Nhm 9

Cng ngh sn xut Viny clorua

MC LC
Hnh3.1: S sn xut VC t C2H2 49 ...........2 CHNG 1: TNG QUAN V VINYL CLORUA......................................................5 1.2. TNH CHT VT L CA VINYLCLORUA.............................................................................6 ............................................................................................................................... 6 1.3. TNH CHT HO HC................................................................................................... 8 CHNG 2: CC QU TRNH SN XUT VC.....................................................11 2.1. TNG QUAN V SN XUT VC.....................................................................................11 2.2. QU TRNH IU CH CV T 1,2DI-CLOETAN ................................................................13 2.3. QU TRNH SN XUT VC T ETYLEN............................................................................19 2.3.2 Cng ngh sn xut.....................................................................................21 2.3.3 u nhc im............................................................................................. 22
a. u im.................................................................................................................. 22 b. Nhc im.............................................................................................................. 22

2.4. SN XUT VC T ETAN..............................................................................................22 2.5. PHNG PHP LIN HP SN XUT VC.........................................................................25 CHNG 3: QU TRNH SN XUT VC T AXETYLEN.......................................29 3.1. NGUYN
c. Phn ng kt hp................................................................................................ 31 3.1.1.3. Sn xut axetylen........................................................................................... 32 b. Sn xut axetylen t nhin v kh ng hnh....................................................34 3.1.2.2 Cc phng php sn xut axit HCl ph bin trn th gii...............................38
LIU CA QU TRNH......................................................................................29

3.2. 3.3. 3.4. 3.5. 3.6.

XC TC CHO QU TRNH........................................................................................... 39 C CH PHN NG................................................................................................... 42 SN XUT VC T AXETYLEN TRONG PHA LNG...............................................................43 SN XUT VC T AXETYLEN TRONG PHA KH..................................................................45 NH GI U NHC IM CA QU TRNH SN XUT VC T AXETYLEN.............................50

CHNG 4 : KT LUN..................................................................................52 TI LIU THAM KHO....................................................................................53

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

Danh mc hnh
Hnh 2.1 S sn xut bng phng php lin hp 26 Hnh 2.2 Sn xut VC t kh cracking du m....................................................28 Hnh3.1: S sn xut VC t C2H2 49

Danh mc bng
Bng 1: Hiu sut chuyn ho ca axetylen ph thuc vo %HgCl2/C*.......41

Vit tt VC= Vinyl clorua

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

LI M U
t nc ta c nhiu than v du m, c ti nguyn khong sn phong ph, li giu v thc vt nhit i, l nguyn liu di do pht trin mt nn cng nghip ho cht. Cng vi nhng tin b khoa hc k thut trn th gii, t nc ta ang y mnh pht trin cc nghnh cng nghip mi nhn, mt trong nhng nghnh l nghnh ho cht. Trong nhng nm qua, hng trm nh my ho cht c xy dng, nhiu c s o to cn b v c s nghin cu khoa hc c pht trin v khng ngng ln mnh cng vi nhp xy dng ch ngha x hi ca nc nh. Cng vi s pht trin ca nghnh khai thc du kh, nghnh cng nghip ho cht ni chung v nghnh cng nghip ch bin cc sn phm du m ni ring khng ngng ln mnh. Song song pht trin cng vi nghnh ho du hin nay, nghnh polyme cng c lng ln mt tm cao mi. Cc sn phm polyme v ang c ng dng rng ri trong cng nghip v i sng. c bit hin nay n c coi l nguyn liu sn xut ra cc vt liu mi c tnh nng p ng c cc yu cu ca cc nghnh k thut cao m cc nguyn liu khc khng th p ng c. Mt trong nhng polyme c ngha to ln nht hin nay l polyvinylclorua. Poly-vilylclorua (PVC) l loai cht do c nhiu tnh cht tt:n nh ho hc cao, t b n mn v ph hu bi H 2SO4 , HCL. .. c kh nng co dn v bn tng i ln, c tnh cch in, khng thm nc, khng b ph hu khi gp nc, nhng li d nhum. Do cc tnh cht tt nh vy, PVC c dng sn xut cc loi ng dn cc cht ho hc, lm vt liu lt bn trong cc thit b ho hc lm vic nhit thp thay th thp khng d v hp kim. Trong cng nghip in PVC c dng sn xut cc loi dy bc, cc dng c cho v tuyn in. PVC dng trong xy dng d lt sn, tng cch m, cc dng c gia nh, bn, gh, t v v.
GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

PVC gia cng vi cc loi cht ho do cho ta cc loi mng mng dng lm o ma, vi bc v v. .. sn xut c PVC cn phi c vinylclorua. Khong 95% vinylclorua trn th gii c s dng tng hp PVC, phn cn li c ng dng trong cc qu trnh sn xut dung mi c bit, cht lm lnh, trong cng nghip tng hp cc ho cht. ng trng hp VC vi cc monome khc nh vinilydenclorit CH 2 = CCl2, vinyl axetat CH2 = CHOCOCH3, acrylnitril CH2 = CHCN to thnh cc polyme gi tr. Vinylclorua cn c dng sn xut si ho hc clorin, sn chu n mn. Vi nhng tnh nng quan trng trn, Ngnh sn xut vinylclorua khng ngng c m rng v ci tin c v qu trnh v cng ngh. Hin nay n c sn xut nhiu nht M v cc nc Ty u.

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

CHNG 1: TNG QUAN V VINYL CLORUA

1.1 Lch s hnh thnh Vinyl clorua Vinylclorua l mt trong nhng sn phm thng dng quan trng trong cng ngh ho hc. Ngi ta s dng vinyl clorua (VC) lm cht trung gian trng hp thnh polyvinyl clorua (PVC) hay ng trng hp vi cc monome khc to ra cc sn phm polyme khc nhau. Qu trnh iu ch VC u tin vo nm 1830-1834 khi m V.regnault tin hnh thc hin phn ng kh HCl ca icloetan trong mi trng kim ru v kh nng trng hp ca vinylclorua di tc dng ca nh sng c pht hin vo nm 1872 bi Baumann. Vo nm 1911 hai nh bc hc F.klatte v Rollet nghin cu phn ng gia C2H2 v HCl sau 2 nm chnh nh phn ng ny iu ch ra xc tc HgCl2 do Griesheim Elektron, nhng sn phm PVC u tin trong cng nghip l vo nm 1930 theo phng php ca F.klatte s dng phn ng C2H2 v HCl to ra VC. Thi gian gn y, do ngun cung cp cao su t nhin sn c v gi thnh r nhng khoa hc cha pht trin nn VC c nhng ng dng rt hn ch. Trong chin tranh th gii th hai, ngun cung cp cao su t nhin gim nhng VC cn tng hp thnh PVC pht trin thnh qui m ln Anh v M. Qu trnh sn xut VC i t C 2H2 i hi cung cp nhiu nng lng sn xut ra nguyn liu axetylen. Do cc nh ho hc nghin cu ra phng php sn xut VC mi i t nguyn liu r tin hn, l nguyn liu Etylen vo nhng nm 1940-1945 . Ngy nay, hn 90% qu trnh sn xut VC i t etylen s dng qu trnh lin hp: etylen-iclo etan- oxy-iclo etan - Vinyl clorua. V qu trnh ny thun li v i tin hnh v i kin kinh t 5

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

1.2. Tnh cht vt l ca Vinylclorua

Khi lng phn t Khi lng ring 14,20C 200C p sut hi -300C -200C -100C 00C 100C 200C 300C 400C 500C Nhit phn ng H0298 (kh) Nhit dung ring lng, 200C hi, 200C Nhit ho hi 259,80K p sut ti hn
GVHD:Ts. NGUYN VN BI

: 62,5 : 0,969g/cm3 : 0,91g/cm3 : 51 kPa : 78 kPa : 115 kPa : 165 kPa : 243 kPa : 333 kPa : 451 kPa : 600 kPa : 756 kPa : 35,2kJ/mol

: 1,352 kJ/kg.0K : 0,86kJ/kg.0K : 20,6kJ/mol : 5600kPa 6

Nhm 9

Cng ngh sn xut Viny clorua

Nhit ti hn nht -400C -100C 200C Hng s in mi 17,20C sc cng b mt -300C -200C -100C n nhit ho hi Nhit nng chy im nng chy Gii hn n trong khng kh 250C tan trong nc 200C Nc tan trong VC -150C im si 760mmHg

: 429,80K : 0,34 x10-3Pa.s : 0,25 x10-3Pa.s : 0,19 x10-3Pa.s : 6,26 : 23,87 dyn/cm : 23,87 dyn/cm : 23,87 dyn/cm : 79,53 cal/g : 18,14 cal/g : -153,70C : 4 22 %V : 0,11%kl : 300g/kg : -13,90C

Vinylclorua nhit v p sut thng l cht kh khng mu, c mi nh ete. VC rt d bt la, c im bc chy thp do d to hn hp n vi oxi khng kh. N t tan trong nc ch yu tan trong cc dung mi hu c nh: axeton, etylic, hydrocacbon thm, hydrocacbon thng. . . N c tnh gy m nh ete, tuy nhin c hi ca n khng cao bng CCl4, clopren.

