Characteristics of CO2 Absorption into Aqueous Ammonia

Abstract

Aqueous ammonia was investigated as a new absorbent of the chemical absorption process for CO₂ capture from combustion flue gas. The effects of the temperature and concentration of aqueous ammonia on CO₂ absorption in a semi‐batch reactor were studied by interpreting breakthrough curves. Raman spectroscopy analysis of CO₂ loaded aqueous ammonia provided concentration changes of bicarbonate, carbonate, and carbamate as well as CO₂ sorption capacity at given time during the absorption with 13 wt% aqueous ammonia at 25°C. It was observed that carbamate formation was dominating at the early stage of absorption. Then, the bicarbonate formation took over the domination at the later stage while the carbonate remained unchanged.     

Synthesis of soluble oligsiloxane-end-capped hyperbranched polyazomethine and their application to CO2/N2 separation membranes

Three soluble hyperbranched polyazomethines containing oligosiloxane end group HBP-PAZ-SiO_n were successfully synthesized. HBP-PAZ-SiO_ns were used as modifiers of ethyl cellulose (EC) and polysulfone (PS) membranes. Blend membranes, HBP-PAZ-SiO_n/EC and HBP-PAZ-SiO_n/PS were prepared by blending the THF solution of HBP-PAZ-SiO_n with ethanol solution of EC and dichloromethane solution of PS, respectively. Surprisingly, the permeabilities for CO₂ of the blend membranes were more than 15–16 times higher than those of pure EC and PS membranes without any drop of pemselectivity to N₂. This unusual improvement has been achieved by both enhancement of diffusivity for carbon dioxide and nitrogen by the oligosiloxane groups and enhancement of affinity of the amino groups with carbon dioxide at the end groups of HBP-PAZ-SiO_n.     

SOLUBILITY OF CO2AND H2S IN A MIXED SOLVENT

Mixed solvents are a combination of chemical and physical solvents and have some advantages over traditional treating solvents for the removal of acid gases from gas streams. The solubility of H₂S and CO₂in a mixed solvent consisting of AMP (2-amino-2-methyl-l-propanol), sulfolane, and water has been measured at 40 and 100°C at partial pressures of the acid gas to 6000 kPa. The solubility in the mixed solvent was compared with the solubility in an aqueous solution of equivalent amine concentration. At solution loadings less than 1 mol acid gas/mol amine, the solubility of the acid gas is lower in the mixed solvent than in the corresponding amine solvent. At higher loadings, the trend is reversed and the solubility is greater in the mixed solvent. The results are rationalized in terms of the effect of the physical solvent component on the chemical reaction and physical vapor-liquid equilibria. The solubility model of Deshmukh and Mather was used to correlate the data.     

CO2 Absorption Mechanism by the Deep Eutectic Solvents Formed by Monoethanolamine-Based Protic Ionic Liquid and Ethylene Glycol

Deep eutectic solvents (DESs) have been widely used to capture CO₂ in recent years. Understanding CO₂ mechanisms by DESs is crucial to the design of efficient DESs for carbon capture. In this work, we studied the CO₂ absorption mechanism by DESs based on ethylene glycol (EG) and protic ionic liquid ([MEAH][Im]), formed by monoethanolamine (MEA) with imidazole (Im). The interactions between CO₂ and DESs [MEAH][Im]-EG (1:3) are investigated thoroughly by applying ¹H and ¹³ C nuclear magnetic resonance (NMR), 2-D NMR, and Fourier-transform infrared (FTIR) techniques. Surprisingly, the results indicate that CO₂ not only binds to the amine group of MEA but also reacts with the deprotonated EG, yielding carbamate and carbonate species, respectively. The reaction mechanism between CO₂ and DESs is proposed, which includes two pathways. One pathway is the deprotonation of the [MEAH]⁺ cation by the [Im]⁻ anion, resulting in the formation of neutral molecule MEA, which then reacts with CO₂ to form a carbamate species. In the other pathway, EG is deprotonated by the [Im]⁻, and then the deprotonated EG, HO-CH₂-CH₂-O⁻, binds with CO₂ to form a carbonate species. The absorption mechanism found by this work is different from those of other DESs formed by protic ionic liquids and EG, and we believe the new insights into the interactions between CO₂ and DESs will be beneficial to the design and applications of DESs for carbon capture in the future.     

