mo cha brom (NaBr).

Phn ng tng ca qu trnh nh- sau:

+3/2 O2

CH3

CH3

COOH

COOH

+ 2 H2O Ho298= - 1360 kJ/mol

Sn axit terephtalic bng qu trnh oxi ho p-xylen. Cng ngh Amoco.


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Ch-ng 6: Sn xut kh tng hpv cc hp cht t kh tng hp


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212

6.1. Ngun nguyn liu v cc ph-ng php sn xut kh tng hp.

-

Kh t nhin

Cc sn phm dum(naphta, FO, VR,

Asphan)

Than

Reforming hi n-c

Oxi ho khng hon ton

Kh tng hp

6.2. Mt s ng dng ca kh tng hp

Tng hp Oxo

Cc sn phm oxo


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Kh tng hpCO+H2

+ olefin

Tng hp Oxo

+ C2H2

Cc qu trnh khc

Tng hpmetanol

CH3OH

+ CH3OH

Metan ha C2H5OH

Metan ha SNG

Sn xut axit Axitaxetic

Tng hp amoniacNH3

Tch H2H2

Fischer-TropschOlefinv

parafin

Tng hpglycol

EG

Sn xut nng l-ng

Hp cht HC...

6.3. Sn xut kh tng hp bng ph-ng php oxi ha khng hon ton.


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* Nhit ng hc v ng hc ca phn ng. Phn ng chy:

Phn ng chuyn ha ca CO: Xy ra do s c mt ca n-c trong qu trnhchy v hi n-c -c -a vo.

Phn ng phn hy hydrocacbon:

Cacbon to thnh tip tc tham gia cc phn ng sau:

* Khi nguyn liu l kh t nhin, phn ng tng qut:

* Khi nguyn liu l cc HC nng hn:

CO2 + C 2CO

C + H2O CO + 2H2

CH4 + 3/2O2 CO + 2H2O

CO + H2O CO2 + H2

CH4 C(K) + 2H2

CnHm + (2n+m)/4O2 nCO + m/2H2O

CH4 + 1/2O2 CO + 2H2

Ho298 = -41kJ/mol

Ho298 =+75 kJ/mol

Ho298 = -519kJ/mol

6.3.1. Cng ngh sn xut kh tng hp bng ph-ng php oxi ha khng hon ton


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6.4. Sn xut kh tng hp bng ph-ng php reforming hi n-c.


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217

Nguyn liu:- Kh t nhin.

- Phn on ca du m (Naphta, FO, VR...)

ng hc v nhit ng hc ca phn ng:

- Qu trnh reforming hi n-c nguyn liu kh t nhin:

- Qu trnh reforming hi n-c nguyn liu Naphta:

CH4 + H2O CO + 3H2

CO + H2O CO2 + H2

H=+206 kJ/molH=- 41 kJ/mol

CnH2n+2 + nH2O nCO + (2n+1)H2O

CO + H2O CO2 + H2

H=-206 kJ/molH=- 41 kJ/mol

CO + 3H2 CH4 + H2O

Cng ngh reforming hi n-c.


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218

Metan

LPG

Naphta

Loi l-u hunh Reforming hi n-c

H2O


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219

Fuel oil

Cn chn khng

Asphal

Than

Sinh khi

Oxi ha chn lc

Ch-ng ct H2O

Khng kh

PX L-u hunh Hp th H2S

L-u hunh

H2OChuyn ha CO

Hp th CO2 (v H2S) CO2

Tinh ch

Lm kh

H2

Mt s phn ng xy ra trong qu trnh sn xut kh tng hp.

* Qu trnh oxi ho chn lc:

- Phn ng chy:

CH4 + 3/2O2 CO + 2H2O Ho298= - 519,515 kJ/mol


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220

298 , /

-Phnng

caCOvihin-c:

CO+H2O CO2 +H2

Ho

298

=-41kJ/mol

-Phn ng phn hu hydrocacbon:

CH4 C(kh) + 2H2Ho298= +74 kJ/mol

* Qu trnh reforming hi n-c:

CH4 + H2O CO + 3H2 Ho298= 206 kJ/mol

- Mt s phn ng c th xy ra trong qu trnh reforming hi n-c:

CO + H2 C + H2O

2 CO C + CO2

CH4 C + 2 H2

Ho298= - 172 kJ/mol

- Phn ng chuyn ho CO:

CO + H2O CO2 + H2 Ho

298= - 41 kJ/mol

6.2. Sn xutAmonictnc=-7

oC, ts=-33,3oC, d-204=0,6650

* Nhng ng dng ca amoniac:


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6.2.1. Nguyn tc tng hp:

N2+3H2 2N H(5000

C) =-109kJ/molN2

-Nhit : 450-500oC

- p sut: 20-25 MPa.

