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%)
3

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

10

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

12

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.

13

* 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).

14

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.

15

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.
16

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

17

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).
18

- 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

19

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
20

* 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

21

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
22

* 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

23

* 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
24

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

Hiu sut (% KL) 40

C5+

30

C2H4

20
C3H6 H2 v CH4

10

C4H8 v C4H10

C4H6

25

khc nghit

2.1.3. Cng ngh sn xut etylen.

2.1.3.1. Cc thng s cng ngh. a. Nhit Nhit phn ng t 700 900oC tu thuc vo nguyn liu u vo. T l sn phm trong phn ng cracking c phn b nh sau:

26

Sn phm Etan H2 CH4 C2H2 C2H4 C2H6 C3H4 C3H6 C3H8 1,3-C4H6 C4H8 C4H10 Xng cracking Du nhin liu 0,9 5,9 0,9 1,6 3,7 1,3 3,6 4,2 0,2 48,2 40,0 Propan 1,3 24,7 0,3 34,5 4,4 0,3 14,0 10,0

Nguyn liu Naphta 0,8 15,3 0,7 29,8 3,8 1,1 14,1 0,3 4,8 4,2 0,3 21,0 3,8 Gas oil 0,6 10,6 0,4 24,0 3,2 1,0 14,5 0,4 4,7 4,5 0,1 18,4 17,6
27

b. Thi gian lu: Thi gian lu khong t 0,2 1,2 giy. nh hng ca nhit v thi gian lu n hiu sut to thnh etylen trong phn ng cracking naphta.

28

c. p sut hi ring phn v vai tr ca hi nc. p sut hi ring phn ca HC gim * Vai tr ca hi nc ? Tc qu trnh gim chn lc tng

* Hn ch ?

29

T l hi nc ph thuc vo nguyn liu khc nhau (KLPT ca HC) Nguyn liu Kg hi nc/kg hydrocacbon

Etan

0,2-0,4

Propan

0,3-0,5

Naphta

0,4-0,8

Gas oil

0,8-1,0

30

Cng ngh cracking hi nc.

Cng ngh cracking hi nc 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.

31

S khi qu trnh cracking hi nc.

32

S dng qu trnh cracking hi nc naphta

33

S chng tch kh sn phm ca qu trnh cracking hi nc Naphta.

1-thp tch metan(30-49 a); 2-thp tch etan(40-50a); 3-thit b hydro ha; 4-thp tch etan-etylen(110120a); 5-thp tch propan(55-60 a); 6-thp tch propan-propylen(220 a trong 2 thp); 7-thp tch butan. 34

2.2. Sn xut cc hp cht t etylen 2.2.1. Tng hp etanol

* Tnh cht Etanol l cht lng tan v hn trong nc, c t trng d = 0,789, nhit sI 78,32oC. * Nhng ng dng ca etanol: - Dung mi cng nghip - Ph gia pha xng.

35

Cc phng php sn xut Etanol

Cng ngh ln men cacbonhydrat s dng nguyn liu c th ln men trc tip nh ma ng hoc mt, tinh bt. Tng hp etanol t etylen bng phng php hydrat ho gin tip etylen c s dng axt sunfuric hoc phng php hydrat ho trc tip etylen c s dng xc tc. Ngoi ra cn c phng php tng hp etanol i t kh tng hp.

36

2.2.1.1. Phng 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 2 CH2=CH2 + H2SO4 C2H5O-SO3H (C2H5O)2SO2

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

37

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. Nhc im: d gy n mn thit b.

38

Cng ngh sn xut etanol bng phng php hydrat ho gin tip etylen
Cc kh t chy Ethylene Dung dch Soda Ete

Chng ct tch ete

Etanol 95%
Chng ct etanol

Stripping

hi nc Cc thp hp ph hi nc Nc N c thi

N c B phn thu phn N c

axit Sunfuric 90% B phn lm khan axit sunfuric

Sn xut Etanol t Etylen bng qu trnh thu phn gin tip.

Thp ra sn phm

39

Thit b phn ng thy phn

40

2.2.1.2. Phng php hydrat ho trc tip etylen. * ng hc ca phn ng.

CH2=CH2 + H2O CH3CH2OH Ho298=-45kJ/mol.

Cht xc tc: H3PO4/SiO2 Nhit khong 300oC p sut khong 7 Mpa (p sut khng c qu cao) chuyn ho etylen: 4% T l H2O/C2H4 l 0,6/1 Thi gian lu rt ngn (tc th tch dng khong 50h-1).

41

Cng ngh sn xut etanol bng phng php hydrat ho trc tip etylen

My nn etylen tun hon

Kh thi

Nc L g ia nhit TB P
Tb hydro ho chn lc acetaldehyde

Bnh tch lng /kh

Secrubbing Stripping

Kh thi

Bnh tch

H i nc

Nc thi H ydro Make-up Ethylene com p ressor My nn H ydro tun hon C c sn ph m nh

Process water
Chng ct sn phm nh

chng ng ph ethanol

E thanol 95%

42
Sn xut Etanol bng phng php hydrat ho trc tip Etylen. Cng ngh Shell

2.2.1.3. Tinh ch etanol khan.

* Phng php c in thu c etanol c nng 95 99,9% l s dng CaO hp th nc nhng qu trnh ny khng kinh t. * Phng php chng ng ph: phng php ny c thc hin vi s c mt ca benzen p sut di 12 kPa s thu c etanol c nng 95-100%, tuy nhin ct ct phi c s a kh ln. * Phng php thm thu qua mng. * Phng php ry phn t.

43

Phng php chng ng ph

44

* Cng ngh thm thu qua mng.

Gia nhit 105oC

Etanol 99,5%

Cn 94-95% Mng

Ngng t

Nc thm thu qua mng

45

Phng php ry phn t.

S nguyn tc tch nc ra khi etanol bng vt liu ry phn t.

H nc/Etanol Ry phn t Etanol > 99,5% Ry phn t cha nc

Phn t nc

Phn t etanol

46

S hp ph nc bng vt liu ry phn t trong pha hi

47

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 v gi 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 lng 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 lng 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.

48

 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 thng c s dng l oxy hoc peoxit hu c. -C ch phn ng nh sau: I 2R* RCH2-CH2* R-(CH2)n-CH2* R-(CH2)2n+1CH2R R-(CH2)n-CH2CH3 + R-(CH2)n-CH=CH2

R* + CH2=CH2 RCH2CH2* + nCH2=CH2

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

49

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) CH3 Cl (C2H5)2 TiCl2 + Al(C2H5)2Cl Cl Ti CH2 CH3 - Phn ng xy ra nhit khong 100oC. - p sut khong 20 atm - Phn ng tin hnh trong dung mi tr hexan trong pha kh. CH2 Al Cl C2H5

50

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

CH3 CH2 Ti CH2= CH2 CH2 CH3 CH3 CH2 Ti+ CH2- CH2 Al
-CH +Ti 2+CH

CH3 CH2 Al
2

CH2 CH3 CH3 CH2

Al CH2-CH3 Ti

Al CH2 CH2- CH2- CH3

Phn ng khng c qu trnh chuyn mch v to ra polime c khi lng phn t rt ln.
51

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.

