Chng II: Qu trnh hydro ha - hydro ha

1. Gii thiu chung Qu trnh hydro ha cng nh qu trnh hydro ha c bit t rt lu, c ng dng nhiu trong cc qu trnh Lc - Ha du. C th nh ngha qu trnh hydro ha, hydro ha nh sau: Qu trnh chuyn ha m trong c s tch nguyn t H ra khi hp cht hu c c gi l qu trnh hydro ha.

Qu trnh chuyn ha m trong c s tc dng ca phn t H2 c gi l qu trnh hydro ha. ng dng trong lnh vc Ha du Trong cng nghip ha du, qu trnh hydro ha c ng dng tng

I.

hp cht hot ng b mt, tng hp cc monome c gi tr nh Butadien_1,3; styren; formaldehyd; aceton; anilin...; cn qu trnh hydro ha th c ng dng chnh trong lnh vc Lc du.
II.

ng dng trong lnh vc Lc du

1. Qu trnh hydro ha Mt cch s b theo phm vi ng dng, c th chia qu trnh hydro ha thnh 3 qu trnh sau:
1) X l bng H2

Mc ch: Lm mm nhm n nh cc sn phm du m

Loi b tp cht ca cc sn phm du m nh S, N, O, halogen, vt kim loi...

CH3SH + H2 CH3SCH3 + 2H2 HC HC S CH CH + 2H2 CH4 + H2S 2CH4 + H2S 2CH4 + H2S

2) Bo ha cc hydrocacbon thm Mc ch: Nng cp du nhin liu: tng ch s Cetan, gim nht, tng ch s nht... Ci thin nguyn liu cho qu trnh Cracking xc tc: vng khng no thnh vng no V d:
Naphtalen

+ 2H2
Tetralin

+ 3H2
Decalin

CH3

+ 3H2

CH3

Toluen Toluen

Metyl cyclo hexan

3) Hydrocracking

Mc ch: nhm ch bin nguyn liu l cc phn on du lng bt k thnh sn phm l kh hydrocacbon, xng, kerosen, diesel hoc nguyn liu cho sn xut du nhn di tc dng ng thi ca nhit cao (300 400oC); p sut cao (50 200 at) v xc tc lng chc Pt, Ni../ Al2O3, zeolit.. trong :

Pt, Ni... : chc kh thc hin cc phn ng hydro ha Al2O3, zeolit... : chc acid thc hin cc phn ng cracking V d : qu trnh hydrocracking Naphtalen

+ C-C-C C - C- C C + C-C-C

+ C-C-C

C - C- C - C - C C C

Hydro ha
+ C-C-C

+ C-C-C

Cracking

2. Qu trnh hydro ha Trong cng ngh Lc du, qu trnh hydro ha ch yu c ng dng trong qu trnh Reforming xc tc thu xng c hm lng hydrocacbon thm cao, tc l xng c ch s octan cao. ( qu trnh ny s c hc k trong Mn: Cc qu trnh chuyn ha Ha hc)

2. Phn loi cc phn ng hydro ha - hydro ha I. Phn loi phn ng hydro ha Phn ng hydro ha c chia lm 3 nhm: 1. Phn ng hydro ha cng hp
CH CH +H2 +H2 R - C - R

CH2 = CH2

+H2

CH3 - CH3

O R-CN

+H2 +H2

R - CH - R

OH R - CH2 - NH2

Lu : y l cc phn ng thun nghch 2. Phn ng hydro ha c s tch loi y l cc phn ng c tch loi cc phn t nh nh H2O, HCl, NH3, H2S...
RCOOH ROH RCONH2 RNO2 RCOCl RSH + 2H2 + H2 + 2H2 + 3H2 + H2 + H2 RCH2OH RH RCH2NH2 RNH2 RCHO RH + + + + + + H2O H2O H2O 2 H2O HCl H2S

3. Phn ng hydrocracking
RCH2R + H2 RCH3 C6H14 + RH + RH

+ 4H2 R + H2

I.

Phn loi phn ng hydro ha

1. Phn ng hydro ha khng c s thay i v tr cc nguyn t khc H

a) Phn ng hydro ti lin kt C C

CH3CH2CH2CH3 C6H5-C2H5 -H 2 -H 2 CH3CH2CH= CH2 C6H5-CH= CH2 -H 2 CH2=CH-CH= CH2

b) Phn ng hydro ti lin kt C - O

- Ru bc 1:
CH3CH2 O RC C H HH -H 2 RCHO

- Ru bc 2:

R C OH C=O -H 2 -2H2 CH3CH2 R RCH2H 2 CNH R RCN C 2. Phn ng hydro c s thay i v tr cc nguyn t khc H

c) Phn ng hydro ti lin kt C - N R

a) Phn ng hydro ng vng y l loi phn ng thu nhn hydrocacbon thm, xy ra ch yu trong qu trnh reforming xc tc sn xut xng c ch s octan cao.
CH3CH2 C6HC 14 C -4H2 C6H6

b) Phn ng hydro ngng t y l cc phn ng to cc hp cht a vng cao phn t v cng chnh l phn ng gy to cc, cn trong sn phm ca cc qu trnh lc du.
2 -4H2

