TRNG I HC M - A CHT KHOA DU KH B MN LOC HOA DU

------- ------

N CNG NGH HA DU V CH BIN POLYME

ti: TM HIU CNG NGH SN XUT PVC V TNH
TON MT S THNG S K THUT CHO THIT B PHN NG VI NNG SUT 150.000 TN/NM

Sinh Vin: L Thi N Gio Vin Hng Dn: Lp : Loc Hoa Du B-K53 TS.Nguyn Th Linh Kha hc: 2008 2013 Nm hc: 2012 - 2013

H NI, 12 - 2012 1

LI GII THIU...............................................................................................................................3

Chng I: l thuyt tng quan...............................................................................4

I. gii thiu chung..............................................................................................................................4 I.1 Lch s pht trin........................................................................................4 II.2 Tnh hnh sn xut v tiu th PVC:...........................................................5 1. Trn th gii..............................................................................................5 2. Ti Vit Nam..............................................................................................8 II. Tng hp PVC.............................................................................................................................13 1. Tnh cht l hc ......................................................................................14 2. Tnh cht ho hc ...................................................................................15 II.2. Phn ng to nha PVC...........................................................................17 1. C cu phn ng.....................................................................................17 2. ng hc qu trnh trng hp.................................................................19 3. trng hp v chiu di ng hc ca mch.......................................20 II.3. Cc yu t nh hng n qu trnh trng hp ......................................21 III. Sn phm PVC...........................................................................................................................22 1. Cu to ......................................................................................................22 2. Tnh cht ca Polyvinylclorua ....................................................................23 3. ng dng .................................................................................................. 27 Trong lnh vc in v in t:....................................................................30 Trong lnh vc t, xe my:........................................................................30 Trong cc lnh vc khc:.............................................................................31

chng ii: cng ngh sn xut pvc......................................................................31

.................................................................................................................... 33 I.1. Quy trnh axetylen....................................................................................33 I.2. Quy trnh kt hp etylen v axetylen.......................................................34 I.3. Quy trnh kh trn t naphta (du m).....................................................35 I. 4. Quy trnh oxy- clo ha.............................................................................36 II. Cng ngh tng hp polyvinylclorua (pvc).................................................................................41 II.1 Trng hp khi.........................................................................................43 II.2. Trng hp hp dung dch........................................................................45 II.3. Trng hp VCM bng phng php nh tng........................................46 II.4. Trng hp huyn ph..............................................................................48

CHNG III: TNH TON CC THNG S K THUT CHO THIT B PHN NG CA CNG NGH SN XUT PVC BNG PHNG PHP HUYN PH......................................................................................................54
I.2. Thnh phn nguyn vt liu.....................................................................55 I.4. Dy chuyn sn xut PVC huyn ph ti nh my TPC Vina:...................60 II. TNH CN BNG VT CHT.................................................................................................64 II.1 Thng s ban u.....................................................................................64 II.2 Tnh cn bng vt cht cho thit b phn ng..........................................65 1. Thi gian cho mt m sn xut...............................................................65 2. Nng sut ca mt m sn xut.............................................................65 3. Tnh cn bng vt cht cho thit b phn ng.........................................66 4. Tnh chi ph nguyn liu u vo cho mt thng sn xut......................72 III. tnh cn bng nhit lng cho thit b phn ng polyme ...........................................................73

KT LUN.........................................................................................................76 TI LIU THAM KHO...................................................................................77

LI GII THIU Trong thi i ngy nay, cng vi nn khoa hc hin i, cng ngh ha hc khng ngng pht trin v chim mt v tr v cng quan trng trong nhiu lnh vc. Cng ngh v hp cht cao phn t l mt trong nhng cng ngh in hnh, rt tiu biu v tc pht trin v phm vi s dng. Tuy ra i c mun hn cc ngnh khc, nhng kh nng ng dng ca n l v cng rng ln. Hu ht cc vt liu trong k thut v i sng ngy nay c thay th bng nhiu loi vt liu mi c ch to t cc hp cht cao phn t. y l hng i mi m nhiu quc gia trn th gii nhn thy.V vy cc nh khoa hc khng ngng u t v nghin cu v lnh vc quan trng ny. C c tm quan trng nh vy l v cc hp cht cao phn t c nhiu tnh cht rt 3

qu nh : bn c hc, n hi, cch m, cch nhit, cch in, nh v d gia cng hn kim loiBn cnh gi thnh li r. Do vic sn xut cc hp cht cao phn t tng hp cng nh cc sn phm t n ngy cng gia tng ng k . Mt trong nhng loi nha tng hp ph bin c sn xut nhiu l nha Polyvinyl Clorua (PVC). Nha Polyvinylclorua l mt trong nhng sn phm ra i sm ca nn sn xut cht do . Trong cng ngh sn xut nha Polyvinyl clorua , ty theo phng php sn xut v thnh phn ca cc cu t tham gia m ta c th thu c mt s loi nha c t trng khc nhau nh : K - 58, K - 66 ,K - 71. Nha Polyvinylclorua c nhiu c im tt nh n nh ha hc, bn c hc, d gia cng ra nhiu loi sn phm thng dng ( mng bao gi, o i ma, dp) v c bit l dng sn xut ng chim ti 50% tng sn lng. Bn cnh nha Polyvinylclorua cn c dng bc dy in, lt nn, trn nh v cc chi tit ca thit b cng nghip ha hc Ngoi ra Polyvinylclorua ng trng hp vi cloruavinilden cn c dng lm si tng hp . Chnh v th m vic tm hiu cng ngh sn xut nha Polyvinylclorua rt l cn thit. c bit l nh my sn xut nha Polyvinylclorua theo phng php huyn ph . l l do em chn ti: Tm hiu cng ngh sn xut PVC v tnh ton mt s thng s k thut cho thit b phn ng vi nng sut 150.000 tn/nm. CHNG I: L THUYT TNG QUAN I. GII THIU CHUNG I.1 Lch s pht trin Trong cng nghip cht do, Polyvinyl clorua (PVC) l mt trong ba cht do ch lc gm Polyolefin (PO), PVC v Polystyren (PS). N ng hng th hai sau Polyolefin vi tng cng sut ton th gii nm 1997 l trn 25 triu tn, tiu th khong 22 triu tn. Vinyl clorua c tm ra ln u tin bi Regnault nm 1835, polyme Polyvinyl clorua (PVC) c quan st thy ln u tin nm 1938. Nm 1912, Baumann trnh by phn ng trng hp monome vinilic gm vinyl clorua s dng nh sng mt tri to ra sn phm PVC dng bt trng. T , cng 4

ngh trng hp PVC c nhng bc pht trin mnh m ch yu M v c. Sn phm thng mi ca PVC ra i ln u tin c vo u nhng nm 30 s dng qu trnh trng hp nh tng. Nm 1932, bc t ph u tin gii quyt vn qu trnh v s n nh nhit din ra khi Semon pht minh ra cht ho do cho PVC, qu trnh s dng cht n nh c pht trin vo nhng nm 30 ca th k 20[5]. Hin nay PVC l mt trong nhng polyme chnh ca th gii. Do tnh cht c l tt nn PVC c sn xut vi sn lng ln. Tuy nhin tnh n nh nhit v tnh mm do ca PVC km hn mt s nha thng phm khc nh Polyetylen (PE) v PS. PVC c sn xut ch yu bng trng hp gc. Tuy nhin, trng hp gc ca PVC cho ra nhiu cc ng phn v cc khuyt tt cu trc. Nhng nhn t ny l quan trng sng cn i vi ngi s dng PVC, v chng to ra nhng vn v mu sc, n nh nhit, tinh th, ng x gia cng v tnh cht c hc ca thnh phm. Nghin cu v khuyt tt cng em li s hiu bit su sc v bn cht ca phn ng ph xy ra trong qu trnh trng hp[5]. Ngoi cc cht ph gia nh cht ho do, cht n nh nhit, cht bi trn, cht n v cc polyme khc, c nhiu cng trnh nghin cu nhm ci thin nhng tnh cht yu km ca PVC, v d nh ng trng hp vi cc monome khc v thay i hnh thi ca ht tng cng tnh d gia cng. Polyme ghp ng trng hp ca PVC vi monome acrylic v vinyl axetat, blend vi MBS v acrylonitryl butadien styren (ABS) c th nghim tng sc chu va p. Copolyme ca PVC vi monome imit v PVC clo ho c nghin cu tng tnh chng chy ca PVC. Tng hp polyme khi lng phn t cao v mt lin kt ngang PVC tng modun. Tng hp PVC ho do ni l mt gii php cho vn ca cht ho do (DOP) di chuyn t bn trong ra bn ngoi vt liu[5]. II.2 Tnh hnh sn xut v tiu th PVC: 1. Trn th gii Trong phn ln thi gian ca thp nin 1990, sn xut PVC l mt lnh vc sn xut khng t li nhun cao. iu ny khin nhiu cng ty ng ca 5

nh my, rt khi sn xut PVC hoc sp nhp vi nhau. Rt t nh my mi c d kin xy dng. Tuy nhin, nhu cu PVC tng mnh vo cui thp nin, bt chp nhng vn mi trng. Kt qu l, sau khi nh hng ca cuc khng hong ti chnh chu gim dn, nhu cu PVC tng ln st sao vi mc cung v li nhun tng tr li trong nm l 999. Sn lng PVC ca th gii nm 2006 t ti hn 32 triu tn v mc tng trng trong giai on 2001 2006 l hn 5 %/nm. D kin n nm 2012, cng sut PVC ca th gii s t 50 triu tn/nm. Khu vc chu c d bo dn u th gii vi mc tng trng nhu cu bnh qun hng nm l khong 7 %/nm trong giai on t nay n nhng nm 2010 v n nm 2012 s chim 50% tng cng sut ca th gii, trong cao nht l Trung Quc, tip n Malaysia, Vit Nam v n . Bng 1 l sn lng PVC ca th gii trong cc nm1991, 2001, 2006 v d bo cho 2011. Bng 2 l cng sut PVC ca Chu Thi Bnh Dng giai on 2000-2007, trong Trung Quc vi s nhy vt t bin vn ln v tr dn u th gii.

Bng 1 : Sn lng PVC trn th gii n v: 1.000 tn TT 1 2 3 4 5 6 7 Khu vc Ty u Trung u CIS NAFTA Nam M Chu Phi- Trung ng Chu -Chu i Dng Cng: 1991 6.030 2.440 6.090 940 830 5.860 22.190 6 2001 5.500 500 300 6.500 1.100 1.400 10.600 25.900 2006 5.800 700 800 7.300 1.500 2.100 14.600 32.800 2011 6.100 1.000 1.700 7.800 1.600 2.700 19.800 40.700

Theo: TPC Vina, CMAI v Vinolit Bng 2: Cng sut nha PVC ca Chu -Thi Bnh Dng giai on 2000-2007 n v tnh: 1.000 tn

Theo: Harriman Report Ngnh xy dng l lnh vc s dng ch yu i vi cc sn phm PVC. Trong lnh vc hng tiu dng v bao b ng gi, cc sn phm PVC ang mt dn th phn v n c thay th bi cc sn phm khc thn mi trng hn. Nhng yu t nh hng n sn xut PVC ton cu l: - S tng trng kinh t s ko theo s tng nhu cu PVC. - Gi nng lng cao c th lm gim tc tng trng kinh t. - Cc vn v mi trng c th khng km hm s tng trng sn xut 7

PVC, nhng c th hn ch vic xy dng cc nh my PVC mi.[6] C cu s dng 5,3 triu tn PVC ti cc nc Ty u nh sau: C cu s dng PVC ti cc nc Ty u : ng dn 27% Kt cu xy dng 18% Tm mng cng 10% Bc cp 9% Chai l 9% Mng mm 7% Lt sn 6% Cc ng dng khc 6% Lp sn lt 3% ng mm 3% 3% Sn phm xp 2% Cng 100%

2. Ti Vit Nam T nhng nm u ca thp k 60 Vit Nam "sn xut c" PVC do Nh my ha cht Vit Tr sn xut. Trong phng n sn phm ca nh my c 150 tn/nm PVC ch yu gii quyt cn bng do vic to ra HCL, cho kt hp vi axetylen t t n nhp ngoi, thnh VCM v trng hp. Nhng tn bt trng ng hng u tin y c Nh my Cao su Sao vng cn thnh tm "nilng" che ma, nh my cquy Hi Phng lm nhng tm l cch in...Song va khng kinh t, li sn lng qu nh, chng gii quyt c vn g nn ngnh sn xut ny sm chm dt, c bit khi bc vo chin tranh ph hoi ca M. Trong nhng nm ca thp k 90 cng nghip gia cng cht do trong nc pht trin mnh vi tc tng bnh qun ti 28%/nm. Nm 1990 tiu th cht do trong nc l 0,5 kg/ngi n nm 1996 ln ti 5,7 kg/ngi. Ton b nha nguyn liu l nhp khu; trong s PVC chim trung bnh 1/3. 8

PVC nhp di 2 dng: Bt PVC (PVC resin) v ht PVC (PVC compound) cha sn cht ha do, cht n nh, cht mu.[6] Nm 2000 c nc tiu th khong 150.000 tn bt PVC, trong nc sn xut p ng c khong 40% nhu cu v phi nhp khu 60% t nhiu nc trn th gii.[7] Nm 2002, ton ngnh nha Vit Nam s dng 1.260.000 tn nguyn liu nha, trong PP, PE, PVC l cc nguyn liu c s dng nhiu nht chim khong 71,3% tng nhu cu nguyn liu.[6.2] Mc tiu th theo tng loi nguyn liu nha nm 2002 nh sau: PP: 380.000 tn PVC: 180.000 tn PE: 340.000 tn Ngun cung cp PVC bt v ht, cng nh mt s bn thnh phm PVC (tm tri nh, v gi da) v ph gia ch yu l cht ha do DOP l cc nc ng v ng Nam (Nht Bn, Singapo, Hn Quc, i Loan, Thi Lan...). Bng 3: thng k nhp khu PVC: vt triu USD [10] Tn nc Hn Quc Singapo Thi Lan Nht Bn Arp x t n Hng Kng Malaixia Tng s Nm 1998 11.7 8.8 12.5 7.7 2.7 0.2 53.5 Nm 1999 7.4 4.9 12.1 4.8 Nm 2000 16.5 16.5 21 7.9 0.4 2.2 73 10thng/2001 6.1 4.0 11.3 0.2 0.4 0.1 36

41

Lng PVC nhp tng hng nm: nm 1997 , ring PVC nhp trn 72.000 tn. Theo k hoch d kin ca Tng cng ty nha Vit Nam nhu cu bt PVC v cht ha do trong thi gian ti nh sau : Nm 2000 2005 2010 PVC 100.000 200.000 400.000 DOP 28.000 28.000 67.000 9

Cc d n sn xut PVC theo danh mc cc d n nguyn liu v bn thnh phm nghnh nha giai on 20012010. (Ban hnh km theo Quyt nh s 11/2004/Q-BCN ngy 17 thng 02 nm 2004 ca B trng B Cng nghip). 2005 Cng su Tng vn a im t (triu (tn/n) USD) ng Nai Vng Tu Vng Tu 120.000 100.000 45 80 200.00 0 147 2010 Cng su Tng t vn (tn/n) (triu USD)