Low Temperature Liquid State Synthesis of Lithium Zirconate and its Characteristics as a CO2 Sorbent

Abstract

In this study, a new preparation method providing greatly improved CO₂ sorption is introduced. Li₂ZrO₃ sorbent was prepared by low temperature co‐precipitation and compared in CO₂ sorption performance with a sorbent prepared by the conventional high temperature solid‐state reaction method. The two sorbents were characterized using scanning electron microscopy, X‐ray diffraction and thermo‐gravimetric analysis. The Li₂ZrO₃ powder prepared by the relatively simple co‐precipitation method showed significantly better performance than the one prepared by solid‐state reaction with respect to both kinetics and CO₂ sorption capacity. Extensive study of the powder prepared by co‐precipitation has been performed at various conditions.     

EFFICIENT DESULFURIZATION IN O2/CO2 COMBUSTION: DEPENDENCE ON COMBUSTION CONDITIONS AND SORBENT PROPERTIES

Based on experiments on desulfurization, CaSO₄ decomposition, and a system approach using theoretical analysis, efficient in-furnace desulfurization in O₂/CO₂ combustion was investigated. The influence of combustion conditions and sorbent properties on system desulfurization efficiency was clarified. The global desulfurization efficiency was found to increase with O₂ purity. The global desulfurization efficiency in a dry recycle was higher than that in a wet recycle. The global efficiency of in-furnace desulfurization decreased with initial O₂ concentration. As the temperature increased, the global desulfurization efficiency increased first and then decreased due to the decomposition of CaSO₄. In the temperature range investigated, the global desulfurization efficiency in O₂/CO₂ coal combustion was much higher than that of conventional coal combustion in air. The global desulfurization efficiency decreased with sorbent size. When the particle radius decreased to one quarter, the global desulfurization efficiency doubled, becoming as high as 80%. The global desulfurization efficiency was very different among the three sorbents investigated, whether in O₂/CO₂ combustion or in conventional air combustion. The global desulfurization efficiency increased in the order of Ca(OH)₂, scallop, and limestone in O₂/CO₂ combustion, but in the order of scallop, Ca(OH)₂, and limestone in conventional air combustion. Nevertheless, all three sorbents demonstrated much higher desulfurization efficiency in O₂/CO₂ combustion than in conventional air combustion.     

A RIGOROUS MODEL FOR ABSORPTION OF CARBON DIOXIDE INTO AQUEOUS N-METHYLDIETHANOLAMINE SOLUTION

A rigorous model for absorption of carbon dioxide into aqueous N-methyldiethanolamine (MDEA) based on the assumption of reversible reactions and the simplified model with a pseudo-first order irreversible reaction hypothesis were employed to compare with experimental data. The experimental absorption rates were obtained from a characterized double stirred-cell absorber with a planar gas-liquid interface. It was demonstrated that the numerical solution of the rigorous model provides a better prediction for the absorption rate of carbon dioxide into aqueous MDEA solution than that of the simplified model. Only in the case of absorption experiments carried out at a low carbon dioxide partial pressure (p < 20 kpa) and low amine concentration (MDEA_total < 1000 mol/m³), the assumption of pseudo-first order irreversible reaction is reasonable.     

PREDICTION OF CO2 FREEZE-OUT CONDITIONS AND CO2 HYDRATE FORMATION CONDITIONS WITH A SINGLE EQUATION OF STATE

A recent study by Eggeman and Chaffin (2005 Eggeman , T. , and Chafin , S. ( 2005 ). Beware of pitfalls of CO₂ freezing predictions , Chem. Eng. Prog. , 101 ( 3 ), 39 – 44 . [Google Scholar]), which showed large discrepancies in CO₂ freeze-out conditions as predicted by several commercial simulators, prompted a reexamination of using the TBS equation of state for phase equilibrium calculations involving solids. Salim and Trebble (1994 Salim , P. , and Trebble , M. A. ( 1994 ). Modelling of solid phases in thermodynamic calculations via translation of a cubic equation of state at the triple point , Fluid Phase Equilib. , 93 , 75 – 99 .[Crossref] , [Google Scholar]) had previously presented a methodology for extending the Trebble-Bishnoi-Salim (TBS) equation of state (Salim, 1990 Salim , P. ( 1990 ). A modified Trebble-Bishnoi equation of state, M.Sc. thesis , University of Calgary . [Google Scholar]) to calculations involving a solid phase. In this study, the CO₂ freeze-out conditions in CO₂/CH₄ and CO₂/C₂H₆ mixtures are calculated from the TBS equation of state, and it is shown that they provide a better data fit than the traditional Poynting correction method. Furthermore, since the use of an equation of state in SLE/SVE calculations does not require the explicit assumption of a pure solid phase, the model was assessed for its ability to correlate CO₂ gas hydrate equilibrium conditions. Gas hydrates were simply treated as an impure solid phase, and it was seen that the predictions of gas hydrate equilibrium were in very good agreement with the experimental data. Computationally, the use of the TBS equation of state has the advantage, over the model of Yokozeki (2005 Yokozeki , A. ( 2005 ). Methane gas hydrates viewed through unified solid-liquid-vapour equation of state , Int. J. Thermophys. , 26 ( 3 ), 743 – 765 . [Google Scholar]), that it does not require a modifying factor (c_b) in the repulsive term to handle the presence of hydrates; they are instead handled using a unique binary interaction parameter for the hydrate phase.     

