CO2 capture performance of calcium-based sorbent doped with manganese salts during calcium looping cycle

The effects of manganese salts including Mn(NO₃)₂ and MnCO₃ on CO₂ capture performance of calcium-based sorbent during cyclic calcination/carbonation reactions were investigated. Mn(NO₃)₂ and MnCO₃ were added by wet impregnation method. The cyclic CO₂ capture capacities of Mn(NO₃)₂-doped CaCO₃, MnCO₃-doped CaCO₃ and original CaCO₃ were studied in a twin fixed-bed reactor and a thermo-gravimetric analyzer (TGA), respectively. The results show that the addition of manganese salts improves the cyclic carbonation conversions of CaCO₃ except the previous cycles. When the Mn/Ca molar ratios are 1/100 for Mn(NO₃)₂-doped CaCO₃ and 1.5/100 for MnCO₃-doped CaCO₃, the highest carbonation conversions are achieved respectively. The carbonation temperature of 700-720 °C is beneficial to CO₂ capture of Mn-doped CaCO₃. The residual carbonation conversions of Mn(NO₃)₂-doped and MnCO₃-doped CaCO₃ are 0.27 and 0.24 respectively after 100 cycles, compared with the conversion of 0.16 for original one after the same number of cycles. Compared with calcined original CaCO₃, better pore structure is kept for calcined Mn-doped CaCO₃ during calcium looping cycle. The pore volume of calcined MnCO₃-doped CaCO₃ is 2.4 times as high as that of calcined original CaCO₃ after 20 cycles. The pores of calcined MnCO₃-doped CaCO₃ in the pore size range of 27-142 nm are more abundant relative to clacined original one. That is why modification by manganese salts can improve cyclic CO₂ capture capacity of CaCO₃.     

Pre-combustion, post-combustion and oxy-combustion in thermal power plant for CO2 capture

This paper presents a summary of technical-economic studies. It allows evaluating, in the French context, the production cost of electricity derived from coal and gas power plants with the capture of CO₂, and the cost per tonne of CO₂ avoided. Three systems were studied: an Integrated Gasification Combined Cycle (IGCC), a conventional combustion of Pulverized Coal (PC) and a Natural Gas Combined Cycle (NGCC). Three main methods were envisaged for the capture of CO₂: pre-combustion, post-combustion and oxy-combustion.For the IGCC, two gasification types have been studied: a current technology based on gasification of dry coal at 27 bars (Shell or GE/Texaco radiant type) integrated into a classical combined cycle providing 320 MWe, and a future technology (planned for about 2015–2020) based on gasification of a coal–water mixture (slurry) that can be compressed to 64 bars (GE/Texaco slurry type) integrated into an advanced combined cycle (type H with steam cooling of the combustion turbine blades) producing a gross power output of 1200 MWe.     

Capturing CO2 in flue gas from fossil fuel-fired power plants using dry regenerable alkali metal-based sorbent

CO₂ capture and storage (CCS) has received significant attention recently and is recognized as an important option for reducing CO₂ emissions from fossil fuel combustion. A particularly promising option involves the use of dry alkali metal-based sorbents to capture CO₂ from flue gas. Here, alkali metal carbonates are used to capture CO₂ in the presence of H₂O to form either sodium or potassium bicarbonate at temperatures below 100 °C. A moderate temperature swing of 120–200 °C then causes the bicarbonate to decompose and release a mixture of CO₂/H₂O that can be converted into a “sequestration-ready” CO₂ stream by condensing the steam. This process can be readily used for retrofitting existing facilities and easily integrated with new power generation facilities. It is ideally suited for coal-fired power plants incorporating wet flue gas desulfurization, due to the associated cooling and saturation of the flue gas. It is expected to be both cost effective and energy efficient.     