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

1.3. Tnh cht ho hc Vinylclorua c cng thc cu to : CH2=CHCl Do trong phn t VC c cha mt lin kt i v c nguyn t clo linh ng nn cac phn ng chnh ca VC l phn ng cng v phn ng th nguyn t clo. 1.3.1 Phn ng ni i ( phn ng cng hp). Trong iu kin kh, nhit 140-1500C hoc 800C v chiu sng xc tc l SbCl3 th VC tc dng vi halogen cho ta 1,2 dicloetan. Khi c xc tc AlCl3, FeCl3 th VC phn ng vi HCl. CH2 = CHCl + HCl Tc dng vi H2: CH2 = CHCl + H2 CH3-CH2-Cl ClCH2-CH2Cl

Do phn t c cha ni i nn VC c th tham gia phn ng trng hp to PVC, mt sn phm quan trng. n CH2 = CHCl [-CH2-CH-] n Cl 1.3.2 Phn ng ca nguyn t Clo Trong phn t VC c s lin hp p- ca cp electron khng chia clo vi ni i C=C theo hng ngc chiu vi s phn cc kiu cm ng lin hp C
+

Cl- . Do c hiu ng lin hp p-, di lin kt C-Cl VC nh 8

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

etylclorua, dn n gim m men lng cc, lin kt C-Cl bn. V vy phn ng th nucleophyl l rt kh khn. Mun phn ng th nucleophyl xy ra i hi iu kin khc nghit. Thu phn:Khi un nng vi kim HCl b tch khi VC cho ta axetylen: +NaOH CH2 = CHCl CH CH + NaCl + H2O

Tc dng vi alcolat hay fenolat cho ta este vinylic: CH2 = CHCl To hp cht c kim: CH2 = CHCl 1. 3.3 Phn ng oxi ho Qu trnh t VC trong khng kh to ra CO2 v HCl. 2CH2=CHCl + 5/2O2 2CO2 + 2HCl + 2H2O Trong phn ng oxi ho VC nhit 501500C c mt HCl d dng to ra mono axetandehit: CH2 = CHCl + 1/2O2 Cl-CH2-CHO + Mg CH2 = CH-Mg-Cl + RONa CH2 = CHOR + NaCl

1.3.4 Phn ng t phn hu Trong iu kin khng c oxy khng kh, kh, vinylclorua tinh khit kh n nh v mt ho hc.

GVHD:Ts. NGUYN VN BI

Nhm 9

Cng ngh sn xut Viny clorua

VC trong iu kin khng c khng kh 450 0C c th b phn hu to thnh axetylen v HCl, do phn ng dime ho axetylen c th phn ng tip tc to ra mt lng nh 2-Cl -1,3Butaien 4500C CH2 = CHCl CH CH + HCl

CH2=CHCl + CH CH CH2=CCH=CH2 Cl

GVHD:Ts. NGUYN VN BI

10

Nhm 9

Cng ngh sn xut Viny clorua

CHNG 2: CC QU TRNH SN XUT VC

2.1. Tng quan v sn xut VC Ln u tin VC c tng hp vo nm 1830 1834. Khi V.Rfgnau tng hp n t qu trnh tch axit clohydric ra khi 1,2-dicloetan. Cng thi gian , ng nhn thy rng khi phi nng dung dch VC trong mt thit b kn, cht lng b lng ng thnh cc vy rn. Trong phm vi ca thuyt ho hc hu c v s hiu bit thi gian v VC cha y , nn ng ch c th miu t hin tng m khng gii thch c v sao t trng thi lng li chuyn sang trng thi rn. Nm 1872, nhng tnh cht c bn ca VC c Baumann nghin cu v gii thch. ng m t dng vt cht rn nh Kauprenchlorid v a ra cng thc tng qut nh sau (C2H3Cl)n. Nm 1902, VC li c iu ch t qu trnh cracking nhit 1,2-dicloetan. Tuy nhin, vo khong thi gian nghnh khoa hc k thut tinh vi cha pht trin mnh v phm vi ng dng cn nhiu hn ch. Do cc qu trnh nghin cu su v p dng khoa hc k thut vo trong cng nghip sn xut VC khng c ch ti. Vo nm 1912, Klatte v Rollett a ra phng php iu ch VC bng qu trnh cng hp axit clohydric vo axetylen. Hai nm sau, Griseheim-Elektron s dng HgCl 2 lm xc tc cho qu trnh v thu c hiu sut cao hn. T hai cch iu ch trn ho nghnh sn xut VC c chnh thc ho sn xut v ng dng vo i sng. Tuy nhin, n ch c s dng trong mt phm vi rt nh, Bi v cao su t nhin l ngun sn c, khng phi tri qua qu trnh sn xut, gi thnh li r. Do , n ngn cn s pht trin mnh nghnh sn xut VC. Cho n tn chin tranh th gii th hai kt thc, ngun cao su t nhin gim xung th sn phm ca VC l PVC mi c pht trin rc r cho n tn ngy nay. Nhng do gi thnh axetylen qu cao cn tr ng k ti th trng tiu th cc sn phm ca VC. Trc tnh hnh , yu cu thay th cng ngh sn xut VC i t axetylen t tin bng qu trnh r hn. l mt thch thc ln i
GVHD:Ts. NGUYN VN BI

11

Nhm 9

Cng ngh sn xut Viny clorua

vi cc nh sn xut lc by gi. T nm 1940 1950, khi m kh thin nhin v du m l ngun nguyn liu r tin nn cc qu trnh tng hp trn c s axetylen dn dn nhng ch cho qu trnh tng hp trn c s olefin: etylen. Propylen, butylen. . .V vy m nguyn liu tng hp VC cng c thay th bng etylen. Clo s cng trc tip vo etylen to thnh 1,2-dicloetan, sau tin hnh cracking nhit tch axit clohydric to thnh vinylclorua. Lng axit clohydric thu c t qu trnh ny s em s dng cho qu trnh hydroclo ho axetylen. Dy truyn sn xut VC kt hp c hai qu trnh trn lm gim chi ph cho qu trnh ng thi thu c VC c cht lng cao. Gn y, qu trnh sn xut VC theo con ng oxy-clo ho etylen to thnh 1,2-dicloetan c cc nh phn tch cho l kh thi hn c . Chnh v vy m qu trnh sn xut VC theo cc con ng: clo ho trc tip etylen v oxy-clo ho etylen chin ti 90%VC c sn xut ra. Nhng nm gn y, nhiu nh khoa hc trn th gii tuyn on rng trong tng lai ngun nguyn liu sn xut VC t etylen s c thay th bng etan-ngun nguyn liu sn c. Tt c cc qu trnh nghin cu trn c s etan ang ngy mt hon thin hn . ph nn n vn cha c ng dng vo sn xut. Hin nay, qu trnh sn xut t etylen vn ang gi vai tr chnh trong sn xut VC v khng ngng c ci tin c v dy truyn sn xut ln cht lng ca VC. Tuy nhin cng vi s pht trin khng ngng v khoa hc k thut c bit l s pht trin ca nghnh ng hc xc tc mi . Nn etan c th tr ln hp dn hn trong tng lai. Cc dy truyn cng ngh sn xut VC cng khng ngng c nng cao. T dy truyn sn xut mt qu trnh c thay th bng dy truyn cng ngh kt hp t hai n ba qu trnh. Thit b phn ng lp xc tc c nh d Do hiu sut thu t qu trnh ny cha cao, chn lc cn thp, c nhiu sn phm

GVHD:Ts. NGUYN VN BI

12

Nhm 9

Cng ngh sn xut Viny clorua

c thay th bng thit b phn ng lp xc tc lu ng, lng si. Nng sut thit b cng ngy cng c nng cao. Cng vi etylen v NaOH, vinylclorua l mt trong nhng hp cht quan trng nht trn th gii. Nm 1984, trn ton th gii c khong 12 15 triu tn VC c tiu th. Khong 25% lng clo trn th gii c s dng sn xut VC. Cc c s sn xut VC trc nm 1986 ch yu M v Ty u. Ngy nay do ngun nguyn liu v th trng tiu th mang tnh cht a l nn cc c s sn xut VC c m rng trn ton th gii, c bit u tin nhng vng c ngun nguyn liu di do v th trng rng ln. Sn phm ca VC cng khng ngng c m rng v nng cao. Tm li qu trnh sn xut VC t cc nguyn liu chnh sau: T axetylen. T dicloetan. T etylen. T etan. 2.2. Qu trnh iu ch CV t 1,2di-cloetan 2.2.1 Qu trnh sn xut VC trong pha lng Trong pha lng, ngi ta thng s dng dung dch ru, kim kh HCl ca dicloetan (C2H4Cl2). a.C s ca qu trnh: da vo phn ng chnh sau:
GVHD:Ts. NGUYN VN BI

