Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

Hollow fiber membrane separation process in the presence of gaseous and particle impurities for post-combustion CO2 capture

The membrane separation process for CO₂ capture can be interfered by the gaseous components and the fine particles in flue gas, especially in desulfurized flue gas. In this work, the pint-sized Polyimide(PI) hollow fiber membrane contactors were self-packed to investigate the membrane CO₂ separation from flue gas containing fine particles and gaseous contaminants (SO₂,SO₃,H₂O). First, the effects of SO₂, SO₃, water vapor, and gypsum particles on the CO₂ capture were studied independently and synergistically. The results showed that the effect of SO₂ on the membrane separation properties is indistinctive; however, the membrane performance was damaged seriously with the addition of SO₃. The high humidity promoted the CO₂ separation initially before inhibiting the PI membrane performance. Moreover, the decrease of the CO₂/N₂ selectivity and the permeation rate were accelerated with the coexistence of SO₂. The membrane performance showed an obvious deterioration in the presence of gypsum particles, with a 21% decrease in the CO₂/N₂ selectivity and 51% decrease in the permeation rate. Furthermore, the gypsum particles exerted dramatic damage. Under the WFGD conditions, the combined effects of SO₂, water vapor, and the gypsum particles influenced the stability of the membrane significantly. This tendency is mainly attributed to the deposition of fine particles and aerosol on the membrane surface, which occupied the effective area and enhanced the mass transfer resistance. This study of impurities’ influence could play an important role in further industrial application of membrane CO₂ capture.     

Gasification of Inferior Coal with High Ash Content under CO2 and O2/H2O Atmospheres

The gasification reaction of Nantong inferior coal was investigated in a laboratory fixed-bed reactor under CO₂ and O₂/H₂O atmospheres. The effects of the bed temperature and inlet-gas concentration on the yields of CO, H₂, and CH₄ were studied. The effects of coal ash and particle size on the fixed-carbon conversion were also investigated, and kinetic analysis was conducted with a homogeneous model. The product-gas-heating value and fixed-carbon conversion increased when the temperature was increased from 950 °C to 1100 °C under CO₂ atmosphere. When the inlet-CO₂ concentration was increased from 50 to 100 vol.%, the low heating value of the product gas and carbon conversion ratio slightly increased. During the gasification of inferior coal under the O₂/H₂O atmosphere, the CO concentration increased rapidly with increasing temperature. The H₂ and CH₄ concentrations increased initially and then decreased. The maximum gas heating value of 7934 kJ/m³ was obtained under the O₂ concentration of 70 vol.% at a bed temperature of 1050 °C. The cold-gas efficiency increased with increasing temperature and became 40.6% and 86.4% at 1100 °C under the CO₂ and O₂/H₂O atmospheres, respectively. The gasification reaction of the Nantong inferior coal strongly depended on the content of inherent inorganic matter. The gasification rates for both the CO₂ and O₂/H₂O atmospheres were independent of the particle size. The activation energy for the CO₂ and O₂/H₂O gasification reactions were 137 and 81 kJ/mol, respectively. The gasification reactions of the Nantong coal, which was performed under two different atmospheres, were compared and the reaction activity of the gasification reaction under CO₂ atmosphere was found to be much lower than that under the O₂/H₂O atmosphere.     

Viscosities, thermal conductivities and diffusion coefficients of CO2 mixtures: Review of experimental data and theoretical models

Accurate experimental data on the thermo-physical properties of CO₂-mixtures are pre-requisites for development of more accurate models and hence, more precise design of CO₂ capture and storage (CCS) processes. A literature survey was conducted on both the available experimental data and the theoretical models associated with the transport properties of CO₂-mixtures within the operation windows of CCS. Gaps were identified between the available knowledge and requirements of the system design and operation. For the experimental gas-phase measurements, there are no available data about any transport properties of CO₂/H₂S, CO₂/COS and CO₂/NH₃; and except for CO₂/H₂O(/NaCl) and CO₂/amine/H₂O mixtures, there are no available measurements regarding the transport properties of any liquid-phase mixtures. In the prediction of gas-phase viscosities using Chapman–Enskog theory, deviations are typically <2% at atmospheric pressure and moderate temperatures. The deviations increase with increasing temperatures and pressures. Using both the Rigorous Kinetic Theory (RKT) and empirical models in the prediction of gas-phase thermal conductivities, typical deviations are 2.2–9%. Comparison of popular empirical models for estimation of gas-phase diffusion coefficients with newer experimental data for CO₂/H₂O shows deviations of up to 20%. For many mixtures relevant for CCS, the diffusion coefficient models based on the RKT show predictions within the experimental uncertainty. Typical reported deviations of the CO₂/H₂O system using empirical models are below 3% for the viscosity and the thermal conductivity and between 5 and 20% for the diffusion coefficients. The research community knows little about the effect of other impurities in liquid CO₂ than water, and this is an important area to focus in future work.     