CO2 capture using carbide slag modified by propionic acid in calcium looping process for hydrogen production

Lime enhanced gasification (LEGS) process based on calcium looping in which CaO is employed as CO₂ sorbent is an emerging technology for hydrogen production and CO₂ capture. In this work, carbide slag which was an industrial solid waste was utilized as CO₂ sorbent in hydrogen production process. Modification of carbide slag by propionic acid was proposed to improve its reactivity. The CO₂ capture behavior of raw and modified carbide slags was investigated in a dual fixed-bed reactor (DFR) and a thermo-gravimetric analyzer (TGA). The results show that modification of carbide slag by propionic acid enhances its CO₂ capture capacity in the multiple calcination/carbonation cycles. The favorable carbonation temperature and calcination temperature for modified carbide slag are 680–700 °C and 850–950 °C, respectively. Prolonged carbonation treatment is beneficial to CO₂ capture of raw and modified carbide slags. The prolonged carbonation for 9 h in the 21st cycle increases the conversions of raw and modified carbide slags in this cycle. And then the carbonation conversions of the two sorbents were also improved in the subsequent cycles. Calcined modified carbide slag shows more porous microstructure compared with calcined raw one for the same number of cycles. Modification of carbide slag by propionic acid increases the surface area, pore volume and pore area. In addition, the volume and area of the pores in 20–100 nm in diameter were improved, which had been proved to be more effective to capture CO₂. The microstructure of calcined modified carbide slag favors its higher CO₂ capture capacity in the multiple calcination/carbonation cycles.     

Calcium looping gasification for high-concentration hydrogen production with CO2 capture in a novel compact fluidized bed: Simulation and operation requirements

The coal/CaO/steam gasification system is one of the clean coal technologies being developed for hydrogen production with inherent carbon dioxide separation. A novel reactor configuration for the system is proposed in this paper. It consists of three major counterparts: a gasifier, a riser and a regenerator. A regenerable calcium-based sorbent CaO is used to remove carbon dioxide. In the gasifier, the coal-steam gasification reaction occurs with in situ carbon dioxide removal by carbonation reaction. The removal of carbon dioxide favors the gasification and water-shift reaction equilibrium and enables the production of a hydrogen-rich gas stream. CaO is regenerated in the regenerator by burning the unreacted char with oxygen, and a pure stream of carbon dioxide is separated after a cyclone. The regenerated CaO then flows into the riser above the gasifier, and removes the carbon dioxide in the outlet gases from the gasifier and drives the water-gas shift reaction forward, further improving the hydrogen purity. In this work, the feasibility and optimum process conditions of the proposed system were described. The hydrogen purity can reach 96 vol% at a steam flow 80 mol/s and CaO recycle rate 30 mol/s when the carbon conversion rate is 0.50. Increasing the steam flow and CaO recycle rate can enhance the hydrogen yield and purity. With the rise of operation pressure from 1 bar to 10 bar, the hydrogen yield and purity decrease and methane yield increases. High pressure leads to higher calcination temperature. At 10 bar, the temperature for CaCO₃ decomposition is approximately 1100 °C, at such temperature, the sorbent is easy to deactivate. The appropriate temperatures in the gasifier and the riser are 700 and 600 °C, respectively. An analysis of heat integration is conducted. The maximum carbon conversion rate is ∼0.65. A hydrogen production efficiency of 58.5% is obtained at a carbon conversion rate 0.50, steam flow 60 mol/s and CaO recycle rate 30 mol/s, with a hydrogen purity of 93.7 vol%.     

On the off-design of a natural gas-fired combined cycle with CO2 capture

During the last 15 years cycles with CO₂ capture have been in focus, due to the growing concern over our climate. Often, a natural gas fired combined cycle with a chemical absorption plant for CO₂ capture from the flue gases have been used as a reference in comparisons between cycles. Neither the integration of the steam production for regeneration of amines in the combined cycle nor the off-design behaviour of such a plant has been extensively studied before.     

Sorbent enhanced hydrogen production from steam gasification of coal integrated with CO2 capture

In this work, CO₂ capture and H₂ production during the steam gasification of coal integrated with CO₂ capture sorbent were investigated using a horizontal fixed bed reactor at atmospheric pressure. Four different temperatures (650, 675, 700, and 750 °C) and three sorbent-to-carbon ratios ([Ca]/[C] = 0, 1, 2) were studied. In the absence of sorbent, the maximum molar fraction of H₂ (64.6%) and conversion of coal (71.3%) were exhibited at the highest temperature (750 °C). The experimental results verified that the presence of sorbent in the steam gasification of coal enhanced the molar fraction of H₂ to more than 80%, with almost all CO₂ was fixed into the sorbent structure, and carbon monoxide (CO) was converted to H₂ and CO₂ through the water gas shift reaction. The steam gasification of coal integrated with CO₂ capture largely depended on the reaction temperature and exhibited optimal conditions at 675 °C. The maximum molar fraction of H₂ (81.7%) and minimum CO₂ concentration (almost 0%) were obtained at 675 °C and a sorbent-to-carbon ratio of 2.     

