n C Nhn

MC LC
TNG QUAN...................................................................................... 2

I.
1.

Sn Phm:......................................................................................... 2

a)
Tnh Cht Vt L:.............................................................................................................................3
b) Tnh Cht Ha Hc:...............................................................................................................................4
c)
Cc nguy him ca etanol:................................................................................................................5
2. Nguyn Liu:......................................................................................5
a)
b)
c)

Thnh phn mt r:...........................................................................................................................5

PH ca mt r:...................................................................................................................................6
Vi sinh vt trong mt r:...................................................................................................................6
3. Cc Phng Php Sn Xut:.....................................................................7

1.
2.
II.

a)
b)
c)

Tng Hp:..........................................................................................................................................7
Ln Men:............................................................................................................................................9
CHNG CT V TINH CH CN ETYLIC.................................................13

1.

L thuyt v l thuyt tinh ch cn.............................................................13

2.

Cc s chng ct v tinh ch:................................................................15

Chng luyn gin on:..................................................................................................................16

S chng luyn bn lin tc:.....................................................................................................19
Chng luyn lin tc:......................................................................................................................20
3. Cc Phng Php Thu Cn Etylic Khan:......................................................24

a)
b)
c)
d)
III.

Chng ng Ph:.............................................................................................................................24
Hp ph sng phn t:...................................................................................................................25
Chng ct chn khng:...................................................................................................................25
Ti Sinh Cht Hp Ph:.................................................................................................................25
TNH TON CN BNG VT CHT, CN BNG NHIT LNG......................27

(M PHNG CNG NGH BNG Aspen Hysys 7.2)...............................................27

a)
b)
c)
d)
e)
f)

1.

M u:.......................................................................................... 27

2.

Nhp cc cu t cho phn ng ln men:........................................................28

3.

Trnh t m phng:..............................................................................31

Thit b phn ng:...........................................................................................................................31

Thp hp th CO2:..........................................................................................................................34
Thp hp th etanol:.......................................................................................................................37
Thp hp th c ngng t nh v hi lu nh:.........................................................................39
Thp chng ct:...............................................................................................................................42
Thp hp ph: (Component Splitter)............................................................................................48
4. Tnh ton cn bng vt cht, cn bng nhit lng:....................................................50

IV.

Kt Lun.............................................................................................................54

V.

Ti Liu Tham Kho.............................................................................................55

I.
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1. Sn Phm:
Etanol cn c gi l ru etylic, ru ng cc hay cn. N l mt hp cht hu c nm
trong dy ng ng ca ru metylic, d chy, khng mu, l mt trong cc thnh phn
ca ung cha cn. Trong dn d, n thng c gi vn tt l ru. Cng thc ho
hc C2H5OH, vit tt l C2H60.
Etanol c con ngi s dng t thi tin s (t thi mi) nh l mt thnh
phn gy cm gic say. Vic chit etanol tng i nguyn cht vi nng 96% c
thc hin vo thi k Abbasid Hi gio (nm 721-815). Etanol tinh khit ln u tin c
Johann Tobias Lowits thu hi vo nm 1796 bng phng php chng ct qua than ci.
Antoine Lavoisier m t etanol l hp cht ca hydro, cacbon v oxy. Vo nm 1808
Nicola-Thodere de Saussure xc nh c cng thc ho hc, nm 1858 Archibald
Scott Couper cng b cng thc cu to, iu ny lm cho etanol tr thnh mt trong
cc hp cht ho hc u tin c s xc nh cu trc ho hc.
Etanol ln u tin c Henry Hennel Anh v Srullas Php tng hp nhn to vo
nm 1826. Faraday tng hp etanol bng phn ng hyrdrat ho etylen vi xc tc axit
vo nm 1828 theo mt cng ngh tng t nh cng ngh tng hp etanol ngy nay.
Etanol d dng ho tan vo nc theo mi t l, vi s gim nh tng th v th tch khi
hai cht ny c trn ln vi nhau. Etanol tinh khit hay etanol 95% l cc dung mi tt,
s dng trong cc loi nc hoa, sn v cn thuc. Cc t l khc ca etanol vi nc
cng c th lm dung mi . Cc loi ung cha cn c hng v khc nhau do c cc
cht to mi khc nhau dc ho tan trong n trong qu trnh v nu ru. Khi etanol
c sn xut nh l ung hn hp th n l ru ng cc tinh khit.
Dung dch etanol 70% ch yu s dng nh l cht ty u. Etanol cng c s dng trong
cc gel v sinh khng khun, ph bin nht c nng khong 62%. Etanol git cht c vi
sinh vt theo c ch bin tnh protein v ho tan lipit ca chng. Do kh nng khng khun
ca etanol nn cc ung cha trn 18% etanol c kh nng bo qun lu di (d ung
cha nh hn 18% etanol khng ngn chn c vi khun pht trin).
Etanol c th s dng trong cc sn phm chng ng lnh v im ng bng thp ca n.
Etanol c th s dng lm nguyn liu trong cng ngh ho hc, nguyn liu cho tng hp
hu c ho du.
Ngy nay, etanol c s dng rng ri pha vo xng to nhin liu sinh hc thn thin
vi mi trng. Ti Hoa K, Iowa l hng sn xut etanol cho nhin liu t vi sn
lng ln nht.
a) Tnh Cht Vt L:
Ru etylic l mt cht lng, khng mu, mi thm d chu, v cay, nh hn nc
(khi lng ring 0,7936 g/ml 15C), si 78,39"C, ho rn -114,15c, tan v hn
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trong nc. S d ru etylic tan tt trong nc v c nhit si cao hn nhiu so vi
este hay aldehit c cng s caccbon l do c s to thnh lin kt hydro gia cc phn t
vi nhau v vi nc.