13

Nhm 9

Cng ngh sn xut Viny clorua

CH2Cl-CH2Cl + NaOH CH2=CHCl + NaCl + H2O Nu d kim th VC s tip tc phn ng vi NaOH to ra axetylen. CH2=CHCl + 2NaOH CH CH + 2NaCl + 2H2O Khi c nc, dicloetan s b thu phn to ra etylen glycol: CH2Cl-CH2Cl + 2H2O CH2OH-CH2OH + 2HCl Nh vy ngoi sn phm chnh l VC, cn c cc sn phm ph nh: ru, kim, axetylen, NaCl, nc, dicloetan d. Hiu sut VC tnh theo axetylen l 75 85%. Thit b phn ng trong cng ngh sn xut VC pha lng l thit b hnh tr kiu ng trc c v bc v cnh khuy. Thit b lm vic gin on. C mt lt dicloetan cn 1,1 lt dung dch kim (42 %NaOH) v 0,26 lt etylic. Do ru ho tan trong kim v dicloetan nn phn ng tin hnh dng ng th. Nhit phn ng l 60 700C, thi gian phn ng l 4 5 gi, p sut 0,2 0,4 at. u tin cho dung dch NaOH ru dicloetan vo thit b phn ng. Nu d qu nhiu kim th sn phm c nhiu sn phm ph khng mong mun. b. u im: Hiu sut kh cao, ch phn ng khng khc nghit lm. c. Nhc im:

GVHD:Ts. NGUYN VN BI

14

Nhm 9

Cng ngh sn xut Viny clorua

Sn phm c sn phm ph l dicloetan, NaCl, HCl, li xy ra trong pha lng do s mt mt Clo khi x l. Qu trnh phn tch ring tng cu t tn nhiu thit b. Dung dch nc thi c cha hp cht Clo gy nh hng n qu trnh x l mi trng. Thit b lm vic gin on, kh t ng ho, dy truyn sn xut c nhiu thit b, kng knh. Ru, kim tiu tn cho qu trnh ny qu nhiu. Do nhng nhc im trn, qu trnh sn xut VC trong pha lng khng kinh t, tn nhiu vn u t, gi thnh sn phm cao. V vy phng php ny t ph bin trong sn xut VC. 2.2.2 Qu trnh sn xut VC trong pha kh Qu trnh dehydroclo ho dicloetan trong pha kh l mt trong nhng qu trnh quan trng v thit thc sn xut VC. N c th tin hnh nhit phn c xc tc hoc khng c xc tc. 2.2.2.1 Qu trnh phn ng khng c xc tc a. C s ca qu trnh: Phn ng xy ra theo c ch chui gc. N c bt u bng phn ng ph v lin kt C-Cl . ClCH2-CH2Cl ClCH2-CH2 + Cl Cl + ClCH2-CH2Cl ClCH2-CHCl + HCl ClCH2-CHCl CH2=CHCl + Cl
GVHD:Ts. NGUYN VN BI

15

Nhm 9

Cng ngh sn xut Viny clorua

to ra gc t do cn mt nng lng ln ph t lin kt C-Cl. Nh vy nhit phn ng phi cao .Khi dicloetan tch ra mt nguyn t Clo to thnh gc ClCH2-CH2n nh. Tuy nhin nhit cao qu s thc y phn ng trng hp to polyme. Do gim nhit ca qu trnh ngi ta thng s dng cc cht khi u d to ra gc t do. trng hp ny thng s dng cc cht cha clo nh tetraclometan, hexancloetan, tricloetan, 1,1-dicloetan. Nhng cht khi u ny c trong nguyn liu khng c vt qu 5%. Nitrometan l cht khi u tt nht, cho hiu sut cao. Nhng do sn phm l VC nn ngi ta thng cho 1,1-dicloetan vo nguyn liu u thc y phn ng. Gc Cl s tng tc vi nguyn liu ban u l dicloetan to ra gc mi. Phn ng s dng li khi tc sinh ra bng tc mt i ca gc t do. S mt cc gc t do c th do cc gc va chm vi nhau, phn ng vi nhau to phn t trung ho. Cng c khi ngi ta s dng cc cht c ch ngn cn s to thnh cc gc t do. Khi cho 110% 1,1-dicloetan trong nguyn liu 1,2-dicloetan, th qu trnh cracking nhit xy ra nhit 450 6500C, p sut 0,1 0,4MPa, mc chuyn ho tt v sn phm to thnh l 95 % . Tuy nhin nguyn liu cng nguyn cht th chuyn ho cng cao. Qu trnh tin hnh p sut cao s thun li hn p sut thp. V p sut cao, s gim kch thc l phn ng, ci tin c thit b trao i nhit, qu trnh phn tch d dng hn. qu trnh ny thi gian phn ng l10 20 giy.

GVHD:Ts. NGUYN VN BI

16

Nhm 9

Cng ngh sn xut Viny clorua

Sn phm ph ca qu trnh l: etylen; axetylen; vinylaxetylen; 1,3butadien; 2-clo1,3-butadien; 1,2-di-cloetylen v 1,1-dicloetan, tricloetan. . Ngoi ra cn c cc, nha. b.Cng ngh Thit b phn ng c trang b bng mt hoc nhiu bung t. Trong l phn ng dc chia ra lm hai phn: +Vng phn ng pha di ca l l vng xy ra qu trnh cracking c nhit cao hn. +Vng bay hi sn phm (vng lnh) pha trn. Khi l phn ng ngng li ly cc, th phi lm lnh sn phm ngay ngn nga phn ng to ra sn phm nng. Trong hu ht qu trnh sn phm c lm lnh trong thit b lm lnh. Nhit to ra c th tn dng un si trong thit b phn tch. Qu trnh tch cc sn phm thng thc hin theo nguyn tc tch HCl trc, tch VC sau. T cc cu t nng s tch ra 1,2-dicloetan. Axetylen s c tch cng vi HCl v bin di thnh VC. 2.2.2.2 Qu trnh phn ng c xc tc. gim s to cc v cc sn phm ph trong qu trnh cracking nhit tch HCl, nhit ca qu trnh phi gim xung. V vy cc nh sn xut tin hnh phn ng dehydroclo ho 1,2-dicloetan khi c mt xc tc. Qu trnh sn xut VC trong pha kh c xc tc xy ra nhit thp 200 4500C, do chn lc to VC cao hn, to cc thp. Tuy nhin mc chuyn ho khng cao hn qu trnh khng c xc tc, thng l 60 70% .

GVHD:Ts. NGUYN VN BI

17

Nhm 9

Cng ngh sn xut Viny clorua

Cc loi xc tc thng dng trong qu trnh ny l silicagel, anilu-kim loi, NaCl, zeolit, ng tan chy hoc cc kim loi khc. Cht xc tc s tng tc vi Cl2 to ra gc t do ban u. Cl2 2Cl

Cl + ClCH2CH2Cl ClCH2CHCl + HCl ClCH2CHCl CH2=CHCl + Cl Cl + Cl Cl2

Hiu sut ca qu trnh ny l 85% . Tuy nhin do qu trnh s dng xc tc t tin. Do n rt tn km trong qu trnh u t, ng thi kt qu thu c cng khng cao hn so vi qu trnh khng c xc tc . Trong thc t qu trnh ny t c s dng hn so vi qu trnh khng c xc tc. Gn y ci tin chuyn ho v cht lng sn phm ca qu trnh sn xut VC trong pha kh ngi ta s dng qu trnh quang ho. Qu trnh quang ho nhm s dng nh sng kch thch thu c t thu ngn, vonfram, tia laze. . . khch thch 1,2-dicloetan tch ra cc gc t do. CH2ClCH2Cl + h (C2H4Cl2)* (C2H4Cl2)* C2H4Cl + Cl Cl + ClCH2CH2Cl ClCH2CHCl + HCl ClCH2CHCl CH2=CHCl + Cl

GVHD:Ts. NGUYN VN BI

18

Nhm 9

Cng ngh sn xut Viny clorua

Qu trnh ny cho chuyn ho cao, chn lc cao, nhit phn ng tin hnh thp hn cc qu trnh trn. Nhng do dy truyn sn xut i hi phi c b phn quang ho rt tn km do n cng t c ng dng rng. 2.2.2.3 u nhc im ca qu trnh sn xut VC pha kh. Phng php ny tt hn phng php sn xut trong pha lng nhng n vn khng c ng dng nhiu trong sn xut VC bi cc nhc im sau: C nhiu sn phm ph, sn phm to ra c sch khng cao gy nh hng xu cho cc qu trnh sn xut sau. Nng sut thp, thit b lm vic gin on. Cng ngh phc tp, rt kh t ng ho trong sn xut. Nhit cung cp cho qu trnh ln, phi s dng cht xc tc v cc cht khi u trong qu trnh, do chi ph sn xut cao, khng thun li v mt kinh t. Thuyt minh dy truyn sn xut: Dicloetan c a vo thit b bay hi phn trn l ng, pha kh tip tc a vo vng nhit phn. Sau khi nhit phn hn hp (a) c a qua thit b trao i nhit (b), ri lm lnh (c). Sau hn hp tip tc c qua thp chng ct (d) tch axit HCl. VC c chng ct ly ra nh thp (e). loi b HCl v EDC, VC tip tc c a qua thp ra kim. EDC sau khi c tch cho qua lm sch ri tun hon tr li. 2.3. Qu trnh sn xut VC t etylen nhng nc c du m ang c thai thc v ch bin, ngun nguyn liu etylen c nhiu rt ph hp vi phng php sn xut VC t etylen. Phng
GVHD:Ts. NGUYN VN BI

