axit axetic 2011

8/4/2019 axit axetic 2011

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GVHD: PGS-TS: Phm Thanh HuynSVTH: 1. inhNgc Phan hd1

2.NguynTrngNgha hd13. PhmSng hd1


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1. Tnh cht 2. Ccphng php snxutcng nghip 3. Tnchaboqun,ng

dng,ch tiu chtlng


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Axit axetic l chtlng khng mu hoc tinhth mu trng, c v chua, c khnng tan v

hn trong nc.Ttrngca axit axetic dnglng l

1.049g/cm3 v dng tinh th l 1.266g/cm3.

Tnc = 16.5o

C, Ts = 118,1o

C

1.1 Tnh cht l hc


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Axit axetic c tnh axit, 25oC n c pKa = 4,26, thhin:

Lm thay i mu qu tm

Khi thm axit axetic vo dung dch Ca(OH)2 cmt phenolphtalein, dung dchmtdn mu hng

phnngvibaz

Axit axetic ha tan CuO thnh dung dch c mu xanhctrngphnngvi oxitbaz

Ha tan Znphnngvi kim loi

Tc dng vi mui ( phn ng vi CaCO3 thot kh

CO2)

1.2 Tnh cht ha hc


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Axit axetic trong cng nghipcsnxut theo 2phng php:phng php sinh hc vphng php tnghp.

Ngy nay, lng axit snxut theophng php sinh hcchchim

khong 10% snlngthgii, nhng n vn l mtphng php quantrng dng snxutgim (mtsiulutv tinh khitthcphm mtsquc gia quy nhrnggimsdng trong thcphmphi cngungct sinh hc).

Phng php tnghpc p dngnhiuhnsnxut axit vinngsut cao. Trong , khong 75% axit axetic csnxut cngnghipcsnxut theophng php cacbonyl ha metanol. Khong15% cn licsnxutt ccphng php thay th khc (oxy hatrctip hydrocacbon no, oxy ha axetaldehit, oxy ha etylen)

2.Phngphp snxutcng nghip


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Cacbonyl ha metanol

Oxy ha axetaldehyt

Oxy ha etylen

Oxy ha RH no(n-butan,naphta)

Ln men oxy ha Ln men k kh

Ccphng php snxut


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Cacbonyl ha metanol

BASF

MonsantoCativa

BP


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2.1.1 Lchspht trinCng nghsnxut axit axetic t metanol v

cacbonmonoxit nhit v p sut cao c hng BASF

a ra trtsm (1913) da trnphnng:

CH3OH + CO --> CH3COOH H298 = - 138,6 KJ/mol

iukintin hnh khcnghitvnhit v p sutcngvis c mtca cc chtn mn mnh (cc hpchtiotua) ngncnvicthngmi ho cng ngh ny.

2.1.Cng ngh cacbonyl ha metanol


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Nm 1914, cc nghin cu ca REPPE (BASF) chothyrng cc kim loi nhm VIII c khnng xc tc

hiuqu cho qu trnh cacbonyl ho. iu ny dnnvic ra i v pht trin cng nghnhit v p sutcao (250oC v 70MPa) vi xc tc CoI2. Qu trnh nyc 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 35.000tn/nm vo nm 1970.Nm 1981 cng sutt 45.000tn/nm.

Nm 1966, Borden Chemical c khing xy dngmt nh my snxut axit axetic trn cscng nghBASF ti Geimak (Bang Louisiana, M) vinngsutban u l 30.000 tn/nm sau tng ln 45.000

tn/nm vo nm 1968.


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Nm 1968, Monsanto cng bmt khm ph mi. Xctc rhodi vihot tnh v chn lc rt cao cho phnng cacbonyl ho metanol thnh axit axetic. Metanol cthc cacbonyl ho ngay cp sutthngvihiusutchuyn ho l 99% ivi metanol v 90% ivicacbon monoxit. Qu trnh c sdng xc tc ny cp dngnm 1970 ti bang Texas, vi cng sut ban ul 135.000 tn/nm, sau tng ln 180.000 tn/nm vonm 1975. iukintin hnh qu trnh Monsanto mm

hn so vi qu trnh BASF (3MPa v 180oC ) .