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Nhit si

78.39 C

Nhit ng c

-114.15 C

p lc b mt ti 20 C

22.03 mN/m

Cp (16 - 21 C)
Nhit lng hnh thnh
Nhit lng bay hi
70C

2.415 J g-1K-1
4.64 kJ/mol
855.66 kJ/kg

80C

900.83 kJ/kg

100C
Nhit bt chy
(vi th tch khng i)

799.05 kJ/kg

dn nhit ti 20 C
nht ng hc

1370.82 kJ/mol
18

Wm1 -1
K
1.19 mPa.s

H s gin n th tch

1.1x10-3 K-1

Nhit chp chy

Nhit t bt chy

13 C
425 C

Gii hn chy
Di, 3.5 vol %

67 g/m3

Trn, 15 vol %

290 g/m3
736 kN/m2

p sut n

b) Tnh Cht Ha Hc:

* Tnh cht ca mt ru n chc
- Phn ng th vi kim loi kim:
2C2H5OH + 2Na 2C2H5ONa + H2
- Phn ng este ho:
C2H5OH + CH3COOH CH3COOC2H5 + H2O
- Phn ng loi nc:
Tch nc to olefin:
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C2H5OH C2H4 + H2O
Tch nc to ete:
2C2H5OH C2H5-O-C2H5 + H2O
- Phn ng oxy ho:
Phn ng oxy ho c th xy ra theo cc mc khc nhau: Oxy ho khng hon
ton to ra aldehit, axit hu c v oxy ho hon ton to thnh CO2 v H2O:
CH3-CH2-OH + CuO CH3-CHO + Cu + H2O
C th oxy ho bng oxy khng kh c xc tc s to axit hu c:
CH3-CH2-OH + O2 CH3COOH + H2O
Oxy ho hon ton:
C2H5OH + 3O2 2CO2 + 3H2O
* Tnh cht ring
Nu cho hi etanol qua xc tc hn hp, v d Cu + A1 203 380 -T 400C c
th xy ra phn ng loi nuc to butadien:
2C2H5OH CH2=CH-CH=CH2 + 2H2O + H2
* Phn ng ln men gim:
Oxy ho ru etylic c nng 10% bng oxy khng kh c mt men gim
khong 25C s to thnh gim n:
CH3-CH2-OH + O2 CH3COOH + H2O
c) Cc nguy him ca etanol:
Etanol l nhng cht d chy v d dng bt la nn cn thit phi c cc bin
php bo v an ton.
Etanol trong c th con ngi c chuyn ho thnh axetaldehit do enzym
alcohol dehydrogenas phn hu ru v sau thnh axit axetic bi enzym
axeadehit dehydrogenas phn hu axetaldehit. Aldehit ny l nguy c ca bnh
x gan, nhiu dng ung th v chng nghin. Nu nng etanol trong mu cao
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(t 0,3 + 0,4%) c th gy hn m, nu t ti 0,5% hoc cao hn c th gy t
vong.
Ngi ta cng ch ra mi lin quan t l thun gia etanol v s pht trin ca
vi khun gy ra vim phi, vim mng no v cc vim nhim h bi tit. S pht
hin ny l tri ngc vi s nhm ln ph bin cho rng ung ru c th git
cht nhiu loi vi khun gy cc bnh truyn nhim.

2. Nguyn Liu:
Mt r hay r ng l th phm ca cng ngh sn xut ng chim 35%
so vi lng ma a vo sn xut ,t l ny ph thuc vo lng ma v cng
ngh sn xut .
a) Thnh phn mt r:
Thnh phn mt ca mt r ph thuc vo ging ma t trng trt v iu
kin canh tc cng nh cng ngh sn xut ng .Bnh thng lng cht kh
trong mt r chim 8085% ,nc chim 1520% .
Trong s cc cht kh th ng chim ti 60% ,gm 3540% l saccaroza v
2025% l ng kh .S cht kh cn li gi chung l cht phi ng v gm
3032% l hp cht hu c v 810% l cht v c.
Hp cht hu c gm cc cht cha nit ,cacbon , oxy v hydro ,cht hu c
khng cha nit gm c : pectin ,cht nhy furfurol v oxymetyl furol , axit v.v
Ngoi ra cn cha cc cht kh nhng khng ln men c nh caramen ,cht
mu v.vHp cht hu c cha nit phn ln l dng amin nh glutamic ,lxin
,alanin v.vLng nit trong r ng ma ch khong 0,51% , t hn so vi r
trong c ci(1,22,2) .Do cha t nit nn khi ln men r ng chng ta phi b
xung lng nit t ure hoc amoni sunfat.
b) PH ca mt r:
Bnh thng pH ca mt r t 6,87,2; r mi sn xut ra c th c
pH=7,28,9 ; kim ca r khong 0,52o (1o kim tng ng 1ml dung dich
H2SO4 1N trung ho ht 100 g r ) . kim gy ra bi cc mui canxi ca axit
cacbonic v cc axit hu c khc.
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c) Vi sinh vt trong mt r:
Mt r nhn c t sn xut lun cha mt lng vi sinh vt trong nguy
him nht l vi khun lactic v axit axetic .Mc nhim khun c xc nh
bng s tng chua khi mt r t ln men ,mc tng chua (khi t ln men
sau 24 gi) trong phm vi 0,20,3o c xem l bnh thng .
Thc t trong 1 gram mt r cha ti 100000 vi sinh vt khng nha bo v
15000 c kh nng to bo t . mt r b nhim nng con s vi sinh vt c th t
500000 v 50000 .Tuy nhin , i vi r ng c nng trn 70% hu ht cc vi
sinh vt trong mt r u chu nm yn ,nhng pha long chng bt u hot ng
tr li v lm gim lng ng nhanh ,dn n tn tht .Trong qu trnh sn xut
cn c bin php x l ph hp nhm dit bt v hn ch hot ng ca tp khun .