52

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 phng 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. Phng php oxi ho gin tip. Phn ng chnh:

CH2=CH2

Cl2/H2O 10- 50oC

CH2 - CH2 + HCl Cl OH

100oC Ca(OH)2 CH2- CH2 + CaCl2 O

53

2.2.3.2. Phng php oxi ho trc tip.

* Phn ng: CH2=CH2 + 1/2O2 250 330oC Ag CH2 - CH2 O Ho298=-105 kJ/mol Ho298=- 135 kJ/mol Ho298=- 1225 kJ/mol

CH2=CH2 + 3O2 CH2=CH2 + 5/2O2

2CO2 + 2H2O 2CO2 + 2H2O

C ch thc hin phn ng trn xc tc kim loi: 5 M + 5 O2 5 MO2 4MO2 + 4 [CH2=CH2]hp

4 CH2 - CH2 + 4 MO O 4MO + [CH2=CH2]hp 2CO + 2H2O + 4M 2CO + MO2 2CO2 + M 5 CH2=CH2 + 5 O2 4 CH2- CH2 + 2CO2 + 2H2O O

54

* Nguyn liu: Nguyn liu etylen s dng sn xut EO phi sch (cha axetylen, hp cht cha lu 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 lu t 1-4 giy. Tc phn ng: v=[etylen].[O2] Nng etylen di 3% V

55

* 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 cha 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 lu cho c hai cng ngh ny l vn tn nhit cho phn ng duy tr nhit phn ng mc ti u nht.
56

* 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.

57

* S cng ngh sn xut EO bng oxi nguyn cht:

Etylen tun hon

CO2

CO2, vt HC,
Cc sn phm nh

Kh giu etylen
Thp loi nc Thp tinh ch sn phm Tch phn nh

EO products

Dng lng ngng t

nh hp ph CO2

CO2
hp ph CO2

kh thi

E
my nn

Dng Giu EO

EO Sp nng

1,2 MPa
cht c ch Methane ng hnh cacbonat mi

CO2

EO,EG
thp nh hp ph

sn phm nng

Nc/glycol

Oxygen Ethylene

250-270oC E.O,CO2, H2O, O2

10-40%V

thp hp ph

axetaldehyt

Axetaldehyt, polyme

Hi nc

EO, EG, Axetaldehyt

thu phn oxit thnh glycol

EG, axetaldehyt, CO2, vt HC

Sn xut Etylen Oxit bng oxi nguyn cht. Cng ngh Shell

58

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

*
Kh thi Khng kh my nn Kh thi
Nh hp ph

KK

my nn

Nc
thit b phn ng s cp Thit b phn ng th cp hp ph s cp Hp ph th cp absorption

Cc sn phm nh products
Nh hp ph

Thp tinh ch sn phm

Thp loi nc

cht c ch

Ethylene

EG
Ethylene glycol thu hi Ethylene glyc ol thu hi Cc sn phm nng

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

tc h phn nng

Etylen oxit

59

60

2.2.4. Sn xut Etylen glycol (EG).

2.2.4.1. Gii thiu chung. Monoetylen glycol thng 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%)
E.G c sn xut ch yu i t E.O bng qu trnh hydrat ho.

CH2-CH2 + H2O O

HOCH2-CH2OH

Ho298=-75 kJ/mol.

Ngoi ra cn c mt s phng 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. Phng php ny c in v khng cn c ng dng:

CH2 = CH2 + HClO HOCH2-CH2Cl HOCH2-CH2Cl + NaHCO3 + H2O HOCH2-CH2OH + CO2 + H2O + NaCl
61

- Phng php da trn qu trnh cacbonyl ho formaldehyt thnh axit glycolic, sau este ho axit ny to hydrin metyl axetat, thu phn este:
HCHO + CO + H2O HOCH2-CH2COOH HOCH2-CH2COOH + CH3OH HOCH2-COOCH3 + H2O HOCH2-COOCH3 + H2O HOCH2-CH2OH + CH3COOH

- Phng php axetoxyl ho etylen thnh diaxetat sau thu phn to glycol:
- CH2=CH2 + CH3OH + 1/2 O2 CH3COOCH2-CH2COOCH3 + H2O Ho298=-125 kJ/mol CH3COOCH2-CH2COOCH3 + 2H2O HOCH2-CH2OH + 2CH3COOH Ho298=-17 kJ/mol - Phng 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

62

- Phng 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-CH2OH - p sut:140 340 MPa - Nhit : 125 130oC. - Sn phm ph:metyl format, metanol, nc. - Phng 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.
Pd

2n-C4H9OH + 2CO + 1/2O2 (n- C4H9COO)2 + H2O Sau , phn ng hydro ho di s c mt ca xc tc ng v crom trong pha lng: (n- C4H9COO)2 + 4H2 200oC HOCH2-CH2OH + 2n-C4H9OH
3MPa
63

2.2.4.2. Cng ngh v iu kin vn hnh sn xut EG bng phng php hydrat ho EO. * iu kin vn hnh: - Nguyn liu E.O ban u c pha long bng hn hp nc 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 lu: 45 pht n 1 gi. - chn lc cc sn phm nh sau: 88,5% mol EG, 10,5% mol DEG, 0,5% mol TEG.
64

Water recycle

Condensates Monoethylene glycol

Diethylene glycol Ethylenne oxide

Dilution

Water

Hydration Triethylene glycol

Vacoum

Vacoum

Vacoum

Vacoum

Triethylene glycol separation

Monoethylene glycol

Second stage

Third stage

Fourth stage

First: stage

Diethylene glycol separation

Denhydration

separation

Heavy products

Cm thit b bay hi
Sn xut Etylen glycol bng phng php hydrat ho Etylen oxit

65

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 phng php chnh:- Phng php c in l cng hp gia axit axetic vi axetylen xy ra trong pha kh. - Phng php ngy nay c s dng l thc hin qu trnh phn ng gia etylen v axit axetic vi s c mt ca oxi. Phng php ny c ng dng nhiu ti M, Nht v mt s nc Ty u.

66

2.2.6.2. Cc qu trnh sn xut VA. A. Qu trnh phn ng trong pha lng: Phn ng chnh O CH2=CH2 + CH3- C OH + PdCl2 Pd + 2CuCl2 PdCl2 + 2CuCl 2CuCl2 + H2O 2CuCl + 2HCl + 1/2O2 O CH2=CH-O-C-CH3 + 2HCl + Pd

- 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 trng axit c cha Cl-).

67

Sn phm ph axetaldehit do phn ng ca etylen vi nc hoc phn ng thu phn VA. CH2=CH2 + H2O + PdCl2 CH3COOCH=CH2
H2O

CH3CHO + Pd + HCl CH3CHO

CH2=CHOH (khng bn)

- Thi gian lu 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...

68

* Cng ngh sn xut VA t etylen trong pha lng

69

- u im:? - Nhc im:?

70

B. Qu trnh sn xut VA trong pha kh * Phn ng: O CH2=CH2 + CH3-C OH + 1/2 O2 * 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. O CH2=CH-O-C-CH3 + H2O Ho298 = - 180 kJ/mol

71

* Cng ngh sn xut VA t etylen trong pha kh

72

- u im ?

73

2.2.6. Sn xut etyldiclorua (EDC), vinyl clorua monome (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. Phng 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...

74

* 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 di s c mt ca cht xc tc trn 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-..ClFeCl3 + CH2Cl-CH2Cl
75

FeCl4-..Cl- + CH2=CH2

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

76

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

FeCl3

77

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

78

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

79

2.2.6.2. Sn xut vinyl clorua (VC). Mt s tnh cht ca VC: d204=0,9834, tnc= -153,8oC, ts= - 13,4oC. 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 phng 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).
80

A. Sn xut VC bng phng php nhit phn EDC.

Cc iu kin chuyn ho: CH2 = CH2Cl + HCl Ho298= + 70 kJ/mol.

