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n mn hc: Thit k dy chuyn sn xut MTBE t iso-Butan.

Vn Huy Vng 1 Ha du 3-K43 HBK HN

Bgio dc v o to Cng ho x hi chngha Vit Nam

Trng i hc Bch Khoa H Ni c lp - Tdo - Hnh phc

Nhim vthit ktt nghip

Hv tn: Nguyn c Ho

Kho: 42- QN

Ngnh hc: Hu c - Ho du

1.ti tt nghip:

Thit kphn xng sn xut MTBE i tisoButan nng sut 50000 tn/nm.

2.Cc sliu ban u:

+Thit bphn ngng chm sdng xc tc nha trao i ion

+Thnh phn nguyn liu gm c:

. Iso-Butan 90%

. n-Butan 6,0%

. C3H8 3%

. nC4H8 0,5%

. C5+ 0,495%

. Cc cht khc 0,005%

. Nguyn liu Metanol kthut vi thnh phn:

Metanol 99,9% khi lng

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Nc 0,1% khi lng

3.Ni dung cc phn thuyt minh v tnh ton:

+Cc nguyn l ca qu trnh tng hp MTBE.

+Thuyt minh s cng ngh.

+Tnh ton:

. Cn bng vt cht v nhit lng ca thit bphn ng.

. Kch thc thit b.

. Xy dng.

4.Cc bn vth(ghi r cc loi bn vvkch thc):

+S cng nghsn xut MTBE dng xc tc nha trao i ion.

+Thit bphn ngng chm.

+Cng ngh......................................................................................................................................

...............................................................................................................................................................

...............................................................................................................................................................

+Xy dng cng nghip: ..........................................................................................................

...............................................................................................................................................................

...............................................................................................................................................................

6.Ngy giao nhim v:Ngy... ... ... ... thng ... ... ... ... nm 200

7.Ngy hon thnh nhim v:Ngy... ... ... ... thng ... ... ... ... nm 200

Ngy... ... ... ... thng ... ... ... ... nm 200

Chnhim khoa Cn bhng dn

(K v ghi r htn) (K v ghi r htn)

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Kt quim nh gi : Sinh vin hon thnh

1.Qu trnh thit k: ... ... ... ... (v np ton bbn thit kcho khoa)

2.im duyt: ... ... ... ... ... ... Ngy.......... thng ............ nm 2002

3.Bn vthit k

Ngy... ... ... ... thng ... ... ... ... nm 2002

Chtch hi ng

(K v ghi r htn)

Mc lc

Li gii thiu ............................................................................................... 1

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Phn I: Tng quan v MTBE .......................................................................... 2

I.Gii thiu chung ..................................................................................... 2

II.Tnh cht ca Metyl Tert Butyl Ete ....................................................... 7

1,Tnh cht vt l....................................................................................... 62,Tnh cht ho hc ................................................................................. 8

3,Tnh cht ca MTBE nh hng n cng ngh..................................... 9

III.Nhu cu MTBE, tnh hnh sn xut MTBE trn

thgii ................................................................................................. 9

IV.Qu trnh tng hp MTBE ................................................................... 11

1,Ho hc ca qu trnh tng hp ........................................................... 11

2,ng hc v c chphn ng .............................................................. 12

V.Xc tc ................................................................................................. 15

1,Cc yu tnh hng n qu trnh ................................................... 16

VI.Nguyn liu v tnh cht ca nguyn liu ............................................ 17

1,Cc ngun nguyn liu ......................................................................... 17

2,Tnh cht ho l ca nguyn liu .......................................................... 19

a,Tnh cht ca isobuten ........................................................................ 19

b,Tnh cht ca Metanol .......................................................................... 21

3,So snh kinh t cc ngun nguyn liu ............................................... 22

VII.Cng nghqu trnh sn xut MTBE................................................... 23

1,Sn xut thn hp kh C4- Raffinat 1 .................................................. 23

2,Sn xut tkh Butan tmkh ........................................................... 27

3,Sn xut MTBE tTert Butyl Alcohol .................................................... 33

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Phn II: So snh nh gi v la chn cng ngh........................................ 34

I.So snh cc cng ngh........................................................................... 34

II.La chn cng ngh............................................................................. 35

Phn III: Tnh ton thit kdy chuyn cng ngh...................................... 41

I.Tnh ton cn bng vt cht .................................................................. 41

1,Tnh cn bng vt cht chung ............................................................... 42

2,Tnh ton cn bng vt cht cho thit bphn ngng chm thnht53

3,Tnh cn bng vt cht cho phn ng chng tch................................ 55

II.Tnh cn bng nhit lng ................................................................... 57

III.Tnh ton thit bphn ng chnh ...................................................... 63

1,Tnh ton thtch lm vic ca thit bphn ng ................................. 63

2,Tnh kch thc thit b phn ng.......................................................... 68

3,Tnh chiu dy y v np thp ............................................................ 73

a,Tnh chiu dy np ............................................................................... 74

b,Tnh chiu dy y ............................................................................... 74

4,Tnh ng knhng dn nguyn liu v sn phm ............................. 75

5,Chn mt bch cho thit b................................................................... 76

Phn IV: Xy dng nh my ........................................................................ 77

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I.Phn tch a im xy dng nh my ................................................... 77

1,Cc yu cu chung ................................................................................ 77

2,Cc yu cu vkhu t xy dng.......................................................... 77

a,Va hnh .......................................................................................... 77

b,Va cht ........................................................................................... 77

3,Cc yu cu vvsinh cng nghip ...................................................... 77

II.Phn tch thit ktng mt bng nh my ........................................... 78

1,Nguyn tc phn vng .......................................................................... 78

2,Cc hng mc cng trnh ...................................................................... 78

III.Thit knh sn xut .......................................................................... 79

1, ngha v tc dng .............................................................................. 79

2,Cc nguyn tc c bn khi xy dng lthin ........................................ 80

3,Gii php kt cu khung phn xng ................................................... 80

4,Gii php btr thit btrn mt bng phn xng ............................. 80

Kt lun ...................................................................................................... 82

Ti li

u tham kh

o .............................................................................................................. 83

Li gii thiu

Trc vn bo v v chng nhim mi trng ang ngy cng c cp nhiu

hin nay, vic thay th xng pha ch, gy nhim mi trng, bng xng khng pha ch l

xu hng chung ca nhiu quc gia trn th gii.

tng tr s octan ca xng, ngi ta thay th s dng ph gia ch bi cc hp cht

cha oxi c ch s octan cao v khng gy nhim mi trng. Nhng hp cht cha oxi

thng c s dng l ru v ete nh Metanol, Etanol, v Metyl tert Butyl Ete (MTBE),

Etyl tert Butyl Ete (ETBE),Tert-amyl Metyl Ete (TAME),..

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y l nhng hp cht c tr s octan rt cao v rt thch hp pha vi xng nhm

lm tng tr s octan ca xng, cithin cht lng xng.

Hp cht oxi c s dng ch yu pha vo xng hin nay l Metyl tert Butyl Ete

(MTBE). y l hp cht oxi c nhng tnh cht ni bt nh: c tr s octan cao, bay

hi thp, bn oxi ho, c nhng tnh cht tng thch tt vixng,.. v c bit l khnggy nhim mi trng. Cc quc gia pht trin hin nay u s dng xng c pha MTBE

nh l: M, Anh, c, Nht, Canada,..

Nhu cu v MTBE trn ton th gii ang tng rt nhanh. Cc qu trnh cng ngh sn

xut MTBE c thit k v lp t nhiu ni nhm p ng nhu cu MTBE ang

tng ln ny.

Hin nay, Vit Nam ang xy dng nh my lc du u tin ti Dung Qut, Qung

Ngi, hn na trc sc p mi trng, chnh ph Vit Nam d tnh s loi b xng pha

ch vo nm 2006. V vy vic tnh ton thit k dy truyn cng ngh sn xut MTBE cho

xng l iu ht sc cn thit v quan trng. cng l l do ti thc hin bn n

ny.

Ni dung chnh ca bn n gm 3 phn:

Sinh vin

Vn Huy Vng

Phn I: Tng quan v MTBE

I.Gii thiu chung:

Metyl tert Butyl Ete l hp cht cha oxi c cha khi lng phn t l 88,15 v c

cng thc cu to nh sau:

CH3

CH3- O - C - CH3CH3

N c vit tt l MTBE. MTBE l

mt trong nhng ete c vai tr quan trng i vi cng nghip sn xut xng. N ng

dng lm cht ph gia cho xng nng cao tr s octan, nhm p ng c yu cu lm

vic ca ng c xng cng nh m bo v yu cu v sinh mi trng v sc kho con

ngi.

Trc y vic nng cao tr s octan cho xng ngi ta dng cht ph gia l nc

ch (CH3)4Pb, (C2H5)Pb. Tuy nhin loi ph gia ny bn cnh vic nng cao tr s octan,gim gi thnh sn phm nhng vn cn nhc im: nh hng n sc kho ca con

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ngi. nhim mi trng nh hng trc tip n ng c, khi ng c lm vic nhiu.

Chnh v cc nhc im ny ca nc ch m mt s nc trn th gii ban lut cm

v hn ch dng nc ch.

Hin nay loi ph gia c dng thay th. Vic thay th ny ng ngha vi vic s

c mt s thay i trong thnh phn xng khng ch, nhng ch yu l s khc nhau ivi ph gia nhm tng cng tr s octan.

C mt s gii php hu hiu t ti tr s octan cao hn khi khng s dng ch:

- Pha trn xng c tr s octan cao (nh xng alkyl ho, izome ho,..) vo nhin liu c

tr s octan thp.

-Nng cp v a thm cc thit b lc du sn xut hn hp xng c tr s octan

cao.

- S dng cc cht ph gia khng cha ch, nh cc hp cht cha oxi: etanol, MTBE,

MTBA, TAME,..

Trong s cc ph gia cha oxi ni trn th MTBE v etanol c s dng vi s lng

nhiu nht. Chng hn nh M, MTBE c pha trn vi 15% th tch, etanol ti 10%

th tch. Braxin pha trn ti 22% etanol vo xng trong nhiu nm.

Bn cnh vic tng tr s octan, hn hp ca xng vi ph gia cha oxi gip thi

hyrocacbonv CO t xe c s dng nhin liu. C th thy r tr

s octan ca mt s cht cha oxi in hnh trong bng:

Bng 1: tr s octan ca mt s cht cha oxi

Ph gia cha oxi RON MON

Metanol

Etanol

Tert-butanol (TBA)

Metanol/TBA (50/50)

Metyl tert-butyl ete(MTBE)

Tert-amyl metyl ete(TAME)Etyl tert-butyl ete (ETBE)

127136

120135

104110

115123

115123

111

116110119

99104

100106

9098

96104

98105

98

10395104

T ta thy, tr s RON ca MTBE vo khong 115123, do hn hp 15%

MTBE trong xng c tr s octan gc l 87 s to nn mt hn hp c tr s RON nm

trong khong 91 n 92, lm tng t 4 n 5 n v octan, tng ng vi hm lng ch

t 0,1 n0,15g/l. Tng t, tr s octan ca etanol l 120135, do hn hp 10% ca

etanol vi xng c tr s octan l 87 s to ra hn hp c tr s RON vo khong 9092.

Nn nhim mi trng trn th gii trong nhng nm gn y gy nh hng

nghim trng. Mt trong nhng nguyn nhn gy nn nn nhim mi trng l kh thica ng c c cha mt lng kh c hi nh: CO, NO, NO 2,.. Lng kh ny gy nh

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hng trc tip n mi trng. Do vy vn t ra u tin l phi gim lng kh thi

lm cho nhin liu ca ng c v lm c iu ny ta phi lm cho nhin liu ca

ng c sch hn, tc l phi sn xut xng sch, hm lng thm trong xng thp, hm

lng benzen thp hn 1%.

Mt khc c hiu sut ca ng c cao hn v tnh nng thot kh thi hon thinhn th ng c phi ts nn ln hn, tc l yu cu nhin liu phi c tr s octan cao,

m xng chng ct trc tip th tr s octan cn thp, cha yu cu ca ng c. Do vy

ngi ta s dng cc hp cht nng cao tr s octan pha vo xng, v ph gia u

tin cs dng lm nhin liu cho xng l TEL (tetra etyl ch) v TML (tetra metyl ch)

loi ph gia ny cho php nng cao ng tr s octan v lm cho gi thnh h. Loi ph gia

ny do MDOLE ngi M tm ra vo thng 11-1921 Vo nm 1929, loi ph gia ny c

mt trong xng thng phm ca M v c trong xng thng phm ca c trc chin

tranh th gii th II khng xa.

