Khao Sat Biodiesel

TRNG I HC B RA-VNG TU
KHOA HA HC V CNG NGH THC PHM

TRNG NGUYN PHNG TRANG

KHO ST QU TRNH TNG HP BIODIESEL T
DU N PH THI V METHANOL

N TT NGHIP I HC
Ngnh: CNG NGH K THUT HA HOC

Ngi hng dn
THS. NGUYN THANH THIN

B RA VNG TU, NM 2012

TRNG I HC B RA-VNG TU
KHOA HA HC V CNG NGH THC PHM

TRNG NGUYN PHNG TRANG

KHO ST QU TRNH TNG HP BIODIESEL T DU N
PH THI V METHANOL

N TT NGHIP I HC
Ngnh CNG NGH K THUT HA HOC

Ngi hng dn
THS. NGUYN THANH THIN

B RA VNG TU, NM 2012

CNG HO X HI CH NGHA VIT NAM
c lp - T do - Hnh phc
------o0o-----

NHIM V N TT NGHIP

H v tn sinh vin: Trng Nguyn Phng Trang
Ngy, thng, nm sinh: 03/09/1990
Ngnh: Cng ngh k thut Ha Hc
MSSV: 0852010191
Ni sinh: ng Nai
I. TN TI: Kho st qu trnh tng hp Biodiesel t du n ph thi v
methanol
II. NHIM V V NI DUNG:
Xc nh thnh phn v mt s ch tiu ca du n ph thi dng lm
nguyn liu.
Tin hnh kho st qu trnh tng hp Biodiesel qua hai giai on tm
ra cc thng s ti u cho cng nghip sn xut Biodiesel.
o cc ch tiu c bn ca Biodiesel thnh phm.
III. NGY GIAO NHIM V N: 28/03/2012
IV. NGY HON THNH NHIM V: 14/07/2012
V. H TN CN B HNG DN: Ths. Nguyn Thanh Thin

CN B HNG DN
B Ra Vng tu, Ngy 28 thng 07 nm 2012
SINH VIN THC HIN
(K v ghi r h tn) (K v ghi r h tn)

TRNG B MN TRNG KHOA
(K v ghi r h tn) (K v ghi r h tn)
TRNG H B RA VNG TU
KHOA HA HC & CNTP

i

M U

Hin nay, mi trng l vn ang c mi quc gia trn th gii quan tm.
nc ta, vn nhim mi trng ang tr thnh mi e ngi ln cho ton th
x hi, trong nhim khng kh l mt trong nhng dng nhim mi trng
c quan tm nhiu nht. nhim khng kh ch yu l do khi thi t cc nh
my, khu cng nghip v t cc phng tin giao thng. c bit, khi cc phng
tin giao thng ngy cng gia tng th nguy c thi ra mi trng cc cht c hi
cng tng theo. Cc phng tin giao thng mun hot ng cn phi c nhin
liu, trong c Diesel. Do vy, mun gim thiu kh thi gy nhim mi trng
th nhin liu cn phi t nhng yu cu cht lng cn thit. V th, vic nng
cao cht lng nhin liu v tm ra nhng nhin liu mi lm gim hm lng
kh thi ang ngy cng c ch trng nghin cu.
Trong nhng nm gn y, rt nhiu nc trn th gii quan tm n vic
sn xut ra cc loi nhin liu sch, ng ch nht l nhin liu sinh hc.
Biodiesel l mt dng nhin liu sinh hc c quan tm hn c do xu hng
Diesel ha ng c trn ton cu, v gi diesel khong ngy cng tng cao. Hn
na, biodiesel c xem l loi ph gia rt tt cho nhin liu diesel khong, lm
gim ng k lng kh thi c hi, v n l ngun nhin liu c th ti to c.
Vit Nam c nhiu ti nghin cu tng hp biodiesel t cc ngun
nguyn liu sn c trong nc nh du u nnh, du ht ci, du cao su, m
c,v thu c kt qu kh tt. Tuy nhin v nn cng nghip sn xut du
m nc ta cn kh non tr, cha p ng c ngun nguyn liu cho sn xut
biodiesel quy m ln. Ngoi ra, nu sn xut biodiesel t du n tinh ch th gi
thnh kh cao, v cn nh hng n an ninh lng thc. Do , vic tm kim
ngun nguyn liu r tin, ph hp vi iu kin ca t nc vn ang c tip
tc nghin cu. Vi mc ch ,
vic tn dng ngun du n ph thi v m c lm nguyn liu cho tng hp
biodiesel l c ngha thc t rt ln. Bi y l ngun nguyn liu c tr lng
tng i ln, li r tin, em li hiu qu kinh t cao. Vic tn dng ngun
nguyn liu ny cn gp phn bo v mi trng v sc khe ngi dn. Chnh v
ii

vy trong bi lun vn ny, ti xin c nghin cu ti Tng hp Biodiesel t
du n ph thi v Methanol nhm kho st cc yu t cn thit c th sn xut
Biodiesel t du n ph thi theo qui m cng nghip t hiu sut cao.

iii

LI CM N

Ti xin php c gi li cm n su sc n Ths. Nguyn Thanh Thin Gio
vin hng dn cho ti trong ln lm lun vn ny. Thy tn tnh hng dn, ch
bo ti c th hon thnh bi lun vn.
Ti cng xin cm n ton b cc thy c gio trong khoa Ha hc v Cng ngh
thc phm trng i hc B Ra-Vng Tu to iu kin cho ti c thc
nghim ti phng th nghim ha ca trng vi cc trang thit b y ti c
th hon thnh bi lun vn tt nghip ng thi gian quy nh.
Cui cng, ti xin c gi li cm n n cc bn b trong khoa Ha hc v
Cng ngh thc phm gip ti trong qu trnh lm bi lun vn ny.
Ti xin chn thnh cm n.

Vng Tu, ngy 3 thng 7 nm 2012
Sinh vin thc hin
Trng Nguyn Phng Trang

iv

v

MC LC
Trang
LI M U............................................................................................................i
LI CM N..........................................................................................................iii
MC LC................................................................................................................iv
DANH MC BNG...............................................................................................vii
DANH MC S .............................................................................................viii
DANH MC HNH.................................................................................................ix
T VIT TT.......................................................................................................... x

CHNG I: TNG QUAN L THUYT.............................................................1
I. NHIN LIU DIESEL.........................................................................................1
1. Khi qut v nhin liu diesel ..............................................................................1
2. Nhu cu s dng nhin liu..................................................................................1
3. Nhin liu diesel khong v vn nhim mi trng ....................................2
II.NHIN LIU SINH HC V BIODIESEL.......................................................4
1. Nhin liu sinh hc...............................................................................................4
2. Biodiese .................................................................................................................5
2.1. Lch s pht trin ca nhin liu biodiesel .......................................................5
2.2. Mt s c tnh ca biodiesel ............................................................................6
2.2.1. Sc cng b mt, nht v im vn c.......................................................6
2.2.2. n nh oxi ha...........................................................................................6
2.2.3. Ch s cetane....................................................................................................7
2.2.4. im chp chy................................................................................................7
2.2.5. Nhit si ......................................................................................................7
2.2.6. Trng lng ring.............................................................................................7
2.3.u, nhc im khi s dng Biodiesel ..............................................................8
2.3.1.u im.............................................................................................................8
vi

2.3.2. Nhc im......................................................................................................9
2.4. Tnh hnh nghin cu, sn xut v s dng biodiesel trn th gii v
Vit Nam................................................................................................................. 10
2.4.1. Trn th gii ................................................................................................... 10
2.4.2. Tnh hnh trong nc...................................................................................... 12
2.5. Nguyn liu sn xut Biodiesel ...........................................................13
a. Du n ph thi..................................................................................................... 13
b. Ru .................................................................................................................... 15
2.6. Phn loi cc phng php tng hp biodiesel .............................................. 16
2.6.1. Phng php sy nng.................................................................................... 16
2.6.2. Phng php pha long................................................................................... 17
2.6.3. Phng php Cracking ................................................................................... 17
2.6.4. Phng php nh tng ha ........................................................................... 18
2.6.5. Phng php ester ha.................................................................................... 18
a. C s ha hc....................................................................................................... 18
b. Cc phng php k thut iu ch ankyl ester................................................ 20
c. Xc tc s dng trong qu trnh ester ha............................................................. 21
d. Cc yu t nh hng n phn ng trao i este ................................................. 23

CHNG II: THC NGHIM............................................................................ 27
I. MC TIU NGHIN CU ............................................................................... 27
II. PHNG PHP NGHIN CU..................................................................... 27
III. THC NGHIM............................................................................................. 27
1. Thit b phn ng ............................................................................................... 27
2. Chun b nguyn liu.......................................................................................... 28
3. Kho st nguyn liu du................................................................................... 28
4. Xc nh cc ch s c bn ca nguyn liu du ............................................... 28
4.1. Cch xc nh nht ....................................................................................... 28
vii

4.2. Cch xc nh ch s axit ................................................................................... 29
5. Kh nc trong du n trc khi phn ng..................................................... 29
6. Kho st qu trnh tng hp biodiesel t du n ph thi ............................... 30
6.1. Thc hin phn ng giai on 1......................................................................... 30
6.2. Thc hin phn ng giai on 2......................................................................... 33

CHNG III: KT QU V BN LUN.......................................................... 35
I. KHO ST NGUYN LIU............................................................................ 35
II. KHO ST HM LNG METHYLESTER TRONG HN HP GIA
DU NGUYN LIU V METHYLESTER N NHT NG HC.... 36
III. KHO ST NH HNG CA CC YU T.......................................... 38
1. Giai on 1.......................................................................................................... 38
1.1. nh hng ca thi gian n nht v ch s axit........................................... 38
1.2. nh hng ca nhit n nht v ch s axit .......................................... 40
1.3. nh hng ca t l Methanol/du n nht v ch s axit (theo th tch)..... 41
1.4. nh hng ca hm lng xc tc n nht v ch s axit............................ 42
2. Giai on 2.......................................................................................................... 43
2.1. nh hng ca thi gian n hiu sut tng hp Biodiesel................................ 43
2.2. nh hng ca nhit n hiu sut tng hp Biodiesel ................................. 44
2.3. nh hng ca t l Methanol/bn sn phm n hiu sut tng hp Biodiesel. 45
2.4. nh hng ca hm lng xc tc n hiu sut tng hp Biodiesel................. 47
IV. XC NH CC CH TIU CHT LNG SN PHM.......................... 48

CHNG IV: KT LUN.................................................................................... 49
I. KT LUN......................................................................................................... 49
II. HNG TIP TC NGHIN CU................................................................ 50
DANH MC TI LIU THAM KHO............................................................... 52

viii

DANH MC BNG
Trang
Bng 1.1: D bo nhu cu nhin liu xng du n nm 2020....................................2
Bng 1.2. Sn lng Biodiesel cc nc Chu u nm 2004................................. 11
Bng 3.1. Kt qu kim nghim................................................................................ 35
Bng 3.2. nh hng ca hm lng Methylester n nht ca hn hp.................
Methylester v du nguyn liu ................................................................................ 36
Bng 3.3. nh hng ca nht v ch s axit theo thi gian ................................ 38
Bng 3.4. nh hng ca nht v ch s axit theo nhit .................................. 40
Bng 3.5. nh hng ca nht v ch s axit theo t l Methanol/du................. 41
Bng 3.6. nh hng ca nht v ch s axit theo hm lng xc tc ................. 42
Bng 3.7. Bng kt qu kho st thi gian................................................................ 43
Bng 3.8. Bng kt qu kho st nhit ................................................................. 44
Bng 3.9. Bng kt qu kho st t l ....................................................................... 45
Bng 3.10. Bng kt qu kho st lng xc tc....................................................... 47
Bng 3.11. Bng so snh ch tiu cht lng ca biodiesel sn phm vi biodiesel.......
chun theo tiu chun ASTM 6751-02..................................................................... 48

