IR monitoring of absorbent composition and degradation during pilot plant operation
- Authors: Puxty, Graeme , Bennett, Robert , Conway, Will , Webster-Gardiner, Mike , Yang, Qi , Pearson, Pauline , Cottrell, Aaron , Huang, Sanger , Feron, Paul , Reynolds, Alicia , Verheyen, Vincent
- Date: 2020
- Type: Text , Journal article
- Relation: Industrial and Engineering Chemistry Research Vol. 59, no. 15 (2020), p. 7080-7086
- Full Text: false
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- Description: The monitoring of the absorbent during the operation of CO2 separation processes is a necessary and challenging task. The most common absorbent used is an aqueous amine solution. Traditional approaches to analysis such as titration and chromatography are time-consuming and only provide limited information. This hinders the ability of process operators to rapidly respond to changes in operating conditions. In this work, a combination of infrared (IR) spectroscopy and principle component regression (PCR) analyses have been demonstrated as a rapid and reliable technique to determine the composition of an absorbent during a pilot plant campaign at a brown coal power station. The concentration of amine, a degradation product, CO2, and water was monitored throughout the campaign by a method that provided results in minutes. The results were verified by independent sample analysis using acid-base titration, high-performance liquid chromatography (HPLC), and 13C NMR spectroscopy. It was necessary to use spectral windowing when building the IR-PCR model, but this resulted in a robust and reliable method that has been demonstrated to work in a real-world process environment. © 2019 American Chemical Society.
- Description: The authors wish to acknowledge the financial assistance provided by the Brown Coal Innovation Australia, Ltd., a private member-based company with funding contracts through the Australian National Low Emissions Coal Research and Development, Ltd. (ANLEC R&D) and the Victorian State Government. The work described here was made possible through the PICA project, a collaboration between AGL Loy Yang, IHI, and CSIRO that aims to advance post-combustion CO 2 -capture technology in Australia.
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
- Full Text: false
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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
- Full Text: false
- Reviewed:
- 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.
Technical evaluation of post-combustion CO2 capture and hydrogen production industrial symbiosis
- Authors: Ghayur, Adeel , Verheyen, Vincent
- Date: 2018
- Type: Text , Journal article
- Relation: International Journal of Hydrogen Energy Vol. 43, no. 30 (2018), p. 13852-13859
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- Description: The aim of this study is to develop an industrial ecosystem whereby wastes/products from a Post-combustion CO2 Capture (PCC) plant are utilised in a hydrogen biorefinery. Subsequently, five hydrogen biorefinery models are developed that use PCC's model amine i.e. monoethanolamine (MEA) as a nitrogen source during microbial hydrogen production and CO2 as a process chemical. Technical evaluations of the five case models are carried out to identify the ones that maximise value by multiproduct generation from biomass and fulfil total/partial parasitic energy demand. The case meeting these criteria, produces 3.1t of succinylated lignin adhesive, 4.9t of dry compost and 2744 kWh of electricity from 10t (dry) of sawdust feedstock, daily. Its daily power and heat duties stand at 3906 kWh and 52.1 GJ respectively. Simulations also demonstrate biohydrogen's potential as an energy storage vector for peak/backup power with an annual 1001.4 MWh of power storage capacity from 10t/d feedstock. © 2018 Hydrogen Energy Publications LLC
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.
Quantification of aqueous monoethanolamine concentration by gas chromatography for postcombustion capture of
- Authors: Reynolds, Alicia , Verheyen, Vincent , Adeloju, Samuel , Chaffee, Alan , Meuleman, Erik
- Date: 2014
- Type: Text , Journal article
- Relation: Industrial and Engineering Chemistry Research Vol. 53, no. 12 (2014), p. 4805-4811
- Full Text: false
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- Description: The availability of reliable analytical methods for measuring amine concentrations is necessary for optimum operation of aqueous amine CO 2 separation systems being employed for postcombustion capture (PCC) of CO2. A GC-FID (gas chromatography with flame ionization detection) method is described for the reliable quantification of 30% (w/w) monoethanolamine (MEA) in severely degraded solvent samples. The observation of intermittent splitting of the MEA peak was a major concern with this approach. The use of a wide-bore column led to improved MEA peak resolution and peak shape. The reliability and robustness of the GC-FID method were assessed by analyzing degraded 30% (w/w) MEA solvent samples from CSIRO's pilot plant at AGL's Loy Yang power station in Victoria, Australia. The results were compared with those obtained by titration and total organic carbon (TOC) measurements of the same samples. The MEA concentrations obtained by the GC-FID and titration methods were statistically similar. In contrast, the MEA concentrations calculated from TOC were consistently higher than those obtained by both GC-FID and titration. © 2014 American Chemical Society.
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
- Reviewed:
- 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.
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
- Full Text: false
- Reviewed:
- 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