DEVELOPMENT OF INEXPENSIVE CELLULOSE-BASED SORBENTS FOR CARBON DIOXIDE

ABSTRACT

Aqueous amine solutions are benchmark solvents for CO₂ capture and their operational drawbacks are well-known. In order to overcome these problems, the support of amines on solid materials appears as an option for CO₂ capture. Cellulose is a versatile and low-cost material that can be used as a support. This study reports chemical modification of cellulose fibers extracted from rice husk with different amines and their potential for CO₂ capture. The obtained compounds were characterized by different techniques. The CO₂ sorption capacity was gravimetrically assessed in a Magnetic Suspension Balance. Quantum mechanical simulations and experimental results revealed that -NH- and -NH₂ represent major working sites of the employed compounds. The best result for CO₂ sorption was attained for the amine-modified cellulose CL-D-400 with a sorption capacity of 409 µmol CO₂/g at 1 bar and 1091 µmol CO₂/g at 10 bar with amine concentrations as low as 2 × 10^{- 6} mol/mg.

Key words:
Cellulose; Rice husk; CO₂ capture; Amines; Simulation

INTRODUCTION

The CO₂ concentration in the atmosphere is increasing every year, as well as global warming and its effect on climate change (Barbosa et al., 2016; Chan et al., 2016; Hussain et al., 2015; Nouri and Ebrahim, 2016; IPCC, 2013; Seo et al., 2014). Preventing the growth of carbon dioxide emissions in the atmosphere is essential for achieving the global warming reduction target (Dutcher et al., 2015). Different strategies have been considered and adopted by several countries aiming to reduce the CO₂ emissions, such as the improvement of energy efficiency, increasing the use of low carbon fuels or nuclear energy, renewable energy development, geo-engineering approaches and CO₂ capture and storage (CCS)(Garcés et al., 2013; Leung et al., 2014). Among these different strategies, CCS is considered crucial because it reduces the CO₂ emission from large emission sources (Arias et al., 2016; Garđarsdóttir et al., 2015; Kamarudin and Alias, 2013; Leung et al., 2014).

Chemical absorption using amine aqueous solutions is a benchmark technology for CO₂ capture (Arias et al., 2016; Bachelor and Toochinda, 2012; Kamarudin and Alias, 2013). However, it has some operational drawbacks, such as high power consumption required for solvent regeneration, equipment corrosion (Gray et al., 2005; Kamarudin and Alias, 2013), degradation/evaporation of amines, the need of a large-volume absorber (Yu et al., 2012), besides additional operating costs due to substitution of solvents (Seo et al., 2014).

To overcome the drawbacks of chemical absorption, the impregnation and grafting of amines on solids have been suggested in the literature (Bachelor and Toochinda, 2012; Gray et al., 2005; Knowles et al., 2005; Lima et al., 2015; Yu et al., 2012). Unfortunately, many of these commercial sorbents remain prohibitively expensive (Bachelor and Toochinda, 2012). This generates the necessity of developing inexpensive sorbents for CO₂ capture. As alternatives for obtaining low-cost sorbents, impregnation of agricultural wastes with amines has been suggested. Some examples are bagasse, rice straw, industrial residues, such as mullite, fly ash and other oxygen rich sorbents (Bachelor and Toochinda, 2012; Gray et al., 2004). Strategies to use residues for CO₂ capture will foster emergence of green technologies and sustainable development.

Brazil is among the ten largest rice producers in the world. By 2017, it produced about 11 759 096 tons of rice. Rice husk (RH) is a major agricultural waste generated as a byproduct during the rice milling stage (Rosa et al., 2012), while cellulose constitutes about 33% of rice husk (Johar et al., 2012).

Cellulose is the most abundant natural polymer (Zhang et al., 2016). It is a low-cost versatile material, thermodynamically stable, presenting crystalline structure and numerous hydrogen bonds (Shukla et al., 2013). Cellulose undergoes functionalization primarily through the hydroxyl groups(Cuadro et al., 2015; Shukla et al., 2013).

Previous studies have been conducted on nanofibrillated cellulose modification using aminosilanes for CO₂ capture from the air (Gebald et al., 2011, 2013). Commercially fibrillated cellulose suspension was used in that work. Herein, we investigated chemical modification of cellulose fibers, extracted from rice husk, with different amines. The potential of the newly developed compounds for CO₂ capture was characterized. Quantum mechanical simulations were employed to elucidate the impact of different functional groups on CO₂ sorption.

EXPERIMENTAL SECTION

Materials

The rice husks were donated by Cooperativa Arrozeira Extremo Sul Ltda. The material was washed with distilled water and dried in an oven at 100°C for 8h. The dried husk was ground in a knife mill. The fraction that passed through the 20 mesh sieve (0.841 mm) was collected. Anhydrous citric acid (CA, 99.5% Synth), sodium hydroxide (NaOH, 97% Vetec), hydrogen peroxide (H₂O₂, 35%, Neon), N,N-dimethylformamide (DMF, 99.5%, Merck), ethanol (CH₃CH₂OH, 99%, Vetec), hydrazine (32.04 g/mol, HYD, aqueous solution 65%), ethylenediamine (60.10 g/mol, EDA, 99%, Vetec), Jeffamine® M-2005 (Mn = 2000 g/mol , Huntsman), Jeffamine® D-4000 (Mn = 4000 g/mol, Huntsman), Jeffamine® D-400 (Mn = 430 g/mol Huntsman), Jeffamine® EDR-148 (Mn = 148 g/mol, Huntsman) were used as purchased.

