Nitrogen-doping activated biomass carbon from tea seed shell for CO2 capture and supercapacitor

Activated carbon is a promising material that has a broad application prospect. In this work, biomass (tea seed shell) was used to prepare activated carbon with KOH activation (referred to as AC), and nitrogen was doped in activated carbon using melamine as the nitrogen source (referred to as NAC-x, where x is the mass ratio of melamine and activated carbon). The obtained activated biomass carbon (activated bio-carbon) samples were characterized by Brunauer–Emmett–Teller (BET)-specific surface area analysis, ultimate analysis, X-ray photoelectron spectroscopy (XPS) analysis, Raman spectrum analysis, and X-ray diffraction (XRD) patterns. The specific surface areas of activated bio-carbons were 1503.20 m²/g (AC), 1064.54 m²/g (NAC-1), 1187.93 m²/g (NAC-2), 1055.32 m²/g (NAC-3), and 706.22 m²/g (NAC-4), revealing that nitrogen-doping process leads to decrease in specific surface area. XPS analysis revealed that the main nitrogen-containing functional groups were pyrrolic-N and pyridinic-N. The capacity of CO₂ capture and electrochemical performance of activated bio-carbon samples were investigated. The CO₂ capturing capacity followed this order: AC (3.15 mmol/g) > NAC-2 (2.75 mmol/g) > NAC-1 (2.69 mmol/g) > NAC-3 (2.44 mmol/g) > NAC-4 (1.95 mmol/g) at 298 K at 1 bar, which is consistent with the order of specific surface area. The specific surface area played a dominant role in CO₂ capturing capacity. As for supercapacitor, AC-4 showed the highest specific capacitance (168 F/g) at the current density of 0.5 A/g, but NAC-2 showed the best electrochemical performance (89 F/g) at 2 A/g. Nitrogen-containing functional groups and specific surface area both had an important impact on electrochemical performance. In general, NAC-3 and NAC-2 produced excellent electrochemical performance. Compared with NAC-3, less melamine was used to prepare NAC-2; therefore, NAC-2 was considered as the best activated bio-carbon for supercapacitor for 141 F/g (at 0.5 A/g), 108 F/g (at 1 A/g), and 89 F/g (at 2 A/g) in this work.     

Lignin‐derived heteroatom‐doped porous carbons for supercapacitor and CO2 capture applications

The present study reports the economic and sustainable syntheses of functional porous carbons for supercapacitor and CO₂ capture applications. Lignin, a byproduct of pulp and paper industry, was successfully converted into a series of heteroatom‐doped porous carbons (LHPCs) through a hydrothermal carbonization followed by a chemical activating treatment. The prepared carbons include in the range of 2.5 to 5.6 wt% nitrogen and 54 wt% oxygen in its structure. All the prepared carbons exhibit micro‐ and mesoporous structures with a high surface area in the range of 1788 to 2957 m² g^?1. As‐prepared LHPCs as an active electrode material and CO₂ adsorbents were investigated for supercapacitor and CO₂ capture applications. Lignin‐derived heteroatom‐doped porous carbon 850 shows an outstanding gravimetric specific capacitance of 372 F g^?1 and excellent cyclic stability over 30,000 cycles in 1 M KOH. Lignin‐derived heteroatom‐doped porous carbon 700 displays a remarkable CO₂ capture capacity of up to 4.8 mmol g^?1 (1 bar and 298 K). This study illustrates the effective transformation of a sustainable waste product into a highly functional carbon material for energy storage and CO₂ separation applications.     

One-pot synthesis of high N-doped porous carbons derived from a N-rich oil palm biomass residue in low temperature for CO2 capture

