()

. , . .


(CH2)7COOH3C

COOH3C

C2 H 5

CH3(CH2)7

(CH2)11COOH3C

C10 C24



.. NaOH , KOH , CH3ONa
(<0.05%) (<0.5%)

(RCOOH) (.. NaOH)

RCOOH + NaOH

RCOONa + H2O (1)

RCOOR + H2O

RCOOH + ROH (2)



-
RCOOH + CH3OH

Cat.

RCOOCH3 + H2O

.. H2SO4



70-120C

3-12 bar.

38.1, 58 100 % ..
2.93 % ..
3.03 % ..
(99.9 %)

-
Acidity (eqH+kg-1) : 5.20
Sg (m2kg-1)

: 31x10-3

Tmax (oC)

: 145


2 %
FFAs (38.1, 58 100 % )
( 99.9%)
/ FFAs : 6.6/1 molmol-1

12-50 h

(90-120C)
VR = 500 ml

P
V-14

GFM-01

RV-01

V-15
GV-01 NV-01

E-10

GR-01

N2

R-01

1.

2.

RCOOH + CH3OH

Mmix

k1
k-1

RCOOCH3 + H2O

dCFFAs
= k FFAs CFFAs CMeOH k FFAs CMEs CH2O mcat
dt



90 - 120 oC
38.1 % ..
/ FFAs : 6.6/1 molmol-1

120 oC
100 oC

Moles FFAs

0.25

110 oC
90 oC

0.20
0.15
0.10
0.05
0.00

600

1200

1800

2400

3000

(min)

90 - 120 oC
38.1 % ..
/ FFAs : 6.6/1 molmol-1
50 h

T (oC)

(%)

(%)

120

38.1

4.59

1.1994

110

38.1

4.78

1.1091

100

38.1

5.58

0.8638

90

38.1

7.44

0.5269

Ke

Ke = k1 / k1


0.3

120C
120C

120 oC

0.2

k1 =8.37 10-4

0.15

k-1=6.98 10-4

0.1
0.05
0
0

20

40
60
-3
x 10 (s)

80

100

0.3

110C
110C

0.25

110 oC
k1 =4.76 10-4

Moles FFAs

Moles FFAs

0.25

k-1=4.32 10-4

0.2
0.15
0.1
0.05
0
0

20

40

60
x 10-3 (s)

80

100

120


0.3

90 oC

90C
90C

0.25

Moles FFAs

k1 = 1.40 10-4
k-1=2.65 10-4

0.2
0.15
0.1
0.05

0.30

0
0

0.20

100
x 10-3 (s)

150

200

NFFAs,calc

0.10

0.00
0.00

50

0.10

120

110

110

110

100

90

0.20

0.30

NFFAs,exp

(% ..)

(% ..)

(% ..)

58.00

58.00

0.00

1 .

6.13

7.62

51.40

2 .

2.23

2.13

57.00

1.02

0.80

58.36

Ke=1.1994

58%
T=120 oC

Ke=1.1994

1 .

(% ..)

(% ..)

(% ..)

100.00

100.00

0.00

20.94

22.32

77.68

4.23

4.68

95.32

100%
T=120 oC

k = A oe

E a

RT

ln Ke, ln kFFAs, ln k-FFAs

2
0
-2

-4

-6
-8
-10
0.0025

0.0026

0.0026

0.0027

0.0027

0.0028

0.0028

1/T (K-1)

Ea
kJmol-1

kg2kg

-1mol-1s-1

cat

R2

70.34

1.12E+11

0.999

37.93

4.19E+06

0.947

Steinigeweg & Gmehling

72.23 kJmol-1

20 gr

( 99.9%)
/FFAs
: 10/1 molmol-1

RV-01

PC
( 20-180 g/h)
(70-100C)

GV-01

GR-01
GFM-01

OP-01
NV-01

LV-04
GR-02

R-01

LV-03

F-01
SP-03
LV-05

LV-02

LLC-01

LV-01
PV-01

DP-01

1.

2.

RCOOH + CH3OH

k1
k-1

RCOOCH3 + H2O

dmcat
QCFFAs
=
dx
k FFAs CFFAs CMeOH k FFAs CMEs CH2O

(%)

80
70
60
50
40
30
20
10
0

100 oC
80 oC

90 oC
70 oC

70-100 oC


/
FFAs : 10/1 molmol-1


.

30

60 90 120 150 180

Q (g/h)


-
-
3.5E-04

T=100 oC

3.0E-04

kffas

2.5E-04
2.0E-04
1.5E-04

20 (g/h)

1.0E-04

60 (g/h)
180 (g/h)

5.0E-05

0.0E+00
0

10

12

14

16

 (1)

: 2 % ..

MeOH / FFAs

: 6.6 / 1

: 5 bara / 110 oC

: 38.1 %

(%)

70
60
50
40
30
20
10
0

12

24

36

48

60

72

84

96

(h)

 (2)
MeOH / FFAs

: 10 / 1

: 12 bara / 100 oC

: 3.03 %

: Q = 60 g/h

(%)

100
80
60

70 h

40
20
0
0

1000

2000
3000
(min)

4000

5000