3. Phn ng hydro tng hp a) Phn ng hydro ngng t in hnh l phn ng tng hp amin, nitril:
CH3CH2 NH RCH3 + C 3 C -H 2 RCH2NH2 -2H2 RCN

b) Phn ng hydro oxy ha

in hnh l phn ng tng hp aldehyd formalic:

5

2 CH3OH + 1/2 O2 2 HCHO + H2O + H2

Thc cht phn ng trn gm 2 phn ng : + Phn ng hydro ha :

CH3OH HCHO + H2

+ Phn ng oxy ha : .
CH3OH + 1/2 O2 HCHO + H2O

Ngoi ra cn c mt s phn ng hydro oxy ha sau:

RCH3 + NH3 + 3/2 O2 RCH2NH2 RCHR

RCN RCN RCR

+ 3 H2O + 2 H2O + H2O

+ +

O2 1/2 O2

OH

 3. C S L THUYT CC QU TRNH
1. Nhit ng hc ca cc phn ng hydro ha v hydro ha a) Phn ng hydro ha l phn ng to nhit v phn ng hydro ha l phn ng thu nhit. Cng mt qu trnh th phn ng hydro ha v phn ng hydro ha s c cng gi tr hiu ng nhit nhng tri du. Hiu ng nhit ca mt s phn ng hydro ha pha kh: Phn ng 1 RCH = CH2 + H2 RCH2 - CH3 2 CH CH + 2 H2 CH3 - CH3 3 RHa + H2 RHN 4 RCHO + H2 RCH2 OH 5 R2CO + H2 R2CHOH 6 RCN + 2 H2 RCH2 NH2 7 RCOOH + 2 H2 RCH2 OH + H2O 8 RNO2 + 3 H2 RNH2 + 2 H2O 9 RHp + H2 R1Hp + R2Hp 10 RHN + H2 RHp 11 RHa + H2 RHp Nhn xt: sau: - H0298 (kJ/mol) 113 134 311 200 217 67 83 58 134 159 38 42 439 472 46 63 42 50 42 46

1) i vi phn ng hydro ha cng hp: nhit sinh ra gim dn theo th t

CC > > CN > C=C > C=O

2) i vi phn ng hydro ha c tch loi (H2O): nhit sinh ra gim dn

theo th t sau:
N

O O

O OH

3) i vi phn ng hydrocracking: nhit sinh ra tng i thp v khng chnh lch nhiu b) Cc yu t nh hng n qu trnh Phn ln cc phn ng hydro ha v hydro ha l phn ng thun nghch.

- Phn ng hydro ha : l phn ng to nhit, gim th tch nn phn ng s xy ra thun li nhit thp, p sut cao; thng thng ch cng ngh cho qu trnh nh sau: + t = 100 350, 4000C + p = 1,5 40 MPa - Phn ng hydro ha :l phn ng thu nhit, tng th tch nn phn ng s xy ra thun li nhit cao, p sut thp; thng thng ch cng ngh cho qu trnh nh sau: + t = 200 600, 6500C + p = p sut kh quyn hoc p sut chn khng V d:
C2H5 CH = CH2

- t = 595oC

p = 0,1Mpa nu p = 0,01 MPa

= 40% = 80%

. 2. Xc tc cho qu trnh :

Ngoi cc phn ng chuyn ha nhit xy ra nhit cao km theo s phn hu v ngng t mnh, tt c cc phn ng hydro ha v hydro ha u c xc tc. C th phn thnh 3 nhm xc tc chnh: 1) Cc kim loi thuc nhm VIII (Fe, Co, Ni, Pt, Pd) v nhm Ib (Cu, Ag) v cc hp kim ca chng.
2) Cc oxyt kim loi: MgO, ZnO, Cr2O3, Fe2O3... 3) Cc oxyt phc hay sulfid (sulfua): CuO.Cr2O3, ZnO.Cr2O3, CoO.MoO3,

NiO.WO3, WS2 (y l xc tc ra i rt sm, c hot tnh cao nhng d mt hot tnh nn hin nay t dng.

Cc xc tc ny c bit l xc tc kim loi thng c phn b trn cc cht mang xp v b sung vo l cc cht kch ng nh l kim loi khc, oxyt khc. 3. C ch phn ng : K hiu K: trung tm hot ng ca xc tc - u tin khi H2 v cc hydrocacbon b hp ph ln xc tc th qu trnh hp ph vt l lm yu cc lin kt H - H, C - H v lin kt khng no ca hydrocacbon V d:
1. K + H2 K... H2 K H... H K H... CH CH3

+K

2KH H H K C CH3 K C CH R R
3

2. K + RCH2CH3

R CH3 hay K CH ... H R 3. K + CH2 = CH2 K... CH2 = CH2

+K

KH +

K CH2 CH2

- Sau s xy ra s hp ph ha hc: * hydro ha:

K CH CH3 R K CH CH2 R

+ K

K CH CH2 R R CH = CH2

+ KH + K

* Hydro ha:
K CH2 CH2 + H2 ... K K CH2 CH3 + KH 2K + CH3 CH3

4. Tnh chn lc ca phn ng: Cc phn ng hydro ha cng nh hydro ha nu khng khng ch iu kin phn ng s xy ra hng lot cc phn ng ni tip hay song song nhau, chng hn nh:
1. RCOOH
+ H2 - H 2O