Qu trnh c thc hin da trn phn ng phn hu thu nhit sau: CH2Cl-CH2Cl

Phn ng bt u xy ra 300oC, p sut kh quyn, nhng phn ng t c tc cao 400oC 550oC. Phn ng xy ra theo c ch gc nh sau: (a) Khi mo: (b) Pht trin mch: (c) t mch: CH2Cl-CH2Cl CH2Cl-*CHCl Cl* + CH2Cl- CH2* CH2Cl- CH2* + Cl* CH2Cl-*CHCl + HCl CH2 = CH2Cl + Cl* CH2 = CH2Cl + HCl

Cl* + CH2Cl-CH2Cl

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

81

Cng ngh sn xut VC bng phng php nhit phn EDC

HCl tun hon

215oC

Thit b lm mt

20 a

60 a

500oC

70-75 a

25 a, 7kPa

20-25 a

15 a

82

Bi tp:
1. Sinh vin t xy dng s khi qu trnh lin hp clo ho etylen, nhit phn EDC v oxiclo ho etylen. 2. Thuyt minh s cng ngh sn xut VC bng phng php lin hp.

83

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

84

* 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 Qu trnh da trn cc phn ng sau: C2H4 + Cl2 2 CH2Cl- CH2Cl Phn ng tng cng: 2 C2H4 + Cl2 + 1/2O2 2 CH2 = CHCl + H2O CH2Cl- CH2Cl 2 CH2 = CHCl + HCl CH2Cl- CH2Cl + H2O Ho298= - 57 kJ/mol. (1) (2) (3)

C2H4 + 2HCl + 1/2O2

u im ca phng php: - Tiu tn t nng lng - S dng sn phm ph HCl - Khng dng axetylen - Chi ph r hn.
85

Sn xut VC bng qu trnh lin hp

86

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 nc 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.

87

Hin nay, nc 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 phng php sn xut PVC: - Trng hp VCM bng phng php huyn ph. - Trng hp VCM bng phng php nh tng. - Trng hp VCM bng phng php khi. - Trng hp VCM bng phng php dung dch.
88

B. Phn ng v iu kin ng hc:

n CH2=CHCl [-CH2-CHCl-]n C ch: I 2 I* I* + CH2=CHCl I-CH2- *CHCl R-CH2- *CHCl +n CH2=CHCl R-[CH2- CHCl]n- CH2- *CHCl 2 R-[CH2- CHCl]n- CH2- *CHCl R-[CH2- CHCl]n- CH=CHCl + R-[CH2- CHCl]n- CH2- CH2 Cl Hoc R-[CH2- CHCl]n- CH2- CHCl-CHCl-CH2[CHCl-CH2]-R

89

B. Cc phng php trng hp VCM sn xut PVC.

B1. Trng hp VCM bng phng php khi. Phn ng tin hnh nhit 40 70oC v p sut 5 12 bar * u im: D thc hin * Nhc im: Trng hp khi kh tch nhit cho phn ng do d xy ra vng qu nhit cc b.

90

C ch hnh thnh cc ht PVC trong phn ng polyme ho VCM bng phng php khi: Kch thc ht chuyn ho (%) 0

Git VCM

Cc ht PVC-VCM u tin

200Ao

Tp hp cc ht PVCVCM

0,1-0,2 m

3- 10

Ht PVC cui cng

2 10 m

90

91

S cng ngh sn xut PVC bng phng php khi

92

B2. Trng hp VCM trong dung dch. - Qu trnh trng hp ng th: polyme/dung mi: > Qu trnh ny ko di > i hi lng dung mi ln, c tinh khit cao.
B3. Trng hp VCM bng phng php nh tng:
H2O Cht khi mo Nh tng VCM H2O Ht nha VCM thu hi Khng kh nng Khng kh + hi nc

t c s dng trong cng nghip

VCM PVC H2O

VCM, H2O Cht nh ho Vi VCM huyn PVC kh H2O ph

VCM PVC PVC kh PVC H2O H2O VCM PVC H2O

Latex

PVC H2O

PVC

PVC
Latex

Monome ho tan Cht khi mo

Chun b nguyn liu Polyme ho Vn chuyn tn tr VCM Latex lm kh

PVC loi

93
nghin to ht ng gi Tn tr

B4. Trng hp VCM bng phng php huyn ph.

Trng hp VCM bng phng php huyn ph l phng 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 tng qu nhit cc b.

94

S khi qu trnh polyme ho VCM sn xut PVCbng phng php huyn ph

VCM Cht khi mo H2 O Cht bo v h keo Khng Khng kh kh v nng hi

VCM thu hi

VCM PVC H2O

VCM PVC H2O

PVC H2O

PVC H2O

PVC H2O

PVC

Nc thi
Polyme ho Loi VCM Tn tr PVC t Loi nc Lm kh ng gi v tn tr

95

C ch hnh thnh cc ht PVC trong phn ng polyme ho VCM bng phng php huyn ph: Kch thc ht Git VCM 0 chuyn ho (%) 0

Cc ht PVC/VCM u tin

0,1 0,2 m

15

Tp hp cc ht PVC/VCM

1 3 m

3 10

Ht PVC cui cng

2 10 m

80 - 90
96

Cng ngh sn xut PVC bng phng php huyn ph

- iu kin vn hnh ca nh my: Nguyn liu chnh:VCM VCM

Polyvinyl ancol

Polyvinyl axetat

mi VCM

tun hon Nc loi khong Cht khi mo S cp Tc nhn to huyn ph

Th cp * C ch hnh thnh cht khi mo:

2NaOH + H2O2 = Na2O2 + 2H2O Na2O2 + C2H5OCOCl

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

97

C2H5OCO-OONa + C2H5OCOCl C2H5OCO-OO-OCOC2H5

2C2H5OCOO

S cng ngh sn xut PVC bng phng php huyn ph

VCM

98

Thit b phn ng (1) Thit b phn ng (2) My khuy xon c o dng i ln (3) My khuy m neo (4) Thit b ngng t ngc dng (5) Thit b lc gii t (6) Mc PVC ti a (7) Van x ra (8) Ca x

99

Chng 3. Sn xut cc hp cht t propylen

CH3-CH=CH2
10%

Propylen oxit Axit acrylic

Propylen glycol

Propylen

13%

Acrylonitril
46%

Si polyacrylat

Nha PP Cumen Ru Axeton

100

3.1. Sn xut propylen oxit (PO).

Propylen oxit l cht lng c ts= 35 oC, nhit tnc = -112oC, t trng d204= 0,830 PO c nhiu ng dng nhng ng dng quan trng nht l c s dng lm nguyn liu sn xut polyuretan (chim 60%) v nha polyeste (20%). Cc phng 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.

101

3.1.2. Cc phng php tng hp P.O v c im ca phn ng 3.1.2.1. Qu trnh clohydrin ho propylen sn xut PO. * Phn ng v iu kin ng hc. Qu trnh ny tng 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 + H2O O

Phn ng to propylen clohydrin to nhit vi Ho298 =-225 kJ/mol Phn ng vi NaOH thu nhit nh Ho298 =5 kJ/mol.
102

S cng ngh sn xut PO bng qu trnh clohydrin propylen

103

Sn xut PO bng phng php oxi ho c s dng peroxit.

Phn ng chnh nh sau CH3-CH - CH2 + ROH O (hoc RCOOH)

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

Khi mo: RH + A R* + AH Pht trin mch: R* + O2 RO2* RO2* + RH ROOH + R* Ngt mch: 2R* R-R R* + RO2* ROOR 2RO2* Sn phm khng hot ng

104

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

iu kin phn ng: - Nhit 110 130oC - p sut 3 3,5 Mpa -Thi gian lu khong 7 gi cho mt lng isobutan chuyn ho l 35%.

- T l oxi v isobutan di 8%, m bo mc ngoi gii hn chy n di * 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 lu 0,5 1 gi/1 giai on, tng thi gian lu l 2,5 gi. - chn lc propylen oxit v ancol t 85.

