n mn hc

Quy trnh sn xut Vinyl clorua

M UVinyl clorua u tin c sn xut vo nm 1835 bi Justus Volt Liebig v sinh vin ca ng l Henry. H thu c n bng vic thc hin clorua kp etylen theo phng php ca Hydroxit kali trong Etanol.Vo nm 1912, mt nh ho hc c l Frans, lm vic cho Griesheim- Elektron c cp bng sang ch v mt phng php sn xut vinylclorua t Axetylen v Hidroclorua s dng thu ngn II clorua nh mt cht xc tc. Phng php ny th c s dng rng ri trong nhng nm 1930 n 1940.ng dng ca n ngy cng c s dng rng ri v ngy cng khng th thiu c trong i sng ca con ngi. Do ngnh cng nghip v vt liu polime cng c pht trin. Vinylclo rua c cng thc ho hc l: CH2=CHCl. cho ngnh cng nghip v vt liu polime tn ti v pht trin hn cn phi nghin cu v sn xut ra ngun nguyn liu cn cung cp cho n l rt quan trng, cho nn vic iu ch Vinylclorua to ra mt bc chuyn ln trong cng nghip ho cht.Vinylclorua c ng dng trong cng nghip ch yu c dung lm monome trong qu trnh polime ha tng hp thnh polivinylclorua (PVC), khong 95% tng hp vinylclorua dung tng hp PVC v cc polime khc. PVC l cht do c nhiu tnh cht m ta mong mun nh n nh ha hc cao t b n mn (t b ph hu bi cc axit mnh nh H2SO4, HCl) c kh nng co gin v bn tng i ln, cch in tt khng thm nc, khng b ph hu khi tip xc vi nc v c mt s tnh nng u vic khc. Do c nhng tnh u vic nh vy nn PVC c dung 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 r v cc hp kim t tin.Tng mc tiu th PVC ton cu hin t khong 32 triu tn/ nm. Sn xut PVC ang tng trng tt ti chu do nhu cu xy dng c s h tng cng nh cc nhu cu xy dng khc tng nhanh ca hot ng sn xut kinh doanh PVC v pha chu . Ti y, tc tng trng ca sn xut PVC t khong 7%, gn bng tc tng trng GDP trung bnh ca chu lc ny. Trong khi , d bo sn xut PVC ti M v chu u trong nm ti ch tng di 3%/ nm. V vy, n nm 2010 tng mc tiu th PVC ti chu s ln hn so vi chu u v M.

n mn hcSV: Nguyn T Quang Huy

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Trong nhng nm gn y, nc ta cng ang rt quan tm n vn ny. Gip chng ta c th t ch ng sn xut VC v PVC trong nc, gim bt tnh trng nhp VC nh hin nay. l vic nh my lc du s I Dung Qut ( Qung Ngi) s i vo hot ng vo u nm 2009, sau s l hn lot cc nh my khc nh Nghi Sn (Thanh Ho), Ph Yn, Nhn Hi (Quy Nhn), v trong min Nam.Trn th gii hin nay, cng ngh sn xut VC i t HCl v C2H2 vn c p dng v cng ngh n gin, li ch t vic gim gi thnh s dng nh trc kia yu cu s dng nguyn liu th l hidrocacbon t tin. V s dng cng ngh ny cng rt ph hp vi iu kin Vit Nam v chng ta c ngun nguyn liu axetylen nc ta rt phong ph v c tr lng t nhin ln, ni vi nhiu. Vi nhng iu kin thun li nh vy chng ta s hn ch c ngun nguyn liu VC ngoi nhp nhng vn p ng y nhu cu ca cc ngnh cng nghip trong nc, cng nghip sn xut VC t C2H2 v HCl cn phi c pht trin hn na.SV Nguyn T Quang Huy

MC LCM U1Phn ITNG QUAN5CHNG I: TNH CHT CA NGUYN LIU V SN PHM5I.1 Tnh cht ca nguyn liu5I.1.1 Tnh cht ca axetylen5I.1.2 Cc phng php iu ch axetylen9Tnh cht ca axit HCl12Tnh cht vt l12Tnh cht ha hc12I.2.3 Cc phng php sn xut axit HCl ph bin trn th gii13Tnh cht ca sn phm VC13Tnh cht vt l13Tnh cht ha hc14nh hng ca VC ti sc khe con ngi v mi trng16i vi sc khe con ngi16i vi mi trng16I.4.3 Bo qun VC16CHNG II: CC PHNG PHP SN XUT VC17Cng ngh tng hp VC t Etylen17Sn xut EDC bng qu trnh clo ho Etylen17Nhit phn DEC to VC20Qu trnh Clo ho Etylen22Sn xut VC bng cc qu trnh lin hp24S 124S 2244.S 425II.3 Sn xut VC i t Axetylen25II.3.1 C s qu trnh sn xut VC t axetylen da trn phn ng25II.3.2 C ch ca qu trnh sn sut VC t axetylen25Mt s s cng ngh sn xut VC t C2H2 v HCl xc tc HgCl2/C*: ... 31S cng ngh sn xut VC c in31S cng ngh sn xut VC hin i32II.4.3 So snh cng ngh35

PHN II. TNH TON36III.1 Xc nh thi gian lm vic ca phn xng36III.2 Tnh cn bng vt cht37PHN 3: TNH HNH CA NGNH CNG NGHIP SN XUT VC CAMT S QUC GIA TRN TH GII V VIT NAM.40K hoch sn xut VCM Wilhelmshaven( CHLB c)40Cng ngh sn xut VCM Kerteh( Malaysia)40Tnh hnh sn xut VCM Vit Nam41KT LUN44TI LIU THAM KHO45

Phn ITNG QUANCHNG I: TNH CHT CA NGUYN LIU V SN PHMI.1Tnh cht ca nguyn liu:Tnh cht ca axetylen:Axetylen c tm quan trng to ln nht trong s cc hidrocacbon cha mt lin kt ba. l cht kh khng mu, dng tinh khit c mi ete nh c tc ng gy m. Axetylen cha tinh t iu ch t canxi cacbua c mi kh chu, mi ny c gy ra bi cc tp cht hiro photphua (PH3) v hiro sunfua. Axetylen nguyn cht c v hi ngt.Trng lng ring ( 0oC, P=760mmHg): d=1,17 kg/m3.Trng lng phn t: 26,02 kg/kmol.Nhit dung ring phn t: Cp = 0,402 kJ/kg.Nhit ngng t: - 83,8oCNhit ti hn: 35,5oCp sut ti hn: 6,04MpaNhit thng hoa: 21,59 kJ/molNhit ha hi: 15,21 kJ/molT trng: 0,686Axetylen tan lnh trong cc dung mi hu c, axetylen cng c th tan trong nc. chn lc ca axetylen trong cc dung mi khc nhau rt quan trng trong qu trnh tinh ch cng nh trong qu trnh bo qun axetylen. Khi chy axetylen ta ra lng nhit ln, kh nng sinh nhit ca axetylen l 13,307 kcal/m3, gii hn n ca axetylen xy ra trong cng mt iu kin nhit v p sut nht nh. nhit 0oC v 1 at Axetylen to vi khng kh hn hp n trong gii hn t 23%-81% th tch v gii hn n vi oxy l 2,8% th tch, nguy him v n ca axetylen cng tng do s phn r ca n thnh nhng cht n gin.y l phn ng phn hy ca C2H2 to thnh C v H2. S phn r ny khng c oxi nhng c nhng cht kch hot tng ng(tia la, t chy do ma st).

Axetylen cng d dng to hn hp n vi Clo v Flo, nht l khi c tc dng vi nh sng. Do vy gim bt kh nng n ca axetylen, khi vn chuyn ngi ta pha thm kh tr, hydro amoniac vo.Axetylen cng c kh nng ha tan tt trong nhiu cht lng hu c v v c. ha tan ca n tng i cao trong dung mi c cc. Trong mt th tch nc 20oC c th ha tan c mt th tch axetylen, cn 60oC mt th tch nc axetylen gim trong dung dch mui n v Ca(OH)2. ha tan ca axetylen c ngha quan trng iu ch v tch ra khi hn hp kh.Tnh cht vt l:Axetylen l hidrocacbon khng no, c lin kt ba trong phn t do kh nng hot ng ha hc cao. Lin kt ba phn t axetylen to thnh do lin kt v .Khi tham gia cc phn ng ha hc, lin kt ba trong phn t b ph v to thnh lin kt i hoc cc hp cht bo ha. Axetylen c kh nng tham gia phn ng th, cng, oxy ha, trng hp. V vy t axetylen c th tng hp cc sn phm khc nhau c th ng dng trong cng nghip v i sng.Tnh cht ha hc:Phn ng th:Nguyn t H ca axetylen th hin tnh axit c kh nng tham gia phn ng th vi kim loi kim, Cu, Ag, Ni, Co, Zn to thnh axetylenit kim loi rt d n.2Me C2 H2 Me2C2 H2 ( Me: kim loi kim )HC CH 2 NaNaC CNa H2HC CH 2CuCu C C Cu H2Axetylen tc dng vi amit ca kim loi kim v kim th trongamoniac lng:HC CH MeNH2 MeC CH NH3Phn ng cng hp:Cng vi hydro vi xc tc Pd p sut 1 at v 250-300oC.