Tn d n

Nh my sn xut PVC1 m rng Nh my sn

B Cng nghip vch ra mt chin lc ca ngnh ha du n u cc bc i tip sau ca s pht trin PVC: to ra etylen t cracking nafta (hoc kh thin nhin), clo ha ri gp nhau VCM, ng thi cung cp 2-etyl hexanol v axit terephtalic. Theo d kin vo khong nm 2010 chng ta s c kh nng sn xut t u n cui 500.000 tn nha PVC v 75.000 tn DOP. Tng lai ca nghnh sn xut nha PVC ti Vit Nam l kh quan.[6] Vit Nam, cng nh tt c cc nc ng Nam khc (k c i Loan), cng ngip sn xut nguyn liu cho ngnh nha u khi u t PVC. S sau cho ta khi qut cc bc pht trin ca qu trnh sn xut PVC t du m v s pht trin ca ngnh ha du Vit Nam:

10

Ngnh sn xut nha PVC Vit Nam bt u vo nm 1998 vi s hin din ca lin doanh TPC Vina (tin thn l Mitsui Vina). Cui nm 2002, nh my sn xut PVC th hai (Lin doanh gia Petronas Malaysia vi B Ra Vng Tu) c cng sut 100.000 tn/nm cng bt u tham gia vo th trng. Bng 4: Lng tiu th cc loi nha v PVC Vit Nam trong nhng nm qua v d on n nm 2011. Nha ni chung Tng cu Bnh qun (tn) tiu th (kg/u ngi) Sn xut Nhp trong khu nc (tn) (tn) PVC Tng Bnh cu (tn) qun tiu th (kg/u ngi) 58500 65000 74000 0,81 0,89 1,00

Nm

1995 1996 1997

280000 420000 500000

3,78 5,60 6,06 11

58500 65000 74000

1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011

625000 780000 950000 1010000 1260000 1450000 1550000 1650000 1967000 2297000 2710000 3200000 3850000 -

8,00 9,80 12,20 13,00 15,60 18,70 20,10 21,00 22,00 26,80 31,50 36,40 42,00 -

12100 47600 24930 78800 102100 119700 127730 145200 176200 195000 215000 250000 290000 290000

92000 61800 85700 52800 52900 47200 51200 64300 69800 65000 66000 54000 40000 64400

104100 109400 110000 131600 155000 166900 178930 209500 246000 260000 281000 304000 330000 356400

1,83 1,41 1,42 1,67 1,94 2,06 2,18 2,52 2,90 3,04 3,25 3,48 3,74 4,00

Tuy nhin, hin nay gi sn phm PVC trong nc cao hn rt nhiu so vi gi mt bng chung trn th gii. Nguyn nhn ca tnh trng trn l do s ht gi ca ng tin cc nc cung cp nguyn liu cho ngnh nha Vit Nam. Hn na, cc nh my mi i vo hot ng gi thnh sn phm vn mang gi tr khu hao ban u nn gi thnh vn cao hn mc bnh thng. Kh nng cung-cu nha PVC Vit Nam c th hin trong biu hnh 1.1:

12

Hnh 1.1: Kh nng cung cu PVC ca Vit Nam Nh vy, cho n nm 2010 2011 v c cc nm sau Vit Nam vn cn phi nhp khu PVC nu nh ngay t by gi khng c nh u t no quan tm n lnh vc ny. II. Tng hp PVC II.1. Nguyn liu Nguyn liu chnh sn xut Polyvinylclorua l vinylclorua (C2H3Cl) v mt s nguyn liu ph khc nh cht khi mo, cht n nh huyn ph, cht n nh nhit cht km hm Ty theo loi v hm lng ca cc nguyn liu ph ny m ta c th to ra c nhiu loi Polyvinylclorua khc nhau ( c trng hp trng hp khc nhau) v d nh: K-58 K-66 K-71 ( trng hp n = 700 ). ( trng hp n = 1020 ). ( trng hp n = 1270 ).

Trong ba loi trn th loi K - 66 c s dng nhiu nht (chim khong 90 % ). Nh vy nh my ny s sn xut loi K66. Cc nguyn liu chnh sn xut loi nha ny gm c: 13

1. Tnh cht l hc nhit v p sut thng l cht kh c mi ete. + Nhit ng rn + Nhit ngng t + Nhit ti hn + Nhit bc chy + Nhit nng chy + Nhit bc hi 250C + Trng lng ring + Nhit to thnh + Nhit trng hp + Nhit dung ring dng lng 250C + Nhit dung ring dng hi 250C + H s khc x ca VC lng + T l ca VC ph thuc vo nhit Nhit (0C) T trng -15 0,9730 -25 0,9014 -159,70C -13,90C 1420C 415kcal/kg 18,4kcal/kg 78,5kcal/kg 0,969kcal/kg -83 8kcal/kg -366 5kcal/kg 0,83kcal/kg 0,207kcal/kg 1,83kcal/kg

+ p sut hi ca VC ph thuc vo nhit Nhit (0C) p sut (mmHg) -87,5 10 -55,8 100 -13,37 760 16,2 22,58 46,8 54,34

+ tan trong nc 1at l 0,5 % trng lng + Gii hn nng ca hn hp vi khng kh t 3,62 26,6% th tch 14

+ Tnh cht c ca VC: VC c hn so vi etylclorua v t c hn clorofom v tetra clorua cacbon. C kh nng gy m qua h thng h hp ca con ngi v c th ng vt. Con ngi khi tip xc hi VC mc 25% th ch trong 3 pht bt u b chong vng v mt thng bng nh hng. Nu hm lng VC trong khng kh l 0,5% th con ngi c th lm vic trong mt vi gi m khng c tc ng sinh l no ng k c. [2] 2. Tnh cht ho hc Cng thc cu to:
C 2C H = H Cl
|

Do c cha lin kt i v nguyn t Clo linh ng nn cc phn ng ho hc ca VC l phn ng ca nguyn t Clo linh ng. VC khng tan trong nc, tan trong cc dung mi hu c nh axeton, ru etylic, cacbon hydro thm, cacbon hydro mch thng. Trong phn t VC c lin kt ni i v mt nguyn t Clo linh ng, do phn ng ho hc ch yu l phn ng kt hp hoc phn ng ca nguyn t Clo trong phn t VC. - Phn ng ni i + Phn ng cng hp: tc dng vi halogen cho ta 1,2 diclo etan iu kin mi trng kh 140 1500C hoc 800C v c chiu sng xc tc SbCl3. Khi c xc tc AlCl3, FeCl3 th VC phn ng vi HCl. CH2 Vi H2 CH2 CH + H2 Cl 15 CH3 CH2 Cl + CH HCl Cl CH2 Cl CH2 Cl

Trong phn ng oxi ho VC nhit 50 1500C c mt HCl d dng to ra monome axetat dehit CH2 CH Cl
+

1/2O2

CH2

CHO

Cl Do phn t c cha ni i VC c th tham gia phn ng trng hp to PVC. CH2 CH Cl - Phn ng ca nguyn t Clo. + Thu phn. Khi un nng vi kim HCl b tch ra khi VC cho ta axetylen CH2 CH Cl n

Tc dng vi acolat hay fenolat cho ta este VC: CH2 CH + RONa Cl - To hp cht c kim CH2 CH + NaCl OR

+ VC trong iu kin khng c khng kh 4500C c th b phn hu to thnh axetylen v HCl do phn ng polyme ho axetylen v c th phn ng tip tc to ra mt lng nh 2- clo- 1,3- butadien. Cn trong iu kin c khng kh VC b oxi ho hon ton.

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- Bo qun: Trc y VC c bo qun v vn chuyn vi s c mt ca mt lng nh phenol c ch phn ng polyme ho. 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 nn VC khng gy n mn c th c bo qun trong cc thng thp cacbon thng. II.2. Phn ng to nha PVC 1. C cu phn ng. C cu phn ng to nha PVC l phn ng trng hp Vinylclorua (VC)

VC cha ni i v c momen lng cc bng 1,44. Phn ng trng hp xy ra di tc dng ca cht khi mo (hoc nhit , nng lng hoc tia phng x). Trung tm hot ng nhn c c dng gc t do, phn ng trng hp theo c ch trng hp gc. - C cu phn ng gm 4 giai on: Giai on khi mo. Giai on pht trin mch. Giai on t mch. Giai oan chuyn mch. + Giai on khi mo: Gi s cht khi mo l Peoxit benzoil. 1. Phn hu cht khi mo.
O
||

O
|| 0

C 6 H 5 C O O C C 6 H 5 t 2C 6 H 5 COO C 6 H 5 COO C 6 H 5 + CO 2

K hiu gc hot ng l R

17

Tuy nhin cc gc ny khng phi u tham gia khi mo qu trnh trung hp, m c mt s khc kt hp vi nhau to thnh phn t trung ho (khong 20-40%). V d:
C 6 H 5 + C 6 H 5 C 6 H 5 C 6 H 5 C 6 H 5 + C 6 H 5 COO C 6 H 5 COOC 6 H 5

2. Khi mo. R + CH2 = CH R CH2 C H | | Cl Cl + Giai 2 C H trin = CH R CHon pht+ CH2mch. R CH2 CH CH2 C H | | | | Cl Cl Cl Cl R CH2 C H - CH2 C H + nCH2 = CH2 | | Cl Cl R CH2 C H - CH2 C H - CH2 - CH | | | Cl Cl Cl

+ Giai on chuyn mch. - Chuyn mch ln Monome. CH2 = CH + CH2 CH | | Cl Cl CH2 = C + CH2 CH2 | | Cl Cl CH3 = CH + CH CH | | Cl Cl Chuyn mch ln Polyme. - CH2 C H + - CH2 CH CH2 CH2 + CH2 C | | | 18 | Cl Cl Cl Cl

Chuyn mch ln cht khi mo. O O || || CH2 CH+ C6H5 C O O C C6H5

O || CH2 CH O C C6H5 + C6H5 COO | Cl + Giai on t mch. Phn ng t mch c th xy ra theo hai cch: Kt hp. - CH2 C H + CH2 C H CH2 CH - CH - CH2 | | | | Cl Cl Cl Cl Phn ly. CH2 CH + CH2 C H CH2 CH2 + CH = CH | | | | Cl Cl Cl Cl 2. ng hc qu trnh trng hp. Trong trng hp s dng cht khi mo giai on khi mo gm 2 phn ng. - Phn ng phn hu cht khi mo. I 2 R . Trong : R : gc t do. Vd = kd [I] = VI : I: Cht khi mo. kd: hng s vn tc phn hu. - Phn ng to gc t do ban du. R + CH2 = CH R CH2 CH | | Cl Cl 19

vn tc ca phn ng ny l V2. V V2>> Vd do Vd s quyt nh vn tc qu trnh khi mo. VKM = 2Vd = 2f . kd [I] = KKM [I]. KKM = 2fkd. f: l h s c trng cho hiu qu khi mo ca cht khi mo. + Giai on pht trin mch. (Giai on ny l phn ng to nhit) y l giai on quyt nh vn tc trng hp, cu to v kch thc, khi lng ca Polyme. Vn tc pht trin mch bng vn tc tiu hao Monome trong mt n v thi gian.

dM = Vpt = K pt[R ].[M ] dt

[M]: Nng Monome.
[R ]: Nng gc t do.

Kpt: Hng s pht trin mch. Vpt: Vn tc pht trin mch, Vd: Vn tc t mch. + Giai on t mch.

dR = Vd = K d[R ]2 dt
Hng s vn tc t mch (106 108. L/mol. S) ln hn rt nhiu hng s vn tc pht trin mch (102 - 104 L/mol.s). Tuy nhin phn ng pht trin mch vn xy ra do phn ng t mch b hn ch bi nng gc t do thp, s khuych tn v cn tr khng gian. 3. trng hp v chiu di ng hc ca mch. - Chiu di ng hc ca mch l t l gia 2 i lng. Vp L= Vd Do mt s thi im khi chuyn ho cha su lm th tc to thnh cc gc t do bng tc tiu hao n. Vd = VKM. Thay gi tr VKM = Vd = Kd [M.]2 20

Thay gi tr Vp = Kp [M] [R.] L= Vi k = K p[M ] K d[R ] Kd

1/ 2

K [M ] K KM [I ]1/ 2

K p .K KM

1/ 2

Chiu di ng hc ca mch t l thun vi nng Monome v t l nghch vi cn bc hai ca nng cht khi mo. Vi trng hp khi t mch theo c ch phn ly, trng hp P bng chiu di ng hc ca mch. K [M ] P= K KM [I ]1/ 2 Vi trng hp khi t mch, theo c ch kt hp, trng hp bng 2 ln chiu di ng hc ca mch.

P=2

K [M ] K KM [I ]1 / 2

II.3. Cc yu t nh hng n qu trnh trng hp 1. Nhit Khi nhit tng, vn tc ca tt c cc giai on phn ng trng hp u tng. Nng lng hot ho ca cc giai on khc nhau. Nng lng hot ho ca phn ng khi mo (112 170kJ/mol) ln hn hn so vi nng lng hot ho ca phn ng pht trin mch 928 40kJ/mol) v phn ng t mch. Do , khi nhit tng mc tng vn tc khi mo l ln nht. Vn tc khi mo tng ko theo vn tc trng hp tng v vn tc t mch cng tng theo. V VKM tng nng gc t do cng tng nn ta c. Vp = kp [ M ].[M ] Vd = kp [M ]2 Do Vd tng nhiu hn Vp. 2. p sut

21

Khi p sut thp v p sut trung bnh tng ln n vi chc vi trm atm thc t khng nh hng g n qu trnh trng hp. Nhng khi p sut tng cao 1000 atm tr ln vn tc trng hp v khi lng phn t ca Polyme u tng. 3. Oxy Oxy tc dng vi Monome to Peroxit. CH2 = CH + O2 CH2 CH Cl | | | Cl O O Peroxit ny phn hu to gc t do. Nu gc hot tnh thp th O2 c tc dng lm hm qu trnh trng hp, nu gc hot ng th oxy s lm tng vn tc trng hp. 4. Nng cht khi mo Khi nng cht khi mo tng, vn tc trng hp tng nhng khi lng phn t Polyme gim [4]. 5. Nng Monome Khi tng nng Monome trong phng php trng hp dung dch, vn tc trng hp v khi lng phn t u tng. Nhng nu dung mi tham gia vo phn ng chuyn mch, th mi lin quan n vn tc trung fhp v khi lng phn t phc tp hn nhiu. III. SN PHM PVC 1. Cu to Polyvinylclorua l nha nhit do, c cu to v nh hnh. Trong cng nghip c sn xut dng bt, t trng 1,38 1,4 g/cm3. Polyvinylclorua c trng hp theo c ch gc t do l s kt hp ca cc phn t theo "u ni ui" thnh mch pht trin. Trong mch phn t, cc nguyn t clo v tr 1;3. CH2 CH CH2 CH CH2 CH Cl Cl 22 Cl

Ngi ta dng nhiu phng php khc nhau nh: ha hc, vt l, quang hc chng minh iu ny. V d: Kh Cl trong Polyvinylclorua bng cch un nng dung dch Polyvinylclorua trong dioxan vi bt km th thy c nhm cyclo propan c to ra.

Ty theo iu kin kh Cl m trong Polyme cn li 13 16% Cl dng nguyn t Cl ring bit.

trng thi khng ko cng th Polyvinylclorua hon ton dng v nh hnh v ch khi no ko tht mnh mi c kh nng nh hng mt phn nhng khng kt tinh. Trong phn t Polyvinylclorua cng c cu to nhnh nhng t, chim khong t 50 100 mc xch mi c mt nhnh. 2. Tnh cht ca Polyvinylclorua Nhit ha thy tinh Tg : Khi lng ring Gii hn bn ko Gii hn bn un : :

75 80 oC. : 1,38 1,4 g/cm3.

