CO2-rich Mixtures Research Articles

Modeling selective absorption of H2S from a gas mixture containing CO2 within rotating packed bed based on surface renewal theory

Compared to conventional packed beds (PBs), the rotating packed beds (RPBs) demonstrate superior selectivity for H2S. RPBs can selectively absorbing more than 99 % of H2S in CO2-rich gas mixtures, while the co-absorption rate of CO2 in RPBs is only 1/9 of that in PB columns. Therefore, RPBs have been well applied in the gas purification for natural gas, blast furnace gas, and refinery gas. While, modeling the selective reaction process in RPBs under conditions of rapid liquid film renewal remains challenging. Here, a diffusion–reaction mass transfer model based on surface renewal theory is established. The model elucidates the mechanism behind the selective absorption of H2S, and also demonstrate how RPBs enhance liquid film absorption. Experimental data collected from an RPB operating under actual conditions were used to validate the model. The model demonstrates high precision in predicting the removal efficiency of H2S and CO2.

Optimization of co-injecting CH4 with CO2 to enhanced oil recovery and carbon storage: A machine-learning based case study on H59 block of Jilin Oilfield, China

During CO2-EOR implementation, CH4 in the reproduced CO2-rich mixture are included in the recycle injection gas. However, improper injection gas composition and operation parameters can reduce the flooding performance.In this study, a machine-learning assisted framework combining Convolutional Neural Networks-Gate Recurrent Unit (CNN-GRU) and Non-dominated Sorting Genetic Algorithm II (NSGA-II) was proposed to obtain the optimal parameters for simultaneous maximum oil production, carbon storage efficiency, and net present value. A case study from the CO2-EOR project in the H59 block of Jilin oilfield, China, was carried out. Base cases were established to evaluate the effects of reinjection CH4 on flooding performance.Results show that the built CNN-GRU model has high prediction accuracy and computational efficiency, and thus can be used as an alternative tool to the reservoir simulator. The proposed framework can find the optimum parameters to improve oil recovery, carbon storage and net present value. The co-injection of CH4 and CO2 improves oil production, and carbon storage performance, but reduces the net present value. This work provides engineers with multiple strategies for decision-making to simultaneously promote flooding performance with CH4 being a co-injectant in CO2-EOR projects.

Performance assessment of residential heat pumps operating in extreme cold climates using zeotropic mixtures

Extremely cold climates subject residential heat pumps to significant temperature differences between the heat source and the ambient being heated, which may lead to system failure and reduced compressor performance. The present study considers the possibility of improving the performance of heat pump systems that are simultaneously used for residential space and domestic water heating while subjected to climates varying from -25 °C to 5 °C by exploring the use of zeotropic mixtures. CO2-based binary mixtures composed of low-GWP (global warming potential) refrigerants are considered – R32, R1234yf, and R290 – aiming to benefit from environmentally friendly and flame suppressants characteristics of CO2, as well as the improved thermal efficiency granted by the addition of a secondary refrigerant. A thermodynamic model was developed for a standard vapor-compression heat pump cycle and used to maximize the coefficient of performance limited by the minimum pinch point in the heat exchangers. Our analysis explores the effect of several parameters, such as, the mixture components, mass fractions, space and water heating demands, and heat source temperature on the heat pump's performance. For cold climates, the mixture of R32 (90%)/CO2 (10%) yields the highest COP and CO2-rich mixtures exhibit the lowest. However, by increasing the mass fraction of CO2 within the zeotropic mixture, the pressure ratio of the heat pump was improved. When considering combined performance criteria, such as the volumetric heating effect and the total heat delivered related to heat pump size, CO2-rich mixtures tend to allow more compact systems, especially in colder climates.

Thermophysical Properties and Phase Behavior of CO2 with Impurities: Insight from Molecular Simulations.

Experimentally determining thermophysical properties for various compositions commonly found in CO2 transportation systems is extremely challenging. To overcome this challenge, we performed Monte Carlo (MC) and Molecular Dynamics (MD) simulations of CO2 rich mixtures to compute thermophysical properties such as densities, thermal expansion coefficients, isothermal compressibilities, heat capacities, Joule-Thomson coefficients, speed of sound, and viscosities at temperatures of (235-313) K and pressures of (20-200) bar. We computed thermophysical properties of pure CO2 and CO2 rich mixtures with N2, Ar, H2, and CH4 as impurities of (1-10) mol % and showed good agreement with available Equations of State (EoS). We showed that impurities decrease the values of thermal expansion coefficients, isothermal compressibilities, heat capacities, and Joule-Thomson coefficients in the gas phase, while these values increase in the liquid and supercritical phases. In contrast, impurities increase the value of speed of sound in the gas phase and decrease it in the liquid and supercritical phases. We present an extensive data set of thermophysical properties for CO2 rich mixtures with various impurities, which will help to design the safe and efficient operation of CO2 transportation systems.