HC CH H Pd CH CH ,H 41, 7kcal / mol.222Cng hydro vi xc tc Ni v nhit :HC CH 2H Ni CH CH2to33Phn ng cng vi nc khi c xc tc HgSO4 75-100oC to raaxetaldehyt:HC CH H O Hg CH CHO , H 38, 8kcal / mol23Cn khi c oxit km v oxit st 360 480oC, axetylen tc dng vihi nc to thnh axeton:2HC CH 3H O ZnOCH COCH CO 2H23322Axetylen tc dng vi ru 160 180oC, p sut P = 4 20 at v cKOH to thnh Vinylete:HC CH ROH KOHCH CH OR2+H2SH2SHCCH+H2CCHSHC2H5SHEtylen mercaptanVinyl mercaptan+C2H2H5C2SCHCH22HCCH2+C2H5SHSH5C2SCH2CH2SC2H5Etylen dietyl sulfitAxetylen tc dng vi H2S 120oC:Axetylen tc dng vi mercaptan c xc tc KOH to raVinyltroete:HC CH RSH CH2 CH SHAxetylen tc dng vi CO v H2 ( cacbonyl ha ) vi xc tc l Ni(CO)4 to ra axit acrylic:HC CH CO H2O CH 2 CH COOHCng vi mui halogen to hp cht c ng phn cis, trans:

HHHCCH+HgCl2CCClHgClCisHgClHHClCCTransCng vi halogen:HC CH Br CHBr CHBr Br2CHBr CHBr222Khi cng vi Cl2 trong pha kh xy ra rt mnh lit d gy n, do ta phi tin hnh trong pha lng c xc tc antimonitriclorua.SbCl3 Cl2 SbCl5HC CH 2SbCl5 CHCl2 CHCl2 2SbCl3 Ngoi ra axetylen cn phn ng cng vi nhiu axit v c v hu c to thnh cc vinyl c gi tr trong cng nghip.Cng vi HCl, phn ng trong pha hi 150 180oC c xc tcHgCl2 than hot tnh, cn trong pha lng dng xc tc CuCl2 thuc VC:HC CH HCl CH 2 CH ClCng vi H2SO4 to thnh Vinylsunfua:HC CH H2 SO4 CH2 CH O SO3H nhit 80oC c CuCl2 v NH4Cl lm xc tc, Axetylen tc dng vi HCN to thnh acrylonitrin:HC CH HCN CH2 CH CNTc dng vi axit axtic 180 200oC pha hi l xc tc l axetat Zn trn than hot tnh hoc trn Cd trn than hot tnh hoc Hg trn than hot tnh to thnh Vinylaxtat:HC CH CH3COOH CH2 CHOCOCH3Axetylen tc dng vi ru:OHO HC CH2HC CH+

Axetylen tc dng vi axit amin:CH CH RCO NH 2 RCO NH CH CH 2c.Phn ng trng hp ca axetylen:Phn ng Dime ha trong mi trng HCl to thnh vinylaxetylen2CH CH xt ,80o C H C CH C CH2 nhit 600oC trn than hot tnh axetylen trng hp to thnh benzen:3CH CH C6 H6I.1.2Cc phng php iu ch axetylen:Trong cng nghip axetylen ch yu c sn xut theo hai hng chnh l: t than , vi, kh t nhin, kh ng hnh. Nc ta do iu kin sn c than , vi, kh t nhin, kh ng hnh nn c th p dng c c hai phng php trn.I.1.2.1Sn xut axetylen t than v vi:Phn ng chnh ca qu trnh ny:CaO 3C 600o C CaC CO2Ch c khong 70-80% vi tham gia phn ng v vy trong sn phmlun lun cha 12-15% CaO.Tc dng nc vi cacbuacanxi to ra axetylen v vi ti.CaC2 H 2O C2 H2 CaONhit ta ra khi phn hy cacbuacanxi k thut l tng nhit ca phn ngtc dng ca cacbuacaxi vi nc v tc dng vi vi nc.CaO + H2O Ca(OH )2Cacbon 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 cc phn ng.MgO 3C MgC2 COCa3 (PO4 )2 8C Ca3 P2 8COCc tp cht ny kh tch ra khi hn hp phn ng. Ch c th tch ra mt phn do vic loi x. Chnh v vy m 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 Axtylen iu ch VC. Do Axetylen to ra phi qua giai on lm sch c th dng anhydric cromic trn t nung

hoc dng nc Javen lm sch. Sau Axetylen thnh phm c rabng kim trung ha axit v sy kh bng H2SO4 hoc CaCl2.T metano400600 C C2CHH 3H42 22NiOxi ha Metan:o1500 C 2C4CH OH 2CO 4H422 222Axetylen sn xut theo phng php cacbuacanxi chi ph nng lng in tiu tn v vn u t ln v vn u t cao nn ngy nay axetylen ch yu c sn xut bng nhit phn hydrocacbon, qu trnh xy ra mt giai on cho php tng hp axetylen vi vn u t v chi ph nng lng t hn.Axetylen sn xut c sch hn, nhng c nng long.I.1.2.2Sn xut axetylen t kh thin nhin v kh ng hnh:Trc chin tranh 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 trong cc phng th nghim vi mc ch xc nh iu kin bin i ca hydrocacbon parafin thnh axetylen. Trong khi qu trnh cracking nhit v nhit phn hydrocacbon sn xut olefin pht trin trong cng nghip. Nh tch ly c kinh nghip c v l thuyt ln thc t ca cng nghip nhit phn, cho php pht trin v thit k cc thit b u tin sn xut axetylen t CH4 v nhng parafin khc bng cch nhit phn nhit cao theo phn ng thun nghch sau:2CH C H 3H ,H o 87, 97kcal / kg42 22298C2 H6 C2 H2 2H2 ,Cc phn ng ny u l cc phn ng thu nhit v phn ng tng th tch, cn bng ca chng ch dch chuyn v pha phi khi nhit khong 100 300oC.Trong thc t vi mc ch tng vn tc phn ng cn nhit ln hn 150-1600oC i vi CH4 v 1200oC i vi hydrocacbon lng, khi nhit phn parafin, phn ng to thnh axetylen c c ch chui gc, trong chui chuynha CH4 v C2H6 c th c trnh by nh sau:2H*-2H*2CH2CH *2CH *2CH*324-H2H C -H2 HCCH CHH2CCH233

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Trong kh thu c, ngoi nhng parafin v olefin phn t thp cn mt lng khng ln benzen, nhm axetylen-metylaxetylen ( CH3-CH2- CH3), Ch bin axetylen bng phng php tng i phc tp do xy xa cc phn ng ph ch yu l phn hy C2H2 thnh C v H2. Phn ng ny mnh litnht 1000oC v t tc ln 1200 1600oC ngha l khi t nhit yucu c c C2H2. Kt qu quan st nhng h phn ng lin tip, trongaxetylen to thnh b phn hy thnh H2 v C (mui than ).2CH 3H2C H 2C H42 22Ngoi ra trong qu trnh cn xy ra nhng phn ng khng mong muncng to thnh C v H2 nh phn ng:CH 4 C 2H 22C H 2 H2 C H 2C 2H2 42 42C2 H6 2C 3H 2Cng nh cc trng hp khc, vic iu chnh hiu chnh hiu sut sn phm trung gian c th t c nh s gim mc chuyn ha hydrocacbon ban u bng cch rt ngn thi gian phn ng. Hiu sutaxetylen cao nht khi s cc ha xy ra vi mc chuyn ha hydrocacbon ban u l 150oC v thi gian lu trong vng phn ng l 0,01 giy. trnh s phn r tip theo ca C2H2 cn phi ti tht nhanh khi phn ng (phun nc). Khi nhit gim nhanh n gi tr m s phn r C2H2 khng xy ra.+ C ch ca qu trnh:Khi ch bin nhit hydrocacbon kh hay phn on du, chng ta hiu phn no c cu bin i nhit ca hydrocacbon khc nhau trong nguyn liu nhng ch iu kin nhit va phi ( 700 n 800 0C) trong phn ng to thnh C2H2 li tin hnh nhit cao ( trn 1000 0C) v c cu cng cha c nghin cu c th,v th cha c mt l thuyt thng nht v s to thnh C2H2 khi phn hy nhit hydrocacbon trong khong 1100 1500 -0C. Tuy nhin nhng nghin cu cho php gi thuyt i n s thay ic cu cracking khi chuyn ha nhit cao lm chm cc phn ng pht trin mch theo c cu gc t do v lm tng tc ca qu trnh phn hy 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 1000 0C, song nhit cao li quan st thy phn ng phn hy to thnh Hydro, mui, cacbon t nng n 1500 1700 0C ( 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 c gii thch bi c cu Kasale nh sau:CH 4 CH 2 H2CH 2 CH4 C2 H6 C2 H6 C2 H4 H2 C2 H4 C2 H2 H 2 C2 H2 2C H2Tm li, nc ta do c cc m kh vi tr lng ln v thnh phn ca kh thu c hu ht l parafin nn hiu sut chuyn ha cao. V vy vic pht trin sn xut axetylen t kh thin nhin v kh ng hnh c trin vng rt ln.I.1.2.3So snh hai phng php sn xut AxetylenQu trnh sn xut Axetylen t hydrocacbon l qu trnh xy ra theo mt giai on, cn vn u t v 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 xut axetylen t cacbua canxi : chi ph nng lng ln ( cho vic thu c CaC2 ) v vn u t cho sn xut ln, vic vn chuyn khng tin, iu kin lm vic nh my rt nng nhc. Tuy nhin qu trnh ny c u im 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 s dng cho qu trnh da trn than rt di do v rt ph hp vi iu kin nc ta. Chnh v vy, sn xut axetylen t than , vi l hng chnh cung cp nguyn liu cho VC.I.2Tnh cht ca axit HCl: I.2.1Tnh cht vt l:Hydro clorua l mt kh khng mu, mi hc gy kch thch nim mc, rtc. Trong khng kh m, HCl kt hp vi hi nc to khi, HCl tan mnh trong nc, n dng khan khng n mn kim loi, l mt kh bn nhit ch b phn hy nh nhit trn 15000C.I.2.2 Tnh cht ha hc:HCl dng nguyn cht l khng mu, t trng d= 1,35g/m3, c phn t lng bng 36,5. L mt axit mnh dung dch 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 + HOHTc dng vi mui:2HCl + CaCO3 CaCl2 + HOH + CO2Tc dng vi kim loi:2HCl +Mg MgCl2 + H2Tc dng vi axetylen:HCl + CH CH CH2 =CHCl Cc phng php sn xut axit HCl ph bin trn th gii:Sn xut H2SO4 v NaCl:NaCl + H2SO4 NaHSO4 + HCl 2NaCl + H2SO4 Na2SO4 +2HClb. Phng php Hargreaves:S + O2 SO24 NaCl + 2SO2 +O2 +2H2O 2NaSO4 +4HClc. Phn ng tng hp H2 v Cl2:H2 +Cl2 2 HClPhng php thu HCl nh l mt sn phm ph ca mt qu trnh cho cc hp cht hu c3Tnh cht ca sn phm VC: I.3.1Tnh cht vt l :+ VC c cng cng thc phn t C2H3Cl+ Cc tn gi: Vinyl clorua, cloruaetylen, Etylen monoclorua, VC, VCM, Cloroeten, Monocloroeten, Monocloroetylen..+ iu kin nhit v p sut thng VC l cht kh khngmu, c mi ete nh.Trng lng phn t: M =62,5 kg/mol.Nhit ng rn: -153,7 0CNhit ngng t: -13,9 0C nn rt kh ha lngNhit ti hn ca VC: 142 0CNhit bc chy: 415 Kcal/kgNhit nng chy: 18,4 Kcal/kg