3. Cc Phng Php Sn Xut:

1. Tng Hp:
a. Tng hp Ethanol bng phng php hydrat ha gin tip Ethylene:
Phng php ny cn c c tn gi khc l phng php este ha hoc s thy
phn, bao gm cc bc chnh sau:
_ S to thnh ethyl sulfate v diethyl sulfate do s hp th ca ethylene trong
dung dch axit sulfuric c:
CH2=CH2 + H2SO4 C2H5O-SO3H
2CH2=CH2 + H2SO4 (C2H5O)2SO2
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_ Thy phn cc este sulfuric to thnh ethanol:
C2H5O-SO3H/(C2H5O)2SO2 + H2O C2H5OH/(C2H5)2O + H2SO4
Sn phm ph to thnh l diethyl ete.
_ C c li sn phm ph axit sulfuric.
Theo nguyn l vn hnh ca thit b trong nh my thc hin cc phn ng ny,
dng Ethylene long c a n thp hp th theo dng i lu c cha 94 n
98% axit sulfuric 80oC v p sut 1.3-1.5 . 106 Pa. Phn ng ta nhit, yu cu
cn c s kim sot nhit cht ch bng cc thit b lm lnh bn ngoi v 1 bn
iu khin th tch axi trong thp bn ngoi. Cc thnh phn sau hp th, cc este
sulfuric v diethyl ete, sau c thy phn bng nc, lng nc ny cng
lm gim i nng axit sulfuric trong thit b xung khong 50%. Cc sn phm
thy phn c a ti thp thu hi axit long. Dng hi trn nh thp c a
sang thp ra, c th bng nc hoc bng NaOH. Sau dng ra c em i
tinh ch loi b diethyl ete. Phn axit sulfuric long c c c trong thit b bay
hi p sut chn khng.

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S cng ngh sn xut ru etylic bng phng php hydrat ha gin tip
etylen [8]
b. Tng hp Ethanol bng phng php hyrat ha trc tip Ethylene:
Phn ng ny l phn ng c mt xc tc, v thc hin trong mi trng nc:
CH2=CH2 + H2O CH3-CH2OH

H298o = -45 kJ mol

Xc tc c s dng rng ri nht l axit photphoric mang trn silic oxit. Do phn
ng l phn ng gim th tch, ta nhit mnh, nn thit b phn ng lm vic ti
nhit thp v p sut chn khng. Nhng trong thc t th nhit v p sut
ny ri vo khong 300oC v 7 . 106 Pa, lc , phn ng mi xy ra. Nhit ny
s gy nh hng n cn bng ca phn ng, cho nn, chuyn ha ca
Ethylene ch ri vo khong 4%. V iu ny, nn 1 lng ln ethylene s c
tun hon li thit b phn ng. p sut cao cng l iu kin tost cho phn ng
polyme ha ethylene xy ra. p sut ca hi nc khng c qu cao, c th gy
ra mt hot tnh ca xc tc axit. iu kin ca phn ng ny l t l gia
H2O/C2H4 ri vo khong 0.6/1 v thi gian lu khng c qu di (khong 1/50
h).
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S cng ngh sn xut ru etylic bng phng php hydrat ha trc tip
etylen [8]
2. Ln Men:

Etanol s dng lm ung cha cn cng nh phn ln etanol s dng

lm nhin liu c sn xut bng phng php ln men, khi mt s loi men ru
nht nh (quan trng nht l men Saccharomyces cerevisiae) chuyn ho ng
trong iu kin khng c oxy (gi l ym kh), chng sn xut ra etanol v cacbon
dioxit CO2. Phn ng tng qut nh sau:
C6Hl2O11 2CH3-CH2-OH + 2CO2
Qu trnh nui cy men ru theo cc iu kin sn xut ru c gi l
ru. Men ru c th pht trin trong iu kin nng ru khong 20%.
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Nng ru trong sn phm cui tng ln nh chng ct. sn xut etanol t
cc nguyn liu cha tinh bt nh ht ng cc th u tin tinh bt phi chuyn
thnh ng, sau mi ln men thnh ru. Trong vic men bia, theo truyn
thng n c to ra bng cch cho ht ny mm hay cn gi l mch nha. Trong
qu trnh ny mm, ht to ra cc enzym c chc nng ph v tinh bt to ra
ng. sn xut etanol lm nhin liu, qu trnh thu phn ny ca tinh bt
thnh glucoza c thc hin nhanh chng hn bng cch x l ht vi axit
sunfuric long.
V tim nng, glucz ln men thnh etanol c th thu c t xenlulz.
Vic thc hin cng ngh ny c th gip chuyn ho mt lot cc ph thi v ph
phm nng nghip cha nhiu xenlulz, chng hn nh li ng, rm r hay mn
ca thnh cc ngun nng lng ti sinh. Hng logen Canada a vo vn
hnh x nghip sn xut etanol trn c s xenlulz vo nm 2004.
Phn ng thu phn xenlulz gm cc bc sau:
Bc 1: Thu phn xenlulz thnh mantz di tc dng ca men
amylaza:
(C6H10O5)n + nH20 nC12H22O11
Bc 2: Thu phn tip mantz thnh glucz hoc fructz di tc dng
ca men mantaza:

C12H22O11 + H2O 2C6H12O6

Bc 3: Ln men ru c xc tc l men zima:

C6Hl2O6 2C2H5OH + 2CO2

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S Ln Men Lin Tc [5]

S gm hai thng gy men cp I (1) c dung tch bng 25-30% so vi thng

gy men cp II (2). Thng cp II c dung tch bng 30-60% thng ln men chnh
(3). Cc thng ln men tip theo 8-10 thng (4). Thng gy ging cp I c t
pha trn thng cp II d t chy. V tr thng cp II t cao hn hai thng ln
men chnh (3). Phn tr ca hai thng ny phi cao hn 1m so vi phn tr cc
thng cn li, v rng ln men chnh xy ra mnh, lng bt s nhiu.
ng dn dung dch ra t cc thng ln men chnh chy sang cc thng (4) t
cch mp trn phn tr 1m, cn ng dn dch ra t cc thng (4) tip theo ch cch
mp trn phn tr 0.1m. Vi hai thng cui cng, khong cch ny l 0.5m. Cch
b tr ny gip cho dch chy nhanh hn. ng knh ng chy truyn ph thuc
vo cng sut nh my. Vi cng sut 10000 lt/ngy cn ng knh ng l
200mm.

