GVHD: PGS-TS: Phm Thanh Huyn SVTH: 1. inh Ngc Phan hd1 2. Nguyn Trng Ngha hd1 3.

Phm S ng hd1

 1. Tnh cht 2. Cc phng php sn xut cng nghip 3. Tn cha bo qun,ng dng,ch tiu cht lng

1.1 Tnh cht l hc

Axit axetic l cht lng khng mu hoc tinh th mu trng, c v chua, c kh nng tan v hn trong nc. T trng ca axit axetic dng lng l 1.049g/cm3 v dng tinh th l 1.266g/cm3. Tnc = 16.5oC, Ts = 118,1oC

1.2 Tnh cht ha hc

Axit axetic c tnh axit, 25oC n c pKa = 4,26, th hin : Lm thay i mu qu tm Khi thm axit axetic vo dung dch Ca(OH)2 c mt phenolphtalein, dung dch mt dn mu hng phn ng vi baz Axit axetic ha tan CuO thnh dung dch c mu xanh c trng phn ng vi oxit baz Ha tan Zn phn ng vi kim loi Tc dng vi mui ( phn ng vi CaCO3 thot kh CO2)

2. Phng php sn xut cng nghip

Axit axetic trong cng nghip c sn xut theo 2 phng php: phng php sinh hc v phng php tng hp. Ngy nay, lng axit sn xut theo phng php sinh hc ch chim khong 10% sn lng th gii, nhng n vn l mt phng php quan trng dng sn xut gim (mt s iu lut v tinh khit thc phm mt s quc gia quy nh rng gim s dng trong thc phm phi c ngun gc t sinh hc). Phng php tng hp c p dng nhiu hn sn xut axit vi nng sut cao. Trong , khong 75% axit axetic c sn xut cng nghip c sn xut theo phng php cacbonyl ha metanol. Khong 15% cn li c sn xut t cc phng php thay th khc (oxy ha trc tip hydrocacbon no, oxy ha axetaldehit, oxy ha etylen)

Cc phng php sn xut

Cacbonyl ha metanol Oxy ha axetaldehyt Oxy ha etylen Oxy ha RH no(n-butan,naphta) Ln men oxy ha Ln men k kh

Cacbonyl ha metanol

Monsanto

Cativa BP

BASF

2.1.Cng ngh cacbonyl ha metanol

2.1.1 Lch s pht trin Cng ngh sn xut axit axetic t metanol v cacbonmonoxit nhit v p sut cao c hng BASF a ra t rt sm (1913) da trn phn ng:
CH3OH + CO --> CH3COOH H298 = - 138,6 KJ/mol

iu kin tin hnh khc nghit v nhit v p sut cng vi s c mt ca cc cht n mn mnh (cc hp cht iotua) ngn cn vic thng mi ho cng ngh ny.

 Nm 1914, cc nghin cu ca REPPE (BASF) cho thy rng cc kim loi nhm VIII c kh nng xc tc hiu qu cho qu trnh cacbonyl ho. iu ny dn n vic ra i v pht trin cng ngh nhit v p sut cao (250oC v 70MPa) vi xc tc CoI2. Qu trnh ny c BASF a vo p dng nm 1960 ti Luwig Shafen. Cng sut ban u l 3.600 tn/nm. Sau tng ln 12.000 tn/nm vo nm 1964 v 35.000 tn/nm vo nm 1970. Nm 1981 cng sut t 45.000 tn/nm. Nm 1966, Borden Chemical c khi ng xy dng mt nh my sn xut axit axetic trn c s cng ngh BASF ti Geimak (Bang Louisiana, M) vi nng sut ban u l 30.000 tn/nm sau tng ln 45.000 tn/nm vo nm 1968.

Nm 1968, Monsanto cng b mt khm ph mi. Xc tc rhodi vi hot tnh v chn lc rt cao cho phn ng cacbonyl ho metanol thnh axit axetic. Metanol c th c cacbonyl ho ngay c p sut thng vi hiu sut chuyn ho l 99% i vi metanol v 90% i vi cacbon monoxit. Qu trnh c s dng xc tc ny c p dng nm 1970 ti bang Texas, vi cng sut ban u l 135.000 tn/nm, sau tng ln 180.000 tn/nm vo nm 1975. iu kin tin hnh qu trnh Monsanto mm hn so vi qu trnh BASF (3MPa v 180oC ) .