Pilot plant study of two new solvents for post combustion carbon dioxide capture by reactive absorption and comparison to monoethanolamine

Application of new solvents will substantially contribute to the reduction of the energy demand for the post combustion capture of CO₂ from power plant flue gases. The present work describes tests of such new solvents in a gas-fired pilot plant, which comprises the complete absorption/desorption process (column diameters 0.125 m, absorber/desorber packing height 4.25/2.55 m, packing type: Sulzer BX 500, flue gas flow 30–100 kg/h, CO₂ partial pressure 35–135 mbar). Two new solvents CESAR1 (0.28 g/g 2-amino-2-methyl-1-propanol+0.17 g/g piperazine+0.55 g/g H₂O) and CESAR2 (0.32 g/g 1, 2-ethanediamine+0.68 g/g H₂O), which were developed in an EU-project, were systematically studied and compared to MEA (0.3 g/g monoethanolamine+0.7 g/g H₂O). The two new solvents and MEA were studied in the same way in the pilot plant and detailed results are reported for all solvents. In the present study the structured packing Sulzer BX 500 is used. The measurements are carried out at a constant CO₂ removal rate of 90% by an adjustment of the regeneration energy in the desorber for systematically varied solvent flow rates. An optimal solvent flow rate leading to a minimum energy requirement is found from these studies. Direct comparisons of such results can be misleading if there are differences in the kinetics of the different solvent systems. The influence of kinetic effects is experimentally studied by varying the flue gas flow rate at a constant ratio of solvent mass flow to flue gas mass flow and constant CO₂ removal rate. Results from these studies indicate similar kinetics for CESAR1, CESAR2 and MEA. The direct comparison of the pilot plant results for these solvents is therefore justified. Both CESAR1 and CESAR2 show improvements compared to MEA. The most promising is CESAR1 with a reduction of about 20% in the regeneration energy and 45% in the solvent flow rate.     

Mesoporous Silica Sorbents Impregnated with Blends of Tetraethylenepentamine and Alkanolamine for CO2 Separation

Mesocellular silica foam (MSU-F) supports were functionalized via wet impregnation with various amine and alcohol compounds for use as high-capacity adsorbents for CO₂ separation. The effect of the amino, hydroxyl, and ether functional groups in the impregnating mixture on the CO₂ adsorption capacity was investigated. Chemical adsorption was controlled by the composition of the compounds, and the blending effect on the adsorption performance was dependent on the temperature. MSU-F (30 wt.%) impregnated with a mixture of tetraethylenepentamine (40 wt.%) and aminoethylethanolamine (30 wt.%) showed a high adsorption capacity of 5.4 mmol/g at 333 K for 15 kPa CO₂.     

Photocatalytic Reduction of CO2 with H2O on Ti-Containing Porous Silica Thin Film Photocatalysts

Two different Ti-containing porous silica thin films having a hexagonal and cubic pore structure were synthesized and used as photocatalysts for the reduction of CO₂ with H₂O at 323 K. UV irradiation of the Ti-containing porous silica thin films in the presence of CO₂ and H₂O led to the formation of CH₄ and CH₃OH with a high quantum yield of 0.28%. These porous silica thin film photocatalysts having a hexagonal pore structure exhibited higher reactivity than the Ti-MCM-41 powder photocatalysts with the same pore structure.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Application of Optical-fiber Photoreactor for CO2 Photocatalytic Reduction