Cellulose extraction

The cellulose extraction was adapted from literature procedures (Johar et al., 2012; Teodoro et al., 2011). The rice husk was treated with 4 wt% NaOH at 90°C for 2h to remove the lignin and hemicellulose of the rice husk fibers. The acid hydrolysis treatment was conducted on the fibers after alkali treatment using 10.0 mol/L H₂SO₄ at 50°C for 40 min under continuous stirring. Afterwards, bleaching was carried out by addition of 16% (v/v) H₂O₂ and 5 wt% NaOH solution in a 1:1 proportion (v/v) at 55°C for 2h to remove the remaining lignin. The rice husk: solution ratio was 0.05 g/mL. Each step was repeated for five times. The solid was filtered and washed with distilled water until neutral pH was achieved and dried at 50°C in the oven after each treatment.

Cellulose chemical modification

Cellulose chemical modification was performed in two stages. The first was modification with citric acid (Figure 1). The second step was functionalization with amines (Figure 2). The modification with citric acid was performed by a similar procedure described elsewhere (Rodrigues et al., 2006; Zhu et al., 2008). The cellulose was poured into a flask containing 1.2 mol/L aqueous solution of citric acid to obtain 100g/L cellulose solution. This solution was stirred for 0.5h at room temperature. The temperature was increased up to 120°C and kept constant 1.5h under stirring. After cooling, the cellulose was washed with distilled water in the proportion of 200 mL/g for several times to remove any excess of citric acid and dried at 55°C for 24h. The concentration of carboxylic groups (mol/mg) introduced into the modified cellulose was determined by back titration (Gurgel et al., 2008; Karnitz et al., 2007; Shang et al., 2016), by treating the material (0.1 g) with 100 mL of an aqueous solution of NaOH (0.02 mol/L) for 1h under constant stirring. The materials were separated by filtration and the solution was titrated with HCl (0.02 mol/L).

Figure 1
Schematic representation of the carboxylic acid functions introduced on the cellulose surface.

Figure 2
Schematic representation of amine-modified cellulose.

The amine functionalization reaction is described elsewhere (Bernard et al., 2016; Magalhaes et al., 2014). In a Schlenk flask, under N₂ atmosphere 1g of citric acid modified cellulose was added to the amine (molar ratio COOH/AMINE = 1:1) dissolved in 15 mL of dimethylformamide (DMF). The mixture was stirred at 40°C for 2h. The materials were separated by filtration, washed repeatedly with distilled water and ethanol and dried at 55°C for 24h. The concentration of amine (mol/mg) introduced into the modified cellulose was determined by back titration, by treating the material (0.1 g) with 100 mL of an aqueous HCl solution (0.02 mol/L) for 1 hour under constant stirring. The materials were separated by filtration and the solution was titrated with NaOH (0.02 mol/L) (Gurgel et al., 2008; Karnitz et al., 2007) (see Figure 2).

Characterization

The synthesized materials were characterized with a Universal Attenuated Total Reflectance sensor (UATR-FTIR) using a Perkin-Elmer Model 100 FTIR Spectrum, in the range 4000-650 cm^-1. Field emission scanning electron microscopy (FESEM) analyses were performed in a FEI Inspect F50 equipment in secondary electrons (SE) mode. Thermogravimetric Analysis (TGA) was performed using a TA Instruments SDT-Q600 between 25°C and 600°C with a heating rate of 10°C/min in nitrogen atmosphere. Specific surface area and pore size were calculated from nitrogen sorption data using Brunauer-Emmett-Teller (BET) at -196°C (Micromeritics, ASAP 2420). Powder X-ray diffraction (XRD) pattern was recorded on Bruker-AXS D8 ADVANCE diffractometer operated at 40 kV and 20 mA using Cu Kα radiation (λ = 1.5406 Å) in the range 3-40° with a step of 0.02° and scanning time of 1.0 min. The Segal method (Eq. 1) was used to calculate the sample crystallinity index (CrI) of the samples (Segal et al., 1959).

$$\mathrm{CrI}=\frac{I_{002}-I_{\mathrm{AM}}}{I_{002}}100$$ (1)

where I₀₀₂ is the maximum intensity of the 002 peak and I_AM is the intensity scattered by the amorphous part of the sample. The diffraction peak for plane (002) is located at diffraction angle around 2θ = 22° and the intensity scattered by the amorphous part is measured as the lowest intensity at a diffraction angle around 2θ = 18° (Johar et al., 2012).

Ab Initio Calculations

Thermodynamics of the reactions was estimated using molecular partition functions obtained from the numerical ab initio calculations and subsequent vibrational frequency analysis. The Gaussian-X composite schemes proposed by Curtiss and coworkers (Curtiss et al., 1998; Curtiss et al., 2007) were used. For an interested reader, we compared G-3 with its simplified modification G-3-MP2, as well as a newer method, G-4-MP2. The term ‘MP2’ in the method designation means that the MP4 stage in the original composite method (G-3, G-4) was substituted by the MP2 stage (Curtiss et al., 1999). The reported results correspond to an ideal gas approximation. Gibbs free energy, enthalpy and entropy of each process, computed at given external conditions, are based on the Hess law of constant heat summation and known relations between these thermodynamic quantities.

Binding energies were computed using the Becke-3-LYP hybrid density functional (Becke, 1988; Lee et al., 1988) with the 6-311+G* atom-centered split-valence triple-zeta basis set. Both polarization and diffuse functions are included in this basis set for higher accuracy of the theoretical results. The basis set superposition error was excluded through the counterpoise approach. The geometries of the molecules were appropriately optimized prior to computing binding energies at the requested level of theory.

