βιοντιζελ

...
biodiesel

:
-
:
16/10/2008
biodiesel

.
,
, .
,
. o
, / , ,
, ,
.
biodiesel .
,

biodiesel.

. biodiesel
.
diesel. ,
biodiesel
, , . biodiesel,

.
,

.
:
()
()
()
()
() .
.

NaOH KOH.
.
, .
, ,
.

.
, ,
, . , ,
, , .
biodiesel
.
:
()
()
()
() .
biodiesel,
.
biodiesel :
()
()
()

() -.

biodiesel.

.
, , /.

NaOH , /
.
,
14104.

, :
1.
2.
3.

:
10% CaO/Al2O3
10% MgO/Al2O3
10% CaO/TiO2
10% MgO/ TiO2
:
10% Mg/ ZrO2-SiO2
10% Ca/ ZrO2-SiO2
:
20% Ca/Al2O3
biodiesel

( ):
12% TiO2/ZrO2 - SiO2

,
.
biodiesel
...........................................................................8
....................................................................................................................9
1.............................................................................................................12
(Biodiesel).....................................................................................12
1.1.
.............................................................................................12
1.2.
...................................................................................12
1.3.
............................................................................................14
1.4.
biodiesel...................................................................................14
1.5.
biodiesel............................................................................................16
1.6.
.............................................................................................22
1.6.1.
1.7.
...........................................................................24
........26
1.7.1.
.........................26
1.7.2.
...............................................................28
1.7.3.
............................................29
1.7.4.
.................................................30
1.7.5.
.............................................................................................31
1.7.6.
.................................................................31
1.8.
...............................................32
1.9.
...................................................................33
1.9.1.
.................................................................33
1.9.2.
...................................34
2.............................................................................................................35
biodiesel.....................................................................................35
2.1
...........................................................................................35
2.2.
............................................................................................................35
biodiesel
2.3.
..................................................................38
2.4.
..................38
2.4.1.
......................................................................................38
2.4.2.
....................................................................................38
2.5.
...........................41
2.5.1.
........................................................................................41
2.5.2.
.....................................................................................41
2.6.
...........................................42
2.6.1.
............................................................................43
2.6.2.
.........................................................................43
3.............................................................................................................44
biodiesel.................................................................44
3.1.
..................................................44
3.2.
.............................................................................................45
3.3.
..............................................................45
3.4.
...............................................................46
3.5.
......................................................................................47
3.5.1.
.....................................................................................47
3.5.2.
.............................................................................................49
3.5.3.
..............................................................................................................51
3.5.4.
................................................................................................52
3.6.
.......................................................................................................53
4.........................................................................................................................54
biodiesel................................................................................................54
4.1.............................................................................................54
4.2.
.......................................54
4.3.
.......................................................................56
4.3.1.
.................................................................................................................56
4.3.2.
..............................................................................................................57
4.3.3.
....................................................................................57
4.3.4.
.................................................................................................................58
4.3.5.
.....................................................................................................58
biodiesel
4.4.
..........58
4.4.1.
ASTMD93.....................................................58
4.4.2.
ASTMD2709......................................................59
4.4.3.
ASTMD445,400C..........................................59
4.4.4.
ASTMD664....................................................59
4.4.5.
ASTMD874......................................................60
4.4.6.
ASTMD2500..........................................................60
4.4.7.
ASTMD130..............................60
4.4.8.
ASTMD6584........................61
....................................................................62
1...........................................................................................................63
.............................................................................................................63
1.1.1.
NaOH.........................................................................63
1.1.2.
14104................64
1.2.
....................................................................66
1.3.
KOH.......................................................................67
1.4.
................................................................................68
1.5.
NaOH...............................................................................69
1.6.
KOH.................................................................................70
2.............................................................................................................71
...................................................................................71
2.1.
...............................................................71
2.2.
..........................71
2.2.1.
...........................................................................................71
2.2.2.
...........................................................................................................72
2.2.3.
...........................................................................................................72
2.3.
10%CaO/TiO2..................73
2.4.
10%MgO/TiO2................74
2.5.
10%MgO/Al2O3..............75
2.6.
10%CaO/Al2O3...............76
biodiesel
2.7.
10%Mg/ZrO2SiO2.........77
2.8
10%Ca/ZrO2SiO2..........78
2.9.
...........................79
2.9.1.
20%Ca/Al2O3...........79
2.10.
.........................80
2.10.1.
12%MgOZrO2/TiO2..80
2.11. ...................................................81
30.....................................................................................................................82
biodieselD4454.....................................82
3.1.....................................................................................................................82
3.2..................................................................................................82
40.....................................................................................................................84
...........................................................................................84
4.1..............................................................................84
4.2.
.....................................................................85
4.3..................................................................................................87
biodiesel
biodiesel
,
, ,
.

, , ,
, ,
.
,
,
.
,
,
18
20 .

(,
)
, ,
.

.

.
,

.

.
.

.
, ,
.
20
:
1. :
, ,
.
2. :
, :
biodiesel

, , ,
.
,
, ,
,
.

:
1. ,
2. .

