BAO CAO TIEU LUAN E TAI: HOA HOC VA CONG NGHE SAN XUAT ACRYLAT.

CAC NG DUNG CUA ACRYLAT

GVHD: PGS.TS TRAN CONG KHANH SVTH: HUYNH HOAN VAN TN HAU

Acrylat la este cua axit acrylic. Cac este phan t lng thap c san xuat bang phng phap tong hp trc tiep, con cac este phan t lng cao c san xuat bang phng phap chuyen hoa este vi metyl acrylat Tnh chat vat ly cua mot so acrylat:[2-229]
Este
Metyl acrylat Etyl acrylat N-butylacrylat Isobutyl acrylat 2-etylhexyl acrylat

Ts(101kPa, 0C
80 99.4 147.4 138 213

ts(0C)
80-ti 101kPa 43ti 13.7kPa 35-ti 1.1kPa 62-ti 6.7kPa 85-ti 1.07kPa

d204
0.9535 0.9234 0.8998 0.8896 0.8852

A-SAN XUAT ACRYLIC: Co 2 phng phap chnh e san xuat axit acrylic I-Oxi hoa propylen san xuat axit acrylic: 1/Hoa hoc cua qua trnh: Qua trnh oxy hoa P= san xuat axit acrylic da tren cac phan ng toa nhiet tien hanh theo hai giai oan vi hp chat trung gian la acrolein:

CH2=CH-CH3 + O2 CH2=CH-CHO + H2O

H0298 = - 340 kJ/mol CH2=CH-CHO + 1/2O2 CH2=CH-COOH H0298 = - 250 kJ/mol

Rat nhieu san pham phu c hnh thanh trong qua trnh chuyen hoa ( axetaldehyt, axit axetic, CO, CO2 ) chu yeu xuat phat t cac phan ng chay mot phan hoac hoan toan va cac san pham cua qua trnh polyme hoa e hng phan ng xay ra theo chieu hng tao acrolein va axit acrylic, rut ngan giai oan cam ng va duy tr nhiet o thap (di 400 hoac 5000C), s dung cac he xuc tac co o chon loc cao.

 C che phan ng [1-190]: la c chuoi goc t do gom 3 giai

oan -Giai oan au: O2 2O* CH2=CH-CH3 + O* CH2=CH-CH2* + *OH -Giai oan phat trien: CH2=CH-CH3 + *OH CH2=CH-CH2* + H2O CH2=CH-CH2* + O* CH2=CH-CH* + *OH -Giai oan cuoi: CH2=CH-CH* + O* CH2=CH-CHO Va sau o: CH2=CH-CHO + *OH CH2=CH-CO* + H2O CH2=CH-CO* + *OH CH2=CH-COOH

P(1):Oxi hoa P= thanh acrolein -Xuc tac: xt au tien c s dung la oxyt ong hoac cac kim loai nang c mang tren chat mang laSiO2 hoac Al2O3. Ngay nay : xt molipdat bismut (Bi2O3.MoO3) -Chat kch ong : P2O5, oxit Telua va ong -Nhiet o p: 340-4000C , P = 0.1-0.3 MPa -Chat oxi hoa: khong kh va oxi ky thuat

Cong nghe mi dung oxi e de tach sp va tuan hoan P= Them 25-50% hi nc nham tang o chon locnh tang nha hap phu acrolein khoi be mat xt oxyt,ong thi pha v gii han no cua hon hp P=/KK -o chuyen hoa mot lan t 0.90-0.95 va hieu suat acrolein va axit acrylic la 0.8-0.9 -San pham phu : axeton, axetaldehyt, axetic, CO. Thanh phan (%V) hon hp kh vao thiet b phan ng *Vi Oxi kt: 42-44% P=, 8-10% oxi,46-50% hi nc va tuan hoan P= *Vi kk: 4-5% P=, 55-65% KK, 30-40% hi nc va khong tuan hoan P=

TBP: loai ong chum, giai nhiet p bang muoi nong chay P(2): oxi hoa acrolein thanh axit acrylic -Xuc tac : hon hp cac oxyt molipden va vanadi tam them mot so hp chat cua vonfram, ong, crom, telur, asen va c thiet ke e cai thien cac hoat tnh , hieu qua lam viec nhiet o thap -Nhiet o p : 250-2800C , P = 0.1-0.2 Mpa -SP phu : axetic axit, CO -Hieu suat :tren 90% va o chuye hoa mot lan 95-97% -TBP: loai ong chum, tach sp bang hap thu nc sau o trch li axit hu c bang EA