105

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

O2

PO C3

100oC

PO th

Chun b nguyn liu 106

* Phn ng oxi ho isobutan: Hiu sut phn ng t 94% T l hai sn phm to thnh (peroxit v ancol): 1,2. Phng php ny trnh c s phn hu nhit ca cc peroxit v khng phi tiu tn nng lng cho s ngng t isobutan. * Phn ng epoxi ho propylen: . Sn phm ph c s dng vo nhiu mc ch c tnh kinh t.

107

3.1.2.5. Sn xut PO bng phng php oxi ho c s dng cc peraxit 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 lu 2 3 gi - chuyn ho axit peraxetic l 97 -98% - Hiu sut to PO l 92%.
108

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

109

3.2. Sn xut Polypropylen (P.P)

-CH-CH2 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 chu nhit tt

CH3

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

Xc tc cho qu trnh l xc tc Ziegler- Natta c hot tnh cao, c tnh chn lc lp th. Cc phng php sn xut PP: - Sn xut PP trong pha kh - Sn xut PP trong pha lng
110

PP 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) CH3 Cl (C2H5)2 TiCl2 + Al(C2H5)2Cl Cl Ti CH2 CH3 - Phn ng xy ra nhit khong 70oC. - p sut khong 35 atm CH2 Al Cl C2H5

111

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

CH3 CH2 Ti CH3-CH= CH2 CH2 CH3 CH3 CH2 Ti+ CH2- CH CH3 Al
+Ti

CH3 CH2 Al CH2 CH3 CH3 CH2 CH2-CH3 Ti Al CH2 CH- CH2- CH3 CH3 CH3-+CH- -CH2

Al

Phn ng khng c qu trnh chuyn mch v to ra polime c khi lng phn t rt ln.
112

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

i phn loi v hon thin sp Propylen/etylen

(1), (5) Thit b phn ng (2), (6) My nn

(3), (7) Thit b trao i nhit (4), (8) Bn cha sn phm

113

u im ca cng ngh pha kh ?

114

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

etylen

Hi nc, etylen, propylen, sp nh

(1) Thit b phn ng dng ng (2), (4) H thng tch to p hai cp

(3) Thit b phn ng copolime ho pha kh (5) Thp stripping 115

 u im ca cng ngh pha lng ?

116

3.3. Sn xut Cumen

CH3 CH3 CH

3.3.1. Gii thiu chung Cumen (isopropylbenzen) l cht lng, tan trong nhiu dung mi hu c, khng ho tan trong nc. Phng 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
117

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

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:
H 3C CH3 CH=CH2 +
-

CH3

H+

* 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.
118

- Aluminosilicat, s dng dng tng t xc tc cracking, lm vic

200oC.

3.3.2.2. Cng ngh sn xut cumen bng phng php alkyl ho bezen.

=1 bezen/propylen = 8/1 10/1

30 a

119

* c im cng ngh
Yu cu i vi cumen thng phm: c cha hm lng 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 + 2 CH(CH3)2

Nhit phn ng: 180 250oC p sut: 2 MPa T l benzen/diisopropyl benzen = 5/10.
120

3.4. Hydroformyl ho propylen sn xut ru butylic (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:
CH3 -(CH2)2-CHO 2CH3 - CH=CH2 +2CO + 2H2 (CH3)2CH-CHO

Ho298= - 125 kJ/mol

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

121

3.4.3. Cng ngh hydroformyl ho propylen sn xut ru butanol.

* iu kin vn hnh: Nhit : 110 180oC p sut 20 35 Mpa T l mol CO/H2 =1/1 1/1,2 Thi gian lu: 1 5 pht

Lng 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 5 10 Mpa. Tuy nhin, hot tnh ca h xc tc ny cn thp v c xu hng to iu kin thun li cho cc phn ng ph hydro ho olefin v aldehyt hn l xc tc thng thng.

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).
122

Hn hp cc n- v iso-aldehyt c hydro ho thnh cc ru tng ng.

CH3 -(CH2)2-CHO (CH3)2CH-CHO

H2/Ni H2/Ni

CH3 -(CH2)2-CH2OH (CH3)2CH-CH2OH

Nhit : 150 200oC p sut 5 10 Mpa, Cht xc tc: ng hoc niken

123

S cng ngh sn xut butanol

CO/H2=1/1-1/2

Cxt Co

124

* 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 ngh c c phn xng cracking xc tc isobutylaldehyt v tun hon cc sn phm cracking ny (propylen, CO, H2). Nu hydro c thay th bng hi nc, c th thu c sn phm c cha 88% n-butanol v 12%isobutanol. Phn ng chnh: CH3-CH=CH2 + 3CO + 2H2O C4H9OH + 2CO2 Ho298 = - 240 kJ/mol H thng lm vic 100oC v 1,5Mpa, c mt cht xc tc pentacacbonyl st, butyl-pyrolidon v nc.
125

3.5. Sn xut Axit Acrylic

Axit acrylic c s dng nh mt cht trung gian cho cc qu trnh tng hp cc este phn t lng thp, cc etyl, butyl v 2-etyl hexyl acrylat Cc phng 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. - Phng php polyme ho -propiolacton thu c nh qu trnh phn ng gia formaldehyt vi ceten. - Phng php oxi cacbonyl ho etylen.

126

Phng php oxi ho propylen

3.5.1. Nguyn tc phn ng.
* Phn ng chnh xy ra nh sau: CH2=CH-CH3 + O2 CH2=CH-CHO + H2O CH2=CH-CHO + 1/2 O2 CH2=CH-COOH * Phn ng xy ra theo c ch gc t do: (a)Khi mo: O2 2O* CH2=CH-CH3 + O* (b) Pht trin mch: CH2=CH-CH3 + *OH CH2=CH-CH2* + O* (c) Ngt mch: CH2=CH-CH2* + O* V CH2=CH-CHO + *OH CH2=CH-CO* + *OH CH2=CH-CHO CH2=CH-CO* + H2O CH2=CH-COOH
127

Ho298 = - 340 kJ/mol Ho298 = - 250 kJ/mol

CH2=CH-CH2* + *OH CH2=CH-CH2* + H2O CH2=CH-CH3 + *OH

* c im ca qu trnh ?

128

* Qu trnh oxi ho propylen: - Cht xc tc: CuO/SiO2 hoc Al2O3. hn hp ca cc oxit bismut, kali, coban, st, niken, thic telu, vonfram...cc axit molipdic hoc silicomolipdic. - Nhit : 300 350oC - p sut: 0,1 0,3 Mpa - T l mol nc/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.
129

* Qu trnh chuyn ho acrolein: - Xc tc trn c s hn hp ca cc oxit molipden v vanadi tm thm mt s hp cht ca vonfram, ng, crom, telu, asen.... - Nhit : 250 280oC - p sut: 0,1 0,2 Mpa - T l mol nc/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 theo acrolein
130

* iu kin cng ngh: Xc tc c trng 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 di qua lp xc tc, pha trn lp xc tc c ph mt lp cht rn tr gia nhit cho nguyn liu.
131

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

4-5%TTpropylen 30 40% TT nc 55-65% TT khng kh

90%TT

Sp giu axit acrylic hydroquinol

70oC

70oC 132

3.6. Sn xut axeton

Axeton l cht lng c t trng d204 = 0,790, tnc=-94,6oC, ts=56,1oC ng dng: - Sn xut cc hp cht nh diaxeto ancol, hexylen glycol, metylisobutylcacbinol, metylisobutyl xeton (bng phn ng ngng t aldol), Bis phenol A, Metylmetacrylat, lm dung mi... Phng php sn xut:

- Dehydro ho isopropanol, lng axeton c sn xut theo phng php ny chim 1/3 tng lng 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 v thu 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 di s c mt ca phc, cng 133 ngh ca Wacker/Hoechst.