RCHO

+ H2

RCH2OH 9

+ H2 - H2O

RCH3

2. R -C N 3. C6H5OH

+ H2 + H2 + 3H2

R-CH=NH C6H6 + H2O C6H11OH

+ H2

R-CH2 -NH2

+ H2

R-CH3 + NH3

Do vy tnh chn lc ca phn ng rt quan trng. N ph thuc vo cc yu t sau: Kh nng phn ng ca cc cht hu c hay cc nhm chc ring bit

Kh nng b hp ph ca cc cht hu c hay cc nhm chc ring bit trn b mt xc tc: hp ph nh ca sn phm chnh cho php tin hnh qu trnh vi tnh chn la tt hn v hiu sut cao hn.

Kh nng hp ph ca cht xc tc

Nhit

Thi gian tip xc o i vi qu trnh hydro ha: + chuyn ha: trn 90% + Thi gian tip xc: t phn trm pht n vi gi o i vi qu trnh hydro ha: do tnh thun nghch cao nn: + chuyn ha: 20 40% + Thi gian tip xc: t phn trm giy n vi giy

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4. HA HC V CNG NGH CA QU TRNH DEHYDRO HA

Trong cc qu trnh dehydro ha, ch kho st 3 nhm c gi tr thc t cao: 1. Qu trnh dehydro oxy ha ru: V d: qu trnh sn xut formaldehyt t ru metanol
2 CH3OH + O2 2 HCHO + H2 + H2O

2. Qu trnh dehydro ha hp cht alkyl thm: V d: qu trnh tng hp styren t etylbenzen

C2H5 CH = CH2 + H2 3. Qu trnh dehydro ha parafin v olefin:

V d: qu trnh tng hp Butadien - 1,3 v isopren CH3CH2CH2CH3 CH3CHCH2CH3 CH3 I.

- H2 - H2

CH2 = CH CH2 CH3 CH2 = CH CH2 CH3 CH3

- H2 - H2

CH2 = CH CH = CH2 CH2 = CH CH = CH2 CH3

Qu trnh tng hp formaldehyt t ru metanol

1. Tnh cht ca Formaldehyt

iu kin thng, formaldehyt l cht kh c mi hc, l loi kh c c th lm hng nim mc mt, c tngng t = 19oC. D tan trong H2O hoc Metanol Dung dch cha 37 40% khi lng HCHO trong nc gi l Formalin. Khi bo qun HCHO d b polyme ha. km ch qu trnh polyme ha su v kt ta formalin, thng b sung thm 712% (m) Metanol lm cht n nh.
11

Kh HCHO d chy, c th to thnh hn hp chy n vi O2 khng kh p sut thng trong gii hn t 7 72% V v hn hp HCHO trong khng kh t 65 70% l d bc la nht

ng dung:l mt cht hu c c gi tr ln, dng trong sn xut polyme (ch yu l cht do); dng lm cht trung gian tng hp cc cht c gi tr khc; dng lm cht st trng, dit khun; dng lm cht p thm, cht bo qun xc thc ng vt

Sn xut: C nhiu phng php sn xut HCHO, nhng phn ln c sn xut t Metanol bng 2 phng php : dehydro ha ng thi vi mt phn oxy ha v phng php oxy ha vi lng d khng kh.

2. Cng ngh sn xut 2.1. Phng php dehydro ha v oxy ha ng thi Metanol Phn ng chnh: CH3OH HCHO + H2 -Ho = -85,3 kJ/mol -Ho = 156,3 kJ/mol

CH3OH + 1/2 O2 HCHO + H2O Phn ng ph:

CH3OH + 1/2 O2 HCOOH (+ 1/2 O2) CO2 + H2O CH3OH + H2 CO2 + H2 CH4 + H2O CO + H2O

Trong 2 phn ng chnh, c th la chn t l ca cc phn ng sao cho phn ng tng cng l to nhit v lc trnh tht thot nhit, ngi ta dng lng nhit ny nung nng hn hp phn ng n nhit phn ng. Trong phng php ny c 2 cng ngh chnh:

Dehydro oxy ha bng khng kh vi s c mt ca tinh th Ag, hi nc v lng d CH3OH nhit 680 720oC. chuyn ha ca CH3OH l 97 98%. Qu trnh ny gi l qu trnh BASF

Dehydro oxy ha bng khng kh vi s c mt ca tinh th Ag, hi nc v lng d CH3OH nhit 600 650oC. chuyn ha ca CH3OH l 77 87% v thu hi CH3OH bng chng ct.