Nhit bc hi 250C Trng lng ring Nhit to thnhNhit trng hp::::78,5 Kcal/kg0,969 g/ cm3-83 8 Kcal/kg-366 5 Kcal/kgNhit dung ring ca VC lng 250C Nhit dung ring ca VC hi 250C Kcal/kg. H s khc x ca VC lng : n0 = 1,83.: 0,83 Kcal/kg. :Cp =0,207T trng: Cng thc thc nghim tnh t trng ca VC lng c xc nh nh sau:d= 0,9471 -0,176.102.t 0,324.105.t2.Trong : d: t trng ca VC lng, g/cm3t: nhit ca VC lng, 0CBng 1 : T trng ca VC ph thuc vo nhit p sut hi: Cng thc thc nghim tnh ap sut hi ca VC l:lgP = 0,8420 - 1130, 9 + 1,75 lgT -0,002415.TTTrong :P: p sut hi ca VC, atT: nhit hi ca VC, 0C Ta c bng sau:+ tan trong nc 1 axetandehit l 0,5 % trng lng.+ Gii hn nng n ca hn hp vi khng kh l t 3,62 - 26,6% th tch.I.3.2Tnh cht ha hc:--VC c cng thc ha hc : CH2 = CHClCng thc cu to ca VC:HHCCHC l

Nhit (0C)-1525

T Trng0,97300,9014

Nhit (0C)-87,50-55,8-13,3716,246,8

p sut(mmHg)1010076022585434

n

Do c cha lin kt i v nguyn t clo linh ng ( Cl c m in ln) nn cc phn ng ha hc ca VC l phn ng ca lin kt i v phn ng ca nguyn t clo linh ng.VC khng tan trong nc, tan trong cc dung mi hu c nh axeton, ru etylic, hydro cacbon thm, hydro cacbon mch thng.Trong phn t VC c mt lin kt ni i v mt nguyn t clo linh ng, do phn ng ha hc ch yu l phn ng kt hp hoc phn ng ca nguyn t clo trong phn t VCSau y ta xem xt cc phn ng m VC c kh nng tham gia :I.3.2.1 Phn ng ni i:Phn ng cng hp:Tc dng vi halogen cho ta 1,2 dicloetan iu kin mi trng kh 140 150 0C hoc 80 0C v c chiu sng xc tc l SbCl3 Khi c xc tc AlCl3, FeCl3 th VC phn ng vi HCl.CH2 = CHCl + HClClCH2-CH2ClVi H2:CH2 = CHCl +H2 CH3 CH2ClTrong phn ng vi oxi ha VC nhit 50 150 0C c mt HCl ddng to ra monoxetandehit:CH2=CHCl + O2 Cl-CH2-CHODo phn t c cha ni i nn VCto PVC, mt sn phm quan trng.c th tham gia phn ng trnghpn H2CCHClCH2 CHClI.3.2.2Phn ng ca nguyn t Clo:Thy phn:Khi un nng vi kim HCl b tch ra khi VC cho ta axetylen.2CH CHCl NaOH CH CH NaCl H O22Tc dng vi acolat hay phenolat cho ta este VC:CH2=CHCl+RONa CH2 =CHOR + NaClTo hp cht c kim:CH2 =CHCl + MgCH2=CH-Mg-Cl

VC trong iu kin khng c khng kh 450 0C c th phn hy to thnh axetylen v HCl, do phn ng dime ha axetylen c th phn ng tip tc to ra mt lng nh 2-Clo-1,3-butandien. Cn trong iu kin c khng kh VC b oxi ha hon ton to thnh CO2 v HClnh hng ca VC ti sc khe con ngi v mi trng:i vi sc khe con ngi:Cng nhn trong cc khu cng nghip s dng hoc sn xut VCM c nhng ri ro khi tip xc vi n. Ngi s dng c th b nh hng VCM qua khng kh trong cc sn phm v trong qu trnh s dng sn phm, trong cc cht thi cha VC hoc qu trnh Clo ha khc. VC xm nhp vo c th con ngi qua khng kh v ngun nc bn m con ngi s dng.Khi ht phi mt lng ln VCM d dn n hn m, nh hng c quan h hp, to ra s bin i ln trong c th v dn ti t vong. mc thp, dn ti triu chng nhc u, hoa mt chng mt. nh hng trong thi gian di c th l nguyn nhn gy bt lc, ri lon tim mch v nhng vn khc nh hng ti s sng. Vin nghin cu ung th th gii phn loi VC nh l mt cht gy ung th ngi, da trn c s biu hin bnh c ngi v ng vt.i vi mi trng:VC xm nhp vo khng kh trong sut qu trnh sn xut v s dng. trong khng kh n s ph v cc lin kt ha hc khc nh formyl clorua v formaldehyt trong 2 ti 3 ngy. Mt d hu ht VC lan ta trong khng kh, khi pht ra t t n cng s bc hi hoc ngm vo trong nc cc mch nc ngm. N s nhanh chng bc hi nu lng hi nc tip xc vi n t. trn b mt nc n c th khng b vi khun phn hy v tn ti trong nhiu thng ti nhiu nm.Bo qun VC:Trc y, VC c bo qun v vn chuyn vi s c mt ca mt lng nh phenol c ch phn ng polyme ha. Ngy nay VC c sn xut vi tinh khit cao v khng cn cht c ch trong bo qun ng thi do c lm sch nc VC khng gy n mn c th c bo qun trong cc thng thp cacbon thng.

CHNG II: CC PHNG PHP SN XUT VCII.1Cng ngh tng hp VC t Etylen:C2H4 r hn C2H2 t 2 n 3 ln. Cc qu trnh gn y u p dng cng ngh Clo ho hay oxyclo ho C2H4 hay p dng c 2 qu trnh ny sn xut 1,2-EDC sau s cracking 1,2-EDC tng hp VC.Sn lng VCM trn th gii c sn xut t 1,2-EDC l ch yu, mtphn nh i t C2H2.II.1.1Sn xut EDC bng qu trnh clo ho Etylen:EDC l 1,2-etylendiclorua ( d204=1,253; trng lng ring 68,0/39,2; to0 onc=35,3 C; t s=-83,7).Khong 85% sn xut VCM, 10% sn xut cha Clo nh 1,1,1-triclo etan, cn li sn xut etylen diamin dng lm cht c ch, sn xut cao su chu xng du nh (CH2-CH2-S4-)nII.1.1.1iu kin sn xut:Phn ng chnh l phn ng sau y, y l phn ng to nhit:CH CH Cl CH Cl CH Cl ,H0= -185kJ/mol.22222298Qu trnh ny c th c thc hin giai on lng hoc hi v chn lc vi s c mt ca xc tc trn ca s clorua kim loi. Trong y Clorua st l xc tc tt cho qu trnh thc hin pha lng.Trong cng nghip ngi ta thng tin hnh pha lng trong khong nhit 500C-900C v p sut thp ( 0,3.106-0,5.106 Pa ). Nhit phn ng c xc nh da vo phng php sn xut EDC: 50-60oC nu phn ng trng thi lng, cn nu thc hin pha kh th nhit 850C-900C.Xc tc FeCl3 c phn cc bng cc thit b hin i, da vo kh nng phn cc ca Clo, tn cng vo ni i ca Etylen.FeCl Cl FeCl...Cl 324FeCl ...ClCH CH FeCl CH Cl CH Cl422322 trng thi lng, FeCl3 c th thm vo giai on trung gian.Sn phm ph ca qu trnh l 1,1,2-tricloetan nhng nhit cao, cloetan v cloetylen cng c th to thnh. S c mt ca oxy trong nguyn liu Clo l mt tp cht c bn bi v n hn ch cc phn ng t