Porous carbon materials have been widely used for CO₂ adsorption, but their preparation was subject to conditions such as raw material cost, activator corrosion, and temperature. In this study, nitrogen-doped porous carbonaceous adsorbents were prepared in a low temperature region (400-550°C) by one-step composite nitrogen doping method, using low-cost oil residue as raw materials and less corrosive NaNH₂ as activator. The CO₂ adsorption performances of the prepared N-doped porous adsorbents were systematically explored. The results showed that optimal oil residue-derived carbonaceous adsorbent owned excellent amount of CO₂ adsorption up to 3.51 and 5.63 mmol/g at 298 and 273 K under 1 bar, respectively. It was discovered that the congenerous influences of porous structure, nitrogen content and V_n of the adsorbent affected their CO₂ adsorption performances under 1 bar. Importantly, these oil residue porous carbonaceous adsorbent also was verified owning fine selectivity of the CO₂ over N₂ (15.7), which attributed to its high V_n and nitrogen content. Furthermore, optimal sample OAC-500-2.5 owned medium Q_st (21-26 kJ/mol), which was beneficial practical application. This work may inspire new sparks on novel nitrogen-doped adsorbent with inexpensive precursor, low activation temperature and simple preparative tactic, indicating that the nitrogen-doped sample is promising in the practical situation of CO₂ adsorption.     

双流化床生物质气化及CO2捕获的模拟

用Aspen Plus建立了双流化床气化和燃烧模型,对生物质在双流化床中气化及CaO吸收合成气中的CO2过程进行了模拟研究;探讨不同反应条件:气化温度、蒸汽与生物质的质量配比(S/B)以及CaO循环量与生物质的质量配比(Ca/B)对合成气成分的影响,为该类型工业反应器的研发提供了理论依据.模拟分析结果表明:气化温度低于700℃时,CaO能很好地吸收气化过程中产生的CO2并促进平衡反应向产氢方向进行;在温度为650℃及CaO作用下,S/B在0.6～1.7内对合成气成分的影响不大;CaO的加入能够有效地改善合成气的组成,合成气中氢气浓度能达到95％以上,氢气产量达到52 mol/kg.     

A coal-fired power plant integrated with biomass co-firing and CO2 capture for zero carbon emission

A promising scheme for coal-fired power plants in which biomass co-firing and carbon dioxide capture technologies are adopted and the low-temperature waste heat from the CO₂ capture process is recycled to heat the condensed water to achieve zero carbon emission is proposed in this paper. Based on a 660 MW supercritical coal-fired power plant, the thermal performance, emission performance, and economic performance of the proposed scheme are evaluated. In addition, a sensitivity analysis is conducted to show the effects of several key parameters on the performance of the proposed system. The results show that when the biomass mass mixing ratio is 15.40% and the CO₂ capture rate is 90%, the CO₂ emission of the coal-fired power plant can reach zero, indicating that the technical route proposed in this paper can indeed achieve zero carbon emission in coal-fired power plants. The net thermal efficiency decreases by 10.31%, due to the huge energy consumption of the CO₂ capture unit. Besides, the cost of electricity (COE) and the cost of CO₂ avoided (COA) of the proposed system are 80.37 $/MWh and 41.63 $/tCO₂, respectively. The sensitivity analysis demonstrates that with the energy consumption of the reboiler decreasing from 3.22 GJ/tCO₂ to 2.40 GJ/ tCO₂, the efficiency penalty is reduced to 8.67%. This paper may provide reference for promoting the early realization of carbon neutrality in the power generation industry.     

Comparison of MEA and DGA performance for CO2 capture under different operational conditions

Carbon capture and storage from flue gases is the most common method to reduce greenhouse gas emissions. Using a primary amine as the solvent of CO₂ capture unit is popular because of its high activity and ability to be used for streams with low concentration and low partial pressure of CO₂. Monoethanolamine(MEA) and Diglycolamine(DGA) are the most common kinds of primary amines which have been traditionally used in many natural gas sweetening plants. In this research, the capture plant has been designed for these two solvents at various CO₂ concentrations in the feed flue gas. This paper proposes different possible alters to overcome the high energy requirements of capture plant. It also presents the results of technical evaluation of different parameters, in order to design an actual plant with minimum energy requirement. The results of different parameters show that for DGA solvent, there will be an improvement in overall energy usage in the capture plant rather than MEA for some special cases. To gain the practical results, actual stages have been used for absorber and stripper instead of equilibrium stages. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication of microporous and mesoporous carbon spheres for high‐performance supercapacitor electrode materials

