TRNG H CNG NGHIP TP.

HCM
KHOA CNG NGH HA HC
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CNG HO X HI CH NGHA VIT NAM

c lp T do - Hnh phc
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NHIM V N CHUYN NGNH

H v tn sinh vin: L THNH LONG
MSSV: 11055001
Chuyn ngnh: CNG NGH HA DU
Lp: DHHD7
1.

Tn ti kha lun/ n: Kho st kh nng tng hp du bin th sinh hc

t du da
Nhim v:

Phn tch thnh phn nguyn liu, xc nh cc tnh cht ha l du da.

Tng hp du bin th sinh hc
Kho st cc yu t nh hng n qu trnh tng hp du bin th sinh hc
nh gi cht lng sn phm da trn mt s ch tiu ho l ,tnh hiu sut
phn ng
2.

Ngy giao kha lun/ n:

3.

Ngy hon thnh kha lun/ n: 29/11/2015

4.

H tn gio vin hng dn: TS. Bch Th M Hin

Tp. H Ch Minh, ngy thng nm
Gio vin hng dn

LI CM N
hon thnh ti n ny tri qua mt thi gian di nghin cu v
thc nghim. Nhn y ti xin gi li cm n chn thnh nht n nhng ngi
st cnh cng ti trong thi gian qua. Trc tin ti xin gi li cm n chn thnh
n TS. Bch Th M Hin, c trc tip hng dn, ch bo, ng vin, cung cp
cho ti mt s ti liu b ch, ng gp kin v ra hng gii quyt tch cc
ti hon thnh tt ti ny.
ng thi cng xin cm n n tp th ging vin Khoa Cng Ngh Ha Hc
trng i Hc Cng Nghip Thnh Ph H Ch Minh ging dy v cung cp
cho ti nhng kin thc b ch trong sut thi gian hc tp trng.
Xin cm n ba m v gia nh nui dng chm sc, to iu kin tt nht
ti c iu kin hc tp nh ngy hm nay, y l ch da vng chc nht l
ngun tip thm sc mnh v ngh lc cho ti c th vng bc trn con ng
m ti chn.
Mt ln na ti xin chn thnh cm n v rt trn trng nhng s gip ny,
xin chc sc khe tt c mi ngi.

Xin chn thnh cm n!

Sinh vin

L Thnh Long

NHN XT CA GIO VIN HNG DN

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Phn nh gi: (thang im 10)
thc thc hin:
Ni dung thc hin:
Hnh thc trnh by:
Tng hp kt qu:
im
bng
s:

im
bng
ch:
..........................................................................................................................

TP. H Ch Minh, ngy thng nm 20

Gio vin hng dn
(K ghi h v tn)

NHN XT CA GIO VIN PHN BIN

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TP. H Ch Minh, ngy thng nm 20

Gio vin phn bin
(K ghi h v tn)

Mc Lc
LI NI U........................................................................... 9
CHNG 1: TNG QUAN........................................................10
1.1Tng quan v du bin th......................................................10
1.1.1.Du bin th l g?........................................................................................ 10
1.1.2.Tnh cht ca du bin th...........................................................................10
1.1.3.Thnh phn ha hc ca du bin th..........................................................10
1.1.4.Phn loi du bin th..................................................................................10
1.1.5.ng dng..................................................................................................... 11
1.1.6. Trm bin p, my bin p s dng du......................................................11
1.1.6.1. in p.................................................................................................. 12
1.1.6.2. Phn loi trm bin p theo in lc.....................................................12
1.1.6.3. Cc loi trm bin p ...........................................................................12
1.1.7 Tnh hnh s dng hin nay..........................................................................13

1.2Tng quan v du bin th sinh hc(Biotrans)..........................14

1.2.1 S lc v du bin th sinh hc..................................................................15
1.2.2 Cc sn phm du bin th sinh hc nghin cu trn th gii......................15
1.2.3. Cc qu trnh chuyn ha to Biotrans........................................................17
1.2.4. Nguyn liu cho qu trnh Biotrans..............................................................19
1.2.5. Qu trnh tng hp Biotrans vi xc tc kim..............................................19
1.2.6. Cc yu t nh hng ti qu trnh Biotrans...............................................20

1.3Tng quan v du thc vt......................................................22

1.3.1Thnh phn ha hc ca du thc vt...........................................................22
1.3.2. Tnh cht l hc ca du thc vt................................................................22
1.3.3. Tnh cht ha hc ca du thc vt.............................................................23
1.3.4. Mt s thng s quan trng ca du thc vt.............................................25
1.3.5. Cc loi du thc vt thng dng hin nay.................................................26
1.4.6. Vi nt v cy da v du da.....................................................................28

CHNG 2. PHNG PHP NGHIN CU.................................32

2.1. Ha cht, thit b, dng c....................................................32
2.1.1. Ha cht...................................................................................................... 32
2.1.2. Thit b........................................................................................................ 32
2.1.3 Dng c........................................................................................................ 33

2.2. Phng php nghin cu.......................................................33

2.2.1. Nguyn liu v xc tc cho qu trnh..................................33
2.2.1.1. Methanol...............................................................................................34
2.2.1.2 Du da.................................................................................................35
2.2.1.3. Xc tc kim......................................................................................... 36
2.2.2. Cch tin hnh tng hp biotrans................................................................37
2.2.2.1. Cc bc tin hnh th nghim..............................................................37
2.2.2.2. Qu trnh tch v tinh ch sn phm ...................................................39
2.2.2.3. S quy trnh to Biotrans..................................................................40
2.2.3. Cc phng php phn tch cht lng sn phm.......................................40
2.2.3.1. Xc nh ch s acid ASTM D664...........................................................41
2.2.3.2. Xc nh nht ng hc ASTM D445.................................................41
2.2.3.3. Xc nh im chp chy cc h ASTM D92..........................................42
2.2.3.4. Xc nh t trng...................................................................................43

2.2.3.5 Xc nh im vn c...........................................................................43
2.2.3.6. Xc nh hm lng nc (theo Karl Fisher)..........................................44
2.2.3.7 Phng php sc k...............................................................................44
2.2.3.8 Xc nh in p nh thng.................................................................45

CHNG 3: KT QU V BN LUN........................................47
3.1 Xc nh tnh cht ca du da nguyn liu............................47
3.1.1 Thnh phn ha hc v khi lng nguyn t..............................................47
3.1.2. Xc nh cc tnh cht ha l ban u ca nguyn liu...............................48

3.2 Kho st cc yu t nh hng n qu trnh tng hp Biotrans

..................................................................................................48
3.2.1 Thi gian phn ng.......................................................................................48
3.2.2. T l xc tc.................................................................................................49
3.2.3. Nhit phn ng.......................................................................................51
3.2.4. T l methanol: du ....................................................................................52

3.3. nh gi cht lng sn phm .............................................53

3.3.1 Thnh phn ha hc ca sn phm v hiu sut phn ng..........................54
3.3.1.1. Thnh phn ca ha hc ca Bitrans....................................................54
........................................................................................................................... 54
3.3.1.2. Hiu sut ca phn ng tng hp.........................................................54
3.3.3. Cc tnh cht ha l ca sn phm..............................................................55

CHNG 4: KT LUN V KIN NGH......................................56

4.1 Kt lun................................................................................56
4.2 Kin ngh .............................................................................56

TI LIU THAM KHO............................................................58

PH LC .............................................................................59

DANH MC HNH NH
Hnh 1.1 Mt s trm bin p ngoi tri thng gp...............13
Hnh 1.2 Trm bin p trong nh...........................................13
Hnh 1.3 Mt s du bin th s dng hin nay......................14
Hnh 2.1 Mu du da nguyn liu.........................................36
Hnh 2.2 H thng th nghim lp t trong phng th nghim.39
Hnh 2.3 S tch pha ca sn phm sau khi phn ng.............40
Hnh 3.1 Biu nh hng ca thi gian phn ng................49
Hnh 3.2 Biu nh hng ca lng xc tc........................50
Hnh 3.3 Biu nh hng ca nhit
........................................................................................... 52
Hnh 3.4 Biu nh hng ca t l methanol: du...............53
Ph lc 1: Kt qu gii ph GC-MS.........................................62
Ph lc2. Kt qu xc nh in tch nh thng mu du da 62

DANH MC BNG BIU

Bng 1.1 Cc thng s tiu chun ASTM.................................15
Bng 1.2 Thng s ha l ca du bin th sinh hc t cy
Jatropha............................................................................... 16
Bng 1.3 chuyn ha biotrans ca mt s loi xc tc........18
Bng 1.4 Cc tnh cht vt l v ha hc ca du thc vt.......25
Bng 1.5 Thnh phn cc gc acid bo trong du da.............29
Bng 1.6 Tnh cht ha l ca du da...................................30
Bng 3.1 Thnh phn ca du da nguyn liu.......................47
Bng 3.2 Tnh cht ha l ca du nguyn liu.......................48
Bng 3.3 Kho st s nh hng ca thi gian.......................48
Bng 3.4 Mi quan h gia lng xc tc vi hiu sut...........50
Bng 3.5 Mi quan h gia nhit phn ng vi hiu sut....51
Bng 3.6 Mi quan h gia t l methanol: du vi khi lng
sn phm............................................................................. 53
Bng 3.7 Thnh phn ha hc trong biotrans.........................54
Bng 3.8 Mt s tnh cht ha l ca du sn phm................55

LI NI U
Trong nhng nm gn y, hi nhp vi nn cng nghip ha hin i
ha nc ta v cc nc trn th gii cng i hi s pht trin ca ngnh in,n
c v nh l yu t tin phong trong vic pht trin t nc.Khi ngnh in pht
trin km theo s xut hin ca cc trm in p,my bin th cng nhiu, chng
hot ng tt cn s dng ngun du bin th c pha ch t du khong gc. Tuy
nhin, ngun nhin liu khong ngy cng cn kit bi s khai thc t ca con
ngi dn n yu cu tm ngun nhin liu thay th tr nn cn thit hn bao gi
ht. Mt trong nhng ngun nhin liu thay th l nhin liu sinh hc, c tng
hp t sinh khi do hon ton c th ti to c.
ti tt nghip Kho st kh nng tng hp du bin th sinh hc t du
da m em tin hnh s gii thiu y hn v du bin th cng nh du bin
th sinh hc, cc tnh cht, thnh phn ha hc cng nh gii thiu cch bin tnh
du da c th ng dng lm du bin th thay th cho cc du bin th hin nay.
Bi bo co ny l nhm mc ch sn xut du bin th khng c hi,
khngd chy, d phn hy sinh hc v cng sn xut du bin p, c thm rng
v nng cao kh nng p dng rng ri hn trong tng lai khi m ngun du
khong ri vo tnh trng cn kit. Kt quthu c c so snh vi cc tiu chun
ASTM, IEC xc nh du sinh hcc th c dng thay th cho du my
bin p thng thng khng?

CHNG 1: TNG QUAN

1.1 Tng quan v du bin th
1.1.1. Khi nim v du bin th
Du bin th c sn xut bng cch lm sch phn on du 300-400oC p
su kh quyn. Trong mt s trng hp c th dng phn on rng c nhit si
t 280-430oC.Du bin th c pha ch t du gc ca qu trnh phn on trn,
tinh ch bng dung mi v hydro sau c kh nc v khng kh di p sut
chn khng trit tiu hi m, tng cng kh nng cch in, n cng c x l
bng nit c ch qu trnh t xi ho. Loi du ny c cha cc ph gia chng
xi ho, do n c tnh lm mt, tnh cht cch in v bn xi ho rt tt.
Du bin th hay du cch in thng thng c 3 loi:
Du silicone: l mt polymer da trn silicone, m cng bao gm
carbon, hydro nguyn t v oxy.c bit sn phm cui cng thu c
bi s trng hp ca polydimetylsiloxan (PDMS).Du silicone c li
th s n nh nhit cao, nhng mt khc hn ch khng phn hy
sinh hc ton b.Du silicone mi phi ph hp vi tiu chun IEC
60.836 v hng dn bo v trong IEC 60.944.
Du khong: c tinh th t du th ph hp vi tiu chun IEC
60.296 hoc ASTM D3487.
Du Ester tng hp: cn gi l ester ca pentaerythirinol thu c do
phn ng ester ha gia pentaerythrinol vi cc axit monocarboxylic.Du ester tng hp phi ph hp tiu chun IEC 61.099 v
mt hng dn bo qun c cng b trong IEC 61.203.
Du bin th (du cch in hay du bin p) l du c s dng trong cc
thit b in, my bin p, trong h thng truyn ti, phn phi v s dng li in.
Vi cng dng lp l trng trong cc lp si, khong cch gia dy dn vi v lm
tng bn ca cch i n. M t khc lm tng kh nng tn nhi t ca cu n dy v
loi my bin th vo mi trng. Du bin p c dng trong my ct cao p.

