A comparative study of MEA and DEA for post-combustion CO2 capture with different process configurations

This paper presented a comparative study of monoethanolamine （MEA） and diethanolamine （DEA） for post- combustion CO2 capture （PCC） process with different process configurations to study the interaction effect between solvent and process. The steady state process model of the conventional MEA-based PCC process was developed in Pro/II and was validated with the experimental data. Then ten different process configurations were simulated for both MEA and DEA. Their performances in energy consumption were compared in terms of reboiler duty and total equivalent work. The results show that DEA generally has better thermal performances than MEA for all these ten process configurations. Seven process configurations provide 0.38%-4.61% total energy saving compared with the conventional PCC process for MEA, and other two configurations are not favourable. For DEA, except one configuration, other process configurations have 0.27%-4.50% total energy saving. This work also analyzed the sensitivities of three key parameters （amine concentration, stripper pressure and lean solvent loading） in conventional process and five process modifications to show optimization strategy.

Economic Comparison of Three Gas Separation Technologies for CO2 Capture from Power Plant Flue Gas

Three gas separation technologies,chemical absorption,membrane separation and pressure swing adsorption,are usually applied for CO2 capture from flue gas in coal-fired power plants.In this work,the costs of the three technologies are analyzed and compared.The cost for chemical absorption is mainly from $30 to $60 per ton(based on CO2 avoided),while the minimum value is $10 per ton(based on CO2 avoided).As for membrane separation and pressure swing adsorption,the costs are $50 to $78 and $40 to $63 per ton(based on CO2 avoided),respectively.Measures are proposed to reduce the cost of the three technologies.For CO2 capture and storage process,the CO2 recovery and purity should be greater than 90%.Based on the cost,recovery,and purity,it seems that chemical absorption is currently the most cost-effective technology for CO2 capture from flue gas from power plants.However,membrane gas separation is the most promising alternative approach in the future,provided that membrane performance is further improved.

Improvement of CO2 capture performance of calcium-based absorbent modified with palygorskite

Limestone can be used for CO_2 capture and sequestration(CCS) in flue gas effectively. However, its CCS capability will dramatically decline after several cycles due to the surface "sintering". In this work, the limestone was modified with palygorskite to reduce sintering phenomenon between the absorbent particles during the CCS process and the carbonation rate of the limestone can be enhanced effectively. Palygorskite is a natural mineral with nano-fibrous structure which can reduce the mutual contact of limestone particles during the CCS process. The results were detected by TGA, SEM, MIP, FTIR and particle size analyzer respectively. The best CO_2 capture performance of modified absorbent was 13.11% improvement with only 5 wt% palygorskite added during the CCS process after 15 cycles compared with natural absorbent. It was found that excellent microscopic structures of absorbent modified with palygorskite was created, and the surface sintering was postponed leading to CO_2 capture performance enhanced under the same conditions.

CO2 capture over molecular basket sorbents:Effects of SiO2 supports and PEG additive

The objective of this work is to study the influences of silica supports and PEG additive on the sorption performance of molecular basket sorbent（MBS） for COcapture consisting of polyethylenimine and one of the following supports: SBA-15（2-D structure）, TUD-1（3-D sponge-like structure） and fumed silica HS-5（3-D disordered structure）. Effects of the supports regarding pore structures and pore properties, the PEI loading amount as well as the sorption temperature were examined. Furthermore, polyethylene glycol（PEG） was introduced as an additive into the sorbents and its effect was investigated at different PEI loadings and sorption temperatures. The results suggest that the pore properties of MBS（after PEI loading） play a more important role in the COsorption capacity, rather than those of the supports alone.MBS with 3D pore structure exhibits higher COsorption capacity and amine efficiency than those with 2D-structured support. Among the sorbents studied, fumed silica（HS-5） based MBS showed the highest COsorption capacity in the temperature range of 30-95 °C, probably due to its unique interstitial pores formed by the aggregation of polymer-loaded SiOparticles. It was found that the temperature dependence is directly related to the PEI surface coverage layers. The more PEI surface coverage layers, the higher diffusion barrier for COand the stronger temperature dependence of COcapacity. 3D MBS exceeds 2D MBS at the same PEI coverage layers due to lower diffusion barrier. Adding PEG can significantly enhance the COsorption capacity and improve amine efficiency of all MBS, most likely by alleviating the diffusion barrier within PEI bulk layers through the inter-molecular interaction between PEI and PEG.