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2.1.2 Nguyn tc chung ca qu trnh Qu trnh cacbonyl ha metanol l mtphnngtanhit

CH3OH + CO CH3COOH H298 = - 138,6 KJ/mol

Phnngxy ra thunli trong pha lng, nhit 220250oC, psutca qu trnhphicgimc 30MPa. S c mtcanc(> 30% TT) v vicsdng xc tc s gip gimbtkhcnghitca cc iukin tin hnh qu trnh, cbit l p sutcgimxung 37 MPa v nhit 150200oC

H xc tc angcsdnggm c 3 thnhphn: pha hotng,cht xc tin v dung mi. Pha hotng (cc oxit, cc hpchtckim, cc hpchtphi trhocmuica kim loi qu himnh Co,Rh) c nngn 10-3M. Cht xc tin, khi mo (1M) l halogen hoccc hpchtcha halogen.


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3.1.3 Cng ngh BASFQu trnh BASF sdng cacbonyl coban lm xc tc

vicht kch ng iotua CoI2c dng ti sinh

tich Co2(CO)8 v HI. Tcphnngphthucvo p sut ringphnca cacbon monoxit v nng metanol. Hiusut thu axit axetic t 90% ivimetanol v 70% ivi cacbon monoxit.


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Cchphnngnh sau:


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Phnng (1) c thchuyn ho CO bnghinc, xctc l Co2(CO)8 v H2cto rabng cch phn lyphc

hydro cacbonyl. Metyl iotua lin tc tn cng bi tcnhn nucleophil l ion [Co(CO)4]- (4). Gc iotua lmcho phnngd dng hn v n d tch hn OH-. CH3I

phn ng viphi tr bo ho d10 Co(CO)4. Qu trnh

oxy ho cnghpca CH3I vo Co(CO)4 kh khnhnvo [Rh(CO)2I2]-. Snphm cng hp ban u l mtphc 5 phi tr d8 CH3Co(CO)4. Giai on chuyn vmetyl (5) xy ra chmhn so vi qu trnh xc tcbi

Rh. Khi to thnh hp cht trung gian axyl ca coban,hp cht ny khng b phn hu to coban iotua v iodkhngphi trvi coban


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Cc giai on lin quan ncchphnng dng xctc rhodi c gii thch bi kh nngphn ng cacoban thp hn ca rhodi. iu ny gii thch ti saonhit ca qu trnh BASF li cao hn ca qu trnhMonsanto. Hn na p sut ring phn ca cacbonmonoxit cngphi cao nnhphc [Cd(CO)4]-.

Snphmph ca BASF l CH4, CH3CHO, C2H5OH,C2H5COOH, CO2. Khong 3,5% CH3OH phnngmtmt di dng metan, 4,5% di dng snphmphlng, 2% di dng kh thi. Khong 10% CO nguyn

liubbini thnh CO2 theophnngchuyn ho khhinc.

CO + H2O --> CO2 + H2 (9)


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CO2, metanol (cha 60% dimetyl ete), xc tc tun hon,xc tc mi, metyl iotua tun hon (t thp ra) can thitbphnng p sut cao (b). Mtphnca nhit

phnngc dng un nng sb nguyn liu, phnnhit cn lic tiu tn dc theo ngphnng.

Snphmphnngc lm lnh v anthitb phnly p sut cao (d). Khthica vo thp ra (o)phnlngcginnti p sut 0,5 1 MPa trong thitb phnly p sut trung bnh (e). Kh thot ra cngc vo thpra (o),phnlngtthitb phn ly p sut trung bnh canbungginn(f). Kh ra khibungcanthitbra (p). Khtthitbra v thp ra l khthi. C

thitbra v thp rau dng metanol nguyn liu thuhi metyl iotua v cc hpcht iotua d bay hi khc. Dungdch metanol ny catrlithitbphnng. Thnh

phn kh thi (% th tch): CO: 65 -75%, CO2: 15-20%,

CH4: 3-5% v hi metanol.