Gas adsorption measurements

Pure gas sorption (CO₂) in the samples was gravimetrically assessed in a Magnetic Suspension Balance (MSB), (Rubotherm Prazisionsmesstechnik GmbH, 35MPa and 400°C) equipped with a single sinker device for absorbate density determination and thermostatized with an oil bath (Julabo F25/± 0.1°C). The apparatus details are described elsewhere (Blasig et al., 2007; Dreisbach and Lösch, 2000). When compared to other gravimetrical sorption methods, the MSB device has the advantage of allowing high-pressure sorption measurements since the sample can be potted into a closed chamber coupled to an external precise accurate balance (accuracy of ±10 μg). The samples (0.06 to 0.09 g) were weighed and transferred to the MSB sample container, and the system was subjected to 10^-7 MPa vacuum at the temperature of the sorption measurement, 25°C, for 24 hours (constant weight was achieved in this time). The gas (CO₂, Air Liquide / 99.998 %) was admitted into the MSB pressure chamber up to the desired pressure, 0.1-3 MPa. In this study, a pressure gauge with an accuracy of 10^-3MPa was used to control the system pressure. The gas solubility in the samples for each isotherm and pressure considered was measured during 3-4 hours until no more weight increase for gas sorption was observed. At this step of gas solubility in the samples, the weight reading from the microbalance at pressure P and temperature T is recorded as W_t(P,T). The mass of the adsorbed gas in the sample (W) was calculated using the following equation (2):

$$W=\left[W_t\left(P,T\right)-W_{\mathrm{sc}}\left(P,T\right)+{\rho }_g\left(P,T\right)\cdot \left(V_{\mathrm{sc}}\left(T\right)+V_s\left(T\right)\right)\right]-W_s\left(\mathrm{vac},T\right)$$ (2)

where W_sc (P,T) is the weight of the sample container, ρ_g (P,T) stands for gas density, directly measured with the MSB coupled single-sinker device, dismissing the application of any equation of state to calculate the gas sorption, V_sc (T) is the volume of the sample container, determined from a buoyancy experiment when no sample is charged into the sample container, V_s (T) the specific solid sample volume, W_s (vac,T) is the weight of samples under vacuum and the term ρg(P, T).(V_sc(T) + V_s(T)) represents the buoyancy force. In this work, the solubility in the sample was treated as the excess solubility.

RESULTS AND DISCUSSION

Specific surface area, amine load and cristallinity

Table 1 shows amine loading and crystallinity for each sample. The specific surface area was insignificant and close to the experimental error, indicating this material does not shows porosity. The concentration determined of carboxylic functions of the CL-CA sample was 2.15×10^-6 (mol/mg). This result is close to the previously known investigations (Gellerested and Gatenholm, 1999). The concentration of the loaded amines ranged from 2.00×10^-6 to 2.04×10^-6 (mol/mg), indicating that almost all supplied carboxyl groups were reacted. The corresponding crystallinity values are discussed bellow.

Table 1
Specific surface area, amine loading and crystallinity.

Sample	Amine loading (mol/mg)	Crystallinity (%)
CELLULOSE	-	87
CL-CA	-	84
CL-HYD	2.00 x10-6	91
CL-EDA	2.04 x10-6	88
CL-M2005	2.02 x10-6	_
CL-D400	2.03 x10-6	63
CL-D4000	2.01x10-6	_
CL- EDR 148	2.03 x10-6	86

X-ray diffraction (XRD)

Figure 3 shows the X-ray diffraction profile of the extracted cellulose and modified cellulose samples. All samples exhibit typical cellulose peaks around 2θ = 16°, 22.6° and 35°(Johar et al., 2012; Zhang et al., 2016). The patterns indicated that the obtained cellulose presented a typical form of cellulose I since there was no doublet in the main peak at 2θ = 22.6°(Li et al., 2009). One can also observe a change in the profile of the x-ray diffraction patterns after the chemical modification. The samples that were modified with amines containing higher molecular weight side chain presented less defined peaks, indicating a lower organization when compared with cellulose and the samples obtained with amines containing lower molecular weight side chains. The crystallinity index values (Table 1) highlight that cellulose modified with low-molecular-weight amines (CL-HYD; CL-EDA, CL-EDR-148) present higher crystallinity values. The compound CL-D-400 functionalizated with Jeffamine® D-400 (Mn = 430 g/mol) showed considerable decrease in crystallinity. The samples synthesized with higher-molecular-weight amines (CL-M-2005 and CL-D-4000) exhibited skewed peaks, which indicate that a new assembly is formed via the inserted side chain. These results indicate that the bigger the size of the inserted side chain the smaller the crystallinity of the sample, probably due to the reduction in the packing degree of cellulose molecules caused by side chains.

Figure 3
XRD pattern of cellulose and modified celluloses samples.

Spectroscopic characterization

The infrared spectra of cellulose in all samples (Figure 4-a, b and c) showed a broad band located at 3330 - 3340 cm^-1, attributed to the stretching of the OH groups, band near 2920 cm^-1 related to C-H stretching, band at 1160 cm^-1 corresponding to C-O-C asymmetrical bridge stretching, broad bands around 1050 cm^-1 and 890 cm^-1 related to the C-H and C-O stretching vibration of the cellulose structure (Johar et al., 2012; Rosa et al., 2012). Having compared spectra for cellulose (Figure 4a) and citric acid modified cellulose (Figure 4b), we identified a strong band at 1740 cm^-1 attributed to the carboxylic acid (X-COOH). This evidences introduction of citric acid into the cellulose chain (Cuadro et al., 2015). Figure 4c presents the FTIR for CL-400 sample. A reduction in intensity of the carboxyl group absorption band (1740 cm^-1) due to the chemical modification with amines was observed. A new band at 1454 cm^-1, characteristic of the symmetric bending of primary amines (NH₂) and at 2869 cm^-1 relative to the CH₂ stretching modes of the amine chains (Yu et al., 2012). A shoulder at 3286 cm^-1 is evidenced which may be attributed to amide N-H stretching vibrations (Yu et al., 2012).