Tuy nc ch khi s dng pha vo xng b p c lng octan thiu ht v gi

thnh xng kh r, song bn cnh vic to nn c cc u im th n cng li nhng

tc hi nghim trng cho sc kho con ngi (v ch l cht c trch lu), cho mi trng

v nh hng trc tip n tnh nng ca ng c nh:

+Trong qu trnh chy to nn hp cht ch rn trong ng c.

+Kch thch s nhim bn bugi, lm tng s mi mn xylanh v cc van.

+Lm mt hot tnh ca xc tc trng hp x l kh thi, chnh v cn nhiu nhc

im nn huht cc nc ban lut cm hay s dng nc ch lm cht mang tr soctan cho xng.

Gii hn TEL cc i trong xng (g/l) nm 1998 mt s nc:

Bng 2: Gii hn TEL cc i trong xng

Nc Lng TEL trong xng (g/l)

M

Canada

, Php, B oNha,TyBan Nha

Cc nc khcAustralia

o, Thu in, Phn Lan

Triu Tin

Venezuela

Nht Bn

0,26

0,291

0,399

0,1510,3040,840

0,151

0,301

0,840

0,000

Xu hng hin nay l s dng hp cht cha oxi lm tng octan. Trong cc hp cht

oxi c ng dng thc tin nht l cc ete: Metyl tert-Butyl ete (MTBE), Tert amyl-metyl

ete (TAME), etyl tert butyl ete (ETBE).

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Khi thm hp cht cha oxi vo xng, ngoi vic lm tng octan, n cn lm gim

lng kh thi CO.

Hm lng Pbv aromatic cng nh hng ti t s octan (ON) ca hn hp nhin

liu cha MTBE v nhit si ca MTBE thp nn nh hng ca n ti ON ca phn

on c nhit si Ts

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CH3

|

CH3- O - C - CH3

|

CH3MTBE c tng hp t metanol v isobuten vi xc tc l acid rn.

Ngoi ra, MTBE cng c nhng ng dng khc trong cng nghip lc ho du nh:

dng sn xut metaacrolein, metacylic acid, v isopren, sn xut isobuten (bng cch

phn hu MTBE, tuy nhin y l bin php khng kinh t).

Nhu cu tiu th MTBE ang tng nhanh, MTBE l mt trong nhng ho cht tng

trng mnh nht trn th gii vi tc tng trng trung bnh 20% mi nm (1989 -

1994). D bo ti nm 2010 nhu cu MTBE s ln ti 29.000 nghn tn/nm.

C nhiu qu trnh cng ngh sn xut MTBE cc hng trn th gii c phtminh v lp t sn xut MTBE. Qu trnh cng ngh sn xut MTBE ca Snamprogetti

(M) s dng nguyn liu l hn hp kh C4cha isobuten. Qu trnh Hiils (CHLB c)

qu trnh ca CD Tech dng nguyn liu C4 v C5 (hn hp kh). Qu trnh ARCO vi

nguyn liu t qu trnh hyrat ho Tert-Butyl Acolhol,.. Tng cng sut ca cc xng

sn sut MTBE ang hot ng vo khong 25.275 nghn tn/nm.

II.Tnh cht ca Metyl Tert Butyl ete:

1.Tnh cht l hc ca Metyl Tert Butyl ete:

Metyl tert butyl ete trng thi bnh thng l cht lng, khng mu, linh ng,

nht thp, d chy,tan v hn trong cc dung mi hu c v cc hydro cacbon.

Mt s tnh cht vt l c trng ca MTBE c a di bng 3 [1]

Bng 3: Tnh cht vt l ca MTBE

Khi lng phn t, M

Nhit si, ts

Nhit nng chy

Hng s in mi (20oC)

nht (20oC)

Sc cn b mt

Nhit dung ring (20oC)

Nhit ho hi

Nhit chy

Nhit chp chy

88,15

55,3oC

-108,6oC

4,5

0,36 mPa.s

20 nN/m

2,18 KJ/kg.

337 KJ/kg

-34,88 MJ/kg

-280C

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Gii hn n vi khng kh

p sut ti hn, Pc

Nhit ti hn, tc

1,6584% th tch

3,43 MPa

224,0oC

T trng, p sut hi v ho tan trong nc ca MTBE theo nhit c cho

bng 4 [1]

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Bng 4: T trng, p sut hi bo ho v ho tan ca MTBE

Nhit oC

p sut

KPa

ho tan T trng

G/cm2Nc trong

MTBE, %KL

MTBE trong

nc, % KL

0

10

12

15

20

30

40

10,8

17,4

26,8

40,6

60,5

1,19

1,22

1,28

1,36

1,47

7,3

5,0

3,3

2,2

1,5

0,7613

0,7510

0,7489

0,7458

0,7407

0,7304

MTBE c th to hn hp ng ph vi nc, hoc vi Metanol.

Bng 5: Hn hp ng ph ca MTBE [1]

Hn hp ng ph Ts,o C Hm lng MTBE, %KL

MTBE - nc

MTBE - Metanol

MTBE - Metanol (1,0MPa)MTBE - Metanol (2,5MPa)

52,6

51,6

130175

96

86

6854

.MTBE khng c gii hn v tan ln vi cc dung mi thng thng.

.MTBE rt n nh trong mi trng kim trung tnh v axit yu.

.Trong mi trng axit mnh MTBE tch metanol v izo buten.

2.Tnh cht ho hc:

MTBE l cht kh n nh di iu kin acid yu, mi trng kim hoc trung tnh.Trong mi trng c cn bng:

CH3 CH3

H+

CH3- O - C - CH3 CH3OH + CH2= C

CH3 CH3

(MTBE) (Metanol) (Iso butylen)

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Trong iu kin phn ng mi trng acid, MTBE gn nh tr vi cc tc nhn

khc nh buten-1, buten-2, n-buten, isobutan,.. iu ny lm gim cc sn phm ph v

tng chn lc. Tuy vy do cn bng c th chuyn dch sang c th to thnh iso

butylen v metanol nn c th gim chuyn ha. Do vy cn phi ly MTBE ra khi

mi trng phn ng lin tc lm cn bng dch chuyn sang tri.3.Tnh cht ca MTBE nh hng n cng ngh:

Vi cc tnh cht vt l nh trnh by, MTBE c th thu hi bng chng tch v

nhit si ca MTBE l 55,3oC tc l ln hn hn hp ng ph ca metanol - hn hp

cc hyrocacbon C4(tos

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Bng 6: nhu cu MTBE trn th gii (n v tnh: 1000 tn) [2]

Nm

Nc

1994 1995 1996 1998 2000 2005 2010 Tc tng trng

1994-

2000

2000-

2010

1994-

2010

M

Canada

Chu M La

tinh

Nht

Trung ng

Chu Phi

Ty u

ng u

Chu i

Dng

Nhng vng

khc

Tng

7990

183

538

388

0

70

2259

388

0

1312

13128

10921

283

1065

427

0

70

2064

505

0

1669

17003

12174

286

1115

434

0

70

2419

542

0

1963

19003

12246

292

1186

444

147

70

2449

594

0

2472

19898

12477

297

1262

471

200

70

2487

624

0

3015

20895

13111

313

1478

534

236

85

2553

812

0

3805

22929

13361

321

1735

581

276

104

2631

1024

0

4722

24763

7,7

8,4

15,3

3,3

0,0

1,6

8,2

14,9

8,1

0,7

1,0

3,2

2,1

3,3

4,0

0,6

5,1

4,6

1,7

3,3

3,7

7,6

2,6

2,5

1,0

6,3

8,3

4,0

Hin nay cc xng sn xut MTBE c lp t nhiu ni trn th gii vi tng

cng sut vo khong 25275 nghn tn MTBE/nm. Cc xng ny c lp t da trn

cc qu trnh cng ngh ca cc hng khc nhau nh: cng ngh ca Snamprogetti (M)

se dng nguyn liu FCC-BB v thit b on nhit, c 21 xng c xy dng

nhiu ni (M, vng vnh,..) da trn cng ngh ca Snamprogetti cng mt s d n ang

c thc thi, [3]. Cng ngh ca Hiils AG cng c p dng nhiu trong cc xng

ca CHLB c,.. Nhng qu trnh cong ngh gn y nh cng ngh ARCO (caTEXACO) ang c s dng trong cc xng sn xut Texas (M) v Ty u. Cng

ngh CD Tech (ABB Lummus) cng c s dng vi hn 60 xng v gn 30 d n [3].

Cng ngh sn xut MTBE ca UOP vi 11 xng vi cng sut 30000 bpsd, s dng

nguyn liul kh butan t m kh. Hn 26 xng sn xut da trn cng ngh ca TFP,

xng sn xut da trn cng ngh ca Phillip (H Lan), cng ngh ca hng Shell,..

c xy dng v ang hot ng khp ni. Nht Bn cc xng sn xut vi cng ngh

ca hngSumimoto c xy dng.

Gn y Arp Xt, Venezuela v cc vng khc ngi ta xy dng cc xng

sn xut MTBE t nguyn liu kh Butane t m kh, s dng cng ngh ca UOP,...

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IV.Qu trnh tng hp MTBE:

1.Ho hc ca qu trnh tng hp: [1]

MTBE c to thnh nh s cng hp ca metyl alcohol vo ni i hot

ng ca iso butylen:

CH3 CH3

| |

CH2= C + CH3OH CH3- C - O - CH3

| |

CH3 CH3

Qu trnh phn ng xy ra d dng iu kin nh nhng v trong pha lng (hoc pha

lng - kh hn hp). Nhit phn ng trong khong 40-90oC v p sut t 7-20at(p sut

duy tr phn ng trng thi lng). y l phn ng to nhit nh,

mol/KJ37H thun nghch, c chn lc cao mc d c mt cc cu t C4khc (buten, n-butan, iso butan...) trong mi trng phn ng. Xc tc cho phn ng thch

hp l xc tc acid rn. C th s dng xc tc acid rn nh bentonit nhng hay s dng

nht l nha trao i ion cationit, gn y ngi ta nghin cu s dng xc tc zeolit.

Phn ng tng hp l phn ng thun nghch, cn bng dch chuyn sang phi th

ngi ta phi ly d lng metanol hn so vi h s t lng.

Qu trnh tng hp MTBE l qu trnh d th E - R

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2. ng hc v c ch phn ng: [4]

Phn ng tng hp MTBE l phn ng thun nghch, xc tc acid, ng hc v c ch

phn ng ph thuc vo mi trng phn ng, iu ny c ngha l ph thuc vo t l:

C th xem l phn ng xyra theo c ch ion vi s proton ho iso buten trc:

CH3 CH3

| +H+ |

C = CH2 C+- CH3

| |

CH3 CH3

Sau ion cacboni s tng tc vi etanol:

CH3 CH3

| |

CH3- C++ CH3OH CH3 - C - O

+- CH3 (2)

| | |

CH3 CH3 H

V cui cng:

CH3 CH3

| |CH3 - C - O - CH3 CH3- C - O - CH3+ H+

| | |

CH3 H CH3

T l R

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Trong :

r: tc phn ng

Kf: hng s tc phn ngthun

KMe: hng s cn bng hp ph ca Metanol

K: hng s cn bng nhit ng

Ci: nng ca cu t i, mol/l

i = Isobuten, Metanol, MTBE

KMT: hng s cn bng hp ph

Khi b hp ph Metanol c ni hyro theo 3 kchthc mng li ca 3 nhm SO3H

v phn ng vi isobuten t dung dch trong cc mao qun v pha to gel. S hot ng

ng tc dng ca c 3 nhm SO3H s to ra nhm tert-butyl c cu trc ging cation, vs trao i phi hp proton xy ra.

Cng theo c ch ny c th xy ra s to thnh Metyl-sec butyl Ete ging nh to ra

MTBE, song s to thnh ny mc nh bi v kh nng phn ng thp ca alken

thng, Buten-1 hu nh khng hp ph R

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Chm t R=0,7 v mn m khi R=1,7. Khi CIB cao, iso butylen trong dung dch, trong

cc mao qun v trong cc th gel phn ng vi cc phn t iso butylen c n nh

trn nha theo c ch E-R to ra di isobutylen (DIB), Metyl Sec-butyl Ete (MSBE) l

cc sn phm ph.

