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
Renewable methane storage in Gippsland for peak and backup power
- Authors: Ghayur, Adeel , Verheyen, Vincent
- Date: 2017
- Type: Text , Conference proceedings
- Relation: 2017 Australasian Universities Power Engineering Conference, AUPEC; Melbourne, Australia; 19th-22nd November 2017. p. 1-5
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- Description: Climate Change mitigation by adopting renewable energies and the depleting gas reservoirs of Australia’s Gippsland Basin have introduced insecurity in the Australian energy sector. Urgent measures are needed to avoid future grid failures. This study proposes underground storage of biomethane (CH4) to meet peak and backup power demands. The depleted gas reservoirs and coal seams of Gippsland are candidates for such a storage. In this study, a facility converting waste biomass into methane and storing it in depleted gas reservoir for meeting peak/backup electricity demand is modelled and simulated. In the model, 200 t/d of biomass is anaerobically digested into methane. Despite this practicable yet relatively small scale when combined with storage, the facility generates 14,000 t (20 million m3) of methane per year, enough to generate over 80,000 MWh of electricity on demand via fuel cells. These results demonstrate the potential for bio-renewables contributing to large scale power demand.
Modelling a biorefinery concept producing carbon fibre-polybutylene succinate composite foam
- Authors: Ghayur, Adeel , Verheyen, Vincent
- Date: 2019
- Type: Text , Journal article
- Relation: Chemical Engineering Science Vol. 209, no. (2019), p. 1-7
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- Description: In this study, a novel biorefinery concept producing carbon fibre-poly(butylene succinate) composite foam (CPC foam) from lignocellulose and CO 2 is modelled. The biodegradable nature of poly(butylene succinate) would allow for easy carbon fibre recovery from the CPC foam for reuse at the end of product lifecycle, thus allowing for a circular materials flow. Technical simulation results show the biorefinery consumes 417 kg of biomass, 33 kg of CO 2 , 86 kg of methanol, 23 kg of acetic anhydride, 130 kWh of electricity and 1166 kW of heat per hour. The facility generates 72 kg of CPC foam, 82 kg of carbon fibre, 24 kg of tetrahydrofuran and 50 kg of dimethyl ether (DME). DME is used to fulfil parasitic electricity requirement. These results demonstrate the technical viability of this biorefinery although, research is needed to reduce parasitic energy demand. This carbon negative biorefinery avoids carcinogens and halogens for polymeric materials synthesis by utilising green chemistry principles and lignocellulose feedstock.
Techno-economic analysis of a succinic acid biorefinery coproducing acetic acid and dimethyl ether
- Authors: Ghayur, Adeel , Verheyen, Vincent , Meuleman, Erik
- Date: 2019
- Type: Text , Journal article
- Relation: Journal of Cleaner Production Vol. 230, no. (2019), p. 1165-1175
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- Description: The production of platform chemicals via carbon negative technologies will play an important role in global efforts to mitigate climate change. Succinic acid biorefineries are commercially mature carbon negative technologies that are plagued with large waste streams in the form of hemicellulose and gypsum. Here, a techno-economic analysis assesses the viability of a succinic acid biorefinery wherein hemicellulose is converted to acetic acid and dimethyl ether, and gypsum generation is avoided. Succinic acid is a feedstock for biodegradable plastics, acetic acid replaces petroleum-derived sources, and dimethyl ether is ideally suited as an energy storage vector. Our novel biorefinery concept presents an innovative integration of commercial technologies including water-splitting bipolar membrane electrodialysis for acid purification. The modelled multiproduct biorefinery (Multi Case)annually consumes 650,000 metric tonnes (t)of pulp logs, 135,000t of methanol, 1,700,000t of water, 42,000t of CO2 and 89 MW of electricity to produce 220,000t of succinic acid, 115,000t of acetic acid and 900t of dimethyl ether. All the parasitic electricity and heat duties are fulfilled within the biorefinery. Results show a CAPEX of AUD $635,000,000, OPEX of $180,000,000 and a succinic acid Minimum Selling Price of $990/t. Sensitivity and uncertainty analyses of the Multi Case biorefinery model show it is also resilient to price fluctuations.