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s khi quy trnh sn xut cn

etylic

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II. CHNG CT V TINH CH CN ETYLIC

Chng ct ru l qu trnh tch C 2H5OH v tp cht d bay hi khi dm
chn, kt qu ta nhn c l ru th hoc cn th. Tinh ch hay tinh luyn l qu
trnh tch cc tp cht khi cn th v nng cao nng cn. Sn phm thu c
gi l cn tinh ch hay cn thc phm c nng 95,596,5%V .Cn thc phm
cha rt t tp cht.
1. L thuyt v l thuyt tinh ch cn
Cn th nhn c sau khi chng ct cn cha rt nhiu tp cht (trn 50
cht), c cu to v tnh cht khc nhau. Trong gm cc nhm cht nh:
aldehyt, este, alcol cao phn t v axit hu c, hm lng chung ca tp cht
khng vt qu 0,5% so vi khi lng cn etylic.
Theo s liu ca Vin nghin cu Ucrain, hm lng tp cht trong cn th
nhn c t mt r dao ng trong gii hn kh ln. Axit t 20200 mg/l, este t
150550 mg/l, aldehyt t 90900 mg/l, alcol cao phn t t 0,20,5% khi lng
v hp cht cha nit tnh theo amoniac chim t 818 mg/l.
Bng phn tch sc k kh ngi ta nhn thy rng trong thnh phn ca axit
gm c : axit axetic 7585%, axit butylic 510% v cn li 1015 l cc axit khc.
Trong s cc aldehyt th aldehyt axetic chim 7590%, cn li 510% aldehyt
propylic, 28% butyric. Trong s cc este th 7585% l este ca axit axetic,
510% gm este ca axit propylic, valeric v.vHm lng cc alcol cao phn t
cng rt khc nhau nhng cha ch yu l alcol amylic v alcol izobitylic.
Mt s tp cht mang tnh c th ca tng nguyn liu nh cn nhn t mt
r cha t furfurol nhng li cha nhiu cc tp cht gy mi ma nht l cn nhn
c t mt r mi sn xut. Theo quan im tinh ch cn, ngi ta chia tp cht
thnh ba loi chnh chnh : tp cht u, tp cht trung gian v tp cht cui. Chia
nh vy ch l tng i v qui c v tnh cht ca tp cht c th thay di tu
theo nng cn trong thp.
Tp cht u gm cc cht d bay hi hn alcol etylic nng bt k,
ngha l h s bay hi ln hn h s bay hi ca ru. Cc cht c nhit si
thp hn nhit si ca alcol etylic gm: aldehyt axetic, axetat etyl, axetat metyl,
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formiat etyl, aldehyt butyric.
Tp cht cui bao gm cc alcol cao phn t nh acol amylic, alcol
izoamylic, izobutylic, propylic,izopropylic. khu vc nng cao ca alcol
etylic, cc tp cht cui c bay hi nh hn so vi bay hi ca alcol etylic.
khu vc nng etylic thp, bay hi ca tp cht cui c th ln hn so vi
alcol etylic. Tp cht cui in hnh nht l axit axetic, v rng bay hi ca n
km hn alcol etylic tt c mi nng .
Tp cht trung gian c hai tnh cht, va c th l tp cht u va c th
l tp cht cui. nng cao ca alcol etylic n l tp cht cui, nng alcol
thp chng c th l tp cht u. l cc cht izobutyrat etyl, izovalerat etyl,
izovalerat, izoamyl v axetat izoamyl.
bay hi ca cc tp cht ph thuc vo nng alcol etylic trong dung
dch, nu hm lng tp cht khng ln th c th xem nh bay hi ca tng
cht ring bit khng ph thuc vo hm lng ca cc tp cht khc trong dung
dch.
Thc nghim cho bit rng khi tng nng alcol etylic th h s bay hi
ca tt c cc tp cht u gim v trong khong nng alcol nh hn 55%V, h
s bay hi ca tt c cc tp cht u ln hn 1, trong c mt s tp cht lun
c h s bay hi ln hn 1 nng bt k. l nhng tp cht in hnh thuc
tp cht u nh: aldehyt axetic, axetat etyl, axetat metyl.

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ng cn bng pha hn hp ru etylic-nc [2]
Hnh trn cho bit ng cn bng pha hn hp etylic-nc ti p sut kh quyn,
trong , x l nng phn mol ca ru etylic trong pha lng, cn y l trong pha
hi. Biu cng c lp cho nng phn trm mol v cho php phn tch h
thng thp chng ct thng qua cc k thut ha. V d, ng thng gc 45o
(tp hp cc im ti , nng pha hi v nng pha lng l cn bng) c th
c dng xc nh cc vng m cc cu t trong hn hp c th c tch ra
hoc khng th tch c. im giao gia ng cn bng pha v ng thng
gc 45o gi l im ng ph. Cn nhin liu gn nh phi kh hon ton, m cc
h thng chng ct n gin khng th to ra cn 100% c, do s hnh thnh
ca im ng ph. Qu trnh chng ct tiu chun ch c th to ra cn etylic 96%
v do , cc qu trnh cn c ci tin loi b nuwosc hon ton khi cn
etylic cho vic ha trn trong xng thng phm.

2. Cc s chng ct v tinh ch:

Thp chng ct bao gm 1 on chng v 1 on luyn. Hnh v di l
mt h thng n gin 1 thp chng. Thp chng c cc a m ti c
s tip xc pha gia lng lng t trn xung v lng hi t di ln
to iu kin tt cho qu trnh chng ct.