Khi R=1,7 th c s tng t ngt tc phn ng khi mo ca phn ng isome hobuten-1, iu ny c th l do gi tr ny hm lng mol butanol trong pha lng ln

(khong 25%). Do s hp ph thun nghch buten-1 ln nha kh ln.

Khi R=3,5, hm lng CH3OH trong pha lng cn t hn 15%mol trong khi hm

lng iso buten l 50% (nu nguyn liu l phn on C4t qu trnh Craking hi nc).

CMethp ny ht nha polime b co li v mng li SO 3H dy c, c ch L-H bt u

chim u th. Do lc ny phn ng tng hp MTBE xy ra ch yu theo c ch L-H. S

to thnh DIB theo c ch L-H cng c tc dng.

Khi R=10, lc ny phn ng ch xy ra theo c ch L-H cui cng khi tng hpMTBE t cn bng ho hc, mt c ch chuyn tip c th xy ra. R

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acid cng mnh th hot tnh xc tc cng cao. acid ph thuc vo kiu loi

v s nhm acid trn nha v b nh hng bi ni ngang (lin kt ngang). hot

ng ca xc tc nha ph thuc ch yu vo hnh thi ban u ca nha v vo tng tc

ca n vi pha phn ng gm c dung mi v nhng cht khc trong h thng phn ng.

Hnh thi ca nha trao i ion lin quan n cch tip cn ca cc phn t vo nhmSulfonic. N c th b nh hng bi tng tc ca dung mi v nhng phn t hp ph

vi nhm nh chc.

Mt s loi xc tc nha trao i ion v tnh cht ca chng c a bng 7.

Bng 7: Tnh cht ca mt s loi nha trao i ion [5]

Tn thng mi

acid

C

B mt

ring

theo

BET,

m2/g

B mt

ring

theo

ISEC,m2

/g

Th tch

mao

qun,

mL/g

ng

knh

mao

qun,

Ao

Kch

thc

ht tb,

nm

Bayer K2631

Bayer OC-1501

Ambalyst 15

Ambalyst 35

Dowex M32

Purolite CT 151

Purolite CT 165

Purolite CT 169

Purolite CT 171

Purolite CT 175

Purolite CT 179

4,83

5,47

4,75

5,32

4,78

5,40

5,00

4,90

4,94

4,98

5,25

41,5

25,0

42,0

34,0

29,0

25,0

6,2

48,1

31,0

29,0

35,0

163,8

156,9

165,7

151,2

220,1

0,67

0,52

0,36

0,28

0,33

0,30

0,16

0,38

0,47

0,48

0,33

650

832

343

329

455

252

1148

342

597

662

386

0,63

0,66

0,74

0,51

0,63

0,43

0,43

0,43

0,40

0,40

0,43

1.Cc yu t nh hng n qu trnh cng ngh:

a.nh hng ca t s Iso butene/Metanol n tc phn ng tng hp:

Khi tng t s IB/MeOH tc l hm lng Iso butylen [6] trong hn hp phn ng

tng s dn n vic gim hng s tc phn ng tng hp. iu ny l do s n nh

ca isobuten v phc hot ho, v do s tng ln nhiu cc proton hot ng.

V vy trong cng ngh cn iu chnh t l ny ph hp trnh lm gim tc

phn ng tng hp.

b.nh hng ca nng MTBE to thnh n phn ng tng hp [6]

Khi nng MTBE tng dn n s tng hng s tc , hng s m khng ph thucv nha trao i ion. C th thy rng s tng hm lng MTBE trong hn hp phn ng

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dn n nhng thay i, khng ph thuc vo nha, ca nhng thng s hot ho ( H v

S), nhng thng s m dn n s thay i phc hot ho. V iu ny lm tng tc

phn ng.

c. nh hng ca s c mt ca nc [7]

S c mt ca nc vi mt lng nh, bng hoc t hn so vi trong hn hp ngph vi metanol khng nh hng nhiu n hng s cn bng ca MTBE, thm ch c th

lm tng chuyn ho iso buten.

Nc vi mt lng nh cng c nh hng c ch v lm gim tc to ra MTBE,

c bit l phn u (phn trn) ca thit b gin on hoc thit b ng chm. nh hng

c ch s mt i khi nc b tiu th to ra TBA. TBA c to thnh rt nhanh. Cn

bng TBA t c nhanh chng hn so vi ete. V vy s c mt ca nc s dn n s

to ra phn ng ph.

VI. Nguyn liu v tnh cht ca nguyn liu cho qu trnh tng hp MTBE

Nguyn liu tng hp MTBE l Metanol v iso buten

1.Cc ngun nguyn liu [2]

Hin ti iso butylen thu c t 4 ngun:

+Iso buten t hn hp Raffinate-1, l hn hp kh thu c t qu trnh Cracking hi

nc, hn hp kh buten t xng etylen. y l ngun iso buten thng c s dng

nhiu trong cc xng sn xut MTBE trn th gii.

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Ngun nguyn liu ny c u im l nng isobuten tng i cao v c th dng trc

tip sn xut MTBE.

+Iso buten t phn on C4ca qu trnh cracking xc tc tng si (FCC-BB). Trong

ngun nguyn liu ny th nng isobuten thp hn nhiu trong butan li chim t l

ln. Do vy nu s dng ngun nguyn liu ny th gi thnh sn xut v vn u t s thn.

+ Iso buten t qu trnh hyrat ho Tert butyl Alcohol. Tert butyl Alcohol thu c

nh l ng sn phm ca qu trnh tng hp propylen oxit. Qu trnh ny c thc hin

bi ARCO chemical and Texaco Company.

+Iso buten i t qu trnh hyro ho isobutan:

Isobutan c th t cc qu trnh chn lc du hoc t qu trnh isome ho kh m n-

butan. y l ngupn nguyn liu ha hn s p ng c nhu cu MTBE v l hng

pht trin c trin vng. Mc d u t cho sn xut i hi hi cao hn.

Tc nhn phn ng th 2 l Metanol c sn xut vi tinh khit ln hn 99% v

c s dng trc tip sn xut MTBE m khng cn phi x l thm. Metanol hin

nay c sn xut vi s lng hon ton c th p ng cho tng hp MTBE c. Cng

sut cc xng sn xut Metanol hin nay cho php sn xut Metanol tng hp MTBE

vi cng sut MTBE ln ti 14.106tn/nm (1993)

2. Tnh cht ho l ca nguyn liu:

a.Tnh cht ca isobuten [8].

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Isobuten l cht kh khng mu, c th chy nhit v p sut thng. N c th

ho tan vi ru, ete v hyro cacbon, ch tan t trong nc.

Mt s tnh cht vt l ca isobuten c da bng 8:

Bng 8: Mt s tnh cht vt l ca isobuten [8]

Nhit si tos, oC (101,3 KPa)

T trng 25oC lng

0oC kh

Nhit ho hi p sut bo ho v 25oC

ts

Nhit dung ring 25oC: kh l tng

Lng (101,3KPa)

Gii hn n vi khng kh ( 20oC,101,3KPa)

p sut hi bo ho theo nhit c th tnh theo.

Trong A,B,C l cc h s c cho khong -

82+13oC

Nhit chy.

-6,90

0,5819g/m3

2,582kg/m-3

366,9J/g

394,2J/g

1589J/kg.

2336J/kg.

1,8-8,8 th tch

log10=A-B/(t+C)

A=6,84134

B=923,20

C=240,00

-2702,3KJ/mol

Iso butan c cc tnh cht ca mt defin c trng vi nhng phn ng chnh nh phn

ng cng, xc tc acid (phn ng cng ru to ete, phn ng cng cc halogen to ccdn xut halogenna, phn ng cng H2O to TBA, phn ng isome ho, phn ng polime

ho to DIB, phn ng vi CO v H2O to ra axit cacbo xlic)(CH3)3C COOH, phn ng

vi fomaldehyde to hp cht dng sn xut isopren.

Ccphn ng:

CH3 CH3

CH2 = C + H2O CH3- C - OH

CH3 CH3

CH3CH3

CH2= C +Cl2 Cl- CH2-CCH3 CH3

Cl

CH3 CH3

CH2= C + CH3OH CH3- C - O - CH3

CH3 CH3

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CH3 CH3 CH3 CH3

CH2= C + CH2= C CH3- C - CH2= C

CH3 CH3 CH3 CH3

H3C CH3 H3C H

C = C C = C

H H H CH3

CH3

CH2= C +CO + H2O (CH3)3CCOOHCH3

CH3CH2 = C +O2, 2k Metacrolein

CH3

b.Tnh cht ca Metanol: [1]

Metanol l cht lng khng mu, linh ng, d chy v tan nhiu trong nc, tan hu

ht trong cc dung mi hu c, tan t trong cht bo v du, Metanol l cht phn cc v

vy n tan nhiu trong cc cht v c phn cc v c bit l cc mui. Metanol to hn

hp ng ph vi nhiu cht nh MTBE, Acrylonitrile, hyrocacbon (n-pentan, benzen,

toluen...), Metyl acetat, Metyl metacrylat...

Mt s tnh cht vt l quan trng ca Metanol c da vo bng 9.

Bng 9: Mt s tnh cht vt l ca Metanol

Nhit si (101,3 KPa)

T trng (101,3 KPa) v 0oC25oC

50oC

Nhit nng chy

T trng nhit

25oC (101,3 KPa ) kh

25oC (101,3 KPa ) lng

nht (25o

C) lng

64,6oC

0,8100g/cm30,78664g/cm3

0,7637g/cm3

44,06J/mol.

81,08J/mol.

0,5513mPas

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hi

Gii hn n vi khng kh

Nhit ho hi (101,3 KPa)

p sut hi Metanol theo to c th tnh

theo

9,68.10- mPas

5,5% - 44%

1128,8KJ/kg

lnP=8,999 + 512,64/T

Metanol l ru n gin nht, hot ng ca n c xc nh vi nhm chc

OH. Phn ng ca Metanol xy ra qua s phn hu ca ni C-O hoc H-O v c trng vi

s thay th H hoc nhm OH.

Mt s phn ng c trng ca Metanol:

xt

CH3OH HCHO + H2

Phn ng loi nc:

-H2O

2CH3OH CH3- O - CH3

Phn ng hyro ho:

CH3OH +H2 CH4+ H2O

Phn ng oxy ho bi oxy khng kh nhit cao:xt KL

CH3OH + 1/2O2 CH2O + H2O

CH2O + 1/2O2 CO +H2O

Khi oxy ho su:

xt oxt

CH3OH + O2 HCOOHCH3OH + 1/2O2 CH2O + H2O

Phn ng to este vi cc axt:

O||

CH3OH + H2SO4 H3C - O - S - O - CH3||O

CH3OH + CH2= C - COOH CH2= C - COOCH3

CH3 CH3

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Phn ng thay th nhm OH:

CH3OH + NH3 CH3NH2+ H2O

3.So snh kinh t cc ngun nguyn liu:

C th so snh gi ca cc ngun Iso buten theo bng 10.

Bng 10: Tng kt gi nguyn liu sn xut MTBE [2]

Iso buten t qu trnh cracking hi nc

Iso buten t qu trnh cracking xc tc (FCC-

BB)

Iso buten t hyrat ho TBA

Iso buten t khs butan m kh

Metanol

Cents/Pound

9,5

9,5

11,1

7,5

5,0

Gi tnh thi im 1995 (qu 4) khu vc vng vnh.

VII.Cng ngh qu trnh sn xut MTBE hin nay c s dng trn th gii.

Cc qu trnh sn xut MTBE khc nhau da trn cc ngun nguyn liu khc nhau.

1.Sn xut MTBE t hn hp kh C4Raffinat-1 tphn xng etylen v t hn

hp FCC-BB t qu trnh cracking xc tc.

S khi ca qu trnh sn xut MTBE t kh C4t xng etylen.

Metanol

Kh Raffinat -1 MTBE

C4S

Nu ngun nguyn liu l isobuten t qu trnh cracking xc tc:

Metanol

FCC - C4S MTBE

yl ngun nguyn liu truyn thng thng c s dng trong cc xng sn xut

MTBE trn th gii. V vy qu trnh sn xut i t hn hp kh Raffinat -1 hoc FCC-BB

l qu trnh sn xut MTBE ph bin trc y. u im ca n l gi thnh sn xut r,

do nguyn liu l c sn gi thnh sn phm r v nguyn liu l cc sn phm th yu ca

Xng

MTBE

Xng

MTBE

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cc qu trnh lc du v c th s dng trc tip sn xut MTBE. Tuy vy do s hn ch

v s lng nguyn liu m phng php ny ang dn b thay th.