ix

DANH MC S
Trang
S 3.1. nh hng ca hm lng Methylester n nht ca hn hp................
Methylester v du nguyn liu ................................................................................ 38
S 3.2. S ph thuc ca nht theo thi gian .................................................. 39
S 3.3. S ph thuc ca ch s axit theo thi gian.............................................. 39
S 3.4. S ph thuc ca nht theo nhit ................................................... 40
S 3.5.S ph thuc ca ch s axit theo nhit ............................................... 40
S 3.6. S ph thuc ca nht vo t l Methanol/du.................................... 41
S 3.7. S ph thuc ca ch s axit vo t l Methanol/du................................ 41
S 3.8. S ph thuc ca nht vo hm lng xc tc .................................... 42
S 3.9. S ph thuc ca ch s axit vo hm lng xc tc ................................ 42
S 3.10. nh hng ca thi gian phn ng n hiu sut................................... 43
S 3.11. nh hng ca nhit phn ng n hiu sut.................................... 44
S 3.12. nh hng ca t l Methanol/bn sn phm n hiu sut ................... 46
S 3.13. nh hng ca lng xc tc n hiu sut........................................... 47

x

DANH MC HNH

Trang
Hnh 1.1. Qu trnh hydrocraking du thc vt......................................................... 17
Hnh 2.1. S thit b phn ng............................................................................. 27
Hnh 2.2. Thao tc kh nc trong du nguyn liu ................................................. 30
Hnh 2.3. Thit b s dng tin hnh phn ng ......................................................... 31
Hnh 2.4. Phu chit ................................................................................................. 32
Hnh 4.1. Bn sn phm sau giai on 1 ................................................................... 49
Hnh 4.2. S phn pha sau giai on 2...................................................................... 50
Hnh 4.3. Biodiesel sn phm sau khi sy, lc .......................................................... 50

xi

T VIT TT

EU : European Union (Khi lin minh Chu u)
ASTM : American Society for Testing and Materials (Hip hi M v
kim nghim v vt liu)
TBHQ : Tert-ButylHydroQinone
HFRR : High-frequency receiprocating rig (Tn s qua li thit b)
B5 : Biodiesel 5%
B20 : Biodiesel 20%

n tt nghip i hc-Kha 2008 2012 Trng HBRVT

Ngnh Cng ngh k thut ha hc - 1 - Khoa Ha hc v Cng ngh thc phm
CHNG I
TNG QUAN L THUYT
I. NHIN LIU DIESEL
1. Khi qut v nhin liu diesel
Diesel l mt loi nhin liu lng c ngun gc t du m. Thng th diesel l
phn on du m c nhit si t 250 n 350
o
C, cha cc hydrocacbon c s
cacbon t C
16
n C
20
, C
21
, vi thnh phn ch yu l n-parafin, iso-parafin v mt
lng nh hydrocacbon thm, trong c mt s hp cht phi hydrocacbon (hp cht
cha N, O, S). Phn on ny c dng lm nhin liu cho mt loi ng c t
trong t bt chy do nh bc hc Rudolf Diesel sng ch, nn gi l nhin liu diesel.
[2]
2. Nhu cu s dng nhin liu
Ngy nay cng vi s gia tng dn s mnh m v nhp pht trin kinh t ngy
cng tng cao, ko theo nhu cu s dng cc ngun nhin liu ngy cng nhiu
phc v cc lnh vc khc nhau. Khi lng nhin liu s dng n nm 2020 d on
t ti 13.6 t tn du quy i, gp 1.5 ln so vi 9.1 t tn nm 2000.
Nhin liu ha thch (than , du v kh t nhin) c d on l ng gp ti
90% trong mc tng s tiu th nng lng ni trn, v v th n tip tc ng vai tr
quan trng trong cc dng nng lng. S tiu th du m d bo l ln nht trong cc
dng nhin liu ha thch, c tnh khong 35% trong tng mc tiu th nng lng
ch yu, tip sau l kh t nhin 30% v than l 26%. Mc tiu th du m c
d on tng t 70 triu thng/ngy trong nm 2000 n 102 triu thng/ngy vo nm
2020, tc tng trung bnh hng nm khong 1.9%. Trong , Chu gp phn tng
50% mc tiu th trn v s dng nhiu nht l lnh vc giao thng vn ti (chim
60%).
i vi nc ta l mt nc ang pht trin, nhp pht trin kinh t - x hi ngy
cng tng, v vy nhu cu v nng lng s tng mnh trong thi gian ti. D bo t l
nhp khu nng lng nc ta n nm 2020 khong 11 20%, v tng ln 50
58% vo nm 2050. Ring ngun du m, theo thng k ca Tng cng ty Xng du

Vit Nam (Petrolimex) vo nm 2004, th mc tiu th xng du ca c nc khong
13.5 triu tn. D bo nhu cu tiu th xng du Vit nam s tng mnh trong giai
on 2005 2020. S liu c th bng 1.1.
Bng 1.1: D bo nhu cu nhin liu xng du n nm 2020
n v: Nghn tn
Sn phm 2005 2010 2015 2020
Gasoline 2.829 4.156 5.090 6.024
Diesel 5.800 8.740 11.140 13.024
Kerosen 440 420 392 360
Nhin liu JA1 419 615 844 1.023
Du FO 2.878 3.665 4.350 5.089
Tng s nhin liu 12.362 17.596 21.816 26.036
Tng s xng diesel 8.629 12.896 16.230 19.564
(Ngun: Vin chin lc pht trin - B K hoch u t)
T bng s liu trn ta thy, trong cc loi nhin liu th diesel l loi nhin liu
c tiu th nhiu nht. iu ny cho thy diesel c tm quan trng rt ln. Do
vic tm cch nng cao cht lng diesel, cng nh tm kim ngun nhin liu thay th
diesel khong ang ngy cng cn kit v thiu ht l ht sc cn thit. [5]
3. Nhin liu diesel khong v vn nhim mi trng
Cc thnh phn phi hydrocacbon trong nhin liu diesel khong, nh cc hp cht
cha lu hunh, nit, nha, asphantenkh cao. Cc thnh phn ny khng nhng
khng tt cho ng c, m cn gy nhim mi trng. Cc loi kh thi ch yu l
SO
2
, NO
x
, CO, CO
2
, hydrocacbon, vt cht dng ht
Kh SO
2
khng nhng gy n mn ng c m cn nh hng n sc khe ca con
ngi, gy ma axit
Kh CO
2
l nguyn nhn gy ra hiu ng nh knh.

Kh CO rt c, vi lng CO khong 70 ppm c th gy ra cc triu chng nh
au u, mt mi, bun nn. Lng CO khong 150 - 200 ppm gy bt tnh, mt tr
nh v c th gy cht ngi.
Cc thnh phn hydrocacbon trong kh thi ca nhin liu diesel c bit l cc hp
cht thm rt c hi cho con ngi, l nguyn nhn gy ra cc bnh v ung th.
Kh thi diesel cha cc phn t c kch thc rt nh v cc kh d chy c th i
vo su bn trong phi. Cc nghin cu trc y chng minh c s lin h gia
cc thnh phn hu c trong kh thi diesel vi d ng, vim ng h hp v bin i
chc nng ng h hp. Nguy c tc nghn phi mn tnh (COPD) gia tng 2.5%
mi nm cc cng nhn b phi nhim trc tip vi khi diesel.
Nh vy, cng vi nhng li ch to ln ca nhin liu diesel khong, th n li gy
ra tc ng xu n mi trng sng v sc khe con ngi. Chnh v vy m vn
t ra l phi tm gii php nng cao cht lng nhin liu diesel, nng cao nng
sut thit b, tui th ng c, cng nh bo v mi trng sinh thi. Hin nay th c
bn phng php nng cp cht lng nhin liu diesel:
- Phng php pha trn: pha trn gia nhin liu diesel sch vi nhin liu diesel
km sch thu c nhin liu diesel m bo cht lng. Phng php ny c hiu
qu kinh t kh cao, c th pha trn vi cc t l khc nhau c nhin liu diesel tho
mn yu cu. Tuy nhin, du m trn th gii ch yu l du c cha nhiu hp cht
phi hydrocacbon (du khng sch) nn phng php ny cng khng phi l kh thi.
- Phng php hydro ho lm sch: phng php ny c u vit l hiu qu lm
sch rt cao. Tuy nhin phng php ny t c la chn v vn u t kh cao,
khong 60 - 80 triu USD cho mt phn xng hydro ho.
- Phng php nh ho nguyn liu diesel: ngi ta a nc vo nhin liu diesel
v to thnh dng nh tng. Loi nhin liu ny c nng oxy cao nn qu trnh
chy sch hn. Phng php ny nu thc hin c th khng nhng gim c
nhim mi trng m cn c gi tr kinh t cao. Tuy nhin, hin ti phng php ny
vn cn ang nghin cu, cha c ng dng thc t.

- Dng kt hp vi biodiesel: biodiesel l methylester ca cc axit bo. Dng nhin
liu ny c nng oxy cao hn, t tp cht, v vy qu trnh chy sch, t to cn,
khi thi t c hi. Biodiesel c xem l loi ph gia rt tt cho diesel khong, n c
th trn ln vi diesel khong theo mi t l.
Trong bn phng php trn th s dng biodiesel l phng php c nhiu
nc quan tm v tp trung nghin cu nhiu nht. Bi biodiesel c sn xut t
ngun nguyn liu sinh hc, l mt ngun nguyn liu v tn, ti to c, d phn
hu, khng gy nhim mi trng. Hn na khi trn diesel vi biodiesel th sn
phm chy cha rt t cc kh thi c hi nh CO
x
, SO
x
, H
2
S, hydrocacbon thm. [5,
7]
II.NHIN LIU SINH HC V BIODIESEL
1. Nhin liu sinh hc
Nhin liu sinh hc (biofuel) l loi nhin liu c sn xut t ngun nguyn liu
sinh hc sinh khi nh du thc vt, m ng vt, tinh bt, thm ch l cht thi
nng nghip, lm nghip (rm r, b ma, tru, mn ca, phn chung). y l
ngun nhin liu sch (cht thi t c hi) v c bit l ngun nhin liu c th ti
to c (renewable fuel) nn n lm gim s ph thuc vo ngun ti nguyn nhin
liu khong vn c hn. Chnh hai c im ni bt ny m nhin liu sinh hc l s
la chn ca nhiu nc trn th gii hin nay v c trong tng lai.
Nhin liu sinh hc c nhiu loi nh xng sinh hc (biogasoil), diesel sinh hc
(biodiesel), v kh sinh hc (biogas) - loi kh c to thnh do s phn hy ym kh
cc cht thi nng nghip, chn nui v lm nghip. Trong cc dng trn th ch c
biogasoil v biodiesel c quan tm nghin cu, sn xut v ng dng trong quy m
cng nghip.
Mt s nc t ra mc tiu thay th dn nguyn liu truyn thng sang nhin
liu sinh khi. M t ra mc tiu thay th khong 30% lng xng tiu th bng cc
sn phm c ngun gc t sinh khi vo nm 2025. n t mc tiu tng dn s
dng nhin liu sinh khi t 5% ln 20% vo nm 2012. EU t ra th phn nhin liu
sinh hc chim 6% trong tng nhin liu tiu th. Braxin l nc ang ng u th

gii v nhin liu sinh hc vi nhin liu sn xut t sinh khi chim ti 30% trong
tng nhin liu ang s dng cho ngnh giao thng vn ti. [1]

2. Biodiesel
2.1. Lch s pht trin ca nhin liu biodiesel
Biodiesel hay diesel sinh hc l mt loi nhin liu c ngun gc t du thc vt
hay m ng vt, c ch tiu k thut gn ging vi diesel khong. V bn cht ha
hc n l ankylester ca cc axit bo. Biodiesel c xem l mt loi ph gia rt tt
cho diesel truyn thng.
Cch y hn 100 nm, nh pht minh Rudolf Diesel pht minh ra ng c chy
bng du thc vt. Vo nhng nm 1930 v 1940, du thc vt c s dng nh l
nhin liu diesel nhng ch c s dng trong tnh trng khn cp. Bt u t nm
1980, c nhiu cuc tranh ci ln v vic s dng du thc vt lm mt nhin liu.
Cng vo nm 1980, Caterpilla Brazil s dng hn hp 10% du thc vt cho ng
c diesel m khng c s thay i cng nh thay th g. Ti thi im ny, cha c
mt thc hnh no s dng 100% du thc vt thay th cho nhin liu diesel, nhng
hn hp pha trn 20% du thc vt vi 80% du diesel mang li thnh cng rc r.
Mt thi gian ngn sau , ngi ta tin hnh th nghim n t l 50/50.
Thng 8 nm 1982, hi ngh u tin ca th gii v vic s dng du thc vt nh
l nhin liu c din ra ti Fargo, pha nam Dakota. Nm 1982 l nm ng c
ghi nhn v y cng chnh l nm bt u d dng du n ph thi, cng l thi im
Vin Ha Hu C ca Graz (o) u tin s dng ester ca du ht ci.
Nm 1985, th im u tin trn th gii sn xut methylester du ht ci c
thc hin ti trng Nng Nghip Silberberg, Styria (o).