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Hnh nh mt thp chng n gin [2]

a) Chng luyn gin on:
Chng ct ru:
Trong chng gin on dm chn c bm vo thng chng ct 1, sau m
hi dun cho ti si. Hi ru bay ln theo chiu cao thp 2 c nng cao nng
ra khi thp vo thit b ngng t v lm lnh 3 ri vo thng cha.
Chng gin on c u im l n gin, d thao tc nhng bc l nhiu
nhc im. Do thi gian ct phi mt 68 gi nn thng cha ln, tn vt liu ch
to m nng sut li thp. Mt khc dm chn a vo khng c dun nng bng
nhit ngng t ca cn th nn tn hi. Nng cn khng n nh v gim dn
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theo gian, lc u c th t 7580% V cui ch cn 56% V, tn tht ru theo b
nhiu gp 3 ln so vi chng lin tc.
Chng lin tc cho php khc phc cc nhc im k trn v c bo m
hiu qu kinh t cao, hin nay nc tin tin khng tn ti s chng gin
on. nc ta nhiu x nghip nh v cc xng t nhn cng ang b dn kiu
chng lc hu v km hiu qu ny.

S chng ct ru [5]
Tinh ch cn:
Cn th nhn c sau khi chung ct cn cha nhiu tp cht, do cn tinh
ch nhm tch cc tp cht nng cao cht lng v m bo an ton cho ngi
tiu dng.
i vi cn th nhn c sau chng ct, nu em tinh ch gin on th cn
x l bng ho cht v da trn phn ng sau:
RCOOC2H5 + NaOH RCOONa + C2H5OH
Ngoi cc axit t do trong cn th cng phn ng vi NaOH to thnh cc
mui khng bay hi v nc:
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R1COOH + NaOH R1COONa + H2O
gim bt aldehyt v cc cht khng no khc ngi ta dng KMnO 4 lm
cht oxy ho ,Phn ng ny c th xy ra trong mi trng kim yu c pH=89
trong iu kin hai phn t KMnO4 s gii phng ra ba nguyn t oxy sau
oxy s tham gia vo phn ng oxy ho:
2KMnO4 + 3CH3CHO + NaOH 2CH3COOK + CH3COONa + 2MnO2 + 2H2O
Lng NaOH v KMnO4 ch nn v nu tha th d dn n alcol etylic
b oxy ho thnh axit v gy tn tht .Mun trnh hin xy ra ta cn phi xc
nh lng tp cht v tnh ton c th lng ho cht a vo.
S ch gin on tuy cho php mhn c cn c cht lng nhng
hiu sut thu hi thp, tn hi v cng sc lao ng do phi ct li v do cng
c t s dng hin nay. khc phc cc nhc im ca chng ct v tinh
luyn gin on ta c th s dng s bn lin tc.

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S tinh ch gin on [5]

1. Thng ct; 2 Thn thp; 3 Bnh ngng t hi lu
4 bnh ngng t lm lnh
I cn u; II Cn 2a+2b; III Sn phm chnh; IV fusel

b) S chng luyn bn lin tc:

Ln men xong dm chn c bm vo thng m v lm vic gin on nn
phi b tr hai thng song song lm vic so le n nh phn no nng cn cho
trc khi vo thp tinh. Cn ct th c un trc tip bng hi nc c p sut
0,81 kg/cm2. Hi ru bay ln ngng t ri vo thng cha ,tip lin tc vo
thng tinh ch . thng tinh ch cng c un bng hi trc tip t a tip liu,
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xung n dy nng cn gim xung dn dn n y thp cn 0,0150,03%
ri ra ngoi. Hi ru bay ln c tng nng dn, phm ln ngng t ri hi
lu tr li thp. Mt phn nh cha kp ngng t cn cha nhiu tp cht u c
a ngng t tip v ly ra dng cn. Cn u ch dng pha vecni, lm cn
t, st trng v em di x l v ct li
Cn sn phm ly ra dng lng cch a hi lu (t trn xung) khong 3
n 6 a c lm lnh, ri vo thng cha v vo kho. Cn ly ra y tuy c
nng thp hn (0,30,5%) so vi hi nh nhng cha t este v aldehyt.
c) Chng luyn lin tc:
Chng luyn lin tc c th thc hin theo nhiu s khc nhau: 2 thp ,3
thp hoc 4 thp. Trn s ny ngi ta li chia h thng chng luyn mt dng
(gin tip) hoc hai dng (va gin tip va trc tip).
S hai thp gin tip 1 dng:

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S chng ct ru 2 thp gin on [5]

1. Thng cao vi; 2. Bnh hm dm; 3.Bnh tch CO2 v kh khng
ngng; 4. Thp ct th; 5.Bnh chng pht dm; 6.Bnh ngng t cn;
7. Bnh lm lnh rut g; 8. thp tinh ch; 9.Bnh ngng t hi lu;
10. Bnh lm lnh cn sn phm; 11 Bnh ngng v lm lnh du
fusel.