The influence of membrane CO2 separation on the efficiency of a coal-fired power plant

In this paper, the influence of membrane separation of CO₂ from flue gases and the impacts of the whole CCS process (CO₂ separation and compression) on the performance of a coal-fired power plant are studied. First, the effects of the characteristics of the membrane (selectivity and permeability) and the parameters of the process (feed and permeate pressure) on two indices, CO₂ recovery rate and CO₂ purity are analysed. Next, a method for determining the minimum power loss and efficiency loss of the power plant as a function of these calculated indices is described. Then, the power requirements and efficiency loss (up to 15.4 percentage points) because of the CCS installation are calculated. A method for reducing these losses through the integration of the CCS installation with the power plant is also proposed. The main aims of the integration are heat exchange between media and a decrease in the CO₂ temperature before compression. Implementing this process can result in a significant reduction of the efficiency loss by 8 percentage points.     

High capacity potassium-promoted hydrotalcite for CO2 capture in H2 production

This paper presents an experimental study for a newly modified K₂CO₃-promoted hydrotalcite material as a novel high capacity sorbent for in-situ CO₂ capture. The sorbent is employed in the sorption enhanced steam reforming process for an efficient H₂ production at low temperature (400–500 ^°C). A new set of adsorption data is reported for CO₂ adsorption over K-hydrotalcite at 400 °C. The equilibrium sorption data obtained from a column apparatus can be adequately described by a Freundlich isotherm. The sorbent shows fast adsorption rates and attains a relatively high sorption capacity of 0.95 mol/kg on the fresh sorbent. CO₂ desorption experiments are conducted to examine the effect of humidity content in the gas purge and the regeneration time on CO₂ desorption rates. A large portion of CO₂ is easily recovered in the first few minutes of a desorption cycle due to a fast desorption step, which is associated with a physi/chemisorption step on the monolayer surface of the fresh sorbent. The complete recovery of CO₂ was then achieved in a slower desorption step associated with a reversible chemisorption in a multi-layer surface of the sorbent. The sorbent shows a loss of 8% of its fresh capacity due to an irreversible chemisorption, however, it preserves a stable working capacity of about 0.89 mol/kg, suggesting a reversible chemisorption process. The sorbent also presents a good cyclic thermal stability in the temperature range of 400–500 °C.     

Thermodynamic analysis of a membrane-assisted chemical looping reforming reactor concept for combined H2 production and CO2 capture

There is great consensus that hydrogen will become an important energy carrier in the future. Currently, hydrogen is mainly produced by steam reforming of natural gas/methane on large industrial scale or by electrolysis of water when high-purity hydrogen is needed for small-scale hydrogen plants. Although the conventional steam reforming process is currently the most economical process for hydrogen production, the global energy and carbon efficiency of this process is still relatively low and an improvement of the process is key for further implementation of hydrogen as a fuel source. Different approaches for more efficient hydrogen production with integrated CO₂ capture have been discussed in literature: Chemical Looping Combustion (CLC) or Chemical Looping Reforming (CLR) and membrane reactors have been proposed as more efficient alternative reactor concepts relative to the conventional steam reforming process. However, these systems still present some drawbacks. In the present work a novel hybrid reactor concept that combines the CLR technology with a membrane reactor system is presented, discussed and compared with several other novel technologies. Thermodynamic studies for the new reactor concept, referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR), have been carried out to determine the hydrogen recovery, methane conversion as well as global efficiency under different operating conditions, which is shown to compare quite favorably to other novel technologies for H₂ production with CO₂ capture.     

Coal gasification with in situ CO2 capture by the synthetic CaO sorbent in a 1 kWth dual fluidised-bed reactor

Coal gasification with in situ CO₂ capture is believed to be able to produce highly concentrated H₂ with little or no CO₂ compared with the conventional process. This has been demonstrated by other researchers working on a single fluidised bed by continuously feeding the CaO sorbent. This work presents the results of coal gasification with in situ CO₂ capture by a synthetic CaO sorbent in a 1 kW_th dual fluidised-bed reactor at atmospheric pressure, which has not been reported in the literature. The synthetic CaO sorbent is cyclically used by going through multiple carbonation/calcination cycles during coal gasification.     

