CO2 absorption into a phase change absorbent: Water-lean potassium prolinate/ethanol solution

Phase change solvents are attractive energy-efficient absorbents for carbon dioxide (CO₂) capture due to CO₂-rich phase formation. Potassium prolinate + water + ethanol (ProK/W/Eth) solution has shown good capture characteristics as a promising one in our previous work. In this work, absorption rate of CO₂, solubility of N₂O, and heat of absorption for ProK/W/Eth solution were investigated using a stirred cell reactor and a CPA201 reaction calorimeter and these results were also compared with the aqueous ProK and 30 mass% MEA solutions. Using ethanol as a solvent can substantially increase the CO₂ physical solubility and the absorption rate of CO₂ in ProK/W/Eth solutions is far higher than that in aqueous 30 mass% MEA solutions especially at a low CO₂ loading range. Solid precipitation, obtained from the liquid-to-solid phase change absorption, was analyzed by ¹³C NMR and DSC-TGA. The enthalpy change for ProK/W/Eth solutions at various CO₂ loading was also discussed.     

Extraction of phenolic compounds and anthocyanins from blueberry (Vaccinium myrtillus L.) residues using supercritical CO2 and pressurized liquids

This work explored the potential of subcritical liquids and supercritical carbon dioxide (CO₂) in the recovery of extracts containing phenolic compounds, antioxidants and anthocyanins from residues of blueberry (Vaccinium myrtillus L.) processing. Supercritical CO₂ and pressurized liquids are alternatives to the use of toxic organic solvents or extraction methods that apply high temperatures. Blueberry is the fruit with the highest antioxidant and polyphenol content, which is present in both peel and pulp. In the extraction with pressurized liquids (PLE), water, ethanol and acetone were used at different proportions, with temperature, pressure and solvent flow rate kept constant at 40 °C, 20 MPa and 10 ml/min, respectively. The extracts were analyzed and the highest antioxidant activities and phenolic contents were found in the extracts obtained with pure ethanol and ethanol + water. The highest concentrations of anthocyanins were recovered with acidified water as solvent. In supercritical fluid extraction (SFE) with CO₂, water, acidified water, and ethanol were used as modifiers, and the best condition for all functional components evaluated was SFE with 90% CO₂, 5% water, and 5% ethanol. Sixteen anthocyanins were identified and quantified by ultra performance liquid chromatography (UPLC).     

Phase equilibrium data of guaçatonga (Casearia sylvestris) extract + ethanol + CO2 system and encapsulation using a supercritical anti-solvent process

The aim of this research was to investigate the phase equilibrium behavior of a system containing guaçatonga extract + ethanol + CO₂ in order to help define the adequate conditions of temperature and pressure for the co-precipitation process, performed by means of supercritical anti-solvent (SAS) technique. Guaçatonga (Casearia sylvestris) is a native medicinal plant from Brazil, rich in valuable components such as β-caryophyllene, α-humulene and bicyclogermacrene. Phase equilibrium data were obtained by the static method using guaçatonga extract dissolved in ethanol (1:100, wt/wt), at temperatures ranging from 35 to 75 °C and CO₂ mass content from 60 to 90 wt%. It was noticed that the system exhibited solid–vapor–liquid, solid–liquid–liquid and solid–vapor–liquid–liquid transition types and a lower critical solution temperature behavior. Phase behavior study was considered for the definition of the SAS conditions applied for the encapsulation of guaçatonga extract in the biopolymer Pluronic F127. The conditions tested ranged from 80 to 140 bar at 45 °C. At 80 bar only segregated particles of extract and the biopolymer were detected, while at 110 and 140 bar an extract encapsulation was achieved.     