Facile synthesis of microporous carbonaceous materials derived from a covalent triazine polymer for CO2 capture

Highly porous nitrogen-doped carbon materials were synthesized by the carbonization of a low-cost porous covalent triazine polymer, PCTP-3, which had been synthesized by the AlClcatalyzed FriedelCrafts reaction of readily available monomers. The nature of the bond and structure of the resulting materials were confirmed using various spectroscopic methods, and the effects of KOH activation on the textural properties of the porous carbon materials were also examined. The KOH-activated porous carbon（aPCTP-3c） materials possessed a high surface area of 2271 mgand large micro/total pore volumes of 0.87/0.95 cmg, respectively, with narrower micropore size distributions than the porous carbon prepared without activation（PCTP-3c）. The aPCTP-3c exhibited the best COuptakes of 284.5 and 162.3 mg gand CHuptakes of 39.6 and 25.9 mg gat 273 and 298 K/1 bar, respectively, which are comparable to the performance of some benchmark carbon materials under the same conditions. The prepared materials exhibited high CO/Nselectivity and could be regenerated easily.

Synthesis and evaluation of carbon nanotubes composite adsorbent for CO2 capture： a comparative study of CO2 adsorption capacity of single-walled and multi-walled carbon nanotubes

As a preliminary investigation towards obtaining carbon nanotube composite adsorbent for CO2 capture, in this study CO2 adsorption performance of three commercial carbon nanotubes （CNTs） one single-walled carbon nanotubes （SWCNTs）, and two （2） different multi-walled carbon nanotubes （referred to as A-MWCNTs and B-MWCNTs） were evaluated and compared. The purpose of this study was to compare the different types of CNTs and select the best to serve as the solid anchor in the development of a hydrophobic composite adsorbent material for CO2 capture. The N2 physi- sorption of the CNTs was conducted to determine their surface area, pore volume and pore size. In addition, morphology and purity of the CNTs were checked with Transmission Electron Microscopy and Raman Spectroscopy, respectively. The CO2 adsorption capacity of the CNTs was evaluated using Thermo-gravimetric analysis （TGA） at 1.1 bar, at operating temperature ranged from 25 to 55 ~C and at different CO2 feed flow rates, in order to evaluate the effects of these variables on the CO2 adsorption capacity. The results of CO2 adsorption with the TGA show that CO2 adsorption capacity for both SWCNTs and MWCNTs was the highest at 25 ~C. Changing the CO2 flowrates had no significant effect on the adsorption capacity of MWCNTs, but decreasing the CO2 flow rate resulted in the enhancement of the CO2 adsorption capacity of SWCNTs. Overall, it was found that the SWCNTs displayed the highest CO2 adsorption capacity （29.97 gCO2/kg ad- sorbent） when compared to the MWCNTs （12.09 gCO2/kg adsorbent）, indicating a 150% increase in adsorption capacity over MWCNTs.

Post-synthesis modification of porous organic polymers with amine： a task-specific microenvironment for CO2 capture

A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of diethylenediamine （DETA）, and poly-amine groups of polyethylenimine （PEI） to the network gave rise to task-specific modification of the microenvironments to make them more suitable for CO2 capture. As a result, significant boost of CO2 adsorption capacity of 4.5 mmol/g （for FC-POP-CH2DETA, 273 K, 1 bar） and the CO2/N2 selectivity of 736.1 （for FC- POP-CH2PEI） were observed after the post-synthesis amine modifications. Furthermore, these materials can be regener- ated in elevated temperature under vacuum without apparent loss of CO2 adsorption capacity.

