We were interested by turning into account of glycerol, a by-product formed in large quantities in...
1
We were interested by turning into account of glycerol, a by-product formed in large quantities in the bio-diesel production, into propylene glycol. This hydrogenolysis reaction could be a useful procedure for glycerol valorification The product can be separated easily from the heterogeneous catalyst. Model predictions agree with experimental data The values for k1, k2, k3 were obtained by using different functions of MATLAB Program. This study could be useful for predicting a laboratory reactor performance. The reaction is straight-forward, does not requires solvents, promoters or hardly RESULTS AND DISCUSSION RESULTS AND DISCUSSION INTRODUCTION INTRODUCTION CONCLUSIONS CONCLUSIONS EXPERIMENTAL EXPERIMENTAL Glycerol can be directly hydrogenated to propylene glycol using copper catalysts (43.89% CuO, 42.09% Cr 2 O 3 , 10.36% BaO). Activation of the catalysts was performed previous to the hydrogenation in following conditions: 10 bar hydrogen pressure, 4 h activation time, 280 0 C reaction temperature. The glycerol hydrogenolysis to propylene glycol in presence of copper chromite as catalysts has been investigated in liquid phase. The main reactions are dehydration to acetol and hydrogenation to propylene glycol. Based on the results of our earlier studies, as well as on data from the literature and the experimental results presented here, a kinetic study for this hydrogenolysis reaction is discussed. A KINETIC STUDY FOR GLYCEROL HYDROGENOLYSIS TO PROPYLENE GLYCOL Adriana Marinoiu 1 , Claudia Cobzaru 2 , Ioan Iordache 3 , Mihaela Iordache 4 1 S.C. OLTCHIM S.A.- Research Center Rm Valcea, 1 Uzinei St., Rm. Valcea 240050, Romania 2 Faculty of Industrial Chemistry, Technical University of Iasi, 71 D, Mangeron Ave., 70050, Iasi 3 National R D Institute for Cryogenics and Isotopic Technologies- ICIT, Rm Valcea, 4 Uzinei St.,240050, Romania 4 The National Research and Development Institut for Industrial Ecology – INCD ECOIND Bucharest-Subsidiary Ramnicu Valcea, 1 Uzinei Street, Ramnicu Valcea 240050,Romania The autoclave containing the activated catalyst was loaded with desired quantity of glycerol and pressurized with hydrogen at room temperature, to the necessary pressure. All the reactions were conducted at the followed conditions: 5 % wt of catalyst, 180-240 °C reaction temperature, reaction pressure in range 10-40 bar, reaction time 8 hours. Technical University „Gheorghe Asachi” Iaşi Faculty of Industrial Chemistry Faculty of Industrial Chemistry Glycerol hydrogenolyis to propylene glycol was carried out over a broad range of reaction conditions. Outlet glycerol conversion, selectivity to propylene glycol and temperature profiles were collected experimentally to characterize the system. The data for the proposed model at different temperatures were processed using MATLAB software. The plots m=f(t) are illustrating an agreement between experimental (1) and predicted values (2) at 463 K (Figure 1), 473 K (Figure 2), 483 K (Figure 3) . Rate constant values were determined by minimizing the sum of squared deviations between the experimental and model predicted values Figure 1. 0 5 10 15 20 0 10 20 30 40 g lyce rol1 a ce tol1 PG1 G lycerol2 A cetol2 PG2 % tim e h 0 5 10 15 20 0 5 10 15 20 25 30 35 40 G lycerol1 A cetol1 PG1 G lycerol2 A cetol2 PG2 % tim e h 0 5 10 15 20 0 5 10 15 20 25 30 35 40 G lycerol1 A cetol1 PG1 G lycerol2 A cetol2 PG2 % tim e (h ) Figure 2. Figure 3.
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Transcript of We were interested by turning into account of glycerol, a by-product formed in large quantities in...
We were interested by turning into account of glycerol, a by-product formed in large quantities in the bio-diesel
production, into propylene glycol.
This hydrogenolysis reaction could be a useful procedure for glycerol valorification
The product can be separated easily from the heterogeneous catalyst.
Model predictions agree with experimental data
The values for k1, k2, k3 were obtained by using different functions of MATLAB Program.
This study could be useful for predicting a laboratory reactor performance.
The reaction is straight-forward, does not requires solvents, promoters or hardly conditions.
Additional studies regarding other kinetic models are currently underway
RESULTS AND DISCUSSIONRESULTS AND DISCUSSION
INTRODUCTIONINTRODUCTION
CONCLUSIONSCONCLUSIONS
EXPERIMENTALEXPERIMENTAL
Glycerol can be directly hydrogenated to propylene glycol using copper catalysts (43.89% CuO, 42.09% Cr2O3, 10.36% BaO).
Activation of the catalysts was performed previous to the hydrogenation in following conditions: 10 bar hydrogen pressure, 4 h activation time, 2800C reaction temperature.
The glycerol hydrogenolysis to propylene glycol in presence of copper chromite as catalysts has been investigated in liquid phase. The main reactions are dehydration to acetol and hydrogenation to propylene glycol. Based on the results of our earlier studies, as well as on data from the literature and the experimental results presented here, a kinetic study for this hydrogenolysis reaction is discussed.
A KINETIC STUDY FOR GLYCEROL HYDROGENOLYSIS TOPROPYLENE GLYCOL
Adriana Marinoiu1, Claudia Cobzaru2, Ioan Iordache3, Mihaela Iordache4
1 S.C. OLTCHIM S.A.- Research Center Rm Valcea, 1 Uzinei St., Rm. Valcea 240050, Romania2 Faculty of Industrial Chemistry, Technical University of Iasi, 71 D, Mangeron Ave., 70050, Iasi
3 National R D Institute for Cryogenics and Isotopic Technologies- ICIT, Rm Valcea, 4 Uzinei St.,240050, Romania4The National Research and Development Institut for Industrial Ecology – INCD ECOIND Bucharest-Subsidiary Ramnicu Valcea, 1 Uzinei Street, Ramnicu
Valcea 240050,Romania
The autoclave containing the activated catalyst was loaded with desired quantity of glycerol and pressurized with hydrogen at room temperature, to the necessary pressure.
All the reactions were conducted at the followed conditions: 5 % wt of catalyst, 180-240 °C reaction temperature, reaction pressure in range 10-40 bar, reaction time 8 hours.
Technical University „Gheorghe Asachi” IaşiFaculty of Industrial ChemistryFaculty of Industrial Chemistry
Glycerol hydrogenolyis to propylene glycol was carried out over a broad range of reaction conditions. Outlet glycerol conversion, selectivity to propylene glycol and temperature profiles were collected experimentally to characterize the system. The data for the proposed model at different temperatures were processed using MATLAB software. The plots m=f(t) are illustrating an agreement between experimental (1) and predicted values (2) at 463 K (Figure 1), 473 K (Figure 2), 483 K (Figure 3) . Rate constant values were determined by minimizing the sum of squared deviations between the experimental and model predicted values
Figure 1.
0 5 10 15 200
10
20
30
40
glycerol1 acetol1 PG1 Glycerol2 Acetol2 PG2
%
time h
0 5 10 15 200
5
10
15
20
25
30
35
40 Glycerol1 Acetol1 PG1 Glycerol2 Acetol2 PG2
%
time h
0 5 10 15 200
5
10
15
20
25
30
35
40 Glycerol1 Acetol1 PG1 Glycerol2 Acetol2 PG2
%
time (h)
Figure 2. Figure 3.