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Axit tbung gin n (f) chim 45% khi lng axitaxetic, 35% khilngnc, 20% khilng este (chyu l metyl axetat). Axit c tinh ch5 thp chng

ct. Thp th nht (h) dng ui kh t hn hp snphm th, kh thot ra c a vo thp ra. Xc tcc tch rabng cch chngct cc cutd bay hithitb tch xc tc (i). Tithitbsy (k) cho php nhn

c axit tinh bngphng php chng ct ng ph.Snphm nh ca thp lm kh cha axit axetic, axitformic, nc, snphmph, chng tohnhpng phvinc. Snphmnh ny l mth hai pha, n c

tch trong bung (g). Mtphnca pha huc, chachyu este ctrli (k), n ng vai tr l mttc nhn ng ph


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. Phn cn lican thpph (n), yphnnngc ly ra phny thp, phn nh nhthp ca tun hon li thitbphnng. Phnchyuthp lm kh can thp lm sch

lncui, axit axetic cly ra nh thp, snphmycan thp tch cn (m). Snphmnh ca thp ny c a ti thp tch nc, sn

phmycha 50% khi lng axit propionic c

ai thu hi.


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Monsanto process

Thng s BASF Monsanto

Thi gian 1941 1960

Xc tc CoI2 RhI2

Nhit (o C) 250 200

p sut ( Mpa) 68 35

chnlc 90% ( MeOH)70% (CO)

99% ( MeOH)90% (CO)

H xc tc Rhonium uvithn Cobalt

So snh cng ngh


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S pht trin xc tc : Nm 1941 Reppe ti BASF chng minh hiu qu ca

nhm carbonyls kim loi VIII nhcht xc tc cho phnngcarbonylation :xc tc cobalt it, p sut cao, xl nhitv p sut cao (700 bar, 250C)

Monsanto pht trin qu trnh snxut axit axetic trongcui thp nin 1960 vih xc tc rhodium , cht xc tcthc ytcphnng v chn lc cao vi quy trnh

da trn h xc tc cobalt ca BASF Monsanto trong u nhng nm 1960 cng pht hin rarng iridi, nh rhodium, l mt cht xc tc carbonylationmethanol c hiu qu. H thng cht xc tc c phttrin BP trong nm 1990 v cgi l qu trnh Cativa

Monsanto process


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Xc tc Rhodium/iodide: Xc tc cacbonyl ha gm 2

thnh phn kim loi Rh c

hot ha trn cht mang iode Xc tc tophccht trung gian

gm Rh,CO v phitl halogen Ti sinh xc : Trc tin loib cc ion kim loi c ln do qu trnh xlbng

nha trao i ion. Sau l sau nhit phn mtphnnhunnng,ri lmlnh, kt ta thu hi cu t cha Rh. Cc hp cht ny scb sung iot mi riha tan trong axit axetic nng di psut CO

Monsanto process


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Thng squ trnh cacbonyl ha metanol :

CH3OH + CO CH3COOH H =137KJ/mol Phnng thu nhit :H > 0

Nhit : khong 200o

C p sut : 35 MPa Xc tc : hpchtphi tr rodi-clorocacbonyl-bis

triphenylphosphin :Rh(CO)[P(C6H5)3]2Cl

Monsanto process


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Monsanto process

Cch


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Methanol

RhI3

Spentcatalyst

Methyl iodideproduction

Methanol

Methyliodide

storage

Ionexchang

eresins

Catalyststorage

Iodide(H2O)

hydro

Carbon

ylation

reactor

Gasscru

bbing

withmethanol

strippin

g

Aceticacid

purificat

ion

Propionic

acid

Water

removal

Dehydroby

azeotro

pic

distillat

ion

Distillationofacid

Enrichedwitacetic

Glacial

Acetic acid

Residual

acetic

acidrecovery

Residualgas

CO,CO2, N2


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Company Logo

Monsanto process

uim 100%, vi tt c cc

nguyn t trong ccchtphnngi vosnphm

S dng nng lngt hn,cbit tchv tinh ch.