Mt s cngngh dng ngun nguyn liu l hn hp Raffinal-1 hoc FCC-BB gm

c:

Hnh 1: S cng ngh ca Snamprogetti

S cng ngh ny s dng nguyn liu l hn hp C4 t qu trnh cracking hi

nc hoc hn hp kh FCC-BB. Thit b phn ng th nht l thit b ng chm thc hin

phn ng ng nhit, thit b th 2 thc hin on nhit. Xc tc c sp xp sao cho vic

iu khin nhit l tt nht v chuyn ho t xp x 100%.

Cng ngh MTBE ca Hiils - c s dng nguyn liu l hn hp kh Raffinal-1.

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Qu trnh tng hp y c chia lm 2 giai on vi chuyn ho isobuten t

99,9%.

S ny c th s dng nguyn liu l hn hp l hyro cacbon C4hoc isobuten t

qu trnh hyro ho isobutan. Cng ngh CD Tech s dng 2 thit b phn ng. Thit b

th nht l thit b phn ng on nhit, cn thit b 2 l thit b phn ng chng tch, vathc hin phn ng va chng tch. Trong thp phn ng chng tch 2 ngi ta b tr

nhng khong chng tch v nhng khong cha xc tc thc hin phn ng

tng chuyn ho sn phm. y l cng ngh mi s dng k thut phn ng chng

tch (3) l ct tch MTBE kkhi Metanol, (4) l ct tch Metanol - nc.

Mt s cng ngh khc cng c s dng nguyn liu t C4nh cng ngh ca IFP

(hnh 4), cng ngh Phillip (hnh 5).

Hnh 3: Cn n h CD

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Qu trnh chuyn i bng phn ng ete ho, c th thu c MTBE, ETBE, TAME,

TAEE, s bin i ca iso butylen ln ti 99%, thit b s dng lp xc tc c nh.

Nguyn l hot ng:

Ngun Metanol v isobuten thit b dehyro ho c trn ln vi ngun Metanol

ti sinh t thit b ti sinh v tt c c a vo phn ng (1). Ti y, mt phn

isobutylen phn ng vi Metanol tuy nhin vn cn mt lng Metanol v isobutylen cha

phn ng. Hn hp gm c sn phm MTBE v phn cha phn ng c dn ra khi y

ca thit b (1) v dn ti thit b phn tch. Ti y, sn phm MTBE c tch ra khi

y thit b, cn nhng cu t cha phn ng c a qua b phn trao i nhit v vo

thit b phn ng (2). Ti (2) tip tc xy ra phn ng ete ho, sn phm c tch ra khiy ca thit b v c chia lm 2 phn: mt quay tr li thp phn tch tch sn phm

MTBE, mt i vo ct phn tch Metanol. Ti ct phn tch Metanol, pha trn nh ca

n l lng isobutan cn ln isobutylen, hn hp ny c a ti thit b dehyro ho.

Metanol c dn ti thit b ti sinh v quay tr li thit b phn ng (1) trn vo dng

Metanol v isobutylen.

H thng thit b ny cho php d dng thay xc tc m khng phi dng qu trnh li.

Qu trnh cho php thu hi MTBE vi hiu sut cao.

2.Sn xut MTBE t kh butan t m kh [9], [10], [2].

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y l xu hng sn xut mi s dng nguyn liu l phn butan tch t kh t nhin

vi tr lng ln.

S qu trnh sn xut MTBE t kh n-butan nh sau:

Qu trnh bao gm 3 giai on:

+Isome ho kh m n-butan to thnh isobutan, qu trnh isome ho xy ra nhit

thp (150-200oC) v p sut l 200-400psig trong pha hi. Xc tc cho qu trnh l Pt hoc

Al2O3hoc Pt/Al2O3c tm mt lng hp cht hu c dn xut clo.

Kh n-butan a vo s chuyn ho thnh isobutan gn im cn bng. Mt s qu

trnh isome ho thc hin isome n-butan to thnh isobutan l : qu trnh isome ho ca

Lummus (hnh 6), qu trnh Butamer (UOP) (hnh 7)

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+Qu trnh hyro ho isobutan thnh isobuten:

Qu trnh hyro ho ny c thc hin t=540760oC v p sut thp. Xc tc

phn ng c th l Cr/Al2O3 hoc Pt. Sn phm thu c cha 7585% iso buten v

isobutan. Cc qu trnh hyro ho hin nay sn xut iso buten l: qu trnh Catofin

(Lummus) hnh 8, qu trnh oleflex ca UOP (hnh9), qu trnh STAR ca Phillip, qu

trnh FBD-4 ca Snamprogetti (hnh10 v11)

Hnh 8: Cng ngh Catofin ca ABB Lummus Crest

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Qu trnh ny s dng xc tc Crom oxit, nhit cp cho phn ng bng cch t chy

ci to thnh xc tc nh dng khng kh nng.

Qu trnh ny thc hin p sut hi chn khng v vy phi ch to thit b kh khn.

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Nhit cp cho cc phn ng c thc hin bng cc thit b gia nhit tng giai

on, v nh dng H2tun hon mang nhit vo.

Qu trnh STAR vi thit b phn ng dng l, qa trnh ny t gn n thc hin

ng nhit v do tng chn lc, xc tc l kim loi qy.

Qu trnh FBD-4 s dng xc tc Crom oxit dng bt, qu trnh ny thc hin lin

tc, xc tc c ti sinh lin tc.

+Qu trnh ete ho isobuten thnh MTBE: qu trnh ny c tin hnh to=40-90oC

v p sut t 7-29 at, xc tc l nha trao i ion. Phn ng thc hin trong qua lng. Cng

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ngh qu trnh ete ho ca mt s hng nh qu trnh CD Tech (Lummus), Ether max

(UOP), Phillip, Etherfication Process (Phillip)...

3.Sn xut MTBE t Tert Butyl Alcohol:

y l qu trnh sn xut MTBE i t nguyn liu iso buten ca qu trnh hyrat

ho TBA. TBA thu c l ng sn phm trong qu trnh sn xut propylen oxit.S qu trnh:

Tert-Butyl Alcohol isobuten

Qu trnh sn xut MTBE t TBA do hng Texaco thchin c s nh sau:

Phn II: So snh nh gi v la chn

cng ngh

I. So snh cc cng ngh:

C th thy rng vic s dng cc cng ngh s dng ngun isobuten trc tip t kh

ca qu trnhcracking hi nc, s dng nguyn liu FCC-BB sn xut MTBE, ch c

th p dng vi quy m nh do ngun nguyn liu hn ch. Cng ngh MTBE t cc

nguyn liu khc nhau c th thy bng 11.

Bng 11: Cng ngh MTBE nm 1995 vng vnh [2]

hyrat

ho MTBE MTBE

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Ngun nguyn liu Cng sut

1000tn/nm Thng/ngy

Kh butan m

Kh cracking hi ncKh cracking xc tc

Nguyn liu t xng PO/TBA

800.000

100.00080.000

100.000

20.000

2.5002.000

25.000

C th s dng cng ngh ca CD Tech sn xut MTBE t ngun nguyn liu hn

hp C4Raffinal-1 hay FCC-BB t chuyn ho cao v n gin (lp t trong nh

my ho du).

V kinh t y l cng ngh c vn t 14,4 triu USD vi gi thnh sn xut 0,096

USD/cn Anh.

MTBE t kh ho du khng my hp dn, cng c th s dng cc cng ngh nh vi

nguyn liu Raffinat (Snamprogetti, Hiils, CD Tech...).

Hin nay cng ngh mi sn xut MTBE c trin vng l cng ngh sn xut

MTBE t kh butan m. Mc d u t ban u cho cng ngh ny ln, song c th sn

xut vi cng sut ln. Cng ngh mi ca UOP (gm qu trnh Butamer, oleflex v

Ethermax), c nhiu u im hn qu trnh ca ABB Lummus v qu trnh ti sinh xc tc

tin hnh lin tc v do xc tc lun c hot cao. Hin nay la chn cng ngh

nn i theo phng php ny.

V kinh t vn u t sn xut MTBE theo phng php ny l 193,1 triu USD,

gi thnh sn xut l 206 USD/1000 tn MTBE.

Sn xut MTBE i theo cng ngh ARCO ca TAXACO c vn u t 68,7 triu

USD. Gi thnh sn xut l 264 USD/1000 tn. Phng php ny cng c th sn xut

MTBE vi cng sut ln 1.000.000 tn/nm, song gi thnh sn xut t hn. V phi kt

hp vi qu trnh sn xut Propylen oxit.

II.La chn cng ngh:

T phn tch trn c th thy rng sn xut MTBE vi cng sut ln th tt nht

l nn i theo cng ngh s dng nguyn liu l kh butan m. Song vi hon cnh Vit

Nam, nhu cu MTBE s cha ln lm, v li nu nh my lc du s 1 i vo hot ng th

lng nguyn liu C4 t cc qu trnh ch bin du s c th p ng sn xut

MTBE, nguyn liu cng c th l kh isobutan t qu trnh isome ho kh butan m. Do

vy nu nguyn liu ca ta l isobutan th ta chn cng ngh cho qu trnh hyro ho l

cng ngh Oleflex v cho qu trnh ete ho isobuten l qu trnh Ethermax.

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S cng ngh sn xut MTBE t isobutan da trn cc qu trnh Ethermax (UOP)

nh hnh 13.

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Ch thch:

1.Thit b gia nhit

2.Thit b phn ng dehydo ho 19.Thit b trao i nhit

3.Thit b ti sinh xc tc 20.Thit b phn lykh khng

4.Thit b lm lnh ngng -IB butan

5.My nn 21.Van iu chnh lu lng

6.Thit b sy 22.Thit b gia nhit y thp

7.My gim p 23. Thit b ngng t hi lu

8. Thp tch kh nh. 24. Pin nhit in

9.Thit b lm lnh 25. Bm

10.Thit b phn ng ng chm

11.Thit b phn ng - chng tch

12.Thp hp th CH3OH

13.Thp chng tch CH3OH - H2O

14. Thng cha mtanol

15.Thng trn mtanol v iso - C4H8

16.Thng cha isobuten

17.Thng cha MTBE

18. Thng cha isobutanThuyt minh s cng ngh:

Kh isobutan lng c cha trong thng cha nguyn liu, kh isobutan c trao i

nhit vi sn phm nng nhit v i vo thit b gianhit (1). Kh isobutan nguyn

liu c trn ln vi kh isobutan tun hon t thit b MTBE ( x l) v c gia nhp

nng nhit n nhit yu cu. Sau isobutan c a vo nh thit b phn

ng cng vi xc tc ri t nh thp xung. H thng thit b phn ng gm nhiu thit b

ni tip nhau. H thng ti sinh cng c b tr bn cnh h thng thit b phn ng.

Trong qu trnh phn ng c th ly mt lng nh xc tc gim hot tnh t ythit b phn ng, cui cng a sang tisinh, cn t y thit b khc c a tr li

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nh ca thit b phn ng sau . Dng ra khi thit b phn ng th nht c gia nhp

v a vo thit b th hai. Sau khi ra khi thit b phn ng th hai, dng sn phm c

gia nhp thit b gia nhit th ba v a vo thit b phn ng th ba v c tip tc.

Dng ra khi h thng thit b phn ng c trao i nhit vi nguyn liu, lm mt,

sy kh v trao i nhit vi dng kh thi trc khi i vo thp tch kh thi giu H 2. Khthi ny l phn khng ngng trong thit b tch c nn v mt phn tun hon li, mt

phn ln c a i thu hi, sn xut in cho phn xng hoc dng cho cc qu trnh

lm lnh hoc s dng lm nhin liu kh hoc dng sn xut H2tinh khit.

Sn phm y cathit b lm lnh (9) l phn lng ngng t cha ch yu l C 4v

isobuten. Cn li l isobutan cha phn ng, n-butan, propan, C3H6,... c a sang phn

tng hp MTBE nh bm.