A comparative process simulation study of Ca-Cu looping involving post-combustion CO2 capture

This work presents a simulation study of several Ca-Cu looping variants with CO(2)capture,aiming at both parameter optimization and exergy analysis of these Ca-Cu looping systems.Three kinds of Ca-Cu looping are considered:(1)carbonation-calcination/reduction-oxidation;(2)carbonation-oxidation-calcination/reduction and (3)carbona tion/oxidation-calcination/reduction.A conventional Ca looping is also simulated for comparison.The influences of the calcination temperature on the mole fractions of CO(2)and CaO at the calciner outlet,the CaCO3 flow rate on the carbonator performance and the Cu/Ca ratio on the calciner performance are analyzed.The second kind of Ca-Cu looping has the highest carbonation conversion.At 1×10^5 Pa and 820℃,complete decomposition of CaCO3 can be achieved in three Ca-Cu looping systems,while the operation condition of 1×10^5 Pa,840℃is required for the conventional Ca looping system.Furthermore,the Cu/Ca molar ratio of 5.13-5.19 is required for the Ca-Cu looping.Exergy analyses show that the maximum exergy destruction occurs in the calciner for the four modes and the second Ca-Cu looping system(i.e.,carbonation-oxidation-calcination/reduction)performs the highest exergy efficiency,up to 65.04%,which is about 30%higher than that of the conventional Ca looping.

Application of Amine-Functionalized Cellulose Foam for CO2 Capture and Storage in the Brewing Industry

Due to a lack of technology,smaller breweries simply dump excess CO2 into the atmosphere,fueling the greenhouse effect and global warming.State-of-the-art CO2 capture technologies using nanofibrillated cellulose are expensive and require laborious freeze-drying.Consequently,there is a high demand for affordable alternatives in order to reduce the environmental impact in this industry sector.This work describes a novel route for a quick and cost-efficient synthesis of amine-functionalized cellulose pellets by a surfactantassisted steam explosion process.Typical values with this method were porosity of 92%and density of 67 g/cm^3.Investigations on polyethylenimine(PEI)content and distribution revealed a maximum PEI concentration of 20 wt%with decreasing concentration to the core of a pellet.Sufficient stability against brewery exhaust gas was determined and CO2 release at^120℃ could be confirmed.Capacity tests under simulated working conditions with a novel laboratory reactor yielded a CO2 capacity of 1.0 mmol/g or 67 mol/m^3,which is comparable to values known from the literature for other cellulose-based adsorbents.

Fundamentals in CO2 capture of Na2CO3 under a moist condition

Capacity and kinetics of COcapture of NaCOwere studied to determine the mechanism for COsequestration under ambient conditions. Bicarbonate formation of NaCOwas examined by a thermogravimetric analysis（TGA） under various COand water vapor concentrations and the accompanying structural changes of NaCOwere demonstrated by X-ray diffraction（XRD）. Morphological variations were observed during the reaction of COcapture through scanning electron microscope（SEM）. Structural changes and morphological variations, which occurred during the course of the reaction, were then connected to the kinetic and exothermic properties of the COcapture process from the XRD and SEM measurements. The results showed that the bicarbonate formation of NaCOhas two different pathways.For higher COand HO concentrations, the bicarbonate formation proceeded effectively. However, for lower COand HO concentrations, the reactions were more complicated. The formation of NaCO·HO from NaCOas the first step, followed by the subsequent formation of NaH（CO）, and then the bicarbonate formation proceeds. To understand such fundamental properties in COcapture of NaCOis very important for utilization of NaCOas a sorbent for COcapture.