do xut hin nhng phn ng t pht, v ci tin ph hp vi chon lcca EDC.II.1.1.2 Dy chuyn cng ngh sn xut:* Nu s bin i nhit trong khong 50-60oC (tin hnh pha lng):Kh giu Clo v Etylen c a vo trong thit b phn ng chnh(1). Hi nng to ra t thit b tng ng vi nhit c iu khin, kt hp vi s phn tn ca kh tng ng, t c bng phng php tc ng bn ngoi tun hon ca phn ct phn on trung gian ny v qua thit b trao i nhit. Sn phm ly ra trong hn hp c a ti thit b phn chia kh lng(2) (lm vic p sut kh quyn trong mi trng kh tr N2 ) ngn chn s bng n nguy him.Thnh phn ca kh thu c s c a vo thit b phn ng cui(3). Ti y n s phn ng vi C2H4 , sn phm thu c s c quay li mt phn v thit b phn ng chnh (1) , thit b trung gian v mt phn ho tan xc tc FeCl3.Thnh phn ca lng thu c t thit b phn chia (2) c a qua thit b trao i nhit v vo thit b n nh (5). Ti y cc kh cn li s c tch ra v c un nng bi l nung (6).EDC th c tinh ch ti 99% trng lng. iu ny c th t c bng cch thm nc nhm to iu kin d dng cho s phn chia FeCl3 ti thit b (7). Pha lng thu c pha trn. C th tinh ch mt lng nh EDC phn hu, cha trong pha lng, bng s ct phn nh v tun hon li kt hp vi lp hu c pha di giu EDC. Pha ny c trung ho vi NH3 sau c lm kh bng thit b chng ct hn hp khng ng si (khong 15 a)(10). Vi lng EDC thu c nh s c ngng t dng hi lu v sau phn chia phn ct cui nng (khong 15a). Cc sn phm nng nh tricloetan, percloetan, etylenclorua, v EDC c th c phn chia v cng c th c s dng nh l nhng dung mi trong thp chng khng (p sut tuyt i 7 kP v 20 a ).

Hnh: Cng ngh Clo ho nhit thp1- Thit b phn ng chnh7- Thit b ra lng 2- Thit b phn li kh lng8-Thit b trung ho 3- Thit b phn ng cui9- Ct chng tchThng chun b xc tc10- Thit b tch ncThit b n nh11- Thit b tch phn cnL nung12- Thit b thu hi EDC* Nu s bin i nhit trong khong 85oC-90oC (tin hnh phakh):Vi nhit ny th gn nhit im si ca EDC do cc sn phm ly ra t thit b trung gian pha hi. Qu trnh sn xut ny rt thun li l trnh c s cun tri xc tc, cho php bc hi nng bng phn ng bi b phn bay hi, v n gin ho b phn lp t. Thit b phn ng kt hp vi ct hi lu ti thit b chnh. Pha lng c gi li v ng thi phn chia tun hon cc sn phm nng, c lm sch t dng ly ra (75- 80% trng lng EDC). Phn ct cha kh cn li c un nng v phn ct cn li EDC th c n nh bi thit b chng ct, trong khi phn ct thu c nh c thu vo phn ct ngn.Qu trnh ny hin ang c pht trin v c ngh ly FeCl3 bng phng php hp th trn oxyt nhm hoc than hot tnh trnh hao ht sn phm. Da vo phng php ny hu ht cc thit b lm bng thp Cacbon.

Pht minh chnh l cc hng: Dow, Ethyl, Goodrich, Hoechst, Huls, Mitsui, Toasu, Monsanto, PPG,Hnh: S sn xut EDC bng cch oxy ho etylen nhit cao1- Thit b phn ng4- Thit b n nh 2- Ct hi lu5- L nung 3- Thng chun b xc tcII.1.2Nhit phn DEC to VC: II.1.2.1iu kin bin i chung:Qu trnh ny c tin hnh da trn phn ng phn hu thu nhit sau:CH Cl CH Cl CH CHCl HCl H0298 = +70kJ/mol.222Phn ng bt u xy ra 300oC, p sut kh quyn, nhng phn ng t c tc cao 400-550oC. Phn ng xy ra theo c ch gc nh sau:Khi mo:ClCH CH Cl ClCH * CH 2 Cl*222Pht trin mch: Cl* ClCH CH Cl ClCH * CHCl HCl222ClCH * CHCl CH CH Cl Cl* 222t mch:Cl* ClCH * CH CH CHCl HCl222Qu trnh to nhiu sn phm ph: l cc sn phm ca qu trnh polyclo ho, sn phm ca qu trnh phn hu, ccdo vy cn s dng cc cht xc tin nh Clo, Brom, Iot, Tetraclocacbon, hoc oxy to thun li cho phn ng chuyn ho chnh.

20

Cc qu trnh trong cng nghip c tin hnh 500-5500C, p sut 2,5-3Mpa, khng s dng xc tc. Mt s h xc tc ( than hot tnh, mui Clo kim loi) c th s dng gim nhit phn ng, tuy nhin thi gian sng ca xc tc thp v cc kh khn v mt cng ngh lm cho cc qu trnh cracking EDC c xc tc khng c ng dng trong cng nghip.II.1.2.2Sn xut cng nghip:Dicloetan c bc hi v gia nhit n 215oC, sau c a vo thit b phn ng l ng ( lm vic theo nguyn tc tng t qu trnh steam cracking). Ti vng i lu, nguyn liu c gia nhit ti nhit phn ng, phn ng thc s xy ra trong vng bc x. Sn phm kh thu c u ra ca thit b l ng c nhit 5000C c ti trnh cc phn ng ph xy ra ni tip bng cch a qua thp ti tip xc vi dng sn phm c lm lnh xung 50oC chy ngc chiu. Kh sn phm s c lm lnh xung 200C. Trong qu trnh lm lnh b sung tip theo s lm ngng t hu ht cc nguyn liu EDC cha phn ng, mt phn s c dng lm cht ti nhit trong thp ti.Phn cn li ca kh khng ngng s c a vo thp chng ct cthit k thc hin cc nhim v sau:Tch sn phm ph HCl dng kh ( thp 20 a )Sn xut VC th ( Thp 60 a )Tinh ch VC ( 15 a ) gim hm lng HCl t 500 xung10ppm v trung ho sn phm vi NaOH.Thu hi EDC cha phn ng t phn on nng ca qu trnh sn xut VC th, tun hon li thit b phn ng. Qu trnh ny bao gm cc thit b sau:+ Tch phn on nh ( 70-75 a)+ Tch phn on nng trong 2 thp: phn ln EDC thu c trong thp th nht lm vic p sut kh quyn ( 20-25 a), phn EDC cn li trong sn phm nng c thu thp th hai lm vic trong chn khng ( 70 kPa, 25 a ).S hot ng ny cn phi cung cp mt lng xt nng ( 6% trng lng ) trong phm vi 150oC, 106 Pa p sut tuyt i theo phn ng sau:CH2Cl CH2Cl NaOH CH2 CHCl NaCl H2O

Ngy nay ngi ta s dng cc thit b to nhit dng ng, l cc ng rng ( nh hng: Allied, BASE, BP, Goodrick, Hoechst, Huls, Knapsack, Kurela, PPG ( qu trnh Pittsburgh Plate Glass Company, Solvay, USSR) hoc c b sung xc tc ( SBA) v t vo l.Hnh: sn xut VC bng phng php Cracking EDCII.1.3Qu trnh Clo ho Etylen:y l quy trnh ca Cng ty EVC sn xut etylen iclorua (EDC) t etylen v clo. Quy trnh ny c hiu qu nng lng cao v s dng nhit phn ng lm bay hi EDC, nh c th tinh ch sn phm bng chng ct phn on. Khc vi nhng quy trnh khc nh quy trnh LTC, quy trnh ny khng cn dng nc ra sn phm loi b clorua st (III), v vy khng cn x l nc thi.Nhit to ra trong qu trnh tinh ch cc dng EDC khc, nh EDC trong nh my VCM cn bng hoc EDC sn sut theo quy trnh oxy - clo ha, nh tiu th hi gim ng k.II.1.3.1M t quy trnh:Thit b phn ng c thit k c o vi mt thanh ch U ni vi bnh tch lng - kh nm ngang. Cc kh phn ng c np vo y ca thanh ch U ny, ti y chng c ha tan v lin kt vi nhau di p sut tnh ln ngn nga s si trong vng phn ng. Trn vng ny, nhit phn ng to ra cc bong bng hi ni ln trn v i vo bnh phn ng

nm ngang. S chnh lch mt trong hai nhnh ca thanh ch U mbo s tun hon t nhin ca EDC.Hnh : S sn sut VC kt hp 2 cng ngh sn xut EDCThit b Clo ha6- Thit b chng ctThit b chng ct7- Thit b tch VCThit b lm sch EDC8-Thit b Clo hoThit b Cracking9- Thit b oxi clo hoThit b lm lnh10- Thp ra 11- Thit b lm khII.1.3.2u im:Cc u im chnh ca quy trnh HTC l:- Tit kim nng lng: lng hi tiu hao thc trong nh my cn bng c th gim 0,8 tn /tn VCM.- Sn phm sch: EDC sn xut theo quy trnh ny c th c s dngtrc tip trong l phn ng cracking hoc bn ra ngoi.- an ton cao: Cng ty EVC pht trin h thng iu khin v bo v chc chn, c kh nng x l tt c cc nguy c bit.