.

.
.

.

, (.. Diesel, )
, .

.

, . ( 2003/30/).
,
.
.
diesel . ,
diesel.
,
.
10
biodiesel

,
.
. ,
,
.
20% 2012.
,
, ,
() .
, .

2% 1/1/2006
5.75% 31/12/2010 2003/30/EC
.
,

.

, 1981 .
, .
,
1985, 1990 .
11
biodiesel
(Biodiesel).
1.1.
20
diesel. ,
diesel, 1940,

.

.

. , ,
, , ,
. '30
'40 diesel
, .

diesel
diesel. ,
diesel
, , 11-17
diesel. ,
, ,
, .
1.2.
100
diesel, Rudolph Diesel,
. Rudolph Diesel
,

. ,
.
12
biodiesel

,
diesel (
) . : [1]
(1)
(2)
(3)
(4) ,
(5)

:
(1) ( 11 17 diesel)
(2) ,
.
(3) ,

(4) .

20-25%
.

.

: (a) 25 75
, 25:75 diesel. (b)
. (c) (d) , (e)

biodiesel.

, ,
.
13
biodiesel
1.3.

. diesel
. ,
diesel.
diesel,

, .
1.4.
biodiesel
biodiesel ( ) (FAME)
, ,

. diesel,
, -
diesel.
; (1.1)
.

40C

(btu/lb)
, %
C
C

(btu/lb)
0,87 0,89
3,7 5,8
46 70
16.928 17.996
0,0 0,0024
-11 16
-15 13
60 135
15.700 16.735
1.1: biodiesel
biodiesel diesel
:
(i)

.
(ii)

(iii)
CO2
(iv)
( SOx)
(v)

14
biodiesel
(vi)
(vii)
(viii)
(ix)
(x)
(xi)

,

diesel

-
.

diesel.

.

75% 85%,
(), 50%.
, 2- 2-
(2- nitrofluorene and 1- nitropyrene) 90%,
.

diesel, . (
150C, 77C
diesel). , .
diesel

, .
0,95 diesel,
. .

, 3,37 .
,
, ,
, . , .

, ,
, ,
, .

( 15 ppm )
, .
15
biodiesel
(
)
biodiesel
diesel.
diesel
biodiesel,
,
. , biodiesel
.

,
1993. ,
.
1.5.
biodiesel
biodiesel
, , .

, . biodiesel ,
.
14
.

biodiesel (1.2)
16
biodiesel
(Caprylic)
(Capric)
(Lauric)
(Myristic)
(Palmitic)
(Palmitoleic)
(Stearic)
(Oleic)
(Linoleic)
C8:0
C10:0
C12:0
C14:0
C16:0
C16:1
CH3(CH2)6COOH
CH3(CH2)8COOH
CH3(CH2)10COOH
CH3(CH2)12COOH
CH3(CH2)14COOH
CH3(CH2)5CH=CH(CH2)7COOH
C18:0
C18:1
C18:2
(Linolenic)
C18:3
(Arachidic)
(Eicosenoic)
(Behenic)
(Eurcic)
C20:0
C20:1
C22:0
C22:1
CH3(CH2)16COOH
CH3(CH2)7CH= CH(CH2)7COOH
CH3(CH2)4CH= CHCH2CH=
CH(CH2)7COOH
CH3(CH2)2CH= CHCH2CH=
CH(CH2)7COOH
CH3 (CH2)18COOH
CH3(CH2)20COOH
1.2: .

.
100 .
biogasoline biodiesel,

.
biodiesel,
,
(biodiesel) diesel. ,

diesel,
() .
biodiesel
.
.
.

. ,
.
17
biodiesel

biodiesel :
:
biodiesel
. ,

. ,
,

.

.
.
.
.
()
.
15%
. trap
50
100%.
. trap
.

, ,
,
.
,

.

, canola, .
.
, , ,
.
.
biodiesel, .

18
biodiesel
,
.
:
biodiesel , , , ,
, .
.

biodiesel ,
. ,
..
biodiesel. '
ASTM6751,
.
, ,
,
,
.

, ,
.

, .
3 mole mole
. , gallon $0,61 93,56
$ 0.00652 .
, gallon , 1,45 $ gallon
-, $ 0.02237 mole, 3,4
.
,
6:1 3:1
. ""
99,7%
biodiesel.

.
.

.
.
.

. 10 C,
8C, .

19
biodiesel
.
.
. 2002
MTBE
,

0,31 $ gallon.

0,6 $ gallon.

.

.
.