Microporous and mesoporous carbon spheres (CSs) were fabricated using resorcinol and formaldehyde as precursors in the presence of Pluronic F127 as porogen and KOH as the active agent. The textural characteristic and morphology were characterized by scanning electron microscopy, transmission electron microscopy, and N₂ adsorption/desorption techniques. Pluronic F127 played an important role for generating mesopores, while KOH activation brought abundant micropores and resulted in a combined microporous and mesoporous structure of the CSs. The results showed that a typical sample (denoted as CS‐F‐K) possessed a spherical shape, with a high specific surface area of 735.4 m²/g, large pore volume of 0.622 cm³/g, and combined microporous and mesoporous structure, which endowed CS‐F‐K good electrochemical performance with a specific capacitance of 182 F/g under a current density of 0.5 A/g, remarkable rate performance, and long‐term cycling stability. After 1000 cycles at 3 A/g, CS‐F‐K electrode can still remain the specific capacitance of 154.8 F/g with a retention of 98.9%. The excellent electrochemical performance of CS‐F‐K was mainly attributed to the micro‐mesoporous structure, which promoted the ion accumulation on the electrode surface and facilitated fast ion transportation. Copyright © 2015 John Wiley & Sons, Ltd.     

Melamine assisted preparation of nitrogen doped activated carbon from sustainable biomass for H2 and CO2 storage

Activated carbon (AC), as an effective solid adsorbent, is extensively employed in H₂ and CO₂ storage. To enhance its adsorption capability and selectivity, it is necessary to increase its surface area and dope heteroatoms by a simple and environment-friendly method. In this work, nitrogen doped activated carbon (NAC) has been synthesized from sustainable biomass by direct activation with the assistance of melamine. The obtained NAC with 2.1 wt% N dopants possesses a high surface area (2477.27 m²/g) and pore volume (1.93 cm³/g). The NAC displayed enhanced H₂ uptake capacity (2.29 wt% at 77 K, 1 bar and 0.83 wt% at 298 K, 100 bar) and adequate CO₂ uptake capacity (2.85 mmol/g at 298 K, 1 bar and 4.49 mmol/g at 273 K, 1 bar). Activation mechanism with the assistance of melamine was proposed in accordance with the experimental data. The facile method of preparing NAC is potential for large-scaled production.     

Microstructure regulation of super activated carbon from biomass source corncob with enhanced hydrogen uptake

A series of super activated carbon have been prepared by potassium hydroxide activation of corncob. The as-obtained samples were characterized by SEM, TEM and N₂-sorption. The results show morphologies and textural of activated carbon are highly depended on the activation temperature, heating rate, whereas the activation time is not a key factor. Morphologies and porous structure of activated carbons can be regulated by adjusting preparation parameters. A super activated carbon with BET surface area of 3530 m²/g and total pore volume of 1.94 cm³/g is obtained. However, the other activated carbon with smaller pore size exhibited the highest hydrogen uptake capacities exceeding 2.85 wt% at −196 °C and 1.0 bar, whose BET surface area is only 2988 m²/g. The correlation investigations show the micropore volume between 0.65 nm and 1.5 nm can be more important than BET surface area and total pore volume for hydrogen uptakes at −196 °C. The present results indicate that the corncob-derived activated carbons can be promising materials for hydrogen storage.     

Analysis of equilibrium CO2 solubility in aqueous APDA and its potential blends with AMP/MDEA for postcombustion CO2 capture

The utility of polyamine-based solvent-activators for the possible application in postcombustion CO₂ capture technology has drawn considerable attention recently owing to its higher loading capacity as well as superior kinetics. The current work involves a comprehensive experimental cum theoretical investigation on the equilibrium solubility of CO₂ pertaining to aqueous N-(3-aminopropyl)-1,3-propanediamine and its blends with N-methyldiethanolamine and 2-amino-2-methyl-1-propanol. The analysis was conducted within the operating temperature and CO₂ partial pressure range of 303.2-323.2 K and 2-200 kPa, respectively. Two different mathematical models based on nonrigorous approaches such as equilibrium based modified Kent-Eisenberg (KE) model and a multilayer feedforward neural network model have been developed to correlate the CO₂ solubility data over a wide range of experimental conditions. Both the model predictions are well-validated with the experimental results. The reaction scheme as well as the prevalence of important reaction products was further confirmed with qualitative ¹³C NMR as well as ATR-FTIR analysis. Apart from these some of the important thermally induced transport properties viz, density, viscosity, and surface tension of the aqueous single and blended systems were measured and correlated with various consistent empirical models such as Redlich-Kister and Grunberg-Nissan model while surface tension data are modeled using temperature-based multiple linear regression technique.     

