cong nghe tong hop hoa dau_tran cong khanh

8/13/2019 Cong Nghe Tong Hop Hoa Dau_Tran Cong Khanh

1/64

CNG NGH TNG HP HO DU

Ngi son: PGS, TS Trn Cng Khanh

I-GII THIU V CNG NGH TNG HP HO DUI-1/V tr ca CNTHHD trong h thng sn xut cc hp cht hu c:

CN ch bin NL rn

Nhin liurn

Du m Kh t nhin

CN ch bin du, kh

H/C thm H2, CO Axtylen H/C no lfin

CNG NGH TNG HP HO DU

Cc hpcht trung

gian

ChtHBM,ty ra

Nhin liudu nhntng hp

Dung miCc

mnme

Cc CN Tng hp hu c CN Cao phn t

Sn TH Si TH

Cao su TH Cht do

Cht mu

Dc phm Nng dc

Cht n

H.1.1-V tr CN THHD trong h thng CN SX cc hp cht hu c

-T nguyn liu than , du m v kh t nhin qua cc qu trnh ch

bin ta c nm loi hp cht ban u l cc hydroccbon thm, H2, COv hn hp H2+CO (c gi l kh tng hp"), axtylen, cc loihydroccbon no ( mch thng, nhnh, vng ) v cc lfin.

Vi s pht trin mnh ca h thng CN SX cc hp cht hu cnhim v ca CN THHD phi ch ng sn xut cc hp cht ban u ny,c bitquan trng l cc lfin, hydro v cc hydroccbon thm.


2/64

-Trong hn nath k quacc cht ban u trn ch yu c sn xutt du kh, do vy CNtng hp hu cc gi l CN THHD.

-Nh vy, CN THHD i t cc hp cht ban u tng i n ginsn xut ra hng lot cc hp cht hu c quan trng, c s dng trc tipnh cht hot ng b mt, ty ra, cc loi du nhn v nhin liu tng hpcng cc ph gia khng th thiu c cho cc sn phm du m, cng nhlm hpchttrung gian, lm nguyn liucho mt lot cc CN sn xut cchp cht hu c khc nh sn xut cht do, sitnghp, cao su tnghp,sn tng hp, cc cht mu, cht n, dc phm, cht bo v thc vt, kchthch sinh trng ...

a/Cc hp cht trung gian:*L cc hp cht c hot tnh ho hc cao nh cc hp cht cha halogen,cha oxy (cc ru, aldhit, xton, axit hu c, cc oxit huc),cc hpcht cha nit, lu hunh.... V d:

+1,2 Dicloetan l hp cht trung gian quan trng sn xut vinylclorua - mt mnme quan trng, cng nh sn xut etylendiamin, vt liucao su chu xng du tiokol.

+Oxit etylen l hp cht trung gian sn xut cc glycol ( MEG,DEG, TEG...), cc etanolamin (MEA, DEA,TEA...), cht HBM khngion...*L sn phm quan trng ca THHD, c sn lng ln, a dng v chngloi, c s dng cho nhiu ngnh THHC, trong c bn thn CNTHHD

b/Cc mnme, cc ph gia cho cng nghip polyme nh cht nnh, cht chngoxi ho, cht ho do... vi cc c im: sn lng ln, adng v chng loi vi cc vt liu polyme mi, yu cu thun ccmnme rt cao m bo tnh nng, mu sc ca polyme (thng yu cutrn 99,9%).

c/Cht HBM v git ra:*Cu to cht HBM c 2 phn: ght v thch nc, nh vy chng tptrung b mt phn chia pha vi cc tnh nng qu gi nh gim sc cng bmt, tng cng thm t b mt, to nh tng, ty ra b mt v do cng dng rt rng ri trong cng nghip cng nh trong i sng.*ng dng trong cng nghip: CN dt nhum (git ty, thm t, to nh),

CN khong sn (dung dch khoan, tuyn khong...), vi hiu ng Rebinderc dng lm ph gia trongdung dchlm mt caqu trnh ct gt kimloi,trong dung dchkhoan, chttrnghin, lm ph gia nh ho cho vtliuxy dng, trong CNho cht,cng nghipsnxutpolyme, thc phm,m phm ...


3/64

*Cc cht HBM v git ra thng c thi ra mi trng, do vy gim nhimcn loi d phn hu sinh hc (phn ght nc c cu tomch thng).

d/Nhin liuv du bi trn tng hp, cc ph gia cho cc sn phmdu m:*To cc vt liu bi trn tng hp lm vic nhng iu kin khc nghit:nhit cao trn 3000C hay nhit thp di -600C, hay iu kin chu titrng ln.*Sn xut cc nhin liu c bit nh nhin liu phn lc c sc y ln.*Sn xut cc loi ph gia cho cc sn phm du: ph gia chng oxi ho vc ch kim loi, ph gia bm dnh b mt, ph gia tng ch s nht, phgia ty ra b mt, ph gia chng kch n cho xng nhin liu, ph giachng ng c v ph gia tng cng bt chy cho du diezel ...

-Nh vy, CN THHD c vai tr v tr bn l trong hthng sn xut

cc sn phm hu c, l mt giai on bin i su sc ca vt chtnn chiu qu kinh t cao, c th ni tim lc cng nghip ho hc ca mi nc

ph thuc vo trnh pht trin ca CN THHD.I.2-Xu th pht trin ca CN THHD:

a/S dng nhng thnh tu khoa hc k thut lin quan: ho hc cchp cht hu c, cc thnh tu v xc tc, v k thut phn ng, v cc qutrnh v thit b ho hc to nn cc cng ngh mit ph thi, m rngngun nguyn liu ban u...

b/Nng cao cng sut ca thit b, c bit TBP lin quan vi tng ho qu trnh.V d sn xut Etylen cng sut thit b tng t 20 nghntn/nm ln 250 nghn tn/nm gi thnh gim 4 ln, u t gim 2-3 ln,nng sut lao ng tng 2,5-3 ln. n nay cng sut ca mt n v snxut Etylen thng t 400-500 nghn tn/nm v Etylen tr thnh nguynliu r, di do, chim v tr quan trng trong CN THHD.

c/Lin hp sn xut nhm tn dng nguyn liu ban u, ci thin chtiu kinh t- k thut ca qu trnh sn xut, to cng ngh sn xut khng

ph thi.V d sn xut mnme vinyl clorua(VCM):

*Lin hp vi cc cng on sn xut Etylen, in phn NaCl sn xut

clo cng nh vi cng on polyme ho VCM thnh PVC.*Kt hp qu trnh clo ho vioxi clo ho Etylen v cng on nhit phn1,2 dicloetan thnh VCM:- Clo ho Etylen CH2=CH2+ Cl2CH2Cl-CH2Cl- Nhit phn 1,2 DCE 2CH2Cl-CH2Cl 2CH2=CHCl + 2HCl- O xiclo ho Etylen CH2=CH2+ 2HCl + 1/2O2CH2Cl-CH2Cl + H2O


4/64

Tng cng 2CH2=CH2+ Cl2+ 1/2O22CH2=CHCl + H2O*Kt hp qu trnh clo ho etylen vi hi droclo ho a xtylen v cng onnhit phn 1,2 dicloetan thnh VCM:- Clo ho Etylen CH2=CH2+ Cl2CH2Cl-CH2Cl

- Nhit phn 1,2 DCE CH2Cl-CH2Cl CH2=CHCl + HCl- Hidroclo ho Axtylen CH CH + HCl CH2=CHClTng cng CH2=CH2+ CHCH + Cl22CH2=CHCl

II-SN XUT CC HP CHT BAN U CHO THHD:

II.1/SN XUT CC OLEFIN.-L nguyn liu quan trng nht ca THHD, c bit l Etylen.-Chia thnh 2 nhm: *Cc lfin thp C2 - C5

*Cc lfin cao C6 - C18II.1.1/Sn xut cc O. thp:

Bng 2.1 Mt s tnh cht ca O thpHp cht TS,

0C T ti hn,0C Gii hnn vi kkh,%V

Etylen -103,7 9,9 3 32Propylen -47,7 91,8 2,2 10Buten-1 -6,3 146,2 1,6 9,4

Cis Buten-2 13,7 157 1,6 9,4Trans Buten-2 0,9 1,6 9,4Iso Buten -7 144,7 1,6 9,4Cc n-Penten 30 37 1,3 8,8Cc i-Penten 20,1 38,6 1,3 8,8

-E=c T ti hn thp, ch ho lng khi nn v lm lnh nhit thp(bng NH3 lng hay propan lng ),cc O khc c th ho lng khi nn v lmlnh bng nc.

-O c Ts thp hn H/C no: E= so vi E(TS = -88,60C) c Ts=150C, c th

tch ring bng chng luyn. Vi P=/P kh hn (Ts = 5,50C). Vi C4khng th tch ring tng cu t bng phng php ny.

-Gii hn n di vi khng kh thp: nguy him cao v d to hn hp nkhi c r r.

-Electron ca lin kt kp c kh nng tng tc mnh vi b mt chtrn, dung mi c cc nh axton, furfural, axtonitril... Nh dng phpchng trch ly c th tch butadien (Ts = -4,40C) t hn hp H/C C4.


5/64

-O thp ch yu c sn xut t kh crcking xc tc v bng cng nghcrcking cc H/C c mt hi ncgi l crcking hi (steam cracking).

II.1.1.A-Cng ngh cracking hia/C s nhit ng:-So vi cc H/C no nhit to thnh cc O tng theo nhit chm hn, dovy nhit cao nhit to thnh cc O nhhn cc H/C no v bn hn.

bn tng theo th t sau:Parafin < Olefin < Diolefin < Alkylbenzen < Benzen < Thm nhiu nhnHnh 2.1 trnh by tng quan nhit to thnh ca cc loi H/C vo nhit

H.2.1.1-Nhit to thnh ca mt s hydrocacbonph thuc vo nhit

-Trn c s ny c th sn xut O. t cc H/C no nhit tng icao, trong sn xut E=thng nhit 8009000C v cp nhiu nhit choqu trnh ct lin kt C-C v C-H.


6/64

b/C ch v ng hc ca phn ng:-C ch chui gc, phc tp:

*Vi etan-To gc t do: C2H6CH3* + CH3*

CH3* + C2H6CH4+ C2H5*-Pht trin chui:To E=: C2H5* C2H4+ H*To H2 v ti sinh gc C2H5*:

H* + C2H6H2 + C2H5*-t chui: H* + H* H2

H* + C2H5* C2H6C2H5* + CH3* C3H8C2H5* + C2H5* C4H10

Do vy, ngoi C2 trong hn hp sn phm cn c C1, C3, C4....Vinguyn liu u l H/C no mch di hn, nh naphta chng hn, th sn

phm cng phc tp. V d vi C8H18-To gc t do: n-C8H18C6H13* + C2H5* (1)

E1= 335 Kj/mol-Ct ca gc to E=v mt gc khc:

C6H13* C4H9* + C2H4 (2)E2= E1/3

-Phn ng gia mt phn t vi gc:C2H5* + C8H18C2H6+ C8H17* (3)

E3= E1/9-Phn ng gia haigc t do:

C2H5* + C4H9* C2H4 + C4H10 (4)E4= E1/50

Ch : Gc t do khng c kh nng ng phn ho (chuyn H* vnhm CH3*) v khi ct mch C- C v tr to sn phm ch yu l E=, donguyn liu naphta c thnh phn n-parafin ln th hiu sut E= cng cao. l c trng ca qu trnh cracking hivi c ch chui gc.