Assessing Coriolis meter performance in multicomponent carbon dioxide-rich mixtures

Accurate flow measurement plays a pivotal role in monitoring CO2 flows across the CCS value chain. This not only bolsters the overall business model of the CCS industry, but also ensures adherence to environmental legislations and regulatory requirements. Unlike other industrial process fluids, such as water, oil & natural gas, it is unclear whether current commercially available metering technologies can meet the requisite accuracy levels, specifically the ±2.5 % recommended within the EU/UK European Trading Scheme for CO2 mass transfer. Accordingly, the aim of this work was to gain a comprehensive understanding of CO2 flow measurement within the context of CCS transport conditions. Firstly, GERG-2008 equation of state was implemented on REFPROP v10 to predict the optimal transport conditions for CO2-rich mixtures and to understand the influence of non-condensable gas impurities in CCS flow operations. Then, a dedicated laboratory-scale gravimetric flow facility was designed and used to evaluate the performance of a Coriolis flow meter under gas, liquid, and supercritical flow conditions. The results indicate that the impurities have a relatively minor impact on the measurement performance of the meter, with maximum mean absolute measurement errors of 0.25 %, 0.12 %, and 0.28 % observed in gas, liquid, and supercritical CO2 flow conditions, respectively. The findings support the use of Coriolis metering technology as a reliable option for CCS metering, underscoring its suitability for accurate measurements in single-phase CO2 transport applications.

Investigation of the transferability of calibration between alternative fluids for liquid and dense phase carbon dioxide flow measurement

Carbon Capture Utilisation and Storage (CCUS) technology is pivotal for achieving global emissions reduction goals. The rise in CCUS facilities, with a near doubling of global capture capacity, indicates industry momentum. Robust flow measurement across the CCUS transport and storage networks are essential for commercial contracts, financial incentives, and regulatory compliance since these are underpinned by accurate quantification of the CO2 quantity transferred across the CCUS chain. However, a critical gap exists in verification and quality assurance of flow meters as currently there are no traceable calibration facilities that operates with liquid and/or dense phase CO2. However, globally there are many accredited traceable water and oil calibration facilities in operation, which can meet the required flow rates and meter sizes. An experimental study was then conducted at TÜV SÜD National Engineering Laboratory, UK, and at the Institute for Energy Technologies, NO, to explore the transferability of calibration between water, oil, and CO2 using five flow meter technologies with the aim of providing a preliminary assessment of whether meters calibrated in alternative fluids can accurately measure liquid and supercritical CO2. The results suggest that this approach could work for Coriolis meters. The results also suggest caution in relying solely on using Equations of State to calculate density values and a recommendation is presented to currently employing direct density measurements until a more comprehensive understanding is achieved on Equations of State performance for CO2-rich mixtures. To the best of the author's knowledge this is the first time that such experimental investigation is conducted, and the results shared publicly.

An experimental and modelling investigation on the water content of CO2and CO2-rich mixtures using the differential scanning hygrometry (DSH) method

Monitoring humidity downstream to conditioning facilities and during transportation is essential for avoiding hydrate deposition. However, water inline monitoring under high pressure is still challenging in the CCS industry. This study presents an experimental and modelling investigation for enhancing field monitoring and model predictions. Measurements are performed using the Differential Scanning Hygrometry (DSH). This novel analytical approach has been successfully tested for measuring dew/frost temperatures for carbon dioxide, CH4+CO2, and CO2-rich mixtures in equilibrium with hydrates, free water and ice. Moreover, the DSH method has been applied for direct HP equilibrium temperature measurements. Also, this work compares three modified versions of the classical SRK EoS with the Multi-Fluid Helmholtz Energy Approximation (MFHEA). This evaluation includes Huron-Vidal and the EMS mixing rules and the cubic-plus association (CPA) approach. A thorough fitting process was carried out and, overall, comparisons with the experimental data showed that SRK + EMS yielded results as satisfactory as sCPA.