Figure 4
FTIR spectra of: (a) cellulose, (b) citric acid modified cellulose and (c) CL-D400.

Thermogravimetric Analysis (TGA)

Figure 5 presents TG and DTG curves obtained for all materials. All samples showed two thermal events. The earlier weight loss was ca. 4% and t_onset below 100°C, attributed to water vaporization. The later weight loss attributed to cellulose degradation (t_onset of 289°C and T_max of 324°C) being 71%. The modified samples presented a higher thermal stability than cellulose. Degradation temperatures varied from t_onset 318°C to 360°C and T_max of 346°C to 392°C with a weight loss around 83%.

Figure 5
TG (a) and DTG (b) curves for cellulose and modified celluloses samples.

Field emission scanning electron microscopy (FESEM)

Figure 6 exemplifies different effects on the rice husk surface after cellulose extraction as well as chemical modification. The cellulose extraction in the form of bundles of fiber (Figure 6b) can be highlighted by comparing with the smooth compact surface of the untreated rice husk (Figure 6a). Citric acid modified cellulose (Figure 6c) showed similar morphology to that shown by the sample after bleaching treatment (Figure 6b). Amine modification of cellulose samples led to a separation of fiber bundles, especially sample CL-D-400 (Figure 6g). This may contribute to the increase of contact surface area and, consecutively, to CO₂ sorption.

Figure 6
Micrographs of the materials: (a) rice husk fibers, (b) cellulose, (c) CL-CA, (d) CL-HYD, (e) CL-EDA, (f) CL-M2005, (g) CL-D-400, (h) CL-D-4000, (i) CL-EDR-148.

Gas sorption measurements

Table 2 presents the experimental results for CO₂ sorption at 1 bar and 10 bar for the synthesized materials. Note that at both pressures all amine-functionalized samples presented higher sorption values when compared with the citric acid modified cellulose (CL-CA).

Table 2
Sorption values for cellulose and amine modified cellulose samples at 25°C.

Sample	10 bar	1 bar
	µmolCO2/g
CL-CA	243	0.227
CL-HYD	864	287
CL-EDA	1045	346
CL-EDR-148	961	330
CL-D-400	1091	409
CL-D-4000	777	264
CL-M-2005	961	334

The experimental results corroborate the thermodynamic potentials obtained by simulation (see section 3.7), which indicated that for CL-CA sample only via physisorption occurs; CO₂ is adsorbed due to electrostatic interactions. However, for samples functionalized with NH and NH₂ groups, chemisorption occurs. It is well-known that the interaction between the basic surface and acidic CO₂ molecules results in the formation of surface ammonium carbamates under anhydrous conditions (Yu et al., 2012). Among the amine-modified cellulose samples, the best CO₂ sorption result was obtained for the sample functionalized with CL-D-400, whereas the worst result was recorded in the case of CL-D-4000. The micrograph images (Figure 6g) showed a better separation of fiber bundles for the sample CL-D-400. This can improve the interaction of CO₂ with the cellulose chain groups. For the CL-D-4000 sample, (Figure 6h) a higher compaction of the fibers is observed, which can hinder the interaction with CO₂. More detailed discussion regarding the interaction of the compounds with CO₂ is available below.

The CO₂ sorption capacity of the amine modified cellulose described in this study was lower when compared with commercial solid adsorbents (1800-2000 µmol/g) of surface areas of 1000 to 1700 m²/g (Gray et al., 2004). However, the cellulose used in this study originates from an agricultural residue and presents a low amount of amine (2×10^{- 6} mol/mg) when compared to the literature (concentrations of 10-20% (w/w)) (Bachelor and Toochinda, 2012). For example, the sorption results at 1 bar and 30°C were 351 µmol CO₂/g (for bagasse enriched with 20% of DEA) and 329 µmol CO₂/g (for rice chaff). These results are similar to that obtained for CL-EDA (346 µmol CO₂/g) and lower than the sorption values obtained for the sample CL-D-400 (409 µmol CO₂/g) using lower amine concentrations of around 2×10^{- 6}(mol/mg).

In order to examine the reusability of the best material, CL-D-400 was subjected to five additional runs. The sorption was carried out at 25°C under 1 bar of CO₂ pressure. The CO₂ desorption was carried out at 100 °C. At the end, a loss of 5% in the sorption capacity was observed. We believe the sorption capacity loss is related to ammonium carbamate formation as evidenced in the proposed mechanism described in the literature (Aboudi and Vafaeezadeh, 2015).

Quantum mechanical simulations

Our experimental results (Table 2 with gas-capture results) indicate that all employed compounds, except CL-CA, exhibit a similar performance. Pressure increase leads to better CO₂ capture, while the order of the compound efficacies persists. A poor performance of CL-CA is due to the absence of chemisorption in this case and weak attraction of the CO₂ molecule to the protonated acetate group. Indeed, the computed binding energy for this case amounts to just 7 kJ mol^-1. The other results can be rationalized via computation of thermodynamic potentials for chemisorption of the molecular fragments (Figure 7), which represent the major working sites, -NH- and -NH₂, of the employed compounds.

Figure 7
Optimized structures of the molecular fragments which are responsible for CO₂ capture in the modified cellulose species.

