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.
Description:
Amine-based carbon dioxide capture is the most mature technology for reducing flue gas CO₂ emissions. It has been postulated and observed during commercialisation of this technology that significant quantities of waste amines are produced. Further industrial implementation of this technology requires adequate disposal or valorisation options for this waste. This review presents an analysis of seven biological and chemical technologies for waste amine amelioration or valorisation. Of these, the biological treatments are identified as being more mature for industrial application with the capacity for marketable product generation. Slow speed is the main drawback of the biological processes but this does not hinder their commercial viability. Using waste amine for NOx reduction in power stations is a secondary option, where it seems probable that the amount of waste amine generated in the CO₂ capture plant is sufficient to fulfil the DeNOx requirements of the flue gas. This route, however, requires investigation into the impact of waste amine impurities on the power station and the CO₂ capture plant operations.
Description:
Amine-based carbon dioxide capture is the most mature technology for reducing flue gas CO emissions. It has been postulated and observed during commercialisation of this technology that significant quantities of waste amines are produced. Further industrial implementation of this technology requires adequate disposal or valorisation options for this waste. This review presents an analysis of seven biological and chemical technologies for waste amine amelioration or valorisation. Of these, the biological treatments are identified as being more mature for industrial application with the capacity for marketable product generation. Slow speed is the main drawback of the biological processes but this does not hinder their commercial viability. Using waste amine for NOx reduction in power stations is a secondary option, where it seems probable that the amount of waste amine generated in the CO capture plant is sufficient to fulfil the DeNOx requirements of the flue gas. This route, however, requires investigation into the impact of waste amine impurities on the power station and the CO capture plant operations.
Description:
Australia has ample geothermal resource, however, it is of low-grade heat and requires Enhanced Geothermal Systems (EGS). Integrating heat recovered via EGS into a lignocellulosic biorefinery opens the avenue for countless opportunities in biomass to products industries. In this study, a biorefinery is modelled that uses heat from a supercritical CO
Description:
Australia has ample geothermal resource, however, it is of low-grade heat and requires Enhanced Geothermal Systems (EGS). Integrating heat recovered via EGS into a lignocellulosic biorefinery opens the avenue for countless opportunities in biomass to products industries. In this study, a biorefinery is modelled that uses heat from a supercritical CO
Description:
Wastewater from a dairy processor is being reused and recycled both within the plant and for irrigation. Flash pyrolysis GC–MS was used to examine nitrogen and phenol containing compounds (M.W. = 35 to 450 g/mol) in the particulate fraction of the milk condensate, combined clean wastewater and aerobic bioreactor effluent. For comparison, the particulates were also prepared for standard GC–MS analyses using conventional solvent extraction methods. Compounds detected by pyrolysis GC–MS were found mostly in the bioreactor with the amino acid arginine (220 mg/kg) and the amino acid derivative 1-methyl-5-oxo-L-proline methyl ester (130 mg/kg) found at the highest concentrations. In comparison, sterols detected in the effluent were found at higher concentrations when using solvent extraction indicating some degradation with pyrolysis GC–MS. However, with few exceptions, particulates were generally found not to act as passive collectors capable of concentrating less water soluble chemicals.
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
Description:
An important step towards commercial scale post-combustion CO2 capture from coal-fired power stations is understanding solvent degradation. Laboratory scale trials have identified three main solvent degradation pathways for 30% MEA: oxidative degradation, carbamate polymerization and formation of heat stable salts. This paper probes the semi-volatile organic compounds produced from a single batch of 30% MEA which was used to capture CO2 from a black coal-fired power station (Tarong, Queensland, Australia) for approximately 700 hours, followed by 500 hours at the brown coal-fired power station (Loy Yang, Victoria, Australia). Comparisons are made between the compounds identified in this aged solvent system with MEA degradation reactions described in literature. Most of semi-volatile compounds tentatively identified by GC/MS have previously been reported in laboratory scale degradation trials. Our preliminary results show low levels of degradation products were present in samples after its use in the pilot plant at Tarong (black coal) and consequent 13 months storage, but much higher concentrations were later found in the same solvent during its at use in the pilot plant at Loy Yang Power (brown coal). Further work includes identifying the cause of poor GC/MS repeatability and investigating the relative rates of reactions described in literature. The impact of inorganic anions and dissolved metals on MEA degradation will also be explored.