Nm 1987, th nghim trn ng c o hm lng khi thi ca methylester du
n ph thi c tin hnh ti AVL List Gmble, Graz.
Trong nhng nm 1989 1990, d n u t ca chnh ph o v Sn xut
biodiesel cht lng cao t du n ph thi c thc hin.
Nm 1994, biodiesel t du n ph thi c bt u a vo sn xut cng
nghip ti Mureck, o.
Nm 1995, thnh cng trong vic sn xut methylester vi hiu sut 100%
c cng b.
Nm 1998, d n sn xut biodiesel t ngun nguyn liu m ng vt cha 20%
hm lng axt bo c thnh lp.
n nm 2003, c 4 quy trnh tin tin cho vic sn xut biodiesel t du thc vt
v du n ph thi c cng b. [1, 4]
2.2. Mt s c tnh ca biodiesel
Biodiesel l mt ngun nhin liu thay th cho xng v diesel. S ni ln ca nhin liu
thay th biodiesel a n nhng nghin cu v c tnh ca n. Nhng c tnh l:
2.2.1. Sc cng b mt, nht v im vn c
Ch tiu k thut ca ASTMD-445 v nht ca biodiesel 40
o
C l 4
centistokes (n v nht ng hc). Tuy nhin, nht ca biodiesel v hn hp
pha trn ca n cao hn diesel. Biodiesel t du u nnh c bo co l c nht
trong khong 3.8 4.1 centistokes 40
o
C. S ln tp glycerine s lm tng nht.
nh gi sc cng b mt ca biodiesel cho thy rng n hn diesel 2 n 3 ln.
nht cao hn v im vn c l mt vn chnh ca vic s dng biodiesel trong
ng c diesel. nht ca du thc vt v m ng vt cao c khuynh hng gy ra
nhng vn khi trc tip s dng trong ng c diesel. Do nht v sc cng b
mt cao lm cho git nhin liu cng ln hn, iu ny gy ra nguyn nhn lm cho n
thi ra ngoi nhiu hn. Nu chuyn ha ester du v m bng alcohol chui ngn th
nht v sc cng b mt ca monoester to ra gn bng vi diesel du ha.
2.2.2. n nh oxi ha

L mt vn k ngh chnh i vi nhin liu diesel v biodiesel. bn oxi
ha c o bng tiu chun ASTM D2274. So vi diesel, biodiesel d b oxi ha hn.
bo ha chui acid bo tng quan vi bn ca n. Cc yu t chi phi s n
nh l s hin din ca khng kh, nhit, du vt kim loi, peroxide, hoc c tnh
cu trc phc hp ca chnh n, ch yu l s hin din ca ni i. Nghin cu n
nh trn methyl v ethyl ester ca du hoa hng dng a ra nhn nh rng lu
tr biodiesel trong iu kin kn hi, nhit thp hn 30
o
C, s dng thng cha bng
thp khng g v tert-butylhydroqinone (TBHQ), mt cht c ch oxi ha, c tc dng
c ch cho bn oxi ha ca biodiesel. Hai yu t, nhit v bn cht ca thng
cha tc ng n bn, c khng nh l c nh hng ln nht n bn lu
tr ca biodiesel. Nhit cao s phn hy nhng hydroperoxide t l nhanh hn
khi n c lu tr nhit phng.
2.2.3. Ch s cetane
Ch s cetane l ch s thng c s dng rng ri cho cht lng nhin liu
diesel, n lin quan n thi gian tr hon s mi la v cht lng chy. Ch s cetane
ca biodiesel cao hn diesel du ha, iu ny cho thy tim nng cho ng c cao
hn. Ch s cetane ca nhin liu, c nh r bi tiu chun ASTM D-613, n l
n v o lng cht lng mi la. Ch s cetane ca biodiesel cao hn diesel thng
thng. Ch s cetane tng theo di chui carbon, gim theo s lng v v tr ca
ni i v thay i theo v tr khc nhau ca nhm carbonyl. Khi nhng lin kt v
carbonyl di chuyn ti pha trung tm ca chui, ch s cetane gim. Ch s cetane
tng t 47.9 n 75.6 khi s lng carbon trong acid bo trong biodiesel tng. Khi s
carbon trong chui acid bo vt qu 12 C, ch s cetane vt qu 60. Ni chung, ch
s cetane i vi hn hp pha trn ca biodiesel v diesel thng thng l mt hm s
tuyn tnh bng vi trung bnh ch s cetane ca cc nhin liu.
2.2.4. im chp chy
im chp chy, c xc nh bi tiu chun ASTMD-93, l mt n v o lng
nhit i vi mt nhin liu phi c un nng n khi hn hp hi v kh bn trn
nhin liu c th b bc chy. Nhng nhin liu diesel thng thng c im chp chy
cao (nh nht 54
o
C; c trng l 71
o
C). im chp chy ca biodiesel nguyn cht ln
hn 93
o
C. T trin vng lu tr v ri ro pht ha, biodiesel an ton hn diesel nhiu.

2.2.5. Nhit si
Nhin liu biodiesel c mt khong nhng im si hp t 327
o
C n 346
o
C.
2.2.6. Trng lng ring
Trng lng ring c xc nh bi ASTMD-287. Diesel c trng lng ring
l 0.85. Trng lng ring ca biodiesel c bo co bin thin gia 0.86 n 0.90,
n ph thuc vo nguyn liu c s dng. Trng lng trung bnh nhng methyl
ester t du u nnh c bo co l 0.85. [1]

2.3. u, nhc im khi s dng Biodiesel
2.3.1.u im
Biodiesel c xem l loi ph gia rt tt cho diesel khong, n c th trn ln
vi diesel khong theo mi t l.
- Tr s cetane cao
Biodiesel l cc alkylester mch thng nn c tr s cetanecao hn hn diesel
khong. Nhin liu diesel khong thng c tr s cetane t 50 n 52 v 53 n 54
i vi ng c cao tc, trong khi vi biodiesel thng l 56 n 58. Nh vy
biodiesel hon ton c th p ng yu cu v tr s cetane m khng cn ph gia,
thm ch n cn c dng nh ph gia tng tr s cetane cho diesel khong.
- Gim lng cc kh pht thi c hi
Biodiesel cha rt t hydrocacbon thm. Hm lng lu hunh rt thp, khong
0,001% . c tnh ny ca biodiesel rt tt cho qu trnh s dng lm nhin liu, v n
lm gim ng k kh thi SO
x
gy n mn thit b v gy nhim mi trng. ng
thi, trong nhin liu biodiesel cha khong 11% oxy nn qu trnh chy ca nhin
liu xy ra hon ton, gim c lng hydrocacbon trong kh thi. Vi biodiesel kh
thi khng c SO
2
, CO
2
v gim 20% kh CO, v cn c nhiu kh O
2
t do. Do s
dng nhin liu biodiesel s rt c li cho mi trng v gim nguy c b bnh ung th
do ht phi khi thi c hi.

- Kh nng bi trn cao nn gim mi mn
Biodiesel c kh nng bi trn bn trong tt hn diesel khong. Kh nng bi
trn ca nhin liu c c trng bi gi tr HFRR (high-frequency receiprocating
rig). Ni chung, gi tr HFRR cng thp th kh nng bi trn ca nhin liu cng tt.
Diesel khong x l lu hunh c gi tr HFRR 500 khi khng c ph gia, nhng
gii hn c trng ca diesel l 450. V vy, diesel khong yu cu phi c ph gia
tng kh nng bi trn. Ngc li, gi tr HFRR ca biodiesel khong 200. V vy,
biodiesel cn nh l mt ph gia rt tt i vi nhin liu diesel thng thng.

- C kh nng phn hy sinh hc
Biodiesel c kh nng phn hy rt nhanh (phn hy n hn 98% ch trong 21
ngy) nn rt tt cho mi trng. Tuy nhin, s thun li ny yu cu s ch c bit
v qu trnh bo qun nhin liu.
- Kh nng thch hp cho ma ng
Biodiesel rt ph hp cho iu kin s dng vo ma ng, n c th lm vic
c nhit -20
o
C.
- An ton v chy n tt hn
Biodiesel c nhit chp chy cao (trn 110
o
C) nn an ton hn trong tn tr
v vn chuyn.
2.3.2. Nhc im
Tuy biodiesel c th trn ln vi diesel khong theo mi t l nhng mt iu rt
ng ch l phi pha trn vi diesel khong, ch khng th s dng 100% biodiesel.
V nu s dng nhin liu 100% biodiesel trn ng c diesel s ny sinh mt s vn
lin quan n kt cu v tui th ng c. Hin nay ngi ta thng s dng hn
hp 5% v 20% biodiesel (k hiu B5, B20), chy ng c.
- Gi thnh kh cao

Biodiesel thu c t du thc vt t hn so vi nhin liu diesel thng
thng. Tuy nhin, trong qu trnh sn xut biodiesel c th to ra sn phm ph l
glyxerin, l mt cht c tim nng thng mi ln v c nhiu ng dng trong cng
nghip sn xut m phm, dc phm, kem nh rng, mc vit,... nn c th b li
phn no gi c cao ca biodiesel.
- D phn hy sinh hc
Biodiesel d phn hy gp 4 ln diesel khong v n vn cn cha cc axit khng
no. Do vn bo qun tn cha phi c quan tm.

- C th gy nhim
Nu qu trnh sn xut biodiesel khng m bo, chng hn ra biodiesel khng
sch th khi s dng vn gy ra cc vn v nhim do vn cn x phng, kim d,
metanol, glyxerin t docng l nhng cht gy nhim. [1, 4, 5]
2.4. Tnh hnh nghin cu, sn xut v s dng biodiesel trn th gii v Vit
Nam
2.4.1. Trn th gii
Nm 1900, khi pht minh ra ng c diesel, nh bc hc Rudolf Diesel dng
du lc th nghim. Mc d lc du thc vt cha tht s c quan tm, nhng
ng c mt nhn xt nh li tin tri v ngun nhin liu sinh hc ny: Ngy nay
vic s dng du thc vt lm nhin liu cho ng c c th cha c quan tm ng
mc, nhng trong tng lai du thc vt s tr nn quan trng nh vai tr ca sn
phm du m v than hin nay. V thc t sau gn 100 nm, khi m cc ngun
nhin liu ha thch ngy cng cn kit, gi du m ngy cng t , v nhng yu
cu ngy cng kht khe hn v mi trng, th ngi ta li ch nhiu hn n ngun
nhin liu t du thc vt, m ng vt.
Vic s dng trc tip du m ng thc vt lm nhin liu c nhiu nhc
im nh: nht ln (gp 11 17 ln so vi diesel du m), bay hi rt thp dn
n qu trnh chy khng hon ton, to cn trong vi phun, ngn cn qu trnh phun,

lm tc vi phun, lm c du nhn do ln du thc vt,...Cc vn ny l do phn t
triglyxerit vi kch thc v phn t lng ln trong du m gy ra. Do vy, ngi ta
phi tm cch khc phc cc nhc im , v to biodiesel l mt trong nhng gii
php tt.
Vo nhng nm 1980, biodiesel bt u c nghin cu v s dng mt s
nc tin tin. n nay, biodiesel c nghin cu v s dng rng ri nhiu
nc trn th gii. Hin nay c hn 28 quc gia tham gia nghin cu, sn xut v s
dng biodiesel. Cc nh my sn xut ch yu nm chu u v chu M. Ti M,
hu ht lng biodiesel c sn xut t du nnh. Biodiesel c pha trn vi diesel
du m vi t l 20% biodiesel v 80% diesel, dng lm nhin liu cho cc xe but
a n hc sinh rt nhiu thnh ph ca M. Hng nm, M bn ra gn hai t
gallon biodiesel. Ti Php, hu ht nhin liu diesel c pha trn vi 5% biodiesel.
Trn 50% ngi dn Php c xe vi ng c diesel s dng nhin liu pha
biodiesel. Hn 4000 phng tin giao thng s dng nhin liu B30, chy hn 200
triu km m khng h c mt hng hc no lin quan n s vn hnh ca ng c.
Theo thng k, th lng biodiesel tiu th trn th trng Php tng mnh trong
nhng nm gn y, nm 2004 tiu th 387 ngn tn, nhng n nm 2008 ln n
gn 1 triu tn. Nm 1991, c bt u a ra chng trnh pht trin biodiesel, n
nm 1995 bt u trin khai d n ny. Nm 2000 ti c c 13 nh my sn
xut biodiesel vi tng cng sut l 1 triu tn/nm. V thng 1 nm 2005, Nh nc
c ban hnh sc lnh buc phi pha biodiesel vo diesel du m theo t l 5%. C
th tham kho sn lng biodiesel ca mt s nc chu u bng 1.2.
Bng 1.2. Sn lng Biodiesel cc nc chu u nm 2004
Nc Sn lng (tn)
c 1.088.000
Php 502.000
Italia 419.000
o 100.000
Ty Ban Nha 70.000
an Mch 44.000