Model prediction on the rise of pCO2 in uniform flows by leakage of CO2 purposefully stored under the seabed

A numerical study was conducted to predict pCO₂ change in the ocean on a continental shelf by the leakage of CO₂, which is originally stored in the aquifer under the seabed, in the case that a large fault connects the CO₂ reservoir and the seabed by an earthquake or other diastrophism. The leakage rate was set to be 6.025 × 10⁻⁴ kg/m²/sec from 2 m × 100 m fault band, which corresponds to 3800 t-CO₂/year, referring to the monitored seepage rate from an existing EOR field. The target space in this study was limited to the ocean above the seabed, the depth of which was 200 or 500 m. The computational domain was idealistically rectangular with the seabed fault-band perpendicular to the uniform flow. The CO₂ takes a form of bubbles or droplets, depending on the depth of water, and their behaviour and dissolution were numerically simulated during their rise in seawater flow. The advection–diffusion of dissolved CO₂ was also simulated. As a result, it was suggested that the leaked CO₂ droplets/bubbles all dissolve in the seawater before spouting up to the atmosphere, and that the increase in pCO₂ in the seawater was smaller than 500 μ atm.     

Study on CO2 capture using dry potassium-based sorbents through orthogonal test method

The effect of reaction conditions on the carbonation characteristics of K₂CO₃ calcined from KHCO₃ was investigated with a pressurized thermogravimetric apparatus. Results show that the conversion rate decreased as the reaction temperature and pressure increased, and the effect of CO₂ and H₂O concentration is little. The mean reaction rate maintained constant of 3%/min. The maximum reaction rate increased as the temperature and H₂O concentration increased, and the pressure decreased. The reaction temperature and pressure are the key factors, and it is important to control those carefully for this technique. The optimum reaction condition is 60 °C, 18% CO₂, 18% H₂O, and 1 atm. K₂CO₃ calcined from KHCO₃ showed excellent CO₂ capture capability in this condition.     

Comparison of several packings for CO2 chemical absorption in a packed column

CO₂ capture and storage has gained widespread attention as an option for reducing greenhouse gas emissions. Chemical absorption and stripping of CO₂ with hot potassium carbonate (K₂CO₃) solutions has been used in the past, however potassium carbonate solutions have a low CO₂ absorption efficiency. Various techniques can be used to improve the absorption efficiency of this system with one option being the addition of promoters to the solvent and another option being an improvement in the mass transfer efficiency of the equipment. This study has focused on improving the efficiency of the packed column by replacing traditional packings with newer types of packing which have been shown to have enhanced mass transfer performance. Three different packings (Super Mini Rings (SMRs), Pall Rings and Mellapak) have been studied under atmospheric conditions in a laboratory scale column for CO₂ absorption using a 30 wt% K₂CO₃ solution. It was found that SMR packing resulted in a mass transfer coefficient approximately 20% and 30% higher than that of Mellapak and Pall Rings, respectively. Therefore, the height of packed column with SMR packing would be substantially lower than with Pall Rings or Mellapak. Meanwhile, the pressure drop using SMR was comparable to other packings while the gas flooding velocity was higher when the liquid load was above 25 kg m⁻² s⁻¹. Correlations for predicting flooding gas velocities and pressure drop were fitted to the experimental data, allowing the relevant parameters to be estimated for use in later design.     

Comparison and application of different component municipal solid wastes based carbon on adsorption of carbon dioxide

The prepared different components municipal solid wastes based carbons were used to investigate the adsorption of CO₂. The optimum conditions for CO₂ adsorption were investigated firstly. And then, the CO₂ adsorption performance of different components based carbon adsorbents were compared with each other under the optimum parameters. The results illustrated that the triple components (pinewood, acrylic textile, and tire) based carbon exhibited the best adsorption performance, which is 1.522 mmol/g and its physical prosperity was also conducted to interpret the adsorption mechanism. Besides, to further approach to the actual gas, the influence of additional O₂ and SO₂ on CO₂ adsorption properties of ternary-component-based carbon was investigated. The results illustrate that O₂ concentration exerts little effect on adsorption capacity. SO₂ plays the dominated role in the competitive adsorption effect.     