3.6.1. Nguyn tc qu trnh Xc tc: paladi clorua v ng clorua, qu trnh chuyn ho tri qua cc giai on sau: To phc gia xc tc vi propylen: CH3-CH=CH2 + PdCl2 + 2 HCl [PdCl3.CH3-CH=CH2] - + Cl- + 2H+ Phc ny s b thu phn to thnh axeton v kim loi paladi: [PdCl3.CH3-CH=CH2] - + H2O Phn ng tng qut : CH3-CH=CH2 + PdCl2 + H2O CH3-CO-CH3 + Pd + 2 H+ +3 ClCH3-CO-CH3 + Pd + 2 HCl

Paladi kim loi phi c hon nguyn li dng ban u nh phn ng vi clorua ng. Pd + 2CuCl2 PdCl2 + 2 CuCl S kt hp ca hai qu trnh chuyn ho ny to nn giai on u tin trong cng ngh oxi ho propylen sn xut axeton: CH3-CH=CH2 + 2CuCl2 + H2O CH3-CO-CH3 + 2CuCl + 2 HCl Giai on th hai trong qu trnh l ti sinh clorua ng I nh khng kh hoc oxi nguyn cht: 134 2 CuCl + 2HCl + 1/2O2 2CuCl2 + H2O
PdCl2

 Phn ng tng ca ton b qu trnh:

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.
135

120oC 99,5%

50oC

Propylen

136

3.7. Sn xut Acrylonitril CH2=CH-CN

Acrylonitril: d204= 0,806, tnc= - 83,5oC, ts=77,3oC 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 phng php sn xut: - Phng php ammoxi ho propylen, cng ngh ny c pht trin bi cng ty Sohio 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 vi hydro cyan. - - Ammoxi ho propylen bng NO2
137

3.7.2.2. Sn xut acrylonitril bng phng php ammoxi ho propylen. * Nguyn tc qu trnh:

CH2=CH-CH3 + 3/2O2
CH2=CH-CH3 + O2 CH2=CH-CHO + NH3
Mt s phn ng ph:
-

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-CHO + H2O CH2=CH-CH=NH + H2O CH2=CH-CN + H2O

CH2=CH CH=NH + 1/2O2

2 CH2=CH-CH3 + 3O2 + 3NH3 CH2=CH-CH3 + 3O2 + 3NH3 CH2=CH-CH3 + 3O2 2CH2=CH-CH3 + 9O2

3CH3CN + 6H2O 3HCN + 6H2O 3CO + 3H2O 6CO2 + 6H2O

138

* Cht xc

tc cho qu trnh:

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)
139

* Cng ngh sn xut acrylonitril: 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 trng 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...). + Nhc 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 + Nhc 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 lu 2 15 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.
140

* iu kin phn ng: V nguyn tc: Phn ng ammoxi ho propylen xy ra vi lng d amoniac v oxi so vi h s t lng. 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 Propylen Sohio Sohio PCUK/Distillers 1 1 1 Thnh phn Amoniac 1,5 2 1,05 1,2 1,1 1,2 Khng kh 10 20 10 15 12 - 15 Hi nc 24 141

Kinh nghim: Hiu sut acrylonitril tng theo t l NH3/propylen. Thc t t l NH3/propylen =1 hoc 0,8. Nhit phn ng trong khong 400 500oC p sut di 0,3 MPa. T l mol acrylonitril/axetonitril tng ln nhanh chng khi nhit trn 400oC v t cc i khong 470 480oC.

142

* Tin hnh phn ng: chuyn ho mt ln ca amoniac t trn 95% (trong cng ngh xc tc tng 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 iu kin phn ng khc nhau Thi gian lu: 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 b thm xc tc c nh. Nhiu loi sn phm ph cng hnh thnh vi t l ln nh axetonitril, HCN... axetonitril thng c chuyn ho thnh acrylonitril theo phn ng s dng xc tc trn c s KBr mang trn cht mang nh sau:
CH3CN + CH4 + O2 + H 2O CH2=CH-CN + CO2 + CO + H2

Hydrocyanua c s dng cho qu trnh tng hp axit metacrylic, methionin... Tuy nhin, trong nhiu trng hp, trnh nhim v m bo an ton, HCN 143 c t b.

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

Tng si Cng ngh xc tc Xc tc Thnh phn sn phm Acrylonitril Hydrocyanua Axetonitril Cacbon monoxit Cacbon dioxit Cc hp cht nitril Cc sn phm nng Propan Propylen Nc Amoniac Oxi Nit Tng 5,2 1,8 0,7 1,0 1,6 Rt t 0,8 0,5 26,3 0,2 2,2 59,7 100,0 5,3 1,1 0,1 0,8 2,9 Rt t 0,8 0,2 25,2 1,0 1,8 60,8 100,0 4,3 1,0 0,3 0,5 1,2 Rt t 0,6 0,3 33,6 1,1 4,0 53,1 100,0 144 Sohio 41 Nitto 13 PCUK/Distillers Thm c nh

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

95%

Chiu cao tng XT

145

Cng ngh ammoxi ho propylen thm xc tc c nh

45-50 a

60-65 a

50-60 a

40-45 a

Nc 146

25-30 a

3.8. Sn xut isopren t propylen.

CH2=C-CH=CH2 CH3
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 nc v c tng hp bng nhiu phng php khc nhau: Phng php dehydro ho isopentan (cng ngh Houdry vad UOP). Phng php dehydro ho isoamylen (cng ngh Shell). Phng php sn xut isopren i t propylen, cng ngh ca Goodyear Scientific Design.
147

* Qu trnh cng ngh sn xut isopren t propylen. Qu trnh sn xut isopren t propylen c tin hnh theo ba bc sau: (a) Qu trnh Dime ho:

2CH3-CH=CH2

CH2=C-CH2-CH2-CH3 CH3
H0289=96 kJ/mol

(b) Qu trnh isome ho:

CH2=C-CH2-CH2-CH3 CH3
(c) Qu trnh cracking: CH3-C=CH-CH2-CH3 CH3

CH3-C=CH-CH2-CH3 CH3 H0289=-6 kJ/mol

CH2= C -CH=CH2 + CH4 CH3
H0289=63 kJ/mol
148

* iu kin tin hnh: Qu trnh dime ho: - Cht xc tc tripropyl nhm - Nhit 150 200oC - p sut 20 MPa. - Thi gian lu: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 nc. - Thi gian lu:1/10 giy.
149

Cng ngh sx isopren t propylen

150

Chng 4. Sn xut Butadien v Buten

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

151

Bng 4.1 . Nhit si ca cc cu t trong phn on C4 Hydrocacbon isobutan isobuten 1- buten Butadien n-butan trans-2-buten cis-2-buten Nhit si (oC) - 11,7 - 6,9 - 6,3 - 4,4 - 0,5 - 0,9 3,7
152

4.2. Sn xut Butadien.

CH2=CH-CH=CH2 ts=- 4,413oC, d204=0,621 * Cc phng php sn xut butadien: Axetylen v formadehyt

Axetaldehyt Etanol dehydro ho v dehydrat ho

Butadien

Phn on C4 (cracking hi nc) n-buten v n-butan

153

4.2.1. Cc phng php sn xut butadien 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 n-C4H10

CH2=CHCH=CH2 + H2 CH2=CHCH=CH2 + 2H2

154

* Dehydro ho buten c xc tc. A. iu kin vn hnh: Nguyn liu phn on C4 c x l t c nng buten thch hp(70-95%KL). Qu trnh dehydro ho buten xy ra theo phn ng sau:
CH2=CH-CH2-CH3 CH3-CH=CH-CH3 CH2=CH-CH=CH2 + H2

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 nc.
155

Bng 4.2. iu kin vn hnh qu trnh dehydro ho buten sn xut butadien trn cc xc tc khc nhau: Xc tc
620 600 76 75 80 27 26 20 300 15 925 10 0,16 0,15

Shell 105 Fe2O3/Cr2O3 680 18/1 20-30 80-70 1 gi n 7 ngy

Shell 205 Fe2O3/Cr2O3 680 0,18 8/1 500 26-28 75-73 1-24 gi

iu kin Nhit (oC) p sut (MPa) Hi nc/buten (mol/mol) Th tch dng (h-1) chuyn ho mt ln (%) chn lc butadien (%) Thi gian ti sinh xc tc

Dow B Ni v Ca photphat 680 0,20 20/1 125-175 > 45 90 15-30 pht

Phillips 1490 Fe2O3/Bauxit 680 0,18 12/1 300-400 27-33 76-69 Khng
156

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

157

* Dehydro ho butan c xc tc.