A two-capillary viscometer for temperatures up to 473 K and pressures up to 100 MPa—operation and verification at low pressure

In this paper, we described the design and construction of a new two-capillary viscometer with several novel technical solutions for viscosity and density measurements. Our design, which is based on the low-pressure principle, featured numerous improvements in hardware and procedure that allowed the greatly extended range of pressure. The new design adopted a (2 × 2) capillary configuration, utilizing different combinations of four capillaries to enable viscosity measurements with a wide range of flow rates, temperatures, and pressures. The design temperature range is 213 K–473 K, and the pressure range is up to 100 MPa. The viscometer was specifically designed for measuring the viscosity of pure CO2 and CO2-rich mixtures, addressing the scarcity of data in conditions relevant to carbon capture, transport, and storage. Our facility is capable of viscosity measurements in different thermodynamic states; gaseous, liquid, supercritical, and critical regions. A commercial densimeter is integrated to measure density under the same temperatures and pressures. We aimed for a total uncertainty target of better than 0.03%. The performance of the viscometer was validated by measurements with pure CO2 at 298.15 K and zero density. We observed a deviation of less than 0.03% between the reference viscosity of CO2 of this work and accurately calculated data using ab initio quantum mechanics with a standard uncertainty of 0.2%. Our primary focus in this paper was to provide a detailed description of the design and construction of the apparatus, emphasizing improvements and introducing new solutions to other research groups in constructing similar instruments suitable for low- and high-pressure viscosity measurements with high accuracy.

Atomic-Scale Insights into the Phase Behavior of Carbon Dioxide and Water from 313 to 573 K and 8 to 30 MPa.

We performed molecular dynamics (MD) simulations of CO2 + H2O systems by employing widely used force fields (EPM2, TraPPE, and PPL models for CO2; SPC/E and TIP4P/2005 models for H2O). The phase behavior observed in our MD simulations is consistent with the coexistence lines obtained from previous experiments and SAFT-based theoretical models for the equations of state. Our structural analysis reveals a pronounced correlation between phase transitions and the structural orderliness. Specifically, the coordination number of Ow (oxygen in H2O) around other Ow significantly correlates with phase changes. In contrast, coordination numbers pertaining to the CO2 molecules show less sensitivity to the thermodynamic state of the system. Furthermore, our data indicate that a predominant number of H2O molecules exist as monomers without forming hydrogen bonds, particularly in a CO2-rich mixture, signaling a breakdown in the hydrogen bond network's orderliness, as evidenced by a marked decrease in tetrahedrality. These insights are crucial for a deeper atomic-level understanding of phase behaviors, contributing to the well-grounded design of CO2 injection under high-pressure and high-temperature conditions, where an atomic-scale perspective of the phase behavior is still lacking.

Direct measurement of hydrate equilibrium temperature in CO2 and CO2 rich fluids with low water content

A high-pressure experimental setup was used to obtain experimental data on the hydrate equilibrium (melting) temperature (HET) of hydrates formed from low water content CO2 and CO2 rich mixtures. A novel method was used to measure hydrate formation temperature in addition to melting temperature directly at realistic temperature/pressure conditions encountered in transport by pipelines or ship. The method can be used to evaluate the likelihood of hydrate formation in pipelines/ships transporting pure CO2 and CO2 coming from capture processes as well as from high CO2 content produced gas. The data generated from the measurement can also be used to investigate the kinetics of hydrate formation and dissociation in low water content fluids at pipeline/ship conditions. This paper details the experimental equipment, methods, test fluids and results. Experimental results are compared against predictions of the simplified cubic plus association equation of state (sCPA-EoS) coupled with the van der Waals and Platteeuw solid solution theory.

