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Synthesis and modification of potential CO2 adsorbents: Amine modified silica and calcium carbonates
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). (Niklas Hedin)
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The prospect of rapid changes to the climate due to global warming is subject of public concern. The need to reduce the emissions of atmospheric green house gases and in particular carbon dioxide is greater than ever. Extensive research is performed to find new solutions and new materials, which tackles this problem in economically benign way. This thesis dealt with two potential adsorbents for post combustion  carbon capture, namely, amine modified silica and calcium carbonates. We modified porous silica with large surface area by propyl-amine groups to enhance the carbon dioxide adsorption capacity and selectivity. Experimental parameters, such as reaction time, temperature, water content, acid and heat treatment of silica substrate were optimized using a fractional factorial design. Adsorption properties and the nature of formed species upon reaction of CO2 and amine-modified silica were studied by sorption and infrared spectroscopy. Physisorbed and chemisorbed amount of adsorbed CO2 were, for the first time, estimated directly in an accurate way. The effects of temperature and moisture on the CO2 adsorption properties were also studied.

Crystallization of calcium carbonate as a precursor to calcium oxide, which can be used as carbon dioxide absorbent, was studied in the second part of this thesis. Structure of different amorphous phases of calcium carbonate was studied in detail. Crystallization of calcium carbonate with and without additives was studied. Parameters like stirring rate, temperature, pH and polymer concentration showed to be important in selection of phase and morphology. An aggregation mediated crystallization was postulated to explain the observed morphologies. 

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University , 2012. , 87 p.
Keyword [en]
Amine-modified silica, carbon capture, Fractional factorial design, IR spectroscopy, calcium carbonate
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-75638ISBN: 978-91-7447-516-6 (print)OAI: oai:DiVA.org:su-75638DiVA: diva2:517545
Public defence
2012-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Accepted.Available from: 2012-05-10 Created: 2012-04-24 Last updated: 2012-04-30Bibliographically approved
List of papers
1. Carbon Dioxide Sorbents with Propylamine Groups-Silica Functionalized with a Fractional Factorial Design Approach
Open this publication in new window or tab >>Carbon Dioxide Sorbents with Propylamine Groups-Silica Functionalized with a Fractional Factorial Design Approach
2011 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 27, no 7, 3822-3834 p.Article in journal (Refereed) Published
Abstract [en]

Mesoporous silica particles (Davisil) were functionalized with aminopropyltriethoxysilane (APTES) in a fractional factorial design with 19 different synthesis and uptake experiments. The number of amino groups and the uptake of CO(2) were optimized in a 2(V)(5-1) design. Most important to functionalizationwas the amount of water present during synthesis, the reaction time, and pretreating the silica with a mineral acid; certain two-way interactions were shown to be statistically significant as well. Modifications performed at 110 or 80 degrees C showed no significant differences concerning amine content or uptake of CO(2). Properly choosing center points for the discrete variables is problematic and is somewhat related to the lack of fit with respect to CO(2) uptake; the regression was good. Solid-state (29)Si NMR showed that the APTES was mainly fully condensed. Specific surface areas did not correlate with the number of n-propylamine groups on the silica, which is indicative of differential levels of heterogeneity in the coverage of propylamines. The uptake of CO(2) and N(2) was measured from -20 to 70 degrees C and from 0 to 1 bar and parametrized by the Freundlich isotherm. Amine-modified silica adsorbed significant amounts of CO(2), especially at the low partial pressure, which is important for CO(2) capture from flue gas. At such pressures, samples with a high density of amine (4 amines/nm(2)) showed a much higher uptake of CO(2) than did those with densities of similar to 2-3 amines/nm(2), reflecting differential tendencies to form propylammonium-propylcarbamate ion pairs; these require close proximity among amine groups to form. Water affected the uptake of carbon dioxide in different ways. Certain samples took up more moist CO(2) gas than dry CO(2), and others took up less moist CO(2) than dry CO(2), which is indicative of differential tendencies toward water adsorption. We conclude that experimental design is a time-efficient approach to the functionalization of silica with propylamine groups.

National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-68812 (URN)10.1021/la104629m (DOI)000288970900079 ()
Note
3Available from: 2012-01-09 Created: 2012-01-07 Last updated: 2017-12-08Bibliographically approved
2. Carbon dioxide adsorption on mesoporous silica surfaces containing amine-like motifs
Open this publication in new window or tab >>Carbon dioxide adsorption on mesoporous silica surfaces containing amine-like motifs
2010 (English)In: Applied Energy, ISSN 0306-2619, E-ISSN 1872-9118, Vol. 87, no 9, 2907-2913 p.Article in journal (Refereed) Published
Abstract [en]

The postcombustion separation of CO2 from a flue gas mixture is a unit operation in carbon capture. Today, CO2 is normally separated with alkanolamines in aqueous solutions. These absorption processes are energy intensive and costly. Increased environmental considerations and the significant footprints of many energy sources warrant the development of new gas separation techniques for the competitive implementation of carbon capture and storage technologies. Improved adsorbent-mediated separation processes are candidates for such new low-energy low-cost processes. In this study, porous silica-based adsorbents with amine-like motifs were synthesized. The temperature- and pressure-dependent adsorption of CO2 and CO2/H2O mixtures were determined and compared for these materials. The experimental uptake capacities of the materials modified with primary propyl amine moieties were significantly higher than those of materials modified with bis-ethanol amine or amidine. The propyl-amine-modified samples also showed good selectivity for CO2 over nitrogen gas.