400 600 kG/cm2. 900 1200 kG/cm2. 23

Gii hn bn nn bn va p gin di tng i

: : :

800 1600 kG/cm2. 70 160 kG/cm2. 10 15 %.

2.1 ha tan ca polyvinylclorua Polyvinylclorua l polyme phn cc nn c th ha tan trong cc dung mi nh este, hydrocacbon clo ha, nitrobenzen. Tuy nhin Polyvinylclorua ch ha tan khi trng lng phn t thp, cn khi trng lng phn t cao th tan rt hn ch, nhit cao tan tng ln. tng ha tan cho Polyvinylclorua thng tin hnh bin tnh Polyvinylclorua nh ng trng hp vi vinylaxetat, vinylindeclorua hoc clo ha polyvinylclorua to thnh polypercloruavinyl. 2.2 Tnh nhit H s gin n ph thuc vo loi lin kt gia cc nhm nguyn t hoc phn t ny v h s ny cng ln khi cng lin kt cng yu. gin n nhit ca Polyvinylclorua rt thp. Bng 5: dn nhit ca mt s vt liu: Vt liu PVC PS Thy tinh Thp H s gin n 10-6C- dn 1 W/moC 50 -180 60 - 80 3-4 11 -12 0,12 - 0,3 0,10 - 0,14 1,25 55 nhitNhit dung (kJ/kgoC) 0,84 -1,25 1,34 0,71 - 0,84 0,437 ring 20oC

Polyvinylclorua c nhit chy mm cao hn mt t so vi nhit phn hy. Khi 140 oC bt u phn hy chm v 170 oC th phn hy nhanh hn.

24

Khi tng nhit , HCl sinh ra nhiu hn v n lm cho PVC xut hin mu, tnh tan ca Polyvinylclorua dn dn mt i theo phn hy ca n. Tnh tan ca Polyvinylclorua mt dn l do to lin kt ngang.

V s i mu ca Polyvinylclorua do to lin kt i lin hp

S phn hy polyvinylclorua khi un nng cng theo phn ng chui, trung tm bt u phn hy l nhng mch m c lin kt C H, C Cl yu. Nhng phn c th l nhng nhm cui ca mch i phn t. Khi trng hp polyvinylclorua theo c ch gc th vic c mch c th xy ra do phn ng truyn mch cho phn t monome hoc cho phn t polyme.

25

Trong trng hp truyn mch cho monome th phn t polyme c ni i cui mch cn truyn mch cho polyme th xut hin mch nhnh v phn t c cha cacbon bc ba. Cc lin kt i hoc cacbon bc ba trong mch lm nh hng n bn lin kt ca nguyn t cacbon bn cnh lm cho lin kt d b t bi i lc in t b gim v c th kch ng qu trnh phn hy to HCl. trong mi trng khng kh c nhit th s phn hy polyvinylclorua xy ra nhanh hn trong mi trng kh tr v khi c mt ca cc vt kim loi c ha tr thay i nh Zn, Fe th chng s xc tin cho qu trnh phn hy polyvinylclorua xy ra nhanh hn. Ph thuc vo thnh phn nguyn liu v mc ch s dng m ngi ta tin hnh gia cng polyvinylclorua 140 170 oC. Trong iu kin ny c xy ra qu trnh phn hy HCl, to mch polyvinylclorua c ni i v c khi to cu ni gia cc mch i phn t. tng n nh nhit cho polyvinylclorua ngi ta thm vo cht n nh nhit, cc cht ny c tc dng lm chm hoc km hm s phn hy polyme. Trong tt c cc loi cht n nh nhit th hp cht v c v c kim l quan trng nht v ngoi tc dng n nh nhit chng cn ngn cn polyvinylclorua khi b phn hy trong iu kin gia cng nhit cao v c kh nng bo v cc tnh cht vt liu trong thi gian di khi s dng vt liu. 2.3 Trn vi cht do v cc loi nha khc gia cng v s dng Polyvinylclorua hiu qu th vic trn n vi cht ha do c ngha rt quan trng. Cht ha do l cht n vi polyvinylclorua lm cho polyvinylclorua c bn un tng, lm gim tnh dn nhit thp, 26

tc l lm gim nhit ha thy tinh, lm gim iu kin gia cng v tng thi gian s dng sn phm v polyvinylclorua l polyme mch cng, nhit cao mi n hi. Cc cht ha do l cc cht c cc, thng dng dng lng thng dng nht l cc este, phtalat, adipat, sebacat. * C ch ha do. Polyvinylclorua l polyme phn cc, polyvinylclorua cng t bin dng l do lc ni ti gia cc phn t.

Cc phn t ha do s chim v tr gia cc mch polyme lm tng khong cch gia cc mch v do lm gim lc lin kt gia chng. Khi un nng, chuyn ng ca cc phn t tng do lm cho cc mch phn t mm do, c th trt ln nhau lm cho polyvinylclorua mm ra. Ngoi ra polyvinylclorua cn c kh nng trn hp vi cc polyeste mch thng, cc nha alkyd, nha epoxi, polyformaldehyd. 2.4 Tnh cht in Thng thng cc polyme trong c Polyvinylclorua khng c nhng phn t tch in. Do vy in tr ca polyme rt ln (1015 1018 m) v th Polyvinylclorua c dng lm v bc dy cch in. 3. ng dng Thnh phn ca PVC c c th m cc loi nha khc khng c: trong phn t monome VCM c ti gn 60% khi lng l t clo, clo c hnh thnh qua qu trnh in phn mui n (NaCl). Do PVC t ph thuc vo sbin i gi ca du m hn so vi nhng loi polyme c tng hp t 100% du m. Ti mi thi im, gi ca PVC bao gi cng thp hn khong t 20 - 30% so vi cc loi cht do cng c ng dng rng ri khc nh PE, PP v PS. 27

u im th hai l do clo em li cho PVC. l tnh km hm s chy. Cng chnh v c im ny m PVC gn nh chim v tr c tn trong lnh vc xy dng dn dng. V mt ng dng, PVC l loi nha a nng nht. Gi thnh r, a dng trong ng dng, nhiu tnh nng vt tri l nhng yu t gip cho PVC tr thnh vt liu l tng cho hng lot ngnh cng nghip khc nhau: xy dng dn dng, k thut in, v tuyn vin thng, dt may, nng nghip, sn xut t, xe my, giao thng vn ti, hng khng, y t ... bt k u chng ta u bt gp s hin din ca PVC. [14]

PVC cng (khng c cht ho do): lm tm, ng dn, vt liu cch in PVC mm: ng dn mm, bc dy in, mng mng, thuc da PVC khng c: thng cha thc phm, mng bao b thc phm, chai l cht do

3.1Trong lnh vc xy dng: Lnh vc xy dng l ni m PVC c s dng nhiu v rng ri nht. Trong , cc loi ng dn v ph kin chim n hn mt phn ba tng sn lng PVC trn ton th gii. Nm 2007, con s ny l 39% trong tng s 33,5 triu tn nhu cu PVC trn th gii. Vit Nam, cc s liu tng ng l 47% ca 240000 tn (Hnh 2.2 v 2.3).

28

Hnh 3.1. Cc lnh vc ng dng ca PVC trn th gii

Hnh 3.2. Cc lnh vc ng dng ca PVC ti Vit Nam ng PVC c s dng trong nhng iu kin k thut cng nh mi trng kht khe chng t l mt loi vt liu c bn v tin cy cao. Chng c dng rng ri cp thot nc sinh hot, thu li, lu chuyn ha cht, bo v cp in v cc loi cp trong ngnh bu chnh vin thng. ng PVC khng b g, b oxi ha hay n mn. Do chi ph bo tr thp, nc trong ng khng b nhim bn. ng PVC cng khng nh hng n mi v ca nc, khng c phn ng ha hc ngay c vi nhng cht lng c hot tnh mnh. ng PVC d un, chu c s va chm v cc chn ng. Khi c lp t, tui th ca ng c th ln ti hn 100 nm. ng PVC cng l s la chn ti u trn phng din gi thnh. ng PVC nh nn chi ph vn chuyn thp v cng lp t thp (ch bng 60 - 70% so vi cc loi ng khc). Ngoi ng dn, PVC c s dng cho xy dng nh ca v trang tr ni ngoi tht. Vt liu PVC dng trong lp t v trang tr nh ca hin nay cha ph bin Vit Nam (ch chim khong 24% tng nhu cu). Nhng trn th gii, nhiu nc t l ny rt cao, v d nh M 60%. iu l do bn lu, kh nng lp t d dng, d bo tr v tnh hp dn ngi tiu th ca cc sn phm PVC. Trong nhiu khu, cc sn phm PVC thay th nhng vt liu 29

truyn thng nh g, ng v nhm. M c c mt hip hi gm hn 100 nh sn xut v nh kinh doanh vn nhn to t PVC v cc cht do khc. H chuyn nghin cu, sn xut v cp chng ch k thut cho cc loi vn sn, vch ngn, tm trang tr ... Theo Hip hi ny, trang tr ngoi tht cho nh bng tm PVC l r nht. Ngoi nhng ng dng trn, PVC cn dng lm mng mng thu li, mng mng phc v nng nghip, hng ro, mi che Trong lnh vc in v in t: y chnh l lnh vc m nh n PVC pht trin mt cch nhanh chng v t ph. Nh trn ni, cch y hn 50 nm, ngi ta pht hin ra PVC c nhng tnh cht khng nhng ging m cn vt tri cao su trong vic bc dy cp in. Ngy nay, PVC chim gn 50% th phn lnh vc sn xut in v in t. Mt s lnh vc sn xut ph bin cn dng PVC:

My iu ho khng kh, my lnh, my git Dng c gia nh. My tnh, a mm cho my tnh, bn phm Cp quang. Dng c in.

Trong lnh vc t, xe my: PVC ng mt vai tr to ln trong ch to t, m t hin i. N c s dng thay th kim loi v vt liu khc ch to cc b phn sn xe, tm chn gi, tm lt sn, tm chn bn v nhiu chi tit khc. Theo ti liu ca Hip hi cc nh sn xut PVC chu u (ECVM), hin nay mt chic t mi sn xut cn 16 kg PVC. Nh dng PVC thay th mt phn kim loi trong ch to t m hng nm Ty u tit kim c khong 800 triu Euro, cn c th gii tit kim c ti 2,5 t Euro. Vic s dng PVC s lm cho:

Tui th ca xe di hn: do bn ca PVC, tui th ca xe tng t 11,5 nm trong nhng nm 1970 ln 17 nm nh hin nay.

30

Khch hng c nhiu la chn hn: do PVC r, nn ty thuc vo yu cu ca th trng, nh sn xut c nhiu phng n s dng nguyn vt liu to ra nhiu mu m hp dn khch hng vi gi c hp l. Cc chi tit t PVC c tnh mm do nn ngi s dng xe s an ton hn trong trng hp xy ra tai nn giao thng.

Vi nhng b phn v chi tit bng nha, xe s nh hn v nh s tiu th t nhin liu hn, gp phn tit kim v bo tn ngun ti nguyn nng lng trn th gii ang ngy cng cn kit trn th gii. Trong cc lnh vc khc: Bao b cho thc phm v hng ha tiu dng, chi tr em, giy dp, o ma, ti xch, v rt nhiu cc mt hng tiu dng khc. Nhng sn phm ny c dng ph bin v ngoi nhng tnh u vit nu trn chng cn d cho nhiu mu sc hp dn, d lp t v lau chi khi lm v sinh.

CHNG II: CNG NGH SN XUT PVC

I.

CC QUY TRNH TNG HP VYNYL CLORUA (MVC) Nhng bin i trong lch s ca cc quy trnh sn xut MVC[5]. 1. Quy trnh axetylen v HCl in phn NaCl HCl Acetylen e Tng hp MVC MVC

Than/Cacbua

2. Quy trnh kt hp etylen v axetylen

31

CH

CH

Hydro-Clo-ha HCl

Tinh ch MVC

MVC CH2 Cl2 CH2 Clo-ha Tinh ch EDC Nhit phn EDC

3. Quy trnh kh trn t Naphta Naphtha Phn hy nhit Naphtha Trn kh Cng hp HCl vo Acetylene HCl Ethylene Clo ha trc tip EDC Phn hy nhit EDC MVC 4. Quy trnh oxy-clo ha Ngy nay, do yu t kinh t trong qu trnh tng hp acetylen (i t than cc, vi vi bc trung gian l ccbua can xy - CaC2 - cn rt nhiu nng lng) nn hu ht cc nh sn xut s dng HCl d ny oxy - clo ha ethylen vi s c mt ca xc tc: CH2 = CH2 + 2HCl + O2 CH2Cl CH2Cl + H2O (6) Kt hp c 3 phn ng (3), (4) (ly h s 2) v (6) ta c: 2 CH2 = CH2 + Cl2 + O2 2 CH2 = CHCl + H2O (7) S ca qa trnh c th hin trong Hnh 7: Cl2

32

Cl2 CH2 O2 CH2

Clo ha

Tinh ch H2O HCl

Nhit phn EDC

Oxy Clo ha

Tinh ch MVC

MVC I.1. Quy trnh axetylen Giai on u ca cng nghip PVC, bt u vo nhng nm 1930 n gia nhng nm 1960, loi nguyn liu thp ca PVC c sn xut bng phng php axetylen. VCM c tng hp t axetylen v HCl bng phn ng trong pha kh vi s c mt ca clorua thy ngn lm xc tc nhit khong 150oC. Axetylen c sn xut t cacbua (carbide) ch to t than [5]. CaC2 + 2H2O CHCH + Ca(OH)2 CHCH + HCl CH2=CHCl (VCM) Qu trnh sn xut MVC t acetylen v HCl c s dng rng ri mt s nc t nhng nm 1950. Ngy nay vi s pht trin ca cng nghip du m, hu ht cc nc chuyn sang s dng ethylen lm nguyn liu ch yu sn xut MVC. Tuy nhin, trong nhng nm gn y, vi vic khng hong nng lng thng xuyn xy ra trn th gii cng vi s gia tng gi c cc phng tin vn chuyn v tn dng nhng thun li ti ch (nh tr lng than di do ti vng Ty Bc v khu vc Ni Mng c th gip pht trin ng thi nhit in yu t chnh quyt nh gi thnh ca acetylen) Trung Quc quay tr li phng php ny. Theo s liu thng k trong tng sn lng nha PVC ca Trung Quc nm 2006 l 6,5 triu tn th 4,2 triu tn c sn xut t ngun acetylen, ch c 2,3 triu tn l i t etylen. Theo s liu mi nht, hin nay Trung Quc t l gia PVC sn xut t acetylen v t etylen l 65:35 (Xem Hnh 8).

33

Theo: Hip hi cng nghip sn xut xut-clo Trung Quc, CCAIA Hnh 8: Trung Quc sn xut PVC t acetylen nhiu hn t etylen Mt tr ngi ca phng php sn xut MVC t acetylen l vn nhim mi trng. V qu trnh ny s dng xc tc l clorua thy ngn (HgCl2) rt c hi, m n nay cha c bin php x l n trit v hiu qu. I.2. Quy trnh kt hp etylen v axetylen Etylen gi r t nghnh cng nghip ha du mi pht trin lc cung cp nguyn liu thp sn xut etylen iclorua (EDC). EDC l tin thn ca VCM. Phn hy nhit ca EDC cho ra VCM v HCl, cht ny khng c s dng cho mc ch no trong cng nghip ha du lc by gi. Qu trnh axetylen ca VCM c coi l thch hp tiu th HCl t s phn hy nhit ca EDC. Cui nhng nm 60 ti Nht, s kt hp gia hai qu trnh etylen v axetylen sn xut VCM c ng dng nh l mt giai on qu ca cng nghip than v ha du[5]. CH2=CH2 + Cl2 CH2Cl CH2Cl (EDC) CH2Cl CH2Cl CH2=CHCl (VCM) + HCl CHCH + HCl CH2=CHCl (VCM) Trong qu trnh sn xut MVC t etylen v clo ngi ta dng xc tc l clorua st hai (FeCl2), nn t tc ng n mi trng hn so vi phng php trn. Phn ng c th thc hin c hai pha: lng v kh.