Dm chn c bm ln thng cao v 1 sau i vo bnh hm dm 2. y

dm chn c hm nng ti 7080oC bng n nhit ho hi ca cn th,sau qu
trnh tch CO2 3 ri vo thp 4.Hi cn bay ln ton b ngng t 2, phn cha
ngng t tip tc sang ngng 6. Ton b cn th ngng t 2,6 v 7 i vo thp
tinh ch 8 a th 1618 tnh t di ln, thp tinh ch cng c cp nhit bng
hi nc c p sut p=0,21 kg/cm2 .Hi ru bay ln c nng cao dn nng
ra khi ngoi thp i vo 9. Ti y ta iu chnh lng nc lm lnh ly cn
ra 7 khong 35% so vi ton b lng cn vo h thng thp. S ngng 9
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c hi lu tr li thp.
Cn thnh phm ly ra dng lng cch a hi lu n 6 a v on lm
lnh 10. Nhit y ca hai thp lun m bo 103105oC, nhit nh thp
4 ph thucc nng cn trong dm v thng vo khong 9397oC, nhit thp
tinh 8 vo khong 78,378,5oC , nhit thn nh thp v tr cch a tip liu
v pha trn 34 a khng ch 8283oC. Du fursel ly ra dng hi t a th
611 (tnh t di ln) c ngng t v lm lonh 11 sau i vo thit b phn
ly du hoc cho vo dm chn ct li ,loi ra y thp th.
H thng chng luyn hai thp tuy c tin tin hn so vi chng luyn gin
on v bn lin tc nhng cht lng cn vn cha cao, mun thu nhn c cn
tt th phi ly tng lng cn u.
H thng ba thp lm vic gin tip:
H thng lm vic ba thp cho php khc phc c nhc im ca s
hai thp ni trn, h thng cho php nhn c 7080% cn loi I theo TCVN-71,
3020% cn loi II v 35% cn u.
S c tin hnh nh sau : dm chn dc bm ln thng cao v 1,sau
t chy vo bnh hm dm 2. y dm chn c hm nng bng hi ru ngng
t n nhit 7080oC ri chy qua bnh tch CO2 s 3 ri vo thp 4. Kh CO2
v hi ru bay ln c ngng t 6 v qua 7 ri ra ngoi. Thp th c un
bng hi trc tip, hi ru i t di ln ,dm chy t trn xung nh qu
trnh chuyn khi din ra , sau hi ru ra khi thp v c ngng t ti 2 v 6
ri qua 7 ra ngoi. Chy xung ti y nng ru trong dm cn khong
0,0150,030% V c thi ra ngoi gi l b ru. Mun kim tra ru st trong
b ta phi ngng t dng hi cn bng vi pha lng, Hi ngng t c nng
0,40,6% l t yu cu v nhit y 103105oC.
Phn ln ru th (9095) lin tc i vo thp aldehyt s 8, thp ny cng
dng hi trc tip , hi ru bay ln c ngng t v hi lu n 95%, ch iu
chnh lng nc lnh v ly khong 35% gi l cn u. Mt phn ru th
(510%) 6 hi lu vo nh thp aldehyt v cha nhiu tp cht.
Sau khi tch bt tp cht, ru th t y thp aldehyt s 8 lin tc i vo
thp tinh 11 vi nng 3545% V. Thp tinh ch 11 cng c cp nhit bng
hi trc tip (c th gin tip) , hi bay ln c nng dn nng sau ngng
t 12 ri hi lu li thp..Nhit y thp th v thp tinh khng ch tng t
nh s hai thp. Nhit y thp aldehyt duy tr 8085oC, nhit dnh duy
tr nht 7879oC.
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S trn c gi l gin tip mt dng v sn phm i vo cc thp ch c
mt dng cht lng duy nht. Cn gi l gin tip v bn thn dng cht lng
khng cha hi n nhit bay hi.
S trn c u im l d thao tc, cht lng cn tt v n nh, nhng tn
hi. Cn s va gin tip va trc tip hai dng c u dim l tit kim nng
lng hi nhng i hi t ng ho tt v chnh xc, nu khng c th hi y
thp tinh 11 s y ngc ln nh thp 4 lm cho mt n nh v cht lng cn
km ng u.

S chng ct ru 3 thp lm vic gin on [5]

1.Thng cha gim; 2.Bnh hm gim; 3.Bnh tch CO2; 4.Thp th; 5.Bnh
chng pht gim; 6.Bnh ngng t cn th; 7.Bnh lm lnh rut g; 8.Thp
aldehyt; 9,10. Bnh ngng t; 11.Thp tinh ch; 12. Bnh ngng t hi lu;
13. Bnh lm lnh sn phm
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Nh vy, tng hiu qu chng ct, vi mc ch thu c cn etanol c nng

