Axit fomic

Mt s lng ng k axt fomic c sn xut nh l mt sn phm ph ca qu trnh sn

xut cc ha cht khc, c bit l axt axetic. Qu trnh sn xut ny khng p ng
yu cu hin nay i vi axt fomic, v mt s lng axt ny phi c sn xut cho mc
ch ring.
Khi mtanol v cacbon mnxt c kt hp vi s c mt ca mt baz mnh s to ra
metyl fomiat, mt dn xut ca axt fomic, theo phng trnh ha hc
CH3OH + CO HCOOCH3
Trong cng nghip, phn ng ny c thc hin trong pha lng vi p sut cao. Cc iu
kin phn ng in hnh l nhit 80 C di p sut 40 atm. S thy phn ca metyl
formiat to ra axt fomic:
HCOOCH3 + H2O HCOOH + CH3OH
qu trnh thy phn trc tip metyl formiat t hiu qu i hi mt s lng nc d,
do mt vi nh sn xut thc hin qu trnh ny bng cch gin tip l cho metyl formiat
phn ng vi amnic to ra formamid, v sau thy phn formamid bng axt sulfuric
to ra axt formic:
HCOOCH3 + NH3 HCONH2 + CH3OH
2HCONH2 + 2H2O + H2SO4 2HCOOH + (NH4)2SO4
K thut ny c vn , c bit l vic thi ra sn phm ph amoni sulfat do mt s nh
sn xut gn y pht trin cc cch hiu qu v nng lng bng cch tch axt formic
khi lng nc d tha ln c s dng trong qu trnh thy phn trc tip. Mt trong
nhng cng ngh ny (c BASF s dng) l axt formic c ly ra khi nc thng
qua vic chit cht lng vi mt baz hu c.
Trong phng th nghim, axt fomic c th thu c bng cch nung nng axt oxalic trong
glyxerol khan v chit bng cch chng hi. Mt cch iu ch khc (phi c thc hin
di mt m trm khi) l thy phn axt etyl isonitril s dng dung dch HCl.[1]
C2H5NC + 2H2O C2H5NH2 + HCOOH

Axit acetic

Axit axetic c th n mn cc kim loi nh st, mangan v km sinh ra kh hydro v cc

mui kim loi tng ng gi l cc axetat. Nhm khi tip xc vi xy s to thnh mt
mng mng nhm xt trn b mt lm cho n c kh nng chng li mt cch tng i s
n mn ca axit, iu ny cho php cc bnh cha bng nhm c th dng vn chuyn
axit axetic. Cc axetat kim loi cng c th c iu ch t axit axetic v mt bazo tng
ng, nh phn ng ph bin l "natri bicacbonat + gim". Ch tr crm(II) axetat, th hu ht
cc axetat cn li u c th ha tan trong nc.
Mg(r) + 2 CH3COOH(l) (CH3COO)2Mg(dd) + H2(k)
NaHCO3(r) + CH3COOH(dd) CH3COONa(dd) + CO2(k) + H2O(l)

Axit axetic c th to cc phn ng ha hc c trng ca nhm axit cacboxylic nh to ra

nc v ethanoat kim loi khi phn ng vi kim; to ra ethanoat kim loi khi phn ng vi
kim loi; v to ra ethanoat kim loi, nc v cacbon dioxit khi phn ng vi cc cacbonat
v bicacbonat. Phn ng c trng nht l to thnh ethanol, v to thnh cc dn xut nh
axetyl clorua bng cch thay th nhm -OH bi -Cl. Cc dn xut thay th khc nh anhydrit
axetic; anhydrit ny c to ra theo phn ng trng ngng rch phn t nc t hai phn t
ca axit axetic. Cc este ca axit axetic tng t c th c to ra bi este ha, v cc amit.
Khi nung trn 440 C, axit axetic phn hy to ra cacbon dioxit v metan, hoc to ra
ethenon v nc.
Axit axetic c th c nhn bit bi mi c trng ca n. Phn ng bin i mu i vi
cc mui ca axit axetic l cho tc dng vi dung dch st(III) clorua, phn ng ny to ra
mu m sau khi axit ha. Khi nung nng cc axetat vi arsen trioxit to ra cacodyl oxit,
cht ny c th c nhn bit bi cc hi c mi hi.