A. iu kin phn ng: Qu trnh xy ra theo phn ng sau:
CH3-CH2-CH2-CH3 CH3-CH2-CH=CH2 CH3-CH=CH-CH3 CH3-CH2-CH=CH2 CH3-CH=CH-CH3

+ H2

Ho298=127 kJ/mol Ho298=124 kJ/mol

CH2=CH-CH=CH2 + H2

- 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.
158

B. Cng ngh sn xut butadien bng qu trnh dehydro ho butan:

* Cng ngh UOP: - Thit b phn ng ng chm - Cht xc tc: oxit crom/oxit nhm - Nhit phn ng: 570oC - p sut u vo: 0,8 MPa, p sut trong cc ng l 0,5 MPa (mi ng di 5 m, ng knh 7,5 cm). - chuyn ho mt ln: 22,5%. - chn lc: 80 - 90% mol. * Cng ngh Phillips: (a) Dehydro ho n-butan thnh buten. (b) Tch buten, butan cha phn ng v cc sn phm khc bng chng ct phn on v chng trch ly bng dung mi lng furfural v sau tun hon butan cha phn ng. (c) Dehydro ho buten thnh butadien. (d) Tch v tinh ch butadien bng chng trch ly c s dng dung mi furfural sau tun hon buten cha phn ng.
159

iu kin vn hnh Nhit p sut Th tch dng

590oC 0,2 MPa 700 h-1 30% 80%(KL)

chuyn ho mt ln Lng ry phn t s dng

- 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 kh cha 2 - 3% oxi.

160

* Cng ngh catadien Hoydry (Air Products). - iu kin vn hnh: 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%.

161

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

162

4.2.1.2. Dehydro ho bng tc nhn oxi hot ng.

Phng 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 nc, qu trnh ny xy ra theo phn ng sau:

C4H8 + 1/2O2

C 4H 6 + H 2 O
Ho298= - 115 -130 kJ/mol (Tu thuc vo sn phm iso)

163

* iu kin vn hnh: 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 nc/buten l 30- 50. chuyn ho mt ln t > 60%. chn lc butadien l 95%.
164

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

165

* u im ?

166

4.3. Mt s ng dng ca Butadien

cao su styren-butadien (SBR). cao su nitril Polybutadien

Sn xut cao su tng hp

H H C C H C H H

H C

H H C C H

H C H C H C H

H H C H C H

H C

cis-1,4 polybutadien Nguyn liu tng hp hu c Sn xut Cloropren Sn xut Adiponitril

167

4.3.2. Sn xut Cloropren (2-clo 1,3-butadien) CH2=CH - CCl = CH2 ts= 59,4oC, d204= 0,9585
(a) Qu trnh xy ra theo cc bc sau: Clo ho butadien:
CH2=CH-CH=CH2 Cl2 300oC ClCH2-CH=CH-CH2Cl CH2=CH-CHCl-CH2Cl

(b)

Isome ho 1,4-diclo 2-buten:

ClCH2-CH=CH-CH2Cl CuCl 100oC CH2=CH-CHCl-CH2Cl

(c)

Dehydro ho 3,4-diclo 1-buten:

CH2=CH-CHCl-CH2Cl +15%NaOH CH2=CH - CCl = CH2 + NaCl + H2O o 100 C
168

Tnh cht ca cloropren thng phm c sn xut t butadien

Cc tnh cht 2-clo butadien 1-clorobutadien 3,4-diclo 1-buten Cc dime Cc andehyt (nh axetaldehyt) Cc peroxit

n v
% KL min % KL max ppm max ppm max ppm max ppm max

Gi tr 98,5 1,0 100 100 1000 1

169

* iu kin vn hnh. A. Qu trnh clo ho: 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%.

170

B. Qu trnh isome ho: . 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%.
171

C. Qu trnh dehydro ho: Nhit : 80 -110oC. p sut kh quyn. Dung dch NaOH (5- 15%). Cht c ch (axit picric). Cc sn phm ph: 1-iclobutadien, diclo 2-buten, polyme, natri clorua v cc mono clobuten (1-clo 1-buten, 2-clo 2- buten, 2-clo 1-buten). Thi gian lu l 1 - 3 gi (Nu qu trnh khng s dng cht xc tc). chn lc > 95%. chuyn ho mt ln gn 95%.
172

S cng ngh sn xut cloropren t butadien.

75oC 95oC

Butadien/clo=3-6/1

65 a, -60oC

173

chng 5 Sn xut cc hp cht t BTX

174

5.1. Gii thiu chung 5.1.1. Ngun cung cp nguyn liu BTX
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 nc phn on naphta.

175

5.1.2. c trng k thut ca nguyn liu.

Tnh cht n v Benzen 78,11 0,879
oC

Toluen 92,13 0,867 -94,99 110,6

o-xylen 106,16 0,876 -25,2 144,4

m-xylen 106,16 0,857 -13,3 138,4

p-xylen 106,16 0,857 -13,3 138,4

Khi lng phn vC t T trng 20oC Nhit chy nng

5,53 80,1

Nhit si

oC

Gii hn chy % th ntrong khng tch kh: Di 1,4 Trn 7,1 Nhit chp chy cc kn T trng hi Gii hn tip xc (ppm; gi)
oC

1,3 6,8 4,4 3,14 50; 8

1,1 6,4 17,2 3,7 100; 8

1,1 6,6 25 3,7 100; 8

1,1 6,6 25 3,7 100; 8 176

-11,1 2,77 5; 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:

CH3 CH3 + 3H2

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

CH3 CH3 + 3H2 CH3

(c) Phn ng dehydro vng ho cc parafin:

CH3 C7H16 + 4H2
177

* Phn tch sn phm:

178

5.1.1.2. Xng nhit phn

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 xng nhit phn. Reformat Xng nhit phn

Benzen Toluen Cc hp cht thm C8

11 55 34

54 31 15
179

5.1.1.3.Cc hp cht thm C8.

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

Hp phn

T l hp phn (% KL) reformat Xng nhit phn 12 25 10 53

Nhit si (oC)

Nhit nng chy (oC) -25 -48 13 -95

180

o-xylen m-xylen p-xylen Etylbenzen

24 40 19 17

144 139 138 136

Hnh 5.2. Quy trnh phn tch xylen t hn hp C8 thm.

