Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
[11]
Patent Number:
5,908,946
Stern et al.
[45]
Date of Patent:
Jun. 1, 1999
[54]
OTHER PUBLICATIONS
[51]
[52]
[58]
[FR]
[57]
[56]
ABSTRACT
References Cited
712,747
7/1902
5,525,126
5,532,392
6/1997
Germany .
44/308
21 Claims, No Drawings
5,908,946
1
15
glycerine.
viable.
Reaction Scheme II
SUMMARY OF THE INVENTION
45
construction-site equipment.
When an ester is produced from oil and monoalcohol, it
automatically forms, depending on the nature of the oil that
is employed at the beginning, 10 to 15% of a secondary
product, Which is glycerine. This glycerine is sold at a high
points of the esters that are formed With these alcohols are
55
loWer than those of the methyl esters, With the gain some
times being 10 C., Which makes it possible to use more
saturated oils from the outset.
Generally, in the conventional processes that use alkaline
5,908,946
4
3
invention, a tWo-stage reaction is often employed; in the
?rst, the ester and the glycerine are decanted When the
evaporate it.
In addition, the US. Pat. No. 4,668,439 is knoWn, Which
alcohol through oil at more than 210 C., most often at 240
C., in the presence of a soluble catalyst, Which can be a Zinc
10
cations.
15
20
system.
Among the prior documents that deal With heterogeneous
and methanol into methyl ester, is an alumina or a mixture 25 chloride, Zinc sulfate, Zinc poWder, barium oxide, calcium
30
potential drawbacks:
the fact that the operation is carried out starting With various
alcohols of C1 to C18 and varied oils, vegetable or animal,
acid or neutral, by using at least one catalyst that is selected
from among Zinc oxide, mixtures of Zinc oxide and alumi
num oxide, and Zinc aluminates that are de?ned by a certain
soluble.
Finally, the prior art does not provide information on a
reaction that can be employed economically on a industrial
patent EP-B-0 193 243, Which cites GB-A 795 573, Zinc
soaps Would be formed With the Zinc compounds, Which
naturally cannot be alloWed in fuels. This is mainly due, it
65
5,908,946
6
5
Among the oils that can be used in the process of the
oils, babassu oils, old or neW colZa oils, sun?oWer seed oils,
oils, and cramble oils and all the oils that come from, for
example, sun?oWer seeds or colZa by genetic engineering or
hybridiZation.
It is even possible to use frying oils, squaring oils, various
animal oils, such as ?sh oils, and even fats because more
10
20
25
35
reasonable VVH.
The operating conditions that are used clearly depend on
the process that is selected. If a discontinuous reaction is
used, it is possible to Work in one or tWo stages, i.e., to
achieve a ?rst reaction With 8590% conversion, to cool
folloWing procedures:
40
30
sion.
The catalyst that is used can be obtained by one of the
1. Impregnating at least one soluble Zinc salt of alumina
gradually decrease.
It may be advantageous to calcine the catalyst at a
suf?cient temperature to combine the alumina and Zinc
tion or oligomeriZation.
The presence of fatty acid in the oils is not detrimental a
55
60
hydrotalcite phase.
65
5,908,946
7
10
15
in the Way of sterol esters. The sterol esters, Which are heavy
20
stages:
25
TABLE 1
Oil
Methanol
Water
Ester
Ester
(g)
(g)
(g)
(O C.)
2 hours (%)
6 hours (%)
120
120
120
120
227
227
57
61
75.6
73.7
120
120*
120
120
227
224-6
28.3
91
56.2
94.3
30
35
EXAMPLE 5
40
EXAMPLE 1
50
Oil
Methanol
Catalyst
after 4
(g)
(g)
(g)
C C.)
hours (0/0)
180
60
227
37
180
60
1.8
227
74.2
55
EXAMPLE 6
In?uence of Water
65
5,908,946
10
Surface area: 65 m2
contacttime :
lyst.
The substrates that are used are the re?ned colZa oil Whose
10
TG=triglyceride
15
TABLE 3
Methanolysis of Colza Oil With the Carrier by Itself
20
pressure, tWo pumps inject the alcohol and the oil upWardly
into the column.
MG=monoglyceride
DG=diglyceride Which does not contain sterol esters
because they do not form under these conditions
R
H/A
(O C.)