R-CH2- CH2-CH2* C2H4 + R-CH2*

So snh vi qu trnh cracking xc tc vi s to thnh phn t hot ng lcacbocation vi kh nng ng phn ho caotrc khict nn ch yu toO. c mch cacbon t 3 tr ln (t E=) v nhiu hp cht izo.

R-CH2-CH2-CH2+R-CH2-CH+-CH3 CH3-CH=CH2 + R+Gc t do cng xc tin phn ngphtrng hp O. to thnh, dn

n to nhav cc lm gim hiu sutsnphm. hn ch phn ng nitip ny cn thi gian phn ng ngn v s dng hi nc.


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c/K thut cracking hi:Trn c s c trng v nhit ng hc v ng hc ca phn ng c

th rt ra yu cu v TBP nh sau:-Nhit cao800 9000C.

-Cp nhiu nhit cho qu trnh.-Gim p sut ring phn ca O bng cch cho thm hi nc.-TGL ngn khong trn di 1 giy ph thuc vo nhit phn ng:

c thc hin bng cch a nhanh n nhit phn ng v sau lmlnh nhanh sn phm (gi l "ti" sn phm) dp tt phn ng chui gc.

C nhng gii php khc nhau nh dng cht mang nhit l cht rnchu nhit dng lp tnh hay chuyn ng (hnh 2.2) hay kh chy nhit cao (hnh 2.3), tuy vy hin nay vn s dng l ng cng sut ln v hini (hnh 2.4 ).


8/64

Naphta

Na

phta

H.2.1.3-TBP cracking hi ACR (Advanced Cracking Reactor)


9/64

S cng ngh cng on nhit phn:Hnh 2.5 trnh by s cng nghca cng oncracking hi.

H.2.1.5-S cng ngh cng on cracking hi-Tn dng nhit ca l ng:

*Khi l c dng un nng nc mm v nguyn liu (naphta v hinc ) trong zn i lu ca l.*Sn phm ra nhit cao cn lm lnh nhanh xung 400 4500C dptt cc phn ng ph theo c ch chui gcv to hi nc p sut cao.nhit cn li trong sn phm dng un nng y thp tch 2 v hmnng naphta cng nh nc mm.

-Sn phm ca cng on ny l du t(F.O.), xng nhit phn vi

hm lnglnH/C thm vO v kh cha O t C2 n C4, trong chyu l etylen. Hn hp kh ny c a quacng on tchtip theo.d/Nguyn liu sn xut O:-Ton th gii dng 50% naphta, 2530% kh etan v propan, 20% gasoil,ring Nht v Ty u - 80% naphta, M - 50% etan.-Hiu sut E=ph thuc vo nguyn liu nh bng 2.1


10/64

Bng 2.1-Hiu sutcc O ph thuc vo nguyn liu, % KL nguyn liuSn phm Etan Propan n-Butan Naphta

nngG.O.

nhG.O.nng

Kh t (H2+CH4) 16,1 30,0 21,4 18,1 11,9 11,8

Etylen 76,2 42,0 36,2 31,2 26,4 24,3Propylen 2,9 16,2 20,4 14,8 14,2 13,8Butadien 1,4 3,2 3,0 3,8 3,9 3,7Cc C4= 0,6 1,4 12,6 4,2 4,7 4,3

Xng nhit phn 2,8 6,0 4,1 24,2 19,5 17,7Du FO -- 1,2 2,3 3,7 19,4 24,4

T bng 2.1:-Etan cho hiu sut E= cao nht, n 76% khi lng nguyn liu.-Cc nguyn liu nng hiu sut E=gim, cc O. C3 v C4 tng , k c

butadien.-Do c ch chui gc ca phn ng, hiu sut E=ph thuc vo thnh

phn ca naphta: n-parafin tng th hiu sut E=tng.-Trong kh sn phm c mt lng nh a xetylen,cn phi x l trc

khi tch ( hidro ho chn lc thnh E=).e/Tch kh cha O ca cracking hi:-Kh sn phm ca cracking hi l nhng cu t c nhit si thp, thngdng cng ngh nn n 4 MPa v lm lnh n -1000C bng cch bay hiEtylen lng( Ts = -103,70C ) c sn trong dy chuyn cng ngh. S

khi ca cng on tch kh cracking hi c trnh by hnh 2.6

H.2.1.6-S khi ca cng on tch kh cracking hi

Qu trnh c tin hnh theo s cng ngh 2.7


11/64

H.2.1.7-S cng ngh tch kh cracking hig/Tch phn on C4:-Thnh phn ca phn on C4 ca kh cracking hi bng 2.2Bng 2.2

Hp cht % khi lng Tsi, 0Ci-Butan < 5 - 11,4

n-Butan < 5 -0,5

i-Buten 20 35 -6,9Buten-1 10 15 -6,3Buten-2 Trans 4 6 0,9Buten-2 Cis 3 5 3,7Butadien-1,3 35 50 -4,4

-Cc hp cht c nhit si gn nhau, c bit butadien cthnh phn caov d b polime ho, sau khi tch butadien ta c hn hp C4 giu i-butenc gi l raffinate-1.

-Tch Butadien:a/Trch li bng dung dch amiac ng 1: [Cu(NH3)2]1+X-.

Butadien tophcnn ho tan vo dung dch ny. Cc buten c ho tanthp hn t 10 n 50 ln.iukin trch li: T = -140C; P = 0,30,4 MPa; T l: Dung dch/C4 = 8.Tin hnh trng thi lng.iu kin nh: T = 800C; P = 0,1 MPa.


12/64

b/Chng trch li:-L qu trnh chng c thm mt cu t th 3l hp cht c cc v nhit si cao, butadien vi hai ni i tng tc mnh vi cu t th 3 v b koxung y thp chng.- bay hi tng i ca cc hp cht trong hn hp C4 khi c cu t th3 c trnh by bng 2.3Bng 2.3Hp cht Khng

c cu tth 3

NMPN-metylpyrroli-doneTs,0C =204209

DMFDimetylformamitTs,0C =

153

ACNAceto-nitrilTs,0C =80 82

DMACDimetylaxetamitTs,0C =165169

Furfural

Ts,0C =162

Butan 1,17 3,66 3,43 3,13 3,13 2,89

1-B= 1,08 2,38 2,17 1,92 2,07 1,78Trs-2-B= 1,23 1,9 1,76 1,59 1,71 1,20Cis-2-B= 1,37 1,63 1,56 1,45 1,52 1,26Butadien 1,00 1,00 1,00 1,00 1,00 1,00

BASF1968

Zeon1965- 68

Shell1956

UC1956

Philipps1940

Hnh 2.8 trnh by s cng ngh chng trch lica Shell dng dung mi laxetonitril.

H.2.1.8-S chng trch li vi axetonitril ca ShellThnh phn ca phn on C4 sau khi tchbutadien (Raffinate-1) v tch i-

buten (Raffinate-2) nh bng 2.4


13/64

Hp cht Raffinate-1,% KL Raffinate-2,% KLi-Butan 3 6n-Butan 11 191-Buten 25 45

2-Buten 16 30i-Buten 45 < 0,1Butadien < 0,5 -

-Raffinate-1 c hm lng i-buten ln l nguyn liu tt cho sn xut MTBEdo kh nng phn ng cao ch c i-buten tham gia phn ng to ete vimetanol.

CH3OH + CH2=C(CH3)2CH3-O-C(CH3)2y cng l phng php tch i-buten sch t hn hp khi kt hp vi cng

ngh phn hu MTBE thnh metanol v i-buten.-Mt cng ngh khc tch i-buten t hn hp l phn ng thun nghch vinc to TBA:

(CH3)2C=CH2 + H2O (CH3)3C-OHVi dung dch H2SO4 4550% 300C i-buten tham gia phn ng nhanhhn n-buten 1500 ln.

II.1.1.B-Cracking xc tc:-Hiu sut cc phn on sn phm ca qu trnh cracking xc tc c th ara nh bng 2.5

Bng 2.5Sn phm % KL nguyn liu vo

Phn on C2 4,4Phn on C3 2,7Phn on C4 4,9Phn on C5 5,0Phn on xng 27,5Phn on gasoil 43,0Phn on du nng 8,5

Cc (t khi ti sinh xc tc) 4,0-Thnh phn cc phn on kh cha O:


14/64

Bng 2.6Phn on C2 Phn on C3 Phn on C4 Phn on C5H/C %KL

H2 1,3

CH4 29,5Etan 25,4Etylen 20,9Propan 3,5P= 11,8Tr 7,6

H/C %KLC2- 0,4

P 26,9P= 72,0C4+ 0,7

H/C %KLC3- 0,5

n-B 11,0i-B 33,0n-B= 37,0i-B= 18,0C5+ 0,5

H/C %KLC4- 2,0

i-Pentan 31,5n-Pentan 5,5i-Penten 37,5n-Penten 22,5

C6+ 1,0

II.1.1.C-Hin nay sn xut O p dng cng ngh cracking su (DCC ), DCC ch 1c hiu sut propylen cao, DCC ch 2 c hiu suti-olefin cao nh bng 2.7Bng 2.7

Hp cht DCC ch 1 DCC ch 2 FCC thng dngEtylen 6,1 2,3 0,9Propylen 20,5 14,3 6,8Butylen

trong i-C4=14,35,4

16,46,1

11,03,3

Amylentrong i-C5=

------

9,86,5

8,54,3

-Gn y c cng ngh sn xut O t kh t nhin qua metanol th dngcng nghUOP/Hydro MTO (Methanol to Olefin) theo s hnh 2.9


15/64


16/64

-Xc tc: Pt/Al2O3, MoO3/Al2O3hay SiO2, lm vic trong mi trngH2( P = 0,30,5 MPa, t l H2/HC = 1/2 ), xc tc mau mt hot tnh do cc

ph b mtnn cn ti sinh bng cch t cc.-Cc cng ngh:

in hnh l cng ngh PACOL ca UOPvi cng ngh xc tcchuyn nglp ri, ngoi ra c mt s cng ngh sn xutolefin thp nhCATOFIN caHoudry (xc tc c nh, ti sinh theo chu k), OLEFLEXca UOP ( xc tc chuyn ng ),STAR caPhilipps (dng hi nc thayhidro).