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Trong cc thit b ny c to nhi t h quang nhi t rt cao, du c kh nng

lm mt nhanh v d p tt h quang. Du bin p cn c dng vo u ra
ca cp, bin tr, v rt nhiu thit b i n khc.

1.1.2. Tnh cht, thnh phn ca du bin th

Du bin th l m t cht lng hu nh khng mu ho c c mu vng s m,
theo thnh phn ho hc l hn hp ca hydrocacbon. Du bin th l m t cht lng
d chy phi ht sc cn th n khi s dng cng nh trong cng nghi p ch to.
Du bin th rt nhy cm vi tp cht nc, ch cn m t lng tp cht nh cng
lm gim bn i n m t cch ng k.
bn i n ca du bin th cng gim rt nhanh nu trong du c tp cht
si. Cc si giy, vi d ht nc. Di tc ng ca i n trng cc si c nc
b keo vo v tr c cng i n trng cao v hng ca n trng vi hng ca
ng sc rt d gy phng i n trong du.
Trong qu trnh s dng du bin th d b lo ha v oxi ha to cc hp cht
phn cc nh cn du, nc.., nh hng n tnh cht ca du.
Du bin th thu c bng cch chng ct phn on v cc bin php x l
tip theo ca du th.Du bin th bao gm cc hp cht hu c c th l paraffin,
napthene, aromatic v mt s thnh phn khc nh sunfure v nitrogen.

1.1.6. Trm bin p, my bin p s dng du

Ta c th thy My bin p c dng mi ni, t my bin p dn dng
dng trong qut in n my bin p dng n p hoc dng trong cc main
board in t.v.v. Mt trong nhng ng dng ph bin l dng trong in lc: Trm
bin p in lc tng h p trong truyn ti in.
T cc loi my bin p nh (my bin p kh gii nhit bng gi, hin ti
ch to c cng sut trn 2000 KVA), n cc my bin p ln hn c cun dy
t ngp trong du (du cch in v tn nhit ra l thep xung quanh my).

1.1.6.1. in p
Ngi ta phn ra lm 4 cp in p:

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Siu Cao p: Ln Hn 220 KV

Cao p: t 35kV ti 220kV
Trung p: t 1- 35 kV
H p: Cc in p nh hn 1 KV.

1.1.6.2. Phn loi trm bin p theo in lc

Theo cch phn loi trn, ta c 2 loi trm bin p:
Trm bin p Trung gian: Nhn in p t 220 KV 35 KV bin i thnh in p
ra 35 KV 15 KV theo nhu cu s dng.
Trm bin p phn Xng hay Trm bin p phn phi: Nhn in p 35 KV 6
KV bin i thnh in p ra 0,4 KV 0,22 KV => y l trm bin p c dng
trong mng h p dn dng ta nh, thng thy l trm 0,22/0,4 KV.

1.1.6.3. Cc loi trm bin p

12

Hnh 1.1 Mt s trm bin p ngoi tri thng gp

Hnh 1.2 Trm bin p trong nh

1.1.7 Tnh hnh s dng hin nay

Ngy nay my bin p thng thng s dng 3 loi du c bn l: du khong,
du silicone, du tng hp ester.Vic s dng nhiu loi chng minh bng vic cc
cng ty ang hng ti nhiu sn phm thn thin vi mi trng, gim s ph
thuc vo nguyn liu ha thch.Vic s dng cc ester c bit l cc ester t
nhin s dng trong sn phm ca h.
Mt s loi du bin th c s dng hin nay l: PLC supertrans
Petrolimex, NyNas Thy in, Shell Diaba BX.vvv

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Hnh 1.3 Mt s du bin th s dng hin nay

Hn mt th k nay cc sn phm du cch in c s dng t qu trnh
tinh ch du th c sn do cht lng tt v chi ph thp.Du khong c s dng
nhiu nht trong cc ngnh cng nghip my bin p v hin ti ch thng ch s
dng cho cc my bin p in phi ph hp vi IEC 60.296 hoc ASTM D3487.
Nhng nm 70 c loi khc c s dng trong my bin p: du silicone v
ester tng hp thay th du c askarels (PCB) do c c tnh.Nhng c th
chnh ca nhng loi du mi l kh nng chng chy cao.Cho n nay vic s
dng chng cn l hn ch cho gi thnh t hn 3-8 ln so vi du khong.
Ngy nay cc cng ty nghin cu ang pht trin cc sn phm du cch in
t cc loi du thc vt thu c cc ester t nhin.Nhng loi du t nhin
c tng hp t cc sinh vt sng v c bit t u nnh, hng dng, ht ci
duvv.C th, ester t nhin c to ra t mt phn ng ester ha gia ru v
axit beo.Cc qu trnh khc cho phep sn phm cui cng l cc mono-ester sau
phn ng transester hoc hn hp mono v tri-ester.Ngy nay vic s dng du thc
vt c s dng rng ri v thch thc cho nhng nm tip theo l m rng v s
dng cho my bin p.Tiu chun hin nay cho du bin th sinh hc l ASTM
D6871.

1.2 Tng quan v du bin th sinh hc(Biotrans)

1.2.1 S lc v du bin th sinh hc
Du bin th sinh hc hay cn gi l du cch in l cc mono alky ester
(ester t nhin) c iu ch bng qu trnh chuyn i ester (transester) gia ru
v cc axit beo.Sau c trit tiu hi m c th s dng trong cc my bin
p vi chc nng cch in v lm mt.
Du bin th sinh hc c cc tnh cht ha l s dng thay th du khong
thng thng lm du bin th hin nay phi ph hp tiu chun ASTM D6871.Cc
ch tiu c th hin di bng 1.1 sau:

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Bng 1.1 Cc thng s tiu chun ASTM

ASTM
Mineral oil
Property
Method
ASTM D3847
Dielectric strength (kV)
D1816
35
o
Disipation(%) 25 C
D924
0.05
Water content
D1533
35
Acid number(mgKOH/g)
D974
0.03
Color
D1500
0.5
Visual examination
D1524
Clear & bright
Relative density
D1298
0.91
o
Flash point ( C)
D92
145
o
Fire point ( C)
D92
o
Viscosity(cSt) 40 C
D445
12
o
Pour point ( C)
D97
-40

Natural Ester
ASTM D6871
35
0.20
200
0.6
1.0
Clear & bright
0.96
275
300
50
-10

1.2.2 Cc sn phm du bin th sinh hc nghin cu trn th gii

Indonesia du bin th sinh hc c nghin cu t cc loi du thc vt
nh du m, du thu du, du da,vvv.Th nghim c tin hnh l du thc
vt phn ng vi methanol qu trnh transester 60 oC v p sut kh quyn vi
NaOH lm xc tc.Kt thc qu trnh transester sn phm c a vo phu chit
phn tch.Phn lp nm trn l cc methyl ester c tinh ch bng chng ct
thu c metyl ester tinh khit. du tr nn tt hn cho my bin p ngi ta cho
thm cc cht ph gia chng oxy ha BHT( butylated hydroxy toluene).
Malaysia ,du bin p Biobased c sn sut t du ht Jatropha.Du c
chit sut t ht bng Soxhlet.Du thu c t ht cy Jatropha c kh nha
bng nc m v ht m b mt bng MgSO4.Cc c tnh ha l ca du thu c
nh sau:
Bng 1.2 Thng s ha l ca du bin th sinh hc t cy Jatropha
Tnh cht
Gi tr

15

Ch s x phng ha

155 mgKOH/g du

Ch s peroxide

7,2

Ch s iod

51,27/100g du

Acid beo t do

0.0718 mgKOH/g du

 nht

8.2 cSt

im si

124 oC

Trng lng ring

0.8480

im chp chy

150 oC

im vn c

14 oC

pH

5.2

in tch nh thng

22kV

im ng c

4oC

T trng 27oC

0.725 g/cm3

Cc thng s trn ca du tinh ch c xem l tng ng vi tiu chun

ASTM D, do du Jatropha c th s dng v tr cho du bin p thng thng
v n d dng phn hy sinh hc v an ton cho mi trng do hm lng acid thp.
M khong thp nin 90. Mt v tai nn ca mt xe ch du bin p b lt
thi im du c cha PCB v ngi ta phi chi ph rt nhiu tin lm sch
hin trng.Ngi ta bt u cho ra khi nim BioTrans thay th du bin p
khong.Cc trng i hc bt du nghin cu v pht trin thnh cng du bin th
sinh hc cho ngnh cng nghip in t du u nnh, du hng dng, du ht
civv.

1.2.3. Cc qu trnh chuyn ha to Biotrans

Biotrans c th c sn xut bi nhiu cng ngh ester ho khc nhau. V
phng din ho hc qu trnh chuyn ho ester (transesterification - hay cn gi l
qu trnh ru ho) c ngha l t mt phn t ester tc dng vi 1 ru khc cho ra
mt ester mi v mt ru mi. Qu trnh tng hp Biotrans bn cht cng l s tc
dng ca triglyxerit (1 loi ester a chc) vi phn t ru to ra cc alkyl ester
ca acid beo vi ru v ru a chc glyxerin. Ru c s dng trong qu
trnh ny thng l cc ru n chc cha khong t mt n tm nguyn t
cacbon: methanol, ethanol, propanol, buthanol.Trong methanol v ethanol
thng hay c s dng nht. Ethanol c u im l sn xut d dng t cc sn
sn phm nng nghip bng phng php ln men, khng c hi v t nhim mi

16

trng hn. Tuy nhin methanol c s dng nhiu hn do gi thnh thp hn, cho
phep tch ng thi pha glyxerin do n l ru mch ngn nht v phn cc. Phn
ng s dng ethanol s i hi lng nc trong ru v du rt thp, do lm
phc tp hn dy chuyn cng ngh. Bn cnh , metyl ester c nng lng ln
hn etyl ester, kh nng to cc vi phun thp.V vy, cho d c hi hn, nhng
methanol vn c s dng rng ri lm nguyn liu tng hp Biotrans trong rt
nhiu nh my trn th gii.
Biotrans c th tng hp t nhiu ngun nguyn liu khc nhau, nhng chung
quy li c ba nhm nguyn liu ch yu: du thc vt, du thi v m ng vt. Do
hm lng acid beo t do trong cc ngun nguyn liu khc nhau nn qu trnh
x l nguyn liu (ch yu l tch cc acid beo t do v khng ch hm lng
nc) cng khc nhau. Trong cc ngun nguyn liu trn th ngun nguyn liu du
thc vt c s dng ph bin nht v cng l ngun nguyn liu di do nht.
Phng php c bn tng hp Biotrans t du thc vt v m ng vt.
Phng php trao i ester c s dng xc tc c ba loi xc tc hay c s dng,
l xc tc acid, xc tc baz, xc tc enzym. Xc tc acid ch yu l acid
Bronted nh H2SO4, HClxc tc ng th trong pha lng. Phng php xc tc
ng th ny i hi nhiu nng lng cho qu trnh tinh ch sn phm. Cc xc tc
ny cho chuyn ho thnh ester cao, nhng phn ng ch t chuyn ho cao
khi nhit cao trn 1000C v thi gian phn ng lu hn, t nht trn 6 gi mi t
chuyn ho hon ton. V d nh s dng xc tc H2SO4 nng 1% vi t l
methanol/du u nnh lnh l 30/1 ti 650C mt 50 gi mi t chuyn ho
99%. Xc tc acid d th s dng trong qu trnh ny nh SnCl2, zeolite USY-292,
nha trao i anion A26, A27Xc tc ny c u im l qu trnh tinh ch sn
phm n gin, khng tn nhiu nng lng nhng t c s dng do c
chuyn ho thp.Xc tc baz: xc tc baz c s dng trong qu trnh chuyn
ho ester du thc vt c th l xc tc ng th trong pha lng nh : KOH, NaOH,
K2CO3, CH3ONa hay xc tc d th nh MgO, nha trao i cation Amberlyst 15,
titanium silicate TISXc tc ng th CH3ONa cho chuyn ho cao nht, thi

17

gian phn ng ngn nht, nhng yu cu khng c c s c mt ca nc v vy

khng thch hp trong qu trnh sn xut cng nghip. Cn xc tc d th c hot
tnh cao nht l MgO nhng hiu sut sn phm vn cn qu thp so vi xc tc
ng th (nh hn 10 ln so vi KOH hay NaOH).
Kt qu th nghim i vi cc loi xc tc khc nhau cng iu kin nhit
l 600C, thi gian phn ng l 8h, cng mt loi du, cng mt tc nhn ru
ho, t l mol ru/du nh nhau c a ra trong bng sau:
Bng 1.3 chuyn ha biotrans ca mt s loi xc tc
Xc tc

chuyn ho (%)

NaOH,KOH

100,0

Amberlyst A26

0,1

Amberlyst A27

0,4

Amberlyst 15

0,7

TIS

0,6

SnCl2

3,0

MgO

11,0

USY-292

0,2

T bng s liu trn nhn thy chuyn ho t cao nht khi s dng xc tc
kim, cn cc loi xc tc d th cho chuyn ho rt thp, cao nht cng ch t
11% vi xc tc MgO.