Biomass-fired cogeneration systems with CO2 capture and storage

In this study, we estimate and analyze the CO₂ mitigation costs of large-scale biomass-fired cogeneration technologies with CO₂ capture and storage. The CO₂ mitigation cost indicates the minimum economic incentive required (e.g. in the form of a carbon tax) to make the cost of a less carbon intensive system equal to the cost of a reference system. If carbon (as CO₂) is captured from biomass-fired energy systems, the systems could in principle be negative CO₂ emitting energy systems. CO₂ capture and storage from energy systems however, leads to reduced energy efficiency, higher investment costs, and increased costs of end products compared with energy systems in which CO₂ is vented. Here, we have analyzed biomass-fired cogeneration plants based on steam turbine technology (CHP-BST) and integrated gasification combined cycle technology (CHP-BIGCC). Three different scales were considered to analyze the scale effects. Logging residues was assumed as biomass feedstock. Two methods were used to estimate and compare the CO₂ mitigation cost. In the first method, the cogenerated power was credited based on avoided power production in stand-alone plants and in the second method the same reference output was produced from all systems. Biomass-fired CHP-BIGCC with CO₂ capture and storage was found very energy and emission efficient and cost competitive compared with other conversion systems.     

Part-load analysis of a chemical looping combustion (CLC) combined cycle with CO2 capture

This paper presents part-load evaluation of a natural gas-fired chemical looping combustion (CLC) combined cycle with CO₂ capture. The novel combined cycle employs an air-based gas turbine, a CO₂-turbine and a steam turbine cycle. In this combined cycle, the CLC reactors replace combustion chamber of the gas turbine. The proposed combined cycle has a net plant efficiency of about 52.2% at full-load, including CO₂ compression to 200 bar. The part-load evaluation shows that reducing the load down to 60% results in an efficiency drop of 2.6%-points. However, the plant shows better relative part-load efficiency compared to conventional combined cycles. The pressure in CLC-reduction and -oxidation reactors is balanced by airflow control, using a compressor equipped with variable guide vanes. A combination of control strategies is discussed for plant start-up and shutdown and for part-load when airflow reduction is not practically possible with current generation of compressors. The results show that the combined cycle has a promising efficiency even at part-load; however, it requires an advanced control strategy.     

The environmental impact of post-combustion CO2 capture with MEA, with aqueous ammonia, and with an aqueous ammonia-ethanol mixture for a coal-fired power plant

In this paper the authors compare monoethanolamine (MEA) to aqueous ammonia (AA) and a solvent mixture of aqueous ammonia and ethanol (EAA) with respect to their post-combustion CO₂ capture performance and their environmental impact. Simulation of all processes was carried out with Aspen Plus^® and compared to experimental results for CO₂ scrubbing with ammonia. Of special interest was the formation of stable salts, which could be observed in the experimental CO₂ capture with both ammonia solvents. If CO₂ can be captured in the form of ammonium salts, energy requirements are greatly reduced, since no energy is required for solvent regeneration and CO₂ compression. The environmental impact of CO₂ capture was investigated for a 500 MW pulverised coal power plant employing Life Cycle Assessment (LCA) using the software SimaPro^®. For a comprehensive evaluation of this impact, influencing factors such as solvent production and solvent emissions were included. With kinetics taken into account, no salt formation could be observed in CO₂ removal with aqueous ammonia. The necessary reduction of ammonia emissions leads to further energy requirements, and solvent production as well as the remaining ammonia losses to the environment have a more significant environmental impact than CO₂ removal with MEA.     

Solar energy powered Rankine cycle using supercritical CO2

A solar energy powered Rankine cycle using supercritical CO₂ for combined production of electricity and thermal energy is proposed. The proposed system consists of evacuated solar collectors, power generating turbine, high-temperature heat recovery system, low-temperature heat recovery system, and feed pump. The system utilizes evacuated solar collectors to convert CO₂ into high-temperature supercritical state, used to drive a turbine and thereby produce mechanical energy and hence electricity. The system also recovers heat (high-temperature heat and low-temperature heat), which could be used for refrigeration, air conditioning, hot water supply, etc. in domestic or commercial buildings. An experimental prototype has been designed and constructed. The prototype system has been tested under typical summer conditions in Kyoto, Japan; It was found that CO₂ is efficiently converted into high-temperature supercritical state, of while electricity and hot water can be generated. The experimental results show that the solar energy powered Rankine cycle using CO₂ works stably in a trans-critical region. The estimated power generation efficiency is 0.25 and heat recovery efficiency is 0.65. This study shows the potential of the application of the solar-powered Rankine cycle using supercritical CO₂.     