Dng kh giu H2tun hon li duy tr n nh xc tc t chy cc to ra v gip

cho qu trnh cp nhit tt hn.Phn hn hp lng cha isobuten c bm sang thit b trn v gia nhit nng

nhit ln 60oC. Metanol sch t b cha c bm ln v trn vi nguyn liu C 4v i

sang thit b phn ng th nht sau khi trao i nhit vi dng sn phm MTBE i ra.

thit b phn ng th nht, xctc c b tr trong cc ng chm v nhit to ra ca

phn ng c ly i bng nc lm lnh. Dng sn phm ra khi thit b phn ng th

nht c a sang thit b phn ng - chng tch nng nhit chuyn ho isobuten

ln 99,9%, ng thi MTBE cng c tch ra y thit b phn ng - chng tch ny.

Nhng tc nhn cha phn ng, Metanol v hn hp C4 t nh thit b phn ngchng tch c ngng t, mt phn hi lu,phn khc c a sang thp hp th

Metanol. Ti y nc c phun t di ln, hn hp hi Metanol + C4s c i t trn

xung, Metanol b tan vo nc v thu c y thp, kh C 4cha phn ng khng tan

c thu hi trn nh thp v c a i x l trc khi tun hon v dy chuyn

dehydro ho.

Hn hp Metanol - H2O y thp hp th c a sang thp chng tch. Ti y

Metanol c tch khi nc v i ln nh thp, Metanol c ngng t lm mt v tun

hon v cng vi Metanol nguyn liu.Nc thu y thp chng tch c bm li thp hp th. Mt phn nc cha trong

nguyn liu ru khng phn ng cng c thu hi thp ny. Do c th ly ra mt

phn nh H2O y thp ny.

MTBE thu c s c a v b cha MTBE.

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Phn III: Tnh ton thit k dy truyn cng ngh.

I.Tnh ton cn bng vt cht:

Dy truyn sn xut MTBE t nguyn liu kh isobutan vi cng sut 50.000 tn/nm.

Dy truyn sn xut 24h/ngy v mt nm lm vic 330 ngy cn 35 ngy ngh sa

cha, bo dng nh k.

*Cc ch tiu sn xut:

Nng sut MTBE: 50.000 tn/nm Nh vy nng sut dy truyn tnh theo

gi l:

Tnh theo Kmol/h:

(khi lng phn t ca MTBE l 88)

Nng sn phm:

MTBE chim 99% (khi lng)

Metanol chim 0,5%

Cn li l dime ca i-Butylen, ru, TBA, nc...

Thnh phn nguyn liu:Nguyn liu l kh iso-butan tiu chun c cho bng 12 (theo TY38.101492-79)

Loi B

h6313,13kg/330.24

50.000.000

h71,74Kmol/88

6313,13

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Bng 12: Thnh phn kh iso-butan nguyn liu

Thnh phn % th tch

Iso butan

Propan

Tng Buten

n-butan

C

Cc cht khc

H2S v Mercaptan

H2O v kim

90

4,5

0,5

6

0,5

0,005

0

Metanol nguyn liu l metanol thng phm vi thnh phn:

Metanol 99,9% (khi lng)

Nc 0,1%

Tng aceton v aldehyd < 30 mg/kg

Tng acid < 30 mg/kg

Phn cn < 10 mg/kg.

1. Tnh cn bngvt cht chung:Qu trnh sn xut MTBE qua 2 giai on: giai on hyro ha isobutan v giai

on tng hp MTBE. Ta tnh cn bng vt cht tng giai on:

Giai on tng hp MTBE:

Cn bng: khi lng vo = khi lng ra

- Cc dng khi lng i vo phn tng hp MTBE gm c:

+ Hn hp C4lng i ra t phn hyro ha: G1, kg/h

+ Dng nguyn liu Metanol : GMeOH , kg/h

- Cc dng sn phm i ra khi phn tng hp MTBE gm c:

+ Hn hp kh C4cha phn ng : GC 4 cha phn ng , kg/h

+ Sn phm MTBE : GMTBE , kg/h

H2O do trong nguyn liu Metanol cha 0,1% (W).

y on gin ta coi rng trong qa trnh hp th Metanol v qa trnh chng

tch thu hi Metanol v nc, lng H2O s dng khng b mt mt v c tun hon li

5

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cho qa trnh hp th Metanol v lng H2O ly ra bng lng nc a vo dy chuyn

do c trong nguyn liu Metanol v bng GH2O, kg/h

Tnh ton cc khi lng G1, GMEOH, GC 4 cha phn ng, GMTBE , nh sau:

+ Khi lng sn phm MTBE i ra phi l nng sut quy nh ca ton dy chuyn

sn xut v bng 6313,13 kg/h.

Vy GMTBE= 6313,13 kg/h

+ giai on tng hp, phn ng tng hp nh sau:

Iso-buten + MeOH MTBE

y l phn ng thun nghch, tuy vy khi qua thp phn ng chng ct (thp CD)

theo cng ngh CD Tech th chuyn ha chung t 99%, chn lc t 100% (tnh

theo iso buten).

Vy to ra MTBE t nng sut yu cu l 71,74 kmol/h th lng iso buten cn tora t phn hyro ha tiu th cho phn ng tng hp l:

72,460,99

71,74 kmol/h

(0,99 l chuyn ha ca phn ng tng hp theo iso buten)

y n gin trong tnh ton ta coi chn lc MTBE t 100% v iso buten khng

tiu th cho phn ng ph to ra TBA v DIB.

Vy GIB =72,46 . 56 = 4057,76 kg/h(MIB = 56)

+ Khi lng Metanol a vo thit b phn ng MTBE theo t l:

buteniso

Metanol1,1 (t l mol).

Vy lng Metanol a vo l:

72,46 . 1,1 = 79,706 kmol/h

Hay 79,706 . 32 = 255,60 kg/h

Lng Metanol a vo thit b = lng metanol (99,9% W) mi a vo

+ lng metanol tun hon.

Trong :

Lng Metanol tun hon = lng Metanol cn li sau phn ng- lng

Metanol trong sn phm MTBE.

Lng Metanol cn li sau phn ng = Lng Metanol a vo - Metanol

tiu th cho phn ng.

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Lng Metanol tiu hao cho phn ng cng bng s kmol MTBE to ra (theo phn

ng tng hp) v bng 71,74 kmol/h.

Vy lng Metanol cn li sau phn ng l:

79,76 -71,74 = 7,966 kmol/h Hay 7,17. 32 = 254,91 kg/h.

Ta coi cc sn phm ph khc trong MTBE sn phm ch gm c Metanol v khngcha DIB, TBA... Lng Me cn li trong sn phm MTBE chim 1% khi lng tc l

bng:

0,01. 6313.13 = 63,13 kg/h.

Coi rng Metanol c thu hi theo dng sn phm chnh ra khi thp phn ng 2 l

100%.

Nh vy lng Metanol tun hon l:

254,91. 63.13 = 191.78 kg/h.

Lng Metanol (100% W) mi cn a vo l:

2550,60 - 191,78 = 2358,82 kg/h.

Lng Metanol (99,9%) mi cn a vo dy chuyn l:

kg/h2361,180,999

2358,82

Vy lng nc a vo dy chuyn l:

GH2

O= 2361,18 - 2358,82 = 2,36 kg/h.

Cn bng ta c:

G1 + GMeOH (99,9%) = GC 4 cha phn ng+ GMTBE+ GMeOH trong MTBE + GH 2 O

Hay G1 + 2361,18 = GC 4 cha phn ng+ 6313,13 + 63,13 + 2,36

tnh G1 v G 4c

ta tnh cn bng vt cht cho giai on hyro ha.

* Cn bng vt cht giai on hyro ha:

Khi cn bng: khi lng vo = khi lng ra.

- Cc dng vt cht i vo phn hyro ha gm:+ Hn hp C4lng iso butan nguyn liu: Giso- 104HC , kg/h

- Cc dng vt cht i ra gm:+ Hn hp lng C4sn phm c cha iso buten: Giso- 104HC , kg/h

+ Hn hp kh thi giu H2: Gkh thi, kg/h

Vy cn bng ta c:

Giso- 104HC nguyn liu = Giso- 84HC sn phm + Gkh thiTnh ton cc khi lng nh sau:

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+ Giso- 84HC nguyn liu:

Ta cphn ng:

iso-C4H10 iso-C4H8+ H2 (*)

Lng iso-C4H8 cn to ra giai on hyro ha tng hp c 6313,13 kg

hMTBE nh ta tnh: 72,46 kmol/h.

Phn ng hyro ha (*) thc hin trong dy chuyn t chuyn ha 40%, v

chuyn ha t 92% mol [2]

Nh vy lng iso-C4H10cn hyro ha cn l:

78,460,92

72,46 kmol/h.

V chuyn ha ca (*) t 40%, vy lng iso -C4H10nguyn cht cn a vo dychuyn l:

90,1964,0

46,78 kmol/h.

Trong 72,46 kmol/h iso-C4H10s tiu hao cho phn ng chnh (*) to ra 72,46

kmol/h iso-C4H8v 78,76 - 72,46 = 6,3 kmol/h s tham gia phn ng ph iso-C4H10.

Gi s iso-C4H10 ch tham gia cc phn ng ph cracking:

iso-C4H10 C2H6+ C2H4 (1)

x (kmol/h) x x

iso-C4H10 CH4+ C3H6 (2)

x (kmol/h) x x

n gin ta gi s cc phn ng (1) v (2) xy ra vi tc nh nhau, tiu th

lng iso-C4H10nh nhau, cc phn ng c hiu sut nh nhau v bng 100%.

Vy lngiso-C4H10 tiu th cho mi phn ng l:

3,12

6,3x kmol/h.

Lng iso-C4H10cn li khng chuyn ha l:

196,90 - 78,76 = 118,14 kmol/h.

V khi lng nguyn liu iso-C4H10cn cha cc thnh phn kh khc nh propan, n-

butan, buten... v iso-C4H10ch chim 90% th tch.

Vy lng kh iso-C4H10nguyn liu cn a vo l:

Giso- 104HC nguyn liu 78,2189,0

90,196 kmol/h

Vy thnh phn v khi lng kh iso-C4H10nguyn liu a vo nh sau:

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Bng 13: Thnh phn v khi lng kh iso-C4H10nguyn liu a vo:

STT Tn cu t % kmol/h kg/h

1

2

3

4

5

6

iso-C4H10

Propan

n- C4H10

Tng n- C4H8

C 5

H2Sv

Meroaptan

90

3

6

0,5

0,495

0,005

196,90

0,03. 218.78 = 6,56

0,06. 218,78 = 13,127

0,005. 218 78 = 1,09

0,495. 10-2.218,78 = 1,08

0,005 . 10-2.218,78 = 0,01

196,90. 58 = 11420,2

6,56. 44 = 288,79

13,127. 58 = 761,35

1,09. 56 = 61,26

1,08. 72 = 77,97

0,01. MTB= 0,45

Tng 100 = 218,78 Vi MTB

142

4834

2

32 SHCHSH MM

Vy Giso- 104HC nguyn liu= 11420,2 + 288,79 + 761,35 +31,26 +77,97 +0,45 = 12610,02

kg/h.

Gi s ch c cc phn ng hyro ha v cc phn ng no cng chuyn ha 40%.

C3H8 C3H6 + H2 (3)

6,56 2,62 2,62

n-C4H10 n-C4H8 + H2 (4)13,127 5,25 5,25

Lng C3H8 tham gia phn ng (3) l:

0,4. 6,56 = 2,62 kmol/h.

Lng n-C4H8 tham gia phn ng (4) l:

13,127. 0,4 = 5,25 kmol/h.

+ Giso- 84HC sn phm :

Dng vt cht i ra khi thit b hyro ha s c ngng t cc cu t t C3tr lns ngng khi b nn p sut. Cc cu t C2tr xung s khng ngng v i ra khi dy

chuyn th kh (kh thi).

Vy hn hp lng Iso- C4H8 sn phm i ra khi phn hyro ha c khi lng v

thnh phn nh sau:

Iso- C4H8: l lng Iso- C4H8to ra: 72,46 kmol/h = 405,76 kg/h

Iso- C4H10: bng lng Iso- C4H10 cn li cha chuyn ha v bng:

196,90 - 78,76 = 118,14 kmol/h = 6852,12 kg/h

n-C4H10 : bng lng c ban u - lng tham gia phn ng v bng:

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13,127 - 5 25 = 7 88 kmol/h = 456,87 kg/h.

n-C4H8 :bng lng c ban u trong nguyn liu + lng to ra phn ng (4):

1,09 + 5 25 = 6 34 kmol/h = 355,04 kg/h.