High-pressure phase equilibrium data for the l-lactic acid + (propane + ethanol) and the l-lactic acid + (carbon dioxide + ethanol) systems

Biodegradable polymers have received increased attention due to their potential applications in the medicine and food industries; in particular, poly(l-lactic acid) (PLA) is of primary importance because of its biocompatibility and resorbable features. Recently, the synthesis of this biopolymer through the enzyme-catalyzed ring-opening polymerization of l-lactic acid in a compressed fluid has been considered promising. The aim of this work was to report the phase equilibrium data (cloud points) of the l-lactic acid + (propane + ethanol) and the l-lactic acid + (carbon dioxide + ethanol) systems. The phase equilibrium experiments were conducted in a variable-volume view cell employing the static synthetic method. These experiments were conducted in the temperature range of 323.15–353.15 K and at pressures up to 25 MPa; the mass ratio of ethanol to either CO₂ or propane was maintained at 1:9. The l-lactic acid + (propane + ethanol) system exhibited vapor–liquid, liquid–liquid and vapor–liquid–liquid transitions, whereas the l-lactic acid + (carbon dioxide + ethanol) system only exhibited liquid–liquid type transitions.     

A study on the carbon dioxide recovery from 2 ton-CO2/day pilot plant at LNG based power plant

A pilot plant of 2 ton-CO₂/day for CO₂ recovery from flue gas emitted from 250 MW LNG based power plant was tested with aqueous absorbents. The absorbent tested were of different nature such as primary amine (MEA), blend of primary, secondary, tertiary and sterically hindered amine such as MDEA + HMDA, AEPD + DPTA, and TIPA + DPTA. We have studied the CO₂ recovery as function of temperature, concentration, and flow rate of absorbent, pressure and temperature of stripper, and flow rate and temperature of flue gas. It was observed that while CO₂ recovery increases with increase in flow rate and concentration of absorbent, it decreases with increase in temperature and flow rate of flue gas. The CO₂ recovery ratio increases with increase in stripper temperature and decrease in stripper pressure. CO₂ loading (mol CO₂/mol amine) also decreases with increase in stripper temperature.For the absorbent flow rate greater than 2.4 N m³/h, the carbon dioxide recovery ratio follows the sequence: MEA > MDEA + HMDA > AEPD + DPTA > TIPA + DPTA.     

Measurement and modeling of the phase behavior of the (carbon dioxide + water) mixture at temperatures from 298.15 K to 448.15 K

An analytical apparatus has been designed to study the phase behavior of fluid mixtures of relevance to CO₂-enhanced oil recovery and carbon dioxide storage in deep aquifers or depleted oil fields. The fluid phases are circulated by means of a dual-channel magnetically-coupled pump and aliquots may be withdrawn from the re-circulation loops, by means of high-pressure sampling valves, for analysis by gas chromatography. The high-pressure cell is fitted with a special probe that may be rotated in order to draw liquid into the re-circulation loop from different heights within the cell, thereby permitting the study of three-phase vapor–liquid–liquid equilibria. The working temperature range of the apparatus is from (298 to 448) K and the maximum working pressure is 50 MPa.In this work, measurements have been made on the binary system (CO₂ + H₂O) at temperatures from (298.15 to 448.15) K and pressure from (1.5 to 18.0) MPa, and the results are compared with the available literature data. Vapor–liquid–liquid and liquid–liquid equilibrium points were also measured at T = 298.15 K. Standard uncertainties were 0.04 K for temperature, 0.04% of reading for pressure, and typically 3 × 10⁻⁴ and 8 × 10⁻⁴ for the mole fractions in liquid and vapor phases respectively. The results have been correlated by means of an asymmetric approach based on the Peng–Robinson equation of state, for the vapor phase, and an extended form of Henry's law incorporating the NRTL solution model, for the aqueous liquid-phase. The ability of the Krichevsky–Kasarnovsky (KK) approach to correlate the data has also been evaluated.     

Comparison of the rate of CO2 absorption into aqueous ammonia and monoethanolamine

Aqueous ammonia has been proposed as an absorbent for use in CO₂ post combustion capture applications. It has a number of advantages over MEA such as high absorption capacity, low energy requirements for CO₂ regeneration and resistance to oxidative and thermal degradation. However, due to its small molecular weight and large vapour pressure absorption must be carried at low temperature to minimise ammonia loss. In this work the rate of CO₂ absorption into a falling thin film has been measured using a wetted-wall column for aqueous ammonia between 0.6 and 6 mol L^?1, 278–293 K and 0–0.8 liquid CO₂ loading. The results were compared to 5 mol L^?1 MEA at 303 and 313 K. It was found that the overall mass transfer coefficient for aqueous ammonia was at least 1.5–2 times smaller than MEA at the measured temperatures. From determination of the second-order reaction rate constant k₂ (915 L mol^?1 s^?1 at 283 K) and activation energy E_a (61 kJ mol^?1) it was shown that the difference in mass transfer rate is likely due to both the reduced temperature and differences in reactivity between ammonia and MEA with CO₂.     