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a. Qu trnh BASF:

hi nc

kh thi g

b i hi nc

c d nc

nc

h b k.kh Metanol, nc a f e HCHO 50%m i hi nc

Hnh 1: S cng ngh tng hp Formaldehyt theo qu trnh BASF a. Thit b bc hi b. My nn kh c. Thit b phn ng nc d. Thit b lm lnh h. Thit b lm lnh e. Thit b trao i nhit f. Thp hp th g. Thit b sn xut hi

i. Thit b trao i nhit dng hi nc Thuyt minh: Metanol v khng kh c trn ln vi nhau trc khi a vo thit b bc hi (a). Khng kh v kh tun hon t nh thp hp th (f) c a vo ct ring l. Qu trnh pha trn th tch gia Metanol v khng kh c hnh thnh vi s c mt ca cc kh tr (N2, H2O, CO2) sao cho vt trn gii hn n. Thng thng th trong 1 lt hn hp to thnh cn cha khong 0,5g Metanol. lm cho Metanol v nc chuyn hon ton thnh hi th hn hp ny c i qua thit b trao i nhit (e) bn ngoi ri a tr li thit b bc hi. Lng nhit

13

dng lm bay hi MeOH, H2O c ly t dng sn phm HCHO y ca thp hp th. Hn hp hi sau khi ra khi thit b bc hi s c a qua thit b gia nhit (i) d t n nhit phn ng trc khi vo thit b phn ng (c). Trong thit b ny hn hp hi c i qua mt lp tinh th Ag c chiu dy 25 30 mm. Nhng tinh th Ag c kch thc ht nm trong mt phm vi nht nh v c t trn mt gi c c l. Lp xc tc c t ngay trn thit b lm lnh bng nc (d). Thit b ny s sn xut hi nc qu nhit v ng thi lm gim nhit ca hn hp hi sn phm xung cn 150oC vi p sut hi l 0,5 MPa. Kh sn phm tip tc i vo y ca thp hp th 4 tng (f). Ti y kh sn phm c lm lnh v ngng t thnh dng lng. Sn phm HCHO i ra t tng u tin c th cha 50% HCHO vi hm lng MeOH trung bnh l 1,3% m; 0,01% m acid formic. Hiu sut ca qu trnh c th t c t 89,5 90,5% mol. Mt phn kh i ra khi giai on 4 ca qu trnh cha hm lng HCHO thp c s dng lm kh tun hon. Phn cn li c a n thit b trao i nhit (g) sn xut hi nc (nng lng kh to ra l 1970 kJ/m 3). Trc khi i n l t th thnh phn ca kh bao gm 4,8% V CO 2, 0,3% CO v 18% H2 cng nh N2, H2O v HCHO. Kh trc khi c thi ra ngoi phi c x l loi b nhng cht c hi nh hng n mi trng. Trong mt trng hp khc, nu khng s dng kh i ra giai on 4 ca thp hp th tun hon th c th s dng hn hp hi c ly ra i n thit b lm lnh ca giai on 3 hoc 4 lm hi tun hon. Lng hi ny c mc ch lm bc hi H2O v MeOH, to ra t l ti u gia MeOH v H2O. i vi trng hp ny th nhit ca hi i ra khi giai on 2 l 65 oC. Hiu sut ca 2 cng ngh tng ng nhau v ph thuc vo lu lng dng trong thp hp th. Thi gian sng trung bnh ca lp xc tc ph thuc vo sch ca nguyn liu: khng kh v MeOH. S nhim c do nguyn liu khng sch lm gim hot tnh ca xc tc ch trong vi ngy. Thi gian sng ca xc tc s gim khi tn ti

14

nhit cao lp xc tc lu qu mc v s lm tng tr lc ca lp xc tc nh hng n lu lng dng i qua. Hin tng ny khng th khc phc c, do vy cn phi thay th lp xc tc sau 3 4 thng. Xc tc c ti sinh bng phng php in phn. Mt vn cn lu trong sn xut HCHO: HCHO l hp cht c kh nng n mn thit b cao, do vy cn phi ch la chn vt liu khi ch to thit b (nh inox...) . Hn na trong cc thit b ng ng vn chuyn nc, khng kh, cn phi s dng thp hp kim loi b bt s u c xc tc do kim loi. b. Qu trnh chuyn ha khng hon ton v thu hi Metanol bng thp chng ct
hi nc nc c i hi nc d nc hi nc h f b k.kh a hi nc h h e kh thi g nc h

Metanol

HCHO 50%m

Hnh 2: S cng ngh tng hp Formaldehyt bng qu trnh chuyn ha khng hon ton v thu hi MeOH bng thp chng ct a. Thit b bc hi b. My nn kh f. Thp hp th g. Thit b sn xut hi nc