An optical-fiber photoreactor, comprised of 216 catalyst-coated fibers, was designed and assembled to transmit and spread light uniformly inside the reactor. The power loss of light transmission inside an optical fiber was calculated using beam propagation method. The optimum length of optical fiber was estimated to be near 11 cm long in order to entirely spread out light energy over surface catalyst. Vapor-phase CO₂ was photocatalytically reduced to methanol using the photoreactor under UV irradiation in a steady-state flow system. The solutions of metal-loaded titania were prepared by thermal hydrolysis method. Metal-loaded TiO₂ film was coated on optical fibers by dip-coating method. TiO₂, Cu/TiO₂ and Ag/TiO₂ films were uniformly on the fibers and their thicknesses ranged from 27 to 33 nm. The films consisted of very fine spherical particles with diameters of 10–20 nm. The XRD spectra indicated anatase phase for all films. Methanol yield increased with UV irradiative intensity. Maximum methanol rate was 4.12 μmole/g-cat h using 1.0 wt%-Ag/TiO₂ catalyst at 1.13 bar of CO₂, 0.03 bar of H₂O pressures, and 5,000 s mean residence time under 10 W/cm² UV irradiation.     

Preparation and characterization of gel polymer electrolyte based on PVA-K2CO3

ABSTRACT

In this study, electrolyte materials were synthesized by mixing a highly conducting salt (K₂CO₃) with the poly(vinyl alcohol) (PVA) in different proportions (from 10 to 50 wt.%). The synthesized electrolyte was characterized using Fourier transform infrared (FTIR) spectroscopy, field-emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) for their functional groups, morphology, thermal stability, glass transition temperature (T_g ), ionic conductivity, and potential window, respectively. Characterization results show that the complex formation between PVA and K₂CO₃ salt has been established by FTIR spectroscopic study, which indicates the detailed interaction between PVA and the salts in PVA-K₂CO₃ composites while the amorphous nature of the electrolyte after incorporation of the salts has been confirmed by FESEM analysis. Similarly, TGA and DSC analysis revealed that both decomposition temperature and T_g of the synthesized electrolytes decrease with the addition of K₂CO₃ due to the strong plasticizing effect of the salt. The results confirm that the electrolytes have sufficient thermal stability for supercapacitor operation, as well as an amorphous phase to effectively deliver high ionic conductivity. The highest ionic conductivity of 4.53 × 10^?3 S cm^?1 at 373 K and potential window of 2.7 V was exhibited by PK30 (30 wt.% K₂CO₃), which can be considered as high value for solid-state electrolytes which are superior to those electrolytes from PVA salts earlier reported. The results similarly show that the prepared electrolyte is temperature-dependent as conductivity increase with increase in temperature. Based on these properties, it can be imply that the PVA-K₂CO₃ gel polymer electrolyte (GPE) could be a promising electrolyte candidate for EDLC applications. The results indicate that the PVA-K₂CO₃ as a new electrolyte material has great potential in practical applications of portable energy-storage devices.     

A Fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO₂ and CO₂/H₂ on a silica-supported caesium-doped copper catalyst. Adsorption of CO₂ on a “caesium”/silica surface resulted in the formation of CO₂ ⁻ and complexed CO species. Exposure of CO₂ to a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm⁻¹. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and H₂, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.     

Alcohol Synthesis from Syngas over K2CO3/CoS/MoS2 on Activated Carbon

Supported K₂CO₃/Co–MoS₂ on activated carbon was prepared by a co-impregnation technique and has been characterized by X-ray diffraction (XRD) and BET. Active ingredients ranged from 39 to 66% and included molysulfide and cobalt sulfide. XRD analysis indicates that cobalt and molybdenum sulfides are found in the Co₃S₄ and Co₉S₈ phases. These catalysts were performance tested in a fixed-bed reactor under higher alcohol synthesis conditions, 2000–2400 psig and 270–330°C. Active chemicals on the carbon extrudates decreased the surface area dramatically, as measured by BET. Surprisingly, at the high level of active chemicals, alcohol productivity and selectivity were decreased. An increase in the reaction temperature led to a decrease in the selectivity of methanol and an increase in selectivity of hydrocarbons. Total alcohol productivity was also increased as gas hourly space velocity (GHSV) was increased. Co₉S₈ may play a role in the catalyst aging process. In prolonged reaction periods (140 h), sulfur is lost from the surface, possibly as H₂S. The quantity of Co₉S₈ on the surface appears to increase as the catalyst ages.     