Chng ct

C8 thm

Kt tinh hoc Hp ph

Cc hp cht C8 thm cn li p-xylen

o-xylen

181

Mt s qu trnh chuyn ha xylen trong hn hp C8 thm. * Isome ha (chuyn ha m-xylen thnh p-xylen):
CH3 H+ CH3 CH3
+

H H CH3

CH3
+

CH3 H CH3
+

CH3

CH3 H CH3

Chng ct C8 thm

Tch p-xylen

Isome ho

p-xylen o-xylen Hnh 5.3. S khi phn xng tch xylen vi giai on isome ho

* Hydrodealkyl ha v phn b li:

CH3

+ H2

+CH4

2 C6H5CH3

C6H6 + C6H4(CH3)2
182

5.2. Sn xut Phenol

d204=1,072, ts=41oC, tnc=182oC * Mt s ng dng ca phenol: Trong cng nghip ho cht: axit adipic, anilin

OH

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

* Cc phng 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 (phng php cumen). (e) Qu trnh oxi ho toluen. (f) Axetoxyl ho benzen.
183

5.2.1. Sn xut phenol bng phng php oxiclo ho benzen.

* Cng ngh Hooker Raschig: Cc phn ng xy ra trong cng ngh nh sau:

C6H6 + HCl + 1/2O2(kk) C6H5Cl + H2O

iu kin vn hnh:

C6H5Cl + H2O Ho298 = - 220 kJ/mol

Ho298 = - 12 kJ/mol

C6H5OH + HCl

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 %.
184

- Giai on th hai: qu trnh tinh ch mono clorobenzen bng chng ct. - Giai on th ba (thu phn monoclobenzen): . Nhit 450 -500oC . T l hi nc/ monoclobenzen: 1/1 (tnh theo khi lng). . 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 phng php chit
185

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

Monoclobenzen, nc

186

Mt s c im ca cng ngh ?

187

5.2.2 Sn xut phenol bng qu trnh Cumen

A. Oxi ho cumen thnh hydroperoxit: * Nguyn tc qu trnh: C6H5 - CH(CH3)2 + O2 C6H5 - COOH(CH3)2 chnh: - Cng ngh nh tng(cng ngh c): . pH=8 10,5. . Cht nh ho: natri stearat. . Nhit 80 120oC . T l nc/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%. - chn lc trn 90% - 97% .
188

Ho298= - 112 kJ/mol

Qu trnh oxi ho cumen thnh hydroperoxit c thc hin bng hai phng php

B. Qu trnh phn hu hydroperoxit: * Nguyn tc qu trnh:

C6H5-COOH(CH3)2 C6H5 - OH + CH3-CO-CH3

Ho298= - 253 kJ/mol

* 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 lu 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:
189

S cng ngh sn xut phenol bng phng php Cumen.

190

* c im cng ngh: - u im ?

191

5.3. Sn xut Styren i t benzen ts=142,5oC, d204=0,906

+ Etylen Benzen Etylbenzen Dehydro ho Styren

5.3.1. Qu trnh etyl ho benzen sn xut etylbenzen.

C6H6 + C2H4
- Nhit < 600oC

C6H5-C2H5

Ho298= - 114 kJ/mol.

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

192

5.3.2. Qu trnh dehydro ho etylbenzen. A. iu kin phn ng:

C6H5-CH2-CH3
-Nhit : 550 - 650oC

C6H5-CH=CH2 + H2

Ho298= 125 kJ/mol.

-p sut 0,1 - 0,3 Mpa (vi cng ngh c) v di 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 nc/etylbenzen : 1-1,2 (vi iu kin ng nhit) v 1,6-2,5 (trong trng hp on nhit).

193

B. Qu trnh cng ngh. (a). Dehydro ho on nhit. 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%.

194

S sn xut styren bng qu trnh dehydro ho etybenzen

115oC 195

(b). Dehydro ho ng nhit. thit b phn ng loi ng chm u im: nhit nguyn liu u vo thp hn, t l hi nc/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 nc: 1,1- 1,2 chuyn ho mt ln: 60% chn lc: 92 - 94% mol.
196

S sn xut styren bng qu trnh dehydro ho etybenzen

197

5.4. Sn xut alkylbenzen mch thng (LAB) 5.4.1. Gii thiu v nguyn liu v sn phm LAB l sn phm ca qu trnh alkyl ho benzen, c s dng sn xut 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:

R- CH- CH3 + RCH = CH2 H+

198

5.4.2. Cng ngh sn xut LAB. 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.

199

(1). Thit b phn ng ehydro ho

(5). Thit b phn ng ankyl ho (6), (7). Thit b chng ct (8). Tinh ch sn phm.

Cng ngh sn xut LAB

(2). Thit b tch lng/kh (3). Thit b chuyn ho diolefin (4). Thit b stripping

Dng giu mono olefin

200

d204=1,02, ts=140oC, tnc=69,3oC

* Cc phng php sn xut caprolactam:
Xyclohexan Phenol

5.5. Sn xut Caprolactam (CH )

NH C=O

2 5

Toluen Axit benzoic

Xyclohexanol Xyclohexanon Xyclohexanonoxim Caprolacton Axit hexahydrobenzoic

Caprolactam

201

5.5.1. Qu trnh sn xut caprolactam t toluen. 5.5.1.1. Giai on oxi ho toluen thnh axit benzoic.

CH3 + 3/2O2
-Nhit : 160 - 170oC - p sut: 0,8 - 1 MPa. - chuyn ho mt ln : 20 - 40%. - chn lc axit benzoic 93% mol.

COOH + H2O

5.5.1.2. Giai on hydro ho axit benzoic thnh hexahydrobenzoic:

COOH + 3 H2

COOH

-Nhit : 170oC - p sut: 1-1,5 MPa - Cht xc tc: Pd

5.5.1.3. Giai on chuyn ho hexahydrobenzoic thnh caprolactam.

COOH NH + HNOSO4 + H2SO4 (CH2)5 C=O + H2SO4 + CO2
202

Cng ngh Snia/ Viscosa sn xut Caprolactam t toluen

(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 nc. (6). Thit b trung ho sn phm. (7). Thit b chit sn phm lactam. (8). Thit b tinh ch sn phm.

203

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 di p sut 101,3 kPa. Bng 5.2: Mt s c tnh k thut ca AP.
Cc ch tiu tnh cht tinh khit Nhit nng chy Axit phtalic Axit maleic Axit benzoic Naphtoquinon Kh nng ho tan trong benzen n v % KL min
oC

Gi tr 99 131 1 000 3 000 1 000 2 Tan hon ton

204

ppm max ppm max ppm max ppm max 1g/20g 25oC

* 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
C C O O O + C8H17OH CO2C8H17 CO2C8H17 + H2O

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

CH3 OC O
- Sn xut nha ankyl.

CO O

OCH2CHO

OCCH= CHCO O O

205

5.6.2. Cc phng php sn xut anhydrit phtalic:

oxi ho naphtalen cng ngh pha lng 5.6.2.2. Oxi ho o-xylen trong pha kh. o-xylen.

cng ngh pha kh

CH3 + 3O2 CH3

- Nhit 380-400oC - Cht xc tc: V2O5-TiO2 /Si.

O C C O O + 3H2O
Ho298= - 1780 kJ/mol.

206

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

207

5.7. Sn xut dimetyl terephtalat v axit terephtalic.

Axit terephtalic: nhit thng hoa 300oC, di p sut 101,3 kPa. Dimetyl terephtalat (d254=1,28): tnc= 141oC, ts= 284oC, di iu kin p sut kh quyn. 5.7.2. Sn xut dimetyl terephtalat v axit terephtalic t p-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 + CH3OH (CH3)C6H4 - COOH + H2O

Ho298= - 690 kJ/mol

- Giai on este ho axit p-toluic bng metanol thnh p-metyl toluate:

CH3 - C6H4 - COO - CH3 + H2O Ho298= - 30 kJ/mol - Giai on oxi ho nhm metyl cn li thnh metyl terephtalat:

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

- Giai on este ho thnh dimetyl terephtalat:
HOOC- C6H4 - COO - CH 3 + CH3OH

HOOC- C6H4 - COO - CH3 + H2O Ho298= - 675 kJ/mol

H3C- OOC- C6H4 - COO - CH3 + H2O
208 Ho298= - 30 kJ/mol

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

250oC

DTP
20 a

209

5.7.2.2. Cng ngh Amoco: A. Nguyn tc: 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:

CH3 +3/2 O2 CH3

COOH + 2 H2O COOH

210

Ho298= - 1360 kJ/mol

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

211

Chng 6: Sn xut kh tng hp v cc hp cht t kh tng hp

6.1. Ngun nguyn liu v cc phng php sn xut kh tng hp. Kh t nhin

Cc sn phm du m(naphta, FO, VR, Asphan) Than

Reforming hi nc Oxi ho khng hon ton

Kh tng hp

212

6.2. Mt s ng dng ca kh tng hp

Cc sn phm oxo Tng hp Oxo NH3 Tng hp amoniac + olefin H2 Olefin v parafin EG Tch H2 Fischer-Tropsch Tng hp metanol Metan ha + CH3OH Kh tng hp CO+H2 CH3OH C2H5OH

Metan ha Sn xut axit

SNG Axit axetic

Tng hp glycol

+ C2H2 Cc qu trnh khc Hp cht HC...