Characterization of trace organic compounds in recycled water used for irrigation on turf and comparison with rain
- Authors: Heaven, M. , Verheyen, Vincent , Cruickshank, Alicia , Wild, Karl , Watkins, Mark , Nash, David
- Date: 2012
- Type: Text , Journal article
- Relation: Agricultural Water Management Vol. 103, no. (2012), p. 176-181
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- Description: Wastewaters are increasingly being reused in public spaces to supplant the use of potable water. In this study we investigated possible trace organic contaminants in wastewater from a dairy factory applied to a recreation reserve. Samples were taken of recycled dairy factory wastewater used to irrigate the reserve and from the subsurface drainage system after irrigation and after rainfall. Using gas chromatography–mass spectrometry, it was found that irrigation drainage mostly contained different compounds to those in rainfall drainage. This drainage water was found to contain residues of three agrochemicals (dicamba, 0.4 ± 0.07
Rapid determination of ultra-trace concentrations of mercury in plants and soils by cold vapour inductively coupled plasma-optical emission spectrometry
- Authors: Hellings, Jacqueline , Adeloju, Samuel , Verheyen, Vincent
- Date: 2013
- Type: Text , Journal article
- Relation: Microchemical Journal Vol. 111, no. 62-66 (2013), p.62-66
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- Description: A method is described for rapid and reliable determination of ultra-trace concentrations of mercury in plant and soil samples by cold vapour inductively coupled plasma-optical emission spectrometry (CV-ICP-OES). Under the established optimum conditions, a detection limit of 3 ng g− 1 was achieved. Rapid decomposition of soil and plant samples were achieved with microwave digestion with a 3:1 HNO3:HCl mixture for only 10 min, enabling close to 100% recovery of mercury. Choice of sample storage condition and nature of sample (dried, wet or frozen) had significant influence on mercury concentrations found in plant and soil samples. Storage of samples as frozen, followed by digestion without drying or on as received basis gave optimum recovery of mercury in the samples. Verification of the effectiveness of the CV-ICP-OES method for reliable mercury determination in plants and soil with microwave digested certified soil and spiked plant samples gave close to 100% and 95–103% recoveries, respectively. The CV-ICP-OES method was successfully applied to the determination of mercury in plant and soil samples from a local Australian forest. The mercury concentrations found in plants range from 23.5 to 78.5 ng g− 1, while those found in soils range from 30.1 to 61.7 ng g− 1.
Soluble organic components of winery wastewater and implications for reuse
- Authors: Mosse, Kim , Verheyen, Vincent , Cruickshank, Alicia , Patti, Antonio , Cavagnaro, Timothy
- Date: 2013
- Type: Text , Journal article
- Relation: Agricultural Water Management Vol. 120, no. (2013), p. 5-10
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- Description: Sustainable reuse of winery wastewaters (WWW) via land application is of interest given the increasing industrialization of wine production. However, before WWW reuse can become widespread, its chemical composition and consequently its potential long-term impact need to be investigated. In this study, soluble materials in influent and effluent waters from different WWW treatment plants were analyzed at the molecular level using Solid Phase Micro Extraction Gas Chromatography/Mass Spectrometry (SPME GC–MS). The analytical focus was on key compound classes with potential for environmental harm, the majority of which were reduced by all treatments considered here. The effluents retained considerable quantities of recalcitrant phenolic compounds, which is of concern due to their potential phytotoxicity and proven resistance to aerobic degradation. This research highlights the importance of understanding the nature of organic material in WWW to ensure sustainable reuse.
Thermochemolysis of winery wastewater particulates-molecular structural implications for water reuse
- Authors: Mosse, Kim , Verheyen, Vincent , Cruickshank, Alicia , Patti, Antonio , Cavagnaro, Timothy
- Date: 2012
- Type: Text , Journal article
- Relation: Journal of Analytical and Applied Pyrolysis Vol. 97, no. 164-170 (2012), p.
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- Description: Environmental concerns have increased the interest in winery wastewater remediation and reuse. These practices require more detailed understanding of wastewater composition to ensure optimum usage, and to minimize the risk of long term soil degradation and grape contamination. Particulate organic matter is an important contributor to the carbon burden in winery wastewaters. This article investigates the molecular structure of particulates from the most common winery wastewater treatment processes via infrared spectroscopic and thermochemolysis-gas chromatography/mass spectrometry techniques. Study of the organic composition of both influent and effluent particles enabled further insight into which compounds could prove problematic during treatment and on discharge. The yield and molecular structure of desorbed or “guest” compounds were found to strongly correlate with those produced during pyrolytic cracking. These “guest” compounds and macromolecular fragments form a continuum whose separation is based on molecular size. Polyphenolic and lignin derived compounds tended to survive the water treatment processes within assemblages of microbial detritus. No evidence was found for particles adsorbing and concentrating other unrelated organics such as anthropogenic chemicals from winery wastewaters. Any release of particulates will require careful management to prevent localized accumulation of recalcitrant compounds to toxic levels.
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.