. ( 1.3).
20
biodiesel
C20:0
C22:0
0.4-1
-
C20:1
C22:1
0.3
2-3
-
1-2
1-2
40-52
76.3
39-66
2-11
16.2
17-38
5-10
1-3
23-41
34-55
2-3
1-2
-
1-4
4.2
30-50
18.7
34-56
69.3
0.3
1.4
0-2
-
7-11
0-1
3-6
22-34
50-60
2-10
5-10
2-5
0.2
1-2
10-15
10-20
5-10
50-60
0.2
5-9
0-1
9-29
8-29
45-67
3.0
1.5
15-60
12
5-10
10-50
C8:1
C10:0
C12:0
C14:0
C16:0
C16:1
C18:0
C18:1
C18:2
C18:3
5-9
4-10
0.2
44-51
2-3
1
13-18
25-30
25-30
7-10
2-3
2-5
-
21-56
12-16
1-4
39-42
41-51
5-8
2
4-22
1-3
2-4
3-7
45-52
14-19
6-9
0-1
1-3
10-18
1-6
0.5
32-47
5.2
6-11
1-2
1-5
2.2
3-6
0-3
17-23
0-2
-
8-11
6.0
0.3
0.5
0.2
-
1.3:
21
biodiesel
biodiesel,

.
.
,
.
. ,
( ), / ,
, ( ),
,
. /
.
. ,
. /
,
. , /
, .

biodiesel: () ()
() ()
.
1.6.
,
,
.
1.1.
.

1.2.
.
1.3.

. , (
) .
22
biodiesel
.1.1
.1.2
.1.3
23
biodiesel
1.6.1.

.
.
.

.
, -
.
.
1.4.

,
.
.
.
Browsed,
.
,
>1000C 3
. ,
( ) 1.5. ,
.
,
. ,

.
24
biodiesel
.1.4
25
biodiesel
.1.5
1.7.

.
.
1.7.1.

.
3%.
,
. ,
.

.
, .
NaOH ,
26
biodiesel

.
,
. Na ,
.
,
.
,
. ,
,
.
,

.
. FFA ( )
.
.

20 40 % FFA, .
, ,
, ,
,

.
1%, .

.
,
12 % FFA 33 % FFA.
1 %,
.

.

.
FFA

.
,
, .

/
27
biodiesel
.
1000gr
/.

. , ,

.
1.7.2.

, , ,
,
, .
,
. ,
, .
NaOH NaOMe.
NaOH NaOMe
NaOH NaOMe 0,3
0,5% w/w .
,
.

/ 6/1 1% NaOH 0,5% aOMe
30 .
,

0.4 2 % .. .
1 % .
1% KOH
.

.
.
, ,
, - .
, , ,
,
, .
.
85% 30
95% 1.5 .
28
biodiesel
75%
30 . .
55% 30 , 80% 1
2.5 .
CaO .

.

.
0.5, 1.0, 1.5, 2.25 M HCl
100% H2SO4 2.25 M

. H2SO4
1.5 2.25 .

, , :
, ,
,
, ,
.

,
.

.
.
1.7.3.

/.

-
. ,

.
6:1.

.

. ,
, .
Gynara
3:1 15:1. ,
29
biodiesel
12:1.
9:1 12:1. 6:1 .
15:1

. 9:1 .
O
. ,

.
, ,
, .
, .
,

. ,

.

.
. ,
,
,
.
.
.
,
.
,
.
, .
1.7.4.
.
, , ,
/ 6:1, 0.5%
600C. 1
80% . 1
(93% - 98%).

.
.
.
15 .

.
30
biodiesel
(6:1) 1% NaOH 3
. 0.1 94,87 64% 60 ,
45 320C .
60 450C 320C.
.
1.7.5.
,

. ,
.
.
NaOH- Me
, .
.
1.7.6.
400C
( / 6:1)

300C.
.
.

.

.
,
, (F), 1.4 , .

. 6:1 / 1,25

.
THF (67 C) 2
.
THF
.
,

. 1.1, 1.3, 1.4 2.0%
82.5, 85, 87, 96.2% .
1.3 % .
95% 15 .
31
biodiesel

.

( ), / 15:1 35:1.

.
.

.
.

.

.
20 , ,
.

.

diesel
diesel.
1.8.
700C
. /
1:1. / 13:1
96% 60 .
(17:1)
99% 15 .
/ ( 9:1 5.8:1) ,
84 58% .

.

.
Batch 3500C 4000C 45 65 MPa,
/ 1:42.
3500C 450 sec
.

, .

.
32
biodiesel

.

biodiesel.
. .
,
.

4000C,
3500C,
.
,
95% 3500C.
.

3500C.
,
,

.
1.9.

-, -
, ,
NMR, NIR.
1.9.1.

, -
. Trimethylsilylation , -
10m
0.1m DB-5
.
, -

.

. Trimethylsilylation -
, - ,
.

33
biodiesel
1.9.2.
HPLC

. HPLC
-
.

GPC, 0,6%
. -
.

.
HPLC (
10-100 ,
1mg/gr)
. HPLC-PAD
, .
.
.

(RPHPLC)

: UV 205 nm,
(ELSD)
. :
() 2-- (5:4v/v) 100% ()
50:50 : ( ) (),
() 2-- 5:4 (C) 30% + 70% B 0
min, 100% B 10 min, 50% B + 50% C 20 min
50% 50%C 5 .

.
. EALD APCL-MS

. , UV
. APCI-MS
.
34
biodiesel
2.
biodiesel
2.1
,
, ,
,

.
2.2.

NaOH KOH.