34

Trong pha lng ngi ta dng chnh sn phm ca phn ng, etylendicloetan (EDC), lm dung mi ho tan etylen v clo. Phn ng xy ra 50-70oC v p sut 4-5 atm. Hiu sut t 95-96% so vi etylen. Qu trnh trong pha kh c tin hnh 90-130oC v p sut 7-10 atm.V y l phn ng ta nhit mnh nn vic kim sot nhit phn ng trnh xy ra chy n l rt quan trng. trnh chy n, ngi ta thit k thit b phn ng dng ng chm, cho kh i qua khong cch gia cc ng chm c lm lnh bn trong. Ngoi ra cn c th dng kh tr lm gim kh nng gy n hoc dng lng etylen d Do nhiu yu t k thut thun li nh nu di y nn phng php tng hp trong pha lng thng c p dng rng ri hn: - Thit b phn ng n gin; - D iu chnh nhit phn ng - Khng cn dng lng etylen d hoc kh tr - Nhit phn ng c dng ngay un nng dung mi v lm bay hi sn phm to thnh. I.3. Quy trnh kh trn t naphta (du m). Trong cc quy trnh c cp trn y th quy trnh axetylen t cc hp cht ca ccbua vn cn n. C etylen v axetylen u c iu ch trc tip t phn ng phn hy nhit cao ca naphta 2000 oC. Trc tin, hn hp kh etylen v axetylen phn ng vi HCl v axetylen c chuyn i thnh VCM. Sau , phn etylen cn li phn ng vi HCl v chuyn thnh EDC. Quy trnh ny c gi l quy trnh kh trn v c pht trin bi KurehaChemical vo nhng nm 60. Sau , Kureha Chemical pht trin tip qu trnh ny bng vic i nguyn liu thp t naphta thnh du th v thnh cng trong vic pht trin dy chuyn mi vo nhng nm 70. Nippon Zeon cng pht trin quy trnh VCM tng t, quy trnh kt hp axetylen v etylen t s phn hy ca naphta. Trong quy trnh ny, trc tin kh phn hy c tch ra ring r thnh axetylen v etylen v sau mi kh c cung cp cho mi phn ng tng ng. axetylen c tch ring bng phng thc hp th dung dch bng dung mi dimetyl formandehyt. Nhng 35

quy trnh ny b loi b vo cui nhng nm 70 do thiu tnh cnh tranh v kinh t so vi quy trnh oxy-clo ha[5]. I. 4. Quy trnh oxy- clo ha u nhng nm 60, quy trnh oxy-clo ha c pht trin bi Dow Chemical, Stauffer v Goodrich M. Ti Nht, Tosoh ng dng quy trnh oxyclo ha vo nm 1966[5]. Tng bc phn ng ca quy trnh oxy clo ha c th c th hin nh di y: CH2=CH2 + Cl2 CH2Cl CH2Cl CH2Cl CH2Cl CH2=CHCl + HCl CH2=CH2 + 2HCl + O2 CH2Cl CH2Cl + H2O Phn ng tng ca quy trnh oxy clo ha cn bng l: 2CH2=CH2 + Cl2 + O2 2CH2Cl CH2Cl + H2O Cc bc ca quy trnh: (1) Clo ha trc tip (2) Tinh ch EDC (3) Oxy-clo ha (4) Phn hy nhit ca EDC (5) Thu hi HCl t lng v kh thi [6]Di y l cng ngh ca Cng ty EVC sn xut VCM v etylen iclorua (EDC) t etylen, clo v oxy, p dng quy trnh oxy-clo ha vi lp xc tc tng c nh, hiu sut cao (quy trnh LTC). Quy trnh cng ngh ny ginh c gii thng Kirkpatrick Chemical Engineering Achievement Award. Trn th gii, hin c 52 nh my p dng cng ngh ny ang vn hnh hoc ang c xy dng, vi tng cng sut 4,7 triu tn VCM/ nm v 11,2 triu tn EDC/ nm. Cng sut ca tng nh my nm trong khong t 10.000 n 650.000 tn VCM/ nm. M t quy trnh: EDC c sn xut c cng on clo ha b sung v cng on oxy clo ha ca quy trnh. cng on clo ha b sung, etyl v clo phn ng vi nhau trong pha lng, to thnh EDC: C2H4 + Cl2 C2H4Cl2 + nhit 36

Nhit ca phn ng c s dng chng ct EDC to thnh cng on clo ha trc tip v cng on oxy - clo ha, nh tit kim c 0,6 tn hi /tn VCM so vi cc quy trnh thng thng. cng on oxy - clo ha, etylen, oxy v HCl phn ng vi nhau to thnh EDC: C2H4 + 2HCl + 1/2O2 C2H4Cl2 + H2O y l phn ng pha hi, din ra trong tng xc tc c nh, nhit phn ng c s dng sinh hi cao p. Bng vic s dng oxy thay cho khng kh, lng kh qut ra gim 95%, chi ph nng lng v chi ph u t cng gim. EDC c ra v lm kh, sau c tinh ch trong b phn clo ha trc tip. VCM c to ra nh cracking EDC hi lu lm sch v EDC t cng on clo ha trc tip. Phn ng cracking ny c thc hin trong l nhit phn: C2H4Cl2 C2H3Cl + HCl Sau khi lm ngui nhanh v thu hi nng lng trong mt h thng c bit, cc sn phm c tch thnh HCl (hi lu v cng on oxy - clo ha), VCM c tinh khit cao v EDC cha phn ng (hi lu v cng on clo ha v tinh ch). Quy trnh sn xut VCM ny c th c iu chnh "cn bng" sao cho nh my ch sn xut sn phm VCM hoc nh my c th c thit k s dng cc dng EDC hoc HCl nhp t ngoi. Quy trnh ny c t ng ha c th vn hnh n nh, an ton, vi kh nng gim nng sut khi cn. Ngoi ra, quy trnh ny cng c thit k c th khi ng v ngng mt cch d dng. Chi ph nhn cng, vn, chi ph vn hnh v bo dng thp. Hiu sut phn ng i vi etylen v clo t trn 98%.[6] b. Quy trnh sn xut EDC bng phn ng clo ho trc tip nhit cao (quy trnh HTC) 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. 37

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. M 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 m bo s tun hon t nhin ca EDC. Uu 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 dng trc 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 theo quy trnh ny, v vy lng nc thi cn phi x l gim. Ngoi ra, mc tiu th xt cng rt thp.[6] c. Quy trnh sn xut EDC bng phng php oxy clo ha y l quy trnh Vinnolit ca Cng ty Vin Tec dng sn xut EDC bng phn ng ta nhit gia cc nguyn liu etylen, HCl khan v oxy. C th s dng HCl khan t qu trnh sn xut VCM hoc t cc qu trnh khc. Cng ngh ny c p dng ti 13 thit b phn ng 10 nh my, hoc nh mt 38

nh my s dng HCl ring r hoc nh mt b phn ca quy trnh VCM cn bng. Trong mt s trng hp n c th thay th cho cc cng ngh oxy - clo ha hin c bng cch thay i thit b phn ng cho ph hp. Hai dy chuyn sn xut theo cng ngh ny cng ang trong giai on hon thin. M t quy trnh: C th s dng oxy t nh my tch khng kh hoc t quy trnh hp ph p sut cao PSA. Quy trnh Vinnolit cng c kh nng dng c etylen v / hoc HCl khan cha cc dng kh ui t cc quy trnh clo ha trc tip, axetalehyt, monoclo axetic axit,... Phn ng ta nhit ca quy trnh din ra trong thit b phn ng tng si c xc tc clorua ng, nhit 200 220C. Nhit phn ng c thu hi sinh hi cao p (10 bar) hoc gia nhit cc cht lng truyn nhit. Bt xc tc c loi b nh b lc xc tc kh nng kiu mi, hoc bng cch x l nc thi sao cho n p ng cc quy nh cht ch nht v gii hn hm lng ng, ioxin v furan. Quy trnh thn mi trng ny s dng kh hi lu, np n tr li thit b phn ng sau khi ngng t EDC v nc. Sau khi loi b EDC, nc thi ca qu trnh p ng nhng yu cu cht ch nht v mi trng. Sau khi loi b CO2 v cloral/ cloetanol, EDC th c tinh ch trong thit b chng ct EDC. N c th c s dng lm nguyn liu np l cracking nhit phn hoc bn ra ngoi. Nhng c im v u im quan trng: * ng tin cy: S khng ch nhit n nh, lin kt vi thit b truyn nhit hiu qu cao v s phn phi nhit ng u (khng c cc im qu nng) trong tng si khin cho dy chuyn thit b c th d dng t t l thi gian vn hnh trn 99% /nm. H thng phun nguyn liu c thit k c bit cho php vn hnh hai nm khng cn bo dng. Din tch truyn nhit ln cho php t nhit v p sut hi nc cao hn trong cc ng xon lm lnh nh tng an ton i vi nhit gii hn b mt, ni c th xy ra s n mn do nhit xung n im sng ca axit HCl. * An ton: oxy c phi trn vi HCl khan bn ngoi thit b phn ng v c np vo tng si c lp vi etylen. Hm lng oxy trong dng hi lu l khong 0,5% (th tch), ngoi gii hn chy n. 39

* Linh hot: thit b c th vn hnh mc 20% cng sut thit k v c th thay i nhanh chng ch np liu cho ph hp. * Chi ph sn xut thp: xc tc c tui th phc v khng hn ch, t l hao ht thp nh h thng xyclon hiu qu cao (tiu hao di 20 gam xc tc/ tn EDC). Hiu sut phn ng cao ca nguyn liu (98,5% i vi etylen, 99% i vi HCl khan, 94% i vi oxy) v kh nng s dng oxy gi thnh thp t quy trnh PSA m bo tnh cnh tranh cao ca quy trnh ny nh gi thnh sn xut thp. * Hiu qu v mi trng: Hiu sut phn ng 99% l yu t then cht gim s hnh thnh cc sn phm ph. H thng lc kh nng hiu qu cao cho php tch nhng lng nh bt xc tc mn. Ngoi vic loi b EDC d trong nc thi bng phng php gii hp vi hi nc, quy trnh ny khng cn thit b x l b sung khc cho nc thi. Nc thi t tiu chun mi trng ca EU i vi cc nh my sn xut vinyl: hm lng EDC < 5 g/ tn cng sut tinh ch EDC, hm lng Cu < 1 g/tn cng sut oxy - clo ha, cc thnh phn tng t ioxin < 1 g TEQ/ tn cng sut oxy - clo ha.[6] Cc thng s vn hnh chnh: Nhit vn hnh: 200 - 225oC p sut vn hnh: 2,5 - 4 bar p sut hi: 0 bar d. Sn xut EDC bng quy trnh oxy- clo ho mt bc y l quy trnh VCM cn bng ca Cng ty EVC, s dng oxy sch v etylen trong phn ng oxy - clo ha chuyn ha HCl thnh EDC vi lng kh ui thp nht, khng c cc cht gy nhim c micro, khng gy nhim c kim loi nng i vi nc thi, khng c s tch tr bn xc tc phi x l mt cch tn km. Quy trnh ny c vn hnh thng mi t nm 1979. T n nay c 18 nh my c a vo vn hnh vi cng sut t 50.000 n 600.000 tn/ nm. M t quy trnh: thit b phn ng vi tng xc tc c nh, v n; nhit phn ng c ly i sinh ra hi cao p. Phn ng c thc hin vi s d tha ln etylen. S chia tng xc tc mt cch linh hot, s phn b nhit phn ng thch hp 40

v lu lng np liu cao, cng vi h thit b phn ng n chic l nhng yu t gip to ra sn lng ti a v hn ch sn phm ph mc ti thiu. Sau khi ngng t v tch cc sn phm phn ng (EDC v nc), etylen d c nn v hi lu tr li dng kh c lm sch ny c rt ra mt phn ngn nga s tch t cc cht tr. Thng thng, dng kh sch ny c lm kh v a n b phn clo ha trc tip thu hi etylen. iu kin vn hnh: Thit b phi trn oxy c thit k c bit v h thng kha lin ng m bo s vn hnh an ton ngoi gii hn chy n. Kiu thit k n gin v quy cch cht lng cao ca vt liu ch to khin cho thi gian s dng gia hai ln sa cha ln n 2 3 nm, t l thi gian vn hnh t 98% trong mt nm. Nhit phn ng c thu hi sinh hi cao p (18 bar) s dng cho cc b phn khc ca quy trnh VCM (v d nhit phn). Nc thi khng cha bt xc tc l lng, v vy khng cn lng v x l nh nc thi c hi. Hm lng ng trong cc dng nc thi ca tng xc tc c nh di 0,3 ppm, v vy khng cn phi x l.[6] Ch tiu tiu hao nguyn vt liu: Quy trnh thng t hiu sut chn lc 98% i vi etylen v HCl, hiu sut chuyn ha HCl t 99,8%. Do vn hnh trong mi trng giu etylen, quy trnh ch to ra khong mt na lng CO v CO2 so vi cc quy trnh tng si thng thng khc. Ch tiu tiu hao i vi 1 tn EDC l: HCl: 0,748 tn etylen: 0,288 tn oxy: 0,170 tn Nc lm lnh: 48 m3 in: 50 kWh Nng lng lm lnh: 1320 kcal Hi sinh ra (17,5 bar): 0,850 tn II. CNG NGH TNG HP POLYVINYLCLORUA (PVC) PVC c sn xut t 4 phng php: - Phng php trng hp khi. - Phng php trng hp dung dch. - Phng php trng hp nh tng. 41

- Phng php trng hp huyn ph. Nha PVC c s dng cho nhng sn phm bn vng nh ng khung ca s, mi nh v dy cp in, sn nh. Hu ht PVC thng mi c sn xut bng phng php huyn ph. Trng hp khi v nh tng c s dng t hn, cn trng hp dung dch him khi c s dng. Trong qu trnh trng hp gc ca vinyl clorua, monome c hng s chuyn mch tng i ln. (Cm= 1,23.103, 60C) dn n gii hn trn ca polyme thp (Pn < 2000). Lin kt tng phn l mt phng php hu ch c s dng tng hp khi lng phn t cao. Mt khc, cht kh vi hng s chuyn mch ln v d nh THF v butyl andehyt c th c s dng nh cht iu chnh iu chnh khi lng phn t [5]. Bng hng s chuyn mch trong trng hp gc ca vinyl clorua ( 50C): Hp cht Butyl clorua Isopropylclorua 1,2 dicloro etan 2,4 diclo pentan Clo benzen Axeto andehyt 2,4,6 tricloheptan C5.104 7,4 7,0 4,5 5,0 7,4 110 5,0 Hp cht Butyl andehyt Tetrahydrofuran Butyl axetat Tetraclometan Tetrabrommetan Dimetylalinin Vinyl clorua C5.104 350 24 8,4 385 47 000 2700 12,3

Trong qu trnh trng hp gc ca vinyl clorua, c rt nhiu c gng tng tnh n nh nhit. V d, chuyn ho ca qu trnh trng hp vinyl clorua thng khng cao chng li s to thnh nhng mch nhnh di. Nhnh di c to thnh do s ly nguyn t hidro t mch chnh. V v vy u tin xy ra giai on cui ca qu trnh trng hp. Ni i ni phn t c to thnh do s ly nguyn t hidro t mch chnh ca polyme trong qu trnh trng hp. C th trnh iu ny bng cch a vo hp cht c nguyn t hidro linh ng nh xyclohecxen.