Modelling of a post-combustion CO2 capture process using extreme learning machine

This paper presents modelling of a post-combustion CO2 capture process using bootstrap aggregated extreme learning machine （ELM）. ELM randomly assigns the weights between input and hidden layers and obtains the weights between the hidden layer and output layer using regression type approach in one step. This feature allows an ELM model being developed very quickly. This paper proposes using principal component regression to obtain the weights between the hidden and output layers to address the collinearity issue among hidden neuron outputs. Due to the weights between input and hidden layers are randomly assigned, ELM models could have variations in performance. This paper proposes combining multiple ELM models to enhance model prediction accuracy and reliability. To predict the CO2 production rate and CO2 capture level, eight parameters in the process were utilized as model input variables： inlet gas flow rate, CO2 concentration in inlet flow gas, inlet gas temperature, inlet gas pressure, lean solvent flow rate, Jean solvent temperature, lean loading and reboiler duty. The bootstrap re-sampling of training data was applied for building each single ELM and then the individual ELMs are stacked, thereby enhancing the model accuracy and reliability. The bootstrap aggregated extreme learning machine can provide fast learning speed and good generalization performance, which will be used to optimize the CO2 capture process.

CO2 Capture by Adsorption on MCM-68 Solid Sorbent Materials

Solid sorbents adsorption is considered as one of the potential options for CO2 capture process. CO2 adsorption on MCM-68 （Si/AI ratio 22） sorbent material was investigated. MCM-68 was synthesized using N,N,N＇,N＇-tetraethylbicyclo [2.2.2] oct-7-ene-2,3：5,6-dipyrrolidinium diiodide （TEBOP^2＋（I^＋）2） as a structure-directing agent （SDA）. CO2 adsorption capacity on MCM-68 sorbent was measured at a broad temperature window i.e. 60 ℃, 300 ℃ and at 400 ℃. The presence of ordered mesoporous structure, high surface area （456 me/g） and high thermal stability （TGA analysis up to 900℃） in MCM-68 are thought to be to be advantageous for the CO2 adsorption in broad temperature window.

Clathrate Hydrate Capture of CO2 from Simulated Flue Gas with Cyclopentane/Water Emulsion

Capture of CO2 by hydrate is one of the attractive technologies for reducing greenhouse effect.The primary challenges are the large energy consumption,low hydrate formation rate and separation efficiency.This work presents a new method for capture of CO2 from simulated flue gasCO2(16.60%,by mole) /N2 binary mixture by formation of cyclopentane(CP) hydrates at initial temperature of 8.1°C with the feed pressures from 2.49 to 3.95 MPa.The effect of cyclopentane and cyclopentane/water emulsion on the hydrate formation rate and CO2 separation efficiency was studied in a 1000 ml stirred reactor.The results showed the hydrate formation rate could be increased remarkably with cyclopentane/water emulsion.CO2 could be enriched to 43.97%(by mole) and 35.29%(by mole) from simulated flue gas with cyclopentane and cyclopentane/water(O/W) emulsion,respectively,by one stage hydrate separation under low feed pressure.CO2 separation factor with cyclopentane was 6.18,higher than that with cyclopentane/water emulsion(4.01) ,in the range of the feed pressure.The results demonstrated that cyclopentane/water emulsion is a good additive for efficient hydrate capture of CO2.

Near-infrared absorbing 2D/3D ZnIn2S4/N-doped graphene photocatalyst for highly efficient CO2 capture and photocatalytic reduction

Hierarchical heterostructure photocatalysts with broad spectrum solar light utilization,particularly in the nearinfrared(NIR)region,are emerging classes of advanced photocatalytic materials for solar-driven CO2 conversion into value-added chemical feedstocks.Herein,a novel two-demensional/three-demensional(2 D/3 D)hierarchical composite is hydrothermally synthesized by assembling vertically-aligned ZnIn2 S4(ZIS)nanowall arrays on nitrogen-doped graphene foams(NGF).The prepared ZIS/NGF composite shows enhancement in photothermal conversion ability and selective CO2 capture as well as solar-driven CO2 photoreduction.At273 K and 1 atm,the ZIS/NGF composite with 1.0 wt%NGF achieves a comparably high CO2-to-N2 selectivity of 30.1,with an isosteric heat of CO2 adsorption of 48.2 kJ mol^-1.And in the absence of cocatalysts and sacrificial agents,the ZIS/NGF composite with cyclability converts CO2 into CH4,CO and CH3 OH under simulated solar light illumination,with the respective evolution rates about 9.1,3.5,and 5.9 times higher than that of the pristine ZIS.In-depth analysis using in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)in conjunction with Kelvin probe measurements reveals the underlying charge transfer pathway and process from ZIS to NGF.