Hydrogen and power co-generation based on coal and biomass/solid wastes co-gasification with carbon capture and storage

This paper investigates the potential use of renewable energy sources (various sorts of biomass) and solid wastes (municipal wastes, sewage sludge, meat and bone meal etc.) in a co-gasification process with coal to co-generate hydrogen and electricity with carbon capture and storage (CCS). The paper underlines one of the main advantages of gasification technology, namely the possibility to process lower grade fuels (lower grade coals, renewable energy sources, solid wastes etc.), which are more widely available than the high grade coals normally used in normal power plants, this fact contributing to the improvement of energy security supply. Based on a proposed plant concept that generates 400–500 MW net electricity with a flexible output of 0–200 MW_th hydrogen and a carbon capture rate of at least 90%, the paper develops fuel selection criteria for coal blending with various alternative fuels for optimizing plant performance e.g. oxygen consumption, cold gas efficiency, hydrogen production and overall energy efficiency. The key plant performance indicators were calculated for a number of case studies through process flow simulations (ChemCAD).     

Effect of CO2 atmosphere on biomass pyrolysis and in-line catalytic reforming

To enhance the conversion efficiency of biomass CO₂ gasification and decrease tar, the experimental study of biomass pyrolysis and in-line catalytic CO₂ reforming (BPy-ILCCR) were investigated in a two-stage reactor. The prepared K-Ni/Al catalyst exhibits superior catalytic activity for gas products in BPy-ILCCR. Results show that both CO₂ concentration and temperature promote the rise of the gas production, but the increase slows down when CO₂ concentration is more than 40 vol%. At 700°C, the gas yield and X_c can reach 0.83 g/g-bio and 92.4%, respectively (40 vol% CO₂, 3 g catalyst). The comparative study indicates that steam is slightly better for reducing liquid product under the same concentration of CO₂ and H₂O, and the X_c at 80 vol% CO₂ can reach 93.9%, close to the value obtained at 40 vol% H₂O. Moreover, there exist similar quantities of coke deposition on the catalyst under the CO₂ and H₂O atmosphere.     

Assessment of flexible energy vectors poly-generation based on coal and biomass/solid wastes co-gasification with carbon capture

This paper evaluates biomass and solid wastes co-gasification with coal for energy vectors poly-generation with carbon capture. The evaluated co-gasification cases were evaluated in term of key plant performance indicators for generation of totally or partially decarbonized energy vectors (power, hydrogen, substitute natural gas, liquid fuels by Fischer–Tropsch synthesis). The work streamlines one significant advantage of gasification process, namely the capability to process lower grade fuels on condition of high energy efficiency. Introduction in the evaluated IGCC-based schemes of carbon capture step (based on pre-combustion capture) significantly reduces CO₂ emissions, the carbon capture rate being higher than 90% for decarbonized energy vectors (power and hydrogen) and in the range of 47–60% for partially decarbonized energy vectors (SNG, liquid fuels). Various plant concepts were assessed (e.g. 420–425 MW net power with 0–200 MW_th flexible hydrogen output, 800 MW_th SNG, 700 MW_th liquid fuel, all of them with CCS). The paper evaluates fuel blending for optimizing gasification performance. A detailed techno-economic evaluation for hydrogen and power co-generation with CCS was also presented.     