2.1.2 Nguyn tc chung ca qu trnh

Qu trnh cacbonyl ha metanol l mt phn ng ta nhit
CH3OH + CO CH3COOH H298 = - 138,6 KJ/mol Phn ng xy ra thun li trong pha lng, nhit 220 250oC, p sut ca qu trnh phi c gi mc 30MPa. S c mt ca nc (> 30% TT) v vic s dng xc tc s gip gim bt khc nghit ca cc iu kin tin hnh qu trnh, c bit l p sut c gim xung 3 7 MPa v nhit 150 200oC H xc tc ang c s dng gm c 3 thnh phn: pha hot ng, cht xc tin v dung mi. Pha hot ng (cc oxit, cc hp cht c kim, cc hp cht phi tr hoc mui ca kim loi qu him nh Co, Rh) c nng n 10-3M. Cht xc tin, khi mo (1M) l halogen hoc cc hp cht cha halogen.

3.1.3 Cng ngh BASF

Qu trnh BASF s dng cacbonyl coban lm xc tc vi cht kch ng iotua CoI2 c dng ti sinh ti ch Co2(CO)8 v HI. Tc phn ng ph thuc vo p sut ring phn ca cacbon monoxit v nng metanol. Hiu sut thu axit axetic t 90% i vi metanol v 70% i vi cacbon monoxit.

C ch phn ng nh sau:

Phn ng (1) c th chuyn ho CO bng hi nc, xc tc l Co2(CO)8 v H2 c to ra bng cch phn ly phc hydro cacbonyl. Metyl iotua lin tc tn cng bi tc nhn nucleophil l ion [Co(CO)4]- (4). Gc iotua lm cho phn ng d dng hn v n d tch hn OH-. CH3I phn ng vi phi tr bo ho d10 Co(CO)4. Qu trnh oxy ho cng hp ca CH3I vo Co(CO)4 kh khn hn vo [Rh(CO)2I2]-. Sn phm cng hp ban u l mt phc 5 phi tr d8 CH3Co(CO)4. Giai on chuyn v metyl (5) xy ra chm hn so vi qu trnh xc tc bi Rh. Khi to thnh hp cht trung gian axyl ca coban, hp cht ny khng b phn hu to coban iotua v iod khng phi tr vi coban

 Cc giai on lin quan n c ch phn ng dng xc tc rhodi c gii thch bi kh nng phn ng ca coban thp hn ca rhodi. iu ny gii thch ti sao nhit ca qu trnh BASF li cao hn ca qu trnh Monsanto. Hn na p sut ring phn ca cacbon monoxit cng phi cao n nh phc [Cd(CO)4]-. Sn phm ph ca BASF l CH4, CH3CHO, C2H5OH, C2H5COOH, CO2. Khong 3,5% CH3OH phn ng mt mt di dng metan, 4,5% di dng sn phm ph lng, 2% di dng kh thi. Khong 10% CO nguyn liu b bin i thnh CO2 theo phn ng chuyn ho kh hi nc. CO + H2O --> CO2 + H2 (9)

 CO2, metanol (cha 60% dimetyl ete), xc tc tun hon, xc tc mi, metyl iotua tun hon (t thp ra) c a n thit b phn ng p sut cao (b). Mt phn ca nhit phn ng c dng un nng s b nguyn liu, phn nhit cn li c tiu tn dc theo ng phn ng. Sn phm phn ng c lm lnh v a n thit b phn ly p sut cao (d). Kh thi c a vo thp ra (o) phn lng c gin n ti p sut 0,5 1 MPa trong thit b phn ly p sut trung bnh (e). Kh thot ra cng c vo thp ra (o), phn lng t thit b phn ly p sut trung bnh c a n bung gin n (f). Kh ra khi bung c a n thit b ra (p). Kh t thit b ra v thp ra l kh thi. C thit b ra v thp ra u dng metanol nguyn liu thu hi metyl iotua v cc hp cht iotua d bay hi khc. Dung dch metanol ny c a tr li thit b phn ng. Thnh phn kh thi (% th tch): CO: 65 -75%, CO2: 15-20%, CH4: 3-5% v hi metanol.