C che phan ng: la c chuoi goc t do gom 3 giai oan -Giai oan au: O2 2O* CH2=CH-CH3 + O* CH2=CH-CH2* + *OH -Giai oan phat trien: CH2=CH-CH3 + *OH CH2=CH-CH2* + H2O CH2=CH-CH2* + O* CH2=CH-CH* + *OH -Giai oan cuoi: CH2=CH-CH* + O* CH2=CH-CHO Va sau o: CH2=CH-CHO + *OH CH2=CH-CO* + H2O CH2=CH-CO* + *OH CH2=CH-COOH

2/Cong nghe
Kh thi

Khng kh Propylen Hi nc

Oxi

Axit Acrylic
Axit Axtic Inh. Inh. Inh. 6 7 8

E-40

4 5 tyl axtat S.P. nng

Thuyet minh s o cong nghe : Propylen vi o tinh khiet hn 90%V va propan vi ham lng nho hn 4.5%V c hoa hi trong thiet b TN s dung cac dong nong lay ra t thiet b x ly lam mat. Sau o hi va kk c tron cung dong nguyen lieu sao cho hon hp cuoi cung co cha trung bnh 4-5%propylen, 30-40% nc, 55-65% kk. Hon hp nay tiep tuc c gia nhiet nh TN vi dong sp t thiet b p th nhat. Sp ra khoi tb p th nhat c bo sung oxi c dan trc tiep vao tbp th hai sau khi c gia nhiet nh TN vi cac sp ra khoi tbp.

Trong cac giai oan lam mat cac dong kh tao ra t qua trnh chuyen hoa can am bao rang nhiet o cua chung van tren iem sng e tranh an mon manh. e tranh nhng s bien oi tiep theo, sp tao thanh c lam lanh nhanh va hap thu. Bang qua trnh tuan hoan nc hoac dung moi hu c co nhiet o soi ln hn nhiet o soi cua axit acrylic ( vd : dietylphtalat), nhiet o cua dong sp c ha t 140-1500C xuong 65-700C. Mot phan dd hap thu c tuan hoan tr lai thap hap thu, phan con lai c lam lanh tiep en 40-500C e a vao tb trch ly cac chat hu c bang etylaxetat

Cac kh thai thoat ra t thap hap thu c ot chay. Axit acrylic c thu hoi t dd nc ( 20% khoi lng ), nh cac qua trnh : -Chiet axit acrylic va axit axetic ra khoi nc bang etylaxetat ( hoac co the la butylaxetat, xylen, diisobutyl xeton, metyl, etyl, va butyl acrylat, hoac cac dung moi khac dang n le hoac hon hp ). Qua trnh nay dien ra vi s tiep xuc ngc dong trong he thong thiet b loai tiep xuc a quay co truc trung tam gan 8-10 tam quay. -Chng dang ph phan dch chiet ( thap 12 a , 20 kPa ) e thu hoi hon hp ang ph d the nc/dung moi nh thap .

 Hon hp tren se c a qua thiet b lang tach , tuan hoan

etylaxetat ve thap chiet va tach nc. -Tinh che phan dd giau axit acrylic bang chng chan khong ( 7-10 kPa ) trong hai thap ( 55 va 30 a ) se thu c lan lt axit axetic va axit acrylic bang hai nh thap vi o tinh khiet ln hn 99% ve khoi lng. Nhiet o trung bnh cua cac ay thap la 700C va co mat chat c che polyme hoa ( ac biet la hydroquinon ) e ngan nga s mat mat axit acrylic trong phan ng dime hoa thanh 3-acryloxy propionic axit. -x ly cac dong dd nc e thu hoi acrolein va etylaxetat bang chng cat ap suat kh quyen ( 65 a )

II-San xuat axit acrylic t axetylen: 1/hoa hoc cua qua trnh: Qua trnh c thc hien da tren phan ng: Ni(CO)4 + 4C2H2 + 4H2O +2HCl 4CH2=CH-COOH +NiCl2 +H2 Phan ng tien hanh nhiet o va ap suat thap:T= 25-700C va ap suat kh quyen Trong phan ng tren Ni(CO)4 la chat phan ng cho vao theo ty lng. Cong nghe BASF s dung Ni(CO)4 lam chat xt, phan ng: C2H2 + CO + H2O CH2=CH-COOH

ieu kien phan ng: -T= 150-2900C ( trung bnh la 2250C ) -P= 3-20 Mpa ( thng 10 Mpa ) -e duy tr moi trng phan ng tien hanh trong pha long vi dung moi la tetrahydrofuran ( THF ) 2/Cong nghe: S o cong nghe :

Inh. THF CO THF Axtylen Xc tc 1 2 3 4 5 6 7 Nc Kh thi

Inh. Inh. Inh.