C3H8 : bng lng c ban u trong nguyn liu - lng phnng theo (3):

6,56 - 2,62 = 3,94 kmol/h = 177,36 kg/h.

C3H6 : bng tng lng to ra do phn ng (2) v (3):

3,16 + 2,62 = 5,77 kmol/h = 242,34 kg/h.

C : bng lng c ban u:

1,08 kmol/h = 77,97 kg/h.

Vy Giso- 84HC sn phm = 12215,46 kg/h.

+Gkh thi : kh thi gm c H2, CH4, C2H4, C2H6, H2S v Mercaptan khi lng vthnh phn hn hp kh thi nh sau:

H2l tng lng kh thi to ra do cc phn ng (*), (3) v (4) bng: 72,46 + 2,62 +

5,25 = 80,33 kmol/h = 160,66 kg/h.

CH4: l lng to ra do phn ng (2) l:

3,15 kmol/h =50,4 kg/h.

C2H4: l lng C2H4to ra do phn ng (1):

3,15 kmol/h = 88,2 kg/h.

C2H6: l lng C2H6 to ra do phn ng (1):

3,15 kmol/h = 94,5 kg/h

H2S: l lng H2S c ban u:

0,01 kmol/h = 0,45 kg/h.

Vy Gkh thi= 394,21 kg/h.

Vy cn bng :

Giso- 104HC nguyn liu = Giso- 84HC sn phm + Gkh thi

12610,02 = 12215,46 + 394,21 2610,02

Hn hp C (iso-C4H8) sn phm i ra khi phn hyro ha c khi lng Giso- 84HC

sn phm v cng l G1:

G1= 12215,46 kg/h

Trong thnh phn v khi lng nh trong bng 14.

Bng 14: Thnh phn v khi lng kh ra khi phn hyro ha:

Thnh phn % Kmol/h Kg/hiso-C4H8 33,6 72,46 4057,76

5

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iso-C4H10

n-C4H10

n-C4H8

C3H8

C3H6

C 5

54,8

3,7

2,9

1,8

2,7

0,5

118,14

7,88

6,34

3,94

5,77

1,08

6582,12

456,87

355,04

173,36

242,34

77,97

Tng 100 215,61 12215,46

Hn hp ny l dng nguynliu i vo phn tng hp MTBE. By gii ta thay G1=

12215,46 kg/h vo phng trnh cn bng vt cht cho giai on tng hp MTBE ta c:

G1 + GMeOH (99,9%) = G

4C cha phn ng+ GMTBE+ GMeOH trong MTBE + GH 2 OG1 = 12215,46 kg/h

GMeOH (99,9%)= 2361,18 kg/h

GMTBE= 6313,13 kg/h

GMeOH trong MTBE = 63,16 kg/h

GH2

O=2,36 kg/h

Ta c G 4C cha phn ng= 8198,02 kg/h

Xc nh thnh phn v khi lng dng C4cha phn ng:

Phnng:

Iso- C4H8 + MeOH MTBE

71,74 71,74 71,74 (kmol/h).

Nu coi rng phn ng t chuyn ha 90% mol (theo iso-C4H8) v chn lc t

100% th lng MTBE to ra 71,74 kmol/h.

Lng iso-C4H8cn to ra lng 71,74 kmol/h MTBE l:

72,460,99

71,74 kmol/h

Lng iso-C4H8cha chuyn ha l:

72,74 - 71,74 = 0,72 kmol/h.

Ngoi ra cc cu t khc trong hn hp l tr khng phn ng. Vy thnh phn v khi

lng ca kh C 4cha phn ng theo bng 15 sau:

Bng 15: Thnh phn v khi lng ca kh C

4cha phn ng.

Thnh phn % Kmol/h Kg/h

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iso-C4H8

iso-C4H10

n-C4H10

n-C4H8

C3H8

C3H6

C 5

0,5

82,1

5,5

4,4

2,7

4,0

0,8

0,72

118,14

7,88

6,34

3,94

5,77

1,08

40,32

6852,12

456,87

355,04

173,36

242,34

77,97

Tng 100 143,87 8198,02

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Tm li ta c bng cn bng vt cht chung cho ton b phn xng bng sau:

Bng 16: Cc dng vt cht cho ton phn xng.

Cc dng vt cht i vo (kg/h) Cc dng vt cht i ra (kg/h)

Giso- 104HC nguyn liu = 12610,02GMeOH (99,9%)= 2361,18

GMTBE

= 6313,13

G 4C cha phn ng

= 8198,02

GMeOH trong MTBE = 63,13

GH 2 O=2,36

Gkh thi= 394,21

Tng = 14971,20 Tng = 14970,85

*Tnh lng nguyn liu mi cn thit a vo dy chuyn:

Kh Raffinat-2 sau khi thu hi c em x l loi cc cu t cha oxi nh: Metanol,

MTBE, H2O (vi lng nh), loi Propan v Propylen... t tiu chun nh kh iso -

butan nguyn liu ri c tun hon trn vi nguyn liu mi.

Ta c:

Dng iso-C4H10 + lng iso-C4H10 tun hon = lng iso-C4H10 i vo dy chuyn.

Tnh theo cu t iso-butan ta c:

196,90- 118,14 = 78,76 (kmol/h).

V trong Iso-butan nguyn liu th isobutan ch chim 90% th tch. Vy trong isobutan

nguyn liu mi cn a vo dy chuyn l:

87,510,9

78,76 kmol/h

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Bng 17: Lng iso-butan nguyn liu mi cn a vo dy chuyn.

Thnh phn % Kmol/h Kg/h

iso-C4H10

Propan

n-C4H10

Tng n-C4H8

C 5

H2S v Mercaptan

90

3

6

0,5

0,495

0,005

78,76

0,03. 87,51= 2,63

0,06. 87,51= 5,25

0,005. 87,51= 0,44

0,495. 10-2. 87,51= 0,43

0,005. 10-2. 87,51= 4,4.10-3

4568,08

2,63. 44= 115,51

5,25. 58= 304,54

0,44. 56= 24,50

0,43. 72= 31,19

4,4.10-3. 41= 0,18

Tng 100 87,51 5044

Giso- 104HC nguyn liu mi = 5044 kg/h.

Isobutan tun hon c thnh phn ging nh nguyn liu mi v khi lng nh sau:

Bng 18: Thnh phn v khi lng ca dng tun hon.

Thnhphn % Kmol/h Kg/h

iso-C4H10 90 118,14 6852,12

Propan 30,03.

9,014,118 = 3,94

3,94. 44 = 137,27

n-C4H10 6 0,06.9,014,118 = 7,88

7,88. 58 = 456.81

Tng n-C4H8 0,50,005. 9,0

14,118= 0,66

0,66. 46 = 36,75

C5 0,495 0,495. 10-2.

9,014,118 = 0,65 0,65. 72 = 46,78

H2S v Mercaptan 0,0050,005. 10

-2

. 9,014,118

= 0,00660,0066. 41= 0,27

Tng 100 131,28 7566

Cn bng ta c:

Lng iso-C4H10mi vo+ lng iso-C4H10tun hon = lng iso-C4H10vo dy

chuyn.

5044 + 7566 = 12610,02

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12160,00 = 12160,02

2.Tnh ton cn bng vt cht cho thit b phn ng ng chm th nht:

Khi cn bng:

Khi lng vo = khi lng ra

GIso- 84HC nguyn liu + GMeOH= GMTBE + GMeOH d+ Ghn hp 4C cn li

Tnh ton cc khi lng nh sau:

GIso- 84HC nguyn liu = 12610,02 kg/h

GMeOH= Lng Metanol mi + Lng Metanol tun hon

= 2361,18 + 191,78 = 2552,96 kg/h

GMeOH = 2552,96 kg/h

Cc cu t i ra thit b phn ng gm:

.GMTBE: thit b phn ng th nht chuyn ho t 85%, chn lc t 100%.

Iso-C4H8+ MeOH MTBE

72,46Kmol/h 61,591Kmol/h

Lng MTBE to ra l:

GMTBE= 0,85 + 72,46 . 88 = 5420,01 Kg/h

.Lng Iso-C4H8cn li cha phn ng l:

72,46 - 61,591 = 10,87 Kmol/h = 608,66 Kg/h

Lng Meta nol cha phn ng l:

79,760 - 61,591 = 18,115 kmol/h = 579,68 kg/h.

Cc cu t khc khng tham gia phn ng:

Bng 19: Cc cu t khng tham gia phn ng trong thit b phn ng ng chm th

nht.

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Thnh phn Kmol/h Kg/h

iso-C4H10

n-C4H10

n-C4H

8

C3H8

C3H6

C 5

118,14

7,88

6,34

3,94

5,77

1,08

6852,12

456,87

355,04

173,36

242,34

77,97

Vy:

Ghn hp 4c cn li = 608,66 + 6852,12 + 456,87 + 355,04 + 173,36 + 242,34 + 77,97

Ghn hp 4c cn li = 8766,36 kg/h.

Vy ta tm tt cn bng vt cht cho thit b phn ng th nht theo bng 20:

Bng 20: Cn bng vt cht cho thit b phn ng th nht.

Cu t Lng vo, kmol/h Lng ra, kg/h

iso-C4H8

Metanol

MTBE

iso-C4H10

n-C4H10

n-C4H8

C3H8

C3H6

C5

Tng

H2O

4077,76

2550,6

0

6852,12

456,87

355,04

173,36

242,34

77,97

14766,06

2,36

608,66

579,68

5420,01

6852,12

456,87

355,04

173,36

242,34

77,97

14766,05

2,36

14768,42 14768,41

3.Tnh ton cn bng vt cht cho thit b phn ng chng tch:

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Dng sn phm i ra khi thit b phn ng th nht c a vo thit b phn ng

chng ct. V vy cc cu t v khi lng ca chng cng l cc cu t v khi lng ca

dng ra thit b phn ng th nht.

Ta c: Gvo= 14768,41 Kg/h

thit b phn ng chngct ny do vic chng tch sn phm MTBE lin tc khimi trng phn ng ln cn bng chuyn ho t cao hn v lm chuyn ho chung

ca qu trnh t 99%.

Phn ng:

Iso-C4H8 + MeOH MTBE

10,149Kmol/h 10,149Kmol/h 10,149Kmol/h

Sn phm ra khi thit b ny l 71,74 Kmol/h (ng vi 6313,13 Kg/h) trong

MTBE to ra thit b phn ng th nht l 61,591 Kmol/h

Lng to ra thit b phn ng chng ct:

71,74 - 61,591 = 10,149 Kmol/h = 893,112 Kg/h

Lng iso-C4H8cn li khng phn ng l:

10,87- 10,149 = 0,721 kmol/h = 40,376 kg/h

Lng Metanol cn li sau thp phn ng chng ct l:

579,68- 10,149. 32 = 254,912 kg/h.

Do vy c th tm tt bng 21.

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Bng 21: Cn bng phn ng cho thit b phn ng chng ct.

Cu t Lng vo, kmol/h Lng ra, kg/h

iso-C4H8

Metanol

MTBE

iso-C4H10

n-C4H10

n-C4H8

C3H8

C3H6

C

5

H2O

608,66

579,68

5420,01

6852,12

456,87

355,04

173,36

242,34

77,97

2,36

40,376

254,91

6313,13

6852,12

456,87

355,04

173,36

242,34

77,97

2,36

14768,41 14768,98

II.Tnh cn bng nhit lng:

Vic tnh ton nhit lng cho thit b phn ng chng tch l rt phc tp v vy

trong khun kh bn n ny, vn tnh ton nhit cho thit b ny khng c cp

n.Vi thit b phn ng th nht c th tnh ton cn bng nhit lng nh sau:

Cc dng nhit vo = cc dng nhit ra

-Cc dng nhit vo gm c:

+Dng nhit do hn hp nguyn liu vo:

Q1= Gnguyn liu. Cp nguyn liu . tng.liu

Nhit nguyn liu vo l: tng.liu= 60oC

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Hn hp nguyn liu vo c tm tt bng 22.

Bng 22: Thnh phn ca hn hp nguyn liu vo thit b

phn ng th nht.

