Comparison of sample preparation methods for the GC–MS analysis of monoethanolamine (MEA) degradation products generated during post-combustion capture of CO2
- Authors: Reynolds, Alicia , Verheyen, Vincent , Adeloju, Samuel , Chaffee, Alan , Meuleman, Erik
- Date: 2016
- Type: Text , Journal article
- Relation: International Journal of Greenhouse Gas Control Vol. 52, no. (2016), p. 201-214
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- Description: As the development of chemical absorption technology for post-combustion capture (PCC) of CO2 from coal-fired power station flue gases proceeds towards commercial deployment, the focus on establishing a thorough understanding of the degradation of the aqueous amine absorbents is increasing. However, there is a need to develop and demonstrate robust analytical methods that are capable of measuring the concentrations of amine degradation products in aqueous monoethanolamine (MEA) matrix during pilot-scale PCC. In this study, sample cleanup and derivatisation methods that enable reliable and robust analysis of MEA degradation products by GC–MS are described. Two sample cleanup methods were evaluated: dehydration (by rotary evaporation and molecular sieves) and cation exchange. The cation exchange sample preparation method was preferred for the analysis of organic degradation products in these samples because it achieved higher recovery and repeatability of GC–MS measurements than those obtained with the dehydration method. Furthermore, the cation exchange method resulted in less continued amine degradation during subsequent analysis steps because of its ability to separate acidic analytes from basic analytes, as well as to remove some inorganic interferences. Further improvement of the sensitivity, repeatability and accuracy of this GC–MS analytical method can be accomplished by: (a) increasing the scale of the cation exchange and/or derivatisation procedures; (b) optimizing the derivatisation reaction conditions; and (c) using a narrower bore (e.g. 0.25 mm ID) GC–MS column. The proposed cation exchange and derivatisation procedures can be readily adopted for the quantification of organic degradation products in other aqueous amine absorbents to provide important insights into the degradation of amine absorbents during PCC of CO2. © 2016 Elsevier Ltd
Evaluation of methods for monitoring MEA degradation during pilot scale post-combustion capture of CO
- Authors: Reynolds, Alicia , Verheyen, Vincent , Adeloju, Samuel , Chaffee, Alan , Meuleman, Erik
- Date: 2015
- Type: Text , Journal article
- Relation: International Journal of Greenhouse Gas Control Vol. 39, no. (2015), p. 407-419
- Full Text: false
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- Description: Amine degradation is an important and current focus in the development of chemical absorption technology based on the use of aqueous amines for post-combustion capture (PCC) of CO
Primary sources and accumulation rates of inorganic anions and dissolved metals in a MEA absorbent during PCC at a brown coal-fired power station
- Authors: Reynolds, Alicia , Verheyen, Vincent , Adeloju, Samuel , Chaffee, Alan , Meuleman, Erik
- Date: 2015
- Type: Text , Journal article
- Relation: International Journal of Greenhouse Gas Control Vol. 41, no. (2015), p. 239-248
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- Description: Post-combustion capture (PCC) of CO2 from fossil fuel-fired power station flue gas is one of many technologies that are being developed to reduce anthropogenic greenhouse gas emissions in the medium term. Wet-gas scrubbing using aqueous amines is currently the most mature PCC technology suitable for separating CO2 from coal-fired power station flue gases. In this study, a series of twelve samples of a degraded 30% (w/w) MEA absorbent were obtained over a six month pilot scale PCC campaign at a brown coal-fired power station in Australia. These samples were used to investigate the accumulation of heat-stable salts, inorganics and minerals. The heat-stable salts concentration increased from 0.80 to 2.29% (w/w, as MEA) and organic acids from the oxidative degradation of MEA were the largest component of heat-stable salts. Acid gases such as SOx and NOx, make-up water, ultra-fine fly-ash and corrosion were all sources of the minerals and inorganics that accumulated in the aqueous MEA absorbent. Corrosion was the single biggest contributor of transition metals and the abrupt change in ratios of Fe, Cr and Mo suggests that the dominant corrosion mechanism may have changed towards the end of the campaign. The rapid accumulation of minerals and inorganics during this PCC campaign highlights the importance of continuing research into the interactions between amine absorbents and inorganic or mineral contaminants. The data presented in this study are an important resource for design of laboratory scale experiments to investigate these physical and chemical interactions between aqueous amines, minerals and inorganics.
