Modified Natural Dolomite and Its Influence on the Production of Glycerol Carbonate: Effects of Structural and Basicity Properties
Abstract
:1. Introduction
2. Materials and Methods
2.1. Dolomite and Various Treatments
2.2. Characterization
2.2.1. XRD Analysis
2.2.2. Rietveld Refinement
2.2.3. Thermogravimetric Analysis (TGA)
2.2.4. Fourier-Transform Infrared (FT-IR) Spectroscopy
2.2.5. N2 Adsorption-Desorption Isotherms Measurements
2.2.6. CO2 Temperature-Programed Desorption (CO2-TPD)
2.3. Glycerol Carbonate Synthesis and Product Analysis
3. Results and Discussion
3.1. XRD Analysis and Rietveld Refinement
3.2. FT-IR Characterization of the Treated Samples Before Calcination
3.3. FT-IR Characterization of the Treated Samples after Calcination
3.4. Thermogravimetric Analysis (TGA) of Uncalcined Samples
3.5. Textural Properties of the Treated Samples
3.6. CO2 Adsorption and Basicity
3.7. Catalytic Activity—Synthesis of Glycerol Carbonate
4. Conclusions
- Different treatments led to the reorganization of the pore system of dolomite by diminishing pore diameter from approximately 17 Å to 4~6 Å and enhancing the surface area by 4~5 times. Hydrothermal and formic acid treatments greatly improved the surface area.
- The use of the different treatments and calcination of the dolomite modified the crystalline structure and composition, determined by the XRD analysis and Rietveld refinements. Most of the samples contained crystalline CaO and Ca(OH)2 in different percentages, resulting the hydrothermal treated sample with the higher content of Ca(OH)2. The presence of the hydroxyl species in the structure and surface could be as a result of the fast rehydration of highly active sites of CaO with moisture.
- The presence of Ca(OH)2 in the materials was related to the presence of active sites needed to catalyze the glycerol carbonate synthesis as evidenced by the fact that glycerol carbonate production rate was proportional to the amount of Ca(OH)2. Among the treatments the hydrothermal led to the highest concentration of active sites with weak and moderate strength basicity. However, the sulfuric and phosphoric acids at stoichiometric molar ratio produced inactive crystalline CaSO4, Ca2P2O7, and Mg2P2O7 phases for the glycerol carbonate synthesis, evidenced by the Rietveld refinement and FTIR results.
- The best catalytic performance for the synthesis of glycerol carbonate was achieved on the C-DH2O and C-DFormic-5 catalysts with apparent carbonate production rate of 3.42 and 3.32 mmol/min·gcat, respectively. Even though most of the materials increased their superficial area, which could be related with the catalytic activity, the obtained results suggest that the key parameter required for good catalytic activity was the formation of more basic sites with weak–moderate strength in the catalysts.
- The hydrothermal treatment has been proven to be an economic and environment friendly method for obtaining dolomite with potential use in processes that require a weak-medium basic catalyst for the transesterification reaction of glycerol and dimethyl carbonate. These may lead to new applications of natural dolomite minerals.