Pathways for CO2 Formation and Conversion During Fischer–Tropsch Synthesis on Iron-Based Catalysts

CO₂ reaction and formation pathways during Fischer–Tropsch synthesis (FTS) on a co-precipitated Fe–Zn catalyst promoted with Cu and K were studied using a kinetic analysis of reversible reactions and with the addition of ¹³C-labeled and unlabeled CO₂ to synthesis gas. Primary pathways for the removal of adsorbed oxygen formed in CO dissociation steps include reactions with adsorbed hydrogen to form H₂O and with adsorbed CO to form CO₂. The H₂O selectivity for these pathways is much higher than that predicted from WGS reaction equilibrium; therefore readsorption of H₂O followed by its subsequent reaction with CO-derived intermediates leads to the net formation of CO₂ with increasing reactor residence time. The forward rate of CO₂ formation increases with increasing residence time as H₂O concentration increases, but the net CO₂ formation rate decreases because of the gradual approach to WGS reaction equilibrium. CO₂ addition to synthesis gas does not influence CO₂ forward rates, but increases the rate of their reverse steps in the manner predicted by kinetic analyses of reversible reactions using non-equilibrium thermodynamic treatments. Thus the addition of CO₂ could lead to the minimization of CO₂ formation during FTS and to the preferential removal of oxygen as H₂O. This, in turn, leads to lower average H_2/CO ratios throughout the catalyst bed and to higher olefin content and C₅₊ selectivity among reaction products. The addition of ¹³CO₂ to H₂/¹²CO reactants did not lead to significant isotopic enrichment in hydrocarbon products, indicating that CO₂ is much less reactive than CO in chain initiation and growth. We find no evidence of competitive reactions of CO₂ to form hydrocarbons during reactions of H₂/CO/CO₂ mixtures, except via gas phase and adsorbed CO intermediates, which become kinetically indistinguishable from CO₂ as the chemical interconversion of CO and CO₂ becomes rapid at WGS reaction equilibrium.     

Pressure-Swing Adsorption Separation of H2S from CO2 with Molecular Sieves 4A, 5A,and 13X

The separation of bulk quantities of H₂S from CO₂ was investigated through a series of pressure-swing adsorption experiments utilizing 4A, 5A, and 13X molecular sieves. High selectivity of H₂S over CO₂ was encountered for all sieves, particularly for the 13X and 5A. Practically pure CO₂ was produced in the adsorption stage with fresh 5A and 13X sieves, at high product recovery rates. Efficient H₂S purification was obtained with fresh 5A and regenerated 4A zeolites. The experimental results were in line with theoretical predictions of the literature.     

Methanol Synthesis from CO2 Using Skeletal Copper Catalysts Containing Co-precipitated Cr2O3 and ZnO

Skeletal Cu-Cr₂O₃-ZnO catalysts have been prepared by leaching CuAl₂ alloy particles at 273 K using 6.1 M aqueous NaOH solutions containing sodium chromate (Na₂CrO₄) and sodium zincate (Na₂Zn(OH)₄). The presence of sodium chromate and sodium zincate in the caustic solution was found to affect the pore structure and surface areas of the resulting catalysts. Both BET and Cu surface areas were increased by increasing the concentration of Na₂CrO₄ and of Na₂Zn(OH)₄.Increasing the Na₂CrO₄ level from 0 to 0.06 M in a 6.1M NaOH solution containing 0.2M Na₂Zn(OH)₄ caused the content of ZnO in the catalyst to decrease from 8.8 to 3.0 wt% whilst increasing the Cr₂ O₃ content from 0 to 1.7 wt%, indicating that the presence of Na₂CrO₄ in the leach liquor not only resulted in deposition of a Cr compound but also inhibited precipitation of zinc hydroxide onto skeletal Cu catalysts. On the other hand, increasing the concentration of Na₂Zn(OH)₄ from 0 to 0.6 M in a 6.1 M NaOH solution containing 0.008 M Na₂ CrO₄ resulted in increasing the ZnO loading from 0 to 8.9wt% with an almost constant content of Cr₂ O₃ (1.3 ± 0.2%) in the catalysts, revealing that sodium zincate only led to precipitation of zinc hydroxide and did not suppress Cr₂O₃ formation.Hydrogenation of CO₂ was studied using a gas mixture of 24% CO₂ in H₂ at a total pressure of 4MPa, space velocities up to 210000L kg^-1h^-1 and temperatures in the range 493-533K. The catalysts were found to be both highly active and selective for methanol synthesis. This study confirms the role of ZnO in promoting the activity of copper for methanol synthesis from CO₂ and improving the selectivity by inhibiting the reverse water-gas shift reaction. The role of Cr₂O₃ is to improve the structural development of high surface area skeletal copper.