- Hiu qu s dng nguyn liu cao: thit b phn ng ca quy trnh HTC chuyn ha cc kh nguyn liu etylen v clo thnh EDC sch vi hiu sut chuyn ha t 98,5% v 99,0% tng ng.Thit k c th nghim tt, ng tin cy: thit b phn ng HTC khng c cc b phn chuyn ng, c ch to t cc vt liu c chn lc tt, biu th tui th vn hnh cao v nhu cu bo dng thp.Lng nc thi gim: khng cn ra sn phm EDC sn xut theoquy trnh ny, v vy lng nc thi cn phi x l gim. Ngoi ra, mc tiu th xt cng rt thp.II.2Sn xut VC bng cc qu trnh lin hp:1.S 1: Ch dng ngun Clo l HCl, kt hp vi oxiclo ho vi nhitphn EDC:HCl 0,62Etylen 0,51Oxi 0,301,2 Dicloetan1,64HCl 0,61Vinyl Clorua 1,002.S 2: Kt hp Clo ho vi Oxiclo ho v nhit phn EDC:3.S 3: Kt hp Clo ho vi Oxiclo ho v nhit phn EDC, tn dngnhit phn ng Clo ho tinh ch EDC ca Oxiclo ho:

Oxiclo hoNhit phn

1,2 Dicloetan4. S 4: Kt hp Oxiclo ho vi nhit phn EDC, dng nguyn liuban u l 1,2-EDC:1,2 Dicloetan0,82Etylen 0,26Vinyl Clorua 1,000,82Oxi 0,15HCl 0,61II.3Sn xut VC i t Axetylen:II.3.1C s qu trnh sn xut VC t axetylen da trn phn ng:Phn ng:CHCH + HCl CH2=CHClH298 24, 6kcal / mol p sut thng khng c xc tc, phn ng khng tin hnh do vy khi khng c xc tc ta phi tin hnh p sut cao, nhng p sut cao cc sn phm ph to ra nhiu ( 1,1-dicloetan v VC b trng hp) nhng sn ph ny khng c li cho vic thu sn phm cng nh bo qun thit b. Do trong sn xut ngi ta phi dng xc tc.Sn xut VC i t axetylen c th tin hnh pha lng hoc pha kh.II.3.2C ch ca qu trnh sn sut VC t axetylen:Phn ng cng HCl v axetylen c trng cho lin kt ni ba:CH CH HCl CH CHCl , H 112,4(kJ / mol)2Theo ta nhit n vt tri hn ba ln so vi phn ng hydro clo ha olefin. N c chiu ngc li cht t, nhng khi gim nhit cn bng hon ton dch chuyn v pha phi. Hng s cn bng khi to VC:Kcb( 200oC) = 8.104Kcb( 300oC) = 7.102Qu trnh cng HCl vo axetylen xy ra lin tip to VC v 1,1- dicloetan:CH CH HCl CH CHCl HCl CH CHCl232V vy hidroclo ha axetylen c thc hin khi c xc tc chn lc, n lm tng vn tc giai on u tin. Xc tc cho mc ch ny l mui Hg+v Cu2+.Hg2+Trong , muingi ta dng clorua thy ngn (HgCl2) ngoiphn ng c bn n cn tng tc phn ng hydrat ha axetylen to thnh

Oxiclo hoNhit phn

axetandehyt. Do nguyn nhn ny ngi ta dng n cho qu trnh pha kh 150-200oC, khi dng nhng cht kh hn. Tng t nh axetandehyt ( dotp cht m khng ln lm ) v 1,1-dicloetan c to thnh khng qu 1%.Cu2+i vi pha lng tt nht l dng muiv n khng b mt hottnh v tng mc ca phn ng cng nc ca axetylen. Xc tc l dung dch CuCl2 trong HCl c cha mui clorua amon. Khi c CuCl2 qu trnh ph dime ha axetylen cng tng v to thnh vinylaxetylen.Tc ng xc tc ca mui thy ngn v ng vo phn ng hydroclo ha c gii thch bng s to thnh nhng phn ng phi hp trong axetylen b kch hot v tc dng vi amoni clo v cht trung gian thu c trng thi chuyn i vi lin kt cacbon hoc nhng hp cht hu c chng b phn gii axit.V s to thnh ng thi t nhiu ca nhng phc khng hot ng viHCl( hoc anion clo), s to thnh ca VC trong pha kh c m t theo phng trnh ng hc sau:PC 2 H 2 .PHCl1 b.PHClR KSn phm thu c l VC. N l mt monome quan trng dng nhiu tng hp cc vt liu polime khc. Khi polime ha c mt peroxit n to raPVC.II.3.2.1Sn xut VC t axetylen theo phng php pha lng:Trong pha lng ngi ta tin hnh thi axetylen v HCl cho qua dung dch xc tc c ha tan thnh phn: Cu2Cl2 23% trng lng, NH4Cl 16% trng lng c thm CaCl2 ha tan trong axit HCl 12 15% duy tr nhit 60 65% . Cng c th dng xc tc Cu c xu hng lm tng phn ngph nh trng hp trng hp axetylen thnh vinylaxetylen.2CH CH Cu HC C CH CH2 ngn nga phn ng ph phi dng HCl c ha tan mui ng. Tc dng xc tc ca mui ng v mui thy ngn c gii thch theo nhiu quan im khc nhau. Mt s quan im cho rng mui thy ngn tc dng vi axetylen thnh hp cht trung gian. Sau hp cht trung gian bphn hy di tc dng HCl, hon nguyn xc tc cho ta vinylclorua.CH CH HgCl CHCl CH HgCl HCl CH CHCl HgCl222

Quan im khc cho rng: mui ng, mui thy ngn tc dng vi axetylen thnh phc cht , trong cc nguyn t cacbon c in tch dng v c kh nng tc dng vi anion Cl- kt qu kim loi c thay thbng proton.Hg2+II.3.2.2Sn xut VC t axetylen theo phng php pha kh:a.Xc tc:Xc tc ca qu trnh tng hp VC theo phng php pha kh trong trng hp ny dng xc tc HgCl2 ngm tm trn than hot tnh. c im ca loi mui ny rt c nn ngi ta c xu hng thay th mui thy ngn bng cc mui kim loi khc nh BaCl2, CdCl2, khi nng HgCl2 trn than hot tnh tng, hiu sut chuyn ha axetylen thnh vinylclorua tng.Ta thy nng HgCl2 tng 5-10% th hiu sut tng vt ln, nhng khi nng HgCl2 ln hn 20% hiu sut chuyn ha tng chm ng thi phn ng ta nhit lm cho xc tc b nung nng cc b HgCl2 b thng hoa, axetylen trng hp bao ph b mt xc tc lm cho xc tc gim hot tnhnhanh.Da vo bng s liu trn cho nn trong cng nghip ngi ta dng loi xctc HgCl2 10%.b. Sn xut VC t axetylen theo phng php pha kh:Ta tin hnh cho ng thi C2H2 v kh HCl qua lp xc tc nhit cao ta c VC. Xc tc dng l HgCl2 ngm trn than hot tnh. Hin nay c

HCCH +HgCl2CHCH ...ClH2CCHCl+

Hg2+Hg2+

% HgCl2 trn than hot tnhHiu sut chuyn ha,%

569,6

1086,7

2092,3

4094,9

6096,8

nhiu gi thit v c cu phn ng c xc tc, mt s quan im cho rngmui thy ngn tc dng vi axetylen to thnh hp cht trung gian:CH CH HgCl2 CHCl CH HgClNhit thch hp cho phn ng l 110-170oC, khi xc tc gim hot tnh c th tng nhit ln 200oC. Khi nhit tng dn n 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 275oC th HgCl2 bt u phn hy 300oC th n thng hoa. Thng th ta lm lnh tun hon vi cc tc nhn lm lnh l nc di p sut hoc du lm lnh tun hon lm mt thit b phn ng chnh, m bo nhit n nh ( khng qu 200oC ) t hiu sut chuyn ha cao nht.+ C mt s nh khoa hc khc cho rng phn ng kt hp axetylen v HCl cng xy ra khi khng c xc tc m p sut cao:CH CH HCl CH 2 CHClPhn ng ny l phn ng thun nghch, p sut thng cn bng chuynv pha tri ngng 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 ha thnh izo-axetylen kt hp vi HCl cho ta VC.HCCHCH2CCH2C+HClCH2=CHClCc gi thit 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 trn than hot tnh.Cng vi cc phn ng chnh, trong qu trnh cn to ra mt s phn ngClCHHgClClCH CHHgHg +Cl-CH=CH-Cl2HC CHClHg CH CH Hg ClHgCl2+ Cl-CH=CH-Cl+ 2HClClClph. Nu d C2H2 s to thnh dicloetan theo phn ng. m bo lng C2H2 phn ng ht ta phi cho tha mt lng HCl ttnht l dng C2H2/HCl theo t l 1/1,1 ( t l mol ).