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Sample-Treatment Acid | Label |
---|---|
Dolomite | U or C-D |
Dolomite-H2O | U or C-DH2O |
Dolomite-Formic Acid | U or C-DFormic-# |
Dolomite-Acetic Acid | U or C-DAcetic-# |
Dolomite-Nitric Acid | U or C-DNitric-# |
Dolomite-Sulfuric Acid | U or C-DSulfuric-# |
Dolomite-Phosphoric acid | U or C-DPhosphoric-# |
Sample | Crystalline Phases | Symmetry | Space Group | Lattice Parameters (Å) | Crystallite Size (Å) | % Vol | %RWP | ||
---|---|---|---|---|---|---|---|---|---|
a | b | c | |||||||
C-D | Ca(OH)2 | Trigonal | P3m1 | 3.5926 | 3.5926 | 4.9189 | 242.1 | 47.80 | 8.29 |
MgO | Cubic | Fm-3m | 4.2132 | 4.2132 | 4.2132 | 3908.2 | 38.02 | ||
CaCO3 | Trigonal | R-3c:H | 4.9950 | 4.9950 | 17.0743 | 692.3 | 7.28 | ||
Orthorhombic | Pbnm | 4.0604 | 7.1536 | 8.3997 | 266.3 | 4.26 | |||
Orthorhombic | Pmcn | 4.9535 | 8.0206 | 5.7447 | 207.8 | 1.53 | |||
CaO | Cubic | Fm-3m | 4.7990 | 4.7990 | 4.7990 | 30.8 | 1.11 | ||
C-DH2O | Ca(OH)2 | Trigonal | P3m1 | 3.5926 | 3.5926 | 4.9226 | 239.9 | 65.35 | 9.12 |
MgO | Cubic | Fm-3m | 4.2152 | 4.2152 | 4.2152 | 377.7 | 24.61 | ||
CaCO3 | Trigonal | R-3c:H | 4.9956 | 4.9956 | 17.0659 | 607.1 | 9.91 | ||
Orthorhombic | Pbnm | 4.1291 | 7.1581 | 8.4764 | 25.3 | 0.13 | |||
C-DFormic-5 | Ca(OH)2 | Trigonal | P3m1 | 3.5935 | 3.5935 | 4.9130 | 249.0 | 58.63 | 10.14 |
MgO | Cubic | Fm-3m | 4.2154 | 4.2154 | 4.2154 | 349.7 | 32.47 | ||
CaCO3 | Trigonal | R-3c:H | 4.9970 | 4.9970 | 17.0600 | 590.5 | 7.10 | ||
Orthorhombic | Pbnm | 4.0768 | 7.1546 | 8.4337 | 127.4 | 1.80 | |||
C-DFormic-3 | Ca(OH)2 | Trigonal | P3m1 | 3.5914 | 3.5914 | 4.9137 | 234.0 | 56.29 | 9.65 |
MgO | Cubic | Fm-3m | 4.2159 | 4.2159 | 4.2159 | 349.6 | 31.92 | ||
CaCO3 | Trigonal | R-3c:H | 4.9950 | 4.9950 | 17.0707 | 530.0 | 9.65 | ||
Orthorhombic | Pbnm | 4.1291 | 7.1581 | 8.4764 | 19.8 | 2.14 | |||
C-DAcetic-S | Ca(OH)2 | Trigonal | P3m1 | 3.5931 | 3.5931 | 4.9164 | 258.8 | 0.25 | 10.03 |
MgO | Cubic | Fm-3m | 4.2131 | 4.2131 | 4.2131 | 583.4 | 32.98 | ||
CaCO3 | Trigonal | R-3c:H | 4.9978 | 4.9978 | 17.0689 | 617.5 | 9.48 | ||
Orthorhombic | Pbnm | 4.0847 | 7.1554 | 8.4764 | 34.2 | 0.49 | |||
CaO | Cubic | Fm-3m | 4.7391 | 4.7391 | 4.7391 | 66.6 | 56.80 | ||
C-DNitric-5 | Ca(OH)2 | Trigonal | P3m1 | 3.5937 | 3.5937 | 4.9110 | 248.8 | 20.71 | 11.31 |
MgO | Cubic | Fm-3m | 4.2144 | 4.2144 | 4.2144 | 422.1 | 74.29 | ||
CaCO3 | Trigonal | R-3c:H | 4.9932 | 4.9932 | 17.0576 | 292.9 | 4.88 | ||
Orthorhombic | Pbnm | 4.0929 | 7.1364 | 8.2680 | 182.4 | 0.12 | |||
C-DSulfuric-1 | Ca(OH)2 | Trigonal | P3m1 | 3.5923 | 3.5923 | 4.9114 | 198.3 | 53.45 | 12.99 |
CaO | Cubic | Fm-3m | 4.8107 | 4.8107 | 4.8107 | 992.5 | 11.52 | ||
MgO | Cubic | Fm-3m | 4.2122 | 4.2122 | 4.2122 | 628.1 | 31.18 | ||
CaSO4 | Orthorhombic | Amma | 6.9929 | 6.9907 | 6.2481 | 802.8 | 3.85 | ||
C-DSulfuric-S | CaSO4 | Orthorhombic | Amma | 6.9978 | 6.9899 | 6.2405 | 2955.7 | 100.00 | 17.51 |
C-DPhosphoric-5 | Ca(OH)2 | Trigonal | P3m1 | 3.5931 | 3.5931 | 4.9164 | 254.0 | 47.56 | 11.77 |
MgO | Cubic | Fm-3m | 4.2131 | 4.2131 | 4.2131 | 435.8 | 39.85 | ||