CH3OH + NaOH CH3O-Na + H2O

H2O H+ OH, CH3O-Na
CH3- Na+ .CH3O
(2.1):
35
biodiesel
2.1
,

( ).
,
2.2.

.
( 2.3)
2.2
OH-,
CH3-O-
.
36
biodiesel
2.3
Na+ .
, R-O-
OH-

.
( )
:
+
,

.
- R-O-
OH-
R-O--., ( )

. ,
, ,
.

.
37
biodiesel
2.3.
.
, .
, ,
.
2.4.
2.4.1.
biodiesel ,

.
(KOH), (NaOH),
(NaOCH3), (NaOCH2CH3).

KOH, KOH
. 30
40-60 C. , ,
, .
,
biodiesel
.

.
,
.

.
2.4.2.
biodiesel

,
petrodiesel. ,
, KOH NaOH,
,
38
biodiesel
.
:
(1)
.
(2) ,
(3)
,
( )
( )
.
biodiesel

.
MgO, Al-Mg hydrotalcites, Cs sepiolite
MCM-42
MgO Al
.
. MgO, CeO2, La2, 3 ZnO

stearate .
, -

( 30% 80%)
Schuchardt
poly (styrene/divinylbenzene)
.

30% 1 , 5 mol%
/.
100gr / 2:1
60C 0,48 lit/h.

. , Sercheli
, , - trricyclohexylguanidine (TCG)
super cages .
( 14%
5 ), , Y
. , (styrene/divinylbezene)

.

.
, , , ,
39
biodiesel
, , , .

/ 6:1 67 wt%
. ,
130 C,
.
95%
260C ,
18.
,
.
NaX faujasites
, ,
/.
/ 6:1
1 .
80%. , - NaX
( 3h )
/
.
NaX (ETS-10) Na K
. ETS-10
( > 80%) , ,
. Na/NaOH/Al2O3

. (>90%) 2h
/ 9:1
60C.
Li-CaO Li 0,26 -4w/t%

tridutyrate btanoate. Li
1,32w/t%
btanoate. Li CaO XPS
SRIFTS
Li OH .
Li Li
LiNO3
. , Mg- Al hydrotalcite
.
glyceryl tributyrate
.
Mg.
Xie
.
40
biodiesel
: Kl/Al2O3 > K2CO3/Al2O3 > KF/ Al2O3 > KOH/

Al2O3 > KNO3/ Al2O3 > K2CO3/ Al2O3 > KBr/ Al2O3.
2.5.
Bronsted,
,
.
2.5.1.
H2SO4 HCl.
Freedman , 1 mol%
H2SO4 / 30:1 65 C,
50 (> 99%),
( 117 C) ( 78C),
, 3 18 , .

(1.5-2.25 ), biodiesel ,
.
2.5.2.
Amberlyst- 15
,
.
-
(WZA), (STO), -
(SZA), WZA ,
> 90% 250o C 20 h. Amberlyst- 15, SZ,
Nafion NR50, WZ 60o C,
;

.
TG (triolen)
.

.

batch
.
.
41
biodiesel
.
oleate
.
alumiun phosphate Al/P
Kernel
. ,

. , (200o C)
/
(60:1).
2.6.

biodiesel,

,
.
2.1.

.

.

. ,
0,5%
,
.
2.1. .

(wt%)

<0.05%

0.3-0.7%

2-7%

5-30%
trap
75-100%
42
biodiesel
2.6.1.

, FFAs

.
20% 49% FFAs,
. - FFAs
< 1% ,
. -

12% FFAs 33% FFAs.
biodiesel -
.

.
- HCl
30 .

(C12 C16) .
Bronsted
. , ..,
,
.
Lewis Bronsted
, Bronsted
-
, Lewis Bronsted
, .
, Lewis BF3
.
2.6.2.

. ,
-
,

.
43
biodiesel
3.
biodiesel
3.1.
, .

biodiesel , ,
.
.
, (< 2%)
.
,
.

.
. ,
biodiesel
.

, .

. .

.

.
biodiesel.
,

.
, .

, ,
.
,
,
99,7% biodiesel.
biodiesel
, .
44
biodiesel

( ).
, ,
. biodiesel ,
. ,
,

.
3.2.

.
.
1%
FFA FFA
.
,
.
.
biodiesel
.
, 5 1 ,
,
/.
3.3.

.
.
,

.
- .

.
, ,
. ,

.

.

45
biodiesel
.
.
.
.
,

.
, ASTM 2274,
.
Rancimat, ,
. ,

.
BHT TBHQ
.
3.4.
,
diesel .
, .
, ,
, . ,
, , , .
diesel
.
,
.

-
. ,
,
, ,
.
46
biodiesel
3.5.
,
30 , .

.
, .