VVH
230
240
230
230
240
240
240
240
1.0
0.5
0.5
0.25
0.125
0.125
0.062
0.062
vol/vol (bar)
1
2
1
0.5
0.5
2
0.5
1
50
50
50
50
50
50
50
50
(%)
(%)
(min)
5.6
5.9
5.95
5.6
3.3
4.5
2.4
2.8
35.5
64.5
52.6
59
91
90
95.1
95.3
30
40
60
80
160
350
350
480
(O C.)
VVH
230
235
230
235
235
240
230
210
210
220
230
235
240
240
230
230
235
235
235
235
240
240
245
260
1
1
2
0.5
1.0
1
2
0.5
1.0
1
1
1
2
1
2
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
vol/vol (bar)
3.3
3.3
05
0.5
0.5
0.5
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
50
50
60
50
60
60
50
50
50
50
50
50
50
50
60
60
50
50
50
50
50
50
50
50
TG
DG
MG
t de
contact
(%)
(%)
(%)
(%)
(min)
16.7
13.4
12.8
4.6
3.4
1.5
6.6
7.78
4.3
2.3
1.15
0.88
0.8
4.7
5.9
12.8
0.3
0.02
0.03
0.02
0.08
0.09
0.10
0.07
10.4
9.1
10.4
4.0
3.6
2.0
5.7
5.20
4.4
3.1
2.4
2.2
2.4
4.5
5.0
10.4
1.25
0.1
0.96
0.88
1.15
1.53
1.34
1.30
12.7
12.1
9.3
11.2
8.1
8.9
6.1
8.9
7.1
7.1
8.8
8.8
7.8
5.6
9.3
9.3
4.0
3.9
3.4
3.9
5.04
5.5
6.0
6.9
59.8
64.8
67.4
80
84.7
89.4
81.2
78.1
84
87.2
89.5
89.9
88.9
85
79
67.4
94.4
95.8
95.5
95.1
93.5
92.5
92.4
91.4
46
46
20
80
40
40
20
80
40
40
40
40
40
20
40
20
60
60
60
60
60
60
60
60
(%)
16.7
9.6
13.1
12.0
2.8
3.0
1.7
1.5
[KeyI]
R
H/A
T
40
(%)
41.9
19.9
28.3
23.3
2.8
2.1
0.8
0.03
Carrier
English).
t de
contact
TABLE 4
35
MG
This table provides the results that are obtained each time
after 24 hours of reaction.
DG
TG
65
5,908,946
11
12
TABLE 5-continued
Methanolvsis of Colza Oil With Alumina Calcined Bv Itself.
240 C., With the optimum being located betWeen 230 and
10
VVH
235
235
235
240
240
245
0.5
0.5
0.5
0.5
0.5
0.5
vol/vol (bar)
1
0.5
0.5
1
0.5
0.5
50
50
50
50
50
50
TG
DG
MG
t de
contact
(%)
(%)
(%)
(%)
(min)
9.6
8.4
7.0
6.1
4.8
4.1
5.5
5.6
4.6
4.6
3.8
3.3
4.4
4.4
4.2
5.1
3.6
3.8
80.4
81.4
84.1
83.9
87.6
88.6
60
40
40
60
40
40
TABLE 6
Methanolysis of Colza Oil on alumina + ZnO
20
R
H/A
( C.)
R
H/A
( C.)
VVH
230
230
240
240
240
235
235
0.5
0.5
0.5
0.5
0.5
0.5
0.5
TG
vol/vol (bar)
1
1
2
1
1
0.5
0.5
50
50
50
50
50
50
30
DG
MG
t de
contact
(%)
(%)
(%)
(%)
(min)
0.3
0.2
0.02
0.23
0.13
0.2
0.3
1.1
1.2
1.3
1.6
1.45
0.95
1.4
3.9
3.9
4.35
5.3
5.2
5.9
4.0
94.3
94.5
94.1
92.6
93.2
92.9
94.1
60
60
80
60
60
40
40
30
EXAMPLE 7
35
45
Example 6.
Examples 6 and 7 shoWed a substantial improvement in
activity. It is still a fact that the distribution of pores is not
identical, nor the surface area, Which is greater for the carrier
performance.
EXAMPLE 8
With alumina gel by itself and, on the other hand, With Zinc
aluminate.
traces of methanol.
TABLE 5
TABLE 7
( C.)