Phase equilibria of (CO2 + H2O + NaCl) and (CO2 + H2O + KCl): Measurements and modeling

We report experimental measurements of the phase behavior of (CO₂ + H₂O + NaCl) and (CO₂ + H₂O + KCl) at temperatures from 323.15 K to 423.15 K, pressure up to 18.0 MPa, and molalities of 2.5 and 4.0 mol kg⁻¹. The present study was made using an analytical apparatus and is the first in which coexisting vapor- and liquid-phase composition data are provided. The new measurements are compared with the available literature data for the solubility of CO₂ in brines, many of which were measured with the synthetic method. Some literature data show large deviations from our results.The asymmetric (γ–φ) approach is used to model the phase behavior of the two systems, with the Peng–Robinson equation of state to describe the vapor phase, and the electrolyte NRTL solution model to describe the liquid phase. The model describes the mixtures in a way that preserves from our previous work on (CO₂ + H₂O) the values of the Henry's law constant and the partial molar volume of CO₂ at infinite dilution Hou et al. [22]. The activity coefficients of CO₂ in the aqueous phase are provided. Additionally, the correlation of Duan et al. [14] for the solubility of CO₂ in brines is tested against our liquid-phase data.     

Measurement of entrainer effects of water and ethanol on solubility of caffeine in supercritical carbon dioxide by FT-IR spectroscopy

The solubilities of caffeine in supercritical CO₂, supercritical CO₂ + water, supercritical CO₂ + ethanol, and supercritical CO₂ + water + ethanol were measured with a circulation-type apparatus combined with an on-line Fourier transform infrared (FT-IR) spectrometer at 313.2 K and 15.0 MPa. The solubilities of caffeine were determined with the peak absorbances of caffeine at 1190 cm⁻¹. The solubilities of caffeine increase until water is saturated in supercritical CO₂. The maximum increase rate is 22%. In CO₂ + caffeine + ethanol system, the solubilities of caffeine increase with increasing the concentration of ethanol. The solubility of caffeine becomes five times when 1000 mol m⁻³ of ethanol is added. In CO₂ + caffeine + water + ethanol system, the solubilities of caffeine are smaller than those with single entrainer of water or ethanol. The shape of the peaks of two CO stretching bands for caffeine were changed by the addition of ethanol. It was confirmed that the interaction species of caffeine interacting with ethanol are produced by deconvolution of the CO stretching bands. The enhancement of solubility for caffeine in supercritical CO₂ by the addition of ethanol is due to the hydrogen bonding between caffeine and ethanol.     

Chitosan nanoparticles generation using CO2 assisted processes

The current concerns of sustainable development make the biobased polymers the object of many studies. Chitosan is a biobased, biocompatible and biodegradable polysaccharide with antibacterial and cytocompatible properties. In this study, we aimed to generate chitosan particles with two processes using CO₂ under pressure, in order to decrease the use of organic solvent and to obtain nanoparticles.The first is a supercritical anti-solvent process: CO₂ acts as an anti-solvent toward an acetic acid aqueous solution of dissolved chitosan in which ethanol was added to enhance the anti-solvent effect. The reciprocal miscibility of CO₂ with the solvents induces the reduction of their solvating power, leading to supersaturation at the capillary outlet and causing the crystallization of the particles.This process led to the generation of more or less agglomerated chitosan nanoparticles with an individual average size of 378 nm.In the second process, the pressurized CO₂ is dissolved in water to lower the pH. This in turn allows the chitosan to be dissolved and the resulting solution is sprayed, thanks to the pressurized CO₂, into a hot air stream. This new process allowed the generation of dried chitosan nanoparticles with a median size of 390 nm.     