Thnh phn Kg/h %khi lng Kmol/h

I so-C4H8I so-C4H10

n-C4H10n-C4H8C3H8C3H6

C5

Metanol

H2O (trong MeOH)

4057,76

6852,12

456,87

355,04

173,36

212,34

77,97

2550,62,36

27,48

46,40

3,09

2,40

1,17

1,64

0,53

17,270,02

72,46

118,14

7,88

6,34

3,94

5,77

1,08

79,7060,131

Tng Gngliu=1476,42 100 Gngliu=295,447

Tnh CPhn hp nguyn liu mang vo:

CPca hn hp lng c tnh theo cng thc:

CP hn hp ii

p.xC [12]

Trong :i

pC : nhit dung ring ca cc cu t i trong dung dch.

xi: phn trm khi lng ca cu t i.

Tnh ca cc cu t trong hn hp: [13]

CP (iso-104

HC lng)=596,89 - 4,6387. T + 1,44.10-2.T2- 1,372.10-5.T3KJ/kmol.

CP(MeOH) =1391,6- 12,364.T + 3,781.10-2.T2- 3,179.10-5.T3 KJ/kmol.

CP (MTBE)=53,176 + 0,7173.T - 0,1533. 10-2.T2+ 0,202. 10-5.T3 KJ/kmol.

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CP (n-104

HC )= 4,347 + 72,552. 10-3.T - 18,14.10-6.T2 Kcal/mol.

CP (n- 84HC )= 20,762 + 250,637. 10-3.T - 75,854. 10-6.T2 KJ/mol.

CP (iso- 104HC )= 9,597 + 344,46. 10-3.T - 162,15. 10-6.T2 KJ/mol.

CP ( 83HC )= 0,41 + 64,71. 10-3.T - 22,582. 10-6.T2 Kcal/mol.

CP (63HC )

= 2,974 + 45,024. 10-3.T - 11,38. 10-6.T2 Kcal/mol.

V C5 phn trong hn hp l nh nn khi tnh ton ta b qua.

Thay nhit t0= 600C (T = 3330K) ta tnh c:

CP (iso- 84HC )= 142,38 KJ/kmol.

CP (MeOH) = 293,22 KJ/kmol.

CP (iso- 104HC ) = 106,32 KJ/kmol.

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CP (n- 84HC ) = 95,72 KJ/mol.

CP (n-104HC )

= 110,95 KJ/mol.

CP( OH2

) = 4190 J/kg. = 75,22 KJ/mol.

CP (83HC ) = 81,44 KJ/mol.

CP (63HC )

= 69,93 KJ/mol.

Thay s vo cng thc:

CP (nguyn liu) ii

p.xC

CP nguyn liu= xiso- 84HC . CP iso- 84HC + xiso- 104HC . CP (iso- 104HC ) + xn- 84HC .CP (n- 84HC ) + xn-

104HC . CP (n-

104HC ) + x

83HC . CP ( 83HC )+ x 63HC . CP ( 63HC )+ xMeOH.CP (MeOH)

CP nguyn liu= 146,922 KJ/mol.

Vy Q1= Qngliu. CP ngliu. tngliu = 295,447. 146,922. 60 = 2604457,597 KJ/h.

+Dng nhit do nc lm lnh mang vo:

Q2= GH2

O.CP H2

O. t1 H2

O

Chn nhit nc lm lnh l 01t = 250C

Tra s tay ta c:

CP (H2O) )C52( o = 75,22 KJ/mol.

+ Nhit ta ra do phn ng tng hp l:Q3= Qr= H.n

Trong :

H: nhit phn ng

n: s mol MTBE to thnh

Thay s ta c:

Q3= 61,591. 103. 37 = 2278867 KJ/h

- Cc dng nhit i ra khi thit b phn ng gm:+ Nhit lng do dng sn phm mang ra:

Q4= Gsp. Gsp. Tsp

Dng sn phm i ra khi thit b phn ng th nht c tm tt bng 23.

Bng 23: Thnh phn ca dng i ra khi thit b phn ng th nht

Thnh phn Kmol/h Kg/h % khi lng

iso-C4H8

Metanol

10,87

18,115

608,66

579,68

4,12

3,93

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MTBE

iso-C4H10

n-C4H10

n-C4H8

C3H8

C3H6

C 5

H2O

61,591

118,14

7,88

6,34

3,94

5,77

1,08

0,131

5420,01

6852,12

456,87

355,04

173,36

242,34

77,97

2,36

36,70

46,40

3,09

2,40

1,17

1,64

0,53

0,02

Tng 233,857 14768,41 100

Thay s vo cci

pC ca cc cu t nhit sn phm ra chn tsp= 800

C

CP (iso- )= 150,297 KJ/mol.

CP (MeOH)= 340,228 KJ/mol.

CP (MTBE)= 204,211 KJ/mol.

CP (n-104HC )

= 110,986 KJ/mol.

CP (n- 84HC )= 115,98 KJ/mol.

CP (iso- 104HC )= 99,785 KJ/mol.

CP (83

HC )= 85,556 KJ/mol.

CP (63

HC )= 73,043 KJ/mol.

CP (H2

O)= 75,42 KJ/mol.

Vy CPsp ii

p.xC

CPsp= 157,73 KJ/mol.

Do :

Q4= Gsp. Gsp. Tsp= 233,857. 159,733. 80 = 2988372,684 KJ/h.

+Dng nhit do cht ti nhit mang ra:

Q5= GH2

O.CP (H2

O). t2 H2

O

Chn nhit ca nc i ra l 02t = 500C

Tra CPca H2O 500C ta c:

CP (H 2 O) )C50( o = 75,285 KJ/mol. [12]

Cn bng nhit lng do thit b ta c:Nhit lng i vo =Nhit lng i ra

84HC

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Q1+ Q2+ Q3= Q4+ Q5

Hay:

Qngliu. CP ngliu. tngliu+ GH2

O. t1 H2

O. CP (H2

O) )C52( o + H.n = Gsp. Gsp. Tsp+ GH2 O. t2 H2 O. CP (H2 O) )C50( o

Thay s vo:

295. 447. 146,922. 60 + GH2

O.75,42. 25 + 61,591. 10. 37

= 233,857. 159,733. 80 + GH2

O. 75,285. 50

Vy lng nc cn lm lnh l:

GH2O= 1005,947 Kmol/h

Hay: GH2 O= 18107,039 kg/h.

Vy cn bng nhit lng c biu din bng sau:

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Bng 24: Cn bng nhit lng cho thit b phn ng th nht.

Nhit vo (KJ/h) Nhit ra (KJ/h)

Q1= 2604457,597

Q2= 1891683,334

Q3= 2278867,0

Q4= 2988327,684

Q5= 3786635,247

Qvo= 6775007,931 Qra= 6775007,931

III. Tnh ton thit b phn ng chnh:

1.Tnh ton th tch lm vic ca thit b phn ng:

Phn ng tng hp MTBE c tin hnh trong iu kin t0= 60800C


y l phn ng bc 2.

Phng trnh ng hc ca phn ng c th vit :

2C.kd

dCr

(coi C(iso- )= CMeOH)

- 2C.kd

dC

d.k

C

dC2

Ly tch phn 2 v ta c:

.kC

1

C

1

o

, (**)

Trong :

: thi gian lu

K: hng s vn tc phn ng

C0, C: nng lc ban u v sau thi gian lu -Xc nh hng s vn tc k:Ta xc nh k t nhng s liu da theo (5).

r = 0,0151 mol/h.mequiv

C = 4,75 mequiv/gxt

XMeOH= 7,2%.

Ta c: W = k. C1. C2

84HC

21.CCWk

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(Trong : C1, C2l nng ca iso-C4H8 v Metanol)

Ta i xc nh C1v C2nh sau:

Trong 1l dung dch hn hp:

V MeOH = 0,7649g/cm3= 764 g/l = 23,875 mol/l

iso- = 0,588 g/cm3= 588g/l = 10,5 mol/l

Vytrong 1l dung dch th:

S mol ca Metanol l 23,875 mol/l

S mol ca iso-C4H8 l 10,5 mol/l.

Vy nu gi x l th tch ca Metanol trong 1l dung dch hn hp th (1 -x) l th tch

ca iso-C4H8

V t l mol: =1,1 nn:

x. 23,875 = 1,1. [(1-x). 10.5]

Do x = 0,326 l

Vy = 0,326. 23,875. 0,336 = 2,615 mol/l

= mol/l

Phn ng:


Ban u 2,378 2,615 0

2,378 - 2,615xMeOH 2,615-2,615 xMeOH 2,615 xMeOH

V ta c xMeOH = 7,2%

Vy sau phn ng:

Ciso- = 2,378 - 2,615. 0,072 = 2,19 mol/l

CMeOH = 2,615 - 2,615. 0,072 = 2,427 mol/l.

Vy

Ta s dng loi xc tc Amberlyst 15 vi cc thng s nh sau: [5]

dht= 0,74mm

B mt ring A= 42m2/g

Trnglng ring ng:

84HC

84HCiso

Metanol

HOeM

0C

84HC-iso

0C 378,21,1

615,2

84HC

xt

2

21 mol.h.g

l0,013

2,19.2,427

50,0151.4,7

CC

r.Ck

xt

236

mol.h.g

)(m0,013.10k

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ng= 760 kg/m3= 760.000 g/m3

Do :

*Xc nh C0v C:

Thnh phn hn hp vo thit b phn ng chnh da vo bng 25:

33

236

xt

2

m760.10

1mol.h.

)(m0,13.10

mol.h.g

l0,013k

mol.h

m0,00988k

3

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Bng 25: Thnh phn hn hp vo thit b phn ng chnh.

Thnh phn Kmol/h Kg/h

(g/l)

Th tch mol

(l/mol)

V(l/h)

iso-C4H8 72,46 4057,76 587,9= 0,095

0,095.72,46.103=6902,1

iso-C4H10 118,14 6852,12 540= 0,107

0,107.118,14.103= 126899,11

n-C4H10 7,88 456,87 573= 0,101

0,101.7,88.103= 797,63

n-C4H8 6,34 355,04 598,4=0,0936

0,0936. 6,34. 103= 593,32

C3H8 3,94 173,36 490 = 0,0898 0,0898. 3,94. 103= 353,8

C3H6 5,77 242,34 510= 0,0824

0,0824. 5,77. 103= 475,18

Metanol 79,706 2550,6 736,7= 0,101

0,042. 79,706.103= 3339,78

H2O ( trong

MeOH)

0,131 2,36 983983

18= 0,0183

0,0183. 0,131. 103= 2,399

Tng th tch ca hn hp nguyn liu vo thit b l:

V= 6902,1 + 12698,11 + 797,63 + 593,32 + 353,80 + 475,18 + 3339,78 + 2,399

V= 25153,32.l/h= 25,15 m3/h

Vy C0= = 288,11 mol/m3

3m,C rah phnt chTh liu)n(nguyrah phntrongHC-isomolS 84

Hn hp sn phm ra khi thit b phn ng theo bng 26:

9,587

56

540

58

573

58

4,598

56

490

44

510

542

7,763

32

15,25

10.46,72 3

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Bng 26: Thnh phn sn phm ra khi thit b phn ng chnh.

Thnh phn Kmol/h Kg/h (g/l) Th tch mol

(l/mol)

V(l/h)

iso-C4H8

iso-C4H10

n-C4H10

n-C4H8

C3H8

C3H6

Metanol

H2O

MTBE

10,87

118,14

7,88

6,34

3,94

5,77

79,706

0,131

61,591

4057,76

6852,12

456,87

355,04

173,36

242,34

2550,6

2,36

5420

587,9

540

573

598,4

490

510

736,7

983

730,4

0,095

0,107

0,101

0,0936

0,0898

0,0824

0,042

0,0183

0,12

1035,41

12689,11

797,63

593,32

353,80

475,18

759,04

2,40

7420,6

Th tch ca dng sn phm ra khi thit b phn ng l:

V= 1035,41 + 12689,11 + 797,63 + 593,32 + 353,8 + 475,18 + 759,04 + 2,40 + 742,6

V= 24126,49 l/h = 24,13 m3/h

Vy C= 47,45013,24

10.87,10 3 mol/m3

Thay vo (*) ta c:

00988,011,2881

1

477,450

1

= 0,1896 h.