15

c. Thit b phn ng d. Thit b lm lnh e. Thp chng tch MeOH a.formic

h. Thit b lm lnh i. Thit b trao i nhit dng hi nc j. Thp trao i ion tch

Thuyt minh: Metanol v khng kh c a vo thit b bc hi (a); ti y xy ra qu trnh trn ln gia hi MeOH v khng kh. Hn hp hi to thnh khi i ra khi thit b bc hi c kt hp vi dng hi bn ngoi sau i qua thit b TN (i) t n nhit phn ng t 590 650oC ri i vo TBP (c). Ti y hn hp hi nguyn liu c i qua lp xc tc cha tinh th Ag hoc chy qua cc lp Ag v xy ra qu trnh chuyn ha khng hon ton. Ngay sau khi ra khi lp Ag xc tc , hn hp sn phm to thnh c a ngay n thit b lm lnh bng nc (d). Thit b lm lnh ny t ngay di TBP. Sau hn hp c a vo y thp hp th (f). Trong thit b ny xy ra s tip xc ngc chiu gia hi sn phm v nc. Qu trnh ny hu nh lm ngng t ton b HCHO, H2O v MeOH c trong hn hp sn phm. y thp thu c dung dch MeOH v HCHO cha khong 42% m HCHO. Dung dch ny c a n thp chng ct (e), mt phn c s dng lm hi lu. Sn phm nh ca thp hp th c a n thit b TN (g) dng sn xut hi nc; sau a n l t x l trc khi thi ra mi trng. Ti thp chng ct (e) c s dng thit b un si li bng hi nc, v y thp thu c dung dch HCHO 50% m vi hm lng MeOH 1%m. dung dch ny c a n thit b trung ha nhm gim lm gim chua gy ra do acid formic n mt ga tr < 50mg/kg. nh ca thp chng ct thu c dung dch MeOH, mt phn c hi lu, mt phn c kt hp vi MeOH nguyn liu lm nguyn liu cho thp bc hi. I.2. Qu trnh oxy ha MeOH thnh HCHO - Qu trnh Formox

y l qu trnh tng hp HCHO mi bng phng php oxy ha MeOH vi lng d khng kh cng vi s c mt ca xc tc Fe ci tin - Molybden - Vanadi

16

oxyt [Fe2(MoO4)3 - V2O5] lm vic theo c ch oxy ha - kh nhit 250400oC cho chuyn ha cao t 98 99%. Tiu biu l qu trnh Formox c m t bng phn ng 2 giai on trong trng thi th kh (g), bao gm s oxy ha (Kox) v s kh (Kred) xc tc. CH3OH (g) + Kox HCHO (g) + H2O + Kred Kred + 1/2 O2 (g) Kox S cng ngh ca qu trnh Formox:
b hi nc kh thi nc d c g b k.kh e nc f

H = -159 kJ/mol

a hi nc h

Metanol

HCHO 55%m

Hnh 3: S cng ngh ca qu trnh Formox a. Thit b bc hi b. My nn kh c. Thit b phn ng d. Thit b lm lnh e. Thit b trao i nhit f. Thp hp th HCHO g. Du ti nhit h. Thit b lm lnh i. Thp trao i ion tch acid formic

17

Thuyt minh: MeOH nguyn liu c cho vo thit b bc hi (a). Khng kh t kh quyn c qut ht vo kt hp vi dng kh thot ra t nh thp hp th (f) c gia nhit nh thit b TN (e) trc khi a vo thit b bc hi (a). Thit b trao i nhit (e) ny nhm thu hi lng nhit ca sn phm khi i ra khi TBP (c). Hn hp hi to thnh s c a n TBP (c). ti y hi nguyn liu s i qua cc ng c cha xc tc. Phn ng xy ra trong cc ng xc tc ny. Mt thit b tiu biu cho qu trnh ny c ng knh 2,5 m ch cha ng cc ng xc tc c chiu si khong 1,0 1,5 m. Bn ngoi cc ng c dng du truyn nhit nhm thu nhit do phn ng to ra t trong ng cha xc tc. lng nhit ny dng sn xut hi nc thng qua thit b TN (d). Qu trnh ny s dng lng d khng kh Sn phm kh to thnh sau khi ra khi TBP s c lm lnh xung cn 110oC nh thit b TN (e) v a qua y thp hp th (f). HCHO trong kh sn phm s c ngng t y thit b hp th, mt phn a i lm lnh s dng lm dng hi lu, phn ln cn li c a i qua thit b trung ha nhm lm gim chua do a.formic gy ra trong sn phm . Sn phm cui cng ca qu trnh c th t 55%m HCHO vi hm lng nh 0,51,5% khi lng MeOH. Kt qu ca s chuyn ha MeOH t t 9599% mol v ph thuc vo chn lc, hot tnh v nhit ca xc tc. Hiu sut ton b ca qu trnh ny l 8891% mol Bng so snh cc ch tiu kinh t cc qu trnh : Cc ch tiu Tng gi tr u t 106.USD Tiu hao nguyn liu MeOH (tnh cho 1 kg HCHO) Gi sn phm USD/t Qu trnh chuyn Qu trnh chuyn ha hon ton ha khng hon ton (BASF) v thu hi MeOH 6,6 1,24 345 8,6 1,22 364 Qu trnh Formox 9,6 1,15 339

18

II.

Qu trnh tng hp Styren: C6H5-CH=CH2

1. Tnh cht ca Styren

iu kin thng, styren l mt cht lng khng mu c ts = 145oC 0,1MPa; d420=0,907

ng dng:
o Styren d polyme ha khi nung nng hay di nh hng ca cc cht

khi u v to ra polyme rn: polystyren n C6H5 CH = CH2 [ CH CH2 ]n C6H5 Polystyren c tnh cch in tt v bn ha hc cao; dng ch to cc chi tit ca cng ngh in - in t, lm cht do, xp, nha. o Styren tham gia qu trnh ng trng hp vi Butadien sn xut cao su tng hp Sn xut : o Hu nh ton b Styren c sn xut bng phng php dehydro ha etylbenzen C6H5 CH2 CH3 C6H5 CH = CH2 + H2

o 2 phng php mi ang nghin cu: kt hp oxy ha benzen vi etylen xc tc bng Pd C6H6 + C2H4 + 1/2 O2 C6H5 CH = CH2 + H2O

ngng t oxy ha toluen thnh Stylben, sau stylben phn hu cng vi etylen to ra styren C6H5 CH3 + O2 C6H5 CH = CH C6H5 + H2O 2 C6H5 CH = CH2