 Axit t bung gin n (f) chim 45% khi lng axit axetic, 35% khi lng nc, 20% khi lng este (ch yu l metyl axetat). Axit c tinh ch 5 thp chng ct. Thp th nht (h) dng ui kh t hn hp sn phm th, kh thot ra c a vo thp ra. Xc tc c tch ra bng cch chng ct cc cu t d bay hi thit b tch xc tc (i). Ti thit b sy (k) cho php nhn c axit tinh bng phng php chng ct ng ph. Sn phm nh ca thp lm kh cha axit axetic, axit formic, nc, sn phm ph, chng to hn hp ng ph vi nc. Sn phm nh ny l mt h hai pha, n c tch trong bung (g). Mt phn ca pha hu c, cha ch yu este c tr li (k), n ng vai tr l mt tc nhn ng ph

 . Phn cn li c a n thp ph (n), y phn nng c ly ra phn y thp, phn nh nh thp c a tun hon li thit b phn ng. Phn ch yu thp lm kh c a n thp lm sch ln cui, axit axetic c ly ra nh thp, sn phm y c a n thp tch cn (m). Sn phm nh ca thp ny c a ti thp tch nc, sn phm y cha 50% khi lng axit propionic c a i thu hi.

Monsanto process
So snh cng ngh

Thng s Thi gian Xc tc Nhit (o C) p sut ( Mpa) chn lc

BASF 1941 CoI2 250 68 90% ( MeOH) 70% (CO)

Monsanto 1960 RhI2 200 35 99% ( MeOH) 90% (CO)

H xc tc Rhonium u vit hn Cobalt

Monsanto process
S pht trin xc tc :
Nm 1941 Reppe ti BASF chng minh hiu qu ca nhm carbonyls kim loi VIII nh cht xc tc cho phn ng carbonylation :xc tc cobalt it, p sut cao, x l nhit v p sut cao (700 bar, 250C) Monsanto pht trin qu trnh sn xut axit axetic trong cui thp nin 1960 vi h xc tc rhodium , cht xc tc thc y tc phn ng v chn lc cao vi quy trnh da trn h xc tc cobalt ca BASF Monsanto trong u nhng nm 1960 cng pht hin ra rng iridi, nh rhodium, l mt cht xc tc carbonylation methanol c hiu qu. H thng cht xc tc c pht trin BP trong nm 1990 v c gi l qu trnh Cativa

Monsanto process
Xc tc Rhodium/iodide:
Xc tc cacbonyl ha gm 2 thnh phn kim loi Rh c hot ha trn cht mang iode Xc tc to phc cht trung gian gm Rh,CO v phi t l halogen Ti sinh xc : Trc tin loi b cc ion kim loi c ln do qu trnh x l bng nha trao i ion. Sau l sau nhit phn mt phn nh un nng,ri lm lnh, kt ta thu hi cu t cha Rh. Cc hp cht ny s c b sung iot mi riha tan trong axit axetic nng di p sut CO

Monsanto process
Thng s qu trnh cacbonyl ha metanol : CH3OH + CO CH3COOH

H =137KJ/mol

Phn ng thu nhit : H > 0 Nhit : khong 200oC p sut : 35 MPa Xc tc : hp cht phi tr rodi-clorocacbonyl-bis triphenylphosphin :Rh(CO)[P(C6H5)3]2Cl

Monsanto process
C ch

Methanol

Distillation of acid Enriched wit acetic

Ion exchange resins

RhI3
Catalyst storage

Methyl iodide Spent production catalyst Methanol

Dehydro by azeotropic distillation

hydro

Iodide (H2O)

Water removal

Methyl iodide storage Carbonylation reactor

Residual acetic acid recovery

Propionic acid

Acetic acid purification Gas scrubbing with methanol

Residual gas

Glacial Acetic acid

CO,CO2, N2

stripping

Monsanto process
nh gi Cng ngh
u im

Company Logo

100%, vi tt c cc nguyn t trong cc cht phn ng i vo sn phm S dng nng lng t hn, c bit tch v tinh ch. C nng sut cao, S dng methanol nguyn liu r hn so vi naphta trc / butan Tc phn ng nhanh. Chu k sng ca xc tc di