High-pressure phase equilibrium measurements and thermodynamic modeling for the systems involving CO2, ethyl esters (oleate,stearate, palmitate) and acetone

The aim of this work was to study the phase behavior of systems involving carbon dioxide (CO₂), fatty acid ethyl esters (ethyl oleate, ethyl stearate and ethyl palmitate) and acetone at high pressures. The phase behavior involving these components is an important step regarding the design and optimization of industrial processes based on supercritical conditions, such as biodiesel production and fatty esters fractionation involving supercritical and/or pressurized solvents. In addition, supercritical CO₂ can offer an interesting alternative for glycerol separation in water-free biodiesel purification processes. The binary systems investigated in this work were CO₂ + ethyl oleate, and CO₂ + ethyl stearate and these were compared with the CO₂ + ethyl palmitate system. The ternary CO₂ + ethyl palmitate + acetone was also investigated at two different ethyl palmitate to acetone molar ratios of (1:1) and (1:3). The static synthetic method using a variable-volume view cell was employed to obtain the experimental data in the temperature range of 303.15–353.15 K. Vapor–liquid (VL), liquid–liquid (LL) and vapor–liquid–liquid (VLL) phase transitions were observed in these systems. In the binary systems, the solubility increased with the presence of unsaturation and decreased with the number of carbon atoms in the fatty ester chain. Addition of acetone as well as ethanol eliminated the liquid–liquid immiscibility and reduced the pressure transitions, therefore increasing the solubility of the ester in supercritical CO₂. The experimental data sets for the binary and ternary systems were successfully modeled using the Peng–Robinson equation of state with the classical van der Waals quadratic mixing rule (PR-vdW2) and Wong-Sandler (PR-WS) mixing rule. Both models showed good performance in the phase equilibrium correlations and in predictions for the binary and ternary systems.     

High-pressure phase equilibria for the binary system carbon dioxide + dibenzofuran

The experimental solubility of dibenzofuran in near-critical and supercritical carbon dioxide and the solid–liquid–vapor (SLV) equilibrium line for the CO₂ + dibenzofuran system are reported. The built in-house static view cell apparatus used in these measurements is described. The solubility of naphthalene in supercritical CO₂ and the CO₂ + naphthalene SLV line are also determined in order to assess the reliability and accuracy of the measurement technique. The solubility of dibenzofuran in carbon dioxide is determined at 301.3, 309.0, 319.2, 328.7 and 338.2 K in the 6–30 MPa pressure range. Solubility data are correlated using the Chrastil model and the Peng–Robinson equation of state. This equation is also used to predict the CO₂ + dibenzofuran SLV line. Results show the feasibility of using supercritical CO₂ to extract dibenzofuran.     

Recovery of carbon dioxide from sugarcane fermentation broth in the ethanol industry

Ethanol is one alternative to the use of petroleum-based fuels. It is produced on a large scale in Brazil from sugarcane to the magnitude of billions of liters per year. During the ethanol production step, a considerable amount of byproducts is obtained and treated as waste. Carbon dioxide is one of these byproducts and a substance of interest especially for food industries. Because the production of 1000 kg of ethanol generates approximately 950 kg of CO₂, this work intends to analyze a cryogenic distillation process for the production of CO₂ by means of computational simulations. The results obtained were in agreement with real operational conditions, achieving CO₂ concentrations up to 100% (v/v). With an initial CO₂ concentration of 95% (v/v), 7 separation stages were obtained, achieving the limit of 5 stages for higher CO₂ concentrations in the raw gas. The effect of initial CO₂ concentrations on the final product and the concentration profiles along the column are also presented. In order to optimize the process, it was observed that, for a maximum feed flow of 3333 kg/h (CO₂ concentration of 99%), the plant was able to obtain 10.48 kgCO₂/kW, recovering about 2828 kgCO₂/h at a final product concentration of 99.90% (v/v) at ?25 °C.     