A natural analogue for CO2 mineral sequestration in Miocene basalt in the Kuanhsi-Chutung area, Northwestern Taiwan

In general, CO₂ sequestration by carbonation is estimated by laboratory experimentation and geochemical simulation. In this study, however, estimation is based on a natural analogue study of the Miocene basalt in the Kuanhsi-Chutung area, Northwestern Taiwan. This region has great potential in terms of geological and geochemical environments for CO₂ sequestration. Outcropping Miocene basalt in the study area shows extensive serpentinization and carbonation. The carbon stable isotopes of carbonates lie on the depleted side of the Lohmann meteoric calcite line, which demonstrates that the carbonates most probably precipitate directly from meteoric fluid, and water–rock interaction is less involved in the carbonation process. Oxygen stable isotope examinations also show much depleted ratios, representative of product formation under low temperatures (∼50–90 °C). This translates to a depth of 1–2 km, which is a practical depth for a CO₂ sequestration reservoir. According to petrographic observation and electron microprobe analysis, the diopside grains in the basalt are resistant to serpentinization and carbonation; therefore, the fluid causing alteration is likely enriched with calcium and there must be additional sources of calcium for carbon mineralization. These derived geochemical properties of the fluid support the late Miocene sandstone and enclosed basalts as having high potential for being a CO₂ sequestration reservoir. Moreover, the existing geochemical environments allow for mineralogical assemblages of ultramafic xenoliths, indicating that forsterite, orthopyroxene and feldspar minerals are readily replaced by carbonates. Based on the mineral transformation in xenoliths, the capacity of CO₂ mineral sequestration of the Miocene basalt is semi-quantitatively estimated at 94.15 kg CO₂ chemically trapped per 1 m³ basalt. With this value, total CO₂ sequestration capacity can be evaluated by a geophysical survey of the amount of viable Miocene basalt at the potential sites. Such a survey is required in the near future.     

Effect of oxygenated liquid additives on the urea based SNCR process

An experimental investigation was performed to study the effect of oxygenated liquid additives, H₂O₂, C₂H₅OH, C₂H₄(OH)₂ and C₃H₅(OH)₃ on NO_x removal from flue gases by the selective non-catalytic reduction (SNCR) process using urea as a reducing agent. Experiments were performed with a 150 kW pilot scale reactor in which a simulated flue gas was generated by the combustion of methane operating with 6% excess oxygen in flue gases. The desired levels of initial NO_x (500 ppm) were achieved by doping the fuel gas with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 800 to 1200 °C for the investigation of the effects of the process additives on the performance of aqueous urea DeNO_x. With H₂O₂ addition a downward shift of 150 °C in the peak reduction temperature from 1130 to 980 °C was observed during the experimentation, however, the peak reduction efficiency was reduced from 81 to 63% when no additive was used. The gradual addition of C₂H₅OH up to a molar ratio of 2.0 further impairs the peak NO_x reduction efficiency by reducing it to 50% but this is accompanied by a downward shift of 180 °C in the peak reduction temperature. Further exploration using C₂H₄(OH)₂ suggested that a 50% reduction could be attained for all the temperatures higher than 940 °C. The use of C₃H₅(OH)₃ as a secondary additive has a significant effect on the peak reduction efficiency that decreased to 40% the reductions were achievable at a much lower temperature of 800 °C showing a downward shift of 330 °C.     

Dynamis CO2 quality recommendations

In the carbon capture and storage (CCS) chain, transport and storage set different requirements for the composition of the gas stream mainly containing carbon dioxide (CO₂). Currently, there is a lack of standards to define the required quality for CO₂ pipelines. This study investigates and recommends likely maximum allowable concentrations of impurities in the CO₂ for safe transportation in pipelines. The focus is on CO₂ streams from pre-combustion processes. Among the issues addressed are safety and toxicity limits, compression work, hydrate formation, corrosion and free water formation, including the cross-effect of H₂S and H₂O and of H₂O and CH₄.     