- Cht xc t c: Fe3O4 + Al2O3+K2O, SiO2, MgO, CaO.

-Nguyn liu khng cha hp cht l-u hunh, asen, phospho, clo, hm l-ng hp cht cha

oxi thp (O2, CO2


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S cng ngh sn xut amoniac bng qu trnh oxi ho chn lc hydrocacbon


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223

S cng ngh sn xut amoniac bng qu trnh reforming hi n-c


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224

6.2. Sn xut Urtnc=132,7

oC, d204=1,335


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225

ng dng: Sn xut phn m.

Ph-ng php tng hp: i t amoniac v cacbondioxit.

Cc phn ng xy ra:

2NH3(k) + CO2 (k) NH2 - COONH4(l)

NH2 - COONH4(l) NH2 - CO - NH2(l) + H2O

Ho198= -151kJ/mol

Ho198= 32kJ/mol

* iu kin vn hnh:

Phn ng tng hp amoni cacbamat:

o


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226

- Nhit : 170-210 C.- p sut: 12-30 MPa (15 MPa).

- NH3/CO2= 4- 6.

- chuyn ho: 75- 80% theo CO2.

. Phn ng phn hu amoni cacbamat:

- Nhit : 160 200oC.

- p sut: 0,1- 0,2 MPa

Sn xut cng nghip

Trong cng nghip, Ur -c sn xut bng hai cng ngh chnh:

- Cng ngh lin tc:


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Cng ngh dngi l-u

g g -Nhit phn ng: 180 190oC.-p sut: 24 MPa.

-Phn hu amoni cacbamat 160oC,0,1-0,2 MPa

Cng ngh tun hon mt phn NH3:

Cng ngh tun hon ton b:-Nhit : 200oC.

-p sut: 20-21 MPa

Cng ngh phc hp


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228

Cng ngh phn huamoni cacbamat s dng

dng kh stripping

Loi CO2

Loi NH3

Loi CO2 v NH3

Cng ngh Conventional Mitsui sn xut Ur


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Cng ngh SNAM/Progetti sn xut Ur


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231

* Mt s tnh cht ha l ca metanol:

- Nhit si: 64,7oC

6.4. Sn xut metanol


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232

- Nhit chp chy: 12oC

- Nhit nng chy: - 97,6oC

- Nhit t bt chy: 470oC

- T trng: d20

4= 0,7915

- p sut hi bo ha:

Ti 25oC, 125 mmHg: 0,160 atm

Ti 20oC, 94 mmHg: 0,123 atm

- Gii hn chy n (% th tch vi khng kh):

Gii hn chy n trn: 36,5%

Gii hn chy n d-i: 6,0%


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S cng ngh sn xut Metanol .(1). Thit b loi l-u hunh. (5). Thit b trao i nhit v tch.(2). Thit b bo ha. (6). Thp ch-ng ct thu hi sn phm nh.(3). Thit b tun hon. (7). Thp loi n-c.(4). Thit b phn ng.

6.5. Sn xut Formaldehyt

Formaldehyt (HCHO): ts=- 19oC, d204= 0,815.


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Formalhehyt th-ng -c tn cha d-i dng dung dch Formalin (cha 37-60%formaldehyt) vi s c mt ca metanol trnh hin t-ng t polyme ha.

Ph-ng php sn xut Formaldehyt:

- Oxi ha trc tip hydrocacbon (qu trnh i t kh tng hp).

- Oxi ha metanol.

Ph-ng php oxi ha metanol:

- Phn ng chnh:

CH3OH + 1/2 O2 HCHO + H2O Ho298= - 156 kJ/mol


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Bai Giang Cong Nghe Hoa Dau 8128