Thermodynamic potentials (Figure 8) were used to rationalize the experimentally observed performances of the cellulose-based compounds. The depicted potentials correspond to the chemisorption reactions, but omitting subsequent solvation and ionization in aqueous media. This is done for simplicity of discussion and straightforward comparison. For instance, a total free energy of ethylamine is 20 kJ mol^-1, due to hydrogen bonds between the products of chemisorption and media. Johnson and coworkers (Xie et al., 2010) thoroughly investigated the mechanism of CO₂ chemisorption by the primary amine and presented extensive evidence that the two-step pathway via a zwitterion intermediate is most energetically favorable and, thus, most expected under the working conditions.

Figure 8
Free energy (top), enthalpy (center) and entropy (bottom) for CO₂ capture through chemisorption at –NH₂ by the molecular fragments depicted in Figure 7. The results from the G-4-MP2 method are red solid lines, from the G-3-MP2 method are green dashed lines, from the G-3 method are blue dash-dotted lines.

The trend of enthalpy completely repeats the trend of free energy (Figure 8). The entropic contribution is similar in all cases. Therefore, the chemical environment (in particular, non-covalent binding energy) is responsible for the difference between the considered molecular fragments. The best performance was found for CL-D-400 and CL-EDA. This is confirmed theoretically by the thermodynamics of fragment 2, whose free energy and enthalpy are lowest. The chemisorption is conducted both through the amide and amine groups and their high concentrations in the compounds. The performance of CL-D-4000 is worse, since that compound contains lots of ether groups, which are not efficient for CO₂ fixation. The ether group itself attracts CO₂ weakly. The binding energy corresponding to this process is 8 kJ mol^-1. The impact of a few available carboxylate groups is even smaller, 4 kJ mol^-1 in terms of binding energy. The performance of CL-HYD is inferior to that of CL-EDA, because the amide group cannot bind CO₂ in the -NH-NH₂ configuration. The resulting compound is unstable (according to the stationary-point-search simulations) and, therefore, is never formed. In turn, separating -NH- and -NH₂ by one or two methylene groups allows to achieve a more decent CO₂ capture.

It is noteworthy that the gas-phase thermodynamics provides a correct account of the reactions occurring in the condensed phase allowing one to rate large molecules with multiple binding sites. This fact also suggests that intra-molecular interactions are more important than inter-molecular ones upon chemical adsorption. All methods, G-3, G-3-MP2, G-4-MP2, for thermodynamic potentials provide very similar results.

Since a total number of molecules decreases upon chemisorption, a pressure increase shifts this reaction rightwards. Figure 9 depicts an effect of pressure up to 1000 MPa. The latter brings the 34 kJ mol^-1 free energy increase. An approximate shift of the chemisorption equilibrium constant can be estimated from the following relationship: Kⁱ = exp (-Gⁱ/R×T), where T is temperature, R is the gas constant, Gⁱ is the free energy at the given conditions. These calculations allow to determine to which extent it is economically feasible to invest in the high-pressure apparatus. The calculated effect of pressure is in concordance with our experimental results. In all systems, higher pressure results in a significantly better CO₂ fixation.

Figure 9
Free energy decrease due to elevation of external pressure. The thermodynamics of the CO₂ capture reaction by ethyl amine were considered for an example.

CONCLUSION

The chemical modification of cellulose fibers, extracted from rice husk, with different amines was performed. The potential of the obtained compounds for use as sorbents for CO₂ capture was evaluated. The quantum mechanical simulations and the experimental results revealed the role of each moiety of the new compounds in the gas capture process. A poor performance of CL-CA was due to the absence of chemisorption in this case and a relatively weak attraction of the CO₂ molecule to the protonated acetate group. The best performance was found in CL-D-400 (409 µmol CO₂/g at 1 bar). This result is confirmed theoretically by the thermodynamics of fragment 2, whose free energy and enthalpy are lowest. The chemisorption is conducted both through the amide and amine groups, therefore, their high concentrations in the compounds are important. On the other hand, when a higher-molecular-weight amine was used (CL-D-4000) the performance was worse, since that compound contained lots of ether groups, which are not efficient for CO₂ fixation. The performance of CL-HYD is inferior to that of CL-EDA, because the amide group cannot chemically bind CO₂ in the -NH-NH₂ configuration. In turn, separating -NH- and -NH₂ by one or two methylene groups results in a more decent CO₂ capture. Higher pressure results in a significantly better CO₂ fixation. The use of an industrial residue, cellulose, is a low-cost option material for CO₂ capture.

ACKNOWLEDGMENTS

This work was achieved in cooperation with Hewlett-Packard Brasil Ltda. using incentives of Brazilian Informatics Law (Law nº 8.2.48 of 1991).The authors would like to thank Cooperativa Arrozeira Extremo Sul Ltda for donating the rice husk and Huntsman Perfomance Products - Brazil for donating the Jeffamines, Sandra Einloft thanks CNPq for research scholarship. Franciele L. Bernard thanks Hewlett-Packard Brasil Ltda for scholarship.