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II.1 Trng hp khi Trng hp khi l phng php n gin sn xut PVC, nhng PVC c to thnh ho tan trong pha vinyl clorua. Trong qu trnh trng hp khi, s kt ta polyme bt u xy ra chuyn ho 0,1%. Sau qu trnh trng hp d th xy ra c trong pha polyme v monome. Trong giai on khi u ca phn ng trng hp, tc trng hp l hng s. iu khin s ngt mch v pht trin mch tr nn u tin hn trong giai on cui ca qu trnh trng hp. Khi nhit phn ng di nhit ho thu tinh (Tg) ca PVC sn phm, s khuych tn monome n cc gc ang pht trin rt chm v chuyn ha t gii hn trn. chuyn ho gii hn l khong 96% 55C, 93% 30C, 90% - 10C. ng ch l c qu trnh khuych tn mch ang pht trin v trng hp trong nhiu pha u quan trng xc nh tc cng ca monome vo gc ang pht trin. Nhiu nh nghin cu a ra cc m hnh ng hc ca phn ng trng hp khi PVC. Talamini xc nhn rng qu trnh trng hp vinyl clorua xy ra c trong pha monome v polyme. Ugelstadt tng kt rng gc ang pht trin c th di chuyn gia hai pha monome v polyme. Olaj cho rng gc trong pha monome pht trin thnh cu trc cun v chng bm vo nhau to pha polyme. Hamielec v ng nghip coi s v cht khi u v th tch l hm ca chuyn ho. Cn thit phi lm sng t thnh phn ca c pha monome va polyme thnh lp phng trnh tc cho qu trnh trng hp khi ca vinyl clorua. Theo Hamielec, mt mu hai pha ca hn hp VC/PVC nh l mt hm ca nhit phn ng c m t nh hnh sau:

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Trng hp khi c th chia ra lm ba giai on. giai on th nht ( chuyn ho 0 0,1%), qu trnh trng hp ng th v tc ca qu trnh tun theo phng trnh tc cho h ng th n gin. giai on hai ( chuyn ho 0,1 77%) trng hp din ra trong h v vinyl clorua b by trong cc phn t polyme, Ngoi ra, vinyl clorua t do trong qu trnh trng hp bin mt chuyn ho ti hn (xc = 77%). giai on ba ( chuyn ho ln hn 77%) xy ra qu trnh trng hp vinyl clorua trong phn t polyme trng. Theo mu ny, phng trnh sau cho qu trnh trng hp khi c a ra: Dx/dt = (kp 2/kt)1/2(fkd[I]1/2 exp{-kdt}[1/(1-Bx)][1+[P(1-xc)-1]/xc]x) (1) 1-Bx l h s bin thin th tch theo chuyn ho. Phng trnh ny p dng cho trng hp thc t ca vinyl clorua vi cht khi u l AIBN, kt qu th nghim cho thy phng trnh ny kh chnh xc. M hnh hai pha gn y c p dng cho qu trnh trng hp khi v huyn ph. Giai on hai ca qu trnh trng hp c m rng t chuyn ho pha phn tn bin mt n chuyn ho gii hn. Trong giai on ny phn ng ng th v cng ngy nht mi trng cng tng. Sn phm polyme dng khi kh gia cng v kh iu ch nhit v vy t c s dng. Phng php ny chim 8% tng sn lng nha PVC. Sn phm c tinh khit cao, dy chuyn sn xut n gin (khng cn b phn lc ra), do c tnh kinh t. Tuy nhin sn phm to ra dng khi kh gia cng, hn na phng php trng hp khi cn xy ra hin tng qu nhit cc b lm nh 44

hng n cht lng sn phm. V th phng php ny t c s dng.

II.2. Trng hp hp dung dch Qu trnh trng hp dung dch ca vinyl clorua ng th khi polyme ho tan trong dung mi. Trong trng hp ny, nhng phng trnh tc thng thng cho qu trnh trng hp gc c p dng. nhng trng hp dung dch thng khng c s dng trong cng nghip. Hng s chuyn mch ln vinyl clorua (Cm), hng s tc pht trin mch (kp), hng s ngt mch (kt) ln hn ca nhng monome thng thng khc nh styren v MMA nh trnh by trong bng 3. v vy, khi lng phn t ca polyme to thnh c gii hn trn bi v gi tr Cm ln. Qu trnh trng hp trong dung dch ko di tng i lu v i hi mt lng dung mi ln v c tinh khit cao nn t c s dng trong cng nghip, thng dng trong phng th nghim nghin cu nhng quy lut phn ng do vn tc trng hp khng ln lm.

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II.3. Trng hp VCM bng phng php nh tng Trng hp nh tng l phng php c ng dng vo cng nghip u tin tng hp PVC. nc Anh ch duy nht c phng php ny c s dng cho mi n nm 1944. Trong trng hp nh tng, monome c phn tn trong nc di dng nh n nh. Sn phm to thnh cng tn ti di dng nh (hay cn gi l latex) ca nhng ht polyme trong nc. n phi liu phn tn monome vo pha nc cn phi dng cht phn tn (cht to nh) v khuy mnh. T l gia monome v nc ty thuc vo qu trnh trao i nhit la chn. T l ny cng ln th nhit phn ng ta ra cng ln v do , lng nhit cn phi ti ra khi thit b phn ng bng tc nhn lm lnh cng ln nu mun duy tr nhit phn ng khng i. Mt khc, t l ny cn ph thuc vo n nh ca latex polyme to thnh. Cc cht khi mo s dng trong trng hp nh tng thng phi tan trong nc nh cc persulphat ca kim loi kim hoc ca amoni. Chng c kch hot bng cc hp cht nh sulphua dioxit, natri sulphit, natri bisulphit, natri hidrosulphit... to thnh mt h gi l hot ha kh. H khi mo cng nh nng ca chng quyt nh n tc phn ng trng hp ti nhit phn ng chn v nh vy s quyt nh chu k thi gian v cui cng l quy m ca nh my. Cc cht hot ng b mt anion l nhng tc nhn to nh c dng ph bin nht. l mui kim loi kim hoc amoni; cc sulphonat hoc sulphat ca cc axit bo mch di nh: natri - hoc amonioleat, palmitat v stearat; cetyl sulphat natri v cc hp cht tng t; mui ca cc axit dialkyl sulphosucinic, alkan- v alkylbenzene-sulphonic;dinonyl-citrat amoni; dialkylphosphit v phosphat natri... Nng cht to nh phi ln hn ngng ca nng to mixen. Trn gii hn ny, c ht (ca polyme to thnh) s gim khi nng cht hot ng b mt tng. Thng th c ht polyme nh tng s dng cho cc qu trnh gia cng nng chy l 0,3 m, cn c ht ca polyme dng past th ln hn, c khi vt 1 m. Sau y l v d v n phi liu tng hp PVC nh tng (tnh theo phn khi lng) [3]: Nc 100 46

Cht to nh 0,0 1 Mui m 0,05 0,1 Persulphat amoni 0,050 0,25 Hydrosulphit natri 0 0,2 Monome vinyl clorua (MVC) 55 90 Qu trnh trng hp Trong quy trnh sn xut theo m (khng lin tc), trc tin nc c np vo thit b phn ng (autoclave) sau n cht to nh, cht khi mo, kim v mui m khng ch pH. Khng kh trong autoclave c la ra ht bng kh nit hoc MVC. Sau np MVC di p sut tng ng p sut ring ca MVC (2 10 atm). Nhit ca khi phn ng c nng dn n mc chn bng hi nc qua lp v o ca autoclave.p sut trong autoclave tng dn ln khong 5 15 atm. Khi polyme bt u c to ra p sut trong thit b phn ng s gim dn cng vi s gim lng monome. Qu trnh gim p sut trong autoclave c th c dng lm thng s kim tra tin trnh trng hp. chuyn ha c la chn mc 85 95%. Thi gian phn ng ph thuc vo nhit , nng v bn cht ca h khi mo, thng l khong 6 gi hoc t hn. Tip , autoclave c nng nhit ln 29 trong chn khng thu hi lng monome d. Latex sau c lm lnh v a vo bn cha sn phm. Latex thng phm thng c hm kh t 32 n 45%, c ht t 0,05 0,25 m. n nh ca latex c duy tr pH = 10 11, i khi b sung thm cht to nh tng thi gian bo qun. Khi mi trng chuyn sang axit th latex b t. tng hm kh ca latex ln khong 50%, ngi ta dng phng php to kem ging nh cch lm vi latex cao su thin nhin, nh thm vo khong 1% cht lm c. Sau 1 2 ngy hn hp phn thnh 2 lp, pha trn long hn v pha di c hn, c th tch d dng. Cc cht do ha c th c trn vo latex PVC bng my nghin keo hoc cc thit b tng t. Latex PVC hoc cha do ha c th dng trc tip to ra sn phm. Nhng hu ht thng c ch bin tip tc to polyme dng bt. Tch polyme khi latex 47

 c PVC nh tng dng bt, ngi ta cho thm cht in ly vo latex ng t. Tip theo l ra, lc v sy kh. Tuy nhin, trn quy m cng nghip th cch ny t c ng dng. Vi cng sut ln, bt PVC nh tng thu c bng phng php sy phun, tng t nh sn xut sa bt. II.4. Trng hp huyn ph V hnh thc, trng hp huyn ph ging trng hp nh tng, trong cc monome c phn tn trong pha nc thnh cc ht rt nh. Tuy nhin, y h phn tn c duy tr bng vic kt hp gia khuy trn v ha cht bo v. Ha cht bo v c th l mt colloit (keo) tan trong nc hoc mt cht v c dng bt mn phn tn trong nc. Mt khc, trong trng hp huyn ph ngi ta s dng cc cht khi mo ho tan c trong monome. Do , v kha cnh no y, c th coi nh trong mi ht polyme nh li ti to thnh din ra qu trnh trng hp khi. n phi liu Nhng cht khi mo ph hp bao gm: Cc peroxit ca benzoyl, lauroyl, caproyl, dodecyl, p-cloo-benzoyl, axetyl-cyclohexane-sulphonyl v 3,5,5trimehylhexanoyl; cc peroxy-dicarbonat ca dietyl v di-izopropyl; cc hp cht azo nh 1,1-azobis-izobutyronitril v dimethyl 1,1-azobis-izobutyrat. Hin nay thng dng nht l cc peroxy-dicarbonat. Tuy nhin nh cp trn, vic la chn cht khi mo thch hp ph thuc vo nhit phn ng trng hp. Nng ca cht khi mo thng mc 0,01-0,1% ty thuc vo bn cht ha hc ca cht khi mo, nhit phn ng v mc chuyn ha. Cht to huyn ph thng s dng l nhng cht colloit (keo) tan trong nc nh polyvinyl alcol, gelatin, protein t nhin, cc dn xut xenlulo tan trong nc nh metyl v cacboxymetyl xenlulo, dextran, tinh bt, natri alginat... Mt s loi bt mn v c khng tan trong nc cng c s dng lm tc nhn to huyn ph. Cc cht l bt talc, cao lanh, betonit, bari sulphat v nhm hydroxit. Cht c s dng ph bin nht l polyvinyl alcol (PA).PA c nhiu loi ty thuc vo mc thu phn cng nh khi lng phn t. Lng PA thng chim t 0,05-0,5% khi lung monome.

48

Ngoi nhng cht trn, ngi ta cn s dng cc loi mui m nh natri hydro pht pht hay borax trnh gim pH ca pha nc khi phn ng trng hp xy ra.i khi mt s cht chng to bt nh Ctanol, polyetylen silicat cng c s dng gim thiu s hnh thnh bt khi tch monome d cui giai on phn ng. Sau y l mt v d n phi liu (tnh theo phn khi lng): Nc 100 Colloit to huyn ph 0,1-0,5 Mui m 0 0,1 Cht khi mo 0,05 0,3 Cht chng to bt 0 0,002 MVC 50 70

Hnh 12 : S quy trnh tng hp PVC huyn ph 1. Bn phn ng, 2. Bn thu hi MVC, 3,5. Bn cha va PVC, 4. Thp chng ct, 6. Bn cha MVC thu hi, 7. My li tm, 8. My sy, 9. X l kh thi, 10. My sng, 11. Xil cha bt PVC, 12. My ng bao, 13. My nn kh Qu trnh trng hp huyn ph theo m c tin hnh trong thit b phn ng c p lc (autoclave) 1. Nc c np vo trc, tip theo l tc nhn to 49

huyn ph, mui m di dng dung dch. Sau khi khng kh c ui ra khi thit b phn ng bng kh tr, MVC v cht khi mo c np vo di p lc.Ch khuy c duy tr sao cho c th ph v pha lng ca MVC to ra nhng ht nh li ti vi kch c mong mun. Qu trnh gia nhit cng nh lm lnh c iu chnh chnh xc theo nhit yu cu sn xut mi loi sn phm (t 50 70oC). Trng hp huyn ph v c bn l nhng chui trng hp khi nh trong pha nc. C ch cng nh ng hc phn ng ging nh trng hp khi.Ngoi ra, cc ht nh li ti c to ra ban u khng nht thit phi tn ti trong sut c thi gian phn ng. Ph thuc vo bn cht v nng ca cht to huyn ph cng nh ch khuy, nhng ht nh li ti c th lin kt li vi nhau v sau li b phn tn. Nhng ht polyme c th c to thnh t mt git hoc t mt s git lin kt vi nhau ti thi im nht nh ca phn ng. Phn ng c xem l kt thc khi p sut trong thit b gim n mt tr s cho trc. Hn hp sau phn ng, c gi l va, khng n nh cha cc ht polyme trong pha nc v monome cha phn ng. Ngng khuy s dn n vic lng t cc ht polyme. Chnh v vy, va PVC vn phi tip tc c khuy cho n khi tho ht sang bnh khc cng c my khuy 2. Lng MVC cn li sau phn ng chim 10-20% khi lng ban u. Phn ln lng MVC s c tch ra bng bay hi v c thu hi ti thit b ngng t v bn cha 6. Do tnh c hi cao ca MVC nn lng MVC d cn phi c tip tc tch trit . V th, va PVC c chuyn sang bn cha 3, gia nhit v chng ct trong thp 4 v lng MVC cn li cng c thu vo bn cha 6. Va PVC sau khi tch MVC d c a n bn cha 5, tch nc ti my ly tm 7, lm kh ti my sy 8. Nhng cht bay hi c dn qua thit b x l kh thi 9, phn cn li khng c hi c thi ra ngoi khng kh. Bt PVC kh sau khi qua my sng 10 loi nhng ht qu c, c kh nn y qua silo cha 11 v c ng bao vi trng lng mi bao l 25 kg ti my ng bao 12. Dy chuyn sn xut S trn Hnh 12 l v d v mt nh my sn xut PVC bng phng php huyn ph. S ny c th s dng cho tng hp PVC nh tng vi vic ch cn thay cng on tch nc bng my ly tm 7 v my sy kh 8 bng h thng sy phun. 50