Study on different zero CO2 emission IGCC systems with CO2 capture by integrating OTM

In this paper, different zero CO₂ emission integrated gasification combined cycle (IGCC) systems based on the oxy‐fuel combustion method by integrating with oxygen ion transfer membrane (OTM) with and without sweep gas are proposed in order to reduce the energy consumption of CO₂ capture. By utilizing the Aspen Plus software, the overall system models are established. The performances of the proposed systems are compared with the traditional IGCC system without CO₂ capture and the zero CO₂ emission IGCC system based on the oxy‐fuel combustion method using the cryogenic air separation unit. In addition, the effects of OTM key parameters on the proposed system performance, such as the feed side pressure, permeate side pressure, and operating temperature, are investigated and analyzed. The results show that the efficiency of the zero CO₂ emission IGCC system based on the oxy‐fuel combustion method integrated with OTM without sweep gas is 6.67% lower than that of the traditional IGCC system without CO₂ capture, but 1.88% higher than that of the zero CO₂ emission IGCC system using the cryogenic air separation unit, and 0.64% lower than that of the proposed system with sweep gas. The research achievements will provide valuable references for further study on CO₂ capture based on IGCC with lower energy penalty. Copyright © 2016 John Wiley & Sons, Ltd.     

A comprehensive techno‐economic analysis method for power generation systems with CO2 capture

A new comprehensive techno‐economic analysis method for power generation systems with CO₂ capture is proposed in this paper. The correlative relationship between the efficiency penalty, investment increment, and CO₂ avoidance cost is established. Through theoretical derivation, typical system analysis, and variation trends investigation, the mutual influence between technical and economic factors and their impacts on the CO₂ avoidance cost are studied. At the same time, the important role that system integration plays in CO₂ avoidance is investigated based on the analysis of a novel partial gasification CO₂ recovery system. The results reveal that for the power generation systems with CO₂ capture, the efficiency penalty not only affects the costs on fuel, but the incremental investment cost for CO₂ capture (U.S.$ kW⁻¹) as well. Consequently, it will have a decisive impact on the CO₂ avoidance cost. Therefore, the added attention should be paid to improve the technical performance in order to reduce the efficiency penalty in energy system with CO₂ capture and storage. Additionally, the system integration may not only decrease the efficiency penalty, but also simplify the system structure and keep the investment increment at a low level, and thereby it reduces the CO₂ avoidance cost significantly. For example, for the novel partial gasification CO₂ recovery system, owing to system integration, its efficiency can reach 42.2%, with 70% of CO₂ capture, and its investment cost is only 87$ kW⁻¹ higher than that of the reference IGCC system, thereby the CO₂ avoidance cost is only 6.23$ t⁻¹ CO₂. The obtained results provide a comprehensive technical–economical analysis method for energy systems with CO₂ capture useful for reducing the avoidance costs. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhanced hetero‐elements doping content in biomass waste‐derived carbon for high performance supercapacitor

Betel nut wastes are firstly modified with nitric acid/thiourea to fabricate hetero‐element doping carbon (C‐H‐T) for energy storage. C‐H‐T exhibits improved content of O (12.27%), N (2.52%), and S (2.88%) compared with that of purely carbonized carbon with O (9.2%) and N (1.76%). Without nitric acid heat treatment, the carbon materials prepared by hydrothermal treatment with thiourea only get increasing hetero‐elements content of O (10.46%), N (2.9%), and S (0.53%). The similar results have been obtained using urea and melamine as dopants. Due to the synergistic effects of the hetero‐elements containing functional groups, C‐H‐T get a significant enhancement in its electrochemical properties with a high capacitance (423 F g^?1 at 0.5 A g^?1) in KOH electrolyte. C‐H‐T based coin‐type symmetric supercapacitors display maximum energy density of 61.7 Wh kg^?1 and considerate cycling ability with 94% capacitance retention after 10 000 cycles. The fabricated two‐step method can inspire the increase of hetero‐elements content in carbon materials to develop its application in energy storage.     

Energy minimization in monoethanolamine‐based CO2 capture using capacitive deionization

Post‐combustion CO₂ capture using monoethanolamine (MEA) is a mature technology; however, the high energy input requirements for solvent regeneration are still a challenge for MEA‐based CO₂ capture. In this paper, a novel approach is presented in which a conventional CO₂ absorption–desorption system is integrated with capacitive deionization (CDI) in such a way to minimize the heat duty requirement of the stripper. The CO₂‐rich solution drawn from the absorber column is first sent to CDI where ionic species are adsorbed at oppositely charged electrodes during the charging cycle, and an ion‐free solution is sent back to the absorber. The adsorbed ions released during the regeneration cycle are sent to the stripper column. The concentrated solution from the CDI process that was sent to the stripper required low heat duty to regenerate the solvent because of the high CO₂ loading of the solution. The feasibility of the suggested modelling technique is verified at various stripper inlet temperatures and lean CO₂ loadings. The results indicate that 10–45% of the total energy supplied to the stripper can be conserved at a lean CO₂ loading of 0.0000–0.0323 using the suggested process model. Moreover, the required size of the stripper column will be small due to the small volume of the concentrated ionic solutions from the CDI cell, eliminating the initial cost of the CO₂ capture system. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrogen storage ability of porous carbon material fabricated from coffee bean wastes