cao, nn la chn h thng lm vic 3 thp gin tip. V s cho kh nng chng su
hn, sn phm etanol cui cng c nng gn xp x 96%.
Thng thng, etanol sn xut ra c nng khong 95-96% l ph bin nht v
i vi h hp etanol-nc, im ng ph ca hn hp ny cho nng etanol l
96% v nc l 4%. Khng th to ra etanol tinh khit hn 96% bng phng php
chng thng thng. M yu cu ca etanol sinh hc pha vo xng, cn c nng
trn 99%, tc l cn tuyt i. Do phi dng cc phng php lm khan cn
ring bit, to ra sn phm nh mong mun.
3. Cc Phng Php Thu Cn Etylic Khan:
Cn tuyt i hay cn gi l cn khan hoc cn khng nc c dng nhiu
trong tng hp hu c, thuc sng khng khi, nhng c trng nht l dng
pha vo xng thng phm lm nhin liu sch cho cc phng tin. Yu cu v
cn tuy i phi t: nng alcol etylic ln hn hoc bng 99.8%, hm lng
aldehyt nh hn hoc bng 5mg/l, axit hu c nh hn hoc bng 10 mg/l.
Ethanol l cht hon ton c th trn c vo xng, nhng ch 1 lng nh nc
c th nhanh chng dn n hin tng phn pha trong xng (ethanol s hp th
nc trong hn hp trong ng c), do c th dn n hng ng c. V vy,
ethanol pha trn trong xng thng phm, cn phi c tch nc hon ton.
Cc phng php thu hi ethanol tuyt i:
a) Chng ng Ph:
Chng ct n gin khng th phn tch c hon ton ethanol ra khi hn hp
ethanol nc bi ro cn v im ng ph gia ru v nc. Chng ng ph da
trn c s hnh thnh hn hp ng ph gia ethanol vi mt dung mi phn cc
khc.
Nc c tch ra khi hn hp ng ph ethanol-nc di dng mt hn hp
n ph 3 cu t bng cch cho thm 1 dng dung mi vo dng ru nguyn liu,
nh benzen hoc heptan, xyclohexan. Dng ethanol khan thu c di y thy
chng v sau c i qua thit b lm lnh v dn n cc thng cha. Hn hp
ng ph 3 cu t i ra trn nh thp, c ngng t sau c tch ra lm 2
pha, 1 pha hu c v 1 pha ngm nc. Nh vy dng sn phm ethanol thu c
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c cn ln n 99.98% (trong c cha <200mg/kg nc v 20 mg/kg cc tp
cht khc).
b) Hp ph sng phn t:
C nhiu bin php thu c ethanol khan, nhng vic s dng bin php hp
ph ry phn t l ph bin v thnh cng hn c. Sieving bao gm cc tnh cht
ca cc loi zeolit tng hp c mao qun va nh (0.3nm) cho php cc phn
t nc (0.28nm) thm qua, m khng cho cc phn t ethanol i qua (0.44nm).
Mt ry phn t c th hp ph c lng nc bng 22% khi lng ca chng.
c) Chng ct chn khng:
Dng nguyn liu ethanol t qu trnh chng ct sau ln men, c chuyn n
thp chng ct ti p sut chn khng di 10 kPa. y l phng php truyn
truyn thng thu cn tuyt i.
Trong cc phng php trn, th phng php chng ng ph thng c s
dng cho cc nh my ln. Nhng hin nay, phng php ny khng cn c s
dng bi, benzen l mt tc nhn c hi, gy nh hng xu n sc khe con
ngi v mi trng.
Hin nay, trn th gii, ngi s dng phng php hp ph sng phn t (s
dng cht hp ph l zeolit 3A) thu c sn phm ethanol tuyt i pha vo
xng thng phm, nng cao tr s octan v thn thin hn vi mi trng.
Zeolit 3A c tng hp bng cch thay th cc ion Na+ bng cc ion K+, v cc
ion K+ c kch thc ln hn cc ion Na+, do kch thc cc mao qun cng s
c rng ln n 3.2 Angstroms.
Zeolit 3A c cc tnh cht ca zeolit tng hp vi kch thc cc mao qun l 3A
hay 0.3 nm. Trong khi , kch thc ca cc phn t nc l 0.28nm v cc phn
t ru etanol l 0.44nm. Cho nn, khi hn hp ru v nc c cho qua lp
cht hp ph zeolit 3A, cc phn t nc s chui qua cc mao qun v c zeolit
gi li ti . Zeolit c th hp ph 1 lng nc tng ng vi 22% trng
lng ca chng. Do , cn sau khi ra khi thp hp ph, s t c tinh
khit nh mong mun, trn 99%.
d) Ti Sinh Cht Hp Ph:
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C nhiu phng php khc nhau ti sinh xc tc qua s dng, nh:
_ Nh hp ph bng 1 dng kh tr p sut thp.
_ Nh hp ph ti nhit cao.
_ Nh hp ph bng cch thay i lc ht gia cht b hp ph v cht hp ph vi
s c mt ca tc nhn ha hc khc.
_ Nh hp ph bng cch s dng mt dung mi khc c kh nng ha tan chn
lc li cht b hp ph.
_ Loi b cht b hp ph bng phng php phn hy nhit hoc phn hy ha
sinh
Nhng ph bin nht l dng dng kh tr, nng thi vo trong thp loi b
nc. Nh vy, s ln s dng zeolit s khng b hn ch, tit kim c kinh ph
u t.
Do , t cc yu t trn, ngoi s chng ct ru 3 thp, chng ta cn thm 1
thp hp ph s dng sng phn t thu c cn tuyt i vi nng trn
99%.

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III. TNH TON CN BNG VT CHT, CN BNG

NHIT LNG
(M PHNG CNG NGH BNG Aspen Hysys 7.2)
1. M u:

S M Phng Cng Ngh Sn Xut Cn Nhin Liu

S gm c 1 thp phn ng, 1 thp hp th, 1 thp chng, 1 thp hp th c
hi lu nh thp v 1 thit b component splitter m phng cho thp hp ph
bng cht hp ph sng phn t trong thc t.
Trong thit b phn ng, xy ra phn ng ln men mt r ng to thnh CO2
v cn etylic. Sau , sn phm lng ra khi thit b phn ng c cho vo
thp hp th bng dng hi nc (steam). Mc ch l li cun phn ru
etylic ra khi tp cht, hn hp ra khi nh thp ch cn li l hn hp ca
ru v nc. Dng lng ra khi thp hp th c em i x l.
Dng hi ra khi thp hp th c a vo thp hp th c hi lu nh thp.
y, ru etylic c thu hi trn nh thp c nng l 74%, c em i
chng tip thu hi cn etylic c nng xp x 94% (gn im ng ph). V
cui cng l thp hp ph s dng ry phn t, hp th nt 6% nc trong
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hn hp ru nc. Sn phm to thnh l cn etylic tuyt i c nng
99,99%.
2. Nhp cc cu t cho phn ng ln men:
a) La chn cc cu t:
Cc cu t cho m phng qu trnh sn xut cn sinh hc: ng saccarozo,
ng glucozo, cn etylic, nc, v CO2:

Qu trnh m phng s dng phng trnh trng thi l UNIQUAC.

b) Thit lp phng trnh phn ng:
Thit lp phn ng thy phn v phn ng ln men:
Phn ng thy phn:
C12H22O11 + H2O 2C6H12O6
chuyn ha ca phn ng thy phn l 90%.

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Phn ng ln men:
C6H12O6 2C2H5OH + 2CO2
chuyn ha ca phn ng ln men l 95%.