(3.1):
3.1
B1
B2
o C
(ml)
(
3000
0,69%)
(
3000
0,1%)
B3
High erucic Brassica
3000
B4
Low erucic Brassica
3000
B5
3000
3.5.1.
,
,
( ).
, ,
,
.
milliequivalents
,
3.1
,
6 .
. ,

47
biodiesel
3.1: , 30 : (a) , (b) .
48
biodiesel
3.5.2.
, , ,
,

.
, , .
( 3.2)
,

(FAME) . 0,5 mg KOH/g
(3,4, 5)
12 .
4 , ,
.
AV
4 .
,
,
.
. ,
,
,
.
49
biodiesel
3.2: , 30 : (a) , (b)

.
50
biodiesel
3.5.3.

.
. ,

( 3.3.)
3.3: , 30-
: () , () .
51
biodiesel
3.5.4.

.

,
30- . ( 3.4)
3.4: , 30-
: () , () .
52
biodiesel
3.6.

.
, , ,
.
.

.
diesel .
( )
diesel,
,
.
.
53
biodiesel
4.
biodiesel
4.1.
, biodiesel
:
.
.

.
-
.
biodiesel
ASTM, . ASTM D 6751:
biodiesel (B100) .
biodiesel
.
diesel,
biodiesel .
, ,
biodiesel,
. ,
ASTM D6751
ASTM. , ,
,
(

ASTM).
biodiesel
-.
4.2.
biodiesel
,

.

diesel.
biodiesel ,
54
biodiesel
biodiesel ,
.
biodiesel
. ,
,

. 4.1 .
4.1
biodiesel
(CSN)
(DIN)
(UNI)
USA
(ASTM)
15C
g/cm2
0.85 - 0.89
0.87 - 0.89
0.87 - 0.89
0.875 0.89
0.86
0.90

40C mm2/s
3.5 - 5.0
3.5 - 5.0
3.5 - 5.0
3.5 - 5.0
3.5 - 5.0
1.9 - 6.0
(0C)
100
110
100
110
100
130
CFPP (0C)
0/-5
-5
0 - 10/-20

(0C)
-10
0/-5
>= 49
>= 48
>= 49
>= 49
>= 47
(mgKOH/g)
<= 0.8
<= 0.5
<= 0.5
<=0.5
<= 0.5
<= 0.8
,
.

.
.

.
.
55
biodiesel
.

.
. , ,
, , CO HC.
diesel,
.

.

.

.
,
.
4.3.

,
, .
,
biodiesel.
biodiesel
, , , .

biodiesel.
4.3.1.
.
,
.
, diesel.
1500 ppm ,
diesel 500 ppm. diesel
(ASTM D 975) (ASTM D 6751) 500
ppm.
1%,

56
biodiesel

. .

.

.
.
4.3.2.
biodiesel

.
trap,
. 100 m
,
5 m.
4.3.3.
(FFAs) biodiesel
. FFAs
, ,
,
biodiesel. biodiesel

ASTM , 0,2-0,3%
FFAs .
4.1.1.
600-900 ppm .
ASTM biodiesel
10 ppm.
biodiesel ,
.

biodiesel.
57
biodiesel
4.3.4.
biodiesel

- diesel 15 ppm
500 ppm 2006. biodiesel .
, biodiesel
40-50 ppm.
4.3.5. .

.

, biodiesel.
biodiesel
, ,
. biodiesel
biodiesel ,
.
100
.
:
4.4.
4.4.1. ASTMD93

101,3 kPa,
.

.

.
.
.
>2000C.
,
1300C.

58
biodiesel
4.4.2. ASTMD2709

400C 1.0 4.1 mm2/s
700 900 kg/m3.
. 100
,
. ,
, biodiesel
.

.
4.4.3. ASTMD445,400C

diesel.
15 %
ASTM D 6584.

biodiesel,
.
4.4.4. ASTMD664

,
.
.
.
.
biodiesel
.

-2

10-9.
10-9 .
10-9 .
59
biodiesel
4.4.5. ASTMD874

.
. biodiesel
,
.
,

.
4.4.6. ASTMD2500

, .

diesel . ,
5 % .
.
.

100 . ,

.
.
4.4.7. ASTMD130

.
. 100
.
, (D 664)

.
60
biodiesel
4.4.8. ASTMD6584

.
.

biodiesel.

.
.
-, -,
.

. ASTM D 6584
,
.
100
ASTM
D93
130 min.
&
,40 Oc
D2709
D445
0,050 max.
1,9-6,0
% vol.
mm2/sec.
D874
0,020 max.
% mass
D130
No. 3 max.
D2500
D664
0,80 max.
mg KOH/gm
D6584
0,020 max.
% mass
D6584
0,240 max.
% mass
14104
< 0,5
mg KOH/g
61
biodiesel
62
biodiesel
,
, .
3/1
.
1.1.1. NaOH
:
:
)
, .
)
.
:
500ml 100ml CH3OH (),
99,9% 1,1575 gr NaOH 200
rpm/ methoxide.
1 . .
, 1 , methoxide
300ml ()
60C.
2 60C.

18 ,
.
18 .

. 1/1 ,
48 .