The hydrogen storage ability at 298 and 77 K of porous carbon materials with microporous structures fabricated from coffee bean wastes through KOH activation was investigated regarding pore structure. The dependence of hydrogen storage ability on the pore structure of porous carbon materials was investigated at 298 and 77 K to clarify the storage mechanism of carbon materials. Hydrogen storage ability at 298 K was increased linearly with increasing of specific surface area increasing. The maximum amount of stored hydrogen was 0.6 wt.% on porous carbon material with 2070 m²/g specific surface area. The hydrogen storage ability at 77 K was 4.0 wt.% on the same sample. The hydrogen storage ability showed a linear relationship with the micro-pore volume size. These changes in the dependence of the hydrogen storage ability on pore size suggested that the storage configuration changed from two- to three-dimensional. The stored hydrogen densities in porous carbon materials calculated from these values were 5.7 and 69.6 mg/cm³ at 298 and 77 K, respectively. The change in density indicated that the state of stored hydrogen in porous carbon materials was filled up aggregational state, which is extremely close to the liquid state, and suggested the realizing of high hydrogen storage ability on carbon materials fabricated from agricultural waste.     

An integrated system for thermal power generation,electrical energy storage and CO2 capture

This work reports a newly proposed system for electrical energy storage. The new system combines a direct open nitrogen (cryogen) expansion cycle with a natural gas‐fuelled closed Brayton cycle and the CO₂ produced in the system is captured in the form of dry ice. Thermodynamic analyses are carried out on the system under the baseline conditions of 1 kg s^?1 natural gas, a combustor operating pressure of 8 bars and a cryogen topping pressure of 100 bars. The results show that the exergy efficiency of the proposed system is as high as 64% under the baseline conditions, whereas the corresponding electricity storage efficiency is about 54%. A sensitivity analysis has also been carried out on the main operating conditions. The results indicate that the baseline performance can be enhanced by increasing the gas turbine (GT) inlet temperature, decreasing the approach temperature of the heat exchange processes, operating the combustor at an optimal pressure of ～7 bars and operating the cryogen topping pressure at ～90 bars. Further enhancement can be achieved by increasing the isentropic efficiency of the GT and the liquefaction process. The results of this work also suggest that the power capacity installation of peak‐load units and fuel consumption could be reduced by as much as 50% by using the newly proposed system. Further work is suggested for an economic analysis of the system. Copyright © 2010 John Wiley & Sons, Ltd.     

Reduction of CO2 capture plant energy requirement by selecting a suitable solvent and analyzing the operating parameters

Among various developed methods for CO₂ capturing from industrial flue gases, chemical absorption system is still considered as the most efficient technique, because of its lower energy requirement and also its applicability for low concentration of CO₂ in the inlet gas stream. Also, it can be used to retrofit the existed power plants, which are the major industrial CO₂ emission sources, without changing their design condition. Selection of a suitable solvent is the first parameter that should be considered in the design of capture plants that use absorption technology. The most important challenge for using chemical solvents is finding the optimum operating conditions to minimize the energy requirement. Study of technical parameters can be helpful to improve the overall capture plant efficiency. In this paper, CO₂ capture plant has been simulated for different solvents to compare their performance and energy requirement. To improve the plant overall efficiency, effect of the main operating factors such as amine flow rate, temperature, inlet gas temperature, and pressure has been studied in this paper. This analysis indicates the best chemical solvent for various cases of inlet flue gas. This parametric study reduces the overall energy requirement and helps design a cost‐effective plant. Copyright © 2012 John Wiley & Sons, Ltd.