C nngsut cao, S dng methanolnguyn liurhn sovi naphta trc /butan

Tc phn ngnhanh. Chu k sngcaxc tc di

nh giCng ngh

Nhc im Rhodium l kim loirt

ttin - thn vng Rhodium cng xc tc

phnngphCO + H20 2+ H2

iu ny lm gim p sutring phn ca kh carbon

monoxide Rhodium ha tan to

mun RhI3. Cn ccng on tch ncgy tn chi ph v nnglng tr li xc tcchophnng chnh


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Theo quan imca BP, CATIVA - mi ba nm sau khi thngmi ha lnu tin -vn l cng nghhiuqunht, quy nhvvn v chi phvnhnh thpnht.

Nm 1986 Monsanto cp php cho mtscng ty, bao gm BP, trong BP mua bnquyn cng nghca Monsanto v carbonylation methanol vpht trin n hnnato ra thnghiucquynca BP : CATIVA

Skhc bitcbnnhtgia cc phin bnca qu trnh carbonylation l

cht xc tc. Cng ngh carbonylation cbnca Monsanto l da trn xctc rhodium, qu trnh CATIVA ca BP nhdumtbc thay i trong cngnghbi v n chuyn hon ton ra khi rhodium thay vo l xc tc iridida trn kthpvimtchthot ha kim loichuyntip

CATIVA process

C g ng k v qu trnh CATIVA ca BP, ngy nay n vn l cngngh tt nht sn xut axit axetic thng mi


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CATIVA process

Cch


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CATIVA process


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u im cng ngh CATIVA :

Xc tc Ir c gi r bng 1/10 gi ca Rh theo cng trnglng.

Lu trnh cng ngh n gin hn monsanto rt nhiu. S

lng cc thp tinh chcngin ha v gimirtnhiu

Sdng thitbphnngdngsc kh thay th cho thitbkhuychcngthi c thm thitbphnngthcpnhm

nng cao hiu sut chuyn ha

CATIVA process


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CATIVA process


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ngdng axit exetic

Monome vinyl axetat

Sn xut este

Axetic anhydrit

Gim

Lm dung mi

Mtsngdng khc

Axitaxetic


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1. Monome vinyl axetat ngdng chyu ca axit axetic l snxut monome vinyl

axetate. ng dng ny tiu th khong 40% n 45% snlng axit axetic trn thgii. Phnng c s tham gia caetylen 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 polyvinylaxetat hoc thnh cc polyme khc ng dng trong sn vchtkt dnh.

ngdng axit exetic


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2. Sn xut este Cc este chnh snxuttaxit axetic csdngchyu lm dung

mi cho mc, sn v cht ph. Cc este nh ethyl axetat, n-butylaxetat, isobutyl axetat, v propyl axetat, chng c sn xut mtcch cbitbngphnng c xc tc taxit axetic v ru tng

ng: H3C-COOH + HO-R H3C-CO-O-R + H2O

Tuy nhin, huht este axetat csnxuttacetaldehyt bngphnng Tishchenko. Thm vo , cc ete axetat csdng lm ccdung mi loib nitrocellulose, sn acrylic, vc-ni, v chttyg.u tin, glycol monoete cto ra tetylene oxit hoc propylen oxitvi ru, sau chng c este ha vi axit axetic. Ba snphmchnh l etylen glycol monoetyl ete axetat (EEA), etylen glycol mono-butyl ete axetat (EBA), v propylen glycol mono-metyl ete axetat(PMA). ngdng ny tiu thkhong 15% n 20% sn lng axitaxetic thgii. Cc ete axetat, vdnhEEA, c cho l c hiivisckhe sinh sn con ngi.

ngdng axit exetic


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3.Axetic anhydrit

Snphm tch phn tncthai phn taxit axetic to thnh mtphn tgi l axetic anhydrit. Snxut axetic anhydrit trn thgii l

mtngdng chnh chimkhong 25% n 30% snlng axit axeticton cu. Axetic anhydrit c thcsnxuttrctipbng cacbonylha metanol taxit, v cc nh my snxut theo cng ngh Cativa cthciuchnhsnxut anhydrit.