Experimental Analysis of the Effect of Cathodic CO2 Supply to Industrial Solid Oxide Fuel Cells

The integration of Solid Oxide Fuel Cells (SOFCs) in hybrid power generation systems offers the opportunity to achieve higher electric efficiencies. In the SOS-CO2 cycle [1], a newly developed cycle for blue power production (i.e., power generated starting from natural gas while capturing CO2), the SOFC cathode is supplied with mixtures of CO2 and O2, up to 79% CO2 molar fraction, while the anode is supplied with a reformate feed, containing H2, CH4, CO, CO2, and water vapour. Aim of this work is to experimentally evaluate the performance and the durability of industrial 5x5 cm2 Ni-YSZ anode-supported SOFCs under the SOS-CO2 cycle conditions, focusing on the effects of the CO2-rich cathodic atmosphere. The cells mounted a LSCF-based (La0.6Sr0.4Co0.2Fe0.8O3) single phase cathode, coated by a current collection layer of LSC (La0.6Sr0.4CoO3). Laboratory tests were performed at 700°C, acquiring polarization (I/V) curves and EIS spectra by means of a Horiba – FuelCon C50 Evaluator test station. Initial investigations with 7% humidified H2 and 21/79 O2/CO2 cathodic mixture revealed 25% power loss compared to the base case with cathodic air. The test showed not only that the loss of performance was stable in time, but also that the power reduction was reversible since the initial performance in air was recovered. The EIS spectra showed an increase of the polarization resistance and of the ohmic resistance upon feeding CO2. This latter observation suggested a reduction of the electronic conductivity of the cathode, compatible with the formation of Sr carbonates on the perovskite surface [2–4]. To assess the performance of the SOFC under the operating conditions of the SOS-CO2 cycle, the anode was supplied with reformate. Compared to the base case with humidified hydrogen and air, the current density at 0.7 V decreased by 37% (490 mA/cm2). When supplying the 21/79 O2/CO2 mixture at the cathode, the current density stabilized at 420 mA/cm2 (Figure 1). Durability tests (over 300 h) at 700°C with reformate and 21/79 O2/CO2 mixture highlighted a moderate decrease of the current density at 0.7 V. After these tests, the cathode was characterized post-mortem with XRD, SEM and Raman to analyse the consequences of the prolonged exposure to CO2. To further quantify the effect of CO2 on the cathode, symmetric button cells were also characterized with EIS, measuring ohmic and polarization resistances. The results suggested that the adsorption of CO2 is reversible and indicated a better suitability of LSCF- compared to LSC-based cathodes for operations with CO2-rich mixtures. Experiments performed between 550 and 700°C at varying CO2 and O2 partial pressures allowed to describe the kinetics of the oxygen reduction reaction and extract its activation energy. Overall, the results provided key elements for the integration of SOFCs in the SOS-CO2 blue power technology.

Characterization and Testing of Exsolution-Based Solid Oxide Cells for Reversible Operations in CO2 Electrolysis