Anh 15.000
Thy in 8.000
Tng lng 2.246.000

Khng ch c chu u, M m chu , chnh ph nhiu nc cng quan
tm rt nhiu n vic pht trin ngun nhin liu sinh hc ni chung v biodiesel ni
ring. Malaysia v Indonesia l hai nc xut khu du c ln nht th gii, xy
dng chin lc m rng th trng sn xut p ng th trng du n v cung cp
nguyn liu cho sn xut biodiesel. Mc d hin nay tr lng du c Malaysia
t mc k lc nhng gi du c th ca nc ny vn tng cao, do nhu cu sn xut
biodiesel trn th gii vn tng cao. y ban du c Malaysia (MPOB) cho bit, t nay
n nm 2015 s c 5 nh my sn xut biodiesel t du c vi tng cng sut gn 1
triu tn p ng nhu cu tiu dng trong nc, v xut khu sang chu u.
Indonesia, ngoi du c cn u t trng 19 triu ha cy J.Curcas ly du lm nhin
liu sinh hc, v phn u n nm 2015 s dng nhin liu B5 cho c nc. Trung
Quc, nc nhp khu nhin liu ln nht th gii khuyn khch s dng nhin liu
sinh hc. Ti Thi Lan, B Nng lng sn sng h tr s dng du c trn phm vi
ton quc. Hin nay B ny ang hon tt cc th tc h tr pht trin biodiesel nhm
xy dng ngun nng lng cho t nc. Thi Lan d kin s dng diesel pha 5%
biodiesel trn ton quc vo nm 2011 v pha 10% biodiesel vo nm 2012. Ngay ti
Lo cng ang xy dng nh my sn xut biodiesel ngoi th Vin Chn. Mt
s nc chu Phi cng ang tip cn n nhin liu sinh hc.
2.4.2. Tnh hnh trong nc
Trc s pht trin mnh m ngun nhin liu sinh hc ni chung v biodiesel
ni ring trn th gii, cc nh khoa hc Vit Nam cng bt tay vo nghin cu v
sn xut biodiesel phng th nghim v quy m sn xut nh. Vic sn xut biodiesel
nc ta c nhiu thun li, v nc ta l mt nc nng nghip, thi tit li thun li
pht trin cc loi cy cho nhiu du nh vng, lc, ci, u nnh,...Tuy nhin
ngnh cng nghip sn xut du thc vt nc ta vn cn rt non tr, tr lng thp,
gi thnh cao. Bn cnh , ngun m ng vt cng l mt ngun nguyn liu tt
sn xut biodiesel, gi thnh m ng vt li r hn du thc vt rt nhiu. Mt vi

doanh nghip Cn Th, An Giang thnh cng trong vic sn xut biodiesel t m
c basa. Theo tnh ton ca cc cng ty ny th biodiesel sn xut t m c c gi
thnh khong 7000 ng/lt (nm 2005). Cng ty TNHH Minh T cng u t xy
dng dy chuyn sn xut t ng hon ton v khp kn, vi tng u t gn 12 t
ng, v k hp ng xut khu biodiesel sang Campuchia. Ngoi ra, mt s vin
nghin cu v trng i hc nc ta, cng c nhng thnh cng trong vic
nghin cu sn xut biodiesel t nhiu ngun nguyn liu khc nhau nh du c, du
da, du bng, du ht ci, du nnh, du ht cao su, du n thi, m c,...s dng xc
tc baz ng th v bc u nghin cu vi xc tc baz d th, xc tc zeolit.
Khng ch c cc nh khoa hc quan tm, m cc nh qun l Vit Nam cng
rt quan tm n ngun nhin liu sinh hc ny. n Pht trin nhin liu sinh hc
n nm 2015, tm nhn 2020 do B Cng nghip ch tr c chnh ph ph
duyt i vo hot ng. Ngoi vic pht trin nhin liu xng pha cn, n cn
cp n vic pht trin nhin liu diesel pha vi methyester du m ng thc vt
(biodiesel), vi mc tiu n nm 2010 nc ta s lm ch c cng ngh sn xut
biodiesel t cc ngun nguyn liu sn c trong nc, v bc u tin hnh pha trn
hn hp B5. Bn cnh , B Khoa hc v Cng ngh, Tng cc Tiu chun o lng
cht lng cng rt quan tm n vn nhin liu sinh hc, v t chc hi ngh
khoa hc v ethanol v biodiesel. Qua hi ngh, lnh o Tng cc c kin ngh v
vic sm xy dng v trin khai mt n nghin cu c nh hng tiu chun v
nhin liu sinh hc Vit Nam, trong c tiu chun cho nhin liu biodiesel. Vo
u nm 2009, Trng i hc Bch Khoa H Ni cng t chc Hi ngh quc t
v nhin liu sinh hc. Hi ngh thu ht c s tham gia ca nhiu nc nh
Php, Thi Lan, n ,... v cc trng i hc ln nc ta. Hi ngh c nhiu
bo co khoa hc v ethanol sinh hc v biodiesel, vi s ch theo di v tho lun
si ni ca nhiu nh khoa hc u ngnh. iu ny cng cho thy s quan tm c
bit ca cc nh khoa hc trong nc v quc t v nhin liu sinh hc. [5]
2.5. Nguyn liu sn xut Biodiesel
Biodiesel c th c sn xut t nhiu ngun nguyn liu khc nhau nh cc
loi du thc vt, m ng vt. Tuy nhin vic la chn nguyn liu phi da theo tiu

ch r tin, d kim, sn lng ln, c th sn xut d dng, khng c gi tr thc phm
m bo an ninh lng thc trong nc.
Theo cc tiu ch trn th ngun nguyn liu ch yu c nghin cu nc ta
hin nay l du ht cao su, du thng, du ht ci, m c tra, c basa, to bin. Gn
y ngun nguyn liu du n ph thi t cc nh hng, qun n, nh my ch bin
thc phmcng c nhiu nh khoa hc quan tm nghin cu.
a. Du n ph thi
Du n ph thi chnh l cn du thc vt ca cc nh my ch bin thc phm,
hay cc nh hng, ca hng n. Chng c c im l qua s dng, gia nhit
nhiu ln nn mu sm v b bin cht. V tnh cht ngun du ny rt phc tp. N
c thu gom t nhiu ni khc nhau, thnh phn du ban u khc nhau, s ln s
dng khc nhau, nn khng c mt s liu c th no chung cho ngun nguyn liu
ny.
- Thnh phn ca du n ph thi
Du n ph thi c thnh phn tng t du thc vt vi 95 - 97% cc triglyxerit
v mt lng nh cc axid bo t do. Cng thc ha hc chung ca triglyxerit l:
R
1
COOCH
2
R
2
COOCH
R
3
COOCH
2

R
1
, R
2
, R
3
l cc gc hydrocacbua ca cc axit bo. Khi chng c cu to ging
nhau th gi l glyxerit ng nht, nu khc nhau th gi l glyxerit hn hp. Cc gc
R ny c th no hoc khng no, v thng c khong 8 30 cacbon.
Ngoi cc hp cht ch yu trn, trong du n ph thi cn cha mt lng nh
cc hp cht khc nh photphatit, cc cht sp, cht nha, cht nhn, cc cht mu,
cc cht gy mi, cc tin t v sinh t v nhiu tp cht nh mui, tp cht c hc,
cn cacbon, nc, lng axit bo t do tng. Do , ngun nguyn liu ny cn c
x l trc khi s dng nh lc tch cn rn, tch nc, trung ha gim lng axit
bo t do,
- nh hng ca vic n du ti s dng v tiu hy du

Thc t, trung bnh mt nh hng thi ra khong 20 30 kg du n trong ngy, sau
em bn li cho tiu thng chin xo tip. iu ny rt nguy hi cho sc khe
ngi tiu dng. V nu ti s dng trn mt ln ch bin thc phm th du n s
tr thnh cht c hi. Du n khi un nhit cao s b xy ha v polyme ha nn
mt dinh dng, c bit khi thc n b chy en trong mi trng du s tr thnh
cht cacbon - y l nguyn nhn gy ung th.
Du n c dng chin nhiu n mc t vng sang en, thm ch vn cc, sau
thng c thng xung cng rnh, lm thnh nhng mng bm y, gy
nhim mi trng. Du nh hn nc v c khuynh hng gin ra thnh mng mng,
lan rng gy cn tr s xy ha trong nc. V l do m 1 lt du c th lm
nhim 1 triu lt nc. Ngoi ra, du c th ng li trong ng ng dn gy tnh
trng nght v nt v ng.
- Kh nng s dng du n ph thi
Nh vy, du n thi sau khi s dng khng cn gi tr dinh dng na. Do ,
vic ti to s dng ngun du ny l rt cn thit v em li nhiu li ch thit thc
thc v kinh t, bo v mi trng v sc khe ngi dn.
Du n thi c s dng sn xut x phng, c bit l c s dng lm
nguyn liu cho qu trnh tng hp biodiesel. Du n thi c gom li t cc h
thng nh hng, nh my ch bin thc phm,...c gi rt r (2000 3000 ng/lt),
nn biodiesel sn xut ra c gi thnh r. c tnh, hin ti ring khu vc pha Nam,
cc nh my tinh luyn du n nh Nh B: 50 tn/thng, Tn Bnh: 50 tn/thng,
ngoi ra cc nh my sn xut m n lin, nh my ch bin thc phm c s dng du
n v mt s nh hng, qun n, c s ch bin thc phm nh vi khi lng 4 - 5
tn/ngy. Nu c k hoch thu gom c th th lng du thi ny cng kh ln. Song
ngun nguyn liu c hn ch l phi thu gom tng ni nh l, nn cn phi c k
hoch thu gom ph hp, v cn nhn c s h tr hp tc ca chnh quyn cng nh
cc nh cung cp, v ngi tiu dng.
Vy, vic a ra gii php ngun nguyn liu tn dng du n ph thi r tin trong
lun vn ny l c nhiu ngha thc t v gp phn a dng ha ngun nguyn liu
tng hp biodiesel.
b. Ru