Influence of natamycin loading methods on the physical characteristics of alginate active films

Natamycin, an antimicrobial agent sparingly soluble in water, was incorporated into alginate films in order to produce antimicrobial packaging, using three different approaches: the conventional loading method, when natamycin is added directly to the polymeric aqueous film-forming solution; the immersion procedure, by which a previously prepared films is contacted with natamycin solution, and by the supercritical solvent impregnation (SSI) method, with loading tests performed in CO₂ containing natamycin, with and without addition of cosolvent (ethanol, 10% molar). The loading capacities were evaluated, as well as the influence on physical attributes of the films and on the release behavior of natamycin in water. The conventional method led to films heterogeneities with high surface roughness, and the immersion technique evinced several disadvantages like low incorporation yields, and negative influence on water vapor permeability and on the swelling degree of the film. The supercritical method showed that longer contact times and the use of ethanol as a cosolvent increased the natamycin loading yields and led to homogeneous films, where SSI (CO₂ + EtOH) process produced visually attractive and tranlucent films.     

Phase behavior of 1,3,5-tri-tert-butylbenzene–carbon dioxide binary system

1,3,5-tri-tert-butylbenzene (TTBB) is solid at ambient conditions, and has substantial solubility in liquid and supercritical carbon dioxide. We present the phase behavior of TTBB–CO₂ binary system at temperatures between 298 and 328 K and at pressures up to 20 MPa. Phase diagrams showing the liquid–vapor, solid–liquid and solid–vapor equilibrium envelopes are constructed by pressure–volume–temperature measurements in a variable-volume sapphire cell. TTBB is highly soluble in CO₂ over a wide range of compositions. Single-phase states are achieved at moderate pressures, even with very high TTBB concentrations. For example, at 328 K, a binary system containing TTBB at a concentration of 95% by weight forms a single-phase above 2.04 MPa. TTBB exhibits a significant melting-point depression in the presence of CO₂, 45 K at 3.11 MPa, where the normal melting point of 343 K is reduced to 298 K. With its high solubility in carbon dioxide, TTBB has potential uses as a binder or template in materials forming processes using dense carbon dioxide.     

Optimization of the supercritical fluid extraction of triterpenic acids from Eucalyptus globulus bark using experimental design

The supercritical CO₂ extraction of E. globulus deciduous bark was carried out at different temperatures (40–60 °C), pressures (100–200 bar), and ethanol contents (0.0–5.0 wt. %) to study triterpenic acids (TTAs) recovery. A factorial design of experiments and response surface methodology were implemented to analyze the influence of these variables upon extraction and perform its optimization. The best conditions were 200 bar, 40 °C and 5% ethanol, for which the statistically validated regression models provided: extraction yield of 1.2% (wt.), TTAs concentration of 50%, which corresponds to TTAs yield of 5.1 g/kg of bark and a recovery of 79.2% in comparison to the Soxhlet value. The trends of the free and acetylated TTAs were very different, due to their distinct CO₂-philic character caused by dissimilar polarities: the acetyl derivatives approached a plateau near 200 bar and 5% ethanol, while the free TTAs extraction always increased in the range of conditions studied.     

Analysis of CO2–NH3 reaction dynamics in an aqueous phase by PCA and 2D IR COS

Both carbamation and bicarbonation are of prime importance in the absorption reactions of CO₂ in an aqueous NH₃ solution, as they are related to the CO₂ working capacity, regeneration energy, and the critical problem of blocking the gas pathway for the CO₂ capture process. Herein, the influence of reaction temperature on the CO₂ and NH₃ reaction in an aqueous solution is demonstrated by a principal component analysis (PCA) and a two dimensional correlation analysis (2D IR COS) obtained from FT-IR, dependent on the reaction time. In contrast to the reaction at 298 K, conversion of the dominant reaction from carbamation to bicarbonation and respective conformational changes were observed at 278 K by PCA and 2D IR COS. The PCA results elucidate that two major reactions following the dependence of reaction time were divided into two regions, I and II. The turnover point was subsequently tracked in these two regions, where precipitation of ammonium bicarbonate occurred due to the limitation of solubility at this turning point. The interrelation and sequential variation of conformations in regions I and II were investigated by synchronous and asynchronous 2D correlation analyses. The combination of PCA and 2D IR COS provides a powerful and useful analytic method to capture and monitor the dynamics of complex chemical reactions.     