II.1.2.c/Phng phpoligome ho etylen:Ttylen thu clfin mch thng,tylen l ngun nguyn liu

ban u r v di do nhcng ngh cracking hi c thc hin qui mln. T P=,B= ch c olefin mch nhnh, kh phn hu sinh hc nn chtgit ra t chng gy nhim mi trng.

A-Cng nghvi xc tc etyl nhm:* Phn ng c hai giai onoligome ho v tch mch.

Giai on1: Oligome ha T = 1000C, P = 10 MPa.-CH2-CH2-R1

Al(C2H5)3 + 3nC2H4 Al {-CH2-CH2-R2-CH2-CH2-R3

R1, R2, R3 c s nguyn t C chn v khng bng nhau.Giai on 2: Tch mch T = 3000C, P = 1MPa.

-CH2-CH2-R1 R1-CH=CH2

Al -CH2-CH2-R2 + 3C2H4 Al(C2H5)3 + R2-CH=CH2-CH2-CH2-R3 R3-CH=CH2*Cc cng ngh:

+Cng ngh Gulf Oil:-C hai giai on tin hnh ng thi trong mt TBP iu kin

T = 2000C, P = 25 MPa.-Sn phm c mch phn bb t C4 n C30,trong c 91 n 97%

-ole fin mch thng.-S dng: Cng ty Gulf Oil v Mitsubishi Chemical Industry.

+Cng ngh Ethyl:

-C ba TBPoligome ho, chuyn alkylv t lng ho nhm kimsot chiu di mch.

-S cng ngh nh hnh 2.10


17/64


18/64

H.2.1.11-S khi cng ngh SHOPXc tc ho tan trong dung mi c ccetylen glycol hay 1,4 butandiol.

-iu kin phn ng: T= 80 - 1200C; P= 7 - 14 MPa.2-Lng tch: lfin to thnh khng tan trong dung mi c cc, lng

tch sn phm v dung dch xc tc quay li h phn ng ligme ho 1.3-Chng tch thnh 3 phn on: C4-C10- S dng hoc a xung

ng phn ho 4; C12-C18- S dng; >C18- a xung ng phn ho.4-ng phn ho: + T=80 - 1400C; P= 0,3 - 2MPa.

+ Pha lng, xc tc MgO.

+ Nguyn liu l -O C4-C10, >C14, >C20, 90%lfin chuyn ni i vo trong.

R-CH=CH2R1-CH=CH-R25-Chuyn v: + Xc tc d th Re, Mo.

+ iu kin phn ng nh ng phn ho.+ Phn ng:

R1-CH=CH-R2+ R3-CH=CH-R4R1-CH=CH-R3+ R2-CH=CH-R4

Phn ng chuyn v c th thc hin gia O mch di vi etylen:

C10H21-CH=CH-C10H21+ CH2=CH22 C10H21-CH=CH2 y cng thc hin phn ng ng phn ho t O c ni i bn

trong thnh -olefin.Nh my u tin theo cng ngh SHOP nm 1977Lousiana vi

cng sut 200.000 tn /nm.Sn xut-olefin cc khu vc:


19/64

Cng ngh Ty u M NhtOligome ho etylen, % 40 93 100Cracking parafin C22-C30 60 7 ---

II.2-SN XUT HC THM.*Mt s tnh cht ca HC thng gpBng 2.2.1

Hp cht Tsi,0C Tnng chy,0C Tbc chy,0CBenzen 80,1 +5,5 -14Toluen 110,6 -9,5 +5o-Xylen 144 -25,2 +29m-Xylen 139,1 -47,9 +29

p-Xylen 138,3 +13,3 +29Etyl benzen 136,2 -95 +15Cumen 152 -96 +43

Naphtalen 218 +80,3 ---

II.2.1-Ngun nguyn liu ban u:a-Du cc:Du cc nh: 10-15l/tn than, c 63% B, 13% T, 8% X.Du cc nng: 30-38l/tn than, cha naphtalen, antraxen. hnh dung vai tr ngun nguyn liu ny cho HC thm:HC thm

t than M: 1957 - 77%, 1970 - 10%, 1981 - 7%.

b-Xng cracking hi:Hiu sut xng20% t naphta. BTX chim trn 60%.Xng cracking hi, du cc u c cha HC khng no nn cn x l

H2 trc khi tch.c-Phn on C6-C9 ca sn phm reforming xc tc:Cha n 70% HC thm, ngoi ra cn HC pa ra fin, naphten c nhit

si xp x. p ng nhu cu HC thm cho THHD ngy nay cn thc hin qu

trnh thm ho phn on C6-C9 ca naphta theo cng ngh tng t refor-ming xc tc.II.2.2-Phng php tch HC thm:

a-Phng php kt tinh:-Dng cho benzen khi tch t nguyn liu c hm lng B cao nh

du cc nh, phn on C6 ca xng cracking hi. -Ph bin hn khi tch p-X t hn hpC8 ( hin nay b cnh tranh bi

phng php hp ph chn lc hin i v hiu qu hn ).


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b-Phng php hpph chn lc:-Hp ph chn lc HC thm ln b mt cht rn t hn hp, sau

tin hnh nh bng nhit trong dng cht cht nh hp ph. Cui cng chngtch cht nh hp ph khi sn phm HC thm v phn on HC x l.

-c trng l cng nghPAREX ca UOP: tch p-X t hn hp ccng phn theo cng nghSORBEX- hp ph v nh lin tc trn lp chthp ph tnh nh thay i dng chy bng van quay.

-Cng nghPAREX c th hnh dung qua s hnh 2.2.1

H.2.2.1-S tch p-Xylen theo cng ngh PAREX-Cng ngh PAREX ca UOPthng tch hp vi ng phn ho hn

hp xylenIZOMAR nh hnh II.2.2.2

H.2.2.2-Tch hp cng ngh tch p-Xylen vi ng phn ho

c-Chng trch li:-Thm dung mi c kh nng tng tc vi HC thm v ko hp cht

ny xung y thp, cn cc hp cht khng thm ln nh thpchng, sau


21/64

tin hnh tch HC thm v dung mi. Nh vy, dung mi thng cchn c nhit si cao, tng tcmnh vi electron ca hp cht thm.

-C nhiu cng ngh chng trch li:*Distapex ca hng Lurgi dng N-metylpyrrolidone (Ts=2020C).

*Morphylane ca Koppers dng N-formylmorpholine (Ts=2440C).*Tetra ca UnionCarbide dng tetraetylenglycol (Ts= 3280C).*Stex caToray dng dimetylacetamide (Ts=1610C).Cng nghDistapex c trnh by hnh II.2.2.3

H.2.2.3-Cng ngh Distapex chng trch li tch benzen tphn on C6 ca cracking hi

d-Trch li lng- lng:-L phng php cong ngh kinh t v ph bin nht, thng kt hpvi chng trch li.

-Dung mi s dng l cc hp cht c cc, ho tan tt HC thmnhng khng tan ln vi cc HC parafinic v naphtenic.Ngoi ra dung micn c khi lng ring nng hn nguyn liu c trch li v c nhit


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23/64

o-Xylen m-Xylen p-Xylen-Hidrodealkyl ho alkylbenzen thnh benzen.

C6H5-CH3 + H2 C6H6 + CH4-Phn b li gc alkyl

2C6H5-CH3 C6H6 + C6H4(CH3)2

II.3-SN XUT H2v CO:Sn xut H2:-Nhu cu H2 ngy cng tng sn xut phn m v nhiu qu trnh

cng ngh ho du khc:V d:*Khlu hunh: cho Xng - 12 m3/m3; Gasoil - 50 m3/m3; Phnon nng - 100 m3/m3

*Hi dro cracking - 240 700 m3/m3.*Sn xut metanol - 1600 m3/tn.

*Sn xut NH3 - 2000 m3/tn.*Sn xut benzen9Hi dro dealkyl ho toluen) - 350 m3/tn.-Cc ngun H2:

+Kh Reforming xc tc, kh cc, kh cracking hi. Cc kh ny thng lnvi HC khc, c bit l metan v etan. Thng yu cu thun H2 t 80 -95% nn kh reforming xc tc l thch hp, vi cc kh khc cn phi xl.+Chuyn ho cc HC, cc vt liu cha C khc (than , g, sinh khi...)

bng cch phn hu nhit, oxi ho mt phn, chuyn ho vi hi nc. +Phn hu nc.

-Cc qu trnh tinh ch H2:a/Hp ph tp cht bng silicagel, than hot tnh, Al2O3 hot tnh,zeolit. Hiu qu ca vic tinh ch ph thuc vo tp cht ca hn hp.

b/Phng php thm thu: qua mng hu c hay mng kim loi.c/Lm lnh thm ho lng.

II.3.1-Cng ngh sn xut H2t cc vt liu hu c:Cc cng ngh v cng on x l nh s khi hnh 2.3.1A-Oxi ho mt phn:

+Phn ng: a/Phn ng chy:-Vi metan:

CH4+ 3/2O2CO + 2H2O H298= -519,5 Kj/mol-Vi HC nng:

CnHm+ (2n+m)/4 . O2nCO + m/2 . H2Ob/Chuyn ho CO:CO + H2O CO2+ H2 H298= -41 Kj/mol

*L phn ng thun nghch to nhit, do T thp, H2 cng nhiu.


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*H2O to thnh t phn nga/ hay a thm vo.c/Phn hu do nhit cao:CH4C + 2H2 H298= 74,8 Kj/molCnHmnC + m/2 . H2

y l phn ng ph to mui, khi c mt H2O, CO2(sn phm caphn ng a/ v b/ ) mt phn mui s phn ng:C + CO22COC + H2O CO + H2

+Cng ngh:*Thng tin hnh on nhit, nhit vo 500-6000C.*T s O2/HC rt quan trng:

Khi O2/CH4< 0,5 - to nhiu mui.O2/CH4tng: tng nhit phn ng (c th t 1000

0Chay cao hn), tng lng hi nc, gim hm lng CH4.

*S cng nghTexaco hnh 2.3.2


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H.2.3.1-S sn xut H2t nguyn liu cha ccbon

TBPoxihomtphn

ThptchFuelOil

Thprakh

Thptchhinc

H.2.3.2-Cng ngh Texaco: sn xut H2bng oxi ho mt phn


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27/64

Nc mm

Nhin liu

Kh thi

Nc ngng

Kh cha H2

Hi ncqu nhit,

PcaoKh tnhin

H2

Hi nc

H.2.3.3-S cng on chuyn ho bng hi nc.