i cng vi dy chuyn cng ngh trn l cc cng trnh ph tr: kho v bn cha nguyn liu, thit b phc v cho vic pha ch cc cht ph gia, xc tc... Thit b phn ng hay cn gi l autoclave, phi chu c p sut lm vic ti 15 kg/cm2 (1500 kN/m2). Autoclave v hu ht cc thit b khc trong dy chuyn sn xut c ch to bng thp khng g chng n mn v nht l trnh cho polyme thu c b ln tp cht kim loi, nh hng xu ti cht lng cng nh yu cu s dng tip theo ca nha PVC. B mt bn trong cc thit b, nht l ca autoclave, phi lun c gi sch v bng. Bi v cc vt bn, vt lm, vt xc u l nhng ni cc ht polyme to thnh bm vo, rt kh ty ra. Mt khc nhng ht bm vo s li l nhng mm cho nhng ht khc bm theo nu khng c ty ra kp thi. Theo thi gian v di tc ng ca nhit phn ng, nhng ht polyme ny s nh hng n cht lng polyme cng nh n qa trnh gia cng bt to sn phm. trnh hin tng bm dnh trn thng sau mi chu k nht nh, ngi ta dng sng phun nc vi p lc cao ra thnh bn trong thit b phn ng. Mt s ha cht cng c s dng chng hin tng bm dnh trn. Kch thc autoclave cng rt khc nhau v ngy cng ln nh my lun cung cp nha cho nhu cu ngy mt tng. Autoclave nh nht c dung tch 1m3 cn loi ln vi dung tch 100 150 m3. Khi dung tch thit b tng, t l gia din tch b mt v th tch thit b s gim, ng thi din tch trao i nhit c gia thnh thit b v lp v bc bn ngoi cng gim. Mt khc, th tch thit b tng s lm cho dy ca thnh thit b tng theo m bo chu c p sut ca qu trnh. trnh vic gim kh nng truyn nhit c th tng t l gia nc v monome. Nh vy, nu thit b phn ng cng ln th phn th tch dnh cho monome cng nh. H qu l sn lng nha mi m s tng chm hn so vi tc tng dung tch thit b. Mt tr ngi na ca s tng th tch autoclave l vn khuy, tc l kch thc cnh khut, cng sut motor khuy cng phi ln duy tr s ng u mi trng phn ng. Tt c nhng tr ngi trn buc nh thit k ch to phi la chn autoclave ph hp vi thc t ch khng th theo mong mun. Cng chnh v 51

vy, nh sn xut phi cn c vo s lng cng nh dung tch ca mi thit b phn ng la chn cng sut cho nh my. Hin nay c rt nhiu nghin cu ci tin cng ngh sn xut PVC nhm to c sn phm c cht lng ngy cng cao, p ng c ngy cng nhiu nhu cu cng nh nng cng sut thit b, gim gi thnh sn phm. Mt v d ca hng nghin cu ny l ci tin ca Cng ty Vinnolit thuc hng ThyssenKrupp. Cng ty ny ch to autoclave vi thnh bnh pha trong c gn (p) thm mt lp cc na ng trn bng thp khng g (xem Hnh 13) tng kh nng truyn nhit v nh t c nhng kt qu nh trong Bng 9.

Hnh 13 : Ci tin thnh thit b phn ng trong cng ngh sn xut PVC-S ca hng Vinnoilt

Bng 2.1: Nhng tnh nng u vit ca thit b ci tin Cc thng s k thut Din tch lm lnh Mc truyn nhit H s truyn nhit C 100% 100% 100% Mi 122% 283% 175%

52

Cng sut

100%

213%

III. SO SNH GIA CC PHNG PHP. So snh cc phng php trng hp gc khc nhau ca vinyl clorua c trnh by trong bng sau. Bng so snh cc phng php trng hp gc ca vinyl clorua. Yu t Khi Kh nng ho tan ca cht khi u Ph gia Tan trong VC Khng Phng php trng hp vinyl clorua Dung dch Tan trong VC Dung mi Nh tng Khng trong VC tan Huyn ph Tan trong VC

Nc, cht to Nc, tc nh tng nhn phn tn Cn thit Cn thit D dng D dng 20-300

Khuy trn iu khin nhit S c lp PVC Kch c ht (m)

Khng cn Khng thit cn Kh Thu VC 60- 300 C c th

D dng D dng 0,1

C th c < 0,1

Mc d trng hp khi l phng php n gin nht sn xut PVC nhng phng php huyn ph li c s dng ch yu trong cng nghip trnh nguy c pht n trong qu trnh trng hp khi. Phng php trng hp dung dch sn xut PVC t c s dng do i hi mt lng dung mi ln v c tinh khit cao vi phng php trng hp khi th sn lng khong 8% so vi tng sn lng PVC.

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Thep phng php ny sn phm c sch cao, dy chuyn sn xut n gin. khng cn b phn lc ra, do kinh t hn. Tuy nhin sn phm to dng khi kh gia cng, ngoi ra n cn nh hng n cht lng sn phm. Nn t c s dng. Hai phng php trng hp nhu tng v trng hp huyn ph vn c xy dng rng ri (nhng phng php huyn ph vn c s dng nhiu hn) do c u im ng k nh sn phm to ra dng ht, gia cng, vn tc trng hp cao, nhit phn ng thp v c bit khng xy ra hin tng qu nhit cc b. Tuy nhin nhc im l sn phm d b nhim bn bi cht n nh v cht nh ho do c cng on ra v sy trong dy chuyn sn xut.

CHNG III: TNH TON CC THNG S K THUT CHO THIT B PHN NG CA CNG NGH SN XUT PVC BNG PHNG PHP HUYN PH

cho n ca em c thc t hn em chn tnh ton cc thng s k thut thit b phn ng ca nh my sn xut nha v ha cht TPC VINA TNG QUAN V CNG NGH SN XUT NHA PVC BNG PHNG PHP HUYN PH NH MY TPC VINA
I.

I.1. Quy cch nguyn liu v thnh phn 54

Nguyn liu phn ng gm: - Monome VC dng trng hp phi th lng nn cn c lm lnh v gi nhit rt thp nh hn 13C l nhit si ca VC. nguyn cht ca VC phi ln hn 99,9% trng lng, phi m bo hm lng axetylen thp hn 0,002% trng lng. - Dung mi nc dng trn hp phi l nc ngng tinh khit. - Cht khi u thng dng: Peroxyt benzoil (POB) l cht rn mu vng nht, d bt la v n khi va chm mnh, c st hay h nng, c th bc chy khi ln H2SO4. V vy, POB cn c bo qun tt. - Cht n nh PVA thuc h polyme v nh hnh, c tnh k nc cao. Bo qun trong cc bao vi hay gai. PVA c a vo dng dung dch 5% trong nc. - Xt NaOH dng x l kim nh tng sau khi trng hp, c th dng dng rn hoc lng - Ngoi cc thnh phn trn cn s dng: dung dch m, tc nhn chng to bt, tc nhn iu chnh khi lng phn t I.2. Thnh phn nguyn vt liu Ty theo loi sn phm v iu kin phn ng m thnh phn nguyn vt liu c th thay i, c th a ra mt v d nh sau: - Nc ct 1300 kg - VC 1000kg - POB 5kg (0,5% lng VC) hay AIBN 3kg (0,3% lng VC) - Cht nh ha glatin 8 kg (0,8% lng VC) a vo dng dung dch 5% trong nc, dng nc nng 60 - 70 C pha ch dung dch v phi dng ngay khng lu qu 4 -5 gi s b hng. I.3. Dy chuyn sn xut v thit b Sau khi chun b xong nguyn liu, tin hnh cho nguyn liu vo thit b phn ng theo th t sau: Nc ct dung dch nh ha cht khi mo cht m VC. Phn ng trng hp trong kh tr v vy cn dng N2 ui ht khng kh ra. Qu trnh phn ng tin hnh qua cc giai on sau: 55

- Trc ht dng nc nng 70 80 C un nng dn dn hn hp phn ng ln 40 70 C v a p sut trong ni ln 5 8 atm kch ng phn ng trng hp. Ty theo loi nha cn quy nh r nhit v p sut thch ng. - Tip theo l phi dng nc lnh duy tr tht ng nhit v p sut quy nh cho phn ng trng hp tip tc pht trin mch polyme (nhit khng sai qu 1 C, p sut khng qu 0,1 kg/cm2), thi gian pht trin mch c th t 20 n 40h gi ty theo loi nha v qu trnh khng ch cng nh quy cch thnh phn nguyn vt liu. - Cui cng p sut h thp xung di mc quy nh th tng dn nhit ln chng 60 70 C lm t mch cho n khi p sut cn khong 2- 3 atm th coi nh phn ng trng hp hon thnh. Trng hp xong thi tp trung VC khng tham gia phn ng ri dng kh nn chuyn c khi phn ng sang thit b x l kim. Giai on x l kim vi mc ch ch yu l lm phn hy cc gc ca cht khi u v cht nh ha (to thnh cc mui natri tan trong nc) keo t v tng tnh n nh nhit ca nha theo phn ng sau: 2(C6H5COO)2 + 4NaOH 4C6H5COONa + 2H2O + O2 Giai on nguy him trong khi trng hp VC l khi nhit , p sut trong ni phn ng vt qu mc quy nh. Khi dng nc ct cao p cho trc tip vo ni phn ng h p sut hoc l cho VC thot ra my to bt hay cho ra ngoi khng kh. Thit b chnh trong dy chuyn l ni trng hp gm cc b phn: Ni phn ng vi kch thc 40 80 m3 dng sn xut (c th c loi ln hn) bn trong ni c trng men gim lng polyme bm vo vch thng, bn ngoi c o gia nhit. Trong ni phn ng c lp cnh khuy (thng l cnh khuy chn vt) phn tn monome trong dung mi. Ngoi ra c cc van cho nguyn liu vo v tho sn phm ra. Trng thi tnh ca ni l sau khi cho nguyn liu vo, ni c hn kn li v to chn khng 28mmHg. Khi p sut trong ni l 0,7 Mpa qu trnh phn ng pht trin. Nhit v p sut duy tr sut qu trnh pht trin mch, khi p sut gim th nhit tng do s tiu tn monome. 56

Cng thc c s dng hin ti khng khc nhiu v c bn so vi cng thc c pht trin ti c nhng c thm PVA (c x phng ho mt phn bi polyvinyl axetat), gelatin, metylxenlulo, v copolyme vinyl axetatmaleic anhyt c s dng vi vai tr cht phn tn. Hnh dng ca phn t polyme c th c iu chnh bng cch thm mt lng nh cht nh ho th hai vo nh sn phm c c etylen oxit v du lu hunh vo cng thc. Nu s dng gelatin, dung dch m c thm vo d pH trn im ng in. Tnh cht cui cng ca nha ph thuc rt nhiu vo h thng trng hp.Gelatin thng to ra cc phn t thu tinh hp ph cht ho do rt km, trong khi PVA cho cc phn t xp c th hp th rt tt cht ho do cho ra hn hp bt kh[11]. V VC l mt cht lng c nhit si rt thp, nn n c cha trong nhng thng p sut cao, p sut ny c iu chnh ph thuc vo nhit , VC c vn chuyn trong cc ng thp khng g, cng c th s dng ng th thng. Thng lng VC c th dng thng lng th tch song c chnh xc khng cao, v vy thng lng trng lng thng c u tin s dng. Qu trnh trng hp c xy ra u tin bi vic np vo thit b phn ng lng yu cu nc kh ion, sau l tc nhn phn tn, dung dch m v cht khi u, v d nh lauryl peroxyt hoc azobisisobutylnitril (AIN) thng rt hay c s dng. Sau khi thit b c hn li, n c to chn khng loi b oxi ri monome s c cho vo t mt thng lng. Sau my khuy c khi ng, nhit ca h thng s c nng ln n nhit trng hp (45 60C) bng phun hi nc vo o gia nhit ca thit b. C mt giai on m u ngn, thng khong mt gi trc khi phn ng trng hp din ra v h thng iu khin s cung cp nc lnh vo o gia nhit iu chnh nhit phn ng n gi tr nh trc. Tc ln nht ti phn ng trng hp c cho php din ra ph thuc vo nng ca cht khi u v nng ca vinyl clorua, v d t l ca monome so vi nc. Tc phn ng khng phi l mt hng s m tng dn dn trong sut qu trnh trng hp n khi t cc i ti chuyn ho 60 80%. iu ny c ngha rng lng vinyl clorua c th chuyn ho thnh polyme b gii hn bi tc tn nhit khi tc phn ng ln nht, nu thu nhit bng nc lnh gi nhit phn ng ti gi tr cn thit. Trong 57

sut giai on u ca qu trnh trng hp, tc phn ng lun thp hn gi tr cc i v vy khng t c nng sut ti a ca thit b phn ng. Thm mt hng s tc na ca phn ng trng hp c th thu c bng cch s dng cht khi iiospropyl percacbonat (DIPP). DIPP em li rt nhiu u im trong vic gim thi gian khi u; n cho php nng sut ca quy trnh trng hp tng t 20 50%. Percacbonat nh hng n cu trc ca ca cc phn t polyme c bit l xp v vy vic s dng loi cht khi u ny b hn ch ch vi mt s loi polyme nht nh. thu c nha c xp cao th chuyn ho phi hn ch khong 50% . tng tnh kinh t th tc trng hp c iu chnh tng ng vi s gim lng polyme thu c t mi thit b v lng VC cha trng hp phi thu hi. Nhng nhc im ny c khc phc mt phn bng k thut thu hi 10 20% huyn ph t thit b phn ng khi chuyn ha t 45 50%. Khi lng phn t ca PVC c quyt nh ch yu bng nhit ca qu trnh trng hp. Tc trng hp tng khi tng nhit , nhit trng hp ln nht thng c s dng l 60C. Tng nhit trng hp thc y qu trnh truyn nhit dn n nng sut ca quy trnh cao hn v nha thu c c khi lng phn t thp hn. Nu c gii hn p sut trong thit b trng hp, i khi tc nhn chuyn mch c s dng to PVC khi lng phn t thp. Nhng tc nhn thng dng l hidr ccbon clo ha v isobutylen. p sut trong h thng khng i trong sut qu trnh trng hp cho n khi chuyn ha t khong 70%, sau gim nhanh theo qu trnh. Trc chuyn ha 75%, VC t do tn ti trong h thng di dng git trong pha lng, nhng khi chuyn ha cao hn th monome hon ton b hp th trong cc phn t polyme. Polyme c t trng cao hn monome nn th tch ca pha hu c co li khong 35% trong qu trnh trng hp. S co ngt ny c li dng gii quyt vn truyn nhit ti nh im ca phn ng, bng cch cho thm nc lnh vo h thng trng hp khi s co ngt t khong 25%. Khi qu trnh trng hp v cn bn hon thnh th tc phn ng gim rt nhanh. Do , s khng kinh t khi tng chuyn ha ln trn 95%.