19

Nhm 9

Cng ngh sn xut Viny clorua

php sn xut VC t etylen l phng php mi ang c p dng rt rng ri vo sn xut. 2.3.1C s ca qu trnh Do qu trnh clo ho v qu trnh oxi-clo ho etylen l hai qu trnh to nhit cao, nn vic kt hp hai qu trnh ny vi qu trnh cracking nhit l qu trnh thu nhit vo sn xut VC l ph hp nht. Qu trnh sn xut VC t etylen l s kt hp ca ba qu trnh: +Cng hp trc tip clo v etylen to ra 1,2-dicloetan. +Dicloetan thc hin cracking HCl to thnh vinyl clorua. +Oxy clo ho etylen to thnh 1,2-dicloetan. CH2=CH2 + Cl2 2ClCH2CH2Cl ClCH2CH2Cl 2CH2=CHCl + 2HCl

CH2=CH2 + 2HCl + 1/2O2 ClCH2CH2Cl + H2O 2 CH2=CH2 +Cl2 + 1/2O2 2CH2=CHCl + H2O

Vy theo kt qu, t etylen, clo, oxy s nhn c vinyl clorua, trong clo c s dng hon ton v khng to thnh HCl. Nguyn liu u vo ch c etylen, clo v oxi khng kh. Cht xc tc s dng cho qu trnh ny l cc mui kim loi chuyn tip. y thng s dng CuCl2, FeCl3 lm xc tc cho qu trnh. Qu trnh oxi-clo ho etylen thng c tin hnh nhit trn 3500C. Nu nhit cao qu s xy ra phn ng polyme ho to cc sn phm nng hn thm ch to ra cc ( Trng hp VC to thnh polymer vi khi lng ohaa
GVHD:Ts. NGUYN VN BI

20

Nhm 9

Cng ngh sn xut Viny clorua

t ln vi tnh cht ha hc km, khng linh ng, d b vn cc ) v kh hot tnh ca xc tc ( c th cc bm trn b mt xc tc gy cn tr qu trnh xc tc ) gy ra phn ng oxi ho trc tip etylen to ra CO, CO 2. . . lm gim hiu sut sn phm. Lng oxi a vo phn ng phi thp hn lng oxi cn thit trnh xy ra phn ng to CO,CO2. Qu trnh clo ho trc tip to ra VC, HCl v 1,2-dicloetan. Lng d etylen s tip tc c oxi clo ho cng vi HCl to ra 1,2-dicloetan. 1,2dicloetan s b cracking to ra VC. y l qu trnh kt hp hu hiu nht khi khng tri qua mt giai on trung gian no, chng cng tin hnh sng song v b tr cho nhau. Nhit to ra ca hai qu trnh oxi-clo ho v clo ho s cung cp cho qu trnh cracking. Ngoi sn phm chnh thu c l VC, cn c cc sn phm ph khc nh: dicloetylen, tricloetylen, tetracloetylen. Cc sn phm ny c th a i ch bin xu thu c cc cu t qu hn. 2.3.2 Cng ngh sn xut c im ni bt ca qu trnh clo v oxi-clo ho l tnh to nhit nn trong thit b phn ng phi b tr thit b trao i nhit. Thng thng ngi ta s dng thit b phn ng vi lp xc tc gi lng ho tan trong nguyn liu lng. Khi nhit to ra s lm bay hi 1,2-dicloetan v mt phn hi nc ngng t. Thuyt minh dy chuyn cng ngh sn xut VC t Etylen: Trong thit b (1) etylen v clo cho phn ng vi nhau cho pha lng to EDC. Nhit to ra t phn ng c thu hi dng cho qu trnh chng ct (3) thu EDC v dng phn hu EDC thu sau khi lm sch sn phm VC. EDC tinh khit c crcking trong (4) v to VC v HCl. Sn phm i ra t (4) c lm sch ri cho qua thit b chng luyn (6) (7) tch VC v HCl. HCl thu c

GVHD:Ts. NGUYN VN BI

21

Nhm 9

Cng ngh sn xut Viny clorua

t nh thp (6) cho qua thit b oxi ho (2). EDC cha b nhit phn c tch ra t (7) v cho tun hon li (3) VC thu c t (7) rt tinh khit ( nng 99,9% ). Trong thit b oxi clo ho, HCl tun hon kt hp vi etylen v oxi trong thit b tng si to 1,2-Dicloetan v nc nhit sinh ra do phn ng c dng cho chng ct VC v EDC. Sau khi lm sch sn phm phn ng trong (8), nc c loi b, EDC cho qua (10) lm kh v tch kh ri c a qua (3) chng ct lm sch. Kh HCl thot ra t (10) a vo (11) thu hi clo. Ti thit b hydro ho (12) chuyn C2H2 trong HCl t (6) thnh etylen, nng cao sch sn phm v hiu sut ca qu trnh. 2.3.3 u nhc im a. u im Tiu tn t nng lng do tn dng c nhit to ra ca phn ng. Tn dng c HCl to thnh, sn phm thu c khng c HCl. Khng dng axetylen nn chi ph cho qu trnh gim gi thnh sn phm gim t 2530%. b. Nhc im Sn phm thu c c nhiu sn phm ph, chn lc khng cao. Thit b phc tp, iu khin qu trnh kh khn. 2.4. Sn xut VC t etan Etan c nhiu trong kh t nhin v kh ng hnh m khng tri qua qu trnh ch bin no. Ngoi ra n cng c nhiu trong cc qu trnh ch bin du m.

GVHD:Ts. NGUYN VN BI

22

Nhm 9

Cng ngh sn xut Viny clorua

Do n l nguyn liu r tin v sn c, gp phn lm gim gi thnh sn phm vinylclorua. Hin nay c rt nhiu cng trnh nghin cu bin i trc tip etan thnh VC. Etan rt c gi tr i vi cc qu trnh ch bin, c bit i vi khu ch xut vng b bin Ng ca M. N c s dng cho qu trnh cracking to etylen. Nu vic nghin cu bin i etan trc tip thnh VC s gim c phn no qu trnh cracking ng thi gim s l thuc vo nng sut ca qu trnh cracking. 2.4.1C s l thuyt S chuyn ho etan thnh vinylclorua theo cc phng php sau: 1. Clo ho nhit cao:

C2H6 + 2Cl2 C2H3Cl + 3HCl 2. Oxi-hydroclo ho nhit cao.

C2H6 + HCl + O2 C2H3Cl + H2O 3. Oxi clo ho.

2C2H6 + Cl2 + 3/2O2 2C2H3Cl + 3H2O. thc hin cc phn ng trn etan phi tin hnh phn ng th theo c ch chui gc. Qu trnh oxi-clo ho etan thnh VC din ra rt phc tp, i hi ch nhit ng nghim ngt. Vic la chn xc tc cho qu trnh cng rt cn thit. Nu chn xc tc thch hp th s chuyn ho ca etan s rt cao trn 96 % i vi qu trnh oxi ho. Tuy nhin lng sn phm to thnh ch t 20 50%VC.

GVHD:Ts. NGUYN VN BI

23

Nhm 9

Cng ngh sn xut Viny clorua

Etylen, etylclorua, 1,2-dicloetan th c kh ln. Ngoi ra cn c th to ra CO; CO2. Chnh v vy vic a etan vo sn xut VC gp rt nhiu kh khn v mt cng ngh, cng nh v mt kinh t. thu c cc kt qu kh quan hn, cc nh nghin cu kt hp qu trnh clo ho etan v clo ho etylen ngn nga cc sn phm c nhiu clo trong phn t. Tuy nhin hiu sut ca qu trnh cng ch bng qu trnh oxi-clo ho trn.

CH3 CH3 CH3CH2Cl CH2=CH2

CH2=CHCl

CH2Cl-CH2Cl

CH3-CHCl2

CH2=CHCl

ClCH=CHCl

CH2Cl-CHCl2

CH3-CCl3

CH2=CCl2

Qu trnh sn xut VC theo etan tuy cha t kt qu mong mun, nhng n vn c cc nh khoa hc tip tc nghin cu trong phng th nghim tm ra phng php hu hiu p dng vo thc t.