Description:
An important step towards commercial scale post-combustion CO2 capture from coal-fired power stations is understanding solvent degradation. Laboratory scale trials have identified three main solvent degradation pathways for 30% MEA: oxidative degradation, carbamate polymerization and formation of heat stable salts. This paper probes the semi-volatile organic compounds produced from a single batch of 30% MEA which was used to capture CO2 from a black coal-fired power station (Tarong, Queensland, Australia) for approximately 700 hours, followed by 500 hours at the brown coal-fired power station (Loy Yang, Victoria, Australia). Comparisons are made between the compounds identified in this aged solvent system with MEA degradation reactions described in literature. Most of semi-volatile compounds tentatively identified by GC/MS have previously been reported in laboratory scale degradation trials. Our preliminary results show low levels of degradation products were present in samples after its use in the pilot plant at Tarong (black coal) and consequent 13 months storage, but much higher concentrations were later found in the same solvent during its at use in the pilot plant at Loy Yang Power (brown coal). Further work includes identifying the cause of poor GC/MS repeatability and investigating the relative rates of reactions described in literature. The impact of inorganic anions and dissolved metals on MEA degradation will also be explored.
Description:
Pulp and paper wastewaters are challenging to treat due to their variability, complexity and toxicity. Membrane Bioreactor’s (MBR’s) provide high-quality filtrates but are subject to periods of low filterability / high capillary suction time (CST) which potentially limit their use in this application. There is a paucity of published literature concerning long-term operational issues in full-scale, industrial MBR’s. We hypothesised that either changes of bacterial population, alteration/reduction of bacterial metabolism or bacterial production of extra-cellular polymers (ESPs) increased CST and reduced filterability. This study, conducted over two years at the 16.4MLD Gippsland Water Factory, was structured to inform this bacterial centric hypothesis. However, no shifts in bacterial population were seen as causative of high CST and microbial stress levels and biological activity were observed to be low during high CST and no sign of toxicity was found. The strongest correlator with CST was the concentration of colloidal Total Organic Carbon of the mixed liquor suspended solids (MLSS) supernatant (following centrifugation). The carbonaceous colloids accumulated in the supernatant were named ‘Non-Centrifugable Total Organic Carbon’ (NCTOC). Their accumulation in the MLSS was found be due to their biologically refractory nature and their retention by the MBR membrane. The accumulation of NCTOC typically followed a period where the influent had a high colour and a high sodium to calcium ratio, which is consistent with a pulping by-product called ‘Black Liquor’. Additional experiments with Black Liquor allowed us to conclude that high CST can be produced by addition of Black Liquor.
Description:
Pulp and paper wastewaters are challenging to treat due to their variability, complexity and toxicity. Membrane Bioreactor’s (MBR’s) provide high-quality filtrates but are subject to periods of low filterability / high capillary suction time (CST) which potentially limit their use in this application. There is a paucity of published literature concerning long-term operational issues in full-scale, industrial MBR’s. We hypothesised that either changes of bacterial population, alteration/reduction of bacterial metabolism or bacterial production of extra-cellular polymers (ESPs) increased CST and reduced filterability. This study, conducted over two years at the 16.4MLD Gippsland Water Factory, was structured to inform this bacterial centric hypothesis. However, no shifts in bacterial population were seen as causative of high CST and microbial stress levels and biological activity were observed to be low during high CST and no sign of toxicity was found. The strongest correlator with CST was the concentration of colloidal Total Organic Carbon of the mixed liquor suspended solids (MLSS) supernatant (following centrifugation). The carbonaceous colloids accumulated in the supernatant were named ‘Non-Centrifugable Total Organic Carbon’ (NCTOC). Their accumulation in the MLSS was found be due to their biologically refractory nature and their retention by the MBR membrane. The accumulation of NCTOC typically followed a period where the influent had a high colour and a high sodium to calcium ratio, which is consistent with a pulping by-product called ‘Black Liquor’. Additional experiments with Black Liquor allowed us to conclude that high CST can be produced by addition of Black Liquor.
Description:
Flexible operation of post-combustion CO2 capture (PCC) plants can improve efficiency through coordinating the balance between consumer demands for electricity and CO2 emission reductions. This strategy however, will impose process disturbances while the PCC plant is ramped up, ramped down or turned off. This paper presents the preliminary development of a dynamic model for PCC in a brown coal-fired power plant using the process simulation software Aspen Plus Dynamics. Validation of the dynamic model will be against both steady state and dynamic data from the pilot plant. By gaining this understanding of the dynamic behavior, the technical and financial performance of PCC can be optimised.