Reversible solid oxide cells (rSOCs) are a promising electrochemical technology able to work both as energy storage devices in solid oxide electrolysis (SOEC) mode, and as power generators in solid oxide fuel cell (SOFC) mode. rSOCs implemented for CO2 electroreduction into valuable CO-rich steams through electrolysis would provide opportunities for CO2 utilization, and hence become useful tools for the reduction of greenhouse gases emissions. High-temperature co-electrolysis of CO2/H2O mixtures has recently become of interest since high conversion and energy efficiency are thermodynamically favored in addition to the reduction in cell area-specific resistance when compared to pure CO2 electrolysis [1]. However, reversible operation with CO2-containing feeds requires developing flexible, high-performing, and long-lasting materials for the rSOCsManaging issues such as coking and low redox tolerance in the state-of-the-art (SoA) Ni-Yttria-stabilized-zirconia (Ni-YSZ) cermet fuel electrode in the rSOCs is crucial. Ni-YSZ cermet exhibits high electronic conductivity and electrochemical activity in hydrogen. Nonetheless, Ni is prone to oxidation due to operation under high steam concentrations, and rapid variations in the fuel supply. Additionally, Ni is well-known for its coke-formation tendency which becomes detrimental in CO2-rich mixtures for electrolysis [2]. Thus, ceramics with mixed ionic and electronic conductivity (MIEC) have emerged as alternative fuel electrodes thanks to the larger electrochemically active area compared to standard cermets. Among the MIEC electrodes, the SrTi0.3Fe0.7O3 (STF) perovskite has proven to give low polarization resistances especially when modification techniques such as exsolution of metal nanoparticles are employed [3]. This work focuses on the investigation of the electrocatalytic properties of exsolution-based STF electrodes operating with CO/CO2 and H2O/CO2 mixtures. The mixtures used were 50% CO2/50% CO, 25% H2O/25% CO2/25%H2/25%CO, and 45% H2O/45% CO2/10% H2. A comparison between the performance and microstructure of the studied electrode formulation is provided.Electrolyte-supported cells were manufactured via screen-printing of the electrode inks on scandia-stabilized zirconia (ScSZ) electrolytes. STF perovskite-based electrodes were used, namely: SrTi0.3Fe0.7O3 (STF), Sr0.95(Ti0.3Fe0.63Ni0.07)O3 (STF-Ni), and Sr0.95(Ti0.3Fe0.63Ru0.07)O3 (STF-Ru). The latter two formulations allowed the enhancement of the perovskite structure via exsolution of catalytic nanoparticles (Ni, Co alloyed with Fe) on the oxide surface during cell operation. Each cell configuration included a gadolinium-doped ceria (GDC) buffer layer coupled with an LSCF-GDC (La0.6Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O1.95) oxygen electrode. Baseline performances of cell mounting the Ni-YSZ cermet electrode were also evaluated for comparison with the perovskite alternatives, both in the short and long term. Electrochemical characterization was done via impedance spectroscopy, polarization experiments, and durability tests in potentiostatic mode. Chemical characterization was performed via X-ray diffraction, scanning electron microscopy, and temperature-programmed reduction analyses.Compared to Ni-YSZ, significant improvement in terms of reversibility and maximum current densities of the current-voltage (I/V) curves in both SOFC and SOEC modes is found on the STF-based cells at 750°C under CO/CO2 mixtures (Figure 1B). The initial difference in the performance of the STF cells with respect to the Ni-YSZ cermet in humidified H2 (SOFC mode, Figure 1A) was overcome by using the exsolved electrode formulations. Aging experiments up to 100 h performed in alternating operation modes from SOFC (6 h) to SOEC (6 h) indicated an initial performance degradation within the first 24 h for both the cermet and perovskite-based fuel electrodes which later stabilized in time. Compared to the undoped STF formulation, improvement in performance stability was observed for the exsolved STF-Ni and STF-Ru fuel electrodes while working under the target CO/CO2 mixture. This was attributed to the combination of the STF structure benefits (low polarization resistance towards CO/CO2 and H2O/CO2 mixtures) with the boost that metallic nanoparticles provide to the electrode’s heterogeneous catalytic reactivity and overall stability over time.

Characterization and Testing of Exsolution-Based Solid Oxide Cells for Reversible Operations in CO2 Electrolysis

Reversible solid oxide cells (rSOCs) are promising electrochemical devices, able to work both in energy storage mode as solid oxide electrolyzes (SOECs), and in power generation mode as solid oxide fuel cells (SOFCs). rSOCs dedicated to high-temperature co-electrolysis of CO2/H2O mixtures are of interest since they could foster the utilization and consequent reduction of CO2 gas emissions while converting it and H2O into valuable fuels (i.e. syngas and H2). However, operation under CO2-rich feeds requires alternatives to the state-of-the-art Ni-Yttria-stabilized-zirconia (Ni-YSZ) cermet fuel electrode in view of its low coking and redox resistance. Perovskites with mixed ionic and electronic conductivity are major alternatives, especially when the functionality of their active surface is enhanced via metal nanoparticle exsolution. This work focuses on the investigation of the electrocatalytic properties of the SrTi0.3Fe0.7O3 (STF), and exsolution Sr0.95(Ti0.3Fe0.63Ni0.07)O3 (STF-Ni) perovskite-based fuel electrodes together with Ni-YSZ while operating with CO2-rich mixtures both in the short and long term.

Net zero Flow Assurance - Validation of various equations of state for the prediction of VLE and density of CO2-rich mixtures for CCUS applications

Carbon dioxide management is becoming a major topic of interest in the energy industry and carbon capture is part of this process. Carbon capture utilization and storage is considered a promising technique to mitigate the impact of the hard-to-abate industries. Despite the high level of accuracy of predictions of the thermodynamic behaviour of pure CO2, there are still several uncertainties when dealing with CO2-rich mixtures. The impact of impurities in the captured stream can impact considerably the sizing and the design of components such as pipelines and related costs. The scope of this work is to assess the capabilities of the most acknowledged Equations of State (EoS) in the energy industry to predict CO2-rich mixtures behaviour. In this work we assess their accuracy in the prediction of Vapour-Liquid Equilibrium (VLE) and density validating numerical results with detailed experimental data available in literature. A quantitative estimation of deviations from experimental data is provided for density and bubble points. The results show that, based on experimental data available, multi-parameters Equations of State, such as GERG-2008 and CSMA, are generally more accurate in the description of both VLE and density if compared with cubic EoS.