GVHD:Ts. NGUYN VN BI

24

Nhm 9

Cng ngh sn xut Viny clorua

2.5. Phng php lin hp sn xut VC Ngoi cc phng php sn xut VC k trn ngi ta cn s dng phng php lin hp sn xut VC. *Lin hp qu trnh clo ho etylen v qu trnh cracking 1,2-dicloetan. Cc phn ng xy ra trong qu trnh: 2HCl + 1/2O2 H2O +Cl2 CH2=CH2 + Cl2 ClCH2-CH2Cl CH2=CHCl + HCl

Qu trnh ny c th biu din bng s sau:

Phn nh HCl

Phn nng

Thit b

clo ho

Thit b tinh ch EDC

Thit b cracking EDC

etylen

GVHD:Ts. NGUYN VN BI

25

Nhm 9 EDC oxi khng kh HCl

Cng ngh sn xut Viny clorua

Thit b oxy-clo ho
HCl H2O

Thit b tinh ch VCM

VCM

Hnh 2.1 S sn xut bng phng php lin hp Phng php sn xut VC t kh cracking du m. Phng php sn xut VC t nguyn liu ca qu trnh cracking cc sn phm du m ch yu l metan v naphtalen. Qu trnh ny rt thun li khi khng phi tch ring etylen v axetylen. Kh cracking du m gm c etylen v axetylen l nguyn liu trc tip cho qu trnh clohydric ho v clo ho sn xut VC. Ton b axetylen c s dng hon ton cho qu trnh clohydric ho, cn etylen c th d dng dehydro ha to thnh axetylen hoc c a vo b phn clo ho trc tip to ra 1,2-dicloetan. Sau i vo b phn cracking to ra VC. Cc phn ng chnh ca qu trnh l: CH2=CH2 + Cl2 ClCH2=CH2Cl ClCH2=CH2Cl CH2=CHCl + HCl CHCH + HCl CH2=CHCl CH2=CH2 + CHCH + Cl2 2CH2=CHCl Qu trnh ny c ng dng rng ri trong cng nghip v n khc phc c nhc im ca c hai qu trnh sn xut t axetylen v etylen nh:

GVHD:Ts. NGUYN VN BI

26

Nhm 9

Cng ngh sn xut Viny clorua

Phng php t etylen v mt kinh t th thun li hn nhng cht lng khng cao bng axetylen. Phng php axetylen khng thun li v mt kinh t nhng cht lng li rt cao. Phng php ny c ng dng rng ri trn th gii. M qu trnh tng hp VC c phn chia nh sau: 41% axetylen, 28% etylen. Nht phng php lin hp c s dng 25% vo nm 1965.

GVHD:Ts. NGUYN VN BI

27

Nhm 9

Cng ngh sn xut Viny clorua

S cng ngh HCl Naphtalen CH4 racking Hydroclo ho Phn tch VC Clo ho Cracking EDC Clo

VC Hnh 2.2 Sn xut VC t kh cracking du m

GVHD:Ts. NGUYN VN BI

28

Nhm 9

Cng ngh sn xut Viny clorua

CHNG 3: QU TRNH SN XUT VC T AXETYLEN

Phng php sn xut VC t axetylen l phng php ph bin v lu i nht. Ngy nay n thng c p dng ch yu nhng nc c nn cng nghip du m cha pht trin. nc ta tuy nghnh du m c trn 20 nm xy dng nhng c s pht trin mt nghnh cng nghip ho cht cha c c bit l ng dng nhng thnh tu t c trn th gii v cng nghip sn xut VC, hn na nc ta li c tim nng v than v vi, rt thun tin cho sn xut axetylen. 3.1. Nguyn liu ca qu trnh Phng php sn xut VC t axetylen gm c hai nguyn liu chnh l axetylen v axit clohydric. 3.1.1 Axetylen 3.1.1.1Tnh cht vt l Axetylen (CHCH) l cht kh khng mu, khi lng phn t 26,038dvC c mi ete yu khng c nhng c tnh gy m, ngng t -83,8 C (0,102MPa), nng chy -80,85C (101,3kPa), thng hoa -83,5C (101,3kPa), nhit ti hn 35,5C, p sut ti hn 6,04MPa Kh nng ho tan ca axetylen trong dung mi ln hn nhiu so vi nhng hydrocacbon kh khc. ha tan ca axetylen trong nc ph thuc vo nhit , nhit cng ln ho tan cng gim. Tnh cht ha tan ca axetylen trong nc v trong cc dung mi rt quan trng i vi qu trnh vn chuyn, phn tch.

GVHD:Ts. NGUYN VN BI

29

Nhm 9

Cng ngh sn xut Viny clorua

Gii hn phn hy n ca axetylen rt rng. Vi khng kh l 20 81% th tch C2H2 v vi oxi l 2,878% th tch C2H2. 3.1.1.2 Tnh cht ha hc Phn t axetylen cha bo ha v nng lng t do dng cao ca qu trnh hnh thnh, axetylen c kh nng phn ng ngay lp tc vi nhiu nguyn t v hp cht. Phn t axetylen c cha lin kt ba to thnh do lin kt v lin kt . Khi tham gia phn ng ho hc, lin kt ba trong phn t b ph v to thnh lin kt i hoc hp cht bo ho. Axetylen c kh nng tham gia phn ng th, phn ng kt hp, phn ng trng hp. a. Phn ng th Axetylen tc dng vi kim loi nh Cu, Ag, Ni, Hg, Co, Zn,. . .to thnh cc axetylenic kim loi rt d n: CHCH + Na CHCNa + Na Na-CC-Na + H2 . CHCH + Cu Cu-CC-Cu + H2. b. Phn ng trng hp nhit 200 3000C, c bt ng xc tc, axetylen trng hp to thnh Kypren: n CHCH [ -CH=CH- ]n.

Khi thi axetylen qua dung dch bo ho CuCl2 xy ra phn ng dime to ra Vinyl axetylen: 2CHCH CH2=CH-CCH.

GVHD:Ts. NGUYN VN BI

30

Nhm 9

Cng ngh sn xut Viny clorua

Di tc dng ca than hot tnh, axetylen trng hp to thnh benzen. 3CHCH c. Phn ng kt hp - Axetylen tc dng vi H2 cho ta etylen. Phn ng tin hnh trn xc tc Pd p = 1 at v t0 = 250/ 3000 C: CHCH + H2 CH2=CH2 ; H=-41,7 Kcal/mol. C6H6.

- Khi c xc tc oxit km v oxit st 360 4500 C, axetylen tc dng vi hi nc to thnh axeton: 2CHCH + 3H2O CH3-CO-CH3 + CO2 + 2H2

-Khi c xc tc thu ngn axetylen tc dng vi nc nhit 75 1000 to thnh axetaldehyl: CHCH + H2O CH3-CHO ; H=-38,8 Kcal/mol.

- Khi c mt xc tc axit v d nht khi c mt xc tc kim 150 1600 C v p sut 4 10 at, axetylen tc dng vi ru to nn ete: CHCH + R-OH CH2=CHOR

-Axetylen tc dng vi sunfua hydro 1200 C to thnh mt s hp cht cha lu hunh: H2 CHCH + H2S CH2=CHSH C2H5SH (etyl mecaptan)

(Vinyl mecaptan)

GVHD:Ts. NGUYN VN BI

31

Nhm 9

Cng ngh sn xut Viny clorua

- Axetylen kt hp vi clo to thnh tetra cloetan. CHCH + Cl2 CHCl2- CHCl2

-Axetylen kt hp vi hydro clorua to thnh vinyl clorua: CHCH + HCl CH2=CHCl

- Cacbonyl ho axetylen c axit acrylic: CHCH + CO + H2O CH2=CH-COOH

-Axetylen tc dng vi kh oxit cacbon v ru cho ete acrylic: CHCH + CO + ROH CH2=CH-COOR

- Axetylen tc dng vi formandehit 90 950 C v p sut 4 6 at c Butadiol 1,4. Hiu sut t 90 92%, phn ng tin hnh qua giai on trung gian to thnh propalgylic: CHCH + HCHO CHC-CH2OH CHC-CH2OH + HCHO HO-CH2-CC-CH2OH - Axetylen tc dng vi cc axit hu c, c mt xc tc cho ta ete: CHCH + RCOOH 3.1.1.3. Sn xut axetylen Hai ngun nguyn liu tng hp axetylen l than v hydrocacbon. Cc cng ngh tng hp axetylen t than c pht trin t cui th k 19 v th n tr thnh cng ngh truyn thng ca rt nhiu cc quc gia cho ti
GVHD:Ts. NGUYN VN BI

CH2=CH-COOR

32

Nhm 9

Cng ngh sn xut Viny clorua

nm 1940 v ti ngy nay n vn ng vai tr ch yu nhiu nc cha pht trin. Tuy nhin hin nay th cc cng ngh tng hp axetylen t hydrocacbon ang dn chim u th do mt s nguyn nhn sau: Nguyn liu hydrocacbon rt sch so vi than. Cc dy chuyn sn xut d dng t ng ha do gim c s

lao ng v mi trng lao ng t c hi hn rt nhiu. Chi ph cho sn xut thp hn, nng sut cao hn.