Sn xut nng lng

213

6.3. Sn xut kh tng hp bng phng php oxi ha khng hon ton.

* Nhit ng hc v ng hc ca phn ng. Ho298 = -519kJ/mol CH4 + 3/2O2 CO + 2H2O Phn ng chy: Phn ng chuyn ha ca CO: Xy ra do s c mt ca nc trong qu trnh chy v hi nc c a vo.

CO + H2O
Phn ng phn hy hydrocacbon:

CO2 + H2
C(K) + 2H2

Ho298 = -41kJ/mol Ho298 =+75 kJ/mol

CH4

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

CO2 + C C + H2O
CH4 + 1/2O2 * Khi nguyn liu l cc HC nng hn: CnHm + (2n+m)/4O2

2CO CO + 2H2
CO + 2H2
214

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

nCO + m/2H2O

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

215

216

6.4. Sn xut kh tng hp bng phng php reforming hi nc.

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 nc nguyn liu kh t nhin:
CH4 + H2O
CO + H2O

CO + 3H2
CO2 + H2

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

Qu trnh reforming hi nc nguyn liu Naphta:

CnH2n+2 + nH2O
CO + 3H2

nCO + (2n+1)H2O
CH4 + H2O

CO + H2O

CO2 + H2

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

217

Cng ngh reforming hi nc.

218

Metan LPG Naphta H2O Fuel oil Cn chn khng Oxi ha chn lc Asphal Chng ct Than Khng kh Sinh khi PX Lu hunh Hp th H2S H2O Loi lu hunh Reforming hi nc

Lu hunh H2O Chuyn ha CO Hp th CO2 (v H2S) Tinh ch Lm kh

CO2

219
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

-Phn ng phn hu hydrocacbon: Ph Ho Ho298= +74 kJ/mol n 298 C(kh) + 2H CH 4 2 ng = ca * Qu trnh reforming hi nc: CO 41 vi CH4 + H2O CO + 3H2 Ho298= 206 kJ/mol kJ hi - Mt s phn /m c th xy ra trong qu trnh reforming hi nc: ng n COc: H ol + C+H O
CO + H2O CO2 + H2

2 CO CH4
CO + H2O

C + CO2 C + 2 H2
CO2 + H2

Ho298= - 172 kJ/mol

220
298=

- Phn ng chuyn ho CO:

Ho

- 41 kJ/mol

6.2. Sn xutAmonic tnc=-7oC, ts=-33,3oC, d-204=0,6650 * Nhng ng dng ca amoniac: Ure

NH3

axit nitric hydrazin

6.2.1. Nguyn tc tng hp:

N32 2H H( + 2H N 3
oC -Nhit : 450-500500

metylamin

C) = - p sut: 20-25 MPa. 109 - Cht xc tc: Fe3O4 + Al2O3+K2O, SiO2, MgO, CaO. kJ/ mol -Nguyn liu khng cha hp cht lu hunh, asen, phospho, clo, hm lng hp cht cha N2
oxi thp (O2, CO2<1ppm; CO, H2O, CO, CO2< 2ppm)
221

6.2.2. Cng ngh sn xut amoniac.

222

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

223

S cng ngh sn xut amoniac bng qu trnh reforming hi nc

224

6.2. Sn xut Ur tnc=132,7oC, d204=1,335

ng dng: Sn xut phn m. Phng php tng hp: i t amoniac v cacbondioxit. Cc phn ng xy ra:
2NH3 (k) + CO2 (k) NH2 - COONH4 (l) NH2 - COONH4 (l)

Ho198= -151kJ/mol

NH2 - CO - NH2 (l) + H2O Ho = 32kJ/mol 198

225

* iu kin vn hnh: Phn ng tng hp amoni cacbamat: Nhit : 170-210oC. 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

226

Sn xut cng nghip Trong cng nghip, Ur c sn xut bng hai cng ngh chnh: Cng ngh lin tc:
-Nhit phn ng: 180 190oC. -p sut: 24 MPa. -Phn hu amoni cacbamat 160oC, 0,1-0,2 MPa Cng ngh dng i lu Cng ngh tun hon mt phn NH3:

Cng ngh tun hon ton b: -Nhit : 200oC. -p sut: 20-21 MPa

Cng ngh phc hp

227

Loi CO2

Cng ngh phn hu amoni cacbamat s dng dng kh stripping

Loi NH3

Loi CO2 v NH3

228

Cng ngh Conventional Mitsui sn xut Ur

229

Cng ngh Stamicarbon sn xut Ur

230

Cng ngh SNAM/Progetti sn xut Ur

231

6.4. Sn xut metanol

* Mt s tnh cht ha l ca metanol: Nhit si: 64,7oC Nhit chp chy: 12oC Nhit nng chy: - 97,6oC Nhit t bt chy: 470oC T trng: d204= 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 di: 6,0%
232

* ng dng: -Dung mi cng nghip - Nguyn liu th sn xut axit axetic, dimetylmetaphtalat, formaldehyt, MTBE... - Cht chng to hydrate. - Hp cht chng ng cho xng du. - Lm nhin liu lng. * Nguyn l ca phn ng: - Qu trnh tng hp metanol c thc hin thng qua hai phn ng chnh sau:

C C

O O
2

+ +

2 H 3 H

2 2

3 3

O O

H H + H
2

C H

Ngoi ra cn c cc phn ng ph: H o

o 2 9 8

CO + 3H2
CO2 + H2
2CH3OH

CH4 + H2O
CO + H2O
CH3 -O -CH3 + H2O Dimetyl ete

= 9 4

233

(1). Thit b loi lu hunh. (2). Thit b bo ha. (3). Thit b tun hon. (4). Thit b phn ng.

S cng ngh sn xut Metanol . (5). Thit b trao i nhit v tch. (6). Thp chng ct thu hi sn phm nh. (7). Thp loi nc. 234

6.5. Sn xut Formaldehyt Formaldehyt (HCHO): ts=- 19oC, d204= 0,815. Formalhehyt thng c tn cha di dng dung dch Formalin (cha 37-60% formaldehyt) vi s c mt ca metanol trnh hin tng t polyme ha. Phng php sn xut Formaldehyt: - Oxi ha trc tip hydrocacbon (qu trnh i t kh tng hp). - Oxi ha metanol. Phng php oxi ha metanol: - Phn ng chnh:

CH3OH + 1/2 O2

HCHO + H2O

Ho298= - 156 kJ/mol

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S cng ngh sn xut formaldehyt . (1). Bm. (2). Thit b trao i nhit. (3). Thit b phn ng. (4). Thit b to hi nc. 5). Thp hp th. (6), (7). Thit b lm mt. (8). L t. (9). Thit b thu hi nhit. (10). Thit b bay hi metanol. (11). H thng un si nc nguyn liu.

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