Axit axetic c sn xut theo c hai phng php sinh hc v 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, theo cc 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. Khong 75%
axit axetic c sn xut cng nghip c dng sn xut theo phng php cacbonyl ha
metanol. Khong 15% cn li c sn xut t cc phng php thay th khc.[9] Tng sn lng
axit axetic gim c tnh khong 5 triu tn/nm, khong na trong s c sn xut Hoa K.
Sn lng chu u khong 1 triu tn/nm v ang gim, trong khi Nht Bn sn xut khong
0,7 triu tn/nm. Khong 1,5 triu tn c ti ch hng nm, nng tng sn lng trn th trng
th gii ln 6,5 triu tn/nm.[10][11] Hai nh sn xut axit axetic gim ln nht l Celanese v Cng ty
ha BP. Cc nh sn xut ln khc nh Millennium Chemicals, Sterling Chemicals, Samsung,
Eastman, v Svensk Etanolkemi.

Cacbonyl ha metanol
Hu ht axit axetic gim c sn xut bng phng php cacbonyl ha metanol. Trong quy trnh
ny, metanol v cacbon monoxit phn ng vi nhau to ra axit aextic theo phng trnh:
CH3OH + CO CH3COOH
Qu trnh ny lin quan n cht trung gian iodometan, v din ra theo 3 bc. Cht xc tc, thng
l phc cht kim loi, c dng trong bc 2.
1. CH3OH + HI CH3I + H2O
2. CH3I + CO CH3COI
3. CH3COI + H2O CH3COOH + HI
Bng cch theo th cc iu kin phn ng, anhydrit axetic cng c th c to ra trong t cc vt
liu ny. Bi v c metanol v cacbon monoxit u l cc hng ha nguyn liu, cacbonyl ha
metanol trong mt thi gian di l phng php sn xut axit axetic c a chung. Henry Drefyus
British Celanese xy dng mt nh my sn xut theo phng php ny vo nm 1925.[12] Tuy
nhin do thiu cc vt liu c th cha cc hp cht gy n mn p sut cao (khong 200 atm hoc
hn) khng c khuyn khch thng mi ha phng php ny. Phng php cacbonyl ha
metanol thng mi u tin, s dng cht xc tc coban, c cng ty ha cht c BASF pht
trin nm 1963. Nm 1968, cht xc tc gc rhodi (cis[Rh(CO)2I2]) c pht hin c th vn
hnh mt cch hiu ph p sut thp m hu nh khng c sn phm ph. Nh my u tin c
dng cht xc tc ny c cng ty ha cht Hoa K Monsanto xy dng nm 1970, v cacbonyl
ha metanol vi xc tc rhodi tr thnh mt phng php ph bin dng sn xut (xem cng
ngh Monsanto). Vo cui thp nin 1990, Cng ty ha cht BP thng mi ha cht xc tc Cativa
([Ir(CO)2I2]), c cht t rutheni. Cng ngh Cativa dng cht xc tc iridi ny sch hn v hiu
qu hn[13] v thay th phn ln cng ngh Monsanto, thng dng trong cng mt nh my sn
xut.

xy ha axetaldehyt

Trc khi thng mi ha cng ngh Monsanto, hu ht axit aextic c sn xut bng cch xy
ha axetaldehyt. Phng php ny l phng php quaan trng th hai vn cn c s dng mc
d n khng th cnh tranh vi phng php carbonyl ha metanol.
Axetaldehyt c th c sn xut bng cch xy ha butan hoc naphtha nh, hoc hydrat ha
etylen. Khi butan hoc naphtha nh c nung n trong khng kh c mt cc ion kim loi khc
nhau nh mangan, coban, v crm, peroxit v sau phn hy to ra axit axetic theo phng trnh
phn ng:
2 C4H10 + 5 O2 4 CH3COOH + 2 H2O
Phn ng c trng l s kt hp ca nhit v p sut c u chnh sau cho nng c th
gi butan dng lng. Cc iu kin phn ng c trng l 150 C v 55atm. Cc sn phm ph
cng c th c to ra, nh butanon, etyl axetat, axit formic, v axit propionic. Cc sn phm ny
cng c gi tr thng mi, v cc iu kin phn ng c th c thay th to ra s lng sn
phm nhiu hn. Tuy nhin, vic phn tch axit axetic ra khi hn hp ny lm cho phng php
ny kh tn km.
Cng cc iu kin v s dng cc cht xc tc tng t trong vic xy ha butan, axetaldehyt c
th b xy ha bi oxy trong khng kh to ra axit axetic:
2 CH3CHO + O2 2 CH3COOH
S dng cc cht xc tc hin i, phn ng ny c th to ra axit axetic hn 95%. Cc sn phm
ph l etyl axetat, axit formic, v formaldehyt u c im si thp hn axit axetic nn s d tch
chng ra bng cch chng ct.[14]

xy ha etylen
Axetaldehyt c th c iu ch t etylen theo phn ng Wacker, v sau xy ha nh nn bn
di. Trong thi gian gn y, vic chuyn i etylen thnh axit axetic qua theo mt bc, chi ph r
hn c cng ty Showa Denko thng mi ha, cng ty ny xy dng mt nh my oxy ha
etylen ita, Nht Bn nm 1997.[15] Qu trnh ny s dng cht xc tc l kim loi palladi vi s
h tr ca axit heteropoly nh axit tungstosilicic. N c xem l mt phng php c th cnh
tranh vi phng php carbonyl ha metanol i vi cc nh my nh hn (100250 ngn tn/nm),
ty thuc vo gi a phng ca etylen.