C-Cng ngh t nhit:Mt s cng ngh t nhit do kt hp hai qu trnh oxi ho mt phn

to nhit vireforming hi nc thu nhit. in hnh l cng nghpht trin

trong nhng nm 50do hp tc gia SBA (Socit Belge de l'azote) vHaldor Topsoe, trn nguyn tc trn kh chy vi hi nc v cho vo lpxc tc c nh trn c s Ni 2 MPa v 9500C. Cng ngh ny ch dngcho cc nguyn liu nh nh kht nhin, LPG v naphta lin quan n ccdn sut lu hunh v to cc ca cc nguyn liu nng.

D-Chuyn ho CO:-Kh thu c t cc cng ngh trn cn cha nhiu CO (bng 2.3.2)

Bng 2.3.2-Oxi ho mt phn Reforming hi

Cu t

H2COCO2CH4

N2Kh khc

Kh TN Naphta FO THAN

61 51 47 4035 45 47 352-3 2-3 4 21- - 1 20-1 0-1 - 22-0 2-0 1 -

Kh TN

55-5712-15

7-12-

22-24*4-2


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*Dng khng kh chuyn ho nt CH4Phnng: CO + H2O CO2+ H2 H298= 41,2 Kj/molL phn ng thun nghch, to nhit: cn tin hnh nhit thp, d

hi nc.

250

0

C, t l H2O/CO = 3 chuyn ho hon ton CO. Tuy vy nhit thp to nhiu metan v cacbon nn trong cng nghip thc hin haigiai on chuyn ho:-Giai on 1: Nhit cao trnh to mui.

Xc tc: 80 -95% oxit st v 5-10% oxit crm.Nhit : 350 4500C.Gii nhit phn ngbng cch phun nc trc tip vo gia cclp

xc tc on nhit.-Giai on 2: Nhit thp chuyn ho hon ton CO ( 0,05 0,1V ).

Xc tc: Oxit ng( 15-30%), oxit km ( 30%) trn Al2O3

Nhit : 200 2500CE-Tinh ch H2:Yu cu thun H2trn 97%, CO < 1%.Kh CO2bng hp thvi dung dch kim, alkanolamin.KhCO: -Hp th bng dung dch ng 1.

-Mtan ho: CO + H2CH4+ H2OXc tc: Ni/Al2O3c kch ng vi Cr2O3

Nhit : 3000C.Nng CO < 20 ppm.

Sn xut CO:-CO c s dng ring l hay dng hn hp vi H2(kh tng hp).-CO c trong cc kh thi cng nghip: kh l cao, kh cc, kh ca

qu trnh sn xut mui than, kh ca sn xut nhm, kh ca sn xut tn): thu hi v tch.

-Ging H2, CO c sn xut t vt liu cha cacbon bng reforminghi v oxi ho mt phn.

-Cc phng php tch:Hp th v nh vi dung dch ng 1.

Lm lnh ho lng nhit thp (Ts = -1910C) vi hai cng ngh:ngng t mt phn v ti bng CH4lng.

II.4-SN XUT CC HC NO:-Chia thnh P. thp: C1 C5 v cao: >C5.-P. c trong cc phn on ca du m: tch v chuyn ho gia

chng theo yu cu.


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30/64

-Dng dung mi gim nht cho cc phn on nng. Dung mithng l hn hp xton va HC thm, propan lng c s dng lm dungmi ng thi l cht lm lnh (T si = -42,10C).

H.2.4.2-S tchn-parafin bng phng php kt tinh2/Phng php cacbamit:-Da vo tnh cht n-p to phc rn viur nhit thp v phn

hu tr lin-p v ur nhit 80 - 1000C.-Phn ng:

RH + nCO(NH2)2RH.nCO(NH2)2.-Phc rn c thnh phn 8 phn t r cho mt nguyn t C.-Vi phn on HC nng thm dung mi (nh CH2Cl2) gim

nht.

-S tch n-p dng ur hnh 2.4.3

H.2.4.3-S tch n-parafin dng cht to phc ur3/Phng php hp ph chn lc:-Parafin mch thng c ng knh ng hc nh hni-p v cc HC

khc nn c th chui vo l xp v hp ph chn lc trn zeolit CaA(zeolit5A).Cc n-p vi chiu di mch khc nhau u c kch thc ng hc theochiu ngang nh nhau v c th tin hnh tch n-p bng hp ph chn lc


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i vi cc hn hp HC pha kh cng nh pha lng. Kch thc l xp camt s zeolitv ng knh ng hc ca mt s cht c trnh by hnh2.4.4

H.2.4.4-Quan h gia kch thc hiu dng cal xp mt s loizeolit v ng knh ng hc phn t ca mt s hp cht.

-C th tin hnh qu trnh tch vi cng ngh gin on theo tngchu k hp ph v nh. Hin nay c cng ngh lin tcvi cc lp zeolit 5Ac nh ca UOP vi thng hiu MOLEX, tng t cng ngh PAREXnh hnh 2.2.1.

III-CC QU TRNH OXI HO.-L cc qu trnh quan trng ca THHD: Sn xut nhiu sn phm c

gi tr nh cc ru, cc aldehit, cc xeton, cc axit hu c, cc oxit, ccmonome ....Tc nhn oxi ho l khng kh v oxi kthutr v sn.

-Phn ngoxi ho c hiu ng nhit cao, c bit i vi cc qutrnh pha kh cn ch cc bin php gii nhit.

-Mt phn ng ph cn lu lphn ngoxi ho hon tonthnh

CO2v nc: lun lun xy ra song song v ni tip vi cc sn phmchnhcaqu trnh oxi ho khng hon ton, lm gim ng k hiu sut ca mtcng ngh sn xut.Ngoi ra, hiu ng nhit ca phn ng ph ny rt ln,gy thm kh khn cho vic duy tr nhit thch hp cho phn ng.

-Cc loi phn ng: Oxi ho theo c ch ng li,chui gc trong phakh v pha lng, oxi ho d th trn xc tc rn, oxi ho vi xc tc phc.


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III.1-Oxi ho theo c ch chui gcbng o xi phn t:-Ph bin, lin quan n qu trnh t o xi ho cc hp cht hu c, cc

sn phm du, cc hp cht polime... trong mi trng c o xi ca bu khquyn.III.1.1-C ch phn ng:Chui gc phn nhnh, t phn t O2(0=0) sthun li hn v mt nng lng khi t ng li ch mt lin kt thnh gctdo *O-O*.

-Giai on khi mo: To gc t do, thng vi s tham gia ca O2.RH + O2R* + *O-O-H ( 1 )RH + O2 + HR R* + H-O-O-H + R* ( 2 )R-R' + hR + R' ( 3 )

-Pht trin chui: To hp cht hidropeoxit(H/P) v hon nguyn gc.R* + O2R-O-O* ( 4 )R-O-O* + RH R-O-O-H + R* ( 5 )

Phn ng 4 v 5 c quay vng vi s tham gia ca RH v O2, dn n tch thp cht trung gian khng bn l cc H/P.

-Phn nhnh: Phn hu ccH/P thnh cc gc t do mi v do tngnhanh vn tc oxi ho.

R-O-O-H R-O* + *O-H ( 6 )R-O-O-H + H-O-O-R R-O-O* + H2O + R-O* ( 7 )R-O-O-H + H-O-R' R-O* + H2O + R'-O* ( 8 )

Phn ng 6 trong pha kh, phn ng 7 v 8 trong pha lng do c linkt hidro.

-t chui: Dokt hp cc gcR* + R* R-R ( 9 )R-O* + R* R-O-R ( 10 )R-O-O* + R-O- O* R-O-O-R + O2 ( 11 )R-O-O* + R* R-O-O-R ( 12 )

*H/P l sn phm phn t u tin ca qu trnh oxi ho. Ph thucvo nguyn liu ban u ta c H/P bc 1,2,3.

V d:Vi nguyn liu etylbenzen c H/P bc 2, vi cumen cH/P bc 3

*H/P l hp cht khng bn, phn hu thnh gc theo 6,7,8. bntheo th t sau:H/P bc 3 > H/P bc 2 > H/P bc 1.

H/P bc 3 bn, c bit khi nhm O-O-H nh vo nguyn t Ccnh nhn thm hay ni i, c th c lp c nh (CH3)3C-O-O-H,C6H5-C(CH3)2-O-O-H.


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*S tch t H/P trong hn hp phn ng n mt nng no btu tng nhanh vn tcoxi ho theo hm m nh hnh 3.1.1. T khi bt un thi im gi l giai on cm ng ca qu trnh oxi ho.

H.3.1-c trng ng hc phn ng oxi ho theo c ch chui gc III.1.2-Phn hu H/P to ru v hp cht ccbonyl:

-To ru:t lin kt yu O-O nh cc phn ng 6,7,8 to gc RO*.Do tn cng ca gc alkyl R*

R-O-O-H + R* R-O* + R-O-HR-O* + RH R-O-H + R*

-To hp cht ccbonyl: t lin kt C-H ti nguyn t C c nhmO-O-H do tn cng ca gc *O-H, sau t lin kt O-O.-To aldehit: T H/P bc 1

R-CH2-O-O-H + *O-H H2O + R-C*H-O-O-HR-C*H-O-O-H R-CHO + *O-H

-To xton: T H/P bc 2R2CH-O-O-H + *O-H H2O + R2C*-O-O-HR2C*-O-O-H R2CO + *O-H

nhit cao, pha kh, phn ng phc tp hn, c th t lin kt

C-C.III.1.3-Oxi ho ru, aldehit v xton to thnh:-Oxi ho ru bc 2: t lin kt C-H nguyn t C c nhm O-H

to gc oxi-alkyl, sau o phn ng vi O2to gc oxi-peoxit v to thnhoxi-H/P, hp cht ny phn hu thnh xton v H2O2.

R2CH-O-H + R2C(OH)-O-O* R2C*-O-H + R2C(OH)-O-O-HR2C*-O-H + O2R2C(OH)-O-O*


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R2C(OH)-O-O-H R2C=O + H-O-O-HTrn c s ny hin nay H2O2 c sn xut ch yu bng qu trnh oxi hoqua tc chthu c nhru izopropylic v anthraquinol.

Vi izopropylic ta c phn ng;

CH3-CH(OH)-CH3+ O2(CH3)2C=O + H2O2(CH3)2C=O + H2CH3-CH(OH)-CH3-Oxi ho aldehit: t lin kt C-H ti nhm -CHO to gc axyl, sau

phn ng vi O2thnh gc axyl-peoxit v chuyn ho thnh peaxit.R-CH=O + R-CO-O-O* R-CO-O-O-H + R -C*=OR-C*=O + O2R-CO-O-O*

Peaxit t phn hu c tham gia ca lin kt hidro thnh gc axyloxi vaxylpeoxit v thnh axit.