Supercritical CO2 oilseed extraction in multi-vessel plants. 2. Effect of number and geometry of extractors on production cost

The objective of this work was to study production costs for the supercritical CO₂ extraction of a pre-pressed oilseed (packed bed with 2-mm particles) in a 2-m³ industrial multi-vessel plant operating at 40 °C and 30 MPa, using a fully predictive mass transfer model to simulate the process. We modified the inner diameter (47.3 ≤ D ≤ 65.6 cm) and number (n = 2, 3, or 4) of extraction vessels, and the mass flow rate of CO₂ (Q = 3000 or 6000 kg/h), thus changing the aspect ratio of the extraction vessels (3 ≤ L/D ≤ 8), and superficial velocity (2.71 ≤ U ≤ 10.8 mm/s) and specific mass flow rate (6 ≤ q ≤ 24 kg/h per kg substrate) of CO₂. Production cost decreased when increasing the mass flow rate of CO₂ or the number of extraction vessels (or when increasing q). Production cost did not depend on the geometry of extraction vessel for a constant specific mass flow rate of CO₂, but it decreased with a decreasing of the L/D ratio of the vessel for a constant superficial velocity of CO₂. For any given plant, the contribution of fixed cost items (capital, labor) to the production cost increased with extraction time, unlike that of variable cost items (substrate, CO₂, energy), which decreased. Thus, there was an optimal extraction time that minimized production cost for each plant. This work proposes an expression for capital cost of an industrial multi-vessel plant as a function of the mass flow rate of CO₂ (which defines the cost of the solvent cycle of the plant), and the volume of the extraction vessels (which together with number of extraction vessels define the cost of extraction section of the plant), with a scaling factor of 0.48 for both items. Under optimal conditions, capital cost represented 30–40% of the production cost, but uncertainties in capital cost estimates (about ±50% using the proposed expression) may largely affect these estimates. The lowest production cost estimated in this work was USD 7.8/kg oil for the extraction of prepressed oilseed in a four-vessel plant using 6000 kg/h of CO₂. The mass flow rate of CO₂ and number of extraction vessels also affected annual productivity that was about 360 ton oil for the same plant operating 7200 h per year. Oil yields were above 90% for both three- and four-vessel plants.     

Phase equilibria of allyl sulfide + carbon dioxide binary mixtures: Experimental data and thermodynamic modeling

This contribution reports new experimental data on vapor–liquid equilibrium of the binary system diallyl sulfide + carbon dioxide, at temperatures between 275 and 370 K and pressures up to 12 MPa. These data are of interest to study the extraction of Allium oils from garlic and onion, using near-critical CO₂. The experimental data were modeled with a group-contribution equation of state. A (CH₂S) functional group has been defined to represent alkyl and allyl sulfides. Pure group and binary interaction parameters for this new functional group have been determined. Good correlation and prediction of phase equilibrium conditions were obtained.     

Prediction of phase equilibrium of CO2/cyclic compound binary mixtures using a rigorous modeling approach

Vapor liquid equilibrium (VLE) data has significant role in designing processes which include vapor and liquid in equilibrium. Since it is impractical to measure equilibrium data at any desired temperature and pressure, particularly near critical region, thermodynamic models based on equation of state (EOS) are usually used for VLE estimating. In recent years due to the development of numerical tools like artificial intelligence methods, VLE prediction has been find new alternatives.In the present study a novel method called Least-Squares Support Vector Machine (LSSVM) used for predicting bubble/dew point pressures of binary mixtures containing carbon dioxide (CO₂) + cyclic compounds as function of reduced temperature of the system, critical pressure, acentric factor of the cyclic compound, and CO₂ composition. A 333 binary equilibrium data points of CO₂ and six cyclic compounds within temperature and pressure ranges of 308.15–473.15 K and 0.5–27.71 MPa were used to develop the model. Results show that the proposed model is able to predict VLE data for binary systems containing supercritical or near-critical CO₂/cyclic compounds with an acceptable average absolute relative deviation percent (AARD%) of 3.9381% and the coefficient of determination (R²) value of 0.9980. For detection of the probable doubtful experimental data, and applicability of the model, the Leverage statistical approach performed on the data sets. This algorithm showed that the proposed LSSVM model is statistically valid for VLE prediction and the whole phase equilibrium data points are in applicability domain of the model.