Post-combustion CO2-capture from coal-fired power plants: Preliminary evaluation of an integrated chemical absorption process with piperazine-promoted potassium carbonate

The simulation tool ASPEN Plus^® is used to model the full CO₂-capture process for chemical absorption of CO₂ by piperazine-promoted potassium carbonate (K₂CO₃/PZ) and the subsequent CO₂-compression train. Sensitivity analysis of lean loading, desorber pressure and CO₂-capture rate are performed for various solvent compositions to evaluate the optimal process parameters. EbsilonProfessional^® is used to model a 600 MW_el (gross) hard coal-fired power plant. Numerical equations for power losses due to steam extraction for solvent regeneration are derived from simulation runs. The results of the simulation campaigns are used to find the process parameters that show the lowest specific power loss. Subsequently, absorber and desorber columns are dimensioned to evaluate investment costs for these main components of the CO₂-capture process. Regeneration heat duty, net efficiency losses and column investment costs are then compared to the reference case of CO₂-capture by monoethanolamine (MEA).CO₂-capture by piperazine-promoted potassium carbonate with subsequent CO₂-compression to 110 bar shows energetic advantages over the reference process which uses MEA. Additionally, investment costs for the main components in the CO₂-capture process (absorber and desorber columns) are lower due to the enhanced reaction kinetics of the investigated K₂CO₃/PZ solvent which leads to smaller component sizes.     

A model for the CO2 capture potential

Global warming is a result of increasing anthropogenic CO₂ emissions, and the consequences will be dramatic climate changes if no action is taken. One of the main global challenges in the years to come is therefore to reduce the CO₂ emissions.Increasing energy efficiency and a transition to renewable energy as the major energy source can reduce CO₂ emissions, but such measures can only lead to significant emission reductions in the long-term. Carbon capture and storage (CCS) is a promising technological option for reducing CO₂ emissions on a shorter time scale.A model to calculate the CO₂ capture potential has been developed, and it is estimated that 25 billion tonnes CO₂ can be captured and stored within the EU by 2050. Globally, 236 billion tonnes CO₂ can be captured and stored by 2050. The calculations indicate that wide implementation of CCS can reduce CO₂ emissions by 54% in the EU and 33% globally in 2050 compared to emission levels today.Such a reduction in emissions is not sufficient to stabilize the climate. Therefore, the strategy to achieve the necessary CO₂ emissions reductions must be a combination of (1) increasing energy efficiency, (2) switching from fossil fuel to renewable energy sources, and (3) wide implementation of CCS.     

Power generation with CO2 capture: Technology for CO2 purification

The goal of this paper is to find methodologies for removing a selection of impurities (H₂O, O₂, Ar, N₂, SO_x and NO_x) from CO₂ present in the flue gas of two oxy-combustion power plants fired with either natural gas (467 MW) or pulverized fuel (596 MW). The resulting purified stream, containing mainly CO₂, is assumed to be stored in an aquifer or utilized for enhanced oil recovery (EOR) purposes. Focus has been given to power cycle efficiency i.e.: work and heat requirements for the purification process, CO₂ purity and recovery factor (kg of CO₂ that is sent to storage per kg of CO₂ in the flue gas). Two different methodologies (here called Case I and Case II) for flue gas purification have been developed, both based on phase separation using simple flash units (Case I) or a distillation column (Case II). In both cases purified flue gas is liquefied and its pressure brought to 110 atm prior to storage.Case I: A simple flue gas separation takes place by means of two flash units integrated in the CO₂ compression process. Heat in the process is removed by evaporating the purified liquid CO₂ streams coming out from both flashes. Case I shows a good performance when dealing with flue gases with low concentration of impurities. CO₂ fraction after purification is over 96% with a CO₂ recovery factor of 96.2% for the NG-fired flue gas and 88.1% for the PF-fired flue gas. Impurities removal together with flue gas compression and liquefaction reduces power plant output of 4.8% for the NG-fired flue gas and 11.6% for the PF-fired flue gas. The total amount of work requirement per kg stored CO₂ is 453 kJ for the NG-fired flue gas and 586 kJ for the PF-fired flue gas.Case II: Impurities are removed from the flue gas in a distillation column. Two refrigeration loops (ethane and propane) have been used in order to partially liquefy the flue gas and for heat removal from a partial condenser. Case II can remove higher amounts of impurities than Case I. CO₂ purity prior to storage is over 99%; CO₂ recovery factor is somewhat lower than in Case I: 95.4% for the NG-fired flue gas and 86.9% for the PF-fired flue gas, reduction in the power plant output is similar to Case I.Due to the lower CO₂ recovery factor the total amount of work per kg stored CO₂ is somewhat higher for Case II: 457 kJ for the NG-fired flue gas and 603 kJ for the PF-fired flue gas.     