Towards an engineering tool for the prediction of running ductile fractures in CO2 pipelines

A prerequisite for the deployment of CO2 capture and storage (CCS) is to establish a large network of high-pressure transport pipelines. It is then vital to assess new and existing pipeline designs for running ductile fracture (RDF). RDF is a phenomenon in which a defect develops into a crack propagating along the pipeline, sustained by the pressure forces from the escaping fluid. The most common engineering method for RDF, the Battelle two-curve method (BTCM), was originally developed for natural gas (NG) and has proved non-conservative for CO2. In this work we examine the BTCM in the light of available RDF experiments with CO2-rich mixtures. We present an improved material curve, in which the change in fluid properties when replacing NG with CO2 results in a new effective toughness correlation. Furthermore, we present an improved method for calculating the crack-tip pressure. This delayed homogeneous equilibrium model (D-HEM) accounts for the non-equilibrium thermodynamics due to the rapid depressurization, resulting in boiling pressures below the saturation pressure. Together, the adaptation of the material and fluid treatment yields improved results, and is a step towards a viable engineering tool for the prediction of RDF in CO2 pipelines.

Molecular guest exchange and subsequent structural transformation in CH4 – CO2 replacement occurring in sH hydrates as revealed by 13C NMR spectroscopy and molecular dynamic simulations

This study adopted experimental and computational approaches to investigate CH4 – CO2 replacement in the structure H (sH) CH4 + methylcyclopentane (MCP) hydrate for its dual functions of CH4 recovery and CO2 sequestration. Hydrate phase equilibria, 13C NMR spectra, and molecular dynamics (MD) simulations of CH4 + MCP – CO2 replacement were examined and compared with those of CH4 + neohexane (NH) – CO2 replacement to elucidate the molecular guest exchange behaviors in both systems. The structure I (sI) hydrates were thermodynamically favored in CO2-rich gas mixtures (CH4 + CO2 + MCP systems), and a structural transformation from sH to sI occurred when CO2 composition in the feed gas was higher than 20 %. The 13C NMR spectra indicated that the CO2 molecules preferred to occupy the large (51262) cages of sI and the medium (435663) cages of sH compared to the small (512) cages of both sI and sH during replacement. Following CO2 injection into the sH CH4 + MCP hydrate, the initial sH hydrate transformed to the sI hydrate with CH4 recovery of approximately 78 %. The MD simulations also demonstrated that structural transformation in the CH4 + MCP – CO2 replacement would occur at the lower CO2 enclathration ratio compared to the CH4 + NH – CO2 replacement, thereby leading to a lower CO2 concentration in the newly formed sI hydrate. This is the first study to provide both experimental and computational evidence of guest-dependent structural transformation in sH CH4 + liquid hydrocarbons – CO2 replacement.

Experimental investigation on the phase behaviour for gas hydrates in CO2 rich gas mixtures & multiphase system

Almost 40% of undiscovered hydrocarbon reserves have high CO2 and H2S concentrations around the globe. So it is crucial to understand these hydrocarbon systems’ thermophysical properties for the excellent design of production facilities. An experimental investigation is conducted in this study to understand and evaluate the thermodynamic conditions of gas hydrate formation in natural gas systems with high CO2 levels gas and dominant multiphase (high CO2 level gases, deionized water, and crude oil). Three gas mixtures were chosen in this study to simulate natural gas with high CO2 content. The experiments are conducted within the critical pressure of the selected gas to avoid any phase change due to pressure. The impact of high CO2 levels in gas systems on the thermodynamic conditions of the gas hydrates was first explored. Then, the effect of a multiphase system was investigated after the addition of the oil phase into the system. The thermodynamic equilibrium conditions obtained from experiments were used to construct the Hydrate liquid–vapour Equilibrium (HLVE) curves, and the phase behaviour was studied. The details about the temperature variance and enthalpy are also clearly discussed. It has been discovered that gas mixtures with a higher CO2 content tend to promote compared to the pure methane gas system but inhibit compared the pure CO2 system. But in the multiphase system, all the gases show an inhibition effect compared to their respective pure gas system results.