Integrated gasification combined cycle and carbon capture: A risky option to mitigate CO2 emissions of coal-fired power plants

The power sectors of many big economies still rely on coal-fired plants and emit huge amounts of carbon dioxide. Emerging countries like Brazil, China and South Africa plan to expand the use of coal-fired thermal plants in the next decade. Integrated gasification combined cycle (IGCC) is an innovative technology that facilitates the implementation of carbon capture (CC). The present work analyzes the maturity and costs of the IGCC technology, with and without CC, and assesses the effect of the technology risk on its economic viability. Findings show that the inclusion of the risk in the economic analysis of IGCC plants raises the cost of CO₂ avoided from 36 US$/t_CO2 to 106 US$/t_CO2 in the case of Shell Gasifiers and from 39 US$/t_CO2 to 112 US$/t_CO2 in the case of GE Gasifiers. Thus, the introduction of IGCC with CC on a wider scale faces huge uncertainties. The feasibility of these plants will rely heavily on the overcoming of the technology risk. Besides, its implementation in the short run will depend on government incentives to bear with the additional cost incurred in the first-generation plants.     

Recent developments in membrane-based technologies for CO2 capture

Developing new methods and technologies that compete with conventional industrial processes for CO₂ capture and recovery is a hot topic in the current research. Conventional processes do not fit with the current approach of process intensification but take advantage due to their maturity and large-scale implementation. Acting in a precombusion scenario or post-combustion scenario involves the separation of CO₂/H₂ or CO₂/N₂, respectively.     

Industrial test and techno-economic analysis of CO2 capture in Huaneng Beijing coal-fired power station

The first industrial-scale CO₂ capture plant in China has been demonstrated at Huaneng Beijing power plant has shown that this technology is a good option for the capture of CO₂ produced by commercial coal-fired power plants. The commissioning and industrial tests are introduced in this paper. The tests show that in the early stages of the passivation phase, the concentration variations of amine, anti-oxidant and Fe³⁺ are in the normal range, and the main parameters achieve the design value. The efficiency of the CO₂ capture was about 80–85%, and by the end of January 2009 about 900 tons of CO₂ (99.7%) have been captured. The equipment investment and consumptive costs, including steam, power, solution and others, have been analyzed. The results show: the cost of the absorber and the stripper account for about 50% of main equipment; the consumptive cost is about 25.3 US$ per metric tons of CO₂, of which the steam requirement accounts for about 55%; the COE increased by 0.02 US$/kW h and the electricity purchase price increased by 29%.     

Optimal operation of an integrated energy system including fossil fuel power generation, CO2 capture and wind

This study considers the optimization of operations for an integrated fossil-renewable energy system with CO₂ capture. The system treated consists of a coal-fired power station, a temperature-swing absorption CO₂ capture facility powered by a natural gas combustion turbine, and wind generation. System components are represented in a modular fashion using energy and mass balances. Optimization is applied to determine hourly system dispatch to maximize operating profit given energy prices and wind generation data. A CO₂ emission constraint, modeled after a California law, is enforced. Idealized and realistic scenarios are considered, along with several different system specifications. For a year of operation, simulated using available wind and energy price data, operating profit for optimized operation is shown to be approximately 20% greater than profit using a heuristic procedure. The benefit from optimization is positively correlated with electricity price variability and mean wind generation. The impact of different component specifications and different CO₂ absorption solvents on the optimal operation of the energy system is also assessed. In total, this study demonstrates that the effective operating cost of an integrated energy system operating under a CO₂ emission constraint can be substantially reduced via optimal flexible operation.     

CO2 capture and storage: Another Faustian Bargain?

A quarter-century ago, one of us termed the use of nuclear energy a Faustian Bargain. In this paper, we discuss what a Faustian Bargain means, how the expression has been used in characterizing other technologies, and in what measure CO₂ capture and storage is a Faustian Bargain. If we are about to enter into another Faustian Bargain, we should understand the contract.