THF

10

11

Axit Acrylic
E-36

S.P. nng Mtyl tyl xtn

Thuyet minh s o cong nghe: qua trnh c tien hanh qua cac cong oan -ieu che xuc tac t muoi niken va ong bromua ( hoac clorua ) va THF tuan hoan trong thiet b co khuay. -Hoa tan axetylen vao trong dung moi THF va nen -Thc hien phan ng: cho CO a c nen trc va dung dch axetylen a tron vi xuc tacvao thiet b phan ng ong chum vi chat tai nhiet chay ngoai ong e san xuat hi nc ap suat thap. Axetylen hau nh c chuyen hoa hoan toan, hieu suat 70-75%

-Tach kh trong thiet b tach kh/long va thu hoi axit acrylic b cuon theo bang cach ra vi THF. -X ly phan oan long ( cha 18% trong lng axit acrylic trong dung moi THF ) bao gom cac cong oan sau: tach CO va ra nc trc khi tuan hoan, chng cat chan khong dung moi, trch ly axit acrylic bang dung moi metyl etyl keton ( MEK ), thu hoi dung moi trch ly MEK va tinh che axit acrylic bang chng chan khong vi s co mat cua chat c che polyme hoa ( hydroquinon ).

B-SAN XUAT ACRYLAT: I-San xuat acrylat bang phng phap este hoa axit acrylic 1/Hoa hoc cua qua trnh : Qua trnh xay ra theo phan ng thu nhiet sau: CH2=CH-COOH +C2H5OH CH2=CHCOO-CH2CH3 + H2O H0298 = +35 kJ/mol -Tien hanh trong pha long -Nhiet o trung bnh : 50-800C -Ap suat thap : P = 20-100 kPa -xuc tac : axit ( thng la axit sunfuric hoac nha trao oi ion )

C che phan ng este hoa: -Tan cong cua H+ ( axit cacboxylic ) R-COOH + H+ R-C-OH +OH -Tan cong cua ru vao dang ion hoat ong va c hnh thanh: ROH R-C-OH + ROH R-C-OH +OH +OH -Chuyen v tr ien tch dng: ROH OH OH R-C-OH R-C-OH R-C-O+H2 +OH R OH OR +

-Tach nc: OH R-C-O+H2 R-C=O+H +H2O OR OR -Tach H+:

2/Cong nghe:

R-C=O+H R-C=O + H+ OR OR

Nc Inh. Axit Acrylic H2SO4 1 Ru Hi Nc Kim Hi Hi Nc 2 3 4 5 6 7 Acrylat Inh.

S.P. nng

 Thuyet minh s o cong nghe : Axit acrylic va xuc tac H2SO4 c bm vao thiet b este hoa

cung vi ru etanol sau khi c un nong trong tthiet b un nong. Trong thap este hoa ( 30 a ) xay ra phan ng este hoa gia axit acrylic va ru etanol. -Tai nh thap thu c hon hp acrylat/ru/nc va co lan mot lng nho axit acrylic cha phan ng. ay giau axit sunfuric va sp nang c trung hoa bang NaOH. Lng ru cha phan ng cung i ra ay c thu hoi bang chng cat 110-120oC, ap suat thap ( 40-120 kPa ) va tuan hoan lai thap este hoa

 -San pham nh c trch ly tach ru bang cach ra vi

nc, neu can thiet co the pha them NaOH e trung hoa vet cua axit acrylic, qua trnh trch ly c tien hanh bang phng phap ngc dong trong thap tiep xuc a quay ( sp nh i t di len, nc c ti t tren xuong ) +Ra khoi nh thap trch ly la pha rafinat co cha este. Este c tach nc trong thap chng cat ang ph ( 20 a,nhiet o nh thap 50-800C phu thuoc vao loai este,ap suat 20-100 kPa ). Sp nh thap chng cat c lang s bo, lp tren thiet b lang la pha hu c dung e hoi lu, pha nc lp di c tuan hoan lai thiet b trch ly.Sp ay thap chng cat ang ph c a sang thiet b tinh che este(20 a, nhiet o nh thap 40-1000C,