Vy th tch lm vic ca thit b l:

Vr=m. v. [15]

Trong :

m: h s d tr (ly m = 1,5)

v: Th tch hn hp dng vo, m3/h

: Thi gian lu, h

Vy Vr = 1,5. 25,15. 0,1896 = 7,153 ,m3

2.Tnh ton kch thc thit b phn ng:

Thit b phn ng l thit b ng chm c cu to bn ngoi l v bc, bn trong l cc

ng cha xc tc nha trao i ion. Hn hp nguyn liu c a vo thit b nh v

t chy trong ng cha xc tc. Phn ng xy ra trong ng t0= 60-800C. y l phn ng

ta nhit, m bo nhit khng tng cao ta cn thit k ng knh ng ph hp vchng nc lnh i ngoi ng ly nhit i.

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Tc dng trong ng ly = 0,01 m/s

Vy chiu cao ca ng l:

hng= .T= 0,01. 0,1896. 3600 = 6,8256 m.

Ly hng= 6,9 m

ng knh ca thit b phn ng ng chm c xc nh da trn s ng theo cng

thc:

D = t(b-1) + 4d ,m [16]

Trong :

D: ng knh thit b, m.

t: bc ng, m.

b: s ng trn ng cho hnh lc gic (b tr ng theo hnh lc gic).

d: ng knh ngoi ca ng, m.

Ta c: Vr= h.S

Trong :

h: chiu cao thit b (h = hng).

S: tit din ngang.

V hn hp phn ng ch i vo trong cc ng cha xc tc nn tit din ngang S l

tng cc tit din ngang ca cc ng chm.

S = n. STrong ;

n: s ng.

S: tit din ngang 1 ng.

Ta c:

(dngl ng knh trong ca ng, m)

Thng th ta ly dng = 2550 mmTa chn dng = 50 mm v chiu dy ng 3 mm.

Vy

Vy Vr= h. S = h. n. S

S ng ca thit b l;

ng

Ta quy chun s ng ca thit b.

4

.dS

22ng

4

.dS

22ng 23

2

m1,9625.104

)3,14.(0,05

3

r

625.106,8256.1,9

7,153

h.S

Vn

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Nu xp ng theo hnh lc gic th ta c cng thc:

n= 3a(a-1) + 1 [16]

Trong :

n: s ng.

a: s ng trn 1 cnh ca hnh lc gic.

Thay n = 533,996 vo cng thc ta c:

533,996 = 3a(a-1) + 1

Gii phng trnh ny ta c a = 13,829

Ta ly a = 14 ng.

V s ng ca thit b theo quy chun phi l:

n = 3a(a-1) + 1 = 3. 14914-1) + 1

n = 547 ng.

Nu ta xp ng thm phn khong khng gia cc cnh hnh lc gic v thnh thit

b th s ng s l 613 ng.

ng knh thit b phn ng l:

D = t(b-1) + 4.d

Bc ng t thng ly l t= 1,25d

d: ng knh ngoi ca ng, d= 0,05 + 0,003. 2= 0,056

Vy t= 1,25. 0,056= 0,07 mb= 2a-1= 2. 14 - 1= 27 ng.

Vy D = 0,07(27-1) + 4. 0,056

D = 2,044 m.

Ta quy chun chn D= 2,2 m [17 - 115]

Chn vt liu lm thit b la thp CT3.

Tm li: kch thc ca thit b phn ng nh sau:

-Chiu cao thit b: h= 6,9 m-ng knh thit b: D= 2,2 m-S ng: n= 534 ng-ng knh ng: d= 0,056 m-Chiu dy ng; 3mm= 0,003 m-Bc ng: t= 0,07 m.*Tnh ton c kh mt s chi tit ch yu ca thit b:

-Chiu dy thn thp.

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,m [17-360]

Trong :

D1: ng knh trong ca thit b, m.

: h s bn thnh hnh tr theo phng trc dc, =0,95.

C: h s b sung do n mn, bo mn v dung sai v chiu dy, m

Vi thit b hn dc, mn tay bng h quang in ng vi thp CT3 vo 2 lp th

=0,95.

Pt: p sut trong ca thit b, N/m2.

p sut trong ca thit b c tnh theo cng thc:

Pt= PLV+ Ptt, N/m2 [17- 366]

Trong :

PLV: p sut lm vic ca thit bN/m2.

PLV= 1,03. 105N/m2

Ptt: p sut thy tnh ca nc.

Ptt= . g. h , N/m2

Trong :

g l gia tc trng trng, g= 9,91 m/s2

h l chiu cao ca ct cht lng, h= 7m

l khi lng ring trung bnh ca hn hp cht lng, = 676 kg/m3.

Do :

Ptt= . g. h = 9,81. 676. 7 = 46420,92 N/m2

Vy p sut trong thit b l:

Pt= 1,03. 105+ 46420,92 = 1,49421. 105N/m2.

Ta tnh h s b sung do n mn, bo mn, dung sai v chiu dy.

C = C1+ C2+ C3, m2 [17-363]

Vi: C1: b sung n mn: vi thp CT3tc g l 0,06 mm/nm, thi gian lm

vic t 1520 nm.

C1= 1mm

C2: b sung do bo mn, C2= 0.

C3: Dung saiv chiu dy, C3= 0,8 mm.

Do : C = 1 + 0 + 0,8 = 1,8 mm = 0,0018 m.

*ng sut cho php ca thp CT theo gii hn bn c xc nh theo cng thc [17-355]:

CP.2

.PDS

t

tt

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.n

k

t

kk , N/m2.

Trong :

: h s iu chnh.

: h s an ton theo gii hn bn.

kt: ng sut gii hn bn, N/m2.

Thit b c cch ly vi ngun nng trc tip nn thuc loi II.

Tra bng XIII.2 [17-356] ta c = 1.

Tra bng XIII.3 [17-356] ta c = 2,6.

Tra bng XII.4 [17-309] ta c kt= 380. 108 N/m2.

Do : N/m2

*ng sut cho php theo gii hn chy xc nh theo cng thc [17-355]:

, N/m2.

Trong :

ct: gii hn chy nhit t, tra bng XII.4 [17-309]

ta c = 240.106N/m2.

nc: h s an ton theo gii hn chy. Tra bng XIII.3 [17-356] ta c

n= 1,5.

N/m2.

m bo b ta ly gi tr b nht trong hai kt qa trn, tc l: [] = [k] =

1,4614.106N/m2.

Trng hp y ng knh thit b Dt= 2,2 m, vi hn tay bng h quang v

cch hn gip mi hai bn ta tra bng XIII.8 [17-362] ta chn

= 0,95

50929,2.0,951,49421.10

1,4615.10.P 5

8

t

s

Theo [17-360]:

th b qua i lng P mu s trong cng thc tnh chiu dy thn thp [17-360].

Do chiu dy thn thp c xc nh nh sau:

86

k 1,4615.101.

2,610380.

.n

c

tc

c

86

c

tc

c 10.60,11.5,1

10.240.

n

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2,98mm1,8.10.0,9502.1,4615.1

.102,2.1,4942S

3

8

5

3.Tnh chiu dy y v np thp:

y v np thp cng c lm t vt liu cng loi vi thn thp. Ta dng loi y,

np elp c g cho thn hn.

Chiu dy ca y v np lm vic chu p sut trong c tnh theo cng thc [17 -

385].

Trong :n: h s bn ca mi hn hng tm (nu c).

hb: chiu cao phn li ca y, m.

k: h s khng th nguyn.

Tra bng XIII.10 [17-382] ta c hb= 550 mm.

bng XIII.8 [17-362] ta c n= 0,95

H s k c xc nh theo cng thc [17-385].

Trong : d l ng knh ln nht ca l khng tng cng d= 0,15m. Np hn t hai

pha bng tay, hn t hai natm vi nhau.

[k]= 1,4615.108N/m2 , c= 240.10

6 N/m2.

Ta tnh gi tr:

30865,895.0,9318.0,1,4942.10

1,4614.10.k.P

5

8

nk s

Do i lng P mu s ca cng thc tnh chiu dy y, np trn c th b

qua.

a.Chiu dy ca np:

C

2

.PDS tt

.

m,C2.h

D.P.k.3,8

PDS

b

t

tkk

tt

tDd1k

0,93182,2

0,151k

m,C2.h

D.P.k.3,8

PDS

b

t

tkk

tt

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C2.0,55

2,2.95.0,9318.0,,103,8.1,4615

.102,2.1,49428

5

S = 0,00195 + C ,m.

i lng b sung C:

S - C = 0,00195 m = 1,95mm

V S-C < 10.

Nn ta tng thm 2mm so vi gi tr C tnh thn thp [6-386].

Vy C = 0,0018 + 2. 10-3= 0,0038 m).

Vy S = 0,00195 + 0,0038 = 0,0575 (m).

Da vo bng XIII.11 [17-384] ta quy chun chiu dy ca np elp c g l S = 6mm.

Chiu cao g h = 50 mm.

Chiu cao phn li hb= 550 mm.

b.Chiu dy y thp:

Trong : Pt- p sut trong thit b, N/m2.

Ptt- p sut thy tnh ca ct cht lng (khi c s c).

C

2.0,55

2,2.

95.0,9318.0,,103,8.1,4615

46420,921,4942.102,2.S

8

5

S = 0,00175 + C.

Ta c S - C = 0,00175 m = 1,75 mm.

V S - C < 10 nn ta tng thm 2mm so vi gi tr C tnh thn thp. tc l C =

0,0018 + 2.10-3= 0,0038 m.

Do : S = 0,00175 + 0,0038 = 0,00555 (m) =5,55mm

Ta quy chun chiu dy y elp c g l S = 6 mm.

Chiu cao g h = 25 mm.Chiu cao phn li hb= 550 mm.

4.Tnh ng knh ng dn nguyn liu vo sn phm:

-ng dn nguyn liu:dnh

Trong :

w: vn tc trung bnh ca hn hp dng chn w= 0,2 m/sv: lu lng th tch ca hn hp , m3/s.

mC,2h

D.k..3,8.

PPDS

b

t

kk

tttt

m,0,785.w

V

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(hh: khi lng ring ca hn hp, = 13,5 kg/m3).

Vi lng nguyn liu vo thp:

GP = 14768,42 kg/h = 4,102 kg/s.

Vy dnh

Ta chn dnh= 200 mm.

-ng dn sn phm:Gi s nguyn liu i ra c Gnh = Gy= 4,102 kg/s v hh= 613,5 kg/m

3th tng t

nh trn, ng knh cht ti nhit tnh c l: d = 150 mm.

Chi tit c th hin trn bn v thit b ng chm.

5.Chn mt bch cho thit b:

Mt bch l b phn quan trng dng ni cc phn ca thit b cng nh ni cc b

phn khc vi thit b.

Ta chn bch lin bng kim loi en ni cc b phn ca thit b v ng dn.

Da vo bng XIII.26 [17 - 409] ta chn kiu bch 1 ng vi kch thc nh sau;

a. Chn bch lin bng thp ni np v y thp vithn thit b. Tra bng XIII. 27[17 - 147] ta c bng sau:

Bng 27: Kch thc bch ni np v y thp vi thn thit b.

Py.10-6

N/m2Dt

mm

Kch thc ni h

D Db D1 D0 Bulng

db z

mm Ci

0,1 2200 2350 2300 2260 2215 M24 56 32

Chn bch lin bng kim loi en ni thit b vi ng dn [17 - 409].

Ta gi ng 1 l ng dn nguyn liu.

ng 2 l ng dn sn phm.

ng 3 l ng dn cht ti nhit.Ta c bng sau:

hh

p

Gv

36,69.10

613,5

4,102v

m0,2070,785.0,2

6,69.103

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ng

dn

Dy ng Dn Kch thc ni h

D Db D1 Bulng

mm Db, mm z, ci Ci

12

3

0,250,25

0,25

200200

150

219219

159

290290

260

255225

225

232232

202

M16M16

M16

88

8

1616

16

Phn IV: Xy dng nh my

I.Phn tch aim xy dng nh my

1.Cc yu cu chung:

Nh my c t trong khu cng nghip Vng Tu, cho php tn dng ngun nng

lng, nguyn liu v s hp tc t cc nh my ln cn> Vi v tr nh vy, nng lng

cho nh my c th ly t cc m kh, du gn nh: m Rng, Bch H, i Hng,

Nam Cn Sn... Nhng s ch yu ly ngun kh qua x l loi b cc hp cht nh t

nh my kh Dinh C.

Vi iu kin xy lp v vn hnh nh my, Vng Tu l mt khu ng dn, v c

mt s nh my cng nghip hin i xy dng trc nn ngun nhn cng xy dng

cng nghip c kinh nghim kh di do. Tuy nhin do trnh k thut Vit Nam cn

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