VVH
220
220
220
230
230
235
1
0.5
0.5
0.5
0.5
0.5
vol/vol (bar)
0.5
1
2
2
1
1
50
50
50
50
50
50
TG
DG
(%)
(%)
15.5
18.2
13.3
13.2
9.4
9.3
9.7
11.2
7.8
7.6
6.0
5.2
t de
contact
(%)
(%)
(min)
4.66
5.1
6.77
6.5
4.5
4.1
69.9
65.3
72.9
73.5
79.9
81.2
40
60
80
80
60
60
MG
( C.)
VVH
250
250
250
0.5
0.5
0.5
vol/vol (bar)
0.5
0.5
0.5
70
70
70
TG
DG
(%)
(%)
0.5
0.9
1.34
1.3
1.7
1.5
t de
contact
(%)
(%)
(min)
3.6
4.07
3.5
94.5
93.2
93.3
40
40
40
MG
5,908,946
14
13
R
H/A
T
R
H/A
(O C.)
VVH
235
240
0.5
0.25
vol/vol (bar)
0.5
1
70
60
TG
DG
MG
t de
contact
(O C.)
VVH
(%)
(%)
(%)
(%)
(min)
1.5
0.01
2.05
0.2
4.1
3.4
92.2
96.3
40
120
235
235
235
1
1
1
50
50
50
t de
contact
(%)
(%)
(min)
5.4
2.7
1.6
88
94.5
97.0
52
48
40
DG
MG
(%)
(%)
1.87
0.5
0.08
4.5
2.0
1.2
vol/vol (bar)
7
4
2
TG
10
[KeyI]
lKeyil
EXAMPLE 9
15
EXAMPLE 11
20
methanol contents.
tions:
The ethanol has 370 ppm of water
25
TABLE 8
Methanol
Ethyl esters
(70)
(70)
1
3
5
10
83.4
89.3
89.2
89.7
slightly
yellow
Acidity: not detectable
Odor: none
35
EXAMPLE 12
40
EXAMPLE 10
235
235
240
240
235
240
240
240
240
50
50
50
50
50
50
50
50
50
35
35
35
35
70
70
70
70
70
70
70
70
70
70
70
70
35
35
[KeyI]
t (jour) = time (day)
t de contact (min) = contact time (min)
65
t de contact
(min)
40
40
40
40
30
30
30
40
40
TG
DG
MG
VVH (70)
(70)
(70)
(70)
1.8
4.7
15.9
17.6
17.4
18.4
22.2
21.5
21.6
3.9
5
6.9
6.1
5.7
5.6
7.5
5.8
5.8
93.6
85.1
55.6
56.9
47.5
43.7
35.7
37.2
30.9
0.5
0.5
0.5
0.5
1
1
1
1
1
0.7
5.2
21.5
18.8
29.2
32.1
33.8
35.3
42
5,908,946
15
16
and Without departing from the spirit and scope thereof, can
make various changes and modi?cations of this invention to
adapt it to various usages and conditions.
We claim:
1. Process for the production of at least one fatty acid ester
EXAMPLE 13
continuously.
10
TABLE 11
Dbit Dbit
T
35
17.5
17.5
17.5
70
35
35
17.5
17.5
17.5
70
70
35
17.5
8.75
8.75
8.75
35
17.5
17.5
8.75
8.75
8.75
35
35
17.5
tde
P
TG
DG
MG
contact
(bar)
<%)
<%)
<%)
<%)
(min)
50
50
50
50
70
50
50
50
50
50
70
50
50
57.2
49.8
31.5
29.1
57.5
39.4
27.1
7.1
3.9
4.55
76.2
67.9
36.3
22.5
22.6
25.9
26
24.2
28.3
23.7
10.3
6.3
6.3
15.8
20.7
25.5
4.9
5.6
9.7
10.5
4.25
8.1
10.8
10.9
8.5
8.1
1.5
2.4
9.1
14.6
21.4
32.2
33.8
13.3
23.4
37.5
71.1
80.7
80.5
5.8
8.4
27
80
160
160
160
40
80
80
160
160
160
40
40
80
of ZnAl2O4;
15
25
30
ometry.
5. Aprocess according to claim 1, Wherein the catalyst has
a surface area of 10 to 200 m2/g, a pore volume of 0.2 to 1.2
35
EXAMPLE 14
40
50
60
erence.
employed discontinuously.
65
5,908,946
17
18