1.2.4. Nguyn liu cho qu trnh Biotrans

Nguyn liu cho qu trnh tng hp Biotrans ch yu chia ra lm 3 loi chnh:
du thc vt, m ng vt v du n thi. C ba loi nguyn liu ny u rt sn c.
Du thc vt c chit xut t rt nhiu cc loi cy nng nghip ngn v di ngy
nh du da, du lc, u nnh, ht ci, cao suTrong s c rt nhiu loi cy
trng din rng lm thc phm. M ng vt cng l mt nguyn liu di do cc
nh my ch bin gia sc, gia cm hay thy sn. Du n thi c th thu mua ti cc
nh my ch bin thc phm, nh hngHm lng acid beo t do (free fatty acid

18

 FFA) trong cc loi du ny cng rt khc nhau. Du tinh luyn (du thc vt nh
du nnh, du da) hm lng FFA < 1.5%. M ng vt t acid beo t do c
hm lng FFA < 4%. M ng vt c hm lng FFA < 20%. Du n thi c hm
lng FFA > 50%.

1.2.5. Qu trnh tng hp Biotrans vi xc tc kim

Hin nay, trn th gii Biotrans c sn xut theo phng php xc tc baz
do hiu sut chuyn ho cao v r tin. Du thc vt hoc m ng vt s c lc
loi b tp cht, sau x l loi b acid beo t do. Qu trnh loi b acid beo
t do vi mc ch trnh tiu hao xc tc trong qu trnh phn ng chnh c
tin hnh theo hai phng php sau. Tch acid beo t do bng cch ra bng dung
dch sa Na2CO3 hay dung dch kim sau ra sch sa hoc kim bng nc
nng 80-900C. Phng php ny thng tin hnh i vi cc ngun nguyn liu c
hm lng acid beo t do nh hn 4%.Phng php chuyn ho cc acid beo thnh
Biotrans bng cch s dng cc cng ngh tin x l c bit, cho acid beo trong
du thc vt kt hp vi methanol trong mi trng acid to ra Biotrans. Phng
php hai giai on ny thng tin hnh vi cc nguyn liu c hm lng acid beo
t do ln hn 4%.
Sau khi gim hm lng acid beo xung di mc cho phep (ch s acid
ca du nguyn liu 1), s tin hnh qu trnh ui nc lm khan nguyn liu.
Qu trnh ny c th thc hin bng cch chng ct chn khng tch nc nhit
thch hp hay s dng cc cht lm khan ha hc. Qu trnh ui nc nhm
trnh phn ng x phng ho xy ra trong qu trnh phn ng chnh lm mt mt
xc tc v gim cht lng sn phm. Khi , du sn sng cho qu trnh tng
hp Biotrans.
Du qua x l c trn vi ru (thng l methanol hay ethanol) v cht
xc tc baz (thng l KOH hay NaOH). Phn ng trao i ester din ra, cc phn
t du glyxerin b b gy v chuyn ho thnh ester v glyxerin.
Phng trnh tng qut ca qu trnh chuyn ha ester triglyxerit sn xut
Biotrans c vit nh sau:

19

Phn ng l thun nghch nn mun t chuyn ho cao ta phi dng d

ru, thng t l mol ru/du t 5/1 n 9/1.
C ch ca phn ng trao i ester c th hin nh sau:

Vi B l gc ru , R, R, R l cc gc acid beo. Qu trnh tin hnh cho

n khi to thnh glyxerin v cc mono ankyl ester ca cc acid beo RCOOR,
RCOOR v RCOOR.

1.2.6. Cc yu t nh hng ti qu trnh Biotrans

C rt nhiu yu t nh hng n qu trnh tng hp Biotrans. nh hng
ca nc v cc acid beo t do, nguyn liu dng tng hp Biotrans cn phi
tho mn mt s iu kin tng i kht khe, ch s acid nh hn 1 v tt c cc
nguyn liu phi khan hon ton. Nu ch s acid ln chng t hm lng acid beo
t do trong nguyn liu cn kh nhiu, v vy i hi mt lng xc tc ln hn v
trong phn ng Biotrans ho phn ng trung ho s xy ra u tin. Mt khc,
lng nc c trong nguyn liu cng thc y qu trnh x phng ho. X phng
to ra do qu trnh ny lm tng nht cho sn phm, vic tinh ch sn phm v
tch glyxerin tr nn rt kh khn.V vy, hiu sut to ester s gim ng k nu
khng tho mn hai yu cu trn ca nguyn liu. c bit mt s loi du c
hm lng acid beo t do cao nh du cao su, du n thihay cc loi m th vic
tch acid beo ban u (tinh ch nguyn liu) gi mt vai tr v cng quan trng.
nh hng ca nhit phn ng, phn ng ester ho cheo c th tin hnh cc
nhit khc nhau ph thuc vo loi du s dng. Nhit cng cao th tc to
thnh metyl ester cng cao. Tuy nhin nu nhit cao qu s khng tt v dn n
s bay hi ca methanol (nhit si 640C) lm gim nng methanol trong hn
hp phn ng, phn ng chuyn dch theo chiu ngc li lm gim hiu sut sn
phm. V vy i vi cc loi du thc vt thng thng th khong nhit tin
hnh phn ng thch hp l 55-700C, trong cng nghip hay tin hnh phn ng

20

600C. nh hng ca thi gian phn ng tc chuyn ho ester tng theo thi
gian phn ng. Freeman v cc ng nghip tin hnh ester ho cheo du lc,
du bng, du hng dng v du u nnh di iu kin t l mol methanol/du
bng 6/1, 0,5% xc tc natri metoxit, nhit phn ng 600C. Sau mt gi
chuyn ho gn nh l nh nhau bn loi du. Thi gian cng lu, chuyn ho
cng tng. Tuy nhin chuyn ho s tng chm li khi t c mc cao nht
nh do vic tip xc kh khn hn gia xc tc v nguyn liu do s cn tr ca
cc sn phm to thnh. nh hng ca tc khuy trn do cc cht phn ng tn
ti trong hai pha cch bit nn tc khuy trn cng ng mt vai tr quan trng.
C nhiu nghin cu chng minh rng vi cng mt iu kin phn ng, phn ng
trao i ester du u nnh ch t hiu sut chuyn ho 12% sau 8h khi tc
khuy 300 vng/pht, nhng khi tng tc khuy ln 600 vng/pht, chuyn
ho t ti 97% ch sau 2h. Do khi tng hp Biotrans cn khuy trn mnh m
gim thi gian phn ng m vn m bo lng sn phm mong mun. nh
hng ca lng ancol mt trong nhng yu t quan trng nht nh hng n hiu
sut ca vic chuyn ho ester l t l mol gia ancol v triglyxerit. T l ng ho
hc i vi phn ng trao i i hi 3 mol ancol v 1 mol triglyxerit to thnh 3
mol ester ca cc acid beo v mt mol glyxerin. T l mol ph thuc vo loi xc
tc c s dng, phn ng bng xc tc acid cn t l mol ln gp nhiu ln phn
ng xc tc bng baz t c cng mt chuyn ho. Theo Bradshaw v
Meuly khong t l mol methanol/du thch hp i vi qu trnh ester ho s dng
xc tc kim l 5/1 n 9/1.

1.3 Tng quan v du thc vt

1.3.1 Thnh phn ha hc ca du thc vt
Thnh phn ha hc ch yu ca du thc vt l cc triglyxerit. N l ester ca
cc acid beo khc nhau vi glycerin. Cng thc cu to ca triglyxerit ny l:
Trong R1, R2, R3 l cc gc acid beo. Cc gc acid ny thng cha t 8
n 22 nguyn t cacbon. Nu trong phn t triglyxerit ba gc acid ny ging nhau

21

ngi ta gi l triglyxerit ng nht, cn nu khc nhau ngi ta gi l triglyxerit

hn tp. Cc loi du thc vt khc nhau th c thnh phn v chng loi triglyxerit
khc nhau, nhng a phn l triglyxerit hn tp.
Mt trong nhng thnh phn khc nhau ca du thc vt l cc acid beo. Acid
beo c trong du thc vt thng c cu to mch thng, c th no v khng no.
Phn ln acid beo trong du thc vt trng thi kt hp trong triglyxerit v mt
phn nh trng thi t do. Hm lng acid beo ny cng khc nhau ty thuc vo
tng loi du. Nu thy phn cc triglyxerit, ta s thu c acid beo v glycerin.
Lng acid beo thu c c th chim 95% so vi trng lng du ban u
Glycerin cng tn ti trong du thc vt, nhng dng t do th thnh phn
ca chng rt nh. Glycerin c th thu c khi thy phn triglyxerit v l mt sn
phm ph c gi tr. Bn cnh cc thnh phn ch yu nh th th du thc vt cn
cha nhiu hp cht khc nhau nh sp, nha, cht mu, cc photphatit, tin t v
sinh t

1.3.2 . Tnh cht l hc ca du thc vt

Nhit nng chy v nhit ng c: v du thc vt c thnh phn khng
ng nht, n l hn hp ca nhiu cht khc nhau nn nhit nng chy v nhit
ng c ca chng khng c mt gi tr nhit xc nh m l mt khong
nhit . Vi mi loi du khc nhau th cc gi tri cng khc nhau. i vi cc
loi du cha nhiu acid beo hay gc acid beo no th thng c nhit nng chy
hay ng c cao hn so vi loi du cha cc gc acid beo hay acid beo khng no.
Du thc vt c thnh phn ch yu l cc cht khng phn cc nn chng
khng tan trong nc, tan t trong ru v tan tt trong dung mi khng phn cc
nh n-hexan, xng, benzen tan ca du vo trong dung mi ph thuc vo
nhit . Khi ha tan mt s loi du vo dung mi, ta cn kt hp gia nhit nng
cao tan ca chng.
Mu sc ca du do cc hp cht mu trong du quyt nh. Du tinh khit
khng c mu. Nu du cha nhiu carotenoit th thng c mu vng, du cha
clorofin s c mu xanh i khi, vi nhng loi du cha nhng gc acid beo

22

khng no trong qu trnh bo qun c th b oxy ha to mu sc khc so vi mu

du gc.
Khi lng ring ca du thc vt nm trong khong 0,907 0,971, do du
nh hn nc v ni trn b mt ca nc. Du c cc gc acid cng nhiu cacbon
v cng no th t trng cng ln.