Ta c s nh hng ca t l nguyn liu n hiu sut chuyn ha sau:Vi t l nguyn liu c chn lc cho qua thit b trn ln gm nhiu vtliu tng tc ng u trc khi vo thit b phn ng. Vn tc thtch cng nh hng n hiu sut chuyn ha.Vy ta chn thit b cho vn tc chuyn ha cao v vn tc th tch ph hp. Trong trng hp vn tc th tch nh 25 m3/m3.xt.h. Tuy nhin, hiu sut chuyn ha cao nhng nng sut ca thit b gim. Do phi cn c v yu cu nng sut t ra cho phn xng sn xut m ta chn vn tc lm vic v cc chi tit ca thit b. Trong thc t khng ch vn tc th tch ph hp trong khong 25 50 m3/m3.xt.h.Nguyn liu trc khi a vo phn ng cn phi lm sch cc tp cht v tp cht d lm xc tc b ng c:H 2 S HgCl2 HgS 2HClH3 P 3HgCl3 HgCl3 P 3HClHoc c th tham gia phn ng:CH CH 2Cl2 Cl2CH CHCl2Clo v axetylen to thnh mt hn hp n. ng thi, nguyn liu phi c sy kh v mui thy ngn cng l xc tc cho phn ng to thnh hydrat ha axetylen thnh axetandehyt:

T l C2H2/HCl(mol)Hiu sut chuynha, %

1/1,0991,05

1/1,196,95

1/1,297,75

Vn tc th tch(m3/m3.xt.h)Hiu sutchuyn ha(%)

12593,66

10094,55

7596,06

5097,40

2597,46

CH CH H 2O CH 3 CHOChnh nhng phn ng ny gy gim hot tnh ca xc tc dn n thi gian sng ca xc tc gim, lm tng gi thnh sn phm, v vy cn lm sch nguyn liu loi cc thnh phn tp cht. Hi axetylen trc khi a vo thit b phn ng c a qua thp cha dung dch K2Cr2O7, ti y xy ra phn ng oxy ha kh loi b H2S, H3P.H 2 S K2 Cr2O7 K 2 SO4 H 2 Cr2O3H 3 P K2 Cr2O7 K3 PO4 H 2Cr2 O3Do , nguyn liu trc khi a vo phn ng phi m bo cc yu cu sau:Kh C2H2 c tinh khit ln hn 99%.Hi nc 0,03%Khng c H2S v H3P.Kh HCl c tinh khit 95%Khng c Oxy v Clo.Trong qu trnh phn ng nhit lng ta ra rt ln, vi phn ng chnh to ra VC nhit lng ta ra l 26900kcal/mol. Cn vi phn ng ph to ra dicloetan nhit lng ta ra l 40200 kcal/mol. Lng nhit ny cng nh hng n vic la chn thit b phn ng loi ng chm, ng knh cc ng trong thit b c cha xc tc cng nh hng n ch v tc dng kh trong ng.Bn ngoi ng ca thit b l cht lm mt, c th dng nc di p sut thng hoc du mt ti nhit. Vic la chn tc nhn lm mt cng ty thuc vo yu cu kinh t, k thut v iu kin tng ni. Trong trng hp s dng nc di p sut thng c mt s u nhc im sau:u im: Nc sn c, khng c c hi, r tin, c nhitdung ln nn iu chnh nhit ca thit b.Nhc im: lng nc cn dng cho thit b ln nn thit b cng knh v lm mt trong khong nhit khng cao ( do nhit si ca nc thp).Vic lm mt bng du khc phc c nhng nhc im trn nhng gi thnh cao hn. Chnh v vy ty tng iu kin m ta chn tc nhn lm mt cho ph hp.

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4Mt s s cng ngh sn xut VC t C2H2 v HCl xc tc HgCl2/C*: II.4.1S cng ngh sn xut VC c in:Hn hp axetylen v hydrocacbon cho qua vng phn ng c cha yxc tc rn HgCl2/C*. Cht ban u phi kh khng to axetylendehyt qu nhiu v gy n mn thit b HCl c t l d mt cht so vi axetylen ( t l C2H2/HCl = 1/1,1) lm tng mc chuyn ha axetylen. Nhit ti u khong 160 1800C, khi qu trnh xy ra nhanh v khng xy ra s li cun HgCl2 nhiu ( do HgCl2 d thng hoa ). Khi HgCl2 hao ht dn v gim hot phn ng ngi ta tng nhit ln n 200 2200CDo ta nhit cao ta thc hin qu trnh trong thit b ng chm, trong ng c cha sn xc tc. Hn hp kh chuyn ng trong lng ng, khong trng gia cc ng l cht lm lnh hon lu. Cht lm lnh l cht truyn nhit hu c, nc hoc phn ngng vi mc ch l tit kim nhit phn ng nhm thu c hi. y ta chn cht lm lnh l du.Axetylen lm sch cho qua thit b chn la v sy. Qu trnh sy din ra theo hai giai on sau:Giai on 1 :l ngng kt phn m trong thit b lm lnh nc muiGiai on 2 :l sy bng kim rn trong thp.Trong b khuy axetylen c trn vi HCl kh v cho v thit b phn ng hnh ng .Mc chuyn ha axetylen l 97 98% kh ph ng c cha 93 % VC, 5 % 10% C2H2, 0,3 % axetandehyt, 1,1% DCE. Kh ph ng cn ko minh hi HgCl2. Kh c lm lnh trong thit b lm lnh v lm sch khi HgCl2 v HCl tip theo trong thit b bng HCl 20 % v kim hon lu. Sau , khi c sy bng thit b lm lnh bng nc mui v nn trong b nn kh n 7 8 at. Hn hp sau c tch trong thp chng ct tch phn cn rn trc( cn l 1,2 Dicloetan) cn sau l phn nh( Phn cn li l axetandehyt). Trong qu trnh ny axetylen sau khi c lm sch khu chun b c lm kh ring bit qua hai giai on trn 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 v t tn nng lng. Tuy nhin, kh cha phn ng khng c tun hon li thit b phn ngnn phn no nh hng n hiu sut s dng ca nguyn liu.

II.4.2S cng ngh sn xut VC hin i:Ngun gc:Phn ng kt hp axit clohidric vi C2H2 xy ra nh sau:CH2=CHCl, H0 298 = -100kj/mol.CH CH +HCl S bin i cc vng kh c mt HgCl2 c s cho ton b xc tc trong khong nhit 100 -1700C v p sut tuyt i khong 0,3.106 Pa. Cht xc tc c th s dng l than hot tnh nhng cng c th thay thbng grafit, nhm v Na2SiO3.....T ng lc ca quan im ny, mc phn ng u tin t ch trong s s dng kt hp cc cht phn ng. iu ni ln s to thnh phc tp ca lin kt , bng cch kt hp HgCl2 vi C2H2, ko theo s bin i HgCl2 v VC. Tc dng HCl sau hon nguyn HgCl2 vi s tothnh ca VC.CHCH+HgCl2HCCHHgClHClClHgCl2+H2CCHClCCHHgClS pht trinthitb phn ngt c nh v thit b dng ngc th hin bi nhit b mt c thit lp. im nhit ny c a ra khng vt qu 2000C v bin i theo thi gian trong qu trnh iu khin dng kh, lm nh vy c th nh gi c s lo ha ca xc tc. Vi chiu cao 5m, bng cch iu chnh thch hp t c trong thi gian di hn 200h. Trong nhng iu kin ny v ngay c khi c nhng bin i ln, nng sut ca s kt hp C2H2 vi axit HCl cng t ti 98 % mol. Trong nhng trng hp ny thi gian sng ca xc tc l 5 thng.S thay i nhng im nng phn x ny lm cho sch HgCl2 tng dn v cun n theo dng kh bn c loi b. Lng Hg tiu tn tng ng 0,5- 0,6 kg/tn sn phm VC nh vy sn phm phc tp thu c cn x l trnh nhim mi trng. iu ny c th lm gim kh nng hot ng ca lp lng, do cho php s lu thng ca hi nng tt hn pht ra t thit b phn ng v nh vy thu c nhiu b mt nhit ngu hn( qu trnh ny c ng dng bi cc hng BASF, USSR.).