Nhc im
Rhodium l kim loi rt t tin - t hn vng Rhodium cng xc tc phn ng ph CO + H20 2+ H2 iu ny lm gim p sut ring phn ca kh carbon monoxide Rhodium ha tan to mun RhI3. Cn c cng on tch nc gy tn chi ph v nng lng tr li xc tc cho phn ng chnh

CATIVA process
C g ng k v qu trnh CATIVA ca BP, ngy nay n vn l cng ngh tt nht sn xut axit axetic thng mi
Theo quan im ca BP, CATIVA - mi ba nm sau khi thng mi ha ln u tin - vn l cng ngh hiu qu nht, quy nh v vn v chi ph vn hnh thp nht. Nm 1986 Monsanto cp php cho mt s cng ty, bao gm BP, trong BP mua bn quyn cng ngh ca Monsanto v carbonylation methanol v pht trin n hn na to ra thng hiu c quyn ca BP : CATIVA S khc bit c bn nht gia cc phin bn ca qu trnh carbonylation l cht xc tc. Cng ngh carbonylation c bn ca Monsanto l da trn xc tc rhodium, qu trnh CATIVA ca BP nh du mt bc thay i trong cng ngh bi v n chuyn hon ton ra khi rhodium thay vo l xc tc iridi da trn kt hp vi mt cht hot ha kim loi chuyn tip

CATIVA process
C ch

CATIVA process

CATIVA process
u im cng ngh CATIVA :
Xc tc Ir c gi r bng 1/10 gi ca Rh theo cng trng lng. Lu trnh cng ngh n gin hn monsanto rt nhiu. S lng cc thp tinh ch c n gin ha v gim i rt nhiu S dng thit b phn ng dng sc kh thay th cho thit b khuy c hc ng thi c thm thit b phn ng th cp nhm nng cao hiu sut chuyn ha

CATIVA process

ng dng axit exetic

Monome vinyl axetat
Sn xut este

Axit axetic

Axetic anhydrit Gim

Lm dung mi

Mt s ng dng khc

ng dng axit exetic

1. Monome vinyl axetat
ng dng ch yu ca axit axetic l sn xut monome vinyl axetate. ng dng ny tiu th khong 40% n 45% sn lng axit axetic trn th gii. Phn ng c s tham gia ca etylen vi xy v cht xc tc l palladi.
2H3C-COOH + 2C2H4 + O2 2H3C-CO-O-CH=CH2 + 2H2O

Vinyl axetate c th c polyme ha to thnh polyvinyl axetat hoc thnh cc polyme khc ng dng trong sn v cht kt dnh.

ng dng axit exetic

Cc este chnh sn xut t axit axetic c s dng ch yu lm dung mi cho mc, sn v cht ph. Cc este nh ethyl axetat, n-butyl axetat, isobutyl axetat, v propyl axetat, chng c sn xut mt cch c bit bng phn ng c xc tc t axit axetic v ru tng ng: H3C-COOH + HO-R H3C-CO-O-R + H2O Tuy nhin, hu ht este axetat c sn xut t acetaldehyt bng phn ng Tishchenko. Thm vo , cc ete axetat c s dng lm cc dung mi loi b nitrocellulose, sn acrylic, vc-ni, v cht ty g. u tin, glycol monoete c to ra t etylene oxit hoc propylen oxit vi ru, sau chng c este ha vi axit axetic. Ba sn phm chnh l etylen glycol monoetyl ete axetat (EEA), etylen glycol monobutyl ete axetat (EBA), v propylen glycol mono-metyl ete axetat (PMA). ng dng ny tiu th khong 15% n 20% sn lng axit axetic th gii. Cc ete axetat, v d nh EEA, c cho l c hi i vi sc khe sinh sn con ngi.

2. Sn xut este

ng dng axit exetic

3.Axetic anhydrit
Sn phm tch phn t nc t hai phn t axit axetic to thnh mt phn t gi l axetic anhydrit. Sn xut axetic anhydrit trn th gii l mt ng dng chnh chim khong 25% n 30% sn lng axit axetic ton cu. Axetic anhydrit c th c sn xut trc tip bng cacbonyl ha metanol t axit, v cc nh my sn xut theo cng ngh Cativa c th c iu chnh sn xut anhydrit.