1.3.3. Tnh cht ha hc ca du thc vt

Thnh phn ha hc ca du thc vt ch yu l cc triglyxerit, mt loi ester
ca acid beo v glycerin nn chng c y ca mt ester in hnh.
Phn ng thy phn. iu kin nhit , p sut v xc tc nht nh
(thng l xc tc acid, enzym) s xy ra phn ng thy phn ester ln lt to
thnh cc ditriglyxerit v monotriglyxerit, cui cng l acid beo v glycerin. y l
phn ng thun nghch:

Phn ng tng qut c th c vit nh sau:

Phn ng x phng ha: trong mi trng kim, ester trong du thc vt s

phn ng vi kim to thnh mui natri (kali) ca acid beo (thnh phn chnh ca
x phng) v glycerin. Qu trnh x phng ha cng xy ra theo tng giai on nh
qu trnh thy phn, cho ta nhiu sn phm khc nhau nhng sn phm cui cng l
x phng v glycerin. Phn ng xy ra hon ton mt chiu:

y l phn ng c bn trong qu trnh sn xut x phng v glycerin t du

thc vt.
Phn ng trao i ester trong mi trng c xc tc v c nh acid H2SO4,
HCl hay cc cht xc tc baz nh NaOH, KOH cc ester trong du thc vt c th
tin hnh ester ha trao i vi cc ru bc 1 nh metylic, etylic to thnh cc
ester acid beo vi cc ru tng ng v glycerin. Vi R l gc hydrocacbon ca
ru, phn ng dng tng qut nh sau:

23

Phn ng ny l phn ng c bn tng hp Biotrans. Ester ca cc acid beo

v ru bc mt c th thay th nhin liu diesel trong cc ng c diesel, gim
thiu mt cch ng k lng kh c hi thi ra mi trng.
Bn cnh , cc gc acid beo trong du thc vt c th dn n mt s tnh
cht ha hc khc. Phn ng cng hp gm c cng hp hydro v cng hp
halogen. Cng hp hydro: khi c mt xc tc Niken v di p sut, nhit cao,
cc gc acid beo khng no trong du thc vt c th cng hp vi hydro to
thnh cc gc acid beo no. Qu trnh no ha du thc vt thng lm tng nht
v lm rn du thc vt. Cng hp halogen: du thc vt c th tc dng vi
halogen nhng lin kt cha n trong gc acid. Phn ng oxy ha, cc lin kt i
trong gc acid cha no ca du thc vt rt d b oxy ha. Ty thuc vo cht oxy
ha v mi trng oxy ha m to ra cc sn phm nh peroxyt, xetoacid hay t
mch to thnh cc phn t lng nh hn. Qu trnh oxy ha c th xy ra khi du
thc vt tip xc trc tip vi khng kh lm cho du b bin cht, gim cht lng.
S i chua ca du do trong du c ln nc, vi sinh vt v cc loi men
nn trong qu trnh bo qun thng xy ra cc phn ng bin i phn huy lm nh
hng n mu sc, mi v m ngi ta gi l s i chua ca du.

1.3.4. Mt s thng s quan trng ca du thc vt

biu th tnh cht v cu to ca tng loi du, ngi ta thng nht quy
nh mt s ch tiu c tnh cht c trng cho du thc vt. Nhng ch s ny c
th gip ta nh gi s b phm cht ca du thc vt, ng thi gip qu trnh tnh
ton thun li hn. Ch s x phng ha l s miligam KOH cn thit trung ha
v x phng ht 1g du. Thng thng du thc vt c ch s x phng khong 170260. Ch s ny cng cao th du cha nhiu acid beo phn t thp v ngc li. Ch
s acid l s miligam KOH cn thit trung ha ht lng cht beo t do c trong
1g du. Ch s acid ca du thc vt khng c nh, du cng bin cht v b oxy
ha th ch s acid cng cao. Ch s iod l s gam iod cn thit tc dng ht vi

24

100g du. Ch s iod biu th mc khng no ca du. Nu ch s ny cng cao th

du thc vt cng cha nhiu cc gc acid beo khng no v ngc li.
Bng 1.4 Cc tnh cht vt l v ha hc ca du thc vt
Tn du

KV

CR

CN

HHV

AC

SC

IV

SV

Du bng

33.7 0.25

33.7

39.4

0.02

0.01

113.20

207.71

Du nho

37.3 0.31

37.5

39.7

0.006

0.01

108.05

197.07

Du hng dng

34.4 0.28

36.7

39.6

0.01

0.01

132.32

191.70

Du vng

36.0 0.25

40.4

36.4

0.002

0.01

91.76

210.34

Du nnh

28.0 0.24

27.6

39.3

0.01

0.01

156.74

188.71

Du thu du

33.1 0.24

38.1

36.6

0.006

0.01

69.82

220.78

Du lc

24.0 0.21

52.9

39.8

0.01

0.02

98.62

197,63

Du c

34.2 0.22

34.5

39.8

0.01

0.01

102.35

197.56

Trong :
KV: nht ng hc, mm2/s ti 311K.
CR: cn cacbon, % khi lng.
CN: tr s cetan.
HHV: nhit tr, MJ/kg.
AC: hm lng tro, % khi lng.
SC: hm lng lu hunh, % khi lng.
IV: ch s iod, g I2/100g du.
SV: ch s x phng, mg KOH/ 1g du.

1.3.5. Cc loi du thc vt thng dng hin nay

Du u nnh: du u nnh c chit xut t ht u nnh. Cy u nnh l
loi cy trng ph bin nhiu ni trn th gii, c bit l Bc M. Du tinh
khit c mu vng sng, thnh phn acid beo ch yu l acid lioleic (50-57%), oleic

25

( 23-29%). Du u nnh c dng nhiu trong thc phm. N c dng lm ch

yu lm du rn, du n. Bn cnh , t du u nnh c th tch ra c lexetin
dng lm dc liu trong sn xut bnh ko. Ngoi ra, du u nnh c th dng
sn xut x phng, vecni, sn v l nguyn liu l tng v rt thng dng sn
xut du bin th sinh hc.
Du da: da l mt loi tri cy nhit i c trng nhiu Chu M La
Tinh, Chu Phi, ng Nam , n . Trong vng ng Nam th Philipine l
nc ni ting v trng v xut khu da. Vit Nam da c trng nhiu cc
vng Nam Trung B nh Bnh nh, Phan Thit Da l cy sinh trng lu nm,
thch hp vi kh hu nng m v c th trng c nhng vng t mn, chua.
Du da c chit t cm da, c cha cc acid beo no mch trung bnh nh acid
lauric (44-52%), myristic (13-19%), panmitic (7.5-10.5%). Hm lng cc acid beo
khng no trong du da rt t. Du da s dng nhiu ch bin thc phm, sn
xut macgarin v l nguyn liu tt sn xut x phng v du bin th sinh hc.
Du c: c l mt loi cy nhit i c trng nhiu Chile, Ghana, Ty Phi
v mt s nc Chu . khu vc ng Nam th Malaysia l nc trng v
xut khu nhiu du c nht. Vit Nam c c trng ch yu trung du pha
Bc vi din tch khng nhiu. T cy c c th sn xut c du nhn c v du
ci c. y l hai loi du khc nhau c nhng ng dng khc nhau. Du ci c c
mu vng c dng n trc tip hay ch bin thnh b, m thc vt. Du ci c
c cha nhiu caroten nn cn c dng nhiu sn xut tin sinh t A. Du
nhn c dng sn xut bnh ko. C hai du ny c th dng nu x phng
hay tng hp du bin th sinh hc.
Du s: cy s l mt loi cy lu nm c trng nhiu vng nhit i.
nc ta, cy s c trng nhiu cc tnh trung du pha Bc. Thnh phn acid beo
ca du s bao gm acid oleic (>60%), acid lioleic (15-24%) v acid panmatic (1526%). Du s sau khi tch saposin dng lm du thc vt rt tt. Du s l nguyn
liu tt trong cng nghip sn xut x phng hay tng hp du bin th sinh hc.

26

Du bng: bng l loi cy trng mt nm. Trong du bng c sc t

carotenoit v c bit l gossipol v cc dn xut ca n lm du bng c mu c
bit: mu en hay mu sm. Gossipol l mt c t mnh nn mun chuyn du
bng thnh du thc phm phi tch gassipol ra bng phng php tinh ch dng
kim hay acid antranilic. Trong du bng c nhiu acid beo no panmitic beeb
nhit phng n th rn. Bng cch lm lnh dy ngi ta c th tch c acid
panmitic dng sn xut macgarin v x phng. Du bng cng dng sn xut
du bin th sinh hc.
Du hng dng: hng dng l loi cy mt nm v c trng rt nhiu
x lnh nh cc nc Chu u, Chu , Bc M v c bit l Lin X (chim
90% sn lng th gii). Du hn dng c mi v c trng v c mu vng sng
ti . Du hng dng c nhiu protein nn l mt loi thc phm rt qu. Du
hng dng cng l nguyn liu tt tng hp du bin th sinh hc.
Du thu du: du thu du hay cn gi l du ve c ly t ht cu cy thu
du. Cy thu du c trng nhiu vng c kh hu nhit i. Nhng nc sn
xut du thu du l Brazil (36%), n (6%), Trung Quc, Lin X c, Thi Lan.
Ti Vit Nam, thu du c trng nhiu vng trung du Bc b, Thanh Ha, Ngh
Tnh. Tuy nhin du thu du Vit Nam vn cn ang nhp t trung quc. Du
thu du l loi du khng kh, ch s acid t 80-90, t trng ln, tan trong ankan,
khng tan trong xng v du ha. Hn na, do nht cao ca du thu du so vi
cc loi du khc nn ngay t u du thu du c s dng trong cng nghip
bi trn. Hin nay du thu du vn l mt trong cc loi du nhn cao cp dng
trong ng c my bay, xe la v cc my c tc d cao, trong du phanh Du
thu du c dng nhiu trong nhiu lnh vc nh y t (lm thuc ty v thuc
nhun trng), cng nghip m phm v hng liu, cng nghip cht do, cng
nghip giy (lm giy than, giy nn v mc in), cng nghip dt, nhum, cng
nghip sn, dng trong thuc da v c th dng tng hp du bin th sinh hc.
Ni chung, hu ht cc loi du thc vt thng dng u c th dng tng
hp du bin th sinh hc. Tuy nhin, ph thuc vo hm lng acid beo t do khc
nhau trong tng loi du m i hi qu trnh x l v tinh ch khc nhau. mi

27

vng, mi quc gia c th mnh v trng loi cy ly du no th c th tng hp

Biotrans t du ca loi cy trng . Nc ta rt c th mnh v cc loi cy nh
da, u nnh, thu du. V vy, cn u t v quy hoch vng trng trt, sn xut
m bo lng nguyn liu cho qu trnh sn xut du bin th sinh hc vn rt
pht trin trong tng lai gn.

1.4.6. Vi nt v cy da v du da
Cy da l mt trong t cc loi cy m tt c cc b phn ca chng u c
cng dng hu ch. Nc da lm nc gii kht, cm da lm thc phm hay ep
ly du, v ngoi da dng lm nguyn liu sn xut than hot tnh cht lng cao,
v trong da (go da) ch tc thnh cc sn phm th cng m ngh, cnh l da
dng lm vt liu lp mi nh, thn v r da phi kh dng lm ci un hay vt
liu xy dng Chnh v vy m da c tn gi l cy ca s sng. Da l loi
cy thn g, sinh trng nhng vng kh hu nhit i, c th chu c t mn,
t ct rt tt, do ta hay gp loi cy ny nhng vng nhit i ven bin hay
trn cc o nhit i. Tuy vy, da khng th sng c vng kh hu lnh gi
bi tnh chu lnh kem, thm ch khi cn nh ch mt t lnh ngn ngy cng c
th lm cht cy. Da l loi cy u sng, cn rt nhiu nng lng t nh sng mt
tri nn khng th pht trin v c th tn li khi trng thnh trong khu vc khng
c nh nng mt tri (trong nh, di tn ca cc loi cy khc). Vi nhng c
tnh nh vy, da tr thnh mt loi cy mang li rt nhiu thu nhp cho nhiu
nc vng nhit i. mt s hn o thuc Thi Bnh Dng, i sng ca nhiu
ngi bn a ph thuc hon ton vo loi tri cy ny.
Du da l loi du c gi tr v c nhiu cng dng nht trong cc loi du
thc vt, chnh v vy du da l mt trong cc loi du thc vt c gi thnh t
nht. Du da c chit xut t cm da kh (cm da c phi kh t nhin
di nh nng mt tri hay sy kh di tc dng ca nhit ), mc ch ca qu
trnh ny l loi b phn ln lng nc c trong cm da, nng cao gi tr du
da. Cm da kh sau c a vo ep ly du, b da sau khi ep c th lm
thc phm, phn bn hay lm thc n cho gia sc rt tt v chng cha nhiu