N cng c xut hot ng trng thi lng khi c mt cadung mi( bi cc hng Distiller, Knapsack, Shell).Trong qu trnh lm vic Tmax chuyn dch theo chiu ca dng kh v pha cui ng v thng hoa HgCl2.V vy trong cc TBP cng nghip ngi ta t cc cp nhit theo sutchiu di ng p theo di v tr v gi tr ca Tmax, qua nm c trngthi ca lp xc tc.Sn phm ph ch yu l axetandehyt, to thnh t mt lng nh nctrong cht phn ng v 1,1-dicloetan thu c t phn ng ca axit HCl vi VC, ph hp theo phn ng sau :CH2 = CHCl + HClCH3CHCl2 (1,1-DCE)

Thuyt minh dy chuyn cng ngh:Qu trnh bao gm ba b phn chnh:Chun b nguyn liu: axetylen c sy, sau c trn vi HCl v kh tun hon.Phn ng: Hn hp kh thu c t thit b trn c a vo thit b phn ng ng chm t song song vi nhau. Mi thit b c ng knh 2m, chiu cao 4m cha t 1500-2000 ng xc tc. Thi gian sng ca xc tc 2000 gi. Nhit phn ng c tch v iu khin bng cch tun hon cht ti nhit lnh bn ngoi ng phn ng, qua thit b trao i nhit bn ngoi.X l kh sn phm: kh sn phm ri vng phn ng c ra vi nc v NaOH tch HCl d, sau c nn ti 0.7 Mpa v lm lnh bng nc, phn ln s c ngng t. Nc c tch ra trong thit b lng v thit b chng ct tch nc. Sn phm VC c tinh ch trong thp chng ct nhit thp 0,4-0,5Mpa. Kh thu hi t thit b lng cha ch yu l axetylen c lm sch bng hp th, tch v tun hon li thit b phn ng. So snh cng nghCng ngh sn xut VC t C2H2 v HCl hin i c nhng c imsau:Nhit phn ng VC t C2H2 v HCl hin i c nhng u imsau:Nhit phn ng thp hn ( 100 -1700C), cng ngh c 1800C.Cht lm lnh l nc rt tit kim v mt kinh t so vi nc mui cng ngh trc kia.Nng sut ca s kt hpC2H2 vi HCl t 98% mol ngay c khi cnhng bin i ln.iu kin a l Vit Nam rt thun li sn xut VC do ngunnguyn liu chnh C2H2 rt di do.Ngnh cng nghip du m Vit Nam ang tng bc pht trin cho php s dng kh nhit phn du m hay nhit phn kh thin nhin trong c hn hp axetylen v etylen. y l con ng iu ch axetylen r tin.

PHN II. TNH TONNng sut 120.000 tn/nmVi cc s liu ban u:a/ C2H2-k thut c nng th tch :99%H2O- 0,03% O2-0,01% N2-0,96%b/ HCl c nng 97,3%H2-0,15% N2-2,40% H2O-0,05%Chn mc chuyn ho C2H2 thnh VC l: 98%Chn mc chuyn ho C2H2 thnh 1,1-DCE l: 0,2%Thnh phn ca sn phm theo khi lng l:+ Vinylclorua: 93%+ HCl:5%+ Tp cht: 2%III.1Xc nh thi gian lm vic ca phn xng:Ta chn dy chuyn vinylclorua lm vic 24/24. V trong mt nm s cnhng thi gian nht nh bo dng sa cha:+ Ngh v l do gp s c, 15 ngy sa cha ln.+ Ngh v l do gp s c nh l 15 ngy.Vy thi gian thc lm vic ca phn xng trong nm l:365-(15+15)=335 ngyMt ngy lm vic 24 gi chia lm 3 ca vi tng s gi lm vic trongmt nm l:335 x 24 = 8040 gi/ nmCc phn ng chnh ca qu trnh:CH CH HCl CH 2 CHCl CH CH 2HCl CH3 CHCl2 CH CH H2O CH2 CHO

III.2Tnh cn bng vt cht:Nng sut ca thit b sn xut trong 1 gi:(120000 x 1000)/8040 = 14925,373 kg/hPhng trnh phn ng to VC:CH CH HCl CH2 CHCl(1) 26 36,562,5Theo phng trnh phn ng (1) lng C2H2 chuyn ho thnh VC trong 1 gi:(14925,373 x 26 )/ 62,5 = 6208,955 kg/hDo mc chuyn ho ca C2H2 thnh VC l 98% nn lng C2H2nguyn cht cn dng:(6208,955 x 100)/98 = 6335,668 kg/hNhng tinh khit ca C2H2 trong nguyn liu a vo l 99% nntrong thc t lng hn hp kh C2H2 a vo thit b l:(6335,668 x 100)/99 = 6399,665 kg/hT gi thuyt ban u l lng hn hp kh C2H2 c cha:H2O- 0,03% O2-0,01% N2-0,96%Lng H2O c trong nguyn liu kh C2H2 l:(6399,665 x 0,03)/100 = 1,919 kg/hLng Oxy c trong nguyn liu kh C2H2 i vo thit b l: (6399,665 x 0,01)/100 = 0,639 kg/hLng Nit trong nguyn liu kh C2H2 i vo thit b l: (6399,665 x 0,96)/100 = 61,436 kg/hV chuyn ho C2H2 thnh DCE l 0,2% nn lng C2H2 tiu tn to 1,1-DCE l:(6399,665 x 0,2)/100 = 12,799 kg/hPhng trnh phn ng to 1,1-DCE:CH CH 2HCl CH3CHCl2 (2) 2699Theo (2) lng 1,1-DCE to ra trong 1h:(12,799 x 99)/26 = 48,735 kg/hTheo (1) lng HCl cn sn xut VC:(14925,373 x 36,5)/ 62,5 = 8716,418 kg/h

Theo (2) lng HCl tham gia to 1,1-DCE:(12,799 x 36,5 x 2)/26 = 35,936 kg/hTheo gi thit VC chim 93% khi lng sn phm. Vy khi lng sn phm l:(14925,373 x 100)/93 = 16048,788 (kg/h)Cng theo gi thuyt lng HCl d trong sn phm l 5% khi lng snphm. Vy lng HCl d l:(16048,788 x 5)/100 = 802,439 (kg/h)Vy tng lng HCl nguyn cht thc t a vo thit b l: 8716,418 + 35,936 +802,439 = 9554,793 (kg/h) tinh khit ca HCl trong hn hp kh l 97,3 % nn lng hp khHCl thc t a vo thit b l:(9554,793 x 100)/97,3 = 9819,931 ( kg/h)T gi thuyt th hp kh HCl c cha: H2-0,15%, N2-2,40%, H2O-0,05%. Do ta c :Lng H2 trong hp kh HCl a vo thit b l: (9819,931 x 0,15)/100 = 14,729 kg/hLng N2 trong hn hp kh HCl a vo thit b l: (9819,931 x 2,40)/100 = 235,678 kg/hLng H2O trong hn hp kh HCl a vo thit b l: (9819,931 x 0,05)/100 = 4,909 kg/hDo C2H2 trc khi vo thit b phn ng c sy kh bng H2SO4 nn lng H2O do C2H2 mang vo thit b coi nh bng khng. Vy lng nc l do nguyn liu HCl mang vo.Phng trnh phn ng:CH CH HOH CH3CHO (3) 261844Theo phn ng (3) ta c lng C2H2 tham gia to CH3CHO:(4,909 x 26)/18 = 7,091 kg/hTheo phn ng (3) ta c lng CH3CHO to thnh l:(4,909 x 44)/18 = 11,999 kg/hVy lng C2H2 cn d l:6335,668- 6208,955 -12,799-7,091 = 106,823 kg/hTng lng N2 do nguyn liu HCl v C2H2 mang vo: 61,436 + 235,678 = 297,114 kg/h

Kt qu thnh phn cn i vt cht c tng kt theo bng sau y:

Lng cht voLng cht ra

Cu tKg/hCu tKg/h

C2H26335,668C2H2d106,823

HCl9554,793HCld802,439

N2297,114N2297,114

O20,639O20,639

H2O4,909H2O0

H214,729H214,729

VC14925,373

DCE48,735

CH2CHO11,999

Tng vo16207,852Tng ra16207,851

PHN 3: TNH HNH CA NGNH CNG NGHIP SN XUT VC CAMT S QUC GIA TRN TH GII V VIT NAM.IV.1K hoch sn xut VCM Wilhelmshaven( CHLB c)European Vinyls Corporation( vit tt EVC) l cng ty xy dng k hoch bn thng mi sn xut VC t etan vi nng sut 1000tn/ nm c quy m ln Wilhelmshaven. Trong thi gian ny EVC chnh thc thng mi ha thit b phn ng. T khi bt u lm vic, cc thit b hot ng trn 200 h nhit phn ng. Cc yu t lin quan cng ngh ny cng c th c tin hnh . Nh vy cht xc tc c n nh v hot ng lin tc khng cn bt k mt tc ng no. y bin i trn 99% v etan l 90%, mc d s tinh ch etan c th bin i vi t l ti 92-95%.Thng 9/1999 EVC thit k thnh cng phn xng sn xut VC Wilhelmshaven. K hoch ny khi tin hnh cn i hi qu trnh maketing v v tr a l sn xut VCM. Do , k hoch ny c tnh ton li v c chp nhn trin khai vo gia nm 2002. K hoch thng mi ha quy m u tin c nh trc v tin hnh vo nm 2004.IV.2Cng ngh sn xut VCM Kerteh( Malaysia):Tp on Vinyl chloride Malaysia Sdn Bhd l s kt hp gia Cng Mitsui (Nht) v cng ty ha du Nasional Berhah ( Petronas) the Nationaled ( Malaysia). Nhim v chnh ca cng ty Vinyl chloride Malaysia l xy dng v iu khin hot ng ca thit b VCM Kerth, Terengganu. VCM l nguyn liu sn xut PVC, nguyn liu th sn xut cc loi ng dn trong i sng con ngi. Hin ti 50% sn phm ca cng ty c xut khu. Petronas l cng ty thc hin k hoch tng i mi ny.250 triu USD l vn u t cho k hoch Kerteh ( Malaysia) bi cng ty Mitsui, Mitsui Toatsu Chemicals v Petronas s sn xut VCM vi nng sut 400,000 tn/ nm/ Phn trm u t ca cc cng ty l: 60% ca Petronas, 20% ca Mitsui v 20 % ca cng ty Plastic Molder Land & General BLD.Qu trnh xy dng nh my bt u t nm 1999, vi nng sut ban u l 280,00 tn/nm.