基于产业链分析的长三角地区CO2与大气污染物排放研究

长三角地区作为我国大气污染较为严重区域之一,如何在保持经济增长的同时减少CO₂与大气污染物的排放已成为一个重要挑战。本研究基于2007年与2012年长三角区域间投入产出表,定量分析了长三角地区省市间贸易引致的二氧化碳和大气污染物排放转移特征和变化趋势。同时,运用产业关联系数法,从前向关联与后向关联双重视角分析了长三角地区减缓CO₂和大气污染物排放的关键行业。研究结果表明,长三角的SO₂、PM_2.5排放总量表现为消费端大于生产端,CO₂、NO_x排放总量表现为生产端大于消费端。安徽省总体呈现为长三角地区贸易的SO₂、NO_x与PM_2.5排放净调出地,而上海与浙江表现为多数污染物排放净调入地。CO₂与大气污染物协同前向减排的关键行业为江苏省、浙江省和安徽省的电力、热力的生产和供应业,安徽省的煤炭开采和洗选业等,可以通过生产端技术革新和能源结构优化来促进减排;CO₂与大气污染物后向协同减排的关键行业为江苏省、浙江省和安徽省的建筑业等,对于这些行业,调整消费结构是有效的减排措施。为更好地制定长三角地区减排与污染防治政策,应当综合考虑行业减排、协同减排等,以确保经济持续增长的同时达到减排目标。     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

Methodology for CO2 chain analysis

The paper presents a methodology for CO₂ chain analysis with particular focus on the impact of technology development on the total system economy. The methodology includes the whole CO₂ chain; CO₂ source, CO₂ capture, transport and storage in aquifers or in oil reservoirs for enhanced oil recovery. It aims at supporting the identification of feasible solutions and assisting the selection of the most cost-effective options for carbon capture and storage. To demonstrate the applicability of the methodology a case study has been carried out to illustrate the possible impact of technology improvements and market development. The case study confirms that the CO₂-quota price to a large extent influence the project economy and dominates over potential technology improvements. To be economic feasible, the studied chains injecting the CO₂ in oil reservoirs for increased oil production require a CO₂-quota price in the range of 20–27 €/tonne CO₂, depending on the technology breakthrough. For the chains based on CO₂ storage in saline aquifers, the corresponding CO₂-quota price varies up to about 40 €/tonne CO₂.     

Predicting δCDIC dynamics in CCS: A scheme based on a review of inorganic carbon chemistry under elevated pressures and temperatures

Stable carbon isotopes are important tools to assess potential storage sites for CO₂, as they allow the quantification of ionic trapping via isotope mass balances. In deep geological formations high p/T conditions need to be considered, because CO₂ dissolution, equilibrium constants and isotope fractionation of dissolved inorganic carbon (DIC) depend on temperature, pressure and solute composition. After reviewing different approaches to account for these dependencies, an expanded scheme is presented for speciation and carbon isotope fractionation of DIC and dissolution of CaCO₃ for pCO₂ up to 100 bar, pH down to 3 and temperatures of up to 200 °C. The scheme evaluates the influence of respective parameters on isotope ratios during CO₂ sequestration. The pCO₂ and pH are the dominant controlling factors in the DIC/δ¹³C/pH system. The fugacity of CO₂ has major impact on DIC concentrations at temperatures below 100 °C at high pCO₂. Temperature dependency of activities and equilibrium dominates at temperatures above 100 °C. Isotope ratios of DIC are expected to be about 1–2‰ more depleted in ¹³C compared to the free CO₂ at pCO₂ values above 10 bar. This depletion is controlled by carbon isotope fractionation between CO₂ and H₂CO₃* which is the dominant species of DIC at the resulting pH below 5.     

A study on oxidative degradation of polyacrylamide in wastewater with UV/FENTON/C4H4O62−

The degradation of polyacrylamide (PAM) in simulate wastewater was studied in UV/Fenton/C₄H₄O₆^2? system. The factors such as molecular ratio of H₂O₂/Fe²⁺/C₄H₄O₆^2?, pH, and the dosage of Fenton reagent that could affect the PAM degradation in the UV/Fenton/C₄H₄O₆^2? system were investigated. The experimental results showed that adding C₄H₄O₆^2? to UV/Fenton system could form photosensitive ferrous complexes, which led to higher degradation efficiency of PAM. The degradation rate of PAM could be up to 95.2% under the following conditions: the concentration of H₂O₂, Fe²⁺, and C₄H₄O₆^2? were 22.5, 2.25, and 2.25 mmol/L, respectively (i.e., molecular ratio of H₂O₂/Fe²⁺/C₄H₄O₆^2? was 10:1:1), the pH value was 3.0.     

Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.