Structural elucidation of humic acids extracted from Pakistani lignite using spectroscopic and thermal degradative techniques
- Authors: Nasir, Saqib , Sarfaraz, Tahira , Verheyen, Vincent , Chaffee, Alan
- Date: 2011
- Type: Text , Journal article
- Relation: Fuel Processing Technology Vol. 92, no. 5 (2011/05/01/ 2011), p. 983-991
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- Description: The present paper describes the characterization of Pakistan lignite coal, derived humic acids (HAL) and nitrohumic acids (NHA) along with the standard leonardite humic acids (LHA). The study utilized chromatographic and spectroscopic techniques to characterize the structure of coal and derived materials. Pyrolysis coupled to gc/ms was conducted with and without methylating agent (tetramethyl ammonium hydroxide). The pyrolysis study resulted in releasing mainly fatty acid methyl esters, different series of hydrocarbons and α, ω-dicarboxylic acid methyl esters. Triterpenoids, syringic and ρ-coumaric compounds and aromatic compounds derived from lignin moieties were also detected. Fourier transform infrared (FT-IR) and NMR data helped to evaluate the influence of coal rank on regeneration and nitration processes with respect to chemical structural composition of coal and derived materials. FT-IR spectra of four materials were similar except that NHA showed an absorption band at 1532cm−1, thus confirming the presence of -NO2 groups. 13C NMR indicated higher aromaticity and less hydroxylalkyl material in HAL than NHA. The elemental composition and acid functional group content of four materials were also reported. The combination of results from different analytical techniques gives an improved understanding of the Pakistan coal nature and helpful for its future utilization.
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
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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.
Solubilisation of Victorian brown coal in 'distillable' DIMCARB
- Authors: Qi, Ying , Tikkoo, Tarun , Verheyen, Vincent , Ranganathan, Vijayaraghavan , MacFarlane, Douglas , Chaffee, Alan
- Date: 2013
- Type: Text , Conference paper
- Relation: 30th Annual International Pittsburgh Coal Conference 2013, PCC 2013
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- Description: Victorian (Australia) brown coal is an abundant and cheap energy resource. There is intense interest in identifying new opportunities for its efficient and clean use, for example by solubilisation to produce high quality fuel or chemicals. Ionic liquids (ILs) have been applied increasingly in recent years to solubilize and recover cellulose, lignin and other components from complex biomass mixtures. Conventional ILs are not distillable and it can be difficult to separate the soluble product from the solvent. However, there is a group of ILs, produced by the association of a secondary amine and CO2 that are 'distillable' in that they will dissociate back to the respective amine and CO2 at moderate temperature to facilitate recovery. They can then be re-associated (recycled) by condensation at lower temperature. The simplest form of such ILs, DIMCARB, consists of dimethylamine associated with CO2 at a molar ratio of 2:1. DIMCARB has previously been found to be superior (in terms of solubility) to other ILs in this group for the extraction of a Victorian brown coal. In this study the extractability of a woody coal sample was compared with a run-of-mine (ROM) sample, both without pretreatment. The wet coal was mixed with DIMCARB at a dry mass ratio of 1 to 20 for 24 hours at room temperature. The soluble product was recovered by centrifuge and acid washed to remove residual DIMCARB. An extraction yield of 25% was achieved for the ROM sample, while for the woody coal the yield was only 10%. The recovered products were characterized by a range of chemical techniques including FTIR and Pyrolysis GC-MS. The lower solubility of the woody coal seems to be associated with a high degree of oxygen containing aromatic components. The nature of this difference and the selectivity of the extraction are discussed.
Ambient temperature solubilisation of brown coal in ammonium carbamate ionic liquids
- Authors: Qi, Ying , Verheyen, Vincent , Vijayaraghavan, Ranganathan , MacFarlane, Douglas , Chaffee, Alan
- Date: 2016
- Type: Text , Journal article
- Relation: Fuel Vol. 166, no. (2016), p. 106-115
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- Description: Coal solubilisation is often a necessary step for the alternative utilisation of the cheap and abundant brown coal resources in the State of Victoria, Australia, such as producing high quality fuel or chemicals. A series of ionic liquids (ILs), ammonium carbamates, formed by the association of carbon dioxide (CO2) with low molecular weight secondary amines, were investigated as solvents for the solubilisation of Victorian brown coal. The ionic liquid was mixed with a Loy Yang coal at a mass ratio of 20 to 1 (dry basis) for 24 h at ambient temperature. The solubilisation yields of the coal using three such ILs from dimethyl-, diallyl- and dipropyl-amines, respectively, were between 18% and 23%. Repeated solubilisation of the coal with fresh solvent achieved higher yields, with the highest at 66% by the carbamate formed from dimethylamine (DIMCARB). The variations in chemical structure between the products were compared by elemental analysis and a variety of spectroscopic techniques (FTIR, Solid State 13C NMR and Py-GC-MS). The soluble products of the initial solubilisation were more aliphatic than their parent coal. The less polar ILs formed from diallyl- and dipropyl-amines (DACARB and DPCARB) appeared to be more selective for high molecular weight triterpenoids than DIMCARB. Subsequent treatment tended to dissolve more aromatic components. © 2015 Elsevier Ltd. All rights reserved.