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IV.3Tnh hnh sn xut VCM Vit Nam:Sn lng ngnh nha Vit Nam trong nhng nm gu y tng mnh l do nhu cu ca x hi v sn phm nha ngy cng ln cng nh th hiu ca ngi tiu dng thch a dng ha mu m v nng cao mc tin ch gia dng, tnh nng ca mt s sn phm nha cng nghip bn v r. Mt phn nguyn nhn ca s tng trng ny l do cc doanh nghip nha c k hoch u t ng n v ph hp vi nhu cu thc t th hin qua cc hot ng ca cc doanh nghip nh nghin cu th trng, nh hng chuyn mn ha sn phm, khng sn xut i tr nhiu ngnh hng.Ch s cht do sn xut c tnh trn u ngi Vit Nam thp hn nhiu so vi cc nc khc trn th gii, nm 1996 l 5,58 kg, nm 2000 l 11,57 kg v nm 2005 l 14kg/u ngi v mc tiu ti nm 2010 l 30kg/u ngi. Ring Thnh Ph H Ch Minh v cc vng ln cn l 100kg/u ngi. Vit Nam cn thc hin chin lc v chng trnh mnh m pht trin ngnh ny.Ngnh nha Vit Nam thc cht l mt ngnh kinh t k thut v gia cng cht do, hin cha c kh nng sn xut ra nguyn vt liu nha, gn nh ton b nguyn vt liu sn xut ra sn phm nha phi nhp t nc ngoi. Ngnh nha c u im l cng ngh cp nht hin i, tc quay vng nhanh, s dng lao ng k thut l chnh, sn phm a dng, phc v c nhiu i tng, lnh vc cng nghip, cng nh trong tiu dng hng ngy ca x hi. Theo thng k ca UNDP, 70% nhu cu vt cht cho i sng con ngi c lm bng nha, t ch s cht do trn u ngi c tha mn l 30 kg/u ngi (Vit Nam hin mi ch t khong 14kg/u ngi), cn t trn 100 kg/u ngi l quc gia c nn cng nghip nha tin tin.Trong vi nm ti, khi ngnh cng nghip ha du ca Vit Nam ra i, s m ra nhiu c hi pht trin hn cho ngnh nha c bit l ngnh cng nghip nguyn liu. Th trng trong nc cng nh th trng th gii ang m ra nhiu c hi pht trin cho ngnh nha do nhu cu v sn phm nha ngy cng tng. Tuy nhin, ngnh nha hin nay cng ang ng trc nhng vn kh khn nh ngun nhn lc cn hn ch c v i ng k s ln cng nhn lnh ngh. Hin nay c trn 11.000 ngi ang lao ng trong ngnh nha v cao su, chim 4,6% lao ng ton ngnh cng nghip. Lao

ng gin tip hin chim 17% so vi tng s lao ng ca ton ngnh, trong s lao ng c trnh i hc v trn i hc chim 6,65%, trung cp chim 2,1%, cng nhn k thut chim 9,97%, nhn vin trung cp 4,6%, lao ng trnh khc (bao gm s lao ng cha qua trng lp, ngh dy ngh) chim ti 69,23%. Nh vy s cng nhn khng c o to tham gia lao ng trc tip ln gp 6,8 ln s cng nhn c k thut v tnh chung th lao ng gin n ca ton ngnh chim ti 76,6%. iu ny chng t s lao ng c k thut trong ngnh cn qu t.sVi i ng cn b c o to trong v ngoi nc, sau nhiu nm cng tc gip cho ngnh nha c pht trin v i mi. Nhng k s tr c kh nng c lp gii quyt nhng cng vic phc tp, qun l k thut. Nhng phn ln cha c kh nng qun l k thut, ch o cng trnh v cha c tm nh hng chin lc cho ngnh. Trong nhiu nm nay vic o to k thut cho ngnh nha cha c mt t chc no m nhn vi quy m cn thit ca n.Nhn chung i ng k thut cn rt thiu nht l i ng cng nhn c tay ngh cao, h thng o to cng nhn cha c v vy thiu i ng b sung, hu b. S k s t c iu kin v kh nng tip cn nhanh chng vi cng ngh tin tin. Chnh iu ny lm nh hng n s pht trin ca ngnh nha. y l vn cn phi nhanh chng khc phc v cn c quan tm ng mc.S u t hn 400 triu USD xy dng T hp Vinyl ti B Ra - VngTu(HNM) - TCty Ha cht Vit Nam (VINACHEM) cho bit, VINACHEM v TPC (Thi Lan) ang ln k hoch hp tc xy dng T hp Vinyl ti khu cng nghip Ph M II (B Ra-Vng Tu).T hp ny gm cc nh my: Vinylclorua (VCM) cng sut 345.000 tn/nm, Etylen iclorua (EDC) cng sut 300.000 tn/nm, Xut-clo (CA) cng sut 250.000 tn/nm. Ngoi ra, trong t hp ny cn d kin xy dng mt nh my in chy than, cng sut 65 MW. Tng mc u t vo T hp hn 400 triu USD (cha k nh my in), trong vn vay khong 297 triu USD, cn li l vn gp.

T hp Vinyl cn mang li hiu qu x hi ln vi vic cung cp khong4.000 c hi vic lm cho ngi Vit Nam trong giai on xy dng, khong 147 v tr lm vic sau khi T hp i vo vn hnh. c bit, T hp Vinyl ra i s s dng c hiu qu cc ngun ti nguyn trong nc (etylen, mui v than), to ra gi tr thng d cho cc sn phm ha cht, ha du tiu th ti th trng ni a.

KT LUNQua mt thi gian lm vic chm ch cng vi s gip tn tnh ca thy o Vn Tng, em hon thnh c nhim v n ca mnh l thit k phn xng sn xut Vinylclorua vi nng sut 120.000 tn/nm v so snh v chn lc c cng ngh ph hp vi iu kin ca Vit Nam. Qua n ln ny em xin rt ra c nhng kinh nghim sau y:+ Trc khi thit k mt phn xng no th cn phi nm r tnh cht l hc v ho hc ca nguyn liu v sn phm. Xem chng c gy nhng nguy him g khng nh chy n, gy c, t trong qu trnh thit k ta c nhng bin php phng trnh.+ i vi mt sn phm no y th c rt nhiu dy chuyn cng ngh khc nhau. Do nhim v t ra cho chng ta l phi hiu r nguyn l ca tng dy chuyn cng ngh t m a ra kin l ta phi dng cng ngh no v cng ngh y c ph hp vi iu kin ca Vit Nam hay khng. y l mt bc rt quan trng.+ Sau khi ta chn c dy chuyn cng ngh th ta tin hnh tnh ton v thit k cho dy chuyn cng ngh y hot ng cho t hiu qu cao, tit kim c nguyn liu nhng vn m bo yu cu cht lng sn phm.Mt ln na em xin chn thnh cm n thy v cc bn gip em hon thnh n ny mt cch tt p!Sinh VinNguyn T Quang Huy

TI LIU THAM KHO1. Vng nh Nhn.S tay k s ho cht.Nh xut bn khoa hc k thut, 1961.Phan Minh TnTng hp hu c ho du, tp I.Trng HBK thnh ph H Ch Minh, 1994.Phan Minh TnTng hp hu c ho du, tp II.Trng HBK thnh ph H Ch Minh, 1994.S tay qu trnh thit b cng ngh ho cht, tp I.Nh sut bn khoa hc v k thut, 2004.S tay qu trnh thit b cng ngh ho cht, tp II.Nh sut bn khoa hc v k thut, 2004.Phm Thanh Huyn-Nguyn Hng Lin Cng ngh tng hp hu c ho du. Nh sut bn khoa hc v k thut, 2006.K Thut sn xut cht do, tp IA. Trng HBK H Ni, 1978.Gio trnh ging dy ca thy Trn Cng Khanh.Cng ngh tng hp hu c ho du.Ullmann'sEncyclopediaofIndustrialChemistry Release 2004, 7th Edition.Ti liu t Internet:http://www.vinachem.com.vn/ViewCSDLFirst.asp?CateCSDL ID=3http://www.vinachem.com.vn/XBPViewContent.asp?DetailXB PID=1192&CateXBPDetailID=93&CateXBPID=1&Year=200 3

http://www.vinachem.com.vn/XBPViewContent.asp?DetailXB PID=154&CateXBPDetailID=13&CateXBPID=1&Year=2001http://www.epa.gov/ttn/atw/hlthef/di-ethyl.htmlhttp://en.wikipedia.org/wiki/Vinylidene_chloridehttp://www.scorecard.org/chemical- profiles/summary.tcl?edf_substance_id=75-35-4