R-CO-O-O-H + R-CO-O-O-H R-CO-O* + H2O + R-CO-O-O*R-CO-O* + R-CHO R-CO-O-H + R-C*=O

Hoc tng tc vi aldehit ban uR-CO-O-O-H + R-CHO R-CO-O-O-CH(OH)-R 2R-CO-O-HCc gc axyl v axyloxi c th phn hu ra CO v CO2, nht l khi

nhit caoR-C*=O R* + COR-CO-O* R* + CO2

-Oxi ho xton:-Xton bn hn ru v aldehit.-t lin kt C-H ti v tr so vi nhm C=O thnh gc -

xetoalkyl,sau phn ng vi O2thnh -xetopeoxit v tip theo thnh-xetohidropeoxit

R-CH2-CO-R' + R-CH(-O-O*)-CO-R' R-C*H-CO-R'+ R-CH(-O-O-H)-CO-R'

R-C*H-CO-R' + O2R-CH(-O-O*)-CO-R'Tip theo -xetoH/P chuyn thnh axit t mch C-C theo c ch ion

v c ch gcC ch ion:R-CH(-O-O-H)-CO-R' + H+ R-CH(-O-O+H2)-CO-R'

R-CH(-O-O+H2)-CO-R' R-CH(-O+

)-CO-R' + H2OR-CH(-O+)-CO-R' R-CHO + R'-C+=OR'-C+=O + H2O R'-CO-O-H + H

+R-CHO +1/2O2R-CO-O-HC ch gc:

R-CH(-O-O-H)-CO-R' + R'-C*=O R-CH(-O*)-CO-R' + R'-CO-O-HR-CH(-O*)-CO-R' R-CHO + R'-C*=O


35/64

Sau , aldehit phn ng vi oxi thnh axit R-CO-O-H theo c ch bit, cn axyl quay v phn ng vi -xetoH/P theo phnng trc vto thnh axit R'-CO-O-H.

Song song vi phn ng chnh trn, t xton c th thnh ruxton, dixeton do oxi ho nhm CH

2 v tr khc , sau d chng tip tc b

oxi ho thnh oxi axit, xto axit, axit hai chc...T ru xton to oxi axit:R-CH(OH)-(CH2)n-CO-R' + 1,5O2R-CH(OH)-(CH2)n-1-CO-O-H

+ R'-CO-O-HT dixeton to xto axit:R-CO-(CH2)n-CO-R' + 1,5O2R-CO-(CH2)n-1-CO-O-H

+ R'-CO-O-HT xeto axit to axit hai chc:R-CO-(CH2)n-1-CO-O-H + 1,5O2R-CO-O-H

+ H-O-CO-(CH2)n-2-CO-O-HIII.2-Sn xut phnol.-Cng thc: C6H5OH ; d4

20= 1,072 ; Tn/c= 410C ; Ts= 182

0C.-Phngdngcaphnol rtrng, l nguyn liuquan trngsn

xutnhaphnol, nhaepoxi (qua bisphnol A), nhapolyamit (quacaprolactam) lm chtktdnh, sn, chtdo, sitnghpv nhiuqutrnh tnghphucnglu khc nhsnxutchtmu, nng dc,dcphm,chtho do, chthotngbmt... Nhngngdngchyu3 vng al ctrnh by bng

Cc sdngchnh, % KL Ty u M NhtNhaphnol fomalhitNhapolyamit (caprolactam)Nhaepoxi (Biphnol A)

341721

351624

475

26

-Cc cng nghsnxutphnol ctrnh by bng

Cc cng nghsnxut, %KL Ty u M NhtTbenzen qua benzen sulfoaxitTcumen qua cumen hidropeoxitTtoluen qua axit benzoicCc cng nghkhc (ccho than ,tbenzen qua clobenzen ...)

82171

9721

2971


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Nhvy, cng nghchyusnxutphnol hinnay l oxi hocumen.a/Cng nghoxi ho cumen:-ctrng caphnng:C hai giai onphnng: oxi ho cumen thnh hidrpeoxit (HP) v

chuynho HP thnh phnol c mtxc tc axit ctinhnh ringbittheo cc phnngnhsau:

C6H5CH(CH3)2+ O2C6H5C-O-OH(CH3)2H298= 112 kj/mol.

C6H5 C-O-OH(CH3)2H+

C6H5OH + CH3-CO-CH3 H298= 253 kj/mol.

+Phnngchnh v phcagiai onoxi ho:

C6H5CH(CH3)2 C6H5C(CH3)2OO*

C6H5C(CH3)2OOH C6H5C*(CH3)2O2

C6H5COCH3+ CH3O*

+R*

C6H5C(CH3)2OH +C6H5C(CH3)2O*+RH

C6H5C(CH3)2OH + R*

CH3OH

HCOOH

Atophenon

Dimetyl phenyl cacbinol

Phnngchnh v phcaqu trnh oxi ho tinhnh theo cch

chuigc, pha lng, khng dng xc tc. Yu cunguyn liuban u, nhtl cumen tunhon, khng chacc hpchtc khnng btgcnh

phnol, styren, cc hpchtc lu hunhv nit... lm chmqu trnh oxiho. Phnngphl chuynho tipcumen HP hay gccumen peoxitthnh dimtyl phnyl ccbinol, axtophnon v mtshpchtkhc. hnchphnngphmtmtduy tr chuynho thp(X = 20 25 %)gimnngHP v gcHP trong hnhpphnngv gimdnnhit

phnngtheo mctch tHP trong snphm(nghal gimnhitphnngtheo tng caX), mt khc TBPcnc TGL capha lngngutrnh chuynho tipHP tothnh theo cchchuigctrongmi trngcaqu trnh oxi ho.

Qu trnh oxi ho cumen l dthkh-lngxyra trong phmvinghc100 - 1300C ( TGL capha lngkhongt2 - 3 h t


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chuynho X cacumen nhtrn ) nn ctinhnh trong TBPloisibtl loithitbc m hnh dng chygnviKLT (btkh i ln kotheo chtlngv toskhuytrnmnhtrong thitb). phn bTGLcapha lng ngucndng 3 - 5 thp sibtnitipnhhnh 3.2. Sdnghthitbnitipcn gip cho vicchnhittrong tngthitbkhc nhau, gimdnkhi X tng nhtrn.

Phnngtonhit, giinhitbngcch bm tunhon hnhpphnngqua thitbtrao inhithay dng vbcngoi.

+Phnngchnh v phcaqu trnh chuynho HP thnh phnol vaxton:

H.3.2-S cng ngh sn xut phnol t cumen.1-TBPoxi ho cumen thnh hidropeoxit. 2-Thp chng chn khngtch cumen. 3-Thng phnngc khuyphn huHP cumen thnh

phnol v axton. 4-Thitbphn huhon ton HP cumen. 5-TchH2SO4dnh anionit. 6-Thp tch axton. 7-Thp tch cumen v -

mtyl styren. 8-Thp tch phnol. 9-Thitbthu hiphnol tcn.10-Thng hpphcumen tkh thi.

III.3-Sn xut axit axtic: Tsi = 117,90

C; Tnng chy = 16,660

C-Tuy c nhit si cao hn nc gn 200C nhng rt kh chng tchnc t dung dch long v thnh phn pha hi trong cn bnghi-lng tkhc vi pha lng. Do vy, nng nng axit axetic t dung dch longthng dng phng php trch li vi dung mi etyl axetat, butyl axetat, izo-

propyl ete hay c th chng ng ph d th vi cc dung mi trn.-Sn xut v s dng nh bng 3.3.1


38/64

Bng 3.3.1S dng, % KL Ty u M Nht

SX anhydric axetic 8 6 4SX axetat xenlul 12 10 18

SX este 16 12 9SX monoclo axtic 9 2 5SX axit terephtalic 6 10 11SX vinyl axetat 37 52 27Dt, nhum, khc 12 8 26

Sn xut, % KLT axetaldehit 45 20 52T butan v naphta 16 17 6T metanol 34 62 42T nguyn liu khc 5 1 -

III.3.1-Phng php oxi ho axtaldehit:-C hai cng ngh: Sn xut AcOH vi xc tc mui Cov sx ng

thi AcOH v (Ac)2O vixc tc hnhpmuiCo v Cu.a/SX AcOH:-Phn ng:CH3-CHO + 1/2O2CH3-CO-O-H H298= 265 Kj/mol-C ch phn ng:CH3-CH=O + CH3-CO-O-O* CH3-CO-O-O-H + CH3-C*=O

CH3-C*=O + O2CH3-CO-O-O*Chuyn ho tip axit peaxetic vi axetaldehit:CH3-CO-O-O-H + CH3-CH=O CH3-CO-O-O-CH(OH)-CH3

CH3-CO-O-O-CH(OH)-CH32CH3-CO-O-H vCH3-CO-O-O-CH(OH)-CH3CH3-CO-O-H + CH3-O-CH=O.

Ngoi ra t gc axtyl peoxit chuyn ho thnh gc axtyloxi vthnh mtanol, fomaldhit, axit fomic:

2CH3-CO-O-O* CH3-CO-O-O-O-O-CO-CH32CH3-CO-O*+O2

2CH3-CO-O* 2CH3* + 2CO22CH3* +2O22CH3-O-O*2CH3-O-O* 2CH3-O* + O2

CH3OH + CH2=O + O2-Vai tr ca xc tc:Xc tin tng tc peaxit vi axtaldehit.


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Gim gc axtyl peoxi v do gim phn ng phnhphn ng:CH3-CO-O-O* + Co

2+CH3-CO-O-O-+ Co 3+

-iu kin phn ng:Cht oxi ho Khng kh Oxi k thut

Nhit , 0C 55 65 70 80p sut, MPa 0,5 1 0,15 0,3-Sn phm ph ch yu l fomaldhit, axit fomic, mtyl v tyl axtat,

axton v CO2.S cng ngh hnh 3.3

Khngkh

H.3.3-S cng ngh oxi ho axetaldehit thnh axit axetic

bng khng kh.

1-Thp x l khng kh. 2- TBP oxi ho. 3-Thp ra kh thi4-Thit b phn hu axit peaxtic. 5-Thp chng axtaldehit.6-Thp tch mtyl axtat. 7-Thp chng ng ph tch nc v tinhch axit axtic. 8-Thp chng ng ph tch tyl axtat trong nc.

b/Sn xut ng thi axit axtic v anhydric axtic (Tsi=139,60C):

-Xc tc l hn hp mui Co hay Mn v Cu vi t l Co (Mn) : Cu =1 : ( 1 3 ).

-Cht oxi ho ngho oxi hn khng kh- hn hp nit vi 7 9% thtch oxi - tng nng gc axtyl CH3-C*=O. T c phn ng:CH3-C*=O + Cu

2+(CH3-CO-O)2CH3-C

+=O + Cu1+(CH3-CO-O)

+CH3-CO-OCH3-C

+=O + CH3-CO-O(CH3-C=O-)2O.