28

protein (18-25%). Cm da cha hm lng ln du, t 65-72% nn trung bnh c

19 qu da cho mt lt du da. Sn lng du da lun ln hn nhiu so vi cc
loi du thc vt khc, chim 20% tng sn lng cc loi du thc vt. Mc d
loi cy ny c trng rng ri nhiu quc gia nh Philipine l nc sn xut
du da ln nht th gii. Trung bnh hng nm nc ny sn xut ti 1,4 t m3 du
da. Ch 20% trong sn lng c s dng cho nhu cu trong nc trong khi
80% lng du da cn li dnh cho xut khu.
Du da l cht lng mu vng nht, kt tinh v ng c khi nhit gim
xung di 250C cho ta cht rn dng sp mm mu trng. Thnh phn cc gc acid
beo trong triglyxerit ca du da trong bng 1.5 nh sau:
Bng 1.5 Thnh phn cc gc acid beo trong du da
Thnh phn
Hm lng (%)
Acid lauric
47.5
Acid myristic
18.1
Palmitic
8.8
Caprylic
7.8
Capric
6.7
Stearic
2.6
Caproic
0.5
Acidlinoleic
1.6
Acidoleic
6.2
Cc thnh phn khc
0.2

Do thnh phn nhiu gc hydrocacbon no dn n tnh cht nhit kt

tinh cao ca du da. Cc thng s l ha c bn ca du da c th hin trong
bng 1.6 sau:
Bng 1.6 Tnh cht ha l ca du da

29

Tnh cht

Gi tr

T trng 400C

0.91-0.92

Tr s cetan

70

Ch s Iod

8-10

Nhit nng chy

250C

nht 400C

33.70 cSt

Nhit vn c

22.50C-230C

Nhit lu chuyn

200C

im chp chy

2250C

Ch s x phng

246-260

Ngoi ra du da c kh nng bi trn tt li d pha trn vi cc loi du

khc, qu trnh chuyn ha thnh du bin th sinh hc mt cch d dng.
Tuy nhin nu xet trong mt thi gian di th loi nhin liu s dng trc tip
du da ny vn mang n nhng vn xu cho my bin p nh b oxy ha, ht
kh nng lm mt, hi m trong du tng dn n s suy gim kh nng cch in
v lm mt ca du m l do chnh vn l linh ng kem ca loi du ny.
Chnh v vy mt vn t ra l phi gim nht, gim nhit ng c
h ch s acid cng nh hm lng nc ca du da bng mt phng php no
m vn m bo kh nng s dng lm du cch in. V phng php tng
hp du bin th sinh hc i t du da tr thnh mt hng nghin cu mi
cho nghnh cng nghip in, v l mt ti c ch cho nhng mc tiu thn thin
hn vi mi trng v gim s ph thuc vo du khong ang dn cn kit.

30

CHNG 2. PHNG PHP NGHIN CU

2.1. Ha cht, thit b, dng c.
2.1.1. Ha cht
Du da.
Kali hydroxit (KOH).
Methanol (CH3OH).
Phenolphtalein.
Ete du ha.
Acid clohydrit (HCl).
Acid sunfuaric( H2SO4)
Ethanol (C2H5OH)
Cc ha cht trn c ngun gc t Trung Quc v c mua ti cng ty
TNHH thng mi Bch Khoa (T Hin Thnh, Phng 14, Qun 10, TP HCM)
ngoi tr du da c mua ti Bn Tre.

2.1.2. Thit b
My khuy t c gia nhit CB162 c sn xut bi Stuart (BIBBY) - Anh.
H thng sinh hn, sn xut t c.
Thit b lc, ht chn khng.
Bp in.
My o pH.
Cn phn tch (4 s).
T sy.
Bnh ht m.
H thng phn tch sc k kh GC.

31

H thng xc nh hm lng nc Karl Fisher

Cc th b s dng trn c mn t phng th nghim ca Khoa Cng
Ngh Ha Hc trng i Hc Cng Nghip Thnh Ph H Ch Minh. Ngoi ra
cn s dng cc thit b khc:
-

My phn tch hm lng axit beo trong du thc vt : Trung tm k thut

th nghim TP.H Ch Minh , S 2 Nguyn Vn Th qun 1 TP.HCM

My xc nh in p nh thng du bin th: Trung tm 3, s 31 Hn

Thuyn, qun 1 TP.HCM.

2.1.3 Dng c
Becher 50ml, 100ml, 250ml, 500ml.
ng nh git
ng ong 100ml.
a thy tinh.
Nhit k 1000C c nt cao su.
C t.
Pipet 25ml.
Phu lc
Phu tch 100ml, 250ml.
Kp pipet.
Giy pH.
Nt cao su.

2.2. Phng php nghin cu

2.2.1. Nguyn liu v xc tc cho qu trnh

32

Nguyn liu cho qu trnh tng hp du bin th sinh hc l du da,

methanol. Xc tc c s dng cho qu trnh tng hp trong n ny l xc tc
KOH, H2SO4.

2.2.1.1. Methanol
Ru c s dng trong qu trnh tng hp du bin th l ru n chc c
t mt n tm nguyn t cacbon. Tuy nhin s lng cacbon phn t ru cng
ngn cng tt v vy chng d dng hn trong vic tip cn vi phn t glyxerit
to hp cht trung gian nh trnh by trong phn c ch. Trong cc loi ru th
methanol lun l s la chn hng u do gi thnh thp, cho phep tch ng thi
pha glyxerin. Mt khc do methanol l ru c mch cacbon ngn nht v phn cc
(methanol c th tan v hn trong nc) nn qu trnh phn ng thun li hn, cho
hiu sut cao, cng on tch sn phm cng d dng hn nhiu v tn t nng
lng vo qu trnh phn tch tinh ch sn phm. Hn na, metyl ester c nng
lng ln hn cc ester ca ru khc nn hn ch c kh nng to cc vi
phun, do methanol tr thnh s la chn ti u cho qu trnh tng hp du
bin th trong cng nghip cng nh trong phng th nghim.
Methanol hin nay c tng hp ch yu t than v kh du m. y l
mt cht lng khng mu, mi hi xc, d bay hi (nhit si ca methanol l
64,70C), d bt chy v rt c. Nu hm lng methanol tn ti trong c th vt
qua mt ngng no s dn ti m mt v t vong. Do vy khi tin hnh th
nghim vi methanol phi tin hnh trong t ht, trnh xa ngun nhit; ngi th
nghim phi eo khu trang v gng tay bo h trnh ng c methanol qua
ng h hp hay qua ng tip xc qua da.
m bo chnh xc cho qu trnh nghin cu, methanol thc hin phn ng
l loi ru tinh khit dnh cho phn tch c hm lng CH 3OH 99,8%. Do nhit
si ca methanol kh thp nn trnh mt mt, cn gi nhit phn ng nh hn
600C v c sinh hn hi lu ngng t hi lu lng methanol bay hi. Lng
methanol dng trong phn ng cn phi d m bo cho phn ng chuyn dch
d dng theo chiu thun cho hiu sut sn phm mong mun cao nht. y cng l

33

nguyn nhn phi m bo iu kin phn ng n nh trnh mt mt methanol

trong qu trnh phn ng do qu trnh bay hi nhit kh cao.

2.2.1.2 Du da
Du da tin hnh th nghim l loi du da th, c chit tch t cm da
kh. Vit Nam, cy da c trng rt nhiu cc vng Nam Trung b nh Bnh
nh, Bn Tre hay cc tnh Nam B nh An Giang Mc d c rt nhiu tc dng
nhng hin cc tnh ny da vn cha c trng mt cch c quy hoch. Du
da Vit Nam ch yu sn xut bi cc nh my nh ngay ti a phng, mt
phn nh p ng nhu cu trong nc, cn li ch yu xut khu. Nhng ng
dng ca du da trong nc cng khng nhiu, ch yu lm nguyn liu cho nh
my sn xut bnh ko. Nhng nghin cu trn th gii (c bit l Philipine, ni
c lng sn lng du da trong nc v xut khu ln nht th gii) ch ra
c rt nhiu u im ca du da. Chnh v vy, du da Vit Nam l ngun
nguyn liu l tng sn xut loi nhin liu sinh hc ny. Tng hp du bin th
t du da s va gp phn lm gim nhim mi trng, va m bo u ra cho
loi du thc vt ny v to thm nhiu cng vic cho ngi dn a phng. Qu
trnh tng hp du bin th khng qu phc tp, khng cn u t my mc phc
tp hin i v hon ton c th sn xut c vi quy m nh l.

34

Hnh 2.1 Mu du da nguyn liu

Du da c mt u im rt ln cho qu trnh tng hp du bin th l ch s
acid (AN) rt thp. Tuy nhin du da cng ty m sn xut m c ch s acid khc
nhau, nn khi mua s dng sn xut du bin th th cng c m c ch s acid
nh hn 1mg KOH/g du ph hp sn xut du bin th cng c m ch s acid
ln hn 1mg KOH/g du nn khng ph hp sn xut du bin th v vy cn x
l du da ch s ca du da nh hn 1 mgKOH/ du ng thi phi tin hnh
tch nc lm khan sn phm sau khi x l. Nu ch s acid ln hn 1 mgKOH/
du trong qu trnh s dng xc tc kim cho phn ng tng hp du bin th s to
ra x phng, x phng nhiu lm ng c khi phn ng dn n hiu sut chuyn
ha thp. Phng php ester ha l mt trong nhng phng php gim ch s acid
tch cc acid beo t do tt x l vn nu trn.

2.2.1.3. Xc tc kim
Qu trnh tng hp du bin th c th s dng xc tc kim, acid hoc
enzym. Tuy nhin v xc tc kim cho hiu sut cao nht, gi thnh r v thi gian
phn ng ngn nn trong cng nghip u s dng xc tc kim m tiu biu nht l
NaOH v KOH. Do trong qu trnh phn ng, NaOH (hoc KOH) rn c ha tan
vo trong ru nn phn ng din ra trong pha lng v xc tc c coi l xc tc
ng th. Hin nay trn th gii tt c cc qu trnh sn xut theo quy m cng
nghip u s dng loi xc tc ny.
Xc tc ng th c u im l hot tnh cao, thi gian phn ng nhanh, phn
b u v tip xc tt vi cht phn ng nn cho hiu sut rt cao.L do m KOH
(NaOH) c th tan trong ru l cc phn t ru c th ph v lin kt mng tinh
th gia cc phn t NaOH vi nhau, lm cho cc phn t NaOH tch ri nhau ra
v khuch tn vo trong ru. Tuy nhin chng cng c kh nhiu nhc im nh
rt d to x phng trong qu trnh phn ng khi c mt ca nc v acid beo. Do
s dng xc tc ng th i hi nguyn liu phi c x l rt trit gim
ch s acid xung mc ti thiu v lm khan hon ton nguyn liu, hm lng
nc c hn ch mt cch kht khe.Thu hi v tinh ch glyxerin gp nhiu kh
khn. Xc tc tn ti trong sn phm nn vic tch xc tc ra khi sn phm rt

35

phc tp. Do du bin th c gii hn hm lng kim tng nn qu trnh ny

khng th b qua.

2.2.2. Cch tin hnh tng hp biotrans

Qu trnh tng hp du bin th da da trong phng th nghim c tin
hnh nhit thp, p sut kh quyn vi s c mt ca xc tc ng th c
hot ha bng KOH hoc H 2SO4. C rt nhiu yu t nh hng n qu trnh phn
ng nh nhit , lng xc tc, tc khuy, thi gian phn ng, t l
methanol/du v hm lng acid beo cng nh hm lng nc. Nhit phn ng
cng cao cng tt nhng phi duy tr di 60 0C trnh bay hi mt mt methanol.
Do s dng cng mt lng mu du c x l m bo nh nhau nn nh
hng ca nc cng nh lng acid beo t do c gim ti thiu. Nhit phn
ng c gi 600C tng vn tc phn ng. Tc khuy trn khng i. Phn
ng tng hp du bin th s c kho st quan h ca lng xc tc, thi gian
phn ng vi hiu sut phn ng ca loi xc tc ng th ny ny.

2.2.2.1. Cc bc tin hnh th nghim

Giai on 1: Do du da nguyn liu c ch s axt cao gn bng 4 nn ta x l
thm 1 giai on na l ester ha. Nhng acid beo c trong du phn ng vi
methanol (t l 1:1 theo phn mol) di s c mt ca cc acid mnh nh H 2SO4
c lm xc tc to thnh metyl este. Hiu sut ca phn ng ny thng t hn
96%, c ngha rng vn cn mt phn khong 4% lng acid beo t do ban u vn
cn tn ti trong nguyn liu v s phn ng vi kim trong giai on tip theo
to thnh x phng. Trong phn ng giai on 2 ny, lng x phng phi c
tch ra kp thi nu khng s to bt cn tr phn ng trao i ester lm hiu sut
gim mt cch ng k. Hiu sut ca phn ng trong giai on 2 to metyl ester
bng phn ng trao i este ny kh cao, ln n hn 99% ty thuc v sch ca
nguyn liu v iu kin phn ng.Nn ester ha l giai on cn thit cho phn
tng hp biotrans.
Tin hnh th nghim nh sau: Du vi methanol c cn theo theo t l
1:1, lng acid H2SO4 bng 0.5% so vi khi lng du v methanol.Phn

36

ng trong 2,5h. tch pha trong 12h sau thu hi phn methanol cn li
vo bnh thu hi.Ly phn cn li ra v chuyn sang giai on 2 khi ch s
acid t <1.