REFERENCES

• Aboudi, J.; Vafaeezadeh, M., Efficient and reversible CO₂ capture by amine functionalized-silica gel confined task-specific ionic liquid system. Journal of Advanced Research, 6, 571-577 (2015). https://doi.org/10.1016/j.jare.2014.02.001
  » https://doi.org/10.1016/j.jare.2014.02.001
• Arias, A. M.; Mores, P. L.; Scenna, N. J.; MussatI, S. F., Optimal design and sensitivity analysis of post-combustion CO₂ capture process by chemical absorption with amines. Journal of Cleaner Production, 115, 315-331 (2016). https://doi.org/10.1016/j.jclepro.2015.12.056
  » https://doi.org/10.1016/j.jclepro.2015.12.056
• Bachelor, T. T. N.; Toochinda, P., Development of low-cost amine-enriched solid sorbent for CO2 capture. Environmental Technology, 33(23) 2645-2651 (2012). https://doi.org/10.1080/09593330.2012.673014
  » https://doi.org/10.1080/09593330.2012.673014
• Barbosa, R. C.; Damasceno, J. J. R.; Hori, C. E., The use of a high limestone content mining waste as a sorbent for CO₂ capture. Brazilian Journal of Chemical Engineering, 33(3) 599-606 (2016). https://doi.org/10.1590/0104-6632.20160333s20150111
  » https://doi.org/10.1590/0104-6632.20160333s20150111
• Becke, A. D., Density-functional exchange-energy approximation with correct asymptotic behavior. Physical Review A, 38(6) 3098-3100, 1 (1988). https://doi.org/10.1103/PhysRevA.38.3098
  » https://doi.org/10.1103/PhysRevA.38.3098
• Bernard, F. L.; Rodrigues, D. M.; Polesso, B. B.; Donato, A. J.; Seferin, M.; Chaban, V. V.; Vecchia, F. D.; Einloft, S., New cellulose based ionic compounds as low-cost sorbents for CO₂ capture. Fuel Processing Technology, 149, 131-138 (2016). https://doi.org/10.1016/j.fuproc.2016.04.014
  » https://doi.org/10.1016/j.fuproc.2016.04.014
• Blasig, A.; Tang, J.; Hu, X.; Shen, Y.; Radosz, M., Magnetic suspension balance study of carbon dioxide solubility in ammonium-based polymerized ionic liquids: Poly(p-vinylbenzyltrimethyl ammonium tetrafluoroborate) and poly([2-(methacryloyloxy)ethyl] trimethyl ammonium tetrafluoroborate). Fluid Phase Equilibria, 256(1-2), 75-80 (2007). https://doi.org/10.1016/j.fluid.2007.03.007
  » https://doi.org/10.1016/j.fluid.2007.03.007
• Chan, W. N.; Walter, A.; Sugiyama, M. I.; Borges, G. C., Assessment of CO₂ Emission Mitigation For a Brazilian Oil Refinery. Brazilian Journal of Chemical Engineering , 33(4) 835-850, (2016). https://doi.org/10.1590/0104-6632.20160334s20140149
  » https://doi.org/10.1590/0104-6632.20160334s20140149
• Cuadro, P. DE; Belt, T.; Kontturi, K. S.; Reza, M.; Kontturi, E.; Vuorinen, T.; Hughes, M., Cross-linking of cellulose and poly(ethylene glycol) with citric acid. Reactive and Functional Polymers, 90, 21-24 (2015). https://doi.org/10.1016/j.reactfunctpolym.2015.03.007
  » https://doi.org/10.1016/j.reactfunctpolym.2015.03.007
• Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Rassolov, V.; Pople, J. A., Gaussian-3 (G3) theory for molecules containing first and second-row atoms. The Journal of Chemical Physics, 109(18), 7764-7776, (1998). https://doi.org/10.1063/1.477422
  » https://doi.org/10.1063/1.477422
• Curtiss, L. A.; Redfern, P. C.; Raghavachari, K., Gaussian-4 theory using reduced order perturbation theory. The Journal of Chemical Physics , 127(12) 124105 (2007). https://doi.org/10.1063/1.2770701
  » https://doi.org/10.1063/1.2770701
• Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Rassolov, V.; Pople, J. A., Gaussian-3 theory using reduced Mo/ller-Plesset order. The Journal of Chemical Physics , 110(10) 4703-4709 (1999). https://doi.org/10.1063/1.478385
  » https://doi.org/10.1063/1.478385
• Dreisbach, F.; Lösch, H. W., Magnetic Suspension Balance For Simultaneous Measurement of a Sample and the Density of the Measuring Fluid. Journal of Thermal Analysis and Calorimetry, 62(2), 515-521 (2000). https://doi.org/10.1023/A:1010179306714
  » https://doi.org/10.1023/A:1010179306714
• Dutcher, B.; Fan, M.; Russell, A. G., Amine-Based CO₂ Capture Technology Development from the Beginning of 2013-A Review. ACS Applied Materials & Interfaces, 7(4), 2137-2148 (2015). https://doi.org/10.1021/am507465f
  » https://doi.org/10.1021/am507465f
• Garcés, S. I.; Villarroel-Rocha, J.; Sapag, K.; Korili, S. A.; Gil, A., Comparative Study of the Adsorption Equilibrium of CO₂ on Microporous Commercial Materials at Low Pressures. Industrial & Engineering Chemistry Research, 52(20), 6785-6793, (2013). https://doi.org/10.1021/ie400380w
  » https://doi.org/10.1021/ie400380w