Keyword
Gas separation, Adsorption, Mesoporous, Carbon dioxide
National Category
Materials Chemistry Environmental Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-43089 (URN)10.1016/j.apenergy.2009.06.008 (DOI)
Conference
1st International Conference on Applied Energy, Hong Kong, PEOPLES R CHINA, JAN 05-07, 2009
Available from: 2010-09-27 Created: 2010-09-27 Last updated: 2017-12-12Bibliographically approved
3. Quantification of chemisorption and physisorption of carbon dioxide on porous silica modified by propylamines: Effect of amine density
Open this publication in new window or tab >>Quantification of chemisorption and physisorption of carbon dioxide on porous silica modified by propylamines: Effect of amine density
2012 (English)In: Microporous and Mesoporous Materials, ISSN 1387-1811, E-ISSN 1873-3093, Vol. 159, 42-49 p.Article in journal (Refereed) Published
Abstract [en]

Detailed molecular aspects of carbon dioxide sorption on porous silica with different amounts of tethered and cross-linked n-propylamine groups were investigated. Infrared spectroscopy was applied to directly quantify physisorbed and chemisorbed CO2 on the amine modified silicas. The fractions of physisorbed CO2 and various chemisorbed species were determined as functions of CO2 pressure and the amine density on the modified silica. Physisorbed CO2 was a minor portion of the total CO2 uptake at low pressures, but it’s contribution increased to ∼35% at 1 bar of CO2 when the propylamine surface density was low or medium (0.87-1.67 NH2/nm2). Chemisorption of CO2 dominated when the propylamine content was high (2.74 NH2/nm2). The quantities of propylammonium propylcarbamate ion pairs increased with increasing propylamine content. At low or medium amine surface densities (0.87-1.67 NH2/nm2) this increase was approximately proportional to the amine density, but the quantity of ion pairs increased very significantly when the propylamine content was high (2.74 NH2/nm2). This dependency on amine density is consistent with the idea that a sufficiently close proximity of propylamine groups allows a formation of ion pairs. The relative fractions of carbamic acid and silylpropylcarbamate were significant for materials on which ion pairs could not form. Furthermore, the quantities of carbamic acid increased with increasing amine densities suggesting that the ion pairs have a role to stabilize the labile carbamic acid through hydrogen bonds.

Keyword
Amine modified silica, CO2 adsorption, IR spectroscopy, Carbon capture
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-75635 (URN)10.1016/j.micromeso.2012.04.007 (DOI)000305917700007 ()
Available from: 2012-04-24 Created: 2012-04-24 Last updated: 2017-12-07Bibliographically approved
4. Kinetic control of particle-mediated calcium carbonate crystallization
Open this publication in new window or tab >>Kinetic control of particle-mediated calcium carbonate crystallization
2011 (English)In: CrystEngComm, ISSN 1466-8033, E-ISSN 1466-8033, Vol. 13, no 14, 4641-4645 p.Article in journal (Refereed) Published
Abstract [en]

By changing the temperature, pH, stirring rate, or time for calcium carbonate crystallization, complex shapes of aggregated calcium carbonates formed. Such shapes have earlier been ascribed to specific interactions with specialized additives. Without polymeric additives, aggregates of vaterite transformed more rapidly into calcite aggregates under slow than under fast stirring. With an anionic polyelectrolyte added, vaterite was stabilized. Larger polycrystalline aggregates of vaterite formed under rapid than under slow stirring, indicative of a particle mediated growth of aggregates controlled by convective currents. The size of the underlying nanoparticles was temperature dependent, with grain sizes of similar to 20 to 50 nm at 20 degrees C and similar to 350 nm at 90 degrees C. The small differences in free energy between the anhydrous polymorphs of calcium carbonate made both kinetic and equilibrium dependencies important.

National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-68150 (URN)10.1039/c1ce05142c (DOI)000292159200025 ()
Available from: 2012-01-04 Created: 2012-01-03 Last updated: 2017-12-08Bibliographically approved
5. Proto-Calcite and Proto-Vaterite in Amorphous Calcium Carbonates
Open this publication in new window or tab >>Proto-Calcite and Proto-Vaterite in Amorphous Calcium Carbonates
Show others...
2010 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 49, no 47, 8889-8891 p.Article in journal (Refereed) Published
Abstract [en]

Amorphous order: Amorphous calcium carbonates (ACC) have an intrinsic structure relating to the crystalline polymorphs of calcite and vaterite. The proto-crystalline structures of calcite and vaterite (pc-ACC and pv-ACC) are analyzed by NMR (see picture), IR, and EXAFS spectroscopy, which shows that the structuring of ACC relates to the underlying pH-dependent equilibria.

Keyword
amorphous materials, calcium carbonate, crystallization, EXAFS spectroscopy, NMR spectroscopy
National Category
Inorganic Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-49833 (URN)10.1002/anie.201003220 (DOI)
Available from: 2010-12-19 Created: 2010-12-19 Last updated: 2017-12-11Bibliographically approved

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