Giai on 2:Tin hnh ln lt cc bc sau

Cn chnh xc lng xc tc v methanol theo t l cn kho st vo bnh cu
phn ng ba c, lp h thng sinh hn v khuy mnh trong vng 30 pht hot
ha xc tc. Cn chnh xc lng du da (m) cho vo bnh phn ng, lp h thng
hon lu, n nh nhit nhit cn kho st bng bp t cch thy v khuy
mnh trong sut thi gian phn ng cn kho st. Sau khi cho ht ru, du da,
xc tc vo phi y np sao cho thit b tht kn, trnh s mt mt methanol trong
qu trnh phn ng v m van nc sinh hn hot ng trnh methanol bay hi.
iu chnh tc khuy ph hp sau gia nhit hn hp ti nhit phn ng
mong mun. C nh nhit v tc khuy trong sut thi gian phn ng. Thi
gian bt u phn ng c tnh t khi rt du da vo hn hp methanol v xc
tc.
Lp s h thng nh sau:

37

Hnh 2.2 H thng th nghim lp t trong phng th nghim

2.2.2.2. Qu trnh tch v tinh ch sn phm

Qu trnh tch v tinh ch sn phm sau khi ester ha:
Khi phn ng kt thc, cho bnh phn ng ngui hn, hn hp phn ng
vo beaker v tin hnh tch lp 12 gi. Hn hp phn ng sau khi lng chia thnh
2pha: lp trn gm c methanol d, lp di gm FAME, cc sn phm ph v du
da d (nu c).Chit ly phn di ra khi phu chit, phn trn a vo bnh thu
hi. Hn hp thu c sau c a vo beaker 250ml, cho khong 20ml nc
ct vo beaker, khuy nh 70 80oC trong 10 pht ra FAME, loi methanol
v cc sn phm ph sau chuyn nh nhng hn hp sang phiu chic trnh
hin tng to bt.Sau cng lm tng t nh trn ra vi nc thu c ester.
Qu trnh tch v tinh ch sn phm sau khi transesterification:
Khi phn ng kt thc, cho bnh phn ng ngui hn, hn hp phn ng
vo beaker v tin hnh tch lp 2 gi. Hn hp phn ng sau khi lng chia thnh 2
pha: lp trn gm c FAME, cc sn phm ph v du da d ( nu c), lp di
gm glycerin, phn ln lng ru methanol cha phn ng c thu hi vo bnh
thu hi.Gn b phn cht lng lp di.Phn FAME sau c a vo beaker
250ml, cho khong 20ml nc ct vo beaker, khuy nh 70 80oC trong 10 pht
ra FAME, loi glycerin v cc sn phm ph sau chuyn nh nhng hn hp
sang phiu chic trnh hin tng to bt.

38

Hnh 2.3 S tch pha ca sn phm sau khi phn ng

Tin hnh tch pha trong 20 pht sau loi b lp nc ra bn di, rt
lp Biotrans trn cho li vo beaker 250ml ri lp li qu trnh trn 5 6 ln cho
n khi nc ra trong v pH t trung tnh. Chuyn lp du trn phiu chit sang
beaker 250ml cn trc khi lng mo (g) sau t beaker vo l vi sng
ci t cng sut 480W, sy sn phm khong 180 pht cho n khi lp du trong
v ng nht, ngui beaker sau lc lp du qua MgSO4v cn ghi nhn khi
lng.

2.2.2.3. S quy trnh to Biotrans

2.2.3. Cc phng php phn tch cht lng sn phm

Phng php phn tch cht lng sn phm bao gm:
Xc nh ch s acid.
Xc nh nht ng hc.
Xc nh im chp chy cc h.
Xc nh t trng.

39

Xc nh im vn c.
Xc nh hm lng nc
Xc nh ch s x phng ha
Xc nh in p nh thng
Xc nh thnh phn ester.(Sc k)

2.2.3.1. Xc nh ch s acid ASTM D664

Ch s acid l s mg KOH cn thit trung ha ht acid beo t do c trong
1g du m hay du bin th. Ch s ny xc nh lng acid beo t do c trong du
bin th v dng nh gi kh nng n mn vt liu ca du.
Nguyn tc xc nh ch s acid da vo phn ng trung ha gia acid beo t
do v KOH 0,1N trong mi trng hn hp gm ethanol: ete du ha theo t l 1:1
vi ch th phenolphtalein 1%.
Cc bc tin hnh nh sau: cn chnh xc khong 1 - 2g mu vo beacher
250ml, thm vo beaker 25ml hn hp dung mi ethanol: ete du ha pha theo t l
1:1, lc nh ha tan hon ton mu (Lu l hn hp dung mi phi c trung
ha trc bng KOH), thm vi git ch th phenolphtalein 1%. Chun bng
dung dch KOH 0,1N trn buret cho n khi xut hin mu hng bn trong 30 giy
(va chun va lc beaker).Tin hnh ng thi 2 th nghim. Nu dung mi
khng c trung ha trc th c th tin hnh mu trng song song.
Ch s acid ca m c tnh nh sau:

Trong :

Av: l ch s acid mgKOH/ 1g du.

VKOH: s ml KOH dng chun .
m: l s gam du dng chun .

2.2.3.2. Xc nh nht ng hc ASTM D445

40

 nht l mt i lng vt l c trng cho tr lc ma st nt ti ca cht

lng sinh ra khi chuyn ng. nht ca du m v du bin th rt quan trng v
n nh hng n kh nng lm mt v gim ma st.
Xc nh nht ca du m v Biotrans bng nht k mao qun Cannon
Fenske Routine. Trc khi o nht k phi c ra sch bng aceton v sy
kh.
Cc bc o nht tin hnh nh sau: trc ht cn ci t b n nh nhit
40oC sau dng pipet ly 10ml mu cho vo nhnh ln ca nht k, lp nht
k vo gi ton b phn mu trong nht k c ngm trong b iu nhit
trong 30 pht. Dng bp cao su t u nh nht k, ht chnh mu sang nhnh
nh mc mu cao hn vch nh du th nht khong 5mm. Sau mu chy
t do v dng ng h bm giy xc nh thi gian mu chy t vch nh du th
nht n vch nh du th hai. Lp li qu trnh ny, kt qu c ghi nhn nu sai
s gia hai ln o nh hn hay bng 0,2%.
nht ng hc ca du m v Biotrans c xc nh nh sau:
= C.t
Trong :

C: hng s nht k s dng

t: thi gian chy ca mu (s)
: nht ng hc ca mu (mm2/s)

2.2.3.3. Xc nh im chp chy cc h ASTM D92

im chp chy ( flash point) ca sn phm du l nhit thp nht c
hiu chnh p sut 101.3 kPa ( 760 mmHg), ti ni hi ca mu th chp chy
khi c mi la di iu kin th nghim.
im chp chy c tin hnh xc nh nh sau: cho 70ml du vo cc t
ln thit b gia nhit.Lp nhit k v mi ngn la th nghim nh.Tin hnh gia
nhit vi mc 5-6oC/pht.Gia nhit ti khong d on th gim mc gia nhit t 12oC/pht.Nhn nhit k sau bt cng tc mi la th nghim. Lp li qu trnh c
tng 2oC/ln.Khi xut hin ngn la trn b mt thong 2 ln ghi nhit li gi tr
nhit

41

2.2.3.4. Xc nh t trng
T trng l t s gia khi lng ring ca mu v khi lng ring ca nc
ct ti cng nhit .
T trng mu c xc nh theo cc bc sau: cn chnh xc n 0,0001g t
trng k 10ml c sy kh ta c c mo (g). Cho nc ct n vch mc ca
ca t trng k, cn v ghi kt qu l m1 (g). Cho mu n vach nh mc ca t
trng k, cn v ghi kt qu l m2 (g).
T trng ca mu c tnh theo cng thc:

o 2 ln trn mt mu ly kt qu trung bnh c lm trn n 4 s l. Chnh

lch kt qu gia hai ln th khng c qu 0,002 n v.

2.2.3.5 Xc nh im vn c
Nhm xc nh nhit vn c ca sn phm du m sng mu. im vn
c ca sn phm du m l nhit thp nht m sn phm vn cn c s dng.
Phng php xc nh im vn c c tin hnh nh sau: ly mu th
nghim nhit cao hn nhit vn c t nht 14 0C, c th loi tr phn m
bng cch lc qua mng lc thm nc n khi mu th sch hon ton (qu trnh
lc phi thc hin nhit cao hn nhit vn c t nht 14 0C). Rt mu th
nghim vo ng th n vch nh mc. y ng nghim bng nt cao su c gn
nhit k v iu chnh sao cho nhit k v tr ng trc vi ng th nghim v bu
nhit k khng c va chm vo y ng nghim. Lp vng m va ng bao sau
khi ng bao c lm sch v kh. Gn ng bao vo gi kp v nhng ng bao
vo trong b lm lnh t nht 25mm. Lp ng th nghim vo ng bao sau khi ng
bao c ngm trong b lm lnh t nht 10 pht. Khng c nhng trc tip
ng th nghim vo b lm lnh. Duy tr nhit lm lnh ca b ti 0 1,50C.
Kim tra hin tng vn c nh k khi nhit gim 1 0C (ly nhanh ng nghim
ra khi ng bao quan st v lp li vo ng bao trong vng 3s), lu trnh lm
xo ng mu th nghim. Nu nhit mu th nghim gim n 9 0C m khng
thy xut hin tng vn c th phi di chuyn ng nghim test sang b 2 c nhit

42

 b lm lnh l -18 1,50C. Ghi nhn nhit xut hin hin tng vn c y
ng nghim chnh xc n 10C. Sau khi thc hin xong cn v sinh sch s thit b.
Bo co nhit vn c xc nh trn chnh xc n 10C.

2.2.3.6. Xc nh hm lng nc (theo Karl Fisher)

Phng php xc nh hm lng nc theo Karl Fisher l mt phng php
chnh xc ti nng ppm ca nc trong cc mu du.
Phng php s dng phn ng gia nc c trong du vi iod v sulfur
dioxide (Apura titrant 5) vi s c mt ca dung mi cha ru thp nh methanol
v mt cht hu c nh pyridine (Solvent).Phng trnh phn ng nh sau:
Phng php tin hnh xc nh nh sau: Ly 1 xilanh cha du em cn phn
tch ghi khi lng m1 (g).Sau bm vo bnh khuy ca thit b 1 lng du cho
chy phn tch ghi c khi lng dung mi phn ng l v1 (ml).Sau em cn
li xilanh cha du ta c khi lng m2 (g).
Theo phng php ta c 1ml ha cht phn ng cho ta bit trong c 5mg
H2O.
Hm lng nc c tnh nh sau:
(mg/g)

2.2.3.7 Phng php sc k

Phng php sc k kh c th xc nh nh tnh v nh lng thnh phn
ca nhiu hp cht phc tp. C th trong ti ny phng php sc k kh dng
xc nh thnh phn cc metyl ester c trong sn phm.
Nguyn tc: mu phn tch s c ha hi trong bung t ri c dng kh
mang a hn hp cc thnh phn trong mu i qua mt cht hp ph nm c nh
trong ct tch (pha tnh). Do p sut ca dng kh mang, ng knh v nhit ct
tch khng i, nn ty vo i lc hp ph ca cht phn tch v pha tnh trong ct
tch cc thnh phn trong mu s chuyn ng vi vn tc khc nhau v ra khi ct
tch vi thi gian lu khc nhau. Lc hp ph ca cu t no vi pha tnh ln th

43

thi gian lu ln v ngc li. Sau khi ghi li thi gian lu v din tch pic ca cc
cht qua sc k , ngi ta a cc cht chun (cht m d on s c trong thnh
phn mu) vo my sc k v ghi li sc k chun so snh vi sc k ca
mu phn tch nhm tm ra thnh phn cng nh khng nh li cc cu t c trong
mu cn phn tch.