Flexible operation of CSIRO's post-combustion CO2 capture pilot plant at the AGL Loy Yang power station
- Authors: Bui, Mai , Gunawan, Indra , Verheyen, Vincent , Feron, Paul , Meuleman, Erik
- Date: 2016
- Type: Text , Journal article
- Relation: International Journal of Greenhouse Gas Control Vol. 48, no. (May 2016), p. 188-203
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- Description: Flexible operation has the potehtial to significantly improve the economic viability of post-combustion CO2 capture (PCC). However, the impact of disturbances from flexible operation of the PCC process is unclear. The purpose of this study was to investigate the effects of flexible operation in a PCC pilot plant by implementing step-changes for improved dynamic data reliability. The flexible operation campaign was conducted at the CSIRO PCC pilot plant at AGL Loy Yang using monoethanolamine (MEA) absorbent. The pilot plant was operated under a broad range of transient conditions (changing flue gas flow, liquid absorbent flow and steam pressure) to capture the dynamics of a PCC process during flexible operation. The study demonstrated that the dynamics of flue gas flow rate was faster than absorbent flow rate. The greatest CO2 removal% was achieved at the lowest flue gas flow rate or at the highest absorbent flow rate; however, the latter provided improved energy efficiency. The steam pressure parameter could adjust the temperature of all columns simultaneously which can be used to compensate for effects from ambient conditions or heat losses. These results verify the technical feasibility of flexible PCC operation and provide a suitable dataset for dynamic model validation. (C) 2015 Elsevier Ltd. All rights reserved.
A technology review for regeneration of sulfur rich amine systems
- Authors: Garg, Bharti , Verheyen, Vincent , Pearson, Pauline , Feron, Paul , Cousins, Ashleigh
- Date: 2018
- Type: Text , Journal article , Review
- Relation: International Journal of Greenhouse Gas Control Vol. 75, no. (2018), p. 243-253
- Full Text: false
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- Description: Reducing the capital cost of post combustion CO2 capture by eliminating flue gas desulfurisation (FGD) pre-treatment, requires management of the amines preferential SO2 absorption. Novel technologies such as CS-Cap restrict the impact of SO2 to only a small fraction of the amine inventory resulting in high sulfate burden amines. Traditional thermal reclamation of these spent absorbents has advantages regarding simplicity, but ranks poorly for industrial ecology around PCC. These amines require low energy regeneration technologies compatible with their physico-chemical properties that also maximise the potential for valorising by-products. This review summarises the sulfur chemistry and outlines several amine reclamation processes. It assesses the status of established and novel regeneration technologies for their applicability to high sulfur loaded amines. Should deep sulfur removal be required, a hybrid approach with initial bulk removal (as product) followed by a polishing step to further reduce sulfur is prospective. A preliminary estimation of the relative cost of using standard reclamation methods for treating Sulfur loaded CS-Cap absorbent revealed the cost would increase due to its higher sulfate burden despite comparable treatment volumes. Research gaps are identified which would enable better comparison between the costs of traditional FGD versus higher reclamation costs for combined capture technologies.