• Garđarsdóttir, S. Ó.; Normann, F.; Andersson, K.; Johnsson, F., Postcombustion CO₂ Capture Using Monoethanolamine and Ammonia Solvents: The Influence of CO₂ Concentration on Technical Performance. Industrial & Engineering Chemistry Research , 54(2), 681-690 (2015). https://doi.org/10.1021/ie503852m
  » https://doi.org/10.1021/ie503852m
• Gebald, C.; Wurzbacher, J. A.; Tingaut, P.; Steinfeld, A., Stability of Amine-Functionalized Cellulose during Temperature-Vacuum-Swing Cycling for CO₂ Capture from Air. Environmental Science & Technology, 47(17), 10063-10070 (2013). https://doi.org/10.1021/es401731p
  » https://doi.org/10.1021/es401731p
• Gellerested, F.; Gatenholm, P., Surface properties of lignocellulosic fibers bearing carboxylic groups, Cellulose, 6, 103-121 (1999). https://doi.org/10.1023/A:1009239225050
  » https://doi.org/10.1023/A:1009239225050
• Gebald, C.; Wurzbacher, J. A.; Tingaut, P.; Zimmermann, T.; Steinfeld, A., Amine-Based Nanofibrillated Cellulose As Adsorbent for CO₂ Capture from Air. Environmental Science & Technology , 45(20), 9101-9108 (2011). https://doi.org/10.1021/es202223p
  » https://doi.org/10.1021/es202223p
• Gray, M. L.; Soong, Y.; Champagne, K. J.; Baltrus, J.; Stevens, R. W.; Toochinda, P.; Chuang, S. S. C., CO₂ capture by amine-enriched fly ash carbon sorbents. Separation and Purification Technology, 35(1), 31-36 (2004). https://doi.org/10.1016/S1383-5866(03)00113-8
  » https://doi.org/10.1016/S1383-5866(03)00113-8
• Gray, M. L.; Soong, Y.; Champagne, K. J.; Pennline, H.; Baltrus, J. P.; Stevens, R. W.; Khatri, R.; Chuang, S. S. C.; Filburn, T., Improved immobilized carbon dioxide capture sorbents. Fuel Processing Technology , 86(14-15), 1449-1455 (2005). https://doi.org/10.1016/j.fuproc.2005.01.005
  » https://doi.org/10.1016/j.fuproc.2005.01.005
• Gurgel, L. V. A.; Júnior, O. K.; Gil, R. P. De F.; Gil, L. F., Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by cellulose and mercerized cellulose chemically modified with succinic anhydride. Bioresource Technology, 99(8), 3077-3083 (2008). https://doi.org/10.1016/j.biortech.2007.05.072
  » https://doi.org/10.1016/j.biortech.2007.05.072
• Hussain, A.; Farrukh, S.; Minhas, F. T., Two-Stage Membrane System for Post-combustion CO 2 Capture Application. Energy & Fuels, 29(10), 6664-6669 (2015). https://doi.org/10.1021/acs.energyfuels.5b01464
  » https://doi.org/10.1021/acs.energyfuels.5b01464
• IBGE - GRUPO DE COORDENAÇÃO DE ESTATÍSTICAS AGROPECUÁRIAS. Levantamento Sistemático da Produção Agrícola. Disponível em: <Disponível em: http://www.ibge.gov.br/home/estatistica/indicadores/agropecuaria/lspa/lspa_201702_5.shtm >. Acesso em: 28 mar. 2017.
  » http://www.ibge.gov.br/home/estatistica/indicadores/agropecuaria/lspa/lspa_201702_5.shtm
• IPCC, Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2013.
• Johar, N.; Ahmad, I.; Dufresne, A., Extraction, preparation and characterization of cellulose fibres and nanocrystals from rice husk. Industrial Crops and Products, 37(1), 93-99 (2012). https://doi.org/10.1016/j.indcrop.2011.12.016
  » https://doi.org/10.1016/j.indcrop.2011.12.016
• K. Shukla, S.; Bharadvaja, A.; C. Dubey, G.; Tiwari, A., Preparation And Characterization Of Cellulose Derived From Rice Husk For Drug Delivery. Advanced Materials Letters, 4(9), 714-719 (2013). https://doi.org/10.5185/amlett.2013.2415
  » https://doi.org/10.5185/amlett.2013.2415
• Kamarudin, K. S. N.; Alias, N., Adsorption performance of MCM-41 impregnated with amine for CO2 removal. Fuel Processing Technology , 106, 332-337 (2013). https://doi.org/10.1016/j.fuproc.2012.08.017
  » https://doi.org/10.1016/j.fuproc.2012.08.017
• Karnitz, O.; Gurgel, L. V. A.; Melo, J. C. P. DE; Botaro, V. R.; Melo, T. M. S.; Freitas Gil, R. P. de; Gil, L. F., Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse. Bioresource Technology , 98(6), 1291-1297 (2007). https://doi.org/10.1016/j.biortech.2006.05.013
  » https://doi.org/10.1016/j.biortech.2006.05.013
• Knowles, G. P.; Graham, J. V.; Delaney, S. W.; Chaffee, A. L., Aminopropyl-functionalized mesoporous silicas as CO2 adsorbents. Fuel Processing Technology , 86(14-15), 1435-1448 (2005). https://doi.org/10.1016/j.fuproc.2005.01.014
  » https://doi.org/10.1016/j.fuproc.2005.01.014
• Lee, C.; Yang, W.; Parr, R. G., Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B, 37(2), 785-789 (1988). https://doi.org/10.1103/PhysRevB.37.785
  » https://doi.org/10.1103/PhysRevB.37.785
• Leung, D. Y. C.; Caramanna, G.; Maroto-valer, M. M., An overview of current status of carbon dioxide capture and storage technologies. Renewable and Sustainable Energy Reviews, 39, 426-443 (2014). https://doi.org/10.1016/j.rser.2014.07.093
  » https://doi.org/10.1016/j.rser.2014.07.093