Trong cng nghip sn xut axetylen ch yu i theo hai hng chnh: t than , vi v kh t nhin, kh ng hnh. Nc ta do iu kin sn c than , vi , kh t nhin v kh ng hnh nn c th p dng c hai phng php ni trn. a. Sn xut axetylen t than v vi. Phn ng chnh ca qu trnh sn xut ny l: CaO + 3C CaC2 + CO Ch c cha khong 70 80% vi tham gia phn ng v vy trong sn phm lun cha 12 15% CaO Tc dng nc vi cacbuacanxi to ra axetylen v vi ti. CaC2 + 2HOH C2H2 + Ca(OH)2 Nhit to ra khi phn hu cacbua canxi k thut l tng nhit ca phn ng tc dng cacbua canxi vi nc v tc dng vi vi nc: CaO + 2HOH Ca(OH)2

GVHD:Ts. NGUYN VN BI

33

Nhm 9

Cng ngh sn xut Viny clorua

Cacbon s dng trong qu trnh ny c th l cc hoc nguyn liu s dng thng c ln cc tp cht nh MgO, hp cht S, P, Al, Fe,. . . . do xy ra cc phn ng ph: MgO + 3C MgC2 + CO Ca3P2 + 8CO

Ca3(PO4)2 + 8C

Cc tp cht ny kh tch ra khi hp cht phn ng. Ch c th tch mt phn qua vic loi x. Chnh v vy axetylen to thnh lun c ln mt lng hp cht nh: PH3 , NH3 , SiH2 , CH4 , H2 , CO2 , CO ,. . . Lng tp cht ny khng c li cho vic s dng axetylen. Do axetylen to ra phi c tri qua giai on lm sch, c th dng Andehit Cromic trn t nung hoc dng nc Javen lm sch. Sau axetylen thnh phm c ra bng kim trung ho axit v sy kh bng H2SO4 hoc CaCl2. b. Sn xut axetylen t nhin v kh ng hnh Trc chin trang th gii th hai, sn xut axetylen ngi ta ch yu dng nguyn liu CaC2. Trong thi gian gn y, cc nh nghin cu ch bt u nghin cu tron cc phng th nghim vi cc mc ch xc nh iu kin bin i ca Hydrocacbon parafin thnh axetylen. trong khi qu trnh Crcking nhit v nhit phn hydrocacbon sn xut olefin pht trin trong cng nghip. Nh tch lu c kinh nghim c v l thuyt ln thc t ca cng nghip nhit phn nhit cao theo phn ng thun nghch sau: CH4 C2H6 C2H2 C2H2 + 3H2 + 2H2

GVHD:Ts. NGUYN VN BI

34

Nhm 9

Cng ngh sn xut Viny clorua

Cc phn ng ny u l phn ng thu nhit v phn ng tng th tch, cn bng ca chng ch dch chuyn v pha phi khi nhit khong 1000 3000
0

C. Trong thc t vi mc ch tng vn tc phn ng phi cn nhit ln

hn 1500 1600 0C i CH4 v 1200 0C i vi Hydrocacbon lng. Khi nhit phn Parafin, phn ng to thnh axetylen c c ch chui gc. Trong kh thu c, ngoi nhng parafin olefin phn t thp cn c mt lng khng ln bezen, nhm axetylen - metylaxetylen (CH3 -C - CH3) cng nh vinyl axetylen (CH2 = CH - C CH3), diaxetylen (CH-C C-CH) ... Ch bin axetylen bng phng php ny tng i phc tp do xy ra cc phn ng ph ch yu l phn hu C2H2 thnh C v H2. Phn ng ph ny mnh lit nht 10000C v t tc ln 1200 1600 0C ngha l khi t nhit yu cu c c C2H2. Kt qu quan st nhng phn ng lin tip, trong axetylen to thnh b phn hu thnh H2, C (mui than). CH4 C2H2 2C + H2

Ngoi ra trong qu trnh cn c phn ng khng mong mun khc cng to mui C v H2 nh phn ng: CH4 C2H4 C2H6 C + 2H2 2C + 2H2 2C + 3H2

Cng nh cc trng hp khc, vic iu chnh hiu sut iu chnh trung gian c th t c nh s gim mc chuyn ho hydrocacbon u bng cch rt ngn thi gian phn ng. Hiu sut axetylen cao nht khi cc ha xy ra vi mc chuyn ho hydrocacbon ban u l 150 0C v thi gian lu trong
GVHD:Ts. NGUYN VN BI

35

Nhm 9

Cng ngh sn xut Viny clorua

vng phn ng l 0,01giy. trnh s phn ra tip theo ca C 2H2 cn phi ti tht nhanh kh phn ng (phun nc). Khi d nhit s gim nhanh n gi tr m s phn ho C2H2 khng xy ra. C cu ca qu trnh: Khi ch bin nhit hydrocacbon kh hay phn on u, chng ta hiu phn no c cu bin i ca hydrocacbon khc nhau trong nguyn liu nhng ch nhit cao va phi (700 8000 C). Trong khi phn ng to thnh C2H2 li tin hnh nhit cao (trn 10000C) v c cu cng cha c nghin cu c th v th cha c mt l thuyt thng nht v s to thnh C 2H2 khi phn hu nhit hydrocacbon trong khong 1100 15000C. Tuy nhin nhng nghin cu c cho php i n gi thuyt v s thay i c cu cracking khi chuyn ho nhit cao l: Lm chm cc phn ng pht trin mch theo c cu gc t do v lm tng tc qu trnh phn hu kh cu trc phn t. Cc phn ng bc hai to thnh cc sn phm ngng t v to cc xy ra trong khong 900 10000C vi s tham gia ca radican, xong nhit cao li quan st thy phn ng phn hu to thnh H 2, mui cacbon va C2H2. Chng hn khi ngin cu s phn hu metan trn y cacbon t nng n 1500 17000C (cc sn phm to ra nhanh chng c tch khi mi trng phn ng) thy rng sn phm bc mt ca s bin i l etan. iu ph hp vi c cu gi thuyt bi Kale nh sau: CH4 [CH2] + CH4 C2H6 C2H4 [CH2] + H2 C2H6 C2H4 + H2 C2H2 + H2

GVHD:Ts. NGUYN VN BI

36

Nhm 9

Cng ngh sn xut Viny clorua

C2H2

2C + H2

Tm li : Nc ta do c cc m kh vi tr lng ln v thnh phn kh thu c hu ht l parafin nn hiu sut chuyn ho cao. V vy, vic pht trin sn xut axetylen t kh thin nhin v kh ng hnh c trin vng ln. c. So snh hai phng php sn xut axetylen Qu trnh sn xut axetylen t cacbua hydro l qu trnh xy ra theo mt giai on, cn vn u t v chi ph nng lng t hn nhng axetylen thu c long v cn c h thng tch v lm lnh phc tp. Cn i vi qu trnh sn sut axetylen t cacbua canxi: chi ph nng lng in ln, vic vn chuyn khng thun tin, iu kin lm vic nh my rt nng nhc. Tuy nhin, qu trnh ny c uim ln l: axetylen thu c m c, c sch cao (99,9 %) c th dng cho bt c qu trnh tng hp no. Ngoi ra nguyn liu cho qu trnh da trn ngun than di do rt ph hp vi iu kin than nc ta. Chnh v vy sn xut axetylen t than , vi l hng chnh cung cp nguyn liu cho ngnh sn xut VC. 3.1.2 Axit clohydric 3.1.2.1.Tnh cht HCl Hydro clorua l m kh khng mu, mi hc, gy kch thch nim mc, c. Trong khng kh m, hydro clorua kt hp vi nc to khi. Hydro clorua tan mnh trong nc. Hydro clorua dng khan khng n mn kim loi, l mt kh bn nhit, ch b phn u nh nhit trn 15000C. HCl dng nguyn cht l khng mu, t trng d = 1,35g/cm 3, phn t lng bng 36,5. L mt axit in hnh, tc dng vi mi kim loi ng trc

GVHD:Ts. NGUYN VN BI

37

Nhm 9

Cng ngh sn xut Viny clorua

H2 trong dy in ho. y l mt axit mnh, dung dc c nng ln nht khong 35%. Axit HCl mang y cc tnh cht ca mt axit mnh nh: Tc dng vi kim: HCl + NaOH NaCl + H2O Tc dng vi mui: 2HCl + CaCO3 CaCl2 + CO2 + H2O Tc dng vi kim loi: 2HCl + Mg MgCl2 + H2 Tc dng vi axetylen: HCl + CH CH CH2=CHCl 3.1.2.2 Cc phng php sn xut axit HCl ph bin trn th gii - Sn xut t H2SO4 v NaCl: NaCl + H2SO4 2NaCl + H2SO4 NaHSO4 + HCl Na2SO4 + 2HCl

- Phng php Hargreaves: S + O2 SO2

4NaCl + 2SO2 + O2 + 2H2O 2Na2SO4 + 4HCl - Phn ng tng hp t H2 v CL2:

GVHD:Ts. NGUYN VN BI

38

Nhm 9

Cng ngh sn xut Viny clorua

H2 + CL2

2HCl

Phng php thu HCl nh mt sn phm ph ca cc qu trnh clo ho cc hp cht hu c. 3.2. Xc tc cho qu trnh i vi mi qu trnh, xc tc l mt yu t ht sc quan trng, mang li hiu qu kinh t cao. Thng thng ci tin mt qu trnh ngoi ci tin cng ngh ngi ta cn ci tin xc tc. S dng cht xc tc cho php tng tc phn ng t tr s v cng nh khi khng s dng xc tc thnh tr s v cng ln v c th iu khin phn ng theo hng mong mun nh: sn phm c chn lc cao, chuyn ho tng trong khi khng cn mt ch lm vic phc tp, tiu tn nguyn liu v nng lng. Trong qu trnh sn xut VC t axetylen, xc tc l mt yu t quan trng lm tng chuyn ho v chn lc ca phn ng , ng thi n gp phn lm gim chi ph cho qu trnh. Phn ng chnh qu trnh sn xut VC t axetylen l phn ng cng hp axit clohydric vo axetylen. N c th xy ra theo hai giai on sau: +Giai on u: +Giai on sau: HCCH + HCl CH2=CHCl + HCl CH2=CHCl CH3-CHCl2

V vy tng tc phn ng u tin v ngn cn phn ng tip theo xy ra, cn phi la chn mt xc tc c tnh chn lc thch hp. Xc tc Hg2+ v xc tc Cu2+ c cc nh nghin cu cho l thch hp i vi qu trnh ny. Cc loi xc tc ny u c s dng trong c pha kh v pha lng.