Axetic anhydrit l mtcht acetyl ha mnh. V vy,ngdng chnhca n l to cellulose acxtat, mtchtdttnghpcngc dngtrong phim chpnh. Axetic anhydrit cng l mtchtphnng dngsnxut aspirin, heroin, v cc hpcht khc.

ngdng axit exetic


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4. Gim

dnggim, cc dung dch axit axetic (nngkhi lng

ca axit 4% n 18%) c dng trctip lm gia v, v cnglm cht trn rau v trong cc thc phm khc. Gim n(table vinegar) th long hn (4% n 8%), trong khi loigimtrnthngmi th nng cao hn.

Lng axit axetic dng lm gim khng chimtlln trn th

gii,nhng l mtngdngni ting v c dng t rtlu.

ngdng axit exetic


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ngdng axit exetic


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5. Lm dung mi

Axit axetic bng l mt dung mi protic phn ccttnhcp trn. Nthngc dng lm dung mi ti kt tinh cho cc hpchthuc tinhkhit. Axit axetic tinh khit c dng lm dung mi trong vic snxutaxit terephthalic (TPA), mt nguyn liu th sn xut polyetylenterephthalat (PET). Nm 2006, khong 20% axit axetic c dng snxut TPA.

Axit axetic thngc dng lm dung mi cho cc phnng lin quan ncacbocation, nh Friedel-Crafts alkylation. V d, mt giai on trong snxut long no tnghp thngmi lin quan ns ti spxp Wagner-Meerwein cato amfen isobornyl axetat; y axit axetic ng vai tr val dung mi, va l cht i nhn gicarbocation ti spxp. Axit axeticl dung mi tchn khi gimmt nhm nit aryl to anilin bng cch sdng cacbon mang palladi.

Axit axetic bngcsdng trong ha phn tch c tnh cc cht ctnh kimyunhcc amit huc. Axit axetic bng c tnh bazyuhnnc, v vy amit ngx nh mt baz mnh trong dung dch axit trungbnh ny. Sau n c thcchunbng cch sdngmt dung dchaxit axetic bngcamt axit rtmnhnhaxit percloric.

ngdng axit exetic


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Axit terephthalic

Nha PET
http://vi.wikipedia.org/w/index.php?title=Axit_terephthalic&action=edit&redlink=1http://vi.wikipedia.org/w/index.php?title=Axit_terephthalic&action=edit&redlink=1http://vi.wikipedia.org/w/index.php?title=Axit_terephthalic&action=edit&redlink=1http://vi.wikipedia.org/w/index.php?title=Axit_terephthalic&action=edit&redlink=1http://vi.wikipedia.org/w/index.php?title=Axit_terephthalic&action=edit&redlink=1


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6. Mtsng dng khc

Cc axit axetic long cngc dng to chua nh. Vdnhtrongquy m gia nh, n c dng lm chttycn vi tvi nc v munnc.

Cc dung dch axit axetic bng long c thc dng trong cc phngthnghim lm sng dung gii cc hngcucngnhmbchcu.

Mtngdng lm sng khc l dung gii cc hngcu, m c thlmm cc thnh phn quan trng khc trong nctiu khi phn tch diknh hin vi.

ngdng axit exetic


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Cc phng php nh gi chtlng:

Ngoi quan: Dng mt, tay, likim tra ch tiungoi quan casnphm. Hm lng Axit acetic, SO4, Fe, Pb, theo cc phng

php phn tch ha hcchun Hm lng cht khng tan trong nuc theo TCVN

5492-1991 Khilngng gi theo quy nhhin hnh

Ch tiu chtlng


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Tn ch tiu Mc cht lngNgoi quan Cht lng, khng mu ,Tinh th trng, khng c

tp cht c hc, c v chua ca chanh

Hm lng Axit Axit acetic tinh khit

(CH3OOH) % khng nh hn99.0

Hm lng Sunphat ( SO4) % khng ;ln hn 0.0005Hm lng st ( Fe) % khng ln hn 0.0005Hm lng kim loI nng ( Pb) % khng ln hn 0.0005