 P = 15-100 kPa) e thu c acryiat vi o tinh khiet 98.5-99%

nh thap.Sp ay co the c tiep tuctinh che e thu hoi lng acrylat con lan. Tai dong hoi lu cua cac thiet b chng eu cho them chat c che hydroquinon va nhiet o ay thap trung bnh khong vt qua 100-1100C +Pha chiet thu c ay thiet b trch ly c a sang thiet b chng cat tach hon hp ang ph acrylat/ru/nc nh tuan hoan lai thap trch ly, hon hp ru/nc thu c ay tiep tuc c a i tach nc bang chng cat ang ph, ru c tuan hoan tr lai thiet b este hoa

 II-San xuat acrylat t axetylen: Acrylat thu c bang phan ng cong hp cua CO va ru

vao axetylen theo kieu phan ng tong hp Reppe vi xuc tac cacbonyl niken Phan ng xay ra theo c che chuoi goc, t xuc tac, xay ra nhanh ngay nhiet o thap 25-700C va ap suat kh quyen.Phan ng tong cong nh sau: Ni(CO)4 + 4C2H2 + 4ROH +2HCl 4CH2=CH-COOR + NiCl2 +H2 ay la phan ng toa nhiet manh,vi H0298= -250 kJ/mol acrylat. Hydro tao thanh nhanh chong tham gia phan ng phu tao thanh propionat va metanol do vay khong co mat trong sp phan ng

 Cong nghe san xuat acrylat t axetylen cua BASF tien hanh

C2H2 + CO + ROH CH2=CH-COOR

H2980

trong ieu kien nhiet o va ap suat cao: 150-2900C(tb la 2250C),3-20 Mpa(thng 10 MPa) e duy tr moi trng phan ng la dung moi tetrahydrofuran(THF) trong pha long. Phan ng tong quat co the viet nh sau:

= -250 kJ/mol acrylat Trong cong nghiep qua trnh tien hanh theo hai giai oan : san xuat axit acrylic va este hoa thanh acrylat. III-Cac phng phap san xuat khac:

1/Thuy phan va ests hoa etylen cyanohydrin: Cyanohydrin thu c t etylen oxyt theo phan ng sau:

HO-CH2-CH2-CN+H2SO4CH2=CH-CO-NH2.H2SO4 +ROHCH2=CH-COOR + NH4HSO4 Hai p nay c dien ra ong thi trong pha long, tai ap suat kh quyen , nhiet o khoang 1500C.

C2H4 O + HCN HO-CH2-CH2-CN Phan ng xay ra nhiet o 55-650C, vi s co mat cua xuc tac kiem la dd nc cua NaOH va dietylamin. Sp tho c lam sach bang chng cat chan khong. Sau o la p thuy phan va este hoa vi s co mat cua axit sunfuric va ru nh sau:

 Ty le mol cyanohydrin/ru/axit la 1/2/2. Sau khi sp c lam

lanh va ra vi nc nong, ru cha p c thu hoi va tuan hoan. Cac cau t khac c lam sach va tinh che bang chng cat. Ham lng acrylat thu c len ti 80%so vi cyanohydrin 2/Ngng tu giua keten va formaldehit: Phng phap nay hien nay khong con c ap dung.Qua trnh da tren p chnh sau:
CH2=C=O + HCHOH2C-CH2 H0298= -190kJ/mol O-C=O oxetan-2-one

 H2C-CH2 + ROH CH2=CH-COOR + H2O O-C=O H0298 = -45 kJ/mol(etyl acrylat) 3/San xuat acrylat t acrylonitril: Qua trnh nay co lien quan en p oxi hoa khong trc tiep

propylen. Tuy nhien do hieu suat qua trnh thap hn so vi qua trnh oxy hoa trc tiep propylen va sp phu co cha nhieu axit sunfuric va sunfat amoni nen t c ap dung. Qua trnh da tren p thuy phan cua acrylonitril thanh acrylamit sunfat trong moi trng axit sunfuric, sau o la p este hoa vi ru tao thanh acrylat theo cac p sau: CH2=CH-CN + H2O +H2SO4 CH2=CH-CO-NH2.H2SO4