-iu kin phn ng: T = 60800C; P = 0,4 1 MPa.-Sn phm c t l AcOH/ (Ac)2O = ( 3 5 ) / ( 7 5 )-Tch ncbng chng ng ph vi Etyl axtat.-S cng ngh hnh 3.4


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H.3.5-S cng ngh sn xut axit axetic t metanol v CO.1-TB ch to phc xc tc. 2-TB trao i ion x l xc tc lm

vic. 3-Thng cha xc tc. 4-TB chto mtyl ioua. 5-Thng cha mtylioua. 6-TBP ccbonyl ho. 7-Thp hp th mtyl ioua bng mtanol.8-Thp tch kh. 9-Thp chng ly phn on giu axit axtic. 10-Thpchng ng ph tch nc. 11-Thp tch nc. 12-Thp tn thu axit axtic t

phn onnng. 13-Thp tinh ch axit axtic.

III.4-Sn xut axit trphtalic(ATP):-L nguyn liu sn xut polytylen trphtalat (PET) bng phn

ng a t vi tylen glycol:HO-CH2-CH2-[O-CO-C6H4-CO-O-CH2-CH2]n-OH

Nha PET dng sn xut si polyeste (7080%), ngoi ra dnglm phim, ng.

-tinh khit ca monome rt quan trng di vi cht lng ca si,do vyqu trnh tinh ch sn phm cn c ch trongcng ngh sn

xut v song song vi ATP ngi ta sn xut c este ca n l dimetylterephtalat (DMTP) d tinh ch: ATP khng nng chy, thng hoa 3000C, cn DMTP c Tnng chy= 141

0C, Tsi= 2840C, ho tan trong te v

mtanol nng, nh vy c th tinh ch bng kt tinh hay chng ct chnkhng.

-Phng php sn xut ch yu l oxi ho p-xylen (c tch bngcng ngh lin tc hp ph chn lc PAREX).


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III.4.1-Oxi ho p-X bng HNO3:C6H4(CH3)2+ 4HNO3C6H4(COOH)2+ 4H2O + 4NO

H298= 750 Kj/mol-KP: 1650C, 1 MPa, pha lng d th TBP loi thng c khuy.

-ATP to thnh khng tan,tch bng li tm v chuyn thnh DMTP 1500C, XT l H2SO4, v chuynqua giai ontinh ch.-Hiu sut tng cngt 90%.-Cn thu hi NO v ti sinh HNO3m bo v kinh t v mi trng:

NO + 1/2O2NO2.4NO2+ O2+ 2H2O 4HNO3.

-y l cng ngh c ca Du Pont, BASF: ln hp cht nit kh tinhch, dng sn xut t 1970.III.4.2-Oxi ho p-xylen thnh DMTP

-Oxi ho nhm etyl th nht to thnh axit p-toluic d, nhm CH3th2 kh oxi ho hn. Khi este ho nhm -CO-O-H th nht th qu trnh oxiho tip theo d hn. Hn na, DMTP d tinh chnh ni trn.

-C 4 phn ng ln lt nh sau1/Oxi ho p-X thnh axit p-toluic:

C6H4(CH3)2+ 3/2O2CH3-C6H4-CO-O-H + H2OH298= 690 Kj/mol

C ch chui gc, xc tc l naphtenat Co,Mn.2/Este ho axit p-toluic vi mtanol thnh p-mtyl toluat:

CH3-C6H4-CO-O-H + CH3OH CH3-C6H4-CO-O-CH3+ H2O

H298= 30 Kj/molPhn ng thun nghch, d metanol v tch nc phn ng n

cng, xc tc axit.3/Oxi ho nhm mtyl cn lithnh mtyl trphtalat:

CH3-C6H4-CO-O-CH3+ 3/2O2H-O-CO-C6H4-CO-CH3+ H2OH298= 675 Kj/mol

4/Este ho thnh DMTP:H-O-CO-C6H4-CO-O-CH3+ CH3OH CH3-O-CO-C6H4-CO-O-CH3

+ H2O

H298 = 30 Kj/molTrong sn xut thc hin p 1 v 3 trong 1 TBP oxi ho, v p 2 v4 trong mt TBP este ho.

-TBP oxi ho:H d th kh-lngthp si bt. Dng h thp ni tip m bo

nglc hc ca TB cao, gii nhit qua thnh bng ng xon hay bm tunhon qua thitbtrao inhit.


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KP: 150 1800C, 0,6 1 MPa, XT: naptenat Co.Nguyn liu vo: Hnhpp-X v p-mtyl toluat.TBP l thp sibtnitip.-TBP este ho:

KP: 2500

C, 2,5 MPa, XT: p-toluen sunfoaxit.TB thng c khuy ni tip c tch nc bng cch bay hi.

H.3.6- Scng nghsnxutimtyl Trphtalat (DMTP).1-Chunbxc tc oxi ho. 2-TBPoxi ho. 3-HTB thu hip-Xylentrong kh thi. 4-TBPeste ho. 5-Chunbxc tc este ho. 6-Thp tchmtanol. 7-Thp tinh chmtanol. 8-Thp tch DMTP. 9-Thp tinh chDMTP. 10-Ho tan DMTP. 11-Kttinh ln1. 12-Li tm. 13-Ratinh th.14-Ho tan DMTP. 15-Kttinh ln2. 16-Nng chyDMTP. 17-Thp chngtinh chDMTP.

III.4.3-Oxi ho p-Xylen thnh ATP theo cng ngh Amoco:

-Trn c s xc tc mi cha Br-: axetat Co + NaBr, dung mi l axitaxetic, c th oxi ho c hai nhm metyl:C6H4(CH3)2+3O2C6H4(CO-O-H)2+ 2H2O

H298= 1360 Kj/mol-KP: 195 2050C, 2 3 MPa, hn hp phn ng: 100 phn

AcOH, 15 phn p-Xylen, 2 phn xc tc (t l Br/Co = 2/1).


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- chuyn ho p-X trn 95%, hiu sut 90 92%, thun ATP t99,5%.

H.3.8-Scng nghsnxutATP bngcch oxi ho trctipp-X theo cng nghAmoco.

1-TB iuchxc tc. 2-HTBPsibtnitip. 3-TB kttinh.4-Lcli tm. 5-TB sykh. 6-Thp hpth. 7-Thp chng tch nc.8-Thp chng tch axit axtic. 9-TB raATP. 10,11-TB ho tan ATP

nhitcao. 12-TB hidro ho. 13-Lcxc tc. 14-TB kttinh.

III.5-Oxi ho trn xc tc rn.III.5.1-Sn xut Fomaldehit:-TS = 190C, l chtkh.-Ho tan ttvo nc, phnng tothnh oxi mtylen glycol:

nCH2O + H2O HO(CH2O)nHn t1 10 phthucvo nng CH2O.

Nhc thvnchuyn, sdngfommalhit dngdung

dch35 55% CH2O, cgil dung dchFomalin, cngnhtch mtanolcha chuynho tdung dchFomalin trong cng nghsnxut.-ngdngcaFomalhit:


45/64

SdngFomaldhit, % Ty u M NhtNhanhitrn

Trong : Mlamin - FomalhitPhnol - Fomalhit

Ur - Fomalhit

6169

46

584

22

32

4669

31Pentaerythritol [ C(CH2OH)4] 8 7 8Nhapolyaxtal 6 8 19Urotropin (hexamtylentetramin) 3 5 5Butaniol [ HO(CH2)4OH ] 5 11 -Cc ngdngkhc 17 11 22

-Fomaldehit csnxuttmtanol bngqu trnh oxi-dehidro hotrn xc tc bcv oxi ho trn xc tc oxit Fe-Mo.

-y l cc qu trnh pha hi nn cntrnh tohnhpnmetanol -

khng kh c thnh phnt6 n40% thtch metanol.a/Cng nghxc tc bc:Nhitphnng: 650 - 7200C.Tinhnh qu trnh trn giihnn, hnhpphnngcha

khong45% thtch mtanol, do thiuoxi cho phnngoxi ho nn cthm phnngchnh dhidro ho mtanol

CH3OH + 1/2O2CH2O + H2O ( 1 ) H298= 156 kJ/molCH3OH CH2O + H2 ( 2 ) H298= + 85 kJ/mol

Phnng(2) thunnghch, thu nhit. Cn bngphthucnhit:

4000C - XCB= 50%; 5000C - XCB= 90%; 6000C - XCB= 99%Tngnhitphnngcaqu trnh l tonhit, qu trnh nmphm

vi khuchtn ngoi, onnhitv tnhit, iuchnhnhitphnngbngcch pha thm hi ncvo hnhpphnng.

Thnh phncakh thisau thp hpthcha15 20% thtchhidro, ctthu hinhittrckhi thi.

Phnngph: CH2O CO + H2(nhitcao, xt st)CH3OH + H2CH4+ H2OCH2O + O2 HCOOH

CH2O + O2 CO2 + H2OTthnh phncakh thisau thp hpthc thtnh cchnlcv hiusutcaqu trnh. Ngay sau lpxc tc cnlm lnhnhanh hnhpphnngtrnh phn hufomalhit.

Thitbphnng vilpxc tc mng(khong30 - 50mm) gmAg tinh thhay Ag trn chtmang lxplnttrn ling, cng b


46/64

phntinmiphnngkhi mmy v lm lnhngchm tstngay sau lpxc tc nhhnh

C hai cng nghsnxut:Cng ngh6500C, XMeOH= 85%, chng thu himtanol cha

chuynho tdung dchfomalin sau thp hpth.Cng ngh7200C caBASF, XMeOH= 98- 99%, khng phichng

thu himtanol.S cng ngh vi xc tc Agtinhnh nhitcao 7200C ca

BASF


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Nc mm

Khng kh

Nc mm

Hi nc

Formalin50% CH2O

Metanol

Hi nc

1

2

35

6

7 7Khngkh

4

Kim thi(+Natri Fomat)

Dung dch kim

H.3.5.2-S cng ngh oxi ho metanol thnh formaldehit

trn xc tc Ag 7200C1-Lc bi khng kh. 2-TB to hn hp hi metanol-khng kh.3-TBP. 4-TB lm lnh ng chm. 5-Thp hp th formaldehit6-L t kh thi. 7-Thit b trao i anion kh axit fomic.

b/Cng nghxc tc oxit Fe-Mo:Xc tc Fe2O3- MoO3vitlmol tng ng1/1,5.Nhitphnng: 290 - 3100C.Lm vicdigiihnn( hnhpkhong6% thtch mtanol ),

doxi nn chc phnngoxi ho (1) tonhiunhitl phnngchnh.

Do nngmtanol thpdnnthtch hnhpphnngrtln(4-5 lnso vixc tc bc) nn cntunhon kh thingho oxi sau thp hpthc tha nngmtanol ln m khng tothnh hnhpn, nhgimckch thcthitb, ngng, cng sutmy nn kh ... cngnhcntinhnh trao inhitgiadng nng v dng lnhcahnhp

phnng.