Ru c s dng trong cc qu trnh ny thng l cc loi ru n chc cha
khong t 1 n 8 nguyn t cacbon: methanol, ethanol, buthanol v amylalcol.
Methanol v ethanol l cc loi ru hay c s dng nht. Nhng hiu qu kinh t
trong sn xut l ru methanol.
Methanol hay cn gi l methyl alcohol, alcohol g, naphtha g hay ru mnh g,
l mt hp cht ha hc vi cng thc phn t CH
3
OH (thng vit tt MeOH), khi
lng phn t M = 32 dvC, khi lng ring d =0,791 g/cm
3
.
y l ru n gin nht, nh, d bay hi, khng mu, d chy cht lng vi mt
mi c trng, rt ging, nhng hi ngt hn ethanol.
Tuy ethanol c u im l sn phm ca nng nghip, c th ti to c, d b
phn hy sinh hc, t nhim mi trng. Nhng methanol (CH
3
OH) li c s dng
nhiu hn do gi thnh thp hn rt nhiu (khong mt na gi etanol), v cho php
tch ng thi pha glyxerin, do methanol l ru mch ngn nht v phn cc.
Trong phn ng tng hp biodiesel ngi ta thng cho d ru, nn vic thu hi
v ti s dng ru c ngha rt ln v kinh t v bo v mi trng. Ru methanol
d thu hi v ti s dng hn ethanol rt nhiu bi n khng to hn hp ng ph vi
nc (trong khi ethanol th to hn hp ng ph vi nc). Nh vy phn ng s
dng methanol n gin hn, chi ph thp hn ethanol v cc loi ru khc v n yu
cu lng nc trong ru v trong du khng qu thp. Ngoi ra, methylester c
nng lng ln hn ethylester, kh nng to cc vi phun thp hn.
Tuy nhin, chng ta phi ht sc thn trng khi lm vic vi methanol. V
methanol l mt cht c, c th gy cht ngi nu ung phi d mt lng rt nh,
nu tip xc trc tip vi mt c th gy m mt. Methanol l cht d bay hi, hi ca
n kch ng h thn kinh rt mnh, gy au u, chng mt, nh hng rt ln n sc
khe. Do , tt c cc thao tc vi methanol cn phi thc hin trong t ht, eo khu
trang phng c, eo gng tay, eo knh mt, dng phu rt, khng methanol ra
ngoi. [1]
2.6. Phn loi cc phng php tng hp biodiesel

s dng du thc vt v m ng vt lm nhin liu, cn p dng nhng
phng php x l du thc vt v m ng vt tnh cht ca n gn ging vi
nhin liu diesel. Theo quan im khai thc ng c th khc nhau c bn gia du
thc vt v m ng vt so vi nhin liu diesel chnh l nht v ch s cetane.
Cc gii php x l du thc vt v m ng vt lm nhin liu l cc phng php
lm gim nht v tng ch s cetane. Ta c cc phng php sau:
2.6.1. Phng php sy nng
Phng php ny da trn th thay i ca nht theo nhit ca du thc
vt v m ng vt. nht ca du thc vt v m ng vt s gim khi nhit
tng ln. Tng nhit ln qu cao lm thay i trng thi nhit v nh hng xu n
h thng cp nhin liu. Mt khc phng php ny khng ci thin c tr s cetane
ca du thc vt v m ng vtDo phng php ny ch thch hp p dng
ng thi vi cc phng php khc.
2.6.2. Phng php pha long
Phng php pha long l mt trong nhng phng php n gin lm gim
nht v tng ch s cetane. Phng php ny c th s dng nhin liu diesel lm mi
cht pha long. Pha long du thc vt v m ng vt bng diesel s to ra mt hn
hp nhin liu mi t du thc vt v m ng vt. y l mt hn hp c hc gia
nhin liu du thc vt, m ng vt v diesel, hn hp ny ng nht v bn vng. Cc
ch s c tnh ca hn hp du hoc m v diesel ty thuc vo t l thnh phn gia
du thc vt hoc m ng vt v diesel. Cc ch s ny khng t c tnh cht nh
diesel nu pha vi t l ln hn 50% th nht ca hn hp thu c s rt ln.
2.6.3. Phng php Cracking (b gy mch Cacbon)
Qu trnh Cracking du thc vt v m ng vt gn ging nh cracking du
m. Nguyn tc c bn l ct ngn mch hydrocacbon ca du thc vt v m
ng vt di tc dng ca nhit v cht xc tc thch hp. Sn phm thng
gm: nhin liu kh, xng, diesel v mt s sn phm ph khcCracking c th
thc hin trong mi trng kh nit hoc khng kh.



Hnh 1.1. Qu trnh hydrocraking du thc vt

Nhc im c bn ca phng php ny l tn nng lng iu ch nhin
liu. Sn phm thu c bao gm nhiu thnh phn nhin liu khc nhau v c bit l
kh thc hin c qui m ln.
2.6.4. Phng php nh tng ha
Nhin liu ban u l du thc vt hoc m ng vt, ru v cht to sc cng b
mt vi thit b to nh c th to ra nh tng du thc vt hoc m ng vt ru,
trong cc ht ru c kch thc ht 150 nm c phn b u trong nh tng.
Nhin liu nh tng c nht tng ng diesel, t l ru cng ln th
nht nh tng cng gim. Tuy nhin lc d to ra cc ht nh tng nh, kh nng
phn lp nh tng tng ln lm nh tng km ng nht do cn c bin php bo
qun nh tng. Nhit ha hi ca ru thp nn mt phn ru bay hi s cn tr
qu trnh lm vic bnh thng ca ng c.
2.6.5. Phng php ester ha
Qu trnh chuyn ha ester l phn ng trao i ester gia du thc vt v ancol.
Qu trnh ny to ra cc alkyl ester axit bo (biodiesel) c trng lng phn t bng
mt phn ba trng lng phn t du thc vt, v nht thp hn nhiu so vi cc
phn t du thc vt ban u (xp x diesel khong). Ngoi ra, ngi ta kim tra cc
c trng ha l khc ca biodiesel th thy chng u rt gn vi nhin liu diesel
khong. V vy, biodiesel thu c c tnh cht ph hp nh mt nhin liu s dng
cho ng c diesel.

a. C s ha hc
V phng din ha hc, qu trnh trao i ester cn gi l qu trnh ru ha,
c ngha l t mt phn t triglyxerit trao i ester vi 3 phn t ru mch thng,
tch ra glyxerin v to ra cc ankyl ester, theo phn ng:

Thc cht qu trnh chuyn ha ny gm mt lot cc phn ng thun nghch
ni tip nhau. Tc l triglyxerit chuyn ha tng bc thnh diglyxerit, ri t
diglyxerit chuyn ha tip thnh monoglixerit v cui cng l glyxerin:
Triglyxerit + ROH diglyxerit + R
1
COOR
Diglyxerit + ROH monoglyxerit + R
2
COOR
Monoglyxerit + ROH glyxerin + R
3
COOR
Nh vy, sn phm ca qu trnh l hn hp cc alkyl ester, glyxerin, ancol, tri-
, di-, monoglyxerin cha phn ng ht. Cc monoglyrexit l nguyn nhn lm cho hn
hp sn phm b m c.
Glycerin d dng c tch ra khi ester v s dng trong cc ngnh cng nghip
khc.
Ester sau khi tch khi glycerin c a n khu trung ha v qua thp tch
methanol. khu trung ha ngi ta dng axit nh HCl, axit citric hay H
3
PO
4

trung ha lng xc tc kim d v lng x phng to thnh. Tt c lng d xc
tc, x phng, mui, methanol v glycerin t do c tch khi biodiesel bng qu
trnh ra nc. Trung ha bng axit trc khi ra nc nhm gim ti a lng x
phng v lng nc ra cn dng do hn ch c qu trnh to nh tng (nc
trong biodiesel vi tc nhn to nh tng l x phng), gy kh khn cho vic tch
R
1
COOCH
2
R
2
COOCH

R
3
COOCH
2
+ 3ROH

R
1
COOR

R
2
COOR

R
3
COOR

CH
2
- OH
CH- OH
CH
2
- OH
+
Du thc vt Glyxerin Ru mch thng Biodiesel
(Xc tc)

nc khi biodiesel. Biodiesel c lm sch nc trong thp bay hi. Nu sn xut
qui m nh ngi ta thng dng cc mui kh ht nc.
Mt s ngun nguyn liu cha mt lng ln axit bo t do. Axit bo t do
phn ng vi xc tc kim sinh ra x phng v nc. Thc t cho thy rng qu trnh
thu biodiesel c th xy ra bnh thng vi hm lng axit bo t do thp hn 5%. Khi
, cn dng thm xc tc trung ha axit bo t do. Khi hm lng axit bo t do
ln hn 5%, lng x phng to ra lm chm qu trnh tch pha ester v glycerin,
ng thi tng mnh s to nh tng trong qu trnh ra nc. gim hm lng
axit bo t do, trc phn ng transester ha, ngi ta dng xc tc axit, nh H
2
SO
4
,
chuyn ha axit bo t do thnh ester (phn ng ester ha). V vy, hm lng axit bo
t do l yu t chnh trong vic la chn cng ngh cho qu trnh sn xut biodiesel. [1,
3, 6]

b. Cc phng php k thut iu ch ankyl ester
Phng php ester ho c nhiu u im nn ngi ta tp trung nhiu vo nghin
cu phn ng chuyn ha ny. Sau y l cc phng php k thut c s dng
chnh iu ch ra alkyl ester:
Phng php khuy gia nhit
y l phng php c in, rt thng c s dng, do p dng v u t thp.
Phng php ny c bn s dng thit b khuy (khuy c hc hoc khuy t) kt hp
vi gia nhit trc tip bng bp, hi nc hay in trtuy nhin phng php ny
cn thi gian phn ng di mi thu c sn phm.
Phng php siu m
Phng php ny hin nay ang c nghin cu v p dng rt nhiu, do gia
nhit nhanh, v h thng t ng khuy trn di tc dng ca sng siu m. Dng
sng siu m ta s tit kim c rt nhiu thi gian phn ng v t c hiu sut

phn ng cao nht. Tuy nhin, phng php ny tng i phc tp v kh ng dng
trong cng nghip, do chi ph u t cho mt thit b siu m c nng sut cao l rt
ln nn phm vi ca phng php ny vn b gii hn trong phng th nghim.
Phng php vi sng
Phng php ny c bn ging phng php khuy gia nhit, ch khc ch
dng l vi sng gia nhit cho h thng. Phng php ny cho hiu sut tng i
cao, v rt ngn c thi gian phn ng. Cng ging nh phng php siu m,
phng php ny kh p dng, do rt kh u t mt thit b vi sng c cng sut ln.
Phng php s dng mi trng alcol siu ti hn
y l phng php cng da trn c s ca phn ng chuyn i ester, cng
thc hin gia triglyceride v alcol. im c bit ca phng php ny l methanol
iu kin siu ti hn, tc l p sut v nhit ti hn (p sut v nhit cao).
Phn ng trong mi trng methanol siu ti hn c th dng xc tc, c th khng
cn.
Tuy vy Vit Nam hin nay vn s dng phng php c in l trao i ester
s dng xc tc v khuy trn c gia nhit. Cc phng php khc cha thch hp s
dng Vit Nam do cng ngh phc tp v rt t tin. [3]
c. Xc tc s dng trong qu trnh ester ha
Xc tc s dng cho qu trnh tng hp biodiesel theo phng php c th l baz,
axit, hoc enzym, s dng dng ng th hay d th.
Xc tc baz
Xc tc baz ng th thng c s dng nht vn l cc baz mnh nh
NaOH, KOH, Na
2
CO
3
,v xc tc ny cho chuyn ha rt cao, thi gian phn ng
ngn (t 1 1,5 gi), nhng yu cu khng c c mt ca nc trong phn ng v
d to x phng gy c qunh khi phn ng, gim hiu sut to biodiesel, gy kh
khn cho qu trnh sn xut cng nghip. Qu trnh tinh ch sn phm kh khn.
khc phc tt c cc nhc im ca xc tc ng th, cc nh khoa hc hin
nay ang c xu hng d th ha xc tc. Cc xc tc d th thng c s dng l

cc hp cht ca kim loi kim hay kim th mang trn cht mang rn nh
NaOH/MgO, NaOH/-Al
2
O
3
, Na
2
SiO
3
/MgO, Na
2
SiO
3
/SiO
2
, Na
2
CO
3
/-Al
2
O
3
, KI/-
Al
2
O
3.
Cc xc tc ny cng cho chuyn ha kh cao (trn 90%), nhng thi gian
phn ng ko di hn nhiu so vi xc tc ng th.
C ch ca phn ng trao i ester s dng xc tc baz c m t nh sau:

Sau , gc RO
-
tn cng vo nhm cacbonyl ca phn t triglyxerit to thnh
hp cht trung gian:

Hp cht trung gian ny khng bn, tip tc to mt anion v mt alkyl ester
tng ng:

Cui cng l s hon nguyn li xc tc theo phng trnh:

Xc tc B li tip tc phn ng vi cc diglyxerit v monoglyxerit ging nh c
ch trn, cui cng to ra cc alkyl ester v glyxerin.
Xc tc axit

Ngoi ra cc axit Bronsted nh H
2
SO
4
, HCl,cng l cc xc tc ng th cho
chuyn ha cao. Nhng phn ng ch t c chuyn ha cao khi nhit t
trn 100
o
C, thi gian phn ng trn 6 gi. Xc tc axit d th cho qu trnh ny zeolit
USY-292, nha trao i anion Amberlyst A26, A27. Cc xc tc d th ny c u im
l d lc tch, tinh ch sn phm n gin, t tiu tn nng lng, nhng t c s
dng v cho chuyn ha thp. C ch ca phn ng trao i ester s dng xc tc
axit c m t nh sau :
u tin tm axit tn cng vo nhm cacbonyl ca phn t glyxerit, to thnh
hp cht trung gian l cation km bn v chuyn sang trng thi cacbocation:

Cacbocation ny tng tc vi phn t ru to thnh mt cation km bn, cation
ny hon nguyn li tm axit cho mi trng phn ng v tch ra thnh hai phn t
trung ha bn vng l alkyl ester v glyxerin.