 CH2=CH-CO-NH2.H2SO4 + ROH CH2=CH-COOR + NH4HSO4 Phn ng chuyen hoa acrylonitril thanh acrylamit sunfat c

ieu khien bang cach han che ham lng nc trong moi trng phan ng va giam thi gian lu trong thiet b phan ng ( 5-10 phut ), nhng mot phan nho acrylonitril van b thuy phan tao axit acry lic. Phan ng xay ra ap suat kh quyen, nhiet o 145-1550C vi s co mat cua axit sunfuric 85% trong thiet b co khuay. San pham c a sang thuet b ests hoa lam viec ap suat kh quyen, nhiet o 160-1800C,tai nhiet o nay san pham phu axit acrylic cung co

the c chuyen hoa. Hon hp acrylat, rou d va noc thu c nh thap, hon hp axit sunfuric, bisunfat amoni va san pham phu la cac hp chat hu c ( nh 3- alkoxypropionat ) c phan huy nhiet e tao thanh sunfat amoni dung lam phan bon. Phan oan nhe c chng cat e thu hoi san pham phu ete va tuan hoan tr lai thiet b este hoa e am bao ieu kien nong o on nh. Ru c tach bang chng cat trch ly , sau o dc a i chng cat tach nc trc khi tuan hoan lai thap ests hoa. Trong thiet b lang cua thap chng cat trch ly se phan lam hai pha. Pha nc c hoi lu, pha hu c co cha nc c a sang thiet b tach nc. Tai thiet b lang cua thap chng

 cat tach nc cung phan lam hai pha. Pha hu c c hoi

lu va pha nc c tuan hoan lai thap chng cat trch ly. San pham ay cua thap tach nc cha este khan c a sang thap tinh che este, tach san pham nang khoi acrylat. Chat c che polyme hoa ( hydroquinon ) c a vao thap chng e tranh phan ng trung hp.

SN XuT ACRYLAT PHN T LNG CAO Cc este acrylat phn t lng cao c th c tng trc tip bng phn ng este ho gia axit acrylic vi ru phn t lng ln hoc bng phn ng chuyn ho este (trans este ho ) vi acrylat phn t lng thp (metyl hoc etyl acrylat) Cc hp cht ny thng c sn xut gin on v nhu cu i vi sn phm ny khng cao v do cc ru cao (vd :t-butanol ,2-etyl hexanol ) thng khng tan trong nc v do vy kh thu hi bng phng php trch ly

 iu kin cng ngh : qu trnh este ho trc tip c tin hnh

vi s c mt ca axit sunfuric , toluen sunfonic axit hoc nha trao i cation c sunfonic ho , ti p sut kh quyn nhit phn ng : T = 20 n 120oC ph thuc vo loi este dung mi c s dng tch nc to ra trong phn ng axit acrylic cha phn ng v xc tc c trung ho v acrylat c lm sch bng chng ct

 Hiu sut ca qu trnh ln n 80 n 90% mol PTP : CH2=CH-COOR + ROH CH2=CH-COOR + ROH Nhit c iu khin tch sn phm ph ru
ngay sau khi chng c sinh ra bng chng ct ng ph (hn hp ng ph to gia ru v este ban u) C th s dng hp cht th ba ph ng ph nh cyclohexan ( to hn hp ng ph gia etanol v cycohexan ) Sau khi tch xc tc , sn phm lng c chng ct lm sch trong iu kin chn khng vi s c mt ca cht c ch trng hp ( nh phenothiazin )

*ng dng ca acrylat: Acrylat l Este khng no c ni i u mch cacbon c dng sx cc polime, c bit l cc Copolyme, c nhiu ng dng trong cng nghip v i sng nh cc tnh nng sau: -Chu bc x t ngoi tt (sn bn ngoi cc cng trnh xy dng, sn qung co). - bng cao. - Sng mu, cho php sx mc in, sn c mu sc phong ph. -Chu nc, chu mi trng n mn v oxi ho.

S dng acrylat S dng (%) Ty u M Nht

Si Acrylic Cht kt dnh Sn Dt Giy Da, cht lm bng, ng dng khc

6 17 36 17 14 10

5 6 40 23 5 19

14 20 23 16 15

Nhu cu s dng cc acrylat:

Nhu cu cc Acrylat (%) Ty u M Nht

Metyl Acrylat
Etyl Acrylat Butyl Acrylat

14
24 38

4
36 46

23
14 31

2-Etyl Hexyl Acrylat

Cc Acrylat khc

16
9

9
5

29
3

 Ti liu tham kho : 1) Translate from the French by Nissim

Marshall , petro chemical processes, 1989 2) Cng ngh tng hp hu c ho du nh xut bn khoa hc v k thut,2006 tc gi : Phm Thanh Huyn Nguyn Hng Lin 3) Bi ging cng ngh tng hp ho du tc gi PGS.TS Trn Cng Khanh HT