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Xc tc lptnh, TBPdngngchm ( hnh 4.22 ), ngknhngtng inhc20 - 25 mm.

H1-TBPngchm. 2-Thp hpthfomalhit. 3-TB xl kh thi4-TB trao ianion khaxit fomic.

III.5.2-Snxutoxit etylen (OE):a/Tnh chtv ngdng:-TS= 10,8

0C, tntrv vnchuyndnglngdip sutnit.-Ho tan ttvo ncv khi c xc tc axit v nhitsphnng

toetylen glycol:CH2-CH2+ H2O HOCH2- CH2OHO

-Giihnnvikhng kh: 2,6 80% thtch OE.-Khnng phnngcao, l hpchttrung gian quan trng.


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Sdng,% Ty u M Nht

SnxutEtanolamin 10 8 6SnxutEtylen Glycol 45 61 58

SnxutEte Glycolic 11 6 6SnxutchtHBM khng ion 21 12 21Cc ngdngkhc 13 13 9

b/Cng nghsnxut:-Chyuhinnay l oxi ho Etylen bngoxi trn xc tc Ag.-Phnng:Chnh:

O

CH2-CH2CH2=CH2+ 1/2O2

0298H = 105 kJ/mol

Ph: CH2=CH2+ 3O2 2CO2+ 2H2O0298H = 1330 kJ/mol

O

CH2-CH2 + 5/2O2 2CO2+ H2O

0298H = 1225 kJ/mol

HiusutOE trong snxutcng nghipthngkhong70% do vynhitphnngc500 kJ/mol Etylen chuynho. y l phnngtonhitcao v chnlcnhyvisthay inhitnn TBPdng loing

chm vingknh ngkh b, c20 25 mm.-Xc tc: Ag/cht mang c xpthp.

Cuthottnh l Ag.Chtkch ng, tng chnlc:

MuiBa, Ca, x phng Na,Li.Hpchtclo huc: Dicloetan, Diclopropan. Cc cht

ny cho ngthivo hnhpphnngvihm lng10 ppm.Chtmang: Dnnhittt, bmtb c0,1 0,2 m2/g.

Thngdng -Al2O3 (Shell), silic ccbua (Scientific Design, Montecatini),

vtliusilicat, ferrosilic (Dyanamit Nobel).Rtnhiupatent vxc tc Ag/chtmang lin quan n

phng php chtoxc tc, chtkch ng, chtmang, xp, bmtring, dnnhitcaxc tc.

-iukincng ngh:Nhit: Tp= 260 290

0C. L thng squan trngsau xctc v nhittng th chnlcgimmnh.


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p sut: Khng nhhngnqu trnh phnng. Trongcng nghipthngtinhnh 1 3 MPa tng cngtrao inhit,gimthtch thitb, dtch OE (hpthvo nc, lm lnhho lng).

. Nguyn liu:

Etylen c hm lng95 98%, schtpchtaxtylen, cc olfinkhc v hpchtlu hunh.Chtoxi ho: khng kh v oxi kthut. Thngdng oxi kthut

trnh tnthtEtylen trong kh thi.GiihnnE-KK l 3 28,6% thtch Etylen

Cc cng ngh:Cng nghShell (H. ): Dng Oxi kthutc thuntrn 95%,

Etylen c thchan10% thtch CH4, tinhnh trn giihnn, dEtylen v tunhon lisau khi khCO2.

H. . -Cng nghShell snxutOE1-TBPngchm. 2-Thp hpthOE bngnc. 3-Thp nhOE.

4-Thp tch kh. 5-Thp tch OE. 6-Thp tinh chOE. 7-Thng chanchpth. 8-Thp hpthbsung. 9-Thp hpthCO2. 10-Thp nhCO2.11-TB tch nc.

Cng nghScientific Design (H. ): Dng khng kh, lm vicdigiihnnvitlthtich KK/E = 10/1, hai TBPnitipchuynhontEtylen sau khi hpthOE. Hnhpkh sau TBPthnhtcha2%

OE, 2-3% E= (XE =25 30%, S = 70%), sau khi hpthOE tunhon likhong60%, kh cn lithm khng kh v a vo TBPth2. y duytr chuynho cao X = 75-80% vichn lcS = 50%. Hiusuttngcngt60 - 65%.


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H. . -Cng nghScientific Design snxutOE.

1-TBPthnht. 2-Thp hpth. 3-TBPth2. 4-Thp hpth.5-Thp nhhpthOE. 6-Thp tch OE. 7,8-Thp tinh chOE. 9-TB tchkh-lng. 10-Thp tch kh thi.III.5.3-SnxutEtylen Glycol (EG).

TNC= ,TS= 1970C.

ngdng:Lnhvcngdng, % Ty u M Nht

Chtchngng lnh 33 47 13SiPolyeste 48 36 64

NhaPolyeste khng no, nhaalkyt,cc ngdngkhc. 19 17 23Snxut: Phng php cng nghipchyul tOE.Phnng:

O

CH2-CH2 + H2O HOCH2-CH2OH

0298H = 75 kJ/mol

Snphmphl DEG [HO(CH2-CH2O)2H] vTEG [ HO(CH2-CH2O)3H]

snxutMEG dng tlOE/H2O = 1/20 25, khi hnhp

phnngc thnh phn88,5% MEG, 10,5% DEG v 0,5% TEG.iukincng ngh:Phnng ngthpha lng, onnhit.Tvo= 150

0C, Tra= 2100C.

Thigian phnng: 45 60 ph. Khng dng xc tc.Cng ngh:


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Sau phnngc ctrong h4 TB nitip, TB sau dng hi thcaTB trc. Tiptheo chng chn khng tch ncv cc glycol.

H. . -Cng nghsnxutEtylen Glycol.1-TB trn. 2-TBPpha lng, onnhit. 3-Hthngc c. 4-Thp

tch nc. 5-Thp tch MEG. 6-Thp tch DEG. 7-Thp tch TEG.III.5.4-SnxutAnhyric Maleic (AM) v Anhyric Phtalic (AP).A-SnxutAM:- TN/C= 53

0C; TS = 2020C.-csdngt50% (M, Nht) n90% (Ty u) cho snxut

nhapolieste khng no l polyme mchthngdnglng, ngrnvimonome vinyl khc nhstyren c mtchtkhi mo thnh polyme mchkhng gian.

nHO-RO-H + H[ORO-C-CH=CH-C-]nOHCH

CH C

O

C

O

O

-csnxutbngoxi ho Benzen, n-Butan v n-Buten pha hi

trn xc tc rn.Nguyn liuban u, % Ty u M Nht

TBenzen 74 - 65Tn-Butan 20 100 14Tn-Buten - - 21SnphmphcasnxutAP 6 - -

a/TBenzen:Phnng:Chnh:

CH

CH C

O

C

O

O

+ 4O2 + CO2+ CO + 2H2O


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0298H = 1470 kJ/molPh:

+ 6O2 3CO2+ 3CO + 3H2O

0298H = 2320 kJ/mol

Nhitphnng(chnh v ph) rtln, cntndngtohi nc.iukincng ngh:TP = 350-400

0C; P = 0,1-0,2 MPa.Xc tc V2O5+ MoO3/Al2O3vichtnnhP2O5.GiihnnBenzen-KK l 1,4 7,1% TT. Tin hnh 1,2-1,3% BZ.TBPdngngchm, giinhitbngmuinng chy. TGL = 0,1s.chuynho X = 95%, chnlcS = 67%.

H. . -Cng nghsnxutAM tBenzen.1-TBPdngngchm trao inhitvi muinng chy. 2-Nihi

3-TB tch lng-kh 600C. 4-Thp hpthAM bngnc. 5-TB bay hichn khng (30-60 kPa) mng mng. 6-TB thu hiAM trong cn. 7,8-Thp

chng chn khng tinh chAM (10-20 kPa).b/Tn-Butan:Snxut50% AM. Gi n-Butan rhn Benzen.Phnng:Chnh:


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CH

CH C

O

C

O

O

CH3-CH2-CH2-CH3+ 7/2O2 + 4H2O

0298H = 1240 kJ/mol

Ph:CH3-CH2-CH2-CH3+ 11/2O22CO2+ 2CO +5H2O

0298H = 2090kJ/mol

iukinphnng:iukinlm vicgingvicng nghsnxuttBenzen. Ddng

chuynhTB tBZ qua nguyn liuny.Xc tc trn csoxit P,V v Fe/chtmang Al2O3,SiO2.Mtkhc bitnglu : lngnctothnh vinguyn liuny

lnhn (gpi) nn hnchnhitlm lnhtch AM, lm lnhtrnimsng cahi ncv chtch c25-30%, sau hpthbngdung mi ibutyl hexahidrophtalat, nhhpthAM v tinh chAM tronghai thp chng chn khng.

H. . -Cng nghsnxutAM tn-Butan.


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1-TBPngchm. 2-Nihi. 3-TBtch kh-lng. 4-Thp hpthAM bngdung mi huc. 5-Thp nhAM. 6,7-Thp chng chn khngtinh chAM. 8-Bchi chn khng mng mngti sinh dung mi.

B-SnxutAP:T

NC= 1310C, T

S= 284,50C.

ngdngv cc phng php snxut:

ng dng, % Ty u M NhtSnxutnhaAlkyd 16 19 14Snxutchtho doPhtalat 63 51 63SnxutnhaPolyeste khng no 19 25 15Cc ngdngkhc 2 5 8

Phng php sn xut, %TNaphtalen 8 15 29

To-Xylen 92 85 71Phnng:Chnh:TNaphtalen:

CO

C

O

O+ 4,5O2

+2CO2+ 2H2O

0298H = 1790 kJ/mol

To-Xylen:

C O

C

O

O

+ 3H2OCH3

CH3+3O2

0298H = 1108 kJ/mol

Ph:ViNaphtalen:

CH

CH C

O

C

O

O

C10H8+ 12O2+ 6CO2+ 3H2O

C10H8+ 12O210CO2+ 4H2O 0298H = 5050 kJ/molVio-Xylen cngc 2 phnngphtrn, khi oxi ho hon ton to

nhit4380 kJ/mol.Do vynhitphnngthctkhi chuynho mtmol nguyn liu:

ViNaphtalen, hiusut80-85%: 2100 - 2500 kJ/mol.Vio-Xylen, hiusut 77-79%: 1300 - 1800 kJ/mol.

iukinphnng: Gingnhau cho chai nguyn liu.


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Xc tc trn csV2O5 c thm phgia tng chnlc.Giihnndicao-Xylen vikhng kh l 1,7% mol (70-80g/m3)

caNaphtalen l 0,9% mol (44g/m3).Tinhnh qu trnh digiihnn,tlmol KK/HC thngt60 - 120.