C6H5 CH = CH C6H5 + C2H4

2. Ch cng ngh dehydro ha etylbenzen tng hp styren C 2 ch cng ngh:

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 Cng ngh khng c xc tc:

o Nhit phn ng t = 700 800oC o chuyn ha C% = 20 30% o Hiu sut sn phm : 50 60%

Cng ngh c xc tc:

o Nhit phn ng: tu thuc loi xc tc s dng, tuy nhin t 600oC o p sut ring phn ca hydrocacbon : thp o chuyn ha cao hn, chn lc cao (khong 90%)

o Xc tc: gm 3 thnh phn chnh:

Pha hot ng: Fe2O3 chim t 55 80% Pha kch ng: Cr2O3 chim t 2 28% Mui Kali: K2CO3 chim t 15 35%

Ngoi ra cn mt vi oxyt ph. Cht xc tc lm vic lin tc t 1 2 thng, sau em t chy lp than cc bng khng kh. Thng tui th ca xc tc t 1 2 nm.
3. S cng ngh: tu thuc phng thc lm vic ca TBP, c 2 dng qu

trnh cng ngh chnh: Qu trnh on nhit Qu trnh ng nhit 3.1.

Qu trnh dehydro ha on nhit c im: nguyn liu phi c gia nhit khong 650oC sau c a n TBP c cha cc tng xc tc. Nng lng b sung cho nguyn liu s c thc hin nh hi nc.

iu kin vn hnh:
o Nhit vo TBP = 650oC ; nhit ra = 580oC o Ap sut : khong 1,4 2 bars

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o T l khi lng Hi nc / Etylbenzen = 2 3 o VVH = 0,45 0,65

o chuyn ha (1 chu trnh) = 40%

o Hiu sut = 88 91%
720oC 520oC 650oC i x l kh

hi nc

TBP styren th l ng 580oC hi nc etylbenzen

Thuyt minh dy chuyn: Etylbenzen nguyn liu v etylbenzen hi lu c cho bay hi v ha trn vi lng 10% hi nc cn dng, sau c gia nhit n 520 550oC nh qu trnh TN vi dng sn phm i ra khi TBP. Trc khi vo TBP, etylbenzen c trn vi 90% hi nc cn li c nhit 720oC v khi s nng nhit nguyn liu ln 650oC. TBP c ch to bng thp Crm (nu c s c mt ca Ni s dn n cc phn ng th cp). Nng sut cc i ca loi thit b ny t t 15000 17000 tn / nm. Dng sn phm ra khi TBP c t = 580oC sau khi TN vi nguyn liu v c ngng t mt phn s c a i phn tch. T phn nh ngi ta s thu c hn hp kh thi c cha khong 90% H2 v 10% CO2. Phn nng gm c benzen v cc hydrocacbon nng khc. 3.2. Qu trnh dehydro ha ng nhit

Tiu biu c qu trnh BASF.

c im: thit b phn ng ng chm c hng = 2,5 4 m; ng = 10 20 cm v xc tc c cha y trong ng iu kin vn hnh:
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o Nhit vo ra khi TBP = 580oC o Nhit ca cht ti nhit: tvo = 750oC ; tra = 630oC

o T l khi lng Hi nc / Etylbenzen = 1/1 o chuyn ha = 40%

o Hiu sut = 92 94%

Ch vn hnh ny c th thay i ty thuc vo bn cht cht ti nhit v h thng thu hi nhit.

i x l kh

580oC

750oC 630oC 375oC TBP 580oC khi

styren th

nhin liu

hi nc etylbenzen qut gi

ng dn khi l

Thuyt minh dy chuyn BASF: trong s BASF, cht ti nhit c s dng l khi l. Etylbenzen v hi nc c cho bay hi v lm nng qu nhit nh qu trnh TN vi dng sn phm ra khi TBP. Khi l sau khi TN s h nhit xung cn 375oC, mt phn c thi ra, v phn cn li c gia nhit trong l tip tc lm cht ti nhit. Nng sut cc i ca qu trnh ny khong 22000 tn/ nm. 3.3. Qu trnh dehydro ha on nhit 2 TBP

khc phc nhc im ca s on nhit v ng nhit, mt cng ngh mi sn xut Styren nhiu u vit c s dng ph bin l qu trnh dehydro ha on nhit s dng 2 TBP ni tip.
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Hi nc

Etylbenzen sch Hi nc

Etylbenzen hi lu 4 2 3 5 Kh H thng chng tch sn phm

6 Styrene th 1 Nc ngng

Styrene

Polystyrene

Hnh 4: S cng ngh dehydro ha on nhit tng hp Styren 2 TBP 1. L gia nhit 2,3. TBP on nhit 4. TB gia nhit 3.4. Tinh ch Styren th 5. Thit b ngng t 6. TB tch 3 pha 7. My nn