GVHD:Ts. NGUYN VN BI

39

Nhm 9

Cng ngh sn xut Viny clorua

Qu trnh xc tc ca mui ng v mui thu ngn c gii thch theo nhiu quan im khc nhau. Mt s quan im cho rng: mui thu ngn tc dng vi axetylen to thnh hp cht trung gian, sau hp cht trung gian b phn hu di tc dng ca HCl, hon nguyn xc tc cho ta vinylclorua: HC CH + HgCl2 ClCH=CH-HgCl CH2=CHCl + HCl + HgCl Quan im khc li cho rng: mui ng v mui thu ngn tc dng vi axetylen to thnh phc cht II, trong cc nguyn t c c in tch dng v c kh nng tc dng vi mono clo, cn Hg2+ s kt hp vi C c in tch m hn.

H+ HCCH + HCl
+

CH-CHCl

CH2=CHCl + Hg2+.

Hg2+

Hg2+

Trong pha lng, xc tc Cu+ l tt nht v n khng b mt hot tnh v t ln tng vn tc phn ng ph cng nc ca axetylen, tuy nhin n li c xu hng lm tng phn ng ph: Trng hp axetylen thnh Vinylaxetylen. Cu 2HCCH CH2=CH-CCH.

GVHD:Ts. NGUYN VN BI

40

Nhm 9

Cng ngh sn xut Viny clorua

ngn nga sn phm ph ngi ta thng cho thm HCl c ho tan mui ng. ng thi trong pha lng Cu + khng b mt hot tnh. Trong pha kh xc tc bng mui ng t c s dng cho qu trnh sn xut VC. Xc tc Hg2+ c nhiu u im hn xc tc Cu2+ : Tng chn lc VC, ng thi tng chuyn ho ca phn ng. N c th xc tc c trong pha kh v pha lng. Trong pha lng xc tc Hg2+ thng dng mui HgCl2 ho tan trong dung dch HCl. Tuy nhin ngoi phn ng c bn xc tc Hg 2+ cn tng tc phn ng hydrat to thnh axetandehit . Do nguyn nhn ny, cng nh s mt hot tnh ca xc tc trong dung dch HCl , ngi ta thng dng n trong qu trnh pha kh nhit 150 2000C, khi dng nhng cht phn ng kh hn. Nhng hm lng tp cht khng ln lm thng nh hn 1%. Trong pha kh n tn ti dng HgCl 2 ngm trn than hot tnh. Khi nng HgCl2/C* tng, hiu sut chuyn ho axetylen thnh VC tng. Bng 1: Hiu sut chuyn ho ca axetylen ph thuc vo %HgCl2/C*

%HgCl2/C * 5 10 20 40

Hiu sut chuyn ho, % 69,6 86,7 92,3 94,9

GVHD:Ts. NGUYN VN BI

41

Nhm 9

Cng ngh sn xut Viny clorua

60

96,8

Nng HgCl2 tng t 5 10% , hiu sut chuyn ho tng nhanh. Nhng nng HgCl2 trn 20% hiu sut chuyn ho tng chm li ng thi thc y qu trnh to nhit mnh lm cho xc tc b nung nng cc b, HgCl2 thng hoa, axetylen tham gia phn ng trng hp bao ph trn b mt xc tc lm gim hot tnh xc tc. V vy trong cng nghip thng dng xc tc HgCl2/C* c nng 10% . Tuy nhin mui thu ngn l mt loa mui c nn khi s dng n cn bo m an ton. Gn y ngi ta ang c xu hng thay th mui thu ngn bng cc mui kim loi khc nh BaCl2, CdCl2. . . 3.3. C ch phn ng C ch phn ng chnh ca qu trnh c th c miu t nh sau: Do phn t axetylen c lin kt ba linh ng, rt d tham gia vo phn ng cng khi gp xc tc HgCl2, Cu2Cl2 l cht rt d to phc chng s tng tc vi nhau v to thnh phc cht trung. u tin phn t axetylen b kch hot bi cation kim loi M+ sau kt hp vi anion Cl- to thnh cht trung gian hu c kim loi, nhng cht ny rt r phn r bi axit.
M+ CHCH ClMCHCHCl MCH=CHCl H+ M+ CH2=CHCl

i vo tng trng hp ta s xt k c ch cho tng trng hp.

GVHD:Ts. NGUYN VN BI

42

Nhm 9

Cng ngh sn xut Viny clorua

3.4. Sn xut VC t axetylen trong pha lng Trong pha lng ngi ta tin hnh thi axetylen v HCl cho qua dung dch xc tc c ho tan thnh phn Cu2Cl2 23% trng lng, NH4Cl 16%c thm CaCl2 ho tan trong axits HCL 12 15%, duy tr nhit 60 650C. Cng c th dng xc tc HgCl2 trong axit HCl nhng nhit tng ln 900C. Phn ng chnh xy ra trong qu trnh l: Cu+ (Hg2+) CHCH + HCl CH2=CHCl

C ch c th c miu t nh sau:
H+ HCCH + HCl
+

CH-CHCl

CH2=CHCl + Cu+ (Hg2+).

Cu+ (Hg2+)

Cu+ (Hg2+)

Ngoi phn ng chnh do phn ng xy ra trong pha lng s c mt lng nc nh c trong dung dch. V vy axetylen rt d cng hp vi nc to andehitaxetic.

GVHD:Ts. NGUYN VN BI

43

Nhm 9

Cng ngh sn xut Viny clorua

CHCH + HOH CH3-CHO Nu s dng xc tc ng c xu hng to lm tng phn ng ph trng hp axetylen thnh Vinyl axetylen. 2CHCH CHC-CH=CH2. Thi gian tip xc gia axetylen v axit clohydric vi xc tc tng c th lm cho s chuyn ho C2H2 gn nh hon ton nhng nng sut ca thit b gim. V vy ngi ta cho thi gian tip xc ngn hn, C 2H2 d s tun hon tr li. Trong cng nghip ngi ta c th tin hnh tng hp VC trong pha lng nh sau: Cho xc tc v 12 15 %HCl vo thit b trc, sau cho C2H2 v HCl vo cng mt lc, nhit phn ng duy tr 60 650C. VC to thnh trong hn hp gm c axetylen, axit clohydric v hi nc. u ra ca thit b a ra b phn ti nc ca thit b lc kh tch HCl. Khi hi nc ngng t s tin hnh lm kh cc kh bng CaCl 2 rn. VC s c ngng t khi lm lnh -200C v i vo thit b phn ly tch axetylen khng ngng t cho tun hon li thit b phn ng. u im: C th tin hnh nhit thp, do d khng ch c nhit , tn t nng lng. Thit b n gin. Nhc im: Tn nhiu nguyn liu v xc tc do mt mt xc tc v nguyn liu trong qu trnh lm vic.

GVHD:Ts. NGUYN VN BI

44

Nhm 9

Cng ngh sn xut Viny clorua

Hiu sut ca qu trnh thp do chn lc khng cao, mc chuyn ho thp hn sn xut trong pha kh. 3.5. Sn xut VC t axetylen trong pha kh. Ta tin hnh cho ng thi cho C 2H2 v kh HCl qua lp tip xc tc rn nhit cao thu c VC. Xc tc dng l HgCl 2 ngm trn than hot tnh. Hin nay c nhiu gi thuyt v c cu phn ng c xc tc, mt s quan im cho rng mui thu ngn tc dng vi axetylen to thnh hp cht trung gian: HCCH + HgCl2 HgCl-CH=CH-Cl

nhit ln hn 1200C, hp cht trung gian km bn tc dng vi kh HCl cho ta VC v hon nguyn xc tc. HgCl-CH=CH-Cl + HCl CH2=CHCl + HgCl2

*C mt s nh khoa hc khc li cho rng phn ng kt hp axetylen vi HCl cng xy ra khi khng c xc tc m p sut cao. HCCH +HCl CH2=CHCl

Phn ng ny l phn ng thut nghch, p sut thng cn bng chuyn v phi tri nhng khi tng p sut cn bng chuyn v pha to VC. * Nh bc hc ngi c N.Koslen li cho rng khi c mt xc tc th axetylen chuyn thnh iso axetylen v iso axetylen kt hp vi HCl cho ta VC.