,
63
biodiesel
14104.
0,8 mg KOH/gr.
1.1.2.
14104
:
C= 0,1
, 95%
Standarlisation KOH
10 ml HCl 1, 100ml
.
, 250ml, 25ml Cl ,
, . 3
.
:
(1) 23 ml
(2) 22,7 ml
(3) 22,5 ml
M.O. : 22,73 ml
:
1 V1 = 2 V2
N V = V
0,1 ml 25ml = 22,73 ml
2,5 ml = 22,73 ml
= 0,10999 ml
:
20,0884 gr HCl
KOH.
100 ml 2-propanol 1,7 ml . 1,7
ml .
:
: 56,1 V N
m
: V =
64
biodiesel
N = Standarlisation
m =
: 56,1 1,7 0,10999 = 0,52

20,0884
/gr
.
:

,
.
.
65
biodiesel
1.2.
300ml
1,1575 gr NaOH
100ml CH3OH ()

:
20,0884 gr
KOH. 100 ml 2propanol 1,32 ml . 1,32 ml .
:
: 56,1 V N
m
: 56,1 1,32 0,10999 = 0,4

20,0884
/gr
66
biodiesel
1.3.
KOH
:
300ml
1,6205 gr OH
100ml CH3OH ()
, ,
methoxide 400-500
cpm/.
:
20,0051 gr
:
: 56,1 V N
m
: 56,1 0,65 0,10999 = 0,20048

20,0051
/gr
67
biodiesel
1.4.
:
300ml
1,6205 gr OH
100ml CH3OH ()
,
:
20,0091 gr
:
: 56,1 V N
m
: 56,1 0,55 0,10999 = 0,1696

20,0091
/gr
68
biodiesel
1.5.
NaOH
:
300ml
1,1575 gr aOH
100ml CH3OH ()
,
:
20,0884 gr
:
: 56,1 V N
m
: 56,1 0,6 0,10999 = 0,1843 /gr

20,0884
.
69
biodiesel
1.6.
KOH
:
300ml
1,6205 gr OH
100ml CH3OH ()
,
:
20,0091 gr
:
: 56,1 V N
m
: 56,1 0,78 0,10999 = 0,24 /gr

20,0091
.
70
biodiesel
, ,
.
2.1.

. ,
.
.
.

,
.
.
2.2.
2.2.1.
,
.

. ,
.

.
, .

,
, , .
.
350-500 nm (
) 120 oC
.

.
, ,
71
biodiesel
, ,
.
,
.

,

.

.
.
2.2.2.
,
,
.
,
.

:
2.2.3.
.
, .

,
.
,
.
.
72
biodiesel
2.3.10%CaO/TiO2
:
Ca(NO3)2 * 4 H2O
CaO = 56,078
Ca(NO3)2 * 4 H2O = 98%
TiO2 = 0,38 ml/g
:
5gr TiO2 0,5gr CaO
:
0,5gr CaO / MB CaO =>
0,5gr CaO /56,078 = 0,0089 mol
0,00357 mol Ca(NO3)2 * 4 H2O=>
0,00357 mol 236,15 = 2,108 gr Ca(NO3)2
0,38 ml 1 gr
5 gr ,TiO2, 1,9 ml
:
2,108 gr Ca(NO2)3 *4 H2O 1,9
ml 2. Ca(NO2)3 ,
. Ca(NO2)3 ,
. 5 gr TiO2
, - 1.9 ml

. ,
120C 24 . 24
, 500C 5 .
73
biodiesel
2.4.10%MgO/TiO2
:
Mg(NO3)2 * 6 H2O = 256,41
MgO = 40,31
Mg(NO3)2 * 6 H2O = 98%
TiO2 = 0,38 ml/g
:
5 gr TiO2 0,5gr MgO
:
0,5gr MgO / MB MgO =>
0,5gr MgO /40,31 = 0,0124 mol
0,0124mol Mg(NO3)2 * 6 H2O=>
0,0124mol 256,41 = 3,056gr Mg(NO3)2
0,38 ml 1 gr
5 gr ,TiO2, 1,9 ml
:
3,056 gr Mg(NO2)3 *6 H2O 1,9 ml 2.
Mg(NO2)3 , .
Mg(NO2)3 , .
2 gr , TiO2,
, - 1,9 ml

. ,
120C 24 . 24
, 500C 5 .
74
biodiesel
2.5.10%MgO/Al2O3
:
Mg(NO3)2 * 6 H2O = 256,41
MgO = 40,31
Mg(NO3)2 * 6 H2O = 98%
Al2O3 = 0,65 ml/g
:
5gr Al2O3 0,5 gr MgO
:
0,5 gr MgO / MB MgO =>
0,5 gr MgO /40,31 = 0,0124 mol
0,0124mol Mg(NO3)2 * 6 H2O=>
0,0124mol 256,41 = 3,18 gr Mg(NO3)2
0,65 ml 1 gr
5 gr ,Al2O3, 3,25 ml
:
3,18 gr Mg(NO2)3 *6 H2O 3,25 ml 2.
Mg(NO2)3 , .
Mg(NO2)3 , .
5 gr , Al2O3
, - 3,25ml