• Li, R.; Fei, J.; Cai, Y.; LI, Y.; Feng, J.; Yao, J., Cellulose whiskers extracted from mulberry: A novel biomass production. Carbohydrate Polymers, 76(1), 94-99 (2009). https://doi.org/10.1016/j.carbpol.2008.09.034
  » https://doi.org/10.1016/j.carbpol.2008.09.034
• Lima, A. E. O.; Gomes, V. A. M.; Lucena, S. M. P., Theoretical study of CO₂:N₂ adsorption in faujasite impregnated with monoethanolamine. Brazilian Journal of Chemical Engineering , 32(3), 663-669 (2015). https://doi.org/10.1590/0104-6632.20150323s00003450
  » https://doi.org/10.1590/0104-6632.20150323s00003450
• Magalhaes, T. O.; Aquino, A. S.; Dalla Vecchia, F.; Bernard, F. L.; Seferin, M.; Menezes, S. C.; Ligabue, R.; Einloft, S., Syntheses and characterization of new poly(ionic liquid)s designed for CO₂ capture. RSC Adv., 4(35), 18164-18170, (2014). https://doi.org/10.1039/c4ra00071d
  » https://doi.org/10.1039/c4ra00071d
• Nouri, S. M. M.; Ebrahim, H. A., Effect of sorbent pore volume on the carbonation reaction of lime with CO₂ Brazilian Journal of Chemical Engineering , 33(2), 383-389 (2016). https://doi.org/10.1590/0104-6632.20160332s20140245
  » https://doi.org/10.1590/0104-6632.20160332s20140245
• Rodrigues, R. F.; Trevenzoli, R. L.; Santos, L. R. G.; Leão, V. A.; Botaro, V. R., Heavy metals sorption on treated wood sawdust. Engenharia Sanitaria e Ambiental, 11(1) (2006). https://doi.org/10.1590/S1413-41522006000100004
  » https://doi.org/10.1590/S1413-41522006000100004
• Rosa, S. M. L.; Rehman, N.; Miranda, M. I. G. DE; Nachtigall, S. M. B.; Bica, C. I. D., Chlorine-free extraction of cellulose from rice husk and whisker isolation. Carbohydrate Polymers , 87(2), 1131-1138 (2012). https://doi.org/10.1016/j.carbpol.2011.08.084
  » https://doi.org/10.1016/j.carbpol.2011.08.084
• Segal, L.; Creely, J. J.; Martin, A. E.; Conrad, C. M., An Empirical Method for Estimating the Degree of Crystallinity of Native Cellulose Using the X-Ray Diffractometer. Textile Research Journal, 29(10) 786-794 (1959). https://doi.org/10.1177/004051755902901003
  » https://doi.org/10.1177/004051755902901003
• Seo, S.; Simoni, L. D.; Ma, M.; Desilva, M. A.; Huang, Y.; Stadtherr, M. A.; Brennecke, J. F., Phase-Change Ionic Liquids for Postcombustion CO 2 Capture. Energy & Fuels , 28(9), 5968-5977 (2014). https://doi.org/10.1021/ef501374x
  » https://doi.org/10.1021/ef501374x
• Shang, W.; Sheng, Z.; Shen, Y.; AI, B.; Zheng, L.; Yang, J.; Xu, Z., Study on oil absorbency of succinic anhydride modified banana cellulose in ionic liquid. Carbohydrate Polymers , 141, 135-142 (2016). https://doi.org/10.1016/j.carbpol.2016.01.009
  » https://doi.org/10.1016/j.carbpol.2016.01.009
• Teodoro, K. B. R.; Teixeira, E. De M.; Corrêa, A. C.; Campos, A. De; Marconcini, J. M.; Mattoso, L. H. C., Whiskers de fibra de sisal obtidos sob diferentes condições de hidrólise ácida: efeito do tempo e da temperatura de extração. Polímeros, 21(4), 280-285 (2011). https://doi.org/10.1590/S0104-14282011005000048
  » https://doi.org/10.1590/S0104-14282011005000048
• Xie, H.-B.; Zhou, Y.; Zhang, Y.; Johnson, J. K., Reaction Mechanism of Monoethanolamine with CO₂ in Aqueous Solution from Molecular Modeling. The Journal of Physical Chemistry A, 114(43), 11844-11852 (2010). https://doi.org/10.1021/jp107516k
  » https://doi.org/10.1021/jp107516k
• Yu, C.H.; Huang, C.H.; Tan, C.S., A Review of CO₂ Capture by Absorption and Adsorption. Aerosol Air Qual. Res., 12(5), 745-769 (2012). https://doi.org/10.4209/aaqr.2012.05.0132
  » https://doi.org/10.4209/aaqr.2012.05.0132
• Yu, J.; Le, Y.; Cheng, B., Fabrication and CO₂ adsorption performance of bimodal porous silica hollow spheres with amine-modified surfaces. RSC Advances, 2(17) 6784-6791, (2012). https://doi.org/10.1039/c2ra21017g
  » https://doi.org/10.1039/c2ra21017g
• Zhang, K.; Sun, P.; Liu, H.; Shang, S.; Song, J.; Wang, D., Extraction and comparison of carboxylated cellulose nanocrystals from bleached sugarcane bagasse pulp using two different oxidation methods. Carbohydrate Polymers , 138, 237-243, (2016). https://doi.org/10.1016/j.carbpol.2015.11.038
  » https://doi.org/10.1016/j.carbpol.2015.11.038
• Zhu, B.; Fan, T.; Zhang, D., Adsorption of copper ions from aqueous solution by citric acid modified soybean straw. Journal of Hazardous Materials, 153(1-2), 300-308 (2008). https://doi.org/10.1016/j.jhazmat.2007.08.050
  » https://doi.org/10.1016/j.jhazmat.2007.08.050

Publication Dates

• Publication in this collection
  15 July 2019
• Date of issue
  Jan-Mar 2019

History

• Received
  09 Apr 2017
• Reviewed
  11 Dec 2017
• Accepted
  30 Jan 2018