Experimental Study on Hydrate Structure Transition Using an In Situ High-Pressure Powder X-ray Diffractometer: Application in CO2 Capture

Clathrate (gas) hydrates as materials have received great interest due to their high-density gas storage potential and separation applications for their ability to preferentially separate a targeted component such as CO2 from waste streams. Among the three clathrate hydrate structures, only sH (structure H) hydrates require a large molecule such as neohexane (NH) or tert-butyl methyl ether (TBME) as well as a “help-gas” molecule such as methane (CH4) to form a stable structure. However, attempts to use CO2 as a help-gas came up with mixed results where it appeared that the sH hydrate formed was stable only at temperatures below the ice point, whereas the compound formed with CH4 was considerably more stable. sH hydrates have considerable potential for gas separation, for instance, of CH4–CO2 mixtures. Thus, in this work, several compositions were tested for their hydrate forming ability. The large cage guests tested were NH and TBME, the help-gas mixtures were a CO2-rich mixture (76% CO2 and 24% CH4), and a CO2 lean mixture (24% CO2 and 76% CH4). The phase behavior of hydrates formed from the various combinations was tested by measuring the endo- and exotherms associated with hydrate formation and decomposition in a high-pressure differential calorimeter. The different phases indicated from the DSC results were identified by employing an in situ high-pressure cell on a powder X-ray diffractometer. Powder patterns were recorded to identify the crystal phase arising from nucleation and possible re-crystallization events after annealing. It was confirmed that the CO2 lean mixture (24% CO2 and 76% CH4) forms structure H (sH) hydrate, while the CO2-rich mixture (76% CO2 and 24% CH4) forms structure I (sI) hydrate presenting a structure transition pattern across the gas mixtures investigated. Further, it was observed that the CO2 lean mixture, which forms sH hydrate, also starts as sI hydrate and gradually converts to the thermodynamically stable sH hydrate. This study, in essence, helps to understand the preference of CH4 and CO2 for three different types of cages in sH hydrates and presents a design framework for a suitable gas separation mechanism for this gas mixture of interest.

Effects of Tween 80 on clathrate and semiclathrate CO2 hydrate formation kinetics for carbon capture from CO2-rich gas mixtures

In this study, Tween 80 was chosen as a kinetic promoter to study the effect of non-ionic surfactant on CO2 hydrate formation kinetics. The experiments were carried out in a thermostatic reactor using CO2-rich gas mixtures with Tween 80 (0–3000 ppm) in both clathrate hydrates and tetra-n-butyl ammonium bromide (TBAB) semiclathrate hydrates. Analysis of variance (ANOVA) was used to analyze the difference among experimental results, and a decision box was proposed to evaluate the performance of systems studied. The apparent improvement in the induction time, gas uptake yield, and gas separation performance were observed in 1000-ppm or 2000-ppm Tween 80 in semiclathrate hydrates. Increased pressure further improved the kinetic promotion effect of Tween 80. However, a higher concentration of 3000-ppm Tween 80 was found to result in an inhibition effect on CO2 uptake yield in semiclathrate hydrates, although the induction time remained short. Compared with common anionic and cationic surfactants, 2000-ppm Tween 80 showed the best CO2 separation performance from gas mixtures in semiclathrate hydrates. No inhibition effect was observed in clathrate hydrates with studied concentrations of Tween 80.

Viscosity measurements of CO2-rich; CO2 + N2 and CO2 + H2 mixtures in gas or supercritical phase at temperatures between 273 and 473 K and pressures up to 8.7 MPa

New experimental viscosity data of three binary CO2-rich mixtures with approximate mole fractions of 0.93 CO2 + 0.07 H2, 0.80 CO2 + 0.20 H2, and 0.90 CO2 + 0.10 N2 are reported. The measurements were performed at four different isotherms between 273 K and 473 K. Two independent rotating body viscometers with different pressure range were utilized, suitable for measurement of pressures up to 2 MPa and 20 MPa, respectively. The maximum expanded combined relative uncertainty (k = 2) in viscosity was 0.25% for the data obtained from the low-pressure viscometer and 0.6% for the data measured by the high-pressure viscometer. The experimental data were compared to the data estimated by the extended corresponding states (ECS) model implemented in the NIST REFPROP 10.0 database. The maximum deviation between the model and the new data is 1.86%. The data measured with the two apparatuses agree within the estimated uncertainty.