CaCO3 | Trigonal | R-3c:H | 4.9978 | 4.9978 | 17.0689 | 260.4 | 7.10 | ||
Orthorhombic | Pbnm | 4.0847 | 7.1554 | 8.4764 | 185.8 | 5.50 | |||
C-DPhosphoric-S | Ca2P2O7 | Tetragonal | P41 | 6.6807 | 6.6807 | 24.1191 | 1334.6 | 67.37 | 14.16 |
Mg2P2O7 | Monoclinic | P21/c:b1 | 6.9438 | 8.2855 | 9.0582 | 539.7 | 32.63 | ||
* Beta = 114° |
Reaction Number | Reaction | ΔH°r (kJ/mol) | ΔG°r (kJ/mol) |
---|---|---|---|
1 | CaO + H2O → Ca(OH)2 | −65.16 | −65.15 |
2 | CaO + 2CHOOH → Ca(CHOO)2 + H2O | 2585.8 | 2560.6 |
3 | Ca(OH)2 + 2CHOOH → Ca(CHOO)2 + 2H2O | 2650.4 | 2664.8 |
4 | CaO + 2CH3–CHOOH → Ca(CH3–CHOO)2 + H2O | −196.0 | −227.1 |
5 | Ca(OH)2 + 2CH3–CHOOH → Ca(CH3–CHOO)2 + 2H2O | −131.3 | −123.0 |
6 | CaO + 2HNO3 → Ca(NO3)2 + H2O | −240.0 | −239.9 |
7 | Ca(OH)2 + 2HNO3 → Ca(NO3)2 + 2H2O | −75.4 | −109.3 |
8 | CaO + H2SO4 → CaSO4 + H2O | −262.6 | −256.6 |
9 | Ca(OH)2 + H2SO4 → CaSO4 + 2H2O | −198.0 | −199.7 |
10 | 3CaO + 2H3PO4 → Ca3(PO4)2 + 3H2O | −528.1 | −598.1 |
11 | 3Ca(OH)2 + 2H3PO4 → Ca3(PO4)2 + 6H2O | −334.1 | −364.7 |
Sample | Brunauer-Emmett-Teller (BET) Surface Area (m2/g) | Barrett-Joyner-Halenda (BJH) Pore Volume (cm3/g) | Barrett–Joyner–Halenda (BJH) Pore Diameter (Å) |
---|---|---|---|
U-D | 8.61 | 0.017 | 16.95 |
C-D | 18.51 | 0.038 | 18.82 |
C-DH2O | 31.88 | 0.059 | 3.56 |
C-DFormic-S | 42.64 | 0.099 | 3.58 |
C-DFormic-1 | N. D. | N. D. | N. D. |
C-DFormic-3 | 46.08 | 0.085 | 3.57 |
C-DFormic-5 | 38.30 | 0.077 | 3.58 |
C-DAcetic-S | 42.01 | 0.137 | 5.57 |
C-DAcetic-1 | 31.39 | 0.070 | 3.59 |
C-DAcetic-3 | 33.46 | 0.072 | 3.58 |
C-DAcetic-5 | 45.79 | 0.086 | 3.60 |
C-DNitric-S | 25.40 | 0.063 | 3.98 |
C-DNitric-1 | 22.00 | 0.050 | 3.58 |
C-DNitric-3 | 33.26 | 0.075 | 3.58 |
C-DNitric-5 | 44.58 | 0.080 | 4.42 |
C-DSulfuric-S | 6.93 | 0.017 | 3.97 |
C-DSulfuric-1 | 20.32 | 0.036 | 3.59 |
C-DSulfuric-3 | 21.87 | 0.050 | 3.96 |
C-DSulfuric-5 | 34.57 | 0.074 | 3.58 |
C-DPhosphoric-S | 6.32 | 0.007 | 14.4 |
C-DPhosphoric-1 | 19.22 | 0.048 | 3.25 |
C-DPhosphoric-3 | 30.99 | 0.056 | 3.97 |
C-DPhosphoric-5 | 40.09 | 0.078 | 3.97 |
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González-García, J.; Chen, L.; Campuzano-Calderon, O.; Núñez-Correa, S.; López-Guajardo, E.A.; Wang, J.A.; Montesinos-Castellanos, A. Modified Natural Dolomite and Its Influence on the Production of Glycerol Carbonate: Effects of Structural and Basicity Properties. Materials 2021, 14, 2358. https://doi.org/10.3390/ma14092358
González-García J, Chen L, Campuzano-Calderon O, Núñez-Correa S, López-Guajardo EA, Wang JA, Montesinos-Castellanos A. Modified Natural Dolomite and Its Influence on the Production of Glycerol Carbonate: Effects of Structural and Basicity Properties. Materials. 2021; 14(9):2358. https://doi.org/10.3390/ma14092358
Chicago/Turabian StyleGonzález-García, Julio, Lifang Chen, Omar Campuzano-Calderon, Sara Núñez-Correa, Enrique A. López-Guajardo, Jin An Wang, and Alejandro Montesinos-Castellanos. 2021. "Modified Natural Dolomite and Its Influence on the Production of Glycerol Carbonate: Effects of Structural and Basicity Properties" Materials 14, no. 9: 2358. https://doi.org/10.3390/ma14092358