. ,
120C 24 . 24
, 550C 5 .
75
biodiesel
2.6.10%CaO/Al2O3
:
Ca(NO3)2 * 4 H2O = 236,15
CaO = 56,078
Mg(NO3)2 * 6 H2O = 98%
Al2O3 = 0,65 ml/g
:
5gr Al2O3 0,5 gr CaO
:
0,5 gr CaO / MB CaO =>
0,5 gr MgO / 56,078 = 0,0089 mol
0,0089mol Ca(NO3)2 * 4 H2O=>
0,0089mol 236,15 = 2,107 gr Ca(NO3)2
0,65 ml 1 gr
5 gr ,Al2O3, 3,25 ml
:
2,107 gr Ca(NO2)3 *4 H2O 3,25 ml 2.
Ca(NO2)3 , .
Ca(NO2)3 , .
5 gr , Al2O3
, - 3,25ml

. ,
120C 24 . 24
, 550C 5 .
76
biodiesel
2.7.10%Mg/ZrO2SiO2
:
Mg(NO3)2 * 6 H2O = 256,41
MgO = 40,31
Mg(NO3)2 * 6 H2O = 98%
ZrO2 SiO2 = 0,4 ml/g
5gr Al2O3 0,5 grZrO2SiO2
:
0,5 gr CaO / MB ZrO2SiO2=>
0,5 gr MgO / 56,078 = 0,0089 mol
0,0089mol Ca(NO3)2 * 4 H2O=>
0,0089mol 236,15 = 2,107 grMgO
5 gr ZrO2SiO2 3,25 ml
:
2,107 gr Mg(NO3)2 * 6 H2O 3,25 ml 2.
Mg(NO3)2 , .
Mg(NO3)2 , .
5 gr , ZrO2SiO2
, - 3,25ml

. ,
120C 24 . 24
, 550C 5 .
77
biodiesel
2.8
10%Ca/ZrO2SiO2
Ca(NO3)2 * 4 H2O = 236,15

CaO = 56,078
Mg(NO3)2 * 6 H2O = 98%
:
5gr Al2O3 0,5 gr CaO
:
0,5 gr CaO / MB CaO =>
0,5 gr CaO / 56,078 = 0,0089 mol
0,0089mol Ca(NO3)2 * 4 H2O=>
0,0089mol 236,15 = 2,107 gr Ca(NO3)2
5 gr ,ZrO2SiO2, 3,25 ml
:
2,107 gr Ca(NO2)3 *4 H2O 3,25 ml 2.
Ca(NO2)3 , .
Ca(NO2)3 , .
5 gr , ZrO2SiO2
, - 3,25ml

. ,
120C 24 . 24
, 550C 5 .
78
biodiesel
2.9.
2.9.1. 20%Ca/Al2O3
:
Ca(NO3)2 * 4 H2O = 236,15
A Ca = 40,08
Mg(NO3)2 * 6 H2O = 98%
Al2O3 = 0,65 ml/g
Al2O3 pauder = 10gr
:
2gr Ca
:
2 gr CaO / B Ca =>
2 gr MgO / 40,08 = 0,0499 mol
0,0499 mol Ca(NO3)2 * 4 H2O=>
0,0499 mol 236,15 = 11,78932 gr Ca(NO3)2
10
.
Al2O3 = 65 ml/gr

V = 6,5 10 = 65ml
V = 70 ml
:
11,78932 gr Ca(NO2)3 *4 H2O, 10gr Al2O3 70 ml 2.
evaporator 75C 100 /, 4 .
4 120C 24
,
500C 5 .
79
biodiesel
2.10.
2.10.1.
12%MgOZrO2/TiO2
:
Mg(NO3)2 * 6 H2O = 256,41
MgO = 40,31
Mg(NO3)2 * 6 H2O = 98%
:
MgO ZrO2 TiO2 (1 - 1 - 2
) , NH3.
, 12.8 Mg(NO3)2 6 H2O 16.89 g ZrO(NO2)3 200 ml
. , 7.987 g TiO.
PH 8,
NH3(-) .
,
, 383 12 773 5
,
80
biodiesel
2.11.
:
250 ml
20 ml CH3OH (), 99,9% 1 gr
50 gr
1000 rpm/, . 5
.
5

, 60C 100 rpm/ 2 .
,
.
:

.
.
(C)
MgOZrO2/TiO2
12%
500
Ca/Al2O3
20%
550
CaO/Al2O3
10%
550
MgO/Al2O3
10%
550
MgO/TiO2
10%
500
10%CaO/TiO2
10%
500
MgO/ZrO2SiO2
10%
550
CaO/ZrO2SiO2
10%
550
81
biodiesel
30
biodieselD4454
3.1.
, .
, .
biodiesel
D445 .
.
biodiesel,
.
,

.
3.2.
, ( )
, [ ,
.