58

Trong trng hp huyn ph, tc dng chnh ca khuy trn l iu chnh kch thc ht, sau l tng cng v iu chnh qu trnh truyn nhit[3]. Trng hp huyn ph rt kh thc hin trn dy chuyn lin tc v s kh khn trong vic cn tr polyme tch ra khi pha nc tr khi h thng c khuy trn mnh. C th dng ba thit b dng thng c khuy chy lin tc, hai chic ngang hng vi chuyn ha ca qu trnh trng hp khong 70%. Sau huyn ph c chuyn sang thit b phn ng th ba, ti phn ng gn nh hon thnh. S lng polyme trong h thng ng ni cng gy tr ngi cho qu trnh, v s to thnh mng polyme trn thnh thit b phn ng lm gim kh nng truyn nhit v lm tng nhng phn t khng tan trong sn phm. Nu nhng vn ny c gii quyt, th nn dng dy chuyn lin tc gim nhn cng v vn u t. T thit b phn ng trng hp, khi phn ng trong thit b s c chuyn sang thit b thu hi thu hi VC t do. Thit b ny gm nhiu vi nc p sut cao v mt thit b ngng t thu hi VC. Bn thu c cn gia nhit, bng cch phun trc tip hi nc nhit cao, cho qu trnh thu hi c thun tin, nhng ch trnh nhit cc b dn n phn hy nhit polyme. Nha huyn ph thng c tch t pha nc bng mt my ly tm lin tc; nc tch ra v vt liu cha khong 25% nc. Sau vt liu c chuyn qua my sy nh vt ti[3]. Sy polyme thng c thc hin trong my sy kh thi vi nhit khng kh khong 80C. Cc phn t polyme c phn tch bng xyclon. Mi giai on s gim hm m xung khong 5%. Qu trnh sy c hon thnh cng bng cch cho vt liu i qua my sy th hai, cng l my sy kh thi hay my sy thng quay. My sy tng si cng c s dng rng ri. Yu cu quan trng nht ca my sy l trnh s bm dnh ca polyme vo thnh thit b lm hng vt liu. Mc d khng kh c gia nhit khong 80C nhng nhit ca polyme ch t khong 60C v thng khng xy ra s phn hy nhit nu polyme khng b cn tr trong thit b sy. S tht thot polyme trong xyclon vo khong di 0,2% v c th hn ch thm bng cch lp thm 59

thit b lc ti u ra ca h thng sy. Polyme kh c sng loi b ht th. Nhng phn t th ny thng c to thnh do s kt t hay mng bm trn thnh thit b sy hoc l cc tp vt ri vo trong h thng. Sng thng s dng l sng 40 mt hoc 60 mt. Sau , nha c ng bao trong bao giy nhiu lp. Quy trnh trng hp c th c iu khin bng h thng iu khin s ha. S trn hp v nhit trng hp c iu khin bng my tnh lm tng cht lng sn phm, gim gi thnh v tng nng sut cho dy chuyn do gim ti a thi gian ngh ca thit b phn ng. Mt h thng my tnh song song khc c chc nng tnh ton khi lng vt liu v iu chnh dng ph gia tng ng. Lng vt liu cho vo my trn v thit b phn ng sau khi x hn hp phn ng c tnh ton v iu khin. Qu trnh trng hp c iu chnh bng cch iu chnh lng hi v nc lnh cho vo o gia nhit ca thit b phn ng. H thng cng s bo khi no qu trnh trng hp c s c hay ang trong trng thi hot ng bnh thng. H thng iu khin s ha cho thy tt hn rt nhiu so vi h thng iu khin tng t[11]. I.4. Dy chuyn sn xut PVC huyn ph ti nh my TPC Vina: TPC Vina l mt nh my sn xut bt nha PVC bng cng ngh hin i (cng ngh ca Mitsui Tosoh Nht Bn) vi dy chuyn thit b tin tin, t ng ha hon ton v c chu trnh khp kn, khng gy nhim mi trng. Cc cng on chnh: 1. Chun b nguyn liu 2. Chun b thit b phn ng 3. Np liu 4. Gia nhit 5. Phn ng chnh 6. Tho liu 7. X l kim 8. Tch VCM 9. Hi lu VCM 10.Tch nc 60

11.Sy 12.Sng phn loi 13.ng bao 14.X l nc thi Chi tit: 1. Chun b nguyn liu: - Nc khong 40 50 tn/m, lng th tch bng van o lu lng. Nc dng l nc ngm c x l bng than hot tnh ri cho qua ct trao i ion. Sau cho qua thit b trao i nhit ri n b cha. trong b cha nc c nhit khong 40C - VCM lng th tch bng van o lu lng. - Cht khi mo: Peroxyt dng dung dch hoc nh tng c bo qun trong kho lnh nhit -10C n -20C. Peroxyt c ong bng can hoc bnh. Lng trng lng, n v tnh l kg. - Cht n nh huyn ph PVA, lng trng lng. 2. Chun b thit b phn ng: - Ht chn khng bng my ht chn khng loi Oxi khng kh. H p sut xung cn ~ 0 atm. - Ph chn khng bng VCM (bm mt lng VCM vo). - Phun cht bm dnh ln b mt thit b. (Khong 100 m th ra cn bm trong thnh thit b mt ln. Ra bng cch dng vi phun nc cao p tch ri cc mng bm) 3. Np liu: Vo thit b phn ng chnh theo th t sau - Nc. - Cht n nh huyn ph PVA. - VCM. - Cht khi mo: dng Cumen peroxyt hoc cc peroxyt khc ty trng hp, nhit phn hy ca peroxyt. (Nh my TPC Vina s dng 2 thit b phn ng chnh vi dung tch mi thit b l 150 m3) 4. Gia nhit: 61

Nc nng c a vo v o ca thit b phn ng chnh. Gia nhit cho n khi t gn nhit phn ng. Khuy trn. 5. Phn ng chnh: Dng nc nng gia nhit thit b phn ng chnh v duy tr nhit t 50 70C ty trng hp (ca loi PVC sn xut) Vi trng hp t 1000 1050 th nhit phn ng khong 57C. Thi gian phn ng: tp = 3h45 4h Thi gian gim p: tga = 1h30 Tng thi gian phn ng: t = 5h15 Cui phn ng sn phm c chuyn ha khong 85%. p sut trong thit b phn ng cn khong 6 bar. 6. Tho liu: T thit b phn ng chnh xung bn Blow Down qua mt b trung gian nh c gn bm p sut. Lc u hn hp c tho nh chnh lch cao, khi gn ht do khi lng hn hp trn thit b phn ng nh v nht ca hn hp cao nn hn hp khng t chy c. Lc , dng bm b trung gian (th tch 1 m3) bm hn hp xung bn Blow Down. T bn Blow Down hn hp c tho xung bn Blend Tank, ti y khuy trn hn hp c th vi vi m khc. 7. X l kim: Sau khi huyn ph chy ra b Blow Down th trong huyn ph vn cn phn ng trng hp. Do cho thm cht AD3 vo km hm phn ng trng hp. Huyn ph giai on ny c pH khong 3. Sau cho NaOH (d) + Bis phenol A + Nc (ha tan) vo x l kim. 8. Tch VCM: Hn hp t Blend Tank c bm ln thp VCM Stripper. Trong thp ny huyn ph i t trn xung cn hi nng i t di ln. Trong thp c cc a l, khng gian gia cc a y m tng s tip xc gia hai pha. VCM thot ra i ln nh thp ra thit b x l VCM. 9. Hi lu VCM: 62

Thu hi hi VCM trong bnh Blow Down bng p sut m, sau thu hi VCM cn li khong 1% trong bnh Blow Down. VCM dng hi thot ra t thit b phn ng chnh, b Blow Down, Blend Tank, Thp VCM Stripper c dn v cc thit b tch bt. Sau cho qua thit b ngng t ngng t VCM (dng nc nhit thng) ri vo bnh cha VCM lng. T bnh cha, VCM lng c bm qua cc thp x l. Gm 2 thp x l. Thp th nht l thp hp ph, trong thp y NaOH dng rn ht nc. Thp th hai l thp chng ct tinh ch VCM. Sau VCM lng c hi lu v thng cha VCM ban u. 10. Tch nc: Hn hp sau khi qua thp VCM Stripper c a qua mt thng khuy trn trung gian. T thng ny hn hp c bm vo my ly tm. Trong my ly tm, PVC m c m khong 70% c tch nc xung cn m khong 20 25%. 11. Sy: Bng thit b sy tng si (my sy 1 tng). PVC t my ly tm c chuyn xung thit b sy tng si. Trong thit b sy tng si, khng kh nng thi t di ln vi tc dng chnh l to lng gi cho bt. Nc nng c bm qua v o c tc dng lm kh vt liu sy. Sau khi sy hm m ca PVC gim xung cn khong 0,3%. 12. Sng phn loi: Bng sng chn ng Bt PVC t thit b sy c chuyn qua sng chn ng. Sau khi sng lng ht th rt t, ch chim khong 0,05%. 13. ng bao: PVC thnh phm dng bt trng ht nh (kch thc khong 100 150 m) c chuyn qua xil cha hoc ng bao. 14. X l nc thi: Nc thi t cc cng on c tp trung ri a qua thp x l nc thi, hi t nh thp a v thit b thu hi VCM. Nc thi chy ra h thng thot nc. 63

II. TNH CN BNG VT CHT Mc ch ca vic tnh cn bng vt cht l bit c lng cc nguyn liu cn cung cp trong qu trnh sn xut, t ta c th lp k hoch chun b nguyn liu d tr cng nh cho qu trnh sn xut ca nh my, trnh trnh trng thiu ht nguyn liu lm gin on qu trnh sn xut. Vic tnh ton cn bng vt cht cn gip cho ta xc nh chnh xc gi thnh ca sn phm trong qu trnh sn xut t iu chnh gi thnh ca sn phm cho ph hp v gip cnh tranh trn th trng. Ngoi ra, vic tnh cn bng vt cht s tnh c thit b c kch thc, trng lng l bao nhiu b tr v xy dng nh my t c chnh xc, an ton trong qu trnh lm vic. II.1 Thng s ban u n phi liu cho qu trnh sn xut PVC huyn ph: Cn c theo n phi liu s dng [29]: Nguyn liu VCM 99,9% Nc Keo PVA 95% Cht khi mo POB 96% Cht m Na4P2O7.10H2O 95% Ch lm vic ca nh my gm c - S ngy lm vic thc t - Hiu sut phn ng to nha - chuyn ha l - Hao ht nguyn liu Phn khi lng 100 phn khi lng 150 phn khi lng 0,05 phn khi lng 0,1 phn khi lng 0,04 phn khi lng : 330 ngy : 90% : 72% : 2%

- Thi gian gia nhit cho thit b phn ng l (40-70 oC) : 1 gi - Thi gian np liu - Thi gian phn ng cho mt m - m ca PVC sau khi ly tm trc khi sy - m ca PVC sau khi sy 64 : 0,5 gi : 6 gi : 29% : 0,3%

- Hn hp nguyn liu u vo thit b phn ng c nhit : 30oC. - Phn ng chnh ta nhit vi hiu ng nhit : 80 kJ/mol. - Nhit ca hn hp sn phm u ra l: 80oC Dng dng nc tn nhit cho phn ng: - Nhit u vo ca nc: 40oC - Nhit u ra ca nc: 110oC Thnh phn nguyn liu u vo: Nguyn liu u vo Vinylclorua mi(99,9) Vinylclorua tun hon Thnh phn nguyn liu (%V) 90 10

II.2 Tnh cn bng vt cht cho thit b phn ng 1. Thi gian cho mt m sn xut Trnh t cc bc din ra trong qu trnh phn ng nh sau: Qu trnh Np liu Gia nhit cho ni phn ng Phn ng chnh Tho liu Tng thi gian Thi gian (pht) 30 60 360 (6 gi) 30 480 (8 gi)

Dy chuyn sn xut gm 3 thit b phn ng hot ng song song. B tr mt ngy lm vic 3 ca, mi ca 24 : 3 = 8 gi. Nh vy mt ngy ta sn xut c 3 m, vi thi gian ca mi m sn phm l 8 gi. 2. Nng sut ca mt m sn xut S dng h thng 3 ni phn ng hot ng song song, thi gian ca mi m sn phm l 8 gi. S ngy lm vic thc t: 330 ngy 65

Nng sut ca thit b phn ng l 150000 tn/nm, do nng sut ca mt ngy lm vic ca thit b phn ng l: 150000 =454,546 [tn/ngy] 330 Nng sut tnh theo mi gi sn xut l: 100 500 =1 ,9 9 8 34 [tn/gi] 302 3x4 S ngy lm vic ca mt nm l: 24 . 330 = 7920 [gi] S dng h thng 3 ni trng hp nu song song, thi gian ca mi m sn phm l 8 gi. Vy s m sn phm ca mt thit b phn ng trong 1 nm l: 7920 3 =2970 [m] 8 Vy nng sut ca mt m sn xut trong mt nm: 1 00 0 5 0 =5 ,5 5 [tn] 0 0 27 90 3. Tnh cn bng vt cht cho thit b phn ng Tnh cn bng vt cht cho mt tn sn phm trong giai on trng hp 3.1. Tnh lng VCM v cht khi mo: Do m trong nha l 0,3%, lng PVC kh trong 1 tn sn phm: 1000.(100 - 0,3) = 997 [Kg] 100 Hiu sut qu trnh trng hp l 90%, do hao ht sn phm trong ton b qu trnh 10%, bao gm: tn tht trong giai on trng hp, sy-ng bao, ly tm-ra nha, x l kim Lng PVC kh thu c sau khi trng hp l: 997x 100 = 1107,78 [Kg] 90 Tng lng PVC kh hao ht trong sut qu trnh sn xut: 1107,78-997 = 110,78 [Kg] + Tnh lng VCM cn dng: 66

Lng PVC trn l do VCM v cht khi u trng hp to thnh. Do lng VCM tham gia vo qu trnh chuyn ha l: 1107.78 [Kg] Vi chuyn ha 72% do lng VCM ban u l: 1107,78x 100 = 1538,583 [Kg] 72 Lng VCM khng phn ng (cha tham gia vo qu trnh chuyn ho) l: 1538.583 1107,78 = 430,803 [Kg] nguyn cht ca VCM l 99,9% do lng VCM cn dng l: 1538,583x 100 = 1540,123 [Kg] 99,9 Hao ht nguyn liu l 2%, do lng VCM thc t dng l: 1540,123x 100 = 1540,123 [Kg] 98 Lng VCM hao ht do s tn tht nguyn liu l: 1571,554 1540,123 = 31,431 [Kg] Nguyn liu VCM u vo: Vinylclorua mi (99,9%) 90 % v Vinylclorua tun hon 10 %. Lng VCM mi cn dng cho 1 tn sn phm l: 1571,554x 90 = 1414,4 [Kg] 100 Lng VCM tun hon cho mt tn sn phm l: 1571,554x 10 = 157,16 [Kg] 100 +Tnh lng cht khi u: Lng cht khi u POB 96% cn dng theo n phi liu l: 1571,554 0,1 M POB = = 1,572 [Kg] 100 Vi nguyn cht 96% th lng POB nguyn cht c a vo: 1,572 100 M POB = = 1,6375 [Kg] 96 Hao ht nguyn liu l 2%, vy lng cht khi mo cn dng l: 1,6375 100 M POB = = 1,6709 [Kg] 98 67

Tn hao do qu trnh chun b nguyn liu l: M POB = 1,6709 - 1,6375 = 0.0334 [Kg] 3.2. Tnh lng cht n nh huyn ph PVA Lng cht n nh bng 0,05% khi lng VC: 1571,554 0,05 M PVA = = 0,7858 [Kg] 100 Vi nguyn cht 95%, lng PVA c a vo: 0,7858 100 M PVA = = 0,8271 [Kg] 95 Hao ht do qu trnh chun b nguyn liu l 2%, vy lng cht n nh huyn ph cn dng l: 0,8271 100 M PVA = = 0,844 [Kg] 98 Tn hao do qu trnh chun b nguyn liu l: M PVA = 0, 844 - 0,8271 = 0,0169 [Kg] 3.3. Tnh lng cht iu chnh pH mi trng Lng cht iu chnh pH mi trng bng 0,04% khi lng VC: 1571,554 0,04 M Na4P2O7 = = 0,6286 [Kg] 100 nguyn cht 95% th lng Na4P2O7.10H2O c a vo: 0,6286 100 M Na4P2O7 = = 0,6617 [Kg] 95 Hao ht nguyn liu l 2%. Lng Na4P2O7.10H2O 95% cn dng: 0,6617 100 M Na4P2O7 = = 0,6752 [Kg] 98 Lng Na4P2O7.10H2O 95% tn hao do qu trnh lng: M Na4P2O7 = 0,6752 - 0,6617 = 0,0135 [Kg] 3.4. Tnh lng nc ct phn ng Lng nc ct dng phn ng theo t l: VCM/H2O = 1/1,5 Vy lng nc ct cn dng l: 1571,554 . 1,5 = 2357,331 [kg] Ta c : Khi lng ring ca VCM l 899 kg/m3 nhit phn ng l 58 oC 68

