Химия и химические технологии/5. Фундаментальные проблемы
создания новых материалов и технологий
D.t.n. Melnik A.P., Papchenko V.Y.
National technical university
«Kharkov polytechnic institute»
THE
INVESTIGATION OF INFLUENCE FOR PARAMETERS IN SUNFLOWER OIL AMIDATION REACTION
ON THE MONO-, DIACYLGLYCEROLS
To
direct the technological process of amidation and to forecast the yield of
mono-, diacylglycerols scientifically grounded and stable under the influence
of mole correlation of outlet reagents, temperature and time of reaction run,
we need have the corresponding tools whose the role could be executed by
mathematical models. Such models could be made and created according the plan
of full factor experiment. To estimate the possibility of forecasting the mono-
(MAG), diacylglycerols (DAG) concentration according the static model of sunflower
oil amidation by the diethanolamine as the regression equation the 2-factor
experiment has been carried out according [1]. Using the results of previous
investigation [2, 3] the results of creating such statistical models are given
below.
In
table 1 the factors levels and intervals of variables, changes in the
experiment plan have been given that has an influence on the yield of MAG and
DAG, namely temperature (T) and reaction duration (τ). The planification
on matrix for the experiment in natural scale in unitless coordinative system
has been described in table 2.
Table 1
Factors,
levels and intervals of variation for variables in experiment plan
|
Levels |
Factors |
|
|
Т, К |
τ, с |
|
|
High |
473 |
10800 |
|
Low |
433 |
1800 |
|
Basic |
453 |
7200 |
|
Variation interval |
20 |
4500 |
Table 2
Experiment
plan
|
№ |
Factors in natural scale |
Factors in unitless system of coordinates |
DAG concentration, mas.part. |
MAG concentration, mas.part. |
||
|
Т, К |
τ, с |
X1 |
X2 |
Y1 |
Y2 |
|
|
1 |
473 |
1800 |
+1 |
–1 |
0,2452 |
0,1358 |
|
2 |
433 |
1800 |
–1 |
–1 |
0,1562 |
0,0904 |
|
3 |
473 |
10800 |
+1 |
+1 |
0,2899 |
0,1924 |
|
4 |
433 |
10800 |
–1 |
+1 |
0,2581 |
0,1594 |
The
regression equation has been obtained:
(1)
(2)
In
order to check out the meaning ness of regression equation factors 3 identicaly
same investigation in arbitrary point Т=453 К and τ=7200 с have been made and following
results 
for DAG have been obtained: 
; for MAG 
The recreation dispersion 
(for DAG) і 
(for MAG) has been determined according [4, 5]. The meaningless of factors for
regression equation has been evaluated according Student's criterion according [4, 5].
On
the basis of calculations made and after checking out the meaning ness of
factors, the regression equations for varib lessen coded have got the following
view:
(3)
(4)
Adequate
ability of the equations obtained (3, 4) has been proved according Fischer criterion
the meaning of the rest dispersion for DAG 
, MAG 
. Because of the meaning calculated
of Fischer criterion for DAG Fр=8,67, MAG Fр=1,86 the table meaning [4] of Fischer criterion Fт=18,51 (while the meaning ability level р=0,05) for the freedom stages of rest dispersion f1=N-l=4-3=1, and the quantity of freedom stages
for dispersion of recreation f2=n-1=3-1=2,
so Fp<Fт.
So the equations obtained according [5] has adequately described the
experiment.
The
equations decoded (3, 4) has such view:
(5)
(6)
де СDAG – diacylglycerols
concentration, mas.part..;
СМAG – monoacylglycerols
concentration, mas.part.
The
equations (tabl. 3, 4) of experimentally obtained concentration MAG, DAG
with concentrations obtained according the regression equations (5, 6) is the prove that the
average deviation is not higher than 10,2 % for DAG and 5,1 % for
MAG, what is been taken for engineering calculations.
Table 3
The
equations of experimental and calculated concentrations DAG while MB of reagents
1:1 temperature 433 K
|
Time, с |
СDAGе, mas.part. |
СDAGр, mas.part. |
Deviation, % |
|
1800 |
0,1562 |
0,1705 |
9,15 |
|
3600 |
0,2116 |
0,1851 |
12,5 |
|
5400 |
0,2268 |
0,1998 |
11,9 |
|
7200 |
0,2439 |
0,2145 |
12,1 |
|
9000 |
0,2550 |
0,2291 |
10,2 |
|
10800 |
0,2581 |
0,2438 |
5,54 |
|
Average deviation |
10,2 |
||
Table 4
The
equations of experimental and calculated concentrations MAG while MB of
reagents 1:2 temperature 473 K
|
Time, с |
СMAGе, mas.part. |
СMAGр, mas.part. |
Deviation, % |
|
1800 |
0,1358 |
0,1327 |
2,28 |
|
3600 |
0,1498 |
0,1453 |
9,1 |
|
5400 |
0,1811 |
0,1578 |
5,3 |
|
7200 |
0,1867 |
0,1704 |
8,7 |
|
9000 |
0,1901 |
0,1829 |
3,8 |
|
10800 |
0,1924 |
0,1955 |
1,6 |
|
Average deviation |
5,1 |
||
According
the obtained equations of regression the maximum concentration of DAG, as
according experimental data, has been obtained while MB of reagents 1:1, and
maximal concentration of MAG – while MB of reagents 1:1 and temperature
473 K during 3 hours. So such statistical model as regression equation
could be used for forecasting of concentration DAG and MAG depending on changes
in technological parameters.
Conclusions:
1. The
statistical mathematical model to evaluate the concentrations of MAG in
technological process of their production by amidation of sunflower oil using
diethanolamine has been created in dependence on changes in time and
temperature.
2. The
mathematical model has been created for evaluation of DAG concentrations in the
time and temperature changes in technological process of sunflower oil
amidation.
3. The
statistical calculation and comparison of experimental and calculated results
have proved the adequacy of models with average deviation ~ 5 % for
MAG and ~ 10 % for DAG.
References: 1. Мельник А.П. Практикум з хімії та
технології поверхнево-активних похідних вуглеводневої сировини: навчальний
посібник / А.П. Мельник,
Чумак О.П., Березка Т.О. - Харків: Курсор, 2004. – 277 с. 2. Мельник А.П. Дослідження амідування триацилгліцеринів
соняшникової олії діетаноламіном / А.П. Мельник,
В.Ю. Папченко, Т.В. Матвєєва // Вісник Національного технічного
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