Diffusion coefficients of CO2 and N-2 in water at temperatures between 298.15 K and 423.15 K at pressures up to 45 MPa

We report measurements of the diffusion coefficients of CO2 and N2 in pure water at temperatures between (298.15 and 423.15) K and pressures between (15 and 45) MPa. The measurements were made by the Taylor dispersion method and have a standard relative uncertainty of 2.3 %. The results were found to be essentially independent of pressure over the range investigated and a simple relation, based on the Stokes–Einstein equation, is proposed to correlate the experimental data. Some experimental difficulties arising in the measurement of the diffusivities of slightly soluble acid-gas solutes such as CO2 in water are also discussed

Experimental and modeling study of the phase behavior of synthetic crude oil + CO2

A full understanding of the phase behavior of CO2–hydrocarbon mixtures at reservoir conditions is essential for the proper design, construction and operation of carbon capture and storage (CCS) and enhanced oil recovery (EOR) processes. While equilibrium data for binary CO2–hydrocarbon mixtures are plentiful, equilibrium data and validated equations of state having reasonable predictive capability for multi-component CO2–hydrocarbon mixtures are limited. In this work, a new synthetic apparatus was constructed to measure the phase behavior of systems containing CO2 and multicomponent hydrocarbons at reservoir temperatures and pressures. The apparatus consisted of a thermostated variable-volume view cell driven by a computer-controlled servo motor system, and equipped with a sapphire window for visual observation. Two calibrated syringe pumps were used for quantitative fluid injection. The maximum operating pressure and temperature were 40 MPa and 473.15 K, respectively. The apparatus was validated by means of isothermal vapor–liquid equilibrium measurement on (CO2 + heptane), the results of which were found to be in good agreement with literature data. In this work, we report experimental measurements of the phase behavior and density of (CO2 + synthetic crude oil) mixtures. The ‘dead’ oil contained a total of 17 components including alkanes, branched-alkanes, cyclo-alkanes, and aromatics. Solution gas (0.81 methane + 0.13 ethane + 0.06 propane) was added to obtain live synthetic crudes with gas-oil ratios of either 58 or 160. Phase equilibrium and density measurements are reported for the ‘dead’ oil and the two ‘live’ oils under the addition of CO2. The measurements were carried out at temperatures of 298.15, 323.15, 373.15 and 423.15 K and at pressures up to 36 MPa, and included vapor–liquid, liquid–liquid and vapor–liquid–liquid equilibrium conditions. The results are qualitatively similar to published data for mixtures of CO2 with both real crude oils or and simple hydrocarbon mixtures containing both light and heavy components. The present experimental data have been compared with results calculated with two predictive models, PPR78 and PR2SRK, based on the Peng–Robinson 78 (PR78) and Soave–Redlich–Kwong (SRK) equations of state with group-contribution formulae for the binary interaction parameters. Careful attention was paid to the critical constants and acentric factor of high molar-mass components. Since the mixture also contained several light substances with critical temperatures below some or all experimental temperatures, we investigated the use of the Boston–Mathias modification of the PR78 and SRK equations. The results showed that these models can predict with reasonable accuracy the vapor–liquid equilibria of systems containing CO2 and complex hydrocarbon mixtures without the need to regress multiple binary parameters against experimental data

Phase Behavior of the System (Carbon Dioxide + n -Heptane + Methylbenzene): A Comparison between Experimental Data and SAFT-γ-Mie Predictions

In this work, we explore the capabilities of the statistical associating fluid theory for potentials of the Mie form with parameter estimation based on a group-contribution approach, SAFT-γ-Mie, to model the phase behavior of the (carbon dioxide + n-heptane + methylbenzene) system. In SAFT-γ-Mie, complex molecules are represented by fused segments representing the functional groups from which the molecule may be assembled. All interactions between groups, both like and unlike, were determined from experimental data on pure substances and binary mixtures involving CO2. A high-pressure high-temperature variable-volume view cell was used to measure the vapor–liquid phase behavior of ternary mixtures containing carbon dioxide, n-heptane, and methylbenzene over the temperature range 298–423 K at pressures up to 16 MPa. In these experiments, the mole ratio between n-heptane and methylbenzene in the ternary system was fixed at a series of specified values, and the bubble-curve and part of the dew-curve was measured under carbon dioxide addition along four isotherms

Solubility of carbon dioxide in aqueous blends of 2-amino-2-methyl-1-propanol and piperazine

In this work, we report new solubility data for carbon dioxide in aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and piperazine (PZ). A static-analytical apparatus, validated in previous work, was employed to obtain the results at temperatures of (313.2, 333.2, 373.2, 393.2) K, and at total pressures up to 460 kPa. Two different solvent blends were studied, both having a total amine mass fraction of 30%: (25 mass% AMP+5 mass% PZ) and (20 mass% AMP+10 mass% PZ). Comparisons between these PZ activated aqueous AMP systems and 30 mass% aqueous AMP have been made in terms of their cyclic capacities under typical scrubbing conditions of 313 K in the absorber and 393 K in the stripper. The Kent–Eisenberg model was used to correlate the experimental data

Pressurized Calcium Looping in the Presence of Steam in a Spout-Fluidized-Bed Reactor with DFT Analysis

Calcium looping is a high-temperature solid-looping process for CO2 capture, exploiting cyclical carbonation of CaO. Previous work investigating the effects of steam on the carbonation reaction has produced conflicting results, with the majority of work conducted using thermogravimetric analyzers (TGA). Here, pressurized carbonation kinetics in the presence of steam in a 3 kWe pressurized spout-fluidized bed reactor, gives a rigorous insight into the effects of steam. Pseudo-intrinsic kinetics were determined using an effectiveness factor model along with activation energies and kinetic expressions. The mechanism in which steam promotes CO2 adsorption on the surface of CaO was investigated using density functional theory (DFT). The molecular-scale changes on the CaO surface owing to the presence of steam compared to the base case of CO2 adsorption on a ‘clean’ (without steam) surface were simulated with the Cambridge Serial Total Energy Package (CASTEP) software. The results suggest that steam promotes CO2 adsorption via the formation of surface OH groups on the CaO surface

Process and reactor design for biophotolytic hydrogen production

The green alga Chlamydomonas reinhardtii has the ability to produce molecular hydrogen (H2), a clean and renewable fuel, through the biophotolysis of water under sulphur-deprived anaerobic conditions. The aim of this study was to advance the development of a practical and scalable biophotolytic H2 production process. Experiments were carried out using a purpose-built flat-plate photobioreactor, designed to facilitate green algal H2 production at the laboratory scale and equipped with a membrane-inlet mass spectrometry system to accurately measure H2 production rates in real time. The nutrient control method of sulphur deprivation was used to achieve spontaneous H2 production following algal growth. Sulphur dilution and sulphur feed techniques were used to extend algal lifetime in order to increase the duration of H2 production. The sulphur dilution technique proved effective at encouraging cyclic H 2 production, resulting in alternating Chlamydomonas reinhardtii recovery and H2 production stages. The sulphur feed technique enabled photobioreactor operation in chemostat mode, resulting in a small improvement in H2 production duration. A conceptual design for a large-scale photobioreactor was proposed based on these experimental results. This photobioreactor has the capacity to enable continuous and economical H 2 and biomass production using green algae. The success of these complementary approaches demonstrate that engineering advances can lead to improvements in the scalability and affordability of biophotolytic H2 production, giving increased confidence that H2 can fulfil its potential as a sustainable fuel of the future. © 2013 the Owner Societies