Mature versus emerging technologies for CO2 capture in power plants： Key open issues in post-combustion amine scrubbing and in chemical looping combustion

Carbon capture and storage （CCS） have acquired an increasing importance in the debate on global wanning as a mean to decrease the environmental impact of energy conversion technologies, by capturing the CO2 produced from the use of fossil fuels in electricity generation and industrial processes. In this respect, post-combustion systems have received great attention as a possible near-term CO2 capture technology that can be retrofitted to existing power plants. This capture technology is, however, energy-intensive and results in large equipment sizes because of the large volumes of the flue gas to be treated. To cope with the demerits of other CCS technologies, the chemical looping combustion （CLC） process has been recently considered as a solution for CO2 separation. It is typically referred to as a technology without energy penalty. Indeed, in CLC the fuel and the combustion air are never mixed and the gases from the oxidation of the fuel （i.e., CO2 and H2O） leave the system as a separate stream and can be separated by condensation of H2O without any loss of energy. The key issue for the CLC process is to find a suitable oxygen carrier, which provides the fuel with the activated oxygen needed for combustion. The aim of this work is to explore the feasibility of using perovskites as oxygen carriers in CLC and to consider the possible advantages with respect to the scrubbing process with amines, a mature post-combustion technology for CO2 separation.

Surface modification of broom sorghum-based activated carbon via functionalization with triethylenetetramine and urea for CO2 capture enhancement

A new type of activated carbon （AC） was synthesized using broom sorghum stalk as a low cost carbon source through chemical activation with H3PO4 and KOH. The AC obtained by KOH had the largest BET surface area of 1619 m^2·g^-1 and the highest micropore volume of 0.671 cm^3·g^-1. CO2 adsorption was enhanced by functionalizing the AC with two different amines： triethylenetetramine （TETA） and urea. The structure of the prepared ACs was characterized by Brunauer-Emmett-Teller method, scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and acid-base Boehm titration analyses. The adsorption behavior of CO2 onto raw and amine-functionalized ACs was investigated in the temperature range of 288-308 K and pressures up to 25 bar. The amount of CO2 uptake at 298 K and 1 bar achieved by AC-TETA and AC-urea was 3.22 and 2.33 mmol·g^-1 which shows a 92% and 40% improvement compared to pristine AC （1.66 mmol·g^-1）, respectively. Among different model isotherms used to describe the adsorption equilibria, Sips isotherm presented a perfect fit in all cases. Gas adsorption kinetic study revealed a fast kinetics of CO2 adsorption onto the ACs. The evaluation of the isosteric heat of adsorption demonstrated the exothermic nature of the CO2 adsorption onto unmodified and modified samples.

Comparison study on strategies to prepare nanocrystalline Li2ZrO3-based absorbents for CO2 capture at high temperatures

A comparison study has been conducted on the strategies for synthesizing nanocrystalline Li2ZrO3 and K- doped Li2ZrO3 absorbents for CO2 capture at high temperatures, including solid-state and liquid-phase meth- ods, citrate route, and starch-assisted sol-gel method combined with freeze-drying technique. The absorption properties, including uptake rate and absorption capacity, of synthesized absorbents were investigated by thermo- gravimetric analysis （TGA） at different CO2 partial pressures. The nanosized Li2ZrO3 crystals synthesized by the citrate route exhibit a faster uptake and a higher, nearly stoichiometric absorption capacity than those synthesized by the solid-state and liquid-phase methods. The doping of K into Li2ZrO3 can significantly improve the uptake rate of CO2, especially at low CO2 partial pressures. For the synthesis of K-doped Li2ZrO3, the citrate route has poor reproducibility and scalability, whereas the starch-assisted sol-gel method combined with freeze-drying technique is reproducible and easily scaled up, and the thus synthesized absorbents possess excellent CO2 capture properties.