Styren th thu c bao gm etylbenzen cha chuyn ha, nc, styren v cc sn phm ph (benzen, toluen ...). u tin sn phm th ny s c em tch thnh pha nc v pha hu c. Pha hu c c em chng phn on tch Styren v thu hi Etylbenzen cha chuyn ha. Kh khn nht l s tch Etylbenzen v Styren, v 2 nguyn nhn sau:
o Chnh lch nhit si b: etylbenzen (136oC) ; styren (145oC)

o Styren rt d b polyme ha Qu trnh tch ny thng thng c thc hin qua 3 giai on chng ct:

Tch loi Benzen, Toluen v H2O. Benzen c th c tch ring v thu hi cho qu trnh alkyl ha
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 Thu hi etylbenzen v hi lu Tinh ch Styren khi b nng (c th t tinh khit 99,8%) Cc giai on ny phi thc hin p sut chn khng duy tr nhit thp (n mc c th) nhm trnh s polyme ha Styren. ng thi trnh hin tng ny ngi ta c s dng cht c ch: Lu hunh hoc dinitrophenol cho 2 giai on u p.tert - butylpyrocatchol cho giai on cui v giai on tn cha. III. Qu trnh tng hp Butadien-1,3 v Isopren

1. Tnh cht Butadien-1,3 v Isopren 1.1.

Tnh cht Butadien-1,3

iu kin thng l cht kh khng mu, c mi nh, c ts = -4,3oC t ha tan trong nc v tan rt t trong metanol, etanol nhng li tan nhiu trong cc dung mi hu c nh dietyl ete, benzen, CCl4. To hn hp n vi khng kh trong khong nng 2,0 11,5% (V)

C c tnh ph hu mng nhy hay gy tc dng ph ng dng: l monome c s tng hp cao su o Polyme ha tng hp cao su Butadien n CH2 = CH - CH = CH2 [- CH2 - CH = CH - CH2 -]n

o Copolyme ha vi Styren, Acrylonitril tng hp cao su ABS Sn xut : c 3 phng php hin nay ang s dng
o Tch Butadien-1,3 t phn on C4 ca sn phm nhit phn phn

on lng du m ( hc trong chng sn xut olefin - mn KTHHHC). y l phng php kinh t nht cho php p ng n 40 50% nhu cu s dng monome ny.

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o Dehydro ha phn on n-buten tch ra t cc sn phm nhit phn hay cracking xc tc. Theo ch tiu kinh t phng php ny ng v tr th hai.
CH2 = CH CH2 CH3
- H2

CH2 = CH CH = CH2

- H2

CH3 CH = CH CH3

o Dehydro ha n-butan tch ra t cc kh thi

C4H10
- H2

C4H8

- H2

C4H6

1.2.

Tnh cht Isopren Isopren l n v cu trc c s ca cao su t nhin.

iu kin thng l cht lng khng mu d bay hi c ts = 34oC Tan hn ch trong nc: 20oC ha tan c 0,029% mol trong nc; tuy nhin n c th trn ln trong dung mi hu c vi mi t l, chng hn nh etanol, dietyl ete, aceton, benzen.

To hn hp n vi khng kh trong khong nng 1,7 11,5% (V) ng dng: o Polyme ha vi xc tc c kim sn xut cao su polyisopren n CH2 = C - CH = CH2 CH3 [- CH2 - C = CH - CH2 -]n CH3

o Copolyme ha vi styren sn xut cao su Isopren - Styren

Sn xut: sn xut isopren cng dng 3 phng php nh trng hp Butadien-1,3. Tuy nhin do s phc tp v thnh phn dn n kh khn ln cho vic phn tch cc phn on ban u hay thu nhn c lm nh hng n gi tr ca phng php tng hp isopren. Ngoi ra cn c 2 phng php khc: o i t Isobuten v formaldehyt HCHO : 2 giai on
CH3 (CH3)2 - C = CH2 + 2 HCHO CH3 C CH3 O - CH2 CH2 - CH2 O 25 C CH3 O - CH2 CH2 - CH2 O

CH2 = C - CH = CH2 + HCHO CH3

o i t Propylen: thc hin phn ng qua 3 giai on Dime ha

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

Isome ha
CH2 = C - CH2 - CH2 - CH3 CH3 CH3 - C = CH - CH2 - CH3 CH3

Cracking
CH3 - C = CH - CH2 - CH3 CH3 CH2 = C - CH = CH2 CH3 + CH4

2. Cng ngh dehydro ha sn xut Butadien-1,3 v Isopren 2.1.

Cng ngh dehydro ha phn on olefin sn xut dien

Xc tc : cht xc tc tt nht hin nay l photphatcanxiniken Ca8Ni(PO4)5 kt hp thm cht ph gia tng hot Cr2O3 (khong 2%). c im ca loi xc tc ny l b than ha nhanh v mt hot tnh, v vy phi thng xuyn loi tr than cc. Do cn phi c nhiu TBP lm vic song song nhau, thc hin lin tc cc bc dehydro ha v ti sinh xc tc. V d nh cng ngh Dow B, 1 chu k gm 30 pht: 15 pht thc hin phn ng, ti sinh xc tc 11 pht, thi khng kh pha long vi hi nc trc v sau khi ti sinh mi lt 2 pht.