2.2.3.8 Xc nh in p nh thng
in p nh thng in mi ca du cch in l thc o kh nng ca n
chu c ng sut in p m khng b hng. N l in p m ti xy ra s
nh thng gia hai in cc trong iu kin th nghim.
Vic xc nh in p nh thng c th gip chng ta pht hin s c mt ca
cc cht gy nhim nh nc, bi bn v cc ht rn.
Nu gi tr in p nh thng thp s gip chng ta xc nh c c mt
hoc nhiu cc cht gy nhim ang tn ti trong my bin th. Tuy nhin gi tr
in p nh thng nu cao th khng nht thit l my bin th cha nhiu cht
gy nhim.
C 2 phng php c cng nhn o in mi in p nh thng ca du
cch in l:
Phng php ASTM D877-00: phng php ny thng c p dng cho cc th
nghim mi, du cha qua qu trnh ch bin s dng trong cc b phn ngt
mch. Phng php ny dng cc in cc hnh tr mng, mt phng vi khong
cch l 2.5 mm. nhy ca phng php ny s gim khi in p th nghim ln
hn 25kV.
Phng php ASTM D 1816-97: phng php ny thng c p dng th
nghim cc cht lng dng trong qu trnh ch bin thnh my bin th hoc cc
cht lng cha trong my bin p. Phng php ny s dng cc in cc c dng
hnh cu khong cch tiu chun l 1mm v 2mm. Phng php ny nh gi tt
hn nhng thay i c th xy ra trong du my bin p v n phn ng nhanh hn
vi cc cht nhim ha tan trong du.

44

CHNG 3: KT QU V BN LUN
3.1 Xc nh tnh cht ca du da nguyn liu
3.1.1 Thnh phn ha hc v khi lng nguyn t
Bng 3.1 Thnh phn ca du da nguyn liu

Stt

Thnh phn
axit beo

CTPT

Caproic

C6H1202

116

0,29

0,34

Caprylic

C8H1602

144

5,23

7,53

Capric

C10H2002

172

5,10

8,77

Lauric

C12H2402

200

48,28

96,56

Tridecanoic

C13H2602

214

0,03

0,06

Myristic

C14H2802

228

19,89

45,35

Tridecanoic

C15H3002

242

0,01

0,02

Palmitic

C16H3202

256

9,84

25,19

Palmitoleic

C16H3002

254

0,01

0,03

10

Margatic

C17H3402

270

0,01

0,03

11

Stearic

C18H3602

284

3,71

10,54

12

Oleic

C18H3402

282

6,36

17,94

13
14
15
16
17

Linoleic
Arachidic
Eicosenoic
Behenic
Lignoceric

C18H3202
C20H3202
C20H3802
C22H4402
C24H4802

280
304
310
340
368

0,94
0,10
0,04
0,02
0,03
99,89

KLTB

684,77

M(g/mol)

%TB

2,63
0,30
0,12
0,07
0,11
215,59

Kt qu khi lng trung bnh phn t c tnh da trn kt qu phn tch

hm lng axit beo ca Trung tm phn tch k thut th nghim TP.HCM , s 2
Nguyn Vn Th,Qun 1,Thnh ph H Ch Minh.

3.1.2. Xc nh cc tnh cht ha l ban u ca nguyn liu

45

Bng 3.2 Tnh cht ha l ca du nguyn liu

Tnh cht

Gi tr

T trng 400C

0.91-0.92

Ch s acid

3.7

nht 400C

26.5 cSt

Nhit vn c

22.50C-230C

im chp chy cc h

2820C

Ch s x phng

263

3.2 Kho st cc yu t nh hng n qu trnh tng hp Biotrans

3.2.1 Thi gian phn ng
Thi gian phn ng l mt trong nhng nhn t quan trng nh hng ti hiu
sut ca phn ng. i vi mt phn ng ha hc thng th khi nhit tng th
hiu sut cng tng. Trong qu trnh tin hnh th nghim, phn ng tng hp
biotrans t du da c kho st vi thi gian thay i t 60p n 180p. Cc iu
kin khc c nh nh sau:
Lng xc tc (% xc tc so vi du): 0.75%
T l mol methanol: du: 6:1.
Thi gian hot ha xc tc: 30 pht.
Nhit phn ng: 600C.

STT

46

Bng 3.3 Kho st s nh hng ca thi gian

Khi
Khi
Khi
Thi gian
Khi
lng
lng
lng xc phn ng lng bio
du da Methanol
tc (g)
(h)
(g)
(g)
(g)

nht

50

14

0,48

60

32,65

4,12

50

14

0,48

90

38,34

2,98

50

14

0,48

120

37,94

3,08

50

14

0,48

150

36,65

3,14

50

14

0.48

180

36.50

3.26

Biu din mi quan h gia thi gian phn ng v khi lng ester th v
nht ln th ta c ng cong sau:

Hnh 3.1 Biu nh hng ca thi gian phn ng

C th thy thi gian phn ng cng di th khi lng ester th tng nhng
n mt gii hn thi gian phn ng th khi lng ester th gim dn. T y cho
thy thi gian phn ng bt u cn bng (v y l phn ng trao i ester l phn
ng thun nghch) v hiu sut cao v n nh nht ng thi va m bo cc chi
tiu kinh t (thi gian phn ng tng va tn nhiu thi gian m hiu sut phn ng
li khng cao).
Nhng iu trn c th c gii thch nh sau do du da nguyn liu v
methyl ester khng tan ln vo nhau nn xy ra phn ng mt cch mnh m cn
phi khuy trn v cn c thi gian cc phn t triglyxerit v methanol tip xc
vi nhau. Mc khc qu trnh ester ha triglyxerit xy ra qua cc giai on to thnh
diglycerit v monoglycerit nn cn c thi gian di th phn ng gn t n
im dng nn hiu sut khng tng c na thm ch l c th gim do sn phm
ph, hay phn hy sn phm chnh, v gy tn nhiu nng lng.Mt khc s tng
quan gia nht vi khi lng ester thu c cng cho thy kh nng to ra
nhiu ester nht th cho nht thp nht,do thi gian khng xy ra phn ng th
cn li mt phn cc tri-ester cha b ct mch ,c nht ln hn cc mono-ester.

3.2.2. T l xc tc
Mt trong cc yu t khc nh hng n phn ng tng hp Biotrans ni
chung v Biotrans da ni ring l khi lng xc tc. Trong qu trnh nghin cu
khi lng xc tc tham gia phn ng, cc iu kin khc c c nh nh sau:
T l mol methanol/du: 6:1

47

Thi gian hot ha xc tc: 30 pht.

Thi gian phn ng: 90 pht.
Nhit phn ng: 600C.
Khi lng xc tc thay i t 0,25% n 1,25% ( so vi khi lng du +
methanol) cho kt qu nh sau:

STT

Bng 3.4 Mi quan h gia lng xc tc vi hiu sut

Khi
Khi
KL xc
Khi
Khi
lng
lng
tc so vi
lng xc
lng
du da Methanol
du+ Me
tc (g)
ester (g)
(g)
(g)
(%)

nht
(cSt)

50

14

0,16

0,25

39,04

3,54

50

14

0,32

0,50

45,52

2,90

50

14

0,48

0,75

43,28

2,98

50

14

0,64

1,00

40,92

3,02

50

14

0,80

1,25

39,00

3,12

Biu din mi quan h gia khi lng xc tc v khi lng ester v nht
ln th ta c ng cong sau:

Hnh 3.2 Biu nh hng ca lng xc tc

Qua th ta thy khi lng xc tc tng th khi lng sn phm tng nhng
khi lng xc tc t 0.25% so vi khi lng du v methanol (0,16 g) ln 0.5%
(0,32 g) so vi khi lng du th khi lng tng t 39,04 ln n 45,52g ng
thi nht gim t 3,54 xung 2,9 cSt Nhng khi lng xc tc tng t 0,5%
(0,32 g) ln n 1,25% so vi khi lng duv methanol (0,8 g) th khi lng
gim u t 45,52g xung cn 39g ng thi d nht tng t 2,9 ln 3,12 cSt iu
ny cho thy khi lng xc tc tng th hiu sut tng nhng nu lng xc tc
nhiu th hiu sut gim dn, trong khi lng xc tc t hn th hiu sut thp nn

48

cng khng t yu cu. T nhng iu ni trn cho thy lng xc tc c hiu

sut phn ng cao nht l 0,5% so vi khi lng du.
T y ta c th gii thch c nh sau, khi lng xc tc tng ln th s tm
hot tnh cng nhiu, tng hot tnh xc tc cho qu trnh nn hiu sut ca qu trnh
cng tng theo. Tuy nhin, hot tnh xc tc l c gii hn, khi tng n im cc
i th chuyn ha cng khng th tng na nn d tng lng xc tc th hiu
sut cng khng tng. Mt l do khc d nhn ra l khi dng d xc tc th trong
qu trnh ra sn phm c th nhn ra. pH th bng giy qu d nhn ra khi xc
tc va th qu trnh ra nhanh d t trung tnh, cn d xc tc th phi ra rt
lu mi c th t c pH trung tnh.

3.2.3. Nhit phn ng

Rt nhiu cc phn ng ha hc u chu nh hng ca nhit , phn ng
tng hp biotrans cng khng phi l ngoi l. Tc phn hy cc triglyxerit bi
ru tng ln theo s tng nhit . Tuy nhin nhit khng c tng cao qu v
methanol c nhit si thp (64,70C) s d bay hi lm gim hiu sut phn ng.
Hiu sut ca phn ng c nghin cu vi s thay i nhit phn ng t
500C n 650C tm c nhit phn ng ti u. Trong qu trnh kho st,
ngoi tr yu t nhit thay i, cc thng s phn ng khc u c gi c
nh.
Bng 3.5 Mi quan h gia nhit phn ng vi hiu sut
Khi
Khi
Khi
Nhit
Khi
lng
lng
STT
lng xc phn ng
lng
du da Methanol
tc (g)
(0C)
ester (g)
(g)
(g)

49

50

14

0,32

50

35,48

50

14

0,32

55

41,60

50

14

0,32

60

45,52

50

14

0,32

65

39,64

Biu din mi quan h gia nhit phn ng v khi lng ester thu c
ln th ta c ng cong sau:

Hnh 3.3 Biu nh hng ca nhit

Nhit phn ng l yu t quan trng nh hng n hiu sut. Nhit
phn ng thp th hiu sut thnh phm mong mun trong thi gian ti u thp, nu
mun tng hiu sut th phi tng thi gian phn ng, iu ny nh hng ln n
nng sut ca qu trnh. T th ta thy c khi nhit phn ng 500C, 550C
th khi lng sn phm khng cao ch c 35,48g v 41,6 nhng khi nhit phn
ng tng ln n 600C th khi lng tng ln n 45,52 g nhng khi nhit tng
ln 650C th khi lng sn phm gim xung 39,64g. T y cho ta thy nhit
phn ng cho hiu sut cao nht cho vic tng hp biotrans du da l 600C. Nhng
iu ny c th c gii thch nh sau:
Khi nhit phn ng thp (nh hn 600C) s chuyn ng ca cc phn t
phn ng cn chm, tc phn ng chm, dn n hiu sut tng hp biotrans
thp. Tng nhit th tc phn ng nhanh, tuy nhin ch trong mt khong thi
gian nht nh. Nu nhit tng ln qu cao (ln hn 600C) s thun li cho qu
trnh x phng ha, ng thi tc bay hi ca methanol tng mnh (nhit si
ca methanol l 64,70C), iu ny lm gim kh nng tip xc ca triglyxerit trong
du da vi methanol nn lm cho khi lng sn phm thu c gim xung.

