CO2 absorption and sequestration as various polymorphs of CaCO3 using sterically hindered amine.

One aspect of the attempt to restrain global warming is the reduction of the levels of atmospheric CO2 produced by fossil fuel power systems. This study attempted to develop a method that reduces CO2 emissions by investigating the absorption of CO2 into sterically hindered amine 2-amino-2-methyl-1-propanol (AMP), the acceleration of the absorption rate by using the enzyme carbonic anhydrase (CA), and the conversion of the absorption product to stable carbonates. CO2 absorbed by AMP is converted via a zwitterion mechanism to bicarbonate species; the presence of these anions was confirmed with (1)H and (13)C NMR spectral analysis. The catalytic efficiency (kcat/Km), CO2 absorption capacities, and enthalpy changes (ΔHabs) of aqueous AMP in the presence or absence of CA were found to be 2.61 × 10(6) or 1.35 × 10(2) M(-1) s(-1), 0.97 or 0.96 mol/mol, and -69 or -67 kJ/mol, respectively. The carbonation of AMP-absorbed CO2 was performed by using various Ca(2+) sources, viz., CaCl2 (CAC), Ca(OOCCH3)2 (CAA), and Ca(OOCCH2CH3)2 (CAP), to obtain various polymorphs of CaCO3. The yields of CaCO3 from the Ca(2+) sources were found in the order CAP > CAA > CAC as a result of the effects of the corresponding anions. CAC produces pure rhombohedral calcite, and CAA and CAP produce the unusual phase transformation of calcite to spherical vaterite crystals. Thus, AMP in combination with CAA and CAP can be used as a CO2 absorbent and buffering agent for the sequestration of CO2 in porous CaCO3.

Carbonic anhydrase promotes the absorption rate of CO2 in post-combustion processes.

The rate of carbon dioxide (CO2) absorption by monoethanol amine (MEA), diethanol amine (DEA), N-methyl-2,2'-iminodiethanol (MDEA), and 2-amino-2-methyl 1-propanol (AMP) solutions was found to be enhanced by the addition of bovine carbonic anhydrase (CA), has been investigated using a vapor-liquid equilibrium (VLE) device. The enthalpy (-ΔHabs) of CO2 absorption and the absorption capacities of aqueous amines were measured in the presence and/or absence of CA enzyme via differential reaction calorimeter (DRC). The reaction temperature (ΔT) under adiabatic conditions was determined based on the DRC analysis. Bicarbonate and carbamate species formation mechanisms were elucidated by (1)H and (13)C NMR spectral analysis. The overall CO2 absorption rate (flux) and rate constant (kapp) followed the order MEA > DEA > AMP > MDEA in the absence or presence of CA. Hydration of CO2 by MDEA in the presence of CA directly produced bicarbonate, whereas AMP produced unstable carbamate intermediate, then underwent hydrolytic reaction and converted to bicarbonate. The MDEA > AMP > DEA > MEA reverse ordering of the enhanced CO2 flux and kapp in the presence of CA was due to bicarbonate formation by the tertiary and sterically hindered amines. Thus, CA increased the rate of CO2 absorption by MDEA by a factor of 3 relative to the rate of absorption by MDEA alone. The thermal effects suggested that CA yielded a higher activity at 40 °C.

Carbonic anhydrase immobilized on encapsulated magnetic nanoparticles for CO2 sequestration.

Bovine carbonic anhydrase (BCA) was covalently immobilized onto OAPS (octa(aminophenyl)silsesquioxane)-functionalized Fe(3)O(4)/SiO(2) nanoparticles by using glutaraldehyde as a spacer. The Fe(3)O(4) nanoparticles were coated with SiO(2), onto which was grafted OAPS, and the product was characterized using SEM, TEM, XRD, IR, X-ray photoelectron spectroscopy (XPS), and magnetometer analysis. The enzymatic activities of the free and Fe(3)O(4)/SiO(2)/OAPS-conjugated BCA (Fe-CA) were investigated by hydrolyzing p-nitrophenylacetate (p-NPA), and hydration and sequestration of CO(2) to CaCO(3). The CO(2) conversion efficiency and reusability of the Fe-CA were studied before and after washing the recovered Fe-CA by applying a magnetic field and quantifying the unreacted Ca(2+) ions by using ion chromatography. After 30 cycles, the Fe-CA displayed strong activity, and the CO(2) capture efficiency was 26-fold higher than that of the free enzyme. Storage stability studies suggested that Fe-CA retained nearly 82 % of its activity after 30 days. Nucleation of the precipitated CaCO(3) was monitored by using polarized light microscopy, which revealed the formation of two phases, calcite and valerite, at pH 10 upon addition of serine. The magnetic nanobiocatalyst was shown to be an excellent reusable catalyst for the sequestration of CO(2).