Hm lng cht khng tan trong nc, % khngln hn 0.005Khi lng ng gi : g ,

: Kg500 +-15

1.0 +-0.015

25.0+-0.25

Ch tiu chtlng


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Sales specifications Limits

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

Ch tiu chtlng


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Axit axetic c thctncha, boqun v vnchuynnh cc thngcha lm bng thp khng g, thy tinh hocbng polyetylen.

Mt vt liu khc cng dng tn cha axit axetic l cc thng nhm.

Cc thng nhm lun c bao phmtlp nhm oxit hoc nhm axetat.Lpv ny t ra rthuhiu trong vicchngn mn. Khi boqunphirt thn trng trnh s xm nhp v lm bn axit ca nc v thyngn. V chmtlngthy ngn hay ncnhcng gy ra sn mn. Donhngnitnchamt lng axit lntuyti khng c dngcc dngc do bngthy ngn nu khng munxy ra thmhacavicn mn

Axit axetic c nhit nng chythp 16oC cho nn khi vnchuyn axitqua cc vng thitit lnh th cc thng cha yu cuphi c cc thitbgia nhit, v cc thng chacng yu cuphi c cc thitbnhvy

Tncha v boqun


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Tncha v boqun


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Axit axetic l mtloi axit yu. Chng yuhnrtnhiu so vi ccaxit v c hay axit formic. Tuy nhin n c th gy n mn da tay

Axit axetic c pha long vinng 5%( gim ) c th gy hiti cc mng nhyca con ngi.

Dmchakhong 3-6% axit . Ngi trn 2 tui c thsdng2.1g/ngy. Tuy nhin axit axetic pha long ph hy da nnghn sovi cc axit v c khc do chng thngctrnvicht bo

Acetic acid tip xc vi mt,mi v chng trn 10 ppm. Tip xcnhiulnn 26 ppm trong khongmi ngy gy ra tc dngph.

Hn 100ppm acid c th lm hngbphncthnhmt, mi, chng Lng acid ln c th lm hng da nghim trng. Trnh tip xcvi acid acetic bnghochi ht vo. Trong trnghp trn cnrasch vng tip xc bngnhiunc. V vy,x l acid yu cuthntrng.

nhhngnsckhe


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nhhngnsckhe


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Cht thi t qu trnh sn xut axit axetic thng c cha axit axetic v

formic cn st li. Cc axit ny phic ti ch, pha long, hocx l hahc v sinh hc.

Acetic acid c th n mn v lm hng da ca con ngi v c quan ni

tng. axit axetic cncx l cn thn trnh hit phi. Nu trn xy ra,phi trung ha t v raschvi tro hay vi soda.

Tic khng qu 3kg/h c thc thi ra trong khng kh, vi tia l150 mg/m3. Cc khthi ra c lm lnhloib cc axit.

Theo quy nh cng c, lng kh thi ti a cho methyl acetate, ethylacetate, butyl acetate, v acetate phenyl l 300 mg/m3. Cc phng php

cngh loib cc acid acetic l nhitngng t, ra khng bay hidung mi huchpthvt l, hoct.

Ti Hoa K, Hoa K Clean Air Act chnhlng khthi. Mitiu bang cngtgiihn kh thi ring. Cc giihnphm 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 NamDakota) n 0,595 mg/m3 (North Carolina)

X l nc v khthi


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Cngnghtnghphuc ha du. Phm Thanh Huynv NguynHngLin. NXB KHKT 2006

Ullmann's Encyclopedia of Industrial ChemistryPublished by Wiley-VCH Verlag GmbH & Co. KGaA

Petrochemical processes technical and economiccharacteristic major oxygenated chlorinated and nitratedderivatives. 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

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