HCCH CH2=C +

CH2=C HCl CH2=CHCl

GVHD:Ts. NGUYN VN BI

45

Nhm 9

Cng ngh sn xut Viny clorua

Cc gi thuyt hin nay cn ang c cc nh khoa hc nghin cu thm. Ngy nay xc tc c dng rng ri trong cng nghip l HgCl2 10% (trng lng ) ngm trn than hot tnh c th thu c VC c cht lng cao chim 99% trong sn phm to thnh. Cng vi cc phn ng chnh, trong qu trnh cn to ra mt s phn ng ph. Nu d C2H2 s to thnh dicloetan theo phn ng: HCCH + HgCl2 Cl-CH - CH-Cl Hg Hg + Cl-CH=CH-Cl

HCCH + 2HCl ClHg-CH-CH-ClHg HgCl2 + Cl-CH=CH-Cl Cl Cl Nu d nhiu kh HCl cng sinh ra phn ng ph: HCCH + 2HCl CH3-CHCl2 (1,1 - dicloetan)

Nhng yu t nhit , xc tc, tc chuyn ho, t l nguyn liu, cht lng nguyn liu v la chn thit b nh hng rt nhiu ti hiu sut phn ng v cht lng VC to thnh. Nhit thch hp cho phn ng l 1601800C. Khi nhit tng dn n tng tc khuyt tn ca cc cu t vo xc tc lm tng s tip xc v vn tc ca phn ng tng ln. Mt khc ta cng cn khng ch nhit nghim ngt v nu vt qu 2750C th HgCl2 bt u phn hu v 3000C th n thng hoa. Thng th ta lm lnh hon ton vi cc tc nhn lnh l nc di p sut

GVHD:Ts. NGUYN VN BI

46

Nhm 9

Cng ngh sn xut Viny clorua

hoc du lm lnh tun hon lm mt thit b phn ng chnh, m bo nhit n nh ( khng qu 2000C ) t hiu sut phn ng cao nht. Cht lng nguyn liu. Nguyn liu trc khi a vo phn ng cn phi lm sch cc tp cht v tp cht lm xc tc b ng c: H2S + HgCl2 HgS + 2HCl H3P + 3HgCl2 (HgCl)3P + 3HCl Hoc c th tham gia phn ng ph: HCCH + Cl2 Cl2CH - CHCl2 Clo v axetylen to thnh mt hn hp n. ng thi nhuyn liu phi c sy kh v mui thu ngn cng l xc tc cho phn ng to thnh hidrat ho axtylen thnh axetandehit. HCCH + H2O CH3CHO Chnh nhng phn ng ny gy gim hot tnh ca xc tc, dn n hi gian sng ca xc tc gim, lm tng gi thnh sn phm, v vy cn phi lm sch nguyn liu loi cc thnh phn hot cht. Hi axetylen trc khi a vo thit b phn ng c a qua thp cha dung dch K 2Cr2O7, ti y xy ra phn ng xi ho kh loi b H2S, H3P. H2S H3P + K2cr2O7 K2SO4 + + K2cr2O7 K3PO4 + H2cr2O3 H2cr2O3

Do , nguyn liu trc khi da vo phn ng phi t tiu chn sau: Kh C2H2 c tinh khit 99 %.

GVHD:Ts. NGUYN VN BI

47

Nhm 9

Cng ngh sn xut Viny clorua

Hi nc 0,03 % Khng c H2S, H3P. Kh HCl c tinh khit 95 %. Hi nc 0,03 % Khng c O2 v Cl2.

Thuyt minh s cng ngh: Axetylen lm sch trong thng cha (1) v c my nn (2) a vo lu lng k trc khi a vo thit b sy (4) tch m. Trong b khuy trn (4) axetylen c trn vi HCl kh v cho vo thit b phn ng hnh ng (6), nhit trong thit b phn c gi n nh 140 1600C bng du lm mt. chuyn ho axetylen l 97-98 %, kh phn ng c cha 93 % VC, 5 % HCl v 5-10 % C2H2, 0,3 % axetandehit v 1,1-dicloetan. Kh phn cn ko theo mnh hi HgCl2. Kh c lm lnh trong thit b lm lnh v lm sch khi HgCl2 v HCl tip theo trong thit b (7) (8) (9) bng dung dch HCl 20 %, nc v kim c hon lu. Sau kh c sy bng thit b lm sch nc mui. Hn hp sau i qua thit b lm lnh trc khi c phn tch. Trong thp trng ct (11) phn cn rn l 1,2-dicloetan tch trc. Cn phn nh (axetylen v axetandehit) c phn tch thit b (12). Trong s ny, axetylen sau khi c lm sch khu chun b li c lm kh nn kh nng loi nc v tp cht kh trit . Trong khu tch v tinh ch sn phm, phn on nng ca tng thp chng ct c tch ring, khng np lin tc vo thp tip theo nn kh nng tch trit , t tn nng lng, kh cha phn ng c tun hon li thit b phn ng lm tng hiu sut s dng nguyn liu.
GVHD:Ts. NGUYN VN BI

48

Nhm 9

Cng ngh sn xut Viny clorua

S sn xut VC t C2H2

Axetylen

Lm sch

Sy tch m

HCl

kh

Trn Axetylen+HCl

To 140-160oC

Thu c EDC

GVHD:Ts. NGUYN VN BI

49 Sn phm Cracking

Nhm 9

Cng ngh sn xut Viny clorua

Hnh3.1: S sn xut VC t C2H2 3.6. nh gi u nhc im ca qu trnh sn xut VC t axetylen u im: Trong cc phng php sn xut vinylclorua trong cc ngun khc nhau th phng php sn xut VC t axetylen l phng php cho hiu sut cao nht. chn lc ca Vc t t 98 99%. Trong khi , cc phng php khc ch t hiu sut l 90%. Sn phm ph cng rt t ch chim 1%. Sn phm to thnh so vi cc qu trnh khc khng tn km trong qu trnh phn tch v lm sch. Dy truyn thit b n gin. ng dng rt tt cho cc nc c ti nguyn l than v vi, nhng nc c nn cng nghip pht trin cha cao. Nhc im: Nguyn liu axetylen t tin do gi thnh sn phm to thnh qu trnh ny rt cao.

GVHD:Ts. NGUYN VN BI

50

Nhm 9

Cng ngh sn xut Viny clorua

Axetylen rt d gy n, xc tc HgCl2/C* rt c.

GVHD:Ts. NGUYN VN BI

51

Nhm 9

Cng ngh sn xut Viny clorua

CHNG 4 : KT LUN
Ngnh cng nghip ho cht ngy cng pht trin v khng ngng cung cp cho cc sn phm mi cho i sng v cc ngnh khoa hc k thut khc.Qu trnh sn xut Vinylclorua khng nhng cung cp cho nghnh vt liu polyme m n cn l nguyn liu sn xut si ho hc Clorin (si chu n mn ), sn xut cc dung mi hu c, cc hp cht hu c, thuc tr su. . . Vinylclorua ng mt vai tr to ln trong ngnh cng nghip nh vy nn qu trnh sn xut VC c gi tr ht sc quan trng. Trn th gii, cng ngh sn xut VC c nhiu ci tin gim gi thnh sn phm, nhng trong iu kin ca Vit Nam hin nay th cng ngh sn xut VC t axetylen v axit clohydric vn c p dng. V cng ngh n gin, ph hp vi nn cng nghip cn hn ch, ng thi nguyn liu sn xut axetylen t than v vi rt di do. Trong qu trnh nghin cu v tm hiu, em phn no hiu r hn v cng ngh sn xut VC trn th gii v Vit Nam. Trong phm vi thi gian c hn, tm hiu bit cn hn ch nn trong vic lm tiu lun c nhiu thiu st, em rt mong c s ng gp kin ca thy bi tiu lun c hon chnh hn. Em xin chn thnh cm n.

GVHD:Ts. NGUYN VN BI

52

Nhm 9

Cng ngh sn xut Viny clorua

TI LIU THAM KHO

1./ Trng i hc Bch Khoa H Ni B mn tng hp hu c. Ho hc v k thut tng hp hu c. Khoa i hc ti chc, 1974. 2./ Phan Minh Tn. Tng hp hu c ho du, tp I. Trng i hc Bch Khoa thnh ph H Ch Minh, 1994. 3./ Phan Minh Tn. Tng hp hu c ho du, tp II. Trng i hc Bch Khoa thnh ph H Ch Minh, 1994. 4./ K thut sn xut cht do, tp IA. Trng i hc Bch Khoa H Ni, 1978. 5./ Vinyl and alied polymers, Vol 2, 1974. 6./ Hong Trng Ym. Ho hc hu c, tp II. Nh xut bn Khoa hc v k thut 1999.

GVHD:Ts. NGUYN VN BI

53