.
35,4 cst,
% ..

biodiesel .
82
biodiesel
% :
biodiesel =>
35,4 5,87 = 29,53
: 35,4 5,87
100 83,4 %
(%)
(cst)
CaO/Al2O3
20
5,87
83,4
MgO/Al2O3
10
5.84
83,7
CaO/TiO2
10
4.98
85,9
MgO/ZrO2SiO2
10
6.67
81,4
CaO/ZrO2SiO2
10
6.52
81,58
MgO/TiO2
10
5.2
85,3
CaO/Al2O3
10
4.684
86,7
MgOZrO2/TiO2
12
6.8
80,79
83
biodiesel
40
4.1.
biodiesel
,
3/1
(KOH NaOH). biodiesel
biodiesel
EN 14104.

biodiesel
KOH 0,1696.
.
(KOH/gr)
NaOH
KOH
NaOH
KOH
NaOH
KOH
0.52
0.1696
0,1843
0,24
0,4
0,20048
84
biodiesel
4.2.

.
biodiesel :
:
Al2O3
CaO/ Al2O3 < MgO/ Al2O
5,88
5,87
5,86
5,85
5,84
CaO/Al2O3
MgO/Al2O3
5,83
5,82
TiO2
MgO/TiO2 < CaO/ TiO2
MgO/TiO2
.
8
6
4
CaO/TiO2
MgO/TiO2
2
0
85
biodiesel
ZrO2-SiO2
MgO/ZrO2- SiO2 < CaO/ ZrO2- SiO2
CaO/ TiO2
6,7
6,65
6,6
6,55
MgO/ZrO2SiO2
CaO/ZrO2SiO2
6,5
6,45
6,4
:
CaO
CaO/ TiO2 > CaO/ Al2O3 > ZrO2- SiO2
7
6
5
4
CaO/Al2O3
CaO/TiO2
CaO/ZrO2SiO2
1
0
86
biodiesel
MgO
MgO/ Al2O3 > MgO/TiO2 > MgO/ZrO2- SiO2
7
6,5
6
5,5
MgO/Al2O3
MgO/TiO2
MgO/ZrO2SiO2

CaO
MgO.
4.3.

.
,

biodiesel
GC.
,
biodiesel
.

Biodiesel
.
87
biodiesel
[1] Subcontractor Deport. Biodiesel Production Tehnology August 2002January

2004.J.VanGerpen,B.ShanksandR.Pruszko.LowastateUninersity.D.Clements
RevewahleProductsDevelopmentLaboratory.G.KnothUSDA/NCAUR
[3] Shay EG. Dirsel fuel from vegetable oil: starus and opportunities. Biomass
Bioenergy1993:22742
[4] Srivastava A.Prased R. Tridlyceridesbased biesell buels Renew Sustain Energy

Rev.2000:4:11133
[4] Zhang Q. Feldman M. Peterson CL Diesel Enyine durability when fuelled with
metylesterofwinterrepeseedoil.AgriculturalEngineers,paperno881562ASAE,st
Joseph,Ml,1988
[5] Possible methods for biodiesel production J.M. Marchetti, V.U. Miguel, A.F.
Errazu.Received18July2005.Accepted25August2005.
[6] Technical aspects of biodiesel production by trasnsesterification a revive. LC.

Mether, Dvidya Sagar, S.N. Naik. Received 17 February 2004 . Accepted 15
September2004.
[7]Biodieselfuelproductionwithsolidsuperacidcatalysisinfixedbedreactorunder
atmospherispressur.SatoshiFuruta,HiromiMatsuhash,KazushiArata.Received10
June2004.Accepted1September2004.
[8]BiodieselproductionandQuality.Lastupdate11March2002
[9]Longstoragestabilityofbiodieselfromvegetableandusedfryingoils.Abderrahim
Bouaid,MercedesMartinez.
[10] Heterogeneous Catalysts for Biodieel production. Martino Di Serio, Riccardo

Tesser,LuPengmei,andElioSantacesana.
88

βιοντιζελ

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

βιοντιζελ

Uploaded by

Copyright:

Available Formats

...

100% H2SO4 2.25 M

CH3OH + NaOH CH3O-Na + H2O

: Kl/Al2O3 > K2CO3/Al2O3 > KF/ Al2O3 > KOH/

High erucic Brassica

Low erucic Brassica

3.1: , 30 : (a) , (b) .

3.2: , 30 : (a) , (b)

: 56,1 1,7 0,10999 = 0,52

: 56,1 1,32 0,10999 = 0,4

: 56,1 0,65 0,10999 = 0,20048

: 56,1 0,55 0,10999 = 0,1696

: 56,1 0,6 0,10999 = 0,1843 /gr

: 56,1 0,78 0,10999 = 0,24 /gr

5gr TiO2 0,5gr CaO

5 gr TiO2 0,5gr MgO

5gr Al2O3 0,5 gr MgO

5gr Al2O3 0,5 gr CaO

5gr Al2O3 0,5 grZrO2SiO2

Ca(NO3)2 * 4 H2O = 236,15

5gr Al2O3 0,5 gr CaO

[1] Subcontractor Deport. Biodiesel Production Tehnology August 2002January

[4] Srivastava A.Prased R. Tridlyceridesbased biesell buels Renew Sustain Energy

[6] Technical aspects of biodiesel production by trasnsesterification a revive. LC.

[10] Heterogeneous Catalysts for Biodieel production. Martino Di Serio, Riccardo

You might also like