Ln men xy ha
Trong lch s nhn loi, axit axetic, dng gim, c to ra t cc vi khun axit axetic thuc chi
Acetobacter. Khi cung cp xy, cc vi khun ny c th to ra gim t cc thc phm sinh cn
khc nhau. Cc loi c s dng nh ru to, ru vang, v cc loi ng cc, go, mch nha hoc
khoai ty ln men. Phn ng ha hc chung nht do cc vi khun thc hin l:
C2H5OH + O2 CH3COOH + H2O

Dung dch ru long trn vi Acetobacter v gi ni thong kh, m s to ra gim trong vng
vi thng. Cc phng php sn xut gim cng nghip, ngi ta tng tc phn ng bng cch
cung cp nhiu xy cho vi khun.
Cc l gim u tin c sn xut bng phng php ln men c th l li trong qu trnh lm ru
vang. Nu hm ru nho c ln men nhit qu cao, acetobacter s pht trin ln n nm men
c mt t nhin trong nho. V nhu cu gim cho mc ch m thc, y t, v v sinh gia tng, nhng
ngi bn ru nho hc nhanh chng cch s dng cc vt liu v c khc sn xut gim trong
cc thng h nng trc khi nho chnh v sn sng sn xut ru vang. Phng php ny
chm, tuy nhin, khng phi lc no cng thnh cng, khi nhng ngi bn ru khng hiu qu
trnh ny.[16]
Mt trong nhng cng ngh thng mi hin i u tin l "phng php nhanh" hoc "phng
php c", c ng dng c nm 1823. Trong phng php ny, qu trnh ln men din ra
trong mt thp bc bng g bo hoc than. Cc cht cung cp cn c cung cp t trn nh thp,
v khng kh sch c cung cp t di ln bng thng kh t nhin hoc bn i lu. Vic cung
cp khng kh c ci thin trong qu trnh ny lm gim bt thi gian iu ch gim t vi thng
cn vi tun.[17]
Ngy nay, hu ht gim c sn xut trong cc thng ngm c Otto Hromatka v Heinrich
Ebner s dng u tin nm 1949.[18] Trong phng php ny, ru c ln men thnh gim trong
bn c o lin tc, v xy c cung cp bng cch thi bt kh qua dung dch. S dng cc ng
dng hin i ca phng php ny, gim cha 15% axit axetic c th c u ch trong vng 24
gi, thm ch t c gim 20% trong vng 60 gi.[16]

Ln men k kh
Cc loi vi khun k kh bao gm c thuc chi Clostridium, c th chuyn i ng thnh axit
axetic mt cch trc tip m khng cn phi qua bc trung gian l to thnh etanol. Phn ng
chung m cc vi khun thc hin c th c biu din:
C6H12O6 3 CH3COOH
Trn quan im ca mt nh ha hc cng nghip, mt im ng ch l cc vi khun acetogen c
th to ra axit axetic t cc hp cht cha 1 cacbon nh metanol, cacbon mnxt, hay hn hp ca
cacbon dioxit v hydro:
2 CO2 + 4 H2 CH3COOH + 2 H2O
Kh nng Clostridium chuyn ha trc tip cc loi ng hoc to ra axit axetic vi chi ph u
vo thp, c ngha rng cc vi khun ny c th c kh nng to ra axit axetic hiu qu hn phng
php xy ha etanol nh Acetobacter. Tuy nhin, vi khun Clostridium y chu axit hn Acetobacter.
Ngay c hu ht cc chng Clostridium chu axit nht c th to ra gim ch t vi phn trm axit
axetic, so vi cc chng Acetobacter c th to ra gim vi nng axit ln n hn 20%. Hin ti,
chi ph sn xut gim bng Acetobacter vn cao hn dng Clostridium v sau tch n. Kt qu
l, mc d vi khun acetogenic c bit n rng ri t nm 1940, vic s dng quy m cng
nghip ca loi vi khun ny vn cn gii hn trong mt vi ng dng.[19]