Axetic anhydrit l mt cht acetyl ha mnh. V vy, ng dng chnh ca n l to cellulose acxtat, mt cht dt tng hp cng c dng trong phim chp nh. Axetic anhydrit cng l mt cht phn ng dng sn xut aspirin, heroin, v cc hp cht khc.

ng dng axit exetic

4. Gim
dng gim, cc dung dch axit axetic (nng khi lng ca axit 4% n 18%) c dng trc tip lm gia v, v cng lm cht trn rau v trong cc thc phm khc. Gim n (table vinegar) th long hn (4% n 8%), trong khi loi gim trn thng mi th nng cao hn. Lng axit axetic dng lm gim khng chim t l ln trn th gii, nhng l mt ng dng ni ting v c dng t rt lu.

ng dng axit exetic

ng dng axit exetic

5. Lm dung mi
Axit axetic bng l mt dung mi protic phn cc tt nh cp trn. N thng c dng lm dung mi ti kt tinh cho cc hp cht hu c tinh khit. Axit axetic tinh khit c dng lm dung mi trong vic sn xut axit terephthalic (TPA), mt nguyn liu th sn xut polyetylen terephthalat (PET). Nm 2006, khong 20% axit axetic c dng sn xut TPA. Axit axetic thng c dng lm dung mi cho cc phn ng lin quan n cacbocation, nh Friedel-Crafts alkylation. V d, mt giai on trong sn xut long no tng hp thng mi lin quan n s ti sp xp WagnerMeerwein ca to amfen isobornyl axetat; y axit axetic ng vai tr va l dung mi, va l cht i nhn gi carbocation ti sp xp. Axit axetic l dung mi t chn khi gim mt nhm nit aryl to anilin bng cch s dng cacbon mang palladi. Axit axetic bng c s dng trong ha phn tch c tnh cc cht c tnh kim yu nh cc amit hu c. Axit axetic bng c tnh baz yu hn nc, v vy amit ng x nh mt baz mnh trong dung dch axit trung bnh ny. Sau n c th c chun bng cch s dng mt dung dch axit axetic bng ca mt axit rt mnh nh axit percloric.

Axit terephthalic

Nha PET

ng dng axit exetic

6. Mt s ng dng khc
Cc axit axetic long cng c dng to chua nh. V d nh trong quy m gia nh, n c dng lm cht ty cn vi t vi nc v m un nc. Cc dung dch axit axetic bng long c th c dng trong cc phng th nghim lm sng dung gii cc hng cu cng nh m bch cu. Mt ng dng lm sng khc l dung gii cc hng cu, m c th lm m cc thnh phn quan trng khc trong nc tiu khi phn tch di knh hin vi.

Ch tiu cht lng

Cc phng php nh gi cht lng :
Ngoi quan: Dng mt, tay, li kim tra ch tiu ngoi quan ca sn phm. Hm lng Axit acetic, SO4, Fe, Pb, theo cc phng php phn tch ha hc chun Hm lng cht khng tan trong nuc theo TCVN 5492-1991 Khi lng ng gi theo quy nh hin hnh

Ch tiu cht lng

Tn ch tiu Mc cht lng

Ngoi quan Hm lng Axit Axit acetic tinh khit

(CH3OOH) % khng nh hn Hm lng Sunphat ( SO4) % khng ;ln hn Hm lng st ( Fe) % khng ln hn

Cht lng, khng mu ,Tinh th trng, khng c tp cht c hc, c v chua ca chanh 99.0

0.0005 0.0005

Hm lng kim loI nng ( Pb) % khng ln hn

Hm lng cht khng tan trong nc, % khng ln hn Khi lng ng gi : g , : Kg

0.0005
0.005 500 +-15 1.0 +-0.015 25.0+-0.25

Ch tiu cht lng

Sales specifications Limits
Acetic acid, wt % Distillation range (including 118.1), C Freezing point, C Color, Pt Co units Water content, wt % Reducing substances, as formic acid, wt % Aldehydes, as acetaldehyde, wt % Iron, ppm min. max. min. max. max. max. max. max. 99.85 1.0 16.35 10 0.15 0.05 0.05 1

Heavy metals, as Pb, ppm

Chlorides, ppm Sulfates, ppm Sulfurous acid, ppm

max.
max. max. max.