Trong :
R l chui cacbon ca axit bo.
R l nhm hydrocacbon ca glyxerin.
R l nhm alkyl ca ru.
Xc tc enzym
Vic s dng xc tc enzym cho phn ng trao i ester c cc nh khoa hc
quan tm nghin cu rt nhiu. Enzym thng c s dng l hai dng lipaza ni bo
v ngoi bo. Xc tc ny c rt nhiu u im nh chuyn ha rt cao (cao nht
trong cc loi xc tc hin nay), thi gian phn ng ngn nht, qu trnh tinh ch sn

phm n gin, v c bit l khng b nh hng bi hm lng nc v axit bo t
do trong nguyn liu. c bit l ngi ta cho enzym mang trn vt liu xp (vt
liu v c hoc nha anionic), nn d thu hi xc tc v c th ti s dng xc tc
nhiu ln, gp phn lm h gi thnh sn phm. Tuy nhin, gi thnh ca xc tc ny
vn cn rt cao nn hin nay cha c ng dng nhiu trong cng nghip. [3]
d. Cc yu t nh hng n phn ng trao i ester
nh hng ca lng nc v axit bo t do trong nguyn liu
Theo Wright v cng s (1944) cho rng nguyn liu cho qu trnh ester ha cht
bo triglycerid cn phi c tr s axit thp hn 1 v tt c cc nguyn liu cn phi
khan hon ton.
Nu tr s axit ln hn 1 cn phi s dng KOH trung ha cc axit bo t do.
Nc cng gy x phng ha lm tiu tn xc tc v gim hiu qu ca xc tc.
X phng sinh ra lm tng nht, to thnh gel v lm cho vic tch glycerin tr
nn rt kh khn.
Kali hydroxit hoc kali methoxit phn ng vi nc v CO
2
c trong khng kh
lm gim hiu qu xc tc. Chnh v c s nh hng mnh ca hm lng nc v
acid bo t do trong nguyn liu n hiu sut chuyn ha ca qu trnh trao i ester
nn nh ta thy, cng ngh sn xut biodiesel ph thuc rt nhiu vo nguyn liu.
Vi nhng ngun nhin liu c hm lng axit bo cao hoc ngun nguyn liu l
du m ph thi, nht thit phi qua cng on x l nguyn liu trc khi a vo
thit b trao i ester.
nh hng ca tc khuy
Cc cht phn ng tn ti 2 pha tch bit nn rt kh tip xc phn ng. Do
cn phi khuy trn, v tc khuy trn nh hng rt ln n thi gian phn
ng, v hiu sut phn ng. Thng hiu sut phn ng tng theo tc khuy trn.
Theo nhiu kt qu nghin cu th tc khuy trn khong 600 vng/pht l tt nht.
nh hng ca t l metanol/du (m)

Do phn ng trao i ester l phn ng thun nghch nn ngi ta thng cho d
methanol tng hiu sut chuyn ha. Tuy nhin, khng nn cho qu nhiu methanol
s tn nhiu chi ph cho qu trnh thu hi v gy tr ngi cho cng on thu hi
glyxerin v tng ha tan. Lng methanol ti u ph thuc vo tng loi xc tc s
dng.
nh hng ca nhit
Phn ng trao i ester c th xy ra cc nhit khc nhau, ty thuc vo cc
loi du s dng (thng dao ng t 55 70
o
C). Khi nhit tng th hiu sut phn
ng tng, nhng thng th thc hin phn ng di nhit si ca methanol,
trnh trng hp methanol bay hi qu nhiu lm gim hiu sut phn ng, cng nh
tn nng lng lm lnh, v hn ch phn ng x phng ha (do nhit cao).

nh hng ca thi gian phn ng
Thi gian phn ng cng nh hng n hiu sut to biodiesel. Nu thi gian
ngn qu th lng nguyn liu phn ng cn t, hiu sut thp. Tuy nhin nu thi
gian phn ng lu qu th c th to sn phm ph v tn nhiu chi ph. Thi gian
phn ng ph hp th cn phi kho st v n cn ph thuc vo loi nguyn liu, xc
tc, v c nhit phn ng.
nh hng ca lng xc tc
Cc loi xc tc vi hot tnh khc nhau nn lng xc tc cn dng cng s khc
nhau. Ngoi ra lng xc tc cn ph thuc vo nguyn liu. Thng th lng xc
tc cng nhiu s cho hiu sut phn ng cng cao.
C ch phn ng transester ha di tc dng ca xc tc kim
Tc nhn xc tc chnh l anion RO - c to thnh trong dung dch ru:


Anion RO - tn cng vo trung tm mang in tch dng ca lin kt C O
-
,
tip theo l s tch phn t ester ra khi phn t triglyceride v s to thnh phn t
diglyceride:

C ch ny lp li cho n khi to thnh phn t glycerin. C th thy rng,
phn ng transester ha xy ra phc tp, vi s to thnh sn phm trung gian l
diglyceride v monoglyceride. [3]



CHNG II
THC NGHIM
I. MC TIU NGHIN CU
T nhng tm hiu v cc ngun nguyn liu, trong bi lun vn ny s tp trung
nghin cu sn xut ra biodiesel s dng phng php truyn thng l ester ha c
khuy trn gia nhit t nguyn liu chnh l du n ph thi v methanol vi xc tc
cho qu trnh tng hp ny l H
2
SO
4
v NaOH.
II. PHNG PHP NGHIN CU
- Xc nh mt s tnh cht ca du thi dng lm nguyn liu.

4
1
2
5
3
- Tin hnh phn ng kho st mt s thng s ti u cho qu trnh tng hp.
- Xc nh cc ch tiu c bn ca methylester thnh phm.
III. THC NGHIM
1. Thit b phn ng
- My khuy t gia nhit. My ny c th iu chnh c tc khuy v nhit ,
c rle ngt nhit nn c th gi nhit , cng nh tc khuy n nh.
- Bnh ba c dung tch 500ml.
- Nhit k 100
o
C.
- Mt b sinh hn ng xon rut g.

2. Chun b nguyn liu
- Du n ph thi
- Methanol
- H
2
SO
4

- NaOH
3. Kho st nguyn liu du
Nguyn liu du n ph thi c th c thu thp cc nh hng nh my ch bin
thc phm nn y l mt ngun nguyn liu di do.
1. ng sinh hn
2. Bnh phn ng
3. Thit b khuy t gia nhit
4. Nhit k
5. Con khuy t

Hnh 2.1. S thit b phn ng

Trong lun vn ny s s dng du thi c cung cp bi Vin sinh hc min
Nam, thnh ph H Ch Minh.
4. Xc nh cc ch s c bn ca nguyn liu du
- Thnh phn axit bo
- T trng
- nht
- Ch s axit
4.1. Cch xc nh nht
S dng nht k xui hiu Ramin c hng s C =0.03619 cSt/s.
t nht k vo b iu nhit, n nh nhit 40
o
C trong 30 pht.
Bm nguyn liu cn o vo bu nht k, sau bm ln trn vch trn cng ca
nht k.
o thi gian nguyn liu chy t vch trn xung vch di ca nht k (t). [1, 6]
nht c tnh theo cng thc:
(cSt)
Trong :
C: hng s ng vi nht k (cSt/s)
t: thi gian chy ca du (s)

4.2. Cch xc nh ch s axit
Ch s acid (AX) c nh ngha l s miligam KOH cn thit trung ha ht
tt c cc acid bo t do cha trong 1 gam mu.

Ch s AX nh hng rt ln ti qu trnh ester ha du m. Theo kinh nghim
nu ch s AX >4 th phi cho phn ng qua 2 giai on vi giai on 1 nhm lm
gim hm lng acid bo t do. [1]
Cch thc hin
Trong bnh tam gic 250ml, cn chnh xc khong 5g mu, thm vo 50ml hn
hp ether ethylic trong ethanol (t l 1:1 c trung ha bng KOH N/10 vi ch th
l phenolphthalein cho n khi c mu hng nht).
Lc trn u v nh nhng lm tan cht bo ri nh phn nhanh bng buret
chun vi KOH N/10 cho n khi c mu hng nht (bn trong 30 giy).
Cng thc tnh:
Ch s acid (AX) =
m
V . 61 , 5

Trong :
5,61: s mg KOH tng ng vi 1ml KOH 0.1N (mg)
V: s ml KOH 0.1N dng chun (ml)
m: trng lng du cn (g)
5. Kh nc trong du n trc khi phn ng
Du n ph thi c cha nc do b thy phn nhit cao, v vy cn thc hin
qu trnh kh nc trnh xy ra hin tng b x phng ha khi trong qu trnh
phn ng c cha nc v NaOH.

Cch kh nc
a du ln nhit 110
o
C, gi mc ny cho nc si ln v bc hi. Cho
my khuy chy ph nhng ti hi hnh thnh di lp du, nu khng n s lm

bn du nng ra ngai, gi mc trong 10 pht. Sau ct ngun nhit, cho du
ngui xung. [3]

Hnh 2.2. Thao tc kh nc trong du nguyn liu
6. Kho st qu trnh tng hp biodiesel t du n ph thi
6.1. Thc hin phn ng giai on 1
Nh trn ni th khi ch s AX ca l nguyn liu >4 th cn phi tin hnh
lm gim lng axit bo t do.
Cch thc hin
- Pha H
2
SO
4
vi methanol.
- un du hn nhit kho st chng 5
o
C (VD: cho ester ho 60
o
C th un
du ln 65
o
C)
- Trn ln methoxide vi du v thc hin phn ng my khuy t c th gia
nhit c, dng nhit k kim sot nhit lun phn ng.



Hnh 2.3. Thit b s dng tin hnh phn ng
i vi tng nguyn liu, lng xc tc, t l methanol/du, nhit phn ng,
thi gian phn ng... khng l nh nhau nn trc ht phi kho st iu kin ti u
cho tng nguyn liu c th.
Vi lng xc tc 0.75% khi lng du, thi gian phn ng 120 pht, nhit
tin hnh phn ng 60
o
C) ta tin hnh:
- Kho st nh hng cc t l methanol/du ln hiu sut phn ng ln lt l
1/8; 1/6; 1/4; 1/3 theo th tch. T rt ra c t l methanol/du thch hp thc
hin phn ng trong cng nghip. (a)
Vi t l nguyn liu methanol/du bng 1/4, thi gian phn ng 120 pht, nhit
tin hnh phn ng 60
o
C) ta tin hnh:
- Kho st hm lng xc tc (H
2
SO
4
) ln lt l 0.25%; 0.75%; 1%; 1.5% (%
theo khi lng du). T tm c % xc tc thch hp thc hin phn ng trong
cng nghip. (b)
Vi t l nguyn liu methanol/du bng 1/4, lng xc tc 0.75% khi lng du,
nhit tin hnh phn ng 60
o
C) ta tin hnh:

- Kho st thi gian phn ng ln lt l 60 pht, 80 pht, 100 pht, 120 pht.
T rt ra c thi gian phn ng thch hp thc hin phn ng tng hp
biodiesel trong cng nghip. (c)
Vi t l nguyn liu methanol/du bng 1/4, lng xc tc 0.75% khi lng du,
thi gian phn ng 120 pht) ta tin hnh:
- Kho st nhit phn ng ln lt l 45, 60, 65, 70
o
C. T rt ra nhit
thch hp thc hin phn ng tng hp biodiesel trong cng nghip. (d)
T (a, b, c, d) ta tin hnh thc hin phn ng tng hp biodiesel thu kt qu. Rt
ra iu kin ti u thc hin phn ng tng hp biodiesel ti giai on 1.
X l sn phm
Sau khi phn ng kt thc ly bnh phn ng ra yn nhit phng cho ngui
dn sau rt vo phu chit.