3.2.4. T l methanol: du
Theo phng trnh phn ng th t l mol methanol: du cn thit cho qu
trnh phn ng l 3:1. Tuy nhin trong thc t th phn ng trao i ester khng xy
ra hon ton vi t l mol nh vy v y l phn ng thun nghch. Trong qu trnh
phn ng, lng methanol thng c ly d cho qu trnh chuyn ha theo
chiu thun to ra nhiu sn phm metyl ester ca acid beo (biotrans) v s cho hiu
sut cao nht. Chnh v vy,t l mol methanol: du cn ln hn 3. Ngoi tr t l
mol methanol: du, cc thng s th nghim khc c c nh nh sau:

50

Lng xc tc (% xc tc so vi du): 0.5%

Thi gian hot ha xc tc: 30 pht.
Thi gian phn ng: 90 pht.
Nhit phn ng: 600C.
Bng 3.6 Mi quan h gia t l methanol: du vi khi lng sn phm
Khi
Khi
Khi
Khi
Thi gian
lng
lng
lng
T l mol
STT
lng bio
tch pha
du da Methano
xc tc methanol/du
(g)
(pht)
(g)
l (g)
(g)
1

50

14

0,32

5:1

44,24

25

50

16,35

0,32

6:1

45,52

50

18,68

0,32

7:1

46,12

50

21,02

0,32

8:1

46,24

10

50

23,36

0,32

9:1

46,12

12

Biu din mi quan h gia t l methanol:du v khi lng ln th ta

c ng cong sau:

Hnh 3.4 Biu nh hng ca t l methanol: du

T l mol methanol: m bng hoc nh hn 5 th lng methanol d trong hn
hp phn ng khng dch chuyn cn bng nn sn phm sau phn ng cn
du nhiu v hiu sut to thnh Biotrans thp. Tng t l mol methanol : du ln
hn 7 th hiu sut to thnh Biotrans khng tng nhiu;gy tn kem lng
methanol v methanol rt c v d bc hi do vy nn thc hin phn ng cn
bng t l mol methanol : du bng 6-7 l tt nht.

3.3. nh gi cht lng sn phm

Nh vy, qua qu trnh kho st cc yu t nh hng n qu trnh tng hp
biotrans t ngun nguyn liu du da, cc thng s ti u cho phn ng c

51

xc nh nh sau: t l mol methanol: du l 6:1, thi gian phn ng 90 pht, lng

xc tc bng 0,5% khi lng du nguyn liu, nhit phn ng l 600C.

3.3.1 Thnh phn ha hc ca sn phm v hiu sut phn ng

3.3.1.1. Thnh phn ca ha hc ca Bitrans
STT
1

Bng 3.7 Thnh phn ha hc trong biotrans

Thnh phn
%
Octanoic acid,metyl ester
7.54

Decanoic acid, methyl ester

10.7

Undecanoic acid, methyl ester

0.23

Dodecanoic acid, methyl ester

30.64

Tridecanoic acid,methyl ester

0.03

Metyl tetradecanoate

30.9

Decanoic acid,2-3dihydro,methyl ester

0.57

Pentadecanoic acid, methyl ester

0.1

Hexadecanoic acid,methyl ester

18.5

10

Glycerine

0.24

3.3.1.2. Hiu sut ca phn ng tng hp

Hiu sut s b ca phn ng c tnh theo cng thc:
H=
Khi lng mol trung bnh, Mtb, ca du da c tnh t phn t gam trung
bnh, M*, ca cc axit chnh trong thnh phn triglyxerit nh sau:
M*=
Mtb= 3M*-3 + 41
Vi m l hm lng i trong mu %.
Da vo cc cng thc trn ta tnh c M* v Mtb ca du da nguyn liu
Mtb= 684.77

52

Theo phng trnh phn ng to biotrans khi cho 1 mol ( 684,77 g) phn ng
vi methanol , nu chuyn ha hon ton thnh Biotrans th cho (689,77 g) .Nh
vy hiu sut chuyn ha thnh Biotrans tnh cho 50g nguyn liu du da l:
H=

3.3.3. Cc tnh cht ha l ca sn phm

Bng 3.8 Mt s tnh cht ha l ca du sn phm
Phng php
Ester tiu chun
Biotrans t du
Tnh cht
th(ASTM)
ASTM D3871
da
in tch nh
35
35
thng (kV)
Hm lng nc
Karl Fisher
200
200
( mg/kg)
Ch s
D974
0,6
0,285
acid(mgKOH/g)
Trc quan

D1524

Trong v sng

Trong v sng

T trng

D1298

0,96

0,912

im chp chy oC

D92

275

164

nht ( cSt)
40 oC

D445

50

2,9

im ng c oC

D97

-10

-8

53

CHNG 4: KT LUN V KIN NGH

4.1 Kt lun
Qua qu trnh nghin cu tng hp thu c nhng kt qu ph hp vi
tiu chun ASTM D3871 cho sn phm du bin th sinh hc tng hp t du thc
vt nh: in tch nh thng t 35kV,hm lng nc nh hn 200mg/l v mt
s ch tiu ha l t kt qu tt tng ng vi tiu chun.Du bin th sinh hc t
du da c th thay th du khong lm vic ti cc trm bin p phn xng hay
trm bin p phn phi: Nhn in p 35 KV 6 KV bin i thnh in p ra 0,4
KV 0,22 KV => y l trm bin p c dng trong mng h p dn dng ta
nh, thng thy l trm 0,22/0,4 KV.
Cc thng s ti u c tm ra cho phn ng tng hp du bin th sinh hc
nh sau:
Thi gian phn ng : 90 pht
Nhit phn ng : 60 oC
Lng xc tc: 0.5% (du + methanol)
T l du/methanol: 1/6
phn tch c thnh phn metyl ester sn phm bng phng php GCMS. Gii ph bit c cc thnh phn v tnh c hiu sut ca phn ng tng
hp du bin th sinh hc l: 90.38%

4.2 Kin ngh

Kt qu t c l mt trong nhng thnh cng ln i vi ti, ti ny c
ngha thc tin trong lnh vc sn xut ra ngun nguyn liu thn thin vi mi
trng gip gim thiu s ph thuc vaog ngun nguyn liu ha thch ang dn
cn kit. Do ti ny cn c m rng vi nhiu ngun nguyn khc tn
dng c cc ngun cht thi sinh hc c th ti ch s dng c.
Hng nghin cu v sau c th tip tc trin khai ti ny nhng cn kho
st thm cc iu kin tng hp xc tc c th tng hp c xc tc tng

54

hiu sut tng hp biotrans ng thi cng phi ti sinh c xc tc gim thiu
chi ph sn xut. Ngoi ra cng cn c thm thi gian chy th nghim cc mu
th nghim c iu ch trn cc my bin p nh gi chnh xc hn cc
thng s ha l ca biotrans tng hp c.

55

TI LIU THAM KHO

[1]. Khoa Cng Ngh Ha Hc, Gio trnh thc hnh phn tch cc sn phm du
kh, Nh xut bn i hc Cng nghip Thnh ph H Ch Minh, 14 18, 24
27, 47 -51, 75 80, 2011.
[2]. B mn Ha Du, Gio trnh thc hnh chuyn ngnh ha du 2, Nh xut bn
i hc Cng nghip Thnh ph H Ch Minh, 45 56, 2012.
[3]. Nguyn nh Thnh, C s cc phng php ph ng dng trong ha hc, Nh
xut bn Khoa hc v K thut, 111 112, 2010.
[4]. Wouter, M.J.A et al. (2010).

Towards domestication of Jatropha

curcas.Biofuels, 1(1), 91-107

[5]. Zaharaddeen Masiru Garba, Casimir Emmanuel Gimba, Paul Emmanuel,
Production and Characterisation of Biobased Tranformer oil from Jatropha
Curcus Seed,Journal of Pysical Science, Vol.24(2),49-61,2013
[6]. Y.Bentrand, L.C.Hoang, 2004, Vegetable oil as substitute for mineral
insulating oils in medium voltage equipment, Proceedings CIGRE conference,
Paris, No.D1-202
[7]. C.Perrier, A.Beroual, J-L.Bessede, 2006, Improvement of power transformers
by using mixture of mineraloil with synthetic esters. IEEE TDEI, No.3, Vol 13,
pp.556-564
[8]. D.C Abeysundara, C.Weerakoon, Lucas, J.R.Gunatunga, K.A.I, and Obadage,
K.C. Coconut oil as an alternative to transformer oil, ERU, Symposium Sri
Lanka, 2011, pp 1-11
[9]. T.V.Oommen Vegetable Oil for Liquid-Filled Transformer, IEEE electrical
Insulation Magazine, Vol.1, No.1, pp 7-11, 2002.
[10]. N.H.Thanh, N.T.T. Nguyen, N.T.P.Hoa. Dieu Che Biodiesel tu mo ca Basa
bang Phuong phap hoa sieu am, Tp ch pht trin KH&CN, Tp 12, s 32009, pp 51-61.

56

PH LC
100

61

74

100

74

100

O
O

OH
HO

50

OH

87

50

55

120
( re p lib ) G ly c e rin

100

55

127

127

158
158
0
50
100
150
50
100
150
( re p lib ) O c ta n o ic a c id , m e th y l e s te r ( re p lib ) O c ta n o ic a c id , m e th y l e s te r
0

240

74

74

100

74

100
O

87

50

87

50

87

50

50

55

55
143

143

143
0

0
0
170
340
70
140
210
70
140
210
( re p lib ) U n d e c a n o ic a c id , m e th y l e s te( rre p lib ) D o d e c a n o ic a c id , m e th y l e s te( rre p lib ) D o d e c a n o ic a c id , m e th y l e s te r

100

87

100

88

100

74

O
OH

50

O
O

50

50

158

143

55
183
0

185

0
0
160
320
190
380
160
320
( m a in lib ) 9 - H y d ro x y - d e c a n o ic a c id , m (erethp ylibl e) sDteo rd e c a n o ic a c id , e th y l e s te r ( m a in lib ) T rid e c a n o ic a c id , m e th y l e s te r

57

74

100

100
O

69

100

74

C16H 32O 2
O

87
N

HN
50

50

50

55
143

180

143 256

199
242
0

80
160
240
( m a in lib ) M e th y l te tra d e c a n o a te

100

74

0
220
440
220
440
( m a in lib ) D a s y c a rp id a n - 1 - m e th a n o l, a (cree ptalibte) P(ees ntetar)d e c a n o ic a c id , m e th y l e s te r
155

100
O
O

C 13H 26O 4
74
50

50

143
227
0

0
160
320
220
440
( m a in lib ) H e x a d e c a n o ic a c id , m e th y l (ems ateinr lib ) D e c a n o ic a c id , 2 , 3 - d ih y d ro x y p ro p y l e s te r

Heade
r=

Pea
k

11=

11

12=

12

13=

13

19=

19

20=

20

26=

26

31=

31

33=
36=

33
36

58

Firs Ma
Las
R.T.
t
x
t
4.68
4 702 736 789
5.08
6 789 800 815
5.23
9 815 824 923
8.74 133 138 142
9
1
6
5
9.01 142 142 148
6
5
8
4
11.0 171 175 184
28
4
0
2
13.7 212 218 236
48
1
5
7
14.9 237 238 242
89
8
3
8
15.6 246 248 250

PK
TY

Height

VV
VV
2
VV
4
PV
3
VV
2

805447
177168
62
175646
41
191204
57
172740
38

81328593
92246866
4
15838747
75
31576957
91
39960417
3

VV
VV
2
VV
4
VV

602259
202486
15
862746
0
189670

74924746
97357324
98
42907980
9
8381670

Area

Pct
Max
0.8
9.08
15.5
9
31.0
7
3.93
0.74
95.8
1
4.22
0.08

Pct
Total
0.22
2
2.51
3
4.31
5
8.60
3
1.08
9
0.20
4
26.5
25
1.16
9
0.02

39=

39

43=

43

52=

52

57=

57

59=

59

60=

60

61=

61

66=

66

67=

67

71=

71

74=

74

59

15
16.1
57
17.1
5
20.4
7
22.6
49
23.1
04
23.2
97
23.6
84
26.1
37
26.5
75
28.2
23
28.9
45

9
255
3
266
5
320
7
354
4
365
9
369
5
374
9
401
8
420
0
443
8
459
7

3
257
0
272
9
325
9
360
8
368
0
371
1
377
3
416
5
423
5
449
9
461
4

6
260
0
279
3
344
2
363
9
369
5
374
9
379
2
420
0
436
0
452
7
465
0

2
PV

518307
233657
9
209734
07
294882
4

22726235
11324265
1
10162018
264
17081594
2

0.22

330873

15560624

0.15

VV

313731

17040133

0.17

PV
PV
6
VV
3

747824

33333751

0.33

77649341
61503482
96
18990816
7

0.76
60.5
2

VV

467689
211234
61
306064
4

VV

851216

68752017

0.68

VV
VV
4
VV
VV
3

1.11
100
1.68

1.87

3
0.06
2
0.30
9
27.6
87
0.46
5
0.04
2
0.04
6
0.09
1
0.21
2
16.7
57
0.51
7
0.18
7

60

Ph lc 1: Kt qu gii ph GC-MS

Ph lc2. Kt qu xc nh in tch nh thng mu du da

61