Description:
Flexible operation of post-combustion CO2 capture (PCC) plants can improve efficiency through coordinating the balance between consumer demands for electricity and CO2 emission reductions. This strategy however, will impose process disturbances while the PCC plant is ramped up, ramped down or turned off. This paper presents the preliminary development of a dynamic model for PCC in a brown coal-fired power plant using the process simulation software Aspen Plus Dynamics. Validation of the dynamic model will be against both steady state and dynamic data from the pilot plant. By gaining this understanding of the dynamic behavior, the technical and financial performance of PCC can be optimised.
Description:
Flexible operation of post-combustion CO2 capture (PCC) plants can improve efficiency through coordinating the balance between consumer demands for electricity and CO2 emission reductions. This strategy however, will impose process disturbances and the immediate and long term impact is unclear. There is a justified need for the development of accurate dynamic PCC models, as well as practical experience in dynamic operation of PCC pilot plants. This paper presents CSIRO PCC pilot plant data from the 2012 and 2013 dynamic campaigns using MEA solvent. The step-change approach to dynamic plant operation was implemented and the use of density meters to instantaneously measure CO2 loading instantaneously was investigated.
Description:
Flexible operation of post-combustion CO2 capture (PCC) plants can improve efficiency through coordinating the balance between consumer demands for electricity and CO2 emission reductions. This strategy however, will impose process disturbances and the immediate and long term impact is unclear. There is a justified need for the development of accurate dynamic PCC models, as well as practical experience in dynamic operation of PCC pilot plants. This paper presents CSIRO PCC pilot plant data from the 2012 and 2013 dynamic campaigns using MEA solvent. The step-change approach to dynamic plant operation was implemented and the use of density meters to instantaneously measure CO2 loading instantaneously was investigated.
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
Description:
Sulfur dioxide (SO2) is a major flue gas contaminant that has a direct effect on the performance of amine-based carbon dioxide capture units operating on power plant flue gases. In many countries, flue gas desulfurisation (FGD) is an essential upstream requirement to CO2 capture systems, thereby increasing the overall operational and capital cost of the capture system. In Australia, the efficacy of CO2 capture may be compromised by the accumulation of SO2 in the absorption solvent. CSIRO’s CS-Cap process is designed to capture of both these acidic gases in one absorption column, thereby eliminating the need for a separate FGD unit which could potentially save millions of dollars. Previous research at CSIRO’s post-combustion capture pilot plant at Loy Yang power station has shown that mono-ethanolamine (MEA) solvent absorbs both CO2 and SO2, resulting in a spent amine absorbent rich in sulfates. Further development of the CS-Cap concept requires a deeper understanding of the properties of the sulfate-rich absorbent and the conditions under which it can be effectively regenerated. In the present study, thermal reclamation and reactive crystallisation processes were investigated, allowing the parameters affecting the regeneration of sulfate-loaded amine to be identified. It was found that amine losses were considerably higher in thermal reclamation than in reactive precipitation. During thermal reclamation, vacuum conditions were more effective than atmospheric, and pH of the initial solution played a significant role in recovery of MEA from the sulfate-rich absorbent. Reactive crystallisation could be effectively accomplished with the addition of KOH. An advantage of this process was that high purity K2SO4 crystals (~99%) were formed, despite the presence of degradation products in the solvent.
Description:
Sulfur dioxide (SO2) is a major flue gas contaminant that has a direct effect on the performance of amine-based carbon dioxide capture units operating on power plant flue gases. In many countries, flue gas desulfurisation (FGD) is an essential upstream requirement to CO2 capture systems, thereby increasing the overall operational and capital cost of the capture system. In Australia, the efficacy of CO2 capture may be compromised by the accumulation of SO2 in the absorption solvent. CSIRO’s CS-Cap process is designed to capture of both these acidic gases in one absorption column, thereby eliminating the need for a separate FGD unit which could potentially save millions of dollars. Previous research at CSIRO’s post-combustion capture pilot plant at Loy Yang power station has shown that mono-ethanolamine (MEA) solvent absorbs both CO2 and SO2, resulting in a spent amine absorbent rich in sulfates. Further development of the CS-Cap concept requires a deeper understanding of the properties of the sulfate-rich absorbent and the conditions under which it can be effectively regenerated. In the present study, thermal reclamation and reactive crystallisation processes were investigated, allowing the parameters affecting the regeneration of sulfate-loaded amine to be identified. It was found that amine losses were considerably higher in thermal reclamation than in reactive precipitation. During thermal reclamation, vacuum conditions were more effective than atmospheric, and pH of the initial solution played a significant role in recovery of MEA from the sulfate-rich absorbent. Reactive crystallisation could be effectively accomplished with the addition of KOH. An advantage of this process was that high purity K2SO4 crystals (~99%) were formed, despite the presence of degradation products in the solvent.