TP

=350-4300C. Cng nghipdng 2 loiTBP:-Loingchm: Dng chttrao inhitl muinng chy

(53%KNO3+ 40% NaNO2+7% NaNO3- l hnhptcti c TNC=1500C,

chunhitn5500C).-Loitngsi: ViloiTBPny c thnng cao nngHC m

khng stohnhpndo hintngkhuytrnmnhtrong lpsi cnhiukh trv hi nc. Ngoi ra cngdo hintng khuytrnmnhcalpsi ddng giinhitphnngv dng tc nhn mang nhitl nc.Tuy vy, hiusutAP thphn khi dng lpxc tc cnh.

Cng ngh:

Tch snphmbngcch lm lnhgin ontrong hai TB theo chuk: Lm lnhkttinh AP v nng chyho lngAP.

Tinh chAP:-Gia nhitn230 - 3000C trong 10 - 24 gitrong TB thng c khuy

c lm lnhhilu bay hi v phn hucc tpchtnhNaphtoquinon,o-Tolualhit, Phtalid. Trong giai onny c ththm NaOH, H2SO4,H3BO3.

-Cuicng chng chn khng.


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H. . -Cng nghsnxutAP to-Xylen.1-TBPngchm. 2-Nihi. 3-TB lm lnhkttinh v nng chy

AP. 4-Thp hpth. 5,6-TB xl AP bngnhit. 7,8-Thp chng tinhchAP.

Ht chn khng

Nc thi

Nc

Kh thi

(i t)

Hi nc

Hi nc

Nc mm

Khng kh

Naphtalen

S.P.nng

Nc

Hi

Anhydr ic Phtali c1

3

4

56

Chn khng

2

2

H. . -Cng nghsnxutAP tNaphtalen.

1-TBPtngsi. 2-Nihi. 3-TB kttinh v nng chyAP. 4-Thphpth. 5-TB xl AP bngnhit. 6-Chng chn khng tinh chAP.

IV-Cc qu trnh clo ho.IV.1-c trng caqu trnh clo ho:Mcch:-Snxutcc monome chaclo: vinyl clorua, cloropren.-Snxutcc hpchttrung gian: CH3Cl, icloetan, Clobenzen.-Snxutdung mi chaClo, chtho do.Cchphnng: Qu trnh clo ho cc hpchthucthngtin

hnh theo hai cch: Cchchuigc v cchion tophc.a/Cchchuigc:

Phnng:-Clo ho cc HC no: Thhidro v toHCl.CH4+ Cl2CH3Cl + HClRH + Cl2RCl + HCl

-Clo ho cngvo nhn thm:C6H6+ 3Cl2C6H6Cl6


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-Thv cngClo vo lfin pha kh, xu thtngloiphnngphthucvo nhit:

CH2=CH-CH3+ Cl2CH2=CH-CH2Cl + HCl ( >3000C)

CH2=CH-CH3 + Cl2CH2Cl-CHCl-CH3(


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CCl -C*+ Cl2 Cl* + CCl - CCl

+tchui:Do kthpcc gctdo tothnh phn t.Do hpphgctdo ln thnh thitb.

Do kthpvicc hpchtbtgc(lu hunhv cc hp chtchalu hunh, cc hpchtphnol, viphn toxi). cbitphn toxi ctrong Clo ingii, nn tinhnh qu trnh Clo ho theo phnngchuigccndng Clo bchi tClo lng.

Cng ngh

V.1-Sn xut1,2 icloetan (1,2 CE):-C hai phng php cng nghip sx 1,2 CE: Clo ho v oxiclo ho

etylen. Phng php sau nhm tn dng HCl to thnh nhng qu trnh cloho theo phn ng th, cng nh qu trnh phn hu nhit 1,2CE snxut vinyl clorua.

a/Qu trnh Clo ha Etylen:Phnng:

CH2=CH2+ Cl2CH2Cl - CH2Cl H298= 220 Kj/molKh Kh Lng( Ts= 85

0C)Thctl phnngkh-lng: scetylen v clo vo 1,2CE lngho

tan FeCl30,5% vivai tr xc tc. Phnngxyra trong pha lngvivntccao ngay nhitthng. Nhvy, qu trnh c ctrng dthkh-

lng, tonhiunhit, tinhnh nhitthpcnhitsi capha lng.nhithi cao ( 80 - 1000C ) phnngphclo ho tipthnh tricloetanc ctng cng, v vycng nghctinhnh clo ho nhitthpv giinhitphnngbngnc.

nnay phnngphtheo cchchuigc bhnchbngcch dng xc tc FeCl3v clo c chaoxi, nn c thtinhnh nhitcao hn v sdngnhitphnng( kh ln) tch snphmdnghikhng blnvixc tc.

Cng nghtinbnhtdng TBPdngCD, kthpvithp

chng, tndngnhitphnngtinh chCE khng chtthitbcloho m tcc bphnkhc cahthnglin hp, v dtcng onoxicloho hay cng onnhitphn CE v tch VC.

Hnh 5.1 trnh by hthngTBPkthpthp chng luyntinhchCE.


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H.5.1.HTBPtnghp1,2 CE nhitcao, tndngnhit

phnngtinh chsnphm.

S cng ngh vi TBPdngthp sibt, tinhnh nhit

xpxnhitsi caCE v giinhitphnngbngcch bay hi snphmphnng, ctrnh by hnh 5.2.

H.5.2-S cng ngh sn xut 1,2 icloetan t Clo v Etylen.1-TBP Clo ho Etylen. 2-Lng tch . 3-Lm lnh trc tip tch CE4-Ra bng nc 5-Phn li lng-lng. 6-Chng ng ph tchCE.7-Chng ng ph kh nc. 8-Chng 1,2 CE.9-Chng thu hi CE

b/Qu trnh oxiclo ho Etylen:-Phn ng:

C2H4+ 2HCl + 1/2O2CH2Cl-CH2Cl + H2OH298= 295 Kj/mol

-Xc tc CuCl2/ cht mang,Tp = 200 3000C.-L qu trnh pha kh to nhiu nhit.


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-C ch cho thy xc tc l cht chuyn Clo:C2H4+ 2CuCl2C2H4Cl2+ Cu2Cl2Cu2Cl2 + 2HCl + 1/2O22CuCl2+ H2O

-p dng trong cng nghip t 1960, khi bt u sn xut vinyl clorua

t Etylen.-TBP: Dng 2 loi ng chm v tng si.Scng nghoxiclo ho vihai loiTBPtrnh by hnh 5.3

v 5.4.

H.5 3- SnxutCE bngoxiclo ho etylen dng TBPdngngchm.

1-HTBPdngngchm. 2-TB lm lnhtrctipv trung hoHCl. 3-TB phn ly kh-lng. 4-TB sykh. 5-TBPclo ho etylen.6,7-TB phn ly tch CE. 8-TB phn lyCE-nc. 9-Thp chngngph tch CE trong nc. 10-Thp chng ngph tch nclm khan CE. 11,12-Hthp tinh chCE.


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H.5.4 -SnxutCE bngoxiclo ho etylen dng TBPdngtngsi.

1-TBPdnglpsi. 2-TB phn ly tch XT. 3,4-Thp lm lnhtrctipv trung ho HCl. 5-Thp hpthCE bngalkylbenzen. 6-ThpnhCE. 7-Thng phn li CE-nc. 8-Thp chng ngph tchCE. 9-Thp chng ngph lm khan CE. 10,11-Hthngthptinh chCE.V.2-Sn xut vinyl clorua: CH2=CHCl, Ts= 13,4

0C-L monome quan trng, sn lng ln.-C 2 cng ngh sn xut: t axetylen v t 1,2 DCE.a/Cng ngh hidroclo ho axetylen:-Phn ng:

CHCH + HCl CH2=CHCl H298= 100 Kj/mol

-Xc tc HgCl210% /than hot tnh,xc tc gim hot tnh do bay hiHgCl2khibmtthan nn, thi gian lm vic ca xc tc t 3 n 6 thng,Tp= 130 170

0C, p sut ch thng tr lc trong h thng, d nh HCl,t lHCl/C2H2= 1,1/1.

-Phn ng ph to thnh 1,1DCE, nhng ch 1-2%:CH2=CHCl + HCl CH3-CHCl2


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-TBP: ngchm, ng knh ng D = 50 mm, c thgiinhitphnngbngdutunhon hay bngcch bay hi ncdip sut0,5 1 MPa, Tmaxkhng c vt qu 200

0C v HgCl2bay hi lm gimnhanhhot tnh xc tc.Trong qu trnh lm vicTmaxchuyn dchtheo dng kh

v pha cui ng v thng hoa HgCl2.-Cng ngh sn xut nh hnh 5.3

H.5.5-S cng ngh sn xutvinyl clorua t axetylen.1-TB trn. 2-TBP hidroclo ho axetylen. 3-Thp ra HCl bng nc.4-Thp ra kim. 5-Thng phn li lng-lng-kh. 6-Thp chng ng phtch nc. 7-Thp hp th axetylen. 8-Thp nh axetylen. 9-Thp chng.

b/Cng ngh crcking1,2DCE:-Phn ng:

CH2Cl-CH2Cl CH2=CHCl + HCl H298=70 Kj/molC ch chui gc nhit cao:Khi u to gc:

CH2Cl-CH2Cl CH2Cl-C*H2 + Cl*Tip tc chui:

Cl* + CH2Cl-CH2Cl CH2Cl-C*HCl + HClCH2Cl-C*HCl CH2=CHCl + Cl*

-KP:Tp = 500 5500C. P = 2 3 MPa . Dng p sut ny

gim kch thc thit b pha kh, tng h s trao i nhit, d tch sn phmvinyl clorua ( lm lnh ngng t bng nc ).

Thi gian lu 10 20 giy, X = 50 60% trnh phn ngph to cc do polime ho VCM tip theo.

Hiu sut t 95 99%-TBP: L ng, lm lnh nhanh bng ti trc tip vi CE tun

hon.-Trong sn phm nhit phn ngoi VCM cn CE cha chuyn ho

v mt lot cchp cht khc nh axetylen, vinyl axetylen, 1,3 butadien,


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2 clo1,3 butadien, benzen, clobenzen v cc dn sut clo khc ca cc hpcht C1,C2,nha v cc.

H.5.6 -SnxutVCM ticloetan1-TBPdngl ng. 2-TB lm lnhtrctip. 3-Thp tch HCl.4-Thp tch CVM. 5,6-Tinh chVCM. 7,8,9-Tinh chCE chachuynho.-Do qu trnh snxutVCM ticloetan tch ra HCl nn thng lin

hp sn xut 1,2 CE bng clo ho v oxiclo ho vi crcking CE thnhVCM nh phn 1 ni. S khi tch hp cc sx trn nh hnh . .

H.5.7-Tch hpsnxut1,2 Dicloean v Vinyl clorua monome.

cong nghe tong hop hoa dau_tran cong khanh

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