Hnh 2.4. Phu chit
Ra sn phm bng nc mui m NaCl 10%, sau ra tip bng nc ct m
(khong 40-60
o
C) cho n khi nc ra trung tnh l c.
Sy sn phm nhit 110
o
C trong 1 gi nc bay hi ht.
o nht v ch s axit mi ln kho st tm ra cc thng s ti u nht cho
giai on 1.


6.2. Thc hin phn ng giai on 2
i vi nguyn liu c ch s AX <4 v sn phm giai on 1 c s dng
trong giai on ny.
Cch thc hin
- Pha NaOH vi methanol, dng khuy t ha tan hon ton NaOH trong
methanol to thnh dung dch potassium methoxide.
- Trn ln methoxide vi sn phm ca giai on 1 v thc hin phn ng my
khuy t c th gia nhit c, dng nhit k kim sot nhit lun nhit phn
ng.
Vi lng xc tc 0.75% khi lng du, thi gian phn ng 120 pht, nhit
tin hnh phn ng 60
o
C) ta tin hnh:
- Kho st nh hng ca t l methanol/sn phm giai on 1 ln hiu sut phn
ng ln lt l 1/8; 1/6; 1/4; 1/3 theo th tch. T rt ra c t l methanol/sn
phm giai on 1 thch hp thc hin phn ng trong cng nghip. (e)
Vi t l nguyn liu methanol/sn phm giai on 1 bng 1/4, thi gian phn ng
120 pht, nhit tin hnh phn ng 60
o
C) ta tin hnh:
- Kho st nh hng ca hm lng xc tc (NaOH) ln hiu sut phn ng ln
lt l 0.25%; 0.75%; 1%; 1.5% (% theo khi lng du). T tmc % xc tc
thch hp thc hin phn ng trong cng nghip. (f)
Vi t l nguyn liu methanol/sn phm giai on 1 bng 1/4, lng xc tc
0.75% khi lng du, nhit tin hnh phn ng 60
o
C) ta tin hnh:
- Kho st nh hng ca thi gian phn ng ln lt l 60 pht, 80 pht, 100
pht, 120 pht. T rt ra c thi gian phn ng thch hp thc hin phn ng
tng hp biodiesel trong cng nghip. (g)
Vi t l nguyn liu methanol/sn phm giai on 1 bng 1/4, lng xc tc
0.75% khi lng du, thi gian phn ng 120 pht) ta tin hnh:
- Kho st nh hng ca nhit phn ng ln lt l 45, 60, 65, 70
o
C. T
rt ra nhit thch hp thc hin phn ng tng hp biodiesel trong cng nghip.
(h)

T (e, f, g, h) ta tin hnh thc hin phn ng tng hp biodiesel thu kt qu v so
snh vi cc hiu sut t c ti e, f, g, h. Rt ra iu kin ti u thc hin
phn ng tng hp biodiesel ti giai on 2.
T a, b, c, d, e, f, g, h. Thc hin phn ng tng hp biodiesel qua 2 giai on, so
snh hiu sut biodiesel va tng hp c vi hiu sut biodiesel ti cc trng
hp a, b, c, d, e, f, g, h. Rt ra c iu kin ti u thc hin phn ng
biodiesel qua 2 giai on.
X l sn phm
Sau khi phn ng kt thc ly bnh phn ng ra yn nhit phng cho ngui
dn sau rt vo bnh lng.
Mt phn ng ti u th sn phm s tch lm 2 pha, pha nh l methylester
(biodiesel) v lp nng l glyxerin c tch ra v cn li sn phm l methylester.
o pH ca sn phm bng giy qu tm, a v pH trung tnh ng thi loi b
kim d v nc trong sn phm bng cch tin hnh ra sn phm bng dung dch
H
3
PO
4
pha long, sau ra tip bng nc mui NaCl v nc ct nhiu ln cho n
khi giy qu khng i mu.



CHNG III
KT QU V BN LUN
I. KHO ST NGUYN LIU
Nguyn liu du thi c em phn tch ti trung tm phn tch dch v th
nghim, thnh ph H Ch Minh.
Bng 3.1. Kt qu kim nghim

STT

Ch tiu kim
nghim

n v
tnh

Kt qu

Cng thc
%
Khi
lng
Khi
lng
phn
t
1

2
3
4
5
6
7
8
9
10
Thnh phn axit
bo

% sc k

Caprillic

Lauric
Myristic
Palmitobic
Palmitic
Margaric
Linolenic
Linoleic
Oleic
Stearic
C
8
H
16
O
2

C
12
H
24
O
2

C
14
H
28
O
2

C
16
H
30
O
2

C
16
H
32
O
2

C
17
H
34
O
2

C
18
H
30
O
2

C
18
H
32
O
2

C
18
H
34
O
2

C
18
H
36
O
2

0.07

0.24
0.9
0.61
29.35
0.12
2.34
24.76
36.68
4.93
128

184
212
238
240
254
262
264
266
268
Du nguyn liu c M = 808.7426 dvC; khi lng ring d =0.9 g/cm
3

Ch s axit:

AX =4.862 (mgKOH/g du)
nht:
(cSt)
II. KHO ST HM LNG METHYLESTER TRONG HN HP GIA
DU NGUYN LIU V METHYLESTER N NHT NG HC
Cc kt qu nghin cu cho thy rng nht ca hn hp sau phn ng ester
ha c lin quan cht ch n thnh phn methylester c trong hn hp. Do , chng
ta c th nh gi s b hiu sut to methylester hay mc chuyn ha ca du
thnh biodiesel da trn thng s nht ca hn hp sn phm. Trn c s , ta tin
hnh xy dng ng cong biu din s ph thuc ca nht theo thnh phn
methylester c trong hn hp gia methyl ester v du thi nguyn liu. Qu trnh
c thc hin nh sau:
u tin, ta tng hp nn biodiesel theo ti liu th nghim chuyn , vi iu
kin phn ng l: thi gian 90 pht; nhit 60
o
C; t l methanol/du l 1/4; lng
xc tc NaOH l 0.75% khi lng du nguyn liu.
Sau em ha trn sn phm thu c vi du nguyn liu theo nhng t l th tch
v tin hnh o nht 40
o
C.
Bng 3.2. nh hng ca hm lng Methylester n nht ca hn hp
Methylester v du nguyn liu
% Th tch Methylester
nht 40
o
C
(cSt)
100 4.669
95 5.067
90 5.718
85 6.369
80 7.238
75 8.179

70 8.577
65 9.482
60 10.531
55 11.219
50 12.305
45 13.861
40 15.489
35 17.479
30 19.941
25 20.447
20 22.148
15 24.103
10 30.581
5 35.321
0 38.253
Qua bng s liu ta nhn thy rng, gi tr nht ca cc mu hn hp bin i
theo chiu hng tng i r rng. Nh vy, chng ta c th s dng nh gi s
b kh nng chuyn ha ca phn ng bng cch o nht ca sn phm. C th
thy rng, khi phn trm methylester trong hn hp tng th nht ca hn hp gim.
l v methylester c nht thp hn nhiu so vi nht ca du thi nguyn
liu. th biu din s ph thuc ca nht theo thnh phn methylester c trong
hn hp gia methylester v du thi nguyn liu c trnh by trong s 1.


0
5
10
15
20
25
30
35
40
45
0 20 40 60 80 100 120
% Methylester (V)

III. KHO ST NH HNG CA CC YU T
1. Giai on 1
1.1. nh hng ca thi gian n nht v ch s axit
Bng 3.3. Kt qu kho st nh hng ca thi gian
STT
Thi gian
(pht)
nht
(cSt)
Ch s axit
(mgKOH/g)
1 60 37.64 4.49
2 80 36.00 3.90
3 100 34.52 2.80
4 120 34.38 3.00
S 3.1. nh hng ca hm lng Methylester n nht ca hn hp
Methylester v du nguyn liu

n
h
t

(
c
S
t
)


34
34.5
35
35.5
36
36.5
37
37.5
38
0 50 100 150

Nhn xt:
Ta thy, trong bn thi gian kho st th thi gian 100 pht l hiu qu nht v cho
sn phm c nht v ch s axit thp nht. Trong khong thi gian t 60 80 pht,
phn ng cha xy ra hiu sut tt nht, v vy nht v ch s axit cn cao. thi
gian l 120 pht nht gim khng ng k m ch s axit li tng. c li trong
sn xut ta chn thi gian l 100 pht. C th l gii iu ny nh sau: Do phn ng
chuyn ha ester l phn ng thun nghch, trong khong thi gian u (t 0 n 100
pht) phn ng xy ra theo chiu thun (to biodiesel v glyxerin t methanol v du)
nn ch s axit ca du nguyn liu gim xung. Trong khong thi gian ln hn 100
pht (120 pht) phn ng chuyn ha ester xy ra theo chiu ngc li (to methanol
v du t biodiesel v glyxerin) nn ch s axit ca nguyn liu c xu th tng ln.

S 3.2. S ph thuc ca nht
theo thi gian
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 50 100 150
Thi gian (pht)
S 3.3. S ph thuc ca ch s
axit theo thi gian
C
h

a
x
i
t

(
m
g
K
O
H
/
g
)

n
h
t

(
c
S
t
)

Thi gian (pht)

33.5
34
34.5
35
35.5
36
36.5
37
37.5
38
38.5
0 20 40 60 80
0
0.5
1
1.5
2
2.5
3
3.5
4
0 50 100
1.2. nh hng ca nhit n nht v ch s axit
Bng 3.4. Kt qu kho st nh hng ca nhit
STT
Nhit
(
o
C)
nht
(cSt)
Ch s axit
(mgKOH/g)
1 50 37.99 3.37
2 60 34.38 3.00
3 65 34.39 3.65
4 70 34.70 3.00

Nhn xt:
Ti nhit 50
o
C, nht v ch s axit cn cao l 37.99 cSt v 3.37 mgKOH/g
du, nguyn nhn l do phn ng chuyn ha ester l phn ng ph thuc vo nhit ,
khi tng nhit th tc phn ng thun s tng, ti nhit 50
o
C th phn ng theo
chiu thun cha t c hiu sut cao. n nhit 60
o
C, phn ng t chuyn
Nhit (
o
C)

n
h
t

(
c
S
t
)

Nhit (
o
C)

C
h

a
x
i
t

(
m
g
K
O
H
/
g
)

theo nhit
axit theo nhit

34.3
34.4
34.5
34.6
34.7
34.8
34.9
35
0 0 1/5 2/7 2/5
0
1
2
3
4
5
6
7
8
0 0 1/5 2/7 2/5
T l methanol/du
ha tt nht, lc ny axit ta thu c l 3 mgKOH/g du. T 65
o
C l nhit si
ca methanol, mt phn methanol ha hi lm cho khng lng cht phn ng
nn hiu sut chuyn ha ca phn ng thp, axit cao (3.65 mgKOH/g du).
1.3. nh hng ca t l Methanol/du n nht v ch s axit (theo th tch)
Bng 3.5. Kt qu kho st nh hng ca t l Methanol/du
STT T l (V)
nht
(cSt)
Ch s axit
(mgKOH/g)
1 1/8 34.89 7.01
2 1/6 34.59 6.17
3 1/4 34.39 3.00
4 1/3 34.42 3.64

Nhn xt:
Ta thy t l 1/8 v 1/6 th nht v ch s axit cn cao do lng methanol
cha (7.01 6.17), ng thi lng xc tc axit ha tan vo methanol cha c
tch ra khi sn phm. Vi t l 1/4 th nht, ch s axit gim (3.00), v sau
khng thay i my t l 1/3 (3.64) chng t phn ng t hiu sut chuyn ha

n
h
t

(
c
S
t
)

C
h

a
x
i
t

(
m
g
K
O
H
/
g

d
u
)

T l methanol/du
vo t l methanol/du
axit vo t l methanol/du

34
34.5
35
35.5
36
36.5
37
37.5
0 0.5 1 1.5 2
Hmlng xc tc (%)
0
1
2
3
4
5
6
7
8
9
0 0.5 1 1.5 2
Hmlng xc tc (%)
tt nht 1/4 do lc ny mt phn axit bo t do ca du chuyn ha thnh
biodiesel.
1.4. nh hng ca hm lng xc tc n nht v ch s axit
Bng 3.6. Kt qu kho st nh hng ca hm lng xc tc
STT
Hm lng xc tc
(%)
nht
(cSt)
Ch s axit
(mgKOH/g)
1 0.5 37.09 7.85
2 0.75 34.39 3
3 1 34.45 3.9
4 1.5 34.89 3.37

