Development of chemically activated N-enriched carbon adsorbents from urea-formaldehyde resin for CO2 adsorption: Kinetics, isotherm, and thermodynamics.

Nitrogen enriched carbon adsorbents with high surface areas were successfully prepared by carbonizing the low-cost urea formaldehyde resin, followed by KOH activation. Different characterization techniques were used to determine the structure and surface functional groups. Maximum surface area and total pore volume of 4547 m2 g-1 and 4.50 cm3 g-1 were found by controlling activation conditions. The optimized sample denoted as UFA-3-973 possesses a remarkable surface area, which is found to be one of the best surface areas achieved so far. Nitrogen content of this sample was found to be 22.32%. Dynamic CO2 uptake capacity of the carbon adsorbents were determined thermogravimetrically at different CO2 concentrations (6-100%) and adsorption temperatures (303-373 K) which have a much more relevance for the flue gas application. Highest adsorption capacity of 2.43 mmol g-1 for this sample was obtained at 303 K under pure CO2 flow. Complete regenerability of the adsorbent over four adsorption-desorption cycles was obtained. Fractional order kinetic model provided best description of adsorption over all adsorption temperatures and CO2 concentrations. Heterogeneity of the adsorbent surface was confirmed from the Langmuir and Freundlich isotherms fits and isosteric heat of adsorption values. Exothermic, spontaneous and feasible nature of adsorption process was confirmed from thermodynamic parameter values. The combination of high surface area and large pore volume makes the adsorbent a new promising carbon material for CO2 capture from power plant flue gas and for other relevant applications.

Melamine-formaldehyde derived porous carbons for adsorption of CO2 capture.

In this work, we report carbon adsorbents obtained from high nitrogen content melamine-formaldehyde resin as starting material and mesoporous zeolite MCM-41 as template through nanocasting technique. To synthesize different carbon structure adsorbents with improved textural and surface properties, the material undergo carbonization followed by physical activation under CO2 atmosphere at different temperatures. Characterizations of the adsorbents using SEM, TEM, XPS, nitrogen sorption, CHN, TKN, and TPD have been carried out. Characterization results reveal the development of nanostructured carbon adsorbents with better texture and surface properties as compared to the sample prepared by direct carbonization. Sample prepared at carbonization-activation temperature of 700 °C shows highest basicity, surface area (193.28 m2 g-1) and pore volume (0.32 cm3 g-1). Performance evaluation of adsorbent was performed thermo gravimetrically at different temperatures and concentrations and was found that the adsorbent synthesized at 700 °C exhibit highest CO2 uptake of 0.93 mmol g-1 with nitrogen content of 22.73%. It was found that both surface area and nitrogen functional group have a major impact on adsorption capacity. Physiosorption process was confirmed by a decrease in adsorption capacity with increase in temperature. Three kinetic models and isotherms were used in this study and found that fractional order kinetic model and Freundlich isotherm best fitted with the experimental data. Isotherm study depicts the heterogeneous nature of adsorbent surface. Adsorbent exhibited complete regenerability and was stable over four adsorption-desorption cycles. Low value of isosteric heat of adsorption of 15.75 kJ mol-1, indicates physiosorption process. Negative value of ΔG0 and ΔH0 confirms spontaneous, feasible and exothermic nature of adsorption process.

Measurement of residence time distribution of liquid phase in an industrial-scale continuous pulp digester using radiotracer technique.

A series of radiotracer experiments was carried out to measure residence time distribution (RTD) of liquid phase (alkali) in an industrial-scale continuous pulp digester in a paper industry in India. Bromine-82 as ammonium bromide was used as a radiotracer. Experiments were carried out at different biomass and white liquor flow rates. The measured RTD data were treated and mean residence times in individual digester tubes as well in the whole digester were determined. The RTD was also analyzed to identify flow abnormalities and investigate flow dynamics of the liquid phase in the pulp digester. Flow channeling was observed in the first section (tube 1) of the digester. Both axial dispersion and tanks-in-series with backmixing models preceded with a plug flow component were used to simulate the measured RTD and quantify the degree of axial mixing. Based on the study, optimum conditions for operating the digester were proposed.

Development of nitrogen enriched nanostructured carbon adsorbents for CO2 capture.

Nanostructured carbon adsorbents containing high nitrogen content were developed by templating melamine-formaldehyde resin in the pores of mesoporous silica by nanocasting technique. A series of adsorbents were prepared by altering the carbonization temperature from 400 to 700 °C and characterized in terms of their textural and morphological properties. CO2 adsorption performance was investigated at various temperatures from 30 to 100 °C by using a thermogravimetric analyzer under varying CO2 concentrations. Multiple adsorption-desorption experiments were also carried out to investigate the adsorbent regenerability. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the development of nanostructured materials. Fourier transform infrared spectroscopy (FTIR) and elemental analysis indicated the development of carbon adsorbents having high nitrogen content. The surface area and pore volume of the adsorbent carbonized at 700 °C were found to be 266 m(2) g(-1) and 0.25 cm(3) g(-1) respectively. CO2 uptake profile for the developed adsorbents showed that the maximum CO2 adsorption occurred within ca. 100 s. CO2 uptake of 0.792 mmol g(-1) at 30 °C was exhibited by carbon obtained at 700 °C with complete regenerability in three adsorption-desorption cycles. Furthermore, kinetics of CO2 adsorption on the developed adsorbents was studied by fitting the experimental data of CO2 uptake to three kinetic models with best fit being obtained by fractional order kinetic model with error% within range of 5%. Adsorbent surface was found to be energetically heterogeneous as suggested by Temkin isotherm model. Also the isosteric heat of adsorption for CO2 was observed to increase from ca. 30-44 kJ mol(-1) with increase in surface coverage.

Mesoporous carbon adsorbents from melamine-formaldehyde resin using nanocasting technique for CO2 adsorption.

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine-formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental (CHN) analysis, Fourier transform infrared (FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO2 capture. The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent-CO2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption-desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.

Bleaching with lignin-oxidizing enzymes.

General concern about the environmental impact of chlorine bleaching effluents has led to a trend towards elementary chlorine-free or totally chlorine free bleaching methods. Considerable interest has been focused on the use of biotechnology in pulp bleaching, as large number of microbes and the enzymes produced by them are known to be capable of preferential degradation of native lignin and complete degradation of wood. Enzymes of the hemicellulolytic type, particularly xylan-attacking enzymes xylanases are now used commercially in the mills for pulp treatment and subsequent incorporation into bleach sequences. Certain white-rot fungi can delignify Kraft pulps increasing their brightness and their responsiveness to brightening with chemicals. The fungal treatments are too slow but the enzymes produced from the fungi can also delignify pulps and these enzymatic processes are likely to be easier to optimize and apply than the fungal treatments. This article presents an overview of the developments in the application of lignin-oxidizing enzymes in bleaching of chemical pulps. The present knowledge of the mechanisms on the action of enzymes as well as the practical results and advantages obtained on the laboratory and industrial scale are discussed.

Biochemical pulping of bagasse.

This study deals with pretreatment of wheat straw with lignin-degrading fungi and its effect on chemical pulping. Ceriporiopsis subvermispora strains, which preferentially attack the lignin, were used for biochemical pulping of bagasse. Treatment of depithed bagasse with different strains of C. subvermispora reduced the kappa number by 10-15% and increased unbleached pulp brightness by 1.1-2.0 ISO points on chemical pulping at the same alkali charge. Bleaching of biopulps at the same chemical charge increased final brightness by 4.7-5.6 ISO points and whiteness by 10.2-11.4 ISO points. Fungal treatment did not result in any adverse effect on the strength properties of pulp.