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Sau thit lp th t xy ra phn ng, phn ng thy phn xy ra trc, phn

ng ln men xy ra sau:

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Ri chuyn 2 phn ng vo h phng trnh trng thi chn trn v bt u

tin hnh m phng.
3. Trnh t m phng:
a) Thit b phn ng:
Khi to dng nguyn liu cho qu trnh m phng (1) vi cc thng s p sut,
nhit , nng mol cu t, v lu lng khi lng dng nh trn hnh:

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Dng nguyn liu sau c a vo thit b phn ng vi 2 phn ng nh

thit lp trn cng vi dng lng c tun hon t thit b hp th CO2, thit
b phn ng lm vic ch ng nhit:

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b) Thp hp th CO2:
Dng hi (Vapour) thot ra khi thp phn ng, ch yu l CO2 vi nng
trn 95%, cn li l nng t ca nc v etanol c a vo t di y
thp hp th. S dng dng dung mi l nc (3) i t trn nh thp xung:

Dng lng ra khi thp hp th c tun hon quay tr li thp phn ng bng
cng c Recycle.
Thng s ca thp hp th CO2 c th hin trong bng di y:

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Nng ca dng hi v dng lng ra khi thp:

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c) Thp hp th etanol:
Thng s ca thp hp th etanol

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Dng lng i ra t thit b phn ng (Liquid) ch yu l etanol v nc. c
a vo thp hp th. Thp hp th ny s dng dng hi nc i t di ln,
mc ch l li cun cu t ethanol trong dng lng Liquid ln ph trn thp
hp th, v dng lng chy xung y thp c nng ch yu l nc.

d) Thp hp th c ngng t nh v hi lu nh:

Dng hi t thp hp th etanol cho ta thy, c 12.72% nng etanol trong
hn hp. Dng hi ny s c a tip sang 1 thp hp th c ngng t v hi
lu nh thp, tch c lng etanol c trong dng hi (ovhd) t qu trnh
hp th etanol. La chn gi tr nng mol ca etanol thu hi c trn nh
thp l 74,22%. Thp hp th Refluxed Absorber:

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e) Thp chng ct:

Phn lng ngng t t nh thp hp th c a sang thp chng, nhm tinh
ch cn etylic n nng xp x 95%. Thp chng l thp loi a chp, vi
16 a, ng knh 1.5m, cc a cch nhau 0.55m. Cc thng s ca thp
chng:

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Dng sn phm ra khi thp chng:

nh thp:

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y thp:
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f) Thp hp ph: (Component Splitter)

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Sau khi ra khi thp chng, sn phm cn etylic c nng xp x 95% c
em i hp ph bng zeolit 3A thu cn tuyt i vi nng trn 99%. Thp
hp ph lm vic p sut thng, nhit khong 78oC.

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4. Tnh ton cn bng vt cht, cn bng nhit lng:
S dng cng c tnh ton ultilities tnh cn bng vt cht v nhit lng cho
c h thng:
Vo Tools, chn Ultilities, trong , chn Property Balance Ultilities. Sau
la chn Scope Objects:

Sau trong gia din, ta la chn Case (Main), chn tt c cc thp c trong
mi trng m phng, v accept list

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Tr v giao din Property Balance Ultilities, la chn Insert Variables v la

chn thng s cn tnh ton, y l chng ta cn tnh cn bng vt cht, ta
chn Mass Flow, v chn Insert Formula. Ri click sang Balance Result.
Kt qu nhn c l sai s 0.00 %.

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Click sang tab Energy Balance, ta s c tnh ton cn bng nhit lng ca
ton qu trnh.
Sai s l 0.00 %

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IV.

Kt Lun.

Vi tnh hnh khoa hc v x hi ang ngy cng pht trin, i sng con
ngi ang ngy cng c ci thin hn, hin i hn, v vn minh hn.
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V cng vi tnh trng ca th gii hin nay, du m ang cn kit. i hi
th gii cn c mt loi nhin liu mi va p ng c vn mi
trng, va p ng c nhu cu s dng ca ngi tiu dng.
Trn c s , cc qu trnh sn xut nhin liu cn sinh hc ra i, nhm
p ng c nhng nhu cu ca ngi tiu dng v th gii.
Nhin liu cn sinh hc ni ring v nhin liu sinh hc ni chung, p ng
y nhu cu v nng nghip,v anh ton cho mi trng, v c v khoa
hc k thut. T , gip cho x hi ngy cng pht trin, mi trng thm
sch hn v ngi nng dn c thm vic lm, tng thm thu nhp cho gia
nh.
Em xin chn thnh cm n PGS. TS. Phm Thanh Huyn gip em hon
thin n ny, v trn ht l gip em hiu r hn phn no v li ch ca
bio-ethanol trong i sng.

V.

Ti Liu Tham Kho

1. PGS. TS. Nguyn Khnh Diu Hng

Nhin Liu Sch, NXB Khoa Hc v K Thut
2. Graeme M. Walker
Bioethanol: science and technology of fuel alcohol, 1st edition, 2010
3. Ruhul Amin M.
Simulation of ethanol production by fermentation of molasses
4. John Wiley and Sons
Ullmanns Encyclopedia of Industrial Chemistry, 2014
5. PGS. TS. Nguyn nh Thng, TS. Nguyn Thanh Hng
Cng ngh sn xut v kim tra cn etylic, NXB Khoa Hc v K Thut, ti
bn ln 3, 2007
6. Prof. Motoyuki Suzuki
Adsorption Engineering, University of Tokyo
7. Helen Magnusson
Process simulation in Aspen Plus of an integrated ethanol and CHP plant
8. Alain Chauvel, Gilles Lefebvre
Petrochemical processes vol 2
Bi Quang Minh
KTHH 08-K57
MSSV: 20123299

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 n C Nhn
9. UOP
An introduction to Zeolite molecular sieves
10. Nguyn Th Minh Hin
M phng cng ngh ha hc, Nhm m phng cng ngh ha hc v du
kh i hc Bch khoa H Ni
11. PGS. TS. Phm Thanh Huyn, PGS. TS. Nguyn Hng Lin
Cng ngh tng hp hu c-ha du, NXB Khoa Hc v K Thut H Ni,
2006

Bi Quang Minh
KTHH 08-K57
MSSV: 20123299

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