Nhn xt:
Vi lng xc tc 0.5% th nht v ch s axit cao chng t xc tc cn thiu
phn ng. nht v ch s axit thp nht (3 mgKOH/g) l vi lng xc tc
0.75% chng t vi lng ny, phn ng t trng thi cn bng. Lng xc tc trn
0.75% (1% - 1.5%) th ch s axit tng i cao (3,9 v 3,37 mgKOH/g) chng t l
lng xc tc dng d so vi yu cu phn ng, nu lng xc tc ln cng s nh
hng n phn ng chuyn ha ester, ngn cn qu trnh khi mo, ngn cn qu

n
h
t

(
c
S
t
)

C
h

a
x
i
t

(
m
g
K
O
H
/
g
)

S 3.8. S ph thuc ca nht vo
hm lng xc tc
S 3.9. S ph thuc ca ch s axit
vo hm lng xc tc

81
82
83
84
85
86
87
88
0 50 100 150 200
Thi gian (pht)
H
i
u
s
u
t

(
%
K
L
)

trnh to anion RO
-
thc y qu trnh phn ng. Vy lng xc tc thch hp xc
tc cho qu trnh tng hp biodiesel giai on 1 l 0.75% (theo khi lng du thc
vt).
2. Giai on 2
2.1. nh hng ca thi gian n hiu sut tng hp Biodiesel
Bng 3.7. Bng kt qu kho st nh hng ca thi gian
STT
Thi
gian
(pht)
Hiu sut
(%KL)
Kh nng
chuyn ha
(% methyl ester)
nht
(cst)
Ch s axit
(mgKOH/g)
1 60 81.39 91.370 5.537 0.561
2 80 86.37 96.364 4.958 0.561
3 100 87.27 97.263 4.886 0.281
4 120 87.27 97.263 4.886 0.842

S 3.10. nh hng ca thi gian phn ng n hiu sut
Nhn xt:

85.800
86.000
86.200
86.400
86.600
86.800
87.000
87.200
87.400
0 10 20 30 40 50 60 70 80
Nhit (
o
C)
Qua bng s liu thu c t thc nghim v s ta thy: khi thi gian phn
ng tng t 60 100 pht th hiu sut phn ng tng nhanh (t 81.39 n 86.37%).
Tuy nhin, khi thi gian phn ng l 100 pht v 120 pht th hiu sut phn ng
chnh lch khng ng k (t 86.37 n 87.27%). iu ny c l gii l do trong
phn ng chuyn ha ester, methanol v nguyn liu l hai pha khng tan ln vo nhau
nn cn phi c thi gian chng c th tip xc pha vi nhau thc hin phn
ng. Tuy nhin, nu thi gian phn ng di qu th hiu sut tng khng ng k do:
phn ng chuyn ha ester l phn ng thun nghch, sau 100 pht phn ng bt u
t c trng thi cn bng nn lc ny thi gian phn ng khng cn nh hng n
hiu sut to thnh biodiesel.
2.2. nh hng ca nhit n hiu sut tng hp Biodiesel
Bng 3.8. Bng kt qu kho st nh hng ca nhit

STT

Nhit
(
o
C)
Hiu sut
(%KL)
Kh nng
chuyn ha
(% methyl ester)
nht
(cst)
Ch s axit
(mgKOH/
g)
1 50 86.000 96.821 4.922 0.842
2 60 87.270 97.263 4.886 0.281
3 65 87.000 96.364 4.958 0.842
4 70 86.370 96.364 4.958 1.122

H
i
u

s
u
t

(
%
K
L
)



S 3.11. nh hng ca nhit phn ng n hiu sut

Nhn xt:
Kt qu thu c cho thy: khi tng nhit t 50
o
C n 60
o
C th hiu sut thu
biodiesel tng nhanh (t 86 n 87.27%), nu thc hin phn ng nhit cao hn
na (65
o
C, 70
o
C) th hiu sut phn ng gim mnh (t 87.27 n 86.37%). C th gii
thch s ph thuc ny nh sau:
Khi nhit phn ng thp (nh hn 60
o
C), s chuyn ng nhit ca cc phn
t phn ng cn chm, tc phn ng chm, dn n hiu sut to biodiesel thp.
Tng nhit th tc phn ng tng nhanh, tuy nhin ch trong mt gii hn nht
nh. Nu nhit phn ng qu cao (ln hn 60
o
C) s thun li cho qu trnh x
phng ha, ng thi tc bay hi ca methanol tng mnh (nhit si ca
methanol l 64,7
o
C), lm gim tc phn ng thun. Hai yu t ny lm hiu sut to
biodiesel gim mnh. V th, ta chn c nhit ti u ca phn ng l 60
o
C.
2.3. nh hng ca t l Methanol/bn sn phm n hiu sut tng hp
Biodiesel
Bng 3.9. Bng kt qu kho st nh hng ca t l
STT

T l
Hiu sut
(%KL)
Kh nng
chuyn ha
(% methyl
ester)
nht
(cst)
Ch s axit
(mgKOH/g
)
1 1/8 83.00 93.065 5.319 0.281
2 1/6 83.61 93.510 5.248 0.561
3 1/4 87.27 97.263 4.886 0.281
4 1/3 86.88 96.364 4.958 0.842


82.50
83.00
83.50
84.00
84.50
85.00
85.50
86.00
86.50
87.00
87.50
88.00
0 0 0 1/7 1/5 1/4 2/7 1/3
T l Methanol/du

S 3.12. nh hng ca t l Methanol/bn sn phm n hiu sut
Nhn xt:
Ta thy khi hm lng methanol tng th hiu sut biodiesel cng tng. Tuy nhin
khi tng ti t l methanol/bn sn phm l 1/4 th hiu sut phn ng hu nh khng
tng na m li c chiu hng gim, c l v phn ng t n trng thi cn bng
ti y. Do ta chn t l th tch methanol/bn sn phm l 1/4. V nu d nhiu
methanol th hiu sut thu biodiesel khng tng, m cn tn nhiu nng lng thu
hi lng methanol d, hn na methanol li rt c hi.

H
i
u

s
u
t

(
%
K
L
)


84.00
84.50
85.00
85.50
86.00
86.50
87.00
87.50
88.00
0 0.5 1 1.5 2
H
i
u
s
u
t

(
%
K
L
)
Hm lng xc tc (%KL)

2.4. nh hng ca hm lng xc tc n hiu sut tng hp Biodiesel
Bng 3.10. Bng kt qu kho st nh hng ca lng xc tc
STT

Xc tc
(%KL)
Hiu sut
(%KL)
Kh nng
chuyn ha
(% methyl
ester)
nht
(cst)
Ch s axit
(mgKOH/g
du)
1 0.5 84.45 94.417 5.139 0.842
2 0.75 87.27 97.263 4.886 0.281
3 1 87.00 96.821 4.922 1.402
4 1.5 87.27 97.263 4.886 2.524

S 3.13. nh hng ca lng xc tc n hiu sut
Nhn xt:

Theo kt qu ta thy: khi tng lng xc tc t 0.5% n 0.75% th hiu sut tng
nhanh (t 84.45 n 87.27%), nhng t 0.75% n 1.5% th hiu sut khng tng na
(t 87.27 n 87%). iu ny c th l gii nh sau: Khi tng lng xc tc ln th s
tm hot tnh cng nhiu, tng hot tnh xc tc cho qu trnh nn hiu sut phn ng
cng tng theo. Tuy nhin, hot tnh xc tc l c gii hn, khi tng n im cc i
th chuyn ha khng th tng na, nn d tng lng xc tc th hiu sut cng
khng tng.
IV. XC NH CC CH TIU CHT LNG SN PHM
Sau khi thc hin o cc ch tiu ca sn phm cui, ta c bng s liu tng hp
sau:
Bng 3.11. Bng so snh ch tiu cht lng ca biodiesel sn phm vi biodiesel
chun theo tiu chun ASTM 6751-02
Ch tiu cht lng
Biodiesel chun
ASTM 6751-02
Biodiesel sn phm
T trng 0.82 0.9 0.87
nht 40
o
C (cSt) 1.9 6.0 4.886
Ch s axit (mgKOH/g du) 0.8 0.281
Nhit chp chy,
o
C 181 175
Cn Cacbon, % khi lng <0.05 0.00

Qua bng s liu ta thy rng sn phm Biodiesel lm t du n ph thi t
c nhng yu cu cht lng tiu chun quy nh.



Chng IV
KT LUN
I. KT LUN
Lun vn c hon thnh vi mt s ni dung sau:
1. kho st thnh phn v nhng ch s c trng ca nguyn liu du n ph thi.
2. kho st cc yu t c nh hng ln n qu trnh phn ng ester ha hai giai
on gia du nguyn liu v methanol vi xc tc giai on 1 l H
2
SO
4
, xc tc giai
on hai l NaOH. Cui cng rt ra c iu kin ti u cho qu trnh tng hp
biodiesel t du n ph thi nh sau:

Giai on 1:
Thi gian: 100 pht
Nhit : 60
o
C
T l methanol/du: 1/4
Hm lng xc tc: 0.75%

Giai on 2:
Thi gian: 120 pht
Nhit : 60
o
C
T l methanol/bn sn phm: 1/4
Hnh 4.1. Bn sn phm sau giai on 1

Hm lng xc tc: 0.75%

3. tin hnh o cc ch tiu cht lng ca biodiesel thnh phm v so snh vi ch
tiu chun ca biodiesel theo ASTM 6751-02.
II. HNG TIP TC NGHIN CU
1. Nghin cu s dng nguyn liu cho qu trnh chuyn methylester ha l cc loi
nguyn liu khc nhau nh to, m c (c Basa), du thc vt dng ng c, hn hp
gia du thc vt v m ng vt
2. Nghin cu s dng tc nhn ester ha l ethanol hoc hn hp methanol v
ethanol. V nguyn tc, khi s dng tc nhn ester ha l ethanol th thi gian phn
ng c th c rt ngn, nhng kh nng phn ng ph x phng ha li tng ln nn
cn tm ra hng gii quyt vn ny.
Hnh 4.2. S phn pha sau giai
on 2
Hnh 4.3. Biodiesel sn phm sau khi
sy, lc

3. Nghin cu kh nng s dng cc loi xc tc khc thay th cho xc tc s dng
sao cho biodiesel tng hp ra s c gi thnh r hn v s dng ngun nguyn liu r
tin, xc tc c th ti s dng nhiu ln, gi thnh h, ng thi khng nh hng n
an ninh lng thc, v gp phn gim c nhim mi trng cng nh bo m
sc khe ca ngi dn. V d nh cc xc tc d th, cc loi xc tc rn thay th xc
tc lng gim giai on ra xc tc



DANH MC TI LIU THAM KHO

1. PGS.TS. inh Th Ng, TS. Nguyn Khnh Diu Hng (2008). Nhin liu sch v
cc qu trnh x l trong ha du. Nh xut bn khoa hc v cng ngh.
2. PGS.TS. inh Th Ng. Ha hc du m v kh. Nh xut bn Khoa hc v K
thut.
3. Trn Danh Th. Th nghim Biodiesel. Phng cng ngh t bo thc vt, Vin sinh
hc nhit i.
4. Biodiesel.com. Biodiesel l g [Internet]. [Trch dn ngy 15/04/2012]. Ly t:
URL:
http://biodiesel.com/index.php/biodiesel
5. vietbao.vn. Biodiesel Vit Nam tim nng, tr ngi cn vt qua [Internet]. [Trch
dn ngy 01/06/2012]. Ly t: URL:
http://vietbao.vn/Khoa-hoc/Biodiesel-VN-tiem-nang-tro-ngai-can-vuot-
qua/20892070/188/
6. vietbiodiesel.blogspot.com. Cng ngh Biodiesel [Internet].[Trch dn ngy
01/06/2012]. Ly t: URL: http://congnghebiodiesel.blogspot.com/
7. Wikipedia. Nhin liu sinh hc [Internet]. [Trch dn ngy 28/05/2012]. Ly t:
URL:
http://vi.wikipedia.org/wiki/Nhi%C3%AAn_li%E1%BB%87u_sinh_h%E1%BB%8Dc

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