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
Monoethanolamine degradation during Pilot-Scale post-combustion capture of CO₂ from a brown coal-fired power station
- Authors: Reynolds, Alicia , Verheyen, Vincent , Adeloju, Samuel , Chaffee, Alan , Meuleman, Erik
- Date: 2015
- Type: Text , Journal article
- Relation: Energy & Fuels Vol. 29, no. 11 (2015), p. 7441-7455
- Full Text: false
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- Description: The use of aqueous amines, such as monoethanolamine (MEA, 2-aminoethanol), for post-combustion capture (PCC) of CO2 from fossil-fuel-fired power station flue gases leads to undesirable reactions with oxygen, SO2, and NO2. This study has used a gas chromatography with mass spectrometry detection (GC-MS) method to measure the changes in concentrations of organic compounds in samples of a 30% (w/w) aqueous MEA absorbent obtained from CSIRO's PCC pilot plant operating at AGL's Loy Yang brown coal-fired power station in Latrobe Valley, Victoria, Australia. This aqueous MEA absorbent was previously used for more than 700 h of PCC, and the collected samples represent a further 834 h of PCC operation. These data provide a new perspective on the close, interdependent relationships between corrosion and amine degradation reactions. Other important outcomes include confirmation that (a) organic degradation products identified during laboratory-scale trials were also produced during pilot-scale PCC and (b) N-(2-hydroxyethyl)imidazole (HEI) is a suitable molecular marker for oxidative degradation of MEA. This investigation has also highlighted areas that require further research, including (a) determination of oxidative degradation mechanisms in both the presence and absence of dissolved transition metals, (b) determination of parameters that limit oxidative degradation during pilot-scale PCC, (c) investigation of the antioxidative or oxygen-scavenging properties of partially oxidized amine absorbents during PCC, and (d) measurement of the concentrations of glycine, glycolic acid, and other potential organic acids during PCC. [ABSTRACT FROM AUTHOR]
- Description: The use of aqueous amines, such as monoethanolamine (MEA, 2-aminoethanol), for post-combustion capture (PCC) of
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
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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.
Degradation of amine-based solvents
- Authors: Reynolds, Alicia , Verheyen, Vincent , Meuleman, Erik
- Date: 2016
- Type: Text , Book chapter
- Relation: Absorption-Based Post-Combustion Capture of Carbon Dioxide Chapter 16 p. 399-423
- Full Text: false
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- Description: Degradation of aqueous amines during post-combustion capture (PCC) of CO2 from fossil-fuel flue gases by wet gas scrubbing can lead to reduced energy efficiency, operational instability, increased corrosion, and unwanted emissions to the environment. Oxidative amine degradation and the accumulation of heat-stable salts primarily occur during absorption of CO2, whereas carbamate polymerization (also called thermal degradation) primarily occurs during desorption of CO2 and thermal amine reclamation. Oxidative degradation is closely related to corrosion, catalyzed by dissolved metal ions, and can be exacerbated by intermittent operation of PCC. Other important reactions, such as nitrosation, occur at much slower rates but can produce environmentally sensitive compounds. The ability to measure the concentrations of individual compounds or monitor amine degradation during PCC is important for managing amine degradation during PCC and demonstrating compliance with environmental regulations. Although some suitable analytical methods are available, further work is needed before they could satisfy the rigorous statutory and legal requirements. Strategies for avoiding and managing amine degradation need to be integrated into all PCC activities including: selecting degradation-resistant amines, ensuring adequate pretreatment of CO2-rich flue gas, avoiding severe CO2 absorption and desorption conditions, and the use of anticorrosion and antioxidation additives. Avoiding intermittent operation of PCC processes and choosing nonmetal column packing may also assist in minimizing amine degradation. © 2016 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.
Use of MEA oxidation intermediates to monitor oxidation conditions during post-combustion capture of CO2
- Authors: Reynolds, Alicia , Verheyen, Vincent
- Date: 2019
- Type: Text , Conference paper
- Relation: 14th Greenhouse Gas Control Technologies Conference (GHGT-14); Melbourne 21-26 ; October 2018 p.
- Full Text:
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- Description: Amine oxidation is a serious concern for post-combustion capture (PCC) of CO2 from fossil-fuel fired power stations. Organic acids are important oxidation products and have been measured in different ratios at different pilot plants. The concentrations of acetate, formate, glycolate and oxalate were measured in samples of degraded monoethanolamine from a variety of PCC pilot plants as well as laboratory-scale degradation experiments. The results suggest that the ratios of monoethanolamine oxidation intermediates (particularly glycolate and oxalate) have potential as process monitoring tools. Ultimately, ratios of these oxidation intermediates could be used to proactively manage and minimise oxidation of amine-based PCC absorbents by indicating the need for oxygen-scavenger addition or alerting operators to imminent increases in oxidative degradation rates.