C pha long bng hi nc gim p sut ring phn v gim hnh thnh cc thng theo t l 20 : 1

VVH = 150 200 h-1

Ap sut tng vt qu cht t so vi p sut kh quyn

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Nhit ti u dehydro ha buten 600 650oC ; %C = 40 50%; %S (sn phm) = 85%. i vi isopenten c kh nng phn ng mnh hn, v cho phn ng ph nhiu hn th nhit ti u gim xung 550 600oC ; %C = 40% ; %S = 82 84%

TBP: loi thit b phn ng on nhit vi tng xc tc c nh c chiu dy 80 90cm. Khi hi gi vai tr l cht mang nhit khng cho hn hp ngui t ngt; chnh lch nhit gia v tr u v v tr cui ca lp xc tc c 30 40oC.

S cng ngh:
khi khng kh 3 hi nc 4 1 olefin 2 hi nc 4 5 5 nc 3 hi nc 8 hi nc sn phm 8 6 7

nc ngng

nc ngng

Hnh5: S cng ngh dehydro ha olefin 1,2. L t ng 3. Thit b trn 4. Thit b phn ng 5. Thit b to hi

6. Thit b lc kh

7. Thit b lnh

8. Thit b thu hi hi

Thuyt minh: phn on olefin v hi nc sau khi nung l t nng (1) v (2) tng ng ln ti 500 v 700oC s trn vo nhau ti b phn trn (3) v a n ca vo ca TBP c nhit thp. Do cn phi phi hp nhanh gia cc giai on dehydro ha v ti sinh nn TBP (4) lm vic theo tng cp; nu 1 thit b ang dehydro ha olefin th thit b kia s ti sinh xc tc bng hn hp khng kh vi nc. Sau mi giai on ny, cc thit b c ra tc thi bng hi nc v thi

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khng kh. Nhit ca cc kh ti sinh v phn ng c dng to hi. Sau cc kh ti sinh s c thi ra ngoi cn kh phn ng th em i phn tch u tin tch c hydrocacbon thp v cao phn t (bng cch chng phn on p sut d nh) v t phn on C4 hay C5 s tch c tng ng l Butadien hay Isopren bng cc phng php trch ly dung mi hay chng ct trch ly ( hc chng olefin - mn KTHHHC). Olefin cha chuyn ha s c tun hon li qu trnh. Nhc im: + chuyn ha v tnh chn la thp + chi ph nng lng 2.2. Qu trnh dehydro oxy ha n-olefin sn xut dien

chuyn ha v tnh chn lc ca qu trnh dehydro ha n-olefin thnh dien c th c ci tin bng vic loi b H2 hnh thnh trong qu trnh phn ng v b sung O2 vo chuyn ha lng H2 ny thnh H2O. CH2 = CH - CH2 - CH3 + 1/2 O2 Cc iu kin cng ngh: o Xc tc: cht xc tc cho qu trnh dehydro oxy ha l hn hp cc oxyt ca Bi + Mo; Bi + Mo + P; Bi + W; Sb + Fe ...
o Nhit : 400 600oC

CH2 = CH - CH = CH2 + H2O

o T l hi nc pha long: t 1:5 n 30:1 (V)

o chuyn ha: 70 80% o chn lc: i vi Butadien-1,3 : 90 95%

i vi Isopren: khong 85% o TBP: qu trnh dehydro ha v oxy ha c tin hnh ng thi trong mt thit b vi lp xc tc c nh
o C ch: c ch oxy ha kh vi s tham gia ca O2 vo mng li tinh th

oxyt kim loi K - O - + C4H8 K - O - C4H8 K + H2O + C4H6

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2 K + O2

2K - O kh t n-buten

S qu trnh dehydro oxy ha n-buten:

10 2 du h.th 1 hi nc 4 5 khng kh hi nc nc nc 3 9 6 7 8 C4

Hnh 6: S cng ngh dehydro oxy ha n-buten thnh butadien-1,3 1. L t ng 2. TBP 3. Thit b to hi 4. Thit b lc kh 5, 7. Thit b lm lnh 6. Thit b hp th 8. Thp tch hi 9. ni un 10. Thit b ngng t

Thuyt minh: Hi nc v khng kh c trn vo nhau v c nung nng trong l ng (1) n 500oC. Phn on n-buten c a trc tip vo hn hp ny trc TBP (2). Qu trnh thc hin trn lp xc tc c nh iu kin ng nhit vi t = 400 500oC v p sut p = 0,6 MPa. Nhit ca hn hp kh phn ng sau khhi ra khi TBP c i qua thit b sinh hi (3) to hi p sut cao. Sau kh c lm lnh bng nc thit b lc kh (4) cng vi thit b lm lnh (5) v ra bng dch khong thit b hp th (6). Ti y s hp th hydrocacbon C4 cn cc sn phm cracking, N2 v phn d O2 s thot ra khi nh ca (6) v s dng lm nhin liu kh trong l t ng (1). Cht lng bo ha t thit b (6) s cho qua thp tch hi (8) ti sinh dung mi hp th v a tr v (6) sau khi thit b lm lnh (7). Phn on C 4 pha trn (8) cha khong 70% Butadien-1,3. Bng cc phng php bit s tch c

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Butadien-1,3 tinh khit; cn n-buten cha chuyn ha s hon lu v qu trnh dehydro oxy ha.

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