Khi lng ring ca PVC l 1400 kg/m3 Do khi phn ng trng hp VCM thnh PVC xy ra th s gy ra hin tng gim th tch trong ni phn ng gim th tch trong mt tn PVC c tnh theo cng thc sau:
1 1 = 1571,554 x 1 1 = 0,656 [m3 ] V = M VCM x giam PVC 899 1400 VCM

Nh vy ta cn phi b sung thm mt lng nc l 0,656 m 3 vo trong qu trnh phn ng m bo gi tr H/D khng i (H: chiu cao ct cht lng trong thit b, D ng knh thit b) Khi lng nc b sung: MH2O= Vgim x = 0,656 x 1000 = 656 [kg] Tng lng nc dng trong qu trnh phn ng Mnc = 656 + 2357,331 = 3013,331 [kg] Do hoa tn nguyn liu l 2% nn lng nc cn dng cho phn ng l: 3013,331 100 MH O = = 3074,483 [kg] 98 2 Lng nc ny bao gm: - Nc cho trc tip vo ni trng hp - Nc pha dung dch cht khi u - Nc pha dung dch cht n nh huyn ph Lng nc pha cht khi u to dung dch cht khi u 30%: 1,6709 x 70 = 3,899 [kg] 30 Lng nc pha cht n nh huyn ph to dung dch 5%: 0,844 x 95 = 16,036 [kg] 5 Lng nc ct cho trc tip vo ni l: Mnc = 3074,483 (3,899 + 16,036) = 3054,548 [kg] Ta c tinh khit ca VCM l 99.9%, do cn li 0.1% l tp cht v i ra theo nc nn khi lng ca 0.1% tp cht ny l 1571,554 x 0,1 = 1,5716 [kg] Mtp cht = 100 Khi lng nc i ra 69

Mnc = 3054,548 + 1,5716 - 3 = 3053,12 [kg] Trong 3 kg l khi lng nc cn d li trong nha T cc s liu tnh ton trn ta lp bng cn bng vt cht cho 1 tn sn phm: Bng 1: Cn bng vt cht cho 1 tn sn phm trong cng on trng hp(kg): STT 1 2 3 4 5 6 7 Tn nguyn liu VC 99,9% POB 96% PVA 95% Na4P2O7.10H2O 95% Nc ct PVC Tng u vo (kg) Lng vo Tham gia 1414,4 1107,78 1,6709 0 0,844 0 0,6752 0 3054,548 0 4472,138 3 0 0,024 u ra (kg) Lng ra Tn hao 430,803 31,431 1,6375 0,0334 0,8271 0,0169 0,6617 0,0135 3056,12 1107,78 4597,829 61,152 110,78 203,4267

Bng 2 Bng cn bng vt cht cho mt gi sn xut: (Ta nhn bng cn bng vt cht ca mt tn sn phm vi h s 18,9394tn/gi) STT 1 2 3 4 5 6 7 Tn nguyn liu VC 99,9% POB 96% PVA 95% Na4P2O7.10H2O 95% Nc ct PVC Tng u vo (kg) Lng vo Tham gia 26787.887 31.646 15.985 12.788 57851.306 0.000 84699.612 20980.68853 0 0 0 u ra (kg) Lng ra Tn hao 8159.150 31.013 15.665 12.532 595.284 0.633 0.320 0.256 1158.182 2098.107 3852.782

56.8182 57881.079 0 20980.689 21037.50673 87080.128

Bng 3. Cn bng vt cht cho mt m sn xut (Ta nhn bng cn bng vt cht ca mt tn sn phm vi h s 50,505 tn) u vo (kg) 70 u ra (kg)

STT 1 2 3 4 5 6 7

Tn nguyn liu VC 99,9% POB 96% PVA 95% Na4P2O7.10H 2O 95% Nc ct PVC Tng

Lng vo 71434.272 84.389 42.626 34.101 154269.947 0.000 225865.335

Tham gia 55948.4289 0 0 0 151.515 0 56099.944

Lng ra 21757.706 82.702 41.773 33.419 154349.341 55948.429 232213.369

Tn hao 1587.423 1.687 0.854 0.682 3088.482 5594.944 10274.071

Bng 4 Bng cn bng vt cht cho mt ngy sn xut (Ta nhn bng cn bng vt cht ca mt gi sn xut vi h s 24 gi) STT 1 2 3 4 5 6 7 Tn nguyn liu VC 99,9% POB 96% PVA 95% Na4P2O7.10H2O 95% Nc ct PVC Tng u vo (kg) Lng vo Tham gia 642909.297 759.500 383.636 306.909 503536.525 0.000 0.000 0.000 u ra (kg) Lng ra 195819.608 744.318 375.955 300.773 Tn hao 14286.823 15.182 7.682 6.136

1388431.353 1363.637 0.000 0.000 2032790.696 504900.162

1389145.899 27796.373 503536.525 50354.562 2089923.078 92466.757

Bng 5: Bng cn bng vt cht cho mt thng sn xut (Ta nhn bng cn bng vt cht ca mt ngy vi h s 330 : 12 = 27,5 ngy) STT 1 2 3 4 5 6 u vo [tn] Tn nguyn liu Lng vo Tham gia VC 99,9% 17680.006 13847.254 POB 96% 20.886 0.000 PVA 95% 10.550 0.000 Na4P2O7.10H2O 8.440 0.000 95% Nc ct 38181.862 37.500 PVC 0.000 0.000 71 u ra [tn] Lng ra Tn hao 5385.039 392.888 20.469 0.418 10.339 0.211 8.271 0.169 38201.512 13847.254 764.400 1384.750

Tng

55901.744

13884.754

57472.885

2542.836

Bng 6: Bng cn bng vt cht cho mt nm sn xut (Ta nhn bng cn bng vt cht ca mt thng vi h s 12 thng) STT 1 2 3 4 5 6 7 u vo [tn] Tn nguyn liu Lng vo Tham gia VC 99,9% 212160.068 166167.053 POB 96% 250.635 0.000 PVA 95% 126.600 0.000 Na4P2O7.10H2O 101.280 0.000 95% Nc ct 458182.347 450.000 PVC 0.000 0.000 Tng 670820.930 166617.053 u ra [tn] Lng ra Tn hao 64620.471 4714.652 245.625 5.010 124.065 2.535 99.255 2.025 458418.147 166167.053 689674.616 9172.803 16617.005 30514.030

Bng 7: Tiu hao nguyn liu vi nng sut thit b phn ng 150000 tn/nm: Tn nguyn liu VC 99,96% POB 96% PVA 95% 1 tn (k 1 m (kg) g) 1414,4 71434.272 1,6709 0,844 84.389 42.626 34.101 154269.94 7 225865.33 5 1 ngy (kg) 1 thng (t n) 642909.29 17680.006 7 759.500 20.886 383.636 306.909 10.550 8.440 1 nm (tn) 212160.068 250.635 126.600 101.280 458182.347 670820.930

Na4P2O7.10H2O 0,6752 95% Nc ct 3054,54 8 Tng 9994,45 3

1388431.3 38181.862 53 172318,157 55901.744

4. Tnh chi ph nguyn liu u vo cho mt thng sn xut Ton b chi ph v gi c c dng tnh ton u da trn ng tin Vit Nam ti thi im thng 12 nm 2012. 72

C ngl = S ngl V A

Trong : Sngl : n gi mt nguyn liu ng/tn. VA : Nhu cu s dng nguyn liu trong 1 nm (tn)
S ngl = S bb + S bg + S vcbq

Trong : Sbb -Gi bn (nghn ng/tn). Sbg -Chi ph tho d. Svcbq -Chi vn chuyn bo qun Tn nguyn liu Lng dng tro ng thng (tn) VCM 212160.068 POB PVA Na4P2O7.10H2O Tng 250.635 126.600 101.280 60983.721 Gi mua mt n 6 v 14.10 15.106 12.106 6.106 Chi ph (VN ) 2970240.952 3759.525 1519.2 607.68 2976127.357

Chi ph nguyn liu VCM trong 1 thng sn xut: 212160.068 [tn] tng ng vi 2970240.952 [Triu] Chi ph nguyn liu trong 1 thng sn xut: 2976127.357 [Triu] III. TNH CN BNG NHIT LNG CHO THIT B PHN NG POLYME - Hn hp nguyn liu u vo thit b phn ng c nhit 30oC. - Phn ng chnh ta nhit vi hiu ng nhit 80 kJ/mol. - Nhit ca hn hp sn phm u ra l: 80oC Dng dng nc tn nhit cho phn ng: - Nhit u vo ca nc: 40oC - Nhit u ra ca nc: 110oC Ta tin hnh xc nh cn bng nhit cho thit b phn ng trong mt m sn xut. Nhit dung ring ca hn hp dung dch c xc nh theo cng thc: Chh = a1.C1 + a2.C2 + a3.C3 + ... [13 189] Trong : C1,C2 ,C3 Nhit dung ring ca cc cu t, kJ/kg. a1, a2 ,a3 Thnh phn ca cc cu t, phn khi lng, 73

Ta tnh c:

a VCM = a H2O = a POB =

71434,272 = 0,31627 225865,335

154269,947 = 0,68302 225865,335

84,389 = 0,000374 225865,335 42,626 = 0,000151 225865,335

a Na4P3O7 = a =
PVA

65,272 = 0,000189 225865,335

Nhit dung ring ca cc cu t: CVCM = 1590 J/kg. CH2O = 4180 J/kg. CPOB = 1237,5 J/kg. CPVA = 1166,6 J/kg. CNa4P3O7 = 1355,9 J/kg. Do : Chh = 502,8693 + 2855,0236 + 0,4628 + 0,1762 + 0,2563 = 3358,7882 J/kg. 1. Tnh ton nhit tiu hao un nng hn hp t nhit u 30 C ln nhit trng hp 80 C Q1 = G1.Chh.(tc td) , [J] G Khi lng ca hn hp phn ng (ca mt ni trong mt m). G = 225865,335 [kg] td, tc Nhit u v nhit cui ca hn hp, Chh Nhit dung ring ca hn hp, Chh = 3358,7882 [J/kg.] T ta c: Q1 = 225865,335. 3358,7882.(80 30) = 37931,691.103 [kJ] Gi Q l nhit ca phn ng to ra ta c: QVCM = Qpu.GVCM , J Phn ng chnh ta nhit vi hiu ng nhit 80 kJ/mol, vy nhit ca phn ng ta ra l: 74

QVCM = H.NVCM , J Lng VCM tham gia phn ng trong mt m sn xut l: 71434,272 [kg]. S mol VCM c dng cho mt m sn phm l: 71434,272 N VCM = = 1142,95 [kmol] 62,5 Vy nhit lng phn ng ta ra l: QVCM = H.NVCM = 80 . 1142,95.103 = 91,436.106 [kJ] 2. Tnh nhit lng ca nc cn thit duy tr nhit ca thit b phn ng Qu trnh phn ng xy ra c ta nhit rt ln, v vy ta phi dng nc lm mt duy tr nhit phn ng 80 C. Xem nh khng c s mt mt nhit ra mi trng xung quanh th nhit lng m nc nhn c cn thit duy tr nhit cu thit b phn ng l: QNc = QVCM = 91,436. 106 [kJ] M : QNc = GNc.CNc(tc-td) Trong : Gn Lng nc dng trong mt m, kg Cn Nhit dung ring ca nc, Cn = 4,18 kJ/kg. tnc, tnd Nhit cui v nhit u ca nc lm mt, C Lng nc lm mt trong mt m l:

91,436.106 Gn = = = 312,495.103 [kg] C .(t t ) 4,180.(110 40)

Nuoc c n d

Lng nc cn dng cho ton b 3 ni phn ng l: Gn = 3 . 312,495.103 = 937,4846.103 [kg] hay 937,485 m3

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KT LUN Cng vi vic pht trin cng nghip du m v kh thin nhin, cc sn phm ha cht hu c cng t c s pht trin nhy vt nh s kt hp (danh t thng dng hin nay l s tch hp intergration) nhanh chng vi cng ngh lc du. Sn phm ha hc t du m m ra mt ngnh mi: ngnh ha du. Trong , Nha tng hp l sn phm c sn lng ln v gi tr nht. Qua n ny em tm hiu c nha PVC, nm c s cng ngh, cc ng dng v tnh cht ca PVC. a ra cc cng ngh sn xut PVC, Cc phng php sn xut PVC t VCM, Hiu c phng php v trnh t sn xut PVC, nh gi c u nhc im ca tng cng ngh, nh hng ca cc iu kin phn ng n cht lng sn phmv cng tnh ton c mt s cc thng s c bn ca thit b phn ng sn xut PVC. t l tin , l c s p dng vo cc nghin cu sau ny. Trong qu trnh tm hiu n em tm thm cc thng s tnh ton , nhm cho n c thit thc hn. n cn nhiu thiu st mong C v cc bn ng gp.

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TI LIU THAM KHO [1] V Tin Trung Tng lun: Cht do Tnh hnh v trin vng pht trin. Trung tm thng tin v khoa hc k thut ha cht H ni 1994. [2] Edward S. Wilk Industrial Polymer Handbook. Vol. 2. WILEY VCH Verlag GmbH. 2001 p.865 905. [3] Leonard I. Nass, Encyclopedia of PVC, Marcel Dekker, Inc., New York and Basel, 1976. [4] B mn Cao phn t K thut sn xut cht do i hc Bch Khoa H ni 1970. [5] G. C Berry, K. Matyjaszecwki. Progress in Polymer Science. O. VOGL, NewYork 2002. [6] www.vinachem.com.vn/Xut bn phm/Tp ch Cng nghip Ho Cht/1998/S 07. [7] www.vinachem.com.vn/Xut bn phm/Tp ch Cng nghip Ho Cht/2003/S 10. [8] www.industry.gov.vn [9] www.vinachem.com.vn/Xut bn phm/Tp ch Cng nghip Ho Cht/1998/S 04. [10] Nguyn Minh Tn K yu hi tho Trin vng ngnh nha Vit Nam gii php v chnh sch. H Ni. 14 12 2001 [11] Herman F. Mark Ecyclopedia of Polymer Science and Technology. John Wiley & Sons, Inc, NewYork, 1971. [12] Nguyn Bin, Vn i, L Nguyn ng, Long Thanh Hng, inh Vn Hunh, Nguyn Trng Khung, Phan Vn Thm, Phm Xun Ton, Trn Xoa S tay qu trnh v thit b cng ngh ha cht tp II. Nh xut bn Khoa hc v K thut, H Ni 1992. [13] George Matthews, PVC: Production, Properties and Uses, The Institute of Materials, London, 1996. [15] http://dc442.4shared.com/doc/XsG7WC49/preview.html [16] Cc n d thc hin trc .

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