Al2O3 and CeO2-promoted MgO sorbents for CO2 capture at moderate temperatures

A series of Al2O3 and CeO2 modified MgO sorbents was prepared and studied for CO2 sorption at moderate temperatures. The CO2 sorption capacity of MgO was enhanced with the addition of either Al2O3 or CeO2. Over Al2O3-MgO sorbents, the best capacity of 24.6 mg- CO2/g-sorbent was attained at 100 ℃, which was 61% higher than that of MgO （15.3 mg-CO2/g-sorbent）. The highest capacity of 35.3 mg-CO2/g-sorbent was obtained over the CeO2-MgO sorbents at the optimal temperature of 200 ℃. Combining with the characterization results, we conclude that the promotion effect on CO2 sorption with the addition of Al2O3 and CeO2 can be attributed to the increased surface area with reduced MgO crystallite size. Moreover, the addition of CeO2 increased the basicity of MgO phase, resulting in more increase in the CO2 capacity than Al2O3 promoter. Both the Al2O3-MgO and CeO2- MgO sorbents exhibited better cyclic stability than MgO over the course of fifteen CO2 sorption-desorption cycles. Compared to Al2O3, CeO2 is more effective for promoting the CO2 capacity of MgO. To enhance the CO2 capacity of MgO sorbent, increasing the basicity is more effective than the increase in the surface area.

CO2 capture by aqueous ammonia process in the clean development mechanism for Nigerian oil industry

The clean development mechanism （CDM） of the Kyoto Protocol offers developing countries the opportunity to participate in the effort to reduce global greenhouse gas levels and also benefit from sustainable development opportunities. To date, the majority of CDM investments have gone to emerging markets such as China, India, Brazil, and Mexico, while developing countries such as Nigeria have largely been absent from the program. Chemical sequestration using aqueous ammonia process （AAP） offers a clean low carbon technology for the efficient conversion of captured C02 into clean C02 which could be injected into oil field for enhanced oil recovery or as fertilizer source. CDM-CCS （carbon capture and storage） project with AAP has the potential as intervention for leveraging sustainable livelihood development （organic fertilizer for food production） as well as for tackling local （land air and water） and global pollution （reduce methane, SOx and NOx emissions）.

Simultaneous CO2 capture and H2 generation using Fe2O3/Al2O3 and Fe2O3/CuO/Al2O3 as oxygen carriers in single packed bed reactor via chemical looping process

The chemical looping concept provided a novel way to achieve carbon separation during the production of energy or substances. In this work, hydrogen generation with inherent CO2 capture in single packed bed reactor via this concept was discussed. Two oxygen carriers, Fe203 60 wt.% and Fe2O3 55 wt.%/CuO 5 wt.% supported by Al2O3, were made by ball milling method. First, according to the characteristics of the reduction breakthrough curve, a strict fuel supply strategy was selected to achieve simultaneous CO2 capture and HE production. Then, in the long term tests using CO as fuel, it was proved that CuO addition improved hydrogen generation with the maximum intensity of 3700 μmol H2·g^-1 Fe2O3 compared with Fe-Al of 2300 μmol HE.g^-1 Fe2O3. The overall CO2 capture efficiency remained 98%- 98.8% over 100 cycles. Moreover, the reactivity of deactivated materials was recovered nearly like that of fresh ones by sintering treatment. Finally, two kinds of complex gases consist of CO, HE, CH4 and CO2 were utilized as fuels to test the feasibility. The results showed all components could be completely converted by Fe-Cu- Al in the reduction stage. The intensity of hydrogen production and the overall CO2 capture efficiency were in the range of 2000-2400 μnol H2^g^-1 Fe2O3 and 89%, 95%, respectively.