0.05
1 1 1

Tn cha v bo qun
Axit axetic c th c tn cha, bo qun v vn chuyn nh cc thng cha lm bng thp khng g, thy tinh hoc bng polyetylen. Mt vt liu khc cng dng tn cha axit axetic l cc thng nhm. Cc thng nhm lun c bao ph mt lp nhm oxit hoc nhm axetat. Lp v ny t ra rt hu hiu trong vic chng n mn. Khi bo qun phi rt thn trng trnh s xm nhp v lm bn axit ca nc v thy ngn. V ch mt lng thy ngn hay nc nh cng gy ra s n mn. Do nhng ni tn cha mt lng axit ln tuyt i khng c dng cc dng c do bng thy ngn nu khng mun xy ra thm ha ca vic n mn Axit axetic c nhit nng chy thp 16oC cho nn khi vn chuyn axit qua cc vng thi tit lnh th cc thng cha yu cu phi c cc thit b gia nhit, v cc thng cha cng yu cu phi c cc thit b nh vy

Tn cha v bo qun

nh hng n sc khe
Axit axetic l mt loi axit yu. Chng yu hn rt nhiu so vi cc axit v c hay axit formic. Tuy nhin n c th gy n mn da tay Axit axetic c pha long vi nng 5%( gim ) c th gy hi ti cc mng nhy ca con ngi. Dm cha khong 3-6% axit . Ngi trn 2 tui c th s dng 2.1g/ngy. Tuy nhin axit axetic pha long ph hy da nng hn so vi cc axit v c khc do chng thng c trn vi cht bo Acetic acid tip xc vi mt, mi v c hng trn 10 ppm. Tip xc nhiu ln n 26 ppm trong khong mi ngy gy ra tc dng ph. Hn 100ppm acid c th lm hng b phn c th nh mt, mi, c hng Lng acid ln c th lm hng da nghim trng. Trnh tip xc vi acid acetic bng hoc hi ht vo. Trong trng hp trn cn ra sch vng tip xc bng nhiu nc. V vy, x l acid yu cu thn trng.

nh hng n sc khe

X l nc v kh thi
Cht thi t qu trnh sn xut axit axetic thng c cha axit axetic v formic cn st li. Cc axit ny phi c ti ch, pha long, hoc x l ha hc v sinh hc. Acetic acid c th n mn v lm hng da ca con ngi v c quan ni tng. axit axetic cn c x l cn thn trnh hit phi. Nu trn xy ra, phi trung ha t v ra sch vi tro hay vi soda. Ti c khng qu 3kg/h c th c thi ra trong khng kh, vi ti a l 150 mg/m3. Cc kh thi ra c lm lnh loi b cc axit. Theo quy nh cng c, lng kh thi ti a cho methyl acetate, ethyl acetate, butyl acetate, v acetate phenyl l 300 mg/m3. Cc phng php c ngh loi b cc acid acetic l nhit ngng t, ra khng bay hi dung mi hu c hp th vt l, hoc t. Ti Hoa K, Hoa K Clean Air Act chnh lng kh thi. Mi tiu bang cng t gii hn kh thi ring. Cc gii hn phm vi t 0,25 n 0,37 mg/m3 mg/m3 (North Dakota), vi 0,4 mg/m3 (Virginia) n 0,5 mg/m3 (Connecticut v Nam Dakota) n 0,595 mg/m3 (North Carolina)

Ti liu tham kho

Cng ngh tng hp hu c ha du. Phm Thanh Huyn v Nguyn Hng Lin. NXB KHKT 2006 Ullmann's Encyclopedia of Industrial Chemistry Published by Wiley-VCH Verlag GmbH & Co. KGaA Petrochemical processes technical and economic characteristic major oxygenated chlorinated and nitrated derivatives. Translate from the France by Nissim Marshall http://www.bp.com http://www.basf.com http://www.monsanto.com http://vi.wikipedia.org/wiki/Ax%C3%ADt_axetic

LOGO