Isolation and characterisation of recalcitrant organic components from an estuarine sediment core
- Authors: Mylotte, Rosaleen , Verheyen, Vincent , Reynolds, Alicia , Dalton, Catherine , Patti, Antonio , Chang, Rung , Burdon, James , Hayes, Michael
- Date: 2015
- Type: Text , Journal article
- Relation: Journal of Soils and Sediments Vol. 15, no. 1 (2015), p. 211-224
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- Description: Purpose The purpose of this research was to isolate humic substances and humin from an estuarine sediment core using a novel sequential extraction procedure to characterise the isolates, to determine their compositions and to understand how the organic matter (OM) changes with time. Materials and methods The sediments were exhaustively extracted using the following media: 0.1 M NaOH; 0.1 M NaOH + 6 M urea; and dimethylsulphoxide (DMSO) + H2SO4 (94:6 v/v). Pyrolysis gas chromatography mass spectroscopy (pyGC/MS), and nuclear magnetic resonance (NMR) spectroscopy were the analytical tools that gave the most significant data for the characterisation of the organic isolates. Results and discussion The results indicate subtle molecular compositional differences in relation to the alkaline and alkaline-urea isolates. The humic acids (HAs) and fulvic acids (FAs) are readily solvated in aqueous alkaline media compared to the aqueous insoluble hydrophobic humin (HU) components. In addition to aliphatic hydrocarbons, peptide materials make considerable contributions to the component structures of the isolates. Aryl and O-aryl C units characteristic of lignin, and of cutan structures from plants, indicate contributions from terrestrial OM to the organic components in the HU, especially from the base of the core. The evidence suggests that components of terrestrial plant materials and of microbial biomass are preferentially preserved with time and make the major contributions to the OM retained over long time scales. The data acquired provide detailed information about the origins, compositions, nature and the associations of the OM in the estuarine sediment core. Such information provides a greater understanding of the role of these organic components in the carbon (C) sink. Conclusions Humic acids and FAs are mineralised with time whereas HU is highly recalcitrant and represents a long-term sink for organic C. Humin is a separate organic entity and does not conform to the definitions of a humic substance. Terrestrial OM is preserved over long time scales in the environment. Protein makes significant contributions to all the organic isolates and its preservation suggests encapsulation in hydrophobic domains, or interactions with clay minerals.
Oxidative degradation of amine absorbents in carbon capture systems – A dynamic modelling approach
- Authors: Dickinson, Jillian , Percy, Andrew , Puxty, Graeme , Verheyen, Vincent
- Date: 2016
- Type: Text , Journal article
- Relation: International Journal of Greenhouse Gas Control Vol. 53, no. (2016), p. 391-400
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- Description: Fossil fuels are used widely for energy production and are likely to continue to play a major role world wide for many years to come. Much work has been done on the technology for capturing CO2 from gaseous industrial effluent. For large-scale applications like coal or natural gas-fired power plants, using amine solvents to capture post-combustion CO2 is the most mature CO2 capture technology. This technique can be used to retrofit existing plants by treating the flue gas after combustion. This paper details a dynamic mathematical model for the absorber column constructed from first principles. The loss of MEA through oxidative degradation has been quantified here for the first time and this is currently not possible using commercial packages. Reaction rate kinetics have been employed to predict the accumulation of oxidation products which is limited by the incomplete knowledge of the dominant reactions between O2 and MEA. When research has produced more detailed information about the products formed during this oxidation, it can be inserted easily into the model. Validation has been performed using data from the CSIRO PCC pilot plant at AGL Loy Yang. A limited parametric study of the impact of operating conditions on oxidation was performed.
Techno-economic evaluation of amine-reclamation technologies and combined CO2/SO2 capture for Australian coal-fired plants
- Authors: Garg, Bharti , Haque, Nawshad , Cousins, Ashleigh , Pearson, Pauline , Verheyen, Vincent , Feron, Paul
- Date: 2020
- Type: Text , Journal article
- Relation: International Journal of Greenhouse Gas Control Vol. 98, no. (2020), p.
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- Description: CSIRO's patented CS-Cap process aims at reducing the costs of amine-based post-combustion capture by combining SO2 and CO2 capture using one absorbent in a single absorber column. By avoiding the need for a separate flue gas desulfurization unit, the process offers potential savings for power plants requiring CO2 capture. High-level cost estimates based on lab and pilot data are presented for two amine reclamation techniques i.e. thermal reclamation and reactive crystallisation. Only regeneration via reactive crystallisation reduces CS-Cap costs below base case FGD/SCR-PCC. Cost estimations suggest a potential reduction of 38–44% in the total plant cost when using the CS-Cap process compared to base case. However, the amine reclaimer operating cost governs the overall cost of the CS-Cap process and is highly sensitive to sulfur content. A 50% reduction is observed when SO2 levels reduce from 700 to 200 ppm. Comparing levelised cost of electricity and CO2 avoided costs for CS-Cap against our base case, low sulfur brown coal has a slight (5–7%) cost advantage; however, confirmation requires pilot data on amine recovery. © 2020